JPS60185963A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To enhance stability of dispersion, redispersibility, and fixability in a liquid developer for electrostatic photography formed by dispersing a resin into a nonaqueous solvent by polymerizing a specified monomer in the presence of a specified dispersion stabilizer in an org. solvent to prepare a nonaqueous system dispersed resin. CONSTITUTION:A monomer A used here is soluble in an org. solvent, but insolubilized in an org. solvent by polymn. in the form of its polymer. Vinyl ester of 1-3C fatty acid is used as A, mixed with a functional monomer B capable of radically copolymerizing with the monomer A and represented by a formula I in 0.1-0.5mol monomer B per mol of monomer A, and they are polymerized in a nonaqueous solvent in the presence of at least one dispersion stabilizing resin obtained by polymerizing a monomer represented by formula II or III. In the formulae I -III, L is a >8C aliphatic group; R is a >=10 conductive substrate aliphatic group; X1, X are each -COO-, -CONH-, or the like; Y is a group for connecting X with Z with C atom or atoms; Z is -COO-, -COOCH2, or the like; and Y1-Y7 are each H or alkyl.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Application of the Invention) The present invention has an electrical resistance of io 9 Ω or more and a dielectric constant of 3.
The present invention relates to a liquid developer for electrostatic photography which is made by dispersing at least a resin in a non-aqueous solvent having a molecular weight of 5 or less, and particularly relates to a liquid developer having excellent storage stability, stability, redispersibility, and fixing properties.

(Prior art) A general liquid developer for electrostatic photography consists of an inorganic or organic pigment or dye such as carbon black, nigrosine, or phthalocyanine blue, and 11 natural or synthetic resins such as alkyd resin, acrylic resin, rosin, or synthetic rubber. Gold maple soap, lecithin, and linseed are used to uniformly disperse and further solidify the charging properties of dispersed particles in highly viscous, green, and low permittivity liquids such as oil-based aliphatic hydrocarbons. It contains oil, higher fatty acids, a polymer containing all vinyl pyrrolidone, etc.

In the development process, such a developer causes electrophoresis in response to the charge of an electrostatic latent image formed on the surface layer of an electrophotographic photosensitive material or an electrostatic recording material, and is collapsed on the surface, forming a visible image ( In conventional liquid developers, the dispersion stabilizing resin and charge control agent diffuse into the liquid, making the charge characteristics unclear, resulting in poor image density and fixing properties. There were drawbacks such as deterioration and increase in background smearing, which made the copied images unclear.

Further, these developers are difficult to use because particles tend to settle or aggregate over time, and once particles settle, they cannot be redispersed.

Furthermore, it was unsuitable for rounding these defects, for offset printing, or for transfer such as charge transfer, suppression transfer, magnetic transfer, etc.

As a method for alleviating these problems, a method has been proposed in which a polymer is grafted onto the surface of a pigment such as carbon black to completely stabilize the dispersion of the particles. However, the nine developers obtained in this manner had the disadvantage that the resin component which adhered to the image surface at the same time as the pigment was relatively weak, and the strength after forming and fixing the subsequent image was insufficient.

Therefore, when these developers are used to form an image sound on zinc oxide photoreceptor paper and used as an offset printing plate, there is a problem that the oil sensitivity to printing ink and the number of printing sheets are insufficient due to the above-mentioned reasons. A sound occurred.

As another method for improving, in the above non-aqueous solvent,
A method in which monomers are polymerized to form fine resin particles in the presence of a dispersion stabilizer, and these are used as whole toner particles.
It is disclosed in U.S. Pat. No. 3, Tata No. 10, etc. However, according to the experimental results of the present inventors, although the dispersion stability of these liquid developing agents against natural sedimentation of particles has improved to some extent, it is not sufficient and when used in an actual developing device. Moreover, the toner adhering to various parts of the device hardens into a film, making it difficult to redisperse, and furthermore causing a malfunction of the device and staining of copied images. In addition, in the method for producing resin particles described above, there are significant restrictions on the combination of the dispersion stabilizer used and the monomer to be insolubilized in order to produce all monodispersed particles with a narrow particle size distribution. In general, particles with a wide particle size distribution containing a large amount of coarse particles, or polydisperse particles with an average particle size of more than 100% were formed. In addition, it is difficult to obtain a desired average particle size with monodisperse particles having a narrow particle size distribution, and large particles of 1 μm or more or 0.5 μm or more are difficult to obtain. /μm or less) very fine particles?
Formed. Unfortunately, the dispersion stabilizer used had to be manufactured through a manufacturing process that was frequent and took a long time.

(Object of the Invention) The present invention is intended to improve the problems of conventional liquid developers as described above.

An object of the present invention is to provide a liquid developer having excellent dispersion stability, redispersibility, and fixing properties.

Another object of the present invention is to provide a liquid developer that enables the production of offset printing original plates having excellent printing ink oil sensitivity and printing durability by electrophotography.

