JPS62231265A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To obtain the titled developer having improved dispersion stability, redispersibility and fixing properties by incorporating a colored copolymer resin which is obtd. by a specific method to the titled developer dispersed the colored resin in a liquid carrier. CONSTITUTION:The colored copolymer resin obtd. by the following step is dispersed in the liquid carrier having >=10<9>OMEGA.cm electric resistance and <=3.5 dielectric constant. The dispersion solution of the copolymer resin is prepared by polymerizing a monofunctional monomer A which is soluble to a non-aqueous solvent and makes insoluble to the solvent by polymerizing it and a monomer B which contains >=2 kinds of polar groups and/or polar linking groups in the non-aqueous solvent solution thereof. The colored copolymer resin is prepared by adding a kind of org. dyestuff to the obtd. dispersion solution followed by heating it. The monomer A is composed of a vinylether of 1-6C aliphatic carboxylic acid, etc. In the formula, V is -O- or -COO group, etc., Y is hydrogen or halogen atom, X1 and X2 are each -O-, -S- or -CO-, etc. Thus, the developer having excellent storage property, stability, redispersibility and fixing property is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION "Field of Industrial Application" The present invention is applicable to electrical resistance of 109Ω on a drawing board and dielectric constant of 3. j
This relates to an electrostatographic liquid developer comprising a small amount of colored resin dispersed in the following carrier liquid, and in particular, it is a liquid developer with excellent storage stability, stability, redispersibility, and fixability. Regarding drugs.

``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. is uniformly dispersed in a highly insulating, low dielectric constant liquid such as a petroleum-based aliphatic hydrocarbon, and the charge JfIL% of the dispersed particles is uniformly dispersed.
In addition, metal soap, lecithin, linseed oil, higher fatty acids, polymers containing vinylpyrrolidone, etc. are added for the purpose of strengthening.

Such a developer undergoes 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.
It forms a visible image (copied image), but in conventional liquid developers, the dispersion stabilizing resin and charge control agent diffuse into the liquid, making the charging characteristics unclear, and as a result, the image cannot be printed once. However, there were drawbacks such as a decrease in fixing properties and an increase in background smearing, which made the copied image unclear.

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

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

As a method for improving these problems, a method has been proposed in which pigment coating IfIK polymer such as carbon black is grafted to stabilize the dispersion of particles. However, the developer obtained in this manner has the drawback that the relative 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, there is a problem that the oil sensitivity to the printing ink and the number of printing sheets are insufficient due to the above-mentioned reasons. 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 stabilizing resin containing a graft group, and the fine resin particles are used as toner particles is disclosed in U.S. Pat. . 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 (
When the toner is placed in an actual developing device and used, the toner that adheres to various parts of the device hardens into a film, making it difficult to redisperse and furthermore causing equipment failure and smudging of copied images. There were some drawbacks, such as:

In addition, in forming preferred resin particles by the above method, there are significant restrictions on the combination of dispersion stabilizer and monomer to be used.
In general, the particles end up containing a large amount of coarse particles and have a wide particle size distribution. Furthermore, there are problems such as the fact that a preferred dispersion stabilizer must be synthesized through a complicated manufacturing process.

Further, as a method for obtaining colored toner particles using the above-mentioned polymerization granulation method, there is a method described in JP-A-3-12111. This method uses, for example, K in a non-polar solvent containing a charge control agent, a monomer that is soluble in the non-polar solvent in its monomer state but becomes insoluble when polymerized, a dye that is soluble in the monomer but insoluble in the non-polar solvent, and a dye that is soluble in the monomer but insoluble in the non-polar solvent. This is a method in which a polymerization reaction is carried out while dropping a solution consisting of the most important initiator.

According to this method, dissolution of the monomer in the non-polar solvent occurs simultaneously with the dropwise addition of the solution, thereby forming fine crystals of the dye, and then polymerization of the monomer takes place, so that the polymer of the monomer is formed in the fine crystals of the dye. An electrostatographic liquid developer having an adsorbed structure 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 phenolic hydroxyl groups, phenylamino groups, and nitrophenyl groups can exist stably, and many dyes with these chemical structures can be used as radical polymerization inhibitors. It acts as a substance that inhibits radical polymerization of monomers. Therefore, when carrying out the radical polymerization of seven polymers as described above, if a dye is present, the 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 must have all the properties as described above (insoluble in non-polar solvents and soluble in the monomers of the resin to be polymerized). Therefore, the range of selection of dyes and dyes to be used is extremely narrow, and there is also the disadvantage that many dyes cannot be used in this method. As mentioned above, there was a problem in that the dispersion stability of particles produced by these polymerization granulation methods was insufficient and it was difficult to put them 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 electrostatic photographs and various types of electrostatic transfers 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. It is to be.

