JPH0812490B2 - Liquid developer for electrostatic photography - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial field of application" The present invention relates to a liquid development for electrostatic photography, which is formed by dispersing at least a resin in a drain solvent having an electric resistance of 10 ⁹ Ω · cm or more and a dielectric constant of 3.5 or less. The present invention relates to a developer, and more particularly to a liquid developer having excellent storage stability, stability, redispersibility and fixability.

"Prior Art" General liquid developers for electrophotography are carbon black,
Inorganic or organic pigments or dyes such as nigrosine and phthalocyanine blue and natural or synthetic resins such as alkyd resin, acrylic resin, rosin and synthetic rubber are used as liquids with high insulation and low dielectric constant such as petroleum aliphatic hydrocarbons. A polymer containing metal soap, lecithin, linseed oil, higher fatty acid, vinylpyrrolidone, etc. is added therein for the purpose of uniformly and strongly enhancing the charge characteristics of the dispersed particles.

In the developing step, such a developer causes electrophoresis in accordance with the charge of the electrostatic latent image formed on the surface layer of the electrophotographic photosensitive material or the electrostatic recording material, and is fixed on the surface to form a visible image ( A method of forming fine resin particles for forming a copied image and using the resin particles as toner particles is disclosed in US Pat.
No. 90980, etc. However, according to the experimental results of the present inventors, these liquid developers have not been sufficiently improved in dispersion stability against spontaneous sedimentation of particles, but are not sufficient when used in an actual developing device. The toner adhering to each part of the apparatus solidifies into a coating film and is difficult to re-disperse, and further, there are drawbacks such as failure of the apparatus and stain of copied images. In the method for producing resin particles described above, in order to produce monodisperse particles having a narrow particle size distribution, a dispersion stabilizer to be used,
There were significant restrictions on the combination with the insolubilizing monomer, and the particles were generally particles having a large particle size distribution containing a large amount of coarse particles, or were polydisperse particles having two or more average particle sizes. Further, it is difficult to obtain a desired average particle diameter with monodisperse particles having a narrow particle size distribution, and it is difficult to obtain large particles of 1 μm or more or 0.
Very fine particles of 1 μm or less were formed. Further, the dispersion stabilizer to be used has a problem that it must be manufactured through a manufacturing process which is frequent and requires a long time.

Also, in conventional liquid developers, dispersion stabilizing resins and home appliance control agents diffuse into the liquid, making the charging characteristics unclear, which causes a decrease in image density, fixability, and increased scumming. There is a drawback that makes the image unclear.

Further, these developers are difficult to use because particles tend to settle or agglomerate with time and cannot be redispersed once settling.

Further, because of these drawbacks, they are unsuitable for offset printing or for transfer such as charge transfer, pressure transfer, and magnetic transfer.

As a method for improving these problems, a method has been proposed in which a polymer is grafted on the surface of a pigment such as carbon black to stabilize the dispersion of particles. However, the developer thus obtained has a drawback in that the relative amount of the resin component attached to the image surface at the same time as the pigment is small, and the strength of the formed image after fixing is not sufficient.

Therefore, when an image is formed on a zinc oxide photoconductor paper by using these developers and used as an offset printing plate, the sensitivity to printing ink and the number of printed sheets are insufficient due to the above-mentioned causes. Caused a problem.

As another improvement method, in the above non-aqueous solvent, in the presence of a dispersion stabilizer, a monomer that polymerizes to insolubilize the monomer and a copolymer containing a long chain alkyl moiety-containing monomer JP-A-60-1859 discloses a method for improving the dispersity, redispersibility, and storage stability of particles by using insoluble dispersed resin particles of
No. 63 etc.

On the other hand, in recent years, a method of printing a large number of 5000 or more sheets by using a master plate for offset printing by an electrophotographic method has been attempted. In particular, the master plate has been improved, and 10,000 or more sheets have been printed in a large plate size. It has become possible. Further, the operation time of the electrophotographic plate making system has been shortened, and improvement in speeding up the development-fixing process has been performed.

"Problems to be Solved by the Invention" According to the results of experiments conducted by the present inventors, the above-mentioned JP-A-60-1859
The particles produced by the method disclosed in No. 63, etc. were good in particle monodispersibility, redispersibility, and storage stability, but printing durability in large plate size and fixing The performance was not satisfactory for speeding up the time.

Therefore, an object of the present invention is to provide a liquid developer having excellent dispersion stability, redispersibility and fixability.

Another object of the present invention is to provide a liquid developer which enables the production of an offset printing original plate having excellent oil sensitivity and printing durability by electrophotography.

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

Still another object of the present invention is to provide a liquid developer which can be used in any system in which the liquid developer can be used such as ink jet recording, cathode ray tube recording and recording of various changing steps such as pressure change or electrostatic change. That is.

