Special wear-resistant color paste for gel ink as well as preparation method and application of special wear-resistant color paste

Abstract

The invention relates to a special wear-resistant color paste for gel ink as well as a preparation method and application thereof, the novel special wear-resistant color paste for gel ink is prepared, inorganic nanoparticles, namely aluminum oxide and / or silicon carbide, are added into the color paste, and in the writing process of a gel ink pen, ink enters between a ball bead and a ball seat, so that the ball bead and the ball seat are not damaged. Aluminum oxide and silicon carbide can form a bearing structure between the ball bead and the ball seat, on one hand, abrasion is resisted through the hardness of aluminum oxide and silicon carbide, and on the other hand, abrasion is reduced through a rolling structure of the bearing structure, so that the problems of ink leakage and white stitch flying are solved; besides, the inorganic nanoparticles are added in the grinding and mixing process, uniform mixing can be achieved while the particle size of the inorganic nanoparticles and other components is controlled, the inorganic nanoparticles are prevented from settling, the stability of the color paste is improved, and therefore the pen point is prevented from being blocked; on the basis of solving the problems, the use of existing polymer resin is avoided, and the prepared color paste is high in pigment content.

Description

Technical Field

[0001] The invention relates to a special wear-resistant color paste for neutral ink and a preparation method and application thereof. Background Art

[0002] Neutral ink is prepared by adding various functional additives to the color paste, such as moisturizers, lubricants, thickeners, pH adjusters, etc. Since there are no neutral ink color paste products, neutral ink is usually prepared using water-based paint and water-based ink color paste. The particle size of water-based paint is coarse and most of them contain polymer resins. The particle size distribution of the prepared neutral ink is difficult to meet the requirements, and the viscosity is unstable, which makes the pen tip easy to clog; the particle size of water-based ink color paste is small but the solid content is generally low, resulting in low pigment content.

[0003] In addition, during the writing process of the gel pen, due to the difference in hardness between the ball and the ball seat, the ball seat is prone to wear, resulting in ink leakage, white lines and other problems, affecting the writing experience. In the prior art, a substance with a higher hardness is added to the ink to reduce the wear problem between the ball and the ball seat. However, a substance with a higher hardness is usually difficult to remain stable in the ink and is prone to sedimentation, resulting in the problem of clogging the pen tip. Summary of the invention

[0004] The first technical problem to be solved by the present invention is to provide a wear-resistant color paste specially used for neutral ink with high pigment content and good stability to avoid clogging of the pen tip in view of the current status of the prior art.

[0005] The second technical problem to be solved by the present invention is to provide a wear-resistant color paste specially used for neutral ink, which can significantly reduce the wear between the ball and the ball seat of the neutral pen, thereby eliminating the problems of ink leakage and white line traces.

[0006] The third technical problem to be solved by the present invention is to provide a preparation method and application of the above-mentioned wear-resistant color paste specially used for neutral ink in view of the current status of the prior art.

[0007] The technical solution adopted by the present invention to solve at least one of the above technical problems is:

[0008] A wear-resistant color paste specially used for neutral ink, comprising the following components by weight percentage:

[0009]

[0010]

[0011] Wherein, the inorganic nanoparticles are aluminum oxide and / or silicon carbide, and the inorganic nanoparticles are added in the form of grinding and mixing during the preparation of the wear-resistant color paste specially used for neutral ink.

[0012] Preferably, the inorganic nanoparticles are at least one of α-aluminum oxide and α-silicon carbide with a spherical spatial structure. Further preferably, the particle size of the inorganic nanoparticles is 200-600nm. The α-aluminum oxide and α-silicon carbide selected by the present invention have suitable hardness and sphericity, and can enter between the ball and the ball seat of the gel pen with the ink during the writing process, play the role of a bearing, reduce the contact surface between the ball and the ball seat, and reduce wear. When the particle size of the inorganic nanoparticles is less than 200nm, the effect of the inorganic nanoparticles on reducing wear is limited. To achieve the expected effect of reducing wear, a larger amount is required, and a large amount of inorganic nanoparticles will cause the smoothness of the ink to decrease; when the particle size of the inorganic nanoparticles is greater than 600nm, the smoothness of the prepared ink is poor, and the large particles are more likely to settle and clog the pen tip. The present invention, on the basis of selecting α-aluminum oxide and α-silicon carbide, limits its particle size to 200-600nm, which can well take into account the problem of reducing wear and ink stability.

[0013] Preferably, the dispersant includes dispersant a and dispersant b, wherein the dispersant a is at least one of anionic dispersant, nonionic dispersant and super dispersant; and the dispersant b is at least one of polycarboxylic acid ammonium salt, ammonium polyacrylate and carboxylic acid copolymer ammonium salt.

[0014] More preferably, the anionic dispersant is selected from sodium methylene dinaphthalene sulfonate and tristyrylphenol polyoxyethylene ether ammonium sulfate; the nonionic dispersant is selected from polyoxyethylene alkylphenol ether and sorbitol alkylate; the hyperdispersant is selected from Solsperse TM Series (Lubrizol); the dispersant b is selected from ARON A-30SL (produced by Toagosei Co., Ltd.), ARON A-6114 (produced by Toagosei Co., Ltd.), D-305 (Chukyō Oil), and Y-181 (Chukyō Oil).

[0015] Preferably, the pH regulator is an organic amine, selected from at least one of monoethanolamine, diethanolamine, triethanolamine, ammonia water, and AMP-95.

[0016] Preferably, the defoaming agent is at least one of a silicone defoaming agent and a mineral oil defoaming agent; and the moisturizing agent is at least one of propylene glycol, glycerin and polyethylene glycol.

[0017] Preferably, the pigment is one of a black pigment, a red pigment and a blue pigment, wherein the black pigment is carbon black; the red pigment is at least one of PR48:1, PR48:2, PR57:1, PR146, PR122, PR254, PR269 and PV19; and the blue pigment is at least one of PB15:1, PB15:2, PB15:3 and PB15:4.

[0018] A method for preparing the above-mentioned wear-resistant color paste for neutral ink comprises the following steps:

[0019] (1) Add deionized water, dispersant a, pH adjuster, and defoamer into a container and mix well according to the formula components and contents;

[0020] (2) adding a pigment to the mixture obtained in step (1) under stirring, and stirring until a pigment slurry is formed;

[0021] (3) The pigment slurry obtained in step (2) is transferred into a sand mill and ground to a pigment particle size D90 < 200 nm. The grinding conditions are: the grinding medium is 0.4 mm zirconium beads, the zirconium bead filling rate is 85%, the grinding speed is 3400 r / min, and the grinding temperature is 20-35° C.;

[0022] (4) Add dispersant b and inorganic nanoparticles to the mixture obtained in step (3), and continue grinding for 0.3 to 0.7 hours to obtain a wear-resistant color paste for neutral ink. The obtained wear-resistant color paste for neutral ink has an average particle size of 100 to 200 nm and a pH of 8 to 9.

[0023] In the above preparation method, the present invention adopts two dispersants, wherein dispersant a is mainly used for dispersing pigments in step (3) (i.e. before the inorganic nanoparticles are added). This is mainly because the mixed slurry before the addition of inorganic nanoparticles is mainly pigments, and dispersant a has a pigment-friendly group at one end, which is easily adsorbed on the surface of the pigment, and one end has a negative charge or a hydrophilic long chain. After grinding, the dispersant attached to the surface of the refined pigment particles prevents the pigment from aggregating due to electrostatic repulsion or steric hindrance, so as to achieve the stable existence of the pigment microparticles. In step (4), dispersant b and inorganic nanoparticles are added simultaneously, mainly because dispersant b is more easily adsorbed on the surface of alumina or silicon carbide, which is conducive to the stability and non-aggregation of alumina or silicon carbide after microparticles, and finally prepares a product with uniform particle size, not easy to settle, and good stability.

