CN113774691B - Printing ink auxiliary agent and preparation method thereof - Google Patents
Printing ink auxiliary agent and preparation method thereof Download PDFInfo
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- CN113774691B CN113774691B CN202111090575.3A CN202111090575A CN113774691B CN 113774691 B CN113774691 B CN 113774691B CN 202111090575 A CN202111090575 A CN 202111090575A CN 113774691 B CN113774691 B CN 113774691B
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5207—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- D06P1/525—Polymers of unsaturated carboxylic acids or functional derivatives thereof
- D06P1/5257—(Meth)acrylic acid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Discloses a printing ink auxiliary agent, which is obtained by copolymerization of acrylic acid, sodium methacrylate sulfonate, 4-hydroxybutyl polyethylene glycol vinyl ether and beta-cyclodextrin monomer with polymerizable groups; the beta-cyclodextrin monomer having a polymerizable group is selected from beta-cyclodextrin monomers of terminal acrylates. In addition, a preparation method of the printing ink auxiliary agent is also disclosed. The printing ink auxiliary agent not only has better dispersion stability, but also has better storage stability.
Description
Technical Field
The invention belongs to the technical field of digital printing, and particularly relates to a printing ink auxiliary agent and a preparation method thereof.
Background
Digital printing is an emerging printing technology in the textile industry in the last twenty years, and the digital printing technology digitizes printing patterns through input equipment such as scanners and the like and inputs the digitized printing patterns into a computer; in the micro-piezoelectric ink-jet system controlled by special software, printing ink is directly sprayed onto textile medium to form the required printing pattern. Compared with the traditional printing, the digital printing has the advantages of low energy consumption, low pollution, rapidness, flexibility and the like, ensures high printing quality, meets the customer requirements of personalized customization, small-batch production and the like, has wide market application prospect, and is an important development direction of printing production and processing. As labor costs rise year by year and environmental regulations tend to be stringent, more and more printing enterprises begin to change production modes to digital printing industries.
In the process of industrial development, digital printing has some problems to be solved, for example, a micro-piezoelectric nozzle is easy to block, the color of printed fabric is not bright enough, the printed pattern is not clear, burrs exist at the edge, the rubbing fastness and washing fastness of the fabric are poor, the storage stability of ink is poor, the performance parameters of the ink and the nozzle are inconsistent, the printing cost is still high, and the like. These specific problems are more or less linked to the performance parameters of the printing inks, and in order to achieve a fundamental revolution in the textile industry, the resolution of these specific problems must be taken as grippers.
The printing ink is taken as a key consumable in the digital printing process, and the cost occupies about 40% of the total production cost, so that the printing ink is one of key influencing factors of printing development, and the research and development of the ink must be emphasized in the digital printing industrialization process.
The ink for ink-jet printing of textiles is divided into dye ink and pigment ink according to the different colorants used in the ink. In theory, all dyes for dyeing and printing textiles can be prepared into digital printing inks, but the types of digital printing inks on the market are mainly reactive dye inks, acid dye inks and disperse dye inks. Currently, the reactive dye ink in the market accounts for about 30%, the acid dye ink accounts for about 7%, and the disperse dye ink accounts for about 60%.
Wherein, the reactive dye contains reactive groups in the molecular structure, and can react with certain groups on the fiber during dyeing to form covalent bonds to bond with the fiber. Therefore, the reactive dye is firmly combined with the fiber, has better washing fastness and rubbing fastness, and is the dye with the largest dyeing dosage of the textile at present. After the reactive dye is desalted to prepare ink, the ink is mainly used for digital printing of textiles such as cotton, silk and the like.
Because the reactive dye is used in a large amount in the printing process, the bath is relatively small, the reactive dye is easy to aggregate, and urea is usually required to be added to improve the solubility of the reactive dye. The urea molecule has hydrophilic group, and can be combined with carboxylic acid group or sulfonic acid group chemical bond on the reactive dye molecule, so that the reactive dye aggregate can be quickly dissociated, and the solubility of the dye can be improved. However, when the solubility of the reactive dye is poor or the content of the reactive dye is high, the reactive dye easily forms aggregates, resulting in deterioration of dispersion stability and storage stability of the printing ink.
