JPH03211565A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To improve the stability of dispersion, redispersibility and fixability by bringing a resin for stabilizing dispersion which is a comb type copolymer consisting of a specific macromonomer and a specific monomer and is soluble in a nonaq. solvent and a monofunctional monomer which is insolubilized by the polymn. in the presence of a specific oligomer into a polymn. reaction. CONSTITUTION:The resin for stabilizing dispersion which is the comb type copolymer consisting of the macromonomer formed by bonding the polymerizable double bonds expressed by formula I and having 1X10<2> to 2X10<4> weight average mol. wt. and the monomer expressed by formula II and the monofunctional monomer which is insolubilized when polymerized in the presence of the oligomer formed by bonding a polar group to one terminal of the main chain of a polymer consisting of the repeating unit expressed by formula III are brought into the polymn. reaction. In the formulas I to III, X1, X2, E1 denote -COO-, -OCO-, etc.; a1, a2, d1, d2 and e1, e2 respectively denote hydrogen atom, halogen atom, cyano group, etc.; G2 denote 1 to 22C hydrocarbon group. The liquid developer having the excellent dispersion stability, redispersibility and fixability is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention has an electrical resistance of 10" Ωcm or more and a dielectric constant of 3.
This invention relates to a liquid developer for electrophotography, which is made by dispersing at least a resin in a carrier liquid having a molecular weight of 5 or less, and particularly to a liquid developer that has excellent redispersibility, storage stability, stability, image reproducibility, and fixing properties. .

(Prior art) General liquid developers for electrophotography are petroleum-based organic or inorganic pigments or dyes such as carbon blank, 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 developers, the resin is dispersed as insoluble latex particles with a diameter of several nanometers to several hundred nanometers, but in conventional liquid developers, a soluble dispersion stabilizing resin, a polarity control agent, and an insoluble latex are dispersed. Due to insufficient bonding with the particles, the soluble dispersion stabilizing resin and polarity control agent were likely to diffuse into the solution. For this reason, there is a drawback that the soluble dispersion stabilizing resin detaches from the insoluble latex particles due to long-term storage or repeated use, causing the particles to settle, aggregate, or accumulate, and the polarity to become 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 was difficult to obtain a desired average particle size with monodisperse particles having a narrow particle size distribution, and large particles of 14 or more or very fine particles of 0.1 or less were 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, attempts have been made to print a large number of 5,000 or more sheets using an electrophotographic offset printing master plate. 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 fixing 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,
In terms of redispersibility, when the fixing time is shortened, or in the case of large-sized master plates (for example, A-3 size or larger), the performance is still not necessarily satisfactory in terms of rigidity resistance.

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 production of offset printing original plates having excellent printing ink oil sensitivity and printing durability by electrophotography.

Another object of the present invention is to provide a liquid developer suitable for various 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 provide an electrostatic photographic liquid developer comprising at least resin particles dispersed in a non-aqueous solvent having an electrical resistance of 109ΩcI11 or more and a dielectric constant of 3.5 or less. In the agent,
The dispersed resin particles include (1) at least one polymer component represented by the following general formula (Ila) or (Ilb) and -〇〇〇) I group, 1 Po, 112 group, -5O3H group, -0f (group, P-R
r group (here, H R1 represents a -R8 group or a -○Rt group, and R1 represents a hydrocarbon group), a -5H group, a formyl group, and an amino group containing at least one polar group. Weight-average molecular weight I 2
Macromonomer of XIO'<M) and the following -formation (Il
(1) A comb-shaped copolymer consisting of at least a heptamer represented by (1) a dispersion stabilizing resin soluble in the non-aqueous solvent, and (1) a polymer main chain consisting of a repeating unit represented by the following general formula (IV). Carboxyl group, sulfo group, hydroxyl group, formyl group, amino group, phosphono group, and ~P-RO group [R, represents H R, 1 group or -〇R0゛ group, is soluble in the non-aqueous solvent in the presence of an oligomer (B) having a number average molecular weight of 1X10' or less, which is formed by bonding at least one polar group selected from R0'' represents a hydrocarbon group. This has been achieved by an electrostatic photographic liquid developer characterized in that it is a polymer resin particle obtained by polymerizing a monofunctional monomer (A) that becomes insolubilized by polymerization.

General formula (1) %Formula% In formula (1), X is -COO--0CO--CI(!0
CO-1R++ R++ -CH, COO-1-o--so, --co-5-CO
N--SOJ represents a hydrocarbon group).

a3 and a2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -CO
O-Z+ or -Coo-Zl (Z.

represents a hydrogen atom or a hydrocarbon group).

-Formation (Ila) bt bt +CH-C)- X+ Q+ General formula (Ilb) bt bz -+CH-C)- In formula (Ila) or (Ilb), X is X in formula (I)
Represents the same content as o.

Q represents an aliphatic group having 1 to 22 carbon atoms or an aromatic group having 6 to 12 carbon atoms.

b3 and b2 may be the same or different from each other, and the formula (1
, ) represents the same content as ao and a2.

Elementary atom, halogen atom, alkoxy group or -COOZZ
(22 represents an alkyl group, an aralkyl group, or an aryl group).

General formula (I[[) %Formula% In formula (I[I), Xs represents the same content as Xo in formula (1), and Q2 represents the same content as Ql in formula (IIa). dl and d may be the same or different, and represent the same content as al and a2 in 2N).

However, in the component represented by -formation (II) and the monomer component represented by -formation (III) in the macromonomer (M), at least one of Q and q8 has 10 to 22 carbon atoms. represents an aliphatic group.

General formula (■) ε1-62 In 2 (!V), El is -COO--0CO-, (CHt
)iCOO-1(CHt)rOCO-1-〇-5-so
, -1-CONHCOO-1-CONHCONH-1 represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms.

l represents an integer from 1 to 3. ) Gt represents a hydrocarbon group having 1 to 22 carbon atoms. however,
-0-1-CO-1-C (h-1-
OCO-1 represents the same content as D2.

el and eg may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, a C00-
Dz or -Coo-Ds via a hydrocarbon (Di represents a hydrogen atom or a hydrocarbon group which may be substituted).

Furthermore, the oligomer (B) in which a specific polar group is bonded to one end of the polymer main chain provided in the present invention can be formed by the following -formation (I).
It is preferable to contain at least a repeating unit consisting of Va).

General formula (TVa) E+ -(L B+hrnWz Bt force "Gs formula (
In IVa), el, eZ, and El represent the same symbols as in formula (IV).

G represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms.

B and Bt may be the same or different and represent s -NGO- (OS represents the same content as Dl in formula (IV)).

, and - may be the same or different from each other, may be substituted, or -CI+- may be interposed in the 1 B3 (w knee B4 to cs bond) of the main chain, and have 1 to 1 carbon atoms. 18 hydrocarbon group, where B3.84 may be the same or different from each other and have the same content as B1 and B2 above, -1
represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted.

m, n and p each independently represent an integer of 0 to 3,
However, both do not become O at the same time.

Further, the resin for dispersion stabilization of the comb-shaped copolymer provided in the present invention has a weight average molecular weight of 2 x 10' to 2 x 105.
and -PO3H! at one end of the polymer main chain! group, 1 SO2 group, -COOH group, -OH group, -3H group, -P
-Z, group H (Kokote, zo represents -ZIO group or -OZ+o group,
Z+.

is a hydrocarbon group), a formyl group, and an amino group.

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

The carrier liquid having an electrical resistance of 109 Ωcm or more and a dielectric constant of 3.5 or less used in the present invention is preferably a linear or branched aliphatic hydrocarbon, alicyclic hydrocarbon, or aromatic hydrocarbon; Halogen substituted products can be used. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane,
Cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, Isopar E
5 Isopar G, Isopar H, Isopar L (Isopar; trade name of Exxon), Shellzol 70, Schelzol 71 (Shellzol; trade name of Shell Oil), Amsco OMS, Amsco 460 solvent (Amsco;
Spirits Co., Ltd.'s product name) etc. are used alone or in combination.

The non-aqueous dispersion resin particles (hereinafter sometimes referred to as latex particles), which are the most important component in the present invention, are the dispersion stabilizing resin and oligomer (B ) in the presence of -functional monomer (A) (so-called polymerization granulation method)
It was manufactured by.

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, and preferably linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic carbons. Examples include hydrogen and halogen-substituted products of these 6, such as hexane, octane, isooctane, decane, isodecane, decalin, nonane, dodecane,
Isopar E1 Isopar G1 Isopar H1 Isopar, which is isododecane and isoparaffin based petroleum cutting, Shelzol 70, Shelzol 71, Amsco OM
S, Amsco 460 solvent, etc. are used alone or in combination.

Solvents that can be mixed with these @R media 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 (e.g. methylene dichloride, chloroform, carbon tetrachloride, etc.) , 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 resin dispersion production, and as mentioned above, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated Examples include hydrocarbons.

The dispersion stabilizing resin used in the present invention is a comb-shaped copolymer polymerized containing at least one type of each of a -functional macromonomer (M) and a monomer represented by -formation <m). In particular, the comb copolymer is characterized in that it is soluble in the non-aqueous solvent.
It is characterized by randomly containing (OO)I groups, formyl groups, amino groups).

Furthermore, more preferably, the above-mentioned specific polar group (-PO, H, group, -5O3H group, -Cool group, -OH group, -5H group,
It is a comb-shaped copolymer formed by bonding P-Zo groups, formyl groups, and amino groups.

The weight average molecular weight of the comb copolymer is 2X10' to 2X
10', preferably 3 x 10' to 1 x 105. When the weight average molecular weight is less than 2X10' or more than 2X10', the average particle size of the resin particles obtained by polymerization granulation becomes coarse or the particle size distribution becomes wide, and monodispersity is impaired. Or even worse, it becomes an aggregate instead of a dispersion.

The proportion of the monofunctional macromonomer (M) as a copolymerization component of the comb-shaped copolymer is 1% to 70% by weight, preferably 5% to 50% by weight. If the proportion is less than 1% by weight, the number of comb parts will be significantly reduced, resulting in a chemical structure similar to that of conventional random copolymers, and the improvement in redispersibility, which is the effect of the present invention, will not be observed. On the other hand, if the proportion exceeds 70% by weight, the copolymerizability with the monomer indicated by -formation (DI) becomes insufficient.

Further, the proportion of the monomer represented by the general formula (III), which is another copolymerization component, in the comb-shaped copolymer is 30
~99% by weight, preferably 50-95% by weight.

On the other hand, the macromonomer (M) of the present invention, which forms the comb portion of the comb copolymer, has a weight average molecular weight of lX10' to
2×10′, preferably 2×10′ to 1×1O”
It is. When the weight average molecular weight is less than 1XIO3,
The redispersibility of the obtained dispersed resin particles will be reduced, and if it exceeds 2X10', the copolymerizability with the monomer represented by -formation (III) will be reduced, resulting in a comb-shaped copolymer. I can't do it anymore.

Since the comb-shaped copolymer of the present invention as described above is soluble in the non-aqueous solvent, it contains a soluble repeating unit in either or both of the polymer main chain portion and the comb portion. For this purpose, the component shown by -formation (n) in the macromonomer (M) and the monomer component shown by -formation ([[I), Q, and Q. Among these, at least one represents an aliphatic group having 10 to 22 carbon atoms.

That is, as a repeating unit of the macromonomer (M) which is a comb part, 01 in - formation (IIa) has a carbon number of 10
When representing an aliphatic group or an aromatic group less than or equal to -formation (
In the case of the repeating unit represented by nb), Q2 represents an aliphatic group having 10 to 22 carbon atoms in the monomer represented by the general formula (I[[) constituting the main chain portion of the polymer, In addition, when 02 in -formation (I [
Ql in Ila) contains a repeating unit of an aliphatic group having 10 to 22 carbon atoms.

The content of the comb copolymer will be explained in more detail below.

The monofunctional macromonomer (M) includes at least one of the polymer components represented by -formation (na) or -formation (nb) (hereinafter referred to as polymer component (A)), and a specific At least one of the polymer components containing at least one polar group (-COO) I group OH formyl group, amino group (hereinafter referred to as polymer component (B
) can be copolymerized with a monomer denoted by -formation (I[[),
-1 A macromonomer having a weight average molecular weight of 1X10j to 2X10', which is formed by bonding polymerizable double bond groups represented by formula (1).

- In formations (1), (■a), (IIb) and (III), xo, al, a8, Xl, ■, b3, b! ,X
z, dd2, Q, and 0. Each of the hydrocarbon groups contained in
In 1), in addition to a hydrogen atom, R in the substituent represented by , 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.), carbon number 4-1
8 optionally substituted alkenyl groups (e.g. 2-
Methyl-1-propenyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, ■-pentenyl Ll-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc. ), a substituted ioyaralkyl group having 7 to 12 carbon atoms (e.g., benzyl group, febbutyl group, 3-phenylpropyl group, naphthylmethyl group, 2
- Naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxyhensyl group, etc.), optionally substituted alicyclic group having 5 to 8 carbon atoms groups (e.g., cyclohexyl group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, etc.), optionally substituted aromatic groups having 6 to 12 carbon atoms (e.g., 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 group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group,
propioamidophenyl group, dobcyroylamidophenyl group, etc.).

χ. When represents -(), the benzene ring may have a substituent. Examples of the substituent include a halogen atom (for example,
chlorine atom, bromine atom, etc.), alkyl groups (e.g., methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.), alkoxy groups (e.g., methoxy group, ethkyne group, propioxy group, butoxy group) base, etc.)
etc.

a and a 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 4 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), -Coo-Zl or -Coo via hydrocarbon
-Z+ (Zl is preferably a hydrogen atom or a carbon number of 1 to
18 alkyl group, alkenyl group, aralkyl group, alicyclic group or aryl group, which may be substituted, specifically, the above [represents the same content as explained for 1++] represent

Examples of the hydrocarbon in the one-coo-z group via the hydrocarbon include a methylene group, an ethylene group, a propylene group, and the like.

More preferably, in general 2N), X is -COO
--0CO--CB! OCO-5-CHgCOO-1-
〇--CONI (-2-501NH- or 4), als at may be the same or different from each other, and each represents a hydrogen atom, a methyl group, -cooz, or -CJCOOZ
Represents +. Here, Z more preferably represents a hydrogen atom or an alkyl group having 1 to G carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, hexyl group, etc.).

Even more preferably, one of al and a2 represents a hydrogen atom.

That is, as the polymerizable double bond 1 represented by the -formation (1), specifically, C)lZ=cH-C-0co
z=c C-0-1 CHz (Jl-C-0, CH1=C O, C-0 C)1. C00)l CHt CH,=C 1CHt-CH-CORN ,C)I,C-C0N)I- 0ζC-0- CHzCII-CON8 ,CH,,CI(-0-C 2CH*:CH-CHt-0- C C)1. +IcH-0, CI(z"C-CHz-C-0-1CH1C-CHz
In C-0- formation (Ila) or (IIb),
Xl represents the same content as xo in formula (1), bl,
bl may be the same or different, and 8 in formula (1)
1, represents the same content as a2.

Ql is an aliphatic group having 1 to 22 carbon atoms or an aliphatic group having 6 to 12 carbon atoms
represents an aromatic group, and specifically represents the same content as R1+ described above.

A preferred example of bI-bt represents the same contents as a5 and a described above.

In general formula (Ilb), ■ is -CN, -CONII
! (e.g., chlorine atom, bromine atom, etc.), alkoxy groups (e.g., methoxy group, ethoxy group, propioxy group,
butoxy group, etc.) or -cooz□ (ZX preferably represents an alkyl group having 1 to 8 carbon atoms, a 7-ralkyl group having 7 to 12 carbon atoms, or an aryl group).
M) may contain two or more types of polymer components (A) represented by formula (na) and/or ([lb).

Furthermore, in the macromonomer (M), formula (Ila)
and/or a polar group (-COOH group, -P(h)It group, ~SO, H group, -OH group, P-R) copolymerized with the polymer component (A) represented by (IIb)
The polymer component (B) containing a + group, -5H group, OH formyl group, amino group) may be a vinyl compound containing the above polar group that can be copolymerized with the above polymer component (A). For example, it is described in Polymer Data ``Polymer Data Handbook [Basic W] J Baifukan (published in 1986).

Specifically, acrylic acid, α- and/or β-substituted acrylic acid (e.g., α-acetoxy form, α-acetoxymethyl form, α-(2-aminoethyl) form, α-chloro form, α-
Bromo form, α-fluoro form, α-tributylsilyl form, α
-cyano form, β-chloro form, β-bromo form, β-fluoro form, β-methoxy form, α, β-dichloro form, etc.), methacrylic acid, itaconic acid, itaconic acid half esters, itaconic acid half amides , crotonic acid, 2-alkenylcarboxylic acids (e.g., 2-pentenoic acid, 2-methyl-2-hexenoic acid, 2-octenoic acid, 4-methyl-2-hexenoic acid, 4-ethyl-2-octenoic acid, etc.) , maleic acid,
Maleic acid half esters, maleic acid half amides, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, vinylsulfonic acid, vinylphosphonic acid, dicarboxylic fiim
, half-ester derivatives of vinyl or allyl groups of alcohols, ester derivatives of these carboxylic acids or sulfonic acids, and compounds containing the polar group in the substituent of amide derivatives.

OH R represents a hydrocarbon group. Examples of the hydrocarbon group represented by R2 include the same hydrocarbon groups as described above for Q+ in formula (Ila).

0) Compounds containing one group include vinyl group- or allyl group-containing alcohols (for example, allyl alcohol, methacrylic acid ester, ester substituent such as acrylamide,
Compounds containing 10H group in the N group (m group), methacrylic acid esters or amides containing hydroxyphenol or hydroxyphenyl group as a substituent.

For example, the monomers listed below are shown as examples of the polar group-containing vinyl compound, but the scope of the present invention is not limited thereto.

Here, on each side below, a is one ■, -CHl, ,
CI, -Br, -CN, -CLCOOCL or-
C1lICool, b represents one or -CL,
j represents an integer of 2 to 18, k represents an integer of 2 to 5,
l represents an integer of 1 to 4, m represents an integer of 1 to 12,
n represents an integer of 2 to 12.

(A-1) C)1. =c COO)l CHi (A2) CH= CI( COOH υto4) CH1=C COO(CHz) ,1COOH (A-5) CH,=C C0NH(CHl) ,C0OH (A-6) C1, =C C00(CHz), 10CO(CHz)lICOOH(
＾ 7) CI,=C COO(CHI)Coo(C)Iri1ICOOH(A 8) CH,=C C0NH(CHriROCO(CHI),C00H(A-
9) GHz=C CONHCOO(CH 00H (A-10) CH,=C C0N)ICON)I (CHt) -COOHCH3 CON)ICH CH2C00H (A43) C)I,=C (A 14) CH,= C C00(CHz)-N)ICO(CHz)-COOH(
A 15) CH,=CH CHzOCO(CHi)-COOH (A 16) CH==CI(4GHz)-COOH (A-18) CH,=C C00(CHI) 70GOCI=CH-COOH(A 20) CHz= C (A 21) C1,=C0 1 COO(CI(z) jO-P-OH H 1 CON) I(CHz) jO-P-OHH C00(CHz) JO-P-OCJs H (A-25) CH ,=C0 1 Coo(CHz) JO-P-CzHsH (A-30) cut=c Coo(CHz), SO! (A 36) CH,=C C0N(CHzC)lzcOOH) t(A 37) cttz=c COO(CL)tcON(CHzCLCOOH)i(A
-42) CH2=C C00 (CHz) 70H CH3 (A 43) CH= CH COO (CHz) 70H (^ 44) CL=C? C0NH(Clh) Joll (A-45) CL=C HtOH COOCHiCHO)1 (A-48) CH,=C CH,01( 0NHCH C1,01( (＾-49) COz = C1i )C) I z floor OH (A-51) coz=c COO(C)Iz) 10cO(C)If) *0H(
A-52) C[1z=CH-(CHz floor COO((:Fh) jO
H(A-53) CI(Z=C CONHCOO(C1,) jOH (A-56) CH2=C C00(CHz), C00(CHz)=OH In the macromonomer (M), the heavy compound containing the polar group Combined component (
The amount contained as B) is preferably 0.5 to 50 parts per 100 parts by weight of all polymer components in the macromonomer (M).
Parts by weight, more preferably 1 to 40 parts by weight.

When the monofunctional macromonomer CM) composed of these polar group-containing random copolymers is contained in a comb-shaped copolymer as a copolymerization component, it is contained in all the graft parts in the comb-shaped copolymer. The total amount of the polar group-containing component (B) is 0 per 100 parts by weight of all polymer components in the comb-shaped copolymer.
．． The content is preferably 1 to 10 parts by weight, more preferably -COOH group, -5o31 (group and -PO3H group).
! When containing an acidic group selected from the following groups, the total amount present in the graft portion in the comb copolymer is 0.1 to 5% by weight.

The macromonomer (M) may contain other polymer components other than the above-mentioned polymer components (A) and (B), for example, polymer components (A) and (B).
Monomers corresponding to other repeating units that can be copolymerized with acrylonitrile, methacrylonitrile, acrylamides, methacrylamides, styrene and its derivatives (for example, vinyltoluene, chlorostyrene, dichlorostyrene, bromostyrene, hydroxy methylstyrene, NN-dimethylaminomethylstyrene, etc.), heterocyclic vinyls (eg, vinylpyridine, vinylimidazole, vinylpyrrolidone, vinylthiophene, vinylpyrazole, vinyldioxane, vinyloxazine, etc.).

When these other monomers are contained, it is preferably 1 to 20 parts by weight per 100 parts by weight of the total polymer components of the macromonomer (M).

The macromonomer provided in the present invention has a random polymer main chain consisting of at least repeating units represented by -formation (IIa) and/or (IIb) and repeating units containing a specific polar group, as described above. 0 formula (1 ) components and formulas (
The linking group that connects the IIa) or (Il b) component or the polar group-containing component is a carbon-carbon bond (-multiple bond or double bond), a carbon-hetero atom bond (the hetero atom is, for example, oxygen atom, a sulfur atom, a nitrogen atom, a silicon atom, etc.), and a heteroatom-heteroatom bond.

More specific linking groups for R are -+c)-(R1!,
RI! R13 represents a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, a hydroxyl group, an alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.), +CH=CH) -1RI4
R14 ■ coo--so□--CON--30,1l-1-NH
From an atomic group such as COORo N) ICONH-1-5i- [R+4, R+s each independently represent a water I5 element, or a hydrocarbon group representing the same content as rho in the above formula (Ila)] It represents a single selected linking group or a linking group composed of any two or more combinations.

The macromonomer (M) used in the present invention can be produced by a conventionally known synthesis method.

Specifically, in the molecule, a carboxyl group, a carboxyhalide group, a hydroxyl group, an amino group, a halogen atom,
Using a polymerization initiator containing a reactive group such as an epoxy group and/or a chain transfer agent, various reagents are reacted with an oligomer with a terminal reactive group bond obtained by radical polymerization.
It is synthesized by a radical polymerization method to form a macromer.

Specifically, P, Dreyfuss & R, P, Qu
irk+ encycle.

Polym, Sci, Eng,, 7.551
(1987), P, F, Re+5ppL E, Fran
ta+ ^dv, Polym, Sci,,
58. 1 (1984), Yuji Yogami “Chemical Industry J.
3JJ-, 56 (1987), Yuya Yamashita “Polymer J
31.988 (1982), Shibe Kobayashi “Polymer”-3
0,625 (1981), Hiroshi Ito - "Polymer Processing" Japan.

262 (1986), Takashi Higashi, Takashi Tsuda “Functional Materials”
It can be synthesized according to the methods described in the reviews of Sumi KlO, 5, etc., and the literature and patents cited therein.

However, since the macromonomer (M) of the present invention contains the polar group as a constituent of its repeating unit, it is synthesized with the following considerations in mind, for example.

As one method, for example, as shown in reaction formula (1), a monomer containing the polar group in the form of a protected functional group is used to carry out radical polymerization and terminal reactive group formation using the above method. This is to be introduced.

Reaction formula (1) %formula% ) CH.

Nero: A protecting group for C0OH, for example, -C(CJs)x The polar group (-50,11 group, -PO3H) randomly contained in the macro-7mer (M) provided in the present invention.

The protective group introduction reaction (mil group, amino group) and the deprotection reaction (eg, hydrolysis reaction, hydrogenolysis reaction, oxidative decomposition reaction, etc.) can be carried out by conventionally known methods.

Specifically, J., F., W., McOmie, “P.
protectiveGroups in Organi
c Chemistry + Plenum Pres
s (1973), T, L Greene+”P
protective Groupsin Organi
c 5yathesi, s”+ John Wile
y & 5ons (1981), 4Jz Ta Ryohei "Polymer Fine Chemicals" Kodansha (1976), Yoshio Iwakura and Keisuke Kurita "Reactive Polymers" Kodansha (1977),
G, Bern@r at al+'J, Radia
tion Curing'+ 1111Jq, t4c
ilO, P 10, JP-A No. 62-212669, No. 6
No. 2-286064, No. 62-210475, No. 62
-195684, 62-258476, 63-
No. 260439, JP 1-63977, JP 1-70
It can be synthesized using the method described in No. 767 and the like.

・As another method, for example, as shown in reaction formula (II), after synthesizing the oligomer using the above-mentioned keyaki,
A polymerizable double that reacts only with the "specific reactive group" by utilizing the difference in reactivity between the "specific reactive group" bonded to one end of the oligomer and the polar group contained in the oligomer. This is a method of synthesis by reacting with a reagent containing a binding group.

Reaction formula (n) 0 part As shown in the reaction formula (It), each specific functional group (A part,
Specific examples of combinations of parts B and 0) are shown in Table -. However, the present invention is not limited to these,
What is important is that macro-thumerization can be achieved by utilizing the reaction selectivity in ordinary organic chemical reactions without protecting the polar groups in the oligomer.

Examples of chain transfer agents that can be used include mercapto' compounds containing the polar group or a substituent that can be derived from the polar group (e.g., oglycolic acid, thio'malic acid, thiosalicylic acid, 2-mercaptopropion acid, 3
-Mercaptopropionic acid, 3! Mercaptoacetic acid, N-
(2-mercaptopropionyl+)' glycidi, 2-mercaptonicotinic acid, 3- (N-(2-mercaptoethyl)carbamoyl]propionic acid, 3- (N-(2
-Mercaptoethyl)aminocopropionic acid, N-(3
-mercaptopropionyl)alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1°2-propanediol, 1-mercapto-2-propane tool, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-
mercapto-3-pyridinol, etc.) or disulfide compounds which are oxidized products of these mercapto compounds, and iodized alkyl compounds containing the polar group or a substituent that can be derived from the polar group (e.g. iodoacetic acid, iodopropionic acid, 2- iodoethanol, 2-iodoethanesulfonic acid, 3-iodofuropanesulfonic acid, etc.). Preferred are mercapto compounds.

Specific reactive group-containing polymerization initiators that can be used include, for example, 2.2'-azobis(2-cyatuburobanol), 2.2'-azobis(2-cyanopentanol), 4.4 '-azobis(4-cyanovaleric acid),
4.4'-azobis(4-cyanovaleric acid chloride)
, 2.2'-azobis[2-(5-methyl-2-imidacillin-2-yl)propane), 2.2'-azobis[
2(2-imidapurin-2-yl)propane], 2.2
'-Azobis(2-(3,4,5,6-tetrahydrobyrimidin-2-yl)propane)], 2'-Azobis(2-(1-(2-hydroxyethyl)-2-imidacillin-2 -yl]propane1.2.2'-azobis[2
-methyl-N(2-hydroxyethyl)-propionamide] and derivatives thereof.

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

Specific examples of the macromonomer (M) of the present invention include the following compounds. However, the scope of the present invention is not limited to these.

Also, on each side below, b represents -H or -CH3; d represents -H1-CN3 or -CHtCOOCHs; R is CIIH! 11-1 (n represents an integer from 1 to 22), -cH, CJs, C0NHz or -cans
represents; h is -CI, -Br, -CN or -0CH3
r represents an integer of 2 to 18; S represents an integer of 2 to 12; L represents an integer of 2 to 4;

(n l) (To 2) (To 3) CN OOR Coo) I (Gate-4) b ShiUUH (Door) Hi (To 8) (M-9) H 0OR COO (CHzJ3Sυ3H (M 10) (?I -11) (i 12) (M 13) (l-11) (i12) ( lhOH (M-16) (M-17) (M 18) OH (M 19) (M-20) (M-21) 0OR COO(CHrito-P-OH 1 (L22) CHz OOR OOH (M-23) coz=c Coo(CHz), 0CO(CIri, C00CHICH
! S-book (M-24) OOR 0OH (L25) C00 (CHz), OH (M-26) On the other hand, the monomer copolymerized with the macromonomer (M) described above is represented by the general formula (II[) . In 2(I[I), dl and mu may be the same or different from each other, and the formula (1
) represents the same content as a8 and az. X2 is formula (I)
In the main chain of the comb-shaped copolymer, -POJ! Group, 11 soyHZ, -COOH group, -〇l (group, -P-R, group, -5)l group H Preferably, it does not contain a copolymerization component containing a polar group such as a formyl group and an amino group.

Further, the comb-shaped copolymer of the present invention may contain monomers other than these as further copolymerization components together with the above-mentioned macromonomer (M) and -forming (I[[) monomers. .

For example, α-olefins, vinyl alkanoates or allyl esters, acrylonitrile, methacrylonitrile, vinyl ethers, acrylamides, methacrylamides, styrenes, hetero-11hinyl I (for example, vinylpyrrolidone, vinylpyridine, vinylimidazole) ,
vinylthiophene, vinylimidacilline, vinylpyrazole, vinyldioxane, vinylquinoline, vinylthiazole, vinyloxazine, etc.).

However, the amount of these other monomers other than the macromonomer (M) and the monomer of formula (III) does not exceed 30% by weight in the comb-shaped copolymer.

Furthermore, the comb-shaped copolymer of the present invention may have the following specific polar group bonded only to one end of the polymer main chain.

That is, -POJz group, -5o, 11 group, -coo, 1,
-OR group, ISH group, -P-Z, group (Kokote, Zo is -Z1. group or -02,.

Indicates the H group and Zl. indicates a hydrocarbon group), formyl group,
It is a polar group selected from amino groups.

1 In the polar group, -P-Z, in the group, Z is -2. or H-OZ+o group, and ZIO preferably has 1-1 carbon atoms.
eZI representing a hydrocarbon group of 8. More preferably, the hydrocarbon group is an optionally substituted aliphatic group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, butenyl group, pentenyl group, hexenyl group). L2-40 loethyl group, 2-cyanoethyl group, cyclopentyl group, cyclohexyl group, hensyl group, phenethyl group, chlorohensyl group, bromohensyl group, etc.), or an optionally substituted aromatic group (e.g. phenyl group, tolyl group, xylyl group) , mesityl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

Furthermore, among the above polar groups of the present invention, the amino group is -NHZ, each independently represents a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrocarbon group having 1 to 8 carbon atoms, and specifically represents the same content as the 2100 hydrocarbon group described above.

Even more preferably, zl. Examples of the hydrocarbon group in %ZI+ and Zlf include an optionally substituted alkyl group having 1 to 4 carbon atoms, an optionally substituted Hensyl group, and an optionally substituted phenyl group.

Here, the polar group is directly bonded to one end of the polymer main chain, or as a group that connects the polar group to a six-comb copolymer component having a chemical structure bonded via an arbitrary linking group, carbon-carbon bond (-double bond or double bond),
It is composed of any combination of atomic groups such as carbon-heteroatom bonds (heteroatoms include, for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.) and heteroatom-heteroatom bonds.

R+x s to RI5 are each 1? +2-Rl5) is a linking group composed of a single atomic group or a combination of two or more.

In the comb-shaped copolymer used in the present invention, in order to synthesize a polymer in which the polar group is bonded to the end of the main chain of the polymer, at least the above-mentioned macromonomer (M) and -formation (
This can be achieved by concurrently using a polymerization initiator or chain transfer agent containing the polar group or a specific reactive group that can be derived therefrom in the molecule during the polymerization reaction with the monomer shown in 1).

Specifically, it can be obtained in the same manner as the method for oligomers having a reactive group bonded at one end as described above in the synthesis of macromonomers.

Next, the oligomer (B) of the present invention will be described in detail.

The oligomer (B) has a number average molecular weight of 1
'The following oligomers.

- in formation (IV) 81, e! The hydrocarbon groups contained in s E+ and G: each have the indicated number of carbon atoms (as an unsubstituted hydrocarbon group), but these hydrocarbon groups may be substituted.

In formula (IV), the substituent represented by E.

In addition to a hydrogen atom, preferable hydrocarbon groups include an optionally substituted alkyl group having 1 to 22 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, eicosanyl group, docosanyl group,
2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), carbon number 4
~18 optionally substituted alkenyl groups (e.g.
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, rilur group, etc.), optionally substituted aralkyl groups having 7 to 12 carbon atoms (e.g. benzyl group, phenethyl group) ,
3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromohensyl group,
methylbenzyl group, ethylhensyl group, methoxyhensyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.)
, an optionally substituted alicyclic group having 5 to 8 carbon atoms (for example,
Cyclohexyl group, 2-cyclohexylethyl group, 2-
cyclopentylethyl group, etc.) or carbon number 6-12
Aromatic groups that 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, ethoxycarbonylphenyl group, phthoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobcyroylamidophenyl group, etc.).

It may have a group. Examples of the substituent include halogen atoms (for example, chlorine atom, bromine atom, etc.), alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group, chloromethyl group, methoxymethyl group, etc.).

G2 preferably represents a hydrocarbon group having 1 to 22 carbon atoms, and specifically represents the same content as described above. However, z ■ in the carbon chain of G2 has -〇-1-CO-1-COZ-, -0CO-,'-
It represents the same content as 5Oz-, -NDl.

e+ and e2 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-ox or -CFlzCOODs (D! is
Represents a hydrogen atom or an alkyl group, alkenyl group, aralkyl group, alicyclic group or aryl group having 1 to 18 carbon atoms,
These may be substituted, specifically as described above,
represents the same content as that described for ).

Furthermore, in the oligomer (B) provided in the present invention, as a repeating unit constituted, G in - formation (IV)
2 is a general formula ( preferably contains a component of rVa).

-・General Ni (IVa) el ez -(CH-C)- E+ HI'l+ B City [Senz Bz) y-Gs Ni (rVa), els et and El are as described above.

B and B2 may be the same or different, and Ds
Ds 0-1-CO-1-C(h-1-OCO-1-SO□-
1-N--CON)IcO- (OS represents the formula (I
V) represents the same content as ``Naka-nori'').

Wl and 6 may be the same or different from each other, may be substituted, or replace -(CH)- with the main chain Bs(Wz-Bn
Tomb G.

A hydrocarbon group having 1 to 18 carbon atoms that may be interposed in the bond (hydrocarbon groups include alkyl groups, alkenyl groups,
represents an aralkyl group or an alicyclic group). Preferred specific examples of these aliphatic groups include the same content as the preferred aliphatic group 62 in formula (■).

However, B1 and B4 may be the same or different and may be the above Bl.

The same content as B2 is shown, and -1 represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms and the same content as 1 or 6.

Furthermore, to give a specific example regarding the edge and h, 1 +ch (t+t, Ds is a hydrogen atom, an alkyl group,
Halogen nCH) - (83, B4, -1, G, and p are u above) (w3-84kG.

It is composed of any combination of atomic groups such as (indicating the same meaning as the symbol).

Furthermore, m, n and p may each be the same or different,
Oll, represents the number of 2.3. However, both do not become 0 at the same time.

G represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, preferably represents an optionally substituted aliphatic group having 1 to 22 carbon atoms, and specifically, 6 in formula (IV) ! represents the same content as .

Furthermore, in formula (IVa), εE1, B1.6,
It is preferable that the total number of atoms of each atomic group of B2 and G is 8 or more. .

More specific examples of the above repeating unit represented by the formula (■a) will be given below. However, the content of the present invention is not limited to these.

In the following, a is -H or -CHl; R is C, - alkyl group; R' is a hydrogen atom or C8 alkyl group; 1, k2 each is an integer from 1 to 12; i is 1 Indicates an integer between ~100.

-(CII C+- COO(CHz 0 COR ■ 1+CH, -C+- Coo(CHz+, ycOOR (B)-4 (B) 5 (B) ACHl-C+- COO(CHziOCOCH=CH-COOR(B) cHt Cl C00CHzC) ICHzOCOR C0R (8)-8 0H2 Cl C00(C)I, ya OCO(CHg) Mushroom!18-R(B
) encHx C+-Coo(CH2C1hO韮-P'(8)-10-fcH.

Cl CH3 ■ Coo　(CHzCHOe7)' (B)-12 -4-C1l.

c)- COOCHCH＊C00R 012COOR -4CI(.

C+- One generation H2 F Coo (CHx) i-7-OCO (fjl mountain SO, R (
13) 5 CH.

-(Cll -CI()-- COO(CH 0COR (8) 6 CH3 -(CH-CH)- COOCI(zcHcHzOcOR ToadCOR (B) 7 -(C)l!-CH)-- OCO(CHz ■0COR (8) 8 HCHArC)I+ (CHz)7COO(CHz 0COI! A polymer main chain with a number average molecular weight of 1 Indicates a polar group bonded only to one end, and Roo has 1 to 1 carbon atoms.
18 hydrocarbon groups. Preferably, the hydrocarbon group of Roo is an optionally substituted aliphatic group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, butenyl group, pentenyl group, xenyl group, 2-chloroethyl group, 2-cyanoethyl group, cyclopentyl group, cyclohexyl group, benzyl group, phenethyl group, chlorobenzyl group, bromobenzyl group, etc.), or an optionally substituted aromatic group (e.g. phenyl group, tolyl group, etc.) group, xylyl group, mesityl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

Moreover, among the polar groups of the present invention, the amino group is -Nllt, number 1
-18 hydrocarbon group, preferably carbon number 1-8
represents a hydrocarbon group, and specifically represents the same content as the hydrocarbon group of Roo described above.

Even more preferably Roo, G, and G. The hydrocarbon group is an optionally substituted alkyl group having 1 to 4 carbon atoms,
Examples include an optionally substituted benzyl group and an optionally substituted phenyl group.

Here, the polar group is directly bonded to one end of the polymer main chain, or as a group that connects the polar group to the component of formula (IV) having a chemical structure bonded via an arbitrary linking group, carbon -Carbon bond (-double bond or double bond), carbon-hetero atom bond (hetero atoms include, for example, oxygen atom, sulfur atom, nitrogen atom, silicon atom, etc.), atomic group of hetero atom-hetero atom bond It is composed of any combination of the following.

Among the oligomers (B) of the present invention, preferred ones are of the formula (
Va) or as shown by formula (Vb).

General formula (Va) el SelfA-Z-4CH-C)-E, -T General formula (vb) e, eg ■ -(CH-C)-Z E+ T In formula (Va) and 2 (Vb), el, e2, El is 2 (
IV), T represents 6 in formula (rV) or +W + -B r hIz - in formula (]Va)
82) Represents T-G s.

A represents the aforementioned polar group bonded to one end in formula (IV).

9 Z is a simple bond or -+C)-CD, ,Dl. ie each independently represents a hydrogen atom, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, etc.), a cyano group, a hydroxy group, an alkyl group (e.g., methyl group, ethyl group, propyl group), etc. ), ACH=CH)-5DI+ 5O7- 0N -SO3H-1 HCOO N)ICON)I-1 D1□ Indicates a hydrocarbon group with the same content as Dl], or a single linking group selected from atomic groups such as Represents a linking group composed of any combination.

If the upper limit of the number average molecular weight of the oligomer (B) exceeds 1×10 4 , the rigidity resistance will decrease. On the other hand, if the molecular weight is too small, stains tend to occur, so it is preferably 1XIO3 or more.

The oligomer (B) of the present invention is a homopolymer component or a copolymer component selected from the repeating units represented by the -ta formula (IV) or a unit corresponding to the repeating unit represented by the general formula (IV). 0 formula (I
Examples of other monomers that become copolymer components together with the polymer component V) include acrylonitrile, methacrylatetrile, and heterocyclic compounds containing polymerizable double bond groups (specifically, the monomers listed below). compounds similar to the heterocyclic compound in mer (A)), compounds containing a carboxamide group or sulfamide group and a polymerizable double bond group (e.g. acrylamide, methacrylamide, diacetone acrylamide, 2-carboxyamidoethyl methacrylate, vinylhenzenecarpoxyamide, vinylhenzene sulfamide, 3-sulfoamidopropyl methacrylate, etc.).

The repeating unit represented by the general formula (IV) or (IVa) described above is suitably 30% to 100% by weight, preferably 50% to 100% by weight in the oligomer (B) used in the present invention. It is.

In addition, it is preferable that the main chain of the polymer does not contain a co-electronically synthesized H component containing polar groups such as a phosphono group, a carboxyl group, a sulfo group, a hydroxyl group, a formyl group, a 1-amino group, and a -p-Ro group. .

The oligomer (B) of the present invention, which has a specific polar group bonded only to one end of the polymer main chain, can be obtained by reacting various reagents at the end of a living polymer obtained by conventionally known anionic polymerization or cationic polymerization. method (method using ionic polymerization method), ■method of radical polymerization using a polymerization initiator and/or chain transfer agent containing a specific polar group in the molecule (method using radical polymerization method), or ■method using ions as described above. It can be easily produced by a synthetic method such as a method in which a polymer having a reactive group at the end obtained by a polymerization method or a radical polymerization method is converted into the specific polar group of the present invention by a polymer reaction.

Specifically, P, Dreyfuss & R,P,
QuirkEncycle, Polym, Sci,
Eng,, 7.551 (1987), Yoshiki Chujo,
Yuya Yamashita [Dye and Medicine J 3Q, 232 (1985)
, Akira Ueda, Susumu Nagai, Science and Industry J, 60.57 (1
986) and the literature cited therein.

As a polymerization initiator containing a specific polar group in the molecule described above, for example, 4,4'-azobis(4-cyanovaleric acid)
, 4,4'-azobis(4-cyanovaleric acid chloride)
, 2.2'-azobis(2-cyatuburobanol),
2.2'-azobis(2-cyanopentanol), 2
．． 2'-azobis(2-methyl-N-(2-hydroxyethyl)-propioamide L 2,2'-azobis(
2-Methyl-N-(1,1-bis(hydroxymethyl)
ethyl]propioamide 1.2.2'-azobis(2
-Methyl-N-11,1-bis(hydroxymethyl)-
2-Hydroxyethyl]propioamide 1.2.2'-
Azobis[2-(5-methyl-2-imidapurin-2-yl)propane], 2゜2'-azobis(2-(4,5,
6,7-titrahydro IH-1,3-diazepine-2
-yl)propane), 2,2°-azobis[2-(3,
4゜5.6-tetrahydrobyrimidin-2-yl)propane], 2.2'-azobis(2-(5-hydroxy-
3,4,5,6-tetrapyrimidin-2-yl)propane L 2.2'-azobis(2(1-(2-hydroxyethyl)-2-imidacillin-2-yl)propane 1.
2.2'-azobis[N-(2-hydroxyethyl)-
2-Methyl-propionamidine L 2. Azobis-based compounds such as 2'-azobis[N-(4-aminophenyl)-2-methylpropionamidine] are excluded.

Examples of chain transfer agents containing a specific polar group in the molecule include mercapto compounds, disulfide compounds, and iodine-substituted compounds, with mercapto compounds being preferred. For example, thioglycolic acid, 2-
Mercaptopropionic acid, thiomalic acid, 2-mercaptoethanesulfonic acid, 2-mercaptoethanol, 2-
Examples include mercaptoethylamine, thiosalicylic acid, α-thousandoglycerin, 2-phosphonoethylmercaptan, hydroxythiophenol, and derivatives of these mercapto compounds.

These polymerization initiators and/or chain transfer agents form (■)
It is used in an amount of 0.5 to 20% by weight, preferably 1 to 141%, based on the total amount of the monomer corresponding to the repeating unit represented by and other polymerizable monomers.

The oligomer (B) used in the present invention is most preferably represented by the general formula (Va) or (Vb), but further specific examples of the moieties represented by A-Z- in these formulas are shown below. It is shown below. However, the scope of the present invention is not limited thereto.

In the following, k is an integer of 1 or 2, and ikz is an integer of 2 to 1.
represents an integer of 1 or 3.

(C)-11 (00C4CIIrhry5(C)-2HO
OC-Cll-5 HOOC-CH.

(C) HOOC(CHx)yroOc-4GHz+US=(C
) HOOC(CHz)yrNHcO(cl(z+-rrs
)100c (C)-7HO(C)lz)rrs-(C)-8HtN(CHxhlS)10cH-CB□5-IOC)I.

(C)-12 HOzS(CHz)J- 5υ3tl CHl (C)-17 HOOC4CHz)IC- N CH3 (C) 8 HO(C)lx)yyC N CH3 (C)-1,9 80(CHz)yroOc(CHxhC-N C11 N CH2 (C) 3 R-NHCO-C- R:　HOfCHz)y,,HsC-C-LOH R’ H z; +CHt+1, iCHHz) r - -C)ltCHGHz- Ro; -H, -CHzCHtOH L (R1; H.

H2 -OH) (C)-26 \SQ, )l (C)-29HOOC(C)It)JH(CHz)yr
S(C)-30HOOC(CHzhCONH(CHz)
yrs-Next, the monofunctional monomer (A) of the present invention will be described in detail.

The monomer (A) in the present invention may be any monofunctional monomer that is soluble in nonaqueous solvents but becomes insolubilized by polymerization. Specifically, for example, -forming ( Examples include monomers represented by Vl).

General formula (Vl) B f CH=C ES-G.

In formula (Vr), C5 is -COO-5-0CO--CHt
OCO-1-C112C00-1-〇-1-CONHC
00-1-CONI(CONI(-1-SO□~, Dh
Dh D is a hydrogen atom or an optionally substituted aliphatic group having 1 to 1 carbon atoms (e.g., 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-methoxy propyl group, etc.).

G is a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 22-dichloroethyl group, 2,2. 2-) Lifluoroethyl 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 L2-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, 2phosphoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 2
-carboxyamidoethyl group, 3-sulfoamidopropyl group, 2-N-methylcarboxyamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

fl and f may be the same or different, and each represents the same content as el or e in the above-mentioned -formation (TV).

As a specific monomer (A), for example, a carbon number of 1 to 6
vinyl esters or allyl esters of aliphatic carboxylic acids (acetic acid, propionic acid, ##, monochloroacetic acid, trifluoropropionic acid, etc.); unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, etc. Alkyl esters or amides having 1 to 4 carbon atoms of carboxylic acids (alkyl groups such as methyl, ethyl, propyl, butyl, 2-chloroethyl, 2-bromoethyl, 2-fluoroethyl) basis,
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-sulfobutyl group, 4-sulfobutyl group, 3-chloropropyl group, 2-hydroxy-3-chloropropyl group, 2-furfurylethyl group, 2 -Pyridinylethyl group, 2-chenylethyl group, trimethoxysilylpropyl group, 2-carboxyamidoethyl group, etc.); Styrene derivatives (steel bars, styrene, vinyltoluene, α
-Methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenesulfonic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, metquinmethylstyrene, NN-dimethylaminomethylstyrene, vinylhenzenecarpo unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid; cyclic acid anhydrides of maleic acid and itaconic acid; acrylonitrile; methacrylotrile; polymerizable Heterocyclic compounds containing a double bond group (specifically, for example, compounds described in "Polymer Data Handbook - Basic Edition" edited by the Society of Polymer Science, p. 175-184, Baifukan (published in 1986), for example , N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.).

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

The dispersion resin of the present invention comprises a dispersion stabilizing resin and an oligomer (B
), and the important thing is that if the resin synthesized from these monomers is insoluble in the non-aqueous solvent, the desired dispersion can be achieved. Resin can be obtained.

More specifically, for the monomer (A) to be insolubilized, -
Formation (rV) of oligomer (B) from 0.05 to
It is preferable to use 10% by weight, more preferably 0.1 to 5% by weight. Even more preferably 0.3~
It is 3% by weight.

Further, the molecular weight of the dispersion resin of the present invention is 103 to 106, preferably IO' to 5X10S.

In order to produce the dispersion resin used in the present invention as described above, generally, the above-mentioned dispersion stabilizing resin, 11 body (A) and oligomer (B) are mixed in a non-aqueous solvent with hendiyl peroxide, azobis The polymerization may be carried out by heating in the presence of a polymerization initiator such as isobutyronitrile or butyllithium. Specifically, ■Dispersion stabilizing resin, monomer (A) and oligomer (B)
) A method of adding a polymerization initiator to a mixed solution of (2), a method of dropping monomer (A) and oligomer (B) together with a polymerization initiator into a solution in which a dispersion stabilizing resin is dissolved, or (2) a method of adding a polymerization initiator to a mixed solution of A method of optionally adding the remaining monomer mixture together with a polymerization initiator into a mixed solution containing the entire amount of the dispersion stabilizing resin and a part of the mixture of monomer (A) and oligomer (B); There is a method of optionally adding a mixed solution of a dispersion stabilizing resin, monomer (A), and oligomer (B) together with a polymerization initiator to a non-aqueous solvent, and any method can be used for production. I can do it.

The total amount of monomer (A) and oligomer (B) is about 5 to 811 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the nonaqueous solvent.

The soluble resin which is the dispersion stabilizing resin is 1 to 100 parts by weight based on 100 parts by weight of the total monomers used above,
Preferably it is 5 to 50 parts by weight.

The appropriate amount of the polymerization initiator is 0.1 to 5% by weight based on the total monomer amount.

Further, the polymerization temperature is about 50-iso'c, preferably 60-120°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 developing speed is increased, the dispersibility is good, and even if the developing speed is increased, redispersion is easy, and no stains are observed on various parts of the device.

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

Furthermore, 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-sized master plate is used.

In particular, the non-aqueous dispersion resin described in JP-A No. 62-151868 is a monomer containing at least two ester bonds or the like in its molecule that can copolymerize with the monomer that polymerizes and becomes insolubilized. The dispersibility and rigidity resistance of these resin particles have been greatly improved compared to conventional particles, but they are not suitable for use with large-sized offset printing master plates. Plate making I! (For example, Fuji Photo Film Manufacturer, ELP-560, ELP-820, etc.), or when the processing speed of the plate making machine is increased,
If the resin particles provided by the present invention are used, even if there is still a problem with the dispersibility of the particles, no problems will occur even under such severe conditions.

The high redispersibility of the latex particles of the present invention as described above is due to the fact that they are polymerized together with the insolubilizing monomer in the presence of a small amount of oligomer (B) to become resin particles, and at this time, the polar group at the end of the oligomer main chain is The oligomer (B) component modifies the particle interface due to the anchoring effect or adsorption, increasing the affinity with the dispersion medium, and the polymer molecular chains form a comb-shaped structure, resulting in a sterically bulky structure. In the dispersion stabilizing resin, particles are more easily entangled and the steric repulsion effect is further enhanced, and furthermore, the dispersion stabilizing resin contains a specific polar group bonded only to the end of the main chain of the comb-shaped structure.
It is presumed that the effect of these polar group parts being taken into the interior of the resin particles as part of the anchor or adsorbed onto the particle surfaces is improved, and the steric repulsion effect for dispersion stability is further enhanced.

In addition, high rigidity resistance means that the monomer to be insolubilized has good compatibility with the physicochemically bonded oligomer (B), and even under mild fixing conditions, it is sufficiently compatible and forms a uniform film. It is estimated that this will be achieved.

A coloring agent may be used in the liquid developer of the present invention if desired. The coloring agent is not particularly limited; 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. Examples of such materials include magnetic iron oxide powder, powdered lead iodide, carbon blank, nigrosine, alkali blue, Hanzaiero, quinacridonelend, phthalocyanine blue, and the like.

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. There is a method of producing a dye-containing copolymer 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 main component of the liquid developer of the present invention are explained below.

The toner particles mainly composed of a resin and an optional colorant are used in an amount of 0.00 parts by weight based on 1000 parts by weight of the carrier liquid.
5 parts by weight to 50 parts by weight are 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, capri will likely occur in non-image areas. Furthermore, the above-mentioned carrier liquid soluble resin for dispersion stabilization is also used as necessary, and the carrier liquid 1
About 0.5 parts by weight to 100 parts by weight can be added to the parts by weight of ooo.

The birch charge control agent 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 109Ωc+w, it will be difficult to obtain a high-quality continuous tone image, so it is necessary to control the addition cap of each additive within this limit. It is.

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

A mixed solution of macromonomers: 90 g of MM-lauryl methacrylate, 10 g of 2-hydroxyethyl methacrylate, 5 g of thioglycolic acid, and 200 g of toluene was stirred under a nitrogen stream.
It was heated to a temperature of 75°C. 2. Add 1.0 g of 2' azobisisobutyronitrile (abbreviation ^, 1.B, N, ),
After reacting for 8 hours, 8 g of glycidyl methacrylate and 1.0 g of N,N-dimethyldodecylamine were added to the reaction solution.
g and [-butylhydroquinone 0.5 g were added, and the mixture was stirred at a temperature of 100'C for 12 hours. After cooling, this reaction solution was reprecipitated into n-hexane 21 to obtain 82 g of white powder. The weight average molecular weight of the polymer was 3.8 x 10''.

(MM-1) L Butyl methacrylate 90g2 Methacrylic acid 10g,
2-mercaptoethanol 4g 1 tetrahydrofuran 2
00 g of the mixed solution was heated to a temperature of 70°C under a nitrogen stream. A.1. 1.2g of B and N were added and reacted for 8 hours.

Next, this reaction solution was cooled in a water bath to a temperature of 20°C, 10.2 g of triethylamine was added, and 14.5 g of methacrylic acid chloride was added dropwise with stirring at a temperature below 25°C. It was further stirred. After that, add 0.5g of t-butylhydroquinone and bring the temperature to 60.
The mixture was warmed to ℃ and stirred for 4 hours. After cooling, the mixture was added dropwise to water 11 while stirring (for about 10 minutes), stirred as it was for 1 hour, left to stand, and then the water was removed by decantation. After two more washes with water, use 100i of tetrahydrofuran.
d and reprecipitated in petroleum ether 2r. The precipitate was collected by decantation and dried under reduced pressure. The yield of the obtained viscous material was 65g, and the weight average molecular weight was 5.6X10
It was 3.

(MM-2) C11゜C00CJv C0OH Macromonomer: MM-3 hensyl methacrylate) 95g, 2-phosphonoethyl methacrylate 5
A mixture of 4 g of g12-aminoethyl mercaptan and 200 g of tetrahydrofuran was heated to 70° C. with stirring under a nitrogen stream.

A.1. 1.5g of B and N were added and reacted for 4 hours, and then A, 1. 0.5g of B and N were added and reacted for 4 hours. Next, this reaction solution was cooled to a temperature of 20°C, acrylic anhydride Log was added, and the mixture was stirred at a temperature of 20-25°C for 1 hour.

Next, t-butylhydroquinone 1. Add Og and temperature 50
The reaction mixture was stirred at ~60"C for 4 hours. After cooling, the reaction mixture was added dropwise to water 11 with stirring over about 10 minutes, and after stirring for 1 hour, it was left to stand, and the water was removed by decantation. After washing with water was repeated two more times, it was dissolved in 100 #ti! of tetrahydrofuran and reprecipitated in 2! petroleum ether.The precipitate was collected by decantation and dried under reduced pressure.

The yield of the obtained viscous material was 70 g, and the weight average molecular weight was 5.
It was 5 x 103.

(MM-3) Dodecyl acrylate 90g 1 monomer Log of the following structure (1), thioglycolic acid 4g and toluene 200g
A mixture of? The 8th liquid was heated to a temperature of 70°C under a nitrogen stream.

^, 1. Add 1.5g of B and N, react for 5 hours, and then add A
, 1. B, 11. 0.5g of was added and reacted for 4 hours. Next, 12.4 g of glycidyl methacrylate, 1. og and 1.5 g of t-butylhydroquinone were added and reacted at a temperature of 110'C for 8 hours.

After cooling, the reaction mixture was added to a solution of 3 g of p-)luenesulfonic acid and 100 g of a 90 vol 1% aqueous solution of tetrahydrofuran, and stirred for 1 hour at a temperature of 30 to 35°C.

In a mixed solution 21 of water/ethanol [l/3 volume ratio],
The above mixture was reprecipitated and the precipitate was collected by decantation. This precipitate was dissolved in 200 d of tetrahydrofuran and reprecipitated in 2 N of n-hexane to obtain 58 g of powder.
The weight average molecular weight was 7.6 x 10'.

Monomer (1) CH.

Hs (MM 4) CH.

95 g of octadecyl acrylate, 5 g of 3-(2'nitrohensyloxysulfonyl)propyl methacrylate
, 150g toluene and 50g isopropyl alcohol
The mixed solution was heated to a temperature of 80°C under a nitrogen stream. 2
．． 2'-azobis(2-cyanovaleric acid) (abbreviation: ^, C
, V, ) was added and reacted for 5 hours, and then A, C,
V, 1. Og was added and the mixture was reacted for 4 hours. After cooling, methanol 2i! , reprecipitate this reaction product in , collect the powder in four groups,
Dry under reduced pressure.

50g of the above powder/4g of glycidyl methacrylate per day.

A mixture of 0.6 g of N,N-dimethyldodecylamine, 1.0 g of t-butylhydroquinone and 100 g of toluene was stirred at a temperature of 110'C for 10 hours. After cooling to room temperature, the mixture was irradiated with light for 1 hour under stirring using an 80 W high-pressure mercury lamp. Thereafter, the reaction mixture was reprecipitated into 1 liter of methanol, and the powder was dried in 4 batches under reduced pressure. The yield was 34 g and the weight average molecular weight was 7.3 x 10''.

(~(M-5) CL COO (CH 6 in SOJ) A mixed solution of 70 g of P stearyl methacrylate, 30 g of the compound (MM-2) of macromonomer synthesis example 2, and 100 g of toluene was heated to temperature under a nitrogen stream. Warmed to 75°C. A.1.
1.5g of B and N were added and reacted for 4 hours, and then A and 1.
0.5g of B and N were added and reacted for 3 hours. After the reaction, it was reprecipitated in methanol 31, and the powder was collected in four batches and dried under reduced pressure.

The yield was 85 g, and the weight average molecular weight was 3.9XIO'.

(P-1) CH3CL COOCJv C0OH ゛” 2: P-2 65 g of lauryl methacrylate, 15 g of t-prol methacrylate, the compound of macromonomer synthesis example 1 (MM
A mixed solution of 20 g of -1) and 200 g of toluene 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 ^
, 1. B.N.

Add 0.5g of A and 1 for 2 hours. B, N, 0.3
g was added and reacted for 3 hours. The weight average molecular weight of the obtained copolymer was 3.6×10′.

(P-2) C1l, CH.

"3:l"3 in C00CIzHzs C00C)lzcHzOH 75 g of lauryl methacrylate, 25 g of the compound (MM-4) of macromonomer synthesis example 4, and 200 g of toluene
The mixed solution of g was heated to a temperature of 85°C under a nitrogen stream. A, C, ν, 1. Og was added and reacted for 5 hours, and then A
, C,v, were added and reacted for 4 hours. The weight average molecular weight of the obtained copolymer was 4.8×10′.

(P-3) 4 to 11: P-4 to P-11 In Production Example 2 of P-2, lauryl methacrylate, L-butyl methacrylate, and macromonomer (MM-1) were replaced with each compound in Table 1 below. Other than that, each dispersion stabilizing resin was produced by reacting in the same manner as in Production Example 2. The weight average molecular weight of each resin is 3.5X10' to 5. It was OX 10'.

12 to 19: P-12 to P-19 In Production Example 3 of P-3, lauryl methacrylate, macromonomer (MM-4), and C1ν were replaced with each compound in Table 2 below. A dispersion stabilizing resin was produced by reacting in the same manner as in Example 3. The weight average molecular weight of each resin is 3X
It was IO'~6X10'.

(Left below) 1st sesame 1:B-1 23-diacetoxypropyl methacrylate 100
g, 3-mercaptopropionic acid 5g, toluene 150
A mixed solution of 50 g of methanol and 50 g of methanol was heated to a temperature of 70"C while stirring under a nitrogen stream.

2.2'-azobis(isobutyronitrile) (abbreviation A,
1. 1.5 g of B, N,) was added and reacted for 4 hours. Furthermore, A.1. 0.4g of B and N were added and reacted for 4 hours.

After cooling, this reaction solution is reprecipitated into methanol/water ((4/1) volume ratio) mixed solution 21, the methanol solution is separated by decantation, the viscous substance is dried, and the colorless viscous substance is separated. I got 75g. The number average molecular weight of the polymer was 3,300.

Oligomer B-1: COCH3 oligomer 〇 1 to 3: B- to B= In Production Example 1, instead of 2゜3-diacetoxypropyl methacrylate and 3-mercaptopropionic acid, oligomers corresponding to Table 3 below were used. Oligomers B-2 to B-31 were produced in the same manner as in Production Example I except for using a methacrylate monomer and a mercapto compound. The number average molecular weight of the obtained oligomer is 2,500~
It was s, ooo.

(Left below) Table 3 lli ＾ S + CM yo C Hi Table (Continued 1) Table (Continued 2) Table (Continued 3) Table 3 (Continued 4) Oligomer 32:B-32 2-(n-nonylcarbonyloxy) 100g of ethyl crotonate, 150g of toluene, and 5g of ethanol
0 g of the mixed solution was heated to a temperature of 75°C while stirring under a nitrogen stream. 4. Add 8 g of 4'-azobis(4-cyanovaleric acid) (abbreviated as A, C, V, ) and react for 5 hours.
Furthermore, 2 g of ^, C, and V were added and reacted for 4 hours. After cooling the resulting reaction solution, it was reprecipitated into a mixed aqueous solution of methanol/water [(4/l) in a volume ratio of 1, and after separating the aqueous methanol solution by decantation, the viscous material was dried. The yield was 70 g, and the number average molecular weight of the polymer was 2,600.

Oligomer B-32: ct+IC)+3 HOOCACHt)t-C-RCHCN-CN
C00(CHz)zOcOcJ+w(n) O Sesame 3-47B-33-B In Production Example 32, the azobis compound shown in Table 4 below was used instead of the polymerization initiator ^, C, V, and 2-(n nonylcarbonyloxy)
Each oligomer B-3 was prepared in the same manner as in Production Example 32 except that ethyl crotonate was replaced with a monomer corresponding to the structure below.
3 to B-41 were manufactured. The obtained oligomer had a number average molecular weight of 2,000 to 4,000.

(Leaving space below) Table ococ A H2 (Weight composition ratio) Azobis compound R-N=N Table 4 (Continued 1) m-x 1:D-1 10 g of dispersion stabilizing resin P-1, 100 g of vinyl acetate,
1.0 g of oligomer B-1 and 380 g of Isopar H
A mixed solution of g was heated to a temperature of 75° while stirring under a nitrogen stream.
It was heated to C. 2,2'-Azobis(ballet o2-+J
/Iz) (abbreviation: A, B, V, 11) was added and reacted for 4 hours, and further 0.4 g of ^, B, V, N was added and reacted for 2 hours. 20 minutes after the addition of the initiator, white turbidity occurred and the reaction temperature rose to 88°C. temperature to 100°C
The mixture was stirred for 1 hour, and unreacted 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 latex with a polymerization rate of 86% and an average particle size of 0.20*.

m-X 2-33: In Production Example 1 of D-2-D-33 latex particles, dispersion stabilizing resin P-1
Latex particles were produced under the same conditions as in Production Example 1, except that Oligomer B-1 was replaced with each compound shown in Table 5 below. The polymerization rate of each latex particle was 80-88%.

Table (Continued) - 34: D-34 Vinyl acetate 85g, N-vinylpyrrolidone 15g 1 Oligomer B-
A mixed solution of 2 g of P-16, 12 g of dispersion stabilizing resin P-16, and 7380 g of n-deca was stirred under a nitrogen stream.
It was heated to a temperature of 75°C.

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

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.

A mixed solution of 20 g of D-35 dispersion stabilizing resin-1 and 470 g of n-dodecane was heated to a temperature of 60'C while stirring under a nitrogen stream.

In this solution, 100 g of methyl methacrylate, 1.0 g of oligomer B-28, and 1 n-totisyl mercaptaf were added.
．． A mixed solution of 0g and 0.8g (7) of A, B, V, and N was added dropwise over 2 hours. After 2 hours of reaction, ^,B
, ν, N, were added and reacted for 2 hours. After cooling, 2
Coarse particles are removed through a 00 mesh nylon cloth.
The resulting white dispersion was a latex with a particle size of 0.28 m.

M-X's "" 36: 18 g of D-36 dispersion stabilizing resin-13, 100 g of vinyl acetate, 5 g of crotonic acid, 1.5 g of oligomer B-31, and Isopar E.
468 g of a mixed solution was heated to a temperature of 70"C while stirring under a nitrogen stream. 0.8 g of A, B, V, N,
After reaction for 6 hours, 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 0.24 m.

-1st Class 7: D-37 18g of dispersion stabilizing resin-17, 100g of vinyl acetate
, 6.0 g of 4-pentenoic acid, and 1.0 g of oligomer B-26.
A mixed solution of 6 g and 380 g of Isopar G was heated to 75° C. with stirring under a nitrogen stream.

Add 0.7g of A, B, V, and N, react for 4 hours, and then
, B, V, 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 0.23-.

-1st batch 3: D-8 100g of styrene, 20g of dispersion stabilizing resin P-19,
2.0 g of oligomer B-12 and 38 g of Isopar H
0g of the mixed solution was heated to a temperature of 60°C while stirring under a nitrogen stream.
Warmed to °C. 0.6 g of A, B, ν, and N were added and reacted for 4 hours, and 0.3 g of A, B, V, and N were added and reacted for 3 hours. After cooling, it was passed through a 200 mesh nylon cloth, and the resulting white dispersion was latex with a particle size of about 0.20-.

m-x 39: A) In Production Example 1 of latex particles D-1, 20 g of poly(octadecyl methacrylate), vinyl acetate loog, 1.0 g of octadecyl methacrylate, and 38 g of Isopar H
The procedure was repeated in the same manner as in Production Example 1, except that 5 g of the mixed solution was used. The obtained white dispersion had a polymerization rate of 85% and an average particle size of 0.
It was 20-g latex. (Unexamined Japanese Patent Publication 1797-1797
Latex particles described in No. 51) "40: B) In production example 1 of latex particles D-1, 20 g of Bo 1 (octadecyl methacrylate) and 100 g of vinyl acetate.
, 1 g of monomer (1) with the following chemical structure and Isopar H
The procedure was carried out in the same manner as in Production Example 1, except that 385 g of the mixed solution was used. The obtained white dispersion was a latex with a polymerization rate of 86% and an average particle size of 0.24 m. (Unexamined Japanese Patent Publication No. 62-1
Latex particles described in No. 51868) Monomer (1) H3 CHt=C Coo(CHt)zOcOcvH+q(n) Example 1 Dodecyl methacrylate/acrylic acid (copolymerization ratio: 95
15 weight ratio) copolymer, 10 g of nigrosine, and 30 g of Schersol 71 were placed in a paint shaker (Tokyo Seiki ■) together with glass beads and dispersed for 4 hours to obtain a fine dispersion of nigrosine.

30g of resin dispersion D-1 of latex particle production example 1
, 2.5 g of the above nigrosine dispersion, FOC-1400
(manufactured by Nissan Chemical ■, tetradecyl alcohol) 15g, [
A liquid developer for electrostatic photography was prepared by diluting 0.08 g of octadecene-half-maleic acid octadecylamide copolymer to an iz of Schersol 71.

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

Comparative liquid developer A Resin dispersion of Nilatex particle production example 39 Comparative liquid developer B Resin dispersion of Nilatex particle production example 40 These liquid developers were processed using a fully automatic plate making machine ELP404V (Fuji Photo Film ■ ELP Master H type (manufactured by Fuji Photo Film), an electrophotographic light-sensitive material, was exposed and developed. The plate making speed was 6 plates/min. Furthermore, after processing 2,000 sheets of the ELP master ■ 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-6.

When plate making was carried out using each developer 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, offset printing master plates (ELP masters) obtained by plate making using each developer were printed using a conventional method, and the number of prints was compared until the printed image showed missing characters, fading in the edges, etc. As a result, the master plate obtained using the developer of the present invention did not cause the problem even after 10,000 sheets or more, and the master plate using Comparative Example B did not cause the problem.
This occurred at 000 sheets. In the case of Comparative Example A, the problem occurred after 5000 sheets were printed.

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 B, the number of printed sheets is relatively large, 80
I can print 00 copies in two colors, but the developing device is extremely dirty.
It could not withstand continuous use.

In addition, in the case of Comparative Example A, when the plate making speed is as high as 6 sheets/min (previously the plate making speed was 2 to 3 sheets/min), the developing device (especially on the back electrode plate) becomes dirty. After 2,000 copies, the image quality of the copied images on the plate began to be affected (1gax decrease, fine line fading, etc.).

Additionally, the number of master plates printed has decreased.

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

Example 2 White dispersion 10 obtained in latex particle production example 17
A mixture of 0 g and 1.5 g of Sumikalon black was heated to 100°C and stirred for 4 hours. After cooling to room temperature, the remaining dye was removed by passing it through a 200-mesh nylon cloth to obtain a black resin dispersion with an average particle size of 0.25 μm.

32 g of the above black resin dispersion, FOC-1600 (
20g of hexadecyl alcohol (manufactured by Nissan Chemical ■) and 0.05g of zirconium naphthenate in 1 liter of Scherzol 71.
A liquid developer was prepared by diluting the solution to 1 ml.

This was developed using the same device as in Example 1.
Even after developing the 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 D- obtained in latex particle production example 37
A mixture of ioog No. 37 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, 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
．． 05 g of Isopar H! ! A liquid developer prepared by diluting it to 2000
Even after developing the sheets, no toner adhesion was observed 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 4 White resin dispersion 32 obtained in latex particle production example 25
g, 2.5 g of nigrosine dispersion obtained in Example 1, FOC
-1800 (Nissan Chemical, octadecyl alcohol)
Isopar G
No. 1! 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 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 clear.

Further, after this developer was left to stand for three 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.

White resin dispersion D obtained in latex particle production example 2
30g of -2, 4.2g of the above alkali blue dispersion,
20 g of FOC-1600 and 0.0 semi-docosanylamidate of copolymer of diisobutylene and maleic anhydride
A liquid developer was prepared by diluting 6 g of Isopar G to 1j2.

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. Moreover, 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 29 Liquid developers were prepared in the same manner as in Example 5, except that each latex shown in Table 7 below was used in place of latex particles D-2.

This was developed using the same device as in Example 1, and 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.

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

(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.

Claims (3)

[Claims] (1) Electrical resistance 10^9Ωcm or more and dielectric constant 3.5
In an electrostatographic liquid developer comprising at least resin particles dispersed in the following non-aqueous solvent, the dispersed resin particles are [1] a polymer component represented by the following general formula (IIa) or (IIb). at least one of the following and -COOH group, -P
O_3H_2 group, -SO_3H group, -OH group, ▲ formula,
There are chemical formulas, tables, etc. ▼ group (here, R_1 is -R_
2 groups or -OR_2 groups, and R_2 represents a hydrocarbon group), -SH groups, formyl groups, and amino groups. A polymer with a weight average molecular weight of 1 x 10^3 to 2 x 10, which is formed by bonding a polymerizable double bond group represented by the following general formula (I) only to one end of the main chain of the polymer.
A comb-shaped copolymer consisting of at least the macromonomer (M) of ^4 and a monomer represented by the following general formula (III), a dispersion stabilizing resin soluble in the non-aqueous solvent, and [2] the following general formula ( There are carboxyl groups, sulfo groups, hydroxyl groups, formyl groups, amino groups, phosphono groups, and ▲mathematical formulas, chemical formulas, tables, etc. at only one end of the main chain of the polymer consisting of repeating units shown in IV)▼ Group [R
_0 represents -R_0' group or -OR_0' group, R_
0' represents a hydrocarbon group]
The number average molecular weight formed by bonding the polar groups of the species is 1×10^4
Polymer resin particles obtained by polymerizing a monofunctional monomer (A) that is soluble in the non-aqueous solvent but becomes insolubilized by polymerization in the presence of the following oligomer (B): A liquid developer for electrostatic photography, characterized in that: General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) In formula (I), X_0 is -COO-, -OCO-, -C
H_2OCO-, -CH_2COO-, -O-, -SO
＿２−, -CO−, ▲There are mathematical formulas, chemical formulas, tables, etc.▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (here, R_1_1 represents a hydrogen atom or a hydrocarbon group). a_1 and a_2 may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -
COO-Z_1 or -COO-Z_1 via hydrocarbon
(Z_1 represents a hydrogen atom or a hydrocarbon group). General formula (IIa) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (IIb) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ In formula (IIa) or (IIb), X_1 is X in formula (I)
Represents the same content as _0. Q_1 is an aliphatic group having 1 to 22 carbon atoms or 6 to 12 carbon atoms
represents an aromatic group. b_1 and b_2 may be the same or different, and represent the same contents as a_1 and a_2 in formula (I). V represents -CN, -CONH_2 or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and Y is a hydrogen atom, a halogen atom,
It represents an alkoxy group or -COOZ_2 (Z_2 represents an alkyl group, an aralkyl group, or an aryl group). General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (III), X_2 represents the same content as X_0 in formula (I), and Q_2 represents the same content as Q_1 in formula (IIa). represents. d_1 and d_2 may be the same or different, and represent the same contents as a_1 and a_2 in formula (I). However, in the component represented by the general formula (II) in the macromonomer (M) and the monomer component represented by the general formula (III), at least one of Q_1 and Q_2 has a carbon number of 10 to 22. Represents an aliphatic group. General formula (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ In formula (IV), E_1 is -COO-, -OCO-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Numerical formulas, chemical formulas, tables, etc. Yes▼, -O-, -SO_2-, -CONHCOO
-, -CONHCONH-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. (D_1 represents a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms. l represents an integer of 1 to 3.) G_2 represents a hydrocarbon group having 1 to 22 carbon atoms, provided that the carbon chain of G_2 -O-, -CO-, -CO_2
-, -OCO-, -SO_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ may be included. Here, D_2 represents the same content as D_1. e_1 and e_2 may be the same or different from each other,
Hydrogen atom, halogen atom, cyano group, hydrocarbon group, -C
OO-D_3 or -COO-D_3 via hydrocarbon (
D_3 represents a hydrogen atom or a hydrocarbon group which may be substituted. (2) The electrostatic photograph according to item (1), wherein the repeating unit represented by the general formula (IV) of the oligomer (B) contains at least a repeating unit represented by the following general formula (IVa). liquid developer. General formula (IVa) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (IVa), e_1, e_2, and E_1 represent the same symbols as in formula (IV). G_5 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,
-O-, -CO-, -CO_2-, -OCO-, -SO
＿２−, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (D_5 represents the same content as D_1 in formula (IV)). W_1 and W_2 may be the same or different from each other,
Represents a hydrocarbon group having 1 to 18 carbon atoms that may be substituted or ▲ may have a numerical formula, chemical formula, table, etc. ▼ interposed in the main chain bond. Here, B_3 and B_4 may be the same or different from each other and have the same content as B_1 and B_2 above, and W_3 represents a hydrocarbon group having 1 to 18 carbon atoms that may be substituted. m, n and p each independently represent an integer of 0 to 3. However, both do not become 0 at the same time. (3) The dispersion stabilizing resin has -PO_3H_2 groups, -SO_3H groups, -COOH groups at one end of its polymer main chain,
-OH group, -SH group, ▲mathematical formula, chemical formula, table, etc.▼ group (here, Z_0 is -Z_1_0 group or -OZ_1
A comb-shaped copolymer with a weight average molecular weight of 2 x 10^4 to 2 x 10^5, which is made by bonding polar groups selected from _0 group and Z_1_0 indicates a hydrocarbon group), formyl group, and amino group. The electrostatic photographic liquid developer according to item (1) or item (2), characterized in that: