Gel pen ink with low temperature resistance

Abstract

The invention relates to gel pen ink with low temperature resistance, which adopts a humectant A capable of enabling an ink system to have a low freezing point, a humectant B capable of endowing the ink system with high moisture retention, and a humectant C capable of endowing the ink system with auxiliary moisture retention and lubricity, so that a water-based organic solvent system has the characteristic of low freezing point; the freezing point of the ink is reduced, so that the problem of phase separation caused at low temperature is avoided, and the gel pen ink can be maintained to have good moisturizing performance and certain lubricity so as to maintain good writing smoothness; a compound system of the high-shear thickening agent A and the low-shear thickening agent B is adopted, so that the ink can still keep good non-Newtonian fluid characteristics at a low temperature and has normal viscosity and thixotropic performance, meanwhile, the viscosity stability of the ink is maintained by using the antifreeze agent, the problem that the viscosity of the ink is suddenly changed due to environment change is avoided, and the viscosity stability of the ink is improved. Therefore, the stability of the ink is maintained.

Description

TECHNICAL FIELD

[0001] The present application relates to a neutral pen ink with low-temperature resistance. BACKGROUND

[0002] As a non-Newtonian fluid, the neutral pen ink has a high viscosity in static state to prevent it from flowing out of the gap, and the viscosity of the ink is reduced due to the shear force applied by the ball rolling during writing, so that the ink flows smoothly. However, in a low-temperature environment of-10℃ or even-20℃, the traditional neutral pen ink is prone to technical challenges such as solidification crystallization, loss of viscosity and flowability, resulting in problems such as writing interruption and incoherent handwriting.

[0003] The essence of the failure of the neutral ink in a low-temperature environment is the low-temperature phase change of the complex component system. The neutral pen ink contains pigments, water-based solvents, thickening agents, lubricants, pH regulators and other functional additives. When the temperature drops, the solvent will crystallize because it reaches the freezing point, causing phase separation; pigment particles will settle and aggregate due to the weakening of Brownian motion at low temperature; the additive system will lose flowability due to glass transition temperature change. The above reasons will cause the ink to fail to function normally at low temperature. SUMMARY

[0004] The technical problem to be solved by the present application is to provide a neutral pen ink with low-temperature resistance, which can reduce the freezing point of the ink to avoid phase separation and maintain the non-Newtonian fluid properties of the ink at low temperature, thereby maintaining the stability and smoothness of the ink.

[0005] The technical solution adopted by the present application to solve the above technical problems is:

[0006] A neutral pen ink with low-temperature resistance, comprising the following components by weight percentage:

[0007] Deionized water, 10% to 60%;

[0008] Humectant, 15% to 35%;

[0009] Antirust agent, 0.1% to 1.5%;

[0010] Antifreeze agent, 0.1% to 5%;

[0011] Lubricant, 0.1% to 2%;

[0012] pH regulator, 1% to 8%;

[0013] Thickening agent, 1% to 10%;

[0014] Preservative, 0.1% to 1.5%;

[0015] Color paste, 25% to 40%;

[0016] The moisturizing agent is compounded by a moisturizing agent A, a moisturizing agent B and a moisturizing agent C, the moisturizing agent A is used to make the ink system have a low freezing point, the moisturizing agent B has a hydroxyl group and is used to give the ink system high moisturizing property, and the moisturizing agent C is used to give the ink system auxiliary moisturizing property and lubricity.

[0017] The thickening agent is compounded by a high-shear thickening agent A and a low-shear thickening agent B.

[0018] Preferably, the moisturizing agent A is selected from at least one of ethylene glycol, 1,2-propanediol and 1,3-propanediol, the moisturizing agent B is selected from at least one of polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400 and polyethylene glycol 600, and the moisturizing agent C is selected from at least one of sorbitol, vinyl pyrrolidone, glycerol and triethylene glycol. Preferably, the percentage content of the moisturizing agent A, the moisturizing agent B and the moisturizing agent C in the ink is 1% to 10%, 5% to 25% and 1% to 10% respectively. By using the above-mentioned moisturizing agent system, the neutral pen ink can still maintain fluidity without crystallization at low temperature, the viscosity stability of the compounded moisturizing agent system at low temperature can be maintained, and the neutral pen ink can maintain good moisturizing property and certain lubricity.

