JP4557811B2 - Toner for electrophotography - Google Patents

Description

  The present invention relates to an electrophotographic toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.

  From the viewpoint of improving the fixability, a toner containing polyester as a binder resin is disclosed (see Patent Document 1).

On the other hand, with the recent demand for higher speed and higher image quality, many studies have been made on crystalline polyester from the viewpoint of improving low-temperature fixability (see Patent Document 2). In particular, when the crystalline polyester is used in combination with the amorphous polyester, a significant low-temperature fixing effect can be obtained as compared with the case where only the amorphous polyester is used.
JP 2000-172009 JP 2001-222138 A

  On the other hand, the thermal stability of the toner is very important. For example, the toner is fixed on paper or the like by heat and pressure, but preferably exhibits similar thermal properties before fixing and after fixing and cooling. However, when crystalline polyester is used in combination with amorphous polyester, the crystallinity of crystalline polyester collapses before fixing and after fixing / cooling due to the interaction between the two, preserving and durability are impaired, and image fixing is degraded. Tend to.

  However, it is inevitable that the crystalline polyester and the amorphous polyester interact with each other due to melting at the time of fixing. Usually, from the viewpoint of maintaining good image fixing properties, the crystalline polyester and the amorphous polyester Combined use is difficult.

  An object of the present invention is to provide an electrophotographic toner that has stable thermal characteristics and can maintain good image fixability even when it contains a crystalline polyester and an amorphous polyester. is there.

  The present invention relates to an electrophotographic toner comprising a crystalline polyester and an amorphous polyester as a binder resin, wherein the amorphous polyester has a content of an alkylene oxide adduct of bisphenol A of 80 mol%. The alcohol component having a content of alkylene oxide adduct of bisphenol A in which 3 mol or more of alkylene oxide is added in the alkylene oxide adduct of bisphenol A and a carboxylic acid component are subjected to polycondensation. The present invention relates to an electrophotographic toner containing the resin obtained as described above.

  Even if the toner of the present invention contains a crystalline polyester and an amorphous polyester, the toner has a stable thermal characteristic and exhibits an excellent effect that a good image fixing property can be maintained. .

  The electrophotographic toner of the present invention contains a crystalline polyester and an amorphous polyester as a binder resin. The crystallinity of polyester is represented by the ratio between the softening point and the highest endothermic peak temperature measured by a differential scanning calorimeter, that is, the crystallinity index defined by the softening point / the highest endothermic peak temperature. Generally, when this value exceeds 1.5, the resin is amorphous, and when it is less than 0.6, the crystallinity is low and there are many amorphous parts. The crystallinity of the resin can be adjusted by the type and ratio of the raw material monomers, production conditions (for example, reaction temperature, reaction time, cooling rate) and the like. For example, crystallization of polyester can be promoted by combining aliphatic alcohols and aliphatic carboxylic acid compounds having a similar short molecular chain and relatively easily arranged as a raw material monomer. Further, the maximum peak temperature of endotherm tends to be higher as the resin has higher crystallinity, and can be adjusted, for example, by the ratio of the monomer that promotes crystallization or the monomer that promotes non-crystallization. The maximum peak temperature of endotherm refers to the peak temperature on the highest temperature side among the observed endothermic peaks. If the maximum peak temperature is within 20 ° C from the softening point, the melting point is determined.

  The crystalline polyester in the present invention refers to those having a crystallinity index of 0.6 to 1.5. The crystallinity index of the crystalline polyester is preferably 0.8 to 1.3, more preferably 0.9 to 1.1, and still more preferably 0.98 to 1.05, from the viewpoint of low-temperature fixability. In addition, the amorphous polyester in the present invention refers to a resin having a crystallinity index greater than 1.5 or less than 0.6, preferably greater than 1.5.

  Both the crystalline polyester and the amorphous polyester are obtained using an alcohol component and a carboxylic acid component as raw material monomers.

  As alcohol components, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-butenediol, 1,2-propanediol, 1,3-butanediol, neopentyl glycol, 2-butyl-2-ethyl-1,3 -Aliphatic diols such as propanediol; polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, etc. Formula (I):

(Wherein R is an alkylene group having 2 or 3 carbon atoms, x and y are positive numbers, and the sum of x and y is 1 to 16, preferably 1.5 to 5.0)
And aromatic diols such as alkylene oxide adducts of bisphenol A represented by the formula: trihydric or higher polyhydric alcohols such as glycerin and pentaerythritol.

  Among these alcohol components, the alcohol components that promote crystallization of polyester include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1 2, aliphatic diols having 2 to 6 carbon atoms such as 4-butenediol.

