JP4750609B2 - Toner binder particles and method for producing the same - Google Patents

Description

  The present invention relates to toner binder particles and a method for producing the same.

  Conventionally, from the viewpoint of fixability, charging stability, and filming resistance, a crystalline polyester having a ratio of the softening point to the maximum peak temperature of heat of fusion (softening point / peak temperature) of 0.6 to 1.3 and softening The amorphous polyester having a ratio of the point to the maximum peak temperature of heat of fusion (softening point / peak temperature) of more than 1.3 and 4 or less, and the number average molecular weight of the crystalline polyester is 4,000 to A toner binder in which the acid value of the amorphous polyester is 10,000 mgKOH / g or less has been proposed (Patent Document 1).

JP 2004-226847 A

However, conventionally, since the crystalline polyester and the amorphous polyester are mixed at the time of forming the toner, the two kinds of polyesters which are difficult to mix cannot be sufficiently uniformly dispersed. There is a problem that the polyester becomes non-uniform. As a result, the toner using the conventional toner binder tends to cause image deterioration. In particular, when this toner is subjected to high-speed continuous printing, image deterioration is remarkable.
An object of the present invention is to provide a toner binder in which image deterioration is unlikely to occur.

The toner binder particles of the present invention are characterized by the crystalline polyester (A) having a ratio of softening point to the maximum peak temperature of heat of fusion (softening point / peak temperature) of 0.92 to 1.08,
Toner binder particles comprising amorphous polyester (B) having a ratio of softening point to maximum peak temperature of heat of fusion (softening point / peak temperature) of greater than 1.3 and 4 or less,
The crystalline polyester (A) is an alcohol component containing 80 to 100 mol% of an aliphatic diol having 2 to 6 carbon atoms and a carboxylic acid component containing 80 to 100 mol% of an aliphatic dicarboxylic acid having 2 to 8 carbon atoms. A polymer obtained by condensation polymerization of
The gist is that the crystalline polyester (A) and the amorphous polyester (B) are uniformly mixed in the particles by melt mixing.

The toner binder of the present invention can be easily and uniformly dispersed in the toner when it is converted into a toner.
Therefore, the toner using the toner binder of the present invention does not cause image deterioration. In particular, even when subjected to high-speed continuous printing, image degradation does not occur.

“Crystallinity” means that the ratio of the softening point to the maximum peak temperature of the heat of fusion (softening point / peak temperature) is 0.92 to 1.08, preferably 0.98 to 1.04.
“Amorphous” means that the ratio of the softening point to the maximum peak temperature of the heat of fusion (softening point / peak temperature) is greater than 1.3 and 4 or less, preferably 1.5 to 2.5. .

  About crystalline polyester (A), ratio (softening point / peak temperature) of a softening point and the maximum peak temperature of a heat of fusion is 0.92-1.08, Preferably it is 0.98-1.04. If it is within this range, the image is more difficult to deteriorate.

The softening point is a value measured as follows.
Using a descending flow tester {for example, CFT-500D, manufactured by Shimadzu Corporation), a load of 1.96 MPa was applied by a plunger while heating a measurement sample of 1 g at a heating rate of 6 ° C./min. Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm, draw a graph of “plunger descent amount (flow value)” and “temperature”, and graph the temperature corresponding to 1/2 of the maximum plunger descent amount And this value (temperature when half of the measurement sample flows out) is taken as the softening point.

Moreover, the maximum peak temperature of the heat of fusion is a value measured as follows.
Using a differential scanning calorimeter {for example, DSC210, manufactured by Seiko Denshi Kogyo Co., Ltd.], the sample to be measured was heated to 200 ° C., cooled to 0 ° C. at a cooling rate of 10 ° C./min, and then heated to 10 ° C. The temperature is increased at a time per minute and the change in endothermic heat is measured. A graph of “endothermic heat generation” and “temperature” is drawn, and the temperature corresponding to the maximum peak of the endothermic heat generation is the maximum peak temperature of the heat of fusion.

The softening point (° C.) of the crystalline polyester (A) is preferably 95 to 155, more preferably 100 to 140, and particularly preferably 110 to 130, from the viewpoint of fixability.
The maximum peak temperature (° C) of the heat of fusion of the crystalline polyester (A) is preferably 110 to 135, more preferably 115 to 130, and particularly preferably 120 to 125, from the viewpoint of fixability.

