CA1183033A - Developer compositions comprising two incompatible resins with interacting polar groups - Google Patents
Developer compositions comprising two incompatible resins with interacting polar groupsInfo
- Publication number
- CA1183033A CA1183033A CA000403032A CA403032A CA1183033A CA 1183033 A CA1183033 A CA 1183033A CA 000403032 A CA000403032 A CA 000403032A CA 403032 A CA403032 A CA 403032A CA 1183033 A CA1183033 A CA 1183033A
- Authority
- CA
- Canada
- Prior art keywords
- developer composition
- group
- toner
- polar functional
- functional group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08797—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their physical properties, e.g. viscosity, solubility, melting temperature, softening temperature, glass transition temperature
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08791—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by the presence of specified groups or side chains
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Developing Agents For Electrophotography (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A developer composition is disclosed which is characterized by containing two binding resinous materials (A) and (B). The material (A) is a resinous material having a polar functional group and a glass transition temperature below 0°C. The material (B) is a resinous material having a glass transition temperature higher than 40°C. The material (B) is incompatible with the material (A). Material (B) has a polar functional group capable of interacting with the polar functional group of material (A). The developer may also contain a fine magnetic powder in an amount of 20 to 80% by weight based on the total weight of the developer composition. The developer composition can be used to form clear images which remain clear even after repeated opera-tion within a copying device. Furthermore, the images formed are securely fixed and can not be wipped off or removed easily.
A developer composition is disclosed which is characterized by containing two binding resinous materials (A) and (B). The material (A) is a resinous material having a polar functional group and a glass transition temperature below 0°C. The material (B) is a resinous material having a glass transition temperature higher than 40°C. The material (B) is incompatible with the material (A). Material (B) has a polar functional group capable of interacting with the polar functional group of material (A). The developer may also contain a fine magnetic powder in an amount of 20 to 80% by weight based on the total weight of the developer composition. The developer composition can be used to form clear images which remain clear even after repeated opera-tion within a copying device. Furthermore, the images formed are securely fixed and can not be wipped off or removed easily.
Description
~EVELOPER CO~IPOSITIONS
FIELD OF THE INVENTION
This inventioll relates to a developer composi~ion for a dry system for developing electric latent images in electrophotography, electrostatic recording, etc., and more particularly to a developer composition having a pressure fixing property.
BACKGROUND OF THE INVENTION
A process of forming electric latent images is well - known. For example, in an electrophotographic process after the usual charging of -the pl}otoconductive layer, the photo-conductive layer is exposed to a light image based on an original to reduce or eliminate elec-trostatic charge at the light-exposed portions, whereby an electrostatic latent image is formed. The latent image is then developed by a developer called a ~Itoner~. As is well-known, a development process is largely classified into a process which uses a liquid developer and a process which uses a dry developer. The latter process ~, .~,~
is further classified into a two-component developmen~ proces using two kinds of particles, carrier and toner, and a one-component development process using a toner only.
If necessary~ the developed image is transferred onto a material such as paper. Thereafter, the toner is fixed - 1- ,~
Oll tne paper by fusing the toner with hea-t or by softening a binding resin of the toner with a solvent, or by deforrn-ing tne toner with only pressure.
A pressure fixing process w~lerein a toner is fixed with only pressure without using heat or a solvent nas various merits with respect to energy savin~, pollution and fire prevention as well as not requiring pre-heating for the fixing means. Other advantages are also obtained as compared with other fixing processes. However~ the property that a toner is deformed by a practical pressure is reciprocal to the strength of the fixed toner image and other properties such as producibility of the toner, antiblocking property, impact resistance, i.e. as one property is improved others are deterioTated. Tilerefore, it is very difficult to meet all tnese properties.
Many investiga-tions and developments have been carried out in order to overcome these diffi-culties. For example~ Japanese Patent Publication No.
9880/69 proposes a toner containing an aliphatic component having 6-25 carbon atoms and Japanese Patent Application (OPI) No. 119,231/77 proposes a toner containing a crystalline wax and an ethylene-vinyl acetate copolymer.
Known wax-like materials may be excellent witn respect to deformability by pressure. However, the strength of the fixed image is weak and hence the image readily comes off or stains when i~ is rubbed witn a finger. Furthermore, the torler is liable to attach to the sur-face of a Photoconductive material, or the surfaces of carrier particles when such a toner is used for a two-componen-t type developer. This results S in deterioration and changes in tne characteristics of the carrier. Fur~hermore, when a crys~alline resin such as polyetnylene, is used as a main binding resin for a toner, the producibility of tne toner is reduced and a toner naving stable characteristics is not obtained since it is difficult 0 to control the degree of crystalli~ation and the crystal form.
Japanese Patent Application (OPI) Nos. 75,033/73 alid 78,931/73 propose a material designed to meet the aforesaid various required properties by using a block copolymer composed of hard and soft resins. However, if the amount of the soft component is increased to the extent necessary to impart sufficient pressure defirmability to the toner, grinding of the toner becomes difficult when preparing a toner powder by a kneading and grinding method. When a toner powder is prepar-ed by a spray dry metilod7 this difficulty does not occur since a grinding step is unnecessary. However, liquid preparation becomes difficult and it is difficult to impart both a good fixing property and anti-blocking property to the toner obtained. Furthermore, w}len preparing a toner by any process, tlle use of a multi-pnase polymer SUCh as a block copolymer or
FIELD OF THE INVENTION
This inventioll relates to a developer composi~ion for a dry system for developing electric latent images in electrophotography, electrostatic recording, etc., and more particularly to a developer composition having a pressure fixing property.
BACKGROUND OF THE INVENTION
A process of forming electric latent images is well - known. For example, in an electrophotographic process after the usual charging of -the pl}otoconductive layer, the photo-conductive layer is exposed to a light image based on an original to reduce or eliminate elec-trostatic charge at the light-exposed portions, whereby an electrostatic latent image is formed. The latent image is then developed by a developer called a ~Itoner~. As is well-known, a development process is largely classified into a process which uses a liquid developer and a process which uses a dry developer. The latter process ~, .~,~
is further classified into a two-component developmen~ proces using two kinds of particles, carrier and toner, and a one-component development process using a toner only.
If necessary~ the developed image is transferred onto a material such as paper. Thereafter, the toner is fixed - 1- ,~
Oll tne paper by fusing the toner with hea-t or by softening a binding resin of the toner with a solvent, or by deforrn-ing tne toner with only pressure.
A pressure fixing process w~lerein a toner is fixed with only pressure without using heat or a solvent nas various merits with respect to energy savin~, pollution and fire prevention as well as not requiring pre-heating for the fixing means. Other advantages are also obtained as compared with other fixing processes. However~ the property that a toner is deformed by a practical pressure is reciprocal to the strength of the fixed toner image and other properties such as producibility of the toner, antiblocking property, impact resistance, i.e. as one property is improved others are deterioTated. Tilerefore, it is very difficult to meet all tnese properties.
Many investiga-tions and developments have been carried out in order to overcome these diffi-culties. For example~ Japanese Patent Publication No.
9880/69 proposes a toner containing an aliphatic component having 6-25 carbon atoms and Japanese Patent Application (OPI) No. 119,231/77 proposes a toner containing a crystalline wax and an ethylene-vinyl acetate copolymer.
Known wax-like materials may be excellent witn respect to deformability by pressure. However, the strength of the fixed image is weak and hence the image readily comes off or stains when i~ is rubbed witn a finger. Furthermore, the torler is liable to attach to the sur-face of a Photoconductive material, or the surfaces of carrier particles when such a toner is used for a two-componen-t type developer. This results S in deterioration and changes in tne characteristics of the carrier. Fur~hermore, when a crys~alline resin such as polyetnylene, is used as a main binding resin for a toner, the producibility of tne toner is reduced and a toner naving stable characteristics is not obtained since it is difficult 0 to control the degree of crystalli~ation and the crystal form.
Japanese Patent Application (OPI) Nos. 75,033/73 alid 78,931/73 propose a material designed to meet the aforesaid various required properties by using a block copolymer composed of hard and soft resins. However, if the amount of the soft component is increased to the extent necessary to impart sufficient pressure defirmability to the toner, grinding of the toner becomes difficult when preparing a toner powder by a kneading and grinding method. When a toner powder is prepar-ed by a spray dry metilod7 this difficulty does not occur since a grinding step is unnecessary. However, liquid preparation becomes difficult and it is difficult to impart both a good fixing property and anti-blocking property to the toner obtained. Furthermore, w}len preparing a toner by any process, tlle use of a multi-pnase polymer SUCh as a block copolymer or
2~ a graft copolymer is disadvantageous in that it is difficult to control the multi-phase structure. ~!ore specifically, it is difficult to control the morphology of the toner as in the case of the aforesaid crystalline polymer. The morphology of the toner is greatly influenced by a slight change in the production conditions and the properties of raw materials, resulting in great changes in the character-istics of the toner. Japanese Patent Application (OPI) No.
87,042/76 discloses an attempt to improve the pressure fixibility of a toner by blending a crystalline resin such as polyethylene wax as a main component with a small amount of material such as a vinylic resin. However, since a crystalline resin is used as the main binding resin, there exist the above-mentioned difficulties which are specific to the crystalline resin.
~hen a resin is blended with a resin having good compatibility therewith it is not possible to obtain a toner meeting many required properties which are reciprocal with each other. On the other hand, when resins incompatible with each other are blended , it is not possible to uniformly mix the resins and slight changes in the production conditions result in the formation of toner having incompatible resins in different dispersed state or dispersed amount.
