JPH03111860A - Liquid developer for electrostatic photography - Google Patents

Abstract

PURPOSE:To speed up developing to fixing stages and to enhance stability and fixability even if the interval for maintenance is prolonged by incorporating the resin particles obtd. by copolymn. in the presence of a specific comb type copolymer into a liquid developer. CONSTITUTION:The developer is formed by dispersing at least the resin particles (A) into a prescribed nonaq. solvent and the particles A are formed by copolymerizing a monofunctional monomer and the monomer of formula V having >=8C aliphat. group in the presence of a resin for stabilizing dispersion consisting of the comb type copolymer (B). The copolymer B is formed of the monofunctional macromonomer of a prescribed mol. wt. formed by bonding the group of formula I only to one terminal of the polymer contg. >=1 kinds of formulas II, III and the monmer of formula IV. In the formulas, V, X0, X1 denote -COO-, -O-, etc.; a1, a2, b1, b2, d1, d2 denote H, halogen, etc.; Q0, Q1 denote 1 to 22C aliphat. group; 6 to 12C arom. group; Q denotes -CN, etc.; R<1> denotes >=8C aliphat. group; G denotes -COO-, -CONH, etc.; e<1>, e<2> denote H, halogen, etc.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to a liquid developer for electrostatic photography comprising at least a resin dispersed in a carrier liquid having an electrical resistance of 10'ΩC11 or more and a dielectric constant of 3.5 or less. In particular, it relates to a liquid developer with excellent redispersibility, storage stability, stability, image reproducibility, and fixing properties.

(Prior art) General electrophotographic liquid developers are petroleum-based organic or inorganic pigments or dyes such as carbon black, nigrosine, and phthalocyanine blue, and natural or synthetic resins such as alkyd resins, acrylic resins, rosins, and synthetic rubbers. Dispersed in highly insulating and low dielectric constant liquids such as aliphatic hydrocarbons, and also metal soaps, lecithin, linseed oil, and high-grade fats + 1 JjM
, a polarity control agent such as a polymer containing vinylpyrrolidone.

In such developers, the resin is dispersed as insoluble latex particles in the form of particles with diameters ranging from several nanoseconds to several hundred 1111 particles, but in conventional liquid developers, a soluble dispersion stabilizing resin, a polarity control agent, and insoluble latex particles are dispersed. Due to insufficient bonding, the soluble dispersion stabilizing resin and polarity control agent were likely to diffuse into the solution. For this reason, 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. In addition, since the particles that have aggregated and accumulated are difficult to redisperse, the particles remain attached to various parts of the developing machine, leading to problems with the developing machine such as staining of the image area and clogging of the liquid feed pump.

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

Furthermore, in order to improve the above-mentioned drawbacks, the dispersity, redispersibility, and A method for improving storage stability was disclosed in Japanese Patent Application Laid-open No. 1797-1987.
It is disclosed in No. 51. Also, in the presence of a polymer using a difunctional monomer or a polymer using a polymer reaction, the insoluble dispersed resin particles are made of a copolymer of a monomer that becomes insolubilized and a monomer containing a long-chain alkyl moiety. A method for improving the dispersibility, redispersibility, and storage stability of particles is disclosed in JP-A-60-185963 and JP-A-61-63855.
Disclosed in the issue etc.

(Problem H to be Solved by the Invention) On the other hand, in recent years, the operating time of electrophotographic engraving systems has been shortened, and improvements have been made to speed up the development and fixation process.

In addition, the demand for rationalization of electrophotographic engraving systems has increased,
Specifically, efforts are being made to extend the maintenance period for plate-making machines. This creates a need for a liquid developer that can be used for a long period of time without being replaced.

JP-A-60-179751 and JP-A-60-18596
The dispersed resin particles produced according to the method disclosed in No. 3, No. 61-63855 still do not necessarily have satisfactory performance in terms of particle dispersibility and redispersibility when the development speed increases. Ta.

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 has excellent dispersion stability, redispersibility, and fixing properties even in an electrophotographic printing system that speeds up the constant development process and uses long maintenance intervals. It is to provide.

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

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

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

(Means for Solving the Problems) An object of the present invention is to provide an electrostatic photographic liquid developer comprising at least a resin dispersed in a nonaqueous solvent having an electrical resistance of 10"0 cm or more and a dielectric constant of 3.5 or less. In this case, the dispersed resin particles contain the following general formula (I) only at one end of the polymer main chain containing at least one of the polymer components represented by the binding margin (na) or (Ilb) below. A weight average molecule formed by bonding polymerizable double bond groups represented by 1tlX10' to 2X
In the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent, the non-aqueous copolymer is a comb-shaped copolymer consisting of at least a 10' monofunctional macromonomer (M) and a monomer represented by the following general formula (I). A monofunctional monomer (A) that is soluble in a solvent but becomes insolubilized by polymerization, and a monomer that contains an aliphatic group having 8 or more carbon atoms and is represented by the following - Tsuzuriyo (IV). Copolymer resin particles obtained by polymerizing a solution containing at least one monomer (A) and a monomer (B) that copolymerizes in a polymerization reaction. This was achieved using an electrostatographic liquid developer.

General formula (I) In formula (1), ■ is -COO--0CO-, (CHz)I
HOCO-1(CHg)WCOO-1-0--CONH
COO--CONIICO-1zIZI Here, 2. represents a hydrogen atom or a hydrocarbon group,
m represents an integer of 1 to 3.

a8, a! may be the same or different, and each represents a hydrogen atom, a halogen atom, a cyano group, a hydrocarbon group, -
COO-Zz or one COO-22 (Z
Z represents a hydrogen atom or an optionally substituted hydrocarbon group)
represents.

General formula (na) bl bz +c H-C+ X6Q@ General formula (I[b) In formula (II a) or (Ilb), xo represents the same content as V in formula (1).

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

Hydrogen atom, halogen atom, alkoxy group or -COOZ
s (Z3 represents an alkyl group, an aralkyl group, or an aryl group).

b3 and bt may be the same or different from each other, and are expressed by the formula (1
) represents the same content as a3 and a2.

-Spelling margin (I[[) (In the formula (I[l), Xl represents the same content as χ in the formula (Ila), and 0. is the same as 0° in the formula (Ila). dl and d, which represent contents, may be the same or different from each other, and represent the same contents as 81 and a2 in formula (1).

However, the macromonomer (M) represented by -8 formula (II)
In the component represented by general formula (III), at least one of Qo and Q represents an aliphatic group having 10 to 22 carbon atoms.

- Tsuzuriyo (IV) In the general formula (IV), R' represents an aliphatic group having 8 or more carbon atoms.

G represents -COO-5-CONH-1-CON- (R'' represents an aliphatic group), -0CO--CHzCOO-1 or -0-.

e l Set may be the same or different, and each represents a hydrogen atom, an alkyl group, -COOR3 or -CIl□
-COOR' (R3 represents an aliphatic group).

The resin for dispersion stabilization of the comb-shaped copolymer provided in the present invention is as follows:
Its weight average molecular weight is 2X10' to 2XIOS,
-PO311□ group, 1-5O3H group, -COOH group, -OH group, -5H group, -
p-z, group H (cocote, 2. indicates -21, group or -OZ+o group,
ZI.