``Means for Solving the Problems'' The present invention provides an electrostatic photographic method comprising dispersing a small amount of colored resin in a carrier liquid having an electrical resistance value of 109 Ω·α or more and a dielectric constant of 36 or less. The present invention is a liquid developer for electrostatic photography, characterized in that the resin is a colored copolymer resin obtained in the following steps (I) and (2).

(Li) In the presence of a resin that is soluble in a non-aqueous solvent and does not contain a graft group that polymerizes with the monomer, it is soluble in the solvent, but
Monofunctional monomer (A) that becomes insolubilized by polymerization
and a solution containing at least one type of monomer (B) containing at least two or more types of polar groups and/or polar linking groups represented by the general formula ([), respectively. Make a dispersion of copolymer resin.

General formula (I) CH=C ■ V4: R, -X1YR2-X2-7y (2) By adding at least /a organic dye to the dispersion obtained in (I) and heating it, Make a colored copolymer resin.

In general formula (1), ■ is -0-1-COO-1-
OCO-1-CH20CO-1-8O-1-CON H
-1-3O2NH-1' group or bonding group in general formula (1): +R1-X, ←-+R2-X2→-Y with the same symbol m
n Express.

Y is a hydrogen atom or a halogen atom, -0H1-CN, -
NH-COOH, -8o3H.

Represents a hydrocarbon group with carbon number/%/l that may be substituted with -PO3H.

X and X2 may be the same or different from each other (, -0-1-S-1-CQ-1-CO2-1 or -NHCON
Represents H- (Y□, Y2, Y3, Y4 and Y5 are the same symbols as Y above).

R1 and R2 may be the same or different from each other, may be substituted, or -CH- (, indicates the same symbol as X1 and X2 above, and R4 is the number of carbon atoms that may be substituted /-/
f represents a hydrocarbon group, and Y6 represents the same symbol as Y] represents a hydrocarbon group having 7 to 1 carbon atoms.

In addition, a0 and R2 may be the same or different from each other (, hydrogen atom, hydrocarbon group, -cooz, or cooz with a hydrocarbon group interposed (however, 2 represents a hydrogen atom or a hydrocarbon group that may be substituted) ).

Furthermore, m, n and p may each be the same or different (O
Or represents an integer from 1 to μ.

Used in the present invention, the electrical resistance is 9Ω・α or more,
i conductivity is 3. Preferably, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons, or the like can be used as the carrier liquid below. From the viewpoint of volatility, stability, toxicity, odor, etc., Aitunoe + B, which is a petroleum solvent of octane, isooctane, decane, isodecane, nonane, dodecane, isododecane, decalin, and isoparaffin, is more preferable.
, Isopar G, Iso, +1 + H, Isopar L
(Isopar: Exxon product name), Shell Silua 1
(trade name of Shell Oil Co.), Amsco OMS, Amsco μ60 solvent (trade name of Spirits Co.), etc. are used alone or in combination.

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

Basically, any non-aqueous solvent can be used as long as it is miscible with the carrier liquid of the electrostatic photographic liquid developer, but the same solvent as the carrier liquid may be used 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,
Preferred are decane, isodeca/, nonane, dodecane, isododecane, imparaffin-based petroleum solvents such as Isopar E, Isopar G1, Isopar H17'f://''-L, Shell Silua/, and Amsco OM8.

The dispersion stabilizer required to polymerize monomers in a non-aqueous solvent and make the resulting solvent-insoluble polymer into a stable resin dispersion is a resin that does not contain a graft group that polymerizes with the monomer. A conventionally known dispersion stabilizer can be used. That is, various synthetic resins or natural resins soluble in non-aqueous solvents are used alone or in combination of two or more. For example, an alkyl chain or an alkenyl chain having a total carbon number of t to 32 [These aliphatic groups may contain substituents such as a halogen atom, a hydroxy group, an amino group, an alkoxy group (or an oxygen atom, a sulfur atom)] , esters of acrylic acid, methacrylic acid, or crotonic acid, higher fatty acid vinyls, alkyl vinyl ethers, or butadiene. , polymers such as olefins such as isoprene and diisoduthylene, or copolymers of two or more in combination, and monomers that form polymers soluble in non-aqueous solvents such as those mentioned above, and the resulting copolymers. It is also possible to use copolymers obtained by polymerizing various monomers/ai or more as shown below in a ratio within a range that is soluble in a non-aqueous solvent.

Examples of such monomers include vinyl acetate, allyl acetate, acrylic acid, methacrylic acid, methyl, ethyl or propyl esters of itaconate such as crotonic acid and maleic acid, styrene derivatives (flu hastyrene, vinyl toluene, α- methylstyrene, etc.), unsaturated carboxylic acids or their acid anhydrides such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itafonic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, diethylaminoethyl methacrylate, N-vinylpyrrolidone, acrylamide, Acrylonitrile/l/, 12-chloroethyl methacrylate, co, λ.

Hydroxy group, amino group, amide group, cyano group, sulfonic acid group, such as coated trichloroethyl methacrylate,
Examples include monomers containing various polar groups such as carbonyl groups, halogen atoms, and petero rings.

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.

The half-mer used in producing the non-aqueous dispersion resin is composed of a monofunctional monomer (A) that is soluble in the solvent but becomes insolubilized by polymerization, and a polar group represented by the general formula (1) above. and/or a monomer (B) containing at least -2 types of polar linking groups and copolymerizing with the monomer (A).
).

As the monomer (A), for example, vinyl esters or allyl esters of aliphatic carboxylic acids having 4 carbon atoms (propionic acetate, butyric acid, monochloroacetic acid, etc.), acrylic acid, methacrylic acid, crotonic acid, itacon acids, alkyl esters or alkylamides having 1 to 3 carbon atoms of unsaturated carboxylic acids such as maleic acid, styrene, vinyltoluene, styrene derivatives such as α-methylstyrene, acrylic acid, methacrylic acid, crotonic acid, maleic acid , unsaturated carboxylic acids or anhydrides thereof such as itaconic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl acrylate, diethylamine ethyl methacrylate, trimethyasilylpropyl methacrylate, N-vinylpyrrolidone, acrylonitrile, etc. be able to.

The monomer (B
) is further explained. In general formula (1), preferably, ■ is -〇-1-COO-1-OCO-1-C
H20CO-1-CONH- or -CON- (W is the total carbon number/%/l, optionally substituted alkyl group, total carbon number 2 to/l, optionally substituted alkenyl group, total carbon number j -/r optionally substituted alicyclic group or bonding group in general formula (1): +R1-X1)-+
Same as R2-X2ner Y-m
Indicates the symbol n. ] Y is a hydrogen atom or a halogen atom (e.g. chloro atom,
bromo atom, etc.), -OH, -CN.

The total number of carbon atoms that may be substituted with -COOH is 1%/l.

represents an aliphatic group (the aliphatic group is, for example, an alkyl group, an alkenyl group, or an aralkyl group).

X□ and X2 may be the same or different, and -0-1-S-1-CO-5-COO-1 and Y3 each represent the same symbol as Y above.

R1 and R2 may be the same or different from each other (or may be substituted, or (CH) X3, -) -y.

A hydrocarbon group having a carbon number of / , /co (the hydrocarbon group is an alkyl group, an alkenyl group, an aralkyl group, or an alicyclic group), which may be interposed in the bond of the main chain.

However, X3 and X4 may be the same or different, and the above X1,
The same symbol as X2 is shown, R4 is an optionally substituted alkylene group, alkenylene group or aralkyl group having / , / carbon atoms, and Y6 is the same symbol as Y above.

In addition, al and R2 may be the same or different from each other, and represent a hydrogen atom, a methyl group, -COOZ or -CH2COOZ(
Z is a hydrogen atom, carbon number 1 to 1 (indicates an alkyl group, alkenyl group, aralkyl group, or cycloalkyl group)
represents. Furthermore, m, n, and p may each be the same or different (, '%' represents the number 3.

Furthermore, more preferably, in formula (1), ■ is -COO-1
-CONH- or -CON-, a□, and R2
may be the same or different (represents a hydrogen atom, a mefAt group, -〇〇〇-Z or -CH2Cooz (z is an alkyl group having a carbon number of /, /2).

Furthermore, to give a specific example regarding R1 and R2, R'(-C+(R',R" is a hydrogen atom, an alkyl group,])
R" represents a rogen atom), (-CH=CH-)-1 (X3,
It is composed of any combination of atomic groups such as (X4, Y6, R4, and p have the same meanings as the above symbols).

Moreover, X□, X2, m, n and p represent the same symbols as described above. In addition, the total number of atoms of each atomic group of V, R□, Xl, R2, X2, and Y is t or more.

More specifically, monomer (B) can be exemplified by the following compounds.

(Re CH8 CH=C COO(CH2-20COC, H□.

(2) CH3 CH=(” COo(CH2)20COC1, H23(3)H CH2=C C00(CH2)20CO(CI(2),0COCH3
(4) CH3 CH2=C Coo(CH2), oOCOC, H43(s)
CH3 CH2=:C C00(CH2)1oCOOC8H17(7)
CH3 CH2=C C0NH(CH2) 6COOC8H1□(8)
CH3 CH2=C Coo (CH2)2NHCO(CH2) 3COOC
H3(e) II CH2=C Coo(CH2) 30COCH=CH-COOC,H
13(10) CH3 CH2:C C00CI(2CHCH20COC51-11□0CO
C, Hll (11) CI (3 CH2=C COOCH2CHCH20COC, H130COC3H
7 CI(3 CH2=C CONCH2CH20COC, H11 CH2CH20COC,H,, (13) CH3 ■ CH3 CH=CH Coo(CH2)1oOCOC6H,3(15)
CH3 (1s) H CH2=:C Coo (CH2) 20CO(CH2) 3 COO
CH2CH2αCH2CH 0CO(CH2)□. Qcoc3) (7) The dispersion resin of the present invention is composed of at least one of monomer B and monomer B, and the important thing is that the resin synthesized from these monomers is insoluble in the non-aqueous solvent. If there is, a desired dispersion resin can be obtained.

More specifically, it is preferable to use o, or to 3θff% of monomer B represented by general formula (1) with respect to monomer A to be insolubilized, and more preferably o, or-zz.
The amount is %. Moreover, the molecular weight of the dispersion resin of the present invention is IQ%IQ
and preferably 10 −10 .

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

(Hiro CH3 Φ)7H3 (d) CH3 (e) CHa OCOC5H1l -3g ・--6 In order to produce the dispersion resin used in the present invention as described above, generally, the above-mentioned dispersion stabilizing resin, monomer (A) and monomer (B) in a non-aqueous solvent with benzoyl peroxide.
The polymerization may be carried out by heating in the presence of a polymerization initiator such as azobisisobutyronitrile butyllithium. Specifically, a method of adding a polymerization initiator to a mixed solution of resin, monomer (A), and monomer (B), and a method of adding a polymerization initiator to a mixed solution of resin, monomer (A), and monomer (B); Add (B) dropwise together with a polymerization initiator [
Alternatively, a method in which the remaining monomer mixture is optionally added together with a polymerization initiator into a mixed solution containing the entire amount of the resin and a portion of the mixture of monomers (A) and monomers (B);
Furthermore, a mixed solution of resin and monomer in a non-aqueous solvent,
There are methods of optionally adding it together with a polymerization initiator, and it can be produced using any of these methods.

The total amount of monomer (A) and monomer CB) is 10% of the nonaqueous solvent.
The amount is about 5-toxx parts per 0 parts by weight, preferably 10 to 10 parts by weight.

The amount of the soluble resin as a dispersion stabilizer is 1%/QQ parts by weight, preferably 5 to 50 parts by weight, based on the ioo parts by weight of the total monomers used above.

The amount of polymerization initiator is 0.0% of the total monomer amount. /, J% (weight i)
is appropriate.

Further, the polymerization temperature is about j0 to /r00c, preferably to-ixooc, and the reaction time is preferably / to /.

The colored dispersed resin particles of the present invention are added to a dispersion liquid containing resin particles obtained by the polymerization granulation method as described above (by dissolving one kind of organic dye and, if necessary, the dye, and dissolving the non-organic dye). It can be produced by adding a second solvent that is miscible with the water solvent and capable of swelling the resin particles in a small amount, and heating.

For example, a physical dyeing method can be used as one method for coloring the resin. That is, heat dyeing is carried out using a dye that is sparingly soluble or insoluble in the non-aqueous solvent and soluble in the copolymer, which is a component of the copolymer. A second solvent may also be present.

This is presumed to be due to the dye being impregnated into or attached to the copolymer particles.

Therefore, it is preferable to select the most suitable dye for dyeing depending on the constituent components of the copolymer resin.

Examples include disperse dyes known for dyeing polyester, polyacrylic or polyacrylonitrile resins. Specifically, Ce1liton Fast
Yellow RR, Kayalon Fast Ye
low G, Kayalon FastBrown
Re Kayalon Fast 5carle
tB.

Ce1liton Fast Rubine JB.

Cel eyes ton Fast 5carlet R, Ka
yalonFast Rubine B, Kaya
lon Fast Red R.

Miketon Fast Pink FR.

Kayalon Fast Violet BBMi
Keton Fast Violet BB, Ka
yalonFast Blue FN, Kaya
lon Fast BlueGreen B, Sum
ikaron Yellow FG.

Sumikaron Blue BR, Sumika
ronNavy Blue R etc. (Dye product name, Caliton: B
ASF, Kayalon: Nippon Kayaku Miket
on: Mitsui Chemicals ■; Sumikaron: Sumitomo Chemical ■. ) Other examples include basic dyes, specific examples include Flavine IfG and Auramine.

Crystal Violet, Methylene
Blue.

Rhodamine 4G, Malachite
Green.

Sumiacryl Yellow JG, Sumi
acrylYellow JR, Sumiacryl
OrangeG, Sumiacryl Orange
e R, Aizen Cathilon Pink, Ai
zen Cathilon Red 4BH.

Aizen Ba5ic Cyanine 4GH.

Primocyanine BX etc. (Among the dye product names, Sumiacryl: Sumitomo Chemical ■, Ai
zenCathilon: represents Hodogaya Chemical ■),
Or, Masao Iizuka, “Dyeing Industry” 13. ≠22~4c
Dyes described in <<r<tytr> and the like can also be mentioned.

The second solvent, which can optionally be used to dissolve the dye, is miscible with the non-polar solvent, and is capable of at least swelling the resin particles, is preferably a second solvent containing a small amount of resin (both monomers as constituent components). The use of a monomer has the advantage that the dissolution of resin particles that occurs when other solvents are used will not cause adverse effects such as aggregation.However, as the second solvent of the present invention, for example, the amount used can be With adjustment, it is also possible to use solvents that satisfy the above conditions, such as, for example, ethanol, acetone, ethyl acetate.

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 When the amount of monomer and second solvent is small, the amount of monomer and second solvent is 1710% based on the weight of resin particles in the dispersion.
It is necessary to add a second solvent to the dispersion liquid to achieve the above.

The second solvent may be added to the resin particle dispersion by adding the dye as a solution dissolved in the solvent, or by adding the dye to the dispersion as a powder and adding the dye before or after the addition of the dye. May be added. In any case, it is sufficient that 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. The solvent may be replenished. The second solvent is 0.0% based on the weight of the resin particles in the dispersion. /,
Although it is IQ times, it is preferable that it does not exceed //J of the volume of the resin particle dispersion in consideration of vacuum removal in the subsequent process.

However, the ratio is not limited to this range since there may be an optimum ratio outside the tube mouth depending on the types of dye, resin particles, non-aqueous solvent, and second solvent used.

In this manner, the second solvent is removed while the dye and the second solvent are being dropped into the dispersion and being 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.

The amount of dye used is determined by the amount of oil particles in the dispersion.
, 1% by weight or more, but preferably 3% by weight or more to obtain good color density.

The maximum amount of dye used is not particularly limited, but is usually 20
It is used in less than % by weight.

The heating temperature for dyeing is ψO0~/jO°C, preferably 10. / Al with richness 0C. Also, the heating time is 3
The time is 0 minutes to 12 hours, preferably 1 hour to j hours.

Another method for dyeing dispersed resins is mordant dyeing. This method uses a basic dye (cationic dye) when at least one of the components constituting the dispersed resin particles contains an acidic group (for example, a carboxy group), or uses a basic dye (cationic dye) or When one component contains a basic group, each component can be dyed using an acidic dye.This is a method based on the so-called ionic bonding of an acidic group and a basic group.

As the basic dye for dyeing the resin particles made of a copolymer containing a carboxyl group or a sulfonic acid group, examples of the above-mentioned dyes or AizenVictoria
Blue BH, Aizen VictoriaP
ure Blue BOH, Aizen Cath
ilonGrey BLH, Aizen Cathil
on BlackGH (all dyes manufactured by Hodogaya Chemical).

On the other hand, the dye for dyeing the resin particles made of a copolymer containing a basic group is a dye containing a carboxy group or a sulfonic acid group, such as Kiton Blu.
e A (CIBA), A11zarine As
trol B (Ikeda Chemical ■), Kayanol B
lue N CoG (Nippon Kayaku@), Kayacyl
Blue BR (Nippon Kayaku ■), Suminol
Fast Sky Blue B (Sumitomo Chemical ■)
, A11zarine Light Brown
BL (Mitsubishi Kasei ■), Aizen Eosine GH
(Hodogaya Chemical ■), A11zarinol R (Yamada Chemical ■), 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 metal 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 nonaqueous 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 extremely stable dispersibility. Even after use, it has good dispersibility and easy redispersion, and no stains are observed on any part of the device.

Various additives may be added to the liquid developer of the present invention, as necessary, in order to strengthen the charging characteristics or improve the image quality (see, for example, Yuji Harasaki, "Electronic Photography", Vol. 16, Vol. 2). No., page φda.

Example ethylhexyl sulfosuccinate metal salt,
Additives include naphthenic acid metal salts, higher fatty acid metal salts, lecithin, poly(vinylpyrrolidone), copolymers containing a hemi-maleic acid amide component, or copolymers containing hemi-maleic acid amide and maleimide components.

The amounts of each main component of the liquid developer of the present invention are explained below.

The toner particles mainly composed of a colored copolymer resin are O0! based on 1000 parts by weight of the carrier liquid. Weight section~! O
Parts by weight are preferred. If the amount is less than 0, rzIk parts, the image density will be insufficient, and if it is more than 50 parts by weight, fogging may easily occur in non-image areas. A carrier liquid soluble resin such as the above-mentioned dispersion stabilizer is also used as necessary, and O0! Approximately 100 parts by weight to 1000 parts by weight can be added.

The charge control agent as described above is preferably used in an amount of 0.00 parts by weight to 9 parts by weight based on the weight of the carrier liquid.

Furthermore, various additives may be added as necessary, 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 is less than 109Ω·α, it will be difficult to obtain a high-quality continuous tone image, so the amount of each additive added is controlled within this limit. It is necessary.

"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 resin particles: Compound poly(lauryl methacrylate) of specific example (a)/29. Specific example (1) of vinyl acetate toog (monomer CB) Compound 0. A mixed solution of j, q, and isododecane 31397 was heated to a temperature of 700 (:) while stirring under a nitrogen stream. 2.2'-Azobis(isobutyronitrile) (abbreviation A, 1.B, N)/ ,7
II was added and allowed to react for an hour. After 30 minutes of adding initiator -
The solution began to become cloudy and the reaction temperature rose to Ir'C.

After cooling, the white dispersion obtained by passing through a 200 mesh nylon cloth had a polymerization rate of l! %, average particle size O.

The latex was 0 μm thick.

Production Example of Resin Particles A mixed solution of the compound poly(lauryl methacrylate) lλl of specific example (b), vinyl acetate 1009, and monomer (C) (compound of 2), jli, isododecane, and itssg, While stirring under a nitrogen stream, it was heated to a temperature of 7o0c.A, 1.B, N/, 7
g was added and reacted for 6 hours. After adding the initiator and ψθ minutes, the average
The solution began to become cloudy and the reaction temperature rose to rr''c. After cooling, the white dispersion obtained by passing through a 200 mesh nylon cloth was a latex with a polymerization rate of re% and an average particle size of 0.23 μm.

Production example 3 of resin particles: Compound poly(lauryl methacrylate)/2II of specific example (e), vinyl acetate/009
A mixed solution of compound/39 of specific example (10) of monomer (C) and Isopar 03rog was heated to a temperature of 7 s 6 CK while stirring under a nitrogen stream. A.1. B, N/,
7# was added and reacted for 6 hours. 20 minutes after the addition of the initiator, white turbidity occurred and the reaction temperature rose to rr''c. After cooling, the resulting white dispersion was passed through a 200 mesh nylon cloth, with a polymerization rate of 0% and an average particle size of 0. .22 μm latex.

Production example 4c of resin particles: Compound poly(stearyl methacrylate)/ILI and shell silua 1 of specific example (b)
The mixed solution of 310/i was heated to temperature t while stirring under nitrogen stream.
It was heated to z@c.

Vinyl acetate 10017, compound of specific example (2) of monomer (C)/, OI and A, 1. A mixed solution of B, N/, and 7N was added dropwise over 2 hours, and the mixture was further stirred for φ hour. After cooling, the resulting white dispersion was passed through a -200 mesh nylon cloth. ! %, and the average particle size of the latex was 0.23 μm.

Example of manufacturing resin particles! : Compound of specific example (f) [lauryl methacrylate-acrylic acid (copolymerization ratio/l solubility ratio)
]Copolymer Ill, vinyl acetate/009s monomer (
Compound/, jII and iso of specific example (15) of C)
The mixed solution of q-0310fi was heated to a temperature of 7!0C while stirring under a nitrogen stream. Benzoyl peroxide/3g
was added and reacted for 6 hours. 19 minutes after the initiator was added, white turbidity occurred and the reaction temperature rose to 20°C. Thereafter, the temperature was raised to ioO"c and stirred for 1 hour to distill off the remaining vinyl acetate. After cooling, the resulting white dispersion was passed through a 200 mesh nylon cloth with a polymerization rate of 0%. The latex had an average particle size of 0.17 μm.

Production example t of resin particles: Compound poly(lauryl methacrylate) lφg of specific example (i), 100Ii on vinyl acetate,
71Jh acetic acid! ,! Specific example of i+, single octane (C) (1
A mixed solution of compound 0), Qll, and Isopar EutH was heated to a temperature of 7o0c while stirring under a nitrogen stream. A.1. B, N/, and 7S were added, and after reaction for 6 hours, the temperature was raised to 100°C and stirred for 1 hour, and the remaining vinyl acetate was distilled off. After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex with a polymerization rate of rr% and an average particle size of 0.11 μm.

Production example 7 of resin particles: Compound poly(lauryl methacrylate) 209 of specific example <t). Cohydro-7-ethyl methacrylate 10077, specific example of monomer (C) (
10) Compound 21! A mixed solution of 70 g of n-deca 7u was heated to a temperature of 7°C under a nitrogen stream while stirring. A.1. B.N.

1.7 g was added and reacted for several hours. A few minutes after the initiator was added, the mixture began to become cloudy and the reaction temperature rose to OoC. After cooling, coarse particles were removed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex with a particle size of about 0.05 μm.

Production example j of resin particles: Compound of specific example (g)) [lauryl methacrylate-2-hydroxyethyl methacrylate (copolymerization ratio ♂/2 molar ratio)] copolymer/lji, vinyl acetate rig, H-vinylpyrrolidone/ jfi, compound of specific example (7) of monomer <C>/, Il, and a mixed solution of n-decane 3109 at a temperature of 7 with stirring under a nitrogen stream.
Warmed to z'c. A.1. B, N, 7.711 were added and reacted for μ hours, and then A, 1. B, N, 0. After adding 1 ml of water, the mixture was reacted for 2 hours. After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth and had an average particle size of O.

The latex was 0 μm thick.

Example of manufacturing resin particles (Comparative Example A) Poly(lauryl methacrylate)/2. A mixed solution of p, vinyl acetate/00fi, and indodecane 3119 was heated to a temperature of 700C while stirring under a nitrogen stream.

A.1. B, N,/, 711 were added and reacted for 6 hours.

After 10 minutes of addition of the initiator, the solution began to become cloudy, and the reaction temperature rose to 000.

After cooling, the resulting white dispersion was passed through a nylon cloth made of COOO mesh.
It was made of latex.

Production Example 10 of Resin Particles (Comparative Example B) Specific compound examples (
2) Monomer 1. ! 9 was added and stirred well.

Manufacturing example of resin particles // (Comparative example C) In Production Example 5, instead of Compound Example (2).

The procedure was carried out in the same manner except that lauryl methacrytone, JP was used. The obtained white dispersion was a latex with a polymerization rate of tr% and an average particle size of 0.21 μm.

Example! White dispersion i obtained in Resin Particle Production Example λ.

Ol, Sumikalon black/, pi and vinyl acetate/u
/l mixture was heated to a temperature of 100°C and heated and stirred for an hour. Thereafter, the reflux vessel was removed at the same temperature, the mixture was stirred for 3 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 to obtain a black resin dispersion with an average particle size of 0° to 0 μm.

The above black resin dispersion! A liquid developer was prepared by diluting 0.03 g of -2//,/-octadecene-maleic acid semi-octadecylamide copolymer into Shell Sila/, /J3.

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

Comparative liquid developer A: Resin dispersion as in the production example of resin particles〃 B: n / Q tt 〃 C: 〃 / l〃 These liquid developers were processed using a fully automatic electronic plate making machine ELP21rO.
It is used as a developer for ELF Master (manufactured by Fuji Photo Film), an electrophotographic light-sensitive material
) was exposed and developed.

Furthermore, after processing 2000 ELP masters, the presence or absence of toner adhesion stains on the developing device was observed.

The results are shown in Table 7.

Table 1 The printing master plate (ELP/master) obtained using the developer of the present invention and Comparative Example C was printed as a printing plate, and the image of the printed matter was missing characters, fading in the solid area, etc. Comparing the number of prints until the occurrence of the offset master, the offset master obtained using the developer of the present invention was 1
Does it not occur with the master plate using Comparative Example C even after 10,000 sheets or more? This occurred at 000 sheets.

As shown in the above results, only the developer using the resin particles of the present invention did not cause any staining of the developing device, and at the same time, the number of prints of the master plate was significantly increased.

That is, in the case of Comparative Examples A and B, the developing device was smeared; in the case of Comparative Example C, the developing device was not smeared, but the printing durability was not sufficient.

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

Example: White dispersion 1001 obtained in Resin Particle Production Example t, Sumikalon Navy Blue/, 777 and Vinyl Acetate/j
The mixture of 9 was heated to a temperature of too0c and stirred with heating for 1.3 hours. After that, remove the reflux device and continue to φ
The mixture was stirred for an hour 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 to obtain a blue resin dispersion with an average particle size of 0.2 μm.

A liquid developer for electrostatic photography was prepared by dispersing 30/l of the above resin dispersion and diisobutylene-hemaleic acid octadecylamide copolymer o, aug in Shell Sila/, /J3.

This was developed using the same device as in Example 1.

Even after developing 200 sheets, no toner adhesion stains occurred 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 10,000 sheets was also very clear.

