CN116520653A - Charge regulator and preparation method and application thereof - Google Patents
Charge regulator and preparation method and application thereof Download PDFInfo
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- CN116520653A CN116520653A CN202210080432.2A CN202210080432A CN116520653A CN 116520653 A CN116520653 A CN 116520653A CN 202210080432 A CN202210080432 A CN 202210080432A CN 116520653 A CN116520653 A CN 116520653A
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- compound
- phthalic acid
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- toner
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- -1 phthalic acid compound Chemical class 0.000 claims abstract description 46
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 238000007648 laser printing Methods 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 6
- 150000003022 phthalic acids Chemical class 0.000 claims abstract 3
- 150000001875 compounds Chemical class 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000001993 wax Substances 0.000 claims description 15
- 239000000049 pigment Substances 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- HGBOETXLQQDHKI-UHFFFAOYSA-N C1(=CC=CC=C1)C1=C(C(C(=O)O)=CC(=C1)C1=CC=CC=C1)C(=O)O Chemical compound C1(=CC=CC=C1)C1=C(C(C(=O)O)=CC(=C1)C1=CC=CC=C1)C(=O)O HGBOETXLQQDHKI-UHFFFAOYSA-N 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical group [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical group [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000007514 bases Chemical class 0.000 claims description 2
- 229910001424 calcium ion Chemical group 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Chemical group 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 238000013459 approach Methods 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract description 2
- 238000003303 reheating Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XGCDBGRZEKYHNV-UHFFFAOYSA-N 1,1-bis(diphenylphosphino)methane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CP(C=1C=CC=CC=1)C1=CC=CC=C1 XGCDBGRZEKYHNV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- VHILMKFSCRWWIJ-UHFFFAOYSA-N dimethyl acetylenedicarboxylate Chemical compound COC(=O)C#CC(=O)OC VHILMKFSCRWWIJ-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 108091008695 photoreceptors Proteins 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N dimethyl benzenedicarboxylate Natural products COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 description 1
- 125000005918 1,2-dimethylbutyl group Chemical group 0.000 description 1
- 125000006218 1-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006176 2-ethylbutyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(C([H])([H])*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000003542 3-methylbutan-2-yl group Chemical group [H]C([H])([H])C([H])(*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- BPOZNMOEPOHHSC-UHFFFAOYSA-N butyl prop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCOC(=O)C=C BPOZNMOEPOHHSC-UHFFFAOYSA-N 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000003538 pentan-3-yl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09733—Organic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09733—Organic compounds
- G03G9/0975—Organic compounds anionic
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
The invention discloses a charge regulator, a preparation method and application thereof, wherein the charge regulator comprises phthalic acid compounds with structures shown in the following formula I. The charge regulator (i.e. phthalic acid compound with the structure shown in the formula I) has excellent durability and stable charge quantity under different temperatures and humidity. The charge regulator is used for preparing the toner, and the pH value of the solution is regulated to induce particles to approach each other and gradually converge into clusters; reheating to grow clusters, limiting further growth when the required size is reached; heating above the Tg temperature of the resin to promote the loose clusters to be bonded to form compact-structure granules; collecting, drying, and adding other necessary components to obtain the toner. The toner of the invention has fast electrification rate, high charge, and the like, and various performance indexes meet the use requirements of monochromatic/color laser printing.
Description
Technical Field
The invention belongs to the technical field of preparation of ink powder; in particular to a charge regulator, a preparation method and application thereof.
Background
Toner (Toner), also known as Toner, electrostatic developer, is a powdered solid for electrostatic imaging that forms a developer with a carrier, participates in the development process, and is ultimately fixed to paper to form text or images. The toner is mainly composed of resin, colorant, charge regulator, auxiliary additive, etc. Charge control agents (charge control agent, CCA) are a class of substances that function to control the charge level of toner in xerography and printing. In printing or copying, an electrostatic latent image is usually formed on a photoreceptor made of a photosensitive material, and then reversely developed with a toner, and transferred to a carrier such as paper to be fixed to obtain a visible image. The photoreceptor is a core member in a developing apparatus, and is classified into a positive type and a negative type according to the structure, and toner is required to be developed on an electrostatic latent image formed on the photoreceptor, and to be charged with an opposite electric charge to the latent image. The charge control agent plays a role in changing the triboelectric charging characteristics of the toner and determining the charging rate at the time of friction, concentrating the toner charge amount distribution, and enabling the toner to perform copying and printing.
