JP2592318B2 - Liquid developer for electrostatic photography - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a liquid developer for electrostatography comprising at least a resin dispersed in a carrier liquid having an electric resistance of not less than 10 ⁹ Ωcm and a dielectric constant of not more than 3.5. In particular, the present invention relates to a liquid developer having excellent redispersibility, storage stability, stability, image reproducibility, and fixability.

(Prior Art) A general liquid developer for electrophotography is a petroleum-based resin obtained by using an organic or inorganic pigment or dye such as carbon black, nigrosine or phthalocyanine blue and a natural or synthetic resin such as alkyd resin, acryl resin, rosin or synthetic rubber. Dispersed in a liquid with high insulation and low dielectric constant such as aliphatic hydrocarbons, and added with a polarity controlling agent such as a polymer containing metal soap, lecithin, linseed oil, higher fatty acid, and vinylpyrrolidone. .

In such a developer, the resin is dispersed in the form of particles having a diameter of several nm to several hundred nm as insoluble latex particles,
In the conventional liquid developer, the soluble dispersion stabilizing resin and the polarity controlling agent were easily diffused into the solution due to insufficient bonding between the soluble dispersion stabilizing resin and the polarity controlling agent and the insoluble latex particles. For this reason, there has been a defect that the soluble dispersion stabilizing resin is detached from the insoluble latex particles due to long-term storage or repeated use, and the particles settle, aggregate, accumulate, and the polarity becomes unclear. Further, since the particles once aggregated and deposited are difficult to re-disperse, the particles remain adhered to various parts of the developing device, leading to failure of the developing device such as contamination of an image area and clogging of a liquid feeding pump.

In order to improve these drawbacks, a means for chemically bonding a soluble dispersion stabilizing resin and insoluble latex particles has been devised, and is disclosed in US Pat. No. 3,990,980.
However, the dispersion stability of these liquid developers against spontaneous sedimentation of particles has been improved to some extent, but it is still insufficient, and when used in an actual developing device, the toner adhered to each part of the device becomes a coating film. In addition, it is difficult to re-disperse, and furthermore, it is not sufficient for re-dispersion stability which can be used practically, for example, it causes a failure of the apparatus, stains of a copied image, and the like. Further, in the method for producing resin particles described above, in order to produce monodisperse particles having a narrow particle size distribution, there are remarkable restrictions on the combination of a dispersion stabilizer to be used and a monomer to be insolubilized. As a result, particles having a large particle size distribution containing a large amount of coarse particles or polydisperse particles having two or more average particle diameters were obtained. In addition, it was difficult to obtain a desired average particle size with monodisperse particles having a narrow particle size distribution, and large particles of 1 μm or more or very fine particles of 0.1 μm or less were formed. Further, there is a problem that the dispersion stabilizer to be used must be produced through a complicated and time-consuming production process.

Furthermore, in order to improve the above-mentioned drawbacks, a copolymer insoluble insoluble swelling resin particle of a monomer to be insolubilized and a monomer containing a long-chain alkyl moiety or a monomer containing two or more polar components is used. The method of improving the degree of dispersion of the particles, redispersibility, storage stability is described in JP-A-60-179951 and JP-A-62-15.
It is disclosed in 1868 and the like. In addition, in the presence of a polymer using a bifunctional monomer or a polymer using a polymer reaction, a copolymer of a monomer to be insolubilized and a monomer containing a long-chain alkyl moiety is used as an insoluble dispersion resin particle. Methods for improving the degree of dispersion, redispersibility and storage stability of the particles are disclosed in JP-A-60-185963 and JP-A-61-63855.

(Problems to be Solved by the Invention) On the other hand, in recent years, a method of printing a large number of 5,000 or more sheets using an offset printing master plate by an electrophotographic method has been attempted. It has become possible to print 10,000 sheets or more in plate size. Further, the operation time of the electrophotographic plate making system has been shortened, and improvement in speeding up the development-fixing process has been performed.

JP-A-60-179951, JP-A-62-151868 and JP-A-60-18
Nos. 5963 and 61-63855 show that the dispersion resin particles produced according to the means disclosed in JP-A-61-63855 have an increased developing speed, dispersibility of the particles, redispersibility, and a reduced fixing time. Alternatively, in the case of a master plate of a large plate size (for example, A-3 size or more), the performance was not always satisfactory in terms of printing durability.

The present invention solves the problems of the conventional liquid developer as described above.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a liquid developer in which the fixing step is accelerated and which has excellent dispersion stability, re-dispersibility and fixability even in an electrophotographic plate making system using a large-size master plate. That is.

Another object of the present invention is to provide a developer capable of producing an offset printing original plate having excellent printing ink oil sensitivity and printing durability by electrophotography.

Another object of the present invention is to provide a liquid developer which can be used as various electrostatographic solutions and various transfer solutions in addition to the above-mentioned applications.

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 ink jet recording, cathode ray tube recording, and recording of various change processes such as pressure change or electrostatic change. That is.

(Means for Solving the Problems) An object of the present invention is to provide an electrophotographic solution developer comprising at least a resin dispersed in a non-aqueous solvent having an electric resistance of 10 ⁹ Ωcm or more and a dielectric constant of 3.5 or less. In the above, the dispersed resin particles are a polymer containing at least a repeating unit represented by the following general formula (I), a part of which is crosslinked, and a monofunctional polymer is provided only at one end of at least one polymer main chain. Is soluble in the non-aqueous solvent in the presence of a dispersion-stable soluble resin that is soluble in the non-aqueous solvent and is formed by bonding a polymerizable double bond group copolymerizable with the water-soluble monomer (A). And a monofunctional monomer (A) which is insolubilized by the following general formula (I)
A solution containing at least one monomer (B) containing an aliphatic group having 8 or more carbon atoms and having a copolymerization reaction with the monomer (A) shown in I) This has been achieved by an electrophotographic solution developer characterized by being copolymer resin particles obtained by the reaction.

General formula (I) In the general formula (I), X ¹ represents —COO—, —OCO—, —CH ₂ OCO
—, —CH ₂ COO—, —O—, or —SO ₂ —.

R ¹ represents a monovalent hydrogen group having 6 to 32 carbon atoms.

a ¹ and a ² may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -COO-R ² or a hydrocarbon group having 1 to 8 carbon atoms. Represents —COO—R ² (R ² represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms).

General formula (II) In the general formula (II), R ³ represents an aliphatic group having 8 or more carbon atoms.

Y ¹ is -COO-, -CONH-, (R ⁴ represents an aliphatic group), —OCO—, —CH ₂ COO—, or —O—.

b ^1, b ^2, which may be the same or different, each represents a hydrogen atom, an alkyl group, -COOR ⁵ or -CH ₂ -COOR ⁵ (R ⁵ represents an aliphatic group).

 Hereinafter, the liquid developer of the present invention will be described in detail.

The electric resistance used in the present invention is 10 ⁹ Ωcm or more, and the dielectric constant is 3.5.
The following carrier liquids and preferably linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons or directional group hydrocarbons, and their halogen-substituted products can be used. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, Isobar E, Icepar G, Isopar H, Isopar L (Isoper; a product of Exxon) Name), Shersol 70, Shersol 71 (Shersol; trade name of Shell Oil Company), AMSCO OM
S, Amsco 460 solvent (Amsco; trade name of Spritz) or the like is used alone or in combination.

