JPS62299859A - Toner for developing electrostatic image and image forming method using said toner - Google Patents

Abstract

PURPOSE:To obtain a toner which is low in fixing temp. and has good offset resistance and a wide fixable temp. range by using a block copolymer or graft copolymer contg. an amorphous polymer block and crystalline polymer block respectively consisting of polyester in the molecule as a binder resin. CONSTITUTION:This binder is the block copolymer or graft copolymer formed by chemically bonding the amorphous polymer block and crystalline polymer block respectively at ratios at which 40-99wt% and 1-60wt% are obtd. Both the amorphous polymer block and the crystalline polymer block consist of the polyester. The amorphous polymer block contg. 1-50mol% trifunctional or higher multifunctional monomer components is used as the binder. The blocking resistance, offset resistance, fluidity and low temp. fixability are thereby improved and the excellent visible image is formed.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention [Field of Industrial Application] The present invention relates to the development of electrostatic latent images formed in electrophotography, electrostatic printing, electrostatic recording, etc. The present invention relates to an electrostatic image developing toner and an image forming method using the toner.

[Technical background]

For example, in electrophotography, an electrostatic latent image is usually formed by charging and exposing an electrostatic image carrier made of a photoconductive photoreceptor, and then this electrostatic latent image is placed in a binder made of resin with a coloring agent. The resulting toner image is transferred to a support such as transfer paper and fixed to form a visible image.

In order to obtain a visible image as described above, it is necessary to fix the toner image, and conventionally, a heat roller fixing method that has high thermal efficiency and can perform high-speed fixing has been widely adopted.

However, in recent years, efforts have been made to (a) suppress overheating deterioration of compound machines, (b) prevent thermal deterioration of photoreceptors, and (
3) To shorten the uptime and the amount of time required to heat the fixing device to a temperature at which it can be fixed after it has been activated, and (d) to reduce the uptime due to heat being absorbed by the transfer paper. The power consumption of the fuser heater has been reduced in response to requests such as reducing the temperature drop of the heat roller to enable continuous copying multiple times, and (e) increasing thermal safety. There is a strong demand for the fixing process to be carried out at a lower temperature of 4°. Therefore, it is necessary to be able to fix well at low temperatures even in the first stage.

Furthermore, toners can exist stably as a powder without agglomerating under the environmental conditions of use or storage;
In other words, it is necessary to have excellent blocking resistance.
Furthermore, in the thermal V1-ra fixing method, which is preferable as a fixing method, there is an offset phenomenon, that is, a part of the toner constituting the image is transferred to the surface of the heat roller during fixing, and this is transferred again to the transfer paper that is sent next. A phenomenon occurs where the image becomes dirty! 1-
Since the toner is easily erased, it is necessary to provide the toner with the ability to prevent the occurrence of offset phenomenon, that is, offset resistance.

For this reason, in the past, for example,
As disclosed in No. 0-87032, at least one crystalline polymer portion having a melting point of 45 to 150°C is replaced with an amorphous polymer having a glass transition point of 0°C or less as a binder resin constituting the toner. As disclosed in JP-A No. 59-3446, a crystalline block with a melting point of 45 to 90° C. and a binder resin constituting the toner are used. A technique using a thermoplastic polymer containing in the molecule an amorphous block whose glass transition point is at least 10'C higher than the melting point of the crystalline block, and the content of the crystalline block is 70 to 95% by weight. Proposed.

Furthermore, JP-A No. 57-8549 discloses a structure comprising a crystalline trunk polymer part consisting of at least one monomer selected from ethylene, propylene, and vinyl acetate, an unsaturated polyethral trunk combination part, and a vinyl acetate polymer part. A toner containing a graft copolymer consisting of the following is disclosed.

However, the toner disclosed in JP-A-50-87032 has a soft crystalline polymer portion and an amorphous polymer portion that is sticky and soft due to its glass transition point being 0°C or lower. Since the toner is composed of a copolymer in which the toner is chemically bonded, it has the drawback that it causes a blocking phenomenon in a developing device, etc. even when kept at room temperature. Furthermore, due to poor triboelectric charging properties and poor fluidity, developability is poor, and the resulting images are of poor quality with a lot of fog. Furthermore, since the toner is soft, a filming phenomenon occurs in which it adheres to carrier particles and the surface of the photoconductor when it is copied many times, and it also fuses to cleaning members such as a cleaning plate, resulting in fogging of the resulting image. This results in a low-density and unclear image. In addition, due to its softness, it tends to form lumps in the pulverizer when pulverized at room temperature, or it is difficult to pulverize, making it impossible to obtain toner with the desired particle size, resulting in poor production efficiency and high cost. It has the disadvantage that it becomes Furthermore, since this toner has high adhesiveness, an off-cent phenomenon is likely to occur in a hot roller fixing device that does not apply oil.

Furthermore, in the technique disclosed in JP-A No. 59-3446, an amorphous block with a high glass transition point of 100°C or higher is used, so crystalline blocks are used as a method to satisfy meltability at low temperatures. It is necessary to use a large amount of 70 to 95% by weight, so that the properties of a soft crystalline block having plastic deformability at room temperature are reflected in the toner.