Another object of the present invention is to provide a liquid developer suitable for various electrostatic photographs and various electrostatic transfers in addition to the above-mentioned uses.

Still another object of the present invention is to provide a liquid that can be used in any system where a liquid developer can be used, such as inkjet recording, cathode ray tube recording, and recording of various change processes such as pressure changes or electrostatic changes. The purpose is to provide a developer.

(Structure of the Invention) The present invention has an electrical resistance value of /-09Ω·F or more and a dielectric constant of 3. j In the electrostatic photographic liquid developer made by dispersing at least a small amount of resin in the following non-aqueous solvent, the monomer formed entirely of the resin is soluble in the organic solvent, but does not polymerize. The monomer that can form a polymer that is insoluble in the solvent is removed. t molti and at least seven or more monofunctional monomers fO,/-j moltiyoshi represented by the general formula (I), and the resin has the following general formulas (I[) and (II
A copolymer resin soluble in the non-aqueous solvent obtained by polymerizing the monomer represented by I). A resin for electrostatic photography, characterized in that the resin is obtained by a polymerization reaction in a solution containing the entire copolymer resin. It is a liquid developer.

In formula (I), R is a fatty group having 70 or more carbon atoms, Xl is -coo-1-CONH-1 R' -CON- (R' represents an aliphatic group), -0CO-1-
C) T20CO- or -〇-, Yo and Y2 may be the same or different, and are hydrogen atoms, alkyl groups, or carboxy groups? , respectively.

In the formula (n), Ll-r, aliphatic group with carbon number or more, Y
3 and Y4 may be the same or different and each represents a hydrogen atom or an alkyl group.

In formula (m), X is -COO-1-CONH- or R
〃 -C0N- (R"Vi indicates an aliphatic group), YFi, a group that connects the above functional group COOCH2-1-〇-1-802- or -C-,
Each ′′ is represented separately.

1 However, when X represents -C00-, Y7 directly represents a hydrogen atom or an alkyl group, which may be the same or different, without intervening Yl and Z.゛The electrical resistance used in the present invention is 109 Ω・min or more, and the dielectric constant is 3. As the nonaqueous solvent below, preferably linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, or halogenated hydrocarbons can be used. Isopar E1 Isopar G Isopar H1 which is a petroleum solvent based on octane, isooctane, decane, isodecane, nonane, dodecane, indodecane, and deca-1 phosphorus isoparaffin is preferred in terms of volatility, stability, toxicity, odor, etc. Isopar L (Iso/ξ-: Exxon product name), Shell Silua/ (Shell Oil Co.)
(product name), Amsco OMS, Amsco ψ6゜solvent (product name of Spirits Inc.), etc.? Use alone or in combination.

The non-aqueous dispersion resin, which is the most important component in the present invention, is produced by the so-called multi-bed granulation method in which the monomers are completely polymerized in an organic solvent in the presence of a dispersion stabilizer. It is something.

Basically, any organic solvent can be used as long as it is miscible with the carrier liquid of the electrostatic photographic liquid developer, but it is also possible to use the same solvent as the carrier liquid at the stage of producing the resin dispersion. is usually preferable.

That is, as the solvent used in producing the dispersion resin, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, etc. are preferable.

More specifically, hexane, octane, isooctane,
Decane, isodecane, nonane, dodecane, isododeca/
, Isopart 1 Iso/ξ-G1 Ainno ξ-H1 Aitsuno ξ-H1 Isopar L1 Shell Silua/, which is an imparaffinic petroleum solvent.

Amsco OMS and the like are preferred.

A monomer represented by the general formula (IF) is used as a dispersion stabilizer necessary for polymerizing monomers in an organic solvent and making the resulting organic solvent-insoluble polymer particles into a stable resin-dispersed koji. At least one resin obtained by total polymerization of a monomer (denoted as monomer (C)) and a monomer represented by general formula (III) (denoted as monomer (D)) is used.

Preferably, in general formula (n), It;t, carbon number 1O-
The alkyl group or optionally substituted alkenyl group k, Y3 and Y4 having 10-2 carbon atoms in 24A represent a hydrogen atom or a methyl group. The monomer (C) is preferably an alkyl ester of acrylic acid or methacrylic acid (
Examples of alkyl groups include octyl group, decyl group, λ-
enalhexyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosanyl group, etc.) or alkenyl esters of acrylic acid or methacrylic acid (for example, octenyl group, thecenyl group, octadecenyl group, oleyl group, lylyl group) (groups, etc.) etc. can all be listed.