Furthermore, the powder fluidity and electrical character istics such as the static property of the toner are greatly reduced. Therefore, when using conventional material "~,,;b'¦ ! t~
compositions it i~ no-t possible to ob-tain a pressure fixing toner having many required properties which are recip.rocal with each o~her. Furthermore, it is difficult to stably produce such a toner.
_M:~RY OF THE INVlENTION
An object of an aspect of the presen-t invention is to produce a developer composit:ion (sometimes herein refer-red to as "~oner") having an excellent pressure fixing property.
An object of an aspect of this inven~ion is to provide a developer composition having good powder fluidity, anti-blocking property.,~impact resistance and abrasion resis-tance.
An object of an aspect of this invention is to provide a developer composition having good production stability.
An object of an aspec-t of this invention is to pro-vide a developer composition stable with respect to environ-mental changes and stable with the passage of time.
An object of an aspect of this invention is to provide a developer composition capable of forming good and stable images for any development or transfer processes.
An object of an aspect of this invention is to provide a developer composition having a good cleaning property.
In accordance with an aspect of this invention there .. is provided a developer composition comprising (A) a binding resinous material having a polar functional group and a glass transition temperature below 0C and (B) a binding resi~ous material having a glass transition temperature above 40C, which is chemically incompatible with material (A). Material (B) has a polar functional group capable of interacting with the polar functional group of afore~
sai~ material (A). Materia:Ls (A) and (B) are i.ndispensable components for the binding resinous material of this inven-tion. Preferred results can be obtained using an olefinic polymer having a hydroxy group, a carboxyl group or a carbonyl group as material tA) and a styrenic polymer or a polyester resin having a hydroxy group, a carboxyl group or a dialkylamino group as material (B).
Another aspect of this invention is an electro-photographic process comprising developing an electric latent ima~e with a developer composition and fixing the thus developed image by the application of pressure, characterised in that the de~eloper composition referred to in the preceding paragraph is employed.
DETAILED DESCRIPTION OF THE INVENTION
. ~ .
The invention will be explained below in detail.
Firstly, the binding resinous material (A) in the developer composition of the present invention includes those having a glass transltion temperature below 0C, preferably below -30C. Material (A) is selected from resinous materials which easily show plastic deformation or viscoelastic deformation with a pressure of less than about 200 kg/cm2 at room temperature and has a polar functional group.
ll ,~. ~Q~
Polar functional groups of Material (A) include a hydroxy group, a carbonyl group, a carboxy group, an epoxy ~roup, a glicidyl g.roup, a nitro group, a sulfonic acid . .
-6a-group, an amino group, an amido group, a cyano group, an isocyanate groupS a diazonium group, an aziridine group, an aldehyde group, an acid anilydride, a methylol group, a tniol group, a mercapto group, a phosphoric acid group, and a halogerl-con~aining group. These functional groups may be substituted by a group such as a methyl group, ethyl group, phenyl group or may have an ether linkage, ester linkage, etc. ~nong these groups, a ihydroxy group, a carboxyl group and a càrbonyl group are preferred, because tiley are very stable, give no bad influences on the charac-teristics of a toner, and have a large interaction with : :
material (B).
The resinous material which has a polar functional group and which is capable of being deformed by pressure at normal temperature may be syntnetic or natural resinous materials. Examples of such materials include higher fatty acids ~e.g., stearic acid, oleic acid, etc.,) and derivatives tllereof (e.g., fatty acid amides), chlorinated paraf~in, chlorinated polyethylene, chlorinated polypropylene, oxidized polyethylene, polypropylene oxideg ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, organic acid graft polyethylene, rubber-like acrylic acid copolymer, polyvinyl acetate, polyvinyl butyral, silicone and modified resins thereof, polycarbonate, fluorinated rubber, fluorinated~a~, nitril rubber, chloroprene rubber, polyamide, ~3 polyester, polyether, polyurethane~ and polyalkyd. Of these, oxidlzed polyethylene, ethylene-acrylic acid copolyme.r and organic acid graft polyethylene, which have a hydroxy group, a carboxyl yroup or a carbonyl group are particularly preferred for material (~).
Binding resinous material (s3 in the developer composi-tion of the present :invention can be selected Erom natural and syrlthetic resi.nous material3 having a glass transition temperature above ~10C, more preferably 60-80C, and having a polar functional group as defined in mate~lal (A) A hydro~y group, a carboxyl group and dialkylamino group are particularly preferred as the polar f~mctional group of materi.al (B). In particular, styrene-acrylic acid copolymer, epoxy resin, phenol resin, polyester resin, etc.~
satisfying the aforesaid factors are preferably used since they meet many required properties for ~onerO
Material ~A) is chemically incompatible with material (B) and the polar functional group of material (A) must be interact.ible with the polar functional group of material (~). Solubility is a suitable parameter for compatibility. With respect to this invention, when the parameter of the solubility of material (A) is taken as SA and the parameter of the solubility of material (B) is taken as ~B~ when 1~ A ~ 3B¦is higher than about 0.5 it is defined as being incompatible. The solubility parameters of the resinous materials can be obtained by calculation.
Howevex, standard values which can be relied on are disclosed in "Polymer Handhook", 2nd Ed. (John Wiley &
Sons) to disclose such values.
The interaction of the functional groups may involve (13 hydrophobic bonding, (2) electrostatic bonding, (3) hydrogen bonding, (4) charge transfer bonding, and (5) covalent bonding interactions.
However since the interaction of polar ~unctional groups is important in this invention, the interaction of (2) to (5) are of greater importance.
With consideration to the factor explained above it should be understood that many combinations of materials ~A) and ~B) are possible in this invention. Hol~ever, preferred materials which meet various electric, mechanical~ rheological, thermal, opticai and chemical properties required for a toner, inclucle the combination of an olefinic polymer having group -OH, -COOH or `C=O as material (A) and a styrenic copolymer or de-natured resin thereof, or a polyester resin each having group -OH, -COOH
or -MRlR2 ~herein Rl and R29 which may be the same or different, each represents an alkyl group (e.g., methyl, ethyl) as material (B). The interaction between an alcoholic -OH group and an acid -COOH group is particularly preferred for the purpose of the present invention. ~Iost preferred combinations of ma~erials (A) and (B) are given in Table 1 below.
Table Material. (A) Material (B) . . _ . _ . _ . _ . _ _ . . _ . . . _ _ . . . _ . _ _ _ _ . _ . . . . _ . . _oxidizecl polyethylene styrene-ally alcohol copolymer organic acid gra~t polyethylene '~
ethylene-acrylic acid copolymer "
ethylene-vinyl acetate styrene-(meth)acrylic acid copolymer copolymer oxidized polyethylene styrene-dimethylaminoethyl methacrylate copolymer organic acid graft polyethylene "
hydroxy group-containing aromatic polyester For example, if polyethylene is consideled as a base for-the olefinic polymer, whose solubility parameter is about 8.0 as compared with about 9.0 for the solubility parameter of polystyrene which is one of the base resins for material (B), it will be understood that both materials are essentially incompatible with each other. ~ere is no particular restriction regarding the position of the polar functional group in both materials (A) and (B). However, ~he materials having the polar functional group on the side chain or the en~l of the molecular chain aTe readily utilizable.
la With respect to the content of the functional group~
when, for example a -COOH is present, the acid ~alue is higher than 5 in both materials (A) and (B). Other polar group contents are similar in this regard. However, considerable care must be taken so that the content of the functional group is not too high. I-f the content gets too high, the interaction or reaction between the same kinds of molecules or different kinds of molecules as well as the intramolecular interaction or reaction become too strong.
This can cause difficulties. Usually, when the functional group is -COOH, a resin having an acid value of from about 10 to about 100 is preferred. The acid value is shown by the milligTam number of potassium hydroxide necessary for neutralizing the acid contained in one gram of the resin.
It has hitherto been at-tempted to introduce a polar functional group into a binder resin in order to control electrical characteristics of a toner. However, the present invention involves introducing a polar functional group into each of binding res:inous materials ~A) and (B) WlliCIl aTe incompatible with each other and have largely di~ferent physical and chemical properties, whereby materials (A) and (~) interact with each other, and thus the objects o this invention can be attained. In other words, it is not possible to achieve the objects of this invention merely by introducing a polar functional group into a binder resin.
The effects and merits of the presen~ invention are briefly explained below. As described above, many reciprocal properties are required for a pressure fixable -toner. The toner must be constructed so that it exllibits these reciprocal properties independently in each step of lS tile image forming processes. In order to attain this purpose 7 it is preferred tnat binding resin materials having different properties are in the state of forming a proper multi-phase structure. When mixing two or more kinds of binding resinous materials having different properties, if they have high compatibility with each other, the mixture obtained canno-t exhibit the individual different properties of each resinous material. On the other hand7 if they are incompatible ~ith each other, the mixture will meet certain of the various required properties which are reciprocal with each other. However, it is difficult to maintain r i ~ ~ 3 ~
tile dispersed multi-phase structure in a stationary sta~e Furthermore the heterogeneous inter~ace between them frequently reduces the properties of the toner.
