JPS6160714A - Nonaqueous resin composition and electrostatic photography liquid developer containing same - Google Patents

Abstract

PURPOSE:The title composition which has electric charges in a nonaqueous 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 compris ing monomer A of formula I [wherein R is H or CH3, X is a group of formula II or III (wherein n is 6-20)], e.g., dodecyl methacrylate, and monomer B of formula IV and/or formula V (wherein R is H or Ch3, n is 1-20, M1 is H, Na, K or Li, M2 is Ca, Mg, Co or Mg), e.g., a compound of formula VI or VII 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 elecrophotographic toners. An electro static 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 Summary The present invention relates to a non-aqueous resin composition and an electrostatic photographic liquid developer containing the same. It can also be applied to

Prior Art Conventionally known polymerizable monomers having a single polar group are:
Acrylic acid, methacrylic acid, itaconic acid, maleic acid,
These include fumaric acid, hydroxyethyl acrylate, 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.

A method such as ionizing a carmexyl group with an #i group has been used, but in this case, the acid-base non-container is difficult to disintegrate and a stable charge cannot be obtained.

Conventional general electrostatographic liquid developers are made of a combination of a coloring agent such as Rikizen black, an organic pigment or dye, and a synthetic or natural resin such as acrylic resin, phenol-modified alkyd resin, rosin, or synthetic rubber. The main ingredient is
A toner containing a polarity control agent such as lecithin, metal soap, flaxseed, or higher fatty acid is added to a medium liquid containing a highly insulating, low-inductivity solvent such as petroleum-based aliphatic hydrocarbon as the main component. It is dispersed. During the development process, such toner undergoes electrophoresis according to the charge of the electrostatic latent image formed on the surface layer of the electrophotographic photosensitive material or electrostatic recording material, and adheres to that area to form an image. However, in conventional liquid developers, the resin and polarity control agent diffuse into the carrier liquid over time, causing aggregation and making the polarity unclear, resulting in significant deterioration of image quality and sometimes image density. In addition to the problems, the adhesion of the toner and therefore the fixation of the image are weak, and the durability when making continuous copies (one copy until the image density drops to a certain level) is poor.
was in short supply. The lack of durability is thought to be because the pigment and resin constituting the toner are not sufficiently adsorbed in the carrier liquid, and the composition of the developer deteriorates with the number of copies.

Purpose The present invention has been made in view of the above-mentioned drawbacks, and an object of the present invention is to provide a resin having a charge in a non-aqueous solvent, which has excellent dispersibility for pigments, etc., and which can be used in paints, printing in, and electrophotography. As a binder for toner, it provides a resin with excellent charge control and fixing properties.

Another object of the present invention is to provide an electrostatographic liquid developer capable of forming high-quality images by clarifying the polarity of the toner and improving its storage stability, and further improving the adhesion of the toner. In particular, it is an object of the present invention to provide a developer which completely improves the fixability of P2 images, and which can form stable color images by increasing the adsorption power between pigment and resin.

The non-constructive invention was made to achieve the above purpose.

In the present invention, in the presence of a polymerization initiator in an aliphatic hydrocarbon solvent, the following general formula (1) OH, -0-R 1 (■) (wherein R is -H4 or -0I (s), and X is 10
〇 〇 〇 n Hz n + 1 or 10000n
Hsn+xsn is an integer of 6 to 20 (7)) and an integer of the following general formula (1) and/or 1), Ml is H, Na, K or Ll, M is Os, Mu, Oot or Mg).

The present invention further provides an e'rs photographic liquid developer comprising a toner containing a colorant and a binder resin as main components dispersed in a carrier liquid containing a petroleum-based aliphatic hydrocarbon as a main component. In the presence of a polymerization initiator in an aliphatic hydrocarbon solvent, the following general formula (1) % formula % (where 几 is -H or -0)1. , X is 10000
nH1n+x or 10000nHmtL+s, n is an integer from 6 to 20) and the following general formula C) and/or Ren) Ml (where R is -H or 10HI, II is 1) An integer of ~20, Ml is H, Na, X or Ll1M1' is Oa.

An electrostatographic liquid developer containing a non-aqueous resin composition obtained by polymerizing a system containing at least a monomer B represented by MnrOo or Mg. .

Solvents used in the present invention include petroleum-based aliphatic hydrocarbons or halogenated aliphatic hydrocarbons, such as kerosene, ligroin, n-hexano, n-hebutane, n-octane,
Examples include 1-octane, 1-dodecane (commercially available products include Exxon's Isono H, G, L, Naphtha Lim 6, Nrubetsuso 100, etc.), carbon tetrachloride, perfluoroethylene, and the like. A small amount of an aromatic solvent such as toluene or xylene can also be added to these aliphatic solvents.