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, and a halogen thereof. Substitutes can be used. For example, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, cyclohexane, cyclooctane, cyclodecane, benzene, toluene, xylene, mesitylene, Isopar E1 Isopar G1 Isopar H, Isopar L (Isopar; trade name of Exxon) , Shellsol 70, Shellsol 71 (Shellsol; trade name of Shell Oil Company),
Amsco OMS, Amsco 460 solvent (Amsco; trade name of Spirits Inc.), etc. are used alone or in combination.

Non-aqueous dispersion resin particles (hereinafter sometimes referred to as Latinx particles), which are the most important component in the present invention, are dispersed in a non-aqueous solvent in the presence of the dispersion stabilizing resin, which is the comb-shaped copolymer described above. , which is produced by copolymerizing and granulating a monofunctional monomer (A) and a monomer (B) having an aliphatic group having 8 or more carbon atoms.

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, hexane, octane, isooctane, decane, isodecane, decalin, nonane, dodecane, isododecane, Isopar E1 Isopar G, Isopar H1 Isopar L1 Sherzol 70, Sherzol 71, Amsco OMS, Amsco 460 TL agents, etc., alone or in combination. use

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

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

Usually, it is preferable to use the same solvent as the carrier liquid at the stage of producing the resin dispersion, and as mentioned above, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons,
Examples include halogenated hydrocarbons.

The solvent-insoluble copolymer produced by copolymerizing the -functional monomer (A) and the monomer (B) having an aliphatic group having 8 or more carbon atoms in a non-aqueous solvent is stabilized. The dispersion stabilizing resin of the present invention used to form a resin dispersion contains at least one type of -functional macromer (M) and a monomer represented by the general formula (III). It is a polymerized comb-shaped copolymer and is characterized by being soluble in the non-aqueous solvent. More preferably, it is a comb-shaped copolymer in which the above-mentioned specific polar group is bonded to one end of the polymer main chain of the comb-shaped copolymer.

The weight average molecular weight of the comb copolymer is 2X10' to 2X
10', preferably 3XIO' to 1x103. When the weight average molecular weight is less than 2 x 104 or more than 2 x 10', 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. I can't do it anymore. On the other hand, if the proportion exceeds 70% by weight, the copolymerizability with the monomer represented by the - format ([n) will not be sufficient.

In addition, the proportion of the monomer represented by the general formula (ml), which is another copolymerization component, in the comb-shaped copolymer is 30 to 30.
It is 99% by weight, preferably 50 to 95% by weight.

On the other hand, the macromonomer (M) of the present invention that forms the comb portion of the comb copolymer has a weight average molecular weight of lX10' to
2X10', preferably 2X10" to 1x103
When the weight average molecular weight is less than 1 x 103,
The redispersibility of the obtained dispersed resin particles will decrease, and if it exceeds 2X10', the copolymerizability with the monomer represented by the -i formula (III) will decrease, resulting in a comb-shaped copolymer. You will no longer be able to obtain it.

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 reason, in the macromonomer (M) component represented by -format (II) and the monomer component represented by general formula (III), at least one of 0° and Ql has a carbon number of 10 to 22. represents an aliphatic group.

That is, Ω in formula -1 (Ila) is a repeating unit of the macromonomer (M) which is a comb portion. has 10 carbons
When representing an aliphatic group or an aromatic group less than or equal to - format (
In the case of the repeating unit represented by Ilb), 0. represents an aliphatic group having 10 to 22 carbon atoms. Also, -0 in format (1). is an aliphatic group or an aromatic group having less than 10 carbon atoms, the macromonomer to be combined (M
) as a repeating unit of at least the general formula (Ila
) in which Qo contains a repeating unit of an aliphatic group having 10 to 22 carbon atoms.

The contents of the comb-shaped copolymer will be further explained below.

The monofunctional macromonomer (M) is a monomer represented by the -i formula (III) only at one end of the main chain of the polymer consisting of repeating units represented by the form (Ila) or (Ilb). A compound having a weight average molecular weight of 1×10 3 to 1×10 3 which is copolymerizable with the polymerizable double bond group represented by format (1)
2 x 104 macromonomers.

In general formula (1) and (I[a), (Ilb), 81
, a2, ■, b3, b2, Xo, Q, and Q each have the indicated number of carbon atoms (as an unsubstituted hydrocarbon group), but these hydrocarbon groups are not substituted. You can.

In formula (1), in addition to a hydrogen atom, Z+ in the substituent represented by ■ is preferably a hydrocarbon group having 1 to 1 carbon atoms.
22 optionally substituted alkyl groups (for example, methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, octyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group) , 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-
methoxyethyl group, 3-bromopropyl group, etc.), an optionally substituted alkenyl group having 4 to 18 carbon atoms (e.g., 2-methyl-1-propenyl group, 2-phthynyl group,
2-pentenyl group, 3-methyl-2-pentenyl! ,1
-pentenyl group, l-hexenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, etc.), carbon number 7 to 1
2 optionally substituted aralkyl groups (e.g., benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group,
bromobenzyl group, methylbenzyl group, ethylbenzyl group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, etc.), optionally substituted alicyclic groups having 5 to 8 carbon atoms (e.g., cyclohexyl group, 2- cyclohexylethyl group, 2-cyclopentylethyl group, etc.),
Or, an optionally substituted aromatic group 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, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dobcyroylamidophenyl group, etc.).

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

al and a2 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-Zz or -CHzCOOZg (Z2 preferably 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, it represents the same content as that described for zI above.

In formulas (I[a) and (Ilb), Xo is represented by formula (1)
bl and b2 may be the same or different, and have the same meaning as 81 or at in the above formula.

Q preferably represents an aliphatic group having 1 to 22 carbon atoms,
Specifically, it represents the same content as the alkyl group explained in Z above.

When Y is an alkoxy group, the alkyl residue is:
Specifically, the same as the example shown above for 0° can be mentioned. Further, Z3 represents an alkyl group, an aralkyl group, or an aryl group, specifically, the above-mentioned group. Examples similar to those shown in .

The preferred ranges of Xo, b+ and s are the same as those explained for each h, the above-mentioned V, a+ and a.

al and a2 of formula (+) or formula (Ila), (I[b
), it is more preferable that either one of bl and b2 is a hydrogen atom.

The repeating unit of the macromonomer (M) of the present invention contains at least one unit represented by the general formula (Ila) or (Ilb), and specific examples are given below. However, the scope of the present invention is not limited thereto.

In the following, Q": -CpHzp, + (p: an integer from i to 18)
or b: ■ or CH3 L: an integer of 2 to 12 R": H or -CrHzr*+ (r: an integer of 1 to 8).

(A) Ichidai H, -C)- “COOQ” (^)-2 -ecH-Cn+- COO[l” (A)-4 →C1l, -C11)- amount N C00Q” C.N. C00Q” Coo(CHt'rUX X: Oi+, -0RIl(R': C, H, □l), F.

C.I.

Br.

or -CN COOQ"C0NII11" (A)-10 b b The macromonomer (M) provided in the present invention contains at least one repeating unit represented by -i formula (Ila) or (Irb) as described above. It has a chemical structure in which a polymerizable double bond group represented by form (1) is directly bonded to only one end of the polymer main chain, or is bonded by an arbitrary linking group. 0 formula (1) components and formula (I
Examples of the group linking component la) or (I[b) include a carbon-carbon bond (-double bond or double bond), a carbon-heteroatom bond (heteroatoms include, for example, an oxygen atom, a sulfur atom, a nitrogen atom, atoms, silicon atoms, etc.), and any combination of atomic groups of heteroatom-heteroatom bonds.

