JPH05158287A - Electrostatic liquid developer - Google Patents

Abstract

PURPOSE:To provide the liq. developer excellent in dispersion stability, redispersibility and resistance to a processing soln. for imparting hydrophilicity by specifying the constitution of a dispersed resin grain. CONSTITUTION:The dispersed resin grain is formed with a monofunctional monomer A insolubilized in nonaqueous solvent when polymerized, a multifunctional monomer D shown by formula I contg. a substituent and having >=2, polymerizable functional group copolymerizable with the monomer A and a block A contg. a polymer component shown by formula II and a block B consisting of the polymer component, etc., contg. a carbonyl group, sulfo group, etc., and a polar group selected from cyclic acid anhydride-contg. groups. A soln. contg. a dispersion stabilizing resin P having 1X10<4> to 5X10<5> weight average mol.wt. and consisting of an A-B block copolymer soluble in nonaqueous solvent is polymerized to obtain the copolymer resin grain. In formulas I and II, E<1> is >=8C aliphatic groups, etc., X<1> is -COO-, -OCO-, etc., Y<1> is >=10C aliphatic groups, and b<1> and b<2> are respectively hydrogen atom, halogen atoms, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid developer for electrostatic photography, in which at least resin particles are dispersed in a carrier liquid having an electric resistance of 10 ⁹ Ωcm or more and a dielectric constant of 3.5 or less. Relates to a liquid developer having excellent dispersibility, redispersibility, and resist properties.

[0002]

2. Description of the Related Art A general liquid developer for electrophotography is 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, acrylic resin, rosin or synthetic rubber, which are petroleum-based. It is dispersed in a liquid with high insulation and low dielectric constant such as aliphatic hydrocarbons, and a polar control agent such as a polymer containing metal soap, lecithin, linseed oil, higher fatty acid, vinylpyrrolidone is added. ..

In such a developer, the resin is dispersed as insoluble latex particles in the form of particles having a diameter of several nm to several hundreds nm, and these particles should be as uniform in particle size as possible over time. It is important that particles do not agglomerate / precipitate, and if they are not satisfied, it may lead to failure of the developing machine such as poor reproducibility of the image area, dirt on the non-image area, or clogging of the liquid feed pump of the developing device. Will end up.

As an improvement of these, a non-aqueous dispersion polymerization method for obtaining insoluble latex particles having a fine particle size and good monodispersity has been proposed and various studies have been made.
For example, U.S. Pat. Nos. 3,990,980 and 4,61
No. 8,557, JP-A Nos. 1-257969 and 2-74.
956, 1-282566, 2-173667
In the No. etc., a method of improving with a soluble dispersion stabilizing resin,
U.S. Pat. No. 4,842,975, JP-A-62-151
No. 868, JP-A Nos. 1-237668 and 2-1682.
No. 76, etc., describes a method of modifying the surface of latex particles by coexisting an insolubilizing monomer and another compound having a physicochemical interaction. The degree of dispersion of particles, particle diameter, redispersibility, It is disclosed that storage stability can be improved.

[0005]

On the other hand, practical use or development of a direct lithographic printing system to which an electrophotographic technique is applied has been actively made in recent years. These systems
A toner image portion is formed on the surface of an electrophotographic photosensitive material by an electrophotographic method, and then processed to convert a non-image portion into a hydrophilic material to obtain a lithographic printing original plate. As a method for making the non-image portion hydrophilic, the portion is eluted with a treatment liquid and the hydrophilicity of the surface of the support of the electrophotographic photosensitive layer is used, or the surface portion of the non-image portion of the photosensitive layer is The main method is to change from lipophilicity to hydrophilicity.

In recent years, as the latter method, as an improvement of the conventionally known method for desensitizing the photoconductive zinc oxide in the photosensitive layer, JP-A-62-21669 and JP-A-1-19 have been proposed.
No. 1157, No. 2-15277, etc., the binder resin used in the photosensitive layer is converted to hydrophilic by treatment.
It is disclosed that the improvement of hydrophilicity is achieved.
In these systems, it is important to maintain the image portion of the toner image portion without any change with respect to the treatment liquid in the hydrophilic treatment (hereinafter referred to as the resist property to the treatment liquid).

When a known liquid developer containing insoluble resin particles having good redispersibility is used for such an electrophotographic plate making system, the resist property of the toner is not sufficient when the non-image area is sufficiently hydrophilized. In some cases, the image part was missing. In particular, this problem becomes noticeable where the area of the toner image portion such as fine lines / characters or halftone dots is small, and the printed matter is deteriorated. Further, insoluble latex particles having high durability to the treatment liquid (for example, styrene-based latex) have sufficient resist properties, but have poor charge stability and redispersibility as toner particles,
Further, since the fixing property of the toner particles is inferior and sufficient fixing requires a high heat and a long fixing time, the complexity of the apparatus becomes a problem.

The present invention solves the problems of the conventional liquid developer described above. The purpose of the present invention is to
It is an object of the present invention to provide a liquid developer having excellent dispersion stability, redispersibility, fixability and hydrophilic treatment liquid resist property in an electrophotographic plate making system. Another object of the present invention is to provide a liquid developer capable of producing an offset printing original plate excellent in reproducibility of a copied image with respect to an original image by an electrophotographic method. Another object of the present invention is to provide a liquid developer capable of producing an original plate for offset printing having excellent oil sensitivity and printing durability of printing ink by an electrophotographic method. Still another object of the present invention is to provide a liquid developer which enables the production of an offset printing original plate using an inkjet recording, a cathode ray tube recording and a recording system of various changing steps such as pressure change or electrostatic change. Is.

[0009]

The above objects of the present invention are as follows.
In a liquid developer for electrostatic photography, in which at least resin particles are 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, the dispersed resin particles are compatible with the non-aqueous solvent. At least one monofunctional monomer (A) that is soluble but insolubilizes by polymerization, represented by the following general formula
At least one monomer (C) represented by (I), which contains a specific substituent and is copolymerizable with the monomer (A),
Contain at least one kind of polyfunctional monomer (D) having two or more polymerizable functional groups copolymerizable with the monomer (A), and at least a polymer component represented by the following general formula (II). Block A, and carboxyl group, sulfo group, hydroxyl group, formyl group, amino group, phosphono group, -P
(= O) (OH) R 1 group [R ¹ is -R ² group or -OR ²
Group, R ² represents a hydrocarbon group], —CON (R
³ ) R ⁴ group, —SO ₂ N (R ³ ) R ⁴ group [R ³ and R ⁴
Each independently represent a hydrogen atom or a hydrocarbon group] and at least one polar group selected from a cyclic acid anhydride-containing group and / or the monofunctional monomer (A). It is composed of a block B comprising a polymer component corresponding to a weight average molecular weight of 1 × 10 ⁴ ~5 × 10
^5. Copolymer resin particles obtained by polymerizing a solution containing at least one dispersion stabilizing resin [P] consisting of an AB type block copolymer soluble in the non-aqueous solvent Is achieved by a liquid developer for electrostatography.

[0010]

[Chemical 5]

In the general formula (I), E ¹ represents an aliphatic group having 8 or more carbon atoms, or a substituent selected from the substituents represented by the following general formula (III).

[0012]

[Chemical 6]

In the formula (III), R ₂₁ represents a hydrogen atom or an aliphatic group having 1 to 18 carbon atoms. B ₁ and B ₂ may be the same or different and each is —O—, —S—, —CO.
_{-, - CO 2 -, -} OCO -, - SO 2 -, - N
_{(R 22) -, - CON} (R 22) -, - N (R 22) CO
_{-, - N (R 22)} SO 2 -, - SO 2 N (R 22) -, -
Represents NHCO ₂ — or —NHCONH— (where R
₂₂ has the same contents as R ₂₁ above). A ₁ and A ₂ are
They represent the same or different ones, each may be substituted, or represent a hydrocarbon group having 1 to 18 carbon atoms, which may be represented by Chemical formula 7 below in the bond of the main chain.

[0014]

[Chemical 7]

In the chemical formula 7, B ₃ and B ₄ may be the same or different from each other and have the same contents as the above B ₁ and B ₂ .
A ₄ represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and R ₂₃ has the same content as R ₂₁ above. m, n and p may be the same or different and each represents an integer of 0 to 4. However, m, n, and p do not become 0 at the same time. In formula (I), U ¹ is —COO—, —CONH—,
-CON (E ²⁾ - [wherein E ² represents a substituent represented by an aliphatic group or the general formula (III)], --OCO
-, - CONHCOO -, - CH 2 COO -, - (CH
₂ ) _s OCO- [where s represents an integer of 1 to 4],
-O- or -C ₆ H ₄ represents a -COO-. a ¹ and a ²
May be the same or different, each represents a hydrogen atom, an alkyl group, -COO-E ³ or -CH ₂ COO-E
³ (wherein E ³ represents an aliphatic group).

[0016]

[Chemical 8]

In the general formula (II), X ¹ is --COO-- or --O.
_{CO -, - (CH 2)} y -COO -, - (CH 2) y -
Represents OCO- or -O- (wherein y represents an integer of 1 to 3). Y ¹ represents an aliphatic group having 10 or more carbon atoms. b ¹ and b ² may be the same or different from each other,
Hydrogen atom, halogen atom, cyano group, hydrocarbon group,
-COO-Z ¹ group or -COO- via a hydrocarbon group
It represents a Z ¹ group (wherein Z ¹ represents a hydrogen atom or an optionally substituted hydrocarbon group).

In the dispersion stabilizing resin [P] used in the present invention, the block B is preferably contained in one end of the polymer main chain of the block B opposite to the end adjacent to the block A. Then, a resin characterized by containing at least one kind of polar group selected from the same specific polar groups can be mentioned. More preferably, in the dispersion-stabilizing resin [P], a polymerization capable of copolymerizing with the monomer (A) at one end of the polymer main chain of block B opposite to the end adjacent to block A. Examples of the resin include a functional group.

The liquid developer of the present invention will be described in detail below. The electric resistance used in the present invention is 10 ⁹ Ωcm or more,
As the carrier liquid having a dielectric constant of 3.5 or less, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and halogen-substituted products thereof can be preferably used. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, Isopar E, Isopar G, Isopar H, Isopar L
(Isopar; trade name of Exxon), Shersol 7
0, Shelsol 71 (Shellsol; trade name of Shell Oil Co., Ltd.), Amsco OMS, Amsco 460 solvent (Amsco; trade name of Spirits Co., Ltd.) and the like are used alone or in combination.

The non-aqueous dispersion resin particles (hereinafter sometimes referred to as latex particles), which is the most important constituent component of the present invention, is an AB type block copolymer soluble in the non-aqueous solvent in the non-aqueous solvent. In the presence of the dispersion stabilizing resin [P], at least one of the monofunctional monomer (A), at least one of the monomer (C) containing a specific substituent, and the polyfunctional monomer. It is polymerized and granulated by copolymerizing at least one of the body (D).

Preferably, the dispersion stabilizing resin [P] is
This is a resin containing the same specific polar group as that contained in the block B at one end of the polymer main chain of the block B opposite to the end adjacent to the block A. More preferably, the dispersion stabilizing resin [P] is copolymerizable with the monomer (A) at one end of the polymer main chain of the block B opposite to the end adjacent to the block A. It is a resin containing a polymerizable functional group.

Here, as the non-aqueous solvent, basically,
Any one can be used as long as it is miscible with the carrier liquid of the liquid developer for electrostatic photography. That is, the solvent used in producing the dispersed resin particles may be any solvent that is miscible with the carrier liquid, and is preferably a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon. Examples thereof include hydrogen and halogen substitution products thereof. Hexane, for example,
Octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, isoper E,
Isopar G, Isopar H, Isopar L, Shelsol 70, Shelsol 71, Amsco OMS, Amsco 460 solvent and the like are used alone or in combination.

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

It is desirable that the non-aqueous solvent used as a mixture of these is distilled off under heating or under reduced pressure after the polymerization and granulation. However, even if it is brought into a liquid developer as a latex particle dispersion, it is developed. There is no problem as long as the liquid resistance of the liquid is in a range that can satisfy the condition of 10 ⁹ Ωcm or more. Usually, it is preferable to use the same solvent as the carrier liquid in the step of producing the resin dispersion, and as described above, a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, aromatic hydrocarbon, halogenated Examples include hydrocarbons.

