JP2005115352A - Toner for forming color image and toner kit - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner binder which makes toner particles free of sticking and agglomeration while maintaining excellent low-temperature fixability of a polyester toner binder, anti-hot-offset properties and a high gloss image, by using a polyester resin formed in the presence of a specified catalyst, in a toner for forming a color image used for electrophotography, etc. <P>SOLUTION: The toner used in a full color image forming system comprises at least a colorant and a binder resin based on a polyester resin, wherein the polyester resin is formed by a polycondensation ester reaction in the presence of at least one titanium-containing catalyst selected from the group consisting of halogenated titanium, titanium diketone enolates, titanium carboxylates, titanyl carboxylates and salts of titanyl carboxylates. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a dry toner and toner kit used for electrophotography, electrostatic recording, and the like, and more specifically, a toner for color image formation using a polyester resin formed by a polycondensation reaction in the presence of a titanium-containing catalyst as a binder. And a toner kit.

  When the polyester-based toner binder used in the dry toner is a toner, the toner can be fixed even when the heat roll temperature is low (low temperature fixability), and the toner is not fused to the heat roll even at a high heat roll temperature ( The amount of use tends to increase due to easy compatibility with hot offset resistance) and excellent low-temperature fixability. In particular, color toners tend to require gloss on fixed images due to color development problems. To achieve both hot offset resistance and high gloss, it is effective to use polyester resin as a binder resin for toner. is there.

However, in the toner using the conventional polyester resin, the toner is fixed and aggregated at the stirring portion of the developing portion, and aggregates are easily generated. In particular, in the case of a color toner, since gloss is required for an image, polyester having a low molecular weight component is increased, and agglomerates are more likely to be generated as compared with a monochrome toner.
In addition, a toner having a small particle diameter is used to increase the resolution of the image. However, when the toner has a small particle diameter, the toner becomes weak against heat, pressure, and impact, and further aggregates are generated.

  In the case of the two-component development method, when the developer is stirred, the toners are fixed and aggregated by the collision compression force between the carriers. In the case of the one-component development method, the toner aggregates due to pressure, frictional heat, and the like when the toner is thinned on the developing roller. In both the two-component development method and the one-component development method, the toner is semi-melted and aggregates are generated by the heat generated from the rubbing of a shaft such as a developer stirring blade or a screw.

  In the case of the two-component development method, the toner agglomerated aggregate develops or adheres to the image portion and appears as a large dark spot on the image. In addition, when transferring an image to paper, an agglomeration between the paper and the photoconductor may act as a spacer, and the image at that portion may fall out white.

  In the case of the one-component developing method, the toner agglomerated aggregate enters between the developing roller and the thin layer forming blade, and becomes a white streak to generate an abnormal image. Particularly in color images, abnormal images are more conspicuous than monochrome images, and fine gradations, color reproducibility, and high resolution images are desired. Abnormal images generated due to the presence of aggregates It is a problem.

  Accordingly, the present invention has been made to solve the above-mentioned problems. By using a polyester resin formed in the presence of a specific catalyst, the polyester toner binder has excellent low-temperature fixability and hot resistance. An object of the present invention is to provide a color image forming toner in which toners are not fixed and aggregated while maintaining an offset property and a high gloss image.

  The above-described problem is (1) “color image forming toner used in a full-color image forming system of the present invention, and the toner comprises at least a binder resin mainly composed of a colorant and a polyester resin, The polyester resin is formed by a polycondensation ester reaction in the presence of at least one titanium-containing catalyst selected from the group consisting of titanium halide, titanium diketone enolate, titanium carboxylate, titanyl carboxylate, and titanyl carboxylate. This is solved by a color image forming toner characterized by being a resin.

  Further, (2) “the toner for forming a color image according to item (1) above, wherein the toner contains a wax,” is solved.

  (3) “The polyester resin has a number average molecular weight Mn of 2,000 to 5,000 and a weight average molecular weight Mw of 10,000 to 30,000,” This is solved by “color image forming toner”.

  (4) “A toner kit comprising the color image forming toner according to any one of (1) to (3), wherein the color image forming toner has a color of yellow, cyan, This is solved by a toner kit characterized by four colors of magenta and black.

  Further, (5) “the toner according to any one of (1) to (4) above, wherein the toner volume average diameter is 3.0 to 7.5 μm or less” is solved. .

  Further, (6) “a full-color image forming apparatus using toner according to any one of (1) to (5) above, wherein the gloss of the solid image is 5 to 80%” Solved.

  According to the color image forming toner described in item (1), the toner is used in a full color image forming system, and the toner comprises at least a binder resin mainly composed of a colorant and a polyester resin. The polyester resin is obtained by a polycondensation ester reaction in the presence of at least one titanium-containing catalyst selected from the group consisting of titanium halide, titanium diketone enolate, titanium carboxylate, titanyl carboxylate, and titanyl carboxylate. The toner, which is a formed resin, contains a polyester-based toner binder with excellent low-temperature fixability, hot offset resistance, and a high-gloss image. The toner binder can be provided so that the toner does not stick and aggregate even if the , It can be obtained without abnormal image full color image.

  According to the color image forming toner described in the item (2), the toner contains a wax, and the toner according to claim 1 may contain a low melting point wax. It is possible to provide a toner binder in which toners do not adhere and aggregate. As a result, the toner can be used in the image forming apparatus of the oil-less fixing system without applying the releasable oil to the fixing unit.

  According to the color image forming toner described in the item (3), the polyester resin has a number average molecular weight Mn of 2,000 to 5,000 and a weight average molecular weight Mw of 10,000 to 30,000. The toner according to claim 1, wherein the peak top molecular weight is 1,000 or more, the heat resistant storage stability and the powder fluidity are good, and the pulverization property of the toner is improved when the Mn is 30,000 or less. As a result, the color toner can obtain low-temperature fixing, a wide fixing temperature range, and appropriate gloss.

  According to the toner kit described in the item (4), a toner kit in which the toner colors are yellow, cyan, magenta, and black, respectively, can be used to produce a color image with low temperature fixing, a wide fixing temperature range, and moderate gloss. Can be obtained.

  According to the toner described in item (5), it is possible to obtain a high-definition full-color image by reducing the toner to a small particle diameter.

  According to the full-color image forming apparatus described in item (6), it is possible to obtain a vivid full-color image with appropriate gloss.

Hereinafter, embodiments of the present invention will be described in detail.
In the present invention, a polycondensation polyester resin formed in the presence of the following titanium-containing catalyst (A) is used. The catalyst (A) includes the following titanium halide (A-1), titanium diketone enolate (A-2), titanium carboxylate (A-3), aromatic polycarboxylic acid titanyl (A-4), Other titanyl carboxylates (A-5) are included. The amount of these titanium catalysts is preferably 0.01 to 5% by weight, more preferably 0.1 to 1% by weight. If the amount is too small, the effect is lost. If the amount is too large, the amount of impurities in the resin increases, which affects the resin characteristics.
Among the catalysts (A), the titanium halide (A-1) is not particularly limited, and examples thereof include dichlorotitanium, trichlorotitanium, tetrachlorotitanium, trifluorotitanium, tetrafluorotitanium, and tetrabromotitanium. .

  Although it does not specifically limit as titanium diketone enolate (A-2), For example, titanium acetylacetonate, titanium diisopropoxide bisacetylacetonate, titanyl acetylacetonate etc. are mentioned. Among these (A-2), titanium acetylacetonate is preferable.

  Although it does not specifically limit as carboxylate titanium (A-3), For example, C1-C32 aliphatic carboxylate titanium (A-3 * 1), C7-38 aromatic titanium carboxylate (A -3) and the like. In the case of titanium polycarboxylate having a valence of 2 or more, the number of carboxyl groups coordinated to titanium may be one or more, and a free carboxyl group may exist without being coordinated to titanium.

