JP3300461B2 - 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 The present invention relates to a liquid developer having excellent stability, storage stability, stability, image reproducibility, and fixability.

[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. . In such a developer, the resin is dispersed as insoluble latex particles in the form of particles having a diameter of several nanometers to several hundreds of nanometers. However, in a conventional liquid developer, a soluble dispersion stabilizing resin or a polarity controlling agent and an insoluble latex particle are used. Insufficient bonding with the polymer resulted in a state where the soluble dispersion stabilizing resin and the polarity controlling agent were easily diffused into the solution. For this reason, the soluble dispersion stabilizing resin is detached from the insoluble latex particles by long-term storage or repeated use,
Particles settle, agglomerate, deposit, or become ambiguous,
There was a disadvantage. Further, since the particles once aggregated and deposited are difficult to re-disperse, the particles remain adhered to various parts of the developing device, leading to failure of the developing device such as contamination of an image area and clogging of a liquid feeding pump.

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

Further, in order to improve the above-mentioned drawbacks, the insolubility of a copolymer of a monomer to be insolubilized and a monomer containing a long-chain alkyl moiety or a monomer containing two or more polar components is considered. A method of improving the degree of dispersion, redispersibility, and storage stability of particles by forming dispersed resin particles is disclosed in JP-A-60-17.
9751, 62-151868 and the like. Further, in the presence of a polymer utilizing a bifunctional monomer or a polymer utilizing a polymer reaction, an insoluble dispersed resin particle of a copolymer of a monomer insolubilized and a monomer containing a long-chain alkyl moiety A method for improving the degree of dispersion, redispersibility and storage stability of particles by using
Nos. 2-166362 and 63-66567. Further, as a dispersion stabilizing polymer, a conventional random copolymer is converted into a block copolymer of a polymer part to be solvated and a non-solvable polymer part, thereby improving redispersibility and storage stability. An improved method is disclosed in Japanese Unexamined Patent Publication No.
6, No. 3-111860, No. 3-225353,
No. 4-45455.

[0005]

On the other hand, in recent years, a method of printing a large number of sheets of 5,000 or more using an electrophotographic offset printing master plate has been attempted. It has become possible to print 10,000 sheets or more in plate size. or,
The operation time of the electrophotographic plate making system has been shortened, and the development-fixing process has been improved to be faster. JP-A-60-179751, JP-A-62-151868, JP-A-62-166362, JP-A-63-66567, JP-A-3-12666, JP-A-3-111860, and JP-A-3-22
Dispersed resin particles produced according to the means disclosed in JP-A Nos. 5353 and 4-45455, when the developing speed is increased, the dispersibility and re-dispersibility of the particles are reduced, and the fixing time is shortened. Or large plate size (for example, A
-3 size or more), the performance was not necessarily satisfactory in terms of printing durability.

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 which has a rapid development-fixing process and is excellent in dispersion stability, re-dispersibility and fixability even in an electrophotographic plate making system using a large-size master plate. 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. Another object of the present invention is to provide a liquid developer suitable for various kinds of electrophotography and various kinds of transfer in addition to the above-mentioned applications. Still another object of the present invention is to provide a liquid developer that can be used in any system where a liquid developer can be used, such as ink jet recording, cathode ray tube recording, and recording of various change processes such as pressure change or electrostatic change. That is.

[0007]

The above objects are attained in a liquid developer for electrophotography comprising at least resin particles dispersed in a carrier liquid having an electric resistance of not less than 10 ⁹ Ωcm and a dielectric constant of not more than 3.5. At least one monofunctional monomer (A) in which the dispersed resin particles are soluble in a non-aqueous solvent but are insolubilized by polymerization; a specific substitution represented by the following general formula (I); At least one monomer (C) containing a group and copolymerizable with the monomer (A);
And a phosphono group, a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, -P (= O) (O
H) R ¹ group [R ¹ represents a -R ² group or -OR ² group, R ²
Represents a hydrocarbon group], -CONR ³ R ⁴ group, -SO ₂ N
A polymer component containing an R ³ R ⁴ group (R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group) and at least one polar group selected from cyclic acid anhydride-containing groups And / or a block A containing at least one polymer component corresponding to the monofunctional monomer (A) and the following general formula (II)
And at least three AB-type block polymer chains composed of a block B containing at least one type of polymer component represented by the following formula: At one end of the polymer main chain of block A opposite to the end bonded to block B, is bonded to the organic molecule, and has a weight average molecular weight of 5 × 10 ³ to
1 × 10 ^6, which is a polymer resin particle obtained by polymerizing a mixture containing at least one dispersion stabilizing resin [P] comprising a star copolymer. Achieved by electrostatographic liquid developers.

[0008]

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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).

[0010]

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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 each is -O-, -S-, -CO-,
—CO ₂ —, —OCO—, —SO ₂ —, —N (R ₂₂ ) —,
_{-CON (R 22) -, -} N (R 22) CO -, - N
_{(R 22) SO 2 -,} - SO 2 N (R 22) -, - NHCO 2
— Or —NHCONH— (where R ₂₂ is the above R
Indicates the same content as 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 7 in the bond of the main chain.

