CN114015285B - Oil stain resistant ink, preparation process thereof and oil stain resistant writing pen - Google Patents

Abstract

The application relates to the technical field of printing ink, and particularly discloses oil stain resistant printing ink, a preparation process thereof and an oil stain resistant writing pen, which are prepared from the following raw materials in parts by mass: the feed is prepared from the following raw materials in parts by mass: 18-24 parts of long-oil alkyd resin, 60-70 parts of ethyl acetate, 20-30 parts of NMP (N-methyl pyrrolidone), 19-25 parts of dispersant, 6-10 parts of polylactic acid-glycolic acid copolymer, 1-2 parts of drying agent, 10-15 parts of pigment and 2-5 parts of auxiliary agent; the preparation method comprises the following steps: preparing a primary mixture, and (2) preparing oil stain resistant ink. The product of the application can be used for writing on the surface of materials such as steel, wooden products or glass, and the like, which are adhered with oil stains.

Description

Oil-stain-resistant ink, preparation process thereof and oil-stain-resistant writing pen

Technical Field

The invention relates to the technical field of ink, in particular to oil stain resistant ink, a preparation process thereof and an oil stain resistant writing pen.

Background

The writing pen is a tool for writing or drawing, and is one of common study articles, including writing pens, highlighters, white board pens, water color pens, ball-point pens, pencils and the like. Wherein, the writing pen is a pen which can write marks or signs on one or more materials such as paper, wood, metal, plastic, enamel and the like. Common writing pens generally write or draw on the surface of one or more materials such as paper, wood, metal, plastic, enamel and the like when marking is needed.

According to the above-described related art, the inventors consider that: when the surface of materials such as steel, woodwork or glass is adhered with the greasy dirt, the greasy dirt on surface influences the inking for the pen is difficult for on the surface mark that adheres with the greasy dirt, has reduced the use experience of pen.

Disclosure of Invention

In order to facilitate marking of a writing pen on a smooth surface with oil stains, the application provides the oil stain resistant ink, the preparation process of the oil stain resistant ink and the oil stain resistant writing pen.

In a first aspect, the present application provides an oil stain resistant ink, which employs the following technical scheme:

the oil stain resistant ink is prepared from the following raw materials in parts by mass: 18-24 parts of long-oil alkyd resin, 60-70 parts of ethyl acetate, 20-30 parts of NMP (N-methyl pyrrolidone), 19-25 parts of dispersing agent, 6-10 parts of polylactic acid-glycolic acid copolymer, 1-2 parts of drying agent, 10-15 parts of pigment and 2-5 parts of auxiliary agent.

Because the oil stain resistant ink prepared by adding the long-oil alkyd resin into the raw materials is coated on a smooth surface and then is cured to form a film, the adhesive force is strong, and the wear resistance and the weather resistance are better, the ink prepared by adopting the long-oil alkyd resin in the raw materials is not easy to wear and peel off after being coated on the smooth surface, and the service life of the oil stain resistant ink prepared by adopting the long-oil alkyd resin in the raw materials is prolonged.

On the other hand, the long-oil alkyd resin has excellent brushing property and weather resistance and longer drying time, so that after the oil stain-resistant ink adopting the long-oil alkyd resin in the raw material is filled in an oil stain-resistant writing pen, the long-oil alkyd resin is not easy to dry during long-time writing or marking, the cap opening time of the oil stain-resistant writing pen is prolonged, and meanwhile, after the oil stain-resistant writing pen is unsealed and used, the oil stain-resistant ink adopting the long-oil alkyd resin in the raw material is not easy to dry, so that the service time of the oil stain-resistant writing pen is prolonged.

The ethyl acetate has excellent solvent capacity, is particularly convenient for uniform dispersion of the pigment, is convenient for full dissolution of other components such as the pigment in the raw material in the ethyl acetate, and is convenient for uniform dispersion of other components such as the pigment in the raw material, so that the oil stain resistant ink prepared by adopting the ethyl acetate in the raw material has uniform color.

