JPH03123362A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To enhance the stability of dispersion, redispersibility and fixability of the liquid developer by using specific resin particles obtd. by copolymn. in the presence of a specific resin for stabilizing dispersion for the dispersed resin particles. CONSTITUTION:This developer is produced by dispersing at least the resin particles in a prescribed nonaq. solvent. The particles are formed by copolymerizing a monofunctional monomer and a monofunctional macromonomer of a prescribed mol. wt. formed by bonding the group of formula III only to the one terminal of the polymer main chain by the unit of formula II in the presence of the resin for stabilizing dispersion which is crosslinked in a part of the polymer by the repeating unit of formula I and has the acid group selected from -PO3H2, -SO3H, -COOH, etc., only at the one terminal of the polymer main chain. In the formulas, T<1> denotes COO, OCO, etc.; A<1> denotes 6 to 32C aliphat. group; a<1>, a<2> denote H, halogen, etc.; R1, R2 denote 1 to 18C hydrocarbon; b1, b2, d1, d2 denote H, halogen, etc.; V1 denotes O, COO, etc.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a liquid developer for electrostatic photography comprising at least a resin dispersed in a carrier liquid having an electrical resistance of 10'Ωcm or more and a dielectric constant of 3.5 or less. In particular, redispersibility, storage stability,
It relates to a liquid developer with excellent stability, image reproducibility, and fixing properties.

(Prior art) General electrophotographic liquid developers are petroleum-based organic or inorganic pigments or dyes such as carbon black, nigrosine, and phthalocyanine blue, and natural or synthetic resins such as alkyd resins, acrylic resins, rosins, and synthetic rubbers. It is dispersed in a liquid with high insulating properties and low dielectric constant, such as aliphatic hydrocarbon, and further contains a polarity control agent such as a metal soap, lecithin, linseed oil, higher fatty acid, or a polymer containing vinyl pyrrolidone. be.

In such a developer, the resin is dispersed as insoluble latex particles in the form of particles with a diameter of several ns to several hundred 011, but in conventional liquid developers, a soluble dispersion stabilizing resin, a polarity control agent, and insoluble latex particles are dispersed. Due to insufficient bonding, the soluble dispersion stabilizing resin and polarity control agent were likely to diffuse into the solution. Therefore, due to long-term storage or repeated use, the soluble dispersion stabilizing resin is detached from the insoluble latex particles, causing the particles to settle, aggregate, or accumulate.
The drawback was that the polarity was unclear. Furthermore, since particles that have aggregated and accumulated are difficult to redisperse, they remain attached to various parts of the developing machine, leading to problems with the developing machine such as staining of the image area and clogging of the liquid feed pump.

In order to improve these drawbacks, a means for chemically bonding a soluble dispersion stabilizing resin and insoluble latex particles has been devised and is disclosed in US Pat. No. 3,990,980 and the like. However, although the dispersion stability of these liquid developers against natural sedimentation of particles has improved to some extent, it is still not sufficient, and when used in an actual developing device, the toner that adheres to various parts of the device forms a film. This has the disadvantage that redispersion stability is insufficient for practical use, such as solidification, making redispersion difficult, and furthermore causing equipment failure and smudging of copied images. In addition, in the method for producing resin particles described above, in order to produce monodisperse particles with a narrow particle size distribution, there are significant restrictions on the combination of the dispersion stabilizer used and the monomer to be insolubilized; The particles had a wide particle size distribution containing a large amount of coarse particles, or the particles had a polydisperse particle size with two or more average particle sizes. Furthermore, it is difficult to obtain a desired average particle size with monodispersed particles having a narrow particle size distribution, and large particles of 1 or more or very fine particles of 0.1 or less are formed. Furthermore, there are problems in that the dispersion stabilizer used must be manufactured through a complicated and time-consuming manufacturing process.

Furthermore, in order to improve the above-mentioned drawbacks, insoluble dispersed resin particles of a copolymer of a monomer to be insolubilized and a monomer containing a long-chain alkyl moiety or a monomer containing two or more types of polar components are used. A method for improving the dispersity, redispersibility, and storage stability of particles by
It is disclosed in No. 62-151868 and the like.

(Problems to be Solved by the Invention) On the other hand, in recent years, a method of printing 5,000 or more sheets using a master plate for offset printing using an electrophotographic method has been attempted, and improvements in the master plate in particular have been progressing. It has become possible to print more than 10,000 sheets in plate size. Further, the operating time of electrophotographic engraving systems has been shortened, and improvements have been made to speed up the development and fixation process.

JP-A-60-179751 and JP-A No. 62-15186
Dispersed resin particles produced according to the method disclosed in No. 8, when the development speed increases, the dispersibility of the particles,
The performance is still not necessarily satisfactory in terms of redispersibility, printing durability when the fixing time is shortened, or in the case of large-sized master plates (for example, A-3 size or larger). .

The present invention solves the problems of conventional liquid developers as described above.

An object of the present invention is to provide a liquid developer that can speed up the development and fixation process and has excellent dispersion stability, redispersibility, and fixation properties even in an electrophotolithography system using a large-size master plate. That's true.

Another object of the present invention is to provide a liquid developer that enables the electrophotographic production of offset printing plates having excellent printing ink oil sensitivity and stiffness resistance.

Another object of the present invention is to provide a liquid developer suitable for various electrostatic photographs and various transfer applications in addition to the above-mentioned applications.

Still another object of the present invention is to provide a liquid developer that can be used in any system where a liquid developer can be used, such as inkjet recording, cathode ray tube recording, and recording of various change processes such as pressure changes or electrostatic changes. That's true.

(Means for Solving the Problems) The above-mentioned aspects of the present invention are characterized in that a non-aqueous solvent having an electrical resistance of 10'ΩC or more and a dielectric constant of 3.5 or less has a small amount of electrostatic In the photographic liquid developer, the dispersed resin particles are partially crosslinked with a polymer containing a repeating unit represented by the following general formula (I), and only one end of at least one polymer main chain is crosslinked. , a posuz group, -SO,
O group, -COOH group, -OH group, -5■ group, However, only at one end of the polymer main chain consisting of a monofunctional monomer (A) that becomes insolubilized by polymerization and a repeating unit shown by the maximum (■) below, Copolymer resin particles obtained by polymerizing a solution containing at least one monofunctional macromonomer (M) having a number average molecular weight of 104 or less, which is formed by bonding polymerizable double bond groups. This was achieved by an electrostatographic liquid developer characterized by the following.

General formula (1) % formula % In general formula (I), 71 is -C00-1-OCO-1-C
I1.0CO-1-cutcoo-1-〇- or -SO
□ Represents -.

AI represents an aliphatic group having 6 to 32 carbon atoms.

al and a! may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group having 1 to 8 carbon atoms, -coo-z', or -coo via a hydrocarbon group having 1 to 8 carbon atoms. -z' (here, 21 is the number of carbon atoms
~22 hydrocarbon groups).

-Max (II) b, bl -+CH-C←- Vo 4R+ X+IRz XtVY6-Max (I
ll) CH=C I- In the general formula (I[), Vo is 10-1-S-1-C
OO-1-OCO--CH20GO- or -C)l,C
Represents oo-.

Y represents a hydrogen atom or a hydrocarbon group having 1 to 1 carbon atoms.

×1 and x2 may be the same or different, and -O
--CO-1-COt--0CO--3o□--N-Y
+ Y represents -CON- or -NCO- (y+ represents the same content as Y0 above).

R3 and R2 may be the same or different from each other, may be substituted, or -CH- in the main chain Xs<R5-X5
Hitomi Y.

(XS, X, may be the same or different from each other and have the same content as XI, Indicates a hydrogen group, Y2 has the same content as Yo] carbon number 1
~18 hydrocarbon groups.

1) Is bt may be the same or different from each other (, hydrogen atom, halogen atom, cyano group, hydrocarbon group, Coo
-R5 or -COO-Rs via a hydrocarbon (Rs represents a hydrogen atom or a hydrocarbon group which may be substituted).

m, n and p may be the same or different, and are 0 to 4
, where m+n is at least 1 or more.

Complying with general formula (1), vl is -o--coo-OC
O--CH20GO-1-cnzcoo-1-8O□-
-CONII-1 or -CONHCONH- (
However, ``represents a hydrogen atom or a hydrocarbon group having 1 to 1 carbon atoms.''

dl and d2 may be the same or different from each other, and each has the same meaning as bt or bl in -maximum (Il) above.

Hereinafter, the liquid developer of the present invention will be explained in detail.

Electrical resistance used in the present invention is 10''ΩC- or more, dielectric constant 3.
5 or less, preferably linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, or aromatic hydrocarbons, and halogen-substituted products thereof. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, Isopar E1 Isopar G1 Isopar H1 Isopar L (Isopar; trade name of Exxon) , Shellsol 70, Shellsol 71 (Shellsol; trade name of Shell Oil Company),
Amsco OMS, Amsco 460 solvent (Amsco; trade name of Spirits Inc.), etc. are used alone or in combination.

