【発明の詳細な説明】[Detailed description of the invention]
本発明は、水不溶性黒色分散染料組成物及びそ
れらの染料組成物を用いたポリエステル系繊維の
染色あるいは捺染方法に関する。
更に詳しくは、本発明は全染料原末に対して、
式（）
で示される染料30〜50重量％、
式（）
で示される染料40〜60重量％、
式（）
で示される染料３〜15重量％、
及び必要に応じて一般式（）
〔式（）中、Ｘは塩素又は臭素原子を表す〕
で示される染料０〜20重量％の割合で配合してな
るポリエステル繊維用黒色分散染料組成物、及び
これを用いた染色またはその捺染方法である。
前記式（）〜式（）で示される染料は、ブ
ルー、バイオレツト、またはイエローブラウン系
の公知染料または類似染料である。
ポリエステル系繊維の染色に分散型水不溶性染
料を使用することはよく知られているが、ポリエ
ステル系繊維を黒色に染色する単品の分散染料は
現在知られていないため、一般には黄、青、赤、
茶色などの分散染料を適当に色合わせした配合染
料が使用されている。しかしながら、濃黒色に染
色できる満足なものは殆どない。
本発明は、ポリエステル繊維を良好な耐光堅牢
度、耐昇華堅牢度、耐洗濯堅牢度、耐水堅牢度、
耐摩擦堅牢度を有する黒色に染色し、かつ、特に
捺染染色時における染料による機内昇華性が小さ
く、又は、染色後の洗浄時の白場汚染性の少ない
染料組成物及びそれを用いた染色法を提供するも
のである。
ポリエステル繊維の染色物は、耐光性、耐昇華
性が良好であることは勿論であるが、近年、更に
各種の後続加工を行つた後の染色物の耐洗濯堅牢
度、耐水堅牢度、耐摩擦堅牢度が良好であること
が要求されるようになつた。
しかし、これらの堅牢度は、染料が単品である
場合と、数種からなる配合品である場合とでは、
異なる挙動を示すことが多く、特に黒色を配合品
で出す必要があるポリエステル用染料では、配合
の組み合わせが重要な問題である。
他方、配合染料を用いた時には、各単体の染料
の場合と異なつた染着挙動をするために、捺染時
における染着率や、染料による白地部分への汚染
である機内昇華性、又、捺染後の末染着染料を洗
浄する時に、染色物の白地部分の汚染性（白場汚
染性）が問題となり、特に、近年、被染物の品位
向上を目指すうえで上記２点は重要なチエツクポ
イントとなつているが、市場の要求を充分に満足
するものはいまだ見い出されていない。
そこで、本発明者らは、これらの問題、特に捺
染時の汚染性について鋭意検討の結果、前記構造
式（），（），（）、及び（）で示されるそ
れぞれの染料を特定組成比で配合することによ
り、各種堅牢度が優れ、しかも捺染時に汚染性の
ない配合染料の開発に成功した。
また、この配合染料は高い染着率を有するの
で、染色後の洗浄工程における洗浄水を削減でき
るという、省エネルギー・省資源にも貢献でき
る。
本発明の黒色染料組成物は、使用する全染料原
末に対し、前記式（）で示される染料30〜50重
量％、式（）で示される染料40〜60重量％、式
（）で示される染料３〜15重量％の割合で配合
すればよく、特に望ましい黒色染色物を得るため
には、式（）で示される染料が35〜45重量％、
式（）で示される染料が45〜55重量％、式
（）で示される染料が５〜10重量％の割合の配
合がよい。
また、前記式（）で示される染料は、本発明
では黒色の調色成分として使用されるものであ
り、従つて必ずしも必要ではなく、所望の色調に
応じて、式（）、式（）、式（）で示される
染料の組成比に合わせて、０〜20重量％の範囲内
で式（）で示される染料の配合比は自由に選択
できる。
本発明で用いる式（）〜式（）で示される
染料は、公知アゾ染料もしくはその類似のアゾ染
料であり、容易に入手もしくは常法に従つて製造
できる。
本発明の実施にあたつては、配合に供する各染
料のプレスケーキを適当な分散剤と共に水性媒体
中で微粒化分散し、そのまま液状であるいはスプ
レー乾燥法等により粉末状とした後、所定の割合
に配合して黒色染料組成物とするのが有利であ
る。
このようにして得られた染料組成物を用いてポ
リエステル系繊維を染色するには、加圧下105℃
以上、好ましくは110〜140℃で染色する方法、ｏ
−フエニルフエノール等のキヤリアーの存在下に
比較的高温、例えば水の沸点で染色する方法、あ
るいは染料分散液を布にパデイングし、150〜230
℃で30〜60秒乾熱処理を行う方法（サーモゾル
法）等が挙げられる。
一方、捺染を行う場合には、染料組成物をグア
ガムやローカストビーンガム等の適当な糊剤と共
に練り合わせ、これを布に印捺して、スチーミン
グ又はサーモゾル法で処理して目的を達する。
以下、本発明の効果を表１によつて説明する。
表１は本発明染料組成物の実施例及び比較例と
しての市販染料を使用して捺染した結果を示した
ものである。
表１から明らかなように本発明の配合染料は、
いずれも比較例としての市販染料より各種堅牢度
が優れており、特に機内昇華性、白場汚染性が少
ないことがわかる。
The present invention relates to water-insoluble black disperse dye compositions and methods for dyeing or printing polyester fibers using these dye compositions. More specifically, the present invention applies to all dye powders,
formula() 30-50% by weight of dye, denoted by formula () 40-60% by weight of the dye, denoted by the formula () 3 to 15% by weight of the dye represented by the formula (), and if necessary, the general formula () [In formula (), X represents a chlorine or bromine atom]
A black disperse dye composition for polyester fibers containing a dye represented by the following formula in a proportion of 0 to 20% by weight, and a dyeing or printing method using the same. The dyes represented by formulas () to () above are known blue, violet, or yellow-brown dyes or similar dyes. Although it is well known that dispersed water-insoluble dyes are used to dye polyester fibers, there are currently no single disperse dyes known for dyeing polyester fibers black, so dyes such as yellow, blue, and red are generally used. ,
A blended dye is used, which is a suitably color-matched mix of disperse dyes such as brown. However, there are almost no satisfactory products that can be dyed deep black. The present invention provides polyester fibers with good light fastness, sublimation fastness, washing fastness, water fastness,