Traditional negative charge regulators comprise azo metal complex series and tert-butyl salicylic acid metal complex series, but the compounds are unevenly dispersed in resin and are easy to decompose at high temperature, so that after the charge regulator is added into toner, the charge regulator cannot have a faster electrification rate in actual printing, and the printing effect is affected.
Disclosure of Invention
The invention discloses a phthalic acid compound, which has the advantages of simple synthesis, good stability, good solubility, good resin compatibility and the like.
The technical scheme of the invention is as follows:
a phthalic acid compound of the structure shown in the following formula I:
wherein R is unsubstituted or substituted by one, two or more C 1-20 Alkyl-substituted phenyl, M is zinc, chromium, aluminum or calcium ion; x is an integer of 1 to 3; y is an integer of 1 to 3;
represents a benzene ring;
2R are positioned at ortho, para or meta positions of the benzene ring; preferably in the meta-position.
According to an embodiment of the invention, said R is preferably unsubstituted or substituted by one, two or more C 1-6 Alkyl substituted phenyl, more preferably phenyl.
According to an embodiment of the invention, said M is preferably a zinc ion or an aluminum ion.
According to an exemplary embodiment of the present invention, the phthalic acid-based compound is CCA-Al or CCa-Zn as shown below;
the invention also provides a preparation method of the phthalic acid compound with the structure shown in the formula I, which comprises the following steps:
mixing a compound of a formula A, an M-containing compound and an alkaline solution to prepare a phthalic acid compound with a structure shown in a formula I;
wherein R has the meaning as above.
According to an embodiment of the invention, the compound of formula a is for example 3, 5-diphenyl phthalic acid.
According to an embodiment of the present invention, the M-containing compound may be at least one of zinc chloride, aluminum nitrate, calcium chloride, chromium chloride.
According to an embodiment of the present invention, the alkaline solution is an aqueous alkaline compound solution, and the alkaline compound may be sodium hydroxide or potassium hydroxide; the mass concentration of the alkaline compound in the alkaline solution is 1 to 5wt%, and is exemplified by 2wt%.
According to an embodiment of the present invention, the molar ratio of the M-containing compound, the compound of formula A, the basic compound is 1 (1-4): 1-10, preferably 1 (1-3): 2-6, and exemplary is 1:1.8:4.
According to an embodiment of the invention, the time for the reaction of the respective starting materials is 24 to 60 hours, and is exemplified by 48 hours.
According to an embodiment of the invention, the preparation method further comprises adjusting the prepared product to be acidic, with an exemplary pH of 3, for example with 5% dilute hydrochloric acid.
According to an embodiment of the present invention, the preparation method further comprises: dispersing the phthalic acid compound with the structure shown in the formula I in deionized water containing a dispersing agent to obtain phthalic acid compound dispersion liquid with the structure shown in the formula I.
According to an embodiment of the present invention, the dispersant is at least one selected from the group consisting of sodium polyacrylate, poly-butyl acrylate copolymer, S-27000, sodium dodecylbenzenesulfonate.
According to an embodiment of the present invention, the phthalic acid compound dispersion can exist stably under alkaline conditions, and preferably the phthalic acid compound dispersion is an emulsion and can be demulsified and precipitated under acidic conditions, with the addition of calcium chloride, or the like.
The invention also provides application of the phthalic acid compound with the structure shown in the formula I as an electronegative charge regulator (CCA).
Illustratively, the phthalic acid compound of the structure shown in formula I is used as an electronegative charge regulator (CCA) to be applied to the preparation of developer toner for laser printing or electrostatic copying.
