WO2009157582A1

WO2009157582A1 - Toner for electrostatic-image development and process for producing the same

Info

Publication number: WO2009157582A1
Application number: PCT/JP2009/061808
Authority: WO
Inventors: 秋山悟; 植田将司; 斉藤勝敏; 坪倉光男; 次井剛健; 中山修造; 浅野成敏
Original assignee: 株式会社アイメックス
Priority date: 2008-06-24
Filing date: 2009-06-23
Publication date: 2009-12-30
Also published as: JP5072104B2; JP2010008481A

Abstract

A toner for electrostatic-image development, characterized by comprising toner base particles obtained by subjecting fine particles comprising a binder resin, a charge control agent, and a colorant to a thermal crosslinking treatment in a suspended state to thereby round the fine particles so as to result in an average roundness of 0.930-0.980. The toner is further characterized in that the charge control agent comprises a product of the reaction of an aromatic hydroxycarboxylic acid or a salt thereof with a zirconium compound. This toner for electrostatic-image development has improved unsusceptibility to hot offset during fixing and mitigates winding on the fixing device. The toner has a satisfactory increase in charge amount and gives high-grade images having a high density and reduced in fogging even in a high-temperature high-humidity atmosphere. When the toner is a color toner, a bright color is obtained.

Description

Description Name of Invention Static ¾ ^ Toner for image development and production thereof; ^ Method Technical Field

The present invention relates to a static image developing toner and a method for producing the same. More specifically, the present invention improves the hot offset resistance at the time of fixing, improves the sticking property, has a good charge rise, high density, and low capri. In addition, the present invention relates to a toner for developing a static image having excellent characteristics such as a clear color even with a strong toner and a method thereof. Background

In the ^ method using electrophotography ^, the photoreceptor is uniformly charged, and then the photoreceptor is exposed to dissipate the m # of the exposed portion, thereby forming a static flaw, and the static image. The toner is made visible by developing toner and developed, the visualized image is transferred onto a material such as paper, and the transferred image is fixed by means such as heating. Such toner used for; ^ is called static S ^ image fine toner.

By the way, in a full color image forming apparatus of t¾, there are many difficulties in having an intermediate transfer member, and the transfer performance of the toner becomes important. Therefore, in the case of conventional particles such as 碎 toner, the ridge between the photosensitive member and the intermediate transfer member has a large area, and the toner adhesion is large, which is disadvantageous in terms of transfer ft. . Further, the toner adhesion becomes large even on the developing roller, so that the charge amount becomes non-uniform, and ¾ IE image S force S may not be obtained or white fog S may occur.

On the other hand, fixing is performed in a fixed position where heat fixing is performed between two rollers: ^ When the hot offset is formed, the paper is stuck to the fixing roller ^^ when forming a high-color full-color image. Ba Indah resin having a certain level of viscoelasticity in order with regularly to avoid and ^J H "Rere. This generation is obtained.

In addition, in the process of calorific treatment, the higher the viscoelasticity of the binder resin, the harder the toner is to be thermally deformed, and the m¾D heat rises, and the occurrence of force pulling between the toners increases. There is a problem that the processing cost rises without raising. In this way, with static toners, it is possible to achieve both good anti-hot offset resistance and high stability and productivity such as processing a * during processing! .

Patent Document 1 discloses a means for spheroidizing toner by calorimetry as the last step to improve image quality such as transferability, image density and suppression of capri. In this method, it is possible to obtain good development and transfer by making the toner spherical by reason, such as hot offset and fixed scratches, etc. Fixing failure may occur.

Patent Document 2 discloses, as m¾u crane ij, an electrophotographic toner containing an aromatic oxycarboxylic acid or a salt thereof, a compound containing zirconium and a zirconium compound obtained by force. . Although this toner has the effect of suppressing the deterioration of the band even under high temperature and high humidity and suppressing fogging, the toner with high circularity: tj ^ has poor transferability and the desired image density. S There was a problem that it was difficult to obtain.

[Reference 1] Japanese Patent Laid-Open No. 2 0 0 7-1 9 9 5 7 9

[TF Reference 2] WO 9 9/1 2 9 4 No. 1 "Refletion of Invention

[Invention S

Under such circumstances, the present invention improves the hot offset resistance during fixing, improves the constant wrapping property, has a good rise in charge amount, a high concentration, and even under high temperature and high humidity. A high quality image with little capri is obtained, and a clear color is also obtained with color toners, and so on. It is for the purpose.