A dye composition that dyes black with abrasion fastness and has low in-machine sublimation, especially during textile dyeing, or has low spot staining when washed after dyeing, and a dyeing method using the same. It provides: It goes without saying that dyed polyester fibers have good light fastness and sublimation resistance, but in recent years, the washing fastness, water fastness, and abrasion resistance of dyed products after various subsequent processing have also increased. Good fastness is now required. However, these fastnesses differ depending on whether the dye is a single dye or a combination of several dyes.
For polyester dyes, which often exhibit different behavior and, in particular, need to produce a black color in the formulation, formulation combinations are an important issue. On the other hand, when blended dyes are used, their dyeing behavior is different from that of each individual dye, so the dyeing rate during printing, the in-machine sublimation (contamination of the white background by the dye), and the printing When cleaning the final dye after dyeing, staining of the white area of the dyed product (white area staining) becomes a problem, and in recent years, the above two points have become important points to check in order to improve the quality of the dyed item. However, no one has yet been found that fully satisfies the market requirements. Therefore, as a result of intensive studies on these problems, especially staining during printing, the present inventors have determined that each dye represented by the above structural formulas (), (), (), and () can be used at specific composition ratios. By blending them, we succeeded in developing a blended dye that has excellent fastness properties and does not cause staining during printing. Furthermore, since this blended dye has a high dyeing rate, the amount of washing water used in the washing process after dyeing can be reduced, contributing to energy and resource saving. The black dye composition of the present invention contains 30 to 50% by weight of the dye represented by the formula (), 40 to 60% by weight of the dye represented by the formula (), and 40 to 60% by weight of the dye represented by the formula (), based on the total dye powder used. The dye represented by the formula () may be blended in an amount of 35 to 15% by weight, and in order to obtain a particularly desirable black dyed product, the dye represented by the formula (
It is preferable to mix the dye represented by the formula () in a proportion of 45 to 55% by weight and the dye represented by the formula () in a proportion of 5 to 10% by weight. In addition, the dye represented by the formula () is used as a black toning component in the present invention, and therefore is not necessarily required, and may be used depending on the desired color tone. The blending ratio of the dye represented by formula () can be freely selected within the range of 0 to 20% by weight, depending on the composition ratio of the dye represented by formula (). The dyes represented by formulas () to () used in the present invention are known azo dyes or similar azo dyes, and can be easily obtained or produced according to conventional methods. In carrying out the present invention, the presscake of each dye to be blended is atomized and dispersed in an aqueous medium together with an appropriate dispersant, and then either left as it is in liquid form or powdered by spray drying, etc. Advantageously, they are blended in proportions to form a black dye composition. In order to dye polyester fibers using the dye composition obtained in this way, it is necessary to dye the dye composition at 105°C under pressure.
