WO2024007865A1 - White dyne liquid - Google Patents

Abstract

The present invention belongs to the technical field of dyne liquids, and particularly relates to a white dyne liquid. The white dyne liquid contains at least one dyne-liquid aqueous solvent and/or contains at least one dyne-liquid oily solvent, wherein a hydrophilic white pigment is added to the at least one dyne-liquid aqueous solvent, and/or an oleophilic white pigment is added to the at least one dyne-liquid oily solvent. By adding the hydrophilic white pigment to the dyne-liquid aqueous solvent and/or adding the oleophilic white pigment to the dyne-liquid oily solvent, the white effect is obtained, such that the liquid can be used on a black substrate. The oleophilic white pigment and the hydrophilic white pigment can be respectively suspended in the dyne-liquid aqueous solvent and the dyne-liquid oily solvent for a long time, such that the normal use requirements can be completely satisfied.

Description

A white dyne liquid Technical field

The invention belongs to the technical field of dyne liquid, and particularly relates to a white dyne liquid.

Background technique

Dyne solution, that is, dyne ink, dyne solution (a mixed solution used to measure the wetting tension of films or sheets) is composed of: glycol ether, formamide, methanol and water. They are based on the national The surface wetting tension of different films or sheets can be measured according to the proportions specified in the standard (GB/T 14216-2018).

In the dyne solution in the prior art, a dye for color development is generally added, which is dispersed in the dyne solution in a molecular form. However, the existing technology lacks a white dyne solution to choose from. During actual use, technicians need to measure black substrates such as black films and black plastic parts. On black substrates, any color dyne solution other than white will seriously reduce the color development effect. Therefore, the existing technology is in urgent need of a white dyne solution. Because the current ordinary untreated white pigment cannot be dissolved or dispersed in dyne ink, ordinary white pigment will settle after being added and left to stand for a while, and is insoluble in the solvent and has a strong graininess, making it unusable.

Contents of the invention

The purpose of the present invention is to provide a white dyne liquid, aiming to solve the technical problem in the prior art that there is a lack of white dyne liquid and that ordinary white pigments will settle after being left to stand for a while after being added to the dyne liquid.

In order to achieve the above object, an embodiment of the present invention provides a white dyne liquid, which contains at least one aqueous solvent of dyne liquid and/or at least one oily solvent of dyne liquid;

Hydrophilic white pigment is added to at least one of the dyne solution aqueous solvents;

And/or, lipophilic white pigment is added to at least one of the dyne oil solvents.

Optionally, the hydrophilic white pigment is a surface-modified hydrophilic white pigment; the lipophilic white pigment is a surface-modified lipophilic white pigment.

Optionally, the surface treatment is a coating treatment; the hydrophilic white pigment is a silicon-coated metal oxide pigment, and the lipophilic white pigment is an aluminum oxide-coated metal oxide pigment; /or organic coated metal oxide pigment, the metal oxide is selected from at least one of titanium dioxide, zinc oxide and zirconium oxide.

Optionally, the aqueous solvent of dyne solution is selected from the group consisting of water, N-methylpyrrolidone, N-ethylpyrrolidone, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerin, isoprene glycol, and ethylene glycol. Alcohol, 1,2-pentanediol, 1,2-propanediol, butylene glycol, 2-methyl 1,3-propanediol, 1,2-hexanediol, benzyl alcohol, polyethylene glycol 200, dipropylene glycol, 1,3- Propylene glycol, sodium pyrrolidone carboxylate, 2-methyl-2,4-pentanediol, formamide, triethanolamine, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether At least one of ether, dipropylene glycol monomethyl ether, ethylene glycol diethyl ether or phenoxyethanol.

Optionally, the aqueous solvent of dyne solution contains at least one of water, N-methylpyrrolidone or N-ethylpyrrolidone.

Optionally, the aqueous solvent of the dyne solution contains at least one of N-methylpyrrolidone or N-ethylpyrrolidone, and 1,2-propylene glycol carbonate and ethyl lactate are added to the aqueous solvent of the dyne solution, At least one of ethylene glycol diacetate, 2-phenylethyl alcohol, propylene glycol diacetate, dimethyl oxalate or dodecanol carbonate.

Optionally, the content of water in the dyne solution aqueous solvent is the equilibrium moisture content of the dyne solution aqueous solvent under the conditions of 23° C. and 50% RH.

Optionally, the total content of at least one of water, N-methylpyrrolidone or N-ethylpyrrolidone in the aqueous solvent of dyne solution is 3%-99% of the mass of the aqueous solvent of dyne solution.

Optionally, the dyne liquid oil solvent is selected from ethanol, benzyl alcohol, 1,2,4-butanetriol, 1,2-propylene glycol carbonate, ethyl acetate, n-hexanol, isoamyl propionate, butyric acid Any one or more of butyl ester, dimethyl oxalate, ethyl caproate, dodecanol carbonate, ethyl lactate, isoamyl butyrate, ethylene glycol diacetate or propylene glycol diethyl ester mixture of the above.

Optionally, the mass of the hydrophilic white pigment accounts for 1-10% of the aqueous solvent of the dyne solution;

And/or, the mass of the lipophilic white pigment accounts for 1-10% of the dyne liquid oil solvent

One or more of the above technical solutions in the white dyne liquid provided by the embodiments of the present invention have at least one of the following technical effects:

1. The present invention obtains a white effect by adding hydrophilic white pigment to the water-based solvent of dyne solution, and/or adding lipophilic white pigment to the oil-based solvent of dyne solution, and can be used on black substrates;

2. The lipophilic white pigment and the hydrophilic white pigment in the present invention are both particulate matter. Compared with other pigments that are dissolved in the solvent in the form of molecules, the lipophilic white pigment and the hydrophilic white pigment have no effect after being added. The dyne value of dyne ink is more convenient to adjust the dyne value of dyne ink;

3. The lipophilic white pigment and the hydrophilic white pigment in the present invention can be suspended in the dyne aqueous solvent and the dyne oil solvent for a long time respectively, which can fully meet the normal use requirements.

Implementation

The present invention will be further described below with reference to examples, but the implementation of the present invention is not limited thereto.

Embodiments of the present invention provide a white dyne liquid, containing at least one dyne liquid aqueous solvent and/or at least one dyne liquid oil solvent; at least one dyne liquid aqueous solvent is added with a hydrophilic white pigment ;

And/or, at least one dyne liquid oil solvent is added with a lipophilic white pigment.

Specifically, the hydrophilic white pigment is a surface-modified hydrophilic white pigment; the lipophilic white pigment is a surface-modified lipophilic white pigment, and the surface treatment is a coating treatment; the hydrophilic white pigment is a silicone coating Films of metal oxide pigments. The lipophilic white pigment is an aluminum oxide coated metal oxide pigment and/or an organic matter coated metal oxide pigment. The metal oxide is at least one selected from titanium dioxide, zinc oxide and zirconium oxide.

By coating the white pigment, a white pigment stably dispersed in a dyne oil solvent and a dyne aqueous solvent can be obtained.

Exemplarily, silicon-coated titanium dioxide pigments can be obtained by the following preparation methods:

Disperse rutile titanium dioxide in deionized water, add sodium hexametaphosphate, and prepare a titanium dioxide aqueous solution with a mass concentration of 150-250g/L; adjust the pH to 8.5~9, and raise the temperature to 80-85°C; add dropwise to the titanium dioxide aqueous solution Sodium silicate solution with a concentration of 0.3-0.4mol/L, while adding 0.1-0.2mol/L sulfuric acid solution dropwise to keep the pH below 10. After the dropwise addition, the slurry is matured at 80-85°C for 1-2 hours. , then washed with deionized water, and heat treated in an environment of 170-180°C for 8-10 hours to prepare silicon-coated titanium dioxide pigment.

Illustratively, aluminum-coated titanium dioxide pigments can be obtained by the following preparation methods:

Configure the anatase titanium dioxide nanopowder into a suspension with a mass fraction of 12-18%, adjust the pH value of the suspension to 8.5, stir and disperse, add an alkali solution of sodium aluminate dropwise, and add sulfuric acid at the same time to maintain the pH value. 8.5, after the dropwise addition, continue to mature for 20-30 minutes, filter, and dry to obtain aluminum-coated titanium dioxide nanoparticles; configure the aluminum-coated titanium dioxide into a slurry, add sodium stearate, sodium stearate, and aluminum coating. The mass ratio of titanium dioxide is 1:10-25; react with stirring for 30-60 minutes. After filtration, the filter cake is dried at 70-80°C for 4-5 hours to obtain aluminum-coated titanium dioxide pigment.

The above is only one of the ways to obtain silicon-coated titanium dioxide pigments and aluminum-coated titanium dioxide pigments. Obtaining silicon-coated titanium dioxide pigments and aluminum-coated titanium dioxide pigments through other methods is also within the scope of the present invention.

In the embodiment of the present invention, the aqueous solvent of dyne solution is selected from the group consisting of water, N-methylpyrrolidone, N-ethylpyrrolidone, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerol, isoprene glycol, and ethanol. Glycol, 1,2-pentanediol, 1,2-propanediol, butylene glycol, 2-methyl 1,3-propanediol, 1,2-hexanediol, benzyl alcohol, polyethylene glycol 200, dipropylene glycol, 1,3 -Propylene glycol, sodium pyrrolidone carboxylate, 2-methyl-2,4-pentanediol, formamide, triethanolamine, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol At least one of methyl ether, dipropylene glycol monomethyl ether, ethylene glycol diethyl ether or phenoxyethanol.

The aqueous solvent of dyne solution contains at least one of water, N-methylpyrrolidone or N-ethylpyrrolidone.

Optionally, the aqueous solvent of the dyne solution contains at least one of N methylpyrrolidone or N ethylpyrrolidone, and 1,2-propylene glycol carbonate, ethyl lactate, and ethylene glycol dicarbonate are added to the aqueous solvent of the dyne solution. At least one of acetate, 2-phenylethyl alcohol, propylene glycol diacetate, dimethyl oxalate or dodecanol carbonate. These solvents have good compatibility with N-methylpyrrolidone or N-ethylpyrrolidone.

Diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether, dipropylene glycol monomethyl ether, ethylene glycol diethyl ether, phenoxyethanol, 1,2-propylene glycol carbonate, Ethyl lactate, ethylene glycol diacetate, 2-phenylethyl alcohol, propylene glycol diacetate, dimethyl oxalate or dodecanol carbonate have poorer affinity for hydrophilic titanium dioxide than other listed aqueous solvents. .

N-methylpyrrolidone or N-ethylpyrrolidone has a super affinity for hydrophilic titanium dioxide, second only to the affinity of water for hydrophilic titanium dioxide. At the same time, N-methylpyrrolidone has a higher affinity for esters and ethers than water. Therefore, when mixing hydrophilic titanium dioxide into esters and ethers, N-methylpyrrolidone needs to be used as a connecting agent. Before mixing, After mixing, the dissolving and suspending effects are completely different. In summary, N-methylpyrrolidone or N-ethylpyrrolidone can couple hydrophilic titanium dioxide and certain ether esters and other solvents that have poor affinity for hydrophilic titanium dioxide. After adding N-methylpyrrolidone or N-ethylpyrrolidone, the dissolution effect obtained is very good, and it plays a role similar to that of water on the mixture of hydrophilic alcohols and hydrophilic titanium dioxide.

In a preferred embodiment of the present invention, the aqueous solvent of the dyne solution contains at least 1,2-pentanediol. In the existing technology, the solvent is composed of a mixture of MPD and diethylene glycol. Although diethylene glycol is a hydrophilic raw material and can be mixed with hydrophilic titanium dioxide, MPD has poor affinity for hydrophilic titanium dioxide and lipophilic titanium dioxide. Therefore, the present invention uses 1,2-pentanediol as the aqueous solvent of dyne solution. 1,2 Pentylene Glycol has very good hydrophilicity. When mixed with hydrophilic titanium dioxide, the suspension of hydrophilic titanium dioxide is very good, and the suspended state is maintained for a long time, which can fully meet the actual needs of use. The content of water in the dyne solution aqueous solvent is the equilibrium moisture content of the dyne solution aqueous solvent under the conditions of 23°C and 50% RH. For example, the content of water in 1,2-pentanediol is the equilibrium moisture content of 1,2-pentanediol at 23°C and 50% RH. At this time, 1,2-pentanediol will not absorb moisture or evaporate water, which is beneficial to improving the stability of the dyne solution. Avoid changes in performance due to changes in moisture content.

In an embodiment of the present invention, the white dyne liquid also contains a moisturizing component, and the moisturizing component at least contains sodium pyrrolidone carboxylate. Most of the water-based raw materials of Indyne liquid are water-absorbent substances. In Dyne liquid that requires a large amount of water to be prepared, different water-based raw materials have different adsorption properties of water, causing the water to evaporate at an inconsistent rate during use. This ultimately leads to changes in the dyne liquid ratio, which leads to changes in the final dyne value, thus affecting the accuracy of use. After comparing the evaporation rate of water in a certain proportion of aqueous solution of sodium pyrrolidone carboxylate, a moisturizing ingredient, and an aqueous solution of the same proportion in other aqueous raw materials, it can be found that the evaporation rate of water in an aqueous solution of sodium pyrrolidone carboxylate is much lower than that of other aqueous raw materials. The rate at which water evaporates from a proportional aqueous solution. Based on this situation, existing products require that when using a Dyne pen, the pen cap must be tightly closed when not in use, and the pen cap must be closed promptly after use. Under such usage requirements, the shelf life is generally 6 months after opening. In view of this situation, the present invention introduces a moisturizing ingredient: sodium pyrrolidone carboxylate (PCA-Na). Compared with other hygroscopic raw materials, PCA-Na can improve the stability of the system several times under normal temperature and humidity. , usually three times.

In the embodiment of the present invention, the total content of at least one of water, N-methylpyrrolidone or N-ethylpyrrolidone in the aqueous solvent of dyne solution is 3%-99% of the mass of the aqueous solvent of dyne solution, More preferably, it is 40%.

In the embodiment of the present invention, the dyne liquid oil solvent is selected from ethanol, benzyl alcohol, 1,2,4-butanetriol, 1,2-propanediol carbonate, ethyl acetate, n-hexanol, isoamyl propionate, butylpropionate. Any one or one of butyl acid, dimethyl oxalate, ethyl hexanoate, dodecanol carbonate, ethyl lactate, isoamyl butyrate, ethylene glycol diacetate or propylene glycol diethyl ester. A mixture of more than one species.

In the embodiment of the present invention, the mass of the hydrophilic white pigment accounts for 1-10% of the aqueous solvent of the dyne solution. Specifically, the above proportions are 3%, 5%, 8% and 10% respectively.

In the embodiment of the present invention, the mass of lipophilic white pigment accounts for 1-10% of the oily solvent of dyne liquid. Specifically, the above proportions are 3%, 5%, 8% and 10% respectively.

In order to further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only to further illustrate the features and advantages of the present invention, rather than to limit the claims of the present invention.

Table 1 records the dyne solution aqueous solvent used in each embodiment of the present invention and the proportion of water added to the dyne solution aqueous solvent. Hydrophilic titanium dioxide was added to the dyne solution aqueous solvent. After the preparation is completed, let it sit for 7 days. The pigment (hydrophilic titanium dioxide) will slowly precipitate. Will the upper layer solution slowly become clearer due to the sedimentation of the pigment? By observing the precipitation of the bottom solution, To judge the solubility of the solution to hydrophilic titanium dioxide, the higher the height of the precipitation, the faster the pigment precipitates in the solution, and the weaker the solubility of the solution to the pigment.

Table 1

Example	Solvent 10g+3% hydrophilic titanium dioxide	Sedimentation depth (mm)	Example	Solvent 10g+3% hydrophilic titanium dioxide	Sedimentation depth (mm)
1	2methyl1,2propanediol	2	11	2 Methyl 1,2 Propylene Glycol + 25% Water	2
2	Ethylene glycol	1.7	12	Ethylene glycol + 25% water	1.5
3	1,3 butanediol	2.5	13	1,3 butanediol + 25% water	2.5
4	1,2 Pentylene Glycol	3	14	1,2 Pentylene glycol + 25% water	2.5
5	Isoprene glycol	2.5	15	Isoprene glycol + 25% water	2.5
6	1,3 propylene glycol	2	16	1,3 propylene glycol + 25% water	1
7	1,2 propylene glycol	3	17	1,2 propylene glycol + 25% water	1.5
8	triethylene glycol	3.5	18	Triethylene glycol + 25% water	1.5
9	dipropylene glycol	4	19	Dipropylene glycol + 25% water	3
10	1,4-butanediol	3	20	1,4 butanediol + 25% water	2

It can be seen from Table 1 that the solvents used in the embodiments of 1,3 propylene glycol + 25% water, 1,2 propylene glycol + 25% water and triethylene glycol + 25% water have the best suspension effect of the pigment in the dyne solution and can last for a long time. Time to set and pigments remain suspended for use.

In addition, the present invention can achieve changes in dyne values through the blending of solvents, see Table 2-4. Examples 21-24 used 1,2-pentanediol and ethanol + hydrophilic titanium dioxide. Examples 25-30 used 1,2-pentanediol and diethylene glycol + hydrophilic titanium dioxide. Examples 31-34 use ethanol and 1,2-propylene glycol carbonate + hydrophilic/lipophilic white pigment.

Table 2

table 3

Table 4

The example in Table 5 provides a comparison of the dissolving and suspending effects of MPD and 1,2-pentanediol on hydrophilic titanium dioxide. Among them, the bottom of the test tube used in the test has an outer diameter of about 15mm, a wall thickness of 1mm, a semicircle with an inner diameter of 13mm, and a radius of 6.5. All the above sedimentation depths are minus 1mm after the wall thickness depth is tested. According to the height, the deposition volumes of 6.1mm, 1.7mm and 0.5mm can be calculated as 522mm^3, 54mm^3 and 5mm^3 respectively. The volume ratio is 104:11:1.

table 5

	3% hydrophilic titanium dioxide (mm)	5% hydrophilic titanium dioxide (mm)	8% hydrophilic titanium dioxide (mm)	10% hydrophilic titanium dioxide (mm)
MPD equilibrium moisture content	5.5	6	8	9.5
40% water with MPD	3.5	4.5	5.5	6.5
Equilibrium moisture content of 1,2-pentanediol	1	1.5	2.5	3
40% water containing 1,2 pentanediol	0.5	1	2	2

It can be seen from Table 5 that the overall bottom of 1,2-pentanediol is about 1.7mm deep; the overall bottom of MPD is about 6.1mm deep on average, and the sedimentation volume is about 4 times that of 1,2-pentanediol.

The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention shall be included in the protection of the present invention. within the range.

Claims (10)

1. A white dyne liquid containing at least one dyne liquid water-based solvent and/or at least one dyne liquid oil-based solvent;

   It is characterized in that at least one hydrophilic white pigment is added to the aqueous solvent of dyne solution;

   And/or, lipophilic white pigment is added to at least one of the dyne oil solvents.
2. The white dyne liquid according to claim 1, characterized in that the hydrophilic white pigment is a surface-modified hydrophilic white pigment; the lipophilic white pigment is a surface-modified lipophilic white pigment. pigment.
3. The white dyne liquid according to claim 2, characterized in that the surface treatment is a coating treatment; the hydrophilic white pigment is a silicon-coated metal oxide pigment, and the lipophilic white pigment is Alumina-coated metal oxide pigments and/or organic matter-coated metal oxide pigments, the metal oxide being at least one selected from the group consisting of titanium dioxide, zinc oxide and zirconium oxide.
4. The white dyne liquid according to claim 1, characterized in that the aqueous solvent of the dyne liquid is selected from the group consisting of water, N-methylpyrrolidone, N-ethylpyrrolidone, diethylene glycol, triethylene glycol, and tetraethylene glycol. , Glycerol, isoprene glycol, ethylene glycol, 1,2-pentanediol, 1,2-propanediol, butylene glycol, 2-methyl 1,3-propanediol, 1,2-hexanediol, benzyl alcohol, poly Ethylene glycol 200, dipropylene glycol, 1,3-propylene glycol, sodium pyrrolidone carboxylate, 2-methyl-2,4-pentanediol, formamide, triethanolamine, diethylene glycol ethyl ether, diethylene glycol butyl ether, At least one of glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether, dipropylene glycol monomethyl ether, ethylene glycol diethyl ether or phenoxyethanol.
5. The white dyne liquid according to claim 4, characterized in that the aqueous solvent of the dyne liquid contains at least one of water, N-methylpyrrolidone or N-ethylpyrrolidone.
6. The white dyne liquid according to claim 4, wherein the aqueous solvent of the dyne liquid contains at least one of N-methylpyrrolidone or N-ethylpyrrolidone, and is added to the aqueous solvent of the dyne liquid. At least one of 1,2-propylene glycol carbonate, ethyl lactate, ethylene glycol diacetate, 2-phenylethyl alcohol, propylene glycol diacetate, dimethyl oxalate or dodecanol carbonate.
7. The white dyne liquid according to claim 5, characterized in that the content of water in the aqueous solvent of the dyne liquid is the equilibrium moisture content of the aqueous dyne liquid solvent under the conditions of 23° C. and 50% RH. .
8. The white dyne liquid according to claim 5, characterized in that the total content of at least one of water, N-methylpyrrolidone or N-ethylpyrrolidone in the aqueous solvent of the dyne liquid is 3%-99% of solvent quality.
9. The white dyne liquid according to any one of claims 1 to 8, characterized in that the oily solvent of the dyne liquid is selected from ethanol, benzyl alcohol, 1,2,4 butanetriol, 1,2-propylene glycol carbonic acid Ester, ethyl acetate, n-hexanol, isopentyl propionate, butyl butyrate, dimethyl oxalate, ethyl hexanoate, dodecyl carbonate, ethyl lactate, isoamyl butyrate, ethylene glycol Any one or a mixture of more than one alcohol diacetate or propylene glycol diethyl ester.
10. The white dyne liquid according to any one of claims 1-8, characterized in that the mass of the hydrophilic white pigment accounts for 1-10% of the aqueous solvent of the dyne liquid;

    And/or, the mass of the lipophilic white pigment accounts for 1-10% of the dyne liquid oil solvent.