WO1987000308A1

WO1987000308A1 - Resin dispersion

Info

Publication number: WO1987000308A1
Application number: PCT/JP1986/000333
Authority: WO
Inventors: Toyokichi Tange; Masatoshi Maruyama; Shoko Nishizono; Tomohiko Minagawa
Original assignee: Toa Paint Co., Ltd.
Priority date: 1985-07-01
Filing date: 1986-06-30
Publication date: 1987-01-15
Also published as: EP0227840A1; JPS625258A; JPH0584515B2; EP0227840A4

Abstract

A resin dispersion suited as electrophotographic liquid developer for offset master, which contains in a highly insulating hydrocarbon medium: (A) a copolymer substantially insoluble in said medium and containing (i) 20 to 99.5 wt % of vinyl acetate, (ii) 0.5 to 12 wt % of a monomer represented by formula (I), (wherein R represents formula (IV), R1, R2, and R4 each independently represents hydrogen, C1-6 alkyl, or alkoxyalkyl containing 1 to 4 carbon atoms in each alkyl moiety, R3 and R'3 each independently represents C1-4 alkylene, and X represents hydrogen or methyl), and (iii) O to 79.5 wt % of C1-20 alkyl ester and/or C3-8 cycloalkyl ester of acrylic or methacrylic acid (provided that the sum of (i), (ii), and (iii) is 100 wt %), with at least part of said monomer (I) being quaternized in its amino group with a quaternizing agent; and (B) a copolymer substantially soluble in said medium and containing (iv) 95 to 15 wt % of a monomer of formula (II), (wherein X is as defined above, Y represents -COOR5, -OCOR5 or -OR5, and R5 represents C4-20 alkyl), (v) 5 to 85 wt % of a monomer of formula (III), (wherein X is as defined above, and R6 represents C3-8 cycloalkyl or aralkyl containing 1 to 3 carbon atoms in the alkyl moiety) (provided that the sum of (iv) and (v) is 100 wt %), and (vi) 0 to 2 wt % (in terms of sulfur content) of an organic mercaptan having at least one thiol group (provided that the sulfur content is represented by weight in terms of a sulfur content based on the soluble copolymer).

Description

Light box

Resin dispersion

Technology field

The present invention provides a novel resin dispersion useful for an electrophotographic liquid developer for offset masters, and is particularly excellent in dispersion stability, free from bleeding and background stain, and capable of removing an image which is eroded by rope. The present invention relates to a novel liquid dispersion which gives a liquid developer to be formed.

Background art

Conventionally, a resin dispersion for an electrophotographic liquid developer includes a polymer that is soluble in a low dielectric constant, highly electrically insulating organic solvent (hereinafter referred to as a “solvent”) and a polymer that is insoluble in the solvent. There is a resin dispersion (eg, JP-A-53-54023) obtained by subjecting the resulting monomer to graft polymerization, but such a resin composition is difficult to construct. In addition, there is a problem that the developer often generates gel and it is difficult to obtain a stable developer.

Attempts have been made in recent years to remedy the drawbacks of such graft copolymer resin dispersions, which consist of a solvent-soluble polymer and a solvent-insoluble polymer, both of which contain one COOH, one "S 0 ₃ H or resin dispersion by utilizing the adsorption capacity between the S functional groups of polar functional groups and the insoluble polymer-soluble polymer by a polar functional group such as one OCOCH 3, There are disclosed techniques for improving the stability of the product (eg, JP-A-59-83174).

However, as described above, the polar functional groups are simply The stability is improved to some extent with the resin dispersion liquid added to the hydrophilic polymer, but image blurring (outlined outline) and background stains occur frequently, especially in electrophotographic liquid development for offset masters. However, it has not been found that there are problems such as insufficient printability when used as an agent. The present invention solves the above-mentioned problems of the prior art, and has excellent stability, is free from image bleeding and background smear, and has an excellent W printability, and a resin dispersion for an electrophotographic liquid developer. Is provided. Here, the background stain refers to a development in which a print ink adheres to a non-image portion in offset printing to cause stain. Also, in offset printing, as the number of printings increases, the offset master is eroded by the solvent of the printing ink, and as a result, the printing does not adhere to the printing area. W printability refers to the property that such development does not occur. DISCLOSURE OF THE INVENTION According to the present invention, (A) 20) to 39.5% by weight, preferably 50 to 99.5% by weight, most preferably 70 to 93.5% by weight, Mouth) expression

X "■ '

CH ₂ = C

ヽ

C

ヽ (I)

0 R z no

[Where R is one 0— R ₃ — N, 0-R ₃ -NR ₂ヽヽ z

R ₂ R ' ₃ -N, ヽ

z no

-N or NR ₂ and R ^ Rs ヽヽ z

R ₂ R ₃ -N

And R ₄ each independently represents hydrogen, C, the number of carbon atoms of ~ _s alkyl or each alkyl le part of the alkoxyalkyl. 1 to 4, R ₃ and R ₃ represents C, and _1-4 alkylene independently , X represents hydrogen or methyl.] 0.5 to 12% by weight, preferably 2 to 12% by weight, most preferably 2 to 6% by weight and c) up to ₂₀ % by weight of acrylic acid or methacrylic acid. alkyl esters and Z or C ₃ ~ ₈ cycloalkyl esters 0 Ma 9.5 wt%, preferably 2-48 wt%, most preferably 5 to 28% by weight of (but above I), mouth) and c) At least a part of the monomer of the formula (I) has its amino group quaternized by a 4-ammonifying agent. A copolymer substantially insoluble in the medium, (B) X

z

CH ₂ = C (Π)

Y

Wherein X has the meaning described above, Y represents one COOR ₅ , one OCOR _s or one OR _s , and R _s represents 0 ^ _-20 alkyl. Preferably 80 to 40% by weight, most preferably 75 to 65% by weight,

E) Formula

X

z

n 2—

C-0-Re

0

[Wherein, X is a defined above, R _s is cycloalkyl or a C ₃ ~ ₈ represent Ararukiru carbon atoms from 1 to 3 alkyl moieties]

5 to 85% by weight, preferably 20 to 60% by weight, most preferably 25 to 35% by weight (however, the sum of the above 2) and e) is 100% by weight) The organic mercaptan having at least one thiol group has a sulfur content of 0 to 2% by weight, preferably 0.03 to 2% by weight, most preferably 0.1 to 1% by weight, particularly 0.2 to 0.3% by weight, A copolymer substantially soluble in the above-mentioned medium, which contains (yellow content in terms of% by weight per copolymer) of

Comprising: an electrophotographic liquid for an offset master; A callus dispersion passed through the imaging agent is provided.

Examples of the monomer of the formula (I) of the formula (I) contained in the insoluble copolymer include methacrylic acid or esters of acrylic acid and the following alcohols; Monoethyl alcohol, mono- or dimethylaminoethyl, mono- or dimethylamido / propyl alcohol, mono- or diethylaminobubyl alcohol, mono- or diphenylaminomethyl alcohol, mono- or diphenylamino-methyl alcohol, di-methoxy alcohol Monoethyl alcohol, diethoxyaminoethyl alcohol, mono- or dimethylaminopropylaminoethyl alcohol, mono- or getylamino knob-mouth bilaminoethyl alcohol. Among the monomers of the above formula (I), dialkylaminoalkyl esters of methacrylic acid are preferred, and dimethylaminoethyl esters and methylaminoethyl esters of methacrylic acid are particularly preferred.

Examples of the monomer of the formula (I) of the formula (I) include amides of methacrylic acid or acrylic acid with the following amines: mono- or dimethylamine, mono- Or getylamine, mono- or dibupyramine, mono- or dimethylaminoethylamine, mono- or dimethylaminoethylamine, mono- or dimethylamino-pyruamine and mo //-ethylamine viramine. Among the monomers of formula (I), acid amides of methacrylic acid or acrylic acid and dialkylamine or dialkylaminoalkylamine, especially dimethylamine, getylamine or dimethylamine. Nobuguchi Vilamin acid amide is preferred. The monomer of the formula (I) contained in the insoluble copolymer may contain one kind or two or more kinds. If the content of these monomers exceeds 12% by weight, the image When the hydrophilicity of the ink is increased, the ink receptivity at the time of 7-set printing is enhanced, which is not preferable. When the amount is less than 0.5% by weight, the printing durability is unfavorably deteriorated.