[0024] The invention discloses an application of a wear-resistant color paste specially used for neutral ink, which is used to make neutral ink for use in a neutral pen. The neutral pen comprises a ball and a ball seat for drawing out ink by writing. During the writing process of the neutral pen, the ink enters between the ball and the ball seat. The α-aluminum oxide or α-silicon carbide constitutes a bearing structure located between the ball and the ball seat and used to reduce the contact surface between the ball and the ball seat.

[0025] Compared with the prior art, the advantages of the present invention are: the present invention prepares a new wear-resistant color paste specially used for neutral ink, and inorganic nanoparticles such as aluminum oxide and / or silicon carbide are added to the color paste. During the writing process of the neutral pen, the ink enters between the ball and the ball seat, and the aluminum oxide and silicon carbide will form a bearing structure between the ball and the ball seat. On the one hand, the hardness of the aluminum oxide and silicon carbide themselves is used to resist wear, and on the other hand, the rolling structure of the bearing structure is used to reduce wear, thereby eliminating the problems of ink leakage and white lines. In addition, the above-mentioned inorganic nanoparticles are added during the grinding and mixing process, and can be evenly mixed with other components while controlling the particle size, preventing the inorganic nanoparticles from settling, improving the stability of the color paste, and thus avoiding clogging of the pen tip. Based on the solution to the above problems, the present application avoids the use of existing polymer resins, and the prepared color paste has a high pigment content. DETAILED DESCRIPTION

[0026] The present invention is further described in detail below with reference to the embodiments.

[0027] The neutral ink wear-resistant color paste of this embodiment includes the following components according to weight percentage:

[0028]

[0029]

[0030] The inorganic nanoparticles are aluminum oxide or silicon carbide, and the inorganic nanoparticles are added in the form of grinding and mixing during the preparation of the wear-resistant color paste specially used for neutral ink.

[0031] The inorganic nanoparticles of this embodiment are at least one of spherical α-alumina and α-silicon carbide. It is further preferred that the particle size of the inorganic nanoparticles is 200-600nm. The α-alumina and α-silicon carbide selected by the present invention have suitable hardness and sphericity, and can enter the ball and the ball seat of the gel pen with the ink during the writing process, play the role of a bearing, reduce the contact surface between the ball and the ball seat, and reduce wear. When the particle size of the inorganic nanoparticles is less than 200nm, the effect of the inorganic nanoparticles on reducing wear is limited. To achieve the expected effect of reducing wear, a larger amount is required, and a large amount of inorganic nanoparticles will cause the smoothness of the ink to decrease; when the particle size of the inorganic nanoparticles is greater than 600nm, the smoothness of the modulated ink is poor, and the large particles are more likely to settle and clog the pen tip. The present invention, on the basis of selecting α-alumina and α-silicon carbide, limits its particle size to 200-600nm, which can well take into account the problem of reducing wear and ink stability.

[0032] The dispersants of this embodiment include dispersant a and dispersant b, wherein dispersant a is at least one of anionic dispersant, nonionic dispersant and super dispersant; dispersant b is at least one of polycarboxylic acid ammonium salt, polyacrylate ammonium and carboxylic acid copolymer ammonium salt. The anionic dispersant is selected from sodium methylene dinaphthalene sulfonate and tristyrylphenol polyoxyethylene ether ammonium sulfate; the nonionic dispersant is selected from polyoxyethylene alkylphenol ether and sorbitol alkylate; the super dispersant is selected from Solsperse TM Series (Lubrizol); the dispersant b is selected from ARON A-30SL (produced by Toagosei Co., Ltd.), ARON A-6114 (produced by Toagosei Co., Ltd.), D-305 (Chukyō Oil), and Y-181 (Chukyō Oil).

[0033] The pH regulator of this embodiment is an organic amine, selected from at least one of monoethanolamine, diethanolamine, triethanolamine, ammonia water, and AMP-95. The defoamer of this embodiment is at least one of a silicone defoamer and a mineral oil defoamer; the moisturizer is at least one of propylene glycol, glycerol, and polyethylene glycol. The pigment of this embodiment is one of a black pigment, a red pigment, and a blue pigment, wherein the black pigment is carbon black; the red pigment is at least one of PR48:1, PR48:2, PR57:1, PR146, PR122, PR254, PR269, and PV19; the blue pigment is at least one of PB15:1, PB15:2, PB15:3, and PB15:4.

