JPS6160715A - Nonaqueous resin and electrostatic photography liquid developer containing same - Google Patents

Abstract

PURPOSE:The title composition which has electric charges in an organic solvent and is useful as, e.g., an electrostatic photography liquid developer which can give an image excellent in fixation, durability and storage stability, prepared by polymerizing a system comprising specified monomers A and B in a specified organic solvent. CONSTITUTION:A nonaqueous resin prepared by polymerizing a system comprising monomer A of formula I [wherein R1 is H or CH3, X is a group of formula II or III (wherein n is 6-20)], e.g., dodecyl methacylate, and monomers B of formulas IV and/or V (wherein R1 is H or CH3, R2 is H, Na, K or Li and n is 1-22), e.g., a compound of formula VI or VII, in the presence of a polymerization initiator (e.g., azobisisobutyronitrile) in an aliphatic hydrocarbon solvent (e.g., isooctane). This resin has electric charges in a nonaqueous solvent, is excellent in charge control and fixation as a binder for paints, printing inks and electrophotographic toners. An electrostatic photography liquid developer containing this resin is excellent in image fixation and improved in durability and storage stability.

Description

Detailed Description of the Invention Technical Field The present invention relates to a non-aqueous resin and an electrostatographic liquid developer containing the same, and the resin can be used in paints, printing inks,
It can also be applied to adhesives and the like.

Prior Art Conventionally, known monomers having polar groups include acrylic monomers, methacrylic acid, itacon #t, maleic monomers,
7 maric acid, hydroxyethyl acrylic V-), and glycidyl methacrylate. In these polymers, the polar groups ionically dissociate in an aqueous solvent, but do not ionically dissociate in a nonaqueous solvent, and no charge is observed on the polymer.Methods such as ionizing the carboxyl groups with a base are used.
In this case, the balance between bases was poor and it was not possible to have a stable charge ft.

General liquid developers for electrostatography mainly consist of a colorant such as carbon black, organic pigment or dye, and a binder such as a synthetic or natural resin such as acrylic resin, phenol-modified alkyd resin, rosin, or synthetic rubber. A toner containing a polarity control agent such as lecithin, metal soap, linseed oil, or higher fatty acid is mixed with a carrier liquid whose main component is a highly insulating, low dielectric constant solvent such as a petroleum-based aliphatic hydrocarbon. It is dispersed inside. In the development process, such toner causes aerophoresis according to the charge of an electrostatic m image formed on the surface layer of an electrophotographic photosensitive material or an F# electrorecording material, and adheres to that part to form an ll1j image. However,
In conventional liquid developers, resins and polarity control agents diffuse into the carrier liquid over time, causing aggregation and making the polarity unclear, resulting in significant deterioration of image quality, especially image performance. In addition to the problems, the adhesion of the toner and therefore the fixation of the image are weak, and the durability of continuous copying (
The number of copies required to reduce the image density to a predetermined value was insufficient. The lack of durability is thought to be due to the fact that the pigment and resin constituting the toner are not adsorbed to the era name in the carrier liquid, and the compositional balance of the developer changes with the number of copies.

Purpose The present invention was made to solve the above-mentioned drawbacks, and the present invention was made to solve the above-mentioned drawbacks.
Excellent at dispersing pigments.

The purpose is to provide a binder for paints, printing inks, and electrophotography that has excellent fixing properties and charge control properties.

More specifically, it has the ability to form high-quality images by improving the storage stability of the toner and improves its storage stability, and improves the fixability of the image by improving the adhesion of the toner. Please improve the adsorption power between pigment and resin.)
An object of the present invention is to provide an electrostatographic liquid developer capable of forming stable color images.

Structure The present invention has been made to achieve the above object.

In the present invention, in the presence of a polymerization initiator in an aliphatic hydrocarbon solvent, the general formula (A) λ (wherein R8 is -H or -""s*X is -COOC
nH2n + 1 or 10-Co-CnH1m+1
, n is an integer of 6 to 20) and general formula (B-1) and/or general formula (B-2) (
However, R1 is -H or -CE'ls * Rt k
1, N&.