"Means for Solving Problems" The present invention has an electric resistance value of 10 ⁹ Ω · cm or more and a dielectric constant of 3.5.
In the liquid developer for electrostatic photography, which is prepared by dispersing at least a resin in the following non-aqueous solvent, the monomer forming the resin is soluble in an organic solvent, A monomer capable of forming a polymer insoluble in an organic solvent (monomer (A)) and at least 1 represented by the following general formula (I) in an amount of 0.05 to 10% by weight based on the monomer (A). The resin comprises a monofunctional monomer (monomer (B)) and a resin represented by the following general formula (II) (monomer (C)) and general formula (III). A resin obtained by a polymerization reaction in a solution containing a copolymer resin soluble in the non-aqueous solvent obtained by polymerizing the monomer (monomer (D)) represented by Is a liquid developer for electrostatic photography.

General formula (I) In the general formula (I), Q is -O-, -COO-, -OCO-,
_{-CH 2 OCO -, - SO 2} -, Or [W represents a hydrogen atom, a hydrocarbon group or a bonding group in the general formula (I): R ₁ -T _{1 m} R ₂ -T _{2 n} S ₁ ].

S ₁ is a hydrogen atom or a halogen atom, -OH, -CN, -N
It represents a hydrocarbon group having 1 to 18 carbon atoms which may be substituted with H ₂ , —COOH, —SO ₃ H, and —PO ₃ H.

T ₁ and T ₂ may be the same or different from each other, and are —O—,
-S -, - CO -, - CO 2 -, - OCO -, - SO 2 -, Represents —NHCO ₂ — or —NHCONH— (S ₂ represents the same symbol as S ₁ above).

R ₁ and R ₂ may be the same as or different from each other, may be substituted, or Represents a hydrocarbon group having 1 to 18 carbon atoms which may be interposed in the bond of the main chain (however, T ₃ and T ₄ may be the same as or different from each other, and the same symbols as those of T ₁ and T ₂ are shown. R ₃ represents an optionally substituted carbon hydroxyl group having 1 to 18 carbon atoms, and S ₃ represents
The same symbols as S ₁ are shown].

Also, a ₁ and a ₂ may be the same or different from each other, and are a hydrogen atom, a hydrocarbon group, —COO—K or —COO via a hydrocarbon.
-K (K represents a hydrogen atom or a hydrocarbon group which may be substituted), m, n and p may be the same or different and each represents an integer of 0-4. However, m and n are never 0 at the same time.

General formula (II) In formula (II), L represents an aliphatic group having 8 or more carbon atoms, Y ₁ and Y ₂ may be the same or different and each represents a hydrogen atom or an alkyl group.

General formula (III) In formula (III), X is -COO-, -CONH- or (R ₆ represents an aliphatic group), Y is a group connecting the functional group X and the atomic group Z with a carbon atom which may have a hetero atom, and Z is the atomic group Y. In group linking the _{door, -COO -, - COOCH 2 -} , - O -, - S
O ₂ −, or Are respectively represented.

However, when X represents -COO-, it does not go through Y and Z, but directly. May be combined with Y ₃ , Y ₄ and Y ₅ may be the same or different and each represents a hydrogen atom or an alkyl group.

Preferably, X is -COO-, -CONH-, or (R ₆ represents an alkyl group or an alkenyl group having 1 to 22 carbon atoms), Z is —COO—, —COOCH ₂ — or —O—
, Y is a group which connects the functional groups X and Z with each other through a carbon atom which may be through a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom, and Y ₃ , Y ₄ and Y ₅ are respectively Represents a hydrogen atom or a methyl group.

Further specific examples of Y include: (R _7, R ₈ represents a hydrogen atom, an alkyl group, a halogen atom, etc.), - CH = CH-, -COO -, - NHCO -, - NHSO 2 -, - NHCONH -, - NHCOO
_{-, - SO 2, -CO -} , - O -, - S-, (R represents a hydrogen atom, an alkyl group, etc.) and the like.

The electric resistance used in the present invention is 10 ⁹ Ω · cm or more, and the dielectric constant is
As the non-aqueous solvent of 3.5 or less, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons or halogenated hydrocarbons can be preferably used. More preferably from the viewpoint of volatility, stability, toxicity, odor, etc., octane, isooctane, decane, isodecane,
Nonane, dodecane, isododecane, decalin, isoparaffin-based petroleum solvent, Isopa-E, Isopa
G, Isopa-H, Isopa-L (Isopar: trade name of Exxon), Cielsol 71 (trade name of Ciel Oil), Amsco OMS, Amsco 460 solvent (trade name of Spirits), etc., alone or in combination. To use.

The non-aqueous dispersion resin which is the most important constituent component of the present invention is produced by a so-called polymerization granulation method obtained by polymerizing the monomer in the presence of a dispersion stabilizer in an organic solvent. Is.

As the organic solvent, basically, any solvent can be used as long as it is miscible with the carrier liquid of the liquid developer for electrostatic photography, but at the stage of resin dispersion production, the same solvent as the carrier liquid is used. Is usually preferred.

That is, as the solvent used for producing the dispersion resin, linear or branched aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and the like are preferable.

