JPH06337549A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To improve dispersibility and redispersibility and printing resistance of the liquid developer of the electrostatic photography, and the resist performance of a toner image part as a developer, for an electrophotographic graphic arts system, and further to improve the printing resistance of the obtained original printing plate for an offset master. CONSTITUTION:A block A contains (a) monofunctional monomer; (b) an oligomer obtained by combining a specified polar group with one end of a main polymer chain and having a molecular weight of <=1X10<4>; (c) a polyfunctional monomer; and (d) a specified polar group-containing polymer component or a polymer component corresponding to the monomer (a). The dispersion stabilizing resin [P] of a star type copolymer having a molecular weight of 2X10<4>-10X10<6> is obtained by combining at least 3 of A-B type block polymer chains comprising the block A and a block B containing a polymer component of the formula. The liquid developer for the electrophotographic photography contains polymer resin particles obtained by polymerizing a solution containing the resin [P]. In the formula, X<1> is a bonding group; Y1 is a >=8C aliphatic group; each of b<1> and b<2> is H, halogen, cyano, a hydrocarbon group, -COO-Z<1> optionally combined through a hydrocarbon group; and Z<1> is H or a hydrocarbon group.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid developer for electrostatic photography, which is obtained by dispersing at least a resin in a carrier liquid having an electric resistance of 10 ⁹ Ωcm or more and a dielectric constant of 3.5 or less, and particularly redispersion. And a liquid developer excellent in resist property.

[0002]

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

In such a developer, the resin is dispersed as insoluble latex particles in the form of particles having a diameter of several nm to several hundreds of nm. However, these particles should be as uniform in particle size as possible over time. It is important that particles do not agglomerate / precipitate, and if these are not satisfied, the reproducibility of the image area will become poor, the non-image area will become dirty, or the developer delivery pump of the developing device will become clogged. Will end up.

As an improvement of these, a non-aqueous dispersion polymerization method for obtaining insoluble latex particles having a fine particle size and good monodispersity has been proposed and various studies have been made.
For example, U.S. Pat. Nos. 3,990,980 and 4,61
No. 8,557, JP-A Nos. 1-257969 and 2-74.
956, 1-282566, 2-173667
No. 4,842,975, JP-A No. 62-151868.
No. 1,237,668, and No. 2-168276.
No. 4,46,354, etc., describes a method of modifying the surface of latex particles by allowing an insolubilizing monomer and another compound having a physicochemical interaction to coexist. It is disclosed that redispersibility and storage stability can be improved.

[0005]

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

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

When a known liquid developer containing insoluble resin particles having good redispersibility is used for such an electrophotographic plate making system, the resist property of the toner image area is sufficiently high when the non-image area is sufficiently hydrophilized. However, there was a case where the image part was missing. In particular, this problem becomes noticeable in areas where the area of the toner image portion such as fine lines / characters or halftone dots is small, and deterioration of the printed matter was observed. Further, insoluble latex particles having high durability to the treatment liquid (for example, styrene-based latex) have sufficient resist properties, but have poor charge stability and redispersibility as toner particles. Since the fixing property of the toner particles is inferior and sufficient fixing requires a high heat and a long fixing time, the complexity of the apparatus has been a problem.

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

[0009]

The above objects of the present invention are as follows.
In a liquid developer for electrostatic photography, wherein at least resin particles are dispersed in a non-aqueous solvent having an electric resistance of 10 ⁹ Ωcm or more and a dielectric constant of 3.5 or less, the dispersed resin particles are compatible with the non-aqueous solvent. A monofunctional monomer (A) which is soluble but is insolubilized by polymerization, a carboxyl group, a sulfo group, or a carboxyl group only at one end of the main chain of the polymer comprising a repeating unit represented by the following general formula (I): A hydroxyl group, a formyl group, an amino group, a phosphono group, and a -P (= O) (OH) G ¹ group [wherein G ¹ represents a hydrocarbon group or an -OG ² group (G ² represents a hydrocarbon group); An oligomer (B) having a number average molecular weight of 1 × 10 ⁴ or less, which is formed by bonding at least one polar group selected from the group consisting of 2) and a polymerizable functional group copolymerizable with the monomer (A). A polyfunctional monomer (D) having at least one, and a phosphono group, Bokishiru group, a sulfo group, a hydroxyl group, a formyl group, an amino group, -P (= O) (OH) R
¹ group [R ¹ represents -R ² group or -OR ² group, R ² represents hydrocarbon group], -CONR ³ R ⁴ group, -SO ₂ NR ³ R ⁴ group [R ³ and R ⁴ are , Each independently represents a hydrogen atom or a hydrocarbon group], and a polymer component containing at least one polar group selected from a cyclic acid anhydride-containing group and / or the monofunctional monomer (A And a block B containing at least one polymer component corresponding to the formula (II) and a block B containing at least one polymer component represented by the following general formula (II): Each of the A-B type block polymer chains is composed of at least three organic molecules bound to each other, and each of the AB type block polymer chains has one end opposite to the end bound to the block B of the polymer main chain of the block A. Are bound and have a weight average molecular weight of 2 × 10 ⁴ to 1 × 1
No. ^6, which is a polymer resin particle obtained by polymerizing a mixture containing a dispersion-stabilizing resin [P] made of a star-type copolymer, each of which is at least one kind. Liquid developer for use.

[0010]

[Chemical 5]

In the formula (I), V ⁰ is --COO-- or --OCO.
_{-, - (CH 2) r} COO -, - (CH 2) r OCO -, - O
_{-, - SO 2 -, -} CONHCOO -, - CONHCO
^{NH -, - COND 11 -,} - SO 2 ND 11 -, or a phenylene group (hereinafter, a phenylene group in the "-Ph-",
"-Ph-" represents a 1,2-phenylene group, a 1,3-phenylene group and a 1,4-phenylene group). Here, D ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, and r represents an integer of 1 to 4. a ¹ and a ² are
Which may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-D ^12, or a hydrocarbon representative of the -COO-D ¹² through a group (wherein D ¹²
Represents a hydrogen atom or an optionally substituted hydrocarbon group).
D ⁰ is a hydrocarbon group having 1 to 22 carbon atoms, or the following general formula
It represents a substituent selected from the substituents represented by (III).

[0012]

[Chemical 6]

In the formula (III), D ²¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. B ¹ and B ² may be the same or different from each other, and each is —O—, —CO—, —CO.
_{2 -, - OCO -, -} SO 2 -, - N (D 22) -, - CO
N (D ²²⁾ - or -N (D ²²⁾ CO- represents a (wherein D ²² represents the same content as the D ^11). A ¹ and A ² are
They represent hydrocarbon groups having 1 to 18 carbon atoms, which may be the same as or different from each other, may be respectively substituted, or may have Chemical Formula 7 below interposed in the bond of the main chain.

[0014]

[Chemical 7]

In the chemical formula 7, B ³ and B ⁴ may be the same as or different from each other, and have the same contents as the above B ¹ and B ^2, and A ⁴
Represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and D ²³ has the same content as D ²¹ above. m, n and p
May be the same as or different from each other and each represents an integer of 0 to 4. However, m, n, and p do not become 0 at the same time.

[0016]

[Chemical 8]

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

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

The non-aqueous dispersion resin particles (hereinafter also referred to as latex particles), which is the most important constituent component of the present invention, is a dispersion-stabilizing resin [P] which is the star block copolymer of the present invention in a non-aqueous solvent. ] And the oligomer (B), in the presence of at least one monofunctional monomer (A) and at least one polyfunctional monomer (D), the mixture is polymerized and granulated. Is.

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

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

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

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

[0024]

[Chemical 9]

In the formula (IV), T ¹ is --COO-- or --OCO.
_{-, - CH 2 OCO -,} - CH 2 COO -, - O -, - C
ONHCOO -, - CONHOCO -, - SO 2 -, -
^{CON (W 1) -, -} SO 2 N (W 1) -, or a phenylene group (-Ph-). W ¹ represents a hydrogen atom or an optionally substituted aliphatic group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group). Base, 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 and the like).

