JP2916553B2 - Liquid developer for electrostatic photography - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention is an electric resistance 10 ⁹ [Omega] cm or more, and relates to an electrostatic photographic liquid developer formed by dispersing at least resin dielectric constant of 3.5 or less of the carrier liquid, especially redispersion And a liquid developer having excellent resist properties.

[0002]

2. Description of the Related Art A general liquid developer for electrophotography uses 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 as a petroleum-based liquid developer. Dispersed in a liquid with high insulation and low dielectric constant such as aliphatic hydrocarbons, and added with a polarity controlling agent such as a polymer containing metal soap, lecithin, linseed oil, higher fatty acid, and vinylpyrrolidone. .

[0003] 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. It is important that the particles do not agglomerate or precipitate, and if they are not satisfied, it will lead to failure of the developing machine such as poor reproducibility of the image area, contamination of the non-image area, or clogging of the liquid feed pump of the developing device. Would.

[0004] As these improvements, non-aqueous dispersion polymerization methods for obtaining insoluble latex particles having a fine particle size and good monodispersity have been proposed, and various studies have been made.
For example, U.S. Patent Nos. 3,990,980 and 4,61.
8,557, JP-A-1-257969, 2-74
No. 956, No. 1-282566, No. 2-173667
In 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-1-237668 and 2-1682
No. 76, No. 2-13973, No. 2-81054 and the like describe a method of modifying the surface of latex particles by coexisting another compound having a physicochemical interaction with a monomer to be insolubilized, It is disclosed that the degree of dispersion, particle size, redispersibility, and storage stability of the particles can be improved.

[0005]

On the other hand, in recent years, the practical use or development of a direct lithographic printing system to which the electrophotographic technique is applied has been actively performed. These systems are
After a toner image portion is formed on the surface of an electrophotographic photosensitive material by electrophotography, the non-image portion is converted into hydrophilic by processing, thereby obtaining a lithographic printing original plate. As a method for hydrophilizing the non-image portion, a method in which the portion is eluted with a processing solution 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 used. The main method is a method of modifying lipophilicity to hydrophilicity.

In recent years, the latter method has been disclosed in Japanese Patent Application Laid-Open Nos. 62-21669 and 1-19 as improvements of conventionally known methods for desensitizing photoconductive zinc oxide in a photosensitive layer.
No. 1157, No. 2-15277, etc., by converting the binder resin used for the photosensitive layer to hydrophilic by treatment,
It is disclosed that improvement in hydrophilicity is achieved.
In these systems, in the process of making the toner hydrophilic, it is important to maintain the image portion of the toner image portion without any change with respect to the processing liquid (hereinafter, referred to as resist properties for the processing liquid).

When a known liquid developer containing insoluble resin particles having good redispersibility is used for such an electrophotographic plate making system, if the non-image area is sufficiently hydrophilized, the resist property of the toner image area becomes insufficient. However, there was a case where the image part was missing. In particular, this problem is remarkable in a place where the area of the toner image portion such as a thin line, a character, or a halftone dot portion is small, and the printed matter is deteriorated. Insoluble latex particles (for example, styrene-based latex) having high durability with respect to the processing solution have sufficient resist properties, but have poor charge stability and re-dispersibility as toner particles. Fixing of toner particles is inferior and sufficient fixing requires a long time with high heat and a long fixing time.

The present invention solves the above-mentioned problems of the conventional liquid developer. The purpose of the present invention is
An object of the present invention is to provide a liquid developer excellent in dispersion stability, redispersibility, fixing property, and resist property of a hydrophilic treatment liquid in an electrophotographic plate making system. Another object of the present invention is to provide a liquid developer capable of preparing 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 offset printing master having excellent printing ink oil sensitivity and printing durability by electrophotography. Still another object of the present invention is to provide a liquid developer capable of preparing an original plate for offset printing using a recording method of various recording processes such as ink jet recording, cathode ray tube recording and pressure change or electrostatic change. It is.

[0009]

The above objects of the present invention are:
In a liquid developer for electrophotography comprising at least resin particles dispersed in a non-aqueous solvent having an electric resistance of not less than 10 ⁹ Ωcm and a dielectric constant of not more than 3.5, the dispersed resin particles are as follows:
At least one monofunctional monomer (A) which is soluble in the non-aqueous solvent but insoluble by polymerization;
At least one kind of a monomer (C) represented by the following general formula (I) and having a specific substituent and copolymerizable with the monomer (A); A) a polymer containing at least one polyfunctional monomer (D) having at least two polymerizable functional groups copolymerizable with (d), and (4) a repeating unit represented by the following general formula (II): Has a weight average molecular weight (hereinafter abbreviated as Mw) of 2 × 10 ^{4 to} 5 × 10 ^5.
And at one end of the polymer main chain, -PO ₃ H
_{2, -SO 3 H, -COOH,} -P (= O) (OH) R
¹ [wherein R ¹ represents a hydrocarbon group or -OR ² (R ² represents a hydrocarbon group)], -OH, a formyl group,
—CONR ³ R ⁴ , —SO ₂ NR ³ R ⁴ [where R ³
And R ⁴ each independently represent a hydrogen atom or a hydrocarbon group], a cyclic acid anhydride-containing group, and at least one polar group selected from amino groups, or copolymerized with the monomer (A). Polymer resin particles obtained by polymerizing a solution containing at least one kind of a dispersion stabilizing resin [P] soluble in the non-aqueous solvent, which is obtained by bonding the resulting polymerizable functional groups. This is achieved by the use of an electrostatographic liquid developer.

[0010]

Embedded image

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]

Embedded image

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 from each other, and are each -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) -, -
NHCO ₂ — or —NHCONH— (where R
₂₂ shows the same contents as the R _21). A ₁ and A ₂ are
Represents a hydrocarbon group having 1 to 18 carbon atoms which may be the same or different from each other, may be substituted each, or may have the following formula 7 intervening in the bond of the main chain.

[0014]

Embedded image

In the chemical formula 7, B ₃ and B ₄ may be the same or different from each other, and have the same content as B ₁ and B ₂ described above;
A ₄ represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and R ₂₃ has the same contents as R ₂₁ . m, n and p may be the same or different and represent an integer of 0 to 4, respectively. However, m, n and p do not become 0 at the same time. In the formula (I), U ¹ represents —COO—, —CONH—,
-CON (E ² )-[where E ² represents an aliphatic group or a substituent represented by the above 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 (where E ³ represents an aliphatic group).

[0016]

Embedded image

In the formula (II), X ¹ is -COO-, -OCO
_{-, - CH 2 OCO -,} - CH 2 COO -, - O-, or -SO ₂ - represent. Y ¹ represents an aliphatic group having 6 to 32 carbon atoms. b ¹ and b ² may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, —COO—Z ¹ , or a carbon atom having 1 carbon atom.
-COO-Z ¹ through a hydrocarbon group of ８8 (where Z ¹
Represents a hydrocarbon group having 1 to 22 carbon atoms).

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

The non-aqueous dispersion resin particles (hereinafter sometimes referred to as latex particles), which are the most important constituents in the present invention, are formed of a specific polar group or a polymer at one end of the polymer main chain in a non-aqueous solvent. In the presence of a dispersion-stabilizing resin [P] containing a functional functional group and soluble in the non-aqueous solvent, at least one monofunctional monomer (A) and a monomer containing a specific substituent (C ) And at least one of the polyfunctional monomers (D) are polymerized and granulated.

Here, as the non-aqueous solvent, basically,
Any material can be used as long as it is miscible with the carrier liquid of the liquid developer for electrostatography. 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. Hydrogen and halogen-substituted products thereof are exemplified. For example, hexane,
Octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, isoper E,
Isopar G, Isopar H, Isopar L, Shellsol 70, Shellsol 71, Amsco OMS, Amsco 460 solvent and the like are used alone or in combination.

Solvents that can be used by mixing with these organic solvents include alcohols (eg, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, fluorinated alcohol, etc.) and ketones (eg, acetone, methyl ethyl ketone, 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, Carbon tetrachloride, dichloroethane, methyl chloroform, etc.).

It is desirable that the non-aqueous solvent used by mixing these is distilled off under heating or under reduced pressure after the polymerization granulation. 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 Hydrocarbons and the like.

The monofunctional monomer (A) in the present invention comprises
Any monofunctional monomer that is soluble in a nonaqueous solvent but insolubilized by polymerization may be used. Specifically, for example, a monomer represented by the following general formula (IV) can be mentioned.

[0024]

Embedded image

In the formula (IV), T ¹ is -COO-, -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, a phenylene group is referred to as “—Ph—”; phenylene groups are 1,2-, 1,3- And 1,4
-Phenylene groups. ). Where W ¹
Is a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (e.g., methyl, ethyl, propyl, butyl, 2-chloroethyl, 2-bromoethyl, 2-cyanoethyl, 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, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group, a 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-carboxyamidoethyl group, 3
-Sulfamidopropyl 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 formula (II).

Specific monofunctional monomers (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, C1-C4 alkyl esters or amides of unsaturated carboxylic acids such as maleic acid (for example, methyl, ethyl, propyl, butyl, 2-chloroethyl, 2-chloroethyl, 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-
Styrene derivatives (eg, styrene, vinyltoluene, α-methylstyrene,
Vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N, N
-Dimethylaminomethylstyrene, vinylbenzenecarboxamide, vinylbenzenesulfonamide, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid; cyclic acid anhydrides of maleic acid and itaconic acid; Acrylonitrile; Methacrylonitrile; Heterocyclic compound containing a polymerizable double bond group (specifically, for example, “Polymer Data Handbook -Basic Part-”, edited by The Society of Polymer Science, pp. 175-184, Baifukan (1986) ), For example, N-vinylpyridine, N
-Vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.)
And the like. Two or more monomers (A) may be used in combination.

