JPS6388565A - Developer composition - Google Patents

Abstract

PURPOSE:To to improve the environmental stability and stability with lapse of time of the electric charge of a toner and by incorporating a substantially amorphous and colorless transparent high-polymer material contg. a polar functional group formed as a neutralizing salt for an acidic component and basic component and having a specific glass transition temp. or above into the titled compsn. CONSTITUTION:The substantially amorphous and colorless transparent high- polymer material contg. the polar functional group formed as the neutralizing salt for the acidic component (A) and the basic component (B) is used for the developer compsn. essentially consisting of a coloring agent and binder resin. The polar functional group is exemplified by carboxylic acid base, sulfate base, phosphate base, phosphonate base, phenol base and boric acid base. The method of introducing an -AB group into the high-polymer material is exemplified by a method of homopolymerizing a polymerizing monomer contg. the -AB group or copolymerizing the same with acrylate, etc., and a method of producing a monomer, then forming the -AB group. The developer compsn. having the excellent environmental stability of the electric charge of the toner and the excellent stability with lapse of time is thereby obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a developer composition for visualizing electrical latent images and electrical signals in electrophotography, electrostatic recording, etc. The present invention relates to a developer composition with excellent properties.

Conventional technology There are various methods for imparting charge to developer (toner), including friction, contact charging, ion beam charging, electrostatic induction using conductivity, and charge injection. There are, but
The easiest and most widely used method is friction or contact charging.

In order to impart an electric charge to the toner as the instant imaging agent used in this case, gear A and rear particles, which are charged to the opposite polarity to the toner, are used at one time.
~ In addition to the two-component phenomenon agent that is mixed with the toner, it can also be used with the charging blade, charging roll, etc.! One-component developers that utilize electrical charging or frictional charging between toners are known.

When toner is charged by contact charging or frictional charging,
I Henner measurement, or KiX rear, blade, etc.

It is necessary to control chargeability by adding an electron-donating substance or an electron-withdrawing substance to the charge-imparting material.

Triboelectric development is complex and its mechanism is not necessarily clear, but in general, the electron-donating biological substance is positively charged and the electron-withdrawing substance vX is negatively charged.

Conventionally, in order to charge toner iilJm, (i)
In the toner or on the surface of the toner particles, dyes and pigments, surfactants, and non-density powders 8 are added and mixed; (11) halogens such as 1000H1-C\, -0ρ, etc. as a binder resin; ,-No
The method used was to use a resin-like substance containing a functional wood such as NH2.

Problems to be Solved by the Invention However, depending on these means, toner charging i.
Control of raw material temporal stability and environmental stability has not been successful and has not reached a satisfactory level.

Furthermore, there are no known colorless or light-colored charge control agents that are sufficient for use in color applications.

Therefore, an object of the present invention is to provide a developer composition in which toner charge rises quickly, and to provide a developer composition in which the charge distribution of L-toner can be controlled and the charge distribution is sharp. , To provide a developer composition with excellent environmental stability and stability over time of toner charging, and therefore, provide a developer composition with improved developability and transferability and always guarantee good image quality; Another object of the present invention is to provide a developer composition using a colorless or light-colored charge control agent that can be used to form a color image.

The above object of the present invention is to neutralize the acidic component (A) and the basic component (B) in a developer composition containing a colorant and a binder resin as main components. This was achieved by using a substantially amorphous, colorless and transparent polymeric substance that has an external functional group formed as a salt and has a glass transition temperature of 50°C or higher.

In the present invention, the polar functional group includes a carboxylic acid group, a sulfuric acid ester group, a phosphoric acid ester group, a phosphonate group, a phenol group, a boronated group, and the like, and is represented by the general formula AB. Here, A is a monovalent or polyvalent metal cation with 10b, an ammonium ion, an alkyl an[
Indicates quaternary ammonium ions such as nium ions, pyridinium ions, quinolinium ions, and imidazolium ions.