D ¹ is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2,2-dichloroethyl group) , 2,2,2-trifluoroethyl group, 2
-Bromoethyl group, 2-glycidylethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2,3-
Dihydroxypropyl group, 2-hydroxy-3-chloropropyl group, 2-cyanoethyl group, 3-cyanopropyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-
Methanesulfonylethyl group, 2-ethoxyethyl group,
N, N-dimethylaminoethyl group, N, N-diethylaminoethyl group, trimethoxysilylpropyl group, 3-bromopropyl group, 4-hydroxybutyl group, 2-furfurylethyl group, 2-thienylethyl group, 2- Pyridylethyl group, 2-morpholinoethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-phosphoethyl group, 3-sulfopropyl group, 4
-Sulfobutyl group, 2-carboxamidoethyl group, 3
-Sulfoamidopropyl group, 2-N-methylcarboxamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

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

As a specific monofunctional monomer (A),
For example, vinyl esters or allyl esters of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.); acrylic acid, methacrylic acid, crotonic acid, itaconic acid, Alkyl esters or amides of an unsaturated carboxylic acid such as maleic acid having 1 to 4 carbon atoms which may be substituted (eg, an alkyl group such as methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2- Bromoethyl group, 2-fluoroethyl group, trifluoroethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-benzenesulfonylethyl group, 2 −
(N, N-dimethylamino) ethyl group, 2- (N, N-
Diethylamino) ethyl group, 2-carboxyethyl group,
2-phosphoethyl group, 4-carboxybutyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-chloropropyl group, 2-hydroxy-3-chloropropyl group, 2-
Furfurylethyl group, 2-pyridinylethyl group, 2-thienylethyl group, trimethoxysilylpropyl group, 2-
Carboxamidoethyl group, etc.); Styrene derivative (for example, styrene, vinyltoluene, α-methylstyrene,
Vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N, N
-Dimethylaminomethylstyrene, vinylbenzenecarboxamide, vinylbenzenesulfoamide, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid; cyclic acid anhydrides of maleic acid, itaconic acid; Acrylonitrile; methacrylonitrile; a heterocyclic compound containing a polymerizable double bond group (specifically, for example, "Polymer Data Handbook-Basic Edition", edited by The Society of Polymer Science, pp. 175-184, Baifukan (1986). ), For example, N-vinyl pyridine, N
-Vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.)
Etc. The monomer (A) may be used in combination of two or more kinds.

Next, the oligomer (B) used in the present invention will be further described. The oligomer (B) has a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, a phosphono group, and-on only one end of the main chain of the polymer composed of the repeating unit represented by the following general formula (I). P (= O) (OH) G ¹ group [wherein G ¹ represents a hydrocarbon group or a -OG ² group (G ² represents a hydrocarbon group)] is bonded to at least one polar group. Is an oligomer having a number average molecular weight of 1 × 10 ⁴ or less.

[0030]

[Chemical 10]

In the formula (I), V⁰Is -COO-, -OCO
-,-(CH₂)_rCOO-,-(CH ₂)_rOCO-, -O
-, -SO₂-, -CONHCOO-, -CONHCO
NH-, -COND¹¹-, -SO₂ND¹¹-Or Fe
It represents a nylene group (-Ph-). Where D¹¹Is a hydrogen atom
Represents a hydrocarbon group having 1 to 22 carbon atoms, r is an integer of 1 to 4
Indicates a number. a¹And a²May be the same as or different from each other
Hydrogen atom, halogen atom, cyano group, hydrocarbon
Group, -COO-D¹², Or -COO via a hydrocarbon group
-D¹²Represents Where D¹²Is a hydrogen atom or substituted
It shows a good hydrocarbon group. D⁰Is carbonization of 1 to 22 carbon atoms
A hydrogen group or a substituent represented by the following general formula (III) is selected.
Represents a substituent group.

[0032]

[Chemical 11]

In the formula (III), D ²¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. B ¹ and B ² may be the same or different from each other, and each is —O—, —CO—, —CO.
_{2 -, - OCO -, -} SO 2 -, - N (D 22) -, - CO
N (D ²²⁾ - or -N (D ²²⁾ representing a CO-. Here, D ²² has the same contents as D ¹¹ . A ¹ and A ² may be the same or different from each other, and each may be substituted,
Alternatively, the following chemical formula 12 represents a hydrocarbon group having 1 to 18 carbon atoms which may be interposed in the bond of the main chain.

[0034]

[Chemical 12]

In the chemical formula 12, B ³ and B ⁴ may be the same or different from each other, and have the same contents as the above B ¹ and B ^2, and A
⁴ represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and D ²³ has the same meaning as D ²¹ above. m, n and p
May be the same as or different from each other and each represents an integer of 0 to 4. However, m, n, and p do not become 0 at the same time.

The hydrocarbon groups contained in a ¹ , a ² , V ⁰ and D ⁰ in formula (I) each have the indicated carbon number (as an unsubstituted hydrocarbon group). The group may be substituted.

In the general formula (I), D ¹¹ in the substituent represented by V ⁰ is a hydrogen atom, and a preferable hydrocarbon group is an optionally substituted alkyl group having 1 to 22 carbon atoms (for example, Methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, nonyl group,
Decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl Group, 3-bromopropyl group, etc.), an alkenyl group having 4 to 18 carbon atoms and which may be substituted (eg, 2-methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl- 2-pentenyl group, 1-pentenyl group, 1-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, decenyl group, dodecenyl group, tridecenyl group, hexadecenyl group, octadecenyl group, linolel group, etc.), carbon Number 7 to 1
2 optionally substituted aralkyl groups (for example, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group,
Bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), alicyclic group having 5 to 8 carbon atoms which may be substituted (eg, cyclohexyl group, 2-cyclohexyl) Ethyl group, 2-cyclopentylethyl group, etc.) or an optionally substituted aromatic group having 6 to 12 carbon atoms (eg, phenyl group, naphthyl group, tolyl group, xylyl group,
Propylphenyl group, butylphenyl group, octylphenyl group, dodecylphenyl group, methoxyphenyl group, ethoxyphenyl group, butoxyphenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group,
Bromophenyl group, cyanophenyl group, acetylphenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group and the like).

When V ⁰ represents a phenylene group (-Ph-), the benzene ring may have a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.),
Alkyl group (eg, methyl group, ethyl group, propyl group,
Butyl group, chloromethyl group, methoxymethyl group, etc.) and the like.

A ¹ and a ² may be the same as or different from each other, and preferably a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom etc.), a cyano group and a carbon number of 1 to 3
Alkyl group (eg, methyl group, ethyl group, propyl group, etc.), —COO-D ¹³ or —CH ₂ COO-D ¹³ (D
¹³ represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group, which may be substituted, and specifically, the above-mentioned D ¹¹ was explained. Represents the same content as).

When D ⁰ represents a hydrocarbon group having 1 to 22 carbon atoms, it has the same contents as those described for D ¹¹ above.

The case where D ⁰ represents a substituent represented by the general formula (III) will be described in detail. A ¹ and A ² may be the same as or different from each other, may be respectively substituted, or may have the above Chemical Formula 12 interposed in the bond of the main chain and have a hydrocarbon group having 1 to 18 carbon atoms (hydrocarbon group). Examples of the group include an alkyl group, an alkenyl group, an aralkyl group, and an alicyclic group, and specific examples thereof include the same contents as the specific examples listed for D ¹¹ . More specific examples of A ¹ and A ² are: -C (D ³¹ ).
(D ³² )-[D ³¹ and D ³² represent a hydrogen atom, an alkyl group, a halogen atom or the like],-(CH = CH)-, a phenylene group (-Ph-), a cyclohexylene group [hereinafter referred to as a cyclohexylene group. the - expressed in, "-C ₆ H _10" "- C ₆ H ₁₀ -"
Includes a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, and a 1,4-cyclohexylene group], and the above chemical formula 12 and the like, which are composed of any combination of atomic groups.