In addition, at least one part of the monomer of the formula (I) contained in the insoluble copolymer (particularly, a monomer contained at or near the surface of the dispersed particles has an amino group of a quaternary ammonium monomer). It is a quaternary ammonium which has been converted to a quaternary ammonium by the use of an insoluble agent whose amount is 0.1 to 5 mol% per monomer of the formula (I). A copolymer is preferable, and an insoluble copolymer having a content of 0.5 to 2 mol% is more preferable.If the amount of the quaternary ammoniating agent exceeds 5 mol%, the image density is lowered. Since the hydrophilicity becomes strong, the affinity with the offset ink after plate-making is lowered, which is not preferable. On the other hand, if it is less than 0.1 mol%, the printing performance is lowered, which is not preferable.

Examples of the quaternary ammoxidizing agent used include organic compounds exhibiting acidity, such as aliphatic or aromatic carboxylic acids, aliphatic or aromatic halides, and aliphatic. Or aromatic sulfonic acid and the like, for example, dimethyl sulfuric acid, methyl chloride and chlorinated chloride and the like can be mentioned. Dimethyl sulfate, methyl chloride and the like are preferably used.

As the C, ~ ₂₀ alkyl ester of acrylic acid or methacrylic acid contained in (c) contained in the insoluble copolymer, methacrylic acid or acrylic acid may be used. Examples of esters of lylic acid with the following alcohols: n-butanol, isobutanol / n-hexyl alcohol, 2-ethylhexyl alcohol, n-octa / nitl, n-nonyl alcohol, iso- / Nyl alcohol, n-decyl alcohol, iso-decyl alcohol, n-dodecyl alcohol, n-tridecyl alcohol, n-octadecyl alcohol, ブロ -brobanol, iso-propanol, ethanol, methanol. Of these, (^ to ₁₂ alkyl esters of methacrylic acid are preferred, and n-butyloctyl ester or 2-ethylhexyl ester is particularly preferred.

The C ₃ ~ _a cycloalkyl ester of Akuriru acid or Metakuriru acids c) contained in the copolymer insoluble can be exemplified an ester of a following alcohol and Metaaku acrylic acid or § click acrylic acid; Shikurobu port Birua alcohol, Cyclohexyl alcohol, cyclohexyl alcohol, cyclopentyl alcohol and cyclooctyl alcohol. Among them, the hexyl ester of meta-atallylic acid is preferred.

~ Of § click acrylic acid or Metaku acrylic acid of c) contained in the copolymer insoluble _2. Alkyl esters and z or c ₃ ~ ₈ consequent opening alkyl Es ether may be contained one or two or more, preferably but contained 2-4 8 wt%, the multi exceed 4 8 wt% If it is too small, it is not preferable because the image density is lowered and printability is enhanced. If it is less than 2% by weight, the particle diameter becomes large and sedimentation stability is unfavorably increased.

Insoluble copolymers include vinyl acetate, monomers of formula (I) and acrylic acid. Or C Metaata acrylic acid, other than the ~ ₂₀ alkyl esters and / or C ₃ - ₈ cycloalkyl esters, the ingredients, optionally in a range that does not adversely affect the various properties such as stability and scumming and Si printing properties Can be contained. Monomers of the formula ()) of-) contained in the soluble copolymer include n-butyl ester, isopropyl ester, n-hexyl ester of methacrylic acid or acrylic acid, and π - old Kuchiruesuteru, Kishiruesute to 2 Echiru Le, n- dodecyl ester, n- Application Benefits decyl ester, .pi. Okutadeshiruesu ether, _n - Bruno - glycol ester, Lee Seo - Bruno - glycol ester, n- decyl ester, i source - The methacrylate 51 such as decyl ester is made of acrylate, fatty acid vinyl such as vinyl brobionate, vinyl acetate, and vinyl versatate, and vinyl ether such as vinyl n-butynole ether and vinyl isobutyl ether. Examples can be given.

Preferred monomers of formula (Π) are of the formula CH ₃

CH ₂ = C

ヽ

CO OR '[Π 3 [where R' represents alkyl of C ₄ ~]

And 2-ethylhexyl methacrylate and n-octyl acrylate are particularly preferred.