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

Formula (V) CH=Cb, b.

V-WT(-CH-C-)- In the summer formula, al, atz b,, bi, and ■ are each represented by the formula (
1), formulas (Ila), and (If b).

T represents -XO-Q11 represented by the general formula (■a) or -0 represented by the -form (Ilb), each represented by the formula (lla
) represents the same content as explained in formula (fib).

4. is a simple bond or -(CH (Z4.2. is water S), a hydrogen atom, a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, etc.), a lower alkyl group (e.g., a methyl group,
ethyl group, propyl group, etc.), cyano group, 0Z.

2゜Z7 represents a hydrogen atom, a hydrocarbon group having the same contents as z1, etc.] or a linking group composed of an arbitrary combination thereof.

- Format (1), (Ila), (Ilb) or (
In V), particularly preferred examples of each of Xo, Y1, al, m, bl, and b2 are shown below.

xo is -COO--0CO--0--cozco
o- or -co, oco-, Y has 18 carbon atoms
The following alkyl groups or alkenyl groups are all of the above (however, 2. is a hydrogen atom),
Examples of als ag, bl, and b2 include a hydrogen atom or a methyl group.

V-do Specific examples of groups are shown below.

but, Of the present invention The contents are not limited to these.

In the following, III: an integer from 1-12, nl　; an integer from 2 to 12, or CHt represents.

(B)-1 C1l□-〇Coo(C1h)-rrs (B)-2 CHt=C COO(CHd770CO(CHr)rrS(B)-4 CIlt=C C0NH(CHz+-rrS- (B)-5 CH2 =C COOCIhCHCHzOOC(CHgh-rSH (B) cut=c COO(CHz)=NHCO(CIIzte5(B) CH!20C00(C1b)i-TNHCOO(Cllz)-f-
rS-(B)-10 C1l□=C C00(CHzhiNHCONII(CHz) revision 5(B
) 3 C1l□=C COIIHCOO(C1l□hWordS- N (B)-19 CH*=C CONHCOO(CHt-)rTS- (B)-20 CHx=CH-OCO(CIlt)TrSCI.

(B)-21 CH=CH ■ COO(CHd-rrS- CHs (B)-22 CH=CH COOCHzclIcHzooc (CHr)-rrS
H CH3 (B)-26 CHt=CI-CHtOCO(CHt+TrS-CI+
.

(B) 7 CIlz□CH-CHzCOO(CHth-rCN CH3 0 8 CHlCH-CHzCHCHzooC(C1b)TTC
H N C00CR1C112 COOCHz GHz The macromonomer (M) of the present invention can be produced by a conventionally known synthesis method. method using ionic polymerization method, (i) terminal obtained by radical polymerization using a polymerization initiator and/or chain transfer agent containing a reactive group such as a carboxyl group, hydroxyl group, or amino group in the molecule. A radical polymerization method in which a reactive group-bonded oligomer is reacted with various reagents to form a macromer; (2) A polymerizable double is formed in the oligomer obtained by polyaddition or polycondensation reaction in the same manner as in the radical polymerization method described above. Examples include a method using a polyaddition condensation method to introduce a bonding group.

Specifically, P, Dreyfuss & R,P,
Quirk+Encyc1. Polym, Sci.
Eng, +7+551 (1987), P.

F., Rempp & B., Franta;
Adv, Po1ya, Sci, +54
゜1 (1984), V. Percec, Appl.
, Polym, Set,, ■Surname 95 (1984
), R, AsamL M, TakaRi, Mak
vasol.

Chew, 5upp1. , 14. 163 (
1985), P. Re5pp, etal.
Makvamol, Chess, 5upp1. +
8. 3 (1984), Yuji Yogami, Chemical Industry,
38.56 (1987), Yuya Yamashita.

Kobunshi, 31.988 (1982), Shibe Kobayashi, Kobunshi, Separate.

625 (1981), Toshinobu Higashimura 9 Japan Adhesive Association Journal,
18.536 (1982), Hiroshi Ito-1 Polymer Processing, Peeling, 262 (1986), Takashi Azuma, Takashi Tsuda, I-No Materials, 1987. It can be synthesized according to the method described in the review of Nα10.5 etc. and the literature/patents cited therein.

Next, the small lid body represented by the general formula (I[l), which is a copolymerization component of the comb-shaped copolymer together with the above-mentioned macromonomer (M), will be explained.

In formula (I[[), xl represents the same content as xo in formula (I[a), preferably -coo--oc.

It will be done.

Ol represents the same content as Q in formula (I[a), preferably represents an aliphatic group having 1 to 22 carbon atoms, and specifically represents 2. in formula (1) above. represents the same content as the aliphatic group.

d+ and di may be the same or different from each other, and specifically represent the same content as als ag in formula (1).

Preferably, either dl or d2 represents a hydrogen atom.

In the comb-shaped copolymer, the general formula (
Along with the monomer represented by I[I], other monomers that can be copolymerized with this monomer may be contained.

For example, acrylonitrile, mecrylonitrile, acrylamide, methacrylamide, styrene, chlorostyrene, bromostyrene, vinylnaphthalene, heterocyclic compounds containing polymerizable double bond groups (e.g., vinylpyridine, vinylimidacilline, vinylthiophene) , vinyl dioxane, vinyl pyrrolidone, etc.), unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, etc.), itaconic anhydride, maleic anhydride, and the like.

Any monomer other than type (III) may be used as long as it is a copolymerizable monomer, but preferably the proportion of these other monomers in the total polymerization component of the comb copolymer is is preferably 30% by weight or less.

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, -P(h11Z group, -3O+11 group, -COOI
I group, -〇11 group, 1 OH group, -P4o group (here, Z is -Zl11 group or -OZ+.

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

1 Among the polar groups, in the -p-z group, zo represents a -210 group or a H-OZ1° group; 2. . preferably has 1 to 1 carbon atoms
zl represents 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). 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) , xylyl group, mesityl group, chlorophenyl group, bromophenyl group, methoxyphenyl group, cyanophenyl group, etc.).

Further, in the polar group of the present invention, the amino group is -NHt, which independently represents a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrocarbon group having 1 to 8 carbon atoms, specifically, It represents the same content as the hydrocarbon group of Zl described above.

Even more preferably, zl. Examples of the hydrocarbon group in %Z11 and 2+2 include an optionally substituted alkyl group having 1 to 4 carbon atoms, an optionally substituted benzyl group, and an optionally substituted phenyl group.

Here, the polar group has a chemical structure in which it is directly bonded to one end of the polymer main chain or bonded via an arbitrary linking group. The group connecting the comb-shaped copolymer component and the polar group is a carbon-carbon bond (-poly bond or double bond).
, carbon-heteroatom bond (heteroatoms include, for example,
(oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc.), heteroatom-heteroatom bond groups.

Among the comb-shaped copolymers of the present invention in which a specific polar group is bonded to one end of the polymer main chain, preferred are those shown by formula (Via) or formula (Vlb).

Formula (Vla) Formula (Vlb) ■ 11rtC, H-C) -- In formulas (Va) and (vb), al, a2, bl, b2,
dl, di, X, , Ql, ■, -1, and T are expressed by the formula (
Each symbol in I) to (nl) and (V) represents the same content.