Further, in the linking group in the general formula (I): -V ^0- (A ¹ -B ¹ ) _m- (A ² -B ² ) _n -D ²¹ , V ⁰ to D ²¹ (that is, V ⁰ , A ¹ , B ¹ , A ² ,
The total number of atoms in the linked main chain composed of B ² and D ²¹ ) is 8
The above-mentioned structure is preferable. Where A ¹ and A ¹
There in the case of the hydrocarbon group interposing the reduction 12 in the binding of the main ^{chain, -B 3 - (A 4 -B} 4) p -D 23 is also included in the connecting backbone. The number of atoms in the main chain is, for example, V
^{When 0} represents -COO- or -CONH-, an oxo group (= O group) and a hydrogen atom are not included as the number of atoms, and a carbon atom, an ether-type oxygen atom, and a nitrogen atom which form the connecting main chain are the atoms. Included as a number. Therefore, -COO-
And -CONH- are counted as 2 atoms. Similarly,
If D ²¹ represents -C ₉ H _19, a hydrogen atom is not contained in the number of atoms, the carbon atoms are included. Therefore, in this case, it is counted as 9 atoms.

In the repeating unit represented by the general formula (I) as described above, when D ⁰ represents a substituent represented by the general formula (III), that is, at least two or more repeating units are contained in the molecule. When it contains a specific polar group, more specifically, the following repeating units can be given as examples. In the following, a is -H or -CH
₃ ; R is a C ₁ -C ₁₈ alkyl group; R'is a hydrogen atom or a C ₁ -C ₁₈ alkyl group; and k ₁ and k ₂ are each 1 to 1.
2 is an integer; m ₁ is an integer of ₁ to 100.

[0044]

[Chemical 13]

[0045]

[Chemical 14]

[0046]

[Chemical 15]

[0047]

[Chemical 16]

Further, the oligomer (B) used in the present invention
In, in addition to the repeating unit represented by the general formula (I), other repeating units may be contained as a copolymerization component. The other copolymerization component may be any compound as long as it is a monomer copolymerizable with the monomer corresponding to the repeating unit of the general formula (I). For example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, vinyl acetic acid, 4-pentenoic acid, etc., and esters or amides of these unsaturated carboxylic acids, having 1 to 1 carbon atoms.
22 fatty acid vinyl esters or allyl esters, vinyl ethers, styrene and styrene derivatives,
Examples thereof include unsaturated bond-containing heterocyclic compounds. Specific examples thereof include the compounds exemplified as the above-mentioned monomer (A), but are not limited thereto.

In the total of the repeating units of the oligomer (B), the repeating unit component represented by the general formula (I) is preferably contained in an amount of 40% by weight or more, more preferably 60 to 100% by weight. is there. When the amount of the component represented by the general formula (I) is less than 40% by weight based on the total amount, the mechanical strength of the image portion formed by the dispersed resin particles is not sufficiently retained, and thus the printing durability when used as an offset master plate. The improvement effect cannot be seen. The oligomer (B) of the present invention has a number average molecular weight of 1 × 10 ⁴ or less, preferably 1 × 10 ³ to 1 × 10 ⁴ , and more preferably 2
× 10 ^{3 to} 9 × 10 ³ . When the upper limit of the number average molecular weight of the oligomer (B) exceeds 1 × 10 ⁴ , the printing durability is deteriorated. On the other hand, if the molecular weight is too small, stains tend to occur, and it is preferably 1 × 10 ³ or more.

In the polar group bonded to only one end of the polymer main chain of the oligomer (B) used in the present invention, -P (=
O) (OH) G ¹ group, G ¹ is a hydrocarbon group or —OG
² groups (G ² represents a hydrocarbon group) are represented. G ¹ or G ²
The hydrocarbon group represented by is preferably a hydrocarbon group having 1 to 18 carbon atoms, more preferably an optionally substituted aliphatic group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, Butyl group, pentyl group, hexyl group, butenyl group, pentenyl group, hexenyl group, 2-chloroethyl group, 2-cyanoethyl group, cyclopentyl group, cyclohexyl group, benzyl group, phenethyl group, chlorobenzyl group, bromobenzyl group, etc.), Or, it represents an aromatic group which may be substituted (eg, phenyl group, tolyl group, xylyl group, mesityl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

In the polar group of the present invention, the amino group is --N.
H _2, represents a -NHG ³ or -NG ³ G ^4. G ³ and G ⁴ each represent a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrocarbon group having 1 to 8 carbon atoms, and specifically, the hydrocarbon group of G ¹ or G ² described above. Represents the same content as. Even more preferably, the hydrocarbon group of G ¹ , G ² , G ³ and G ⁴ may be an alkyl group having 1 to 4 carbon atoms which may be substituted, an optionally substituted benzyl group, or an optionally substituted one. A phenyl group is mentioned.

Here, the polar group has a chemical structure in which it is directly bonded to one end of the polymer main chain or bonded through an arbitrary linking group. The group connecting the polymer main chain component of the oligomer (B) and the polar group includes a carbon-carbon bond (single bond or double bond), a carbon-hetero atom bond (as a hetero atom, for example, an oxygen atom, a sulfur atom). , Nitrogen atom, silicon atom, etc.), and any combination of atomic groups of heteroatom-heteroatom bond. Among the oligomers (B) of the present invention, preferred are those represented by the following general formula (Ia) or general formula (Ib).

[0053]

[Chemical 17]

In the general formulas (Ia) and (Ib), a ¹ ,
a ² , V ⁰ and D ⁰ have the same contents as those in the general formula (I), and G ⁰ represents the above-mentioned polar group bonded to one end in the formula (I). L represents a single bond or, -CG ⁵ G ⁶ -
[Here, G ⁵ and G ⁶ are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, an alkyl group (for example, a methyl group, an ethyl group). , Propyl group) and the like], −
(CH = CH) -, - C≡C -, - C 6 H 10 - ( cyclohexylene group), - Ph- (phenylene group), - O-,
-S -, - CO -, - NG 7 -, - COO -, - SO
^{_{2 -, - CONG 7 -,}} - SO 2 NG 7 -, - NHCOO
It represents a linking group composed of any combination of —, —NHCONH— and the like. However, G ⁷ is a hydrogen atom or a carbon number of 1 to
18 hydrocarbon group, specifically D ^{11 in} formula (I)
The same contents as those explained in are mentioned. In the polymer main chain, phosphono group, carboxyl group, sulfo group,
Hydroxyl group, formyl group, amino group, -P (= O)
Those which do not contain a copolymerization component containing a polar group of (OH) G ¹ group are preferable.

The oligomer (B) of the present invention in which a specific polar group is bonded only to one end of the polymer main chain has various reagents at the end of a living polymer obtained by conventionally known anionic polymerization or cationic polymerization. A method of reacting (method of ionic polymerization method), a method of radical polymerization using a polymerization initiator and / or a chain transfer agent containing a specific polar group in the molecule (method of radical polymerization method),
Alternatively, it can be easily produced by a synthetic method such as a method of converting a polymer having a reactive group at a terminal obtained by an ionic polymerization method or a radical polymerization method as described above into a specific polar group of the present invention by a polymer reaction. You can Specifically, P. Dreyfuss & R. P. Quir
k, Encycl. Polym. Sci. Eng. ，
7 , 551 (1987), Yoshiki Nakajo, Yuya Yamashita "Dyes and Pharmaceuticals" 30 , 232 (1985), Akira Ueda, Susumu Nagai "Science and Industry" 60 , 57 (1986), etc. and references cited therein. It can be produced by the method described.