In the present invention, the cationic component in the polar functional group need not be one type, and two or more types of cationic components may be used. Further, a plurality of types of external functional groups may be present in the toner.

Examples of methods for introducing an external functional group represented by the general formula AB (hereinafter referred to as -AB group) into a polymeric substance include the following methods. (1) Acrylic MNa, methacrylic acid\a, vinylbenzoic MNa, vinylphosphophone MN
(2) A method of homopolymerizing or copolymerizing a ferromerizable hexamer containing an -AB group such as a with styrene, acrylic acid varnish, methacrylic acid ester, etc.; (2) acrylic acid, vinylbenzoic acid, terephthalic acid, A polymer is produced by monopolymerizing or copolymerizing a monomer containing an acidic functional group such as mellitic acid or fumaric acid, and then the -A8 group is produced by neutralizing it with, for example, zinc acetate, which becomes the base of the cation. (3) A method in which all or part of the cation of the -AB group in the formed polymer substance is replaced with another cation by an ion exchange reaction to form a new -A8 group. It will be done.

Furthermore, it is also possible to react a substance having a functional group that serves as a base for -AB groups or -A8 groups with another polymeric substance to introduce -AB groups into the polymeric substance, or to introduce a component that serves as a base for cations into the polymeric substance. Inorganic particles having, for example, ~l to 10. ZnO, CaO
etc. may be reacted with a polymeric substance containing a free acidic group.

The concentration of -AB group is -A for toner stone resin loading.
It is preferably about 0.05 mol % to about 10 mol % based on the monomer having the B group.

For example, if the concentration is changed to the free -COOH group concentration, the concentration will be from about 0.25 to about 50 in one acid display. The optimum concentration of -AB male in the toner binder resin varies depending on the usage form of the toner, but in general it is about 0.5 mol% with respect to the toner binder resin Φ71 ．． When the kneading degree is 5 mol %, good charge control property of 13 fl is achieved. =AB
If the base concentration is too low, little charge control effect will be obtained; conversely, if it is excessive, the environmental dependence of the charging characteristics of the 1-ner, such as temperature solubility, will become large, or the conductivity will become extremely high. , and the charge retention ability decreases. In addition, the ionic crosslinking efficiency of -An becomes too strong, and the glass transition temperature and )H melt viscosity increase extremely, resulting in a decrease in the overall content ↑1 of the toner.

In the polymeric substance used in the present invention, the -A8 group may be introduced anywhere, such as at the end of the molecular chain or in the side chain of the parent polymeric substance.

In the present invention, the polymeric substance having an -A8 group may be a homopolymer or a copolymer as described above, but generally,
Since the -AB group is a hydrophilic group, it is more advantageous to use it in a copolymer with another hydrophobic monomer than in a homopolymer.9 In the present invention, the -AB group is The polymer 71 is a substantially amorphous polymer with a glass transition temperature of about 50°C or higher, preferably about 60°C to 90°C. (
1. This is undesirable because toner blocking is likely to be induced and the charge control effect is difficult to exhibit.Also, if the glass transition temperature is too high as 120°C, depending on the additive strength, especially In the case of heat fixing type 1 to toner, it is not preferable because it often has an adverse effect on the fixing properties of the toner.

In the present invention, since the ionic cross-linking effect of the -AB group is not particularly actively utilized, the molecular distribution of the polymer substance containing the -AB group can be arbitrarily selected according to the purpose. In order to effectively exhibit the charge control effect, G
The number average molecule ♀ of styrene itch measured by PC method is approximately 10
000 or less, preferably about 2000 to about 8000.

- It is better to control charging when the A8 group is uniformly dispersed in a certain degree of agglomeration state, or locally dispersed near the toner particle surface, than when it is uniformly dispersed in molecular molecules in the toner binder resin. The effects are often more pronounced. Therefore, −A
The amount of -AB in the polymeric material containing the B group is adjusted to about 1 mol% or more, preferably about 3 mol% or more based on the -A8 group-containing matsumer unit, and it is melted with other stone resin. Mixing, solution mixing, chemical mixing by coexistence method, emulsion mixing, etc. are mixed and diluted, and the final amount is about 0.05 mol % to 10 mol % based on the toner binder resin content. Good too.