More specifically, hexane, octane, isooctane, decane, isodecane, nonane, dodecane, isododecane, and isoparaffin-based petroleum solvent isopar.
E, Isopa-G, Isopa-H, Isopa-H, Isopa-L, Cielsol 71, Amsco OMS and the like are preferable.

The following compounds may be mentioned as examples of the monomer (D).

In order to produce the soluble copolymer resin used in the present invention described above, the monomer (C) and the monomer (D) are generally used.
And in the same solvent used when producing the dispersion resin,
The reaction may be performed at a reaction temperature of 60 to 100 ° C. for a reaction time of 2 to 10 hours in the presence of a polymerization initiator such as benzoyl peroxide or azobisbutyronitrile. Under the above-mentioned polymerization conditions, gelation due to the crosslinking reaction of the copolymer does not occur at all, and a copolymer having a desired double bond in the side chain can be obtained.

In the present invention, a ternary or higher copolymer can be obtained by adding another monomer to the reaction system and carrying out a polymerization reaction. In any case, the composition ratio of the monomer (C) and the monomer (D) is preferably 50:50 to 99.5: 0.5 (weight ratio), and the molecular weight of the copolymer is preferably 5,000 to 500,000. is there.

Specific examples of the resin obtained as described above are shown below, but the contents of the present invention are not limited to these.

Furthermore, when obtaining the resin dispersion of the present invention, a conventionally known dispersion stabilizer can be used together.

That is, various synthetic resins or natural resins soluble in an organic solvent can be used alone or in combination of two or more kinds. For example, an alkyl chain having a total of 4 to 30 carbon atoms (which may contain a substituent such as a halogen atom, a hydroxyl group, an amino group, an alkoxy group, or a hetero atom such as an oxygen atom, a nitrogen atom, a sulfur atom, etc. A carbon-carbon atom bond may be present), an alkyl ester of acrylic acid or methacrylic acid, a vinyl ester of a fatty acid, or a vinyl alkyl ether or a monomer such as olefin such as butadiene, isoprene, or diisobutylene. Or a copolymer of a combination of two or more kinds thereof, and further, a monomer forming a polymer soluble in an organic solvent as described above and one or more kinds of various monomers as described below. It is also possible to use a copolymer which is a copolymer using the following monomers within a range in which the obtained copolymer is soluble in an organic solvent.

For example, methyl acetate such as vinyl acetate, acrylic acid, methacrylic acid or crotonic acid, n-propyl or
iso-propyl ester; styrene; vinyltoluene,
Styrene derivatives such as α-methylstyrene; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid or their anhydrides; hydroxyethyl methacrylate, hydroxyethyl acrylate, diethylaminoethyl methacrylate, N-vinylpyrrolidone , Acrylamide, acrylonitrile, 2-
A unit containing various polar groups such as hydroxy group, amino group, amide group, cyano group, sulfonic acid group, carbonyl group, halogen atom and hetero ring such as chloroethyl methacrylate and 2,2,2-trifluoroethyl methacrylate. Examples thereof include a polymer. Alternatively, in addition to the above synthetic resins, natural resins such as alkyd resins, alkyd resins modified with various fatty acids, linseed oil, and modified polyurethane resins can also be used.

The monomer used in producing the non-aqueous dispersion resin of the present invention is soluble in an organic solvent as described above, but is insolubilized by polymerization (referred to as a monomer (A)).
And a monofunctional monomer represented by the general formula (I) (referred to as a monomer (B)).

Examples of the monomer (A) include vinyl esters or allyl esters of aliphatic carboxylic acids having 1 to 3 carbon atoms (acetic acid, propionic acid, butyric acid, monochloroacetic acid, etc.); acrylic acid, methacrylic acid, crotonic acid, and itacone. C1 to C3 alkyl esters or alkylamides of unsaturated carboxylic acids such as acids and maleic acids; styrene; styrene derivatives such as vinyltoluene and α-methylstyrene; acrylic acid, methacrylic acid, crotonic acid, maleic acid, itacone Unsaturated carboxylic acids such as acids or anhydrides thereof; hydroxyethyl methacrylate, hydroxyethyl acrylate, diethylaminoethyl methacrylate, N-vinylpyrrolidone, acrylonitrile, vinyl ether and the like can be mentioned.

The monomer (B), which is a constituent factor of the present invention, is a monofunctional monomer of the general formula (I) which undergoes a copolymerization reaction with the monomer (A) by a radical reaction, and is preferably , In the general formula (I), Q is —O—, —COO—, —OCO—, —CH ₂ OCO.
-, Represents [Wherein W is a hydrogen atom, an alkyl group having a total carbon number of 1 to 16 that may be substituted, an alkenyl group having a total carbon number of 2 to 16 that may be substituted, or a total carbon number of 5 to 18 may be substituted] Good alicyclic group or linking group in general formula (I): R ₁ —
The same symbols as those for T _{1 m} R ₂ -T _{2 n} S are shown].