As the polymerization initiator containing a specific polar group in the above-mentioned molecule, for example, 4,4'-azobis (4-cyanovaleric acid), 4,4'-azobis (4-cyanovaleric acid chloride), 2,2'-azobis (2-cyanopropanol), 2,2'-azobis (2-cyanopentanol), 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propioamide], 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propioamide}, 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ) -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- (5-
Hydroxy-3,4,5,6-tetrapyrimidine-2-
Il) 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] and other azobis compounds.

Further, examples of the chain transfer agent containing a specific polar group in the molecule include mercapto compounds, disulfide compounds, iodine-substituted compounds and the like, but mercapto compounds are preferable. For example, thioglycolic acid, 2-mercaptopropionic acid, thiomalic acid,
Examples thereof include 2-mercaptoethanesulfonic acid, 2-mercaptoethanol, 2-mercaptoethylamine, thiosalicylic acid, α-thioglycerin, 2-phosphonoethylmercaptan, hydroxythiophenol, and derivatives of these mercapto compounds.

These polymerization initiators and / or chain transfer agents are contained in an amount of 0.5 to 20 parts by weight based on the total amount of the monomers corresponding to the repeating unit represented by the general formula (I) and other polymerizable monomers. %, Preferably 1 to 10% by weight.

Preferred oligomers (B) for use in the present invention are represented by the general formula (Ia) or (Ib). Specific examples of the moiety represented by G--L-- in these formulas are shown below. Show. However, the scope of the present invention is not limited to these. In the following, k
₁ is an integer of 1 or 2, k ₂ is an integer of ₂ to 16, and k ₃ is an integer of 1 or 3. R represents an alkyl group having 1 to 6 carbon atoms.

[0060]

[Chemical 18]

[0061]

[Chemical 19]

[0062]

[Chemical 20]

Next, a monomer (D) which is used together with the monofunctional monomer (A) and the oligomer (B) and has two or more polymerizable functional groups copolymerizable with the monomer (A). (Less than,
The polyfunctional monomer (D) will be described below.
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, it is represented by the following general formula (V). The functional groups shown may be mentioned.

[0064]

[Chemical 21]

[0065] 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) And the oligomer (B) and polymerize with the monomer (A) to form a polymer insoluble in the non-aqueous solvent.

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

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

The dispersion resin of the present invention comprises at least one kind of each of the monomer (A), the oligomer (B) and the monomer (D), and importantly, is synthesized from these monomers and oligomers. If the obtained resin is insoluble in the non-aqueous solvent, a desired dispersed resin can be obtained. Specifically, the oligomer (B) is added in an amount of 0.1 to 0.1 with respect to the insolubilizing monomer (A).
It is preferable to use 10% by weight, and more preferably 0.3 to 5% by weight. The monomer (D) having two or more polymerizable functional groups used in the present invention is 2 of all the monomers.
It is used in an amount of 0 mol% or less, preferably 10 mol% or less, 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 , and more preferably 1 × 10 ⁴ to 1 × 10 ⁶ .

Next, the dispersion stabilizing resin [P] of the present invention will be described. A stable resin dispersion of the solvent-insoluble polymer produced by polymerizing a mixture containing at least one monomer (A), an oligomer (B) and a monomer (D) in a non-aqueous solvent. The dispersion-stabilizing resin [P] of the present invention used for the above purpose has a weight-average molecular weight of 2 × 10 4, which is formed by bonding at least three polymer chains of the AB type block copolymer component in the organic molecule. ^{It is a 4} to 1 × 10 ⁶ star-type copolymer. One block (block A) bonded to the organic molecule includes a phosphono group, a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, and -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 NR ³
R ⁴ group [R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group], and a polymer component containing at least one polar group selected from a cyclic acid anhydride-containing group, and / or Alternatively, it is constituted by containing at least one polymer component corresponding to the monofunctional monomer (A). Another block (block B) contains at least one polymer component composed of the repeating unit represented by the general formula (II). Here, the order of arrangement in the polymer chains of block A and block B is such that the polymer main chain of block A is bound to an organic molecule at one end opposite to the end bound to block B. Then, the resin [P] is schematically shown as the following chemical formula 22.

[0071]

[Chemical formula 22]

In Chemical formula 22, X represents an organic molecule,
(A) represents block A, (B) represents block B,
(A)-(B) represents a polymer chain. Also, such AB
The upper limit of the type block polymer chains contained in the organic molecule is at most 15, usually about 10.

The abundance ratio of the block A and the block B in the star type copolymer is 1 to 50/99 to 50 (weight ratio), and preferably 5 to 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, and more preferably 1 to 15 parts by weight in 100 parts by weight of the dispersion stabilizing resin [P]. Further, when the specific polar group-containing polymer component does not exist in the block A, the polymer component corresponding to the monofunctional monomer (A) is preferably 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 is
50% by weight of the dispersion stabilizing resin [P] is preferable.
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)
Of the specific polar group-containing polymer component contained in the block A or the polymer component represented by the general formula (II) contained in the block B). The redispersion stability of the dispersed resin particles obtained by polymerizing the monofunctional monomer (A) and the polyfunctional monomer (D) will decrease. On the other hand, when the proportion exceeds the predetermined proportion, the average particle size of the dispersed resin particles obtained by the polymerization reaction of the monofunctional monomer (A) and the polyfunctional monomer (D) becomes coarse,
The monodispersity of the particle distribution of the particles is reduced.

Dispersion stabilizing resin [P] used in the present invention
Is soluble in an organic solvent, and specifically, at least 5 parts by weight or more of the dispersion stabilizing resin is dissolved in 100 parts by weight of a toluene solvent at a temperature of 25 ° C. The weight average molecular weight (Mw) of the dispersion stabilizing resin [P] of the present invention is 2 × 10 ⁴ to 1 × 10 ⁶ , and preferably 3 × 10 ⁴ to 1 × 10 ⁵ .

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

In a specific polar group, -P (= O) (OH) R ¹
In the group, R ¹ represents -R ² group or -OR ² group, and R ²
Represents a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group for R ² is preferably an optionally substituted aliphatic group having 1 to 8 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, butenyl group, pentenyl group, Hexenyl group, 2-chloroethyl group, 2-cyanoethyl group, cyclopentyl group, cyclohexyl group, benzyl group, phenethyl group, chlorobenzyl group, bromobenzyl group, etc., and optionally substituted aromatic group (eg, phenyl group, tolyl group). Group, xylyl group, mesityl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

In a 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 4 carbon atoms). 10, preferably a hydrocarbon group having 1 to 8 carbon atoms which may be substituted)
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, and examples of the cyclic acid anhydride contained include aliphatic dicarboxylic acid anhydride and aromatic dicarboxylic acid anhydride. Things can be mentioned. Examples of the aliphatic dicarboxylic acid anhydride include succinic anhydride, glutaconic anhydride, maleic anhydride, cyclopentane-1,2.
-Dicarboxylic acid anhydride, cyclohexane-1,2-dicarboxylic acid anhydride, cyclohexene-1,2-dicarboxylic acid anhydride, 2,3-bicyclo [2,2,2] octanedicarboxylic acid anhydride, and the like, These aliphatic dicarboxylic acid anhydrides may be substituted with, for example, a halogen atom such as a chlorine atom or a bromine atom, an alkyl group such as a methyl group, an ethyl group, a butyl group or a hexyl group. Examples of aromatic dicarboxylic acid anhydrides include phthalic anhydride, naphthalene-dicarboxylic acid anhydride, pyridine-dicarboxylic acid anhydride, thiophene-dicarboxylic acid anhydride, and the like. Examples include halogen atoms such as chlorine atom and bromine atom, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, hydroxyl group, cyano group, nitro group, alkoxycarbonyl group (as an alkoxy group, For example, it may be substituted with a methoxy group, an ethoxy group or the like).

Further, among the specific polar groups, the amino group is -N
H _2, represents a -NHR ⁵ or -NR ⁵ R ^6. R ⁵ and R ⁶ represent a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms. More preferably, it represents a hydrocarbon group having 1 to 7 carbon atoms, and specific examples thereof include those having the same contents as the hydrocarbon group represented by R ² .