K, Ll, n is an integer from 1 to 22, and in a carrier liquid mainly composed of a non-aqueous resin and a petroleum-based aliphatic hydrocarbon obtained by polymerizing a system containing at least a monomer B represented by In an electrostatographic liquid developer comprising a toner containing a colorant and a binder resin as main components dispersed therein, a general formula (but not limited to , R1 is -R or 10) Is, X is -C00
CnH1rs+ 1 or -0-Co-CnH1n+
1, n is an integer from 6 to 20) and the general formula (B-1) and/or the general formula (B-2
) (However, %R3 is 1 ■ or -C) I, , - is Ei,
Na.

IC, Ll,! The present invention is an electrostatic photographic liquid developer containing a non-aqueous resin obtained by polymerizing a system containing at least a monomer B (I is an integer from 1 to 22).

Solvents used in the present invention include petroleum aliphatic hydrocarbons or halogenated aliphatic hydrocarbons, such as kerosene, ligroin, n-hexane, n-heptane, n-octane, l-octane, l-dodecane (commercially available Exxon products include Isopar H, G, L, Naphtha 16, Tsurpez 100, etc.), carbon tetrachloride, perfluoroethylene, and the like. A small amount of an aromatic solvent such as toluene or xylene may also be added to these aliphatic solvents.

As the polymerization catalyst, a normal radical polymerization catalyst is used.
Specific examples include benzoyl di-t-butyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide), t-7't-7' t-t-butyl peroxide, t-7'-f ruperhensoate, and methyl isobutyl ketone. Peroxide, lacroyl peroxide, cyclohexyl peroxide, 2,5-dimethyl-2,5
-di-1-butyl peroxyhexane, t-7' tyl peroctanoate, t-butyl perisobutyrate, t
-Organic peroxides such as butyl peroxyinopropyl carbonate Jf% Methyl-2,2'-azobisisobutyrate, 1.1'-7zobiscyclohexanecarponitrile, 2-phenyla I-2,4-dimethyl -Azo compounds such as 4-methoxyvaleronitrile, 2-carbomoyl azobisisobuderonitrile, 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobisinbutyminitrile, etc. can be mentioned. The appropriate amount of the catalyst to be used is about 0.1 to 2.0% by weight based on the total weight of the monomers.

Specific examples of monomers used in the present invention are lauryl methacrylate, lauryl acrylate, stearyl methacrylate, stearyl acrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate.

Examples include dobucul methacrylate, dodecyl acrylate, hexyl methacrylate, hexyl acrylate, octyl methacrylate, octyl acrylate, cetyl methacrylate, cetyl acrylate, vinyl laurate, and vinyl stearate.

Examples of monomer B used in the production of the resin of the present invention include the following.

隘3 し Uυh II 翫 10 ARASHI 12 υ IL14 翫 15 %16 YORSHIP 8 DEN 19! 1&L20 Positive 21 On the other hand, monomer A has the property of solvating with the solvent both before and after polymerization. Therefore, the obtained comonomer has the monomer B component as the center in the solvent, and the monomer A component solvated with the solvent is dispersed in a bonded state around the monomer B component. Here, the monomer A component in the copolymerization contributes to improving the dispersion stability (and therefore storage stability) and adhesion of the toner.
I will. The ratio of monomer B to monomers is 0.
Approximately 01 to 1:1 (IL) is suitable. In addition, these monomer A and monomer B components contain other polymerizable heptamers.
(hereinafter referred to as monomer C) can be added, and the usage ratio of monomer C to monomer A is 0.01 to 1.
; 1 (miL) 8 degrees is appropriate. Monomer B is a polymer, and unlike acrylic acid, it does not dissolve well in aqueous solutions, but has the property of being solvated in non-aqueous solvents. Therefore, it can be considered that in copolymerization with a long-chain acrylic ester, an organic polar elimer having a carboxyl group generates an appropriate amount of carboxylate anion, inducing charge generation in the polymer.

In the present invention, polymers that are soluble in non-aqueous solvents, partially gelled semi-soluble polymers, and particulate YTR IJ mom-insoluble polymers can be prepared by known methods.