That is, since it is soft, it has poor triboelectric charging properties and poor fluidity, resulting in poor developability and images that are foggy and unclear. Furthermore, due to repeated copying, a filming phenomenon occurs in which toner adheres to carrier particles and the surface of the photoconductor, and the triboelectric charging properties become even worse, which may cause the toner to fuse to cleaning members such as cleaning blades. As a result, the image becomes blurry with a lot of fog and low density. Furthermore, in a fixing method that uses heating for a short time, such as a hot roller fixing device that does not apply a large amount of oil, the glass transition point of the amorphous block is as high as 100°C, so the fixing temperature is high, and the crystalline Since the quality block is as large as 70 to 95% by weight, an offset phenomenon is likely to occur.

Furthermore, the toner disclosed in JP-A No. 57-8549 has poor fluidity, which makes it impossible to obtain a developer in which the toner is uniformly dispersed in the carrier, and as a result, the toner does not have sufficient triboelectric chargeability and development P1. As a result, image blurring occurs and the image becomes unclear. Furthermore, when copying is performed many times, the fluidity of the toner is poor, so even if the toner is replenished, the toner is not evenly dispersed in the developer, resulting in an unclear image.

In the past, the reality is that toners that eliminate all of these drawbacks have not been put to practical use.

[Purpose of the invention]

The present invention has been made based on the above circumstances, and its first object is to provide a toner for electrostatic image development that has a low fixing temperature, good offset resistance, and a wide fixable temperature range. It is.

A second object of the present invention is to provide a toner that does not cause the off-set phenomenon even in a hot roller fixing method that does not apply oil.

A third object of the present invention is to provide an I-ner with good blocking resistance of 1:1.

A fourth object of the present invention is to provide a toner that has good fluidity, triboelectric charging stability, and developability, and provides a clear image without fogging.

A fifth object of the present invention is to provide a toner that does not cause filming on carrier particles, the surface of a photoreceptor, or a cleaning member, has good cleaning properties, and can form clear images without fog. It is.

A sixth object of the present invention is to provide a toner that provides images with high image density.

The seventh RJ objective of the present invention is that even after multiple uses, the filming resistance, cleaning performance, uniform dispersion of toner in the developer, and development performance are good, and the image density is high without fogging. An object of the present invention is to provide a toner having excellent durability and capable of forming clear images.

An eighth object of the present invention is to provide an image forming method using the above toner for developing electrostatic images.

As a result of extensive research, the present inventors have found that 40 to 99% by weight of an amorphous polymer block made of polyester containing 1 to 50 mol% of a trifunctional or higher polyfunctional monomer component and a crystalline polymer block made of polyester 1-60% by weight of polymer block
The present inventors have discovered that the above object can be achieved by an electrostatic image developing toner characterized by using a block copolymer or a graft copolymer containing in the molecule as a binder resin, and have completed the present invention. .

In the electrostatic image developing toner of the present invention, (1) a copolymer formed by chemically bonding an amorphous polymer block and a crystalline polymer block in a specific ratio is used as a binder; (2) The above-mentioned amorphous polymer block and crystalline polymer block are both made of polyester, and the above-mentioned amorphous polymer block has a specific proportion of a polyfunctional monomer component. The object of the present invention is achieved when all conditions are met.

In addition, here, "crystalline polymer block-1" means a polymer part that has a melting point, and "amorphous polymer block" means a non-quality polymer part that does not have a melting point. be.

The present invention will be explained in detail below.

In the toner of the present invention, (1) 40 to 99% by weight and 1 to 60% by weight of an amorphous polymer block and a crystalline bone aggregate block, respectively.
(2) the amorphous polymer block and the crystalline polymer block are both made of polyester; The regular polymer block is constructed using a binder containing 1 to 50 mol% of a trifunctional or higher polyfunctional monomer component.

The toner of the present invention that satisfies these conditions has good anti-blocking properties, anti-offset properties, fluidity, and low-temperature fixing properties, and can form excellent visible images.

The amorphous polymer block is a polyester obtained from a carboxylic acid monomer and an alcohol monomer, and at least one of the carboxylic acid and the alcohol used as the monomer is trifunctional or higher. It is necessary that the material be crosslinkable and obtained from a polymerizable composition containing body components.

The proportion of the trifunctional or higher functional monomer component in the polymerizable composition needs to be 1 to 50 mol%, particularly preferably 5 to 40 mol%. Then, the crystalline polymer block is chemically bonded to 40 to 99 weight % of the crosslinked amorphous polymer block at a ratio of 1 to 60 weight %, forming a block copolymer or graft copolymer as a whole. This copolymer is used as a binder.

In this way, by using a crosslinked amorphous polymer block with a crystalline polymer block as a binder, the resulting toner basically has a softening point equal to that of the crystalline polymer block. Since it is determined dominantly by the melting point of the crystalline polymer block, by using a polyester with a low melting point for the crystalline polymer block, the minimum fixing temperature can be lowered, and the amorphous polymer block can be crosslinked. Because of this, large viscoelasticity can be obtained when melted, and as a result, excellent anti-offset properties can be obtained while ensuring low-temperature fixing properties.

The ratio of the amorphous polymer block and crystalline polymer block constituting the copolymer is 40 to 99:1 to 6 by weight.
0, especially 50 to 90:1
It is preferable that it is 0-50. If the proportion of the crystalline polymer block is less than 1% by weight, the effect on low-temperature fixing properties will be small, and if the proportion of the amorphous polymer block is less than 40% by weight, the resulting toner will have poor fluidity, development performance, and fill resistance. (printability, offset resistance, and durability) become important.

