A positive polymer charge control agent, its preparation method and use

Abstract

The application discloses a positive electric polymer charge control agent P3-CRR shown in formula I and a preparation and application thereof. The P3-CRR polymer charge control agent has the advantages of fast electrification rate, high electric charge and good electric charge retention, and the performance thereof is not inferior to that of a currently commercially used benchmark positive electric charge control agent dimethyl di(tetradecyl) molybdate amine salt, and fully meets the performance requirements of high-speed printing carbon powder. Meanwhile, the polymer charge control agent P3-CRR is a colorless or nearly colorless solid, and also meets the preparation requirements of color carbon powder.

Description

Technical Field

[0001] This invention belongs to the field of electrophotography. Specifically, this invention relates to charge control agents (CCA) used in the preparation of developer toners for laser printing and electrostatic copying. More specifically, this invention relates to a class of positively charged polymeric charge control resins (CCRs) characterized by pyridinium tetrafluoroborate salts, their preparation methods, and applications. Background Technology

[0002] Toner (also known as ink powder or colorant) is a developer used in laser printers / electrostatic copiers based on electrophotographic technology, and is an important and widely used consumable. The main components of toner include resin, pigment, wax, and charge control agent (CCA). Toner is a fine powder composite material, obtained through steps such as mixing, kneading, pulverizing, and classifying the various components according to a formula (conventional physical method). The polymer resin is the main component, acting as a binder; the pigment is the source of visibility and color; the wax is a release agent, solving the problem of adhesion to the fixing roller during fixing; and the charge control agent is the most important component that imparts the charged properties to the toner, determining the charge polarity, charging rate, charge quantity, charge distribution uniformity, and charge stability.

[0003] The developing process of printing / copying is based on electrostatic principles, and the electrical properties of toner strongly influence its performance and print quality. Triboelectric charging is the primary factor contributing to toner's charge. Using charge control agents can determine charge polarity, adjust the charging rate, and maintain a sufficient and stable charge level, thus significantly improving the triboelectric characteristics of toner. In short, toner is toner precisely because it uses CCA (triboelectric charge control agent).

[0004] Charge control agents are classified into two categories: negative and positive. Among the most widely used charge control agents, negative ones include azo dye metal complexes (e.g., Azo-iron complex T-77) and salicylic acid metal salts (e.g., Zincsalicylate). Positive ones include aniline black (Nigrosine), azine dyes, and aliphatic quaternary ammonium salts (e.g., Quaternary ammonium Salt TP-415).

[0005] However, these commonly used charge control agents still have several aspects that need improvement or unresolved issues. For example, aniline black and metal complexes have poor compatibility and dispersibility. In toner preparation, both physical methods (i.e., melt-pulverization) and chemical methods (such as suspension polymerization and aggregation-fusion) require CCA to be uniformly and stably dispersed in the binder resin in the form of nano-sized particles to obtain high-performance toner products. Organic small molecules such as salicylates and aliphatic quaternary ammonium salts generally do not have strong enough adhesion to the surface of toner particles, making them prone to detachment during printing (especially high-speed printing), resulting in reduced toner performance and deteriorated print quality. Furthermore, substances such as aniline black and dye metal complexes have extremely deep colors, making them unsuitable for color toner preparation. Therefore, there is still significant room for improvement and refinement in charge control materials used for printing / copying toners. Summary of the Invention

[0006] One of the objectives of this invention is to provide a class of positively charged polymeric charge regulators for use in the preparation of developer toners for laser printing and electrostatic copying.

[0007] This invention first provides a functional polymeric compound P3-CCR containing a pyridine tetrafluoroborate salt, as shown in Formula I:

[0008]

[0009] In formula I, R is selected from hydrogen atoms, C 1-20 Alkyl, C 3-20 Cycloalkyl, 3-20 membered heterocyclic groups, C 6-20 Aryl or 5-20 heteroaryl; the C 6-10 Aryl or 5-20 aryl groups can be selectively coated with C. 1-20 Alkyl, C 3-20 Cycloalkyl substitution;

[0010] When R is not H, m is the number of substituents R, which is an integer selected from 1 to 5;

[0011] n is a number between 10 and 100.

[0012] According to an embodiment of the present invention, when R is a substituent other than a hydrogen atom and m is 1 or 2, R can be located at the ortho, meta, or para position of the pyridine structural unit.

[0013] According to an embodiment of the present invention, R is selected from hydrogen atom, C 1-6 Alkyl, C 6-12 Aryl or 5-12 heteroaryl groups;

[0014] n is a number between 30 and 50.

[0015] According to a preferred embodiment of the present invention, R is selected from any one of the following: H, 4-methyl, 3-phenyl or [3,2-b]benzo[n]; n is a number from 35 to 45.

[0016] In one embodiment, the functional polymeric compound containing a tetrafluoroborate pyridine salt of formula I is P3-CCR-H, where n is approximately 40:

[0017]

[0018] The present invention also provides a method for preparing the functional polymer compound P3-CCR containing pyridine tetrafluoroborate as shown in Formula I above, comprising the following steps:

[0019]

[0020] In compounds I-1 and I-3, X is defined the same way and is selected from leaving group halogens; other groups have the same definition as in Formula I as described above.

[0021] S1. Compounds I-1 and I-2 were subjected to a nucleophilic substitution reaction to give compound I-3;

[0022] S2. Compound I-3 undergoes anion exchange reaction with sodium fluoroborate to yield compound I-4;

[0023] S3. Compound I-4 undergoes free radical polymerization to obtain the polymeric compound P3-CCR shown in Formula I.

[0024] According to an embodiment of the present invention, the catalyst used in the free radical polymerization reaction in step S3 is selected from ammonium persulfate (APS).

[0025] According to an embodiment of the present invention, the free radical polymerization reaction in step S3 is carried out in the presence of dodecyl mercaptan and hexadecyltrimethylammonium bromide (CTAB).

[0026] The present invention also provides the application of the functional polymer compound P3-CCR containing pyridine tetrafluoroborate salt as shown in Formula I as a positively charged polymer charge control agent (CCR).

[0027] Specifically, the functional polymer compound P3-CCR containing pyridine tetrafluoroborate as shown in Formula I is used as a positive charge control agent (p-type CCR) in the preparation of developer toner for laser printing and electrostatic copying.

[0028] The present invention also provides a positively charged toner comprising: a binder resin, pigment, wax, a polymeric compound P3-CCR containing pyridine tetrafluoroborate as shown in Formula I as above as a charge control agent, and optionally, an external additive to adjust flowability.

[0029] According to an embodiment of the present invention, the binder resin may be a styrene-acrylate copolymer resin, polyester, or polycarbonate;

[0030] According to an embodiment of the present invention, the pigment may be carbon black, phthalocyanine pigment, pigment red, pigment yellow, etc.

[0031] According to an embodiment of the present invention, the wax includes natural waxes (paraffin wax, carnauba wax, refined wax, etc.) and synthetic waxes (polyethylene wax, polypropylene wax, etc.).

[0032] According to a preferred embodiment of the present invention, the charge control agent is a functional polymeric compound P3-CCR-H containing pyridine tetrafluoroborate salt as shown in Formula I above.

[0033] According to an embodiment of the present invention, the external additive for adjusting fluidity is selected from silica powder or titanium dioxide, etc.

[0034] According to an embodiment of the present invention, the weight ratio of the binder resin, pigment, wax and the pyridine salt containing tetrafluoroborate as shown in Formula I above is (80-120):(5-15):(5-15):(1-20), preferably (90-110):(8-12):(8-12):(4-12).

[0035] The present invention also provides a method for preparing positively charged toner as described above, which is prepared by a traditional physical method, including the following steps: (1) melt mixing: the raw materials, binder resin, pigment, wax, and the polymer compound P3-CCR containing tetrafluoroborate pyridine salt as shown in Formula I above are added to a mixer according to the formula, and then melted, stirred and extruded at high temperature to mix evenly; (2) pulverization: after the mixed material is cooled and pressed into tablets, the tablets are mechanically pulverized to coarse particles with a particle size of 0.5 to 3 mm; (3) fine pulverization and classification collection: the coarse particles are sent to an air jet mill and an ultrafine pulverization and classification system to collect raw powder samples of 5 to 20 μm (D50); optionally, (4) final mixing: an external additive to adjust the flowability is added to obtain the finished product.

[0036] According to an embodiment of the present invention, in step (1), the mixing temperature is 120-170°C, the extrusion rate is 4-10 kg / h, and the mixing time is 1-5 h.

[0037] According to an embodiment of the present invention, in step (3), the pressure of the air jet mill is 0.5 to 1 MPa and the frequency is 20 to 50 Hz.

[0038] According to an embodiment of the present invention, in step (3), the rotational speed of the ultrafine grinding and classification system is 10,000 to 15,000 rpm, and the air volume is 50 to 100 m³ / h. 3 / h.

[0039] Beneficial effects

[0040] The electrical properties of the raw starch sample described in this invention can be determined using the q / m method (charge-to-mass ratio stripping method). By obtaining the two parameters of charging time and charge, the polarity, charging rate, charge, and charge stability of the sample can be analyzed, thereby evaluating and judging the quality of the charge control agent.

[0041] The test results show that the P3-CCR polymeric charge control agent of the present invention has the advantages of fast charging rate, high charge and good charge retention. Its performance is no less than that of the currently commercially available benchmark positive charge control agent dimethyl di(tetradecyl)molybdate ammonium salt, which fully meets the performance requirements of high-speed printing toner. At the same time, the P3-CCR polymeric charge control agent of the present invention is a colorless or nearly colorless solid, which also meets the preparation requirements of color toner.

[0042] Furthermore, based on the structure of the P3-CCR polymer charge control agent of the present invention, it is known that it has good compatibility with polymer binder resin and has certain application prospects. Attached Figure Description

[0043] Figure 1 This is a synthetic route diagram for preparing the polymeric charge control agent P3-CCR-H in Example 1.

[0044] Terminology Definitions and Explanations

[0045] Unless otherwise stated, the definitions of groups and terms recorded in this application specification and claims, including their definitions as examples, exemplary definitions, preferred definitions, definitions recorded in tables, and definitions of specific compounds in the examples, can be arbitrarily combined and combined with each other. Such combinations and combinations of group definitions and compound structures shall fall within the scope of this application specification.

[0046] The numerical ranges described in this application specification and claims, when defined as "integers," should be understood to include the two endpoints of the range and every integer within that range. For example, "integers from 1 to 5" should be understood to include every integer of 1, 2, 3, 4, and 5.

[0047] When a range of values ​​is defined as a "number," it should be understood as including the two endpoints of the range, every integer within the range, and every decimal within the range. For example, "numbers from 10 to 100" should be understood as including not only every integer of 10, 11, 12, 13, 14, 15... and 100, but also at least the sum of each of these integers with 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, and 0.9. Other similar definitions of ranges include "numbers from 30 to 50" and "numbers from 35 to 45."

[0048] Term "C" 1-20 "alkyl" should be understood to refer to a straight or branched saturated monovalent hydrocarbon group having 1 to 20 carbon atoms, preferably C12. 1-10 Alkyl group. "C" 1-10 "alkyl" should be understood to preferably represent a straight-chain or branched saturated monovalent hydrocarbon group having 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, or 1,2-dimethylbutyl, etc., or isomers thereof. In particular, the group has 1, 2, 3, 4, 5, 6, or 10 carbon atoms ("C"). 1-6 Alkyl groups, such as methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl, and more particularly, the groups having 1, 2, or 3 carbon atoms (“C”). 1-3 Alkyl), such as methyl, ethyl, n-propyl or isopropyl.

[0049] Term "C" 3-20 "Cycloalkyl" should be understood to refer to a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3 to 20 carbon atoms, preferably "C". 3-10 cycloalkyl. The term "C" 3-10 "Cycloalkyl" should be understood to refer to a saturated monovalent monocyclic or bicyclic hydrocarbon ring having 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. The C... 3-10 Cycloalkyl groups can be monocyclic hydrocarbon groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl, or bicyclic hydrocarbon groups such as decahydronaphthalene ring.