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

[0030]

Embedded image

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).

[0032]

Embedded image

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 from each other, and are each -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) -, -
NHCO ₂ — or —NHCONH— (where R
₂₂ shows the same contents as the R _21). A ₁ and A ₂ are
And represents a hydrocarbon group having 1 to 18 carbon atoms which may be the same or different from each other, may be substituted, or may have the following formula 12 intervening in the bonding of the main chain.

[0034]

Embedded image

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

The case where E ¹ represents an aliphatic group having 8 or more carbon atoms in the monomer (C) represented by the general formula (I) will be described in detail. In the general formula (I), preferably,
E ¹ represents an alkyl group having 10 or more carbon atoms which may be substituted or an alkenyl group having 10 or more carbon atoms. U ¹ is -COO -, - CONH -, - CON (E 2) - [where, E ² is preferably, for example an alkyl group as the aliphatic group (the aliphatic group of 1 to 32 carbon atoms, alkenyl or aralkyl group showing a shown) or the like], -OCO -, - CH ₂ O
Represents CO- or -O-. a ¹ and a ² may be the same or different and are 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 formula (I), U ¹ is-
Represents COO—, —CONH—, or —CON (E ² ) —, a ¹ and a ² may be the same or different and represent a hydrogen atom or a methyl group, and E ¹ has the same contents as described above. Express.

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

The case where E ¹ in the monomer (C) represented by the formula (I) represents a substituent represented by the formula (III) will be described in detail. More specific examples of A ₁ and A ₂ include those represented by —C (R ₂₄ )
(R ₂₅₎ - [R _24, R ₂₅ represents a hydrogen atom, an alkyl group, a halogen atom, etc.], - (CH = CH) - , cyclohexylene group [hereinafter, "-C ₆ H cyclohexylene
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 consists of any combination of groups.

In the general formula (I), in the bonding group: -U ^1- (A ₁ -B ₁ ) _m- (A ₂ -B ₂ ) _n -R ₂₁ , U ¹ to R ₂₁ (that is, _{^{1, A 1, B 1,}} A
₂ , B ₂ , and R ₂₁ ) preferably have a total number of atoms of 8 or more. Where U ¹
Represents —CON (E ² ) —, and E ² represents the general formula
A substituent represented by (III) [that is,-(A ₁ -B ₁ ) _m-
When representing the _{(A 2 -B 2) n -R} 21 ], linked backbone consists of E ² are also included in the connecting backbone. Furthermore,
-A _3- (A ₄ -B ₄ ) _p -R in the case where A ₁ and A ₂ are a hydrocarbon group which makes the above-mentioned formula 12 intervene in the bond of the main chain.
₂₃ is also included in the connecting main chain. As the number of atoms in 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 in the number of atoms, and carbon atoms constituting the connecting main chain are not included. Atoms, ether-type oxygen atoms, and nitrogen atoms are included in the number of atoms. Therefore, -COO- and -CONH- are counted as 2 atoms. Similarly, when R ₂₁ represents —C ₉ H ₁₉ , the number of hydrogen atoms is not included, and the number of carbon atoms is included.
Therefore, in this case, it is counted as 9 atoms. In the monomer (C) represented by the general formula (I) as described above,
^{When 1} represents the 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 exemplified.

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

[0045]

Embedded image

Next, a polymerizable functional group capable of copolymerizing with the monomer (A), which is used together with the monofunctional monomer (A) and the monomer (C) having a specific substituent, is used. (D) having at least one monomer (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 can be copolymerized with the monomer (A). Specifically, the polymerizable functional group represented by the following general formula (V) The functional groups shown are mentioned.

[0047]

Embedded image

[0048] 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).

The polyfunctional monomer (D) may be a monomer having two or more of the same or different polymerizable functional groups, and the monomer (A) By co-polymerizing, a polymer insoluble in a non-aqueous solvent is formed.

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 alcohols (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 and the like, or polyhydroxyphenol (for example, hydroquinone, resorcinol, catechol and the like) 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) Vinyl esters, allyl esters, vinylamides or allylamides of itaconic acid; polyamines (eg, ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, etc.) and vinyl Carboxylic acids having (e.g.,
Condensates with methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.).

As the monomer having a different polymerizable functional group, for example, a carboxylic acid having a vinyl group [eg,
Methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloyl propionic acid, acryloyl propionic acid, itaconiloyl acetic acid, itaconiloyl propionic acid, a reactant of a carboxylic anhydride with an alcohol or an amine (for example, allyloxycarbonylpropionic acid, Ester derivatives or amide derivatives containing a vinyl group such as oxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropionic acid, etc. (for example, vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate) , Allyl acrylate, allyl itaconate, vinyl methacryloyl acetate, vinyl methacryloyl propionate,
Allyl methacryloylpropionate, vinyloxycarbonylmethyl methacrylate, vinyloxycarbonylmethyloxycarbonylethylene acrylate, N-allylacrylamide, N-allylmethacrylamide, N-allylitaconamide, allylamide methacryloylpropionate); or And amino alcohols (eg, aminoethanol, 1-aminopropanol, 1-aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and carboxylic acids containing vinyl groups.

The dispersing resin of the present invention comprises at least one of each of the monomers (A), (C) and (D). If the obtained resin is insoluble in the non-aqueous solvent, a desired dispersed resin can be obtained. More specifically, the monomer (A) to be insolubilized
With the monomer (C) represented by the general formula (I) in 0.1.
It is preferably used in an amount of 1 to 20% by weight, more preferably 0.3 to 8% by weight. The monomer (D) having two or more polymerizable functional groups used in the present invention accounts for 0.01 mol% or more and 20 mol% or less, preferably 0.1 mol% or less of all monomers.
It is used in an amount of from 05 mol% to 10 mol% and polymerizes to form a resin. The molecular weight of the dispersion resin of the present invention is preferably 1 × 10 ³ to 1 × 10 ⁶ , more preferably 1 × 10 ⁴ to 1 × 10 ⁶ .

The dispersion stabilizing resin [P] of the present invention used for preparing a stable resin dispersion of the solvent-insoluble polymer produced by polymerizing the monomer in a non-aqueous solvent is as follows: A polymer containing a repeating unit represented by the general formula (II), whose Mw is 2 × 10 ^{4 to} 5 × 10 ⁵ , and -PO ₃ H ₂ ,- SO
₃ H, -COOH, -P (= O) (OH) R ¹ [where R ¹ represents a hydrocarbon group or -OR ² (R ² represents a hydrocarbon group)], -OH, formyl group , -CON
R ³ R ⁴ , —SO ₂ NR ³ R ⁴ [where R ³ and R ⁴
Each independently represents a hydrogen atom or a hydrocarbon group],
A resin which is at least one polar group selected from a cyclic acid anhydride-containing group and an amino group or a polymerizable functional group capable of copolymerizing with the monomer (A), and which is soluble in the non-aqueous solvent. is there.

[0054]

Embedded image

In the formula (II), X ¹ represents —COO—, —OCO
_{-, - CH 2 OCO -,} - CH 2 COO -, - O-, or -SO ₂ - represent. Y ¹ represents an aliphatic group having 6 to 32 carbon atoms. b ¹ and b ² may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, —COO—Z ¹ , or a carbon atom having 1 carbon atom.
-COO-Z ¹ through a hydrocarbon group of ８8 (where Z ¹
Represents a hydrocarbon group having 1 to 22 carbon atoms).

Dispersion stabilizing resin [P] used in the present invention
Is soluble in an organic solvent, and more specifically, it is sufficient that at least 5 parts by weight or more of the resin for dispersion stabilization is dissolved at 25 ° C. with respect to 100 parts by weight of a toluene solvent. Mw of the dispersion stabilizing resin [P] of the present invention is 2 ×
10 ^{4 to} 5 × 10 ⁵ , preferably 2.5 × 10 ⁴
１1 × 10 ⁵ .

Hereinafter, the dispersion stabilizing resin [P] of the present invention will be described in more detail. In the repeating unit represented by the general formula (II), the aliphatic group and the hydrocarbon group may be substituted. In the general formula (II), X ¹ is preferably -COO-, -OCO-, -CH ₂ OCO-, -CH
₂ represents COO- or -O-, more preferably -CO
O -, - represents a CH ₂ COO- or -O-.

Y ¹ preferably represents an optionally substituted alkyl, alkenyl or aralkyl group having 8 to 22 carbon atoms. Examples of the substituent include a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and the like), -O
^{-Z 2, -COO-Z 2,} -OCO-Z 2 ( wherein, Z
^{And 2} represents an alkyl group having 6 to 22 carbon atoms, such as hexyl, octyl, decyl, dodecyl, hexadecyl, and octadecyl. More preferably, Y ¹ represents an alkyl group or an alkenyl group having 8 to 22 carbon atoms. For example, an octyl group,
Decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosanyl group,
A decenyl group, a dodecenyl group, a tetradecenyl group, a hexadecenyl group, an octadecenyl group, and the like.