The crystalline polymer block constituting the copolymer used as a binder in the present invention is polyester, and its structure is not particularly limited, but polyalkylene polyester is particularly preferred. As a specific example of such a polyalkylene polyester, for example, poly 1
rimethylene oxalate-1, 1zorite; ramethylene oxalate, polyhexamethylene oxalate-1, polyhebutamethylene oxalate L/-1, poly1 rimethylene oxalate, polyethylene succinate, polydecamethylene succinate, polytetramethylene succinate,
Polyhexamethylene azelate, polydecamethylene succinate, polytrimethylene glutarate, polyethylene adipate, polytrimethylene acelate, polytetramethylene adipate, poly-keystone 7-dibe-1-, polydecamethylene acylate P-1-, poly-1-rimethylene bimelate, polytetrame-TL, -ne bimelate, polypentamethylene pimelate, polyhexamethylene azelate, polyethylene adipate, polytrimethylene helate, polytetramethylene Adipate, polyhexamethylene azelate, polytrimethylene acelate, polytetramethylene azelate-1, polyhexamethylene azelate, polyethylene sebacate 1-, polytrimethylene sebacate, polytetramethylene sebacate, poly Hexamethylene azelate, polydecamethylene sebacate, poly-10-hydroxycaprylic acid, poly-
Examples include 6-hydroxycaproic acid, poly-3-hydroxypropionic acid, and others.

When polyalkylene polyesters such as those mentioned above are used as a crystalline polymer block, they are effective in improving the low-temperature fixing properties of toners and can improve their fluidity due to the following reasons. Seem. That is,
Condensation resins such as polyester resins can easily be obtained with low molecular weight, and when melted, they do not cause a slight "wetting" on the support such as transfer paper, compared to vinyl resins such as styrene. This is because sufficient fixing can be performed at a lower temperature than toners containing other resins as binders having the same softening point.

In the above, it is preferable that the crystalline polymer block has a melting point of 50 to 120°C, particularly 55 to 110°C. If the melting point of the crystalline polymer block used is less than 50°C, the resulting toner will have poor blocking resistance, and if it exceeds 120°C, the melt fluidity of the toner at low temperatures will decrease, resulting in poor fixing properties. There is a risk that this may occur.

Here, the melting point of the crystalline polymer Pro-7 means the melting point of the crystalline polymer block in a state where it is not bonded to an amorphous polymer block.

The crystalline polymer block preferably has a number average molecular weight Mn of 1,000 to 20,000 and a weight average molecular weight M- of 2,000 to 100,000.

When the molecular weight is within this range, the offset resistance of the toner and the pulverization efficiency in toner production will be even better.

The amorphous polymer block constituting the copolymer used as a binder in the present invention is polyester, and its structure is not particularly limited, but aromatic polyester is particularly preferred. When such an aromatic polyester is used as an amorphous polymer block, the resulting toner has good triboelectric chargeability and stable chargeability even after repeated use, and is hard. It has good fluidity and durability and can form clear images. This is for the same reason that polyalkylene polyester is preferably used in the crystalline polymer portion. Such an aromatic polyester may be a polyhydric carboxylic acid or a polyhydric alcohol, as long as one of them is an aromatic monomer.

In order to obtain the amorphous polymer block, alcohol monomers and carboxylic acid monomers, at least one of which contains a trifunctional or higher polyfunctional monomer, are used in the proportions within the above range.

In the present invention, examples of alcohol monomers include ethylene glycol, diethylene glycol, l-diethylene glycol, L2-propylene glycol, 1.3
- Diols such as propylene glycol, 1,4-butanediol, neopentyl glycol, 1゜4-butynediol, ■, 4-bis(hydroxymethyl)cyclohexylene, and bisphenol A1 hydrogenation bisphenol A1 polyoxyethylenization Bisphenol A1 includes etherified bisphenol A such as polyoxypropylenated bisphenol A, and other mono-dihydric alcohol monomers.

Examples of carboxylic acid metapods include maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid,
Cyclohexanedicarboxylic acid, succinic acid, adipic acid,
Examples include sebacic acid, malonic acid, anhydrides of these acids, a dimorphic form of a lower aryl ester and lylunic acid, and other monovalent organic acid monomers.

The trifunctional or higher polyfunctional monomer required to make the amorphous polymer ZOLOK crosslinkable may be an alcohol monomer or a carboxylic acid monomer.

Examples of such polyfunctional monomers, such as trivalent or higher polyhydric alcohol monomers, include sorbitol, 1,2.3
．． 6-hexantetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1,2.4-butane 1-liol, 1,2.5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2
, 4-butanetriol, trimethylolethane, trimethylolpropane, I+3,5-trihydroxomethylbenzene, and others.

Examples of trivalent or higher polycarboxylic acid monomers include 1.2.4-benzenetricarboxylic acid, 1.2.5-benzenetricarboxylic acid, 1.2.4-Schiff 1'1 hexanetricarboxylic acid, 2,5.7-naphthalenetricarboxylic acid, 1,2.4-naphthalenetricarboxylic acid, 1.2
．． 4-butanetricarboxylic acid, 1.2.5-hexanetricarboxylic acid, 113-dicarboxy 2-methylcarboxypropene, 1.3-dicarboxy-2-methyl-
2-methylenecarboxypropane, tetra(methylenecarboxy)methane, 1.2,7.8-octante1-
Examples include lacarboxylic acids, embol trimer acids, their acid anhydrides, and others.

The amorphous polymer block has a glass transition point of 50
The temperature is preferably 100°C to 100°C, particularly 50 to 85°C, and when the temperature is lower than 50°C, the resulting toner has poor fluidity, offset resistance, crushability, blocking resistance, filming resistance, and durability. If the temperature exceeds 100° C., the low-temperature fixability of the resulting toner may deteriorate. Here, the glass transition point of the amorphous polymer block means the glass transition point of the amorphous polymer block in a state where it is not bonded to a crystalline polymer block.

