CN107012732A - Fluorescent whitening agent composition - Google Patents
Fluorescent whitening agent composition Download PDFInfo
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- CN107012732A CN107012732A CN201610061331.5A CN201610061331A CN107012732A CN 107012732 A CN107012732 A CN 107012732A CN 201610061331 A CN201610061331 A CN 201610061331A CN 107012732 A CN107012732 A CN 107012732A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0083—Solutions of dyes
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/09—Sulfur-containing compounds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
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Abstract
Description
技术领域technical field
本发明涉及一种荧光增白剂，特别是涉及一种用于造纸的荧光增白剂组合物及其应用方法。The invention relates to a fluorescent whitening agent, in particular to a fluorescent whitening agent composition for papermaking and an application method thereof.
背景技术Background technique
在造纸领域中，将纸浆中加入适量的荧光增白剂(Optical Brightening Agents，OBA)，以利用荧光增白剂的光学作用增加制造出的纸张或纸板的白度是不可或缺的步骤之一。目前广泛在造纸行业使用的二苯乙烯三嗪类化合物的荧光增白剂，依其化学式结构中磺酸根数目，分为二磺、四磺与六磺三类别。然而，现有技术中，若仅利用二苯乙烯三嗪类化合物作为荧光增白剂，其普遍存在增白度的限制，无法充分发挥及提升荧光增白剂的增白效率的缺点。In the field of papermaking, it is one of the indispensable steps to add an appropriate amount of optical brightening agents (Optical Brightening Agents, OBA) to the pulp to increase the whiteness of the produced paper or cardboard by utilizing the optical effect of the optical brightening agent . At present, the optical brighteners of diphenylethylene triazine compounds widely used in the paper industry are divided into disulfonate, tetrasulfonate and hexasulfonate according to the number of sulfonate groups in the chemical formula. However, in the prior art, if only stilbene triazine compounds are used as fluorescent whitening agents, there is generally a limitation in the degree of whitening, and there is a shortcoming that the whitening efficiency of fluorescent whitening agents cannot be fully utilized and improved.
由此可见，上述现有技术仍有诸多缺失，仍有改善空间，亟待加以改良。It can be seen that the above-mentioned prior art still has many deficiencies, and there is still room for improvement, which needs to be improved urgently.
发明内容Contents of the invention
发明人鉴于上述现有技术所衍生的各项缺点，乃亟思加以改良创新，并经多年苦心孤诣潜心研究后，终于成功研发完成本发明一种荧光增白剂组合物。In view of the shortcomings derived from the above-mentioned prior art, the inventor is eager to improve and innovate, and after years of painstaking research, he finally successfully developed a fluorescent whitening agent composition of the present invention.
本发明提供一种荧光增白剂组合物，由荧光增白剂、分散剂及水组成，其中荧光增白剂为二苯乙烯三嗪类化合物、分散剂为亚甲基二萘磺酸钠类化合物。其中二苯乙烯三嗪类化合物为式(1)所示化合物：The invention provides a fluorescent whitening agent composition, which is composed of a fluorescent whitening agent, a dispersant and water, wherein the fluorescent whitening agent is a stilbene triazine compound, and the dispersant is sodium methylene dinaphthalene sulfonate compound. Wherein the stilbene triazine compound is a compound shown in formula (1):
所述亚甲基二萘磺酸钠类化合物选自化学式(2)、化学式(3)或化学式(4)所示化合物中的一种：The sodium methylene dinaphthalene sulfonate compound is selected from one of the compounds shown in chemical formula (2), chemical formula (3) or chemical formula (4):
其中R1选自化学式(5)、化学式(6)及化学式(7)中的一种：Wherein R is selected from one of chemical formula (5), chemical formula (6) and chemical formula (7):
其中R2选自化学式(8)、化学式(9)及化学式(10)中的一种：Wherein R is selected from one of chemical formula (8), chemical formula (9) and chemical formula (10):
当二苯乙烯三嗪类化合物的R1为化学式(5)取代时，为二磺二苯乙烯三嗪；当二苯乙烯三嗪类化合物的R1为化学式(6)取代时，为四磺二苯乙烯三嗪；当二苯乙烯三嗪类化合物的R1为化学式(7)取代时，为六磺二苯乙烯三嗪。When the R of the stilbene triazine compound is substituted by the chemical formula (5), it is a disulfo-stilbene triazine; when the R of the stilbene triazine compound is substituted by the chemical formula (6), it is a tetrasulfonate Stilbene triazine; When the R of the toluene triazine compound is replaced by chemical formula (7), it is hexasulfo-stilbene triazine.