Examples of monomers used in the present invention include styrene, vinyltoluene, vinyl acetate, acrylic acid or methacrylic acid, or their alkyl (carbon number: 1 to 5) esters (
For example, methyl methacrylate, ethyl acrylate, methyl acrylate, ethyl methacrylate, butyl methacrylate], polyhydric alcohol di(meth)acrylate (e.g. ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol methacrylate, diethylene glycol triacrylate) Acrylate, triethylene glycol trimethacrylate, butanediol diacrylate, butanediol dimethacrylate, 1
．． 6-hexanediol diacrylate% 1.6-hexanediol diacrylate, trimethylolhexane triacrylate.

Trimethylolzolonone trimethacrylate.

Tetramethylolmethane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethanetetraacrylate, tetramethylolmethanetetramethacrylate, diprotolene glycol diacrylate, dipropylene glycol dimethacrylate, trimethylolhexane triacrylate, trimethylolhexane trimethacrylate, penta Erythritol tetraacrylate, pentaerythritol tetramethacrylate, 1,3-butylene glycol diacrylate), 1
．． 3-7' ethylene glycol dimethacrylate, trimethylolethane triacrylate, trimethylolethane methacrylate, allyl methacrylate, methalyl methacrylate, etc., 0-divinylbenzene, m-') vinylbenzene, p-divinylbenzene, p-methyldivinylbenzene , 0-ethyldivinylbenzene, p-butyldivinylbenzene, m-hexyldivinylbenzene%
0-nonyldivinylbenzene, p-decyldivinylbenzene, o-') undecyldivinylbenzene, p-stearyldivinylbenzene, O-methyldivinylbenzene, 0-ethyldivinylbenzene, p-hexyldivinylbenzene, p-/ Nyldivinylbenzene, m-decyldivinylbenzene7. Examples include p-undecyldivinylbenzene and 〇-stearyldivinylbenzene.

In the present invention, silica fine particles, wax or polyolefin having a softening point of about 60 to 13 G'C can be added to the copolymer manufacturing process. When fine silica particles are used, it is thought that the copolymer is obtained in a state in which the silica particles are incorporated in its network structure. Note that silica itself does not undergo physical changes such as dissolution during the reaction. In any case, silica is useful for improving toner dispersion stability because its specific gravity is similar to that of the aliphatic hydrocarbon or halogenated aliphatic hydrocarbon medium used as the dispersion medium, and because it prevents gelation of the copolymer. Helpful. -・way.

When wax or polyolefin is used, it is dissolved in one reaction system during the polymerization reaction, and after the reaction, it is precipitated in the form of fine particles in this system upon cooling. It is believed that the copolymer can thus be obtained adsorbed or mixed with wax or polyolefin microparticles. Here, wax or polyolefin, like silica, has a specific gravity similar to that of the dispersion medium, and in addition to preventing gelation of the copolymer, the molecular structure is also similar to that of the dispersion medium, so wax or polyolefin is only useful for improving the dispersion stability of the toner. Since it has a low softening point, it also helps improve adhesion (fixing properties). The amount of silica, wax or polyolefin added is 5 to 50 parts by weight per 100 parts by weight of the copolymer.

Further, specific examples of commercially available waxes or polyolefins having a softening point of 60 to 130°C are as follows.

Union Carbide (USA) DYNI
102DYNF 102 DYNH102 DYNJ 102 DYNK 102-syfy) (
US) ORE, IZON 805 116
#705 116 Philips (USA) MARLEX 1005
92 Dupont (USA) ALATHON −
3103 Manufacturer Product name Softening point (to)
Allied Chemical (US) AC-Boη Ethylene 1
702 98// 6&-6A
102 Sanyo Chemical Sunwax 13
1-F' 108// 151-P
107// 161-P 1 11
#165-P2O3 // 171-P 105//l-20
095 Gensei Kagaku Norifin Wax 6
0-98 Kobayashi Kako Sarashi Mitsuro 5 65 Setanol 80 Mizuben Kako Sarashi Mitsuro 65 Steel Chemical
70-Cen 110 Production examples and examples of copolymers are shown below.

