TWI790535B - Dispersion and ink - Google Patents

Abstract

A dispersion includes 100 parts by weight of powder, 1 to 80 parts by weight of dispersant, and 80 to 900 parts by weight of polar solvent. The dispersant is a diblock copolymer having a chemical structure of:

, wherein Ini and Ini’ are residue groups of an initiator of polymerization, each of R ¹is independently H or methyl group, R ²is

,

, or

; B is alkali metal or N(R ³) ₄, and each of R ³is independently H, C _1-4alkyl group, or C _1-4hydroxyalkyl group; m and n have a ratio of 3:1 to 1:2, and x is 0.7 to 1. The dispersant has a weight average molecular weight (Mw) of 1500 to 4500.

Description

Dispersions and Inks

This disclosure relates to dispersions and inks, and more particularly to the dispersants employed therein.

Micro-powder dispersion technology is widely used in digital inkjet printing inks and coatings. Dispersants used to disperse organic/inorganic micropowders are in great demand in the market, especially polymer dispersants used in aqueous dispersions that meet environmental protection requirements. Water-based dispersions can be combined with resins to form water-based inks. The advantages include safety, non-toxicity, harmlessness, and almost no volatile organic gases. Therefore, the development of dispersants is extremely important. Dispersants play a key role in the technology of stabilizing the dispersion of conductive carbon black and achieving high conductivity. In order to achieve the above purpose, it is urgent to design the structure of the water-based dispersant for the micropowder.

，其中Ini與Ini’係聚合反應所用之起始劑的殘基；每一R ¹各自為H或甲基；R ²係

、

、或

；B係鹼金族金屬或N(R ³) ₄，且每一R ³各自為H、C _1-4的烷基、或C _1-4的烷基醇，m與n的比例為3:1至1:2；以及x係0.7至1，其中該分散劑的重量平均分子量(Mw)為1500至4500。 The dispersion provided by an embodiment of the present disclosure includes: 100 parts by weight of powder; 1 to 80 parts by weight of a dispersant; and 80 to 900 parts by weight of a polar solvent, wherein the dispersant is a double block copolymer, which The chemical structure is:

, wherein Ini and Ini' are the residues of the initiator used in the polymerization reaction; each R ¹ is independently H or methyl; R ² is

,

,or

; B is an alkali metal or N(R ³ ) ₄ , and each R ³ is independently H, C _1-4 alkyl, or C _1-4 alkyl alcohol, and the ratio of m to n is 3: 1 to 1:2; and x is 0.7 to 1, wherein the weight average molecular weight (Mw) of the dispersant is 1500 to 4500.

，其中Ini與Ini’係聚合反應所用之起始劑的殘基；每一R ¹各自為H或甲基；R ²係

、

、或

；B係鹼金族金屬或N(R ³) ₄，且每一R ³各自為H、C _1-4的烷基、或C _1-4的烷基醇，m與n的比例為3:1至1:2；x係0.7至1，其中分散劑的重量平均分子量(Mw)為1500至4500。 The ink provided in an embodiment of the present disclosure includes: a dispersion liquid and a resin, and the weight ratio of the dispersion liquid to the resin is 100:10 to 100:120, wherein the dispersion liquid includes: 100 parts by weight of powder; 1 to 80 parts by weight A dispersant; and a polar solvent of 80 to 900 parts by weight, wherein the dispersant is a double block copolymer, and its chemical structure is:

, wherein Ini and Ini' are the residues of the initiator used in the polymerization reaction; each R ¹ is independently H or methyl; R ² is

,

,or

; B is an alkali metal or N(R ³ ) ₄ , and each R ³ is independently H, C _1-4 alkyl, or C _1-4 alkyl alcohol, and the ratio of m to n is 3: 1 to 1:2; x is 0.7 to 1, and the weight average molecular weight (Mw) of the dispersant is 1500 to 4500.

The dispersion liquid provided by an embodiment of the present disclosure includes: 100 parts by weight of powder; 1 to 80 parts by weight of dispersant; and 80 to 900 parts by weight of polar solvent. If the proportion of dispersant is too low, the powder cannot be effectively dispersed. If the proportion of dispersant is too high, the cost will be increased if the powder cannot be further dispersed. In addition, if the dispersion is used in ink later, too high a proportion of dispersant will affect the coating properties (such as conductivity) formed by the ink. If the proportion of the polar solvent is too low, the powder is easy to precipitate. If the proportion of polar solvent is too high, it will reduce the practicality of the product.

。Ini與Ini’係聚合反應所用之起始劑的殘基。舉例來說，若採用原子轉移自由基聚合(ATRP)的聚合機制，則Ini可為C ₁-C ₁₂脂肪族烷基、C ₆-C ₁₂芳香族烷基、或一般市售的ATRP起始劑的殘基，而Ini’可為Cl或Br。若採用其他聚合機制如陽離子型聚合或陰離子型聚合，則Ini與Ini’可為對應的殘基。每一R ¹各自為H或甲基；R ²係

、

、或

；B係鹼金族金屬或N(R ³) ₄，且每一R ³各自為H、C _1-4的烷基、或C _1-4的烷基醇。m與n的比例為3:1至1:2。若m的比例過低且n的比例過高，則分散劑不易溶於水。若m的比例過高且n的比例過低，則分散劑不易吸附粉體。x係0.7至1。舉例來說，可中和大部分的酸基(x=0.7)，或將所有的酸基中和(x=1)。上述分散劑的重量平均分子量(簡稱重均分子量)為1500至4500。若分散劑的重均分子量過低，則分散劑不易吸附粉體。若分散劑的重均分子量過高，則無法有效分散粉體。若分散劑為無規共聚物，則無法有效分散粉體。 The aforementioned dispersant is a double-block copolymer, and its chemical structure is:

. Ini and Ini' are the residues of the initiator used in the polymerization reaction. For example, if the polymerization mechanism of atom transfer radical polymerization (ATRP) is adopted, Ini can be a C ₁ -C ₁₂ aliphatic alkyl group, a C ₆ -C ₁₂ aromatic alkyl group, or a general commercially available ATRP initiator Residue of the agent, while Ini' can be Cl or Br. If other polymerization mechanisms such as cationic polymerization or anionic polymerization are used, Ini and Ini' can be the corresponding residues. Each R ¹ is independently H or methyl; R ² is

,

,or

; B is an alkali metal or N(R ³ ) ₄ , and each R ³ is independently H, C _1-4 alkyl, or C _1-4 alkyl alcohol. The ratio of m to n is 3:1 to 1:2. If the ratio of m is too low and the ratio of n is too high, the dispersant is not easily soluble in water. If the ratio of m is too high and the ratio of n is too low, the dispersant will not easily adsorb the powder. x ranges from 0.7 to 1. For example, most of the acid groups can be neutralized (x=0.7), or all acid groups can be neutralized (x=1). The weight average molecular weight of the above-mentioned dispersant (abbreviated as weight average molecular weight) is 1500 to 4500. If the weight-average molecular weight of the dispersant is too low, the dispersant will not easily adsorb powder. If the weight average molecular weight of the dispersant is too high, the powder cannot be effectively dispersed. If the dispersant is a random copolymer, the powder cannot be effectively dispersed.

In one embodiment, the synthesis method of the above-mentioned dispersant is as follows. It should be noted that the following methods are only used as examples rather than limiting the present disclosure. Those skilled in the art can synthesize the above-mentioned dispersants by using available equipment and medicines.

First, you can take t-butyl acrylate ( tBMA ) and an initiator (Initiator, such as p-methylphenylsulfonyl chloride) to form a polymer, as shown below. In the following formula, Ini may be CH ₃ —Ph—SO ₂ —, and Ini′ may be —Cl.

Then another acrylate after deoxygenation, such as isobutyl methacrylate ( iBMA ), is added to the above polymer and reacted to form a double block copolymer. It can be understood that since the two monomer systems of tBMA and iBMA react sequentially rather than simultaneously, the formed copolymer is a double block copolymer rather than a random copolymer. The above polymerization mechanism is ATRP, and its reaction is as follows:

The block corresponding to m is then deprotected with an acid, and the deprotected copolymer is optionally neutralized, as follows:

In the above reaction, the definitions of Ini, Ini′, R ¹ , R ² , m, n, x, and B are the same as those described above, and will not be repeated here.

In some embodiments, the aforementioned powders include carbon materials, pigments, metals, metal oxides, or combinations thereof. For example, the carbon material may include carbon black, graphite, graphene, carbon nanotubes, fullerene, or other suitable carbon materials, or combinations thereof. Pigments can be yellow pigments such as cadmium yellow (PY35, C.I.77205, CAS# 12237-67-1), titanium nickel yellow (PY53, C.I.77788, CAS#8007-18-9), zirconium yellow (PY159, C.I.77997, CAS#68187-15-5), Chrome Titanium Yellow (PY162, C.I.77896, CAS#68611-42-7; PY163, C.I.77897, CAS# 68186-92-5), or Bismuth Yellow (PY184, C.I.771740, CAS #14059-33-7). The pigment can be magenta pigment such as iron red (PR101, C.I.77491, CAS# 1317-60-8), cadmium red (PR108, C.I.77202, CAS#58339-34-7), lead chrome red (PR104, C.I.77605, CAS#12656-85-8; PR105, C.I.77578, CAS#1314-41-6), or Iron Zirconium Red (PR232, C.I.77996, CAS#68412-79-3). The pigments may be cyan pigments such as cobalt blue (PB28, C.I.77364, CAS# 68187-40-6) and cobalt chrome blue (PB36, C.I.77343, CAS#68187-11-1). Pigments can be black pigments such as manganese black (PBK26, C.I.77494, CAS# 68186-94-7; PBK33, C.I.77537, CAS #75864-23-2), cobalt iron chrome black (PBK27, C.I.77502, CAS#68186 -97-0), Copper Chrome Black (PBK28, C.I.77428, CAS#68186-91-4), Chrome Iron Black (PBK30, C.I.77504, CAS#71631-15-7), or Titanium Black (PBK35, C.I.77890 , CAS# 70248-09-8). Pigments can be white inorganic pigments such as titanium white (PW6, C.I.77891, CAS#13463-67-7), zirconium white (PW12, C.I.77990, CAS#1314-23-4), or zinc white (PW4, C.I.77947, CAS#1314-13-2). The pigments may be orange pigments such as Cadmium Orange (PO20, C.I.77199, CAS#12656-57-4) and Orange Chrome Yellow (PO21, C.I.77601, CAS#1344-38-3). Pigments can be green pigments such as chrome green (PG17, C.I.77288, CAS#1308-38-9), cobalt green (PG19, C.I.77335, CAS#8011-87-8), cobalt chrome green (PG26, C.I.77344, CAS #68187-49-5), or Cobalt Titanium Green (PG50, C.I.77377, CAS#68186-85-6). The pigment can also be other suitable pigments, not limited to the above-mentioned pigments.

In some embodiments, the average particle diameter of the powder may be 100 nm to 550 nm, such as 100 nm to 350 nm. Generally speaking, the smaller the average particle size of the pigment powder, the better. In addition, the above dispersion was stored at room temperature for more than half a year, and the particle size of the powder can still be maintained without significant change. It is obvious that the stability of the above dispersion is excellent. In some embodiments, the aforementioned polar solvents include water, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, diethylene glycol butyl ether acetate, ethylene glycol butyl ether, tetra Ethylene glycol dimethyl ether, or a combination of the above.

The ink provided in an embodiment of the present disclosure includes: the above-mentioned dispersion liquid and resin, and the weight ratio of the dispersion liquid to the resin is 100:10 to 100:120. The resin may include polypropylene resin, polyurethane resin, or a combination thereof. If the ratio of the resin is too low, powder adhesion will deteriorate. If the proportion of resin is too high, the properties of powder are not easy to show. For example, commercially available adhesives such as VSR-50 (available from Dow Chemical), ESP-2293 (available from ESP materials), SP3901 (available from Ji Li Chemical), and 2026c (available from Liuhe Chemical) and The dispersions are mixed to form the ink. In some embodiments, the average particle size of the powder in the ink is 100 nm to 550 nm. Generally speaking, if the average particle size of the powder in the ink is much larger than the average particle size of the powder in the dispersion, it means that the compatibility between the dispersant and the resin is not good. In some embodiments, the difference between the average particle size of the powder in the ink and the average particle size of the powder in the dispersion may be less than 5%.

In order to make the above content and other purposes, features, and advantages of this disclosure more comprehensible, the preferred embodiments are listed below and described in detail as follows:

[Example]

In the following examples, the measurement methods of the particle size of the powder in the dispersion or the ink, such as Da _ave , D ₉₅ , and D ₁₀₀ , are the ISO-13320 standard method.

Synthesis Example 1 (DBDI-01)

After dissolving N,N,N',N',N" -pentamethyldiethylenetriamine (PMDETA, 7.90 g, 45.59 mmole) in tetrahydrofuran (THF, 65 mL), nitrogen gas was blown into the THF solution to remove oxygen. Then CuBr (6.54 g, 45.59 mmole) was added into the solution and stirred evenly. Then CuBr ₂ (2.04 g, 9.12 mmole) was added into the THF solution and stirred evenly.

Tert-butyl methacrylate ( tBMA , 77.80g, 547.12mmole) and p-tolylsulfonyl chloride ( p -TsCl, 8.69g, 45.59mmole) were dissolved in THF (65mL), and nitrogen was passed into Deoxygenation in THF solution. Then, this solution was added to the PMDETA solution, and the above reactant was heated to 40°C under nitrogen to react for about 18 hours to form PtBMA . The above polymerization mechanism is atom transfer radical polymerization (ATRP), and its reaction is as follows:

Nitrogen gas was passed into isobutyl methacrylate ( iBMA , 77.80g, 547.12 mmole) to remove oxygen, then the iBMA after oxygen removal was added to the PtBMA solution, and the above reactant was heated to 40°C under nitrogen to react for about At 24 hours, a double block copolymer PtBMA - b - PiBMA was formed. It can be understood that since the two monomer systems of tBMA and iBMA react sequentially rather than simultaneously, the formed copolymer is a double block copolymer rather than a random copolymer. The above polymerization mechanism is ATRP, and its reaction is as follows:

After the above reaction was cooled, the crude product solution after the above reaction was filtered through a neutral alumina column, and the filtrate was reprecipitated with n-hexane, and a white solid (P t BMA- b -P i BMA) was collected. The Mw of the above product was about is 6600, Mn is 4300, and PDI is 1.5. In the above formula, m=10, n=19.

Then take PtBMA - b - PiBMA (100g, 23.25mmol) and dioxane (120mL) and mix and stir under nitrogen, then add hydrochloric acid (11.0mL, 128mmol) to the above mixture, and heat to 85°C for reaction 18 hours. After cooling the reaction, it was concentrated to remove the solvent. The crude product was dissolved in THF until it had low viscosity and fluidity, and the insoluble matter was filtered off. Then the solution was added into n-hexane for reprecipitation, and the filter cake was collected by filtration. After drying the filter cake, a white solid PMAA- b -P i BMA (acid value about 200-215 mg KOH/g) was obtained. PMAA- b -P i BMA has Mw=4900, Mn=2700, and PDI=1.8. Next, 60 g of PMAA- b -P i BMA powder was stirred and dispersed in 267 mL of deionized water, 28% ammonia solution (14.9 g) was added dropwise into the above dispersion, and heated to 70° C. for 5 hours. After complete dissolution, adjust the pH value of the above solution to above 8 with ammonia water to obtain the double block copolymer DBDI-01 (solid content: 18.2wt%). The above reaction is as follows:

Synthesis Example 2 (DBDI-02)

After PMDETA (7.90 g, 45.59 mmole) was dissolved in THF (65 mL), nitrogen was bubbled into the THF solution to remove oxygen. Then CuBr (6.54 g, 45.59 mmole) was added into the solution and stirred evenly. Then CuBr ₂ (2.04 g, 9.12 mmole) was added into the THF solution and stirred evenly.

tBMA (77.80 g, 547.12 mmole) and p -TsCl (8.69 g, 45.59 mmole) were dissolved in THF (65 mL), and nitrogen gas was blown into the THF solution to remove oxygen. Then this solution was added to the PMDETA solution, and the above reactant was heated to 40° C. for 18 hours under nitrogen to form P t BMA. The above polymerization mechanism is atom transfer radical polymerization (ATRP), and its reaction is as follows:

Introduce nitrogen gas into iBMA (38.90g, 273.56mmole) to remove oxygen, then add iBMA after deoxygenation into the PtBMA solution, heat the above reactant to 40°C under nitrogen gas for 24 hours to form double clusters Copolymer PtBMA - b - PiBMA . It can be understood that since the two monomer systems of tBMA and iBMA react sequentially rather than simultaneously, the formed copolymer is a double block copolymer rather than a random copolymer. The above polymerization mechanism is ATRP, and its reaction is as follows:

After the above reaction was cooled, the crude product solution after the above reaction was filtered through a neutral alumina column, and the filtrate was reprecipitated with n-hexane, and a white solid (P t BMA- b -P i BMA) was collected. The Mw of the above product is 3800, the Mn is 2500, and the PDI is 1.5. In the above formula, m=10, n=6.

Then take PtBMA - b - PiBMA (70g, 28.00mmol) and dioxane (140mL) and mix and stir under nitrogen, then add hydrochloric acid (23.0mL, 140mmol) into the above mixture, and heat to 85°C for reaction 18 hours. After cooling the reaction, it was concentrated to remove the solvent. The crude product was dissolved in THF until it had low viscosity and fluidity, and the insoluble matter was filtered off. Then the solution was added into n-hexane for reprecipitation, and the filter cake was collected by filtration. After drying the filter cake, a white solid PMAA- b -P i BMA (acid value about 280-305 mg KOH/g) was obtained. PMAA- b -P i BMA has Mw=2100, Mn=1400, and PDI=1.5. Next, 30 g of PMAA- b -P i BMA powder was stirred and dispersed in 72 mL of deionized water, 28% ammonia solution (11 g) was added dropwise into the above dispersion, and heated to 70° C. for 5 hours. After complete dissolution, adjust the pH value of the above solution to above 8 with ammonia water to obtain the double block copolymer DBDI-02 (solid content: 26.8wt%). The above reaction is as follows:

Synthesis Example 3 (DBDT-01)

After PMDETA (12.18 g, 70.32 mmole) was dissolved in THF (65 mL), nitrogen gas was bubbled into the THF solution to remove oxygen. Then CuBr (10.08 g, 70.32 mmole) was added into the solution and stirred evenly. Then CuBr ₂ (3.14 g, 14.06 mmole) was added into the THF solution and stirred evenly.

tBMA (100 g, 703.23 mmole), p -TsCl (13.40 g, 70.32 mmole) were dissolved in THF (65 mL), and nitrogen gas was blown into the THF solution to remove oxygen. Then, this solution was added to the PMDETA solution, and the above reactant was heated to 40° C. for 22 hours under nitrogen to form P t BMA. The above polymerization mechanism is ATRP, and its reaction formula is as follows:

Nitrogen was introduced into tetrahydrofuryl methacrylate (THFMA, 119.70 g, 703.23 mmole) to remove oxygen, then THFMA after deoxygenation was added to the PtBMA solution, and the above reactants were heated to 40 °C under nitrogen for 24 hours to form Double block copolymer PtBMA - b -PTHFMA. It can be understood that since the two monomer systems of tBMA and THFMA react sequentially rather than simultaneously, the formed copolymer is a double block copolymer rather than a random copolymer. The above polymerization mechanism is ATRP, and its reaction is as follows:

After the above reaction was cooled, the crude product solution after the above reaction was filtered through a neutral alumina column, and the filtrate was reprecipitated with n-hexane, and a white solid (P t BMA- b -PTHFMA) was collected. The Mw of the above product is 3600, the Mn is 2400, and the PDI is 1.5. In the above formula, m=9, n=5.

Then PtBMA -b -PTHFMA (151g, 6401mmol) and dioxane (300mL) were mixed and stirred under nitrogen, and then hydrochloric acid (27.5mL, 320mmol) was added to the above mixture, heated to 85°C for 18 hours. After cooling the reaction, it was concentrated to remove the solvent. The crude product was dissolved in THF until it had low viscosity and fluidity, and the insoluble matter was filtered off. Then the solution was added into n-hexane for reprecipitation, and the filter cake was collected by filtration. After drying the filter cake, a white solid PMAA- b -PTHFMA (acid value 210-215 mg KOH/g) was obtained. PMAA- b -PTHFMA has Mw=2700, Mn=1800, and PDI=1.5. Next, 60g of PMAA -b -PTHFMA powder was stirred and dispersed in 60mL of deionized water, 28% ammonia solution (15.2g) was added dropwise into the above dispersion, and heated to 70°C for 5 hours. After complete dissolution, adjust the pH value of the above solution to above 8 with ammonia water to obtain double block copolymer DBDT-01 (solid content: 45wt%). The above reaction is as follows:

Synthesis Example 4 (DBMA-01)

After PMDETA (12.18 g, 70.32 mmole) was dissolved in THF (65 mL), nitrogen gas was bubbled into the THF solution to remove oxygen. Then CuBr (10.08 g, 70.32 mmole) was added into the solution and stirred evenly. Then CuBr ₂ (3.14 g, 14.06 mmole) was added into the THF solution and stirred evenly.

After vacuuming the two-necked flask with nitrogen, add tBMA (100g, 703.23mmole), p -TsCl (13.40g, 70.32mmole), and THF (85mL), and pass nitrogen into the THF solution to remove oxygen. Then, this solution was added into the PMDETA solution, and the above reactant was heated to 40° C. for 7 hours under nitrogen to form P t BMA. The above polymerization mechanism is ATRP, and its reaction formula is as follows:

Nitrogen gas was passed into hydroxyethyl methacrylate (HEMA, 113.22g, 843.88 mmole) to remove oxygen, then THFMA after oxygen removal was added to the PtBMA solution, and the above reactant was heated to 40°C under nitrogen to react for 18 hours, the double block copolymer P t BMA- b -PHEMA was formed. It can be understood that since the two monomer systems of tBMA and HEMA react sequentially rather than simultaneously, the formed copolymer is a double block copolymer rather than a random copolymer. The above polymerization mechanism is ATRP, and its reaction is as follows:

After the above reaction was cooled, the crude product solution after the above reaction was filtered through a neutral alumina column, and the filtrate was reprecipitated with n-hexane, and a white solid (P t BMA- b -PHEMA) was collected. The Mw of the above product is 4100, the Mn is 2800, and the PDI is 1.5. In the above formula, m=11, n=7.

Then PtBMA -b -PHEMA (120g, 42.86mmol) and dioxane (250mL) were mixed and stirred under nitrogen, then hydrochloric acid (17.9mL, 214mmol) was added to the above mixture, and heated to 85°C for 18 hours . After cooling the reaction, it was concentrated to remove the solvent. The crude product was dissolved in THF until it had low viscosity and fluidity, and the insoluble matter was filtered off. Then the solution was added into n-hexane for reprecipitation, and the filter cake was collected by filtration. After drying the filter cake, a white solid PMAA- b -PHEMA (acid value 230-250 mg KOH/g) was obtained. Mw=3500, Mn=2300, and PDI=1.5 of PMAA- b- PHEMA. Next, 60g of PMAA -b -PHEMA powder was stirred and dispersed in 93mL of deionized water, and 28% ammonia solution (17.1g) was added dropwise into the above dispersion, and then heated to 70°C for 5 hours. After the dissolution is complete, adjust the pH value of the above solution to above 8 with ammonia water to obtain the double block copolymer DBMA-01 (solid content: 35.5wt%). The above reaction is as follows:

Example 1

Get the double block copolymer DBDI-02 of 1.68g as dispersant, after adding the water stirring and dissolving of 15.32g, after adding 3g of carbon black (XC72R, purchased from Cabot), and keep stirring to obtain carbon black dispersion liquid WB38, The average particle diameter (D _ave ) of the carbon black is 305nm, and the D ₉₅ is 689nm. The weight ratio (D/P) of dispersant to carbon black in carbon black dispersion WB38 is 0.15, and has good fluidity.

Get 1.38g of polyurethane resin (2026C, purchased from Liuhe Chemical Industry) and mix it with 4.61g of carbon black dispersion liquid WB38, stir to obtain conductive ink, and the average particle diameter (D _ave ) of its carbon black is 307nm (△D _ave = 2nm), and D ₉₅ is 694nm. The conductive ink was coated on the PET film with a No. 44 wire rod, heated to 150° C. and baked for 30 minutes to obtain a conductive layer. Measure the sheet resistance (31Ω/□/mil) of the conductive layer with a four-point probe conductivity meter (5601Y, purchased from Quatek Co., Ltd.), and use a high-precision thickness meter (sylvac D50S display, manufacturer sylvac) Measure the thickness of the conductive layer and calculate the bulk resistance (78mΩ.cm) of the conductive layer.

Example 2

Get 1.00g of double block copolymer DBDT-01 as a dispersant, add 24.50g of water and stir to dissolve, add 4.5g of carbon black (XC72R), and continue to stir to obtain carbon black dispersion WB24, its carbon The average particle diameter (D _ave ) of black was 333 nm, and D ₉₅ was 918 nm. The carbon black dispersion WB24 has a weight ratio (D/P) of dispersant to carbon black of 0.10 and good fluidity.

Get 2.30g of resin (2026C) and mix it with 7.68g of carbon black dispersion liquid WB24, stir to obtain conductive ink, the average particle diameter (D _ave ) of its carbon black is 310nm (△D _ave =-23nm), and D ₉₅ 718nm. The conductive ink was coated on the PET film with a No. 44 wire rod, heated to 150° C. and baked for 30 minutes to obtain a conductive layer. Measure the sheet resistance (34Ω/□/mil) of the conductive layer with a four-point probe conductivity meter (5601Y), measure the thickness of the conductive layer with a high-precision thickness gauge (sylvac D50S) and calculate the volume resistance of the conductive layer ( 86mΩ.cm).

Example 3

Get 1.50g of double block copolymer DBDT-01 as a dispersant, add 24.00g of water and stir to dissolve, add 4.5g of carbon black (XC72R), and keep stirring to obtain carbon black dispersion WB25, its carbon The average particle diameter (D _ave ) of black is 315 nm, and D ₉₅ is 757 nm. The weight ratio (D/P) of dispersant to carbon black in carbon black dispersion WB25 is 0.15, and has good fluidity.

Get 2.30g of resin (2026C) and mix it with 7.68g of carbon black dispersion liquid WB25, stir to obtain conductive ink, the average particle diameter (D _ave ) of its carbon black is 329nm (△D _ave =14nm), and _D95 is 933nm. The conductive ink was coated on the PET film with a No. 44 wire rod, heated to 150° C. and baked for 30 minutes to obtain a conductive layer. Measure the sheet resistance (39Ω/□/mil) of the conductive layer with a four-point probe conductivity meter (5601Y), measure the thickness of the conductive layer with a high-precision thickness gauge (sylvac D50S) and calculate the volume resistance of the conductive layer ( 99mΩ.cm).

Example 4

Get the double block copolymer DBDT-01 of 1.99g as dispersant, add the water of 23.51g and after stirring and dissolving, after adding the carbon black (XC72R) of 4.5g, and keep stirring to obtain carbon black dispersion liquid WB26, its carbon The average particle size (D _ave ) of black was 317 nm, and the D ₉₅ was 861 nm. The weight ratio (D/P) of dispersant to carbon black in carbon black dispersion WB26 is 0.20, and has good fluidity.

Get 2.30g of resin (2026C) and mix it with 7.68g of carbon black dispersion liquid WB26, stir to obtain conductive ink, the average particle diameter (D _ave ) of its carbon black is 313nm (△D _ave =-4nm), D ₉₅ is 595nm. The conductive ink was coated on the PET film with a No. 44 wire rod, heated to 150° C. and baked for 30 minutes to obtain a conductive layer. Measure the sheet resistance (86Ω/□/mil) of the conductive layer with a four-point probe conductivity meter (5601Y), measure the thickness of the conductive layer with a high-precision thickness gauge (sylvac D50S) and calculate the volume resistance of the conductive layer ( 218mΩ.cm).

Example 5

Get the double block copolymer DBMA-01 of 0.85g as dispersant, add the water of 16.15g and after stirring and dissolving, add after the carbon black (XC72R) of 3g, and keep stirring to obtain carbon black dispersion liquid WB39, its carbon black The average particle diameter (D _ave ) is 330nm, and the D ₉₅ is 814nm. The weight ratio (D/P) of dispersant to carbon black in carbon black dispersion WB39 is 0.10, and has good fluidity.

Take 1.38g of resin (2026C) and mix it with 4.61g of carbon black dispersion liquid WB39, stir to obtain conductive ink, the average particle diameter (D _ave ) of the carbon black is 536nm (△D _ave =206nm), D ₉₅ is 1260nm . The conductive ink was coated on the PET film with a No. 44 wire rod, heated to 150° C. and baked for 30 minutes to obtain a conductive layer. Measure the sheet resistance (55Ω/□/mil) of the conductive layer with a four-point probe conductivity meter (5601Y), measure the thickness of the conductive layer with a high-precision thickness gauge (sylvac D50S) and calculate the volume resistance of the conductive layer ( 139mΩ.cm).

Comparative example 1

Get 1.65g of double-block copolymer DBDI-01 as a dispersant, add 15.35g of water and stir to dissolve, add 3g of carbon black (XC72R), and continue stirring to obtain Blend WB44. The weight ratio (D/P) of dispersant to carbon black in the mixture WB44 is 0.10, but it cannot be dispersed and presents a colloidal state.

Comparative example 2

Take 1.69g of commercially available dispersant BYK2015 (solid content 40wt%, purchased from BYK), add 23.81g of water and stir to dissolve, add 4.5g of carbon black (XC72R), and continue stirring to obtain the mixture WB27. The weight ratio (D/P) of dispersant to carbon black in the mixture WB27 is 0.15, which cannot be dispersed and presents a colloidal state.

Comparative example 3

Get the commercially available dispersant BYK2015 of 2.25g, add the water of 23.25g and after stirring and dissolving, after adding the carbon black (XC72R) of 4.5g, and keep stirring to obtain the carbon black dispersion liquid WB28, the average particle diameter of its carbon black (D _ave ) is 406nm, D ₉₅ is 1180nm. The weight ratio (D/P) of the dispersant to carbon black in the carbon black dispersion WB28 is 0.20, and the fluidity is poor.

Get 2.30g of resin (2026C) and mix it with 7.68g of carbon black dispersion liquid WB28, stir to obtain conductive ink, the average particle diameter (D _ave ) of its carbon black is 346nm (△D _ave =-60nm), D ₉₅ is 1290nm. The conductive ink was coated on the PET film with a No. 44 wire rod, heated to 150° C. and baked for 30 minutes to obtain a conductive layer. Measure the sheet resistance (143Ω/□/mil) of the conductive layer with a four-point probe conductivity meter (5601Y), measure the thickness of the conductive layer with a high-precision thickness gauge (sylvac D50S) and calculate the volume resistance of the conductive layer ( 363mΩ.cm).

Comparative example 4

Get the commercially available dispersant BYK2015 of 4.50g, add the water of 21.00g and after stirring and dissolving, after adding the carbon black (XC72R) of 4.5g, and keep stirring to obtain the carbon black dispersion liquid WB29, the average particle diameter of its carbon black (D _ave ) is 330nm, D ₉₅ is 725nm. The carbon black dispersion WB29 has a weight ratio (D/P) of dispersant to carbon black of 0.40 and good fluidity.

Get 2.30g of resin (2026C) and mix it with 7.68g of carbon black dispersion liquid WB29, stir to obtain conductive ink, the average particle diameter (D _ave ) of its carbon black is 319nm (△D _ave =-11nm), D ₉₅ is 766nm. The conductive ink was coated on the PET film with a No. 44 wire rod, heated to 150° C. and baked for 30 minutes to obtain a conductive layer. Measure the sheet resistance (126Ω/□/mil) of the conductive layer with a four-point probe conductivity meter (5601Y), measure the thickness of the conductive layer with a high-precision thickness gauge (sylvac D50S) and calculate the volume resistance of the conductive layer ( 320mΩ.cm).

From the comparison of Examples 1 to 5 and Comparative Examples 1 to 4, it can be known that the examples have good dispersibility (D _ave =305~333nm) with less dispersant dosage (D/P=0.10~0.15). In addition, the conductivity of the conductive layer of the embodiment is greatly improved, and the sheet resistance is greatly reduced.

Example 6

Take 2.50 g of double block copolymer DBDT-01 as a dispersant, add 23.00 g of water and stir to dissolve, add 4.5 g of carbon black (EMPEROR ^® 2000, purchased from Cabot), and stir for another 0.5 hours. After taking out the magnet, add 60g of zirconium beads (size: 0.2mm) and shake and disperse for 8 hours. After shaking, filter through a filter cloth with a filter hole size of 25 μm to obtain carbon black dispersion K151a. The average particle diameter of its carbon black ( D _ave ) was 76 nm, and D ₁₀₀ was 396 nm. The weight ratio (D/P) of the dispersant to carbon black in the carbon black dispersion K151a is 0.25, and the carbon black content is 15wt%.

After 3.0 g of the carbon black dispersion K151a was placed in an oven at 60°C for 7 days, the average particle size (D _ave ) of the carbon black was 74 nm (ΔD _ave =-2 nm), and the D ₁₀₀ was 295 nm. After taking 3.0g of carbon black dispersion K151a and 0.53g of 1,2-propanediol (as an antifreeze agent) and putting them in a refrigerator at -17°C for 7 days, the average particle diameter (D _ave ) of the carbon black was 71nm ( ΔD _ave =-5nm), D ₁₀₀ is 295nm.

Example 7

Take 3.33g of double-block copolymer DBDT-01 as a dispersant, add 20.67g of water and stir to dissolve, then add 6.0g of carbon black (EMPEROR ^® 2000), and stir for another 0.5 hours. After taking out the magnet, add 60g of zirconium beads (size: 0.2mm) and disperse by shaking for 8 hours. After the shaking is completed, filter through a filter cloth with a filter hole size of 25 μm to obtain carbon black dispersion K152a. The average particle diameter of its carbon black ( D _ave ) was 91 nm, and D ₁₀₀ was 396 nm. The weight ratio (D/P) of the dispersant to carbon black in the carbon black dispersion K152a is 0.25, and the carbon black content is 20wt%.

After 3.0 g of the carbon black dispersion K152a was placed in an oven at 60°C for 7 days, the average particle size (D _ave ) of the carbon black was 98 nm (ΔD _ave =7 nm), and the D ₁₀₀ was 396 nm. After taking 3.0g of carbon black dispersion K152a and 0.53g of 1,2-propanediol (as an antifreeze agent) and placing it in a refrigerator at -17°C for 7 days, the average particle diameter (D _ave ) of its carbon black was 96nm ( ΔD _ave =5nm), D ₁₀₀ is 396nm.

Example 8

Take 3.36g of double block copolymer DBDI-02 as a dispersant, add 22.14g of water and stir to dissolve, then add 4.5g of carbon black (EMPEROR ^® 2000) and stir for 0.5 hours. After taking out the magnet, add 60g of zirconium beads (size: 0.2mm) and shake and disperse for 8 hours. After shaking, filter with a filter cloth with a filter hole size of 25 μm to obtain carbon black dispersion K153a. The average particle diameter of its carbon black ( D _ave ) was 80 nm, and D ₁₀₀ was 342 nm. The weight ratio (D/P) of the dispersant to carbon black in the carbon black dispersion K153a is 0.20, and the carbon black content is 15wt%.

After 3.0 g of the carbon black dispersion K153a was placed in an oven at 60°C for 7 days, the average particle size (D _ave ) of the carbon black was 84 nm (ΔD _ave =4 nm), and the D ₁₀₀ was 531 nm. After 3.0 g of carbon black dispersion K153a and 0.53 g of 1,2-propanediol (as an antifreeze agent) were placed in a refrigerator at -17°C for 7 days, the average particle diameter (D _ave ) of the carbon black was 92nm ( ΔD _ave =12nm), D ₁₀₀ is 342nm.

Example 9

Take 5.71g of double block copolymer DBDI-02 as a dispersant, add 18.29g of water and stir to dissolve, then add 6.0g of carbon black (EMPEROR ^® 2000) and stir for 0.5 hours. After taking out the magnetite, add 60g of zirconium beads (size: 0.2mm) and shake and disperse for 8 hours. After the shaking is completed, filter through a filter cloth with a filter hole size of 25 μm to obtain carbon black dispersion K154a. The average particle diameter of its carbon black ( D _ave ) was 102 nm, and D ₁₀₀ was 459 nm. The weight ratio (D/P) of the dispersant to carbon black in the carbon black dispersion K154a is 0.20, and the carbon black content is 20wt%.

After 3.0 g of the carbon black dispersion K154a was placed in an oven at 60°C for 7 days, the average particle size (D _ave ) of the carbon black was 102 nm (ΔD _ave =0 nm), and the D ₁₀₀ was 459 nm. After taking 3.0g of carbon black dispersion K154a and 0.53g of 1,2-propanediol (as an antifreeze agent) and putting them in a refrigerator at -17°C for 7 days, the average particle diameter (D _ave ) of the carbon black was 106nm ( ΔD _ave =4nm), D ₁₀₀ is 615nm.

Example 10

Take 2.52g of double-block copolymer DBDI-02 as a dispersant, add 22.98g of water and stir to dissolve, then add 4.5g of carbon black (EMPEROR ^® 2000) and stir for 0.5 hours. After taking out the magnetite, add 60g of zirconium beads (size: 0.2mm) and shake and disperse for 8 hours. After the shaking is completed, filter through a filter cloth with a filter hole size of 25 μm to obtain carbon black dispersion K147a. The average particle diameter of its carbon black ( D _ave ) was 76 nm, and D ₁₀₀ was 255 nm. The weight ratio (D/P) of the dispersant to carbon black in the carbon black dispersion K147a is 0.15, and the carbon black content is 15wt%.

After 3.0 g of the carbon black dispersion K147a was placed in an oven at 60°C for 7 days, the average particle size (D _ave ) of the carbon black was 89 nm (ΔD _ave =13 nm), and the D ₁₀₀ was 396 nm. After taking 3.0g of carbon black dispersion K147a and 0.53g of 1,2-propanediol (as an antifreeze agent) and putting them in a refrigerator at -17°C for 7 days, the average particle diameter (D _ave ) of the carbon black was 111nm ( ΔD _ave =35nm), D ₁₀₀ is 531nm.

Comparative Example 5

Take 6.75g of commercially available dispersant BYK2015, add 18.75g of water and stir to dissolve, then add 4.5g of carbon black (EMPEROR ^® 2000) and stir for 0.5 hours. After taking out the magnetite, add 60g of zirconium beads (size: 0.2mm) and shake and disperse for 8 hours. After shaking, filter through a filter cloth with a filter hole size of 25 μm to obtain carbon black dispersion K179a. The average particle diameter of its carbon black ( D _ave ) is 63 nm, and D ₁₀₀ is 295 nm. The weight ratio (D/P) of the dispersant to carbon black in the carbon black dispersion K179a is 0.60, and the carbon black content is 15wt%. It is worth noting that if the weight ratio (D/P) of the dispersant to carbon black of this carbon black dispersion is reduced to 0.4 or lower, it will gel (Gel) and cannot flow.

Take 3.0 g of carbon black dispersion K179a and place it in an oven at 60° C. for 7 days, and then it becomes gelled and cannot flow. After taking 3.0g of carbon black dispersion K179a and 0.53g of 1,2-propanediol (as an antifreeze agent) and putting them in a refrigerator at -17°C for 7 days, the average particle diameter (D _ave ) of the carbon black was 77nm ( ΔD _ave =14nm), D ₁₀₀ is 6440nm.

Comparative example 6

Take 7.88g of commercially available dispersant BYK2012 (purchased from BYK), add 17.63g of water and stir to dissolve, then add 4.5g of carbon black (EMPEROR ^® 2000) and stir for 0.5 hours. After taking out the magnet, add 60g of zirconium beads (size: 0.2mm) and shake and disperse for 8 hours. After shaking, filter with a filter cloth with a filter hole size of 25 μm to obtain carbon black dispersion K184a. The average particle diameter of its carbon black ( D _ave ) is 134 nm, and D ₁₀₀ is 615 nm. The weight ratio (D/P) of the dispersant to carbon black in the carbon black dispersion K184a is 0.70, and the carbon black content is 15wt%. It is worth noting that if the weight ratio (D/P) of the dispersant to carbon black of this carbon black dispersion is reduced to 0.5 or lower, it will gel (Gel) and cannot flow.

3.0 g of the carbon black dispersion K184a was placed in an oven at 60° C. for 7 days and then gelled. Take 3.0g of carbon black dispersion K184a and 0.53g of 1,2-propanediol (as an antifreeze agent) and put it in a refrigerator at -17°C for 7 days, and then it will gel.

Comparative Example 7

Take 9.00g of commercially available dispersant BYK2010 (purchased from BYK), add 16.50g of water and stir to dissolve, then add 4.5g of carbon black (EMPEROR ^® 2000) and stir for 0.5 hours. After taking out the magnet, add 60g of zirconium beads (size: 0.2mm) and shake and disperse for 8 hours. After shaking, filter with a filter cloth with a filter hole size of 25 μm to obtain carbon black dispersion K188a. The average particle diameter of its carbon black ( D _ave ) was 105 nm, and D ₁₀₀ was 396 nm. The weight ratio (D/P) of the dispersant to carbon black in the carbon black dispersion K188a is 0.80, and the carbon black content is 15wt%. It is worth noting that if the weight ratio (D/P) of the dispersant to carbon black of this carbon black dispersion is reduced to 0.5 or lower, it will gel (Gel) and cannot flow.

Take 3.0 g of the carbon black dispersion K188a and place it in an oven at 60° C. for 7 days, and after 7 days, it becomes gelatinized and unable to flow. After taking 3.0g of carbon black dispersion K188a and 0.53g of 1,2-propanediol (as an antifreeze agent) and putting them in a refrigerator at -17°C for 7 days, the average particle diameter (D _ave ) of the carbon black was 105nm ( ΔD _ave =0 nm), D ₁₀₀ is 615 nm.

Comparative Example 8

Take 3.65g of commercially available dispersant BYK9151 (purchased from BYK), add 21.85g of water and stir to dissolve, then add 4.5g of carbon black (EMPEROR ^® 2000) and stir for 0.5 hours. After taking out the magnet, add 60g of zirconium beads (size: 0.2mm) and shake and disperse for 8 hours. After shaking, filter through a filter cloth with a filter hole size of 25 μm to obtain carbon black dispersion K189a. The average particle diameter of its carbon black ( D _ave ) is 135 nm, and D ₁₀₀ is 615 nm. The carbon black dispersion K189a has a weight ratio (D/P) of dispersant to carbon black of 0.80, and a carbon black content of 15 wt%. It is worth noting that if the weight ratio (D/P) of the dispersant to carbon black of this carbon black dispersion is reduced to 0.5 or lower, it will gel (Gel) and cannot flow.

3.0 g of the carbon black dispersion K189a was placed in an oven at 60° C. for 7 days and then gelled. Take 3.0g of carbon black dispersion K189a and 0.53g of 1,2-propanediol (as an antifreeze agent) and place it in a refrigerator at -17°C for 7 days and then it will gel.

From the comparison of Examples 6 to 10 and Comparative Examples 5 to 8, it can be known that the dispersant of the examples can disperse high specific surface area carbon black up to 20wt% under the condition of less usage amount (D/P=0.15~0.25) , and good thermal storage and low temperature storage stability.

Example 11

Take 1.00 g of double block copolymer DBDT-01 as a dispersant, add 14.00 g of water and stir to dissolve, then add 15.00 g of titanium dioxide (TiO ₂ , CR828, purchased from the manufacturer TRONOX) and stir for 0.5 hours. After taking out the magnet, add 60g of zirconium beads (size: 0.2mm) and shake and disperse for 8 hours. After shaking, filter through a filter cloth with a filter hole size of 25 μm to obtain the titanium dioxide dispersion LAW184. The average particle size of the titanium dioxide ( D _ave ) was 464 nm, D ₉₅ was 930 nm, and the particle size distribution (D ₉₅ /D _ave ) was 2.00.

Example 12

Take 1.68g of double block copolymer DBDI-02 as a dispersant, add 13.32g of water and stir to dissolve, then add 15.00g of titanium dioxide (CR828) and stir for 0.5 hours. After taking out the magnet, add 60g of zirconium beads (size: 0.2mm) and shake and disperse for 8 hours. After shaking, filter through a filter cloth with a filter hole size of 25 μm to obtain the titanium dioxide dispersion LAW206. The average particle size of the titanium dioxide ( D _ave ) was 278 nm, D ₉₅ was 524 nm, and the particle size distribution (D ₉₅ /D _ave ) was 1.88.

Comparative Example 9

Take 1.13g of commercially available dispersant BYK2015, add 13.88g of water and stir to dissolve, then add 15.00g of titanium dioxide (CR828) and stir for 0.5 hours. After taking out the magnet, add 60g of zirconium beads (size: 0.2mm) and shake and disperse for 8 hours. After shaking, filter through a filter cloth with a filter hole size of 25 μm to obtain the titanium dioxide dispersion LAW211. The average particle size of the titanium dioxide ( D _ave ) was 883 nm, D ₉₅ was 4710 nm, and the particle size distribution (D ₉₅ /D _ave ) was 5.33.

From the comparison between Examples 11 and 12 and Comparative Example 9, it can be known that the dispersion liquid obtained by using the dispersant of the example to disperse titanium dioxide has a smaller particle size and a narrower distribution of titanium dioxide, showing a better dispersion effect.

Example 13

Get 2.50g of double-block copolymer DBDT-01 as a dispersant, add 17.00g of water and 3.00g of 1,2-propanediol and stir to dissolve, add 7.50g of blue pigment (B-432, purchased from Fuda pigment) was stirred for 0.5 hours. After taking out the magnet, add 60g of zirconium beads (size: 0.2mm) and shake and disperse for 8 hours. After shaking, filter with a filter cloth with a filter hole size of 25 μm to obtain the blue dispersion B07. The average particle size of the blue pigment is (D _ave ) was 122 nm, and D ₁₀₀ was 396 nm. The weight ratio (D/P) of the dispersant to the blue pigment of the blue dispersion liquid B07 is 0.15, and the content of the blue pigment is 25wt%.

After 3.0 g of the blue dispersion B07 was placed in an oven at 60°C for 7 days, the average particle size (D _ave ) of the blue pigment was 117 nm (ΔD _ave =-5 nm), and the D ₁₀₀ was 396 nm. After 3.0 g of the blue dispersion B07 was placed in a refrigerator at -17°C for 7 days, the average particle size (D _ave ) of the blue pigment was 120 nm (ΔD _ave =-2 nm), and the D ₁₀₀ was 342 nm.

Example 14

Take 4.20g of double block copolymer DBDI-02 as dispersant, add 15.30g of water and 3.00g of 1,2-propanediol and stir to dissolve, then add 7.50g of blue pigment (B-432) and stir for 0.5 hours. After taking out the magnet, add 60g of zirconium beads (size: 0.2mm) and shake and disperse for 8 hours. After shaking, filter through a filter cloth with a filter hole size of 25 μm to obtain the blue dispersion B08. The average particle size of the blue pigment is (D _ave ) was 118 nm, and D ₁₀₀ was 459 nm. The weight ratio (D/P) of the dispersant to the blue pigment of the blue dispersion liquid B08 is 0.15, and the content of the blue pigment is 25wt%.

After 3.0 g of the blue dispersion B08 was placed in an oven at 60° C. for 7 days, the average particle size (D _ave ) of the blue pigment was 126 nm (ΔD _ave =8 nm), and the D ₁₀₀ was 531 nm. After 3.0 g of the blue dispersion B08 was placed in a refrigerator at -17°C for 7 days, the average particle size (D _ave ) of the blue pigment was 122 nm (ΔD _ave =4 nm), and the D ₁₀₀ was 531 nm.

Example 15

Take 5.60g of double block copolymer DBDI-02 as dispersant, add 13.90g of water and 3.00g of 1,2-propanediol and stir to dissolve, then add 7.50g of blue pigment (B-432) and stir for 0.5 hours. After taking out the magnet, add 60g of zirconium beads (size: 0.2mm) and shake and disperse for 8 hours. After shaking, filter through a filter cloth with a filter hole size of 25 μm to obtain the blue dispersion B09. The average particle size of the blue pigment is (D _ave ) was 125 nm, and D ₁₀₀ was 396 nm. The weight ratio (D/P) of the dispersant to the blue pigment of the blue dispersion liquid B09 is 0.20, and the content of the blue pigment is 25wt%.

After 3.0 g of the blue dispersion B09 was placed in an oven at 60° C. for 7 days, the average particle diameter (D _ave ) of the blue pigment was 140 nm (ΔD _ave =15 nm), and the D ₁₀₀ was 459 nm. After 3.0 g of the blue dispersion B09 was placed in a refrigerator at -17°C for 7 days, the average particle diameter (D _ave ) of the blue pigment was 126 nm (ΔD _ave =1 nm), and the D ₁₀₀ was 396 nm.

Example 16

Take 3.33g of double block copolymer DBDT-01 as a dispersant, add 17.67g of water and 3.00g of 1,2-propanediol and stir to dissolve, then add 6.00g of yellow pigment (Y-310, purchased from Daifuku Pigment) Stir for 0.5 hours. After taking out the magnet, add 60g of zirconium beads (size: 0.2mm) and shake and disperse for 8 hours. After shaking, filter through a filter cloth with a filter hole size of 25 μm to obtain yellow dispersion Y08. The average particle diameter of its yellow pigment (D _ave ) is 138nm, D ₁₀₀ is 459nm. The weight ratio (D/P) of the dispersant to the yellow pigment of the yellow dispersion liquid Y08 is 0.25, and the content of the yellow pigment is 18wt%.

