JPS60254050A - Electrostatic image developing toner and its manufacture - Google Patents

Abstract

PURPOSE:To obtain an electrostatic image developing toner uniform in particle diameter, good in fluidity, and high in function by polymerizing a polymerizable compsn. composed of a colorant and a phenol-terpene copolymer. CONSTITUTION:As the phenol-terpene copolymer, a copolymer of a phenol resin component obtained by polymerizing a phenol type monomer with an aldehyde type monomer, and a terpene resin component made from monomers, such as menthene, pinene, or norpinene, are useful. As a colorant, carbon black, nigrosine dye, etc., are enumerated. The phenol-terpene copolymer, a colorant, a polymn. initiator, and further, when needed, additives, such as a cross-linking agent, a releasing agent, and an electrostatic charge controller, are dispersed into an aq. medium, and suspended in it, and temp. and other conditions are controlled to advance polymn. reaction. The polymerizable compsn. suspended in fine oil globules in the medium polymerizes as it is, without agglomerating, and solid spherical resin grains are obtained.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a toner for developing electrostatic images formed in electrophotography, electrostatic printing, electrostatic recording, etc., and a method for producing the same. ,do.

[Prior art]

In image recording methods that utilize electrostatic phenomena such as electrophotography, selenium, silicon, zinc oxide, cadmium sulfide,
Fine particles made of a coloring agent called a toner, a binder resin, etc. are applied to an electrostatic image formed on an electrostatic image carrier such as a photoconductive photoreceptor made of various organic compounds with photoconductivity by electrostatic attraction. Usually, the toner image is deposited and developed, and the resulting toner image is transferred as it is or onto a support such as paper and fixed by a fixing process to obtain a desired recorded matter.

Development is roughly divided into two types: methods using a so-called two-component developer made of a mixture of a carrier made of magnetic powder and toner, and methods using a so-called one-component developer made only of toner containing a magnetic material. In either case, the toner is required to have fine particles, uniform particle size, and good fluidity.

In addition, a heat fixing method is widely used to fix toner images, in which the toner image is heated by various means to melt the binder resin and fix it to the support.The heating means involves rotating the support carrying the toner image. The most commonly used method is to pass the fixing roller between a pair of fixing rollers consisting of a heat roller and a pressure roller. In this case, since the toner is melted by direct contact with the heat roller, it is necessary that the toner can be melted and fixed at a relatively low temperature, and that the molten toner is difficult to adhere to the fixing roller. Ru.

The toner used in the above development method is conventionally made by mixing a binder resin and a coloring agent, kneading the mixture in a molten state for a long time using an extruder, etc., cooling the resulting mixture to room temperature, and then mixing it with the coloring agent necessary for the toner. It is manufactured through complicated processes such as pulverizing into fine particles, further classification to make the particle size uniform, and in some cases, sphericalizing the particles by hot air treatment.

The toner manufacturing method described above requires melting, mixing, and pulverization processes, so the mixture of toner materials, such as resin colorants, charge control agents, etc., must be in a state where they can be fluidized at an appropriate temperature and mixed uniformly. It is required that the particles be easily pulverized to a desired particle size. However, if a material that is easy to crush is used, it will be further crushed in the developing device during use, resulting in equipment stains and image fogging1.If a material that is easily melted is used, the toner may become caked or photoconductive. Problems such as easy formation of stains (toner filming) on the surface of the layer occur, and there is a problem in that the selection of the resin is severely restricted. Further, it is difficult to completely uniformize the distribution of the charge control agent and the like within the particles by kneading alone, resulting in disadvantages such as unstable charging properties of the toner particles.

In order to solve these problems, for example,
JP 231, JP 47-51830, JP 51-14895, JP 53-17735, JP 53-17736, and JP 53-1
．． A production method using a polymerization method as disclosed in Japanese Patent No. 7737 has been proposed.