Non-aqueous dispersion resin particles, which are the most important components in the present invention (hereinafter sometimes referred to as latex particles)
Is a polymer containing at least a repeating unit represented by the above general formula (I) in a non-aqueous solvent, a part of which is crosslinked, and monofunctional at only one end of at least one polymer main chain. A monofunctional monomer (A) and a carbon number in the presence of a dispersion-stable soluble resin soluble in the non-aqueous solvent and formed by bonding a polymerizable double bond group copolymerizable with the functional monomer (A). It is produced by polymerizing and granulating by copolymerizing with a monomer (B) having 8 or more aliphatic groups.

Here, as the non-aqueous solvent, basically, any solvent can be used as long as it is miscible with the carrier liquid of the electrophotographic solution developer.

That is, the solvent used again to produce the dispersed resin particles may be any solvent that can be mixed with the carrier liquid, and is preferably a linear or branched aliphatic hydrocarbon, an alicyclic hydrocarbon, or the like. Group hydrocarbons and their halogen-substituted products. For example, hexane, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, isopaffin petroleum solvents such as Isopar E, Isopar G, Isopar H, Isopar L, Shersol 70, Shersol 71, Amsco OM
S, Amsco 460 solvent or the like is used alone or as a mixture.

Solvents that can be used in combination with these organic solvents include alcohols (eg, methyl alcohol,
Ethyl alcohol, propyl alcohol, butyl alcohol, fluorinated alcohol, etc.), ketones (eg, acetone, methyl ethyl ketone, cyclohexanone, etc.), carboxylic esters (eg, methyl acetate, ethyl acetate, propyl acetate, betyl acetate, methyl propionate) ,
Ethyl propionate, etc.), ethers (eg, diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons (eg,
Methylene dichloride, chloroform, carbon tetrachloride, dichloroethane, methyl chloroform, etc.).

The non-aqueous solvent used by mixing these, after polymerization granulation,
It is desirable to evaporate under heating or under reduced pressure.However, as a latex particle dispersion, even if brought into the liquid developer, there is a problem if the liquid resistance of the developer can satisfy the condition of 10 ⁹ Ωcm or more. No.

Usually, it is preferable to use the same solvent as the carrier liquid in the step of producing the resin dispersion. As described above, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated Hydrocarbons and the like.

The solvent-insoluble copolymer produced by copolymerizing a monofunctional monomer (A) and a monomer (B) having an aliphatic group having 8 or more carbon atoms in a non-aqueous solvent is The dispersion stabilizing resin of the present invention used to obtain a resin dispersion has a general formula (I)
Is a polymer containing at least a repeating unit represented by the formula: partially crosslinked, and capable of copolymerizing with the monomer (A) only at one end of at least one polymer main chain. The resin is characterized by being a resin which is soluble in the non-aqueous solvent and has a bonding group.

 Hereinafter, the dispersion stable solution resin will be described in detail.

In the general formula (I) represented as a repeating unit of the polymer component, the hydrocarbon base may be substituted.

In the general formula (I), X ¹ is preferably -COO-,
_{-OCO -, - CH 2 OCO -} , - represents a CH ₂ COO-.

R ¹ preferably represents a hydrocarbon group having 8 to 22 carbon atoms, specifically, octyl, decyl, dodecyl,
And aliphatic groups such as tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosanyl group, eicosanyl group, octenyl group, decenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group and dococenyl group.

a ¹ and a ² may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (for example, a fluorine atom,
A chlorine atom, a bromine atom), a cyano group, a hydrocarbon group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, phenyl group, etc.), - COO-R ² group or a carbon number of 1 to
Represent -COO-R ² via 6 hydrocarbon group. Where R
² is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms (eg, methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl) Group, butenyl group, hexenyl group, octenyl group, decenyl group, benzyl group, phenethyl group, phenyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, chlorophenyl group, bromophenyl group, tolyl group, etc.). More preferably, one of a ¹ and a ² is a city lie atom.

As the repeating unit of the polymer main chain of the present invention, a repeating unit other than the unit represented by the general formula (I) may be contained.

As a repeating unit other than the general formula (I), for example,
Any monofunctional monomer copolymerizable with the monomer corresponding to the repeating unit represented by the general formula (I) may be used.

Specific examples include a repeating unit represented by the general formula (III).

General formula (III) In the formula (III), T ¹ represents —COO—, —OCO—, —CH ₂ OCO—,
_{-CH 2 COO -, - SO 2} -, - O -, - S-, _{-NHCO -, - CH 2 NHCO -} , - NHSO 2 -, - CH 2 NHSO 2 -, -
CONHCOO−, −CONHSO ₂ −, −NHCONH−, And the like.

W ¹ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms which may be substituted (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group,
Dodecyl group, tridecyl group, octadecyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 2-chloroethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-carboxyethyl group, butenyl group,
Hexenyl group, octenyl group, cyclohexyl group, benzyl group, phenethyl group, phenyl group, tolyl group, naphthyl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, bromobenzyl group, methylbenzyl group, methoxybenzyl group, etc.).

W ² represents a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group (eg, a methyl group, an ethyl group, a propyl group, a chloromethyl group, a hydroxymethyl group, an N, N-dimethylaminomethyl A N, N-diethylaminomethyl group), a hydroxy group, a carboxy group, or a sulfo group. n represents an integer of 1 to 4.

Z ¹ represents a linking group or a bond linking a benzene ring and R ⁶ , -COO-, -CH ₂ O-, -O-, -S-, And a direct bond between a benzene ring and R ⁶ (W ³ is
It represents a W ¹ same content and).

R ⁶ is a hydrogen atom, an unsubstituted hydrocarbon group having 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, heptyl, hexyl, cycloheptyl,
A cyclohexyl group, a hexenyl group, a phenyl group, etc.), a substituted aliphatic group having 1 to 22 carbon atoms [as the substituent, for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), -OH, _{-SH, -COOH, -SO 3 H,} -SO
_{2 H, -PO 3 H 2,} CH, -CONH 2, -SO 2 NH 2, (W ⁴ and W ⁵ each represent the same contents as W ¹ ), -OCO
W ₆ , -O-W ⁶ , -S-W ⁶ , _{^{-COOW 6, -SO 2 W 6 (}} W 6, W 7, W 8 each represents a substituted also good C1-18 hydrocarbon groups, specifically the same meaning of W ¹ ) Etc.), a heterocyclic group (for example, a thiophene ring, a pyran ring, a furan ring, a pyridine ring, a morpholine ring, a piperidine ring, an imidazole ring, a benzimidazole ring, a thiazolol ring and the like), or an aromatic group which may be substituted (for example, Phenyl, naphthyl, tolyl, xylyl, mesityl, fluorophenyl, chlorophenyl, bromophenyl, dichlorophenyl, dibromophenyl, trifluoromethylphenyl, hydroxyphenyl, methoxyphenyl, carboxyphenyl , Sulfophenyl group, carboxamidophenyl group, sulfamidophenyl group, methoxycarbonylphenyl group, acetamido Phenyl group, cyanophenyl group,
Nitrophenyl group, methanesulfonylphenyl group, etc.).

d ¹ and d ² may be the same or different from each other, and each represents the same content as a ¹ or a ² in the general formula (I).

