CN115353770B

CN115353770B - Gel pen ink with optimized writing performance

Info

Publication number: CN115353770B
Application number: CN202211024666.1A
Authority: CN
Inventors: 刘闯; 张世著; 石欣超; 张连斌; 张尚峰
Original assignee: Nanjing Yimo Nanotechnology Co ltd
Current assignee: Nanjing Yimo Nanotechnology Co ltd
Priority date: 2022-08-25
Filing date: 2022-08-25
Publication date: 2023-10-20
Anticipated expiration: 2042-08-25
Also published as: CN115353770A

Abstract

The invention relates to gel pen ink with optimized writing performance, which comprises the following materials: 15.7 to 21.8 parts of pigment color paste, 1.5 to 4.3 parts of thickener, 7.2 to 13.5 parts of dispersant, 2.0 to 5.4 parts of modifier, 6.8 to 10.7 parts of film forming resin, 0.8 to 2.0 parts of surfactant, 0.1 to 0.2 part of insecticidal sterilizing agent and 50.8 to 60.6 parts of deionized water; the thickening agent is polyurethane; the dispersing agent is amino alcohol; the modifier is a combination of thioglucoside, silicon dioxide and aluminum oxide; the surfactant is alcohol ether surfactant. The gel pen ink with optimized writing performance improves the drying resistance of the ink, is smooth in intermittent writing and has good storage and use stability.

Description

Gel pen ink with optimized writing performance

Technical Field

The invention belongs to the field of ink, and particularly relates to neutral pen ink.

Background

As a neutral pen of the mainstream writing pen, the stability and the pseudoplasticity of the ink determine the storage property and the writing property of the ink of the neutral pen, respectively. Therefore, in order to improve the stability and pseudoplasticity of the neutral pen ink, various neutral pen ink systems have been tried.

At present, the gel pen ink system with the most mature technology and the most perfect process is an ink system based on polysaccharide as a thickener, for example, in China patent CN105524524B, which is a gel ink prepared from self-dispersion pigment color paste, and a preparation method thereof, xanthan gum and guar gum which belong to polysaccharide are used as the thickener, and China patent CN105348916B, which is a high-dispersibility and high-thixotropic gel ink, and a preparation method thereof, are used, and cellulose which belongs to polysaccharide is used as the thickener. Is easily decomposed by microorganisms in a long-term state, and causes deterioration of performance. For this reason, researchers have started to use synthetic polymers that are not easily decomposed, such as acrylic and polyurethane, as thickeners, for example, alkali-swellable acrylic thickeners used in chinese patent CN109021697a, a method for preparing a lubricating pigment-type neutral ink; in China patent CN103333552B, a pigment type neutral ink and a production method thereof, a polyether polyurethane associative thickener is used. Acrylic acid, particularly alkali-swellable acrylic acid, acts as a thickener, limiting its use in neutral pen inks due to its inherent disadvantages of flammability and chemical instability. Polyurethane has stable chemical properties, is not easy to burn and dry and harden, but the associated polyurethane resin has complex molecular structure and difficult synthesis, and when writing is performed after standing for a long time, the balance of association and dissociation realized under the action of shearing force can cause the viscosity of ink to be reduced to some extent, so that writing is not smooth due to higher viscosity of the ink when writing is started.

How to apply polyurethane with stable chemical property as a thickener of gel ink and how to improve writing performance (especially intermittent writing performance) of gel ink using polyurethane as the thickener becomes a problem to be solved for developing gel ink.

Disclosure of Invention

The invention adopts water-soluble anionic polyurethane as a thickening agent, amino alcohol as a dispersing agent and the combination of thioglucoside, silicon dioxide and aluminum oxide as a modifying agent, thereby improving the drying resistance and intermittent writing performance of the ink and having good storage and use stability of the ink.

Technical proposal

The invention provides a gel ink with optimized writing performance, which comprises the following materials in parts by weight: 15.7 to 21.8 parts of pigment color paste, 1.5 to 4.3 parts of thickener, 7.2 to 13.5 parts of dispersant, 2.0 to 5.4 parts of modifier, 6.8 to 10.7 parts of film forming resin, 0.8 to 2.0 parts of surfactant, 0.1 to 0.2 part of insecticidal sterilizing agent and 50.8 to 60.6 parts of deionized water; the thickening agent is polyurethane; the dispersing agent is amino alcohol; the modifier is a combination of thioglucoside, silicon dioxide and aluminum oxide; the surfactant is alcohol ether surfactant.

