JP2001305798A - Toner for development of electrostatic charge image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for development of an electrostatic charge image which is excellent in fixing properties, offset resistance and durability, which shows stable electrification behavior even for continuous printing and with which a high density and high quality printed image can be obtained. SOLUTION: The toner consists of a polyvalent metal salt polymer (b) prepared by producing a carboxyl group-containing polymer (a) obtained by copolymerization of an addition polymerizable unsaturated carboxylic acid and other copolymerizable monomers and making the polymer (a) to a polyvalent salt, and wax being an ester of a carboxylic acid and alcohol and having a 12-40C chain hydrocarbon group in part of the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic image developer used in an electrophotographic method, an electrostatic recording method, or an electrostatic printing method.

[0002]

2. Description of the Related Art As an electrophotographic method, US Pat.
No. 97,691, JP-B-42-23910 and JP-B-43-24748, various methods are described. Usually, various methods are described on an electrostatic latent image carrier such as a photoconductive photoreceptor. An electrostatic latent image is formed by charging and exposure, and then the electrostatic latent image is developed with a toner composition containing a colorant in a binder resin, and the obtained toner image is transferred to a support such as transfer paper. In general, a visible image is formed by fixing.

[0003] Further, many methods are known as a developing method in electrophotography, but when roughly classified, fine particles (20 to 500) such as iron powder, ferrite, nickel, and glass are used.
μm) as a developer, and a one-component development method using a developer consisting of only the toner.

Typical examples of the two-component developing method include a cascade method described in US Pat. No. 2,618,552 and a magnetic brush method described in US Pat. No. 2,874,063.
In these methods, the carrier shares functions such as agitating, transporting, and charging the developer, and the function separation between the carrier and the toner is clear. For this reason, it is widely used at present because charge control of the toner and formation of the developer layer are relatively easy, and high-speed operation is possible.

[0005] With the development of the information society in recent years, in each field of electrophotography, electrostatic recording, and electrostatic printing, high quality of printed images, high speed of recording, high density, and long-term storage stability have been achieved. Demands for improvement of toner characteristics for recording an electrostatic latent image on a non-printing medium have been greatly increased. In particular, in toners for two-component developers suitable for high-speed printing, the mechanical strength to withstand friction with the carrier, stable fixing behavior in a wide temperature range in the heat roll fixing method, stable charging behavior in multi-copy printing, It is an important issue to eliminate scattered toner that does not contaminate the inside of the machine even when used for a long period of time, and these issues greatly depend on the properties of additives such as a binder resin and wax used in the toner composition.

Hitherto, as binder resins for toners, polystyrene, styrene-acrylate copolymer, styrene-butadiene copolymer, polyester,
Epoxy resins, polybutyral resins, xylene resins, coumarone indene resins, and the like have been researched and used, and various proposals have been made in designing these resins depending on the application.

In general, there are various characteristics required for the binder resin, such as charging and fixing characteristics. Particularly, the binder resin used for the toner for heat roll fixing includes a transfer paper. Improvements in fixing performance and anti-offset performance are required. In the heat roll fixing, the toner particles electrostatically attached to the transfer paper are pressed,
It is melted and fixed on the transfer paper by passing between heated heat rolls. However, at this time, if the surface temperature of the roll is too low, the entire toner particle layer is not sufficiently heated,
Only the surface in contact with the heating roll softens and adheres to the heating roll. Since the toner on the transfer paper side is not softened, no adhesive force is generated, and as a result, most of the toner layer on the transfer paper is transferred to the fixing roll side without being fixed to the transfer paper. This is called a cold offset.

Conversely, if the temperature of the roll surface is too high, the viscosity of the melted toner decreases. Along with this, the internal cohesive force of the melted toner layer also sharply decreases and falls below the adhesive force to the heating roll. As a result, the melted toner layer breaks and moves to both the transfer paper and the fixing roll. This is called hot offset and causes the contamination of the heating roll. The toner adhered to the heat roll is re-transferred to the transfer paper and stains the non-image area, thereby lowering print quality.

The anti-offset performance means that the toner has the ability to prevent cold offset or hot offset at a certain temperature, and the binder resin for toner has anti-offset performance over a wide temperature range, and It is required to have excellent fixing characteristics.

Numerous design examples have been proposed to achieve the above objects. Among them, in order to maintain the viscoelasticity at the time of heating and melting, or to suppress the viscosity change due to temperature fluctuation, the molecular weight distribution is increased and the crosslinking is increased. Techniques for providing a structure, applying a rubber elastic material, and the like have been studied.
For example, Japanese Patent Publication No. 52-25420, 53-174
Nos. 96, 55-49305, and JP-A-55-3852.
No. 4, No. 57-37353, No. 58-11952, and the like, a polyester resin for heat roll fixing is proposed.
No. 48335 proposes a polyvalent metal chloride polymer as a binder resin. However, in these conventionally proposed inventions, a binder resin for toner which sufficiently satisfies the anti-offset performance and the fixing performance in a wide temperature range currently required has not been obtained.

On the other hand, a technique of adding wax to the toner to impart releasability from a heat roll at the time of fixing and to prevent occurrence of offset has been studied in parallel. Until now, polypropylene wax,
Synthetic waxes such as polyethylene wax have been mainly studied, but are disclosed in JP-A-1-238672 and JP-A-3-23867.
No. 5764, Japanese Patent Application Laid-Open No. 5-119509 and the like disclose examples using natural waxes such as montan wax, carnauba wax and rice wax.