A represents the aforementioned polar group bonded to one end of the comb-shaped copolymer.

-2 represents a simple bond or a group connecting the specific polar group A and the main chain portion of the polymer, and specifically represents the same content as explained for -6.

As mentioned above, in the case of a comb-shaped copolymer in which a specific polar group is bonded to the end of the polymer main chain, phosphono groups, carboxyl groups, sulfo groups, hydroxyl groups, formyl groups are present in the polymer main chain. Those containing no group, amino group, or gold component are preferred.

In order to produce comb-shaped copolymers in which a specific polar group is bonded only to one end of the polymer main chain, various reagents are added to the ends of living polymers obtained by conventionally known anionic or cationic polymerization. A method of reacting (method using ionic polymerization method), a 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 It can be easily produced by a synthetic method such as a method in which a polymer containing a terminal reactive group obtained by an ionic 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 Nakajo, Yuya Yamashita, Dyes and Medicines, 30.232 (1985).
), Akira Ueda, Susumu Nagai, ``Science and Industry'' 1 Rule.

57 (1986) and the literature cited therein.

As the 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-cyanoprobanol), 2.
2''-azobis(2-cyanopentanol), 2.2'
-Azobis[2-methyl-N-(2-hydroxyethyl)-propioamide L 2.2° -Azobis(2methyl-N-(1,1-bis(hydroxymethyl)ethyl)propioamide 1.2.2°- Azobis(2-methyl-N-(1,1-bis(hydroxymethyl)-2-hydroxyethyl)propioamide), 2,2°-azobis(2-(5-methyl2-imidacillin-2-yl)propane) , 2°2°-azobis(2-(4,5,6,7-
titrahydro IH-1,3-diazepin-2-yl)
Propane L2,2°-azobis(2-(3,4°5,
6-tetrahydropyrimidin-2-yl)propane),
2.2”-azobis(2-(5-hydroxy-3,4,
5,6-tetrapyrimidin-2-yl)propane), 2
, 2°-azobis(2-(1-(2-hydroxyethyl)-2-imidacillin-2-yl]propane), 2.2
' -azobis(N-(2-hydroxyethyl)-2-
Examples include azobis-based compounds such as methyl-propionamidine) and 2,2°-azobis(N-(4-aminophenyl)-2-methylpropionamidine).

In addition, as a chain transfer agent containing a specific polar group in the molecule, for example, a mercapto compound containing the polar group or a substituent that can be derived from the polar group (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, -Mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptoacetic acid, N(2-mercaptopropionyl)glycine,
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- propatool, 3-mercapto-2-butanol, mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2
-mercapto-3-pyridinol, etc.), or iodized alkyl compounds containing the above polar groups or substituents (e.g., iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid) etc.). Preferred are mercapto compounds.

These chain transfer agents or polymerization initiators are each used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total monomers,
Preferably it is 0.5 to 5 parts by weight.

In the comb-shaped copolymer of the present invention having a polar group bonded to one end of the polymer main chain, the preferred one is the formula -a (Vla
) or (Vlb), where A in these formulas
Further specific examples of the portion represented by L- are shown below. However, the scope of the present invention is not limited thereto.

In the following, k: an integer of 1 or 2, k2: an integer from 2 to 16, k3=represents an integer of 1 or 3.

(C)-1 1100C(C1l z)rrS (C)-2 HOOC-CI-S IIoocmCHg (C)-3 HOOC(COz)T! oOc (CHz)yrS(C
)-4 1100C(CHt)yrNHCO(Clh+TrS-
(C) 80(CHz)yrS (C)-8 H! N(CHzhIS (C) -9 HOCH-CH!S~ 0CHt (C)-10 IO-P-0(CHz)yrS 0■ 1 R-0-P-0(CI(z)-Trs 0HR:C.

, alkyl group of tlO+5 (CHz) is 1h (C)-17 HOOC+CHthe N h (C)-18 80 (CHzhgoC N CHt (C) 9 IO(CHz)ryoOc(CHz)rCN CH2 (C)-20 HOOC(CTohτC00(CI, stone CN lh CH3 l1z (C) 3 R-NIICO-C II HzOH R: HO(CHz)r, HzC-CC)1. OH R’ 11 Z; (CHg)r.

(Chzego, CH2CHCH1 R゛; -H, -cnxcna0■ CHg (R1; ■.

N1(z.

0)1) CH3 (C)-26 OHC(CHr)yC- N (C) 7 1 R, -P-0(C11□)2S- 11 R2; C0-6 alkyl group (C)-30 HOOC+CIl z )rrcONH(C1l z″)
The monomers used in producing the yrS non-aqueous dispersion resin include a monofunctional monomer (A) which is soluble in the non-aqueous solvent but becomes insolubilized by polymerization, and a monomer having the general formula (TV
) can be distinguished into monomers (B) which contain an aliphatic group having 8 or more carbon atoms and copolymerize with monomer (A).

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, the general formula (■
) are mentioned.

General formula (■) E-R' General formula () % formula % Here, BS 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, benzyl group, chlorobenzyl group, methylbenzyl group, methoxybenzyl group, phenethyl group, 3-phenylpropyl group, dimethylbenzyl group, fluorobenzyl group, 2-methoxy ethyl group, 3-methoxypropyl group, etc.).

R4 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, 2°2-dichloroethyl L 2,2. 2-) lyfluoroethyl group, 2-bromoethyl group, 2-glycidylethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, 2-hydroxy-3-chloropropyl group,
2-cyanoethyl group, 3-cyanopropyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-ethoxyethyl group, N,N-dimethylaminoethyl group, N,N-jethylamino Ethyl 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 5.2-N-methylcarboxyamidoethyl group, cyclopentyl group, chlorocyclohexyl group, dichlorohexyl group, etc.).

fl and f2 may be the same or different, and each represents the same content as al or a2 in the above-mentioned format (1).

Specific monofunctional monomers (A) include, for example, vinyl esters of aliphatic carboxylic acids having 1 to 6 carbon atoms (acetic acid, propionic acid, butyric acid, monochloroacetic acid, trifluoropropionic acid, etc.) or allyl Esters; optionally substituted alkyl esters or amides having 1 to 4 carbon atoms of unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, and maleic acid (as an alkyl group, for example, methyl group, ethyl group, propyl group, butyl group, 2
-chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group, trifluoroethyl L2-hydroxyethyl group,
2-cyanoethyl group, 2-nitroethyl group, 2-methoxyethyl group, 2-methanesulfonylethyl group, 2-benzenesulfonylethyl group, 2-(N,N-dimethylamino)ethyl group, 2-(N,N-diethylamino) ) Ethyl group, 2-carboxyethyl group, 2-phosphoethyl group, 4-
Carboxybutyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-chloropropyl group, 2-hydroxy-
3-chloropropyl group, 2furfurylethyl group, 2-pyridinylethyl group, 2-thienylethyl group, trimethoxysilylpropyl group, 2-carboxyamidoethyl group, etc.); Styrene derivatives (e.g. styrene, vinyltoluene, α- Methylstyrene, vinylnaphthalene, chlorostyrene, dichlorostyrene, bromostyrene, vinylbenzenecarboxylic acid, vinylbenzenesulfonic acid, chloromethylstyrene, hydroxymethylstyrene, methoxymethylstyrene, N.

