A cab pigment solid color chip and a method for preparing the same

Abstract

This invention belongs to the field of pigment technology, and specifically discloses a CAB pigment solid color sheet and its preparation method, comprising the following raw materials: pigment, carrier resin, dispersant, stabilizer, and hydroxyl-terminated hyperbranched polyester; the carrier resin comprises a first cellulose acetate butyrate and a second cellulose acetate butyrate in a mass ratio of 1:(0.75~1.5); the molecular weight of the first cellulose acetate butyrate is 16000~20000; and the molecular weight of the second cellulose acetate butyrate is 40000~70000. This invention uses pigment and carrier resin as the matrix, and under the combined action of dispersant, stabilizer, and hydroxyl-terminated hyperbranched polyester, obtains a CAB pigment solid color sheet with excellent stability and tinting strength, effectively improving the storage stability of the CAB pigment solid color sheet and reducing long-term storage color difference. The CAB pigment solid color sheet is suitable for preparing coatings and inks.

Description

Technical Field

[0001] This invention relates to the field of pigment technology, specifically to a CAB pigment solid color sheet and its preparation method. Background Technology

[0002] Pigment solid color chips, also known as pre-dispersed pigment color chips or solid color pastes, are solid homogeneous mixtures made by pre-dispersing pigments in a carrier resin. They are widely used in coloring fields such as coatings, inks, and plastics.

[0003] Compared to traditional powder pigments, solid pigment flakes offer advantages such as good dispersibility, no dust generation, accurate metering, and convenient storage, simplifying downstream production processes and improving production efficiency. As the coatings and inks industries continue to demand higher product performance, they are placing greater emphasis on the storage stability and tinting strength of solid pigment flakes.

[0004] The carbon black pigments used in the prior art are usually unmodified raw carbon black, which has strong hydrophobicity and low polarity, poor compatibility with carrier resin, and is prone to agglomeration during dispersion, resulting in insufficient tinting strength and stability.

[0005] Therefore, this application is submitted. Summary of the Invention

[0006] This invention provides a CAB pigment solid color sheet and its preparation method. The CAB pigment solid color sheet has excellent stability and tinting strength, effectively improves the storage stability of the CAB pigment solid color sheet, and reduces color difference during long-term storage. The CAB pigment solid color sheet is suitable for preparing coatings and inks.

[0007] The present invention solves its technical problem by adopting the following technical solution:

[0008] A CAB pigment solid color chip comprises the following raw materials by weight percentage: 45-65% pigment, 28-42% carrier resin, 4-6% dispersant, 1-2% stabilizer, and 2-5% hydroxyl-terminated hyperbranched polyester.

[0009] The carrier resin comprises a first cellulose acetate butyrate and a second cellulose acetate butyrate in a mass ratio of 1:(0.75~1.5); the first cellulose acetate butyrate has a molecular weight of 16,000~20,000; and the second cellulose acetate butyrate has a molecular weight of 40,000~70,000.

[0010] As an embodiment of this application, the glass transition temperature of the first cellulose acetate butyrate is 85~123℃;

[0011] The glass transition temperature of the second cellulose acetate butyrate is 133~141℃.

[0012] As an embodiment of this application, the molecular weight of the terminal hydroxyl hyperbranched polyester is 2400~2600;

[0013] The hydroxyl-terminated hyperbranched polyester has a hydroxyl value of 500~560 mg KOH / g.

[0014] As an embodiment of this application, the dispersant is sodium carboxymethyl cellulose and rosin in a mass ratio of 1:(0.4~0.8);

[0015] The softening point of the rosin is 125~135℃.

[0016] As an embodiment of this application, the stabilizer is at least one of calcium stearate, zinc stearate, and antioxidant.