In that case, the other binder resins include vinyl homopolymers or copolymers of styrene, methacrylic acid and methacrylic esters, acrylic acid and acrylic esters, and diene, polyethylene, Olefin polymers such as polypropylene, natural and synthetic waxes, polyesters, polyamides, epoxy resins, polycarbonates, polyurethanes, silicone resins, fluorine resins, petroleum resins, etc. The molecular number and degree of crosslinking of these polymeric substances is selected arbitrarily depending on the purpose. Furthermore, as pressure fixing materials, those having a glass transition temperature ≦0° can also be used.

In the developer composition of the present invention, known colorants and other components can be used. For example, dyes and pigments such as carbon black, cyan, magenta, and yellow colors can be used as colorants, magnetic materials such as ferrite, conductivity modifiers, inorganic materials such as metal oxides, reinforcing fillers, and oxidized An inhibitor or the like may be included. Further, a known charge control agent may be used in combination.

The developer composition of the present invention may contain external additives. As external additives, conventionally known additives such as silica, carbon, alumina, titanium oxide, zinc oxide, fine resin powder, and tin oxide are used.

In the developer composition of the present invention, the toner 7 is produced by a kneading and pulverizing method.
It can be produced by any method of common lambda, such as spray drying or direct molding.

The particle size of the toner is preferably in the range of 1 to 20 tin, more preferably in the range of 5 μTrL to 15 μm based on the average particle size d50 measured by Coulter Counter method.

Hitherto, low-molecular anionic surfactants containing functional groups similar to -A8 groups or -AB groups, such as Yarosin fatty acid salts, have been studied as toner charge control agents, but none of them are effective for charge control. However, the principle of why the polymer material of the present invention exhibits an excellent charge control Ofd effect is unknown, or if a specific -A8 group is added to a polymer at a specific concentration. Since it is introduced into the substance, it is thought that the dispersion state of the ΔB group as a charging site in the substance is good and stable, and this contributes considerably.

Examples Next, the present invention will be explained by examples.
It is not limited to these.

Example 1 Styrene/'n-butyl methacrylate 60 parts by weight-1
Partial copolymer (Tg=65°C, Hn=30000,)lvv=70
000) Styrene 2/Acrylic mNa 30
Weight parts copolymer (acrylic acid approx. 6m01%, Tg=70°C, )In=4000, )ltv=90
00 > Carphone black 10 parts by weight Mix the above ingredients and crush, +rf diameter d 50=
A 13 μm groove was adjusted and the amount of charge was measured.

The charge amount itself is about -7μG/9 for the iron carrier, which is not that large, but at high temperature (35°C)
, RH 80%) and low temperature and low humidity (10° C., RH 20%), there is almost no difference from normal temperature and humidity, and it was confirmed that environmental dependence is small. In addition, compared to Comparative Examples 1 and 2 described below, 1. It showed a quick charging start-up and stable charging properties over a similar period of time.

The charge portion 7F was also narrow, and the amount of reverse polarity l-ner was also small.

Furthermore, when combined with a carrier coated with a methyl methacrylate copolymer, the amount of charge was measured, and the result was approximately -30t.
IC/! It exhibits a high charge amount of 7, and the charge rises quickly.
The charge distribution was also sharp at t*, and it was confirmed that the environmental dependence was small.

This toner contains 0.7% by weight of hydrophobic silica fine powder and 0.5% by weight of fatty acid metal salt? A was added and mixed with a carrier to form a tax image agent, and a running test was conducted using a copying machine MFX-2300 (manufactured by Fuji Xerox Co., Ltd.). Good copies were obtained with almost no change in image quality over time. Copying tests of 5,000 sheets each were conducted under high temperature and high humidity conditions, and low temperature and low humidity conditions, and the phenomena, transfer quality, and image quality were similarly good.