Toner production by the polymerization method involves mixing colorants, polymerization initiators, other additives, etc. into polymerizable monomers, which are the materials of the binder resin, and homogenizing them to form a polymerizable composition. The idea is to polymerize monomers to form a binder resin to obtain a toner, and in each of the above proposals, the polymerizable composition is dispersed and suspended in an aqueous medium and then polymerized to directly form a toner. A suspension polymerization method for obtaining the above is shown.

This method solves some of the problems in the kneading and pulverizing methods described above, and also has the advantages that the resulting toner particles are spherical and have good fluidity, the manufacturing process is simple, and the cost is low. have However, polymerizable compositions tend to aggregate easily in suspension, and especially when additives such as carbon black as a coloring agent or charge control agent are added, the suspension state becomes unstable and many aggregates occur. This method has a major disadvantage in that the yield of the desired fine powder toner is significantly reduced.

[Purpose of the invention]

The purpose of the present invention is to provide a high-performance electrostatic image developing toner (hereinafter also simply referred to as toner) with uniform particle size and good fluidity.
Another object of the present invention is to provide a new toner production method that can stably produce the above-mentioned toner at a high yield.

[Structure of the invention]

The above purpose is to produce a toner obtained by polymerizing a polymerizable product consisting of at least a polymerizable monomer, a colorant, and a phenol-terpene copolymer, and a toner obtained by polymerizing a polymerizable product consisting of at least a polymerizable monomer, a colorant, and a phenol-terpene copolymer. This was achieved by a toner manufacturing method that includes a step of polymerizing a polymerizable composition comprising a polymer.

As mentioned above, when producing toner by suspension polymerization +f,
Agglomeration of suspended polymerizable composition oil droplets is a cause of decreased yield, but as a result of intensive research, the present inventors have found that the presence of phenol-esterpene copolymer in the polymerizable composition is a concern. It was discovered that this method is extremely effective in stabilizing cloudy liquids, leading to the present invention.

The phenol resin components constituting the phenol terpene copolymer used in the present invention include phenol monomers such as phenol, cresol, xinol 1, naphthol, carvacrol, thymol, anthrol, and phenanthrol, and formaldehyde, Those obtained by polymerizing aldehyde monomers such as acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, valeraldehyde, butyraldehyde, and cinnamaldehyde are useful, and terpene resin components include menthene, pinene, norpinene. , Karene, Norkanene, Norbornene Binadienrene, etc. as monomers are useful. These thunol resin component and terpene resin component are made into a copolymer in the form of a block, a graft, or the like.

In this case, the ratio of the phenol resin component to the terpene resin is preferably in the range of 1:99 to 95:5 by weight. If the phenolic resin component is too small, the polymerization stabilizing effect of the present invention will not be achieved, and if it is too large, it will tend to inhibit polymerization.

Phenol-terpene resins useful in the present invention can be obtained by any combination of the monomers described above, so long as they are soluble in the polymerizable monomers in the production of the toners of the present invention to the concentrations of the present invention. Can it be used effectively?

The amount of the thunol terpene resin added is 0.00000000000000000000000000000000000000000000000000000000000000 1 to 10 weight percent is preferred, and 1 to 7 weight percent is particularly preferred. Addition amount is 0. If it is less than 1% by weight, it will not have this effect, and if it exceeds 10% by weight, the polymerization will become unstable due to the influence of the terminal functional group of the phenol/terpene resin, which is not preferable.

Examples of the polymerizable monomer that can be used in the present invention include styrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene,
p-ethylstyrene, 2,4-dimethylstyrene, p-
n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene, p=n-octylstyrene, pn-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxy Styrene, p-phenylstyrene, p-chlorostyrene, 3.

Preferred examples include monostyrene such as 4-dichlorostyrene. In addition, examples include ethylenically unsaturated monoolefins such as ethylene, propylene, butylene, and imbutylene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl acetate, propionic acid, etc. Vinyl esters such as vinyl, vinyl benzoate, vinyl butyrate; methyl acrylate, ethyl acrylate, #n-butyl acrylate, isbutyl acrylate, propyl acrylate, n-acrylate
octyl, dodecyl acrylate, lauryl acrylate,
2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate,
Methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate,
α- such as n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylamine ethyl methacrylate, etc. Methylene aliphatic monocarboxylic acid esters; Acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide; Vinyl ethers such as vinyl methyl ether vinyl isobutyl ether; Vinyl methyl ketone, vinyl bexyl ketone, methyl isopropenyl ketone, etc. Vinyl ketones; N-vinyl repip
-N-vinyl compounds such as N-ol, N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone; vinylnaphthalenes, and others. I can do that. These monomers can be used alone or in combination, or can be polymerized to form a copolymer.

For the polymerization of vinyl monomers as described above, a polymerization initiator is usually used in an amount of 0.5 to 10% by weight based on the polymerizable monomer. Specific examples of typical polymerization initiators include acetylcyclohexylsulfonyl peroxide, indibutyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl oxydicarbonate), 2.

4-dichlorobenzoyl peroxide, t-butyl peroxypivalate, 3,5.5-trimethylhexanoyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide,
Stearoyl peroxide, propionyl peroxide, succinic acid peroxide, acetyl peroxide, t-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, parachlorobenzoyl peroxide, t-butyl peroxyiso Butyrate, t-butyl peroxymaleic acid, t-butyl peroxylaurate, cyclohexanone peroxide, t-butyl baroxyisopropyl carbonate, 2,5-dimethyl-2,5-dibenzoyl peroxy hexane, t-7' methyl peroxyacetate), t-' butyl peroxybenzoate, diisobutyl ciba-oxyphthalate, methyl ethyl ketone peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di t-Butyl peroxyhexane, t-butylcumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di-t-butyl peroxyhexane, diisopropylbenzene hydroperoxide oxide, paramenthane hydroperoxide, pinane hydroperoxide,
Peroxide initiators such as 2,5-dimethylhexane-2,5-dihydroperoxide and cumene hydroperoxide, 2,2'-azobisisobutyronitrile,
1.1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis4-methoxy-2,4-dimethylvaleronitrile, 2.2'-7zobis-2,4-
Examples include azo initiators such as dimethylvaleronitrile.

In carrying out the method of the present invention, a plurality of polymerization initiators having different radical half-lives can be used. In this case, at a certain polymerization temperature, a polymerization initiator with a short half-life forms a so-called rapid initiation system, and a polymerization initiator with a long half-life forms a so-called slow initiation system, so that polymerization occurs in a rapid initiation system. A polymer with a low degree of polymerization and a low molecular weight is formed, and at the same time a polymer with a high degree of polymerization and a high molecular weight is formed in the slow initiation system. According to a toner made of a polymer consisting of a low molecular weight polymer portion and a high molecular weight polymer portion, the minimum fixing temperature is low due to the low molecular weight polymer portion, and offset occurs due to the high molecular weight polymer portion. The temperature becomes high.

Preferred examples of polymerization initiators with short half-lives include 2,2
'-Azobis-4-methoxy-2,4-dimethylvaleronitrile, 2,2'-7zobis-2,4-dimethylvaleronitrile, etc. can be used as a polymerization initiator with a long half-life. Preferred examples include 1,1-azobis(cyclohexane-1-carbonitrile).

As a coloring agent, carbon black, nigrosine dye (
c, i, 50415B), aniline blue (C, 1,
A30405), Calco Oil Blue (C, I.

Aazoic Blue 8), Chrome: r-ro
(C, I, A 14090), Ultramarine Blue (C0, B 77103), DuPont Oil Red (
C,1,ya 26105), quinoline yellow (C,1,
A47005), methylene blue chloride (c, 1
．． Jf652015), phthalocyanipsalate (C,
1, A42000), lamp black (C.

■, Bian 77266), Rose Bengal (C, I, A
45435), mixtures thereof, and others. These colorants must be contained in a sufficient proportion to form a visible image at a sufficient temperature.
It is usually added in an amount of 1 to 20 parts by weight per 100 parts by weight of the binder resin.

Although the molecular weight of the polymer according to the present invention is arbitrary, the weight average molecular weight is preferably 50,000 to 1,000.000.
and the number average molecular weight is 1,000 to 100,'000
It is. .

The polymer according to the present invention has a crosslinking agent present during polymerization,
It may be polymerized to form a crosslinked polymer.

Preferably used crosslinking agents mainly include compounds having two or more polymerizable double bonds, such as aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene and their derivatives, such as ethyne glycol dimethacrylate, diethylene glycol methacrylate, etc. rate, triethylene glycol methacrylate, trimethylolpropane triacrylate, allyl methacrylate, t
- All divinyl esters such as butylaminoethyl methacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, etc., NIN dipinyl anion, divinyl ether, divinyl sulfide, divinyl sulfone, etc. A compound and a compound having three or more vinyl groups are selected singly or as a mixture.

The amount of the crosslinking agent added to the monomer is selected to be in the range of 0.005 to 20% by weight, preferably 0.1 to 5% by weight.

If the amount added is too large, the toner will not melt and will tend to lose its fixing properties as a toner. In addition, if the amount is too low, it becomes difficult to impart toner properties such as durability, storage stability, and abrasion resistance, and the molecular weight distribution of the polymer expands due to crosslinking and as a result, especially in hot roll fixing type copiers, etc. of the toner itself.

Due to its properties, it becomes difficult to achieve the effect of preventing the offset phenomenon during fixing.

Further, the toner of the invention can contain a low molecular weight olefin polymer known as a so-called mold release agent.

A prepolymer (particularly a reactive prepolymer) may be added to the toner of the present invention during the polymerization process for the purpose of improving fixing performance such as anti-offset effect. The reactive prepolymer has a reactive group in the main chain and/or side chain of the prepolymer, and examples of such prepolymers include unsaturated polyester, unsaturated polybutadiene, and the like.

When polymerizing a polymerizable composition by a suspension polymerization method, the polymerization composition is dispersed and suspended in a dispersion medium such as water as dispersed particles of a desired particle size by mechanical stirring, and polymerization is carried out. It is necessary to prevent the dispersed particles from coalescing into large particles due to increased stickiness as the process progresses, and a suspension stabilizer is used for this purpose.

The suspension stabilizers used as such suspension stabilizers are generally divided into water-soluble polymeric substances and fine powders of poorly soluble inorganic compounds.The former includes gelatin, starch, polyvinyl alcohol, and others, and the latter includes Barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, calcium phosphate, and other sparingly soluble salts, and combinations of sparingly soluble salts and surfactants such as sodium dodecylbenzenesulfonate and sodium dodecyl sulfate, talc, viscosity, and silicic acid. , inorganic polymeric substances such as diatomaceous earth, metal oxides, and other powders. In addition, when the polymer composition contains an ionic substance, for example, a cationic substance or anionic substance such as a nitrogen-containing polymerizable monomer or poorly water-soluble amines, the dispersed particles have a positive effect when dispersed in water. Or, in the case of being charged to one negative polarity, an ionic powder that is charged to the other polarity when dispersed in water, such as (1) negatively charged colloidal silica, positively charged aluminum oxide, etc., is suspended. It can be effectively used as a stabilizer.

□ In addition to these, the toner of the present invention may contain a magnetic material, a charge control agent, a dispersant, etc., as necessary.

Magnetic materials include ferrite, magnetite, iron, cobalt, nickel, and other ferromagnetic metals or alloys, or compounds containing these elements, or materials that do not contain ferromagnetic elements but can be made ferromagnetic by applying appropriate heat treatment. Mention may be made of alloys which become magnetic, such as alloys of the type called Heusler alloys containing manganese and copper, such as manganese-copper-aluminum, manganese-copper-tin, or chromium dioxide, among others.

