CN1294327C - 涉及荧光增白剂的改进 - Google Patents
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Abstract
本发明涉及通式(I)的化合物作为荧光增白剂的应用,其中所有取代基的定义见权利要求,以及涉及荧光增白剂的新颖混合物。
Description
本发明涉及作为荧光增白剂的化合物的应用以及荧光增白剂的新混合物。
纸张和纸板制品的白度是最终产品的基本技术参数。造纸工业最重要的原材料是纤维素、纸浆和木素,它们自然吸收蓝光,从而呈现黄色,使纸张的外观灰暗。荧光增白剂用于造纸工业中,通过吸收最大波长为350-360nm的紫外光,并将其转化为最大波长440nm的可见蓝光,以补偿蓝光的吸收。
由于荧光增白剂的高效率,仅仅少量加入就能大大提高纸张的亮度。
荧光增白剂通常带有负电荷,其在许多情况下表现类似于直接染料。
不管是通过应用到纸浆,还是应用到纸张表面来增白纸张,所用增白剂几乎都属于三嗪基氨基茋类型。尽管施加到纸浆的三嗪基氨基茋增白剂的耐光性是中度的(在“Blue Wool Scale”上约为3),但公知的是这些增白剂在涂料中的的耐光性很差(在“Blue Wool Scale”上为1到最大1.5)(参见“Optische Aufheller-neuere Erkenntnissezu Eigenschaf ten und Verhalten im Papier”,F.Müller,D.Loewe和B.Hunke,Wochenblatt für Papierfabrikation 1991,6,191-203页)。因此要求保护增白的纸张,尤其是通过以表面涂料涂覆增白剂制备的纸张受光变黄。
三嗪基氨基茋增白剂一般通过以下3步法制备
其中所有取代基的定义如下。
制造商付出了极大的努力,以保证最终产品中剩余的卤三嗪(特别是氯三嗪)尽可能少,因为公知的是,这种中间体的存在降低了三嗪基氨基茋增白纸张的能力;增白剂中一般应含有少于1%的卤三嗪(特别是氯三嗪)。
令人吃惊地发现,卤三嗪(特别是氯三嗪)的存在保护增白的纸张不受光变黄。可能的解释是,在光的存在下,C-Cl键转化成C-O键,从而形成更有效的增白剂。这样,在增白剂被光破坏的同时,也受到光补充的影响。
因此,本发明涉及通式(I)的化合物,以及它们的混合物,作为荧光增白剂的应用。
其中
R1和R2互相独立地指H;卤素;未取代的C1-6烷基;取代的C1-6烷基和C1-6烷氧基,
每个B独立地指-O-或-NR3-,其中R3指H;未取代的C1-4烷基或取代的C1-4烷基,
X指卤素,优选F或Cl,更优选Cl,
Y指卤素;OR4;SR4或NR4R5,其中
R4指未取代的C1-6烷基;取代的C1-6烷基;未取代的苯基或取代的苯基;
R5指H;未取代的C1-6烷基或取代的C1-6烷基,或
R4和R5与它们所键合的氮原子一起形成吡咯烷基、哌啶基或吗啉基,
n和m相互独立地指0、1或2
每个M指阳离子。
烷基可以是直链或支化的。
对于烷基优选的取代基是卤素、-OH、-COOH、-CONH2、SO3H和-CN。
对于苯基优选的取代基是C1-4烷基、C1-4烷氧基、-SO3H、-COOH、-SO2NH2或卤素。
优选的采用根据通式(I)的化合物,以及它们的混合物,其中
R1和R2互相独立地指H;Cl;F;未取代的C1-2烷基;取代的C1-2烷基和C1-2烷氧基,
每个B独立地指-O-或-NR3-,其中
R3指H;未取代的C1-2烷基或取代的C1-2烷基,
X指F或Cl,
Y指Cl;F;OR4;SR4或NR4R5,其中
R4指未取代的C1-6烷基;取代的C1-6烷基;未取代的苯基或取代的苯基;
R5指H;未取代的C1-6烷基或取代的C1-6烷基,或
R4和R5与它们所键合的氮原子一起形成吡咯烷基、哌啶基或吗啉基,
n和m相互独立地指0、1或2,
每个M指阳离子。
