Marker pen ink washable auxiliary polymer as well as preparation method and application thereof

Abstract

The invention discloses a washable auxiliary polymer for mark pen ink, and a preparation method and application of the washable auxiliary polymer. Wherein the polymer of the washable auxiliary agent for the mark pen ink comprises sulfonated polyvinylpyrrolidone with a structure as shown in a formula I, # imgabs0 #, and n is equal to 2-4. According to the mark pen ink, sulfonated polyvinylpyrrolidone of a specific structure is adopted, the water solubility of sulfonated polyvinylpyrrolidone is improved, meanwhile, the adhesive force of sulfonated polyvinylpyrrolidone to base materials such as skin and cloth is reduced, and therefore the washability of the ink is improved. Moreover, 75% medical alcohol is selected as the ink for the mark pen, and the main component of the ink is ethanol, so that the ink has no pungent smell.

Description

Technical Field

[0001] The invention belongs to the technical field of ink manufacturing, and in particular relates to a marker pen ink washable auxiliary agent polymer and a preparation method and application thereof. Background Art

[0002] Marker is a kind of drawing color pen specially used for writing or painting, which is used for quick one-time drawing. Alcohol marker is the most widely used type in the marker family. This type of ink pigment is highly stable and not easy to erase. It is generally used for marking operations that need to be retained for a long time. Since the main component of alcohol marker is alcohol, and the main solvent on the market is industrial ethanol, in addition to ethanol, industrial ethanol also contains a large amount of methanol or other aldehydes, so there is odor irritation. In addition, alcohol markers are mostly used by children because their solvent is alcohol, which is insoluble in water and cannot be washed off when it comes into contact with clothes or skin. Summary of the invention

[0003] In order to improve the washability of marker pen ink, the present invention provides a marker pen ink washability aid polymer and a preparation method and application of the polymer.

[0004] The first aspect of the present invention provides a marker pen ink wash aid polymer, the polymer comprising a sulfonated polyvinyl pyrrolidone having a structure shown in Formula I,

[0005]

[0006] Among them, n=2-4.

[0007] The second aspect of the present invention provides a method for preparing the above-mentioned marker pen ink washable aid polymer, comprising: S1, reacting a sulfonating agent with 1-vinyl-2-pyrrolidone to obtain sulfonated 1-vinyl-2-pyrrolidone; and S2, polymerizing the sulfonated 1-vinyl-2-pyrrolidone to obtain sulfonated polyvinyl pyrrolidone.

[0008] According to one embodiment of the present invention, the sulfonating agent is one or more of ammonium persulfate, sodium persulfate, and potassium persulfate.

[0009] According to another embodiment of the present invention, in the step S1, 1-vinyl-2-pyrrolidone and the sulfonating agent are reacted in an aqueous solution at 110-120° C. for 4-6 hours to obtain a sulfonated 1-vinyl-2-pyrrolidone aqueous solution; wherein the mass concentration of 1-vinyl-2-pyrrolidone in the aqueous solution is 40-50%.

[0010] According to another embodiment of the present invention, in the step S2, the polymerization reaction is performed by adding an initiator to the aqueous solution of sulfonated 1-vinyl-2-pyrrolidone under an inert atmosphere and reacting at 60-80° C. for 4-8 hours.

[0011] According to another embodiment of the present invention, the initiator is one or more of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisovaleronitrile, and dimethyl azobisisobutyrate.

[0012] According to another embodiment of the present invention, the amount of the initiator used is 0.4%-0.6% of the mass of the sulfonated 1-vinyl-2-pyrrolidone aqueous solution.

[0013] The third aspect of the present invention provides a marker pen ink, comprising a dye, a moisturizer, a preservative, sulfonated 1-vinyl-2-pyrrolidone, isomeric alcohol polyether phosphate and 75% medical alcohol; wherein, by weight, the marker pen ink comprises: 1.0-5.0 parts of the dye; 5.0-10.0 parts of the moisturizer; 0.1-1.0 parts of the preservative; 5.0-10.0 parts of the washable aid polymer according to claim 1; 0.1-0.5 parts of isomeric alcohol polyether phosphate; and 72.3-88.6 parts of 75% medical alcohol.

[0014] According to one embodiment of the present invention, the dye is one or more combinations of water-alcohol universal acid dye blue, water-alcohol universal acid dye red, and water-alcohol universal acid dye yellow; and / or the moisturizer is one or more combinations of glycidyl ether, ethylene glycol, glycerol, propylene glycol, and dipropylene glycol butyl ether; and / or the preservative is one or more combinations of kasone, isothiazolinone, bromophenol, and dodecyldimethylbenzyl ammonium bromide.

