JPS6366567A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To obtain the titled developer having less tendency for reducing redispersibility and stability of the titled developer, even in case of preserving for a long period and repeatedly using it by dispersing a specific resin into a prescribed carrier solution. CONSTITUTION:The titled developer is formed by dispersing the resin (A) in the carrier solution such as an aliphatic hydrocarbon which has >=10<9>OMEGA.cm electric resistance and <=3.5 dielectric constant. The resin A is produced by forming a copolymer composed of monomers shown by formulas I and II, followed by reacting the obtd. copolymer with the monomer shown by formula III. Next, the obtd. copolymer, the monomer such as vinylacetate which remains insoluble to the carrier solution by polymerizing, and the monomer shown by formula IV are effected a solution polymerization to form the resin A. In the formulas, a1-e3 are each H or a hydrocarbon, etc., X-Z are each -O-, group, etc., L is a hydrocarbon group of binding X and Q, etc., F is a hydrocarbon group binding V and G, etc., Q and G are each -CO2H or -OH group, etc., R1 is 4-20C hydrocarbon, R2 and R3 are each 1-18C hydrocarbon, U is H or halogen atom, etc., T1 and T2 are each -S-, etc., (m), (n) and (p) are each 0-4.

Description

[Detailed Description of the Invention] "Industrial Application Field" The present invention has an electrical resistance of 109 Ωcm or more and a dielectric constant of 3°! It relates to a liquid developer for electrostatic photography which is made by dispersing at least a resin in the following carrier liquid, and has particular characteristics such as redispersibility, storage stability,
It relates to a liquid developer with excellent stability, image reproducibility, and fixing properties.

``Prior art'' General electrostatic photographic liquid developers are made by combining organic or inorganic pigments or dyes such as carbon black, nigrosine, and phthalocyanine blue with natural or synthetic resins such as alkyd resins, acrylic resins, rosins, and synthetic rubbers. Dispersed in highly insulating and low dielectric constant liquids such as aliphatic hydrocarbons,
In addition, polarity control agents such as metal soaps, lecithin, linseed oil, higher fatty acids, and polymers containing vinylpyrrolidone are added. In such developers, the resin is dispersed as insoluble latex particles with a diameter of several μm to several hundred μm, but in conventional liquid developers, a soluble dispersion stabilizing resin, a polarity control agent, and insoluble latex particles are dispersed. Because of insufficient bonding, the soluble dispersion stabilizing resin and polarity control agent were likely to diffuse into the solution. For this reason, there is a drawback that the soluble dispersion stabilizing resin is detached from the insoluble latex particles due to long-term storage or repeated use, and the polarity of the particles becomes unclear due to sedimentation, aggregation, or accumulation. In addition, particles that have aggregated and accumulated are difficult to redisperse, so they can remain stuck all over the developing machine, which can lead to developing machine failures such as stains in the image area and clogging of the liquid pump. was. In order to improve these drawbacks, a method for chemically bonding a soluble dispersion stabilizing resin and insoluble latex particles was devised and patented in the United States! , 990, 91θ, etc.

However, according to the experimental results of the present inventors, particles produced by the means disclosed in the above-mentioned US patent etc. have two or more peak values in the particle size distribution curve,
It is difficult to control the particle size uniformly due to the wide distribution width, and the reproducibility of these results is also poor.

A means to improve the shortcomings of the above US patent is published in Japanese Patent Application Publication No. 2003-63-63! ! Disclosed in the issue.

Particles loaded by this means are characterized by their monodispersity,
Although the redispersibility and storage stability are good, it has been desired to further improve the printing durability, especially the printing durability in large plate sizes.

"Problems to be Solved by the Invention" The present invention aims to improve the above-mentioned drawbacks of the electrostatic photographic liquid developers proposed so far. Therefore, an object of the present invention is to provide a liquid developer whose redispersibility and stability do not deteriorate even after long-term storage or repeated use. Another object of the present invention is to provide a liquid developer having a uniform particle size and excellent image reproducibility. Still another object of the present invention is to provide a liquid developer that does not cause malfunctions of the developing device such as clogging of the liquid pump or staining of images even after repeated use over a long period of time.

Still another object of the present invention is to provide a liquid developer that does not change the polarity of its particles even after long-term storage or repeated use and always reproduces clear images. Still another object of the present invention is to provide a liquid developer which has good image fixability after development and forms a strong outer image. Still another object of the present invention is to provide a liquid developer that forms images with excellent printing durability on large size plates.

"Means for Solving the Problems" The present invention has an electrical resistance of 109 Ω·cm or more and a dielectric constant of 3!
In an electrostatographic liquid developer comprising at least a resin dispersed in the following carrier liquid, the resin may be one of the following (1) and (2).
This is a liquid developer for electrostatic photography, characterized in that it is obtained by the process of (a).

(1) A copolymer obtained by polymerizing a monomer (A) represented by general formula (III) and a monomer (B) represented by general formula (II), and further a monomer represented by general formula (III) A step of reacting (C) to obtain a copolymer having an unsaturated bond introduced from K.

(2) At least the copolymer obtained in step (1), the monomer (D) that is soluble in the carrier liquid but becomes soluble upon polymerization, and the monomer represented by the general formula (1'v') ( A step of polymerizing a solution containing one or more of each of E) to obtain a resin dispersion.