Means for solving C]

The inventors of the present invention have made arbitrary efforts to achieve the purpose of selfishness, and as a result, they have become a product of Ninder Indore oil and aromatic hydroxycarboxylic acid ¾Χ with its salt and zirconium-containing compounds. Including toner particles obtained by applying a bridge treatment in a floating state so that the average circularity is in a specific range, and a crane containing at least Based on this finding, he found out that his purpose was to humiliate him and led the present invention. That is, the present invention

[1] A powder containing a binder resin, m ^ lj crane IJ, and a colorant. It contains toner insulators obtained by spheronizing so that the average circularity becomes 0.93 0 to 0 · 9 8 0 by Tachibana treatment, and the reading agent is an aromatic hydroxycarboxylic acid or Seiken Imagine Toner, which has a salt that it contains at least the salt and zirconium-containing material

[2] Noku Inter, 'Silver image presenting toner according to item [1], wherein one resin is a polyester resin,

[3] The static image present toner according to item [2], wherein the polyester resin has an acid value of 2 to 25 mg KOHZ g.

[4] The flow-softening of the polyester resin ^ gT _1/2 is 1 00 to: 1 50 ° C. The static image presently fine toner according to the above [2] or [3],

[5] The above-mentioned [1] to [4] items in which the salt of sucrose hydroxycarbon ^ X is salicino ^ or a salt thereof;

[6] The powder containing the binder resin, crane, and agent is sphere-opened so that the average circularity becomes 0.93 0 to 0.98 0 by the calorie bridge treatment in the floating state. And the step of preparing a toner particle, and as a force squeeze IJ, the above-mentioned hydroxycarboxyl X is used as a glue paste to use at least the product of its salt and zirconium-containing product. [1] to [5], the manufacturing male of the toner for developing a still image according to any one of

This is what you do.

[The invention's effect]

According to the present invention, the resistance to hot offset during fixing is improved, the sticking property is improved, the rising amount of charge is high, the density is high, and the amount of fog is low even under high temperature and high humidity. It is possible to obtain a static image developing toner having excellent characteristics such as that a crisp image can be obtained and a clear color strength S can be obtained even in a color toner, and the production thereof. BEST MODE FOR CARRYING OUT THE INVENTION

The static image present toner according to the present invention (hereinafter sometimes simply referred to as toner) is composed of a kneading resin, a ¾¾ IJ crane IJ, and a glaze containing material, and a carotrophic bridge treatment in a floating state. The toner obtained by spheroidizing so that the average degree of circularity becomes 0.93 0 -0.98 0 containing a magnetic element, the strength of the tflt self ¾¾¾J agent is an aromatic hydroxycarboxylic acid Or it should be a tree that contains at least the salt and its zirconium-containing product. [Toner eggplant]

The static image actual fine toner of the present invention contains a kinder resin, ¾ ^ crane IJ, and a toner stand that contains a difficult agent as an essential component.

(Binder-resin)

The binder resin used in the present invention is not particularly limited, and examples thereof include polyester resins, polyamide resins, polyurethane resin, acrylic resins, polyethylene resins, polyolefin resins such as polyethylene, and polypropylene, and ethylene mono-no-replenene copolymers. Cyclic olefin copolymer, Gen resin, Silicone resin, Ketone resin, Maleic acid resin, Coumarone resin, Phenol resin, Epoxy resin, Terpene resin, Petroleum resin, Polystyrene, Styrene monobutadiene copolymer, Styrene one Mention may be made of styrene resins such as maleic acid copolymers, styrene mono (meth) acrylo-ester copolymers, poly (meth) atari / butyl, polyvinyl petital, and the like. Among these, polyester resin can be preferably used. Examples of polyester resins include condensation polyesters of aromatic dicarboxylic acids and alkylene etherified bisphenol A.

This polyester resin preferably has a gravimetric range of 2 to 25 mg KºHZg. When this surface is in the range of ¾δ above, the aromatic hydroxycarboxylic acid used as ¾¾U crane U, which will be described later, is well-suited to the binder resin of the product of its salt and zirconium-containing resin), and dispersibility is good. It is excellent in that the S ^ product is prevented from falling off from the toner insulator, and it is possible to obtain uniform charge and durable stability of charge. If the wrinkle exceeds 25 mg KOHZ g, there is a possibility that the band qualitative characteristics under high humidity may be lowered. More preferred les, cocoons range from 2 to: 15 mg KOHZg. In the present invention, the acid value of the polyesterol shelf is obtained by dissolving the funnel with benzyl alcohol in a nitrogen atmosphere and titrating with sodium hydroxide in benzyl alcohol.

Further, the flow softening fi¾T _1/2 of the polyester-based resin is preferably in the range of 100 ° to: 1550 ° C. The flow in one softening is less than 1 0 0 ° C, occurs hot offset Ya constant winding force ^J H "Ku, whereas when it exceeds 1 5 0 ° C, to rise ^^ when spherical Lee ^ L sense, sexual And a poor fixing force S may occur. Self-flow softening ¾Τ1 _/ 2 is more preferably in the range of 120 ° to 140 ° C.

