JP2003173047A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner excellent in grindability, low temperature fixability and preservability and excellent also in environmental stability. <P>SOLUTION: The toner comprises a colorant and a bonding resin comprising a resin (crystalline resin) having a ratio of its softening point to the highest peak temperature of heat of fusion [(softening point)/(peak temperature)] of 0.6 to <1.1 and a hybrid resin (amorphous hybrid resin) having a ratio of its softening point to the highest peak temperature of heat of fusion [(softening point)/(peak temperature)] of 1.1-4.0, the amorphous hybrid resin is obtained by partial chemical bonding of two polymeric resin components having independent reaction paths, at least one of these is the same polymeric resin component as the crystalline resin, and the weight ratio of the crystalline resin to the amorphous hybrid resin is 1:99 to 50:50. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.

[0002]

2. Description of the Related Art Toners using a crystalline polyester as a binder resin have been studied with the aim of improving low-temperature fixability, which is one of the major problems of electrophotography (Patent Document 1, etc.). However, although the crystalline polyester has excellent low-temperature fixability, it has the drawback that when used alone, the pulverizability, storability, charge stability and the like are deteriorated.

In view of this, Patent Document 2 reports a toner in which a crystalline polyester and an amorphous resin are used in combination, but since such a toner has different skeletons of both resins, the dispersibility of the crystalline polyester is poor. It becomes sufficient, the effect of improving fixability and storability is small, and charging stability becomes insufficient.

When the skeletons of the crystalline polyester and the amorphous polyester are almost the same as in the toner reported in Patent Document 3, the dispersibility of the crystalline polyester is too high, and a large amount is present on the toner surface. The exposed crystalline polyester causes deterioration of pulverizability and storability.

Further, in Patent Documents 4 and 5 as well, the combined use of crystalline polyester and amorphous polyester is being investigated, and although some improvement in low temperature fixing property is recognized, pulverizability and storability are improved. In addition, further improvement is required for environmental stability.

[0006]

[Patent Document 1] JP-A-49-129540 (claim 1)

[Patent Document 2] Japanese Patent Publication No. 5-44029 (Claim 1)

[Patent Document 3] Japanese Patent Publication No. 62-39428 (Claim 1)

[Patent Document 4] Japanese Patent Laid-Open No. 2001-222138 (Claim 1)

[Patent Document 5] Japanese Unexamined Patent Publication No. 11-249339 (Claim 1)

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a toner having excellent pulverizability, low temperature fixability and storability, and excellent environmental stability.

[0008]

According to the present invention, the ratio of the softening point to the maximum peak temperature of heat of fusion (softening point / peak temperature) is 0.
A resin having a ratio of 6 or more and less than 1.1 (hereinafter, referred to as a crystalline resin) and a hybrid resin having a ratio of the maximum peak temperature of the softening point to the heat of fusion (softening point / peak temperature) of 1.1 to 4.0 ( Hereinafter, referred to as an amorphous hybrid resin) and a toner containing a binder resin and a colorant,
The amorphous hybrid resin is formed by partially chemically bonding two polymerization resin components each having an independent reaction path, and at least one of them is the same polymerization resin component as the crystalline resin, The present invention relates to a toner in which the weight ratio of the crystalline resin to the amorphous hybrid resin (crystalline resin / amorphous hybrid resin) is 1/99 to 50/50.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, by combining a crystalline resin and an amorphous hybrid resin, pulverizability, storability, and environmental stability of charging are improved as compared with a toner containing a conventional crystalline resin. Remarkably improved.

That is, the amorphous hybrid resin according to the present invention is formed by partially chemically bonding two polymerization resin components each having an independent reaction path, and at least one of them is the same as the crystalline resin. Since it is the resin component, the dispersion state of the crystalline resin can be easily adjusted. As a result, the crystalline resin maintains an appropriate dispersed state without being miscible more than necessary, thereby improving the pulverizability, the storage stability and the charge stability without adversely affecting the fixability. .

The weight ratio of the crystalline resin and the amorphous hybrid resin (crystalline resin / amorphous hybrid resin) is 1 /
99-50 / 50, preferably 3 / 97-40 / 60,
It is more preferably 5/95 to 30/70.

Examples of the crystalline resin include crystalline polyester, crystalline polyester polyamide, crystalline polyamide and the like. Among them, the crystalline polyester is preferable from the viewpoint of fixability and compatibility with the amorphous hybrid resin. Is preferred.

In the present invention, the crystalline polyester is
An alcohol component containing 80 mol% or more of an aliphatic diol having 2 to 6 carbon atoms, preferably 4 to 6 carbon atoms and 2 to 6 carbon atoms
A resin obtained by polycondensing a carboxylic acid component containing 80 mol% or more of an aliphatic dicarboxylic acid compound of 8, preferably 4 to 6, and more preferably 4, is preferable.

As the aliphatic diol having 2 to 6 carbon atoms,
Ethylene glycol, 1,2-propylene glycol,
1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-butenediol and the like can be mentioned. Among these, α, ω-straight chain alkanediol, preferably 1,4-butanediol and 1,
6-hexanediol is more preferred.

The aliphatic diol having 2 to 6 carbon atoms is 80 mol% or more, preferably 85 to 10 in the alcohol component.
It is desirable that the content is 0 mol%, more preferably 90 to 100 mol%, and in particular, one type of aliphatic diol therein is 70 mol% or more, preferably 80 mol% or more, more preferably in the alcohol component. Is preferably 85 to 95 mol%.

The alcohol component may contain a polyhydric alcohol component other than the aliphatic diol having 2 to 6 carbon atoms, and the polyhydric alcohol component may be polyoxypropylene (2.2) -2, 2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2)-
Divalent aromatic alcohol such as alkylene (C2-3) oxide (average addition mole number 1-10) adduct of bisphenol A such as 2,2-bis (4-hydroxyphenyl) propane, glycerin, pentaerythritol And trihydric or higher alcohols such as trimethylolpropane.

Examples of the aliphatic dicarboxylic acid compound having 2 to 8 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, and anhydrides of these acids. And alkyl (having 1 to 3 carbon atoms) esters, and fumaric acid is preferable among them. In addition, an aliphatic dicarboxylic acid compound refers to an aliphatic dicarboxylic acid, an anhydride thereof and an alkyl (C1 to C3) ester thereof as described above, and of these, the aliphatic dicarboxylic acid is preferable.

The aliphatic dicarboxylic acid compound having 2 to 8 carbon atoms is contained in the carboxylic acid component in an amount of 80 mol% or more, preferably 85 to 100 mol%, more preferably 90 to 100 mol%. In particular, it is desirable that one kind of the aliphatic dicarboxylic acid compound therein accounts for 60 mol% or more, preferably 80 mol% or more, more preferably 85 to 100 mol% or more in the carboxylic acid component. Among them, from the viewpoint of storage stability of the crystalline polyester, fumaric acid is contained in the carboxylic acid component in an amount of preferably 60 mol% or more, more preferably 70 to 100 mol%, and particularly preferably 80 to 100 mol%. Is desirable.

The carboxylic acid component may contain a polyvalent carboxylic acid component other than the aliphatic dicarboxylic acid compound having 2 to 8 carbon atoms. Examples of the polyvalent carboxylic acid component include phthalic acid, isophthalic acid, Aromatic dicarboxylic acids such as terephthalic acid; aliphatic dicarboxylic acids such as sebacic acid, azelaic acid, n-dodecylsuccinic acid, n-dodecenylsuccinic acid;
Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid;
Examples thereof include trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid; and anhydrides of these acids and alkyl (C1 to C3) esters.

The alcohol component and the carboxylic acid component are subjected to polycondensation by reacting in an inert gas atmosphere, if necessary, with an esterification catalyst, a polymerization inhibitor and the like at a temperature of 120 to 230 ° C. You can In particular,
Charge all the monomers at once to increase the strength of the resin, or first react the divalent monomers to reduce the low molecular weight components and then add the trivalent or higher monomers to react You may use the method of making it. Further, the reaction may be promoted by reducing the pressure of the reaction system in the latter half of the polymerization.

In the present invention, "crystalline" means
The ratio between the softening point and the maximum peak temperature of heat of fusion (softening point / peak temperature) is 0.6 or more and less than 1.1, preferably 0.9 or more and less than 1.1, and more preferably 0.98 to 1.05. "Amorphous" means that the ratio between the softening point and the maximum peak temperature of heat of fusion (softening point / peak temperature) is 1.1 to.
It means 4.0, preferably 1.5 to 3.0.

The softening point of the crystalline resin is preferably 85 to
The temperature is 150 ° C, more preferably 90 to 140 ° C, and particularly preferably 100 to 135 ° C. The maximum peak temperature of heat of fusion is preferably 77 to 166 ° C, more preferably 82 to 155 ° C, and particularly preferably 91 to 150 ° C.

Similarly, the softening point of crystalline polyester is
Preferably 85-150 ° C, more preferably 90-14
It is 0 ° C, particularly preferably 100 to 135 ° C. Also,
The maximum peak temperature of heat of fusion is preferably 77 to 166.
° C, more preferably 82 to 155 ° C, particularly preferably 9
It is 1 to 150 ° C.

When the crystalline polyester is composed of two or more kinds of resins, it is desirable that at least one kind, and preferably all of them is the crystalline polyester described above.

In the present invention, the hybrid resin in which two polymerization resin components each having an independent reaction route are partially chemically bonded, even if one obtained from two or more resins as a raw material, In order to efficiently obtain a hybrid resin, it may be obtained from the above-mentioned resin and a raw material monomer of another kind of resin, or may be obtained from a mixture of two or more kinds of raw material monomers of the resin. Is 2
Those obtained from a mixture of raw material monomers of one or more resins are preferable. Note that, as described above, from the viewpoint of compatibility with the crystalline resin, at least one of the resin components of the hybrid resin is the same resin component as the crystalline resin.

Therefore, as the hybrid resin, two raw material monomers of the polymerization type resin having independent reaction paths, preferably the raw material monomer of the polycondensation type resin and the raw material monomer of the addition polymerization type resin are mixed and the two A resin obtained by carrying out a polymerization reaction is preferable.

Typical examples of the polycondensation resin include polyester, polyester-polyamide, polyamide and the like, and typical examples of the addition polymerization resin include a vinyl resin obtained by a radical polymerization reaction.

As the raw material monomer of polyester, 2
Examples thereof include polyhydric alcohols having a valency of 2 or more and polyhydric carboxylic acid compounds having a valency of 2 or more. However, in order to obtain an amorphous polyester, when a monomer that promotes crystallization of a resin such as an aliphatic diol having 2 to 6 carbon atoms or an aliphatic carboxylic acid compound having 2 to 8 carbon atoms is used, In a resin in which two or more kinds of monomers are used in combination to suppress crystallization, that is, in each of the alcohol component and the carboxylic acid component, one kind of these monomers is 10 to 70 mol%, preferably 20 to 6 in each component.
0% by mole of these monomers, 2 or more, preferably 2 to 4 of these monomers are used, or a monomer that promotes non-crystallization of the resin, preferably an alkylene oxide adduct of bisphenol A in the alcohol component. , Or succinic acid substituted with an alkyl group or an alkenyl group in the carboxylic acid component, in the alcohol component or the carboxylic acid component, preferably in both components, 30 to 100 mol%, preferably 50 to
It is preferably used at 100 mol%.

As the raw material monomer used for forming the polyester / polyamide or the amide component in the polyamide, various known polyamines, aminocarboxylic acids, amino alcohols and the like can be mentioned, preferably hexamethylenediamine and ε-caprolactam. Is.

As raw material monomers for vinyl resins, styrene compounds such as styrene and α-methylstyrene; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; Vinyl esters such as vinyl acetate and vinyl propionate; alkyl (C1-18) esters of (meth) acrylic acid, ethylenic monocarboxylic acid esters such as dimethylaminoethyl (meth) acrylate; vinyl methyl ether, etc. Vinyl ethers; vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinylpyrrolidone;
From the viewpoint of pulverizability and charge stability, the alkyl ester of styrene and / or (meth) acrylic acid is 50% by weight.
As described above, it is desirable that the content is 80 to 100% by weight.

When the raw material monomer for the vinyl resin is polymerized, a polymerization initiator, a cross-linking agent or the like may be used if necessary.

In the present invention, the weight ratio of the polycondensation resin component to the addition polymerization resin component (polycondensation resin component /
Addition polymerization resin component), that is, the weight ratio of the raw material monomer of the condensation polymerization resin to the raw material monomer of the addition polymerization resin is
From the viewpoint of offset resistance, the continuous phase is preferably a polycondensation resin, and is usually 50/50 to 95/5, preferably 60/40 to 95/5.

As the amorphous hybrid resin in the present invention, in addition to the mixture of the raw material monomers of the two polymerization type resins each having an independent reaction path, the raw material of the two polymerization type resins is further used as one of the raw material monomers. A resin obtained by mixing monomers (both reactive monomers) capable of reacting with any of the monomers is preferable.

The bireactive monomer has a hydroxyl group in the molecule,
A monomer having at least one functional group selected from the group consisting of a carboxyl group, an epoxy group, a primary amino group and a secondary amino group, and an ethylenically unsaturated bond is preferable. By using the bireactive monomer, it is possible to improve the dispersibility of the resin as the dispersed phase. Specific examples of the bireactive monomer include:
Examples thereof include acrylic acid, fumaric acid, methacrylic acid, citraconic acid, maleic acid, and the like, and among these, acrylic acid, methacrylic acid, and fumaric acid are preferable.

The amount of the both-reactive monomer used is 0.1 to 10 with respect to 100 parts by weight of the raw material monomer of the polycondensation resin.
Parts by weight are preferred. In the present invention, the bireactive monomer is treated as a monomer different from the raw material monomer of the polycondensation resin and the raw material monomer of the addition polymerization resin because of its unique performance.

In the present invention, when the hybrid resin is obtained by carrying out the two polymerization reactions using the above-mentioned raw material monomer mixture and the bireactive monomer, the progress and completion of the polymerization reaction are time-wise. It is not necessary to be simultaneous, and the reaction temperature and time may be appropriately selected according to each reaction mechanism to proceed and complete the reaction.

For example, in the method for producing a hybrid resin in the present invention, a raw material monomer for a condensation polymerization type resin, a raw material monomer for an addition polymerization type resin, a bireactive monomer, a catalyst such as a polymerization initiator, etc. are mixed, and first, mainly 50-180 ° C
To obtain an addition polymerization type resin component having a functional group capable of undergoing a polycondensation reaction by a radical polymerization reaction, and then setting the reaction temperature to 19
After the temperature is raised to 0 to 270 ° C., it is preferable to form the polycondensation resin component mainly by the polycondensation reaction.

The softening point of the amorphous hybrid resin is 80.
It is desirable that the temperature is ˜170 ° C., preferably 90 to 160 ° C., more preferably 95 to 155 ° C.

The weight ratio of the crystalline polyester to the amorphous hybrid resin (crystalline polyester / amorphous hybrid resin) is 1/99 to 50/50, preferably 3
/ 97-40 / 60, more preferably 5 / 95-30 /
It is preferably 70.

The binder resin may contain other resins such as amorphous polyester, styrene-acrylic resin, epoxy resin, polycarbonate and polyurethane.

As the colorant, all of the dyes and pigments used as the colorant for toner can be used. Black colorants such as carbon black and metal complex oxides; phthalocyanine blue, permanent brown F
G, Brilliant First Scarlet, Pigment Green B, Rhodamine-B Base, Solvent Red 49, Solvent Red 146, Solvent Blue 3
5, quinacridone, carmine 6B, disazo yellow, and the like, which may be used alone or in combination of two or more. In the present invention, the toner may be a black toner, a color toner or a full color toner. May be The content of the colorant is preferably 1 to 40 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the binder resin.

In the present invention, wax is preferably contained from the viewpoint of fixability.

Examples of the waxes include polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax, polyolefin wax such as Fischer-Tropsch wax, carnauba wax, wax wax, beeswax wax, whale wax, montan wax,
Examples thereof include ester waxes such as rice wax and amide waxes such as fatty acid amide wax. These may be used alone or in combination of two or more. Among these, Fischer-Tropsch wax and carnauba wax are preferable from the viewpoint of fixability and storability, and Fischer-Tropsch wax is more preferable from the viewpoint of dispersibility.

The content of the wax is preferably 0.1 to 20 parts by weight, and 0.5 to 100 parts by weight with respect to 100 parts by weight of the binder resin.
10 parts by weight is more preferable.

The wax may be melt-kneaded together with the binder resin and the like, but is preferably finely dispersed in the amorphous hybrid resin from the viewpoint of pulverizability and storability. In the production stage of the crystalline hybrid resin, it is more preferable to add it to the reaction system together with the raw material monomer such as the polycondensation resin raw material monomer and the addition polymerization resin raw material monomer.

Further, in the toner of the present invention, a charge control agent, a release agent, a conductivity adjusting agent, an extender pigment, a reinforcing filler such as a fibrous substance, an antioxidant, an antiaging agent, a fluidity improving agent,
An additive such as a cleaning property improver may be appropriately contained.

The toner of the present invention is preferably a pulverized toner obtained by a kneading pulverization method or the like. For example, a binder resin, a colorant and the like are uniformly mixed with a mixer such as a Henschel mixer or a ball mill, and then a closed type kneader or Melt and knead with a single-screw or twin-screw extruder, continuous two-roll type kneader, etc.,
It can be manufactured by cooling, pulverizing and classifying. further,
If necessary, a fluidity improver or the like may be added to the surface of the toner. The volume average particle diameter of the toner thus obtained is preferably 3 to 15 μm.

The toner of the present invention may contain a magnetic substance as a colorant because a good fixing property can be obtained even if it is a magnetic toner.

Examples of the magnetic material include alloys such as magnetite, hematite and ferrite, and ferromagnetic metal powders such as iron, cobalt and nickel. The addition amount of the magnetic material is
30 to 200 parts by weight is preferable with respect to 100 parts by weight of the binder resin. When it contains a magnetic material, it can be used as a black toner and does not need to contain any other coloring agent.

The toner of the present invention containing no magnetic substance can be used as a non-magnetic one-component developer or a two-component developer mixed with a carrier.

[0051]

[Softening point] Using a Koka-type flow tester (CFT-500D, manufactured by Shimadzu Corporation), while heating 1 g of a sample at a temperature rising rate of 6 ° C / min, a plunger of 1.96 MPa was used. 1mm in diameter and 1mm in length
Of the flow tester's plunger drop amount (flow value) -temperature curve is drawn, and when the height of the S-shaped curve is h, the temperature corresponding to h / 2 (half of the resin is The flow-out temperature) is the softening point.

[Maximum peak temperature of melting heat and glass transition point] Differential scanning calorimeter (DSC2 manufactured by Seiko Instruments Inc.)
10) is used to raise the temperature to 200 ° C., and the sample cooled from that temperature to 0 ° C. at a temperature lowering rate of 10 ° C./min is measured at a temperature raising rate of 10 ° C./min to obtain the maximum peak temperature of heat of fusion. Further, the glass transition point peculiar to the amorphous resin is the temperature at the intersection of the tangent line showing the maximum slope from the extension line of the baseline and the rising portion of the peak below the maximum peak temperature to the apex of the peak in the above measurement. .

Production Example of Crystalline Polyester The raw material monomers shown in Table 1 and 2 g of hydroquinone were reacted at 160 ° C. for 5 hours in a nitrogen atmosphere, and then 20
The temperature was raised to 0 ° C., the reaction was performed for 1 hour, and the reaction was further performed at 8.3 kPa for 1 hour. The obtained resins are referred to as resins a and b.

[0054]

[Table 1]

Production Example 1 of Amorphous Hybrid Resin A mixture of a raw material monomer for an addition polymerization type resin shown in Table 2, a bireactive monomer, a wax and 50 g of ditertiary butyl peroxide as a polymerization initiator is shown in Table 2. The mixture was added dropwise to a mixture of the raw material monomer of the polymer resin and 4 g of dibutyltin oxide at 160 ° C. over 1 hour. After further addition polymerization at 160 ° C. for 1 hour, the temperature was raised to 230 ° C. to carry out a polycondensation reaction, and the reaction was terminated when the predetermined softening point was reached while appropriately reducing the pressure of the reaction system. The obtained resins are referred to as A to C and E. The average dispersed diameter of the wax in the resin B was 4.5 μm.

Production Example 2 of Amorphous Hybrid Resin A mixture of a raw material monomer for an addition polymerization resin shown in Table 2, a bireactive monomer, and 50 g of ditertiary butyl peroxide as a polymerization initiator was used in a condensation polymerization system shown in Table 2. The mixture was added dropwise to a mixture of the resin raw material monomer, wax and 4 g of dibutyltin oxide at 160 ° C. over 1 hour. After further addition polymerization at 160 ° C. for 1 hour, the temperature was raised to 230 ° C. to carry out a polycondensation reaction, and the reaction was terminated when the predetermined softening point was reached while appropriately reducing the pressure of the reaction system. Let the obtained resin be F and G. The average dispersed diameter of the wax in Resin F was 4.1 μm, and the average dispersed diameter of the wax in Resin G was 4.2 μm.

Production Example of Amorphous Polyester A raw material monomer for a condensation-polymerized resin shown in Table 2 and 6.5 g of dibutyltin oxide are heated at 230 ° C. in a nitrogen atmosphere while the pressure of the reaction system is appropriately reduced until a predetermined softening point is reached. Resin D was obtained by reacting.

[0058]

[Table 2]

Examples 1 to 8 and Comparative Examples 1 to 4 The binder resin, colorant, charge control agent, magnetic powder and wax shown in Table 3 were premixed with a Henschel mixer, and then
The mixture was melt-kneaded with a twin-screw extruder, cooled, pulverized, and classified to obtain a powder having a volume average particle diameter of 9 μm. In the crushing process, it passes through a 16-mesh (mesh size: 1.0 mm) sieve and then 22 mesh (mesh size: 0.710 mm).
The coarse powder that did not pass through the sieve was subjected to Test Example 1 described later.

To 100 parts by weight of the obtained powder, 0.3 part by weight of hydrophobic silica "HVK2150" (manufactured by Clariant Co., Ltd.) was mixed and adhered by a Henschel mixer to obtain a toner.

Test Example 1 From the pulverizability index of the coarse powder obtained in the toner manufacturing process, the pulverizability was evaluated according to the following evaluation criteria. Precisely weigh 20.00 g of coarse powder, and use a coffee mill (PHILI
After crushing for 10 seconds with HR-2170 manufactured by PS, 30
It was passed through a mesh (mesh size: 500 μm) sieve, the weight (A) g of the coarse powder that did not pass was precisely weighed, and the residual rate was determined by the following formula. Residual rate = (A) / Weight of coarse powder before coffee mill crushing (20.00) × 100 The average value of three measurements of the residual rate is taken as the crushability index.
The lower the pulverizability index, the better the pulverizability of the toner in the manufacturing facility. The results are shown in Table 3. (Evaluation criteria) ◎: Less than 30 ○: 30 or more, less than 50 ×: 50 or more

Test Example 2a [Magnetic toner (Examples 1 to 4,
Evaluation of Comparative Examples 1 to 5)] A commercially available monochrome copying machine "NP6045" (manufactured by Canon Inc., printing speed: 45 sheets of A4 paper / minute) is modified to be a device capable of arbitrarily setting the temperature of the fixing roller. After mounting the toner, the temperature of the fixing roller was sequentially raised from 90 ° C. to 240 ° C., an image was formed, and the low temperature fixability was evaluated by the following method. The results are shown in Table 3.

[Low-temperature fixing property] A sand eraser having a bottom surface of 15 mm × 7.5 mm under a load of 500 g was used. The image fixed through a fixing device was rubbed 5 times, and the optical reflection density before and after rubbing was measured by a reflection densitometer “ RD-915 "(manufactured by Macbeth) and the ratio of both (after rubbing / before rubbing)
First, the temperature of the fixing roller exceeding 70% is set as the minimum fixing temperature. From the obtained minimum fixing temperature, the low temperature fixability is evaluated according to the following evaluation criteria. (Evaluation criteria) ◎: less than 130 ° C ○: 130 ° C or more, less than 150 ° C ×: 150 ° C or more

Test Example 2b [Non-magnetic toner (Example 5,
6. Evaluation of Comparative Example 4)] 4 parts by weight of toner was mixed with 96 parts by weight of a silicon-coated ferrite carrier (manufactured by Kanto Denka Kogyo Co., Ltd.) having an average particle diameter of 90 μm for 10 minutes with a turbuler mixer to prepare a developer. . The obtained developer was mounted on a device obtained by modifying a copying machine "AR-505" (manufactured by Sharp Corporation), and the reflection densitometer "while increasing the temperature of the fixing roller from 90 ° C to 240 ° C in steps of 5 ° C. RD-915 "(manufactured by Macbeth) having an average image density of 1.4 (2 cm x 12
cm) and the low temperature fixability was evaluated in the same manner as in Test Example 2a. The results are shown in Table 3.

Test Example 3 5 g of toner was placed in a cylindrical container, left at 50 ° C. for 72 hours, and then passed through a 200 mesh (opening: 75 μm) sieve,
The weight of the passed toner was weighed and the storability was evaluated according to the following evaluation criteria. The results are shown in Table 3. (Evaluation Criteria) Toner that has passed through the sieve is ⊚: more than 90% by weight ◯: 80 to 90% by weight ×: less than 80% by weight

Test Example 4 Toner was mounted in the same apparatus as in Test Examples 2a and 2b,
1% of the image with a printing rate of 5% under the environment of 35 ° C and 85% RH
After continuous printing of 0,000 sheets, the number of printed sheets with background stain was shown, and the environmental stability of the image was evaluated. The results are shown in Table 3.

[0067]

[Table 3]

From the above results, it is understood that Examples 1 to 8 are excellent in crushability, low-temperature fixability, storage stability and environmental stability. In particular, in Example 4 in which wax was added at the production stage of the hybrid resin, excellent results were obtained in all evaluations, regardless of the magnetic toner. On the other hand, the toners of Comparative Examples 1 and 4 which did not contain the crystalline polyester lacked the low temperature fixability, and the toner of Comparative Example 2 which contained the amorphous polyester instead of the amorphous hybrid resin showed the crystalline property. Polyester and amorphous polyester are too compatible with each other, resulting in poor grindability and storability, and poor environmental stability in image quality. Further, the toner of Comparative Example 3 containing a large amount of crystalline polyester lacks pulverizability and storability.

[0069]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a toner having excellent pulverizability, low-temperature fixability and storability, and excellent environmental stability.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yasunori Inagaki             1334 Minato Minato, Wakayama Kao Corporation             Within F-term (reference) 2H005 AA01 AA06 CA08 CA14 CA16                       EA03 EA07

Claims (7)

[Claims] 1. A resin having a ratio (softening point / peak temperature) between the softening point and the maximum peak temperature of the heat of fusion of 0.6 or more and less than 1.1 (hereinafter referred to as crystalline resin), and the softening point and the heat of fusion. The maximum peak temperature ratio (softening point / peak temperature) of 1.1 to
A toner containing a binder resin containing a hybrid resin of 4.0 (hereinafter referred to as an amorphous hybrid resin) and a colorant, wherein the amorphous hybrid resin has independent reaction paths. The two polymerizable resin components having are partially chemically bonded, and at least one of them is the same polymerizable resin component as the crystalline resin, and the weight ratio of the crystalline resin and the amorphous hybrid resin ( Crystalline resin / amorphous hybrid resin) is 1/99 to 50 /
Toner that is 50. 2. The softening point of the crystalline resin is 85 to 150 ° C., and the softening point of the amorphous hybrid resin is 80 to 170.
The toner according to claim 1, which has a temperature of ℃. 3. The toner according to claim 1, wherein the crystalline resin is crystalline polyester. 4. A crystalline polyester comprising an alcohol component containing 80 mol% or more of an aliphatic diol having 2 to 6 carbon atoms and a carboxylic acid component containing 80 mol% or more of an aliphatic dicarboxylic acid compound having 2 to 8 carbon atoms. The toner according to claim 3, which is a resin obtained by polycondensation of. 5. The amorphous hybrid resin is obtained by mixing raw material monomers of two polymerization type resins each having an independent reaction route and carrying out the two polymerization reactions. The toner described. 6. The toner according to claim 5, wherein a wax is added together with the raw material monomer. 7. The toner according to claim 1, which is a magnetic toner.
The toner according to any one of the items.