CN113292783A - Black master batch with high tinting strength and preparation method thereof - Google Patents

Abstract

The application relates to the technical field of coloring master batches, and particularly discloses a black master batch with high tinting strength and a preparation method thereof. The black master batch comprises the following components in parts by weight: 35-49 parts of carrier resin; 75-90 parts of modified carbon black; 1-5 parts of a dispersant; 1-5 parts of a coloring assistant; the dispersing agent is one or a combination of polyethylene wax and metal stearate; the metal stearate is one of barium stearate, zinc stearate, calcium stearate and magnesium stearate; the preparation method comprises the following steps: d1, putting the carrier resin into a mixing roll, heating to 200 ℃, mixing for 1-1.5h, and then putting the dispersing agent into the mixing roll, mixing for 0.5-1 h; d2, averagely dividing the modified carbon black into three parts, putting the three parts of the modified carbon black into a mixing roll at intervals of 30-40min, mixing for 2-2.5h in total, adding a coloring auxiliary agent, and mixing for 2.5-3h to obtain a black master batch; d3, extruding and granulating the black master batch, and drying to obtain the black master batch. The black master batch can be used for dyeing plastic products and has the advantage of high tinting strength.

Description

Black master batch with high tinting strength and preparation method thereof

Technical Field

The application relates to the technical field of coloring master batches, in particular to a black master batch with high tinting strength and a preparation method thereof.

Background

Synthetic resin and plastic are indispensable important materials in various fields of production and life, plastic coloring is an indispensable ring in plastic production, and the synthetic resin and the plastic not only add harmonious colors to plastic products to beautify the surrounding world, but also can endow the plastic with multiple functions, improve certain application properties of the plastic and endow the plastic with new characteristics.

Conventional methods for coloring plastics include dry (float) coloring, paste coloring, liquid coloring, and the like. The pigment is generally powdery, has poor dispersibility, difficult control of metering, poor coloring effect and high cost, and can cause color difference in products with extremely small pigment addition amount; for products with high pigment concentration, the affinity between the pigment and the resin is poor, so that the processing performance of the products is poor, and the physical and mechanical properties are reduced; moreover, the pigments are easy to fly during adding and mixing, and the health of operators is affected after the pigments are inhaled by human bodies. The existence of these problems limits the application of traditional plastic coloring methods, and the color masterbatch coloring can better solve the problems.

Color concentrates are aggregates prepared by uniformly loading a constant amount of pigment into a resin. The color masterbatch generally consists of a colorant, a carrier and a dispersant, and is generally prepared by mixing the colorant, the carrier and the dispersant through a high-speed mixer, crushing, extruding and drawing into particles. Therefore, the color master batch is a plastic colorant formed by well dispersing a high proportion of pigment or additive and thermoplastic resin, the selected resin has good wetting and dispersing effects on the colorant, and has good compatibility with a material to be colored and better affinity for the pigment.

The black master batch is one of the master batches, is the most commonly used master batch in plastic processing, and is also the master batch with the largest use amount. The black master batch is a plastic colorant which is well dispersed by carbon black, additives and thermoplastic resin with high proportion, and the selected resin has good wetting and dispersing effects on the colorant and has good compatibility with a colored material. However, when the existing black master batch is added into a plastic product, the black master batch is easy to separate out, and the coloring effect is poor.

Disclosure of Invention

In order to improve the coloring capability of the black master batch, the application provides the black master batch with high tinting strength and a preparation method thereof.

In a first aspect, the application provides a black masterbatch with high tinting strength, which adopts the following technical scheme:

a black master batch with high tinting strength comprises the following components in parts by weight:

the dispersing agent is one or a combination of polyethylene wax and metal stearate;

the metal stearate is one of barium stearate, zinc stearate, calcium stearate and magnesium stearate.

By adopting the technical scheme, the carrier resin is used as the matrix resin of the black master batch, and can adsorb the modified carbon black after being heated and melted, so that the effect of color master batch is achieved; the modified carbon black is used as a black pigment provider, so that the black pigment can play a role in dyeing a plastic product after being added into the plastic product, and compared with common carbon black, the modified carbon black is more easily distributed in carrier resin and has stronger tinting strength; the dispersant can help the modified carbon black to be uniformly distributed in the carrier resin; the coloring auxiliary agent enables the black master batch to be added into the plastic product, the black master batch can be distributed more uniformly, and the coloring capability of the modified carbon black is improved.

Preferably, the modified carbon black is prepared from the following raw materials in parts by weight:

by adopting the technical scheme, when the modified carbon black is prepared, the carbon black is a main substance; the activator improves the activity of the surface of the carbon black, and the coupling agent enables the polyvinyl alcohol and the carbon black to generate a coupling reaction.

Preferably, the modified carbon black is prepared by the following preparation steps:

s1, grinding and sieving carbon black to obtain carbon black powder, placing the carbon black powder in a vacuum environment, heating to 85 ℃ and keeping for 0.5h, adding the carbon black powder into absolute ethyl alcohol, and stirring to obtain mixed slurry;

s2, keeping the temperature in S1, adding an active agent into the mixed slurry, stirring at the rotating speed of 500r/min for 10min, sequentially adding the polyethanol and the coupling agent into the mixed slurry, and stirring at the rotating speed of 600r/min for 15min to obtain modified mixed slurry;

and S3, cooling the modified mixed slurry to room temperature under stirring at the rotating speed of 70r/min, carrying out suction filtration on the modified mixed slurry, and drying the suction filtration to obtain the modified carbon black.

Preferably, the active agent is sodium dodecyl benzene sulfonate.

Preferably, the coupling agent is hexamethyldisilazane.

Preferably, the dispersing agent comprises polyethylene wax and metal stearate, and the weight part ratio of the polyethylene wax to the metal stearate is 1: (0.3-0.5).

Preferably, the polyethylene wax has a molecular weight of 3000-4000.

Preferably, the coloring assistant is diatomite.

In a second aspect, the application provides a preparation method of a black master batch with high tinting strength, which adopts the following technical scheme:

a preparation method of a black master batch with high tinting strength comprises the following steps:

d1, putting the carrier resin into a mixing roll, heating to 200 ℃, mixing for 1-1.5h, and then putting the dispersing agent into the mixing roll, mixing for 0.5-1 h;

d2, averagely dividing the modified carbon black into three parts, putting the three parts of the modified carbon black into a mixing roll at intervals of 30-40min, mixing for 2-2.5h in total, adding a coloring auxiliary agent, and mixing for 2.5-3h to obtain a black master batch;

d3, extruding and granulating the black master batch, and drying to obtain the black master batch.

By adopting the technical scheme, in D1, the carrier resin is heated and mixed to soften the carrier resin and have activity, and then the dispersing agent is put into a mixing roll to be mixed to uniformly disperse the dispersing agent in the carrier resin; in D2, evenly dividing the modified carbon black into three parts, sequentially putting the three parts into a mixing roll to ensure that the modified carbon black is more uniformly distributed, and adding a coloring auxiliary agent for mixing to ensure that the modified carbon black is uniformly distributed; in D3, the black master batch is obtained by extrusion granulation, and is convenient to transport and put into use.

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

1. the black master batch comprises the following components in parts by weight: 35-49 parts of carrier resin; 75-90 parts of modified carbon black; 1-5 parts of a dispersant; 1-5 parts of a coloring assistant; the dispersing agent is one or a combination of polyethylene wax and metal stearate; the metal stearate is one of barium stearate, zinc stearate, calcium stearate and magnesium stearate; the carrier resin is used as matrix resin of the black master batch, and can adsorb modified carbon black after being heated and melted, so that the function of the black master batch is achieved; the modified carbon black is used as a black pigment provider, so that the black pigment can play a role in dyeing a plastic product after being added into the plastic product, and compared with common carbon black, the modified carbon black is more easily distributed in carrier resin and has stronger tinting strength; the dispersant can help the modified carbon black to be uniformly distributed in the carrier resin; the coloring auxiliary agent enables the black master batch to be added into the plastic product, the black master batch can be distributed more uniformly, and the coloring capability of the modified carbon black is improved.

2. The modified carbon black used in the application is prepared from the following raw materials in parts by weight: 80-90 parts of carbon black; 10-15 parts of polyethanol; 1-3 parts of an active agent; 1-3 parts of a coupling agent; when the modified carbon black is prepared, the carbon black is a main substance; the activator improves the activity of the surface of the carbon black, and the coupling agent enables the polyvinyl alcohol and the carbon black to generate a coupling reaction.

3. The method of the present application comprises the steps of: d1, putting the carrier resin into a mixing roll, heating to 200 ℃, mixing for 1-1.5h, and then putting the dispersing agent into the mixing roll, mixing for 0.5-1 h; d2, averagely dividing the modified carbon black into three parts, putting the three parts of the modified carbon black into a mixing roll at intervals of 30-40min, mixing for 2-2.5h in total, adding a coloring auxiliary agent, and mixing for 2.5-3h to obtain a black master batch; d3, extruding and granulating the black master batch, and drying to obtain the black master batch; in D1, heating and mixing the carrier resin to soften the carrier resin and enable the carrier resin to have activity, and then putting the dispersing agent into a mixing roll for mixing to enable the dispersing agent to be uniformly dispersed in the carrier resin; in D2, evenly dividing the modified carbon black into three parts, sequentially putting the three parts into a mixing roll to ensure that the modified carbon black is more uniformly distributed, and adding a coloring auxiliary agent for mixing to ensure that the modified carbon black is uniformly distributed; in D3, the black master batch is obtained by extrusion granulation, and is convenient to transport and put into use.

Detailed Description

The present application will be described in further detail with reference to examples 1 to 21 and comparative examples 1 to 3.

Examples

Examples 1 to 3

The parts by weight of the components of the black master batch in examples 1-3 are shown in Table 1.

TABLE 1 parts by weight of the components of the black master batch in examples 1-3

In examples 1-3, modified carbon blacks were prepared by the following preparation steps:

s1, grinding and sieving 85 parts by weight of carbon black to obtain carbon black powder, placing the carbon black powder in a vacuum environment, heating to 85 ℃ and keeping for 0.5h, adding the carbon black powder into absolute ethyl alcohol, and stirring to obtain mixed slurry;

s2, keeping the temperature in S1, adding 2 parts by weight of an active agent into the mixed slurry, stirring at the rotating speed of 500r/min for 10min, sequentially adding 13 parts by weight of polyethanol and 2 parts by weight of a coupling agent into the mixed slurry, and stirring at the rotating speed of 600r/min for 15min to obtain modified mixed slurry; the activator is sodium dodecyl benzene sulfonate, and the coupling agent is hexamethyldisilazane;

and S3, cooling the modified mixed slurry to room temperature under stirring at the rotating speed of 70r/min, carrying out suction filtration on the modified mixed slurry, and drying the suction filtration to obtain the modified carbon black.

The polyethylene waxes used in examples 1-3 had molecular weights between 3000 and 4000.

In examples 1 to 3, the preparation method of the black masterbatch includes the following steps:

d1, placing the carrier resin into a mixing roll, heating to 200 ℃, mixing for 1.2h, and then adding polyethylene wax into the mixing roll, mixing for 0.7 h;

d2, averagely dividing the modified carbon black into three parts, putting the three parts of the modified carbon black into a mixing roll at intervals of 35min, mixing for 2.3h in total, adding a coloring auxiliary agent, and mixing for 2.7h to obtain a black master batch; the coloring auxiliary agent is diatomite;

d3, placing the black master batch in an extruder, performing extrusion granulation, and drying to obtain the black master batch.

Examples 4 to 7

The parts by weight of the components of the black master batch in examples 4-7 are shown in Table 2.

TABLE 2 parts by weight of the components of the black master batches in examples 4 to 7

In examples 4 to 7, the modified carbon black was prepared in the same manner as in examples 1 to 3.

In examples 4 to 7, the preparation method of the black masterbatch includes the following steps:

d1, putting the carrier resin into a mixing roll, heating to 200 ℃, mixing for 1.2h, then putting the metal stearate into the mixing roll, and mixing for 0.7 h;

d2, averagely dividing the modified carbon black into three parts, putting the three parts of the modified carbon black into a mixing roll at intervals of 35min, mixing for 2.3h in total, adding a coloring auxiliary agent, and mixing for 2.7h to obtain a black master batch; the coloring auxiliary agent is diatomite;

d3, placing the black master batch in an extruder, performing extrusion granulation, and drying to obtain the black master batch.

Examples 8 to 10

The parts by weight of the components of the black master in examples 8-10 are shown in Table 3.

TABLE 3 parts by weight of the components of the black master batches in examples 8-10

Examples 11 to 13

The parts by weight of the components of the black master batch in examples 11 to 13 are shown in Table 4.

TABLE 4 parts by weight of the components of the black master batches of examples 11 to 13

Examples 14 to 16

The parts by weight of the components of the black master batch in examples 14-16 are shown in Table 5.

TABLE 5 parts by weight of the components of the black master batches of examples 14-16

Examples 17 to 19

The parts by weight of the components of the black master batch in examples 17 to 19 are shown in Table 6.

TABLE 6 parts by weight of the components of the black master batches of examples 17 to 19

In examples 8 to 19, the modified carbon blacks were prepared in the same manner as in examples 1 to 3.

The polyethylene waxes used in examples 8-19 had molecular weights between 3000 and 4000.

In this embodiment 8-19, the preparation method of the black masterbatch includes the following steps:

d1, placing the carrier resin into a mixing roll, heating to 200 ℃, mixing for 1.2h, mixing the polyethylene wax and the metal stearate, and then putting into the mixing roll, mixing for 0.7 h;

d2, averagely dividing the modified carbon black into three parts, putting the three parts of the modified carbon black into a mixing roll at intervals of 35min, mixing for 2.3h in total, adding a coloring auxiliary agent, and mixing for 2.7h to obtain a black master batch; the coloring auxiliary agent is diatomite;

d3, placing the black master batch in an extruder, performing extrusion granulation, and drying to obtain the black master batch.

Examples 20 to 21

Examples 20 to 21 were different from example 19 in the weight parts of the raw materials used for the production of the modified carbon blacks, and the weight parts of the raw materials of the modified carbon blacks used in examples 20 to 21 are shown in Table 7.

TABLE 7 parts by weight of each raw material of examples 20 to 21 of modified carbon blacks

	Example 20	Example 21
			Carbon black	80	90
Polyethanolic acid	10	15
			Active agent	1	3
Coupling agent	1	3

In examples 1 to 21, the carrier resins used were all LLDPE.

Comparative example

Comparative example 1

The difference between the comparative example 1 and the example 19 is the components of the black master batch and the preparation method thereof.

In the comparative example 1, the black master batch comprises the following components in parts by weight: 42 parts of a carrier resin; 82 parts of carbon black; 1.8 parts of polyethylene wax with the molecular weight of 3000-4000; 0.7 part of magnesium stearate; 2.5 parts of a coloring assistant. The coloring auxiliary agent is diatomite.

In comparative example 1, the preparation method of the black master batch comprises the following steps:

d1, placing the carrier resin into a mixing roll, heating to 200 ℃, mixing for 1.2h, mixing the polyethylene wax and the metal stearate, and then putting into the mixing roll, mixing for 0.7 h;

d2, equally dividing the carbon black into three parts, putting the three parts of carbon black into a mixing roll at intervals of 35min, mixing for 2.3h in total, adding diatomite, and mixing for 2.7h to obtain a black master batch;

d3, placing the black master batch in an extruder, performing extrusion granulation, and drying to obtain the black master batch.

Comparative example 2

The difference between the comparative example 2 and the example 19 is the components of the black master batch and the preparation method thereof.

In the comparative example 2, the black master batch comprises the following components in parts by weight: 42 parts of a carrier resin; 82 parts of modified carbon black; 1.8 parts of polyethylene wax with the molecular weight of 3000-4000; 0.7 part of magnesium stearate.

In the comparative example 2, the preparation method of the black master batch comprises the following steps:

d1, placing the carrier resin into a mixing roll, heating to 200 ℃, mixing for 1.2h, mixing the polyethylene wax and the metal stearate, and then putting into the mixing roll, mixing for 0.7 h;

d2, averagely dividing the modified carbon black into three parts, putting the three parts of the modified carbon black into a mixing roll at intervals of 35min, and mixing for 2.3h to obtain a black master batch;

d3, placing the black master batch in an extruder, performing extrusion granulation, and drying to obtain the black master batch.

Comparative example 3

The difference between the comparative example 3 and the example 19 is the components of the black master batch and the preparation method thereof.

In the comparative example 3, the black master batch comprises the following components in parts by weight: 42 parts of a carrier resin; 82 parts of carbon black; 1.8 parts of polyethylene wax with the molecular weight of 3000-4000; 0.7 part of magnesium stearate.

In the comparative example 3, the preparation method of the black master batch comprises the following steps:

d1, placing the carrier resin into a mixing roll, heating to 200 ℃, mixing for 1.2h, mixing the polyethylene wax and the metal stearate, and then putting into the mixing roll, mixing for 0.7 h;

d2, evenly dividing the carbon black into three parts, putting the three parts of the carbon black into a mixing roll at intervals of 35min, and mixing for 2.3h to obtain a black master batch;

d3, placing the black master batch in an extruder, performing extrusion granulation, and drying to obtain the black master batch.

In comparative examples 1-3, the carrier resins used were all LLDPE.

Performance test

Detection method

Using PP as a resin to be colored, the masterbatches of examples 1 to 21 and comparative examples 1 to 3 were each mixed with a PP resin in a proportion of 2%, injection-molded into a color plate, and the dispersibility, blackness and gloss of the color plate were examined. The results are shown in Table 8.

Dispersing performance: and observing whether the surface of the colorimetric plate has flow marks/color marks.

Blackness: and (4) testing by using a color difference meter, and taking the L value, wherein the smaller the L value is, the higher the blackness is.

Gloss: the surface gloss measurements were performed using a gloss meter.

TABLE 8 results of the Performance test of examples 1 to 21 and comparative examples 1 to 3

Combining examples 1-21 and comparative examples 1-3, and table 8, it can be seen that the black masterbatch in this application has higher jetness and gloss when combined with PP resin, i.e. the black masterbatch in this application has better tintability.

Combining examples 1-3, examples 4-7, and examples 8-19, and combining Table 8, it can be seen that the use of polyethylene wax or a metal stearate salt as a dispersant alone affects the dispersibility of the carbon black in the carrier resin, and thus the jetness and gloss of the colored article when the colored resin is colored.

In combination with examples 8-19, and in combination with Table 8, it can be seen that example 19 is the preferred example.

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 (9)

1. The black master batch with high tinting strength is characterized by comprising the following components in parts by weight:

35-49 parts of carrier resin;

75-90 parts of modified carbon black;

1-5 parts of a dispersant;

1-5 parts of a coloring assistant;

the dispersing agent is one or a combination of polyethylene wax and metal stearate;

the metal stearate is one of barium stearate, zinc stearate, calcium stearate and magnesium stearate.

2. The black master batch with high tinting strength as claimed in claim 1, wherein the modified carbon black is prepared from the following raw materials in parts by weight:

80-90 parts of carbon black;

10-15 parts of polyethanol;

1-3 parts of an active agent;

1-3 parts of a coupling agent.

3. The black master batch with high tinting strength as claimed in claim 2, wherein the modified carbon black is prepared by the following preparation steps:

s1, grinding and sieving carbon black to obtain carbon black powder, placing the carbon black powder in a vacuum environment, heating to 85 ℃ and keeping for 0.5h, adding the carbon black powder into absolute ethyl alcohol, and stirring to obtain mixed slurry;

s2, keeping the temperature in S1, adding an active agent into the mixed slurry, stirring at the rotating speed of 500r/min for 10min, sequentially adding the polyethanol and the coupling agent into the mixed slurry, and stirring at the rotating speed of 600r/min for 15min to obtain modified mixed slurry;

and S3, cooling the modified mixed slurry to room temperature under stirring at the rotating speed of 70r/min, carrying out suction filtration on the modified mixed slurry, and drying the suction filtration to obtain the modified carbon black.

4. A black master batch with high tinting strength according to any one of claims 2 or 3, wherein: the active agent is sodium dodecyl benzene sulfonate.

5. A black master batch with high tinting strength according to any one of claims 2 or 3, wherein: the coupling agent is hexamethyldisilazane.

6. The black master batch with high tinting strength of claim 1, wherein: the dispersing agent comprises polyethylene wax and a metal stearate, and the weight part ratio of the polyethylene wax to the metal stearate is 1: (0.3-0.5).

7. The black master batch with high tinting strength according to claim 1 or 6, wherein: the molecular weight of the polyethylene wax is 3000-4000.

8. The black master batch with high tinting strength of claim 1, wherein: the coloring auxiliary agent is diatomite.

9. A preparation method of a black master batch with high tinting strength is characterized by comprising the following steps:

d1, putting the carrier resin into a mixing roll, heating to 200 ℃, mixing for 1-1.5h, and then putting the dispersing agent into the mixing roll, mixing for 0.5-1 h;

d2, averagely dividing the modified carbon black into three parts, putting the three parts of the modified carbon black into a mixing roll at intervals of 30-40min, mixing for 2-2.5h in total, adding a coloring auxiliary agent, and mixing for 2.5-3h to obtain a black master batch;

d3, extruding and granulating the black master batch, and drying to obtain the black master batch.