Production Example 1 300 I of isooctane was placed in a 2-OL four-bottle flask equipped with a stirrer, a thermometer, and a reflux condenser. Take 95″
CK was heated. In this, dodecyl methacrylate 190
．． 9% 0-butyldivinylbenzene10. p, Monomer B (4) 20J and azobisisobutyronitrile 6
After a solution consisting of I was added dropwise over 3 hours, the mixture was heated and stirred at the same temperature for an additional 1 c4 hours to carry out a polymerization reaction to obtain a resin liquid with a polymerization rate of 96.2% and a viscosity of 180 cp.

Preparation Example 2 The resin dispersion 300Ii obtained in Preparation Example 1 was mixed with colloidal silica xog in a flask.

After heating at 100° C. for 3 hours, the mixture was cooled to obtain a colloidal silica-containing resin dispersion having a viscosity of 160 cp and a particle size of 0.3 to 0.4 μm.

Production Example 3 Isododecane 3001 was placed in the same flask as in Production Example 1 and heated to 90''CK.Next, 25 lauryl methacrylate 300i monomers B (ffil), allyl methacrylate 28I, and benzoyl peroxide 31 were added to the flask.
A different solution was added dropwise over 1.5 hours, and the temperature was further heated to 95°C.
The polymerization reaction was carried out by heating and stirring for 4 hours, and the polymerization rate was 9G.
A resin solution having a viscosity of 180 cp was obtained by adding 50 JI of vinyl toluene and 11 benzoyl peroxide dropwise to the resin solution at 90° C. and polymerizing for 4 hours. Polymerization rate: 94.
6%, the polymer had a negative charge of π.

The charge measurement of the polymer was carried out as follows.

Take 25 g of a 3 wt % polymer dispersion in kerosene in a 1001 beaker, and set the electrode spacing to 20 g. wing x40
An applied voltage of 1000 V is applied between the 11 copper electrodes.

In the judgment, a polymer electrodeposited on the positive electrode was classified as a negatively charged polymer, and a polymer electrodeposited on the negative electrode was classified as a positively charged polymer.

Production Example 4 Resin dispersion i 3009 obtained in Production Example 3 was mixed with 20 g of bleached beeswax in a flask, and heated at 90°C for 2 hours and 11 hours.
After 1 stirring, it is cooled to a viscosity of 160 cp and a particle size of 0.1~
A resin dispersion liquid of 1.0μ was obtained. PoIJ -r- had a negative charge.

Production example 5 Sunwax 171P300 in the same flask as production example 1
F was taken and heated to 90°C. In this, 2-ethylhexyl methacrylate 15ON, monomer B (lI4A
xs) so! 1. A solution of p-divinylbenzene 2079 and lauroylnoseoxide 6,3I was added dropwise over a period of 3 hours, and the polymerization reaction was carried out by further stirring at the above temperature for 4 hours, resulting in a polymerization rate of 97.3% and a viscosity of 180. c.
A resin dispersion having a p1 particle size of 0.15 to 0.33 μm was obtained.

The polymer had a positive charge.

Production Example 6 Add 300 g of Ainno #-L to the same flask as Production Example 1.
and polyethylene (AC-6 manufactured by Allied Chemical Company) 6
0JI was added and heated to 95°C.

Next, in this, 180 g of stearyl methacrylate, 20 g% of monomer B (ru 11), 20 g% allyl methacrylate.
9 and lauryl peroxide 41 were added dropwise over a period of 3 hours, and further stirred at the above temperature for 3 hours to carry out a polymerization reaction, resulting in a polymerization rate of 95.4%, a viscosity of 180 ep, and a particle size of 0.5 to 0. , a resin dispersion of 8μ was obtained. The polymer carried a negative charge.