[0017] As an embodiment of this application, the pigment is modified carbon black, and the preparation method of the modified carbon black is as follows:

[0018] (1) Add carbon black (also known as carbon black) to the mixture, stir at 65~90℃ for 1~5h, filter, and dry to obtain pretreated carbon black; the mixture includes hydrogen peroxide solution and nitric acid solution;

[0019] (2) The pretreated carbon black is subjected to plasma modification treatment to obtain the precursor;

[0020] (3) Add the precursor, acetic anhydride, butyric anhydride and catalyst to the solvent, stir at 65~90℃ for 1~5h, filter and dry to obtain modified carbon black.

[0021] As an embodiment of this application, the volume ratio of the hydrogen peroxide solution to the nitric acid solution is 1:(0.5~2).

[0022] The mass fraction of the hydrogen peroxide solution is 25-35%;

[0023] The nitric acid solution has a mass fraction of 1-20%.

[0024] As an embodiment of this application, the mass ratio of carbon black to the mixed liquid is 1:(4~20).

[0025] The mass ratio of the precursor, acetic anhydride, butyric anhydride, catalyst, and solvent is 1:(0.05~0.08):(0.05~0.08):(0.02~0.1):(2~10).

[0026] As an embodiment of this application, the plasma modification treatment has a voltage of 220V, a power of 600~1000W, and a time of 2~10min.

[0027] This application also provides a method for preparing CAB pigment solid color sheets, comprising the following steps: mixing the raw materials evenly, kneading, grinding, drawing into sheet shape, and crushing to obtain CAB pigment solid color sheets.

[0028] The beneficial effects of this invention are as follows: Using pigments and carrier resins as the matrix, and with the combined action of dispersants, stabilizers, and terminal hydroxyl hyperbranched polyesters, this invention yields CAB pigment solid color sheets with excellent stability and tinting strength. This effectively improves the storage stability of the CAB pigment solid color sheets and reduces color difference during long-term storage. The CAB pigment solid color sheets are suitable for preparing coatings and inks. Detailed Implementation

[0029] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0030] In this invention, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions that include the listed features.

[0031] In this invention, numerical ranges are involved. Unless otherwise specified, the numerical ranges are considered continuous and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe features or characteristics, the ranges may be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are included.

[0032] In this invention, there are no particular limitations on the specific dispersion and stirring methods.

[0033] Unless otherwise specified, all reagents or instruments used in this invention are commercially available conventional products. Unless otherwise specified, the raw materials used in each comparative example and the parallel experiments of each embodiment are the same commercially available products.

[0034] The raw materials used in the examples and comparative examples are as follows:

[0035] Cellulose acetate butyrate-1: Molecular weight 20000, glass transition temperature 123℃, Eastman, CAB-381-0.1.

[0036] Cellulose acetate butyrate-2: Molecular weight 16000, glass transition temperature 85℃, Eastman, CAB-551-0.01.

[0037] Cellulose acetate butyrate-3: molecular weight 40,000, glass transition temperature 133°C, Eastman, CAB-381-2.

[0038] Cellulose acetate butyrate-4: Molecular weight 70,000, glass transition temperature 141°C, Eastman, CAB-381-20.

[0039] Cellulose acetate butyrate-5: molecular weight 30,000, glass transition temperature 130°C, Eastman, CAB-381-0.5.

[0040] Hydroxyl-terminated hyperbranched polyester-1: molecular weight 2400, hydroxyl value 560 mg KOH / g, Wuhan hyperbranched, H103.

[0041] Hydroxyl-terminated hyperbranched polyester-2: molecular weight 2600, hydroxyl value 500 mg KOH / g, Wuhan hyperbranching, H2O3.

[0042] Hydroxyl-terminated hyperbranched polyester-3: molecular weight 500, hydroxyl value 670 mg KOH / g, Wuhan hyperbranching, H101.

[0043] Hydroxyl-terminated hyperbranched polyester-4: molecular weight 5500, hydroxyl value 240 mg KOH / g, Wuhan hyperbranching, H3O3.

[0044] Rosin; softening point is 125~135℃, Kemaolin Chemical, type 401.

