WO2020151282A1

WO2020151282A1 - Nanocellulose-based refill ink and preparation method therefor

Info

Publication number: WO2020151282A1
Application number: PCT/CN2019/113816
Authority: WO
Inventors: 付时雨; 王文波
Original assignee: 华南理工大学
Priority date: 2019-01-25
Filing date: 2019-10-29
Publication date: 2020-07-30
Also published as: CN109852139A

Abstract

A preparation method for nanocellulose-based refill ink, comprising the following steps: (1) adding a dye to a nanocellulose suspension, stirring the mixture until the dye is completely dissolved, wherein nanocellulose and dye molecules interpenetrate to each other to maintain a stable colloid state; and (2) adding a surfactant to the solution obtained in step (1), and mixing the two evenly to obtain nanocellulose-based refill ink.

Description

Nano cellulose-based refill ink and preparation method thereofTechnical field

[0001] The present invention belongs to the field of refill inks, and specifically relates to a nano-cellulose-based refill ink and a preparation method thereof. BACKGROUND

[0002] As a new type of biomass-based polymer material, nanocellulose not only has the characteristics of green, environmentally friendly and renewable fibers, but also has many other excellent properties such as nanomaterial scale effect, special rheology, and good dispersibility. It has been widely researched and applied in many fields such as biomedicine, food safety, fine chemicals and composite materials. In the pen industry, because the refill ink contains nano-level pigments, dispersants, viscosity modifiers and other complex ingredients, the potential interaction of these organic reagents makes the ink system unstable, resulting in refill inks, especially color refills. The development of ink is difficult and the preparation process is complicated. If nano cellulose is used in the preparation of refill inks, because it has good rheology and dispersibility, it can reduce or even eliminate the use of organic dispersants, viscosity modifiers, etc., which can greatly reduce the preparation of inks. Difficult, and because of the green and renewable properties of nanocellulose, the prepared ink is environmentally friendly.

Summary of the invention

technical problem

The solution to the problem

Technical solutions

[0003] In order to overcome the deficiencies of the prior art, the present invention provides a nano-cellulose-based refill ink and a preparation method thereof. In this method, water-soluble dye and a small amount of surface active agent are added to a certain concentration of nanocellulose suspension, and the dye is fully dissolved and the surface active agent is evenly mixed to obtain nanocellulose-based refill ink.

[0004] The present invention is achieved through the following technical solutions.

[0005] A method for preparing nano-cellulose-based refill ink includes the following steps:

[0006] (1) Add the dye to the nanocellulose suspension, stir until the dye is completely dissolved, and the nanocellulose and the dye molecules intersect each other to maintain a stable colloidal state; [0007] (2) In the solution obtained in step (1), a surfactant is added to adjust the viscosity and mixed uniformly to obtain a nanocellulose-based refill ink.

[0008] Preferably, the nanocellulose described in step (1) is one or more of nanocellulose obtained by an acid hydrolysis method, nanocellulose obtained by a TEMPO oxidation method, and nanocellulose obtained by an ultrasonic method.

[0009] Preferably, the nanocellulose suspension described in step (1) is obtained by dispersing cellulose in water.

[0010] Preferably, the dye described in step (1) is one or more of water-soluble dyes such as acid dyes, neutral dyes, basic dyes, and reactive dyes.

[0011] Preferably, the concentration of nanocellulose in step (1) is 1-5 wt%.

[0012] Preferably, the amount of dye described in step (1) is 0.1-10% of the total liquid mass.

[0013] Preferably, the surfactant described in step (2) is alkylphenol polyoxyethylene ether, high-carbon fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, fatty acid methyl ester ethoxylate, polypropylene glycol Among the nonionic surfactants such as ethylene oxide adducts, polyoxyethylated ionic surfactants, sorbitan esters, sucrose esters, alkyl alcohol amides, nonionic fluorocarbon surfactants, etc. One or more mixtures.