Furthermore, various known charge control agents, such as nigrosine dye, may be added to the toner according to the present invention in order to adjust its triboelectric charging properties.

In order to produce the toner according to the present invention by a suspension polymerization method, the above-mentioned phenol, terpene copolymer, and colorant polymerization initiator are added to the commercially available polymer, and if necessary, a crosslinking agent,
Additives such as a mold release agent and a charge control agent are added, and the mixture is homogenized using a sand stirrer to form a polymerizable composition. The polymerization reaction is allowed to proceed by adjusting the temperature and other conditions.

The polymerizable composition suspended in the form of fine oil droplets in the medium (due to the effect of the phenol terpene resin added in advance, the polymerizable composition is directly polymerized without agglomeration to obtain spherical resin particles. Resin particles (or may be further crushed to form a toner with the required particle size, but the particle size of the yuzu oil particles is the same as the suspended if
Since the ratio depends on the silk composition and the dispersion state, it is preferable to adjust the dispersion conditions in advance and suspend the toner to the desired particle size, so that the resulting resin particles can be used as is as a toner. .

The toner of the present invention is mixed with a carrier made of iron powder, glass beads, etc. to form a two-component developer, but when it contains a magnetic material, it can be directly used as a one-component developer for development to eliminate electrostatic charges. Ru.

Examples] The present invention will be specifically described below with reference to Examples, but the embodiments of the present invention are not limited thereto. Incidentally, the numbers in this example represent parts by weight unless otherwise specified.

Example +1 90 parts of styrene, 10 parts of n-butyl acrylate, "Mitsubishi Carbon Black +30 (Mitsubishi Kasei ■W) 1
0 <, low molecular weight polypropylene “Viscol 550P
j (manufactured by Mitsubishi Chemical Corporation) 10 parts, 3 parts of phenol/terpene resin [YS Polyster S 145J (cheap crude oil business book)], 3 g of 2,2-azobis(2,4-demethylvaleronitrile) dispersed Mix to form a polymeric composition, which is combined with 3 weight percent calcium phosphate and 0
, 04ttj Amount of sodium dodecylbenzenesulfonate containing sodium dodecylbenzene sulfonate was added in an amount of 30 percent, and then heated at 9.00 Or, p, m using a homogenter (manufactured by Tokushu Kika Kogyo Neto).

The mixture was stirred at a stirring speed of . After stirring for 30 minutes, the particle size range of the dispersed particles varied from 10 to 15 μm. After that, the humidity was raised to 50°C, and the rotation speed was 1. O
The polymerization reaction was carried out for 20 hours while entraining at a stirring speed i1 of 100 pm, and the polymerization reaction was completed. After the polymerization was completed, the solid matter was separated, dried, and analyzed using an analyzer to remove particles having a particle size of 5 μm or less and 15 μm or more to obtain the toner of the present invention having an average particle size of 12 μm.

Example 2 The toner of the present invention was obtained in the same manner as in Example 1, except that YS Polyster 81451 was replaced and phenol-chill resin YS Polyster'r (Yasuyu Kogyo (Nikudan)) was used. .

Example-3 Instead of YS Polyster 8145, phenol red terpene resin [Mighty Ace G125 J
+Q':"W, l), outside is Example-1
I got the toner in the same way.

Example-4 Styrene 85 tJ<, cubyl acrylate 15 parts,
A toner was obtained in the same manner as Example 1 and Old 1 except that 0.4 part of ethylene glycol dimethacrylate was used and the reaction humidity was 60°C.

Example 5 11. Using Mighty Ace G125 j instead of YS-Polystar 8145. A toner was obtained in the same manner as in Example-4.

Example-6 82 parts of styrene, 18 parts of warp tyl acrylate, Mitsubishi carbon black 4+3010 parts, Viscol 550P
10 parts 2,2'-azobis(2,4-dimethylvaleronitrile) 0.8 part, 1. r-Azobi(cyclohexane l)
-Carbonitrile') 0.2 part MS-Polyster 5L
1.S- was obtained in the same manner as in Example-1, except that 455 parts of the product was used and the reaction was carried out at a reaction temperature of 85° C. for 20 hours.

Example-7 2,2'-azobis(thimethoxy-2,4) was used as an initiator.
A toner was obtained in the same manner as in Example 6, except that 0.4 part of azobisisobutyronitrile was used and the reaction temperature was 65°C.

Comparative Example-1 A comparative test was conducted in the same manner as in Example-1 except for IzL without using YS-Polyster 8145.

Comparative Example-2 A comparative test was conducted in the same manner as in Example-6 except that YS-Polyster 145 was not used.

In Examples 1 to 7 in which the phenol/terpene resin was added to the polymerizable composition according to the present invention, the suspension was extremely stable, and the polymerizable composition remained stable throughout the entire period of polymerization. In Comparative Example 2, which does not contain phenol/terpene resin, fine oil droplets were retained and polymerization proceeded as is.

Or 2. In this case, the dispersion of the polymerizable composition was poor, the suspension state was unstable, a large number of aggregated suspended particles were generated during the polymerization reaction, and an extremely large number of coarse particles were removed when the resulting toner was classified. The yield of the toner in each Example and Comparative Example, that is, the ratio of the toner weight after particle sizes of 5 μm or less and particles of 15 μm or more were removed by classification and the polymerizable composition used was as shown in Table 1. .

Table 1 Example 1 according to the present invention. It is clear that the yields of the toners of Comparative Examples 1 and 2 are extremely low, whereas the yields of the toners of Comparative Examples 1 to 7 are all extremely high.

2 parts by weight of each toner obtained by classification and 98 parts by weight of magnetic carrier
Adjust the developer by mixing in the weight section and use the electronic copying machine U-B.
When a copying test was carried out by loading the toners into an i

〔Effect of the invention〕

The present invention, in which a phenol/terpene resin is added to a polymerizable composition, has made it possible to obtain toner for electrostatic image development with high fluidity and uniform particle size in a high yield and in a stable manner.

Agent: Patent attorney: Yoshichika Noda Procedural Amendment July 3, 1985 Director of the Tokyo Metropolitan Patent Office Michibu Uga 1, Indication of the case 1982 Patent Application No. 94809 2, Name of the invention Toner for electrostatic image development and Manufacturing method 3, relationship with the case of the person making the amendment Patent applicant Konishiroku Photo Industry Co., Ltd., 1 Sakura-cho, Hino-shi, Tokyo (Telephone 0425-83-15)
21) Patent Department 5, Column 6 of ``Detailed explanation of the invention'' in the specification to be amended, Column 1 of ``Detailed explanation of the invention'' of the specification of contents of the amendment (1. To do.

Claims (6)

[Claims] (1) At least a polymerizable monomer, a colorant, and a phenol.
A toner for electrostatic image development, characterized in that it is obtained by polymerizing a polymerizable composition comprising a terpene copolymer. (2) The content of the phenol-terpene copolymer in the polymerizable composition is from 0.1 to 10% by weight of the polymerizable monomer. toner for electrostatic image development. (3) The electrostatic image according to claim 1 or 2, wherein the polymerization of the polymerizable composition is carried out by suspending the polymerizable composition in an aqueous medium. Toner for development. (4) A method for producing a toner for electrostatic image development, which comprises the step of polymerizing a polymerizable composition consisting of a small amount of polymerizable monomers, a colorant, and a phenol-terpene copolymer. (5) The content of the supplementary funol-terpene copolymer in the polymerizable composition is 0.1 to 10 weight percent of the polymerizable monomer. Method for manufacturing toner for electrostatic image development (6) Electrostatic image development according to claim 4 or 5, wherein the polymerization of the polymerizable composition is carried out in a state where the polymerizable composition is suspended in an aqueous medium. method for producing toner for use in