In the present invention, the flow softening _1/2 is a value measured as follows. Measurement of flow softening Z2> Use a capillary rheometer specified in JISK 7 19 9 with a cylinder inner diameter of 1 1.3 3 9 mm, an inner diameter of a capillary die of 1 mm, and a length of 1 mm. and, a load 9 8 N on the piston, at 5 ° C / min from 5 0 ° C? to显, from when the one-half of the male resinous flows out, full opening one softening T _{l / 2} t. Shelf Zirconization>

In the present invention, ¾ ^ IJ crane IJ may be an abbreviation (hereinafter referred to as organic zirconium conversion!) Of an aromatic hydroxycarboxylic acid or a salt thereof and a zirconium-containing compound). ) Must be used at least.

膽 ¾ $ ι [By using this organozirconium compound as a class, it is possible to use a rusting resin, a class and a bulking agent. Addition of polyester resin, which is suitable for use as a binder resin, with carboxylic acid, resulting in toner tension s thickening, resistance to hot offset during fixing and resistance to scratching on heat rollers Improves. The effect of the carousel bridge can be determined by measuring the binder HF resin and the spherical toner i after toner treatment or the THF insoluble fraction increment of the toner carrier. The offset resistance at the time of fixing is preferably 2.0 or more, more preferably 3.0 or more, from the parent to improve the adhesion to the heat roller.

In the present invention, the content of Zirconium ^^ in the toner insulator is 0.1 to 3.0% *% from the standpoint of balance between the lift self-effect and ¾¾1 preferably in the range of, 0.2 - 2. more preferably in the range of 0 mass ^_0/0, more preferably the range of 0.3 to 1.0 mass ^_0/0 Rere. For example, aromatic hydroxycarboxylic acid or a salt thereof used as one of the raw materials for zircination is, for example, the following (1):

(In the formula, Ar represents an aromatic group which may have a substituent, M represents a hydrogen atom or an alkali metal, and R represents an alkyl group having from! To 3 carbon atoms.)

Can be given by In (1), the aromatic group which may have a substituent represented by Ar is, as an elementary group, an optionally substituted benzene mono-1,2-dinole S¾. Naphthalene-1,3-diyl group, etc. can be mentioned. In addition, the substituent includes, for example, a cage-like, a-like, or a cyclic alkyl or alkenyl group having 6 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, Examples include halogen atoms, 7 acid groups, and carboxyl groups, and one or more of these may be introduced on the aromatic ring. .

Examples of the alkyl group include sodium and potassium, and are represented by R:! To 3 alkyl groups include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. be able to.

Specific examples of the aromatic hydroxycanolevonic acid represented by 1) and its salts include salicylic acid, 3,5-di-t-butylsalicylic acid, 5-methoxysalitino, 2-hydroxy 3-naphtho Acid, 3,5-disopropoxysalitin, 3,5-di-butyltinole 2 -methoxy, ^ benzoic acid, 6-butinoleol 2-hydroxyl 3-naphthoic acid, 3-tert-butinole-2-methoxy 5-Metinobenzoic acid, 3,5-dichlorosalitino! ^ ¾ and their sodium and strength salts.

In the present invention, among these, salicino can preferably mention its sodium salt or strength salt. On the other hand, Fijf As his own aromatic hydroxycarboxylic acid or free zirconium I spoon for its salt ^, for example _{Z r OC 1 2, Z r} OF 2, Z r OB r Okishiharogen zirconium, such as ₂ or Z r, ( Te-alkoxyzirconium such as i-Pro) ₄ (i-Pro = isopropoxy ¾) can be used.

Zirconium-containing zirconium ¾Hydroxycarboxylic acid or its salt 1 monole, 45 moles of zirconium atoms are introduced.

OH L I I

L— Zr— 0— Zr— L

I I

O O---(2)

L-Zr— O -Zr— L

I I

OH OH

(In the formula, L is the hydrogen atom of the carboxyl group in aromatic hydroxycarboxylic acid removed. Indicates residue. )

The organic zirconium compound represented by these is obtained.

Ingredients, τΚ, ft below alkali oxide in τΚ medium! ¾Hydroxycanolebonic acid and chemistry * ^ From the target amount ¾ ^{: After} ¾1¾ zirconium halide is kept at 40-60 ° C key for an appropriate time, filter, wash and treat Thus, the shelf zirconiumization represented by (1) can be obtained. On the other hand, in order to use selfish tetraalkoxyzirconium as a zirconium-containing element, aromatic hydrocarbon levone must have 1 to 4 moles of zirconium atoms introduced per mole of its salt. «(3)

| _

L-Zr- L…)

I

(In the formula, L is the same as tijf self.)

The organic zirconium compound strength S expressed by

In an appropriate organic material such as toluene, the aromatic hydroxycarboxylic acid and the tetrahydroreoxyxidylcolium of fil J are more An organic zirconium compound represented by the above-mentioned Ippune-wipe (3) can be obtained by allowing the material to be filtered for a suitable period of time at ° C m¾ and then »,".