[0012]

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[0013] Among of 7, B ₃ and B _4, which may be the same or different, indicates the B _1, B ₂ identical contents and, A ₄
Represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and R ₂₃ has the same contents as R ₂₁ described above. m, n and p
May be the same or different, and each represents an integer of 0 to 4. However, m, n and p do not become 0 at the same time. In the formula (I), U ¹ is -COO-, -CONH-,-
CON (E ² ) — [E ² represents an aliphatic group or a substituent represented by the general formula (III)], —OCO—,
_{CONHCOO -, - CH 2 COO -} , - (CH 2) s O
CO- [wherein s represents an integer of 1 to 4], represents a -COO- -O- or -C ₆ H _4. a ¹ and a ² may be the same or different, and each represents a hydrogen atom, an alkyl group,
OO-E ³ or -CH ₂ COO-E ³ (where E ³ represents an aliphatic group).

[0014]

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In the general formula (II), X ¹ is -COO-, -O
_{CO -, - (CH 2)} x COO -, - (CH 2) x OCO-
[Where x represents an integer of 1 to 3], or -O-. Y ¹ represents an aliphatic group having 8 or more carbon atoms. b ¹ and b ²
May be the same or different from each other, and each may be a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-Z ¹ ,
Or —COO—Z ¹ via a hydrocarbon group (where Z ¹ represents a hydrogen atom or a hydrocarbon group which may be substituted).

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 used in a non-aqueous solvent to disperse the star-type block copolymer of the present invention. Polymerizing at least one monofunctional monomer (A) and at least one monomer (C) containing a specific substituent in the presence of the resin [P] (so-called polymerization granulation method). ).

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 in combination 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 be distilled off under heating or under reduced pressure after polymerization granulation. However, even if the non-aqueous solvent is brought into a liquid developer as a latex particle dispersion, the liquid There is no problem as long as the resistance is within the range of 10 ⁹ Ωcm or more. Normal,
It is preferable to use the same solvent as the carrier liquid at the stage of producing the resin dispersion. As described above, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and 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.

[0021]

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In the general formula (IV), T ¹ is -COO-, -O
_{CO -, - 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-”. The phenylene group includes 1,2-, 1,3- and 1,4-phenylene groups. ]. W ¹ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, a butyl group, a 2-chloroethyl group, a 2-bromoethyl group, a 2-cyanoethyl group) , A 2-hydroxyethyl group, a benzyl group,
Chlorobenzyl, methylbenzyl, methoxybenzyl, phenethyl, 3-phenylpropyl, dimethylbenzyl, fluorobenzyl, 2-methoxyethyl, 3-methoxypropyl, 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 the above 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.

[0027]

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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).

[0029]

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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 each is -O-, -S-, -CO-,
—CO ₂ —, —OCO—, —SO ₂ —, —N (R ₂₂ ) —,
_{-CON (R 22) -, -} N (R 22) CO -, - N
_{(R 22) SO 2 -,} - SO 2 N (R 22) -, - NHCO 2
— Or —NHCONH— (where R ₂₂ is the above R
Indicates the same content as 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 12 intervening in the bond of the main chain.

[0031]

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

The case where E ¹ in the monomer (C) represented by the general formula (I) represents an aliphatic group having 8 or more carbon atoms will be described in detail. In the general formula (I), preferably,
E ¹ represents an alkyl group having a total of 10 or more carbon atoms which may be substituted or an alkenyl group having a total of 10 or more carbon atoms. U ¹ is -
COO -, - CONH -, - CON (E 2) - [However,
E ² is preferably an aliphatic group having 1 to 32 carbon atoms (aliphatic As the base for example an alkyl group, an alkenyl group or an aralkyl group)], -OCO -, - CH ₂ OCO
-Or -O-. a ¹ and a ² may be the same or different and are preferably a hydrogen atom, a methyl group, -COO-
E ³ or —CH ₂ COO—E ³ [where E ³ preferably represents 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 -COO-, -CO
NH-, or -CON (E ²⁾ - represents, a ¹ and a
² may be the same or different, represent a hydrogen atom or a methyl group, E ¹ represents the same content as described above.

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 represents the same range as the aliphatic group of the acid).

The case where E ¹ in the monomer (C) represented by the general formula (I) represents a substituent represented by the general formula (III) will be described in detail. More specific examples of A ₁ and A ₂ include those represented by —C (R ₂₄ ) (R
₂₅₎ - [R _24, R ₂₅ is a hydrogen atom, an alkyl group, a halogen atom, etc.], - (CH = CH) -, cyclohexylene group [hereinafter, a cyclohexylene group - the "-C ₆ H _10" It represents, "- C ₆ H ₁₀ -" is 1,2-cyclohexylene group, 1,3-cyclohexylene, 1,4 include cyclohexylene], the reduction 12, etc. atomic group any of It is composed of a combination.

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 , R ₂₁ ) has a total number of atoms of 8
What is comprised from the above is preferable. Where U ¹ −
CON (E ² ) —, and E ² is a substituent represented by the general formula (III) [that is,-(A ₁ -B ₁ ) _m- (A _2-
B ₂₎ when it represents an _n -R _21], linked backbone consists of E ² are also included in the connecting backbone. Further, in the case where A ₁ and A ₂ are a hydrocarbon group which causes the chemical formula 12 to intervene in the bonding of the main chain, -B _3- (A ₄ -B ₄ ) _p -R 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
Groups) and hydrogen atoms are not included in the number of atoms, and carbon atoms, ether-type oxygen atoms, and nitrogen atoms constituting the connecting main chain are included in the number of atoms. Therefore, -COO- and -C
ONH- is 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 E ¹ represents a substituent represented by the general formula (III), that is, when the monomer having a specific polar group is In this case, more specifically, the following compounds can be exemplified.