B ¹ and b ² may be the same or different from each other, and are preferably a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, and a C 1 -C 1 atom. 3 alkyl group, -COO-Z ³ or -CH ₂ COO-Z ³ (wherein, Z ³ is from 1 to 22 carbon atoms
Represents, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a hexadecyl group, an octadecyl group, a docosanyl group, and a pentenyl group A hexenyl group, a heptenyl group, an octenyl group, a decenyl group, a dodecenyl group, a tetradecenyl group, a hexadecenyl group, an octadecenyl group, and the like.These aliphatic groups may have the same substituents as those represented by Y ¹ above. Good). More preferably, b ¹ and b
² is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (e.g., methyl group, ethyl group, propyl group, etc.), -COO
-Z ⁴ or -CH ₂ COO-Z ⁴ (where, Z ⁴ represents an alkyl or alkenyl group having 1 to 12 carbon atoms, e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl Group, decyl group, dodecyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group,
A decenyl group, and the like, and these alkyl groups and alkenyl groups may have the same substituents as those described above for Y ¹ ).

In the dispersion stabilizing resin [P] of the present invention, the polymer component is a homopolymer component or a copolymer component selected from the repeating units represented by the general formula (II),
Or a copolymer component obtained by copolymerizing a monomer corresponding to the repeating unit represented by the general formula (II) and another monomer copolymerizable with the monomer, Further, it is a polymer containing the specific polar group or polymerizable functional group at one end of the polymer main chain. Other monomers that can be copolymerized may be any as long as they contain a polymerizable double bond group. For example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and itaconic acid; Ester derivatives or amide derivatives of carboxylic acids; vinyl esters or allyl esters of carboxylic acids; styrenes; methacrylonitrile; acrylonitrile; heterocyclic compounds containing a polymerizable double bond group. More specifically, a compound having the same content as the above-mentioned monomer (A) to be insolubilized may be used.

In the polymer component of the dispersion stabilizing resin [P], the content of the repeating unit represented by the general formula (II) is at least 30% by weight, preferably at least 50% by weight, based on all the components of the polymer. , More preferably 70% by weight or more. The upper limit is 100% by weight. Further, it is preferable that the polymer main chain of the dispersion stabilizing resin [P] does not contain the specific polar group or polymerizable functional group.

The dispersion stabilizing resin [P] used in the present invention
Is a resin having a specific polar group at one end of the polymer main chain (hereinafter referred to as a dispersion stabilizing resin [PA] or a resin [PA]), and the monomer at one end of the polymer main chain. Resins having a polymerizable functional group copolymerizable with (A) [hereinafter referred to as dispersion stabilizing resin [PB] or resin [PB]].

The dispersion stabilizing resin [PA] having a specific polar group at one end of the polymer main chain will be described below. Particular polar _{group, -PO 3 H 2, -SO 3} H, -C
OOH, -P (= O) ( OH) R 1 [R ¹ represents a hydrocarbon group or -OR ² (R ² represents a hydrocarbon group)], -OH, formyl group, -CONR ³ R ^4, -SO
₂ NR ³ R ⁴ [R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group], a cyclic acid anhydride-containing group, and at least one polar group selected from an amino group.

In the polar group represented by -P (= O) (OH) R ¹ , the hydrocarbon group represented by R ¹ or R ² is preferably a hydrocarbon group having 1 to 10 carbon atoms.
More preferably, an aliphatic group having 1 to 8 carbon atoms which may be substituted (for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, butenyl, pentenyl, hexenyl, 2-chloroethyl) A 2-cyanoethyl group, a cyclopentyl group, a cyclohexyl group, a benzyl group, a phenethyl group, a chlorobenzyl group, a bromobenzyl group, etc., or an aromatic group which may be substituted (for example, a phenyl group, a tolyl group, a xylyl group, Mesityl group, chlorophenyl group, bromophenyl group, methoxyphenyl group,
A cyanophenyl group).

The above -CONR ³ R ⁴ and -SO ₂ NR
^{In the} polar group represented by ³ R ⁴ , R ³ and R ⁴ each independently represent 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 ¹ and R ² .

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

In the polar group of the present invention, the amino group is represented by -N
Represents H ₂ , —NHR ⁵ or —NR ⁵ R ⁶ . R ⁵ , R ⁶
Represents a hydrocarbon group having 1 to 8 carbon atoms, and preferably represents a hydrocarbon group having 1 to 7 carbon atoms.
Those having the same contents as the hydrocarbon group represented by ¹ can be mentioned.

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, or may be bonded via a linking group. Examples of the linking group for linking the main chain component and the specific polar group-containing component include a carbon-carbon bond (single bond or double bond) and a carbon-hetero atom bond (hetero atoms include, for example, an oxygen atom and a sulfur atom. , Nitrogen atom, silicon atom, etc.),
It is composed of any combination of heteroatom-heteroatom bond atomic groups. More specific linking groups include
-CR ⁷ R ⁸ - [R ^7, R ⁸ are each independently a hydrogen atom, a halogen atom (fluorine atom, a chlorine atom, a bromine atom), a cyano group, a hydroxyl group, an alkyl group (a methyl group, an ethyl group, Propyl, etc.), and-(CH =
_{CH) -, - C 6 H} 10 - ( cyclohexylene group), - P
h -, - O -, - S -, - CO -, - NR 9 -, - CO
_{O -, - SO 2 -,} - CONR 9 -, - SO 2 NR
^{9 -, - NHCOO -, -} NHCONH -, - Si R 9
R ^10- wherein R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a hydrocarbon group having the same content as R ¹ in the polar group, etc. A linking group or a linking group constituted by a combination of two or more atomic groups is exemplified.

The dispersion stabilizing resin polymer [PA] of the present invention comprising a specific polar group bonded only to one end of the polymer main chain.
Are a method of reacting various reagents with the terminal of a living polymer obtained by a conventionally known anionic or cationic polymerization (method by an ionic polymerization method), a polymerization initiator containing a specific polar group in a molecule, and / or a chain. A method of radical polymerization using a transfer agent (a method by a radical polymerization method), or a polymer containing a reactive group at a terminal obtained by an ionic polymerization method or a radical polymerization method as described above is specified by the polymer reaction. Can be easily produced by a synthesis method such as a method of converting to a polar group. Specifically, P.S. Dreyfuss &
R. P. Quirk, Encycl. Polym. Sc
i. Eng. , 7 , 551 (1987), Yoshiki Chujo, Yuya Yamashita, "Dyes and Pharmaceuticals" 30 , 232 (1985), Akira Ueda, Susumu Nagai, "Science and Industry" 60 , 57 (1986), and references cited therein. Can be produced.

Examples of the above-mentioned specific polar group or a chain transfer agent having a substituent capable of deriving to the polar group include, for example, the reactive group or a mercapto compound having a substituent capable of being derivable to the reactive group (for example, Thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid,
3-mercaptopropionic acid, 3-mercaptobutyric acid, N
-(2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- ( 3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4
-Mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1
-Mercapto-2-propanol, 3-mercapto-2
-Butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol and the like, or an iodoalkyl compound containing the reactive group or a substituent capable of being induced to the reactive group (for example, , Iodoacetic acid, iodopropionic acid,
2-iodoethanol, 2-iodoethanesulfonic acid,
3-iodopropanesulfonic acid and the like). Preferably, a mercapto compound is used.

Examples of the specific polar group or a polymerization initiator containing a substituent which can be derived to the polar group include, for example, 4,
4'-azobis (4-cyanovaleric acid), 4,4'-azobis (4-cyanovaleric chloride), 2,2'-azobis (2-cyanopropanol), 2,2'-azobis (2-cyanovaleric acid) Pentanol), 2,2′-azobis [2
-(5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane], 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2- Hydroxyethyl] propioamide｝, 2,
2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propioamide}, 2,2 '
-Azobis [2-methyl-N- (2-hydroxyethyl) propioamide], 2,2'-azobis (2-amidinopropane), 2,2'-azobis [2-methyl-N
-(2-hydroxyethyl) -propioamide], 2,
2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane], 2,2'-azobis [2-
(4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane], 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidine-2
-Yl) propane], 2,2'-azobis {2- [1-
(2-hydroxyethyl) -2-imidazolin-2-yl] propane {, 2,2'-azobis [N- (2-hydroxyethyl) -2-methyl-propionamidine],
2,2'-azobis [N- (4-aminophenyl) -2
-Methylpropionamidine].

The amount of the chain transfer agent or the polymerization initiator used is 0.1% to 100 parts by weight of the total monomers.
10 to 10 parts by weight, preferably 0.5 to 5 parts by weight.

Next, in the dispersion stabilizing resin [P] used in the present invention, a polymerizable functional group copolymerizable with the monofunctional monomer (A) is provided at one end of the polymer main chain. The dispersion stabilizing resin [PB] will be described.

