JPH0619218A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To obtain a liq. developer excellent in dispersion stability, redispersibility, fixability and hydrophilic processing soln. resistance by dispersing a resin grain in a nonaqueous solvent. CONSTITUTION:The dispersion resin grain is an interdigital copolymer contg. a monofunctional monomer A, an oligomer B with a polar group linked to the end of the principal chain of a polymer consisting of a unit shown by formula I and having <=1X10<4> number average mol.wt., a multifunctional monomer D and a macromonomer M with a polymerizable double-bonded group shown by formula II linked to the end of the polymer principal chain as the coplymeizable components, and a component shown by formula III is incorporated as the unit of the principal chain of copolymer. The soln. contg. a dispersion stabilizing resin P is polymerized in the nonaqueous solvent. In the formulas I, II and III, V<0> is -COO-, etc., a<1> and a<2> are hydrogen atom, etc., D<0> is a 1-22C hydrocarbonic group, X<0> and X<1> are -CH2OCO-, etc., and b<1>, b<2>, d<1> and d<2> are halogen atom, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a liquid developer for electrostatic photography, 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 electrophotographic liquid developer 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 an aliphatic hydrocarbon, 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, and these particles should be as uniform in particle size as possible over time. It is important that particles do not agglomerate / precipitate, and if these are not satisfied, the reproducibility of the image area may become poor, the non-image area may become dirty, or the developer delivery pump of the developing device may 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. 3,12,666, No. 3-15862, etc., a method of improving with a resin for stabilizing soluble dispersion is disclosed in U.S. Pat. No. 4,842,975, JP-A-62-151868,
In JP-A-1-237668, JP-A-2-168276, JP-A-3-77965, JP-A-3-91765 and the like, latex particles are formed by coexisting an insolubilizing monomer and another compound having a physicochemical interaction. A method for modifying the surface is described, and it is disclosed that the dispersibility of particles, particle size, redispersibility, and storage stability can be improved.

[0005]

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

In recent years, as the latter method, 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., by converting the binder resin used in the photosensitive layer 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 which enables the production of an offset printing original plate having excellent oil sensitivity and printing durability by electrophotography. Still another object of the present invention is to provide a liquid developer which enables the production of an original plate for offset printing using ink jet recording, cathode ray tube recording and recording methods of various changing steps such as pressure change or electrostatic change. Is.

[0009]

The above objects of the present invention are as follows.
In a liquid developer for electrostatic photography, in which at least resin particles are dispersed in a non-aqueous solvent having an electric resistance of 10 ⁹ Ωcm or more and a dielectric constant of 3.5 or less, the dispersed resin particles are compatible with the non-aqueous solvent. At least one monofunctional monomer (A) that is soluble but is insolubilized by polymerization, a carboxyl group only at one end of the main chain of the polymer composed of repeating units represented by the following general formula (I) , Sulfo group, hydroxyl group, formyl group, amino group, phosphono group, and -P (= O) (OH) G ¹ group [wherein G ¹ is a hydrocarbon group or -OG ² group (G ² is a hydrocarbon group. At least one of 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 Many having two or more possible polymerizable functional groups At least one potential monomer (D), and the main polymer at one end of the chain only formed by combining a polymerizable double bond group represented by the following general formula (II) weight average molecular weight 1 × 10 A comb-type copolymer containing ^{3 to} 2 × 10 ⁴ macromonomers (M) as a copolymerization component, and the following general formula as a repeating unit of the main chain part and / or comb part of the copolymer. A polymer resin particle obtained by polymerizing a solution containing a dispersion-stabilizing resin [P] soluble in the non-aqueous solvent, containing at least the component (III). This is achieved by a liquid developer for electrophotography.

[0010]

[Chemical 6]

In the formula (I), V ⁰ is --COO-- or --OCO.
_{-, - (CH 2) r} COO -, - (CH 2) r OCO
-, - O -, - SO 2 -, - CONHCOO -, - CO
^{NHCONH -, - COND 11 -,} - SO 2 ND 11 -,
Alternatively, it represents a phenylene group (hereinafter, the phenylene group is represented by -Ph-, and -Ph- includes 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 may be the same or different from each other, each is a hydrogen atom,
Halogen atom, cyano group, hydrocarbon group, -COO-
D ¹² or —COO—D ¹² via a hydrocarbon group (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 (IV).

[0012]

[Chemical 7]

In the formula (IV), 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) -,
-CON (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 may be the same as or different from each other, and may each be substituted, or represent a hydrocarbon group having 1 to 18 carbon atoms, which may have the following Chemical Formula 8 interposed in the bond of the main chain.

[0014]

[Chemical 8]

In the chemical formula 8, B ³ and B ⁴ may be the same or different from each other and have the same contents as the above B ¹ and B ² .
A ⁴ represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and D ²³ has the same content 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.

[0016]

[Chemical 9]

In the formula (II), X ⁰ is --COO-- or --OCO.
_{-, - CH 2 OCO -,} - CH 2 COO -, - O -, -
_{SO 2 -, - CO -,} - CONR 11 -, - SO 2 NR 11
-Or a phenylene group (-Ph-) (wherein R
¹¹ represents a hydrogen atom or a hydrocarbon group). b ¹ and b
² may be the same or different from each other, each is a hydrogen atom,
Halogen atom, cyano group, hydrocarbon group, -COO-
Z ¹ or —COO—Z ¹ via a hydrocarbon group (wherein Z ¹ represents a hydrogen atom or a hydrocarbon group).

[0018]

[Chemical 10]

In formula (III), X ¹ has the same meaning as X ⁰ in formula (II). Q ¹ represents an aliphatic group having 6 to 32 carbon atoms. d ¹ and d ² may be the same as or different from each other, and have the same contents as b ¹ and b ² in the formula (II).

Preferably, the dispersion stabilizing resin [P] used in the present invention has --PO _{3 at} one end of its polymer main chain.
_{H 2, -SO 3 H, -COOH} , -P (= O) (OH)
R ¹ [wherein R ¹ represents a hydrocarbon group or —OR ² (R ² represents a hydrocarbon group)], —OH, a formyl group,
_{^{-CONR 3 R 4, -SO 2 NR}} 3 R 4 [wherein R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group], are selected from cyclic acid anhydride-containing group and an amino group, It is a resin containing at least one polar group.

More preferably, the dispersion stabilizing resin [P]
Is a resin having a polymerizable functional group copolymerizable with the monomer (A) at one end of the polymer main chain.

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

The non-aqueous dispersion resin particles (hereinafter, also referred to as latex particles), which is the most important constituent component in the present invention, is a macro-monomer (M) in a non-aqueous solvent.
Is a comb-type copolymer containing as a copolymerization component, at least one of the monofunctional monomer (A) and the oligomer (B) in the presence of the dispersion stabilizing resin [P] soluble in the non-aqueous solvent.
Polymerization granulation by polymerizing at least one of the above and at least one of the polyfunctional monomer (D).

Preferably, the dispersion stabilizing resin [P] is
It is a resin containing the above-mentioned specific polar group at one end of its polymer main chain. More preferably, the dispersion stabilizing resin [P] has the monomer (A) at one end of the polymer main chain.
It is a resin containing a polymerizable functional group copolymerizable with.

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 include monomers represented by the following general formula (V).

[0029]

[Chemical 11]

In the formula (V), T ¹ is --COO-- or --OCO.
_{-, - CH 2 OCO -,} - CH 2 COO -, - O -, -
CONHCOO -, - CONHOCO -, - SO 2 -,
^{-CON (W 1) -, -} SO 2 N (W 1) -, or a phenylene group (-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, 2-hydroxyethyl group, benzyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, phenethyl group, 3-phenylpropyl group, dimethylbenzyl group, fluorobenzyl group , 2-methoxyethyl group, 3-
A methoxypropyl group).

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.).