S ₁ is a hydrogen atom, or a halogen atom (for example, a chloro atom, a bromo atom, etc.), —OH, —CN, an aliphatic group having a total of 1 to 16 carbon atoms which may be substituted with —COOH (as an aliphatic group, for example, Indicates an alkyl group, an alkenyl group or an aralkyl group)
Indicates.

T ₁ and T ₂ may be the same as or different from each other, and —O
-, -S-, -CO-, -COO-, -OCO-, Or (S ₂ represents the same symbol as S ₁ above).

R ₁ and R ₂ may be the same as or different from each other, may be substituted, or Represents a hydrocarbon group having 1 to 12 carbon atoms (which may be an alkyl group, an alkenyl group, an aralkyl group or an alicyclic group) which may be present in the bond of the main chain. However, T ₃ and T ₄ may be the same or different and represent the same symbols as the above T ₁ and T _2, and R ₃ may be substituted and has 1 to 1 carbon atoms.
12 represents an alkylene group, an alkenylene group or an aralkyl group, and S ₃ represents the same symbol as S ₁ above.

Further, a ₁ and a ₂ may be the same as or different from each other, and are a hydrogen atom, a methyl group, —COO—K or —CH ₂ COO—K (K is
Hydrogen atom, alkyl group / alkenyl group having 1 to 18 carbon atoms
Represents an aralkyl group or a cycloalkyl group). Further, m, n and p may be the same or different and each represents a number of 0, 1, 2, and 3. However, m and n are 0 at the same time
Never be.

Even more preferably, in formula (I), Q is -COO.
-Or And a ₁ and a ₂ may be the same or different and each represent a hydrogen atom, a methyl group, —COO—K or —CH ₂ COOK (K represents an alkyl group having 1 to 12 carbon atoms).

Further specific examples of R ₁ and R ₂ (R 'and R "represent a hydrogen atom, an alkyl group, a halogen atom, etc.), CH = CH, (T ₃ , T ₄ , S ₃ , R ₃ , and p have the same meanings as the above symbols), and the like.

Further, T ₁ , T ₂ , m, n and p represent the same symbols as described above. And linking _{groups: -QR 1 -T 1 m R 2} -T 2 n atoms of the sum of the respective atomic groups S ₁ is are those composed of 8 or more.

More specifically, the monomer (B) can be exemplified by the following compounds.

The dispersing resin of the present invention comprises at least one kind of each of the monomer (A) and the monomer (B). What is important is that the resin synthesized from these monomers is insoluble in the non-aqueous solvent. If so, a desired dispersion resin can be obtained. More specifically, it is preferable to use the monomer (B) represented by the general formula (I) in an amount of 0.05 to 10% by weight, more preferably 0.1 to 5 with respect to the insoluble monomer (A). % By weight. The molecular weight of the dispersion resin of the present invention is 10 ³ -10 ⁶ , preferably 10 ⁴ -10 ⁶ .

In order to produce the dispersion resin used in the present invention as described above, generally, the dispersion stabilizing resin and the monomer (A) as described above are used.
And the monomer (B) may be heated and polymerized in a non-aqueous solvent in the presence of a polymerization initiator such as benzoyl peroxide, azobisisobutyronitrile, and butyllithium. Specifically, a method of adding a polymerization initiator to a mixed solution of a resin, a monomer (A) and a monomer (B), a monomer (A) and a monomer in a solution in which a resin is dissolved The method of dropping (B) together with the polymerization initiator, or the mixed solution containing the entire amount of the resin and a part of the mixture of the monomer (A) and the monomer (B) is used together with the remaining amount of the polymerization initiator. There is a method of arbitrarily adding a monomer mixture, and further, a method of adding a mixed solution of a resin and a monomer together with a polymerization initiator in a non-aqueous solvent, and any method may be used. It can be manufactured.

The total amount of the monomers (A) and (B) is
0 to 5 parts by weight to about 5 to 80 parts by weight, preferably 10
~ 50 parts by weight.

The soluble resin which is a dispersion stabilizer is 1 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of all the monomers used above.

The amount of the polymerization initiator is 0.1 to 5% (weight) of the total amount of the monomers.
Is appropriate.

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

The non-aqueous dispersion resin produced according to the present invention as described above exists as fine particles having a uniform particle size distribution and, at the same time, exhibits very stable dispersibility, and is particularly repeatedly used for a long time in a developing device. However, the dispersibility is good and the re-dispersion is easy, and it is not observed at all that adhered dirt is generated on each part of the apparatus.

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

Conventionally, compounds such as methacrylate, acrylate, fatty acid vinyl, or fatty acid allyl used as the monomer (A) usually have 1 to 4 carbon atoms in the alkyl group contained in the molecule, and at most 6 It was within. This means that the produced resin is solubilized in a non-aqueous solvent and particle formation becomes difficult, or the softening point of the produced resin is lowered and the resin is weak against thermal changes and the storage stability is deteriorated. It was because of the problem of. However,
With respect to the monomer (A), a monomer (A) which contains at least two polar components copolymerizable with the monomer (A) together with the monomer (A) which polymerizes and becomes insoluble, Small amount 0.
The dispersion resin obtained by polymerizing and granulating the resin in the same amount at the same time (05 to 10% by weight) does not cause a decrease in the solubilization of the resin and the softening point of the resin as described above, which makes the resin impractical. The monodisperse resin particles having an average particle diameter of 1 are formed, and the redispersibility is remarkably improved.