Example 3 White dispersion IQ011 obtained in Production Example t of resin particles,
Aizen Ba5ic Cyanine 4GHB
A mixture of Jy and ethanol/Ill at a temperature of 7o
The mixture was heated to ro0c and stirred for 2 hours. After, aspirator
The mixture was stirred at the same temperature for 2 hours while reducing the pressure.

After heating and cooling, the remaining dye was removed by passing it through a nylon cloth with a λ00 mesh to obtain a blue resin dispersion with an average particle size of o and it μm.

The above blue resin dispersion 32! A liquid developer was prepared by diluting 0.0 μl of i,/-octadecene-half-maleic acid octadecylamide copolymer into Isopar H1-e.

When this was developed using the same device as in Example 1, 20
Even after developing 10,000 sheets, no toner adhesion stains were observed on the device.Also, the image quality of the obtained offset printing master plate was clear, and the image quality of the printed matter after printing 10,000 sheets was also very clear. .

Example μ~7 In Example 3, the dye Aizen Ba5icCy
A liquid developer was prepared in the same manner using the following dye instead of anine 6GHBK.

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

Example 4' Aizen Cathilon Ye
lowjGLH (Hodogaya Chemical) ゛j Aizen Astra Ph1oxin
e FF (Hodogaya Chemical) 4 Aizen Cathilon Pink FG
H (Hodogaya Chemical) 7 Methylene blue example! Kayalon Fast Brown R (manufactured by Nippon Kayaku) 0.0% was added to the white dispersion 1001 obtained in Resin Particle Production Example t). jol, Mikcton FastPin
k FR (Mitsui Chemicals) 0. /j1. Victoria Blue B/, 011i and vinyl acetate i1. g each,
The mixture was stirred at OoC for 2 hours, and then the reflux vessel was removed and the mixture was stirred for 2 hours.

After cooling to room temperature, the resulting black resin dispersion was passed through a 200-mesh nylon cloth, with an average particle size of 0.177μ.
It was m.

The above black resin dispersion 3λI, octadecyl vinyl ether-half maleic acid hexadecylamide, polymer 000
A liquid developer was prepared by diluting 3 g into Isopar G/A.

When this was developed using the same device as in Example 1, the result was 200
Even after developing 0 sheets, no toner adhesion stains were observed on the device. The image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after printing 10,000 sheets was also very clear.

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
A liquid developer for electrophotography, characterized in that it is a colored copolymer resin obtained by the methods of 1) and (2). (1) In the presence of a resin that is soluble in a non-aqueous solvent and does not contain a graft group that polymerizes with the monomer, it is soluble in the solvent, but
Monofunctional monomer (A) that becomes insolubilized by polymerization
and a monomer (B) containing at least two types of polar groups and/or polar linking groups represented by general formula (I)
A dispersion of a copolymer resin is prepared by subjecting a solution containing at least one of each to a polymerization reaction. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (2) By adding at least one kind of organic dye to the dispersion obtained in (1) and heating it, a colored common polymer resin is produced. make. In general formula (I), V is -O-, -COO-,
-OCO-, -CH_2OCO-, -SO_2-, -CONH-, -SO_2NH-, ▲Mathematical formulas, chemical formulas, tables, etc.▼, or ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼ (W is a hydrocarbon group or a general formula (
I) Bonding group in: ▲There are mathematical formulas, chemical formulas, tables, etc. Represents the same symbol as ▼. ) Y is a hydrogen atom or a halogen atom, -OH, -CN, -
Represents a hydrocarbon group having 1 to 18 carbon atoms that may be substituted with NH_2, -COOH, -SO_3H, or -PO_3H. X_1 and X_2 may be the same or different from each other,
-O-, -S-, -CO-, -CO_2-, -OCO-
, -SO_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲Mathematical formulas, chemical formulas,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
,▲There are mathematical formulas, chemical formulas, tables, etc.▼, -NHCO_2- or -NHCONH- (Y_
1, Y_2, Y_3, Y_4 and Y_5 indicate the same symbol as Y above). R_1 and R_2 may be the same or different from each other,
may be substituted, or ▲a mathematical formula, chemical formula, table, etc.▼ may be interposed in the bond of the main chain [X_3, X_4 are
They may be the same or different from each other, and represent the same symbol as X_1 and X_2 above, R_4 represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and Y_6 represents the same symbol as Y. ] Represents a hydrocarbon group having 1 to 18 carbon atoms. In addition, a_1 and a_2 may be the same or different from each other, and represent a hydrogen atom, a hydrocarbon group, -COO-Z, or -COO-Z via a hydrocarbon (or a hydrogen atom or a hydrocarbon group that may be substituted). ), and m, n and p may each be the same or different and represent 0 or an integer from 1 to 4.