The invention adopts water-soluble anionic polyurethane as a thickening agent, preferably aliphatic polyurethane, in particular IPDI, HDI, H MDI and CHDI polyurethane. The aliphatic water-soluble anionic polyurethane has the characteristics of good weather resistance and no yellowing caused by ultraviolet irradiation, and improves the preservation performance of written handwriting.

The invention adopts amino alcohol as dispersing agent, wherein the amino alcohol is selected from one of 3- (methylamino) -1-propanol, L-phenylalaninol, 4-amino-1-butanol and 4- (N-tert-butoxycarbonylamino) -1-butanol, and preferably 4-amino-1-butanol. the-N-group or-OH group of the amino alcohol can form a chemical bond with an anionic group existing on the surface of pigment particles in the pigment paste, so that the bleeding resistance of the writing effect of the ink is improved, and the density and uniformity of writing colors are improved.

The invention adopts the combination of thioglucoside, silicon dioxide and aluminum oxide as a modifier. The thioglucoside is aliphatic thioglucoside, specifically one of glucoraphanin and curculin. Thioglucoside as a water-soluble organic anionic compound. The hydroxyl group carried by the ink is utilized to regulate and optimize the surface tension of the ink together with amino alcohols serving as dispersing agents, and the stability of an ink system is improved; in addition, the thioglucoside also has a sulfonic acid group, can form a chemical bond with an-N-group or an-OH group of amino alcohol, and improves the bleeding resistance of the writing effect of the ink, thereby improving the density and uniformity of writing handwriting color. Silica and alumina with low charge density and charge sensitive to the pH value of the ink are added to the neutral pen ink, so that improved water phase separation can be obtained, and good pigment paste stability is maintained. Also, alumina and silica can provide an elastic component to the stylus ink under electrostatic interaction to form a three-dimensional network structure. The three-dimensional network structure with elasticity has positive improvement effect on avoiding the phenomenon that the ink leakage-proof film formed at the pen point is hardened in a long-time non-writing state and the writing is blurred when writing is just performed, and is beneficial to improving the intermittent writing performance of the gel ink pen after the gel ink is kept for a long time.

The invention adopts polysorbate as film forming agent. The polysorbate has the function of a viscosity-increasing inhibitor, can improve the viscosity of an ink system, and can improve the stability of the ink system.

The invention adopts alcohol ether as a surfactant, preferably oil-based polyoxyethylene glycol ether.

The oil-based polyoxyethylene glycol ether is added into the ink, so that the surface tension of the gel ink pen ink is effectively controlled to be close to the surface tension of writing paper, and further, the phenomenon that handwriting color is uneven due to accumulation and too fast diffusion of the writing ink after writing is effectively slowed down; meanwhile, the color of the writing is further stable, and no obvious bright and dark color difference exists.

The insecticidal sterilizing agent is one of Nuosept or BIT-20.

The pigment paste of the invention is a CAB-O-JET series pigment paste produced by CABOT company in the United states or a Colanil 100 series pigment paste produced by Clariant company in Switzerland, preferably a Colanil 100 series pigment paste produced by Clariant company, specifically Colanyl Yellow SGX, colanil Red FGR 131, colanil Blue A2R 131 and Colanil Black N131.

Detailed Description

Example 1

Black gel ink YM-PK-01

Under the room temperature condition, firstly adding 12.6 parts of 4-amino-1-butanol and 24 parts of deionized water into a beaker, then sequentially adding 3.8 parts of IPDI polyurethane, 10.1 parts of polysorbate, 3.5 parts of glucoraphanin, 0.4 part of silicon dioxide and 0.3 part of aluminum oxide, stirring 1.5 parts of h, and fully and uniformly mixing to form mother liquor; sequentially adding the mother solution, 15.7 parts of Colan Black N131 and 26.8 parts of deionized water into a stirring kettle, adding 0.2 part of BIT-20 and 2.0 parts of oil-based polyoxyethylene glycol ether, stirring 2 h, and uniformly mixing; heating to 60 ℃, stirring for curing to 3.5 and h to obtain a liquid to be treated; and sequentially carrying out vacuum defoaming, high-speed centrifugal filtration and filtrate collection on the liquid to be treated, and carrying out secondary defoaming to finally prepare the black gel ink YM-PK-01.