The above is preferably a method of dyeing at 110 to 140°C, o
- A method of dyeing at a relatively high temperature, e.g. the boiling point of water, in the presence of a carrier such as phenylphenol, or by padding the fabric with a dye dispersion,
Examples include a method of performing dry heat treatment at ℃ for 30 to 60 seconds (thermosol method). On the other hand, in the case of printing, the dye composition is kneaded with a suitable thickening agent such as guar gum or locust bean gum, and this is printed on cloth and treated by steaming or thermosol method to achieve the purpose. The effects of the present invention will be explained below with reference to Table 1. Table 1 shows the results of printing using Examples of the dye composition of the present invention and commercially available dyes as comparative examples. As is clear from Table 1, the blended dye of the present invention is
It can be seen that all of the dyes are superior in various fastness properties to the commercially available dyes used as comparative examples, and in particular have less in-machine sublimation and spot staining.
〔実施例 １〕[Example 1]
前記式（）の染料原体10.5部を、デモールＮ
（花王アトラス社製品）９部、及び水18部と共に
微粒化分散し、配合成分(A)を調整した。同じく前
記式（）の染料原体15部を、デモールN10部、
及び水35部と共に微粒化分散し、配合成分(B)を、
また前記式（）の染料原体1.5部を、デモール
N3部と水６部と共に微粒化分散し、配合成分(C)
をそれぞれ別々に調整した。さらに前記式（）
の染料のうち、Ｘが臭素原子である染料原体３部
を、デモールN3部と水６部と共に微粒化分散し、
配合成分(D)を調整し、これらの配合成分(A)、(B)、
(C)、および(D)を配合して黒色染料組成物120部を
得た。
この黒色染料組成物100部に水200部を加えた後
Ｏ／Ｗ型エマルジヨン糊280部、メイプロガム
NP（加工・ローカストビーン系ガムMAYHALL
社製品）12％ペースト420部と共に練り合わせ、
ポリエステル繊維上に印捺し、175℃で８分間高
温スチーミングを行つた。
その後、染色物をソーダ灰３部、ハイドロサル
フアイト３部、スコアロール400（ノニオン型界面
活性剤、花王アトラス社製品）1.5部と水3000部
よりなる浴中で65℃、10分間還元洗浄処理を行
い、水洗、乾燥して濃度の高い黒色染色物が得ら
れた。
捺染物は還元洗浄時の白場汚染性、発色時の機
内昇華汚染性等が極めて少なく、また、耐光、昇
華、水、洗濯等の諸堅牢度は優秀であつた。
〔実施例 ２〕
前記式（）の染料のＸが、塩素原子である染
料原体を用いて配合成分(E)を調整したほかは、実
施例１と全く同じ配合組成比、配合成分よりなる
(A)，(B)，(C)，(E)の四成分の配合黒色染料組成物
120部を得た。
この黒色染料組成物100部を用いて実施例１と
同様にして捺染したら、還元洗浄時の白場汚染、
発色時の機内昇華の少なく、耐光、昇華、水、洗
濯等の諸堅牢度の優れた黒色捺染物が得られた。
〔実施例 ３〕
前記式（）の染料原体13.5部を、デモール
N12部および水24部と共に微粒化分散し、配合成
分(F)を調整した。これに、前記式（）の染料原
体13.5部を、デモールN10部および水35部と共に
微粒化分散して調整した配合成分(G)及び、前記式
（）の染料原体３部を、デモールN3部と水６部
と共に微粒化分散して調整した配合成分(H)を配合
して、(F)，(G)，(H)の３成分よりなる黒色染料組成
物100部を得た。
これを用いて実施例１と同様にして捺染した
ら、還元洗浄時の白場汚染、発色時の機内昇華が
少なく、耐光、昇華、水、洗濯等の諸堅牢度の優
れた黒色捺染物が得られた。
〔実施例 ４〕
実施例１で得られる黒色染料組成物10部を高級
アルコール硫酸エステル３部を含む水3000部中に
均一に分散させて染浴を調整する。
次いでテトロンスパン糸100部を浸漬し、130℃
で60分間染色後、染色物をカセイソーダ３部、ハ
イドロサルフアイト３部、ベタイン型両性界面活
性剤３部と水3000部よりなる浴中で65℃で10分間
還元洗浄処理を行い、水洗、乾燥して濃度の高い
黒色染色物が得られた。
本染色物は耐光、昇華、水等の諸堅牢度が優れ
ていた。
10.5 parts of the dyestuff of formula () above was added to Demol N
(Kao Atlas Co., Ltd. product) and 18 parts of water were atomized and dispersed to adjust the blended component (A). Similarly, 15 parts of the dyestuff of the formula () above, 10 parts of Demol N,
and 35 parts of water to atomize and disperse the compounded component (B).