The polymerizable functional group bonded to one end of the polymer main chain of the dispersion stabilizing resin [PB] includes, for example, the general formula described as the polymerizable functional group in the polyfunctional monomer (D). Examples are the same as the functional groups represented by (V). Specific examples of the polymerizable functional group include the following. _{CH 2 = CH-COO-, CH} 2 = C (CH 3) -CO
_{O-, CH 3 -CH = CH-} COO-, CH 2 = C (C
_{H 2 COOCH 3) -COO-, CH} 2 = CH-CON
_{H-, CH 2 = C (CH} 3) -CONH-, CH 3 -C
_{H = CH-CONH-, CH 2} = CH-OCO-, CH
_{2 = CH-CH 2 -OCO-,} CH 2 = C (CH 3) -
_{OCO-, CH 2 = CH-Ph-} , CH 2 = CH-CH
_{2 -NHCO-, CH 2 = CH-} SO 2 -, CH 2 = C
_{H-CO-, CH 2 = CH} -O-, CH 2 = CH-S
—, CH ₂ ＣＨCH—, CH ₂ ＣＨCH—CH ₂ — and the like. or,
The polymerizable functional group may be directly bonded to one end of the polymer main chain, 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 [PB] of the present invention can be prepared by reacting a terminal containing a living polymer obtained by conventionally known anionic or cationic polymerization with a reagent containing various polymerizable double bond groups, or A specific reactive group (for example, -O
_{H, -COOH, -SO 3 H,} -SH, -NH 2, -P
After reacting a reagent containing O ₃ H ₂ , —NCO, —NCS, an epoxy group represented by the following formula (21), —COCl, —SO ₂ Cl, etc.), a polymerizable double bond group is formed by a polymer reaction. After the method of introducing (method by ionic polymerization method) or radical polymerization using a polymerization initiator and / or a chain transfer agent containing the specific reactive group in the molecule,
The polymer can be easily produced by a synthesis method such as a method of introducing a polymerizable double bond group by conducting a polymer reaction using a specific reactive group bonded only to one end of the polymer main chain.

[0076]

Embedded image

More specifically, P.S. Dreyfuss &
R. P. Quirk, Encycl. Poly. Sc
i. Eng. , 7 , 551 (1987), Yoshiki Chujo, Yuya Yamashita, "Dyes and Chemicals", 30 , 232 (1985), Akira Ueda, Susumu Nagai, "Chemistry and Industry" 60 , 57 (1986),
P. F. Rempp & E. Franta, Adva
nces in Polymer Science, 5
8 , 1 (1984), Koichi Ito "Polymer processing", 35 ,
262 (1986); Persec, Applie
d Polymer Science, 285 , 97
(1984), and a polymerizable double bond group can be introduced according to the method described in the literature and the like cited therein.

More specifically, a dispersion stabilizing resin [PA
The method of introducing a polymerizable double bond group by carrying out a polymer reaction using the specific polar group of the above [1] is preferable.

In order to produce the latex particles used in the present invention, generally, the dispersion stabilizing resin [P] as described above is used.
(At least one or both of resin [PA] and resin [PB]), monofunctional monomer (A), monomer (C) containing a specific substituent, and polyfunctional monomer ( D)
Heat polymerization may be performed in a non-aqueous solvent in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, and butyllithium. Specifically, the dispersion stabilizing resin [P], the monomer (A), the monomer (C) and the monomer (D)
A method of adding a polymerization initiator to a mixed solution containing
A method of dropping monomer (A), monomer (C) and monomer (D) together with a polymerization initiator into a solution in which dispersion stabilizing resin [P] is dissolved, dispersion stabilizing resin [P] In a solution containing the total amount and a part of the monomers (A), (C) and (D), the remaining monomer (A) and the monomer together with the polymerization initiator. (C) and a method of optionally adding the monomer (D), or a dispersion stabilizing resin [P], a monomer (A), a monomer (C) and a monomer ( D)
And a method of arbitrarily adding the mixed solution together with the polymerization initiator, and any method can be used for the production.

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 as the dispersion stabilizing resin [P] is used in an amount of 1 to 100 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the total monomers used above. The amount of the polymerization initiator is suitably from 0.1 to 5% by weight based on the total amount of the monomers. Further, 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 above-mentioned polar solvents such as alcohols, ketones, ethers and esters are used in combination in the non-aqueous solvent used in the reaction, or when the monomer (A) to be polymerized and granulated, When the unreacted product of the compound (C) or the monomer (D) remains, the solvent or the monomer (A) or the monomer (C)
It is preferable to remove the solvent by heating it to a temperature higher than the boiling point of the monomer (D) or distilling it off, or distilling it off under reduced pressure.

The non-aqueous latex particles produced as described above exist as fine particles having a uniform particle size distribution, and at the same time, exhibit extremely stable dispersibility. However, it has good dispersibility and does not show any aggregation or precipitation in the developing device. Further, when fixed by heating or the like, a strong film was formed, and excellent fixability was exhibited. Further, when the liquid developer of the present invention is used in a plate making system,
The toner image portion had excellent resist properties even after the non-image portion hydrophilizing step, and showed excellent original image reproducibility of the printed image portion.

The liquid developer of the present invention having the above effects is made possible by the insoluble latex particles provided by the present invention. The insoluble resin particles of the present invention are polymerized and granulated using the monomer (C) having a specific substituent and the dispersion stabilizing resin [P] of the present invention, whereby the particles are monodispersed and redispersed. Has improved. That is, the monomer (C) is copolymerized with the monomer (A) which is insolubilized during polymerization granulation, but the specific substituent portion contained in the monomer (C) is non-aqueous dispersion polymerized. Since the particles are formed by the, the affinity with the non-aqueous solvent is designed to be good, so that the solvation with the dispersion medium is better than that penetrating into the inside of the particle structure, It is presumed that the particles are oriented at the interface (surface) of the particle structure, and as a result, the affinity of the particle surface with the dispersion medium is improved, and the effect of preventing aggregation between the particles is significantly enhanced. At the same time, the dispersed resin particles of the present invention comprise the dispersion stabilizing resin [P].
Interacts with the insoluble resin particles and is adsorbed on the insoluble resin particles. Since the resin [P] adsorbed on the resin particles is soluble in the non-aqueous solvent, the resin [P] has a so-called steric repulsion effect which is known as stabilization of dispersion of the non-aqueous latex. At the same time, since the resin [P] is a soluble resin having an aliphatic group having 6 or more carbon atoms in its repeating unit, the affinity for the non-aqueous solvent is significantly improved, and the adsorbed resin [P] is It is presumed that the compound has a polar group or a polymerizable functional group and therefore exists near the particle interface, thereby improving the amphiphilic property near the particle interface. In particular, when a dispersion stabilizing resin [PA] containing a specific polar group at one end of the polymer main chain is used, the interaction with the insoluble resin particles is further improved,
It is considered that the effect of the dispersion stabilization described above is further improved by increasing the adsorptivity to the particles. Also,
When a dispersion stabilizing resin [PB] containing a polymerizable functional group at one end of the polymer main chain is used, the monomers (A), (C) and the monomers which are insolubilized during the dispersion polymerization reaction It copolymerizes with (D) and is more efficiently bonded to insoluble resin particles. By these, aggregation and precipitation of insoluble particles are suppressed,
It is considered that redispersibility is significantly improved.

On the other hand, the insoluble resin particles of the present invention are characterized in that the particles form a crosslinked structure by polymerization and granulation using a polyfunctional monomer (D). This allows
After forming an image as toner particles, even after going through a hydrophilization treatment step to make a printing original plate, the suitability of the processing liquid (resist property) is improved, and damage to the toner image area can be significantly reduced. Was. Further, in order to ease the fixing conditions, it is important for the apparatus to have a resin structure having a low glass transition point as the insoluble resin particles, and these resins having a low glass transition point include, for example, an ester structure, Since a polar structure such as an ether structure or an amide structure is contained, the compound is easily dissolved in a treatment liquid in the hydrophilic treatment step, and as a result, the resist property of the toner portion on the image portion is reduced. This undesirable phenomenon can be significantly suppressed by partially crosslinking the inside of the resin particles. The dispersed resin particles of the present invention bring about the effects of the present invention by these effects.

In the liquid developer of the present invention, a coloring agent 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 the coloring methods, there is a method of physically dispersing the dispersion resin in a dispersion resin using a pigment or a dye. I have. For example, magnetic iron oxide powder, powdered lead iodide, carbon black, nigrosine, alkali blue, Hansa Yellow, quinacridone red,
And phthalocyanine blue. As another method of coloring, there is a method of dyeing a dispersion resin with a preferable dye as described in JP-A-57-48738. Alternatively, another method is disclosed in
As disclosed in JP-A-54029, there is a method in which a dispersing resin and a dye are chemically bonded, or as described in JP-B-44-22955, etc. In addition, there is a method of using a monomer containing a dye in advance to obtain a dye-containing copolymer.

Various additives may be added to the liquid developer of the present invention, if desired, for the purpose of enhancing charging characteristics or improving image characteristics. For example, Yuji Harazaki, "Electrophotography", Vol. What is specifically described in No. 2, p. 44 is used. For example, a copolymer containing a metal salt of di-2-ethylhexyl sulfosuccinic acid, a metal salt of naphthenic acid, a metal salt of a higher fatty acid, lecithin, poly (vinylpyrrolidone), and a hemimaleamide component;
Examples include polyethers and waxes. But,
It is not limited to these.

The amounts of the main components of the liquid developer of the present invention will be described below. The toner particles mainly composed of a resin (and a coloring agent used as desired) are used in an amount of 0.5 parts by weight to 1000 parts by weight of the carrier liquid.
50 parts by weight are preferred. If the amount is less than 0.5 parts by weight, the image density becomes insufficient, and if it exceeds 50 parts by weight, fogging to a non-image portion is apt to occur. Further, the carrier liquid soluble resin for dispersion stabilization is also used as needed, and can be added in an amount of about 0.5 to 100 parts by weight based on 1000 parts by weight of the carrier liquid. The charge control agent as described above is a carrier liquid 100
0.001 part by weight to 1.0 part by weight based on 0 part by weight is preferred. If desired, various additives may be added. The upper limit of the total amount of these additives is regulated by the electric resistance of the developer. That is, if the electric resistance of the liquid developer from which the toner particles have been removed is lower than 10 ⁹ Ωcm, it becomes difficult to obtain a high-quality continuous tone image. Therefore, the amount of each additive is controlled within this limit. It is necessary.

