Bonding resin for toner, toner and electrostatic charge image developer

Abstract

The invention discloses a bonding resin for a toner, which is obtained by condensation polymerization of a bisphenol compound, aliphatic dihydric alcohol, dicarboxylic acid, a compound as shown in a formula (1) and a salt thereof, and the compound as shown in the formula (1) is as shown in the specification: # imgabs0 #, in the formula (1), R1, R2 and R3 are respectively and independently alkyl groups or alkoxy groups or alkyl ester groups with the hydrogen atom number of 1-10 and the carbon atom number of 1-10. The resin provided by the invention has an improved glass transition temperature and a reduced softening point temperature, and can improve the storage performance and low-temperature fixing performance of a toner.

Description

Technical Field

[0001] The present invention relates to the field of printing and copying developers, and more particularly to a binder resin for toner, toner and electrostatic charge image developer. Background Art

[0002] Toner is a key consumable used in the field of laser printing and digital copying, and its preparation methods are divided into physical and chemical methods. Toners prepared by chemical methods are mainly composed of binder resins, pigments, additives, waxes, etc. Among them, binder resins usually include styrene / acrylic resins and polyester resins. The main advantage of polyester resins over styrene / acrylic resins is that they have better color rendering and light transmittance, but their preservation, hygroscopicity and fixing properties are often weaker. Therefore, these factors must be considered during the research and development of polyester resins. Summary of the invention

[0003] An object of the present invention is to solve at least the above problems and to provide at least the advantages which will be described hereinafter.

[0004] Still another object of the present invention is to provide a binder resin for toner having an increased glass transition temperature and a decreased softening point, thereby improving the storage performance and low-temperature fixing performance of the toner.

[0005] In order to achieve these objects and other advantages according to the present invention, the present invention provides a binder resin for toner, which comprises a bisphenol compound, an aliphatic diol, a dicarboxylic acid and a compound represented by formula (1) and a salt thereof, wherein the compound represented by formula (1) is:

[0006]

[0007] In formula (1), R1, R2 and R3 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group.

[0008] Preferably, the glass transition temperature T g The softening temperature of the adhesive resin is 50 to 70°C. 1 / 2 It is 80~98℃.

[0009] Preferably, R2 is an alkyl ester group having 1 to 10 carbon atoms.

[0010] Preferably, it comprises 1 to 1.8 mole parts of a bisphenol compound, 1 to 1.2 mole parts of an aliphatic diol, 1 to 3 mole parts of a dicarboxylic acid, and 0.018 to 0.022 mole parts of a compound represented by formula (1) and a salt thereof.

[0011] Preferably, the dicarboxylic acid comprises an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid, and the molar ratio of the aromatic dicarboxylic acid to the aliphatic dicarboxylic acid is 1:(5-8).

[0012] Preferably, 1 to 1.8 mole parts of bisphenol compound, 1 to 1.2 mole parts of aliphatic diol, 1 to 3 mole parts of dicarboxylic acid, 0.018 to 0.022 mole parts of the compound represented by formula (1) and its salt, and 0.001 to 0.002 mole parts of catalyst are added to a container, polycondensed at 160 to 180° C. for 6 to 10 hours, and then polycondensed under vacuum conditions for 2 to 4 hours to obtain a binder resin having a molecular weight M of the binder resin. w 20000~60000, T g 50~70℃, T 1 / 2 The temperature is 80-98°C, and the acid value is 10-25 mg KOH / g.

[0013] The present invention provides a toner for developing an electrostatic charge image, comprising a binder resin for the toner.

[0014] Preferably, an external additive is included, wherein the density of the silanol groups in the surface is 4.5 / nm 2 The following silica particles.

[0015] Preferably, the content of the external additive is 0.3-5 wt %.

[0016] Preferably, the external additive is obtained by reacting an alkyl or alkoxy compound having an amine group with a siloxane compound, and then further reacting with a siloxane compound and a siloxane compound having an amine group.

[0017] The present invention provides an electrostatic charge image developer, including a toner for developing an electrostatic charge image.