合适的阳离子M是碱金属、碱土金属、铵、链烷醇铵或烷基铵阳离子。阳离子的实例是钠、锂或铵阳离子或一-、二-或三乙醇铵阳离子。
通式(I)的荧光增白剂可以任何商购形式使用,例如可溶于水的粉状或颗粒状,它们也可以直接生产的含水分散体或水溶液形式使用。
通式(I)的化合物适用于荧光增白天然和再生的纤维素纤维、天然和合成的聚酰胺和聚氨酯纤维、纺织品和纸张。为了荧光增白,通式(I)的化合物可固定在材料上,或掺入材料中。在纸张上获得了特别有价值的增白效果。
通式(I)的荧光增白剂可通过在纸页形成前加入纸料中施用,或掺入涂料组合物中,并最终施用到纸页上。尤其有效的是掺入涂料组合物中。因此本发明还提供包含通式(I)的荧光增白剂和常用的其它涂料成分,特别是填料和/或颜料,和任选的树脂和/或粘合剂,和任选的表面活性剂的涂料组合物,其中这些常用成分可具体地以涂料组合物中常采用的浓度使用。
涂料组合物可通过任何常用的方法,例如通过气刀、刮板、刷、辊、涂覆棒或在施胶机(size-press)上施用于纸张。
增白剂的应用可包括用化合物的溶液,特别是水溶液浸渍所要增白的材料,然后使已浸渍材料在其上干燥。也可以用分散体形式的本发明的产物,例如用诸如皂、类皂物质、脂肪醇的聚二醇醚、亚硫酸盐废液,或萘磺酸(可被烷基化)与甲醛的缩合产物的分散剂制备的分散体,处理材料。
作为荧光增白剂的优选应用的特征在于,应用至少一种上述通式(I)的化合物与至少一种通式(II)的化合物的混合物
其中所有取代基的定义如上,Z指OR4、SR4或NR4R5,其中R4和R5具有与以上定义相同的含义。
至少一种通式(I)的化合物与至少一种通式(II)的化合物的混合物包含约2wt%-95wt%通式(I)的化合物,优选5wt%-80wt%通式(I)的化合物。wt%以荧光增白剂的总量计。
在一个实施方案中,本发明混合物包含约2wt%-95wt%的通式(I)的化合物,优选5wt%-80wt%通式(I)的化合物和98wt%-5wt%通式(II)的化合物。
在另一个实施方案中,本发明混合物包含约5wt%-80wt%通式(I)的化合物和98wt%-20wt%通式(II)的化合物。
纸张还可包含本领域公知的控制亮度转化率的其它添加剂。这种添加剂的实例包括紫外线吸收剂,例如2,4-二羟基二苯酮;诸如“Fadex”(商标)F液和“Tinuvin”(商标)1130的苯并三唑紫外线吸收剂;抗坏血酸、抗坏血酸钠、乙二醇双硫代甘醇酸酯、S-甲基-1-硫代甘油、次磷酸钠、聚(乙二醇)和聚(四氢呋喃)。
纸张还可含有造纸工业中常用的其他添加剂。这种添加剂的实例包括施胶剂(例如松香、淀粉、烷基乙烯酮二聚物、链烯基琥珀酸酐)、湿强度树脂(例如聚氨基酰胺-表氯醇树脂)、助留剂和助滤剂(例如聚氯化铝、聚二烯丙基二甲基氯化铵),以及荧光增白剂。
以下实施例用于进一步描述本发明。实施例中的所有份和所有百分比均为重量,温度为摄氏度,除非另外指出。
实施例1
将21.3份苯胺-2,5-二磺酸和6.7份氢氧化钠在30份水中的溶液加入15.5份氰尿酰氯在50份冰水中的搅拌悬浮液中。通过滴加30%的氢氧化钠保持pH值为6。在10℃以下搅拌混合物,直到通过重氮化反应不再检测出伯芳族胺基。然后加入14.8份4,4’-二氨基茋-2,2’-二磺酸和3.2份氢氧化钠在20份水中的溶液,通过加入30%的氢氧化钠将pH值调节到6.5-7.5,在30℃下搅拌混合物,直至获得负性重氮化反应。加入5.3份L-天冬氨酸在10份16%氢氧化钠中的溶液,加热回流混合物6小时,通过加入碳酸钠保持pH在7.5-8.5。用水将溶液稀释到320份,得到以20/40/40的摩尔比含有通式(IIIa)、(IIIb)和(IIIc)的化合物的澄清溶液(SOLUTION A)
实施例2