The monofunctional monomer (A) in the present invention is
Any monofunctional monomer that is soluble in the non-aqueous solvent but is insolubilized by polymerization may be used. Specific examples thereof include monomers represented by the following general formula (IV).

[0026]

[Chemical 9]

In the formula (IV), T ¹ is --COO-- or --OCO.
_{-, - CH 2 OCO -,} - CH 2 COO -, - O -, -
CONHCOO -, - CONHOCO -, - SO 2 -,
^{-CON (W 1) -, -} SO 2 N (W 1) -., Or a phenylene group (hereinafter referred to as a phenylene group and "-Ph-" Incidentally, phenylene group 1,2-, 1,3- And 1,4
-Including phenylene groups. ) Is represented. W ¹ represents a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group). Group, 2-hydroxyethyl group, benzyl group,
Chlorobenzyl group, methylbenzyl group, methoxybenzyl group, phenethyl group, 3-phenylpropyl group, dimethylbenzyl group, fluorobenzyl group, 2-methoxyethyl group, 3-methoxypropyl group, etc.).

D ¹ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2,2-dichloroethyl group). , 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-dimethylaminoethyl group, N, N-diethylaminoethyl group, trimethoxysilylpropyl 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.).

D ¹ and d ² may be the same or different and each has the same content as b ¹ or b ² in the general formula (II).

Specific examples of the monofunctional monomer (A) include
For example, vinyl esters or allyl esters of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.); acrylic acid, methacrylic acid, crotonic acid, itaconic acid, Alkyl esters or amides of an unsaturated carboxylic acid such as maleic acid having 1 to 4 carbon atoms which may be substituted (eg, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a 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-pyridinylethyl group, 2-thienylethyl group, trimethoxysilylpropyl group, 2-
Carboxamidoethyl group, etc.); Styrene derivative (for example, styrene, vinyltoluene, α-methylstyrene,
Vinyl naphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N, N
-Dimethylaminomethylstyrene, vinylbenzenecarboxamide, vinylbenzenesulfoamide, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid; cyclic acid anhydrides of maleic acid, itaconic acid; Acrylonitrile; methacrylonitrile; a heterocyclic compound containing a polymerizable double bond group (specifically, for example, "Polymer Data Handbook-Basic Edition" edited by The Society of Polymer Science, pp. 175-184, Baifukan (1986) ), For example, N-vinyl pyridine, N
-Vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.)
Etc. The monomer (A) may be used in combination of two or more kinds.

Next, the monomer (C) containing a specific substituent represented by the general formula (I) used in the present invention will be further described.

[0032]

[Chemical 10]

In the general formula (I), E ¹ represents an aliphatic group having 8 or more carbon atoms, or a substituent selected from the substituents represented by the following general formula (III).

[0034]

[Chemical 11]

In the formula (III), R ₂₁ represents a hydrogen atom or an aliphatic group having 1 to 18 carbon atoms. B ₁ and B ₂ may be the same or different and each is —O—, —S—, —CO.
_{-, - CO 2 -, -} OCO -, - SO 2 -, - N
_{(R 22) -, - CON} (R 22) -, - N (R 22) CO
_{-, - N (R 22)} SO 2 -, - SO 2 N (R 22) -, -
Represents NHCO ₂ — or —NHCONH— (where R
₂₂ has the same contents as R ₂₁ above). A ₁ and A ₂ are
They represent the same or different ones, and each represent a hydrocarbon group having 1 to 18 carbon atoms, which may be substituted or may have the following chemical formula 12 interposed in the bond of the main chain.

[0036]

[Chemical 12]

In the chemical formula 12, B ₃ and B ₄ may be the same or different from each other, and have the same contents as B ₁ and B _2, and A ₄ is an optionally substituted carbon atom having 1 to 18 carbon atoms. A hydrogen group is shown, and R ₂₃ has the same contents as R ₂₁ above. m, n
And p may be the same or different from each other, and each is 0 to 4
Represents the integer. However, m, n, and p do not become 0 at the same time. In formula (I), U ¹ is -COO-, -CONH.
^{-, - CON (E 2)} - [wherein E ² represents a substituent represented by an aliphatic group or the general formula (III)], -O
CO -, - CONHCOO -, - CH 2 COO -, -
(CH _{2) s} OCO- [where s represents an integer of 1 to 4], represent -COO- -O- or -C ₆ H _4. a ¹
And a ² may be the same as or different from each other, and each is a hydrogen atom, an alkyl group, —COO—E ³ or —CH ₂ COO.
Represents -E ³ (wherein E ³ represents an aliphatic group).

The case where E ¹ in the monomer (C) represented by the general formula (I) represents an aliphatic group having 8 or more carbon atoms will be described in detail. In the general formula (I), preferably,
E ¹ represents an optionally substituted alkyl group having 10 or more total carbon atoms or an alkenyl group having 10 or more total carbon atoms. U ¹ is -COO-, -CONH-, -CON (E ² )-[wherein E ² is preferably an aliphatic group having 1 to 32 carbon atoms (eg, an aliphatic group is an alkyl group, an alkenyl group or an aralkyl group). Etc.)), —OCO—, —CH ₂ O
Represents CO- or -O-. a ¹ and a ² may be the same or different, and preferably a hydrogen atom, a methyl group,
Represents a COO-E ³ or -CH ₂ COO-E ³ [where E ³ is preferably an alkyl group, an alkenyl group, an aralkyl group or a cycloalkyl group having 1 to 32 carbon atoms. ]. Still more preferably, in the formula (I), U ¹ is-
COO -, - CONH-, or -CON (E ²⁾ - represents, a ¹ and a ^2, which may be the same or different, represent a hydrogen atom or a methyl group, the same contents as E ¹ has been described above Represent.

When E ¹ represents an aliphatic group having 8 or more carbon atoms in the monomer (C) represented by the above general formula (I), specific examples thereof include those having 10 to 32 total carbon atoms. Aliphatic group (The aliphatic group may contain a substituent such as a halogen atom, a hydroxyl group, an amino group or an alkoxy group, or a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom, which is a carbon atom of its main chain. Having a carbon bond), acrylic acid, methacrylic acid, crotonic acid, maleic acid,
Esters of unsaturated carboxylic acids such as itaconic acid (for example, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosenyl group, dodecenyl group, hexadecenyl group as an aliphatic group,
Oleyl group, linoleyl group, docosenyl group, etc.); amides of unsaturated carboxylic acids described above (aliphatic groups represent the same as those shown for esters); vinyl esters or allyl esters of higher fatty acids (higher fatty acids) Examples thereof include lauric acid, myristic acid, stearic acid, oleic acid, linoleic acid, and behenic acid); or vinyl ethers substituted with an aliphatic group having a total carbon number of 10 to 32 (wherein the aliphatic group is the unsaturated carboxylic acid described above). The same range as the aliphatic group of the acid) and the like.

The case where E ¹ in the monomer (C) represented by the general formula (I) represents a substituent represented by the general formula (III) will be described in detail. More specific examples of A ₁ and A ₂ are: -C (R ₂₄ )
(R ₂₅ )-[R ₂₄ and R ₂₅ represent a hydrogen atom, an alkyl group, a halogen atom or the like],-(CH = CH)-, a cyclohexylene group [hereinafter, a cyclohexylene group is referred to as "-C ₆ H
₁₀ - expressed in "" - C ₆ H ₁₀ - "is 1,2-cyclohexylene group, 1,3-cyclohexylene group, include 1,4-cyclohexylene group], the reduction 12, atoms etc. It is composed of any combination of groups.

Further, in the linking group in the general formula (I): --U ^1- (A ₁ --B ₁ ) _m- (A ₂ --B ₂ ) _n --R ₂₁ , U ¹ to R ₂₁ (ie U) ¹ , A ₁ , B ₁ , A
It is preferable that the total number of atoms of the connecting main chain composed of ₂ , B ₂ , R ₂₁ ) is 8 or more. Where U ¹
There -CON (E ²⁾ - the stands, and E ² is the formula
A substituent represented by (III) [that is,-(A ₁ -B ₁ ) _m-
In the case of representing (A ₂ -B ₂ ) _n -R ₂₁ ], the linking main chain composed of E ² is also included in the above linking main chain. Furthermore,
When A _1, A ₂ is a hydrocarbon group of interposing the reduction 12 in the binding of the main _{chain, -B 3 - (A 4 -B} 4) p -R
₂₃ is also included in the linking backbone. As the number of atoms of the connecting main chain, for example, when U ¹ represents —COO— or —CONH—, an oxo group (═O group) and a hydrogen atom are not included as the number of atoms, and the carbon atoms constituting the connecting main chain are included. Atoms, ether type oxygen atoms, and nitrogen atoms are included as the number of atoms. Therefore, -COO- and -CONH- are counted as having 2 atoms. Similarly, if R ₂₁ represents -C ₉ H _19, a hydrogen atom is not contained in the number of atoms, the carbon atoms are included.
Therefore, in this case, the number of atoms is 9. In the monomer (C) represented by the general formula (I) as described above, E
^{When 1} represents a substituent represented by the general formula (III), that is, in the case of a monomer containing a specific polar group, more specifically, the following compounds can be given as examples.

[0042]

[Chemical 13]

[0043]

[Chemical 14]

[0044]

[Chemical 15]

[0045]

[Chemical 16]

[0046]

[Chemical 17]

[0047]

[Chemical 18]

Next, 2 polymerizable functional groups copolymerizable with the monofunctional monomer (A) and the monomer (C) containing a specific substituent are used. Monomer (D) having more than one (hereinafter, also referred to as polyfunctional monomer (D))
Will be described. The polymerizable functional group contained in the polyfunctional monomer (D) may be any as long as it is copolymerizable with the monomer (A), and specifically, it is represented by the following general formula (V). The functional groups shown are mentioned.

[0049]

[Chemical 19]

[0050] In the formula ^{(V), d 1, d} 2 and T ¹ have the same meanings as d ^1, d ² and T ¹ in the general formula (IV).

Further, the polyfunctional monomer (D) may be a monomer having two or more of the same or different polymerizable functional groups, and the monomer (A) And a monomer (C) are polymerized to form a polymer insoluble in the non-aqueous solvent.

Specific examples of the monomer (D) having two or more polymerizable functional groups include, for example, styrene derivatives such as divinylbenzene and trivinylbenzene as monomers having the same polymerizable functional group; Polyhydric alcohol (for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol # 200, # 40
0, # 600, 1,3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc., or polyhydroxyphenols (for example, hydroquinone, resorcin, catechol and them. Derivatives of methacrylic acid, acrylic acid or crotonic acid esters, vinyl ethers or allyl ethers; dibasic acids (eg, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, Itaconic acid etc.) vinyl esters, allyl esters, vinyl amides or allyl amides; polyamines (eg ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine etc.) and vinyl Carboxylic acids having (e.g.,
Methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.) and the like.

As a monomer having different polymerizable functional groups, for example, a carboxylic acid having a vinyl group [for example,
Reactants of methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, acryloyl propionic acid, itaconiloyl acetic acid, itaconiloyl propionic acid, carboxylic acid anhydrides and alcohols or amines (e.g., allyloxycarbonylpropionic acid, allyl). Oxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc.) or a vinyl group-containing ester derivative or amide derivative (eg, vinyl methacrylate, vinyl acrylate, vinyl itaconic acid, allyl methacrylate) , Allyl acrylate, allyl itaconic acid, methacryloyl vinyl acetate, methacryloyl vinyl propionate,
Allyl methacryloylpropionate, vinyloxycarbonylmethylmethacrylate methacrylic acid, vinyloxycarbonylmethyloxycarbonylethylene acrylate, N-allylacrylamide, N-allylmethacrylamide, N-ally itaconic acid amide, methacryloylpropionic acid allylamide, etc.); or , Amino alcohols (for example, amino ethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and vinyl group-containing carboxylic acid condensates.

The dispersion resin of the present invention comprises at least one kind of each of the monomer (A), the monomer (C) and the monomer (D), and importantly, is synthesized from these monomers. If the obtained resin is insoluble in the non-aqueous solvent, a desired dispersed resin can be obtained. More specifically, the insolubilizing monomer (A)
On the other hand, the monomer (C) represented by the general formula (I) was added in an amount of 0.
It is preferable to use 1 to 20% by weight, and more preferably 0.3 to 8% by weight. The monomer (D) having two or more polymerizable functional groups used in the present invention is used in an amount of 20 mol% or less, preferably 10 mol% or less of all monomers, and polymerized to give a resin. Form. The molecular weight of the dispersed resin of the present invention is preferably 1 × 10 ³ to 1 × 10 ⁶ , and more preferably 1 × 10 ⁴ to 1 × 10 ⁶ .

Dispersion stabilizing resin [P] used in the present invention
Is an AB block copolymer, one block (referred to as block A) is composed of a polymer component composed of a repeating unit represented by the general formula (II), and another block (block) is B)) is composed of a polymer component containing at least one polar group selected from the above-mentioned specific polar groups and / or a polymer component corresponding to the above-mentioned monofunctional monomer (A). The weight average molecular weight is 1 × 10 ^{4 to} 5 × 10 ⁵ . The A
The abundance ratio of the block A and the block B in the -B type block copolymer is preferably 99/1 to 50/50 (weight ratio).

The specific polar group-containing polymer component contained in the block B is preferably 1 to 30 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the dispersion stabilizing resin.
15 parts by weight. When there is no specific polar group-containing polymer component in block B, the polymer component corresponding to the monofunctional monomer (A) is preferably the resin 1
5 to 50 parts by weight in 00 parts by weight, more preferably 1
It is 0 to 40 parts by weight. The weight average molecular weight of the AB block copolymer is preferably 2 × 10 ⁴ to 1 × 10 ⁵ .

The repeating unit represented by the general formula (II) which constitutes the block A will be described in detail. General formula (I
In I), X ¹ is preferably —COO—, —OCO.
Represents -or-O-. Y ¹ represents an alkyl group or an alkenyl group having 10 or more carbon atoms, which may be linear or branched. Specifically, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, linolel group and the like can be mentioned. .. b
¹ and b ² may be the same as or different from each other, and preferably a hydrogen atom, a halogen atom (eg, chlorine atom, bromine atom, etc.), a cyano group, an alkyl group having 1 to 3 carbon atoms (eg, methyl group, ethyl group). Group, propyl group, etc.), -COO-
Z ¹ groups, or -CH ₂ COO-Z ¹ group [Z ¹ is a hydrogen atom or a substituted carbon atoms and optionally more than 22 hydrocarbon group (e.g., an alkyl group, an alkenyl group, an aralkyl group,
Represents an alicyclic group, an aryl group, etc.)].

Z ¹ is specifically a hydrogen atom, and as a preferable hydrocarbon group, an alkyl group having 1 to 22 carbon atoms which may be substituted (eg, methyl group, ethyl group, propyl group, butyl group). Group, heptyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, 2-chloroethyl group, 2-bromoethyl group, 2- Cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3
-Bromopropyl group, etc., an alkenyl group having 4 to 18 carbon atoms which may be substituted (for example, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group) , 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, linolel group, etc.),
Aralkyl groups having 7 to 12 carbon atoms which may be substituted (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, Ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), alicyclic group having 5 to 8 carbon atoms which may be substituted (eg, cyclohexyl group, 2
-Cyclohexylethyl group, 2-cyclopentylethyl group, etc.) and optionally substituted aromatic group having 6 to 12 carbon atoms (eg, phenyl group, naphthyl group, tolyl group, xylyl group, propylphenyl group, butylphenyl group) , Octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxy Carbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group, etc.).

In addition, the block A of the dispersion stabilizing resin used in the present invention may contain another repeating unit as a copolymerization component in addition to the repeating unit represented by the general formula (II). The other copolymerization component may be any compound as long as it is composed of a monomer that is copolymerizable with the monomer corresponding to the repeating unit of the general formula (II). However, it is preferable that no other component is contained, and it is used in a range not exceeding 20 parts by weight in the block A at most. If it exceeds 20 parts by weight, the dispersion stability of the dispersed resin particles deteriorates. In the block A, the repeating unit represented by the general formula (II) may be used in combination of two or more kinds.

Next, the polymer component constituting the block B of the block copolymer of the present invention will be described in detail. The block B is composed of a polymer component corresponding to the monofunctional monomer (A) and / or the polymer component containing the specific polar group described above. Examples of the polymer component corresponding to the monofunctional monomer (A) include those having the same contents as those described above for the insolubilizing monomer (A). Preferably, it is composed of the same monomer as the monofunctional monomer (A) to be the dispersed resin particles.

In a specific polar group, -P (= O) (OH) R
^{In one} group, R ¹ represents -R ² group or -OR ² group,
R ² represents a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group for R ² is preferably an optionally substituted aliphatic group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, butenyl group,
Pentenyl group, hexenyl group, 2-chloroethyl group, 2
-Cyanoethyl group, cyclopentyl group, cyclohexyl group, benzyl group, phenethyl group, chlorobenzyl group, bromobenzyl group, etc.) or an aromatic group which may be substituted (for example, phenyl group, tolyl group, xylyl group, mesityl group, chlorophenyl) Group, bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

Among the specific polar groups, R ³ and R in the —CON (R ³ ) R ⁴ group and the —SO ₂ N (R ³ ) R ⁴ group.
Each of ^4's independently represents a hydrogen atom or a hydrocarbon group (preferably a hydrocarbon group having 1 to 8 carbon atoms which may be substituted). Specific examples of the hydrocarbon group represented by R ³ and R ⁴ include those having the same contents as the hydrocarbon group represented by R ² .

The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride, and the cyclic acid anhydride to be contained is an aliphatic dicarboxylic acid anhydride or an aromatic dicarboxylic acid anhydride. Things can be mentioned. Examples of the aliphatic dicarboxylic acid anhydride include succinic anhydride, glutaconic anhydride, maleic anhydride, cyclopentane-1,2.
-Dicarboxylic acid anhydride, cyclohexane-1,2-dicarboxylic acid anhydride, cyclohexene-1,2-dicarboxylic acid anhydride, 2,3-bicyclo [2,2,2] octanedicarboxylic acid anhydride, and the like, These aliphatic dicarboxylic acid anhydrides may be substituted with, for example, a halogen atom such as a chlorine atom or a bromine atom, an alkyl group such as a methyl group, an ethyl group, a butyl group or a hexyl group. Examples of aromatic dicarboxylic acid anhydrides include phthalic anhydride, naphthalene-dicarboxylic acid anhydride, pyridine-dicarboxylic acid anhydride, thiophene-dicarboxylic acid anhydride, and the like. Examples include halogen atoms such as chlorine atom and bromine atom, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hydroxyl group, cyano group, nitro group, alkoxycarbonyl group (as an alkoxy group, For example, it may be substituted with a methoxy group, an ethoxy group or the like).

In the polar group of the present invention, the amino group is -N
H _2, represents a -NHR ⁵ or -NR ⁵ R ^6. R ⁵ and R ⁶ represent a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 7 carbon atoms, and specifically,
It has the same contents as the above-mentioned hydrocarbon group for R ² . Even more preferably, the hydrocarbon groups of R ² , R ⁵ and R ⁶ are
Examples thereof include an optionally substituted alkyl group having 1 to 4 carbon atoms, an optionally substituted benzyl group, and an optionally substituted phenyl group.

The monomer corresponding to the polymer component containing the above specific polar group may be any monofunctional monomer containing at least one specific polar group.
For example, it is described in "Polymer Data Handbook [Basic Edition]" edited by The Society of Polymer Science, Ltd., Baifukan (1986).
Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α- (2-amino) methyl form, α-chloro form, α
-Bromo form, α-fluoro form, α-tributylsilyl form,
α-cyano compound, β-chloro compound, β-bromo compound, α-chloro-β-methoxy compound, α, β-dichloro compound, etc.), methacrylic acid, itaconic acid, itaconic acid half-esters, itaconic acid half-amides , Crotonic acid, 2-alkenylcarboxylic acids (for example, 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid,
4-ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half-esters, maleic acid half-amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acid vinyl group or allyl Examples thereof include half-ester derivatives of groups, ester derivatives of these carboxylic acids or sulfonic acids, and compounds having the polar group in the substituent of the amide derivative.

The following can be mentioned as specific examples of these compounds. However, in each of the following examples, e
Is _{-H, -CH 3, -Cl, -Br} , -CN, -CH 2
COOCH ₃ or indicates -CH ₂ COOH, f represents -H or -CH _3, n is an integer of 2 to 10, m is 1
The integer of 10 is shown, p shows the integer of 1-4. X ₁ is -COOH, -O-P (= O ) (OH) 2, -SO
₃ H, -OH, -N (R _a ) R _b , -CHO, or -O
-P (= O) (OH) -OR _a is shown. Where R _a ,
R _b represents an alkyl group having 1 to 4 carbon atoms. X ₂ is -CO
Indicates OH or -OH.

[0067]

[Chemical 20]

[0068]

[Chemical 21]

[0069]

[Chemical formula 22]

[0070]

[Chemical formula 23]

The AB type block copolymer of the present invention can be produced by a conventionally known polymerization reaction method. Specifically, in the monomer corresponding to the polymer component containing the specific polar group, the polar group is preliminarily protected as a functional group, and an organometallic compound (for example, alkyllithium, lithium diisopropylamide, alkyl Magnesium halides) or hydrogen iodide / iodine-based ionic polymerization reaction, photopolymerization reaction using a porphyrin metal complex as a catalyst, group transfer polymerization reaction, or other known so-called living polymerization reaction, and AB type block copolymerization A method of forming a polar group by synthesizing a combined product, and then deprotecting a functional group having a protected polar group by a hydrolysis reaction, a hydrogenolysis reaction, an oxidative decomposition reaction, a photodecomposition reaction, or the like can be mentioned. One example thereof is shown in the following reaction scheme (1).

[0072]

[Chemical formula 24]

For example, P. Lutz, P .; Masson
et al, Polym. Bull. , 12 , 79
(1984); C. Anderson, G.M. D. A
ndrews et al, Macromolecule
es, 14 , 1601 (1981); Hatad
a, K.A. Ute et al, Polym. J. , 1
7 , 977 (1985); ibid. 18 , 1037 (198).
6); Koichi Right Hand, Koichi Hatada "Polymer Processing" 36 , 366
(1987); Toshinobu Higashimura, Mitsuo Sawamoto "Polymer Papers" 4
6 , 189 (1989); Kuroki, T .; Ai
da, J .; Am. Chem. Soc. , 109 , 473
7 (1987); Takuzo Aida, Shohei Inoue "Synthetic Organic Chemistry"
43 , 300 (1985); Y. Sogah, W .;
R. Hertler et al, Macromole
Cules, 20 , 1473 (1987) and the like.

Further, the A-B type block copolymer uses a monomer in which the polar group is not protected and uses a compound containing a dithiocarbamento group and / or a compound containing a xanthate group as an initiator. It can also be synthesized by performing a polymerization reaction under light irradiation. For example, Takayuki Otsu "Polymer" 37 , 248 (1988); Shunichi Hinomori, Ryuichi Otsu,
Polym. Rep. Jap. , 37 , 3508 (19
88); JP-A-64-111; JP-A-1-26619.
No. Higashi Nobuyuki, Polymer Preprints,
Japan, 36 , (6), 1511 (1987);
M. Niwa, N.N. Higashi et al.
Macromol. Sci. Chem. , A24 ,
(5), 567 (1987) and the like.

The protecting group for protecting the specific polar group of the present invention and the elimination of the protecting group (deprotection reaction) can be easily carried out by utilizing the conventionally known knowledge. For example, various references are described in the above-mentioned references, and further, Yoshio Iwakura and Keisuke Kurita "Reactive Polymer", Kodansha Co., Ltd. (1977); W. Greene, "Prot
active Groups in Organic
Synthesis ”, John Wiley & S
ons (1981); F. W. McOmie,
"Protective Groups in Org
anic Chemistry ", Plenum Pr
The method described in detail in the review article such as ess, (1973) can be appropriately selected and performed.

Furthermore, for the AB type block copolymer, an azobis compound (that is, a high molecular weight azobis polymerization initiator) containing either block A or block B is synthesized, and this is used as a polymerization initiator. Alternatively, the monomers corresponding to forming the other one of the blocks may be polymerized by radical polymerization reaction to be synthesized. Specifically, it can be synthesized according to the method described in Akira Ueda, Susumu Nagai, “Polymer Papers” 44 , 469 (1987); Akira Ueda, Report of Osaka City Institute of Industrial Research, 84 (1987) and the like. . In the case of synthesizing an AB type block copolymer by utilizing this reaction, the high molecular weight azobis polymerization initiator is used because of the ease of synthesis of the high molecular weight azobis polymerization initiator and the regularity of the polymerization reaction of blocking. The weight average molecular weight of is preferably 2 × 10 ⁴ or less. On the other hand, in the dispersion stabilizing resin [P] of the present invention, the polymer chain of the block B is preferably longer than that of the block A. From the above, in the case of synthesizing the AB block copolymer by the above reaction, the method of using the high molecular weight azobis polymerization initiator containing the block A is preferable. For example, it can be synthesized by the reaction scheme (2) as shown below.

[0077]

[Chemical 25]

Dispersion stabilizing resin [P] used in the present invention
Is preferably one in which the same specific polar group as contained in block B is bonded to one end of the polymer main chain of block B opposite to the end adjacent to block A. To be [Hereinafter, referred to as dispersion stabilizing resin [PA] or resin [PA]. Examples of the specific polar group bonded to one end of the block B include those described as the polar group contained in the block B. The polar group bonded to one end of the block B is the same polar group as contained in the block B. For example, block B
When contains a plurality of polar groups, the polar group bonded to one end of the block B is at least one polar group selected from the plurality of polar groups.

In the dispersion stabilizing resin [PA], at least one of the above-mentioned specific polar groups may be directly bonded to one end of the polymer main chain of block B, or may be bonded via a linking group. Good. As the linking group for linking the main chain component and the specific polar group-containing component, a carbon-carbon bond (single bond or double bond), a carbon-hetero atom bond (as a hetero atom, for example, an oxygen atom, a sulfur atom) , A nitrogen atom, a silicon atom, etc.), and any combination of heteroatom-heteroatom bond atomic groups. More specific linking group, -CR ⁷ R ⁸ - [R ^7, R ⁸ are each independently a hydrogen atom, a halogen atom (fluorine atom, chlorine atom,
Bromine atom, etc.), cyano group, hydroxyl group, alkyl group (methyl group, ethyl group, propyl group, etc.)], −
(CH = CH) -, - C 6 H 10 - ( cyclohexylene group), - Ph -, - O -, - S -, - CO -, - NR 9
-, - COO -, - SO 2 -, - CONR 9 -, - SO
^{_{2 NR 9 -, - NHCOO -}} , - NHCONH -, - S
i R ⁹ R ^10- [R ⁹ and R ¹⁰ each represent a hydrogen atom, a hydrocarbon group having the same content as R ² in the polar group, etc.] Alternatively, a connecting group composed of a combination of any two or more atomic groups can be mentioned.

Further, a preferred embodiment of the dispersion stabilizing resin [P] of the present invention is that the monomer (A) is attached to one end of the polymer main chain of the block B opposite to the end adjacent to the block A. ) And a polymerizable functional group capable of being copolymerized with each other. [Hereinafter, referred to as dispersion stabilizing resin [PB] or resin [PB]. ]

Specific contents of the polymerizable functional group of the dispersion stabilizing resin [P B] are the functional group represented by the general formula (V) described as the polymerizable functional group in the polyfunctional monomer (D). The same thing as is mentioned. Further, the polymerizable functional group may be directly bonded to one end of the polymer main chain of block B, or may be bonded via a linking group. Examples of the linking group include those having the same contents as the linking group in the dispersion stabilizing resin [PA].

The dispersion stabilizing resin [P] of the present invention has a weight average molecular weight of 1 × 10 ^{4 to} 5 × 10 ⁵ , and preferably 2
× 10 ⁴ to 1 × 10 ⁵ . Weight average molecular weight is 1 × 1
When it is less than 0 ⁴ , the average particle size of the resin particles obtained by polymerization granulation becomes large (for example, larger than 0.5 μm) and the particle size distribution becomes broad. On the other hand, when it exceeds 5 × 10 ⁵ , the average particle size of the resin particles obtained by the polymerization granulation becomes too large, and it becomes difficult to make the average particle size within the preferable range of 0.15 to 0.4 μm. Sometimes.

Dispersion stabilizing resin [P] used in the present invention
Is soluble in an organic solvent, and specifically, at least 5 parts by weight or more of the dispersion stabilizing resin is dissolved in 100 parts by weight of a toluene solvent at a temperature of 25 ° C.

The dispersion stabilizing resin [PA] of the present invention, which is a preferred embodiment in which a specific polar group is bonded to one end of the polymer main chain of the block B, is the above-mentioned conventionally known anionic or cationic polymerization. The method of reacting various reagents at the terminals when carrying out the termination reaction of the living polymer obtained by (see reaction scheme (1)) (method by ionic polymerization method), or dithiocarbamate used in the method by photopolymerization reaction described above The compound can be easily synthesized by incorporating a specific polar group of the present invention in a group- or xanthate-group-containing compound (polymerization initiator), and using this compound as a polymerization initiator for polymerization. Specifically, it is described in the literature cited in the method of synthesizing the dispersion stabilizing resin [P].

The weight average molecular weight of the dispersion stabilizing resin [PA] of the present invention is preferably 1 × 10 ^{4 to} 5 × 10 ⁵ , and more preferably 2 × 10 ⁴ to 1 × 10 ⁵ . When the weight average molecular weight is less than 1 × 10 ⁴ , the average particle size of the resin particles obtained by polymerization granulation becomes large (for example, larger than 0.5 μm) and the particle size distribution becomes broad. On the other hand, when it exceeds 5 × 10 ⁵ , the average particle size of the resin particles obtained by the polymerization granulation becomes too large, and it becomes difficult to make the average particle size within the preferable range of 0.15 to 0.4 μm. Sometimes.

Furthermore, the dispersion stabilizing resin [PB] of the present invention, which is a preferred embodiment in which a polymerizable double bond group is bonded to one end of the polymer main chain of block B, is a conventionally known anionic polymerizing or A living polymer obtained by cationic polymerization is reacted with a reagent containing various double bond groups at the end, or a specific reactive group (for example, —OH, —COOH, —SO ₃₎ is added to the end of the living polymer.
_{H, -SH, -NH 2, -PO} 3 H 2, -NCO, -N
CS, an epoxy group represented by the following chemical formula 26, -COCl,
-SO ₂ Cl etc.) and then introducing a polymerizable double bond group by polymer reaction (method by ionic polymerization method), or by adding the above-mentioned specific reactive group in the molecule. After radical polymerization using the included polymerization initiator and / or chain transfer agent, a polymer reaction is carried out by carrying out a polymer reaction utilizing a specific reactive group bonded only to one end of the polymer main chain. It can be easily produced by a synthetic method such as a method of introducing a heavy bond group.

[0087]

[Chemical formula 26]

Specifically, P. Dreyfuss &
R. P. Quirk, Encycl. Poly. Sc
i. Eng. , 7 , 551 (1987); Yoshiki Nakajo, Yuya Yamashita "Dyes and Pharmaceuticals", 30 , 232 (1985); Akira Ueda, Susumu Nagai "Chemicals and Industry" 60 , 57 (1986);
P. F. Rempp & E. France, Adva
nces in Polymer Science, 5
8 , 1 (1984); Koichi Ito "Polymer Processing", 35 ,
262 (1986); Percec, Applie
d Polymer Science, 285 , 97
The polymerizable double bond group can be introduced according to the method described in the review article (1984) and the like and references cited therein.

More specifically, the dispersion stabilizing resin [PA
] The method of introducing a polymerizable double bond group by carrying out a polymer reaction of the specific polar group of the above] is mentioned as a preferable method.

To produce the latex particles (dispersed resin particles) used in the present invention, generally, the above-mentioned AB is used.
The dispersion-stabilizing resin [P] of the mold block copolymer, the monofunctional monomer (A), the monomer (C) containing a specific substituent and the polyfunctional monomer (D) are added to a non-aqueous solution. The polymerization may be carried out by heating in a solvent in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile or butyllithium. Specifically, a method for adding a polymerization initiator to a mixed solution of the dispersion stabilizing resin [P], the monomer (A), the monomer (C) and the monomer (D), and the dispersion stabilizing resin. A method of dropping monomer (A), monomer (C) and monomer (D) together with a polymerization initiator into a solution in which [P] is dissolved, or a total amount of dispersion stabilizing resin [P] And a monomer (A), a monomer (C) and a part of the monomer (D), a polymerization initiator and the remaining monomer (A), monomer (C) and Monomer (D)
Of the dispersion stabilizing resin [P], the monomer (A), the monomer (C) and the monomer (D) in a non-aqueous solvent to initiate polymerization. There is a method of optionally adding it together with the agent, and it can be produced by any method.

The total amount of the monomer (A), the monomer (C) and the monomer (D) is 5 to 8 with respect to 100 parts by weight of the non-aqueous solvent.
It is about 0 parts by weight, preferably 10 to 50 parts by weight. The soluble resin which is the dispersion stabilizing resin [P] is 1 to 100 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of all the monomers used above. The amount of the polymerization initiator is appropriately 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 120 ° C. The reaction time is preferably 1 to 15 hours.

When the polar solvent such as alcohols, ketones, ethers and esters described above is used in combination in the non-aqueous solvent used in the reaction, or the monomer (A) to be polymerized and granulated, a single amount When unreacted products of the body (C) and the monomer (D) remain, the solvent or the monomer (A), the monomer (C)
It is preferable to remove it by heating it to a temperature not lower than the boiling point of the monomer (D) and distilling it off, or by distilling it off under reduced pressure.

The non-aqueous latex particles produced as described above are present as fine particles having a uniform particle size distribution and, at the same time, exhibit very stable dispersibility, and particularly, they can be repeatedly used for a long time in a developing device. However, the dispersibility is good and no aggregation or precipitation is observed in the developing device. Further, when fixed by heating or the like, a strong coating film was formed, and excellent fixability was exhibited. Furthermore, the liquid developer of the present invention, when used in a plate making system,
Even after the hydrophilic treatment process of the non-image area, the toner image area has excellent resist property, and the original area reproducibility of the image area of the printed matter is excellent.

The liquid developer of the present invention which brings about the above effects is made possible by the insoluble latex provided by the present invention. The insoluble resin particles of the present invention are polymerized and granulated by using the monomer (C) containing a specific substituent and the dispersion stabilizing resin [P] of the present invention to obtain monodispersity and redispersion of the particles. The nature is improving. That is, monomer (C)
Is copolymerized with the monomer (A) which is insolubilized during the polymerization and granulation, but the specific substituent moiety contained in the monomer (C) is
Since the particles are formed by non-aqueous dispersion polymerization, it is designed to have a good affinity with the non-aqueous solvent, so that the solvatability with the dispersion medium is higher than that of the inclusion in the particle structure. Since it is good, it is presumed that it is oriented at the interface (surface) part of the particle structure, and as a result, the affinity for the dispersion medium on the particle surface is improved and the effect of preventing agglomeration between particles is significantly enhanced. To be done. At the same time, the dispersion stabilizing resin of the present invention comprises a block A composed of a polymer component containing a long-chain aliphatic group having a high affinity for a non-aqueous solvent.
And a block B composed of a polymer component having a low affinity for the non-aqueous solvent and having an affinity for the insoluble monomer (A), which is an AB type block copolymer. It is characterized by As a result, the block B portion is sufficiently adsorbed to the dispersed resin particles by physicochemical interaction during polymerization granulation, and the block A portion having a large affinity for the non-aqueous dispersion medium is for the solvent. It is presumed that the effect of the present invention has been achieved because it is possible to sufficiently solvate and sufficiently act the steric repulsion effect (so-called tail-like adsorption). It is considered that these factors suppress the aggregation / precipitation of the insoluble particles and significantly improve the redispersibility.

In the present invention, when a dispersion stabilizing resin [PA] containing a specific polar group at at least one end of the polymer main chain, which is a preferred embodiment, is used, the interaction with the insoluble resin particles is prevented. It is considered that the effect of stabilizing the dispersion described above is further improved by further improving the adsorption property to the particles.

When a dispersion stabilizing resin [PB] having a polymerizable functional group at at least one end of the polymer main chain is used, which is a more preferred embodiment, a monomer (insoluble) which becomes insoluble during the dispersion polymerization reaction ( It is copolymerized with A) and the monomer (D) and is more efficiently bound to the insoluble resin particles.

As described above, when the dispersion stabilizing resin [P] of the present invention is used, the dispersion stability is improved, and further,
When the resin [PA] or the resin [PB] is used, the same or higher effect can be obtained even if the amount used is reduced. On the other hand, in the case of the resin [PA] or the resin [PB], it can be mentioned that dispersion stabilization can be achieved with a small amount used and that the resin [P] which is not adsorbed on the particles is reduced. These are concentrated in the developer when the liquid developer is repeatedly used for a long period of time, and the concern that various problems may occur is improved.

On the other hand, the insoluble resin particles of the present invention are characterized in that the particles are polymerized and granulated using the polyfunctional monomer (D) to form a crosslinked structure. This allows
After the image is formed as toner particles, the suitability for treatment liquid (resist property) is improved even after a hydrophilic treatment step for making a printing original plate, and it is possible to significantly reduce damage to the toner image area. It was Further, in order to alleviate the fixing conditions, it is important in the apparatus that the insoluble resin particles have a resin structure having a low glass transition point. These resins having a low glass transition point are, for example, ester structures, Since it contains a polar structure such as an ether structure or an amide structure, it easily dissolves in the treatment liquid in the hydrophilic treatment step, and as a result, the resist property of the toner portion on the image portion deteriorates. This unfavorable phenomenon can be remarkably suppressed by partially crosslinking the inside of the resin particles. These effects of the dispersed resin particles of the present invention bring about the effects of the present invention.

In the liquid developer of the present invention, a colorant may be used if desired. 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 coloring methods, there is a method of physically dispersing in the dispersion resin by using a pigment or a dye. There is. For example, magnetic iron oxide powder, powdered lead iodide, carbon black, nigrosine, alkali blue, Hansa yellow, quinacridone red,
Examples include phthalocyanine blue. As another method of coloring, there is a method of dyeing a dispersed resin with a preferable dye as described in JP-A-57-48738. Alternatively, as another method, JP-A-53-53
There is a method of chemically bonding a dispersion resin and a dye as disclosed in JP-A-54029, or when a polymerization granulation method is used as described in JP-B-44-22955. There is a method of preparing a dye-containing copolymer by using a monomer containing a dye in advance.

If desired, various additives may be added to the liquid developer of the present invention in order to enhance the charging characteristics or improve the image characteristics. For example, Yuji Harazaki, "Electrophotography", Vol. 16, Vol. No. 2, page 44 is used. For example, di-2-ethylhexyl sulfosuccinic acid metal salt, naphthenic acid metal salt, higher fatty acid metal salt, lecithin, poly (vinylpyrrolidone), a copolymer containing a half-maleic acid amide component, and higher alcohols,
Examples thereof include polyethers and waxes. But,
It is not limited to these.

The amount of each main component of the liquid developer of the present invention will be described below. Toner particles containing a resin (and a coloring agent used as desired) as a main component are contained in an amount of 0.5 part by weight to 1000 parts by weight of the carrier liquid.
50 parts by weight is preferred. If it is less than 0.5 parts by weight, the image density will be insufficient, and if it exceeds 50 parts by weight, fog will easily occur in the non-image area. Furthermore, the carrier liquid-soluble resin for stabilizing the dispersion is also used as necessary, and can be added in an amount of about 0.5 to 100 parts by weight with respect to 1000 parts by weight of the carrier liquid. The charge control agent as described above is used as the carrier liquid 100.
0.001 to 1.0 parts by weight is preferable with respect to 0 parts by weight. Further, various additives may be added if desired, and the upper limit of the total amount of these additives is restricted by the electric resistance of the developer. That is, if the electric resistance of the liquid developer with the toner particles removed is lower than 10 ⁹ Ωcm, it becomes difficult to obtain a good quality continuous tone image. Therefore, the amount of each additive added is controlled within this limit. It is necessary.

[0102]

EXAMPLES The effects of the present invention will be described in more detail below with reference to production examples of dispersion-stabilizing resin, production examples of latex particles and examples of the present invention. However, the present invention is not limited to these. Absent.

Production Example of Dispersion Stabilizing Resin [P] 1: Resin [P-1] A mixed solution of 95 g of dodecyl methacrylate and 200 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream to give -7.
Cooled to 8 ° C. 1.0 g of 1,1-diphenylbutyllithium was added and reacted for 12 hours. Further, a mixed solution of 5 g of triphenylmethyl methacrylate and 25 g of tetrahydrofuran was sufficiently degassed under a nitrogen stream and added to this mixed solution, and the mixture was further reacted for 8 hours. 0 for this mixture
After adjusting to ℃, add 10 ml of methanol,
After reacting for a minute, the polymerization was stopped. The temperature of the obtained polymer solution was raised to 30 ° C. with stirring, 15 ml of a 30% hydrogen chloride ethanol solution was added thereto, and the mixture was stirred for 1 hour. Next, the solvent was distilled off from the reaction mixture under reduced pressure until the total amount became half, and the mixture was reprecipitated in 1 liter of methanol. The precipitate was collected and dried under reduced pressure to obtain a polymer. The obtained polymer had a weight average molecular weight (hereinafter abbreviated as Mw) of 4.5 × 10 ⁴ and a yield of 70 g.

[0104]

[Chemical 27]

Production Example 2 of Dispersion Stabilizing Resin [P]: Resin [P-2] A mixed solution of 100 g of dodecyl methacrylate and 200 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream,
Cooled to 20 ° C. 1.3 g of 1,1-diphenylbutyllithium was added and reacted for 12 hours. Further, to this mixed solution, a mixed solution of 62 g of methyl acrylate, 12 g of triphenylmethyl methacrylate and 5 g of tetrahydrofuran was thoroughly degassed under a nitrogen stream and added, and the mixture was further reacted for 8 hours. The mixture was brought to 0 ° C. and then methanol 1
Polymerization was stopped by adding 0 ml and reacting for 30 minutes. The temperature of the resulting polymer solution was raised to 30 ° C. with stirring, 3 ml of a 30% hydrogen chloride ethanol solution was added thereto, and the mixture was stirred for 1 hour. Then, the solvent was distilled off from the reaction mixture under reduced pressure until the total amount was halved, followed by reprecipitation in 1 liter of petroleum ether. The precipitate was collected and dried under reduced pressure to obtain a polymer. The polymer obtained has an Mw of 4.3 × 10 ^4.
The yield was 78 g.

[0106]

[Chemical 28]

Production Example 3 of Resin [P] for Dispersion Stabilization: Resin [P-3] A mixed solution of 46 g of octadecyl methacrylate, 0.4 g of (tetraphenylporphinato) aluminum methyl and 60 g of methylene chloride was heated at a temperature of 30 under a nitrogen stream. ℃ was made. This was irradiated with light of 300 W-xenon lamp through a glass filter from a distance of 25 cm and reacted for 12 hours. Add benzyl methacrylate 4 to this mixture.
After irradiating with light for 8 hours in the same manner, 3 g of methanol was added to this reaction mixture and stirred for 30 minutes to stop the reaction. Next, Pd-C was added to this reaction mixture, and catalytic reduction reaction was performed at a temperature of 25 ° C. for 1 hour. The insoluble material was filtered off, and then reprecipitated in 500 ml of methanol, and the precipitate was collected and dried. The yield of the obtained polymer is 33 g.
The Mw was 4 × 10 ⁴ .

[0108]

[Chemical 29]

Production Example 4 of dispersion stabilizing resin [P]: Resin [P-4] A mixed solution of 70 g of octadecyl methacrylate, 30 g of dodecyl acrylate, 0.5 g of (tetraphenylporphinato) aluminum methyl and 60 g of methylene chloride was used as a nitrogen stream. The temperature was set to 30 ° C. below. 300W-
25cm xenon lamp light through glass filter
Light was irradiated from a distance of and reacted for 12 hours. Further, 60 g of methyl acrylate and 9.3 g of trimethylsilyl methacrylate were added to this mixture, and after similarly irradiating with light for 8 hours, 3 g of methanol was added to this reaction mixture and stirred for 30 minutes to stop the reaction. Then add 3 to this reaction mixture.
10 g of a methanol-water (95/5) solution containing 0% hydrogen chloride was added, and the mixture was reacted at 25 ° C. for 1 hour to hydrolyze the trimethylsilyl methacrylate component. This was reprecipitated in 1.5 liters of methanol to collect the precipitate,
After further thorough washing with methanol, it was dried. The yield of the obtained polymer was 70 g, and the Mw was 5 × 10 ⁴ .

[0110]

[Chemical 30]

Production Example 5 of dispersion stabilizing resin [P]: Resin [P-5] 100 g of dodecyl methacrylate and 200 g of toluene.
The mixed solution of was thoroughly degassed under a nitrogen stream and cooled to 0 ° C. Next, 2.5 g of 1,1-diphenyl-3-methylpentyllithium was added, and the mixture was stirred for 6 hours. Further, 30 g of methyl methacrylate and 4.6 g of 4-vinylphenyloxytrimethylsilane were added to this mixture and stirred for 6 hours, then 3 g of methanol was added and stirred for 30 minutes. Then, the reaction mixture was mixed with 10% 30% hydrogen chloride ethanol
After adding g, the mixture was stirred at 25 ° C. for 1 hour and then reprecipitated in 1 liter of methanol to collect the precipitate. The precipitate was washed twice with 300 ml of methanol and dried. The yield of the obtained polymer was 102 g, and the Mw was 6 × 10 ⁴ .

[0112]

[Chemical 31]

Production Example 6 of dispersion stabilizing resin [P]: Resin [P-6] Hexadecyl methacrylate 95 g, benzyl N, N-
A mixture of 2.0 g of dimethyldithiocarbamate was sealed in a container under a nitrogen stream and heated to a temperature of 60 ° C. This was irradiated with light from a high pressure mercury lamp of 400 W from a distance of 10 cm through a glass filter for 6 hours to perform photopolymerization. this,
After dissolving in 100 g of tetrahydrofuran, 5 g of acrylic acid was added, the atmosphere was replaced with nitrogen, and light was again irradiated for 10 hours. The obtained reaction mixture was reprecipitated in 1.5 liter of methanol, collected, and dried. The yield of the obtained polymer was 68 g, M
w was 3.5 × 10 ⁴ .

[0114]

[Chemical 32]

Production Example 7 of Dispersion Stabilizing Resin [P]: Resin [P-7] A mixed solution of 80 g of stearyl methacrylate and 200 g of tetrahydrofuran was thoroughly deaerated under a nitrogen stream,
Cooled to 78 ° C. 1.0 g of 1,1-diphenyl-3-methylpentyl potassium was added and stirred for 10 hours. Further, 20 g of styrene was added to this mixture and the mixture was stirred for 8 hours, then, the reaction mixture was brought to 0 ° C. and 10 cc of methanol was added. Next, this was reprecipitated in 1.5 liter of methanol, the precipitate was collected by filtration and dried, and the yield of the polymer obtained was 68 g and the Mw was 3 × 10 ⁴ .

[0116]

[Chemical 33]

Production Example 8 of Dispersion Stabilizing Resin [P]: Resin [P-8] Methyl acrylate 97 g, methacrylic acid 3 g, 2-mercaptoethanol 2 g, and tetrahydrofuran 20.
While stirring 0 g of the mixed solution under a nitrogen stream, a temperature of 60
Warmed to ° C. To this, 1.0 g of 2,2'-azobis (isovaleronitrile) (abbreviation AIVN) was added and reacted for 4 hours. I. V. N. Add 0.5g of 4
Reacted for hours. After bringing the reaction mixture to a temperature of 20 ° C.,
8.6 g of 4,4'-azobis (cyanovaleric acid), 12 g of dicyclohexyldicarbodiimide, 0.2 g of 4- (N, N-dimethyl) pyridyl and tetrahydrofuran 3
0 g of the mixed solution was added dropwise over 1 hour. After stirring for 2 hours as it is, add 5 g of 85% formic acid aqueous solution for another 30
Stir for minutes. Next, the precipitated crystals were separated by filtration, and the filtrate was evaporated under reduced pressure to remove the solvent. The Mw of the obtained polymer (polymerization initiator) was 6.3 × 10 ³ .

[0118]

[Chemical 34]

While stirring a mixed solution of 70 g of tridecyl methacrylate and 170 g of toluene under a nitrogen stream,
The temperature was raised to 70 ° C. After preliminarily purging a solution of 30 g of the above polymer dissolved in 30 g of toluene with nitrogen,
In addition, it reacted for 8 hours. The polymer obtained is methanol 2
Reprecipitated in liters, collected and dried. The yield of the obtained polymer was 72 g, and the Mw was 4 × 10 ⁴ .

[0120]

[Chemical 35]

Production Examples 9-18 of Dispersion Stabilizing Resin [P]: Resins [P-9] to [P-18] In Production Example 6 of dispersion stabilizing resin [P], 95 g of hexadecyl methacrylate and 5 g of acrylic acid. In the same manner as in Production Example 6 except that each of the monomers shown in Table A below was used instead of, each dispersion stabilizing resin was produced.

[0122]

[Table 1]

[0123]

[Table 2]

[0124]

[Table 3]

Production Example 1 of Dispersion Stabilizing Resin [PA] 1: Resin [PA -1] In the production example of resin [P-1], a polymerization reaction was first carried out in the same manner as in [P-1]. Then, after the mixture was heated to 0 ° C., carbon dioxide gas was bubbled at a flow rate of 10 ml / min for 1 hour to terminate the polymerization. The temperature of the obtained polymer solution was raised to 30 ° C. with stirring, 15 ml of a 30% hydrogen chloride ethanol solution was added thereto, and the mixture was stirred for 1 hour. This was reprecipitated in 1.5 liter of methanol, and the precipitate was collected and dried. The Mw of the obtained polymer was 4 × 10 ⁴ , and the yield was 65 g.

[0126]

[Chemical 36]

Production Examples 2 to 4 of Dispersion Stabilizing Resin [PA]:
Resins [PA-2] to [PA-4] In the production examples of the resins [P-2] to [P-4], the polymerization reaction was performed in the same manner as the synthesis of each resin. afterwards,
As a reaction to stop each reaction, carbon dioxide at a temperature of 0 ° C and a flow rate of 1
Polymerization was stopped by bubbling at 0 ml / min for 1 hour. Next, each reaction product was treated in the same manner as in the treatment of the corresponding synthesis example to isolate each polymer.

[0128]

[Chemical 37]

[0129]

[Chemical 38]

Preparation Example 5 of dispersion stabilizing resin [PA]: Resin [PA-5] 45 g of methyl acrylate, 5 g of acrylic acid and 2.0 g of 2-carboxyethyl-N, N-dimethyldithiocarbamate [I-1]. The mixture was sealed in a container under a stream of nitrogen and warmed to a temperature of 40 ° C. Then, with a 400W high-pressure mercury lamp, pass a glass filter from a distance of 10 cm.
It was irradiated with light for an hour and photopolymerized. The reaction product was dissolved in 100 g of tetrahydrofuran and then reprecipitated in 800 ml of methanol to obtain an intermediate having the following structure.

[0131]

[Chemical Formula 39]

A mixed solution of 15 g of the above intermediate, 85 g of tetradecyl methacrylate and 100 g of tetrahydrofuran was heated to a temperature of 50 ° C. under a nitrogen stream. This was irradiated with light for 10 hours under the same conditions as above. Next, this polymer was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried to obtain 75 g of a polymer having Mw of 6 × 10 ⁴ .

[0133]

[Chemical 40]

Production Examples 6 to 13 of Dispersion Stabilizing Resin [PA]:
Resins [PA-6] to [PA-13] In the production examples of the resin [PA-5], compounds shown in the following Table-B are used instead of 2-carboxyethyl-N, N-dimethyldithiocarbide [I-1]. Polymers were obtained in the same manner as in the resin [PA-5] except that 0.018 mol of each was used. The Mw of each polymer obtained was 5.5 × 10 ^{4 to} 7 ×.
The yield was in the range of 70 to 80 g in the range of 10 ⁴ .

[0135]

[Table 4]

[0136]

[Table 5]

[0137]

[Table 6]

Production Examples 14 to 22 of dispersion stabilizing resin [PA]:
Resin [PA-14] to [PA-22] A monomer corresponding to the polymer component of the block B part of the following Table-C, and an initiator [I-10] having the following structure (6.2 g) are added at a concentration of 50% of tetrahydrofuran. And a temperature of 50 ° C. under a nitrogen stream. 10 times with 400W high pressure mercury lamp
Light was irradiated for 10 hours through a glass filter from a distance of cm. Next, the monomer corresponding to the polymer component of the block A portion of the following Table-C is dissolved in tetrahydrofuran to 50%.
The concentrated solution was degassed under a nitrogen stream, added to the above reaction solution, and reacted again for 12 hours under the above light irradiation conditions. The obtained polymer was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried. Mw is 3 × 10 ^{4 to} 6 ×
In the range of 10 ^4, the yield was 75% to 80% (by weight).

[0139]

[Chemical 41]

[0140]

[Table 7]

[0141]

[Table 8]

[0142]

[Table 9]

Production Example 1 of Dispersion Stabilizing Resin [PB]: Resin [PB -1] In the production example of resin [PA -1], the same operation was carried out until the termination of the polymerization reaction due to the inflow of carbon dioxide gas. 12 g of 2-hydroxyethyl methacrylate was added to the obtained polymer solution.
Was added to bring the temperature to 25 ° C. 8 g of dicyclohexylcarbodiimide (abbreviated D.C.C.) was added to this mixed solution.
A mixed solution of 0.2 g of-(N, N-diethylamino) pyridine and 20 g of methylene chloride was added dropwise over 1 hour. The reaction was further continued for 3 hours to complete the reaction. Next, 20 g of 30% hydrogen chloride ethanol solution was added to this reaction mixture, and the mixture was stirred for 1 hour, then the insoluble matter was filtered off, and the filtrate was reprecipitated in 1 liter of methanol. The precipitate was collected by filtration, dissolved again in 90 g of toluene, the insoluble matter was filtered off, and the filtrate was reprecipitated in 500 ml of methanol. The precipitate was collected by filtration and dried. The yield of the obtained polymer was 63 g, and the Mw was 4.3 × 10 ⁴ .

[0144]

[Chemical 42]

Production Examples 2 to 4 of Dispersion Stabilizing Resin [PB]:
Resin [PB-2] to [PB-4] In each polymer of resin [PA-2] to [PA-4],
By operating in the same manner as in the case of the resin [PB-1], a polymerizable group was introduced into each polymer. The polymer obtained is as follows.

[0146]

[Chemical 43]

Production Examples 5 to 12 of Dispersion Stabilizing Resin [PB]:
Resins [PB-5] to [PB-12] of tetrahydrofuran containing 4.5 g of a monomer corresponding to the block B part and an initiator [I-5] in an amount corresponding to the weight ratio shown in Table D below. The 50 wt% concentration mixed solution was heated to a temperature of 50 ° C. under a nitrogen stream. In addition to this, the resin [P
Light irradiation was carried out for 10 hours under the same conditions as in [A-5]. Next, an amount of block A corresponding to the weight ratio shown in Table-D below is used.
Part of tetrahydrofuran containing a monomer corresponding to 5 parts
Add a mixed solution of 0 wt% concentration, and set the temperature to 50 under a nitrogen stream.
Further irradiation with light was carried out at 10 ° C. for 10 hours. The temperature of this reaction product was adjusted to 25 ° C., and 0.025 mol of each of the polymerizable group-introducing compounds shown in Table D below and 30 g of tetrahydrofuran were added. With stirring, D.I. C. C. 5.2 g, 4-
A mixed solution of 0.2 g of (N, N-dimethylamino) pyridine and 10 g of methylene chloride was added dropwise over 1 hour, and the reaction was continued for another 3 hours. After adding 10 g of 80% formic acid solution to this and stirring for 1 hour, the insoluble matter was filtered off, and the obtained filtrate was reprecipitated in 1.5 liter of methanol. The precipitate was collected, dissolved in 200 ml of toluene, and then reprecipitated again in 1 liter of methanol to collect and dry the precipitate. The Mw of the obtained polymer was 3.5 × 10 ^{4 to} 7 × 10.
Within the range of ⁴ , the yield was 70-80% (by weight).

[0148]

[Table 10]

[0149]

[Table 11]

[0150]

[Table 12]

Production Examples 13 to 20 of Dispersion Stabilizing Resin [PB]:
Resin [PB-13] to [PB-20] 43 g of methyl acrylate, an initiator of the following structure [I-1
A mixed solution of 3.9 g of 1] and 43 g of tetrahydrofuran was subjected to a polymerization reaction for 12 hours by the same photopolymerization method as for the resin [PA-5]. Furthermore, octadecyl methacrylate 7
A mixed solution of 0 g, 30 g of dodecyl acrylate and 100 g of tetrahydrofuran was added, and the photopolymerization reaction was carried out similarly to 1
It was carried out for 2 hours. After adding 334 g of tetrahydrofuran to the polymer solution obtained as described above, the temperature was raised to 20 ° C. After adding 0.04 mol of each of the polymerizable group-containing carboxylic acid compounds shown in Table E below, D.I. C. C. 8.3 g, 4- (N, N-dimethylamino) pyridine 0.4 g and methylene chloride 15 g were added dropwise over 1 hour, and the mixture was further stirred for 3 hours. Next, 15 g of 80% formic acid solution was added to this reaction mixture and the mixture was stirred for 1 hour, then the insoluble matter was filtered off, the filtrate was reprecipitated in 1.5 liters of methanol, and the precipitate was collected and dried. Mw of each polymer
Was about 4 × 10 ⁴ and the yield was 100-110 g.

[0152]

[Chemical 44]

[0153]

[Table 13]

[0154]

[Table 14]

Production Example 1 of Latex Particles: Latex particles D-1 12 g of dispersion stabilizing resin [PA -4], and 90% of vinyl acetate.
g, 10 g of methyl vinyl ether, 3 g of octadecyl methacrylate, 3 g of divinyl adipate and 384 g of Isopar H were heated to 70 ° C. while stirring under a nitrogen stream. 2,2'-azobis (isovaleronitrile) (abbreviation AIVN) as a polymerization initiator
0.8 g was added and reacted for 3 hours. Add the initiator 2
A cloudiness occurred after 0 minutes, and the reaction temperature rose to 88 ° C.
Further, 0.5 g of an initiator was added and reacted for 2 hours, then the temperature was raised to 100 ° C. and stirred for 2 hours to distill off unreacted vinyl acetate. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion had a polymerization rate of 90% and an average particle size of 0.22μ.
m latex. The particle size was measured by CAPA-500 (manufactured by Horiba, Ltd.).

Production Examples 2 to 21 of Latex Particles: Latex Particles D-2 to D-21 In Production Example 1 of latex particles, the following tables are used instead of the dispersion stabilizing resin [PA-4], octadecyl methacrylate and divinyl adipate. The latex particles D-2 to D of the present invention were operated in exactly the same manner as in Production Example 1 except that the dispersion stabilizing resin described in -F, the monomer (C) and the monomer (D) were used. -21 was produced. The degree of polymerization of each latex particle obtained was 85 to 90%, and the average particle diameter was 0.15 to 0.15.
Within the range of 0.25 μm, the monodispersity was good.

[0157]

[Table 15]

[0158]

[Table 16]

Production Example 22 of Latex Particles: Latex Particle D-22 16 g of dispersion stabilizing resin [PB-19], 80 g of methyl methacrylate, 20 g of ethyl acrylate, 3 g of octadecyl acrylate, 3.5 g of ethylene glycol diacrylate and Isopar H were used. The mixed solution of 375 g was heated to a temperature of 40 ° C. while stirring under a nitrogen stream. A.
I. V. N. 0.7 g was added and the mixture was reacted for 4 hours.
I. V. N. 0.5 g was added and reacted for 4 hours. After cooling, it was passed through a nylon cloth of 200 mesh, and the obtained white dispersion was a latex having a polymerization rate of 98% and an average particle size of 0.25 μm.

Production Example 23 of Latex Particles: Latex Particle D-23 18 g of dispersion stabilizing resin [PB-14] and Isopar H
177 g of the mixed solution was stirred at a temperature of 6 while stirring under a nitrogen stream.
Warmed to 0 ° C. 60 g of methyl methacrylate, 40 g of methyl acrylate, 3.4 g of dodecyl acrylate,
4 g of ethylene glycol diacrylate and 200 g of Isopar G and A. I. V. N. 1.0 g of a mixed solution was added dropwise over 2 hours, and the mixture was stirred as it was for 2 hours. Furthermore, A. I. V. N. Was added and stirred for 3 hours. After cooling, it was passed through a nylon cloth of 200 mesh, and the obtained white dispersion was a latex having a polymerization rate of 100% and an average particle size of 0.25 μm.

Production Examples of Latex Particles 24 to 30: Latex Particles D-24 to D-30 Monomers (A) (that is, methyl methacrylate and methyl acrylate) used in Production Example 23 of latex particles for stabilizing dispersion Resin [PB-14], Monomer (C)
(Ie, dodecyl acrylate) and monomer (D)
Instead of (ie, ethylene glycol diacrylate), each of the compounds shown in Table G below was used,
Latex particles were produced in the same manner as in Production Example 23 above. The polymerization rate of the obtained latex particles is 95 to 100.
%, The average particle size was in the range of 0.17 to 0.30 μm, and the monodispersity was good.

[0162]

[Table 17]

[0163]

[Table 18]

Production Example 31 of Latex Particles: (Comparative Example A) The procedure of Production Example 1 of Latex Particles was repeated except that a mixed solution of 20 g of poly (octadecyl methacrylate), 100 g of vinyl acetate and 380 g of Isopar H was used. A white dispersion was obtained which was latex particles having a polymerization rate of 88% and an average particle size of 0.23 μm.

Production Example 32 of Latex Particles: (Comparative Example B) 12 g of a dispersion stabilizing resin (1) having the following structure synthesized by the method disclosed in JP-A-61-43757, 90 g of vinyl acetate and methyl vinyl ether. A white dispersion of latex particles having a polymerization rate of 88% and an average particle size of 0.18 μm was prepared by the same procedure as in Preparation Example 1 of latex particles except that a mixed solution of 10 g, 3 g of divinylbenzene and 388 g of Isopar H was used. Obtained.

[0166]

[Chemical 45]

Production Example 33 of Latex Particles: (Comparative Example C) In the same manner as in Production Example 1 except that 3 g of divinyl adipate as the monomer (D) was removed from Production Example 1 of latex particles, Polymerization rate 90%, average particle size 0.22 μm
A white dispersion of latex particles was obtained.

Production Example 34 of Latex Particles: (Comparative Example D) A mixed solution of 97 g of octadecyl methacrylate, 3 g of acrylic acid and 200 g of toluene was heated under a nitrogen stream at a temperature of 75.
Warmed to ° C. A. I. V. N. 1.0 g was added and reacted for 8 hours. Next, 6 g of glycidyl methacrylate, t-
Butylhydroquinone (1.0 g) and N, N-dimethyldodecylamine (1.2 g) were added, and the mixture was stirred at a temperature of 100 ° C. for 18 hours. After cooling, the reaction solution was reprecipitated in 2 liters of methanol, collected by filtration and dried to obtain 84 g of a white powder. The Mw of the obtained dispersion stabilizing resin (2) having the following structure was 5 × 10 ⁴ .

[0169]

[Chemical 46]

In the same manner as in Production Example 23 of Latex Particles, except that in Comparative Example 23 of Latex Particles, 20 g of the above Comparative Dispersion Stabilizing Resin was used instead of 18 g of the dispersion stabilizing resin [PB-14]. A white dispersion which is latex particles having a polymerization rate of 98% and an average particle size of 0.30 μm was obtained.

Production Example 35 of Latex Particles: (Comparative Example E) Except that 4 g of ethylene glycol diacrylate as the monomer (D) was removed from Production Example 23 of latex particles, exactly the same as Production Example 23. A white dispersion was obtained which was latex particles having a polymerization rate of 100% and an average particle size of 0.23 μm.

Example 1 10 g of a dodecyl methacrylate / acrylic acid copolymer (copolymerization ratio; 95/5 weight ratio), 10 g of nigrosine and 30 g of Isopar G were placed in a paint shaker (manufactured by Tokyo Seiki Co., Ltd.) together with glass beads. Put in, disperse for 4 hours,
A fine dispersion of nigrosine was obtained. 30 g of the resin dispersion of Production Example 1 of latex particles, 2.5 g of the above nigrosine dispersion, and branched octadecyl alcohol FOC-180.
A liquid developer for electrostatic photography was prepared by diluting 15 g of 0 (manufactured by Nissan Chemical Industries, Ltd.) and 0.07 g of octadecene-half-maleic acid octadecylamide copolymer to 1 liter of Isopar G.

(Production of Comparative Developers A to C) Three types of comparative liquid developers A, B and C were produced by replacing the resin dispersion with the following resin dispersion in the production of the above liquid developer. .. Comparative Liquid Developer A: Resin dispersion of Preparation Example 31 of latex particles. Comparative liquid developer B: resin dispersion of Production Example 32 of latex particles. Comparative liquid developer C: resin dispersion of Production Example 33 of latex particles.

Various properties were evaluated by using these liquid developers for electrophotographic plate making system, and the results are shown in Table-H.

[0175]

[Table 19]

The measurement of each evaluation item in Table-H was carried out as follows. (Note 1) Dirt on developing device and 2000th plate image: Liquid developer was used as a developer for fully automatic plate-making machine ELP404V (manufactured by Fuji Photo Film Co., Ltd.), and ELP master II type electrophotographic photosensitive material was used. (Fuji Photo Film Co., Ltd.) was exposed and developed. Plate making speed is 7
Plates / minute. Furthermore, after processing 2000 sheets of ELP Master II type, the presence or absence of toner adhesion stains on the developing device was observed. The blackening rate (image area) of the copied image is 30
% Manuscript was used.

(Note 2) Image fixability: EL liquid developer
The electrophotographic photosensitive material P-1 prepared as described below was used as a developer of P404V to make a plate, and the strength of the image area was visually evaluated using a friction tester. A liquid developer ELP-T (manufactured by Fuji Photo Film Co., Ltd.), which has a practically sufficient fixing property, was used as a liquid developer serving as a reference for evaluation. <Production of Electrophotographic Photosensitive Material P-1> 34 g of a binder resin B-1 having the following structure, 6 g of a binder resin B-2 having the following structure, 200 g of photoconductive zinc oxide, 0.03 g of uranine, and rose bengal 0. 0.06 g, tetrabromophenol blue 0.02 g, phthalic anhydride 0.30 g, o-chlorophenol 0.01 g, and toluene 300 g were mixed with a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at 1 × 10 ⁴ r.
Dispersion was carried out for 10 minutes at a rotation speed of pm. This photosensitive layer-forming dispersion was applied to a conductive-treated paper with a wire bar so that the dry adhesion amount was 26 g / m ² , dried at 100 ° C. for 30 seconds, and then heated at 120 ° C. for 1 hour. Then in the dark 2
The electrophotographic photosensitive material P-1 was produced by leaving it under conditions of 0 ° C. and 65% RH for 24 hours.

[0178]

[Chemical 47]

(Note 3) Toner image resist property: An original plate prepared by the same method as the above (Note 2) was etched using a desensitizing solution ELP-EX (manufactured by Fuji Photo Film Co., Ltd.). After passing through once, it was dipped in the hydrophilic treatment liquid E-1 for the photoconductive layer binder resin having the following formulation for 5 minutes, washed with water and dried. The image portion of the obtained printing original plate was observed with an optical microscope, and the presence or absence of damage in the image portion was visually evaluated. <Preparation of Hydrophilization Treatment Liquid E-1> Monoethanolamine 8
0g, Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) 8
g and 100 g of benzyl alcohol are dissolved in distilled water 1
After the volume was adjusted to 1 liter, the pH was adjusted to 11.0 with potassium hydroxide to prepare a treatment liquid E-1.

(Note 4) Printing durability: The printing plate precursor made by plate-making and hydrophilic treatment according to the conditions of (Note 3) above was used as a fountain solution, and the hydrophilic treatment liquid E-1 was diluted 20 times with distilled water. Printing machine Hamada Star 800SX type (manufactured by Hamada Star Co., Ltd.) under the condition that the solution is used and the neutral paper is used as the printing base paper
Was used to check the number of printed sheets that did not cause loss of the image portion of the printed matter.

From the results shown in Table H, the developers of the present invention and Comparative Example C did not cause stains on the developing device, and the image on the 2000th plate was clear, showing good results.
This shows that the dispersibility and redispersibility are good. On the other hand, in the developers of Comparative Examples A and B, the redispersibility was deteriorated and the reproducibility of the actual copied image was adversely affected. In addition, when the mechanical strength of the toner image area was evaluated by forcibly rubbing, each toner particle was good. That is, it was confirmed that the particles of the present invention have a sufficient fixability in practical use. Furthermore, when the zinc oxide and the binder resin B-1 in the non-image area of the plate surface after the plate making are chemically treated to be hydrophilic, the image area is sufficiently resisted with the toner layer, and the image area is defective. When the presence or absence of the toner particles was checked under a forced condition, defects other than the toner particles of the present invention occurred in the fine areas of the toner image portion such as fine lines and fine characters. Further, when printing was carried out as an offset master original plate after processing under ordinary desensitizing conditions, only a clear printing product was obtained even after printing 5,000 sheets of the present invention. In Comparative Examples A and B, the deterioration of the reproducibility of the copied image at the time of plate making appeared on the printed matter as it was, and the lack of fine lines, fine characters and the like was observed from the imprinting. Further, in Comparative Example C, thin lines, thin characters, and the like were missing about 2,000 sheets after printing when printing. As mentioned above,
Only the liquid developer of the present invention, in an electrophotographic plate making system utilizing an electrophotographic photoreceptor having improved printing characteristics,
It had excellent dispersibility / redispersibility and printing durability.

Example 2 Preparation of Latex Particles 30 g of the resin dispersion of Example 23, 10 g of branched hexadecyl alcohol FOC-1600 (manufactured by Nissan Kagaku Co., Ltd.), and octadecyl vinyl ether /
A liquid developer for electrostatic photography was prepared by diluting 0.06 g of a half-maleic acid dodecylamide copolymer with 1 liter of Isopar G.

(Production of Comparative Developers D and E) Two types of comparative liquid developers D and E were produced by replacing the resin dispersion with the following resin dispersion in the production of the above liquid developer. Comparative liquid developer D: resin dispersion of Production Example 34 of latex particles. Comparative liquid developer E: resin dispersion of Preparation Example 35 of latex particles.

Various properties were evaluated by using these liquid developers for an electrophotographic plate making system, and the results are shown in Table-I.

[0185]

[Table 20]

In Table-I, the developing device contamination and 20
The measurement of the evaluation items of the 00th plate image was carried out in Example 1
I went in the same way. The other evaluation items were measured as follows. (Note 5) Toner image resisting property: electrophotographic photosensitive material P-2 prepared according to the following formulation was used, and the surface potential was +450 V in a dark place.
After being electrically charged to 280 mW, a 2.8 mW output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780
nm) on the surface of the light-sensitive material at 60 erg / cm
² irradiation amount, pitch 25μm and scanning speed 3
After exposure at a speed of 00 m / sec, a toner image was obtained by applying a bias voltage of 30 V to the counter electrode and developing using each of the liquid developers described above. Further, the toner image was fixed by heating at 100 ° C. for 1 minute.

<Preparation of Electrophotographic Photosensitive Material P-2> 1.9 parts by weight of X-type metal-free phthalocyanine (manufactured by Dainippon Ink and Chemicals, Inc.) as an organic photoconductive compound, and thiobarbitur of the following structure as an additive 0.15 parts by weight of an acid compound, 17 parts by weight of a binder resin B-3 having the following structure, and 1: 1 of a mixed solution of tetrahydrofuran / cyclohexane in an 8/2 weight ratio.
00 parts by weight was put into a 500 ml glass container together with glass beads and dispersed for 60 minutes with a paint shaker, and then the glass beads were filtered to obtain a dispersion liquid for a photoconductive layer. Next, this photoconductive layer dispersion is applied onto a grained aluminum plate having a thickness of 0.25 mm and dried to obtain an electrophotographic printing plate precursor having a photoconductive layer having a dry film thickness of 6.0 μm. It was adjusted.

[0188]

[Chemical 48]

Each of the original plates thus obtained was immersed in the processing liquid E-2 having the following formulation for 30 seconds to remove the photoconductive layer in the non-image area, washed with water for 30 seconds, and then dried with a dryer. Air dried. <Prescription of Treatment Liquid E-2> Potassium silicate 40 g Potassium hydroxide 10 g Ethanol 100 g Water 800 g The presence or absence of defects in fine lines and fine characters in the image portion of this printing plate was determined with a 60-fold loupe (PEAK ( (Manufactured by Co., Ltd.).

(Note 6) Printing durability: An offset printing original plate prepared by operating each light-sensitive material under the same conditions as in (Note 5) was gummed and then subjected to an offset printing machine (Sakurai Seisakusho Co., Ltd. ) Manufactured by Oliver 52 type) indicates the number of sheets that can be printed without causing a background stain on the non-image portion of the printed matter and on the image quality of the image portion (the larger the number of printed sheets, the better the printing durability).

From the results shown in Table I, the liquid developers of the present invention and Comparative Example E exhibited good redispersibility, and the image of the plate after 2000 sheets was also good. However, Comparative Example D
Toner dust was generated, the developing part was stained, and the image on the plate was also missing after 2000 sheets, such as thin lines and thin characters.

Next, the plate after plate making was made to elute the non-image area by using an alkaline processing liquid to obtain a master plate for offset master. At this time, in Comparative Example E, a small area portion of the toner image portion such as a thin line or a thin character was missing. This indicates that the resist property of the toner layer with respect to the treatment liquid was not sufficient and the toner layer was dissolved and eluted during the treatment. On the other hand, in the present invention and Comparative Example D, these phenomena were not observed and sufficient resist properties were shown. Further, when actually printed as an offset master original, the image quality of the printed matter of the present invention was clear even after printing 100,000 sheets or more. However, Comparative Example D is poor in reproducibility of copied images during plate making, and Comparative Example E is insufficient in resist property to the processing solution for dissolving and removing the non-image area, both of which are sufficient as the master plate for offset master. Since the image reproducibility was not obtained, the image quality of the printed matter deteriorated after printing, and the printed matter of sufficient image quality could not be obtained. As described above, only the liquid developer of the present invention satisfies excellent dispersibility / redispersibility and printing durability in an electrophotographic plate making system in which a non-image area is eluted to be a printing original plate. It was

Example 3 10 g of tetradecyl methacrylate / methacrylic acid copolymer (copolymerization ratio; 95/5 weight ratio), and nigrosine 1
0 g and 30 g of Isopar G were put together with glass beads in a paint shaker (manufactured by Tokyo Seiki Co., Ltd.) and dispersed for 4 hours to obtain a fine dispersion of nigrosine. 30 g of the resin dispersion of Production Example 2 of latex particles, 2.5 g of the above nigrosine dispersion, 0.06 g of hexadecene / semi-maleic acid octadecylamide copolymer and FOC-180.
A liquid developer for electrostatic photography was prepared by diluting 20 g of 0 with 1 liter of Isopar G. The obtained liquid developer of the present invention was evaluated for stains on the developing device and the 2000th plate image under the same conditions as (Note 1) of the evaluation items of Example 1, and both were evaluated as Example 1. Similarly good results have been obtained.

Next, the electrophotographic photosensitive material P-3 prepared according to the following formulation was charged to -6 kV in the dark, and a 2.0 mW output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780 nm) was used as a light source. Using a pitch of 25μ on the surface of the photosensitive material under an irradiation amount of 45 erg / cm ^2.
m and a scanning speed of 330 m / sec, the film was exposed, developed with the liquid developer of the present invention, and further heated at 60 ° C. for 30 seconds to obtain a toner image.

<Production of Electrophotographic Photosensitive Material P-3> 25 g of Binder Resin B-4 having the following structure, Binder Resin B- having the following structure
5 g, 6 g of the binder resin B-6 having the following structure, 200 g of photoconductive zinc oxide, 0.3 g of phthalic anhydride, 0.01 g of phenol, and 0.018 of the cyanine dye A having the following structure.
A mixture of g and 300 g of toluene was dispersed for 10 minutes at a rotation speed of 1 × 10 ⁴ rpm using a homogenizer to prepare a photosensitive layer forming dispersion. This is applied to a conductively treated paper with a wire bar so that the dry adhesion amount becomes 25 g / m ² , dried at 100 ° C for 20 seconds, and further dried at 120 ° C for 1 second.
Heated for hours. Then, by leaving it in the dark at 20 ° C. and 65% RH for 24 hours, the electrophotographic photosensitive material P
-3 was produced.

[0196]

[Chemical 49]

The thus obtained master plate was passed through an etching machine once using ELP-EX, and then immersed in a hydrophilic treatment liquid E-3 for a photoconductive layer binder resin having the following formulation for 3 minutes. After that, it was washed with water and dried. <Preparation of Treatment Liquid E-3> 80 g of diethanolamine, 5 g of Neosoap (manufactured by Matsumoto Yushi Co., Ltd.) and 80 g of methyl ethyl ketone were dissolved in distilled water to 1 liter, and the pH was adjusted to 11.0 with potassium hydroxide, Treatment liquid E-3
Was produced.

When the image area of the obtained printing original plate was observed with an optical microscope, no defects such as fine lines or fine characters in the toner image area were observed, and the toner particles of the present invention had good resist properties. Next, printing was carried out in the same manner as in Example 1 except that the above original plate was used as an offset master original plate, and the fountain solution used was a solution prepared by diluting the above-mentioned processing liquid E-3 with distilled water 10 times. When the property was evaluated, 3,000 prints with good print quality were obtained.

Examples 4 to 15 Same as Example 1 except that latex particles shown in Table J below were used instead of the latex particles D-1 of the liquid developer of the present invention. Then, each liquid developer was prepared.

[0200]

[Table 21]

Each of the obtained liquid developers was used in an electrophotographic plate making system in the same manner as in Example 1 and its performance was examined. Each liquid developer exhibits the same performance as in Example 1,
The redispersibility, fixing property, resist property, and printing durability were good.

Examples 16 to 25 Similar to Example 2 except that the latex particles D-23 of the liquid developer of the present invention were replaced with the latex particles shown in Table K below. Then, each liquid developer was prepared.

[0203]

[Table 22]

Each of the obtained liquid developers was used in an electrophotographic plate making system in the same manner as in Example 2 and its performance was examined. Each liquid developer shows the same performance as in Example 2,
The redispersibility, resist property, and printing durability were good.

Example 26 Preparation of Latex Particles A mixture of 100 g of the white resin dispersion obtained in Example 30 and 1.5 g of Sumikaron black was heated to a temperature of 100 ° C. and heated and stirred for 4 hours. After cooling to room temperature, a 200-mesh nylon cloth was passed through to remove the residual dye, thereby obtaining a black resin dispersion having an average particle size of 0.21 μm. A liquid developer was prepared by diluting 30 g of the black resin dispersion and 0.05 g of zirconium naphthenate to 1 liter of Shellzol 71. When this was developed by the same apparatus as in Example 1, no toner adhesion stains occurred on the apparatus even after development of 2000 sheets. Further, in the same manner as in Example 1, a plate-making and etching treatment was carried out to print an offset master original plate,
The printed matter after 3,000 sheets had a clear image quality.

Example 27 Preparation of Latex Particles A mixture of 100 g of the white resin dispersion obtained in Production Example 28 and 3 g of Victoria Blue B was heated to a temperature of 70 ° C. to 80 ° C. and stirred for 6 hours. After cooling to room temperature, a 200-mesh nylon cloth was passed through to remove the residual dye, thereby obtaining a blue resin dispersion having an average particle size of 0.25 μm. A liquid developer was prepared by diluting 32 g of the blue resin dispersion and 0.05 of zirconium naphthenate to 1 liter of Isopar H. When this was developed by the same apparatus as in Example 3, no toner adhesion stain was found on the apparatus even after development of 2000 sheets. Further, the image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after printing 3,000 sheets was also very clear.

[0207]

According to the present invention, a liquid developer having excellent dispersion stability, redispersibility and fixability can be obtained. In particular, as a developer for an electrophotographic plate making system, the resist property of the toner image portion is excellent, and thus the printing durability of the obtained master plate for offset master is remarkably improved.

Claims (3)

[Claims] 1. A liquid developer for electrostatic photography comprising at least resin particles 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, wherein the dispersed resin particles are At least one monofunctional monomer (A), which is soluble in an aqueous solvent but is insoluble by polymerization, contains a specific substituent represented by the following general formula (I), At least one monomer (C) copolymerizable with the polymer (A), and a polyfunctional monomer (D) having at least two polymerizable functional groups copolymerizable with the monomer (A). ), And a block A containing at least a polymer component represented by the following general formula (II), a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, a phosphono group, and -P (= O). (OH) R ¹ group [R ¹ is -R ² group or -OR ² The indicated, R ² represents a hydrocarbon group], -C
ON (R ³⁾ R ^{4 _{group, -SO 2 N (R 3)}} R 4 group [R ³
And R ⁴ each independently represent a hydrogen atom or a hydrocarbon group] and a cyclic acid anhydride-containing group, and / or a polymer component containing at least one polar group and / or the monofunctional monomer. And a block B composed of a polymer component corresponding to (A) and having a weight average molecular weight of 1 × 10 ^{4 to} 5 ×.
Copolymer resin particles obtained by polymerizing a solution containing 10 ⁵ and at least one dispersion-stabilizing resin [P] made of an AB block copolymer soluble in the non-aqueous solvent. A liquid developer for electrostatic photography, characterized in that [Chemical 1] In the general formula (I), E ¹ represents an aliphatic group having 8 or more carbon atoms, or a substituent selected from the substituents represented by the following general formula (III). [Chemical 2] In formula (III), R ₂₁ represents a hydrogen atom or an aliphatic group having 1 to 18 carbon atoms. B ₁ and B ₂ may be the same as or different from each other, and each is —O—, —S—, —CO—, —CO ₂
-, - OCO -, - SO 2 -, - N (R 22) -, - CO
N (R ₂₂ )-, -N (R ₂₂ ) CO-, -N (R ₂₂ ) SO
_{2 -, - SO 2 N (} R 22) -, - NHCO 2 - or -
Represents NHCONH- (where R ₂₂ has the same meaning as R ₂₁ above). A ₁ and A ₂ may be the same as or different from each other, and each may be substituted, or represent a hydrocarbon group having 1 to 18 carbon atoms which may have the following Chemical Formula 3 interposed in the bond of the main chain. [Chemical 3] In the chemical formula 3, B ₃ and B ₄ may be the same or different from each other, and have the same contents as the above B ₁ and B _2, and A ₄ represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. R ₂₃ has the same content as R ₂₁ above. m, n and p may be the same or different and each represents an integer of 0 to 4. However, m, n, and p do not become 0 at the same time. formula
(I) in, U ¹ is -COO -, - CONH -, - CON
(E ² )-[wherein E ² is an aliphatic group or the above general formula
Represents a substituent represented by (III)], -OCO-, -C
_{ONHCOO -, - CH 2 COO -} , - (CH 2) s O
CO- [wherein s represents an integer of 1 to 4], it represents -COO- -O- or -C ₆ H _4. a ¹ and a ^2, which may be the same or different, (the E ³ here represents an aliphatic group) each represents a hydrogen atom, an alkyl group, -COO-E ³ or -CH ₂ COO-E ³ represent. [Chemical 4] In the general formula (II), X ¹ is -COO-, -OCO-,-.
_{(CH 2) y -COO -,} - (CH 2) y -OCO-,
Or represents -O- (where y represents an integer of 1 to 3). Y ¹ represents an aliphatic group having 10 or more carbon atoms. b ¹
And b ² may be the same as or different from each other, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group or —COO.
-Z ¹ group, or -COO-Z ¹ group via a hydrocarbon group (wherein Z ¹ represents a hydrogen atom or an optionally substituted hydrocarbon group). 2. The dispersion stabilizing resin [P] has the same specific content as that contained in the block B at one end of the polymer main chain of the block B opposite to the end adjacent to the block A. The liquid developer for electrostatic photography according to claim 1, which is a resin containing at least one kind of polar group selected from polar groups. 3. The dispersion stabilizing resin [P] is copolymerized with the monomer (A) at one end of the polymer main chain of the block B opposite to the end adjacent to the block A. A liquid developer for electrostatic photography according to claim 1, which is a resin containing a polymerizable functional group capable of being treated.