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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The dispersing resin of the present invention comprises at least one kind of each of the monomers (A) and (C). What is important is that the resin synthesized from these monomers is used in the non-aqueous solvent. If it is insoluble in, a desired dispersion resin can be obtained. More specifically, the monomer (C) represented by the general formula (I) is added in an amount of 0.1 to 20% by weight based on the monomer (A) to be insolubilized.
Preferably used, more preferably 0.3 to 8
% By weight. The molecular weight of the dispersion resin of the present invention is preferably 1 × 10 ³ to 1 × 10 ⁶ , more preferably 1 × 10 ^3.
10 ^{4 to} 5 × 10 ⁵ .

The dispersion stabilizing resin [P] of the present invention, which is used for forming a stable resin dispersion from the solvent-insoluble polymer produced by polymerizing the above monomer in a non-aqueous solvent, will be described. . The dispersion stabilizing resin [P] is a star-shaped resin having a weight average molecular weight of 2 × 10 ⁴ to 1 × 10 ⁶ , comprising at least three polymer chains of an AB type block copolymer component bonded to an organic molecule. It is a copolymer. One block (block A) bonded to the organic molecule is a phosphono group, a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, a —P (＝ O) (OH) R ¹ group [R ¹ is — R ² or —OR ² , wherein R ² represents a hydrocarbon group], —CON
At least one selected from an R ³ R ⁴ group, a —SO ₂ NR ³ R ⁴ group (R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group), and a cyclic acid anhydride-containing group And / or at least one polymer component corresponding to the monofunctional monomer (A). Another one block (Block B)
Comprises at least one polymer component comprising a repeating unit represented by the general formula (II). Here, the order of the sequence in the polymer chain of the block A and the block B is such that the block A is one end of the polymer main chain opposite to the end bonded to the block B and is bonded to an organic molecule. The resin [P] is schematically shown as in the following formula (19).

[0045]

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In the chemical formula 19, X represents an organic molecule;
(A) represents block A, (B) represents block B,
(A)-(B) represent a polymer chain. In addition, such AB
The upper limit of the number of the type block polymer chains contained in the organic molecule is at most 15, usually about 10.

The proportion of the blocks A and B in the star type copolymer is from 1/50/99 to 50 (weight ratio), preferably from 5/40/95 to 60 (weight ratio). The specific polar group-containing polymer component contained in the block A is preferably 1 to 30 parts by weight, more preferably 1 to 15 parts by weight, per 100 parts by weight of the dispersion stabilizing resin [P]. When no specific polar group-containing polymer component is present in the block A, the polymer component corresponding to the monofunctional monomer (A) preferably has a content of 5 to 100 parts by weight of the resin [P]. It is 50 parts by weight, more preferably 10 to 40 parts by weight. The polymer component represented by the general formula (II) contained in the block B includes:
Preferably 50 in 100 parts by weight of the dispersion stabilizing resin [P].
To 99 parts by weight, more preferably 60 to 95 parts by weight. In the dispersion stabilizing resin [P], the above-mentioned predetermined existence ratio (that is, the above-mentioned block A and block B
, The proportion of the specific polar group-containing polymer component contained in the block A, and the proportion of the polymer component represented by the general formula (II) contained in the block B). The re-dispersion stability of the dispersed resin particles obtained by polymerizing the monofunctional monomer (A) and the monomer (C) is reduced. On the other hand, when the content exceeds a predetermined ratio, the average particle size of the dispersed resin particles obtained by the polymerization reaction of the monofunctional monomer (A) and the monomer (C) becomes coarse, and the particle distribution of the particles becomes simple. Dispersion is reduced.

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. The weight average molecular weight (Mw) of the dispersion stabilizing resin [P] of the present invention is 5 × 10 ³ to 1 × 10 ⁶ , preferably 1 × 10 ⁴ to 2 × 10 ⁵ .

Next, block A of dispersion stabilizing resin [P]
Will be described in detail. The block A is composed of a polymer component corresponding to the monofunctional monomer (A) and / or the above-mentioned polymer component containing a specific polar group. Examples of the polymer component corresponding to the monofunctional monomer (A) include the same contents as described above for the insoluble monomer (A). Preferably, it is composed of the same monomer as the monofunctional monomer (A) to be the dispersed resin particles.

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

In the specific polar group, in the —CONR ³ R ⁴ group and the —SO ₂ NR ³ R ⁴ group, R ³ and R ⁴ are each independently a hydrogen atom or a hydrocarbon group (having 1 to 1 carbon atoms). 10, preferably an optionally substituted hydrocarbon group having 1 to 8 carbon atoms)
Represents Specific examples of the hydrocarbon group represented by R ³ and R ⁴ include those having the same contents as the hydrocarbon group represented by R ² .

The cyclic acid anhydride-containing group is a group containing at least one cyclic acid anhydride. 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.

Further, among the specific polar groups, the amino group is
Represents H ₂ , —NHR ⁵ or —NR ⁵ R ⁶ . R ⁵ and R ⁶ represent a hydrocarbon group having 1 to 10, preferably 1 to 8 carbon atoms. More preferably represents a hydrocarbon group having 1 to 7 carbon atoms, specifically, include those of the same contents as the hydrocarbon group represented by R ^2.

The hydrocarbon group of R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is still more preferably an alkyl group having 1 to 4 carbon atoms which may be substituted, a benzyl group which may be substituted, Or a phenyl group which may be substituted.

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

The following can be mentioned as specific examples of these compounds. However, in each of the following examples, e
Is _{-H, -CH 3, -Cl, -Br} , -CN, -CH 2 C
OOCH ₃ or —CH ₂ COOH, and f represents —H or —H.
CH ₃ , n is an integer of 2 to 10, m is 1 to 1
0 represents an integer, and p represents an integer of 1 to 4. X ₁ is -C
OOH, -O-P (= O ) (OH) 2, -SO 3 H, -O
H, -NR _a R _b, -CHO or -O-P (= O) ( O
H) Shows _Ra . Here, R _a and R _b represent an alkyl group having 1 to 4 carbon atoms. X ₂ represents a -COOH or -OH.

[0057]

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[0058]

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[0059]

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Next, the block B of the dispersion stabilizing resin [P] is used.
The repeating unit represented by the general formula (II) constituting the following will be described in detail. In the general formula (II), X ¹ preferably represents -COO-, -OCO- or -O-. Y ¹
Preferably represents an alkyl group or an alkenyl group having 10 or more carbon atoms, which may be linear or branched. Specifically, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group,
And linolel groups.

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 chlorine atom, a bromine atom, etc.), a cyano group, and a carbon number of 1 to 3.
Alkyl group (e.g., methyl group, ethyl group, propyl group, etc.), - COO-Z ¹ or -CH ₂ COO-Z ¹ [Z ¹
Represents a hydrogen atom or an optionally substituted hydrocarbon group having 22 or less carbon atoms (eg, an alkyl group, an alkenyl group, an aralkyl group, an alicyclic group, an aryl group, etc.).

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

Further, in the block B of the dispersion stabilizing resin used in the present invention, other repeating units may be contained as a copolymer component together with the repeating units represented by the general formula (II). The other copolymer component may be any compound as long as it is composed of a monomer copolymerizable with the monomer corresponding to the repeating unit of the general formula (II). However, it is preferable not to contain other components, and it is used in an amount not exceeding 20 parts by weight in the block B at most. If the amount exceeds 20 parts by weight, the dispersion stability of the dispersed resin particles will be deteriorated. In the block B, two or more kinds of repeating units represented by the general formula (II) may be used in combination.

On the other hand, the organic molecule according to the present invention comprising at least three polymer chains bonded is not particularly limited as long as the molecular weight of the molecule is 1,000 or less. For example, a trivalent hydrocarbon residue represented by the following formula (23) may be mentioned.

[0065]

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Wherein r ^{1 to} r ⁶ each represent a hydrogen atom or a hydrocarbon group. However, at least one of r ¹ and r ² is connected to the polymer chain, and at least one of r ^{3 to} r ⁶ is connected to the polymer chain. These organic residues are composed of a single compound or an arbitrary combination thereof, and in the case of a combination, -O-, -S-, -N
^{(R 7) -, - COO} -, - CON (r 7) -, - SO
_{2 -, - SO 2 N (} r 7) - { wherein r ⁷ represents a hydrogen atom or a hydrocarbon group}, - NHCOO -, - NHCONH
-A heterocycle containing a hetero atom such as an oxygen atom, a sulfur atom, a nitrogen atom or the like (for example, thiophene ring, pyridine ring, pyran ring, imidazole ring, benzimidazole ring, furan ring, piperidine ring, pyrazine ring, pyrrole ring, piperazine ring) Etc.) may be included.

Examples of other organic molecules that bind the polymer chain include those composed of a combination of the following chemical formula (24) and the above-mentioned binding unit. However, specific examples of the organic molecule according to the present invention are not limited to these.

[0068]

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The star-type copolymer [P] of the present invention can be synthesized using a conventionally known method of synthesizing a star-type polymer of a monomer containing a polar group and having a polymerizable double bond group. it can. For example, one of them is a polymerization reaction using a carbanion as an initiator. Specifically, M. Morton,
TE Helminiak et al “J. Polym. Sci.” 57, 471 (19
62), B. Gordon III, M, Blumenthal, JE Loftus et
al “Polym. Bull.” 11,349 (1984), RB Bates, W.
A. Beavers et al “J. Org. Chem.” 44, 3800 (1979)
Can be synthesized according to the method described in (1). However, when this reaction is used, the “specific polar group” of the present invention is used as a protected functional group, polymerized, and then the protective group is eliminated. The protection of the specific polar group by the protecting group of the present invention and the elimination of the protecting group (deprotection reaction) can be easily carried out by utilizing conventionally known knowledge. For example, various descriptions are given in the above cited references. Furthermore, Yoshio Iwakura and Keisuke Kurita, "Reactive Polymers", published by Kodansha (1977)
TW Greene “Protective Groups in Organic S”
ynthesis ”(JohnWiley & Sons, 1981), JFW Mc
Omic “Protective Groups in Organic Chemistry” (Pl
enum Press, 1973) and the like.

Another method is to use a specific polar group of the present invention.
Using unprotected monomer
And / or contains a xanthate group
Using the compound as an initiator, perform a polymerization reaction under light irradiation
It can also be synthesized. For example, Takayuki Otsu “Polymer”Three
7, 248 (1988), Shunichi Himori, Ryuichi Otsu “Polym. Rep. Ja
p. ”37, 3508 (1988), JP-A-64-111,
64-26619, Nobuyuki Higashi, "Polymer Preprints, J
apan ”36 (6), 1511 (1987), M. Niwa, N. Higashi et.
 al “J. Macromol. Sci. Chem.”A24(5), 567 (198
7) can be synthesized according to the synthesis method described in
You.

In order to produce the dispersed resin particles used in the present invention, generally, the dispersion stabilizing resin [P], monomer (A) and monomer (C) as described above are mixed in a non-aqueous solvent. And heat polymerization in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, and butyllithium. Specifically, a method of adding a polymerization initiator to a mixed solution of the dispersion stabilizing resin [P], the monomer (A) and the monomer (C), and a solution in which the dispersion stabilizing resin [P] is dissolved A method in which the monomer (A) and the monomer (C) are added dropwise together with a polymerization initiator, or the total amount of the dispersion stabilizing resin [P] and the monomer (A) and the monomer (C) A method of optionally adding the remaining monomer (A) and monomer (C) together with a polymerization initiator to a mixed solution containing a part of the above, and further, a dispersion stabilizing resin [ P], a method of arbitrarily adding a mixed solution of the monomer (A) and the monomer (C) together with the polymerization initiator, and the like, and any method can be used.

The total amount of the monomers (A) and (C) is
It is about 5 to 50 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the non-aqueous solvent. The dispersion stabilizing resin [P] is used in an amount of 1 to 50 parts by weight, preferably 5 to 30 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. The polymerization temperature is about 40 to 180 ° C, preferably 50 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, the monomer (A) to be polymerized and granulated and When the unreacted product of the monomer (C) remains, it is preferable to remove the unreacted product by heating it to a temperature higher than the boiling point of the solvent or the monomer or distilling it off under reduced pressure.

As described above, the non-aqueous dispersed resin particles produced according to the present invention exhibit very stable dispersibility while existing as fine particles having a uniform particle size distribution.
In particular, even if the toner is repeatedly used for a long time in the developing device, the dispersibility is good and the re-dispersion is easy even if the developing speed is improved. Further, when fixed by heating or the like, a strong film was formed, and excellent fixability was exhibited. Further, the liquid developer of the present invention has a rapid development-fixing process and is excellent in dispersion stability, re-dispersibility and fixability even when a large-size master plate is used.

As described above, the high redispersibility of the latex particles of the present invention is attributable to the specific substituent-containing monomer (C) copolymerized with the insolubilizing monomer (A) and the specific And a star-type copolymer composed of the following blocks. That is, the monomer (C) is copolymerized with the monomer (A) which is insolubilized during polymerization granulation, but the monomer (C)
The specific substituent moiety contained therein forms particles by non-aqueous dispersion polymerization, so that it is designed to have good affinity for non-aqueous solvents, and thus penetrates into the particle structure. Since the solvation with the dispersion medium is better than the above, it is 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 aggregation between the particles is reduced. It is presumed that the effect of prevention is significantly enhanced. At the same time, the dispersion stabilizing resin [P] of the present invention has a block B composed of a long chain aliphatic group-containing polymer component having a high affinity for the non-aqueous solvent, and an affinity for the non-aqueous solvent. Small, insoluble monomer (A)
A star-type copolymer in which at least three or more polymer chains of an AB type block in which a block A composed of a polymer component having an affinity for is bonded to an organic molecule. Features. Thereby, the block A portion is sufficiently adsorbed by the physicochemical interaction at the time of polymerization granulation with respect to the dispersed resin particles, and the block B portion having a high affinity for the non-aqueous dispersion medium is formed with respect to the solvent. It is sufficiently solvated and has a steric repulsion effect (so-called,
Since there are at least three or more polymer chains (which result in tail-like adsorption), it is presumed that the effects of the present invention have been achieved by sufficiently and efficiently exhibiting the adsorption effect and the steric repulsion effect.

On the other hand, in a conventionally known random copolymer of the polymer component used in the block A and the polymer component used in the block B, a high-concentration component in which the component serving as the adsorbed portion is a solvate component is used. Adhesion to the dispersed resin particles is not sufficient because they are randomly bonded in the molecular chain, and furthermore, the adsorption pattern becomes a loop, so that the steric repulsion effect is also excluded, and the dispersion stability is sufficient. Was not. Further, A composed of block A and block B
A -B type block copolymer was developed, and the effect of improving dispersion stability was recognized as compared with the above random copolymer. However, in recent years, the effect of dispersion stability has not been sufficient for increasing the development speed of a plate making machine.

Further, high printing durability which does not cause deterioration of the toner image portion when printed as an offset master original plate is caused by the insolubilized monomers (A) and (C) and the dispersed polymer adsorbed thereon. It is presumed that this is achieved by good compatibility with each other, sufficient compatibility even under mild fixing conditions, and formation of a uniform and strong film.

A coloring agent may be used in the liquid developer of the present invention, 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 of chemically bonding a dispersing resin and a dye.
As described in JP-A-4-22955 and the like, there is a method of producing a dye-containing copolymer by using a monomer containing a dye in advance when producing by a polymerization granulation method.

Various additives may be added to the liquid developer of the present invention, if desired, for the purpose of enhancing the charge characteristics or improving the image characteristics. For example, Yuji Harazaki, "Electrophotography", Vol. What is specifically described in No. 2, p. 44 is used. For example, di-2-ethylhexylsulfosuccinic acid metal salt, naphthenic acid metal salt, higher fatty acid metal salt, lecithin, poly (vinylpyrrolidone), a copolymer containing a semi-maleic acid amide component, higher alcohols having 8 or more carbon atoms, Examples include compounds such as polyethers and silicone oil.

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 stabilizing the dispersion is also used as desired, and about 0.5 to 100 parts by weight can be added to 1000 parts by weight of the carrier liquid. The charge control agent as described above is a carrier liquid 100
0.001 to 1.0 parts by weight per 0 parts by weight is preferred. If desired, various additives may be added. The upper limit of the total amount of these additives is regulated by the electric resistance of the developer. That is, 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.
It is necessary to control within this limit.

[0081]

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.

Synthesis Example 1 of Dispersion Stabilizing Resin [P] Resin [P-1] Methyl methacrylate 50 g, methyl acrylate 50
g, a mixture of 7.8 g of an initiator [I-1] having the following structure and 100 g of tetrahydrofuran at a temperature of 50 ° C. under a nitrogen stream.
Was heated. This solution was added with a 400 W high-pressure mercury lamp at 10 c.
m for 8 hours through a glass filter from a distance of m for photopolymerization. The polymer was reprecipitated in 1 liter of methanol, and the precipitate was collected and dried. Next, the polymer 3
A mixed solution of 0 g, 70 g of stearyl methacrylate and 100 g of tetrahydrofuran was heated again to a temperature of 50 ° C. under a nitrogen stream. Next, after performing light irradiation for 16 hours in the same manner as described above, the obtained reaction product was treated with methanol 1.5 times.
The precipitate was collected in a liter, and the precipitate was collected and dried. The yield was 80 g, and the weight average molecular weight (Mw: Mw was a value determined by a GPC method in terms of polystyrene (GPC: size exclusion chromatography)) was 6 × 10 ^4. Was obtained.

[0083]

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[0084]

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Synthesis Examples 2 to 14 of Dispersion Stabilizing Resin [P]: Resins [P-2] to [P-14] In the synthesis example 1 of the dispersion stabilizing resin, the initiator [I-1]
A polymer was synthesized in the same manner as in Synthesis Example 1 except that 0.011 mol of an initiator described in Table A below was used instead of
The Mw of each polymer obtained was in the range of 4 × 10 ^{4 to} 6 × 10 ⁴ .

[0086]

[Table 1]

[0087]

[Table 2]

[0088]

[Table 3]

[0089]

[Table 4]

Synthesis Examples 15 to 28 of Dispersion Stabilizing Resin [P]: Resins [P-15] to [P-28] Each monomer corresponding to the polymer component of block A shown in Table B below, A mixture of 0.01 mol of the initiator [I-7] and 100 g of tetrahydrofuran was heated to 50 ° C. under a nitrogen stream with respect to all the monomers used. In this solution,
In the same manner as in Synthesis Example 1, light irradiation was performed for 12 hours to perform a polymerization reaction. Next, each of the obtained polymers was subjected to a predetermined amount (x: as solid content) shown in Table-B and each monomer corresponding to the polymer component of block B shown in Table-B below as Table-B
And a mixed solution to which tetrahydrofuran was added so that the concentration of all compounds was 60% by weight was again heated to a temperature of 55 ° C. under a nitrogen stream. Next, after performing light irradiation for 16 hours in the same manner as described above, the obtained reaction product was reprecipitated in 1.5 liters of methanol, and the precipitate was collected and dried. Yield 60-80
g of each polymer of 3 × 10 ^{4 to} 6 × 10 ⁴ was obtained.

[0091]

[Table 5]

[0092]

[Table 6]

[0093]

[Table 7]

[0094]

[Table 8]

Latex Particle Production Example 1: Latex Particle D-1 18 g of dispersion stabilizing resin [P-1] and 1 g of Isopar H
Temperature of 60 ° C. while stirring 77 g of the mixed solution under a nitrogen stream.
Was heated. 50 g of methyl methacrylate, 50 g of methyl acrylate, 3.0 g of octadecyl acrylate,
As a polymerization initiator, a mixed solution of 1.0 g of 2,2'-azobis (isovaleronitrile) (abbreviated to AIVN) and 200 g of Isopar H was added dropwise over 2 hours, followed by stirring for 2 hours. Further, A. I. V. N. Was added and stirred for 3 hours. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex having a polymerization rate of 95% and an average particle size of 0.20 μm. Particle size is CAPA-
500 (manufactured by Horiba, Ltd.).

Latex Particle Production Examples 2 to 11: Latex Particles D-2 to D-11 In Latex Particle Production Example 1, the dispersion stability described in Table C below was used instead of the dispersion stabilizing resin [P-1]. Latex particles D-2 to D-11 of the present invention were produced in exactly the same manner as in Production Example 1 except that a resin for use was used. The polymerization rate of each of the obtained latex particles was 90 to 95%, the average particle size was in the range of 0.15 to 0.20 μm, and the monodispersity was good.

[0097]

[Table 9]

Preparation Example 12 of Latex Particles: Preparation of Latex Particles D-12 12 g of dispersion stabilizing resin [P-17] and vinyl acetate 10
A mixture of 0 g, 2.0 g of octadecyl methacrylate and 384 g of Isopar H was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. As a polymerization initiator, A.I. I. V.
N. Was added and 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 88% polymerized and had an average particle size of 0.1%.
It was a 22 μm latex.

Latex Particle Production Examples 13 to 21: Monomer (A) (namely, methyl methacrylate and methyl acrylate), monomer used in Latex Particle Production Example 1 In place of (C) (that is, octadecyl acrylate) and dispersion stabilizing resin [P-1], the following table was used.
Preparation Example 1 except that the compounds described in D were used.
Latex particles were produced in the same manner as described above. The polymerization rate of each of the obtained latex particles was 85 to 98%, the average particle size was in the range of 0.15 to 0.25 μm, and the monodispersity was good.

[0100]

[Table 10]

[0101]

[Table 11]

Production Example 22 of Latex Particles: (Comparative Example A) In Production Example 1 of latex particles, instead of 14 g of the dispersion stabilizing resin [P-1], a resin [RP-
1] Except that 30 g was used, the polymerization rate was 98% and the average particle diameter was 0.40 μm in the same manner as in Production Example 1 of latex particles.
A white dispersion as latex particles was obtained.

[0103]

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Production Example 23 of Latex Particles: (Comparative Example B) In Production Example 1 of latex particles, instead of 14 g of the dispersion stabilizing resin [P-1], a resin [RP-
2] Except that 20 g was used, the polymerization rate was 90% and the average particle diameter was 0.26 μm in exactly the same manner as in Production Example 1 of latex particles.
A white dispersion as latex particles was obtained. (Japanese Unexamined Patent Publication No.
(Equivalent to -45455)

[0105]

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Production Example 24 of Latex Particles: (Comparative Example C) In Production Example 1 of latex particles, instead of 14 g of the dispersion stabilizing resin [P-1], a resin [RP-
3] Except that 20 g was used, the polymerization rate was 92% and the average particle size was 0.25 μm
A white dispersion as latex particles was obtained. (Japanese Unexamined Patent Publication
(Equivalent to -111860)

[0107]

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Example 1 A paint shaker (manufactured by Tokyo Seiki Co., Ltd.) containing 10 g of dodecyl methacrylate / acrylic acid copolymer (copolymerization ratio: 95/5 by weight), 10 g of nigrosine and 30 g of Shellsol 71 together with glass beads. And dispersed for 4 hours to obtain a fine dispersion of nigrosine. 6 g (as solid content) of resin particles of Production Example 1 of latex particles, 2.5 g of the above nigrosine dispersion, 15 g of FOC-1400 (manufactured by Nissan Chemical Co., Ltd., tetradecyl alcohol), and octadecene-half-maleic acid octadecylamide A liquid developer for electrostatography was prepared by diluting 0.08 g of the copolymer to 1 liter of Isopar G.

(Preparation of Comparative Developers A to C) Three kinds of comparative liquid developers A, B and C were prepared by replacing the resin particles in the production of the above liquid developer with the following resin particles. Comparative liquid developer A: resin particles obtained in Production Example 22 of latex particles. Comparative liquid developer B: resin particles obtained in Production Example 23 of latex particles. Comparative liquid developer C: resin particles obtained in Production Example 24 of latex particles.

These liquid developers were used in a fully automatic plate making machine ELP.
An ELP Master II type (manufactured by Fuji Photo Film Co., Ltd.), which is an electrophotographic photosensitive material, was exposed and developed using a 404V (manufactured by Fuji Photo Film Co., Ltd.) developer.
The plate making speed was 4 plates / min. Further, after 2500 sheets of ELP Master II type were processed, the presence or absence of toner adhesion to the developing device was observed. The blackening rate (image area) of the copied image was determined using a 30% original. The results are shown in Table-E.

[0111]

[Table 12]

When plate making was performed using each developer under the above-described plate making conditions, the developer which did not cause staining of the developing device and had a clear image on the 2500th plate making plate was only in the case of the present invention. . On the other hand, a master plate for offset printing (ELP master) obtained by making a plate from each developer is printed by an ordinary method, and the number of printed sheets until the occurrence of missing characters, blurred solid portions, etc. in the printed image is compared. As a result, the master plate obtained using the developer of the present invention was 100
It did not occur even with more than 00 sheets, and occurred on 3000 sheets in the master plate using Comparative Example A. In the case of Comparative Example B, 7000 sheets were generated, and in the case of Comparative Example C, 6,000 sheets were generated. As described above, only the developer using the resin particles of the present invention as a developer did not cause any stain on the developing device, and also significantly improved the number of printed master plates. In the case of Comparative Example B and Comparative Example C,
When used under severe plate making conditions (conventionally, the blackening rate of a copied image is about 8 to 10% at a plate making speed of 2 to 3 sheets / min), contamination of the developing device (especially on the back electrode plate) And the image quality of the copied image on the plate is affected after 2500 sheets (Dmax reduction, thin line blurring, etc.)
Came out. Also, the number of printed master plates was significantly reduced in Comparative Example A. These results
This shows that the resin particles of the present invention are clearly superior.

Example 2 White dispersion 10 obtained in Production Example 14 of latex particles
0 g and 1.5 g of Sumicalon Black at a temperature of 1
The mixture was heated to 00 ° C. and heated and stirred for 4 hours. After cooling to room temperature 2
By removing the remaining dye through a 00 mesh nylon cloth, a black resin dispersion having an average particle size of 0.24 μm was obtained. 32 g of the above black resin dispersion, 0.05 g of zirconium naphthenate, FOC-1600 (Nissan Chemical Co., Ltd.)
20 g of Hexadecyl alcohol)
A liquid developer was prepared by diluting 1 to 1 liter. When this was developed by the same device as in Example 1,
Even after the development of 2500 sheets, no toner adhesion stains occurred on the apparatus. Further, the image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after printing 10,000 sheets was also very clear.

Example 3 White dispersion 10 obtained in Production Example 16 of latex particles
0 g and 3 g of Victoria Blue B at a temperature of 7
The mixture was heated to 0 ° C 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 0.23 μm. A liquid developer was prepared by diluting 32 g of the above blue resin dispersion and 0.05 g of [octadecyl vinyl ether / tridecylamide half-maleic acid] copolymer to 1 liter of Isopar H. When this was developed with the same apparatus as in Example 1, no toner adhesion stains were seen on the apparatus even after 2500 sheets were developed. Further, the image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after printing 10,000 sheets was also very clear.

Example 4 White resin dispersion 32 obtained in Production Example 15 of latex particles
g, 2.5 g of the nigrosine dispersion obtained in Example 1, FOC
A liquid developer was prepared by diluting 20 g of -1400 (manufactured by Nissan Chemical Co., Ltd., tetradecyl alcohol) and 0.02 g of a semi-docosanilamide of a copolymer of diisobutylene and maleic anhydride to 1 liter of Isopar G. did. When this was developed by the same apparatus as in Example 1, no toner adhesion stains were seen on the apparatus even after 2500 sheets were developed. Further, the image quality of the obtained master plate for offset printing and the image quality of the printed matter after printing 10,000 sheets were clear. After the developer was allowed to stand for three months, the same treatment as above was performed, but it was not different from that before the lapse of time.

Example 5 10 g of poly (decyl methacrylate), 30 g of Isopar H and 8 g of alkali blue were placed in a paint shaker together with glass beads, and dispersed for 2 hours to obtain a fine dispersion of alkali blue. 30 g of the white resin dispersion D-12 obtained in Production Example 12 of latex particles, 4.2 g of the above-mentioned alkali blue dispersion, 15 g of isostearyl alcohol, and a half-docosanyl amidated product of a copolymer of diisobutylene and maleic anhydride 0 A liquid developer was prepared by diluting 0.06 g to 1 liter of Isopar G. When this was developed by the same apparatus as in Example 1, no toner adhesion stains were seen on the apparatus even after 2500 sheets were developed. In addition, the image quality of the obtained master plate for offset printing and the image quality of printed matter after 10,000 sheets were printed were very clear.

Examples 6 to 19 Liquid developers were prepared in the same manner as in Example 5 except that the latex particles D-12 were replaced by the respective latexes shown in Table F below.

[0118]

[Table 13]

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,
Both redispersibility and printing durability were good.

[0120]

According to the present invention, a liquid developer having excellent redispersibility, storage stability and stability, and excellent image reproducibility and fixability can be obtained. In particular, a liquid having excellent redispersibility and stability of particles even when the development-fixing process for an electrophotographic plate making system is accelerated, and excellent printing durability even when a large-size master plate is used. A developer was obtained.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03G 9/13 G03G 9/135

Claims (2)

(57) [Claims] 1. A resistance 10 ⁹ [Omega] cm or more and a dielectric constant of 3.5 or less of the carrier liquid, the liquid developer for electrostatic photography composed by dispersing at least resin particles, the dispersion resin particles, non-aqueous At least one monofunctional monomer (A) that is soluble in a solvent but insolubilized by polymerization, containing a specific substituent represented by the following general formula (I), and At least one monomer (C) copolymerizable with (A), a phosphono group, a carboxyl group,
Sulfo group, hydroxyl group, formyl group, amino group,-
P (＝ O) (OH) R ¹ group [R ¹ is a —R ² group or —OR ²
R ² represents a hydrocarbon group], -CONR ³ R ⁴
A —SO ₂ NR ³ R ⁴ group (R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group), and at least one polar group selected from cyclic acid anhydride-containing groups. Block A containing at least one polymer component and / or at least one polymer component corresponding to the monofunctional monomer (A)
And at least one polymer component represented by the following general formula (II):
AB-type block polymer chain composed of the seed-containing block B is bonded to at least three organic molecules,
And each AB type block polymer chain is bonded to the organic molecule at one end opposite to the end bonded to block B of the polymer main chain of block A, and has a weight average molecular weight of Polymer resin particles obtained by polymerizing a mixture containing at least one kind of a dispersion stabilizing resin [P] of 5 × 10 ³ to 1 × 10 ⁶ each comprising a star copolymer. A liquid developer for electrostatography, comprising: 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) -, - CON
_{(R 22) -, - N} (R 22) CO -, - N (R 22) SO 2
_{-, - SO 2 N (R} 22) -, - NHCO 2 - or -NH
It represents a CONH- (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 may be substituted, or represents a hydrocarbon group having 1 to 18 carbon atoms which may have the following formula 3 in the main chain bond. 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 is -COO-, -CONH-, -CON
(E ² )-[where E ² is an aliphatic group or a group represented by the aforementioned general formula (I)
II), -OCO-, -CON
_{HCOO -, - CH 2 COO -} , - (CH 2) s OCO-
[Where s represents an integer of 1 to 4], -O- or -C ₆
Represents H ₄ —COO—. a ¹ and a ² may be the same or different from each other, and each represents a hydrogen atom, an alkyl group, —COO
-E ³ or ^{_{-CH 2 COO-E 3 (E}} 3 where represents an aliphatic group). Embedded image In the general formula (II), X ¹ represents -COO-, -OCO-,-(C
H ₂ ) _x COO-,-(CH ₂ ) _x OCO- [where x is 1
Represents an integer of to 3], or represents -O-. Y ¹ represents an aliphatic group having 8 or more carbon atoms. b ¹ and b ^2, which may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-Z ^1, or a hydrocarbon -COO-Z ¹ via a hydrogen group (wherein Z ¹ represents a hydrogen atom or a hydrocarbon group which may be substituted). 2. In the dispersion stabilizing resin [P], each block of the AB block copolymer component constituting each polymer chain has a block A / block B ratio of 1 to 50.
The liquid developer for electrostatography according to claim 1, wherein the liquid developer has a weight ratio of / 99 to 50 (weight ratio).