[0014] Preferably, the amount of the surfactant described in step (2) is 0.1-5% of the total liquid mass.

[0015] Preferably, a method for preparing a nano-cellulose-based refill ink specifically includes the following steps:

[0016] Add 0.1-10 wt% (relative to the total liquid mass) of the water-soluble dye in the nanocellulose suspension with a concentration of 1-5 wt%, stir and mix uniformly to fully dissolve the dye. Add to this solution

wt% (relative to the total liquid mass) of non-ionic surfactant, stir and mix well. The obtained mixed liquid can be used as a water-based pen or gel pen refill ink.

The beneficial effects of the invention

Beneficial effect

[0017] Compared with the prior art, the present invention has the following advantages and excellent effects:

[0018] The nano-cellulose-based refill ink prepared by the present invention has the advantages of environmental protection, diverse color types, and simple preparation process. The use of complex organic chemical reagents in the traditional ink preparation process is abandoned, which greatly simplifies the preparation process and the development and production process of new color inks.

Brief description of the drawings

Description of the drawings

[0019] Type the description of the figure description here. Invention embodiment

Embodiments of the invention

[0020] The specific implementation of the present invention will be further described below in conjunction with examples, but the implementation of the present invention is not limited thereto.

[0021] Embodiment 1

[0022] Add 0.1% (relative to the mass of the total solution) of the reactive red dye to the nanocellulose suspension with a concentration of 1 wt%, stir and mix evenly to fully dissolve the dye. Add 0.1% (relative to the total mass of the solution) of alkylphenol polyoxyethylene ether to the solution, stir and mix well, and the resulting mixture can be used as a water-based pen or gel pen refill ink.

[0023] The nanocellulose-based refill ink prepared in this embodiment is red. In the application of water-based pens or gel pens, you can write smoothly and continuously. Because the amount of dye is less, the color of the ink is lighter. The brightness (L) of the handwriting measured by the residual ink meter is 65.73, which is "powerful" The brightness of S761" is 33.18 different.

[0024] Embodiment 2

[0025] 0.1% (relative to the mass of the total solution) of the reactive red dye was added to the nanocellulose suspension with a concentration of 5 wt%, stirred and mixed uniformly to fully dissolve the dye. Add 5% (relative to the total quality of the solution) of alkylphenol polyoxyethylene ether to the solution, stir and mix well, and the resulting mixture can be used as a water-based pen or gel pen refill ink.

[0026] The nanocellulose-based refill ink prepared in this embodiment is red. In the application of water-based pen or gel pen, the writing is smooth and continuous ink, because the amount of dye is less and the ink color is lighter. The brightness (L) of the handwriting measured by the residual ink tester is 65.03, which is quite different from the 33.18 of the commercially available ink "Deli S761".

[0027] Embodiment 3

[0028] 0.1% (relative to the total solution mass) of the reactive red dye was added to the nanocellulose suspension with a concentration of 2.5 wt%, stirred and mixed uniformly to fully dissolve the dye. Add 2.5% (relative to the mass of the total solution) of alkylphenol polyoxyethylene ether to the solution, stir and mix evenly, and the resulting mixture can be used as a water-based pen or gel pen refill ink.

[0029] The nanocellulose-based refill ink prepared in this embodiment is red. In the application of water-based pen or gel pen, the writing is smooth and continuous, because the amount of dye is less and the ink color is lighter. The brightness (L) of the handwriting measured by the residual ink meter is 65.22, which is quite different from the brightness 33.18 of the commercially available ink "Deli S761". [0030] Example 4

[0031] Add 10% (relative to the mass of the total solution) of the reactive red dye to the nanocellulose suspension with a concentration of 2.5 wt%, stir and mix evenly to fully dissolve the dye. Add 2.5% (relative to the mass of the total solution) of alkylphenol polyoxyethylene ether to the solution, stir and mix evenly, and the resulting mixture can be used as a water-based pen or gel pen refill ink.