  Examples of carboxylic acid components include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, etc. An aliphatic dicarboxylic acid such as cyclohexanedicarboxylic acid; an aromatic dicarboxylic acid such as phthalic acid, isophthalic acid or terephthalic acid; a trivalent or higher polyvalent carboxylic acid such as trimellitic acid or pyrrolemetic acid; and An anhydride of these acids, alkyl (C1-C3) ester, etc. are mentioned. Such acids, anhydrides of these acids, and alkyl esters of these acids are collectively referred to herein as carboxylic acid compounds.

  Among these carboxylic acid components, the carboxylic acid component that promotes crystallization of polyester includes aliphatic dicarboxylic acid compounds having 2 to 6 carbon atoms such as oxalic acid, malonic acid, maleic acid, fumaric acid, succinic acid, and adipic acid. Etc.

  Furthermore, from the viewpoint of molecular weight adjustment and the like, the raw material monomer may appropriately contain a monovalent alcohol or a monovalent carboxylic acid compound as long as the effects of the present invention are not impaired.

  The polyester is obtained by polycondensing an alcohol component and a carboxylic acid component, for example, in an inert gas atmosphere, if necessary, in the presence of an esterification catalyst. The reaction temperature is preferably 120 to 230 ° C. in the production of crystalline polyester, 150 to 280 ° C. is preferred in the production of amorphous polyester, and 200 to 250 ° C. is more preferred.

  As the alcohol component which is a raw material monomer of the crystalline polyester, an aliphatic diol having 2 to 6 carbon atoms is preferable, among which α, ω-linear alkanediol is preferable, 1,4-butanediol and 1,6-hexane. Diols are more preferred. Further, as the carboxylic acid component, fumaric acid is preferable from the viewpoint of promoting crystallization of polyester, and terephthalic acid is preferable from the viewpoint of chargeability.

  Therefore, the crystalline polyester has an alcohol component containing 2 to 6 carbon atoms aliphatic diol of 60 mol% or more, preferably 70 mol% or more, fumaric acid and / or terephthalic acid of 60 mol% or more, preferably 70 mol%. % Is preferably a resin obtained by polycondensation of a carboxylic acid component contained in an amount of at least%, and in particular, from the viewpoint of fixability, a crystalline polyester is present in an amorphous resin in an incompatible state. Is preferably the main component.

  The melting point of the crystalline polyester is preferably 70 to 150 ° C, more preferably 90 to 130 ° C.

  From the viewpoint of chargeability, the amorphous polyester comprises an alcohol component containing 80 mol% or more, preferably 90 mol% or more, more preferably substantially 100 mol% of an bisphenol A alkylene oxide adduct, and a carboxylic acid component. The present invention has a great feature in the alkylene oxide adduct of bisphenol A. That is, the content of the alkylene oxide adduct of bisphenol A in which 3 mol or more of alkylene oxide in the alkylene oxide adduct of bisphenol A is added is 15% by weight or less, preferably 10% by weight or less, more preferably 5%. % By weight or less.

  An alkylene oxide adduct of bisphenol A to which 3 mol or more of alkylene oxide has been added (hereinafter also referred to as an AO 3 mol or more adduct) has a high compatibility with the crystalline polyester, so the adduct of AO 3 mol or more is adduct. It is presumed that the amorphous polyester in which the amount of is reduced reduces the interaction with the crystalline polyester.

  If the number of moles of alkylene oxide added is the same, propylene oxide is preferable to ethylene oxide, and 50 mole% or more, preferably 70 mole% or more, more preferably 90 mole% or more of the alkylene oxide adduct of bisphenol A is propylene. It is preferable that it is an oxide adduct.

The average addition mole number of the bisphenol A alkylene oxide adduct in the alcohol component that is the raw material monomer of the amorphous polyester is preferably 1.8 to 2.18, more preferably 2.0 to 2.15, and even more preferably 2.0 to 2.10.

  Further, the content of the alkylene oxide adduct of bisphenol A in which 4 mol or more of alkylene oxide is added in the alkylene oxide adduct of bisphenol A is preferably 0.1 mol% or less from the viewpoint of image-fixing property.

  The softening point of the amorphous polyester is preferably 80 to 160 ° C, more preferably 90 to 150 ° C. Moreover, 50-75 degreeC is preferable and, as for a glass transition point, 53-65 degreeC is more preferable.

  The content of the resin obtained using the alcohol component in which the content of the alkylene oxide adduct of bisphenol A to which 3 moles or more of the alkylene oxide has been added is controlled is preferably 60% by weight or more in the total amount of the amorphous polyester, 80% by weight or more is more preferable and substantially 100% by weight is further preferable.

  The acid value of the crystalline polyester and the amorphous polyester is preferably 3 to 40 mgKOH / g.

  The weight ratio of amorphous polyester to crystalline polyester (weight ratio of amorphous polyester / crystalline polyester) is preferably 50/50 to 98/2, more preferably 60/40 to 95/5, and 70/30 More preferably, ˜90 / 10.

  In the binder resin, the total content of the amorphous polyester and the crystalline polyester is preferably 50% by weight or more, more preferably 70% by weight or more, and further preferably 90% by weight or more. Examples of the resin that may be included as a binder resin in addition to the amorphous polyester and the crystalline polyester include vinyl resins such as styrene-acrylic resins, epoxy resins, polycarbonates, and polyurethanes.

  Further, the toner obtained by the present invention includes additives such as a colorant, a release agent, a charge control agent, a conductivity regulator, an extender pigment, a reinforcing filler such as a fibrous substance, an antioxidant, and an anti-aging agent. However, it may be added as appropriate.

  There is no restriction | limiting in particular as a coloring agent in this invention, A well-known coloring agent is mentioned, According to the objective, it can select suitably. Specifically, carbon black, chrome yellow, hansa yellow, benzidine yellow, selenium yellow, quinoline yellow, permanent orange GTR, pyrazolone orange, balkan orange, watch young red, permanent red, brilliantamine 3B, brilliantamine 6B, dupont oil Various pigments and acridines such as red, pyrazolone red, resol red, rhodamine B lake, lake red C, Bengal, aniline blue, ultramarine blue, calco oil blue, methylene blue chloride, phthalocyanine blue, phthalocyanine green, malachite green oxalate Xanthene, azo, benzoquinone, azine, anthraquinone, indico, thioindico, phthalocyanine, Phosphorus black dyes, polymethine dyes, triphenylmethane dyes, diphenylmethane dyes, thiazine, various dyes thiazole, etc. may be used in conjunction with one or more kinds.

The toner of the present invention can be produced by a known method such as a kneading and pulverizing method, an emulsion aggregation method, a spray drying method, or a polymerization method. As a general method for producing a pulverized toner by a kneading pulverization method, for example, a binder resin, a colorant, a charge control agent and the like are uniformly mixed with a mixer such as a ball mill, and then a sealed kneader or a single screw or two Examples thereof include a method of melt-kneading with a shaft extruder or the like, cooling, pulverizing, and classifying. Furthermore, a fluidity improver such as hydrophobic silica may be added to the coarsely pulverized product in the production process or the surface of the obtained toner, if necessary. The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably 3 to 15 μm, more preferably 4 to 8 μm. In the present specification, the volume-median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size.

  The toner of the present invention has stable thermal characteristics. The endothermic ratio in differential scanning calorimetry is preferably from 0.6 to 1.1, more preferably from 0.7 to 1.05, and even more preferably from 0.8 to 1.0, from the viewpoint of image quality fixability. The closer the endothermic ratio value is to 1, the faster the crystallization recovery rate. For this reason, the higher the heat absorption ratio, the higher the image quality fixability because the original crystallinity can be maintained through the heat fixing step.

  The toner of the present invention can be used as a one-component developing toner as it is, or as a two-component developer mixed with a carrier, and can be used in either a one-component developing method or a two-component developing method.

[Softening point of resin]
Using a flow tester (Shimadzu Corporation, CFT-500D), a 1 g sample is heated at a heating rate of 6 ° C / min, and a 1.96 MPa load is applied by a plunger and extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. . The amount of plunger drop of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is taken as the softening point.

[Maximum peak temperature and melting point of resin endotherm]
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), the temperature is raised to 200 ° C, and the sample cooled to 0 ° C at a temperature drop rate of 10 ° C / min is measured at a temperature rise rate of 10 ° C / min. . Among the observed endothermic peaks, the temperature of the peak on the highest temperature side is defined as the highest endothermic peak temperature. If the maximum peak temperature is within 20 ° C. from the softening point, the melting point is set, and the peak having a difference from the softening point exceeding 20 ° C. is a peak due to glass transition.

[Glass transition point of resin]
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), the temperature is raised to 200 ° C, and the sample cooled to 0 ° C at a temperature drop rate of 10 ° C / min is measured at a temperature rise rate of 10 ° C / min. .
When the difference between the maximum endothermic peak temperature and the softening point is within 20 ° C, an extension of the baseline below the maximum endothermic peak temperature, and a tangent line indicating the maximum slope from the peak of the peak to the peak apex The temperature at the intersection is read as the glass transition point.
When the difference between the maximum endothermic peak temperature and the softening point exceeds 20 ° C, the peak is observed from the baseline extension below the peak temperature observed at a temperature lower than the maximum endothermic peak temperature, and from the peak of the peak. The temperature at the point of intersection with the tangent indicating the maximum inclination to the top of is read as the glass transition point.

[Resin crystallinity index]
The crystallinity index is calculated from the following formula using the softening point and endothermic maximum peak temperature measured according to the above.
Crystallinity index = softening point / maximum endothermic peak temperature

[Acid value of the resin]
Measured by the method of JIS K0070.

Production Example 1 of Amorphous Polyester
Raw material monomers other than trimellitic anhydride shown in Tables 1 and 2 and 4 g of tin octylate were placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple. After reacting over time, it was reacted at 8.3 kPa for 1 hour. Further, trimellitic anhydride was added at 210 ° C. and allowed to react until the desired softening point was reached to obtain Resins A to K.

Production Example 2 of Amorphous Polyester
Raw material monomers other than fumaric acid and trimellitic anhydride shown in Table 2 and 4 g of tin octylate were placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer and thermocouple at 230 ° C. After reacting for 20 hours, cool to 200 ° C, add 1 g of fumaric acid and hydroquinone, react for 5 hours, further add trimellitic anhydride and react at 100 ° C for 1 hour, then to 8.3 kPa The resin L was obtained by reacting until the desired softening point was reached.

Production Example 3 of Amorphous Polyester
Raw material monomers other than trimellitic anhydride shown in Table 3 and 1 g of hydroquinone were placed in a 5-liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer and thermocouple, and reacted at 200 ° C for 8 hours. And then reacted at 8.3 kPa for 1 hour. Further, trimellitic anhydride was added at 210 ° C. and reacted until the desired softening point was reached to obtain resins M to O.

  Tables 4 and 5 show the breakdown of the number of moles added in BPA-PO (propylene oxide adduct of bisphenol A) and BPA-EO (ethylene oxide adduct of bisphenol A) used in resins A to O. About the breakdown of each alcohol, the weight ratio was calculated | required from the peak area ratio of the gas chromatography.

Production Example 1 of Crystalline Polyester
The raw material monomers shown in Table 6, 4 g of dibutyltin oxide and 1 g of hydroquinone were placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer and thermocouple, and reacted at 160 ° C. for 5 hours. Then, the temperature was raised to 200 ° C. and reacted for 1 hour. The reaction was further proceeded at 8.3 kPa to obtain resin a.

Production Example 2 of Crystalline Polyester
The raw material monomer shown in Table 6 and 4 g of dibutyltin oxide were placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, and reacted at 160 ° C. for 5 hours. The temperature was raised to 200 ° C. and reacted for 1 hour. The reaction was further proceeded at 8.3 kPa to obtain resin b.

Examples 1-9 and Comparative Examples 1-3 (Example 7 is a reference example)
Binder resin shown in Table 7, colorant “Regal 330R” (Cabot) 4 parts by weight, charge control agent “Bontron S-34” (Orient Chemical Industries) 1 part, polypropylene wax “SP-105” 1 part by weight (manufactured by Sasol) and 1 part by weight of polyethylene wax “Paraflint C80” (manufactured by Sasol) were stirred with a Henschel mixer for 5 minutes.

  The obtained mixture was melt-kneaded using a co-rotating twin screw extruder having a total length of 1560 mm, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm. The roll rotation speed was 200r / min. The set temperature in the roll was 100 ° C., the outlet temperature of the kneaded product was about 150 ° C., the feed rate of the mixture was 10 kg / h, and the average residence time was about 18 seconds.

The obtained kneaded product was cooled and coarsely pulverized, and then finely pulverized and classified by a jet mill to obtain a powder having a volume median particle size (D ₅₀ ) of 7.5 μm.

  To 100 parts by weight of powder, 0.7 part by weight of hydrophobic silica “R972” (manufactured by Nippon Aerosil Co., Ltd.) was added as an external additive and mixed with a Henschel mixer to obtain a toner.

Test Example 1 [Endothermic Ratio]
Using a differential scanning calorimeter “Pyris6” (manufactured by Perkin Elmer), 0.1g of toner was heated from -50 ° C. to 10 ° C./min to 160 ° C. (1st) and then to 10 ° C./min to -50 ° C. Then, the temperature was increased again to 160 ° C. at 10 ° C./min (2nd), and the ratio of the endothermic amount when the temperature was increased from −50 ° C. to 160 ° C. (1st and 2nd) was calculated. The closer the endothermic ratio is to 1.0, the smaller the modification of the polyester due to the interaction between the crystalline polyester and the amorphous polyester, indicating that the crystallinity of the crystalline polyester is maintained. The results are shown in Table 7.