However, none of these reports discloses an invention which satisfies all the characteristics required for the high-speed printing toner described above. In particular, in toners for two-component developers suitable for high-speed printing, the mechanical strength to withstand friction with the carrier, stable fixing behavior in a wide temperature range in the heat roll fixing method, stable charging behavior in multi-copy printing, Even after long-term use, no toner has been obtained which has eliminated the scattered toner which does not contaminate the inside of the machine.

[0013]

DISCLOSURE OF THE INVENTION The present invention is excellent in heat roll fixing property and offset resistance, shows stable charging behavior in multi-copy printing without generating scattering toner, and has high durability and long service life. It is an object to provide a toner for developing a charge image.

[0014]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems, and as a result, have reached the present invention.

That is, the present invention provides a toner comprising a binder resin, a colorant and a wax, wherein the binder resin comprises an addition-polymerizable unsaturated carboxylic acid and another copolymerizable monomer. A polyvalent metal chloride polymer (b) (hereinafter simply referred to as polymer (b)) obtained by copolymerizing carboxyl group-containing polymer (a) (hereinafter simply referred to as polymer (a)) with polyvalent metal Wherein the wax is an ester of a carboxylic acid and an alcohol and is a wax having a chain hydrocarbon group having 12 to 40 carbon atoms in a part of the molecule. Is what you do.

The polymer (b) used as a binder resin in the present invention is a thermoplastic resin which is also broadly referred to as an ionomer, and has a crosslinked structure by ionic bonds or coordinate bonds. At room temperature, this kind of resin has toughness and excellent abrasion resistance due to the presence of the cross-linked structure, and under heat, the cross-linked structure is broken and becomes a molten state. Suitable for toners.

Specific examples of the addition-polymerizable unsaturated carboxylic acid constituting the polymer (a) which is the base resin of the polymer (b) used in the present invention include acrylic acid, methacrylic acid, α-ethylacrylic acid, Crotonic acid, α-methyl crotonic acid, α
Addition-polymerizable unsaturated aliphatic monocarboxylic acids such as ethyl crotonic acid, isocrotonic acid, tiglic acid, ungeric acid, or additions such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, dihydromuconic acid And polymerizable unsaturated aliphatic dicarboxylic acids.

In the present invention, as the other monomer component used by being copolymerized with the above-mentioned addition-polymerizable unsaturated carboxylic acid, various ones can be mentioned, and it is not particularly limited. Examples include the following monomers.

That is, in addition to styrene, derivatives thereof such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, alkylstyrene such as hexylstyrene, heptylstyrene, and octylstyrene; , Chlorostyrene,
Examples include halogenated styrenes such as bromostyrene, dibromostyrene, and iodostyrene, and nitrostyrene, acetylstyrene, and methoxystyrene.

The above-mentioned addition-polymerizable unsaturated carboxylic acid and alkyl alcohol, halogenated alkyl alcohol,
Examples thereof include an esterified product with an alcohol such as an alkoxyalkyl alcohol, an aralkyl alcohol and an alkenyl alcohol. And, as specific examples of the alcohol, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol,
Alkyl alcohols such as hexyl alcohol, hebutyl alcohol, octyl alcohol, nonyl alcohol, dodecyl alcohol, tetradecyl alcohol, and hexadecyl alcohol; halogenated alkyl alcohols obtained by partially halogenating these alkyl alcohols; methoxyethyl alcohol, ethoxyethyl alcohol, Alkoxyalkyl alcohols such as ethoxyethoxyethyl alcohol, methoxypropyl alcohol and ethoxypropyl alcohol; aralkyl alcohols such as benzyl alcohol, phenylethyl alcohol and phenylpropyl alcohol; and alkenyl alcohols such as allyl alcohol and crotonyl alcohol.

Among the above-mentioned addition-polymerizable unsaturated aliphatic carboxylic acid esters, alkyl acrylate, alkyl methacrylate, alkyl fumarate, alkyl maleate and the like are particularly preferred.

Further, amides and nitriles derived from the above-mentioned addition-polymerizable unsaturated carboxylic acids; aliphatic monoolefins such as ethylene, propylene, butene and isobutylene; vinyl chloride, vinyl bromide, vinyl iodide, 1,2-
Dichloroethylene, 1,2-dibromoethylene, 1,2
-Diiodoethylene, isopropenyl chloride, isopropenyl bromide, allyl chloride, allyl bromide, vinylidene chloride,
Halogenated aliphatic olefins such as vinyl fluoride and vinylidene fluoride; 1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2 , 4-hexadiene, 3-
Conjugated diene-based aliphatic diolefins such as methyl-2,4-hexadiene are exemplified.

As the method for producing the polymer (a), a usual polymerization method can be employed, and a method of performing a polymerization reaction in the presence of a polymerization catalyst, such as solution polymerization, suspension polymerization, or bulk polymerization, can be mentioned. .

Examples of the polymerization catalyst include 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, and 1,1′-azobis (cyclohexane-1-yl).
(Carbonitrile), benzoyl peroxide, dibutyl peroxide, butyl peroxybenzoate, and the like, and the amount used is 0.1 to 10.
0% by weight is preferred.

The metal which forms a salt by binding as a cation to the carboxyl anion contained in the polymer (a) includes Al, Ba, Ca, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn,
Examples include polyvalent metals such as Ni, Pb, Sn, Sr, and Zn.