The invention also provides a toner, and the preparation raw materials of the toner comprise phthalic acid compounds with the structure shown in the formula I; preferably comprises phthalic acid compound, wax, resin and pigment with the structure shown in the formula I.
According to an embodiment of the present invention, in the toner, the phthalic acid compound of the structure shown in formula I may be a phthalic acid compound dispersion of the structure shown in formula I.
According to an embodiment of the present invention, the wax includes natural waxes (paraffin wax, palm wax, spermatid wax, etc.) and synthetic waxes (polyethylene wax, polypropylene wax, etc.).
According to an embodiment of the present invention, the resin may be a styrene-propylene ester copolymer resin, a polyester, or a polycarbonate.
According to an embodiment of the present invention, the pigment may be carbon black, pigment yellow, pigment cyan, or the like.
According to the embodiment of the invention, the mass ratio of the phthalic acid compound, wax, resin and pigment with the structure shown in the formula I is (1-10): (1-20): (60-100): (5-30), preferably (1-5): (5-10): (60-90): (10-20).
The invention also provides a preparation method of the toner, which comprises the following steps:
(1) Mixing phthalic acid compound with a structure shown in formula I, wax, resin and pigment, adjusting the mixed solution to be acidic, and heating;
(2) And (3) regulating the mixed solution in the step (1) to be alkaline, and heating to prepare the toner.
According to an embodiment of the present invention, in step (1), the phthalic acid compound of the structure represented by formula I, the wax, the resin and the pigment are all introduced in the form of their dispersion.
Preferably, the step (1) comprises mixing the aqueous dispersion of the phthalic acid compound of the structure shown in formula I, wax emulsion, resin emulsion, pigment aqueous dispersion, adjusting the mixed solution to be acidic, and heating.
According to an embodiment of the invention, in step (1), the pH of the mixed solution is 2-4.
According to an embodiment of the invention, in step (1), the heating temperature is 40-60 ℃, preferably 50-60 ℃; the heating time is 0.5-5h, preferably 1-3h.
According to an embodiment of the invention, in step (2), the pH of the mixed solution is 8-10.
According to an embodiment of the invention, in step (2), the heating temperature is 80-110 ℃, preferably 90-100 ℃; the heating time is 1-6 hours, preferably 3-5 hours.
According to the embodiment of the invention, the preparation method of the toner further comprises a post-treatment step (3), and the toner is prepared by filtering, washing and drying the product obtained in the step (2).
The invention has the beneficial effects that:
the charge regulator (i.e. phthalic acid compound with the structure shown in the formula I) has excellent durability and stable charge quantity under different temperatures and humidity. The charge regulator is used for preparing the toner, and the pH value of the solution is regulated to induce particles to approach each other and gradually converge into clusters; reheating to grow clusters, limiting further growth when the required size is reached; heating above the Tg temperature of the resin to promote the loose clusters to be bonded to form compact-structure granules; collecting, drying, and adding other necessary components to obtain the toner. The toner of the invention has fast electrification rate, high charge, and the like, and various performance indexes meet the use requirements of monochromatic/color laser printing.
Definition and description of terms
Unless otherwise indicated, the terms and descriptions in the context of the present invention have the meanings set forth below.
More means 3 or more.
The term "C 1-20 Alkyl "is understood to mean a straight-chain or branched saturated monovalent hydrocarbon radical having from 1 to 20 carbon atoms. For example, "C 1-10 Alkyl "means straight-chain and branched alkyl having 1,2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms," C 1-6 Alkyl "means straight and branched alkyl groups having 1,2, 3, 4, 5 or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3-dimethylbutyl, 2-dimethylbutyl, 1-dimethylbutyl, 2, 3-dimethylbutyl, 1, 3-dimethylbutyl, or 1, 2-dimethylbutyl, or the like, or an isomer thereof.
Drawings
FIG. 1 is a synthetic route to 3, 5-diphenylphthalic acid.
