JPH09244295A - Resin composition for toner and toner - Google Patents

Abstract

(57) Abstract: [PROBLEMS] To provide a resin composition for a toner for obtaining a heating roller fixing toner having a wide fixing temperature range and excellent in offset resistance and blocking resistance, and a toner using the same. The maximum value in the molecular weight distribution is 3 × 10 ^3.
A low molecular weight polymer component in the range of 5 × 10 ⁴ to a high molecular weight polymer component having a maximum in the molecular weight distribution in the range of 3 × 10 ^{5 to} 5 × 10 ^6. Having a acid value of 10 KOHmg / g or more and a high molecular weight polymer component having an acid value higher than the acid value of the low molecular weight polymer component (A) and a glycidyl group or β. A resin (B) made of a copolymer of a vinyl-based monomer having a methylglycidyl group and a vinyl-based monomer other than the vinyl-based monomer as a main resin component, and the resin (A) includes A vinyl-based monomer having an acid group is copolymerized, and at least one of the vinyl-based monomer having the acid group and the vinyl-based monomer having the glycidyl group or the β-methylglycidyl group is a resin. Block copolymerized inside.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for toner used in electrophotography and the like, and more specifically, it is a toner used in a so-called dry developing method among methods for developing an electrostatic charge image. The present invention relates to a resin composition for use and a toner using the same.

[0002]

2. Description of the Related Art In electrophotography and the like, a dry developing method is often used as a method for developing an electrostatic charge image. In this dry development method, a triboelectric charge fine powder developer called a toner in which a colorant such as carbon black is dispersed in a resin is used.

Usually, toner charged by friction adheres to an electrostatic latent image on a photoconductor by an electric attraction to form a toner image, and then this toner image is transferred onto a sheet,
The toner is fixed to the toner by a heating roller having releasability.

Such a toner has anti-offset property (no toner adheres to the heating roller), fixability (toner adheres strongly to the paper), anti-blocking property (toner particles do not aggregate). Various performances are required. In particular, a toner having a wide fixing temperature range and excellent offset resistance is required.

To meet this demand, Japanese Patent Laid-Open No.
In JP-A-118552, a resin containing a glycidyl group or a β-methylglycidyl group is mixed with a resin obtained by reacting a styrene-acrylic copolymer containing a carboxyl group with a polyvalent metal compound, and crosslinking reaction is performed when heated. It has been proposed to obtain good blocking resistance, offset resistance, and fixing property by raising it, but it is the low molecular weight portion and the glycidyl group-containing resin that undergo a crosslinking reaction when heated, and to obtain a wide fixing temperature range. However, in some cases, sufficient offset resistance could not be obtained, and in some cases, fixability was deteriorated.

Further, Japanese Patent Application Laid-Open No. 7-191496 proposes to include a carboxylic acid component in the high molecular weight portion, but although the charging property is improved, a wider fixing temperature range and further good It was difficult to obtain excellent offset resistance.

[0007]

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned various drawbacks of the prior art, to obtain a toner for fixing on a heating roller which has a wide fixing temperature range and is excellent in offset resistance and blocking resistance. To provide a resin composition for a toner and a toner using the same.

[0008]

The present invention has been made to achieve the above-mentioned object, and the invention according to claim 1 has a maximum value in the molecular weight distribution of 3 × 10 ^{3 to} 5 ×.
A low molecular weight polymer component in the range of 10 ⁴ and a high molecular weight polymer component having a maximum value in the molecular weight distribution in the range of 3 × 10 ^{5 to} 5 × 10 ⁶ , and the acid value of the high molecular weight polymer component. Is 10 KOHmg / g or more and the acid value of the high molecular weight polymer component is higher than the acid value of the low molecular weight polymer component, and the resin (A) is a glycidyl group or β-methylglycidyl group. A resin (B) made of a copolymer of a vinyl-based monomer having a group and a vinyl-based monomer other than the vinyl-based monomer is a main resin component, and the resin (A) has an acid group. The vinyl monomer having is copolymerized, and at least one of the vinyl monomer having the acid group and the vinyl monomer having the glycidyl group or the β-methylglycidyl group is blocked in the resin. Characterized by being copolymerized A toner resin composition.

A second aspect of the present invention is a toner containing the toner resin composition of the first aspect as a main component.