In order to bond these metals to the polymer (a) to form a salt, the polymer (a) is added to a halide, hydroxide, oxide, carbonate, carboxylate, An alkoxylate, a chelate or the like may be appropriately reacted. This reaction can be sufficiently achieved either by heating and stirring the required components in the presence of a solvent or by melt-kneading in the absence of a solvent. Polyvalent metal as described above is not bonded to the carboxyl anion of the polymer (a),
When a cation such as NH is bound, the resulting salt is thermally unstable and not only releases gas upon heating, but may also lose the reversibility of the ionic bond. Also, when a cation such as Na binds,
As a result, the resulting salt becomes a hydrophilic salt, and the toner using the salt has a large dependence on humidity and has a drawback that the charge decay rate is extremely fast. The reason for using the polyvalent metal in the present invention is to eliminate the above-mentioned disadvantages.

It is desirable that the polymer (a) and the polymer (b) used in the present invention satisfy the relations represented by the following formulas (1), (2) and (3). 10 ⁻⁵ ≦ N ≦ 2 × 10 ⁻³ (1) T ₁ −T _S ≧ 20 ° C. (2) 35 ° C. ≦ Tg ≦ 75 ° C. (3) [In the above formula, N represents a polyvalent metal chloride polymer (b ) The number of moles of carboxyl ions converted into metal contained in 1 g, T ₁ is the softening point of polyvalent metal chloride polymer (b) by ring and ball method, and T _S is the softening point of carboxyl group-containing polymer (a) by ring and ball method. Point, T
g represents the glass transition temperature of the polyvalent metal chloride polymer (b). ]

In the formula (1), when N is 10 ^-5 or less, there is no viscosity effect due to metal chloride, and N is 2 × 10 ^-3.
If it is above, there is a possibility that the charging characteristics of the toner may be hindered, and the fixing start temperature is increased. A more specific preferred viscoelastic range is described by equation (2). That is, the ring-and-ball method softening point temperature that measures the temperature at the time of constant deformation under a constant load is a kind of viscosity index, but the polymer (b) according to the present invention.
Softening point T _1, the polymer T softening point in the non-metallic chloride state, that the softening point of the polymer (a) is taken as T _S in (b) ₁ -
T _S is a toner using a polymer showing a is at least 20 ° C. or more values preferably in the heat roll fixing method. Also, T ₁
Is preferably from 120 to 180 ° C, more preferably from 140 to 170 ° C. If the temperature is lower than 120 ° C., offset at a high temperature tends to occur, and if the temperature is higher than 180 ° C., the fixability at a low temperature deteriorates. Further, the polymer (b) according to the present invention is characterized in that Tg is in the range of 35 to 75 ° C., thereby enabling fixing at a lower fixing roll surface temperature while preventing blocking at a high temperature. be able to.

The polymer (b) used in the present invention desirably accounts for all of the binder resin, but preferably at least 30% by mass. A thermoplastic resin used for an electrophotographic toner may be mixed, for example, polystyrene, styrene-acrylate copolymer resin, polyacrylate, polyethylene, styrene-butadiene copolymer resin, polyamide, polyvinyl chloride, vinyl chloride-vinyl acetate. Copolymer resin, Coumarone-
Indene resin or the like can be used.

As the coloring agent that can be used in the present invention, well-known coloring agents can be mentioned. Carbon blacks such as furnace black, channel black, acetylene black, thermal black, and lamp black classified according to the production method are used as black colorants, and phthalocyanine C.I. I. PigmentBl
ue 15-3, an indanthrone C.I. I. Pigm
ent Blue 60 and the like, and quinacridone C.I. I. Pigment Red 122,
Azo-based C.I. I. Pigment Red 22, C.I.
I. Pigment Red 48: 1, C.I. I. Pig
Ment Red 48: 3, C.I. I. Pigment
Red 57: 1, etc., and an azo-based C.I. I. Pigment Yellow 12, C.I. I.
Pigment Yellow 13, C.I. I. Pigm
ent Yellow 14, C.I. I. Pigment
Yellow 17, C.I. I. Pigment Yellow
ow 97, C.I. I. Pigment Yellow 1
55, isoindolinone-based C.I. I. Pigment
Yellow 110, a benzimidazolone C.I.
I. Pigment Yellow 151, C.I. I. P
pigment yellow 154, C.I. I. Pigm
ent Yellow 180, and the like. The content of the colorant is preferably in the range of 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the binder resin. These colorants are 1
Species or a combination of two or more can be used.

The wax used in the present invention, which is an ester of a carboxylic acid and an alcohol and has a chain hydrocarbon group having 12 to 40 carbon atoms in a part of the molecule, includes the following <
It is preferable that the compound contains at least one selected from the compounds represented by Formulas 1 to 5.

<General formula 1>

[0033]

Embedded image (R1 and R2 are a hydrocarbon group having 1 to 40 carbon atoms,
At least one of them represents a chain hydrocarbon group having 12 or more carbon atoms. <General formula 2>

[0034]

Embedded image (R1, R2 and R3 are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them represents a chain hydrocarbon group having 12 or more carbon atoms.) <General formula 3>

[0035]

Embedded image (R1, R2 and R3 are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them represents a chain hydrocarbon group having 12 or more carbon atoms.) <General formula 4>

[0036]

Embedded image (R1 is a hydrocarbon group having 12 to 40 carbon atoms. R2 is a hydrocarbon group having 1 to 40 carbon atoms. A + b = 4, a represents an integer of 1 to 4, and b represents an integer of 0 to 3. <General formula 5>

[0037]

Embedded image (R1, R2 and R3 are hydrocarbon groups having 1 to 40 carbon atoms, at least one of which is a chain hydrocarbon group having 12 or more carbon atoms, and a and c are integers of 0 to 2,
a + c = 2. b is an integer from 1 to 4, and d is 1
Or 2. Furthermore, e = d-1. Specific examples of the wax represented by the above general formula include the following compounds. <Wax 1>: Specific example of general formula 1

[0038]

Embedded image <Wax 2>: Specific example of general formula 2

[0039]

Embedded image <Wax 3>: Specific example of general formula 3

[0040]

Embedded image <Wax 4>: Specific example of general formula 4

[0041]

Embedded image <Wax 5>: Specific example of general formula 5

[0042]

Embedded image <Wax 6>: Specific example of general formula 5

[0043]

Embedded image Of the above specific examples, wax 1 and wax 4 can be preferably used, and wax 4 is the most preferred wax that can be used in the present invention.

In the present invention, the wax comprising an ester of a unit price or polyvalent carboxylic acid having a chain hydrocarbon group having 12 to 40 carbon atoms and a unit price or a polyhydric alcohol prevents the offset phenomenon at the time of heat roll fixing. In addition to its function as a release agent, it gives a stable charge to the toner without adhering to the carrier surface even when printing a large number of sheets for a long time, and produces high-quality and high-definition images without generating scattering toner. Enable printing.

In particular, in high-speed development, the resin of the present invention works synergistically with the tough and naturally excellent abrasion resistance, and the above effect is remarkable.

It is desirable that the wax is contained in an amount of 0.3 to 15 parts by mass, preferably 1 to 5 parts by mass, based on the binder resin. If the amount is less than 0.3 part by mass, the offset resistance is poor. If the amount is more than 15 parts by mass, the fluidity of the toner is deteriorated, and the development stability is adversely affected.

In the present invention, various known waxes such as polypropylene wax, polyethylene wax, polyamide wax, Fischer-Tropsch wax, synthetic ester wax, montan ester wax, carnauba wax, rice wax and / or scale insect A wax can be used in combination.

The charge control of the toner may be carried out with the binder resin and the colorant itself, but a charge control agent may be used if necessary. Examples of the negative charge control agent that can be used in the present invention include a trimethylethane dye, a metal complex salt of salicylic acid, a metal complex salt of benzyl acid, copper phthalocyanine, perylene, quinacridone, an azo pigment, a metal complex salt azo dye,
Examples include heavy metal-containing acid dyes such as azochrome complexes, calixarene-type phenol-based condensates, cyclic polysaccharides, and resins containing a carboxyl group and / or a sulfonyl group.

More specifically, "Bontron S-34" manufactured by Orient Chemical Co., Ltd., and "Aizen Spiron Black TR" manufactured by Hodogaya Chemical Co., Ltd. as metal complex salt azo dyes.
H "and the like are preferably used.

In particular, it is desirable to use a colorless charge control agent in a color toner, and "Bontron E-84" manufactured by Orient Chemical Co., Ltd. as a metal complex compound of salicylic acid.
However, as the metal complex compound of benzylic acid, "LR-147" and "LR-297" manufactured by Nippon Carlit are preferably used.

Although the structure is not clear, "TN-105" manufactured by Hodogaya Chemical can also be suitably used as a colorless negative charge control agent.

As the positive charge control agent, a triphenylmethane dye, a nigrosine dye, a quaternary ammonium salt compound, a resin containing an amino group, or the like can be used. The quaternary ammonium salt compound is particularly preferably at least one selected from the following <General Formula 6> or <General Formula 8>. Bontron P-51; (manufactured by Orient Chemical) for the compound having the structure of <General Formula 6>, and TP-3 for the compound of <General Formula 7>.
02, TP-415, TP-610; (manufactured by Hodogaya Chemical)
There is.

<General formula 6>

[0054]

Embedded image [Wherein, R _{1 to} R ₃ represent a CnH2n + 1 group. Where n
Represents an integer of 1 to 10. Further, R _{1 to} R ₃ may be the same or different. ] <General formula 7>

[0055]

Embedded image Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently a hydrogen atom, an alkyl or alkenyl group having 1 to 22 carbon atoms, an unsubstituted or substituted aromatic group having 1 to 20 carbon atoms, Represents an aralkyl group having 7 to 20 carbon atoms, A ^- is a molybdate anion or a tungstate anion,
Represents a heteropolyacid anion containing molybdenum or tungsten atoms. <General formula 8>

[0056]

Embedded image Wherein m represents 1, 2 or 3, and n represents 0, 1
Or 2, and M is a hydrogen atom or a monovalent metal ion. X and Z each represent 1 or 2, and Y represents 0 or 1. Further, when X = 1, Y = 1 and Z = 1, and when X = 2, Y = 0 and Z = 2. R _{5 to} R ₁₂ are hydrogen, a linear or branched saturated or unsaturated alkyl group having 1 to 30 carbon atoms, an alkoxylene group having 1 to 4 carbon atoms, or a general formula (-C 2-5 alkylene-O ) N-R
(Where R is hydrogen or an alkyl group or acyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 10), wherein R ₁ , R ₂ ,
R ₃ and R ₄ are hydrogen, a linear or branched saturated or unsaturated alkyl group having 1 to 30 carbon atoms, or a general formula (—CH ₂ —CH ₂ —O) n—R (however, R is hydrogen or an alkyl group or an acyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 10), an oxyethyl group represented by the formula: and a mononuclear or polynuclear alicyclic group having 5 to 12 carbon atoms. Residue, mononuclear or polynuclear aromatic residue or araliphatic residue. ]

More specifically, there are the following compounds. (6-1)

[0058]

Embedded image

(7-1)

[0060]

Embedded image

(7-2)

[0062]

Embedded image

(7-3)

[0064]

Embedded image

(7-4)

[0066]

Embedded image

(7-5)

[0068]

Embedded image

(7-6)

[0070]

Embedded image

(7-7)

[0072]

Embedded image

(7-8)

[0074]

Embedded image

(7-9)

[0076]

Embedded image

(7-10)

[0078]

Embedded image

(7-11)

[0080]

Embedded image

(8-1)

[0082]

Embedded image

(8-2)

[0084]

Embedded image The charge control agents exemplified above may be used in combination of two or more. For example, when a nigrosine dye and a quaternary ammonium salt compound are used in combination, the use ratio is preferably 1/9 to 9/1, and more preferably 2/8 to 8/2.

The nigrosine dye has a high positive charge-imparting ability, and the quaternary ammonium salt compound has excellent charge uniformity and stability. By using both of them, a clear printed image without fog can be stably obtained during continuous printing.

The content of the charge control agent is determined by the binder resin 10
It is preferably used in an amount of 0.3 to 10 parts by mass, more preferably 1 to 5 parts by mass, per 0 parts by mass.

The toner of the present invention can be obtained by an extremely general manufacturing method without depending on a specific manufacturing method.
For example, it can be obtained by melt-kneading a resin and a colorant at a temperature equal to or higher than the melting point (softening point) of the resin, followed by pulverization and classification.

Specifically, for example, the above-mentioned resin and colorant are mixed as essential components by a kneading means such as a two-roll, three-roll, pressure kneader or a twin-screw extruder. At this time, the colorant may be uniformly dispersed in the resin, and the conditions for the melt-kneading are not particularly limited, but are usually from 80 to 180 ° C. for from 30 seconds to 2 hours. The coloring agent may be previously subjected to a flushing treatment so as to be uniformly dispersed in the resin, or a master batch melt-kneaded with the resin at a high concentration.

Next, after cooling, the mixture is finely pulverized by a pulverizer such as a jet mill and classified by an air classifier or the like.

The average particle diameter of the particles constituting the toner matrix is as follows:
Although not particularly limited, it is usually adjusted to be 5 to 15 μm.

Usually, an external additive is mixed with the thus obtained toner base using a mixer such as a Henschel mixer.

The external additives are used for modifying the surface of the toner matrix, for example, by improving the fluidity of the toner and the charging characteristics, and include inorganic fine powders such as silicon dioxide, titanium oxide and alumina, and silicone oils. What has been subjected to a surface treatment with a hydrophobizing agent such as, or a fine resin powder is used.

Examples of the silica include those having hydrophobicity and the like among silicon dioxides, and examples thereof include those obtained by subjecting silicon dioxide to a surface treatment with various polyorganosiloxanes, silane coupling agents, or the like. For example, there is one that is commercially available under the following trade names.

AEROSIL R972, R974, R
202, R805, R812, RX200, RY20
0, R809, RX50, RA200HS, RA20
0H [Nippon Aerosil Co., Ltd.] WORKER HDK H2000, H2050EP
HDK H3050EP, HVK2150 [Wacker Chemicals East Asia Co., Ltd.] Nipsil SS-10, SS-15, SS-2
0, SS-50, SS-60, SS-100, SS-5
0B, SS-50F, SS-10F, SS-40, SS
-70, SS-72F, [Nippon Silica Industry Co., Ltd.] CABOSIL TG820F, TS-530, TS-
720 [Cabot Specialty Chemicals
ink〕

These silicas have different average particle sizes.
More than one species may be used in combination. Further, the usage ratio of silica is usually 0.05 to 5 parts by mass, preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the toner base.

In the present invention, the toner is a binder resin,
Although a colorant and a wax are used as main components, other additives may be included. For example, as a lubricant, metal soap, zinc stearate or the like can be used, and as an abrasive, for example, cerium oxide or silicon carbide can be used.

When a part or all of the colorant is replaced with magnetic powder, it can be used as a magnetic one-component developing toner. As the magnetic powder, a ferromagnetic metal such as iron, cobalt, and nickel, or a powder of an alloy or a compound such as magnetite, hematite, or ferrite is used. As these magnetic powders, those subjected to a hydrophobic treatment with an organic silicon or a titanium compound or the like, if necessary, are preferably used. The content of the magnetic powder is 1 to the total mass of the toner.
5 to 70% by mass is good.

In order to use the toner of the present invention as a two-component developer, known carriers such as iron oxide powder can be used as a carrier for the two-component developer. In the present invention, a magnetic carrier having a resin-coated surface is particularly used. Is desirable.

As the core agent of the carrier which can be used in combination with the toner of the present invention, iron powder, magnetite, ferrite and the like used in a usual two-component developing system can be used. Among them, the true specific gravity is low and the resistance is high. Ferrite with excellent fluidity due to excellent environmental stability and easy to be spherical,
Alternatively, magnetite is preferably used. The shape of the core agent can be used without any particular problem, such as spherical or amorphous. The average particle size is generally from 10 to 500 µ, but is preferably from 30 to 80 µ for printing a high-resolution image.

Examples of the coating resin for covering these core agents include polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether polyvinyl ketone, and vinyl chloride. / Vinyl acetate copolymer, styrene / acrylic copolymer, straight silicone resin comprising organosiloxane bond or its modified product, fluororesin, (meth) acrylic resin, polyester, polyurethane, polycarbonate, phenolic resin, amino resin, melamine resin , Benzoguanamine resin, urea resin, amide resin, epoxy resin and the like can be used. Among these, silicone resin, fluororesin, and (meth) acrylic resin are particularly excellent in charge stability and coating strength, and can be more preferably used. That is, the resin-coated carrier used in the present invention is a resin-coated magnetic carrier coated with at least one resin selected from silicone resin, fluororesin, and (meth) acrylic resin using ferrite or magnetite as a core agent. Is preferred.

The method of coating the surface of the carrier core material with the resin is not particularly limited, but a dipping method of dipping in a solution of the coating resin, a spray method of spraying the coating resin solution onto the surface of the carrier core material, or a carrier method. Fluidized bed method in which the carrier is sprayed while being floated by flowing air, a kneader coater method in which a carrier core material and a coating resin solution are mixed in a kneader coater, and a solvent is removed.

The solvent used in the coating resin solution is not particularly limited as long as it dissolves the coating resin. For example, toluene, xylene, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane and the like can be used. The thickness of the coating layer on the carrier surface is usually 0.1
~ 3.0μ.

The mass ratio of the toner containing the colored resin particles to the resin-coated magnetic carrier is not particularly limited, but usually 0.5 to 0.5 parts per 100 parts by mass of the carrier.
5 parts by mass.

[0104]

EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, "parts" represents "parts by mass" unless otherwise specified. (Resin Synthesis Example 1) Styrene 368.5 parts Butyl methacrylate 119.5 parts Acrylic acid 12.0 parts Benzoyl peroxide 5.0 parts Two-volume with thermometer, glass air flow inlet tube, stirrer with vacuum sealing device and water-cooled Jimroth condenser Into a four-necked round bottom flask were charged 500 parts of xylene and the total amount of the above monomers and initiator. After the inside of the reactor was replaced with an inert atmosphere by introducing nitrogen gas from a glass air flow inlet tube, the content was gradually heated to 75 ° C. by a mantle heater with a slider box. Reaction is 65 ° C to 80 ° C
After 10 to 12 hours, the temperature was raised to 130 ° C. to complete the polymerization, and the polymerization was completed. Next, the water-cooled condenser and the glass air flow introducing tube were removed from the flask, and a capillary for vacuum distillation and a Claisen fractionating tube were attached instead. A thermometer and a water-cooled Liebig condenser are connected to the Klaisen distillation tube, and the outlet of the condenser is connected to an eggplant-shaped flask via a suction adapter. The suction adapter and the vacuum pump are connected by a rubber tube for decompression via a manometer and a trap, and the preparation for decompression distillation is completed. When the mantle heater is heated and the contents are sufficiently stirred and the vacuum pump is operated to reduce the pressure to 20 mmHg, the xylene or unreacted monomer starts to distill at a liquid temperature of 75 ° C. and a distilling temperature of 38 ° C. Finally, the pressure was reduced to 0.5 mmHg at a liquid temperature of 180 ° C. to completely remove the solvent. The obtained polymer (hereinafter referred to as polymer (A)) was poured into a stainless steel pan in a molten state at a high temperature, cooled to room temperature, and crushed.

The obtained polymer (A) had a softening point of the ring and ball method of 119 ° C.
Measurement by GPC (gel permeation chromatography), for which a calibration curve is obtained using monodisperse polystyrene as a standard substance, shows a number average molecular weight of about 12000 and a weight average molecular weight of about 3
It was 0000.

The polymer (A) was crushed into small pieces each having a side of 5 mm or less, and 300 parts thereof were weighed and charged into a one-capacity four-necked round bottom flask. The flask was equipped with a high-speed stirrer, a thermometer, and a drying tube filled with silica gel, and heating was started with a mantle heater. The charged resin gradually melted, and when the temperature was further increased, a completely mucous state was obtained. When the high-speed stirrer is slowly rotated and the temperature reaches 160 ° C, while increasing the stirring, 3.7 parts of calcium hydroxide (equivalent to about 0.5 equivalents of all free carboxyl groups contained in the polymer (A)) is added to 20 parts.
The mixture was gradually added over a period of minutes, and reacted at a liquid temperature of 150 to 195 ° C. for 10 hours. After the reaction, the hot melt was spread on a stainless steel pan, cooled to room temperature, and then crushed to obtain a calcium metal chloride polymer (hereinafter, referred to as polymer (B)).

The obtained polymer (B) was quantified by FTIR (Fourier transform infrared spectrometer, “FTS-10” manufactured by Digilab, USA). As a result, the reaction rate of calcium hydroxide was about 25%.
≒ 8.3 la 10 ^-5 . The softening point of the polymer (B) is 148
T ₁ -T _S = 29 ° C. and Tg = 63 ° C.

(Resin Synthesis Example 2) Styrene 570 parts Diethyl fumarate 42 parts Butyl acrylate 75 parts α-ethylcrotonic acid 16 parts Benzoyl peroxide 4 parts With the above composition, polymerization was carried out in substantially the same manner as in Resin Synthesis Example 1. . The obtained polymer had a softening point of 115 ° C., a number average molecular weight of about 7,500, and a weight average molecular weight of about 20,500. This polymer 3
To 00 parts, 4.4 parts of aluminum isopropoxide (corresponding to about 1 equivalent of all free carboxylic acids contained in the polymer) was reacted in the same manner as in Example 1.

The obtained aluminum metal chloride polymer (hereinafter referred to as polymer (C)) had a softening point of 166 ° C., and the conversion of aluminum isopropoxide by FTIR was about 95%. Therefore, N ≒ 2.1 × 10 ⁻⁴ , and T ₁ −T _S = 51 ° C.
Tg = 55 ° C.

(Resin Synthesis Example 3) Styrene 805 parts Lauryl methacrylate 124 parts Vinylpyridine 25 parts Methacrylic acid 46 parts Azobisisobutyronitrile 10 parts With the above composition, polymerization was carried out in substantially the same manner as in Resin Synthesis Example 1. I got it. The obtained polymer had a softening point of 120 ° C. 500 parts of this polymer is melted in a kneader, and 17.2 parts of magnesium acetate tetrahydrate (corresponding to 1 equivalent of the total free carboxylic acid contained in the polymer) is added and melt-kneaded for 30 minutes or more. The obtained magnesium metal chloride polymer (hereinafter referred to as polymer (D)) had a softening point of 155 ° C., a reaction rate of about 30% by FTIR, and T ₁ −
T _S = 35 ° C., Tg = 50 ° C.

(Resin Synthesis Example 4)
The same operation as in Resin Synthesis Example 1 was performed using 300 parts of the polymer (A).
0.37 parts of calcium hydroxide (total contained in polymer (A)
About 0.1 equivalent of free carboxyl group)
Was. The obtained calcium metal chloride polymer (hereinafter referred to as polymer
(E)) was determined by FTIR and found to be calcium hydroxide.
The reaction rate is about 27.5%, the softening point is 134 ° C,₁-T _S
= 15 ° C, N = 9.1 la 10^-6Met.

(Example 1) <Production of Toner> Polymer (B) 100 parts Carbon black; Black Pearls 460 5 parts (manufactured by Cabot Specialty Chemicals Ink) Charge control agent (positive charge control agent); Bontron N-01 3 parts (manufactured by Orient Chemical Industry Co., Ltd.) wax; 4 parts of wax are mixed with a Henschel mixer and kneaded with a twin-screw kneader. The kneaded material thus obtained was pulverized and classified to obtain “toner α before external addition” having a volume average particle diameter of 10.1 μm.

100 parts of the above “toner α before external addition” silica; 1 part of TG820F (manufactured by Cabot Specialty Chemicals, Inc.) was mixed with a Henschel mixer and then sieved.
“Toner α” was obtained.

<Adjustment of Developer> A developer α was prepared by mixing and stirring 5 parts of the “toner α” and 95 parts of a carrier (silicone resin-coated ferrite carrier).

In the same manner, toners were prepared according to the formulations shown in Table 1, and the developer α (Example 1) to the developer η (Example 7) and the developer θ (Comparative Example 1) to the developer κ (Comparative Example) 3) was manufactured.

Note that the developer η is a magnetic powder BL as a colorant.
Use 40 parts of -200 (manufactured by Titanium Industry). A magnetic one-component developer was used without being mixed with a carrier (a ferrite carrier coated with a silicon resin).

Table 1. Recipe

[0118]

[Table 1]

* 5 parts of Black Pearls 460 (manufactured by Cabot Specialty Chemicals, Inc.) was added as a colorant to all developers except for Example 7.

Viscol 550P; polypropylene wax Nigrosine N-01 manufactured by Sanyo Kasei Co., Ltd .; Bontron N-01 manufactured by Orient Chemical Industry Co., Ltd. <Fixing offset test and printing test> Obtained in the above Examples and Comparative Examples. For the developer, a fixing start temperature, a hot offset start temperature, and a print test were performed as follows.

(Fixing Offset Test by Heat Roll Fixing) An unfixed image sample of A-4 paper size was prepared using a test machine modified from a commercially available two-component developing copier, and a heat roll fixing unit having the following specifications was mounted. The fixing start temperature and the presence or absence of an offset phenomenon were confirmed under the following test conditions.

With respect to the toner of Example 7, an unfixed image sample was prepared by modifying a commercially available magnetic one-component developing type printer.

[0123]

In order to measure the fixing start temperature, an image density remaining ratio calculated by the following equation was obtained.

Image density remaining ratio = image density after fastness test / image density before left test * Image density was measured by Macbeth image densitometer RD-918. * The image density after fastness test is the image density after rubbing the fixed image using a Gakushin type friction fastness tester (load: 200 g, rubbing operation: 5 strokes).

An image density remaining ratio of 80% or more was set to a practically acceptable level, and the lowest temperature was defined as a fixing start temperature.

The offset start temperature was a temperature at which the offset phenomenon was visually observed by observing the fixed image sample. (Printing test) The printing quality of continuous printing was evaluated using a commercially available laser beam printer (with a selenium photosensitive member), and the charge amount of the developer was measured. Replenishment of toner during continuous printing was performed automatically by filling the toner after silica addition into a replenishment toner hopper of the machine.

The charge amount was measured by a blow-off charge amount measuring device. The image density was measured with a Macbeth densitometer RD-918, and the background stain was determined by subtracting the white paper density before printing from the white background density.

The toner of Example 7 was tested by modifying a commercially available magnetic one-component developing printer. Regarding the charge amount, a toner is sampled from the inside of the developing device for each number of printed sheets, a developer is prepared with toner / carrier (silicone resin-coated ferrite carrier) = 5/95 (mass ratio), and another two-component developer It measured similarly to. (Toner scattering amount) Observe the inside of the machine after printing 50KP (50,000 sheets). ○: When there is almost no dirt due to scattered toner around the photoconductor, developing device peripheral part, etc., Δ: When a little dirt is generated, Severe dirt Was evaluated as x when the occurrence of.

Table 2 shows the evaluation results.

Table 2. Evaluation results

[0132]

[Table 2]

The indications in the table are as follows.

* ΔT; T _L −T _H * “Charge amount”; μC / g * “Background dirt evaluation” ○: less than 0.01, Δ: 0.01 to less than 0.03, la: 0.03 or more * “Toner scattering”: 50 KP ( (50,000 sheets) Visual observation after printing ○: Almost no scattering △: Slight scattering caused ×: Intense scattering occurred

As is clear from Table 2, the toner of the present invention is superior in both low-temperature fixability and high-temperature offset resistance to the toner of the comparative example.

Furthermore, the toner of the present invention is a developer having stable charging performance without causing background stain on a white background portion of a printed matter in continuous printing and toner scattering inside the machine.

In order to confirm the difference between the wax according to the present invention and the polypropylene wax widely used for toner, the dispersion state of the polypropylene wax in the toner used in Comparative Example 1 was observed with a microscope. It was found that the dispersion particles were very large compared to the dispersion of the wax used in the above. In addition, since the carrier surface after 50KP printing had attached polypropylene and the occurrence of spent carrier was observed, the difference in the dispersibility of the wax appeared as background contamination, toner scattering, and the difference in developer life. Inferred. In Examples according to the present invention, generation of spent carrier was not recognized.

[0138]

As shown in the above examples, a polyvalent metal salt of a carboxyl group-containing polymer (a) obtained by copolymerizing an addition-polymerizable unsaturated carboxylic acid and another copolymerizable monomer is converted into a polyvalent metal salt. According to the toner of the present invention using a wax comprising an ester of a monovalent or polyvalent carboxylic acid having a monovalent metal chloride polymer (b) and a chain hydrocarbon group having 12 to 40 carbon atoms with a monovalent or polyhydric alcohol. Thus, a developer exhibiting good fixing characteristics and offset resistance in a wider temperature range can be obtained. At the same time, since the toner of the present invention has sufficient mechanical strength and stable charging behavior, it withstands friction with the carrier in the developing device, does not generate spent carrier and toner scattering, and has a high density without fog. In addition, a high-quality printed image can be stably obtained.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 9/08 365 G03G 9/08 325 368 361 (72) Inventor Masamichi Asai 4 Tobe-cho, Nishi-ku, Yokohama, Kanagawa Prefecture −119 F term (reference) 2H005 AA01 AA06 AA21 CA04 CA14 CA16 CB00 EA03 EA07 4J002 BB081 BB141 BB171 BB181 BC041 BC081 BC111 BC121 BD021 BD101 BD111 BD131 BD141 BF011 BF021 BG011 BG031 BG091 BG121 BL011

Claims (4)

[Claims] 1. A toner containing a binder resin, a colorant and a wax, wherein the binder resin is obtained by copolymerizing an addition-polymerizable unsaturated carboxylic acid and another copolymerizable monomer. (a) is a polyvalent metal chlorinated polymer (b) obtained by chlorinating a polyvalent metal, wherein the wax is an ester of a carboxylic acid and an alcohol, and a part of the molecule is a chain hydrocarbon having 12 to 40 carbon atoms. An electrostatic image developing toner having a structure having a group. 2. The electrostatic image according to claim 1, wherein the wax contains at least one selected from compounds represented by the following formulas 1 to 5. Development toner. <General formula 1> (R1 and R2 are a hydrocarbon group having 1 to 40 carbon atoms,
At least one of them represents a chain hydrocarbon group having 12 or more carbon atoms. <General formula 2> (R1, R2 and R3 are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them represents a chain hydrocarbon group having 12 or more carbon atoms.) <General formula 3> (R1, R2 and R3 are a hydrocarbon group having 1 to 40 carbon atoms, and at least one of them represents a chain hydrocarbon group having 12 or more carbon atoms.) <General formula 4> (R1 is a hydrocarbon group having 12 to 40 carbon atoms. R2 is a hydrocarbon group having 1 to 40 carbon atoms. A + b = 4, a represents an integer of 1 to 4, and b represents an integer of 0 to 3. <General formula 5> (R1, R2 and R3 are a hydrocarbon group having 1 to 40 carbon atoms, at least one of which is a chain hydrocarbon group having 12 or more carbon atoms, and a and c are integers of 0 to 2,
a + c = 2. b is an integer from 1 to 4, and d is 1
Or 2. Furthermore, e = d-1. ) 3. The polyvalent metal chloride polymer (b) is represented by the following formula (1):
3. The toner according to claim 1, wherein the polymer satisfies the relationship represented by the formulas (2) and (3). 10 ⁻⁵ ≦ N ≦ 2 × 10 ⁻³ (1) T ₁ −T _S ≧ 20 ° C. (2) 35 ° C. ≦ Tg ≦ 75 ° C. (3) [In the above formula, N represents a polyvalent metal chloride polymer (b ) The number of moles of carboxyl ions converted into metal contained in 1 g, T ₁ is the softening point of polyvalent metal chloride polymer (b) by ring and ball method, and T _S is the softening point of carboxyl group-containing polymer (a) by ring and ball method. Point, T
g represents the glass transition temperature of the polyvalent metal chloride polymer (b). ] 4. The method according to claim 1, wherein the polyvalent metal is Al, Ag, Ba, Ca, Cd, Co,
4. The method according to claim 1, wherein the material is at least one selected from the group consisting of Cr, Cu, Fe, Hg, Mg, Mn, Ni, Pb, Sn, Sr, Ti, and Zn. The toner for an electrostatic developer as described in the above item.