The number average molecular weight (Mn) of the crystalline polyester (A) is preferably 1,000 to 10,000, more preferably 1,500 to 9,000, particularly preferably 2,000 to 7,000.
The number average molecular weight (Mn) is measured by gel permeation chromatography (GPC) using polystyrene having a known molecular weight as a standard substance {JIS K0124: 2002 (general rule for high performance liquid chromatography), corresponding ISO; ISO 11843-1: 1997 (capability of detection-Part1: Terms and definitions.)} (For example, measurement conditions are as follows). The crystalline polyester (A) is dissolved in chloroform {concentration: 0.5 g / 100 ml}, and the amorphous polyester (B) is dissolved in tetrahydrofuran {concentration: 0.5 g / 100 ml. Subsequently, this solution is filtered using a fluororesin filter having a pore size of 2 μm (for example, FP-200, manufactured by Sumitomo Electric Industries, Ltd.) to remove insoluble components to obtain a measurement sample solution.
Apparatus: CO-8010 {manufactured by Tosoh Corporation}
Column: GMLX and G3000HXL (both manufactured by Tosoh Corporation) each connected in series Column injection amount: 100 μL
Eluent: Crystalline polyester (A): Chloroform Amorphous polyester (B): Flow rate of tetrahydrofuran eluent: 1 mL / min Detector: Differential refractive index detector (RID)

  As the above crystalline polyester (A), an alcohol component containing 80 to 100 mol% of an aliphatic diol having 2 to 6 carbon atoms and 80 to 100 mol% of an aliphatic dicarboxylic acid having 2 to 8 carbon atoms. A polymer obtained by condensation polymerization of the contained carboxylic acid component is preferred.

Examples of aliphatic diols include α, ω-linear alkanediols, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, Examples include 1,6-hexanediol, neopentyl glycol, and 1,4-butenediol.
Of these, 1,2-propylene glycol, 1,3-propylene glycol and 1,4-butanediol are preferable, and 1,4-butanediol is more preferable.

The aliphatic diol is preferably contained in the alcohol component in an amount of 80 to 100 mol% (preferably 90 to 100 mol%).
The alcohol component may contain a polyhydric alcohol other than the aliphatic diol having 2 to 6 carbon atoms.
Examples of the polyhydric alcohol include bisphenol A alkylene (2 to 3 carbon atoms) oxide (average added mole number 1 to 10) adduct {polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene -2,2-bis (4-hydroxyphenyl) propane}, glycerin, pentaerythritol, trimethylolpropane and the like.

Examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, and adipic acid. In addition, anhydrides of these dicarboxylic acids, Alkyl (C1-C3) ester etc. are contained.
Of these, fumaric acid and adipic acid are preferable, and fumaric acid is more preferable.

The aliphatic dicarboxylic acid is preferably contained in the carboxylic acid component in an amount of 80 to 100 mol% (preferably 90 to 100 mol%).
The carboxylic acid component may contain a polyvalent carboxylic acid other than the aliphatic dicarboxylic acid having 2 to 8 carbon atoms.
Examples of the polyvalent carboxylic acid include aromatic dicarboxylic acids {phthalic acid, isophthalic acid, terephthalic acid, etc.}, aliphatic dicarboxylic acids {sebacic acid, azelaic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, etc.}, alicyclic Dicarboxylic acids {cyclohexanedicarboxylic acid and the like} and trivalent or higher polyvalent carboxylic acids {trimellitic acid and pyromellitic acid and the like}, and the like. ) Esters are included.

  The molar ratio of the carboxylic acid component to the alcohol component (carboxylic acid component / alcohol component) in the crystalline polyester (A) is preferably higher than the carboxylic acid component, more preferably 0, from the viewpoint of molecular weight. .9 or more and less than 1, particularly preferably 0.95 or more and less than 1.

  The condensation polymerization of the alcohol component and the carboxylic acid component is preferably performed in an inert gas atmosphere. The reaction temperature (° C.) is preferably from 100 to 250, more preferably from 110 to 240, particularly preferably from 120 to 230. If necessary, an esterification catalyst or a polymerization inhibitor may be used.

  The ratio of the softening point of the amorphous polyester (B) to the maximum peak temperature of the heat of fusion (softening point / peak temperature) is greater than 1.3 and 4 or less, preferably 1.5 to 2.5. If it is within this range, the image is more difficult to deteriorate.

The softening point (° C.) of the amorphous polyester (B) is preferably from 80 to 180, more preferably from 100 to 155, particularly preferably from 105 to 150, from the viewpoint of fixability.
The maximum peak temperature (° C.) of the heat of fusion of the amorphous polyester (B) is preferably 50 to 90, more preferably 55 to 80, and particularly preferably 60 to 80 from the viewpoint of fixability.

The glass transition point (° C.) of the amorphous polyester (B) is preferably from 45 to 80, more preferably from 55 to 75, particularly preferably from 60 to 70, from the viewpoint of fixability.
The glass transition point is a physical property peculiar to an amorphous resin, and is distinguished from the maximum peak temperature of heat of fusion. The glass transition point is the maximum from the extension of the baseline below the maximum peak temperature in the graph of `` endothermic heat generation '' and `` temperature '' in the measurement of the maximum peak temperature of heat of fusion, and the rising part of the maximum peak. The temperature corresponding to the intersection point with the tangent indicating the maximum inclination to the peak apex is defined as the glass transition point.

  The number average molecular weight (Mn) of the amorphous polyester (B) is preferably 1,000 to 6,000, more preferably 2,000 to 5,000, and particularly preferably 3,000 to 4,000.

The acid value (mgKOH / g) of the amorphous polyester (B) is preferably 0 to 30, more preferably 1 to 25, and particularly preferably 2 to 23 from the viewpoint of the chargeability of the toner.
The acid value is measured according to JIS K0070-1992.

The amorphous polyester (B) as described above can be produced by polycondensing an alcohol component and a carboxylic acid component in the same manner as the crystalline polyester (A). However, in order to make it amorphous, it is preferable to apply the following method (1) or (2).
(1) In the case of using only a monomer that promotes crystallization of a resin such as an aliphatic diol having 2 to 6 carbon atoms or an aliphatic carboxylic acid having 2 to 8 carbon atoms, two or more of these monomers are used in combination. The method of suppressing the conversion {in any of the alcohol component and the carboxylic acid component, one of these monomers accounts for 10 to 70 mol% (preferably 20 to 60 mol%) of each component, and these monomers are 2 More than one species (preferably 2 to 4 species) are preferably used. }
(2) Monomer that promotes amorphization {alcohol component: alkylene oxide adduct of bisphenol A, carboxylic acid component: succinic acid substituted with alkyl group or alkenyl group, etc.} in the alcohol component or carboxylic acid component A method of using 30 to 100 mol% (preferably 50 to 100 mol%) in the inside (preferably both components).

The amorphous polyester (B) is composed of a low softening point amorphous polyester (B1) and a high softening point amorphous polyester (B2) from the viewpoint of low-temperature fixability and high-temperature offset resistance. The difference (B2-B1) between the softening point and the softening point of (B2) is preferably 10 to 80 ° C, more preferably 30 to 60 ° C, and particularly preferably 45 to 55 ° C.
The softening point (° C.) of the low-softening point amorphous polyester (B1) is preferably 70 to 120, more preferably 90 to 115, particularly preferably 95 to 105, from the viewpoints of low-temperature fixability and high-temperature offset resistance. It is. In order to make such a range, for example, the molar ratio of the carboxylic acid component and the alcohol component (carboxylic acid component / alcohol component) is made smaller than 1.0 (for example, about 0.90 to 0.95) or This can be achieved by increasing the size (for example, about 1.05 to 1.10).
The softening point (° C.) of the high softening point amorphous polyester (B2) is preferably 120 to 180, more preferably 130 to 170, and particularly preferably 150 to 160, from the viewpoint of low temperature fixability and high temperature offset resistance. It is. In order to make such a range, for example, the molar ratio of the carboxylic acid component to the alcohol component (carboxylic acid component / alcohol component) is brought close to 1.0 (for example, about 0.95 to 1.05). It can be achieved by increasing the content of a polyhydric alcohol component having a valence of at least and / or a polycarboxylic acid component having a valence of 3 or more (for example, about 5 to 30 mol% based on the number of moles of all monomers).

  When the amorphous polyester (B) comprises a low softening point amorphous polyester (B1) and a high softening point amorphous polyester (B2), the low softening point amorphous polyester (B1) and the high softening point amorphous The content ratio (B1 / B2) to the polyester (B2) is preferably 50/50 to 1/99, more preferably 40/60 to 5/95, and particularly preferably 30/70 to 10/90.