Furthermore, in the non-aqueous dispersion resin of the content described in JP-A-60-185963, a monomer that polymerizes and becomes insoluble and a monomer that contains a copolymerizable long-chain alkyl group component coexist. Although the resin particles obtained by the above, as described above, the dispersibility of the particles is excellent, printing in a large-scale printing machine using a master plate for offset printing of a large plate size, or of the plate-making machine In the case of printing using an offset master plate, which was obtained when the processing speed was increased, the number of printed sheets was about 5000 to 8000.

In the case of using the particles obtained in the present invention, in printing with a large-sized printing machine of the large plate size as described above, or in printing of a master plate obtained with a plate-making machine in which the plate-making speed is accelerated, any of In this case, it was possible to print more than 10,000 sheets.

From the above experimental facts, the remarkable performance-improving effect of the present invention is that the soluble component contained in the monomer (B) is present at the particle interface of the insolubilized and dispersed resin, and the particle surface has some improvement. And that the thermal compatibility of each copolymer component in the insoluble resin particles composed of the copolymer of the monomer (A) and the monomer (B) is improved. .

If necessary in the present invention, a colorant may be used, and the colorant is not particularly specified, and various conventionally known pigments or dyes can be used.

When the dispersed resin itself is colored, for example, as one of coloring methods, there is a method of physically dispersing it in a dispersed resin by using a pigment or a dye, and many pigments or dyes to be used are known. There is. Examples thereof include magnetic iron oxide powder, powdered lead iodide, carbon black, nigrosine, alkali blue, Hansa yellow, quinacridone red, and phthalocyanine blue.

As another method of coloring, there is a method of dyeing a dispersed resin material with a preferable dye as described in JP-A-57-48738. Or, as another method,
As disclosed in JP-A-53-54029, there is a method of chemically bonding a dispersed resin material and a dye, or
Further, as described in JP-B-44-22955 and the like, there is a method of preparing a dye-containing copolymer by using a dye-containing monomer in advance in the production by the polymerization granulation method.

Various additives may be added to the liquid developer of the present invention as needed in order to enhance charging characteristics or improve image quality. For example, Yuji Harazaki "Electrophotography" Vol. 16, Vol.
No., p. 44.

For example, di-2-ethylhexyl sulfosuccinic acid metal salt, naphthenic acid metal salt, higher fatty acid metal salt, lecithin,
Examples include poly (vinylpyrrolidone) and a copolymer containing a semi-maleic acid amide component.

The amounts of the main components of the liquid developer of the present invention will be described below.

Toner particles containing a resin (and a colorant) as a main component are preferably 0.5 to 50 parts by weight with respect to 1000 parts by weight of the carrier liquid. If it is 0.5 parts by weight or less, the image density will be insufficient, and if it is 50 parts by weight or more, fog will easily occur on the non-image area. A carrier liquid soluble resin such as the above-mentioned dispersion stabilizer is also used as needed, and can be added in an amount of about 0.5 to 100 parts by weight based on 1000 parts by weight of the carrier liquid. The charge control agent as described above is preferably used in an amount of 0.001 to 1.0 part by weight based on 1,000 parts by weight of the carrier liquid. Further, various additives may be added if necessary, and the upper limit of the total amount of these additives is restricted by the electric resistance of the developer. That is, when the electric resistance of the liquid developer with the toner particles removed is 10 ⁹ Ωcm or less, it becomes difficult to obtain a high-quality continuous tone image. It is necessary to control.

The embodiments of the present invention will be illustrated below, but the contents of the present invention are not limited thereto.

Production Example of Dispersion Stabilizing Resin 1: Compound Example (a) A mixed solution of 96.7 g of lauryl methacrylate, 2.2 g of vinyl methacrylate and 400 g of isodecane was heated to 70 ° C. under a nitrogen stream. While stirring, 1.0 g of 2,2'-azobis (butyronitrile) was added, and the mixture was reacted for 3 hours.
1.0 g of 2'-azobis (butronitrile) was added and the reaction was carried out for 4 hours. The solid content concentration of the obtained solution was 19.4%.

The colorless and transparent viscous product obtained by introducing 1 part of the above reaction solution into 10 times its amount of methanol solvent had a molecular weight of 3.8 × 10 ^{4 as} measured by high performance liquid chromatography.

Production Example 2 of dispersion stabilizing resin: Compound example (b) A mixed solution of 128.7 g of stearyl methacrylate, 2.2 g of vinyl methacrylate and 300 g of isodecane under a nitrogen stream,
The temperature was raised to 75 ° C., 1.3 g of 2,2′-azobis (butyronitrile) was then added, and the mixture was stirred for 3 hours. Further 2,2'-
1.3 g of azobis (butronitrile) was added and reacted for 5 hours. The solid content concentration of the obtained solution was 30.0%.
It processed and measured like manufacture example 1. The molecular weight of the white solid is 3.
It was 5 × 10 ⁴ .