[0050] The term "3-20 membered heterocyclic group" refers to a saturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1-5 heteroatoms independently selected from N, O, and S, preferably a "3-10 membered heterocyclic group". The term "3-10 membered heterocyclic group" refers to a saturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1-5, preferably 1-3, heteroatoms selected from N, O, and S. The heterocyclic group can be connected to the rest of the molecule via any one of the carbon atoms or a nitrogen atom (if present). Specifically, the heterocyclic group can include, but is not limited to: 4-membered rings, such as azirrobutyl or oxobutyl; 5-membered rings, such as tetrahydrofuranyl, dioxacyclopentenyl, pyrrolyl, imidazoalkyl, pyrazolyl, or pyrrololinyl; or 6-membered rings, such as tetrahydropyranyl, piperidinyl, morpholinyl, dithiaalkyl, thiomorpholinyl, piperazinyl, or trithiaalkyl; or 7-membered rings, such as diazacycloheptyl. Optionally, the heterocyclic group may be benzo-fused. The heterocyclic group may be bicyclic, for example, but not limited to, a 5,5-membered ring, such as a hexahydrocyclopentano[c]pyrrole-2(1H)-yl ring, or a 5,6-membered bicyclic ring, such as a hexahydropyrrolo[1,2-a]pyrazin-2(1H)-yl ring. The nitrogen-containing ring may be partially unsaturated, i.e., it may contain one or more double bonds, for example, but not limited to, 2,5-dihydro-1H-pyrrole, 4H-[1,3,4]thiadiazinyl, 4,5-dihydrooxazolyl, or 4H-[1,4]thiazinyl, or it may be benzo-fused, for example, but not limited to, dihydroisoquinolinyl. According to the invention, the heterocyclic group is non-aromatic.

[0051] Term "C" 6-20 "Aryl" should be understood as representing a monocyclic, bicyclic, or tricyclic hydrocarbon ring with 6 to 20 carbon atoms that is monovalent and partially aromatic, preferably "C". 6-14 Aryl. The term "C" 6-14 "Aryl" should be understood to preferably represent a monovalent aromatic or partially aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring ("C") having 6, 7, 8, 9, 10, 11, 12, 13, or 14 carbon atoms. 6-14 Aryl), particularly a ring with 6 carbon atoms (“C6 aryl”), such as phenyl; or biphenyl, or a ring with 9 carbon atoms (“C9 aryl”), such as indenyl or indenyl, or a ring with 10 carbon atoms (“C9 aryl”). 10 Aryl groups, such as tetrahydronaphthyl, dihydronaphthyl, or naphthyl, or rings with 13 carbon atoms (“C”). 13 Aryl groups, such as fluorene groups, or rings with 14 carbon atoms (“C”). 14 Aryl), for example, anthracene.

[0052] The term "5-20-membered heteroaryl" should be understood to include monovalent monocyclic, bicyclic, or tricyclic aromatic ring systems having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O, and S, such as "5-14-membered heteroaryl". The term "5-14-membered heteroaryl" should also be understood to include monovalent monocyclic, bicyclic, or tricyclic aromatic ring systems having 5, 6, 7, 8, 9, 10, 11, 12, 13, or 14 ring atoms, particularly 5, 6, 9, or 10 carbon atoms, and containing 1 to 5, preferably 1 to 3, heteroatoms independently selected from N, O, and S, and in each case, may be benzofused. Specifically, the heteroaryl group is selected from thienyl, furanyl, pyrroleyl, oxazolyl, thiazolyl, imidazoleyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl, and their benzo[derivatives], such as benzofuranyl, benzothienyl, benzooxazolyl, benzoisooxazolyl, benzoimidazolyl, benzotriazolyl, indazole, indolyl, isindolyl, etc.; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and their benzo[derivatives], such as quinolinyl, quinazolinyl, isoquinolinyl, etc.; or acrylinyl, inazinyl, purinyl, and their benzo[derivatives]; or terpenolyl, phthalazinyl, quinazolinyl, quinoxolinyl, naphridinyl, pteridinyl, carbazolyl, acridineyl, phenazinyl, phenothiazinyl, phenothiazinyl, etc.

[0053] Unless otherwise stated, heterocyclic, heteroaryl, or heteroaryl groups include all their possible isomers, such as their positional isomers. Thus, for some illustrative, non-limiting examples, pyridyl or pyridylene includes pyridin-2-yl, pyridin-2-yl, pyridin-3-yl, pyridin-3-yl, pyridin-4-yl, and pyridin-4-yl; thiophene. Detailed Implementation

[0054] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0055] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0056] Example 1

[0057] The synthetic route of the polymeric charge control agent P3-CCR-H involved in this invention is as follows: Figure 1As shown, the main steps include: using pyridine and 4-vinylbenzyl chloride as starting materials, intermediate compound 1 is obtained through nucleophilic substitution reaction, intermediate compound 2 is obtained through anion exchange reaction, and the target product can be obtained through free radical polymerization reaction of intermediate compound 2.

[0058] Synthesis of 4-vinylbenzylpyridine chloride (compound 1): Pyridine (101.4 mL, 0.72 mol) and 4-vinylbenzyl chloride (57.6 mL, 0.72 mol) were added separately to a 1-liter single-necked round-bottom flask containing 450 mL of acetonitrile; the reaction mixture was stirred overnight (approximately 18 h) at 50 °C. After cooling the reaction mixture, approximately 400 mL of diethyl ether was added with stirring, resulting in the precipitation of a large amount of pale yellow solid; the mixture was filtered under reduced pressure, washed with diethyl ether until the filtrate was colorless, and the filter cake was dried under vacuum at room temperature to obtain 165 g of pale yellow solid powder (yield 99%). Mp 65 °C; 1 ¹H NMR (400MHz, D₂O, ppm): δ 8.88 (d, J = 5.6Hz, 2H), 8.54 (t, J = 7.6Hz, 1H), 8.05 (t, J = 6.4Hz, 2H), 7.32–7.52 (m, 4H), 6.65–6.78 (m, 1H), 5.84 (d, J = 17.6Hz, 1H), 5.76 (s, 2H), 5.35 (d, J = 11.2Hz, 1H). Elemental analysis: Measured values ​​C – 72.09, H – 6.23, N – 6.10, Cl – 14.86; Theoretical values ​​C – 72.57, H – 6.09, N – 6.04, Cl – 15.30.

[0059] Synthesis of 4-vinylbenzylpyridine tetrafluoroborate (compound 2): Compound 1 (82.2 g, 0.36 mol) and sodium fluoroborate (42.0 g, 0.42 mol) were added separately to 500 mL single-necked round-bottom flasks, followed by 360 mL of acetone dried with anhydrous sodium sulfate. The mixture was stirred at room temperature for 2 days. The mixture was filtered under reduced pressure, and the solid was washed repeatedly with acetone. Most of the acetone was removed by rotary evaporation under reduced pressure at room temperature. Then, approximately 300 mL of diethyl ether was added with stirring, and the oily substance gradually solidified into a solid powder. The mixture was filtered under reduced pressure, and the powder was washed with diethyl ether until the filtrate was colorless, yielding 102 g of a nearly white solid powder (100% yield). The melting point of the product was 35–40 °C. 1¹H NMR (400MHz, D₂O, ppm): δ 8.88 (d, J = 6.0Hz, 2H), 8.54 (t, J = 8.0Hz, 1H), 8.05 (t, J = 6.8Hz, 2H), 7.35–7.55 (m, 4H), 6.72–6.85 (m, 1H), 5.88 (d, J = 17.6Hz, 1H), 5.78 (s, 2H), 5.37 (d, J = 11.2Hz, 1H). Elemental analysis: Measured values ​​C–59.00, H–5.42, N–4.37; Theoretical values ​​C–59.40, H–4.99, N–4.95.

[0060] Synthesis of polymer P3-CCR-H: In a 500 mL three-necked flask equipped with a mechanical stirrer and a thermometer, 25 g of intermediate compound 2 and 300 mL of toluene solvent were added, and the mixture was heated to 30 °C with stirring to promote dissolution. Dodecyl mercaptan (0.6 g) was added to the three-necked flask with stirring, and stirring was continued for 5 minutes. Then, hexadecyltrimethylammonium bromide (CTAB) (2 g) was added, and the temperature was gradually increased until the reaction system temperature reached 95 °C. A solution of ammonium persulfate (APS) (0.12 g) and sodium bicarbonate (0.1 g) dissolved in 25 mL of deionized water was added dropwise to 5 mL of the reaction mixture. After stirring and heating for 1 h, the remaining initiator was added dropwise. After the addition was completed, the reaction was stirred at 95 °C overnight. Under mechanical stirring, the hot reaction mixture was slowly poured into 5L of methanol to precipitate the polymerization product; the mixture was filtered under reduced pressure, and the filter cake was washed multiple times with deionized water and methanol; it was then air-dried to obtain 19.5g of the target product (yield 81%) as a nearly colorless solid powder. 1 H NMR (400MHz, CDCl3, ppm): δ6.82-7.20(shoulder,19H); 6.40-6.80(shoulder,10H); 1.70-2.03(br.s,5H); 1.30-1.70(br.s,10H).IR(KBr.cm -1 ):3059,3024,2925,2850,1604,1540,1494,1447,1028,755,702. Tg 70℃; Tf 129℃ (20Kg weighted); Mw=56165Da, Mn=11234, DPI=5. The calculated number of chain segments n is approximately 40.

[0061] Example 2

[0062] In the preparation of the raw starch sample of this invention, styrene-butyl acrylate copolymer resin (Tf 150℃; Sanyo Chemical Co., Ltd., Japan), β-copper phthalocyanine (Ciba Corporation, Japan), and polypropylene wax (Tm) were used. 120℃; Sanyo Chemical Co., Ltd., Japan) and the polymer charge control agent P3-CCR-H prepared in Example 1 were used as the formulation components and prepared according to the following operation steps: (1) According to a certain formula (specifically 100 parts by weight of styrene-butyl acrylate copolymer resin, 10 parts by weight of β-copper phthalocyanine, 10 parts by weight of polypropylene wax and 10 parts by weight of P3-CCR-H), the four components were added to a high-speed mixer and stirred evenly. The mixture was melt-mixed using a mixer (mixing temperature 120–170℃, extrusion rate 4–10kg / h, mixing time 1–5h). The composite was cooled and pressed into sheets, and the sheets were then mechanically crushed to coarse particles with a particle size of 1–2mm; (2) The coarse particle composite was fed into an air jet mill (pressure 0.5–1MPa, frequency 20–50Hz) for crushing, and then transferred to an ultrafine grinding and classification system (speed 10000–15000rpm, air volume 50–100m³ / h). 3 Fractionation was performed at / h, and fractions with D50 of 5–12 μm were collected.

[0063] 100 parts by weight of styrene-butyl acrylate copolymer resin, 10 parts by weight of β-copper phthalocyanine, 10 parts by weight of polypropylene wax, and 10 parts by weight of P3-CCR-H were mixed evenly in a high-speed mixer, then melt-blended in a kneader, cooled, and compressed into sheets. The sheets were first mechanically pulverized into coarse particles, then ultra-finely pulverized in an air jet mill, and finally graded toner raw powder with a D50 of 10 μm was obtained through a classification system. The electrical properties of the samples are shown in Table 1.

[0064] Example 3

[0065] Except for reducing the amount of charge control resin P3-CCR-H to 5 parts by weight, everything else was the same as in Example 2. The electrical properties of the samples are shown in Table 1.

[0066] Comparative Example 1

[0067] Everything was identical to Example 2 except that 10 parts by weight of dimethyl di(tetradecyl)molybdate ammonium salt (trade number TP-415, a commercially available positive charge control reference material, manufactured by Hodogaya Co., Ltd., Japan) were used instead of P3-CCR-H. The electrical properties of the samples are shown in Table 1.

[0068] The triboelectric properties of the raw carbon powder samples were determined using the q / m method (charge-to-mass ratio stripping method). The specific procedure was as follows: 3 parts by weight of the carbon powder sample were mixed with 97 parts by weight of a coated magnetite carrier (Nippon Plasma Materials Co., Ltd.: the coating is a styrene-methacrylate polymer, coating / core ratio 10:90 w / w, average carrier particle size approximately 90 μm). The carbon powder / carrier mixture was then filled into an activation cell (insulating metal) for rolling triboelectric charging. The charge-to-mass ratio was determined using a commercial charge analyzer (TB-200q / m-meter, Toshiba Corporation, Japan). All measurements were performed at 25°C and 50% RH.

[0069] Table 1. Results of charge (μC / g) test on raw toner samples by q / m method

[0070]

[0071]

[0072] The data in Table 1 show that the P3-CCR-H polymeric charge control agent of the present invention has the advantages of fast charging rate, high charge capacity and good charge retention. Its performance is no less than that of the currently commercially available benchmark positive charge control agent, dimethyl di(tetradecyl)molybdate ammonium salt, which fully meets the performance requirements of high-speed printing toner. At the same time, the polymeric charge control agent P3-CCR of the present invention is a colorless or nearly colorless solid, which also meets the preparation requirements of color toner.

[0073] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. Application of P3-CCR, a functional polymer compound containing pyridine tetrafluoroborate salt as shown in Formula I, as a positively charged polymer charge control agent: Formula I in, R is selected from hydrogen atoms or C1-6 alkyl groups; When R is not H, m is the number of substituents R, which is an integer selected from 1 to 5; n is a number between 10 and 100.

2. The application according to claim 1, characterized in that, n is a number between 30 and 50.

3. The application according to claim 1, characterized in that, R is selected from any one of the following: H, 4-methyl; n is a number between 35 and 45.

4. The application according to claim 1, characterized in that, The functional polymer containing pyridine tetrafluoroborate salt shown in Formula I is P3-CCR-H, where n is 40: 。 5. The application according to any one of claims 1-4, characterized in that, The functional polymer P3-CCR containing pyridine tetrafluoroborate salt, as shown in Formula I, was prepared using the following steps: In compounds I-1 and I-3, X is defined in the same way and is selected from leaving group halogens; S1. Compounds I-1 and I-2 were subjected to a nucleophilic substitution reaction to give compound I-3; S2. Compound I-3 undergoes anion exchange reaction with sodium fluoroborate to give compound I-4; S3. Compound I-4 undergoes free radical polymerization to obtain the polymer compound P3-CCR shown in Formula I.

6. The application according to any one of claims 1-4, characterized in that, The functional polymer compound P3-CCR, containing pyridine tetrafluoroborate as shown in Formula I, is used as a positive charge control agent in the preparation of developer toners for laser printing and electrostatic copying.

7. A positively charged toner, comprising: The binder resin, pigment, wax, the polymeric compound P3-CCR containing pyridine tetrafluoroborate as shown in Formula I as a charge control agent, and optionally, external additives to adjust flowability; Formula I Wherein, R is selected from hydrogen atoms or C1-6 alkyl groups; When R is not H, m is the number of substituents R, which is an integer selected from 1 to 5; n is a number between 10 and 100; The binder resin is a styrene-acrylate copolymer resin, polyester, or polycarbonate. The weight ratio of the binder resin, pigment, wax and the polymer compound P3-CCR containing pyridine tetrafluoroborate as shown in Formula I is (80~120):(5~15):(5~15):(1~20).

8. The positively charged toner according to claim 7, characterized in that, The weight ratio of the binder resin, pigment, wax and the tetrafluoroborate pyridine salt shown in Formula I is (90~110):(8~12):(8~12):(4~12).

9. The positively charged toner according to claim 7, characterized in that, The pigment is carbon black, phthalocyanine pigment, pigment red, or pigment yellow.

10. The positively charged toner according to claim 7, characterized in that, The waxes include natural waxes and synthetic waxes.

11. The positively charged toner according to any one of claims 7-10, characterized in that, The external additives used to adjust flowability are selected from silica powder or titanium dioxide.

12. The method for preparing the positively charged toner according to any one of claims 7-11, characterized in that, The preparation is carried out by traditional physical methods, including the following steps: (1) Melt mixing: The raw materials, binder resin, pigment, wax, and the high molecular compound P3-CCR containing tetrafluoroborate pyridine salt as shown in Formula I are added to the mixer according to the formula, and then melted, stirred and extruded at high temperature to mix evenly; (2) Crushing: After the mixed material is cooled and pressed into tablets, the tablets are mechanically crushed to coarse particles with a particle size of 0.5~3mm; (3) Fine crushing and classification collection: The coarse particles are sent to an air jet mill and an ultrafine crushing and classification system to collect raw powder samples with a particle size of 5~20 µm (D50); Optionally, (4) Final mixing: Additives to adjust the flowability are added to obtain the finished product.

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