After 3.0 g of the yellow dispersion liquid Y08 was placed in an oven at 60° C. for 7 days, the average particle diameter (D _ave ) of the blue pigment was 134 nm (ΔD _ave =-4 nm), and the D ₁₀₀ was 459 nm. After 3.0 g of the yellow dispersion liquid Y08 was placed in a refrigerator at -17°C for 7 days, the average particle diameter (D _ave ) of the yellow pigment was 138 nm (ΔD _ave =0 nm), and the D ₁₀₀ was 459 nm.

Example 17

Take 6.72g of double block copolymer DBDI-02 as a dispersant, add 14.28g of water and 3.00g of 1,2-propanediol and stir to dissolve, then add 6.00g of yellow pigment (Y-310), and stir for another 0.5 hours . After taking out the magnet, add 60g of zirconium beads (size: 0.2mm) and shake and disperse for 8 hours. After shaking, filter through a filter cloth with a filter hole size of 25 μm to obtain yellow dispersion Y10. The average particle size of the yellow pigment (D _ave ) is 153nm, D ₁₀₀ is 459nm. The weight ratio (D/P) of the dispersant to the yellow pigment of the yellow dispersion liquid Y10 is 0.30, and the content of the yellow pigment is 20wt%.

After 3.0 g of the yellow dispersion Y10 was placed in an oven at 60°C for 7 days, the average particle size (D _ave ) of the blue pigment was 171 nm (ΔD _ave =18 nm), and the D ₁₀₀ was 459 nm. After 3.0 g of the yellow dispersion Y10 was placed in a refrigerator at -17°C for 7 days, the average particle size (D _ave ) of the yellow pigment was 184 nm (ΔD _ave =31 nm), and the D ₁₀₀ was 531 nm.

Example 18

Take 4.00g of double block copolymer DBDT-01 as a dispersant, add 17.00g of water and 3.00g of 1,2-propanediol and stir to dissolve, then add 6.00g of red pigment (R-220, purchased from Daifuku Pigment) Stir for 0.5 hours. After taking out the magnet, add 60g of zirconium beads (size: 0.2mm) and shake and disperse for 8 hours. After shaking, filter through a filter cloth with a filter hole size of 25 μm to obtain red dispersion R09. The average particle size of the red pigment (D _ave ) is 130nm, D ₁₀₀ is 459nm. The weight ratio (D/P) of the dispersant to the red pigment of the red dispersion liquid R09 is 0.30, and the content of the red pigment is 20wt%.

After 3.0 g of the red dispersion R09 was placed in an oven at 60°C for 7 days, the average particle size (D _ave ) of the blue pigment was 126nm (ΔD _ave =-4nm), and the D ₁₀₀ was 459nm. After 3.0 g of the red dispersion R09 was placed in a refrigerator at -17°C for 7 days, the average particle size (D _ave ) of the red pigment was 130 nm (ΔD _ave =0 nm), and the D ₁₀₀ was 459 nm.

Example 19

Take 5.60g of double block copolymer DBDI-02 as dispersant, add 15.40g of water and 3.00g of 1,2-propanediol and stir to dissolve, then add 6.00g of red pigment (R-220) and stir for 0.5 hours. After taking out the magnet, add 60g of zirconium beads (size: 0.2mm) and shake and disperse for 8 hours. After shaking, filter through a filter cloth with a filter hole size of 25 μm to obtain the red dispersion R10. The average particle size of the red pigment (D _ave ) is 132nm, D ₁₀₀ is 459nm. The weight ratio (D/P) of the dispersant to the red pigment of the red dispersion liquid R10 is 0.25, and the content of the red pigment is 20wt%.

After 3.0 g of the red dispersion R10 was placed in an oven at 60° C. for 7 days, the average particle size (D _ave ) of the blue pigment was 128 nm (ΔD _ave =-4 nm), and the D ₁₀₀ was 459 nm. After 3.0 g of the red dispersion R10 was placed in a refrigerator at -17°C for 7 days, the average particle size (D _ave ) of the red pigment was 132 nm (ΔD _ave =0 nm), and the D ₁₀₀ was 459 nm.

It can be known from Examples 13 to 19 that the dispersants of the examples can be used to disperse pigments, and the obtained dispersions have good stability in heat storage and low temperature storage.

Although the present disclosure has been disclosed above with several preferred embodiments, it is not intended to limit the present disclosure. Arbitrary changes and modifications can be made within the spirit and scope of this disclosure. Therefore, the scope of protection of this disclosure should be defined by the scope of the appended patent application.

none.

none.

Claims (10)

A dispersion liquid, comprising: 100 parts by weight of powder; 1 to 80 parts by weight of a dispersant; and 80 to 900 parts by weight of a polar solvent; wherein the dispersant is a double block copolymer, and its chemical structure is:

Wherein Ini and Ini' are the residues of the initiator used in the polymerization reaction; each R ¹ is independently H or methyl; R ² is

,

,or

; B is an alkali metal or N(R ³ ) ₄ , and each R ³ is independently H, C _1-4 alkyl, or C _1-4 alkyl alcohol; the ratio of m to n is 3: 1 to 1:2; and x is 0.7 to 1; wherein the weight average molecular weight of the dispersant is 1500 to 4500. The dispersion according to claim 1, wherein the powder includes carbon materials, pigments, metals, metal oxides, or combinations thereof. The dispersion according to claim 2, wherein the carbon material includes carbon black, graphite, graphene, carbon nanotubes, fullerene, or a combination thereof. The dispersion according to claim 1, wherein the average particle size of the powder is 100 nm to 550 nm. Such as the dispersion of claim 1, wherein the polar solvent includes water, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, diethylene glycol butyl ether acetate, ethylene glycol butyl ether , tetraethylene glycol dimethyl ether, or a combination of the above. An ink, comprising: a dispersion liquid and a resin, and the weight ratio of the dispersion liquid to the resin is 100:10 to 100:120; wherein the dispersion liquid comprises: 100 parts by weight of powder; 1 to 80 parts by weight of a dispersant and the polar solvent of 80 to 900 parts by weight; Wherein the dispersant is a double block copolymer, and its chemical structure is:

Wherein Ini and Ini' are the residues of the initiator used in the polymerization reaction; each R ¹ is independently H or methyl; R ² is

,

,or

; B is an alkali metal or N(R ³ ) ₄ , and each R ³ is independently H, C _1-4 alkyl, or C _1-4 alkyl alcohol; the ratio of m to n is 3: 1 to 1:2; x is 0.7 to 1; wherein the weight average molecular weight of the dispersant is 1500 to 4500. The ink according to claim 6, wherein the resin comprises polypropylene resin, polyurethane resin, or a combination thereof. The ink according to claim 6, wherein the powder includes carbon materials, pigments, metals, metal oxides, or combinations thereof. The ink of claim 8, wherein the carbon material includes carbon black, graphite, graphene, carbon nanotubes, fullerene, or a combination thereof. The ink according to claim 6, wherein the powder has an average particle size of 100 nm to 550 nm.