CN106120388B - 高固着数码纺织印花墨水组合物 - Google Patents

高固着数码纺织印花墨水组合物 Download PDF

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CN106120388B
CN106120388B CN201610097770.1A CN201610097770A CN106120388B CN 106120388 B CN106120388 B CN 106120388B CN 201610097770 A CN201610097770 A CN 201610097770A CN 106120388 B CN106120388 B CN 106120388B
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陈小山
李传喜
陈建宇
吴姉依
杨翾
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Everlight Chemical Industrial Corp
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Abstract

一种新颖的高固着数码纺织印花墨水组合物,包括:(A)至少一个双活性基的反应性染料化合物,含量为1至50重量百分比;(B)一有机缓冲剂,含量为0.05至10重量百分比;(C)一墨水保湿剂,含量为10至50重量百分比;以及(D)余量溶剂。上述的高固着数码纺织印花墨水组合物可适用于织物上的数码喷印应用,并具有优异固着率等优势。

Description

高固着数码纺织印花墨水组合物
技术领域
本发明涉及一种新颖的高固着数码纺织印花墨水组合物,尤其涉及一种包含双活性基反应性染料的高固着数码纺织印花墨水组合物。
背景技术
数码喷印的技术逐渐受到重视,而目前用于数码纺织喷印的墨水是以传统的单反应基染料进行配制,然而在沿用传统的染料时,单反应基染料对织物的反应性较弱,也会有上色不均及染色固着率不佳等缺点,一般而言,包含单反应基染料的印花墨水只有50%至70%的固着率,因为固着率低,导致有30~50%未固着的染料被洗除,有色废水在后续的废水处理程序相当繁复。
此外,大多数的反应性染料的反应基团为卤素基团或尼古丁酸,容易水解造成印花墨水的pH值降低,使得储存稳定性不佳,因此,进而影响印花墨水的储存以及使用期限。
因此,目前亟需一种具有高pH质稳定性、高固着率、以及高染色浓度特性的高固着数码纺织印花墨水组合物,可应用在纺织织物的数码喷印。
发明内容
本发明的目的在于提供一种新颖高固着数码纺织印花墨水组合物,其所包含的染料化合物具有两个反应基团,故反应性高,此外,本发明的高固着数码纺织印花墨水组合物适用于数码喷印技术,且具有pH值稳定性高、储存安定性好,以及改善染料的固着率等,减少有色污水等特性。
为了达到上述的目的,本发明所提供的高固着数码纺织印花墨水组合物包括:(A)至少一由式(I)所示的反应性染料化合物,含量为1至50重量百分比;(B)一有机缓冲剂,含量为0.05至10重量百分比;(C)一墨水保湿剂,含量为10至50重量百分比;以及(D)余量溶剂;
其中,A1为染料发色基团;X1及X2各自独立为离去基;C1为未经取代或经磺酸基或羟基取代的苯环;R1、R2、R3及R4各自独立为氢、未经取代或经取代的C1-6烷基;以及n1为1或2。
在本发明的一实施方式中,式(I)所示的反应性染料化合物中,A1可为本领域中已知的染料发色基团,并无特别的限制。举例而言,A1可为表1中式(I-1)至(I-34)所示的染料发色基团,其颜色如表1所示:
表1
根据本发明的一优选实施方式,式(I)所示的反应性染料化合物中,染料发色基团A1优选可为式(I-1)至(I-5)所示的基团;而X1及X2优选可为卤素或尼古丁酸基。
再则,根据本发明的一实施方式,式(I)所示的反应性染料化合物中,X1及X2优选可为氯(Cl);C1优选可为经磺酸基取代的苯环;R1、R2、R3及R4优选可为氢。当X1及X2为氯时,式(I)所示的反应性染料化合物具有两个一氯均三嗪(monochlorotriazine)反应基。
另外,根据本发明的另一优选实施方式,该高固着数码纺织印花墨水组合物中:(A)至少一由式(I)所示的反应性染料化合物的含量优选可为3至45重量百分比;(B)该有机缓冲剂的含量优选可为0.1至8重量百分比;(C)该墨水保湿剂的含量优选可为10至35重量百分比;以及(D)余量溶剂。
根据本发明另一实施方式,该反应性染料化合物由式(II)所示:
其中,A1为染料发色基团;以及n1及n2各自独立为1或2。
在本发明的一实施方式中,式(II)所示的反应性染料化合物中,A1可为本领域中已知的染料发色基团,并无特别的限制。举例而言,A1亦可为表1中式(I-1)至(I-34)所示的染料发色基团,其颜色如上述表1所示。而其中,A1又以式(I-1)至(I-5)所示的染料发色基团为优选。另外,在式(II)中,n2优选可为1。
接着,在本发明的高固着数码纺织印花墨水组合物中,由于式(I)或式(II)所示的该反应性染料化合物包括两个卤素基团(如Cl)作为反应基,容易在水解形成后造成pH下降,因此,该有机缓冲剂可稳定墨水组合物的pH值,而该有机缓冲剂可为3-(N-吗啉基)丙烷磺酸(3-(N-morpholino)propanesulfonic acid,MOPS)、N,N-二乙基氨基苯磺酸(N,N-diethylsulphanilic acid,DEAS)、多聚磷酸盐(Polyphosphate)、或N,N-二(2-羟乙基)-2-氨基乙磺酸(N,N-bis(2-Hydroxyethyl)-2-aminoethanesulfonic acid;BES)或其盐类。其中,BES的结构如下式(III)所示:
在本发明的高固着数码纺织印花墨水组合物中,该墨水保湿剂可为本领域中已知的任何一种墨水保湿剂,举例而言,例如可以为乙二醇、二乙二醇、三乙二醇、多伸乙二醇、四乙二醇、丙二醇、多伸丙二醇、1,3-丙二醇、丙三醇、硫乙二醇等多元醇类,如乙二醇单乙醚、乙二醇单丁醚、一缩二(乙二醇)单丁醚、一缩二(丙二醇)单乙醚、二缩三(乙二醇)单甲醚、二乙二醇醚、1,2-己二醇等的多元醇醚类,如丙酮、甲基乙基酮等的酮类,如己内酰胺、N,N-二乙基甲酰胺、N,N-二甲基乙酰胺等的酰胺类,如2-吡咯烷酮、2-吡咯啶酮、N-甲基-2-吡咯啶酮、N-乙烯-2-吡咯啶酮、1,3-二甲基-2-四氢咪唑酮等的含氮化合物,如四氢呋喃、二氧六环等的醚类,如甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇等的醇类等。其中,又以丙二醇、二乙二醇醚、1,2-己二醇、2-吡啶酮、或其混合物为优选。
再则,在本发明的高固着数码纺织印花墨水组合物中,该溶剂可为本领域中常用的溶剂,而其中,优选为水。