If the amount of the monomer of the formula (II) is more than 95%, it is not preferable because the bleeding of the image and the printability are deteriorated, and if the amount is too small, the sedimentation stability is lowered. Not preferred. Examples of the monomer of formula (m) of e) contained in the copolymer soluble, c) of c ₃ ~ ₈ cycloalkyl esters及Pi Akuriru acid or exemplified acrylic acid or Metakuriru acid as monomer Examples include y-phenyl bromoyl ester, -phenyl-ethyl ester, and benzyl ester of meta-atalylic acid.

Suitable monomers of the formula (IB) is also C ₃ ~ ₈ consequent opening alkyl meth Ata Li rate is C ₃ ~ ₈ cycloalkyl Atari rate, preferably Kishirumeta Atari rate or consequent opening Arukiruakuri rate especially cyclohexylene It is.

If the amount of the monomer of the formula (m) exceeds 85% by weight and is too large, the solubility is lowered and the stability of the dispersion is lowered, which is not preferable. If the amount is less than 5% by weight, image bleeding occurs. It is not preferable because the property is lowered.

Organic mercatanes having at least one thiol group (contained in soluble copolymers) have from 1 to about 4 thiol groups per molecule and from 1 to about 12 carbon atoms per thiol group. And preferably contains 2 to 8 carbon atoms. These organic mercaptans can contain other substituents in addition to the hydrocarbon groups, such as carboxylic acid groups, hydroxy groups, ether groups, ester groups, sulfido groups, amine groups. The base group is included. Examples of useful mercaptans include methyl mercaptan, ethyl mercaptan, butyl mercaptan, octyl mercaptan, vinyl mercaptan, mercaptoethanol, mercaptoprohanol, mercaptobutanol, mercaptoacetic acid, mercaptoacetic acid. Probionic acid, titanium linoleic acid, benzylmercaptan, phenylmenolecabbutane, cyclohexane Xylmer ^ butane, 1-thioglycerol, 2,2'-dimer * Butjethyl ether, 2,2 Dimercapto dibuvir ether, 2,2'-Dimerbuto diisobrovir ether, 3,3'-Dimercapto jibulovir Ter, 2,2'-dimercaptocetyl sulfide 7, 3,3 dimercapto jib mouth bilsulfide, 1,11-dimercapto-3,9-dioxa-6-thiaoundene, bis (-mercapto Ethoxy) methane, bis (-mercaptoethylthio) methane, ethanedithio-1,2, propanedithiol-1,2, butanedithiol 1,4,3,4-dimercaptobutanol-1, trimethylolethane tri (3-mercaptopropionate), pentaerythritol tetra (3-mercaptoprobionate), trimethylol broban and lithoglycolate Fine Pentaeri door Li door one Rute door Rachio glycolate is included.

Examples of suitable organic mercaptans are butyl mercaptan, butyl mercaptan, butyryl merbutane, lauryl mercaptan, mercaptoethanol, mercaptobrono, nol, mercaptoethanol, mercaptobutanol, mercaptobutanol, mercapto tungstic acid, mercaptobutrionic. Acids, benzyl mercaptan, phenyl mercaptan and the like, and in particular, lauryl mercaptan, mercaptoethanol, mercaptopropanol, mercaptobutanol, mercaptoacetic acid, and merbutobrovionic acid are preferable. The content of the organic mercaptan per soluble copolymer is preferably 0.03 to 2% by weight in terms of the S content. If the content is more than 2% by weight, the sedimentation stability of the dispersion liquid is reduced, which is not preferable. , And less than 0.03% by mass If the content is too small, the dilution stability of the dispersion and the background contamination of the developed product are not preferred.

Soluble copolymers The monomer of the formula (Π), the monomer of the formula (及び) and components other than the organic mercaptan are adversely affected by various properties such as stability, background fouling and surface printing. Can be contained as necessary within a range that does not affect

The soluble polymer used in the present invention is preferably 500,000 or less, more preferably 3,000 to 30,000, and most preferably 5,000 to 25,000. It has a molecular weight of 0. If the molecular weight is more than 50, 000, the dispersion stability is diminished or the developer tends to stain, which is not preferable.If the molecular weight is too low, the dispersion is too low. It is not preferable because the stability of the rubber becomes poor.

The ratio of the soluble copolymer (B) to the insoluble polymer (A) in the resin dispersion of the present invention is not particularly limited, but the soluble copolymer is preferably 5 to 50% by weight, more preferably 20 to 50% by weight, more preferably 30 to 40% by weight, and insoluble polymer 35 to 50% by weight, preferably 80 to 50% by weight, and more preferably 70 to 60% by weight. % Percentages are used. If the content of the soluble copolymer is less than 20% by weight, the stability of the resin dispersion is undesirably reduced. If the content is more than 50% by weight, the image is blurred or the density becomes low. In addition, it is not preferable that the printing durability is reduced.

The particle size distribution of the dispersed particles of the resin dispersion of the present invention is such that 70% or less, preferably S 0% or more, of particles having a size of 0.5 # or less.

The insulating hydrocarbon medium contained in the resin dispersion of the present invention has a low dielectric constant. And an electrically insulating organic solvent. Examples of such an organic solvent include normal paraffinic hydrocarbons, isobaraffin yarn hydrocarbons, aromatic hydrocarbons, and halogenated aliphatic hydrocarbons. However, a paraffinic or alicyclic hydrocarbon-based medium having a boiling point of 150 to 200 is preferably used in view of odor, safety, drying property and the like.

In general, the resin dispersion of the present invention can be easily produced by polymerizing an insoluble polymer in a solution of a soluble polymer in a medium, but a soluble copolymer and an insoluble polymer are separately prepared. It is also possible to suitably produce the compound by dissolving both polymers in a common solvent of both polymers, and then dropping the mixture in a hydrocarbon medium with stirring.

The particle size distribution of the resin dispersion can be adjusted by may varying the proportion of soluble copolymer insoluble polymers, also C _[1-2 of the c) insoluble polymer. It can also be adjusted by changing the amount of the alkyl meta acrylate or acrylate.

In order to convert at least a part of the monomer of the formula (I) contained in the insoluble polymer into a quaternary ammonium, it is necessary to prepare a resin dispersion liquid and then use a sensitized ammonium salt such as dimethyl sulfate. The monomer (I) may be ammoniated by a conventional method such as dimethyl sulfate or methyl chloride prior to the polymerization reaction as described above. .

In order to produce an electrophotographic liquid developer from the resin dispersion of the present invention, the dispersion particles may be colored and charged as necessary.

In order to impart a charge to the resin dispersion of the present invention, a charge inhibitor is used, Examples of such charge control agents include zinc naphthenate, manganese naphthenate, oleic acid, cobalt octoate, lecithin, sodium dioctyl sulfosuccinate, and aluminum stevelite rosin. For coloring the resin dispersion of the present invention, a grossine dye / phthalocyanine pigment, oil black, carbon black or the like is used.

BEST MODE FOR CARRYING OUT THE INVENTION

Example 1

In a reactor equipped with a stirrer, a reflux condenser, and a dropping device, put 120s of hebutane, 4Os of toluene and 4g of azobisuisopti-tril, and heat 4g of n-octyl methacrylate under heating. Then, a mixture of cyclohexyl methacrylate 70 g and azobisisobutyrate-tolyl 2 s was dropped in 1 hour, and after reacting for 1 hour, a mixture of 40 s of toluene and 1.5 g of azobisisobutyronitrile was added dropwise in 30 minutes, followed by 2 more drops. I let the time go. Next, a mixture of vinyl acetate 30 Os and benzoyl oxide 3 s was added dropwise over 2.5 hours, and after 30 minutes, a mixture of 200 g of _π -heptane and varoyl L (manufactured by NOF CORPORATION) 28 was added 30 minutes later. After a reaction for 20 minutes, a mixture of getylaminoethyl methacrylate 128, n-heptane 4 g, and bar αyl L 1 s was added, and after 1 hour reaction, bar 100 g of Isobar G and 0.28 of dimethyl sulfate were added and cooled to obtain a milky white stable dispersion.

20 s of this resin dispersion, 1.6 s of Bontron N-04 (Oriental Chemical Industry Co., Ltd.), 80 g of Isopar G, and 18 zinc naphthenate are mixed at room temperature. A concentrated developer was obtained by kneading with a mixer for 11 hours, and this was diluted 10 times with Isopar G to obtain a developer.

Example 2

To the same reactor as in Example 1, n-yearly butyl methacrylate 125s, cyclohexyl methacrylate 79g, and mercaptoethanol 2g were added, and agitated while sending a small amount of air to the liquid surface, and at 80 for 16 hours. After keeping the air, the air was stopped, 35 s of n-heptane was added, and the mixture was heated and a mixture of 4 Og of toluene and 1.5 s of azobisisobutyronitrile was added dropwise in 3 hours under reflux, and the reaction was continued for 2 hours. I did. The molecular weight of the obtained copolymer was about 15,000.

Next, n-heptane-Og was added, and the mixture was refluxed with vinyl acetate: a mixture of I5Os and n-methyloctyl methacrylate, 25 g, and benzoyl peroxide, 4 s, was added in 2 hours. 1 50 g, a mixture of 40 s of n-heptane and 4 s of benzoyl peroxide was added dropwise over 1 hour, and the mixture was allowed to evaporate for 30 min. Add the mixture of Le Is and add 30 g of the mixture of Paryl L Is and 5 g of n-heptane.Add 1.5 g of the mixture, add Isobar G 13 Og and cool to 10 or less. Further, 0.1 lg of ethyl chloride was added. The resulting dispersion was a very stable, slightly translucent, slightly yellowish emulsion.

5.5 _g of surface-treated Fudarocyanine Blue, Isopar G 3 14 s and 4 g of zinc stearate were added to 50 s of the resulting resin dispersion, and the mixture was pole milled.

The mixture was kneaded for 24 hours to obtain a concentrated developer. Use this concentrated developer with Isopar G A 10-fold dilution was used as a developer.

Example 3

The reactor of Example 1 was charged with 140 s of 2-ethylhexyl methacrylate, 60 parts of benzyl methacrylate, 0.4 g of azobisisobutymouth-tolyl, 3 g of mercaptoacetic acid and 358 of n-hexane. Heated until flowing. After refluxing for 2 hours under the reflux condition, a mixture of 10 g of toluene and 0.3 s of azobisisopti-tol-tolyl 0.3 s was added dropwise in 2 hours, and the mixture was further reacted for 2 hours to obtain a copolymer solution having a molecular weight of about 11,000. Obtained.

Then, a mixture of 346 s of vinyl acetate, 50 s of 2-ethylhexyl acrylate, 8 g of perbutyl 0 (manufactured by Nippon Oil S), and π-heptane 1508 was added dropwise over 4 hours, and after 1 hour of reaction, 04 g of bar butyl was added to the mixture. After 20 minutes, a mixture of 4 g of dimethyl acrylamide, 5 g of n-heptane and verbutyl 018 was added.After 30 minutes, 0 lg of perbutyl was added, and the mixture was inverted for 2 hours.100 g of Isopar G was added, followed by cooling. g was added.

The resulting dispersion was a slightly transparent, pale brown emulsion having an average particle size of 0.2 m.

A mixture of 5 g of oil black HBB and xylene 208 was added dropwise to 100 s of the resulting resin dispersion liquid and 150 g of Isobar G with stirring, and aluminum stearate Is was added, followed by 10 addition of Isobar G to prepare a developer.

Example 4

N-octyl methacrylate obtained according to Example 2 and cyclohexylmethacrylate 70 g of n-hexane, 130 g of Isopar G, 27 g of vinyl nitrate, 35 g of n-octyl methacrylate, 35 s of cyclohexyl methacrylate 2 lg and benzoyl peroxide 6 s were added, and the mixture was reverted under the flow of S. After 3 hours, whitening occurred. Further, a mixed solution of 45 g of n-heptane and benzoyl peroxide 28 was added and reacted for 1 hour. Next, 24 g of N, N-dimethylaminobutyral viracrylamide, 30 g of methyl acrylate, 0.4 g of dimethyl methaminoethylmethyl chloride, and 0.4 g of benzoyl oxide benzene are added for 1 hour. On the other hand, benzoyl peroxide 18 was further added, and the mixture was allowed to stand for 2 hours to obtain a slightly transparent and pale brown emulsion.

A developer was prepared from the resulting resin dispersion in the same manner as in Example 2. Comparative Example 1

A developer was prepared in the same manner as in Example 1 except that stearyl methacrylate was used instead of cyclohexyl methacrylate in Example 1. Comparative Example 2

A developer was prepared in the same manner as in Example 1, except that a mixture of 12 g of getylaminoethyl methacrylate, 4 g of n-heptane, and parlor L 1 s was not added when the dispersion was polymerized. .

Comparative Example 3

A developer was prepared in the same manner as in Example 2, except that the amount of methyl sulfate after dispersion polymerization was changed from 0.1 g to 1 g.

Comparative Example 4

A developer was prepared in the same manner as in Example 3, except that No addition of methyl was made.

Using the developer obtained as described above, an image was formed on an offset master electrostatic recording coated with zinc oxide, an etching process was performed, and then printing was performed using a commercially available offset ink.

The compositions of the resin dispersions obtained in Examples 1 to 4 and Comparative Examples 1 to 4 are shown in Table 1, and the results of the printing test are shown in Table 2.

Table 1

Insoluble copolymer component (% by weight) Quaternary ammolyzing agent Patent No. 1 in the scope of the patent application (1) (A) mouth) (A) c) (A) c) Example 1 96.2 3.8 0 2.4

2 85.7 2.9 11.4 IA

3 86.5 1.0 12.5 1.0

4 67.4 7.1 25.5 1.3 Thigh 1 96.2 3.8 0 2.4

2 100 0 0 oo

3 85.7 2.9 11.4 10

4 86.5 1.0 12.5 0

Table 1 (string)

Soluble copolymer component (% by weight) Organic mercaptan Soluble copolymer component 1 ■ —

Monomer of formula (11) Monomer of formula (BI) (% by weight sulfur) Example 1 OD 3D 0

2 62.5 37.5 0.4

3 70 30 0.5

4 62.5 37.5 0.4 Comparative example 1 100 0 0

2 65 35 0

3 62.5 37.5 0.4

4 70 30 0.5

Table 1

Ltd. Version picture image printed matter concentration ^υ bleeding ²⁾ printing of ³⁾ vividness-stain ^s> Example 1 3 4 4 4 4

2 4 4 5 5 5

3 5 4 4 5 5

4 3 4 5 4 5 Comparative example 1 3 1 4 1 1

2 3 4 1 4 3

3 1 2 5 1 2

4 5 4 1 5 5

1) Using Example 1 as standard (3), the number was increased as the concentration increased.

2) Image bleeding was determined by the following 5-point method

5: No image blur

4: II Slightly recognized

3: There is a little II

2: Yes

1: Large

3) Using the plate-making image subjected to the etching process as the original plate, printing was performed on a high quality coll with a commercially available offset ink, and the evaluation was made based on the number of prints until the image of the fine dot portion disappeared.

5: 5,000 or more

4: 4,000-5,000 sheets

3: 3,000-4,000 sheets

2: 2,000 to 3,000 sheets

1: More than 2,000 sheets

4) The printability was evaluated based on the density of the printing paper obtained by the printability test, the bleeding at the edges of the image area, and the sharpness of the fine spots.

5: High density, no bleeding of image and fine spots

4: Slight bleeding is observed in the dark print area

3: Yasushi Wakasen is recognized by Yasushi Printing

2: The image is generally blurred, and the fine dots are slightly unclear.

1: The image is blurred or thinned, or fine dots are appearing And black solid printing

5) The prints obtained by the face-to-face printability test (5 sheets were superimposed with the image portion overlapped, and non-print portions and unprinted portions of the same number as the print portions) were compared side by side and compared to determine the stain condition.

5: No difference is observed even when layered

4: Slight difference is observed

3: A slight difference is observed

2: A difference is observed

1: The difference is very large

Example 5

In the reactor of Example 1, 2-ethylhexyl methacrylate 140 s, benzyl methacrylate 60 s, azobisisobutyronitrile 0.4 g, mercaptoacetic acid 3 s and n-hexane 35 s were heated until arrest. did. After reacting for 2 hours under the arrest condition, a mixture of 10 _g of toluene and 0.3 _g of azobisisobutyronitrile was added dropwise in 2 hours, and the mixture was further reacted for 2 hours to give a copolymer solution having a molecular weight of about 11,000. Obtained.

Then Kishiruaku Li rate 5 60 ₈ It齚酸vinyl 2, 240s and the 2 Echiru, Perbutyl 0 (Nippon Oil膪製) 56 g, added dropwise to 1 hour reaction at 4 hours a mixture of butane 1 050G to π- After that, perbutyl 0 28 s was dropped in 30 minutes, and 20 minutes later, a mixture of 28 g of dimethyl acrylamide, 35 g of n-heptane and 07 s of perbutyl was added, and 30 minutes later, perbutyl 07 s was added. After reacting for 2 hours, 350 s of Isopar G was added and cooled, and then 0.35 s of dimethyl sulfate was added. The resulting dispersion was a slightly transparent, pale blue milk rinse having an average particle size of 0.2 #a.

A mixture of 5 g of oil black HBB and xylene 208 was added dropwise to 100 _g of the resulting dispersion and 100 _g of dispersion, and 10 _g of Isopar G was added while adding aluminum stearate-aluminum Is. A developer was used.

The respective values of the resulting resin dispersion corresponding to columns 2 to 8 of Table 1 are as follows. Inert copolymer component (% by weight); monomer (A) 73.2, monomer (A) 1.0), monomer (A) c) in claim 1 19.8, 4-pig ammonifying agent; monomer (mol%) of claim 1 (port (A)) 1.0; soluble copolymer component (wt%); monomer of formula (II-) 70 , Monomer 30 of the formula (BI), organic mercaptan; soluble copolymer component (sulfuric acid weight%) 0.5.

The printing test using the developer obtained here is as follows. Degree 4, bleed 4, it printability 4, clarity 5, background dirt 4,

Industrial applicability

Since the resin dispersion of the present invention is extremely excellent in stability, the electrophotographic liquid developer for offset master, which uses the resin dispersion of the present invention extremely, is diluted about 160 times to obtain a developing margin. Is extremely stable and does not cause development such as generation of a large amount of sediment or gel-like aggregates. There is no bleeding (blur of the outline) or background smear when performing offset printing, and 5,000 times The excellent clear image can be obtained even after printing It has face printability.

Claims

Scope of Claim 1. (1) In an insulating hydrocarbon medium, (A) i) butyl acetate 20 ~ 99.5% by weight, mouth) formula

X CH ₂ = C

ヽ

C

\ (I)

0 R

No Z

[Where R is 1—R ₃ —N, 1—R ₃ — NR ₂ヽヽ z

R ₂ R ₃ -N,

R ₄

-N or NR ₂ and R ,, R ₂

\ ヽ z

R ₂ R ₃ -N

And RJ or each independently a hydrogen, the carbon number of 1-6 alkyl or calamity s alkyl Le portion represents alkoxyalkyl. 1 to 4, R ₃ and R ₃ are independently C, represent _1-4 alkylene, X Represents hydrogen or methyl

Monomer 0.5 - 12 wt%及Piha) through Akuriru acid or Metakuriru acid _2. Alkyl esters and / or C ₃ ~ ₈ consequent opening alkyl esters from 0 to 73.5 weight However, the above I), mouth)及Piha total 100 weight) % Of the monomer of the formula (I), wherein at least a part of the monomer of the formula (I) has its amino group quaternized with a 4-ammonifying agent. Insoluble copolymer in (B)

X

z

CH ₂ = C (Π)

ヽ

Y

[Wherein, X is a defined above, Y one COOR _s, represents -OCOR _s or single 0 R _{_s,} R _s represents alkyl of C ₄ ~ _20] monomers body 95 to 15 weight of %, E) formula

X

z

CH ₂ = C

ヽ

C-O-Re (I)

0

[Wherein, X is a defined above, R ₆ Ho C ₃ cycloalkyl or a _1-8 alkyl moiety of a carbon number represents Ararukiru 1-3] monomer 5-85% by weight of ( However, the sum of the above 2) and e) is assumed to be 100% by weight) and f), and the organic mercaptan having at least one thiol group is 0 to 2% by weight in sulfur content (however, the following soluble copolymer A copolymer substantially soluble in the medium, comprising a sulfur content per body in weight percent). A resin dispersion suitable for an electrophotographic liquid image for offset masters, characterized by comprising:

2. The resin according to claim 1, wherein said soluble copolymer contains said organic mercaptan in a sulfur content of 0.03 to 2% by weight.

3. The resin dispersion according to claim 2, wherein the amount of said 4-sensitive amohumulating agent is 0.1 to 5 mol% per monomer of the formula (I).

4. The resin drinking liquid according to any one of claims 1 to 3, wherein the soluble copolymer has a molecular weight of 50,000 or less.