CN107354745B - Reusable writing cloth and special writing liquid thereof - Google Patents

Reusable writing cloth and special writing liquid thereof Download PDF

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Publication number
CN107354745B
CN107354745B CN201710559457.XA CN201710559457A CN107354745B CN 107354745 B CN107354745 B CN 107354745B CN 201710559457 A CN201710559457 A CN 201710559457A CN 107354745 B CN107354745 B CN 107354745B
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Prior art keywords
cloth
writing
cyclodextrin
water
stirring
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CN201710559457.XA
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CN107354745A (en
Inventor
杜芳芳
韩辉
杨振华
李明璐
双少敏
董川
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Shanxi University
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Shanxi University
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/16—Writing inks
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/332—Di- or polyamines
    • 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
    • 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
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/02—After-treatment
    • D06P5/04—After-treatment with organic compounds
    • D06P5/08—After-treatment with organic compounds macromolecular

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Preparation (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)

Abstract

The invention provides reusable writing cloth and a special writing liquid thereof. The preparation of the writing cloth comprises the following steps: carrying out puffing pretreatment on the cloth, and then repeatedly washing the cloth by using secondary water; grafting carboxylated cyclodextrin onto cloth through esterification, clathrating triphenylmethane dye with the carboxylated cyclodextrin, drying the cloth coated with the triphenylmethane dye, soaking the cloth in a polyvinyl alcohol aqueous solution with the mass fraction of 5-15% at 95 ℃ for half an hour, taking out the cloth, and naturally drying. The preparation of the special writing liquid comprises the following steps: adding emulsifier OP-10 into the alkali solution, adding flavoring agent, and stirring. The special liquid can be used for writing blue, pink, purple and orange writings on different writing cloths, and the writing is faded after being washed with water, can be naturally dried in the air in a short time, and can be used for writing again. The writing cloth and the special writing liquid thereof are simple to prepare, and the writing cloth can be repeatedly used.

Description

Reusable writing cloth and special writing liquid thereof
Technology neighborhood
The invention relates to the field of writing and drawing tools, in particular to reusable writing cloth, a special writing liquid thereof and a preparation method of the reusable writing cloth and the special writing liquid.
Background
Children like to scribble the random picture, often scribble wantonly on it with the clothes of oneself as the canvas, this can let clean father and mother be worried for this reason, prevent to wipe out children's nature, destroy children and arouse the inspiration of creation, put down and can cause the destruction of clothes because the painting on the clothes is difficult to wash, if can make any children scribble the picture at will can the color development and wash cloth that just can fade and special color development liquid, and make children's clothes with this cloth, the color development liquid is adorned in the pen container and is made the painting brush, so the head of a family just need not be for children to scribble wantonly on the clothes and worry again.
In addition, banner fabrics are one of the most widely used and largest in demand cloth materials. It is mainly used for indoor and outdoor scroll, flag, curtain, scenery and picture. However, the handwriting on the banner cloth is difficult to remove, the same banner cloth can only be used in a fixed situation and a fixed occasion, if a special writing liquid can be used for developing the color of the banner cloth, the writing cloth which can fade after being washed by water can be used as the banner cloth, so that the same banner cloth can be used for repeatedly writing different characters in different situations and situations, and the waste of a large amount of cloth can be avoided.
At present, message leaving cloth is arranged on some large-scale activity sites and tourist sites, guests and tourists on the sites sign and leave messages on the message leaving cloth, however, the writing on the message leaving cloth is difficult to clean, so that the cloth cannot be reused, if a special writing liquid can be used for developing the color of the cloth, the writing cloth which can fade after washing can be made to serve as the message leaving cloth, and the guests and the tourists can continue to use the message leaving cloth, so that the waste of the cloth is avoided, and the environment is protected.
Therefore, it is necessary to invent a reusable writing cloth and a special writing liquid thereof.
Disclosure of Invention
The invention aims to provide writing cloth and a preparation method thereof, the writing cloth is simple to manufacture, easily available in raw materials and low in cost, can be used for drawing and writing exercises, and can be repeatedly used after written handwriting is erased by water or wet cloth.
The invention also aims to provide the special writing liquid for the writing cloth and the preparation method thereof, and the writing liquid is simple to prepare and low in cost.
The invention provides a preparation method of writing cloth, which comprises the following steps:
1) according to the mass ratio of 1: 1-8: 6 to 10, dissolving cyclodextrin and NaOH in secondary water, heating and stirring for 5 to 10 minutes at the temperature of between 60 and 100 ℃, and adding BrCH with the mass of 1 to 3 times that of the cyclodextrin2COOH, continuously stirring for 2h, cooling to room temperature, adjusting the pH value of the system to 5 with hydrochloric acid, adding a proper amount of methanol to generate white precipitate, continuously adding methanol until the white precipitate is not generated, filtering, and vacuum-drying the white precipitate at 50 ℃ to obtain carboxylated cyclodextrin;
2) puffing the cloth at normal temperature, washing with secondary water for several times, soaking the washed cloth in water, and adding cotton cloth1-2 times of the above carboxylated cyclodextrin at 60-100 deg.C, N2Rapidly stirring for 10min in an air atmosphere, adjusting pH to 9 with 25% ammonia water, stirring for 1-3 hr, and cooling to room temperature;
3) according to the mass ratio of 1-12: 100 dissolving the triphenylmethane dye and the cloth treated in the step 2) in a volume ratio of 1: 5-15, performing ultrasonic treatment for 5 minutes, and then transferring to a shaking table to vibrate for 4-6 hours;
4) repeatedly washing the cloth treated in the step 3) with secondary water, and drying in an oven;
5) and (3) soaking the dried cloth in a polyvinyl alcohol aqueous solution with the mass fraction of 5-15% at 95 ℃ for half an hour, taking out the cloth and naturally airing.
The cyclodextrin in the step (1) is α -cyclodextrin, β -cyclodextrin or gamma-cyclodextrin.
The cloth in the step (2) can be pure cotton cloth, chemical fiber cloth or cotton and chemical fiber blended cloth.
And (2) the swelling treatment is to dissolve the cloth in an ethylenediamine solution with the mass fraction of 75% to soak for 15-30 minutes.
The triphenylmethane dye in the step (3) is o-cresolphthalein, phenolphthalein, thymolphthalein or guaiacol.
The invention provides a special writing liquid matched with writing cloth, which comprises the following components in percentage by mass: 0.4-8% of food-grade trisodium phosphate, 81-94.6% of water, 0-1% of flavoring agent and 105-10% of OP.
The preparation method of the writing liquid comprises the following steps: dissolving food grade trisodium phosphate in water according to the above proportion, adding OP10 and flavoring agent, and stirring.
Compared with the prior art, the invention has the beneficial effects that:
(1) the manufacturing method of the writing cloth is simple. The writing on the writing cloth can fade after being washed by water, so that the writing can be repeatedly written.
(2) The polyvinyl alcohol film on the surface of the cloth can allow water molecules to pass through, but the nonpolar dye cannot pass through, so that the loss of the dye during washing can be prevented.
(3) The alkaline color developing solution uses food-grade trisodium phosphate, and has the advantages of no toxicity, no harm, easily obtained raw materials, low price and simple formula.
The writing cloth and the special writing liquid thereof provided by the invention are simple to manufacture, easily available in raw materials and low in cost, and can be used for drawing and writing exercises, and can be repeatedly used after being erased by water or wet cloth.
Detailed description of the invention
Example 1
1) Dissolving α -cyclodextrin 1.5g and sodium hydroxide 4g in secondary water 10ml, heating and stirring at 60 deg.C for 5 min, adding BrCH 2.5g2And (3) stirring for 2 hours, cooling to room temperature, adjusting the pH value of the system to 5 with hydrochloric acid, adding a proper amount of methanol to generate white precipitate, adding methanol continuously until the white precipitate is not generated, filtering, and finally drying the white precipitate in vacuum at 50 ℃ to obtain the carboxylated cyclodextrin.
2) Carrying out swelling treatment on the cloth at a constant temperature, then washing the cloth for multiple times by using secondary water, and putting the washed cloth into a bath in a ratio of 1: 10 g of cotton and 0.3g of carboxylated cyclodextrin were added to water at 60 ℃ and N2Rapidly stirring for 10min under air atmosphere, adjusting pH to 9 with 25% ammonia water, stirring for 1 hr, and cooling to room temperature.
3) Dissolving 0.02g of phenolphthalein and 0.3g of the cloth treated in step 2) in a centrifuge tube containing 2mL of ethanol and 8mL of water, performing ultrasonic treatment for 5 minutes, and then transferring to a shaker to shake for 4 hours.
4) And repeatedly washing the treated cloth with secondary water, and drying in an oven.
5) And (3) soaking the dried cloth in a polyvinyl alcohol aqueous solution with the mass fraction of 5-15% at 95 ℃ for half an hour, taking out the cloth and naturally airing the cloth.
The preparation method of the writing liquid comprises the following steps: dissolving food grade trisodium phosphate 0.04g in water 10mL, adding OP10 1mL and flavoring agent 0.01g, and stirring.
The clear pink writing is displayed by writing on the prepared writing cloth with the writing liquid, the writing is erased by wet cloth after being dried, and the writing can be continued after 5 minutes.
Example 2
1) 1.5g of α -cyclodextrin and 6g of sodium hydroxide,dissolving in 10ml of secondary water, heating and stirring at 60 ℃ for 5 minutes, adding 3g of BrCH2And (3) stirring for 2 hours, cooling to room temperature, adjusting the pH value of the system to 5 with hydrochloric acid, adding a proper amount of methanol to generate white precipitate, adding methanol continuously until the white precipitate is not generated, filtering, and finally drying the white precipitate in vacuum at 50 ℃ to obtain the carboxylated cyclodextrin.
2) Carrying out swelling treatment on the cloth at a constant temperature, then washing the cloth for multiple times by using secondary water, and putting the washed cloth into a bath in a ratio of 1: 10 g of cotton and 0.6g of carboxylated cyclodextrin were added to water at 60 ℃ and N2Rapidly stirring for 10min under air atmosphere, adjusting pH to 9 with 25% ammonia water, stirring for 1 hr, and cooling to room temperature.
3) Dissolving 0.05g of thymolphthalein and 0.3g of the cloth treated in step 2) in a centrifuge tube mixed with 2mL of ethanol and 8mL of water, performing ultrasonic treatment for 5 minutes, and then transferring to a shaking table to shake for 4 hours.
4) And repeatedly washing the treated cloth with secondary water, and drying in an oven.
5) And (3) soaking the dried cloth in a polyvinyl alcohol aqueous solution with the mass fraction of 5-15% at 95 ℃ for half an hour, taking out the cloth and naturally airing.
The preparation method of the writing liquid comprises the following steps: dissolving food grade trisodium phosphate 0.04g in water 10mL, adding OP10 1mL and flavoring agent 0.01g, and stirring.
The special writing cloth is written with the writing liquid, clear blue writing is displayed, after the writing is dry, the writing is erased by wet cloth, and the writing can be continued after 5 minutes.
Example 3
1) Dissolving α -cyclodextrin 1.5g and sodium hydroxide 4g in secondary water 10ml, heating and stirring at 60 deg.C for 5 min, adding BrCH 2.5g2And (3) stirring for 2 hours, cooling to room temperature, adjusting the pH value of the system to 5 with hydrochloric acid, adding a proper amount of methanol to generate white precipitate, adding methanol continuously until the white precipitate is not generated, filtering, and finally drying the white precipitate in vacuum at 50 ℃ to obtain the carboxylated cyclodextrin.
2) Puffing the cloth at constant temperature, and performing multiple times with secondary waterWashing, namely putting the washed cloth into a bath in a ratio of 1: 10 g of cotton and 0.3g of carboxylated cyclodextrin were added to water at 60 ℃ and N2Rapidly stirring for 10min under air atmosphere, adjusting pH to 9 with 25% ammonia water, stirring for 1 hr, and cooling to room temperature.
3) Dissolving 0.05g of p-cresolphthalein and 0.3g of the cloth obtained in step 2) in a centrifuge tube mixed with 2mL of ethanol and 8mL of water, carrying out ultrasonic treatment for 5 minutes, and then transferring to a shaking table to shake for 4 hours.
4) And repeatedly washing the treated cloth with secondary water, and drying in an oven.
5) And (3) soaking the dried cloth in a polyvinyl alcohol aqueous solution with the mass fraction of 5-15% at 95 ℃ for half an hour, taking out the cloth and naturally airing.
The preparation method of the writing liquid comprises the following steps: dissolving food grade trisodium phosphate 0.04g in water 10mL, adding OP10 1mL and flavoring agent 0.01g, and stirring.
The special writing cloth is written with the writing liquid, clear purple writing is shown, after the writing is dry, the writing is erased by wet cloth, and the writing can be continued after 5 minutes.
Example 4
1) Dissolving α -cyclodextrin 1.5g and sodium hydroxide 6g in secondary water 10ml, heating and stirring at 60 deg.C for 5 min, adding BrCH 3g2And (3) stirring for 2 hours, cooling to room temperature, adjusting the pH value of the system to 5 with hydrochloric acid, adding a proper amount of methanol to generate white precipitate, adding methanol continuously until the white precipitate is not generated, filtering, and finally drying the white precipitate in vacuum at 50 ℃ to obtain the carboxylated cyclodextrin.
2) Carrying out swelling treatment on the cloth at a constant temperature, then washing the cloth for multiple times by using secondary water, and putting the washed cloth into a bath in a ratio of 1: 10 g of cotton and 0.6g of carboxylated cyclodextrin were added to water at 60 ℃ and N2Rapidly stirring for 10min under air atmosphere, adjusting pH to 9 with 25% ammonia water, stirring for 1 hr, and cooling to room temperature.
3) 0.02g of guaiacol and 0.3g of the cloth treated in step 2) were dissolved in a centrifuge tube containing 2mL of ethanol and 8mL of water, sonicated for 5 minutes, and then transferred to a shaker to shake for 4 hours.
4) And repeatedly washing the treated cloth with secondary water, and drying in an oven.
5) And (3) soaking the dried cloth in a polyvinyl alcohol aqueous solution with the mass fraction of 5-15% at 95 ℃ for half an hour, taking out the cloth and naturally airing.
The preparation method of the writing liquid comprises the following steps: dissolving food grade trisodium phosphate 0.04g in water 10mL, adding OP10 1mL and flavoring agent 0.01g, and stirring.
The special writing cloth is used for writing by using the writing liquid, clear orange writing is shown, after the writing is dry, the writing is erased by using wet cloth, and the writing can be continued after 5 minutes.

Claims (7)

1. The preparation method of the reusable writing cloth is characterized by comprising the following steps:
1) according to the mass ratio of 1: 1-8: 6 to 10, dissolving cyclodextrin and NaOH in secondary water, heating and stirring for 5 to 10 minutes at the temperature of between 60 and 100 ℃, and adding BrCH with the mass of 1 to 3 times that of the cyclodextrin2COOH, continuously stirring for 2h, cooling to room temperature, adjusting the pH value of the system to 5 with hydrochloric acid, adding a proper amount of methanol to generate white precipitate, continuously adding methanol until the white precipitate is not generated, filtering, and vacuum-drying the white precipitate at 50 ℃ to obtain carboxylated cyclodextrin;
2) puffing the cloth at room temperature, washing with secondary water for several times, soaking the washed cloth in water, adding carboxylated cyclodextrin 1-2 times the mass of the cotton cloth, and heating at 60-100 deg.C under N2Rapidly stirring for 10min in an air atmosphere, adjusting pH to 9 with 25% ammonia water, stirring for 1-3 hr, and cooling to room temperature; the swelling treatment is to dissolve the cloth in 75 percent ethylene diamine solution by mass fraction and soak the cloth for 15 to 30 minutes;
3) according to the mass ratio of 1-12: 100 dissolving the triphenylmethane dye and the cloth treated in the step 2) in a volume ratio of 1: 5-15, performing ultrasonic treatment for 5 minutes, and then transferring to a shaking table to vibrate for 4-6 hours;
4) repeatedly washing the cloth treated in the step 3) with secondary water, and drying in an oven;
5) and (3) soaking the dried cloth in a polyvinyl alcohol aqueous solution with the mass fraction of 5-15% at 95 ℃ for half an hour, taking out the cloth and naturally airing.
2. The method of claim 1, wherein the cyclodextrin of step (1) is α -cyclodextrin, β -cyclodextrin or γ -cyclodextrin.
3. The method for preparing a reusable writing cloth according to claim 1, wherein the cloth of the step (2) is a pure cotton cloth, a chemical fiber cloth, or a blended cloth of cotton and chemical fiber.
4. The method of claim 1, wherein the triphenylmethane dye in the step (3) is o-cresolphthalein, phenolphthalein, thymolphthalein or guaiacol.
5. A writing cloth prepared by the method of any one of claims 1 to 4.
6. A writing liquid for use with the writing cloth of claim 5, wherein: the components by mass percent are as follows: 0.4-8% of food-grade trisodium phosphate, 81-94.6% of water, 0-1% of flavoring agent and 105-10% of OP.
7. The method for preparing the writing liquid according to claim 6, wherein the food grade trisodium phosphate is dissolved in water according to the above ratio, and OP10 and the flavoring agent are added and stirred uniformly.
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US20220064469A1 (en) 2019-01-04 2022-03-03 Sanko Tekstil Isletmeleri San. Ve Tic. A.S. Writing and/or drawing system comprising ph sensitive dye and method thereof
CN110593000A (en) * 2019-08-13 2019-12-20 山西大学 Water-induced color development material and preparation method thereof

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US6818047B2 (en) * 1999-12-24 2004-11-16 Mitsubishi Pencil Kabushikikaisha Ink for ball pen and ball pen
CN102837532B (en) * 2012-09-17 2015-03-04 山西大学 Writing board coated with surface-modified paint and writing liquid matched with writing board
CN103434309B (en) * 2013-09-09 2015-06-10 吉林大学 Novel reusable water writing paper
CN105522839B (en) * 2015-11-24 2018-02-09 吉林大学 A kind of reusable water writing paper
CN105860664B (en) * 2016-06-08 2019-06-28 山西大学 It is a kind of can water cause the white board pen ink and preparation method thereof to fade

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