  Although it does not specifically limit as aliphatic carboxylate titanium (A-3 * 1), For example, aliphatic monocarboxylate titanium (A-3 * 1a), aliphatic dicarboxylate titanium (A-3 * 1b), fat And titanium tricarboxylate (A-3 · 1c) and tetravalent to octavalent or higher aliphatic polycarboxylic acid titanium (A-3 · 1d).

  The aliphatic monocarboxylic acid titanium (A-3 · 1a) is not particularly limited, and examples thereof include titanium formate, titanium acetate, titanium propionate, and titanium octoate.

  The aliphatic dicarboxylic acid titanium (A-3 · 1b) is not particularly limited, and examples thereof include titanium oxalate, titanium succinate, titanium maleate, titanium adipate, and titanium sebacate.

  Although it does not specifically limit as aliphatic tricarboxylate titanium (A-3 * 1c), For example, hexane tricarboxylate titanium, isooctane tricarboxylate titanium, etc. are mentioned.

  Although it does not specifically limit as aliphatic polycarboxylic acid titanium (A-3 * 1d), For example, octane tetracarboxylic acid titanium, decane tetracarboxylic acid titanium, etc. are mentioned.

  Although it does not specifically limit as aromatic carboxylate titanium (A-3 * 2), For example, aromatic monocarboxylate titanium (A-3 * 2a), aromatic dicarboxylate titanium (A-3 * 2b), aromatic And titanium tricarboxylate (A-3 · 2c) and tetravalent to octavalent or higher aromatic polycarboxylic acid titanium (A-3 · 2d).

  The aromatic monocarboxylic acid titanium (A-3 · 2a) is not particularly limited, and examples thereof include titanium benzoate.

  Although it does not specifically limit as aromatic dicarboxylate titanium (A-3 * 2b), For example, a titanium phthalate, a titanium terephthalate, a titanium isophthalate, a 1, 3- naphthalene dicarboxylic acid titanium, 4, 4-biphenyl dicarboxylic acid Examples include titanium, titanium 2,5-toluene dicarboxylate, titanium anthracene dicarboxylate and the like.

  Although it does not specifically limit as aromatic tricarboxylate titanium (A-3 * 2c), For example, a trimellitic acid titanium, 2,4,6- naphthalene tricarboxylic acid titanium, etc. are mentioned.

  Although it does not specifically limit as aromatic polycarboxylic acid titanium (A-3 * 2d), For example, pyromellitic acid titanium, 2,3,4,6- naphthalene tetracarboxylic acid titanium, etc. are mentioned.

  Among these titanium carboxylates (A-3), aromatic titanium carboxylates (A-3 · 2) are preferable, and aromatic dicarboxylate titanium (A-3 · 2b) is more preferable.

  The titanyl carboxylate (A-4) is not particularly limited, but for example, an aliphatic carboxylate titanyl (A-4 · 1) having 1 to 32 carbon atoms, an aromatic carboxylate titanyl having 7 to 38 carbon atoms (A- 4.2). In the case of titanyl polycarboxylate having a valence of 2 or more, the number of carboxyl groups coordinated to titanium may be one or more, and a free carboxyl group may be present without being coordinated to titanium.

  Although it does not specifically limit as aliphatic carboxylate titanyl (A-4 * 1), For example, aliphatic monocarboxylic acid titanyl (A-4 * 1a), aliphatic dicarboxylic acid titanyl (A-4 * 1b), fat Examples thereof include titanyl group tricarboxylate (A-4 · 1c) and titanyl tetravalent or higher valent aliphatic polycarboxylic acid (A-4 · 1d).

  The aliphatic monocarboxylic acid titanyl (A-4 · 1a) is not particularly limited, and examples thereof include titanyl formate, titanyl acetate, titanyl propionate, and titanyl octoate.

  The aliphatic dicarboxylic acid titanyl (A-4 · 1b) is not particularly limited, and examples thereof include titanyl oxalate, titanyl succinate, titanyl maleate, titanyl adipate, and titanyl sebacate.

  Although it does not specifically limit as aliphatic tricarboxylic acid titanyl (A-4 * 1c), For example, hexane tricarboxylic acid titanyl, isooctane tricarboxylic acid titanyl, etc. are mentioned.

  Although it does not specifically limit as aliphatic polycarboxylic acid titanyl (A-4 * 1d), For example, octane tetracarboxylic-acid titanyl, decane tetracarboxylic-acid titanyl, etc. are mentioned.

  Although it does not specifically limit as aromatic carboxylate titanyl (A-4 * 2), For example, aromatic monocarboxylic acid titanyl (A-4 * 2a), aromatic dicarboxylic acid titanyl (A-4 * 2b), aromatic And titanyl group tricarboxylate (A-4 · 2c) and titanyl 4-8 or higher aromatic polycarboxylate (A-4 · 2d).

  Although it does not specifically limit as aromatic monocarboxylic acid titanyl (A-4-2a), For example, benzoic acid titanyl etc. are mentioned.

  Although it does not specifically limit as aromatic dicarboxylic acid titanyl (A-4 * 2b), For example, a titanyl phthalate, a titanyl terephthalate, a titanyl isophthalate, a 1, 3- naphthalene dicarboxylic acid titanyl, 4, 4- biphenyl dicarboxylic acid Examples thereof include titanyl, titanyl 2,5-toluenedicarboxylate, and titanyl anthracene dicarboxylate.

  The titanyl aromatic tricarboxylate (A-4 · 2c) is not particularly limited, and examples thereof include titanyl trimellitic acid and titanyl 2,4,6-naphthalene tricarboxylate.

  Although it does not specifically limit as aromatic polycarboxylic acid titanyl (A-4 * 2d), For example, pyromellitic acid titanyl, 2,3,4,6-naphthalene tetracarboxylic acid titanyl, etc. are mentioned.

  Although it does not specifically limit as carboxylic acid titanyl salt (A-5), For example, (A-4 * 1b), (A-4 * 1c), (A-4 * 1d), (A-4 * 2b) Alkaline metal (lithium, sodium, potassium, etc.) or alkaline earth metal (magnesium, calcium, barium, etc.) salts of titanyl carboxylates listed in (A-4 · 2c) or (A-4 · 2d) [(A-5 · 1b), (A-5 · 1c), (A-5 · 1d), (A-5 · 2b), (A-5 · 2c), and (A-5 · 2d)] Etc. Among these (A-5), titanyl maleate and titanyl oxalate are preferable.

  The amount of (A) used is not particularly limited, but the lower limit is preferably 0.01%, more preferably 0.02%, based on the total weight of the polyol and polycarboxylic acid used to obtain the polyester resin. 0.03% is particularly preferred and 0.05% is most preferred. The upper limit is preferably 5%, more preferably 2%, particularly preferably 1.5%, and most preferably 0.8%. When it is 0.01% or more, the effect as a polycondensation catalyst is sufficiently obtained, and when it is 5% or less, high catalytic action is obtained according to the amount of catalyst. In addition, when the amount is within the above-mentioned range of the catalyst amount, the necessary characteristics of the toner using the toner binder made of the polyester resin, particularly, the image quality of the photoreceptor under low temperature and low humidity conditions are improved. Above and below,% indicates% by weight unless otherwise specified.

  Of these catalysts (A), preferred are titanium diketone enolate (A-2), carboxylic acid titanium (A-3), carboxylic acid titanyl salt (A-5), and combinations thereof, and more preferred. (A-2), aromatic carboxylic acid titanium (A-3.2), aliphatic carboxylic acid titanyl salt (A-5.1), aromatic carboxylic acid titanyl salt (A-5.2) and these. More preferably, titanium acetylacetonate, alkali metal salt among (A-3 · 2b) and (A-5 · 1b), alkali metal salt among (A-5 · 2b), and these Particularly preferred are titanium terephthalate, titanium isophthalate, titanium orthophthalate, titanyl oxalate, titanyl maleate, and combinations thereof, most preferably titanium terephthalate. Potassium titanyl oxalate and their combinations.