The content weight ratio (A / B) of the crystalline polyester (A) and the amorphous polyester (B) is 1/99 to 50/50 from the viewpoints of fixability, charging stability and filming resistance. More preferably, it is 5/95 to 40/60, and particularly preferably 10/90 to 30/70.
The toner binder particles of the present invention may contain a known vinyl resin and / or a known wax in addition to the crystalline polyester (A) and the amorphous polyester (B).

The toner binder particles of the present invention are not limited in the production method as long as the crystalline polyester (A) and the amorphous polyester (B) are uniformly mixed in the particles by melt mixing, but the following step (1) And (2).
<Step (1)>
A crystalline polyester (A) having a ratio of the softening point to the maximum peak temperature of heat of fusion (softening point / peak temperature) of 0.92 to 1.08;
Amorphous polyester (B) in which the ratio of the softening point to the maximum peak temperature of the heat of fusion (softening point / peak temperature) is greater than 1.3 and less than or equal to 4 is melt-mixed at 80 to 180 ° C. and uniform in the particles Mixing to obtain a molten mixture.
<Step (2)>
A step of cooling the molten mixture from the melting temperature to 60 ° C. or lower to obtain toner binder particles.

Step (1) will be described.
The melt mixing of the crystalline polyester (A) and the amorphous polyester (B) is not limited as long as the molten mixture is uniformly mixed in the particles.
The melt mixing temperature (° C.) is preferably from 100 to 180, more preferably from 110 to 170, and particularly preferably from 120 to 160, from the viewpoint of uniform mixing and transesterification.
The melt mixing time is preferably from 10 seconds to 30 minutes, more preferably from 20 seconds to 10 minutes, and particularly preferably from 30 seconds to 5 minutes, from the viewpoint of uniform mixing and transesterification.

The melt mixing apparatus may be either a batch type or a continuous type, but a continuous type melt mixing apparatus is preferable.
As the continuous mixing device, an extruder, a continuous kneader, a three-roller, or the like can be used. Among these, an extruder and a continuous kneader are preferable, and a continuous kneader is more preferable.

Step (2) will be described.
The cooling time for the molten mixture from the melting temperature to 60 ° C. or lower is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 8 minutes, and particularly preferably 30 seconds to 3 minutes from the viewpoint of fixability.
As the cooling device, a steel belt cooler, a drum cooler, a roll cooler, an air cooling belt, a strand cooling, and the like can be used. Among these, a steel belt cooler, a drum cooler, and a roll cooler are preferable, and a steel belt cooler is more preferable.

In the step (2), it may be formed into particles while being cooled, or may be formed into particles by pulverization or the like after cooling the molten mixture.
As a method of forming particles while cooling, the molten mixture is placed in a liquid (for example, water) of 60 ° C. or less (preferably 0 to 50 ° C., more preferably 1 to 30 ° C., particularly preferably 2 to 10 ° C.). A method of cooling while dropping (may be accompanied by stirring), a molten mixture in an atmosphere of 60 ° C. or less (preferably 0 to 50 ° C., more preferably 1 to 30 ° C., particularly preferably 2 to 10 ° C.). A method of cooling while spraying (discharging) can be applied.

As a method of forming particles by pulverization after cooling the molten mixture, a method of pulverizing with a pulverizer {pin mill, roll mill, hammer mill, cutter mill, etc.} can be applied.
The toner binder particles of the present invention preferably have a weight average particle diameter (mm) of 0.02 to 20, more preferably 0.05 to 5, and particularly preferably 0.1 to 3. Within this range, it is easier to produce toner.

  In addition, a weight average particle diameter is measured using the sieve prescribed | regulated to the low tap test sieve shaker and JISZ8801-1: 2000 based on JISZ8815-1994. That is, among the JIS standard sieves (the following numbers are nominal openings, combined from the top in the order of 22.4 mm, 13.2 mm, 8 mm, 4 mm, 1.4 mm, 500 μm, 180 μm and saucer, etc.) About 50 g of measurement sample particles are put in a sieve and vibrated for 5 minutes on a low-tap test sieve shaker. Weigh the measurement sample on each sieve and pan, and calculate the weight fraction of the measurement sample on each sieve with the total as 100% by weight. The value of each sieve is logarithmic probability paper (the horizontal axis is the nominal value of the sieve). After opening (particle diameter) and plotting the vertical axis as weight fraction}, a line connecting the points is drawn to obtain a “particle diameter-weight fraction” line. The weight average particle size is calculated by reading the coordinates (particle size) on the horizontal axis corresponding to the point where the “particle size-weight fraction” line intersects the 50% weight fraction axis.

The toner binder particles of the present invention can be mixed with a colorant, a charge control agent, and the like to form a toner. In addition, a mold release agent, a fluidizing agent, etc. can be further contained as needed.
If necessary, the toner is mixed with carrier particles {iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite (surface coated with acrylic resin, silicone resin, etc.)} to obtain an electric latent image. It can be used as a developer. Further, instead of the carrier particles, an electric latent image can be formed by friction with a charging blade or the like.
The electric latent image is fixed on a support (paper, polyester film, etc.) by a known hot roll fixing method or the like.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. Unless otherwise specified, “%” means “% by weight” and “part” means “part by weight”.
<Example 1>
1010 parts (102 moles) of 1,4-butanediol, 1276 parts (100 moles) of fumaric acid, 2 parts of hydroquinone and 4 parts of dibutyltin oxide were reacted at 160 ° C. for 5 hours in a nitrogen atmosphere, and then 220 The mixture was allowed to react at 1 ° C. for 1 hour. Then, it was made to react at 8.3 kPa and 220 degreeC for 6 hours, and crystalline polyester (AA1) was obtained.
On the other hand, 1960 parts (70 mol parts) of bisphenol A propylene oxide adduct (average addition mole number 2.2 mol), 780 parts (30 mol parts) of bisphenol A ethylene oxide adduct (average mol number 2.2 mol), dodecenyl 257 parts (12 parts by mole) of succinic anhydride, 770 parts (58 parts by mole) of terephthalic acid, and 4 parts of dibutyltin oxide were reacted at 235 ° C. for 8 hours in a nitrogen atmosphere, and further at the same temperature at 8.3 kPa. The reaction was carried out for 1 hour. Subsequently, the temperature was raised to 180 ° C., 230 parts (15 mole parts) of trimellitic anhydride was added, the temperature was raised to 210 ° C. at 10 ° C. per hour, and the reaction was carried out at 210 ° C. for 5 hours to produce amorphous polyester (BB1) Got.

10 parts of crystalline polyester (AA1) and 90 parts of amorphous polyester (BB1) were put into a continuous kneader, and melt mixed at a jacket temperature of 120 ° C. and a residence time of 5 minutes. The molten resin was put into a steel belt cooler and cooled to 60 ° C. or lower in 10 minutes. Subsequently, it was pulverized with a hammer mill to obtain toner binder particles (1) of the present invention.
The number average molecular weight, the softening point, the maximum peak temperature of the heat of fusion, and the ratio (softening point / peak temperature) of the crystalline polyester are shown in Table 1, and the number average molecular weight, the softening point, and the maximum heat of fusion of the amorphous polyester. The peak temperature, ratio (softening point / peak temperature), glass transition temperature, and acid value are summarized in Table 2 (hereinafter the same).

<Example 2>
1,4-butanediol 1010 parts (102 mole parts), fumaric acid 1276 parts (100 mole parts), 1,4-butanediol 812 parts (82 mole parts), 1,6-hexanediol 260 parts (20 moles) Part) and 1276 parts (100 mole parts) of fumaric acid, in the same manner as in Example 1, to obtain a crystalline polyester (AA2).

  30 parts of the crystalline polyester (AA2) and 70 parts of the amorphous polyester (BB1) obtained in the same manner as in Example 1 were put into a continuous kneader, and melt mixed at a jacket temperature of 160 ° C. and a residence time of 30 seconds. The molten resin was put into a steel belt cooler and cooled to 60 ° C. or lower in 10 minutes. Subsequently, the toner binder particles (2) of the present invention were obtained by grinding with a hammer mill.

<Example 3>
1,4-butanediol 1010 parts (102 mole parts), fumaric acid 1276 parts (100 mole parts), 1,4-butanediol 812 parts (82 mole parts), 1,6-hexanediol 260 parts (20 moles) Part) and 1270 parts (100 mole parts) of fumaric acid, and in the same manner as in Example 1, a crystalline polyester (AA3) was obtained.

  40 parts of crystalline polyester (AA3) and 60 parts of amorphous polyester (BB1) obtained in the same manner as in Example 1 were put into a continuous kneader, and melt mixed at a jacket temperature of 100 ° C. and a residence time of 10 minutes. The molten resin was put into a steel belt cooler and cooled to 60 ° C. or lower in 10 minutes. Subsequently, it was pulverized with a hammer mill to obtain toner binder particles (3) of the present invention.

<Example 4>
257 parts (12 mole parts) of dodecenyl succinic anhydride and 770 parts (58 mole parts) of terephthalic acid were changed to 530 parts (40 mole parts) of terephthalic acid, and 230 parts (15 mole parts) of trimellitic anhydride Amorphous polyester (BB2) was obtained in the same manner as in Example 1 except that the content was changed to 237 parts (25.5 parts by mole) of fumaric acid and 353 parts (23 parts by mole) of trimellitic anhydride.

  5 parts of the crystalline polyester (AA1) and 95 parts of the amorphous polyester (BB2) obtained in the same manner as in Example 1 were put into a continuous kneader, and melt mixed at a jacket temperature of 170 ° C. and a residence time of 20 seconds. The molten resin was put into a steel belt cooler and cooled to 60 ° C. or lower in 10 minutes. Subsequently, the toner binder particles (4) of the present invention were obtained by grinding with a hammer mill.

<Example 5>
1960 parts (70 mol parts) of bisphenol A propylene oxide adduct (average mol number 2.2 mol), 780 parts (30 mol parts) of bisphenol A ethylene oxide adduct (average mol number 2.2 mol), bisphenol A Propylene oxide adduct (average addition mol number 2.2 mol) changed to 2800 parts (100 mol parts), dodecenyl succinic anhydride 257 parts (12 mol parts), terephthalic acid 770 parts (58 mol parts) In the same manner as in Example 1, except that the acid was changed to 398 parts (30 mole parts), and 230 parts (15 mole parts) trimellitic anhydride was changed to 650 parts (70 mole parts) fumaric acid. Crystalline polyester (BB3) was obtained.

  50 parts of crystalline polyester (AA1) and 50 parts of amorphous polyester (BB3) obtained in the same manner as in Example 1 were put into a continuous kneader, and melt mixed at a jacket temperature of 180 ° C. and a residence time of 10 seconds. The molten resin was put into a steel belt cooler and cooled to 60 ° C. or lower in 10 minutes. Subsequently, it was pulverized with a hammer mill to obtain toner binder particles (5) of the present invention.

<Example 6>
1 part of the crystalline polyester (AA2) obtained in the same manner as in Example 2 and 99 parts of the amorphous polyester (BB2) obtained in Example 4 were put into a continuous kneader, the jacket temperature was 110 ° C., and the residence time was 30. Melt mixed for minutes. The molten resin was put into a steel belt cooler and cooled to 60 ° C. or lower in 10 minutes. Subsequently, the toner binder particles (6) of the present invention were obtained by pulverization with a hammer mill.

<Example 7>
20 parts of the crystalline polyester (AA2) obtained in the same manner as in Example 2 and 80 parts of the amorphous polyester (BB3) obtained in Example 5 were put into a continuous kneader, the jacket temperature was 150 ° C., and the residence time was 5 Melt mixed for minutes. The molten resin was put into a steel belt cooler and cooled to 60 ° C. or lower in 30 seconds. Subsequently, it was pulverized with a hammer mill to obtain toner binder particles (7) of the present invention.

<Example 8>
25 parts of the crystalline polyester (AA3) obtained in the same manner as in Example 3 and 75 parts of the amorphous polyester (BB2) obtained in Example 4 were put into a continuous kneader, the jacket temperature was 160 ° C., and the residence time was 3 Melt mixed for minutes. The molten resin was put into a steel belt cooler and cooled to 60 ° C. or lower in 20 seconds. Subsequently, the toner binder particles (8) of the present invention were obtained by grinding with a hammer mill.

<Example 9>
25 parts of the crystalline polyester (AA3) obtained in the same manner as in Example 3 and 75 parts of the amorphous polyester (BB3) obtained in Example 5 were put into a continuous kneader, the jacket temperature was 150 ° C., and the residence time was 3 Melt mixed for minutes. The molten resin was put into a steel belt cooler and cooled to 60 ° C. or lower in 108 minutes. Subsequently, it was pulverized with a hammer mill to obtain toner binder particles (9) of the present invention.

<Example 10>
50 parts of crystalline polyester (AA1) obtained in the same manner as in Example 1, 35 parts of amorphous polyester (BB1) obtained in Example 3, and 15 parts of amorphous polyester (BB3) obtained in Example 5 Was put into a continuous kneader and melt-mixed with a jacket temperature of 150 ° C. and a residence time of 5 minutes. The molten resin was put into a steel belt cooler and cooled to 60 ° C. or less in 3 minutes. Subsequently, the toner binder particles (10) of the present invention were obtained by grinding with a hammer mill.

<Example 11>
50 parts of crystalline polyester (AA1) obtained in the same manner as in Example 1, 45 parts of amorphous polyester (BB2) obtained in Example 4, and 5 parts of amorphous polyester (BB3) obtained in Example 5 Was put into a continuous kneader and melt-mixed with a jacket temperature of 150 ° C. and a residence time of 5 minutes. The molten resin was put into a steel belt cooler and cooled to 60 ° C. or lower in 10 seconds. Subsequently, it was pulverized with a hammer mill to obtain toner binder particles (11) of the present invention.

<Example 12>
100 parts of toner binder particles (1) obtained in Example 1, 0.2 part of quaternary ammonium salt {COPY CHARGE PSY, Clariant Japan Ltd.}, 7 parts of carbon black {R330R, manufactured by Cabot Corporation} and carnauba wax {Carnauba wax no. 1, 1.5 parts of Hiroyuki Kato Co., Ltd.} are premixed for 2 minutes using a Henschel mixer, melt-kneaded (150 ° C., 1 minute) with a twin screw extruder, cooled to about 25 ° C., hammer mill In addition, 0.3 parts of HDK H3050VP {manufactured by Clariant Japan Co., Ltd.} was added and mixed with a Henschel mixer to obtain toner (1) of the present invention.

<Examples 13 to 22>
Example 12 except that 100 parts of the toner binder particles (1) obtained in Example 1 are changed to 100 parts of any of the toner binder particles (2) to (11) obtained in any of Examples 2 to 11. In the same manner, toners (2) to (11) of the present invention were obtained.

<Comparative Example 1>
10 parts of crystalline polyester (AA1) obtained in Example 1 and 90 parts of amorphous polyester (BB1) obtained in Example 1, quaternary ammonium salt {COPY CHARGE PSY, Clariant Japan Ltd.} 0.2 Part, carbon black {R330R, manufactured by Cabot Corporation} 7 parts and carnauba wax {carnauba wax no. 1, 1.5 parts of Hiroyuki Kato Co., Ltd.} are premixed for 2 minutes using a Henschel mixer, melt-kneaded (150 ° C., 1 minute) with a twin screw extruder, cooled to about 25 ° C., hammer mill Then, 0.3 part of HDK H3050VP {manufactured by Clariant Japan Co., Ltd.} was added and mixed with a Henschel mixer to obtain a comparative toner (H1).

<Comparative example 2>
8 parts of the crystalline polyester (AA1) obtained in Example 1 and 72 parts of the amorphous polyester (BB1) obtained in Example 1 were replaced with 30 parts of the crystalline polyester (AA2) obtained in Example 2 and Example 1 A comparative toner (H2) was obtained in the same manner as in Comparative Example 1, except that the amount was changed to 70 parts of the amorphous polyester (BB1) obtained in the above.

<Comparative Example 3>
8 parts of the crystalline polyester (AA1) obtained in Example 1 and 72 parts of the amorphous polyester (BB1) obtained in Example 1 were replaced with 40 parts of the crystalline polyester (AA3) obtained in Example 3 and Example 1. A comparative toner (H3) was obtained in the same manner as in Comparative Example 1 except that the amount was changed to 60 parts of the amorphous polyester (BB1) obtained in the above.

<Comparative example 4>
8 parts of the crystalline polyester (AA1) obtained in Example 1 and 72 parts of the amorphous polyester (BB1) obtained in Example 1 were replaced with 50 parts of the crystalline polyester (AA1) obtained in Example 1 and Example 5. A comparative toner (H4) was obtained in the same manner as in Comparative Example 1 except that the amount was changed to 50 parts of the amorphous polyester (BB3) obtained in the above.

<Minimum fixing temperature (MFT)>
30 parts of evaluation toner and 800 parts of ferrite carrier (F-150; manufactured by Powdertech) are uniformly mixed to form a two-component developer for evaluation. Using this developer, a developing machine {copier (AR5030; sharp) Unfixed image developed with the product excluding the fixing unit} manufactured by the fixing unit {the copier (SF8400A; manufactured by Sharp) with the fixing unit of the copying machine modified to make the heat roller temperature variable} the process speed 145 mm / sec. To obtain a fixed image {the heat roller temperature was changed from 110 ° C. to 230 ° C. every 10 ° C.}. Subsequently, the minimum temperature of the hot roller at which the residual ratio of the image density after rubbing the fixed image 5 times with a PPC pad paper to which a load of 300 g was applied was 70% or more was defined as the minimum fixing temperature.

<Hot offset generation temperature (HOT)>
While obtaining a fixed image in the same manner as the minimum fixing temperature (MFT), the minimum temperature of the hot roller when hot offset (visual observation) occurred was defined as the hot offset generation temperature.

<Image degradation>
Continuous development was performed in the same manner as the minimum fixing temperature (MFT) to obtain an unfixed image, and the 1000th and 5000th unfixed images were determined according to the following criteria.
○: Image deterioration (density unevenness, etc.) cannot be confirmed visually. Δ: Image deterioration (density unevenness) can be confirmed visually. X: Some results are not developed. Table 3 shows these results.

注）「２３０＜」は、２３０℃でもホットオフセットが発生しなかったことを示す。

Note) “230 <” indicates that hot offset did not occur even at 230 ° C.

As described above, all of the toners using the toner binder particles of the present invention obtained remarkably good results as compared with the toner of the comparative example.

Claims (9)

A crystalline polyester (A) having a ratio of the softening point to the maximum peak temperature of heat of fusion (softening point / peak temperature) of 0.92 to 1.08;
Toner binder particles comprising amorphous polyester (B) having a ratio of softening point to maximum peak temperature of heat of fusion (softening point / peak temperature) of greater than 1.3 and 4 or less,
The crystalline polyester (A) is an alcohol component containing 80 to 100 mol% of an aliphatic diol having 2 to 6 carbon atoms and a carboxylic acid component containing 80 to 100 mol% of an aliphatic dicarboxylic acid having 2 to 8 carbon atoms. A polymer obtained by condensation polymerization of
A toner binder particle, wherein the crystalline polyester (A) and the amorphous polyester (B) are uniformly mixed in the particles by melt mixing. The number average molecular weight of the crystalline polyester (A) is 1,000 to 10,000,
The toner binder particles according to claim 1, wherein the amorphous polyester (B) has an acid value of 30 mgKOH / g or less. The toner binder particles according to claim 1 or 2, wherein the crystalline polyester (A) has a softening point of 95 to 155 ° C. The amorphous polyester (B) comprises a low softening point amorphous polyester (B1) and a high softening point amorphous polyester (B2), and the difference between the softening point of (B1) and the softening point of (B2) (B2 The toner binder particles according to claim 1, wherein -B1) is from 10 to 80 ° C. The toner binder particles according to claim 4, wherein the content weight ratio (B1 / B2) of the low softening point amorphous polyester (B1) and the high softening point amorphous polyester (B2) is 50/50 to 1/99. . The toner binder particle according to any one of claims 1 to 3, wherein the content weight ratio (A / B) of the crystalline polyester (A) to the amorphous polyester (B) is 1/99 to 50/50. A ratio of a softening point to a maximum peak temperature of heat of fusion (softening point / peak temperature) of 0.92 to 1.08, and an alcohol component containing 80 to 100 mol% of an aliphatic diol having 2 to 6 carbon atoms; A crystalline polyester (A) which is a polymer obtained by condensation polymerization of a carboxylic acid component containing 80 to 100 mol% of an aliphatic dicarboxylic acid having 2 to 8 carbon atoms;
Amorphous polyester (B) in which the ratio of the softening point to the maximum peak temperature of the heat of fusion (softening point / peak temperature) is greater than 1.3 and less than or equal to 4 is melt-mixed at 80 to 180 ° C. and uniform in the particles A method of producing toner binder particles, comprising: (1) mixing to obtain a molten mixture; and (2) obtaining toner binder particles by cooling the molten mixture from a melting temperature to 60 ° C. or less. . The production method according to claim 7, wherein the melt mixing time in step (1) is 10 seconds to 30 minutes, and the cooling time from the melting temperature in step (2) to 60 ° C or less is 10 seconds to 10 minutes. A toner comprising the toner binder particles according to claim 1, a colorant, and a charge control agent.