On the other hand, in the general formula (I[[), X is -C00-15 -CONH-1 or -CON-(R5 is the number of carbon atoms 1-,
(representing two alkyl or alkenyl groups) gold,
Z is -C00-1-COOCH2- or -〇-, Y is the functional groups X and Z, and is a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom? Group kz R2: R3 and R4 each represent a hydrogen atom or a methyl group, and when Z represents -coo-y, a group kz connected via a carbon atom which may be interposed, R2: R3 and R4 each represent a hydrogen atom or a methyl group; Indicates that it may be combined with

Furthermore, to give a specific example from YK, +C-←(R,
Is R' a hydrogen atom, an alkyl group, a halogen atom, etc.? ), -CH=CH-1-N HC0
-1-NH3O2-1-NHCONH-1-NHCOO
-1-so2-1-CQ-1-0-1).

It is a monomer (D), and more specifically, the following compounds can be mentioned as examples.

H3 ■ (1) CH2= C COOCR= CH2 ■ (21CH2= C Hot C00CH2COOCH=CH2 H3 (a) Cn 2 = C COOCH2COOCH=CH2 (4(a 1 CH3 (5) CH2= C C00(CH2) 3COOC1l=C H2 (6)C
H2= C C00(CH2) 2COOCH2Coo α2H3 CH2=C C0NH(CH2)2COOCH=CH2II3 α(To) CH2=C C0NH(CH2), COOCH=CH2I-f3 CH3 Q21 CH2=C C0NH(CH2), oCO OCH2CH=CH2Co
o(CH2")2-0-C) CH2H3 C4) CH2=C C0NH(CH2) 4-O-CH=CH2H3 (151CH2=C 061CH2=C Soluble copolymer resin used in the present invention described above In general, monomer (C), monomer (D), and benzoyl peroxide, azobisbutyronitrile are mixed in the same solvent as used to produce the fully dispersed resin as described above. In the presence of a polymerization initiator such as
'c-c reaction time -2~/0 hour reaction? Just do it. Under the above-mentioned polymerization conditions, gelation due to crosslinking reaction of the copolymer does not occur at all, and a copolymer containing desired side double bonds can be obtained.

In the present invention, other monomers may be added to the reaction system. In addition, by performing a polymerization reaction, a ternary or more copolymer can be obtained. In any case, monomer (C) and monomer (D)
The composition ratio is jO:jO~tata, yo:0. j (weight ratio) is preferable, and the molecular weight of the copolymer is preferably jt000 to j00,000.

Specific examples of the resin obtained as described above are shown below, but the content of the present invention is not limited thereto.

0OUHIH37COOCH=CH2H3 1 H3 (7(3?'(=H3 H3) Furthermore, when obtaining the resin dispersion of the present invention, a conventionally known dispersion stabilizer can also be used.

That is, various synthetic resins or natural resins soluble in organic solvents can be used alone or in combination of 2'm or more. For example, an alkyl chain with a total number of carbon atoms ranging from 30 to 30 [which may contain substituents such as halogen atoms, hydroxyl groups, amine groups, alkoxy groups, and heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms] alkyl esters of acrylic acid or methacrylic acid, vinyl esters of fatty acids, or vinyl alkyl ethers or monomers such as olefins such as butadiene, isoprene, diindutyrene, etc. polymers or copolymers formed by combinations of fJ 2 fJli or more, and furthermore, polymers soluble in organic solvents such as those mentioned above, monomers that form the entire structure, and various monomers of H4° as shown below. 7
- Copolymers using the following monomers can also be used as long as the resulting copolymers are soluble in organic solvents.

For example, methyl, ethyl, n-propyl or u such as vinyl acetate, acrylic acid, methacrylic acid or crotonic acid.
is o-propyl ester; styrene; derivatives such as vinyltoluene and α-methylstyrene; unsaturated carboxylic acids or their anhydrides such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid; hydroxyethyl methacrylate , hydroxyethyl acrylate, diethylaminoethyl meccrylate, N-vinylpyrrolidone, acrylamide, 7°crylonitrile,
λ-chloroethyl methacrylate, 0.2I-coated trifluoroethyl methacrylate-1, hydroxy group,
Examples include metals containing various polar groups such as an amino group, an amide group, a cyano group, a sulfonic acid group, a carbonyl group, a halogen atom, and a petero ring. Alternatively, in addition to the above synthetic resins, natural resins such as alkyd resins, alkyd resins modified with various fatty acids, linseed oil, and modified polyurethane resins can also be used.

As mentioned above, the monomers used in the production of the non-aqueous dispersion resin of the present invention are monomers that are soluble in organic solvents but become insolubilized by polymerization (referred to as monomers (A)).
and a monofunctional monomer (referred to as monomer (B)) represented by the general formula (I).