[0018] The present invention has at least the following beneficial effects:

[0019] 1. In the present invention, the pyrene unit with a multi-benzene ring structure is introduced to effectively increase the glass transition temperature Tg of the resin. At the same time, due to the sulfonic acid structure, it is easy to form intramolecular hydrogen bonds, thereby reducing the softening temperature Tg of the resin. 1 / 2 , while improving the toner's preservation performance, it also gives the toner low-temperature fixing performance.

[0020] 2. In the present invention, using a smaller amount of aromatic dicarboxylic acid in the dicarboxylic acid compound can lower the softening temperature of the adhesive resin.

[0021] 3. In the present invention, the density of silanol groups added to the surface of the toner is 4.5 / nm 2The following modified silica particles can be used as external additives to increase the fixing strength of the toner.

[0022] Other advantages, objectives and features of the present invention will be embodied in part through the following description, and in part will be understood by those skilled in the art through study and practice of the present invention. DETAILED DESCRIPTION

[0023] The present invention provides a binder resin for a toner, a toner and an electrostatic charge image developer, and the present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, but not to limit the present invention. Other combinations and various improvements within the concept of the present invention may be made without departing from the gist or scope of the present invention.

[0024] <Binder Resin for Toner>

[0025] The first aspect of the present invention provides a binder resin for toner, which is obtained by polycondensation of a bisphenol compound, an aliphatic diol, a dicarboxylic acid, and a compound represented by formula (1) and a salt thereof.

[0026] In some embodiments of the present invention, the compound represented by formula (1) is as follows:

[0027]

[0028] In formula (1), R1, R2, and R3 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or an alkyl ester group; R2 is preferably a hydrogen atom or an alkyl ester group having 1 to 10 carbon atoms.

[0029] The compound represented by formula (1) and its salt may be, for example, compound A and compound B as shown below:

[0030]

[0031] The structure shown in formula (1) mainly plays a cross-linking role. The sulfonic acid group shown in formula (1) combines with the hydroxyl group to form a branched polymer. In the polycondensation process, the pyrene unit with a multi-benzene ring structure is introduced as a cross-linking agent, which effectively increases the glass transition temperature T of the adhesive resin. g , which improves the heat-resistant storage stability of the toner. At the same time, due to the sulfonic acid structure, it is easy to form intramolecular hydrogen bonds, which reduces the softening temperature T of the binding resin. 1 / 2 Therefore, the toner's preservation is improved while the final low-temperature fixing performance is taken into account. The toner has good preservation under relatively high temperature conditions, the toner has weak density decay during continuous printing, and the waste toner rate will not increase.

[0032] In some embodiments of the present invention, the bisphenol compound includes one or more of bisphenol A, bisphenol S, bisphenol F, hydroquinone, resorcinol, dihydroxybenzophenone, dihydroxydiphenyl ether, 4,4′-biphenol, hexafluorobisphenol A, tetrabromobisphenol A, and dihydroxynaphthalene.

[0033] In some embodiments of the present invention, the aliphatic diols may include: aliphatic diols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol and glycerol; alicyclic diols such as cyclohexanediol, cyclohexanedimethanol and hydrogenated bisphenol A; and aromatic diols such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol and 1,14-eicosanoid.

[0034] In some embodiments of the present invention, the dicarboxylic acid compound includes aromatic dicarboxylic acids and aliphatic dicarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, tert-butylisophthalic acid, tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, p-carboxyphenylacetic acid, terephthalic acid, isophenylene glycolic acid, p-phenylene glycolic acid, o-phenylene glycolic acid, diphenylacetic acid, 4,4'-biphenyl dicarboxylic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, anthracene dicarboxylic acid, 1,2-dicarboxylic acid, 1,6-dicarboxylic acid, 1,2 ... Carboxylic acid, cyclohexane dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, hexahydroterephthalic acid, etc.; aliphatic dicarboxylic acids such as maleic anhydride, succinic anhydride, acetic anhydride, propionic anhydride, caronic anhydride, alkenyl succinic anhydride, oxalic acid, glutaric acid, succinic acid, maleic acid, adipic acid, β-methyl adipic acid, azelaic acid, sebacic acid, nonane dicarboxylic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-carboxylic acid, malic acid, citric acid, hexahydroterephthalic acid, malonic acid, pimelic acid, tartaric acid. Preferably, the molar ratio of the aromatic carboxylic acid to the aliphatic dicarboxylic acid is 1:(5-8). Using a smaller amount of aromatic dicarboxylic acid in the dicarboxylic acid compound can reduce the softening temperature of the adhesive resin.