[0032] The nanocellulose-based refill ink prepared in this embodiment is red. In the application of water-based pen or gel pen, the writing is smooth and continuous, and the ink color is darker. The brightness (L) of the handwriting measured by the residual ink tester is 27.55, the color is smaller than the 33.18 of the commercially available ink "Deli S761", and the color is deeper.

[0033] Embodiment 5

[0034] Add 5% (relative to the mass of the total solution) of the reactive red dye to the nanocellulose suspension with a concentration of 2.5 wt%, stir and mix evenly to fully dissolve the dye. Add 2.5% (relative to the total quality of the solution) of alkylphenol polyoxyethylene ether to the solution, stir and mix well, and the resulting mixture can be used as a water-based pen or gel pen refill ink.

[0035] The nanocellulose-based refill ink prepared in this embodiment is red. In the application of water-based pen or gel pen, writing smoothly and continuously,

The ink is dark. The lightness (L) of the handwriting measured by the residual ink meter is 33.04, which is not much different from the brightness 33.18 of the commercially available ink "Deli S761".

[0036] Example 6

[0037] Add 5% (relative to the mass of the total solution) of the reactive blue dye to the nanocellulose suspension with a concentration of 2.5 wt%, stir and mix uniformly to fully dissolve the dye. Add 2.5% (relative to the total quality of the solution) of alkylphenol polyoxyethylene ether to the solution, stir and mix well, and the resulting mixture can be used as a water-based pen or gel pen refill ink.

[0038] The nanocellulose-based refill ink prepared in this embodiment is blue. In the application of water-based pen or gel pen, the writing is smooth and continuous, and the ink is dark. The brightness (L) of the handwriting measured by the residual ink meter is 33.26, which is not much different from the brightness 33.18 of the commercially available ink "Deli S761".

[0039] Example 7

[0040] Add 5% (relative to the mass of the total solution) neutral red dye into the nanocellulose suspension with a concentration of 2.5 wt%, stir and mix uniformly, so that the dye is fully dissolved. Add 2.5% to the solution (relative to the total solution quality The amount) of alkylphenol polyoxyethylene ether, stir and mix evenly, and the resulting mixture can be used as a water-based pen or gel pen refill ink.

[0041] The nanocellulose-based refill ink prepared in this embodiment is red. In the application of water-based pen or gel pen, writing smoothly and continuously,

The ink is dark. The lightness (L) of the handwriting measured by the residual ink meter is 33.95, which is not much different from the brightness 33.18 of the commercially available ink "Deli S761".

[0042] Embodiment 8

[0043] Add 2% (relative to the mass of the total solution) of the orange II dye into the nanocellulose suspension with a concentration of 2.5 wt%, stir and mix evenly to fully dissolve the dye. Add 2.5% (relative to the total quality of the solution) of alkylphenol polyoxyethylene ether to the solution, stir and mix well, and the resulting mixture can be used as a water-based pen or gel pen refill ink.

[0044] The nanocellulose-based refill ink prepared in this embodiment is yellow. In the application of water-based pen or gel pen, writing smoothly and continuously,

The ink is dark. The lightness (L) of the handwriting measured by the residual ink tester is 40.32, which is not much different from the 33.18 of the commercially available ink "Deli S761".

[0045] Example 9

[0046] Add 2% (relative to the mass of the total solution) of acid fuchsin dye into the nanocellulose suspension with a concentration of 2.5 wt%, stir and mix uniformly to fully dissolve the dye. Add 2.5% (relative to the mass of the total solution) of alkylphenol polyoxyethylene ether to the solution, stir and mix evenly, and the resulting mixture can be used as a water-based pen or gel pen refill ink.

[0047] The nanocellulose-based refill ink prepared in this embodiment is red. In the application of water-based pen or gel pen, writing smoothly and continuously,

The ink is dark. The lightness (L) of the handwriting measured by the residual ink tester is 40.01, which is not much different from the brightness 33.18 of the commercially available ink "Deli S761".

