JPS59232357A - Electrostatic charge image developing toner - Google Patents

Abstract

PURPOSE:To provide a toner having an excellent electrostatic charge characteristic and good other characteristics and to enable formation of a stable and excellent visible image by using a block copolymer contg. a block copolymer component by a fluoromonomer as a binder resin. CONSTITUTION:A binder resin contains a block copolymer. The block copolymer contains a block copolymer component by a fluoromonomer. The block copolymer can be adequately produced, for example, by putting a polymer obtd. by addition polymn., condensation polymn. or ring opening polymn. and a radical polymerizable fluoromonomer into a solvent and subjecting the soln. to a mechanochemical treatment such as ultrasonic wave irradiation, high-speed stirring, etc. to cut the molecular chain of the polymer and to form radical, thereby polymerizing the fluoromonomer. The block copolymer obtd. here consists of the ordinary block component by said polymer and the fluoroblock component. For example, a radical polymerizable monomer is used for the fluoromonomer. The proportion of the fluoroblock component to be incorporated into the block copolymer is adjusted preferably to 0.5-30wt%.

Description

Detailed Description of the Invention The present invention is applicable to electrophotography, electrostatic recording, electrostatic printing, etc.
This invention relates to a toner for developing an electrostatic charge image formed by a toner.

At present, as an image forming method, a method using an electrostatic image is widely adopted. The electrostatic charge image needs to be developed into a visible image using a developer, and such a developer includes a toner containing a coloring agent etc. in particles of a non-inner resin and iron powder. , a two-component developer mixed with a carrier made of glass peas, etc., and a one-component developer made of a magnetic toner containing a magnetic material etc. in binder resin particles are preferably used. There is.

However, no matter which developer contains J6, the toner particles are deposited on the electrostatic image support using the electrostatic attraction caused by the electrostatic image, and development is thereby performed. It is necessary to have excellent charging properties and to be able to be charged stably and with a sufficient amount of charge to a desired polarity.

As a means to improve the charging characteristics of toner,
It is known that toner is made to contain a charge control substance, but in this method, the affinity and stability of the charge control substance and the binder resin, or the effect of the charge control substance is small. There is a problem with point 3.

For example, in order to improve the negative chargeability of toner, powder of fluoropolymer such as polytetrafluoroethylene is used.
) A method of incorporating toner particles into the toner particles or a method of coating the surface of the toner particles is known (Japanese Unexamined Patent Application Publication No. 1983-1993).
-8141, Japanese Patent Application Laid-open No. 138737/1983)
. However, fluoropolymer has low compatibility with the toner binder resin and cannot be incorporated in a sufficient proportion, and it easily falls off after being coated on the surface of the toner particles, making it impossible to custom-order the electrification. It becomes stable.

As described above, although the method of using a charge control substance is an effective method, it is difficult to use it at a rate sufficient to obtain a large control effect, and other properties may be inhibited.

Even without considering the above-mentioned circumstances, it is most advantageous to use a binder resin that can provide the required charging characteristics, and the charging characteristics of the resulting toner are predominantly determined by the type of binder resin. This is because it will be done. It is possible to roughly control the charging characteristics of toner using the characteristics of the binder resin, and the required characteristics can be obtained without any adverse effects by using a small amount of charge control substance. You will be able to do it.

The toner having negative Teiden characteristics is used to develop an electrostatic image using positive charges formed on an electrostatic image support made of a selenium photoreceptor or the like. Conventionally, polyester resins and others have been known as binder resins that can be used in toners to provide negative charging characteristics, but other characteristics are not necessarily satisfactory.

The present invention was made against the above background, and its object is to develop a static electrostatic material that has excellent charging characteristics, has good other characteristics, and is capable of forming stable and excellent visible images. The present invention provides a toner for developing a charge image.

The above object is characterized in that the nonon inder resin contains a block copolymer, and the block copolymer contains a block symbiotic component of a fluorine-containing monomer. This is achieved using a toner for developing a charged image.

The present invention will be specifically explained below.