The molecular weight of the amorphous polymer block is a number average molecular weight M
n is 500 to 20,000, weight average molecular weight is i,
It is preferably from ooo to 100,000. When the molecular weight is within this range, the toner has better blocking resistance, pulverization efficiency, and low-temperature fixing properties.

The crystalline polymer block and the amorphous polymer block are
They may be compatible or incompatible with each other, but are preferably immiscible. This is because when a crystalline polymer block and an amorphous polymer block that are compatible with each other are used, the crystalline portion and the amorphous portion easily mix with each other, so the glass transition point of the resulting copolymer is This is because a decrease in crystallinity and a decrease in crystallinity occur. When an amorphous polymer block having a low glass transition point is used, the toner tends to be prone to cracking and kinging, and its pulverizability is reduced due to the above-mentioned causes.

Here, "incompatibility" refers to the fact that the chemical structures of the two are the same or similar, or that the two do not have the property of being sufficiently dispersed due to the action of functional groups, and the solubility parameters, for example,
s, p by Fedose's method.

Value (R, F, Fedors, Polys+, En
g, Sci, 1-4. (2) 147 (197
4)) The difference is greater than 0.5.

The copolymer used as a binder in the present invention is a copolymer composed of mutually different block parts as described above, and at least one crystalline polymer block and at least one amorphous polymer block are chemically linked. That's what happens.

Structurally, it may be a block copolymer or a graft copolymer having a block moiety grafted to a side chain in addition to the main chain. Further, the entire molecule may be linear or may have branches.

Among these, block copolymers are particularly preferred.

The molecular weight of the copolymer cannot be determined unconditionally because it varies depending on the composition and ratio of the crystalline polymer block and the amorphous polymer block, as well as other factors, but it is generally determined by its number average molecular weight i1M.
n is 1,000 or more, weight average molecular weight M- is 5,00
It is sufficient that the number average molecular weight Mn is 0 or more, especially when the number average molecular weight Mn is 1
,000-30,000 and weight average molecular weight is 5,
000 to 300,000 is preferable from the viewpoint of offset resistance, durability, and pulverization efficiency, and it is preferable that the copolymer contains chloroform-insoluble matter in a proportion of 3% or more.

The softening point of the copolymer varies depending on the type of polyester used as each block, and is not particularly limited, but is in the range of 50 to 150°C, particularly 50 to 120°C.
Preferably, it is in the range of °C. When the softening point of the copolymer is within this range, the resulting toner will have better offset resistance, filming resistance, and low-temperature fixing properties.

The glass transition point of the copolymer has a correlation with the glass transition point of the amorphous polymer block, and if the crystalline polymer block and the amorphous polymer block are incompatible with each other, the copolymer The glass transition point of the amorphous polymer block is approximately the same as that of the amorphous polymer block, but specifically, it is preferably 50 to 85°C.

In the present invention, the specific copolymer as described above is present in the binder in an amount of at least 10% by weight, preferably 30% by weight.
It is necessary that the content be in the range of 100% by weight.

Examples of other resins used in combination include styrene-acrylic resin, styrene-butadiene resin, polyester resin, and others. Among these, polyester resin is particularly preferred.

The toner of the present invention has a dynamic elastic modulus G' of 70 to 140°C.
2.0X10' to 1.0X10' d in the temperature range of
It is preferable that the dynamic viscosity η' is within the range of yn/cd, and that the dynamic viscosity η' is below lXl0'voices in the temperature range of 70 to 140°C.

The melting point of the crystalline polymer block of the present invention, the glass transition point of the amorphous polymer block, the dynamic elastic modulus G' and the dynamic viscosity η' of the toner of the present invention can be measured as follows. .

Precise penetration To melting of blocks (2) Suri 1 According to differential scanning calorimetry (DSC), for example rDSC-20J (
(manufactured by Seiko Electronics Co., Ltd.), and the measurement conditions are approximately 10 mg of sample at a constant heating rate (10°C/win).
The melting peak value when heated at is defined as the melting point.

According to differential scanning calorimetry (DSC), e.g.
It can be measured by DS (>20J (manufactured by Seiko Electronics Co., Ltd.). Specifically, approximately 10 mg of the sample is heated at a constant temperature increase rate (10°C/+win), and the temperature is measured from the intersection of the baseline and the endothermic peak at 111 m. Obtain the glass transition point.

Toner q dynamic - Dan Oshi rate Dan O-yo p Neken dynamic charcoal 11 hair rate -
For example, it can be measured using the "Shimadzu Rheometer RM-1" (manufactured by Shimadzu Corporation).Specifically, the sample is melted at a certain temperature, and a sinusoidal vibration is applied to the sample in this molten state to cause twisting. The dynamic elastic modulus σ and the dynamic viscosity modulus η are obtained from the amplitude ratio and phase difference.

The softening point of the Kisato Kaneo Soft Decoy Kaq Translucent Copolymer was measured using an elevated flow tester (manufactured by Shimadzu Corporation) under the following conditions: load 20kg, 7cm'';
Nozzle diameter 111111% Nozzle lengthllll11
1 Preheating at 50℃ for 10 minutes, heating rate 6℃/min, sample amount ICll13 (intrinsic specific gravity x ICll1f)
When the weight expressed as f) is measured and recorded, the height of the S-curve in the plunger drop-temperature curve (softening flow curve) of the flow tester is h, and the temperature is measured at h/2.