[0048] Embodiment 10

[0049] 2% (relative to the mass of the total solution) of Congo red dye was added to the nanocellulose suspension with a concentration of 2.5 wt%, stirred and mixed uniformly to fully dissolve the dye. Add 2.5% (relative to the mass of the total solution) of alkylphenol polyoxyethylene ether to the solution, stir and mix evenly, and the resulting mixture can be used as a water-based pen or gel pen Refill ink.

[0050] The nanocellulose-based refill ink prepared in this embodiment is red. In the application of water-based pen or gel pen, writing smoothly and continuously,

The ink is dark. The lightness (L) of the handwriting measured by the residual ink tester is 41.13, which is not much different from the brightness 33.18 of the commercially available ink "Deli S761".

[0051] Example 11

[0052] Add 2% (relative to the mass of the total solution) of Congo red dye to the nanocellulose suspension with a concentration of 2.5 wt%, stir and mix uniformly to fully dissolve the dye. Add 2.5% (relative to the total solution quality) of high-carbon fatty alcohol polyoxyethylene ether to the solution, stir and mix evenly, and the resulting mixture can be used as a water-based pen or gel pen refill ink.

[0053] The nanocellulose-based refill ink prepared in this embodiment is red. In the application of water-based pen or gel pen, writing smoothly and continuously,

The ink is dark. The brightness (L) of the handwriting measured by the residual ink tester is 40.51, which is not much different from the brightness 33.18 of the commercially available ink "Deli S761".

[0054] Embodiment 12

[0055] 2% (relative to the mass of the total solution) of Congo red dye was added to the nanocellulose suspension with a concentration of 2.5 wt%, stirred and mixed uniformly to fully dissolve the dye. Add 2.5% (relative to the total solution quality) of fatty acid polyoxyethylene ester into the solution, stir and mix well, and the resulting mixture can be used as a water-based pen or gel pen refill ink.

[0056] The nanocellulose-based refill ink prepared in this embodiment is red. In the application of water-based pen or gel pen, writing smoothly and continuously,

The ink is dark. The brightness (L) of the handwriting measured by the residual ink tester is 40.68, which is not much different from the 33.18 of the commercially available ink "Deli S761".

[0057] Embodiment 13

[0058] 2% (relative to the mass of the total solution) of Congo red dye was added to the nanocellulose suspension with a concentration of 2.5 wt%, stirred and mixed uniformly to fully dissolve the dye. Add 2.5% (relative to the mass of the total solution) of fatty acid methyl ester ethoxylate to the solution, stir and mix uniformly, and the resulting mixture can be used as a water-based pen or gel pen refill ink. [0059] The nanocellulose-based refill ink prepared in this embodiment is red. In the application of water-based pen or gel pen, the writing is smooth and continuous,

The ink is dark. The lightness (L) of the handwriting measured by the residual ink meter is 40.93, which is not much different from the 33.18 of the commercially available ink "Deli S761".

[0060] Example 14

[0061] 2% (relative to the mass of the total solution) of Congo red dye was added to the nanocellulose suspension with a concentration of 2.5 wt%, stirred and mixed uniformly, so that the dye was fully dissolved. Add 2.5% (relative to the total solution quality) of the ethylene oxide adduct of polypropylene glycol to the solution, stir and mix well, and the resulting mixture can be used as a water-based pen or gel pen refill ink.

[0062] The nanocellulose-based refill ink prepared in this embodiment is red. In the application of water-based pen or gel pen, writing smoothly and continuously,

The ink is dark. The brightness (L) of the handwriting measured by the residual ink tester is 40.28, which is not much different from the brightness 33.18 of the commercially available ink "Deli S761".

[0063] Embodiment 15

[0064] 2% (relative to the mass of the total solution) of Congo red dye was added to the nanocellulose suspension with a concentration of 2.5 wt%, stirred and mixed uniformly, so that the dye was fully dissolved. Add 2.5% (relative to the total solution quality) of the polyoxyethylene ionic surfactant to the solution, stir and mix well, and the resulting mixture can be used as a water-based pen or gel pen refill ink.

[0065] The nanocellulose-based refill ink prepared in this embodiment is red. In the application of water-based pen or gel pen, writing smoothly and continuously,

The ink is dark. The brightness (L) of the handwriting measured by the residual ink tester is 40.76, which is not much different from the 33.18 of the commercially available ink "Deli S761".

[0066] Example 16

[0067] 2% (relative to the mass of the total solution) of Congo red dye was added to the nanocellulose suspension with a concentration of 2.5 wt%, stirred and mixed uniformly to fully dissolve the dye. Add 2.5% (relative to the total solution quality) of sorbitan ester into the solution, stir and mix well, and the resulting mixture can be used as a water-based pen or gel pen refill ink.

[0068] The nanocellulose-based refill ink prepared in this embodiment is red. Application in water-based pen or gel pen Chinese writing is smooth and continuous,

The ink is dark. The brightness (L) of the handwriting measured by the residual ink tester is 41.98, which is not much different from the brightness 33.18 of the commercially available ink "Deli S761".

[0069] Example 17

[0070] 2% (relative to the mass of the total solution) of Congo red dye was added to the nanocellulose suspension with a concentration of 2.5 wt%, stirred and mixed uniformly to fully dissolve the dye. Add 2.5% (relative to the total mass of the solution) of sucrose ester into the solution, stir and mix well, and the resulting mixture can be used as a water-based pen or gel pen refill ink.

[0071] The nanocellulose-based refill ink prepared in this embodiment is red. In the application of water-based pen or gel pen, writing smoothly and continuously,

The ink is dark. The brightness (L) of the handwriting measured by the residual ink tester is 41.01, which is not much different from the brightness 33.18 of the commercially available ink "Deli S761".

[0072] Embodiment 18

[0073] Add 2% (relative to the mass of the total solution) of Congo red dye to the nanocellulose suspension with a concentration of 2.5 wt%, stir and mix uniformly to fully dissolve the dye. Add 2.5% (relative to the total mass of the solution) of the alkyl alcohol amide to the solution, stir and mix well, and the resulting mixture can be used as a water-based pen or gel pen refill ink.

[0074] The nanocellulose-based refill ink prepared in this embodiment is red. In the application of water-based pen or gel pen, writing smoothly and continuously,

The ink is dark. The lightness (L) of the handwriting measured by the residual ink tester is 41.35, which is not much different from the brightness 33.18 of the commercially available ink "Deli S761".

[0075] Embodiment 19

[0076] Add 2% (relative to the mass of the total solution) of Congo red dye to the nanocellulose suspension with a concentration of 2.5 wt%, stir and mix uniformly, so that the dye is fully dissolved. Add 2.5% (relative to the total solution quality) of non-ionic fluorocarbon surfactant to the solution, stir and mix evenly, and the resulting mixture can be used as a water-based pen or gel pen refill ink.

[0077] The nanocellulose-based refill ink prepared in this embodiment is red. In the application of water-based pen or gel pen, writing smoothly and continuously,

The ink is dark. The brightness (L) of the handwriting measured by the residual ink meter is 41.64, which is similar to that of commercially available ink. The brightness of Deli S761" is not much different from 33.18.

[0078] Embodiment 20

[0079] 2% (relative to the mass of the total solution) of the gardenia blue dye was added to the nanocellulose suspension with a concentration of 2.5 wt%, stirred and mixed uniformly, so that the dye was fully dissolved. Add 2.5% (relative to the total solution quality) of high-carbon fatty alcohol polyoxyethylene ether to the solution, stir and mix evenly, and the resulting mixture can be used as a water-based pen or gel pen refill ink.