Detailed Description
According to an embodiment of the present invention, the process for the preparation of a compound precursor of formula I (e.g. 3, 5-diphenyl phthalic acid) comprises the steps of:
(S1) Ni (PPh) 3 ) 2 Cl 2 Mixing dppm, zinc powder, zinc iodide, dimethyl butynedioate, phenylacetylene and an organic solvent, and heating for reaction to prepare 3, 5-diphenyl dimethyl phthalate;
(S2) reacting dimethyl 3, 5-diphenyl phthalate under alkaline conditions to prepare the 3, 5-diphenyl phthalate.
According to an embodiment of the present invention, ni (PPh 3 ) 2 Cl 2 The mole ratio of dppm, zinc powder, zinc iodide, dimethyl butynedioate and phenylacetylene is 1:1 (1-2): (1-2): (8-20): (20-40), and the exemplary ratio is 1:1:2:2:10:30.
According to an embodiment of the present invention, the organic solvent is illustratively acetonitrile.
According to an embodiment of the present invention, in step (S1), the heating temperature is 60 to 90 ℃, and is exemplified by 80 ℃; the heating reaction is carried out for a period of 5 to 8 hours, and is exemplified by 6 hours.
According to an embodiment of the present invention, in step (S2), the alkaline condition is, for example, a methanol solution of sodium hydroxide; illustratively, the concentration of sodium hydroxide is 2M.
According to an embodiment of the present invention, in step (S2), the reaction time is 12 to 48 hours, and is exemplified by 24 hours.
According to an embodiment of the present invention, in the step (S2), after the reaction is completed, the pH is adjusted to 1 to 2 with an acid; illustratively, the adjustment is performed using dilute hydrochloric acid.
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Preparation example 1
The synthetic route of 3, 5-diphenyl phthalic acid is shown in figure 1.
Synthesis of dimethyl 3, 5-diphenylphthalate: into a 250mL three-necked flask, 6.6 g (10 mmol) of Ni (PPh) 3 ) 2 Cl 2 3.9 g (10 mmol) dppm, 1.3 g (20 mmol) zinc powder, 6.4 g (20 mmol) zinc iodide; firstly, vacuumizing and then introducing nitrogen, repeating the operation for three times, dissolving 14.2 g (100 mmol) of dimethyl butynedioate and 30.6 g (300 mmol) of phenylacetylene in 120mL of acetonitrile, and adding the mixture into a three-necked flask under the protection of nitrogen; the reaction is carried out at 80 ℃ for 6 hours, after the reaction is finished, the reaction is cooled to room temperature, the organic solvent is distilled off under reduced pressure after the filtration, and the mixture in the reaction liquid is separated and purified by column chromatography, thus obtaining 24.3 g (yield 70%) of the target product of 3, 5-diphenyl dimethyl phthalate. 1 H NMR(400MHz,CDCl 3 ):δ8.23(d,J＝1.2Hz,1H),7.77(d,J＝1.2Hz,1H),7.64(d,J＝7.4Hz,2H),7.49–7.39(m,8H),3.94(s,3H),3.69(s,3H)； 13 C NMR(100MHz,CDCl 3 ):δ169.20,166.22,142.24,141.24,139.33,139.12,133.40,132.67,129.02,128.87,128.64,128.34,128.30,127.98,127.49,127.24,52.65,52.31；MS(EI,m/z,rel.％):346(M + ,46％),315(M + -31,89％).
Synthesis of 3, 5-diphenyl phthalic acid: dimethyl 3, 5-diphenylphthalate (18.7 g,54 mmol) was dissolved in 2M in 250ml of sodium hydroxide in methanol, refluxed for 24 hours, cooled, methanol was removed under reduced pressure, and the pH was adjusted to 1-2 with dilute hydrochloric acid. The precipitate was filtered, washed and dried to give 3, 5-diphenylphthalic acid (i.e., CCA precursor) (15.5 g, 90%), melting point: 196-197 ℃.