[0088]

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

Production Example of Dispersion Stabilizing Resin [PA] 1: Resin [PA-1] Octadecyl methacrylate 100 g, toluene 150
g, and a mixed solution of 50 g of isopropanol was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. 2,2'-azobis ( 4- cyanovaleric acid ) (abbreviated as ACV) was 5.0
g was added and reacted for 8 hours. After cooling, the precipitate was reprecipitated in 2 liters of methanol, and the white powder was collected by filtration and dried to obtain a powder having a weight average molecular weight (Mw) of 26,000 in a yield of 85 g.

Production Example 2 of dispersion stabilizing resin [PA]: Resin [PA-2] Same as Production Example 1 of dispersion stabilizing resin [PA] except that a mixed solution of 100 g of dodecyl methacrylate, 150 g of toluene and 50 g of isopropanol was used. To carry out a polymerization reaction. After cooling, reprecipitate in 2 liters of methanol,
83 g of a colorless and transparent viscous substance was obtained. Mw was 27,000.

Production Example 3 of dispersion stabilizing resin [PA]: resin [PA-3] 100 g of octadecyl methacrylate and 30 of toluene
0 g of the mixed solution was stirred at a temperature of 70
Warmed to ° C. 6 g of 4,4'-azobis (4-cyanopentanol) was added and reacted for 8 hours. After cooling, the precipitate was reprecipitated in 2 liters of methanol to obtain 86 g of a white powder. Mw
Was 28,000.

Production Example 4 of dispersion stabilizing resin [PA]: resin [PA-4] 70 g of dodecyl methacrylate, 30 g of butyl methacrylate, 150 g of toluene and 50 g of isopropanol
Was heated to 70 ° C. while stirring under a nitrogen stream. A. C. V. Was added and reacted for 8 hours. Mw of the copolymer was 23,000.

Production Example 5 of Dispersion Stabilizing Resin [PA]: Resin [PA-5] A mixed solution of 98.5 g of tridecyl methacrylate, 1.5 g of thioglycolic acid and 200 g of toluene was heated to a temperature of 65 ° C.
Warmed to ° C. 1.0 g of 2,2'-azobis (isobutyronitrile) (abbreviated as AIBN) was added, and the mixture was stirred for 5 hours. I. B. N. Was added and stirred for 4 hours. Mw of the obtained polymer was 24,000.

Production Example 6 of Dispersion Stabilizing Resin [PA]: Resin [PA-6] A mixed solution of 98.0 g of octadecyl methacrylate, 2.0 g of 2-mercaptoethanesulfonic acid, 200 g of toluene and 100 g of methanol was placed in a nitrogen stream. Temperature 65 ° C
Was heated. A. I. B. N. Was added and reacted for 5 hours. I. B. N. 0.3 g
Allowed to react for hours. The reaction solution was reprecipitated in 2 liters of acetonitrile to obtain 88 g of a white powder. Mw is 25.0
00.

Production Example 7 of Dispersion Stabilizing Resin [PA]: Resin [PA-7] A mixed solution of 90 g of hexadecyl methacrylate, 8 g of 2-chloroethyl methacrylate, 2.0 g of thiomalic acid, 150 g of toluene and 50 g of isopropanol was heated to a temperature of 75. Warmed to ° C. 1.0 g of 1,1'-azobis (cyclohexane-1-carbonitrile) was added and reacted for 6 hours. Further , 0.4 g of the azobis compound was added and reacted for 6 hours. After cooling, the precipitate was reprecipitated in 2 liters of methanol to obtain 86 g of a colorless and transparent viscous substance. Mw was 23,000.

Production Example 8 of Dispersion Stabilizing Resin [PA]: Resin [PA-8] A mixed solution of 100 g of tetradecyl methacrylate, 100 g of tetrahydrofuran and 100 g of methanol was heated to 70 ° C. while stirring under a nitrogen stream. . 2,
5 g of 2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propioamide} was added and reacted for 8 hours. After cooling, the precipitate was reprecipitated in 2 liters of a mixed solution of methanol / water (7/3 volume ratio) to obtain 80 g of a colorless viscous substance. Mw was 28,000.

Production Example 9 of Dispersion Stabilizing Resin [PA]: Resin [PA-9] A mixed solution of 95 g of dodecyl methacrylate and 200 g of toluene was heated to 70 ° C. in a nitrogen stream. 4,4 '
5 g of -azobis (4-cyanopentanol) was added and reacted for 8 hours. Next, 1.0 g of N, N-dimethylaniline and 10 g of glutaconic anhydride were added to the reaction solution, and the mixture was stirred at a temperature of 90 ° C. for 12 hours. After cooling, the precipitate was reprecipitated in 2 liters of methanol to obtain 88 g of a pale yellow viscous substance. Mw is 2
It was 8,000.

Production Examples of Dispersion Stabilizing Resin [PA] 10-1
7: Resins [PA-10] to [PA-17] In Production Example 1 of dispersion stabilizing resin [PA], octadecyl methacrylate and A.I. C. V. In place of the above, the dispersion stabilizing resins [PA-10] to [PA-17] were respectively produced in place of the compounds shown in Table A below.

[0099]

[Table 1]

Production Example 1 of Dispersion Stabilizing Resin [PA]
To [PA-1] to [PA-1]
The repeating unit of the main chain and the terminal portion containing the polar group of the formula [-17] is shown below.

[0101]

Embedded image

[0102]

Embedded image

[0103]

Embedded image

[0104]

Embedded image

Production Example 1 of Dispersion Stabilizing Resin [PB] Resin [PB-1] Octadecyl methacrylate 100 g, toluene 150
g and a mixed solution of 50 g of isopropanol were heated to a temperature of 75 ° C. while stirring under a nitrogen stream. A. C. V.
Was added and reacted for 8 hours. After cooling, methanol 2
After reprecipitation in a liter, the white powder was collected by filtration and dried. 6. 50 g of the obtained white powder, glycidyl methacrylate
A mixture of 6 g, 0.5 g of t-butylhydroquinone, 0.5 g of N, N-dimethyldodecylamine and 100 g of toluene was heated to a temperature of 100 ° C. and stirred for 12 hours.
The reaction mixture was reprecipitated in 1 liter of methanol,
The pale yellow powder was collected by filtration and dried. The yield was 43 g and the Mw was 28,000.

Production Examples 2 to 9 of Dispersion Stabilizing Resin [PB]:
Resins [PB-2] to [PB-9] Except for using the monomers shown in Table B below in place of octadecyl methacrylate in Production Example 1 of dispersion stabilizing resin [PB], By operation, each dispersion stabilizing resin [PB-2] to [PB-9] was produced. The Mw of the obtained resin was in the range of 30,000 to 50,000.

[0107]

[Table 2]

Production Example 10 of Dispersion Stabilizing Resin [PB]: Resin [PB-10] Resin Stabilizing Resin [PB] was prepared in the same manner as in Production Example 1 except that a mixed solution of 100 g of dodecyl methacrylate, 150 g of toluene and 50 g of isopropanol was used. A polymerization reaction was performed in the same manner. After cooling, reprecipitate in 2 liters of methanol,
After obtaining a colorless transparent viscous substance by a decantation method, it was dried. 50 g of the obtained viscous material, 1.5 g of glycidyl acrylate, 1.0 g of 2,2'-methylenebis- (6-t-butyl-p-cresol), 0.5 g of N, N-dimethyldodecylamine and 100 g of toluene The mixture was warmed to a temperature of 100 ° C. and stirred for 12 hours. The reaction mixture was reprecipitated in 1 liter of methanol to obtain a pale yellow viscous substance by a decantation method, and then dried. Yield 39g
Mw was 30,000.

Production Example 11 of Dispersion Stabilizing Resin [PB]: Resin [PB-11] 100 g of octadecyl methacrylate and 30 parts of toluene
0 g of the mixed solution was heated to 70 ° C. while stirring under a nitrogen stream. 6 g of 4,4'-azobis (4-cyanopentanol) was added and reacted for 8 hours. Next, after cooling the reaction product, 6.2 g of methacrylic anhydride, 0.8 g of t-butylhydroquinone and 1 drop of concentrated sulfuric acid were added, and the mixture was heated at 30 ° C. for 1 hour.
The mixture was stirred for 50 hours and then at 50 ° C. for 3 hours. After cooling, the precipitate was reprecipitated in 2 liters of methanol, and the white powder was collected by filtration and dried. The yield was 88 g and the Mw was 35,000.

Production Example 12 of Dispersion Stabilizing Resin [PB] Resin [PB-12] A mixed solution of 100 g of octadecyl methacrylate and 200 g of tetrahydrofuran was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. 5 g of 4,4'-azobis (4-cyanopentanol) was added and reacted for 5 hours. Further, 1.0 g of the above azobis compound was added and reacted for 5 hours. The reaction mixture was cooled to a temperature of 20 ° C. in a water bath, and 3.2 g of pyridine and 1.0 g of 2,2′-methylenebis- (6-t-butyl-p-cresol) were added thereto, followed by stirring. To this mixed solution, 4.2 g of methacrylic acid chloride was added dropwise over 30 minutes so that the reaction temperature did not exceed 25 ° C. The mixture was stirred at a temperature of 20 ° C to 25 ° C for 4 hours. Next, this reaction product was reprecipitated in a mixture of 1.5 liter of methanol and 0.5 liter of water, and a white powder was collected by filtration and dried. 86g yield
And Mw was 33,000.