Production Example 3 of dispersion stabilizing resin: Compound example (c) Lauryl methacrylate 71.0 g, vinyloxycarbonylmethyloxycarbonylcarbonyl acrylate 2.2 g
And a mixed solution of Isopar H293g under a nitrogen stream at a temperature of 70
The mixture was heated to ℃, after which 1.1 g of 2,2'-azobis (butyronitrile) was added and stirred for 3 hours. Further, 1.1 g of 2,2'-azobis (butronitrile) was added and reacted for 5 hours.
The solid content concentration of the obtained solution was 19.6%. Production example 1
The molecular weight of the colorless and transparent viscous substance treated and treated as described in 3.
It was 5 × 10 ⁴ .

Production Example 4 of Dispersion Stabilizing Resin: Compound Example (h) A mixed solution of 59.0 g of hexadecyl acrylate, 3.1 g of allyloxycarbonyl decamethylene methacrylamide and 145 g of n-dodecane was heated to 75 ° C. under a nitrogen stream,
Then, 0.9 g of 2,2'-azobis (butyronitrile) was added and stirred for 3 hours. Further, 0.9 g of 2,2'-azobis (butronitrile) was added and the reaction was carried out for 4 hours. The solid content concentration of the obtained solution was 29.4%. The molecular weight of the white solid treated and measured as in Production Example 1 was 4.1 × 10 ⁴ .

Production Example 5 of Dispersion Stabilizing Resin: Compound Example (i) A mixed solution of 45 g of stearyl methacrylate, 1.7 g of vinyloxyethyl acrylate and 109 g of Isopar G,
After heating to a temperature of 75 ° C under a nitrogen stream, post-benzoyl peroxide 0.
7 g was added and stirred for 3 hours. Furthermore, benzoyl peroxide 0.7g
Was added and reacted for 4 hours.

The solid content concentration of the obtained solution was 29.0%. The white solid had a molecular weight of 3.8 × 10 ^4, which was treated and measured as in Production Example 1.

Production Example 1 of Resin Particles Polymer solution 41.2 obtained in Production Example 1 of resin for dispersion stabilization
A mixed solution of g, 100 g of vinyl acetate, 1.0 g of the compound of the specific example (a) of monomer (B) and 355 g of isodecane was heated to a temperature of 75 ° C. with stirring under a nitrogen stream. Benzoyl peroxide 2.
0g was added and it reacted for 4 hours. After 40 minutes from the addition of the initiator, the homogeneous solution became cloudy and the reaction temperature rose to 88 ° C. After cooling, the white dispersion obtained by passing through a 200 mesh nylon cloth was a latex having a polymerization rate of 90% and an average particle size of 0.20 μm.

Production Example 2 of Resin Particles 51.5 Polymer Solution Obtained in Production Example 2 of Dispersion Stabilizing Resin
A mixed solution of g, 100 g of vinyl acetate, 0.8 g of the compound of the specific example (b) of the monomer (B) and 345 g of isodecane was heated to 75 ° C. while stirring under a nitrogen stream. Benzoyl peroxide
2.0 g was added and reacted for 4 hours. After cooling, it was passed through a nylon cloth of 200 mesh and the white dispersion obtained had a polymerization rate of 93%.
The average particle size was 0.21 μm.

Production Example 3 of Resin Particles 30 g of the polymer solution obtained in Production Example 3 of dispersion stabilizing resin,
Vinyl acetate 100g, compound of monomer (B) specific example (G)
A mixed solution of 1.0 g and n-dodecane (375 g) was added under a nitrogen stream,
After heating to a temperature of 70 ° C., 2.0 g of 2,2′-azobis (butyronitrile) was added and reacted for 4 hours.

After cooling, it was passed through a 200-mesh nylon cloth, and the obtained white dispersion had a polymerization rate of 95% and a latex having an average particle size of 0.18 μm.

Production Example 4 of Resin Particles 30.6 Polymer Solution Obtained in Production Example 3 of Resin for Dispersion Stabilization
A mixed solution of g, 100 g of vinyl acetate, 5 g of crotonic acid, 0.5 g of the compound of the specific example (nu) of monomer (B) and 365 g of Isopar H was heated to 70 ° C. while stirring under a nitrogen stream. 2,
1.8 g of 2'-azobis (butyronitrile) was added and reacted for 4 hours. After cooling, pass a 200 mesh nylon cloth,
The obtained white dispersion had a polymerization rate of 93% and a latex having an average particle size of 0.20 μm.

Production Example 5 of Resin Particles 34 g of the polymer solution obtained in Production Example 4 of resin for dispersion stabilization,
100 g of vinyl acetate, 5 g of N-vinylpyrrolidone, 1.0 g of the compound (a) of the monomer (B) and n-dodecane 36
1 g of the mixed solution was heated to a temperature of 70 ° C. while stirring under a nitrogen stream. 1.8 g of 2,2'-azobis (butyronitrile) was added and reacted for 4 hours. After cooling, it was passed through a 200-mesh nylon cloth, and the resulting white dispersion had a polymerization rate of 92% and a latex having an average particle size of 0.18 μm.