Further, a monomer other than the monomer corresponding to the repeating unit represented by the above general formula (III) may be used. For example, maleic acid, maleic anhydride, itaconic anhydride, vinylnaphthalenes, vinyl group Are substituted directly with a ring (for example, vinyl pyridine, vinyl imidazole, vinyl thiophene, vinyl pyrrolidone, vinyl benzimidazole, vinyl triazole, etc.).

The dispersion stabilizing resin of the present invention corresponds to a polymer component selected from the repeating units represented by the general formula (I) as a homopolymer component or a repeating unit represented by the general formula (I). Contained as a copolymer component obtained by copolymerization with another monomer copolymerizable with the monomer (for example, a monomer corresponding to the repeating unit represented by the general formula (III)). And a polymer in which a part thereof is crosslinked, and further, a polymerizable double bond group is bonded to only one end of at least one of the polymer main chains.

The dispersion-stable resin of the present invention comprises a monomer corresponding to the repeating unit represented by the general formula (I) and another monomer copolymerizable with the monomer (for example, the monomer represented by the general formula (III) And the like, a monomer corresponding to the repeating unit represented by the general formula (I) 100
The amount is at least 30 parts by weight, preferably at least 50 parts by weight, more preferably at least 70 parts by weight with respect to parts by weight.

As a method for introducing a crosslinked structure into the polymer, a generally known method can be used. That is, in the polymerization reaction of the monomer, there are a method of polymerizing in the presence of a polyfunctional monomer and a method of including a functional group which advances a crosslinking reaction in a polymer and crosslinking by a polymer reaction. Preferably, a method of bridging between polymer chains by polymerizing a monomer having two or more polymerizable functional groups together with a monomer corresponding to the above general formula (I) is preferable.

Specifically, as the polymer functional group, CH ₂ —CH—, CH ₂ CHCH
−CH ₂ −, CH ₂ = CH-CONHCOO-, _{CH 2 = CH-NHCO-, CH} 2 = CH-CH 2 -NHCO-, CH 2 = CH-SO
_2- , CH ₂ CHCH—CO—, CH ₂ CHCH—O—, CH ₂ CHCH—S— and the like can be mentioned, and the monomer having two or more polymerizable functionalities is A monomer having two or more of the same or different polymerizable functional groups may be used.

Specific examples of the monomer having two or more polymerizable functional groups include, for example, as monomers having the same polymerizable functional group, styrene derivatives such as divinylbenzene and trivinylbenzene;
Polyhydric alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 200, # 400, # 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylol Methane, pentaerythritol, etc.) or polyhydroxyphenol (eg, hydroquinone, resorcin, catechol and derivatives thereof)
Esters, vinyl ethers or allyl ethers of methacrylic acid, acrylic acid or crotonic acid; dibasic acids (eg, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid) Vinyl esters, allyl esters, vinyl amides or allyl amides; polyamines (eg, ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, etc.) and carboxylic acids containing vinyl groups (eg, methacrylic acid, acrylic Acid, crotonic acid, allyl acetic acid, etc.).

Further, as a monomer having a different polymerizable functional group, for example, a carboxylic acid containing a vinyl group (for example, methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, acryloyl propionic acid, itaconiloyl acetic acid, itaco Reactant of niloylpropionic acid, carboxylic anhydride and alcohol or amine (eg, allyloxycarbonylpropionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonibenzoic acid, allylaminocarbonylpropionic acid, etc.)
Ester derivatives or amide derivatives containing a vinyl group (e.g., vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate, vinyl methacryloyl propionate, methacryloyl Allyl propionate, vinyloxycarbonylmethyl methacrylate, vinyloxycarbonylmethyloxycarbonylethylene acrylate, N-allylacrylamide, N-allylmethacrylamide, N
-Allyl itaconamide, methacryloyl propionate allyl amide, etc.); or amino alcohols (for example, aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-akinobutanol, etc.) and a vinyl group. Condensates with carboxylic acids and the like can be mentioned.

In the present invention, a partially crosslinked resin is formed by polymerizing a monomer having two or more polymerizable functional groups using 15% by weight or less, preferably 10% by weight or less of all monomers. can do.

Further, the polymerizable double bond group bonded only to one terminal of the polymer main chain has a chemical structure bonded directly to one terminal of the polymer main chain or bonded via an arbitrary linking group.

Specifically, for example, the chemical structure represented by the general formula (IV) can be mentioned.

General formula (IV) Wherein (IV), T ² represents T ¹ same contents as in the general formula (III).

e ¹ and e ² may be the same or different from each other, and d ¹ in the general formula (III) also represents the same content as d ² .

Q ¹ is Represents a bond directly linking to one end of the polymer main chain, or a linking group via an arbitrary linking group.

Examples of the bonding group include a carbon-carbon bond (single bond or double bond), a carbon-heteroatom bond (for example, an oxygen atom, a sulfur atom, a nitrogen atom, and a silicon atom), and a heteroatom-heteroatom bond. It is composed of any combination of atomic groups. For example, [Z ² and Z ³ are each a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxy group, an alkyl group (eg, a methyl group, an ethyl group, a propyl group, etc.), etc. ), CH = CH, -O-, -S-, -COO -, - SO ₂ -, -NHCOO-, -NHCONH-, [Z ⁴ and Z ⁵ are each a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms (eg, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenethyl, phenyl) , Tolyl group, etc.) or -OZ ⁶ (Z ⁶ is Z ⁴
Represents the same content as the hydrocarbon group in the above)).

Specific examples of the polymerizable double bond-bonding group represented by the general formula (IV) that is bonded to only one terminal of the polymer main chain as described above are shown below. However, in the following embodiment, A represents -H, a -CH ₃ or -CH ₂ COOCH _3, B is -H or -
It represents a CH _3. Further, n represents an integer of 2 to 10, m represents 2 or 3, l represents 1, 2 or 3, and p represents 1
Represents an integer of ~ 4, and q represents 1 or 2.

(1) CH ₂ = CH-COO-, _{(4) CH 2 = CH-} CH 2 COO-, (5) CH 2 = CH-OCO-, (6) CH 2 = CH-CH 2 OCO
−, _{(19) CH 2 = CH-} CH 2 COO (CH 2 n S-, _{(24) CH 2 = CH-} OCO (CH 2 l S-, (25) CH 2 = CH-CH 2 -OCO- (CH 2 l S-, The dispersion-stable soluble resin of the present invention comprising a polymerizable double bond group bonded to only one terminal of the polymer main chain has various double bonds at the terminal of a living polymer obtained by conventionally known anionic or cationic polymerization. Reacting a reagent containing a group, or adding a “specific reactive group” (eg, —OH, —COOH, —SO ₃ H, —N
_{H 2, -SH, -PO 3 H} 2, -NCO, -NCS, -COCl, was reacted a reagent containing -SO ₂ Cl, etc.),
A method of introducing a polymerizable double bond group by a polymer reaction (method by an ionic polymerization method) or a radical using a polymerization initiator and / or a chain transfer agent containing the above “specific reactive group” in the molecule. After polymerization, the polymer is easily reacted by a synthetic method such as a method of introducing a polymerizable double bond group by conducting a polymer reaction using a “specific reactive group” bonded only to one end of the polymer main chain. Can be manufactured.

