JPS6156359A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To improve a disperse stability and a fixing property of the liquid developer by dispersing a specific acrylic ester resin in an organic liquid having a specific electric property. CONSTITUTION:The acrylic ester resin is prepared by copolymerizing a monofunctional monomer e.g. vinyl ester and acrylic ester etc. with a compd. represented by the formula I e.g. acrylic acid, methacrylic acid or crotonic acid etc. and also adding a dye soluble to the above monomer. The liquid developer is prepared by dispersing the obtd. acrylic ester resin into the organic liquid having >=10<9>OMEGA.cm electric resistance and <=3.5 permittivity e.g. octand, decane, nonane etc. As the obtd. liquid developer for the electrostatic photography contains the acrylic ester resin, the developer having the good disperse stability of the resin, free from a contamination of a developing apparatus and giving a clean image is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention provides an electrical resistance of 109 Ω·α or more and a dielectric constant J, j
This relates to a liquid developer for electrophotography comprising at least a colored resin dispersed in the following carrier liquid. .

``Prior Art'' General electrostatic photographic liquid developers are made of inorganic or organic pigments or dyes such as carbon black, nigrosine, and phthalocyanine blue, and natural or synthetic resins such as alkyd resins, acrylic resins, rosins, and synthetic rubbers. are dispersed uniformly in a highly insulating, low-charging rate liquid such as petroleum-based aliphatic hydrocarbons, and metal soap and lecithin are added for the purpose of making the charging characteristics of the dispersed particles uniform and strong. , linseed oil, higher fatty acids, and polymers containing vinyl pyrrolid.

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 in the development process, and is fixed on the surface. ,
A visible image (copied image) is formed, but in conventional liquid developers, the dispersion stabilizing resin and charge control agent diffuse into the liquid, making the charging characteristics unclear, and thus the image There were drawbacks such as a decrease in density and fixability, and an increase in background smearing, which made the copied image unclear.

In addition, these developers are difficult to use because particles tend to settle or agglomerate over time, and once they settle or aggregate, they cannot be redispersed! ′! It was h.

Furthermore, due to these drawbacks, it was unsuitable for offset printing, or for transfer such as charge transfer, suppression transfer, and magnetic transfer.

As a method for improving these problems, a method has been proposed in which a polymer is grounded on the surface of a pigment such as carbon black to stabilize the dispersion of particles. However, the developer obtained in this manner has a drawback that the amount of the resin component that adheres to the image surface at the same time as the pigment is small, and the strength of the formed image after fixing is not sufficient.

Therefore, when these developers are used to form an image on zinc oxide photoreceptor paper and used as an offset printing plate, the oil sensitivity to the printing ink and the number of printed sheets may be insufficient due to the aforementioned reasons. problem
gave rise to I.

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 stabilizing resin containing a graft group, and the fine resin particles are used as toner particles is disclosed in US Patent No. 39-09. ! However, according to the experimental results of the present inventors, although the dispersion stability of these liquid developers against natural sedimentation of particles has improved to some extent, it is not sufficient, and in practice When used in a developing device, the toner that adheres to various parts of the device solidifies into a film, making it difficult to redisperse and further causing device failure and smudging of copied images. In addition, the formation of preferable resin particles by the above method has significant restrictions on the combination of dispersion stabilizer and monomer used, and in general, the particle size distribution contains a large amount of coarse particles. It becomes a wide 0
Furthermore, there are problems in that a preferred dispersion stabilizer must be synthesized through a complicated manufacturing process.

Furthermore, as a method for obtaining colored toner particles using the above-mentioned polymerization granulation method, there is a method described in JP-A-63-126-1. In this method, for example, in a non-polar solvent containing a charge control agent, a monomer, which is soluble in the non-polar solvent in its state but becomes insoluble when polymerized, and a dye soluble in the monomer but insoluble in the non-polar solvent, and This is a method in which a polymerization reaction is carried out while dropping a solution consisting of a polymerization initiator.

According to this method, the monomer is dissolved in the non-polar solvent at the same time as the solution is added dropwise, thereby forming fine crystals of the dye.Then, as a result of polymerization of the monomer, the fine crystals of the dye contain seven monomers. An electrostatographic liquid developer having a structure in which a polymer is adsorbed is obtained.