Production Example 6 of resin particles Polymer solution 30.6 obtained in Production Example 3 of resin for dispersion stabilization
g, poly (lauryl methacrylate) 8g; vinyl acetate 100
g, a mixed solution of 0.8 g of the compound of the specific example (b) of the monomer (B) and 375 g of Isopar while stirring under a nitrogen stream,
Heated to 70 ° C. 2,2'-azobis (butyronitrile)
1.8 g was added and reacted for 4 hours. After cooling, it was passed through a 200-mesh nylon cloth, and the white dispersion obtained had a polymerization rate of 93% and a latex having an average particle size of 0.16 μm.

Production Example 7 of Resin Particles Polymer solution 41.2 obtained in Production Example 1 of resin for dispersion stabilization
g, vinyl acetate 100g, specific example of monomer (B) (L) 1.0g
A mixed solution of 353 g of isodecane and isodecane was heated to 70 ° C. while stirring under a nitrogen stream. 1.8 g of 2,2'-azobis (butyronitrile) was added and reacted for 4 hours. After cooling, the mixture was passed through a 200-mesh nylon cloth, and the white dispersion obtained had a polymerization rate of 95% and a latex having an average particle size of 0.23 μm.

Production Example 8 of Resin Particles: Comparative Example A The same procedure as in Production Example 1 of resin particles except for the compound of the specific example (a) of the monomer (B) was performed in the same manner. The latex had a polymerization rate of 85% and an average particle size of 0.22 μm.

Production Example 9 of Resin Particles: Comparative Example B In Production Example 1 of resin particles, stearyl methacrylate was used instead of the compound of Specific Example (a) of the monomer (B).
The same operation as in Production Example 1 was carried out except that 0.8 g was used.

The white dispersion obtained had a polymerization rate of 88% and an average particle size of 0.21 μm.
It was a lattex.

Example 1 10 g of poly (lauryl methacrylate), 10 g of nigrosine
And 71.30 g of Cielsol together with glass beads were placed in a paint shaker (Tokyo Seiki Co., Ltd.) and dispersed for 90 minutes,
A fine dispersion of nigrosine was obtained.

30 g of the resin dispersion prepared in Production Example 1 of resin particles, 2.5 g of nigrosine dispersion: 0.05 g of zirconium naphthenate were mixed with Sielsol 7
A liquid developer was prepared by diluting to 1.1 l.

(Comparative Developers A to B) Two types of liquid developers A and B for comparison were prepared by replacing the resin dispersion with the following resin particles in the above production example.

Comparative liquid developer A: Resin dispersion of resin particle production example 8 〃 B: 〃 9 〃 These liquid developers were used as developers for fully automatic plate-making machine ELP404V (Fuji Photo Film Co., Ltd.) ELP master II type (manufactured by Fuji Photo Film Co., Ltd.), which is a photographic light-sensitive material, was exposed and developed. Further, after processing 2000 sheets of ELP master II type, the presence or absence of toner adhesion stain on the developing device was observed. The results are shown in Table 1.

The offset printing master plate (ELP / master) obtained by using the developer of the present invention and Comparative Example B was printed as a printing plate, and characters such as missing characters and solid spots were generated in the image of the printed matter. When the numbers of printed sheets were compared, the offset master obtained using the developer of the present invention did not occur even after 10,000 or more sheets and the master plate using Comparative Example B occurred at 8,000 sheets.

As described above, only the developer using the resin particles of the present invention as the developer did not cause the developing device to be contaminated at all, and the number of prints on the master plate was significantly improved.

That is, in the case of Comparative Example A, the developing device was contaminated; in the case of Comparative Example B, the developing device was not contaminated, but the number of printable sheets in printing was not sufficient.

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

Example 2 A mixture of 100 g of the white background dispersion liquid obtained in Production Example 1 of resin particles and 1.5 g of Sumicaron black was heated to a temperature of 100 ° C.,
The mixture was heated and stirred for 4 hours. After cooling to room temperature, a 200 mesh nylon cloth was passed through to remove the residual dye, thereby obtaining a black resin dispersion having an average particle size of 0.20 μm.

32 g of the above black resin dispersion, zirconium naphthenate 0.0
A liquid developer was prepared by diluting 5 g of Cielsol 71.1.

When this was developed by the same apparatus as in Example 1, 2000
Even after the development of one sheet, the toner adhered to the apparatus did not stain at all.

The image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after printing 10,000 sheets was also very clear.

Example 3 A mixture of 100 g of the white dispersion obtained in Production Example 4 of resin particles and 3 g of Victoria Blue B was heated to a humidity of 70 ° to 80 ° C. and stirred for 6 hours. After cooling to room temperature, pass through a 200 mesh nylon cloth to remove residual dye, and average particle size 0.20 μm
Was obtained as a blue resin dispersion.