The values of the weight-average molecular weight M- and the number-average molecular weight Mn can be determined by various methods, and may differ slightly depending on the measurement method. However, in the present invention, it is determined by the following measurement method.

That is, the weight average molecular weight and number average molecular weight Mn are measured by gel permeation chromatography (GPC) under the conditions described below. 1.2 ml of solvent (tetrahydrofuran) per minute at a temperature of 40°C
A sample solution of 3 mg of tetrahydrofuran sample solution having a concentration of 0.2 g/20 d was injected into the sample at a flow rate of 1, and the measurement was performed. When measuring the molecular weight of a sample, select measurement conditions in which the molecular weight of the sample falls within a range where the logarithm of the molecular weight and the count number of the calibration curve prepared using several types of monodispersed polystyrene standard samples are linear. .

The reliability of the measurement results is determined by the N
B5706 polystyrene standard sample has a weight average molecular weight M
w -28,8X 10' number average molecular weight Mn -13,
This can be confirmed by calculating 7X 10'.

Moreover, any column may be used as the GPCO column as long as it satisfies the above conditions. Specifically, for example, TSK-GBL, GMH (manufactured by Toyo Soda Co., Ltd.), etc. can be used.

Note that the solvent and measurement temperature are not limited to the conditions described and may be changed to appropriate conditions.

In order to obtain a copolymer formed by chemically linking the crystalline polymer block and the amorphous polymer block, for example, a coupling reaction between terminal functional groups present in each polymer may be performed in a head-to-tail manner. They can be directly coupled to each other.

Alternatively, the terminal functional groups of each polymer can be bonded by a difunctional coupling agent, such as urethane bonds or terminal groups formed by the reaction of a polymer whose terminal group is hydroxyl with diisocyanate-1. An ester bond formed by the reaction of a polymer whose terminal group is hydroxyl with dicarboxylic acid or a reaction between a polymer whose terminal group is carboxy and a glycol, or a polymer whose terminal group is hydroxyl and phosgene or dichlorodimethylsilane. They can be linked by other bonds formed by reaction.

Specific examples of the campling agent include difunctional isocyanates such as hexamethylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, tolidine diisocyanate, naphdylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate; for example, ethylenediamine, hexamethylenediamine, Difunctional amines such as phenylenediamine; difunctional carboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid; Difunctional acid chlorides such as terephthalic acid chloride, isophthalic acid chloride, adipic acid chloride, sebacic acid chloride; Other bifunctional coupling agents such as oceanates, bisketenes, biscarbodiimides, etc. may be mentioned.

The coupling agent may be used in a proportion of 1 to 10% by weight, preferably 2 to 7% by weight based on the total weight of the crystalline polymer and the amorphous polymer.
The resulting copolymer has an excessively high molecular weight, resulting in a high softening point, resulting in a toner with poor low-temperature fixing properties; Offset resistance, filming resistance, and durability tend to deteriorate.

In the present invention, it is particularly preferable to obtain the copolymer as follows. That is, while a crystalline polymer is synthesized by a conventional method, a polymerizable composition for forming an amorphous polymer is reacted and polymerized to some extent, and the above-mentioned crystalline polymer is added thereto to form an amorphous polymer. A copolymer is synthesized by reacting unreacted groups of a regular polymer and a crystalline polymer. According to such a method, a copolymer with desired characteristics can be produced by monitoring the progress of the reaction by an appropriate method.

The electrostatic image developing toner of the present invention contains a coloring agent in a binder made of the above-mentioned specific copolymer, and if necessary, a magnetic material and a property improver are also added to the resin. May contain.

Examples of the coloring agent include carbon black, nigrosine dye (C, L level 50415B), aniline blue (C, 1, positive 50405), calco oil blue (C,
1,l1hazoic Blue 3), chrome yellow (C,1,1lh14090), ultramarine blue (C,I, Na77103), DuPont oil red (C,1,Pk26105), quinoline yellow (C,1, 4TOO5), Methylene blue chloride (C, I.

52015), phthalocyanine blue (C, l Na
74160), malachite green offsalate (C,
1, positive 42000), lamp black (c, r, magnetic 77)
266), Rose Bengal (C, T, Yang 45435)
), mixtures thereof, etc. can be used. The amount of colorant used is usually 0.1 per 100 parts by weight of toner.
~20 parts by weight, particularly preferably 0.5 to 10 parts by weight.

The magnetic material may be a ferromagnetic metal or alloy such as iron, cobalt, or nickel, including ferrite and magnetite, or a compound containing these elements, or a material that does not contain a ferromagnetic element but can be prepared by subjecting it to appropriate heat treatment. Alloys that become ferromagnetic, such as manganese-w
4-aluminum, a type of alloy called Heusler alloy containing manganese and copper, such as manganese-copper-tin, chromium dioxide, and others. For example, when obtaining a black toner, magnetite, which is black in itself and also functions as a coloring agent, can be particularly preferably used.

Further, when obtaining a color toner, it is preferable to use a material with little darkness, such as metal iron. Some of these magnetic materials also function as a coloring agent, and in that case, they may also serve as a coloring agent. These magnetic substances are uniformly dispersed in the resin in the form of fine powder with an average particle size of 0.1 to 1 μm, for example. In the case of magnetic toner, the content is 20 to 100 parts by weight of toner.
It is 70 parts by weight, preferably 40 to 70 parts by weight.

Improving agents include fixing V1 improvers, charge control agents, and others.