Preparation example 2
Preparation of CCA-Zn: zinc chloride (3.4 g,25 mmol), 3, 5-diphenylphthalic acid (14.3 g,45 mmol) from preparation 1 and 2wt% sodium hydroxide in water were refluxed for 48 hours, cooled to room temperature and brought to pH 3 with 5% dilute hydrochloric acid. Filtering, washing and drying the precipitate to obtain CCA-Zn, namely phthalic acid compound with a structure shown in a formula I, wherein X, Y is 2.
Preparation example 3
Preparation of CCA-Al: 200mL of an aqueous solution of aluminum nitrate (4.3 g,20 mmol), 3, 5-diphenylphthalic acid (14.3 g,45 mmol) of preparation example 1 and 2wt% sodium hydroxide was refluxed for 48 hours, cooled to room temperature, and adjusted to pH 3 with 5% dilute hydrochloric acid. Filtering, washing and drying the precipitate to obtain CCA-Al, namely the phthalic acid compound with the structure shown in the formula I, wherein X, Y is 2 and 1 respectively.
Preparation example 4
Preparation of CCA-Zn dispersion: in a 500 ml ball milling pot containing zirconium beads, add 175 ml of deionized water containing 2 g sodium polyacrylate and 3g S-27000, 20 g CCA-Zn of example 2, stir (500 rpm) for 0.5 hours and mix well; ball milling at 5000rpm for 3 hours gave a stable CCA-Zn dispersion (particle size 100nm, solids 10 wt.%).
Preparation example 5
Preparation of the CCA-Al dispersion: in a 500 ml ball milling pot containing zirconium beads, adding 175 ml of deionized water containing 2 g of the poly (acrylic acid-butyl acrylate) copolymer and 3g of sodium dodecyl benzene sulfonate of CCA-Al in example 3 and 40 g, stirring (500 rpm) for 0.5 hour and uniformly mixing; ball milling at 5000rpm for 2 hours gave a stable CCA-Al dispersion (particle size 110nm, solids content 20 wt.%).
Example 1 (preparation of black toner):
in a 500 ml pressure reaction kettle, adding the CCA-Zn water-based dispersion liquid (5 g, 10 wt.%), wax emulsion (15 g,20 wt.%), styrene-acrylate emulsion (150 g,20 wt.%) and carbon black water-based dispersion liquid (40 g, 15 wt.%), which are prepared in the preparation example 4, and adding 100 g of deionized water containing 1 g of sodium dodecyl benzene sulfonate, and uniformly mixing and stirring; regulating the pH value of the system to 3, heating to 50-60 ℃, strongly stirring (2000-5000 rpm) for 1-3 hours, regulating the pH value to 9, raising the temperature to 95 ℃ and stirring for 3-5 hours; cooling, filtering, washing and drying to obtain powdered ink (the powder particles are nearly spherical and the size is 6-10 mu m). And adding an external silica additive component which is 2% of the mass of the toner and is a fluidity enhancer, so as to obtain the black toner suitable for laser printing.
The method and procedure of example 1 above were used to replace the black pigment dispersion with yellow, magenta and cyan pigment dispersions, respectively (the specific various material ratios can be adjusted by means conventional in the art) to obtain yellow, magenta and cyan toners suitable for color laser printing.
Example 2
The procedure was the same as in example 1 except that CCA-Zn was replaced with the charge regulator CCA-Al in preparation example 5.
Comparative example 1
The procedure was the same as in example 1, except that the charge regulator CCA-Zn was not used.
Comparative example 2
The procedure was as in example 1, except that the charge regulator DL-N24, which was widely used in industry, was used instead of CCA-Zn.
The charge amount was measured by a standard blowing method, and the electrical properties of the toners of examples 1-2 and comparative examples 1-2 are shown in tables 1 and 2.