The inventors have discovered that these .5 difficulties can be overcome by introducing a functional group interaction between binding resinous materials (A) and (B) which are incompa~ible wit:h e~ac3L other and have dif~erent properties. Since binding resinous materials ~A) and (B) are properly incompatible with each other, when the materials are mixed, materials (A) and (B) maintain thei.r indivi-dual domain, thereby`a desired multi-phase structure can be attained. Furthermore, since there is an interaction between ~ -the polaT function groups of materials (A) and the polar functional group of material ~B), the heteroge~eous interface between materials (A) and (B) is fixed and the multi-layer dispersion structure itsel:f becomesstable. The interaction in this ~Lse may be a secondary bonding tyye of interaction sucn as hydrogen bonding, electrostatic bonding or alternatively may be a covalent bonding type of interaction such as grafting or crosslinking It has also been found that when secondary bonding takes place the stabilization in multi-phase dispersion structure not only facilitates the control of electric characteristics and mechanical properties, but also strengthens tne shearing stress and shearing time reliance of the mechanical properties of the toner, which are advantageous because the resulting fixed toner image is free of smudges or smears even when rubbed with finger.
When magnetic powder and other fillers having polar surfaces are contained in the ~oner, the interaction between the polar funct.ional groups of binding resinous materials (A) and (B) and these fillers can be expected.
Due to this interaction the multi-phase dispersion structure of the toner is more stabilized. Fur~hermore, mechanical and thermal properties can be improved.
It is possible to control the electrical characteris~ics of the toner in a conventional manner by adjusting the electron donative or electron acceptive propeTty of the polar functional groups of materials (A) and (B).
Preferably material (A) ~ which is a soft component having a glass transition temperature below 0C , is present in an amoun~ within the range of 5-50% by weight, preferably 10-30% by weight to the total weight of binding resinous materials. If it is contained in an amount below 5% by weight, the toner is poor witll respect to pressure deformability during pressure fixing. If the content is higher than 50% by weight, the anti-blocking property, powder fluidity and producibility of the toner are greatly reduced.
On the other lland, it is preferred that material (B), which is -tAe hard component and have a glass transition temperature above 40C,be contained in the range of 5-95%
by weight, preferably 10-80% by weight~ more preferably 35-65% by weight~ based on the tota]. weight o-f binding resinous materials.
When the toner further contains a binding resinous material other than materials (A~ and (B), it is preferred to employ the resinous material having good compatibility with ma~erial (A), if the resinous material is a soft component having a glass transition temperature below 0C
or with materia3 (B) if the resinous material is a hard component having a glass transition temperature above 40~.
In the case, it is necessary to prepare a toner in such a manner that the proportion of the total soft components containing material (A) be 5-50% by weight of binding resinous materials and the proportion of the total hard components containing material (B) be 50-95% by weight.
The toner may contain various kinds of additives such as coloring agents. Examples of useful coloring agents used in this invention include carbon black, magenta, yellow, cyan series pigments as well as Nigrosine, Fast Blue and other dyes. When the toner of this invention is used, for example, in one-component development method, etc., as a pressure ~ixing magnetic toner, various kinds of magnetic powders can be included in the toners. The amount of magnetic powder in the toner depends upon various factors such as the conditions ~ 3;~
of ~he development process, but generally in the ran~e of 20-80% by weight based on the total weigh-t of the toner.
The magnetic toner is preferably adjusted to have an electric resistance of lol 2 to 1016 Qcm in view of its transferring and developing properties. When the electric resis~ance is too low~ a so-called "blur" phenomenon that a toner image is scattered during the transferring step takes place. When it is too high, bac~ ground fog is gradually increased or image density is decreased during the developing step. For the purpose, the magnetic powder is preferably added in an amount of 30-60~ by weight based on the total weight o-f the - toner. Examples of useful magnetic powder includ~ metals such as iron, cobalt, nickel, and alloys and oxides of these metals. With respect to magnetic toners, Fe304, y-Fe203, cobalt-doped iron oxide~ ferrite powders SUC}l as powders of MnZn ferrite, NiZn ferrite, etc., are preferably used. Such magnetic powders may be granular form or acicular form depending on the application of the toner, and the size of the powders is generally from 0.01 to 2~. Furt]lermore, these magnetic powders may be treated on their surfaces with a surface active agent or a fatty acid-, silane- or titanate-series coupling agent before being used.
If necessary, the toners may further contain materials such as plasticizers, granular or fibrous organic or inorganic reinforcing fillers, extenders, antioxidants, ',31 ~,.3 ;3 foaming agents, conduc-tivity or static controlling agents, ionic or nonionic surface active agents.
In order to further improve the 1uidity, develop-ing and transerring property, and preservative stability o the toner particles or powders, or to prevent filming o the toners on the surface of a photoconductor or improve the cleaning property of the toners, an external additive may be used in combination with the toners. Examples of useful external addi~ives, include long chain fatty acids (e. g., stearic aid) and amides or metal salts thereof, fine powders of molybdenum disulfide~ carbon black, graphite, fluorinated graphite, silicon carbide, boron nitride, silica, aluminum oxide, titanium dioxide, ~inc oxide, fine powders of fluorine resins, polycyclic aromatic compounds, wax-like materials, and fine powders of crosslinked or non-crosslinked resins.
These additives are usually solid fine particles having a low surface energy, below 30 dyn/cm in critical surface tension or having a smooth surface which is below 0.1 in friction coefficient. The additives may also be comprised of fine partiles having non-tackiness and some abrasive property.
~owever the additives are not restricted to any such materials.
In addition, if necessary, these external additives may be fixed on ~he surfaces of toner powders by a hot blast method or otherwise.
The developer composition of this invention can be produced by any conven-tional methods, ~or example, a method comprising fusing whole components, k.neading and grinding, a method comprising mixing the binding resinous materials in the form of solution followed by Xusing wnole componen~s, neading and griding, or a spray dry method. W}len producing a developer composition by a kneading-gTinding method, the molecular weight of the hard components including material (B) is preferably controlled so as to make the composition of the particle surface of the developer compositi.on uniform.
By controlling the number average molecular weight to about l,000 - 30,000, the ground interfaces can selectively become - a.hard component phase containing component ~B). - . -The particle sizes of the toner are generally 1-50~, preferably 5-30u. The particle sizes may be controlled by classification if necessary.
There is no particular restriction regardi.ng the form of the developer composition of this invention. When the developer composition is used as a toner for a two-component developer, after controlling the static property of the toner with a static controlling agent, the toner is used as a mixture thereof with a carrier material such as an iron powder. The developer composition of this invention can also be used as:magnetic toner for a one-component developer by mixing the developer composition with à magnetic powder as described above. When it is used as a magnetic tcner, it is possible to develop not only electric la~ent images but also also magnetic latent images. Furthermore, the developer composition of this invention shows excellent fixibllity with only the application of pressure. However~ as a matter of course, the composîtion of this invention can be securely fixed by heat and pressure or by heating or by the use of a solvent.
Specific examples of this invention and comparative examples are shown below. However, the invention is not limited to these examples CO~IPARATIVE EXr~MPLE 1 A mixture of 70 parts of a polystyrene resin (Picolastic~D-125, made by Esso Chemical Co.; Mw=52,000;
Mn=3,000; and Tg=55C), 30 parts of an ethylene-vinyl l~
acetate copolymer (Evaflex~220, made by ~litsui Polychemical Co., Ltd.; MI=150g/10 min; Tg<-30C; and content of vinyl acetate 28 wt%), and 10 parts of carbon black ~BP-1300, made by Cabot Corporation) were fused and kneaded for 10 min~ in a rotor-type kneader. After cooling, the mixture was roughly ground by means of a crusher. Furthermore, the mixture was finely ground by a jet crusher. The fine powders below 5 ~m and rough particles over 40 ~m were removed by means o-f a classifier to provide a toner having a mean paticle size of 14 ~m.
-f /'~ n.~ r The toner was mixed with 0.8~ by weight fine powder of hydrophobic colloidal silica. After further mixing a carrier iron powder having particle size of about ~O~m was added. The carrier/toner weight ratio was then adjusted to about 100/5~ An i~lage test was then perorrned using a copying machine, reconstructed Xerox ~2300, by Fuji Xerox Co. In addition, fixing was performed using a pressure fixing apparatus composed of 3 metallic rolls at a line pressure of 25 kg/cm. The initial image quality was relatively good,but when 5,0~0 copies were made by repeating the operation , the image density was reduced and background fog increased greatly.
Fixing was good in appearance but when the i'mages were ru'b'bed by a finger, the images came off partially, and ~ingers and clothes were readily stained.
lS When the properties of the developer were evaluated in order to investingate the cause, it was confirmed that the distribution o:f charge was broad and the toner stuck onto the carrier surface to deteriorate the image quality. Wllen the toner was further classified into a toner below 10~, a toner of 10-20~m, and a toner over 20~, and the rheology characteristics of each toner were evaluated, it was confirmed that the characteristics differed between the fine powder side and the rough particle side. Different from other characteristics such as electrical characteristics, the rheology characteristics were not influenced by any difference d-ue to a difference in particle sizes of the powder. Tha~ is, it is considered that since the toner which is a mixture of binding resinous materials incompatible Wit}l eacil other llave wide distribution in ~he inside composition and structure and is unstable, the composition or structure of toner differs betwe0n the fine powder side and the rough powder side and the cnaracteristics differ between them.
The toner was also found to be inferior in powder 1uidity and an~iblocking property at high temperature.