将66.5份苯胺-2,5-二磺酸和21份氢氧化钠在100份水中的溶液加入48.4份氰尿酰氯在150份冰水中的搅拌悬浮液中。通过滴加30%的氢氧化钠保持pH值为6。在10℃以下搅拌混合物,直到通过重氮化反应不再检测出伯芳族胺基。然后加入46.3份4,4’-二氨基茋-2,2’-二磺酸和10.0份氢氧化钠在62.5份水中的溶液,通过加入30%的氢氧化钠将pH值调节到6.5-7.5,在30℃下搅拌混合物,直至获得负性重氮化反应。然后用80.0份甲醇处理搅拌的混合物,并加热回流2.5小时,通过滴加30%氢氧化钠保持pH值为8。冷却后过滤收集沉淀物,用甲醇洗涤并溶解在水中,得到320份以20/50/30的摩尔比含有通式(IVa)、(IVb)和(IVc)的化合物的澄清溶液(SOLUTION C)
实施例3
将14.8份4,4’-二氨基茋-2,2’-二磺酸和3.2份氢氧化钠在74份水中的溶液用1小时滴加到14.8份氰尿酰氯在125份丙酮与60份冰搅拌的溶液中。滴加完成后,通过加入碳酸钠将pH值调节到6-7。将搅拌混合物加热到室温,并保持pH值为6-7,直到通过重氮化反应不再检测出伯芳族胺基。然后加入7.5份苯胺,在40℃下搅拌混合物并保持pH 6-7,直到获得负性重氮化反应。然后用4.2份二乙醇胺处理搅拌混合物,蒸馏除去丙酮。在pH 8下加热到78-82℃1小时完成反应。分离沉淀物并在pH 8(氢氧化钠)下再溶解在32份脲在水中的水溶液中,得到190份以25/50/25的摩尔比含有通式(Va)、(Vb)和(Vc)的化合物的澄清溶液(SOLUTION D)
实施例4
将53.2份苯胺-2,5-二磺酸和16.8份氢氧化钠在75份水中的溶液加入38.7份氰尿酰氯在125份冰水中的搅拌悬浮液中。通过滴加30%的氢氧化钠保持pH值为6。在10℃以下搅拌混合物,直到通过重氮化反应不再检测出伯芳族胺基。然后加入37.0份4,4’-二氨基茋-2,2’-二磺酸和8.0份氢氧化钠在50份水中的溶液,通过加入30%的氢氧化钠将pH值调节到6.5-7.5,在30℃下搅拌混合物,直至获得负性重氮化反应。产物是457份含有27wt%以下通式化合物的含水悬浮液。
向274.2份根据通式(IIIa)的化合物的含水悬浮液中加入17.6份L-天冬氨酸在33份16%氢氧化钠中的溶液。然后加热回流混合物2小时,通过加入30%的氢氧化钠保持pH在7.5-8.5。将这样形成的通式(IIIc)
的化合物的溶液冷却到40-50℃,并用剩余的182.8份通式(IIIa)的化合物的含水悬浮液处理。将所得溶液调节到pH 8-9,并用水稀释到800份,得到以40/60的摩尔比含有通式(IIIa)和通式(IIIc)的化合物的澄清的、可稳定储存的溶液(SOLUTION F)
表1/实施例5-29
优选的结构是Ia和Ib(应用于纸料或通过涂料应用)和Ic(通过涂料应用)。
实施例 | B | X | Y |
24 | -O- | -Cl | -Cl |
25 | -O- | -Cl | -N(CH2CH2OH)2 |
26 | -O- | -Cl | -N(CH2CH2OH)CH2CH2CONH2 |
27 | -NH- | -F | -F |
28 | -NH- | -F | -N(CH2CH2OH)2 |
29 | -NH- | -F | -N(CH2CH2OH)CH2CH2CONH2 |
表2/实施例30-58
实施例 | B | X | Y | -SO3H的位置 |
30 | -NH- | -Cl | -Cl | 2 |
31 | -NH- | -Cl | -Cl | 3 |
32 | NH | -Cl | -N(CH2CH2OH)2 | 3 |
33 | -NH- | -Cl | -NHCH(CO2H)CH2CO2H | 3 |
34 | -NH- | -Cl | -Cl | 4 |
35 | -NH- | -Cl | -NHCH2CH2OH | 4 |
36 | -NH- | -Cl | -NHCH2CH2SO3H | 4 |
37 | -NH- | -Cl | -N(CH3)CH2CH2OH | 4 |
38 | -NH- | -Cl | -N(CH3)CH2CH2SO3H | 4 |