Specifically, P.Dreyfuss & RPQuirk, Encycl.Poly
m.Sci.Eng., 7 , 551 (1987), Yoshiki Chujo, Yuya Yamashita, "Dyes and Drugs", 30 , 232 (1985), Akira Ueda, Susumu Nagai, "Science and Industry", 60 , 57 (1986), PFRemmp & E.Franta, Adv
ances in Polymer Science, 58 , 1 (1984), Koichi Ito "Polymer Processing", 35 , 262 (1986), V. Percec, Applied P
A polymerizable double bond group can be introduced according to a method described in a review such as Polymer Science, 285 , 97 (984) and references cited therein.

More specifically, at least one monomer corresponding to the repeating unit represented by the general formula (I), a polyfunctional monomer for introducing the above-mentioned crosslinked structure, and the above-mentioned “ A method of polymerizing a mixture of a chain transfer agent containing a “specific reactive group” with a polymerization initiator (for example, an azobis compound, peroxide or the like), or without using the above chain transfer agent, Polymerization using a polymerization initiator containing a “reactive group”, or a method using a compound containing the above “specific reactive group” in the molecule for both the chain transfer agent and the polymerization initiator, etc. A polymer having a crosslinked structure and having a “specific reactive group” bonded only to one end of a polymer seed chain is synthesized. Next, there is a method in which a polymerizable double bond is introduced by performing a polymer reaction using the “specific reactive group”.

As the chain transfer agent to be used, for example, the “specific reactive group” or a mercapto compound containing a substituent derivable to the “specific reactive group” {eg, thioglycolic acid, thiomalic acid, thiosalicylic acid, -Mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptoacetic acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N
-(2-Mercaptoethyl) amino] propionic acid, N
-(3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 1-mercapto-2-propanol,
3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, etc., or the “specific reactive group” or the “specific reactive group” Examples thereof include iodized alkyl compounds containing a derivable substituent (for example, mode acetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, and 3-iodopropanesulfonic acid). Preferably, a mercapto compound is used.

Further, examples of the polymerization initiator containing a substituent which can be derived to “specific reactive group” or “specific reactive group” include, for example, 4,4′-azobis (4-cyanovaleric acid),
4,4'-azobis (4-cyanovaleric chloride), 2,
2'-azobis (2-cyanopropanol), 2,2'-azobis (2-cyanopentanol), 2,2'-azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidine- 2-yl) propane], 2,2'-azobis ｛2
-Methyl-N- [1,1-bis (hydroxymethyl) -2
-Hydroxyethyl] propioamide}, 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propioamide}, 2,2'-azobis [2
-Methyl-N- (2-hydroxyethyl) -propioamide] 2,2'-azobis (2-amidinopropane).

The amount of these chain transfer agents or polymerization initiators used is
The amount is 0.5 to 15 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the total monomers.

The dispersion stabilizing resin of the present invention is soluble in an organic solvent, specifically, a temperature of 2 with respect to 100 parts by weight of a toluene solvent.
What is necessary is just to dissolve at least 5 parts by weight of the dispersion-stable soluble resin at 5 ° C.

The weight average molecular weight of the dispersion stabilizing resin of the present invention is 1 × 10
^{It is 4} to 1 × 10 ⁶ , preferably 3 × 10 ^{4 to} 5 × 10 ⁵ .

Monomers used in producing the non-aqueous dispersion resin,
It contains a monofunctional monomer (A) which is soluble in the non-aqueous solvent but is insolubilized by polymerization, and an aliphatic group having 8 or more carbon atoms represented by the general formula (II) and It can be distinguished from the monomer (A) and the monomer (B) which undergoes copolymerization.

The monomer (A) in the present invention may be any monofunctional monomer which is soluble in a non-aqueous solvent but insolubilized by polymerization. Specifically, for example, a monomer represented by the general formula (V) can be mentioned.

General formula (V) In the general formula (V), Y ² represents —COO—, —OCO—, —CH ₂ OCO
_{-, CH 2 COO -, -} O-, Represents Here, R ⁸ is a hydrogen atom or an aliphatic group having 1 to 18 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group, a 2-chloroethyl group).
Bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, benzyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, phenethyl group, 3-phenylpropyl group, dimethylbenzyl group, fluorobenzyl group, 2-methoxyethyl A 3-methoxypropyl group).

R ⁷ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, 2-chloroethyl, 2,2-dichloroethyl, 2, 2,2-trifluoroethyl group, 2-bromoethyl group, 2-glycidylethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, 2-hydroxy-3-chloropropyl group, 2
-Cyanoethyl group, 3-cyanopropyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-ethoxyethyl group, N, N-dimethyllaminoethyl group, N, N-diethylaminoethyl Group, trimethoxysilpropyl group, 3-bromopropyl group, 4-hydroxybutyl group, 2-furfurylethyl group, 2-thienylethyl group, 2-pyridylethyl group, 2-morpholinoethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-phosphoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 2-
Carboxamidoethyl group, 3-sulfoamidopropyl group, 2-N-methylcarboxamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

f ¹ and f ² may be the same or different from each other, and each represents the same content as a ¹ or a ² in the general formula (I).

Specific monofunctional monomers (A) include, for example, aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, propionic acid,
Acetic acid, monochloroacetic acid, trifluoropropionic acid, etc.) vinyl esters or allyl esters; unsaturated carboxylic acids, such as acrylics, methacrylic acid, crotonic acid, itaconic acid, and maleic acid, having 1 to 4 substituents Alkyl esters or amides (for example, as an alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group,
2-chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group, trifluoroethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2 −
Benzenesulfonylethyl group, 2- (N, N-dimethylamino) ethyl group, 2- (N, N-diethylamino) ethyl group, 2-carboxyethyl group, 2-phosphoethyl group, 4
-Carboxybutyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-chloropropyl group, 2-hydroxy-3-chloropropyl group, 2-furfurylethyl group, 2
A pyridinylethyl group, a 2-thienylethyl group, a trimethoxysilpropyl group, a 2-carboxamidoemitz group, etc.); styrene derivatives (for example, styrene, vinyltoluene, α-methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, Bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N, N-dimethylaminomethylstyrene, vinylbenzenecarboxamide, vinylbenzenesulfonamide, etc.); acrylic acid, methacrylic acid Unsaturated carboxylic acids such as acids, crotonic acid, maleic acid and itaconic acid;
Maleic acid, cyclic anhydride of itaconic acid; acrylonitrile; methacrylonitrile; a polymerizable double bond group-containing heptyl ring compound (specifically, for example, "Polymer Data Handbook-Basic Edition-" edited by the Society of Polymer Science, Japan, p175-184, compounds described in Baifukan (1986), such as N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidonevinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc. Is mentioned.

 Two or more monofunctional monomers (A) may be used in combination.

Next, the monomer (B) represented by the general formula (II) used in the present invention will be further described.

In the general formula (II), preferably, R ³ represents an alkyl group which may be substituted having 10 or more carbon atoms or an alkenyl group having 10 or more carbon atoms, and Y ¹ represents -COO-, -CONH-, [However, R ⁴ preferably represents an aliphatic group having 1 to 32 carbon atoms (the aliphatic group represents, for example, an alkyl group, an alkenyl group or an aralkyl group)], -OCO-, -CH ₂ OCO- or Represents -O-. b ¹ and b ² may be the same or different and are preferably a hydrogen atom, a methyl group, -COOR ⁵ or -CH ₂
COOR ⁵ (wherein R ⁵ preferably represents an alkyl group, alkenyl group, aralkyl group or cycloalkyl group having 1 to 32 carbon atoms).

Still more preferably, in the formula (II), Y ¹ is -COO-,
-CONH- or Wherein b ¹ and b ² may be the same or different and each represent a hydrogen atom or a methyl group, and R ³ has the same contents as described above.

Specific examples of the monomer (B) represented by the general formula (II) include an aliphatic group having a total of 10 to 32 carbon atoms (the aliphatic group is a halogen atom, a hydroxyl group, an amino group alkoxy group, or the like). Acrylic acid, methacrylic acid, crotonic acid, maleic acid which may contain a substituent, or may have a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom or the like, and a carbon-carbon bond in its main chain may be interposed. Acid, ester acid of unsaturated carboxylic acid such as itaconic acid (for example, aliphatic group such as decyl group, dodecyl group, tridecyl group, tetradecyl group,
Hexadecyl group, octadecyl group, docosanyl group, dodecenyl group, hexadecenyl group, oleyl group, linoleyl group, docosenyl group, etc .; amides of unsaturated carboxylic acids described above (the aliphatic groups are the same as those shown for esters) Vinyl esters or allyl esters of higher fatty acids (higher fatty acids such as lauric acid, myristic acid, stearic acid, oleic acid, linoleic acid, behenic acid, etc.); or aliphatic groups having 10 to 32 carbon atoms in total. (The aliphatic group represents the same range as the aliphatic group of the unsaturated carboxylic acid).

The dispersing resin of the present invention comprises at least one kind of each of the monomer (A) and the monomer (B). What is important is that the resin synthesized from these monomers is insoluble in the non-aqueous solvent. If so, a desired dispersion resin can be obtained. More specifically, the monomer (B) represented by the general formula (II) is preferably used in an amount of 0.1 to 20% by weight, more preferably 0.3 to 8% by weight, based on the monomer (A) to be insolubilized. % By weight. Further, the molecular weight of the dispersion resin of the present invention is preferably from 10 ³ to 10 ⁶ , more preferably from 10 ⁴ to 10 ⁶ .

In order to produce the dispersion resin used in the present invention as described above, generally, the dispersion-stable soluble resin, monomer (A) and monomer (B) as described above are mixed in a non-aqueous solvent. Heat polymerization may be performed in the presence of a polymerization initiator such as benzoyl oxide, azobisisobutyronitrile, and butyllithium.

Specifically, a method of adding a polymerization initiator to a mixed solvent of a dispersion-stable resin, a monomer (A) and a monomer (B),
A method in which the monomer (A) and the monomer (B) are dropped together with the polymerization initiator into a solution in which the dispersion-stable resin is dissolved,
Alternatively, a method of optionally adding the remaining monomer mixture together with the polymerization initiator to a mixed solution containing the entire amount of the dispersion-stable resin and a part of the mixture of the monomer (A) and the monomer (B),
Further, there is a method of optionally adding a mixed solution of the dispersion-stable resin and the monomer together with the polymerization initiator in a non-aqueous solvent, and the like, and any of these methods can be used.

The total amount of the monomers (A) and (B) is
0 to 5 parts by weight to about 5 to 80 parts by weight, preferably 10
5050 parts by weight.

The amount of the soluble dispersion-stabilized resin which is a dispersion stabilizer is 1 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of all the monomers used above.

The amount of the polymerization initiator is suitably from 0.1 to 5% by weight based on the total amount of the monomers.

The polymerization temperature is about 50 to 180 ° C., preferably 60 to 1
20 ° C. The reaction time is preferably 1 to 15 hours.

In the non-aqueous solvent used for the reaction, the alcohols described above,
When polar solvents such as ketones, ethers and esters are used in combination, or when unreacted monomer (A) or monomer (B) to be polymerized and granulated remains, the solvent or monomer may be used. It is preferred to remove by heating to a temperature higher than the boiling point of the body or distilling it off or by distilling it off under reduced pressure.

Non-aqueous latex particles produced as described above,
At the same time as being fine and having a uniform particle size distribution, the particles exhibit extremely stable dispersibility. It is easy and no contamination is observed on each part of the apparatus.

Further, when fixed by heating or the like, a strong film was formed, and excellent fixability was exhibited.

Further, the liquid developer of the present invention has a rapid development-fixing process and is excellent in dispersion stability, re-dispersibility and fixability even when a large-size master plate is used.

If desired, a colorant may be used in the liquid developer of the present invention. The colorant is not particularly limited, and various conventionally known pigments or dyes can be used.

In the case of coloring the dispersion resin itself, for example, as one of the coloring methods, there is a method of physically dispersing the dispersion resin in a dispersion resin using a pigment or a dye. I have. For example, magnetic iron oxide powder, powdered lead iodide, carbon black, nigrosine, alkali blue, Hansa Yellow, quinacridone red, phthalocyanine blue and the like can be mentioned.

As another method of coloring, there is a method of dyeing a dispersion resin with a preferable dye as described in JP-A-57-48738. Alternatively, as another pope, there is a method in which a dispersing resin and a dye are chemically bonded as disclosed in JP-A-53-54029.
As described in -22955 and the like, there is a method of producing a dye-containing copolymer by using a monomer containing a dye in advance when producing by a polymerization granulation method.

Various additives may be added to the liquid state-of-the-art agent of the present invention as needed in order to enhance charging characteristics or improve image characteristics. For example, Yuji Harazaki “Electrophotography” Vol. 16, No. 2
And those specifically described on page 44 are used.

For example, di-2-ethylhexylsulfosuccinic acid metal salt, naphthenic acid metal salt, higher fatty acid metal salt, lecithin,
Examples include poly (vinylpyrrolidone) and a copolymer containing a semi-maleic acid amide component.

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

The amount of the toner particles containing the resin and the optional coloring agent as a seed component is preferably 0.5 parts by weight to 50 parts by weight with respect to 1000 parts by weight of the carrier liquid. If the amount is less than 0.5 part by weight, the image density becomes insufficient, and if it exceeds 50 parts by weight, fogging to a non-image portion is liable to occur. Further, the carrier liquid-soluble resin for stabilizing the dispersion is also used as desired, and can be added in an amount of about 0.5 to 100 parts by weight based on 1,000 parts by weight of the carrier liquid.
The charge control agent as described above is used for 1,000 parts by weight of the carrier liquid.
0.001 to 1.0 parts by weight is preferred. If desired, various additives may be added. The upper limit of the total amount of these additives is regulated by the electric resistance of the developer. That is, the electric resistance of the liquid developer from which the toner particles have been removed is 10 ⁹
If it is lower than Ωcm, it becomes difficult to obtain a high quality continuous tone image, so it is necessary to control the amount of each additive within this limit.

(Examples) Examples of the present invention will be shown below, but the contents of the present invention are not limited thereto.

Production Example 1 of dispersion stabilizing resin: Production of P-1 100 g of octadecyl methacrylate, divinylbenzene
A mixed solution of 2.0 g, 150 g of toluene and 50 g of isopropanol was heated to a temperature of 80 ° C. while stirring under a nitrogen stream.
2,2'-azobis (4-cyanovaleric acid) (ACV)
Was added and reacted for 8 hours. After cooling, methanol 2
After reprecipitation, the white powder was collected by filtration and collected. White powder obtained
A mixture of 50 g, 7.6 g of glycidyl methacrylate, 0.5 g of t-butylhydroquinone, 0.5 g of N, N-dimethyldodecylamine and 100 g of toluene was heated to a temperature of 100 ° C. and stirred for 20 hours. The reaction mixture was reprecipitated in methanol 1, the pale yellow powder was collected by filtration and dried. The yield was 43 g and the weight average molecular weight was 9.5 × 10 ⁴ .