Example 2

Blue gel ink YM-PB-01

Under the room temperature condition, 13.5 parts of 4-amino-1-butanol and 25 parts of deionized water are firstly added into a beaker, then 2.7 parts of HDI polyurethane, 9.6 parts of polysorbate, 3.2 parts of curculin, 0.3 part of silicon dioxide and 0.2 part of aluminum oxide are sequentially added, and 1.5 h parts of silicon dioxide and aluminum oxide are stirred, and are fully and uniformly mixed to form mother liquor; sequentially adding the mother solution, 19.6 parts of Colany Blue A2R 131 and 28.1 parts of deionized water into a stirring kettle, adding 0.1 part of Nuosept and 1.6 parts of oil-based polyoxyethylene glycol ether, stirring 2 h, and uniformly mixing; heating to 60 ℃, stirring for curing to 3.5 and h to obtain a liquid to be treated; and sequentially carrying out vacuum defoaming, high-speed centrifugal filtration and filtrate collection on the liquid to be treated, and carrying out secondary defoaming to finally obtain the blue gel ink YM-PB-01.

Example 3

Red gel pen ink YM-PR-01

Under the room temperature condition, firstly adding 10.7 parts of 4-amino-1-butanol and 24 parts of deionized water into a beaker, then sequentially adding 4.3 parts of H12MDI polyurethane, 10.7 parts of polysorbate, 4.4 parts of curculin, 0.5 part of silicon dioxide and 0.5 part of aluminum oxide, stirring 1.5 and H, and fully and uniformly mixing to form mother liquor; adding the mother solution, 21.8 parts of Colany Red FGR 131 and 28.6 parts of deionized water into a stirring kettle in sequence, adding 0.1 part of Nuosept and 1.5 parts of oil-based polyoxyethylene glycol ether, stirring 2 h, and uniformly mixing; heating to 60 ℃, stirring for curing to 3.5 and h to obtain a liquid to be treated; and sequentially carrying out vacuum defoaming, high-speed centrifugal filtration and filtrate collection on the liquid to be treated, and carrying out secondary defoaming to finally obtain the red gel ink YM-PR-01.

Example 4

Yellow gel ink YM-PY-01

Under the room temperature condition, 7.2 parts of 4-amino-1-butanol and 24 parts of deionized water are firstly added into a beaker, then 1.5 parts of IPDI polyurethane, 6.8 parts of polysorbate, 1.6 parts of curculin, 0.2 part of silicon dioxide and 0.2 part of aluminum oxide are sequentially added, and 1.5 parts of aluminum oxide are stirred for h, and the mixture is fully and uniformly mixed to form mother liquor; sequentially adding the mother solution, 17.4 parts of Colanyl Yellow SGX and 36.6 parts of deionized water into a stirring kettle, adding 0.2 part of BIT-20 and 0.8 part of oil-based polyoxyethylene glycol ether, stirring for 2 h, and uniformly mixing; heating to 60 ℃, stirring for curing to 3.5 and h to obtain a liquid to be treated; and sequentially carrying out vacuum defoaming, high-speed centrifugal filtration and filtrate collection on the liquid to be treated, and carrying out secondary defoaming to finally obtain the yellow gel ink YM-PY-01.

Characterization of results Performance

The method adopts a model BLD-8032 circular writing machine manufactured by Dongguan Boleder corporation and an 80 g engineering drawing paper of Jinfeng paper industry, and adopts the ' pen point classification ' in QB/T2625-2011 neutral ink ball-point pen and pen core ' according to the specific requirements of QB/T2625-2011 neutral ink ball-point pen and pen core: thin, nib code: the tip of F' (ball diameter D: 0.55 mm. Ltoreq.D < 0.75 mm) was tested on the ink of the examples of this patent.

The writing performance of the ink is shown in table-1, the intermittent writing performance of the ink is shown in table-2, and the storage performance of the ink is shown in table-3.