Production Examples of Dispersion Stabilizing Resin [PB] 13-2
1: Resins [PB-13] to [PB-21] Except for using the acid chloride of Table-C below in place of methacrylic acid chloride in Production Example 12 of dispersion stabilizing resin [PB], the same as Production Example 12 was used. The same operation was carried out to produce dispersion stabilizing resins [PB-13] to [PB-21].

[0112]

[Table 3]

[0113]

[Table 4]

Production Example 22 of Dispersion Stabilizing Resin [PB] 22: Resin [PB-22] A mixed solution of 98.5 g of dodecyl methacrylate, 1.5 g of thioglycolic acid and 200 g of toluene was heated to a temperature of 75 ° C. under a stream of nitrogen. did. 0.5 g of 1,1'-azobis (cyclohexane-1-carbonitrile) was added, and the mixture was reacted for 5 hours.
Reacted for hours. Glycidyl methacrylate (3.0 g), t-butyl hydroquinone (1.0 g) and N,
0.6 g of N-dimethylaniline was added and the mixture was heated to
Reacted for hours. After cooling, the precipitate was reprecipitated in 2 liters of methanol to obtain a pale yellow viscous substance by decantation and then dried. The yield was 80 g and the Mw was 21,000.

Production Example 23 of dispersion stabilizing resin [PB]: Resin [PB-23] 98.5 g of hexadecyl methacrylate, 1.5 g of 2-mercaptoethylamine and 200 g of tetrahydrofuran
g of the mixed solution was heated to a temperature of 80 ° C. under a nitrogen stream.
0.3 g of 1,1'-azobis (cyclohexane-1-carbonitrile) was added and reacted for 5 hours. Further, 0.3 g of the azobis compound was added and reacted for 5 hours. 2.5 g of acrylic anhydride, 2,2'-methylenebis-
1.0 g of (6-t-butyl-p-cresol) was added, and the mixture was stirred at a temperature of 40 ° C. for 5 hours. After cooling, the reaction product was reprecipitated in 2 liters of methanol to obtain a colorless viscous substance. The yield was 82 g and Mw was 20,000.

Production Example 24 of Dispersion Stabilizing Resin [PB]: Resin [PB-24] A mixed solution of 100 g of dodecyl methacrylate and 200 g of tetrahydrofuran was heated to a temperature of 65 ° C. under a nitrogen stream. 6 g of 2,2'-azobis (4-cyanovaleric acid chloride) was added and the mixture was stirred for 10 hours. The reaction solution was cooled in a water bath to a temperature of 25 ° C. or lower, and allyl alcohol 2.4
g was added. 2.5 g of pyridine was added dropwise without exceeding the reaction temperature of 25 ° C., and the mixture was stirred for 1 hour. After further stirring at a temperature of 40 ° C. for 2 hours, the mixture was reprecipitated in 2 liters of methanol. After obtaining a pale yellow viscous substance by decantation, it was dried. The yield was 80 g and Mw was 38,000.

Production Example 25 of Dispersion Stabilizing Resin [PB]: Resin [PB-25] Resin [PB-1] of Production Example 1 of Dispersion Stabilizing Resin [PB]
Octadecyl methacrylate was converted to A. C. V. To carry out a polymerization reaction. The reaction solution was reprecipitated in 3 liters of methanol, and the precipitate was collected by filtration and dried. The yield was 73 g. Next, this powder 5
0 g, methylene chloride 100 g and allyl alcohol 6 g
Was dissolved under stirring at a temperature of 25 ° C. In addition, dicyclohexylcarbodiimide (abbreviated as DCC) 8
g, a mixed solution of 0.3 g of 4- (N, N-dimethylamino) pyridine (abbreviated as D.M.A.P.) and 20 g of methylene chloride were added dropwise over 30 minutes, and the mixture was further stirred for 4 hours. 5 g of formic acid was added thereto, and the mixture was stirred for 30 minutes. Then, insolubles were filtered off, and the filtrate was reprecipitated in 1 liter of methanol. After the precipitate was collected by filtration and dried, Mw4 was obtained in a yield of 38 g.
000 white powder was obtained.

Production Example 26 of Dispersion Stabilizing Resin [PB]: Resin [PB-2]
6] Tree fat of Preparation 11 of the dispersion stabilizing resin [PB] [PB -1
1), and octadecyl acrylate 100
g, 4,4'-azobis (4-cyanopentanol) 5
The polymerization reaction was performed under the conditions of g. The reaction solution is heated to a temperature of 25.
After cooling to 8 ° C., 8 g of vinyl acetic acid was added, and under stirring,
D. C. C. 10 g, D.I. M. A. P. Was added dropwise over 30 minutes to a mixed solution of 0.5 g and 20 g of methylene chloride.
The mixture was further stirred for 4 hours. To this, 5 g of formic acid was added, and after stirring for 30 minutes, insolubles were removed by filtration, and the filtrate was reprecipitated in 3 liters of methanol. The precipitate was collected by filtration and dried to give a white powder of Mw 42,000 in a yield of 75 g.

Production Example 1 of Latex Particle 1: Latex Particle D-1 10 g of dispersion stabilizing resin PB-1, 80 g of vinyl acetate,
Styrene 20 g, octadecyl methacrylate 2.5
g, 5 g of divinyl adipate and 384 of Isopar H.
g of the mixed solution was heated to 70 ° C. while stirring under a nitrogen stream. 0.8 g of 2,2'-azobis (isovaleronitrile) (abbreviated AIVN) was added as a polymerization initiator, and the mixture was reacted for 3 hours. Twenty minutes after addition of the initiator, cloudiness occurred and the reaction temperature rose to 88 ° C. Further, after adding 0.5 g of an initiator and reacting for 2 hours, the temperature was raised to 100 ° C. and the mixture was 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 was a latex having a conversion of 90% and an average particle size of 0.18 μm. The particle size was measured with CAPA-500 (manufactured by Horiba, Ltd.).

Latex Particle Production Examples 2 to 24: Latex Particles D-2 to D-24
B-1, instead of octadecyl methacrylate and divinyl adipate, dispersion-stabilizing resins described in Table D below,
Except that the monomer (C) and the monomer (D) were used, the same procedure as in the above Production Example 1 was carried out, and the latex particles D-
2 to D-24 were produced. The polymerization rate of each of the obtained latex particles is 85 to 90%, and the average particle size is 0.15 to 0.2.
The monodispersity was good within the range of 5 μm.

[0121]

[Table 5]

[0122]

[Table 6]

[0123]

[Table 7]

Production Example 25 of Latex Particles: Latex Particle D-25 14 g of dispersion stabilizing resin PB-22, 80 g of methyl methacrylate, 20 g of ethyl acrylate, 4 g of dodecyl acrylate, 5 g of ethylene glycol diacrylate
And a mixed solution of 375 g of Isopar H were heated to a temperature of 40 ° C. while stirring under a nitrogen stream. A. I. V. N. Was added and reacted for 4 hours. I. V. N. Was added and reacted for 4 hours. After cooling, the mixture was passed through a 200-mesh nylon cloth.
% And a latex having an average particle size of 0.25 μm.

Production Example 26 of Latex Particles: Latex Particles D-26 14 g of dispersion stabilizing resin PB-23 and 1 g of Isopar H
Temperature of 60 ° C. while stirring 77 g of the mixed solution under a nitrogen stream.
Was heated. 60 g of methyl methacrylate, 40 g of methyl acrylate, 3 g of octadecyl acrylate, 5 g of ethylene glycol diacrylate, and 2 g of Isopar G
00g and A.I. I. V. N. 1.0 g of the mixed solution
The mixture was added dropwise over time, and the mixture was stirred for 2 hours. Further, A. I.
V. N. Was added and stirred for 3 hours. 20 after cooling
After passing through a 0-mesh nylon cloth, the obtained white dispersion was a latex having a conversion of 100% and an average particle size of 0.24 μm.

Latex Particle Production Examples 27 to 33: Latex Particles D-27 to D-33 Monomer (A) (that is, methyl methacrylate and methyl acrylate) used in Latex Particle Production Example 26, for dispersion stabilization Resin PB-23, monomer (C) (ie octadecyl acrylate) and monomer (D)
(Ie, ethylene glycol diacrylate), except that the compounds shown in Table E below were used, respectively.
Latex particles were produced in the same manner as in Production Example 26. The polymerization rate of each obtained latex particle is 95-100.
%, The average particle size was in the range of 0.20 to 0.35 μm, and the monodispersity was good.

[0127]

[Table 8]

[0128]

[Table 9]

Production Example 34 of Latex Particles: (Comparative Example A) A treatment was carried out in the same manner as in Production Example 1 of latex particles 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 as latex particles having a polymerization rate of 88% and an average particle size of 0.23 μm was obtained.

Production Example 35 of Latex Particles: (Comparative Example B) A comparative dispersion stabilizing resin (1) having the following structure, which was synthesized by the method disclosed in JP-A-61-43775, was prepared as follows.
Except that a mixed solution of 2 g, 100 g of vinyl acetate, 6 g of divinylbenzene and 388 g of Isopar H was used, the same treatment as in Production Example 1 of latex particles was carried out to obtain a conversion of 88%.
As a result, a white dispersion as latex particles having an average particle size of 0.18 μm was obtained.