Example 2 10 parts by weight of carphone black of Example 1 was added to cyan pigment (
C, 1, Pigment Blue 15:3) 5
Particle size d 50= with the same formulation as Example 1.
iJI with 13 μm cyan toner? J, I did.

When the charge amount was measured in 1) (same as in Example 1), a good charge amount of -20 μC/9 was observed for both the iron-based carrier and the methyl methacrylate-based co-coated carrier. Ta.

By the way, there was a tendency for charging to rise a little slower for carriers coated with methacrylate copolymers.
Practical - F It is guaranteed that there is no problem at all, and even with Torara, the rise of charging is extremely fast compared to conventional toner, and
The charge ITi was also low at -° C., and the environmental stability was also good.

The cyan pigment (copper phthalocyanine) is positively charged [it is surprising that such good negative chargeability control is possible even though it is a raw pigment. Of course, the polymer substance containing the acrylic salt of the present invention is a colorless and transparent resin, and does not have any adverse effect on the color tone and transparency of the color toner.

This toner contains 0.6fiff1 of hydrophobic silica powder.
%, and 0.6% by weight of acrylic resin fine powder were added and mixed, and further mixed with an iron powder carrier to prepare a color developer. A continuous copy test was conducted using this developer with a copy amount of FX-2300, and the image quality and stability were good (deteriorating).

Example 3 Styrene/butyl acrylate-1 to 50 parts copolymer (Tr+=60°C1Hn=18000,)lXv=
52000) Styrene/'vinylbenzoic acid Na copolymer 35 parts by weight (approximately 50'≦ of vinylbenzoic acid, 2 m of vinylbenzoic acid
o1%, vinylbenzoic acid Na 2mo1%, T! :I=70°C5Mn=3500, )1w=9
000 >Cyan face f-to (nail-q phthalocyanine)
5 parts by weight Carbon black 1 part
A toner of 60 .mu.m in particle size was prepared, and charging was measured at a toner temperature of about 35.degree. Approximately -20u, C/'7 in all environments, good charging [
Showed life. The rise of the charge and the sharpness of the charge distribution were also very good.

Hydrophobic silica fine powder 0.7 quick for this toner? 6,)
A continuous copy test of 10,000 sheets was performed using a copying machine FX 2300 after adding and mixing 0.5% by weight of 7 acrylic resin powder, and further mixing with Ferrai 1 to carrier to adjust the amount of development. The stability was extremely good.

Example 4 The styrene/vinylbenzoic acid \a copolymer 1* of Example 3 was mixed with the ammonium salt of styrene/vinylbenzoic acid (approximately 50%
9'o), and the toner was adjusted in the same α direction.

Measurement similar to Example 3, approximately 20μC7'7 in all environments
It showed good charging I. In addition, the rise rate of charging and the sharpness of the electric charge distribution Ib were also very high.
=65°C,)In=30000. Hw=70000>
Carbon black 10 parts by weight The above components were kneaded, pulverized, and divided into plates to prepare a toner having a particle size d50=13 μm. , the particle size d=
When the mixture was mixed with 100 parts by weight of 100 .mu.m iron powder C/R, and the charge was measured, a specific charge of about -7 .mu.C/'3 was obtained. When checking the environmental dependence of the amount of charge, it was found that the amount of charge decreased significantly under high humidity. Further, when the charge distribution was measured using a charge spectrograph method, it was found that the charge portion ifi was wide and there were many toners of opposite polarity. Furthermore, the rise in the amount of charge was slow in all environments.