As the monomer (A), for example, vinyl esters of aliphatic carboxylic acids having 1 to 3 carbon atoms (acetic acid, -propio/acid, butyric acid, monochloroacetic acid, etc.) or allylnisder; acrylic acid, methacrylic acid, chloro/acid Alkyl esters or alkylamides of unsaturated phosphor/acids having a carbon number of ~3, such as , itaconic acid, and maleic acid; Styrene; Styrene derivatives, such as vinyltoluene and α-methylstyrene; Acrylic acid, methacrylic acid, and crotonic acid , unsaturated carboxylic acid such as maleic acid, itaconic acid, or anhydride thereof; 1:
1) 'loxoethyl methacrylate, hydroxyethyl acrylate, diethylaminoethyl methacrylate,
N-hinylpyrrolidone, acrylonitrile, vinyl ether and the like can be mentioned.

The monomer (B) which is the core component of the present invention is the monomer t
The general formula (
1) -functional monomer, preferably having the general formula (
In I), R is an optionally substituted alkyl group having 10 to 3 λ carbon atoms, or an optionally substituted alkenyl group having 10 to 3-2 carbon atoms, and Xl is -COO-1-CONH-1 R ' -C0N- ('R' represents an alkyl group having 1 to 3.2 carbon atoms or an aralkyl group), -0CO-1-CH20
CO- or u-0-, Yt and Y2 may be the same or different, and represent a hydrogen atom, a methyl group, a carboxy group, etc.
Each is represented.

More specific monomers (B) include, for example, alkyl esters of unsaturated carboxylic acids having 10 or more carbon atoms (as alkyl groups, for example, , decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosanyl group, etc.) or optionally substituted alkenyl esters having 70 or more carbon atoms (
Examples of alkenyl groups include decenyl group, dobutenyl group, tetradecenyl group, octadecenyl group, docosanyl group, lylyl group, etc.), vinyl esters or allyl esters of higher fatty acids (such as fatty acids such as lauric acid, myristic acid, stearic acid, behenic acid, oleic acid, linoleic acid, etc.) or optionally substituted alkyl vinyl ethers having 2 or more carbon atoms (for example, as an alkyl group,
octyl group, dodecyl group, hexadecyl group, octadecyl group, etc.), optionally substituted alkenyl vinyl ethers with carbon number r or more (alkenyl group, !: such as octenyl group, decenyl group, octadecenyl group, tocosenyl group, etc.), etc. You can get the whole amount.

The dispersion resin of the present invention consists of at least seven or more types of monomers (A) and monomers (B) as described above, and the important thing is that the copolymer resin synthesized from these monomers If it is insoluble in the hydrocarbon solvent, a desired dispersed resin can be obtained. More specifically, it is preferable to use the monomer (B) that is not to be insolubilized in an amount of kO,/~j mol to the monomer (A) that is to be insolubilized, and more preferably 0, r to 3 mol.

To produce the dispersion resin used in the present invention as described above, generally, the dispersion stabilizing resin as described above and the monomers (A) and (B) are mixed in a non-aqueous solvent with base/diyl peroxide. The polymerization may be carried out by heating in the presence of a polymerization initiator such as azobisisozotyronitrile. Specifically, a polymerization initiator is added to a mixed solution of resin, monomer (A), and monomer (B). how to add,
Monomer (A) and monomer (B) are added to the solution in which the resin is completely dissolved.
) A method in which the remaining monomers are added dropwise together with the entire polymerization initiator, or the remaining monomers are added together with the polymerization initiator into a mixed solution containing the entire amount of the resin and a portion of the mixture of monomer (B) and monomer (B). There are methods in which a mixture is optionally added, and there are also methods in which the entire mixed solution of the resin and monomer is optionally added together with a polymerization initiator in an organic solvent, and it can be produced using either method. .

The total amount of monomer (A) and monomer (B) is about 2.10 parts by weight based on 10 parts by weight of the organic solvent, preferably 1,000 parts by weight.

The amount of the soluble resin as a dispersion stabilizer is i, ioo parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the total monomers used above.

The amount of polymerization initiator is 0.0% of the total monomers. /~jchi (weight) is appropriate.

In addition, the polymerization temperature is about O~/εc (lc), preferably 60~1200C, and the reaction time is /-/J
r time is preferred.

The nonaqueous dispersion resin produced according to the present invention as described above exists as fine particles with a uniform particle size distribution, and monodisperse particles having a desired average particle size can be easily produced. These dispersion resins exhibit very stable dispersibility, and have good dispersibility even when used repeatedly over a long period of time, especially in the developing device.They are also easy to redisperse, and do not cause contamination or gold to adhere to various parts of the device. Totally unacceptable. Furthermore, when the film was completely fixed by heating or the like, a strong film was formed and good fixing properties were exhibited.

Although it is not possible to explain this remarkable performance improvement theoretically, it is possible to polymerize the monomer (A) and a small amount of the monomer (B) with a long alkyl carbon number in the presence of a small amount of the monomer (B) in the dispersed resin. Effects occur only when fully manufactured (see examples)
The monomer C is present at the particle interface of the insolubilized and dispersed resin.
B) It is presumed that there is a soluble component containing K, and that the particle surface has undergone some kind of modification.