在其中一个实施例中，所述荧光增白剂组合物，以重量百分比计，包括荧光增白剂20～40％，分散剂5～25％以及水35～75％。In one embodiment, the fluorescent whitening agent composition includes, by weight percentage, 20-40% fluorescent whitening agent, 5-25% dispersant and 35-75% water.
在其中一个实施例中，所述荧光增白剂组合物，以重量百分比计，包括荧光增白剂15～40％，分散剂2～25％以及水35～83％。In one embodiment, the fluorescent whitening agent composition includes, by weight percentage, 15-40% fluorescent whitening agent, 2-25% dispersant and 35-83% water.
本发明所述荧光增白剂组合物，当其制备时，将水与二苯乙烯三嗪类化合物的荧光增白剂依比例混合均匀，或直接取二苯乙烯三嗪类化合物的荧光增白剂的浓缩溶液，边搅拌边添加所述分散剂，添加完成后继续搅拌，直到混合均匀，以水调整浓度，即得本发明所述荧光增白剂组合物。The fluorescent whitening agent composition of the present invention, when it is prepared, mixes water and the fluorescent whitening agent of stilbene triazine compound in proportion, or directly takes the fluorescent whitening agent of stilbene triazine compound Add the dispersant to the concentrated solution of the dispersant while stirring, continue to stir until the mixture is uniform, and adjust the concentration with water to obtain the fluorescent whitening agent composition of the present invention.
本发明提供一种荧光增白剂组合物的用途，用作纸或纸板的光学增白的增白剂。The invention provides an application of a fluorescent whitening agent composition, which is used as a whitening agent for optical whitening of paper or cardboard.
在其中一个实施例中，用作纸的表面或纸板的表面的光学增白的增白剂。In one of the embodiments, it is used as a brightener for the optical brightening of the surface of paper or paperboard.
在其中一个实施例中，使用方法为：直接在纸或纸板的表面进行涂覆，或，在施胶过程中进行添加并压制。In one embodiment, the application method is: directly coating the surface of the paper or cardboard, or adding and pressing during the sizing process.
在其中一个实施例中，将所述荧光增白剂组合物用于纸浆悬浮液、纸浆悬浮浆料或纸浆中。In one of the embodiments, the fluorescent whitening agent composition is used in pulp suspension, pulp suspension slurry or pulp.
在其中一个实施例中，将所述荧光增白剂组合物用于无木纸浆或含木纸浆中。In one of the embodiments, the optical brightener composition is used in wood-free pulp or wood-containing pulp.
本发明提供一种荧光增白剂组合物用于纸的增白作用的方法，在纸浆悬浮液、纸浆悬浮浆料或纸浆中任一者或二者以上的组合中，添加本发明所述荧光增白剂组合物，制造纸张或纸板，并干燥所述纸张或纸板。The invention provides a method for the whitening effect of a fluorescent whitening agent composition on paper, adding the fluorescent whitening agent described in the present invention to any one of pulp suspension, pulp suspension slurry, or a combination of more than two pulps. Brightener composition for making paper or board and drying said paper or board.
在其中一个实施例中，所述添加的方法为：将所述荧光增白剂组合物以水稀释后，添加在所述纸浆悬浮液、纸浆悬浮浆料或纸浆其中任一者或二者以上的组合中。In one of the embodiments, the method of adding is: after diluting the fluorescent whitening agent composition with water, add it to any one or more of the pulp suspension, pulp suspension slurry or pulp in the combination.
在其中一个实施例中，所述稀释的方法为：将所述荧光增白剂组合物以水稀释至重量百分比为0.1％。In one embodiment, the dilution method is: diluting the fluorescent whitening agent composition with water to 0.1% by weight.
本发明还提供所述用于纸的增白作用的方法制得的纸或纸板。The invention also provides paper or paperboard produced by the method for whitening paper.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明所述荧光增白剂组合物，通过采用二苯乙烯三嗪类化合物作为荧光增白剂，配合亚甲基二萘磺酸钠类化合物作为分散剂，突破了现有增百度的限制，有效提高了组合物的增白效率，适用于纸张或纸板的工业生产，提升纸张或纸板的品质。The fluorescent whitening agent composition of the present invention breaks through the existing limitation of increasing degree by adopting diphenylethylene triazine compound as fluorescent whitening agent and coordinating sodium methylene dinaphthalene sulfonate compound as dispersant. The whitening efficiency of the composition is effectively improved, and it is suitable for industrial production of paper or cardboard, and improves the quality of paper or cardboard.
附图说明Description of drawings
图1为本发明所述荧光增白剂组合物一实施例的白度比较示意图；Fig. 1 is the comparative schematic diagram of the whiteness of an embodiment of the optical brightener composition of the present invention;
图2为本发明所述荧光增白剂组合物一实施例的视白度比较示意图；Fig. 2 is the comparative schematic diagram of the apparent whiteness of an embodiment of the optical brightener composition of the present invention;
图3为本发明所述荧光增白剂组合物另一实施例的白度比较示意图；Fig. 3 is a whiteness comparison schematic diagram of another embodiment of the optical brightener composition of the present invention;
图4为本发明所述荧光增白剂组合物另一实施例的视白度比较示意图；Fig. 4 is the comparison schematic diagram of the apparent whiteness of another embodiment of the fluorescent whitening agent composition of the present invention;
图5为本发明所述荧光增白剂组合物又一实施例的白度比较示意图；Fig. 5 is the whiteness comparison schematic diagram of another embodiment of the fluorescent whitening agent composition of the present invention;
图6为本发明所述荧光增白剂组合物又一实施例的视白度比较示意图。Fig. 6 is a schematic diagram showing the comparison of the apparent whiteness of another embodiment of the fluorescent whitening agent composition of the present invention.
具体实施方式detailed description
以下将参照相关图式，说明依本发明所述荧光增白剂组合物及其应用的实施例，为使便于理解，下述实施例中的相同组件以相同的符号标示来说明。The following will refer to the related drawings to illustrate the embodiment of the fluorescent whitening agent composition and its application according to the present invention. For easy understanding, the same components in the following embodiments are described with the same symbols.
实施例Example
本实施例提供一种荧光增白剂组合物，由荧光增白剂、分散剂及水组成，其中荧光增白剂为二苯乙烯三嗪类化合物、分散剂为亚甲基二萘磺酸钠类化合物。其中二苯乙烯三嗪类化合物为二磺二苯乙烯三嗪、四磺二苯乙烯三嗪或六磺二苯乙烯三嗪；所述亚甲基二萘磺酸钠类化合物选自化学式(2)、化学式(3)或化学式(4)所示化合物中的一种：This embodiment provides a fluorescent whitening agent composition, which is composed of a fluorescent whitening agent, a dispersant and water, wherein the fluorescent whitening agent is a stilbene triazine compound, and the dispersant is sodium methylene dinaphthalene sulfonate class of compounds. Wherein the stilbene triazine compound is disulfonyl stilbene triazine, tetrasulfonyl stilbene triazine or hexasulfonyl stilbene triazine; the sodium methylene dinaphthalene sulfonate compound is selected from chemical formula (2 ), chemical formula (3) or one of the compounds shown in chemical formula (4):
依重量百分比调整所述荧光增白剂组合物的浓度，其中荧光增白剂占总重量百分比的22％，分散剂占总重量百分比的5％、10％或15％，其余为水。The concentration of the fluorescent whitening agent composition is adjusted by weight percentage, wherein the fluorescent whitening agent accounts for 22% of the total weight percentage, the dispersant accounts for 5%, 10% or 15% of the total weight percentage, and the rest is water.
首先，将水与二苯乙烯三嗪类化合物的荧光增白剂依比例混合均匀，或直接取二苯乙烯三嗪类化合物的荧光增白剂的浓缩溶液，边搅拌边添加分散剂，添加完成后继续搅拌，直到混合均匀，完成本发明的荧光增白剂组合物的制备。其中二苯乙烯三嗪类化合物的荧光增白剂为二磺二苯乙烯三嗪、四磺二苯乙烯三嗪或六磺二苯乙烯三嗪其中之一。First, mix the water and the fluorescent whitening agent of stilbene triazine compounds in proportion, or directly take the concentrated solution of the fluorescent whitening agent of stilbene triazine compounds, add the dispersant while stirring, and the addition is completed Then continue to stir until the mixture is uniform, and the preparation of the fluorescent whitening agent composition of the present invention is completed. Wherein the fluorescent whitening agent of the stilbene triazine compound is one of disulfonyl stilbene triazine, tetrasulfonyl stilbene triazine or hexasulfonyl stilbene triazine.
请参阅如下表1所示，其中未添加分散剂的荧光增白剂组合物设为对照组1，即四磺二苯乙烯三嗪，其为化学式(1)的二苯乙烯三嗪类化合物，其中R1取代基为化学式(6)，R2取代基为化学式(9)；以及将以四磺二苯乙烯三嗪作为荧光增白剂的本发明所述荧光增白剂组合物依分散剂添加占总重量百分比的5％、10％、15％分别设为组合1、组合2及组合3，将对照组1、组合1、组合2及组合3分别加水稀释至重量百分比为0.5％、1％、1.5％后，分别添加到纸浆悬浮液浆料中，抄造成纸，并检测白度GE与视白度CIE(Commission internationale del'éclairage)的测试，比较结果如表1及图1、图2所示，其中分散剂为化学式(2)的亚甲基二萘磺酸钠类化合物。Please refer to Table 1 below, wherein the fluorescent whitening agent composition without adding a dispersant is set as the control group 1, that is, tetrasulfonyl stilbene triazine, which is a stilbene triazine compound of chemical formula (1), Wherein R 1 substituting group is chemical formula (6), R 2 substituting group is chemical formula (9); Adding 5%, 10%, and 15% of the total weight percentage are respectively set as combination 1, combination 2, and combination 3, and the control group 1, combination 1, combination 2, and combination 3 are diluted with water to 0.5%, 1% by weight, respectively. % and 1.5%, respectively added to the pulp suspension slurry, made into paper, and tested for brightness GE and apparent whiteness CIE (Commission internationale del'éclairage), the comparison results are shown in Table 1 and Figure 1, Figure 1 2, wherein the dispersant is the sodium methylene dinaphthalene sulfonate compound of chemical formula (2).
表1Table 1
如表1所示，本发明荧光增白剂组合物的组合1、组合2及组合3在使用率5％、10％、15％的状况下，白度GE与视白度CIE的效果，皆明显优于照组1的四磺二苯乙烯三嗪。As shown in Table 1, the combination 1, combination 2 and combination 3 of the fluorescent whitening agent composition of the present invention have the effects of whiteness GE and apparent whiteness CIE under the conditions of usage rates of 5%, 10%, and 15%. Obviously better than the tetrasulfontilbene triazine of group 1.