On the other hand, the ethyl acetate is a quick-drying solvent, when the ethyl acetate is matched with long-oil-length alkyd resin, the drying speed of the oil-stain-resistant ink on a smooth surface can be accelerated, so that the oil-stain-resistant ink added with the ethyl acetate in the raw materials can be quickly dried after writing, and the oil-stain-resistant ink prepared by adding the ethyl acetate in the raw materials can be quickly dried after being coated on the surface of materials such as steel, wood products or glass.

Because NMP can dissolve most of organic and inorganic compounds, polar gases, natural and synthetic high molecular compounds and is relatively stable in a neutral solution, when the oil stain resistant ink prepared by adding NMP into the raw material is written on the surfaces of materials such as steel, wooden products or glass, and the like, the NMP can dissolve oil stains, so that the oil stain resistant ink can be conveniently coated on the surfaces of the materials such as the steel, wooden products or glass, and the writing pens filled with the oil stain resistant ink can conveniently mark on the smooth surfaces with the oil stains.

After the polylactic acid-glycolic acid copolymer is added into the raw materials, the pigment in the raw materials is uniformly dispersed in the long-oil alkyd resin through the polylactic acid-glycolic acid copolymer, so that the prepared oil stain resistant ink is uniform in color.

In addition, because the polylactic acid-glycolic acid copolymer has excellent film forming effect, the ink prepared by mixing the polylactic acid-glycolic acid copolymer in the raw materials can quickly form a film after being coated on the surface of materials such as steel, wood products or glass, and is not easy to be tinged.

On the other hand, the degradation products of the polylactic acid-glycolic acid copolymer are lactic acid and glycolic acid and are byproducts of human metabolic pathways, so that the oil stain resistant ink added with the polylactic acid-glycolic acid copolymer is not easy to pollute the environment in the production process, and the oil stain resistant ink is not easy to degrade after being coated on the surfaces of materials such as steel, wood products or glass, so that toxic and harmful substances are generated, and the ink is safe and environment-friendly.

Preferably, the dispersant is one or a mixture of anhydrous ethanol and propylene glycol methyl ether.

The absolute ethyl alcohol is a common solvent and is also an excellent vehicle, so that the pigment in the raw material can be uniformly dispersed in other components in the raw material after the absolute ethyl alcohol is added into the raw material, and the color of the ink prepared by adding the absolute ethyl alcohol into the raw material is uniform.

Since propylene glycol methyl ether is an excellent dispersant and diluent, when propylene glycol methyl ether is added into the raw material, other components such as pigment in the raw material are uniformly dispersed through the propylene glycol methyl ether after being mixed, so that the ink prepared by adding the propylene glycol methyl ether into the raw material has uniform color and smooth water outlet.

In addition, after the propylene glycol methyl ether is added into the raw materials, the propylene glycol methyl ether can adjust the volatilization speed of the solution, so that when the oil stain resistant ink prepared by mixing the propylene glycol methyl ether in the raw materials is coated on the surface of materials such as steel, wood products or glass, the oil stain resistant ink is convenient to adhere to the surface of the materials such as the steel, the wood products or the glass and form a film.

On the other hand, after the propylene glycol methyl ether is added into the raw material, the prepared ink still has good fluidity at a lower temperature, so that the ink prepared by adding the propylene glycol methyl ether into the raw material can keep smooth water outlet at the lower temperature after being filled in an oil stain resistant writing pen.

Preferably, the dispersing agent is formed by mixing anhydrous ethanol and propylene glycol methyl ether in a mass ratio of (3-8) to (10-20).

After the anhydrous ethanol and the propylene glycol methyl ether are mixed according to the mass part ratio in the preferable range of the application, the propylene glycol methyl ether is fully dissolved in the anhydrous ethanol and is fully dispersed in the raw material through the anhydrous ethanol, so that the enhancement effect of the propylene glycol methyl ether on the fluidity of the solution at low temperature is further improved. On the other hand, the dispersant formed by mixing the anhydrous ethanol and the propylene glycol monomethyl ether in the preferable range has better dispersing effect and diluting effect, is convenient for uniformly dispersing other components in the raw materials, and can reduce the viscosity of the oil-stain-resistant ink prepared from the components, so that the oil-stain-resistant ink can smoothly discharge water during writing.

Preferably, the dispersing agent is formed by mixing anhydrous ethanol and propylene glycol methyl ether in a mass ratio of (4-5) to (15-20).

When the anhydrous ethanol and the propylene glycol methyl ether are mixed according to the mass part ratio in the preferable range, the obtained dispersing agent has a better dispersing effect and a better diluting effect, the uniformity of the raw materials after mixing other components is improved, namely, the uniformity of the pigment mixed in other components is improved, so that the uniformity of the color of the oil stain resistant ink prepared from the pigment is improved, and the smoothness of the water outlet of the oil stain resistant ink is improved.

Preferably, the molar ratio of lactic acid to glycolic acid in the polylactic acid-glycolic acid copolymer is 60.

Because the degradation degree of the polylactic acid-glycolic acid copolymer is related to the monomer ratio, the larger the glycolide ratio is, the more easily degradable is, but when the molar ratio is 50, the degradation speed is faster, so that the polylactic acid-glycolic acid copolymer which is preferably adopted by the application has a lower degradation speed, the storage time of the oil stain resistant ink is prolonged, and the oil stain resistant ink after being sealed for a period of time still has better dispersibility.

Preferably, the auxiliary agent is nano alumina slurry, and the nano alumina slurry contains 30-60wt% of nano alumina and 2-10wt% of high molecular dispersing agent.

Due to the high porosity of the nano-alumina, after the nano-alumina slurry is mixed in the raw materials, the pigment is attached to the surface of the nano-alumina, and the nano-alumina is uniformly dispersed in the solution, so that the prepared oil stain resistant ink has uniform color.

On the other hand, when the oil stain resistant ink added with the nano alumina slurry in the raw materials is coated on the surface of materials such as steel, wooden products or glass, the abrasion resistance of the surface ink after film forming can be improved, so that the time for coating the ink on the surface of the materials such as the steel, the wooden products or the glass is prolonged.

The high molecular dispersing agent has the ionic surfactant with a special structure, so that the nano particles can obtain enough acting force to be mutually dispersed, the agglomeration probability of the nano particles is reduced, and the dispersion efficiency of the nano aluminum oxide is improved. The nanometer alumina is uniformly dispersed in the raw material through the macromolecular dispersing agent, so that the uniformity of the mixture of other components in the raw material and the nanometer alumina is improved, the uniformity of the mixture of the pigment adsorbed on the surface of the nanometer alumina and other components is improved, and the uniformity of the color of the oil stain resistant ink prepared from the nanometer alumina is improved.

Preferably, the surface of the nano-alumina is infiltrated and treated by one or more of stearic acid, lauric acid, oleic acid and simethicone.

After the nano alumina is soaked, the dispersibility and stability of the nano alumina in an oil solvent medium are obviously improved, so that the compatibility of the nano alumina powder and an organic matrix is obviously improved. Therefore, when the nano alumina powder subjected to coating treatment and the polymer dispersing agent which are optimized in the application are matched in a solvent for dispersion, the nano alumina powder is not easy to agglomerate for the second time, so that the dispersion stability and the dispersion efficiency of the nano alumina in the solvent are improved.

Preferably, the desiccant is zinc oleate.

The zinc oleate is a common drying agent, and when the oil stain resistant ink prepared by adding the zinc oleate into the raw materials is coated on the surfaces of materials such as steel, wood products or glass, the oil stain resistant ink can be quickly dried, so that the oil stain resistant ink is convenient to adhere to the surfaces of the materials such as the steel, the wood products or the glass and form a film.