另外,在本发明的一优选实施方式中,该高固着数码纺织印花墨水组合物还可以包括一表面活性剂,其含量可为0.1至2重量百分比。本发明中所使用的表面活性剂可为本领域中已知的表面活性剂,并无特别的限制,然而优选可为炔二醇基表面活性剂、烷氧基化物表面活性剂、或非离子型聚合物的含氟表面活性剂。举例而言,炔二醇基表面活性剂的具体实例,包括:Surfynol 485、Surfynol 465、Surfynol 440、Surfynol 420、Surfynol 104(Air Products&Chemicals,Inc.所贩售);烷氧基化物表面活性剂的具体实例,包括:Tergitol 15-S-5、Tergitol 15-S-7、Tergitol 15-S-9(Dow Chemical Company所贩售);非离子型聚合物的含氟表面活性剂的具体实例,包括FC-4430(3M所贩售),但本发明不受限于此。
在本发明的一优选实施方式中,该高固着数码纺织印花墨水组合物还可以包括一抑菌剂,其含量可为0.1至0.3重量百分比。本发明中所使用的抑菌剂可为本领域中已知的抑菌剂,并无特别的限制,然优选可为NUOSEPT(Nudex Inc.,a division of HulsAmerical所贩售)、UCARCIDE(Dow Chemical Company所贩售)、VANCIDE(RT Vanderbilt Co.所贩售)、或PROXEL(ICIAmericas所贩售)。
本发明的高固着数码纺织印花墨水组合物优选适用于数码印花喷印技术,且印制在常见的纤维材料上。纤维材料可为本领域常见的材料,而其中优选为天然纤维素纤维及其再生纤维,例如棉麻、嫘萦、蚕丝、羊毛及其混织物等。
本发明所提供的高固着数码纺织印花墨水组合物,由于含有有机缓冲剂,故可降低反应性染料的反应基在储存后水解的现象,因而解决染色力度衰退的问题,具备优良上色强度,其储存安定性高、不易析出,以及印染安定性良好。此外,由于本发明的高固着数码纺织印花墨水组合物中的反应性染料化合物包括两个反应基,故具有高度的纤维-染料结合稳定性,因此,使用本发明的高固着数码纺织印花墨水组合物,经数码喷印印染而获得的印花布,具有优异的综合性能,如具有优异的日光牢度、耐湿摩擦牢度、耐水牢度、耐氯漂牢度、耐交染牢度等。也由于该高固着数码纺织印花墨水组合物优异的反应性,可减少数码喷印所产生的废水,以达到环保及节能的目的。
具体实施方式
以下通过特定的具体实施例说明本发明的实施方式。本说明书中的各项细节亦可基于不同观点与应用,在不悖离本发明的精神下进行各种修饰与变更。实施例仅是为了方便说明而举例而已,本发明的申请专利范围并不会因此而受限制。若无特别注明,则温度为摄氏温度,份数及百分比以重量计。
实施例1
取9份的反应性染料化合物,其由下式(i-1)所示、23份保湿剂(包括8份2-吡啶酮以及15份二乙二醇醚)、1.5份非离子型表面活性剂Surfynol 465、1份的缓冲剂,由以下式(III)所示、0.2份的杀菌剂Proxel XII、以及65.3份的水,在室温下搅拌混合,以制备本实施例的黄色反应性印花墨水。
比较例1
本比较例的黄色反应性印花墨水的制备方法与实施例1大致相同,其不同在于所使用的反应性染料化合物为式(i-2)所示的CI.Reactive Yellow95。
测试例1
本测试例是测量上述实施例1及比较例1所制备的黄色反应性印花墨水的粘度、pH值、UV/吸收值、以及其表面张力,其测量结果如比较表2所示。
另外,本测试例亦评估了实施例1及比较例1的黄色反应性印花墨水的固着率,其测量方法如下:使用桌上型印表机Epson XP-202,且使用同一喷头在两块棉布上喷印相同大小色块。列印完毕后,测量其中一块未经蒸处的棉布墨水浓度作为原始喷印浓度(a)。另一棉布在喷印后进行蒸处水洗处理,其步骤包括:墨水喷印至棉布上后烘干10分钟,蒸处10分钟,接着将棉布和500g的水加热至沸腾,水洗10分钟后,测试该水洗液中的染料浓度(b),其固着率的计算方式如以下方程式所计算,其结果如表2所示:
固着率(%)=棉布上色浓度(a-b)/原始喷印浓度(a)×100%
表2
实施例2-1