Comparative Example 2 Styrene/n-butyl methacrylate copolymer 60 parts by weight (Tg=
65°C, Hn=30000. MW=70000) Styrene, 30 parts by weight of acrylic acid copolymer (approximately 6m01% between acrylics, Tg=70℃, Mn-400
0,)by-9000) Carbon black 10 parts by weight The above ingredients were kneaded and ground to prepare a toner having a particle size d50=13 μm, and the amount of charge was measured in the same manner as in Comparative Example 1. Approximately -10μC7/' at normal temperature and humidity, and even higher temperature Ir! I Humid Burning-13
11G, /3, (1"bFiifft hot water temperature l'l'l 8
It showed a charge amount of uC7/7, and it was confirmed that the amount of band clearly increased due to the addition of the acrylic acid component, and that the charge amount did not decrease even under high temperature and high humidity, but on the contrary increased. .

However, the charge rise was still '1' slow, and as a result of the charge distribution measurement, it was found that the reverse polarity toner was faster than Comparative Example 1, or the reverse polarity toner was decreasing, or the opposite polarity toner was noticeable earlier.

Subsequently, when a similar test was carried out by replacing the carrier with iron cauterization coated with a methyl methacrylate copolymer, the charge amount was significantly reduced to about -4 .mu.c7t3 at room temperature and humidity, and the number of toner products with opposite polarity increased.

Comparative Example 3 Styrene/n-butyl methacrylate copolymer 88 parts by weight (9=
65°C, )1n=30000, )Iw=70000
>Stearic acid N8 2 parts by weight Carphone black 10 parts by weight The above ingredients were kneaded and pulverized to form a toner with a particle size d50 = 13 μm, and the amount of charge was measured in the same manner as in Comparative Example 1. , showed positive chargeability, and became negative chargeability as the mixing time increased. However, in the end,
It exhibited a low charge amount of about -3 μC/g at room temperature and humidity, and the amount of toner with opposite polarity was extremely large. In the case of high temperature and high humidity F-(, the charge distribution was further expanded.

Comparative Example 4 Styrene/n-butyl methacrylate copolymer 8 parts, 1 part (Il =
65°C, Hn=30000. )1w=70000
) Dodecylbenzenesulfonic acid \a 2 wa parts Carbon black 10 parts by weight The above components were kneaded and pulverized to prepare a toner having a particle size d50 = 13 μm. This toner exhibited a chargeability of approximately -7 μC/'q in a normal environment, which is approximately the same as that of Comparative Example 1. However, the chargeability under high humidity was even greater than that of Comparative Example 1, and when the charge distribution was measured, most of the toners were reverse circular toners. The appearance of the rise in charging was approximately the same as in Comparative Example 1.

Effects of the Invention The developer composition of the present invention contains a polar functional group formed as a neutralized salt of an acidic component and a medium component, and is substantially amorphous, colorless and transparent with a glass transition temperature of 50° C. or higher. Because it contains a polymeric substance, it has excellent negative chargeability, developability, and transferability. That is, the developer composition of the present invention has a quick rise in toner charge, allows control of the amount of charge on the toner, and has a sharp charge distribution, and also has excellent environmental stability of toner charge and excellent stability over time. ing. Therefore, the developability and transferability of conventional developer compositions are improved,
Always get good quality copies. Furthermore, since the polymeric substance is colorless or light-colored and transparent, it is particularly effective in forming color images in the developer composition of the present invention.

The developer composition of the present invention can be applied to both a two-component development method using a carrier and a one-component development method using no carrier.

Claims (3)

[Claims] (1) A developer composition containing a colorant and a binder resin as main components, containing a polar functional group formed as a neutralized salt of an acidic component and a basic component, and having a glass transition temperature of 50°C.
A developer composition comprising the above-mentioned substantially amorphous, colorless and transparent polymeric substance. (2) The developer composition according to claim 1, wherein the polymeric substance is composed of a neutralized salt of acrylic acid as a monomer unit. (3) Claim 1, wherein the polymeric substance is composed of a neutralized salt of vinylbenzoic acid as a monomer unit.
The developer composition described in .