In the present invention, a fluorine-containing monomer, such as a radically polymerizable fluorine-containing a-mer, is used, and a block copolymerization component (hereinafter referred to as "fluorine-containing component") and other block copolymerization components are used. (hereinafter referred to as "normal block component") is obtained, and this is used as a binder resin together with 'f, 'f, or other resins, and the toner is made up of this binder resin.

For example, a binder resin containing a block copolymer as described above, a colorant or a magnetic material, and other toner materials are melt-kneaded, cooled, pulverized, and further classified to obtain the toner of the present invention.

The block copolymer used as the binder resin of the uninvented toner is obtained by, for example, adding a monopolymer obtained by addition polymerization, condensation polymerization, or ring-opening polymerization and a radical monopolymerizable fluorine-containing monomer in a solvent. It can be suitably produced by cutting the molecular chain of the polymer to generate radicals by subjecting it to mechanochemical treatment such as ultrasonic wave irradiation, high-speed stirring, etc., and thereby polymerizing the fluorine-containing monomer. . The block copolymer obtained here is said to be composed of a normal block component and a fluorine-containing block component in a proportion of 1. The solvent used in this method is preferably one having a small chain transfer constant, such as benzene or toluene.

Examples of polymers used at 8°C when using the mechanochemical treatment described above include olefin resins such as polyethylene and polyzolopyrene, polyacrylic acid esters, polymethacrylic acid nisful, acrylic acid copolymers,
Acrylic resin such as methacrylic acid combination, polyethylene, hydrogen decorated 7-tyrene resin, ethylene-vinyl acetate x*
Synthesis n, styrene copolymer, vinyl chloride, vinyl chloride IJ
Ten, vinyl resin such as vinyl acetate, nylon-12
, nylon-6, N@ polyamide resins such as fatty acid modified polyamides, polyester resins such as polyethylene terephthalate/isophthalate, polytetramethylene terephthalate/inphthalate, alkyl resins such as phthalic acid resins, maleic acid resins)'a:1 synthetic resins such as oil, phenol-formaldehyde resin, coumaron resin, epoxy resin, natural rubber, chlorinated rubber, styrene-tutadiene rubber,
Natural and synthetic rubbers such as silty rubber can be mentioned.

Further, as a specific example of a radical monomerizable fluorine-containing monomer, C
F2=CF2, CH2=CF2, CHF-CF2,
CH2=CHF.

CHF=CHF, CH2=CF-CH3, CH2=
CH-CF3, CF2=CF-CF3%CCL2=
CF2%CF C1=CH2, CF2=CF2. C
H2=CH2-CF-COOCH3, CH2-CIK
C00CF 3, CH2=CHC00CH2CH2
F% CH2-=CH-C00CH2CF20HF C
F s, CH2-=CH-COOCH2(CF2)
5CHF2, CH2=CH-C00CH2 (CF2)
nH1 CH2=CH-COOCH2CF2CHF S CH
2=C-COOCH3, CHF2
CJ1 CH2=CC00C2FI5, CH2-C-C0
0CH2CF3, H3 CH2=C-COOCH2(CF2)nH(n=
2-8), CH3 CH2=CC00CH2CF2CHFCF3, C112
=CH-COOCH2CH20CH2CF3, CH
2” CHCOOCH2CH20CF 2 CHF 2
, CH2=CHC00CH2CF2CF20(CF
2) 3CF3, CH2=CHOCO(CF'2
) nF (n = 1-8).

CH2=CHC00CH2CH20CJ12CF2CF
2H.

2 22 7+ - C2, H5 CH2=CH-1'cOoC■(2CH2-N-Co(
CP'2)nF (n = 1~8), CIK
3 TeH3 CH2=C-COOCH2CH2-N-802(CF2
), F (n = t ~ B), C2F" 5 (R = H, CH3), CF3 (CF2) nCf12 CH20COC
H-CH2OCH2CH2(CF2)nCF6(n-
1 to 8), and others to mention.

The method for producing the block copolymer used as the binder resin of the toner of the present invention +-i is not limited to the method described above. Although the content of the fluorine-containing block component in the block copolymer is not a matter of concern, it is usually 0.5 to 30% by weight or 1 to 20% by weight. is within the range of

The toner of the present invention uses the above-mentioned Zoroku copolymer itself or a combination thereof with other resins as a binder resin, and in this binder resin, if necessary,
Colorants, magnetic substances, and other additives are dispersed and contained.

As the resin constituting the inder resin together with the block copolymer, a polymer of the same type as that used in the production of the Zoroku copolymer described above may be used.

As a coloring agent, carbon black, nigrosine dye (
C, t, 50415B), aniline blue (C, 1,
A, 5U41J5), force n, co-oil full (C
,l.

Azoec Blue 3), Chrome x o - (C, 1, A14090), 'j Leto y Marie y f Roux (C, 1, A77] 03), :y'
:x-7n:t4leV7F(C,1,A2
6105), Ki/Jyye o-(C,1,A4
7UO5), methylene blue chloride (C,1,A
52015 ) ~ 7 Talosif: N'Blue (C, 1
, A 7416 (, 1), 75 Kite Green Oxalate (C, 1, width 4200U), Lamp Black (C, 1, Notification 77266 >, Rose Bengal (C, 1)
, A45435), mixtures thereof, and others. These colorants need to be contained in a sufficient proportion to form a visible image of sufficient density, and are usually 1 to 2
The ratio is said to be about 0.

The magnetic material may be a ferromagnetic metal or alloy such as ferrite, magnetite, iron, cobalt, or nickel, or a compound containing these elements, or a material that does not contain ferromagnetic materials but is subjected to appropriate heat treatment. Mention may be made, for example, of the type of alloys called Heusler alloys containing manganese and copper, such as manganese-copper-aluminum, manganese-copper-tin, or chromium dioxide, etc., which exhibit ferromagnetic properties. These magnetic substances are uniformly dispersed in the binder in the form of fine powder with an average particle size of 0,605 to 5 microns. The content thereof is 920 to 70 parts by weight per 100 parts by weight of toner.

Preferably it is 40 to 70 parts by weight.

Other additives used include silicone oil, low softening point polyethylene, low softening point polypropylene, and charge control agents.

The toner of the present invention is in the form of powder with an average particle size of 5 to 20 microns, and is combined with known carriers such as iron powder, ferrite powder, nickel powder, cobalt powder, resin-coated iron powder, glass peas, etc. It is considered a two-component developer. ! When the 7'C4 magnetic material is contained, it is considered as the 'ffc'-b57rj yarn developing agent.

Because the toner of the present invention is as described above, as will be clear from the description of the examples below, it has excellent charging characteristics that are always stable even after being used many times, and has other characteristics as well. Good, extremely clear and excellent visible images are produced in a stable manner.

This is because the toner of the present invention contains a resin Y containing a block copolymer consisting of a fluorine-containing block component and a normal Pronk component.
This is because it is used as a binder resin. That is,
The block copolymer has both the properties due to the fluorine-containing block component and the properties due to the normal block component, and the properties do not cancel each other out. Therefore, both the excellent charging characteristics due to the fluorine-containing block component and the other characteristics due to the ordinary block component are satisfied.

In addition, since the fluorine-containing block component is a component of a block copolymer, it is usually not separated from the block component (it is uniform and stable), and has great compatibility when mixed with other resins. By controlling the state of the fluorine-containing block component in the block copolymer (8), for example, the content ratio, degree of development, etc., by changing the reaction conditions, the block copolymer can have both the required charging characteristics and other characteristics. It is possible to obtain toner.

The block copolymer has a large negative chargeability due to the fluorine-containing block component, and is therefore preferable as a negative Teiden injection toner. However, in order to suppress excessive positive chargeability, the block copolymer is used as a binder. It may be used as a resin or a part thereof.

Examples of the present invention will be described below, but the embodiments of the present invention are not limited thereby. N,
"Part" represents the N foot part.

Example! 100 parts of a copolymer obtained by copolymerizing styrene 65i and 35 parts of n-butyl methacrylate was dissolved in 500 parts of benzene, and purified by a conventional method.
30 parts of 1-dihydro-2,2,3,3.4.4-hexafluorobutyl methacrylate were added thereto, and the mixture was heated in a nitrogen atmosphere.

"UH-s-3 type ultrasonic homogenizer" (manufactured by Ultrasonic Kogyo Co., Ltd., frequency 19 KH,z, output 300W) <J:
! 1. Apply ultrasound for 1 hour. ]-Dihydro-2,2°3.3,4.4-hexafluorodithyl methacrylate-(styrene-butyl methacrylate) block copolymer (97 parts) was prepared and 1ζ was prepared. Elemental analysis of this block copolymer revealed that the content of the fluorine-containing block component Z
The sum is 2.5. ) i (amount%).

Block copolymer obtained as described above 10
0 carbon blank 1゛Mogal L'' (manufactured by Casette) 10 parts low softening point polypropylene
More than 3s? The toner of the present invention having an average particle size of about 12 microns was produced by mixing the mixture and kneading it using a heated roll, and after cooling, crushing and classifying.

Conodore was mixed with a resin carrier with an average particle size of 1 (10 microns) to prepare a developer with a toner concentration of 2ON amount %, and the developer was subjected to a copying test using an electrophotographic reproduction machine [U-Bix 30 (IUJ)]. As a result, the image is clear and crisp (
, an excellent copy image with sufficiently high image density was formed. Even after 20,000 consecutive copying tests, the last case produced a copy image as good as the initial copy.

The king of toner again! , when the amount was measured at the beginning of the continuous copying test, it was 16 to 123 microcoulombs/1.20
-215 microcoulombs/1 after 000 copies
It was stable.

Example 2 100 parts of a copolymer obtained by copolymerizing 95 parts of styrene with 5 parts of butadiene was dissolved in 500 parts of benzene. 8 in the atmosphere and a high-speed stirrer [Model 4
5 Homogenizer (manufactured by Vertis, maximum no-load rotation speed 45.0 (ILI r, p, m, 1 combination 1 (
Got 35 copies. Elemental analysis of one cup of this block revealed that the content of the fluorine-containing block component was 9% by weight.

A toss of the present invention was produced in the same manner as in Example 1 except that 10 parts of this block copolymer 1 was used.

Using this toner, a developer was prepared in the same manner as in Example 1 except for 1ξ, and the same copying test was carried out. Excellent copying with sufficiently high image density! A II image was obtained. Furthermore, even in a continuous copying test over 2 U (J 00 times), an excellent copy image equivalent to the initial one was obtained at the last f.

Example 3 Combined blocks similar to Example 2 50 parts polystyrene 501! i15 Carbon Black [Mogul L J 10 frA1
Low softening point polyzolopyrene If a substance with 3 or more is used, implementation is 1 tari 1? A toner of the present invention was produced by applying the same pressure as in Example 2, and a developer was also prepared and tested, and the same favorable results were obtained as in Example 2, except that the image density was slightly lower. It was done.

Comparative Example Copolymer obtained by copolymerizing 65 parts of styrene and n-butyl methacrylate 3585 100 parts Polytetrafluoroethylene [L, DI J (manufactured by Meikin Kogyo Co., Ltd.) 1 part Carzen Black "Mogal L" J 10 part low softening point polypropylene
3 or more copies of begging example 1K? Then, a comparison toner was produced by processing in the same manner, and a developer was also produced. When I carried out this process, I was able to obtain a satisfactory copy image at the beginning, and the amount of toner was 121 microcoulombs/1, but after 5000 times of bale copying, it was -IO microcoulombs/1, which was large II@K. This resulted in the formation of copied images with low image density and no practical value.

1ξiiii

Claims (1)

[Claims] l) A toner for developing electrostatic images, characterized in that the binder resin contains a block copolymer, and the block copolymer contains a block copolymer component of a fluorine-containing monomer.