[0015] A fourth aspect of the present invention provides a marker pen, comprising the above-mentioned marker pen ink.

[0016] The marker pen ink of the present invention adopts sulfonated polyvinyl pyrrolidone of a specific structure, which improves the water solubility of sulfonated polyvinyl pyrrolidone and reduces the adhesion of sulfonated polyvinyl pyrrolidone to substrates such as skin and cloth, thereby improving the water washability of the ink. In addition, the marker pen ink of the present invention uses 75% medical alcohol, the main component of which is ethanol, so the ink has no irritating odor. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 It is a schematic diagram of the principle of improving the water washability of the washable aid polymer of the present invention in marker pen ink.

[0018] Figure 2 It is a reaction schematic diagram of the preparation method of the washability aid polymer of the present invention. DETAILED DESCRIPTION

[0019] The present invention is described in detail below in conjunction with specific implementation modes.

[0020] The marker pen ink washable aid polymer of the present invention comprises a sulfonated polyvinyl pyrrolidone having a structure shown in Formula I.

[0021]

[0022] Among them, n=2-4.

[0023] The polymer has high water solubility and can improve the water washability of the ink when applied to the ink. Figure 1 The schematic diagram shows the principle of improving the water washability of the polymer when used in ink. As can be seen from the figure, when the ink sticks to the cloth or skin, the sulfonated polyvinyl pyrrolidone shown in Formula I encapsulates the dye molecules, forming a bridge structure between the dye and the skin and cloth, blocking its contact with the skin and cloth, thereby achieving a washable effect.

[0024] The method for preparing the sulfonated polyvinyl pyrrolidone shown in formula I comprises: S1, reacting a sulfonating agent with 1-vinyl-2-pyrrolidone to obtain sulfonated 1-vinyl-2-pyrrolidone; and S2, polymerizing the sulfonated 1-vinyl-2-pyrrolidone to obtain sulfonated polyvinyl pyrrolidone.

[0025] The reaction process is as follows Figure 2 As shown. First, in step S1, sulfonated 1-vinyl-2-pyrrolidone is obtained. 1-vinyl-2-pyrrolidone and a sulfonating agent are dissolved in water. The mass concentration of 1-vinyl-2-pyrrolidone in the aqueous solution is 40-50%. 1-vinyl-2-pyrrolidone and a sulfonating agent are reacted in an aqueous solution at 110-120° C. for 4-6 hours to obtain a sulfonated 1-vinyl-2-pyrrolidone aqueous solution.

[0026] The sulfonating agent may be one or more of ammonium persulfate, sodium persulfate, and potassium persulfate.

[0027] Next, in step S2, a polymerization reaction is carried out. The polymerization reaction is carried out by adding an initiator to an aqueous solution of sulfonated 1-vinyl-2-pyrrolidone under an inert atmosphere and reacting at 60-80° C. for 4-8 hours.

[0028] The initiator can be one or more of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisovaleronitrile, and dimethyl azobisisobutyrate. The amount of the initiator used is 0.4%-0.6% of the mass of the sulfonated 1-vinyl-2-pyrrolidone aqueous solution.

[0029] The marker ink of the present invention comprises a dye, a moisturizer, a preservative, sulfonated 1-vinyl-2-pyrrolidone, isomeric alcohol polyether phosphate and 75% medical alcohol. In parts by weight, the marker ink comprises: 1.0-5.0 parts of a dye; 5.0-10.0 parts of a moisturizer; 0.1-1.0 parts of a preservative; 5.0-10.0 parts of a washable aid polymer shown in formula I; 0.1-0.5 parts of isomeric alcohol polyether phosphate; and 72.3-88.6 parts of 75% medical alcohol. The marker ink of the present invention has high washability because it uses a washable aid polymer shown in formula I, and because the polymer has high water solubility and low adhesion to substrates such as skin and cloth. In addition, the ink of the present invention uses medical alcohol and does not contain methanol or other aldehyde substances, so it does not have a pungent odor.

[0030] The dye, moisturizing agent, preservative and other additives used in the marker ink of the present invention are commonly used additives for marker ink. Specifically, the dye can be one or more combinations of water-alcohol universal acid dye blue, water-alcohol universal acid dye red, and water-alcohol universal acid dye yellow. The moisturizing agent can be one or more combinations of glycidyl ether, ethylene glycol, glycerol, propylene glycol, and dipropylene glycol butyl ether. The preservative can be one or more combinations of kason, isothiazolinone, bromophenol, and dodecyl dimethyl benzyl ammonium bromide.

[0031] The present invention is further described below by specific application examples. However, these application examples are merely exemplary and do not constitute any limitation to the scope of protection of the present invention. In the following examples and comparative examples, the reagents, materials and instruments used are commercially available unless otherwise specified. The "parts" described in the following examples all refer to "parts by weight".

[0032] Example 1

[0033] Under the protection of nitrogen, 400 g of deionized water, 300 g of 1-vinyl-2-pyrrolidone and 300 g of ammonium persulfate were reacted at 120° C. for 4 hours to obtain a sulfonated 1-vinyl-2-pyrrolidone aqueous solution.

[0034] Add 2.5 g of initiator AIBN to 500 g of sulfonated 1-vinyl-2-pyrrolidone aqueous solution, react at 65-75 ° C under nitrogen protection for 6 hours, then heat to 100 ° C, evaporate to dryness to obtain powder A, add powder A to ethyl acetate solution, stir well, filter insoluble matter and dry to obtain sulfonated polyvinyl pyrrolidone.

[0035] Example 2

[0036] Under the protection of nitrogen, 400 g of deionized water, 300 g of 1-vinyl-2-pyrrolidone and 300 g of ammonium persulfate were reacted at 110° C. for 4 hours to obtain a sulfonated 1-vinyl-2-pyrrolidone aqueous solution.

[0037] Add 2.5 g of initiator AIBN to 500 g of sulfonated 1-vinyl-2-pyrrolidone aqueous solution, react at 65-75 ° C under nitrogen protection for 6 hours, then heat to 100 ° C, evaporate to dryness to obtain powder A, add powder A to ethyl acetate solution, stir well, filter insoluble matter and dry to obtain sulfonated polyvinyl pyrrolidone.

[0038] Example 3

[0039] Under the protection of nitrogen, 400 g of deionized water, 400 g of 1-vinyl-2-pyrrolidone and 200 g of ammonium persulfate were reacted at 120° C. for 4 hours to obtain a sulfonated 1-vinyl-2-pyrrolidone aqueous solution.

[0040] Add 2.5 g of initiator AIBN to 500 g of sulfonated 1-vinyl-2-pyrrolidone aqueous solution, react at 65-75 ° C under nitrogen protection for 6 hours, then heat to 100 ° C, evaporate to dryness to obtain powder A, add powder A to ethyl acetate solution, stir well, filter insoluble matter and dry to obtain sulfonated polyvinyl pyrrolidone.

[0041] Example 4

[0042] Under the protection of nitrogen, 400 g of deionized water, 400 g of 1-vinyl-2-pyrrolidone and 200 g of ammonium persulfate were reacted at 120° C. for 5 hours to obtain a sulfonated 1-vinyl-2-pyrrolidone aqueous solution.

[0043] Add 2.5 g of initiator AIBN to 500 g of sulfonated 1-vinyl-2-pyrrolidone aqueous solution, react at 65-75 ° C under nitrogen protection for 6 hours, then heat to 100 ° C, evaporate to dryness to obtain powder A, add powder A to ethyl acetate solution, stir well, filter insoluble matter and dry to obtain sulfonated polyvinyl pyrrolidone.

[0044] The finished product content and average degree of polymerization of the sulfonated polyvinyl pyrrolidone prepared in Examples 1-4 are shown in Figure 1.

[0045] Table 1

[0046] Example Quality of Sulfonated Polyvinyl Pyrrolidone Average degree of polymerization Example 1 183.83g 2.3 Example 2 144.7g 1.8 Example 3 239.4g 3.1 Example 4 269.2g 3.7

[0047] In order to test the washability of the sulfonated polyvinyl pyrrolidone prepared in Examples 1-4 for use in ink, the sulfonated polyvinyl pyrrolidone prepared in Examples 1-4 was used to prepare inks and verify the results. The ink preparation process is as follows.

[0048] 10 parts of sulfonated poly 1-vinyl-2-pyrrolidone and 35 parts of 75% medical alcohol prepared in Examples 1-4 were added to a stirring device for stirring at a speed of 400 rpm for 40 minutes to obtain an intermediate. 3.1 parts of acid dye red 18, 1.5 parts of acid pigment blue 9, 0.22 parts of acid dye yellow 23, 6.0 parts of glycerol, 0.2 parts of preservative, and 0.2 parts of isomeric alcohol polyether phosphate were added, and then the intermediate was added, and the stirring machine was stirred at a speed of 400 rpm for 1 hour, and then 43.28 parts of 75% medical alcohol were added and stirred for 1 hour, and then the black ink of Application Examples 1-4 was obtained respectively. The components of the ink prepared in Application Examples 1-4 are shown in Table 2.

[0049] Table 2

[0050]

[0051] The inks prepared in Application Examples 1-4 were made into pens and their washability was tested. The test steps are as follows:

[0052] (1) Assembling the prepared ink into a pen, the pen parts include a fiber water storage core, a fiber pen head and a plastic pen shell, and the ink filling amount is 2.0g;

[0053] (2) The test surfaces included A4 copy paper, six-textile fabric, skin and glass;

[0054] (3) Washability: A spiral line with a diameter of 10 mm to 20 mm was manually drawn on the surface of six woven fabrics (DW multi-fiber adjacent fabric), skin, and glass.

[0055] Six fabrics: After the stitches are kept for 1 hour, soak the six fabrics in tap water for 30 minutes. During this period, it should be gently stirred and cleaned several times, and then the sample should be rinsed in running water for 1min to 2min. Take out the sample and unfold it, place it in a ventilated and dark room to dry naturally, and visually inspect the stitches remaining on the sample (this test method and judgment standard refer to QB / T 5969-2023 watercolor pen). The washability level is: Level 1: No stitches remain on all 6 materials; Level 2: No stitches remain on 4 or 5 materials; Level 3: No stitches remain on less than 4 materials.

[0056] Skin: Keep the stitches for 30 minutes, then scrub them back and forth 4 times with clean water and check whether there are any remaining stitches.

[0057] Glass: Leave the trace for 1 hour, then wipe it off with a wet tissue.

[0058] The test results are shown in Table 3.

[0059] Table 3

[0060] Test items (washability) Application Example 1 Application Example 2 Application Example 3 Application Example 4 Six weaving Level 3 Level 4 Level 3 Level 2 skin Partially washable Partially washable Partially washable Washable Glass Washable Partially washable Washable Washable

[0061] From the test data in Table 3, it can be seen that the sulfonated 1-vinyl-2-pyrrolidone prepared in Example 4 has the best test effect under the same conditions, that is, the best washability. The following application examples 5-7 use the sulfonated poly 1-vinyl-2-pyrrolidone prepared in Example 4 to prepare ink, and test the washability and odor removal of the ink.

[0062] Application Example 5

[0063] 10 parts of sulfonated poly 1-vinyl-2-pyrrolidone and 35 parts of 75% medical alcohol are added to a stirring device and stirred at a speed of 400 rpm for 40 minutes to obtain an intermediate. 3.1 parts of acid dye red 18, 1.5 parts of acid pigment blue 9, 0.22 parts of acid dye yellow 23, 6.0 parts of glycerol, 0.2 parts of preservative, and 0.2 parts of isomeric alcohol polyether phosphate are added, and then the intermediate is added, and the stirring is carried out for 1 hour with a stirring machine at a speed of 400 rpm, and then 43.28 parts of 75% medical alcohol are added and stirred for 1 hour to obtain black ink.

[0064] Application Example 6

[0065] 8 parts of sulfonated poly 1-vinyl-2-pyrrolidone and 35 parts of 75% medical alcohol are added to a stirring device and stirred at a speed of 400 rpm for 40 minutes to obtain an intermediate. 3.1 parts of acid dye red 18, 1.5 parts of acid pigment blue 9, 0.22 parts of acid dye yellow 23, 6.0 parts of glycerol, 0.2 parts of preservative, and 0.2 parts of isomeric alcohol polyether phosphate are added, and then the intermediate is added, and the stirring is carried out for 1 hour with a stirring machine at a speed of 400 rpm, and then 45.28 parts of 75% medical alcohol are added and stirred for 1 hour to obtain black ink.

[0066] Application Example 7

[0067] Add 5 parts of sulfonated poly 1-vinyl-2-pyrrolidone and 35 parts of 75% medical alcohol into a stirring device and stir at a speed of 400rpm for 40 minutes to obtain an intermediate. Add 3.1 parts of acid dye red 18, 1.5 parts of acid pigment blue 9, 0.22 parts of acid dye yellow 23, 6.0 parts of glycerol, 0.2 parts of preservative, 0.2 parts of isomeric alcohol polyether phosphate, then add the intermediate, stir at a speed of 400rpm for 1 hour, then continue to add 50.28 parts of 75% medical alcohol and continue to stir for 1 hour to obtain black ink.

[0068] Comparative Example 1

[0069] Except that the ink does not contain sulfonated poly-1-vinyl-2-pyrrolidone, the other components are the same as those in Application Example 5. 45 parts of 75% medical alcohol and other components are mixed and stirred at 400 rpm for 1 hour, and then 43.28 parts of 75% medical alcohol are added and stirred for 1 hour to obtain black ink.

[0070] Comparative Example 2

[0071] Except for using commercially available polyvinylpyrrolidone (PVP) to replace the sulfonated poly (1-vinyl-2-pyrrolidone) in Application Example 5, other components and preparation methods are the same as those in Application Example 5 to prepare black ink.

[0072] The components of the inks prepared in Application Examples 5-7 and Comparative Examples 1-2 are shown in Table 4.

[0073] Table 4

[0074]

[0075] The inks prepared in Example 5-7 and Comparative Example 1-2 were tested for washability and odor. The washability test method was the same as that in Example 1-4. The odor test was as follows:

[0076] (1) Assemble the odorless washable ink into a pen, the pen parts include a fiber water storage core, a fiber pen head and a plastic pen shell, and the ink filling volume is 2.0g;

[0077] (2) The test surfaces included A4 copy paper, six-textile fabric, skin and glass;

[0078] (3) Smell: Five 10 cm straight lines were drawn on the surface of A4 paper by hand and then the smell was blindly measured by a human.

[0079] The odor rating is expressed as: 1-no noticeable odor, 2-odor is only perceived but still difficult to define, 3-tolerable odor, 4-unpleasant odor, and 5-intolerable odor.

[0080] The test results are shown in Table 5.

[0081] Table 5

[0082]

[0083]

[0084] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A marker pen ink washable additive polymer, characterized in that: The polymer comprises a sulfonated polyvinyl pyrrolidone having a structure shown in Formula I, Among them, n=2-4.

2. A method for preparing the marker pen ink washable aid polymer according to claim 1, characterized in that: include: S1, reacting a sulfonating agent with 1-vinyl-2-pyrrolidone to prepare sulfonated 1-vinyl-2-pyrrolidone; as well as S2, polymerizing the sulfonated 1-vinyl-2-pyrrolidone to obtain sulfonated polyvinyl pyrrolidone.

3. The preparation method according to claim 2, characterized in that: The sulfonating agent is one or more of ammonium persulfate, sodium persulfate, and potassium persulfate.

4. The preparation method according to claim 2, characterized in that: In the step S1, 1-vinyl-2-pyrrolidone and the sulfonating agent are reacted in an aqueous solution at 110-120° C. for 4-6 hours to obtain a sulfonated 1-vinyl-2-pyrrolidone aqueous solution; The mass concentration of 1-vinyl-2-pyrrolidone in the aqueous solution is 40-50%.

5. The preparation method according to claim 4, characterized in that: In the step S2, the polymerization reaction is carried out by adding an initiator to the aqueous solution of sulfonated 1-vinyl-2-pyrrolidone under an inert atmosphere and reacting at 60-80° C. for 4-8 hours.

6. The preparation method according to claim 5, wherein the initiator is one or more of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisovaleronitrile, and dimethyl azobisisobutyrate.

7. The preparation method according to claim 5, wherein the amount of the initiator used is 0.4%-0.6% by mass of the sulfonated 1-vinyl-2-pyrrolidone aqueous solution.

8. A marker pen ink, characterized in that: Including dyes, moisturizers, preservatives, sulfonated 1-vinyl-2-pyrrolidone, isomeric alcohol polyether phosphate and 75% medical alcohol; Wherein, the marker pen ink comprises, by weight: 1.0-5.0 parts of the dye; 5.0-10.0 parts of the moisturizer; 0.1-1.0 parts of the preservative; 5.0-10.0 parts of the washable aid polymer according to claim 1; 0.1-0.5 parts of isomeric alcohol polyether phosphate; and 72.3-88.6 parts of 75% medical alcohol.

9. The marker ink according to claim 8, characterized in that: The dye is one or more combinations of water-alcohol universal acid dye blue, water-alcohol universal acid dye red, and water-alcohol universal acid dye yellow; and / or The moisturizing agent is one or more combinations of glycidyl ether, ethylene glycol, glycerol, propylene glycol, and dipropylene glycol butyl ether; and / or The preservative is one or more combinations of kasone, isothiazolinone, bromophenol, and dodecyldimethylbenzyl ammonium bromide.

10. A marker pen, characterized in that: Including the marker ink according to claim 8 or 9.

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