[0034] In this embodiment, the application of wear-resistant color paste specially used for neutral ink is used to make neutral ink for use in a neutral pen. The neutral pen includes a ball and a ball seat for drawing out the ink by writing. During the writing process of the neutral pen, the ink enters between the ball and the ball seat. α-alumina and / or α-silicon carbide constitute a bearing structure located between the ball and the ball seat for reducing the contact surface between the ball and the ball seat.

[0035] Embodiment 1:

[0036] In terms of weight percentage, the wear-resistant color paste for neutral ink in this embodiment includes the following components:

[0037]

[0038] The rest is deionized water.

[0039] The preparation method of the above-mentioned wear-resistant color paste for neutral ink comprises the following steps:

[0040] (1) According to the formula components and contents, deionized water, dispersant a (Solsperse(TM) 24000SC), p-triethanolamine, Foamex825 defoaming agent and propylene glycol were added into a container and mixed evenly;

[0041] (2) adding carbon black to the mixture obtained in step (1) under stirring, and stirring at 1000 r / min for 2 h to form a carbon black slurry;

[0042] (3) the carbon black slurry obtained in step (2) is transferred into a sand mill and ground to a carbon black particle size D90 < 200 nm, the grinding conditions are: the grinding medium is 0.4 mm zirconium beads, the zirconium bead filling rate is 85%, the grinding speed is 3400 r / min, and the grinding temperature is 20-35° C.;

[0043] (4) Add dispersant b (ARON A-6114) and α-alumina to the mixture obtained in step (3), and continue grinding for 0.5 h to obtain a wear-resistant color paste specially used for neutral ink.

[0044] Embodiment 2:

[0045] In terms of weight percentage, the wear-resistant color paste for neutral ink in this embodiment includes the following components:

[0046]

[0047] The preparation method of the above-mentioned wear-resistant color paste specially used for neutral ink is consistent with that in Example 1.

[0048] Embodiment 3:

[0049] In terms of weight percentage, the wear-resistant color paste for neutral ink in this embodiment includes the following components:

[0050]

[0051] The preparation method of the above-mentioned wear-resistant color paste specially used for neutral ink is consistent with that in Example 1.

[0052] Comparative Example 1:

[0053] The only difference from Example 1 is:

[0054] No inorganic nanoparticle α-alumina was added. Instead, all materials were ground and mixed together.

[0055] According to weight percentage, the color paste of this comparative example includes the following components:

[0056]

[0057] The preparation method of the above-mentioned color paste comprises the following steps:

[0058] (1) According to the formula components and contents, deionized water, dispersant a (Solsperse(TM) 24000SC), dispersant b (ARON A-6114), triethanolamine, Foamex 825 defoamer and propylene glycol were added into a container and mixed evenly;

[0059] (2) adding carbon black to the mixture obtained in step (1) under stirring, and stirring at 1000 r / min for 2 h to form a carbon black slurry;

[0060] (3) The carbon black slurry obtained in step (2) is transferred to a sand mill and ground until the carbon black particle size D90 is less than 200 nm, thereby obtaining the color paste of comparative example 1. The grinding conditions are: the grinding medium is 0.4 mm zirconium beads, the zirconium bead filling rate is 85%, the grinding speed is 3400 r / min, and the grinding temperature is 20-35°C.

[0061] Comparative Example 2:

[0062] The only difference from Example 1 is that the inorganic nanoparticles used are β-alumina. The preparation method is the same as that of Example 1.

[0063] Comparative Example 3:

[0064] The only difference from Example 1 is that the inorganic nanoparticles used are silicon dioxide instead of α-aluminum oxide or α-silicon carbide. The preparation method is the same as that of Example 1.

