JPH03144581A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To improve dispersion stability, redispersibility and fixability by bringing a monofunctional monomer A which is insolubilized by polymn. and a specific oligomer B into polymn. reaction. CONSTITUTION:Dispersing resin particle are obtd. by bringing the monofunctional monomer A which is insolubilized by polymn. and the oligomer B which is formed by bonding a polar group only to one terminal of the main chain of a polymer consisting of the repeating unit expressed by formula II and has <=10<4> number average mol. wt. into polymn. reaction in the presence of the resin for stabilizing dispersibility which is a polymer contg. the repeating unit expressed by formula I, is formed by crosslinking a part thereof and bonding a polymerizable double bond group thereto and is soluble in nonaq. solvents. In the formula I, T<1> denotes -COO-, -OCO-, etc.; A<1> denotes an aliphat. group; a<1> and a<2> respectively denote a hydrogen atom, halogen atom, etc. In the formula II, V<0> denotes -O-, -S-, etc.; Y<0> denotes a hydrogen atom or hydrocarbon group; X<1> and X<2> denote -O-, -S-, etc.; R<2> and R<3> denote a hydrocarbon group; b<1>, b<2> denote a hydrogen atom, halogen atom, etc. The excellent stability of dispersion, redispersibility and fixability are obtd. in this way.

Description

[Detailed description of the invention]

(Field of Industrial Application) The present invention relates to a liquid developer for electrostatic photography, which is made by dispersing at least a resin in a carrier liquid having an electrical resistance of 109 Ωcm or more and a current ratio of 3.5 or less, and in particular has excellent redispersibility. , shelf life,
It relates to a liquid developer with excellent stability, image reproducibility, and fixing properties. (Prior art) General liquid developers for electrophotography contain organic or inorganic pigments or dyes such as carbon black, nigrosine, and phthalocyanine blue, and natural or synthetic resins such as algin 1' resin, acrylic resin, rosin, and synthetic rubber. Dispersed in a liquid with high insulating properties and low dielectric constant, such as petroleum-based aliphatic hydrocarbons, and added with a polarity control agent such as metal soap, lecithin, linseed oil, higher fatty acids, or a polymer containing vinylpyrrolidone. It is. In such developers, the resin is dispersed as insoluble latex particles in the form of particles with a diameter of several nanometers to several il nm, but in conventional liquid developers, a soluble dispersion stabilizing resin, a polarity control agent, and insoluble latex particles are dispersed. Because of insufficient bonding, the soluble dispersion stabilizing resin and polarity control agent were likely to diffuse into the solution. Therefore, due to long-term storage or repeated use, the soluble dispersion stabilizing resin is detached from the insoluble latex particles, causing the particles to settle, aggregate, or accumulate.
The drawback was that the polarity was unclear. Furthermore, since particles that have aggregated and accumulated are difficult to redisperse, they remain attached to various parts of the developing machine, leading to problems with the developing machine such as staining of the image area and clogging of the liquid feed pump. In order to improve these drawbacks, a means for chemically bonding a soluble dispersion stabilizing resin and insoluble Latinx 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 has improved to some extent due to the natural settling of particles, it is still not sufficient, and when used in an actual developing device, the toner adhering to various parts of the device may be removed. It solidifies into a film, making it difficult to redisperse, and furthermore, it causes equipment failure, stains on copied images, etc., and has the disadvantage that redispersion stability is insufficient for practical use. In addition, in the method for producing resin particles described in -1-, in order to produce monodisperse particles with a narrow particle size distribution, the dispersion stabilizer used,
There are significant restrictions on the combination of insolubilizing monomers, and the result is generally particles with a wide particle size distribution containing a large amount of coarse particles, or polydisperse particles with two or more average particle sizes. In addition, it is difficult to obtain a desired average particle size with monodispersed particles with a narrow particle size distribution, and large 117- or 0.
．． Very fine particles of 1p 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 drawbacks mentioned in L, an insoluble dispersion 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 is added. A method of improving the dispersibility, redispersibility, and storage stability of particles by forming them into resin particles is disclosed in JP-A-60-179751 and JP-A-62-151868. In addition, in the presence of a polymer using a difunctional monomer or a polymer using a polymer reaction, the monomer to be insolubilized is polymerized to form insoluble dispersed resin particles, which improves particle dispersion, redispersibility, and storage stability. A method for improving the properties is disclosed in JP-A-60-1.85962 and JP-A-61-43757. (Problems to be Solved by the Invention) On the other hand, in recent years, a method of printing a large number of sheets (5000 sheets or more) using a master plate for off-cent printing using an electronic force type has been attempted, and improvements in the master plate are particularly important. As progress has been made, it has become possible to print more than one sheet with large size printing. 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-60-17975] and JP-A-62-15186
The particles produced according to the method disclosed in 8:9:1 had good particle monodispersity, repartitionability, and storage stability, but the printing durability and fixing time in large plate sizes were poor. The performance was not satisfactory for speeding up the process. Also, the above-mentioned Japanese Patent Application Laid-Open Nos. 60-185962 and 61437
Dispersed resin particles prepared according to the procedure disclosed in No. 57B have advantages in terms of development speed, particle dispersibility and redispersibility, shortening of fixing time, and large plate size. In the case of master plates (for example, A3 size or larger), their performance has not always been satisfactory in terms of rigidity resistance. The present invention solves the problems of conventional liquid developers as described below. An object of the present invention is to provide a liquid developer with excellent dispersion stability, redispersibility, and fixing properties. In particular, an object of the present invention is to provide a liquid developer that has excellent dispersion stability, redispersibility, and fixing properties even in an electrophotolithography system that speeds up the development and fixation process and uses a large-format master plate. . Another object of the present invention is to provide a liquid developer that enables the electrophotographic production of offset printing plates having excellent printing ink oil sensitivity and stiffness resistance. Another object of the present invention is to provide a liquid developer suitable for various electrostatic photographs and various transfer applications in addition to the above-mentioned applications. Still another object of the present invention is to provide a liquid developer that can be used in any system in which a liquid developer can be used, such as inkjet recording, cathode ray tube recording, and recording of various pressure change or electrostatic change processes. That's true. (Means for Solving the Problems) The above-mentioned aspects of the present invention [1] electric resistance of 109 Ωcm or more;
In an electrostatic photographic liquid developer comprising at least a resin dispersed in a non-aqueous solvent having a dielectric constant of 3.5 or more, the dispersed resin particles have a repeating medium represented by the following general formula (1). At least a polymer containing at least a portion thereof is crosslinked, and
In the presence of a dispersion stabilizing resin soluble in the nonaqueous solvent, which has a polymerizable double bond group copolymerizable with the monofunctional monomer (A) bonded to only one end of at least one polymer main chain. , one of the main chains of a polymer consisting of a monofunctional monomer (A) that is soluble in the non-aqueous solvent but becomes insolubilized by polymerization and a repeating unit represented by the following general formula (n). Carboxyl group, sulfo group, hydroxyl group only at the terminal,
At least one polar group selected from formyl group, amino group, 1 phosphono group, and -P-170 group (RO represents -R1 group or -0RO!1 group, 1?1 represents hydrocarbon Z) Copolymer #A fat particles obtained by polymerizing and pouring a solution containing at least one oligomer (I3) having a molecular weight of 104 or less, which is formed by bonding groups. This was achieved by a liquid developer for electrostatography which is characterized by certain characteristics: General formula (1) In general formula (+), TI is -000-1-OCO-1-c
o, oco-1C1, COO-1-〇- or -3O□-
represents. A1 represents an aliphatic group having 6 to 32 carbon atoms. a+ and R2 may be the same or different, and each represents a hydrogen atom, a hydrogen atom, a cyano group, and a carbon number of 1 to 8.