[0045] Carbon black: Tianjin Jindadi, S666.

[0046] This application provides a CAB pigment solid color sheet, comprising the following raw materials by mass percentage: 45-65% pigment, 28-42% carrier resin, 4-6% dispersant, 1-2% stabilizer, and 2-5% hydroxyl-terminated hyperbranched polyester.

[0047] The carrier resin comprises a first cellulose acetate butyrate and a second cellulose acetate butyrate in a mass ratio of 1:(0.75~1.5); the molecular weight of the first cellulose acetate butyrate is 16,000~20,000, for example, it can be 16,000, 16,500, 17,000, 17,500, 18,000, 18,500, 19,000, 19,500, 20,000 or any two of these values; the molecular weight of the second cellulose acetate butyrate is 40,000~70,000, for example, it can be 40,000, 45,000, 50,000, 55,000, 60,000, 65,000, 70,000 or any two of these values.

[0048] This invention creatively combines the above-mentioned raw materials, using pigments and carrier resins as the matrix, and with the combined action of dispersants, stabilizers, and terminal hydroxyl hyperbranched polyesters, obtains CAB pigment solid color sheets with excellent stability and tinting strength. This effectively improves the storage stability of the CAB pigment solid color sheets and reduces color difference during long-term storage. The CAB pigment solid color sheets are suitable for preparing coatings and inks.

[0049] This application uses cellulose acetate butyrate and cellulose acetate butyrate in a mass ratio of 1:(0.75~1.5) as carrier resins, and controls the molecular weight of both. The first cellulose acetate butyrate mainly serves to wet and initially disperse the pigment. Its low molecular weight provides good flowability, which is beneficial for quickly wetting the pigment surface during the mixing process and reducing pigment agglomeration. The second cellulose acetate butyrate provides mechanical support and long-term stability. Its high molecular weight gives the color flakes good mechanical strength and morphological stability, preventing deformation or breakage during storage and use. The two work together to achieve wettability and excellent stability, ensuring that the pigment is fully dispersed and that the color flakes have sufficient mechanical strength and processing performance.

[0050] In some embodiments, the glass transition temperature of the first cellulose acetate butyrate is 85~123°C, for example, it can be 85°C, 86°C, 88°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 123°C or any two of these values.

[0051] In some embodiments, the glass transition temperature of the second cellulose acetate butyrate is 133~141°C, for example, it can be 133°C, 134°C, 135°C, 136°C, 138°C, 140°C, 141°C or any two of these values.

[0052] In some embodiments, the molecular weight of the terminal hydroxyl hyperbranched polyester is 2400 to 2600, for example, it can be 2400, 2420, 2450, 2480, 2500, 2520, 2550, 2580, 2600 or any two of these values.

[0053] In some embodiments, the hydroxyl-terminated hyperbranched polyester has a hydroxyl value of 500-560 mg KOH / g, for example, 500 mg KOH / g, 510 mg KOH / g, 520 mg KOH / g, 540 mg KOH / g, 550 mg KOH / g, 560 mg KOH / g, or any two of these values. The hydroxyl-terminated hyperbranched polyester exhibits excellent lubrication properties, effectively lubricating the interfaces between components. Furthermore, it possesses a dendritic three-dimensional structure with numerous hydroxyl functional groups at the molecular ends. These hydroxyl groups can form multi-point hydrogen bonds with polar groups on the pigment surface, while the three-dimensional dendritic structure provides steric hindrance, effectively preventing pigment particle aggregation and sedimentation during storage, significantly improving the long-term storage stability of the color chips, enhancing processing performance, and improving tinting strength.

[0054] In some embodiments, the dispersant is sodium carboxymethyl cellulose and rosin in a mass ratio of 1:(0.4~0.8);

[0055] The softening point of the rosin is 125~135℃, for example, it can be 125℃, 126℃, 127℃, 128℃, 130℃, 132℃, 134℃, 135℃ or any two of these values.

[0056] By using sodium carboxymethyl cellulose and rosin in a mass ratio of 1:(0.4~0.8) as a dispersion system, the dispersant provides charge stabilization by forming electrostatic adsorption between the carboxyl groups and the pigment surface. Simultaneously, the hydrophobic resin acid structure coats the pigment surface, providing steric hindrance protection and effectively improving the pigment dispersion effect.

[0057] In some embodiments, the stabilizer is at least one of calcium stearate, zinc stearate, and antioxidant, which effectively prevents aging phenomena such as oxidation and degradation of the color chips during storage and use, and improves the weather resistance and storage stability of the color chips.

[0058] In some embodiments, the antioxidant includes at least one of thioester antioxidants, hindered phenolic antioxidants, hydroxylamine antioxidants, phosphite antioxidants, and phosphate antioxidants.

[0059] In some embodiments, the pigment is modified carbon black, and the method for preparing the modified carbon black is as follows:

[0060] (1) Add carbon black to the mixture, stir at 65~90℃ for 1~5h, filter, and dry to obtain pretreated carbon black; the mixture includes hydrogen peroxide solution and nitric acid solution;

[0061] (2) The pretreated carbon black is subjected to plasma modification treatment to obtain the precursor;

[0062] (3) Add the precursor, acetic anhydride, butyric anhydride and catalyst to the solvent, stir at 65~90℃ for 1~5h, filter and dry to obtain modified carbon black.

[0063] This application improves the surface polarity and activity of carbon black by first treating it with hydrogen peroxide and nitric acid solutions, followed by plasma modification. This process introduces hydroxyl and carboxyl functional groups, and then grafts acetyl and butyryl groups onto the carbon black surface. This makes the carbon black surface structure match the molecular structure of the CAB carrier resin, significantly improving their compatibility and dispersion.

[0064] In some embodiments, the volume ratio of the hydrogen peroxide solution to the nitric acid solution is 1:(0.5~2).

[0065] In some embodiments, the hydrogen peroxide solution has a mass fraction of 25-35%.

[0066] In some embodiments, the nitric acid solution has a mass fraction of 1-20%.

[0067] In some embodiments, the mass ratio of carbon black to the mixture is 1:(4~20).

[0068] In some embodiments, the mass ratio of the precursor, acetic anhydride, butyric anhydride, catalyst, and solvent is 1:(0.05~0.08):(0.05~0.08):(0.02~0.1):(2~10).

[0069] In some embodiments, the plasma modification treatment is performed at a voltage of 220V, a power of 600~1000W, and a time of 2~10min.

[0070] In some embodiments, the catalyst is p-benzenesulfonic acid.

[0071] One embodiment of this application provides a method for preparing CAB pigment solid color sheets, comprising the following steps: mixing each raw material evenly, kneading, grinding, drawing into sheet shape, pulverizing, and obtaining CAB pigment solid color sheets.

[0072] The present application is further illustrated below with specific embodiments:

[0073] Example 1

[0074] A CAB pigment solid color chip comprises the following raw materials in weight percentage: 54.5% modified carbon black, 35% carrier resin, 5% dispersant, 1.5% calcium stearate, and 4% hydroxyl-terminated hyperbranched polyester-1.

[0075] The carrier resin comprises cellulose acetate butyrate-1 and cellulose acetate butyrate-3 in a mass ratio of 1:1.

[0076] The dispersant is sodium carboxymethyl cellulose and rosin in a mass ratio of 1:0.5.

[0077] The modified carbon black is prepared by:

[0078] (1) Mix a 30% hydrogen peroxide solution and a 5% nitric acid solution at a volume ratio of 1:1 to obtain a mixed solution;

[0079] Carbon black was added to the mixture and stirred at 100 rpm for 2 hours at 75°C. The mixture was then filtered and dried to obtain pretreated carbon black. The mass ratio of carbon black to the mixture was 1:5.

[0080] (2) The pretreated carbon black was placed in a plasma reaction vessel and treated for 8 minutes at a voltage of 220V, ambient temperature and pressure (one atmosphere) and a power of 800W to obtain the precursor.

[0081] (3) The precursor, acetic anhydride, butyric anhydride, and catalyst were added to methyl ethyl ketone (MEK). Under nitrogen protection, the mixture was stirred at 100 rpm for 2 hours at 80°C. After filtration, the mixture was dried to constant weight to obtain modified carbon black. The mass ratio of the precursor, acetic anhydride, butyric anhydride, catalyst, and solvent was 1:0.06:0.06:0.03:5.

[0082] The method for preparing CAB pigment solid color chips includes the following steps: mixing all raw materials evenly, kneading at 135℃ for 1 hour, grinding with a three-roll mill to a fineness ≤10μm, drawing into sheet form, pulverizing, and obtaining CAB pigment solid color chips.

[0083] Example 2

[0084] A CAB pigment solid color chip comprises the following raw materials by weight percentage: 45% modified carbon black, 42% carrier resin, 6% dispersant, 2% calcium stearate, and 5% hydroxyl-terminated hyperbranched polyester-1.

[0085] The carrier resin comprises cellulose acetate butyrate-1 and cellulose acetate butyrate-3 in a mass ratio of 1:1.

[0086] The dispersant is sodium carboxymethyl cellulose and rosin in a mass ratio of 1:1.5.

[0087] The modified carbon black is prepared by:

[0088] (1) Mix a 30% hydrogen peroxide solution and a 5% nitric acid solution at a volume ratio of 1:1 to obtain a mixed solution;

[0089] Carbon black was added to the mixture and stirred at 100 rpm for 2 hours at 75°C. The mixture was then filtered and dried to obtain pretreated carbon black. The mass ratio of carbon black to the mixture was 1:5.

[0090] (2) The pretreated carbon black was placed in a plasma reaction vessel and treated for 8 minutes at a voltage of 220V, ambient temperature and pressure (one atmosphere) and a power of 800W to obtain the precursor.

[0091] (3) The precursor, acetic anhydride, butyric anhydride, and catalyst were added to methyl ethyl ketone (MEK). Under nitrogen protection, the mixture was stirred at 100 rpm for 2 hours at 80°C. After filtration, the mixture was dried to constant weight to obtain modified carbon black. The mass ratio of the precursor, acetic anhydride, butyric anhydride, catalyst, and solvent was 1:0.06:0.06:0.03:5.

[0092] The method for preparing CAB pigment solid color chips includes the following steps: mixing all raw materials evenly, kneading at 135℃ for 1 hour, grinding with a three-roll mill to a fineness ≤10μm, drawing into sheet form, pulverizing, and obtaining CAB pigment solid color chips.

[0093] Example 3

[0094] A CAB pigment solid color chip comprises the following raw materials by weight percentage: 65% modified carbon black, 28% carrier resin, 4% dispersant, 1% calcium stearate, and 2% hydroxyl-terminated hyperbranched polyester-1.

[0095] The carrier resin comprises cellulose acetate butyrate-1 and cellulose acetate butyrate-3 in a mass ratio of 1:1.

[0096] The dispersant is sodium carboxymethyl cellulose and rosin in a mass ratio of 1:0.75.

[0097] The modified carbon black is prepared by:

[0098] (1) Mix a 30% hydrogen peroxide solution and a 5% nitric acid solution at a volume ratio of 1:1 to obtain a mixed solution;

[0099] Carbon black was added to the mixture and stirred at 100 rpm for 2 hours at 75°C. The mixture was then filtered and dried to obtain pretreated carbon black. The mass ratio of carbon black to the mixture was 1:5.

[0100] (2) The pretreated carbon black was placed in a plasma reaction vessel and treated for 8 minutes at a voltage of 220V, ambient temperature and pressure (one atmosphere) and a power of 800W to obtain the precursor.

[0101] (3) The precursor, acetic anhydride, butyric anhydride, and catalyst were added to methyl ethyl ketone (MEK). Under nitrogen protection, the mixture was stirred at 100 rpm for 2 hours at 80°C. After filtration, the mixture was dried to constant weight to obtain modified carbon black. The mass ratio of the precursor, acetic anhydride, butyric anhydride, catalyst, and solvent was 1:0.06:0.06:0.03:5.

[0102] The method for preparing CAB pigment solid color chips includes the following steps: mixing all raw materials evenly, kneading at 135℃ for 1 hour, grinding with a three-roll mill to a fineness ≤10μm, drawing into sheet form, pulverizing, and obtaining CAB pigment solid color chips.

[0103] Example 4

[0104] A CAB pigment solid color chip comprises the following raw materials in weight percentage: 54.5% modified carbon black, 35% carrier resin, 5% dispersant, 1.5% calcium stearate, and 4% hydroxyl-terminated hyperbranched polyester-1.

[0105] The carrier resin comprises cellulose acetate butyrate-2 and cellulose acetate butyrate-4 in a mass ratio of 1:1.

[0106] The dispersant is sodium carboxymethyl cellulose and rosin in a mass ratio of 1:0.5.

[0107] The modified carbon black is prepared by:

[0108] (1) Mix a 30% hydrogen peroxide solution and a 5% nitric acid solution at a volume ratio of 1:1 to obtain a mixed solution;

[0109] Carbon black was added to the mixture and stirred at 100 rpm for 2 hours at 75°C. The mixture was then filtered and dried to obtain pretreated carbon black. The mass ratio of carbon black to the mixture was 1:5.

[0110] (2) The pretreated carbon black was placed in a plasma reaction vessel and treated for 8 minutes at a voltage of 220V, ambient temperature and pressure (one atmosphere) and a power of 800W to obtain the precursor.

[0111] (3) The precursor, acetic anhydride, butyric anhydride, and catalyst were added to methyl ethyl ketone (MEK). Under nitrogen protection, the mixture was stirred at 100 rpm for 2 hours at 80°C. After filtration, the mixture was dried to constant weight to obtain modified carbon black. The mass ratio of the precursor, acetic anhydride, butyric anhydride, catalyst, and solvent was 1:0.06:0.06:0.03:5.

[0112] The method for preparing CAB pigment solid color chips includes the following steps: mixing all raw materials evenly, kneading at 135℃ for 1 hour, grinding with a three-roll mill to a fineness ≤10μm, drawing into sheet form, pulverizing, and obtaining CAB pigment solid color chips.

[0113] Example 5

[0114] Example 5 differs from Example 1 in that an equal amount of end-hydroxyl hyperbranched polyester-2 is used to replace end-hydroxyl hyperbranched polyester-1.

[0115] A CAB pigment solid color chip comprises the following raw materials in weight percentage: 54.5% modified carbon black, 35% carrier resin, 5% dispersant, 1.5% calcium stearate, and 4% hydroxyl-terminated hyperbranched polyester-2.

[0116] Example 6

[0117] Example 6 differs from Example 1 in that an equal amount of end-hydroxyl hyperbranched polyester-3 is used to replace end-hydroxyl hyperbranched polyester-1.

[0118] A CAB pigment solid color chip comprises the following raw materials in weight percentage: 54.5% modified carbon black, 35% carrier resin, 5% dispersant, 1.5% calcium stearate, and 4% hydroxyl-terminated hyperbranched polyester-3.

[0119] Example 7

[0120] Example 7 differs from Example 1 in that an equal amount of end-hydroxyl hyperbranched polyester-3 is used to replace end-hydroxyl hyperbranched polyester-1.

[0121] A CAB pigment solid color chip comprises the following raw materials in weight percentage: 54.5% modified carbon black, 35% carrier resin, 5% dispersant, 1.5% calcium stearate, and 4% hydroxyl-terminated hyperbranched polyester-4.

[0122] Comparative Example 1

[0123] The difference between Comparative Example 1 and Example 1 is that Comparative Example 1 is a single cellulose acetate butyrate-1, while all other aspects are the same.

[0124] A CAB pigment solid color chip comprises the following raw materials in weight percentage: 54.5% modified carbon black, 35% carrier resin, 5% dispersant, 1.5% calcium stearate, and 4% hydroxyl-terminated hyperbranched polyester-1.

[0125] The carrier resin is cellulose acetate butyrate-1.

[0126] Comparative Example 2

[0127] The difference between Comparative Example 2 and Example 1 is that Comparative Example 2 is a single cellulose acetate butyrate-3, but everything else is the same.

[0128] A CAB pigment solid color chip comprises the following raw materials in weight percentage: 54.5% modified carbon black, 35% carrier resin, 5% dispersant, 1.5% calcium stearate, and 4% hydroxyl-terminated hyperbranched polyester-1.

[0129] The carrier resin is cellulose acetate butyrate-3.

[0130] Comparative Example 3

[0131] The difference between Comparative Example 3 and Example 1 is that Comparative Example 3 is a single cellulose acetate butyrate-5, but everything else is the same.

[0132] A CAB pigment solid color chip comprises the following raw materials in weight percentage: 54.5% modified carbon black, 35% carrier resin, 5% dispersant, 1.5% calcium stearate, and 4% hydroxyl-terminated hyperbranched polyester-1.

[0133] The carrier resin is cellulose acetate butyrate-5.

[0134] Comparative Example 4

[0135] The difference between Comparative Example 4 and Example 1 is that Comparative Example 4 uses an equal amount of carbon black to replace the modified carbon black, while everything else is the same.

[0136] A CAB pigment solid color chip comprises the following raw materials in weight percentage: 54.5% carbon black, 35% carrier resin, 5% dispersant, 1.5% calcium stearate, and 4% hydroxyl-terminated hyperbranched polyester-1.

[0137] Comparative Example 5

[0138] The difference between Comparative Example 5 and Example 1 is that the preparation method of the modified carbon black is different, but everything else is the same.

[0139] The preparation method of the modified carbon black described in this comparative example is as follows:

[0140] (1) Mix a 30% hydrogen peroxide solution and a 5% nitric acid solution at a volume ratio of 1:1 to obtain a mixed solution;

[0141] Carbon black was added to the mixture and stirred at 100 rpm for 2 hours at 75°C. The mixture was then filtered and dried to obtain pretreated carbon black. The mass ratio of carbon black to the mixture was 1:5.

[0142] (2) The pretreated carbon black was placed in a plasma reaction vessel and treated for 8 minutes at a voltage of 220V, ambient temperature and pressure (one atmosphere) and a power of 800W to obtain modified carbon black.

[0143] Comparative Example 6

[0144] The difference between Comparative Example 6 and Example 1 is that hydroxyl-terminated hyperbranched polyester-1 is not added, but everything else is the same.

[0145] A CAB pigment solid color chip comprises the following raw materials in weight percentage: 58.5% modified carbon black, 35% carrier resin, 5% dispersant, and 1.5% calcium stearate.

[0146] Test case

[0147] 1. Dissolve the color chips in a solvent (mass ratio 1:5) and store them in a constant temperature and humidity chamber at 40℃ and 75% relative humidity for 6 months. Then, use a Konica Minolta CR-400 colorimeter to test the color difference ΔE before and after storage.

[0148] 2. Dissolve the color chips in a solvent (mass ratio 1:5) and store them in a constant temperature and humidity chamber at 40℃ and 75% relative humidity for 6 months. Test the change in relative tinting strength immediately after preparation (before storage) and after 6 months of storage. Use each color paste immediately after preparation (before storage) as a standard color paste with 100% tinting strength and test the relative tinting strength after 6 months of storage.

[0149] Table 1

[0150]

[0151] As can be seen from Table 1, the CAB pigment solid color chips described in this application have excellent stability and tinting strength, effectively improving the storage stability of the CAB pigment solid color chips and reducing color difference during long-term storage. The CAB pigment solid color chips are suitable for preparing coatings and inks.

[0152] Comparing Example 1 with Comparative Examples 1-3, it can be seen that by using cellulose acetate butyrate and cellulose acetate butyrate in a mass ratio of 1:(0.75-1.5) as carrier resins, this application effectively improves stability and coloring power, and significantly improves color difference and coloring power.

[0153] As can be seen from the comparison between Example 1 and Comparative Examples 4-5, the modified carbon black described in this application can significantly improve color difference and tinting strength.

[0154] Comparing Example 1 and Comparative Example 6, it can be seen that the present application significantly improves color difference and coloring power by adding terminal hydroxyl hyperbranched polyester.

[0155] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present invention and not to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A CAB pigment solid color chip, characterized in that, The preparation raw materials include the following percentages by weight: 45-65% pigment, 28-42% carrier resin, 4-6% dispersant, 1-2% stabilizer, and 2-5% hydroxyl-terminated hyperbranched polyester. The carrier resin comprises a first cellulose acetate butyrate and a second cellulose acetate butyrate in a mass ratio of 1:(0.75~1.5); the first cellulose acetate butyrate has a molecular weight of 16,000~20,000; and the second cellulose acetate butyrate has a molecular weight of 40,000~70,000.

2. The CAB pigment solid color chip according to claim 1, characterized in that, The glass transition temperature of the first cellulose acetate butyrate is 85~123℃; The glass transition temperature of the second cellulose acetate butyrate is 133~141℃.

3. The CAB pigment solid color chip according to claim 1, characterized in that, The molecular weight of the terminal hydroxyl hyperbranched polyester is 2400~2600; The hydroxyl-terminated hyperbranched polyester has a hydroxyl value of 500~560 mg KOH / g.

4. The CAB pigment solid color chip according to claim 1, characterized in that, The dispersant is sodium carboxymethyl cellulose and rosin in a mass ratio of 1:(0.4~0.8); The softening point of the rosin is 125~135℃.

5. The CAB pigment solid color chip according to claim 1, characterized in that, The stabilizer is at least one of calcium stearate, zinc stearate, and antioxidant.

6. The CAB pigment solid color chip according to claim 1, characterized in that, The pigment is modified carbon black, and the preparation method of the modified carbon black is as follows: (1) Add carbon black to the mixture, stir at 65~90℃ for 1~5h, filter, and dry to obtain pretreated carbon black; the mixture includes hydrogen peroxide solution and nitric acid solution; (2) The pretreated carbon black is subjected to plasma modification treatment to obtain the precursor; (3) Add the precursor, acetic anhydride, butyric anhydride and catalyst to the solvent, stir at 65~90℃ for 1~5h, filter and dry to obtain modified carbon black.

7. The CAB pigment solid color chip according to claim 6, characterized in that, The volume ratio of the hydrogen peroxide solution to the nitric acid solution is 1:(0.5~2). The mass fraction of the hydrogen peroxide solution is 25-35%; The nitric acid solution has a mass fraction of 1-20%.

8. The CAB pigment solid color chip according to claim 6, characterized in that, The mass ratio of carbon black to the mixed liquid is 1:(4~20). The mass ratio of the precursor, acetic anhydride, butyric anhydride, catalyst, and solvent is 1:(0.05~0.08):(0.05~0.08):(0.02~0.01):(2~10).

9. The CAB pigment solid color chip according to claim 6, characterized in that, The plasma modification treatment is performed at a voltage of 220V, a power of 600~1000W, and a time of 2~10min.

10. The method for preparing CAB pigment solid color plates according to any one of claims 1 to 9, characterized in that, The process includes the following steps: mixing all raw materials evenly, kneading, grinding, drawing into sheets, and crushing to obtain CAB pigment solid color sheets.

Images