Polyester resin composition, tonner for development of electrostatic charge image, developer, and image formation method

Abstract

To provide a polyester resin composition capable of improving low temperature fixability, heat proof storage property, and fracture resistivity of a tonner, a tonner for development of an electrostatic charge image containing the polyester resin composition, a developer, and an image formation method using the developer.SOLUTION: A polyester resin composition includes a polyester resin, where the total number N of peaks having a retention time of 4,4'-dihydroxybiphenyl or shorter in 20 peaks of relative large present amount is 1-17, and at least any element of boron, aluminum, and phosphor is further included in a chromatogram obtained by heat decomposition gas chromatograph mass analysis.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyester resin composition, a toner for developing electrostatic images, a developer, and an image forming method. [Background technology]

[0002] Patent Document 1 discloses a polyester resin composition containing a catalyst made of an inorganic tin (II) compound and a polyester that does not contain bisphenol A as a constituent monomer. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-231744 Summary of the Invention [Problem to be solved by the invention]

[0004] The polyester composition described in Patent Document 1 is more susceptible to heat than polyesters containing a large amount of bisphenol derivative components in the constituent monomers of the polyester, and is prone to deformation in the fixing temperature range. Therefore, while such polyester compositions have good low-temperature fixing properties, they also have poor heat-resistant storage stability, making it difficult to achieve both. Furthermore, toners containing the polyester resin composition described in Patent Document 1 tend to be brittle and have low shatter resistance. Toners with low shatter resistance tend to shatter when mixed with the carrier in the developing machine, and the shattered components cover the carrier surface. Therefore, toners with low shatter resistance tend to inhibit charging with replenished toner, causing fogging and toner scattering.

[0005] The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a polyester resin composition capable of improving the low-temperature fixability, heat-resistant storage stability, and crush resistance of a toner, a toner and developer for developing electrostatic images containing the polyester resin composition, and an image forming method using the developer. [Means for solving the problem]

[0006] The above-mentioned problems of the present invention can be solved by the following means.

[0007] 1. A polyester resin composition containing a polyester resin, In a chromatogram obtained by pyrolysis gas chromatography mass spectrometry, the total number N of peaks having retention times equal to or shorter than the retention time of 4,4'-dihydroxybiphenyl among 20 peaks with high relative abundance is 1 to 17, Further containing at least one element of boron, aluminum, and phosphorus, Polyester resin composition.

[0008] 2. The total content of boron, aluminum, and phosphorus is within the range of 300 to 3,000 ppm by mass relative to 100% by mass of the polyester resin. 2. The polyester resin composition according to item 1.

[0009] 3. The sum of the acid value and the hydroxyl value of the polyester resin is within the range of 200 to 1000 mgKOH / g. 2. The polyester resin composition according to item 1.

[0010] 4. A polyester resin composition according to any one of items 1 to 3, comprising 30 to 97% by mass of the polyester resin composition. Toner for developing electrostatic images.

[0011] 5. The average circularity is within the range of 0.950 to 0.995. 5. The toner for developing electrostatic images according to item 4.

[0012] 6. The toner for developing electrostatic images according to item 4, Specific gravity: 4-6g / cm 3 and a carrier having a volume average particle size in the range of 20 to 40 μm. Developer.

[0013] 7. A developer containing the toner for developing electrostatic images according to item 4 is used. Image forming method.

[0014] 8. Using a developing means that forms a layer of the developer on a developing roller, The peripheral speed of the developing roller is within the range of 200 to 800 mm / s. 8. The image forming method according to item 7. [Effects of the Invention]

[0015] According to the present invention, it is possible to provide a polyester resin composition capable of improving the low-temperature fixability, heat-resistant storage stability, and crush resistance of a toner, a toner and developer for developing electrostatic images containing the polyester resin composition, and an image forming method using the developer.

[0016] The mechanism by which the effects of the present invention are exhibited or the mechanism of action is presumed to be as follows.

[0017] The polyester resin composition of the present invention is characterized in that, in a chromatogram obtained by pyrolysis gas chromatography-mass spectrometry, the total number N of peaks having retention times equal to or shorter than that of 4,4'-dihydroxybiphenyl is 1 to 17 out of 20 peaks with high relative abundance. Here, polyester resin components with a number N of 1 or more indicate that they have small molecular weight cleavage energy during the pyrolysis process, are easily affected by heat, and contain many components with small molecular weights and strong polarity. The present inventors have discovered that polyester resin compositions containing such components further improve the low-temperature fixability of toners containing the polyester resin composition.

[0018] On the other hand, polyester resin compositions with a molecular weight N of 18 or more tend to significantly reduce the crush resistance of toner, making them prone to cracking in a developing unit at temperatures within an operating machine (approximately 55°C or less). However, the polyester resin composition of the present invention, in addition to having a molecular weight N of 17 or less, further contains at least one element selected from the group consisting of boron, aluminum, and phosphorus. These boron, aluminum, and phosphorus elements become trivalent cations in the polyester resin. These elements form ionic bridges within the polyester resin main chain, particularly with ionized functional groups and electron-biased portions of the molecule. The inventors have discovered that this effect improves the brittleness resistance of polyester resins within machines and the crush resistance of toners.

[0019] Furthermore, polyester resin compositions that are susceptible to heat also tend to reduce the heat-resistant storage stability of toner. However, the polyester resin composition of the present invention can improve the heat-resistant storage stability while maintaining the low-temperature fixability of the toner by the ionic crosslinking effect of boron, aluminum, and phosphorus.

[0020] Therefore, the polyester resin composition of the present invention can improve the low-temperature fixability, heat-resistant storage stability, and crush resistance of the toner. [Brief explanation of the drawings]

[0021] [Figure 1] Chromatogram of 4,4'-dihydroxybiphenyl alone [Figure 2] Chromatogram of a polyester resin composition according to one embodiment of the present invention [Figure 3] Chromatogram of a polyester resin composition as a comparative example [Figure 4] An example of a flowchart of an image forming method [Figure 5] 1 is a schematic diagram of an example of an image forming apparatus that can be used in the image forming method. [Figure 6] Cross-sectional view showing part of the imaging unit [Figure 7]A cross-sectional view showing the arrangement of magnetic poles in a magnet roller provided in a developing roller. [Figure 8] Schematic diagram of the charge amount measuring device DETAILED DESCRIPTION OF THE INVENTION

[0022] The following description describes embodiments of the present invention. The advantages and features of one or more embodiments of the present invention can be understood from the following detailed description and drawings. It should be noted that the following detailed description and drawings are provided for illustrative purposes only and do not limit the scope of the present invention.

[0023] The following description refers to the drawings and describes one or more embodiments of the invention, although the scope of the invention is not limited to the disclosed embodiments.

[0024] In this application, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit.

[0025] [1. Polyester resin composition] [1-1. Polyester resin] The polyester resin composition of the present invention contains a polyester resin. The polyester is, for example, a polycondensation product of a polycarboxylic acid and a polyhydric alcohol. The polyester includes amorphous polyester and crystalline polyester.

[0026] "Amorphous" means that it does not have a melting point. In other words, "amorphous" means that it does not have a clear endothermic peak when heated in an endothermic curve obtained by differential scanning calorimetry (DSC). "Clear endothermic peak" means a peak with a half-width of 15°C or less in an endothermic curve when heated at a heating rate of 10°C / min.

[0027] "Crystalline" means having a melting point. In other words, "crystalline" means having a clear endothermic peak when heating in an endothermic curve obtained by differential scanning calorimetry (DSC). A "clear endothermic peak" means a peak with a half-width of 15°C or less in an endothermic curve when heating at a rate of 10°C / min.

[0028] Polyesters can be synthesized, for example, by esterifying polycarboxylic acids and polyhydric alcohols through polycondensation using an esterification catalyst. The polyesters synthesized in this manner have a structure derived from the polycarboxylic acid and a structure derived from the polyhydric alcohol. The polycarboxylic acid has two or more carboxy groups per molecule. The polyhydric alcohol has two or more hydroxy groups per molecule.

[0029] Examples of polycarboxylic acids that can be used in the synthesis of amorphous polyesters include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, mesaconic acid, dimethyl isophthalate, fumaric acid, dodecenyl succinic acid, and 1,10-dodecanedicarboxylic acid. Among these, dimethyl isophthalate, terephthalic acid, dodecenyl succinic acid, and trimellitic acid are preferred. The polycarboxylic acids used in the synthesis may be one type or two or more types.

[0030] Examples of polyhydric alcohols that can be used in the synthesis of amorphous polyesters include dihydric alcohols such as ethylene glycol, propylene glycol, butanediol, diethylene glycol, pentanediol, neopentyl glycol, hexanediol, heptanediol, cyclohexanediol, octanediol, decanediol, and dodecanediol; trihydric or higher polyols such as glycerin, pentaerythritol, hexamethylolmelamine, hexaethylolmelamine, tetramethylolbenzoguanamine, and tetraethylolbenzoguanamine; and ester compounds thereof; hydroxycarboxylic acid derivatives, bisphenols, and bisphenol derivatives. The polyhydric alcohols used in the synthesis may be one type or two or more types.

[0031] Bisphenols and bisphenol derivatives can be esterified in the same way as alcohols. Therefore, in the present invention, the term "polyhydric alcohol" includes bisphenols and bisphenol derivatives. Examples of bisphenols include bisphenol A. Examples of bisphenol derivatives include ethylene oxide adducts of bisphenol A (BPA-EO) and propylene oxide adducts of bisphenol A (BPA-PO).

[0032] The polyhydric alcohol is preferably an aliphatic polyhydric alcohol having 5 to 7 carbon atoms. Aliphatic polyhydric alcohols having 5 to 7 carbon atoms have a relatively small bulk, which makes it easy to make the bond distances between ester bonds uniform in the polyester obtained by synthesis. Furthermore, it is unlikely that localized areas with high ester group density will be formed. Specifically, it is believed that the hydrophilic moieties derived from the ester bonds and the hydrophobic moieties derived from the hydrocarbon groups are dispersed appropriately, thereby suppressing charge leakage.

[0033] In particular, aliphatic polyhydric alcohols having 5 to 7 carbon atoms are smaller in bulk than bisphenol A or derivatives of bisphenol A. Therefore, it is believed that aliphatic polyhydric alcohols having 5 to 7 carbon atoms can suppress charge leakage more effectively than bisphenol A or derivatives of bisphenol A.

[0034] Examples of the aliphatic polyhydric alcohol having 5 to 7 carbon atoms include pentanediol, neopentyl glycol, hexanediol, heptanediol, and cyclohexanediol.

[0035] From the viewpoint of low-temperature fixability, the proportion of bisphenol A and bisphenol A derivatives in the polyhydric alcohol is preferably low. Specifically, the total proportion of structural units derived from bisphenol A and bisphenol A derivatives relative to the total number of moles of structural units derived from the polyhydric alcohol is preferably 10 mol % or less, more preferably 5 mol % or less, more preferably 1 mol % or less, and even more preferably 0 mol %.

[0036] Examples of polycarboxylic acids that can be used in the synthesis of crystalline polyesters include saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, n-dodecylsuccinic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid (dodecanedioic acid), and tetradecanedicarboxylic acid (tetradecanedioic acid); alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid; and anhydrides of these carboxylic acid compounds. Other examples include alkyl esters having 1 to 3 carbon atoms.

[0037] Examples of polyhydric alcohols that can be used in the synthesis of crystalline polyesters include aliphatic diols such as 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, dodecanediol, neopentyl glycol, and 1,4-butenediol; and trihydric or higher polyhydric alcohols such as glycerin, pentaerythritol, trimethylolpropane, and sorbitol.

[0038] The crystalline polyester preferably has structural units derived from an aliphatic diol and structural units derived from an aliphatic carboxylic acid, and more preferably has only structural units derived from an aliphatic diol and structural units derived from an aliphatic carboxylic acid.

[0039] The number of carbon atoms in the aliphatic diol or aliphatic carboxylic acid is more preferably within a range of 6 to 10. By making the crystalline polyester have a structure that is relatively not bulky, it is thought that the ester groups can be prevented from becoming locally highly dense, and charge leakage can be suppressed.

[0040] The ratio of polyhydric alcohol to polycarboxylic acid in the synthesis of polyester is not particularly limited. The equivalent ratio of hydroxyl groups of polyhydric alcohol to carboxyl groups of polycarboxylic acid is preferably within the range of 1.5 / 1 to 1 / 1.5, more preferably within the range of 1.2 / 1 to 1 / 1.2.

[0041] Examples of catalysts that can be used in polyester synthesis include metal-containing compounds, phosphorous compounds, phosphoric acid compounds, amine compounds, etc. Examples of metals contained in metal-containing compounds include sodium, lithium, magnesium, calcium, aluminum, zinc, manganese, antimony, titanium, tin, zirconium, germanium, etc. These may be used alone or in combination of two or more.

[0042] The polymerization temperature is not particularly limited, but is preferably within a range of, for example, 150 to 250° C. The polymerization time is not particularly limited, but is preferably within a range of, for example, 0.5 to 10 hours. During the polymerization, the reaction system may be reduced in pressure as necessary.

[0043] The weight average molecular weight Mw of the polyester resin is not particularly limited. The weight average molecular weight Mw of the amorphous polyester resin is preferably within a range of 10,000 to 100,000. The weight average molecular weight Mw of the crystalline polyester resin is preferably within a range of 1,000 to 29,000, more preferably within a range of 1,000 to 20,000, and still more preferably within a range of 1,000 to 15,000.

[0044] The weight-average molecular weight Mw of a polyester resin can be measured, for example, by the following method. A gel permeation chromatograph "HLC-8320GPC" (manufactured by Tosoh Corporation) equipped with one "TSKgel guard column SuperHZ-L" column and three "TSKgel SuperHZM-M" columns (all manufactured by Tosoh Corporation) is used. The column (TSK-) is stabilized at 40°C, and tetrahydrofuran (THF) is passed through the column at this temperature as a carrier solvent at a flow rate of 0.35 mL / min. A THF sample solution containing the measurement sample, adjusted to a sample concentration of 1 mg / mL, is treated on a roll mill for 10 minutes at room temperature. The solution is filtered through a 0.2 μm pore membrane filter to obtain a sample solution. 10 μL of this sample solution, along with the carrier solvent, is injected into the instrument and detected using a refractive index detector (RI detector). A calibration curve is prepared using a polystyrene standard sample with a monodisperse molecular weight distribution. The molecular weight distribution of the measurement sample is calculated based on this calibration curve. The calibration curve is prepared from 10 samples of "Polystylene Standard Sample TSK Standard" manufactured by Tosoh Corporation: "A-500", "F-1", "F-10", "F-80", "F-380", "A-2500", "F-4", "F-40", "F-128", and "F-700". The data collection interval for sample analysis is 300 ms.

[0045] The glass transition temperature Tg of the amorphous polyester resin is preferably in the range of 30 to 70° C., more preferably in the range of 40 to 65° C. This allows the toner containing the amorphous polyester resin to achieve both low-temperature fixability and high-temperature storage stability at high levels. The glass transition temperature Tg of the amorphous polyester resin can be controlled by the resin composition.

[0046] The glass transition temperature Tg can be measured, for example, by the following method. Differential scanning calorimetry (DSC) was performed using a differential scanning calorimeter "DSC7000X" (Hitachi Corporation) and a thermal analyzer controller "AS3 / DX" (Hitachi Corporation). Specifically, 5 mg of sample was first sealed in an AL autosampler sample container (φ6.8 H2.5 mm) (Hitachi Corporation) and an AL autosampler cover (Hitachi Corporation). This was then placed in the sample holder of the "AS3 / DX" and the temperature was cycled in the following order: heating, cooling, and heating again. During the first and second heating runs, the temperature was increased from 0°C to 150°C at a rate of 10°C / min and held at 150°C for 1 minute. During cooling, the temperature was decreased from 150°C to 0°C at a rate of 10°C / min and held at 0°C for 1 minute. A baseline shift was observed in the measurement curve obtained during the second heating run. The intersection of the extension of the baseline before the shift and the tangent line showing the maximum slope of the shifted portion of the baseline is taken as the glass transition point Tg. An empty aluminum pan is used as a reference.

[0047] The melting point Tm of the crystalline polyester resin is preferably in the range of 55 to 90°C, more preferably in the range of 60 to 85°C, and still more preferably in the range of 60 to 75°C. This tends to improve the low-temperature fixability and hot offset resistance of the toner containing the crystalline polyester resin. The melting point Tm of the crystalline polyester resin can be controlled by the resin composition.

[0048] The melting point (Tm) is the temperature at the peak of the endothermic peak and can be measured by differential scanning calorimetry (DSC). For example, differential scanning calorimetry (DSC) is performed using a differential scanning calorimeter (DSC7000X, manufactured by Hitachi) and a thermal analysis controller (AS3 / DX, manufactured by Hitachi). Specifically, 5 mg of sample is sealed in an AL autosampler sample container (φ6.8 mm, H2.5 mm, manufactured by Hitachi) and an AL autosampler cover (manufactured by Hitachi). This is placed in the sample holder of the AS3 / DX, and the temperature is changed in the following order: heating, cooling, and heating again. During the first and second heating cycles, the temperature is raised from 0°C to 150°C at a rate of 10°C / min and held at 150°C for 1 minute. During cooling, the temperature is lowered from 150°C to 0°C at a rate of 10°C / min and held at 0°C for 1 minute. The melting point (Tm) is determined by the temperature at the top of the endothermic peak in the endothermic curve obtained during the second heating. An empty aluminum pan is used as a reference.

[0049] The total acid value and hydroxyl value of the polyester resin is preferably within the range of 200 to 1000 mgKOH / g. When the total acid value and hydroxyl value is 200 mgKOH / g or more, the brittleness resistance of the polyester resin is further improved. This further improves the crush resistance of the toner containing the polyester resin. When the total acid value and hydroxyl value is 1000 mgKOH / g or less, polymerization is sufficiently carried out, thereby further improving the heat-resistant storage stability of the toner containing the polyester resin.

[0050] The acid value of polyester resin can be measured according to the method of JIS K 0070:1992. However, the measurement solvent is changed from the ethanol and ether mixed solvent specified in JIS K 0070. For measurements of amorphous polyester resin, the solvent is changed to a mixed solvent of acetone and toluene (acetone:toluene = 1:1 (volume ratio)). For measurements of crystalline polyester resin, the solvent is changed to a mixed solvent of chloroform and dimethylformamide (chloroform:dimethylformamide = 7:3 (volume ratio)).

[0051] The hydroxyl value of polyester resin can be measured based on the method of JIS K 0070: 1992. However, the measurement solvent is changed from the ethanol and ether mixed solvent specified in JIS K 0070 to tetrahydrofuran.

[0052] [1-2. Metal elements] The polyester resin composition of the present invention further contains at least one element selected from the group consisting of boron, aluminum, and phosphorus. As described above, boron, aluminum, and phosphorus can form trivalent cations. Therefore, boron, aluminum, and phosphorus improve the brittleness resistance of the polyester resin and the crush resistance of the toner through an ionic crosslinking effect with ionized functional groups and / or electron bias in the polyester resin. In addition, boron, aluminum, and phosphorus also have the effect of improving the heat-resistant storage stability of the toner while maintaining its low-temperature fixability through the same ionic crosslinking effect.

[0053] The total content of boron, aluminum, and phosphorus is preferably within a range of 300 to 3,000 ppm by mass relative to 100% by mass of the polyester resin content. When the total content is 300 ppm by mass or more, the crush resistance of the toner containing the polyester resin composition is further improved. When the total content is 3,000 ppm by mass or less, discoloration of the polyester resin can be prevented. This prevents the color of the toner containing the polyester resin composition from becoming dull.