[0035] In some embodiments of the present invention, the binder resin for toner includes 1 to 1.8 mole parts of bisphenol compounds, 1 to 1.2 mole parts of aliphatic diols, 1 to 3 mole parts of dicarboxylic acids, and 0.018 to 0.022 mole parts of the compound represented by formula (1) and its salt.

[0036] In some embodiments of the present invention, the preparation method of the binder resin for colorant is as follows: 1 to 1.8 mole parts of bisphenol compounds, 1 to 1.2 mole parts of aliphatic diols, 1 to 3 mole parts of dicarboxylic acids, 0.018 to 0.022 mole parts of the compound represented by formula (1) and its salt, and 0.001 to 0.002 mole parts of a catalyst are added to a container, polycondensed at 160 to 180° C. for 6 to 10 hours, and then polycondensed under vacuum conditions for 2 to 4 hours to obtain a binder resin, wherein the molecular weight Mw of the binder resin is controlled to be 20,000 to 60,000, and the acid value is 10 to 25 mg KOH / g.

[0037] The catalyst is selected from any one or more of tin catalysts, titanium catalysts, germanium catalysts, antimony catalysts, zinc catalysts or manganese catalysts. Suitable tin catalysts can be selected from any one or more of dibutyltin dichloride, dibutyltin oxide or diphenyltin oxide; suitable titanium catalysts can be selected from any one or more of isopropyl titanate, tetrabutyl titanate or tetrabutoxytitanium; suitable germanium catalysts can be selected from germanium dioxide; suitable antimony catalysts can be selected from any one or more of ethylene glycol antimony, antimony trioxide or antimony triacetate; suitable zinc catalysts can be selected from any one or more of zinc acetate, zinc lactate, zinc nitrate or zinc citrate; suitable manganese catalysts can be selected from any one or more of manganese acetate, manganese oxide, manganese dichloride or manganese glycol.

[0038] In some embodiments of the present invention, the glass transition temperature Tg of the adhesive resin is 50 to 70°C, preferably 55 to 70°C, and more preferably 60 to 70°C. 1 / 2 It is 80 to 98°C, preferably 80 to 95°C, more preferably 85 to 95°C.

[0039] <Toner>

[0040] A second aspect of the present invention provides a toner for developing electrostatic charge images, comprising the toner binder resin provided in the first aspect, a colorant dispersion, a wax dispersion, and an external additive.

[0041] The colorant dispersion includes a colorant, a surfactant and deionized water, which is obtained by mixing and stirring the colorant, the surfactant and the deionized water in a homogenizer. The colorant is selected from any one or a combination of inorganic pigments, organic pigments or organic dyes. Cyan colorants include pigment blue 15:3, pigment blue 15:4, etc.; yellow colorants include pigment yellow 74, pigment yellow 93, pigment yellow 94, pigment yellow 155, solvent yellow 162, pigment yellow 180, pigment yellow 185, etc.; magenta colorants include pigment red 31, pigment red 122, pigment red 150, pigment red 184, pigment red 185, pigment red 57:1, pigment red 238, pigment red 269, etc.; black colorants include carbon black, magnetite, etc. The solid content of the colorant dispersion is 10-50wt%, preferably 10-40wt%, more preferably 10-20wt%, etc.

[0042] The content of the colorant in the toner is 2 parts by mass to 15 parts by mass based on 100 parts by mass of the polyester resin in the toner.