General formula (1) General formula (IV) The symbols in general formula (1) (U) (III) (fV) represent the following. al + a2 + a3 + b
l + b2 + b31dIId2Id31eIIe2t
e3 may be the same or different from each other, and each represents a hydrogen atom, a hydrocarbon group, -CO2J or 10H2C02
J (J is a hydrogen atom or a hydrocarbon group). X, Y
.

V, Zi O, S, CO, CO2.

-0CO-, -8O2-, -CH20CO-, -CON
H-.

-8O2NB-, -NHCO-, -NHCONH-, -
CON-.

-3O2N-. However, W is a hydrocarbon group or +R2
-T1 represents R3-T2-U. L is atomic group X
and atomic group Q, and F is a hydrocarbon group or a chemical bond that connects atomic group V and atomic group G, respectively, and may be through a heteroatom. Q and G are selected from -NHR4 (R4 is a hydrocarbon group) and -NGO, respectively, and are a combination that allows Q and G to easily form a chemical bond through reaction. R1 is a hydrocarbon group having a carbon number of glucoθ. U is a hydrogen atom or a halogen atom, -OH, -CN, -NH2゜-
A hydrocarbon group having a carbon number of // or less that may be substituted with CO2H, -8o3I (or -PO3H).

TI and T2 may be the same or different, and are -o-, -s-, -co-, -co2-, respectively.

-NHCONH-. However, 1. U:i, tJ2. U
3.

U4. U5 represents the same meaning as U. R2゜R3 may be the same or different from each other, each may be substituted, or -CH- may be interposed in the main chain. Carbonization of T 3 + R5 - T 4 Narrow U6 ♂ or less It is a hydrogen group. However, T3. T4 may be the same or different, and each has the same meaning as T1 and T2. R5 represents a hydrocarbon group having 7 or less carbon atoms which may be substituted. U6 represents the same meaning as U. m, n, and p may be the same or different from each other and each is an integer from θ to 4t.

The electrostatic photographic liquid developer of the present invention is characterized by the use of the monomer (E) represented by the general formula (IV) as a resin component, and is a liquid that forms images with excellent printing durability by introducing this component. A developer is obtained.

Hereinafter, the electrostatic photographic liquid developer of the present invention will be explained in detail.

Electrical resistance used in the present invention/θ9Ω・cm or more, dielectric constant 3
．． ! As the following carrier liquid, preferably linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogen-substituted products thereof can be used. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, indodecane, iso-ξ-E
, Isono G, Isono (H, Isopar L (Isopar; trade name of Exxon), Shellzol 70. Schelzol 7/ (Shellzol: trade name of Shell Oil), Amsco OMS, Amscoda Otsu 0 solvent (Amsco) (trade name of Spirits Co., Ltd.) may be used alone or in combination.The insoluble latex particles in the present invention are produced by the so-called polymerization granulation method using a soluble dispersion stabilizing resin. Linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogen-substituted products thereof may be used as long as they are miscible with the carrier liquid.For example, octane, isooctane , decane, indecane, decalin, nonane,
Dodecane, isododecane, iso/1! -E, Isopar G, Isopar H5 Isopar L % Scherzol 7θ, Scherzol 7/, Amscog OMS, Amscog 6θ solvents, etc. are used alone or in combination. In order to stably obtain insoluble latex particles in such nonaqueous solvents, at least one type of soluble dispersion stabilizing resin synthesized from the monomers (A), (B), and (C) is used. There are no particular restrictions on the solvent used when synthesizing the resin, but in order to apply the resin to the next polymerization granulation without removing the solvent, it is desirable to use a solvent that is miscible with the solvent used in the polymerization granulation. For example, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogen-substituted products thereof may be used alone or in combination.

Since the monomer (B) represented by the above general formula (■) imparts solubility to the resin, the hydrocarbon group R1 has an electrical resistance of 109 Ω·cm or more and a dielectric constant of 3°! It is desirable to have a form that is easily miscible with the following carrier liquid. For example, alkyl esters of acrylic acid or methacrylic acid (alkyl groups include octyl, decyl, dodecyl,
Tetradecyl group, hexadecyl group, octadecyl group, -
Alkenyl esters of acrylic acid or methacrylic acid (alkenyl groups include, for example, octenyl, decenyl, octadecenyl, and oleyl groups) can be used. or,
The monomer (A) represented by the general formula (III) includes unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, etc.);
or their chlorides (for example, acrylic acid chloride, methacrylic acid chloride, crotonic acid chloride, etc.), or unsaturated alcohols (for example, allyl alcohol, etc.), or unsaturated amines (for example, allyl amine, etc.) Furthermore, glycidyl ester, hydroxypropyl ester, hydroxyethyl ester, etc. of acrylic acid or methacrylic acid can be used. As the monomer (C) represented by the general formula (I [ The G moiety in general formula (III) is a monomer (
It is necessary to select a material that can easily form a chemical bond with the Q portion of A) through a reaction such as condensation or addition. For example, monomer (
When a substance in which the Q moiety is -CO2H is used as A), the monomer (C) is used, and the G moiety is 10".
If the Q moiety of the monomer (A) is 10H, the HGG moiety -CO can be selected as the monomer (C).
2H,-Cocl.

-NCO may be selected. There are various other combinations, but they can be easily selected in the field of organic chemistry.

The soluble copolymer resin containing unsaturated bonds used in the present invention can be produced using the materials described above in the following manner. The above-mentioned solvent-based monomer (A) and monomer (B
) in the presence of a polymerization initiator to0cmλθo
Heat at 'C for several hours.

Next, the monomer (C) and, if necessary, a known polymerization inhibitor commonly used in polymerization systems are added, and the reaction pattern is determined. If necessary, add any catalyst such as lauryldimethylamine and heat at the same temperature for several hours.

The molar ratio of monomer (A) and monomer (B) used at this time is to: to~θ,! : Tata,!
The molar ratio of monomer (A) to monomer (C) is preferably in the range of 2:3 to 2:3. When using a polymerization inhibitor, the above solvent/l weight is converted to 0.
．． 0/g~/Which amount to use? The molecular weight of the soluble copolymer containing unsaturated bonds obtained as described above is 100.
0~! It is 00,000.

Specific examples of soluble dispersion stabilizing resins that are copolymers containing unsaturated bonds are shown below, but the present invention is not limited thereto.

(ii*) (IV) (V) (■1) Next, the process of obtaining a resin dispersion will be explained.

As the monomer (D), a monomer that is soluble in the carrier liquid and the nonaqueous solvent but becomes insolubilized by polymerization is used. For example, acrylic acid, methacrylic acid, crotonic acid,
Alkyl esters of unsaturated carboxylic acids with up to 3 carbon atoms such as itaconic acid and maleic acid; vinyl or allyl esters of aliphatic carboxylic acids with up to 3 carbon atoms; acrylic acid, methacrylic acid, crotonic acid, maleic acid, Unsaturated carboxylic acids such as itaconic acid or their anhydrides; co-hydroxyethyl acrylate or methacrylate; N-vinylpyrrolidone; acrylonitrile; vinyl ether, etc. can be used.

Monomers represented by the general formula <IV) used in the present invention (
To further explain E), in general formula (IV), preferably 2 is -0-1-COO-5-0CO-1
-CH20CO-1-CONH- or -CON- [W is the total number of carbon atoms/-/B, an optionally substituted alkyl group, the total number of carbons--/A, the optionally substituted alknyl group, and the total number of carbon atoms! ~//optionally substituted alicyclic group or -+R2-
T14 Tomo R3-T2 piece U is shown. ]U is a hydrogen atom or a halogen atom (e.g. chloro atom, bromo atom, etc.), -
An aliphatic group having the total number of carbon atoms/the following (the aliphatic group is, for example, an alkyl group, an alkenyl group, or an aralkyl group) which may be substituted with OH, -CN, or -COOH.

T1 and T2 may be the same or different, and each is -〇-1-S-5-CO-2-COO-1U2
U3 -OCO-1-CON-1 or -NGO-(U2 and U
3 indicates the same meaning as U above.

R2 and R3 may be the same or different from each other, each may be substituted, or -CH- may be interposed in the bond of the main chain. A hydrocarbon group (the hydrocarbon group includes an alkyl group, an alkenyl group, an aralkyl group, or an alicyclic group). T3 and T4 may be the same or different and have the same meaning as T1 and T2 above, R5 represents an optionally substituted alkylene group, alkenylene group or aralkylene group having 7.2 or less carbon atoms, and U6 represents the above U has the same meaning as

el, C2, and C3 may be the same or different, and each represents a hydrogen atom, a methyl group, -Co2J, or -C
H2CO2J (J represents a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, or a cycloalkyl group having a carbon number of // or less).

m, n and p may be the same or different, and respectively θ, /
, ko, represents the number of 3.

Preferably, in formula (M), 2 is -COO-1-CO
NH- or -CON-, el, C2, C3 are
They may be the same or different, and each hydrogen atom, methyl group, -
Co2J-1, or -CH2CO2J (J is the number of carbon atoms/~
/2 represents an alkyl group).

Regarding R2 and R3, to give a specific example, R/ -C-(R', R" is a hydrogen atom, an alkyl group, R -CH-(T3, T4, U6, R5 and T3 + R5- It is composed of any combination of atomic groups such as T4+ili'''U6 and p have the same meanings as above).

Also, T1, T2, m, n and p are the same as described above (7)
Table meaning-bf. In addition, the total number of atoms of each atomic group of z, R2, T1, R3, T2, and U is 2 or more.

More specific examples of the monomer (E) include the following compounds.

CH3 CI-I□=C Spirit C00 (CH2)2oCOC9H19!・ CH2=C COO(CH2)20COC11H23CH3 CH2=C C00(CH2)1ooCoC6■(13CH3 CH2=C Coo (CH2)10COOC8H17CH2COO
CH3 CH2=C C00(CH2)3COoC4H9 IH3 CH2=C C0NH(CH2)6COOC8H17CH3 CH2=C C00(CH2)2Nl(CO(CH2)3COOCH
3■ CH2=C C00(CH2)30COC:)I=CHCOOC6H
13I CH3 CH2:C C00CH2CHCH20COC5H11 Taki0COC5H11 CH3 CH2=C C00CJ(2CHCH20COC6H130COC3
H7 CH3 cII2=C C0NCH2CH20COC5H11 CH2CH20COC5H11 αQ CH3 Joy C4) CH3 α9 CH3 CH2=CCH3: I C0NHCC) (20COC4H9 CH20COC4H9 CH2=6 Coo (CH 2) 2α:'O(CH2)3COOCH
2CH2C/! (L7) CH2=C oCO(CH2)□ooCoC3H7 Seven or two of the above monomers (D)
a mixture of seven or more types of monomers (E), a mixture of seven or more types of monomers (E), and a mixture of seven or more types of copolymers having unsaturated bonds obtained in the step (1) above. The mixture is dissolved in the nonaqueous solvent, and if necessary, in the presence of a known polymerization initiator commonly used in polymerization systems. Heat at θ0C - λθθ0C for several hours.

At this time, a conventionally known dispersion stabilizer may also be used. That is, various synthetic or natural resins soluble in non-aqueous solvents can be used alone or in combination of 28i or more. For example, an alkyl chain having 4 to 30 carbon atoms (which may contain substituents such as a halogen atom, a hydroxyl group, an amino group, an alkoxy group, etc.) or a hetero atom such as an oxygen atom, a nitrogen atom, a sulfur atom, etc. - alkyl esters of acrylic acid or methacrylic acid, vinyl esters of fatty acids, vinyl alkyl ethers, or monomers such as olefins such as butadiene, isoprene, diisobutylene, etc. Polymers or copolymers formed by a combination of two or more types, and copolymers of monomers that form polymers soluble in the above non-aqueous solvents and various monomers/types or more as shown below. A copolymer containing the following monomers within a range that is soluble in a nonaqueous solvent.

For example, vinyl acetate; methyl, ethyl, n-propyl or 1ji such as acrylic acid, methacrylic acid or crotonic acid;
so-i robyl ester; styrene, vinyltoluene,
Kystyrene derivatives such as α-methylstyrene; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid or their anhydrides; hydroxyethyl methacrylate, hydroxyethyl acrylate,
Diethylaminoethyl methacrylate, N-vinylpyrrolidone, acrylamide, acrylonitrile, cochloroethyl methacrylate, 2,2. ．． Hydroxyl group such as 2-trifluoroethyl methacrylate, amino group, amide group, cyano group, sulfonic acid group, carbonyl group,
Examples include monomers containing various polar groups such as a halogen atom and a Peter term. Alternatively, in addition to the above-mentioned synthetic resins, natural resins such as alkyd resins, alkyd resins modified with various fatty acids, linseed oil, and modified polyurethane resins can be used. Monomer used (D)
may be the same type as mentioned above or two or more types, but in any case, the total amount is based on 700 parts by weight of the non-aqueous solvent as the reaction solvent! ~♂Q parts by weight, preferably 70~0 weight parts. Monomer (E) Hayake b/
It doesn't matter if there are two or more types of Class 91, but the total amount in moles is 0 □ / ratio to the total number of moles of monomer (D) ~! Q
preferably 0. ! Chill 10chi. The resin used for dispersion stabilization is preferably 7 to 700 parts by weight based on 700 parts by weight of all the monomers mentioned above! ~! O parts by weight. When using a polymerization initiator, total monomer 100
0.0% by weight. /~! Parts by weight are appropriate.

The non-aqueous dispersion resin produced as described above has a uniform and monodisperse particle size distribution, and can be easily controlled to a desired particle size. These dispersion resins have very good redispersibility, stability, and fixing properties. Even after long-term storage and repeated use in an actual developing machine, there is no sedimentation, agglomeration, or adhesion of stains on the container or other parts of the device, and when it is fixed by heating, etc., a strong film is formed and is durable. A powerful image is formed.

In the present invention, a coloring agent may be used if necessary, and the coloring agent is not particularly specified, and various conventionally known pigments or dyes can be used. The colorant may be used alone or dispersed in the non-aqueous solvent in combination with a dispersion accelerator or the like, or it may be used as a graft particle having a polymer chemically bonded to the surface of the colorant (for example, grafted carbon; (Product name manufactured by Mitsubishi Gas Chemical Co., Ltd.) may also be used.

Moreover, a coloring agent may be contained in the above-mentioned resin for use. As a method for coloring the dispersed resin, for example, JP-A-4T
/-7, t, 2 (dispersing machine, which is a known method such as No. tj)
There are many known methods for physically dispersing pigments and dyes into resins using a paint shaker, colloid mill, vibration mill, ball mill, etc. For example, magnetic iron oxide powder, carbon black, nigrosine, alkali blue, Hansa yellow, quinacridone red,
Examples include phthalocyanine blue, phthalocyanine black, and benzidine yellow.

Another coloring method is Tokukai Shoyo 2-da♂73! There is a method of thermally dyeing a dispersed resin material with a preferred dye, as described in No. 1, etc.

Examples include Hansa Yellow, Crystal Violet, Victoria Blue, Malachite Green, Seriton Fast Red, Despers Yellow, Despers Red, Tesno ξ-Sprue, and Solvent Red.

Still another method of coloring is a method of chemically bonding a dispersion resin and a dye. For example, Tokukai Shoyo 3-! A method of reacting a resin with a dye as disclosed in ``Gu θ Kowa No. 1'' or the like, or a method of bonding a dye to a resin monomer that can be made insolubilized and dispersed by polymerization disclosed in Tokko Sho Tag-2, 2 Liyo 1, etc. You can use a method such as keeping the

If necessary, additives may be added to the liquid developer of the present invention in order to strengthen charging characteristics or improve image reproducibility. ``Floating child''
, Vol. 76, No. 2, p. 4tg.

Example Ehazicoethylhexyl sulfosuccinate metal salt,
Additives such as naphthenic acid metal salts, higher fatty acid metal salts, lecithin, and poly(vinylpyrrolidone) may be mentioned.The amounts of each of the main components of the liquid developer of the present invention will be explained below.

The insoluble latex particles mainly composed of a resin and a colorant are used in a quantity of 0.tM per 7000 parts by weight of the carrier liquid. 0 parts by weight is preferred. If it is less than 0.5 parts by weight, the image density will be insufficient! If the amount exceeds 0 parts by weight, fogging tends to occur in non-image areas. A carrier liquid soluble resin such as the above-mentioned dispersion stabilizer is also used as necessary, and can be added in an amount of about o, r parts by weight to /θ0 parts by weight based on 10 θθ parts by weight of the carrier liquid. The charge control agent as described above is preferably used in an amount of 0.0Q/ to 0 parts by weight based on 1000 parts by 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. In other words, if the electrical resistance of the liquid developer with insoluble latex particles removed becomes lower than /θ9Ω・am, it will be difficult to obtain a high-quality continuous tone image. It is necessary to control it.

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

Production example of soluble dispersion stabilizing resin: Compound example (1) Stearyl methacrylate)/, I/, 7 g, -monohydroxyethyl methacrylate), z, 4 g, and toluene 2
A mixed solution of 4 tOg was heated to a temperature of 7 t'C under a nitrogen stream, and 7.3 g of azobisisobutyronitrile was added while stirring. After some time, put a Dean-Stark water separator on the reaction vessel and remove 0.0% hydroquinone. ．． 2g, sulfuric acid θ
6/g, and 7.7 g of Metakudimetha were added. While stirring, raise the temperature to /10'C until the added methacrylic acid reaches 6.
! The reaction was carried out until it was consumed. After the reaction, the reaction solution was diluted with y.

oog methanol and reprecipitation purification to obtain a slightly yellowish powder. When the average molecular weight of the obtained powder was measured by high performance liquid chromatography, it was /7. /X/θ4
Met.

Production Example 2 of Soluble Dispersion Stabilizing Resin: Compound Example (ii) A mixed solution of 3.5 g of lauryl methacrylate, glycidyl methacrylate <t, rgz, and 230 g of toluene was heated to 230 g under a nitrogen stream. ! The mixture was heated to 0C, and 7.0 g of Pencilium chloride oxide was added while stirring. After a period of time, lower the temperature to 0C. Hydroquinone 0.2g
, lauryldimethylamine θ.

, 2g, methacrylic acid λ, and ♂g were added. Adjust the temperature while stirring! Methacrylic acid added to 0C! ! The reaction continued until the person in charge was no longer detected.

After the reaction, the reaction solution was poured into 4t000g of methanol and purified by reprecipitation to obtain a brown viscous substance. Average molecular weight measured in the same manner as in the above production example/! , θ×/θ4.

Production example 3 of soluble dispersion stabilizing resin: Compound example <m) Stearyl methacrylate/30g, methacrylic acid/,
A mixed solution of 20g of toluene and 2'lOg of toluene was heated to a temperature of ♂t'C under a nitrogen stream, and 3g of 1 oxide/g was added to penzoylno while stirring. After 2 hours, the temperature was lowered to 4t
Lower the temperature to 0°C, add 0.2 g of hydroquinone, and 0.0 g of lauryldimethylamine. ．． 2g.

2.0 g of glycidyl acrylate was added. While stirring, raise the temperature to //l 0c and use the methacrylic acid!
! The reaction was carried out until no trace was detected. After the reaction, the reaction solution was added to yooog methanol and purified by reprecipitation to obtain a slightly yellowish powder. The average molecular weight of this substance is 2
/, 3×704.

Example of production of soluble dispersion stabilizing resin: Compound example (iV)' The same procedure as in Production Example 3 was carried out using 9782 g of lauryl methacrylate in the stearyl methacrylate paste used in Production Example 3, resulting in a slightly brown color. A thick viscous substance was obtained. The average molecular weight of this product was 7×104.

Example of manufacturing soluble dispersion stabilizing resin! : Compound Example (V) A mixed solution of stearyl methacrylatene, 2/, 9 g, methacrylic acid chloride, 2 g, and toluene 30 og was heated to a temperature of 710 C under a nitrogen stream and stirred to obtain azobisisobutyronitrile 7. .2g was added. Hydroquinone O, Sg after 6 hours.

Add 2.3g of allylamine and mourn. While stirring, the temperature was raised until the reaction solution slowly refluxed, and the reaction was allowed to continue for an additional hour. After the reaction, 4t of the reaction solution was added.

It was poured into 0 gg of methanol and purified by reprecipitation to obtain a white powder. The average molecular weight of this product is 2'l, 7X104
Met.

Production Example 6 of Soluble Dispersion Stabilizing Resin: Compound Example (vl) Instead of stearyl methacrylate used in Production Example 1, allyl alcohol was added to lauryl methacrylate 9/, 6g1 allylamine glue].

Manufacturing example using 3g! The same procedure as above was carried out to obtain a slightly π-brown viscous substance. The average molecular weight of this thing is /21!
It was ×704.

Production example 2 of soluble dispersion stabilizing resin: Compound example (vii) Glutaric anhydride co♂,! g, 2-hydroxynitel methacrylate! 2. J'g, sulfuric acid θ,! ml.

A mixed solution of benzene J-Oml was stirred at room temperature. Although heat generation started after about 3Q minutes, stirring was continued for 1 hour with natural reflux. The reaction solution was washed with water, dried, and the solvent was removed under reduced pressure. Although the product is mostly single, it may be purified by silica gel column chromatography if necessary. Monomer thus obtained /, /
A mixed solution of stearyl methacrylate/-23,-2g5 and toluene 4tOg was heated at a temperature of 7.0g under a nitrogen stream.
Heat to C and stir and wash azobisisobutyroni) +7 /
l//, 2g was added. After 6 hours, 0.2 g of hydroquinone O0λg1 lauryl dimethylamine and glycidyl methacrylate z and ig were added. The temperature was raised to 10°C while stirring, and the reaction was carried out until the 2θ chain of the carboxylic acid derived from the monomer used was consumed. After the reaction,
The reaction solution was poured into <10θoz methanol and purified by reprecipitation to obtain a white powder. The average molecular weight of this product is 2/, 7
It was X#74.

Production example of soluble dispersion stabilizing resin ♂: Compound example (Mount V) In the stearyl methacrylate glue used in Production Example 7, lauryl methacrylate ter, 6 g, in the glycidyl methacrylate glue, allylamine 2.1 g, lauryl dimethylamine glue The same operation as in Production Example 7 was carried out using 0.1 g of sulfuric acid to obtain a colorless and transparent viscous substance. The average molecular weight of this product was 26.3×104.

Production example of resin particles/Production example of soluble dispersion stabilizing resin/Compound obtained in 1. j
g, (compound tg of 11 in the specific example of monomer (E),
Vinyl acetate/! θg and 3.2gg of Shersol 70
The mixed solution was heated to a temperature of 700C under a nitrogen stream, and azobisinvaleronitrile-g was added while stirring. Approximately after adding a polymerization initiator! The reaction solution started becoming cloudy at θ minute diameter at 26°C.
The temperature rose to. After an hour, 1 g of 7zobisisopareronitrile was added and the reaction was continued for a further 7 hours. After cooling, the white dispersion obtained by passing through a 200-mesh cloth was latex with an average particle size θ of 30 μm.

Production Example of Resin Particles λ Compound Jug obtained in Production Example of Soluble Dispersion Stabilizing Resin
A mixed solution of 20 g of the compound (2) in the specific example of monomer (E), 00 g of vinyl acetate, and 4 g and 70 g of Isopar H was heated to a temperature of 700 C under a nitrogen stream, and 4 tg of azobisinvaleronitrile was added while stirring. . Approximately 30 minutes after the addition of the polymerization initiator, the reaction solution began to become cloudy and the temperature rose to 0'C.

/,! After an hour, add another 2 g of azobisisovaleronitrile and further/! Allowed time to react.

After cooling, the white dispersion obtained by passing through the mesh cloth had an average particle size of 0. /μm latex.

Production Example 3 of Resin Particles Compound λθg obtained in Production Example 3 of Soluble Dispersion Stabilizing Resin,
Compound 01♂g of (2) in the specific examples of monomer (E),
A mixed solution of 90 g of vinyl acetate rOg and Scherzol 70 was heated to a temperature of 7 o 0 C under a nitrogen stream, and azobisisovaleronitrile was added while stirring.

4g was added. After the addition of the polymerization initiator, the reaction solution began to become cloudy at about /J minute diameter and the temperature rose at ♂θ0C1. 2 more after 7 hours. , rH azobisisovaleronitrile was added and the reaction was allowed to proceed for an additional hour.

After cooling, the white dispersion obtained through a 2Q0 mesh cloth had an average particle size of 0. ．． It was 27 μm latex.

Example of manufacturing resin particles Compound obtained in Example of manufacturing soluble dispersion stabilizing resin! θg,
Compound (5) in the specific examples of monomer (E), 2tg,
7300g of vinyl acetate roog and Sherzol 20
The mixed solution was heated to a temperature of 200C under a nitrogen stream, and azobisisovaleronitrile was added while stirring. g was added. When the polymerization initiator was added, the reaction solution began to become cloudy at a diameter of about 3°.
The temperature rose to c. Two hours later, more λ,! g of azobisisovaleronitrile was added and the reaction was further continued for 7 hours. After cooling, the white dispersion obtained by passing through a 20θ mesh cloth has an average particle size of 0.2! It was micrometer latex.

Example of manufacturing resin particles! Example of manufacturing soluble dispersion stabilizing resin! Compound obtained with /Jg,
Compound (5) in the specific examples of monomer (E)! A mixture of 100 g of vinyl acetate and 210 ff of Scherzol 7° was heated to a temperature of 206° C. under a nitrogen stream, and 0.9 g of azobisisovaleronitrile was added with stirring. Approximately after adding a polymerization initiator! The reaction solution started to become cloudy at 0 minute diameter, r, 2°
Temperature increased with cf. Ko,! More o after hours, 4
Further by adding tzg of azobisisovaleronitrile [7
Allowed time to react. After cooling, the resulting white dispersion was passed through a 2OO mesh cloth with an average particle size of 0.3! It was micrometer latex.

Production Example 6 of Resin Particles Compound obtained in Production Example t of Soluble Dispersion Stabilizing Resin/! g5
Compound (4) in the specific example of monomer (E)/♂g, ?
! )! Vinyl/nijOg and Scherzol 20 230
The mixed solution of g was heated to a temperature of 7θ0C under a nitrogen stream, and azobisisovaleronitrile yg was added while stirring. Approximately 20 minutes after adding the polymerization initiator, the reaction solution started to become cloudy.
The temperature rose to 0c. After one hour, another 7 g of azobisisovaleronitrile was added and the reaction was continued for another 7 hours. After cooling, the obtained white dispersion was passed through a SOO mesh cloth and was a latex with an average particle size θ and strpm.

Production example 7 of resin particles 30 g of the compound obtained in production example 7 of soluble dispersion stabilizing resin,
In the specific example of monomer (E), a mixture of 70 g of compound (II), 5 vinyl acetate, 20 g and 200 g of -H was heated under a nitrogen stream to a temperature of 20°C, and with stirring [2 g of azobisisovaleronitrile was added]. After the addition of the polymerization initiator, the reaction solution began to become cloudy at about tio minutes, and the temperature rose to !0C.

After 2 hours, 1/2 g of azobisisovaleronitrile was added and the reaction was continued for another 2 hours. After cooling, the white dispersion obtained by passing through the mesh cloth was a latex with an average particle diameter of θ and cog μm.

An example of manufacturing resin particles? Example of manufacturing soluble dispersion stabilizing resin! Compound obtained with! θg,
Compound jug with a value in the specific examples of monomer (E), vinyl acetate, 2! A mixed solution of r41og of Og and Scherzol 70 was heated to a temperature of 7θ0C under a nitrogen stream, and azobisisovaleronitrile sawdust, Jg was added while stirring. Approximately 3θ minutes after adding the polymerization initiator, the reaction solution started to become cloudy.
The temperature increased at °c-1. Ko,! After an hour, 2 more.
Add 6g of azobisinvaleronitrile and add 0.
The reaction was allowed to take place for J' hours. After cooling, the obtained white dispersion was passed through a θO mesh cloth and was a latex with an average particle size of 0.3.2 μm.

An example of manufacturing resin particles or an example of manufacturing a soluble dispersion stabilizing resin? Compound obtained in 22.
6g, compounds a, t of aυ in the specific examples of monomer (E)
g, vinyl acetate/! A mixed solution of 600 g of Og and Isopar H was heated to a temperature of 700 C under a nitrogen stream and mixed with azobisisovaleronitrile/3! g was added. Approximately <10 minutes after adding the polymerization initiator, the reaction solution begins to become cloudy.
The temperature rose to /'C. After 2 hours, add another 100 g of azobisisovaleronitrile and add more /,!
Allowed time to react. After cooling, the white dispersion obtained by passing through a 20θ mesh cloth has an average particle size of 0. ．． It was a 241 μm latex.

Production Example 10 of Qf fat particles (Comparative Example A) Lauryl methacrylate 1 was added to the base of the compound (1) in the specific example of monomer (E) used in Production Example of Resin Particles/
When the same operation as in Production Example 1 was carried out using G, a latex with an average particle size of O6 and 22 μm was produced.

Manufacturing Example of Resin Particles//(Comparative Example B) Stearyl methacrylate rg was used in place of the compound (1) in the specific example of Natsumar (E) used in Manufacturing Example of Resin Particles/, and the rest were manufactured as follows. When the same operation as in Example 1 was performed, a latex with an average particle diameter of θ and 3θ μm was produced.

Example/Poly(lauryl methacrylate)/Qg, Nigrosine 1
0 g and 2/JOg of shell sol were placed together with glass beads in an India shaker (Tokyo Seiki ■) and dispersed for 0 minutes to obtain a fine dispersion of nigrosine.

Manufacturing Example of Resin Particles / 30 g of the resin dispersion 1 of the above nicrosine molecules ls, rgs octadecene-half maleic acid octadecylamide copolymer 0, 0 jg was added to Shell Sol 77
A liquid developer for electrophotography was prepared by diluting the solution to /l.

(Comparative Developers A and B) Two types of comparative liquid developers A1BO were prepared by replacing the resin dispersion in the liquid developer production example described above with the following resin dispersion.

Comparative liquid developer A: Resin dispersion of resin particle production example 10 Comparative liquid developer B: These liquid developers were processed using fully automatic plate making machines ELP and TOV (
ELP master type (manufactured by Fuji Photo Film), which is an electrophotographic light-sensitive material, was exposed and developed to form a 140mm x 7σOm.
An offset mister with a large size of m was obtained. Furthermore, after processing 2,000 sheets of ELP master ■ type of the same size, the presence or absence of toner adhesion stains on the developing device was observed. or,
The obtained offset master was printed using a large plate printing machine Heidelberg 5OR-KZ type printing machine to adjust the printing pressure to an appropriate value.
Printing was performed with the θ setting set to a strong setting, and the number of sheets with faded letters and the like was observed through an accelerated test.

The results are shown in Table 1.

As shown in the results in Table 7 and Table 1, the developer made from the resin particles of the present invention did not stain the developing device and at the same time significantly increased the number of master plates printed. It can be seen that the liquid developer of the present invention forms images with excellent printing durability even in large plate sizes.

Example 1 A mixture of 100 g of the white dispersion obtained in Example 1 and Sumikalon Black/Jg was heated to a temperature of 100°C.
The mixture was heated and stirred for y hours.

After cooling to room temperature, the remaining dye was removed by passing it through a 2Qθ mesh nylon cloth to obtain a black resin dispersion with an average particle size of 0.2 opm.

A liquid developer was prepared by diluting 3.2 g of the above black resin dispersion and zirconium naphthenate to 27 g/l of Shell Sol.

When this was developed using the same apparatus as in Example/, a
Even after developing oooo sheets, no toner adhesion stains occurred on the device. Further, the image quality of the obtained master plate for offset printing was clear and the image quality of the printed matter after printing 70,000 sheets was also very clear.

Example 3 A mixture of the white dispersion/θOg obtained in Production Example 3 of resin particles and Victoria Blue BJH was heated at a temperature of 70° to r
The mixture was heated to ooC and stirred for an hour. After cooling to room temperature, 2OO
The remaining dye was removed by passing it through a mesh nylon cloth to obtain a blue resin dispersion with an average particle size of 0-0 μm.

3.2 g of the above-mentioned backing resin dispersion, 0.0 g of zirconium naphthenate. A liquid developer was prepared by diluting OJg to /l of Aituno R-H.

When this was developed using the same device as in Example/, -00
Even after developing 0 sheets, no toner adhesion stains were observed on the device. Further, the image quality of the obtained master plate for offset printing was clear and the image quality of the printed matter after printing 70,000 sheets was also very clear.

Example 32g of the white resin dispersion obtained in Production Example 2 of resin particles, and the nigrosine dispersion obtained in Example 1. A liquid developer was prepared by diluting 0.02 g of semi-docosanylamidated product of copolymer of tg and diimbutylene and maleic anhydride to ξ-G/l.

This was developed using the same device as in Example/, and the result was 200
Even after developing 0 sheets, no toner adhesion stains were observed on the device. In addition, the image quality of the obtained master plate for offset printing and the image quality of the printed matter after printing 10,000 copies were both clear.

After this developer was left to stand for three months, the same treatment as above was carried out, but the results were completely the same as before.

Example! 10 g of poly(decyl methacrylate), 30 g of Isopar H, and alkaline blue ♂g were placed in an Indian shaker together with glass beads, and dispersed for 2 hours to obtain a fine dispersion of alkaline blue.

30 g of white resin dispersion obtained in the example of manufacturing resin particles,
A liquid developer was prepared by diluting 1.2 g of the above alkali blue dispersion and 0.02 g of a semi-docosanylamidate of a copolymer of diisobutylene and maleic anhydride to a ratio of Isopar G/l.

When this was developed using the same device as in Example/, it was found that
Even after developing 0 sheets, no toner adhesion stains were observed on the device. Furthermore, both the image quality of the obtained master plate for offset printing and the image quality of the printed matter after printing one sheet were very clear.

Claims (1)

[Scope of Claims] An electrostatic photographic liquid developer comprising at least a resin dispersed in a carrier liquid having an electrical resistance of 10^9 Ω·cm or more and a dielectric constant of 3.5 or less, wherein the resin has the following (1) and A liquid developer for electrostatic photography, characterized in that it is obtained by the step (2). (1) A copolymer obtained by polymerizing the monomer (A) represented by the general formula (I) and the monomer (B) represented by the general formula (II), and further a monomer represented by the general formula (III) (
A step of obtaining a copolymer having an unsaturated bond introduced by reacting C). (2) At least the copolymer obtained in step (1), the monomer (D) that is soluble in the carrier liquid but becomes insolubilized by polymerization, and the monomer (E) represented by general formula (IV)
A step of polymerizing a solution containing one or more of each to obtain a resin dispersion. General formula (I) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (II) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (III) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ The symbols in general formulas (I), (II), (III), and (IV) represent the following. a_1, a_2, a_3, b_1, b_
2, b_3, d_1, d_2, d_3, e_1, e_2
, e_3 may be the same or different, and each represents a hydrogen atom, a hydrocarbon group, -CO_2J or -CH_
2CO_2J (J is a hydrogen atom or a hydrocarbon group). X, Y, V, Z are -O-, -S-, -CO-, -C
O_2-, -OCO-, -SO_2-, -CH_2OC
O-, -CONH-, -SO_2NH-, -NHCO-
, -NHCONH-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼. However, W
represents a hydrocarbon group or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. L is a hydrocarbon group or chemical bond that connects atomic group X and atomic group Q, and F connects atomic group V and atomic group G, respectively, and may be through a hetero atom. Q and G are each -CO_2H, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -
COCl, -OH, -NH_2, -NHR_4(R_4
is a hydrocarbon group), -NCO, and Q and G
are combinations that can easily form chemical bonds through reaction. R_1 is a hydrocarbon group having 4 to 20 carbon atoms. U is a hydrogen atom or a halogen atom, -OH, -CN,
-NH_2, -CO_2H, -SO_3H or -P
It is a hydrocarbon group having 18 or less carbon atoms that may be substituted with O_3H. T_1 and T_2 may be the same or different, and are -O-, -S-, -CO-, -CO_2-, -, respectively.
OCO-, -SO_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, -NH
CO_2-, -NHCONH-. However, U_1, U_2, U_3
, U_4, U_5 represent the same meaning as U. R_2,
R_3 may be the same or different, each may be substituted, or a hydrocarbon group having 1 to 8 carbon atoms may have a ▲ mathematical formula, chemical formula, table, etc. ▼ interposed in the main chain. It is. However, T_3 and T_4 may be the same or different, and T_1 and T_4 respectively.
It has the same meaning as 2. R_5 represents an optionally substituted hydrocarbon group having 18 or less carbon atoms. U_6 represents the same meaning as U. m, n, and p may be the same or different, and each is an integer of 0 to 4.