Test Example 2 [low temperature fixability]
The toner is mounted on the copier “AR-505” (manufactured by Sharp Corporation), and the toner adhesion amount is 0.55 mg / cm ^{2 on} plain paper (CopyBond SF-70NA, manufactured by Sharp Corporation, 75 g / m ² ). An unfixed solid image (15 cm × 25 cm) was obtained. The fixing machine (fixing speed: 150mm / sec) improved so that the fixing machine of the copier "AR-505" (manufactured by Sharp Corporation) can be fixed off-line, in increments of 5 ° C from 90 ° C to 240 ° C. The fixing test was conducted while raising the temperature.

  “UNICEF cellophane” (Mitsubishi Pencil Co., Ltd., width: 18 mm, JISZ-1522) was attached to the fixed image, passed through a fixing roll set at 30 ° C., and then the tape was peeled off. The optical reflection density before and after the tape is peeled off is measured using a reflection densitometer “RD-915” (manufactured by Macbeth), and the ratio of both (after peeling / before sticking) first exceeds 70%. The low-temperature fixability was evaluated according to the following evaluation criteria with the temperature (temperature of the thermostatic bath) as the minimum fixing temperature. The results are shown in Table 7.

〔Evaluation criteria〕
A: The minimum fixing temperature is 135 ° C. or less. ○: The maximum fixing temperature is 140 to 155 ° C.
×: Maximum fixing temperature of 160 ° C or higher

Test Example 3 [Image fixability]
The toner is mounted on a copier “AR-505” (manufactured by Sharp Corporation), and the toner adhesion amount is 0.55 mg / cm ^{2 on} plain paper (CopyBond SF-70NA, Sharp Corporation, 75 g / m ² ). A solid image (15 cm × 25 cm) was printed. Place 1000 sheets of plain paper (CopyBond SF-70NA, manufactured by Sharp Corporation, 75 g / m ² ) on the solid image and leave it in a constant temperature bath at a temperature of 50 ° C and a relative humidity of 60% for 10 hours. It was confirmed whether or not it was stuck to the paper stacked on top, and image fixability was evaluated according to the following evaluation criteria. The results are shown in Table 7.

〔Evaluation criteria〕
A: Not attached at all.
○: Slightly attached but easily peeled off and no damage to the image.
Δ: Slightly adhered and easily peeled off, but slightly damages the image.
X: It sticks firmly and damages an image significantly in peeling off.

  From the above results, it can be seen that the toners of the examples have excellent low-temperature fixability as compared with the toners of the comparative examples, and can maintain better image fixability than the comparative examples even in a severe environment.

  The toner for electrophotography of the present invention is suitably used for developing a latent image formed in electrophotography, electrostatic recording method, electrostatic printing method and the like.

Claims (5)

An electrophotographic toner comprising a crystalline polyester and an amorphous polyester as a binder resin, wherein the amorphous polyester has a content of an alkylene oxide adduct of bisphenol A of 80 mol% or more, More than 50 mol% of the alkylene oxide adduct of bisphenol A is a propylene oxide adduct of bisphenol A, and the alkylene oxide adduct of bisphenol A containing 3 mol or more of alkylene oxide in the alkylene oxide adduct of bisphenol A is contained. and an alcohol component amount is 10 wt% or less, a resin obtained a carboxylic acid component by polycondensing, in the amorphous polyester total, Ri Na contain 60 wt% or more, the crystalline polyester, 1 Alcohol component containing 60 mol% or more of 1,6-hexanediol Fumaric acid and / or resin der Ru toner for electrophotography obtained carboxylic acid component terephthalic acid 60 mol% or more by polycondensing. The electrophotographic toner of claim 1 Symbol placement average addition mole number of alkylene oxide adducts are from 1.8 to 2.18 of bisphenol A. The electrophotographic toner according to claim 1 or 2 , wherein the content of the alkylene oxide adduct of bisphenol A in which 4 mol or more of alkylene oxide is added in the alkylene oxide adduct of bisphenol A is 0.1 mol% or less. The toner for electrophotography according to any one of claims 1 to 3, wherein the weight ratio of amorphous polyester to crystalline polyester (weight ratio of amorphous polyester / crystalline polyester) is 50/50 to 98/2. The toner for electrophotography according to any one of claims 1 to 4 , wherein a heat absorption ratio of the toner in differential scanning calorimetry is 0.6 to 1.1.