Non-aqueous dispersed resin particles (hereinafter sometimes referred to as latex particles), which are the most important component in the present invention, are polymers containing repeating units represented by the above general formula (I) in a non-aqueous solvent. A portion of the polymer chain of the dog is cross-linked and only one end of at least one polymer backbone has -POsT.
The monomer (A) and the macromonomer ( M) (so-called polymerization granulation method).

Here, as the non-aqueous solvent, basically any solvent can be used as long as it is miscible with the carrier liquid of the electrostatic photographic liquid developer.

That is, the solvent used in producing the dispersed resin particles may be any solvent as long as it is miscible with the carrier liquid (preferably linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, etc.). Examples include hexane, octane, isooctane,
Decane, isodecane, decalin, nonane, dodecane, isododecane, isoparaffin-based petroleum solvent Isopar E1 Isopar G1 Isopar H2 Isopar L,
Sherzoll 70. Sherzoll 71. Amsco OMS
, Amsco 460 solvent, etc. may be used alone or in combination.

Solvents that can be used in combination with these organic solvents include alcohols (e.g., methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, fluorinated alcohol, etc.), ketones (e.g., acetone, methyl ethyl ketone, cyclohexanone, etc.), Carboxylic acid esters (e.g. methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, etc.), ethers (e.g. diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons (For example, methylene dichloride, chloroform, carbon tetrachloride, dichloroethane, methylchloroform, etc.).

It is preferable that the non-aqueous solvent used in the mixture be removed by heating or distillation under reduced pressure after polymerization and granulation, but even if it is brought into the liquid developer as a latex particle dispersion, it will not affect the liquid in the developer. There is no problem as long as the resistance is within a range that satisfies the condition of 10<9 >[Omega]C- or more.

Usually, it is preferable to use the same solvent as the carrier liquid at the stage of producing the resin dispersion, and it is preferable to use the same solvent as the carrier liquid. Examples include hydrogenated hydrocarbons.

Dispersion according to the present invention used to make a stable resin dispersion of a solvent-insoluble copolymer produced by copolymerizing a monomer (A) and a macromonomer (M) in a nonaqueous solvent. The stabilizing resin is a polymer containing a repeating unit represented by the general formula (1), and a portion of the polymer chain is crosslinked, and at least one end of the polymer main chain has a POsHi group, - 801 group, -COOH group, -OH group,
-511 group, Δ□ is a polymer soluble in the non-aqueous solvent, which is formed by bonding acidic groups.

Below, the repeating unit represented by general formula (1) will be explained in more detail.

In the repeating unit represented by general formula (1), aliphatic groups and hydrocarbon groups may be substituted.

In general formula (1), T1 is preferably -COO-1
OCO--CH*0CO-1-CItCOO- or -0
-, more preferably -000-1-CH, CO
Represents 0- or -〇-.

AI preferably has 8 to 22 carbon atoms and may be substituted,
represents an alkyl group, alkenyl group or aralkyl group,
Examples of the substituent include halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), -0-Z''-C
oo-Z"-0CO-Z"(cocot'Z" represents an alkyl group having 6 to 22 carbon atoms, such as hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, etc. ), and other substituents.

More preferably, ^1 represents an alkyl group or alkenyl group having 8 to 22 carbon atoms, such as octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosanyl group, octenyl group , decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, etc.

al and at may be the same or different, preferably a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a carbon number 1
~3 alkyl group, -coo-z' or -GHzCOO
-Z' (here, Zl represents an aliphatic group having 1 to 22 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group) group, hexadecyl group, octadecyl group, docosanyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, etc., and these aliphatic groups include the above-mentioned A1
may have the same substituents as those represented by). More preferably, al and a2 are each a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.), -coo-z3 or -CH
ICoO-Z' (,:,:: Te23 has 1 to 1 carbon atoms
2 represents an alkyl group or an alkenyl group, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a pentenyl group,
Examples include hexenyl group, heptenyl group, octenyl group, decenyl group, etc., and these alkyl groups and alkenyl groups may have the same substituents as those represented by AI above.

Monomer (A) and macromonomer (M
) The dispersion stabilizing resin of the present invention, which is used to make a stable resin dispersion from the solvent-insoluble copolymer produced by copolymerizing A polymer containing a portion of which is crosslinked, and at least one end of the polymer main chain contains a carboxy group, a sulfo group, a phosphono group, a hydroxyl group, or a hydrocarbon having 1 to 18 carbon atoms. group (more preferably an optionally substituted aliphatic group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, hexyl group,
Octyl group, 2-chloroethyl group, 2-methoxyethyl group, butenyl group, pentenyl group, hexenyl group, benzyl group, phenethyl group, bromobenzyl group, methoxybenzyl group, chlorobenzyl group, methylbenzyl group, cyclopentyl group, cyclohexyl group etc.), an optionally substituted aryl group (e.g., phenyl group, tolyl group, xylyl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, ethylphenyl group, methoxycarbonylphenyl group, etc.)] It is a polymer formed by bonding at least one type of acidic group selected from the following. here,
The acidic group has a chemical structure in which it is directly bonded to one end of the polymer main chain or bonded via an arbitrary linking group.

Linking groups include carbon-carbon bonds (-double bonds or double bonds), carbon-heteroatom bonds (heteroatoms include:
(for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.), and any combination of atomic groups of heteroatom-heteroatom bonds. For example, -(C)-(where z4 and ZS
is ZS, hydrogen atom, halogen atom (e.g. fluorine atom,
chlorine atom, bromine atom, etc.), cyano group, hydroxyl group,
-4CH, CH)-17 hydrogen atom, hydrocarbon group having the same meaning as zl in the general formula (I), etc. A single linking group or a linking group composed of any combination selected from atomic groups such as

The polymer component of the dispersion stabilizing resin of the present invention has the general formula (I)
A homopolymer component or a copolymer component selected from among the repeating units represented by or with another monomer that can be copolymerized with a monomer corresponding to the repeating unit represented by general formula (1). It is a partially crosslinked polymer that contains a copolymer component obtained by polymerization.

Here, other monomers that can be copolymerized with the monomer corresponding to the repeating unit represented by general formula (I) include, for example, -
In the monomer corresponding to the repeating unit represented by formula i (summer), al, a2 and tl each have the same meaning as that of general formula (1), and 80 represents an aliphatic group having 1 to 5 carbon atoms (e.g. ,
Methyl group, ethyl group, butyl group, pentyl group, cyclopentyl group, 2chloroethyl group, 2-bromoethyl group, 2
-cyanoethyl group, 3-chloropropyl group, 2-(methylsulfonyl)ethyl group, etc.) or aromatic groups (e.g.
Examples include monomers such as phenyl group, tolyl group, xylyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, etc.

Furthermore, as specific examples of other copolymerizable monomers,
For example, 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 and Technology, pp. 175-184, Baifukan ( (published in 1986), such as N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.), with a carboxamide group or a sulfoamide group. and a polymerizable double bond group-containing compound (e.g., acrylamide, methacrylamide, diacetone acrylamide, 2-carboxyamidoethyl methacrylate, vinylbenzenecarboxamide, vinylbenzenesulfamide, 3-sulfamidopropyl methacrylate, etc.), Examples include styrene and its derivatives (eg, styrene, chlorostyrene, vinyltoluene, vinylnaphthalene, chloromethylstyrene, etc.).

In the dispersion stabilizing resin of the present invention, the monomer corresponding to the repeating unit represented by the general formula (I) is 40% by weight to 1% by weight.
00% by weight is suitable, preferably 60% by weight to 10% by weight.
It is 0% by weight.

In the dispersion stabilizing resin of the present invention, a commonly known method can be used to introduce a crosslinked structure into the polymer. Namely, (1) a method in which a polyfunctional monomer is coexisting in the polymerization reaction of a monomer, and (2) a method in which a functional group that promotes a crosslinking reaction is contained in the polymer and crosslinked by a polymer reaction. .

The dispersion stabilizing resin of the present invention has a simple manufacturing method (for example, a long reaction time is required, the reaction is not quantitative, impurities are mixed in due to the use of a reaction accelerator, etc.).
Functional group with self-crosslinking reaction: CONHCHZO
Z' (here zl represents a hydrogen atom or an alkyl group)
Alternatively, a crosslinking reaction based on polymerization is effective.

In the polymerization reaction, preferably, a method of crosslinking between polymer chains by polymerizing a monomer having two or more polymerizable functional groups together with a monomer corresponding to the repeating unit represented by the above formula (1). It is.

Specifically, as the polymerizable functional group, C11z・C11;
b+IC-0-C-1CHm=CIC-0-C-1CH
,CH! =CH-NHCO-1CHz=CH-CHy-
NHCO-1CHt=CH-5(h-, CHz=CJI
-CO-1C11!・CH-0-, CH-0-Cl-5-
, etc., but if the above polymerizable functional group is
The monomer having two or more of these polymerizable functional groups may be a monomer having two or more of the same or different polymerizable functional groups.