请参阅如下表2所示，其中未添加分散剂的荧光增白剂组合物设为对照组2，即六磺二苯乙烯三嗪，其为化学式(1)的二苯乙烯三嗪类化合物，其中R1取代基为化学式(7)，R2取代基为化学式(10)；以及将以六磺二苯乙烯三嗪作为荧光增白剂的本发明的荧光增白剂组合物依分散剂添加占总重量百分比的5％、10％、15％分别设为组合4、组合5及组合6，将对照组2、组合4、组合5及组合6分别加水稀释至重量百分比为0.5％、1％、1.5％后，分别添加到淀粉糊液中，再均匀涂于原纸表面，干燥压光，并检测白度GE与视白度CI的测试，比较结果如表2及图3、图4所示，其中分散剂为化学式(3)的亚甲基二萘磺酸钠类化合物。Please refer to the following table 2, wherein the fluorescent whitening agent composition without dispersant is set as control group 2, that is, hexasulfonyl stilbene triazine, which is a stilbene triazine compound of chemical formula (1), Wherein R 1 substituting group is chemical formula (7), R 2 substituting group is chemical formula (10); 5%, 10%, and 15% of the total weight percentage are respectively set as combination 4, combination 5, and combination 6, and the control group 2, combination 4, combination 5, and combination 6 are respectively diluted with water to 0.5%, 1% by weight , 1.5%, respectively added to the starch paste liquid, and then evenly spread on the surface of the base paper, dried and calendered, and tested for whiteness GE and apparent whiteness CI, the comparison results are shown in Table 2 and Figure 3 and Figure 4 , wherein the dispersant is a sodium methylene dinaphthalene sulfonate compound of chemical formula (3).
表2Table 2
如表2所示，本发明荧光增白剂组合物的组合4、组合5及组合6在使用率5％、10％、15％的状况下，白度GE与视白度CIE的效果，皆明显优于照组2的六磺二苯乙烯三嗪。As shown in Table 2, the effects of whiteness GE and apparent whiteness CIE of the combination 4, combination 5 and combination 6 of the fluorescent whitening agent composition of the present invention are both Obviously better than the hexasulfonyl-stilbene triazine of group 2.
请参阅如下表3所示，其中未添加分散剂的荧光增白剂组合物设为对照组3，即二磺二苯乙烯三嗪，其为化学式(1)的二苯乙烯三嗪类化合物，其中R1取代基为化学式(5)，R2取代基为化学式(8)或化学式(9)；以及将以二磺二苯乙烯三嗪作为荧光增白剂的本发明的荧光增白剂组合物依分散剂添加占总重量百分比的5％、10％、15％分别设为组合7、组合8及组合9，将对照组3、组合7、组合8及组合9分别加水稀释至重量百分比为0.5％、1％、1.5％后，分别添加到淀粉糊液中，再均匀涂于原纸表面，干燥压光，并检测白度GE与视白度CIE的测试，比较结果如表3及图5、图6所示，其中分散剂为化学式(4)的亚甲基二萘磺酸钠类化合物。Please refer to the following table 3, wherein the fluorescent whitening agent composition without adding a dispersant is set as the control group 3, that is, disulfonyl stilbene triazine, which is a stilbene triazine compound of chemical formula (1), Wherein R 1 substituting group is chemical formula (5), R 2 substituting group is chemical formula (8) or chemical formula (9); Thing accounts for 5%, 10%, 15% of total weight percentage according to dispersing agent and is respectively set as combination 7, combination 8 and combination 9, and matched group 3, combination 7, combination 8 and combination 9 are diluted with water respectively to the weight percentage of After 0.5%, 1%, and 1.5%, add them to the starch paste liquid respectively, and then evenly spread them on the base paper surface, dry and calender, and test the whiteness GE and apparent whiteness CIE. The comparison results are shown in Table 3 and Figure 5 , shown in Fig. 6, wherein dispersant is the sodium methylene dinaphthalene sulfonate compound of chemical formula (4).
表3table 3
如表3所示，本发明荧光增白剂组合物的组合4、组合5及组合6在使用率5％、10％、15％的状况下，白度GE与视白度CIE的效果，皆明显优于照组3的二磺二苯乙烯三嗪。As shown in Table 3, the effects of whiteness GE and apparent whiteness CIE of the combination 4, combination 5 and combination 6 of the fluorescent whitening agent composition of the present invention are all the same under the conditions of usage rates of 5%, 10%, and 15%. Obviously better than the disulfodiphenylethylene triazine of group 3.
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。The technical features of the above-mentioned embodiments can be combined arbitrarily. To make the description concise, all possible combinations of the technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, should be considered as within the scope of this specification.
以上所述实施例仅表达了本发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。The above-mentioned embodiments only express several implementation modes of the present invention, and the descriptions thereof are relatively specific and detailed, but should not be construed as limiting the patent scope of the invention. It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention should be based on the appended claims.
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