The hydrocarbon group represented by R ² , R ³ , R ⁴ , R ⁵ and R ⁶ is even 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 may be mentioned.

The monomer corresponding to the polymer component containing the above specific polar group may be any monofunctional monomer containing at least one specific polar group.
For example, it is described in "Polymer Data Handbook [Basic Edition]" edited by the Society of Polymer Science, Japan, and Fuifukan (1986). Specifically, acrylic acid, α- and / or β-substituted acrylic acid (for example, α-acetoxy form, α-acetoxymethyl form, α- (2-amino) methyl form, α-chloro form, α-form)
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 (for example, 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4
-Ethyl-2-octenoic acid, etc.), maleic acid, maleic acid half-esters, maleic acid half-amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic acid vinyl group or allyl group And a compound containing the polar group in the substituent of the amide derivative and the ester derivative of these carboxylic acids or sulfonic acids.

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, f is —H or —
CH ₃ is shown, n is an integer of 2 to 10, and 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) ( OH)
R _a is shown. Here, R _a, R _b represents an alkyl group having 1 to 4 carbon atoms. X ₂ represents a -COOH or -OH.

[0083]

[Chemical formula 23]

[0084]

[Chemical formula 24]

[0085]

[Chemical 25]

Next, block B of dispersion stabilizing resin [P]
The repeating unit represented by the general formula (II) which constitutes is 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,
Examples thereof include a linolel group.

B ¹ and b ² may be the same as or different from each other, and are preferably a hydrogen atom, a halogen atom (eg chlorine atom, bromine atom etc.), a cyano group and a carbon number of 1 to 3.
Alkyl group (eg, methyl group, ethyl group, propyl group, etc.), —COO-Z ¹ or —CH ₂ COO-Z ¹ [Z
¹ is a hydrogen atom or an optionally substituted hydrocarbon group having 22 or less carbon atoms (for example, an alkyl group, an alkenyl group,
Aralkyl group, alicyclic group, aryl group, etc.)].

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

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

On the other hand, the organic molecule according to the present invention, which is formed by binding at least three polymer chains, is not particularly limited as long as the molecular weight of the molecule is 1,000 or less. For example, a trivalent hydrocarbon residue shown in Chemical formula 26 below can be mentioned.

[0091]

[Chemical formula 26]

[Here, 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 linked to the polymer chain, and at least one of r ^{3 to} r ⁶ is linked to the polymer chain. ] These organic residues consist structure alone or any combination thereof, in the case of combination, -O -, - S -, - N (r 7) -, - COO -, - C
^{ON (r 7) -, -} SO 2 -, - SO 2 N (r 7) - { wherein r ⁷ represents a hydrogen atom or a hydrocarbon group}, - NHCOO
-, -NHCONH-, a hetero ring containing a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom (for example, a thiophene ring,
Pyridine ring, pyran ring, imidazole ring, benzimidazole ring, furan ring, piperidine ring, pyrazine ring, pyrrole ring, piperazine ring, etc.) and the like.

As another example of the organic molecule which binds the polymer chain, there is mentioned one constituted by a combination of the following chemical formula 27 and the above-mentioned binding unit. However, specific examples of the organic molecule according to the present invention are not limited to these.

[0094]

[Chemical 27]

The star type copolymer [P] of the present invention can be synthesized by utilizing the conventionally known method for 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. However, when this reaction is used, the "specific polar group" of the present invention is used as a protected functional group to polymerize, and then the protective group is removed. The protection of the specific polar group of the invention with a protecting group and the elimination of the protecting group (deprotection reaction) can be easily carried out by utilizing the conventionally known knowledge. For example, various references are given in the above cited document, and further, Yoshio Iwakura and Keisuke Kurita "Reactive Polymer", Kodansha Co., Ltd. (1977
), TW Greene “Protective Groups in Organic S
ynthesis ”(John Wiley & Sons, 1981), JFW Mc
Omic “Protective Groups in Organic Chemistry” (Pl
The method described in detail in a review article such as enum Press, 1973) can be appropriately selected and performed.

As another method, a monomer of the present invention which is not protected with a specific polar group is used, and a compound containing a dithiocarbament group and / or a compound containing a xanthate group is used as an initiator. It can also be synthesized by performing a polymerization reaction under light irradiation. For example, Takayuki Otsu “Polymer” 3
7 , 248 (1988), Shunichi Hinomori, Ryuichi Otsu “Polym. Rep. Ja
p. " 37 , 3508 (1988), JP-A 64-111, JP-A 64-26619, Nobuyuki Higashi et al.," Polymer Preprints, J. "
apan ” 36 (6), 1511 (1987), M. Niwa, N. Higashi et
al “J. Macromol. Sci. Chem.” A24 (5), 567 (198
It can be synthesized according to the synthetic method described in 7) and the like.

In order to produce the latex particles used in the present invention, generally, the dispersion stabilizing resin [P] as described above,
A polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, butyllithium, etc., prepared from a monofunctional monomer (A), an oligomer (B) and a polyfunctional monomer (D) in a non-aqueous solvent. It may be carried out by heat polymerization in the presence of. In particular,
Method of adding polymerization initiator to mixed solution of dispersion stabilizing resin [P], monomer (A), oligomer (B) and monomer (D), solution in which dispersion stabilizing resin [P] is dissolved A method of dropping the monomer (A), the oligomer (B) and the monomer (D) together with the polymerization initiator, or the total amount of the dispersion stabilizing resin [P] and the monomer (A) and the oligomer. A method of optionally adding the remaining monomer (A), oligomer (B) and monomer (D) together with a polymerization initiator to a solution containing (B) and a part of the monomer (D), Further, there is a method of optionally adding a mixed solution of the dispersion stabilizing resin [P], the monomer (A), the oligomer (B) and the monomer (D) together with the polymerization initiator into a non-aqueous solvent. Yes,
It can be manufactured by any method.

The total amount of the monomer (A), the oligomer (B) and the monomer (D) is 5 with respect to 100 parts by weight of the non-aqueous solvent.
It is about 80 parts by weight, preferably 10 to 50 parts by weight. The amount of the oligomer (B) is about 0.1 to 10 parts by weight, preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the monomer (A). Dispersion stabilizing resin [P]
The soluble resin is 1 to 100 parts by weight of all the monomers [monomer (A) and monomer (D)] used above.
It is 100 parts by weight, preferably 10 to 50 parts by weight. The amount of the polymerization initiator is 0.1 to 5% by weight based on the total amount of the monomers.
Is appropriate. The polymerization temperature is about 50 to 180 ° C, preferably 60 to 120 ° C. Reaction time is 1
15 hours is preferred.

When a polar solvent such as the alcohols, ketones, ethers and esters described above is used in combination with the non-aqueous solvent used in the reaction, or the monomer (A) and the monomer which are polymerized and granulated are used. When the unreacted substance of the body (D) remains, it is removed by heating the solvent or above the boiling point of the monomer (A) or the monomer (D) and then distilling off or distilling under reduced pressure. Is preferred.

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

The liquid developer of the present invention which brings about the above effects is a star-type copolymer containing a specific block used together with the insolubilizing monomer (A) and monomer (D), and further the oligomer (B). It depends on coalescence. That is, the dispersion stabilizing resin [P] of the present invention comprises a block B composed of a polymer component containing a long-chain aliphatic group having a high affinity for the non-aqueous solvent and a low affinity for the non-aqueous solvent. , 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 the insolubilizing monomer (A) is bound in an organic molecule, It is a star type copolymer. As a result, the block A portion is sufficiently adsorbed to the dispersed resin particles by physicochemical interaction during polymerization granulation, and the block B portion having a large affinity for the non-aqueous dispersion medium is for the solvent. Since there are at least three polymer chains that are sufficiently solvated and have a sufficient steric repulsion effect (so-called tail-like adsorption), the adsorption effect and steric repulsion effect are sufficiently efficiently expressed. It is estimated that the effect of the present invention was achieved by doing so.