Ku other wisteria]〉

In the present invention, other ®¾f control crane IJ that can be used in combination with fit's own shelf zirconization ^ is, for example, monoazo aphrodisiac acetylacetone ^ «formation ^), melamine hydroxycarboxylic acid, etc. Metallic salicino! Examples of compounds include boron compounds, boron compounds, and calixarene.

By adding such toner to the toner, the charging characteristics of the toner for developing a static image can be stabilized and the occurrence of capri can be prevented.

According to the present invention, as ¾¾0 crane IJ, を ίΙ 己 organic dinoconium can be used in combination with 1 ¾ ^ or 2S¾. The above may be used in combination with one or more other pills.

The amount of the «¾IJ crane IJ depends on the cocoon, but the above-mentioned knucker, one resin 100 parts by mass From the viewpoint of stabilizing the charging characteristics of the toner and preventing the occurrence of capri, it is usually 0.2 to

3. onmm, preferably o. 5 to 2. o parts by mass. The agent used in the present invention is not particularly limited. Various organic pigments and dyes can be used. Examples of black materials include carbon black, acid, quaternary, manganese dioxide, and aniline black. Examples of yellowing materials include: Ha ^0- Manent Yellow, Chrome Yellow, Quinoline Yellow, Benzine Yellow, Yellow Acid Salt Iron, CI Pigment 'Yellow 97, C.I. Pigment' Yellow 17, C. I. Pigment 'Yello 1 80, C. I. Sonorevent' Yello 1 6 2 and the like. Examples of red pigments include Bengala, Lake Red, Rhodamine 6 B, Quinacridone, Carmine 6 B, C.I. Pigment 'Red 48: 1, C.I. Pigment' Led 1 2 2, C. I. Pigment 'Red 5 7: 1, C.I. Pigment' Red 1 8 4 can be listed. Blue feffi charges include, for example, bitumen and Konoruto Puno! ^, Phthalocyanine puno ~, anilymbuno ^ ", C.I. pigment pu, ~ 15: 1, C.I. pigment bull 1 15: 3, etc. In the present invention, a static image The content of the agent in the developing toner is preferably from! To 20% by mass, more preferably from 2 to 8% by mass, and the content of the colorant is less than 1% by mass. If the content of satiety agent exceeds 20% by mass, the toner fixing 14 may decrease (optional component).

The toner insulator according to the present invention may contain wax, silica powder and the like in addition to the binder resin and crane sucking agent described above.

<Wax>

In the present invention, the wax used for the toner carrier is used for the purpose of improving the reversibility at the time of heat roll fixing. Examples of such a wax include plant waxes such as carnauba wax and rice wax, Oil wax such as paraffin wax, microcrystalline wax, mineral wax such as montan wax, canderia wax, carbowax, polyethylene wax, polypropylene wax, ethylene-propylene copolymer wax, ^ naphthalene wax Synthetic waxes, stearic acid, arachidic acid, behenic acid and other high-fine fatty acids, seryl alcohol, melicyl alcohol, and other high-grade alcohols, stearic acid amide, behenic acid amide-based wax, fatty acid ester Examples include steal, alcohol esters such as glycerol monostearate and glycerol distearate, and silicone varnish. One of these waxes can be used alone, or two or more of these waxes can be used in combination.

The melting point of this wax is preferably 50 to 160 ° C, more preferably 60 to 150 ° C. If the melting point of the wax is less than 50 ° C, the storage stability of the toner may be deteriorated. If the melting point of the wax exceeds 150 ° C, the low adhesion of the toner may be insufficient. There is. The “Tassus” can be obtained as an endothermic peak when the temperature is 10 ° CZ by using the display (DSC).

In the present invention, the content of the wax in the toner辦立child is preferably 0.5 to 5 mass ^_0/0,:! More preferably, it is 3 mass%. If the wax content is less than 0.5 mass%, the low-temperature fixing of the toner may be insufficient. If the wax content exceeds 5% by mass, particles will be deposited in the manufacturing process, and the “x” component will ooze out on the surface of the toner, especially during sphere formation. In addition, the toner's property may be reduced.

By adding silica powder to the toner fine particles, the wax having a low affinity with the non-resin resin is adsorbed on the sill-force particles, and is uniformly dispersed in the binder resin, to the surface of the toner particles. Suppression is suppressed. As a result, the size of the powdered toner particles is improved, and adhesion and accumulation in the s ^ are prevented.

The average primary particle size of the silli force powder used in the present invention is preferably 0.05 to 0.02 / zm, and preferably 0.00 to 0.01 6 μπι. More preferred.

The silica powder is not particularly limited, and examples thereof include dry method silica, wet i¾fc descending silica, and wet genore method silica. In addition, it is also possible to use a silica-based silica having a silanol group, a trimethylsilanol-modified silanol group, or a silica treated hydrophobically with silicone oil. Among them, ¾7 silica is particularly suitable because it has a large affinity for the binder tree.