N-dimethylaminomethylstyrene, vinylbenzenecarboxamide, vinylbenzenesulfamide, etc.); unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid; cyclic anhydrides of maleic acid and itaconic acid; Acrylonitrile; methacriconitrile; heterocyclic compound containing a polymerizable double bond group (specifically, for example, "Polymer Data Handbook - Basic Edition - J," edited by The Society of Polymer Science, P. 175-184, Baifukan ( 198
For example, N-vinylpyridine, N-vinylimidazole, N-vinylpyrrolidone, vinylthiophene, vinyltetrahydrofuran, vinyloxazoline, vinylthiazole, N-vinylmorpholine, etc.).

- Two or more functional monomers (A) may be used in combination.

Next, the monomer (B) represented by the general formula (IV) used in the present invention will be further explained.

- In form (IV), R+ preferably has a total number of carbon atoms of 1
0 or more optionally substituted alkyl groups or a total of 10 carbon atoms
The above alkenyl group is represented by -COO-1z -CONB-1-CON- (wherein R2 is preferably an aliphatic group having 1 to 32 carbon atoms (the aliphatic group is, for example, an alkyl group, an alkenyl group, or an aralkyl group). ) represents -0CO--CHzOCO- or -〇-.

el and e may be the same or different, preferably a hydrogen atom, a methyl group, -GOOR3 or -C82GOOR
(However, R3 preferably represents an alkyl group, an alkenyl group, an aralkyl group, or a cycloalkyl group having 1 to 32 carbon atoms.)

More preferably, in formula (TV), G represents 2 COO--CONH- or -CON-, bl and b2 represent a hydrogen atom or a methyl group, which may be the same or different, and R' is the above-mentioned It represents the same content as .

Specific examples of the monomer (B) represented by the above general formula (IV) include aliphatic groups having a total of 10 to 32 carbon atoms (aliphatic groups include halogen atoms, hydroxyl groups, amino groups, alkoxy groups, etc.). acrylic acid, which may contain a substituent of
Esters of unsaturated carboxylic acids such as meccrylic acid, crotonic acid, maleic acid, itaconic acid (aliphatic groups such as decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosanyl group, dodecenyl group, (hexadecenyl group, oleyl group, lylyl group, tocosenyl group, etc.); Amides of the aforementioned unsaturated carboxylic acids (aliphatic groups are the same as those shown for esters); vinyl esters or allyl esters of higher fatty acids (As higher fatty acids, for example, lauric acid, myristic acid, stearic acid, oleic acid, linoleic acid, behenic acid, etc.); or vinyl ethers substituted with an aliphatic group having a total of 10 to 32 carbon atoms (the aliphatic group is (representing the same range as the aliphatic group of unsaturated carboxylic acid), etc.

The dispersion resin of the present invention consists of at least one each of monomer (A) and monomer (B), and the important thing is that the resin synthesized from these monomers is insoluble in the non-aqueous solvent. if there is,
A desired dispersed resin can be obtained. More specifically,
It is preferable to use 0.1 to 20% by weight of the monomer (B) represented by the - format (rV), more preferably 0.3 to 8% by weight, based on the monomer (A) to be insolubilized. It is. Further, the molecular weight of the dispersion resin of the present invention is preferably 10" to 1
0', more preferably 104 to 106.

To produce the dispersion resin (latex particles) used in the present invention, -i is mixed with the above-mentioned dispersion stabilizing resin, monomer (A), and monomer (B) in a non-aqueous solvent. , benzoyl peroxide, azobisisobutyronitrile, butyllithium, or the like may be heated and polymerized in the presence of a polymerization initiator.

Specifically, (1) a method of adding a polymerization initiator to a mixed solution of a dispersion stabilizing resin, monomer (A), and monomer (B), (2)
A method in which monomer (A) and monomer (B) are dropped together with a polymerization initiator into a solution in which a dispersion stabilizing resin is dissolved; A method of optionally adding the remaining monomer mixture together with a polymerization initiator into a mixed solution containing a part of the mixture of monomers (B),
Furthermore, there are methods such as (1) optionally adding a mixed solution of a dispersion stabilizing resin and a monomer together with a polymerization initiator to a non-aqueous solvent, and any method can be used for production.

The total amount of monomer (A) and monomer (B) is 10% of the nonaqueous solvent.
The amount is about 5 to 80 parts by weight, preferably 10 to 50 parts by weight.

The amount of the soluble resin as a dispersion stabilizer is 1 to 100 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the total monomers used above.

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 to 180''C, preferably 60 to 120C.The zero 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 nonaqueous solvent used in the reaction, or when the monomer (A) or monomer (B) to be polymerized and granulated is ) If unreacted substances remain, it is preferable to remove them by heating the solvent or monomer to a temperature higher than its boiling point or distilling it off, or by distilling it off under reduced pressure.

The non-aqueous latex particles produced as described above exist as fine particles with a uniform particle size distribution, and at the same time exhibit extremely stable dispersibility, especially after repeated use over a long period of time in a developing device. It has good dispersibility (and improved development speed), and is easy to redisperse, and no stains are observed on various parts of the device.

Further, when fixed by heating or the like, a strong adhesion was formed and excellent fixing properties were exhibited.

Furthermore, the liquid developer of the present invention has excellent dispersion stability, redispersibility, and fixing properties even when the development and fixation process is accelerated and the maintenance interval is extended for a long time.

In the liquid developer of the present invention, a colorant may be used 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. There is. Examples include magnetic iron oxide powder, powdered lead iodide, carbon black, nigrosine, alkali blue, Hanzai Elo, quinacridone red, and phthalocyanine blue.

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

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

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

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

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

The charge control agent as described above is preferably used in an amount of 0.001 to 1.0 parts by weight based on 1000 parts by weight of the carrier liquid. Furthermore, various additives may be added as desired, and the upper limit of the total amount of these additives is regulated by the electrical resistance of the developer. That is, if the electrical resistance of the liquid developer with toner particles removed becomes lower than 10'' Ωcow, it becomes difficult to obtain a high-quality continuous tone image, so the amount of each additive added is controlled within this limit. It is necessary.

(Example) Examples of manufacturing the dispersion stabilizing resin, manufacturing examples of latex particles, and examples of the present invention are illustrated below, but the present invention is not limited thereto.

A mixed solution of 100 g of methyl methacrylate, 115 g of mercaptopropion f, and 200 g of toluene was heated to 75° C. with stirring under a nitrogen stream. 2,2゛-azobisisobutyronitrile (abbreviation ^, 1.B, N,
) was added and reacted for 4 hours, and then 11. Add 0.5g of B and N for 3 hours, and then add A.1. B, N, 0.3
Next, to this reaction solution were added 8 g of glycidyl methacrylate and 1. g of N,N-dimethyldodecylamine. Og and 0.5 g of t-butylhydroquinone were added, and the mixture was stirred at a temperature of 100°C for 12 hours. After cooling, this reaction solution was reprecipitated in methanol 21, and white powder was dissolved in 8
The weight average molecular weight of 2g of the obtained 0 polymer was 6,500.

Macromonomer M-1: Macromonomers M-2 to M-2 were reacted in the same manner as in Production Example 1, except that only methacrylate was replaced with a compound corresponding to Table 1 below.
7 was synthesized. The weight average molecular weight of each macromonomer obtained ranges from 500 to 7000.