Li Baoquan and the like uniformly mix reactive dye, tetrahydrofuran, hydroxypropyl methacrylate and sodium hydroxide, stir and heat up, and keep the temperature for 8 hours to carry out substitution reaction to obtain the red high polymer reactive dye. And preparing the high-molecular reactive dye ink from the high-molecular reactive dye, ethylene glycol butyl ether, N-methyl-2-pyrrolidone, octyl phenol polyoxyethylene ether, ethylene glycol, bactericide and deionized water. The physical and chemical parameters of the high molecular reactive dye ink accord with the conventional parameters, and the high molecular reactive dye ink has good adaptability in the inkjet printing process.
Chinese patent application CN106675093a discloses a reactive dye composition, its preparation method and application. The reactive dye composition comprises a reactive dye, an auxiliary agent and water, but does not comprise a high boiling point solvent; wherein the auxiliary agent comprises a macromolecular thickener and a macromolecular surfactant, the molecular weight of the macromolecular surfactant is 500-2000, the dosage of the macromolecular surfactant is 0.1-5%, the dosage of the macromolecular thickener is 0.3-10%, the dosage of the reactive dye is 3-15%, and the percentages are the percentages of the mass of each component and the total mass of the reactive dye composition. The preparation method comprises mixing the above materials, and filtering. The reactive dye composition is applied to the wet printing digital printing process technology, can greatly reduce the line burr phenomenon of wet printing digital printing, improves the vividness of textiles, the pattern definition and the color stability of textiles after batch printing and dyeing, and effectively solves the printing permeability problem of thick textiles.
However, the above prior art uses a polymer reactive dye or a polymer thickener and a polymer surfactant, respectively, and the resulting printing ink still has disadvantages of poor dispersion stability and storage stability.
In view of the above-mentioned drawbacks of the prior art, there is still a need to find a printing ink auxiliary agent with better dispersion stability and storage stability and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a printing ink auxiliary agent for digital printing and a preparation method thereof. Compared with the prior art, the printing ink auxiliary agent not only has better dispersion stability, but also has better storage stability.
In order to solve the technical problems, the invention adopts the following technical scheme: a printing ink auxiliary agent is prepared by copolymerization of acrylic acid, sodium methacrylate sulfonate, 4-hydroxybutyl polyethylene glycol vinyl ether and beta-cyclodextrin monomer with polymerizable group; characterized in that the beta-cyclodextrin monomer having a polymerizable group is selected from beta-cyclodextrin monomers of terminal acrylates.
The printing ink auxiliary agent provided by the invention, wherein the molar ratio of the beta-cyclodextrin monomer with the polymerizable group to the 4-hydroxybutyl polyethylene glycol vinyl ether is 1: (2-4).
Preferably, the molar ratio of the beta-cyclodextrin monomer having a polymerizable group to 4-hydroxybutyl polyethylene glycol vinyl ether is 1: (2.5-3.5).
The printing ink auxiliary agent provided by the invention, wherein the beta-cyclodextrin monomer with a polymerizable group comprises beta-cyclodextrin and p-benzenesulfonyl chloride according to a molar ratio of 1: and 1, reacting with 2-hydroxyethylamine and glycidyl methacrylate in turn.
The printing ink auxiliary agent according to the invention, wherein the number average molecular weight mn=1500-3500 g/mol of the 4-hydroxybutyl polyethylene glycol vinyl ether.
Preferably, the number average molecular weight mn=1800-3000 g/mol of the 4-hydroxybutyl polyethylene glycol vinyl ether.
The printing ink auxiliary according to the invention, wherein the molar ratio of the beta-cyclodextrin monomer with a polymerizable group to acrylic acid and sodium methacrylate sulfonate is 1: (5-9): (0.5-1.5).
Preferably, the molar ratio of the beta-cyclodextrin monomer having a polymerizable group to acrylic acid and sodium methacrylate sulfonate is 1: (6-8): (0.8-1.2).
The printing ink auxiliary agent provided by the invention, wherein the initiation system of the copolymerization reaction is a hydrogen peroxide/Vc system.
Advantageously, the molar ratio of hydrogen peroxide to Vc is (2.4-3.6): 1, a step of; preferably, the molar ratio of hydrogen peroxide to Vc is (2.7-3.3): 1.
the printing ink auxiliary according to the invention, wherein the hydrogen peroxide is added in an amount of 5-15% of the sum of the moles of all the comonomers.
Preferably, the hydrogen peroxide is added in an amount of 8-12% of the sum of the moles of all the comonomers.
The printing ink auxiliary agent provided by the invention, wherein the reaction temperature of the copolymerization reaction is 40-80 ℃.