取12份的反应性染料化合物,其由下式(ii-1)所示、11份保湿剂(包括3份的1,2-丙二醇、7份的二乙二醇醚、以及1份的丙三醇)、0.5份非离子型表面活性剂Surfynol 465、1份的缓冲剂,由式(III)所示、0.2份的杀菌剂Proxel XII、以及75.3份的水,分别在室温下搅拌混合,以制备本实施例的红色反应性印花墨水:
实施例2-2
取11.9份的反应性染料化合物,其由下式(ii-2)所示、11份保湿剂(包括10份的二乙二醇醚、以及1份的丙三醇)、0.5份非离子型表面活性剂Surfynol 465、1份的缓冲剂,由式(III)所示、0.2份的杀菌剂Proxel XII、以及75.4份的水,分别在室温下搅拌混合,以制备本实施例的红色反应性印花墨水:
比较例2-1
取12份的反应性染料化合物CI.Reactive Red 3:1(如下式(ii-3)所示)、21份保湿剂(包括12份的2-吡啶酮、8份的1,2-丙二醇、以及1份的丙三醇)、0.5份非离子型表面活性剂Surfynol 465、1份的缓冲剂,由式(III)所示、0.2份的杀菌剂Proxel XII、以及65.3份的水,分别在室温下搅拌混合,以制备本比较例的红色反应性印花墨水:
比较例2-2
取10.9份的反应性染料化合物CI.Reactive Red 245(如下式(ii-4)所示)、24份的保湿剂(包括12份的二乙二醇醚、11份的1,2-丙二醇、以及1份的丙三醇)、0.5份非离子型表面活性剂Surfynol 465、1份的缓冲剂,由式(III)所示、0.2份的杀菌剂Proxel XII、以及63.4份的水,分别在室温下搅拌混合,以制备本比较例的红色反应性印花墨水:
测试例2
本测试例是测量上述实施例2-1、2-2及比较例2-1、2-2所制备的红色反应性印花墨水的粘度、pH值、UV/吸收值、其表面张力、及其固着率,测量结果如比较表3所示,其中,固着率的测量方法与测试例1相同:
表3
实施例3
取6.5份的反应性染料化合物,其由下式(iii-1)所示、32份保湿剂(包括15份的1,2-丙二醇、15份的2-吡啶酮、以及1份的1,2-己二醇)、1份非离子型表面活性剂Surfynol465、1份的缓冲剂,由式(III)所示、0.2份的杀菌剂Proxel XII、以及59.3份的水,分别在室温下搅拌混合,以制备本实施例的蓝色反应性印花墨水:
比较例3
取4份的反应性染料化合物CI.Reactive Blue 176,其由下式(iii-2)所示、36份保湿剂(包括16份的1,2-丙二醇、18份的2-吡啶酮、以及2份的1,2-己二醇)、1份非离子型表面活性剂Surfynol 465、1份的缓冲剂,由式(III)所示、0.2份的杀菌剂Proxel XII、以及57.8份的水,分别在室温下搅拌混合,以制备本实施例的蓝色反应性印花墨水:
测试例3
本测试例是测量上述实施例3及比较例3所制备的蓝色反应性印花墨水的粘度、pH值、UV/吸收值、其表面张力、及其固着率,测量结果如比较表4所示,其中,固着率的测量方法与测试例1相同:
表4
实施例4
取8.9份的反应性染料化合物,其由下式(iv-1)所示、18份保湿剂(包括8份的2-吡啶酮、以及10份的二乙二醇醚)、1份非离子型表面活性剂Surfynol 465、0.1份的非离子型表面活性剂Tergitol 15-S-5、1份的缓冲剂,由式(III)所示、0.2份的杀菌剂Proxel XII、以及70.8份的水,分别在室温下搅拌混合,以制备本实施例的金黄色反应性印花墨水:
比较例4
