KR101184788B1 - Modified polyester resin and a toner comprising the same - Google Patents

Abstract

The present invention provides an acid component selected from aromatic dicarboxylic acid or a mixture of aromatic dicarboxylic acid and trivalent or higher polyhydric carboxylic acid; Aromatic diols; Aliphatic diols; And a modified polyester resin prepared by a polycondensation reaction of a reactant containing a trivalent or higher polyhydric alcohol component as an optional component, and a toner having excellent thermal stability, low temperature fixability, and long-term storage stability prepared by using the same as a binder resin. In this regard, the aromatic diol is a bisphenol A derivative to which ethylene oxide or propylene oxide is added. will be.

Polyester, Binder, Thermal Stability, Toner, Bisphenol A Derivative, Acidity

Description

Modified polyester resin and a toner comprising the same

The present invention relates to a modified polyester resin and a toner including the same. More specifically, the present invention relates to a modified polyester resin comprising an acid component which is an aromatic dicarboxylic acid and / or a trivalent or higher polyhydric carboxylic acid, and an aromatic diol, an aliphatic diol, and an optional component trivalent or higher polyhydric alcohol. In this regard, by using bisphenol A derivative having a specific range of α as an aromatic diol, a modified polyester resin having a wide molecular weight distribution, which is advantageous to have a wide offset range by controlling unreacted monomer and molecular weight distribution in polyester melt polymerization, is used. By using this as a binder resin for toner, a toner excellent in thermal stability, low temperature fixability, and long-term storage stability can be produced.

Due to the generalization of office equipment and personal computers, the spread of printers has also increased, and as a result, consumer's desire to settle high-quality images at high speed is increasing. To meet these needs, in terms of energy saving, toner particles have been refined for low temperature fixing and high resolution. However, in the case of miniaturization of the toner particles, there is a problem that toner particles of 5 m or less can be sucked into the human respirator. On the other hand, in order to satisfy the low temperature fixability, a method of lowering the softening temperature of the polyester resin has been attempted. However, if the softening temperature is lowered, an offset phenomenon that contaminates the next image during image formation occurs and storage stability is reduced due to a decrease in glass transition temperature. There is a problem that goes bad. Therefore, many attempts have been made to solve this problem and satisfy the market demand. The most frequently used method is to use a polyester resin synthesized using a bisphenol A derivative. A polyester resin having a low softening point is a method of satisfying low temperature fixability while maintaining storage stability using a bisphenol A derivative. Is used as the binder resin to improve the low temperature fixing characteristics of the toner. However, a polyester resin having a low softening point has a problem of deteriorating image quality due to low durability and storage stability. In order to solve this problem, a method of using a nonlinear polyester resin by melt polymerization with a monomer having a trivalent or higher functional group has been proposed. However, since the softening point of the nonlinear polyester is high, the thermal and storage stability are improved, but the fastening property is insufficient. It does not satisfy the image formation. On the other hand, in order to produce a toner having excellent fixing properties, a polyester may be obtained by polymerizing a polyester resin having a low softening point together with an aliphatic diol, dicarboxylic acid, a trihydric or higher polyhydric alcohol, and a trivalent or higher polyhydric carboxylic acid. The glass transition temperature is so low that there is a problem of low storage stability of the toner, that is, agglomeration of toner particles occurs during toner storage, thereby degrading image quality.

In order to solve this problem, various methods using bisphenol A derivatives have been proposed. US Pat. Nos. 4,804,622, 4,849,495, 5,057,596 and the like limit only the number of moles of ethylene oxide or propylene oxide added to bisphenol A as aromatic diols used to improve storage stability and low temperature fixation properties. Japanese Patent Application Laid-Open No. 2007-264623 shows that the purity of 2 mole of ethylene oxide added to bisphenol A is 93% or more. However, the polyester binder resin described in the above prior art documents did not provide a toner excellent in all of thermal stability, storage stability, and low temperature fixability.

The inventors have noted that the bisphenol A derivatives are important alcohol groups and acidic end groups in terms of reactivity as alcohol monomers, and have a great influence on the physical properties of the polyester resin. At the same time, the modified polyester resin is appropriately adjusted by appropriately adjusting the composition and content of the acid component which is an aromatic dicarboxylic acid and / or a trivalent or higher polyhydric carboxylic acid, and an aliphatic diol, an aromatic diol, and an optional component of a trivalent or higher polyhydric alcohol. The modified polyester binder resin having a wide molecular weight distribution, which is advantageous to have a wide offset range by controlling the molecular weight of the resin used as the binder for toner, in particular, low molecular weight, and thermal stability, storage stability using the same To provide excellent toner with low temperature and low temperature fixing ability A.

The present invention relates to an aromatic dicarboxylic acid or a mixture of aromatic dicarboxylic acid and a trivalent or higher polyhydric carboxylic acid in the presence of a polycondensation reaction catalyst selected from the group consisting of titanium-based catalysts, zinc acetate catalysts, and mixtures thereof. It relates to a modified polyester resin prepared by polycondensing 100 mole parts by weight of the selected acid component, 30 to 80 mole parts by weight of aromatic diol, and 10 to 50 mole parts by weight of aliphatic diol.

The aromatic dicarboxylic acid may be used together with aliphatic dicarboxylic acid if necessary, and the aromatic diol is a bisphenol A derivative to which ethylene oxide or propylene oxide is added, and α values of the ethylene oxide adduct and the propylene oxide adduct are respectively Formulas (1) and (2) are satisfied, and the acidity (pH) is preferably 7.0 to 8.5.

< 444Formula (1): 277 <

<444

< 362Formula (2): 224 <

<362

Wherein R is 8.314 and T is 25.

The modified polyester resin according to the present invention has a content of high molecular weight resin eluted at 0 to 10 minutes as a result of LC (Liquid chromatography) analysis, and a content of low molecular weight resin eluted at 20 to 30 minutes is 20 to 20 minutes. It is preferable that it is 40%.

In order to obtain the modified polyester resin according to the present invention, 1.0 to 20 mole parts by weight of a trivalent or higher polyhydric alcohol component may be further added and polycondensed based on 100 mole parts by weight of the acid component as necessary.

Hereinafter, the resin and its components according to the present invention will be described in more detail.

Polycondensation catalyst

The polycondensation catalyst according to the invention is selected from titanium based catalysts, zinc acetate catalysts, or mixtures thereof. The polycondensation catalyst is added at a concentration of 500-1000 ppm based on the content of the aromatic dicarboxylic acid, which is the acid component of the resin according to the present invention, or the mixture content of the aromatic dicarboxylic acid and the trivalent or higher polyhydric carboxylic acid. If the polycondensation catalyst concentration is less than 500ppm, the polyester resin may not be polymerized to the desired degree of polymerization, and if the concentration is more than 1000ppm, the catalyst may precipitate as a precipitate, resulting in a slow polymerization reaction and a decrease in transparency of the polyester resin.

(A) acid component

The acid component according to the present invention uses the aromatic dicarboxylic acid (A1) alone, or in order to improve the fixability of the polyester resin, the aromatic dicarboxylic acid (A1) and the trivalent or higher polyhydric carboxylic acid (A2). ) Is used by mixing. 100 mole parts by weight of the mixture of the aromatic dicarboxylic acid and the trivalent or higher polyhydric carboxylic acid are composed of 80 to 99 mole parts by weight of the aromatic dicarboxylic acid and 1 to 20 mole parts by weight of the trivalent or higher polyhydric carboxylic acid.

The aromatic dicarboxylic acid (A1) is 1 selected from terephthalic acid, isophthalic acid, dimethyl terephthalate, dimethyl isophthalate, diethyl terephthalate, diethyl isophthalate, dibutyl terephthalate, dibutyl isophthalate or acid anhydrides thereof. It is an aromatic diacid more than one species, and if necessary, adipic acid, oxalic acid, mesaconic acid, itaconic acid, repagiline acid, alkenylsuccinic acid, glutamic acid, azelanic acid, succinic acid, citraconic acid, fumaric acid, maleic acid and Aliphatic diacids selected from sebacic acid may be used alone or in combination of two or more thereof.

The trivalent or higher polyhydric carboxylic acid component (A2) includes trimellitic acid, pyromellitic acid, 1,2,4-cyclohexane tricarboxylic acid, benzophenone tetracarboxylic acid, 2,5,7-naphthalene tricarboxylic acid Acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, and 1,3-dicarboxy-2--2-methyl One or more types selected from 2-methylenecarboxypropane can be used.

(B) aromatic diols

The aromatic diol according to the present invention is a bisphenol A derivative to which ethylene oxide or propylene oxide is added, and the α value of the ethylene oxide adduct is 277 to 444, the α value of the propylene oxide adduct is 224 to 362, and their acidity (pH ) Is preferably 7.0 to 8.5. α value can be obtained through the following equation.

Wherein R is 8.314 and T is 25.

If the α value of the ethylene oxide adduct is less than 277 and the α value of the propylene oxide adduct is less than 224, the reactivity decreases and the conversion of the polymerization reaction is lowered, thereby lowering the glass transition temperature of the resin during polymerization, thereby lowering the thermal stability and storage stability. There is a problem causing the offset phenomenon. When the α value of the ethylene oxide addition is 444 or more and the α value of the propylene oxide adduct is 362 or more, the conversion is increased, but the molecular weight distribution is narrow, which makes it difficult to obtain a wide offset range, and also has a low molecular weight, which is disadvantageous for low temperature fixation.

The aromatic diol according to the present invention is used 30 to 80 mole parts based on 100 mole parts by weight of the acid component (A). When the aromatic diol is less than 30 mole parts by weight, the reaction rate is increased but the thermal stability, storage stability is insufficient, when it exceeds 80 mole parts by weight, the thermal stability and storage stability increases but the reaction rate is lowered. In particular, it is preferable that the bisphenol A derivative added with ethylene oxide is 10-30 mole parts by weight and the bisphenol A derivative added with propylene oxide is 20-50 molar parts by weight based on 100 mole parts by weight of the acid component (A).

Examples of the aromatic diols include polyoxyethylene- (n) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (n) -2,2-bis (4-hydroxyphenyl) propane, Or these derivatives can be mentioned, These can be used individually or in mixture of 2 or more types.

(C) aliphatic diols

The aliphatic diols according to the present invention are ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butanediol, 1,4-butenediol, neopentylglycol, 2,3-butanediol, 1, 5-pentanediol, 2,3-pentanediol, 1,6-hexanediol, 2,3-hexanediol, 3,4-hexanediol, 1,7-heptanediol, dodecanediol, 1,4-cyclohexane Dimethanol, 1,4-cyclohexanediol and the like can be used, and 10 to 50 mole parts by weight based on 100 mole parts by weight of the acid component (A). When the aliphatic diol is used at less than 10 mole parts, the reaction rate is significantly lowered. When the aliphatic diol is used at more than 50 mole parts, the glass transition point (Tg) of the product is lowered, thereby lowering thermal stability and storage stability.

(D) trihydric or higher polyhydric alcohol

The present invention can further advance the polycondensation reaction by further adding a trivalent or higher polyhydric alcohol component as necessary in order to improve the thermal stability of the resulting resin. The polyhydric alcohol is trimethylol ethane, trimethylol propane, 2-methyl propane triol, glycerol, 1,2,5-pentane triol, 1,2,4-butane triol, pentaerythritol, dipentaerythritol, Tripentaerythritol, sorbitol, 2-hydroxymethylpropane-1,3-diol, 2-methyl-1,2,4-butanetriol, 1,3,5-trihydroxymethylbenzene, 1,2, 3,6-hexanetetrol, 1,4-sorbitan, and the like, and 1.0 to 20 mole parts by weight based on 100 mole parts by weight of the acid component (A). If the content of the polyhydric alcohol is less than 1.0 mole parts by weight, the thermal stability of the produced resin is insufficient and the molecular weight distribution is narrow, the low-temperature fixability is worse, if it exceeds 20 mole parts by weight it is difficult to obtain a polymer due to the gelation of the resin.

Modified polyester resin

The modified polyester resin according to the present invention is a polyvalent or higher polyhydric carbohydrate with the above-mentioned aromatic dicarboxylic acid or aromatic dicarboxylic acid in the presence of a polycondensation reaction catalyst selected from a titanium-based catalyst, a zinc acetate catalyst, or a mixed catalyst thereof. An acid component selected from the mixture of acids, aromatic diols, aliphatic diols, and optional trivalent or higher polyhydric alcohol components are prepared by polycondensation reaction.

It is preferable that Tg of the modified polyester resin which concerns on this invention is 55-70 degreeC. If the Tg of the modified polyester resin is less than 55 ° C., the storage stability of the toner becomes low, and if it exceeds 70 ° C., there is a possibility that low temperature fixability is deteriorated. In addition, the softening temperature of the modified polyester resin is preferably 110 ℃ to 150 ℃. If the softening temperature is less than 110 ℃ Tg is lowered because the storage stability is poor, the particles may aggregate, may cause an offset phenomenon. If the softening temperature exceeds 150 ℃, low temperature fixability may be lowered, the crushability is worse.

The modified polyester resin according to the present invention has a content of high molecular weight resin eluted at 0 to 10 minutes in liquid chromatography (LC) analysis of 10 to 25%, and a content of low molecular weight resin to be eluted at 20 to 30 minutes. It is preferable that it is 40%. If the ratio of the high molecular weight resin is less than 10%, the thermal stability is poor, if more than 25% the low-temperature fixability and the crushing properties are poor and may cause an offset phenomenon. If the ratio of the low molecular weight resin is 40% or more, the storage stability is poor due to the reduction of the glass transition temperature, and may cause an offset phenomenon. If it is less than 20%, the low temperature fixability is poor due to the increase of the softening temperature. Do.

In addition, the modified polyester resin according to the present invention preferably has a number average molecular weight (Mn) of 3000 to 7000 by GPC.

The present invention also provides a toner comprising the modified polyester resin according to the present invention described above. The toner according to the present invention further includes conventional toner additives such as colorants, charge control agents and waxes. The content of the modified polyester resin and conventional additives can be easily determined by those skilled in the art, and toner may be prepared according to a manufacturing method known in the art.

The toner according to the present invention preferably has a decomposition start temperature of 280 ° C. or more and a residual amount of 450% or more when analyzed by a thermogravimetric analyzer, and most preferably, a decomposition start temperature of 290 ° C. or more and a residual amount of 450 ° C. More than 60%.

As described above, the modified polyester resin according to the present invention can be usefully used as a binder because of excellent thermal stability, storage stability, pulverization, and low temperature fixability, in particular, when the resin is used as a binder for toner, A toner excellent in storage stability and low temperature fixability can be produced.

The present invention will be described in detail based on the following examples. However, the present invention is not limited by the following examples.

Example

Α values and acidity (pH) of bisphenol A derivatives to which ethylene oxide or propylene oxide, which is an aromatic diol (B), used in Examples and Comparative Examples were added, are shown in Tables 1 and 2 below.

BHEP-1 BHEP-2 BHEP-3 BHEP-4 BHEP-5 BHEP-6 alpha 372.8 307.7 345.9 266.6 468.9 255.8 PH (pH) 7.91 7.5 8.0 7.1 8.5 6.0

1) BHEP: Polyoxyethylene- (n) -2,2-bis (4-hydroxyphenyl) propane

BHPP-1 BHPP-2 BHPP-3 BHPP-4 BHPP-5 BHPP-6 alpha 351.4 319.7 288.3 206.0 393.3 217.8 PH (pH) 8.4 7.65 7.1 7.0 8.2 5.8

1) BHPP: Polyoxypropylene- (n) -2,2-bis (4-hydroxyphenyl) propane

Examples 1-6 and Comparative Examples 1-6

After adding 900 ppm of titanium-based catalyst to the reactants of the contents and composition as shown in Table 3 below based on the acid component (A1 and A2 component) content, the temperature was raised to 230 ° C. using a 15 liter melt condensation reactor. After removing the by-products, the pressure of the reaction system was gradually reduced to 0.1 mmHg while increasing the temperature to 250 ° C., thereby preparing a modified polyester resin for a binder.

Ingredients (parts by weight) Example Comparative example One 2 3 4 5 6 One 2 3 4 5 6 Terephthalic Acid (A1) 100 100 100 100 85 82 100 100 100 100 85 70 Trimellitic anhydride (A2) - - - - 15 18 - - - - 15 30 BHPP-1 (B) - - 25 - 50 - - - 5 - - - BHPP-2 (B) 45 - - 25 - - 50 - - 30 - 45 BHPP-3 (B) - 50 - - - 50 - 45 - - 5 - BHEP-1 (B) 25 - - 25 - - 40 - 5 - - - BHEP-2 (B) - - 25 - 20 - - 45 - - 5 25 BHEP-3 (B) - 20 - - - 20 - - - 10 - - Ethylene Glycol (C) 12 15 30 30 30 30 5 - 75 25 90 30 Trimethylolpropane (D) 18 15 20 20 - - 5 10 15 35 - -

Property measurement

Reaction conversion (%), softening temperature, Tg, and gel content (%) of the modified polyester resins prepared according to Examples 1 to 6 and Comparative Examples 1 to 6 are shown in Table 4 below.

Reaction conversion (%) was calculated by conventional methods based on methanol effluent.

The softening temperature was measured using a flow tester (CFT-500D) at a heating rate of 6 ° C. per minute under a load of 20 kgf using a nozzle of 1.5 mm in diameter and 1 mm in height.

Tg was measured by using a differential scanning calorimeter (DSC) to raise the temperature rate to 10 ° C. per minute, increase the temperature, and then increase the temperature.

The gel content (%) was obtained by dispersing 0.5 g of the sample in 50 ml of tetrahydrofuran (THF) solution, heating under reflux for 3 hours, separating the 3G3 micro glass filter, and drying and remaining.

Meanwhile, 92% by weight of the modified polyester resin, 4% by weight of carbon black, 1% by weight of charge control agent, and 3% by weight of carnauba wax, prepared according to the above-described examples and comparative examples, were mixed in a Henkel mixer for 5 minutes, followed by a twin screw extruder. Melt kneading was carried out to obtain a toner composition. The obtained toner composition was pulverized to an average particle size of 9.1 mu m using a jet mill-type 100AFG grinder (PULVERIZER), and the storage stability, thermal stability, and fixability of the toner were measured and shown in Table 4 below.

The storage stability was measured in the degree of aggregation and wax blooming after 10g of the pulverized toner particles in a 20ml vial and left for 48 hours in an oven at 60 ℃. Thermal stability was measured in a range of 50 to 600 ° C. using a thermogravimetric analyzer (manufacturer: PerkinElmer) at a rate of temperature increase of 10 ° C. per minute. Fixability was evaluated by the amount of toner remaining when the 3M tape was attached to the printed paper, the weight of 500 g was rubbed 10 times, and the tape was removed.

Meanwhile, the toner particles prepared from the polyester resin according to Example 1 were analyzed by LC (Liquid Chromatography), and the analysis results are shown in FIG. 1, and the weight ratio (%) of the high molecular weight resin fraction eluted at 0 to 10 minutes after the analysis was performed. ) And the weight ratio (%) of the low molecular weight resin fraction eluted at 20 to 30 minutes are shown in Table 4, respectively. LC was measured by placing 50 mg of toner in 10 ml of THF and heating in a 50 ° C. water bath for 1 hour and then cooling.

Example Comparative example Properties One 2 3 4 5 6 One 2 ^* 3 4 5 6 % Conversion 80 82 75 79 83 81 55 50 82 64 81 63 Softening Temperature (℃) 133 112 146 122 140 144 104 97 153 162 168 165 Tg (占 폚) 67 62 66 63 66 65 57 49 55 59 58 60 Gel content (%) 10 2 20 10 18 25 One - 7 33 8 40 Storage stability ¹⁾ 5 5 5 5 5 5 2 One 2 2 2 3 Thermal stability ²⁾ 5 4 5 5 5 5 One One 3 3 2 2 Settling ³⁾ 5 5 4 4 5 5 2 One 2 One One One LC high molecular weight (% by weight) 19 15 24 18 21 22 5 One 30 38 40 41 LC low molecular weight (% by weight) 30 39 24 35 28 26 50 One 10 5 6 4

^* : Unreacted

1) Storage stability

5-aggregation not occurring; 4-fine surface agglomeration, dispersion at 1 or 2 vibrations; 3-fine flocculation, dispersion at 3-4 vibrations; 2-part cohesion, microdispersion on vibration; 1-complete aggregate formation

2) thermal stability

5- Decomposition start temperature is above 290 ℃, remaining amount over 450% at 450 ℃

4- Decomposition start temperature is above 280 ℃, remaining amount over 450% at 450 ℃

3- Decomposition start temperature is over 270 ℃, remaining amount over 450% at 450 ℃

2- Decomposition start temperature is above 260 ℃, 30% remaining amount at 450 ℃

1-Decomposition start temperature is less than 260 ° C, remaining amount less than 30% at 450 ° C

3) Settleability

5-91% or more; 4- residual amount 81-90%; 3- 71% to 80% remaining; 2-61-70% remaining;

1- Less than 61% remaining

As shown in Table 4, the toner prepared according to the embodiment had excellent storage stability, thermal stability, and fixability. As in Examples 1 and 6, 2 and 5, one of the trivalent or higher polyhydric carboxylic acid (A2) or the trivalent or higher polyhydric alcohol (D) is used, while the aromatic diol (B) according to the present invention is used. In producing the resin, all of them were excellent without any difference in storage stability, thermal stability, and fixability of the toner. In Examples 3 and 4, aromatic diols (B) satisfying the range of α values according to the present invention were used in combination. In this case, the storage stability, thermal stability, and fixability of the toner were also excellent without any difference. However, even in the case of using BHPP and BHEP according to the present invention as aromatic diols (B) as in Comparative Examples 1 and 2, 3 and 5, when the content ratio is not included within the scope of the present invention, the storage stability of the toner, Both thermal stability and fixability were deteriorated. In addition, even when using the bisphenol A derivative according to the present invention as in Comparative Examples 4 and 6, the content of the trivalent or higher polyhydric carboxylic acid (A2) or the trivalent or higher polyhydric alcohol (D) is not included within the scope of the present invention. The storage stability, thermal stability, and fixability of the toner were also low. In particular, in the case of Comparative Example 2, since the total content of the aromatic diol (B) exceeded 80 molar parts, the reactivity was poor, and it was difficult to obtain a toner having a desired physical property in the present invention.

Examples 7-9 and Comparative Examples 7-9

A polyester resin was prepared under the same composition, content, and reaction conditions as in Example 1, except that different kinds of bisphenol A derivatives were mixed as shown in Table 5, and the same method as in Example 1 was used. Toner was prepared. Physical properties of the prepared resin and toner were measured in the same manner as in Example 1, and the results are shown in Table 5 below.

Example Comparative example 7 8 9 7 8 9 BHPP BHPP-1 BHPP-2 BHPP-3 BHPP-4 BHPP-5 BHPP-6 BHEP BHEP-1 BHEP-1 BHEP-1 BHEP-1 BHEP-1 BHEP-1 % Conversion 76 80 82 54 51 59 Softening Temperature (℃) 130 136 108 102 98 122 Tg (占 폚) 64 66 63 50 49 52 Gel content (%) 8 10 4 2 One 3 Storage stability 5 5 5 2 One 2 Thermal stability 5 5 4 2 One 2 Fixability 5 5 5 2 One 2 LC high molecular weight (% by weight) 18 21 10 2 One 8 LC low molecular weight (% by weight) 30 25 38 4 One 15

Examples 10-12 and Comparative Examples 10-12

A polyester resin was prepared under the same composition, content, and reaction conditions as in Example 1, except that different kinds of bisphenol A derivatives were mixed as shown in Table 6, and the same method as in Example 1 was used. Toner was prepared. Physical properties of the prepared resin and toner were measured in the same manner as in Example 1, and the results are shown in Table 6 below.

Example Comparative example 10 11 12 10 11 12 BHPP BHPP-1 BHPP-1 BHPP-1 BHPP-1 BHPP-1 BHPP-1 BHEP BHEP-1 BHEP-2 BHEP-3 BHEP-4 BHEP-5 BHEP-6 % Conversion 82 78 79 55 53 52 Softening Temperature (℃) 144 140 135 104 99 123 Tg (占 폚) 66 64 63 50 49 51 Gel content (%) 10 9 7 2 One 3 Storage stability 5 5 5 One One 2 Thermal stability 5 5 5 One 2 2 Fixability 5 5 4 One One 2 LC high molecular weight (% by weight) 20 17 15 3 One 7 LC low molecular weight (% by weight) 24 29 31 5 One 18

Examples 13-15 and Comparative Examples 13-15

A polyester resin was prepared under the same composition, content, and reaction conditions as in Example 1, except that different kinds of bisphenol A derivatives were mixed as described in Table 7, and the same method as in Example 1 was used. Toner was prepared. Physical properties of the prepared resin and toner were measured in the same manner as in Example 1, and the results are shown in Table 7 below.

Example Comparative example 13 14 15 13 14 15 BHPP BHPP-2 BHPP-3 BHPP-2 BHPP-2 BHPP-3 BHPP-5 BHEP BHEP-2 BHEP-3 BHEP-3 BHEP-5 BHEP-6 BHEP-5 % Conversion 80 81 79 52 49 47 Softening Temperature (℃) 146 138 113 128 118 104 Tg (占 폚) 62 63 62 52 50 48 Gel content (%) 15 11 4 2 One One Storage stability 5 5 5 One One One Thermal stability 5 5 4 2 One One Fixability 5 5 5 One One One LC high molecular weight (% by weight) 23 19 11 9 8 2 LC low molecular weight (% by weight) 30 28 22 18 14 3

1 is a result of analyzing the toner particles prepared from the polyester resin according to Example 1 by liquid chromatography (LC). 1, the horizontal axis represents time (min) and the vertical axis represents height.

Claims (6)

Acid component selected from aromatic dicarboxylic acids or mixtures of aromatic dicarboxylic acids and trivalent or higher polyhydric carboxylic acids in the presence of a polycondensation reaction catalyst selected from the group consisting of titanium-based catalysts, zinc acetate catalysts, and mixtures thereof. A modified polyester resin prepared by polycondensing a reactant comprising 100 mole parts by weight, 30 to 80 mole parts by weight of aromatic diol and 10 to 50 mole parts by weight of aliphatic diol, The aromatic diol is composed of 10 to 30 mole parts by weight of bisphenol A derivative added with ethylene oxide and 20 to 50 mole parts by weight of bisphenol A derivative added with propylene oxide, based on 100 mole parts by weight of the acid component, wherein the ethylene oxide is added Modified polyester resin wherein the α value of the bisphenol A derivative and the bisphenol A derivative to which the propylene oxide is added satisfy the following formulas (1) and (2): Formula (1): 277 <

<444 Formula (2): 224 <

<362 Wherein R is 8.314 and T is 25. The modified polyester resin according to claim 1, wherein the aromatic diol has an acidity of 7.0 to 8.5. The modified polyester resin of claim 1, wherein the reactant further comprises 1 to 20 mole parts by weight of a trivalent or higher polyhydric alcohol. delete The modified polyester resin according to any one of claims 1 to 3, wherein the modified polyester resin has a content of 10-25% of a high molecular weight resin eluted within 10 minutes by liquid chromatography analysis based on the total weight, and 20-30 A modified polyester resin, wherein the content of the low molecular weight resin eluted in the powder is 20 to 40%. A toner produced by using the polyester resin of any one of claims 1 to 3 as a binder resin.

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