E ¹ and e ² may be the same or different and each has the same meaning 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 unsaturated carboxylic acid such as maleic acid having 1 to 4 carbon atoms which may be substituted (for example, 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,
Vinyl naphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N, N
-Dimethylaminomethylstyrene, vinylbenzenecarboxamide, vinylbenzenesulfoamide, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid; cyclic acid anhydrides of maleic acid, itaconic acid; Acrylonitrile; methacrylonitrile; a heterocyclic compound containing a polymerizable double bond group (specifically, for example, "Polymer Data Handbook-Basic Edition", edited by The Society of Polymer Science, pp. 175-184, Baifukan (1986). ), For example, N-vinyl pyridine, N
-Vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.)
Etc. The monomer (A) may be used in combination of two or more kinds.

Next, the 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). At least one polar group selected from the group consisting of P (= O) (OH) G ¹ [wherein G ¹ represents a hydrocarbon group or an -OG ² group (G ² represents a hydrocarbon group)]; Is an oligomer having a number average molecular weight of 1 × 10 ⁴ or less.

[0035]

[Chemical 12]

In the formula (I), V ⁰ is --COO--, --OCO.
_{-, - (CH 2) r} COO -, - (CH 2) r OCO
-, - O -, - SO 2 -, - CONHCOO -, - CO
^{NHCONH -, - COND 11 -,} - SO 2 ND 11 -,
Or a phenylene group (—Ph—) (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 represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, —COO-D ¹² or —COO-D ¹² via a hydrocarbon group ( Here, 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 (IV).

[0037]

[Chemical 13]

In the formula (IV), 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) -,
-CON (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 may be the same as or different from each other, and each may be substituted, or represent a hydrocarbon group having 1 to 18 carbon atoms, which may have the following Chemical Formula 14 in the bond of the main chain.

[0039]

[Chemical 14]

In the chemical formula 14, 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 is an optionally substituted carbon atom having 1 to 18 carbon atoms. A hydrogen group, and D ²³ has the same meaning as D ²¹ above. m, n
And p may be the same or different from each other, and each is 0 to 4
Represents the integer. However, m, n, and p do not become 0 at the same time.

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 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 (eg, 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, etc.).

When V ⁰ represents a phenylene group (-Ph-), the benzene ring may have a substituent. As the substituent, a halogen atom (for example, chlorine atom, bromine atom, etc.), an alkyl group (for example, 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, 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, an alkenyl group, an aralkyl group, an alicyclic group or an aryl group having 1 to 18 carbon atoms, 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 details as described for D ¹¹ above.

The case where D ⁰ represents a substituent represented by the general formula (IV) will be described in detail. A ¹ and A ² are
They may be the same as or different from each other, each may be substituted, or the Chemical formula 14 may be interposed in the bond of the main chain,
A hydrocarbon group having 1 to 18 carbon atoms (the hydrocarbon group includes an alkyl group, an alkenyl group, an aralkyl group, and an alicyclic group; specific examples thereof include the same contents as the specific examples listed in D ^11; Is represented). 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 is composed of any combination of atomic groups such as the above chemical formula 14 is there.

[0047] Also, the linking group in the general formula ^{(I): -V 0 - (} A 1 -B 1) m - in _{^{(A 2 -B 2) n -D}} 21, from V ⁰ D ²¹ (ie, V ⁰ , A ¹ , B ¹ , A
It is preferable that the connecting main chain composed of ² , B ² , D ²¹ ) has a total number of atoms of 8 or more. here,
When A ^1, A ¹ is a hydrocarbon group of interposing the reduction 14 in the binding of the main ^{chain, -B 3 - (A 4 -B} 4) p -D
^{23 is} also included in the linking backbone. As the number of atoms of the connecting main chain, for example, when V ⁰ represents —COO— or —CONH—, an oxo group (═O group) and a hydrogen atom are not included as the number of atoms, and the carbon atoms constituting the connecting main chain are included. Atoms, ether type oxygen atoms, and nitrogen atoms are included as the number of atoms. Therefore, -COO- and -CONH- are counted as having 2 atoms. Similarly, if the 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 the substituent represented by the general formula (IV), that is, at least two or more repeating units are contained in the molecule. When containing a specific polar group,
More specifically, the following repeating units can be mentioned 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; k ₁ and k ₂ are each 1 to
12 is an integer; m ₁ is an integer of ₁ to 100.

[0049]

[Chemical 15]

[0050]

[Chemical 16]

[0051]

[Chemical 17]

[0052]

[Chemical 18]

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 sum 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, and 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-
It represents an OG ² group (G ² represents a hydrocarbon group). G ¹
Alternatively, the hydrocarbon group represented by G ² has 1 carbon atom
To 18 hydrocarbon groups are preferable, and more preferably aliphatic groups having 1 to 8 carbon atoms which may be substituted (eg, methyl group,
Ethyl group, propyl group, butyl group, pentyl group, hexyl group, butenyl group, pentenyl group, hexenyl group, 2-
Chloroethyl group, 2-cyanoethyl group, cyclopentyl group, cyclohexyl group, benzyl group, phenethyl group, chlorobenzyl group, bromobenzyl group, etc.), or an aromatic group which may be substituted (for example, phenyl group, tolyl group, xylyl group, Mesityl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

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

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).

[0058]

[Chemical 19]

In the general formulas (Ia) and (Ib), a ¹ ,
a ² , V ⁰ and D ⁰ have the same meanings 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 is a single bond or -CG ⁵ G
^6- [wherein 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, ethyl group, a propyl group)], - (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 -, - N
It represents a linking group composed of any combination of HCOO-, -NHCONH- and the like. However, G ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and specific examples thereof include those described for D ¹¹ in the formula (I). Further, the main chain of the polymer contains a copolymer component containing a phosphono group, a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, an amino group, and a polar group such as -P (= O) (OH) G ¹ group. Those that do not are preferred.

The oligomer (B) of the present invention in which a specific polar group is bonded only to one end of the main chain of the polymer, the living polymer obtained by conventionally known anionic polymerization or cationic polymerization has various reagents at the end. 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. 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, with preference given to mercapto compounds. 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 formula (Ia) or (Ib). Specific examples of the moiety represented by GL- 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, k ₃
Represents an integer of 1 or 3. R represents an alkyl group having 1 to 6 carbon atoms.

[0065]

[Chemical 20]

[0066]

[Chemical 21]

[0067]

[Chemical formula 22]

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 (VI). The functional groups shown may be mentioned.

[0069]

[Chemical formula 23]

[0070] In the formula ^{(VI), e 1, e} 2 and T ¹ have the same meanings as e ^1, e ² and T ¹ in the general formula (V).

The polyfunctional monomer (D) may be a monomer having two or more of the same or different polymerizable functional groups, and the monomer (A) And a polymer which is insoluble in a non-aqueous solvent by polymerizing with the oligomer (B).

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

The dispersion resin of the present invention comprises at least one kind of each of the monomer (A), the 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 dispersed resin of the present invention is preferably 1 × 10 ³ to 1 × 10 ⁶ , and more preferably 1 × 10 ⁴ to 1 × 10 ⁶ .

The solvent-insoluble polymer produced by polymerizing the monomer (A), the oligomer (B) and the monomer (D) in a non-aqueous solvent is used to form a stable resin dispersion. The dispersion-stabilizing resin [P] of the present invention has a weight average molecular weight of 1 × 10 ^{3 which is} obtained by bonding the polymerizable double bond group represented by the general formula (II) to only one end of the polymer main chain. ~ 2 x 10
⁴ is a comb-type copolymer containing at least one macromonomer (M) as a copolymerization component, and has the above general formula as a repeating unit of the main chain part and / or the comb part of the copolymer.
It is a resin soluble in the non-aqueous solvent, containing at least the component represented by (III).

The dispersion-stabilizing resin [P] has, as the repeating unit of the main chain portion and / or comb portion, the above-mentioned general formula (II
It contains at least one component represented by I). Preferably, both the main chain part and the comb part contain the repeating unit represented by the general formula (III). General formula (III)
The proportion of the repeating unit represented by in the dispersion-stabilizing resin [P] is such that the repeating unit as a copolymerization component other than the macromonomer (M) in the main chain part and the macromonomer (M) constituting the comb part are 5 for the total number of repeating units
It is 0 to 100% by weight, preferably 70 to 100% by weight. When the repeating unit of the general formula (III) is less than 50% by weight, the redispersibility of the resin particles obtained by the polymerization granulation is deteriorated, which is not preferable.