Hereinafter, the present invention will be described in detail. The vinyl copolymer used for the resin (A) in the present invention preferably contains, for example, a styrene monomer, a (meth) acrylic acid ester monomer, or the like as a structural unit.

Examples of the styrene-based monomer include
Styrene, o-methylstyrene, m-methylstyrene,
p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-ter-butylstyrene, pn-hexylstyrene, pn-octylstyrene, Examples thereof include pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, and 3,4-dichlorostyrene, among which styrene. Is most preferred.

Examples of the (meth) acrylic acid ester-based monomer include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate. , 2-ethylhexyl acrylate, stearyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate,
Isobutyl methacrylate, n-octyl methacrylate,
In addition to acrylic acid such as dodecyl methacrylate and stearyl methacrylate, or alkyl esters of methacrylic acid, 2-chloroethyl acrylate, phenyl acrylate, α-
Examples include methyl chloroacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate, glycidyl methacrylate, bisglycidyl methacrylate, polyethylene glycol dimethacrylate, methacryloxyethyl phosphate, and the like. You can
Among them, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl acrylate and the like are preferably used.

The vinyl copolymer of the present invention has a maximum molecular weight distribution of the low molecular weight polymer component of 3 × 10 ^{3 to} 5 × 10 ⁴ in the molecular weight distribution measured by gel permeation chromatography (GPC). And the maximum value of the molecular weight distribution of the high molecular weight polymer component is 3 × 1.
It is required to be in the range of 0 ^{5 to} 5 × 10 ⁶ .

If the maximum value of the molecular weight distribution of the low molecular weight polymer component is smaller than the above range, the blocking resistance of the toner may be lowered, and if it is larger than the above range, the fixing property of the toner may be lowered.

If the maximum value of the molecular weight distribution of the high molecular weight polymer component is smaller than the above range, the offset resistance of the toner may be lowered, and if it is larger than the above range, the fixing property of the toner may be lowered. is there.

In the above vinyl-based copolymer containing a low molecular weight polymer component and a high molecular weight polymer component, when the content of the high molecular weight polymer component is less than 10% by weight in the vinyl copolymer, Offset resistance may be reduced. Therefore, the content of the high molecular weight polymer component in the vinyl copolymer is preferably 10% by weight or more, more preferably 20% by weight or more.

Further, when the content of the high molecular weight polymer component in the vinyl-based copolymer is higher than 50% by weight, sufficient fixing property may not be obtained. The content of the polymer component is 50% by weight or less.

Further, the vinyl copolymer preferably has a glass transition point of 50 ° C. or higher in order to enhance the blocking resistance of the toner.

The acid value of the high molecular weight polymer component in the vinyl copolymer must be 10 KOHmg / g or more. When the acid value of the high molecular weight polymer component becomes small, the cohesive force of the acid component contained in the vinyl-based copolymer becomes weak, and sufficient fixability and blocking resistance may not be obtained. Further, the upper limit of the acid value is not limited, but since the cohesive force due to the acid component is too strong and the viscosity becomes high, or the solvent solubility may be extremely deteriorated, 150 KOHmg / g or less is preferable. It is preferably used.

In the vinyl copolymer used for the resin (A) in the present invention, the acid value of the high molecular weight polymer component needs to be higher than the acid value of the low molecular weight polymer component. When the acid value of the low molecular weight polymer component is not less than the acid value of the high molecular weight polymer component, the acid value of the high molecular weight polymer component is 1
When it is 0 KOHmg / g or more, and the acid value of the low molecular weight polymer component becomes larger than that, the acid value of the vinyl copolymer as a whole becomes very high and the blocking resistance is lowered, Both the low molecular weight polymer component and the high molecular weight polymer component may have a strong cohesive force due to the acid component, resulting in a decrease in fixing property.

By increasing the acid value of the high molecular weight polymer, a crosslinking reaction with the glycidyl group or β-methylglycidyl group in the resin (B) occurs preferentially, and more excellent offset resistance is obtained. It becomes possible.

The resin (A) in the present invention contains a vinyl monomer having an acid group in order to increase the acid value of the resin (A). Examples of the acid group include a carboxylic acid group, a sulfonic acid group, a sulfinic acid group, a phosphonic acid group,
Examples thereof include a boric acid group, and among them, a carboxylic acid group is preferably used from the viewpoint of acid strength and ease of copolymerization.

Examples of vinyl monomers having a carboxylic acid group include (meth) acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid and crotonic acid, and α or β-alkyl derivatives thereof; fumaric acid. , Unsaturated dicarboxylic acids such as maleic acid, citraconic acid, itaconic acid; succinic acid monoacryloyloxyethyl ester,
Unsaturated dicarboxylic acid monoester derivatives such as succinic acid monomethacryloyloxyethyl ester, phthalic acid monoacryloyloxyethyl ester and phthalic acid monomethacryloyloxyethyl ester are listed, and among these, acrylic acid, methacrylic acid, succinic acid monoester Acryloyloxyethyl ester and succinic acid monomethacryloyloxyethyl ester are preferably used.

As the method for producing the vinyl copolymer in the resin (A), for example, suspension polymerization, emulsion polymerization, solution polymerization, bulk polymerization and the like are used. The low molecular weight polymer component and the high molecular weight polymer component may be hot melt blended, but in order to disperse more uniformly, it is preferable to be desolvated after being dispersed in a solvent, and more preferable. Examples of the method include a method of polymerizing a low molecular weight polymer component in the presence of a high molecular weight polymer component. The weight average molecular weight of the resin (A) is preferably in the range of 50,000 to 500,000.

Further, in the present invention, a polyvalent metal compound which reacts with the acid group in the resin (A) may be contained if necessary, and the metal in the polyvalent metal compound is, for example, Cu. , Ag, Be, Mg, Ca, Sr, Ba, Z
n, Cd, Al, Ti, Ge, Sn, V, Cr, Mo,
Mn, Fe, Co, Ni, etc. are mentioned. Among these, alkaline earth metals and zinc group metals are preferable, and Mg and Zn are particularly preferable.

Examples of the above polyvalent metal compounds include fluorides, chlorides, chlorates, bromides, iodides, oxides, hydroxides, sulfides, sulfites, sulfates, selenides, tellurides, Nitride, nitrate, phosphide, phosphinate, phosphate, carbonate, orthosilicate, acetate,
Examples thereof include lower alkyl metal compounds such as oxalate, methylated products, ethylated products, and the like. Of these, acetates and oxides are preferable.

The polyvalent metal compound is preferably contained in an amount of 0.1 to 1 mol with respect to 1 mol of the vinyl monomer having an acid group. The reaction temperature is generally 100 to 200 ° C.
Is preferred.

As a method for reacting the polyvalent metal compound with the vinyl-based copolymer, for example, a solution of the vinyl-based copolymer is polymerized and then the polyvalent metal is dispersed in an organic solvent, if necessary. A method of introducing a compound into the system and carrying out a reaction at an appropriate temperature, a method of dispersing a polyvalent metal compound with an organic solvent in the system before starting the polymerization reaction of a vinyl-based copolymer, and a vinyl-based copolymer. Examples include a method in which a polyvalent metal compound is mixed with the product obtained by distilling the solvent after the solution polymerization of the polymer and melt-kneading at a suitable temperature using a roll mill, a kneader, or an extruder.

In the present invention, examples of the vinyl monomer having a glycidyl group or a β-methylglycidyl group used for the resin (B) include glycidyl acrylate,
Β-methyl glycidyl acrylate, glycidyl methacrylate, β-methyl glycidyl methacrylate, allyl glycidyl ether and the like can be mentioned.

As the vinyl-based monomer other than the vinyl-based monomer copolymerized with the vinyl-based monomer having the glycidyl group or β-methylglycidyl group, for example, the above resin (A) is used. Examples thereof include styrene-based monomers, acrylic acid ester, methacrylic acid ester-based monomers used, and other vinyl acetate, vinyl propionate, vinyl chloride, ethylene, propylene and the like. Among these,
Both styrenic monomers and acrylic or methacrylic acid ester monomers are preferably used.

In the resin (B), a glycidyl group or β
Examples of the method for synthesizing a copolymer of a vinyl monomer having a methylglycidyl group and a vinyl monomer other than the vinyl monomer include suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization. Etc. are available. In this case, a glycidyl group or β
It is preferable that the content of the vinyl-based monomer component having a methylglycidyl group is at least 5% by weight or more. When the content of the vinyl-based monomer component having a glycidyl group or β-methylglycidyl group is less than 5% by weight, the reaction with the resin (A) becomes insufficient and the offset resistance of the toner is improved. May become difficult to appear.

The weight average molecular weight of the resin (B) is 1
The range of 50,000 to 500,000 is preferable. Also,
In order to improve the blocking resistance of the resin (B), its glass transition point is preferably 40 ° C or higher.

The resin composition for a toner of the present invention comprises the resin (A) and the resin (B) as main resin components, and the resin (A).
At least one of the vinyl monomer having an acid group and the vinyl monomer having a glycidyl group or a β-methylglycidyl group in the resin (B) needs to be block-copolymerized in each resin. There is. Compared with the case of random copolymerization, resin (A) can be obtained by block copolymerization.
And the resin (B) easily occur, the reaction rate can be further increased, and more excellent offset resistance can be obtained.

As the method of synthesizing the block copolymer, for example, a method of synthesizing a block copolymer by reacting two or more kinds of resins, and a two-step decomposition type polymerization initiator having two or more decomposition temperatures is used. A method of synthesizing a block copolymer by such a method may be mentioned, and a synthesis method using a two-step decomposition type polymerization initiator is preferable from the viewpoint of easiness of synthesis.

Examples of the above-mentioned two-step decomposition type polymerization initiator include 1,1-bis (t-butylperoxy) cyclohexane, poly (hexamethyleneazobiscyanopentanoate), tetraethylthiuraum disulfide,
Poly (2,5-dimethylhexane-2,5)-(cyclohexane-1,4-dipercarboxylate), polyazeroyl peroxide, poly-2,5-dimethyl-2,
5-diperazelate and the like can be mentioned.

In the present invention, the resin composition for toner is prepared by mixing or kneading the above resin (A) and resin (B). As for the compounding ratio of the resin (A) and the resin (B), when the amount of the resin (B) is small, the reaction with the resin (A) may be insufficient and the effect of improving the offset resistance of the toner may not be exhibited. When the amount of B) is large, the fixability of the toner may be deteriorated, and the fixability and offset resistance of the resin (A) may be impaired. A range of parts is preferred.

As a method for mixing or kneading the resin (A) and the resin (B), for example, the resin (A) and the resin (B) are finely pulverized and then mixed with a ribbon blender, a Hensell mixer or the like. The resin (A) and the resin (B) using a roll mill, a kneader, an extruder or the like, for example, 100
A method of melt-kneading at a temperature of ˜200 ° C., cooling and finely pulverizing, a method of dissolving the resin (A) and the resin (B) in an organic solvent and mixing, and then distilling the solvent to finely powder, Etc.

In the resin composition for toner of the present invention,
As long as the object of the present invention can be achieved, vinyl acetate, vinyl chloride, ethylene, etc. may be copolymerized in the vinyl copolymer, and a polymer of these monomers is blended. May be. Further, polyester resin, epoxy resin or the like may be mixed, and further aliphatic amide, bisaliphatic amide, metal soap, paraffin or the like may be mixed.

Further, as long as the object of the present invention can be achieved, dyes such as nigrosine and Spiron Black (manufactured by Hodogaya Chemical Co., Ltd.) and other phthalocyanine pigments may be added as charge control agents. Good. Further, as the release agent, for example, low molecular weight polyethylene, polypropylene wax or the like may be added, or hydrophobic silica or the like may be added to improve fluidity. As the colorant, for example, carbon black, chrome yellow, aniline blue or the like is used.

The toner according to claim 2 of the present invention is characterized in that the above-mentioned resin composition for toner is used, and the above-mentioned resin composition for toner is provided with a coloring agent such as carbon black and other additives. A fine powder containing is mixed with a carrier such as iron powder or glass beads.

To produce a toner using the toner resin composition of the present invention, a finely pulverized product of the resin (A) and the resin (B), a coloring agent such as carbon black, and other additives are added as necessary. A conventionally known toner additive is added to a ribbon blender,
Mixing with a Henschel mixer or the like, or mixing a colorant such as carbon black with the resin (A) and the resin (B), and using a roll mill, a kneader, an extruder or the like, for example, 100 to 200 ° C. Melt-knead at the temperature of, cool and pulverize.

In the above melt-kneading, kneading temperature, kneading time,
By changing the type of the kneading screw and the like, the degree of reaction between the resin (A) and the resin (B) can be easily adjusted, and a toner having physical properties suited to the purpose can be obtained.

[0043]

The toner resin composition of the present invention has a molecular weight distribution
The maximum value is 3 × 10^Three~ 5 × 10^FourIs in the range
Low molecular weight polymer component and maximum value of 3 x 10^Five~ 5 × 10
⁶At least contains high molecular weight polymer components in the range of
Containing a resin (A) which is a vinyl polymer
With the same good offset resistance and fixing as conventional toner
And blocking resistance are obtained.

The acid value of the high molecular weight polymer is 10 KO.
It is presumed to be Hmg / g or more, the cohesive force due to the acid group becomes strong, the cohesive force works at room temperature, and the coagulation is dissociated by heat at high temperature, but at room temperature the glass transition point is It is high and has a low softening point at a high temperature, resulting in a very good balance between blocking resistance and fixing property.

Further, by making the acid value of the high molecular weight polymer larger than that of the low molecular weight polymer, the influence of the cohesive force due to the acid groups is exerted more strongly on the high molecular weight polymer, and the original viscosity is higher. The high molecular weight polymer, which has hindered the fixability, can contribute to the fixability.

Further, in the present invention, a resin (B) which is a copolymer of a vinyl monomer having a glycidyl group or a β-methylglycidyl group and another vinyl monomer is contained as a constituent component. The glycidyl group or β-methylglycidyl group of the resin (B) causes a crosslinking reaction with the acid group of the resin (A) when heated.

Further, since at least one of the vinyl monomer having an acid group and the vinyl monomer having a glycidyl group or a β-methylglycidyl group is block-copolymerized in the resin, a crosslinking reaction is caused. It is likely to occur easily, and the reaction rate can be further increased, and more excellent offset resistance can be obtained.

Therefore, the degree of the cross-linking reaction can be adjusted in the manufacturing process of the toner, the physical properties of the toner can be controlled according to the purpose of the toner, and the blocking resistance and offset resistance can be improved as compared with the conventional toner. And a toner having a wide fixing temperature range is obtained.

[0049]

The present invention will be described in more detail by giving non-limiting examples and comparative examples of the present invention. The term "parts" means "parts by weight".

Production Example 1 of Resin (A) The maximum molecular weight obtained by polymerizing 65 parts of styrene, 23 parts of n-butyl acrylate and 12 parts of methacrylic acid is 85.
In the meanwhile, 30 parts of a polymer having an acid value of 75 KOHmg / g and 100 parts of toluene were put into a flask and dissolved. After replacing the inside of the flask with nitrogen gas, while stirring under reflux of toluene, 70 parts of styrene, 10 parts of methyl methacrylate, 20 parts of n-butyl acrylate and benzoyl peroxide (polymerization initiator) 5 3 parts of mixed solution
Solution polymerization was performed by dropwise addition over time.

After completion of dropping, aging was carried out for 3 hours while stirring under reflux of toluene. Thereafter, while gradually raising the temperature in the flask to 180 ° C., toluene was removed under reduced pressure to obtain a resin. The resin (A-1) was produced by cooling and crushing this resin. Obtained resin (A-
1) gel permeation chromatography (GP
The maximum values of the molecular weight distribution measured by C) are 10,000 and 8
The weight average molecular weight was 50,000, the weight average molecular weight was 150,000, and the glass transition point was 62.3 ° C. Separately, only the low molecular weight polymer was polymerized, and the acid value was measured.
g / g.

The GPC measurement conditions were column temperature:
40 ° C, solvent: tetrahydrofuran, flow rate: 1 mm /
Min, sample concentration: 0.2%, sample amount: 100 μl, column: 2 KF-80M and KF-802.5 (both are manufactured by Shodex), and the glass transition point is a differential thermal balance (DSC). ) Represents the inflection point of the peak.

As the method for measuring the acid value, Sample 2.
0 g was precisely weighed and dissolved with 30 ml of methyl ethyl ketone, and the resulting solution was titrated with 1/50 N potassium hydroxide / isopropyl alcohol solution (KOH / IPA solution) using 1% phenolphthalein solution as an indicator,
It was calculated by the following calculation formula.

<< Acid Value Calculation Formula >> Acid Value (KOHmg / g) = {(1/50) × F × 56.11 ×
(AB)} / MF: Titer of 1 / 50N KOH / IPA solution A: Amount of KOH / IPA solution required for titration of solution B: KOH / required for titration of blank test (only methyl ethyl ketone)
IPA solution volume M: sample weight

Production Example 2 of Resin (A) 74 parts of styrene, 10 parts of methyl methacrylate, 15 parts of 2-ethylhexyl acrylate and 1 part of acrylic acid were polymerized to obtain a maximum molecular weight of 25,000 and an acid value. Is 4 KOHm
100 parts of low molecular weight polymer of g / g, 62 parts of styrene, 20 parts of methyl methacrylate, and 15 parts of 2-ethylhexyl acrylate block polymerization of 3 parts of acrylic acid gave a maximum molecular weight of 410,000, 60 parts of high molecular weight polymer having an acid value of 14 KOHmg / g, 0.5 part of zinc oxide and 20 parts of toluene
0 parts were charged into the flask and dissolved.

After replacing the inside of this flask with nitrogen gas,
Heated to the boiling point of toluene. The mixture was stirred for 3 hours under the reflux of toluene, and then the temperature in the flask was adjusted to 18
While gradually raising the temperature to 0 ° C., the solvent was removed from the toluene under reduced pressure to obtain a resin. The resin (A-2) was manufactured by cooling the obtained resin and pulverizing it.

The maximum values of the molecular weight distribution measured by GPC using the resin (A-2) were 25,000 and 410,000, the weight average molecular weight was 210,000, and the glass transition point was 65.8 ° C.
And 103.7 ° C. Since both the glass transition point (65.8 ° C.) of the styrene- (meth) acrylic acid ester copolymer and the glass transition point (103.7 ° C.) of acrylic acid appear, the acrylic acid moiety is block copolymerized. Was confirmed.

Production Example 3 of Resin (A): 55 parts of styrene and 30 parts of n-butyl acrylate were subjected to block polymerization of 15 parts of acrylic acid to obtain a maximum molecular weight of 2,000,000 and an acid value of 96 KOHmg / g. 15 parts of a certain polymer and 100 parts of toluene were put into a flask and dissolved. After replacing the inside of the flask with nitrogen gas, the flask was heated to the boiling point of toluene. While stirring under reflux of toluene, 85 parts of styrene and 1 part of n-butyl acrylate were stirred.
5 parts and benzoyl peroxide (polymerization initiator) 10
Part of the mixed solution was added dropwise over 3 hours to carry out solution polymerization.

After completion of dropping, the mixture was aged for 3 hours while stirring under reflux of toluene. Then, the temperature in the flask is raised to 18
While gradually raising the temperature to 0 ° C., the solvent was removed from the toluene under reduced pressure to obtain a resin. The resin (A-3) was manufactured by cooling the obtained resin and pulverizing it.

The maximum values of the molecular weight distribution measured by GPC using the resin (A-3) are 4,000 and 2,000,000, the weight average molecular weight is 150,000, and the glass transition point is 5
The temperatures were 9.1 ° C and 98.7 ° C. Both the glass transition point (59.1 ° C.) of the styrene-acrylic acid ester copolymer and the glass transition point of acrylic acid (98.7 ° C.) appear, indicating that the acrylic acid moiety is block-copolymerized. Was confirmed. Separately, only the low molecular weight polymer was polymerized, and the acid value was measured and found to be 0 KOHmg / g.

Resin (A-1) to Resin (A
-3) is shown in Table 1.

[0062]

[Table 1]

Production Example 1 of Resin (B) 100 parts of toluene was put into a flask, the inside of the flask was replaced with nitrogen gas, and then 52 parts of styrene and acrylic resin were stirred while stirring the toluene at 90 ° C. Acid n-
8 parts butyl and 1,1-bis (t-butylperoxy)
A mixed solution of 2.5 parts of cyclohexane (two-step decomposition type polymerization initiator) was added dropwise over 2 hours. Then, the temperature in the system was raised to the reflux temperature of toluene, 40 parts of glycidyl methacrylate was added dropwise over 1 hour, and two-step solution polymerization was carried out.

After completion of dropping, aging was carried out for 3 hours while stirring under reflux of toluene. Thereafter, while gradually raising the temperature in the flask to 180 ° C., toluene was removed under reduced pressure to obtain a resin. The resin (B-1) was produced by cooling and crushing this resin.

The maximum value of the molecular weight distribution measured by GPC using the resin (B-1) is 21,000, the weight average molecular weight is 28,000, and the glass transition point is 42.3.
And 55.3 ° C. Since both the glass transition point (55.3 ° C.) of styrene-n-butyl acrylate copolymer and the glass transition point (42.3 ° C.) of glycidyl methacrylate appear, the glycidyl methacrylate portion is block copolymerized. It was confirmed that

Production Example 2 of Resin (B) 10 parts of a polymer having a maximum molecular weight of 600,000 obtained by polymerizing 60 parts of styrene, 15 parts of methyl methacrylate and 25 parts of n-butyl acrylate, and 100 parts of toluene. And parts were put into a flask and dissolved. After replacing the inside of the flask with nitrogen gas, the flask was heated to the boiling point of toluene. While stirring under reflux of toluene, styrene 40
Solution, 60 parts of glycidyl acrylate and 5 parts of benzoyl peroxide (polymerization initiator) were added dropwise over 3 hours to carry out solution polymerization.

After completion of dropping, the mixture was aged for 3 hours while stirring under reflux of toluene. Then, the temperature in the flask is raised to 18
While gradually raising the temperature to 0 ° C., the solvent was removed from the toluene under reduced pressure to obtain a resin. The resin (B-2) was produced by cooling and crushing this resin.

The maximum values of the molecular weight distribution measured by GPC using the resin (B-2) were 9,000 and 600,000, the weight average molecular weight was 140,000, and the glass transition point was 52.2.
° C.

Production Example 3 of Resin (B) 100 parts of toluene was put into a flask, the inside of the flask was replaced with nitrogen gas, and then 77 parts of styrene and acrylic acid were stirred while stirring under reflux of toluene. A mixed solution of 15 parts of n-butyl and 3.5 parts of polyazeroyl peroxide (two-step decomposition type polymerization initiator) was added dropwise over 2 hours. Then, the temperature in the system was raised to the reflux temperature of toluene, 8 parts of glycidyl methacrylate was added dropwise over 1 hour, and two-step solution polymerization was carried out.

After completion of dropping, aging was carried out for 3 hours while stirring under reflux of toluene. Thereafter, while gradually raising the temperature in the flask to 180 ° C., toluene was removed under reduced pressure to obtain a resin. The resin (B-3) was manufactured by cooling and crushing this resin.

The maximum value of the molecular weight distribution measured by GPC using the resin (B-3) is 12,000, the weight average molecular weight is 17,000, and the glass transition point is 41.7 ° C.
And 54.1 ° C. Since both the glass transition point (54.1 ° C.) of styrene-n-butyl acrylate copolymer and the glass transition point (41.7 ° C.) of glycidyl methacrylate appear, the glycidyl methacrylate portion is block copolymerized. It was confirmed that

Example 1 75 parts of resin (A-1), 25 parts of resin (B-1) and 4 parts of carbon black (MA-100 manufactured by Mitsubishi Chemical Co., Ltd.) were added, and roll kneading was carried out at 170 ° C. for 10 minutes. After cooling, it was roughly pulverized and then finely pulverized by a jet mill to prepare a toner having an average particle diameter of 13 to 15 μm. 10 g of this toner
Was placed in a 100 ml sample bottle and left in a constant temperature bath at 50 ° C. for 16 hours, and the blocking resistance was evaluated by the presence or absence of particle coalescence. As a result, the blocking resistance was good.

The fine powder developer using this toner was mounted in a modified electrophotographic copying machine (U-Bix2500: manufactured by Konica) to measure the fixing temperature range. The fixing temperature range is indicated by changing the setting temperature of the heating roller for fixing so as to achieve good fixing without causing offset. As a result, the fixing temperature range was 160 to 235 ° C., and good fixing was possible in a wide temperature range.

Example 2 A toner and a fine powder developer were prepared and evaluated in the same manner as in Example 1 except that 95 parts of the resin (A-2) and 5 parts of the resin (B-2) were used. It was As a result, the blocking resistance was good, and the fixing temperature range was 160 to 235 ° C., and good fixing was possible in a wide temperature range.

Example 3 A toner and a fine powder developer were prepared and evaluated in the same manner as in Example 1 except that 60 parts of the resin (A-3) and 40 parts of the resin (B-3) were used. It was As a result, the blocking resistance was good, and the fixing temperature range was 160 to 235 ° C., and good fixing was possible in a wide temperature range.

Example 4 A toner and a fine powder developer were prepared and evaluated in the same manner as in Example 1 except that the roll kneading condition was changed to 180 ° C. for 20 minutes. As a result, the blocking resistance was good, and the fixing temperature range was 170 to 240 ° C., and good fixing was possible in a wide temperature range.

Comparative Example 1 A toner and a fine powder developer were prepared and evaluated in the same manner as in Example 1 except that only 100 parts of the resin (A-1) was used. As a result, the blocking resistance is as good as in Example 1, but the fixing temperature range is narrow at 160 to 220 ° C., the high temperature offset property is weaker than in Example 1, and a wide fixing temperature range cannot be obtained. It was

Comparative Example 2 A toner and a fine powder developer were prepared and evaluated in the same manner as in Example 1 except that only 100 parts of the resin (B-2) was used. As a result, the blocking resistance was as good as that of Example 2, but the fixing temperature range was as narrow as 150 to 190 ° C., and the fixing start temperature was lower than that of Example 2, but the high-temperature offset property was weak and the fixing temperature range was wide. Couldn't get

Comparative Example 3 A toner and a fine powder developer were prepared and evaluated in the same manner as in Example 2 except that the block copolymer of acrylic acid was changed to a random copolymer in the resin (A-2). went. As a result, the blocking resistance is as good as in Example 2, and although the fixing temperature range is relatively good at 160 to 230 ° C., the high temperature offset property is weaker than in Example 2, and a wide fixing temperature range can be obtained. I couldn't.

Table 2 shows the evaluation results of the above Examples and Comparative Examples.

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[Table 2]

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As described above, the toner resin composition and toner of the present invention are composed of a low molecular weight polymer component and a high molecular weight polymer component, and can be fixed in a wide fixing temperature range. . Also, the acid value of the high molecular weight product is 10 KOHmg / g
By the above, the balance between blocking resistance and fixing property becomes good, and further, the acid value of the high molecular weight polymer is made higher than that of the low molecular weight polymer, thereby further widening the fixing temperature range. It has become possible.

Further, at least one of the vinyl monomer containing an acid group and the vinyl monomer containing a glycidyl group or a β-methylglycidyl group in the resin (A) is block-copolymerized in the resin. Therefore, the crosslinking reaction between the resin (A) and the resin (B) easily occurs, and the high molecular weight region of the molecular weight distribution is widened, whereby the offset resistance is improved.

Further, the reactivity of the resin (A) and the resin (B) can be controlled by adjusting the kneading conditions for forming the toner, and the toner physical properties can be adjusted to suit the purpose. Therefore,
The resin composition for a toner and the toner of the present invention can be suitably used for a heat roller fixing type electrophotographic copying machine from low speed to high speed.

Claims (2)

[Claims] 1. The maximum value in the molecular weight distribution is 3 × 10 ^3.
A low molecular weight polymer component in the range of 5 × 10 ⁴ to a high molecular weight polymer component having a maximum in the molecular weight distribution in the range of 3 × 10 ^{5 to} 5 × 10 ^6. A resin (A) made of a vinyl-based copolymer having an acid value of 10 KOHmg / g or more and a high molecular weight polymer component acid value higher than that of a low molecular weight polymer component, and a glycidyl group or β A resin (B) made of a copolymer of a vinyl monomer having a methylglycidyl group and a vinyl monomer other than the vinyl monomer as a main resin component,
The resin (A) is copolymerized with a vinyl-based monomer having an acid group, and the vinyl-based monomer having the acid group and the vinyl-based monomer having the glycidyl group or the β-methylglycidyl group. A resin composition for a toner, wherein at least one of the two is block-copolymerized in the resin. 2. A toner comprising the toner resin composition according to claim 1 as a main component.