[0080] The nanocellulose-based refill ink prepared in this embodiment is blue. In the application of water-based pen or gel pen, writing smoothly and continuously,

The ink is dark. The brightness (L) of the handwriting measured by the residual ink tester is 41.89, which is not much different from the brightness 33.18 of the commercially available ink "Deli S761".

[0081] Embodiment 21

[0082] Add 2% (relative to the mass of the total solution) of Gardenia Red dye to the nanocellulose suspension with a concentration of 2.5 wt%, stir and mix evenly to fully dissolve the dye. Add 2.5% (relative to the total solution quality) of high-carbon fatty alcohol polyoxyethylene ether to the solution, stir and mix evenly, and the resulting mixture can be used as a water-based pen or gel pen refill ink.

[0083] The nanocellulose-based refill ink prepared in this embodiment is red. In the application of water-based pen or gel pen, writing smoothly and continuously,

The ink is dark. The brightness (L) of the handwriting measured by the residual ink tester is 40.52, which is not much different from the brightness 33.18 of the commercially available ink "Deli S761".

[0084] Embodiment 22

[0085] Add 2% (relative to the mass of the total solution) of carmine acid dye to the nanocellulose suspension with a concentration of 2.5 wt%, stir and mix evenly, so that the dye is fully dissolved. Add 2.5% (relative to the mass of the total solution) of high-carbon fatty alcohol polyoxyethylene ether to the solution, stir and mix well, and the resulting mixture can be used as a water-based pen or gel pen refill ink.

[0086] The nanocellulose-based refill ink prepared in this embodiment is red. In the application of water-based pen or gel pen, writing smoothly and continuously,

The ink is dark. The brightness (L) of the handwriting measured by the residual ink tester is 40.27, which is not much different from the brightness 33.18 of the commercially available ink "Deli S761".

Claims

Claims [Claim 1] A method for preparing nano-cellulose-based refill ink, characterized in that it comprises the following steps:

(1) Add the dye to the nanocellulose suspension, stir until the dye is completely dissolved, the nanocellulose and the dye molecules intersect each other to maintain a stable colloidal state;

(2) Add surfactant to the solution obtained in step (1) and mix evenly to obtain nano-cellulose-based refill ink.

[Claim 2] A method for preparing nano-cellulose-based refill ink according to claim 1, characterized in that:

The nanocellulose in step (1) is one or more of nanocellulose obtained by acid hydrolysis, nanocellulose obtained by TEMPO oxidation, and nanocellulose obtained by grinding or ultrasonic methods.

[Claim 3] A method for preparing nanocellulose-based refill ink according to claim 1, wherein the dyes described in step (1) are acid dyes, neutral dyes, basic dyes, and reactive dyes. One or more of the dyes.

[Claim 4] A method for preparing nanocellulose-based refill ink according to claim 1, wherein the concentration of nanocellulose in step (1) is 1-5 wt%.

[Claim 5] A method for preparing nano-cellulose-based refill ink according to claim 1, characterized in that:

Step (1) The amount of dye is 0.1-10% of the mass of the obtained nanocellulose-based refill ink

[Claim 6] A method for preparing nano-cellulose-based refill ink according to claim 1, wherein the surfactant in step (2) is alkylphenol polyoxyethylene ether, high carbon Fatty alcohol polyoxyethylene ether, fatty acid polyoxyethylene ester, fatty acid methyl ester ethoxylate, polypropylene glycol ethylene oxide adduct, polyoxyethylated ionic surfactant, sorbitan ester, sucrose One or more mixtures of ester, alkyl alcohol amide type, and non-ionic fluorocarbon surfactants.

[Claim 7] A method for preparing nanocellulose-based refill ink according to claim 1, wherein the amount of the surfactant described in step (2) is the obtained nanocellulose-based refill ink 0.1-5% of the quality.

[Claim 8] A nano-cellulose-based refill ink prepared by the preparation method of any one of claims 1-7.