Production Examples 2 to 10 of Dispersion Stabilizing Resins: Production of P-2 to P-10 In Production Example 1, exactly the same as Production Example 1 except that the monomers shown in Table 1 below were used instead of octadecyl methacrylate. To produce the dispersion stabilizing resins P-2 to P-10. The average weight of each resin is 9.0 × 10 ^{4 to} 10.5 ×
It was 10 ⁴ .

Production Examples 11 to 23 of Resin for Stabilizing Dispersion: Production of P-11 to P-23 In Production Example 1, instead of 2.0 g of divinylbenzene which is a polyfunctional monomer for crosslinking, a polyfunctional compound shown in Table 2 below was used. Each dispersion stabilizing resin P-11 to P-23 was produced in the same manner as in Production Example 1 except that a hydrophilic monomer or oligomer was used.

Production Example 24 of dispersion stabilizing resin Production of P-24 Octadecyl methacrylate 100 g, thiomalic acid 3 g,
4.5 g of divinylbenzene, 150 g of toluene and 50 of ethanol
g of the mixed solution was heated to a temperature of 60 ° C. under a nitrogen stream.
2,2'-azobis (isobutylnitrile) (abbreviation AIB
N.) was added and reacted for 5 hours, then 0.3 g of AIBN was added and reacted for 3 hours, and 0.2 g of AIBN was further added and reacted for 3 hours. After cooling, the precipitate was reprecipitated in methanol 2, and the white powder was collected by filtration and dried, yielding 85 g.

A mixture of 50 g of the above powder and 100 g of toluene was heated to a temperature of 40 ° C. and dissolved with stirring. Next, 0.2 g of t-butyl hydroquinone, 8 g of vinyl acetate, and 0.03 g of mercury acetate were added and reacted for 2 hours. Then raise the temperature to 70 ° C, 100%
1.2 × 10 ⁻³ ml of sulfuric acid was added and reacted for 18 hours. After the reaction, add 3.6 g of sodium acetate trihydrate to the reaction solution and add
After stirring for minutes, the precipitate was reprecipitated in cooled methanol 1.5. 41 g of a slightly brownish powder was obtained. The weight average molecular weight of this powder was 10.5 × 10 ⁴ .

Production Example 25-30 of dispersion stabilizing resin: Production of P-25 to P30 In the above Production Example 24, except that 3 g of thiomalic acid was replaced with a mercapto compound shown in Table 3 below, in the same manner as in Production Example 24 By operation, dispersion stabilizing resins P-25 to P-30 were produced.

Production Example 31 of dispersion stabilizing resin: Production of P-31 Production Example 24 except that a mixed solution of 100 g of dodecyl methacrylate, 4 g of ethylene glycol dimethacrylate, 4 g of 2,3-epoxypropyl ester thioglycolate, and 200 g of triene was used. A polymerization reaction was performed in the same manner.

Next, 6 g of crotonic acid, 2,2'-methylenebis- (6-
1.0 g of t-butyl-p-cresol) and 0.8 g of N-N'-dimethyldodecylamine, and the mixture was stirred at a temperature of 100 ° C under stirring.
Reacted for 0 hours. The reaction mixture was reprecipitated in methanol 2 to obtain a pale yellow viscous substance by a decantation method and then dried. The yield was 75 g and the weight average molecular weight was 6.5 × 10 ⁴ .

Production Examples 32 to 40 of dispersion stabilizing resin: Production of P-32 to P-40 In the above Production Example 31, dodecyl methacrylate 100 g
In place of 6 g of crotonic acid and carboxylate containing a polymerizable double bond group shown in Table 4 below, each dispersion stabilizing resin P- 32-40 were produced. The weight average molecular weight of each resin was 6.0 × 10 ^{4 to} 7.5 × 10 ⁴ .

Production Example 41 of dispersion stabilizing resin: Production of P-41 Tridecyl methacrylate 100 g, divinylbenzene 1.
A mixed solution of 2 g and 200 g of tetrahydrofuran was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. 6 g of 4,4'-azobis (4-cyanopetanol) was added and reacted for 8 hours.
Next, after cooling the reaction, 6.2 g of methacrylic anhydride,
0.8 g of t-butylhydroquinone and 1 drop of concentrated sulfuric acid were added, and the mixture was stirred at a temperature of 30 ° C. for 1 hour, and further at a temperature of 50 ° C. for 3 hours. After cooling, the precipitate was reprecipitated in methanol 2 and the solution was removed by decantation. A brown viscous substance was collected and dried. yield
The weight average molecular weight was 11.3 × 10 ⁴ at 88 g.

Production Example 42 of Dispersion Stabilizing Resin: Production of P-42 A mixed solution of 100 g of octadecyl methacrylate, 1.1 g of ethylene grill diacrylate and 200 g of tetrahydrofuran was heated to a temperature of 70 ° C. while stirring under a nitrogen stream.
5 g of 4,4'-azobis (4-cyanopentanol) was added and reacted for 5 hours. Further, the above azobis compound 1.0 was added and reacted for 5 hours. The reaction mixture was cooled in a water bath to a temperature of 20 ° C., and 3.2 g of pyridine and 2,2′-methylenebis-
1.0 g of (6-t-butyl-p-cresol) was added and stirred. To this mixed solution, 4.2 g of methacrylic acid chloride was added dropwise over 30 minutes so that the reaction temperature did not exceed 25 ° C. temperature
Stirred at 20 ° C to 25 ° C for 4 hours. Next, the reaction product was reprecipitated in a mixture of methanol 1.5 / water 0.5, and a white powder was collected by filtration and dried. The yield was 82 g and the weight average molecular weight was 11.2 × 10 ⁴ .

Production Examples 43 to 51 of Dispersion Stabilizing Resins: Production of P-43 to P-51 Production Example 4 was the same as in Production Example 42 except that the acid chlorides in Table 5 below were used instead of methacrylic acid chloride.
Are operated in exactly the same manner to obtain each dispersion stabilizing resin P-43 to P-43.
51 were manufactured. The weight average molecular weight of each resin is 10 × 10 ^{4 to} 20
× 10 ⁴

Production Example 52 of Dispersion Stabilizing Resin: Production of P-52 A mixed solution of 100 g of dodecyl dimethacrylate, 0.8 g of ethylene glycol methacrylate and 200 g of tetrahydrofuran was heated to a temperature of 65 ° C. under a nitrogen stream. 4 g of 2,2'-azobis (4-cyanovaleric acid chloride) was added and the mixture was stirred for 10 hours. The reaction mixture was cooled to a temperature of 25 ° C. or lower in a water bath, and 2.4 g of allyl alcohol was added. 2.5 g of pyridine was added dropwise so that the reaction temperature did not exceed 25 ° C., and the mixture was stirred for 1 hour. After stirring at a temperature of 40 ° C. for 2 hours, the mixture was reprecipitated in methanol 2. A decanted pale yellow viscous material was obtained and dried. The yield was 80 g and the weight average molecular weight was 10.5 × 10 ⁴ .

Dispersion stabilizing resin production examples 53 to 61: Production of P-53 to 61 In the above production example 24, instead of octadecyl methacrylate and divinylbenzene, the methacrylates and polyfunctional monomers shown in Table 6 below were used. Is Production Example 24
Resins P-53 to P61 were produced in the same manner as described above. The weight average molecular weight of each of the obtained resins was 9.0 × 10 ^{4 to} 12 × 10 ⁴ .

Production Example 1 of Latex Particles 1: Production of Latex Particles D-1 12 g of dispersion stabilizing resin P-1, 100 g of vinyl acetate, 1.0 g of octyl methacrylate and 384 g of Isopar H were stirred under a nitrogen stream while stirring. Heated to a temperature of 70 ° C. 2,2'-azobis (isovaleronitrile) (abbreviation A.
(IVN) 0.8 g was added and reacted for 6 hours. Twenty minutes after the initial addition, cloudiness occurred and the reaction temperature rose to 88 ° C. Temperature 10
The temperature was raised to 0 ° C and the mixture was stirred for 2 hours to distill off unreacted vinyl acetate. After cooling, the white dispersion obtained by passing through a 200-mesh nylon cloth was a latex having a conversion of 90% and an average particle size of 0.24 μm.

Production Examples 2 to 12 of Latex Particles: Latex Particles D-2
Production of D-12 The same procedure as in Production Example 1 was carried out except that the resin for dispersion stabilization described in Table 7 below was used instead of Resin P-1 in Production Example 1 of latex particles. Latex particles D-2 to D-12 were produced.

Production Examples 13-18 of Latex Particles: Latex Particles D-13
Production of D-18 In the production example of latex particles D-1, each latex particle was produced in the same manner as in Production Example 1 except that 1 g of each of the monomers in Table 8 was used instead of 1 g of octadecyl methacrylate. did.

Production Example 19 of Latex Particles: Production of Latex Particles D-19 A mixed solution of 6 g of the dispersion stabilizing resin P-10, 8 g of poly (octadecyl methacrylate), 100 g of vinyl acetate, 0.8 g of dodecyl methacrylate and 400 g of Isopar H under a nitrogen stream. While stirring, the mixture was heated to a temperature of 75 ° C. 0.7 g of 2,2'-azobis (isobutylnitrile) (abbreviated AIBN) was added and reacted for 4 hours, and 0.5 g of AIBN was further added and reacted for 2 hours. After cooling, the white dispersion obtained through a 200-mesh nylon cloth was a latex having an average particle size of 0.17 μm.

Production Example 20 of Latex Particles: Production of Latex Particles D-20 10 g of dispersion stabilizing resin P-11, 90 g of vinyl acetate, 10 g of N-vinylpyrrolidone, 1.5 g of octadecyl methacrylate
And 400 g of isododecane were heated to a temperature of 65 ° C. while stirring under a nitrogen stream. Add 1.5g of AIBN and add 4
Reacted for hours. After cooling, the white dispersion obtained by passing through a 200-mesh nylon cloth was a latex having an average particle size of 0.25 μm.

Production Example 21 of Latex Particles: Production of Latex Particles-21 A mixed solution of 20 g of dispersion stabilizing resin P-1, 94 g of vinyl acetate, 6 g of crotonic acid, 2 g of hexadecyl methacrylate and Isopar G was stirred under a nitrogen stream while stirring. Heated to a temperature of 60 ° C. 1.0 g of AIVN was added and reacted for 2 hours. Further, 0.5 g of AIVN was added and reacted for 2 hours. 20 after cooling
The white dispersion obtained through a 0-mesh nylon cloth was a latex having an average particle size of 0.28 μm.

Production Example 22 of Latex Particles: Production of Latex Particles D-22 25 g of dispersion stabilizing resin P-16, metal methacrylate 1
A mixed solution of 00 g, 2 g of decyl methacrylate, and Isopar H was heated to a temperature of 60 ° C. while stirring under a nitrogen stream.
0.7 g of AIVN was added and reacted for 4 hours. After cooling, the white dispersion obtained by passing through a 200-mesh nylon cloth has an average particle size of 0,0.
It was a 38 μm latex.

Production Example 23 of Latex Particles: Production of Latex Particles D-23 A mixed solution of 25 g of dispersion stabilizing resin P15, 100 g of styrene, 2 g of octadecyl vinyl ether, and 380 g of Isopar H was heated to a temperature of 45 ° C. while stirring under a nitrogen stream. . n
A hexane solution of -butyllithium was added in an amount of 1.0 g as a solid amount of n-butyllithium, and reacted for 4 hours.
After cooling, the white dispersion obtained by passing through a 200-mesh nylon cloth was a latex having an average particle size of 0.35 μm.

Production Example 24 of Latex Particles: (Comparative Example A) Latex particles except that a mixed solution of 20 g of poly (octadecyl methacrylate) <dispersion stabilizing resin [R] -1>, 100 g of vinyl acetate, 1 g of octadecyl methacrylate and 380 g of Isopar H was used. In the same manner as in Production Example 1, a white dispersion which was a latex particle having a conversion of 88% and an average particle size of 0.27 μm was obtained.

Production Example 25 of Latex Particles: (Comparative Example B) A mixed solution of 97 g of octadecyl methacrylate, 3 g of acrylic acid and 200 g of toluene was heated to a temperature of 75 ° C. under a nitrogen stream. 1.0 g of AIBN was added and reacted for 8 hours. Next, 12 g of glycidyl methacrylate, t-butyl hydroquinone
1.0 g, 1.2 g of N, N-dimethyldotecilamine were added, and the temperature was 100.
Stirred at 40 ° C. for 40 hours. After cooling, the precipitate was reprecipitated in methanol 2 and the white powder was collected by filtration and dried. A resin [R] -2 for stabilization having the following structure was obtained. The yield is 84 g and the weight average molecular weight is 35,00
It was 0.

Dispersion stabilizing resin [R] -2: 10 g of this dispersion stabilizing resin [R] -2,
g, octadecyl methacrylate 1.0 g and Isopar H38
Production example 1 of latex particles except using 4 g of mixed solution
In the same manner as in the above, a white dispersion as latex particles having a polymerization rate of 89% and an average particle size of 0.15 μm was obtained.

Production Example 26 of Latex Particles: (Comparative Example C) A dispersion stabilizing resin [R] having the following structure produced by the method described in JP-A-61-63855 (weight-average carried amount: 46,
000) is treated in the same manner as in Example 1 of the manufacture of latex particles except that a mixed solution of 12 g of vinyl acetate, 100 g of vinyl acetate, 1.0 g of octadecyl methacrylate and 382 g of Isopar H is used.
% Of a latex particle having an average particle diameter of 0.23 μm.

Dispersion stabilizing resin [R] -3: Example 1 10 g of a dodecyl methacrylate / acrylic acid copolymer (copolymerization ratio (95/5) by weight), 10 g of Niglon and 30 g of Isopar G were put together with glass beads into a paint shaker (Tokyo Seiki Co., Ltd.) and Time-dispersed to obtain a fine dispersion of nigrosine.

30 g of the resin dispersion of Production Example 1 for latex particles, 2.5 g of the above nigrosine dispersion, and 0.07 g of octadecene / half-maleic acid octadecylamide copolymer were added to Isopar G
To obtain a liquid developer for electrostatography.

(Comparative Liquid Developers A to C) Three kinds of comparative liquid developers A, B and C were prepared in place of the following resin particles of the resin dispersion in the above Production Examples.

Comparative Liquid Developer A: Latex Particle Production Example 24 Resin Dispersion Comparative Liquid Developer B: Latex Particle Production Example 25 Resin Dispersion Comparative Liquid Developer C: Latex Particle Production Example 26 Resin Dispersion Materials These liquid developers are used as a developer for the fully automatic plate making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.), and the ELP Master II type electrophotographic photosensitive material (manufactured by Fuji Photo Film Co., Ltd.) is exposed and developed. Processed. The plate making speed was 7 plates / min. In addition, set the ELP Master II type to 2000
After the sheet processing, it was observed whether or not the toner adhered to the developing device. The blackening rate (image area) of the copied image was determined using a document having a 40% density. The results are shown in Table-9.

As described above, where plate making is performed using each developer under plate making conditions,
As is evident from the results in Table 9, the developer of the present invention did not cause staining of the developing device and had a clear image on the 2000th plate making plate.

On the other hand, a master plate for offset printing (ELP master) obtained by making a plate from each developer was printed by a conventional method, and the number of printed sheets until the occurrence of missing characters, blurred solid portions, etc. in the printed image was compared. Place, the present invention, Comparative Example A,
The master plates obtained using the developers of Comparative Example B and Comparative Example C did not generate even 10,000 sheets or more.

As described above, only the developer using the resin particles of the present invention as a developer did not cause any stain on the developing device, and the number of printed master plates was good.

That is, in the case of Comparative Examples A, B and C, there was no problem with the number of printed sheets, but the developing device was stained and could not withstand continuous use.

In Comparative Examples B and C, the contamination of the developing device
However, when the developing conditions are severe, the performance has not yet reached a satisfactory level. That is, the known dispersion stabilizing resins of Comparative Examples B and C are:
A compound having a polymerizable double bond group copolymerized with the monomer [A] (vinyl acetate in this example) contained in the polymer is randomly copolymerized in the polymer. Therefore, it is considered that latex particles are inferior in redispersibility as compared with the dispersion stabilizing resin of the present invention.

Example 2 White resin dispersion obtained in Production Example 2 of latex particles
The mixture was heated to 100 ° C. and the mixture was stirred for 4 hours while heating. After cooling to room temperature, a 200-mesh nylon cloth was passed through to remove the remaining dye, thereby obtaining a black resin dispersion having an average particle size of 0.20 μm.

32 g of the above black resin dispersion, zirconium naphthenate 0.0
A liquid developer was prepared by diluting 5 g into 1 of Shellsol 71.

When this was developed by the same apparatus as in Example 1, 2000
Even after the development of the sheet, no toner contamination occurred on the apparatus.

Further, 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 resin dispersion obtained in Production Example 21 of latex particles
A mixture of 100 g and 3 g of Victoria Blue B at 70 ° C
The mixture was heated to 8080 ° C. and stirred for 6 hours. After cooling to room temperature, the mixture was passed through a 200-mesh nylon cloth to remove a residual dye, thereby obtaining a blue resin dispersion having an average particle size of 0.16 μm.

32 g of the above blue resin dispersion, zirconium naphthenate 0.0
A liquid developer was prepared by diluting 5 g to 1 of Isopar H.

When this was developed by the same apparatus as in Example 1, 2000
Even after sheet development, no toner adhesion stains occurred on the apparatus. Further, 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 4 White resin dispersion obtained in Production Example 12 of latex particles
A liquid developer was prepared by diluting 32 g, 2.5 g of the nigrosine dispersion obtained in Example 1, and 0.02 g of a half-dosanyl amidated copolymer of diisobutylene and maleic anhydride into 1 of Isopar G.

When this was developed by the same apparatus as in Example 1, 2000
Even after sheet development, no toner adhesion stains were observed on the apparatus. Further, the image quality of the obtained master plate for offset printing and the image quality of the printed matter after 10,000 sheets were printed were clear.

After the developer was allowed to stand for 3 months, the same treatment as above was performed, but it was not different from that before the lapse of time.

Example 5 10 g of poly (decyl methacrylate), 30 g of Isopar H
Then, 8 g of alkali blue and glass beads were put into a paint shaker together with glass beads, and dispersed for 2 hours to obtain a fine dispersion of alkali blue.

White resin dispersion obtained in Production Example 1 of latex particles
30 g, 4.2 g of the above-mentioned alkali blue dispersion, 15 g of higher alcohol FOC-1400 (manufactured by Nissan Chemical Industries, Ltd.) and 0.06 g of a semi-docosanyl amidated copolymer of diisobutylene and maleic anhydride are diluted to 1 in Isopar G. Thus, a liquid developer was prepared.

When this was developed by the same apparatus as in Example 1, 2000
Even after sheet development, no toner adhesion stains were observed on the apparatus. In addition, the image quality of the obtained master plate for offset printing and the image quality of printed matter after 10,000 sheets were printed were very clear.

Examples 6 to 21 Example 5 was repeated except that the white resin dispersion of Production Example 1 of latex particles was replaced with 6.0 g as the solid content of latex particles shown in Table 10 in Example 5. A liquid developer was prepared in the same manner as described above.

This was developed by the same apparatus as in Example 1, and even after the development of 2,000 sheets, no toner adhesion stains were observed on the apparatus. In addition, the image quality of the obtained master plate for offset printing and the image quality of printed matter after 10,000 sheets were printed were very clear.

(Effect of the Invention) According to the present invention, a developer having excellent dispersion stability, redispersibility, and fixability was obtained. In particular, even when used under plate-making conditions with extremely high plate-making speed, the developing device did not become stained, and the image quality of the obtained master plate for offset printing and the image quality of the printed matter after 10,000 sheets were printed were very clear. Was.

Claims (1)

(57) [Claims] 1. A liquid developer for electrophotography comprising at least a resin dispersed in a non-aqueous solvent having an electric resistance of not less than 10 ⁹ Ωcm and a dielectric constant of not more than 3.5. A polymer containing at least a repeating unit represented by I), a part of which is crosslinked, and which is copolymerized with a monofunctional monomer (A) only at one end of at least one polymer main chain. A monofunctional monomer which is soluble in the non-aqueous solvent but is insolubilized by polymerization in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent, which is formed by bonding a polymerizable double bond group. Body (A) and the following general formula (II)
A monomer (B) containing an aliphatic group having 8 or more carbon atoms and copolymerizing with the monomer (A) by a polymerization reaction
Is a copolymer resin particle obtained by subjecting a solution containing at least one of the following to a polymerization reaction. General formula (I) In the general formula (I), X ¹ represents —COO—, —OCO—, —CH ₂ OCO—,
-CH ₂ COO -, - O-, or -SO ₂ - represent. R ¹ represents a hydrocarbon group having 6 to 32 carbon atoms. a ¹ and a ² may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -COO-R ² or a hydrocarbon group having 1 to 8 carbon atoms. Represents —COO—R ² (R ² represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms). General formula (II) In the general formula (II), R ³ represents an aliphatic group having 8 or more carbon atoms. Y ¹ is -COO-, -CONH-, (R ⁴ represents an aliphatic group), —OCO—, —CH ₂ COO—, or —O—. b ^1, b ^2, which may be the same or different, each represents a hydrogen atom, an alkyl group, -COOR ⁵ or -CH ₂ -COOR ⁵ (R ⁵ represents an aliphatic group).