[0019] Preferably, the thickening agent is an acrylic thickening agent and / or a polyurethane thickening agent, and the mass ratio of the high-shear thickening agent A to the low-shear thickening agent B is (4 to 7):1. Preferably, the acrylic thickening agent is selected from one or more of BASF HS1152, BASF AS1130, Dow TT615 and Dow TT93, and the polyurethane thickening agent is selected from one or more of VA01, VA02 and VA03 of Guangzhou Yangsong Technology Co., Ltd. Further preferably, the mass ratio of the thickening agent A to the thickening agent B is 5:1. Since the viscosity of the thickening agent changes differently when the thickening agent is subjected to force due to different shear degrees, the thickening agent is compounded in the application, so that the viscosity can be maintained within a reasonable range when the thickening agent is subjected to shear force at low temperature, and the ink cannot be written and the ink leaks from the pen tip gap due to extreme change of viscosity at low temperature.

[0020] Preferably, the rust preventive agent is one or more of benzotriazole, methylbenzotriazole, diethanolamine oleate and dialkyl thiourea.

[0021] Preferably, the lubricant is one or more of phosphate ester lubricant, fatty acid amide lubricant and polyether modified silicone oil lubricant.

[0022] Preferably, the pH regulator is one or more of diethanolamine, triethanolamine, 2-amino-2-methyl-1,3-propanediol, ammonia, sodium carbonate, alkanolamine.

[0023] Preferably, the preservative is one or more of potassium sorbate, benzisothiazolinone, methylisothiazolinone, sodium methylglycinate.

[0024] Preferably, the anti-freezing agent is at least one of FA2216 and FA2218 of Guangzhou Yangsong Technology Co., Ltd.

[0025] The color paste of the present application is an aqueous neutral color paste.

[0026] Compared with the prior art, the present application has the following advantages:

[0027] The present application adopts a moisturizing agent A that can make the ink system have a low freezing point, a moisturizing agent B that gives the ink system high moisturizing properties, and a moisturizing agent C that gives the ink system auxiliary moisturizing properties and lubricity, not only making the aqueous organic solvent system have the characteristics of a low freezing point, reducing the freezing point of the ink and thus avoiding the problem of phase separation at low temperatures, but also being able to maintain the neutral pen ink with good moisturizing properties and certain lubricity to maintain good writing smoothness.

[0028] The present application adopts a complex system of high-shear thickening agent A and low-shear thickening agent B, making the ink still maintain good non-Newtonian fluid characteristics at low temperatures, having normal viscosity and thixotropic properties, and at the same time using an anti-freezing agent to maintain the viscosity stability of the ink, avoiding the problem of sudden change in the viscosity of the ink due to environmental changes, thereby maintaining the stability of the ink.

[0029] The hydroxyl groups of the above-mentioned moisturizing agent system and thickening agent system can jointly construct a strong hydrogen bond network structure, which provides support for the low-temperature stability of the entire ink system; specifically, the moisturizing agent and the anti-freezing agent jointly maintain a stable liquid phase environment, the thickening agent plays its rheological regulation function in this stable liquid phase environment, and through the balance of high and low shear viscosities, it compensates for the deterioration of the rheological properties at low temperatures, thereby taking into account the anti-bleeding performance of the ink in the storage state and the smooth writing performance in the use state; at the same time, the balanced stable rheological property of the thickening agent also feeds back the viscosity stability regulation function of the anti-freezing agent, making the role of the anti-freezing agent in the ink system more uniform, and further strengthening the strong hydrogen bond network structure constructed by the moisturizing agent system and the thickening agent system; finally, the moisturizing system, the thickening system, and the anti-freezing system jointly cooperate to resist the writing challenge brought by low temperature from three aspects of inhibiting phase change, stabilizing rheology, and maintaining stable chemical state, realizing the smooth writing goal of the ink at low temperature, i.e., "not freezing (phase change stable), not bleeding (static viscosity stable), writable (dynamic viscosity controllable), and performance unchanged (component stable)". DETAILED DESCRIPTION

[0030] In order to make the above objectives, features and advantages of the present application more clear and comprehensible, the specific embodiments of the present application are described in detail below. In the following description, a lot of specific details are set forth in order to provide a thorough understanding of the present application. However, the present application can be implemented in many different ways other than those described herein, and one of ordinary skill in the art can make similar improvements without departing from the scope of the present application, and therefore the present application is not limited to the specific embodiments disclosed below.