TABLE 1 results of measurement of the charge amount of the toners in examples 1-2 and comparative examples 1-2 over time
TABLE 2 environmental stability parameter Table for toners in examples 1-2 and comparative examples 1-2
As can be seen from the data in tables 1 and 2, the electrical performance parameters of the toners (especially example 1) prepared according to the present invention are relatively stable within the composition and formulation ranges of the present invention; the quality evaluation of the sample manuscript printed by the real machine basically meets the standard requirement. The test data for comparative examples 1-2 in tables 1 and 2 indicate that: the toner without charge regulator has poor electrification speed, electrification amount, stability and environmental experiment; meanwhile, the charge regulator of the invention is superior to the charge regulator DL-N24 widely applied in industry.
The embodiments of the present invention have been described above by way of example. However, the scope of the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc. made by those skilled in the art, which fall within the spirit and principles of the present invention, are intended to be included within the scope of the present invention.
Claims (10)
1. A phthalic acid compound of the structure shown in the following formula I:
wherein R is unsubstituted or substituted by one, two or more C 1-20 Alkyl-substituted phenyl, M is zinc, chromium, aluminum or calcium ion; x is an integer of 1 to 3; y is an integer of 1 to 3;
represents benzeneA ring;
2R are located in ortho, para or meta positions of the benzene ring.
2. The compound of claim 1, wherein R is unsubstituted or substituted with one, two or more C 1-6 Alkyl substituted phenyl, more preferably phenyl.
Preferably, 2R are located meta to the benzene ring.
Preferably, the M is zinc ion or aluminum ion.
3. A compound according to claim 1 or 2, wherein the phthalic acid compound is CCA-Al or CCa-Zn as shown below;
4. a process for the preparation of a phthalic acid compound of the structure according to any one of claims 1 to 3, characterized in that it comprises the following steps:
mixing a compound of a formula A, an M-containing compound and an alkaline solution to prepare a phthalic acid compound with a structure shown in a formula I;
5. the method of claim 4, wherein the alkaline solution is an aqueous alkaline compound solution, and the alkaline compound is sodium hydroxide, and/or potassium hydroxide; the mass concentration of the alkaline compound in the alkaline solution is 1-5wt%.
Preferably, the molar ratio of the M-containing compound, the compound of formula A and the basic compound is 1 (1-4): 1-10.
6. The process according to claim 4 or 5, wherein the compound of formula a is 3, 5-diphenyl phthalic acid.
Preferably, the M-containing compound is at least one of zinc chloride, aluminum nitrate, calcium chloride and chromium chloride.
7. The method of any one of claims 4-6, wherein the method of preparing further comprises: dispersing the phthalic acid compound with the structure shown in the formula I in deionized water containing a dispersing agent to obtain phthalic acid compound dispersion liquid with the structure shown in the formula I.
Preferably, the dispersing agent is at least one selected from sodium polyacrylate, poly-butyl acrylate copolymer, S-27000 and sodium dodecyl benzene sulfonate.
Preferably, the phthalic compound dispersion is stable under alkaline conditions and can be demulsified out in the presence of acid or added calcium chloride.
8. Use of a phthalic acid compound of the structure of formula I according to any one of claims 1 to 3 as a electronegative charge regulator (CCA).
Preferably, the process is used for preparing developer toner for laser printing and electrostatic copying.
9. A toner, wherein the raw materials for preparing the toner comprise phthalic acid compounds with the structure shown in the formula I as defined in any one of claims 1-3;
preferably, the raw materials for preparing the toner comprise phthalic acid compounds with the structure shown in the formula I, wax, resin and pigment.
Preferably, in the toner, the phthalic acid compound with the structure shown in the formula I is phthalic acid compound dispersion liquid with the structure shown in the formula I.
Preferably, the mass ratio of the phthalic acid compound, the wax, the resin and the pigment is (1-10): (1-20): (60-100): (5-30), preferably (1-5): (5-10): (60-90): (10-20).
10. A method of preparing toner as claimed in claim 9, wherein the method comprises:
(1) Mixing phthalic acid compound with a structure shown in formula I, wax, resin and pigment, adjusting the mixed solution to be acidic, and heating;
(2) And (3) regulating the mixed solution in the step (1) to be alkaline, and heating to prepare the toner.
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