[0054] The metal element content in a polyester resin composition can be measured, for example, as follows. First, 3 parts by mass of the polyester resin composition is added to and dispersed in 35 parts by mass of a 0.2% by mass aqueous solution of polyoxyethyl phenyl ether. This dispersion is treated with an ultrasonic homogenizer US-1200T (manufactured by Nippon Seiki Seisakusho) at 25°C for 5 minutes to obtain a measurement sample. Next, the emission lines of the measurement sample are obtained by acid decomposition and inductively coupled plasma-optical emission spectrometry (ICP-OES). The content of each metal element is determined from the emission lines and a calibration curve created in advance by measuring intensity values ​​for multiple known amounts, starting from small amounts, using the element as a standard sample.

[0055] The forms of boron, aluminum, and phosphorus present in the polyester resin composition are not particularly limited. From the viewpoint of the ionic crosslinking effect, these elements are preferably present in the form of ions containing these metal elements.

[0056] These metal elements are contained in the polyester resin composition as metal element additives added in the production process of the polyester resin composition, for example. The metal element additive may be an esterification catalyst for synthesizing the polyester resin.

[0057] Examples of boron additives among the metal element additives include boric acid, diboron trioxide, boron trichloride, boron tribromide, boron triiodide, boron trifluoride-n-hexylamine, boron trifluoride-monoethylamine, boron trifluoride-benzylamine, boron trifluoride-diethylamine, boron trifluoride-piperidine, boron trifluoride-triethylamine, boron trifluoride-aniline, boron tetrafluoride-n-hexylamine, boron tetrafluoride-monoethylamine, boron tetrafluoride-benzylamine, boron tetrafluoride-diethylamine, boron tetrafluoride-piperidine, boron tetrafluoride-triethylamine, boron tetrafluoride-aniline, tetrahydrofuran-borane complex, and dimethyl sulfide-borane complex.

[0058] Examples of aluminum additives among the metal element additives include carboxylates such as aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, aluminum laurate, aluminum stearate, aluminum benzoate, aluminum trichloroacetate, aluminum lactate, aluminum citrate, and aluminum salicylate; inorganic acid salts such as aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, aluminum carbonate, aluminum phosphate, and aluminum phosphonate; aluminum alkoxides such as aluminum methoxide, aluminum ethoxide, aluminum n-propoxide, aluminum iso-propoxide, aluminum n-butoxide, and aluminum t-butoxide; aluminum chelate compounds such as aluminum acetylacetonate, aluminum acetylacetate, aluminum ethylacetoacetate, and aluminum ethylacetoacetate diso-propoxide; organic aluminum compounds such as trimethylaluminum and triethylaluminum, and partial hydrolysates thereof; and aluminum oxide. Of these, carboxylates, inorganic acid salts, and chelate compounds are preferred, and aluminum acetate, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, and aluminum acetylacetonate are more preferred.

[0059] The amount of aluminum additive used is preferably 0.001 to 1.0 mol % relative to the number of moles of polycarboxylic acid, and more preferably 0.005 to 0.5 mol %. Because catalytic activity varies significantly depending on the type and combination of polycarboxylic acid and polyhydric alcohol used, and the polymerization method, a wide range of aluminum additive usage is required. This tendency is similar for other polymerization catalysts. In particular, when polymerization is not carried out under reduced pressure, the amount of polymerization catalyst must be significantly increased. The polymerization catalyst of the present invention exhibits sufficient catalytic activity, resulting in excellent thermal stability, thermo-oxidative stability, and hydrolysis resistance of the resulting polyester, and suppressing the generation of foreign matter and coloration due to aluminum.

[0060] A specific example of a method for preparing the solution using basic aluminum acetate as the aluminum additive is shown below.

[0061] An example of preparing an aqueous solution of basic aluminum acetate is as follows. That is, water is added to basic aluminum acetate, and the mixture is thoroughly dispersed at room temperature, followed by dissolution at room temperature to 100°C to obtain an aqueous solution. In this case, a lower temperature is preferable, and a shorter heating time is preferable. The concentration of the aqueous solution is preferably 10 to 30 g / L, and particularly preferably 15 to 20 g / L.

[0062] In order to prevent heat shock during the addition of the catalyst, a preferred embodiment is to convert the basic aluminum acetate aqueous solution into an ethylene glycol solution. That is, ethylene glycol is added to the above-mentioned aqueous solution. The amount of ethylene glycol added is preferably 0.5 to 5.0 times, by volume, the amount of the aqueous solution. More preferably, it is 0.8 to 2.0 times. After the solution is stirred to obtain a uniform water / ethylene glycol mixed solution, the solution is heated to distill off the water, thereby obtaining an ethylene glycol solution. The temperature is preferably 70°C or higher and 130°C or lower. More preferably, the solution is heated and stirred at 80 to 120°C to distill off the water. Even more preferably, the catalyst solution is prepared by heating under reduced pressure and / or in an inert gas atmosphere such as nitrogen or argon, and distilling off the water.

[0063] The above ethylene glycol is just an example, and other alkylene glycols can be used in the same manner.

[0064] The basic aluminum acetate is preferably solubilized in a solvent such as water or glycol, particularly in water and / or ethylene glycol, which can improve catalytic activity and reduce foreign matter.

[0065] Examples of phosphorus additives among metal element additives include phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds. The use of these phosphorus additives not only improves catalytic activity but also improves physical properties such as the thermal stability of polyesters. Among these, the use of phosphonic acid compounds is preferred because of their significant effects of improving physical properties and catalytic activity. Among the above-mentioned phosphorus additives, compounds having an aromatic ring structure are preferred because of their significant effects of improving physical properties and catalytic activity.

[0066] In the present invention, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds refer to compounds having structures represented by the following formulas 1 to 6, respectively. In formulas 1 to 6, "*" represents a bonding site to another substituent or atom.

[0067] [ka]

[0068] Examples of phosphonic acid compounds include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate, etc. Examples of phosphinic acid compounds include diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, phenyl phenylphosphinate, etc. Examples of phosphine oxide compounds include diphenylphosphine oxide, methyldiphenylphosphine oxide, triphenylphosphine oxide, etc.

[0069] Among the phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds and phosphine compounds, the compounds represented by the following formulas 7 to 12 are preferred.

[0070] [ka]

[0071] Among the above phosphorus additives, compounds having an aromatic ring structure are preferably used because they have a significant effect of improving physical properties and catalytic activity.

[0072] Furthermore, it is preferable to use a compound represented by any one of the following general formulas 13 to 15 as the phosphorus additive, as this has a particularly large effect of improving physical properties and catalytic activity.

[0073] General formula 13:P(=O)R 1 (OR 2 )(OR 3 ) General formula 14:P(=O)R 1 R 4 (OR 2 ) General formula 15:P(=O)R 1 R 5 R 6

[0074] In general formulas 13 to 15, R 1 , R 4 , R 5 , and R 6 R each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms containing a hydroxyl group, a halogen group, an alkoxy group, or an amino group. 2 , and R 3 each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms and containing a hydroxyl group or an alkoxyl group. The hydrocarbon group may contain an alicyclic structure or an aromatic ring structure.

[0075] As the phosphorus additive, R 1 , R4 , R 5 , and R 6 is a group having an aromatic ring structure is particularly preferred.

[0076] Examples of phosphorus additives include dimethyl methylphosphonate, diphenyl methylphosphonate, dimethyl phenylphosphonate, diethyl phenylphosphonate, diphenyl phenylphosphonate, dimethyl benzylphosphonate, diethyl benzylphosphonate, diphenylphosphinic acid, methyl diphenylphosphinate, phenyl diphenylphosphinate, phenylphosphinic acid, methyl phenylphosphinate, phenyl phenylphosphinate, diphenylphosphine oxide, methyldiphenylphosphine oxide, triphenylphosphine oxide, etc. Among these, dimethyl phenylphosphonate and diethyl benzylphosphonate are particularly preferred.

[0077] Among the above-mentioned phosphorus additives, phosphorus metal salt compounds are particularly preferred. The phosphorus metal salt compound is not particularly limited as long as it is a metal salt of a phosphorus additive. When the phosphorus metal salt compound is a metal salt of a phosphonic acid compound, it is preferable because it has a significant effect of improving the physical properties of polyester and enhancing catalytic activity. Examples of the metal salt of a phosphorus additive include monometal salts, dimetal salts, trimetal salts, etc.

[0078] Among the above phosphorus additives, those in which the metal moiety of the metal salt is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, and Zn are used, and are therefore preferred because they have a significant effect of improving catalytic activity. Of these, Li, Na, and Mg are particularly preferred.

[0079] As the phosphorus metal salt compound, it is preferable to use at least one compound selected from the compounds represented by the following general formula 16, as this has a significant effect of improving physical properties and catalytic activity.

[0080] [ka]

[0081] In general formula 16, R 1 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms containing a hydroxyl group, a halogen group, an alkoxy group, or an amino group. 2 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms containing a hydroxyl group or an alkoxyl group. 3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms containing a hydroxyl group, an alkoxyl group, or a carbonyl group. l represents an integer of 1 or more. m represents 0 or an integer of 1 or more. l+m is 4 or less. M represents a metal cation with a valence of (l+m). n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure, a branched structure, or an aromatic ring structure.

[0082] The above R 1 Examples of R include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, and 2-biphenyl. 2 Examples of R include hydrogen, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a long-chain aliphatic group, a phenyl group, a naphthyl group, a substituted phenyl group, a naphthyl group, and a group represented by -CHCHOH. 3 O - Examples of the cation include hydroxide ion, alcoholate ion, acetate ion, and acetylacetone ion.

[0083] Among the compounds represented by general formula 16, it is preferable to use at least one selected from the compounds represented by the following general formula 17.

[0084] [ka]

[0085] In general formula 17, R 1 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms containing a hydroxyl group, a halogen group, an alkoxyl group, or an amino group.3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms containing a hydroxyl group, an alkoxyl group, or a carbonyl group. l represents an integer of 1 or more. m represents 0 or an integer of 1 or more. l+m is 4 or less. M represents a metal cation with a valence of (l+m). The hydrocarbon group may contain a branched structure, an alicyclic structure, or an aromatic ring structure.

[0086] The above R 1 Examples of R include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, and 2-biphenyl. 3 O - Examples of the cation include hydroxide ion, alcoholate ion, acetate ion, and acetylacetone ion.

[0087] Among the above phosphorus additives, compounds having an aromatic ring structure are preferably used because they have a significant effect of improving physical properties and catalytic activity.

[0088] Among the compounds of the general formula 17, M selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, and Zn is preferably used because it has a significant effect of improving catalytic activity. Of these, Li, Na, and Mg are particularly preferred.

[0089] Examples of phosphorus metal salt compounds include lithium [ethyl (1-naphthyl)methylphosphonate], sodium [ethyl (1-naphthyl)methylphosphonate], magnesium bis[ethyl (1-naphthyl)methylphosphonate], potassium [ethyl (2-naphthyl)methylphosphonate], magnesium bis[ethyl (2-naphthyl)methylphosphonate], lithium [ethyl benzylphosphonate], sodium [ethyl benzylphosphonate], magnesium bis[ethyl benzylphosphonate], beryllium bis[ethyl benzylphosphonate], strontium bis[ethyl benzylphosphonate], manganese bis[ethyl benzylphosphonate], sodium benzylphosphonate, and magnesium Examples of suitable bis[benzylphosphonic acid], sodium [ethyl (9-anthryl)methylphosphonate], magnesium bis[ethyl (9-anthryl)methylphosphonate], sodium [ethyl 4-hydroxybenzylphosphonate], magnesium bis[ethyl 4-hydroxybenzylphosphonate], sodium [phenyl 4-chlorobenzylphosphonate], magnesium bis[ethyl 4-chlorobenzylphosphonate], sodium [methyl 4-aminobenzylphosphonate], magnesium bis[methyl 4-aminobenzylphosphonate], sodium phenylphosphonate, magnesium bis[ethyl phenylphosphonate], zinc bis[ethyl phenylphosphonate], and the like. Among these, lithium [ethyl (1-naphthyl)methylphosphonate], sodium [ethyl (1-naphthyl)methylphosphonate], magnesium bis[ethyl (1-naphthyl)methylphosphonate], lithium [ethyl benzylphosphonate], sodium [ethyl benzylphosphonate], magnesium bis[ethyl benzylphosphonate], sodium benzylphosphonate, and magnesium bis[benzylphosphonic acid] are particularly preferred.

[0090] Among the above-mentioned phosphorus additives, compounds having at least one P-OH bond are particularly preferred. The inclusion of such phosphorus additives enhances the effect of improving the physical properties of polyesters. Furthermore, the use of such phosphorus additives in combination with aluminum additives during polyester polymerization significantly improves catalytic activity.

[0091] The phosphorus additive having at least one P-OH bond is not particularly limited as long as it is a phosphorus additive having at least one P-OH in the molecule. Among these phosphorus additives, a phosphonic acid compound having at least one P-OH bond is preferably used, since it facilitates complex formation with the aluminum additive and has a significant effect of improving the physical properties of the polyester and enhancing the catalytic activity.

[0092] Among the above phosphorus additives, compounds having an aromatic ring structure are preferably used because they have a significant effect of improving physical properties and catalytic activity.

[0093] As the phosphorus additive having at least one P—OH bond, it is preferable to use at least one compound selected from the compounds represented by the following general formula 18, which has a significant effect of improving physical properties and catalytic activity.

[0094] [ka]

[0095] In general formula 18, R 1 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms containing a hydroxyl group, a halogen group, an alkoxyl group, or an amino group. 2 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms containing a hydroxyl group or an alkoxyl group. n represents an integer of 1 or more. The hydrocarbon group may contain a branched structure, an alicyclic structure, or an aromatic ring structure.

[0096] The above R 1 Examples of R include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, and 2-biphenyl. 2 Examples of such groups include hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic groups, phenyl, naphthyl, substituted phenyl, naphthyl, and groups represented by -CHCHOH.

[0097] Among the above phosphorus additives, compounds having an aromatic ring structure are preferably used because they have a significant effect of improving physical properties and catalytic activity.

[0098] Examples of phosphorus additives having at least one P-OH bond include ethyl (1-naphthyl)methylphosphonate, (1-naphthyl)methylphosphonic acid, ethyl (2-naphthyl)methylphosphonate, ethyl benzylphosphonate, benzylphosphonic acid, ethyl (9-anthryl)methylphosphonate, ethyl 4-hydroxybenzylphosphonate, ethyl 2-methylbenzylphosphonate, phenyl 4-chlorobenzylphosphonate, methyl 4-aminobenzylphosphonate, ethyl 4-methoxybenzylphosphonate, etc. Among these, ethyl (1-naphthyl)methylphosphonate and ethyl benzylphosphonate are particularly preferred.

[0099] Preferred examples of the phosphorus additive include the phosphorus additive represented by the following general formula 19. General formula 19:R 1 -CH2-P(=O)(OR 2 )(OR 3 )

[0100] In general formula 19, R 1 represents a hydrocarbon group having 1 to 49 carbon atoms, or a hydrocarbon group having 1 to 49 carbon atoms containing a hydroxyl group, a halogen group, an alkoxyl group, or an amino group. 2 and R 3 each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group containing a hydroxyl group or an alkoxyl group and having 1 to 50 carbon atoms. The hydrocarbon group may contain an alicyclic structure, a branched structure, or an aromatic ring structure.

[0101] The phosphorus additive is more preferably R in general formula 19 1 , R 2 and R 3 At least one of the compounds contains an aromatic ring structure.

[0102] Specific examples of these phosphorus additives are shown below.

[0103] [ka]

[0104] The phosphorus additive having a larger molecular weight is more effective and is therefore more preferable since it is less likely to be distilled off during polymerization.

[0105] The phosphorus additive is preferably a phosphorus additive having a phenol moiety in the same molecule. By including a phosphorus additive having a phenol moiety in the same molecule, the effect of improving the physical properties of the polyester is enhanced. Furthermore, by using a phosphorus additive having a phenol moiety in the same molecule during polyester polymerization, the effect of enhancing catalytic activity is greater, and therefore polyester productivity is excellent.

[0106] The phosphorus additive having a phenol moiety in the same molecule is not particularly limited as long as it is a phosphorus additive having a phenol structure. The use of a compound selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphineous acid compounds, and phosphine compounds, which have a phenol moiety in the same molecule, is preferred because it has a significant effect of improving the physical properties of polyesters and enhancing catalytic activity. Among these, the use of a phosphonic acid compound having a phenol moiety in the same molecule is particularly preferred because it has a particularly significant effect of improving the physical properties of polyesters and enhancing catalytic activity.

[0107] As the phosphorus additive having a phenol moiety in the same molecule, compounds represented by the following general formulas 20 to 22 are preferred.

[0108] General formula 20:P(=O)R 1 (OR 2 )(OR 3 ) General formula 21:P(=O)R 1 R 4 (OR 2 ) General formula 22:P(=O)R 1 R 5 R 6

[0109] In general formulas 20 to 22, R 1 R represents a hydrocarbon group having 1 to 50 carbon atoms and containing a phenol moiety. 1 R may contain substituents such as hydroxyl groups, halogen groups, alkoxyl groups, and amino groups. 4 , R 5 and R 6 R each independently represents hydrogen or a hydrocarbon group having 1 to 50 carbon atoms. This hydrocarbon group having 1 to 50 carbon atoms may contain a substituent such as a hydroxyl group, a halogen group, an alkoxyl group, or an amino group. 2 and R 3 R each independently represents hydrogen or a hydrocarbon group having 1 to 50 carbon atoms. This hydrocarbon group having 1 to 50 carbon atoms may contain a substituent such as a hydroxyl group or an alkoxyl group. The hydrocarbon group may contain a branched structure, an alicyclic structure, or an aromatic ring structure. 2 and R 4 The ends of may be bonded together.

[0110] Examples of phosphorus additives having a phenol moiety in the same molecule include p-hydroxyphenylphosphonic acid, dimethyl p-hydroxyphenylphosphonate, diethyl p-hydroxyphenylphosphonate, diphenyl p-hydroxyphenylphosphonate, bis(p-hydroxyphenyl)phosphinic acid, methyl bis(p-hydroxyphenyl)phosphinate, phenyl bis(p-hydroxyphenyl)phosphinate, p-hydroxyphenylphenylphosphinic acid, methyl p-hydroxyphenylphenylphosphinate, phenyl p-hydroxyphenylphenylphosphinate, p-hydroxyphenylphosphinic acid, methyl p-hydroxyphenylphosphinate, phenyl p-hydroxyphenylphosphinate, bis(p-hydroxyphenyl)phosphine oxide, tris(p-hydroxyphenyl)phosphine oxide, bis(p-hydroxyphenyl)methylphosphine oxide, and compounds represented by the following formulas 23 to 26. Among these, the compound represented by the following formula 23 and dimethyl p-hydroxyphenylphosphonate are particularly preferred.

[0111] [ka]

[0112] As the compound represented by formula 25, SANKO-220 (manufactured by Sankosha) is available.

[0113] Among the phosphorus additives having a phenol moiety in the same molecule, at least one selected from the specific phosphorus metal salt compounds represented by the following general formula 27 is particularly preferred.

[0114] [ka]

[0115] In formula 27, R 1 and R 2 R each independently represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms. 3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms containing a hydroxyl group or an alkoxyl group. 4 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms containing a hydroxyl group, an alkoxyl group, or a carbonyl group. 4 O - Examples of the cation include hydroxide ion, alcoholate ion, acetate ion, and acetylacetone ion. l represents an integer of 1 or more. m represents 0 or an integer of 1 or more. l+m is 4 or less. M represents a metal cation with a valence of (l+m). n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure, a branched structure, or an aromatic ring structure.

[0116] Among these, at least one compound selected from the compounds represented by the following general formula 28 is preferred.

[0117] [ka]

[0118] In general formula 28, M n+ represents a metal cation with a valence of n, where n is an integer of 1 to 4.

[0119] Among the compounds of general formula 27 or 28, those in which M is selected from Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, and Zn are preferably used, as this significantly improves catalytic activity. Of these, Li, Na, and Mg are particularly preferred.