[0031] Example 1

[0032] The neutral pen ink formulation with low temperature resistance of the present embodiment is as follows:

[0033] Component Manufacturer Addition amount / mass percentage Ethylene glycol Guangzhou Tongjie Chemical Co., Ltd. 10％ Polyethylene glycol 300 Haian Petrochemical Factory of Jiangsu Province 5％ Glycerin Guangzhou Tongjie Chemical Co., Ltd. 10％ Benzotriazole Germany Yang Cherry 0.5％ FA 2216 Guangzhou Yangsong Technology Co., Ltd. 2.5％ Iso-tridecyl alcohol phosphate Tokyo Chemical Industry Co., Ltd. 2％ Triethanolamine Dow Chemical 5％ TT 935 Dow Chemical 5％ VA 01 Guangzhou Yangsong Technology Co., Ltd. 1％ Methyl isothiazolinone Shanghai Borei Australia Trading Co., Ltd. 0.5％ Color paste Naimex New Material Co., Ltd. 30％ Deionized water Balance

[0034] The preparation method of the neutral pen ink with low temperature resistance of the present embodiment is as follows: 100 g of deionized water, 50 g of ethylene glycol, 25 g of polyethylene glycol 300, 50 g of glycerol and 2.5 g of benzotriazole are put into a beaker at room temperature, and a stirrer is used to stir at a speed of 400 r / min for 20 min until the benzotriazole in the solution is completely dissolved; then 12.5 g of FA2216 and 10 g of isotridecanol phosphate are added to the beaker for stirring, and the pH value of the solution is tested after 10 min, and then triethanolamine is added for pH value adjustment, and after the pH value of the solution reaches 8.2-8.5, continue to stir for 10 min; then add 15 g of TT935 and 3 g of VA01 in proportion for viscosity pre-adjustment, and after stirring for 30 min, test the pH value, and if it is less than 8.2, continue to add triethanolamine to adjust the pH value to 8.2-8.5; continue to add 2.5 g of methylisothiazolinone and 150 g of color paste, stir for 30 min, test the pH value, and add triethanolamine to adjust the pH value to 8.2-8.5, and finally add TT935 and VA01 in proportion for viscosity adjustment until the ink viscosity is adjusted to 900-1200 mpa·s, and finally add deionized water to 100%, and stir for 120 min. Filter paper with a particle size of 2 μm is used for filtration, and the pen core is assembled.

[0035] Example 2

[0036] The difference from Example 1 is only that the type of humectant is changed. The rest of the conditions remain unchanged.

[0037] The neutral pen ink formulation with low temperature resistance of the present embodiment is as follows:

[0038] Raw material name Manufacturer Addition amount 1,3-Propanediol Guangzhou Tongjie Chemical Co., Ltd. 10％ Polyethylene glycol 600 Haian Petrochemical Factory of Jiangsu Province 5％ Vinyl pyrrolidone Jiangsu Wenru Science and Technology Chemical Co., Ltd. 10％ Benzotriazole Germany Yang Cherry 0.5％ FA 2216 Guangzhou Yangsong Technology Co., Ltd. 2.5％ Iso-tridecyl alcohol phosphate Tokyo Chemical Industry Co., Ltd. 2％ Triethanolamine Dow Chemical 5％ TT 935 Dow Chemical 5％ VA 01 Guangzhou Yangsong Technology Co., Ltd. 1％ Methyl isothiazolinone Shanghai Borei Australia Trading Co., Ltd. 0.5％ Color paste Naimex New Material Co., Ltd. 30％ Deionized water Balance

[0039] The preparation method of this example is consistent with Example 1, and only the difference of the added component substances is adjusted.

[0040] Example 3:

[0041] The difference from Example 1 is that the type of humectant and thickener is changed. The rest of the conditions remain unchanged.

[0042] The neutral pen ink formula with low temperature resistance of this example is as follows:

[0043]

[0044]

[0045] The preparation method of this example is consistent with Example 1, and only the difference of the added component substances is adjusted.

[0046] Example 4:

[0047] The difference from Example 1 is that the type, proportion of humectant and the type of antifreeze are changed. The rest of the conditions remain unchanged.

[0048] The neutral pen ink formula with low temperature resistance of this example is as follows:

[0049] Raw material name Manufacturer Addition amount Ethylene glycol Guangzhou Tongjie Chemical Co., Ltd. 5％ Polyethylene glycol 600 Haian Petrochemical Factory of Jiangsu Province 15％ Glycerin Guangzhou Tongjie Chemical Co., Ltd. 5％ Benzotriazole Germany Yang Cherry 0.5％ FA 2218 Guangzhou Yangsong Technology Co., Ltd. 2.5％ Iso-tridecyl alcohol phosphate Tokyo Chemical Industry Co., Ltd. 2％ Triethanolamine Dow Chemical 5％ TT 935 Dow Chemical 5％ VA 01 Guangzhou Yangsong Technology Co., Ltd. 1％ Methyl isothiazolinone Shanghai Borei Australia Trading Co., Ltd. 0.5％ Color paste Naimex New Material Co., Ltd. 30％ Deionized water Balance

[0050] The preparation method of this example is consistent with Example 1, and only the difference of the added component substances is adjusted.