39 | -NH- | -Cl | -NHCH2CH(CH3)OH | 4 |
40 | -NH- | -Cl | -N(CH2CO2H)2 | 4 |
41 | -NH- | -Cl | -NHCH(CO2H)CH2CO2H | 4 |
表3/实施例59-77
表4/实施例78-97
表5/实施例98-119
表6/实施例120-135
应用实施例1
制备含有500份白垩(从OMYA以商品名Hydrocarb90市购)、500份粘土(从IMERYS以商品名KaolinSPS市购)、494份水、6份分散剂(从BASF以商品名PolysalzS市购的聚丙烯酸的钠盐)、200份胶乳(从BASF以商品名AcronalS320D市购的丙烯酸酯共聚物)和400份的20%水溶液淀粉(从Avebe以商品名PerfectamylA4692商购)的涂料组合物。通过加入水将固体含量调节到66.7%,用氢氧化钠调节pH值到8-9。
将实施例1的SOLUTION A以1.5%的浓度加入搅拌的涂料组合物中。然后用自动绕线棒涂覆器,以标准设定速度和标准棒载荷将增白涂料组合物涂覆到商品75gm-2中性施胶的白色纸基页上。然后在热气流中干燥已涂覆纸张5分钟。调理干燥后的纸张,然后在校准的ELREPHO(Datacolor的商标)分光光度计上测量CIE白度。为了比较,用仅含有通式(IIIc)的增白剂的含水SOLUTION B制备CIE白度水平近似相同的涂覆纸张。
通过将纸张直接暴露在日光下进行加速老化试验。CIE白度测量按规定的间隔进行。结果以表(表1)和图解(图1)形式表示如下。
表1
时间(h) | CIE W1 | ΔCIE W2 | |
未增白的纸基 | 0 | 94.0 | - |
2 | 88.7 | - | |
6 | 88.3 | - | |
24 | 86.5 | - | |
48 | 83.2 | - | |
72 | 78.5 | - | |
用SOLUTION B增白 | 0 | 104.0 | 10.0 |
2 | 97.9 | 9.2 | |
6 | 97.4 | 9.1 | |
24 | 95.4 | 8.9 | |
48 | 91.1 | 7.9 | |
72 | 85.5 | 7.0 | |
用SOLUTION A增白 | 0 | 104.9 | 10.9 |
2 | 100.9 | 12.2 | |
6 | 101.5 | 13.2 | |
24 | 101.7 | 15.2 | |
48 | 98.4 | 15.2 | |
72 | 93.6 | 15.1 |
1CIE W是CIE白度;2ΔCIE W是已增白纸张的CIE白度与未增白纸张在所列时间下的CIE白度之间的差。
应用实施例2
如应用实施例1描述制备涂料组合物。将实施例2的SOLUTION C以2.0%的浓度加入搅拌涂料组合物中。然后用自动绕线棒涂覆器,以标准设定速度和标准棒载荷将增白的涂料组合物涂覆到市购75gm-2中性施胶的白色纸基页上。然后在热气流中干燥已涂覆纸张5分钟。调理干燥的纸张,然后在校准的ELREPHO分光光度计上测量CIE白度。为了比较,用仅含有通式(IIIc)的增白剂的含水SOLUTION B制备CIE白度水平近似相同的涂覆纸张。
通过将纸张直接暴露在日光下进行加速老化试验。CIE白度测量按规定的间隔进行。结果以表(表2)和图解(图2)形式表示如下。
表2
时间(h) | CIE W1 | ΔCIE W2 | |
未增白的纸基 | 0 | 94.1 | - |
2 | 88.1 | - | |
5 | 86.9 | - | |
24 | 85.8 | - | |
48 | 84.2 | - | |
120 | 80.1 | - | |
用SOLUTION B增白 | 0 | 103.3 | 9.2 |
2 | 97.1 | 9.0 | |
5 | 95.7 | 8.8 | |
24 | 94.4 | 8.6 | |
48 | 92.4 | 8.2 | |
120 | 86.9 | 6.8 | |
用SOLUTION C增白 | 0 | 102.7 | 8.6 |
2 | 99.1 | 11.0 | |
5 | 99.7 | 12.8 | |
24 | 100.2 | 14.4 | |
48 | 99.9 | 15.7 | |
120 | 94.9 | 14.8 |
应用实施例3
将来自实施例3的SOLUTION D以1.2%(重量)干纤维的浓度加入搅拌的50∶50漂白的软木与打到20-300SR游离度的硬木浆的混合物的2.5%含水悬浮液中。搅拌5分钟后,将纸浆悬浮液稀释到0.5%,通过将1升分散的悬浮液倒到网目上制备纸页。压平并干燥后,在校准的ELREPHO分光光度计上测量已增白纸张的CIE白度。为了比较,用仅含有通式(Vc)的增白剂的含水SOLUTION E制备CIE白度水平近似相同的纸张。
通过将纸张直接暴露在日光下进行加速老化试验。CIE白度测量按规定的间隔进行。结果以表(表3)和图解(图3)形式表示如下。
表3
时间(h) | CIE W1 | ΔCIE W2 | |
未增白的纸基 | 0 | 77.2 | - |
2 | 79.8 | - | |
21 | 78.4 | - | |
44 | 76.3 | - | |
用SOLUTION E增白 | 0 | 121.3 | 44.1 |
2 | 127.8 | 48.0 | |
21 | 126.5 | 48.1 | |
44 | 111.9 | 35.6 | |
用SOLUTION D增白 | 0 | 121.4 | 44.2 |
2 | 125.7 | 45.9 | |
21 | 129.3 | 50.9 | |
44 | 128.4 | 52.1 |
应用实施例4
制备含有500份白垩(Hydrocarb90)、500份粘土(KaolinSPS)、494份水、6份分散剂(PolysalzS)、200份胶乳(AcronalS320D)和400份20%淀粉(Perfectamyl A4692)的水溶液的涂料组合物。通过加入水将固体含量调节到66.7%,用氢氧化钠调节pH值到8-9。
将来自实施例4的SOLUTION F以1.0%的浓度加入搅拌涂料组合物中。然后用自动绕线棒涂覆器,以标准设定速度和标准棒载荷将增白的涂料组合物涂覆到市购75gm-2中性施胶的白色纸基页上。然后在热气流中干燥已涂覆纸张5分钟。调理干燥的纸张,然后在校准的ELREPHO分光光度计上测量CIE白度。为了比较,用仅含有通式(IIIc)的增白剂的含水SOLUTION B制备CIE白度水平近似相同的涂覆纸张。
通过将纸张直接暴露在日光下进行加速老化试验。CIE白度测量按规定的间隔进行。结果以表(表4)和图解(图4)形式表示如下。
表4
时间(h) | CIE W | ΔCIE W | |
未增白的纸基 | 0 | 94.0 | - |
3 | 88.3 | - | |
7 | 87.4 | - | |
24 | 86.1 | - | |
48 | 85.1 | - | |
72 | 83.1 | - | |
96 | 82.1 | - | |
用SOLUTION B增白 | 0 | 104.2 | 10.2 |
3 | 98.0 | 9.7 | |
7 | 97.1 | 9.7 | |
24 | 95.7 | 9.6 | |
48 | 93.7 | 8.6 | |
72 | 91.2 | 8.1 | |
96 | 90.0 | 7.9 | |
用SOLUTION F增白 | 0 | 104.0 | 10.0 |
3 | 99.5 | 11.2 | |
7 | 99.3 | 11.9 | |
24 | 97.9 | 11.8 | |
48 | 96.5 | 11.4 | |
72 | 94.4 | 11.3 | |
96 | 93.4 | 11.3 |
应用实施例5
将实施例4的SOLUTION F以30g/l的浓度加入在60℃下搅拌的阴离子氧化的马铃薯淀粉(PerfectamylA4692)水溶液中。用水稀释溶液到淀粉浓度为5%并使之冷却。将施胶溶液倒入实验室施胶机的运动辊之间,并涂覆到市购75gm-2中性施胶的白色纸基页上。在平板床干燥器中在70℃下干燥已处理的纸张5分钟。调理干燥的纸张,然后在校准的ELREPHO分光光度计上测量CIE白度。为了比较,用仅含有通式(IIIc)的增白剂的含水SOLUTION B制备CIE白度水平近似相同的纸张。
通过将纸张直接暴露在日光下进行加速老化试验。CIE白度测量按规定的间隔进行。结果以表(表5)和图解(图5)形式表示如下。
表5
时间(h) | CIE W | ΔCIE W | |
未增白的纸基 | 0 | 98.2 | - |
3 | 95.6 | - | |
7 | 94.7 | - | |
48 | 90.3 | - | |
72 | 87.7 | - | |
96 | 85.7 | - | |
用SOLUTION B增白 | 0 | 115.7 | 17.5 |
3 | 114.9 | 19.3 | |
7 | 113.8 | 19.1 | |
48 | 108.7 | 18.4 | |
72 | 105.8 | 18.1 | |
96 | 103.6 | 17.9 | |
用SOLUTION F增白 | 0 | 115.4 | 17.2 |
3 | 117.7 | 22.1 | |
7 | 118.2 | 23.5 | |
48 | 115 | 24.7 | |
72 | 113.3 | 25.6 | |
96 | 111.5 | 25.8 |
应用实施例6
制备含有500份白垩(Hydrocarb90)、500份粘土(KaolinSPS)、494份水、6份分散剂(PolysalzS)、200份胶乳(AcronalS320D)和400份20%淀粉(PerfectamylA4692)的水溶液的涂料组合物。通过加入水将固体含量调节到66.7%,用氢氧化钠调节pH值到8-9。
将来自实施例4的SOLUTION F以1.5%的浓度加入搅拌的涂料组合物中。然后用自动绕线棒涂覆器,以标准设定速度和标准棒载荷将增白的涂料组合物涂覆到市购75gm-2中性施胶的白色纸基页上。然后在热气流中干燥已涂覆纸张5分钟。调理干燥的纸张,然后在校准的ELREPHO分光光度计上测量CIE白度。为了比较,用仅含有通式(IIIc)的增白剂的含水SOLUTION B制备CIE白度水平近似相同的涂覆纸张。
通过将纸张暴露在MEGASOL Xenon Arc Lightfastness Tester(氙弧耐光测试仪)中进行加速老化试验。CIE白度测量按规定的间隔进行。结果以表(表6)和图解(图6)形式表示如下。
表6
时间(h) | CIE W | ΔCIE W | |
未增白的纸基 | 0 | 82.3 | - |
0.25 | 81.9 | - | |
0.5 | 81.4 | - | |
1.0 | 79.0 | - | |
2.0 | 76.2 | - | |
5.0 | 70.0 | - | |
用SOLUTION B增白 | 0 | 100.9 | 18.6 |
0.25 | 98.8 | 16.9 | |
0.5 | 96.1 | 14.7 | |
1.0 | 93.2 | 14.2 | |
2.0 | 88.0 | 11.8 | |
5.0 | 79.1 | 9.1 | |
用SOLUTION F增白 | 0 | 100.2 | 17.9 |
0.25 | 99.8 | 17.9 | |
0.5 | 99.6 | 18.2 | |
1.0 | 96.6 | 17.6 | |
2.0 | 93.9 | 17.7 | |
5.0 | 86.3 | 16.3 |
Claims (9)
1、至少一种通式(I)的化合物与至少一种通式(II)的化合物的混合物作为荧光增白剂的应用,
其中
R1和R2互相独立地指H;卤素;未取代的C1-6烷基;取代的C1-6烷基和C1-6烷氧基,
每个B互相独立地指-O-或-NR3-,其中R3指H;未取代的C1-4烷基或取代的C1-4烷基,
X指卤素,
Y指卤素;OR4;SR4或NR4R5,其中
R4指未取代的C1-6烷基;取代的C1-6烷基;未取代的苯基或取代的苯基,
R5指H;未取代的C1-6烷基或取代的C1-6烷基,或
R4和R5与它们所键合的氮原子一起形成吡咯烷基、哌啶基或吗啉基,
n和m相互独立地指0、1或2,
每个M指阳离子,
Z指OR4、SR4或NR4R5,其中R4和R5具有与上述相同的含义。
2、根据权利要求1的应用,其特征在于应用至少一种通式(I)的化合物与至少一种通式(II)的化合物的混合物,其中
R1和R2互相独立地指H;Cl;F;未取代的C1-2烷基;取代的C1-2烷基和C1-2烷氧基,
每个B互相独立地指-O-或-NR3-,其中R3指H;未取代的C1-2烷基或取代的C1-2烷基,
X指F或Cl,
Y指Cl;F;OR4;SR4或NR4R5,其中
R4指未取代的C1-6烷基;取代的C1-6烷基;未取代的苯基或取代的苯基;
R5指H;未取代的C1-6烷基或取代的C1-6烷基,或
R4和R5与它们所键合的氮原子一起形成吡咯烷基、哌啶基或吗啉基,
n和m相互独立地指0、1或2,
每个M指阳离子,
Z指OR4、SR4或NR4R5,其中R4和R5具有与上述相同的含义。
3、根据权利要求1的应用,其特征在于应用至少一种通式(I)的化合物与至少一种通式(II)的化合物的混合物,其中
R1和R2互相独立地指H;Cl;F;未取代的C1-2烷基;取代的C1-2烷基和C1-2烷氧基,
每个B互相独立地指-O-或-NR3-,其中R3指H;未取代的C1-2烷基或取代的C1-2烷基,
X指Cl,
Y指Cl;F;OR4;SR4或NR4R5,其中
R4指未取代的C1-6烷基;取代的C1-6烷基;未取代的苯基或取代的苯基;
R5指H;未取代的C1-6烷基或取代的C1-6烷基,或
R4和R5与它们所键合的氮原子一起形成吡咯烷基、哌啶基或吗啉基,
n和m相互独立地指0、1或2,
每个M指阳离子,
Z指OR4、SR4或NR4R5,其中R4和R5具有与上述相同的含义。
4、根据权利要求1的应用,其特征在于混合物包含2wt%-95wt%的通式(I)的化合物和98wt%-5wt%通式(II)的化合物。
5、根据权利要求1的应用,其特征在于天然和再生的纤维素纤维、天然或合成的聚酰胺或聚氨酯纤维、纺织品或纸张被增白。
6、根据权利要求5的应用,其特征在于纸张被增白。
7、包含至少一种通式(I)的化合物和至少一种通式(II)的化合物的混合物,
其中
R1和R2互相独立地指H;卤素;未取代的C1-6烷基;取代的C1-6烷基和C1-6烷氧基,
每个B互相独立地指-O-或-NR3-,其中R3指H;未取代的C1-4烷基或取代的C1-4烷基,
X指卤素,
Y指卤素;OR4;SR4或NR4R5,其中
R4指未取代的C1-6烷基;取代的C1-6烷基;未取代的苯基或取代的苯基,
R5指H;未取代的C1-6烷基或取代的C1-6烷基,或
R4和R5与它们所键合的氮原子一起形成吡咯烷基、哌啶基或吗啉基,
n和m相互独立地指0、1或2,
每个M指阳离子,
Z指OR4、SR4或NR4R5,其中R4和R5具有与上述相同的含义。
8、根据权利要求7的包含至少一种通式(I)的化合物和至少一种通式(II)的化合物的混合物,其特征在于,
R1和R2互相独立地指H;Cl;F;未取代的C1-2烷基;取代的C1-2烷基和C1-2烷氧基,
每个B互相独立地指-O-或-NR3-,其中R3指H;未取代的C1-2烷基或取代的C1-2烷基,
X指F或Cl,
Y指Cl;F;OR4;SR4或NR4R5,其中
R4指未取代的C1-6烷基;取代的C1-6烷基;未取代的苯基或取代的苯基;
R5指H;未取代的C1-6烷基或取代的C1-6烷基,或
R4和R5与它们所键合的氮原子一起形成吡咯烷基、哌啶基或吗啉基,
n和m相互独立地指0、1或2,
每个M指阳离子。
9、根据权利要求7的包含至少一种通式(I)的化合物和至少一种通式(II)的化合物的混合物,其特征在于,
R1和R2互相独立地指H;Cl;F;未取代的C1-2烷基;取代的C1-2烷基和C1-2烷氧基,
每个B互相独立地指-O-或-NR3-,其中R3指H;未取代的C1-2烷基或取代的C1-2烷基,
X指Cl,
Y指Cl;F;OR4;SR4或NR4R5,其中
R4指未取代的C1-6烷基;取代的C1-6烷基;未取代的苯基或取代的苯基;
R5指H;未取代的C1-6烷基或取代的C1-6烷基,或
R4和R5与它们所键合的氮原子一起形成吡咯烷基、哌啶基或吗啉基,
n和m相互独立地指0、1或2,
每个M指阳离子。
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EP1712677A1 (en) * | 2005-04-08 | 2006-10-18 | Clariant International Ltd. | Aqueous solutions of optical brighteners |
EP1752453A1 (en) * | 2005-08-04 | 2007-02-14 | Clariant International Ltd. | Storage stable solutions of optical brighteners |
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Also Published As
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CA2456908C (en) | 2011-07-19 |
TWI300065B (en) | 2008-08-21 |
US7198731B2 (en) | 2007-04-03 |
JP2005509735A (ja) | 2005-04-14 |
KR100952554B1 (ko) | 2010-04-12 |
ES2329558T3 (es) | 2009-11-27 |
KR20050044562A (ko) | 2005-05-12 |
ZA200401324B (en) | 2005-05-25 |
PT1448853E (pt) | 2009-11-04 |
US20050022320A1 (en) | 2005-02-03 |
NO20042534L (no) | 2004-08-23 |
AU2002347452B2 (en) | 2008-01-31 |
GB0127903D0 (en) | 2002-01-16 |
DE60233516D1 (de) | 2009-10-08 |
CA2456908A1 (en) | 2003-05-30 |
WO2003044275A1 (en) | 2003-05-30 |
CN1589352A (zh) | 2005-03-02 |
ES2329558T5 (es) | 2015-09-23 |
EP1448853A1 (en) | 2004-08-25 |
BR0214268A (pt) | 2004-09-21 |
JP4550419B2 (ja) | 2010-09-22 |
EP1448853B1 (en) | 2009-08-26 |
AU2002347452A1 (en) | 2003-06-10 |
BRPI0214268B1 (pt) | 2016-12-13 |
EP1448853B2 (en) | 2015-07-22 |
ATE440999T1 (de) | 2009-09-15 |
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