Specific examples of monomers having two or more polymerizable functional groups include, for example, styrene derivatives such as divinylbenzene and trivinylbenzene as monomers having the same polymerizable functional group;
Polyhydric alcohols (e.g. ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol #200, #40G, #600.1.
3-butylene glycol, neopentyl glycol, dipropylene glycol, polypropylene glycol, trimethio-Jl/7'lopane, trimethylolethane,
esters, vinyl ethers or allyl ethers of polyhydroxyphenols (e.g. hydroquinone, resorcinol, catechol and their derivatives); dibasic acids (e.g. malonic acid); , succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, phthalic acid, itaconic acid, etc.); , 4-butylene diamine, etc.) and a carboxylic acid containing a vinyl group (for example, methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.).

Further, monomers having different polymerizable functional groups include, for example, carboxylic acids containing vinyl groups [e.g., methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloylpropionic acid, acryloylpropionic acid, itaconylyl acetic acid, Itaconiloylpropionic acid, reactants of carboxylic acid anhydrides and alcohols or amines (e.g. allyloxycarbonylpropionic acid,
ester derivatives or amide derivatives containing vinyl groups (e.g., vinyl methacrylate, vinyl acrylate, vinyl itaconate, methacrylic acid) Allyl, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate, vinyl methacryloylpropionate, allyl methacryloylpropionate, vinyloxycarbonyl methyl methacrylate, vinyloxycarbonyl acrylate methyloxycarbonyl ethylene ester, N-allylacrylamide, N- Allyl methacrylamide, N
- allyl itaconic acid amide, methacryloyl propionic acid allyl amide, etc.); or amino alcohols (e.g., aminoethanol, 1-amitubupanol, 1-aminobutanol, ■-aminohexanol, 2-aminobutanol, etc.) and vinyl groups. Examples include carboxylic acid condensates.

The monomer having two or more polymerizable functional groups used in the present invention is 15% by weight or less of the total monomers, preferably 10% by weight or less of the total monomers.
The dispersion stabilizing resin which is soluble in the non-aqueous solvent of the present invention is formed by polymerizing in an amount of % by weight or less.

In addition, the dispersion stabilizing resin of the present invention, which has a specific acidic group bonded only to one end of at least one polymer main chain, can be prepared by: A method of reacting reagents (a method using an ionic polymerization method), a method of radical polymerization using a polymerization initiator and/or a chain transfer agent containing a specific acidic group in the molecule (a method using a radical polymerization method), or (2) Easily produced by a synthetic method such as a method in which a polymer containing a reactive group at the end obtained by the above-mentioned ionic polymerization method or radical polymerization method is converted into the specific acidic group of the present invention by a polymer reaction. I can do it.

Specifically, P, Dreyfuss & R,P,
QuirkEncycle, Polym, Sci,
Eng, +7, 551 (1987), Yoshiki Nakajo, Yuya Yamashita, Dyes and Chemicals J, :m, 232 (19
85), Akira Ueda, Susumu Nagai, “Science and Industry J Toughness,” 57 (1)
986) and the literature cited therein.

The weight average molecular weight of the dispersion stabilizing resin of the present invention is lXl0'
~6X10' is preferred, more preferably 2X10'~
When the weight average molecular weight of 3X10' is less than 1X10', the average particle size of the resin particles obtained by polymerization granulation becomes large (for example, larger than 0.5) and the particle size distribution becomes wide. In addition, if it exceeds 6X10', the average particle size of the resin particles obtained by polymerization granulation becomes large and 0.1
It may become difficult to align the average particle size within the preferred range of 5 to 0.4 ts.

Specifically, the dispersion stabilizing resin polymer used in the present invention contains a monomer corresponding to the repeating unit represented by general formula (1), the above-mentioned polyfunctional monomer, and the acidic group. A method in which a mixture of chain transfer agents is polymerized using a polymerization initiator (for example, an azobis compound, a peroxide, etc.), or (2) a method in which a polymerization initiator containing the acidic group is used without using the above chain transfer agent, A method of polymerization, or (1) a method in which a compound containing the acidic group is used as both a chain transfer agent and a polymerization initiator, and (2) a method in which a compound containing the acidic group is used as a substituent for the chain transfer agent or polymerization initiator in the above three methods. , amino group,
After a polymerization reaction using a compound containing a halogen atom, an epoxy group, an acid halide group, etc., the acidic group is introduced by reacting with these functional groups in a polymer reaction. I can do it.

The chain transfer agent used is, for example, the acidic group or
A mercapto compound (with a substitution fund that can be induced into the acidic group)
For example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N-(2-mercaptopropionyl)glycine, 2-mercaptonicotinic acid, 3[N(2 -mercaptoethyl)carbamoyl]propionic acid, 3-[N-(2-mercaptoethyl)amidinopropanoic acid, N-(3-mercaptopropionyl)
Alanine, 2-mercaptoethanesulfonic acid, 3-mercaptoethanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,
2-propanediol, 1-mercapto-2-propatol, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mecarb-limidazole, 2-mercapto-3-viridinol, etc.), or the above acidic groups Or an iodized alkyl compound containing a substituent (for example, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.).

Preferred are mercapto compounds.

In addition, examples of polymerization initiators containing "the acidic group" or a substituent that can be induced into "the acidic group" include 4.4
'-azobis(4-cyanovaleric acid), 4,4'-azobis(4-cyanovaleric acid chloride L2,2'-azobis(2-cyatuburobanol), 2,2'-azobis(2
-cyanopentanol), 2,2'-azobis(2-(
5-hydroxy-3,4,5,6-tetrahydrobyrimidin-2-yl)propane), 2,2'-azobis(2
-Methyl-N-(1,1-bis(hydroxymethyl)-
2-Hydroxyethyl]propioamide l, 2.2'-
Azobis(2-methyl-N-(1,1-bis(hydroxymethyl)ethyl)propioamide), 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)-propioamide L 2,2'- Examples include azobis(2-amidinopropane).

The amount of each of these chain transfer agents or polymerization initiators is 0.1 to 15% by weight, preferably 0.5 to 10% by weight, based on 100 parts by weight of the total monomers.

The dispersion stabilizing resin of the present invention produced as described above is
The acidic group bonded only to one end of the polymer main chain interacts with the insoluble resin particles, and the component that becomes soluble in non-aqueous solvents is cross-linked, thereby increasing the affinity for non-aqueous solvents. It is estimated that this is a significant improvement, and it is thought that these factors suppress aggregation and precipitation of insoluble particles and significantly improve redispersibility.

The monomers used in producing the non-aqueous dispersion resin include a monofunctional monomer (A) which is soluble in the non-aqueous solvent but becomes insolubilized by polymerization, and a co-monomer (A) that is soluble in the non-aqueous solvent. A distinction can be made between monofunctional macromonomers (M) that undergo polymerization.

Examples of the monomer (A) include vinyl esters or furyl esters of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, propionic acid, butyric acid, monochloroacetic acid, etc.);
Acrylic acid, methacrylic acid, crotonic acid, itaconic acid,
C1-3 alkyl esters or alkylamides of unsaturated carboxylic acids such as maleic acid; styrene derivatives such as styrene, vinyltoluene, chlorostyrene, and α-methylstyrene; acrylic acid, methacrylic acid, crotonic acid, maleic acid acids, unsaturated carboxylic acids such as itaconic acid, their anhydrides or amides; hydroxyethyl methacrylate, hydroxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl acrylate, dimethytaminoethyl methacrylate, diethylaminoethyl methacrylate, trimethoxysilylpropyl methacrylate, N-vinylpyrrolidone, acrylonitrile, methacrylaterile, 2-cyanoethyl methacrylate, 2-chloroethyl methacrylate, N-vinylpyridine, N-vinylimidazole, 2-furfurylethyl methacrylate, hydroxy group, amino group, amide group, Examples include polymerizable monomers containing various polar groups such as cyano groups, sulfonic acid groups, carbonyl groups, halogen atoms, and heterocyclic groups.

Two or more types of monomers (A) may be used in combination.

-Functional macromonomer (M) can be copolymerized with monomer (A) only at one end of the polymer main chain consisting of repeating units represented by -C formula ([1)]. It is a macromonomer having a number average molecular weight of 10' or less, which is formed by bonding a polymerizable double bond group shown in III).

In the general formulas (I[) and (III), 3, bt,
The hydrocarbon groups contained in Yo, Vo, Yt, d+, R2, and R6 each have the indicated number of carbon atoms (as an unsubstituted hydrocarbon group), but these hydrocarbon groups may be substituted.

The repeating unit represented by the general formula (n) used in the present invention will be further explained.

vo is -o--s--coo--0CO--CH2O
Represents CO- or -cozcoo-.

Yo preferably represents a hydrogen atom or an optionally substituted aliphatic group having 1 to 1 B carbon atoms in total. Preferred aliphatic groups include optionally substituted alkyl groups having 1 to 18 carbon atoms (e.g., methyl group, methyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), substitution with 4 to 18 carbon atoms an optionally substituted alkenyl group (for example, 2-methyl-1
-propenyl group, 2-butenyl group, 2pentenyl group, 3
-Methyl-2-pentenyl group, 1-pentenyl L 1
-hexenyl group, 2-hexenyl group, 4-methyl-2-
hexenyl group, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g. 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.)
, an optionally substituted alicyclic group having 5 to 8 carbon atoms (for example,
cyclohexyl group, 2cyclohexylethyl group, 2-cyclopentylethyl group, etc.).

xl and Xt may be the same or different from each other, and V.

O--CO-1-COO--QCO--5Oz--NY
+ Yt represents -CON- or -NGO- (Yt indicates the same content as v0 above), more preferably -O--CO-
1I represents -coo--oco or -N-.

R1 and R8 may be the same or different from each other, may be substituted, or -CH- may be replaced by X 3 (Ra
-X a )TY A hydrocarbon group having 1 to 18 carbon atoms that may be interposed in the z bond (the hydrocarbon group includes an aliphatic group such as an alkyl group, an alkenyl group, an aralkyl group, or an alicyclic group) Preferred specific examples of these aliphatic groups are the same as the above-mentioned preferred aliphatic groups of Yo. However, Xl and X4 may be the same or different and have the same content as X9 and x2 above, and R4
is an optionally substituted alkylene group having 1 to 18 carbon atoms,
Represents an alkenylene group or an aralkyl group, and Yo is the above Y
Indicates the same content as 0.

Furthermore, regarding R and R2, to give a specific example, R
F+ch (Ilt, Re are hydrogen atoms, alkyl groups, halogen a +cl+) --(X 3, Xl, Yt, R, and p
is composed of any combination of atomic groups such as the above X5 (which has the same meaning as the symbol Rn-X4i'h).

b, and b! may be the same or different from each other,
Preferably a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.), -
COO-Rs or -CIlgCOORs (Rs is a hydrogen atom or a C1-18 alkyl group, alkenyl group,
represents an aralkyl group, an alicyclic group, or an aryl group, which may be substituted, and specifically represents the same content as described for Y above.

Furthermore, m, n and p may each be the same or different,
Represents the number 0.1, 2.3.4. However, m+n is at least 1 or more.

More specific examples of the above-mentioned repeating unit represented by -maximum (I[) will be given below. However, the content of the present invention is not limited to these. In the following, a represents ) or CHl, R represents an alkyl group of CI-Im, and P'' represents a hydrogen atom or an alkyl group of Cl-1@. , k8,
k2 is an integer from 1 to 12, and j! 2 represents an integer from 1 to 100.

(＾)-18 ■ -(CHl2-CI- Coo(CHliOCOR (A)-2 cHs CI- Coo (Increase CH GOOR (A)-3 -ECHz -CI- Coo(CIIz%, 0CO(Cllx pigeon ocoρ(
A)-4 4cut CH C00(CIIffiiOCO(C112iCOOR(
A)-5 (A) (CHl-CH Coo (CHz埴-〇C0CR=CI(-C(!0R
(A) -4CHZ CH (A) -12a -(CHz C) - COOCHgCIICIlzOCOR C0R COOCRCII□GOOR CHzCOOR (A) (＾) -13 -1+cut-c+- C00(C11! YaOCO(CH mountain NH-R 4CH,-
C÷-" (A) 云CHz-C+- cozcoo(cnz spear C00R (A) 0 Coo(C)IiCHzO pigeon R" 1+CH!-C)-COO(Add C1l-0CO(CI+□), so□ R
→CH-CH and m=Coo(C1hdanOCOR (A)-16 CI.

-(CH-C11 and m- C00C1liCHC)IxOCOR C0R (8) -17 -(C1h-CIlh OCO(Cllt)170COR (A)-18 -(C1, -cllHea(CHt)2bu00(CHx)r; C00R-Max(I
ll), V is -0-COO C0 ct+toco-1-CIl, COO-1-3O7CO
Represents NII-1 or -CONHCONH-. However, R7 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. As the hydrocarbon group, an aliphatic group having 1 to 18 carbon atoms is preferable, and specific examples thereof include those described for Y0 above.

dl and d2 may be the same or different, and have the same meaning as bl or s in maximum (II) above. Preferred ranges of dl and d2 are the above-mentioned bl and b2, respectively.
The content is similar to that explained in .

-a It is more preferable that either bl or b2 in formula (II) or dl or d2 in general formula (I) be a hydrogen atom.

The macromonomer provided in the present invention has at least one repeating unit represented by -a formula (II) at one end of the polymer main chain, as described above.
It has a chemical structure in which the polymerizable double bond group represented by [l) is directly bonded or bonded by an arbitrary linking group. Examples of the group connecting the formula (II) component and the formula (III) component include a carbon-carbon bond (-double bond or double bond), a carbon-heteroatom bond (heteroatoms include, for example, an oxygen atom and a sulfur atom). , nitrogen atom, silicon atom, etc.), and any combination of atomic groups of heteroatom-heteroatom bonds.

Among the macromonomers (M) of the present invention, preferred are those represented by the formula ('rV).

Formula ([V) In formula (IV), bl, b! , dl, dt, Ye, vo
, Vo, R1, R2, Xl, ×2, m, n are each -
Maximum represents the same content as explained in (I[) and (III).

9 W is a simple bond or (C)-(R9, R1゜ is water IG. , methyl group, ethyl group, 11 11 Si- (R++, R1! each represents a hydrogen atom or a hydrocarbon group expressing the same content as the above RI!Yo). Represents a linking group composed of a group or an arbitrary combination.

The upper limit of the number average molecular weight of the macromonomer (M) is lXl0
If it exceeds ', printing durability will decrease. On the other hand, if the molecular weight is too small, stains tend to occur, so it is preferably 1×10 3 or more.

- In maximum (II), (III) or (IV), Yo, Vo, -:V+, b3, b3, d5, dt
A particularly preferable example will be shown for each k.

As vo, -COO--0CO--0--(:1h
COO mapo is -CHJCO-, vo is an alkyl group or alkenyl group having 18 or less carbon atoms, and vl is all of the above (however, R,, is a hydrogen atom), bl, b2 , dl, and d2 include a hydrogen atom or a methyl group.

SO, -1-CON-1-3O, N-1-NHCoo-
1-1111CONI, V, -W- (B)-4 CHl=C C0NH(CIlt)-r7S One specific example will be shown.

but, The content of the invention is It is not limited to these.

In the following, (B)-5 CIltlIC represents ■ or CHff, 11+ represents an integer from 2 to 12, n,
represents an integer from 1 to 12.

C00CToCHCHzOOC(CHt)=〒S-0■ CH1=C Coo(CHl)ir7S (B)-2 CH*=C C00(C1h)v70co(CHz)r7 SC1,
=C 萱C00(CHl 萑NHCO(C1h 埴SCH*=C C0C00(CH'17NHcOO(CHx)i7 S
-0 cui=c COO(CH NHCONH(CHx) i75(B)
-13 coz=c C0NIICOO(Cut)i7 S In the macromonomer (M) used in the present invention, in addition to the repeating unit represented by the general formula (It), other repeating units are contained as copolymerization components. Good too.

As the other copolymerization component, any repeating unit may be used as long as it is a repeating unit composed of another monomer that can be copolymerized with the monomer corresponding to the -maximum (II) repeating unit. Examples of such other monomers include acrylic acid, methacrylic acid,
Icconic acid, crotonic acid, maleic acid, vinyl acetic acid, 4
-Unsaturated carboxylic acids such as pentenoic acid and esters or amides of these unsaturated carboxylic acids; C1-22 fatty acid vinyl esters or allyl esters; vinyl ethers; styrene and histyrene gs form; unsaturated bond metals Examples include heterocyclic compounds.

Specifically, examples thereof include the compounds exemplified as monomer (A) described above, but are not limited thereto.

In the total sum of repeating units of the macromonomer (M),
-i The repeating unit represented by formula (II) has a total of 40
The content is preferably at least 60% by weight, more preferably from 60 to 100% by weight.

- If the component represented by the maximum (n) is less than 40% by weight of the total, the mechanical strength of the image area formed by dispersed resin particles will not be maintained sufficiently, and therefore the printing life when used as an offset master plate will be reduced. The effect of improving sex will no longer be seen.

The macromonomer (M) of the present invention can be produced by a conventionally known synthesis method. For example, (1) a method using ionic polymerization in which the ends of living polymers obtained by anionic polymerization or cationic polymerization are reacted with various reagents to form macromers, (2) methods of reacting carboxyl groups, hydroxyl groups, amino groups, etc. in molecules. A method using a radical polymerization method in which various reagents are reacted with an oligomer with a terminal reactive group bond obtained by radical polymerization using a polymerization initiator and/or a chain transfer agent containing a reactive group to form a macromer; Examples include a method using a polyaddition condensation method in which a polymerizable double bond group is introduced into an oligomer obtained by a polyaddition or polycondensation reaction in the same manner as the above-mentioned radical polymerization method.

Specifically, P, Dreyfuss & R,P, 口uirk+'Encyc1. Polym,
Sci, Eng., 7.551 (1987),
PF, Rempp+ E, Franta, Ad
v, Polym, Sci, +581 (19
84), Percec, V., Appl, Po.
1y+*, Sci, + I+95 (1984)
, R, ^sami+ M, TakaR4, M
akvas+ol.

Chew, 5uP91. +12. 163 (1
985), P. Rempp, etal Mak
vamol, Chew, 5upp1. , 8
+ 3 (1984), Yuji Yogami, Kagaku Kogyo Betsu, 56 (1987), Yuya Yamashita.

Polymer, 31.988 (1982), Shibe Kobayashi, Polymer, Betsu 625 (1981), Toshinobu Higashimura 1 Journal of Japan Adhesive Association, ■536 (1982), Hiroshi IH-1 Polymer Processing, Japan, 262 ( 1986), Higashi Takashibe, Tsuda Takashi, 8g Noh Materials, ■Nugi.

It can be synthesized according to the methods described in reviews such as Klo, 5, and the literature and patents cited therein.

The dispersion resin of the present invention comprises a monomer (A) and a macromonomer (
It consists of at least one or more of each of M), and the important thing is that
If the resin synthesized from these monomers is insoluble in the nonaqueous solvent, a desired dispersed resin can be obtained. More specifically, it is preferable to use the macromonomer (M) in an amount of 0.05 to 10% by weight, more preferably 0.1 to 5% by weight, based on the monomer (A) to be insolubilized. More particularly preferably, it is 0.3 to 3%. Further, the molecular weight of the dispersion resin of the present invention is IO3 to 10', preferably 1
04-5X10'.

To produce the dispersion resin used in the present invention as described above, generally, the above-mentioned dispersion stabilizing resin, monomer (A), and macromonomer (M) are mixed in a non-aqueous solvent with benzoyl peroxide, The polymerization may be carried out by heating in the presence of a polymerization initiator such as abbisisobutyronitrile or butyllithium. Specifically, (1) a method of adding a polymerization initiator to a mixed solution of a dispersion stabilizing resin, a monomer (A), and a macromonomer (M);
■ A method in which the monomer (A) and the macromonomer (M) are dropped together with a polymerization initiator into a solution in which the dispersion stabilizing resin is dissolved, or ■ The total amount of the dispersion stabilizing resin and the monomer (A
) and a part of the macromonomer (M) mixture, the remaining monomer mixture is optionally added together with a polymerization initiator; There are also methods of optionally adding a mixed solution of the monomer (A) and the macromonomer (M) together with a polymerization initiator, and it can be produced using either method.

The total amount of the monomer (A) and macromonomer (M) is about 5 to 80 parts by weight based on 100 parts by weight of the nonaqueous solvent,
Preferably it is 10 to 50 parts by weight.

The soluble resin, which is a dispersion stabilizing resin, is used in an amount of 1 to 100 parts by weight of the total N of the monomers and macromonomers used above.
100 parts by weight, preferably 5 to 50 parts by weight.

The amount of polymerization initiator is 0 of the total amount of monomer and macromonomer.
．． 1-5% by weight is suitable.

Further, the polymerization temperature is about 50 to 180°C, preferably 60 to 120°C. The reaction time is preferably 1 to 15 hours.

When a polar solvent such as the above-mentioned alcohols, ketones, ethers, and esters is used in combination with the nonaqueous solvent used in the reaction, or when unreacted monomers (A) to be polymerized and granulated are If it remains, it is preferable to remove it by heating it to a temperature above the boiling point of the solvent or monomer or distilling it off under reduced pressure.

The non-aqueous dispersion resin produced according to the present invention as described above exists as fine particles with a uniform particle size distribution, and at the same time exhibits extremely stable dispersibility, and can be used repeatedly for a long time, especially in a developing device. Even if the dispersibility is improved, re-dispersion is easy even when the development speed is increased, and no stains are observed on various parts of the apparatus.

Furthermore, when fixed by heating or the like, a strong film was formed and exhibited excellent fixing properties.

In particular, in the non-aqueous dispersion resin described in JP-A No. 62-151868, monomers that polymerize and become insolubilized, and monomers that contain at least two ester bonds or the like in the molecule that can be copolymerized. These resin particles are obtained by coexisting polymers, and the dispersibility and rigidity resistance of the particles are significantly improved compared to conventional particles. A plate making machine using a plate (e.g. manufactured by Fuji Photo Film ■, EPL-560, EPL-82)
0, etc.), or when the processing speed of the plate making machine was increased, there was still a problem with the dispersibility of the particles. However, when the resin particles provided by the present invention are used, no problem occurs even under such severe conditions.

As described above, the liquid developer of the present invention speeds up the development and fixation process, and has excellent dispersion stability, redispersibility, and fixation properties even when a large-size master plate is used.

In the liquid developer of the present invention, a coloring agent may be used if desired, but the coloring agent is not particularly specified, and various conventionally known pigments or dyes can be used.

When coloring the dispersion resin itself, for example, one method of coloring is to physically disperse the dispersion resin using pigments or dyes, and there are a large number of known pigments or dyes. There is. Examples include magnetic iron oxide powder, powdered lead iodide, carbon black, nigrosine, alkali blue, Hanzai Elo, quinacridone red, and phthalocyanine blue.

Another coloring method is disclosed in Japanese Patent Application Laid-open No. 57-4873.
There is a method of dyeing the dispersed resin with a preferred dye, as described in No. 8 and others. Alternatively, as another method, there is a method of chemically bonding a dispersion resin and a dye, as disclosed in JP-A No. 53-54029, or as described in JP-B No. 44-22955, etc. As described above, there is a method of producing a copolymer containing a dye by using a monomer containing a dye in advance during production by a polymerization granulation method.

If desired, various additives may be added to the liquid developer of the present invention in order to strengthen charging characteristics or improve image characteristics.
No., page 44, those specifically described are used.

Examples include EVA, di-2-ethylhexyl sulfosuccinic acid metal salts, naphthenic acid metal salts, higher fatty acid metal salts, lecithin, poly(vinylpyrrolidone), and copolymers containing half-maleic acid amide components.

The amounts of each of the main components of the liquid developer of the present invention are explained below.

The toner particles mainly composed of resin (and optionally used colorant) are preferably 0.5 parts by weight to 50 parts by weight based on 1000 parts by weight of the carrier liquid.

If it is less than 0.5 parts by weight, the image density will be insufficient, and if it exceeds 50 parts by weight, fogging will tend to occur in non-image areas.

Furthermore, the above-mentioned carrier liquid soluble resin for dispersion stabilization may be used if desired, and the amount is 0.5 parts by weight per 1000 parts by weight of the carrier liquid.
Approximately 100 parts by weight can be added.

The charge control agent as described above is preferably used in an amount of 0.001 to 1.0 parts by weight based on 1000 parts by weight of the carrier liquid. Furthermore, various additives may be added as desired, and the upper limit of the total amount of these additives is regulated by the electrical resistance of the developer. That is, if the electrical resistance of the liquid developer with toner particles removed becomes lower than 109 Ωcm, it becomes difficult to obtain a continuous tone image of good quality, so it is necessary to control the amount of each additive added within this limit. is necessary.

(Example) Examples of the present invention are illustrated below, but the content of the present invention is not limited thereto.

A mixed solution of 97 g of t:pt octadecyl methacrylate, 3 g of thioglycolic acid, 5.0 g of divinylbenzene, and 200 g of toluene was heated to 85° C. with stirring under a nitrogen stream. 1.
0.8 g of 1'-azobis(cyclohexane-1-carbonitrile) (abbreviation ^, C, H, N, ) was added and reacted for 4 hours, and then ^, C, I1. Add 0.4g of N, react for 2 hours, and then add ^, C, I1. 0.2 g of N was added and reacted for 2 hours. After cooling, this mixed solution was reprecipitated in 1.5 ml of methanol, and the white powder was filtered and dried to obtain powder 8.
8g was obtained. The weight average molecular weight of the obtained polymer was 30,
It was 000.

Inside &2~9: P-2~P-
9 Each dispersion stabilizing resin was produced in the same manner as in Production Example 1, except that the monomers shown in Table 1 below were used instead of octadecyl methacrylate.

10 to 22: P-10 to P-22 In Production Example 1, instead of 5 g of divinylbenzene, which is a crosslinking polyfunctional monomer, the polyfunctional monomer or oligomer shown in Table 2 below was used. Other than using, operate in the same manner as in Production Example 1,
Each dispersion stabilizing resin was manufactured.

'''2 P Octadecyl methacrylate 97g, thiomalic acid 3g
A mixed solution of 4.5 g of divinylbenzene, 150 g of toluene, and 50 g of ethanol was heated to 60°C under a nitrogen stream.
It was heated to ゛C. 2. Add 0.5 g of 2'-azobis(isobutyronitrile) (abbreviation A, 1.B, N,),
React for 5 hours, then A, 1. Add 0.3g of B, N, and 3
Time reaction and further A.1. Add 0.2g of B, N, and 3
Time reacted. After cooling, it was reprecipitated into methanol 2E, and the white powder was filtered and dried. The yield was 185 g, and the weight average molecular weight of the polymer was 35.000.

2~: P-~P-9 In the above Production Example 23, the dispersion stabilizing resin was prepared in the same manner as in Production Example 23, except that 3 g of thiomalic acid was replaced with the mercapto compound shown in Table 3 below. Manufactured.

3Q: A mixture of 94 g of P-30 hexadecyl methacrylate, 1.0 g of diethylene glycol dimethacrylate, 150 g of toluene, and 50 g of isopropyl alcohol was heated at a temperature of 90° under a nitrogen stream.
It was heated to C. 2.2゛Azobis(4-cyanovaleric acid)
(abbreviation A, C, V, ) was added to the mixture and reacted for 8 hours.

After cooling, this reaction solution was reprecipitated in 1.5 mL of methanol, and the white powder was filtered and dried. The yield was 83 g, and the weight average molecular weight of the polymer was 65.000.

・P docosanil itetaku route 92g5ISP-22GA
(manufactured by Okamura Oil ■) A mixed solution of 1.5 g, 150 g of toluene, and 50 g of ethanol was heated at 80°C under a nitrogen stream.
After heating, 8 g of 4.4'-azobis(4-cyanopentanol) was added and reacted for 8 hours. After cooling, this reaction solution was reprecipitated into 1.5 mL of methanol, and the white powder was filtered and dried. The yield was 78 g, and the weight average molecular weight of the polymer was 41,000.

32:P-32 Octadecyl methacrylate 95g, 2-mercaptoethylamine 5g1 divinylbenzene 5g and toluene 2
00g of the mixed solution was heated to a temperature of 85°C under a nitrogen stream. 0.7 g of A, C, H, and N were added and reacted for 8 hours.

Next, 8 g of glutaconic acid anhydride and concentrated sulfuric acid were added and reacted at a temperature of 100'C for 6 hours. After cooling, it was reprecipitated into 1.5 liters of methanol, and the white powder was filtered and dried. The yield was 83 g and the weight average molecular weight was 31,000.

h-33: 95 g of p-33 octadecyl meccrylate, 3 g of thioglycolic acid, 6 g of ethylene glycol dimethacrylate, 150 g of toluene
A mixed solution of 50 g of ethanol and 50 g of ethanol was heated to a temperature of 80"C under a nitrogen stream.

Add 2g of A, C, V, and react for 4 hours.
0.5 g of V was added and reacted for 4 hours. After cooling, it was reprecipitated into 1.5 liters of methanol, and the white powder was filtered and dried.

The yield was Bog and the MW average molecule was 1135.000.

34:P-34 Tridecyl methacrylate 94g, 2-mercaptoethanol 6g1 Divinylhenzene 9g1 Toluene 150
A mixed solution of g and 50 g of ethanol was heated to a temperature of 80° C. under a nitrogen stream. 4g of A, C, H, and N were added and reacted for 4 hours, and further 2g of A, C, H, and N were added and reacted for 4 hours.

After cooling, it was rewashed in 1.5 liters of methanol, the methanol was removed by decantation, and the viscous mass was dried. Collection
The weight average molecular weight was 29,000 at 75 g.

Inner Output 35: P-35 A mixture of the above dispersion stabilizing resin P-34 (Ig, 100 g of toluene, 10 g of succinic anhydride and 0.5 g of pyridine) was heated at a temperature of 9.
The reaction was carried out at 0°C for 10 hours. After cooling, methanol 0.8I
! , the methanol was removed by decantation, and the viscous substance was dried. The yield was 43 g and the weight average molecular weight was 30,000.

Inside ``36~39:P-36~P-
39 In Production Example 35 of the dispersion stabilizing resin P-35, each dispersion was prepared in the same manner as in Production Example 35, except that the dicarboxylic acid anhydride shown in Table 4 below was used instead of succinic anhydride. A stabilizing resin was produced.

A mixture of 86 g of 4Q: P-40 (octadecyl methacrylate), 10 g of N-methoxymethylacrylamide, 4 g of thioglycolic acid, 150 g of toluene, and 50 g of isopropanol was heated to a temperature of 80° C. under a nitrogen stream.

Added 0.8g of A,C,l(,11,) and reacted for 8 hours. Next, using a mouth ean-3 tark, the temperature was 110'.
C. and stirred for 6 hours. The solvent used, isopropanol, and methanol produced as a by-product in the reaction were removed.

After cooling, it was reprecipitated into 1.5 liters of methanol, and the white powder was filtered and dried. Yield: 82g, weight average molecular weight: 45.0
It was 00.

A mixed solution of 96 g of 3M 2-(n-hexylcarbonyloxy)ethyl methacrylate, 4 g of thioglycolic acid, and 200 g of toluene was heated to 70° C. while stirring under a nitrogen stream. 1.0 g of 2,2°-azobis(isobutyronitrile) (abbreviation ^, 1.B, N,) was added and reacted for 8 hours. Next, 8 g of glycidyl methacrylate and N,N-dimethyldodecylamine were added to this reaction solution. 1.0g
and 0.5 g of t-butylhydroquinone, and the temperature was 1.
The mixture was stirred at 00°C for 12 hours. After cooling, the second reaction solution was reprecipitated into methanol 21 to obtain 82 g of an oily product. The number average molecular weight of the 0 polymer was 5.600.

Macromonomer M-1: Hs In Production Example 1 of Macromonomer, the reaction was carried out in the same manner as in Production Example 1, except that only 2-(n-hexylcarbonyloxy)ethyl methacrylate was replaced with a compound corresponding to Table 5 below. A macromonomer was synthesized. The number average molecular weight of each macromonomer obtained was 5000 to 7000.
It was within the range of

Table-5 Table-5 (continued 1) CH8 Table-5 (continued 2) Methanol 21! It sank back inside. The precipitated oil was collected by decantation, dissolved in 150 d of methylene chloride, and 21 d of methanol. It re-sinked inside. The oil was collected and dried under reduced pressure, with a yield of 54 g and a number average molecular weight of 38.
00 polymer was obtained.

Macromonomer M-22: 2.3-diacetoxypropyl methacrylate) 96 g
A mixed solution of 4 g of thioethanol and 200 g of toluene was heated to 70° C. with stirring under a nitrogen stream. A.1. B, N, 1. Og was added and the mixture was reacted for 4 hours. Furthermore, A.1. Add 0.5g of B and N for 3 hours, then add A and 1. 0.3g of B and N were added and reacted for 3 hours. This reaction solution was cooled to room temperature, 9.6 g of 2-carboxyethyl methacrylate was added, and a mixed solution of 12.7 g of dicyclohexylcarbodiimide (abbreviated as C, C) and 50 g of methylene chloride was added dropwise thereto over 1 hour. did.

1.0 g of t-butylhydroquinone was added, and the mixture was stirred for 4 hours. The filtrate obtained by filtering the precipitated crystals was
CHzCHC41tOCOCIhC0C1h Macromonomer ″23~2:M-23~M-29
In the production example of macromonomer M-22, the following table was prepared in the same manner as in the production example of M-22, except that 2゜3-diacetoxypropyl methacrylate and unsaturated carboxylic acid (corresponding to 2-carboxyethyl methacrylate) were changed. -6
The following macromonomers were prepared. The number average molecular weight of each macromonomer obtained was in the range of 3,000 to 6,000.

Table 6 Table 6 (continued) Macromomer 3Q: M-302-[3-methoxycarbonylpropyleneoxy]ethyl methacrylate 96 g, 2-mercaptoethylamine 4
A mixed solution of 200 g of tetrahydrofuran and 200 g of tetrahydrofuran was heated to a temperature of 70° C. under a nitrogen stream.

A.1. B, N, 1. Add Og and react for 4 hours, then further ^
, lB, N.

Then, the reaction solution was cooled in a water bath to a temperature of 20°C, and triethylamine 6 was added to react for 4 hours.
．． Then, 5.6 g of acrylic acid chloride was added dropwise with stirring at a temperature of 25° C. or lower. After the dropwise addition, the mixture was further stirred for 1 hour. Then, t-butylhydroquinone 0
．． 5 g was added, heated to 60°C, and stirred for 4 hours. After cooling, reprecipitation into methanol 21 was performed twice to obtain 54 g of a pale yellow viscous substance. The number average molecular weight was 4,300.

Macromonomer M-30: Macromonomer +M-2,3-dipropyloxypropyl methacrylate) 95
A mixed solution of 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: 4.0g of A, C, V) was added and reacted for 5 hours, and 1.0g of A, C, V was added. Og was added and the mixture was reacted for 4 hours.

After cooling, the reaction solution was reprecipitated into 1.5 ffi of water, and the oil was collected with decanethisilane and dried under reduced pressure. Yield is 8
It was 5g.

50 g of this oil (oligomer), 15 g of glycidyl methacrylate SN, 1.0 g of N-dimethyldodecylamine and 2,2°-methylenebis(6-t-butyl-
1.0 g of p-cresol) was added and stirred at a temperature of 100°C for 15 hours. After cooling, this reaction solution was reprecipitated into petroleum ether 12 to obtain 36 g of a transparent viscous substance. The number average molecular weight was 3.600.

Macromonomer M-31? Macromonomer M-32: OHCM COOC1lxCHCHiOCOC1l (sOCOCg
In Production Example 31 of 3:M-3 macromonomer of Hs macromonomer, a mixed solution of 50 g of the obtained intermediate oligomer (oil), 5.6 g of 2-hydroxyethyl methacrylate) and long methylene chloride, While stirring at room temperature, O, C, C, 9, Og,
A mixed solution of 0.5 g of 4-dimethylaminopyridine and 20 g of methylene chloride was added dropwise over 1 hour. 4 more as is
Stir for hours. The precipitated crystals were separated by filtration and the filtrate was reprecipitated twice in 1ffi of petroleum ethanol, and the resulting oil was dried under reduced pressure.

The yield was 28 g and the number average molecular weight was 3,000.

A mixed solution of 95 g of 2M-2-(n-nonylcarbonyloxy)ethyl crotonate of C0CJs malomomer and 200 g of tetrahydrofuran was heated to a temperature of 75° C. under a nitrogen stream. 5 g of 2゜2゛-azobis (cyanoheptator) was added and reacted for 8 hours.

After cooling, the reaction solution was brought to a temperature of 20° C. in a water bath, 1.0 g of triethylamine and 21 g of methacrylic anhydride were added, and the mixture was stirred for 1 hour, and then stirred at a temperature of 60° C. for 6 hours.

After cooling the obtained reaction product, the operation of reprecipitating it into methanol 21 was performed twice to obtain 62 g of a colorless and transparent viscous material.

The number average molecular weight was 6.200.

macromonomer M 33; CH.

In the production example of macromonomer M-1, a methacrylate monomer [corresponding to 2-(n-hexylcarbonyloxy)ethyl methacrylate], a mercapto compound [corresponding to thioglycolic acid], and an epoxy group-containing monomer [corresponding to glycidyl methacrylate] were each used. Instead, M-1
Each of the macromonomers shown in Table 7 below was produced in the same manner as in the production example.

-One batch: D- 20g of dispersion stabilizing resin P-1, 100g of vinyl acetate,
1.0 g of macromonomer M-11 and Isopar H
380g of the mixed solution was heated to a temperature of 7 while stirring under a nitrogen stream.
Warmed to 5°C. ^, 1. Add 0.8g of B, N, and react for 4 hours, and then add A, 1. B.N. Add 0.4g of
Time reacted. 20 minutes after the addition of the initiator, white turbidity occurred and the reaction temperature rose to 88°C. Raise the temperature to 100℃ 1
The mixture was stirred for hours and unreacted vinyl acetate was distilled off. After cooling 2
The white dispersion obtained by passing through a 00 mesh nylon cloth was a latex with a polymerization rate of 90% and an average particle size of 0.25 μm.

m-x 2: D-2 16g of dispersion stabilizing resin P-2, 100g of vinyl acetate,
A mixed solution of 1.0 g of Macromonomer M-2 and 385 g of Isopar H was heated to a temperature of 70° C. while stirring under a nitrogen stream. 2. 1.0 g of 2°-azobis(isovaleronitrile) (abbreviated as A, 1.V, N) was added and reacted for 2 hours, and then A, 1. Add 0.4g of V, N, and 2
After reacting for an hour, the temperature was raised to 100°C, and the mixture was stirred for 1 hour to distill off the remaining vinyl acetate. 20 minutes after cooling
The white dispersion obtained by passing through a 0 mesh nylon cloth was a latex with a polymerization rate of 85% and an average particle size of 0.224.

m-X 3 to 31: In Production Example 2 of D-3 to D-31 latex particles, the same procedure as Production Example 2 was carried out except that the dispersion stabilizing resin and macromonomer were replaced with the compounds in Table 8 below. Each latex particle was manufactured under the following conditions. The polymerization rate of each latex particle was 80-85%.

-32: 14g of D-32 dispersion stabilizing resin P-6, 100g of vinyl acetate, 5g of crotonic acid
A mixed solution of 1.0 g of 2-macromonomer M-6 and 468 g of Isopar E was heated to a temperature of 70° C. while stirring under a nitrogen stream. A.1. V.N.

After 6 hours of reaction, the temperature was raised to 100°C and stirred for 1 hour, and the remaining vinyl acetate was distilled off.

After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth, and the resulting white dispersion was a latex with a polymerization rate of 85% and an average particle size of 0.23.

--S 3: A mixed solution of 15 g of D-33 dispersion stabilizing resin P-7, vinyl acetate loog, 6.0 g of 4-pentenoic acid, 11.5 g of macromonomer M-' and 380 g of Isopar G, The mixture was heated to 75°C while stirring under a nitrogen stream.

A.1. Add 0.7g of B and N, react for 4 hours, and then
, 1. B.N.

0.5g of was added and reacted for 2 hours. After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.24.

--Scope: 18 g of D dispersion stabilizing resin P-32, 85 g of vinyl acetate, 15 g of N-vinylpyrrolidone, 1.2 g of macromonomer M1, and n
- A mixed solution of 380 g of decane was heated to a temperature of 75°C while stirring under a nitrogen stream.

A.1. Add 1.7g of B and N, react for 4 hours, and then
, 1. B.N.

0.5g of was added and reacted for 2 hours. After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.20.

-35: D-35 dispersion stabilizing resin P-39 18g, isopropyl methacrylate 100
g, 1.0 g of macromonomer M-8 and n-decane 4
70g of the mixed solution was heated to a temperature of 7 while stirring under a nitrogen stream.
Warmed to 0°C. 1.0g of A, r, V, and N were added and reacted for 2 hours. A few minutes after the initiator was added, the mixture began to become cloudy and the reaction temperature rose to 90°C. After cooling, coarse particles were removed through a 200-mesh nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.45 pa.

--S; D 16g of dispersion stabilizing resin P-7, 100g of styrene, 0.6g of macromonomer M-25 and 3g of Isopar H
80g of the mixed solution was heated to a temperature of 6 while stirring under a nitrogen stream.
Warmed to 0°C. Add 0.6g of A, lV, N, and react for 4 hours, and then add A, 1. 0.3g of V and N were added and reacted for 3 hours. After cooling, pass through 200 mesh nylon cloth.
The obtained white dispersion was a latex with an average particle size of 0.28 m.

--3 A) In production example 1 of latex particles, macromonomer M-1
The white dispersion obtained was a latex with a polymerization rate of 85% and an average particle size of 0.25-.

B) A mixed solution of 385 g of poly(octadecyl methacrylate), 100 g of vinyl acetate, octadecyl methacrylate, Og, and Isopar H was prepared, and the other operations were carried out in the same manner as in Production Example 1.

The obtained white dispersion had a polymerization rate of 85% and an average particle size of 0.2.
It was 2- latex. (Unexamined Japanese Patent Publication No. 60-17975
Corresponding to No. 1 latex particles) ---x 39 0) Poly(
Octadecyl methacrylate)) 18g, vinyl acetate 10
A mixed solution of 0 g, 1 g of a monomer (summer) having the following chemical structure, and 385 g of Isopar H was operated in the same manner as in Production Example 1.

The obtained white dispersion had a polymerization rate of 86% and an average particle size of 0.2.
It was 4- latex. (Unexamined Japanese Patent Publication No. 62-15186
(equivalent to latex particles No. 8) Monomer (1) CHx CHz, C Coo(CHx)tOcOcJ+*(n) Example 1 Dodecyl methacrylate/acrylic acid (copolymerization ratio; 95
15 weight ratio) copolymer, 10 g of nigrosine, and 30 g of Shell Silua 1 were placed in a paint shaker (Tokyo Seiki ■) together with glass beads and dispersed for 4 hours to obtain a fine dispersion of nigrosine.

3 resin dispersion (D-1) of latex particle production example 1
0 g 1 2.5 g of the above nigrosine dispersion, FOC-
1400 (manufactured by Nissho Kagaku ■: Tetradecyl alcohol) 1
A liquid developer for electrostatic photography was prepared by diluting 5 g of octadecene and 0.08 g of (octadecene-half-maleic acid octadecylamide copolymer) to 12 parts of Shersol 71.

"ANC" Three types of liquid developers A, B, and C for comparison were prepared by replacing the resin dispersion with the following resin particles in the above production example.

"A Resin dispersion of latex particle production example 37"
B Resin dispersion ζ of latex particle production example 38
C. Resin dispersion of latex particle production example 39 These liquid developers were used as a developer in a fully automatic plate making machine ELP404V (manufactured by Fuji Photo Film), and electrophotographic photosensitive material ELP Master ■ type (Fuji Photo Film ■) was prepared. ) was exposed and developed. The plate making speed was 5 plates/min. Furthermore, after processing 2000 sheets of ELP Master H type, the presence or absence of toner adhesion stains on the developing device was observed. The blackening rate (image area) of the copied image was determined using a 30% original.

The results are shown in Table-9.

Table 9 When each developer was plate-made under the above-mentioned plate-making conditions, the developer of the present invention was the only one that did not cause staining of the developing device and provided a clear image on the 2000th plate-making plate.

On the other hand, an offset printing master plate (ELP master) obtained by plate making using each developer was printed using a conventional method, and the number of prints was compared until the printed image showed missing characters, fading in solid areas, etc. Then, the present invention, comparative example A
The master plate obtained using the developer of Comparative Example C was too.

The problem did not occur even when the master plate was used for more than 8,000 sheets of the master plate using Comparative Example B.

As can be seen from the above results, only the developer made from the resin particles of the present invention caused no staining of the developing device and at the same time significantly increased the number of master plates printed.

That is, in the case of Comparative Example A, although there was no problem with the number of prints, the developing device was extremely dirty and could not withstand continuous use.

In addition, in the case of Comparative Example B and Comparative Example C, the plate making speed was 5.
When used at high plate-making speeds such as sheets/minute (conventionally, the plate-making speed was 2 to 3 sheets/minute), the developing device (especially on the back electrode plate) becomes dirty, and after 2,000 sheets, the plate becomes dirty. This has affected the image quality of the copied images (decreased CDmax, blurred fine lines, etc.). The number of master plates printed was not a problem in Comparative Example C, but decreased in Comparative Example B.

These results demonstrate that the resin particles of the present invention are clearly superior.

Example 2 White dispersion 100 obtained in latex particle production example 2
A mixture of 1.5 g and Sumikaron black was heated to 10 g.
The temperature was heated to 0"C and stirred for 4 hours. After cooling to room temperature,
The remaining dye was removed by passing it through a 0.00 mesh nylon cloth to obtain a black resin dispersion with an average particle size of 0.25.

32 g of the above black resin dispersion, FOC-1600 (
20g of hexadecyl alcohol (manufactured by Nissan Chemical ■) and 0.05g of zirconium naphthenate were added to Sielsol 71 II.
! A liquid developer was prepared by diluting it to .

When this was developed using the same device as in Example 1, the result was 200
Even after developing 0 sheets, no toner adhesion stains occurred on the device.

Moreover, the image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after single-sheet printing was also very clear.

Example 3 White dispersion 10 obtained in latex particle production example 33
A mixture of 0 g and 3 g of Victoria Blue B was heated to a temperature of 70
The mixture was heated to 80°C to 80°C and stirred for 6 hours. After cooling to room temperature, the remaining dye was removed by passing it through a 200 mesh nylon cloth to obtain a blue resin dispersion with an average particle size of 0.25.

32g of the above blue resin dispersion, 0 zirconium naphthenate
．． A liquid developer was prepared by diluting 05 g of Isopar H to 11.

When this was developed using the same device as in Example 1, 20
Even after developing 00 sheets, no toner adhesion stains were observed on the device. In addition, the image quality of the obtained master plate for off-cent printing was clear, and the image quality of the printed matter after single-sheet printing was also very clear.
, 2.5 g of the nigrosine dispersion obtained in Example 1, FOC-
1800 (manufactured by Nissan Chemical ■, octadecyl alcohol) 1
5 g and 0.02 g of a semi-docosanylamidated copolymer of diisobutylene and maleic anhydride were added to 1 of Isopar G.
A liquid developer was prepared by diluting the developer to J2.

When this was developed using the same device as in Example 1, the result was 200
Even after developing 0 sheets, no toner adhesion stains were observed on the device. In addition, the image quality of the obtained master plate for offset printing and the image quality of printed matter after single-sheet printing were both clear.

Further, after leaving this developer for 3 months, the same treatment as above was performed, but there was no difference at all from before the aging.

Example 5 10 g of poly(decyl methacrylate), 30 g of Isopar H and 8 g of Alkali Blue were placed in a paint shaker together with glass beads and dispersed for 2 hours to obtain a fine dispersion of Alkali Blue.

30 g of the white resin dispersion obtained in Production Example 23 of Latex Particles, 4.2 g of the above alkali blue dispersion, and 0.06 g of a semi-docosanylamidated product of a copolymer of diisobutylene and maleic anhydride were added to Isopar G 11. A liquid developer was prepared by diluting it.

When this was developed using the same device as in Example 1, the result was 200
Even after developing 0 sheets, no toner adhesion stains were observed on the device. In addition, both the image quality of the obtained master plate for offset printing and the image quality of the printed matter after single-sheet printing were very clear.

Examples 6 to 27 In Example 5, D- of latex particle production example 23
A liquid developer was prepared in the same manner as in Example 5, except that each latex shown in Table 1O below was used in place of Example 23.

Table 10 After this developer was left to stand for 3 months, the same treatment as above was carried out, but there was no difference at all from before.

(Effects of the Invention) According to the present invention, a developer with excellent dispersion stability, redispersibility, and fixing properties was obtained. In particular, even when used under plate-making conditions with extremely high plate-making speeds, the developing device does not become contaminated, and both the image quality of the obtained offset printing master plate and the image quality of the printed matter after single-sheet printing are very clear. Ta.

When this was developed using the same device as in Example 1, the result was 200
Even after developing 0 sheets, no toner adhesion stains occurred on the device.

Moreover, the image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after single-sheet printing was also very clear.

Claims (1)

[Scope of Claims] An electrostatic photographic liquid developer comprising at least a resin dispersed in a non-aqueous solvent having an electrical resistance of 10^9 Ωcm or more and a dielectric constant of 3.5 or less, wherein the dispersed resin particles are as follows: A polymer containing repeating units represented by general formula (I) is partially crosslinked, and at least one end of the main chain of the polymer has a -PO_3H_2 group, -SO_3
This non-containing compound is formed by bonding an acidic group selected from H group, -COOH group, -OH group, -SH group, ▲mathematical formula, chemical formula, table, etc.▼ group (here, Z^0 indicates a hydrocarbon group). In the presence of a dispersion stabilizing resin soluble in an aqueous solvent, a monofunctional monomer (A) which is soluble in the non-aqueous solvent but becomes insolubilized by polymerization and represented by the following general formula (II) A monofunctional macromonomer having a number average molecular weight of 10^4 or less and having a polymerizable double bond group represented by the following general formula (III) bonded to only one end of a polymer main chain consisting of repeating units ( A liquid developer for electrophotography, characterized in that it is a copolymer resin particle obtained by polymerizing a solution containing at least one type of M). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula (I), T^1 is -COO-, -OCO-,
-CH_2OCO-, -CH_2COO-, -O- or -SO_2-. A^1 represents an aliphatic group having 6 to 32 carbon atoms. a^1 and a^2 may be the same or different from each other,
Each hydrogen atom, halogen atom, cyano group, carbon number 1-8
hydrocarbon group, -COO-Z^1 or -COO-Z^1 via a hydrocarbon group having 1 to 8 carbon atoms (here, Z^1 represents a hydrocarbon group having 1 to 22 carbon atoms) represent. General formula (II) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (III) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ In general formula (II), V_0 is -O-, -S-, -C
OO-, -OCO-, -CH_2OCO- or -CH_
Represents 2COO-. Y_0 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. X_1 and X_2 may be the same or different from each other,
-O-, -CO-, -CO_2-, -OCO-, -SO
＿２−, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
Represents ▼ or ▲ There are chemical formulas, tables, etc. (Y_1 represents the same content as Y_0 above). R_1 and R_2 may be the same or different from each other,
It may be substituted, or ▲A mathematical formula, a chemical formula, a table, etc.▼ may be interposed in the bond of the main chain [X_3 and X_4 may be the same or different from each other, and have the same content as X_1 and , R_4 represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and Y_2 has the same content as Y_0] represents a hydrocarbon group having 1 to 18 carbon atoms. b_1 and b_2 may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -CO
O-R_5 or -COO-R_5(R
_5 represents a hydrogen atom or a hydrocarbon group that may be substituted. m, n and p may be the same or different, and are 0 to 4
represents an integer. However, m+n is at least 1 or more. In general formula (III), V_1 is -O-, -COO
-, -OCO-, -CH_2OCO-, -CH_2CO
O-, -SO_2-, -CONH-, -SO_2NH-
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -CONHCOO-, or -CONHCONH- (However, R_6 is hydrogen (represents an atom or a hydrocarbon group having 1 to 18 carbon atoms). d_1 and d_2 may be the same or different from each other,
Each has the same meaning as b_1 or b_2 in the above general formula (II).