[0051] Example 5:

[0052] The difference from Example 1 is that the type, proportion of humectant, the type of antifreeze and thickener are changed. The rest of the conditions remain unchanged.

[0053] The neutral pen ink formula with low temperature resistance of this example is as follows:

[0054]

[0055]

[0056] The preparation method of this example is consistent with Example 1, and only the difference of the added component substances is adjusted.

[0057] Comparative Example 1:

[0058] The difference from Example 1 is that 50g of ethylene glycol is removed. The rest of the conditions remain unchanged.

[0059] Raw material name Manufacturer Addition amount Glycerin Guangzhou Tongjie Chemical Co., Ltd. 10％ Polyethylene glycol 300 Haian Petrochemical Factory of Jiangsu Province 5％ Benzotriazole Germany Yang Cherry 0.5％ FA 2216 Guangzhou Yangsong Technology Co., Ltd. 2.5％ Iso-tridecyl alcohol phosphate Guangzhou Yangsong Technology Co., Ltd. 2％ Triethanolamine Dow Chemical 5％ TT 935 Dow Chemical 5％ VA 01 Guangzhou Yangsong Technology Co., Ltd. 1％ Methyl isothiazolinone Shanghai Borei Australia Trading Co., Ltd. 0.5％ Color paste Naimex New Material Co., Ltd. 30％ Deionized water Balance

[0060] The preparation method of this example is consistent with Example 1, and only adaptive adjustment is made for the difference of the added component substances.

[0061] Comparative Example 2:

[0062] The difference from Example 1 is only that 12.5 g of FA 2216 is removed. The rest of the conditions remain unchanged.

[0063] Raw material name Manufacturer Addition amount Ethylene glycol Guangzhou Tongjie Chemical Co., Ltd. 10％ Polyethylene glycol 300 Haian Petrochemical Factory of Jiangsu Province 5％ Glycerin Guangzhou Tongjie Chemical Co., Ltd. 10％ Benzotriazole Germany Yang Cherry 0.5％ Iso-tridecyl alcohol phosphate Guangzhou Yangsong Technology Co., Ltd. 2％ Triethanolamine Dow Chemical 5％ TT 935 Dow Chemical 5％ VA 01 Guangzhou Yangsong Technology Co., Ltd. 1％ Methyl isothiazolinone Shanghai Borei Australia Trading Co., Ltd. 0.5％ Color paste Naimex New Material Co., Ltd. 30％ Deionized water Balance

[0064] The preparation method of this example is consistent with Example 1, and only adaptive adjustment is made for the difference of the added component substances.

[0065] Comparative Example 3:

[0066] The difference from Example 1 is only that the thickening agent VA01 is removed. The rest of the conditions remain unchanged.

[0067]

[0068]

[0069] The preparation method of this example is consistent with Example 1, and only adaptive adjustment is made for the difference of the added component substances.

[0070] Comparative Example 4:

[0071] The difference from Example 1 is only that the thickening agent ratio is changed to 10:1. The rest of the conditions remain unchanged.

[0072] Raw material name Manufacturer Addition amount Ethylene glycol Guangzhou Tongjie Chemical Co., Ltd. 10％ Polyethylene glycol 300 Haian Petrochemical Factory of Jiangsu Province 5％ Glycerin Guangzhou Tongjie Chemical Co., Ltd. 10％ Benzotriazole Germany Yang Cherry 0.5％ FA 2216 Guangzhou Yangsong Technology Co., Ltd. 2.5％ Iso-tridecyl alcohol phosphate Guangzhou Yangsong Technology Co., Ltd. 2％ Triethanolamine Dow Chemical 5％ TT 935 Dow Chemical 5％ VA 01 Guangzhou Yangsong Technology Co., Ltd. 0.5％ Methyl isothiazolinone Shanghai Borei Australia Trading Co., Ltd. 0.5％ Color paste Naimex New Material Co., Ltd. 30％ Deionized water Balance Raw material name Manufacturer Addition amount

[0073] The preparation method of this example is consistent with Example 1, and only adaptive adjustment is made for the difference of the added component substances.

[0074] The neutral pen ink prepared in each of the examples and comparative examples of the present application is subjected to performance testing, and the test results are shown in Table 1.

[0075] Table 1 Test results of the neutral pen ink prepared in each of the examples and comparative examples

[0076]

[0077]

[0078] *Under low temperature conditions at -15°C

[0079] As can be seen from Table 1, when the humectant is not modified, and no antifreezing agent is added, the prepared ink cannot be normally written in a low-temperature environment, while the neutral pen ink prepared according to the provided scheme can be normally written in a low-temperature environment, which indicates that the low-temperature writing ability of the neutral pen ink is effectively improved, and meanwhile, the writing performance is still good.