In the present invention, is there a coloring agent if necessary? The coloring agent is not particularly specified, and various conventionally known pigments or dyes can be used. The colorant may be used alone by being dispersed in the nonaqueous solvent in combination with a dispersion accelerator, or by chemically bonding a polymer to the surface of the colorant to form graft-type particles (for example, grafted carbon : Mitsubishi Gas Chemical product name) may be used. The coloring agent may be entirely contained in the resin described above.

As a method for completely coloring the dispersed resin, for example,
- Dispersion machine (paint shaker colloid mill, vibration mill, ball mill, etc.) which is a known method in No. 712≠2?
There are many known pigments and dyes that can be used. Examples include magnetic iron oxide powder, carbon black, nigrosine, alkali blue, no-nza yellow, quinacridone red, phthalocyanine blue, phthalocyanine black, and benzidine yellow.

Another coloring method is Tokukai Sho! 7-≠1173g, etc., there is a method of heat dyeing a dispersed resin material with a preferred dye.

For example, Hansa Yellow, Crystal Violet, Victoria Love, Lou, Malachite Green/, Seriton Fast Red, Despers Yellow, Despers Red,
Examples include death chisel sprue and solvent red.

Furthermore, as another method of coloring, there is a method of chemically bonding the dye to the dispersion resin. For example, JP-A-J°
≠For OJ, 2, etc., there is a method in which the resin is completely reacted with the dye, or in the case of Tokko Sho 4, Ko-22zsr, etc., the dye is bonded to the monomer of the resin, which can be made insolubilized and dispersed by polymerization. All can be used.

The liquid developer of the present invention may contain various additives as necessary in order to strengthen charging characteristics or improve image quality. It is specifically described on the No. Hiro≠ page.

51J engineering td, /-λ-ethylhexyl sulfocono＼
Examples of additives include metal salts of phosphoric acid, metal salts of naphthenate, metal salts of higher fatty acids, lecithin, and poly(hinylpyrrolidone).

Colorant? The toner particles made of a resin which may be contained are preferably 6.5 parts by weight to 1 part by weight of vehicle fluid per 100 parts by weight of carrier liquid. If it is less than 0.5 parts by weight, the image density will be insufficient, and if it is more than 0.5 parts by weight, fogging will easily occur in non-image areas.

Carrier liquid soluble resins, such as the fractional stabilizers mentioned above, may also be used as needed, with COS
It is possible to add about 1 to 1 cio Tsumeyobe. The charge control agent as described above preferably has an amount of 0.00/~i,oN parts per 7000 parts of carrier liquid. Furthermore, if necessary, ・Various additives? They may be added, and the upper limit of the total amount of these additives is regulated by the electrical resistance of the developer. That is, if the electrical resistance of the liquid developer with toner particles removed becomes less than io'Ω・α, it will be difficult to obtain a high-quality continuous tone image, so the amounts of each additive should be adjusted within this limit. It is necessary to control it.

All embodiments of Yoriaki Yoriaki are shown below, but the content of the present invention is not limited thereto.

Production example 1 of resin for dispersion stabilization: Compound example (a) lauryl methacrylate 1, 7 g, vinyl methacrylate 2
．． A mixed solution of 29 and .

While stirring, 2.2'-azobis(butyronitrile)"9 was added, reacted for 3 hours, and further λ.

It was added to λ'-azobis(butyronitrile)/1' and reacted during the daytime. The solid content concentration of the obtained solution was ≠1.

A colorless and transparent viscous substance obtained by pouring a portion of the above reaction solution into 70 times the volume of methanol solvent had a molecular weight of 3°1\, I04, as measured by high performance liquid chromatography.

Production example 2 of dispersion stabilizing resin: Compound example (b) stearyl methacrylate 12t, 711. A mixed solution of vinyl methacrylate J, 2!9 and indecane J (76 g) was heated to a temperature of 7!0C under a total nitrogen stream, and then
Azobis (butyroni) /, 3. ! 9f was added and stirred for 3 hours. Even more.

3 gk of λ'-azobis(butyronitrile) was added and reacted for 5 hours.The solid content concentration of the obtained solution was Vi30.
．． It was 0%. Treat and measure as in Production Example 1. The molecular weight of the white solid was J, jX/0.

Production of dispersion stabilizing resin F! AU3: Compound example (c) lauryl methacrylate 7/, 01i, vinyloxycarbonylmethyloxy carbonylethyl acrylate λ,
A mixed solution of 223 g of λg and iso, t H was heated to a temperature of 700 C under a nitrogen stream, and then λ1.2'-azobis(butyronitrile) i and ig2 were added and stirred for 3 hours. Furthermore, -2'-azobis(butyronitrile)/,
/9f was added and reacted for 5 hours. The solid content concentration of the obtained solution was about 60%. The molecular weight of the colorless and transparent viscous material treated and measured as in Production Example 1 was 3.1'110'.