The content of silica powder in the toner fine particles is usually from 0.25 to 5%. When the content of the fine silica powder is less than 0.2 5 mass ^_0/0, there is a risk that the wax Ru adsorption ¾ T effect is not sufficiently exhibited. If the content of silica powder exceeds 5% by mass, toner fixing 14 is inhibited, and color toner may reduce the transparency of the toner. As the material of U Ryukyu aqueous silicic power powder as U, it is produced from dry silica powder, which is made of halogenated silane such as silicon tetrachloride by vapor phase oxidation, and called fumed silica, and water glass. The so-called wet squeeze powder misalignment can also be used, but there are few silanol groups on the surface and inside, and there are few production residues such as Na ₂ O, S 0 ₃ —! Powder is preferred.

Examples of treatments used to hydrophobize the silica powder include silicone varnish, various modified silicone varnishes, silicone oils, various modified silicone oils, silazaneized ^, and cyclic dimethylsiloxa silane coupling agents. it can. Of these, silicone oil, silazane compound, cyclic dimethylolene siloxane, and silane coupling agent are preferable.

Examples of silicone oils include dimethyl silicone oil, methylphenyl silicone oil, α-methylolene styrene modified silicone resin, and fluorine modified silicone oil. Examples of silazane compounds include cyclic hexamethyldisilazane. Examples of dimethylsiloxane include hexamethylcyclotricyclohexane, octamethylcyclotetracyclohexane, decamethinorecyclopentasiloxane, and the like. Examples of the silane coupling agent include vinylenotrimethoxysilane, biertriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methylenotriethoxysilane, isop'tinotritrimethoxysilane, dimethinoresimethoxy. Examples include silane, dimethyl / letetoxy silane, trimethino methoxy silane, hydroxypropyl trimethoxy silane, phenyl trimethy silane, η-hexadecyl trimethoxy silane, and η-octadecyl trimethoxy silane.

(Translation of Toko Naoko

In the present invention, the toner can be formed by the following method. First, Noku-inter, 'One machine, crane; melt and knead wax and silica powder if desired. There are no particular restrictions on this method. For example, these materials are mixed in advance using a ribo-mixer, double-circular mixer, high-speed mixer, circular β-screw mixer, etc. Two lte¾ffi machines can be used.

The molten kneaded product is pulverized after cooling. Examples of the powder pestle used include impact stones, hammer mark lashers and other types of stone pestle, rod minoles, ball mills, etc. For example, a jet-type pestle that uses a compressed air source such as a blow-type sarcophagus or a counter jet mill can be used. The powdered particles are preferably classified to remove coarse particles and fine particles to form a narrow distribution toner particle. However, there is no particular limitation, for example, it can be classified using an airflow type ^ β device.

In the present invention, the particles are expanded by adding powder in which the distribution has been narrowed by 立 and using the toner particles in a floating state. In the case of calorie processing, the silica powder, and preferably silica powder, is preferably used as a fluidizing agent in advance to improve the spheroidizing process. The addition amount of the external addition force is preferably 0.1 to 8 parts by mass, more preferably 0.5 to 6 parts by mass with respect to 1 part by mass of the toner insulator. As a means for adding the toner insulator, for example, a bed tank or a thermoforming device that disperses the toner in a hot air flow and melts the surface to open the ball is used. be able to. The average circularity of the toner insulator is set in the range of 0.930 to 0.980 by heat treatment.

If the average circularity is less than 0.930, the transferability of the toner is reduced, or the cap is generated by being tapped without being sufficiently charged on the developing roller. On the other hand, when the average circularity exceeds 0.998, it may be difficult to remove the toner particles adhering to the photosensitive member or the intermediate transfer member by the cleaning blade. A preferable average circularity is 0.94 5 to 0.97 70. Note that in the present invention, the average circularity of the spherical toner is the same as that of a particle having an equivalent circular diameter of 3 μm or more (for example, “FPI A_ manufactured by Sysmetas Corporation”). 2 1 0 0 ”], and is defined as follows.

Circularity = (circumference of a circle having the same fineness as the shadow area of the particle), (contour length of the particle chart) As described above, it is used as a ¾¾¾IJ agent. Organic Zirconium ^) and a carboxylic acid with a polyester shelf suitable for use as a binder resin are formed, and the resulting toner insulator is cured and resistant to fixing. Hot offset improves wrapping resistance to heat rollers.

(Shinran Elephant Toner Fine

The toner particles as described above can be used as a static image developing toner as they are. However, from the desired point of view, as shown below, IJ is further added to the job IJ. A toner for developing a work image can be obtained.