Production Example 7 Iso'-FI 30011 was added to the same flask as Production Example 1.
1 cetyl methacrylate-h18 (Ml, Dobucle acrylate 409.methallyl methacrylate) 15. 30 g of 1 monomer B (1V&L7) and 39 g of benzoyl peroxide were taken, and a polymerization reaction was carried out at 90'C for 6 hours to obtain a resin dispersion with a polymerization rate of 97%, a viscosity of 140 cp, and a particle size of 0.8 to 2 .mu.m. / Rimmer had a positive charge M.

Production Example 8 300p of isooctane was placed in a 2.0L four-bottle flask equipped with a stirrer, a thermometer, and a reflux condenser, and heated to 95°C.

A solution of dodecyl methacrylate 190II, methacrylic filOF, monomer i(ffi2) 1op, and azobisisobutyronitrile 6I was added dropwise to this solution over a period of 3 hours, and the mixture was further stirred at the above temperature for 4 hours to carry out the polymerization reaction. The polymerization rate was 94.0% and the viscosity was 200 cp.
A resin dispersion gY was obtained.

Manufacturing example 9 &! Preparation Example 8 300 I of the obtained resin dispersion was mixed with 10 jl of colloidal silica in a flask and heated at 100°C for 3
After heating for an hour and cooling, the viscosity is 270ap and the particle size is 4 to 6.
A resin dispersion containing microscopic powder of 7 μm was obtained.

Production Example 10 Isododecane 3009 was taken in the same flask as Production Example 8 and heated to 90°C. Next, lauryl methacrylate 3 Q O, 9% N-vinylpyridine 51. Monomer B
(4) A solution of 23J and benzoyl peroxide 31) was flowed south for 1.5 hours, and then stirred at the above temperature for 4 hours to carry out a polymerization reaction, with a polymerization rate of 94.0% and a viscosity of 230c.
p.

A resin dispersion having a particle size of 3 to 4.7 μm was obtained.

Production Example 11 300g of the resin dispersion obtained in Production Example 10 was exposed in a flask, mixed with beeswax 2 (M+), stirred at 95°C for 22 hours, cooled, and exposed to a viscosity of 280 cp and a particle size of 6 to 8μ. A beeswax-containing resin dispersion was obtained.

Production Example 12 Aitsuno #-G3001 and 30 fine silica powder in the same 7 lasco as Production Example 8! Take i, add it to 90℃,
2-ethylhexyl methacrylate 151. Glycidyl methacrylate 15g, Nanatsuma-B(-7)2
ON, methyl methacrylate) 40II and lauroyl peroxide 6.311 were added dropwise, and the polymerization reaction was carried out by further stirring at the above temperature for 4 hours. A resin dispersion of 280 ap and a particle size of 2 to 3 μm was obtained.

Production Example 13 Add Iso-L 3001 to the same flask as Production Example 8.
and polyethylene (AC-6 manufactured by Allied Chemical Company) 6
0. p was added and heated to 95°C.

Next, stearyl methacrylate 18011 lauryl methacrylate 4011. A solution consisting of fumaric acid 3F, monomer B (-9) 2 ([1) and lauryl peroxide 49 was added dropwise over 3 hours, and further added at the same temperature for 3 hours.
The polymerization reaction was carried out by stirring for a period of time, and the polymerization rate was 93.0%.
A resin dispersion having a viscosity of 580 cp and a particle size of 2.5 to 3 μm was obtained.

Production Example 14 In the same flask as Production Example 8, Isopar H3O09 and cetyl methacrylate 180. p, dodecyl acrylate 401. Nanatsuma-B (slow 10) 15I, acrylic acid 51
and benzoyl peroxide 311 were collected and stirred at 90°C for 6 hours to perform a polymerization reaction, with a polymerization rate of 97.0% and a viscosity of 3.
A resin dispersion of 70 ap and a particle size of 1 to 3 μm was obtained.

In order to make an 'rL developer using the copolymer thus obtained, generally 0.3 parts of the copolymer is added to 1 part by weight of the colorant.
~3 parts by weight of the aliphatic hydrocarbon or halogenated aliphatic hydrocarbon carrier gxo~20:dj is sufficiently dispersed in the presence of a dispersing machine such as an attritor, a ball mill, or a kedimir. The condensation toner may be first diluted 5 to 10 times with a similar solvent. In this case, the copolymer liquid obtained as described above can be used as the copolymer and solvent.