Production example 4 of dispersion stabilizing resin: Compound example (mixed solution of hexadecyl acrylate, Og, allyloxycarbonyltecamethylene methacrylamide 3,/9 and n-dodecane/≠!g under a total nitrogen stream, Warm to a temperature of 74"C, then λ.

Add 2g of λ'-azobis(butyronitrile) and add 3
Stir for hours. Further, all of 2,2'-azobis(butyronitrile) was added and the reaction was carried out during the daytime. The solid content concentration of the obtained solution was Kota, II-H. The molecular weight of the white solid treated and measured as in Production Example 1 is ≠, i×to
Met.

Production Example 5 of Dispersion Stabilizing Resin: Compound Example (i) A mixed solution of stearyl methacrylate atg, vinyloxyethyl acrylate/, 7.9, and iso/e''-G10 was brought to a temperature of 7 J'C under a nitrogen stream. After heating, a total of 0.7 g of benzoyl peroxide was added and stirred for 3 hours.Furthermore, a total of 0.79 g of benzoyl peroxide was added and the reaction was carried out during the daytime.

The solid content concentration of the obtained solution was λ and 0. The molecular weight of the white solid treated and measured as in Production Example 1 is y,
It was txi o.

Manufacturing Example 1 of Resin Particles 'fC Polymer Solution Hiroshi' obtained in Manufacturing Example 1 of Resin for Dispersion Stabilization
"-2&% D Enemy vinyl lccg, stearyl methacrylate≠g and isodecane sszg mixed bath solution [, 9
Under an air flow (1) was heated to a temperature of 7J0C without stirring. 0Cg of benzoyl peroxide was slowly added and reacted for a long time. After ≠0 minutes of addition of all the initiator, the bath liquid became cloudy. Initially, the reaction temperature rose to f♂0C1. After cooling, the white dispersion obtained by passing through a 206 mesh nylon cloth had a polymerization rate of 7.
At 0%, a latex with an average particle size of O0λlμ was produced.

Production Example 2 of Resin Particles Polymer bath liquid j/ obtained in Production Example 2 of Dispersion Stabilizing Resin,
jjJ, vinyl acetate icog, lauryl methacrylate 3g and isodeca 73≠! A total of 1 g of the mixed solution was heated to a temperature of 7j'C while stirring under a nitrogen stream. Benzoyl peroxide λ and Ogk were added and the reaction was carried out during the daytime. JO after cooling
The white dispersion obtained by passing through an O-mesh nylon cloth was a latex with a polymerization rate of 3 cm and an average particle size of 0.23 μm.

Production Example 3 of Resin Particles 36 g of the polymer solution obtained in Production Example 3 of Motion Stabilizing Resin,
Vinyl acetate ioc! y, stearyl acrylate! ! A mixed solution of 375I and n-dodecane was heated to a temperature of /6°C in a nitrogen stream, and then heated.

λ'-Azobis(butyronitrile'gk) was added and reacted for V hours.

Cooling 9.20 (1/Mesh nylon cloth? IT y
The obtained white dispersion had a polymerization rate of 5% and an average particle size (% (j, 4.r 1 piece for 117 μm latex).

Manufacturing Example 4 of Resin Particles The juice obtained in Manufacturing Example 3 of Motion Stabilizing Resin? Rimmer solution 30.
1g, vinyl acetate/0091 crotonic acid g1 stearyl methacrylate rig and Arr buckwheat H, 3A
! The mixed solution of ji was heated at a temperature of 7c and 0ctrt while stirring for 15 minutes under a nitrogen stream. λ·co′-azobis(butyronitrile)/, ♂91 was added and reacted for φ time. After removal, the nylon surface of the 00 mesh was completely penetrated, and the obtained white dispersion was a latex with a polymerization rate of 23% and an average particle size of 0.2 μm.

Production example 5 of resin particles Polymer solution 34Af obtained in production example 4 of resin for dispersion stabilization
A mixed solution of i, vinyl acetate ioog, N-methyl-N-stearyl methacrylamide, N-methyl-N-stearylethacrylamide p, zg and n-totican 3tig was heated to a temperature of 700C while stirring under a total nitrogen stream. did. -2'-azobis(butyronitrile)/1# and reacted for μ hours. After cooling, a 200 mesh nylon cloth was passed through, and the resulting white dispersion had a polymerization ratio of 7.2% and an average particle size of 0. /μm latex.

Production Example 6 of Resin Particles Polymer solution obtained in Production Example 3 of Dispersion Stabilizing Resin 30.4
1! , poly(lauryl methacrylate) rg; vinyl acetate/00 fl, a mixed solution of lauryl methacrylate≠J and Isopar 3j 7 fl was heated to a temperature of 7 C'C while stirring under a nitrogen stream.

λ, 2/-Azobis(butyronitrile)/, 19 were added in total and reacted during the daytime. After cooling, it was passed through a 200-mesh nylon cloth, and the resulting pale white dispersion was latex with a polymerization rate of 3 mm and an average particle size of 0.11 μm.

Production Example 7 of Resin Particles Polymer solution obtained in Production Example 1 of Dispersion Stabilizing Resin ≠/, 2
A mixed solution of i, vinyl acetate/00, iil, 6 g of vinyl stearate, and 3!3 ji of isodecane was heated to a temperature of 700 C while stirring under a total nitrogen stream. λ, λI
-Azobis(butyronitrile)/.

All of tI was added and the reaction was carried out during the daytime. After cooling, it was passed through a 200 mesh nylon cloth, and the resulting white dispersion was a latex with a polymerization rate of 5% and an average particle size of 0.23 μm.

Production Example 8 of Resin Particles: Comparative Example The same procedure as in Production Example 1 of Human Resin Particles was repeated except that stearyl methacrylate was completely removed, and the resulting white dispersion had a polymerization rate of is% and an average particle size of 0°2. .2 μm latex.

Production Example 9 of Resin Particles: Comparative Example B In Production Example 1 of Resin Particles, poly(stearyl methacrylate) JP was used instead of stearyl methacrylate.
', and the other operations were the same as in Production Example 1.

The obtained white dispersion had a polymerization rate of rr% and an average particle size of 0.2.
/μm latex.

Production Example 1o of Resin Particles: Comparative Example C" Stearyl methacrylate≠g was added to the white dispersion obtained in Production Example 8 of Resin Particles, and the mixture was thoroughly stirred.

Example L Poly(lauryl methacrylate)/Og, along with Nigrosin IOY and Shell Silua 1,309f glass beads were placed in an India shaker (Tokyo S machine ■) and heated to 0.
The mixture was dispersed for a minute to obtain a fine dispersion of nigrosine.

30 g of the resin dispersion of Resin Particle Production Example 1, 3 g of Nigrosine Dispersion 'fllJ2? Zirconium Nanthenate O
A liquid developer was prepared by diluting it to osg2shellsilua/,/l.

(Comparative Developers A to C) In the above production example, three types of comparative liquid developers A, B, and C were prepared in place of all the resin particles in the resin dispersion.

Comparative liquid developer A: Resin dispersion of resin particle production example 8 B: # 9 r # C: # 10 # The obtained liquid developer was manufactured using Fuji fully automatic plate making machine ELF corc<
ELF master (manufactured by Fuji Photo Film) is used as a developer for the ELF master (manufactured by Fuji Photo Film) as an electrophotographic photosensitive material for printing masters. Plate gold part.

The resulting image of the companion master plate was a good continuous tone image. In the same way, 2000 sheets of gLP master were processed and 1.2 oooc sheets were developed, and then the presence or absence of toner adhesion stains on the developing device was observed, and it was found that the developer using the separation resin of the present invention did not cause any stains. However, in the three comparative liquid developers A to C, there was significant adhesion and staining around the rollers.

When monomer (-B) k is not used (comparative example), when monomer (B) is post-added to the dispersion after polymerization and granulation of particles (comparative example C), and when monomer (B) is not used (comparative example), ) was polymerized completely independently of the monomer (A) forming the particles, and the monomer (
B) Polymer? When added in advance and granulated (Comparative Example B)
This shows that the resin particles are clearly different from the resin particles of the present invention.

The master plates for offset printing obtained using the developer of the present invention had very clear images both in the initial development and after 2,000 sheets were developed. Furthermore,
Using these master plates, 3,000 sheets were printed in a conventional manner, and even after printing 3,000 sheets, clear printed matter could be obtained. Furthermore, after leaving this developer session for 3 months,
The grapes were treated in the same way as above, but there was no difference at all from before aging.

Example 2 White dispersion i obtained in Resin Particle Production Example 1.

Total temperature of mixture of OI and Sumikalon Black i, sg 1
The mixture was heated to 000C and stirred for a while.

After cooling to room temperature, a 200-mesh nylon cloth was passed through and all remaining dye was removed to obtain a black resin dispersion with an average particle size of 0.0 μm.

30 g of the above black resin dispersion, zirconium naphthenate a, c zg2 gel silua 1. A liquid developer was prepared by diluting the solution to 1 liter.

This ELP mass was developed using the same equipment as in Example 1. Even after developing 2,000 sheets, no toner adhesion stains occurred on the equipment.

Example & Mixture of white dispersion 10op obtained in Resin Particle Production Example 4 and Victoria Blue BJII Total temperature 700~♂
The mixture was heated to O0C and stirred for 6 hours. -200 after cooling to room temperature
The dye that remained after passing through the mesh nylon cloth? Remove all blue resin particles with an average particle size of 0.20 μm.

A liquid developer was prepared by diluting the blue resin dispersion 21fi, zirconium naphthenate o, and ot112 to ξ-H/A.

This is carried out using the same device as in the example.
000 sheets development laboratory, 20 (i) Even after developing 0 sheets, there was no toner adhesion stain on the device. Also, the image quality of the obtained offset printing master plate was clear, and the printed matter after printing 300 sheets. The image quality was also very clear.

Example 3011 White resin dispersion obtained in Production Example 2 of Resin Particles 0. ! g and semi-docosanylamidates of copolymers of diisobutylene and maleic anhydride o, o, zg2 Aitsuno ξ-G/A [All liquid developers were prepared by diluting.

this? ELP master f2 using the same device as in the example.
Even after developing 2000 sheets, no toner adhesion stains were observed on the device. In addition, the image quality of the nine offset printing master plates obtained and 300
The image quality of the printed matter after printing 0 sheets was clear.

Further, after leaving this developer for 3 months, the same treatment as above was performed, but there was no difference at all from before the aging.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment Letter, June 1, 1980, Commissioner of the Japan Patent Office, 8k, 1) “ 1. Indication of the case: Showa-Year Patent Application No. ≠ 773 Hiroshi No. 2, Title of the invention: Electrostatic Photographic adult developer 3, relationship with the person making the amendment Patent application Dalian 1r Address: IOG bundle 3; Partially No. 4, 2-26-30 Nishi-Azabu, Minato-ku, subject of amendment Detailed description of the invention in the specification ”
In Column 5, the description in the section "Detailed Explanation of the 4th Amendment" in Al 11th Statement of Contents of Amendment is amended as follows.

■) Page 7, lines 16-17 Delete "in all available systems".

2) Page 7, line 20 After “this invention” "teeth" Insert.

3) Page 10, line 14 "Decalin Isoparaffin" "Decalin, isoparaffin" and correct it.

4) Page 12, line 8 After “L is” "May be replaced" Insert.

5) Page 13, line 8 rR2SR3J "R2, R3" and correct it.

6) Page 13, line 10 "Z" "X" and correct it.

7) Page 13, line 11 “Directly to X without going through Y” “Directly without going through Y and 2. and correct it.

8) Page 22, line 11 "Linseed oil, denatured" "Linseed oil denatured" and correct it.

9) Page 22, line 12 Delete "natural".

10) Page 25, line 1 "8 carbons" "Carbon number 10-1 and correct it.

11) Page 25, line 4 ``The number of carbon atoms is 8j. "Carbon number 10" and correct it.

12) Page 27, line 19 "Particles of resin" "Resin particles" and correct it.

13) On page 30, line 5, after “mentioned.” “Also, the semi-alkylamidated diisobutylene-maleic acid copolymer described in Japanese Patent Publication No. 49-26594, and the specification of Japanese Patent Application No. 1983-36787.” A copolymer comprising a copolymer of maleic anhydride as described above and an amino compound, which has a hemi-maleic acid amide component and a maleimide component as repeating units in the copolymer, is used to adjust the charging characteristics. "can be used."

14) Delete "N-methyl-N-stearylethacrylamide" on page 36, lines 5-6.

15) Page 42, line 9 1-0.5gJ r2.5gJ and correct it.

Claims (1)

[Claims] The electrical resistance value is 109Ω·α or more and the dielectric constant is 3! In the electrostatic photographic liquid developer comprising at least resin gold dispersed in the following non-aqueous solvent, the monomer forming the resin is soluble in the organic solvent, but by polymerization, the monomer is dissolved in the organic solvent. Monomers that can form polymers that are insoluble in
the law of nature! molti and at least one or more monofunctional monomer fO,/-j molti represented by the general formula (I), and the resin has monomers represented by the following general formulas (n) and (III). 1. A liquid developer for electrostatic photography, which is obtained by a polymerization reaction in a solution containing a copolymer resin soluble in the non-aqueous solvent obtained by polymerizing a copolymer resin. In formula (I), Rid is an aliphatic group having 10 or more carbon atoms,
l is -COO-1-CONH-1 R' -CON- (R' represents an aliphatic group), -0CO-1-
CH20CO- or -o-1:, Yl and Y2 may be the same or different and each represents a hydrogen atom, an alkyl group or a carboxy group. In formula (II), L is an aliphatic group having at least r carbon atoms, and Y3 and Y4 may be the same or different, and each is a hydrogen atom or an alkyl group. Each is represented. X-Y-Z-C=CH In formula (m), X is -COO-1-CONH- or R
"-CON-(R" represents an aliphatic group)? , Y represents a group that connects the functional group X and the atomic group Z with a carbon atom which may be via a hetero atom, and Z represents the atomic group Y and 0, respectively. However, when X represents -coo-'i, it may be directly bonded to 6Y7 -C=CH without going through Yl and Z. Further, Y5, Y6 and Y7 may be the same or different and each represents a hydrogen atom or an alkyl group.