In a second aspect, the present application provides a preparation process of an oil stain resistant ink, which adopts the following technical scheme: a preparation process of oil stain resistant ink comprises the following steps:

(1) Preparation of a primary mix: taking 18-24 parts of long-oil alkyd resin, 60-70 parts of ethyl acetate, 20-30 parts of NMP, 19-25 parts of dispersant, 10-15 parts of pigment and 2-5 parts of auxiliary agent according to parts by mass, mixing, uniformly stirring, and standing for 6-8 hours to obtain a primary mixture;

(2) Preparing oil stain resistant ink: and grinding the primary mixture, adding 6-10 parts of polylactic acid-glycolic acid copolymer and 1-2 parts of drying agent, uniformly stirring, and standing for 1h to obtain the oil stain resistant ink.

The long-oil alkyd resin, the ethyl acetate, the NMP, the dispersing agent, the pigment and the auxiliary agent are added to be fully mixed, and the mixture is stood for a long time to prepare a uniformly mixed primary mixture, wherein the long-oil alkyd resin, the ethyl acetate, the NMP, the dispersing agent, the pigment and the auxiliary agent are mixed and are not easy to volatilize and dry, and not easy to form a film, and the primary mixture has the stability after dispersion, and is uniformly dispersed and stable in property after standing; the film-forming aid and the drying agent are added into the ground primary mixture, the particle size of the ground primary mixture is small, the primary mixture is conveniently and uniformly mixed with the film-forming aid and the drying agent, the uniformity of mixing of all components can be further improved, meanwhile, the mixture of the primary mixture into which the film-forming aid and the drying agent are added has good leveling property, and after the primary mixture is ground, the film-forming aid and the drying agent are added, stirred and kept stand for a short time, the obtained oil stain-resistant ink has stable dispersibility.

In a third aspect, the present application provides an oil stain resistant pen, which adopts the following technical scheme:

an oil stain resistant writing pen is filled with the oil stain resistant ink.

When the oil stain resistant writing pen filled with the oil stain resistant ink is used on the surface of a steel material, a wooden product or glass and other materials attached with oil stains, the oil stain resistant ink can dissolve the oil stains on the surface, and meanwhile, the oil stain resistant ink can be quickly attached to the surface of the steel material, the wooden product or the glass and other materials to form a film quickly, so that the writing pen is not easy to scrape flowers and be stained; on the other hand, in the writing process of the oil stain resistant writing pen, the filled oil stain resistant ink is not easy to volatilize and dry, so that the cap opening time of the oil stain resistant writing pen is prolonged, and the service life of the oil stain resistant writing pen is prolonged.

In summary, the present application has the following beneficial effects:

1. the oil stain resistant ink can dissolve oil stains when being used for writing on the surfaces of materials such as steel, wooden products or glass, which are attached with oil stains, and meanwhile, the oil stain resistant ink can be quickly attached to the surfaces and dried to form films, and the films are left on the surfaces of the materials such as the steel, the wooden products or the glass and are not easy to be tinged and abraded.

2. The oil stain resistant ink is filled in the oil stain resistant writing pen, is not easy to volatilize and dry in the writing process of the oil stain resistant writing pen, increases the cap opening time of the oil stain resistant writing pen, and prolongs the service life of the oil stain resistant writing pen.

Detailed Description

The present application will be described in further detail with reference to examples.

Raw materials

The raw material components of the invention are shown in the table 1:

TABLE 1 sources of the raw material components

Examples

Examples 1-21 were prepared in the same manner, except that the component materials were varied in weight as shown in Table 2.

Preparation example 1

The preparation method of the nano alumina slurry comprises the following steps:

s1: soaking nano aluminum oxide in stearic acid for 2h;

s2: mixing 2kg of high molecular dispersant with 68kg of ethyl acetate, adding 30kg of soaked nano-alumina, and dispersing in a high-speed dispersion machine at 2000rpm for 30min to obtain primary slurry;

s3: and grinding the primary slurry in a ball mill for 18 hours to obtain the nano alumina slurry.