In addition, 1.5 parts of the dyestuff of the formula () above was added to Demol.
Atomized and dispersed with 3 parts of N and 6 parts of water, compounded component (C)
were adjusted separately. Furthermore, the above formula ()
Among the dyes, 3 parts of the dye base material in which X is a bromine atom are atomized and dispersed together with 3 parts of Demol N and 6 parts of water,
Adjust the compounding ingredient (D) and add these compounding ingredients (A), (B),
(C) and (D) were blended to obtain 120 parts of a black dye composition. After adding 200 parts of water to 100 parts of this black dye composition, 280 parts of O/W type emulsion glue, Mappro gum
NP (processed/locust bean gum MAYHALL
Knead with 420 parts of 12% paste,
It was printed on polyester fiber and subjected to high temperature steaming at 175°C for 8 minutes. Thereafter, the dyed material was subjected to reduction cleaning treatment at 65°C for 10 minutes in a bath consisting of 3 parts of soda ash, 3 parts of hydrosulfite, 1.5 parts of Score Roll 400 (nonionic surfactant, a product of Kao Atlas Co., Ltd.) and 3000 parts of water. After washing with water and drying, a highly concentrated black dyed product was obtained. The printed material had extremely low white spot staining during reduction washing and in-machine sublimation staining during color development, and was excellent in light fastness, sublimation, water fastness, washing fastness, etc. [Example 2] The composition ratio and ingredients were exactly the same as in Example 1, except that the compounding component (E) was adjusted using a dye base material in which X of the dye of formula () is a chlorine atom.
Black dye composition containing four components (A), (B), (C), and (E)
Got 120 copies. When printing was carried out in the same manner as in Example 1 using 100 parts of this black dye composition, there was no white area staining during reduction cleaning.
A black printed product was obtained with little in-machine sublimation during color development and excellent fastness to light, sublimation, water, washing, etc. [Example 3] 13.5 parts of the dyestuff of the above formula () was added to Demol.
It was atomized and dispersed with 12 parts of N and 24 parts of water to adjust the blended component (F). To this, blended component (G) prepared by atomizing and dispersing 13.5 parts of the dyestuff of the formula () above with 10 parts of Demol N and 35 parts of water, and 3 parts of the dyestuff of the formula () were added to Demol. Component (H) prepared by atomization and dispersion was blended with 3 parts of N and 6 parts of water to obtain 100 parts of a black dye composition consisting of the three components (F), (G), and (H). When this was used for printing in the same manner as in Example 1, a black printed product was obtained with less white field contamination during reduction washing, less in-machine sublimation during color development, and excellent fastness to light, sublimation, water, washing, etc. It was done. [Example 4] A dye bath is prepared by uniformly dispersing 10 parts of the black dye composition obtained in Example 1 in 3,000 parts of water containing 3 parts of higher alcohol sulfate. Next, 100 parts of Tetron spun yarn was immersed at 130°C.
After dyeing for 60 minutes, the dyed product was subjected to a reduction cleaning treatment at 65°C for 10 minutes in a bath consisting of 3 parts caustic soda, 3 parts hydrosulfite, 3 parts betaine type amphoteric surfactant, and 3000 parts water, washed with water, and dried. A black dyed product with high density was obtained. This dyed product had excellent light fastness, sublimation fastness, water fastness, etc.