Table 1 C10° Table 1 (Continued 1) Table 1 (Continued 2) Malomonomer 28:M-28 dodecyl methacrylate 90 g, methacrylic acid 1.

g1 A mixed solution of 5 g of thioethanol and 200 g of toluene was heated to a temperature of 70° C. while stirring under a nitrogen stream. A.1. B, N, 1. Og was added and the mixture was reacted for 4 hours.

Furthermore, A.1. Add 0.5g of B and N for 3 hours, then further ^, 1. 0.3g of B and N were added and reacted for 3 hours. This reaction solution was cooled to room temperature, 2-carboxyethyl methacrylate-1-18.2 g was added, and to this was added 24 g of dicyclohexylcarbodiimide (abbreviated as C, C).
A mixed solution of 150 g of methylene chloride was added dropwise over 1 hour.

Add 1.0 g of t-butylhydroquinone and leave as is for 4
Stir for hours.

The precipitated crystals were separated by filtration, and the resulting filtrate was reprecipitated into 2N methanol. The precipitated oil was collected with decanethisilane, dissolved in 150 methylene chloride, and reprecipitated again in 1ffi methanol. The oil was collected and dried under reduced pressure to yield a polymer with a weight average molecular weight of 15,800 in a yield of 54 g.

Macromonomer M-287 C11°C00C+zllzs C0OH Macromonomer 29-35: In the production example of M-29-35 macromonomer M-28, methacrylate monomer (corresponding to dodecyl methacrylate) and unsaturated carboxylic acid (2-carboxyethyl methacrylate) The macromonomers shown in Table 2 below were produced in the same manner as in the production example of M2S, except that the following macromonomers were changed. The weight average molecular weight of each macromonomer obtained is 5000 to 7000.
Met.

Table 2 (Continued) Macromomer's 36: M-36n-dodecyl methacrylate 70g St-butyl methacrylate 30
g, A mixed solution of 4 g of 2-mercaptoethylamine and 200 g of tetrahydrofuran was heated to 70° under a nitrogen stream.
It was heated to C. ^, lB, N, 1. Og was 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 in a water bath to a temperature of 20°C.
Then, 6.5 g of triethylamine was added, and 5.6 g of acrylic acid chloride was added dropwise with stirring at a temperature of 25° C. or lower. After 0 dropwise addition, the mixture was further stirred for 1 hour. Then t-
0.5 g of butylhydroquinone was added, heated to 60°C, and stirred for 4 hours. After cooling, reprecipitation in methanol 21 was performed twice to obtain 63 g of pale yellow viscous material.
The weight average molecular weight was 6,600.

Macro-Natsuma-M-36: A mixed solution of 100 g of macromonomer ``-37:M-37 octadecyl methacrylate, 150 g of tetrahydrofuran, and 50 g of isopropyl alcohol was heated to 75°C under a nitrogen stream.

4.4'-7zobis(4-cyanovaleric acid) (abbreviation: A
, C, V, ) was added and reacted for 5 hours.
C, V, 1. Og was added and the mixture was reacted for 4 hours. After cooling, the reaction solution was reprecipitated into 1.5 liters of methanol, and the oil was collected by decantation and dried under reduced pressure. Yield was 85g.

50 g of the obtained oil (oligomer), 15 g of glycidyl methacrylate, 1.0 g of N,N-dimethyldodecylamine, and 2,2゛-methylenebis(6-t-
butyl-p-cresol) 1. Add og, temperature 10
Stirred at 0°C for 15 hours. After cooling, this reaction solution was reprecipitated into 1ffi of petroleum ether to obtain 42 g of white powder. The weight average molecular weight was 7.500.

Macromonomer M-37: CHl OHCN C00C+5H3t Macromonomer 38: In Production Example 37 of M-38 macromonomer, 50g of the intermediate oligomer obtained
, 2.8 g of 2-hydroxyethyl methacrylate and 100 g of methylene chloride was added with O,
C, C, 4. Og, 4-dimethylaminopyridine 0.
A mixed solution of 5 g and 10 g of methylene chloride was added dropwise over 1 hour. The mixture was further stirred for 4 hours. The precipitated crystals were separated by filtration, the filtrate was reprecipitated into 1 liter of methanol, and the resulting powder was dried under reduced pressure. The yield was 43 g, and the weight average molecular weight was 7,300.

Macromonomer M-38: C.I.

CN C00C1lH3? 1:P octadecyl methacrylate 80g 1 macromonomer M
A mixed solution of 20 g of -1 and 150 g of toluene was heated to 75°C while stirring under a nitrogen stream.

8.C,V,1. Add Og and react for 4 hours.
, V, was added for 2 hours, and then 0.3 g of A, C, and V were added.
3g was added and reacted for 3 hours. After cooling, it was reprecipitated into methanol 21, and after collection by filtration, the obtained white powder was dried to obtain 76 g of powder having a weight average molecular weight of 4.8 XIO'.

Dispersion Stabilizing Resin P-1 CN C00C+ 5Hst Book H3 In Production Example 1 of P-1, the reaction was carried out in the same manner as in Production Example 1, except that octadecyl methacrylate and macromonomer M-1 were replaced with each compound in Table 3 below. Each dispersion stabilizing resin was manufactured using the following methods. Weight average molecular weight of each resin: 3.5 x 1
0'~5. It was OX 10'.

16:P-16 octadecyl methacrylate 70g1 macromonomer M
A mixed solution of 0.8 g of -10 to 3081 thiomalic acid, 100 g of ) toluene, and 50 g of isopropyl alcohol was heated to a temperature of 80° C. under a nitrogen stream. ■, 1°Azobis(cyclohexane-1-carbocyanide) (abbreviation:
Add 0.8g of A, B, C, C,) and react for 4 hours, then add 0.4g of A, B, C, C, for 3 hours, and then react for 8.
0.3g of B, C, and C were added and reacted for 4 hours. After cooling, it was reprecipitated into methanol 21, collected by filtration, and dried to obtain 78 g of a white powder with a zero weight average molecular weight of 3.8XIO'.

Dispersion stabilizing resin P-167 CH3CHHz C1(.

C00CHxCHCTo00C(Chh-3(CHz-
C) -H COOC+Jst's ゛'' 17~25:P-17~P-25P-1
In Production Example 6, octadecyl methacrylate, macromonomer M-10, and mercapto compound (thiomalic acid) were each replaced with compounds corresponding to Table 4 below, and the reaction was carried out in the same manner as in Production Example 16 to produce each resin P-17. ~P-25
was manufactured. The weight average molecular weight of each resin is 3. OX10
It was '~4X10'.

26-31: In P-26-P-31 Production Example 1, the following table-
Each resin was produced in the same manner as in Production Example 1 except that the azobis compound No. 5 was used.

The weight average molecular weight of each resin obtained was 3.0xlO' to 6
It was XIO'.

Table 5 (Continued) 85 g of n-dodecyl methacrylate, Macromonomer M
A mixed solution of 15 g of -28 and 150 g of toluene was heated to a temperature of 75° C. under a nitrogen stream. A.1. B.N.
Add 1.0g of 1.0g for 4 hours, then 8.1. B, N, 0.5
g was added and reacted for 3 hours. Furthermore, A.1. B, N, 0
．． After adding 3g, it was heated to a temperature of 90"C and reacted for 2 hours. After cooling, the reaction product was reprecipitated into 2Il of methanol,
The precipitated viscous material was collected by decantation and dried under reduced pressure.

The yield of a transparent viscous substance was 76 g, and the weight average molecular weight was 4.
It was 3 x 10'.