The hydrocarbon group -COO- represents or -coo-z' via a hydrocarbon group having 1 to 8 carbon atoms. Here, Zl represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. Format (II) 1 b2 −

[CH-C-V"-(R2-X'), (R"X"), Y' general formula (I
l) Nioiite, vo is -0-1-S-1-COO-1O
Represents CO--CHzOCO- or -cH, coo-. Vo represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. x' and x2 may be the same or different, and o-
1-s--co-2-CO2--0CO--8Oxy
I y + v ' 1 1 1 N---CON- or -NGO- (V 鈇i represents the same content as Y' above). R2 and R3 may be the same or different from each other, may be substituted, or -C)I- in the main chain)(3, (R4
44) -p-y2 may be interposed in the bond [x3 and x4 may be the same or different from each other and have the same contents as XI and Xt above, and R4 is an optionally substituted carbon number of 1 to 18 represents a hydrocarbon group, Y2 has the same content as Yo] carbon number 1-
Represents hydrocarbon groups per day. bl and b2 may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, a Coo-R
' or 1Coo-11' (R5 represents a hydrogen atom or an optionally substituted hydrocarbon group) via a hydrocarbon. m, n and p may be the same or different, and are 0 to 4
represents an integer. However, m+n is 1 or more. Hereinafter, the liquid developer of the present invention will be explained in detail. Electrical resistance used in the present invention: 109 Ωcm or more, dielectric constant: 3
．． 5 or less, preferably linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, or aromatic hydrocarbons, and halogen-substituted products thereof. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, isopar
Isopar G1 Isopar 11, Isopar L (Isopar; trade name of Exxon), Scherzol 7o, Scherzol 71 (Shelzol; trade name of Nel Oil), Amsco OMS, Amsko+460iW agent (Amsco; trade name of Svirinot) ) etc. can be used alone or in combination. Non-aqueous dispersed resin particles (hereinafter sometimes referred to as latex particles), which are the most important component in the present invention, are polymers containing at least the repeating unit represented by the general formula (1) in a non-aqueous solvent. A part of it is cross-linked, and
In the presence of a dispersion stabilizing resin soluble in the nonaqueous solvent, which has a polymerizable double bond group copolymerizable with the monofunctional monomer (A) bonded to only one end of at least one polymer main chain. , polymerizing the monomer (A) and the oligomer (B) (
It is manufactured by the so-called polymerization granulation method. Here, as the non-aqueous solvent, basically any solvent can be used as long as it is miscible with the carrier liquid of the electrostatic photographic liquid developer. That is, the solvent used in producing the dispersed resin particles may be any solvent as long as it is miscible with the carrier liquid, and preferably linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, and aromatic hydrocarbons. and halogen-substituted products thereof. For example, hexano, octane, isooctane, decane, isodecane, decalin, nonane, dodecane,
isototican, isoparaffinic petroleum solvents Isopar E, Isopar G1 Isopar I11 Isopar L1 Scherzol 70, Scherzol 71, Amsco O
MS, Amsco 460 solvent, etc. are used alone or in combination. Solvents that can be mixed with these organic solvents include alcohols (for example, methyl alcohol,
ethyl alcohol, propyl alcohol, methyl 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, propion ethyl acid, etc.), ethers (e.g. diethyl ether, dipropyl ether, tetrahydrofuran, dioxane, etc.), halogenated hydrocarbons (e.g. methylene dichloride, chlorophor 11, carbon tetrachloride, 5 dichloroethane, methyl chloroform, etc.). . It is preferable that the non-aqueous solvent used in combination be removed by heating or distillation under reduced pressure F after polymerization and granulation, but even if it is brought into the liquid developer as a latex particle dispersion, There is no problem as long as the resistance is within a range that satisfies the condition of 109ΩC11l or more. Usually, it is preferable to use the same solvent as the carrier liquid at the stage of resin dispersion production, and as described in 1-1, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic carbon Examples include hydrogen and halogenated hydrocarbons. The present invention is used to make a stable resin dispersion of a non-aqueous solvent-insoluble copolymer produced by copolymerizing a -functional 1iit compound (A) and an oligomer (B) in a non-aqueous solvent. The dispersion stabilizer (resin for dispersion stabilization) related to the general formula (+
), a part of which is crosslinked, and a polymerizable double that can be copolymerized with the monomer (A) at only one end of at least one polymer main chain. It is characterized by being a resin soluble in the non-aqueous solvent, which is formed by bonding a heavy bond group. The dispersion stabilizer (dispersion stabilizing resin) will be explained in detail below. General formula (1) shown as a repeating unit of a polymer component
may be substituted with a hydrocarbon group number. In general formula (1), TI is preferably -C00-1
OCO-, -C1 (zOCO-1 or -Cl-12CO
Does not represent O-. AI preferably represents a hydrocarbon group having 8 to 22 carbon atoms, specifically octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosanyl group, eicosanyl group, octenyl group. , decenyl group, dodecenyl group, l.lysocenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, and tocosenyl group. al and a2 may each be the same or different,
Preferably a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, and a carbon number of 1 to 6
hydrocarbon group (e.g., methyl group, xf-ru%, propyl group, butyl group, phenyl group, etc.), -coo-z'
-coo-z via a group or a hydrocarbon group having 1 to 6 carbon atoms
' represents. Here, Zl is a hydrogen atom or a carbon number of 1 to
18 hydrocarbon groups (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, butenyl group, hexenyl group, octenyl group, decenyl group, hensyl group, phenethyl group, phenyl group, chlorohensyl group, pro-hensyl group, methylhensyl group, monophenyl group, bromophenyl group, tolyl group, etc.). More preferably al,
Either one of a2 is a hydrogen atom. As the repeating unit of the polymer main chain in the dispersion stabilizing resin of the present invention, a repeating unit other than the repeating center represented by the above-mentioned general formula (1) may be contained. The repeating unit other than -C2(1) may be, for example, any -monofunctional monomer that can be copolymerized with the monomer corresponding to the repeating unit represented by general formula (1). Specific examples include repeating units represented by general formula (Ill). --Format (III) dl d2 1,000CH-C)-2-Z2 In formula (III), T2 is -COO--0CO--CIl
□0CO-. Examples include NlIC0-2 CI(2NHCO ll5Oz Cll□Nll5O2-1). Wl represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms which may be substituted (for example, a methyl group, an ethyl group, a buIcobyl group, etc.). group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, octadecyl group, 2
-Hydroxyethyl group, 3-hydroxypropyl group, 2-
Chloroethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-carboxyethyl group, butenyl group, hexenyl group, octenyl group, cyclohexyl group, benzyl group, phenethyl group, phenyl group, tolyl group, naphthyl group, chlorophenyl group group, bromophenyl group, methoxyphenyl group, bromohensyl group, methylhensyl group,
[me], xybenzyl group, etc.). h2 is a hydrogen atom, a halogen atom (for example, a fluorine atom,
chlorine atom, bromine atom, etc.), alkyl groups (e.g. methyl group, ethyl group, propyl group, chloromethyl group, and 1.a
oxymethyl group, N, N-dimethylaminomethyl group, N,
N-diethylaminomethyl group, etc.), a hydroxy group, a carboxyl group, or a sulfo group. S represents an integer from 1 to 4. Z3 is a linking group or bond o- that connects the Hensen ring and Z2,
Examples include -sl, -so□N-, and a direct 3-junction bond between the Hensen ring and Z2 (3 represents the same content as 4+). Z2 is a hydrogen atom, an unsubstituted hydrocarbon group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, cyclohebutyl group,
cyclohexyl group, hexenyl group, phenyl group, etc.), substituted aliphatic groups having 1 to 22 carbon atoms [as substituents,
For example,)\Rogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), -0ff, -5H, -CO
OH, -5 (hl, -3O2■, each represent the same content as Prisoner 1), -ocow6, I0-i -3-匈6, -5i-W7, -COOi, -S
O□w6 (w6, 匈8 W?, hll each represent the number of carbon atoms 1 to 18 that may be substituted.
(specifically the same content as -1)], heterocyclic groups (e.g., 100-offene ring, biran ring, furan ring, pyridine ring, morpholine ring, piperidine ring, imidazole ring) , henshidandazole ring, thiazolole ring, etc.), or an optionally substituted aromatic group (e.g., phenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, etc.), phenyl group, chlorophenyl group, bromophenyl group, Dichlorophenyl group, dibromophenyl group, trifluoromethylphenyl group, hydroxyphenyl group, methoxyphenyl group, carboxyphenyl group, sulfophenyl group, carboxy≧1゛soenyl group, sulfamidophenyl group, methoxycarbonylphenyl group, acetamidophenyl group group, cyanophenyl group, nitrophenyl group, methanesulfonylphenyl group, etc.). dl and d2 may be the same or different, and each represents the same content as al or a2, which satisfies the above general formula (1). Furthermore, monomers other than those corresponding to the repeating unit represented by general formula (III) as shown below may be used, for example,
Maleic acid, maleic anhydride, itaconic acid hydrate, vinylnaphthalenes, vinyl heterocyclic compounds in which a hinyl group is directly substituted on the ring (e.g., vinylpyridine, vinylimidazole, vinylthiophene, vinylpyrrolidone, vinylbenzimine) Dazur, vinyltriazole, etc.). The dispersion stabilizing resin of the present invention uses a polymer component selected from the repeating units represented by -formation (1) as a homopolymer component, or corresponds to the repeating units represented by -formation (1). Contained as a copolymer component obtained by copolymerizing with other monomers that can be copolymerized with the monomer, such as the above-mentioned -formation (monomer corresponding to the repeating unit shown by [[l], etc.) However, it is a polymer in which one portion is crosslinked, and furthermore, it is a polymer in which a polymerizable double bond group is bonded only to one end of at least one polymer main chain. The dispersion stabilizing resin of the present invention comprises a monomer corresponding to the repeating unit represented by -formation (1) and another monomer copolymerizable with the monomer (for example, the above-mentioned -formation (III)). 3 as a copolymer component obtained by copolymerizing the monomers corresponding to the repeating units shown in (1), the monomers corresponding to the repeating units shown in formation (1) are 30 per 100 parts by weight
The amount is at least 50 parts by weight, preferably at least 50 parts by weight, and more preferably at least 70 parts by weight. As a method for introducing a crosslinked structure into a polymer, commonly known methods can be used. That is, in the polymerization reaction of monomers, there are two methods: a method in which a polyfunctional monomer is coexisting, and a method in which a functional group that promotes a crosslinking reaction is contained in the polymer and crosslinked by a polymer reaction. Preferably, a method in which a monomer having two or more polymerizable functional groups -L is polymerized together with a monomer corresponding to the above general formula (1) to crosslink polymer chains is preferred. Specifically, the polymerizable functional group is CHz=CIC1]. 1 CH2・CII -CI□-1C1h-CIl-C-0
, C11゜=C, C-0-31 113 CIl□=CI(-CONHCOO-, CL-C-CO
)LflCOO-1d CH2・CI(-N11CO-1CI.・C)1-C1
12-NHCO-1CI+2・Cl-5O□C112・
Cl1-CO-1CIl□-CH-0-, CH2・CH
-5- etc., but monomers having two or more of the above polymerizable functional groups are monomers having two or more of the same or different polymerizable functional groups. That's fine. Specific examples of monomers having two or more polymerizable functional groups include styrene derivatives such as divinylhenzen and trivinylhenzen; polyhydric alcohols (e.g. , ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol 11200, 11400, #600.1.3
-butylene glycol, neopentyl glycol, dibutylene glycol, polypylene glycol, trimethylolpropane, trimethylolethane, pentaerythritol, etc.) or polyhuman-11oxyphenols (e.g., hydroquinone, resolucin, catenyl glycol, etc.) −
esters, vinyl ethers or allyl ethers of methacrylic acid, acrylic acid or crotonic acid (and their derivatives); dibasic acids (e.g. malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, vinyl esters, allyl esters, vinylamide FM or allylamides of fucuric acid, itaconic acid, etc.; Examples include condensates with methacrylic acid, acrylic acid, crotonic acid, allyl acetic acid, etc.). Further, monomers having different polymerizable functional groups include, for example, carboxylic acids containing vinyl groups [e.g., methacrylic acid, acrylic acid, methacryloyl acetic acid, acryloyl acetic acid, methacryloylpropionic acid, acryloylpropionic acid, icconyloyl acetic acid, :'4 Niloylbrobionic acid, reactants of carboxylic acid anhydrides and alcohols or atoms (e.g., allyloxyproponylprobionic acid, allyloxycarbonylacetic acid, 2-allyloxycarbonylbenzoic acid, allylaminocarbonylpropion) ester derivatives or atho derivatives containing vinyl groups (e.g., vinyl methacrylate, vinyl acrylate, vinyl itaconate, allyl methacrylate, allyl acrylate, allyl itaconate, vinyl methacryloyl acetate, methacryloyl Vinyl propionate, allyl methacryloylpropionate, vinyloxycarbonylmethyl methacrylate, vinyloxycarbonylmethyloxycarbonyl ethylene acrylate, N-
Allyl acrylamide, N-allyl methacrylamide,
N-allyl itaconic acid amide, methacryloylpropionic acid allylamide, etc.); or amino alcohols (e.g., aminoethanol, 1-aminopropanol, 1-
Examples include condensates of aminobutanol, 1-aminohexanol, 2-aminobutanol, etc.) and carboxylic acids containing vinyl groups. 7 In the present invention, a partially crosslinked resin is produced by polymerizing a monomer having two or more polymerizable functional groups at 15% by weight or less, preferably 10% by weight or less of the total monomers. can be formed. In addition, the polymerizable double bond group that is bonded only to the 31-terminus of at least one polymer main chain is either directly bonded to one end of the polymer main chain, or has a chemical structure bonded via an arbitrary linking group. have Specifically, for example, a chemical structure represented by -formation (IV) may be mentioned. General formula (TV) e e" CII = C T3-υ In formula (IV), T3 represents the same content as T2 in general formula (Ill). el and C2 may be the same or different from each other, Each represents the same content as dl or C2 in the above-mentioned -formation (III). Represents a bonding group. Examples of bonding groups include carbon-carbon bonds (-multiple bonds or double bonds), carbon-heteroatom bonds (heteroatoms include, for example, oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.), heteroatoms, etc. A group consisting of any combination of atom-hetero atom bond groups, halogen atoms (e.g., fluorine atom, chlorine source γ, bromine atom, etc.), cyano group, hydroxyl group, alkyl group (
For example, methyl group, ethyl group, proS02, ON b SO□N1 6 NIICOO-1 N It C011+1 , 6 Si [Z6 and Z7 are each a hydrogen atom, a hydrocarbon group having 1 to 8 carbon atoms (for example, a methyl group) , ethyl group, propyl group,
butyl group, pentyl group, hexyl group, hensyl group, phenethyl group, phenyl group, tolyl group, etc.), or -0Zll
(Z!' represents the same content as the hydrocarbon Jl! in Z6)], etc. The general formula (
The polymerizable double bond group represented by IV) is specifically shown below. However, in the following specific example, A is -1
1, -CII3 or -Ct12COOCtL+, and B represents -11 or -CJb. Also, n is 2 to 1
o represents an integer, m represents 2 or 3, l represents 1.2
or 3, p represents an integer of 1 to 4, and q does not represent 1 or 2. CH. (1) CL=CII-COO-1(2) C
ll=C-COOC1+. ■ (3) CIl・CH-C,00-, (J)
CIl□=CB-CH2COO (5) C112・CH-OCO (6) C1,=C11-, CII□OC0 A CIh=C-Coo (CH2)-5OCOC11□・
C-C00CII□CIC)lzoOci1 (]0) CI+,,C Coo(CHz)55 (12) ■ CH2=C C0NH(CL),S 1 (14) CIl□=C11 (15) CHI□+C Coo( CIl□hs 8 (17) CH2・C (19) CI+2−CI!−CHzCOO(CIlz)−HS2 113 (22) C11,=C C0NIC0O(Cllz) 2S C)1°(23) CIl□・C C0NIC0NH( C1lz) zS (24) CHz, CH-OCO(CHz)-1'5(25) C11, = CII -CII□-0C0(C11□-
)rS ShiN 1h (32) C11,・Cl1-CH□Coo(C11□)3CN Cl13 CN 113 CN 8H The present invention in which a polymerizable double bond group is bonded only to one end of the polymer main chain The dispersion stabilizing resin can be prepared by: (1) reacting the ends of living polymers obtained by conventionally known anionic polymerization or cationic polymerization with reagents containing various double bond groups, or (2) reacting the ends of this living polymer with a specific reaction.・Gender base (e.g. -011, -C0011
, -5O111, -1111z, -511, /\, PO, II2, -NCO, -NC3, -Cll-Cll
z, -cocz, -so□C1, etc.), and then introduce a polymerizable double bond group by polymer reaction (ionic polymerization method); or After radical polymerization using a polymerization initiator and/or chain transfer agent containing a specific reactive group, the specific reactive group bonded only to one end of the polymer main chain is used. It can be easily produced by a synthetic method such as a method of introducing a polymerizable double bond group by performing a polymer reaction. Specifically, P, Dreyfuss & R, P,
QuirkEncycle, Polym, Sci,
Eng., 7, 551 (+987), Yoshiki Nakajo, Yuya Yamashita [Dye Drug J, 3-232 (+985)
), Akira Nita, Susumu Nagai F Science and Industry”, So, 57 (198
6), P., F., Rempp & E., Frant.
a. Advancesin Polymer 5ci
ence, 58.1 (1984), Hiroshi Ito - “Polymer Processing J, 35.262 (1986L V, P
ercec 8ppli d Polymer 5cie
A polymerizable double bond group can be introduced according to the method described in a review article such as NCE, 285+97 (+984) and the literature cited therein. Furthermore, specifically, (1) at least one monomer corresponding to the repeating unit represented by general formula (1), a polyfunctional intermediate for introducing the above-mentioned crosslinked structure, and the above-mentioned monomer into the molecule. A method in which a mixture of chain transfer agents containing "specific reactive groups" is polymerized with a polymerization initiator (e.g. azobis compound, peroxide, etc.), or (2) A method of polymerization using a polymerization initiator containing the "specific reactive group" as described above, or (2) A method in which both the chain transfer agent and the polymerization initiator contain the "specific reactive group" in the molecule. A polymer having a crosslinked structure and having a specific reactive group bonded only to one end of the polymer main chain is synthesized by a method using a compound.Next, this specific reactive group is An example of this method is to introduce a polymerizable double bond by performing a polymer reaction using ``. Chain transfer agents used include, for example, mercapto compounds containing the "specific reactive group" or a substituent that can be introduced into the specific reactive group (for example, thioglycolic acid, thiomalic acid, diosalicyl). Acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N(2-mercaptopropionyl)glycine, 2mercaptonicotinic acid, 3-[N-(2-mercaptoethyl)carbamoyl]propionic acid, 3 (N-(
2-Mercaptoethyl)amino)butionic acid, 1l
-(3-mercapdobu I:]pionyl)alanine, 2-
Mercaptoethanesulfonic acid, 3mercapdobu 1] pansulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercap I ethanol, 1-mercap l--2-plcobanol, 3-mercapto-2-butanol, mercap]・phenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-viridinol, etc.), or the "specific reactive group" or the '
Iodoalkyl compounds containing a substituent that can be induced into a "specific reactive group" (e.g. iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.) Can be mentioned. Preferred examples include mercap].compounds. In addition, as a polymerization initiator containing a "specific reactive group" or a substituent that can be induced into a "specific reactive group",
For example, 4.4''-azobis(4-anozoic acid), 4.
4'-Azobis (4-cyanoacrylic acid chloride F'), 2
．． 2' ~ Azobis (2-cyatuburobanol), 2
2'-azobis(2-cyanopentanol), 2.2
'-azobis[2-(5-hy]roxy-3,4,5,6
-tet-rahitropyrimidine-2-4)bucopan]
, 2,2'-Azobis(2-methyl-N-(1,1His(HisI.roxymethyl)-2-hydroxyethyl)propioaξN,2 , 1-bis(hydroxymethyl)ethyl]propioa=51), 2 2'azobis[2
-Methyl-N-(2-hydroxyethyl)-butylene J Pioa Kure F'), 2,2'-azobis(2-azobis dinopropane), and the like. The amount of each of these chain transfer agents or polymerization initiators used is 0.5 to 5 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the total monomers. The dispersion stabilizing resin of the present invention is soluble in an organic solvent,
Specifically, it is sufficient that the dispersion stabilizing resin dissolves at least 5 parts by weight or more at a temperature of 25°C in 100 parts of the toluene solvent. The weight average molecular weight of the dispersion stabilizing resin of the present invention is lX10
4-1. X106, preferably 2X104 to 5x
10! ′. The lit body used in manufacturing non-aqueous dispersion resin is
Monofunctional monomers (A), which are soluble in the non-aqueous solvent but become insolubilized by polymerization, and oligomers (B), which copolymerize with monomer (A), can be distinguished. . The monomer (A) in the present invention may be any monofunctional monomer that is soluble in a nonaqueous solvent but becomes insolubilized by polymerization. Specifically, for example - formation (
Examples include monomers represented by V). It represents the general formula (V) l r2 CII=C ---J. Here, J' is a hydrogen atom or a carbon number of 1 to 18
optionally substituted aliphatic groups (e.g., methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl group, 2
-bromoethyl group, 2-cyanoethyl group, 2-hydroxyethyl group, hensyl group, colobenzyl group, methylhensyl group, methoxyethyl group, phenethyl group, 3-phenylpropyl group, dimethylhensyl group, furobenzyl group, J represents a hydrogen atom or an optionally substituted aliphatic group having 1 to 6 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group). , 2-chloro17J ethyl group, 2゜2-dichloroethyl L 2,2.24 lyfluoroethyl group, 2-bromoethyl group, 2-glycidylethyl group, 2-hydroxoethyl L2-hydroxypropyl group, 2,3-dihydroxypropyl group, 2-hydroxy-3-chloropropyl group, 2
Cyanoethyl group, 3-cyanopropyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-ethyl-xyethyl group, N,N-dimethylaminoethyl group, N,N-diethylaminoethyl group , trimethoxysilylpropyl group, 3-bromopropyl group, 4
-Hydroxybutyl group, 2-furfurylethyl group, 2-
Thienylethyl group, 2-biwadylethyl group, 2-morpholinoethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 2-phosphoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 2
Carboxyamidoethyl group, 3-sulfo-dobropyl group, 2-N-methylcarboxyamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl Me). fl and f2 may be the same or different, and each represents the same content as bl or bl in the above-mentioned -formation (1). 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, acetic acid, monochloroacetic acid, trifluoropropion M, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, etc. C1-4 optionally substituted alkyl esters or amino acids of acids (alkyl groups such as methyl group, ethyl group, propyl group, butyl group, 2-chloroethyl L2-bromoethyl L2-) loiconityl basis,
Trifluoroethyl group, 2-hydroxyethyl group, 2-cyanoethyl 1.2-Nikawaconidel group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-henzenesulfonylethyl group, 2-(N , N-diethylamino)
Ethyl group, 2(N,N-diethylamino)ethyl group, 2
-Carboxyethyl group, 2-phosphoethyl group, 4-carboxybutyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-chloropropyl group, 2-hydroxy-3-
Chlorol-1 propyl group, 2-furfurylethyl group, 2-
pyridinyl ethyl group, 2'-thiconinylethyl group, trimethoxysilylpropyl group, 2-carboxyamidoethyl group, etc.); styrene derivatives (e.g. eva, styrene, vinyl 1-helene, α-methylstyrene, vinyltifen, polystyrene, dichlorostyrene , solomostyrene,
Vinylbenzenecarboxylic acid, vinylbenzenecarboxylic acid, chloroethylstyrene, hydroxymethylstyrene,
methoxymethylstyrene, N,N-dimethylaminomethylstyrene, vinylhenzenecarboxamide, vinylbenzenesulfamide, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid; maleic acid, Cyclic anhydride of itaconic acid; acrylonitrile; methacrylonitrile; heterocyclic compound containing a polymerizable double bond group (specifically, for example, the Polymer Society of Japan LIR Polymer Data Handbook - Basics! -, +, p
175-184, and compounds described in Baifukan (published in 1986), such as N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc. ) etc. Two or more types of monomers (A) may be used in combination. Oligomer (B) is an oligomer with a number average molecular weight of 104 or less, which is formed by bonding the above-mentioned specific polar group only to one end of the main chain of the polymer consisting of repeating units represented by -formation (II). It is. - in formation (11) hl, bl, yo, Yl and Y
Each of the hydrocarbon groups contained in 2 has the indicated number of carbon atoms (as an unsubstituted hydrocarbon group), but these hydrocarbon groups may be substituted. -Formation (DH,, -ite v0 is -〇-1-S-2-
COO-1OCO--CH□0CO- or -C12CO
Represents O-. Yo preferably does not represent a hydrogen atom or an optionally substituted aliphatic group having 1 to 18 carbon atoms in total. Preferred L7 aliphatic groups include substituted alkyl groups having 1 to 18 carbon atoms (e.g., methyl, ethyl, propyl, butyl, heptyl, octyl, decyl). , todenyl group, hexenyl group, octadecyl group, 2
-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group, etc.), carbon number 4-18
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, etc.), an optionally substituted aralkyl group having 7 to 12 carbon atoms (e.g., hensyl group, phenethyl group,
3-phenyl group [7-biru group, naphthylmethyl group, 2-naphthylethyl group, RI: J lohenzyl group, bromohen,
'sil group, methylhensyl group, ethylhensyl group, methoxyhensyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), optionally substituted alicyclic group having 5 to 8 carbon atoms J
, ((e.g., soclohexyl group, 2cyclohexylethyl group, 2-noclobentylethyl group, etc.). R1 and R2 may be the same or different from each other, and o-
-s--co-1-C:OO--0CO--5OzY'
Y' Y N--CON- or -11CO- (Y' indicates the same content as Y0 above). More preferably -〇C
0-1 represents coo-, -oco- or -N-. R2 and R3 may be the same or different from each other, may be substituted, or -C1t- may be replaced by main chain X'J (R'-X
') A hydrocarbon group having 1 to 18 carbon atoms that may be interposed in the bond of yY2 (hydrocarbon groups include aliphatic groups such as alkyl groups, alkyl groups, aralkyl groups, and alicyclic groups) Preferred specific examples of these aliphatic groups include the same content as the preferred aliphatic group of Yo mentioned above.However, R3 and R4 may be the same or different, and the above XI, Shows the same content as XZ, R" is an alkylene group having 1.-Ill carbon atoms even if substituted,
represents an alkenylene group or an aralkyl group, and Y2 is the above Y
Indicates the same content as 0. Further, regarding R2 and R3, to give a specific example, 6 eC)-[R6 and R7 are hydrogen atoms, carbon atoms 1 to 12 (
Preferably 7 alkyl groups having 1 to 6 carbon atoms, halogen atoms (R3
, R4, Y2, R4, and p has the same meaning as the above symbol W2). bl and b2 may be the same or different from each other,
Preferably a hydrogen atom, a halogen atom (e.g., a chlorine atom, a bromine atom, etc.), a cyano group, an alkyl group having 1 to 3 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, etc.), -Coo-R5 or - CH2COOR5 (R' represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms, an alkenyl group, an aralkyl group, an alicyclic group, or an aryl group, which may be substituted; specifically, the above Y
0) represents the same content as described for 0. m, n and p may be the same or different, and are 0 to 4.
represents an integer. However, mn≧1. Further specific examples of the repeating unit represented by the general formula (1) as described above are given below. However, the content of the present invention is not limited to these. In the following, a is H or CL; R is an alkyl group of Cl-18; R'' is a hydrogen atom or an alkyl group of CI-Ill; , kz is an integer from 1 to I2; Eo, 12 are Indicates an integer from 1 to 100. (A) −(C11□ C−)− Coo(CI+□>, 0COR (A) −[CI12 C)− Coo(C1lz+kCOOR (A) =011°C) − C00(C11 □>k-1-OCO(CHr)k-2-
OCOR(A) −(CI+□ F C00(C11□) Shoulder 0CO(CIl□) After C00R(
A) (A) 6 -(CL h COO(C112-)fiOcOc)l=c)I-CO
OR(＾) -”-'(GHz C)- COOCII□CII CII□0CORC0R (＾) 1E〇H2 C〉- C00(CII2i0CO(CH2) 2NH-R(＾
〉-fcH. Cu-- C00(C112CII□O+-1TR'(A) 0 1 →CH2 C)- C00C1ICII2COOR CI-12COOR (8)-13! 1 C112-C3- C11zCOO(CH2el, C0OR→C1(2 C)-C00(CII2'3TT 0CO(CH2) zsO
J1h -(CH--CH)--- COO(CIl□9-I-OCOR 9 (A) 6 CT. 14C1+-～-CII)-C00(:I(zCIfCII□0CORC0R (8)-17- (CI□-C1+)-10C0(C11
□)i 0COR (A)-18BaC1l□-CIlto(C11゜)-, -7COO(CIl□ is also C00I? Also, in the oligomer (B) provided in the present invention, it is represented by the general formula (II) Other repeating units may be contained as copolymerization components together with the repeating units represented by formula (If).Other copolymerization components include monomers copolymerizable with monomers corresponding to the repeating units of general formula (If). For example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, chloro]-nic acid, maleic acid, vinyl acetic acid, 4-pentenoic acid, and esters of these unsaturated carboxylic acids. or amides; carbon number 1~
22 fatty acid vinyl esters or allyl esters; vinyl ethers; styrene and styrene derivatives;
Examples include heterocyclic compounds containing unsaturated bonds. Specifically, examples thereof include the compounds exemplified as monomer (A) described above, but are not limited thereto. In the total number of repeating units in the oligomer (B), the repeating unit represented by the general formula (IT) is preferably contained in an amount of 40% by weight or more, more preferably 60 to 100% by weight. If the content of the component represented by general formula (II) is less than 40% by weight of the total, the mechanical strength of the image area formed by the dispersed phase resin particles will not be maintained sufficiently, and therefore the durability when used as an offset master plate will be insufficient. The effect of improving printability is no longer visible. Among the polar groups bonded only to one end of the main chain of a polymer having a number average molecular weight of 1 represents ~R1 group or -0R1 group 01 ( , R1 preferably represents a hydrocarbon group having 1 to 18 carbon atoms. More preferably, the hydrocarbon group of R1 is
An optionally substituted aliphatic group having 1 to B carbon atoms (e.g. methyl group, ethyl group, propyl group, butyl group, pendel group,
Hexyl group, phthynyl group, hentenyl group, hexenyl group, 2-r? rJ conityl group, 2 cyanoethyl group, cyclopentyl group, cyclohexyl group, benzyl group, phenethyl group, chlorohensyl group, bromohensyl group, etc.),
or an aromatic group which may be substituted (eg, phenyl group, tolyl group, 4-solyl group, mesityl group, chlorophenyl group, commophenyl group, methoxyphenyl group, cyanophenyl group, etc.). Furthermore, among the polar groups of the present invention, the amino group is -N If t,
Represents a hydrocarbon group having 1 to 18 carbon atoms, preferably having 1 to 18 carbon atoms.
8 represents a hydrocarbon group, and specifically represents the same content as the hydrocarbon group of Ra described above. Even more preferably, the hydrocarbon groups of ll', R' and R9 are an optionally substituted alkyl group having 1 to 4 carbon atoms, an optionally substituted benzyl group, or an optionally substituted phenyl group. Can be mentioned. Here, the polar group has a chemical structure in which it is directly bonded to one end of the polymer main chain of the oligomer (B) or via an arbitrary linking group. Examples of the group connecting the formula (II) component and the polar group include a carbon-carbon bond (-double bond or double bond), a carbon-hetero atom bond (hetero atoms include, for example, an oxygen atom, a sulfur atom, a nitrogen atom, a (subatomic atoms, etc.), and any combination of atomic groups of heteroatom-heteroatom bonds. Among the oligomers (B) of the present invention, preferred ones are of the formula (
Vla)X6 is as shown by the formula (Vlb). Formula (Via) I b2 0-ToyC1(-C)- ν0(+7''-χ')n(R'-X2).-Y'5 Formula (V[b) bl b2-(CIl-C)~ E-0 ν'(R"-X'), -(R'-X2iY' formula (Via
) and (Vlb)φ, blXb! , R2, R3, xl,
×2, vo, Yo, m and n represent the same contents as the symbols in formula (II). Q represents the aforementioned polar group bonded to one end of formula (II). Rr. E is a simple bond or -(C) (R10, Ra
1 is 11 hydrogen atom, halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), cyano group, hydroxy group, alkyl group (e.g. methyl group, ethyl group, 0N SO2~N) IC (1O NIICONI+- 1 I Ra2 712 +++3 5 is also a single linking group or any combination selected from atomic groups such as [Ra2 and R13 each independently represent a hydrogen atom, a hydrocarbon group, etc. representing the same content as Y0]. Represents a linking group composed of. If the upper limit of the number average molecular weight of the oligomer (B) exceeds 1 x 104, the rigidity resistance will decrease. On the other hand, if the molecular weight is too small, stains tend to occur. It is preferable that the polymer main chain of the oligomer (B) contains a phosphono group,
It is preferable that it does not contain a covalent component containing a polar group i1 such as a carboxyl group, a sulfo group, a hydroxyl group, a phorgol group, an amino group, or a -11-R' 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: (1) reacting various reagents to the ends of living polymers obtained by conventionally known anionic or cationic polymerization; (horn method using ionic polymerization method), (1) radical polymerization method using a polymerization initiator and/or chain transfer agent containing a specific polar group in the molecule (method using radical polymerization method), or (2)
It can be easily produced by a synthetic method such as a method in which a polymer containing a terminal reactive group obtained by the above-mentioned ionic polymerization method or radical polymerization method is converted into the specific polar group of the present invention by a polymer reaction. can. Specifically, P, Dreyfuss, R, P, Q
uirk. Encycle, F'olym, Sci, Eng,
, 7.551 (1987), Yoshiki Chujo, Yuya Yamashita, Dyes and Pharmaceuticals J, 30.232 (1985), Akira Ueda, Susumu Nagai, Science and Industry, Rhosako, 57 (1986), and other reviews and citations. It can be produced by the method described in the literature etc. Examples of the polymerization initiator containing a specific polar group in the molecule include 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-A9 Zobis[2-methyl N-(2-hydroxyethyl)-
2,2'-Azobis(2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propiodine), 2,2'Azobis(2-methyl-N-
[1,1-bis(hydroxymethyl)-2-hydroxyethyl)zo11bioamide 1.2,2'-azobis(2
-(5methyl-2-imidacillin-2-yl)propane), 2.2''-azobis(2(4,5,6 futetrahydro IH-1,3-diazepin-2-yl)propane L
2.2°-azobis(2(3,4,5,6-tetrahydrobirigodin-2-yl)propane), 2.2”-azobis[2(5-hydroxy-3,4,5,6tetra pyrimidin-2-yl)propane], 2.2'-azobis(2-(1-(2-hydroxyethyl)2-yridacylin-2-yl)propane), 2゜2-azobis(N-(
2-Hydroxyethyl〉2-methyl-propionamidine), 2.2azobisCN-(4-aminophenyl)-
2-methylpropionamidine] and the like. In addition, examples of chain transfer agents containing a specific polar group in the molecule include mercapto compounds, disulfide compounds,
Examples include iodine-substituted compounds, preferably mercapto compounds. For example, thioglycolic acid, 2-mercaptopropionic acid, thiomalic acid, 2-mercaptoethanesulfonic acid,
Examples include 2-mercaptoethanol, 2-mercaptoethyl acetate, thiosalicylic acid, α-thioglycerin, 2-phosphonoethylmercaptan, hydroxythiophenol, and derivatives of these mercapto compounds. These polymerization initiators and/or chain transfer agents may be of the type (IT
) is used in an amount of 0.5 to 20% by weight, preferably 1 to 10% by weight, based on the total amount of the monomer corresponding to the repeating unit represented by () and other polymerizable monomers. Preferred oligomers (B) used in the present invention are represented by the general formula (Vla) or (Vlb), and the moiety represented by Q-1i- in these formulas will be more specifically exemplified below. However, the scope of the present invention is not limited thereto. In the following, kl is an integer of 1 or 2, k2 is 2 to 1
k3 indicates an integer of 6, and k3 indicates an integer of 1 or 3. (B)-1: l100C-4C82u1
5(B)-2: )100cmCIl-5II
OOC-C11□ (B) HooC(CIlz)-00C(Cll□)-ni-1S
2 (It) 4: tlook(Ctlz)-NIICO(C1l□)i7
-52 ) 100c (8) 7: 110(CIl□buS (B) 8: 11□N(CI-12) 5 (B) 9: 110cII-CH2S 1(OC11□ 0 10: 11 (B) 11 : 11 R+C alkyl group (B) 12: tloas(CHz)zS 3 (B) 17: 113 1100C(CIl□)TC N (B) 18: CI+. N (B) 19: C11゜110(C)12 00C(Cllz)rCN 4 (11) 20: CH. 1113C-C CI+2011 R' Z :BaC1l□)T, -(CI!□)T. (', II, ClIC11□ R; 11, CII□CIl□0H (R1: Nl+□, 113 OflC(CILz)r -C N 1 P-0(CL)2s 11 20. 6 alkyl group\5O3H (R)-29: l100C(Cllz)JH(Cl
lz)US(B)-30: HooC(C!12)5
CONIl(C)IziS The dispersion resin of the present invention consists of at least one each of monomers (A) and oligomers (B), and the important thing is that the resin threatened by these monomers is If the resin is insoluble in the resin, the desired dispersed resin can be obtained. More specifically, the monomer (A) to be insolubilized
- Oligomer of format (II) (B
) is preferably used in an amount of 0.05 to 10% by weight, more preferably 0.1 to 5% by weight. Even more preferably it is 0.3 to 3% by weight. Further, the amount of the dispersion resin of the present invention is 103 to 104, preferably 104 to 5×104. To produce the dispersion resin used in the present invention as described above, generally, the above-mentioned dispersion stabilizing resin, monomer (A) and oligomer (B) are mixed with hendiyl peroxide in a non-aqueous solvent. , azobisisobutyronitrile, butyllithium or the like in the presence of a polymerization initiator such as azobisisobutyronitrile or butyllithium. Specifically, the resin for fixing 11 minutes, the monomer (
A method of adding a polymerization initiator to a mixed solution of A) and oligomer (B), ■Dropping monomer (A) and oligomer (B) together with a polymerization initiator into a solution in which a dispersion stabilizing resin is dissolved. or (2) Optionally add the remaining monomer mixture together with a polymerization initiator to a mixed solution containing part of the mixture of dispersion stabilizing resin Venus, monomer (A), and oligomer (B). 1. Mixing the dispersion stabilizing resin, monomer (A), and oligomer (B) in a nonaqueous solvent? There is a method of optionally adding 8 liquid to a polymerization initiator, etc., and it can be produced using any method. The total amount of monomer (A) and oligomer (B) is about 5 to 80 parts by weight, preferably 10 to 50 parts by weight, based on 100 parts by weight of the nonaqueous solvent. The amount of the soluble resin as the dispersion stabilizing resin is 1 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the monomer (A) and oligomer (B) used above. . The amount of polymerization initiator is monomer (A) and oligomer (B)
0.1 to 5% by weight of the total amount is suitable. Further, the polymerization temperature is about 50 to +80'C, preferably 60 to 120'C. The reaction time is preferably 1 to 15 hours. When the above-mentioned polar solvents such as alcohols, ketones, ethers, and esters are used in combination with the non-aqueous solvent used in the reaction, or when unreacted monomers (A) to be jointly 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 over a long period of time, especially in a developing device. Even if the dispersibility is good and the development speed is improved, re-dispersion is also 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. Although the details of the reason why the redispersion and toner image fixing properties are significantly improved as described above when the resin particles of the present invention are used as a liquid developer are unknown, in the polymerization granulation method of the resin particles of the present invention, Even when oligomer (B) was added as a post-addition after polymerization and granulation without using oligomer CB>, the above effect was not observed. This is considered to be because the oligomer (B) used in the resin particles of the present invention modifies the surface of the resin particles. That is, since the polar group specifically bound only to one end of the polymer main chain is polymerized and granulated in a non-aqueous solvent, the resin n
It is assumed that one of the main factors is that the polymer main chain portion modifies the surface of the resin particles and improves the affinity with the dispersion medium. In addition, the non-aqueous dispersion resin described in JP-A-62-151868 contains at least two or more ester bonds or the like in the molecule that can be copolymerized with a monomer that is polymerized and made insolubilized. This is a resin particle obtained by coexisting with a monomer that can be used for large size offset printing masters. Plate-making machine using a plate (e.g., manufactured by Fuji Photo Film ■, EI'L-560, EPL-82)
0, etc.), or when the processing speed of the plate making machine was increased, there was still a problem with the dispersibility of the particles. However, when the resin particles provided by the present invention are used, no problem occurs even under such severe conditions. In the liquid developer of the present invention, a coloring agent may be used if desired. The coloring agent is not specified in particular.
Various conventionally known pigments or dyes can be used. 1. 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. ing. Examples include magnetic iron oxide powder, powdered lead iodide, carphone blank, nigrosine, alkali blue, Hanzaier I'J, quinacridonelet, and phthalocyanine blue. Another coloring method is disclosed in Japanese Patent Application Laid-open No. 57-4873.
There is a method of dyeing the dispersed resin with a preferred dye, as described in No. 8 and others. Alternatively, as another method, there is a method of chemically bonding a dispersion resin and a dye, as disclosed in JP-A No. 53-54029, or as described in JP-B No. 44-22955, etc. As described above, there is a method of producing a copolymer containing a dye by using a monomer containing a dye in advance during production by a polymerization granulation method. If desired, various additives may be added to the liquid developer of the present invention in order to strengthen charging characteristics or improve image characteristics. , page 44 is used. Examples include di-2-ethylhexylsulfosuccinic 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, which are mainly composed of a resin and an optional colorant, are prepared in a proportion of 0.0% to 1000% 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, fogging will tend to occur in non-image areas. Furthermore, the carrier liquid soluble resin for dispersion stabilization described above may be used as desired, and the carrier liquid 10
Approximately 0.5 parts by weight to 100 parts by weight can be added to 00 parts by weight. The charge control agent as described above is preferably used in an amount of 0.001 to 1.0 parts by weight based on 1000 parts by weight of the carrier liquid. Furthermore, various additives may be added as desired.
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 109ΩCl11, it becomes difficult to obtain a continuous tone image of good quality, so it is necessary to control the amount of each additive added within this limit. is necessary. (Example) Examples of the present invention are illustrated below, but the content of the present invention is not limited thereto. Final step 1: P-1 A mixed solution of 100 g of octadecyl meccryle-1, 2.0 g of divinylbenzene, 150 g of toluene, and 50 g of isopropanol was heated to a temperature of 8 ml while stirring under a nitrogen stream.
Warmed to 0°C. 5.0 g of 2,2'-azobis(4-cyanovaleric acid) (abbreviated as A, C, V) was added and reacted for 8 hours. After cooling, it was reprecipitated into methanol 21, and the self-colored rice powder was collected by filtration and dried. 50 g of white powder obtained 8.0 g of allyl glycidyl ether, 0.5 g of t-butylhydroquinone, 0.5 g of N,N-dimethyl 1-denruene and 100 g of l-luene Total temperature: 100°C
and stirred for 20 hours. This reaction mixture solution was reprecipitated into methanol (LE), and a pale yellow powder was collected by filtration and dried. The yield was 43g, and the weight average molecular weight was 9.5X104. 2 to 10: P-2 to P-1
0 In Production Example 1, each dispersion stabilizing resin P-2 to I)-1 was prepared in exactly the same manner as Production Example 1, except that the monomers shown in Table 1 below were used instead of octadecyl methacrylate.
0 was manufactured. The weight average molecular weight of each resin is 9.0XIO
'~10.5X104. (Margins below) 11-23 in Table b: P-1
1-P-23 Production Example 1 except that the polyfunctional monomer or oligomer shown in Table 2 below was used instead of 2.0 g of divinylhenzene, which is a crosslinking polyfunctional monomer. Operate in the same manner as above to add each dispersion stabilizing resin P-11 to P-1.
-23 was manufactured. (Left below) During the production of dispersion stabilizing resin Φ [100 g of 1-100 g of octadenyl methacrylate, 3 g of thiomalic acid, 4.5 g of vinyl methacrylate, 3 g of thiomalic acid, 4.5 g of vinyl henzene, etc.) A mixed solution of 150 g of toluene and 50 g of ethanol was added under a nitrogen stream. Then, the temperature was increased to 60°C. 2.2'-Azobis(isobutyronitrile) (
Abbreviation ^, 1. l'1. ) was added to 0.5 and reacted for 5 hours, then 8.1. Add 0.3g of B, N, and react for 3 hours, and then add A, 1. 0.2g of B and N were added and reacted for 3 hours. After cooling, it was reprecipitated into methanol 21, and a white powder was collected by filtration and dried. The yield was 85g. A mixture of 50 g of the above powder and 100 g of l.luene was heated to a temperature of 40'C and dissolved in stirring F. Next, 0.2 g of L-butylhydroquinone, 8 g of vinyl acetate, and 0.03 g of mercury acetate were added and reacted for 2 hours. Next, the temperature was raised to 70°C, 1.2 x 10" ml of 100% sulfuric acid was added, and the reaction was allowed to proceed for 18 hours. After the reaction, 3.6 g of sodium acetate trihydrate was added to the reaction solution. Stir for 30 minutes f'l'
After that, it was cooled and reprecipitated in 1.5N methanol. 41 g of a product with a slightly brownish taste was obtained. The weight average molecular weight of this 9 powder was 10.5Xlo'. Stable distribution, use 4□ Manufacturing example ≧ - H -, =:
, -2fFhi=a-Q In the above Production Example 24, 3 g of thiomalic acid was replaced with the mercapto compound shown in Table 3 below, but the same procedure as in Production Example 24 was carried out to prepare dispersion stabilizing resin P-25. ~P-30 was manufactured. Table 3 0 P- Output 3]: Production except that a mixed solution of 1.00 g of P-31 dodecyl methacrylate, 4 g of ethylene glycol dimethacrylate, 4 g of 23-epoxypropyl thioglycolic acid, and 200 g of toluene was used. A polymerization reaction was carried out in the same manner as in Example 24. Next, 6 g of crotonic acid, 2,2'-methylenebis-(
6-L-butyl-p-cresol) to 1. OK and N,
Add 0.8 g of N-dimethyldodecylamine and reduce the temperature to 10
The reaction was carried out at 0°C for 200 hours with stirring. This reaction mixture was reprecipitated in methanol 21, and a pale yellow viscous substance was obtained by decantation and dried. The yield was 75 and the weight average molecular weight was 6.5 x 104. Circle 32: P-32 tridecyl methacrylate 100g, divinylhenzene 1.2g
A mixed solution of 200 g of tetrahydrofuran and 200 g of tetrahydrofuran was heated to 70° C. while stirring in a nitrogen stream. 4.4'
6g of azobis(4-cyanopentanol) was added and reacted for 8 hours. Next, after cooling this reaction product, 6.21 g of methacrylic acid hydrate, 0.8 g of L-butylhydroquinone
and 1 drop of concentrated sulfuric acid, stirred for 1 hour at a temperature of 30°C, and further stirred for 3 hours at a temperature of 50'C.After cooling, the solution was reprecipitated in methanol 21, and the solution was removed by decantation to form a brown viscous substance. was collected and dried. The yield was 88 g, and the average weight molecular weight was 11.3xlO'. and tetrahydrofuran 200
g of mixed solution was heated to a temperature of 70°C while stirring under nitrogen stream
'C. 5 g of 4.4'-azobis(4-cyanopentanol) was added and reacted for 5 hours. Furthermore, 1.0 g of the above Azubis compound was added and reacted for 5 hours. The reaction mixture was cooled to a temperature of 20°C in a water bath, and 3.2 g of pyridine and 1.0 g of 2.2'methylenebis-(6-1-butyl-p-cresol) were added and stirred. To this mixed solution, 4.2 g of methacrylic acid chloride F was added dropwise over a period of 30 minutes so that the reaction temperature did not exceed 25"C. The reaction mixture was heated for 4LX at a temperature of 20 DEG (~25 DEG C.) for 1'+H'1'. Next, this warped material was mixed with methanol 1.5ff/water 0.5p.
The white powder was collected by filtration and dried. Yield 8
At 2g, the weight average molecular weight was 11.2X104. 134-42:P-3,1-P-
, 12 In Production Example 33, each dispersion stabilizing resin P-
34 to P-42 were manufactured. The weight average molecular weight of each resin was 10XIO' to 20X104. Table 4 3 Table (continued) Dodecyl dimethacrylate-1-100g, ethylene glycol methacrylate 0.8g and tetrahydrofuran 2
00g of the mixed solution was heated to a temperature of 65°C under a nitrogen stream. 4 g of 2,2'-azobis (4-cyanokichi A grass acid chloride) was added and stirred for 10 hours. The reaction solution was cooled to a temperature of 25°C or less in a water bath, and 2.4 g of allyl alcohol was added. 2.5 g of pyridine was added dropwise without exceeding the reaction temperature of 25°C, and the mixture was stirred for 1 hour. After further stirring at a temperature of 40°C for 2 hours, the mixture was reprecipitated into methanol 21. A pale yellow viscous substance was obtained by decantation and dried. The yield was 80 g and the weight average molecular weight was 10.5×104. '' 44~52: P-44~
P-52 In the above Production Example 24, instead of octadecyl methacrylate and divinylhenzene, the following table--
In addition to using methacrylate and polyfunctional monomer of No. 5,
Resins P-44 to P-52 were produced in the same manner as in Production Example 24. The weight average molecular weight of each resin obtained was 9. OX
104-12X]0'. (Left below) 53:P-53 octadecyl methacrylate 97g 1 thioglycolic acid 3g
A mixed solution of 6 g of 1-divinylhenzene and 200 g of toluene was heated to a temperature of 85° C. while stirring under a nitrogen stream. 2.2'-azobis(cyclo-xylcyanamide) (
1.0g of A, B, C, C) was added and reacted for 5 hours, and further 0.6g of A, B, C, C was added and reacted for 4 hours. After cooling to a temperature of 25°C, 6 g of allyl alcohol was added, and while stirring, 8 g of dicyclohexyl-carbodiimide] (abbreviated as C,C,) and 4-(N,N-dimethylamino)pyridine ( A mixed solution of 0.4 g of M, Δ, P) and 10 g of methylene chloride was added dropwise over 30 minutes.
Further, the reaction was continued for 4 hours. After adding 5 g of formic acid to this and stirring for 1 hour, insoluble matter was filtered off, and the filtrate was reprecipitated into methanol 31. A white precipitate was collected by filtration and dried. The yield was 66 g and the weight average molecular weight was 3.6 x 104. ``Gakean-yodo use'' side fat p-manufacturing-example-1: Eni 54 hexadecyl methacrylate) 96 g, 2-Merka 7 Butethanol 4 g 1 Divinylhenzene 7 g 3 A mixed solution of toluene 160 g and ethanol 40 g. The mixture was heated to a temperature of 80°C while stirring under a nitrogen stream. /1.1. Add 2g of B and N, react for 4 hours, and then
1. B.N. 1. Og was added and the mixture was reacted for 4 hours. This reaction solution was reprecipitated into methanol 31, and the precipitate was collected by filtration and dried. Yield was 78g. A mixture of 50 g of the above reactant, 5 g of 4-pentenoic acid, and 150 g of tetrahydrofuran was melted at a temperature of 25°C with stirring. With this, C, C, 6g, D, gate, 8, P
. A mixed solution of 0.3 g and 10 g of methylene chloride, 30
The mixture was added dropwise over a period of minutes, and the mixture was further stirred for 5 hours. 10 g of water was added, and after stirring for 1 hour, the precipitate was filtered off, the resulting filtrate was reprecipitated in methanol/water, and the precipitate was collected by filtration and dried. Yield: 38g, weight average molecular weight: 4
．． It was 0x104. B-] 2,3-diacetoxypropyl methacrylate to the oligomer 10
0g, 3-mercaptopropionic acid 5g, toluene 15
A mixed solution of 0 g and 50 g of methanol was heated to 70° C. while stirring under a nitrogen stream. 2.2'-azobis(isobutyronitrile) (abbreviation A, 1.B, N,)
1.5 g of was added and reacted for 4 hours. Furthermore, A.1. B, N
, and reacted for 4 hours. After cooling, this reaction solution was mixed with methanol/water [(4/l) volume ratio] 2
The methanol solution was separated by decantation, and the viscous substance was dried to obtain 75 g of a colorless viscous substance. The number average molecular weight of the polymer was 3,300. Oligomer B-1; C00CIlzCllCtl□0COC11°0COC
In Production Example 1 of Sesame 2-137B-2-B-13 oligomer, the same procedure as Production Example 1 was used except that the mercapto compound shown in Table 6 below was used instead of 5 g of 3-mercaptopropionic acid. Each oligomer I3
-2 to B-13 were manufactured. The number average molecular weight of the obtained oligomer was 2,500 to 5,000. Table 6 (Continued) 1 1st sesame ``' 14-33: B-14-B-3
3 In Production Example I, each oligomer B
-14 to B-33 were manufactured. (The number average molecular weight of the oligomer was found to be 2,500 to 3.500. 100g, toluene 1508 and ethanol 50g
The mixed solution was heated to 75°C while stirring under a nitrogen stream. 2.2'-azobis(cyanovaleric acid) (
8 g of A, C, V) was added and reacted for 5 hours, and further,
2g of A, C, and V were added and reacted for 4 hours. After cooling the obtained reaction solution, methanol/water ((4/1) volume ratio)
After reprecipitation in a mixed aqueous solution and separating the methanol aqueous solution by decantation, the viscous substance was dried. The yield was 10 g, and the number average molecular weight of the polymer was 2,600. Oligomer B-34: Clh CH3 1100cm (-C11□)2-CMoyoH-CHTodoC
N C00(CIlzlzOCOC7ll+,(
n) Otomigoma 35-43: B-35-B-4
3 In Production Example 34, each oligomer B-35 to B43 was produced in the same manner as Production Example 34, except that the azobis compounds shown in Table 8 below were used instead of polymer initiators A, C, and V. . The number average molecular weight of the obtained oligomer was 2.0.
00-4,000. 5 Table R: Azobis compound 6 Table 8 (Continued) L of Larx: D-1 8 g of dispersion stabilizing resin P-1, 100 g of vinyl acetate, 0.8 g of oligomer B~1, and 380 g of Isopar 11
The mixed solution of g was heated to 70°C while stirring under a nitrogen stream. 2.2'-Azubis (isovaleronitrile)
Add 0.8 g of (abbreviation: angle, ■, ν, N,) and react for 2 hours. 0.3g of V and N were added and reacted for 2 hours. 20 minutes after the addition of the initiator, white turbidity occurred, and the temperature of the J5 rose by 1 to 88°C. The temperature was raised to 100°C and the mixture was stirred for 2 hours to distill off unreacted vinyl acetate. 200 after cooling
The white dispersion obtained is passed through a mesh nylon cloth.
The latex had a polymerization rate of 88% and an average particle size of 0.22μ. In Production Example 1 of D-2 to D-30 latex particles, the conditions were the same as in Production Example 1, except that the dispersion stabilizing resin and oligomer were replaced with the compounds in Table 9 below. Each latex 117 was manufactured in the following manner. The polymerization rate of each Latinx particle was 85 to 90%. 9 100 1-nx 31: 9 g of D-31 dispersion stabilizing resin P-7, 100 g of vinyl acetate, 5 g of crotonic acid,
1.0 g of oligomer B-3 and 468 g of isoper E
A mixture of g? While stirring the 8 liquid under a nitrogen stream, the temperature was 70°.
It was heated to C. A.1. ν, N. After 6 hours of reaction, the temperature was raised to 100°C and the mixture was stirred for 1 hour at 71 yen per hour, and the remaining vinyl acetate was distilled off. After cooling, pass through a 200 mesh nylon cloth.
The obtained white dispersion had a polymerization rate of 86% and an average diameter of 0.
It was made of 231tm latex. -Tex's 32: A mixed solution of 8 g of D-32 dispersion stabilizing resin P-53, 100 g of vinyl acetate, 6.0 g of 4-pentenoic acid, 0.8 g of oligomer n-9, and 380 g of Isopar G was heated in a nitrogen stream. While stirring,
It was heated to a temperature of 75°C. Add 0.7g of A, 1B, and N and react for 4 hours, and then add A, 1. B, +1. 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 a latex with a polymerization rate of 88% and an average particle size of 0.20 μm. -Tex's "' 33: 9 g of D-33 dispersion stabilizing resin-6, 85 g of vinyl acetate, 15 g of N-vinylpyrrolidone, 1.0 g of oligomer 13-39 and n
- A mixed solution of 380 g of decane was heated to a temperature of 75°C while stirring under a nitrogen stream. A.1. B.N. Added 1.7g of A, 1. and reacted for 4 hours. B.N.
0.5g of was added and reacted for 2 hours. After cooling, the resulting white dispersion was passed through a 200 mm thick nylon cloth with a polymerization rate of 8.
7%, the latex had an average particle size of 0.201M. -Tex's 34: I) A mixed solution of 12 g of -34 dispersion stabilizing resin-37, 100 g of isopropyl methacrylate, 0.7 g of oligomer B-29, and 470 g of n-decane was heated to a temperature of 70 with stirring under a nitrogen stream. Warmed to °C. A.1. 1.0 g of V, li was added and reacted for 2 hours. A few minutes after the initiator was added, the mixture began to become cloudy and the reaction temperature rose to 90°C. After cooling, coarse particles were removed by passing through a 200-molecular weight nylon cloth, and the resulting white dispersion was a latex with a polymerization rate of 88% and an average particle size of 0.25-. -Tex's 35:D-3503 12g of dispersion stabilizing resin P-36, 100g of
, 0.6 g of oligomer B-19 and 3 g of Isopar H
While stirring 80 g of the mixed solution under a nitrogen stream, the temperature was increased to 6.
Warmed to 0°C. A.1. Add 0.6g of ν, N, 4
Time reaction and further A.1. 0.3 g of ν, N, was added and the reaction was carried out for 3 hours. After cooling, the resulting white dispersion was passed through a 200 mesh nylon cloth with a polymerization rate of 83%.
The latex had an average particle size of 0.24. A) Production of latex particles In Example 1, the same procedure as in Production Example 1 was carried out except for oligomer B-1. The obtained white dispersion was a latex with a polymerization rate of 85% and an average particle size of 0.25. -37B) Poly(octadecyl methacrylate) 18g, vinyl acetate 100g,
A mixed solution of 385 g of octadecyl methacrylate-H, Og and Isopar H was prepared, and the other operations were carried out in the same manner as in the production example. The obtained white dispersion had a polymerization rate of 85% and an average particle size of 0.
22- latex. (Unexamined Japanese Patent Publication 1797-1797
Latex equivalent to No. 51)-"Cus'-h3B
C) Poly(octadecyl methacrylate) 18
g, vinyl acetate 100g, monomer (1) with the following chemical structure
A mixed solution of 1 g of and 385 g of Isopar 11,
The other operations were the same as in Production Example 1. The obtained white dispersion was a latex with a polymerization rate of 8 G% and an average particle size of 0.24 IIm. (Latex corresponding to JP-A No. 624518 et al. No. 8) Monomer (I) (Jl. CIl□=C C00CII□ClIC1hOCOC1hOCOCI+
. Example 1 F-decyl methacrylate-1/acrylic acid (copolymerization ratio: 9
515 weight ratio) copolymer, 10 g of nigrosine, and 30 g of Schersol 71 were placed in a paint shaker (Tokyo Seiki 913) 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 following nigrosine dispersion, FOC-MO
O (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 occudecylamide copolymer] with 1 part of Shersol 71. Three types of liquid developers A, B, and C were prepared for comparison by replacing the resin dispersion with the following resin particles in the production example. Comparison of the resin dispersion of production example 36 of latex particles] Citrus dispersion of production example 37 of latex particles - Resin dispersion of Production Example 38 of Nilatex Particles These liquid developers were used in a fully automatic plate making machine ELI"404V (manufactured by Fuji Photo Film) in a developer and C2 to produce electrophotographic light-sensitive materials El and P. A master n type (manufactured by Fuji Photo Film 0-Ko) was exposed and developed.The plate-making speed was 5 plates/min.Furthermore, an ELP master type was exposed and developed.
After processing 000 sheets, the presence or absence of toner adhesion stains on the developing device was observed. The blackening rate (image area) of the copied image is 30
% of manuscripts were used. The results are shown in Table-10. Table Io When each developer was plate-made under the above-mentioned plate-making conditions, the developer of the present invention was the only one that did not cause swamping of the developing device and provided a clear image on the 2000th plate-making plate. . On the other hand, the off-cent printing master plate (ELP master) obtained by plate making using each developer is printed by a conventional method, and the printed image shows missing characters, solid areas, etc. I4: Printing A comparison of the number of sheets revealed that the master plates obtained using the developers of the present invention, Comparative Example A, and Comparative Example C did not produce any problem even after 10,000 sheets or more, and Comparative Example B
In Master Play 1 using , this occurred at 8000 sheets. As shown in the results below, only the developer using the resin particles-r of the present invention caused no QQ deviation in the developing device, and at the same time, the number of prints of the master plate was significantly improved. Ta. That is, in the case of the comparative example, there was no problem with the number of prints, but the developing device was extremely dirty and could not withstand continuous use. In addition, in the case of Comparative Example B and Comparative Example C, when the plate-making speed is used at a fast speed of 5 sheets/min (previous plate-making speed of 2 to 3 sheets/min), the developing device υ I position (especially the back electrode The surface of the board) started to get dirty, and 2
After 000 sheets, the image quality of plated copies is 9
(Decrease in Dmax, thin line scum, etc.) started to appear. There was no problem in the number of printed master plates in Comparative Example C, but it decreased in Comparative Example B. These results demonstrate that the resin particles of the present invention are clearly superior. Example 2 White dispersion 100 obtained in latex particle production example 2
A mixture of g and 1.5 g of Sumikaron Black was heated to +
The mixture was heated to 00'C and stirred for 4 hours. After cooling to room temperature, the remaining dye zero-1 was removed by passing it through a 200-mesh nylon cloth to obtain a black resin dispersion with an average particle size of 0.24. 32 g of the above black resin dispersion, 20 g of FOC-1600 (manufactured by Nissan Chemical ■, hexadecyl alcohol), and 0.05 g of zirconium naphthenate were added to Schersol 71 Il.
A liquid developer was prepared by diluting it to . When this was developed using the same device as in Example 1, no toner adhesion stains occurred on the device even after developing 2,000 sheets. Moreover, the image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after printing 10,000 sheets was also very clear. Example 3 White dispersion 10 obtained in latex particle production example 32
A mixture of 0g and 3g of Victoria Blue 13 was heated to a temperature of 7.
The mixture was heated to 0°C to 80°C and stirred for 6 hours. After cooling to room temperature, the remaining dye was removed by passing through a 200-mesh sieve to obtain a blue resin dispersion with an average particle size of 0.25. 32g of the above blue resin dispersion, 0 zirconium naphthenate
．． A liquid developer was prepared by diluting 0.05 g to 11 of Isopar 1]. When this was developed using the same device as in Example 1, 20
Even after developing 00 sheets, no toner adhesion to the device caused any deterioration. In addition, the image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after printing 10,000 sheets was also very clear.Example 4 White resin dispersion obtained in Manufacturing example 3 of latex particles 32g
, 2.5 g of the nigrosine dispersion obtained in Example 1, FOC,
A liquid developer was prepared by diluting 15 g of -1800 (manufactured by Mesan Kagaku ■, octadecyl aluminum 1-l) and 0.02 g of a semi-docosanylamidate of a copolymer of diisobutylene and maleic anhydride into Isopar G IR. Created. 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 play 1 for offset printing and the image quality of the printed matter after single-sheet printing were clear. Furthermore, after leaving this developer for 3 months, the same treatment as above was carried out, but there was no difference at all from before the aging. Example 5 Poly (decyl methacrylate) 10g, Isopar H
and 8 g of Alkali Blue were placed in a paint shaker together with Glass His and dispersed for 2 hours to obtain a fine dispersion of Alkali Blue. 30 g of white resin dispersion D-23 obtained in Production Example 23 of Latex Particles, Alkali Blue Dispersion 4.2 of L.
A liquid developer was prepared by diluting 0.06 g of nonyl azide of a copolymer of diisobutylene and maleic anhydride to 11 of Isopar G. 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. Both the image quality of the obtained master plate for offset printing and the image quality of the printed matter after the offset printing were extremely clear. Examples 6 to 27 In Example 5, D- of latex particle production example 23
A liquid developer was prepared in the same manner as in Example 5, except that each latex shown in Table 11 below was used in place of Example 23. Table 1 When this was developed using the same device as in Example 1, 200
Even after developing 0 sheets, no toner adhesion stains occurred on the device. In addition, the image quality of the obtained master plate for offset printing is clear, and the printed matter after printing one sheet is i8! The image quality was also very clear.6 Furthermore, after leaving this developer for 3 months, the same treatment as above was carried out, but there was no difference at all from before aging. (Effects of the Invention) According to the present invention, a developer with excellent dispersion stability, redispersibility, and fixing properties was obtained. In particular, the image quality of the obtained master plate for offset printing and 1.
The image quality of the printed matter after printing was very clear.

Claims (1)

[Scope of Claims] An electrostatic photographic liquid developer comprising at least a resin dispersed in a non-aqueous solvent having an electrical resistance of 10^9 Ωcm or more and a dielectric constant of 3.5 or less, wherein the dispersed resin particles are as follows: A polymer containing at least a repeating unit represented by general formula (I), a portion of which is crosslinked, and a monofunctional monomer (A) at one end of at least one polymer main chain.
) is soluble in the non-aqueous solvent, but becomes insolubilized by polymerization. A carboxyl group, sulfo group, hydroxyl group, formyl group, amino group, or phosphono group is present only at one end of the main chain of a polymer consisting of a functional monomer (A) and a repeating unit represented by the following general formula (II). , and -P-R^0 group (R^0 represents -R^1 group or -OR^1 group, R^
1 represents a hydrocarbon group), each containing at least one type of oligomer (B) having a number average molecular weight of 10^4 or less, which is formed by bonding at least one type of polar group selected from the following, is subjected to a polymerization reaction. A liquid developer for electrostatic photography, characterized in that it is a copolymer resin particle obtained by. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula (I), T^1 is -COO-, -OCO-,
-CH_2OCO-, -CH_2COO-, -O- or -SO_2-. A^1 represents an aliphatic group having 6 to 32 carbon atoms. a^1 and a^2 may be the same or different from each other,
Each hydrogen atom, halogen atom, cyano group, carbon number 1-8
represents a hydrocarbon group, -COO-Z^1, or -COO-Z^1 via a hydrocarbon group having 1 to 8 carbon atoms. Here Z
^1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In general formula (II), V^0 is -O-, -S-, -C
OO-, -OCO-, -CH_2OCO- or -CH_
Represents 2COO-. Y^0 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms. X^1 and X^2 may be the same or different from each other,
-O-, -S-, -CO-, -CO_2, -OCO-,
-SO_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ mathematical formulas, chemical formulas,
There are tables, etc. Represents ▼ (Y^1 represents the same content as Y^0 above). R^2 and R^3 may be the same or different from each other,
It may be substituted, or ▲There is a mathematical formula, chemical formula, table, etc.▼ may be interposed in the bond of the main chain [X^3, X^4 may be the same or different from each other, and the above X^1 , X^2, R^4 represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, Y^2 has the same content as Y^0] C1 to 18 hydrocarbon groups. b^1 and b^2 may be the same or different from each other, and represent a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -CO
O-R^5 or -COO-R^5(R
^5 represents a hydrogen atom or a hydrocarbon group that may be substituted. m, n and p may be the same or different, and are 0 to 4
represents an integer. However, m+n is 1 or more.