Further, when preparing the condensed toner, other resins other than the copolymer of the present invention or a polarity control agent such as a metal soap may be added to the mixture as necessary. The developer obtained in this way has a low viscosity, so it is easy to handle, can be sufficiently sucked when toner is supplied to a copying machine, and has the advantage that it does not harden easily even when stored for a long period of time.

Next, one material used in the present invention will be explained.

Examples of the layer colorant include dyes or pigments such as carbon black, oil blue, alkali blue, phthalocyanine green, spirit black, aniline black, oil violet, benzidine yellow, methyl orange, brilliant carmine, fast red, and crystal violet.

Other resins that can be added to the present preparation include acrylic resins; ester gums; natural resins such as hardened rosin; maleinha resins modified with these natural resins, phenolic resins, polyesters, pentaerythritol resins, and the like.

Examples of the present invention are shown below.

Example 1 Carbon black 109 (5-ben 100 manufactured by Colombian Carbon) Resin dispersion obtained in Production Example 1 50I Isopar G
10019 was dispersed for 6 hours using a kedimir, and the viscosity was 17. A concentrated toner of Oap was prepared, and the lOI was dispersed in kerosene 12 to prepare a electrophotographic liquid developer.

When this developer was put into a commercially available photocopying machine and copies were made on commercially available zinc oxide photosensitive paper, copies with an image fixation rate of 8% and an image fixation rate of 8% and 0% were obtained.

Furthermore, the fixation rate - is 'f(
ll image density).

In addition, when we investigated the durability of the developer by performing continuous copying until the image density decreased to 0.60, we found that it was 12.0.
00 sheets, which was good.

Further, the developing solution was stored at 50° C. for 3 months to forcefully deteriorate the image, and then copying was performed as described above to determine the image density, which was 1.29 and showed almost no deterioration.

Examples 2 to 11 Using the pigments, resins, and dispersion medium shown in Table 1, liquid developers were prepared in the same manner as in Example 1 according to the dispersion method described in the table, and the same tests as in Example 1 were conducted. The results shown in Table 2 were obtained.

(Table 2) Effects As described above, according to the present invention, a resin can be obtained which has a charge in a non-aqueous solvent, is excellent in dispersing pigments, and has excellent fixing properties and charge control properties.

Furthermore, according to the present invention, by containing the resin, the polarity of the toner is made clear and storage stability is improved,
By improving the adhesion of the toner to improve image fixing and increasing the adsorption power between the pigment and the resin, a 1E photographic liquid developer capable of forming stable color images is obtained.

Claims (1)

[Claims] 1. In the presence of a polymerization initiator in an aliphatic hydrocarbon solvent, general formula (A) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (A) (However, R_1 is -H or -CH_3 , X is -CO
OC_nH_2_n_+_1 or -O-CO-C_n
Monomer A represented by H_2_n_+_1, n is an integer from 6 to 20), General formula (B-1) and/or General formula (B-2) ▲ Numerical formula,
There are chemical formulas, tables, etc. ▼ (B-1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (B-2) (However, R_1 is -H or -CH_3, R_2 is H
, Na, Li, and n is an integer of 1 to 22). 2. An electrostatic photographic liquid developer comprising a toner containing a colorant and a binder resin as a main component dispersed in a carrier liquid containing a petroleum-based aliphatic hydrocarbon as a main component, wherein the resin is an aliphatic hydrocarbon. In the presence of a polymerization initiator in a solvent, general formula (A) ▲Mathematical formulas, chemical formulas, tables, etc.▼(A) (However, R_1 is -H or -CH_3, X is -CO
OC_nH_2_n_+_1 or -O-CO-C_n
Monomer A represented by H_2_n_+_1, n is an integer from 6 to 20), General formula (B-1) and/or General formula (B-2) ▲ Numerical formula,
There are chemical formulas, tables, etc. ▼ (B-1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (B-2) (However, R_1 is -H or -CH_3, R_2 is H
, Na, Li, and n is an integer of 1 to 22).