In other words, the toner spheroidized into a spherical shape by the addition of -m, The toner for static image development is sickened by exciting fine particles of oxide such as titanium oxide or fine fine particles such as polymethyl methacrylate. These outermost IJs are added to improve the charging characteristics and fluidity of the toner. At first, the amount of calories added by lj is 0.:! To 6 parts by mass with respect to 100 parts by mass of toner particles, and preferably 0.3 to 5 parts by mass. .

According to the present invention, the powder containing the kinder inner fat, the thoracic agent, and the agent is opened to a mean circularity of 0.930 to 0.980 by a color treatment in a floating state. A process for preparing toner particles, and as a powerful IJ Crane IJ, the aromatic hydroxycanolebon ^ X uses at least the product of its salt and a zirconium-containing product. The process of producing the above-described static image present toner of the present invention is also considered. Example

Next, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.

Various properties of the glue were determined according to the following methods.

(1) Sphere 匕 Toner Average circularity of Tachiko

Description »The average circularity of particles having a circle-equivalent diameter of 3 μπι or more was determined according to the method described in ¾ E«, using a flow separation apparatus [manufactured by Sysmex Corporation, “FPIA-2100”].

(2) Flow softening ^ T _1/2

Measured according to the rest of the specification book tf.

(3) Polyester nore shelf

We crushed the waile and sieving at 2 mm, and took 0.2000 ± 0.0002 g of polyester resin ^ S in a 100 ml branched Erlenmeyer flask and flattened it. Add Benzyl Alconole 1 Oml with a dispenser, attach a cooling pipe while flowing nitrogen gas with a rubber hose, set it in the hole of a dry block bath (225 ° C), and cover with a lid. After melting for 12 minutes, the triangular flask was removed from the drive lock bath, the lid was removed, and the mixture was allowed to cool for about 6 minutes. Next, while flowing a small amount of nitrogen gas from the Erlenmeyer flask, benzyl alcoholone 1 Om 1 and chlorohonolem 20 m 1 were applied with a dispenser while flowing through the inner wall of the Erlenmeyer flask with a whole pipette. Carry 8 drops of Crezonoleret as an indicator and stir with a wheel: 1 / 5 ON sodium hydroxide was titrated at night. The end point of the titration was the point at which the color of Neto changed from yellow to purple and lasted for about 15 seconds, and was calculated using the following formula. The value was rounded off to the first place / J¾ ^.

(A-B) X f X 20 56.11

薩 (KOHmg / kg) = X

W 1000

A: 1/50 NzK sodium oxide titration (πι 1)

B: Titration volume of blank (m 1) (Titration when the subsequent operation is performed without dissolving / cooling the polyester resin in the above operation *)

f: 1/50 N sodium hydroxide

W: Weight of the weighed polyester resin sample (g)

* Titer was determined as follows.

Special grade oxalic acid 0.2000 g! ^ Flatten, dissolve in AL and special grade methanol in a 50 ml volumetric flask, and align the mark .: Collect 5 ml of it into a 100 ml conical beaker, and use it as a medicine to force 5 drops of cresol red. Titrate with a 1 Z 50 N aqueous solution of sodium hydroxide in the same manner as above using a ferrule while stirring with a diluter, and titrate three times.

W X 5000

Titer =

63.03 X A '

In the above formula,

W: Weight of grated oxalic acid (g)

A ': 1/50 Ντ Sodium oxide 滴 titration (m 1)

(4) THF insoluble matter in binder resin or toner fine particle

Tetrahydrofuran (THF) insoluble content of the toner binder resin was measured as follows.

Cylindrical glass filter with an inner diameter of 3.5 cm “1 GP 100” Tanashin ^ t $ ¾, “Selite 545” [Kididized ± ¾] 2 gA L, Celite 545 layer height force S variation The glass filter was lightly struck against the cork base until it disappeared. This operation was repeated four times, and the Celite 545 was shaped into the glass filter so that the height of the Celite 545 layer was 2 cm from one side of the filter. The glass filter in which Celite 545 was clarified was dried at 105 ° C. for 3 hours or more and weighed (Yg). Next, as About 0.5 g of mother particles were placed in an Erlenmeyer flask and weighed precisely (Xg), and then 50 mL of THF was added and heated in a 70 ° C water bath for 3 hours to dissolve the sample. This midnight was put into a glass filter ii ^^ g containing the above Celite 545 and suction filtered. A glass filter ii ^ containing THF-insoluble matter was allowed to incubate at 80 ° C for 3 hours or longer, weighed (Zg), and THF-insoluble matter was calculated according to the following formula.

THF content = [(Z-Y) / X] 100 (mass%)

This THF-insoluble matter is a measure of the amount of cross-linked components in the polyester resin. The increment of THF-insoluble matter can be calculated by subtracting the value of THF-insoluble matter obtained from the polyester resin as the raw material from the value of the THF content obtained for Tona ¾ * -Ritsuko.

(5) Fixed student

After sticking the cellophane adhesive tape on the solid printing surface, peel it off, measure the image density after peeling, using a Macbeth densitometer [Macbeth Co., Ltd.]

Fixability = (Tape peeling density, Tape peeling density) X 100 (%)

0: 93.0% or more

△: 90 ・ 0% or more, less than 93.0%

X: Less than 90.0%

(6) Definitely ^ stickiness

The following criteria were used to describe the stability of the paper.

Y: Good

Δ: No practical problem

X: Bad

(7) Capri in high temperature and high humidity (30 ° C / 80% RH)

Visually, f fffi was evaluated with the following.

Y: Good

No problem in practical use

X: Bad

Example 1

Polyester resin (noodles: 6. OmgKOH / g, flow softening _{& ¾Τ 1/2: 130. (:,} T HF insoluble matter 1.5 wt ^_0/0) 91.00 parts by weight of carbon black [Cabot Japan Society ¾ Product name “Black Pe arls L”] 5.00 parts by mass, Salicy Λ Zirconium! ¾U agent [Hodogegakigaku Kogyo Co., Ltd., trade name “TN105”] 0.75 parts by mass, Salicy type [Orient Kagaku Kogyo Co., Ltd., trade name “BONTRON E-304”] 1.00 Parts by mass, «^ Re-Rice Wax [manufactured by Borso Oil Tsuki Co., Ltd.,“ LAX_N—300A ”, DSC endothermic peak: 80 ° C] and 1.00 parts by mass [manufactured by Sanyo Engineering Co., Ltd. 110 TS "] 2.00 parts by mass of melt-mixed kneaded mixture with a twin screw extruder at a temperature of 150. After C), the mixture was crushed with a jet and a cocoon to a mean value of 7.5 / m, and the coarse powder and fine powder were classified with difficulty to obtain a ton * with a sharp ¾¾¾ distribution.

After adding 3.0 parts by weight of hydrophobic silica (Nippon Jiaguchi Jil Co., Ltd., trade name “RX 1 50”) to 100 parts by weight of this toner, the mixture is mixed using a Henschel mixer, ^ Oki [Nippon Pneumatic Kogyo Co., Ltd., “SFS-3 type”] is used, fSag305 ° C, feed amount is 5.0 k _{§ /} / 11, and the average circularity is 0.962. The toner of the spoiled toner “Tachiko” was obtained.

The resulting sphere 匕 toner Tachiko was removed from the butterfly [Nippon Kogyo Co., Ltd., “Elbow Jet EJ—PUROJ”, and the coupling particles were removed to remove {-^ ^ 7.8μm Got Toner Reiko.

To 100 parts by mass of the classified toner particles, 0.5 part by mass of hydrophobic silica [manufactured by CB Corporation, trade name “CAB-O-SIL TS-530”] and strontium titanate (B

Nitrogen adsorption specific surface area by ET method: 1.85m ² / g) After adding 1.0 part by mass and packing with a Henschel mixer, it is equipped with a 200 mesh mesh screen. Toner was produced. The flow softening temperature T _1/2 of this toner is 132.

6 ° C, THF insoluble matter 6.1 Quality 4 percent, is now calculated THF-insoluble matter increment was 4.6 mass ^_0/0.

Using this toner, marking was carried out as follows, and the stickiness, high-temperature and high-humidity (30 ° C / 80% RH), and the fixing I life were evaluated.

Gu seal ^^>

Using a commercially available color laser printer equipped with a one-component development system, a black cartridge was filled with the above toner and a 3,000 sheet print test was conducted. In printing, an image pattern with a printing rate of 5% was printed.

Example 2 The toner was removed in the same manner as in Example 1 except that “E 304” manufactured by Orient Chemical Industry Co., Ltd. was used as the toner crane IJ. Manufactured and stamped ^^^. Ball rot! ^ Thermal heat JW¾t is 300 ° C, the feed amount is 5.0 kgZh, and the toner flow softening T _1/2 is 131.4 ° C, THF insoluble content is 6.0 mass ⁰ The increment of THF-insoluble matter is 4.5 mass ⁰ /. Met. Example 3

In the summary of toner toner in Example 1, as ¾¾¾ IJ crane IJ, except that the amount of TN105J was changed to 0.25 parts by mass, the toner was manufactured in the same way as in Example 1, and the mark ^^ The heat JffiJ in the ball-opening treatment was 290 ° C, the feed amount was 5.0 kgZh, and the obtained toner flow softened ^ JtT _1/2 was 130.6 ° C, THF insoluble matter was 4.3 * %, The increment of THF-insoluble matter calculated from this was 2.8% by mass.

Comparative Example 1

Use in Lee ^ M toner «* Ritsuko in Example 1, as a polyester resin, flow軟I匕¾Τ _1/2 ^ ι 57 ° C, Hokusatsu 6.0MgKOH / g, those THF insoluble matter 1.5 wt ^_0/0 A toner was manufactured and stamped in the same manner as in Example 1 except that “TN105” as ¾ $ IJii | ¾IJ was not used.

