JP4085705B2 - Image forming toner, manufacturing method thereof, developer using the same, image forming method, and image forming apparatus - Google Patents

Description

【０１６５】
【発明の効果】
本発明によれば、定着性に特に優れた立体画像を、容易に形成し得る画像形成用トナー、およびそのトナーの作成方法、ならびに該トナーを含む現像剤を提供できる。また、簡易に立体画像を形成し得る画像形成方法および画像形成装置を提供することができる。
【図面の簡単な説明】
【図１】 本発明の画像形成用トナーを用いた画像形成方法に利用される画像形成装置（カラープリンタ）の一例を示す模式図である。
【図２】 本発明の実施例の評価に用いた引っ張り試験改造機を示す模式図である。
【図３】 本発明の実施例の評価に用いた引っ張り試験改造機の一部を示す模式図である。
【符号の説明】
１ 感光体（静電潜像担持体）、２ 露光装置、３ コロナ帯電器、４ 中間転写体、５ａ，５ｂ，５ｃ，５ｄ 現像装置（現像手段）、６ 転写器（転写手段）、７ クリーニング手段、８ 加熱ロール（定着手段）、９ 加圧ロール（定着手段）、１０ 記録媒体、１１ 基材、１２ 立体画像、１３ 荷重測定器、１４ 基材把持部材、１５ 台、１６ 刃、１７ 突き当て部材、１８ シャフト、１９ ダイヤルゲージ、２０ 被検査体、２１ シャフト固定部材、３０ ブロック、Ａ 移動方向。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an image forming toner, a manufacturing method thereof, a developer using the toner, an image forming method, and an image forming apparatus. More specifically, the present invention relates to an image forming toner suitably used for forming a stereoscopic image using an electrostatic process or the like, a manufacturing method thereof, a developer using the toner, an image forming method, and an image forming apparatus.
[0002]
[Prior art]
Three-dimensional image materials are used as materials for advertising and educational materials. A stereoscopic image is useful because it gives not only a flat visual information but also a three-dimensional information to the receiver from a shadow and a finger feeling, thereby giving a strong impression and understanding. In particular, Braille characters and Braille images can be used effectively. Stereoscopic images are used not only for language information but also for image information such as maps, and are indispensable for visually impaired people.
[0003]
Conventionally, the following methods are known as methods for forming a stereoscopic image. For example, for producing Braille characters and the like, a method is widely used in which protrusions are embossed on a paper surface with a Braille typewriter. In addition, as a method of duplicating a three-dimensional image and producing a Braille book, etc., using a Braille image formed on a zinc plate according to the same principle as the Braille typewriter, the Braille plate making machine or Braille There is a method of copying using a printing press. Further, as a method for producing a stereoscopic image pamphlet, etc., ultraviolet curable high-viscosity polymer ink is printed in a mountain shape by using a printing technique such as a normal silk screen, and then ultraviolet cured to obtain a stereoscopic image. However, it is not a method that can be easily used in general offices.
[0004]
The conventional three-dimensional image forming method is disadvantageous in that it takes time and the place of use is limited. Furthermore, in the case of duplicating a stereoscopic image, the duplication process and the apparatus to be used are complicated and large, and are not suitable for today's information society. Today's office equipment has made tremendous progress, especially with the advancement and penetration of personal computers, making the creation of documents quicker and easier, and the output equipment has also been reduced in size, weight, cost, speed, and color. Have been doing. There is a demand for a device that can easily output and copy a stereoscopic image. In particular, if software that can convert normal characters (planar characters) into Braille characters or vice versa can be obtained at low cost, it is possible to further promote social participation of visually impaired persons. Also, an output device that can easily output Braille characters and the like is desired in order to expand the possibility of exchange of e-mail between visually impaired persons. That is, the present situation is that an easy and high-speed system compatible with today's office environment is desired in place of the conventional complicated and large system for outputting and copying a stereoscopic image.
[0005]
On the other hand, JP-A-8-60054 proposes an inkjet ink containing an ultraviolet-decomposable gas generating photosensitive compound, a device using the same, and a method for forming a stereoscopic image using the same. . Since the output device disclosed in this document is small and can also be output from a personal computer, it is useful as means for forming a stereoscopic image. However, when a stereoscopic image is to be output on plain paper, there is a problem that liquid ink penetrates between the fibers of the paper and a sufficient stereoscopic image cannot be obtained even if the image is expanded with ultraviolet rays. For this reason, there is a proposal to use a non-liquid-absorbing recording material such as PET (polyterephthalate), but it is expensive and is not suitable for bookbinding, and is difficult to put into practical use.
[0006]
Therefore, as a method for easily forming a braille image, a method using an electrophotographic method widely used for offices and personal use has been proposed. For example, Japanese Patent Publication No. 59-35359 and Japanese Patent Application Laid-Open No. 61-72589 propose a method using a thermally expandable sheet. This is a method of forming a stereoscopic image by uniformly applying a thermally expandable sheet on a support such as paper and thermally expanding only the image portion. According to this method, a normal copying machine can be used, and this thermally expandable sheet is used in place of the conventional plain paper, and an image made of black toner is produced on the sheet, and the heat absorption property of the black toner is utilized. Then, the thermal expansion material under the toner image can be expanded to form a three-dimensional image. This method is preferable in that a three-dimensional image can be easily formed. However, in order to sufficiently expand the thermal expansion material, black toner is required, another heating device is required, and sufficient image thickness is obtained. It is not preferable from the viewpoint that it takes time to form a three-dimensional image having, and that it is necessary to apply a heat-expandable material to the entire surface of the sheet, which makes it impossible to meet the demand for resource saving. Furthermore, the sheet is thick and unsuitable for binding a large number of sheets such as books, and is difficult to put into practical use.
[0007]
On the other hand, JP-A-4-333858 and JP-A-8-63039 propose a method of forming a stereoscopic image by using a conventional electrophotographic method and increasing the amount of toner on the image. This method is a method in which a conventional toner is used in a larger amount than in the past to form a toner image and increase the image height. If high-temperature fixing is performed in order to sufficiently fix the toner, there is a problem that the toner melts and penetrates into the fiber of the paper and the image height becomes insufficient.
[0008]
Further, JP-A-52-28325 proposes a toner for electrophotography containing a dry foaming agent. This is a technique in which a conventional toner and dry foaming agent powder mixed are used, and after the image formation, the dry foaming agent is expanded by heat to obtain a three-dimensional image. However, depending on the powder mixing, the toner and the foaming agent cannot be mixed sufficiently uniformly, so there are many cases where there is a foaming agent having no adhesive force at the interface with the paper, and sufficient fixing properties are obtained. A three-dimensional image having In addition, since the adhesiveness between the dry foam boiling agent and the toner particles is not sufficient, a dry foam boiling agent is included in the toner to some extent in order to further improve the adhesiveness. Bubbles are boiled due to overheating kneading at the time, and the thermal expansibility disappears), and the dry foaming agent is further mixed with powder to improve the adhesion between the toner particles and the foaming agent. Yes. However, the adhesion between the paper and the toner does not improve, and the fixability between the image and the paper is still insufficient. In general, since the chargeability of the binder resin and the dry foaming agent are different, the charge distribution of the toner is widened due to the difference in chargeability, the image quality of the image obtained as the environment changes and as it is used for a long time. Decreases.
[0009]
Japanese Patent Laid-Open No. 7-061047 proposes an information input / output method for forming a protruding image using a thermal foaming agent-containing toner. The toner used in this method is a toner prepared by mixing a toner binder resin, a colorant, and a thermal foaming agent, and finely pulverizing the toner. The thermal foaming agent is exposed on the surface of the pulverized toner. ing. Accordingly, the thermal foaming agent is exposed at the interface between the paper and the toner, and the adhesiveness between the toner and the paper is lowered as in the above proposal, and the fixability of the obtained image is inferior. Further, since the heat-sensitive foaming agent is exposed on the toner surface, the chargeability of the toner surface becomes non-uniform. Accordingly, the charge distribution of the toner becomes wide, and when the toner is used in a low temperature and low humidity environment or for a long period of time, the image quality such as fogging is deteriorated. Furthermore, since the toner used is produced by a normal kneading and pulverizing method, it is considered that most of the heat-sensitive foaming agent is foamed and loses its effectiveness due to heat during kneading. As a result, since the foaming agent cannot be sufficiently expanded only by heat fixing of a normal copying machine or the like, it is necessary to pass the output image through a superheater, which is insufficient in terms of simplicity.
[0010]
As described above, it is easy to use a normal electrophotographic copying machine or small printer, without necessarily requiring a separate heating device, without requiring substantial modifications, and without making substantial modifications. Actually, there is no toner capable of forming a stereoscopic image.
[0011]
[Problems to be solved by the invention]
The first object of the present invention is a stereoscopic image that is particularly excellent in fixing property, uniformity of image height, etc. when used in a general copying machine or printer without causing the above-mentioned problems or disadvantages. It is to provide a novel image-forming toner capable of easily forming the toner, to produce the toner, and to provide a developer containing the toner.
[0012]
The second object of the present invention is to form a stereoscopic image having an image height that can be practically sufficiently recognized in Braille, even on plain paper, and to provide a stereoscopic image having practically sufficient fixability and image quality. An image forming toner that can be formed, a method for producing the toner, and a developer containing the toner.
[0013]
A third object of the present invention is to provide a novel image forming toner capable of forming a three-dimensional image and corresponding to resource saving, a method for producing the toner, and a developer containing the toner.
[0014]
A fourth object of the present invention is to provide a three-dimensional image forming toner excellent in charging stability, environmental stability and productivity, a method for producing the toner, and a developer containing the toner.
[0015]
A fifth object of the present invention is to provide an image forming method and an image forming apparatus capable of easily forming a stereoscopic image.
[0016]
[Means for Solving the Problems]
As a result of repeated studies on the above problems, the present inventors have found that the above problems can be solved by the following image forming toner and the like, and have completed the present invention.
[0017]
That is, the means for achieving the above object are as follows.
[0018]
<1> An image forming toner characterized in that the toner contains at least a binder resin and a foaming agent having an outer shell, and contains a compound that binds the binder resin and the outer shell of the foaming agent. .
[0019]
<2> An image forming toner, wherein the toner contains at least a binder resin, a foaming agent, a metal compound or a polyvalent amine.
[0020]
<3> A step of adjusting an oil component by mixing at least a binder resin and a foaming agent having an outer shell in an organic solvent in which the binder resin can be dissolved; and An image forming method comprising: a step of preparing a suspension by suspending in an aqueous solvent containing a compound that binds the shell and preparing the suspension; and a step of removing the organic solvent from the suspension. This is a manufacturing method for toner.
[0021]
<4> A developer comprising a toner and a carrier, wherein the toner is the image forming toner according to <1> or <2>.
[0022]
<5> A developing step of developing a latent image formed on the surface of the electrostatic latent image carrier with toner to form a toner image; and a toner image formed on the surface of the electrostatic latent image carrier. And a fixing step of fixing a toner image on a recording medium. In the image forming method, the toner is the toner described in <1> or <2>, and the toner in the fixing step The foaming agent contained in is foamed to form a three-dimensional image on a recording medium.
[0023]
<6> An electrostatic latent image carrier, developing means for developing a latent image formed on the surface of the electrostatic latent image carrier with toner to form a toner image, and on the surface of the electrostatic latent image carrier The image forming apparatus according to <1> or <2>, wherein the toner is a transfer unit that transfers the toner image formed on the recording medium, and a fixing unit that fixes the toner image on the recording medium. An image forming apparatus, wherein the fixing unit is a unit that foams a foaming agent contained in the toner to form a three-dimensional image on a recording medium.
[0024]
According to the toner for image formation of the present invention (hereinafter sometimes simply referred to as “toner”), the binder resin and the foam are defined by defining the toner (and the binder resin, the foaming agent, especially the additive). Since both the adhesiveness to the agent and the adhesiveness of the toner to the recording medium (paper, etc.) are not hindered, a stereoscopic image having good fixability can be obtained.
[0025]
As a form of the image forming toner of the present invention, it is preferable that the foaming agent having an outer shell is a microcapsule particle containing a low-boiling point substance from the viewpoint of improving thermal expansion.
[0026]
In addition, the method for producing a toner for image formation or the like in the present invention may be a production method including a step of dispersing and polymerizing a binder resin monomer in which a foaming agent is dispersed in an aqueous phase. . According to these production methods, the toner can be easily produced.
[0027]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is described in detail below.
[0028]
(Image forming toner)
The toner for image formation of the present invention includes at least a binder resin, a foaming agent having an outer shell, and a compound (hereinafter referred to as “third component material”) that binds the binder resin and the outer shell of the foaming agent. ) And.
[0029]
In the image forming toner of the present invention, the binder resin in the image forming toner is fixed to the recording medium, while the outer shell of the foaming agent and the binder resin are bonded together by a third component material described later. The foaming agent foams at the time of fixing, and the fixability of the convex image is improved.
[0030]
The toner for image formation of the present invention has a sphericity of 100 or more and 130 or less, more preferably 100 or more and 120 or less. When the sphericity exceeds 130, the contact area between the photoconductor and the toner increases, so that the transferability is lowered and it is difficult to obtain a good convex image. In order to improve the blade cleaning property, those having a sphericity of 140 to 150 are preferably used.
[0031]
Here, the degree of spheroidization is, for example, using Hitachi FE-SEM (S = 800), randomly sampling 100 toner images magnified to a magnification of 500 times, and the image information is sent to, for example, Nireco via an interface. It is an average value of values (shape factor MSL2) obtained by introducing into an image analysis apparatus (Luzex III) manufactured by a company, performing analysis, and calculating by the following equation (1). Incidentally, the shape of the toner prepared by the ordinary kneading and pulverizing method is indefinite, and MLS2 is about 140.
[0032]
[Expression 1]
MSL2 = (maximum length of toner particles)²/ (Projection area of toner particles) × π × 1/4 × 100 (1)
[0033]
The image forming toner of the present invention preferably has a volume average particle size of 3 to 50 μm. Especially preferably, it is 20-30 micrometers. The volume average particle diameter is a value measured using a particle size measuring device Multisizer (aperture diameter 100 μm, volume average diameter) manufactured by Coulter Counter.
[0034]
The toner for image formation according to the present invention is suitably applied to a system that does not require oil supply to a fixing device (heat roll) by inserting a release agent, an image forming apparatus having a so-called oilless fixing mechanism, or an image forming method. Can be made.
[0035]
The image forming toner of the present invention can be preferably obtained while the degree of spheroidization satisfies the above conditions, but is preferably obtained by the image forming toner manufacturing method of the present invention described later.
[0036]
Hereinafter, each toner material will be described in detail.
[0037]
Next, the third component material contained in the image forming toner of the present invention will be described.
[0038]
As the third component material, a material that can be coordinated to the binder resin and the outer shell of the foaming agent or a material that can be ionically bonded is preferably used. Specific examples include water-soluble metal compounds and polyvalent amines. The metal compound is preferably a metal salt, and more preferably a polyvalent metal salt. Examples of the metal compound include those that undergo ionic crosslinking, such as CaCl.₂MgCl₂, NaCl, Al₂(SO_Four)_ThreePAC (Poly Alminium Chloride), metal salts such as calcium nitrate, barium chloride, zinc chloride, aluminum chloride, aluminum sulfate, polyaluminum hydroxide, calcium polysulfide and the like.
[0039]
The polyvalent amine is preferably a diamine, more preferably a diamine having 2 to 12 carbon atoms. Examples of the polyvalent amine include 1,10-diaminodecane, 1,12-diamidodecane, 1,6-diaminohexane, 1,8-diaminooctane, ethylenediamine, and 1,4-diaminobutane. Can be mentioned.
[0040]
Next, the binder resin contained in the image forming toner of the present invention will be described.
[0041]
The binder resin in the present invention is not particularly limited, and a known fixing resin can be used. Below, the specific example of binder resin which can be used for this invention is given with the resin kind.
[0042]
-Polyester obtained by condensation polymerization of an alcohol component and a carboxylic acid component (as the alcohol component, for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, xylene glycol, Dipropylene glycol, polypropylene glycol, bisphenol A, hydrogenated bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, dihydric or higher alcohols and alcohol derivatives such as sorbitol, glycerin, etc .; For example, maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, trimellitic acid, Pyromellitic acid, cyclopentanedicarboxylic acid, succinic anhydride, trimellitic anhydride, maleic anhydride, dodecenyl succinic anhydride and other carboxylic acids, carboxylic acid derivatives and carboxylic anhydrides; alcohol components and carboxylic acids Two or more types of acid components may be combined.
[0043]
Acrylic acid or methacrylic acid ester polymers (for example, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyethyl acrylate 2-ethylhexyl, polyacrylate, lauryl acrylate, etc .; polymethyl methacrylate, poly Methacrylic acid ester polymers such as butyl methacrylate, polyhexyl methacrylate, poly 2-ethylhexyl methacrylate, and polylauryl methacrylate).
[0044]
-A copolymer of acrylic acid ester and methacrylic acid ester.
[0045]
A copolymer of a styrene monomer and an acrylic ester or methacrylic ester.
[0046]
-Ethylene polymers (for example, polyvinyl acetate, vinyl polypropyleneate, polyethylene, polypropylene, etc.) and copolymers thereof.
[0047]
-Styrene copolymers (for example, styrene / butadiene copolymers, styrene / isoprene copolymers, styrene / maleic acid copolymers, etc.).
[0048]
In addition, polyvinyl ether, polyvinyl ketone, polyester, polyamide, polyurethane, rubber, epoxy resin, polyvinyl butyral, rosin, modified rosin, terpene resin, phenol resin, and the like.
[0049]
Among these, polyester is particularly preferable. These may be used alone or in combination of two or more.
[0050]
The foaming agent having an outer shell in the present invention is a microcapsule particulate foaming agent (hereinafter sometimes referred to as “microcapsule type foaming agent”) enclosing a foaming agent to be described later. The foaming agent to be included is not particularly limited, and any foaming agent can be used as long as it expands by heat. It may be solid at room temperature, liquid, or gaseous.
[0051]
Further, the foaming agent is not limited to a material composed of a single substance, and may be a material composed of a plurality of substances or a functional material such as microcapsule particles. The foaming temperature of the foaming agent varies depending on the apparatus used to form the stereoscopic image. However, when forming a stereoscopic image using an ordinary copying machine, the foaming temperature is the heat fixing temperature. The following is preferable.
[0052]
As the foaming agent, for example, a foaming agent mainly composed of a substance that generates gas by thermal decomposition can be used. Specifically, a bicarbonate such as sodium hydrogen carbonate that generates carbon dioxide by thermal decomposition, NaNO that generates nitrogen gas₂And NH_FourExamples thereof include a mixture of Cl, an azo compound such as azobisisobutylnitrile and diazoaminobenzene, and a peroxide that generates oxygen and the like.
[0053]
Moreover, as another foaming agent, the low boiling point substance (it may be a liquid state or a solid state at normal temperature) vaporized at low temperature is mentioned. The microcapsule type foaming agent containing the low boiling point substance is more preferable because of its high foamability. When the image forming toner of the present invention is used in an ordinary copying machine, the low boiling point substance contained in the microcapsule type foaming agent needs to be vaporized at a temperature lower than at least the heat fixing temperature. Specifically, it is a substance that vaporizes at 100 ° C. or lower, preferably 50 ° C. or lower, more preferably 25 ° C. or lower. However, since the thermal responsiveness of the microcapsule type foaming agent depends not only on the boiling point of the low-boiling substance as the core material, but also on the softening point of the outer shell (that is, the wall material), the preferred boiling range of the low-boiling substance is It is not limited to the said range. Examples of the low boiling point substance include neopentane, neohexane, isohexane, isobutylene, and isobutane. Among them, isobutane which is stable with respect to the wall material of the microcapsule and has a high thermal expansion coefficient is preferable.
[0054]
The outer shell (ie, wall material) of the microcapsule type foaming agent has solvent resistance to various solvents used in the toner manufacturing process, and the low-boiling substance contained in the microcapsule type foaming agent is vaporized. In this case, a material that is impermeable to gas is preferable. Further, when the image forming toner of the present invention is used in a normal copying machine, the wall material needs to be softened and expanded at a temperature lower than the heat fixing temperature. Conventionally used wall materials can be widely used as wall materials for microcapsules. For example, acrylic resins such as polyvinyl chloride, polyvinyl acetate, polystyrene, copolymers of vinylidene chloride and acrylonitrile, polyacrylonitrile, polybutadiene, polyacrylic acid ester, polyacrylic acid ester, and other acrylic resins, polyesters, or the above-mentioned A copolymer in which two or more monomers forming the polymer are combined is preferably used. Among these, a copolymer of vinylidene chloride and acrylonitrile is preferable in terms of high adhesiveness to the binder resin and high solvent resistance. The functional group of the outer shell may be either an acidic group or a basic group. In addition, when the third component material is ion-crosslinked with a metal compound, an acidic group that easily becomes an anion is preferable.
[0055]
The preferred range of the foaming agent content in the image forming toner of the present invention varies depending on the type of foaming agent, but is usually 5% by mass to 50% by mass, and preferably 10% by mass to 40% by mass. If the foaming agent is less than 5% by mass, the thermal expansion of the toner may be insufficient in practice, while if it exceeds 50% by mass, the proportion of the binder resin in the toner is relatively insufficient. There may be a problem that sufficient fixing property cannot be obtained.
[0056]
In addition to the above components, the image forming toner of the present invention contains a colorant, a release agent, inorganic fine particles (internal additive), a charge control agent (internal additive), inorganic fine particles (external additive), and the like. You may contain as another additive.
[0057]
Known pigments and dyes can be used as the colorant.
[0058]
For example, carbon black (eg, furnace black, channel black, thermal black, etc.), inorganic pigment (eg, bengara, bitumen, titanium oxide, etc.), azo pigment (eg, fast yellow, disazo yellow, pyrazolone red, chelate red, brilliant carmine, para Brown, benzimidazolone, etc.), phthalocyanine pigments (eg, copper phthalocyanine, metal-free phthalocyanine, etc.), condensed polycyclic pigments (eg, flavantron yellow, dibromoanthrone orange, perylene red, quinacridone red, dioxazine violet, etc.), carmine lake And pigments.
[0059]
Examples of pigments include CI Pigment Yellow 93, CI Pigment Yellow 180, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Red 122, CI Pigment Red 57: 1, CI Pigment Red 185, and Carbon Black. This is preferable from the viewpoint of the reproducibility of intermediate colors.
[0060]
The pigment is preferably used in combination with a pigment dispersant in order to keep the dispersion state stable. Specific examples of the pigment dispersant include EFKA47, EFKA4009, EFKA4010 (modified polyurethane: manufactured by EFKA CHEMICALS), Ajisper PA111 (manufactured by Ajinomoto Co., Inc.), Disparon DA-705, Disparon DA-725, Disparon DA-400N (Polyester) : Manufactured by Enomoto Kasei Co., Ltd.).
[0061]
The pigment is preferably used in combination with a pigment derivative or the like or a surface-treated pigment for the purpose of further stabilizing the dispersion of the pigment by further bonding with the pigment dispersant. Specific examples of the pigment derivative include dimethylaminoethylquinacridone, sulfonic acid derivatives of anthraquinone, carboxylic acid derivatives of anthraquinone, Solsperse 5000, Solsperse 12000, Solsperse 2000 (manufactured by Geneca), EFKA745, LP6750 (manufactured by EFKA CHEMICALS), and the like. Can be mentioned. Examples of the pigment surface treatment agent include natural rosin (eg, gum rosin, wood rosin, tall rosin, etc.), abietic acid derivatives (eg, abietic acid, levopimaric acid, dextropimaric acid, etc.) and metal salts thereof (eg, calcium salt, sodium salt, Potassium salt, magnesium salt, etc.), rosin / maleic acid resin, rosin / phenol resin and the like. The pigment derivative amount or the pigment surface treatment agent amount is preferably 0.1 to 100% by mass, more preferably 0.1 to 10% by mass with respect to the pigment.
[0062]
As the colorant, when the electrophotographic toner of the present invention is used as a magnetic one-component toner, all or part of the black colorant can be replaced with magnetic powder. Examples of the magnetic powder include simple metals (for example, magnetite, ferrite, cobalt, iron, nickel, etc.) and alloys thereof.
[0063]
It is preferable that content of a coloring agent is about 1-50 mass parts with respect to 100 mass parts of binder resin, More preferably, it is 2-20 mass parts.
[0064]
The image forming toner of the present invention may contain a release agent. It is preferable to include a release agent since an offset phenomenon at the time of contact fixing can be prevented.
[0065]
The release agent has an average particle size (dispersed particle size) of 0.1 μm to 1 μm, preferably 0.3 μm to 0.8 μm. When the average particle size is less than 0.1 μm, the release agent does not act effectively at the time of fixing, and the transfer medium may be wound around the fixing machine. On the other hand, if it exceeds 1 μm, the color developability may be lowered.
[0066]
Here, the average particle diameter of the release agent is obtained by randomly sampling 50 release agent fine particle images magnified at a magnification of 10,000 times from a transmission electron microscope of the toner cross section, (Major axis + minor axis) / 2 is a value calculated by averaging 50 pieces.
[0067]
The ratio of the major axis to the minor axis of the release agent is 1.1 or more and 10 or less, preferably 1.2 or more and 5 or less. When the major axis / minor axis ratio is less than 1.1, the release agent is difficult to penetrate during fixing, and the fixing medium is wound around the fixing machine. On the other hand, if it exceeds 10, the color developability deteriorates.
[0068]
Here, the major axis / minor axis ratio of the release agent is determined by randomly sampling 50 release agent fine particle images magnified at a magnification of 10000 times from a transmission electron microscope of the cross section of the toner. It is a value calculated by measuring the diameter ratio and averaging 50 pieces.
[0069]
In general, the release agent is preferably added in the form of fine particles. Further, it is preferable that the release agent is not exposed on the toner surface. The exposure of the release agent to the toner surface causes a decrease in toner powder fluidity and a decrease in developability, particularly image maintainability.
[0070]
As a method of making the release agent fine particles, a method in which the release agent is wet pulverized in an organic solvent by a media mill to form fine particles, and the release agent is dissolved in an organic solvent and then cooled and precipitated to form fine particles. Or a method of evaporating the release agent in the gas phase to form fine particles. The organic solvent used here is not necessarily the same as the organic solvent used when dissolving the binder resin described later. As for the quantity of this organic solvent, 0.1-20 mass parts is preferable with respect to 1 mass part of mold release agents. The mold release agent can be dissolved by heating, pressurizing, or the like. In the method of evaporating the release agent in the gas phase to make fine particles, an inert gas such as helium, argon and nitrogen is used, and the release agent is heated to a temperature of 100 ° C. to 400 ° C. It has a specific shape by evaporating under reduced pressure of 333 to 1333 Pa (0.01 to 10 torr), adhering the evaporated release agent fine particles to a cooled substrate, and then scraping or dispersing in a solvent. Fine particles can be obtained. In this method, a fraction having a narrow molecular weight distribution can be separated by adjusting the temperature and the degree of vacuum.
[0071]
Specific examples of the release agent include petroleum wax (for example, paraffin wax, oxidized paraffin wax, microcrystalline wax), mineral wax (for example, montan wax), animal and plant wax (for example, beeswax, carnauba wax, etc.), synthetic wax (for example, Polyolefin wax, oxidized polyolefin wax, Fischer-Tropsch wax, etc.). Among these, paraffin wax is preferable. These release agents may be used alone or in combination of two or more.
[0072]
The melting point of the release agent is preferably 50 ° C. to 110 ° C., more preferably 60 ° C. to 100 ° C. In particular, as a mold release agent, paraffin wax having a melting point of 50 ° C to 110 ° C is preferable.
[0073]
The content of the release agent is preferably about 0.5 to 10 parts by mass, more preferably 1 to 7 parts by mass with respect to 100 parts by mass of the binder resin.
[0074]
The image forming toner of the present invention may contain inorganic fine particles. The inorganic fine particles referred to here are so-called internally added substances contained in the toner.
[0075]
Examples of inorganic fine particles include metal salts (for example, calcium carbonate, calcium phosphate, barium sulfate, etc.), metal oxides (for example, silicon oxide, titanium oxide, aluminum oxide, barium titanate, strontium titanate, calcium titanate, cerium oxide, oxidation) Zirconium, magnesium oxide, etc.) and ceramics. Among these, inorganic fine particles having good color developability and a small difference in refractive index from a binder resin such as silicon oxide are preferable. The inorganic fine particles may be used alone or in combination of two or more.
[0076]
Inorganic fine particles usually have a low lipophilicity, so that the incorporation rate into the toner particles tends to be small. Therefore, in order to prevent detachment from the toner particles during the production process, the inorganic fine particles are subjected to a hydrophobic surface treatment. It is preferable to use the same. Examples of such a hydrophobic surface treatment agent include a coupling agent. Specific examples of coupling agents include methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, and diphenyldiethoxy. Silane, isobutyltrimethoxysilane, decyltrimethoxysilane, hexamethyldisilazane, N, N- (bistrimethylsilyl) acetamide, N, N- (trimethylsilyl) urea, tert-butyldimethylchlorosilane, vinyltriethoxysilane, γ-methacrylic Roxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ Glycidoxypropylmethyldiethoxysilane, .gamma.-mercaptopropyltrimethoxysilane, .gamma.-chloropropyl trimethoxysilane silane coupling agent, a titanium coupling agent, and the like. In particular, it is preferable to use silicon oxide subjected to such a hydrophobic treatment as the inorganic fine particles.
[0077]
The average particle size of the inorganic fine particles is preferably 4 nm or more and 500 nm or less, and particularly preferably 6 nm or more and 50 nm or less. If the particle size is outside the above range, sufficient fixability may not be obtained.
[0078]
The content (internal addition amount) of the inorganic fine particles is preferably 20 parts by mass or less, particularly preferably 2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the toner. If this content is outside the above range, the fixability may be insufficient.
[0079]
The image forming toner of the present invention may contain a charge control agent (internal additive).
[0080]
As the charge control agent, those conventionally used for developers can be used. Specifically, metal salts of benzoic acid, metal salts of salicylic acid, and metals of alkyl salicylic acid used in electrophotographic powder toners. Salts, metal salts of catechol, metal-containing bisazo dyes, tetraphenylborate derivatives, quaternary ammonium salts, compounds selected from the group consisting of alkylpyridium salts, resin-type charge control agents containing polar groups, and these A suitable combination is preferred. The addition amount (internal addition amount) of these charge control agents is generally preferably about 10% by mass or less based on the solid content of the toner.
[0081]
The image forming toner of the present invention may contain inorganic fine particles (external additives).
[0082]
Inorganic fine particles (external additives) are added to the surface of the toner in order to give fluidity of the toner. Specifically, metal salts, resins, silicon oxide, titanium oxide, aluminum oxide, titanic acid are used. Examples thereof include metal oxides such as barium, strontium titanate, calcium titanate, cerium oxide, zirconium oxide, and magnesium oxide, ceramics, and carbon black.
[0083]
As the inorganic fine particles (external additives), it is preferable to use those which have been subjected to hydrophobic surface treatment for the purpose of controlling chargeability and the like. Examples of such a hydrophobic surface treatment agent include a coupling agent. Specific examples of the coupling agent include those described above.
[0084]
Further, the image forming toner of the present invention may contain other known external additives as necessary.
[0085]
(Method for producing image-forming toner)
In the first method for producing a toner for image formation according to the present invention, a step of adjusting an oil component (hereinafter referred to as “below”) by mixing at least a binder resin and a foaming agent in an organic solvent capable of dissolving the binder resin. A mixing step), a step of suspending the oily component in an aqueous medium to which the third component material is added, and preparing a suspension by preparing particles (hereinafter referred to as a “suspension step”); And a step of removing the organic solvent from the suspension (hereinafter referred to as “solvent removal step”).
[0086]
The materials used here are the same as those mentioned for the image forming toner of the present invention. Moreover, in addition to each process, you may perform another process suitably.
[0087]
The mixing step of the first production method includes a binder resin, a foaming agent having an outer shell, a colorant dispersion, a release agent dispersion, inorganic fine particles, and, if necessary, in an organic solvent in which the binder resin can be dissolved. Accordingly, it is preferable to adjust the oil component by mixing other additives. As the organic solvent, general organic solvents are used. Specifically, hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane, ethers such as tetrahydrofuran, ethyl acetate, acetic acid Examples thereof include esters such as butyl and ketones such as methyl ethyl ketone and cyclohexane. These organic solvents may be used alone or in combination of two or more.
[0088]
In addition, these organic solvents mainly need to dissolve the binder resin, but the colorant and other additives may be dissolved or only dispersed.
[0089]
The mass ratio of the toner component to the organic solvent is preferably 10/90 to 80/30 from the viewpoint of easy granulation or the final toner yield.
[0090]
In the mixing step and the suspension preparation step, the colorant may be directly mixed with other materials in an organic solvent, but it is preferable to use a colorant dispersion in which a colorant is dispersed in advance. This colorant mixed liquid is, for example, a media type dispersing machine such as a sand mill, ball mill, attritor, or coball mill, a roll mill such as a three roll mill, a cavitation mill such as a nanomizer, a colloid mill, or the like, and a colorant in the organic solvent. Can be obtained by dispersing. At this time, if necessary, other additives such as a pigment dispersant and a pigment derivative are also dispersed. In order to apply an appropriate shearing force when adjusting the colorant dispersion, a part of the binder resin may be added to adjust the viscosity. In addition, the organic solvent used here does not necessarily need to be the same as the organic solvent used when adjusting an oil-based component.
[0091]
In the mixing step and the suspension preparation step, the inorganic fine particles may be mixed with other materials as they are in an organic solvent as in the case of the colorant and the release agent, but the inorganic fine particles are dispersed in advance. A liquid can also be used. This inorganic fine particle dispersion can be obtained, for example, by dispersing inorganic fine particles in an organic solvent like the colorant. In addition, the organic solvent used here does not necessarily need to be the same as the organic solvent used when adjusting an oil-based component.
[0092]
In the mixing step and the suspension preparation step, mixing (stirring) when adjusting the oil component uses a rotor-stator stirrer such as a homogenizer or a colloid mill, an impeller stirrer such as a dissolver, or an ultrasonic stirrer. It is done.
[0093]
In the suspending step, the oily component obtained in the mixing step is suspended in an aqueous medium and granulated to prepare a suspension. However, water is mainly used as the above-mentioned aqueous medium. In addition, a water-soluble solvent may be used in combination. Examples of the water-soluble medium include methyl alcohol, ethyl alcohol, acetone, ethyl acetate and the like, and these can be used within a range that dissolves in water.
[0094]
In the suspension step, it is preferable to use a dispersion stabilizer in order to stabilize the oil component in the aqueous medium. Examples of such a dispersion stabilizer include inorganic fine particles and water-soluble polymers. Examples of the inorganic fine particles include calcium phosphate, hydroxyapatite, calcium carbonate, titanium oxide, aluminum hydroxide, magnesium hydroxide, barium sulfate, and silicon oxide. Examples of the water-soluble polymer include cellulose, hydroxypropylmethylcellulose, methylcellulose, carboxymethylcellulose, starch, polyvinyl alcohol, and polyacrylic acid. The amount of the dispersion stabilizer is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the aqueous medium. The average particle size of the inorganic fine particles used as the dispersion stabilizer is preferably 1 μm or less.
[0095]
In the suspension step and suspension preparation step, a dispersion stabilizing aid may be used in combination. Various surfactants can be used as the dispersion stabilizing aid. Examples of the surfactant include ionic and nonionic surfactants. Specifically, examples of the anionic surfactant include alkylbenzene sulfonate, alkylphenyl sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, sulfate of higher fatty acid ester, sulfonate of higher fatty acid ester, and the like. Can be used. As the cationic surfactant, primary to tertiary amine salts, quaternary ammonium salts and the like can be used. Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan Fatty acid esters, fatty acid alkylolamides and the like can be used. These dispersion stabilizers are preferably used in the range of 0.001 to 5 parts by mass with respect to the aqueous medium.
[0096]
The mass ratio of the oily component and the aqueous component in the suspension process and the suspension preparation process is preferably 10/90 to 90/10, although it varies depending on the final toner particle size and the production apparatus.
[0097]
Moreover, it is preferable that the oil component is granulated under high-speed shearing. Among them, it is preferable to use a high-speed blade rotating type or forced interval passing type emulsifier such as various homomixers, homogenizers, and colloid mills.
[0098]
In the solvent removal step, the organic solvent is removed from the suspension, whereby a particleized toner can be obtained. Alternatively, the organic solvent may be removed after adding a poor solvent to the suspension to precipitate the toner (particles). Examples of the poor solvent include methanol and ethanol.
[0099]
The removal of the solvent may be performed at normal pressure or at reduced pressure. When performing at normal pressure, it is necessary to set the temperature of solvent removal below the boiling point of the solvent and to take into consideration the glass transition temperature of the resin (hereinafter sometimes referred to as “Tg”). If it is carried out at a temperature that greatly exceeds the Tg of the resin, toner coalescence occurs, which is not preferable. The removal of the solvent is usually preferably carried out with stirring at around 40 ° C. for 3 to 24 hours. When removing the solvent under reduced pressure, 2.67 × 10^Three~ 2.00 × 10^FourIt is preferable to carry out at Pa (20-150 mmHg).
[0100]
After the toner obtained through the above steps is taken out by filtration, it is usually washed, dried and classified.
[0101]
The washing is preferably performed with an acid such as hydrochloric acid, nitric acid, formic acid or acetic acid which dissolves the inorganic dispersion stabilizer or the like adhering to the toner surface. When the idle dispersion stabilizer or the organic dispersion stabilizer remains on the toner surface, the humidity dependency of the residual deposit may increase the humidity dependency of the chargeability of the toner. Therefore, it is preferable to remove the dispersion stabilizer by washing because the charging stability of the toner is further improved. After the toner is washed with an acid, it may be washed again with an alkaline water such as sodium hydroxide if desired. As a result, by placing in an acidic atmosphere, a part of the ionic substance on the surface of the insolubilized toner is solubilized and removed again to further improve the chargeability and powder flowability.
[0102]
Washing can be efficiently performed by adjusting conditions such as pH at the time of washing, the number of times of washing, and temperature at the time of washing. Furthermore, it is preferable to use a stirrer or an ultrasonic dispersion device because the cleaning operation can be carried out more effectively. After washing the toner, if desired, further steps such as filtration, decantation, and centrifugation are carried out to dry the toner.
[0103]
Drying is performed using a known apparatus such as aeration drying apparatus, spray drying apparatus, rotary drying apparatus, airflow drying apparatus, fluidized drying apparatus, electrothermal heating drying apparatus, and freeze drying apparatus.
[0104]
In the toner manufacturing method of this aspect, since any process that is performed under high-temperature heating is not included in any process, the thermal expansion property of the foaming agent is not deactivated during the manufacturing process, and the obtained toner Has a high thermal expansibility.
[0105]
In the method for producing an electrophotographic toner of the present invention, an external additive such as inorganic fine particles is added as necessary. The external additive may be added by drying the toner, and then adding a V blender, Henschel. Using a mixer such as a mixer, the external additive may be attached to the toner surface in a dry manner, or suspended in an aqueous solvent and granulated, and then added to the slurry toner (suspension). The external additive may be adhered to the toner surface by drying, or the external additive may be adhered to the toner surface by drying while spraying a slurry toner (suspension) on the external additive. Good.
[0106]
As a method for producing the image forming toner of the present invention, there is a method using suspension polymerization in addition to the above-described dissolution suspension method. In this suspension method, a microcapsule type foaming agent and optionally other additives are dissolved or dispersed in advance in the binder resin monomer. The binder resin monomer is suspended and dispersed in an aqueous medium. At this time, the microcapsule type foaming agent is held inside the particles composed of the monomer dispersed in the aqueous medium. Next, when an arbitrary initiator is added to the aqueous medium and the monomer is subjected to suspension polymerization, the polymerization proceeds while the foaming agent is contained inside the monomer particles. As a result, particles in which the foaming agent is not substantially exposed on the surface can be produced efficiently and easily. The progress of suspension polymerization varies depending on the type of monomer, but generally proceeds in a temperature range of 60 to 90 ° C. As described above, in the suspension polymerization method, the production process can be carried out at a lower temperature than in the case of producing by the conventional kneading and pulverization method, and the thermal expansion of the foaming agent is suppressed from being deactivated during the production process. can do. Other additives may be dispersed in an aqueous medium in addition to being previously dispersed in the monomer.
[0107]
After completion of suspension polymerization, the obtained toner may be subjected to washing treatment and drying treatment, if desired. The specific operation of each process is the same as described above.
[0108]
The image forming toner of the present invention can be obtained by the image forming toner manufacturing method of the present invention.
[0109]
(Developer)
The developer of the present invention is a two-component developer containing the image forming toner of the present invention and a carrier. There is no restriction | limiting in particular as a carrier which can be used for the developing agent of this invention, A well-known carrier can be used. For example, a resin-coated carrier having a resin coating layer on the surface of the core material can be exemplified. Further, a resin-dispersed carrier in which a conductive material or the like is dispersed in a matrix resin may be used.
[0110]
Coating resins and matrix resins used for carriers include polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl bratil, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether, polyvinyl ketone, vinyl chloride copolymer , Styrene-acrylic acid copolymer, straight silicone resin composed of organosiloxane bond or modified product thereof, fluorine resin, polyester, polyurethane, polycarbonate, phenol resin, amino resin, melamine resin, benzoguanamine resin, urea resin, amide resin, epoxy Although resin etc. can be illustrated, it is not limited to this.
[0111]
Examples of the conductive material include metals such as gold, silver, and copper, carbon black, titanium oxide, zinc oxide, barium sulfate, aluminum borate, potassium titanate, and tin oxide, but are not limited thereto. It is not a thing.
[0112]
Examples of the carrier core material include magnetic metals such as iron, nickel, and cobalt, magnetic oxides such as ferrite and magnetite, and glass beads. However, the carrier must be a magnetic material for use in the magnetic brush method. Is preferred.
[0113]
The volume average particle diameter of the carrier core material is generally 10 to 500 μm, preferably 30 to 200 μm.
[0114]
In order to coat the surface of the core material of the carrier with a resin, there may be mentioned a method of coating with a coating layer forming solution in which the coating resin and, if necessary, various additives are dissolved in an appropriate solvent. The solvent is not particularly limited and may be appropriately selected in consideration of the coating resin to be used, coating suitability, and the like.
[0115]
Specific resin coating methods include an immersion method in which the carrier core material is immersed in the coating layer forming solution, a spray method in which the coating layer forming solution is sprayed onto the surface of the carrier core material, and the carrier core material is fluidized air. And a kneader coater method in which the carrier core material and the coating layer forming solution are mixed in a kneader coater and the solvent is removed in a kneader coater.
[0116]
The mixing ratio (mass ratio) of the electrophotographic toner of the present invention to the carrier in the electrophotographic developer of the present invention is in the range of toner: carrier = 1: 100 to 50: 100, preferably 3: The range is about 100 to 30: 100.
[0117]
(Image forming method and image forming apparatus)
The image forming method of the present invention includes a development step of developing a latent image formed on the surface of the electrostatic latent image carrier with toner to form a toner image, and the image forming method formed on the surface of the electrostatic latent image carrier. In the image forming method comprising a transfer step of transferring a toner image to a recording medium and a fixing step of fixing the toner image on the recording medium, the toner is the image forming toner of the present invention, and in the fixing step, A foaming agent contained in a toner is foamed to form a three-dimensional image on a recording medium.
[0118]
The image forming apparatus according to the present invention further includes a developing unit that develops a latent image formed on the surface of the electrostatic latent image carrier with toner to form a toner image, and the image forming apparatus that is formed on the surface of the electrostatic latent image carrier. An image forming apparatus comprising: transfer means for transferring the toner image to a recording medium; and fixing means for fixing the toner image on the recording medium. The toner is the image forming toner of the present invention, and the fixing The means is a means for foaming a foaming agent contained in the toner to form a three-dimensional image on a recording medium.
[0119]
The image forming method and the image forming apparatus of the present invention are described in detail below.
[0120]
When the image forming toner of the present invention is used, a fixing device of an electrophotographic image forming apparatus such as a general copying machine or printer is used as it is to fix an image on a recording medium and foam a foaming agent in the toner. Thus, a stereoscopic image can be formed. As the fixing device, a conventional heating method fixing device such as an oven method, a heat roll method, a heat belt method, or the like can be used as appropriate. Is preferred. As described above, by using the image forming toner of the present invention, a general electrophotographic system is used without newly designing an image forming apparatus for forming a stereoscopic image and without substantially modifying the image forming apparatus. A stereoscopic image can be easily formed using the apparatus. In addition, since a large number of stereoscopic images can be easily copied as easily as copying in an office, a booklet including Braille characters and a stereoscopic image can be easily created.
[0121]
The toner weight (TMA) per unit area in an image obtained using the image forming toner of the present invention is 5 to 150 g / m.²Is preferred, 50-130 g / m²Is more preferred, 70-80 g / m²Is particularly preferred.
[0122]
In order to foam the image forming toner of the present invention, the fixing temperature is set to 120 to 250 ° C., preferably 130 to 240 ° C., more preferably 140 to 200 ° C. If the fixing temperature is 120 ° C. or lower, the foaming agent may not be sufficiently foamed and a sufficient image thickness may not be obtained. On the other hand, when the temperature exceeds 250 ° C., the binder resin or the like may be decomposed. It is not always necessary to perform fixing and foaming of the foaming agent at the same time. Once the image is fixed with a relatively low-temperature fixing roll or the like, a foaming agent is separately added with a relatively high-temperature fixing roll in the above temperature range. You may make it foam.
[0123]
In addition, when the image forming toner of the present invention is used, an image that can form both a normal image (planar image) and a stereoscopic image can be formed simply by adding a means for controlling the fixing temperature to a conventional electrophotographic image forming apparatus. It becomes a forming device. As a means for controlling the fixing temperature, for example, a heater built in the fixing roll is controlled in accordance with information from the user, and a fixing temperature T of the fixing roll in the normal image forming mode is controlled.₀Temperature T higher than ℃₁A control system for setting the temperature in degrees Celsius is included. Fixing temperature T at this time₁° C. is a temperature sufficient for foaming of the foaming agent contained in the toner at the set fixing temperature. In addition, since the start of foaming of the foaming agent depends not only on the fixing temperature but also on the fixing speed, it is possible to form both a flat image and a three-dimensional image by adding a means for controlling the fixing speed to a conventional image forming apparatus. The image forming apparatus can also be made. As a means for controlling the fixing speed, for example, the rotation speed of the fixing roll is controlled in accordance with the input of information from the user, and the speed at which the recording medium having an unfixed image passes through the nip portion is determined by V₀Speed V slower than mm / sec₁An example of the system is mm / sec. Speed V₁mm / sec is the speed of the recording medium at the set temperature of the fixing roll.₁The speed is sufficient for the foaming agent in the toner to foam when passing through the nip at mm / sec.
[0124]
The toner obtained by the production method of the present invention can be used without any limitation in the known development method for dry electrostatic charge. For example, two-component development methods such as cascade method, magnetic brush method, microtoning method, one-component development method such as conductive one-component development method, insulating one-component development method, and non-magnetic one-component development method are adopted. The image forming apparatus can be used. Furthermore, it is also possible to design a unique process that efficiently utilizes the low toner adhesion caused by the spherical toner shape. A decrease in toner transfer efficiency is recognized when MLS2 exceeds 140, and MLS2 is preferably about 100 to 120 in order to increase transfer efficiency. It is possible to design a small and simple process that employs the high transfer efficiency characteristic of the toner and employs no cleaning member, and the toner of the present invention is suitable for use in such a process.
[0125]
Examples of the image forming apparatus used in the image forming method using the image forming toner of the present invention will be described below with reference to FIGS. 1 and 2, but the embodiments of the present invention are not limited thereto. Absent.
[0126]
FIG. 1 is an example of a process for forming a full-color image using the toner of the present invention. The photoreceptor (electrostatic latent image carrier) 1 is a photosensitive drum or belt having a photoconductive insulating layer such as OPC (organic photoreceptor), a-Se, a-Si, or ZnO. Of these, OPC and a-Si photoreceptors are preferably used. The OPC may be provided with a silicone-based protective layer. The photoreceptor 1 is uniformly charged by a corona charger 3. In addition to such a non-contact charging device, a contact-type charging device using a roller or a magnetic brush may be used for charging the photoreceptor 1.
[0127]
The photoreceptor 1 is exposed imagewise by the exposure device 2, and an electrostatic latent image is formed on the photoreceptor 1. In the electrostatic latent image, cyan, magenta, yellow, and black developers are introduced into the individual developing devices (developing units) 5a to 5d in the case of a full-color machine. Any of the developers stored in the developing devices 5a to 5d may be a developer containing the toner of the present invention as a main component, or only one color or two to three colors of the present invention. A developer mainly composed of toner may be used. In addition, by adding a means for controlling the developing devices 5a to 5d and incorporating a system capable of selecting the developing device for storing the toner of the present invention in accordance with an input from the user or the like, a stereoscopic image can be selectively formed. Good. The developing devices 5a to 5d may be a magnetic brush developing system or a non-magnetic one-component developing system. The toner of the present invention has high charging stability because the foaming agent is not substantially exposed on the surface, and can exhibit good development characteristics with a conventional developing device.
[0128]
The toner images of the respective colors formed on the photoconductor 1 are sequentially transferred to an intermediate transfer body (belt) 4. The intermediate transfer member (belt) 4 has a configuration in which an elastic layer whose electric resistance value is controlled is provided around the intermediate transfer member (belt) 4. The toner image transferred to the surface of the intermediate transfer body (belt) 4 is transferred to the surface of the recording medium 10 by applying a bias having a polarity opposite to the frictional charge of the toner by a transfer device (transfer means) 6 (transfer process). . Thereafter, the photoreceptor 1 returns to the initial state through a cleaning process by the removable cleaning means 7.
[0129]
The recording medium on which the toner image has been transferred is supplied to a fixing device (fixing means) comprising a heating roll 8 and a pressure roll 9, and a heating roll 8 containing a heating element such as a halogen heater and a pressure contact with the heating roll 8. By passing through the nip portion of the elastic pressure roll 9 to be fixed, it is fixed on the recording medium, and the foaming agent contained in the toner is foamed to form a three-dimensional image (fixing step). A three-dimensional image obtained by this process using the toner of the present invention has a sufficiently recognizable image thickness and has high fixability to paper such as a recording medium.
[0130]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. However, these examples do not limit the present invention.
[0131]
  Example 1
  Polyester resin comprising bisphenol A propylene oxide adduct, bisphenol A ethylenoxide adduct, and terephthalic acid derivative (Mn6700: Mn36000: acidPrice15 mg KOH / g: hydroxyl value 27 mg KOH / g: Tg 62 ° C .: softening point 110 ° C .: mechanical tangent loss 2.8 at 130 ° C. 300 parts by mass and blowing agent (Expansel 461: manufactured by Nippon Philite Co., Ltd.) 497 Part by mass, 2000 parts by mass of ethyl acetate, and 20 parts by mass of hydrophobic silicon oxide fine particles (Aerosil Co., R972, average particle size 16 nm) were mixed and stirred well until uniform (this solution is designated as solution A) ). “Expansel 461” in this example is a microcapsule type foaming agent whose outer shell is made of a vinyl chloride-acrylonitrile copolymer and encapsulates isobutane (boiling point: 11.7 ° C.).
[0132]
On the other hand, 40 parts by mass of calcium carbonate and magnesium chloride (MgCl₂) 1 part by mass, 124 parts by mass of calcium carbonate dispersion dispersed in 60 parts by mass of water, 99 parts by mass of a 2% by weight aqueous solution of Serogen BS-H (Daiichi Kogyo Seiyaku Co., Ltd.), and 157 parts by mass of water The mixture was stirred for 3 minutes using a homogenizer (Ultra Turrax: manufactured by IKA) (this liquid is referred to as B liquid).
[0133]
Further, after 345 parts by mass of the B liquid and 250 parts by mass of the A liquid were stirred at 10,000 rpm for 1 minute using a homogenizer (Ultra Turrax: manufactured by IKA), 0.3% ammonia water was suspended. 110 parts by mass was added, and the solvent was removed by stirring with a propeller-type stirrer at room temperature and normal pressure for 48 hours. Next, hydrochloric acid was added to remove calcium carbonate, followed by washing with water, drying and classification to obtain a toner. The obtained toner volume average particle diameter was 20 μm. The shape factor was 115.
[0134]
Next, to 100 parts by mass of the toner, 1.3 parts by mass of silicon oil-treated silicon oxide fine particles (RY50: manufactured by Nippon Aerosil Co., Ltd.) having an average particle size of 40 nm and deflagration silicon oxide fine particles (KMP-105: Shin-Etsu) having an average particle size of 100 nm are used. 2 parts by weight of a chemical (classified product manufactured by Kagaku Co., Ltd.), 1.5 parts by weight of fine particles obtained by treating 20% of decyltrimethoxysilane with titanium oxide having an average particle size of 20 nm (MT150AW: manufactured by Teika Co., Ltd.), and mixing them with a sample mill. Was made.
[0135]
  (Example 2)
  Polyester resin comprising bisphenol A propylene oxide adduct, bisphenol A ethylenoxide adduct, and terephthalic acid derivative (Mn6700: Mn36000: acidPrice15 mg KOH / g: hydroxyl value 27 mg KOH / g: Tg 62 ° C .: softening point 110 ° C .: mechanical tangent loss at 130 ° C. 2.8) 300 parts by mass and blowing agent (Expansel 461: manufactured by Nippon Ferrite Co., Ltd.) 497 Part by mass, 2000 parts by mass of ethyl acetate, and 20 parts by mass of hydrophobic silicon oxide fine particles (Aerosil Co., R972, average particle size 16 nm) were mixed and stirred well until uniform (this solution is designated as solution A) ).
[0136]
On the other hand, 40 parts by weight of calcium carbonate, 1 part by weight of PAC (Poly Aluminum Chloride (polyaluminum chloride)), 124 parts by weight of a calcium carbonate dispersion dispersed in 60 parts by weight of water, and Serogen BS-H (Daiichi Kogyo Seiyaku ( Ltd.) was stirred for 3 minutes using a homogenizer (Ultra Turrax: manufactured by IKA) (a liquid C).
[0137]
Furthermore, 345 parts by mass of the liquid C and 250 parts by mass of the liquid A were stirred for 1 minute at 10,000 rpm using a homogenizer (Ultra Turrax: manufactured by IKA), and then the mixed liquid was suspended. 110 parts by mass was added, and the solvent was removed by stirring with a propeller-type stirrer at room temperature and normal pressure for 48 hours. Next, hydrochloric acid was added to remove calcium carbonate, followed by washing with water, drying and classification to obtain a toner. The obtained toner volume average particle diameter was 25 μm. The shape factor was 118.
[0138]
Next, to 100 parts by mass of the toner, 1.3 parts by mass of silicon oil-treated silicon oxide fine particles (RY50: manufactured by Nippon Aerosil Co., Ltd.) having an average particle size of 40 nm and deflagration silicon oxide fine particles (KMP-105: Shin-Etsu) having an average particle size of 100 nm are used. 2 parts by weight of a chemical (classified product manufactured by Kagaku Co., Ltd.), 1.5 parts by weight of fine particles obtained by treating 20% of decyltrimethoxysilane with titanium oxide having an average particle size of 20 nm (MT150AW: manufactured by Teika Co., Ltd.), and mixing them with a sample mill. Was made.
[0139]
  (Example 3)
  Polyester resin comprising bisphenol A propylene oxide adduct, bisphenol A ethylenoxide adduct, and terephthalic acid derivative (Mn6700: Mn36000: acidPrice15 mg KOH / g: hydroxyl value 27 mg KOH / g: Tg 62 ° C .: softening point 110 ° C .: mechanical tangent loss at 130 ° C. 2.8) 300 parts by mass and blowing agent (Expansel 461: manufactured by Nippon Ferrite Co., Ltd.) 497 Parts by weight, 2000 parts by weight of ethyl acetate, 19 parts by weight of copper phthalocyanine (CI Pigment Blue 15: 3) as a colorant, 1 part by weight of a pigment dispersant, hydrophobic silicon oxide fine particles (R972 manufactured by Aerosil), average 20 parts by mass of (particle diameter 16 nm) were mixed and stirred well until uniform (this liquid is referred to as A liquid).
[0140]
On the other hand, 40 parts by weight of calcium carbonate, 1 part by weight of 1,10-diaminodecane, 124 parts by weight of a calcium carbonate dispersion dispersed in 60 parts by weight of water, and 2 of Serogen BS-H (Daiichi Kogyo Seiyaku Co., Ltd.) 99 parts by mass of a mass% aqueous solution and 157 parts by mass of water were stirred for 3 minutes using a homogenizer (Ultra Turrax: manufactured by IKA) (this liquid is designated as D liquid).
[0141]
Furthermore, after 345 parts by mass of the D liquid and 250 parts by mass of the A liquid were stirred for 1 minute at 10,000 rpm using a homogenizer (Ultra Turrax: manufactured by IKA), 0.3% ammonia water was suspended. 110 parts by mass was added, and the solvent was removed by stirring with a propeller-type stirrer at room temperature and normal pressure for 48 hours. Next, hydrochloric acid was added to remove calcium carbonate, followed by washing with water, drying and classification to obtain a toner. The obtained toner volume average particle diameter was 30 μm. The shape factor was 112.
[0142]
Next, 1.3 parts by mass of silicon oil-treated silicon oxide fine particles (RY50: manufactured by Nippon Aerosil Co., Ltd.) having an average particle size of 40 nm and deflagration silicon oxide fine particles (KMP-105: Shin-Etsu) having an average particle size of 100 nm are added to 100 parts by mass of the toner. 2 parts by weight of a chemical (classified product manufactured by Kagaku Co., Ltd.), 1.5 parts by weight of fine particles obtained by treating 20% of decyltrimethoxysilane with titanium oxide having an average particle size of 20 nm (MT150AW: manufactured by Teika Co., Ltd.), and mixing them with a sample mill. Was made.
[0143]
  Example 4
  Polyester resin comprising bisphenol A propylene oxide adduct, bisphenol A ethylenoxide adduct, and terephthalic acid derivative (Mn6700: Mn36000: acidPrice15 mg KOH / g: hydroxyl value 27 mg KOH / g: Tg 62 ° C .: softening point 110 ° C .: mechanical tangent loss at 130 ° C. 2.8) 300 parts by mass and blowing agent (Expansel 461: manufactured by Nippon Ferrite Co., Ltd.) 497 Part by mass, 2000 parts by mass of ethyl acetate, and 20 parts by mass of hydrophobic silicon oxide fine particles (Aerosil Co., R972, average particle size 16 nm) were mixed and stirred well until uniform (this solution is designated as solution A) ).
[0144]
On the other hand, 40 parts by weight of calcium carbonate, 1 part by weight of 1,4-diaminobutane, 124 parts by weight of a calcium carbonate dispersion dispersed in 60 parts by weight of water, and 2 of Serogen BS-H (Daiichi Kogyo Seiyaku Co., Ltd.) 99 parts by mass of a mass% aqueous solution and 157 parts by mass of water were stirred for 3 minutes using a homogenizer (Ultra Turrax: manufactured by IKA) (this liquid is referred to as E liquid).
[0145]
Furthermore, after 345 parts by mass of the E solution and 250 parts by mass of the A solution were stirred for 1 minute at 10,000 rpm using a homogenizer (Ultra Turrax: manufactured by IKA), 0.3% ammonia water was suspended. 110 parts by mass was added, and the solvent was removed by stirring with a propeller-type stirrer at room temperature and reduced pressure for 48 hours. Next, hydrochloric acid was added to remove calcium carbonate, followed by washing with water, drying and classification to obtain a toner. The obtained toner volume average particle diameter was 22 μm. The shape factor was 145.
[0146]
Next, to 100 parts by mass of the toner, 1.3 parts by mass of silicon oil-treated silicon oxide fine particles (RY50: manufactured by Nippon Aerosil Co., Ltd.) having an average particle size of 40 nm and deflagration silicon oxide fine particles (KMP-105: Shin-Etsu) having an average particle size of 100 nm are used. 2 parts by weight of a chemical (classified product manufactured by Kagaku Co., Ltd.), 1.5 parts by weight of fine particles obtained by treating 20% of decyltrimethoxysilane with titanium oxide having an average particle size of 20 nm (MT150AW: manufactured by Teika Co., Ltd.), and mixing them with a sample mill. Was made.
[0147]
(Example 5)
30 parts by weight of paraffin wax (melting point: 89 ° C.) and 270 parts by weight of ethyl acetate were cooled to 5 ° C. using a DCP mill, and wet pulverized to prepare a wax (release agent) dispersion (this liquid was F liquid).
[0148]
  Polyester resin comprising bisphenol A propylene oxide adduct, bisphenol A ethylenoxide adduct, and terephthalic acid derivative (Mw6700: Mn36000: acidPrice15 mg KOH / g: hydroxyl value 27 mg KOH / g: Tg 62 ° C .: softening point 110 ° C .: mechanical tangent loss at 130 ° C. 2.8) 420 parts by mass and foaming agent (Expansel 461: manufactured by Nippon Ferrite Co., Ltd.) 497 Mass parts, 300 parts by mass of the above-mentioned F liquid (wax dispersion), 1700 parts by mass of ethyl acetate, and 20 parts by mass of hydrophobic silicon oxide fine particles (R972 manufactured by Aerosil Co., Ltd., average particle diameter 16 nm) are mixed uniformly. It stirred well until it became (it makes this liquid G liquid).
[0149]
On the other hand, 40 parts by mass of calcium carbonate and magnesium chloride (MgCl₂) 1 part by weight, 124 parts by weight of calcium carbonate dispersion dispersed in 60 parts by weight of water, 99 parts by weight of 2% aqueous solution of Serogen BS-H (Daiichi Kogyo Seiyaku Co., Ltd.), and 157 parts by weight of water (Ultra Turrax: manufactured by IKA) was stirred for 3 minutes (this liquid is referred to as B liquid).
[0150]
Furthermore, 345 parts by weight of the B liquid and 250 parts by weight of the G liquid were stirred for 1 minute at 10,000 rpm using a homogenizer (Ultra Turrax: manufactured by IKA), and then the mixed liquid was suspended. Part by weight was added, and the solvent was removed by stirring with a propeller-type stirrer at room temperature and normal pressure for 48 hours. Next, hydrochloric acid was added to remove calcium carbonate, followed by washing with water, drying and classification to obtain a toner. The obtained toner volume average particle diameter was 24 μm. The shape factor was 117. The release agent had an average particle size of 0.3 μm and a major axis / minor axis ratio of 2.0.
[0151]
Next, 100 parts by weight of this toner, 1.3 parts by weight of silicon oxide-treated silicon oxide fine particles having an average particle size of 40 nm (RY50: manufactured by Nippon Aerosil Co., Ltd.), deflagration silicon oxide fine particles having an average particle size of 100 nm (KMP-105: Shin-Etsu) (Chemicals classification) 2 parts by weight, 1.5 parts by weight of fine particles obtained by treating 20% of decyltrimethoxysilane with titanium oxide (MT150AW: manufactured by Teika Co., Ltd.) having an average particle diameter of 20 nm are mixed with a sample mill to prepare a toner. Was made.
[0152]
(Comparative Example 1)
  Polyester resin comprising bisphenol A propylene oxide adduct, bisphenol A ethylenoxide adduct, and terephthalic acid derivative (Mn6700: Mn36000: oxidation 15 mgKOH / g: hydroxyl value 27 mgKOH / g: Tg62 ° C: softening point 110 ° C: 130 ° C Tangent loss 2.8) 300 parts by mass, foaming agent (Expancel 461: manufactured by Nippon Philite Co., Ltd.) 497 parts by mass, ethyl acetate 2000 parts by mass, and hydrophobic silicon oxide fine particles (Aerosil Co., Ltd.) R972, average particle size 16 nm) and 20 parts by mass were mixed and stirred well until uniform (this solution is referred to as “A solution”). “Expansel 461” in this example is a microcapsule type foaming agent whose outer shell is made of a vinyl chloride-acrylonitrile copolymer and encapsulates isobutane (boiling point: 11.7 ° C.).
  Further, 250 parts by mass of the liquid A was stirred at 10,000 rpm for 1 minute using a homogenizer (Ultra Turrax: manufactured by IKA), and the mixed liquid was suspended. Then, 110 parts by mass of 0.3% aqueous ammonia was added, and The solvent was removed by stirring with a propeller stirrer at normal pressure for 48 hours. Next, it was washed with water, dried and classified to obtain a toner..
  Next, to 100 parts by mass of the toner, 1.3 parts by mass of silicon oil-treated silicon oxide fine particles (RY50: manufactured by Nippon Aerosil Co., Ltd.) having an average particle size of 40 nm and deflagration silicon oxide fine particles (KMP-105: Shin-Etsu) having an average particle size of 100 nm are used. 2 parts by weight of a chemical (classified product manufactured by Kagaku Co., Ltd.), 1.5 parts by weight of fine particles obtained by treating 20% of decyltrimethoxysilane with titanium oxide having an average particle size of 20 nm (MT150AW: manufactured by Teika Co., Ltd.), and mixing them with a sample mill. Was made.
[0154]
  <Evaluation>
  Example 15And comparative examples1“Fixability (fixing strength (N))” of the obtained toner was measured.
[0155]
The results are shown in Table 1. The evaluation method for fixability is as follows.
[0156]
-Fixability-
For Examples 1 to 4 and Comparative Example 1, the fixability was measured using a DocuColor 1250 (Fuji Xerox Co., Ltd.) remodeling machine and the toner weight per unit area TMA = 72 g / m.²After forming an unfixed φ1.5 mm circular dot image and heating and fixing at 145 ° C. to obtain a three-dimensional image, the transverse shear force at the interface between the paper and the image of the φ1.5 mm circular dot three-dimensional image was pulled by a test modification machine. Measured and evaluated as fixing strength (N). As a developer, a carrier in which methyl methacrylate and perfluorooctylethyl acrylate copolymer were coated on a 100 μm ferrite core was used, and the carrier: toner ratio was set to 80:20.
[0157]
  ExampleTo 5Toner weight per unit area TMA = 72 g / m using a modified DocuCentreColor400CP (Fuji Xerox)²After forming an unfixed image of φ1.5 mm circular dots, heat fixing at 145 ° C. to obtain a three-dimensional image, and then remodeling the test by pulling the transverse shear force at the interface between the three-dimensional image of φ1.5 mm circular dots and 300 μm It was measured by a machine and evaluated as fixing strength (N). As a transfer paper, Fuji Xerox color paper (pink) was used.
[0158]
The following describes the tensile test modified machine used for the evaluation.
[0159]
The tensile test remodeling machine is an apparatus for measuring the adhesive strength between a three-dimensional image printed on a base material (recording medium) such as paper or film and the base material, and the three-dimensional image is peeled off or destroyed. The resistance force in a direction substantially parallel to the base material is measured.
[0160]
2 and 3 are schematic diagrams of the tensile test modified machine used in this evaluation. FIG. 3 is a view of FIG. 2 viewed from the side. However, some members drawn in one drawing are omitted in the other drawing.
[0161]
  The object to be inspected 20 is obtained by forming the stereoscopic image 12 on the base material 11 using the image forming toner of each of the above examples or comparative examples. The flat blade 16 has a cutting edge in one piece for scratching the stereoscopic image 12 on the substrate 11. The shaft 18 tightly connects the dial gauge 19 and the abutting member 17. block30Is provided at a position facing the blade 16, touches the back surface of the substrate 11, and is fixed to the table 15. Blade 16 and block30The dial gauge 19 is zero-adjusted in the state where it is abutted, and the blade 16 is blocked with the blade 1630The slit spacing is 20 μm wider than the thickness of the base material 11 and then fixed with the shaft fixing member 21. Reference numeral 13 denotes a load measuring instrument, which measures a resistance force when the substrate 11 is pulled.
[0162]
In the measurement, the end of the base material 11 is gripped by the base material gripping member 14 attached to the load measuring device 13, and the load measuring device 13 is moved in a horizontal direction (arrow A) by a moving means (not shown). By moving in the direction). As the stereoscopic image is peeled off by the blade 16, the reading of the measuring instrument changes. The peak value was defined as the fixing strength (N) value.
[0163]
In addition, the evaluation of the image surface defect in Table 1 was performed silently. Those with no defects were marked with “◯”, and those with some defects were marked with “x”.
[0164]
[Table 1]

[0165]
【The invention's effect】
According to the present invention, it is possible to provide an image forming toner capable of easily forming a stereoscopic image particularly excellent in fixability, a method for producing the toner, and a developer containing the toner. Further, it is possible to provide an image forming method and an image forming apparatus that can easily form a stereoscopic image.
[Brief description of the drawings]
FIG. 1 is a schematic diagram showing an example of an image forming apparatus (color printer) used in an image forming method using an image forming toner of the present invention.
FIG. 2 is a schematic view showing a tensile test remodeling machine used for evaluation of an example of the present invention.
FIG. 3 is a schematic diagram showing a part of a tensile test remodeling machine used for the evaluation of the examples of the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 Photoconductor (electrostatic latent image carrier), 2 Exposure device, 3 Corona charger, 4 Intermediate transfer body, 5a, 5b, 5c, 5d Developing device (developing means), 6 Transfer device (transfer means), 7 Cleaning Means, 8 heating roll (fixing means), 9 pressure roll (fixing means), 10 recording medium, 11 base material, 12 stereoscopic image, 13 load measuring device, 14 base material gripping member, 15 units, 16 blades, 17 butt Contact member, 18 shaft, 19 dial gauge, 20 object to be inspected, 21 shaft fixing member, 30 blocks, A moving direction.

Claims (5)

  An image forming toner comprising: a toner containing at least a binder resin and a foaming agent having an outer shell; and a compound that binds the binder resin and the outer shell of the foaming agent. A step of adjusting an oil component by mixing at least a binder resin and a foaming agent having an outer shell in an organic solvent in which the binder resin can be dissolved;
Suspending the oily component in an aqueous solvent containing a compound that binds the binder resin and the outer shell to form particles and preparing a suspension;
Removing the organic solvent from the suspension;
A method for producing an image forming toner, comprising:   A developer comprising a toner and a carrier, wherein the toner is the image forming toner according to claim 1. A developing step of developing a latent image formed on the surface of the electrostatic latent image carrier with toner to form a toner image, and transferring the toner image formed on the surface of the electrostatic latent image carrier to a recording medium In an image forming method comprising: a transfer step; and a fixing step of fixing a toner image on a recording medium.
The toner is an image forming toner according to claim 1,
An image forming method, wherein the fixing step foams a foaming agent contained in the toner to form a three-dimensional image on a recording medium. An electrostatic latent image carrier, developing means for developing a latent image formed on the surface of the electrostatic latent image carrier with toner to form a toner image, and formed on the surface of the electrostatic latent image carrier. An image forming apparatus comprising: a transfer unit that transfers the toner image to a recording medium; and a fixing unit that fixes the toner image to the recording medium.
The toner is an image forming toner according to claim 1,
An image forming apparatus, wherein the fixing unit is a unit that foams a foaming agent contained in the toner to form a three-dimensional image on a recording medium.

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