  Although it does not specifically limit as polycondensation polyester resin which comprises the toner binder of this invention, For example, polyepoxide (C) etc. are further added to polyester resin (X) and (X) which are polycondensates of a polyol and polycarboxylic acid. Examples thereof include a modified polyester resin (Y) obtained by reacting. (X), (Y) and the like may be used alone or in combination of two or more.

  Although it does not specifically limit as a polyol, For example, diol (G), a trihydric or more polyol (H), etc. are mentioned. Although it does not specifically limit as polycarboxylic acid, For example, dicarboxylic acid (I), polycarboxylic acid (J) more than trivalence, etc. are mentioned. A polymerization catalyst other than the titanium-containing catalyst, for example, dioctyltin oxide, monobutyltin oxide, zinc acetate, tetrabutoxy titanate, and the like can be used in combination.

  Although it does not specifically limit as a polyester resin which comprises the toner binder of this invention, For example, the following are specifically mentioned, These can also be used together. (X1): Linear polyester resin using (G) and (I) (X2): Non-linear polyester resin using (H) and / or (J) together with (G) and (I) ( Yl): A modified polyester resin obtained by reacting (C2) with (X2). The diol (G) is not particularly limited. For example, diols having a hydroxyl value of 180 to 1,900 mgKOH / g, specifically, alkylene glycols having 2 to 12 carbon atoms (ethylene glycol, 1,2-propylene glycol) , 1,3-propylene glycol, 1,4-butylene glycol and 1,6-hexanediol); alkylene ether glycols (such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polybutylene glycol); Alicyclic diols (such as 1,4-cyclohexanedimethanol and hydrogenated bisphenol A); bisphenols (such as bisphenol A, bisphenol F and bisphenol S); Alkylene oxides having 2 to 4 prime numbers [ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.) adducts; And adducts of alkylene oxide (such as EO, PO and BO).

  Among these, preferred are alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols, and combinations thereof, and particularly preferred are alkylene oxide adducts of bisphenols, and those having 2 to 2 carbon atoms. Combination with 12 alkylene glycols. In the above and below, the hydroxyl value and the acid value are measured by the method defined in JIS K 0070.

  The trihydric or higher polyol (H) is not particularly limited. For example, polyols having a hydroxyl value of 150 to 1900 mgKOH / g, specifically, 3 to 8 or higher aliphatic polyhydric alcohols (glycerin, trie Tyrolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); adducts of the above aliphatic polyhydric alcohols with 2 to 4 carbon atoms, such as EO, PO, and BO; trisphenols (such as trisphenol PA) A novolak resin (such as phenol novolak and cresol novolac); an adduct of the above trisphenols having 2 to 4 carbon atoms, such as EO, PO and BO; an alkylene oxide having 2 to 4 carbon atoms of the above novolak resin (EO) , PO, BO, etc.) That.

  Among these, preferred are aliphatic polyhydric alcohols having 3 to 8 valences or higher and alkylene oxide adducts of novolak resins, and particularly preferred are alkylene oxide adducts of novolak resins.

  Although it does not specifically limit as dicarboxylic acid (I), For example, the dicarboxylic acid of acid value 180-1250 mgKOH / g, Specifically, C4-C36 alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, and dodecenyl succinic acid). Acid etc.): C4-C36 alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); C8-36 aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.), etc. It is done. Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Moreover, even if these use together 2 or more types, there is no problem. As (I), the above acid anhydrides or lower (1 to 4 carbon atoms) alkyl esters (methyl ester, ethyl ester, isopropyl ester, etc.) may be used.

  Although it does not specifically limit as polycarboxylic acid (J) more than trivalence, For example, polycarboxylic acid with an acid value of 150-1250 mgKOH / g, specifically, C9-C20 aromatic polycarboxylic acid (trimerit Acid, pyromellitic acid, etc.); vinyl polymer of unsaturated carboxylic acid (styrene / maleic acid copolymer, styrene / acrylic acid copolymer, α-olefin / maleic acid copolymer, styrene / fumaric acid copolymer) Etc.). Among these, preferred are aromatic polycarboxylic acids having 9 to 20 carbon atoms, and particularly preferred are trimellitic acid and pyromellitic acid. As the trivalent or higher polycarboxylic acid (J), acid anhydrides or lower (1 to 4 carbon atoms) alkyl esters (methyl ester, ethyl ester, isopropyl ester, etc.) described above may be used. Moreover, hydroxycarboxylic acid (K) can also be copolymerized with (G), (H), (I) and (J). Although it does not specifically limit as hydroxycarboxylic acid (K), For example, a hydroxy stearic acid, hydrogenated castor oil fatty acid, etc. are mentioned.

  Although it does not specifically limit as polyepoxide (C), For example, polyglycidyl ether [ethylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, glycerin triglycidyl ether, bentaerythritol tetra Glycidyl ether, phenol novolac (average degree of polymerization 3 to 60) glycidyl ether, etc.]; diene oxide (pentadiene dioxide, hexadiene dioxide, etc.) and the like. Among these, polyglycidyl ether is preferable, and ethylene glycol diglycidyl ether and bisphenol A diglycidyl ether are more preferable.

  The number of epoxy groups per molecule of the polyepoxide (C) is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 2 to 4. Although it does not specifically limit as an epoxy equivalent of polyepoxide (C), Preferably it is 50-500. The lower limit is more preferably 70, particularly preferably 80, and the upper limit is more preferably 300, particularly preferably 200. When the number of epoxy groups and / or the epoxy equivalent is within the above range, both developability and fixability are improved. More preferably, the above-mentioned ranges of the number of epoxy groups per molecule and the range of epoxy equivalents are satisfied at the same time.

The ratio of the polyol and the polycarboxylic acid is preferably 2/1 to 1/2, more preferably 1.5 / 1 to 1 as an equivalent ratio (OH) / (COOH) of the hydroxyl group (OH) to the carboxyl group (COOH). 1 / 1.3, particularly preferably 1.3 / 1 to 1 / 1.2.
The types of polyol and polycarboxylic acid to be used are preferably selected in consideration of molecular weight adjustment so that the glass transition point of the polyester toner binder finally adjusted is 40 to 90 ° C.

Although it does not specifically limit as a specific example of (X1), For example, the following (1)-(3) etc. are mentioned.
(1) Bisphenol A · PO2 molar adduct / terephthalic acid polycondensate.
(2) Bisphenol A · EO 4 mol adduct / bisphenol A · PO 2 mol adduct / terephthalic acid polycondensate.
(3) Bisphenol A · PO2 mol adduct / bisphenol A · PO3 mol adduct / terephthalic acid / isophthalic acid / maleic anhydride polycondensate.

Although it does not specifically limit as a specific example of (X2), For example, the following (4)-(10) etc. are mentioned.
(4) Bisphenol A · EO 2 mol adduct / bisphenol A · PO 3 mol adduct / terephthalic acid / phthalic anhydride / trimellitic anhydride polycondensate.
(5) Bisphenol A · PO2 mol adduct / bisphenol A · PO3 mol adduct / bisphenol A · EO2 mol adduct / phenol novolac PO5 mol adduct / terephthalic acid / maleic anhydride / dimethyl terephthalic acid ester / trimellitic anhydride Acid polycondensate.
(6) Bisphenol A · EO 2 mol adduct / bisphenol A · PO 2 mol adduct / terephthalic acid / trimellitic anhydride polycondensate.
(7) Bisphenol A · EO 2 mol adduct / bisphenol A · PO 2 mol adduct / terephthalic acid / maleic anhydride / trimellitic anhydride polycondensate.
(8) Bisphenol A · PO 2 mol adduct / bisphenol A · PO 3 mol adduct / terephthalic acid / isophthalic acid / maleic anhydride / trimellitic anhydride polycondensate.
(9) Bisphenol A • PO2 molar adduct / bisphenol A • P03 molar adduct / phenol novolak EO adduct / isophthalic acid / trimellitic anhydride polycondensate.
(10) Bisphenol A · EO 2 mol adduct / bisphenol A · PO 2 mol adduct / phenol novolak PO5 mol adduct / terephthalic acid / fumaric acid / trimellitic anhydride polycondensate.