The proportion of the macromonomer (M) as a copolymerization component of the comb-type copolymer is 5 to 80% by weight, preferably 10 to 10% by weight, based on the total components of the dispersion stabilizing resin [P]. It is 60% by weight. When the proportion of the macromonomer (M) is less than 5% by weight, the number of comb portions is significantly reduced, and the redispersibility of the resin particles, which is an effect of the present invention, is deteriorated. On the other hand, the ratio of macromonomer (M) is 8
When it exceeds 0% by weight, the copolymerizability of the macromonomer (M) with the other monomer to be copolymerized at the time of synthesizing the comb-type copolymer is lowered.

The weight average molecular weight (hereinafter abbreviated as "Mw") of the dispersion stabilizing resin [P] which is a comb-type copolymer of the present invention is 2 × 10 ⁴ to 1 × 10 ⁶ , preferably 3 ×.
It is 10 ^{4 to} 5 × 10 ⁵ . Mw less than 2 × 10 ⁴ or 1
When it exceeds × 10 ⁶ , the redispersibility of the resin particles obtained by polymerization granulation is deteriorated, which is not preferable. The Mw of the macromonomer (M) is 1 × 10 ³ to 2 × 1.
It is 0 ⁴ , and preferably 3 × 10 ³ to 1 × 10 ⁴ .

The dispersion stabilizing resin [P] of the present invention will be described in more detail below. In formula (II), X ⁰ is —CO
O -, - OCO -, - CH 2 OCO -, - CH 2 COO
-, - O -, - SO 2 -, - CO -, - CONR 11 -,
Represents —SO ₂ NR ¹¹ — or —Ph— (wherein R ¹¹
Represents a hydrogen atom or a hydrocarbon group). b ¹ and b ² are
Which may be the same or different, each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -COO-Z ^1, or hydrocarbons represent -COO-Z ¹ via a group (wherein Z
¹ represents a hydrogen atom or a hydrocarbon group). In the formula (III), X
¹ has the same meaning as X ⁰ in formula (II). Q ¹ represents an aliphatic group having 6 to 32 carbon atoms. d ¹ and d ² may be the same or different from each other, and are b ¹ and b ² in the formula (II).
Represents the same content as. In the general formulas (II) and (III), the hydrocarbon group and the aliphatic group may be substituted.

In the general formula (II), R ¹¹ in the substituent represented by X ⁰ is a hydrogen atom, and a preferable hydrocarbon group is an alkyl group having 1 to 22 carbon atoms which may be substituted (for example, Methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group,
Dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl 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, a 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, 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.), aromatic group having 6 to 12 carbon atoms which may be substituted (for example, 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, ethoxycarbonyl Phenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodecyloylamidophenyl group and the like).

When X ⁰ represents -Ph- (phenylene group), the benzene ring may have a substituent. As the substituent, a halogen atom (eg, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), an alkoxy group (eg, methoxy group, Ethoxy group,
Propyloxy group, butoxy group, etc.) and the like.

B ¹ and b ² may be the same or different from each other, and preferably a hydrogen atom or a halogen atom (for example,
Chlorine atom, bromine atom, fluorine atom, etc., cyano group, alkyl group having 1 to 4 carbon atoms (eg, methyl group, ethyl group,
Propyl group, butyl group, etc.), - COO-Z ^1, or -COO-Z ¹ via a hydrocarbon group (Z ¹ is preferably a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group Represents an alicyclic group or an aryl group, which may be substituted, and specifically represents the same as those described for R ¹¹ above. Examples of the hydrocarbon in the —COO—Z ¹ group via the above hydrocarbon group include a methylene group, an ethylene group, a propylene group and the like.

More preferably, in the general formula (II),
X ⁰ is -COO-, -OCO-, -CH ₂ OCO-,-.
_{CH 2 COO -, - O -} , - CONH -, - SO 2 NH
Represents-, or -Ph-, and b ¹ and b ² may be the same or different from each other, and each is a hydrogen atom, a methyl group, or -C.
OO-Z ^1, or represents a -CH ₂ COO-Z ^1. Here, Z ¹ is more preferably a hydrogen atom or a carbon number of 1 to 6.
Represents an alkyl group (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.). More preferably, either ^one of b ¹ and b ² represents a hydrogen atom.

That is, as the polymerizable double bond group represented by the general formula (II), specifically, CH ₂ ═CH—COO
_{-, CH 2 = C (CH} 3) -COO-, CH 3 -CH =
_{CH-COO-, CH 2 = C} (CH 2 COOCH 3) -
_{COO-, CH 2 = C (CH} 2 COOH) -COO-,
_{CH 2 = CH-CONH-, CH} 2 = C (CH 3) -C
_{ONH-, CH 3 -CH = CH-} CONH-, CH 2 =
_{CH-OCO-, CH 2 = CH} -CH 2 -OCO-, C
_{H 2 = CH-O-, CH} 2 = C (COOH) -CH 2 -
_{COO-, CH 2 = C (COOCH} 3) -CH 2 -CO
O-, CH ₂ = CH-Ph-, and the like.

In the general formula (III), d ¹ and d ² are
They may be the same as or different from each other, and are b ¹ and b in the formula (II).
Indicates the same content as ² . Preferred examples of d ¹ and d ² are the same as the preferred examples of b ¹ and b ^{2 in} the formula (II). X ¹
Represents the same content as X ⁰ in formula (II), and is preferably —COO—, —OCO—, —O—, or —CH ₂ OCO.
-, or represents a -CH ₂ COO-. Q ¹ has 6 to 6 carbon atoms
It represents an aliphatic group having 32 carbon atoms, and preferably has 8 to 22 carbon atoms.
Represents an alkyl group or an alkenyl group, for example, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosanyl group, eicosanyl group, octenyl group, decenyl group,
Examples thereof include dodecenyl group, tridecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, linoleyl group and docosenyl group.

The repeating unit of the main chain portion and the comb portion of the dispersion stabilizing resin [P] of the present invention may contain other repeating units in addition to the repeating unit represented by the general formula (III). Other repeating units include those represented by the general formula (III)
The repeating unit is not particularly limited as long as it is a repeating unit composed of another monomer copolymerizable with the monomer corresponding to the repeating unit represented by. The other copolymerizable monomer may be any as long as it contains a polymerizable double bond group, for example,
Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and itaconic acid; ester derivatives or amide derivatives of unsaturated carboxylic acids having 6 or less carbon atoms; vinyl esters or allyl esters of carboxylic acids; styrenes; methacryloyl Nitrile; acrylonitrile; and a heterocyclic compound containing a polymerizable double bond group. More specifically, compounds having the same content as the above-mentioned insolubilizing monomer (A) and the like can be mentioned.

The macromonomer (M) of the present invention can be produced by a conventionally known synthetic method. For example,
A method by an ionic polymerization method, in the molecule, by reacting various reagents to the ends of a living polymer obtained by anionic polymerization or cationic polymerization to form a macromer,
Using a polymerization initiator and / or a chain transfer agent containing a reactive group such as a carboxyl group, a hydroxy group and an amino group,
In the same manner as the above radical polymerization method, a method by a radical polymerization method of reacting an oligomer having a terminal reactive group bond obtained by radical polymerization with various reagents to form a macromer, or an oligomer obtained by a polyaddition or polycondensation reaction is used. Examples thereof include a method by a polyaddition condensation method of introducing a polymerizable double bond group. Specifically, P. Dreyfus
s & R. P. Quirk, Encycl. Poly
m. Sci. Eng. , 7 , 551 (1987), p.
F. Rempp & E. Franta, Adv. Po
lym. Sci. , 58 , 1 (1984), V.I. Per
cec, Appl. Polym. Sci. , 285 , 9
5 (1984), R.A. Asami, M .; TakaRi,
Makvamol. Chem. Suppl. , 12 , 1
63 (1985), p. Rempp et al, Ma
kvamol. Chem. Suppl. , 8 , 3 (19
84), Yusuke Kawakami "Chemical Industry" 38 , 56 (198)
7), Yuya Yamashita "Polymer" 31 , 988 (1982),
Shiro Kobayashi "polymer" 30, 625 (1981), Higashimura Satoshinobe "Journal of the Adhesion Society of Japan" 18, 536 (1982), Ito, Koichi "Polymer Processing" 35, 262 (1986), AzumaTakashi Shiro, Takashi Tsuda " Functional Material " 1987 , No. It can be synthesized according to the methods described in the reviews such as 10, 5 and the references and patents cited therein.

Examples of the polymerization initiator containing a reactive group in the molecule include 4,4'-azobis (4-cyanovaleric acid) and 4,4'-azobis (4-cyanovaleric acid chloride). , 2,2'-azobis (2-cyanopropanol), 2,2'-azobis (2-cyanopentanol), 2,2'-azobis [2- (5-hydroxy-
3,4,5,6-tetrahydropyrimidin-2-yl)
Propane], 2,2'-azobis {2-methyl-N-
[1,1-bis (hydroxymethyl) -2-hydroxyethyl] propioamide}, 2,2'-azobis {2-
Methyl-N- [1,1-bis (hydroxymethyl) ethyl] propioamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propioamide],
2,2'-azobis (2-amidinopropane), 2,
2'-azobis [2-methyl-N- (2-hydroxyethyl) -propioamide], 2,2'-azobis [2-
(5-Methyl-2-imidazolin-2-yl) propane], 2,2′-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane] , 2,2'-azobis [2- (3,4,5,6
-Tetrahydropyrimidin-2-yl) propane],
2,2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane}, 2,
2'-azobis [N- (2-hydroxyethyl) -2-
Examples thereof include azobis compounds such as methyl-propionamidine] and 2,2′-azobis [N- (4-aminophenyl) -2-methylpropionamidine].

Examples of the chain transfer agent containing a reactive group in the molecule include, for example, a mercapto compound containing the reactive group or a substituent capable of inducing the reactive group (eg, thioglycolic acid, thiomalic acid). , Thiosalicylic acid, 2-
Mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3-
[N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino]
Propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-
1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, etc.) or the reactivity thereof A group or a substituent-containing iodinated alkyl compound that can be introduced into the reactive group (eg, iodoacetic acid, iodopropionic acid, 2-iodoethanol,
2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.) and the like. Preferred are mercapto compounds. The amount of each of these chain transfer agents or polymerization initiators used is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of all monomers.

The dispersion-stabilizing resin polymer [P] used in the present invention is specifically a known method represented by the general formula (II
A method in which at least a monomer corresponding to the repeating unit represented by I) and the above-described macromonomer (M) are allowed to coexist and polymerization is performed with a polymerization initiator (eg, azobis compound, peroxide, etc.) is simple and convenient. ,preferable. The polymerization initiators used here are all monomers and all macromonomers (M).
The total amount is 0.5 to 15% by weight, preferably 1 to 10% by weight.

The dispersion stabilizing resin [P] used in the present invention is preferably a resin having a specific polar group bonded to one end of the polymer main chain. [Hereinafter, referred to as dispersion stabilizing resin [PA] or resin [PA]. ] The specific polar _{group, -PO 3 H 2, -SO 3} H, -COO
H, -P (= O) (OH) R ¹ [wherein R ¹ represents a hydrocarbon group or -OR ² (R ² represents a hydrocarbon group)], -OH, formyl group, -CONR ³ R ⁴ , -SO
₂ NR ³ R ⁴ [wherein R ³ and R ⁴ are each independently
A hydrogen atom or a hydrocarbon group], a cyclic acid anhydride-containing group, and at least one polar group selected from amino groups.

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

The above-mentioned --CONR ³ R ⁴ and --SO ₂ NR
^{In the} polar group represented by ³ R ⁴ , R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group (preferably a hydrocarbon group having 1 to 8 carbon atoms which may be substituted).
Specific examples of the hydrocarbon group represented by R ³ and R ⁴ include the same as those of the hydrocarbon group represented by R ¹ and R ² .

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

In the polar group of the present invention, the amino group is -N
H _2, represents a -NHR ⁵ or -NR ⁵ R ^6. R ⁵ , R ⁶
Represents a hydrocarbon group having 1 to 8 carbon atoms, preferably a hydrocarbon group having 1 to 7 carbon atoms, and specifically, the above R
Examples thereof include those having the same contents as the hydrocarbon group represented by ¹ and R ² .

In the dispersion stabilizing resin [PA], at least one of the above-mentioned specific polar groups may be directly bonded to one end of the polymer main chain, or may be bonded via a linking group. The linking group for linking the main chain component and the specific polar group-containing component, carbon-carbon bond (single bond or double bond), 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. Further specific examples of the linking group include —CR ⁷ R ⁸ — [wherein R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a cyano group, hydroxyl group, an alkyl group (methyl group, ethyl group, propyl group, etc.) indicating the like], - (CH = CH) - , - C 6 H 10 - ( i.e., cyclohexylene), - Ph -, - O- , -S-, -CO
^{-, - NR 9 -, -} COO -, - SO 2 -, - CONR
_{^{9 -, - SO 2 NR 9}} -, - NHCOO -, - NHCO
^{NH -, - SiR 9 R 10} - [wherein, R ⁹ and R ¹⁰ each independently represent a hydrogen atom, a hydrocarbon group which represents the same content as that of R ¹ in the polar group] atomic group such as A single linking group selected from the above or a linking group composed of a combination of any two or more atomic groups can be mentioned.

The dispersion stabilizing resin polymer [PA] used in the present invention is specifically a monomer corresponding to the repeating unit represented by the general formula (III), the above macromonomer (M), and A method of polymerizing a mixture of the chain transfer agent containing the specific polar group with a polymerization initiator (eg, azobis compound, peroxide, etc.) or containing the polar group without using the chain transfer agent. A method of polymerizing using a polymerization initiator, or both a chain transfer agent and a polymerization initiator, a method of using a compound containing the polar group,
Furthermore, in the above three methods, as a substituent of the chain transfer agent or the polymerization initiator, an amino group, a halogen atom,
It can be produced by a method of introducing the polar group by polymerizing a compound containing an epoxy group, an acid halide group or the like and then reacting these functional groups with a polymer reaction. Specifically, P. Dreyfuss
& R. P. Quirk, Encycl. Polym.
Sci. Eng. , 7 , 551 (1987), Yoshiki Nakajo, Yuya Yamashita "Dyes and Pharmaceuticals" 30 , 232 (198)
5), Akira Ueda, Susumu Nagai "Science and Industry" 60 , 57 (19
86) etc. and the methods described in the references cited therein and the like.

Specific examples of the chain transfer agent containing a specific polar group or a substituent capable of inducing the polar group include the above-mentioned mercapto as a chain transfer agent containing a reactive group in the method of synthesizing the macromonomer (M). Examples thereof include compounds and iodinated alkyl compounds. Preferred are mercapto compounds. Further, as the polymerization initiator containing the specific polar group or the substituent capable of being induced to the polar group, the azobis compounds described above can be mentioned as the polymerization initiator containing the reactive group in the macromonomer (M). The amount of each of these chain transfer agents or polymerization initiators used is 0.1 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the total amount of all monomers and all macromonomers (M). 5 to 5 parts by weight.

More preferably, the dispersion stabilizing resin [P] used in the present invention has a polymerizable functional group copolymerizable with the monomer (A) at one end of the polymer main chain. There are things that consist of. [Hereinafter, referred to as dispersion stabilizing resin [PB] or resin [PB]. ]

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

Furthermore, the dispersion stabilizing resin [PB] of the present invention, which is a preferred embodiment and has a polymerizable functional group bonded to one end of the polymer main chain, can be obtained by conventionally known anionic polymerization or cationic polymerization. either reacting a reagent containing various polymerizable double bond group at the end of the living polymer, or a specific reactive group at the end of the living polymer _{(e.g., -OH, -COOH, -SO 3 H} , -
_{SH, -NH 2, -PO 3 H} 2, -NCO, -NCS,
Epoxy group represented by the following chemical formula 24, -COCl, -SO
₍₂ Cl, etc.) and then introducing a polymerizable double bond group by polymer reaction (method by ionic polymerization method), or containing the above specific reactive group in the molecule After radical polymerization using a polymerization initiator and / or a chain transfer agent, a polymeric double bond is formed by carrying out a polymer reaction using a specific reactive group bonded to only one end of the polymer main chain. It can be easily produced by a synthetic method such as a method of introducing a group.

[0102]

[Chemical formula 24]

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

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

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.

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., obtained by treating the monofunctional monomer (A), the oligomer (B), and the polyfunctional monomer (D) in a non-aqueous solvent. It may be carried out by heat polymerization in the presence of. In particular,
Method for adding a polymerization initiator to a 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 a monomer (A), an oligomer (B) and a monomer (D) together with a polymerization initiator, or a total amount of a dispersion stabilizing resin [P] and a monomer (A), an 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), Furthermore, a method of optionally adding a mixed solution of the dispersion stabilizing resin [P], the monomer (A), the oligomer (B) and the monomer (D) to the non-aqueous solvent together with the polymerization initiator, etc. 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 the polar solvent such as alcohols, ketones, ethers and esters described above is used in combination with the non-aqueous solvent used in the reaction, or the monomer (A) or a single amount to be polymerized and granulated is 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 the hydrophilic treatment process of the non-image area, the toner image area has excellent resist property, and the original image reproducibility of the image area of the printed matter is excellent.

The liquid developer of the present invention which brings about the above effects is made possible by the insoluble latex provided by the present invention. That is, in the dispersed resin particles of the present invention, the dispersion stabilizing resin [P] interacts with the insoluble resin particles and is adsorbed to the insoluble resin particles. Since the resin [P] adsorbed on the resin particles is soluble in the non-aqueous solvent, it brings about a so-called steric repulsion effect, which is known as dispersion stabilization of the non-aqueous latex. At the same time, since the resin [P] is a soluble resin containing a comb structure, the affinity for the non-aqueous solvent is remarkably improved and the adsorbed resin [P]
Exists in the vicinity of the particle interface because it has a comb structure, and it is presumed that this improves the amphiphilicity in the vicinity of the particle interface.
It is considered that these factors suppress the aggregation / precipitation of the insoluble particles and significantly improve the redispersibility.

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

In a more preferred embodiment, a dispersion stabilizing resin [PB containing a polymerizable functional group at one end of the polymer main chain [PB
Is used, it is copolymerized with the insoluble monomer (A) and the monomer (D) during the dispersion polymerization reaction, and is more efficiently bound to the insoluble resin particles.

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

On the other hand, the insoluble resin particles of the present invention are characterized in that the particles are polymerized and granulated using the polyfunctional monomer (D) to form a crosslinked structure. This allows
After 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.

Various additives may be added to the liquid developer of the present invention, if desired, for the purpose of enhancing charging characteristics or improving image characteristics. For example, Yuji Harazaki, “Electrophotography”, Vol. 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.

[0118]

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.

[0120]

[Chemical 25]

Preparation Examples 2 to 31 of Oligomer (B): Oligomer B-2 to B-31 In Preparation 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.

[0122]

[Table 1]

[0123]

[Table 2]

[0124]

[Table 3]

[0125]

[Table 4]

Production Example 32 of Oligomer (B): Oligomer B-32 100 g of 2- (n-nonylcarbonyloxy) ethyl crotonate, 150 g of toluene, and 50 g of ethanol
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.

[0127]

[Chemical formula 26]

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.

[0129]

[Table 5]

[0130]

[Table 6]

Production Example of Macromonomer (M) 1: Macromonomer M-1 A mixed solution of 100 g of methyl methacrylate, 5 g of mercaptopropionic acid and 200 g of toluene was heated to a temperature of 75 ° C. while stirring under a nitrogen stream. 1.0 g of 2,2'-azobisisobutyronitrile (abbreviation AIBN) was added and reacted for 4 hours. I. B. N. Was added for 3 hours, and A. I. B. N. 0.3 g
The reaction was continued for 3 hours. Next, 8 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and 0.5 g of t-butylhydroquinone were added to this reaction solution, and the mixture was stirred at 100 ° C. for 12 hours. After cooling, the reaction solution was reprecipitated in 2 liters of methanol to obtain 82 g of white powder. The weight average molecular weight of the polymer was 6,500.

[0132]

[Chemical 27]

Production Examples 2 to 27 of Macromonomer (M): Macromonomers M-2 to M-27 In Production Example 1 of macromonomer (M), only methyl methacrylate was replaced with compounds corresponding to the following Table-C. Others react in the same manner as in Production Example 1 to produce macromonomer M.
-2-M-27 were synthesized. The weight average molecular weight of each obtained macromonomer was in the range of 5,000 to 7,000.

[0134]

[Table 7]

[0135]

[Table 8]

[0136]

[Table 9]

Production Example 28 of Macromonomer (M): Macromonomer M-28 90 g of dodecyl methacrylate, 10 g of methacrylic acid,
A mixed solution of 5 g of thioethanol and 200 g of toluene was heated to 70 ° C. while stirring under a nitrogen stream. A.
I. B. N. 1.0 g was added and reacted for 4 hours. Furthermore,
A. I. B. N. 0.5 g was added for 3 hours, and then A. I. B. N. 0.3 g was added and reacted for 3 hours. This reaction solution was cooled to room temperature, 18.2-g of 2-carboxyethyl methacrylate was added, and a mixed solution of 24 g of dicyclohexylcarbodiimide (abbreviated as D.C.C.) and 150 g of methylene chloride was added dropwise thereto over 1 hour. t-
Butylhydroquinone (1.0 g) was added, and the mixture was stirred as it was for 4 hours. The precipitated crystals were filtered off and the obtained filtrate was reprecipitated in 2 liters of methanol. The precipitated oily substance was collected by decantation, dissolved in 150 cc of methylene chloride, and reprecipitated again in 1 liter of methanol. The oily substance was collected and dried under reduced pressure to obtain a polymer having a weight average molecular weight of 5,800 with a yield of 54 g.

[0138]

[Chemical 28]

Production Examples 29-35 of Macromonomer (M): Macromonomers M-29 to M-35 In the production examples of Macromonomer M-28, a methacrylate monomer (corresponding to dodecylmethacrylate) and an unsaturated carboxylic acid (2- (Equivalent to carboxyethylmethacrylate), respectively, and macromonomers shown in Table D below were produced in the same manner as in Production Example of M-28. The weight average molecular weight of each obtained macromonomer is 5,000 to 7,000.
Met.

[0140]

[Table 10]

[0141]

[Table 11]

Production Example 36 of Macromonomer (M): Macromonomer M-36 A mixed solution of 70 g of n-dodecyl methacrylate, 30 g of t-butyl methacrylate, 4 g of 2-mercaptoethylamine and 200 g of tetrahydrofuran was heated to a temperature of 70 ° C. under a nitrogen stream. Warmed. A. I. B. N. 1.0 g was added and the mixture was reacted for 4 hours. I. B. N. Add 0.5g of 4
Reacted for hours. Next, this reaction solution was cooled in a water bath to a temperature of 20 ° C., 6.5 g of triethylamine was added, and 5.6 g of acrylic acid chloride was stirred and added dropwise at a temperature of 25 ° C. or lower. After dropping, the mixture was further stirred for 1 hour as it was. Then, 0.5 g of t-butyl hydroquinone was added and the temperature was adjusted to 60.
The mixture was warmed to ℃ and stirred for 4 hours. After cooling, the operation of reprecipitation in 2 liters of methanol was performed twice, and a pale yellow viscous material 6
3 g was obtained. The weight average molecular weight was 6,600.

[0143]

[Chemical 29]

Production Example 37 of Macromonomer (M): Macromonomer M-37 A mixed solution of 100 g of octadecyl methacrylate, 150 g of tetrahydrofuran and 50 g of isopropyl alcohol was heated to 75 ° C. under a nitrogen stream. 4,4 '
-Azobis (4-cyanovaleric acid) (abbreviation: AC).
V. ) Was added and reacted for 5 hours. C. V.
1.0 g was added and reacted for 4 hours. After cooling, the reaction solution was reprecipitated in 1.5 liter of methanol, the oily matter was collected by decantation, and dried under reduced pressure. The yield was 85g. 50 g of the obtained oily substance (oligomer), 15 g of glycidyl methacrylate, 1.0 g of N, N-dimethyldodecylamine and 2,2'-methylenebis (6-t
-Butyl-p-cresol) 1.0 g was added, and the temperature was adjusted to 10
The mixture was stirred at 0 ° C for 15 hours. After cooling, the reaction solution was reprecipitated in 1 liter of petroleum ether to obtain 42 g of white powder. The weight average molecular weight was 7,500.

[0145]

[Chemical 30]

Preparation Example 38 of Macromonomer (M): Macromonomer M-38 In Preparation Example 37 of Macromonomer, 50 g of the intermediate oligomer obtained, 2.8 g of 2-hydroxyethyl methacrylate and 100 g of methylene chloride were mixed. Into the solution,
D. with stirring at room temperature. C. C. A mixed solution of 4.0 g, 4-dimethylaminopyridine 0.5 g and methylene chloride 10 g was added dropwise over 1 hour. The mixture was stirred as it was for 4 hours. The precipitated crystals were separated by filtration, the operation of reprecipitating the filtrate in 1 liter of methanol was performed twice, and the obtained powder was dried under reduced pressure. Yield 43g, weight average molecular weight 7,300
Met.

[0147]

[Chemical 31]

Preparation Example of Dispersion Stabilizing Resin [P] 1: Resin P
-1 Octadecyl methacrylate 70g, macromonomer M
A mixed solution of 30 g of -1 and 200 g of toluene was heated to a temperature of 85 ° C while stirring under a nitrogen stream. 2,2'-
Azobis (isobutyronitrile) (abbreviation A.I.B.
N. ) Was added and reacted for 4 hours. Furthermore, A. I.
B. N. 1.0 g was added and the mixture was reacted for 2 hours.
I. B. N. 0.5 g was added and reacted for 2 hours. After cooling, the mixed solution was reprecipitated in 1.5 liter of methanol, and the powder was collected by filtration and dried to obtain 88 g of a white powder.
The weight average molecular weight (abbreviated as Mw) of the obtained polymer was 4.5 × 10 ⁴ .

Production Examples 2 to 14 of Dispersion Stabilizing Resin [P]:
Resins P-2 to P-14 In Production Example 1 of the resin [P] for dispersion stabilization, octadecyl methacrylate and macromonomer M-1 are replaced with the monomer and macromonomer (M) shown in Table E below. In the same manner as in Production Example 1, each dispersion stabilizing resin was produced. Mw of each resin is 4.0 × 10 ^{4 to} 6 × 10
^{Was 4} .

[0150]

[Table 12]

Production Example of Dispersion Stabilizing Resin [PA] 1: Resin PA -1 octadecyl methacrylate 80 g, macromonomer M
A mixed solution of 20 g of -1 and 150 g of toluene was heated to a temperature of 75 ° C while stirring under a nitrogen stream. A.
C. V. 1.0 g was added and the mixture was reacted for 4 hours. C.
V. 0.3 g was added for 2 hours, and A. C. V. 0.3
g and reacted for 3 hours. After cooling, it was reprecipitated in 2 liters of methanol, collected by filtration and dried to obtain 76 g of a white powder. The Mw of the obtained resin was 4.8 × 10 ⁴ .

[0152]

[Chemical 32]

Production Examples 2-1 of Dispersion Stabilizing Resin [PA]
5: Resin PA-2 to PA-15 In Production Example 1 of Resin PA-1, the reaction was the same as in Production Example 1 except that octadecyl methacrylate and macromonomer M-1 were replaced with the compounds shown in Table F below. Thus, each dispersion stabilizing resin was manufactured. Mw of each resin is 3.5 × 10 ⁴
It was ˜5.0 × 10 ⁴ .

[0154]

[Table 13]

[0155]

[Table 14]

Production Example 16 of dispersion stabilizing resin [PA]: Resin PA-16 70 g of octadecyl methacrylate, macromonomer M
-30 g, thiomalic acid 0.8 g, toluene 10
A mixed solution of 0 g and 50 g of isopropyl alcohol,
The temperature was raised to 80 ° C. under a nitrogen stream. 1,1'-azobis (cyclohexane-1-carbocyanide) (abbreviation: A.I.
B. C. C. ) Is added and reacted for 4 hours.
B. C. C. 0.4 g was added for 3 hours, and A. B.
C. C. 0.3 g was added and reacted for 4 hours. After cooling, it was reprecipitated in 2 liters of methanol, collected by filtration and dried to obtain 78 g of a white powder. The Mw of the obtained resin is 3.8 × 10.
^{Was 4} .

[0157]

[Chemical 33]

Production Examples 17 to 2 of Dispersion Stabilizing Resin [PA]
5: Resin PA-17 to PA-25 In Production Example 16 of Resin PA-16, octadecyl methacrylate, macromonomer M-10, and mercapto compound (thiomalic acid) were replaced with compounds corresponding to Table G below. React in the same manner as in Example 16 to obtain each resin P
A-17 to PA-25 were produced. Mw of each resin is 3.
It was 0 × 10 ⁴ to 4 × 10 ⁴ .

[0159]

[Table 15]

[0160]

[Table 16]

Production Examples 26 to 3 of dispersion stabilizing resin [PA]
1: Resin PA-26 to PA-31 In Production Example 1 of resin PA-1, the polymer initiator A.
C. V. In the same manner as in Production Example 1 except that the azobis compound shown in the following Table-H was used in place of, each resin PA-26-
PA-31 was produced. The Mw of each resin obtained is 3.0
It was x10 ^{4 to} 6x10 ⁴ .

[0162]

[Table 17]

Production Example 32 of dispersion stabilizing resin [PA]: Resin PA-32 n-dodecyl methacrylate 85 g, macromonomer M
A mixed solution of 15 g of −28 and 150 g of toluene was heated to a temperature of 75 ° C. under a nitrogen stream. A. C. V. 1.0 g was added for 4 hours, and A. C. V. 0.5 g was added and reacted for 3 hours. Furthermore, A. C. V. After adding 0.3 g, the mixture was heated to a temperature of 90 ° C. and reacted for 2 hours. After cooling, the reaction product was reprecipitated in 2 liters of methanol, the precipitated viscous product was collected by decantation, and dried under reduced pressure.
The yield of the transparent viscous product was 76 g, and the weight average molecular weight was Mw.
Was 4.3 × 10 ⁴ .

[0164]

[Chemical 34]

Production Example 1 of dispersion stabilizing resin [PB]: Resin PB-1 Resin PA synthesized in Production Example 1 of dispersion stabilizing resin [PA]
The temperature was set to 25 ° C. while stirring a mixed solution of 50 g of −1, 5 g of allyl alcohol and 100 g of tetrahydrofuran under stirring. To this solution, 8 g of dicyclohexyldicarbodiimide (abbreviated D.C.C.), 0.2 g of 4- (N, N-diethylamino) pyridine and 20 methylene chloride were added.
The mixed solution of g was added dropwise over 1 hour. The reaction was further continued for 3 hours to complete the reaction. Then add 8 to this reaction mixture.
After adding 10 g of 0% formic acid and stirring for 1 hour, the insoluble matter was filtered off, and the filtrate was reprecipitated in 1 liter of methanol. The precipitate was collected by filtration, dissolved again in 90 g of toluene, the insoluble matter was filtered off, and the filtrate was reprecipitated in 500 cc of methanol. The precipitate was collected by filtration and dried. The yield of the obtained polymer is 32.
In g, Mw was 3 × 10 ⁴ .

[0166]

[Chemical 35]

Production Examples 2 to 7 of Dispersion Stabilizing Resin [PB]:
Resin PB-2 to PB-7 In the production example 1 of the dispersion stabilizing resin [PB], the resin PA
-1 and allyl alcohol instead of resin P in Table I below.
Except for using A and the polymerizable group-introduced compound, the same procedure as in Production Example 1 was repeated to produce each dispersion stabilizing resin.

[0168]

[Table 18]

Production Example 8 of dispersion-stabilizing resin [PB]: Resin PB-8 A mixed solution of 75 g of octadecyl methacrylate, 2 g of 2-mercaptoethanol, 25 g of macromonomer M-29 and 250 g of tetrahydrofuran was heated at 70 ° C. under a nitrogen stream. Warmed to. A. I. B. N. 0.5 g was added and the mixture was reacted for 4 hours. I. B. N. 0.3g of 4
Reacted for hours. Then, the reaction mixture was cooled to 25 ° C., 8 g of vinyl acetic acid was added thereto, and D.I. C.
C. 10 g, a mixed solution of 0.4 g of 4- (N, N-diethylamino) pyridine and 30 g of methylene chloride was added dropwise over 1 hour, and the mixture was further stirred as it was for 4 hours. Next, 30%
5 g of hydrogen chloride ethanol solution and 5 g of water were added, and the mixture was stirred as it was for 1 hour. After the insoluble matter was filtered off, the filtrate was reprecipitated in 2 liters of methanol. The precipitate was collected by filtration and dried. The Mw of the obtained polymer was 3 × 10 ⁴ .

[0170]

[Chemical 36]

Production Example 9 of dispersion stabilizing resin [PB]: Resin PB-9 60 g of hexadecyl methacrylate, macromonomer M
A mixed solution of 40 g of -30 and 200 g of tetrahydrofuran was heated to a temperature of 75 ° C under a nitrogen stream. 2,2'-
Azobis (2-cyanoheptanol) (abbreviation: A.B.
C. H. ) Was added and reacted for 4 hours. B. C.
H. 0.5 g was added and reacted for 4 hours. Next, the reaction mixture was cooled to 25 ° C., 6 g of methacrylic acid was added thereto, and D. C. C. 9.5 g, 4- (N, N
A mixed solution of 0.4 g of -diethylamino) pyridine and 40 g of methylene chloride was added dropwise over 1 hour, and 4
Stir for hours. Next, add 10 g of 85% formic acid aqueous solution,
The mixture was stirred as it was for 1 hour. After the insoluble matter was filtered off, the filtrate was reprecipitated in 2 liters of methanol. The precipitate is collected by filtration,
Dried. The Mw of the obtained polymer was 5.5 × 10 ⁴ .

[0172]

[Chemical 37]

Production Examples 10-1 of Dispersion Stabilizing Resin [PB]
8: Resin PB-10 to PB-18 In Production Example 9 of dispersion stabilizing resin [PB], hexadecyl methacrylate, macromonomer M-30, and methacrylic acid as a polymerizable group-introducing compound are used instead of methacrylic acid as shown in Table J below. Production Example 9 except that each compound corresponding to each of the above components is used.
Each dispersion-stabilizing resin was produced in the same manner as in. The Mw of the obtained resin was in the range of 4.5 × 10 ^{4 to} 6 × 10 ⁴ .

[0174]

[Table 19]

[0175]

[Table 20]

Production Example 19 of dispersion stabilizing resin [PB]: Resin PB-19 Resin P synthesized in Production Example 17 of dispersion stabilizing resin [PA]
100 g of A-17, 8 g of glycidyl methacrylate,
A mixture of 1.0 g of N, N-dimethyldodecylamine, 0.5 g of t-butylhydroquinone and 200 g of toluene was stirred at a temperature of 100 ° C. for 12 hours. After cooling, this reaction solution was reprecipitated in 1.5 liter of methanol, collected by filtration and dried to obtain 78 g of a pale yellow powder. The Mw of the obtained polymer was 6.8 × 10 ⁴ .

[0177]

[Chemical 38]

Production Example 20 of dispersion stabilizing resin [PB]: Resin PB-20 Resin P synthesized in Production Example 25 of dispersion stabilizing resin [PA]
A solution of 100 g of A-25 dissolved in 200 g of tetrahydrofuran was cooled to a temperature of 20 ° C. in a water bath, 10.2 g of triethylamine was added, and 14.5 g of methacrylic acid chloride was added dropwise with stirring at a temperature of 25 ° C. or lower. After dropping, the mixture was further stirred for 1 hour as it was. Then, 0.5 g of t-butyl hydroquinone was added, and the mixture was heated to a temperature of 60 ° C. and stirred for 4 hours. After cooling, add dropwise to 1 liter of water with stirring (for about 10 minutes), stir for 1 hour and let stand,
Water was removed by decantation. 2 more washing with water
After being stirred, it was dissolved in 100 ml of tetrahydrofuran and reprecipitated in 2 liters of petroleum ether. The precipitate was collected by decantation and dried under reduced pressure. The obtained viscous product had a yield of 65 g and Mw of 4.5 × 10 ⁴ .

[0179]

[Chemical Formula 39]

Production Example 1 of Latex Particles: Latex Particles D-1 14 g of dispersion stabilizing resin P-1, 50 g of methyl methacrylate, 50 g of methyl acrylate, oligomer B-1.
1.0 g of 7 and ethylene glycol dimethacrylate 3
A mixed solution of g and Isopar H (384 g) was heated to a temperature of 60 ° C. with stirring under a nitrogen stream. 2,2'-azobis (isovaleronitrile) as a polymerization initiator (abbreviation A.
I. V. N. ) Was added thereto and reacted for 3 hours. Twenty minutes after the addition of the initiator, white turbidity occurred and the reaction temperature was 88 ° C.
Rose to. 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. After cooling, it was passed through a nylon cloth of 200 mesh, and the obtained white dispersion was a latex having a polymerization rate of 98% and an average particle size of 0.24 μm. The particle size was measured by CAPA-500 (manufactured by Horiba, Ltd.).

Production Examples 2 to 21 of Latex Particles: Latex Particles D-2 to D-21 In Production Example 1 of latex particles, the dispersion stabilizing resin P is used.
-1, the oligomer B-17, and the above Production Example 1 except that the dispersion stabilizing resin, the oligomer (B) and the monomer (D) shown in Table K below were used instead of the ethylene glycol dimethacrylate. By operating in exactly the same manner, latex particles D-2 to D-21 of the present invention were produced. The degree of polymerization of each latex particle obtained was 95 to 98%, and the average particle diameter was 0.1.
Within the range of 15 to 0.25 μm, the monodispersity was good.

[0182]

[Table 21]

[0183]

[Table 22]

Production Example 22 of Latex Particles: Latex Particle D-22 8 g of dispersion stabilizing resin PB-9, 100 g of vinyl acetate,
2.4g of Oligomer B-2, 5g of divinyl adipate
And a mixed solution of 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. Furthermore, temperature 10
The mixture was stirred at 0 ° C for 2 hours, and unreacted vinyl acetate was distilled off.
After cooling, the mixture was passed through a 200-mesh nylon cloth, and the obtained white dispersion was a latex having a polymerization rate of 93% and an average particle size of 0.20 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. Latex particles were prepared in the same manner as in Production Example 22 except that the compounds shown in Table L below were used instead of the stabilizing resin PB-9 and the monomer (D) (that is, divinyl adipate). Manufactured. The degree of polymerization of each latex particle obtained was 90 to 98%, and the average particle diameter was 0.15 to 0.3.
Within the range of 0 μm, the monodispersity was also good.

[0186]

[Table 23]

Production Example 31 of Latex Particles: (Comparative Example A) 25 g of a comparative dispersion-stabilizing resin (1) having the following structure, which was synthesized by the method disclosed in JP-A-3-12666.
Methyl methacrylate 50g, methyl acrylate 50
g and Isopar H were used in the same manner as in Production Example 1 of latex particles except that a mixed solution of 380 g was used to obtain a white dispersion of latex particles having a polymerization rate of 98% and an average particle size of 0.30 μm.

[0188]

[Chemical 40]

Production Example 32 of Latex Particles: (Comparative Example B) The same as the above except that 15 g of the comparative dispersion stabilizing resin (2) having the following structure synthesized by the method disclosed in JP-A-3-15862 is used. The same procedure as in Production Example 31 (Comparative Example A) of latex particles was conducted to obtain a polymerization rate of 99% and an average particle size of 0.2.
A white dispersion was obtained which was 5 μm latex particles.

[0190]

[Chemical 41]

Production Example 33 of Latex Particles: (Comparative Example C) Production Example 3 except that 2.4 g of oligomer B-17 was further added in Production Example 31 (Comparative Example A) of latex particles.
Treated in the same manner as No. 1, with a conversion of 98% and an average particle size of 0.28
A white dispersion of latex particles of μm was obtained. (JP-A-3-77965)

Production Example 34 of Latex Particles: (Comparative Example D) Production Example 3 except that 2.4 g of oligomer B-17 was further added in Production Example 32 (Comparative Example B) of latex particles.
Treated in the same manner as No. 2, with a polymerization rate of 99% and an average particle size of 0.23
A white dispersion of latex particles of μm was obtained. (Japanese Patent Laid-Open No. 3-91765)

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 types 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-M.

[0196]

[Table 24]

The measurement of each evaluation item in Table-M 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: Liquid developer EL
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 dispersion for forming a photosensitive layer was coated on 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.

[0199]

[Chemical 42]

(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 of Table-M, the developers of the present invention, Comparative Examples C and D did not stain the developing device, and the image on the 2000th plate was clear, and good results were obtained. 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 found to be 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, a clear printed matter was obtained only after printing 5,000 sheets of the present invention. Comparative Examples A and B
, The deterioration of the reproducibility of the copied image at the time of plate making appeared on the printed matter as it was, and 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 Production Example 30 of Latex Particles: 30 g of a resin dispersion of D-30, 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 ') Two types of comparative liquid developers C'and D'were used instead of the following resin dispersions in the production of the above liquid developers. 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-N.

[0209]

[Table 25]

In Table-N, the dirt on the developing device 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.

[0212]

[Chemical 43]

Each of the original plates thus obtained was immersed in the processing liquid E-2 having the following formulation for 30 seconds to remove the photoconductive layer in the non-image area, washed with water for 30 seconds, and then dried with a dryer. Air dried. <Prescription of Treatment Liquid E-2> Potassium silicate 40 g Potassium hydroxide 10 g Ethanol 100 g Water 800 g The presence or absence of 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 (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-N, 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, and was used as an offset master original plate. 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 an original plate 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 28 of Latex Particles: 30 g of the resin dispersion of D-28, 2.5 g of the above nigrosine dispersion, 0.06 g of hexadecene / half-maleic acid octadecylamide copolymer and F
A liquid developer for electrostatic photography was prepared by diluting 20 g of OC-1800 with 1 liter of Isopar G.

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 produced by the following formulation was charged to -6 kV in the dark, and then 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.

[0223]

[Chemical 44]

[0224]

[Chemical formula 45]

The original plate thus obtained was passed through an etching machine once using ELP-EX, and then immersed for 3 minutes in a hydrophilizing treatment liquid E-3 for a photoconductive layer binding resin having the following formulation. 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 plate precursor was observed with an optical microscope, no defects such as fine lines or fine characters in the toner image area were observed, and the toner particles of the present invention had good resist properties. Next, printing was carried out in the same manner as in Example 1 except that the above original plate was used as an 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 The same as Example 1 except that the latex particles shown in Table 0 below were used in place of the latex particles D-1 of the liquid developer of the present invention. Then, each liquid developer was prepared.

[0228]

[Table 26]

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 P below were used in place of the latex particles D-30 of the liquid developer of the present invention. Then, each liquid developer was prepared.

[0231]

[Table 27]

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.

[0235]

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 (3)

[Claims] 1. A liquid developer for electrostatic photography comprising at least resin particles dispersed in a non-aqueous solvent having an electric resistance of 10 ⁹ Ωcm or more and a dielectric constant of 3.5 or less, wherein the dispersed resin particles are At least one monofunctional monomer (A) that is soluble in an aqueous solvent but becomes insoluble by polymerization, one of the main chains of the polymer composed of the repeating unit represented by the following general formula (I) Carboxyl group, sulfo group, hydroxyl group, formyl group, amino group, phosphono group, and -P (= O) (OH) G ¹ group only at the terminal [wherein G ¹ is a hydrocarbon group or -OG ² group (G ² represents a hydrocarbon group)], at least one 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 Two polymerizable functional groups copolymerizable with A) A weight average molecular weight obtained by bonding at least one kind of the above-mentioned polyfunctional monomer (D) and a polymerizable double bond group represented by the following general formula (II) to only one end of the polymer main chain. A comb-type copolymer containing at least one macromonomer (M) of 1 × 10 ^{3 to} 2 × 10 ⁴ as a copolymerization component, and as a repeating unit of a main chain portion and / or a comb portion of the copolymer. A polymer resin particle obtained by polymerizing a solution containing a dispersion-stabilizing resin [P] soluble in the non-aqueous solvent, which contains at least a component represented by the following general formula (III): Liquid developer for electrostatic photography. [Chemical 1] In formula (I), V ⁰ is -COO-, -OCO-,-(CH
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 is the number of hydrogen atoms or carbon 1-2
2 represents a hydrocarbon group, 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 -CO.
O-D ^12, or represents a -COO-D ¹² through a hydrocarbon group (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 (IV). [Chemical 2] In formula (IV), 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 as or different from each other, and each is —O—, —CO—, —CO ₂ —, —.
_{OCO -, - SO 2 -,} - N (D 22) -, - CON (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 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 carbon atom
~ 18 hydrocarbon groups. [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] Wherein (II), X ⁰ is -COO -, - OCO -, - CH 2
_{OCO -, - CH 2 COO -} , - O -, - SO 2 -, -
^{CO -, - CONR 11 -,} - SO 2 NR 11 -, or a phenylene group (wherein R ¹¹ represents a hydrogen atom or a hydrocarbon group). 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 —C via a hydrocarbon group.
It represents a OO-Z ¹ (wherein Z ¹ represents a hydrogen atom or a hydrocarbon group). [Chemical 5] In formula (III), X ¹ has the same meaning as X ⁰ in formula (II). Q ¹ represents an aliphatic group having 6 to 32 carbon atoms. d ¹
And d ² may be the same or different from each other and have the formula (II)
It has the same contents as b ¹ and b ^{2 in the above} . 2. The dispersion-stabilizing resin [P] has --PO ₃ H ₂ , --SO ₃ H, and --COO at one end of its polymer main chain.
H, -P (= O) (OH) R ¹ [wherein R ¹ represents a hydrocarbon group or -OR ² (R ² represents a hydrocarbon group)], -OH, formyl group, -CONR ³ R ⁴ , -SO
₂ NR ³ R ⁴ [wherein R ³ and R ⁴ each independently represent a hydrogen atom or a hydrocarbon group], a cyclic acid anhydride-containing group, and at least one polar group selected from an amino group The liquid developer for electrostatic photography according to claim 1, wherein 3. The dispersion stabilizing resin [P] contains a polymerizable functional group copolymerizable with the monomer (A) at one end of its polymer main chain. Item 1. A liquid developer for electrostatic photography according to Item 1.