[0131]

Embedded image

Production Example 36 of Latex Particles: (Comparative Example C)
Except that 5 g of divinyl adipate was removed as in Example 1, the polymerization rate was 90% and the average particle size was 0.22.
A white dispersion as μm latex particles was obtained.

Production Example 37 of Latex Particles: (Comparative Example D) 97 g of octadecyl methacrylate, acrylic acid 3
g and a mixed solution of 200 g of toluene were heated to a temperature of 75 ° C. under a nitrogen stream. A. I. V. N. 1.0 g
Reacted for hours. Next, 6 g of glycidyl methacrylate,
1.0 g of t-butylhydroquinone and 1.2 g of N, N-dimethyldodecylamine were added, and 18
Stirred for 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.
I got Mw of the obtained comparative dispersion stabilizing resin (2) having the following structure was 5 × 10 ⁴ .

[0134]

Embedded image

In the same manner as in Preparation Example 26 of latex particles, except that 18 g of the comparative dispersion stabilizing resin (2) was used instead of 14 g of the dispersion stabilizing resin PB-23 in Preparation Example 26 of latex particles. Thus, a white dispersion as latex particles having a polymerization rate of 98% and an average particle diameter of 0.30 μm was obtained.

Preparation Example 38 of Latex Particles: (Comparative Example E) In Preparation Example 26 of latex particles, 5 g of ethylene glycol diacrylate was used as the monomer (D).
The polymerization rate was 1 in exactly the same manner as in Production Example 26 except that
A white dispersion was obtained which was a latex particle having an average particle size of 0.23 μm at 00%.

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 on a paint shaker (manufactured by Tokyo Seiki Co., Ltd.) together with glass beads. Put it in for 4 hours,
A fine dispersion of nigrosine was obtained. The resin dispersion of Production Example 1 of latex particles (latex particle D-1) was mixed with 30
g, 2.5 g of the above nigrosine dispersion, branched octadecyl alcohol FOC-1800 (manufactured by Nissan Chemical Industries, Ltd.) 1
A liquid developer for electrostatography was prepared by diluting 5 g and 0.07 g of octadecene-half-maleic acid octadecylamide copolymer into 1 liter of Isopar G.

(Preparation of Comparative Developers A to C) Three kinds of liquid developers A, B and C for comparison were prepared by replacing the resin dispersion in the production of the above liquid developer with the following resin dispersion. . Comparative liquid developer A: resin dispersion of Production Example 34 of latex particles. Comparative liquid developer B: resin dispersion of Production Example 35 of latex particles. Comparative liquid developer C: resin dispersion of Production Example 36 of latex particles.

Using these liquid developers for an electrophotographic plate making system, various characteristics were evaluated. The results are shown in Table F.

[0140]

[Table 10]

The measurement of each evaluation item in Table-F was performed as follows. (Note 1) Stain on the developing device and plate image of the 2000th sheet: ELP404V, a fully automatic plate making machine (manufactured by Fuji Photo Film Co., Ltd.), and ELP Master II type electrophotographic photosensitive material using liquid developer (Fuji Photo Film Co., Ltd.) was exposed and developed. Plate making speed is 7
Performed at plate / min. Further, the presence or absence of toner adhesion stains on the developing device after processing 2,000 sheets of the ELP Master II type was observed. The blackening rate (image area) of the copied image is 30
% Of the manuscript.

(Note 2) Fixing property of image: Liquid developer was used for EL
A plate was prepared using the electrophotographic photosensitive material P-1 prepared as described below, using the developer of P404V, 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 practically sufficient fixability, was used as a liquid developer as a reference for evaluation. <Preparation of electrophotographic photosensitive material P-1> 34 g of binder resin B-1 having the following structure, 6 g of binder resin B-2 having the following structure, 200 g of photoconductive zinc oxide, 0.03 g of uranine, and 0 Rose Bengal A mixture of 0.06 g, 0.02 g of tetrabromophenol blue, 0.30 g of phthalic anhydride, 0.01 g of o-chlorophenol and 300 g of toluene was treated with a homogenizer (manufactured by Nippon Seiki Co., Ltd.) at 1 × 10 ⁴ r.
The dispersion was performed at a rotation speed of pm for 10 minutes. This dispersion for forming a photosensitive layer was applied to a conductive treated paper with a wire bar so as to have a dry adhesion amount of 26 g / m ² , dried at 100 ° C. for 30 seconds, and then heated at 120 ° C. for 1 hour. Then 2 in the dark
The mixture was allowed to stand for 24 hours at 0 ° C. and 65% RH to produce an electrophotographic photosensitive material P-1.

[0143]

Embedded image

(Note 3) Resist properties of toner image: An etching machine was used to make a plate using a desensitizing liquid ELP-EX (manufactured by Fuji Photo Film Co., Ltd.) under the same conditions as in (Note 2) above. Was passed through once, immersed in a hydrophilic treatment solution E-1 of a photoconductive layer binder resin having the following formulation for 5 minutes, and then 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 to the image portion was visually evaluated. <Preparation of Hydrophilizing Solution E-1> Monoethanolamine 8
0 g, Newcol B4SN (Nippon Emulsifier Co., Ltd.) 8
g and 100 g of benzyl alcohol in distilled water.
After adjusting to 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 subjected to plate making and hydrophilizing treatment under the conditions of (Note 3) was diluted 20 times with distilled water as a fountain solution. Using a solution and a neutral paper as a base paper for printing, under the condition that a printing machine Hamadaster 800SX (manufactured by Hamadastar Co., Ltd.)
And the number of printed sheets in which the image portion of the printed matter was not lost was examined.

From the results shown in Table-F, the developers of the present invention and Comparative Example C did not cause staining on the developing device, and the image on the 2000th plate was clear, showing good results. This indicates that the dispersibility and the redispersibility are good. On the other hand, in the developers of Comparative Examples A and B, the redispersibility deteriorated, and the reproducibility of the actual copied image was adversely affected. Further, 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 had practically sufficient fixability.

Further, when the zinc oxide and the binder resin B-1 in the non-image area of the plate surface after plate making are converted to hydrophilic by chemical treatment, the image area is sufficiently resisted by the toner layer, and the image area is deficient. Examination was made under forced conditions to determine whether or not the toner particles were generated. As a result, defects were found in fine areas of the toner image portion such as fine lines and fine characters, except for the toner particles of the present invention. In addition, when processed under normal desensitizing conditions and printed as an offset master plate, clear prints were obtained with only the present invention even after printing 5,000 sheets. Comparative Examples A and B
In the case of, a decrease in the reproducibility of the copied image at the time of plate making appeared in the printed matter as it was, and the lack of fine lines and fine characters was observed from the start of printing. Further, in Comparative Example C, at the time of printing, thin lines, fine characters, and the like were missing on about 2,000 sheets from the start of printing. As described above, only the liquid developer of the present invention satisfies excellent dispersibility / redispersibility and printing durability in an electrophotographic plate making system using an electrophotographic photoreceptor having improved printing characteristics. there were.

Example 2 Production Example 26 of Latex Particle (Latex Particle D-2)
30 g of the resin dispersion of 6) , 10 g of branched hexadecyl alcohol FOC-1600 (manufactured by Nissan Chemical Industries, Ltd.), and 0.06 g of octadecyl vinyl ether / half maleic acid dodecylamide copolymer were diluted to 1 liter of Isopar G. Thus, a liquid developer for electrostatography was prepared.

(Preparation of Comparative Developers D and E) Two kinds of liquid developers D and E for comparison were prepared by replacing the resin dispersion in the production of the liquid developer with the following resin dispersion. Comparative liquid developer D: a resin dispersion of Production Example 37 of latex particles. Comparative liquid developer E: resin dispersion of Production Example 38 of latex particles.

Using these liquid developers for an electrophotographic plate making system, various characteristics were evaluated. The results are shown in Table G.

[0151]

[Table 11]

In Table G, the contamination of the developing device and
The measurement of the evaluation items of the 00th plate image was performed in Example 1.
Was performed in the same manner as described above. The other evaluation items were measured as follows. (Note 5) Resist property of toner image: Electrophotographic photosensitive material P-2 prepared according to the following prescription was used in a dark place with a surface potential of +450 V.
2.8-mW output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength 780)
nm) on the photosensitive material surface using 60 erg / cm
Under the irradiation amount of ² , 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 above liquid developers. Further, the toner image was fixed by heating at 100 ° C. for 1 minute.

<Preparation of Electrophotographic Photosensitive Material P-2> X-type metal-free phthalocyanine (manufactured by Dainippon Ink Co., Ltd.) as an organic photoconductive compound was 1.9 parts by weight, and as an additive, a thiobarbitur tool having the following structure was used. 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 part by weight of a mixed solution of tetrahydrofuran / cyclohexane in an 8/2 weight ratio.
00 parts by weight were put together with glass beads in a glass container of 500 ml and dispersed with a paint shaker for 60 minutes. Then, the glass beads were separated by filtration to obtain a dispersion for a photoconductive layer. Next, the dispersion liquid for a photoconductive layer is coated on 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.

[0154]

Embedded image

Each of the original plates thus obtained was immersed in a processing solution E-2 having the following formulation for 30 seconds to remove the non-image portion of the photoconductive layer, washed with water for 30 seconds, and then dried with a drier. 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 fine lines / fine characters in the image portion of this printing original plate was checked with a 60-fold loupe (PEAK ( Co., Ltd.).

(Note 6) Printing durability: The original plates for offset printing prepared by operating each photosensitive material under the same conditions as in (Note 5) above were gummed, and then subjected to an offset printing machine (Sakurai Seisakusho Co., Ltd.). ) Oliver 52 type) indicates the number of sheets that can be printed without causing any problem in background stain on the non-image area of the printed matter and the image quality of the image area (the larger the number of printed sheets, the better the printing durability).

From the results shown in Table-G, the liquid developers of the present invention and Comparative Example E showed good redispersibility, and the image on the plate after 2,000 sheets was also good. However, Comparative Example D
Toner scum was generated, the developing portion was stained, and the plate image was also missing after 2000 sheets of fine lines and fine characters.

Next, the plate after plate making was eluted from the non-image area with an alkaline processing solution to obtain an offset master 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 properties of the toner layer with respect to the processing liquid were not sufficient, and the toner layer was dissolved and eluted during the processing. On the other hand, in the present invention and Comparative Example D, these phenomena were not observed, and sufficient resist properties were shown.

Furthermore, as an offset master master,
As a result of actual printing, 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 copy image reproducibility during plate making, and Comparative Example E is because the resist of the processing solution dissolving and removing the non-image area is not sufficient, both well as precursor for an offset master Since high image reproducibility was not obtained, the image quality of the printed matter was deteriorated from the start of printing, and a printed matter having a sufficient image quality was not obtained.

As described above, only the liquid developer of the present invention
In an electrophotographic plate making system in which a non-image portion was eluted to be a printing original plate, excellent dispersibility, re-dispersibility and printing durability were satisfied.

Example 3 10 g of a tetradecyl methacrylate / methacrylic acid copolymer (copolymerization ratio: 95/5 by weight), 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 27 of latex particles (latex particle D-27) , 2.5 g of the above nigrosine dispersion, 0.06 g of hexadecene / hema maleic acid octadecylamide copolymer, and 20 g of FOC-1800 A liquid developer for electrostatography was prepared by diluting to 1 liter of Isopar G.

The obtained liquid developer of the present invention was used in Example 1.
When the contamination of the developing device and the 2000th plate image were evaluated under the same conditions as (Note 1) of the evaluation items, good results were obtained as in Example 1 in each case.

Next, the electrophotographic photosensitive material P-3 prepared according to the following prescription was charged to -6 kV in a dark place, and a 2.0 mW output gallium-aluminum-arsenic semiconductor laser (oscillation wavelength: 780 nm) was used as a light source. And a pitch of 25 μm on a photosensitive material surface under an irradiation dose of 45 erg / cm ^2.
After exposure at a scanning speed of m and a scanning speed of 330 m / sec, development was performed using the liquid developer of the present invention, and further heating at 60 ° C. for 30 seconds to obtain a toner image.

<Preparation of Electrophotographic Photosensitive Material P-3> 25 g of a binder resin B-4 having the following structure was prepared.
5, 9 g of 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, 0.018 of cyanine dye A having the following structure
g and 300 g of toluene were dispersed at a rotation speed of 1 × 10 ⁴ rpm for 10 minutes using a homogenizer to prepare a dispersion for forming a photosensitive layer. This was applied to a conductive treated paper with a wire bar so that the dry adhesion amount was 25 g / m ² , dried at 100 ° C. for 20 seconds, and further dried at 120 ° C. for 1 second.
Heated for hours. Then, the electrophotographic photosensitive material P is allowed to stand in a dark place at 20 ° C. and 65% RH for 24 hours.
-3 was prepared.

[0165]

Embedded image

[0166]

Embedded image

The master thus obtained was passed through an etching machine once using ELP-EX, and then immersed for 3 minutes in a photoconductive layer binder resin hydrophilizing solution E-3 having the following formulation. Then, 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 make 1 liter, and the pH was adjusted to 11.0 with potassium hydroxide. Treatment liquid E-3
Was prepared.

Observation of the image portion of the obtained printing original plate with an optical microscope revealed that there were no defects such as fine lines and fine characters in the toner image portion, and the resist properties of the toner particles of the present invention were good. Next, the printing durability was the same as in Example 1, except that the above-mentioned master was used as an offset master master, and a solution obtained by diluting the processing solution E-3 ten times with distilled water was used as a dampening solution. As a result, 3,000 prints having good print quality were obtained.

Examples 4 to 19 The same procedures as in Example 1 were carried out except that the latex particles D-1 of the liquid developer of the present invention were replaced by the latex particles shown in Table H below. To prepare each liquid developer.

[0170]

[Table 12]

Each of the obtained liquid developers was used in an electrophotographic plate making system in the same manner as in Example 1 to examine the performance. Each liquid developer shows the same performance as in Example 1,
Redispersibility, fixability, resistability and printing durability were all good.

Examples 20 to 35 The same procedures as in Example 2 were carried out except that the latex particles D-26 of the liquid developer of the present invention were replaced by the latex particles shown in Table I below. To prepare each liquid developer.

[0173]

[Table 13]

Each of the obtained liquid developers was used in an electrophotographic plate making system in the same manner as in Example 2 to examine the performance. Each liquid developer shows the same performance as in Example 2,
Redispersibility, resist properties and printing durability were all good.

Example 36 A mixture of 100 g of the white resin dispersion obtained in Production Example 30 of latex particles and 1.5 g of Sumicalon Black was heated to a temperature of 100 ° C., and heated and stirred for 4 hours. After cooling to room temperature, the remaining dye was removed by passing through a 200-mesh nylon cloth to obtain a black resin dispersion having an average particle size of 0.21 μm. A liquid developer was prepared by diluting 30 g of the above black resin dispersion and 0.05 g of zirconium naphthenate into 1 liter of Shellsol 71. When this was developed by the same apparatus as in Example 1, no toner stain was generated on the apparatus even after 2,000 sheets were developed. Also, in the same manner as in Example 1, the plate was made into a plate for offset master by performing plate making and etching treatment.
The printed matter after 3,000 sheets was a printed matter of clear image quality.

Example 37 A mixture of 100 g of the white resin dispersion obtained in Production Example 33 of latex particles and 3 g of Victoria Blue B was heated to a temperature of 70 to 80 ° C. and stirred for 6 hours. After cooling to room temperature, the remaining dye was removed through a 200-mesh nylon cloth to obtain a blue resin dispersion having an average particle size of 0.25 μm. A liquid developer was prepared by diluting 32 g of the above blue resin dispersion and 0.05 g of zirconium naphthenate into 1 liter of Isopar H. When this was developed by the same apparatus as in Example 3, no toner adhesion stains were observed on the apparatus even after 2,000 sheets were developed. or,
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.

[0177]

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

Claims (1)

(57) [Claims] 1. A liquid developer for electrophotography comprising at least resin particles dispersed in a non-aqueous solvent having an electric resistance of not less than 10 ⁹ Ωcm and a dielectric constant of not more than 3.5. 1) At least one of the monofunctional monomers (A) that are soluble in the non-aqueous solvent but are insolubilized by polymerization
Species, (2) a monomer (C) represented by the following general formula (I), which has a specific substituent and is copolymerizable with the monomer (A)
(3) at least one of the polyfunctional monomers (D) having two or more polymerizable functional groups copolymerizable with the monomer (A);
A seed, and (4) a polymer containing a repeating unit represented by the following general formula (II), having a weight average molecular weight of 2 × 1
0 ⁴ a to 5 × 10 ^5, and one terminal of the polymer main _{chain, -PO 3 H 2, -SO 3} H, -COOH, -P
(= O) (OH) R ¹ wherein R ¹ represents a hydrocarbon group or —OR ² (R ² represents a hydrocarbon group);
OH, formyl _{^{group, -CONR 3 R 4, -SO 2}} NR 3
R ⁴ (where R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group), a cyclic acid anhydride-containing group, and at least one polar group selected from an amino group, or the monomer Dispersion stabilizing resin [P] soluble in said non-aqueous solvent, comprising a polymerizable functional group which can be copolymerized with isomer (A)
A liquid developer for electrophotography, comprising polymer resin particles obtained by polymerizing a solution containing at least one of the following. Embedded image 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). Embedded image 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 from each other, and are each -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 a -NHCONH- (wherein R ₂₂ represents the same meaning as above R _21). A ₁ and A ₂ may be the same or different from each other, each represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted, or may have the following formula 3 intervening in the bond of the main chain. Embedded image In Chemical Formula 3, 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 above, and A ₄ represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted. And R ₂₃ has the same contents as R ₂₁ described above. m, n and p may be the same or different and represent an integer of 0 to 4, respectively. However, m, n and p do not become 0 at the same time. formula
In (I), U ¹ represents -COO-, -CONH-, -CON.
(E ² )-[where E ² is an aliphatic group or
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 may be the same or different from each other and each represent a hydrogen atom, an alkyl group, —COO-E ³ or —CH ₂ COO-E ³ (where E ³ represents an aliphatic group). Embedded image In the formula (II), X ¹ represents —COO—, —OCO—, —CH _{2
OCO -, - CH 2 COO -} , - O-, or -SO ₂ -
Represents Y ¹ represents an aliphatic group having 6 to 32 carbon atoms.
b ¹ and b ² may be the same or different from each other, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, —COO-Z ¹ , or a hydrocarbon having 1 to 8 carbon atoms. -COO-Z ¹ through a group (where Z ¹ has 1 to ¹ carbon atoms)
22 hydrocarbon groups).