TABLE-1 writing Property of ink

Ink serial number	Writing performance
		YM-PK-01	The scribing line is more than 300 m, the stitch is free from obvious lightening and broken line, and the thickness of the line is uniform
YM-PB-01	The scribing line is more than 300 m, the stitch is free from obvious lightening and broken line, and the thickness of the line is uniform
		YM-PR-01	The scribing line is more than 300 m, the stitch is free from obvious lightening and broken line, and the thickness of the line is uniform
YM-PY-01	The scribing line is more than 300 m, the stitch is free from obvious lightening and broken line, and the thickness of the line is uniform

TABLE-2 intermittent writing Property of inks

Ink serial number	Intermittent writing performance
		YM-PK-01	Intermittent 24 h, normal writing in 100 mm, and uniform line thickness
YM-PB-01	Intermittent 24 h, normal writing in 100 mm, and uniform line thickness
		YM-PR-01	Intermittent 24 h, normal writing in 100 mm, and uniform line thickness
YM-PY-01	Intermittent 24 h, normal writing in 100 mm, and uniform line thickness

TABLE-3 preservation Properties of inks

Ink serial number	Preservation Property
		YM-PK-01	The writing performance is kept for 10 days at 48.5 DEG CNormal state
YM-PB-01	The writing performance is normal after being stored for 10 days at 48.5 DEG C
		YM-PR-01	The writing performance is normal after being stored for 10 days at 48.5 DEG C
YM-PY-01	The writing performance is normal after being stored for 10 days at 48.5 DEG C

As can be seen from Table-1, the writing performance of the ink meets the specific requirements of QB/T2625-2011 neutral ink ball point pens and cartridges; as can be seen from Table-2, the intermittent writing performance of the ink meets the specific requirements of QB/T2625-2011 neutral ink ball point pen and refill; as can be seen from Table-3, the preservation performance of the ink meets the specific requirements of QB/T2625-2011 neutral ink ball point pens and cartridges.

The gel ink of the gel pen improves the drying resistance and intermittent writing performance of the ink, is smooth in writing, has good storage and use stability, and is suitable for large-scale production and popularization.

Claims

1. The gel pen ink with optimized writing performance is characterized by comprising the following materials in parts by weight: 15.7 to 21.8 parts of pigment color paste, 1.5 to 4.3 parts of thickener, 7.2 to 13.5 parts of dispersant, 2.0 to 5.4 parts of modifier, 6.8 to 10.7 parts of film forming resin, 0.8 to 2.0 parts of surfactant, 0.1 to 0.2 part of insecticidal sterilizing agent and 50.8 to 60.6 parts of deionized water; the thickener is water-soluble anionic aliphatic polyurethane; the dispersing agent is amino alcohol; the modifier is a combination of thioglucoside, silicon dioxide and aluminum oxide; the surface active agent is alcohol ether surface active agent, and the pigment color paste is pigment color paste with anionic groups on the surface.

2. The writing performance optimizing gel pen ink of claim 1, wherein the aliphatic polyurethane is one of IPDI, HDI, H MDI and CHDI polyurethane.

3. The writing performance optimizing gel ink of claim 1, wherein the amino alcohol is one of 3- (methylamino) -1-propanol, L-phenylalaninol, 4-amino-1-butanol, and 4- (N-t-butoxycarbonylamino) -1-butanol.

4. A writing performance optimizing gel pen ink as in claim 3 wherein said amino alcohol is 4-amino-1-butanol.

5. The writing performance optimized neutral pen ink as claimed in claim 1, wherein said thioglucoside is aliphatic thioglucoside, said silica has a particle size of 0.2-1.0 μm, and said alumina has a particle size of 0.1-1.0 μm.

6. The writing performance optimizing gel ink of claim 5 wherein the silica has a particle size of 0.5 μm and the alumina has a particle size of 0.2 μm; the thioglucoside is one of glucoraphanin and curculin.

7. The writing performance optimizing gel pen ink of claim 1, wherein the film forming resin is polysorbate.

8. The writing performance optimizing gel pen ink as in claim 1, wherein said alcohol ether surfactant is specifically oil-based polyoxyethylene glycol ether.

9. The writing performance optimizing neutral pen ink as claimed in claim 1, wherein the pigment paste is selected from the group consisting of CAB-O-JET pigment paste produced by CABOT corporation of united states.