COMPARArIVE EXA,~IPLE 2 Using a mixture of 28 parts of a polystyrene resin (SI-120, made by Sanyo Chemical Industries 9 Ltd.;
~Iw=12,000; i~l=5,500 and Tg=70C), 12 parts of a low molecular weight polyethylenic wax having -COOH ~2203 A, made by Mitsui Peterochemical Industries, Ltd.; acid value =40, ~[v(~iscosity average molecular weight)=2,700 ;
p=0.93g/cm3; and mp=108C), and 60.parts of a magnetic powder (EPT-1000, made by Toda Kogyo KoK~) ~ a toner having a mean particle size of 16 ~m was prepared in the manner as in Comparative Example 1. The toner was mixed with 0.5% by weight carbon black and a copy test was performed using a one component-type developing machine, reconstructed Xerox ~ 2300.
In the early stage, good development and good transferring property were shown under ordinary circumstances,but when ~ 33 20`00 copies were continuously made, a roughness o image was observed. The cause is considered to be that since filming of the toner onto the photoconductive material occurred and the development and transfer were carried out selec~ively, the particle sizes of the toner changed with the passage of time.
In this connection, when the properties of the rough par~icle portion of the toner were compared with that of the fine powder portion, they differed from each other and it is considered that the distribution of the composition and mul~i-phase dispersion structure of the toner were broad and the toner was unstable.
Further, the pressuTe fixing of the toner at a line pressure of 25 Kg/cm showed the same defec~s as in Comparative Example 1.
COMPA~TIVE EXAMPLE 3 The same procedure as in Comparative Example 2 was repeated using unmodified polyethylene wax (171-P, made by Sanyo Chemical Industries, Ltd.; ~fv=1,500; p=0.93g/cm3; and mp=105C) in place of the wax having a carboxy group used in Comparative Example 2. No remarkable difference in image characteristics and fixing property was observed as compared with Comparative Example 2.
COMPARATI~E EXA~fPLE 4 The same procedure as in Comparative Examples 2 and 3 was repea~ed using a polyester resin having -OH at ~he terminal (GV-700, made by Toyobo Co., Ltd.; Mn=3,000;
and Tg=67C) in place of the polystyrene resi.n used in Comparative Example 3. The image charac~eristics and fixing priperty were not improved as compared with Comparative Examples 2 and 3.
EX~IPLE l A toner having a mean particle size of 14 ~rn was prepared by the same manner as in Comparative Example 1 using the following components;
Polystyrene~ resin (Picolatex D-125, made by ~ Esso chemical Co.) 30 parts Styrene-allyl alcohol copolymer (RJ-100, made by ~ionsanto Company; ~In=1,150; and Tg=50C) 40 parts Ethylenic modified resin having -OH and ~COOH
(Dulamin~C-2280, made by Takeda Chemical Industries, Ltd.;
hlI=93g/10 min; and mp=93C) 30 parts Carbon black (BP-1300, made by Cabot Corporation) 10 parts A developer was prepared by mixing the toner with 0.8% by weight fine powder of hydrophobic colloidal silica and further mixing with an iron carrier powder having a particle size of about 80 ~m in such manner that the carrier/
toner weight ratio became about 100/5 and a copy test was per~ormed using reconstructed Xerox ~ 2300 as in Comparative Example 1. When 20,000 copies were made by repeating the -f-r~)~e ~
~3~
operation, images were good. Furthermore, no change with the passage of ~ime was observed.
The pressure fixing property was evaluated at a line pressure of 20 kg/cm, 25 kg/cm and 30 kg/cm and each case showed good fixing propertyO This is believed that a stable and proper mul~i-phase dispersion structure was formed by the interaction of the functional group of the styrenic copolymer and that of the modified ethylene resin. Also, it is considered that since the surface composition of the toner particle was mainly composed of the styrenic resin and was uniform, the charge distribution was narrow. This was also confirmed by the analytical result by ESCA, etc.
....
A magnetic toner having a mean particle size of 15 ~m was prepared in the same manner as in Comparative Example 2 using the following components;
Polystyrene resin (ST-120, made by Sanyo Chemical Industries, Ltd.) 12 parts Styrene-allyl alcohol copolymer (RJ-100, made by l~lonsanto Corporation~ 12 parts Organic acid graft ethylene wax (2203 A, made by ~litsui Petrochemical Industries, Ltd.) 12 parts ~ 2~3~
Styrenic block copolymer (G-1652, made by Shell Chemical Co.; ratio of styrene to ethyl butylate=29/71; p=0.91g/cm3)4 parts ~lagnetic powder (EPT-1000, made by Toda Kogyo K. K.) 60 parts The toner was mixed with 0.5% by weight carbon black and when a copy test was performed using a one-component copying machine, reconstructed Xerox 2300 ~ all good development and transferring property were shown under all circumstances. Also, when 10,000 copies were continuously made, no change in image quality was observed. When a pressure fixing was applied at a line pressure of 25 kg/cm, the image was strongly fixed. ~Yhen the fixed image was subjected to a friction test using an adhesii~e tape or rubbed by a finger, the image did not come off or stain clothes.
EXAMPLE_3 A toner having a mean particle size of 17 ~Im was prepared in the manner as in the other examples from the following composition;
Polyester resin ~GV-700, having -OH, made by Toyobo Co., Ltd.;
~[n=3,000; and Tg=67C) 20 parts Oxidized polyethylene wax (E-300, made by Santo Chemical Industries~ Ltd.;
acid value 22,; ~Iv=2,000;
and mp=104C) 7 parts z~, Ethylene-vinyl acetate copolymer (UE-722, made by Toyo Soda Manifacturing Co., Ltd.; ~II=400g/
10 min; Tg~-30C; and content of vinyl aceta~e 28 wt%) 3 parts Magnetic powder (RB-BL, made by Titan Kogyo K. K.) 70 parts The toner was mixed with 0.4% by weight carbon black and 0.2~ by weight silica powder. When a copy test was performed as in Example 2, a good pressure fixing level and good image quality was obtained.
A magnetic toner having a mean particle size of _ 13 ~m was prepared by fusing and kneading a mix~ure of 45 parts of a styrenic copolymer produced by copolymerizing styrene, methyl methacrylate, butyl methacrylate and methacrylic acid and having an acid value of 30, Tg of 65C, Mw of 36,000 and ~In of ~,000; 2S parts of a modified ~ ethylenic resin having a hydroxy group (Dumilan~D-219, made by Takeda Chemical Indus~ries, Ltd.; MI=170g/10 min.; and mp=93C); 5 parts of carbon black (Raven~3500, Colombian Carbon Co.) and 30 parts of a magnetic powder (EPT-1000, made by Toda Kogyo K. K.), following by grinding and classifying.
The toner was mixed with 0.2% by weight zinc stearate and 0.6% by weight fine powder of hydrophobic silica, and a copy test was performed using a one-component copying machine, ~oJ-P ~
J !;,~ .3 reconstructed Xerox ~ 2300. Wllen 10,000 copies were made by repeating the opera~ion, the development, transferring property and image quality were good and ~he pressure fixin.g at a line pressure of 30 kg/cm was very excellent.
Ihe results obtained in Examples 1-4 and Comparative Examples 1-4 are summarized in Table 2.
.:L~ ?I~ t~3 ~ _~o' ~'0 ~ Vl,,=) 50'' :a'',~ ~''u, C~ 7 u~
OOIV,~Q
~ _ _ ~ ¦ 1~1 ~r ~ Lr~ In Lrl U~
~ _~-lCo ~ l ~ l ll l l l ~ v o ~ ~r. ~ ~o ~ n ~o ~ ~ n ~ ~ ~ ~ ~ u~
v ,~1 31 ~:a a) O I O~ ,, o O, ~O 1l 0 ~0 1 ~O, O, O r~ O ~_~
-1 o , _ O I OO I O O I O O I O O I O O ' O O I O G I O
~ ~ a ' o v,~ . ~ ~ ' ~t ~ ' ~ J ~ ~ 1'~ ~ ~ O ~ ~ ~ O
87,042/76 discloses an attempt to improve the pressure fixibility of a toner by blending a crystalline resin such as polyethylene wax as a main component with a small amount of material such as a vinylic resin. However, since a crystalline resin is used as the main binding resin, there exist the above-mentioned difficulties which are specific to the crystalline resin.
~hen a resin is blended with a resin having good compatibility therewith it is not possible to obtain a toner meeting many required properties which are reciprocal with each other. On the other hand, when resins incompatible with each other are blended , it is not possible to uniformly mix the resins and slight changes in the production conditions result in the formation of toner having incompatible resins in different dispersed state or dispersed amount.
Furthermore, the powder fluidity and electrical character istics such as the static property of the toner are greatly reduced. Therefore, when using conventional material "~,,;b'¦ ! t~
compositions it i~ no-t possible to ob-tain a pressure fixing toner having many required properties which are recip.rocal with each o~her. Furthermore, it is difficult to stably produce such a toner.
_M:~RY OF THE INVlENTION
An object of an aspect of the presen-t invention is to produce a developer composit:ion (sometimes herein refer-red to as "~oner") having an excellent pressure fixing property.
An object of an aspect of this inven~ion is to provide a developer composition having good powder fluidity, anti-blocking property.,~impact resistance and abrasion resis-tance.
An object of an aspect of this invention is to provide a developer composition having good production stability.
An object of an aspec-t of this invention is to pro-vide a developer composition stable with respect to environ-mental changes and stable with the passage of time.
An object of an aspect of this invention is to provide a developer composition capable of forming good and stable images for any development or transfer processes.
An object of an aspect of this invention is to provide a developer composition having a good cleaning property.
In accordance with an aspect of this invention there .. is provided a developer composition comprising (A) a binding resinous material having a polar functional group and a glass transition temperature below 0C and (B) a binding resi~ous material having a glass transition temperature above 40C, which is chemically incompatible with material (A). Material (B) has a polar functional group capable of interacting with the polar functional group of afore~
sai~ material (A). Materia:Ls (A) and (B) are i.ndispensable components for the binding resinous material of this inven-tion. Preferred results can be obtained using an olefinic polymer having a hydroxy group, a carboxyl group or a carbonyl group as material tA) and a styrenic polymer or a polyester resin having a hydroxy group, a carboxyl group or a dialkylamino group as material (B).
Another aspect of this invention is an electro-photographic process comprising developing an electric latent ima~e with a developer composition and fixing the thus developed image by the application of pressure, characterised in that the de~eloper composition referred to in the preceding paragraph is employed.
DETAILED DESCRIPTION OF THE INVENTION
. ~ .
The invention will be explained below in detail.
Firstly, the binding resinous material (A) in the developer composition of the present invention includes those having a glass transltion temperature below 0C, preferably below -30C. Material (A) is selected from resinous materials which easily show plastic deformation or viscoelastic deformation with a pressure of less than about 200 kg/cm2 at room temperature and has a polar functional group.
ll ,~. ~Q~
Polar functional groups of Material (A) include a hydroxy group, a carbonyl group, a carboxy group, an epoxy ~roup, a glicidyl g.roup, a nitro group, a sulfonic acid . .
-6a-group, an amino group, an amido group, a cyano group, an isocyanate groupS a diazonium group, an aziridine group, an aldehyde group, an acid anilydride, a methylol group, a tniol group, a mercapto group, a phosphoric acid group, and a halogerl-con~aining group. These functional groups may be substituted by a group such as a methyl group, ethyl group, phenyl group or may have an ether linkage, ester linkage, etc. ~nong these groups, a ihydroxy group, a carboxyl group and a càrbonyl group are preferred, because tiley are very stable, give no bad influences on the charac-teristics of a toner, and have a large interaction with : :
material (B).
The resinous material which has a polar functional group and which is capable of being deformed by pressure at normal temperature may be syntnetic or natural resinous materials. Examples of such materials include higher fatty acids ~e.g., stearic acid, oleic acid, etc.,) and derivatives tllereof (e.g., fatty acid amides), chlorinated paraf~in, chlorinated polyethylene, chlorinated polypropylene, oxidized polyethylene, polypropylene oxideg ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, organic acid graft polyethylene, rubber-like acrylic acid copolymer, polyvinyl acetate, polyvinyl butyral, silicone and modified resins thereof, polycarbonate, fluorinated rubber, fluorinated~a~, nitril rubber, chloroprene rubber, polyamide, ~3 polyester, polyether, polyurethane~ and polyalkyd. Of these, oxidlzed polyethylene, ethylene-acrylic acid copolyme.r and organic acid graft polyethylene, which have a hydroxy group, a carboxyl yroup or a carbonyl group are particularly preferred for material (~).
Binding resinous material (s3 in the developer composi-tion of the present :invention can be selected Erom natural and syrlthetic resi.nous material3 having a glass transition temperature above ~10C, more preferably 60-80C, and having a polar functional group as defined in mate~lal (A) A hydro~y group, a carboxyl group and dialkylamino group are particularly preferred as the polar f~mctional group of materi.al (B). In particular, styrene-acrylic acid copolymer, epoxy resin, phenol resin, polyester resin, etc.~
satisfying the aforesaid factors are preferably used since they meet many required properties for ~onerO
Material ~A) is chemically incompatible with material (B) and the polar functional group of material (A) must be interact.ible with the polar functional group of material (~). Solubility is a suitable parameter for compatibility. With respect to this invention, when the parameter of the solubility of material (A) is taken as SA and the parameter of the solubility of material (B) is taken as ~B~ when 1~ A ~ 3B¦is higher than about 0.5 it is defined as being incompatible. The solubility parameters of the resinous materials can be obtained by calculation.
Howevex, standard values which can be relied on are disclosed in "Polymer Handhook", 2nd Ed. (John Wiley &
Sons) to disclose such values.
The interaction of the functional groups may involve (13 hydrophobic bonding, (2) electrostatic bonding, (3) hydrogen bonding, (4) charge transfer bonding, and (5) covalent bonding interactions.
However since the interaction of polar ~unctional groups is important in this invention, the interaction of (2) to (5) are of greater importance.
With consideration to the factor explained above it should be understood that many combinations of materials ~A) and ~B) are possible in this invention. Hol~ever, preferred materials which meet various electric, mechanical~ rheological, thermal, opticai and chemical properties required for a toner, inclucle the combination of an olefinic polymer having group -OH, -COOH or `C=O as material (A) and a styrenic copolymer or de-natured resin thereof, or a polyester resin each having group -OH, -COOH
or -MRlR2 ~herein Rl and R29 which may be the same or different, each represents an alkyl group (e.g., methyl, ethyl) as material (B). The interaction between an alcoholic -OH group and an acid -COOH group is particularly preferred for the purpose of the present invention. ~Iost preferred combinations of ma~erials (A) and (B) are given in Table 1 below.
Table Material. (A) Material (B) . . _ . _ . _ . _ . _ _ . . _ . . . _ _ . . . _ . _ _ _ _ . _ . . . . _ . . _oxidizecl polyethylene styrene-ally alcohol copolymer organic acid gra~t polyethylene '~
ethylene-acrylic acid copolymer "
ethylene-vinyl acetate styrene-(meth)acrylic acid copolymer copolymer oxidized polyethylene styrene-dimethylaminoethyl methacrylate copolymer organic acid graft polyethylene "
hydroxy group-containing aromatic polyester For example, if polyethylene is consideled as a base for-the olefinic polymer, whose solubility parameter is about 8.0 as compared with about 9.0 for the solubility parameter of polystyrene which is one of the base resins for material (B), it will be understood that both materials are essentially incompatible with each other. ~ere is no particular restriction regarding the position of the polar functional group in both materials (A) and (B). However, ~he materials having the polar functional group on the side chain or the en~l of the molecular chain aTe readily utilizable.
la With respect to the content of the functional group~
when, for example a -COOH is present, the acid ~alue is higher than 5 in both materials (A) and (B). Other polar group contents are similar in this regard. However, considerable care must be taken so that the content of the functional group is not too high. I-f the content gets too high, the interaction or reaction between the same kinds of molecules or different kinds of molecules as well as the intramolecular interaction or reaction become too strong.
This can cause difficulties. Usually, when the functional group is -COOH, a resin having an acid value of from about 10 to about 100 is preferred. The acid value is shown by the milligTam number of potassium hydroxide necessary for neutralizing the acid contained in one gram of the resin.
It has hitherto been at-tempted to introduce a polar functional group into a binder resin in order to control electrical characteristics of a toner. However, the present invention involves introducing a polar functional group into each of binding res:inous materials ~A) and (B) WlliCIl aTe incompatible with each other and have largely di~ferent physical and chemical properties, whereby materials (A) and (~) interact with each other, and thus the objects o this invention can be attained. In other words, it is not possible to achieve the objects of this invention merely by introducing a polar functional group into a binder resin.
The effects and merits of the presen~ invention are briefly explained below. As described above, many reciprocal properties are required for a pressure fixable -toner. The toner must be constructed so that it exllibits these reciprocal properties independently in each step of lS tile image forming processes. In order to attain this purpose 7 it is preferred tnat binding resin materials having different properties are in the state of forming a proper multi-phase structure. When mixing two or more kinds of binding resinous materials having different properties, if they have high compatibility with each other, the mixture obtained canno-t exhibit the individual different properties of each resinous material. On the other hand7 if they are incompatible ~ith each other, the mixture will meet certain of the various required properties which are reciprocal with each other. However, it is difficult to maintain r i ~ ~ 3 ~
tile dispersed multi-phase structure in a stationary sta~e Furthermore the heterogeneous inter~ace between them frequently reduces the properties of the toner.
The inventors have discovered that these .5 difficulties can be overcome by introducing a functional group interaction between binding resinous materials (A) and (B) which are incompa~ible wit:h e~ac3L other and have dif~erent properties. Since binding resinous materials ~A) and (B) are properly incompatible with each other, when the materials are mixed, materials (A) and (B) maintain thei.r indivi-dual domain, thereby`a desired multi-phase structure can be attained. Furthermore, since there is an interaction between ~ -the polaT function groups of materials (A) and the polar functional group of material ~B), the heteroge~eous interface between materials (A) and (B) is fixed and the multi-layer dispersion structure itsel:f becomesstable. The interaction in this ~Lse may be a secondary bonding tyye of interaction sucn as hydrogen bonding, electrostatic bonding or alternatively may be a covalent bonding type of interaction such as grafting or crosslinking It has also been found that when secondary bonding takes place the stabilization in multi-phase dispersion structure not only facilitates the control of electric characteristics and mechanical properties, but also strengthens tne shearing stress and shearing time reliance of the mechanical properties of the toner, which are advantageous because the resulting fixed toner image is free of smudges or smears even when rubbed with finger.
When magnetic powder and other fillers having polar surfaces are contained in the ~oner, the interaction between the polar funct.ional groups of binding resinous materials (A) and (B) and these fillers can be expected.
Due to this interaction the multi-phase dispersion structure of the toner is more stabilized. Fur~hermore, mechanical and thermal properties can be improved.
It is possible to control the electrical characteris~ics of the toner in a conventional manner by adjusting the electron donative or electron acceptive propeTty of the polar functional groups of materials (A) and (B).
Preferably material (A) ~ which is a soft component having a glass transition temperature below 0C , is present in an amoun~ within the range of 5-50% by weight, preferably 10-30% by weight to the total weight of binding resinous materials. If it is contained in an amount below 5% by weight, the toner is poor witll respect to pressure deformability during pressure fixing. If the content is higher than 50% by weight, the anti-blocking property, powder fluidity and producibility of the toner are greatly reduced.
On the other lland, it is preferred that material (B), which is -tAe hard component and have a glass transition temperature above 40C,be contained in the range of 5-95%
by weight, preferably 10-80% by weight~ more preferably 35-65% by weight~ based on the tota]. weight o-f binding resinous materials.
When the toner further contains a binding resinous material other than materials (A~ and (B), it is preferred to employ the resinous material having good compatibility with ma~erial (A), if the resinous material is a soft component having a glass transition temperature below 0C
or with materia3 (B) if the resinous material is a hard component having a glass transition temperature above 40~.
In the case, it is necessary to prepare a toner in such a manner that the proportion of the total soft components containing material (A) be 5-50% by weight of binding resinous materials and the proportion of the total hard components containing material (B) be 50-95% by weight.
The toner may contain various kinds of additives such as coloring agents. Examples of useful coloring agents used in this invention include carbon black, magenta, yellow, cyan series pigments as well as Nigrosine, Fast Blue and other dyes. When the toner of this invention is used, for example, in one-component development method, etc., as a pressure ~ixing magnetic toner, various kinds of magnetic powders can be included in the toners. The amount of magnetic powder in the toner depends upon various factors such as the conditions ~ 3;~
of ~he development process, but generally in the ran~e of 20-80% by weight based on the total weigh-t of the toner.
The magnetic toner is preferably adjusted to have an electric resistance of lol 2 to 1016 Qcm in view of its transferring and developing properties. When the electric resis~ance is too low~ a so-called "blur" phenomenon that a toner image is scattered during the transferring step takes place. When it is too high, bac~ ground fog is gradually increased or image density is decreased during the developing step. For the purpose, the magnetic powder is preferably added in an amount of 30-60~ by weight based on the total weight o-f the - toner. Examples of useful magnetic powder includ~ metals such as iron, cobalt, nickel, and alloys and oxides of these metals. With respect to magnetic toners, Fe304, y-Fe203, cobalt-doped iron oxide~ ferrite powders SUC}l as powders of MnZn ferrite, NiZn ferrite, etc., are preferably used. Such magnetic powders may be granular form or acicular form depending on the application of the toner, and the size of the powders is generally from 0.01 to 2~. Furt]lermore, these magnetic powders may be treated on their surfaces with a surface active agent or a fatty acid-, silane- or titanate-series coupling agent before being used.
If necessary, the toners may further contain materials such as plasticizers, granular or fibrous organic or inorganic reinforcing fillers, extenders, antioxidants, ',31 ~,.3 ;3 foaming agents, conduc-tivity or static controlling agents, ionic or nonionic surface active agents.
In order to further improve the 1uidity, develop-ing and transerring property, and preservative stability o the toner particles or powders, or to prevent filming o the toners on the surface of a photoconductor or improve the cleaning property of the toners, an external additive may be used in combination with the toners. Examples of useful external addi~ives, include long chain fatty acids (e. g., stearic aid) and amides or metal salts thereof, fine powders of molybdenum disulfide~ carbon black, graphite, fluorinated graphite, silicon carbide, boron nitride, silica, aluminum oxide, titanium dioxide, ~inc oxide, fine powders of fluorine resins, polycyclic aromatic compounds, wax-like materials, and fine powders of crosslinked or non-crosslinked resins.
These additives are usually solid fine particles having a low surface energy, below 30 dyn/cm in critical surface tension or having a smooth surface which is below 0.1 in friction coefficient. The additives may also be comprised of fine partiles having non-tackiness and some abrasive property.
~owever the additives are not restricted to any such materials.
In addition, if necessary, these external additives may be fixed on ~he surfaces of toner powders by a hot blast method or otherwise.
The developer composition of this invention can be produced by any conven-tional methods, ~or example, a method comprising fusing whole components, k.neading and grinding, a method comprising mixing the binding resinous materials in the form of solution followed by Xusing wnole componen~s, neading and griding, or a spray dry method. W}len producing a developer composition by a kneading-gTinding method, the molecular weight of the hard components including material (B) is preferably controlled so as to make the composition of the particle surface of the developer compositi.on uniform.
By controlling the number average molecular weight to about l,000 - 30,000, the ground interfaces can selectively become - a.hard component phase containing component ~B). - . -The particle sizes of the toner are generally 1-50~, preferably 5-30u. The particle sizes may be controlled by classification if necessary.
There is no particular restriction regardi.ng the form of the developer composition of this invention. When the developer composition is used as a toner for a two-component developer, after controlling the static property of the toner with a static controlling agent, the toner is used as a mixture thereof with a carrier material such as an iron powder. The developer composition of this invention can also be used as:magnetic toner for a one-component developer by mixing the developer composition with à magnetic powder as described above. When it is used as a magnetic tcner, it is possible to develop not only electric la~ent images but also also magnetic latent images. Furthermore, the developer composition of this invention shows excellent fixibllity with only the application of pressure. However~ as a matter of course, the composîtion of this invention can be securely fixed by heat and pressure or by heating or by the use of a solvent.
Specific examples of this invention and comparative examples are shown below. However, the invention is not limited to these examples CO~IPARATIVE EXr~MPLE 1 A mixture of 70 parts of a polystyrene resin (Picolastic~D-125, made by Esso Chemical Co.; Mw=52,000;
Mn=3,000; and Tg=55C), 30 parts of an ethylene-vinyl l~
acetate copolymer (Evaflex~220, made by ~litsui Polychemical Co., Ltd.; MI=150g/10 min; Tg<-30C; and content of vinyl acetate 28 wt%), and 10 parts of carbon black ~BP-1300, made by Cabot Corporation) were fused and kneaded for 10 min~ in a rotor-type kneader. After cooling, the mixture was roughly ground by means of a crusher. Furthermore, the mixture was finely ground by a jet crusher. The fine powders below 5 ~m and rough particles over 40 ~m were removed by means o-f a classifier to provide a toner having a mean paticle size of 14 ~m.
-f /'~ n.~ r The toner was mixed with 0.8~ by weight fine powder of hydrophobic colloidal silica. After further mixing a carrier iron powder having particle size of about ~O~m was added. The carrier/toner weight ratio was then adjusted to about 100/5~ An i~lage test was then perorrned using a copying machine, reconstructed Xerox ~2300, by Fuji Xerox Co. In addition, fixing was performed using a pressure fixing apparatus composed of 3 metallic rolls at a line pressure of 25 kg/cm. The initial image quality was relatively good,but when 5,0~0 copies were made by repeating the operation , the image density was reduced and background fog increased greatly.
Fixing was good in appearance but when the i'mages were ru'b'bed by a finger, the images came off partially, and ~ingers and clothes were readily stained.
lS When the properties of the developer were evaluated in order to investingate the cause, it was confirmed that the distribution o:f charge was broad and the toner stuck onto the carrier surface to deteriorate the image quality. Wllen the toner was further classified into a toner below 10~, a toner of 10-20~m, and a toner over 20~, and the rheology characteristics of each toner were evaluated, it was confirmed that the characteristics differed between the fine powder side and the rough particle side. Different from other characteristics such as electrical characteristics, the rheology characteristics were not influenced by any difference d-ue to a difference in particle sizes of the powder. Tha~ is, it is considered that since the toner which is a mixture of binding resinous materials incompatible Wit}l eacil other llave wide distribution in ~he inside composition and structure and is unstable, the composition or structure of toner differs betwe0n the fine powder side and the rough powder side and the cnaracteristics differ between them.
The toner was also found to be inferior in powder 1uidity and an~iblocking property at high temperature.
COMPARArIVE EXA,~IPLE 2 Using a mixture of 28 parts of a polystyrene resin (SI-120, made by Sanyo Chemical Industries 9 Ltd.;
~Iw=12,000; i~l=5,500 and Tg=70C), 12 parts of a low molecular weight polyethylenic wax having -COOH ~2203 A, made by Mitsui Peterochemical Industries, Ltd.; acid value =40, ~[v(~iscosity average molecular weight)=2,700 ;
p=0.93g/cm3; and mp=108C), and 60.parts of a magnetic powder (EPT-1000, made by Toda Kogyo KoK~) ~ a toner having a mean particle size of 16 ~m was prepared in the manner as in Comparative Example 1. The toner was mixed with 0.5% by weight carbon black and a copy test was performed using a one component-type developing machine, reconstructed Xerox ~ 2300.
In the early stage, good development and good transferring property were shown under ordinary circumstances,but when ~ 33 20`00 copies were continuously made, a roughness o image was observed. The cause is considered to be that since filming of the toner onto the photoconductive material occurred and the development and transfer were carried out selec~ively, the particle sizes of the toner changed with the passage of time.
In this connection, when the properties of the rough par~icle portion of the toner were compared with that of the fine powder portion, they differed from each other and it is considered that the distribution of the composition and mul~i-phase dispersion structure of the toner were broad and the toner was unstable.
Further, the pressuTe fixing of the toner at a line pressure of 25 Kg/cm showed the same defec~s as in Comparative Example 1.
COMPA~TIVE EXAMPLE 3 The same procedure as in Comparative Example 2 was repeated using unmodified polyethylene wax (171-P, made by Sanyo Chemical Industries, Ltd.; ~fv=1,500; p=0.93g/cm3; and mp=105C) in place of the wax having a carboxy group used in Comparative Example 2. No remarkable difference in image characteristics and fixing property was observed as compared with Comparative Example 2.
COMPARATI~E EXA~fPLE 4 The same procedure as in Comparative Examples 2 and 3 was repea~ed using a polyester resin having -OH at ~he terminal (GV-700, made by Toyobo Co., Ltd.; Mn=3,000;
and Tg=67C) in place of the polystyrene resi.n used in Comparative Example 3. The image charac~eristics and fixing priperty were not improved as compared with Comparative Examples 2 and 3.
EX~IPLE l A toner having a mean particle size of 14 ~rn was prepared by the same manner as in Comparative Example 1 using the following components;
Polystyrene~ resin (Picolatex D-125, made by ~ Esso chemical Co.) 30 parts Styrene-allyl alcohol copolymer (RJ-100, made by ~ionsanto Company; ~In=1,150; and Tg=50C) 40 parts Ethylenic modified resin having -OH and ~COOH
(Dulamin~C-2280, made by Takeda Chemical Industries, Ltd.;
hlI=93g/10 min; and mp=93C) 30 parts Carbon black (BP-1300, made by Cabot Corporation) 10 parts A developer was prepared by mixing the toner with 0.8% by weight fine powder of hydrophobic colloidal silica and further mixing with an iron carrier powder having a particle size of about 80 ~m in such manner that the carrier/
toner weight ratio became about 100/5 and a copy test was per~ormed using reconstructed Xerox ~ 2300 as in Comparative Example 1. When 20,000 copies were made by repeating the -f-r~)~e ~
~3~
operation, images were good. Furthermore, no change with the passage of ~ime was observed.
The pressure fixing property was evaluated at a line pressure of 20 kg/cm, 25 kg/cm and 30 kg/cm and each case showed good fixing propertyO This is believed that a stable and proper mul~i-phase dispersion structure was formed by the interaction of the functional group of the styrenic copolymer and that of the modified ethylene resin. Also, it is considered that since the surface composition of the toner particle was mainly composed of the styrenic resin and was uniform, the charge distribution was narrow. This was also confirmed by the analytical result by ESCA, etc.
....
A magnetic toner having a mean particle size of 15 ~m was prepared in the same manner as in Comparative Example 2 using the following components;
Polystyrene resin (ST-120, made by Sanyo Chemical Industries, Ltd.) 12 parts Styrene-allyl alcohol copolymer (RJ-100, made by l~lonsanto Corporation~ 12 parts Organic acid graft ethylene wax (2203 A, made by ~litsui Petrochemical Industries, Ltd.) 12 parts ~ 2~3~
Styrenic block copolymer (G-1652, made by Shell Chemical Co.; ratio of styrene to ethyl butylate=29/71; p=0.91g/cm3)4 parts ~lagnetic powder (EPT-1000, made by Toda Kogyo K. K.) 60 parts The toner was mixed with 0.5% by weight carbon black and when a copy test was performed using a one-component copying machine, reconstructed Xerox 2300 ~ all good development and transferring property were shown under all circumstances. Also, when 10,000 copies were continuously made, no change in image quality was observed. When a pressure fixing was applied at a line pressure of 25 kg/cm, the image was strongly fixed. ~Yhen the fixed image was subjected to a friction test using an adhesii~e tape or rubbed by a finger, the image did not come off or stain clothes.
EXAMPLE_3 A toner having a mean particle size of 17 ~Im was prepared in the manner as in the other examples from the following composition;
Polyester resin ~GV-700, having -OH, made by Toyobo Co., Ltd.;
~[n=3,000; and Tg=67C) 20 parts Oxidized polyethylene wax (E-300, made by Santo Chemical Industries~ Ltd.;
acid value 22,; ~Iv=2,000;
and mp=104C) 7 parts z~, Ethylene-vinyl acetate copolymer (UE-722, made by Toyo Soda Manifacturing Co., Ltd.; ~II=400g/
10 min; Tg~-30C; and content of vinyl aceta~e 28 wt%) 3 parts Magnetic powder (RB-BL, made by Titan Kogyo K. K.) 70 parts The toner was mixed with 0.4% by weight carbon black and 0.2~ by weight silica powder. When a copy test was performed as in Example 2, a good pressure fixing level and good image quality was obtained.
A magnetic toner having a mean particle size of _ 13 ~m was prepared by fusing and kneading a mix~ure of 45 parts of a styrenic copolymer produced by copolymerizing styrene, methyl methacrylate, butyl methacrylate and methacrylic acid and having an acid value of 30, Tg of 65C, Mw of 36,000 and ~In of ~,000; 2S parts of a modified ~ ethylenic resin having a hydroxy group (Dumilan~D-219, made by Takeda Chemical Indus~ries, Ltd.; MI=170g/10 min.; and mp=93C); 5 parts of carbon black (Raven~3500, Colombian Carbon Co.) and 30 parts of a magnetic powder (EPT-1000, made by Toda Kogyo K. K.), following by grinding and classifying.
The toner was mixed with 0.2% by weight zinc stearate and 0.6% by weight fine powder of hydrophobic silica, and a copy test was performed using a one-component copying machine, ~oJ-P ~
J !;,~ .3 reconstructed Xerox ~ 2300. Wllen 10,000 copies were made by repeating the opera~ion, the development, transferring property and image quality were good and ~he pressure fixin.g at a line pressure of 30 kg/cm was very excellent.
Ihe results obtained in Examples 1-4 and Comparative Examples 1-4 are summarized in Table 2.
.:L~ ?I~ t~3 ~ _~o' ~'0 ~ Vl,,=) 50'' :a'',~ ~''u, C~ 7 u~
OOIV,~Q
~ _ _ ~ ¦ 1~1 ~r ~ Lr~ In Lrl U~
~ _~-lCo ~ l ~ l ll l l l ~ v o ~ ~r. ~ ~o ~ n ~o ~ ~ n ~ ~ ~ ~ ~ u~
v ,~1 31 ~:a a) O I O~ ,, o O, ~O 1l 0 ~0 1 ~O, O, O r~ O ~_~
-1 o , _ O I OO I O O I O O I O O I O O ' O O I O G I O
~ ~ a ' o v,~ . ~ ~ ' ~t ~ ' ~ J ~ ~ 1'~ ~ ~ O ~ ~ ~ O
3~ '~ ~ 1 ~1 ~ l ~ ~ ~1~ 1 ~1 1 0~ I ~i -I I O r~ , ., ~_~o l l l ~ ,' l l ~ ~ U I V o ~ V o . V ~ V .
Q ¦ _ ~ O V _ .~C lo ~ ~ V _~
V ~ ~ o ~ V ~ ~ V ~ ~ D --_ ~ V~ C~ o ~ .~ ~O~J :t~
_ ~ Q U ~ U ;~ U r .
A v V _I v _ V O V _ . , , V 3:
~- ~ ~ u ~ jw ~
.~ ,, .~S
~ote: *l Image density was measured when an original having an optical density of 0.7 was copied.
*2 Finger smudge shows the degree of smudge of an image or finger upon rubbing the image with 5finger af-ter pressure fixing. Grade 5 shows that smudges occur in handling of the copied sheet and the fixed image is transferred to a back surface of sheet which is in contact with the image when the copied sheets are piled.
10*3 Toner transfer rate is the rate of toner amount to a sheet on which a toner image is fixed.
- Higher value shows a better toner pro~erty.
It is clearly seen from Table 2 that the toner of the present invention provides an excellent toner image free lS o background fogs with high resolution even after 5,000 reproductions and is thoroughly fixed by the application of pressure so that, in contrast to a conventional toner for pressure fixing, the fixed toner image does not smudge or adhere to a finger when rubbed with finger. F~rther the fixed toner image does not transfer to a back surface of sheet which contacts with the image during piling storage~
Furthermore, the toner transfer rate of the toner of the present invention is no~ so decreased even at an increased hùmidity. In particular, the magnetic toner of the present invention has a markedly stable ~oner transfer rate as compared to a conventional magnetic toner.
~ hile the invention has been described in detail and with reference to specific embodiment thereo7 it will be apparent to one skilled in ~he art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Q ¦ _ ~ O V _ .~C lo ~ ~ V _~
V ~ ~ o ~ V ~ ~ V ~ ~ D --_ ~ V~ C~ o ~ .~ ~O~J :t~
_ ~ Q U ~ U ;~ U r .
A v V _I v _ V O V _ . , , V 3:
~- ~ ~ u ~ jw ~
.~ ,, .~S
~ote: *l Image density was measured when an original having an optical density of 0.7 was copied.
*2 Finger smudge shows the degree of smudge of an image or finger upon rubbing the image with 5finger af-ter pressure fixing. Grade 5 shows that smudges occur in handling of the copied sheet and the fixed image is transferred to a back surface of sheet which is in contact with the image when the copied sheets are piled.
10*3 Toner transfer rate is the rate of toner amount to a sheet on which a toner image is fixed.
- Higher value shows a better toner pro~erty.
It is clearly seen from Table 2 that the toner of the present invention provides an excellent toner image free lS o background fogs with high resolution even after 5,000 reproductions and is thoroughly fixed by the application of pressure so that, in contrast to a conventional toner for pressure fixing, the fixed toner image does not smudge or adhere to a finger when rubbed with finger. F~rther the fixed toner image does not transfer to a back surface of sheet which contacts with the image during piling storage~
Furthermore, the toner transfer rate of the toner of the present invention is no~ so decreased even at an increased hùmidity. In particular, the magnetic toner of the present invention has a markedly stable ~oner transfer rate as compared to a conventional magnetic toner.
~ hile the invention has been described in detail and with reference to specific embodiment thereo7 it will be apparent to one skilled in ~he art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (10)
1. A developer composition comprising:
a binding resinous material (A) having a polar functional group and a glass transition temperature below 0°C; and a binding resinous material (B) having a glass transition temperature above 40°C, wherein the resinous material (B) is incompatible with the material (A), further wherein the material (B) has a polar functional group capable of interacting with the polar functional group of the material (A).
a binding resinous material (A) having a polar functional group and a glass transition temperature below 0°C; and a binding resinous material (B) having a glass transition temperature above 40°C, wherein the resinous material (B) is incompatible with the material (A), further wherein the material (B) has a polar functional group capable of interacting with the polar functional group of the material (A).
2. A developer composition as claimed in Claim 1, further comprising a fine magnetic powder present in an amount of from 20 to 80% by weight based on the total weight of the developer composition.
3. A developer composition as claimed in Claim 1, wherein the material (A) is an olefinic polymer having a hydroxy group, carboxyl group or carbonyl group as the polar functional group and wherein the material (B) is a styrenic polymer having a hydroxy group, carboxyl group, a dialkylamino group as the polar functional group.
4. A developer composition as claimed in Claim 1, wherein the material (A) is an olefinic polymer having a hydroxy group,carboxyl group or carbonyl group as the polar functional group and the material (B) is a polyester resin having a hydroxy group, carboxyl group or dialkylamino group as the polar functional group.
5. A developer composition as claimed in Claim 3, wherein the olefinic polymer is oxidized polyethylene, ethylene-acrylic acid copolymer or organic acid graft poly-ethylene.
6. A developer composition as claimed in Claim 4, wherein the olefinic polymer is oxidized polyethylene, ethylene-acrylic acid copolymer or organic acid graft poly-ethylene.
7. A developer composition as claimed in Claim 1 or 2, wherein the combination of the materials (A) and (B) is oxidized polyethylene and styrene-ally alcohol copolymer, organic acid graft polyethylene and styrene-ally alcohol copolymer, ethylene-acrylic acid copolymer and styrene-ally alcohol copolymer, ethylene-vinyl acetate copolymer and styrene-(meth)acrylic acid copolymer, oxidized polyethylene and styrene-dimethylaminoethyl methacrylate copolymer, organic acid graft polyethylene and styrene-dimethylamino-ethyl methacrylate copolymer, or organic acid graft poly-ethylene and hydroxy group-containing aromatic polyester.
8. A developer composition as claimed in Claim 1 or 2, wherein the material (B) is contained in an amount of from 35 to 65% by weight based on the total weight of binding resinous materials.
9. A developer composition as claimed in Claim 2, wherein the magnetic powder is contained in an amount of from 30 to 60% by weight based on the total weight of the developer composition and the developer composition has an electric resistance of from 1012 to 1016 .OMEGA.cm.
10. An electrophotographic process comprising develop-ing an electric latent image with a developer composition and fixing the thus developed image by the application of pressure, characterized in that said developer composition comprises;
a binding resinous material (A) having a polar functional group and a glass transition temperature below 0°C; and a binding resinous material (B) having a glass transition temperature above 40°C, wherein the resinous material (B) is incompatible with the material (A) a further wherein the material (B) has a polar functional group capable of interacting with the polar functional group of the material (A).
a binding resinous material (A) having a polar functional group and a glass transition temperature below 0°C; and a binding resinous material (B) having a glass transition temperature above 40°C, wherein the resinous material (B) is incompatible with the material (A) a further wherein the material (B) has a polar functional group capable of interacting with the polar functional group of the material (A).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56-72201 | 1981-05-15 | ||
| JP56072201A JPS57188045A (en) | 1981-05-15 | 1981-05-15 | Developer composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1183033A true CA1183033A (en) | 1985-02-26 |
Family
ID=13482376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000403032A Expired CA1183033A (en) | 1981-05-15 | 1982-05-14 | Developer compositions comprising two incompatible resins with interacting polar groups |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0066395B1 (en) |
| JP (1) | JPS57188045A (en) |
| CA (1) | CA1183033A (en) |
| DE (1) | DE3273295D1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5213740A (en) * | 1989-05-30 | 1993-05-25 | Xerox Corporation | Processes for the preparation of toner compositions |
| US8278018B2 (en) | 2007-03-14 | 2012-10-02 | Xerox Corporation | Process for producing dry ink colorants that will reduce metamerism |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4656111A (en) * | 1983-04-12 | 1987-04-07 | Canon Kabushiki Kaisha | Pressure-fixable toner comprising combination of a compound having hydrocarbon chain and a compound having amino group |
| JPS60164754A (en) * | 1984-02-06 | 1985-08-27 | Hitachi Chem Co Ltd | Toner for developing electrostatic charge image |
| JPS60225168A (en) * | 1984-04-23 | 1985-11-09 | Hitachi Chem Co Ltd | Toner for developing electrostatic charge image |
| JPH0740142B2 (en) * | 1985-11-05 | 1995-05-01 | 日本カーバイド工業株式会社 | Toner for electrostatic image development |
| JPH075850B2 (en) * | 1986-04-05 | 1995-01-25 | 株式会社リコー | Colorants and their use |
| EP0380813A1 (en) * | 1989-01-31 | 1990-08-08 | Agfa-Gevaert N.V. | Dry electrophotograhic toner composition |
| JPH0588406A (en) * | 1991-04-16 | 1993-04-09 | Minolta Camera Co Ltd | Toner for electrophotograph and manufacture thereof |
| JPH07181727A (en) * | 1993-12-24 | 1995-07-21 | Kao Corp | Electrophotographic toner and reinforcing agent for toner |
| JPH07209905A (en) * | 1994-01-13 | 1995-08-11 | Ricoh Co Ltd | Method for regenerating copying member and electrophotographic developing toner |
| WO1996007702A1 (en) * | 1994-09-09 | 1996-03-14 | Shell Internationale Research Maatschappij B.V. | Block copolymer containing binder composition and electrophotographic toner composition derived therefrom |
| JPH1090947A (en) * | 1996-09-18 | 1998-04-10 | Toshiba Corp | Developer and image forming device |
| JP3946518B2 (en) | 2001-12-28 | 2007-07-18 | 株式会社リコー | Color toner for image formation, image forming apparatus and toner container |
| KR20080033622A (en) * | 2006-10-12 | 2008-04-17 | 삼성전자주식회사 | Binder resin composition for toner, toner composition and preparing method thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE789988A (en) * | 1971-10-12 | 1973-04-12 | Xerox Corp | COMPOSITION OF DEVELOPER AND METHOD FOR ITS USE |
| BE793248A (en) * | 1971-12-30 | 1973-06-22 | Xerox Corp | ELECTROSTATOGRAPHIC DEVELOPER |
| BE793554A (en) * | 1971-12-30 | 1973-06-29 | Xerox Corp | ELECTROSTATOGRAPHIC DEVELOPER |
| JPS5751669B2 (en) * | 1974-12-16 | 1982-11-02 | ||
| CA1062946A (en) * | 1974-12-19 | 1979-09-25 | Xerox Corporation | Electrostatographic pressure-fixable toner composition |
| JPS5289928A (en) * | 1976-01-22 | 1977-07-28 | Mita Industrial Co Ltd | Pressure fixing developing agent for electrostatography |
| JPS542741A (en) * | 1977-06-08 | 1979-01-10 | Canon Inc | Pressure fixing toner |
| JPS5589855A (en) * | 1978-12-28 | 1980-07-07 | Canon Inc | Pressure-fixable capsule toner |
-
1981
- 1981-05-15 JP JP56072201A patent/JPS57188045A/en active Granted
-
1982
- 1982-05-14 DE DE8282302468T patent/DE3273295D1/en not_active Expired
- 1982-05-14 CA CA000403032A patent/CA1183033A/en not_active Expired
- 1982-05-14 EP EP19820302468 patent/EP0066395B1/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5213740A (en) * | 1989-05-30 | 1993-05-25 | Xerox Corporation | Processes for the preparation of toner compositions |
| US8278018B2 (en) | 2007-03-14 | 2012-10-02 | Xerox Corporation | Process for producing dry ink colorants that will reduce metamerism |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0237585B2 (en) | 1990-08-24 |
| EP0066395A1 (en) | 1982-12-08 |
| EP0066395B1 (en) | 1986-09-17 |
| JPS57188045A (en) | 1982-11-18 |
| DE3273295D1 (en) | 1986-10-23 |
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