[0120] Specific phosphorus metal salt compounds include lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], potassium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis[ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], magnesium bis[ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], beryllium bis[3,5-di-tert-butyl bis[3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid methyl], strontium bis[3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl], barium bis[3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid phenyl], manganese bis[3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl], nickel bis[3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl], copper bis[3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl], zinc bis[3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid ethyl], and the like. Among these, lithium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], sodium [ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate], and magnesium bis[ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate] are particularly preferred.

[0121] Among phosphorus additives having a phenol moiety in the same molecule, at least one selected from specific phosphorus additives having at least one P—OH bond represented by the following general formula 29 is particularly preferred.

[0122] [ka]

[0123] In general formula 29, R 1 and R 2 R each independently represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms. 3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms containing a hydroxyl group or an alkoxyl group. n represents an integer of 1 or more. The hydrocarbon group may contain a branched structure, an alicyclic structure, or an aromatic ring structure.

[0124] Among these, at least one compound selected from the compounds represented by the following general formula 30 is preferred.

[0125] [ka]

[0126] In general formula 30, R 3 represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms and containing a hydroxyl group or an alkoxyl group. The hydrocarbon group may contain a branched structure, an alicyclic structure, or an aromatic ring structure.

[0127] The above R 3 Examples of such groups include hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic groups, phenyl, naphthyl, substituted phenyl, naphthyl, and groups represented by -CHCHOH.

[0128] Specific phosphorus additives having at least one P—OH bond include ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, isopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, phenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, etc. Among these, ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and methyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.

[0129] Among phosphorus additives having a phenol moiety in the same molecule, at least one phosphorus additive selected from specific phosphorus additives represented by the following general formula 31 is preferred.

[0130] [ka]

[0131] In general formula 31, R 1 and R 2 R each independently represents hydrogen or a hydrocarbon group having 1 to 30 carbon atoms. 3 and R 4 each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms containing a hydroxyl group or an alkoxyl group. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure, a branched structure, or an aromatic ring structure.

[0132] Among the compounds of general formula 31, it is preferable to use at least one compound selected from the compounds represented by the following general formula 32, since this has a high effect of improving the physical properties of the polyester and the catalytic activity.

[0133] [ka]

[0134] In general formula 32, R 3 and R 4 each independently represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group containing a hydroxyl group or an alkoxyl group and having 1 to 50 carbon atoms. The hydrocarbon group may contain an alicyclic structure, a branched structure, or an aromatic ring structure.

[0135] The above R 3 and R 4 Examples of the alkyl group include hydrogen, short-chain aliphatic groups such as methyl and butyl groups, long-chain aliphatic groups such as octadecyl, aromatic groups such as phenyl, naphthyl, substituted phenyl and naphthyl groups, and groups represented by -CHCHOH.

[0136] Specific phosphorus additives include diisopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di-n-butyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, etc. Among these, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and diphenyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate are particularly preferred.

[0137] Among phosphorus additives having a phenol moiety in the same molecule, particularly desirable compounds are those represented by the following formula 33 or 34.

[0138] [ka]

[0139] Irganox 1222 (manufactured by Ciba Specialty Chemicals) is a commercially available compound represented by the above formula 33. Irganox 1425 (manufactured by Ciba Specialty Chemicals) is a commercially available compound represented by the above formula 34.

[0140] Other preferred phosphorus additives include phosphonic acid compounds represented by the following formula 35 or 36 having a linking group (X), and phosphonic acid compounds represented by the following formula 37 not having a linking group (X).

[0141] Formula 35:R 1 -X-(P=O)(OR 2 )(OR 3 )

[0142] In formula 35, R 1 represents an aromatic ring structure having 6 to 50 carbon atoms or a heterocyclic structure having 4 to 50 carbon atoms. The aromatic ring structure or heterocyclic structure may have a substituent. X is a linking group selected from aliphatic hydrocarbons having 1 to 10 carbon atoms, aliphatic hydrocarbons having 1 to 10 carbon atoms and containing a substituent, -O-, -OCH2-, -SO2-, -CO-, -COCH2-, -CHOCO-, -NHCO-, -NH-, -NHCONH-, -NHSO2-, and -NHC3H6OCH2CH2O-. The aliphatic hydrocarbon may have any of a straight-chain structure, a branched structure, and an alicyclic structure. R 2 and R 3 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having 1 to 20 carbon atoms and containing a hydroxyl group or an alkoxyl group. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure.

[0143] The substituents of the aromatic ring structure and heterocyclic ring structure of the phosphorus additive represented by formula 35 are one or more selected from the following group: A hydrocarbon group having 1 to 50 carbon atoms (which may have a linear structure, an alicyclic structure, a branched structure, or an aromatic ring structure, and these may be substituted with halogen). Hydroxyl groups Halogen groups Alkoxy group with 1 to 10 carbon atoms Amino group (optionally substituted with alkyl or alkanol having 1 to 10 carbon atoms) Nitro group Carboxy group Aliphatic carboxylic acid ester group with 1 to 10 carbon atoms Formyl group Acyl group Sulfonic acid group Sulfonic acid amide group (which may be substituted with an alkyl or alkanol group having 1 to 10 carbon atoms) Phosphoryl-containing groups Nitrile group Cyanoalkyl groups

[0144] Examples of phosphorus additives represented by formula 35 include benzylphosphonic acid, benzylphosphonic acid monoethyl ester, 1-naphthylmethylphosphonic acid, 1-naphthylmethylphosphonic acid monoethyl ester, 2-naphthylmethylphosphonic acid, 2-naphthylmethylphosphonic acid monoethyl ester, 4-phenyl,benzylphosphonic acid, 4-phenyl,benzylphosphonic acid monoethyl ester, 2-phenyl,benzylphosphonic acid, 2-phenyl,benzylphosphonic acid monoethyl ester, 4-chlorobenzylphosphonic acid, 4-chlorobenzylphosphonic acid monoethyl ester, and 4-chlorobenzylphosphonic acid diethyl ester. ter, 4-methoxybenzylphosphonic acid, 4-methoxybenzylphosphonic acid monoethyl ester, 4-methoxybenzylphosphonic acid diethyl ester, 4-methylbenzylphosphonic acid, 4-methylbenzylphosphonic acid monoethyl ester, 4-methylbenzylphosphonic acid diethyl ester, 4-nitrobenzylphosphonic acid, 4-nitrobenzylphosphonic acid monoethyl ester, 4-nitrobenzylphosphonic acid diethyl ester, 4-aminobenzylphosphonic acid, 4-aminobenzylphosphonic acid monoethyl ester, 4-aminobenzylphosphonic acid diethyl ester, 2-methyl Benzylphosphonic acid, 2-methyl, benzylphosphonic acid monoethyl ester, 2-methyl, benzylphosphonic acid diethyl ester, 10-anthranimethylphosphonic acid, 10-anthranimethylphosphonic acid monoethyl ester, 10-anthranimethylphosphonic acid diethyl ester, (4-methoxyphenyl-, ethoxy-)methylphosphonic acid, (4-methoxyphenyl-, ethoxy-)methylphosphonic acid monomethyl ester, (4-methoxyphenyl-, ethoxy-)methylphosphonic acid dimethyl ester, (phenyl-, hydroxy-)methylphosphonic acid, (phenyl-, hydroxy-)methylphosphonic acid monoethyl ester, (phenyl-, hydroxy-)methylphosphonic acid diethyl ester, (phenyl-, chloro-)methylphosphonic acid, (phenyl-, chloro-)methylphosphonic acid monoethyl ester, (phenyl-,Chloro-)methylphosphonic acid diethyl ester, (4-chlorophenyl)-iminophosphonic acid, (4-chlorophenyl)-iminophosphonic acid monoethyl ester, (4-chlorophenyl)-iminophosphonic acid diethyl ester, (4-hydroxyphenyl-,diphenyl-)methylphosphonic acid, (4-hydroxyphenyl-,diphenyl-)methylphosphonic acid monoethyl ester, (4-hydroxyphenyl-,diphenyl-)methylphosphonic acid diethyl ester, (4-chlorophenyl-,hydroxy-)methylphosphonic acid, (4- Examples include chlorophenyl-, hydroxy-)methylphosphonic acid monomethyl ester, (4-chlorophenyl-, hydroxy-)methylphosphonic acid dimethyl ester, 2-benzofuranylmethylphosphonic acid diethyl ester, 2-benzofuranylmethylphosphonic acid monoethyl ester, 2-benzofuranylmethylphosphonic acid, 2-(5-methyl)benzofuranylmethylphosphonic acid diethyl ester, 2-(5-methyl)benzofuranylmethylphosphonic acid monoethyl ester, and 2-(5-methyl)benzofuranylmethylphosphonic acid. The phosphorus additives having the above linking groups are preferred in terms of polymerization activity.

[0145] Formula 36:(R 0 ) m -R 1 -(CH2) n -(P=O)(OR 2 )(OR 3 )

[0146] In formula 36, ​​R 0 represents a hydroxyl group, a C1-C10 alkyl group, a -COOH group, a -COOR group 4 , an alkylene glycol group, or a monoalkoxyalkylene glycol group. 4 represents a C1 to C4 alkyl group. Monoalkoxyalkylene glycol represents a C1 to C4 glycol. R 1 R represents an aromatic ring structure such as benzene, naphthalene, biphenyl, diphenyl ether, diphenyl thioether, diphenyl sulfone, diphenylmethane, diphenyldimethylmethane, diphenyl ketone, anthracene, phenanthrene, and pyrene.2 and R 3 each independently represents a hydrogen atom, a C1-C4 hydrocarbon group, or a C1-C4 hydrocarbon group having a hydroxyl group or an alkoxy group, m represents an integer of 1 to 5, and R 0 When there are a plurality of n, they may be the same or different substituents.

[0147] Among the phosphorus additives represented by formula 36, ​​examples of phosphorus additives in which the aromatic ring structure having a substituent is benzene include benzylphosphonic acids in which a hydroxyl group has been introduced into the benzene ring, such as 2-hydroxybenzylphosphonic acid diethyl ester, 2-hydroxybenzylphosphonic acid monoethyl ester, 2-hydroxybenzylphosphonic acid, 4-hydroxybenzylphosphonic acid diethyl ester, 4-hydroxybenzylphosphonic acid monoethyl ester, 4-hydroxybenzylphosphonic acid, 6-hydroxybenzylphosphonic acid diethyl ester, 6-hydroxybenzylphosphonic acid monoethyl ester, and 6-hydroxybenzylphosphonic acid; 2-n-Butylbenzylphosphonic acid diethyl ester, 2-n-butylbenzylphosphonic acid monomethyl ester, 2-n-butylbenzylphosphonic acid, 3-n-butylbenzylphosphonic acid diethyl ester, 3-n-butylbenzylphosphonic acid monoethyl ester, 3-n-butylbenzylphosphonic acid, 4-n-butylbenzylphosphonic acid diethyl ester, 4-n-butylbenzylphosphonic acid monoethyl ester, 4-n-butylbenzylphosphonic acid, 2,5-n-dibutylbenzylphosphonic acid diethyl ester, 2,5-n-dibutylbenzyl Benzylphosphonic acids with alkyl groups introduced into the benzene ring, such as phosphonic acid monoethyl ester, 2,5-n-dibutylbenzylphosphonic acid, 3,5-n-dibutylbenzylphosphonic acid diethyl ester, 3,5-n-dibutylbenzylphosphonic acid monoethyl ester, and 3,5-n-dibutylbenzylphosphonic acid, 2-carboxybenzylphosphonic acid diethyl ester, 2-carboxybenzylphosphonic acid monoethyl ester, 2-carboxybenzylphosphonic acid, 3-carboxybenzylphosphonic acid diethyl ester, and 3-carboxybenzylphosphonic acid. Phosphonic acid monoethyl ester, 3-carboxybenzylphosphonic acid, 4-carboxybenzylphosphonic acid diethyl ester, 4-carboxybenzylphosphonic acid monoethyl ester, 4-carboxybenzylphosphonic acid, 2,5-dicarboxybenzylphosphonic acid diethyl ester, 2,5-dicarboxybenzylphosphonic acid monoethyl ester, 2,5-dicarboxybenzylphosphonic acid, 3,5-dicarboxybenzylphosphonic acid diethyl ester, 3,5-dicarboxybenzylphosphonic acid monoethyl ester, 3,5-dicarboxybenzylphosphonic acid Sulfonic acid, 2-methoxycarbonylbenzylphosphonic acid diethyl ester, 2-methoxycarbonylbenzylphosphonic acid monoethyl ester, 2-methoxycarbonylbenzylphosphonic acid, 3-methoxycarbonylbenzylphosphonic acid diethyl ester, 3-methoxycarbonylbenzylphosphonic acid monoethyl ester, 3-methoxycarbonylbenzylphosphonic acid, 4-methoxycarbonylbenzylphosphonic acid diethyl ester, 4-methoxycarbonylbenzylphosphonic acid monoethyl ester, 4-methoxycarbonylbenzylphosphonic acid, 2,Benzylphosphonic acids with a carboxyl group or a carboxylic acid ester group introduced into the benzene ring, such as 5-dimethoxycarbonylbenzylphosphonic acid diethyl ester, 2,5-dimethoxycarbonylbenzylphosphonic acid monoethyl ester, 2,5-dimethoxycarbonylbenzylphosphonic acid, 3,5-dimethoxycarbonylbenzylphosphonic acid diethyl ester, 3,5-dimethoxycarbonylbenzylphosphonic acid monoethyl ester, and 3,5-dimethoxycarbonylbenzylphosphonic acid, and 2-(2-hydroxyethoxy)benzylphosphonic acid diethyl ester 2-(2-hydroxyethoxy)benzylphosphonic acid monoethyl ester, 2-(2-hydroxyethoxy)benzylphosphonic acid, 3-(2-hydroxyethoxy)benzylphosphonic acid diethyl ester, 3-(2-hydroxyethoxy)benzylphosphonic acid monoethyl ester, 3-(2-hydroxyethoxy)benzylphosphonic acid, 4-(2-hydroxyethoxy)benzylphosphonic acid diethyl ester, 4-(2-hydroxyethoxy)benzylphosphonic acid monoethyl ester, 4-(2-hydroxyethoxy)benzylphosphonic acid, 2,5-di (2-Hydroxyethoxy)benzylphosphonic acid diethyl ester, 2,5-di(2-hydroxyethoxy)benzylphosphonic acid monoethyl ester, 2,5-di(2-hydroxyethoxy)benzylphosphonic acid, 3,5-di(2-hydroxyethoxy)benzylphosphonic acid diethyl ester, 3,5-di(2-hydroxyethoxy)benzylphosphonic acid monoethyl ester, 3,5-di(2-hydroxyethoxy)benzylphosphonic acid, 2-(2-methoxyethoxy)benzylphosphonic acid diethyl ester, 2-(2-methoxyethoxy)benzylphosphonic acid phosphonic acid monoethyl ester, 1-(2-methoxyethoxy)benzylphosphonic acid, 3-(2-methoxyethoxy)benzylphosphonic acid monomethyl ester, 3-(2-methoxyethoxy)benzylphosphonic acid diethyl ester, 3-(2-methoxyethoxy)benzylphosphonic acid monoethyl ester, 3-(2-methoxyethoxy)benzylphosphonic acid, 4-(2-methoxyethoxy)benzylphosphonic acid diethyl ester, 4-(2-methoxyethoxy)benzylphosphonic acid monoethyl ester, 4-(2-methoxyethoxy)benzylphosphonic acid, 2,Examples include benzylphosphonic acids in which an alkylene glycol group or a monoalkoxylated alkylene glycol group has been introduced into the benzene ring, such as 5-di(2-methoxyethoxy)benzylphosphonic acid diethyl ester, 2,5-di(2-methoxyethoxy)benzylphosphonic acid monoethyl ester, 2,5-di(2-methoxyethoxy)benzylphosphonic acid, 3,5-di(2-methoxyethoxy)benzylphosphonic acid diethyl ester, 3,5-di(2-methoxyethoxy)benzylphosphonic acid monoethyl ester, and 3,5-di(2-methoxyethoxy)benzylphosphonic acid.

[0148] Among the phosphorus additives represented by formula 36, ​​the phosphorus additives in which the aromatic ring structure having a substituent is benzene are not limited to the above-mentioned single-substituent species. As the phosphorus additive, a mixture of the above-mentioned substituents, a hydroxyl group, an alkyl group, a carboxy group, a carboxy ester group, a 2-hydroxyethoxy group, or a 2-methoxyethoxy group can also be used.

[0149] Among the phosphorus additives represented by formula 36, ​​examples of the phosphorus additive in which the aromatic ring structure having a substituent is naphthalene include 1-(5-hydroxy)naphthylmethylphosphonic acid diethyl ester, 1-(5-hydroxy)naphthylmethylphosphonic acid monoethyl ester, 1-(5-hydroxy)naphthylmethylphosphonic acid, 1-(5-hydroxy)naphthylmethylphosphonic acid diethyl ester, 1-(5-hydroxy)naphthylmethylphosphonic acid monoethyl ester, 1-(5-hydroxy)naphthylmethylphosphonic acid, 1-(5-n-butyl)naphthylmethylphosphonic acid, Sulfonic acid diethyl ester, 1-(5-n-butyl)naphthylmethylphosphonic acid monoethyl ester, 1-(5-n-butyl)naphthylmethylphosphonic acid, 1-(4-carboxy)naphthylmethylphosphonic acid diethyl ester, 1-(4-carboxy)naphthylmethylphosphonic acid monoethyl ester, 1-(4-carboxy)naphthylmethylphosphonic acid, 1-(4-methoxycarbonyl)naphthylmethylphosphonic acid diethyl ester, 1-(4-methoxycarbonyl)naphthylmethylphosphonic acid monoethyl ester, 1-(4-methoxycarbonyl )Naphthyl methylphosphonic acid, 1-[4-(2-hydroxyethoxy)]naphthyl methylphosphonic acid diethyl ester, 1-[4-(2-hydroxyethoxy)]naphthyl methylphosphonic acid monoethyl ester, 1-[4-(2-hydroxyethoxy)]naphthyl methylphosphonic acid, 1-(4-methoxyethoxy)naphthyl methylphosphonic acid diethyl ester, 1-(4-methoxyethoxy)naphthyl methylphosphonic acid monoethyl ester, 1-(4-methoxyethoxy)naphthyl methylphosphonic acid, 1-(5-hydroxy)naphthyl methylphosphonic acid phosphonic acid diethyl ester, 2-(6-hydroxy)naphthyl methylphosphonic acid diethyl ester, 2-(6-hydroxy)naphthyl monoethyl phosphonic acid, 2-(6-hydroxy)naphthyl methylphosphonic acid, 2-(6-n-butyl)naphthyl methylphosphonic acid diethyl ester, 2-(6-n-butyl)naphthyl methylphosphonic acid monoethyl ester, 2-(6-n-butyl)naphthyl methylphosphonic acid, 2-(6-carboxy)naphthyl methylphosphonic acid diethyl ester, 2-(6-carboxy)naphthyl methylphosphonic acid monoethyl ester,Examples of phosphonic acids include those in which an alkyl group, a carboxyl group, a carboxylic acid ester group, an alkylene glycol group, a monoalkoxyalkylene glycol group, or the like is introduced into a naphthalene ring, such as 2-(6-carboxy)naphthylmethylphosphonic acid, 2-(6-methoxycarbonyl)naphthylmethylphosphonic acid diethyl ester, 2-(6-methoxycarbonyl)naphthylmethylphosphonic acid monoethyl ester, 2-(6-methoxycarbonyl)naphthylmethylphosphonic acid, 2-[6-(2-hydroxyethoxy)]naphthylmethylphosphonic acid diethyl ester, 2-[6-(2-hydroxyethoxy)]naphthylmethylphosphonic acid monoethyl ester, 2-[6-(2-hydroxyethoxy)]naphthylmethylphosphonic acid, 2-(6-methoxyethoxy)naphthylmethylphosphonic acid diethyl ester, 2-(6-methoxyethoxy)naphthylmethylphosphonic acid monoethyl ester, and 2-(6-methoxyethoxy)naphthylmethylphosphonic acid. ,

[0150] Among the phosphorus additives represented by formula 36, ​​the phosphorus additives in which the aromatic ring structure having a substituent is naphthalene are not limited to the above-mentioned single-substituent types. As the phosphorus additive, those having a mixture of the above-mentioned substituents, a hydroxyl group, an alkyl group, a carboxy group, a carboxy ester group, a 2-hydroxyethoxy group, or a 2-methoxyethoxy group can also be used.

[0151] Among the phosphorus additives represented by formula 36, ​​examples of the phosphorus additive in which the aromatic ring structure having a substituent is biphenyl include 4-(4-hydroxyphenyl)benzylphosphonic acid diethyl ester, 4-(4-hydroxyphenyl)benzylphosphonic acid monoethyl ester, 4-(4-hydroxyphenyl)benzylphosphonic acid, 4-(4-n-butylphenyl)benzylphosphonic acid diethyl ester, 4-(4-n-butylphenyl)benzylphosphonic acid monoethyl ester, 4-(4-n-butylphenyl)benzylphosphonic acid, 4-(4-carboxyphenyl)benzylphosphonic acid diethyl ester, Examples thereof include phosphonic acids in which an alkyl group, a carboxyl group, a carboxylic acid ester group, an alkylene glycol group, a monomethoxyalkylene glycol group, or the like is introduced into a biphenyl ring, such as 4-(4-carboxyphenyl)benzylphosphonic acid monoethyl ester, 4-(4-carboxyphenyl)benzylphosphonic acid, 4-(4-methoxycarbonylphenyl)benzylphosphonic acid diethyl ester, 4-(4-methoxycarbonylphenyl)benzylphosphonic acid monoethyl ester, 4-(4-methoxycarbonylphenyl)benzylphosphonic acid, 4-(4-hydroxyethoxyphenyl)benzylphosphonic acid diethyl ester, 4-(4-hydroxyethoxyphenyl)benzylphosphonic acid monoethyl ester, 4-(4-hydroxyethoxyphenyl)benzylphosphonic acid, 4-(4-methoxyethoxyphenyl)benzylphosphonic acid diethyl ester, 4-(4-methoxyethoxyphenyl)benzylphosphonic acid monoethyl ester, and 4-(4-methoxyethoxyphenyl)benzylphosphonic acid.

[0152] Among the phosphorus additives represented by formula 36, ​​the phosphorus additives in which the aromatic ring structure having a substituent is biphenyl are not limited to the above-mentioned single-substituent types. The phosphorus additives may also be those having a mixture of the above-mentioned substituents, hydroxyl group, alkyl group, carboxy group, carboxy ester group, 2-hydroxyethoxy group, or 2-methoxyethoxy group.

[0153] Among the phosphorus additives represented by formula 36, ​​examples of phosphorus additives in which the aromatic ring structure having a substituent is diphenyl ether include 4-(4-hydroxyphenyloxy)benzylphosphonic acid diethyl ester, 4-(4-hydroxyphenyloxy)benzylphosphonic acid monoethyl ester, 4-(4-hydroxyphenyloxy)benzylphosphonic acid, 4-(4-n-butylphenyloxy)benzylphosphonic acid monoethyl ester, 4-(4-n-butylphenyloxy)benzylphosphonic acid monoethyl ester, 4-(4-butylphenyloxy)benzylphosphonic acid, 4-(4-carboxyphenyloxy)benzylphosphonic acid monoethyl ester, 4-(4-carboxyphenyloxy)benzylphosphonic acid monoethyl ester, 4-(4-carboxyphenyloxy)benzylphosphonic acid, 4-(4-methoxycarbonylphenyloxy)benzylphosphonic acid monoethyl ester and phosphonic acids in which an alkyl group, a carboxylate group, an alkylene glycol group, a monomethoxyalkylene glycol group, or the like is introduced into a diphenyl ether ring such as ester, 4-(4-methoxycarbonylphenyloxy)benzylphosphonic acid monoethyl ester, 4-(4-methoxycarbonylphenyloxy)benzylphosphonic acid, 4-(4-hydroxyethoxyphenyloxy)benzylphosphonic acid monoethyl ester, 4-(4-hydroxymethoxyphenyloxy)benzylphosphonic acid monoethyl ester, 4-(4-hydroxymethoxyphenyloxy)benzylphosphonic acid, 4-(4-methoxyethoxyphenyloxy)benzylphosphonic acid monoethyl ester, 4-(4-methoxyethoxyphenyloxy)benzylphosphonic acid monoethyl ester, 4-(4-methoxyethoxyphenyloxy)benzylphosphonic acid monoethyl ester, and 4-(4-methoxyethoxyphenyloxy)benzylphosphonic acid.

[0154] Among the phosphorus additives represented by formula 36, ​​the phosphorus additive whose substituted aromatic ring structure is diphenyl ether is not limited to the above-mentioned single-substituent type. The phosphorus additive may also be a mixture of the above-mentioned substituents, hydroxyl group, alkyl group, carboxy group, carboxy ester group, 2-hydroxyethoxy group, or 2-methoxyethoxy group.

[0155] Among the phosphorus additives represented by formula 36, ​​examples of phosphorus additives in which the aromatic ring structure having a substituent is a diphenylthioether include 4-(4-hydroxyphenylthio)benzylphosphonic acid diethyl ester, 4-(4-hydroxyphenylthio)benzylphosphonic acid monoethyl ester, 4-(4-hydroxyphenylthio)benzylphosphonic acid, 4-(4-n-butylphenylthio)benzylphosphonic acid monoethyl ester, 4-(4-n-butylphenylthio)benzylphosphonic acid monoethyl ester, 4-(4-butylphenylthio)benzylphosphonic acid, 4-(4-carboxyphenylthio)benzylphosphonic acid monoethyl ester, 4-(4-carboxyphenylthio)benzylphosphonic acid monoethyl ester, 4-(4-carboxyphenylthio)benzylphosphonic acid, 4-(4-methoxycarbonylphenylthio)benzylphosphonic acid monoethyl ester and phosphonic acids in which an alkyl group, a carboxyl group, a carboxylic acid ester group, an alkylene glycol group, a monomethoxyalkylene glycol group, or the like is introduced into a diphenyl thioether ring, such as 4-(4-methoxycarbonylphenylthio)benzylphosphonic acid monoethyl ester, 4-(4-methoxycarbonylphenylthio)benzylphosphonic acid, 4-(4-hydroxyethoxyphenylthio)benzylphosphonic acid monoethyl ester, 4-(4-hydroxymethoxyphenylthio)benzylphosphonic acid monoethyl ester, 4-(4-hydroxymethoxyphenylthio)benzylphosphonic acid, 4-(4-methoxyethoxyphenylthio)benzylphosphonic acid monoethyl ester, 4-(4-methoxyethoxyphenylthio)benzylphosphonic acid monoethyl ester, 4-(4-methoxyethoxyphenylthio)benzylphosphonic acid, and the like.

[0156] Among the phosphorus additives represented by formula 36, ​​the phosphorus additive in which the aromatic ring structure having a substituent is a diphenylthioether is not limited to the above-mentioned single-substituent type. The phosphorus additive may also be a mixture of the above-mentioned substituents, a hydroxyl group, an alkyl group, a carboxyl group, a carboxy ester group, a 2-hydroxyethoxy group, or a 2-methoxyethoxy group.

[0157] Among the phosphorus additives represented by formula 36, ​​examples of the phosphorus additive in which the aromatic ring structure having a substituent is diphenyl sulfone include 4-(4-hydroxyphenylsulfonyl)benzylphosphonic acid diethyl ester, 4-(4-hydroxyphenylsulfonyl)benzylphosphonic acid monoethyl ester, 4-(4-hydroxyphenylsulfonyl)benzylphosphonic acid, 4-(4-n-butylphenylsulfonyl)benzylphosphonic acid monoethyl ester, 4-(4-n-butylphenylsulfonyl)benzylphosphonic acid monoethyl ester, 4-(4-butylphenylsulfonyl)benzylphosphonic acid, 4-(4-carboxyphenylsulfonyl)benzylphosphonic acid monoethyl ester, 4-(4-carboxyphenylsulfonyl)benzylphosphonic acid monoethyl ester, 4-(4-carboxyphenylsulfonyl)benzylphosphonic acid, 4-(4-methoxycarbonylphenylsulfonyl)benzylphosphonic acid monoethyl ester, and phosphonic acids in which an alkyl group, a carboxylate group, an alkylene glycol group, a monomethoxyalkylene glycol group or the like is introduced into a diphenyl sulfone ring, such as 4-(4-methoxycarbonylphenylsulfonyl)benzylphosphonic acid monoethyl ester, 4-(4-methoxycarbonylphenylsulfonyl)benzylphosphonic acid, 4-(4-hydroxyethoxyphenylsulfonyl)benzylphosphonic acid monoethyl ester, 4-(4-hydroxymethoxyphenylsulfonyl)benzylphosphonic acid monoethyl ester, 4-(4-hydroxymethoxyphenylsulfonyl)benzylphosphonic acid, 4-(4-methoxyethoxyphenylsulfonyl)benzylphosphonic acid monoethyl ester, 4-(4-methoxyethoxyphenylsulfonyl)benzylphosphonic acid monoethyl ester, 4-(4-methoxyethoxyphenylsulfonyl)benzylphosphonic acid monoethyl ester, and 4-(4-methoxyethoxyphenylsulfonyl)benzylphosphonic acid.

[0158] Among the phosphorus additives represented by formula 36, ​​the phosphorus additive whose substituted aromatic ring structure is diphenyl sulfone is not limited to the above-mentioned single-substituent type. The phosphorus additive may also be a mixture of the above-mentioned substituents, hydroxyl group, alkyl group, carboxy group, carboxy ester group, 2-hydroxyethoxy group, or 2-methoxyethoxy group.

[0159] Among the phosphorus additives represented by formula 36, ​​examples of phosphorus additives in which the substituted aromatic ring structure is diphenylmethane include 4-(4-hydroxybenzyl)benzylphosphonic acid diethyl ester, 4-(4-hydroxybenzyl)benzylphosphonic acid monoethyl ester, 4-(4-hydroxybenzyl)benzylphosphonic acid, 4-(4-n-butylbenzyl)benzylphosphonic acid monoethyl ester, 4-(4-n-butylbenzyl)benzylphosphonic acid monoethyl ester, 4-(4-butylbenzyl)benzylphosphonic acid, 4-(4-carboxybenzyl)benzylphosphonic acid monoethyl ester, 4-(4-carboxybenzyl)benzylphosphonic acid monoethyl ester, 4-(4-carboxybenzyl)benzylphosphonic acid, and 4-(4-methoxycarbonylbenzyl)benzylphosphonic acid monoethyl ester. , 4-(4-methoxycarbonylbenzyl)benzylphosphonic acid monoethyl ester, 4-(4-methoxycarbonylbenzyl)benzylphosphonic acid, 4-(4-hydroxyethoxybenzyl)benzylphosphonic acid monoethyl ester, 4-(4-hydroxymethoxybenzyl)benzylphosphonic acid monoethyl ester, 4-(4-hydroxymethoxybenzyl)benzylphosphonic acid, 4-(4-methoxyethoxybenzyl)benzylphosphonic acid monoethyl ester, 4-(4-methoxyethoxybenzyl)benzylphosphonic acid monoethyl ester, 4-(4-methoxyethoxybenzyl)benzylphosphonic acid monoethyl ester, 4-(4-methoxyethoxybenzyl)benzylphosphonic acid, and the like, phosphonic acids in which an alkyl group, a carboxyl group, a carboxylic acid ester group, an alkylene glycol group, a monomethoxyalkylene glycol group, or the like is introduced into a diphenylmethane ring, such as 4-(4-methoxycarbonylbenzyl)benzylphosphonic acid monoethyl ester, 4-(4-methoxycarbonylbenzyl)benzylphosphonic acid, 4-(4-hydroxyethoxybenzyl)benzylphosphonic acid monoethyl ester, 4-(4-methoxyethoxybenzyl)benzylphosphonic acid

[0160] Among the phosphorus additives represented by formula 36, ​​the phosphorus additive in which the aromatic ring structure having a substituent is diphenylmethane is not limited to the above-mentioned single-substituent type. The phosphorus additive may also be a mixture of the above-mentioned substituents, hydroxyl group, alkyl group, carboxy group, carboxy ester group, 2-hydroxyethoxy group, or 2-methoxyethoxy group.

[0161] Among the phosphorus additives represented by formula 36, ​​examples of phosphorus additives in which the aromatic ring structure having a substituent is diphenyldimethylmethane include 4-(4-hydroxyphenyldimethylmethyl)benzylphosphonic acid diethyl ester, 4-(4-hydroxyphenyldimethylmethyl)benzylphosphonic acid monoethyl ester, 4-(4-hydroxyphenyldimethylmethyl)benzylphosphonic acid, 4-(4-n-butylphenyldimethylmethyl)benzylphosphonic acid monoethyl ester, 4-(4-n-butylphenyldimethylmethyl)benzylphosphonic acid monoethyl ester, 4-(4-butylphenyldimethylmethyl)benzylphosphonic acid, 4-(4-carboxyphenyldimethylmethyl)benzylphosphonic acid monoethyl ester, 4-(4-carboxyphenyldimethylmethyl)benzylphosphonic acid monoethyl ester, 4-(4-carboxyphenyldimethylmethyl)benzylphosphonic acid, 4-(4-methoxycarbonylphenyldimethylmethyl)benzylphosphonic acid monoethyl ester, 4-(4-methoxycarbonylphenyldimethylmethyl)benzylphosphonic acid monoethyl ester, 4-(4-methoxycarbonylphenyldimethylmethyl)benzylphosphonic acid, 4-(4-hydroxyethoxyphenyldimethylmethyl)benzylphosphonic acid monoethyl ester, 4-(4-hydroxymethoxyphenyldimethylmethyl)benzylphosphonic acid monoethyl ester, 4-(4-hydroxymethoxyphenyldimethylmethyl)benzylphosphonic acid, 4-(4-methoxyethoxyphenyldimethylmethyl)benzylphosphonic acid monoethyl ester, 4-(4-methoxyethoxyphenyldimethylmethyl)benzylphosphonic acid monoethyl ester, 4-(4-methoxyethoxyphenyldimethylmethyl)benzylphosphonic acid monoethyl ester, 4-(4-methoxyethoxyphenyldimethylmethyl)benzylphosphonic acid monoethyl ester, 4-(4-methoxyethoxyphenyldimethylmethyl)benzylphosphonic acid, and the like.

[0162] Among the phosphorus additives represented by formula 36, ​​the phosphorus additive in which the substituted aromatic ring structure is diphenyldimethylmethane is not limited to the above-mentioned single-substituent type. The phosphorus additive may also be a mixture of the above-mentioned substituents, hydroxyl group, alkyl group, carboxy group, carboxy ester group, 2-hydroxyethoxy group, or 2-methoxyethoxy group.

[0163] Among the phosphorus additives represented by formula 36, ​​examples of phosphorus additives in which the substituted aromatic ring structure is diphenyl ketone include 4-(4-hydroxybenzoyl)benzylphosphonic acid diethyl ester, 4-(4-hydroxybenzoyl)benzylphosphonic acid monoethyl ester, 4-(4-hydroxybenzoyl)benzylphosphonic acid, 4-(4-n-butylbenzoyl)benzylphosphonic acid monoethyl ester, 4-(4-n-butylbenzoyl)benzylphosphonic acid monoethyl ester, 4-(4-butylbenzoyl)benzylphosphonic acid, 4-(4-carboxybenzoyl)benzylphosphonic acid monoethyl ester, 4-(4-carboxybenzoyl)benzylphosphonic acid monoethyl ester, 4-(4-carboxybenzoyl)benzylphosphonic acid, 4-(4-methoxycarbonylbenzoyl)benzylphosphonic acid monoethyl ester and phosphonic acids in which an alkyl group, a carboxylate group, an alkylene glycol group, a monomethoxyalkylene glycol group, or the like is introduced into a diphenyl ketone ring such as 4-(4-methoxycarbonylbenzoyl)benzylphosphonic acid monoethyl ester, 4-(4-methoxycarbonylbenzoyl)benzylphosphonic acid, 4-(4-hydroxyethoxybenzoyl)benzylphosphonic acid monoethyl ester, 4-(4-hydroxymethoxybenzoyl)benzylphosphonic acid monoethyl ester, 4-(4-hydroxymethoxybenzoyl)benzylphosphonic acid, 4-(4-methoxyethoxybenzoyl)benzylphosphonic acid monoethyl ester, 4-(4-methoxyethoxybenzoyl)benzylphosphonic acid monoethyl ester, and 4-(4-methoxyethoxybenzoyl)benzylphosphonic acid.

[0164] Among the phosphorus additives represented by formula 36, ​​the phosphorus additive in which the substituted aromatic ring structure is diphenyl ketone is not limited to the above-mentioned single-substituent type. The phosphorus additive may also be a mixture of the above-mentioned substituents, hydroxyl group, alkyl group, carboxy group, carboxy ester group, 2-hydroxyethoxy group, or 2-methoxyethoxy group.

[0165] Among the phosphorus additives represented by formula 36, ​​examples of phosphorus additives in which the aromatic ring structure having a substituent is anthracene include 9-(10-hydroxy)anthrylmethylphosphonic acid diethyl ester, 9-(10-hydroxy)anthrylmethylphosphonic acid monoethyl ester, 9-(10-hydroxy)anthrylmethylphosphonic acid, 9-(10-n-butyl)anthrylmethylphosphonic acid diethyl ester, 9-(10-n-butyl)anthrylmethylphosphonic acid monoethyl ester, 9-(10-n-butyl)anthrylmethylphosphonic acid, 9-(10-carboxy)anthrylmethylphosphonic acid diethyl ester, 9-(10-carboxy)anthrylmethylphosphonic acid monoethyl ester, 9-(10-carboxy)anthrylmethylphosphonic acid, 9-(10-carboxy)9-(2-hydroxyethoxy)anthrylmethylphosphonic acid, and phosphonic acids in which an alkyl group, a carboxylate group, an alkylene glycol group, a monomethoxyalkylene glycol group, or the like is introduced into an anthracene ring, such as phosphonic acid diethyl ester, 9-(2-hydroxyethoxy)anthrylmethylphosphonic acid monoethyl ester, 9-(2-hydroxyethoxy)anthrylmethylphosphonic acid, 9-(2-methoxyethoxy)anthrylmethylphosphonic acid diethyl ester, 9-(2-methoxyethoxy)anthrylmethylphosphonic acid monoethyl ester, 9-(2-methoxyethoxy)anthrylmethylphosphonic acid, 9-(2-methoxycarbonyl)anthrylmethylphosphonic acid diethyl ester, 9-(2-methoxycarbonyl)anthrylmethylphosphonic acid monoethyl ester, and 9-(2-methoxycarbonyl)anthrylmethylphosphonic acid.

[0166] Among the phosphorus additives represented by formula 36, ​​the phosphorus additives in which the aromatic ring structure having a substituent is anthracene are not limited to the above-mentioned single-substituent types. As the phosphorus additive, those having a mixture of the above-mentioned substituents, hydroxyl group, alkyl group, carboxy group, carboxy ester group, 2-hydroxyethoxy group, or 2-methoxyethoxy group can also be used.

[0167] Among the phosphorus additives represented by formula 36, ​​examples of the phosphorus additive in which the aromatic ring structure having a substituent is phenanthrene include 1-(7-n-butyl)phenanthrylmethylphosphonic acid diethyl ester, 1-(7-n-butyl)phenanthrylmethylphosphonic acid monoethyl ester, 1-(7-n-butyl)phenanthrylmethylphosphonic acid, 1-(7-carboxy)phenanthrylmethylphosphonic acid diethyl ester, 1-(7-carboxy)phenanthrylmethylphosphonic acid monoethyl ester, 1-(7-carboxy)phenanthrylmethylphosphonic acid, 1-(7-hydroxyethoxy)phenanthrylmethylphosphonic acid diethyl ester, 1-(7-hydroxyethoxy)phenanthrylmethylphosphonic acid monoethyl ester, 1-(7- Examples thereof include phosphonic acids in which an alkyl group, a carboxyl group, a carboxylic acid ester group, an alkylene glycol group, a monomethoxyalkylene glycol group, or the like is introduced into a phenanthrene ring, such as 1-(7-hydroxyethoxy)phenanthrylmethylphosphonic acid, 1-(7-methoxyethoxy)phenanthrylmethylphosphonic acid diethyl ester, 1-(7-methoxyethoxy)phenanthrylmethylphosphonic acid monoethyl ester, 1-(7-methoxyethoxy)phenanthrylmethylphosphonic acid, 1-(7-methoxycarbonyl)phenanthrylmethylphosphonic acid diethyl ester, 1-(7-methoxycarbonyl)phenanthrylmethylphosphonic acid monoethyl ester, and 1-(7-methoxycarbonyl)phenanthrylmethylphosphonic acid.

[0168] Among the phosphorus additives represented by formula 36, ​​the phosphorus additive in which the aromatic ring structure having a substituent is phenanthrene is not limited to the above-mentioned single-substituent type. The phosphorus additive may also be a mixture of the above-mentioned substituents, a hydroxyl group, an alkyl group, a carboxy group, a carboxy ester group, a 2-hydroxyethoxy group, or a 2-methoxyethoxy group.

[0169] Among the phosphorus additives represented by formula 36, ​​examples of phosphorus additives in which the aromatic ring structure having a substituent is pyrene include 1-(5-hydroxy)pyrenylmethylphosphonic acid diethyl ester, 1-(5-hydroxy)pyrenylmethylphosphonic acid monoethyl ester, 1-(5-hydroxy)pyrenylmethylphosphonic acid, 1-(5-n-butyl)pyrenylmethylphosphonic acid diethyl ester, 1-(5-n-butyl)pyrenylmethylphosphonic acid monoethyl ester, 1-(5-n-butyl)pyrenylmethylphosphonic acid, 1-(5-carboxy)pyrenylmethylphosphonic acid diethyl ester, 1-(5-carboxy)pyrenylmethylphosphonic acid monoethyl ester, 1-(5-carboxy)pyrenylmethylphosphonic acid, and 1-(5-hydroxyethoxy)pyrenylmethylphosphonic acid diethyl ester. , 1-(5-hydroxyethoxy)pyrenylmethylphosphonic acid monoethyl ester, 1-(5-hydroxyethoxy)pyrenylmethylphosphonic acid, 1-(5-methoxyethoxy)pyrenylmethylphosphonic acid diethyl ester, 1-(5-methoxyethoxy)pyrenylmethylphosphonic acid monoethyl ester, 1-(5-methoxyethoxy)pyrenylmethylphosphonic acid, 1-(5-methoxycarbonyl)pyrenylmethylphosphonic acid diethyl ester, 1-(5-methoxycarbonyl)pyrenylmethylphosphonic acid monoethyl ester, 1-(5-methoxycarbonyl)pyrenylmethylphosphonic acid, and the like phosphonic acids in which an alkyl group, a carboxyl group, a carboxylic acid ester group, an alkylene glycol group, a monomethoxyalkylene glycol group, or the like is introduced into the pyrene ring, such as 1-(5-hydroxyethoxy)pyrenylmethylphosphonic acid monoethyl ester, 1-(5-hydroxyethoxy)pyrenylmethylphosphonic acid, 1-(5-methoxyethoxy)pyrenylmethylphosphonic acid diethyl ester, 1-(5-methoxycarbonyl)pyrenylmethylphosphonic acid monoethyl ester, and 1-(5-methoxycarbonyl)pyrenylmethylphosphonic acid.

[0170] Among the phosphorus additives represented by formula 36, ​​the phosphorus additive in which the substituted aromatic ring structure is pyrene is not limited to the above-mentioned single-substituent type. The phosphorus additive may also be a mixture of the above-mentioned substituents, a hydroxyl group, an alkyl group, a carboxy group, a carboxy ester group, a 2-hydroxyethoxy group, or a 2-methoxyethoxy group.

[0171] The substituents introduced into the aromatic rings, such as hydroxyl, alkyl, carboxy, carboxy ester, 2-hydroxyethoxy, and 2-methoxyethoxy groups, are thought to be closely involved in the formation of complexes with aluminum atoms during polyester polymerization. These groups also contain groups similar to the carboxy and hydroxyl groups that are functional groups in polyester formation, and are easily dissolved or incorporated into the polyester matrix, making them particularly effective for improving polymerization activity and reducing foreign matter.

[0172] Aromatic ring structure (R 1 ) bound to R 0 Compared to unsubstituted groups where the substituent is a hydrogen atom, C1-C10 alkyl groups, -COOH groups, -COOR 4 Phosphorus additives substituted with alkylene glycol groups or monoalkoxyalkylene glycol groups are preferred not only in terms of improving catalytic activity but also in terms of the effect of reducing foreign matter. 4 represents a C1 to C4 alkyl group. Monoalkoxyalkylene glycol represents a C1 to C4 glycol.

[0173] Examples of the substituent bonded to the aromatic ring structure include a C1 to C10 alkyl group, a carboxy group, a carboxy ester group, an alkylene glycol, and a monoalkoxyalkylene glycol. In terms of the foreign matter reduction effect, a carboxy group, a carboxy ester group, an alkylene glycol, and a monoalkoxyalkylene glycol are more preferred. The reason for this is unclear, but it is presumed to be due to improved compatibility with the polyester and alkylene glycol, which is the catalyst medium.

[0174] Formula 37:R 1-(P=O)(OR 2 )(OR 3 )

[0175] R 1 represents an aromatic ring structure having 6 to 50 carbon atoms or a heterocyclic ring structure having 4 to 50 carbon atoms. The aromatic ring structure or heterocyclic ring structure may have a substituent. R 2 and R 3 each independently represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group containing a hydroxyl group or an alkoxyl group and having 1 to 20 carbon atoms. The hydrocarbon group may have an alicyclic structure, a branched structure, or an aromatic ring structure.

[0176] The substituents of the aromatic ring structure and heterocyclic ring structure of the phosphorus additive represented by formula 37 are one or more selected from the following group: A hydrocarbon group having 1 to 50 carbon atoms (which may have a linear structure, an alicyclic structure, a branched structure, or an aromatic ring structure, and these may be substituted with halogen). Hydroxyl groups Halogen groups Alkoxy group with 1 to 10 carbon atoms Amino group (optionally substituted with alkyl or alkanol having 1 to 10 carbon atoms) Nitro group Carboxy group Aliphatic carboxylic acid ester group with 1 to 10 carbon atoms Formyl group Acyl group Sulfonic acid group Sulfonic acid amide group (which may be substituted with an alkyl or alkanol group having 1 to 10 carbon atoms) Phosphoryl-containing groups Nitrile group Cyanoalkyl groups

[0177] The aromatic ring structure of Formula 37 is selected from benzene, naphthalene, biphenyl, diphenyl ether, diphenyl thioether, diphenyl sulfone, diphenyl methane, diphenyl dimethyl methane, anthracene, phenanthrene, and pyrene. The heterocyclic ring structure of Formula 37 is selected from furan, benzofuran, isobenzofuran, dibenzofuran, naphthalane, and phthalide. R in Formula 37 2 and R 3 At least one of these is preferably a hydrogen atom.

[0178] Examples of phosphorus additives represented by formula 37 include (3-nitro-5-methyl)-phenylphosphonic acid diethyl ester, (3-nitro-5-methyl)-phenylphosphonic acid monoethyl ester, (3-nitro-5-methyl)-phenylphosphonic acid, (3-nitro-5-methoxy)-phenylphosphonic acid diethyl ester, (3-nitro-5-methoxy)-phenylphosphonic acid monoethyl ester, (3-nitro-5-methoxy)-phenylphosphonic acid, (4-chloro)-phenylphosphonic acid diethyl ester, (4-chloro)-phenylphosphonic acid monoethyl ester, (4-chloro)-phenylphosphonic acid, (5-chloro)-phenylphosphonic acid diethyl ester, (5-chloro)-phenylphosphonic acid monoethyl ester, (5-chloro)-phenylphosphonic acid, (3 -nitro-5-methyl)-phenylphosphonic acid diethyl ester, (3-nitro-5-methyl)-phenylphosphonic acid monoethyl ester, (3-nitro-5-methyl)-phenylphosphonic acid, (4-nitro)-phenylphosphonic acid diethyl ester, (4-nitro)-phenylphosphonic acid monoethyl ester, (4-nitro)-phenylphosphonic acid, (5-nitro)-phenylphosphonic acid diethyl ester, (5-nitro)-phenylphosphonic acid monoethyl ester, (5-nitro)-phenylphosphonic acid, (6-nitro)-phenylphosphonic acid diethyl ester, (6-nitro)-phenylphosphonic acid monoethyl ester, (6-nitro)-phenylphosphonic acid, (4-nitro-6-methyl)-phenylphosphonic acid diethyl ester, (4-nitro-6-methyl)- Examples include phenylphosphonic acid monoethyl ester, (4-nitro-6-methyl)-phenylphosphonic acid, a phosphorus additive obtained by removing the methylene chain that is the linking group from a phosphorus additive represented by formula 36, ​​5-benzofuranylphosphonic acid diethyl ester, 5-benzofuranylphosphonic acid monoethyl ester, 5-benzofuranylphosphonic acid, 5-(2-methyl)benzofuranylphosphonic acid diethyl ester, 5-(2-methyl)benzofuranylphosphonic acid monoethyl ester, and 5-(2-methyl)benzofuranylphosphonic acid.

[0179] Phosphorus additives have been known as heat stabilizers for polyesters. However, it has not been known that these compounds significantly accelerate melt polymerization when used in combination with conventional metal-containing polyester polymerization catalysts. In fact, when melt polymerizing polyesters using typical catalysts such as antimony compounds, titanium compounds, tin compounds, or germanium compounds, the addition of phosphorus additives has not been found to accelerate polymerization to a substantially useful level.

[0180] On the other hand, it is preferable to coexist, in addition to the aluminum additive, at least one selected from alkali metals, alkaline earth metals, and compounds thereof as a second metal-containing component. The coexistence of these second metal-containing components is preferable because, compared to the coexistence of the above-mentioned phosphorus additive, contamination of the glycol component distilled during polymerization is more suppressed. When an alkylene oxide adduct of a dicarboxylic acid with bisphenol A or F or the like forms a secondary glycol, particularly propylene oxide, the coexistence of the above-mentioned second metal-containing component, particularly a lithium compound, in the catalyst system dramatically enhances catalytic activity. This results in a catalyst component with a higher reaction rate, which is effective in improving productivity. Furthermore, the coexistence of the above-mentioned second metal-containing component, particularly a lithium compound, in the catalyst system is preferable because, when the polymerization temperature needs to be kept low, for example, to 240 to 260°C, polymerization activity can be maintained by increasing the amount of the second metal-containing component added. Furthermore, favorable catalytic activity can also be achieved by adding a small amount of phosphorus additive to a system containing the above-mentioned aluminum compound and an alkali metal and / or alkaline earth metal.

[0181] The second alkaline earth metal is preferably at least one selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, and Ba. Among these, it is more preferable to use at least one selected from Li, Na, Mg, and compounds thereof. Among these, Li is most preferable. Examples of the alkali metal or alkaline earth metal compound include saturated aliphatic carboxylates of these metals such as formic acid, acetic acid, propionic acid, butyric acid, and oxalic acid; unsaturated aliphatic carboxylates such as acrylic acid and methacrylic acid; aromatic carboxylates such as benzoic acid; halogen-containing carboxylates such as trichloroacetic acid; hydroxycarboxylates such as lactic acid, citric acid, and salicylic acid; inorganic acid salts such as carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, and bromic acid; organic sulfonates such as 1-propanesulfonic acid, 1-pentanesulfonic acid, and naphthalenesulfonic acid; organic sulfates such as lauryl sulfate; alkoxides such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy; and chelate compounds, hydrides, oxides, and hydroxides of these metals with acetylacetonate.

[0182] Among these alkali metals, alkaline earth metals, or compounds thereof, when highly alkaline ones such as hydroxides are used, they tend to be difficult to dissolve in organic solvents such as diols (e.g., ethylene glycol) or alcohols. Therefore, they must be added to the polymerization system in the form of an aqueous solution, which can cause problems during the polymerization process. Furthermore, when highly alkaline ones such as hydroxides are used, the polyester is more susceptible to side reactions such as hydrolysis during polymerization, and the polymerized polyester tends to be more easily discolored and has reduced hydrolysis resistance. Therefore, suitable alkali metals, alkaline earth metals, or compounds thereof are saturated aliphatic carboxylates, unsaturated aliphatic carboxylates, aromatic carboxylates, halogen-containing carboxylates, hydroxycarboxylates, inorganic acid salts selected from sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, and bromic acid, organic sulfonates, organic sulfates, chelate compounds, and oxides of alkali metals or alkaline earth metals. Among these, saturated aliphatic carboxylates of alkali metals or alkaline earth metals, particularly acetates, are preferred from the standpoints of ease of handling and availability.

[0183] It is also possible to use a mixture of several types of catalysts.

[0184] [1-3. Thermal decomposition characteristics] In the polyester resin composition of the present invention, the total number N of peaks having a retention time equal to or shorter than that of 4,4'-dihydroxybiphenyl among the 20 peaks with the highest relative abundance in a chromatogram obtained by pyrolysis gas chromatography mass spectrometry is 1 to 17. As described above, in a polyester resin composition having a number N of 1 or more, the molecular cleavage energy and molecular weight of the components after thermal decomposition are relatively small, and the polarity of the components after thermal decomposition is strong. Such polyester resin compositions are susceptible to heat and improve the low-temperature fixability of toners. Furthermore, since the number N of the polyester resin composition of the present invention is 17 or less, even when thermally decomposed, the amount of short-chain components is not too large, and the crush resistance of the toner is not reduced.

[0185] The number N can be controlled by selecting the structure, molecular weight, dispersive power, polarity, etc. of the pyrolysis components of the polyester resin. The number N can also be controlled by adjusting the amount of monomers, reaction conditions, etc., when synthesizing the polyester resin. For example, by not using bisphenol A or bisphenol A derivatives as the polyhydric alcohols used when synthesizing the polyester resin, the number N can be controlled to 1 to 17. On the other hand, if the polyhydric alcohols used when synthesizing the polyester resin are all bisphenol A or bisphenol A derivatives, the pyrolysis product will be retained in the column due to the interaction between its molecular weight and polarity, and the number N will be 0. Furthermore, if the polyester resin is synthesized by ring-opening polymerization of L-lactone, the pyrolysis product will appear on the short-term side, and the number N will be 18 or more.

[0186] The analytical equipment used in pyrolysis gas chromatography mass spectrometry (pyrolysis GC / MS) is a gas chromatograph mass spectrometer with a pyrolysis device installed at the sample introduction point. This analytical equipment consists of a pyrolysis device, a gas chromatograph, and a mass spectrometer. The sample is heated instantaneously in an inert atmosphere in the pyrolysis device, and then decomposed into small molecules. The various types of small molecules that are decomposed are separated in columns using a gas chromatograph. Each separated component is detected by a mass spectrometer, and a chromatogram is obtained.

[0187] In the pyrolysis process using a pyrolyzer, the application of thermal energy to a sample causes the molecules themselves to thermally vibrate, irreversibly cleaving molecular bonds and / or changing their physical state when they are unable to withstand the thermal vibrations. In the gas chromatography process using a gas chromatograph, the decomposed small molecules are introduced into a column along with a carrier gas. Due to interactions with the stationary phase in the column based on the physical properties of the small molecules, such as molecular weight, molecular structure, polarity, and dispersion force, the small molecules move through the column, repeatedly adsorbing and distributing to the stationary phase. This results in differences in the arrival times of various small molecules at the column outlet, resulting in the separation of each small molecule. Furthermore, the masses of the small molecules are detected in a mass spectrometer, and the amount of the detected small molecules relative to their retention time is represented as a peak in a chromatogram.

[0188] The time from when a sample is injected until a peak appears is called the retention time. This retention time varies depending on the small molecule and is highly reproducible. Therefore, retention time is a crucial value for identifying components.

[0189] In the pyrolysis GC / MS of the present invention, the retention time of 4,4'-dihydroxybiphenyl is an index, so 4,4'-dihydroxybiphenyl does not necessarily have to be detected as a pyrolysis product. However, it is necessary to analyze 4,4'-dihydroxybiphenyl itself under the same analytical conditions and know its retention time.

[0190] Figure 1 shows a chromatogram of 4,4'-dihydroxybiphenyl alone obtained by pyrolysis GC / MS under certain conditions. The horizontal axis of the chromatogram represents retention time [min]. The vertical axis of the chromatogram represents relative abundance. From this chromatogram, it can be confirmed that the retention time of 4,4'-dihydroxybiphenyl under the specified conditions is 26.859 min.

[0191] Figure 2 is a chromatogram of a polyester resin composition according to one embodiment of the present invention, obtained by pyrolysis GC / MS under the same conditions as above. The peaks indicated by arrows in Figure 2 are the 20 peaks with the highest relative abundance in this chromatogram. Of these 20 peaks, the total number N of peaks with retention times equal to or shorter than that of 4,4'-dihydroxybiphenyl (26.859 min) is 14. The polyester resin contained in this polyester resin composition does not contain bisphenol A or a bisphenol A derivative as a constituent monomer, i.e., it does not have structural units derived from bisphenol A or bisphenol A derivatives.

[0192] Figure 3 shows a chromatogram of a comparative polyester resin composition obtained by pyrolysis GC / MS under the same conditions as above. Of the 20 peaks with high relative abundance in this chromatogram, the total number N of peaks with retention times shorter than that of 4,4'-dihydroxybiphenyl (26.859 min) is 0. The polyester resin contained in this polyester resin composition contains a bisphenol A derivative as a constituent monomer, i.e., has structural units derived from a bisphenol A derivative.

[0193] The detailed conditions for pyrolysis GC / MS are not particularly limited, and can be, for example, the conditions described in the Examples below.

[0194] [2. Toner for developing electrostatic images] The polyester resin composition of the present invention can be contained in, for example, a toner for developing electrostatic images. In this specification, "toner for developing electrostatic images" is also simply referred to as "toner." "Toner" refers to an aggregate of toner particles. The toner particles are composed of, for example, toner base particles and external additives.

[0195] The toner preferably contains the polyester resin composition of the present invention in an amount ranging from 30 to 97% by mass relative to the total amount of the toner (including external additives). When the content of the polyester resin composition is 30% by mass or more, the toner has better low-temperature fixability, heat-resistant storage stability, and crush resistance. When the content of the polyester resin composition is 97% by mass or less, other components such as external additives that contribute to improving heat-resistant storage stability can be contained in amounts greater than or equal to the required amount. In a toner containing a colorant, a release agent, and an external additive, the content of the polyester resin composition is more preferably 90.2% by mass or less. In a toner that does not contain a colorant, the content of the polyester resin composition is more preferably 95.1% by mass or less. The polyester resin composition is contained, for example, in toner base particles as a binder resin.

[0196] The toner base particles may contain, in addition to the polyester resin composition, other resins, a release agent, a colorant, a charge control agent, and other additives.

[0197] Other resins include vinyl resins, which are obtained by polymerization of at least vinyl monomers. Specific examples of vinyl resins include acrylic resins and styrene-acrylic copolymer resins.

[0198] Examples of polymerizable monomers used in styrene-acrylic resins include aromatic vinyl monomers and (meth)acrylic acid ester monomers.

[0199] Examples of aromatic vinyl monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, p-ethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, 2,4-dimethylstyrene, 3,4-dichlorostyrene, and derivatives thereof. These aromatic vinyl monomers can be used alone or in combination of two or more.

[0200] Examples of (meth)acrylic acid ester monomers include methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, ethyl β-hydroxyacrylate, propyl γ-aminoacrylate, stearyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc. These (meth)acrylic acid ester monomers can be used alone or in combination of two or more.

[0201] Among the above, it is preferable to use a styrene-based monomer in combination with an acrylic acid ester-based monomer or a methacrylic acid ester-based monomer.

[0202] The polymerizable monomer may also be a third vinyl monomer, such as an acid monomer such as acrylic acid, methacrylic acid, maleic anhydride, or vinylacetic acid, acrylamide, methacrylamide, acrylonitrile, ethylene, propylene, butylene vinyl chloride, N-vinylpyrrolidone, or butadiene.

[0203] The polymerizable monomer may further include a polyfunctional vinyl monomer. Examples of the polyfunctional vinyl monomer include diacrylates of ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and the like, and dimethacrylates and trimethacrylates of tertiary or higher alcohols such as divinylbenzene, pentaerythritol, and trimethylolpropane. The copolymerization ratio of the polyfunctional vinyl monomer to the total polymerizable monomers is usually within the range of 0.001 to 5% by mass, preferably within the range of 0.003 to 2% by mass, and more preferably within the range of 0.01 to 1% by mass.

[0204] Examples of release agents that the toner base particles may contain include waxes. Examples of waxes include hydrocarbon waxes such as low-molecular-weight polyethylene wax, low-molecular-weight polypropylene wax, Fischer-Tropsch wax, microcrystalline wax, and paraffin wax, and ester waxes such as carnauba wax, pentaerythritol behenate, behenyl behenate, and behenyl citrate. These may be used alone or in combination of two or more.

[0205] The melting point of the release agent is preferably within a range of 50 to 95° C. in order to improve the low-temperature fixability and releasability of the toner.

[0206] The melting point of the release agent can be determined by differential scanning calorimetry. For differential scanning calorimetry, a differential scanning calorimeter "Diamond DSC" (manufactured by PerkinElmer) can be used. The measurement is performed under the following measurement conditions (heating and cooling conditions): a first heating process in which the temperature is raised from 0°C to 200°C at a rate of 10°C / min and isothermal maintained at 200°C for 5 minutes; a cooling process in which the temperature is lowered from 200°C to 0°C at a rate of 10°C / min and isothermal maintained at 0°C for 5 minutes; and a second heating process in which the temperature is raised from 0°C to 200°C at a rate of 10°C / min. The above measurement is performed by sealing 3.0 mg of the release agent in an aluminum pan and setting it in the sample holder of the differential scanning calorimeter "Diamond DSC." An empty aluminum pan is used as a reference. In the above measurement, an analysis is performed on the endothermic curve obtained in the first temperature rise process, and the top temperature of the endothermic peak derived from the release agent component is taken as the melting point [°C].

[0207] The content of the release agent is preferably in the range of 2 to 20% by mass, more preferably in the range of 3 to 18% by mass, and even more preferably in the range of 4 to 15% by mass, based on the total amount of resin contained in the toner base particles.

[0208] Examples of colorants that can be contained in the toner base particles include carbon black, magnetic materials, dyes, and pigments.

[0209] Examples of carbon black include channel black, furnace black, acetylene black, thermal black, and lamp black.

[0210] Examples of magnetic materials include ferromagnetic metals such as iron, nickel, and cobalt, alloys containing these metals, and compounds of ferromagnetic metals such as ferrite and magnetite.

[0211] Examples of pigments include CI Pigment Red 2, 3, 5, 7, 15, 16, 48:1, 48:3, 53:1, 57:1, 81:4, 122, 123, 139, 144, 149, 166, 177, 178, 208, 209, 222, CI Pigment Orange 31, 43, CI Pigment Yellow 3, 9, 14, 17, 35, Examples of pigments that can be used include phthalocyanine pigments having a central metal such as zinc, titanium, magnesium, etc., such as CI Pigment Green 7, CI Pigment Blue 15:3, CI Pigment Blue 15:4, CI Pigment Green 60, and mixtures of these pigments.

[0212] Examples of dyes include CI Solvent Red 1, 3, 14, 17, 18, 22, 23, 49, 51, 52, 58, 63, 87, 111, 122, 127, 128, 131, 145, 146, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 176, 179, and pyrazolothria. Examples of suitable dyes include azole azo dyes, pyrazolotriazole azomethine dyes, pyrazolone azo dyes, pyrazolone azomethine dyes, CI Solvent Yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162, CI Solvent Blue 25, 36, 60, 70, 93, and 95, and mixtures thereof can also be used.

[0213] The content of the colorant is preferably in the range of 1 to 30% by mass, more preferably in the range of 2 to 20% by mass, based on the total amount of resin contained in the toner base particles.

[0214] As the charge control agent that can be contained in the toner base particles, various known ones can be used.

[0215] As the charge control agent, for example, various known compounds that can be dispersed in an aqueous medium can be used, and specific examples include nigrosine dyes, metal salts of naphthenic acid or higher fatty acids, alkoxylated amines, quaternary ammonium salt compounds, azo metal complexes, metal salicylate salts or metal complexes thereof, etc.

[0216] The content of the charge control agent is preferably in the range of 0.1 to 10.0% by mass, more preferably in the range of 0.5 to 5.0% by mass, based on the total amount of the resin for the toner base particle precursor.

[0217] The toner base particles may contain other additives as needed, such as magnetic powder, a flowability improver, a conductivity adjuster, a reinforcing filler such as a fibrous substance, an antioxidant, and a cleaning property improver.

[0218] The average circularity of the toner is preferably in the range of 0.950 to 0.995 from the viewpoint of improving crush resistance. The average circularity of the toner is measured using an "FPIA-2100" (manufactured by Sysmex Corporation). Specifically, the sample (toner) is first soaked in an aqueous solution containing a surfactant, and then dispersed by ultrasonic dispersion treatment for 1 minute. Then, using the "FPIA-2100" (manufactured by Sysmex Corporation), an image is taken using the measurement conditions HPF (high magnification imaging) mode at an appropriate density of 3,000 to 10,000 HPF detection counts. The circularity of each toner particle is calculated according to the following formula (T), and the circularity of each toner particle is added and divided by the total number of toner particles. This calculates the average circularity. Formula (T): Circularity = (perimeter of a circle with the same projected area as the particle image) / (perimeter of the projected particle image)

[0219] The toner may contain an external additive that is added to the surface of the toner base particles as a post-treatment agent in order to improve the fluidity, chargeability and cleaning properties of the toner particles.

[0220] The external additive is preferably an inorganic particle such as silica particles, alumina particles, zirconia particles, titanium oxide particles, strontium titanate particles, zinc oxide particles, chromium oxide particles, cerium oxide particles, antimony oxide particles, tungsten oxide particles, tin oxide particles, tellurium oxide particles, manganese oxide particles, boron oxide particles, etc. These inorganic particles may be hydrophobized with a surface treatment agent such as a silane coupling agent or silicone oil, as necessary.

[0221] The number-average primary particle diameter of the inorganic particles is preferably within a range of 20 to 200 nm, more preferably within a range of 30 to 150 nm. As the number-average primary particle diameter of the external additive, image data captured by a scanning electron microscope (SEM) is binarized using an image processing analyzer (LUZEX AP, manufactured by Nireco Corporation), and the average value of the Feret diameters in the horizontal direction measured for 100 particles can be used.

[0222] The external additive may be organic particles. Examples of organic particles include particles of a styrene homopolymer, a methyl methacrylate homopolymer, and a styrene-methyl methacrylate copolymer. The peak top particle size of the organic particles measured in the same manner as for inorganic particles is preferably within the range of 10 to 1000 nm.

[0223] The external additive may be a lubricant such as a metal salt of a higher fatty acid. Examples of the higher fatty acid include stearic acid, oleic acid, palmitic acid, linoleic acid, and ricinoleic acid. Examples of the metal constituting the metal salt include zinc, manganese, aluminum, iron, copper, magnesium, and calcium.

[0224] The content of the external additive is preferably in the range of 0.05 to 10.00% by mass, more preferably in the range of 0.10 to 5.00% by mass, based on the total amount of the toner. The external additive contained in the toner may be one type or two or more types.

[0225] The method for producing the toner is not particularly limited, and may be an emulsion aggregation method, a kneading and pulverization method, or the like.

[0226] As an example of the toner manufacturing method, a manufacturing method including a step of forming toner base particles having a core-shell structure by an emulsion aggregation method will be described below.

[0227] First, a water-based dispersion is prepared by dispersing various binder resin particle dispersions, a release agent particle dispersion, and a colorant particle dispersion in a water-based medium.

[0228] The aqueous dispersion refers to a dispersion in which dispersed bodies (particles) are dispersed in an aqueous medium whose main component (50% by mass or more) is water. The aqueous medium may contain a water-soluble organic medium in addition to water. Examples of the water-soluble organic medium include methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, and tetrahydrofuran.

[0229] A flocculant such as aluminum sulfate is added to the aqueous dispersion, and the dispersion is agglomerated by heating while warming, thereby forming core particles.

[0230] Separately prepared resin particles for forming the shell are added to the dispersion of core particles. This causes the resin particles for forming the shell to aggregate on the surface of the core particles. This forms toner base particles with a core-shell structure.

[0231] After the toner base particles are formed, the toner base particles are mixed with external additives to obtain a toner having the toner base particles and the external additives.

[0232] [3. Developer] The toner can be used as a magnetic or non-magnetic one-component developer, but is preferably mixed with a carrier and used as a two-component developer.

[0233] The carrier may be, for example, magnetic particles made of a conventionally known material. Examples of magnetic particles include metals such as iron, ferrite, and magnetite, and alloys of these metals with metals such as aluminum and lead. Ferrite particles are particularly preferred as the carrier.

[0234] Coated carrier particles or dispersed carrier particles may be used as the carrier. "Coated carrier particles" are magnetic particles whose surfaces are coated with a coating agent such as a resin. "Dispersed carrier particles" are particles in which magnetic fine powder is dispersed in a binder resin. Coated carrier particles are preferred as the carrier from the viewpoint of suppressing adhesion of the carrier to the photoreceptor.

[0235] The specific gravity of the carrier is 4 to 6 g / cm 3 The carrier specific gravity is preferably within the range of 4 g / cm 3 If the specific gravity of the carrier is 6 g / cm or more, a sufficient magnetic force can be obtained by the magnetic flux inside the developing sleeve. 3 If the amount is less than this, the toner is less likely to be crushed by the carrier.

[0236] The volume average particle diameter of the carrier is preferably within the range of 20 to 40 μm. When the volume average particle diameter of the carrier is 20 μm or more, the magnetic force of the magnetic flux inside the developing sleeve can be sufficiently obtained. When the volume average particle diameter of the carrier is 40 μm or less, the toner is less likely to be crushed by the carrier.

[0237] [4. Image forming method] The image forming method of the present invention uses a developer containing a toner, and the toner contains the polyester resin composition of the present invention.

[0238] Fig. 4 is an example of a flowchart of an image forming method. As shown in Fig. 4, the image forming method of the present invention includes a toner image forming step S1 and a toner image fixing step S2. In the toner image forming step S1, a toner image is formed on a recording medium. In the toner image fixing step S2, the formed toner image is fixed to the recording medium.

[0239] 5 is a schematic diagram of an example of an image forming apparatus that can be used in the image forming method. The image forming apparatus 1 shown in FIG.

[0240] The document reading unit 100 uses an automatic document feeder (ADF) to transport a document placed on a document tray, and optically reads the document to generate image data. The image data is stored in the control unit 112.

[0241] Image forming unit 110 includes imaging units 111Y to 111K, control unit 112, intermediate transfer belt 113, secondary transfer roller pair 114, timing roller pair 115, cleaner 116, fixing unit 117, paper discharge roller pair 118, paper discharge tray 119, density sensor 102, and primary transfer rollers 103Y to 103K. Toner cartridges 101Y to 101K for the respective colors of Y (yellow), M (magenta), C (cyan), and K (black) are installed in image forming unit 110.

[0242] Receiving toner supply from toner cartridges 101Y-101K, imaging units 111Y-111K form toner images of the respective colors YMCK under the control of control unit 112. Primary transfer rollers 103Y-103K electrostatically transfer (primary transfer) these toner images onto intermediate transfer belt 113 so that they overlap. Intermediate transfer belt 113 is an endless rotating body that rotates in the direction of arrow A and transports the primarily transferred toner images to a secondary transfer position. The intermediate transfer belt 113 can be made of a semiconductive material such as polycarbonate, polytetrafluoroethylene (PTFE), or polyimide with dispersed carbon as the main ingredient.

[0243] The paper feed unit 120 includes a paper feed cassette 121 that stores recording media P by paper size. The paper feed unit 120 supplies the recording media P one by one to the image forming unit 110. The supplied recording media P are conveyed out in parallel with the intermediate transfer belt 113 conveying the toner image, and are conveyed to the secondary transfer roller pair 114 via the timing roller pair 115.

[0244] The timing roller pair 115 is made up of a pair of rollers. The timing roller pair 115 adjusts the timing at which the recording medium P reaches the secondary transfer roller pair 114.

[0245] The secondary transfer roller pair 114 consists of a pair of rollers to which a transfer voltage is applied. The secondary transfer roller pair 114 are pressed against each other to form a transfer NIP section. In this transfer NIP section, the toner image on the intermediate transfer belt 113 is electrostatically transferred (secondary transfer) onto the recording medium P. The recording medium P onto which the toner image has been transferred is transported to a fixing section 117. After the secondary transfer, the residual toner remaining on the intermediate transfer belt 113 is further transported in the direction of arrow A, and then scraped off by a cleaner 116 and discarded.

[0246] The fixing unit 117 heats and melts the toner image carried on the recording medium P, and presses it onto the recording medium P. The recording medium P with the fused toner image is discharged onto a discharge tray 119 by a pair of discharge rollers 118.

[0247] The control unit 112 controls the operation of the image forming apparatus 1. The control unit 112 also transmits and receives image data to and from other devices such as a personal computer, and receives print jobs.

[0248] The image forming apparatus 1 may perform image stabilization processing to stabilize the image quality to be formed. The density sensor 102 is a reflective density sensor that illuminates an object and measures the density based on the amount of reflected light, and optically detects the test pattern formed on the intermediate transfer belt 113 during the image stabilization processing.

[0249] A transfer charger or a transfer belt may be used instead of the transfer roller. A cleaning brush, a cleaning roller, or the like may be used instead of the cleaner 116 (cleaning blade). As for the fixing unit 117, instead of the electromagnetic induction heating system, a halogen lamp, a resistance heating element, or the like may be used as the heat source. The fixing heating element may be in the form of a roller or a belt.

[0250] Next, the configuration of the image forming units 111Y to 111K will be described, focusing particularly on the developing means. Note that since the image forming units 111Y to 111K all have the same configuration, in the following description they will be simply referred to as 111, omitting the letters YMCK that represent the toner colors.

[0251] Fig. 6 is a cross-sectional view showing a part of the image forming unit 111. The image forming unit 111 has a photosensitive drum 210, a charging unit, an exposure unit, a developing unit 200, and a cleaning unit, which are arranged in this order along the outer circumferential surface of the photosensitive drum 210. Of these, the photosensitive drum 210 and the developing unit 200 are shown in Fig. 6.

[0252] The photosensitive drum 210 is driven to rotate in the direction of arrow B by a driving means (not shown). The photosensitive drum 210 is a laminated photosensitive body in which an undercoat layer, a charge generation layer, a charge transport layer, and an overcoat layer are sequentially laminated on the outer surface of, for example, an aluminum tube. The charge transport layer has a thickness of, for example, approximately 25 μm. The overcoat layer has a thickness of, for example, 2 to 3 μm. After the outer surface of the photosensitive drum 210 is uniformly charged by a charging means, an exposure means irradiates it with laser light to form an electrostatic image.

[0253] The developing means 200 has a developing housing 201 that opens toward the photosensitive drum 210. A developing roller 202 is disposed in this opening. A regulating blade 203 that regulates the layer thickness of the developer carried on the outer peripheral surface of the developing roller 202 is also provided on one edge of the opening.

[0254] Developing roller 202 has a structure in which a fixedly arranged magnet roller is enclosed in a rotatable sleeve roller. Developing roller 202 rotates, for example, in the counter direction (direction of arrow C) relative to photosensitive drum 210.

[0255] 7 is a cross-sectional view showing the arrangement of magnetic poles in the magnet roller of the developing roller 202. The magnet roller shown in FIG. 7 has five magnetic poles, N1, S1, N2, S2, and S3, arranged in that order along the circumferential direction. Of these five magnetic poles, the developing magnetic pole N1 is arranged in a position facing the photosensitive drum 210.

[0256] Downstream of the developing magnetic pole N1, there are arranged a transport magnetic pole S1 and repulsion magnetic poles S2 and S3. The regulating magnetic pole N2 is arranged in a position facing the regulating blade 203. The repulsion magnetic poles S and S3 generate a repulsive magnetic field to separate the developer from the sleeve roller, and in particular, the magnetic pole S3 also functions as a pickup pole.

[0257] Developing means 200 receives a supply of developer from toner cartridge 101 via a toner hopper (not shown). The supplied developer is stirred by stirring screw 204 and supply screw 205, and is given a predetermined charge. Then, the developer is guided onto the outer circumferential surface of developing roller 202 by the action of supply magnetic pole S2 of developing roller 202.

[0258] The developer carried on the outer peripheral surface of developing roller 202 is transported in the direction of arrow C by the rotation of developing roller 202 and the action of the magnetic field between supply magnetic pole S2 and regulating magnetic pole N2. On the outer peripheral surface of developing roller 202, the developer is regulated to a predetermined layer thickness by regulating blade 203, and then transported to the development region where photosensitive drum 210 and developing roller 202 face each other. Regulating blade 203 regulates the height of the developer spikes to prevent toner fogging and scattering.

[0259] The peripheral speed of the developing roller 202 is not particularly limited, but is preferably within the range of 200 to 800 mm / s. As the peripheral speed of the developing roller 202 increases, the toner tends to break down, so the peripheral speed is preferably 800 mm / s. On the other hand, the toner according to the present invention has high resistance to breaking down, and therefore does not easily break down even when the peripheral speed of the developing roller 202 is 200 mm / s or more.

[0260] A DC bias is applied as a development bias from a power supply (not shown) to the development roller 202. This development bias causes an electrostatic attraction to act between the development roller 202 and the photosensitive drum 210 in the development area. This causes the toner in the developer to be supplied from the development roller 202 onto the outer circumferential surface of the photosensitive drum 210, thereby visualizing the electrostatic image.

[0261] The developer that has passed through the development zone is further transported in the direction of arrow C on the outer peripheral surface of the development roller 202. The developer is then separated from the development roller 202 by the action of the repulsive magnetic poles S2 and S3 and returned to the supply screw 205 side. The regulating blade 203 is made of, for example, a magnetic material. Therefore, the regulating blade 203 can form effective spikes of the developer between the regulating magnetic pole N2 of the development roller 202 and the regulating blade 203, and can stably regulate the layer thickness.

[0262] A toner concentration sensor 220 is disposed along the outer peripheral surface of photosensitive drum 210, immediately downstream of the development area in the direction of rotation of photosensitive drum 201 (the direction of arrow B). Toner concentration sensor 220 detects the concentration of the toner image formed on the outer peripheral surface of photosensitive drum 201.

[0263] The outer peripheral surface of the photosensitive drum 210 is in contact with the intermediate transfer belt 113, which is pressed by the primary transfer roller 103. The toner image formed on the outer peripheral surface of the photosensitive drum 210 is transferred onto the intermediate transfer belt 113 by a transfer electric field formed by a primary transfer bias applied to the primary transfer roller 103.

[0264] The cleaning unit mechanically scrapes off and cleans the toner remaining on the outer peripheral surface of the photosensitive drum 210 after the primary transfer by bringing a cleaning blade into contact with the outer peripheral surface of the photosensitive drum 210. The scraped off toner is discharged as waste toner by a screw.

[0265] The eraser lamp exposes the outer peripheral surface of the photosensitive drum 210, from which residual toner has been cleaned, through the gap between the cleaning blade and the charging means. This eliminates static electricity from the outer peripheral surface of the photosensitive drum 210, setting it to a uniform potential of, for example, about -30V.

[0266] Thereafter, the above-described operations are repeated to form images one after another.

[0267] The photoreceptor drum 210 may be replaced by a photoreceptor belt.

[0268] The charging means applies a uniform potential to the photosensitive drum 210. It may be a corona discharge type, a roller charging type, or a charging type using a charging blade, a charging brush, a proximity charging member, or the like.

[0269] The exposure unit exposes the photosensitive drum 210, to which a potential has been applied by the charging unit, based on an image signal to form an electrostatic image. The exposure unit may be, for example, a unit consisting of an LED in which light-emitting elements are arranged in an array in the axial direction of the photosensitive drum 210 and an imaging element, or a laser optical system.

[0270] The cleaning means may be a brush, a roller, etc. instead of a cleaning blade. The developing means 200 may be used to collect the residual toner.

[0271] Although embodiments of the present invention have been described and illustrated in detail, the disclosed embodiments are for purposes of illustration and example only and not limitation, and the scope of the present invention should be interpreted by the following claims. [Example]

[0272] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the following examples, unless otherwise specified, operations were performed in a standard environment of 25°C and 50% RH. Furthermore, unless otherwise specified, "%", "ppm", and "parts" mean "% by mass", "ppm by mass", and "parts by mass", respectively.

[0273] [Preparation of amorphous polyester resin composition a1] The following monomers were charged into a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube, and the atmosphere in the reaction vessel was replaced with dry nitrogen gas.

[0274] <Monomer> Neopentyl glycol 624 parts by mass Ethylene glycol 248 parts by mass Terephthalic acid 1245 parts by mass Trimellitic anhydride 480 parts by mass

[0275] The following metal element additives were added to the reaction vessel.

[0276] <Metal element additives> Boric acid 1 part by mass Basic aluminum acetate 9 parts by mass Irganox1222 18 parts by mass

[0277] Irganox 1222 is diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate (a phosphorus-containing compound) manufactured by BASF Japan.

[0278] The temperature in the reaction vessel was raised to 235°C over 1 hour under a nitrogen gas stream, and the reaction was carried out for 3 hours. The pressure in the reaction vessel was reduced to 10.0 mmHg, and the mixture was stirred and reacted. The reaction was terminated when the product reached the desired molecular weight. This yielded an amorphous polyester resin composition a1.

[0279] [Preparation of amorphous polyester resin compositions a2 and a3] In the preparation of amorphous polyester resin composition a1, the types and amounts of monomers and metal element additives were changed as shown in Table I to prepare amorphous polyester resin compositions a2 and a3.

[0280] [Preparation of crystalline polyester resin composition c1] The following monomers were placed in a reactor equipped with a stirrer, a thermometer, a condenser, and a nitrogen gas inlet tube, and the atmosphere in the reactor was replaced with dry nitrogen gas. Then, tin dioctanoate was added in an amount of 0.3 parts by mass per 100 parts by mass of the total amount of monomers.

[0281] <Monomer> Ethylene glycol 621 parts by mass Tetradodecanedioic acid 1312 parts by mass Stearic acid 1562 parts by mass

[0282] The following metal element additives were added to the reaction vessel.

[0283] <Metal element additives> Basic aluminum acetate 37 parts by mass Irganox1222 86 parts by mass

[0284] The contents of the reaction vessel were stirred and reacted at 160°C for 3 hours under a nitrogen gas flow, and then the temperature was further increased to 180°C over 1.5 hours. The pressure in the reaction vessel was reduced to 3 kPa, and the reaction was terminated when the product reached the desired molecular weight. This yielded a crystalline polyester resin composition c1.

[0285] [Preparation of crystalline polyester resin composition c2] In the preparation of the crystalline polyester resin composition c1, the types and amounts of the monomers and metal element additives were changed as shown in Table I to prepare a crystalline polyester resin composition c2.

[0286] [Preparation of amorphous polyester resin composition Ha1 (comparative example)] The following monomers were charged into a reaction vessel equipped with a stirrer, a thermometer, a condenser and a nitrogen gas inlet tube, and the atmosphere in the reaction vessel was replaced with dry nitrogen gas.

[0287] <Monomer> BPA-PO 3514 parts by mass BPA-EO 1296 parts by mass Terephthalic acid 664 parts by mass Trimellitic anhydride 1152 parts by mass

[0288] "BPA-PO" means bisphenol A propylene oxide. "BPA-EO" means bisphenol A ethylene oxide.

[0289] The following metal element additives were added to the reaction vessel.

[0290] <Metal element additives> Boric acid 1 part by mass Basic aluminum acetate 9 parts by mass Irganox1222 18 parts by mass

[0291] The temperature in the reaction vessel was raised to 235°C over 1 hour under a nitrogen gas stream, and the reaction was carried out for 3 hours. The pressure in the reaction vessel was reduced to 10.0 mmHg, and the mixture was stirred and reacted. The reaction was terminated when the product reached the desired molecular weight. This yielded an amorphous polyester resin composition Ha1 (comparative example).

[0292] [Preparation of amorphous polyester resin composition Ha2 (comparative example)] The following ingredients were charged into an autoclave reactor equipped with a thermometer and a stirrer:

[0293] Polypropylene glycol 100 parts by mass L-lactide 500 parts by mass Titanium terephthalate 1 part by mass

[0294] After purging the autoclave reactor with nitrogen, the reaction was carried out at 160 °C for 6 hours. As a result, an amorphous polyester resin composition Ha2 (comparative example) was obtained.

[0295]

Table 1

[0296] [Pyrolysis Gas Chromatography-Mass Spectrometry] For the polyester resin composition prepared above, pyrolysis gas chromatography-mass spectrometry was performed under the following conditions.

[0297] <Pyrolysis Conditions> Pyrolysis furnace: Frontier Lab EGA / PY-3030D Pyrolysis time: 20 seconds Pyrolysis temperature: 600 °C

[0298] <GC Conditions> Gas chromatograph: ThermoFisher Scientific TRACE1310 Analysis column: Frontier Lab Ultra ALLOY-5 (MS / HT) (column length 30 m, inner diameter 0.25 mm, film thickness 0.25 μm) Initial temperature: 45 °C (0 min) Final temperature: 320 °C (10.5 min) Inlet conditions: Injection mode Split method Carrier gas: Helium

[0299] The initial temperature and the final temperature were set in advance by measuring the retention time of 4,4'-dihydroxybiphenyl as a single substance so that the retention time was from 25 min to  30 min.

[0300] Mass spectrometer: ThermoFisher Scientific Exactive GC Ionization method: Electron ionization method Detection conditions: Scan Scan range: m / z 50 - 750 Sample preparation: Weigh the sample into a measuring cup so that it is approximately 0.1 mg or less. Data processing method: In TIC (total ion current), the ratio of each peak height to the total height of the highest point of each peak relative to the baseline, taken as 100%

[0301] A chromatogram of each polyester resin composition was obtained by pyrolysis gas chromatography mass spectrometry under the above conditions. Of the 20 peaks with the highest relative abundance in the chromatogram, the total number of peaks with retention times equal to or shorter than that of 4,4'-dihydroxybiphenyl was counted. The total numbers are shown in Table II.

[0302] [Metal element content measurement] 3 parts by mass of the polyester resin composition was dispersed in 35 parts by mass of a 0.2% by mass aqueous solution of polyoxyethyl phenyl ether, and the resulting dispersion was treated at 25°C for 5 minutes using an ultrasonic homogenizer US-1200T (manufactured by Nippon Seiki Seisakusho Co., Ltd.) to obtain a sample for measurement.

[0303] Acid decomposition: The emission lines of the samples for measurement were obtained by inductively coupled plasma-optical emission spectrometry (ICP-OES).

[0304] The contents of boron, aluminum, phosphorus, and titanium in each polyester resin composition were determined from the above-mentioned emission lines and a calibration curve created by measuring the intensity values ​​for multiple known amounts of each element, starting from the smallest amount, using the element as a standard sample.These contents are expressed in ppm by mass relative to 100% by mass of the polyester resin.These contents are shown in Table II.

[0305] [Measurement of acid value and hydroxyl value] The acid value of the polyester resin in each polyester resin composition was measured according to the method of JIS K 0070:1992. However, the measurement solvent was changed from the ethanol and ether mixed solvent specified in JIS K 0070. For measurements of amorphous polyester resins, the solvent was changed to a mixed solvent of acetone and toluene (acetone:toluene = 1:1 (volume ratio)). For measurements of crystalline polyester resins, the solvent was changed to a mixed solvent of chloroform and dimethylformamide (chloroform:dimethylformamide = 7:3 (volume ratio)).

[0306] The hydroxyl value of the polyester resin in each polyester resin composition was measured according to the method of JIS K 0070: 1992. However, the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K 0070 to tetrahydrofuran.

[0307] The measured acid value, hydroxyl value and total value thereof are shown in Table II.

[0308] [Measurement of weight average molecular weight Mw] The weight average molecular weight Mw was measured using an apparatus connected as follows: Gel permeation chromatography "HLC-8320GPC" (Tosoh Corporation) Column "TSKgel guardcolumn SuperHZ-L" (Tosoh Corporation) - 1 - 3 columns "TSKgel Super HZM-M" (Tosoh Corporation)

[0309] The column was stabilized at 40°C, and tetrahydrofuran (THF) was passed through the column at this temperature as a carrier solvent at a flow rate of 0.35 mL / min. A THF sample solution of the measurement sample (resin composition) adjusted to a sample concentration of 1 mg / mL was treated using a roll mill at room temperature for 10 minutes. The solution was treated with a membrane filter with a pore size of 0.2 μm to obtain a sample solution. 10 μL of this sample solution was injected into the above-mentioned device together with the above-mentioned carrier solvent, and detected using a refractive index detector (RI detector).

[0310] A calibration curve was created using a polystyrene standard sample with a monodisperse molecular weight distribution. The molecular weight distribution of the measured sample was calculated based on this calibration curve. The calibration curve was created from 10 samples of "polystylene standard sample TSK standard" manufactured by Tosoh Corporation: "A-500," "F-1," "F-10," "F-80," "F-380," "A-2500," "F-4," "F-40," "F-128," and "F-700." The data collection interval for sample analysis was 300 ms.

[0311] The measured weight average molecular weights Mw are shown in Table II.

[0312] [Measurement of glass transition temperature Tg] Differential scanning calorimetry (DSC) was performed using a differential scanning calorimeter "DSC7000X" (Hitachi Corporation) and a thermal analyzer controller "AS3 / DX" (Hitachi Corporation) to measure the glass transition temperature. Specifically, 5 mg of sample was sealed in an AL autosampler sample container (φ6.8 H2.5 mm, Hitachi Corporation) and an AL autosampler cover (Hitachi Corporation). This was placed in the sample holder of the "AS3 / DX" and the temperature was cycled in the following order: heating, cooling, and heating again. During the first and second heating runs, the temperature was increased from 0°C to 150°C at a rate of 10°C / min and held at 150°C for 1 minute. During cooling, the temperature was decreased from 150°C to 0°C at a rate of 10°C / min and held at 0°C for 1 minute. A baseline shift was observed in the measurement curve obtained during the second heating run. The glass transition point Tg was determined as the intersection of an extension of the baseline before the shift and a tangent line showing the maximum slope of the shifted portion of the baseline. An empty aluminum pan was used as a reference.

[0313] The glass transition temperature Tg was measured only for the amorphous polyester resin composition, and the measured glass transition temperature Tg is shown in Table II.

[0314] [Measurement of melting point Tm] Differential scanning calorimetry (DSC) was performed using a differential scanning calorimeter "DSC7000X" (Hitachi Corporation) and a thermal analyzer controller "AS3 / DX" (Hitachi Corporation) to measure the melting point. Specifically, 5 mg of sample was sealed in an AL autosampler sample container (φ6.8 H2.5 mm) (Hitachi Corporation) and an AL autosampler cover (Hitachi Corporation). This was placed in the sample holder of the "AS3 / DX" and the temperature was cycled in the following order: heating, cooling, and heating again. During the first and second heating runs, the temperature was increased from 0°C to 150°C at a rate of 10°C / min and held at 150°C for 1 minute. During cooling, the temperature was decreased from 150°C to 0°C at a rate of 10°C / min and held at 0°C for 1 minute. The temperature at the top of the endothermic peak in the endothermic curve obtained during the second heating run was taken as the melting point (Tm). An empty aluminum pan was used as a reference.

[0315] The melting point Tm was measured only for the crystalline polyester resin composition, and the measured melting point Tm is shown in Table II.

[0316] [Table 2]

[0317] [Preparation of amorphous polyester resin dispersion A1] The following components were placed in a reaction vessel equipped with a stirrer and dissolved at 60°C.

[0318] Amorphous polyester resin composition a1 100 parts by mass Methyl ethyl ketone 60 parts by mass Isopropyl alcohol 10 parts by mass

[0319] After confirming dissolution, the reaction vessel was cooled to 35°C, and then 10% aqueous ammonia solution (3.5 parts by mass) was added. Next, ion-exchanged water (300 parts by mass) was added dropwise to the reaction vessel over 3 hours to prepare a polyester resin dispersion. Next, methyl ethyl ketone and isopropyl alcohol were removed using an evaporator to obtain amorphous polyester resin dispersion A1.

[0320] [Preparation of amorphous polyester resin dispersion A2] Amorphous polyester resin dispersion A2 was prepared by changing the amorphous polyester resin composition a1 in the preparation of amorphous polyester resin dispersion A1 to amorphous polyester resin composition a2.

[0321] [Preparation of amorphous polyester resin dispersion A3] Amorphous polyester resin dispersion A3 was prepared by changing the amorphous polyester resin composition a1 in the preparation of amorphous polyester resin dispersion A1 to amorphous polyester resin composition a3.

[0322] [Preparation of crystalline polyester resin dispersion C1] Crystalline polyester resin dispersion C1 was prepared by changing the amorphous polyester resin composition a1 in the preparation of amorphous polyester resin dispersion A1 to a crystalline polyester resin composition c1.

[0323] [Preparation of Crystalline Polyester Resin Dispersion C2] Crystalline polyester resin dispersion C2 was prepared by changing the amorphous polyester resin composition a1 in the preparation of amorphous polyester resin dispersion A1 to crystalline polyester resin composition c2.

[0324] [Preparation of amorphous polyester resin dispersion HA1] Amorphous polyester resin dispersion HA1 was prepared by changing the amorphous polyester resin composition a1 in the preparation of amorphous polyester resin dispersion A1 to amorphous polyester resin composition Ha1.

[0325] [Preparation of amorphous polyester resin dispersion HA2] Amorphous polyester resin dispersion HA2 was prepared by changing the amorphous polyester resin composition a1 in the preparation of amorphous polyester resin dispersion A1 to amorphous polyester resin composition Ha2.

[0326] [Preparation of vinyl resin dispersion V1] (a) First stage polymerization Sodium dodecyl sulfate (8 parts by mass) and ion-exchanged water (3,000 parts by mass) were charged into a 5 L reaction vessel equipped with a stirrer, temperature sensor, condenser, and nitrogen inlet. The contents were stirred at 230 rpm under a nitrogen stream while the internal temperature was raised to 80°C. After the temperature was raised, a solution of potassium persulfate (10 parts by mass) dissolved in ion-exchanged water (200 parts by mass) was added, and the liquid temperature was again raised to 80°C. A mixed solution of the following monomers was added dropwise to the vessel over one hour.

[0327] n-Butyl acrylate 526 parts by mass Methacrylic acid 474 parts by mass

[0328] After the dropwise addition, polymerization was carried out by heating and stirring at 80° C. for 2 hours, to prepare a vinyl resin particle dispersion liquid d1.

[0329] (b) Second stage polymerization A solution of sodium dodecyl sulfate (7 parts by mass) dissolved in ion-exchanged water (3,000 parts by mass) was placed in a 5 L reaction vessel equipped with a stirrer, a temperature sensor, a cooling tube, and a nitrogen introducing device, and heated to 98°C. Thereafter, the vinyl resin particle dispersion d1 (300 parts by mass (solid content equivalent)) prepared by the first-stage polymerization and a mixed solution prepared by dissolving the following components at 90°C were added to the reaction vessel.

[0330] 2-Ethylhexyl acrylate 90.5 parts by mass Methacrylic acid 33.1 parts by mass n-Octyl mercaptan (chain transfer agent) 5.5 parts by mass

[0331] A dispersion containing emulsified particles (oil droplets) was prepared by mixing and dispersing for one hour using a mechanical disperser with a circulation path, CLEARMIX (M Technique Co., Ltd.). A polymerization initiator solution of potassium persulfate (6 parts by weight) dissolved in ion-exchanged water (200 parts by weight) was added to this dispersion. The system was heated and stirred at 78°C for one hour to polymerize, producing vinyl resin particle dispersion d2.

[0332] (c) Third stage polymerization To the vinyl resin particle dispersion d2 obtained by the second-stage polymerization, 400 parts by mass of ion-exchanged water was added and mixed thoroughly. A polymerization initiator solution prepared by dissolving 6.0 parts by mass of potassium persulfate in 400 parts by mass of ion-exchanged water was then added. A mixture of the following components was then added dropwise over one hour at a temperature of 81°C:

[0333] n-Butyl acrylate 143.2 parts by mass Methacrylic acid 52.0 parts by mass n-Octyl mercaptan (chain transfer agent) 8.0 parts by mass

[0334] After the dropwise addition was completed, polymerization was carried out by heating and stirring for 2 hours, and then the mixture was cooled to 28°C.

[0335] By the above operations, a vinyl resin dispersion liquid V1 was obtained. The vinyl resin contained in the vinyl resin dispersion liquid V1 is referred to as "vinyl resin v1." The weight average molecular weight of the vinyl resin d1 was 35,000.

[0336] [Preparation of release agent dispersion W1] The following components were mixed, and the release agent was dissolved in a pressure discharge homogenizer (Gaulin Homogenizer, manufactured by Gaulin) at an internal liquid temperature of 120° C. Teika Power BN2060 (active ingredient content: 60%) manufactured by Teika Corporation was used as the anionic surfactant.

[0337] Behenyl behenate (mold release agent) 270 parts by mass Anionic surfactant 13.5 parts by mass Ion-exchanged water 700 parts by mass

[0338] The amount of anionic surfactant added in terms of active ingredient was 8.1 parts by mass, which was 3.0% by mass relative to the amount of release agent added. After dissolution, the dispersion was performed at a dispersion pressure of 5 MPa for 120 minutes, followed by a dispersion treatment at 40 MPa for 360 minutes, and then cooled. The volume average particle size D50v of the particles contained in the obtained dispersion was 220 nm. Ion-exchange water was then added to the dispersion to adjust the solid content to 20.0% by mass. This yielded release agent dispersion W1.

[0339] [Preparation of Black Colorant Dispersion P1] REGAL330 (Cabot Japan, carbon black, pigment) was used as the black colorant. Neogen SC (Dai-ichi Kogyo Seiyaku, active ingredient: 60%) was used as the anionic surfactant. A stainless steel container was used so that the liquid level would be 1 / 3 of the height of the container when 750 parts by mass of ion-exchanged water, 33 parts by mass of the anionic surfactant, and 200 parts by mass of the black colorant were added.

[0340] Ion-exchanged water (280 parts by mass) and anionic surfactant (33 parts by mass) were placed in a container, and the surfactant was thoroughly dissolved. Then, black colorant (200 parts by mass) was added, and the mixture was stirred using a stirrer until no unwetted black colorant remained. Ion-exchanged water (470 parts by mass) was then added, and the mixture was further stirred and thoroughly degassed. The amount of anionic surfactant added in terms of active ingredient was 20 parts by mass, which was 10% by mass of the amount of black colorant added.

[0341] After degassing, the mixture was dispersed at 5,000 rpm for 10 minutes using a homogenizer (IKA Ultra Turrax T50), and then stirred overnight with a mixer to degas. After degassing, the mixture was dispersed again at 6,000 rpm for 10 minutes using a homogenizer, and then stirred overnight with a mixer to degas.

[0342] After degassing, the mixture was dispersed at a pressure of 240 MPa using a high-pressure impact disperser, Ultimizer (HJP30006, manufactured by Sugino Machine Co., Ltd.) The dispersion was carried out for a number of passes equivalent to 25, calculated based on the total amount charged and the processing capacity of the apparatus.

[0343] The resulting dispersion was left to stand for 72 hours to remove precipitates, and ion-exchanged water was added to adjust the solids concentration to 15%, yielding black colorant dispersion P1. The volume average particle size D50v of the particles contained in black colorant dispersion P1 was 110 nm.

[0344] [Preparation of Toner A] (Preparation of toner base particles) The following materials were premixed in a Henschel mixer, and then melt-kneaded using a PCM-30 (manufactured by Ikegai Iron Works Co., Ltd.) with the temperature set so that the melt temperature at the discharge outlet was 150°C.

[0345] Amorphous polyester resin composition a1 92 parts by mass Carbon black 5 parts by mass Behenyl behenate (mold release agent) 3 parts by weight

[0346] The resulting kneaded product was cooled, coarsely pulverized using a hammer mill, and then finely pulverized using a Turbo Mill T250 (manufactured by Turbo Kogyo Co., Ltd.) The resulting finely pulverized powder was classified using a multi-division classifier utilizing the Coanda effect to obtain toner base particles a with a volume average particle size of 6.5 μm.

[0347] (External addition treatment) The following components were mixed in a Henschel mixer (manufactured by Nippon Coke & Engineering Co., Ltd.) at a rotor peripheral speed of 40 m / sec and 32°C for 20 minutes. The hydrophobic silica particles had a number-average primary particle size of 12 nm and a hydrophobicity degree of 68. The sol-gel silica particles had a number-average primary particle size of 110 nm.

[0348] Toner base particles a 100.0 parts by mass Hydrophobic silica particles (external additive) 1.0 parts by mass Sol-gel silica particles (external additive) 1.0 parts by mass

[0349] After mixing, coarse particles were removed using a sieve with 45 μm openings to obtain Toner A.

[0350] [Preparation of Toner B] (Preparation of toner base particles) The following amounts of each of the dispersions prepared above were placed in a round stainless steel flask.

[0351] Amorphous polyester resin dispersion A1 89 parts by mass (solid content equivalent) Colorant dispersion P1 6 parts by mass (solid content) Release agent dispersion W1 5 parts by mass (solid content)

[0352] Subsequently, ion-exchanged water was added to the flask so that the solids concentration of the contents in the flask was 12.5% ​​by mass, and then 6.3 parts by mass of a 10% aqueous solution of aluminum sulfate was added. The contents were then mixed and dispersed at 5,000 rpm for 10 minutes using a homogenizer (Ultra Turrax T50, manufactured by IKA). The contents in the flask were then heated to 40°C while stirring, and the temperature was then increased at a rate of 0.5°C per minute, and the temperature was maintained at a value where the particle size reached 6.1 μm.

[0353] Then, 11 parts by mass of ethylenediaminetetraacetic acid (EDTA) tetrasodium salt (Chilest 40, manufactured by Chelest Corporation) was added. Then, an aqueous sodium hydroxide solution was added to adjust the pH to 8. The temperature was then raised to 82.5°C, and the pH was lowered by 0.05 every 10 minutes with nitric acid, and stirring was continued for 45 minutes. After cooling, the mixture was filtered, thoroughly washed with ion-exchanged water, and dried to obtain toner base particles b.

[0354] (External addition treatment) The following components were mixed in a Henschel mixer (manufactured by Nippon Coke & Engineering Co., Ltd.) at a rotor peripheral speed of 40 m / sec and 32°C for 20 minutes. The hydrophobic silica particles had a number-average primary particle size of 12 nm and a hydrophobicity degree of 68. The sol-gel silica particles had a number-average primary particle size of 110 nm.

[0355] Toner base particles b 100.0 parts by mass Hydrophobic silica particles (external additive) 1.0 parts by mass Sol-gel silica particles (external additive) 1.0 parts by mass

[0356] After mixing, coarse particles were removed using a sieve with 45 μm openings to obtain Toner B.

[0357] [Preparation of Toner C] (Preparation of toner base particles) The following ingredients were placed in a round stainless steel flask:

[0358] Vinyl resin dispersion V1 58 parts by mass (solids equivalent) Crystalline polyester resin dispersion C1 23 parts by mass (solid content equivalent) Black colorant dispersion P1 6 parts by mass (solid content) Release agent dispersion W1 5 parts by mass (solid content) 10% aluminum sulfate aqueous solution 63 parts by mass Ion-exchanged water 750 parts by mass

[0359] Next, the mixture was mixed and dispersed at 5,000 rpm for 10 minutes using a homogenizer "Ultra Turrax T50" (manufactured by IKA). The reactant in the flask was then heated to 40°C while stirring. Thereafter, the temperature was increased at a rate of 0.5°C per minute, and the temperature was maintained when the particle size of the reactant reached 5.5 μm. This resulted in the formation of core particles.

[0360] Next, the following components were added dropwise to the flask over 1 hour: "Chilest 40" (manufactured by Chelest Co.) was used as ethylenediaminetetraacetic acid (EDTA) tetrasodium salt.

[0361] Amorphous polyester resin dispersion A1 6 parts by mass (solid content) Ethylenediaminetetraacetic acid (EDTA) tetrasodium salt 18 parts by mass

[0362] Aqueous sodium hydroxide solution was then added to adjust the pH of the reaction solution to 8. The temperature of the reaction solution was then raised to 82.5°C, and the pH of the reaction solution was then lowered by 0.05 every 10 minutes with nitric acid, and stirring was continued for 45 minutes. The reaction solution was then cooled to a temperature of 40°C or below, and stirring was stopped. This resulted in the formation of a shell.

[0363] The aggregates were then removed by filtration using a filter with 45 μm openings. The pH of the reaction solution was adjusted to 4 with hydrochloric acid, and a centrifuge was used to extract the water-containing cake (aggregates of toner base particles). While centrifuging, the water-containing cake was washed with ion-exchanged water in an amount 10 times the solid content of the toner base particles. The mixture was then dehydrated for 10 minutes, and the water-containing cake was extracted.

[0364] The resulting wet cake was then fed into a dryer (flash jet dryer, manufactured by Seishin Co., Ltd.) and dried. The drying conditions were set to an air temperature of 80°C, an air velocity of 10 m / sec, and an outlet temperature of 35°C. This yielded core-shell toner base particles c. The water content of toner base particles c was 1.2% by mass relative to the total mass of the toner base particles.

[0365] (External addition treatment) The following components were mixed in a Henschel mixer (manufactured by Nippon Coke & Engineering Co., Ltd.) at a rotor peripheral speed of 40 m / sec and 32°C for 20 minutes. The hydrophobic silica particles had a number-average primary particle size of 12 nm and a hydrophobicity degree of 68. The hydrophobic titanium oxide particles had a number-average primary particle size of 20 nm and a hydrophobicity degree of 63. The sol-gel silica particles had a number-average primary particle size of 110 nm.

[0366] Toner base particles c 100.0 parts by mass Hydrophobic silica particles (external additive) 1.0 parts by mass Hydrophobic titanium oxide particles (external additive) 0.5 parts by mass Sol-gel silica particles (external additive) 1.0 parts by mass

[0367] After mixing, coarse particles were removed using a sieve with 45 μm openings to obtain Toner C.

[0368] [Production of Toners D to G] In the preparation of toner C, the type and amount of each resin dispersion was changed as shown in Table III to prepare toners D to G, respectively.

[0369] [Table 3]

[0370] [Preparation of Toner H (Comparative Example)] Toner H was prepared by changing the amorphous polyester resin composition a1 in the preparation of toner A to amorphous polyester resin composition Ha1.

[0371] [Preparation of Toner I (Comparative Example)] In the preparation of toner A, the amorphous polyester resin composition a1 was changed to the amorphous polyester resin composition Ha2, and toner I (comparative example) was prepared.

[0372] [Composition and Properties of Toners A to I] The types of resins and the content of the polyester resin composition contained in the toners A to I are as shown in Table IV.

[0373] The volume average particle diameter, average circularity, and glass transition temperature Tg of each of the toners A to I were measured by the methods described above, and the measurement results are shown in Table IV.

[0374] [Evaluation of low-temperature fixability of toner] For the evaluation, a commercially available digital full-color multifunction printer "bizhub C650i" (manufactured by Konica Minolta) was used, which was modified so that the surface temperatures of the upper fixing belt and the lower fixing roller could be changed. 2 ) with a toner adhesion of 11.3 g / m 2The test to output a solid image was repeatedly performed while changing the fixing temperature in 5°C increments in the range of 100 to 200°C. The nip width was 11.2 mm. The fixing time was 34 msec. The fixing pressure was 133 kPa. The lowest fixing temperature at which image staining due to fixing offset was not visually confirmed was defined as the minimum fixing temperature. The low-temperature fixing ability of each toner was evaluated based on the following criteria. The evaluation results are shown in Table IV.

[0375] A: The minimum fixing temperature is less than 130°C. (This is an excellent toner with excellent low-temperature fixing properties.) B: The minimum fixing temperature is 130°C or higher and lower than 150°C. (This is a toner that can be controlled by the machine and is at a level that does not cause any problems in practical use.) C: The minimum fixing temperature is 150°C or higher. (The toner is not sufficiently fixed at the target paper feed speed, and is at a level that is problematic for practical use.)

[0376] [Evaluation of heat-resistant storage stability of toner] 0.5 g of the prepared toner was placed in a 10 mL glass bottle with an inner diameter of 21 mm, the lid was closed, and the bottle was shaken 600 times at room temperature using a Tap Denser KYT-2000 (Seishin Enterprise Co., Ltd.). The lid was then removed and the entire bottle was left at 55°C and 35% RH for 2 hours. The toner was then placed on a 48 mesh (350 μm opening) sieve, taking care not to break up the toner aggregates, and placed in a powder tester (Hosokawa Micron Corporation). The pressure bar and knob nut were fixed, and the vibration intensity was adjusted to a feed width of 1 mm. Vibration was applied for 10 seconds. The mass of the toner on the sieve (g) was then measured. The toner cohesion rate (%) was calculated using the following formula:

[0377] Toner cohesion rate [%] = toner mass on sieve [g] / 0.5g x 100

[0378] The heat-resistant storage stability of each toner was evaluated based on the following criteria, and the evaluation results are shown in Table IV.

[0379] A: The toner cohesion rate is less than 5%. (The toner has excellent heat-resistant storage properties.) B: The toner has a cohesion rate of 5% or more and less than 15%. (The toner has good heat-resistant storage properties and is suitable for practical use.) C: The toner has a cohesion rate of 15% or more. (The toner has poor heat-resistant storage properties and is not suitable for use.)

[0380] [Evaluation of toner crush resistance] The above-prepared toner (10 g), commercially available titanium oxide microparticles (0.05 g), and commercially available glass beads (30 g) with a diameter of 3 mm were placed in a polyethylene container and mixed for 10 minutes using a Turbula mixer. The particle size distribution of the toner before and after the mixing process was measured using a Coulter Counter (manufactured by Nikkiso Co., Ltd.). The number ratio [%] of toner particles with a particle size of 4 μm or less was determined before and after the mixing process. The number ratio [%] before and after the mixing process was compared, and the increase in the number ratio [%] was determined. The crush resistance of each toner was evaluated based on the following criteria. A and B are acceptable. The evaluation results are shown in Table IV.

[0381] A: The increase is less than 3.0%. B: The increase is 3.0% or more and less than 10.0%. C: The increase is 10.0% or more.

[0382] [Preparation of developer] Toluene (14.0 parts by mass), cyclohexyl methacrylate / dimethylaminoethyl methacrylate copolymer (weight ratio 99:1, Mw 80000) (2.0 parts by mass), and glass beads (φ1 mm) (14.0 parts by mass) were mixed. This was stirred at 1200 rpm for 30 minutes using a sand mill (Kansai Paint Co., Ltd.) to obtain a solution for forming a resin coating layer. The solution for forming a resin coating layer and ferrite particles were placed in a vacuum degassing kneader, the pressure was reduced, and the toluene was distilled off and dried. Mn-Mg-Sr ferrite particles with an average particle size of 30 μm were used as the ferrite particles. A resin-coated carrier was produced using this. The specific gravity of the carrier was 5.2 g / cm 3 The volume average particle size of the carrier was 33.1 μm.

[0383] The toner (100 parts by mass) and the resin-coated carrier (7 parts by mass) were placed in a 2 L V-blender and stirred for 20 minutes under normal temperature and humidity conditions. After that, the mixture was sieved through a 105 μm sieve to obtain a developer.

[0384] By the above-mentioned procedure, developers containing the respective toners prepared above were prepared.

[0385] [Evaluation of charge retention] Continuous printing was performed using a chart with a coverage rate of 2%, and the charge amount was measured at the start of printing and after printing 10,000 sheets. The image forming apparatus used was a "bizhub C650i" (manufactured by Konica Minolta). This apparatus has a developing unit that forms a layer of developer on a developing roller. The peripheral speed of the developing roller in this apparatus is usually 350 mm / sec, but this was modified to increase this peripheral speed to 750 mm / sec, and charge retention was evaluated under these strict conditions. Evaluation was performed using the black position installed in this apparatus. The charge amount was measured using the apparatus shown in Figure 8 as follows. First, 1 g of two-component developer weighed using a precision balance was placed evenly over the entire surface of the conductive sleeve 11. A voltage of 2 kV was applied to the conductive sleeve 11 from the bias power supply 13, and the rotation speed of the magnet roller 12 installed inside the conductive sleeve 11 was set to 1,000 rpm. The apparatus was left under these conditions for 30 seconds, and the two-component developer was collected on the cylindrical electrode 14. After 30 seconds, the potential Vm of the cylindrical electrode 14 was read and the charge amount of the two-component developer was calculated. The mass of the collected two-component developer was measured using a precision balance. The average charge amount [μC / g] was calculated from the charge amount and mass of the two-component developer. The charge amounts at the start of printing and after printing 10,000 sheets are shown in Table IV.

[0386] The change in the amount of charge was calculated using the following formula (1).

[0387] Equation (1) a=|(bc)| a: Change in charge amount [μC / g] b: Charge amount at the start of printing [μC / g] c: Charge amount after printing 10,000 sheets [μC / g]

[0388] The charge retention of each toner was evaluated based on the following criteria, with A and B being acceptable. The evaluation results are shown in Table IV.

[0389] A: The change in charge amount is 4 μC / g or less. B: The change in charge amount is more than 4 μC / g and 10 μC / g or less. C: The change in charge amount exceeds 10 μC / g.

[0390] [In-flight scattering resistance evaluation] Before printing began, double-sided tape was attached to the top of the developing means. After printing 10,000 sheets, the toner contamination components due to toner scattering inside the machine were measured using a reflection densitometer (RD-918; Macbeth). The difference in reflection density between the start of printing and after printing 10,000 sheets was determined. The resistance to scattering inside the machine for each toner was evaluated based on the following criteria. The image forming apparatus used was a "bizhub C650i" (manufactured by Konica Minolta). This apparatus has a developing means that forms a layer of developer on the developing roller. The peripheral speed of the developing roller of this apparatus is usually 350 mm / sec, but this peripheral speed was changed to 250 mm / sec, 500 mm / sec, 750 mm / sec, and 1000 mm / sec. Evaluation at a peripheral speed of 1000 mm / sec was not performed for Toner H and Toner I. A and B are acceptable. The evaluation results at each peripheral speed are shown in Table IV.

[0391] A: Almost no increase in density due to toner scattering is observed from the start of printing, and the difference in reflection density is 0.1 or less. B: Although some toner scattering is observed from the start of printing, it does not pose a problem in practical use, and the difference in reflection density is more than 0.1 and 0.8 or less. C: The amount of toner scattering from the start of printing is large, which is problematic for practical use, and the difference in reflection density is more than 0.8.

[0392] [Table 4]

[0393] From the above results, it was confirmed that the polyester resin composition of the present invention can improve the low-temperature fixability, heat-resistant storage stability, and crush resistance of the toner.

[0394] In addition, it was confirmed that the polyester resin composition of the present invention can also improve the charge retention of the toner. This is due to the fact that the polyester resin composition of the present invention improves the crush resistance of the toner. In the toner of the comparative example, the toner broke into small pieces due to mixing stress caused by the weight of the carrier and the peripheral speed of the developing roller. The broken toner covered the carrier surface and prevented contact between the carrier and newly replenished toner. This caused a significant decrease in the charge amount in the toner of the comparative example. In contrast, it was confirmed that the toner of the examples of the present invention had improved crush resistance and did not exhibit the above-mentioned phenomenon. [Explanation of symbols]

[0395] 1. Image forming device 100 Document reading unit 110 Image forming unit 111, 111Y~111K Imaging section 112 Control Unit 113 Intermediate transfer belt 114 Secondary transfer roller pair 115 Timing Roller Pair 116 Cleaner 117 Fixing section 118 Paper ejection roller pair 119 Paper output tray 101Y~101K Toner Cartridge 102 Concentration sensor 103Y~103K Primary transfer roller 200 Developing means 202 Developing roller 203 Regulatory Blade 204 stirring screw 205 supply screw 210 Photosensitive drum 220 Toner density sensor S1 Carrying pole S2, S3 anti-magnetic pole N1 Phenomenon Magnetic Pole N2 Regulated Magnetic Pole 120 Paper feeding unit 121 Give paper カセット P Recording Media

Claims

1. A polyester resin composition containing a polyester resin, In a chromatogram obtained by pyrolysis gas chromatography mass spectrometry, the total number N of peaks having retention times equal to or shorter than the retention time of 4,4'-dihydroxybiphenyl among 20 peaks having high relative abundance is 1 to 17, Further containing at least one element of boron, aluminum, and phosphorus, Polyester resin composition.

2. The total content of boron, aluminum, and phosphorus is within the range of 300 to 3,000 ppm by mass relative to 100% by mass of the polyester resin. The polyester resin composition according to claim 1.

3. The sum of the acid value and the hydroxyl value of the polyester resin is in the range of 200 to 1000 mgKOH / g. The polyester resin composition according to claim 1.

4. The polyester resin composition according to any one of claims 1 to 3 is contained in an amount of 30 to 97% by mass. Toner for developing electrostatic images.

5. The average circularity is in the range of 0.950 to 0.

995. The toner for developing electrostatic images according to claim 4.

6. The toner for developing electrostatic images according to claim 4, Specific gravity: 4 to 6 g / cm ３ and a carrier having a volume average particle size in the range of 20 to 40 μm. Developer.

7. A developer containing the toner for developing electrostatic images according to claim 4 is used. Image forming method.

8. using a developing means for forming a layer of the developer on a developing roller; The peripheral speed of the developing roller is within the range of 200 to 800 mm / s. The image forming method according to claim 7.

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