In addition, in the spherical shape, is 390 ° C, the treatment amount is 2.5 kgZh, and the inertia was not satisfactory. Although the hot offset resistance was good, wax bleeding occurred, and the toner on the charging blade was severely damaged. Further, the flow softening of the obtained toner was _{1 /} 20.2 at 160.2 ° C., the THF insoluble content was 4.0 mass ⁰ , and the increment of THF insoluble content calculated from this was 2.5 mass%.

Comparative Example 2

Te Contact Rere to toner Ritsuko in Example 1, in place of the polyester resin, styrene emissions acrylic resin (flow softening Ding ₂ = 143 ° C, Hokusatsu 5MgKOHZg, THF insoluble matter 2.0 wt ^_0/0) Yore ,, force Next, a toner was manufactured and stamped in the same manner as in Example 1 except that “TN 105” as IJ crane ij was used.

Note that in the ball opener ft ^ L theory, 390 ° C and the throughput was 2.5 kgZh, and the productivity was not satisfactory. Furthermore, flow softening T _1/2 of obtained toner 13 2.8 ° C, THF-insoluble matter is 3.5 mass ^_0/0, was now calculated THF insoluble matter increment 1.5 mass%. Comparative Example 3

Toner in Example 1 “In the case of Tachiko, except that TN 1 0 5J was used as m¾WiP ^, toner was manufactured in the same manner as in Example 1, and the mark ^^ was The theory was 300 ° C and the throughput was 5.1 kgZh, which was sufficient to increase productivity, but a fixed force S was generated on the heat roller. The toner flow softening ΤΓ _1/2 was 1 34 ° C, the THF insoluble content was 3.1 mass ⁰ , and the increment of THF insoluble content calculated from this was 1.6 mass%.

The results of Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table 1.

Table 1

Spheroidizing treatment Toner flow Binder resin

THF HH environment

THF fixer from throughput

Temperature Softening temperature T _1/2 Fixability at insoluble content [Feed amount] Incremental stickiness of insoluble content

(° C) Capri ability

(k g / h) (.c)

Example 1 305 5.0 132.6 6. 1 4. 6 ○ ○ ○ Example 2 300 5.0 131.4 6.0 4.5 ○ ○ ○ Example 3 290 5.2 1 30. 6 4. 3 2.8 Δ ○ ○ Comparative Example 1 390 2. 5 160 2 4.0 2. 5 ○ Δ X Comparative example 2 360 2. 5 132.8 3. 5 1.5 ○ Δ Δ Comparative example 3 300 5. 1 127.0 3. 1 1.6 X ○ ○

From the above results, the average circularity becomes 0.93 0-0.98 due to the force theory in the floating state of the fluid containing nodder resin, ¾¾ glaze agent, and satiety agent. Spheroidizing to prepare a toner insulator, and as a force tilting agent, at least a TN 1 0 5 Si ^ product of an aromatic hydroxycarboxylic acid or a salt thereof and a zirconium-containing compound is used. By using the toner, the toner can be increased to ¾ to satisfy the fixing property without impairing the heat resistance of the heat ball, and high quality with good capriability even under high temperature and high humidity. It can be seen that images can be obtained.

According to the static image present toner of the present invention, the hot offset resistance at the time of fixing is improved, the sticking property is improved, the rising of the charge amount is good, the density is high, the high temperature and the high humidity A high-quality image with little capri can be obtained even underneath, and a clear color can be obtained with color toners.

Claims

Claims Claims ι · Nokuta, 'One shelf effect, crane ij, agent ¾ ^

«Contains toner toner obtained by spheronization so that the average circularity becomes 0.930 to 0.980 by bridge treatment, and the force aversion agent is an aromatic hydroxycarboxylic acid or a salt thereof and a zirconium-containing compound. This is a static image toner that has at least a bandit. [Claim 2] The knowledge of the static toner image according to claim 1, wherein the binder is a polyester resin. [Claim 3] The toner according to claim 2, wherein the polyester resin has 2 to 25 mg KOHZ g. 4. The image expressing toner according to claim ₂ , wherein the flow softening T ₂ of the polyester resin is 100 to 150 ° C. [Claim 5] The salt of a fine image of hydroxycarboxylic acid X is salicino or a salt thereof. Claim 6. The toner inner shelf shelf, «¾IJ crane IJ, and powder powder are expanded to a mean circularity of 0.930 to 0.980 by bridge treatment in the floating state, and the toner The method according to claim 1, further comprising a step of forming an insulator, wherein at least one of a hydroxy hydroxy acid or a salt thereof and a zirconium-containing compound is used as the force IJ ¾t ^ crane IJ. The key to the toner for crab static image development ¾¾.