Although it does not specifically limit as a specific example of (Yl), For example, the following (11)-(20) etc. are mentioned.
(11) Modification obtained by reacting tetramethylene glycol diglycidyl ether with a polycondensate of bisphenol A · PO 2 mol adduct / bisphenol A · EO 2 mol adduct / phenol novolak PO5 mol adduct / terephthalic acid / dodecenyl succinic anhydride polyester.
(12) Bisphenol A · PO2 mol adduct / bisphenol A · PO3 mol adduct / bisphenol A · EO2 mol adduct / PO5 mol adduct of phenol novolac / terephthalic acid / dodecenyl succinic anhydride heavy bond ethylene glycol diglycidyl ether Modified polyester obtained by reacting
(13) Reaction of bisphenol A diglycidyl ether with bisphenol A · PO 2 mol adduct / bisphenol A · PO 3 mol adduct / phenol novolak EO adduct / isophthalic acid / maleic anhydride / trimellitic anhydride polycondensate The resulting modified polyester.
(14) Bisphenol A / PO 2 mol adduct / Bisphenol A / PO 3 mol adduct / Bisphenol A / EO 2 mol adduct / EO adduct of phenol novolac / Terephthalic acid / Isophthalic acid / Trimellitic anhydride polycondensate A modified polyester obtained by reacting diglycidyl ether.
(15) Bisphenol A / PO 2 mol adduct / bisphenol A / PO 3 mol adduct / bisphenol A / EO 2 mol adduct / phenol novolak PO5 mol adduct / terephthalic acid / isophthalic acid / maleic anhydride / trimellitic anhydride heavy A modified polyester obtained by reacting a condensate with bisphenol A diglycidyl ether.
(16) A modified polyester obtained by reacting ethylene glycol diglycidyl ether with bisphenol A · PO 3 mol adduct / phenol novolac PO 5 mol adduct / terephthalic acid / fumaric acid / trimellitic anhydride polycondensate.
(17) A modified polyester obtained by reacting tetramethylene glycol diglycidyl ether with a polycondensate of bisphenol A · PO 2 mol adduct / phenol novolac PO 5 mol adduct / terephthalic acid / dodecenyl succinic anhydride / trimellitic anhydride.
(18) Modified polyester obtained by reacting bisphenol A · PO2 molar adduct / bisphenol A · EO2 molar adduct / phenol novolak EO adduct / terephthalic acid / trimellitic anhydride polycondensate with ethylene glycol diglycidyl ether .
(19) Modification obtained by reacting bisphenol A diglycidyl ether with bisphenol A · PO2 mol adduct / bisphenol A · PO3 mol adduct / PO5 mol adduct of phenol novolac / terephthalic acid / trimellitic anhydride polycondensate polyester.
(20) A modified polyester obtained by reacting a phenol novolac glycidyl etherified product with a bisphenol A · PO 2 mol adduct / bisphenol A · EO 2 mol adduct / terephthalic acid / trimellitic anhydride polycondensate.
The toner binder is required to have different physical properties for full color and monochrome use, and the design of the polyester resin is also different.

That is, since a high-gloss image is required for full color use, it is necessary to use a low-viscosity binder. However, for monochrome use, gloss is not particularly required, and hot offset properties are important, so a high-elasticity binder is required. .
(X1), (X2), (Yl) and mixtures thereof are preferred for obtaining a high gloss image useful for a full-color copying machine or the like. In this case, since it is preferable that the viscosity is low, the ratio of (H) and / or (J) constituting these polyester resins is such that the sum of the number of moles of (H) and (J) is (G) to Preferably it is 0-20 mol% with respect to the total number of moles of (J), More preferably, it is 0-15 mol%, Especially 0-10 mol%.

In the case of a full-color polyester resin, the temperature TE at which the complex viscosity becomes 100 Pa · S is preferably 90 to 170 ° C, more preferably 100 to 165 ° C, and particularly 105 to 150 ° C. Sufficient gloss is obtained at 170 ° C. or lower, and heat resistant storage stability is improved at 90 ° C. or higher.
The TE is prepared by, for example, using a lab plast mill for melting and kneading a resin at 130 ° C. and 70 rpm for 30 minutes, and then using a commercially available dynamic viscoelasticity measuring device to change the complex viscosity (η *) By measuring the shear strain that periodically changes with time, η * (ω) = {(G ″ (ω) / ω) −i (G ′ (ω) consisting of a real part and an imaginary part. / Ω)} dγ / dt (where G ″ (ω) is the shear loss modulus, G ′ (ω) is the shear storage modulus, ω is the angular frequency and ω = 2πf (f is the frequency), and γ is the strain. The real number part is determined by the temperature at which 100 Pa · S is obtained.
Further, the THF-insoluble content of the full-color polyester resin is preferably 10% or less, and more preferably 5% or less, from the viewpoint of glossiness.

The THF-insoluble content and the THF-soluble content can be obtained by the following method.
About 0.5 g of a sample is precisely weighed into a 200 ml stoppered Meyer flask, 50 ml of THF is added, and the mixture is stirred and refluxed for 3 hours. After cooling, the insoluble matter is filtered off with a glass filter. The value (%) of THF-insoluble matter is calculated from the weight ratio of the resin content on the glass filter after vacuum drying at 80 ° C. for 3 hours and the weight of the sample.
The filtrate is used as a THF soluble component for the molecular weight measurement described later.

  The peak top molecular weight of the polyester resin is preferably 1,000 to 30,000, more preferably 1,500 to 25,000, and particularly 1,800 to 20,000. When the peak top molecular weight is 1,000 or more, the heat-resistant storage stability and the powder flowability are good, and when the peak top molecular weight is 3,0000 or less, the pulverization property of the toner is improved and the productivity is good.

In the above and the following, the peak top molecular weight, number average molecular weight, and weight average molecular weight of the polyester resin are measured under the following conditions using GPC for the THF soluble component.
Apparatus: Tosoh HLC-8120
Column: TSKgelGMHXL (2)
TSKgelMultiporeHXL-M (1 pc.)
Measurement temperature: 40 ° C
Sample solution: 0.25% THF solution Injection volume: 100 μl
Detector: Refractive index detector Reference material: Polystyrene The molecular weight showing the maximum peak height on the obtained chromatogram is called the peak top molecular weight.

The Tg of the polyester resin is preferably 40 to 90 ° C, more preferably 50 to 80 ° C, particularly 55 to 75 ° C. When the Tg is in the range of 40 to 90 ° C., the heat-resistant storage stability and the low-temperature fixability become better.
In the above and below, the Tg of the polyester resin is measured by a method (DSC method) defined in ASTM D3418-82 using DSC20, SSC / 580 manufactured by Seiko Denshi Kogyo Co., Ltd.

Although it does not specifically limit as a manufacturing method of linear polyester resin (X1), For example, diol (G), dicarboxylic acid (I), and a polycondensation catalyst are heated to 180-260 degreeC, and it is a normal pressure and / or pressure reduction conditions. Examples thereof include a method of obtaining a polyester resin (X1) by dehydration condensation.
Although it does not specifically limit as a manufacturing method of non-linear polyester resin (X2), For example, diol (G), dicarboxylic acid (I), trihydric or more polyol (H), and a polycondensation catalyst are 180 to 260 degreeC. Examples include a method of obtaining polyester resin (X2) by heating and dehydrating and condensing under normal pressure and / or reduced pressure conditions, and further reacting with trivalent or higher polycarboxylic acid (J). A tricarboxylic or higher polycarboxylic acid (J) can be reacted simultaneously with the diol (G), the dicarboxylic acid (I) and the trivalent or higher polyol (H).

Although it does not specifically limit as a manufacturing method of modified polyester resin (Yl), For example, modified polyester is added by adding polyepoxide (C) to non-linear polyester resin (X2), and performing the molecular elongation reaction of polyester at 180-260 degreeC. Examples thereof include a method for obtaining a resin (Yl).
In the toner binder of the present invention, two or more polyester resins can be used in combination.

In the present invention, the main binder resin is the polyester resin described above, but other resins may be included as necessary. The ratio as the main binder resin is 60% or more, and other resins can be contained up to 40%.
Examples of the binder resin to be included include styrene such as polystyrene, poly p-chlorostyrene, and polyvinyltoluene, and substituted polymers thereof; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene. Copolymer, Styrene-vinylnaphthalene copolymer, Styrene-methyl acrylate copolymer, Styrene-ethyl acrylate copolymer, Styrene-butyl acrylate copolymer, Styrene-octyl acrylate copolymer, Styrene- Methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer Polymer, styrene-butadiene copolymer , Styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer and other styrenic copolymers; polymethyl methacrylate, polybutyl methacrylate, Polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, aliphatic or alicyclic hydrocarbon resin , Aromatic petroleum resin, chlorinated paraffin, paraffin wax, and the like, and can be used alone or in combination.

In the color toner of the present invention, the number average molecular weight Mn of the resin in the toner is 2,000 to 7,000 and the weight average molecular weight Mw is 10,000 to 70 in order to obtain low-temperature fixing, a wide fixing temperature range, and appropriate gloss. 1,000 is desirable. That is, it is desirable that the toner has a number-soluble molecular weight Mn of 2,000 to 7,000 and a weight average molecular weight Mw of 10,000 to 70,000.
Furthermore, in order to obtain a vivid full-color image, it is preferable to increase the glossiness, and it is more preferable that the number average molecular weight Mn is 2,000 to 5,000 and the weight average molecular weight Mw is 10,000 to 30,000.
The preferable gloss for a vivid full-color image is 5 to 80%. By making such a high-gloss image, the fusion of the toner becomes complete, light passes through the toner layer attached to the image, and the light is reflected back by the paper that is the base material, so that the image is bright. Color development is obtained.

  In the toner of the present invention, a wax can be contained as necessary. By containing the wax, the cohesive force between the toners becomes strong and the softening due to heat easily occurs, which is disadvantageous for the binder aggregation of the toner. However, by using the resin of the present invention, the binder coagulation is not caused. It is possible to suppress the occurrence of aggregation. Particularly in the full-color electrophotographic system, oilless fixing that does not require oil in the fixing portion is required for cost reduction and downsizing, and it is important to include wax in the toner.

  The wax used in the toner of the present invention preferably has a melting point of 40 to 120 ° C, particularly preferably 50 to 110 ° C. When the melting point of the wax is higher than 120 ° C., the fixing property at a low temperature may be insufficient. On the other hand, when the melting point is lower than 40 ° C., the offset resistance and durability may be lowered. The melting point of the wax can be obtained by differential scanning calorimetry (DSC). That is, the melting peak value when a sample of several mg is ripened at a constant temperature increase rate, for example, (10 ° C./min) is defined as the melting point.

  Examples of the wax that can be used in the present invention include solid paraffin wax, micro wax, rice wax, fatty acid amide wax, fatty acid wax, aliphatic monoketone, fatty acid metal salt wax, fatty acid ester wax, and partial kenne. And fatty acid ester waxes, silicone varnishes, higher alcohols and carnauba waxes. Also, polyolefins such as low molecular weight polyethylene and polypropylene can be used.

The toner used in the present invention may contain a charge control agent, a release agent, and an external additive as necessary.
All known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-304, X-11, phenolic condensate E-89 (above, manufactured by Orient Chemical Industries), quaternary ammonium salt molybdenum complex TP-302, TP-415, salicylic acid metal complex TN -105 (above, manufactured by Hodogaya Chemical Co., Ltd.), quaternary ammonium salt copy charge PSY VP2038, triphenylmethane derivative copy blue PR, quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (above , Manufactured by Hoechst), LRA-901, LR-147, a boron complex (Japan) Ritto Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigments, sulfonate group, carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

  In the present invention, the amount of charge control agent used for reinforcement is determined by the toner production method including the amount of charge control agent, the type of binder resin, the presence or absence of additives used as necessary, and the dispersion method. Although it is not limited uniquely, Preferably it is used in 0.1-10 weight part with respect to 100 weight part of binder resin. The range of 0.3 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline.

As the external additive used in the toner of the present invention, inorganic fine particles can be preferably used. The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and particularly preferably 5 mμ to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight.

Specific examples of the inorganic fine particles include silica, titanium oxide, alumina, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, and diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.
In addition, polymer fine particles such as polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization and dispersion polymerization, polycondensation resin such as silicone resin, benzoguanamine resin and nylon Thermosetting resin polymer particles can also be used.

  Such external additives can be surface treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, a silane coupling agent, a silylating agent, a silane coupling agent having a fluorinated alkyl group, an organic titanate coupling agent, an aluminum coupling agent and the like are preferable surface treatment agents.

Further, the toner of the present invention can contain a cleaning improver in order to remove the developer after transfer remaining on the photoreceptor or the primary transfer medium. Examples of such a cleaning improver include: Examples thereof include fatty acid metal salts such as zinc stearate and calcium stearate, and polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.
The color of the resin, charge control agent, release agent, and external additive used in the color toner of the present invention is preferably colorless and transparent, translucent, white, light translucent, and light.

  As the colorant that can be used in the toner of the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow , Yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Tan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Faiselle Parachlor ortho nitroaniline red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Quinacridone , Pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue , Indanthrene Blue (RS, BC), Indigo, Ultramarine, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian , Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Maracay Togreen lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof can be used. The amount used is generally 0.1 to 50 parts by weight per 100 parts by weight of the binder resin. In the present invention, these colorants are used alone, or two or more colorants are mixed to adjust the color of the toner of the present invention.

The volume average particle diameter of the toner is generally 5 to 15 μm, but in order to obtain a high-definition image, it is preferable to reduce the particle diameter. That is, the volume average particle diameter D4 is preferably 3.0 to 7.5 μm, and more preferably 4.0 to 7.0 μm.
The toner particle size of the present invention was measured by a Coulter counter method.
As an apparatus for measuring the particle size distribution of toner particles by the Coulter counter method, there are Coulter Multisizer II (manufactured by Coulter) and Coulter Multisizer III (manufactured by Coulter). The measurement method is described below.
First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is an about 1% NaCl aqueous solution prepared using sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated.

An example of an image forming apparatus using the toner of the present invention as a developer will be described.
FIG. 1 is a schematic configuration diagram illustrating an example of an image forming apparatus according to the present invention. In the figure, reference numeral (100) is a copying apparatus main body, (200) is a paper feed table on which the copying apparatus is placed, (300) is a scanner mounted on the copying apparatus main body (100), and (400) is an automatic document feeder mounted thereon. (ADF).
The copying apparatus main body (100) includes four image forming means (18) including various means for performing an electrophotographic process such as charging, developing, and cleaning around a photosensitive member (40) as a latent image carrier. Two parallel tandem image forming apparatuses (20) are provided. Above the tandem image forming apparatus (20), there is provided an exposure apparatus (21) that exposes the photoreceptor (40) with laser light based on image information to form a latent image. An intermediate transfer belt (10) made of an endless belt member is provided at a position facing each photoconductor (40) of the tandem type image forming apparatus (20). Primary transfer means (62) for transferring the toner images of the respective colors formed on the photoconductor (40) to the intermediate transfer belt (10) at positions facing the photoconductor (40) via the intermediate transfer belt (10). ) Is arranged.

Further, below the intermediate transfer belt (10), a secondary transfer device (for transferring the toner images superimposed on the intermediate transfer belt (10) onto transfer paper conveyed from the paper feed table (200) in a batch. 22) is arranged. The secondary transfer device (22) is configured by spanning a secondary transfer belt (24), which is an endless belt, between two rollers (23), and a support roller (16) via an intermediate transfer belt (10). The toner image on the intermediate transfer belt (10) is transferred to the transfer paper. Next to the secondary transfer device (22), a fixing device (25) for fixing the image on the transfer paper is provided. The fixing device (25) is configured by pressing a pressure roller (27) against a fixing belt (26) which is an endless belt.
The secondary transfer device (22) described above also has a sheet transport function for transporting the transfer paper after image transfer to the fixing device (25). Of course, as the secondary transfer device (22), a transfer roller or a non-contact charger may be arranged. In such a case, it is difficult to provide this sheet conveying function together.
In the illustrated example, the transfer paper is inverted under the secondary transfer device (22) and the fixing device (25) so as to record images on both sides of the transfer paper in parallel with the tandem image forming device (20). An inverting device (28) is provided.

The developer containing the toner is used for the developing device (4) of the image forming means (18).
In the developing device (4), the developer carrying member carries and conveys the developer, and an alternating electric field is applied at a position facing the photoconductor (40) to develop the latent image on the photoconductor (40). By applying the alternating electric field, the developer is activated, the charge amount distribution of the toner can be narrowed, and the developability can be improved.

  Further, the developing device (4) can be a process cartridge that is integrally supported together with the photoreceptor (40) and is detachably formed on the image forming apparatus main body. In addition, the process cartridge may include a charging unit and a cleaning unit.

The operation of the image forming apparatus is as follows.
First, the document is set on the document table (30) of the automatic document feeder (400), or the document is opened on the contact glass (32) of the scanner (300) by opening the automatic document feeder (400). Then, the automatic document feeder (400) is closed and pressed by it.
When a start switch (not shown) is pressed, when the document is set on the automatic document feeder (400), the document is transported and moved onto the contact glass (32), and then the other contact glass (32). When the document is set on the scanner, the scanner (300) is immediately driven to travel on the first traveling body (33) and the second traveling body (34). Then, the first traveling body (33) emits light from the light source, and the reflected light from the document surface is further reflected toward the second traveling body (34) and reflected by the mirror of the second traveling body (34). Then, the image is placed in the reading sensor (36) through the imaging lens (35), and the content of the original is read.

  When a start switch (not shown) is pressed, one of the support rollers (14), (15), and (16) is driven to rotate by the drive motor (not shown), and the other two support rollers are driven to rotate. The transfer belt (10) is rotated and conveyed. At the same time, the individual image forming means (18) rotates the photoreceptor (40) to form monochrome images of black, yellow, magenta, and cyan on each photoreceptor (40). Then, along with the conveyance of the intermediate transfer belt (10), these monochrome images are sequentially transferred to form a composite color image on the intermediate transfer belt (10).

On the other hand, when a start switch (not shown) is pressed, one of the paper feed rollers (42) of the paper feed table (200) is selectively rotated, and one of paper feed cassettes (44) provided in multiple stages in the paper bank (43). The sheet is fed out from the sheet, separated one by one by a separation roller (45), put into a sheet feeding path (46), and conveyed by a conveyance roller (47) to a sheet feeding path (48) in the copying machine main body (100). Guide and stop against the registration roller (49).
Alternatively, the sheet feeding roller (50) is rotated to feed out the sheets on the manual feed tray (51), separated one by one by the separation roller (52), and placed in the manual sheet feeding path (53). ) And stop.
Then, the registration roller (49) is rotated in synchronization with the composite color image on the intermediate transfer belt (10), and the sheet is fed between the intermediate transfer belt (10) and the secondary transfer device (22). The image is transferred by the next transfer device (22) and a color image is recorded on the sheet.

The sheet after the image transfer is conveyed by the secondary transfer device (22) and sent to the fixing device (25). The fixing device (25) applies heat and pressure to fix the transferred image, and then the switching claw. It is switched at (55), discharged by the discharge roller (56), and stacked on the discharge tray (57). Alternatively, it is switched by the switching claw (55) and put into the sheet reversing device (28), where it is reversed and guided again to the transfer position, and an image is recorded also on the back surface, and then the paper discharge tray (56) is discharged by the discharge roller (56). 57) Drain up.
On the other hand, the intermediate transfer belt (10) after the image transfer is removed by the intermediate transfer belt cleaning device (17) to remove residual toner remaining on the intermediate transfer belt (10) after the image transfer, and the tandem image forming device (20). To prepare for image formation again.

  Next, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples. In the examples, all parts represent parts by weight.

In addition, the softening point in an Example and a comparative example is measured with the following method.
1. Method of measuring softening point Using a flow tester, raise the temperature at a constant speed under the following conditions, and set the softening point at the temperature at which the outflow is halved.
Apparatus: Shimadzu Corporation flow tester CFT-500D
Load: 20 kgf / cm ²
Die: 1mmφ-1mm
Temperature increase rate: 6 ° C / min
Sample amount: 1.0 g

Example 1
[Synthesis of linear polyester resin]
In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 395 parts of bisphenol A / EO 2 mol adduct, 285 parts of bisphenol A / PO 2 mol adduct, 265 parts of terephthalic acid, 65 parts of fumaric acid and polycondensation catalyst 2 parts of potassium titanyl oxalate was added and reacted at 220 ° C. for 10 hours while distilling off the water generated under a nitrogen stream. Subsequently, it was made to react under the reduced pressure of 5-20 mmHg, and when the acid value became 18, it took out, cooled to room temperature, and grind | pulverized, and the linear polyester resin (X1-1) was obtained.
The linear polyester resin (X1-1) does not contain a THF-insoluble component, its acid value is 28, hydroxyl value is 25, Tg is 58 ° C., number average molecular weight is 3,400, weight average molecular weight is 14, 300, the peak top molecular weight was 7,400.

[Synthesis of non-linear polyester resin]
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tank, 350 parts of bisphenol A / EO 2 mol adduct, 326 parts of bisphenol A / PO 3 mol adduct, 278 parts of terephthalic acid, 40 parts of phthalic anhydride and polycondensation catalyst As a solution, 1.5 parts of potassium titanyl oxalate was added and reacted at 230 ° C. for 10 hours while distilling off the water generated in a nitrogen stream.
Next, the reaction is carried out under reduced pressure of 5 to 20 mmHg. When the acid value becomes 2 or less, the mixture is cooled to 180 ° C., added with 62 parts of trimellitic anhydride, taken out after reaction for 2 hours under sealed at normal pressure, and cooled to room temperature. To obtain a non-linear polyester resin (X2-1).
The non-linear polyester resin (X2-1) does not contain a THF-insoluble component, and its acid value is 36, hydroxyl value is 17, Tg is 69 ° C., number average molecular weight is 3,810, and weight average molecular weight is 20 300, and the peak top molecular weight was 11,400.

[Synthesis of toner binder]
800 parts of linear polyester resin (X1-1) and non-linear polyester resin (X2-1) 2
00 parts were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to 30 ° C. for 4 minutes using a steel belt cooler and then pulverized to obtain the toner binder (TBl) of the present invention.

[Create Toner]
Using the toner binder (TB1), eight types of toners were prepared as follows.
Cyan toner prescription:
Toner binder (TBl) 100 parts Cyan pigment (pigment blue 15-3) 3.5 parts E-84 manufactured by Orient Chemical Co., Ltd. 1 part Magenta toner formulation:
Toner binder (TBl) 100 parts Magenta pigment (pigment red 122) 7 parts E-84 manufactured by Orient Chemical Co., Ltd. 1 part Yellow toner formulation:
Toner binder (TBl) 100 parts Yellow pigment (pigment yellow 180) 7 parts Orientation Chemical Industries E-84 1 part Black toner formulation:
Toner binder (TBl) 100 parts Black pigment (carbon black) 4 parts E-84 made by Orient Chemical Co., Ltd. 1 part

Among the above materials, pigment, polyester resin, and pure water were mixed at a ratio of 1: 1: 0.5 and kneaded by two rolls. Kneading was performed at 70 ° C., and then the roll temperature was raised to 120 ° C. to evaporate water and prepare a master batch in advance.
Using the prepared masterbatch, the material was premixed using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.] so as to be the same as the above recipe, and then a twin-screw kneader [manufactured by Ikekai Co., Ltd.] PCM-30]. Then, after finely pulverizing using a supersonic jet crusher, Labojet [manufactured by Nippon Pneumatic Industry Co., Ltd.], it is classified by an airflow classifier [MDS-I made by Nippon Pneumatic Industry Co., Ltd.], and the volume average particle size is reduced. About 7 μm toner particles were obtained. Next, 1.0 part of colloidal silica [H-2000: manufactured by Clariant Co., Ltd.] is mixed with 100 parts of toner particles by a sample mill, and yellow toner (Y1-1), magenta toner (M1-1), and cyan are mixed. Toners (C1-1) and black toner (BK1-1) containing no wax were obtained.

Cyan toner prescription:
Toner binder (TBl) 100 parts Cyan pigment (pigment blue 15-3) 3.5 parts Wax (desorbed fatty acid type carnauba wax) 5 parts E-84 manufactured by Orient Chemical Industry Co., Ltd. 1 part magenta toner formulation:
Toner binder (TBl) 100 parts Magenta pigment (pigment red 122) 7 parts Wax (desorbed fatty acid type carnauba wax) 5 parts E-84 made by Orient Chemical Industries 1 part Yellow toner formulation:
Toner binder (TBl) 100 parts Yellow pigment (pigment yellow 180) 7 parts Wax (desorbed fatty acid type carnauba wax) 5 parts Orient Chemical Industries E-84 1 part Black toner formulation:
Toner binder (TBl) 100 parts Wax (desorbed fatty acid type carnauba wax) 5 parts Black pigment (carbon black) 4 parts 1 part of E-84 manufactured by Orient Chemical Industries

Among the above materials, pigment, polyester resin, and pure water were mixed at a ratio of 1: 1: 0.5 and kneaded by two rolls. Kneading was performed at 70 ° C., and then the roll temperature was raised to 120 ° C. to evaporate water and prepare a master batch in advance.
Using the prepared masterbatch, the material was premixed using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.] so as to be the same as the above recipe, and then a twin-screw kneader [manufactured by Ikekai Co., Ltd.] PCM-30]. Then, after finely pulverizing using a supersonic jet crusher, Labojet [manufactured by Nippon Pneumatic Industry Co., Ltd.], it is classified by an airflow classifier [MDS-I made by Nippon Pneumatic Industry Co., Ltd.], and the volume average particle size is reduced. About 7 μm toner particles were obtained. Next, 1.0 part of colloidal silica [H-2000: manufactured by Clariant Co., Ltd.] is mixed with 100 parts of toner particles by a sample mill, and yellow toner (Y1-2), magenta toner (M1-2), and cyan are mixed. Toners containing toner (C1-2) and black toner (BK1-2) were obtained.

Example 2
[Synthesis of linear polyester resin]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 430 parts of bisphenol A / PO2 molar adduct, 300 parts of bisphenol A / PO3 molar adduct, 257 parts of terephthalic acid, 65 parts of isophthalic acid, maleic anhydride 10 2 parts of titanyl potassium oxalate as a polycondensation catalyst and a polycondensation catalyst were added and reacted at 220 ° C. for 10 hours while distilling off the water produced in a nitrogen stream. Subsequently, it was made to react under the reduced pressure of 5-20 mmHg, and when the acid value became 5, it took out, cooled to room temperature, and grind | pulverized, and the linear polyester resin (X1-2) was obtained.
(X1-2) does not contain THF-insoluble matter, its acid value is 8, hydroxyl value is 12, Tg is 59 ° C., number average molecular weight is 6,890, weight average molecular weight is 32,100, peak top The molecular weight was 19,800.
This polyester (X1-2) is used as the toner binder resin (TB2) of the present invention.

[Create Toner]
Using toner binder resin (TB2) in the same manner as in Example 1, yellow toner (Y2-1), magenta toner (M2-1), cyan toner (C2-1), and black toner not containing wax Yellow toner (Y2-2), magenta toner (M2-2), cyan toner (C2-2), and black toner (BK2-2) containing (BK2-1), wax were obtained.

Example 3
[Synthesis of linear polyester resin]
A linear polyester resin (X1-3) was obtained by reacting in the same manner as (X1-1) in Example 1 except that the polycondensation catalyst was replaced with 2 parts of titanium terephthalate, cooling to room temperature, and pulverizing. (X1-3) does not contain THF-insoluble matter, its acid value is 27, hydroxyl value is 24, Tg is 58 ° C., number average molecular weight is 3,500, weight average molecular weight is 14,500, peak top The molecular weight was 7,500.

[Synthesis of non-linear polyester resin]
A linear polyester resin (X2-3) was obtained by reacting in the same manner as (X2-1) in Example 1 except that the polycondensation catalyst was replaced with 1.5 parts of titanium terephthalate, cooling to room temperature, and pulverizing.
(X2-3) does not contain THF-insoluble matter, its acid value is 33, hydroxyl value is 15, Tg is 69 ° C., number average molecular weight is 4,130, weight average molecular weight is 21,500, peak top The molecular weight was 11,830.

[Synthesis of toner binder]
800 parts of polyester (X1-3) and 200 parts of polyester (X2-3) were powder mixed for 5 minutes with a Henschel mixer to obtain a toner binder resin (TB3) of the present invention.

[Create Toner]
Using toner binder resin (TB3) in the same manner as in Example 1, yellow toner (Y3-1), magenta toner (M3-1), cyan toner (C3-1), and black toner not containing wax Yellow toner (Y3-2), magenta toner (M3-2), cyan toner (C3-2), and black toner (BK3-2) containing (BK3-1), wax were obtained.

Example 4
[Synthesis of linear polyester resin]
Except for replacing the polycondensation catalyst with 2 parts of titanium terephthalate, the reaction was conducted in the same manner as (X1-2) in Example 1, cooled to room temperature and pulverized to obtain a linear polyester resin (X1-4). (X1-4) does not contain THF-insoluble matter, its acid value is 7, hydroxyl value is 11, Tg is 59 ° C., number average molecular weight is 7,010, weight average molecular weight is 33,200, peak top The molecular weight was 20,100.
This polyester (X1-4) is used as the toner binder resin (TB4) of the present invention.

[Create Toner]
Using toner binder resin (TB4) in the same manner as in Example 1, yellow toner (Y4-1), magenta toner (M4-1), cyan toner (C4-1), and black toner not containing wax (BK4-1), yellow toner (Y4-2), magenta toner (M4-2), cyan toner (C4-2), and black toner (BK4-2) containing wax were obtained.

Example 5
In the same manner as in the toner of Example 1, the pulverization classification conditions are adjusted, and a volume average particle diameter of about 5 μm is made as a trial product. Yellow toner (Y1-1-5), magenta toner (M1-1-5), 4 toners without cyan wax (C1-1-5) and black toner (Bk1-1-5), yellow toner (Y1-2-5), magenta toner (M1-2-5), Four toners containing cyan toner (C1-2-5) and black toner (Bk1-2-5) containing wax were obtained.

Example 6
In the same manner as in the toner of Example 1, the pulverization and classification conditions are adjusted, and a volume average particle size of about 9 μm is made as a prototype. Yellow toner (Y1-1-9), magenta toner (M1-1-9), 4 toners without cyan wax (C1-1-9) and black toner (Bk1-1-9), yellow toner (Y1-2-9), magenta toner (M1-2-9), Four toners containing cyan toner (C1-2-9) and black toner (Bk1-2-9) containing wax were obtained.

Comparative Example 1
[Synthesis of linear polyester resin]
A linear polyester resin (X1-5) was obtained by reacting in the same manner as (X1-1) in Example 1 except that the polycondensation catalyst was replaced with 2 parts of dibutyltin oxide, cooling to room temperature, and pulverizing. (X1-5) does not contain THF-insoluble matter, its acid value is 28, hydroxyl value is 25, Tg is 58 ° C., number average molecular weight is 3,300, weight average molecular weight is 14,000, peak top The molecular weight was 7,300.

[Synthesis of non-linear polyester resin]
A linear polyester resin (X2-5) was obtained by reacting in the same manner as (X2-1) in Example 1 except that the polycondensation catalyst was replaced with 1.5 parts of dibutyltin oxide, cooling to room temperature, and pulverizing.
(X2-5) does not contain THF-insoluble matter, its acid value is 34, hydroxyl value is 16, Tg is 69 ° C., number average molecular weight is 4,050, weight average molecular weight is 20,500, peak top The molecular weight was 11,800.

[Synthesis of toner binder]
800 parts of polyester (X1-5) and 200 parts of polyester (X2-5) were powder-mixed with a Henschel mixer for 5 minutes to obtain a resin for toner binder (TB5) of the present invention.

[Create Toner]
Using toner binder resin (TB5) in the same manner as in Example 1, yellow toner (Y5-1), magenta toner (M5-1), cyan toner (C5-1), and black toner not containing wax Yellow toner (Y5-2), magenta toner (M5-2), cyan toner (C5-2), and black toner (BK5-2) containing (BK5-1), wax were obtained.

Comparative Example 2
[Synthesis of linear polyester resin]
A linear polyester resin (X1-6) was obtained by reacting in the same manner as (X1-2) in Example 1 except that the polycondensation catalyst was replaced with 2 parts of dioctyltin oxide, cooling to room temperature, and pulverizing. (X1-6) does not contain THF-insoluble matter, its acid value is 8, hydroxyl value is 12, Tg is 59 ° C., number average molecular weight is 6,900, weight average molecular weight is 32,800, peak top The molecular weight was 19,900.
This polyester (X1-6) is used as the toner binder resin (TB6) of the present invention.

[Create Toner]
Using toner binder resin (TB6) in the same manner as in Example 1, yellow toner (Y6-1), magenta toner (M6-1), cyan toner (C6-1), and black toner not containing wax (BK6-1), yellow toner (Y6-2), magenta toner (M6-2), cyan toner (C6-2), and black toner (BK6-2) containing wax were obtained.

Comparative Example 3
In the same manner as in the toner of Comparative Example 1, the pulverization classification conditions were adjusted, and a volume average particle size of about 5 μm was prototyped. Yellow toner (Y5-1-5), magenta toner (M5-1-5), Cyan toner (C5-1-5), black toner (Bk5-1-5) 4 toners without wax, yellow toner (Y5-2-5), magenta toner (M5-2-5), Four colors of toner containing wax of cyan toner (C5-2-5) and black toner (Bk5-2-5) were obtained.

Comparative Example 4
In the same manner as in the toner of Example 1, by adjusting the pulverization classification conditions, a volume average particle size of about 9 μm was made as a trial product, and yellow toner (Y5-1-9), magenta toner (M5-1-9), 4 toners without cyan wax (C5-1-9) and black toner (Bk5-1-9), yellow toner (Y5-2-9), magenta toner (M5-2-9), Four toners containing cyan toner (C5-2-9) and black toner (Bk5-2-9) containing wax were obtained.

The toner was put into a Ricoh color laser printer IPSiO CX 8200 for evaluation. However, since this color printer uses an oil application fixing method, when evaluating toner containing wax, the fixing unit was modified to an oilless fixing method.
Since this color printer is a two-component developing system, toner aggregates generated in the developing unit were evaluated.
For each of yellow, cyan, magenta, and black, 5,000 A4 sheets were run with an image area of 5%. Thereafter, two solid A3 sheets were output for yellow, cyan, magenta, and black single colors, and the number of toner aggregates on the solid image was measured.
In addition, the glossiness of the solid image was measured.
The glossiness was measured using a Murakami gloss meter TAPPI T480 om-90 under the condition of 60 degrees.

Further, as a one-component development system test, evaluation was performed using a Ricoh color laser printer IPSiO Color 6000. However, since this color printer uses an oil application fixing method, when evaluating toner containing wax, the fixing unit was modified to an oilless fixing method.
Since this color printer is a one-component developing system, white streaks due to toner aggregates generated in the developing unit were evaluated.
For each of yellow, cyan, magenta, and black, 5,000 A4 sheets were run with an image area of 5%. Thereafter, solid images for yellow, cyan, magenta, and black were output to A4 paper, and the number of white lines appearing on the solid image was measured. In addition, the glossiness of the solid image was measured.
Table 1 shows the results. The actual measurement value of the volume average particle diameter of the toner is also described.

  By using the color toner of the present invention, it is possible to obtain a full color image with less toner aggregation and no abnormal image. Further, even if the toner contains wax or increases the gloss of the image, the toner aggregation hardly occurs. Further, even when a toner having a small particle diameter is used, the occurrence of toner aggregation is small.

An example of an image forming apparatus using the toner of the present invention as a developer is shown.

Explanation of symbols

4 Developing Device 10 Intermediate Transfer Belt 14 Support Roller 15 Support Roller 16 Support Roller 17 Intermediate Transfer Belt Cleaning Device 18 Image Forming Unit 20 Tandem Image Forming Device 21 Laser Exposure Device 22 Secondary Transfer Device 23 Roller 24 Endless Secondary Transfer Belt 25 Fixing device 26 Fixing belt 27 Pressure roller 25 Fixing device 28 Sheet reversing device 30 Document table 32 Contact glass 33 First traveling member 34 Second traveling member 35 Imaging lens 36 Reading sensor 40 Photosensitive member 42 Feeding roller 43 Paper bank 44 Paper feed cassette 45 Separator roller 46 Paper feed path 47 Transport roller 48 Paper feed path 49 Registration roller 50 Paper feed roller 51 Manual feed tray 52 Separation roller 53 Manual feed path 54 Registration roller 55 Switching claw 56 Ejection roller 57 Ejection tray 62 Primary Transfer means 100 Body,
200 Paper feed table 300 Scanner 400 Automatic document feeder (ADF)

Claims (6)

  A toner for color image formation used in a full-color image forming system, the toner comprising at least a colorant and a binder resin mainly comprising a polyester resin, the polyester resin comprising a titanium halide, a titanium diketone enolate A color image formed by a polycondensation ester reaction in the presence of at least one titanium-containing catalyst selected from the group consisting of carboxylic acid, titanium carboxylate, titanyl carboxylate, and titanyl carboxylate Toner.   The color image forming toner according to claim 1, wherein the toner contains a wax.   The color image forming toner according to claim 1, wherein the polyester resin has a number average molecular weight Mn of 2,000 to 5,000 and a weight average molecular weight Mw of 10,000 to 30,000.   4. A toner kit comprising the color image forming toner according to claim 1, wherein the color image forming toner has four colors of yellow, cyan, magenta, and black, respectively. Toner kit.   The toner according to claim 1, wherein the toner volume average diameter is 3.0 to 7.5 μm or less. 6. The full-color image forming apparatus using toner according to claim 1, wherein the solid image has a gloss of 5 to 80%.

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