Examples of fixing property improvers include polyolefins, fatty acid metal salts, fatty acid esters and fatty acid ester waxes, partially saponified fatty acid esters, higher fatty acids, higher alcohols, paraffin wax in liquid form or solid form, polyamide waxes, and polyhydric alcohols. Ester, silicone varnish, MFJ aliphatic fluorocarbon, etc. can be used. In particular, the softening point (ring and ball method JIS K2531) is 6.
Wax having a temperature of 0 to 150°C is preferred.

As the charge control agent, conventionally known ones can be used, and examples thereof include nigrosine dyes, metal-containing dyes, and the like.

Further, the toner of the present invention is preferably mixed with inorganic fine particles such as a fluidity improver.

The inorganic fine particles used in the present invention include -
The secondary particle size is 5 my to 2 pm, preferably 51
The particles are μ~500I−. Further, the specific surface area measured by the L3ET method is preferably 20 to 500 m''/g. The proportion mixed in the toner is 0.01 to 5% by weight, preferably 0.01 to 2.0% by weight.

Examples of such inorganic fine powder include fine silica powder,
Alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, gay sand, clay, mica, wollastonite, diatomaceous earth, 1com oxide, cerium oxide, red iron oxide, trioxide Examples include antimony, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride, and fine silica powder is particularly preferred.

The silica fine powder referred to herein is a fine powder having a 5i-0-Si bond, and includes both those produced by a dry method and a wet method. In addition to anhydrous silicon dioxide, aluminum silicate, sodium silicate, potassium silicate,
Any of magnesium silicate, zinc silicate, etc. may be used, but those containing 85% by weight or more of SiO□ are preferred.

Specific examples of these fine silica powders include various commercially available silicas, but those having hydrophobic groups on the surface are preferred;
For example, AERO5IL L-972, l? -974,
Examples include R-805, R-812 (manufactured by Aerosil), Tarasox 500 (manufactured by Talco), and the like.

Other silane coupling agents, titanium coupling agents,
Silica fine powder treated with silicone oil, silicone oil having an amine in its side chain, etc. can be used.

To give an example of a preferred method for producing the toner of the present invention, first, a binder material resin or a toner component such as a colorant is added thereto as necessary is melt-kneaded using, for example, an extruder, and after cooling, a jet A toner having a desired particle size can be obtained by pulverizing the toner using a mill or the like and classifying the powder. Alternatively, a toner having a desired particle size can be obtained by melting and kneading the toner using an extruder and then spraying it in a molten state using a spray dryer or dispersing it in a liquid.

In the image forming method of the present invention, a developer is prepared using the above-mentioned specific toner, and an electrostatic image is formed and developed using a commonly used electrophotographic copying machine, and the resulting toner is The image is electrostatically transferred onto the transfer paper 1- and fixed by a heating roller fixing device whose temperature is set at a constant temperature to form a copy image.

The image forming method of the present invention is particularly preferably used when performing high-speed fixing in which the contact time between the toner on the transfer paper and the heating roller is within 1 second, particularly within 0.5 seconds.

〔Example〕

Examples of the present invention will be described in detail below, but the present invention is not limited to these examples.

Example 1 Irritability (1500 g of sebacic acid and 9 hexamethylene glycol)
64 g, capacity 57 with thermometer, stainless steel stirrer, glass nitrogen inlet tube and 1 J'' flowing condenser! This flask J was then placed in a mantle heater, and nitrogen gas was introduced through a glass nitrogen introduction tube to raise the temperature while maintaining an inert atmosphere inside the reactor. Then, 13.2 g of p-toluenesulfonic acid was added and reacted at a temperature of 150°C. The reaction was stopped when 250% of water was distilled off, and the reaction system was cooled to room temperature to obtain polyhexamethylene sebacate, which is a crystalline polyester. The melting point of this crystalline polyester (value measured with a differential scanning calorimeter rDsc-20J (manufactured by Seiko Electronic Industries, Ltd.; the same applies hereinafter) was 64°C.

498 g of isophthalic acid, 420 g of trimellitic acid,
456 g of propylene glycol was placed in a reaction device similar to that used in Synthesis Example 1, and 1.2 g of dibutyltin oxide was added and reacted at a temperature of 220°C.
An amorphous polyester was produced. The progress of this polymerization reaction was followed by the ring and ball softening point measurement method of the reaction product, and when the softening point reached 110°C, the reaction product was sampled and its glass transition point was measured with a differential calorimeter. The temperature was 60°C.

To this reaction system, 568 g of polyhexamethylene sebacate obtained in Synthesis Example 1 was added, mixed uniformly, and further reacted. When the softening point of the product reached 100°C, the reaction was terminated. was cooled to room temperature to obtain a white copolymer resin. This copolymer resin was a solid that was easily powdered.

Toner 111: 100 parts by weight of the copolymer resin obtained in Synthesis Example 2, 10 parts by weight of carbon black [Mogul LJ (manufactured by Cabot), and polypropylene [Viscol 660].
3 parts by weight of PJ (manufactured by Sanyo Chemical Industries, Ltd.), kneaded with a heating roll, cooled and pulverized, and 100 parts by weight of the obtained colored fine particles were mixed with 3 parts by weight of hydrophobic silica fine powder "Aerosil R172J (manufactured by Aerosil Co., Ltd.)". A toner of the present invention was produced by mixing 0.8 parts by weight of the following products (manufactured by Toner Co., Ltd.) in a type 1 mixer.This is referred to as toner 1.

The composition and characteristics of this toner 1 are as follows.

[Crystalline block]

Polyhexamethylene sebacate Softening point 64℃, s, p, value 10.2 [Amorphous block] Acid component: Isophthalic acid (60 mol%) Trimellitic acid (40 mol%) Alcohol component: Propylene glycol glass transition Point 6
0°C, s, p, 13.0 [Copolymer] Ratio of crystalline polyester and amorphous polyester (C
/Δ): 30/70 Examples 2 to 7 According to the method according to Example 1, except that the crystalline polyester and the amorphous polyester were as follows.
A total of six types of toners of the present invention were manufactured. This is l・ner 2
~ Toner 7.

Toner 2 [Crystalline block] Polyhexamethylene sebacate similar to Toner 1 Softening point 64°C, s, p, value 10.2 [Amorphous block] Acid Components: Isophthalic acid (90 mol%) Trimellitic acid (10 mol%) Alcohol component: Propylene glycol Glass transition point 5
8°C, s, p, value 13.1 [copolymer] C/A:
30/70 Shishi 2 main [crystalline block] Polyhexamethylene sebacate similar to toner 1 Softening point 64°C, s, p, value 10.2 [amorphous block] Acid Component: Isophthalic acid (20 mol %) Trimellitic acid (80 mol%) Alcohol component: Propylene glycol Glass transition point 6
0°C, s, p, value 13.2 [copolymer] C/A:
30/70 Toner 4 [Crystalline block] Polydecamethylene succine obtained in the same manner as Toner 1
1. Softening point 71.5℃, s, p, 4 straight 9.7 [amorphous block] Acid component: Terephthalic acid (40 mol%) Trimellitic acid (60 mol%) Alcohol component: Polyoxypropylene-( 2,2)-
Bis(4-hydroxyphenylpropane glass transition point 6
5°C, s, p, value 15.7 [copolymer] C/A:
10/90 History 2” - [Crystalline block] Polydecamethylene succinate similar to Toner 4
Softening point 71.5°C, S, P, A straight 9.7 [Amorphous block] Acid component: Terephthalic acid (40 mol%) Trimellitic acid (60 mol%) Alcohol component: Polyoxypropylene-(2, 2)-
Bis(4-hydroxyphenylpropane glass transition point 6
5°C, s, p, value 15.7 (copolymer) C/A:
50150 Toner 6 [Crystalline block] Polydecamethylene adipate obtained in the same manner as Toner 1 Softening point 71.5°C, s, p, value 9.7 [Amorphous block] Acid Component: Fumaric acid (60 mol% ) Trimellitic acid (40 mol%) Alcohol component: Polyoxypropylene-(2,2)-
Bis(4-hydroxyphenylpropane glass transition point 6
3℃, s, p, (direct 12.9 [copolymer) C/A
: 20/80 Toner 7 [Crystalline block] Polyethylene sebacate obtained in the same manner as Toner 1 Softening point 72.0°C, s, p, value 10.7 [Amorphous block] Acid Component: Fumaric acid (60 mol%) trimellitic acid (40 mol%) Alcohol component: polyoxypropylene = (2,2)-
Bis(4-hydroxyphenyl di-11 pan glass transition point 63℃, s, p, value 12.9 [copolymer) C/A
: 40/60 Example Day: 100 parts by weight of copolymer resin obtained in the same manner as in Example 1, 60 parts by weight of magnetic material rBL-5004 (manufactured by Titanium Industries, Ltd.), and polypropylene [Viscol 660PJ (manufactured by Sanyo Chemical Industries, Ltd.)]. ) and 3 parts by weight of the charge control agent "Nigrosine SO
A one-component magnetic toner was produced in the same manner as in Example 1, except that 1.5 parts by weight of "1.5 parts by weight" (manufactured by Orient Kagaku Co., Ltd.) was used.

This is referred to as toner 8.

The composition and characteristics of this toner 8 are as follows.

[Crystalline block]

Polyhexamethylene sebacate Softening point 64℃, s, p, value 10.2 [Amorphous block] Acid component: Isophthalic acid alcohol component: Propylene glycol (60 mol%) Pentaerythritol (40 mol%) Glass transition point 56°C, s, p, value 11.9 [copolymer]
C/A: 30/70 Comparative Example 1 Polyhexamethylene sebacate 300 similar to Toner 1
g and 700 g of polypropylene isophthalate obtained in the same manner as in Synthesis Example 1 were placed in a reactor similar to that used in Synthesis Example 1, heated to a temperature of 200 ° C., and 40 g of hexamethylene diisocyanate was added dropwise. After reacting for 30 minutes, the mixture was cooled to room temperature to produce a copolymer. The amorphous polyester of this copolymer is not crosslinked.

A toner was produced in the same manner as in Example 1 except that this copolymer resin was used. This is referred to as comparison toner 1.

The composition and characteristics of this comparative toner 1 are as follows.

[Crystalline block]

Polyhexamethylene sebacate Softening point 64℃, s, p, value 10.2 [Amorphous block] Acid component: Isophthalic acid alcohol component: Propylene glycol Glass transition point 5
4.5℃, s, p, value 11.2 (copolymer) C/A
: 30/70 Comparative Example 2 A toner was produced in the same manner as in Example 4 except that crystalline polyester was not used. This is referred to as comparison toner 2.

Comparative Example 3 A toner was produced in the same manner as in Example 1, except that the ratio (C/A) of crystalline polyester and amorphous polyester in the copolymer was 70/30. This is referred to as comparison toner 3.