[0080] The comparison between Example 1 and Comparative Example 1 shows that although the addition of ethylene glycol can effectively improve the low-temperature writing ability of the neutral pen ink, it will bring negative effects on the smoothness and abrasion.

[0081] The comparison between Example 1 and Comparative Example 2 shows that the addition of the antifreezing agent not only helps to improve the low-temperature writing ability of the neutral pen ink, but also enhances the smoothness, but will bring negative effects on the abrasion.

[0082] The comparison between Example 1 and Comparative Example 3 shows that the compounding of the thickening agent not only helps to improve the low-temperature writing ability of the neutral pen ink, but also enhances the smoothness, but will bring negative effects on the abrasion.

[0083] The comparison between Example 1 and Comparative Example 4 shows that the preferred compounding ratio of the thickening agent not only helps to improve the low-temperature writing ability of the neutral pen ink, but also enhances the smoothness, but will bring negative effects on the abrasion.

[0084] The above-described examples only express several embodiments of the present application, and the description is more specific and detailed, but it should not be understood as limiting the scope of the patent application. It should be pointed out that for ordinary skilled in the art, without departing from the concept of the present application, several modifications and improvements can be made, which are all within the protection scope of the present application. Therefore, the protection scope of the present application patent should be subject to the appended claims.

Claims

1. A neutral pen ink with low-temperature resistance, characterized in that: By weight percentage, it includes the following components Deionized water, 10%–60%; Moisturizer, 15%–35%; Rust inhibitor, 0.1%–1.5%; Antifreeze agent, 0.1%–5%; Lubricant, 0.1%–2%; pH adjuster 1%–8%; Thickener, 1%–10%; Preservatives, 0.1%–1.5%; Color paste, 25%–40%; The humectant is composed of humectant A, humectant B, and humectant C. Humectant A is used to give the ink system a low freezing point, humectant B has hydroxyl groups and is used to give the ink system high moisturizing properties, and humectant C is used to give the ink system auxiliary moisturizing and lubricating properties. The thickener is a compound of high-shear thickener A and low-shear thickener B.

2. The gel pen ink with low-temperature resistance according to claim 1, characterized in that: The moisturizer A is selected from at least one of ethylene glycol, 1,2-propanediol, and 1,3-propanediol; the moisturizer B is selected from at least one of polyethylene glycol 200, polyethylene glycol 300, polyethylene glycol 400, and polyethylene glycol 600; and the moisturizer C is selected from at least one of sorbitol, vinylpyrrolidone, glycerin, and triethylene glycol.

3. The gel pen ink with low-temperature resistance according to claim 2, characterized in that: The percentage contents of humectant A, humectant B, and humectant C in the ink are 1%–10%, 5%–25%, and 1%–10%, respectively.

4. The gel pen ink with low-temperature resistance according to claim 1, characterized in that: The thickener is an acrylic thickener and / or a polyurethane thickener, and the mass ratio of the high-shear thickener A to the low-shear thickener B is (4-7):

1.

5. The gel pen ink with low-temperature resistance according to claim 4, characterized in that: The acrylic thickener is selected from one or more of BASF HS1152, BASF AS1130, Dow TT615, and Dow TT93; the polyurethane thickener is selected from one or more of VA01, VA02, and VA03.

6. The gel pen ink with low-temperature resistance according to any one of claims 1 to 5, characterized in that: The rust inhibitor is one or more of benzotriazole, methylbenzotriazole, diethanolamine oleate, and dialkylthiourea.

7. The gel pen ink with low-temperature resistance according to any one of claims 1 to 5, characterized in that: The lubricant is one or more of the following: phosphate ester lubricants, fatty acid amide lubricants, and polyether-modified silicone oil lubricants.

8. The gel pen ink with low-temperature resistance according to any one of claims 1 to 5, characterized in that: The pH adjuster is one or more of diethanolamine, triethanolamine, 2-amino-2-methyl-1,3-propanediol, ammonia, sodium carbonate, and alkanolamine.

9. The gel pen ink with low-temperature resistance according to any one of claims 1 to 5, characterized in that: The preservative is one or more of potassium sorbitol, benzisothiazolinone, methylisothiazolinone, and sodium hydroxymethylglycinate.

10. The gel pen ink with low-temperature resistance according to any one of claims 1 to 5, characterized in that: The antifreeze agent is selected from at least one of FA2216 and FA2218.

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