Preferably, the reaction temperature of the copolymerization reaction is 50 to 70 ℃.
The printing ink auxiliary according to the invention, wherein the weight average molecular weight Mw of the printing ink auxiliary is=10000-18000 g/mol; number average molecular weight mn=4000-6000 g/mol; pdi=2.5-2.9.
Preferably, the weight average molecular weight Mw of the printing ink auxiliary is from 12000 to 15000g/mol; a number average molecular weight mn=4500-5500 g/mol; pdi=2.6-2.8.
On the other hand, the invention also provides a preparation method of the printing ink auxiliary agent, which comprises the following steps: copolymerization of acrylic acid, sodium methacrylate sulfonate, 4-hydroxybutyl polyethylene glycol vinyl ether and beta-cyclodextrin monomer having polymerizable group in the presence of an initiator system in an inert atmosphere; after the reaction is finished, adjusting the pH value to be 6-7 to obtain a transparent solution; precipitating with precipitant, and vacuum drying.
The inventors found that the printing ink auxiliary is better in dispersion stability and storage stability than the prior art.
Detailed Description
The invention is further described below in conjunction with the detailed description.
It should be understood that the description of the specific embodiments is merely illustrative of the principles and spirit of the invention, and not in limitation thereof. Further, it should be understood that various changes, substitutions, omissions, modifications, or adaptations to the present invention may be made by those skilled in the art after having read the present disclosure, and such equivalent embodiments are within the scope of the present invention as defined in the appended claims.
EXAMPLE 1 beta-cyclodextrin monomer of terminal acrylate
160mL of NaOH solution (2.34M) was added to 350mL of a suspension containing 25g (22 mmol) of beta-cyclodextrin over 30min, and the reaction was vigorously stirred at room temperature for 3h, then 8.39g (44 mmol) of p-benzenesulfonyl chloride was added, and the reaction was vigorously stirred at 4℃for 5h. Unreacted p-benzenesulfonyl chloride was removed by filtration, neutralized to ph=6.5 by adding hydrochloric acid, and allowed to stand overnight at 4 ℃. Suction filtration gives a white precipitate. Recrystallizing in water for 3 times, and vacuum drying at 60deg.C for 24h to obtain white solid 1.
20g (15.5 mmol) of white solid 1, 20mL of LDMF and 20mL of 2-hydroxyethylamine were sequentially added to a round-bottomed flask, and the reaction was stirred at 75℃for 6 hours, cooled to room temperature, and ended. The reaction solution was poured into 300mL of cold acetone to give a white precipitate as a crude product. The crude product was redissolved in water and reprecipitated using acetone; repeating for 3 times. Vacuum drying at 60 ℃ for 48h to obtain white solid 2.
30g (25.5 mmol) of white solid 2 were dissolved in 80mL volume ratio 1: DMF/H of 1 2 To the O mixture solution, 4.35g (30.6 mmol) of glycidyl methacrylate was added and the mixture was stirred at 80℃for 10 hours. Cooled to room temperature and the reaction was completed. The reaction solution was poured into 400mL of cold acetone to give a white precipitate as a crude product. The crude product was redissolved in water and reprecipitated using acetone; repeating for 3 times. Vacuum drying for 48h at room temperature to obtain white solid 3, namely beta-cyclodextrin monomer of terminal acrylate. 1 H NMR(600MHz,DMSO-d6)δ:6.08(s,1H),5.97(d,1H),5.82-5.55(m,14H),4.87(s,5H),4.82(s,2H),4.53-4.35(m,7H),4.06(m,1H),3.98(m,1H),3.78-3.46(m,28H),3.45-3.22(m,16H),3.17(m,1H),2.94(m,1H),2.74-2.35(m,4H),1.89(s,2H),1.87(s,1H)。
Example 2 Polymer printing ink Assistant
23.8g (18 mmol) of beta-cyclodextrin monomer of the terminal acrylate and 130g (54 mmol) of 4-hydroxybutyl polyethylene glycol vinyl ether (number average molecular weight Mn=2400 g/mol) are introduced into a round-bottomed flask, followed by 200mL of deionized water. Under the protection of nitrogen atmosphere, the water bath is heated to 60 ℃ and the transparent solution is obtained under the stirring condition. 0.73g (21.6 mmol) of hydrogen peroxide was added. 1.26g (7.2 mmol) of Vc was then dissolved in 50mL of deionized water to give an initiator solution.9.2g (126 mmol) of acrylic acid and 2.9g (18 mmol) of sodium methacrylate sulfonate were further dissolved in 30mL of deionized water to obtain a monomer solution. And (3) dropwise adding the monomer solution and the initiator solution into the transparent solution, and continuing to react for 1h after the dropwise adding is finished. After the reaction, cooling to room temperature. Ph=6.5 was adjusted using 30wt% sodium hydroxide solution to give a pale yellow transparent solution. The pale yellow clear solution was poured into 500mL of cold absolute ethanol to give a pale yellow precipitate as a crude product. The crude product was redissolved in water and reprecipitated using absolute ethanol; repeating for 3 times. And (5) drying in vacuum for 48 hours at room temperature to obtain the polymer printing ink auxiliary agent. IR (KBr) v=3390 cm -1 ，2930cm -1 ，1722cm -1 ，1643cm -1 ，1460cm -1 ，1340cm -1 ，1082cm -1 ，960cm -1 . The weight average molecular weight mw=13684 g/mol of the polymeric printing ink aid was determined using agilent PL-GPC 50; number average molecular weight mn=5035 g/mol; pdi=2.71.
Application example 1-composition comprising a polymeric printing ink auxiliary and a reactive dye
12wt% of c.i. reactive red 111, 1.5wt% of a polymer printing ink aid and deionized water are weighed, and ph=8 is adjusted; stirring for 2h by using a stirrer (400 rpm) and sanding for 8h by using a sand mill (1200 rpm) respectively; the product was taken out and left to stand for 48 hours, and filtered with a filter membrane having a pore size of 0.45 μm to obtain a composition comprising the polymer printing ink auxiliary and the reactive dye.
Application example 2-composition comprising a polymeric printing ink auxiliary and a reactive dye
12wt% of c.i. reactive red 111, 0.8wt% of a polymer printing ink aid and deionized water are weighed, and ph=8 is adjusted; stirring for 2h by using a stirrer (400 rpm) and sanding for 8h by using a sand mill (1200 rpm) respectively; the product was taken out and left to stand for 48 hours, and filtered with a filter membrane having a pore size of 0.45 μm to obtain a composition comprising the polymer printing ink auxiliary and the reactive dye.
Comparative example 1-composition comprising a polymeric printing ink adjuvant and a reactive dye
12wt% of c.i. reactive red 111, 0.4wt% of a polymer printing ink aid and deionized water are weighed, and ph=8 is adjusted; stirring for 2h by using a stirrer (400 rpm) and sanding for 8h by using a sand mill (1200 rpm) respectively; the product was taken out and left to stand for 48 hours, and filtered with a filter membrane having a pore size of 0.45 μm to obtain a composition comprising the polymer printing ink auxiliary and the reactive dye.
Comparative example 2-composition comprising a polymeric printing ink adjuvant and a reactive dye
The polymer printing ink auxiliary of comparative example 2 was prepared without adding the beta-cyclodextrin monomer of the terminal acrylate, and the other conditions were the same as in example 2. Then 12wt% of c.i. reactive red 111, 2wt% of the polymer printing ink aid of comparative example 2 and deionized water were weighed, and ph=8 was adjusted; stirring for 2h by using a stirrer (400 rpm) and sanding for 8h by using a sand mill (1200 rpm) respectively; the product was taken out and left to stand for 48 hours, and filtered with a filter membrane having a pore size of 0.45 μm to obtain a composition comprising the polymer printing ink auxiliary and the reactive dye.
Performance testing
A certain amount of the composition containing the polymer printing ink auxiliary agent and the reactive dye is added into a centrifuge tube, and the mixture is centrifuged for 30min at 8000 rpm. The supernatant was taken and diluted by a factor, and its absorbance was measured at the maximum absorption wavelength using a spectrophotometer. The dispersion stability was determined by using the ratio of absorbance of the system before and after centrifugation, that is, the specific absorbance R 1 Evaluation was performed. R is R 1 Absorbance of the system after centrifugation/absorbance of the non-centrifuged system is 100%.
A certain amount of the composition containing the polymer printing ink auxiliary agent and the reactive dye is placed in a glass bottle, and is placed in a baking oven at 40 ℃ for aging for one week. The supernatant was taken and diluted by a factor, and its absorbance was measured at the maximum absorption wavelength using a spectrophotometer. Storage stability Using the ratio of absorbance of the system before and after aging, i.e., the specific absorbance R 2 Evaluation was performed. R is R 2 Absorbance of the system after=absorbance of the unaged system 100%.
The results are shown in Table 1.
TABLE 1
| R 1 | R 2 | |
| Application example 1 | 98％ | 97％ |
| Application example 2 | 96％ | 94％ |
| Comparative example 1 | 91％ | 87％ |
| Comparative example 2 | 82％ | 79％ |
As can be seen from Table 1, the printing ink auxiliaries of the present invention of examples 1 and 2 were better in dispersion stability and storage stability than those of comparative examples 1 and 2.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention are included in the protection scope of the present invention.
Claims (6)
1. A printing ink auxiliary agent is prepared by copolymerization of acrylic acid, sodium methacrylate sulfonate, 4-hydroxybutyl polyethylene glycol vinyl ether and beta-cyclodextrin monomer with polymerizable group; wherein the beta-cyclodextrin monomer having a polymerizable group is selected from beta-cyclodextrin monomers of terminal acrylate esters;
wherein the molar ratio of the beta-cyclodextrin monomer with the polymerizable group to the 4-hydroxybutyl polyethylene glycol vinyl ether is 1: (2-4); the molar ratio of the beta-cyclodextrin monomer with the polymerizable group to the acrylic acid and the sodium methacrylate sulfonate is 1: (5-9): (0.5-1.5);
the beta-cyclodextrin monomer with the polymerizable group is prepared from beta-cyclodextrin and p-benzenesulfonyl chloride according to a molar ratio of 1:1, and then sequentially reacting with 2-hydroxyethylamine and glycidyl methacrylate;
the number average molecular weight Mn of the 4-hydroxybutyl polyethylene glycol vinyl ether is=1500-3500 g/mol;
the weight average molecular weight Mw of the printing ink auxiliary agent is=10000-18000 g/mol; number average molecular weight mn=4000-6000 g/mol; pdi=2.5-2.9.
2. A printing ink auxiliary according to claim 1 wherein the initiating system for the co-polymerization is a hydrogen peroxide/Vc system.
3. A printing ink auxiliary according to claim 2 wherein the molar ratio of hydrogen peroxide to Vc is (2.4-3.6): 1.
4. a printing ink aid according to claim 2 wherein hydrogen peroxide is added in an amount of 5 to 15% of the sum of the moles of all co-monomers.
5. A printing ink aid according to claim 1, wherein the reaction temperature of the copolymerization is 40-80 ℃.
6. A process for preparing a printing ink adjuvant according to any one of claims 1 to 5 comprising: copolymerization of acrylic acid, sodium methacrylate sulfonate, 4-hydroxybutyl polyethylene glycol vinyl ether and beta-cyclodextrin monomer having polymerizable group in the presence of an initiator system in an inert atmosphere; after the reaction is finished, adjusting the pH value to be 6-7 to obtain a transparent solution; precipitating with precipitant, and vacuum drying.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789345A (en) * | 2004-12-18 | 2006-06-21 | 青岛大学 | Method for preparing polyocarboxy acid type pigment ink |
| CN104817663A (en) * | 2015-04-10 | 2015-08-05 | 广州市建筑科学研究院有限公司 | Preparation method of polycarboxylate water-reducer capable of inhibiting side-effect of montmorillonite and polymeric monomer |
| CN106480753A (en) * | 2016-08-31 | 2017-03-08 | 浙江德誉进出口有限公司 | A kind of real silk blend polyester fabric digit printing ink and preparation method thereof |
| CN111499775A (en) * | 2017-11-27 | 2020-08-07 | 湖南辰砾新材料有限公司 | Polyamino modified cyclodextrin and application thereof |
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2021
- 2021-09-17 CN CN202111090575.3A patent/CN113774691B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789345A (en) * | 2004-12-18 | 2006-06-21 | 青岛大学 | Method for preparing polyocarboxy acid type pigment ink |
| CN104817663A (en) * | 2015-04-10 | 2015-08-05 | 广州市建筑科学研究院有限公司 | Preparation method of polycarboxylate water-reducer capable of inhibiting side-effect of montmorillonite and polymeric monomer |
| CN106480753A (en) * | 2016-08-31 | 2017-03-08 | 浙江德誉进出口有限公司 | A kind of real silk blend polyester fabric digit printing ink and preparation method thereof |
| CN111499775A (en) * | 2017-11-27 | 2020-08-07 | 湖南辰砾新材料有限公司 | Polyamino modified cyclodextrin and application thereof |
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