Preparation example 2

The present preparation example differs from preparation example 1 only in that the amount of nano alumina added in S2 was 45kg, and correspondingly, the amount of ethyl acetate added as a solvent in S1 was 53kg.

Preparation example 3

The present preparation example differs from preparation example 1 only in that the amount of nano alumina added in S2 was 60kg, and correspondingly, the amount of ethyl acetate added as a solvent in S1 was 38kg.

Preparation example 4

The present production example differs from production example 1 only in that the amount of the polymeric dispersant added in S2 was 6kg, and the amount of ethyl acetate added as a solvent in S1 was 49kg.

Preparation example 5

The present production example differs from production example 1 only in that the amount of the polymeric dispersant added in S2 was 10kg, and the amount of ethyl acetate added as a solvent in S1 was 45kg.

A preparation process of the oil stain resistant ink comprises the following steps:

(1) Preparation of a primary mix: taking 18kg of long-oil alkyd resin, 60kg of ethyl acetate, 20kg of NMP, 4kg of absolute ethyl alcohol, 15kg of propylene glycol methyl ether, 10kg of carbon black and 2kg of nano alumina slurry, putting the mixture into a stirrer, uniformly stirring the mixture, and standing the mixture for 8 hours to obtain a primary mixture;

(2) Preparing oil stain resistant ink: grinding the primary mixture in a grinder until the particle size is less than 90 μm, and adding 6kg of polylactic acid-glycolic acid copolymer and 1kg of zinc oleate to obtain an intermediate mixture;

and (3) stirring the intermediate mixture in a stirrer for 30min, standing for 1h, and filtering with a 200-mesh filter screen to obtain the oil stain resistant ink.

TABLE 2 materials and their weights in examples 1-21

Because the content of ethyl acetate in the nano alumina slurry is very small compared with the addition amount of ethyl acetate in the raw material, when the mass fractions of the surface-coated nano alumina and the polymer dispersant in the nano alumina slurry are adjusted, the change of the addition amount of ethyl acetate in the nano alumina slurry hardly affects other components in the raw material.

In examples 1 to 15, preparation example 1 was used for the nano alumina slurry.

Example 16

The difference from example 13 is that the nano alumina paste was prepared according to preparation example 2.

Example 17

The difference from example 13 is that the nano alumina paste was prepared according to preparation example 3.

Example 18

The difference from example 16 is that the nano alumina paste of preparation example 4 was used.

Example 19

The difference from example 16 is that the nano alumina paste of preparation example 5 was used.

Example 20

The difference from example 18 is that the molar ratio of lactic acid to glycolic acid in the polylactic acid-glycolic acid copolymer is 50.

Example 21

The difference from example 18 is that the molar ratio of lactic acid to glycolic acid in the polylactic acid-glycolic acid copolymer is 75.

Comparative example

Comparative example 1

The difference from example 5 is that NMP was not added to the starting material.

Comparative example 2

The difference from example 5 was that NMP was added in an amount of 50kg in the starting material.

Comparative example 3

The difference from example 5 is that the long oil alkyd resin in the stock is a short oil alkyd resin.

Comparative example 4

The difference from example 5 is that the amount of long oil alkyd resin added to the stock was 50kg.

Comparative example 5

The difference from example 5 is that no polylactic acid-glycolic acid copolymer was added to the starting material.

Comparative example 6

The difference from example 5 is that the amount of polylactic acid-glycolic acid copolymer added to the starting material was 20kg.

Performance test

The inks prepared in examples 1 to 21 and comparative examples 1 to 4 were randomly set to 20g each in one set of 3, and the following performance test experiments were carried out for each set of samples, and the three monitored data of each set were averaged.

1. Surface tension test

The surface tension (mN/m) of the patterns in examples and comparative examples was calculated by examining the patterns and recording the data with reference to the surface tension test of 5.3 in QB/T4169-2011.

2. Viscosity test

The viscosity (mPas) of the samples of examples and comparative examples was calculated by examining the samples and recording the data with reference to the 5.2 viscosity test in QB/T4169-2011.

3. Intermittent writing Performance test

Referring to the 5.6 intermittent writing performance test in QB/T4169-2011, each sample was filled in a writing pen of the same specification, and the sample was examined and data was recorded, and the interval time (min) of the trace within 100mm of the sample in the example and the comparative example was calculated.

4. Drying test

Referring to the 6.6 dryness test in QB/T2777-2006, each sample was filled in a writing pen of the same specification, and the sample was examined and data was recorded, and the dryness of the samples in examples and comparative examples, which were no ink on the A-coated paper and ink on the B-coated paper, was calculated.

5. Adhesion test

Referring to the 6.7 adhesion test in QB/T2777-2006, each sample was filled in a writing pen of the same specification, the patterns were detected and data were recorded, and the case where the stitches of the patterns in the examples and comparative examples were erased, the case where the A-stitch was not erased, and the case where the B-stitch was erased were calculated.

6. Oil stain resistance test

At 1m ² Spraying the higher fatty glyceride mixture on the glass plate until the surface area of the glass plate is uniformly covered by the higher fatty glyceride mixture by 90%, filling each sample into writing pens with the same specification under the conditions that the environmental temperature is 20 +/-5 ℃ and the relative humidity is 65 +/-5%, taking down the writing pens, marking a straight line on the surface of the glass plate by hand, and measuring the distance (mm) from the starting point of the upper writing pen to the starting point of the lower writing pen to the marking line of the glass plate.

7. Aging resistance test

According to a 6.2 writing performance test in QB/T2777-2006, heating each sample at 100 ℃ for 1h, filling the heated sample into writing pens with the same specification, and detecting the aged writing performance of the sample; the stitches in the A-100m are smooth, and the phenomena of obvious fading and breakage do not occur; the phenomena of trace lightening and line breakage occur within B-100m, and the length of the trace which shows the phenomena of lightening and line breakage is less than or equal to 1m; the phenomena of trace lightening and line breakage occur within C-100m, and the length of the trace with the phenomena of lightening and line breakage is less than or equal to 5m and more than 1m.

And (3) detection results: the results of the tests on the samples obtained in examples 1 to 21 and comparative examples 1 to 4 are shown in Table 3.

Table 3 type performance test results table

It can be seen from the combination of example 5 and comparative examples 1 and 2 and table 3 that the samples prepared from raw materials using NMP in the range of the present application have shorter stitch length, the samples prepared from raw materials not using NMP have longer stitch length, the samples prepared from raw materials using excessive NMP have shorter stitch length than the samples prepared from raw materials not using NMP, but the samples prepared from raw materials using excessive NMP have ink marks on the cover paper, and the samples prepared from raw materials using NMP and samples prepared from raw materials not using NMP have no ink marks on the cover paper. Therefore, the oil stain resistant ink prepared from the raw material by adopting the NMP in the range of the application is easier to write on the smooth surface with oil stains, the oil stain resistant ink prepared from the raw material without adopting the NMP is not easy to write on the smooth surface with oil stains, the oil stain resistant ink prepared from the raw material by adopting excessive NMP is easier to write on the smooth surface with oil stains compared with the oil stain resistant ink prepared from the raw material without adopting the NMP, but the oil stain resistant ink prepared from the raw material by adopting excessive NMP has poorer drying property.

It can be seen from the combination of example 5 and comparative examples 3 and 4 and from table 3 that the stitches of the samples made with long oil alkyd resins in the range of the present application were not erased and the intervals between the scribing were longer in the raw material, the intervals between the scribing of the samples made with short oil alkyd resins in the raw material were shorter, and the stitches of the samples made with too much long oil alkyd resin in the raw material were erased. Therefore, the oil stain resistant ink made of the long oil alkyd resin in the range of the application in the raw material has better drying property, better intermittent writing property and better adhesiveness, namely, longer cap opening time, the trace intermittent writing property of the ink made of the short oil alkyd resin in the raw material is poorer, namely, shorter cap opening time, and the adhesiveness of the ink made of the excessive long oil alkyd resin in the raw material is poorer.

As can be seen by combining example 5 with comparative examples 5 and 6 and table 3, after the aging treatment, the trace drawn by the sample made of the pla-glycolic acid copolymer in the range of the present application in the raw material is smooth, the interval time between the traces drawn by the sample is longer, the distance of the trace sliding out of the glass plate is longer, and the ink mark exists in the cover of the sample made of the raw material without the pla-glycolic acid copolymer and the trace is erased; after a sample prepared by adding excessive polylactic acid-glycolic acid copolymer into the raw materials is aged, the trace becomes light and breaks, the interval time for marking the trace by the sample is short, and the distance for marking the trace on a glass plate is long; namely, the oil stain resistant ink prepared by adopting the polylactic acid-glycolic acid copolymer in the range has longer service life, better intermittent writing performance, drying performance and adhesiveness, the oil stain resistant ink prepared by not adopting the polylactic acid-glycolic acid copolymer in the raw materials has poorer adhesiveness and drying performance, and the oil stain resistant ink prepared by adding excessive polylactic acid-glycolic acid copolymer in the raw materials has shorter cap opening time and poorer aging resistance and oil stain resistance.

It can be seen from the combination of examples 1-3 and Table 3 that the samples made from the materials using long oil alkyd resins and ethyl acetate in the preferred ranges of the present application have slightly higher surface tension and lower viscosity, i.e., the ink-resistant inks made from long oil alkyd resins and ethyl acetate in the preferred ranges of the present application have slightly higher surface tension and lower viscosity.

In combination with examples 2, 4 and 5 and in combination with table 3, it can be seen that samples of the stock made with NMP in the preferred range of the present application slipped out of the trace on a stained glass plate for a shorter distance, i.e. the oil stain resistant ink made with NMP in the preferred range of the present application written more easily on a stained smooth surface.

It can be seen from the combination of examples 4, 6 and 7 and table 3 that the coated paper of the sample made of the pla-glycolic acid copolymer in the range of the present application has no ink mark, but the sample made of the pla-glycolic acid copolymer in the range of the present application has a longer interval time, that is, the antifouling ink made of the pla-glycolic acid copolymer in the range of the present application has a better intermittent writing ability, that is, a longer cap opening time, while maintaining the dryness.

In the combination of examples 6, 8 and 9 and Table 3, it can be seen that the interval time between samples made of the raw material using anhydrous ethanol in the preferred range of the present application is slightly longer and the surface tension is slightly smaller, i.e., the surface tension of the raw material using the sample in the preferred range of the present application is smaller and the intermittent writing ability is better, so the uncapping time is longer.

It can be seen from the combination of examples 6, 10 and 11 and table 3 that the samples made of propylene glycol methyl ether in the preferred range of the present application have a lower viscosity and a longer interval time, that is, the oil stain resistant ink made of propylene glycol methyl ether in the preferred range of the present application has a lower viscosity and a better intermittent writing ability, thereby having a longer decap time.

It can be seen from the combination of examples 10, 12 and 13 and table 3 that the samples made with zinc oleate in the preferred range of the present application in the raw materials all had no ink marks on the coated paper and had similar time intervals, but the samples made with zinc oleate in the preferred range of the present application had shorter slip-out traces on the stained glass plate, i.e., the samples made with zinc oleate in the preferred range of the present application all had dryness and similar intermittent writing ability, but the samples made with zinc oleate in the preferred range of the present application had better writing ability on the stained smooth surface.

It can be seen from the combination of examples 10, 14 and 15 and table 3 that the surface tension of the sample made of the nano alumina paste in the preferred range of the present application is relatively large, and the time interval is relatively long, i.e. the surface tension of the oil stain resistant ink made of the nano alumina paste in the preferred range of the present application is relatively large, and the intermittent writing capability is relatively good, i.e. the cap opening time of the oil stain resistant ink made of the nano alumina paste in the preferred range of the present application is relatively long.

It can be seen from the combination of examples 14, 16 and 17 and table 3 that the surface tension of the sample made of nano alumina in the preferred range of the present application is slightly larger and the time interval is longer, that is, the surface tension of the ink made of nano alumina in the preferred range of the present application is slightly larger and the intermittent writing ability is better, that is, the cap opening time of the ink made of nano alumina slurry in the preferred range of the present application is longer.

In examples 16, 18 and 19 and table 3, it can be seen that the surface tension of the sample prepared by using the polymeric dispersant in the preferred range of the present application in the raw material is slightly lower, and the distance of the trace sliding out of the surface of the glass plate with oil stains is slightly shorter, i.e. the surface tension of the oil stain resistant ink prepared by using the polymeric dispersant in the preferred range of the present application is slightly lower, and it is easier to write on the smooth surface with oil stains.

It can be seen from the combination of examples 18, 20 and 21 and table 3 that the aged traces of the samples made from the raw materials using the pla-glycolic acid copolymer in the preferred range of the present application are smooth, and the aged traces of the samples not made from the pla-glycolic acid copolymer in the preferred range of the present application are weakened or broken, i.e. the inks made from the pla-glycolic acid copolymer in the preferred range of the present application have better aging resistance.

In summary, in the oil-stain resistant ink in which the surface tension, viscosity, intermittent writing performance, drying property, adhesion and aging resistance all meet the standards, the sample prepared in example 18 is easier to write on the surface of the glass plate with oil stains, that is, example 18 has the performance of being most easy to write on the smooth surface with oil stains; meanwhile, the interval time of the embodiment 18 is longer, namely, the embodiment 18 has longer cap opening time.

The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.

Claims (8)

1. An oil stain resistant ink, characterized in that: the feed is prepared from the following raw materials in parts by mass: 18-24 parts of long-oil alkyd resin, 60-70 parts of ethyl acetate, 20-30 parts of NMP (N-methyl pyrrolidone), 19-25 parts of dispersant, 6-10 parts of polylactic acid-glycolic acid copolymer, 1-2 parts of drying agent, 10-15 parts of pigment and 2-5 parts of auxiliary agent;

the dispersing agent is formed by mixing anhydrous ethanol and propylene glycol methyl ether according to a mass ratio of (3-8) to (10-20).

2. The ink as claimed in claim 1, wherein: the dispersing agent is formed by mixing anhydrous ethanol and propylene glycol methyl ether according to a mass ratio of (4-5) to (15-20).

3. The ink as claimed in claim 1, wherein: the molar ratio of lactic acid to glycolic acid in the polylactic acid-glycolic acid copolymer is 60.

4. The ink as claimed in claim 1, wherein: the auxiliary agent is nano alumina slurry, and the nano alumina slurry contains 30-60wt% of nano alumina and 2-10wt% of high molecular dispersing agent.

5. The ink as claimed in claim 4, wherein: the surface of the nano-alumina is soaked by one or a mixture of stearic acid, lauric acid, oleic acid and dimethyl silicone oil.

6. The ink as claimed in claim 1, wherein: the drying agent is zinc oleate.

7. A process for preparing the oil stain resistant ink as claimed in any one of claims 1-6, wherein: the method comprises the following steps:

(1) Preparation of a primary mix: taking 18-24 parts of long-oil alkyd resin, 60-70 parts of ethyl acetate, 20-30 parts of NMP, 19-25 parts of dispersant, 10-15 parts of pigment and 2-5 parts of auxiliary agent according to parts by mass, mixing, uniformly stirring, and standing for 6-8 hours to obtain a primary mixture;

(2) Preparing oil stain resistant ink: and grinding the primary mixture, adding 6-10 parts of polylactic acid-glycolic acid copolymer and 1-2 parts of drying agent, uniformly stirring, and standing for 1h to obtain the oil stain resistant ink.

8. An oil stain resistant writing pen, which is characterized in that: filled with an ink resistant to oil soiling according to any one of the preceding claims 1 to 6.