[0065] Comparative Example 4:

[0066] The only difference from Example 1 is that only one dispersant a is used. In terms of weight percentage, the following components are included:

[0067]

[0068] The corresponding preparation method is consistent with that in Example 1.

[0069] Comparative Example 5:

[0070] The only difference from Example 1 is that the inorganic nanoparticle α-alumina is mixed and ground together with other materials, rather than being mixed and ground with other materials and then added and ground together with the dispersant b.

[0071] According to weight percentage, the color paste of this comparative example includes the following components:

[0072]

[0073] The preparation method of the above-mentioned wear-resistant color paste for neutral ink comprises the following steps:

[0074] (1) According to the formula components and contents, deionized water, dispersant a (Solsperse(TM) 24000SC), dispersant b (ARON A-6114), triethanolamine, Foamex825 defoaming agent and propylene glycol were added into a container and mixed evenly;

[0075] (2) adding carbon black and α-alumina to the mixture obtained in step (1) under stirring, and stirring at 1000 r / min for 2 h to form a carbon black slurry;

[0076] (3) The pigment slurry obtained in step (2) is transferred into a sand mill and ground to a pigment particle size D90 < 200 nm. The grinding conditions are: the grinding medium is 0.4 mm zirconium beads, the zirconium bead filling rate is 85%, the grinding speed is 3400 r / min, and the grinding temperature is 20-35° C.;

[0077] The color paste prepared above was subjected to performance testing.

[0078] Evaluation of color paste stability:

[0079] Grade A: The color paste is sealed and stored at 50°C for more than 3 months without stratification, and the particle size change does not exceed 20% compared with the initial stage;

[0080] Grade B: The color paste is sealed and stored at 50°C for 2 to 3 months without stratification, and the particle size does not change by more than 20% compared with the initial stage;

[0081] Grade C: The color paste is sealed and stored at 50°C for 0 to 2 months without stratification, and the particle size change does not exceed 20% compared with the initial stage.

[0082] <Preparation of ink composition>

[0083] Prepare pigment paste, moisturizer, lubricant, thickener, pH adjuster, preservative, corrosion inhibitor and deionized water according to the following neutral ink composition ratio, add them to a container with a stirring device, stir, and after obtaining a uniform mixture, add appropriate amounts of thickener and pH adjuster and stir evenly, adjust to pH 8.2-8.7, and viscosity 800-1000mPa.s. After stirring for an appropriate time, filter with filter paper with a pore size of 1μm, take the filtrate, and degas to obtain an ink composition.

[0084]

[0085] The color paste in the above formula is the color paste prepared in the examples and comparative examples, the humectant is PEG400, the lubricant is a phosphate lubricant, the thickener is an alkali-swellable acrylate thickener, the pH regulator is a 50% triethanolamine aqueous solution, the preservative is 1,2-benzisothiazolin-3-one, and the corrosion inhibitor is benzotriazole.

[0086] The main properties of the prepared neutral ink composition are shown in Table 1.

[0087] Stitch evaluation:

[0088] Grade A: The writing and drawing instrument can draw 2000m without obvious line breaks, hollows, etc.

[0089] Grade B: The writing and drawing instrument draws 2000m, and the traces have slight disconnection, hollowness and other defects

[0090] Grade C: The writing and drawing instrument draws 2000m, and the traces have obvious defects such as broken lines and hollows.

[0091] Wear:

[0092] Grade A: After 1000m of marking, the difference in ball exposure is less than 0.005mm

[0093] Grade B: After 1000m of marking, the difference in ball exposure is less than 0.01mm and greater than 0.005mm

[0094] Grade C: After 1000m of marking, the difference in ball exposure is greater than 0.01mm

[0095] Ink stability evaluation:

[0096] Grade A: The ink is sealed and stored at 50°C for more than 3 months without stratification, and the particle size does not change by more than 20% compared with the initial stage;

[0097] Grade B: The ink is sealed and stored at 50°C for 2 to 3 months without stratification, and the particle size does not change by more than 20% compared with the initial stage;

[0098] Grade C: The ink is sealed and stored at 50°C for 0 to 2 months without stratification, and the particle size change does not exceed 20% compared with the initial stage.