32 g of the above blue resin dispersion, zirconium naphthenate 0.0
A liquid developer was prepared by diluting 5 g to Isopar H / l.

This was developed with the same apparatus as in Example 1, and
Even after development of 00 sheets, no toner adhesion stain was found on the apparatus. The image quality of the obtained master plate for offset printing was clear, and the image quality of the printed matter after printing 10,000 sheets was also very clear.

Example 4 32 g of the white resin dispersion obtained in Production Example 2 of resin particles, 2.5 g of the nigrosine dispersion obtained in Example 1 and half-docosanil amidation product of a copolymer of diisobutylene and maleic anhydride.
A liquid developer was prepared by diluting 02g into Isopar G1.

When this was developed by the same apparatus as in Example 1, 2000
No toner adhesion stain was found on the device even after development of one sheet. 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 clear.

After this developer was allowed to stand for 3 months, the same treatment as above was carried out, but it was completely the same as before the passage of time.

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

30 g of the white resin dispersion obtained in Production Example 3 of resin particles,
4.2 g of the above alkali blue dispersion, and a half-docosanil amidation product of a copolymer of diisobutylene and maleic anhydride
A liquid developer was prepared by diluting 0.02g into Isopar G1.

When this was developed by the same apparatus as in Example 1, 2000
Even after sheet development, no toner adhesion stains were observed on the apparatus. Further, 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.

Continuation of the front page (72) Inventor Sera Hideshi, Kawajiri 4000, Yoshida-cho, Haibara-gun, Shizuoka Prefecture Fuji Sha Photo Film Co., Ltd. Examiner Hiroshi Fukatsu (56) References JP-A-60-185963 (JP, A)

Claims (1)

[Claims] 1. An electric resistance value of 10 ⁹ Ω · cm or more and a dielectric constant of
In a non-aqueous solvent of 3.5 or less, in a liquid developer for electrostatic photography, in which at least a resin is dispersed, the monomer forming the resin is soluble in an organic solvent, A monomer capable of forming a polymer insoluble in a solvent (monomer (A)) and at least one type represented by the following general formula (I) in an amount of 0.05 to 10% by weight based on the monomer (A). Which is a monofunctional monomer (monomer (B)), and the resin comprises a monomer (monomer (C)) represented by the following general formula (II) and the following general formula (III) Is a resin obtained by a polymerization reaction in a solution containing a copolymer resin soluble in the non-aqueous solvent obtained by polymerizing the monomer (monomer (D)) Characteristic liquid developer for electrostatic photography. General formula (I) In the general formula (I), Q is -O-, -COO-, -OCO-,
_{-CH 2 OCO -, - SO 2} -, Or [W represents a hydrogen atom, a hydrocarbon group or a bonding group R ₁ -T _{1 m} R ₂ -T _{2 n} S ₁ in the general formula (I)]. S ₁ is a hydrogen atom, a halogen atom, -OH, -CN, -NH
_2, -COOH, represent -SO ₃ H, a hydrocarbon group -PO ₃ H carbon atoms which may be substituted with 1 to 18. T ₁ and T ₂ may be the same or different from each other, and are —O—,
-S -, - CO -, - CO 2 -, - OCO -, - SO 2 -, Represents —NHCO ₂ — or —NHCONH— (S ₂ represents the same symbol as S ₁ above). R ₁ and R ₂ may be the same or different from each other and may be substituted or Represents a hydrocarbon group having 1 to 18 carbon atoms which may be interposed in the bond of the main chain (however, T ₃ and T ₄ may be the same or different from each other, and the same symbols as those of T ₁ and T ₂ R ₃ represents an optionally substituted hydrocarbon group having 1 to 18 carbon atoms, and S ₃
Represents the same symbols as S _1. ] Further, a ₁ and a ₂ may be the same or different from each other, and are a hydrogen atom, a hydrocarbon group, —COO—K or —COO via a hydrocarbon.
-K (K represents a hydrogen atom or a hydrocarbon group which may be substituted), m, n and p may be the same or different and each represents an integer of 0-4. However, m and n are never 0 at the same time. Further, the total number of atoms of binding to atomic bonding group _{-QR 1 -T 1 m R 2 -T} 2 n S 1 is 8 or more. General formula (II) In formula (II), L is an aliphatic group having 8 or more carbon atoms, and Y ₁ and Y ₂
May be the same or different and each represents a hydrogen atom or an alkyl group. General formula (III) In formula (III), X is -COO-, -CONH- or (R ₆ represents an aliphatic group), Y is a group connecting the functional group X and the atomic group Z with a carbon atom which may have a hetero atom, and Z is the atomic group Y. In group linking the _{door, -COO -, - COOCH 2 -} , - O -, - S
O ₂ −, or Represents However, when X represents -COO-, it does not go through Y and Z, but directly. May be combined with Y ₃ , Y ₄ and Y _{5, which} may be the same or different, each represents a hydrogen atom or an alkyl group.