Dispersion stabilizing resin P-32: In the production example of P-32, the reaction was carried out in the same manner as in production example 32, except that n-dodecyl methacrylate and macromonomer M-28 were replaced with a mixture corresponding to Table 6 below. , each resin P-33 to P-42 were manufactured. The weight average molecular weight of each resin was 3.5X10' to 4.5XIO'.

--Sus No. 2 --Sus D-10g of dispersion stabilizing resin P-4, 100g of vinyl acetate, 1.0g of octadecyl methacrylate) and Isopar H
384 g of mixed solution was heated to 70°C while stirring under nitrogen flow.
'C. 0.8 g of 2.2'-azobis(invaleronitrile) (abbreviation ^, 1.V, N,) was added and reacted for 6 hours. 20 minutes after adding the initiator, a cloudy appearance occurred;
The reaction temperature rose to 88°C. The temperature was raised to 100°C, and the mixture was stirred for 2 hours, and unreacted vinyl acetate was distilled off. After cooling 2
The white dispersion obtained by passing through a 00 mesh nylon cloth was a latex with a polymerization rate of 90% and an average particle size of 0.24-.

In production example 1 of latex particles, dispersion stabilizing resin P
Latex particles D-2 to D-12 of the present invention were produced in the same manner as in Production Example 1 except that the dispersion stabilizing resin shown in Table 7 below was used instead of -4.

Table 13-1a: -- In the production example of rubber latex particles D-1, each monomer tg of Table 8 was used instead of 1 g of octadecyl methacrylate.
Each latex particle was produced in the same manner as in Production Example 1 except that .

--S No. 19: --A mixed solution of 6 g of Dispersion Stabilizing Resin P-10, 8 g of poly(octadecyl methacrylate), 100 g of vinyl acetate, 0.8 g of dodecyl methacrylate, and 400 g of Isopar H was heated to temperature while stirring under a nitrogen stream. Warmed to 75°C.

2.2'-azobis(isobutylnitrile) (abbreviation A,
1. B, N,) 0.7g was added and reacted for 4 hours, and then A
, 1. 0.5g of B and N were added and reacted for 2 hours. After cooling, the resulting white dispersion was passed through a 200 mesh nylon cloth and was a latex with an average particle size of 0.201M.

10g of dispersion stabilizing resin P-25, 90g of vinyl acetate,
A mixed solution of 10 g of N-vinylpyrrolidone, 1.5 g of octadecyl methacrylate, and 400 g of isododecane was heated to 65° C. with stirring under a nitrogen stream.

^, 1. 1.5g of B and N were added and reacted for 4 hours. After cooling, the resulting white dispersion was passed through 200 meshes of nylon cloth, and the resulting white dispersion was latex with an average particle size of 0.251 m.

20g of dispersion stabilizing resin P-10, 94g of vinyl acetate,
A mixed solution of 6 g of crotonic acid, 2 g of hexadecyl methacrylate, and Isopar G was heated to 60° C. with stirring under a nitrogen stream. A.1. V, N, 1. Og was added and the mixture was reacted for 2 hours. Sarani A, 1. 0.5 g of V and N were added and reacted for 2 hours. After cooling, the resulting white dispersion was passed through a 200-mesh nylon cloth and was a latex with an average particle size of 0.24*.

A mixed solution of 25 g of dispersion stabilizing resin P-1, 100 g of methyl methacrylate, 2 g of decyl methacrylate, 0.8 g of n-dodecyl mercaptan, and Isopar H was heated to 60° C. with stirring under a nitrogen stream. A,
1. 0.7g of V and N were added and reacted for 4 hours.

After cooling, the white dispersion obtained by passing through a 200 mesh nylon cloth was latex with an average particle size of 0.25μ.
A mixed solution of 25 g of 23Nex D dispersion stabilizing resin P-34, 100 g of styrene, 2 g of octadecyl vinyl ether, and 380 g of Isopar H was heated to 45° C. with stirring under a nitrogen stream. n
A hexane solution of -butyllithium was added in an amount to give a solid amount of n-butyllithium of 1.0 g, and the mixture was reacted for 4 hours. After cooling, the resulting white dispersion was passed through a 200 mesh nylon cloth and was a latex with an average particle size of 0.27 um.

Production example 1 of latex particles except that a mixed solution of 20 g of poly(octadecyl methacrylate) (dispersion stabilizing resin (R)-1), 100 g of vinyl acetate, 380 g of octadecyl methacrylate Ig and Isopar H was used. A white dispersion of latex particles with a polymerization rate of 88% and an average particle size of 0.27 was obtained by processing in the same manner as above. (Unexamined Japanese Patent Publication No. 60-1
A mixed solution of 25:B octadecyl methacrylate (97 g), 3 g of acrylic acid, and 200 g of toluene (latex particles described in No. 79751) was heated under a nitrogen stream at a temperature of 7
It was heated to 5°C. A.1. B, N, 1. Og was added and the mixture was reacted for 8 hours. Next, glycidyl methacrylate 12
g, t-butylhydroquinone 1. Add 1.2 g of og, N, N dimethyldodecylamine and heat at 100°C for 40 minutes.
Stir for hours. After cooling, it was reprecipitated into methanol 21, and a white powder was collected by filtration and dried. Dispersion stabilizing resin (R) with the following structure-
I got 2. The yield is 84g'? ? Weight average molecular weight is 35
,000.

Dispersion stabilizing resin (R)-2: CH.

H (Weight composition ratio) 10 g of this dispersion stabilizing resin (R)-2, 1 part vinyl acetate
A white dispersion, which is a latex particle with a polymerization rate of 89% and an average particle size of 0.15-, was prepared in the same manner as in Production Example 1 of Latex Particles, except that a mixed solution of 00 g, 1.0 g of octadecyl methacrylate, and 4 g of Isopar H3B was used. I got it. (Latex particles described in JP-A No. 61-63855) - 26:C 12 g of dispersion stabilizing resin (R)-3 having the following structure and acetic acid were prepared by the method described in JP-A No. 60-185963. 100 g vinyl, 1.0 octadecyl methacrylate
The process was carried out in the same manner as in latex particle production example 1 except that a mixed solution of 382 g of Isopar H was used, and the polymerization rate was 87.
A white dispersion of latex particles with an average particle size of 0.23 mm in % was obtained. (Latex particles described in JP-A-60-185963) Dispersion stabilizing resin (R) -37 (Weight composition ratio) Weight average molecular weight? 46.000 Example 1 10 g of dodecyl methacrylate-acrylic acid copolymer (copolymerization ratio; 9515 weight ratio), 10 g of Nigrosine, and 30 g of Isopar G were placed in a paint shaker (Tokyo Seiki ■) with glass beads and dispersed for 4 hours. A fine dispersion of nigrosine was obtained.

30 g of the resin dispersion of latex particle production example 1, 2.5 g of the above nigrosine dispersion, 0.07 g of octadecene-half-maleic acid octadecylamide copolymer, and 15 g of higher alcohol F OC-1600 (manufactured by Nissan Chemical Co., Ltd.). An electrostatic photographic liquid developer was prepared by diluting Isopar G to If.

' A to C Three types of liquid developers A, B, and C for comparison were prepared by replacing the resin dispersion with the following resin dispersion in the production of the liquid developer described above.

6゛　　　A ni Resin dispersion of latex particle production example 24.

To “ B ni Resin dispersion of latex particle production example 25.

″／　　　　　C Ni Resin dispersion of latex particle production example 26.

These liquid developers were used as a developer for a fully automatic plate making aELP404V (manufactured by Fuji Photo Film ■), and an electrophotographic light-sensitive material, ELP Master ■ type (manufactured by Fuji Photo Film ■), was exposed and developed. Plate making speed is 7 editions/
I did it in minutes. In addition, 30 ELP master types
After processing 00 sheets, the presence or absence of toner adhesion stains on the developing device was observed. The blackening rate (image area) of the copied image was determined using a 30% original. The results are shown in Table-9.

As is clear from the results in Table 9, when plates were made using each developer under severe forced plate-making conditions with very high plate-making speeds as described above, no staining of the developing device occurred, and 30%
The developer of the present invention was the only developer that produced a clear image on the 00th 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 solid areas, etc. place, the present invention, comparative example A,
In the master plates obtained using the developers of Comparative Example B and Comparative Example C, no problem occurred even after 10,000 sheets or more.

As shown in the above results, only the developer made using the resin particles of the present invention does not cause any staining of the developing device, and
The number of printed master plates was also good.

That is, in the case of Comparative Examples A, B, and C, there was no problem with the number of prints, but the developing device was stained and could not withstand continuous use.

Although the staining of the developing devices in Comparative Examples B and C was dramatically improved compared to Comparative Example A, satisfactory performance was still not achieved when the developing conditions were severe.

That is, the known dispersion stabilizing resin (R)-2 of Comparative Example B was
In the component containing a polymerizable double bond group that copolymerizes with the monomer (A) [vinyl acetate in this example] contained in the polymer, the polymerizable double bond group is attached to the main chain of the polymer. It is characterized by being a random copolymer that exists in close proximity to each other, and for this reason, it is thought that the redispersibility of latex particles is inferior to that of the dispersion stabilizing resin of the present invention.

In addition, the known dispersion stabilizing resin (R)-3 of Comparative Example C was
It is characterized by a chemical structure in which the total number of atoms of the linking group that connects the polymerizable double bond group in the resin copolymerized with the monomer (A) and the polymer main neck of the resin is 9 or more, Furthermore, the polymerizable double CH of Comparative Example B.

The structure of the bonding group is CH2・c-coo-,
The structure of the polymerizable double bond group in Comparative Example C is cuz=co-o
It is preferable because it is co- and has a good reactivity with vinyl acetate [monomer (A)]. Therefore, the image of the 3000th plate making plate was clear, which was dramatically improved compared to the case of Comparative Example B. However, even in Comparative Example C, the developing device was contaminated, and when the developing conditions became severe, satisfactory performance was still not achieved.

Example 2 White resin dispersion t obtained in latex particle production example 1
A mixture of 1.5 g of Sumikalon Black and 1.5 g of Sumikalon Black was heated to a temperature of 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 0.251 Im.

30g of the above black resin dispersion, 0 zirconium naphthenate
．． 05 g, F OC-1600 (manufactured by Nissan Chemical ■)
A liquid developer was prepared by diluting 20 g of Shersol 71 in 1Il.

When this was developed using the same device as in Example 1, the result was 300
Even after developing 0 sheets, no toner adhesion stains occurred on the device.

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

Example 3 A mixture of 100 g of the white resin dispersion obtained in Production Example 21 of latex particles 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
．． 05g, FOC-1400 (manufactured by Nissan Chemical ■) 1
A liquid developer was prepared by diluting 5 g of Isopar H to 12.

When this was developed using the same device as in Example 1, the result was 300
Even after developing 0 sheets, no toner adhesion stains on the device were observed. 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.

Example 4 Poly(decyl methacrylate) 10g, Isopar 8
30 g of alkali blue 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 3 obtained in latex particle production example 1
0 g, 4.2 g of the above alkali blue component 11, 15 g of higher alcohol F OC-1400 (manufactured by Nissan Chemical ■)
A liquid developer was prepared by diluting 0.06 g of a semi-docosanylamidate of a copolymer of diisobutylene and maleic anhydride to 12 of Isopar G.

When this was developed using the same device as in Example 1, the result was 300
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 5 to 21 In Example 4, the latex particles shown in Table 1O were used in place of the white resin dispersion of Production Example 1 of latex particles in an amount that gave a solid content of 6.0 g. 4
A liquid developer was prepared in the same manner as above.

Table 10 Table 10 (Continued) When this was developed using the same device as in Example 1, 300
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 printing 10,000 sheets were very clear.

(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 very high plate-making speeds, the developing device does not become dirty, and maintenance intervals can be extended for a long period of time. After printing 10,000 copies, the image quality of the printed matter was very clear.

Claims (2)

[Claims] (1) Electrical resistance 10^9Ωcm or more and dielectric constant 3.5
In the electrostatographic liquid developer comprising at least a resin dispersed in the following non-aqueous solvent, the dispersed resin particles contain at least one of the polymer components represented by the following general formula (IIa) or (IIb). A polymer with a weight average molecular weight of 1 x 10^3 to 2
A comb-shaped copolymer consisting of at least a 10^4 monofunctional macromonomer (M) and a monomer represented by the following general formula (III) is prepared in the presence of a dispersion stabilizing resin soluble in the non-aqueous solvent. A monofunctional monomer (A) that is soluble in a water solvent but becomes insolubilized by polymerization, and a monomer that contains an aliphatic group having 8 or more carbon atoms and is represented by the following general formula (IV). Copolymer resin particles obtained by polymerizing a solution containing at least one monomer (A) and a monomer (B) that copolymerizes in a polymerization reaction. Liquid developer for electrostatic photography. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (I), V is -COO-, -OCO-, ▲Mathematical formula,
There are chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, -O-, -CONHCOO-, -CONHC
Represents 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,
Z_1 represents a hydrogen atom or a hydrocarbon group, m is 1 to 3
represents an integer. 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_2, or -COO-Z via a hydrocarbon.
_2 (Z_2 represents a hydrogen atom or an optionally substituted 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_0 is V in formula (I) represents the same content as . Q_0 is an aliphatic group having 1 to 22 carbon atoms or 6 to 12 carbon atoms
represents an aromatic group. Q represents -CN or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. Here, Y represents a hydrogen atom, a halogen atom, an alkoxy group, or -COOZ_3 (Z_3 represents an alkyl group, an aralkyl group, or an aryl 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). General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In formula (III), X_1 represents the same content as X_0 in formula (IIa), and Q_1 is the same as Q_0 in formula (IIa). d_1 and d_2, which represent the contents of , may be the same or different from each other, and represent the same contents as a_1 and a_2 in formula (I). However, in the macromonomer (M) component represented by general formula (II) and the monomer component represented by general formula (III),
At least one of Q_0 and Q_1 represents an aliphatic group having 10 to 22 carbon atoms. General Formula (IV) In General Formula (IV), R^1 represents an aliphatic group having 8 or more carbon atoms. G is -COO-, -CONH-, ▲Mathematical formula, chemical formula, table, etc.▼(R^2 represents an aliphatic group), -OCO
-, -CH_2COO-, or -O-. e^1 and e^2 may be the same or different, and each represents a hydrogen atom, an alkyl group, -COOR^3 or -CH_2
-COOR^3 (R^3 represents an aliphatic group). (2) 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), characterized in that: