JP5505692B2 - Image forming toner, image forming apparatus, image forming method, and process cartridge - Google Patents

Description

  The present invention relates to a toner used for electrophotographic image formation such as a copying machine, electrostatic printing, printer, facsimile, electrostatic recording, and the like, and an image forming apparatus, an image forming method, and a process cartridge using the toner.

  Conventionally, in an electrophotographic image forming apparatus or the like, a latent image formed electrically or magnetically has been visualized with an image forming toner (hereinafter also simply referred to as “toner”). For example, in electrophotography, an electrostatic charge image (latent image) is formed on an electrostatic latent image carrier (hereinafter also referred to as “photosensitive member”), and then the latent image is developed with toner. A toner image is formed. The toner image is usually transferred onto a transfer material such as paper and then fixed on the transfer material such as paper. In the process of fixing a toner image onto a transfer paper, a heat fixing method such as a heating roller fixing method or a heating belt fixing method is widely used because of its energy efficiency.

  In recent years, demands from the market for increasing the speed and energy saving of image forming apparatuses are increasing, and there is a demand for toners that are excellent in low-temperature fixability and transparency and that can provide high-quality images. However, in order to achieve the low-temperature fixability of the toner, it is necessary to lower the softening point of the binder resin. If the softening point of the binder resin is low, a part of the toner image adheres to the surface of the fixing member at the time of fixing, and a so-called offset (hereinafter also referred to as hot offset) occurs on the copy sheet. Further, the heat resistance of the toner is lowered, and so-called blocking occurs in which toner particles are fused with each other particularly in a high temperature environment. In addition, in the developing device, there are problems that the toner is fused and contaminated inside the developing device and the carrier, and that the toner is liable to film on the surface of the photoreceptor.

  One of the measures taken to address these problems is to improve toner physical properties by improving the binder resin. Toners using polylactic acid-containing polyester resins are storage-stable, low-temperature fixability, offset resistance, and environmental stability. It has been proposed as an excellent material and environmental conservation. Compared to polyester resins that have been used in conventional toner applications, the thermal properties of polyester resins containing polylactic acid are not sufficiently controlled, so there are many restrictions on the amount of resin formulated and the manufacturing method, and sufficient storage stability. Low temperature fixability and offset resistance have not been achieved. (See Patent Documents 1 and 2).

  The present invention has been made in view of the above circumstances in the prior art. That is, the present invention provides an image forming toner excellent in thermal characteristics, heat-resistant storage stability, and transparency, and an image forming apparatus, an image forming method, and a process cartridge using the toner.

As a result of intensive studies, the present inventors have found that the above problems can be solved by using a toner having the following constitution, and have reached the present invention.
That is, the present invention is as follows.
(1) A toner containing at least a binder resin and a wax (c), containing a resin (b1) containing a polyhydroxycarboxylic acid skeleton as the binder resin, and the polyhydroxycarboxylic acid of the resin (b1) The monomer that forms the acid skeleton includes an optically active monomer,
The ratio Tm / Tg of the melting point Tm of the wax to the glass transition temperature Tg is in the range of 1.05 to 1.25, the acid value is 6 mgKOH / g or less, and the melting point Tm of the wax is the resin ( An image forming toner characterized by being 15 ° C. or more higher than the glass transition temperature Tg of b1).
(2) Optical purity X (%) in terms of monomer component of the resin (b1) = | X (L form) −X (D form) | [where X (L form) is L in terms of optically active monomer Body ratio (mol%), X (D form) represents D form ratio (mol%) in terms of optically active monomer]] is 80% or less, or the content of the resin (b1) in the total binder resin Y (mass%) and optical purity X (mol%) in terms of monomer component = | X (L form) −X (D form) | [where X (L form) is L form in terms of optically active monomer Ratio (mol%), X (D isomer) represents D isomer ratio (mol%) in terms of optically active monomer], and the relationship satisfies Y ≦ −1.5X + 220 (80 <X ≦ 100) The toner for image formation as described in (1) above.
(3) The image forming toner according to (1) or (2), wherein the polyhydroxycarboxylic acid skeleton is a skeleton obtained by (co) polymerizing a hydroxycarboxylic acid having 2 to 6 carbon atoms.
(4) The above-mentioned (1) to (3), wherein the resin (b1) containing a polyhydroxycarboxylic acid skeleton is a polyester resin comprising a polyester diol (b11) containing a polyhydroxycarboxylic acid skeleton. The toner for image formation as described in any one of 1).
(5) The resin (b1) containing the polyhydroxycarboxylic acid skeleton is a linear polyester resin obtained by reacting a polyester diol (b11) containing a polyhydroxycarboxylic acid skeleton together with an extender. The image forming toner according to any one of (1) to (3), wherein:
(6) The resin (b1) containing the polyhydroxycarboxylic acid skeleton reacts the polyester diol (b11) containing the polyhydroxycarboxylic acid skeleton with a polyester diol (b12) other than (b11) together with an extender. The image-forming toner according to any one of (1) to (3), wherein the toner is a linear polyester-based resin obtained as described above.
(7) The toner for image formation according to any one of (1) to (6), wherein the wax (c) is a wax having an ester bond in a main skeleton.
(8) The image forming toner according to any one of (1) to (7), wherein an inorganic filler is contained in the toner.
(9) The image forming apparatus as described in any one of (1) to (8) above, wherein the image forming toner further contains a modified wax (d) obtained by grafting a vinyl polymer chain onto a wax. Toner.
(10) An electrostatic latent image carrier, charging means for charging the surface of the electrostatic latent image carrier, and exposure means for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image Developing means for developing the electrostatic latent image with toner to form a visible image; transfer means for transferring the visible image to a recording medium; and fixing the transferred image transferred to the recording medium. An image forming apparatus having at least a fixing unit, wherein the toner is the image forming toner according to any one of (1) to (9).
(11) A charging step for charging the surface of the electrostatic latent image carrier, an exposure step for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and the electrostatic latent image with toner. An image forming method comprising at least a developing step for developing a visible image by using the developing method, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium An image forming method, wherein the toner is the image forming toner according to any one of (1) to (9).
(12) At least an electrostatic latent image carrier and a developing unit that develops the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image, and forms an image. A process cartridge that is detachable from an apparatus main body, wherein the toner is the image forming toner according to any one of (1) to (9).

  According to the present invention, it is possible to provide an image forming toner, an image forming apparatus, an image forming method, and a process cartridge that are excellent in thermal characteristics, heat-resistant storage stability, and transparency.

1 is a schematic configuration diagram of an image forming apparatus including a process cartridge having an image forming toner of the present invention.

Regarding the resin (b1) As a result of intensive studies, the inventors have compared conventional resins having a main chain with an aromatic chain, such as styrene acrylic resins and polyester resins, which are binder resins for toners that are often used in the past. The present inventors have found that the resins (b1) containing a polyhydroxycarboxylic acid skeleton are excellent in transparency and excellent in pigment dispersibility and fixability. However, when the monomer that forms the polyhydroxycarboxylic acid skeleton is an optically active monomer such as lactic acid, if the optical purity in terms of monomer component is high, the polyhydroxycarboxylic acid skeleton will have crystallinity, so other constituent materials It has also been found that there is a problem that the resin cannot enter the resin (b1) and the dispersibility with other materials is extremely deteriorated.

  When the monomer that forms the polyhydroxycarboxylic acid skeleton is an optically active monomer such as lactic acid, the optical purity X (%) = | X (L isomer) −X (D isomer) | [where X (L ) Represents the L isomer ratio (mol%) in terms of optically active monomer, and X (D isomer represents the D isomer ratio (mol%) in terms of optically active monomer). It is preferable to reduce the content of the resin (b1) in the binder resin and to increase the portion in the toner where other materials can be dispersed. As a result of the examination, the optical purity X (%) = 80% or less as the optical purity at which the crystallinity of the resin (b1) is lowered and the dispersion failure with other toner constituents derived from crystallization does not manifest. Is more preferable, and 60% or less is more preferable. Within this range, the crystallinity of the resin (b1) is reduced, and poor dispersion with other toner constituent components derived from crystallization can be prevented. From the viewpoint of dispersibility, when the optical purity X (%) is 80% or less, the content of the resin (b1) contained in the total binder resin may be appropriately adjusted within a preferable range depending on the application. Preferably, it is 40-100 mass% with respect to all the binder resin, More preferably, it is 60-100 mass%.

  On the other hand, when the optical purity exceeds 80%, the content of the resin (b1) is preferably adjusted according to the optical purity. From the viewpoint of dispersibility, the content of (b1) with respect to the total binder resin By setting the relationship between the content Y (mass%) of the resin (b1) in the binder resin and X to satisfy the relation Y ≦ −1.5X + 220, poor dispersion with other toner components derived from crystallization can be achieved. Since it can prevent, it is preferable. As a specific example of poor dispersion with other toner constituent components derived from crystallization, for example, when the dispersion of the pigment is poor, a decrease in image density, a decrease in charge amount under high temperature and high humidity conditions, and the like are likely to occur.

  The monomer that forms the polyhydroxycarboxylic acid skeleton constituting (b1) includes an optically active monomer. The polyhydroxycarboxylic acid skeleton has a skeleton obtained by polymerizing hydroxycarboxylic acid, and uses a method of directly dehydrating condensation of hydroxycarboxylic acid, a method of ring-opening polymerization of a corresponding cyclic ester, or an enzymatic reaction such as lipase. It may be created by any known method such as a synthesis method. Examples of the hydroxycarboxylic acid include aliphatic hydroxycarboxylic acids (such as glycolic acid, lactic acid, and hydroxybutyric acid), aromatic hydroxycarboxylic acids (such as salicylic acid, creosote acid, mandelic acid, burric acid, and syringic acid), or a mixture thereof. Corresponding cyclic esters include glycolide, lactide, γ-butyrolactone, 6-valerolactone and the like. Among these, from the viewpoints of transparency and thermal properties, the monomer that forms the polyhydroxycarboxylic acid skeleton is preferably an aliphatic hydroxycarboxylic acid and a cyclic ester, more preferably a hydroxycarboxylic acid having 2 to 6 carbon atoms ( The corresponding cyclic ester is also included, and lactic acid and lactide are particularly preferable as the optically active monomer, and lactic acid is most preferable. Moreover, as a monomer which can be used with an optically active monomer, glycolic acid and glycolide are preferable.

  In addition, when the monomer that forms the polyhydroxycarboxylic acid skeleton is an optically active monomer such as lactic acid, X (D form) and X (L form) of the monomer that forms the hydroxycarboxylic acid skeleton of the resin (b1) are: It becomes equal to the ratio of the D-form and L-form of the monomer used when forming the hydroxycarboxylic acid skeleton. Therefore, the optical purity X (%) in terms of the monomer component of the hydroxycarboxylic acid skeleton of the resin (b1) can be controlled by using a suitable amount of L and D monomers as monomers to obtain a racemate. In the case of using lactide, L-lactide and D-lactide can be mixed and used, but meso-lactide can be used after ring-opening polymerization, or either D-form or L-form lactide and meso-lactide can be used. The optical purity X (%) can also be controlled by using a mixture.

Examples of the resin (b1) containing a polyhydroxycarboxylic acid skeleton include a polyester-based resin composed of a polyester diol (b11) containing a polyhydroxycarboxylic acid skeleton, and a polyester diol (b11) containing a polyhydroxycarboxylic acid skeleton. You may use the linear polyester-type resin obtained by making it react with.
In the resin (b1) containing a polyhydroxycarboxylic acid skeleton, the polyhydroxycarboxylic acid skeleton and a skeleton having another structure may coexist. As a specific example, a linear polyester resin obtained by reacting a polyester diol (b11) other than (b11) with a polyester diol (b12) containing a polyhydroxycarboxylic acid skeleton together with an extender is used. Also good. Linear polyester has a simple structure, and it is easy to control the molecular weight and physical properties (thermal characteristics, compatibility with other resins, etc.) generated thereby. Moreover, the linear polyester-type resin obtained by making polyester diol (b12) other than the polyester diol (b11) and (b11) containing the said polyhydroxycarboxylic acid frame | skeleton with an extending | stretching agent is (b11) and ( b12) unit, and the advantage is that the physical properties of the linear polyester resin can be controlled by the polyester type, molecular weight, and structure used in the unit (b12), and only the polyhydroxycarboxylic acid skeleton is used. The physical property control means can be clearly provided for the resin.

About Resin (b11) When forming a polyhydroxycarboxylic acid skeleton, a polyester diol (b11) containing a polyhydroxycarboxylic acid skeleton is obtained by adding and copolymerizing a diol (11) described later. Preferred as diols are alkylene oxides of 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) (Alkylene oxide is hereinafter abbreviated as AO. Specific examples include ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.) 2-30), and combinations thereof, more preferably 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, and AO adducts of bisphenol A, particularly preferably With 1,3-propylene glycol That.

The polyester diol (b12) other than (b11) can be the same as the reaction product of the diol (11) and the dicarboxylic acid (13) among the polyester resins described later, and charged with the diol and the dicarboxylic acid during the polymerization. It is obtained by adjusting the ratio to make the hydroxyl group excessive. Preferred as (b12) is 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.). One or more diols selected from AO (EO, PO, BO, etc.) adducts (addition moles 2 to 30) and combinations thereof, terephthalic acid, isophthalic acid, adipic acid, succinic acid, and combinations thereof A reaction product with one or more dicarboxylic acids selected from
The hydroxyl value of (b11) and (b12) is preferably 3 to 224, more preferably 5 to 112, and most preferably 10 to 56, from the viewpoint of adjusting the physical properties of (b1).

  Number average molecular weight of resin (b1) (measured by gel permeation chromatography, abbreviated as Mn), melting point (abbreviated as Tm, measured by DSC), glass transition temperature (abbreviated as Tg, measured by DSC) May be adjusted appropriately within the preferred range.

In the present invention, the number average molecular weight (Mn) and the weight average molecular weight (hereinafter abbreviated as Mw) of resins other than polyurethane resins such as polyester resins are gel permeation chromatography for tetrahydrofuran (THF) soluble components. (GPC) is used under the following conditions.
Device (example): Tosoh HLC-8120
Column (example): TSKgelGMHXL (2)
: TSKgelMultiporeHXL-M (1 pc.)
Sample solution: 0.25% THF solution Injection volume: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Tosoh standard polystyrene (TSKstandardPOLYS)
TYRENE) 12 points (molecular weight 500 1050 2800 5970 9100 18
100 37900 96400 190000 355000 1090000 28
90000)

Moreover, Mn and Mw of a polyurethane resin are measured on condition of the following using GPC.
Equipment (example): Tosoh HLC-8220GPC
Column (example): Guardcolumn α TSKgel α-M
Sample solution: 0.125% dimethylformamide solution Solution injection amount: 100 μl
Flow rate: 1 ml / min Temperature: 40 ° C
Detection apparatus: Refractive index detector Reference material: 12 standard polystyrene (TSK standard POLYSTYRENE) manufactured by Tosoh (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000)

  The glass transition temperature (Tg) of the resin was measured using a differential scanning calorimeter (TA-60WS and DSC-60, manufactured by Shimadzu Corporation). 10 mg of a sample was weighed into an aluminum sample pan, and while performing a nitrogen flow (flow rate 50 mL / min), the temperature was increased from 20 ° C. to 200 ° C. at a rate of temperature increase of 10 ° C./min. After the temperature was lowered at min, the DSC curve was measured when the temperature was raised from 20 ° C. to 200 ° C. at a rate of temperature rise of 10 ° C./min. From the obtained DSC curve, the temperature of the intersection of the extended line of the base line below the endothermic peak temperature and the tangent showing the maximum inclination from the peak rising portion to the peak apex was determined and used as the glass transition temperature (Tg).

The number average molecular weight (hereinafter abbreviated as Mn) of (b11) and (b12) is preferably from 500 to 30,000, more preferably from 1000 to 20,000, most preferably from 2000, from the viewpoint of adjusting the physical properties of (b1). 5000.
The Mn of the resin (b1) is preferably 1,000 to 5,000,000, more preferably 2,000 to 500,000. The melting point of the resin (b1) is preferably 20 ° C to 200 ° C, more preferably 80 ° C to 180 ° C. The Tg of the resin (b1) is preferably 20 ° C to 100 ° C, more preferably 40 ° C to 80 ° C.

The extender to be reacted with (b11) and the extender used for extending (b11) and (b12) have two functional groups capable of reacting with the hydroxyl group contained in (b11) and (b12). If it is, it will not restrict | limit in particular, However, The bifunctional thing is mentioned among the below-mentioned dicarboxylic acid (13) and its anhydride, polyisocyanate (15), and polyepoxide (19). Of these, from the viewpoint of compatibility with (b11) and (b12), preferred are diisocyanate compounds and dicarboxylic acid compounds, and more preferred are diisocyanate compounds. Specifically, succinic acid, adipic acid, maleic acid and its anhydride, fumaric acid and its anhydride, phthalic acid, isophthalic acid, terephthalic acid, 1,3- and / or 1,4-phenylene diisocyanate, 2, 4- and / or 2,6-tolylene diisocyanate (TDI), 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane 4,4'- Examples include diisocyanate (hydrogenated MDI), isophorone diisocyanate (IPDI), bisphenol A diglycidyl ether, and among these, succinic acid, adipic acid, isophthalic acid, terephthalic acid, maleic acid (and its anhydride) are preferred. ), Fumaric acid (and its anhydride) HDI, an IPDI, most preferably maleic acid (and its anhydride), fumaric acid (and its anhydride), and IPDI.
The content of the extender in (b1) is preferably 0.1 to 30% by mass, more preferably 1 to 20% by mass, from the viewpoints of transparency and thermal characteristics.

Content of Resin (b1) The content of the resin (b1) contained in the total binder resin may be appropriately adjusted within a preferable range depending on the use. From the viewpoint of dispersibility, preferably, the total binder resin It is 40-100 mass% with respect to it, More preferably, it is 60-100 mass%. Even when the hydroxycarboxylic acid contained in the resin (b1) is an optically active monomer such as lactic acid, the above content is preferable if the optical purity is 80% or less in terms of monomer components. When the optical purity in terms of monomer component exceeds 80%, from the viewpoint of dispersibility, the content of (b1) with respect to the total binder resin is the content Y (mass%) of the resin (b1) in the total binder resin. ) And X preferably satisfy Y ≦ −1.5X + 220.

  The mass ratio of the polyester diol (b11) containing a polyhydroxycarboxylic acid skeleton and the polyester diol (b12) other than (b11) constituting the linear polyester resin is preferably 31:69 to 90: 10 and more preferably 40:60 to 80:20 from the viewpoint of transparency and thermal characteristics.

The toner of the present invention contains at least the above-described resin (b1) as a binder resin, and other resins can be used in combination with (b1). As a binder resin to be used in combination, any known resin may be used in combination, for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin. Aniline resin, ionomer resin, polycarbonate resin and the like. Of these, vinyl resins, polyester resins, polyurethane resins, epoxy resins, and combinations thereof are preferred, polyurethane resins and polyester resins are more preferred, and 1,2-propylene glycol is particularly preferred. Is a polyester resin and a polyurethane resin.
In addition, a non-linear polyester resin obtained by extending the polyester diol (b11) and the trivalent to octavalent or higher polyol (12) with an extender may be used in combination.

(About wax (c))
In general toner, wax has a function of preventing adhesion between the fixing member and the toner by melting at the time of heat fixing (exhibiting releasability), whereas in the toner of the present invention, the wax is It has a function of suppressing the temporal change of the glass transition temperature, which is a problem peculiar to the resin (b1) containing a polyhydroxycarboxylic acid skeleton, and stabilizing thermal characteristics such as heat-resistant storage stability and fixing minimum temperature.

Therefore, as an essential requirement regarding the thermal properties of the wax (c) combined with the resin (b1) containing a polyhydroxycarboxylic acid skeleton, the ratio Tm / Tg of the melting point Tm of the wax and the glass transition temperature Tg is 1.05-1. The melting point Tm of the wax is preferably 15 ° C. or higher than the glass transition temperature Tg of the resin (b1). When using a plurality of resins (b1), the melting point Tm of the wax is 15 ° C. or more higher than the glass transition temperature Tg of the resin (b1). The melting point Tm of the wax is higher than all the glass transition temperatures of the plurality of resins (b1). Means higher by 15 ° C. or more.
Moreover, it is preferable that an acid value is 6 mgKOH / g or less as characteristics other than a thermal characteristic. This is because, in the combination with the resin (b1) containing a polyhydroxycarboxylic acid skeleton, the wax having a lower acid value is more easily dispersed in the resin (b1) and functions as a nucleating agent that promotes crystallization. Easy to demonstrate.

The presence of the wax having Tg, Tm and acid value in the resin (b1) promotes the crystallization of the resin (b1) and quickly terminates the change of the crystalline state, and is inherent to the polyhydroxycarboxylic acid skeleton. Slow changes in glass transition temperature can be suppressed. Further, the resin (b1) containing a polyhydroxycarboxylic acid skeleton is likely to be crystallized when the optical purity of the monomer is high as described above, and the dispersion failure of other toner components tends to be manifested. By setting the optical purity of the monomer of the resin (b1) containing a polyhydroxycarboxylic acid skeleton within a specific range, it is possible to improve poor dispersion of other toner constituent components.
When the melting point Tm of the wax is 15 ° C. or more higher than the glass transition temperature Tg of the resin (b1), the melting point Tm, which is the substantial crystallization temperature of the wax, is higher than the glass transition temperature of the resin (b1). The wax is easily crystallized first with respect to the resin (b1), and the function as a nucleating agent for promoting crystallization is easily exhibited. The effect of promoting the crystallization of the resin (b1) by the wax is that the melting point Tm of the wax is the resin. It becomes remarkable when it is 15 ° C. or more higher than the glass transition temperature Tg of (b1). The smaller the ratio Tm / Tg between the melting point Tm of the wax and the glass transition temperature Tg, the higher the degree of crystallinity of the wax, and the higher the function as a crystal nucleating agent. For this reason, Tm / Tg is in the range of 1.05 to 1.25, and preferably in the range of 1.10 to 1.25. However, if Tm / Tg is less than 1.05, the difference between the crystallization degree of the wax and the crystallization degree of the resin (b1) is too large. Particles are deposited on the surface, and blocking is likely to occur. On the other hand, if it exceeds 1.25, the crystallization promoting effect of the resin (b1) becomes low because the crystallization degree of the wax is small.

  The wax (c) is an unmodified wax and is not particularly limited and can be appropriately selected from known ones according to the purpose. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax Aliphatic hydrocarbon waxes such as paraffin wax and sazol wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; candelilla wax, carnauba wax, wood wax, jojoba wax Plant waxes such as beeswax, animal waxes such as beeswax, lanolin, and whale wax; mineral waxes such as ozokerite, ceresin, and petrolatum; waxes mainly composed of fatty acid esters such as montanate ester wax and caster wax; Acid carnauba Those deoxidizing a part or all of the scan fatty acid esters such as the, and the like.

  Examples of the wax further include saturated straight chain fatty acids such as palmitic acid, stearic acid, montanic acid, and straight chain alkyl carboxylic acids having a straight chain alkyl group, pranzic acid, eleostearic acid, valinal acid, and the like. Unsaturated fatty acid, stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnapyl alcohol, seryl alcohol, mesyl alcohol, saturated alcohol such as long chain alkyl alcohol, polyhydric alcohol such as sorbitol, linoleic acid amide, olefinic acid amide, Fatty acid amides such as lauric acid amide, methylene biscapric acid amide, ethylene bis lauric acid amide, saturated fatty acid bisamides such as hexamethylene bisstearic acid amide, ethylene bisoleic acid amide, hexamethylene bisoleic acid Unsaturated fatty acid amides such as acid amide, N, N′-dioleyl adipate amide, N, N′-dioleyl sepasin amide, m-xylene bisstearic acid amide, N, N-distearyl isophthalic acid Hydrogenating aromatic bisamides such as amides, fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate, fatty acid and polyhydric alcohol partial ester compounds such as behenic acid monoglyceride, and vegetable oils and fats And a methyl ester compound having a hydroxyl group obtained by the above method.

  Further, polyolefins obtained by radical polymerization of olefins under high pressure, polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins, polyolefins polymerized using catalysts such as Ziegler catalysts and metallocene catalysts under low pressure, radiation, electromagnetic waves Or synthesized by light-polymerized polyolefin, low molecular weight polyolefin obtained by thermal decomposition of high-molecular-weight polyolefin, paraffin wax, microcrystalline wax, Fitzscher-Tropsch wax, Jintole method, hydrocol method, age method, etc. Synthetic hydrocarbon wax, synthetic wax using a compound having one carbon atom as a monomer, hydrocarbon wax having a functional group such as hydroxyl group or carboxyl group, hydrocarbon wax and hydrocarbon wax having a functional group Compounds, and the like.

  In particular, the resin (b1) containing a polyhydroxycarboxylic acid skeleton used in the present invention has a skeleton similar to the resin (b1) containing a polyhydroxycarboxylic acid skeleton, and contains a polyhydroxycarboxylic acid skeleton. Among the above waxes, waxes having an ester bond in the main skeleton are preferable, and carnauba wax is particularly preferable among them, in that the crystallization of the resin (b1) is promoted and the change in the crystalline state is quickly terminated. It is more preferable since it shows dispersibility. Among the carnauba waxes, those from which free fatty acids have been eliminated are particularly preferred.

The total content of the wax is preferably 0.2 to 30 parts by mass, more preferably 1 to 15 parts by mass, and still more preferably 3 to 10 parts by mass with respect to 100 parts by mass of the binder resin.
The wax (c) is dispersed in the binder resin after being melt-kneaded in the absence of a solvent and / or heat-dissolved and mixed in the presence of the organic solvent (u) with the modified wax (d) grafted with the vinyl polymer chain. It is preferable. By this method, the wax base portion of the modified wax (d) is efficiently adsorbed on the surface (c) or partially entangled with the matrix structure of the wax, whereby the surface of the wax (c) and the polyester resin (b1) (C) can be more uniformly encapsulated in (b1), and the dispersion state can be easily controlled.
The glass transition temperature (Tg) and melting point (Tm) of the wax were measured using a differential scanning calorimeter (TA-60WS and DSC-60, manufactured by Shimadzu Corporation). 10 mg of a sample was weighed into an aluminum sample pan, and while performing a nitrogen flow (flow rate 50 mL / min), the temperature was increased from 20 ° C. to 200 ° C. at a rate of temperature increase of 10 ° C./min. After the temperature was lowered at min, the DSC curve was measured when the temperature was raised from 20 ° C. to 200 ° C. at a rate of temperature rise of 10 ° C./min. From the obtained DSC curve, the temperature of the intersection of the base line extension below the endothermic peak temperature and the tangent indicating the maximum slope from the peak rising portion to the peak apex is obtained, and the glass transition temperature (Tg) of the wax is determined. did. The endothermic peak temperature was defined as the melting point (Tm) of the wax.

Modified wax (d) The modified wax (d) is obtained by grafting a vinyl polymer chain onto a wax. Examples of the wax used in (d) include the same waxes as the wax (c), and preferred ones are also the same. The vinyl monomer constituting the vinyl polymer chain of (d) includes (1) vinyl hydrocarbon, (2) carboxyl group-containing vinyl monomer and its metal salt, (3) sulfone group-containing vinyl monomer, vinyl sulfate monoester and These salts, (4) phosphate group-containing vinyl monomers and salts thereof, (6) nitrogen-containing vinyl monomers, (7) epoxy group-containing vinyl monomers, (8) halogen element-containing vinyl monomers, (9) vinyl esters, vinyl ( Thio) ethers, vinyl ketones, vinyl sulfones, (10) other vinyl monomers, and the like are mentioned, among which (1), (2), and (6) are particularly preferable. The vinyl polymer chain may be a homopolymer of a vinyl monomer or a copolymer.

  The amount of the wax component (including the unreacted wax) in the modified wax (d) is preferably 0.5 to 99.5% by mass, more preferably 1 to 80% by mass, particularly preferably 5 to 50% by mass, most preferably Preferably it is 10-30 mass%. Moreover, Tg of (d) is from 40 to 90 degreeC from a viewpoint of heat-resistant storage stability, More preferably, it is 50 to 80 degreeC. Mn of (d) is preferably 1500 to 10,000, particularly 1800 to 9000. When Mn is in the range of 1500 to 10,000, the resulting toner has good mechanical strength.

The modified wax (d) is prepared by, for example, dissolving or dispersing the wax (c) in an organic solvent (for example, toluene or xylene), heating to 100 to 200 ° C., and then converting the vinyl monomer to a peroxide initiator (benzoyl peroxide, ditertiary). Butyl peroxide, tertiary butyl peroxide benzoate, etc.) and after polymerization, the solvent is distilled off. The amount of the peroxide-based initiator in the synthesis of the modified wax (d) is preferably 0.2 to 10%, more preferably 0.5 to 5%, based on the total mass of the raw material (d).
As the peroxide polymerization initiator, an oil-soluble peroxide polymerization initiator and a water-soluble peroxide polymerization initiator are used. Specific examples of these initiators include those described above. The content of (d) is preferably 10% by mass or less, more preferably 0.5 to 8% by mass, based on the toner.

(Coloring agent)
The colorant used in the present invention is not particularly limited, and a commonly used colorant can be appropriately selected and used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G , GR), Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Lead Red, Lead Zhu, Cadmium Red, Cadmium Mercury Red, antimony vermilion, permanent red 4R Parared, Faisered, Parachlor ortho nitroaniline red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon Oil Red, Quinacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal-Free Phthalocyanine Blue, Phthalocyanine Blue , Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome oxide, pyridian, emerald green, pigment green B, naphthol green B, green gold, a Cid green lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof.
The content of the colorant is preferably 1 to 15% by mass, and more preferably 3 to 10% by mass with respect to the toner.

The colorant used in the present invention can also be used as a master batch combined with a resin. As the binder resin kneaded together with the master batch, various resins that can be used for the binder resin of the toner of the present invention described above can be used.
The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. There is also a method of removing water and organic solvent components by mixing and kneading an aqueous paste containing water, which is a so-called flushing method, together with a resin and an organic solvent, and transferring the colorant to the resin side. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, for example, a high shearing dispersion device such as a two-roll mill or a three-roll mill is preferably used.
As the usage-amount of the said masterbatch, 0.1-20 mass parts is preferable with respect to 100 mass parts of binder resin.

Further, a pigment dispersant may be used together with the masterbatch resin and the colorant, but it is preferable that the compatibility with the binder resin is high in terms of pigment dispersibility. Specific commercial products include “Azisper PB821”, “Azisper PB822” (manufactured by Ajinomoto Fine Techno Co.), “Disperbyk-2001” (manufactured by BYK Chemie), “EFKA-4010” (manufactured by EFKA), and the like. It is done.
The pigment dispersant is preferably blended in the toner at a ratio of 0.1 to 10% by mass with respect to the colorant. When the blending ratio is less than 0.1% by mass, the pigment dispersibility may be insufficient, and when it is more than 10% by mass, the chargeability under high humidity may be deteriorated.

(Magnetic material)
In the present invention, a magnetic substance can be contained together with the binder resin and the colorant.
Examples of the magnetic material that can be used in the present invention include (1) iron oxide containing magnetic iron oxide such as magnetite, maghemite, and ferrite, and other metal oxides, and (2) metals such as iron, cobalt, and nickel, or Alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, (3) and these A mixture of

Specific examples of the magnetic material include Fe ₃ O ₄ , γ-Fe ₂ O ₃ , ZnFe ₂ O ₄ , Y ₃ Fe ₅ O ₁₂ , CdFe ₂ O ₄ , Gd ₃ Fe ₅ O ₁₂ , CuFe ₂ O ₄ , _{PbFe 12 O, NiFe 2 O 4} , NdFe 2 O, BaFe 12 O 19, MgFe 2 O 4, MnFe 2 O 4, LaFeO 3, iron powder, cobalt powder, nickel powder, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, fine powders of triiron tetroxide and γ-iron trioxide are particularly preferable.

  Further, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements, or a mixture thereof can be used. Examples of different elements include, for example, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, And gallium. Preferred heterogeneous elements are selected from magnesium, aluminum, silicon, phosphorus, or zirconium. The foreign element may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as an oxide, or may be present on the surface as an oxide or hydroxide. Is preferably contained as an oxide.

The different elements can be incorporated into the particles by mixing the salts of the different elements at the time of producing the magnetic substance and adjusting the pH. Moreover, it can precipitate on the particle | grain surface by adjusting pH after magnetic body particle | grain production | generation, or adding salt of each element and adjusting pH.
As the usage-amount of the said magnetic body, 10-200 mass parts of magnetic bodies are preferable with respect to 100 mass parts of binder resin, and 20-150 mass parts is more preferable. The magnetic material can also be used as a colorant.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary.
Any known charge control agent can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine) Modified quaternary ammonium salts), alkylamides, simple substances or compounds of phosphorus, simple substances or compounds of tungsten, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge NEGVP2036 of quaternary ammonium salt, copy charge NX VP434 (above, manufactured by Hoechst), LRA-901, LR-147 which is a boron complex ( Nippon Carlit), copper phthalocyanine, perylene, quinacridone, Zone-based pigment, a sulfonic acid group, a carboxyl group, and polymer compounds having a functional group such as a quaternary ammonium salt.

  In the present invention, the amount of charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, etc., and is not uniquely limited. It is used in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the resin. Preferably, the range of 0.1-2 mass parts is good. When the amount exceeds 5 parts by mass, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attraction force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents can be dissolved and dispersed after being melt-kneaded together with the masterbatch and resin, or of course, may be added when directly dissolving or dispersing in an organic solvent. Further, after the toner base particles are prepared, they may be fixed on the surface thereof.

(External additive)
An external additive may be added to the toner of the present invention as necessary.
The external additive is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica fine particles, hydrophobized silica fine particles, fatty acid metal salts (for example, zinc stearate, And aluminum oxide stearate); metal oxides (for example, titania, alumina, tin oxide, antimony oxide, etc.) or their hydrophobized products, fluoropolymers, and the like. Among these, hydrophobized silica fine particles, titania particles, and hydrophobized titania fine particles are preferable.

  Examples of the silica fine particles include HDK H 2000, HDK H 2000/4, HDK H 2050EP, HVK21, HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, R812 (all Nippon Aerosil Co., Ltd.). Examples of the titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.); STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.); TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.); MT -150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Co., Ltd.) and the like. Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both made by Titanium Industry Co., Ltd.); TAF-500T, TAF-1500T ( Both are manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (both manufactured by Teika Co., Ltd.);

In order to obtain the hydrophobized silica fine particles, the hydrophobized titania fine particles, and the hydrophobized alumina fine particles, the hydrophilic fine particles are made of silane cups such as methyltrimethoxysilane, methyltriethoxysilane, and octyltrimethoxysilane. It can be obtained by treating with a ring agent.
Examples of the hydrophobizing agent include silane coupling agents such as dialkyl dihalogenated silanes, trialkyl halogenated silanes, alkyl trihalogenated silanes, and hexaalkyldisilazanes, silylating agents, and silane couplings having a fluorinated alkyl group. Agents, organic titanate coupling agents, aluminum coupling agents, silicone oils, silicone varnishes and the like.

Further, silicone oil-treated inorganic fine particles obtained by treating the inorganic fine particles with silicone oil if necessary are also suitable.
Examples of the inorganic fine particles include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, iron oxide, copper oxide, zinc oxide, tin oxide, silica sand, clay, mica, silica Examples include apatite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, parium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride. Among these, silica and titanium dioxide are particularly preferable.

  Examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, chlorophenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, polyether-modified silicone oil, alcohol-modified silicone oil, amino-modified. Examples thereof include silicone oil, epoxy-modified silicone oil, epoxy-polyether-modified silicone oil, phenol-modified silicone oil, carboxyl-modified silicone oil, mercapto-modified silicone oil, acrylic or methacryl-modified silicone oil, and α-methylstyrene-modified silicone oil.

1-100 nm is preferable and, as for the average particle diameter of the primary particle of the said inorganic fine particle, 3-70 nm is more preferable. If the average particle size is less than 1 nm, the inorganic fine particles are embedded in the toner, and the function may not be effectively exhibited. If the average particle size exceeds 100 nm, the surface of the electrostatic latent image carrier may be damaged unevenly. May end up. As the external additive, inorganic fine particles or hydrophobized inorganic fine particles can be used in combination, but the specific surface area of the inorganic fine particles by BET method is preferably 20 to 500 m ² / g.
The amount of the external additive added is preferably 0.1 to 5% by mass and more preferably 0.3 to 3% by mass with respect to the toner.

  Resin fine particles can also be added as the external additive. For example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, or dispersion polymerization; copolymer of methacrylic acid ester, acrylic acid ester; condensation polymerization system such as silicone, benzoguanamine, nylon; polymer particles by thermosetting resin It is done. By using such resin fine particles in combination, the chargeability of the toner can be enhanced, the reversely charged toner can be reduced, and the background stain can be reduced. The addition amount of the resin fine particles is preferably 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass with respect to the toner.

(Internally added inorganic filler)
In the present invention, the toner is used to suppress the temporal change of the glass transition temperature, which is a problem specific to the resin (b1) containing a polyhydroxycarboxylic acid skeleton, and to stabilize the thermal characteristics such as heat-resistant storage stability and fixing minimum temperature. It is preferable to internally add an inorganic filler. The thermal properties are stabilized by the presence of the aforementioned wax and inorganic filler. As described above, the resin (b1) containing a polyhydroxycarboxylic acid skeleton is likely to be crystallized when the optical purity of the monomer is high, and the glass transition temperature is likely to change gradually with time. By being present in b1), a gradual change in the glass transition temperature inherent to the polyhydroxycarboxylic acid skeleton can be suppressed.

  Examples of the inorganic filler for internal use used in the present invention include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, clay (montmorillonite, or organic thereof) (Including modified products), mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride, etc. In particular, silica, silica sand, clay (including montmorillonite or an organic modification thereof), mica, wollastonite, and diatomaceous earth are preferable.

  Moreover, from the viewpoint of dispersibility of the inorganic filler in the resin (b1), it is preferable to use a surface-treated inorganic filler for the inorganic filler. Examples of the hydrophobic treatment agent include silane coupling agents, silylating agents, silane coupling agents having a fluorinated alkyl group, organic titanate coupling agents, aluminum coupling agents, and the like. Further, sufficient effects can be obtained even when silicone oil is used as a hydrophobizing agent.

  The dielectric constant of the inorganic fine particles is preferably 0.2 to 7.5, more preferably 1.3 to 3.5, and particularly preferably 1.7 to 2.5. By setting the dielectric constant of the inorganic filler within this range, the amount of accumulated charge can be maintained moderately, and abnormal charge increase in a low temperature and low humidity environment can be suppressed. This can provide stable image quality.

The dielectric constant of the inorganic filler used in the present invention is measured by placing the inorganic filler in a cylindrical cell having an inner diameter of 18 mm to which an electrode is attached, and pushing the inorganic filler in the cell into a disk shape having a thickness of 0.65 mm and a diameter of 18 mm. In a solidified state, measurement is performed with a TR-10C type dielectric loss measuring device (manufactured by Ando Electric Co., Ltd.). The frequency is 1 KHz and RATIO is 11 × 10 ⁻⁹ . The inorganic filler is preferably added by melt-kneading with a raw material such as a resin, a colorant, and wax in the melt-kneading step. By setting it within this range, the grindability in the grinding step and the charging performance can be improved. The amount of the inorganic filler added is preferably 0.1 to 10 parts by mass in 100 parts by mass of the toner, and if it is less than 0.1 parts by mass, the content is insufficient and the purpose of the addition is not observed, and exceeds 10 parts by mass. As a result, the inorganic filler cannot be uniformly dispersed, and the inorganic filler is unevenly distributed, resulting in deterioration of chargeability and fixability.

  Moreover, the average diameter of the primary particle of an inorganic filler is 5-1000 nm, More preferably, it is 10-500 nm. By setting it within this range, both improvement in chargeability and pulverization of the toner can be achieved. If the thickness is smaller than 5 nm, the inorganic filler aggregates, the inorganic filler is not uniformly dispersed in the toner, and the uniformity of the charging property is lost. When it is larger than 1 μm, it is necessary to contain a large amount of an inorganic filler in order to obtain an additive effect. Here, the average particle size is the number average particle size, and is measured by a particle size distribution measuring device using dynamic light scattering, such as DSL-700 manufactured by Otsuka Electronics Co., Ltd. or Coulter N4 manufactured by Coulter Electronics. Is possible. When it is difficult to deviate from the secondary aggregation, it is also possible to directly determine the particle diameter from a photograph obtained by a transmission electron microscope. In this case, at least 100 particles are observed and the average of the major axis is observed. It is preferable to use a value. These inorganic fillers may be used alone or in combination of two or more.

(Toner production method)
The method for producing the toner is not particularly limited and can be appropriately selected according to the purpose from conventionally known toner production methods. For example, a kneading / pulverizing method, a polymerization method, a dissolution suspension method, The spray granulation method etc. are mentioned. Among these, the kneading / pulverizing method and the polymerization method are preferable from the viewpoints of dispersibility and productivity of the wax and the colorant.

--Kneading and grinding method--
In the kneading and pulverizing method, for example, a toner material containing at least a binder resin, a colorant, and a wax is melt-kneaded, and the obtained kneaded material is pulverized and classified to produce the toner base particles. It is a method to do.
In the melt kneading, the toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, a KTK type twin screw extruder manufactured by Kobe Steel, a TEM type extruder manufactured by Toshiba Machine Co., Ltd., a twin screw extruder manufactured by Casey Kay Co., Ltd., a PCM type twin screw extruder manufactured by Ikegai Co., Ltd. Used. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt-kneading temperature is determined with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

  In the pulverization, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used. In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. The classification can be performed, for example, by removing the fine particle portion with a cyclone, a decanter, a centrifuge, or the like. After the pulverization and classification are completed, the pulverized product is classified into an air stream by centrifugal force or the like, and toner base particles having a predetermined particle diameter can be produced.

  Next, the external additive is externally added to the toner base particles. By mixing and stirring the toner base particles and the external additive using a mixer, the surface of the toner base particles is coated while being crushed. At this time, it is important from the viewpoint of durability that the external additives such as inorganic fine particles and resin fine particles are uniformly and firmly attached to the toner base particles.

--- Polymerization method--
As a method for producing a toner by the polymerization method, for example, a toner containing a resin (b1) having at least a polyhydroxycarboxylic acid skeleton in an organic solvent, a modified polyester resin capable of urea or urethane bonding, a wax, and a colorant. Dissolve or disperse the material. Then, this dissolved or dispersed material is dispersed in an aqueous medium, subjected to a polyaddition reaction, and the solvent of this dispersion is removed and washed.
Examples of the modified polyester resin capable of being bonded with urea or urethane include, for example, polyester prepolymer having an isocyanate group obtained by reacting a carboxyl group or a hydroxyl group at a terminal of a polyester with a polyvalent isocyanate compound (PIC). Can be mentioned. The modified polyester resin obtained by crosslinking and / or extending the molecular chain by the reaction of this polyester prepolymer and amines can improve the hot offset property while maintaining the low temperature fixability.

(Developer)
The developer contains at least the toner of the present invention, and other components appropriately selected such as a carrier. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.

(Career)
There is no restriction | limiting in particular as a carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers this core material is preferable.
There is no restriction | limiting in particular as a material of the said core material, It can select suitably from well-known things, For example, 50-90 emu / g manganese-strontium (Mn-Sr) type material, manganese-magnesium (Mn-) Mg) -based materials and the like are preferable, and highly magnetized materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. In addition, the copper-zinc (Cu-Zn) system (30 to 80 emu / g) or the like is advantageous in that it can weaken the contact with the electrostatic latent image carrier in which the toner is in a spiked state, and is advantageous in improving the image quality. The weakly magnetized material is preferred. These may be used alone or in combination of two or more.

  The particle diameter of the core material is preferably an average particle diameter (weight average particle diameter (D50)) of 10 to 200 μm, and more preferably 40 to 100 μm. When the average particle diameter (weight average particle diameter (D50)) is less than 10 μm, in the distribution of carrier particles, the fine powder system increases, the magnetization per particle is lowered, and carrier scattering may occur. If it exceeds 200 μm, the specific surface area may decrease and toner scattering may occur, and in the case of a full color with many solid portions, reproduction of the solid portions may be particularly poor.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride And fluorinated terpolymers (triple fluorinated (multiple) copolymers) such as terpolymers of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomers, silicone resins, etc. It is done. These may be used individually by 1 type and may use 2 or more types together. Among these, a silicone resin is particularly preferable.

  The silicone resin is not particularly limited and can be appropriately selected according to the purpose from generally known silicone resins. For example, a straight silicone resin consisting only of an organosilosan bond; an alkyd resin; Examples thereof include polyester resins, epoxy resins, acrylic resins, silicone resins modified with urethane resins, and the like.

Commercially available products can be used as the silicone resin. Examples of straight silicone resins include KR271, KR255, and KR152 manufactured by Shin-Etsu Chemical Co., Ltd .; SR2400, SR2406, and SR2410 manufactured by Toray Dow Corning Silicone Co., Ltd. Etc.
Commercially available products can be used as the modified silicone resin. For example, KR206 (alkyd modified), KR5208 (acryl modified), ES1001N (epoxy modified), KR305 (urethane modified) manufactured by Shin-Etsu Chemical Co., Ltd .; SR2115 (epoxy-modified), SR2110 (alkyd-modified) manufactured by Dow Corning Silicone Co., Ltd., and the like.
In addition, although a silicone resin can be used alone, it is also possible to simultaneously use a component that undergoes a crosslinking reaction, a charge amount adjusting component, and the like.

The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.
For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the application method include an immersion method, a spray method, and a brush coating method.

There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.
The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.

  The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by mass. When the amount is less than 0.01% by mass, the uniform resin layer may not be formed on the surface of the core material. When the amount exceeds 5.0% by mass, the resin layer becomes thick. In some cases, granulation of carriers occurs, and uniform carrier particles may not be obtained.

  When the developer is a two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose, for example, 90 to 98 mass. % Is preferred.

(Image forming apparatus and image forming method)
An image forming apparatus according to the present invention includes an electrostatic latent image carrier, a charging unit that charges the surface of the electrostatic latent image carrier, and an electrostatic latent image formed by exposing the charged electrostatic latent image carrier surface. An exposure unit for forming, a developing unit for developing the electrostatic latent image with toner to form a visible image, a transfer unit for transferring the visible image to a recording medium, and the image transferred to the recording medium A fixing unit for fixing the transferred image, and a cleaning unit, and other units appropriately selected as necessary, for example, a discharging unit, a recycling unit, a control unit, and the like. The charging unit and the exposure unit may be collectively referred to as an electrostatic latent image forming unit. The toner used for the developing means is the image forming toner of the present invention.

  The image forming method of the present invention comprises a charging step of charging the surface of the electrostatic latent image carrier, an exposure step of exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and the electrostatic A developing process for developing a latent image with toner to form a visible image, a transfer process for transferring the visible image to a recording medium, and a fixing process for fixing the transferred image transferred to the recording medium. It includes at least a cleaning process, and other processes appropriately selected as necessary, for example, a static elimination process, a recycling process, a control process, and the like. The charging process and the exposure process may be collectively referred to as an electrostatic latent image forming process. The toner used in the developing step is the image forming toner of the present invention.

  The image forming method of the present invention can be preferably carried out by the image forming apparatus of the present invention, the charging step can be performed by the charging unit, the exposure step can be performed by the exposing unit, The developing step can be performed by the developing unit, the transferring step can be performed by the transferring unit, the fixing step can be performed by the fixing unit, and the cleaning step can be performed by the cleaning unit. The other steps can be performed by the other means.

The toner for image formation of the present invention can be used by being housed in a process cartridge having at least the electrostatic latent image carrier and a developing unit and detachable from the image forming apparatus main body.
FIG. 1 shows a schematic configuration of an image forming apparatus provided with a process cartridge having image forming toner of the present invention.
In the figure, reference numeral 1 denotes the entire process cartridge, 2 denotes a photoreceptor, 3 denotes charging means, 4 denotes developing means, and 5 denotes cleaning means.

In the present invention, a plurality of components such as the photosensitive member 2, the charging unit 3, the developing unit 4, and the cleaning unit 5 described above are integrally combined as a process cartridge. The image forming apparatus main body such as a copying machine or a printer is configured to be detachable.
The operation of the image forming apparatus provided with the process cartridge having the image forming toner of the present invention will be described as follows.
The photoreceptor 2 is driven to rotate at a predetermined peripheral speed. In the rotation process, the photosensitive member 2 is uniformly charged with a positive or negative predetermined potential on the peripheral surface thereof by the charging unit 3, and then receives image exposure light from an image exposure unit such as slit exposure or laser beam scanning exposure. In this way, electrostatic latent images are sequentially formed on the circumferential surface of the photosensitive member, and the formed electrostatic latent image is then toner developed by the developing means 4, and the developed toner image is transferred from the paper feeding unit to the photosensitive member. The image is sequentially transferred by the transfer means to the transfer material fed in synchronism with the rotation of the photoreceptor between the transfer means. The transfer material that has received the image transfer is separated from the surface of the photosensitive member, introduced into the image fixing means, and fixed on the image, and printed out as a copy (copy). The surface of the photoconductor after the image transfer is cleaned by removing the transfer residual toner by a cleaning means, and after being further neutralized, it is repeatedly used for image formation.

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following description, “parts” indicates parts by mass.
In the examples and comparative examples, toner may be obtained by using a plurality of resins in combination as the resin (b1) having a polyhydroxycarboxylic acid skeleton. In this case, the optical purity of the resin (b1) is as follows. Define as follows.
1) When two resins use the same optically active monomer, the weight average of the optical purity and the resin mixing ratio is obtained.
2) When the optically active monomers having different structures are used for the two resins, only the resin with high optical purity has optical purity, and the optical purity of the other resin is assumed to be 0%. Weighted average with.

[Production Example 1] (Production of linear polyester resin (b1))
In an autoclave reaction vessel equipped with a thermometer, a stirrer and a nitrogen insertion tube, 3 parts of 1,3-propanediol, 450 parts of L-lactic acid lactide, 50 parts of D-lactic acid lactide and 2 parts of tin 2-ethylhexylate The ring-opening polymerization was carried out at 160 ° C. for 3 hours at normal pressure, and further reacted at 130 ° C. at normal pressure. The resin taken out was cooled to room temperature, and then pulverized into polyester diol containing a polyhydroxycarboxylic acid skeleton (optical purity 80 mol%). 400 parts of a polyester diol containing a polyhydroxycarboxylic acid skeleton having a hydroxyl value of 11.2 and a polyester diol having a hydroxyl value of 56 [bisphenol A · EO 2-mol adduct and terephthalic acid were dehydrated at a molar ratio of 1: l. 100 parts obtained by condensation and synthesis] are dissolved in methyl ethyl ketone, followed by addition of 20 parts of IPDI as an extender, an extension reaction is carried out at 50 ° C. for 6 hours, and the solvent is distilled off [polyester b1- 1] was obtained. [Polyester b1-1] had a Tg of 43 ° C.

[Production Example 2] (Production of linear polyester resin (b1))
In an autoclave reaction vessel equipped with a thermometer, a stirring frame and a nitrogen insertion tube, 3 parts of 1,4-butanediol, 400 parts of L-lactic acid lactide, 100 parts of D-lactic acid lactide and 2 parts of tin 2-ethylhexylate The mixture was subjected to ring-opening polymerization at 160 ° C. for 3 hours at normal pressure, and further reacted at 130 ° C. at normal pressure. The taken-out resin was cooled to room temperature, and then pulverized into a polyester diol containing a polyhydroxycarboxylic acid skeleton (optical purity 60 mol%). 200 parts of a polyester diol containing a polyhydroxycarboxylic acid skeleton having a hydroxyl value of 11.2 and a polyester diol having a hydroxyl value of 56 [bisphenol A · EO 2 mol adduct and terephthalic acid are dehydrated and condensed in a molar ratio of 1: 1. 300 parts is dissolved in methyl ethyl ketone, followed by adding 38 parts of IPDI as an extender, performing an extension reaction at 50 ° C. for 6 hours, and distilling off the solvent [polyester b1-2. ] Was obtained. [Polyester b1-2] had a Tg of 46 ° C.

[Production Example 3] (Production of linear polyester resin (b1))
In an autoclave reaction vessel equipped with a thermometer, a stirrer and a nitrogen insertion tube, 3 parts of 1,3-propanediol, 400 parts of L-lactic acid lactide, 100 parts of glycolide and 2 parts of tin 2-ethylhexylate were added. The ring-opening polymerization was performed at 160 ° C. for 3 hours at a pressure, and further reacted at 130 ° C. at a normal pressure. The taken-out resin was cooled to room temperature and then pulverized into a polyester diol containing a polyhydroxycarboxylic acid skeleton (optical purity 100 mol%). 250 parts of a polyester diol containing a polyhydroxycarboxylic acid skeleton having a hydroxyl value of 11.2 and a polyester diol having a hydroxyl value of 56 [bisphenol A · EO 2 mol adduct and terephthalic acid are dehydrated and condensed in a molar ratio of 1: 1. 250 parts of adipic acid was added as an extender, and the reaction was performed at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Polyester b1-3]. [Polyester b1-3] had a Tg of 49 ° C.

[Production Example 4] (Production of linear polyester resin (b1))
In a reaction vessel equipped with a condenser, a stirring machine and a nitrogen insertion tube, 3 parts of 1,4-butanediol, 450 parts of L-lactic acid, 50 parts of D-lactic acid and 2 parts of tetrabutoxytitanate are added at normal pressure. Dehydration condensation was performed at 160 ° C. for 3 hours, and dehydration condensation was further performed at 160 ° C. under a reduced pressure of 10 to 15 mmHg. The resin taken out was cooled to room temperature, and then pulverized into polyester diol containing a polyhydroxycarboxylic acid skeleton (optical purity 80 mol%). 400 parts of a polyester diol containing a polyhydroxycarboxylic acid skeleton having a hydroxyl value of 11.2 and a polyester diol having a hydroxyl value of 56 [bisphenol A · EO 2 mol adduct and terephthalic acid are dehydrated and condensed in a molar ratio of 1: 1. 100 parts were dissolved in methyl ethyl ketone, followed by addition of 20 parts of IPDI, an extension reaction was carried out at 50 ° C. for 6 hours, and the solvent was distilled off to obtain [Polyester b1-4]. . [Polyester b1-4] had a Tg of 48 ° C.

[Production Example 5] (Production of linear polyester resin (b1))
In a reaction vessel equipped with a cooling tube, a stirring frame, and a nitrogen insertion tube, 3 parts of 1,4-butanediol, 450 parts of L-lactic acid, 50 parts of D-lactic acid and 2 parts of tetrabutoxytitanate are added at normal pressure. The mixture was dehydrated and condensed at 160 ° C. for 3 hours, and further dehydrated and condensed at 160 ° C. under a reduced pressure of 10 to 15 mmHg. The resin taken out was cooled to room temperature, and then pulverized into polyester diol containing a polyhydroxycarboxylic acid skeleton (optical purity 80 mol%). 400 parts of a polyester diol containing a polyhydroxycarboxylic acid skeleton having a hydroxyl value of 11.2 and a polyester diol having a hydroxyl value of 56 [1,2-propylene glycol and terephthalic acid were dehydrated and condensed at a molar ratio of 1: 1. 100 parts were dissolved in methyl ethyl ketone, followed by the addition of 20 parts of IPDI, an extension reaction was carried out at 50 ° C. for 6 hours, and the solvent was distilled off to obtain [Polyester b1-5]. [Polyester b1-5] had a Tg of 48 ° C.

[Production Example 6] (Production of polyester resin)
9 parts of glycerin, 288 parts of glycolic acid lactide and 2 parts of dibutyltin oxide were charged into an autoclave reaction vessel equipped with a thermometer and a stirring frame, and after nitrogen substitution, ring-opening polymerization was performed at 160 ° C. for 6 hours at atmospheric pressure. Furthermore, after reacting at a reduced pressure of 10 to 15 mmHg for 5 hours, cooling to 110 ° C., adding 18 parts of IPDI in toluene, reacting at 110 ° C. for 5 hours, then removing the solvent, weight average molecular weight Mw 70,000, [Urethane-modified polyester] having a free isocyanate content of 0.5% was obtained (optical purity 0 mol%). [Urethane-modified polyester] had a Tg of 47 ° C.

[Production Example 7] (Production of polyester resin)
6 parts of ethylene glycol, 400 parts of glycolic acid lactide and 2 parts of dibutyltin oxide are put into an autoclave reaction vessel equipped with a thermometer and a stirring frame. After nitrogen substitution, ring-opening polymerization is carried out at 160 ° C. for 8 hours at normal pressure. Further, the reaction was carried out at a reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Polyester 1] (optical purity 0 mol%). [Polyester 1] had a Tg of 40 ° C.

[Production Example 8] (Production of polyester resin)
In a reaction vessel equipped with a cooling pipe, a stirring frame and a nitrogen introduction pipe, 781 parts of 1,2-propylene glycol, 794 parts of dimethyl terephthalate, 66 parts of adipic acid, 38 parts of trimellitic anhydride and terephthalic acid as a polymerization catalyst 1 part of titanium oxide was added and reacted for 8 hours at 180 ° C. under a nitrogen stream while distilling off the methanol produced. Next, while gradually raising the temperature to 230 ° C., the reaction is carried out for 4 hours while distilling off the 1,2-propylene glycol and water produced under a nitrogen stream, and further the reaction is carried out for 1 hour under a reduced pressure of 5 to 20 mmHg to soften. It was taken out when the point reached 160 ° C. to obtain [Polyester 2]. [Polyester 2] had a Tg of 61 ° C.

[Production Example 9] (Production of modified wax)
454 parts of xylene and 150 parts of low molecular weight polyethylene (Sanwa Kasei Kogyo Co., Ltd. sun wax LEL-400: softening point 128 ° C.) were introduced into an autoclave reaction vessel equipped with a thermometer and a stirring frame. The temperature was raised to 0 ° C. and dissolved sufficiently, and a mixed solution of 595 parts of styrene, 255 parts of methyl methacrylate, 34 parts of di-t-butylperoxyhexahydroterephthalate and 119 parts of xylene was added dropwise at 170 ° C. over 3 hours for polymerization. And kept at this temperature for 30 minutes. Next, the solvent was removed to obtain [modified wax l]. [Modified Wax 1] had a graft chain sp value of 10.35 (cal / cm ³ ) ^1/2 , Mn of 1872, Mw of 5194, and Tg of 56.9 ° C.

[Production Example 10] (Production of resin)
200 parts of [Polyester 2] and 800 parts of [Polyester b1-2] were melted and kneaded at a temperature of 100 to 130 ° C. with a biaxial kneader (Ikegai, PCM-30). Next, the obtained kneaded product was cooled to room temperature, and then coarsely pulverized to 200 to 300 μm with a hammer mill to obtain [Resin 1] (content of (b1) in resin is 80%, optical of (b1) 60% purity).
[Production Example 11] (Production of resin)
[Polyester b1-1] 1000 parts were coarsely pulverized to 200 to 300 μm with a hammer mill to obtain [Resin 2] (content of (b1) in resin is 100%, optical purity of (b1) is 80%) .

[Production Example 12] (Production of resin)
200 parts of [Polyester 2] and 800 parts of [Polyester b1-3] were melted, kneaded and pulverized in the same manner as in Production Example 10 to obtain [Resin 3] (content of (b1) in resin 80% , (B1) optical purity 100%).
[Production Example 13] (Production of resin)
200 parts of [urethane-modified polyester] and 800 parts of [polyester b1-4] were melted, kneaded and pulverized in the same manner as in Production Example 10 to obtain [Resin 4] (content (b1) in resin 80 %, Optical purity of (b1) 80%).

[Production Example 14] (Production of resin)
200 parts of [urethane-modified polyester] and 800 parts of [polyester b1-5] were melted, kneaded and pulverized in the same manner as in Production Example 10 to obtain [Resin 5] (content (b1) in resin 80 %, Optical purity of (b1) 80%).
[Production Example 15] (Production of resin)
350 parts of [Polyester 2] and 650 parts of [Polyester b1-3] were melted, kneaded and pulverized in the same manner as in Production Example 10 to obtain [Resin 6] (content of (b1) in resin: 65% , (B1) optical purity 100%).

[Production Example 16] (Production of resin)
200 parts of [urethane modified polyester] and 800 parts of [polyester 1] were melted, kneaded and pulverized in the same manner as in Production Example 10 to obtain [Resin 7] (content of (b1) in the resin was 0%, (B1) optical purity 0%).
[Production Example 17] (Production of polyester resin)
In an autoclave reaction vessel equipped with a thermometer, a stirring frame, and a nitrogen insertion tube, a toluene solution of 10 parts of L-lactide, 10 parts of D-lactide and 0.006 part of stannous octylate was stirred, and a nitrogen introduction tube Was vacuum dried for 2 hours and purged with nitrogen, and then heated to 190 ° C. in a nitrogen atmosphere to conduct a ring-opening polymerization reaction for 2 hours. While maintaining the temperature in the reaction system, the mixture was deaerated with a vacuum pump and decompressed to 5 mmHg, and continued for 1 hour. The obtained resin [Polyester a-1] had a Tg of 48 ° C.
[Production Example 18] (Production of resin)
1000 parts of [Polyester a-1] was coarsely pulverized to 200 to 300 μm with a hammer mill to obtain [Resin 8] (content of (b1) in resin is 100%, optical purity of (b1) is 0%). .

[Method for measuring weight average particle diameter of toner]
Measuring instrument: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 100 μm
Analysis software: Coulter Multisizer AccuComp version 1.19
(Made by Beckman Coulter)
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether
, HLB: 13.6) 5% electrolytic solution Dispersion condition: 10 mg of a measurement sample is added to 5 ml of the dispersion, and is mixed for 1 minute with an ultrasonic disperser.
And then add 25 ml of electrolyte, and further with an ultrasonic disperser
Disperse for 1 minute.
Measurement conditions: Add 100 ml of electrolyte and dispersion into a beaker, and adjust the particle size of 30,000 particles.
Measure 30,000 particles at a concentration that can be measured in 20 seconds.
Determine the weight average particle size.

Example 1
(Toner prescription)
Resin 1 82 parts Carnauba Wax A
(Tm 80 ° C., Tg 67 ° C., Tm / Tg = 1.19, acid value 5 mg KOH / g) 5 parts Modified wax 1 1 part Carbon black (Mitsubishi Chemical # 44) 9 parts Silica: HDK H 2000 3 parts The raw materials are premixed using a Henschel mixer (Mitsui Miike Chemical Co., Ltd., FM10B) and then melted at a temperature of 100 to 130 ° C. with a twin-screw kneader (Ikegai Co., Ltd., PCM-30). Kneaded. The obtained kneaded product was cooled to room temperature and then coarsely pulverized to 200 to 300 μm with a hammer mill. Next, after finely pulverizing using a supersonic jet pulverizer, Labojet (manufactured by Nippon Pneumatic Industry Co., Ltd.), adjusting the pulverization air pressure appropriately so that the weight average particle size becomes 6.2 ± 0.3 μm. The louver opening is adjusted so that the weight average particle size is 7.0 ± 0.2 μm and the amount of fine powder of 4 μm or less is 10% by number or less with an air classifier (manufactured by Nippon Pneumatic Industry Co., Ltd., MDS-I). Classification was carried out with appropriate adjustment to obtain toner base particles. Next, 1.0 part by mass of an additive (silica: HDK H 2000, manufactured by Clariant Co., Ltd.) was stirred and mixed with 100 parts by mass of toner base particles with a Henschel mixer to produce toner 1.

(Example 2)
(Toner prescription)
Resin 2 53.9 parts Resin 4 23.1 parts Paraffin wax A
(Tm 73 ° C., Tg 65 ° C., Tm / Tg = 1.12, acid value 0.5 mgKOH / g)
5 parts Modified wax 1 1 part Carbon black (Mitsubishi Chemical # 44) 9 parts Silica: HDK H 2000 8 parts Toner 2 was produced in the same manner as in Example 1 except that the toner formulation was changed as described above.

(Example 3)
(Toner prescription)
Resin 2 41 parts Resin 3 41 parts Carnauba wax A
(Tm 80 ° C., Tg 67 ° C., Tm / Tg = 1.19, acid value 5 mgKOH / g)
5 parts Modified wax 1 1 part Carbon black (Mitsubishi Chemical # 44) 9 parts Silica: HDK H 2000 3 parts Toner 3 was produced in the same manner as in Example 1 except that the toner formulation was changed as described above.

(Example 4)
(Toner prescription)
Resin 3 82 parts Paraffin Wax A
(Tm 73 ° C., Tg 65 ° C., Tm / Tg = 1.12, acid value 0.5 mgKOH / g)
5 parts Modified wax 1 1 part Carbon black (Mitsubishi Chemical # 44) 9 parts Silica: HDK H 2000 3 parts Toner 4 was produced in the same manner as in Example 1 except that the toner formulation was changed as described above.

(Example 5)
(Toner prescription)
Resin 4 41 parts Resin 3 41 parts Carnauba wax A
(Tm 80 ° C., Tg 67 ° C., Tm / Tg = 1.19, acid value 5 mgKOH / g)
5 parts Modified wax 1 1 part Carbon black (Mitsubishi Chemical # 44) 9 parts Silica: HDK H 2000 3 parts Toner 5 was produced in the same manner as in Example 1 except that the toner formulation was changed as described above.

(Example 6)
(Toner prescription)
Resin 5 82 parts Carnauba Wax A
(Tm 80 ° C., Tg 67 ° C., Tm / Tg = 1.19, acid value 5 mgKOH / g)
5 parts Modified wax 1 1 part Carbon black (Mitsubishi Chemical # 44) 9 parts Silica: HDK H 2000 3 parts Toner 6 was produced in the same manner as in Example 1 except that the toner formulation was changed as described above.

(Example 7)
(Toner prescription)
Resin 6 82 parts Carnauba Wax A
(Tm 80 ° C., Tg 67 ° C., Tm / Tg = 1.19, acid value 5 mgKOH / g)
5 parts Modified wax 1 1 part Carbon black (Mitsubishi Chemical # 44) 9 parts Silica: HDK H 2000 3 parts Toner 7 was produced in the same manner as in Example 1 except that the toner formulation was changed as described above.

(Comparative Example 1)
(Toner prescription)
Resin 7 82 parts Paraffin Wax A
(Tm 73 ° C., Tg 65 ° C., Tm / Tg = 1.12, acid value 0.5 mgKOH / g)
5 parts Modified wax 1 1 part Carbon black (Mitsubishi Chemical # 44) 9 parts Silica: HDK H 2000 3 parts Toner 8 was produced in the same manner as in Example 1 except that the toner formulation was changed as described above.

(Example 8)
(Toner prescription)
Resin 8 84 parts Paraffin wax A
(Tm 73 ° C., Tg 65 ° C., Tm / Tg = 1.12, acid value 0.5 mgKOH / g)
5 parts Modified wax 1 1 part Carbon black (Mitsubishi Chemical # 44) 10 parts Toner 9 was produced in the same manner as in Example 1 except that the toner formulation was changed as described above.

(Comparative Example 2)
In the toner formulation of Example 1, Example 5 was carried out except that 5 parts of paraffin wax A was changed to 5 parts of paraffin wax B (Tm 69 ° C., Tg 54 ° C., Tm / Tg = 1.28, acid value 0.5 mgKOH / g). Toner 10 was produced in the same manner as in Example 1.
(Comparative Example 3)
Example 1 except that 5 parts of paraffin wax A was changed to 5 parts of paraffin wax C (Tm 102 ° C., Tg 81 ° C., Tm / Tg = 1.26, acid value 0.5 mgKOH / g) in the toner formulation of Example 1. Toner 11 was produced in the same manner as in Example 1.

(Comparative Example 4)
Example 1 is the same as Example 1 except that 5 parts of paraffin wax A is changed to 5 parts of synthetic ester wax (Tm 83 ° C., Tg 65 ° C., Tm / Tg = 1.27, acid value 4 mgKOH / g) in the toner formulation of Example 1. Toner 12 was produced in the same manner.
(Comparative Example 5)
In the toner formulation of Example 1, Example 5 was changed except that 5 parts of paraffin wax A was changed to 5 parts of Carnauba wax B (Tm 84 ° C., Tg 70 ° C., Tm / Tg = 1.20, acid value 6.43 mg KOH / g). Toner 13 was produced in the same manner as in Example 1.

(Comparative Example 6)
Except that 5 parts of paraffin wax A was changed to 5 parts of synthetic ester wax A (Tm 82.5 ° C., Tg 79 ° C., Tm / Tg = 1.04, acid value 2 mgKOH / g) in the toner formulation of Example 1. Toner 14 was produced in the same manner as in Example 1.
(Comparative Example 7)
Example 1 except that 5 parts of paraffin wax A were changed to 5 parts of paraffin wax D (Tm 73 ° C., Tg 56 ° C., Tm / Tg = 1.30, acid value 0.7 mgKOH / g) in the toner formulation of Example 1. Toner 15 was produced in the same manner as in Example 1.

(Comparative Example 8)
Example 1 except that 5 parts of paraffin wax A was changed to 5 parts of carnauba wax C (Tm 80 ° C., Tg 63 ° C., Tm / Tg = 1.27, acid value 6.2 mgKOH / g) in the toner formulation of Example 1. Toner 16 was produced in the same manner as in Example 1.
(Comparative Example 9)
In the toner formulation of Example 1, 5 parts of paraffin wax A were changed to 5 parts of paraffin wax D (Tm 60 ° C., Tg 50 ° C., Tm / Tg = 1.2, acid value 0.4 mgKOH / g). Toner 17 was produced in the same manner as in Example 1.

Example 9
Example 1 except that 5 parts of paraffin wax A was changed to 5 parts of synthetic ester wax B (Tm 62 ° C., Tg 55 ° C., Tm / Tg = 1.15, acid value 4 mgKOH / g) in the toner formulation of Example 1. Toner 18 was produced in the same manner as described above.

[Production Example 19] (Production of polyester resin (b1))
In a reaction vessel equipped with a cooling tube, a stirring frame, and a nitrogen insertion tube, 3 parts of 1,4-butanediol, 450 parts of L-lactic acid, 50 parts of D-lactic acid and 2 parts of tetrabutoxytitanate are added at normal pressure. The mixture was dehydrated and condensed at 160 ° C. for 3 hours, and further dehydrated and condensed at 160 ° C. under a reduced pressure of 10 to 15 mmHg. The resin taken out was cooled to room temperature, and then pulverized into polyester diol containing a polyhydroxycarboxylic acid skeleton (optical purity 80 mol%). Obtained [Polyester b1-6] was obtained. [Polyester b1-6] had a Tg of 47 ° C.

[Production Example 20] (Production of polyester resin (b1))
In a reaction vessel equipped with a cooling tube, a stirring frame, and a nitrogen insertion tube, 3 parts of 1,4-butanediol, 450 parts of L-lactic acid, 50 parts of D-lactic acid and 2 parts of tetrabutoxytitanate are added at normal pressure. The mixture was dehydrated and condensed at 160 ° C. for 3 hours, and further dehydrated and condensed at 160 ° C. under a reduced pressure of 10 to 15 mmHg. The resin taken out was cooled to room temperature, and then pulverized into polyester diol containing a polyhydroxycarboxylic acid skeleton (optical purity 80 mol%). 400 parts of a polyester diol containing a polyhydroxycarboxylic acid skeleton having a hydroxyl number of 11.2 was dissolved in methyl ethyl ketone, followed by addition of 20 parts of IPDI, and an extension reaction was carried out at 50 ° C. for 6 hours to remove the solvent. To obtain [Polyester b1-7]. [Polyester b1-7] had a Tg of 49 ° C.

[Production Example 21] (Production of resin)
200 parts of [urethane-modified polyester] and 800 parts of [polyester b1-6] were melted, kneaded and pulverized in the same manner as in Production Example 10 to obtain [Resin 9] (content (b1) in the resin was 80 %, Optical purity of (b1) 80%).
[Production Example 22] (Production of resin)
200 parts of [urethane-modified polyester] and 800 parts of [polyester b1-7] were melted, kneaded and pulverized in the same manner as in Production Example 10 to obtain [Resin 10] (content (b1) in resin 80) %, Optical purity of (b1) 80%).

(Example 10)
(Toner prescription)
Resin 9 82 parts Carnauba Wax A
(Tm 80 ° C., Tg 67 ° C., Tm / Tg = 1.19, acid value 5 mgKOH / g)
5 parts Modified wax 1 1 part Carbon black (Mitsubishi Chemical # 44) 9 parts Silica: HDK H 2000 3 parts Toner 19 was produced in the same manner as in Example 1 except that the toner formulation was changed as described above.

(Example 11)
(Toner prescription)
Resin 10 82 parts Carnauba Wax A
(Tm 80 ° C., Tg 67 ° C., Tm / Tg = 1.19, acid value 5 mgKOH / g)
5 parts Modified wax 1 1 part Carbon black (Mitsubishi Chemical # 44) 9 parts Silica: HDK H 2000 3 parts Toner 20 was produced in the same manner as in Example 1 except that the toner formulation was changed as described above.

The toners obtained in Examples 1 to 11 and Comparative Examples 1 to 8 were measured and evaluated based on the toner characteristic measuring method described below. The evaluation results are shown in Table 1.
[Charging characteristics under high temperature and high humidity conditions]
Under an atmosphere of 30 ° C. and 80% RH, 10 g of toner and iron powder (“F-150” manufactured by Nippon Iron Powder Co., Ltd.) are accurately weighed in a 50 cc glass bottle with a stopper, and left for 30 minutes. Next, the glass bottle was stoppered and moved under an atmosphere of 23 ° C. and 50% RH, set in a turbula shaker mixer (manufactured by Willy a Baschofen), and stirred at a rotation speed of 90 rpm for 2 minutes. The mixed powder O2g after stirring was loaded into a blow-off powder charge measuring device (TB-203 manufactured by Kyocera Chemical Co., Ltd.) in which a 20 μm stainless steel mesh was set, and remained under conditions of a blow pressure of 10 KPa and a suction pressure of 5 KPa. The charge amount of the iron powder was measured, and the charge amount of the resin particles was calculated by a conventional method. For toners, the higher the negative charge amount, the better the charging characteristics. The evaluation criteria are as follows.
A: Less than −15 μC / g ○: −15 μC / g or more, −10 μC / g or less Δ: −10 μC / g or more, −8 μC / g or less ×: −8 μC / g or more

[Storage stability under high temperature and high humidity conditions]
The toner was allowed to stand for 15 hours so that the temperature was controlled at 50 ° C., and evaluated according to the following criteria based on the degree of blocking.
○: Blocking does not occur.
Δ: Blocking occurs but disperses easily when force is applied.
X: Blocking occurs and does not disperse even when force is applied.

[Melting property]
The toner is uniformly placed on the paper surface so as to be 0.6 mg / cm ² (At this time, the method of placing the powder on the paper surface is to use a printer from which the heat fixing machine is removed (the powder is uniformly placed at the above weight density). Other methods may be used as long as they can be used.) This paper is fixed to a pressure roller at a fixing speed (heating roller peripheral speed) of 213 mm / sec and a fixing pressure (pressure roller pressure) of 10 kg / cm ² . The temperature at which the cold offset was generated was measured, and the evaluation criteria are as follows.
○: Less than 120 ° C, Δ: 120 ° C or more and less than 140 ° C, ×: 140 ° C or more

[Haze degree]
An image was formed on the OHP sheet by the same operation as in the above-described meltability test, and measurement was performed using a haze meter (“NDH2000”, manufactured by Nippon Denshoku Industries Co., Ltd.) in accordance with JISK7136. The haze degree is also referred to as the haze degree, and is measured as a scale indicating the transparency of the resin film. The lower the value, the higher the transparency. The evaluation criteria are as follows.
○: Less than 20%, Δ: 20% or more and less than 30%, ×: 30% or more

[Image density]
In the same manner as in the evaluation of the meltability, the toner is uniformly placed on the paper surface so as to be 0.4 mg / cm ^2. The paper is placed on a pressure roller at a fixing speed (heating roller peripheral speed) of 213 mm / sec, a fixing pressure ( The image density of the sample passed under a pressure roller pressure of 10 kg / cm ² was evaluated by measuring the visual density using X-Rite 938 (manufactured by X-Rite). The evaluation criteria are as follows.
○: Visual density 1.4 or more △: Visual density 1.2 or more and less than 1.4 ×: Visual density 1.2 or less

DESCRIPTION OF SYMBOLS 1 Process cartridge 2 Photoconductor 3 Charging means 4 Developing means 5 Cleaning means

JP 2006-208455 A JP 2006-091278 A

Claims (12)

A toner containing at least a binder resin and a wax (c), wherein the binder resin contains a resin (b1) containing a polyhydroxycarboxylic acid skeleton, and the resin (b1) has a polyhydroxycarboxylic acid skeleton. The monomer that forms comprises an optically active monomer;
The ratio Tm / Tg of the melting point Tm of the wax to the glass transition temperature Tg is in the range of 1.05 to 1.25, the acid value is 6 mgKOH / g or less, and the melting point Tm of the wax is the resin ( An image forming toner characterized by being 15 ° C. or more higher than the glass transition temperature Tg of b1).   Optical purity X (%) in terms of monomer component of resin (b1) = | X (L isomer) −X (D isomer) | [wherein X (L isomer) is an L isomer ratio in terms of optically active monomer ( Mol%), X (D form) represents the D form ratio (mol%) in terms of optically active monomer] is 80% or less, or the content Y of the resin (b1) in the total binder resin Y ( %) And optical purity X (mol%) in terms of monomer component = | X (L form) −X (D form) | [where X (L form) is the L form ratio (mole in terms of optically active monomer) %) And X (D isomer represents D isomer ratio (mol%) in terms of optically active monomer)] satisfy the relationship Y ≦ −1.5X + 220 (80 <X ≦ 100). 1. The toner for image formation according to 1.   The image forming toner according to claim 1, wherein the polyhydroxycarboxylic acid skeleton is a skeleton obtained by (co) polymerizing a hydroxycarboxylic acid having 2 to 6 carbon atoms.   The resin (b1) containing the polyhydroxycarboxylic acid skeleton is a polyester resin composed of a polyester diol (b11) containing a polyhydroxycarboxylic acid skeleton. The toner for image formation described in 1.   The resin (b1) containing a polyhydroxycarboxylic acid skeleton is a linear polyester resin obtained by reacting a polyester diol (b11) containing a polyhydroxycarboxylic acid skeleton together with an extender. The image forming toner according to any one of claims 1 to 3.   The resin (b1) containing the polyhydroxycarboxylic acid skeleton is obtained by reacting a polyester diol (b11) containing a polyhydroxycarboxylic acid skeleton with a polyester diol (b12) other than (b11) together with an extender. The toner for image formation according to any one of claims 1 to 3, wherein the toner is a linear polyester resin.   The image forming toner according to claim 1, wherein the wax (c) is a wax having an ester bond in a main skeleton.   The image forming toner according to claim 1, wherein the toner contains an inorganic filler.   The image forming toner according to claim 1, wherein the image forming toner further contains a modified wax (d) obtained by grafting a vinyl polymer chain onto a wax.   An electrostatic latent image carrier, a charging unit for charging the surface of the electrostatic latent image carrier, an exposure unit for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and the static Developing means for developing an electrostatic latent image with toner to form a visible image; Transfer means for transferring the visible image to a recording medium; Fixing means for fixing the transferred image transferred to the recording medium; An image forming apparatus comprising: the image forming apparatus according to claim 1, wherein the toner is the image forming toner according to claim 1.   A charging process for charging the surface of the electrostatic latent image carrier, an exposure process for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and developing the electrostatic latent image using toner. An image forming method including at least a developing step for forming a visible image, a transferring step for transferring the visible image to a recording medium, and a fixing step for fixing the transferred image transferred to the recording medium. The image forming method according to claim 1, wherein the toner is an image forming toner according to claim 1.   The image forming apparatus main body includes at least an electrostatic latent image carrier and developing means for developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible image. A process cartridge that is detachable, wherein the toner is the image forming toner according to claim 1.

Images