[0099] Table 1

[0100]

Claims

1. A wear-resistant color paste for neutral ink, characterized by: According to weight percentage, it includes the following components: Wherein, the inorganic nanoparticles are aluminum oxide and / or silicon carbide, and the inorganic nanoparticles are added in the form of grinding and mixing during the preparation of the wear-resistant color paste specially used for neutral ink.

2. The wear-resistant color paste for neutral ink according to claim 1, characterized in that: The inorganic nanoparticles are at least one of α-aluminum oxide and α-silicon carbide with a spherical spatial structure.

3. The wear-resistant color paste for neutral ink according to claim 2, characterized in that: The particle size of the inorganic nanoparticles is 200-600 nm.

4. The wear-resistant color paste for neutral ink according to claim 1, characterized in that: The dispersant includes dispersant a and dispersant b, wherein the dispersant a is at least one of anionic dispersant, nonionic dispersant and super dispersant; and the dispersant b is at least one of polycarboxylic acid ammonium salt, polyacrylate ammonium and carboxylic acid copolymer ammonium salt.

5. The wear-resistant color paste for neutral ink according to claim 4, characterized in that: The anionic dispersant is selected from sodium methylene dinaphthalene sulfonate and tristyrylphenol polyoxyethylene ether ammonium sulfate; the nonionic dispersant is selected from polyoxyethylene alkylphenol ether and sorbitol alkylate; the hyperdispersant is selected from Solsperse TM Series (Lubrizol); The dispersant b is selected from ARON A-30SL (produced by Toagosei Co., Ltd.), ARON A-6114 (produced by Toagosei Co., Ltd.), D-305 (produced by Chukyo Oil), and Y-181 (produced by Chukyo Oil).

6. The wear-resistant color paste for neutral ink according to claim 1, characterized in that: The pH regulator is an organic amine, selected from at least one of monoethanolamine, diethanolamine, triethanolamine, ammonia water and AMP-95.

7. The wear-resistant color paste for neutral ink according to claim 1, characterized in that: The defoaming agent is at least one of a silicone defoaming agent and a mineral oil defoaming agent; the moisturizing agent is at least one of propylene glycol, glycerin and polyethylene glycol.

8. The wear-resistant color paste for neutral ink according to claim 1, characterized in that: The pigment is one of a black pigment, a red pigment and a blue pigment, wherein the black pigment is carbon black; the red pigment is at least one of PR48:1, PR48:2, PR57:1, PR146, PR122, PR254, PR269 and PV19; and the blue pigment is at least one of PB15:1, PB15:2, PB15:3 and PB15:

4.

9. A method for preparing the wear-resistant color paste for neutral ink according to any one of claims 1 to 8, characterized in that The following steps are involved: (1) Add deionized water, dispersant a, pH adjuster, and defoamer into a container and mix well according to the formula components and contents; (2) adding a pigment to the mixture obtained in step (1) under stirring, and stirring until a pigment slurry is formed; (3) The pigment slurry obtained in step (2) is transferred into a sand mill and ground to a pigment particle size D90 < 200 nm. The grinding conditions are: the grinding medium is 0.4 mm zirconium beads, the zirconium bead filling rate is 85%, the grinding speed is 3400 r / min, and the grinding temperature is 20-35° C.; (4) Add dispersant b and inorganic nanoparticles to the mixture obtained in step (3), and continue grinding for 0.3 to 0.7 hours to obtain a wear-resistant color paste specially used for neutral ink.

10. Application of a wear-resistant color paste for neutral ink, characterized in that: Neutral ink is prepared for use in a gel pen, wherein the gel pen comprises a ball and a ball seat for drawing out the ink during writing. During the writing process of the gel pen, the ink enters between the ball and the ball seat, and the α-aluminum oxide and / or α-silicon carbide constitute a bearing structure located between the ball and the ball seat for reducing the contact surface between the ball and the ball seat.

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