However, as a result of experiments conducted by the present inventors, it has become clear that this method has the following major problems. In other words, many dyes have chemical structures in which radicals such as phenol 1 hydroxyl M, phenylamino groups, and nitrophenyl groups can exist stably, and many dyes with these chemical structures undergo radical polymerization. It acts as a substance that inhibits radical polymerization of monomers, such as when used as an inhibitor. Therefore, as mentioned above, when radical polymerization of monomers is carried out, if a dye is present, polymerization will not take place, and in extreme cases, there is a serious drawback that no polymer will adhere to the fine crystals of the dye at all. Furthermore, in addition to the requirement that the dye that can be used in this method not act as a radical polymerization inhibitor, it also has all the properties of being insoluble in nonpolar solvents and soluble in the monomer of the resin to be polymerized, as described above. Therefore, the range of selection of dyes and monomers to be used is extremely narrow, and in fact, many dyes cannot be used in this method. In addition, as mentioned above, there was a problem in that the dispersion stability of particles produced by these polymerization granulation methods was insufficient, making them difficult to put into practical use.

"Problems to be Solved by the Invention" The present invention aims to improve the problems of conventional liquid developers as described above.

An object of the present invention is to provide a liquid developer with 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 electrostatographic and mild electrostatic transfer applications in addition to the above-mentioned uses.

Still another object of the present invention is to provide a liquid developer 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. That's true.

"Means for Solving the Problems" The present invention has an electrical resistance value of /θ9Ω·α or more and a dielectric constant of 3.9Ω·α or more. - in an electrostatographic liquid developer comprising at least a colored resin dispersed in the following carrier liquid:
(This is an electrostatic photographic liquid developer characterized in that the resin is a colored copolymer resin obtained in the following steps (1) and (2).

(1) Monofunctional monomer (A) and general formula (I) that are soluble in non-aqueous solvents but become insolubilized by polymerization
A dispersion of a copolymer resin is prepared by polymerizing at least 7 or more types of monomers (B), each of which is represented by the formula and causes a copolymerization reaction with the monomer (A). 0 (z) A colored copolymer resin is made by adding at least seven kinds of organic dyes to the dispersion obtained in (1) and heating it. General formula (I) X-Formula (I ), R' is an aliphatic group having 2 or more carbon atoms, R'
or -〇-, Yl and Y2 may be the same or different, and represent a hydrogen atom,
Alkyl group, -COOR'' or -CH2COOR'' (R
0 represents an aliphatic group) The carrier liquid used in the present invention and having an electrical resistance of 10 9 Ω·α or more and a dielectric constant of 3.5 or less is preferably a linear or branched aliphatic hydrocarbon, Alicyclic hydrocarbons, aromatic hydrocarbons, % halogenated hydrocarbons, etc. can be used.Octane, inoctane, decane, isodecane,
Isopar E1 Isopar G coated with Nona/, dodecane, isododecane, decalin, and isoparaffin-based petroleum solvents
1 Ainpar H1 Isopar L (Aitsuno ξ-: trade name of Exxon Corporation), Shell Silua/ (trade name of Shell Oil Co.), Amsco OMS, Amsco 4ttO solvent (trade name of Spirits Corporation), etc. are used alone or in combination.

The non-aqueous dispersion resin, which is the most important planting component in the present invention, is obtained by polymerizing the monomers (A) and (B) in a non-aqueous solvent, if necessary in the presence of a dispersion stabilizer. After manufacturing the resin, the dispersed resin is dyed with an organic dye.

Basically, any non-aqueous solvent that can be used is one that can be mixed with the carrier liquid of the electrostatic photographic liquid developer, but the same solvent as the carrier liquid can be used at the stage of producing the resin dispersion. However, it is usually preferred to use

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.

Specifically, the levers include hexane, octane, isooctane,
Deca/, indecane, nonane, dodecane, indodecane, and isoparaffin-based petroleum solvents such as Isopar E1 Isopar G1 Itsuno ξ-H1 Iso, e L, Shell Silua/, and Amsco OM8 are preferred.

The monomer used in the production of all non-aqueous dispersion resins,
A monofunctional monomer (A) which can be dissolved in the solvent but becomes insolubilized by polymerization, and a monomer having the general formula (
It can be classified into monomers (B) which contain an aliphatic group having 2 or more carbon atoms and copolymerize with monomer (A) as shown in I).

As the monomer (A), for example, vinyl esters or allyl esters of aliphatic carboxylic acids having up to 3 carbon atoms (propionyl acetate, butyric acid, monochloroacetic acid, etc.), acrylic acid, methacrylic acid, crotonic acid, itacon acids, alkyl esters or alkylamides of unsaturated carboxylic acids such as maleic acid having a carbon number of up to 3, styrene rust conductors such as α-methylstyrene, unsaturated carboxylic acids such as crotonic acid, maleic acid, itaconic acid, or Mention may be made of its anhydride, hydroxyethyl methacrylate, hydroxyethyl acrylate, diethylaminoethyl methacrylate, N-vinylpyrrolidone, and the like.

The monomer (B
), in the general formula (I), preferably, mackerel represents an optionally substituted alkyl group having a total carbon number of 72 or more or an alkenyl group having a carbon number of 7.2 or more, and X is -COO-1R' ■ -CONH-1 or -CON (however, R' is carbonff1a
7 to 32 aliphatic groups (aliphatic groups include, for example, alkyl groups, alkenyl groups, or aralkyl groups)]
, and Yl and Y2 may be the same or different and represent a hydrogen atom, a methyl group, -COOR" or -CH2COOR"
(However, 几" indicates an alkyl group, an alkenyl group, an aralkyl group having a carbon number of up to 32, or a cycloalkyl group with a class number of up to 32.)

Specific examples of the monomer (B) represented by the above general formula (I) include aliphatic groups having a total carbon number of ♂ to 32 (including substituents such as halogen atoms, hydroxy groups, amine groups, alkoxy groups, etc.). acrylic acid, methacrylic acid, crotonic acid, maleic acid, itacon, which may contain a carbon-return bond in the main chain with a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Esters of unsaturated carboxylic acids such as acids (aliphatic groups such as decyl, dotecyl, tridecyl, tetradecyl, hexadecyl,
octadecyl group, docosanyl group, dodecenyl group, hexadecenyl group, oleyl group, lylyl group, tocosenyl group, etc.), the above-mentioned amides of unsaturated carboxylic acids (aliphatic groups are the same as those shown for esters), etc. can be mentioned.

The dispersion resin of the present invention is composed of at least 7 or more types of monomers (A) and monomers (B), and the important thing is that the resin synthesized from these monomers is mixed with the non-aqueous solvent. If it is insoluble, a desired dispersed 4νI fat can be obtained. Specifically, for the monomer (A) to be insolubilized, general formula (I)
The monomer (B) represented by θ,! ~! It is preferred to use θ% by weight.

On the other hand, when producing the dispersion resin of the present invention, polymerization and granulation may be carried out in the presence of a soluble resin for dispersion stabilization in the solvent.

The soluble resin used is a resin that does not contain a graft group that polymerizes with the monomer, and a conventionally known dispersion stabilizer can be used. That is, various synthetic resins or natural resins soluble in non-aqueous solvents are used singly or in combination of two or more. For example, an alkyl chain or an alkenyl chain having a total carbon number of g to 32 [These fatty radicals may contain substituents such as a halogen atom, a hydroxy group, an amino group, an alkoxy group, or an oxygen atom, a sulfur atom, A carbon-carbon bond in the main chain may be mediated by a heteroatom such as a nitrogen atom.]
esters of acrylic acid, metafluric acid, or crotonic acid, higher fatty acid vinyls, alkyl vinyl ethers, or olefins such as butadiene, isoprene, diynebutylene, etc., or copolymers by combining one or more of them, Furthermore, monomers that form polymers soluble in non-aqueous solvents as described above, and various monomers/species or more as shown below in proportions within a range that allows the resulting copolymer to be soluble in non-aqueous solvents. A copolymer obtained by polymerizing these can also be used.

Examples of such monomers include vinyl acetate, allyl acetate; methyl, ethyl, or propyl esters of acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid; styrene derivatives (such as styrene, vinyltoluene, α-methylstyrene, etc.); unsaturated carmenic acids or their acid anhydrides such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid; hydroxyethyl methacrylate, hydroxyethyl acrylate, diethylamine ethyl methacrylate, N-vinylprolidone ,
Acrylamide, acrylonitrile, cochloroethyl methacrylate, 'l' 12-trifluoroethyl methacrylate, and various polarity groups such as doxy groups, amino groups, amide groups, cyano groups, sulfonic acid groups, carbonyl groups, halogen atoms, heterocycles, etc. Examples include monomers containing groups.

Alternatively, in addition to the above synthetic resins, alkyd resins, alkyd resins modified with various fatty acids, 7 W = i
? f″′″″1””)’yVl’7t!M””;l″0
“”゛“ (I can be there.

Further, the molecular weight of the dispersion resin of the present invention is 703 to 106,
Preferably it is 104-106.

Specific examples of these dispersion resins are shown below, but the scope of the present invention is not limited thereto.

H3 H3 (I-1). Depending on the situation, the above-mentioned soluble resin for dispersion stabilization may be heated and polymerized in a non-aqueous solvent in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, or butyl lithium. .Specifically 1□ Specifically, a method of adding a polymerization initiator to a mixed solution of monomer (A) and monomer (B) and further resin, monomer (A) and monomer (B) is added dropwise to a non-aqueous solvent in which the resin may be dissolved together with a polymerization initiator, or when a resin is used, the total amount and monomer (8) and monomer (8) are added together.
A method of optionally adding the remaining monomer mixture together with a polymerization initiator into a mixed solution containing a part of the mixture of B), and furthermore, a method of mixing the resin and O monomer in a non-aqueous solvent. There are methods in which a solution is optionally added together with a polymerization initiator, and any method can be used for production.

The total amount of monomer (A) and monomer (B) is 70% of the nonaqueous solvent.
5 to 0 parts by weight? It's about θ heavy and I like tL<10~! θ is the heavy view part.

When using a soluble resin as a dispersion stabilizer, the amount is 7 to 700 parts by weight, preferably 50 parts by weight, based on 700 parts by weight of the total monomers used above.

The amount of heavy @ initiator is 0.7 to t% (weight) of the total active mass
is appropriate.

Also, what is the polymerization temperature? The reaction time is preferably about θ~/♂00(', preferably 60~/200C, and the reaction time is /~/j hours).

The colored dispersed resin particles of the present invention are obtained by dissolving at least /m of an organic dye and, if necessary, the dye in a dispersion containing resin particles obtained by the polymerization granulation method as described above, and dissolving the dye in the non-aqueous solvent. It can be produced by adding a second solvent that is miscible with the resin particles and capable of at least swelling the resin particles, and heating the mixture.

For example, physical dyeing methods can be used as one of the seven methods for coloring resin. That is, heat dyeing is performed using a dye that is sparingly soluble or insoluble in the non-aqueous solvent and is soluble in the monomers that are the constituent components of the copolymer. A second solvent may also be present.

This is because the dye used is thought to be dyed by impregnating or adhering to the copolymer particles. Therefore, depending on the constituent components of the copolymer resin, the most suitable dye for dyeing is selected. It is preferable to choose.

Examples include disperse dyes known for dyeing polyester, polyacrylic resin, polyacrylonitrile resin, and the like. Specifically, Cetti ton Fas.
t Yettow RR, KayaAonFas
t Yettow G, Kayaton F
astBrown R, Kayaton Fast
5cart B.

CetAiton Fast l(+ubine
J.B.

Cettiton Fast 5carlet
R, KayatonFast Rubine B
Kayaton Fast Red R.

Miketon Fast Pink FR.

Kayaton Fast Viotet BB
Miketon Fast Viojet
BB, Kaya tonFast Btue
FN+ Kayaton Fast Btu
eGreen B, Sumikaron Y
e4! ow FG.

Sumikaron Butue BR, Sumik
aronNavy Blue R etc. (Dye product name, CattitOn:B
ASF, Kayaton: Nippon Kayaku Miket
on: Mitsui Chemicals ■, Sumikaron: Resident Chemicals ■
are represented respectively. ) Other examples include basic dyes, specific examples include Ftavinp /G, ~uramir, e
+Crystat Viotet, Methytene
Btue +Rhodamine jG, Ma/
, achite Green.

Sumiacryt Yettow JG, Su
Sumi
acrytOranyL G.

8umiacryt 0ranfe R, Aizen
CathitonPink, Aizen
Cathi Aon Red tBH.

Aizen Ba5ic Cyaninc l+
G.H.

Pr imocyan ine B
, Aize nCathiton: Hodogaya Chemical■), or Masao Iizuka, "Dyeing Industry"/3
,4t2ri~4tgu? (Dye described in /96 etc. can also be mentioned.

As the second solvent which can dissolve the dye, which can be used as required, is miscible with the non-polar solvent, and can at least swell the resin particles, a resin is preferably used! A monomer that is at least one constituent of The advantage of using a monomer is that the dissolution of resin particles that occurs when using other solvents does not cause adverse effects such as aggregation. However, as the second solvent of the present invention, it is also possible to use a solvent that satisfies the above conditions, such as ethanolopacetone and ethyl vinegar, by adjusting the amount used.

For example, if a sufficient amount of monomer residue remains when resin particles are formed by the polymerization granulation method described above, there is no need to add the second solvent to the resin particle dispersion, but the monomer residue If the amount of the monomer and the second solvent is less than 7710% based on the weight of the resin particles in the dispersion,
It is necessary to add medium No. 208 to the dispersion liquid so that the above results are achieved.

The second solvent may be added to the resin particle dispersion by adding the dye as a solution in the solvent, or by adding the dye to the dispersion as a powder and adding it to the dispersion at hIJ or after the addition of the dye. May be added. In any case, it is fine as long as the dye and the second solvent are contained in the resin particle dispersion in the next step of removing the second solvent.

However, the addition of these dyes and the second solvent need not necessarily be completed before the subsequent step of removing the second solvent, for example adding the dye and/or the second solvent while removing the second solvent. of? You may also replenish your plans. “
In addition, the second solvent has a temperature of θ relative to zH7 of the resin particles in the dispersion
, /-10 times, but considering the vacuum removal in the subsequent step (it is preferable that the volume does not exceed /3 of the volume of the fat particle dispersion).

However, depending on the types of dye, resin particles, nonaqueous solvent, and second solvent used, there may be an optimum ratio outside the above range, so the ratio is not limited to this range.

In this manner, the dye and the second solvent are dropped into the dispersion liquid through the V strainer, and the second solvent is removed while the dye and the second solvent are completely mixed or after the mixing is completed. The step of removing the second solvent is carried out by reducing the pressure of the mixed dispersion of the dye and the second solvent, or by applying heat while reducing the pressure.
Ru.

The amount of dye used is 0% of the amount of resin particles in the dispersion.
．． ! It is fine if the weight is at least σ, but in order to obtain good color density, it is preferably at least 3% by weight.

In addition, the maximum usage amount of dye is not particularly limited, but it is usually
It is used in less than % by weight.

The heating temperature for dyeing is 4toQ~/j'QOC, preferably /θ~/2θ0C. Also, the heating time is 30 minutes to 72 hours, preferably 1 hour! It's time.

Another method for dyeing dispersed resins is mordant dyeing. This method uses a basic dye (cationic dye) when at least seven components constituting the dispersed resin particles contain an acidic group (for example, a carboxy group), or If the components contain basic groups, they can each be dyed with acid dyes. This is a so-called method based on ionic bonding between an acidic group and a basic group.

As basic dyes for dyeing the resin particles made of a copolymer containing a carboxyl group, examples of the above-mentioned dyes, Aizen Victoria BAuetsu BH, Aizen Victoria Pur
e B tueBOH, Aizen Cati
ton Gray BLH.

Aizen CathiAon Btack G
On the other hand, dyes that dye the resin particles made of copolymers containing basic groups include dyes containing carboxylic groups or sulfonic acid groups. For example, Kiton B
tue A ((IHA), AAizarine
AstrotB (Ikeda Chemical ■), KayanotB
tue N, 2G (Nippon Kayaku ■), Kayac
yL Btue B L ((Nippon Kayaku@), Sum
inotFast Sky Btue B (Living Chemistry■), At1zatine Lifeh Bro
wn BL (Mitsubishi Kasei @) 1Aizen Ho5in
e ()H (Hodogaya Chemical■), At1zarinot
R (Yamada Kagaku ■) and the like. The carboxy group or sulfonic acid contained in these acidic dyes can be used in the form of a free acid, a mineral salt, a salt with an organic base, or a quaternary ammonium salt, if necessary.
! The amount of dye used and the dyeing conditions are the same as those for the physical dyeing described above.

The non-aqueous colored dispersion resin produced according to the present invention as described above exists as fine particles with a uniform particle size distribution, and at the same time exhibits very stable dispersibility, especially in the developing device. Good dispersibility even after repeated use,
In addition, redispersion is easy, and no stains are observed on the reeds or other parts of the device.

Various additives may be added to the liquid imaging agent of the present invention in order to strengthen charging characteristics or improve image quality, etc., as necessary. Volume, No. 2
No. 4t4 is specifically described on page 4.

For example, di-2-ethylhexyl sulfosuccinate metal salt,
Examples of additives include naphthenic acid metal salts, higher fatty acid metal salts, lecithin, poly(vinylpyrrolidone) copolymers containing hemi-maleic acid amide components, or copolymers containing hemi-maleic acid amide and maleimide components.

The amounts of each of the main components of the liquid developer of the present invention will be explained below.

The toner particles mainly composed of a colored copolymer or resin are 0° with respect to 7000 parts by weight of the carrier liquid! Weight section~!
I'd prefer Ojutsubu. If it is less than 0.5 parts by weight, the image will be insufficient! When the weight is 0 or more, capri is likely to occur in non-image areas. A carrier liquid soluble resin such as the above-mentioned dispersion stabilizer can also be used if necessary, and may be added in an amount of about 11 parts by weight of 70°tI to 10θ parts by weight per part of 7000 parts of the housing liquid. is the carrier residue 10θ
A preferable amount is 0.007 to 7.0 parts by weight based on 0 weight parts.

Furthermore, various additives may be added as necessary, and the upper limit of the total amount of these additives is regulated by the resistance of the developer. That is, if the electrical resistance of the liquid developer with toner particles removed is less than 109Ω·α, it becomes difficult to obtain good quality gradation, so the amount of each additive added is
It is necessary to control within this limit.

"Example" The embodiments of the present invention are illustrated below, but the content of the present invention is not limited thereto.

Production example 1 of tlε anterograde particles: Compound vinyl acetate 700 of specific example (1)? , lauryl methacrylate 2Of and indodecane 3♂0? A mixed solution of 02.2'-azobis(imbutyronitrile) (abbreviation A, 1.B, N)/, which was heated to a temperature of 7 (170 °C) while stirring under a nitrogen stream,
7F was added and reacted for some time. After 30 minutes of adding initiator -
The solution begins to become cloudy and the reaction temperature does not rise until ♂t 0c-5. After cooling, the white dispersion obtained by passing it through a 1.2 QO mesh nylon cloth has a high polymerization rate! ! 9C, average particle size 0.2
Made of micron latex.

Production example 2 of resin particles: Compound vinyl acetate 100? of specific example (2) , stearyl methacrylate)/, 2F and isododecane 3? ! ? The mixed solution was heated to a temperature of 70'c while stirring under a nitrogen stream. A.1. B, N/, 7y
was added and reacted for 6 hours. After a few minutes after adding the initiator, the solution begins to become cloudy. What is the reaction temperature? ! It rose to OC. After cooling, what is the polymerization rate of the white dispersion obtained by passing it through a nylon cloth with 0 mesh? ! % and had an average particle size of 0.20 μm.

Production Example 3 of Resin Particles: Compound Vinyl Acetate/θ0f1 Croton Ugly! of Specific Example (16) ? , stearyl ivy acrylate 10r and U Aitsuno ξ-E4? The mixed solution was heated to a temperature of 700C while stirring under a nitrogen stream. A,
1. B, N/, 7r were added, and the reaction temperature was kept at low temperature/Qθ0 for 6 hours.
The mixture was stirred for 7 hours, and the remaining vinyl acetate was distilled off. cooling? & t%, and the average particle size of the latex was 0.76 μm.

Production example 4 of resin particles: Compound of specific example (1) (using dispersion stabilizer) poly(lauryl methacrylate)/2f1 vinyl acetate 100f, lauryl methacrylate 3P and indodecane 3? ! ? The mixed solution was heated to 70°C while stirring under a nitrogen stream. A.I.

B, N/, 7F1ka. Eh, 6, 9. picture. □ 30 minutes after adding Step 1, the solution begins to become cloudy. What is the reaction temperature? It rose until evening QC. After cooling, the white dispersion obtained by passing it through a 200 mt nylon cloth has a polymerization rate of ? ! %, average particle size θ
, -〇μ was normal latex.

Manufacturing example 5 of resin particles: Compound of specific example (2) (using dispersion stabilizer) poly(lauryl methacrylate)/2f, vinyl acetate 100f, stearyl methacrylate 4t? and Indo Deccan 3? Evening 2
The mixed solution was heated to 70°C while stirring under a nitrogen stream.
It was heated to

Eight, 1. B, N/, 77 were added and reacted for 3 hours.

After a minute of adding the initiator, the solution begins to become cloudy. What is the reaction temperature? ! The temperature rose to 0C. After cooling, what is the polymerization rate of the white dispersion obtained by passing it through a 200 mesh nylon cloth? The latex had an average particle size Q of 23 μm at r%.

Production example 6 of resin particles: Compound of specific example (16) (using dispersion stabilizer) poly(lauryl methacrylate) t1 vinyl acetate 100f1 crotonic acid j?, stearyl methacrylate)/P and isoper 1)% 4?2 The mixed solution was heated to a temperature of 700 (: A, 1.B, N/, 7) while stirring under a nitrogen stream.
After reacting for 2 hours, the temperature was raised to θ0°C and the mixture was stirred for 7 hours. After cooling, the obtained white dispersion was passed through a 200-mesh nylon cloth, and the polymerization rate was ? At t%,
The latex had an average particle size of 0176 μm.

Production example 7 of resin particles: Specific example (one compound (using dispersion stabilizer) poly(stearyl methacrylate)) 4F, vinyl acetate 100y, allyl acetate 2, stearyl methacrylate r? A mixed solution of Isopar Hg g g y was heated to a temperature of 70° CK while stirring under a nitrogen stream. k, 1. B, N/, 6
After adding f and reacting for 6 hours, the temperature was raised to /θ0QC and stirred for -1:17 hours.

After cooling, the obtained white dispersion has a high polymerization rate! At 7%, the average particle size is 0. /! It was micrometer latex.

Production Example 8 of Resin Particles: Compound of Specific Example (9) (using dispersion stabilizer) poly(stearyl methacrylate)/, 2F, methacrylic 32 methylg! 2. Stearyl meccrylate/79 and Isopar G! A mixed solution of Otsu02 was heated to temperature Otsu QC while stirring under a nitrogen stream.2'-Azobis-(2,
41-dimethylnoζleronitrile) o, ty added Z
Time reacted. After that, raise the temperature to 10θ0C and let it roar 7
Stir for hours.

After cooling, the white dispersion obtained by passing through a 20θ mesh nylon cloth was a latex with a polymerization rate of 0% and an average particle size of 0./4tμm.

Production example 9 of resin particles (proportionate person) Kuzukuri; IJ! The procedure was carried out in the same manner except for lauryl methacrylate, and the obtained white dispersion had a polymerization rate cr! The latex had an average particle size of θ, lpm in %.

Production Example 10 of Resin Particles (Comparative Example B) Poly(2uryl methacrylate)/Yo? , 10 oy of vinyl acetate, and 3.1' j f of -(sodecane), and the subsequent operations were carried out in the same manner as in Production Example 4.

The white dispersion obtained is a polymerized part! Average particle size 0 at r%, /♂
Production Example 11 (Comparative Example C) Lauryl methacrylate 3 was added to the white latex obtained in Production Example 9. Added and stirred well.

Production Example 12 of Resin Particles (Comparative Example D) In Production Example 5, instead of stearyl methacrylate, υ
, n-butyl methacrylatene, Z? The other procedures were performed in the same manner. What is the polymerization rate of the obtained white dispersion? The latex had an average particle size of 0.32 μtn.

Example 1 White dispersion obtained in Production Example 1 of resin particles/θOri, Sumikalon Black/,! ? and a mixture of vinyl acetate/gP was heated to a temperature of θθ0C and heated and stirred for 2 hours. Afterwards, remove the reflux vessel at the same temperature, stir for 3 hours, and... 8
The medium was distilled off.

After cooling to room temperature, the remaining dye was removed by passing it through a -200 mesh nylon cloth, resulting in an average particle size of 0°. ””“f)Me (1)m mfj□ t&4m'x
K4=Sfc°' [1 Above point 8 Resin dispersion! 27,/-ocucudecene-manninic acid half-octadecylamide copolymer θ.

03? A liquid developer was prepared by diluting Shell Silua/, /l.

(To Comparative Developer ~ C) Three types of comparative liquid developers A, B, and C were prepared by replacing the resin dispersion with the following resin particles in the above production example.

Comparative liquid developer A: Resin dispersion of resin particle production example 10 B: 11 〃 〃 C: tt 12 tt These liquid developers were processed using a fully automatic electronic plate making machine ELP Co♂Q (Fuji Photo Film ELP master (g ± photographic film @ Yin) is used as a developer for the back side), and E[, IP master, 20
After processing the θθ sheets, the presence or absence of toner adhesion stains on the developing technique 1r1 was observed.

The results are shown in Table/.

Table/Developers of Melon 1 to A4 in Table 7 were prepared in exactly the same manner except for the resin dispersion. Only the developer made from the resin particles of the present invention did not stain the developing device at all, but in Comparative Examples A to C, toner adhesion was observed around the roller. When monomer B of developer A-C is not used (Comparative example A) In the dispersion after polymerization and granulation of particles Polymerization with post-addition of monomer B (Comparative example C) In the case where a polymer of monomer B was added in advance and granulated, assuming that the polymer was polymerized completely independently of monomer A forming particles (Comparative Example B)
This shows that these are clearly different from the resin particles of the present invention.

The master plates for offset printing (BI, P master) obtained using the developer of the present invention had very clear images both in the first developed one and in the one after 2000 sheets were developed. . Furthermore, these master plates,
When p3ooo sheets were printed using the conventional method, clear printed matter could be obtained even after printing 3θ00 sheets.

In addition, the master plates for offset printing obtained using the developers of Comparative Examples A to C had clear images when first developed, but after processing 2000 sheets, there were some missing characters and The image was unclear, with smudges and burrs in the solid areas.

Example 2 White dispersion obtained in Production Example 5 of Resin Particles 100? , Sumikaron Navy Blue/,! ? and vinyl acetate/! ?
The mixture was heated to 100°C and stirred for 5 hours. Thereafter, the reflux vessel was removed, the mixture was stirred for an additional y hours, and the solvent was distilled off. After cooling to room temperature, the remaining dye was removed by passing it through a 200 mesh nylon cloth.
A blue resin dispersion with an average particle size of 0.2 μm was obtained.

A liquid developing agent for electrostatic photography was prepared by dispersing the above resin dispersion 30t1 diynebutylene-half-maleic acid octadecylamide copolymer o, oat in Shell Sila /, /l.

(Comparative Developer D) In the above production example, a comparative liquid developer D1 was prepared by replacing the resin dispersion with the following resin particles.

Comparative liquid developer D=resin dispersion of resin particle production example 1) These liquid developers were processed using a fully automatic electronic plate making machine ELF2r0.
It is used as a developer for ELF Master (manufactured by Fuji Photo Film), an electrophotographic light-sensitive material
) was exposed and developed.

Eyo, ELPff-1' t20001f! ni,,&f
MLJc*. (The presence or absence of toner adhesion to the developing device was observed.

The results are shown in Table 2. Only the developer made using the resin particles of the present invention did not stain the developing device at all, while the comparative example showed toner adhesion around the roller. It was done. The comparative example uses resin particles obtained by using n-butyl methacrylate as the monomer (B) in an equimolar amount with stearyl methacrylate as the monomer (B) used in the resin particles of the present invention. .

These results demonstrate that the resin particles of the present invention are clearly superior.

In addition, the master plate for offset printing obtained using the developer of the present invention has a 2ooo
Very clear images were also obtained after sheet processing.

Furthermore, these master plates are
After printing o sheets, clear prints could be obtained even after 3000 sheets.

On the other hand, the master plates obtained using the developers of Comparative Example and Comparative Example E had clear images when first developed, but after processing 2000 sheets, there were missing characters and solid images. The result was an unclear image with smearing and soil blemishes in the parts.

Example 3 White dispersion obtained in Resin Particle Production Example 6/QOj'
Aizen Ba5ic Cyanine &
GHB3? and ethanol/yo? the mixture at a temperature of 7
The mixture was heated to a temperature of 0.00 to 0.000 m° and stirred for several hours. Thereafter, the mixture was stirred at the same temperature for 2 hours while reducing the pressure using an aspirator.

After cooling, the remaining dye was removed by passing it through a 200-mesh nylon cloth until the average particle size was 0. A blue resin dispersion with a particle size of 1/l, .mu.m was obtained.

A liquid developer was prepared by diluting the above blue resin dispersion 32f and /-octadecene-octadecylamide semi-maleic acid copolymer 0°04tf in Isopar Hat.

When this was developed using the same apparatus as in Example 1, 20
Even after developing 00 sheets, no toner adhesion stains were observed on the device. Moreover, the image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after printing 300 sheets was also very clear.

Examples 4 to 7 Liquid developers were prepared in the same manner as in Example 3 except that the following dyes were used in place of the Victoria Blue B dye.

When developed using the same apparatus as in Example 1, the same results as in Example 3 were obtained.

Example 4 Aizen Catiton Ye
ttowjGLH (Hodogaya Chemical) 5 Aizen Astra Phtoxine
FF (Hodogaya Chemical) 6Aizen Cathiton Pink F
GH (Hodogaya Chemical) 7 Methylene Blue Example 8 Kayaton Fast Brown R (
Nippon Kayaku JJ) 0, 6 OPlMiketon
B'ast PinkPR (manufactured by Mitsui Chemicals) 0. /J
r? , Victoria Blue B/, OJ-? and vinyl acetate/62 were added respectively and the temperature? The mixture was stirred at 0°C for 2 hours, and the reflux vessel was drained, and the mixture was stirred for 2 hours. After cooling to room temperature, the resulting black resin dispersion was passed through a 2Q0 mesh nylon cloth and had an average particle size of θ,/j μm.

The above black resin dispersion 32? , octadecyl vinyl ether-semi-maleic acid hexadecylamide copolymer 0.0j
A liquid developer was prepared by diluting f to Isopar G/l.

2□E□1] 10 months. Ya□yoyo9.・1
Even after developing 2,000 sheets, toner adhesion to the device still remains.
I couldn't see it at all. In addition, the image quality of the seven master plates for offset printing obtained and the image quality of the printed matter after printing 1000 sheets were both clear.

After leaving the developer for 3 months, the above and all 1. −
A second similar treatment was performed, but there was no difference at all from before aging.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment
φ Showa! 2nd year 1st/3rd

Claims (1)

[Claims] Electrical resistance value is 10^9Ω・cm or more and dielectric constant is 3.5
In an electrostatographic liquid developer comprising at least a colored resin dispersed in the following carrier liquid, the resin is
Liquid developer for electrostatography characterized by being a colored copolymer resin obtained by the methods of 1) and (2) (1) It is soluble in non-aqueous solvents, but is Monofunctional monomer (A) and the following general formula (I) that become insolubilized by
A dispersion of a copolymer resin is prepared by polymerizing at least one monomer (B) which causes a copolymerization reaction with the monomer (A). (2) A colored copolymer resin is produced by adding at least one organic dye to the dispersion obtained in (1) and heating the mixture. General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc. are available▼ In formula (I), R is an aliphatic group with 8 or more carbon atoms, and X is
-COO-, -CONH-, ▲Mathematical formulas, chemical formulas, tables, etc.▼(R' indicates an aliphatic group), -OCO-, -C
H_2OCO- or -O-, Y_1 and Y_2 may be the same or different and represent a hydrogen atom, an alkyl group, -COOR'' or -CH_2COOR''(R'' represents an aliphatic group).