On the other hand, in the conventionally known random copolymer of the polymer component used in the block A and the polymer component used in the block B, the component serving as the adsorbing part is composed of a solvating component. Adhesion to dispersed resin particles is not sufficient because they are randomly bonded in the molecular chain, and the steric repulsion effect is also excluded due to the adsorption pattern becoming a loop, and dispersion stability is sufficient. It wasn't. Furthermore, 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, the effect of dispersion stability is still insufficient for recent developments such as speeding up of the development speed of a plate making machine.

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

In the liquid developer of the present invention, a colorant may be used if desired. The colorant is not particularly limited, and various conventionally known pigments or dyes can be used. When the dispersed resin itself is colored, for example, as one of coloring methods, there is a method of physically dispersing it in a dispersed resin by using a pigment or a dye, and many pigments or dyes to be used are known. There is. For example, magnetic iron oxide powder, powdered lead iodide, carbon black, nigrosine, alkali blue, Hansa yellow, quinacridone red,
Examples include phthalocyanine blue. As another method of coloring, there is a method of dyeing a dispersed resin with a preferable dye as described in JP-A-57-48738. Alternatively, as another method, JP-A-53-53
There is a method of chemically bonding a dispersion resin and a dye as disclosed in JP-A-54029, or in the case of producing by a polymerization granulation method as described in JP-B-44-22955. There is a method of preparing a dye-containing copolymer by using a monomer containing a dye in advance.

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

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

[0107]

EXAMPLES The following will describe the effects of the present invention in more detail by showing Production Examples of dispersion stabilizing resin, latex particles and Examples of the present invention, but the present invention is not limited to these. Absent.

Production Example of Oligomer (B) 1: Oligomer B-12,3-Diacetoxypropylmethacrylate 100
g, 5-mercaptopropionic acid 5 g, toluene 150
A mixed solution of 50 g of methanol and 50 g of methanol was heated to a temperature of 50 ° C. while stirring under a nitrogen stream. 1.5 g of 2,2'-azobis (isobutyronitrile) (abbreviation AIBN) was added and reacted for 4 hours. Furthermore, A. I. B. N.
0.4 g was added and reacted for 4 hours. After cooling, the reaction solution was reprecipitated in 2 liters of a mixed solution of methanol / water [(4/1) volume ratio], the methanol solution was separated by decantation, and the viscous material was dried, followed by a colorless viscous material. Was obtained. The number average molecular weight of the polymer was 3,300.

[0109]

[Chemical 28]

Production Examples 2 to 31 of Oligomer (B): Oligomer B-2 to B-31 In Production Example 1 of Oligomer B-1, instead of 2,3-diacetoxypropyl methacrylate and 3-mercaptopropionic acid. , Except that a methacrylate monomer and a mercapto compound corresponding to Table-A below were used,
Operating in the same manner as in Production Example 1, each oligomer B-2 to B-3
1 was produced. The number average molecular weight of the obtained oligomer was 2,500 to 5,000.

[0111]

[Table 1]

[0112]

[Table 2]

[0113]

[Table 3]

[0114]

[Table 4]

Production Example 32 of Oligomer (B): Oligomer B-32 2- (n-nonylcarbonyloxy) ethyl crotonate 100 g, toluene 150 g, and ethanol 50 g.
The mixed solution of 1 was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 4,4'-azobis (4-cyanovaleric acid)
(Abbreviation: ACV) 8g was added and reacted for 5 hours. C. V. 2 g was added and reacted for 4 hours. The obtained reaction solution was cooled and then reprecipitated in a mixed aqueous solution of methanol / water [(4/1) volume ratio], the aqueous methanol solution was separated by decantation, and the viscous material was dried. The yield was 70 g and the number average molecular weight of the polymer was 2,600.

[0116]

[Chemical 29]

Production Examples 33 to 41 of Oligomer (B): Oligomer B-33 to B-41 In Production Example 32, the polymerization initiator A. C. V. In the same manner as in Production Example 32 except that the azobis compound of the following Table-B was used in place of and the monomer corresponding to the following structure was used in place of 2- (n-nonylcarbonyloxy) ethyl crotonate. Each oligomer B-33 to B-41 was produced. The number average molecular weight of the obtained oligomer is 2,000 to
It was 4,000.

[0118]

[Table 5]

[0119]

[Table 6]

Synthesis example of dispersion stabilizing resin [P] 1: Resin [P-1] 50 g of methyl methacrylate and 50 g of methyl acrylate
g, a mixture of 7.8 g of an initiator [I-1] having the following structure and 100 g of tetrahydrofuran under a nitrogen stream at a temperature of 50 ° C.
Warmed to. 10c of this solution with 400W high pressure mercury lamp
Light was irradiated from a distance of m through a glass filter for 8 hours to perform 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, in the same manner as above, after performing light irradiation for 16 hours, the obtained reaction product was treated with methanol 1.5
It is reprecipitated in liter, the precipitate is collected, dried and the weight average molecular weight [Mw: Mw is a value by polystyrene conversion GPC method (GPC: size exclusion chromatography)] is 6 × 10 ⁴ at a yield of 80 g. A polymer of

[0121]

[Chemical 30]

[0122]

[Chemical 31]

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

[0124]

[Table 7]

[0125]

[Table 8]

[0126]

[Table 9]

[0127]

[Table 10]

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

[0129]

[Table 11]

[0130]

[Table 12]

[0131]

[Table 13]

[0132]

[Table 14]

Production Example 1 of Latex Particles: Latex Particles D-1 20 g of dispersion stabilizing resin [P-1], 50 g of methyl methacrylate, 50 g of methyl acrylate, oligomer B.
A mixed solution of 1.0 g of -17, 1 g of ethylene glycol dimethacrylate and 384 g of Isopar H was heated to a temperature of 60 ° C. while stirring under a nitrogen stream. 0.8 g of 2,2'-azobis (isovaleronitrile) (abbreviation AIVN) was added as a polymerization initiator, and the reaction was carried out for 3 hours.
After 20 minutes from the addition of the initiator, white turbidity occurred and the reaction temperature was 8
It rose to 8 ° C. 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 under a reduced pressure of 20 mmHg to distill off unreacted monomers. 20 after cooling
The resulting white dispersion was a latex having a polymerization rate of 98% and an average particle size of 0.28 μm. The particle size is CAPA-500 (manufactured by Horiba, Ltd.)
It was measured at.

Production Examples 2 to 21 of Latex Particles: Latex Particles D-2 to D-21 In Production Example 1 of latex particles, the dispersion stabilizing resin [P-1], oligomer B-17, and ethylene glycol dimethacrylate are used. Instead of using the dispersion stabilizing resin, the oligomer (B) and the monomer (D) shown in Table E below, the same operation as in Production Example 1 was repeated except that the latex particles D-2 of the present invention were used. ~ D-21 was produced. The degree of polymerization of each latex particle obtained was 95 to 98%, the average particle diameter was in the range of 0.15 to 0.30 μm, and the monodispersity was good.

[0135]

[Table 15]

[0136]

[Table 16]

Production Example 22 of Latex Particles: Latex Particle D-22 18 g of dispersion stabilizing resin [P-25], vinyl acetate 10
A mixed solution of 0 g, 2.4 g of oligomer B-2, 5 g of divinyl adipate and 375 g of Isopar H was heated to a temperature of 40 ° C. with stirring under a nitrogen stream. A. I.
V. N. 0.7 g was added and the mixture was reacted for 3 hours. I.
V. N. 0.5 g was added and reacted for 3 hours. Further, the mixture was stirred at a temperature of 100 ° C. for 2 hours, and unreacted vinyl acetate was distilled off. After cooling, it was passed through a nylon cloth of 200 mesh, and the obtained white dispersion was a latex having a polymerization rate of 93% and an average particle size of 0.25 μm.

Production Examples 23-30 of Latex Particles: Latex Particles D-23 to D-30 Monomer (A) (that is, vinyl acetate), oligomer B-2, and dispersion used in Production Example 22 of latex particles. A latex was prepared in the same manner as in Production Example 22 above except that the compounds shown in Table F below were used instead of the stabilizing resin [P-25] and the monomer (D) (that is, divinyl adipate). Particles were produced. The degree of polymerization of each latex particle obtained was 90 to 98%, and the average particle diameter was 0.15 to 0.15.
Within the range of 0.30 μm, the monodispersity was also good.

[0139]

[Table 17]

Production Example 31 of Latex Particles: (Comparative Example A) 20 g of a dispersion stabilizing resin [RP-1] having the following structure, 50 g of methyl methacrylate, 50 g of methyl acrylate,
Latex particles having a polymerization rate of 99% and an average particle size of 0.30 μm were obtained in exactly the same manner as in Production Example 1 of latex particles except that a mixture of 3 g of ethylene glycol diacrylate and 384 g of Isopar H was used. (JP-A-4-3
(Corresponding to No. 13763)

[0141]

[Chemical 32]

Production Example 32 of Latex Particles: (Comparative Example B) A mixture of 20 g of the dispersion stabilizing resin [RP-1], 50 g of methyl methacrylate, 50 g of methyl acrylate, and 384 g of Isopar H was used. In the same manner as in Production Example 1 of Latex Particles, latex particles having a polymerization rate of 99% and an average particle size of 0.18 μm were obtained. (Corresponding to JP-A-3-225353)

Production Example 33 of Latex Particles: (Comparative Example C) Production Example 3 except that 1.0 g of oligomer B-17 was further added in Production Example 32 (Comparative Example B) of latex particles.
The same treatment as in No. 2 was conducted to obtain a polymerization rate of 98.5% and an average particle diameter of 0.1
20 μm latex particles were obtained. (JP-A-4-463
(Equivalent to No. 54)

Production Example 34 of Latex Particles: (Comparative Example D) A latex was synthesized in the same manner as in Production Example 1 except that 3 g of ethylene glycol diacrylate was used in Production Example 1 of latex particles. The obtained latex had a polymerization rate of 99% and an average particle size of 0.25 μm.

Example 1 10 g of a dodecyl methacrylate / acrylic acid copolymer (copolymerization ratio; 95/5 weight ratio), 10 g of nigrosine and 30 g of Isopar G were placed in a paint shaker (manufactured by Tokyo Seiki Co., Ltd.) together with glass beads. Put in, disperse for 4 hours,
A fine dispersion of nigrosine was obtained. Latex Particle Production Example 1: 30 g of D-1 resin dispersion, 2.5 g of the above nigrosine dispersion, branched octadecyl alcohol FOC
-1800 (manufactured by Nissan Chemical Industries, Ltd.) 15 g, and octadecene-half-maleic acid octadecylamide copolymer 0.0
A liquid developer for electrostatic photography was prepared by diluting 7 g to 1 liter of Isopar G.

(Preparation of Comparative Developers A to D) In the production of the above liquid developer, four kinds of comparative liquid developers A, B, C and D were used instead of the resin dispersion described below. It was made. Comparative liquid developer A: Resin dispersion of Production Example 31 of latex particles. Comparative liquid developer B: resin dispersion of Production Example 32 of latex particles. Comparative liquid developer C: resin dispersion of Production Example 33 of latex particles. Comparative liquid developer D: resin dispersion of Production Example 34 of latex particles.

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

[0148]

[Table 18]

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

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

[0151]

[Chemical 33]

(Note 3) Toner image resist property: An original plate prepared by the same method as the above (Note 2) was etched using a desensitizing solution ELP-EX (manufactured by Fuji Photo Film Co., Ltd.). After passing through once, it was dipped in the hydrophilic treatment liquid E-1 for the photoconductive layer binder resin having the following formulation for 5 minutes, washed with water and dried. The image portion of the obtained printing original plate was observed with an optical microscope, and the presence or absence of damage in the image portion was visually evaluated. <Preparation of Hydrophilization Treatment Liquid E-1> Monoethanolamine 8
0g, Newcol B4SN (manufactured by Nippon Emulsifier Co., Ltd.) 8
g and 100 g of benzyl alcohol are dissolved in distilled water 1
After the volume was adjusted to 1 liter, the pH was adjusted to 13.0 with potassium hydroxide to prepare a treatment liquid E-1.

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

From the results shown in Table-G, the developers of the present invention, Comparative Examples C and D did not cause stains on the developing device, and the image on the 2000th plate was clear. Indicated. This shows that the dispersibility and redispersibility are good. On the other hand, in the developers of Comparative Examples A and B, the redispersibility was deteriorated and the reproducibility of the actual copied image was adversely affected.

When the mechanical strength of the toner image area was evaluated by forcibly rubbing, each toner particle was good. That is, it was confirmed that the particles of the present invention have a sufficient fixability in practice.

Further, when the zinc oxide and the binder resin B-1 in the non-image area of the plate surface after plate-making are chemically treated to be hydrophilic, the image area is sufficiently resisted by the toner layer and the image area is deficient. When it was examined under a forced condition whether or not the toner particles did not occur, defects other than the toner particles of the present invention occurred in the fine areas of the toner image portion such as fine lines and fine characters. Further, when printing was carried out as an offset master original plate after processing under ordinary desensitizing processing conditions, clear printed matter was obtained after printing 5,000 sheets of the invention and Comparative Example A. Comparative Example B
, The deterioration of the reproducibility of the copied image at the time of plate making appeared on the printed matter as it was, and thin lines and fine characters were missing from the imprinting. Further, in Comparative Examples C and D, thin lines and thin characters were missing about 2,000 sheets after printing during printing.

As described above, only the liquid developer of the present invention is
In an electrophotographic plate making system using an electrophotographic photosensitive member having improved printing characteristics, excellent dispersibility / redispersibility and printing durability were satisfied.

Example 2 Latex Particle Production Example 29: 30 g of a resin dispersion of D-29, branched hexadecyl alcohol FOC-1600
(Nissan Chemical Co., Ltd.) 10 g, and octadecyl vinyl ether / semi-maleic acid dodecylamide copolymer 0.0
A liquid developer for electrostatic photography was prepared by diluting 8 g to 1 liter of Isopar G.

(Preparation of Comparative Developers C'and D ') In the production of the above liquid developer, two types of liquid developers C'and D'for comparison were used instead of the resin dispersion described below. It was made. Comparative liquid developer C ′: resin dispersion of Preparation Example 33 of latex particles. Comparative liquid developer D ′: resin dispersion of Production Example 34 of latex particles.

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

[0161]

[Table 19]

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

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

[0164]

[Chemical 34]

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 photoconductive layer in the non-image area, washed with water for 30 seconds, and then dried with a dryer. Air dried. <Prescription of Treatment Liquid E-2> Potassium silicate 40 g Potassium hydroxide 10 g Ethanol 100 g Water 800 g The presence or absence of fine lines and fine characters in the image portion of this printing plate was checked with a magnifying glass (PEAK (PEAK ( Manufactured by K.K.).

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

From the results of Table-H, the present invention and Comparative Example D '
The liquid developer of No. 3 showed good redispersibility, and the image of the plate after 2000 sheets was also good. However, Comparative Example C '
Causes toner dust and stains on the developing section.
With respect to the image of the plate, after 2000 sheets, thin lines and fine characters were missing.

Next, the plate after plate making was made to elute the non-image area by using an alkaline processing liquid to obtain a master plate for offset master. At this time, in Comparative Example D ′, a small area portion of the toner image portion such as a thin line or a thin character was missing. This indicates that the resist property of the toner layer with respect to the treatment liquid was not sufficient, and the toner layer was dissolved and eluted during the treatment. On the other hand, in the present invention and Comparative Example C ′, these phenomena were not observed and sufficient resist properties were shown.

Further, as the master for offset master,
When actually printed, the image quality of the printed matter of the present invention was clear even after printing 100,000 sheets or more. However, Comparative Example C'has poor reproducibility of the copied image at the time of plate making, and Comparative Example D'has insufficient resist property to the processing liquid for dissolving and removing the non-image area. Since sufficient image reproducibility cannot be obtained, the image quality of the printed matter deteriorates after printing, and a printed matter with sufficient image quality cannot be obtained.

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

Example 3 10 g of tetradecyl methacrylate / methacrylic acid copolymer (copolymerization ratio; 95/5 weight ratio), 1 nigrosine
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. Production Example 30 of Latex Particles: 30 g of the resin dispersion of D-30, 2.5 g of the above nigrosine dispersion, and 0.0 of hexadecene / half-maleic acid octadecylamide copolymer.
6 g and 20 g of FOC-1800 to 1 of Isopar G
A liquid developer for electrostatic photography was prepared by diluting to 1 liter.

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

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

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

[0175]

[Chemical 35]

[0176]

[Chemical 36]

The original plate thus obtained was passed through an etching machine once using ELP-EX, and then immersed in a hydrophilic treatment liquid E-3 for a photoconductive layer-binding resin having the following formulation for 3 minutes. After that, it was washed with water and dried. <Preparation of Treatment Liquid E-3> 80 g of diethanolamine, 5 g of Neosoap (manufactured by Matsumoto Yushi Co., Ltd.) and 80 g of methyl ethyl ketone were dissolved in distilled water to 1 liter, and then adjusted to pH 13.5 with potassium hydroxide, Treatment liquid E-3
Was produced.

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

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

[0180]

[Table 20]

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

Examples 16 to 25 Similar to Example 2 except that the latex particles shown in Table J below were used in place of the latex particles D-29 of the liquid developer of the present invention. Then, each liquid developer was prepared.

[0183]

[Table 21]

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

Example 26 Production Example 25 of Latex Particles A mixture of 100 g of the white resin dispersion obtained in D-25 and 1.5 g of Sumicaron Black was heated to a temperature of 100 ° C. and heated and stirred for 4 hours.
After cooling to room temperature, a 200-mesh nylon cloth was passed through to remove residual dye, whereby a black resin dispersion having an average particle size of 0.21 μm was obtained. 30 g of the above black resin dispersion and 0.05 g of zirconium naphthenate were added to Shellsol 7
A liquid developer was prepared by diluting 1 to 1 liter. When this was developed by the same apparatus as in Example 1,
Even after the development of 2000 sheets, the toner adhesion stain on the apparatus did not occur at all. Further, in the same manner as in Example 1, printing was performed as a master plate for offset master by plate making and etching treatment, and after 3000 sheets, the printed matter had clear image quality.

Example 27 Production Example 26 of Latex Particles A mixture of 100 g of the white resin dispersion obtained in D-26 and 3 g of Victoria Blue B was heated to a temperature of 70 ° C. to 80 ° C. and stirred for 6 hours.
After cooling to room temperature, a 200-mesh nylon cloth was passed through to remove the residual dye, thereby obtaining a blue resin dispersion having an average particle size of 0.25 μm. A liquid developer was prepared by diluting 32 g of the blue resin dispersion and 0.05 of zirconium naphthenate to 1 liter of Isopar H. When this was developed by the same apparatus as in Example 3, no toner adhesion stain was found on the apparatus even after development of 2000 sheets. Further, the image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after printing 3,000 sheets was also very clear.

[0187]

According to the present invention, a liquid developer having excellent dispersion stability, redispersibility and fixability can be obtained. In particular, as a developer for an electrophotographic plate making system, it has excellent resist properties in the toner image area, and thus markedly improves the printing durability of the obtained offset master original plate.

Claims (2)

[Claims] 1. A liquid developer for electrostatic photography comprising at least resin particles dispersed in a non-aqueous solvent having an electric resistance of 10 ⁹ Ωcm or more and a dielectric constant of 3.5 or less, wherein the dispersed resin particles are A monofunctional monomer (A) that is soluble in an aqueous solvent but becomes insoluble by polymerization, and a carboxyl group only at one end of the main chain of a polymer composed of repeating units represented by the following general formula (I). group, a sulfo group, a hydroxyl group, a formyl group, an amino group, a phosphono group, and -P (= O) (OH) G 1 group [wherein G ¹ is a hydrocarbon group or -OG ² group (G ² are hydrocarbon Represents a group)] and has a number average molecular weight of 1 × 10 ⁴ or less, which is formed by bonding at least one polar group selected from the group (A), and a polymerization copolymerizable with the monomer (A). Polyfunctional monomer (D) having two or more functional groups, and Honomoto, carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, -P (= O) (OH) R
¹ group [R ¹ represents -R ² group or -OR ² group, R ² represents hydrocarbon group], -CONR ³ R ⁴ group, -SO ₂ NR ³ R ⁴ group [R ³ and R ⁴ are , Each independently represents a hydrogen atom or a hydrocarbon group], and a polymer component containing at least one polar group selected from a cyclic acid anhydride-containing group and / or the monofunctional monomer (A And a block B containing at least one polymer component corresponding to the formula (II) and a block B containing at least one polymer component represented by the following general formula (II): Each of the A-B type block polymer chains is composed of at least three organic molecules bound to each other, and each of the AB type block polymer chains has one end opposite to the end bound to the block B of the polymer main chain of the block A. Are bound and have a weight average molecular weight of 2 × 10 ⁴ to 1 × 1
0 ⁶ a, electrostatographic, characterized in that the dispersion of the stabilizing resin (P) consisting of star copolymer is a polymer resin particles obtained by each polymerizing reaction mixture containing at least one Liquid developer. [Chemical 1] In formula (I), V ⁰ is -COO-, -OCO-,-(C
_{H 2) r COO -, -} (CH 2) r OCO -, - O -, - SO
_2- , -CONHCOO-, -CONHCONH-,-
COND ¹¹ −, —SO ₂ ND ¹¹ —, or a phenylene group (wherein D ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, and r represents an integer of 1 to 4). a ¹ and a ² may be the same as or different from each other, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group or —COO—.
D ¹² or —COO—D ¹² via a hydrocarbon group is represented (wherein D ¹² represents a hydrogen atom or an optionally substituted hydrocarbon group). D ⁰ represents a hydrocarbon group having 1 to 22 carbon atoms or a substituent selected from the substituents represented by the following general formula (III). [Chemical 2] In formula (III), D ²¹ represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. B ¹ and B ² may be the same or different from each other, and each is —O—, —CO—, —CO ₂ —, —OC.
_{O -, - SO 2 -,} - N (D 22) -, - CON (D 22)
- or an -N (D ²²⁾ CO- (wherein D ²² represents the same content as the D ^11). A ¹ and A ² may be the same as or different from each other, and each may be substituted, or the following chemical formula 3 may be interposed in the bond of the main chain, having 1 to 18 carbon atoms.
Represents a hydrocarbon group of. [Chemical 3] In the chemical formula 3, B ³ and B ⁴ may be the same as or different from each other, and have the same contents as the above B ¹ and B ^2, and A ⁴ represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms. D ²³ shows the same contents as D ²¹ above. m, n and p may be the same or different and each represents an integer of 0 to 4. However, m, n, and p do not become 0 at the same time. [Chemical 4] In formula (II), X ¹ is —COO—, —OCO—, — (C
H ₂ ) _x COO-,-(CH ₂ ) _x OCO- [where x is 1 to
Represents an integer of 3], or represents -O-. Y ¹ has 8 carbon atoms
The above aliphatic groups are represented. b ¹ and b ² may be the same as or different from each other, and each is a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO—Z ¹ , or —COO—Z ¹ via a hydrocarbon group (wherein Z ¹ represents a hydrogen atom or an optionally substituted hydrocarbon group). 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 electrostatic photography according to claim 1, wherein the liquid developer is / 99 to 50 (weight ratio).