JP2005300609A - Image forming apparatus and toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner which is superior in quick startability and electric power saving, and suppresses image defects, such as offsets, and with which the gloss of a fixed image can be uniformly maintained and high quality images can be obtained, and to provide an image forming apparatus. <P>SOLUTION: The toner used for the image forming apparatus, including a heat pressurizing fixing device 10 for fixing the toner image to a material to be heated, by heating the material by the heat of a rotating body 1 is so prepared as to satisfy the following (a) to (c): (a) The addition ratio of a polyester base resin occupying in the entire part of the toner, defined as C (mass%), the acid value, as A (mgKOH/g), and the hydroxyl group value, as B (mgKOH/g), is 50≤C, 10≤(A+B)×C/100≤50; (b) (G'<SB>50</SB>/G'<SB>100</SB>) of the toner is 5,000 to 70,000, (G'<SB>150</SB>) is 1.0×10<SP>2</SP>to 1.0×10<SP>5</SP>(dN/m<SP>2</SP>) and (P/G'<SB>150</SB>) is 10 to 1,500; (c) the glass transition temperature of the toner is 50 to 750°C, where Mp is 5,000 to 15,000, Mw is 8,000 to 150,000 and Mw/Mn is 1.5 to 20. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a toner and an image forming apparatus applied to an image forming apparatus using a heat and pressure fixing device. More specifically, the present invention relates to a toner and an image forming apparatus applied to an image forming apparatus using a surface heating type heat and pressure fixing device.

  In an image forming apparatus, recording materials (transfer material sheet, electrofax sheet, electrostatic recording paper, OHP (over head projector) sheet, etc.) by image forming process means such as electrophotographic process, electrostatic recording process, magnetic recording process, etc. As a fixing device that heats and fixes an unfixed image (toner image) of the target image information formed and supported on a recording material surface by a transfer method or a direct method on a recording material surface as a permanently fixed image, An internal heating type heat roller type fixing device is widely used. Recently, a film heating type fixing device has been put into practical use from the viewpoint of quick start and energy saving. The apparatus configurations and advantages / problems of these fixing devices are as follows.

i) Internal heating type heat roller type fixing device An internal heating type heat roller type fixing device is basically composed of a pressure roller pair of a fixing roller (heating roller) and a pressure roller, and rotates the roller pair. A recording material on which an unfixed toner image to be image-fixed is formed and supported is introduced into the fixing nip portion where the roller pair is in mutual contact, and is nipped and conveyed by the heat of the fixing roller and the pressing force of the fixing nip portion. An unfixed toner image is fixed to a recording material surface by heat and pressure.

  In general, the fixing roller has an aluminum hollow metal roller as a base body (core metal), and a halogen lamp as a heat source is inserted and disposed in the inner space thereof. The temperature is adjusted by controlling the energization of the halogen lamp so that the temperature is maintained.

  In particular, a fixing device of an image forming apparatus that performs full-color image formation that requires the ability to sufficiently melt and mix a maximum of four toner image layers, has a high heat capacity in the core of the fixing roller. The toner image is heated through the rubber elastic layer by providing a rubber elastic layer for enveloping and uniformly melting the toner image on the outer periphery of the core metal. There is also a configuration in which a heat source is provided in the pressure roller so that the pressure roller is also heated and temperature-controlled.

  However, in the heat roller type fixing device, since the heat capacity of the fixing roller is large even if power is supplied to the halogen lamp that is the heat source of the fixing device at the same time when the power of the image forming apparatus is turned on, the fixing roller and the like are cooled down. A considerable waiting time (wait time) is required until the temperature rises to a predetermined fixing temperature from the existing state, and the quick start property is lacking. In order to avoid this, the halogen lamp is energized to maintain the fixing roller in a predetermined temperature control state so that the image forming operation can be executed at any time even when the image forming apparatus is in a standby state (non-image output). However, there is a problem that power consumption is large.

  Further, in the case of using a fixing roller having a particularly large heat capacity, such as the fixing device of the above-described full-color image forming apparatus, a delay occurs between the temperature adjustment and the temperature increase of the surface of the fixing roller. Problems such as offset have occurred.

ii) Film heating type fixing device A film heating type fixing device has a heat resistant film (fixing film) sandwiched between a ceramic heater as a heating element and a pressure roller as a pressure member, and a nip portion is formed. A recording material on which an unfixed toner image to be image-fixed is formed and supported is introduced between the film in the nip portion and the pressure roller, and is nipped and conveyed together with the film. The heat of the ceramic heater is applied to the recording material through a film, and the unfixed toner image is fixed to the surface of the recording material by applying pressure at the nip portion (for example, see Patent Documents 1 to 4). .

  This film heating type fixing device can constitute an on-demand type device using a low-heat capacity member as a ceramic heater and a fixing film, and energizes the ceramic heater as a heat source only when image forming of the image forming apparatus is executed. Thus, it is only necessary to generate heat at a predetermined fixing temperature, the waiting time from the power-on of the image forming apparatus to the image forming executable state is short (quick start property), and the power consumption during standby is greatly reduced ( There are advantages such as (power saving).

  However, these configurations are suitable for fixing a monochrome image with low glossiness, and there is room for improvement as a full-color image forming apparatus or a fixing device for high-speed models that require relatively high glossiness and color mixing. is there.

  On the other hand, with respect to the toner, a toner focusing on the viscoelasticity of the resin is disclosed (for example, see Patent Documents 5 to 7). However, improvement is still required to achieve both low-temperature fixability and high-temperature offset resistance while adapting to a film heating type fixing device.

  In order to improve the high temperature offset resistance at the time of fixing, a material having a relatively high releasability such as polyethylene wax or polypropylene wax is generally used as a toner material, but a large amount of such a low softening point substance is contained. Then, it is often inferior in developability.

  In general, in color toners, high temperature offset resistance is improved by applying silicone oil or the like to the surface of the heat fixing roller without adding a release agent. However, the output transfer member obtained in this way has problems such as an unpleasant feeling to the user due to excess silicone oil or the like adhering to the surface, and high glossiness that makes it difficult to see.

  In order to solve these problems, a toner is prepared by a polymerization method, a low softening point substance is contained inside the toner, and further, by controlling the physical properties of the resin, the low temperature fixing property, the high temperature offset resistance, the image glossiness, and the OHP permeability are improved. A combination of a satisfactory toner and a heat fixing device has been proposed (see, for example, Patent Document 8).

  However, this heat-fixing device has a heat roller system, and has an advantage such as a long life and pressure applied during fixing, but there are problems such as a long wait time and high power consumption as described above. .

  Further, it is generally preferable to use a low molecular weight binder resin having a sharp melt property for a full color image toner. However, when a sharp-melt binder resin is used, when the toner is melted in the heat and pressure fixing process, the self-cohesion force of the binder resin is low, and thus a problem with high-temperature offset resistance tends to occur.

In general black toner for black-and-white copying machines, a relatively high crystalline wax typified by polyethylene wax or polypropylene wax is used as a release agent in order to improve high temperature offset resistance during fixing. However, in full-color image toner, when it is projected on OHP due to the high crystallinity of the release agent itself and the difference in refractive index from the material of the OHP sheet,
Transparency is hindered, and the projected image has low saturation and lightness.

  In order to solve this problem, a method of reducing the crystallinity of wax by using a nucleating material in combination with wax has been proposed (see, for example, Patent Documents 9 and 10). However, these waxes do not satisfy all of transparency in OHP, low-temperature fixability at the time of heat and pressure fixing, and high-temperature offset resistance. For this reason, in ordinary color toners, an oil such as silicone oil or fluorine oil is applied to the heat-fixing roller without adding a release agent as much as possible to improve high-temperature offset resistance and transparency with OHP.

However, the fixed image obtained in this way has extra oil attached to the surface thereof, so that the oil adheres to the photoconductor and becomes contaminated, or the oil swells the fixing roller, thereby prolonging the life of the fixing roller. May be shortened. On the other hand, materials such as polyester resins and colorants that are often used in toners have a large difference in chargeability, and are therefore prone to offset, and improvements are required.
As described above, there is no combination of a toner and a heat fixing device that solves various problems.
JP-A-63-313182 Japanese Patent Laid-Open No. 2-157878 JP-A-4-44075 JP-A-4-204980 Japanese Patent Laid-Open No. 1-128071 JP-A-4-353866 JP-A-6-59504 Japanese Patent Laid-Open No. 10-282822 JP-A-4-149559 JP-A-4-107467

  An object of the present invention is to provide an image forming apparatus and toner that solve the problems of the prior art. More specifically, an object of the present invention is to bring a rotating body of a heat and pressure fixing device for fixing a toner image onto a heated material carrying an unfixed toner image to a predetermined temperature in a short time. It is an object of the present invention to provide an image forming apparatus and a toner that can (quick start property) and can sufficiently secure a fixing property of a toner image in a wide temperature range without applying oil to a rotating body.

  Another object of the present invention is to provide an image forming apparatus and a toner that can achieve excellent offset resistance without contaminating a rotating body.

  Another object of the present invention is to provide an image forming apparatus and a toner capable of obtaining an image with excellent color reproducibility by sufficiently mixing multicolor toners and excellent in transparency of an overhead projector film (OHP) image. There is.

  As a result of intensive studies, the present inventors have found that even when using a surface heating type heat and pressure fixing device excellent in quick start property and image uniformity, the acid value, hydroxyl value, molecular weight, viscoelasticity, melt index, It has been found that by adjusting the methanol wettability half-value and the average circularity to a specified range, problems such as toner contamination of the rotating body and offset due to surface potential can be solved.

That is, the present invention relates to a rotating member, a counter member that forms the fixing nip portion with the rotating member, and a heating member that forms the nip portion at a portion different from the fixing nip portion and heats the surface of the rotating member. And heating and pressurizing the heated material carrying the unfixed toner image in the fixing nip portion, sandwiching and transporting the heated material, and heating the heated material by the heat of the rotating body to fix the toner image on the heated material. An image forming apparatus comprising a fixing device,
The toner used in the image forming method is a toner having toner particles having at least a binder resin, a colorant and a wax, and an external additive, and satisfies the following a) to c): It is.
a) The binder resin contains at least one polyester resin or a polyester unit-containing resin, and the addition ratio of the polyester resin and / or the polyester unit-containing resin in the whole toner is C (mass%). And / or when the acid value of the polyester unit-containing resin is A (mgKOH / g) and the hydroxyl value of the polyester resin and / or polyester unit-containing resin is B (mgKOH / g),
50 ≦ C and 10 ≦ (A + B) × C / 100 ≦ 50;
b) The ratio (G ′ ₅₀ / G ′ ₁₀₀ ) between the storage elastic modulus (G ′ ₅₀ ) of the toner at ₅₀ ° C. and the storage elastic modulus (G ′ ₁₀₀ ) of the toner at 100 ° C. is 5,000 to 70. The storage elastic modulus (G ′ ₁₅₀ ) at a temperature of 150 ° C. of the toner is 1.0 × 10 ^{2 to} 1.0 × 10 ⁵ (dN / m ² ). When the surface pressure at the fixing nip portion is P, the ratio (P / G ′ ₁₅₀ ) to the storage elastic modulus (G ′ ₁₅₀ ) at a temperature of 150 ° C. is 10 to 1500;
c) The toner has a glass transition temperature of 50 to 70 ° C., and in the molecular weight distribution by gel permeation chromatography (GPC) of tetrahydrofuran (THF) soluble matter, the peak molecular weight (Mp) of the main peak is 5000 to 15000. The weight average molecular weight (Mw) is 8000-150000, and Mw / Mn is 1.5-20.

  In addition, the present invention is a toner having the above characteristics used in the image forming apparatus of the present invention.

  Provided are an image forming apparatus and a toner which are excellent in quick start property and power saving and which can suppress image defects such as offset. Further, the present invention provides an image forming apparatus and a toner that can maintain a uniform glossiness of a fixed image and can obtain a high-quality image excellent in transparency of an overhead projector film (OHP) image.

(1) Toner of the present invention The toner of the present invention is a toner having toner particles having at least a binder resin, a colorant and a wax and an external additive, and is different from the fixing nip portion between the rotating body and the opposing member. The toner can provide good fixing characteristics by fixing with a surface heating type fixing device that forms a nip portion at a portion and heats the surface of the rotating body.

  In general, the surface heating type fixing device according to the present invention is excellent in quick start property, image uniformity, etc., but there are concerns about problems such as toner contamination of the rotating body and offset due to surface potential. The toner of the present invention solves these problems by adjusting the acid value, hydroxyl value, molecular weight, viscoelasticity, melt index, half-value of methanol wettability, and average circularity of the toner to specified ranges. Preferred forms of the toner of the present invention are shown below.

The binder resin of the toner of the present invention contains at least one polyester resin and / or polyester unit-containing resin, and the addition ratio of the polyester resin and / or polyester unit-containing resin in the whole toner is C (mass%). When the acid value of the polyester resin and / or polyester unit-containing resin is A (mgKOH / g), and the hydroxyl value of the polyester resin and / or polyester unit-containing resin is B (mgKOH / g),
50 ≦ C and 10 ≦ (A + B) × C / 100 ≦ 50.

  When the addition ratio C of the polyester resin and / or the polyester unit-containing resin is less than 50% by mass, the chargeability in the development with the polyester and the dispersion effect of the wax and the colorant are unfavorable.

  If the value of (A + B) × C / 100 is less than 10, the affinity between the binder resin and additives such as waxes and colorants is low, which leads to poor dispersion and is satisfactory in fixability and coloring power? There is no tendency. Furthermore, the chargeability related to the developability of the toner is inferior. When the value of (A + B) × C / 100 exceeds 50, the toner is excessively charged, and offset, particularly charging offset is likely to occur. Further, the charging property at high temperature and high humidity related to the developing property of the toner is inferior.

In the present invention, (A + B) × C / 100 is more preferably 15 to 40 in order to obtain good fixability.
In order for (A + B) × C / 100 to satisfy 10 to 50, the addition ratio C of the polyester resin and / or polyester unit-containing resin is changed, or the monomer type is selected and the polyester resin and / or polyester unit-containing resin is selected. This can be achieved by adjusting the acid value or hydroxyl value of the above.

The acid value and hydroxyl value of the binder resin of the toner are measured as follows.
<Measurement of acid value and hydroxyl value of toner binder resin>
The acid value can be measured as follows.
2-10 g of sample is weighed into a 200-300 ml Erlenmeyer flask, and about 50 ml of a mixed solvent of methanol: toluene = 30: 70 is added to dissolve the resin. If solubility is poor, a small amount of acetone may be added. Using a mixed indicator of 0.1% bromthymol blue and phenol red, titration is performed with a pre-standardized N / 10 caustic potassium to alcohol solution, and the acid value is obtained from the consumption of the alcohol potassium solution by the following calculation.
Acid value = KOH (ml) × N × 5.61 / sample weight (where N is a factor of N / 10 KOH)

The hydroxyl value can be measured as follows.
A 6 ml sample is precisely weighed in 1 mg units in a 200 ml Erlenmeyer flask, a mixed solution of acetic anhydride / pyridine = 1/4 is added with a 5 ml hole pipette, and 25 ml of pyridine is further added with a graduated cylinder. Attach a condenser to the Erlenmeyer flask and react in an oil bath at 100 ° C. for 90 minutes. Add 3 ml of distilled water from the top of the cooling section, shake well and let stand for 10 minutes. With the cooler attached, the Erlenmeyer flask is pulled out of the oil bath and allowed to cool. When the temperature reaches about 30 ° C., the cooler and the flask mouth are washed with a small amount of acetone (about 10 ml) from the upper mouth of the cooler. 50 ml of THF is added with a graduated cylinder, and neutralization titration is performed with a 50 ml burette of N / 2 KOH-THF solution using an alcohol solution of phenolphthalein as an indicator. Immediately before the end of neutralization, 25 ml of neutral alcohol (methanol / acetone = 1/1 volume ratio) is added, and titration is performed until the solution becomes slightly reddish. At the same time, a blank test is performed.

(In the formula, A: ml number of N / 2KOH-THF solution required for this test, B: ml number of N / 2OH-THF solution required for blank test, f: titer of N / 2KOH-THF solution, S: Sampling amount (g), C: Acid value)

  In addition, the average value of two measured values is employ | adopted for a hydroxyl value.

  As the polyester resin and / or the polyester unit-containing resin used as the binder resin of the toner of the present invention, resins having alcohol and carboxylic acid, carboxylic acid anhydride, carboxylic acid ester or the like as raw material monomers can be used.

  Specific examples of the raw material monomer for the polyester resin and / or the polyester unit-containing resin are as follows.

  Examples of the alcohol component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane, poly Oxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) Alkylene oxide adducts of bisphenol A such as propane and polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3 -Propylene glycol, 1,4-butanediol, neopentyl glycol 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol A, and dihydric alcohol components such as bisphenol derivatives represented by the following general formula (1).

(In the formula, R represents an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)

  Also, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol Trihydric or higher alcohol components such as glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene Used as an ingredient.

Examples of the acid component include aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof; And succinic acid substituted with an alkyl group or an alkenyl group or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, and citraconic acid, or anhydrides thereof.

  As the binder resin contained in the toner of the present invention, a mixture of the above polyester resin and vinyl copolymer may be used. Further, as the binder resin contained in the toner of the present invention, a mixture of a polyester unit-containing resin (hybrid resin) described later and a vinyl copolymer may be used. As the binder resin contained in the toner of the present invention, a mixture of a vinyl copolymer may be used in addition to the polyester resin and a polyester unit-containing resin (hybrid resin) described later.

  As the polyester unit-containing resin, a resin in which a vinyl polymer unit and a polyester unit are chemically bonded is used. Specifically, a polyester unit and a vinyl polymer unit obtained by polymerizing a monomer having a carboxylic ester group such as (meth) acrylic acid ester are formed by a transesterification reaction, and preferably a vinyl polymer. A graft copolymer (or a block copolymer) is formed by using as a trunk polymer and a polyester unit as a branch polymer.

  The following are mentioned as a vinyl-type monomer for producing | generating a vinyl-type copolymer or a vinyl-type polymer unit. Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert- Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-chloro styrene, 3, Styrene derivatives such as 4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene; styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene ; Vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, etc. Vinyl halides; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, methacryl Α-methylene aliphatic monocarboxylic acid esters such as dodecyl acid, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, acrylic acid Propyl, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, acrylic Acrylic acid esters such as phenyl acid; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl N-vinyl compounds such as carbazole, N-vinylindole and N-vinylpyrrolidone; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

Unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; unsaturated such as maleic acid anhydride, citraconic acid anhydride, itaconic acid anhydride and alkenyl succinic acid anhydride Dibasic acid anhydride: maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl succinic acid Half esters of unsaturated dibasic acids such as acid methyl half ester, fumaric acid methyl half ester, and mesaconic acid methyl half ester; Unsaturated dibasic acid esters such as dimethyl maleic acid and dimethyl fumaric acid; Acrylic acid, Methacrylic acid, Croto Α, β-unsaturated acids such as acids and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic acid anhydride, anhydrides of the α, β-unsaturated acid and lower fatty acids Monomers having a carboxyl group such as alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof are also exemplified as vinyl monomers.

  Acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1-methyl) (Hexyl) Styrene derivatives having a hydroxy group such as styrene may also be mentioned as vinyl monomers.

  In the toner of the present invention, the vinyl polymer unit and the vinyl copolymer of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the crosslinking agent used in this case include divinylbenzene and divinylnaphthalene as aromatic divinyl compounds. Examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, and 1,6 hexanediol. Examples include diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylate of the above compounds with methacrylate; examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate and triethylene glycol. Diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate Examples of the diacrylate compounds connected by a chain containing an aromatic group and an ether bond include polyoxyethylene (2) -2,2-bis ( Examples include 4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate, and those obtained by replacing acrylates of the above compounds with methacrylate.

  The vinyl polymer and the vinyl polymer unit may have a structure crosslinked with a polyfunctional crosslinking agent. Examples of the polyfunctional crosslinking agent used at that time include pentaerythritol triacrylate, trimethylolethane triacrylate, Trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate and those obtained by replacing the acrylate of the above compound with methacrylate; triallyl cyanurate and triallyl trimellitate.

  In the present invention, it is preferable that a monomer component capable of reacting with both unit components is contained in the vinyl copolymer unit and / or the polyester unit. Examples of the monomer constituting the polyester unit that can react with the vinyl copolymer include unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. Among the monomers constituting the vinyl copolymer, those capable of reacting with the polyester unit include those having a carboxyl group or a hydroxy group, acrylic acid or methacrylic acid esters.

As a method for obtaining a polyester unit-containing resin having a vinyl polymer unit and a polyester unit, a polymer containing a monomer component capable of reacting with each of the vinyl polymer unit and the polyester unit listed above is present. A method obtained by polymerizing one or both of the resins is preferred.

  Examples of the polymerization initiator used for producing the vinyl copolymer and vinyl polymer unit in the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4- Methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′- Azobisisobutyrate, 1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2- Phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetate Ketone peroxides such as luacetone peroxide and cyclohexanone peroxide, 2,2-bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetra Methylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α, α'-bis (t-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide Oxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioyl peroxide, di-isopropyl peroxydicarbonate, di-2-ethyl Xyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-methoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, Acetylcyclohexylsulfonyl peroxide, t-butyl peroxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxylaur Rate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, di-t-butyl peroxyisophthalate, t-butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate , Di -t- butyl peroxy hexahydro terephthalate, di -t- butyl peroxy azelate, and the like.

Examples of the method for preparing the polyester unit-containing resin (hybrid resin) used in the toner of the present invention include the following production methods (1) to (5).
(1) A method in which a vinyl copolymer and a polyester resin are separately produced and then dissolved and swollen in a small amount of an organic solvent, an esterification catalyst and an alcohol are added, and the ester exchange reaction is performed by heating to synthesize.
(2) A method for producing a polyester unit and a hybrid resin in the presence of a vinyl copolymer after the production thereof. The hybrid resin comprises a reaction between a vinyl polymer unit (adding a vinyl monomer if necessary) and either a polyester monomer (polyhydric alcohol, polycarboxylic acid) or a polyester unit, or both. Produced by reaction. An organic solvent can be appropriately used.

(3) A method for producing a vinyl copolymer unit and a hybrid resin in the presence of the polyester resin after the production. The hybrid resin is produced by a reaction between a polyester unit (added with a polyester monomer if necessary) and one or both of a vinyl polymer unit and a vinyl monomer. An organic solvent can be appropriately used.
(4) After producing a vinyl polymer unit and a polyester unit, a hybrid is obtained by adding one or both of a vinyl monomer and a polyester monomer (polyhydric alcohol, polycarboxylic acid) in the presence of these polymer units. A resin component is produced. An organic solvent can be appropriately used.

(5) A vinyl copolymer unit, a polyester unit, and a hybrid resin component are prepared by mixing a vinyl monomer and a polyester monomer (polyhydric alcohol, polyvalent carboxylic acid) and continuously performing addition polymerization and condensation polymerization reaction. Is manufactured. An organic solvent can be appropriately used.
In the production methods (1) to (5), a plurality of types of polymer units having different molecular weights and different degrees of crosslinking can be used for the vinyl polymer unit and the polyester unit.

The toner of the present invention, a storage elastic modulus at a temperature of 50 ° C. of the toner (G _'50) and a storage modulus at a temperature 100 ° C. of the toner (G' ratio of _{100) (G '50 / G} ' 100) of 5, The storage elastic modulus (G ′ ₁₅₀ ) at a temperature of 150 ° C. of the toner is 1.0 × 10 ^{2 to} 1.0 × 10 ⁵ (dN / m ² ). Further, the surface heating type heat and pressure fixing device in the image forming apparatus of the present invention has a rotating body and an opposing member that forms the fixing nip portion with the rotating body. Then, the ratio (P / G ′ ₁₅₀ ) to the storage elastic modulus (G ′ ₁₅₀ ) at a temperature of 150 ° C. of the toner is 10 to 1500. When the storage elastic modulus of the toner is in the above range, it is possible to obtain a good fixed image while solving problems such as contamination of the heating member, which is a concern in the surface heating type heat and pressure fixing device.

In the present invention, G ′ ₅₀ , G ′ ₁₀₀ and a ratio thereof (G ′ ₅₀ / G ′ ₁₀₀ ) indicate a storage elastic modulus at 50 ° C., a storage elastic modulus at 100 ° C., and a ratio thereof, respectively. G ′ ₅₀ / G ′ ₁₀₀ indicates the ease of melting when the toner is heated from room temperature. G ′ ₁₅₀ indicates the storage elastic property of the toner at 150 ° C. Further, when the surface pressure P at the fixing nip is high, high temperature offset is likely to occur, and when the value of G ′ ₁₅₀ is small, high temperature offset is likely to occur. Therefore, the ratio (P / G ′ ₁₅₀ ) with the fixing nip portion indicates the likelihood of high temperature offset.

Since the toner of the present invention has a storage elastic modulus (G ′ ₁₅₀ ) at a temperature of 150 ° C. of 1.0 × 10 ^{2 to} 1.0 × 10 ⁵ (dN / m ² ), the gloss stability and offset resistance are improved. Good in terms of sex. If the value of the storage elastic modulus (G ′ ₁₅₀ ) is smaller than 1.0 × 10 ² , the change in glossiness at the front and rear ends and the change in glossiness on the front and back sides during double-sided printing are large, and it is difficult to obtain a stable image. . On the other hand, if the storage elastic modulus (G ′ ₁₅₀ ) is larger than 1.0 × 10 ⁵ , the change in the glossiness is small even when the temperature of the fixing device is changed or the process speed is changed. Is not fully dissolved and the OHT permeability is not satisfactory, and it is difficult to correspond to the mode that outputs high gloss.

The ratio (P / G ′ ₁₅₀ ) between the surface pressure P at the fixing nip portion between the rotating body of the heat and pressure fixing device and the opposing member and the storage elastic modulus (G ′ ₁₅₀ ) at a toner temperature of 150 ° C. is 10 to 1500. If it is, it is good from a viewpoint of glossiness stability and high temperature offset resistance. When the value of (P / G ′ ₁₅₀ ) is less than 10, the fixing nip surface pressure is low with respect to the toner melt viscosity, and low temperature fixing failure is particularly likely to occur. When the value of (P / G ′ ₁₅₀ ) exceeds 1500, the surface pressure at the fixing nip portion is high with respect to the toner melt viscosity, and glossiness change and offset are likely to occur. The surface pressure P will be described later in the description of the image forming apparatus.

In the present invention, in order to make (P / G ′ ₁₅₀ ) in the range of 10 to 1500, there is a method of adjusting the pressure of the roller in order to change the surface pressure P. Further, there is a method of changing the degree of crosslinking of the binder resin in order to change the storage elastic modulus (G ′ ₁₅₀ ) at 150 ° C.

Here, the measuring method of storage elastic modulus is shown below.
<Measurement of storage modulus of toner>
Viscoelasticity measuring device (rheometer) RDA-II type (manufactured by Rheometrics) is used for measurement.

Measuring jig: A parallel plate having a diameter of 7.9 mm is used when the elastic modulus is high, and a parallel plate having a diameter of 25 mm is used when the elastic modulus is low.
Measurement sample: Toner is heated and melted and molded into a cylindrical sample having a diameter of about 8 mm and a height of 1.5 to 5 mm, or a disk sample having a diameter of about 25 mm and a height of 1.5 to 3 mm.
Measurement frequency: 6.28 radians / second Measurement strain setting: The initial value is set to 0.1%, and measurement is performed in automatic measurement mode.
Sample extension correction: Adjust in automatic measurement mode.
Measurement temperature: The temperature is raised to 5 to 160 ° C. at a rate of 2 ° C. per minute.

  The toner of the present invention has a glass transition temperature of 50 to 70 ° C., and the molecular weight distribution by gel permeation chromatography (GPC) soluble in tetrahydrofuran (THF) has a peak molecular weight (Mp) of 5000 to 15000 in the main peak. Since the weight average molecular weight (Mw) is 8000 to 150,000 and Mw / Mn is 1.5 to 20, it is excellent in low-temperature fixability and offset resistance, and other fixing defects can be suppressed. . In addition, even when a plurality of resins are mixed, actual measurement values measured from toner are used.

When the glass transition temperature of the toner is less than 50 ° C., the toner blocking property (storability) is not satisfactory. On the other hand, when the glass transition temperature of the toner is higher than 70 ° C., the low-temperature fixability is remarkably deteriorated.
In order to set the glass transition temperature of the toner within the above range, a binder resin in the toner having a glass transition temperature within the above range may be used. In order to set the glass transition temperature of the binder resin used in the present invention within the above range, it may be appropriately determined from the molecular weight, the material and the like.

The measuring method of glass transition temperature is shown below.
<Measuring method of glass transition temperature>
It measures according to ASTM D3418-82 using a differential scanning calorimeter (DSC measuring apparatus) “DSC 2920 (manufactured by TA Instruments)”. 5 mg of a measurement sample is precisely weighed, put in an aluminum pan, and an empty aluminum pan is used as a reference, and measurement is performed at a temperature rising rate of 10 ° C./min in a temperature range of 30 to 200 ° C. In this temperature rising process, a DSC curve in a temperature range of 60 to 200 ° C. is measured. The toner glass transition temperature can be obtained from this DSC curve.

  In the present invention, when the molecular weight Mp of the main peak in the molecular weight distribution of the THF-soluble component is less than 5000, the high-temperature storage stability is weak, the high-temperature offset resistance is inferior, and the glossiness (gross) variation on the image is large and difficult to see. It is easy to become. When the molecular weight Mp of the main peak is larger than 15000, the low-temperature fixability tends to be inferior.

  Furthermore, when the weight-average molecular weight (Mw) of the THF soluble part of the toner is 8000 to 150,000, low-temperature fixability, high-temperature offset resistance, and other fixing defects can be suppressed. When the weight-average molecular weight (Mw) of the THF-soluble component is less than 8000, high-temperature offset resistance is inferior, and the glossiness (gross) variation on the image is large, and it is easy to form a hard-to-see surface image. When the weight average molecular weight (Mw) is larger than 150,000, the low-temperature fixability is inferior, and the color reproducibility tends to be poor in a full-color image.

In order to make the molecular weight distribution of the THF soluble part of the toner within the above range, a method of adjusting the addition amount of the polymerization initiator, the addition amount of the crosslinking agent, or the like is generally used.

A method for measuring the molecular weight distribution of the THF-soluble component is shown below.
<Method for measuring molecular weight distribution by GPC of THF-soluble matter>
A sample for GPC measurement is prepared as follows.
The toner is put in tetrahydrofuran (THF) and allowed to stand for several hours, then shaken well and mixed well with THF (until the resin is united), and left to stand for 12 hours or more. At this time, the standing time in THF is set to be 24 hours or longer. Thereafter, a sample processing filter (pore size 0.45 to 0.5 μm, for example, manufactured by Maisho Disc H-25-5 manufactured by Tosoh Corporation, Excro Disc 25CR manufactured by Gelman Science Japan, etc.) can be used. Is a GPC sample. The resin concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

The molecular weight and molecular weight distribution by GPC of the THF soluble component of the toner was stabilized by a column in a 40 ° C. heat chamber measured by the following method, and THF was used as a solvent at a flow rate of 1 ml / min. And inject about 100 μl of the THF sample solution. In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polyester sample for preparing a calibration curve, for example, a standard polystyrene sample having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko Co., Ltd. is used. Is appropriate. An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, a combination of shodex GPC KF-801, 802, 803, 804, 805, 806, 807, 800P manufactured by Showa Denko K.K. TSKgel G1000H (H _XL ), G2000H (H _XL ), G3000H (H _XL ), G4000H (H _XL ), G5000H (H _XL ), G6000H (H _XL ), G7000H (H _XL ) It is done.
In particular, the column structure is preferably a combination of A-801, 802, 803, 804, 805, 806 and 807 manufactured by Showa Denko K.K.

  In the present invention, in Soxhlet extraction of a toner using tetrahydrofuran (THF) as a solvent, if the THF-insoluble content B of the binder resin component is 1 to 10% by mass at 16 hours from the start of extraction, low temperature fixability and OHT permeability are obtained. Gloss uniformity can be achieved while maintaining the above.

  When the insoluble content of the toner by Soxhlet extraction with tetrahydrofuran solvent is less than 1% by mass, the toner melt viscosity becomes too low when the fixing speed is low or when fixing on both sides, the glossiness changes greatly, and high temperature offset It tends to occur.

  On the other hand, if the insoluble content of the toner by Soxhlet extraction with a tetrahydrofuran solvent exceeds 10% by mass, the toner will be incompletely melted even if heat is sufficiently applied, and the color mixing and OHT permeability will be poor.

  The amount of THF-insoluble matter in the toner can be adjusted within the above range by appropriately selecting the amount of the toner raw material insoluble in THF such as a colorant or adjusting the amount of the crosslinking agent added during the production of the binder resin. .

The method for measuring the THF-insoluble content is shown below.
<Measurement of THF-insoluble matter>
The THF-insoluble content refers to the mass ratio of the ultra-high polymer component (substantially crosslinked polymer) that has become insoluble in the THF solvent in the resin composition in the toner. The THF-insoluble content is defined as a value measured as follows.

A toner sample of 0.5 to 1.0 g is weighed (W ₁ g), put into a cylindrical filter paper (for example, No. 86R manufactured by Toyo Filter Paper Co., Ltd.), and subjected to a Soxhlet extractor, and 100 to 200 ml of THF is used as a solvent for 6 hours. Extraction and evaporation of the soluble component extracted with the THF solvent are followed by vacuum drying at 100 ° C. for several hours, and the amount of the THF-soluble resin component is weighed (W ₂ g). The mass of a component insoluble in THF such as a colorant in the toner is defined as (W ₃ g). The THF-insoluble content can be obtained from the following formula.

In the present invention, by setting the toner melt index (temperature 135 degrees, load 2.2 kg) in 10 minutes to 5 to 100 g, the low temperature fixability is not impaired, and fatigue is observed even when a large number of sheets are viewed. An image with a stable glossiness can be obtained. When the melt index of the toner is less than 5, the fixed image tends to have low gloss. Inferior in low-temperature fixability and OHP permeability. When the melt index of the toner exceeds 100, the glossiness becomes too high, and the image quality is rather poor psychologically.
In the present invention, a method of adjusting the addition amount of a polymerization initiator, the addition amount of a crosslinking agent, etc. in order to make the discharge amount of a toner melt index (temperature 135 degrees, load 2.2 kg) in 10 minutes 5 to 100 g Is generally used.

A method for measuring the melt index of the toner is shown below.
<Measurement of melt index>
The melt index indicates a discharge amount in 10 minutes at an arbitrary temperature and load. In this invention, it is set as the value measured on condition of the following. This basically conforms to <JlS standard K-7210>.

  Semi-automatic 2-A Melt Index (Toyo Seiki Co. Ltd) is used as a measuring device. An orifice having a cavity inner diameter of 2.095 mm is put, the temperature is adjusted to 135 ° C. in advance, and 3 to 8 g of a toner sample is weighed and put therein. At this time, set the metal piston while being careful not to enter air bubbles, and keep the temperature for 5 minutes or more. Thereafter, measurement is performed while applying a constant load such that the total of the piston and the weight is 2.2 kg. The measurement may be performed at an arbitrary time and converted to a discharge amount of 10 minutes.

  In the present invention, the average circularity is preferably 0.940 to 1.000 (in the particle size distribution based on the equivalent circle diameter measured by the flow particle image analyzer of toner. Here, the flow particle image measurement device. Is an apparatus that statistically performs image analysis of particle imaging, and the average circularity is calculated by the arithmetic average of the circularity obtained by the following equation using the apparatus.

  In the above formula, the perimeter of the particle projection image is the length of the contour line obtained by connecting the edge points of the binarized particle image, and the perimeter of the equivalent circle is the binarized particle This is the length of the outer circumference of a circle having the same area as the image.

The equivalent circle diameter is the diameter of a circle having the same area as the area of the measured two-dimensional image of the particles.
FPIA-1000 (manufactured by Toa Medical Electronics Co., Ltd.) is used as a flow type particle image measuring device.
As a measurement method, a measurement sample is added to 10 ml (20 ° C.) of a solution prepared by adding 0.1 to 0.5% by mass of a surfactant (preferably Contaminone manufactured by Wako Pure Chemical Industries, Ltd.) to ion-exchanged water. 0.02 g is added and uniformly dispersed to prepare a sample dispersion.

  The dispersion is prepared by using an ultrasonic disperser UM-50 manufactured by SMT Co., Ltd. (vibrator is a titanium alloy chip having a diameter of 5 mm), the dispersion time is 5 minutes, and the temperature of the dispersion medium is 40 ° C. or higher. Cool so that it does not become. In the measurement, the range of 0.60 to 400 μm is divided into 226 channels, and in the actual measurement, particles are measured in a range where the equivalent circle diameter is 0.60 μm or more and less than 159.21 μm.

  When the average circularity is 0.940 to 1.000, the density of the toner layer increases and the toner is easily welded when heated. Further, it is possible to improve the transparency and minimize the change in hue angle even in the transmitted light of the transparency image.

  On the other hand, when the average circularity is less than 0.940, the surface of the toner is rough, so that the transmittance is lowered and the hue angle is easily changed due to irregular reflection. In addition, since the toner is irregularly shaped, bubbles remain in the interior and the OHT permeability is lowered. Black toner is also less likely to cause offset because of its low fillability.

  In the present invention, examples of the method for producing the toner having the specific average circularity described above include a method for producing a toner by mechanically or thermally spheroidizing toner particles produced by a pulverization method, and Examples thereof include a method for producing a toner by a suspension granulation method.

  In the present invention, the average circularity is more preferably 0.950 to 1.000 in the particle size distribution by the equivalent circle diameter measured by the flow type particle image analyzer of toner.

In the present invention, the methanol wettability half value of the toner particles is preferably 50 to 75%. As a result, an image having good low-temperature fixability and stable gloss can be obtained.
The toner of the present invention has an external additive added, and the toner including the external additive is referred to as “toner”, and the toner before the external additive is added is referred to as “toner particle”.

  When the methanol wettability half-value is in the above range, the toner particles contain an appropriate amount of wax on the toner surface, which is excellent in low-temperature fixability and offset resistance, and the hydrophilic group on the surface is appropriate. It is preferable because the development characteristics are good. If the methanol wettability half-value of the toner particles is less than 50%, the hydrophilicity of the toner tends to be too high and the chargeability under high temperature and high humidity tends not to be satisfactory, and there is almost no wax on the toner particle surface. It is difficult to achieve satisfactory low-temperature fixability. If the half-value of methanol wettability of the toner particles exceeds 75%, too much wax is present on the toner particle surface, and it is difficult to satisfy storage stability and development stability.

  In order for the methanol wettability half-value of the toner particles to fall within the above range, an appropriate amount of wax existing on the surface of the toner particles may be present. Specifically, the amount of wax on the surface may be controlled by changing the amount of wax added or by performing a heat treatment after the toner particles are produced.

<Measurement of methanol wettability half value>
In the present invention, the methanol wettability half value is determined as follows. Ion-exchanged water 42cm ³ in a beaker, weighed the methanol 28cm ^3. In the present invention, since the methanol wettability half-value is 50% or more, the measurement is started from an initial concentration of 40%. 0.0100 g of a sample is placed in an aqueous methanol solution, and the transmittance is measured using a powder wettability tester WET-100P (manufactured by Resuka Co., Ltd.). For the transmittance measurement, a semiconductor laser having an output of 3 mW and a wavelength of 780 nm was used. Measurement conditions are a stirrer rotational speed of 5 s ⁻¹ and a methanol flow rate of 1.3 cm ³ per minute. When the transmittance before addition of the sample is I _{0 (} 100%), the transmittance at the time of measurement is I (%), and the minimum measured transmittance is I _min (%), the methanol wettability half-value is the transmittance I Is expressed as the volume% of methanol used when I = 100 − [(I ₀ −I _min ) / 2] (%). The methanol wettability half value is calculated as follows.

Methanol wettability half value (%) = {[methanol use amount (cm ³ )] / [methanol use amount + 42.0 (cm ³ )]} × 100

Here, the volume% of methanol used at the transmittance I _min has the same meaning as the degree of hydrophobicity of methanol, and this point is defined as the end point of methanol wettability.

Methanol wettability end point (%) = {[total amount of methanol used up to the minimum transmittance (cm ³ ))
] / [Total amount of methanol used up to the minimum transmittance +42.0 (cm ³ )]} × 100

The toner of the present invention contains 0.5 to 10% by mass of wax.
When the amount of the wax is less than the lower limit, the offset prevention effect tends to be lowered, and when the upper limit is exceeded, the anti-blocking effect is lowered and the offset effect is liable to be adversely affected. It tends to cause fusion to the developing sleeve.

  Examples of the wax used in the toner of the present invention include paraffin wax, polyolefin wax, modified products thereof (for example, oxides and grafted products), higher fatty acids and metal salts thereof, amide wax, ketone wax, and the like. Examples include ester waxes.

In the molecular weight distribution measured by GPC (gel permeation chromatography), the wax used in the present invention has a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (Mw / Mn) of 1.0 to 2.0. 0 is preferred. The closer the value of Mw / Mn of the wax is to 1.0, the sharper the molecular weight distribution. Specifically, it exhibits good melting characteristics when heat is applied during fixing, quickly exudes to the toner surface, and shows good fixing characteristics. Thus, a synergistic effect can be obtained by combining with the control of the material on the toner surface described above. On the other hand, if Mw / Mn is larger than 2.0, the seepage of the wax onto the toner surface is delayed, and the fixing characteristics are deteriorated.

The molecular weight of the wax is measured by GPC under the following conditions.
[GPC measurement conditions]
Apparatus: GPC-150C (Waters)
Column: GMH-HT30cm ² series (manufactured by Tosoh Corporation)
Temperature: 135 ° C
Solvent: o-dichlorobenzene (0.1% ionol added)
Flow rate: 1.0 ml / min
Sample: 0.4 ml injection of 0.15% sample A molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used to calculate the molecular weight of the sample. Furthermore, it calculates by converting into polyethylene by the conversion formula derived from the Mark-Houwink viscosity formula.

The toner of the present invention may contain a charge control agent for controlling the toner to be negatively charged or positively charged.
The following substances are used for controlling the toner to be negatively charged. For example, there are organometallic compounds, chelate compounds, monoazo metal compounds, acetylacetone metal compounds, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid metal compounds. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol. Also, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, silicon compounds, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, styrene- An acrylic-sulfonic acid copolymer, a nonmetal carboxylic acid compound, etc. are mentioned. Further, a resin having the charge control compound pendant may be internally added to the toner.

  The following substances are used to control the toner to be positively charged. For example, modified products with nigrosine and fatty acid metal salts, guanidine compounds, imidazole compounds, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like Onium salts such as phosphonium salts and their lake pigments, triphenylmethane dyes and their lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, Gallic acid, ferricyanide, ferrocyanide, etc.), metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate Dioctyl tin borate, diorgano tin borate such as dicyclohexyl tin borate; can be used in combination of these alone, or two or more kinds. Among these, charge control agents such as nigrosine and quaternary ammonium salts are particularly preferably used. Further, a resin having the charge control compound pendant may be internally added to the toner.

  These charge control agents may be used in an amount of 0.01 to 20 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin in the toner.

As the colorant used in the present invention, generally used black colorant, yellow colorant, magenta colorant, and cyan colorant are used.
Specifically, as the black colorant, a black colorant that is toned in black using the following yellow / magenta / cyan colorant in addition to carbon black is used.

  As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, allylamide compounds, and the like are used. Specifically, C.I. I. Pigment Yellow 3, 7, 10, 12, 13, 14, 15, 17, 23, 24, 60, 62, 74, 75, 83, 93, 94, 95, 99, 100, 101, 104, 108, 109, 110 111, 117, 123, 128, 129, 138, 139, 147, 148, 150, 166, 168, 169, 177, 179, 180, 181, 183, 185, 191, 192, 170, 199, etc. Used. In addition, C.I. I. Solvent Yellow 33, 56, 79, 82, 93, 112, 162, 163, C.I. I. Disperse Yellow 42, 64, 201, 211 etc. are mentioned. If necessary, yellow pigments and dyes may be used alone, or pigments and dyes may be used in combination.

As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds and the like are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 169, 177, 184, 185, 202, 206 220, 221, 254 and C.I. I. Pigment Violet 19 and the like are particularly preferable. If necessary, magenta pigments and dyes may be used alone or in combination with pigments and dyes.

  As the cyan colorant used in the present invention, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like can be used particularly preferably. Further, if necessary, a cyan pigment and a dye may be used alone, or a pigment and a dye may be used in combination.

  These colorants may be used alone or in combination, and can be used in the form of a solid solution. The colorant in the present invention is appropriately selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The addition amount of the colorant is used by adding 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

The toner of the present invention preferably contains at least one colorant having an absolute value of a two-component tribo with a ferrite carrier at room temperature and normal humidity of 5 to 60 (mC / kg).
In the present invention, by selecting the colorant so that the absolute value of the two-component tribo is within the above range, good offset resistance and good charging characteristics can be obtained. When the absolute value of the tribo of the colorant to be used is less than 5 (mC / kg), the chargeability of the toner is inferior and the development characteristics such as fog tend to be unsatisfactory. On the other hand, when the tribo absolute value of the colorant used exceeds 60 (mC / kg), the chargeability of the toner is too high, and the development characteristics such as image uniformity are not satisfactory, or the fixing member such as a roller is not satisfactory. Electrostatic offset is likely to occur.

The absolute value of tribo is measured as follows.
<Tribo measurement of colorant>
The tribo amount of the colorant is obtained by mixing 99.5 parts by mass of a resin-coated ferrite carrier with 0.5 parts by mass of the colorant, and then leaving it at room temperature and normal pressure for 24 hours, and then using a good shaker for 2 minutes. After shaking, measure as follows. The ferrite carrier used at this time was a ternary ferrite core of Cu—Zn—Fe (Fe about 50%, Cu about 10%, Zn about 10%), polyvinylidene fluoride and styrene- A mixture prepared by coating about 1% by mass of a mixture of methyl methacrylate copolymer in a ratio of 50:50 and using 250 mesh pass and 350 mesh on at 70% by mass or more is used.

FIG. 3 is an explanatory diagram of an apparatus for measuring the tribo charge amount of toner. First, in a metal measuring container 102 having a 500 mesh screen 103 at the bottom, a mixture of toner and carrier in a weight ratio of 1:19 to be measured for triboelectric charge is put in a polyethylene bottle having a capacity of 50 to 100 ml. Shake by hand for 5-10 minutes, put about 0.5-1.5 g of the mixture and cap the metal lid 104. The total weight of the measurement container 102 at this time is weighed and is defined as W ₁ (g). Next, in the suction machine 101 (at least the part in contact with the measurement container 102 is an insulator), the pressure of the vacuum gauge 105 is set to 250 mmAq by suction from the suction port 107 and adjusting the air volume control valve 106. In this state, the toner is removed by suction for 2 minutes. The potential of the electrometer 109 at this time is set to V (volt). Here, 108 is a capacitor, and the capacity is C (μF). The total weight of the measurement container after the suction is weighed and defined as W ₂ (g). The triboelectric charge of this colorant (
mC / kg) is calculated using the following equation.

Next, a method for producing the toner of the present invention will be described. The toner of the present invention can be produced using a pulverized toner production method, a suspension granulation toner production method, or the like.
The pulverized toner manufacturing method is performed by sufficiently mixing a binder resin, wax, a pigment as a colorant, a dye, and if necessary, a magnetic material, a charge control agent, and other additives using a mixer such as a Henschel mixer or a ball mill; The obtained mixture is melt-kneaded using a heat kneader such as a heating roll, a kneader, or an extruder, and the wax, pigment, dye or the like is dispersed or dissolved in the resin components mutually compatible; After cooling and solidifying, toner particles can be obtained by pulverization and classification.

In the suspension granulated toner production method, at least a colorant, a wax and, if necessary, a magnetic substance, a charge control agent, a polymerization initiator, a crosslinking agent and other additives are added to the polymerizable monomer constituting the binder resin, Cleamix (M Technique Co., Ltd.) in a dispersion medium containing a dispersion stabilizer, a polymerizable monomer composition that has been uniformly dissolved or dispersed by a commonly used stirrer, homogenizer, ultrasonic disperser, etc. Made of a polymerizable monomer composition, dispersed by a high shearing stirrer used as a polymerization vessel having a heating / stirring means, such as a homomixer (made by Koki Kogyo Kogyo Co., Ltd.). The stirring speed and time are adjusted so that the droplets have the desired toner particle size, and a polymer particle suspension is prepared.

  Polymerization is carried out at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. Further, for the purpose of obtaining a desired molecular weight distribution, the temperature may be raised in the latter half of the polymerization reaction, and in order to remove unreacted polymerizable monomers, by-products, etc. May be distilled off by distillation. The distillation operation can be performed under normal pressure or reduced pressure.

  After completion of the polymerization reaction or subsequent distillation operation, the produced toner particles are filtered / washed, and the dispersion stabilizer on the obtained particulate surface is removed by acid and / or alkali treatment before or after this step. You can also. The toner particles finally separated from the liquid phase are dried by a known method.

  Any appropriate stabilizer is used for the dispersion medium used when the toner particles are produced by the suspension granulated toner production method. For example, as an inorganic compound, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate , Bentonite, silica, alumina and the like. Organic compounds include polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, polyacrylic acid and its salts, starch, polyacrylamide, polyethylene oxide, nonionic or ionic surfactants, etc. used.

  Among these stabilizers, when an inorganic compound is used, a commercially available one may be used as it is, but in order to obtain fine particles, the inorganic compound may be produced in a dispersion medium.

  Moreover, you may use 0.001-0.1 mass part surfactant for fine dispersion | distribution of these stabilizers. This is to promote the desired action of the dispersion stabilizer, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, lauric acid. Examples thereof include sodium, potassium stearate, calcium oleate and the like.

  The toner particles of the present invention can be obtained by sufficiently mixing the obtained toner particles and a desired external additive by a mixer such as a Henschel mixer.

As the external additive, inorganic fine powder such as silicate fine powder, titanium oxide, and aluminum oxide is preferable, and it is further hydrophobized with a hydrophobizing agent such as a silane coupling agent, silicone oil, or a mixture thereof. Is more preferable.
The external additive is usually used in an amount of 0.5 to 2.0 parts by mass with respect to 100 parts by mass of the toner particles.

(2) Image forming apparatus of the present invention The toner of the present invention is exemplified below with reference to the drawings. However, the toner of the present invention is used in an image forming apparatus having at least a surface heating type heat and pressure fixing device. Combinations of the image forming apparatuses are also within the scope of the present invention.

  The image forming apparatus of the present invention heats the surface of the rotating body by forming a rotating body, a counter member that forms the fixing nip with the rotating body, and the rotating body at a portion different from the fixing nip. A heating member including a heating member carrying an unfixed toner image in the fixing nip portion, being nipped and conveyed, and heated by the heat of the rotating body to fix the toner image on the heating material. At least a heat and pressure fixing device is provided, and a photoreceptor, an electrostatic latent image forming device, a charging device, a developing device, a transfer device, and the like can be the same as those in a normal image forming device.

  FIG. 2 is a schematic configuration diagram of an example of the image forming apparatus, but the present invention is not limited to this. The image forming apparatus of the present invention is an electrophotographic full color printer.

  Reference numeral 11 denotes an electrophotographic photosensitive drum (hereinafter referred to as “photosensitive drum”) made of an organic photosensitive member, which is rotated counterclockwise at a predetermined process speed as indicated by an arrow.

  The photosensitive drum 11 undergoes a uniform charging process with a predetermined polarity and potential by a charging device 12 such as a charging roller during the rotation process. Next, the charged surface is subjected to scanning exposure processing of target image information by a laser beam 13a output from a laser optical box (laser scanner) 13 which is an electrostatic latent image forming apparatus. The laser optical box 13 scans the surface of the photosensitive drum by outputting a laser beam 13a modulated (on / off) corresponding to a time-series electric digital pixel signal of target image information from an image signal generator such as a computer (not shown). In this exposure, an electrostatic latent image corresponding to the target image information scanned and exposed on the surface of the photosensitive drum 11 is formed by this scanning exposure. A mirror 13 b reflects the output laser beam 13 a from the laser optical box 13 to the exposure position of the photosensitive drum 11.

  In the case of full-color image formation, scanning exposure and electrostatic latent image formation are performed on a first color separation component image of a target full-color image, for example, a yellow component image, and the electrostatic latent image is formed by the four-color developing device 14. Of these, the yellow developing device 14Y is operated to develop a yellow toner image. The yellow toner image is transferred onto the surface of the intermediate transfer drum 16 at the primary transfer portion T1 which is a contact portion (or proximity portion) between the photosensitive drum 11 and the intermediate transfer drum 16. The surface of the photosensitive drum 11 after the transfer of the toner image to the surface of the intermediate transfer drum 16 is cleaned by the cleaner 17 after removing adhesion residue such as transfer residual toner.

  The process cycle of charging, scanning exposure, development, primary transfer, and cleaning as described above is performed when the target full-color image is second (for example, magenta component image, magenta developing device 14M is activated), and third (for example, cyan component image, Cyan developing device 14C is operated) and fourth (for example, black component image, black developing device 14BK is operated) color separation component images are sequentially executed, and a yellow toner image, a magenta toner image, and a cyan toner are formed on the surface of intermediate transfer drum 16. The four color toner images of the image and the black toner image are sequentially superimposed and transferred, and a color image corresponding to the target full-color image is synthesized and formed.

The intermediate transfer drum 16 has a middle resistance elastic layer and a high resistance surface layer on a metal drum, and is in a clockwise direction indicated by an arrow at substantially the same peripheral speed as the photosensitive drum 11 in contact with or close to the photosensitive drum 11. And a bias potential is applied to the metal drum, and the toner image on the photosensitive drum 11 side is transferred to the surface of the intermediate transfer drum 16 by the potential difference from the photosensitive drum 11.
The color toner image synthesized on the surface of the intermediate transfer drum 16 is transferred at a predetermined timing from a paper supply unit (not shown) at a secondary transfer unit T2 which is a contact nip portion between the intermediate transfer drum 16 and the transfer roller 15. The recording material P is transferred to the surface of the recording material P conveyed to the next transfer portion T2, and the recording material P is in a state of carrying an unfixed toner image. The transfer roller 15 supplies a charge having a polarity opposite to that of the toner from the back surface of the recording material P to the intermediate transfer drum 16, whereby the combined color toner images are sequentially and collectively transferred from the surface of the intermediate transfer drum 16 to the recording material P side. .

The recording material P that has passed through the secondary transfer portion T2 is separated from the surface of the intermediate transfer drum 16 and introduced into the heat and pressure fixing device 10, and the unfixed toner image carried on the recording material P undergoes heat fixing processing. As a full-color image formed product, it is discharged to a discharge tray (not shown) outside the apparatus.
The heat and pressure fixing device 10 is a heat and pressure fixing device according to the present invention. The heat and pressure fixing device 10 will be described in detail in the next section (3).

After the color toner image is transferred onto the recording material P, the intermediate transfer drum 16 is cleaned by removing residual toner and paper dust and the like by a cleaner 18. The cleaner 18 is normally held in a non-contact state with the intermediate transfer drum 16, and is held in contact with the intermediate transfer drum 16 during the secondary transfer of the color toner image from the intermediate transfer drum 16 to the recording material P. The
The transfer roller 15 is also held in a non-contact state with the intermediate transfer drum 16 before the fourth color (BK in the present embodiment) is formed, and the color from the intermediate transfer drum 16 to the recording material P is maintained. The toner image is held in contact with the intermediate transfer drum 16 in the secondary transfer execution process.

In contrast to the full-color image forming operation, in the mono-color image forming operation, only the black developing device 14BK is operated and the developing device is not switched. The next page image can be continuously formed on the intermediate transfer drum 16, and the transfer roller 15 and the cleaner 18 perform a series of image forming operations while being in contact with the intermediate transfer drum 14.
By repeating the above operation, image formation can be performed one after another.

(3) Heating and Pressing Fixing Device According to the Present Invention FIG. 1 is a schematic cross-sectional view of a surface heating type heating and pressing fixing device 10 according to the present invention. The heat and pressure fixing device 10 includes a fixing roller 1 as a rotating body for heating the recording material P that is a material to be heated, and a pressure roller 3 as an opposing member that forms the fixing nip portion N1 with the fixing roller 1. And a surface heating unit 2 as a heating member for heating the surface of the fixing roller 1, and temperature control means 5, 100, 101 for controlling the heating temperature of the fixing roller by the surface heating unit 2.

The fixing roller 1 is formed of a core metal 1a made of a material such as aluminum or SUS, and a silicone rubber, fluoro rubber, fluorosilicone rubber, or the like having a thickness of 0.5 to 10 mm that covers the outer periphery of the core metal. An elastic roller having an outer diameter of 30 to 60 mm composed of the elastic layer 1b and a layer 1c having an outer periphery coated with PFA, PTFE, FEP resin or the like with a thickness of 1 to 100 μm is preferably used.

Similarly, the pressure roller 3 is made of a core metal 3a made of a material such as aluminum or SUS, and a silicone rubber, a fluoro rubber, a fluorosilicone rubber, etc. having a thickness of 0.5 to 10 mm that covers the outer periphery of the core metal. It is an elastic roller having an outer diameter of 30 to 60 mm composed of an elastic layer 3b to be formed and a layer 3c whose outer periphery is coated with PFA, PTFE, FEP resin or the like with a thickness of 1 to 100 μm, and has a predetermined pressure (50 to 800 N). ) To pressurize the fixing roller 1 to form a fixing nip portion N1 as a heated material heating nip portion.

  The surface heating unit 2 is obtained by externally fitting an endless belt-shaped (cylindrical) heating film 2a around a heater holder 2c that supports a heater 2b such as a ceramic heater as a heating means (heating source). The pressure stay 2d presses the heater holder 2c against the fixing roller 1 against the elasticity of the elastic layer 1b of the fixing roller 1, and presses the heater 2b against the fixing roller 1 via the heating film 2a, thereby heating the nip. Part N2 is formed.

  As the heating film 2a, a surface of PI (polyimide) having a thickness of 10 to 1000 μm coated with 1 to 100 μm of PFA, PTFE, FEP resin or the like can be used.

  The heating source used for the surface heating unit 2 is not limited to a ceramic heater. For example, a PTC (Positive Temperature Coefficient) heater, an electromagnetic induction heating member, or the like can be used. As the ceramic heater, a ceramic plate whose surface is insulated can be used instead of the ceramic insulating substrate. Further, a non-contact type heating member such as an infrared lamp device may be used.

  The fixing roller 1 is driven to rotate in the clockwise direction indicated by the arrow in FIG. As the fixing roller 1 is driven to rotate, the pressure roller 3 is driven to rotate counterclockwise as indicated by an arrow due to friction in the fixing nip portion N1. Further, the heating film 2a of the surface heating unit 2 is rotated in the counterclockwise direction indicated by the arrow around the outer side of the heater holder 2c while the inner surface thereof is in sliding contact with the surface of the heater 2b by friction in the heating nip portion N2.

In addition, the heater 2b as a heating unit of the surface heating unit 2 rapidly rises in temperature by being energized from the power supply circuit 101 to the heater 2b. Due to the heat generated by the heater 2b, the surface of the rotary fixing roller 1 is heated through the heating film 2a in the heating nip portion N2.
In the present embodiment, the thermistor 5 as temperature detecting means is brought into contact with the back surface of the heater 2b. Based on the temperature detected by the thermistor 5, the control circuit 100 as temperature control means controls the power supply state from the power supply circuit 101 to the heater 2b so that the surface temperature of the fixing roller 1 is maintained at a predetermined fixing temperature. Temperature control is controlled.

  As the fixing roller 1 is driven to rotate, the pressure roller 3 and the heating film 2a of the surface heating unit 2 are driven to rotate, and the heater 2b of the surface heating unit 2 is energized so that the surface temperature of the fixing roller 1 is a predetermined value. In a state where the heating temperature is adjusted to the fixing temperature, the recording material P carrying the unfixed toner image t as the material to be heated is introduced into the fixing nip portion N1 between the fixing roller 1 and the pressure roller 3. As a result, the recording material P is brought into close contact with the outer surface of the fixing roller 1 and passes through the fixing nip portion N1 together with the fixing roller 1, and in the process of passing through the fixing nip portion, the toner is generated by heat conduction from the fixing roller 1. The image t is heated and fixed to the recording material P by heating. The recording material P that has passed through the fixing nip portion N1 is separated from the outer surface of the fixing roller 1 and conveyed on the recording material outlet side of the fixing nip portion N1.

Although the roller of the heating / pressurizing apparatus is exemplified in FIG. 1, the rotating body is not limited to the roller, but may be a rotating belt. Also for the pressure roller 3, a pressure film unit comprising an endless belt and a pressure member as disclosed in JP-A-2001-228731 can be used instead of the roller.
The fixing nip portion N1 composed of the rotating body and the opposing member in the heat and pressure fixing device of the present invention is formed with a nip portion having a width of 5.0 to 15.0 mm in order to ensure good fixability. preferable. If the width of the fixing nip portion N1 is less than 5.0 mm, it becomes difficult to give a sufficient amount of heat for fixing the toner to the unfixed toner at the time of full color image formation, and the toner cannot be melted and mixed, resulting in an unnatural color. Since it tends to be an image, it is not preferable.

  If the width of the fixing nip N1 exceeds 15.0 mm, a sufficient amount of heat can be applied to fix the toner image, but it is not preferable because hot offset tends to occur during fixing.

Further, the pressure (surface pressure) of the fixing nip portion N1 in the heat and pressure fixing device of the present invention is in the range of surface pressure 9 × 10 ^{3 to} 3 × 10 ⁵ (N / m ² ) through the recording material. Is preferred. When the surface pressure is less than 9 × 10 ³ N / m ^2, it is not preferable because conveyance blur of the recording material is likely to occur and fixing failure due to insufficient fixing pressure is likely to occur. Further, when the surface pressure exceeds 3 × 10 ⁵ N / m ² , the durability deterioration of the rotating body is likely to be deteriorated and the offset is likely to be deteriorated, which is not preferable.

  The surface pressure here refers to the pressure applied to the recording material and the length that the recording material is in contact with the fixing roller (the length in the direction transverse to the paper discharge direction of the recording material (the length in the longitudinal direction of the roller). )) From the following formula.

回転体の回転移動速度（定着速度）は、１００〜２００ｍｍ／ｓｅｃが実用性と定着性を両立して確保する上で好ましい。

The rotational movement speed (fixing speed) of the rotating body is preferably 100 to 200 mm / sec in order to ensure both practicality and fixability.

  The heat-pressure fixing device according to the present invention is not limited to the above-described heat-fixing device, but an image heating device that modifies the surface properties such as gloss by heating a recording material carrying an image, an image heating device that is assumed, It can also be widely used as a means / device for heat-treating a material to be heated, such as a heating / drying device or a heating laminating device.

  EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but this does not limit the present invention in any way.

<Synthesis of binder resin>

<Synthesis example of polyester resin (1)>
The following raw materials are put in a four-neck flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas introduction tube, a catalytic amount of dibutyltin oxide is put, and nitrogen gas is passed through the four-neck flask. The temperature was gradually raised while stirring, the reaction was carried out at 150 ° C. for 10 hours, the temperature was raised to 200 ° C. in the latter half of the condensation polymerization reaction, and the condensation polymerization reaction was promoted under reduced pressure, and the precursor polyester resin (1) (acid value 3 mgKOH / g Thus, a hydroxyl value of 25 mgKOH / g) was obtained.
-55 mol% of diol component represented by the following general formula (1)

(In the formula, R represents an ethylene or propylene group. In this example, the ratio of ethylene-modified diol to propylene-modified diol is a mixed diol of 2: 1.)

・ Fumaric acid 20mol%
・ Terephthalic acid 25mol%
Thereafter, 100 parts by mass of the precursor polyester resin (1) is placed in a four-necked flask and heated to a temperature of 150 ° C., then 1.5 parts by mass of trimellitic anhydride is added and gradually heated to form a polymer of the precursor polyester resin (1). A polyester resin (1) having a terminal modified with trimellitic acid was prepared. The polyester resin (1) had an acid value of 12 mgKOH / g and a hydroxyl value of 15 mgKOH / g.

<Synthesis example of styrene acrylic resin (1)>
The following raw materials are put into a four-neck flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas introduction tube, a catalytic amount of azoisobutyronitrile is put, and nitrogen is put into the four-neck flask. Gradually raise the temperature while stirring through the gas, at 70 ℃
It reacted for 12 hours and obtained the styrene acrylic resin (1) (acid value 1 mgKOH / g).
・ Styrene 75% by mass
・ 25% by mass of n-butyl acrylate
・ Divinylbenzene 0.05 mass%

<Synthesis example of polyester resin (2)>
The amount of addition of the above-mentioned polyester resin synthesis example (1) was changed as follows to obtain a precursor polyester resin (2).
-52 mol% of diol components represented by the above general formula (1)
・ Fumaric acid 20mol%
・ Terephthalic acid 28mol%
Thereafter, 100 parts by mass of the precursor polyester resin (2) was put in a four-necked flask and heated to a temperature of 150 ° C., 0.5 parts by mass of trimellitic anhydride was added, and the mixture was gradually heated to form a polymer of the precursor polyester resin (2). A polyester resin (2) whose terminal was modified with trimellitic acid was prepared. The polyester resin (2) had an acid value of 6 mgKOH / g and a hydroxyl value of 7 mgKOH / g.

<Synthesis example of polyester resin (3)>
The amount of addition of the above-mentioned polyester resin synthesis example (1) was changed as follows to obtain a precursor polyester resin (3).
-58 mol% of diol components represented by the above general formula (1)
・ Fumaric acid 20mol%
・ Terephthalic acid 22mol%
Thereafter, 100 parts by mass of the precursor polyester resin (3) was placed in a four-necked flask and heated to a temperature of 150 ° C., then 2.5 parts by mass of trimellitic anhydride was added, and the mixture was gradually heated to form a polymer of the precursor polyester resin (3). A polyester resin (3) whose terminal was modified with trimellitic acid was prepared. The polyester resin (3) had an acid value of 24 mgKOH / g and a hydroxyl value of 28 mgKOH / g.

<Synthesis example of polyester resin (4)>
The addition amount of the above-mentioned polyester resin synthesis example (1) was changed as follows, and a polyester resin (4) was obtained without subsequent modification treatment. The acid value and hydroxyl value are shown in Table 1.
-55 mol% of diol components represented by the above general formula (1)
・ Fumaric acid 20mol%
・ Terephthalic acid 19mol%
・ Trimellitic acid 6mol%

<Synthesis example of polyester resin (5)>
A polyester resin (5) was obtained in the same manner as in Synthesis Example (1) for polyester resin described above except that the reaction time was shortened to synthesize the precursor polyester. The acid value and hydroxyl value are shown in Table 1.

(Synthesis example of polyester resin (6))
Styrene 8.9 mol%, 2-ethylhexyl acrylate 0.9 mol%, fumaric acid 0.7 mol%, α-methylstyrene dimer 0.1 mol%, dicumyl peroxide 0.8
2 mol% is put into the dropping funnel. Further, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 31.3 mol%, polyoxyethylene (2.2
) -2,2-bis (4-hydroxyphenyl) propane 13.4 mol%, terephthalic acid 13.4 mol%, trimellitic anhydride 8.9 mol%, succinic acid 22.3 mol% and catalytic amount of dibutyltin oxide in glass The flask was placed in a 4-liter four-necked flask and a thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached and placed in a mantle heater. Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually raised while stirring, and while stirring at a temperature of 140 ° C., the monomer of the vinyl resin, the crosslinking agent and the polymerization initiator were added from the previous dropping funnel. The solution was added dropwise over 3 hours. Next, the temperature was raised to 200 ° C. and reacted for 3 hours to obtain a polyester resin (3) (acid value: 16 mgKOH / g). The acid value and hydroxyl value are shown in Table 1.

<Synthesis Example of Comparative Polyester Resin (7)>
The following raw materials are put in a four-neck flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen gas introduction tube, a catalytic amount of dibutyltin oxide is put, and nitrogen gas is passed through the four-neck flask. The temperature was gradually raised with stirring, the reaction was carried out at 150 ° C. for 10 hours, the temperature was raised to 200 ° C. in the latter half of the polycondensation reaction, and the polycondensation reaction was promoted under reduced pressure. Comparative polyester resin (7) (acid value 3 mgKOH / g Thus, a hydroxyl value of 6 mgKOH / g) was obtained.
-50 mol% of diol component represented by the above general formula (1)
・ Fumaric acid 25mol%
・ Terephthalic acid 25mol%

<Synthesis Example of Comparative Polyester Resin (8)>
The amount of addition of the above-mentioned polyester resin synthesis example (1) was changed as follows to obtain a precursor comparative polyester resin (8).
-62 mol% of diol components represented by the above general formula (1)
・ Fumaric acid 20mol%
・ Terephthalic acid 18mol%
Thereafter, 100 parts by mass of the precursor comparative polyester resin (8) was placed in a four-necked flask and heated to a temperature of 150 ° C., then 3.5 parts by mass of trimellitic anhydride was added, and the mixture was gradually heated to prepare the precursor comparative polyester resin (8). A comparative polyester resin (8) in which the polymer terminal was modified with trimellitic acid was prepared. The comparative polyester resin (8) had an acid value of 39 mgKOH / g and a hydroxyl value of 46 mgKOH / g.

<Synthesis Example of Comparative Polyester Resin (9)>
A comparative polyester resin (9) was obtained in the same manner as in the above polyester resin synthesis example (1) except that the reaction time was shortened to synthesize the precursor polyester. Table 3 shows the acid value and hydroxyl value.

<Synthesis Example of Comparative Polyester Resin (10)>
The amount of addition of the above-mentioned polyester resin synthesis example (1) was changed as follows, and a comparative polyester resin (10) was obtained without subsequent modification treatment. Table 3 shows the acid value and hydroxyl value.
-55 mol% of diol components represented by the above general formula (1)
・ Fumaric acid 20mol%
・ Terephthalic acid 13mol%
・ Trimellitic acid 12mol%

<Synthesis Example of Comparative Polyester Resin (11)>
The amount of addition of the above-mentioned polyester resin synthesis example (1) was changed as follows, and a comparative polyester resin (11) was obtained without subsequent modification treatment. Table 3 shows the acid value and hydroxyl value.
-55 mol% of diol components represented by the above general formula (1)
・ Fumaric acid 20mol%
・ Terephthalic acid 15mol%
・ Trimellitic acid 10mol%

<Synthesis Example of Comparative Polyester Resin (12)>
A comparative polyester resin (12) was obtained in the same manner as in Synthesis Example (1) of the polyester resin described above except that the reaction time was slightly shortened to synthesize the precursor polyester. Table 3 shows the acid value and hydroxyl value.

<Manufacture of toner>
(Toner Production Example 1)
Polyester resin (1) 95 parts by mass Styrene acrylic resin (1) 5 parts by mass Paraffin wax (1) 5 parts by mass (DSC endothermic peak: 69 ° C., Mw: 700, Mn: 500)
Charge control agent: aromatic oxycarboxylic acid Zn compound (Bontron E-84: manufactured by Orient Chemical Co., Ltd.) 4 parts by mass Pigment: Yellow pigment 3 parts by mass (CI Pigment. Yellow 185)

The above materials were kneaded and pulverized to obtain a pulverized product.
Thereafter, the pulverized product was subjected to surface treatment with a machine of a type in which a rotor rotates and classified to obtain yellow particles (1). Thereafter, 100 parts by mass of yellow particles (1), 1.0 part by mass of hydrophobized titania fine powder, and 1.0 part by mass of hydrophobized silica fine powder were added. The yellow toner (1) was obtained by uniform diffusion using a Henschel mixer. The physical properties of the yellow toner (1) are shown in Tables 1 and 2.

(Toner Production Examples 2 to 5)
The toner was manufactured in the same manner as in Toner Preparation Example 1 except that the polyester resins (2) to (5) shown in Table 1 were changed to the polyester resin (1) of Toner Preparation Example 1, and the yellow toner was prepared. 2 to 5 were obtained. Table 2 shows the physical properties of Toner 2 to 5 obtained.

(Toner Production Examples 6 and 7)
Toner Production Example 1 except that the amount of paraffin wax (1) added in Toner Production Example 1 was changed from 5 parts by mass as shown in Table 2, and the addition ratio of the polyester resin in the toner was changed as shown in Table 1. The toner was manufactured in the same manner as above, and yellow toners 6 and 7 were obtained. Table 2 shows the physical properties of Toner 6 and 7 obtained.

(Toner Production Example 8)
Instead of the polyester resin (1) of Toner Production Example 1, the polyester resin (2) as shown in Table 1 was changed, and the toner was produced in the same manner as in Toner Production Example 1 except that the surface treatment was not performed after pulverization. As a result, yellow toner 8 was obtained. Table 2 shows the physical properties of Toner 8 thus obtained.

(Toner Production Example 9)
The toner was produced in the same manner as in Toner Production Example 1 except that the polyester resin (1) in Toner Production Example 1 was changed to a polyester resin (6) as shown in Table 1 and subjected to a weak surface treatment after pulverization. As a result, yellow toner 9 was obtained. Table 2 shows the physical properties of Toner 9 thus obtained.

(Toner Production Example 10)
(Pigment dispersion method)
The pigment dispersion was prepared according to the following procedure.
Yellow pigment: (CI Pigment. Yellow 185)
96 parts by mass, pigment dispersant: alcohol-modified polyethylene resin (Mw: 7000) 4 parts by mass, ethyl acetate 100 parts by mass

  Dispersion was carried out with a disperser such as a dispersion liquid attritor (manufactured by Mitsui Mining Co., Ltd.) having the above material composition, and then diluted with ethyl acetate to prepare a pigment dispersion liquid having a pigment concentration of 15% by mass.

(Creation of wax dispersion particles)
A dispersion of micronized wax was prepared by the following procedure.
Paraffin wax (1): 20 parts by mass (DSC endothermic peak: 69 ° C., Mw: 700, Mn: 500)
-Toluene 80 parts by mass The above materials were charged into a disperser. While stirring, the temperature was gradually raised to 100 ° C. and then cooled to room temperature to precipitate finely divided wax. The prepared dispersion of micronized wax was diluted with ethyl acetate so that the mass concentration of the wax was 20% by mass.

[Creation of toner particles]
Polyester resin (1) 95 parts by mass Styrene acrylic resin (1) 5 parts by mass 30 parts by mass of the pigment dispersion, 25 parts by mass of the wax-dispersed particle liquid, and 50 parts by mass of ethyl acetate were dispersed by a ball mill ( This solution was designated as solution A). On the other hand, 60 parts by mass of calcium carbonate (average particle size 80 nm) and 40 parts by mass of water were dispersed with a ball mill, and then 7 parts by mass of calcium carbonate dispersion and carboxymethyl cellulose (trade name “Serogen BS-H”: Daiichi Kogyo Seiyaku Co., Ltd. 100 parts by mass of a 2% aqueous solution of (made)) was stirred (this liquid was designated as B liquid).
Next, 100 parts by mass of B liquid is agitated with an emulsifier (trade name “Auto Homo Mixer” manufactured by Tokushu Kika Kogyo Co., Ltd.), and 50 parts by mass of A liquid is slowly added to suspend the mixed liquid. did. Thereafter, the solvent was removed and hydrochloric acid was added to remove calcium carbonate, followed by washing with water, drying and classification to obtain yellow particles (10). Thereafter, 100 parts by mass of yellow particles (10) were added with 1.0 part by mass of titania fine powder subjected to hydrophobization treatment and 1.0 part by mass of silica fine powder subjected to hydrophobization treatment. The yellow toner (10) was obtained by uniformly diffusing using a Henschel mixer. The physical properties are shown in Tables 1 and 2.

(Toner Production Example 11)
Toner was produced in the same manner as in Toner Production Example 1 except that the yellow colorant in Toner Production Example 1 was changed from PY185 to PY111, and Yellow Toner 11 was obtained. Table 2 shows the physical properties of the obtained toner.

(Toner Production Example 12)
Toner was produced in the same manner as in Toner Production Example 1 except that the yellow colorant in Toner Production Example 1 was changed from PY185 to PY128, and yellow toner 12 was obtained. Table 2 shows the physical properties of the obtained toner.

(Toner Production Examples 13 and 14)
Toner Production Example 1 except that the amount of paraffin wax (1) added in Toner Production Example 1 was changed from 5 parts by mass as shown in Table 2, and the addition ratio of the polyester resin in the toner was changed as shown in Table 1. The toner was manufactured in the same manner as above to obtain yellow toners 13 and 14. Table 2 shows the physical properties of the obtained toner.

(Production Examples 15 and 16 for comparison toner)
The toner was produced in the same manner as in Toner Production Example 1 except that the polyester resin (7) was changed to the polyester resin (7) or (8) as shown in Table 3 in place of the polyester resin (1) of Toner Production Example 1. 15 and 16 were obtained. The obtained toner physical properties are shown in Tables 3 and 4.

(Comparative toner production examples 17 and 18)
Instead of the polyester resin (1) of toner production example 1, the polyester resin (9) or (10) is changed as shown in Table 3, and the addition amount of the paraffin wax (1) of toner production example 1 is 5 parts by mass. To Toner 4 were produced in the same manner as in Toner Production Example 1 except that the changes were made as shown in Table 4. Thus, yellow toners 17 and 18 were obtained. The obtained toner physical properties are shown in Tables 3 and 4.

(Comparative toner production examples 19 and 20)
The polyester resin (1) of toner production example 1 is changed to the polyester resin (11) or (12) as shown in Table 3, and the addition amount of paraffin wax (1) of toner production example 1 is 5 parts by mass. To toner, toner was manufactured in the same manner as in Toner Preparation Example 1 except that the changes were made as shown in Table 4, and yellow toners 19 and 20 were obtained. The obtained toner physical properties are shown in Tables 3 and 4.

(Comparative Toner Production Example 21)
Toner was produced in the same manner as in Toner Production Example 1 except that the material of Toner Production Example 1 was changed as follows, and Yellow Toner 21 was obtained. The obtained toner physical properties are shown in Tables 3 and 4.
Polyester resin (1) 29 parts by mass Styrene acrylic resin (1) 71 parts by mass Paraffin wax (1) 5 parts by mass (DSC endothermic peak: 69 ° C., Mw: 700, Mn: 500)
Charge control agent: aromatic oxycarboxylic acid Zn compound (Bontron E-84: manufactured by Orient Chemical Co., Ltd.) 4 parts by mass Pigment: Yellow pigment 3 parts by mass (CI Pigment. Yellow 185)

(Toner Production Examples 22 to 24)
The pigment is C.I. I. Pigment Yellow 185 instead of C.I. I. Pigment Red 122; magenta toner (1) was obtained in the same manner as in Toner Production Example 1 except that 5 parts by mass were used. In addition, C.I. I. Pigment Blue 15: 3; cyan toner (1) was obtained in the same manner as in Toner Production Example 1 except that 5 parts by mass were used. Carbon black; black toner 1 was obtained in the same manner as in Toner Production Example 1 except that 5 parts by mass was used. The obtained physical properties are shown in Tables 1 and 2.

<Example 1>
Using the yellow toner (1) obtained in Toner Production Example 1 as a one-component yellow developer, the fixing device of a commercially available plain paper full color printer (LBP-2160, manufactured by Canon Inc.) is modified as shown in FIG. With regard to the evaluation of the fixing temperature range and the fixing characteristics, the fixed image is output while changing the set temperature of the fixing device in a single color mode in a normal temperature and humidity environment (23 ° C., 60%), and gloss (glossiness) It evaluated by performing image evaluation, such as.

Specifically, the fixing device was modified as follows.
The fixing roller 1 is an elastic roller having an outer diameter of 20 mm made of a core metal 1a, a 3 mm thick silicone rubber layer 1b covering the outer periphery of the core metal, and a 50 μm thick PFA resin 1c covering the outer periphery. .
Similarly, the pressure roller 3 is composed of a cored bar 3a, a 3 mm thick silicone rubber layer 3b covering the outer periphery of the cored bar, and a 50 μm thick PFA resin 3c coated on the outer periphery. It is a roller and is pressed against the fixing roller 1 with a predetermined pressure (100 N) to form a fixing nip N1 as a heated material heating nip.

The surface heating unit 2 is an outer end belt (cylindrical) heating film 2a that is rotatably fitted around a heater holder 2c that supports a ceramic heater 2b as a heating means (heating source). The heater holder 2c is pressed against the fixing roller 1 against the elasticity of the elastic layer 1b of the fixing roller 1, and the heater 2b is pressed against the fixing roller 1 via the heating film 2a, thereby forming the heating nip N2. I'm allowed.
The heating film 2a was obtained by coating the surface of a PI (polyimide) resin having a thickness of 40 μm with a 10 μm PFA resin and having a circumference of 56.5 mm. As the ceramic heater 2b, a ceramic heater having an output of 700 W in which a resistor was formed by printing on alumina having a width of 8 mm and a thickness of 1 mm, and the top was protected with glass.

(Measurement method of evaluation items)
Using yellow toner (1), a belt-like shape having a toner carrying amount of 0.5 to 0.6 dg / m ² on the leading edge of the recording paper (tip margin 5.0 mm) having a basis weight of 75 or 80 g / m ² . A toner image was formed, and a fixing test was performed at a process speed of 120 mm / sec using the above-described fixing apparatus shown in FIG. The fixing evaluation results are shown in Table 5.

The fixability test is performed at normal temperature and humidity (23 ° C./60%) unless otherwise specified. As the pressing force, a contact pressure of 1 × 10 ⁵ (N / m ² ) was applied to the fixing nip of 7.5 mm through a paper of 80 g / cm ² .

(Fixing start temperature)
Fixing device rotating body 1 The temperature of the surface layer of the fixing device is adjusted at every 5 ° C. in the temperature range of 100 to 210 ° C., and fixed, and the obtained fixed image is rubbed twice with Sylbon paper applied with a load of 4900 N / m ^2. The temperature at which the image density reduction rate before and after rubbing becomes 10% or less is set as the fixing start temperature. The following four ranks were evaluated according to the degree.
A: The fixing start temperature is less than 125 ° C.
B: The fixing start temperature is 125 ° C. or higher and lower than 140 ° C.
C: The fixing start temperature is 140 ° C. or higher and lower than 155 ° C.
D: The fixing start temperature is 155 ° C. or higher.

(Offset resistance)
The fixing temperature is raised, and the highest temperature at which no offset phenomenon occurs visually is defined as a high temperature offset free temperature, which is used as an index of offset resistance. The following four ranks were evaluated according to the degree. A: The high temperature offset free temperature is 190 ° C. or higher.
B: High temperature offset free temperature is 180 ° C. or higher and lower than 190 ° C.
C: High temperature offset free temperature is 170 ° C. or higher and lower than 180 ° C.
D: High temperature offset free temperature is less than 170 ° C.

(Fixing stability)
10,000 sheets are continuously fed under the condition of the heating member set temperature of 155 ° C., and the fixing properties of the first and 10,000th sheets are confirmed. The obtained fixed image is rubbed twice with Sylbon paper applied with a load of 4900 N / m ² , and fixing is performed when the image density reduction rate before and after the rubbing becomes 10% or less. The following four ranks were evaluated according to the degree.
A: Initially fixed after passing 10,000 sheets and the reduction rate is 10% or less.
B: Fixed at the beginning, but not offset after passing 10,000 sheets, but the density reduction rate is 10% or more.
C: Initially fixed, but offset after 10,000 sheets passed, and the back surface is dirty. D: Offset is in the initial stage.

(Image gross difference)
Nine patch images of 30mm x 30mm size are output on Xerox 4024 paper (75g paper, legal size) or CLC-SK A3 size paper (manufactured by Canon Inc.), heating member set temperature 155 ° C The paper was passed under the condition of a process speed of 120 mm / sec.
From the standpoint of quick start and follow-up of the fixing temperature, in the fixing device cooled in the preheating mode to 50 ° C. or less, printing is started again 30 seconds after the start of heating, 50 sheets are continuously fed, The tip average gloss value and the rear end average gloss value at three positions at the rear end of the image were measured. Evaluation was made according to the following four ranks depending on the degree of the front-rear end gloss difference on the first sheet, the front-rear end gross difference on the 50th sheet, and the gloss difference on the first sheet and the 50th sheet.
The glossiness measuring instrument used in the present invention uses PG-3D (incident angle θ = 75 °) manufactured by Nippon Denshoku Industries Co., Ltd., and the standard surface uses black glass with a glossiness of 96.9. did.
A: The maximum gross difference is less than 4.
B: The maximum gloss difference is 4 or more and less than 8.
C: The maximum gloss difference is 8 or more and less than 12.
D: The maximum gross difference is 12 or more.

(OHP permeability)
The transmittance with respect to the amount of each toner per unit area of the fixed image obtained on the OHP sheet is measured, and the transparency is evaluated using a numerical value at a toner mass of 0.60 dg / m ² per unit area. Paper was passed under conditions of a heating member set temperature of 155 ° C. and a process speed of 40 mm / sec. The transmittance measurement method is described below.
The transmittance is measured using a Shimadzu spectrophotometer UV2200 (manufactured by Shimadzu Corporation), and the transmittance of the OHP film alone is 100%.
For magenta toner: 550 nm
For yellow toner: 410 nm
For cyan toner: 650 nm
The transmittance at the maximum absorption wavelength at is measured. The following four ranks were evaluated according to the degree.
A: The transmittance is 80% or more.
B: The transmittance is 70% or more and less than 80%.
C: The transmittance is 60% or more and less than 70%.
D: The transmittance is less than 60%.

(Image unevenness)
Under the condition of the heating member set temperature of 155 ° C., 10,000 sheets are continuously fed, and unevenness between the first and 10,000th fixed images is confirmed. The following four ranks were evaluated according to the degree.
A: The initial image is uniform after 10,000 sheets are passed.
B: Initially uniform image, but after 10,000 sheets have passed, the image is slightly uneven.
C: The image is slightly uneven at the beginning, but after 10,000 sheets are passed, there is unevenness in any image.
D: There is unevenness in any image already in the initial stage.

(Heating member dirty)
The heating member contamination was evaluated based on the following evaluation criteria by passing 10,000 sheets continuously under the condition of the heating member set temperature of 155 ° C., visually observing the member surface, and further observing image defects.
A: Defects are not recognized at all on the member surface and the image.
B: In the latter half of the durability, the surface of the member is slightly stained but does not appear in the image.
C: In the latter half of the durability, some stains are observed on the surface of the member, and some stains are generated on the image.
D: In the latter half of the durability, the surface of the member is very dirty, and the image is also dirty.

  By controlling the toner shape and toner physical properties to the values specified in the present invention, it is possible to ensure good fixing properties, and in accordance with this, the surface of the system in which the rotating body is heated at a surface of the rotating body different from the fixing nip portion. A heat-type heat and pressure fixing device has good quick start properties, and can obtain images with excellent low-temperature fixing properties and offset resistance.

(Examples 2 to 14)
Evaluation was performed in the same manner as in Example 1 except that yellow toner (2) to (14) was changed to yellow toner (1) instead of yellow toner (1). The results are shown in Table 5.

(Examples 15 to 17)
Evaluation was performed in the same manner as in Example 1 except that the toner was changed to magenta toner (1), cyan toner (1) and black toner (1) as shown in Table 5 instead of yellow toner (1). The results are shown in Table 5.

(Examples 18 to 21)
Evaluation was performed in the same manner as in Example 1 except that the conditions (nip length and nip surface pressure P) of the fixing device were changed as shown in Table 5. The results are shown in Table 5.

(Comparative Examples 1-7)
Evaluation was performed in the same manner as in Example 1 except that yellow toners (15) to (21) were changed as shown in Table 6 instead of yellow toner (1). The results are shown in Table 6.

(Comparative Examples 8 and 9)
Evaluation was performed in the same manner as in Example 1 except that the conditions (nip length and nip surface pressure P) of the fixing device used were changed as shown in Table 6. The results are shown in Table 6.

(Comparative Example 10)
The fixing device used is a conventional fixing device (fixing roller: heated from inside, silicone rubber roller: Asker C hardness 80 °, diameter 46 mm, and pressure roller: unheated silicone rubber roller: Asker C hardness 80 °, diameter 46 mm. Evaluation was carried out in the same manner as in Example 1 except that the change was made to). The results are shown in Table 6.

1 is a schematic cross-sectional view of one embodiment of a heat and pressure fixing device of an image forming apparatus of the present invention. 1 is a schematic configuration diagram of one embodiment of an image forming apparatus of the present invention. It is a schematic explanatory drawing of the measuring apparatus for measuring the triboelectric charge amount of a coloring agent.

Explanation of symbols

1: fixing roller 2a: heating film 2b: ceramic heater 2c: heater holder 3: pressure roller 5: temperature detecting means 10: fixing device 11: photosensitive drum 12: charging device 13: laser scanner 14: developing device 15: transfer roller 16 : Intermediate transfer drum

Claims (19)

A rotating member, a counter member that forms the fixing nip portion with the rotating member, and a heating member that forms a nip portion at a site different from the fixing nip portion and heats the rotating member surface, At least a heating and pressure fixing device for inserting and holding a heated material carrying an unfixed toner image in the fixing nip portion and heating the heated material by the heat of the rotating body to fix the toner image on the heated material. An image forming apparatus that
The toner used in the image forming apparatus is a toner having toner particles having at least a binder resin, a colorant and a wax, and an external additive, and satisfies the following a) to c). .
a) The binder resin contains at least one polyester resin or a polyester unit-containing resin, and the addition ratio of the polyester resin and / or the polyester unit-containing resin in the whole toner is C (mass%). And / or when the acid value of the polyester unit-containing resin is A (mgKOH / g) and the hydroxyl value of the polyester resin and / or polyester unit-containing resin is B (mgKOH / g),
50 ≦ C and 10 ≦ (A + B) × C / 100 ≦ 50;
b) The ratio (G ′ ₅₀ / G ′ ₁₀₀ ) between the storage elastic modulus (G ′ ₅₀ ) of the toner at ₅₀ ° C. and the storage elastic modulus (G ′ ₁₀₀ ) of the toner at 100 ° C. is 5,000 to 70. The storage elastic modulus (G ′ ₁₅₀ ) at a temperature of 150 ° C. of the toner is 1.0 × 10 ^{2 to} 1.0 × 10 ⁵ (dN / m ² ). When the surface pressure at the fixing nip portion is P, the ratio (P / G ′ ₁₅₀ ) to the storage elastic modulus (G ′ ₁₅₀ ) at a temperature of 150 ° C. is 10 to 1500;
c) The toner has a glass transition temperature of 50 to 70 ° C., and in the molecular weight distribution by gel permeation chromatography (GPC) of tetrahydrofuran (THF) soluble matter, the peak molecular weight (Mp) of the main peak is 5000 to 15000. The weight average molecular weight (Mw) is 8000-150000, and Mw / Mn is 1.5-20. The addition ratio of the polyester resin and / or polyester unit-containing resin in the whole toner is C (mass%), the acid value of the polyester resin and / or polyester unit-containing resin is A (mg KOH / g), and the polyester resin and / or The image forming apparatus according to claim 1, wherein the following formula is satisfied when the hydroxyl value of the polyester unit-containing resin is B (mg KOH / g).
15 ≦ (A + B) × C / 100 ≦ 40 2. The toner according to claim 1, wherein, in Soxhlet extraction of toner using tetrahydrofuran (THF) as a solvent, the THF-insoluble content of the binder resin component at 16 hours from the start of extraction is 1 to 15% by mass. The image forming apparatus according to 2. The image forming apparatus according to claim 1, wherein the toner contains 0.5 to 10% by mass of wax. 5. The image forming apparatus according to claim 1, wherein the toner has a melt index (temperature: 135 ° C., load: 2.2 kg) discharged in 5 minutes in an amount of 5 to 100 g. . The image forming apparatus according to claim 1, wherein the toner has an average circularity measured by a flow type particle image analyzer of 0.940 to 1.000. The image forming apparatus according to claim 1, wherein the toner has an average circularity measured by a flow type particle image analyzer of 0.950 to 1.000. The image forming apparatus according to claim 1, wherein the toner particles have a methanol wettability half value of 50 to 75%. 9. The toner according to claim 1, wherein the toner contains at least one colorant having an absolute value of a two-component tribo with a ferrite carrier at room temperature and normal humidity of 5 to 60 (mC / kg). The image forming apparatus according to claim 1. The image forming apparatus according to claim 1, wherein the heat and pressure fixing device is not provided with an oil application mechanism. In the heating and pressing apparatus, a nip width of a fixing nip portion formed by the rotating body and the facing member is 5 to 15 mm, and the rotating body is subjected to a surface pressure of 9 × 10 ^{3 to} 3 through a material to be heated. The image according to any one of claims 1 to 10, wherein the image is a heat-pressure fixing device that heat-presses and fixes a toner image while pressing the opposing member at × 10 ⁵ (N / m ² ). Forming equipment. A rotating member, a counter member that forms the fixing nip portion with the rotating member, and a heating member that forms a nip portion at a site different from the fixing nip portion and heats the rotating member surface, At least a heating and pressure fixing device for inserting a heated material carrying an unfixed toner image into the fixing nip portion, nipping and conveying the heated material, and fixing the toner image on the heated material by heating with the heat of the rotating body is provided. Toner used in an image forming apparatus,
A toner comprising toner particles having at least a binder resin, a colorant, and a wax, and an external additive satisfying the following a) to c).
a) The binder resin contains at least one polyester resin or a polyester unit-containing resin, and the addition ratio of the polyester resin and / or the polyester unit-containing resin in the whole toner is C (mass%). And / or when the acid value of the polyester unit-containing resin is A (mgKOH / g) and the hydroxyl value of the polyester resin and / or polyester unit-containing resin is B (mgKOH / g),
50 ≦ C and 10 ≦ (A + B) × C / 100 ≦ 50;
b) The ratio (G ′ ₅₀ / G ′ ₁₀₀ ) between the storage elastic modulus (G ′ ₅₀ ) of the toner at ₅₀ ° C. and the storage elastic modulus (G ′ ₁₀₀ ) of the toner at 100 ° C. is 5,000 to 70. And the storage elastic modulus (G ′ ₁₅₀ ) of the toner at a temperature of 150 ° C. is 1.0 × 10 ^{2 to} 1.0 × 10 ⁵ (dN / m ² ),
When the surface pressure at the fixing nip portion of the heating device is P, the ratio (P / G ′ ₁₅₀ ) to the storage elastic modulus (G ′ ₁₅₀ ) at a temperature of 150 ° C. is 10 to 1500;
c) The toner has a glass transition temperature of 50 to 70 ° C., and in the molecular weight distribution by gel permeation chromatography (GPC) of tetrahydrofuran (THF) soluble matter, the peak molecular weight (Mp) of the main peak is 5000 to 15000. The weight average molecular weight (Mw) is 8000-150000, and Mw / Mn is 1.5-20. The addition ratio of the polyester resin and / or polyester unit-containing resin in the whole toner is C (mass%), the acid value of the polyester resin and / or polyester unit-containing resin is A (mg KOH / g), and the polyester resin and / The toner according to claim 12, wherein the following formula is satisfied when the hydroxyl value of the polyester unit-containing resin is B (mg KOH / g).
15 ≦ (A + B) × C / 100 ≦ 40 13. The toner according to claim 12, wherein, in the Soxhlet extraction of the toner using tetrahydrofuran (THF) as a solvent, the THF-insoluble content of the binder resin component at 16 hours from the start of extraction is 1 to 15% by mass. The toner according to 13. The toner according to any one of claims 12 to 14, wherein the toner contains 0.5 to 10% by mass of a wax. The toner according to claim 12, wherein the toner has a melt index (temperature of 135 ° C., load of 2.2 kg) discharged in a period of 5 minutes to 5 to 100 g. The toner according to any one of claims 12 to 16, wherein the toner has an average circularity measured by a flow type particle image analyzer satisfying 0.940 to 1.000. The toner according to any one of claims 12 to 16, wherein the toner has an average circularity measured by a flow-type particle image analyzer satisfying 0.950 to 1.000. The toner according to claim 12, wherein the toner particles have a methanol wettability half value of 50 to 75%.

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