[0043] The wax dispersion comprises wax, surfactant and deionized water, and is obtained by mixing and stirring the wax, surfactant and deionized water in a homogenizer. The wax can be hydrocarbon wax such as low molecular weight polyethylene wax, maleic anhydride modified polyethylene wax, low molecular weight polypropylene wax, low molecular weight copolymerized olefin wax, oxidized paraffin, paraffin, micro wax, natural wax such as octadecyl octadecyl, behenyl octadecyl, beeswax, carnauba wax, higher fatty amide such as oleic acid amide or stearic acid amide, etc. The solid content is 10-50wt%, preferably 10-40wt%, more preferably 10-20wt%.

[0044] The wax content in the toner is 2 to 15 parts by mass relative to 100 parts by mass of the polyester resin in the toner. The wax particle size in the wax dispersion is ≤ 1 micron, preferably 100 to 500 nm.

[0045] The surfactants in the colorant dispersion and the wax dispersion are the same or different, preferably the same compounds. They are selected from at least one or more combinations of carboxylates, sulfonates, sulfate esters and structured mixed surfactants. Examples include: fatty alcohol polyoxyethylene ether carboxylates, sodium stearate, linear alkyl benzene sodium sulfonate, branched alkyl benzene sodium sulfonate, sodium diisopropylnaphthalene sulfonate, sodium alkyl sulfonate, linear alkyl sulfate, branched alkyl sodium sulfate, fatty alcohol polyoxyethylene ether sulfate, etc. Preferably, linear alkyl sulfate and fatty alcohol polyoxyethylene ether sulfate.

[0046] The external additive has a silanol group density of 4.5 / nm 2 The following silica particles are added to increase the fixing fastness of the toner.

[0047] The content of the external additive in the toner is 0.3 to 5 parts by mass, preferably 0.3 to 2 parts by mass, based on 100 parts by mass of the polyester resin in the toner.

[0048] The external additive is obtained by reacting an alkyl or alkoxy compound having an amine group with a siloxane compound, and then further reacting with the siloxane compound and the siloxane compound having an amine group.

[0049] The mass ratio of the alkyl or alkoxy compound having an amino group to the siloxane compound is 1:(100-150), preferably 1:(100-140), and more preferably 1:(1-136). Too much alkyl or alkoxy compound having an amino group may affect the morphology of the silica particles.

[0050] As the alkyl or alkoxy compound having an amino group, at least one selected from the group consisting of ammonia, 3-ethoxypropylamine, 3-ethoxypentylamine, 3-ethoxyhexylamine, dipropylamine, and triethylamine can be cited. Ammonia, 3-ethoxypropylamine, dipropylamine, or triethylamine is preferably selected. Furthermore, considering that the storage stability of silica is further improved, 3-ethoxypropylamine is preferred.

[0051] Examples of the siloxane compound include tetramethyl orthosilicate, tetraethyl orthosilicate, tetraisopropoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, ethyltrimethoxysilane, diethyldimethoxysilane, ethyltriethoxysilane, diethyldiethoxysilane, n-propyltrimethoxysilane, and n-propyltriethoxysilane. Tetramethyl orthosilicate is preferred.

[0052] Examples of the siloxane compound having an amino group include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyldimethylethoxysilane, (aminoethyl)aminopropyltrimethoxysilane, (aminoethyl)aminopropyltriethoxysilane, aminopropylmethyldiethoxysilane, (aminoethyl)aminopropylmethyldimethoxysilane, and aminobutyltriethoxysilane, among which aminopropyltrimethoxysilane, aminopropyltriethoxysilane, and (aminoethyl)aminopropyltriethoxysilane are preferred.

[0053] The specific preparation method of the above-mentioned silica is: add an alkyl or alkoxy group having an amino group into pure water to form a mixed liquid, heat the mixed liquid to 80-100°C, add silica to the mixed liquid at a constant speed, and after the addition is complete, continue stirring and reacting for a period of time, concentrate and dehydrate, dry, and crush to obtain modified silica particles.

[0054] The present invention is further described in detail below in conjunction with embodiments so that those skilled in the art can implement the invention with reference to the description.

[0055] It should be noted that the experimental methods described in the following embodiments are conventional methods unless otherwise specified, and the reagents and materials can be obtained from commercial channels unless otherwise specified.

[0056] <Preparation Example 1>

[0057] 1.03 g of 3-ethoxypropylamine was added to 1000 g of pure water to form a mixed solution, the mixed solution was heated to 100° C., tetramethyl orthosilicate was added to the mixed solution at a constant rate of 10 g / min, a total of 152 g was added, and after the addition was complete, 1.03 g of 3-ethoxypropylamine was added thereto, the reaction was continued with stirring for 6 hours, and the mixture was cooled to prepare colloidal silica;

[0058] 1000 g of water was added to the colloidal silica, the temperature was raised to 80°C, 100 g of tetramethyl orthosilicate and 1.8 g of 3-aminopropyltrimethoxysilane were added, the reaction was continued for 1 h, concentrated and dehydrated, dried, and crushed to obtain modified silica particles. The measured silanol group density was 3.4 / nm 2 .

[0059] <Preparation Example 2>

[0060] 1.03 g of 3-ethoxypropylamine was added to 1000 g of pure water to form a mixed solution, the mixed solution was heated to 100° C., tetramethyl orthosilicate was added to the mixed solution at a constant rate of 8 g / min, a total of 137 g was added, and after the addition was complete, 1.03 g of 3-ethoxypropylamine was added thereto, the reaction was continued with stirring for 6 hours, and the mixture was cooled to prepare colloidal silica;

[0061] 1000 g of water was added to the colloidal silica, the temperature was raised to 80°C, 90 g of tetramethyl orthosilicate and 1.6 g of 3-aminopropyltrimethoxysilane were added, the reaction was continued for 1 h, concentrated and dehydrated, dried, and crushed to obtain modified silica particles. The measured silanol group density was 3.8 / nm 2 .

[0062] The test method for silanol base density is:

[0063] The silanol density of silica particles is determined by the Sears method. The Sears method is carried out with reference to the description of GW Sears, Jr., "Determination of Specific Surface Area of ​​Colloidal Silica by Titration with Sodium Hydroxide", Analytical Chemistry, 28 (12), 1981 (1956). In the measurement, a 1 wt % silica particle dispersion is used and titrated with a 0.1 mol / L sodium hydroxide aqueous solution, and the silanol density is calculated based on the following formula.

[0064] ρ=(a×f×6022)÷(c×S)

[0065] In the above formula, they are respectively expressed as, ρ: silanol group density (pieces / nm 2 ), a: the amount of 0.1 mol / L sodium hydroxide aqueous solution added at pH 4-9 (mL), f: the factor of 0.1 mol / L sodium hydroxide aqueous solution, c: the mass of silica particles (g), S: BET specific surface area (m 2 / g).

[0066] <Example 1>

[0067] 1 mol (228 g) of bisphenol A, 1 mol (90 g) of butanediol, 1 mol (166 g) of terephthalic acid, 1 mol (100 g) of succinic anhydride, 0.02 mol (8.85 g) of compound A, and 0.001 mol (0.249 g) of dibutyltin oxide were added to a reaction container, polycondensed at 180°C for 7 hours, and then polycondensed under vacuum for 2 hours to obtain polyester resin A1.

[0068] 50 g of polyester resin was added to 40 mL of toluene, heated to 50° C. and stirred to dissolve to prepare a toluene solution of the resin. Subsequently, the toluene solution of the resin was slowly added dropwise to 300 mL of a 10 wt% sodium dodecylsulfonate solution (addition time was about 1 h). Subsequently, the toluene was distilled off under vacuum at 80° C. to obtain a polyester emulsion B1 with a particle size of 203 nm.

[0069] To 40 g of polyester emulsion B1, add 4 g of colorant dispersion and 2 g of wax dispersion, adjust the pH to 3.5-4.0 under the action of potassium persulfate or ammonium persulfate, slowly heat to 70-80°C, keep warm for 1-2 hours, then cool to 50-60°C, keep warm for 2-3 hours, cool to room temperature, wash and dry to obtain carbon powder matrix particles, and then add 1 g of commercially available silica particles as an external additive to obtain colorant C1.

[0070] <Example 2>

[0071] 1 mol (228 g) of bisphenol A, 1 mol (118 g) of hexanediol, 1 mol (166 g) of terephthalic acid, 1 mol (100 g) of succinic anhydride, 0.018 mol (11.7 g) of compound B, and 0.001 mol (0.249 g) of dibutyltin oxide were added to a reaction container, polycondensed at 180°C for 7 hours, and then polycondensed under vacuum for 2 hours to obtain polyester resin A2.

[0072] The subsequent steps are the same as those in Example 1.

[0073] <Example 3>

[0074] 1 mol (228 g) of bisphenol A, 1 mol (146 g) of octanediol, 1 mol (166 g) of terephthalic acid, 1 mol (146 g) of adipic acid, 0.02 mol (8.85 g) of compound A, and 0.001 mol (0.249 g) of dibutyltin oxide were added to a reaction container, polycondensed at 180°C for 7 hours, and then polycondensed under vacuum for 2 hours to obtain polyester resin A3.

[0075] The subsequent steps are the same as those in Example 1.

[0076] <Example 4>

[0077] 1 mol (228 g) of bisphenol A, 1 mol (174 g) of decanediol, 0.25 mol (41.5 g) of terephthalic acid, 1.75 mol (175 g) of succinic anhydride, 0.02 mol (13 g) of compound B, and 0.001 mol (0.249 g) of dibutyltin oxide were added to a reaction vessel, polycondensed at 180°C for 7 hours, and then polycondensed under vacuum for 2 hours to obtain polyester resin A4.

[0078] The subsequent steps are the same as those in Example 1.

[0079] <Example 5>

[0080] 1.1 mol (250.8 g) of bisphenol A, 1 mol (174 g) of decanediol, 0.35 mol (58 g) of terephthalic acid, 1.75 mol (175 g) of succinic anhydride, 0.02 mol (8.85 g) of compound A, and 0.001 mol (0.249 g) of dibutyltin oxide were added to a reaction vessel, polycondensed at 180°C for 7 hours, and then polycondensed under a vacuum of -0.09 MPa for 2 hours to obtain polyester resin A5.

[0081] The subsequent steps are the same as those in Example 1.

[0082] <Example 6>

[0083] 1 mol (228 g) of bisphenol A, 1 mol (174 g) of decanediol, 1 mol (166 g) of terephthalic acid, 1 mol (156 g) of butyl succinic anhydride, 0.02 mol (13 g) of compound B, and 0.001 mol (0.249 g) of dibutyltin oxide were added to a reaction vessel, polycondensed at 180°C for 7 hours, and then polycondensed under a vacuum of -0.09 MPa for 2 hours to obtain polyester resin A6.

[0084] 50 g of polyester resin was added to 40 mL of toluene, heated to 50° C. and stirred to dissolve to prepare a toluene solution of the resin. Subsequently, the toluene solution of the resin was slowly added dropwise to 300 mL of a 10 wt% sodium dodecylsulfonate solution (addition time was about 1 h). Subsequently, toluene was distilled off at -0.09 MPa and 80° C. to obtain a polyester emulsion B6 with a particle size of 201 nm and a solid content of 18.15%.

[0085] To the above 40g polyester emulsion B6, add 4g colorant dispersion and 2g wax dispersion, adjust the pH to 3.5-4.0 under the action of potassium persulfate or ammonium persulfate, slowly heat to 70-80°C, keep warm for 1-2 hours, then cool to 50-60°C, keep warm for 2-3 hours, cool to room temperature, wash and dry to obtain carbon powder matrix particles, and then add 1.0g modified silica particles prepared in Preparation Example 1 as an external additive to obtain colorant C6.

[0086] <Example 7>

[0087] The same as Example 6, except that 1.0 g of the modified silica particles prepared in Preparation Example 2 was added as an external additive to obtain Toner C7.

[0088] <Comparative Example 1>

[0089] 1 mol (228 g) of bisphenol A, 1 mol (174 g) of decanediol, 1 mol (166 g) of terephthalic acid, 1 mol (100 g) of succinic anhydride, 0.02 mol (3.84 g) of trimellitic anhydride, and 0.33 mol (10 g) of dibutyltin oxide were added to a reaction container, polycondensed at 180° C. for 7 hours, and then polycondensed under vacuum for 2 hours to obtain polyester resin DA1.

[0090] The subsequent steps are the same as those in Example 1.

[0091] <Comparative Example 2>

[0092] 1 mol (228 g) of bisphenol A, 1 mol (90 g) of butanediol, 1 mol (166 g) of terephthalic acid, 1 mol (100 g) of succinic anhydride, and 0.001 mol (0.249 g) of dibutyltin oxide were added to a reaction container, polycondensed at 180° C. for 7 h, and then polycondensed under vacuum for 2 h to obtain polyester resin DA2.

[0093] The subsequent steps are the same as those in Example 1.

[0094] <Evaluation Method of Polyester Resin>

[0095] The polyester resins prepared in Examples 1 to 7 and Comparative Examples 1 to 2 were selected for evaluation tests. The evaluation test methods are shown below. The evaluation results of the polyester resins are shown in Table 1.

[0096] 1. Weight average molecular weight (Mw)

[0097] The polystyrene conversion value was determined by measuring the polystyrene conversion value using a gel permeation chromatograph (Agilent 1260) and recorded as the Mw of the polyester resin.

[0098] 2. Glass transition temperature (T g )Measurement

[0099] The measurement was performed using a differential scanning calorimeter (DSC), the instrument model was DSC-60Plus / 60APlus, 10 mg of the sample was accurately weighed, and the measurement was performed at a heating rate of 5°C / min. The temperature at the intersection of the baseline of the graph and the tangent of the endothermic curve near the glass transition temperature was taken as the glass transition temperature. This temperature is recorded as the T of the polyester resin. g temperature.

[0100] 3. Softening temperature (T 1 / 2 )Measurement

[0101] The softening point temperature was measured by Vicat softening point temperature tester (model RHWK-300), which was recorded as the softening point temperature T of polyester resin. 1 / 2 .

[0102] 4. Acid value measurement

[0103] Weigh 0.2g of sample accurately in a conical flask, add 10ml of benzyl alcohol, and heat in a 230℃ heater for 15min to dissolve the polyester resin. After cooling to room temperature, add 10ml of benzyl alcohol, 20ml of chloroform, and a few drops of phenolphthalein, and then titrate with 0.02N KOH solution. (Sample mass = A (g), titration = B (ml)). Perform a blank experiment in the same way (titration = C (ml)) and calculate according to the following formula.

[0104] Acid value (mgKOH / g) = {(B-C) × 0.02 × 56.11} / A

[0105] Table 1

[0106]

[0107]

[0108] As can be seen from Table 1, the polyester resins prepared in Examples 1-7 have a higher glass transition temperature, a lower softening point temperature and a relatively higher acid value, and Examples 4-5 have a lower softening temperature than the polyester resins in Examples 1-3.

[0109] <Toner Evaluation Method>

[0110] The toners prepared in Examples 1 to 7 and Comparative Examples 1 to 2 were selected for evaluation tests. The evaluation test methods are as follows. The evaluation results of the toners are shown in Table 2.

[0111] 1. Preservation evaluation

[0112] Put 10g of toner into a sample bottle, place it in a 60℃, 50% humidity environment for 72h, then gently transfer it to a container containing toner to check whether the toner has condensed. If no condensation is observed on the toner surface, it means that the preservation is excellent; if there is condensation on the toner surface, but it can be eliminated without vibration during transfer and does not affect the actual printing effect, it means that the preservation is good; if there is condensation on the toner surface and vibration cannot be eliminated during transfer, it means that the preservation is poor.

[0113] 2. Evaluation of fixing temperature

[0114] The measurement is carried out using a commercially available printer. The temperature of the printer's fixing roller is changed by 5°C, and the fixing rate of the toner at each temperature is measured. The fixing rate is calculated by the ratio of the image density of the printed black area before and after the tap peeling operation. The lowest temperature of the fixing roller when the fixing rate is greater than or equal to 80% can be regarded as the fixing temperature of the toner.

[0115] 3. Evaluation of fixing firmness

[0116] The toner was tested for printing on a low-temperature fixing printer Fuji Xerox DocuPrint CP105b (normal temperature 25 degrees, normal humidity 60%), and the fixing fastness was recorded. Fixing fastness = M 前 / M 后 *100%, M 前 is the measured density at a certain point, M 后 The density is measured again after rubbing with gauze. The M in this evaluation is 前 and M 后It is the average value of 6 sampling points, and the diameter of each sampling point is 6mm.

[0117] Table 2

[0118]

[0119]

[0120] It can be seen from Table 2 that the toners prepared from the polyester resins of Examples 1 to 7 have better storage stability, lower fixing temperature and higher fixing fastness.

[0121] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and the implementation modes. They can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to the specific details and the embodiments shown and described herein.

Claims

1. A binder resin for toner, characterized in that: It comprises bisphenol compounds, aliphatic diols, dicarboxylic acids and compounds represented by formula (1) and their salts through polycondensation, wherein the compound represented by formula (1) is: In formula (1), R1, R2 and R3 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkyl ester group.

2. The binder resin for toner according to claim 1, wherein The glass transition temperature T of the adhesive resin g The softening temperature of the adhesive resin is 50 to 70°C. 1 / 2 It is 80~98℃.

3. The binder resin for toner according to claim 1, wherein The R2 is an alkyl ester group having 1 to 10 carbon atoms.

4. The binder resin for toner according to claim 1, wherein The invention comprises 1 to 1.8 mole parts of a bisphenol compound, 1 to 1.2 mole parts of an aliphatic diol, 1 to 3 mole parts of a dicarboxylic acid, and 0.018 to 0.022 mole parts of a compound represented by formula (1) and a salt thereof.

5. The binder resin for toner according to claim 1, wherein The dicarboxylic acid includes an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid, and the molar ratio of the aromatic dicarboxylic acid to the aliphatic dicarboxylic acid is 1:(5-8).

6. The binder resin for toner according to claim 3, wherein 1 to 1.8 mole parts of bisphenol compound, 1 to 1.2 mole parts of aliphatic diol, 1 to 3 mole parts of dicarboxylic acid, 0.018 to 0.022 mole parts of the compound represented by formula (1) and its salt, and 0.001 to 0.002 mole parts of catalyst are added to a container, polycondensed at 160 to 180° C. for 6 to 10 hours, and then polycondensed under vacuum conditions for 2 to 4 hours to obtain a binder resin having a molecular weight M of the binder resin. w 20000~60000, Tg is 50~70℃, T 1 / 2 The temperature is 80-98°C, and the acid value is 10-25 mg KOH / g.

7. A toner for electrostatic charge image development, characterized in that: The toner binder resin comprises the toner binder resin according to any one of claims 1 to 6.

8. The electrostatic charge image developing toner according to claim 7, wherein: Including external additives, the external additives are silanol groups with a density of 4.5 / nm on the surface 2 The following silica particles.

9. The electrostatic charge image developing toner according to claim 8, wherein: The external additive is obtained by reacting an alkyl or alkoxy compound having an amine group with a siloxane compound, and then further reacting with the siloxane compound and the siloxane compound having an amine group.

10. An electrostatic charge image developer, characterized in that: A toner for developing an electrostatic charge image comprising the toner according to any one of claims 7 to 9.

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