The following tests were conducted on each of the above Toners 1 to 8 and Comparative Toners 1 to 3. Zunawara, 1 part of 3 flji of each tree and an average particle size of 1100
A developer was prepared by mixing with 97 parts by weight of a carrier coated with a styrene-methyl methacrylate copolymer resin. Using this developer, an electrophotographic copying machine r U-Bi
x 1600J (manufactured by Konishi Roku Photo Industry '4.1) to form and develop an electrostatic image, and the resulting toner image is transferred onto transfer paper and fixed by a heating roller fixing device to form a copy image. A test was conducted, and the minimum fixing temperature (minimum temperature of the heating roller capable of fixing) and offset occurrence temperature (minimum temperature at which an offset phenomenon occurs) was measured using the method described below, and the possible fixing range was also determined.

Minimum fixing temperature: After creating an unfixed image with the above copying machine, a heated roller with a diameter of 30 mm whose surface layer is made of Teflon (polytetrafluoroethylene manufactured by DuPont) and a heated roller whose surface layer is made of silicone rubber rKE-1300RTVJ (Shin-Etsu Chemical Co., Ltd.) (manufactured by Kogyosha)
A fixing device consisting of a pressure roller formed of 64
The toner image of the sample toner was transferred onto the transfer paper of g/n (linear velocity 70 mm, 7 seconds, linear pressure 0.8 kg/cm)
, the operation of fixing with a nip width of 4.9 mm was repeated at each temperature by raising the set temperature of the heat roller in steps of 5 degrees Celsius within the range of 80 to 240 degrees Celsius. The lowest setting temperature for a fixed image that showed sufficient scratch resistance after rubbing was defined as the lowest fixing temperature.

Note that the fixing device used here has a silicone oil supply mechanism.

Offset generation 7.1 Temperature: The measurement of the offset generation temperature is based on the measurement of the minimum fixing temperature, but after creating an unfixed image with the L copying machine, the toner image is transferred and fixed with the above-mentioned fixing device. After processing, the blank transfer paper is sent to the fixing device under the same conditions and visually observed to see if toner stains occur on it, and the set temperature of the heating roller of the fixing device is sequentially increased. This was repeated in the same state, and the lowest setting temperature at which lη deviation caused by the toner was set as the off-mono one-shot 11 temperature.

Fixable range: The difference between the off-mono 1 shot/1 temperature and the minimum fixing temperature was defined as the fixable range.

The results are shown in Table 1.

One more note!・For each glue, blocking resistance,
Grinding efficiency, filming properties, cleaning properties, charge amount (Q/M), and fluidity of a developer prepared using the toner were measured as follows.

Blocking resistance: Blocking resistance test was conducted at a temperature of 45°C and a relative humidity of 43°C.
% environmental conditions for 2 hours, and whether or not agglomerates were formed was examined.

Grinding efficiency: Judgment was made based on the amount of feed when finely pulverized using a supersonic jet mill under the conditions of a pressure of 5.4 kg/cII 1 g.

Filming property: Filming property was determined by observing the surface of the carrier or photoreceptor and determining the presence or absence of deposits.

Cleanability: Cleanability was determined by observing the surface of the photoreceptor after cleaning it with a cleaning member and determining the presence or absence of deposits.

Fluidity of the developer: The fluidity of the developer was determined by viewing the L1 of the developer in the developing device, and the fluidity of the developer was determined to be good if it was at a practical level.

Charge amount (Q/M): Charge amount is measured per 1 g of toner using a known blow-off method.
This is the value of the amount of triboelectric charge per unit.

The results are also shown in Table 1.

Furthermore, regarding images obtained using each of the above toners,
Fog, maximum image density (D wax), and sharpness were measured and evaluated as follows.

Fog: Indicated by the relative density with respect to the developed image of a white background area with an original density of 0.0. In other words, the white background reflection density is set to 0.0,
Evaluation was made according to the following.

0 Less than 0.01 Δ 0.01 to less than 0.03 x Q, 03 or more Maximum image density (Dmax): Indicated by the relative density of the developed image when the image density of the original image is 1.3. The measurement was performed using a Sakura densitometer (manufactured by Konishiroku Photo Industry Co., Ltd.).

Sharpness: Using line drawing Char 1 of the manuscript as the original norm, its reproducibility was enlarged and visually judged.

The obtained results are also shown in Table 1.

Furthermore, durability tests were conducted using each of the above toners. In other words, after repeating the development process 30,000 times, the amount of charge of the toner (Q/M) and the amount of change in the amount of charge (ΔQ/M)
, fluidity, filming and cleaning properties of the developer, fogging of the obtained image, maximum image density (D l
1ax), and the sharpness was measured and evaluated in the same manner as above. The results are shown in Table 2.

Claims (1)

[Scope of Claims] 1) 40 to 40% of an amorphous polymer block made of polyester containing 1 to 50 mol% of a trifunctional or higher polyfunctional monomer component
Electrostatic image development characterized in that a block copolymer or graft copolymer containing in the molecule 99% by weight and 1 to 60% by weight of a crystalline polymer block made of polyester is used as a binder resin. toner. 2) 40 to 40% of an amorphous polymer block made of polyester containing 1 to 50 mol% of a trifunctional or higher polyfunctional monomer component
A toner for electrostatic image development using a block copolymer or a graft copolymer containing 99% by weight and 1 to 60% by weight of a crystalline polymer block made of polyester as a binder resin can be photosensitive. An image forming method characterized by developing an electrostatic image formed on a body, transferring the formed toner image onto a transfer body, and performing heat roller fixing to form a fixed image.