取12.9份的反应性染料化合物C.I.Reactive Orange 12,其由下式(iv-2)所示、23份保湿剂(包括8份的2-吡啶酮、以及15份的二乙二醇醚)、1份非离子型表面活性剂Surfynol465、0.1份的非离子型表面活性剂Tergitol15-S-5、1份的缓冲剂,由式(III)所示、0.2份的杀菌剂Proxel XII、以及65.7份的水,分别在室温下搅拌混合,以制备本比较例的橘色反应性印花墨水:
测试例4
本测试例是测量上述实施例4及比较例4所制备的反应性印花墨水的粘度、pH值、UV/吸收值、其表面张力及其固着率,测量结果如比较表5所示,其中,固着率的测量方法与测试例1相同:
表5
通过以上实施例以及比较例的测试结果,可明显发现,由于本发明所提供的高固着数码纺织印花墨水组合物包括双活性基的反应性染料化合物,容易与织物反应键结,故其固着率皆提升至80%以上,明显优于比较例的单活性基反应性染料化合物。因此,本发明所提供的高固着数码纺织印花墨水组合物可减少印染有色污水的问题,达到降低成本的功效,且符合目前环保节能的趋势。

Claims (9)

1.一种高固着数码纺织印花墨水组合物,包括;
(A)至少一由式(I)所示的反应性染料化合物,含量为1至50重量百分比;
(B)一有机缓冲剂,含量为0.05至10重量百分比;
(C)一墨水保湿剂,含量为10至50重量百分比;以及
(D)余量溶剂;
其中,A1为染料发色基团;X1及X2各自独立为离去基;C1为未经取代或经磺酸基或羟基取代的苯环;R1、R2、R3及R4各自独立为氢、未经取代或经取代的C1-6烷基;以及n1为1或2;
其中,该染料发色基团选自由(I-1)至(I-27)、(I-29)至(I-34)所示的基团所组成的群组:
2.如权利要求1所述的高固着数码纺织印花墨水组合物,在式(I)中,X1及X2各自独立为卤素或尼古丁酸根。
3.如权利要求1所述的高固着数码纺织印花墨水组合物,其中,该由式(I)所示的反应性染料化合物为由式(II)所示的反应性染料化合物:
其中,A1为染料发色基团;以及n1及n2各自独立为1或2。
4.如权利要求3所述的高固着数码纺织印花墨水组合物,其中,该染料发色基团选自由(I-1)至(I-5)所示的基团所组成的群组:
5.如权利要求1所述的高固着数码纺织印花墨水组合物,其中,该有机缓冲剂选自由3-(N-吗啉基)丙烷磺酸、N,N-二乙基氨基苯磺酸、多聚磷酸盐、N,N-二(2-羟乙基)-2-氨基乙磺酸或其盐类、及其混合物所组成的群组。
6.如权利要求1所述的高固着数码纺织印花墨水组合物,其中,该墨水保湿剂选自由乙二醇、二乙二醇、三乙二醇、多伸乙二醇、四乙二醇、丙二醇、多伸丙二醇、1,3-丙二醇、丙三醇、硫乙二醇、乙二醇单乙醚、乙二醇单丁醚、一缩二(乙二醇)单丁醚、一缩二(丙二醇)单乙醚、二缩三(乙二醇)单甲醚、二乙二醇醚、1,2-己二醇、丙酮、甲基乙基酮、己内酰胺、N,N-二乙基甲酰胺、N,N-二甲基乙酰胺、2-吡咯烷酮、2-吡咯啶酮、N-甲基-2-吡咯啶酮、N-乙烯-2-吡咯啶酮、1,3-二甲基-2-四氢咪唑酮、四氢呋喃、1,4-二氧杂环己烷、甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇及其混合物所组成的群组。
7.如权利要求1所述的高固着数码纺织印花墨水组合物,其中,该溶剂为水。
8.如权利要求1所述的高固着数码纺织印花墨水组合物,还包括一表面活性剂,该表面活性剂选自炔二醇基表面活性剂、烷氧基化物表面活性剂或一种非离子型聚合物的含氟表面活性剂,该表面活性剂的含量为0.1至2重量百分比。
9.如权利要求1所述的高固着数码纺织印花墨水组合物,还包括一抑菌剂,其含量为0.1至0.3重量百分比。
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