As the polymerization solvent, ordinary radical polymerization catalysts can be used, and specifically, benzoyl oxide, di-t-butyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, t-butyl peroxide, t-butyl peroxide, etc. Benzoate, methyl imptyl ketone peroxide, lafuroyl peroxide, cyclohexyl peroxide, 2,5-dimethyl-2,5-di-t-butyl peroxyhexane, t-butyl peroctanoate, t-butyl peroxide Organic peroxides such as inzotyrate, t-butylperoxyinopropylcarbonate, methyl-2,2'-7zo♂sinbutyrate, 1
゜1, /-azobiscyclo to Φsancarzenitrile, 2
-Phenylua I-z, 4-dimethyl-4-methoxyno 9
Examples of azo compounds include leronitrile, 2-calzemoyl-azobisisobutyronitrile, 2,2-azogysu-(2,4-dimethylnonereronitrile) 2,2'-azobisisobutyronitrile, etc. It will be done. The amount of the polymerization catalyst used is preferably about 0.1 to 2.0 k by weight based on the total amount of monomers.

Specific examples of monomers include lauryl acrylate,
lauryl acrylate, stearyl methacrylate, stearyl acrylate, 2-ethylhexyl methacrylate), 2-1-thyl hexyl acrylate, dodecyl methacrylate, dodecyl acrylate, hexyl methacrylate, hexyl acrylate, octyl methacrylate, octyl acrylate, cetyl methacrylate,
Examples include cetyl acrylate, vinyl laurate, and vinyl stearate.

As a specific example of monomer B, 11 0H1=0 (0Hs) Grave 2 0H%OH Bu3 0H2=O (0Hs) Peek 44 0 Hz = OH & 5 0 Hz = G (OH3) A6
0) (2=OH M7 0)(,=O(0)(3)00H 16130H,=O(OH,) % 14 0Ht=O(0Hx) (Ja K15 0H1=OH M160f(2:0- OH gog A17 C!H,=O1( 0ONm A18 0H2-so-OH3 ■ 419 0 Hz= OH turtle A 2 o OH!= OOHs421
0H1=O-H On the other hand, monomers have the property of solvating with the solvent both before and after polymerization. Therefore, the resulting copolymer has the monomer B component as the center in the solvent, and the monomer component solvated with the solvent is dispersed around it in a bonded state. Here, the monomer component in the copolymer contributes to improving the dispersion stability (and therefore storage stability) and adhesion of the toner. Note that the ratio of monomer B to monomer AK is 0.0
A ratio of about 1 to 1:1 (by weight) is appropriate. Further, other polymerizable additives (hereinafter referred to as monomer 0) can be added to these monomers and monomer B component. In this case, the usage ratio of Nanatsuma-0 to monomer people is 0.0
Approximately 1 to 1 j 1 (l [(amount)) is appropriate.

Monomer B is (0H10H1)! l +Ofi: An organic polar monomer having the property of not being well soluble in aqueous solutions like acrylic acid, but solvating in non-aqueous solvents. Therefore, an organic polar 4 with a carmethyl group in copolymerization with & chain acrylic ester? It can be considered that the remer generates an appropriate amount of calxylate anion and induces charge generation in the polymer.

In the present invention, it is dissolved in a non-aqueous solvent. If polymer, partially gelled semi-dissolved polymer, particulate polymer, insoluble I polymer, etc. can be produced by known methods.

Examples of monomers O include styrene, vinyltoluene, vinyl acetate, acrylic acid or methacrylic acid, or alkyl (1 to 5 carbon atoms) esters thereof (e.g. methyl methacrylate, ethyl acrylate, methyl acrylate, ethyl methacrylate, butyl methacrylate),
Polyhydric alcohol di(meth)acrylates (e.g. ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate,
Diethylene glycol methacrylate, triethylene glycol triacrylate, triethylene glycol trimethacrylate, butanediol diacrylate, butanediol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol diacrylate, trimethylolgulono-9-triacrylate , trimethylolpro, bentrimethacrylate, dimethylolmethane triacrylate, tetramethylolmethane trimethacrylate, tetramethylolmethanetetraacrylate, tetramethylolmethanetetramethacrylate, dipropylene glycol diacrylate, diethylene glycol diacrylate, trimethylolhexane diacrylate, Trimethylolhexane trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, 1
．． 3-gutylene gelicol diacrylate, 1,3-butylene glycol dimethacrylate, trimethylolethane triacrylate, trimethylolethane methacrylate, allyl methacrylate, methalyl methacrylate), 0-divinylbenzene, etc. -Divinylbenzene, p-divinylbenzene, p-methyldivinylbenzene, O-ethyldivinylbenzene, p-butyldivinylbenzene, m-hexyldivinylbenzene, 0-nonyldivinylbenzene, p-f sildivinylbenzene, 0-kundesiM Divinylbenzene, p-stearyldivinylbenzene, 0-methyldivinylbenzene, 0-ethyldivinylbenzene, p-hexyldivinylbenzene, p-nonyldivinylbenzene, m-decludipinylbenzene,
Examples include pindecyldivinylbenzene and 0-stearyldivinylbenzene.

