JP2011085795A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fixing method capable of imparting high glossiness and its uniformity to an image, and preventing dullness in color, electrostatic color shift, or electrostatic offset on the image. <P>SOLUTION: In the toner having toner particles including at least a binder resin and a mold release agent, the binder resin is a polyester resin synthesized by using aliphatic polyhydric alcohol as an alcoholic component and by using a titanium compound as a catalyst, and includes a binder resin A having a softening point in the range of 120°C-200°C. A chroma (C*) and a lightness (L*) of a molding acquired by applying pressure molding to the toner satisfy inequalities: 0.0≤(C*)≤15.0, 88.0≤(L*)≤100.0. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a toner used in electrophotography and an image forming method using the toner.

  In color copying in which a multicolor image is formed by transferring and fixing a plurality of colored toners on a transfer medium, for example, Patent Documents 1 to 5 disclose transparent toner or colorless toner, Alternatively, a multicolor image forming method using these toners is described. These methods can form high gloss images. However, there has been a big problem in stably obtaining a higher-quality image such as a photographic image and obtaining a high-quality image having sufficient image protection properties such as weather resistance and abrasion resistance.

For example, with the toner described in Patent Document 1, sufficient image gloss (gloss) cannot be obtained, or image gloss unevenness due to uneven fixing oil tends to occur. In addition, since the temperature at which the image is discharged is high, there is a need to improve the discharge adhesion in which the images are brought into close contact with each other when cooled.
In the image forming apparatus described in Patent Document 2, color misregistration and offset due to fixing are likely to occur, and furthermore, paper discharge adhesion also occurs, so it has to be improved.
Patent Document 3 discloses a transparent toner containing an ultraviolet absorber and an ultraviolet shielding agent. Addition of these materials adversely affects the charging characteristics and charging stability of the toner. Further, the transparency of the clear image is impaired, and the image gloss imparting property and the image gloss are not uniform. Furthermore, since it is not considered about imparting rubbing resistance to the image, it is necessary to improve.
Patent Document 4 discloses a toner having a resin obtained by using a titanium compound as a catalyst. However, since these inventions do not consider image protection by clear images such as weather resistance and abrasion resistance of clear images, they need to be improved.

  Further, Patent Document 5 discloses a transparent toner having a polyester containing an aliphatic polyhydric alcohol. However, these inventions need to be improved because they do not consider image protection such as imparting weather resistance and rubbing resistance to colored toner images and recording media by a clear layer. Furthermore, since charging characteristics and charging stability as a transparent toner are insufficient, it has been necessary to improve them.

Japanese Patent Laid-Open No. 2001-175022 JP 2006-209090 A JP-A-10-213942 JP 2005-338816 A JP 2005-99122 A

An object of the present invention is to provide a toner and an image forming method that can solve the above-described problems of the prior art.
That is, a toner that imparts high and uniform glossiness to images, imparts weather resistance to colored toner images and recording media to prevent fading, and prevents dullness, electrostatic color shift and electrostatic offset of colored toner images, and It is an object to provide an image forming method.

The present inventors not only achieve high glossiness and uniformity of images such as silver salt photographs, but also provide excellent image protection such as weather resistance and abrasion resistance of colored toner images and recording media. And completed the invention. The present invention is
(1) A toner having toner particles containing at least a binder resin and a release agent,
The binder resin is a polyester resin synthesized using an aliphatic polyhydric alcohol as an alcohol component and a titanium compound as a catalyst, and has a softening point of 120 ° C. or higher and 200 ° C. or lower. Including
The saturation (C *) and lightness (L *) of the molded product obtained by pressure molding the toner are as follows:
0.0 ≦ (C *) ≦ 15.0
88.0 ≦ (L *) ≦ 100.0
It is related with the toner characterized by being.

(2) In the image forming method including the step of forming a toner image on a recording medium, the toner image is formed over the entire image formable region on the recording medium, and the toner forming the toner image is The present invention relates to an image forming method, wherein the toner is the toner described in (1).

  By using the toner of the present invention, it is possible to stably output a high-gloss image having excellent uniformity over a long period of time. Further, by using the toner of the present invention, excellent weather resistance and abrasion resistance can be imparted to the colored toner image and the recording medium. Furthermore, by using the toner of the present invention, it is possible to effectively prevent the color toner from scattering during fixing.

  By using the toner of the present invention, it is possible to output an image excellent in reducing the occurrence of paper discharge adhesion according to a preferred embodiment, and further, even if an image is formed on a fixed image, the chromaticity of the image and the recording medium A good image that does not adversely affect the image can be output.

1 is a schematic configuration diagram of a fixing device used in an embodiment. It is explanatory drawing of the image for evaluation of fine line reproducibility.

  The toner of the present invention is a toner having toner particles containing at least a binder resin and a release agent, and the binder resin is synthesized using an aliphatic polyhydric alcohol as an alcohol component and a titanium compound as a catalyst. It is characterized by having a binder resin A which is a polyester resin and has a softening point (Tm) of 120 ° C. or higher and 200 ° C. or lower. Since the binder resin is obtained using a titanium compound as a catalyst and has the binder resin A having a softening point in the above range, the dispersion state of the titanium compound in the binder resin is extremely high. Get higher. Accordingly, it is considered that the toner of the present invention can impart excellent weather resistance to the color toner image and the recording medium. Furthermore, it has been found that low chargeability and charge nonuniformity, which are problems specific to toners that do not use a colorant, can be improved, and a toner having stable electrophotographic characteristics can be obtained.

  When the softening point of the binder resin A is less than 120 ° C., the titanium compound is not sufficiently dispersed, and the effects of the present invention are not exhibited. On the other hand, when the softening point is higher than 200 ° C., the aggregation tendency of the titanium compound and the toner constituting material becomes remarkable, and the effect of the present invention is not exhibited. More preferably, the softening point of the binder resin A is 120 ° C. or higher and 140 ° C. or lower, and the effect of the present invention becomes more remarkable.

Further, the binder resin A contained in the toner of the present invention preferably contains 5% by mass or more and 50% by mass or less of the binder resin A. If the content is out of the range, it tends to adversely affect the gloss level and charge level of the fixed image and recording medium, which is not preferable. More preferably, the binder resin A is contained in an amount of 5% by mass to 30% by mass.

The binder resin A used in the present invention is a polyester resin, which is a resin having an ester bond synthesized by a reaction between an acid and an alcohol. As the alcohol component for synthesizing the binder resin A, an aliphatic polyhydric alcohol is used.
Preferred aliphatic polyhydric alcohols used for the synthesis of the binder resin A are divalent aliphatic alcohols, specifically, propylene glycol, ethylene glycol, tricyclodecane dimethanol, ethylene. Examples include glycol and cyclohexanedimethanol.
Other than these, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, spiroglycol, 1,4-phenylene glycol, 1,4- Ethylene oxide adducts of phenylene glycol, para-xylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and other diols, and trimethylolethane, trimethylolpropane, if necessary Lactone-based polyester polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone can be used, in addition to triols such as glycerol and tetraols such as pentaelsitol. .

Although the acid component used for the synthesis | combination of the binder resin A used by this invention is not specifically limited, For example, bivalent or more carboxylic acid, bivalent or more carboxylic anhydride, and bivalent or more carboxylic acid ester are mentioned.
Divalent carboxylic acids include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid, fumaric acid, maleic acid and citraconic acid. And unsaturated dicarboxylic acid.
Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, and benzophenone tetracarboxylic acid.

  The method of synthesizing the binder resin A is not particularly limited except that it is performed using a titanium compound described later as a catalyst, and can be synthesized by a conventionally known method. The molecular weight is not particularly limited, but usually a resin having a number average molecular weight of about 4,000 to 10,000 is used. The softening point of the binder resin A can be adjusted to the above range by changing the type, amount ratio, reaction time, and the like of the acid and alcohol.

The binder resin A used in the present invention is obtained using at least a titanium compound as a catalyst. Specific examples of the titanium compound include titanium diisopropylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₃ H ₇ O) ₂ ], titanium diisopropylate bisdiethanolamate [Ti (C ₄ H ₁₀ O ₂ N) ₂ (C ₃ H ₇ O) ₂ ], titanium dipentylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₅ H ₁₁ O) ₂ ], titanium diety rate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 2 H 5 O) 2 ], titanium dihydroxy octylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (OHC 8 H ₁₆ O) ₂ ], titanium distearate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₁₈ H ₃₇ O) ₂ ], titanium triisopropylate triethanolamate [Ti (C _{6 H 14 O 3 N) 1 (} C 3 ₇ O) _3], titanium monopropylate tris (triethanolaminate) _{[Ti (C 6 H 14 O 3} N) 3 (C 3 H 7 O) 1 ], and the like, titanium diisopropylate Among these Preference is given to rate bistriethanolamate, titanium diisopropylate bisdiethanolamate and titanium dipentylate bistriethanolamate.

Specific examples of other titanium catalysts include tetra-n-butyl titanate [Ti (C ₄ H ₉
O) ₄ ], tetrapropyl titanate [Ti (C ₃ H ₇ O) ₄ ], tetrastearyl titanate [Ti (C ₁₈ H ₃₇ O) ₄ ], tetramyristyl titanate [Ti (C ₁₄ H ₂₉ O) ₄ ], Tetraoctyl titanate [Ti (C ₈ H ₁₇ O) ₄ ], dioctyl dihydroxyoctyl titanate [Ti (C ₈ H ₁₇ O) ₂ (OHC ₈ H ₁₆ O) ₂ ], dimyristyl dioctyl titanate [Ti (C ₁₄
H ₂₉ O) ₂ (C ₈ H ₁₇ O) ₂ ] and the like, among which tetrastearyl titanate, tetramyristyl titanate, tetraoctyl titanate and dioctyl dihydroxyoctyl titanate are preferable. These can be obtained, for example, by reacting titanium halide with the corresponding alcohol.

Further, it is more preferable that the titanium compound contains an aromatic carboxylic acid titanium compound from the viewpoint of imparting good charge controllability and weather resistance to the toner of the present invention.
It is preferable that the said aromatic carboxylic acid titanium compound is a thing obtained when aromatic carboxylic acid and titanium alkoxide react. The aromatic carboxylic acid is preferably a divalent or higher valent aromatic carboxylic acid (that is, an aromatic carboxylic acid having two or more carboxyl groups) and / or an aromatic oxycarboxylic acid.
Examples of the divalent or higher aromatic carboxylic acid include dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid or anhydrides thereof, trimellitic acid, benzophenone dicarboxylic acid, benzophenone tetracarboxylic acid, naphthalene dicarboxylic acid, and naphthalene tetracarboxylic acid. Examples thereof include polyvalent carboxylic acids such as acids, anhydrides thereof, esterified products, and the like. Examples of the aromatic oxycarboxylic acid include salicylic acid, m-oxybenzoic acid, p-oxycarboxylic acid, gallic acid, mandelic acid, and tropic acid.
Among these, as the aromatic carboxylic acid, it is more preferable to use a divalent or higher carboxylic acid, and it is particularly preferable to use isophthalic acid, terephthalic acid, trimellitic acid, or naphthalenedicarboxylic acid.

As said titanium alkoxide, what is shown by following General formula (1) is used preferably.

In the general formula (1), R ₁ , R ₂ , R ₃ and R ₄ are alkyl groups having 1 to 20 carbon atoms, which may be the same or different, and have a substituent. It may be. n shows the integer of 1-10.

  The titanium compound in the present invention is preferably used in an amount of 0.001 to 5.0 parts by mass, more preferably 0.005 to 2.0 parts by mass, per 100 parts by mass of the binder resin A.

In the toner of the present invention, the saturation (C *) and lightness (L *) of a molded product obtained by pressure molding the toner are
0.0 ≦ (C *) ≦ 15.0
88.0 ≦ (L *) ≦ 100.0
It is.

Saturation (C *) and lightness (L *) are obtained by measuring L *, a ^* , and b ^* using SpectroScan Transmission (manufactured by GretagMacbeth). Specific measurement conditions are shown below.
<Measurement conditions>
Observation light source: D50
Observation field: 2 °
Concentration: DIN NB
White standard: Pap
Filter: None

In general, L *, a ^* , and b ^* are values used in the L ^* a ^* b ^* color system which is a useful means for expressing a color numerically. a ^* and b ^* both represent hue. Hue is red,
Yellow, green, blue, purple, etc. Each of a ^* and b ^* indicates a color direction, a ^* indicates a red-green direction, and b ^* indicates a yellow-blue direction. In the present invention, C * is defined as follows.
C * = (a ^{* 2} + b ^{* 2} ) ^1/2

  The saturation (C *) and lightness (L *) of the toner molded product are affected by the toner composition material and the thermal history in the toner manufacturing process, etc., in order to obtain good chromaticity of the toner fixed image. Is an important physical property value.

  Since powders such as the toner of the present invention tend to be whiter as they are fine particles, the color definition of the toner molded product has an extremely higher detection sensitivity than the color specification of the toner powder, and a high-quality image. It is preferable as a rule for obtaining In the present invention, a molded product obtained by pressure molding of toner refers to a product in which 2.5 g of toner is put into a tablet molding compressor having a diameter of 25 mm, compression molded at a pressure of 10 MPa for 90 seconds, and pelletized to a diameter of 25 mm. In the present invention, if the saturation (C *) and lightness (L *) of the toner molded product are out of the above range, the fixed image and the chromaticity of the recording medium are adversely affected, so that a high-quality image can be obtained. I can't.

The saturation is preferably 0.0 ≦ (C *) ≦ 10.0, and the lightness is 90.0.
It is preferable that ≦ (L *) ≦ 100.0. The brightness of the toner of the present invention can be adjusted to the above range by adjusting the color of the binder resin by changing the production conditions of the binder resin or adding a small amount of white colorant. The saturation of the toner of the present invention can be adjusted to the above range by adjusting the color of the binder resin by changing the production conditions of the binder resin and adding a small amount of various colorants.

  The binder resin of the toner of the present invention is a polyester resin synthesized using an alkylene oxide adduct of bisphenol A as an alcohol component, and has a softening point (Tm) of 60 ° C. or higher and 100 ° C. or lower. It is preferable that the resin B is further included. By using the binder resin B in combination with the binder resin A, the toner of the present invention can improve the adhesion to a colored toner image or a recording medium, and an image with extremely high abrasion resistance can be obtained.

The binder resin B is more preferably a polyester resin obtained using at least a titanium compound as a catalyst. As a result, the toner of the present invention can impart and impart both weather resistance and abrasion resistance to colored toner images and recording media at a high level, and a high-quality image can be obtained. The present inventors have found that the rub resistance of an image can be obtained characteristically by suppressing internal stress generated during toner fixing. As the binder resin characteristic, it is important to suppress the linear shrinkage rate. In the toner of the present invention, the linear shrinkage rate is controlled by allowing the binder resin B having a softening point (Tm) of 60 ° C. or higher and 100 ° C. or lower to be present in the binder resin.
It is possible to develop good image abrasion resistance, which is preferable.

The method for synthesizing the binder resin B is not particularly limited, and can be synthesized in the same manner as the binder resin A except that it is synthesized using an alkylene oxide adduct of bisphenol A as an alcohol component. Moreover, although the molecular weight is not specifically limited, Usually, resin whose number average molecular weight is about 1,500-4,000 is used.
When a titanium compound is used for the synthesis of the binder resin B, it is preferable to use 0.001 to 5.0 parts by mass per 100 parts by mass of the binder resin B.

  When the binder resin B is contained in the binder resin used in the toner of the present invention, the content is preferably 50% by mass or more and 95% by mass or less in the total binder resin. The content ratio of the binder resin A and the binder resin B in the binder resin is preferably 1: 1 to 1:19, and more preferably 1: 1 to 1: 4. In addition to the binder resin A and the binder resin B, the binder resin used in the toner of the present invention may be combined with a general resin used for the toner to the extent that the effects of the present invention are not impaired. it can. As resins other than the binder resin A and the binder resin B, a vinyl copolymer represented by a styrene- (meth) acryl copolymer, a vinyl copolymer unit and a polyester unit are chemically bonded. Examples thereof include a hybrid resin, an epoxy resin, and a styrene-butadiene copolymer. The content is preferably 10% or less to the extent that the effects of the present invention are not impaired.

  The toner of the present invention has a release agent. In the present invention, the type of release agent can be used without any particular limitation, but it is preferable to use one having good wax dispersibility. About the above-mentioned binder resin A and binder resin B, the compatibility of both resin is favorable and the toner design which utilized both resin characteristics is possible. On the other hand, it is extremely disadvantageous for the dispersibility of the additive material. However, the toner containing no pigment like the toner of the present invention does not cause a problem of pigment dispersibility, and by sufficiently ensuring the dispersibility of the toner raw material components, it is possible to design a toner that takes advantage of the resin characteristics. I found out. Therefore, as the mold release agent, it is preferable to use a hydrocarbon wax from the viewpoint of ensuring sufficient dispersibility, and it is more preferable to use a mold release agent treated with a styrene monomer.

  The release agent component used in the present invention is not particularly limited, and examples thereof include the following. Oxides of aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight olefin copolymer wax, microcrystalline wax, Fischer-Tropsch wax and paraffin wax, and aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or Block copolymers; waxes based on fatty acid esters such as carnauba wax and montanic acid ester wax; ester waxes that are a synthetic reaction product of higher fatty acids such as behenyl behenate and behenyl stearate and higher alcohols; and Examples include those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax.

Further, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassic acid, eleostearic acid, and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, and seryl alcohol , Saturated alcohols such as melyl alcohol; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis laurin Saturated fatty acid bisamides such as acid amides and hexamethylene bis stearic acid amides; ethylene bis oleic acid amides, hexamethylene bis oleic acid amides, N, N′dioleyl adipic acid amides, N, N ′ geos Unsaturated fatty acid amides such as irsevacinamide; Aromatic bisamides such as m-xylene bis stearamide, N, N ′ distearyl isophthalamide; calcium stearate, calcium laurate, zinc stearate, magnesium stearate, etc. Aliphatic metal salts (generally referred to as metal soaps); waxes grafted with aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; fatty acids such as behenic acid monoglycerides and many others Examples include partially esterified products of monohydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils and the like. Among them, the above-mentioned aliphatic hydrocarbon wax is preferable.

  In the present invention, the release agent contains at least a wax treated with a styrenic monomer, so that the release agent in the toner has a high dispersibility, resulting in a high release effect and gloss uniformity of the fixed image. It is preferable at the point obtained. Examples of styrenic monomers for treating the release agent include styrene, methyl styrene, ethyl styrene, etc., and the treatment method is not particularly limited, the treatment method by melt mixing, the treatment method by dope, and the treatment by spray spraying. A known processing method such as a method can be used.

  The toner of the present invention preferably has 1 to 8 parts by mass of a release agent with respect to 100 parts by mass of the binder resin. Moreover, when processing a mold release agent with a styrene-type monomer, it is preferable to use 20-50 mass parts processing agent with respect to 100 mass parts of mold release agents.

  The toner of the present invention preferably has fine titanium oxide particles treated with a silane compound. By having the titanium oxide fine particles treated with the silane compound, it is possible to obtain better charging characteristics and weather resistance. The titanium oxide fine particles are added to the toner particles, but the addition method is not particularly limited. The titanium oxide fine particles are preferably added in an amount of 0.1 to 3 parts by mass with respect to 100 parts by mass of the toner particles.

The titanium oxide fine particles used in the toner of the present invention are oxidized by a sulfuric acid method, a chlorine method, or low-temperature oxidation (thermal decomposition, hydrolysis) of a volatile titanium compound (for example, titanium alkoxide, titanium halide, titanium acetylacetonate). Titanium fine particles are preferably used. As the crystal system of the titanium oxide fine particles, any of anatase type, rutile type, mixed crystal type thereof, and amorphous type can be used.
Examples of silane compounds for treating titanium oxide fine particles include hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and isobutyltrimethoxy. Silane, n-octyltrimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, etc. be able to. The treatment amount of these silane compounds is preferably 3 to 30 parts by mass with respect to 100 parts by mass of the titanium oxide fine particles.

  The toner of the present invention can contain a charge control agent. As the charge control agent that can be used, a known charge control agent can be used, and in particular, a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferable. Specific compounds include, as negative charge control agents, metal compounds of aromatic carboxylic acids such as salicylic acid, naphthoic acid, dicarboxylic acid, polymer compounds having sulfonic acid or carboxylic acid groups in the side chain, boron compounds, urea A compound, a silicon compound, calixarene, etc. are mentioned. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, and an imidazole compound.

Among the above, the charge control agent that is particularly preferably used is an aromatic carboxylic acid derivative selected from aromatic oxycarboxylic acid and aromatic alkoxycarboxylic acid, and a metal compound of the aromatic carboxylic acid derivative. It is preferable that it is more than the value. The example of manufacture of the metal compound of aromatic carboxylic acid is shown. For example, an aqueous solution in which a divalent or higher valent metal ion is dissolved is dropped into an aqueous sodium hydroxide solution in which an aromatic carboxylic acid is dissolved and heated and stirred. Next, it can be synthesized by adjusting the pH of the aqueous solution, cooling to room temperature, and then washing with filtered water, but is not limited to the above synthesis method. Examples of the divalent metal include Mg ²⁺ , Ca ²⁺ , Sr ²⁺ , Pb ²⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Zn ²⁺ and Cu ²⁺ . Of these, Zn ²⁺ , Ca ²⁺ , Mg ²⁺ and Sr ²⁺ are preferable. Examples of the trivalent or higher metal include Al ³⁺ , Cr ³⁺ , Fe ³⁺ , Ni ³⁺ and Zr ⁴⁺ . Among these trivalent or higher metals, Al ³⁺ , Cr ³⁺ and Zr ⁴⁺ are preferable, and Al ³⁺ and Zr ⁴⁺ are particularly preferable. As the aromatic carboxylic acid derivative, a salicylic acid derivative is preferable. The charge control agent is preferably used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin. If the content falls within this range, the charge level of the toner can be adjusted appropriately, so that the charge amount necessary for development can be easily obtained. Further, at the time of kneading, which is a part of the toner manufacturing process, a metal cross-linking reaction between the carboxyl group present in the binder resin and the central metal of the above-described aromatic carboxylic acid metal compound can be appropriately caused. Thereby, the viscoelasticity of the toner can be adjusted, and the heat melting property of the toner can be improved. Further, as described above, the charge control agent concentration on the toner particle surface is made higher than that in the toner, and a charge control agent having a higher charging property than the charge control agent existing in the toner is present on the toner particle surface. This is preferable because the charging characteristics can be easily controlled.

The toner of the present invention is preferably externally added with a fluidity improver (hereinafter referred to as external addition). Here, the fluidity improver has a function of increasing fluidity by being externally added to the toner particles, and is added from the viewpoint of improving the image quality. Examples thereof include fluorine resin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder; silica fine powder such as silica fine powder by a wet process and silica fine powder by a dry process. And the silica fine powder which surface-treated these silica fine powders with processing agents, such as a silane compound, a titanium coupling agent, and silicone oil; Titanium oxide fine powder; Alumina fine powder, Treated titanium oxide fine powder, Treated alumina Fine powder is used. Such a fluidity improver gives a good result when the specific surface area by nitrogen adsorption measured by the BET method is 30 m ² / g or more, preferably 50 m ² / g or more.
The fluidity improver is used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the toner particles.

  The toner of the present invention preferably has a weight average particle diameter of 4 to 9 μm. Thus, by reducing the weight average particle diameter of the toner, the reproducibility in the development of the contour portion of the image, particularly the character image or the line pattern is improved. When the weight average particle diameter is less than 4 μm, for example, the adhesion force to the surface of the photosensitive drum is increased, which tends to cause uneven image unevenness due to transfer defects. In addition, the charge amount per unit mass of toner becomes high, and the image density may be lowered in a low temperature and low humidity environment, for example. Furthermore, due to a decrease in fluidity and an increase in adhesion to a member, for example, frictional charging with a carrier is difficult to be performed smoothly, toner that cannot be sufficiently charged increases, and fogging of non-image areas becomes conspicuous. . Also, if the weight average particle size exceeds 9 μm, there are few fine particles that can contribute to high image quality, so there is a merit that the fluidity of the toner is excellent, but it adheres faithfully on the fine electrostatic charge image on the photosensitive drum. In some cases, the halftone portion reproducibility is lowered and the gradation is also lowered. In addition, fusion to a member such as the surface of the photosensitive drum is likely to occur. Further, when the content of the toner having a particle size of 4 μm or less is 3 to 40% by number and the content of the toner having a particle size of 9 μm or more is 10% by volume or less, the balance between developability and transferability is improved. It is particularly preferable because it is easy to obtain a removed toner.

Next, the replenishment developer and the carrier used for the two-component developer when the toner of the present invention is used in the two-component development method will be described.
Examples of the magnetic carrier include surface oxidized or unoxidized iron, lithium, calcium, magnesium, nickel, copper, zinc, cobalt, manganese, chromium, rare earth metal particles, alloy particles thereof, oxide particles, ferrite and the like. Can be used.

  The coated carrier obtained by coating the surface of the magnetic carrier particles with a resin is particularly preferable in a developing method in which an AC bias is applied to the developing sleeve. Coating methods include a method in which a coating solution prepared by dissolving or suspending a coating material such as a resin in a solvent is adhered to the surface of the magnetic carrier core particles, and a method in which the magnetic carrier core particles and the coating material are mixed with powder. A conventionally known method can be applied.

  Examples of the coating material on the surface of the magnetic carrier core particle include silicone resin, polyester resin, styrene resin, acrylic resin, polyamide, polyvinyl butyral, and aminoacrylate resin. These are used alone or in plural. The treatment amount of the coating material is preferably 0.1 to 30% by mass (preferably 0.5 to 20% by mass) with respect to the carrier core particles. The number average particle diameter of these carriers is 10 to 100 μm, preferably 20 to 70 μm.

  When a two-component developer is prepared by mixing the toner of the present invention and a magnetic carrier, the mixing ratio is usually 2 to 15% by mass, preferably 4 to 13% by mass, as the toner concentration in the developer. Good results are obtained. If the toner concentration is less than 2% by mass, the image density tends to decrease, and if it exceeds 15% by mass, fogging or in-machine scattering tends to occur.

  The toner of the present invention has one or more endothermic peaks in the temperature range of 30 to 200 ° C. in the endothermic curve in the differential thermal analysis (DSC) measurement of the toner, and the peak of the maximum endothermic peak in the endothermic peak. The temperature is more preferably in the range of 60 to 105 ° C. In the present invention, in order to sufficiently obtain the glossiness of the fixed image and the releasability between the fixed image and the fixing member, the above characteristics are more preferable.

  Various methods can be applied as a method for producing the toner of the present invention. For example, in the toner of the present invention, a binder resin, a release agent and other optional materials are melt-kneaded, cooled and pulverized, and a pulverized product is spheroidized or classified as necessary. Furthermore, it can be produced by mixing inorganic fine particles.

  The image forming method of the present invention includes a step of forming a toner image on a recording medium, wherein the toner image is formed on the entire area of the image forming area on the recording medium, and the toner for forming the toner image includes: The toner of the present invention described above. As a result, it is possible to impart very good glossiness, weather resistance, and abrasion resistance to the entire image including the color toner image area and the recording medium area without the color toner image. Such an image forming method can be performed by adjusting the image forming area of the image forming apparatus, and the structure and type of the apparatus are not particularly limited.

In the image forming method of the present invention, the above-described toner image of the present invention is preferably formed on a recording medium on which a colored toner image is fixed in advance. Accordingly, by using a color toner image fixed in advance, it is possible to impart extremely good glossiness, weather resistance, and abrasion resistance without deteriorating high image quality. At this time, the colored toner image may be attached to the fixing member due to offset, but the concern can be solved by using the toner of the present invention having high adhesion to the colored toner image or the recording medium. .
The method for forming a toner image of the present invention on a recording medium on which a colored toner image is fixed in advance uses, for example, an apparatus capable of outputting a five-color full-color image. After fixing and outputting the toner image, the recording medium is returned to the paper feeding unit again, and the toner image of the present invention is formed on the recording medium.

The heating and pressing means is not particularly limited as long as it is normally used for image fixing. For example, a fixing roller having a heat generating unit that is a fixing unit and a pressure roller that is a pressing unit may be used. The temperature is usually set to 120 to 200 ° C., and the pressure is set to a range of 9.0 × 10 ^{3 to} 1.0 × 10 ⁶ N / m ² .

  The color toner used for image formation in combination with the toner of the present invention is not particularly limited, and may be any configuration that the normal toner has. For example, a colored toner having toner particles containing a binder resin, a colorant, and a release agent and an external additive may be mentioned. Although it does not specifically limit as a coloring agent of a colored toner, For example, the following are mentioned. As the colorant, a pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the sharpness by using a dye and a pigment together.

  Examples of the black colorant include carbon black; a magnetic material; a color toned to black using a yellow colorant, a magenta colorant, and a cyan colorant.

Colorant for magenta toner:
Examples of the magenta toner pigment include the following. C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 49, 50, 51, 52, 53, 54, 55, 57, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 163, 202, 206, 207.209, 238; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35.

  Examples of the magenta toner dye include the following. C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 81, 82, 83, 84, 100, 109, 121; I. Disper thread 9; I. Solvent violet 8, 13, 14, 21, 27; C.I. I. Oil-soluble dyes such as Disper Violet 1, C.I. I. B. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40; I. Basic dyes such as Basic Violet 1, 3, 7, 10, 14, 15, 21, 25, 26, 27, 28.

Colorant for cyan toner:
Examples of the cyan toner pigment include the following. C. I. Pigment blue 2, 3, 15: 3, 15: 4, 16, 17; I. Bat Blue 6; C.I. I. Acid Blue 45, a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted on the phthalocyanine skeleton.

Colorant for yellow toner:
Examples of the yellow pigment include the following. C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 62, 65, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 127, 128, 129, 147, 151, 154, 155, 168, 174, 175, 176, 180, 181, 185; I. Bat yellow 1, 3, 20
Examples of yellow dyes include C.I. I. There is Solvent Yellow 162.

The amount of the colorant used is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, most preferably 100 parts by weight of the binder resin. Is 3 parts by mass or more and 15 parts by mass or less.

Hereafter, the measuring method of each physical property in this invention is demonstrated.
<Measurement method of softening point (Tm) of binder resin>
In accordance with JIS K 7210, it refers to that measured by a Koka type flow tester. A specific measurement method is shown below. While a 1 cm ³ sample was heated at a heating rate of 6 ° C./min using a Koka flow tester (manufactured by Shimadzu Corporation), 1960 N / m ² (2
0 kg / cm ² ) and extruding a nozzle with a diameter of 1 mm and a length of 1 mm,
This draws a plunger drop (flow value) -temperature curve, and when the height of the S-shaped curve is h, the temperature corresponding to h / 2 (the temperature at which half of the resin has flowed out) is softened. Let it be a point (Tm).

<Measurement method of weight average particle diameter (D4)>
The weight average particle diameter (D4) of the toner is calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

Prior to measurement and analysis, the dedicated software was set as follows.
On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.
The specific measurement method is as follows.

  (1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.

  (2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. As a dispersant, “Contaminone N” (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH 7 precision measuring instrument cleaning, made of organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.

(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.

  (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.

  (5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.

  (6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.

  (7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set with the dedicated software is the weight average particle diameter (D4).

<Measurement of peak temperature of maximum endothermic peak of toner>
The peak temperature of the maximum endothermic peak of the wax and toner is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.

  Specifically, about 10 mg of toner is precisely weighed, put in an aluminum pan, and an empty aluminum pan is used as a reference. Measurement is performed at ° C / min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C., and then the temperature is raised again. The maximum endothermic peak of the DSC curve in the temperature range of 30 to 200 ° C. in the second temperature raising process is defined as the maximum endothermic peak of the endothermic curve in the DSC measurement of the toner of the present invention.

<Measurement of molecular weight distribution by gel permeation chromatograph (GPC)>
The molecular weight distribution of the THF-soluble component of the binder resin is measured by gel permeation chromatography (GPC) as follows.

First, the binder resin is dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is prepared so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml

  In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

  Specific examples of the present invention will be described below, but the present invention is not limited to these examples.

(Production example of binder resin A-1)
The following materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube.
Terephthalic acid 42.8 parts by mass Propylene glycol 40.0 parts by mass Isophthalic acid and titanium tetra-i-propoxide compound 0.7 parts by mass Thereafter, the mixture is heated to 220 ° C. while removing nitrogen and introducing water. The reaction was allowed for 10 hours.
Furthermore, 17.2 parts by mass of trimellitic anhydride was added, heated to 180 ° C. and reacted for 2 hours to synthesize Resin A-1. The molecular weight of the resin A-1 determined by GPC is as follows: weight average molecular weight (Mw) 93,000, number average molecular weight (Mn) 6,400, peak molecular weight (Mp) 13,800, glass transition point 61 ° C., softening point Was 140 ° C.

(Production example of binder resins A-2 to A-8)
Binder resins A-2 to A-8 were produced in the same manner as the binder resin A-1, except that the catalyst type and alcohol component were changed as shown in Table 1. The catalyst is shown in Table 2.

(Production example of binder resin B-1)
The following materials were weighed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube.
Terephthalic acid 22.6 parts by weight trimellitic anhydride 1.7 parts by weight polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
Compound of 75.6 parts by mass of trimellitic acid and titanium tetra-n-butoxide 0.7 parts by mass Thereafter, the mixture is heated to 200 ° C. and reacted for 10 hours while removing water generated while introducing nitrogen, and then 10 mmHg The mixture was reacted for 1 hour under reduced pressure to synthesize Resin B-1. The molecular weight of resin B-1 determined by GPC is weight average molecular weight (Mw) 6,200, number average molecular weight (Mn) 2,500, peak molecular weight (Mp) 2,900, glass transition point is 55 ° C., The softening point was 90 ° C.

(Production example of binder resins B-2 to B-7)
Binder resins B-2 to B-7 were produced in the same manner as the binder resin B-1, except that the catalyst type and the alcohol component were changed as shown in Table 3. The catalyst is shown in Table 2.

<Example of production of release agent 1>
- the low-density polyethylene (endothermic peak by DSC is 100 ° C.) 30 parts by mass Styrene 54 parts by mass n-Butyl acrylate 13 parts by mass of acrylonitrile, 3 parts by mass were charged into an autoclave, after the inside of the system N ₂ substitutions, heating stirring While maintaining at 180 ° C.
A polymer in which 50 parts by mass of a 2% by mass t-butyl hydroperoxide xylene solution was continuously dropped into the system for 5 hours, the solvent was separated and removed after cooling, and the vinyl resin component reacted with the low-density polyethylene. A was obtained. When the molecular weight of the polymer A was measured, it was the weight average molecular weight (Mw) 5,500 and the number average molecular weight (Mn) 2,800.

  Next, 30 parts by mass of the above polymer A was melt-mixed at 130 ° C. for 20 minutes with respect to 100 parts by mass of paraffin wax (peak temperature of maximum endothermic peak: 75 ° C.), cooled and pulverized to obtain a release agent 1. The peak temperature of the maximum endothermic peak of the release agent 1 was 75 ° C.

<Example of production of release agent 2>
After adding 100 g of dicumyl peroxide as a reaction initiator to 600 g of styrene monomer, the mixture was added dropwise to 2000 g of heated and melted paraffin wax (peak temperature of maximum endothermic peak 75 ° C.) with stirring and reacted for 4 hours to release mold 2 Got. The peak temperature of the maximum endothermic peak of the release agent 2 was 75 ° C.

<Example of carrier production>
4.0% by mass of a silane coupling agent (3- (2-aminoethylaminopropyl) trimethyl) with respect to a magnetite powder having a number average particle size of 0.30 μm and a hematite powder having a number average particle size of 0.30 μm. Methoxysilane) was added, and the mixture was stirred at a high speed at 100 ° C. or higher in the container to treat each fine particle.
・ Phenol 10 parts by mass ・ Formaldehyde solution 6 parts by mass (formaldehyde 40%, methanol 10%, water 50%)
-Treated magnetite 80 parts by weight-Treated hematite 4 parts by weight The above materials, 5 parts by weight of 28% ammonia water, and 20 parts by weight of water are placed in a flask, and heated to 85 ° C for 30 minutes while stirring and mixing. The resulting phenol resin was cured by a polymerization reaction for 3 hours. Thereafter, the cured phenol resin was cooled to 30 ° C., water was further added, the supernatant was removed, the precipitate was washed with water, and then air-dried. Subsequently, this was dried under reduced pressure (5 mmHg or less) at a temperature of 60 ° C. to obtain a spherical magnetic substance-containing resin carrier core in which the magnetic substance was dispersed.

  As a coating material, a copolymer of methyl methacrylate and perfluorooctyl acrylate (copolymerization ratio (mass% ratio) 8: 2, weight average molecular weight 44,000) was used, which was 100 mass of the magnetic material dispersed resin core at the time of coating. A carrier coat solution containing 10% by mass of a copolymer of methyl methacrylate and perfluorooctyl acrylate was prepared using a mixed solvent of methyl ethyl ketone and toluene as a solvent so that the amount was 1.2 parts by mass with respect to parts. In addition, 0.4 parts by mass of melamine resin (number average particle size 0.2 μm) and 0.6 parts by mass of carbon black (number average particle size 30 nm, DBP oil absorption 50 ml / 100 g) may be added to the carrier coat solution using a homogenizer. Mix. Next, the magnetic material-dispersed resin core is added to the mixed solution, and the solvent is volatilized at 70 ° C. while continuously applying a shear stress to the mixed solution. And a copolymer.

The resin-coated magnetic material-dispersed resin core coated with a copolymer of methyl methacrylate and perfluorooctyl acrylate is heat-treated by stirring at 100 ° C. for 2 hours, cooled, crushed, and classified with a 200 mesh sieve. Thus, a magnetic carrier having a number average particle diameter of 37 μm, a true specific gravity of 3.7 g / cm ³ and a magnetization strength of 56.5 (Am ² / kg) was obtained.

<Example 1>
As shown in Table 5, 30 parts by weight of binder resin A-1, 70 parts by weight of binder resin B-1, 5 parts by weight of mold release agent 1, aluminum 3,5-di-tert-butylsalicylate as a charge control agent 0.5 parts by mass of the compound was sufficiently premixed with a Henschel mixer. Melt kneading was performed with a rotary twin screw extruder. The length from the raw material supply port to the outlet of the rotary twin screw extruder is 1560/926 mm, the screw diameter is 42 mm, and the barrel inner diameter is 43 mm. The heating temperature in the barrel was 100 ° C., the screw rotation speed was 300 rotations / minute, the mixture supply speed was 10 kg / hour, and the average residence time was about 14 seconds. In addition, the length from the raw material supply port of the rotary biaxial extrusion to the outlet is 1560 mm, and the vent port is vacuumed.

The obtained kneaded material was passed while being sandwiched by a steel belt type rolling mill, further rolled and cooled by a cooling roller, and cooled to room temperature by a cooling conveyor.
The obtained cooling product was roughly pulverized to a particle size of about 1 to 2 mm with a hammer mill. Next, the coarsely pulverized product was finely pulverized to a particle size of 20 μm or less with an air jet fine pulverizer.
Thereafter, the resulting finely pulverized product was subjected to surface modification and classification using a surface modification device, and toner particles having a weight average particle diameter (D ₄ ) of 6.0 μm were obtained.

Next, titanium oxide 1 (number average particle diameter: 40 nm, crystal form: rutile form, treatment agent: i-butyltrimethoxysilane, treatment amount: 10 parts by mass) was added to 100 parts by mass of the obtained toner particles.
Toner 1 was obtained by externally mixing 8 parts by mass.

  Further, a two-component developer was prepared with the magnetic carrier and toner 1 obtained above. The two-component developer was mixed with 92% by mass of magnetic carrier and 8% by mass of toner. The replenishment developer was mixed with 7% by mass of magnetic carrier and 93% by mass of toner.

<Examples 2 to 10, Comparative Examples 1 to 7>
Toners 2 to 17 were produced in the same manner as Toner 1 except that the types and blending amounts of the toner raw materials were as shown in Table 5. The external additives used are shown in Table 4. However, when using the additive, the following were used. As additive Cy, C.I. I. Pigment Blue 15: 3 was used. As the additive Ti, a fine powder of titanium oxide subjected to hydrophobic treatment having a number average particle diameter of 50 nm was used. As additive Ye, C.I. I. Pigment Yellow 74 was used. In addition, Table 6 shows the physical properties of the toners 1 to 17.

[Production examples of yellow, cyan, magenta and black toners]
(Example of production of binder resin 2)
Terephthalic acid 30mol%
Adipic acid 10 mol%
Trimellitic acid 8mol%
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
31 mol%
Polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane
23 mol%
A 4-necked flask was charged with the acid component and alcohol component shown above and tin 2-ethylhexanoate as an esterification catalyst, and was equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, and nitrogen. The reaction was performed by raising the temperature to 240 ° C. in an atmosphere. After completion of the reaction, the product was taken out of the container, cooled and pulverized to obtain a binder resin 2 having a softening point of 145 ° C. (Mn: 4,200, Mw: 490,000).

<Production example of cyan toner>
Binder resin 2 100 parts by mass Release agent 1 5 parts by mass C.I. I. Pigment Blue 15: 3 5 parts by mass, aluminum compound for charge control agent 3,5-di-tert-butylsalicylate
Using 0.2 part by mass, a cyan toner was obtained in the same manner as in the production example of colorless toner 1.

  Further, a two-component developer was prepared with a magnetic carrier and cyan toner. The two-component developer was mixed with 92% by mass of magnetic carrier and 8% by mass of toner. The replenishment developer was mixed with 7% by mass of magnetic carrier and 93% by mass of toner.

<Example of manufacturing yellow toner>
Binder resin 2 100 parts by mass Release agent 1 5 parts by mass C.I. I. Pigment Yellow 74 8 parts by mass, charge control agent 3,5-di-tert-butylsalicylate aluminum compound
Using 0.5 parts by mass, a cyan toner was obtained in the same manner as in the production example of colorless toner 1.

  Further, a two-component developer was prepared with a magnetic carrier and yellow toner. The two-component developer was mixed with 91% by mass of magnetic carrier and 9% by mass of toner. The replenishment developer was mixed with 7% by mass of magnetic carrier and 93% by mass of toner.

<Example of manufacturing magenta toner>
Binder resin 2 100 parts by mass Release agent 1 5 parts by mass C.I. I. Pigment Red 122 6 parts by mass, charge control agent 3,5-di-tert-butylsalicylate aluminum compound
Using 0.5 parts by mass, a cyan toner was obtained in the same manner as in the production example of colorless toner 1.

  Further, a two-component developer was prepared with a magnetic carrier and magenta toner. The two-component developer was mixed with 92% by mass of magnetic carrier and 8% by mass of toner. The replenishment developer was mixed with 7% by mass of magnetic carrier and 93% by mass of toner.

<Production example of black toner>
Binder resin 2 100 parts by weight Release agent 1 5 parts by weight Carbon black (average primary particle size: 60 nm) 6 parts by weight Charge control agent 3,5-di-tert-butylsalicylate aluminum compound
Using 0.5 parts by mass, a cyan toner was obtained in the same manner as in the production example of colorless toner 1.

  Further, a two-component developer was prepared with a magnetic carrier and black toner. The two-component developer was mixed with 92% by mass of magnetic carrier and 8% by mass of toner. The replenishment developer was mixed with 7% by mass of magnetic carrier and 93% by mass of toner.

<Image evaluation>
The toners 1 to 17 were evaluated as follows. A commercially available full-color copier imagePRESS C1 (Canon Inc.) was modified so that it could be output under the following conditions. Moreover, evaluation was implemented on condition of the following, and various evaluations were performed with the initial test for the first sheet and the durability test for the 10,000th sheet.
For toners 9 to 11, the toner of the present invention was fixed only on the colored toner, and for the other toners, the toner of the present invention was fixed over the entire image formable area on the recording paper.
As for the toners 8 to 11, the toner of the present invention was stacked before fixing the colored toner, and the five color toners were simultaneously fixed on the recording paper. For the other toners, the colored toner was fixed on the recording paper and discharged, and then the recording paper was again placed in the paper feed unit, and the toner of the present invention was fixed.

conditions:
Printing environment Temperature 23 ° C / Humidity 60RH% (hereinafter “N / N”)
Temperature 30 ° C / Humidity 80RH% (hereinafter "H / H")
Temperature 23 ° C / Humidity 5RH% (hereinafter “N / L”)
Recording medium Color laser copier glossy cardboard NS-701
(Glossiness of recording medium: 70.3%, 150 g / m ² , Canon Marketing Japan Inc.)
Image formation speed As color toners, yellow, cyan, magenta, black toners, and toners of the examples and comparative examples of the present invention were modified so that all five color full-color images could be output. (A4 size, 60 sheets / minute for single color, 11 sheets / minute for 5-color full color)
Fixing conditions The copying machine body was modified so that the fixing temperature was set to 170 ° C. and the fixing device shown in FIG. 1 could be installed.
Output image 5 colors solid black: 1.5 mg / cm ² toner applied amount per unit area
(Each color 0.3mg / cm ² )

The fixing device used in the embodiment will be described with reference to FIG.
In FIG. 1, a fixing roller 39 as a fixing unit includes, for example, a 2 mm thick RTV (room temperature vulcanization type) silicone rubber layer 42 on an aluminum cored bar 41 having a thickness of 5 mm, and a fluorine film having a thickness of 50 μm on the outside. The rubber layer 68 has an HTV (high temperature vulcanization type) silicone rubber layer 43 on the outside and has a diameter of 60 mm.

  On the other hand, the pressure roller 40 as a pressure means is composed of, for example, an RTV silicone rubber layer 45 having a thickness of 2 mm on an aluminum cored bar 44 having a thickness of 5 mm, a fluorine rubber layer 69 having a thickness of 50 μm on the outer side, and It has an HTV silicone rubber layer 70 having a thickness of 230 μm and a diameter of 60 mm.

  The fixing roller 39 is provided with a halogen heater 46 as a heat generating means, and the pressure roller 40 is similarly provided with a halogen heater 47 in a metal core for heating from both sides. The thermistors 48a and 48b in contact with the fixing roller 39 and the pressure roller 40 detect the temperatures of the fixing roller 39 and the pressure roller, and the halogen heaters 46 and 47 are controlled by the control devices 49a and 49b based on the detected temperatures, respectively. Then, both the temperature of the fixing roller 39 and the temperature of the pressure roller 40 are controlled so as to be kept at a constant temperature (for example, 160 ° C. ± 10 ° C. The fixing roller 39 and the pressure roller 40 have a pressure mechanism (not shown). Z)) with a total pressure of about 40 kg.

  The cleaning device C cleans the nonwoven web 56 made of Nomex (trade name) by pressing it against the fixing roller 39 with the pressing roller 55. The web 56 is appropriately wound by a winding device (not shown) so that toner or the like does not accumulate at the contact portion with the fixing roller 39.

<Measurement of image gloss (gloss)>
Under the condition of N / N, an image at the end of durability (first sheet) and an image after durability (10,000 sheets) were output, and the image gloss (%) was measured.
The image glossiness (gloss) was measured using a handy type gloss meter PG-1M (manufactured by Nippon Denshoku Industries Co., Ltd.). As a measurement, the light projection angle and the light reception angle were adjusted to 60 °. For the image glossiness, the glossiness (gross) of 20 points on the output image was measured, and the average value was defined as the image glossiness (%).

The evaluation criteria were determined as follows.
A: Difference from the gloss of the recording medium is less than 3% B: Difference from the gloss of the recording medium is from 3% to less than 7% C: Difference from the gloss of the recording medium is from 7% to less than 11% D: The difference from the recording medium glossiness is 11% or more and less than 15%. E: The difference from the recording medium glossiness is 15% or more.

<Evaluation of image gloss (gloss) uniformity>
The evaluation of the image glossiness (gloss) uniformity was evaluated based on the difference between the maximum value and the minimum value when the image glossiness (gross) was measured.
A: Less than 2.0% Very good.
B: 2.0% or more and less than 3.5%
C: 3.5% or more and less than 5.0% Although gloss unevenness can be confirmed, there is no problem in use.
D: 5.0% or more and less than 7.0% Gloss unevenness can be confirmed, and there is a sense of incongruity.
E: 7.0% or more. There is a problem.
Note that the level having no problem is A to C.

<Evaluation of color variation of toner image or recording medium>
Color variation is set to 50% image area ratio, evaluation paper is color laser copier paper, evaluation environment is set to N / N, and the initial durability image (first sheet) and the endurance image (10,000 sheets) are displayed. Output. The output images are green (toner applied amount of 0.3 mg / cm ^{2 for both} yellow toner and cyan toner), red (toner applied amount of 0.3 mg / cm ^{2 for both} magenta toner and cyan toner).
/ Cm ² ) and blue (both the amount of applied toner is 0.3 mg / magenta toner and cyan toner)
cm ² ). For each color, an image using the toner of the present invention having an applied amount of 0.4 mg / cm ² and an image not using it were used as measurement samples, and the difference in color of the toner image or the recording medium was measured. Further, as a weather resistance test, a long-term exposure evaluation was performed on the image sample with a commercially available weather meter in accordance with JISK7102.

Further, the difference in color variation (ΔC) was defined as follows.
ΔC = {(a ^* colorless toner usage image - a ^* a colorless toner unused image) ²
+ (Colorless toner used image b ^* - colorless toner unused image b ^{*) 2} 1/2}

In the measurement, arbitrary five points in the image were measured and the average value was obtained, and ΔC was obtained by the above formula.
A: 0 ≦ ΔC <1.0 (a level that cannot be judged visually)
B: 1.0 ≦ ΔC <2.0 (It is barely noticeable visually, but it is not worrisome)
C: 2.0 ≦ ΔC <3.0 (usable level)
D: 3.0 ≦ ΔC <4.5 (a change in the color of the toner image or the recording medium is seen, and there is a sense of incongruity)
E: 4.5 ≦ ΔC (the color of the toner image or the recording medium is remarkably changed)
Note that levels A to C are acceptable as a product. The results are shown in the table.

<Evaluation of fine line reproducibility during fixing>
For evaluation of scattering at the time of fixing, a striped latent image as shown in FIG. 2 was formed, and the image after fixing was evaluated. FIG. 2 shows a latent image having a latent image portion width of 4 dots (170 μm) and a non-latent image portion width of 10 dots (420 μm) at a resolution of 600 dpi. The latent image portion uses four color toners of yellow, cyan, magenta, and black, and the latent image portion and the non-latent image portion are overcoated with colorless toner. The evaluation environment was N / L environment and the evaluation paper was color laser copier paper.

The evaluation criteria are shown below.
A: A fine thin line is fixed.
B: Less than 3 out of 19 light splatters are observed.
C: Minor scattering is observed from 3 to less than 7 out of 19.
D: 7 or more of 19 light splatters are observed.
Or, a little noticeable scattering around the fine line is observed in less than 5 out of 19 lines.
D: Slightly conspicuous scattering around the fine line is observed from 5 to less than 10 out of 19.
E: 11 or more of 19 observable scatters around the fine line are observed.
The levels usable as products are A to C.

<Evaluation of abrasion resistance during fixing>
The image was rubbed with a dedicated rubbing tester, and the glossiness (gloss) of the toner image portion of the present invention before and after rubbing was measured to evaluate the difference in glossiness. The rubbing tester has a structure in which five 5 mm square, 200 g brass weights placed on a sheet are placed on a table for fixing the sheet by static electricity. Silbon C paper (manufactured by Ozu Sangyo Co., Ltd.) is sandwiched between the paper and the weight. The table for fixing the paper can reciprocate in the longitudinal direction of the paper. At this time, the image is rubbed against the Sylbon C paper and lost. In this example, the image was rubbed by 10 reciprocations.
The difference between the average value of image gloss before rubbing (gloss) and the average value of image gloss after rubbing was evaluated based on the following criteria.
A: Less than 5.0% Very good.
B: 5.0% or more and less than 10.0% Almost no concern.
C: 10.0% or more and less than 15.0% Although gloss unevenness can be confirmed, there is no problem in use.
D: 15.0% or more and less than 20.0% Gloss unevenness can be confirmed, and there is a feeling of strangeness.
E: 20.0% or more. There is a problem.
Note that the level having no problem is A to C.

<Evaluation of paper discharge adhesion during fixing>
Evaluation of the paper discharge adhesion at the time of fixing was carried out by forming a striped latent image as shown in FIG. 2 and evaluating the image after fixing. FIG. 2 shows a latent image having a latent image portion width of 4 dots (170 μm) and a non-latent image portion width of 10 dots (420 μm) at a resolution of 600 dpi. The latent image portion uses four color toners of yellow, cyan, magenta, and black, and the latent image portion and the non-latent image portion are overcoated with colorless toner. The evaluation environment is H / H environment, the evaluation paper is color laser copier paper, and 1000 sheets are output continuously. Then, after leaving the output image for 1 hour in an N / N environment, the evaluation is performed.

The evaluation criteria are shown below.
A: There is no occurrence of adhesion of paper discharge, indicating a good state.
B: Although slight adhesion between images can be seen, there is no problem.
C: Adhesion between images occurs in part. The image can be easily peeled off and no influence on the image is seen.
D: Adhesion between images occurs. When the image is peeled off, the glossiness of the toner portion changes, which is not preferable for use as an output image.
E: Adhesion between images occurs remarkably. When the image is peeled off, the toner part is peeled off and cannot be used as an output image.
The levels usable as products are A to C. The results are shown in the table.

Claims (9)

A toner having toner particles containing at least a binder resin and a release agent,
The binder resin is a polyester resin synthesized using an aliphatic polyhydric alcohol as an alcohol component and a titanium compound as a catalyst, and has a softening point of 120 ° C. or higher and 200 ° C. or lower. Including
The saturation (C *) and lightness (L *) of the molded product obtained by pressure molding the toner are as follows:
0.0 ≦ (C *) ≦ 15.0
88.0 ≦ (L *) ≦ 100.0
Toner characterized by being.   The toner according to claim 1, wherein the binder resin includes the binder resin A in an amount of 5% by mass to 50% by mass.   The binder resin is a polyester resin synthesized using an alkylene oxide adduct of bisphenol A as an alcohol component, and further includes a binder resin B having a softening point of 60 ° C. or higher and 100 ° C. or lower. The toner according to claim 1, wherein the toner is a toner.   The toner according to claim 1, wherein the release agent includes a hydrocarbon wax.   The toner according to claim 1, wherein the release agent includes a wax treated with a styrene monomer.   The toner according to claim 1, wherein the titanium compound includes an aromatic carboxylic acid titanium compound.   The toner according to claim 1, wherein the toner includes titanium oxide fine particles treated with a silane compound.   8. An image forming method including a step of forming a toner image on a recording medium, wherein the toner image is formed over the entire image formable area on the recording medium, and the toner forming the toner image is defined in claims 1 to 7. An image forming method comprising the toner according to any one of the above.   The image forming method according to claim 8, wherein the toner image is formed by a heating and pressing unit on a recording medium on which a colored toner image is fixed in advance.

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