In the present invention, silica fine particles, wax or polyolefin having a softening point of about 60 to 130 C can be added to the copolymer manufacturing process. When fine silica particles are used, it is thought that the copolymer is obtained with the fine silica particles incorporated in its network structure. In addition, the silica itself is reacting,
It is not subject to physical changes such as dissolution. In any case, in the case of silica, the specific gravity is similar to that of the aliphatic hydrocarbon or halogenated aliphatic hydrocarbon solvent used as the dispersion medium, and since it prevents gelation of the copolymer, it is useful for improving toner dispersion stability. Helpful. On the other hand, when wax or polyolefin is used, it is dissolved in the reaction system during the polymerization reaction, and after the reaction is cooled, it precipitates in the system in the form of fine particles. In this way, the copolymer is thought to be obtained in a good state by being adsorbed or mixed with wax or polyolefin fine particles. Here, wax or polyolefin, like silica, has a specific gravity similar to that of the dispersion medium, and also has a molecular structure similar to that of the dispersion medium, which prevents gelation of the copolymer, so wax or polyolefin only serves to improve 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 5 parts by weight per 100 parts by weight of the copolymer! I.

Parts by weight are appropriate.

Specific examples of commercially available waxes or polyolefins having a softening point of 60 to 130 G are as follows.

Union Carbide (i) DYNI 1
02DYNF 102 DYNH102 DYNJ 102 DYNK 102 Manufacturer Product name Softening point (C)
Moresant (i) 0RLIZON BO2116
y 705 1161
50 12G Filituzos (USA) MARL13X 1005
92 Du Pont (i) ALATHO
N-3103# 12 B4 z 16 95 z 20 86y
22 84 Allied Chemical (US)
AO-Polyethylene: /1702 98
I 6 Todoroki - 6 people 102 #615 105 Sanyo Chemical
SUNWAX 131-P 108If
151-P 107 #161-Pill 1165-PIOγ #171-P105 #Ii! -20095 Side line of wax (paraffin wax) Positive Chemistry Paraffin wax 60
~98 Kobayashi Kako Sarashi Beeswax 65 Setanol 80 Mizuben Kako Sarashi Beeswax 65 Steel Manufacturing Chemical Frocene 110 Production examples and examples of the copolymer of the present invention are shown below.

Production Example 1 Isooctane 30011c was placed in a 2.0 mm four-hole flask equipped with a stirrer, a thermometer, and a rapid flow condenser.
It was heated to C. In this, dodecyl methacrylate 190
F, monomer B (Al ) 10I and azobisisobutyronitrile 61! A different solution was added dropwise over a period of 3 hours. After fc, the mixture was further heated and stirred at the above temperature for 4 hours to carry out a polymerization reaction, thereby obtaining a mercury with a polymerization rate of 94.8% and a viscosity of 120 ap.

Production Example 2 @ 300 g of the resin dispersion obtained in Production Example 1 was mixed with 10 g of colloidal silica in a flask, heated at 100 G for 3 hours, and then cooled to give a viscosity of 160 eps and a particle size of 0.3 to 0.
．． A 4μ colloidal silica-containing resin dispersion was obtained.

Production Example 3 Indodecane 3001' was placed in the same flask as in Production Example 1 and heated to 9.90C. Next, in this, 7uryl methacrylate) 300#, monomer B (j≦2) 30#SP
- A solution consisting of divinylbenzene 251 and hyponzoyl peroxide 3I was added dropwise over 1.5 hours, and the polymerization reaction was carried out by heating and stirring at 95G for 4 hours, resulting in a polymerization rate of 93.8% and a viscosity of 290 (! p, particle size 0.1
A resin dispersion of ~0.3μ was obtained. This resin liquid had a negative charge.

, tP 'J Mama - Charge measurements were made as follows.

A beaker of a 3 wt.
Copper 1 of X401111! An applied voltage of 1000 V is applied between the electrodes.

The judgment is that if the polymer has TrL attached to the positive electrode, it is a negatively charged polymer, and negative 1! A polymer with 'fX' attached to the pole was treated as a positively charged polymer.

Production Example 4 The resin dispersion obtained in Production Example 3 was mixed with 20 g of bleached beeswax in a 300 Iffi flask, stirred at 90C for 2 hours, and cooled to give a viscosity of 320 and ap1 particle size of 0.1 to 1.
A resin dispersion liquid of 0μ was obtained.

Production Example 5 Isopar 03001 and colloidal Kurimoto 301 were placed in the same flask as in Production Example 1 and heated to 90C. Among these is 2-ethylhexyl methacrylate 1501! , Monomer B (genus 5) 40ISP-divinylbenzene 2o
After dropping a solution consisting of I and 2 chloroyl peroxide 663I over 3 hours, the polymerization reaction was carried out by further stirring at the above temperature for 4 hours, resulting in a polymerization rate of 98.2% and a viscosity of 1.
6 Q ep, particle size 0.1-3. A resin dispersion of Ott was obtained. This resin liquid also had a negative charge.

Production Example 6 In the same flask as Production Example 1, Isopar L3001 and Dariethylene (manufactured by Allied Chemical Co., Ltd. 0-6) 60.9
and heated to 95DK.

Next, in this, stearyl methacrylate 1809% Monomer B (Al 5 ) 301% k! A solution of Ninitoni24M+, )rimethylolzolonone trimethacrylate 201 and lauryl oxide 4I) was added dropwise over a period of 3 hours, and the polymerization reaction was carried out by further stirring at the above temperature for 3 hours. Viscosity 130 e at 95.4%
A resin dispersion liquid having a particle size of 0.5 to 1.0 μm was obtained. This resin liquid contained a positive charge.

Production Example 7 In the same flask as Production Example 1, 0 g of Isopar H3O, Monomer B (A21) 2011, and Cetyl Methacrylate 180
1! % 40 g of dodecyl acrylate, 15,9 ataryl methacrylate, and 3 g of benzoyl oxide were taken, and the entire polymerization reaction was carried out at 901:' for 6 hours, and the polymerization rate was 9.
A resin liquid with a viscosity of 60 cp was obtained at 6.4%.

Furthermore, dropwise polymerization was performed with methyl methacrylate 50F and azobisisobutyronitrile 2#t-80C to obtain a viscosity of 2606PN.
A resin liquid with a particle size of 3 to 4 μm was obtained.

This resin liquid had a negative charge.

ml Preparation Example 8 Isooctane 300 if sampled, 95r in a 2.0 mm four-hole flask equipped with a stirrer, a thermometer, and a reflux condenser.
heated to. In this, dodecyl methacrylate) 190#
% methacrylic acid 10g.

After dropping a solution consisting of Nanatsuma-B (AI) IOJI and azobisisobutyronitrile 6I over a period of 3 hours,
The polymerization reaction was carried out by further stirring at the above temperature for 4 hours to obtain a resin dispersion having a polymerization rate of 93.0% and a viscosity of 180 ep.

Production Example 9 Resin dispersion 3001117 obtained in Production Example 8 was mixed with colloidal silica 101 in Cusco, heated at 100C for 3 hours, and then cooled to give a viscosity of 270 cp and a particle size of 4 to 6μ.
A fine silica powder base and an Arita fat dispersion were obtained.

Production Example 1Idadodecane 300I was added to the same flask as Production Example 8.
．． It was heated to 90tll'. Next, a solution consisting of 300 # of diuryl methacrylate, 5 g of N-vinylpyridine, 25 g of monomer B (2) and 3 g of benzoyl peroxide was added dropwise to this over a period of 1.5 hours, followed by stirring at the above temperature for 4 hours. The polymerization reaction was carried out with a polymerization rate of 94.8% and a viscosity of 24.
0ap.

A resin dispersion having a particle size of 3 to 4.5 μm was obtained.

Production Example 11 Resin dispersion 300I obtained in Production Example 10 was mixed with bleached beeswax 201 in a flask, stirred at 95C for 22 hours, and then cooled to give a viscosity of 290ep.

A bleached beeswax-containing resin dispersion having a particle size of 6 to 8 μm was obtained.

Production Example 12 Into the same flask as in Production Example 8, Aitu no Kai-G300I and silica fine powder 3011i were taken and heated to 90C. In this, 150 g of 2-ethylhexyl methacrylate, 1511 glycidyl methacrylate, 20 g of monomer B (geese 5)
After adding dropwise a solution consisting of methyl methacrylate) 40j' and lauroyl oxide 6.31, the polymerization reaction was carried out by further stirring at the above temperature for 4 hours, and the polymerization rate was 9.
At 5.0%, a resin dispersion with a viscosity of 270 ep% and a particle size of 2 to 3 μm was obtained.

Production Example 13 In the same flask as Production Example 8, Isopar L 300I and polyethylene (manufactured by Allied Chemical Co., Ltd. 00-6) 6 (
+ and heated to 95C.

Next, in this, 180 g of stearyl methacrylate, 1 lauryl methacrylate 4 ON, 7 malic acid 31, and 7 maric acid B
(Mu10) A solution consisting of 20.9 and lauryl peroxide 41 was added dropwise over a period of 3 hours, and then further heated at the above temperature for 3 hours.
A polymerization reaction was carried out by stirring for hours to obtain a resin dispersion with a polymerization rate of 95.0%, a viscosity of 600 cps, and a particle size of 2.5 to 3 μm.

Production Example 14 In the same flask as Production Example 8, add Isonose H3O011 Cetyl methacrylate) 180#, Dodecyl acrylate) 4
01? , Monomer B (A8) 151, 5 g of acrylic acid and 3 g of benzoyl peroxide were collected and stirred at 90 rpm for 6 hours to perform a polymerization reaction, and the polymerization rate was 97.0% and the viscosity was 3.
A 60 ep% resin dispersion with a particle size of 1 to 3 μm was obtained.

In order to make a liquid developer using the copolymer obtained in this way, generally 0.3 to 0.3 to 100% of the copolymer is added to 1 part by weight of the colorant.
3 parts by weight, and thoroughly dispersed in the presence of 10 to 20 g parts of an aliphatic hydrocarbon or halogenated aliphatic hydrocarbon carrier liquid using a dispersing machine such as Attritor, I-Lumil, or Kedimil. The concentrated toner may then be 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 the solvent.

Further, when preparing the ea) car, 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 and is therefore 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, the materials used in the present invention will be explained.

Examples of colorants include dyes or pigments such as carzen black, oil blue, alkali blue, phthalocyanine green, spirit black, aniline black, oil violet, benzidine yellow, methyl orange, brilliant carmizo, fast red, and crystal violet. .

Other resins that can be added to the developer include acrylic resins; ester gums; natural resins such as hardened rosin; maleic acid resins modified with these natural resins; phenolic resins:
Polyester: Examples include pentaerythritol resin.

Examples of the present invention are shown below.

Example 1 50g of the resin dispersion obtained in Production Example 8 was dispersed for 6 hours in a Kedaimill to obtain a concentrated toner with a viscosity of 17.0@P, and the resulting concentrated toner was dispersed in 10I't'' kerosene for electrostatic photography. A liquid developer was created.

Next, this developer was put into a commercially available electrophotographic copying machine, and copies were made on commercially available zinc oxide photosensitive paper. The image density was 1.30 and the image fixation rate was 82. A copy of O Rumor was obtained.

The fixation rate (5) is XXtoo (x is the initial image density of the copy, Y is the image density after erasing 5 times with an eraser tester)
It was calculated from the formula.

Furthermore, when the durability of the developer was examined by carrying out copying until the image density decreased to 0.60, it was found to be 12.000.
It was in good condition.

Further, after being stored for 3 months in a developer solution tsoc to forcefully deteriorate the image, the image was copied as described above and the image density was determined, and it was found that there was almost no deterioration at L29.

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 I-2 were obtained.

(Table-1) (Table-2) (Note) ID + image density effect As is clear from the above explanation, the resin of the present invention has a charge in a non-aqueous solvent, and the resin containing this resin Liquid developers for electrophotography have good image fixing properties, and have improved fade, durability, and storage stability.

Claims (1)

[Claims] 1. In the presence of a polymerization initiator in an aliphatic hydrocarbon solvent, the following general formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) (However, R is -H or - OH_2, X is -OOOC
nH_2_n_+_1 or -OCOCnH_2_n_
+_1, n is an integer from 6 to 20) Monomer A represented by the following general formula (II) and/or (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ Numerical formulas, chemical formulas, tables etc.▼(III) (However, R is -H or -CH_3, n is an integer from 1 to 20, M_1 is H, Na, K or Li, M_2 is Ca
, Mn, Co, or Mg). 2. An electrostatographic 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, the following general formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (However, R is -H or -CH_2, X is -COOC
nH_2_n_+_1 or -OCOCnH_2_n_
+_1, n is an integer from 6 to 20) Monomer A represented by the following general formula (II) and/or (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ Numerical formulas, chemical formulas, tables etc.▼(III) (However, R is -H or -CH_3, n is an integer from 1 to 20, M_1 is H, Na, K or Li, M_2 is Ca
, Mn, Co, or Mg).