JPH0854753A - Toner for developing electrostatic image - Google Patents

Abstract

PURPOSE:To obtain a toner excellent especially in low-temp. fixability and anti-offsetting property, ensuring the amt. of electric charges and image quality independently of the environment and fixable at a low temp. in a heat roller fixing system without using an anti-offsetting liq. CONSTITUTION:This toner contains at least a bonding resin and a colorant. The bonding resin is a resin obtd. by bringing a mixture contg. the stock monomer of a condensation-polymerized resin, the stock monomer of vinyl resin and a compd. capable of reacting with both the monomers into a condensation polymn. reaction and an addition polymn. reaction at the same time in the same reactor. The bonding resin contains 10-30wt.% component insoluble in chloroform at 25 deg.C and a component soluble in chloroform has at least one maximal value peak in the range of 5X10<3>-5X10<4> when the mol.wt. distribution is measured by gel permeation chromatography.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to electrophotography, electrostatic recording,
The present invention relates to an electrostatic image developing toner for developing an electrostatic latent image formed in electrostatic printing or the like.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been described in US Pat.
No. 21776, No. 2297691, No. 2357809, etc., the photoconductive insulating layer is uniformly charged, and then the layer is exposed to dissipate the charge in the exposed portion. To form an electrical latent image, and then a fine image powder having a colored charge called toner is attached to the latent image to form a visible image (developing step). After being transferred to a transfer material such as transfer paper (transfer step), it is permanently fixed by heating, pressure or any other suitable fixing method (fixing step).

In the fixing process, there are a contact heating fixing method such as a heat roller fixing method and a non-contact heating method such as an oven fixing method. The contact method is characterized by high thermal efficiency,
Compared with the non-contact method, the temperature required for the fixing machine can be lowered, which is effective for energy saving and downsizing of the copying machine. From this point, it is clear that the contact-type heat fixing method is a useful fixing method, but in this fixing method, the problem of offset development easily occurs. In this phenomenon, a part of the toner melted at the time of fixing is transferred to a heat roller and transferred to a transfer sheet or the like which follows.

In order to prevent this phenomenon, conventionally, the surface of the heat roller is processed with a material having excellent mold release property such as fluorine resin, or a mold release agent such as silicone oil is applied to the surface of the heat roller. I am. However, the method using silicone oil or the like is not preferable because the fixing device becomes large and complicated, which may increase the cost and cause troubles.

Conventionally, a vinyl resin represented by a styrene-acrylic copolymer has been used for this type of toner. In the case of a vinyl-based resin, when it is attempted to improve the offset resistance, the softening point and the crosslink density of the resin are unavoidably increased, and low temperature fixing is sacrificed. On the other hand, if low temperature fixing is emphasized, offset resistance and blocking resistance will be impaired.

Further, JP-A-49-65232, JP-A-50-28840, and JP-A-50-81342.
As described in Japanese Patent Publication No. JP-A-2003-264, there is known a method of adding paraffin wax, low-molecular-weight polyolefin or the like as an offset preventive agent, but it is confirmed that if the addition amount is small, there is no effect, and if the addition amount is large, the deterioration of the developer is rapid. ing.

On the other hand, as a binder resin for toner, a polyester resin is used because of its excellent low-temperature fixing property. The polyester resin is inherently good in fixing properties, and as described in US Pat. No. 3,590,000,
It can be sufficiently fixed even in the non-contact fixing method, but it is difficult to use in the heat roller fixing method because the offset phenomenon easily occurs. In addition, JP-A-50-44836, JP-A-57-37353, and JP-A-57-1.
No. 09875 describes polyester resins having improved offset resistance using a polycarboxylic acid, but these also do not have sufficient offset resistance to be used, or have In addition to sacrificing the low temperature fixing property originally possessed by the polyester resin, there is a problem that the pulverizability of the resin and toner is extremely poor.

Therefore, the following attempts have been made to use a mixture of a polyester resin having excellent fixability and a styrene-acrylic resin.

A method of mixing a polyester resin and a styrene-acrylic resin (JP-A-49-6931 and JP-A-5-6931).
4-114245, JP-A-57-70523, JP-A-2-161464); Method for chemically bonding polyester resin and styrene-acrylic resin (JP-A-56-116043); to unsaturated polyester A method of copolymerizing a vinyl monomer (JP-A-57-60339 and JP-A-63-2).
79265, JP-A-1-156759, JP-A-2-
No. 5073); a method of copolymerizing a vinyl monomer with a polyester resin having a (meth) acryloyl group (JP-A-59-59).
45453); a method of copolymerizing a reactive polyester and a vinyl monomer in the presence of a polyester resin (JP-A-2-2966).
No. 4); and a method of blocking a polyester resin and a vinyl resin with an ester bond (JP-A-2-881).

However, since the polyester resin and the styrene-acrylic resin are inherently poor in compatibility, when merely mechanically mixing, depending on the mixing ratio, the resin and the internal additive such as carbon black may be added depending on the mixing ratio. Dispersion becomes poor and chargeability becomes non-uniform, which causes problems such as scumming in image evaluation. Further, when the molecular weights of the two types of resins are different, the melt viscosities of the two types may be different, so that it becomes difficult to make the dispersed particle size of the resin of the dispersed phase fine, and when toner is formed. The dispersion of the internal additives such as carbon black is very poor, and there is a problem that the image stability is greatly deteriorated. Further, when polymerizing a vinyl monomer with a reactive polyester, there is a problem that the composition is limited to prevent gelation.

From this point of view, Japanese Laid-Open Patent Publication No. 4-1423.
As described in JP-A No. 01-201, a mixture of two raw material monomers of a polymerization system in which the polymerization reaction is performed in independent reaction paths in the same reaction vessel is pre-blended, and the two polymerization reactions are performed in parallel. A developer composition using a binder resin characterized by the above has been developed. However, even if such a binder resin is used, it is considered that there is room for improvement in terms of obtaining further low-temperature fixability with respect to recent speeding up, downsizing, and energy saving of copying machines.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems, and in particular, electrostatic image development which is excellent in low temperature fixing property and anti-offset property and whose charge amount and image quality are not affected by environment. To provide toner for use.

[0013]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that a resin obtained by carrying out a condensation polymerization reaction and an addition polymerization reaction in the same reaction vessel in parallel. Therefore, it was found that the above object can be achieved by producing a toner for electrostatic image development using a binder resin having a specific molecular weight distribution, and completed the present invention.

That is, the gist of the present invention is (1) In an electrostatic image developing toner containing at least a binder resin and a colorant, the binder resin is a raw material monomer of a condensation polymerization resin or a vinyl resin. A resin obtained by conducting a polycondensation reaction and an addition polymerization reaction in parallel in the same reaction vessel using a raw material monomer and a mixture containing a compound capable of reacting with any of these raw material monomers, the binder resin 25 ℃
The content of chloroform-insoluble matter is 10 to 30% by weight, and the content of chloroform-soluble matter is 5 × 10 ^{3 to} 5 × 1 as measured by molecular weight distribution measurement by gel permeation chromatography.
Electrostatic latent image developing toner having at least one maximum peak between 0 ⁴ and (2) the raw material monomer of the polycondensation resin is a trivalent or higher carboxylic acid or its acid anhydride, The electrostatic image developing toner according to (1) above, which contains an alkyl ester and / or a trivalent or higher alcohol, (3) a weight ratio of the raw material monomer of the polycondensation resin and the raw material monomer of the vinyl resin (polycondensation system). / Vinyl type)
Is the above (1) or (2), which is 50/50 to 95/5.
(4) The toner for electrostatic image development described in (4), wherein the polycondensation resin is one or more selected from the group consisting of polyester, polyester-polyamide, and polyamide.
(3) The electrostatic image developing toner according to any one of (1) to (4), wherein the binder resin has an acid value of less than 30 KOHmg / g. (6) Chloroform-soluble component was 5 × 10 as measured by gel permeation chromatography.
^The present invention relates to the electrostatic image developing toner according to any one of (1) to (5), which has a maximum peak serving as a main peak between ^{3 and} 5 × 10 ⁴ .

The toner for electrostatic image development of the present invention uses a mixture of a binder resin containing a raw material monomer of a condensation polymerization type resin, a raw material monomer of a vinyl type resin, and a compound capable of reacting with any of these raw material monomers. A resin obtained by performing a condensation polymerization reaction and an addition polymerization reaction in parallel in the same reaction vessel, wherein the binder resin has the following properties.

That is, in the present invention, the content of the binder resin insoluble in chloroform at 25 ° C. is usually 10 to 30% by weight, and more preferably 15 to 30% by weight. If the content of chloroform insolubles is less than this range, an offset phenomenon tends to occur in a high temperature range when the toner is converted into a toner and fixing evaluation is performed. On the other hand, if the content of chloroform insolubles exceeds this range, the fixing strength of the toner tends to decrease, and fixing failure tends to occur.

In the present invention, the chloroform-soluble component at 25 ° C. of the binder resin is in the range of 5 × 10 ^{3 to} 5 × 10 ⁴ as determined by gel permeation chromatography (hereinafter abbreviated as GPC) molecular weight distribution measurement. Although it has at least one maximum peak, it is particularly preferable that the maximum peak serving as the main peak is in the range of 5 × 10 ^{3 to} 5 × 10 ⁴ . Here, the main peak refers to the highest maximum peak in the GPC molecular weight distribution. Soluble GP
In the C molecular weight distribution, if there is no maximum peak between 5 × 10 ^{3 and} 5 × 10 ⁴ , fixing failure occurs. Especially when there is no local maximum peak in this range, low temperature fixing is difficult to achieve.

Further, the binder resin has an acid value of 30 KOHmg / from the viewpoint of maintaining the charge amount of the toner under high temperature and high humidity.
It is preferably less than g, more preferably 5 to 25.
KOH mg / g. If the acid value is 30 KOHmg / g or more, the charge amount may decrease depending on the toner formulation and the type of carrier, which is not preferable. Above all, in the case of positively chargeable toner, 20 KOHmg / g or less is preferable.

In the present invention, the glass transition point of the binder resin is preferably 40 to 80 ° C, more preferably 50 to 70 ° C. By selecting one having a glass transition point in such a range, more excellent low-temperature fixability, smoothness of the fixing surface, and blocking resistance can be obtained. That is, when the glass transition point is higher than the above range, the fixability tends to deteriorate, and when the glass transition point is lower than the above range, the blocking resistance tends to decrease.

The glass transition point in the present invention is measured as follows. That is, using a differential scanning calorimeter (DSC210, manufactured by Seiko Denshi Kogyo Co., Ltd.), the temperature was raised to 200 ° C., left at that temperature for 3 minutes, and then cooled to room temperature at a temperature lowering rate of 10 ° C./min. When measured at a temperature rate of 10 ° C / min., The temperature at the intersection of the extension line of the baseline below the glass transition point and the tangent line showing the maximum slope from the rising portion of the peak to the apex of the peak is The transition point (Tg).

In the present invention, the molecular weight distribution of the binder resin,
To set the acid value, the glass transition point, etc. to the above range,
It can be easily performed by adjusting the composition ratio of the raw material monomers, the amount of the polymerization initiator, the amount of the catalyst, etc., or selecting the reaction conditions. In particular, a method of measuring the softening point of the binder resin with time and ending the reaction when the softening point reaches a predetermined softening point is effective for obtaining the above-mentioned desired physical properties.

That is, in the present invention, the softening point of the binder resin is preferably controlled to be 95 to 170 ° C.
More preferably, the temperature is controlled to 95 to 150 ° C. The softening point is measured by a method based on ASTM E28-67.

As the binder resin in the present invention, a polycondensation polymer resin raw material monomer, a vinyl resin raw material monomer, and a mixture containing a compound capable of reacting with any of these raw material monomers are used, and polycondensation is carried out in the same reaction vessel. It is obtained by carrying out the reaction and the addition polymerization reaction in parallel.

In the present invention, as the condensation resin, polyester, polyester-polyamide, polyamide, etc. are preferably used. As the raw material monomer of the polycondensation resin, polyester, polyester
There is no particular limitation as long as polyamide, polyamide or the like can be obtained.

As the raw material monomer of polyester, 2
A divalent or trivalent or higher alcohol, a divalent or trivalent or higher carboxylic acid, an acid anhydride thereof, or a lower alkyl ester is used. Here, when offset resistance is particularly required, partial crosslinking in the molecule of the binder resin is effective, and this can be achieved by using a trifunctional or higher polyfunctional compound. Therefore, in the present invention, from the viewpoint of offset resistance, it is preferable that the raw material monomer contains a trivalent or higher carboxylic acid or an acid anhydride thereof, a lower alkyl ester, and / or a trivalent or higher valent alcohol.

Examples of the dihydric alcohol component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,
2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis Alkylene oxide adducts of bisphenol A such as (4-hydroxyphenyl) propane and polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, ethylene glycol, diethylene glycol, triethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol,
1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol A and the like can be mentioned.

Of these, preferred are alkylene oxide adducts of bisphenol A, ethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol and neopentyl glycol are used.

Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol and 1,4
-Sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,
4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene and the like can be mentioned. Of these, glycerol and trimethylolpropane are preferably used.

In the present invention, these dihydric alcohols and trihydric or higher alcohols may be used alone or in combination.

Examples of the divalent carboxylic acid component include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid and azelaic acid. , Malonic acid, n-dodecenyl succinic acid, isododecenyl succinic acid, n-dodecyl succinic acid, isododecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid,
And anhydrides of these acids, or lower alkyl esters. Of these, maleic acid, fumaric acid, terephthalic acid and alkenylsuccinic acid are preferably used.

Examples of the trivalent or higher carboxylic acid or its acid anhydride and lower alkyl ester include, for example, 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid and 1,2,4-naphthalenetricarboxylic acid. Acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, tetra (Methylenecarboxyl) methane, 1,2,
Examples thereof include 7,8-octanetetracarboxylic acid, pyromellitic acid, empol trimer acid, their acid anhydrides and lower alkyl esters. Of these, especially 1,2,4-
Benzenetricarboxylic acid, that is, trimellitic acid or its derivative is inexpensive and easy to control the reaction, and thus is preferably used.

In the present invention, these divalent carboxylic acids and the like and trivalent or higher carboxylic acids can be used alone or in combination.

As a raw material monomer for polyester / polyamide and polyamide, a raw material monomer for forming an amide component is necessary in addition to the above raw material monomers.
Examples of the raw material monomers include polyamines such as ethylenediamine, pentamethylenediamine, hexamethylenediamine, diethylenetriamine, iminobispropylamine, phenylenediamine, xylylenediamine, triethylenetetramine, and aminocarboxylic acids such as 6-aminocaproic acid and ε-caprolactam. Examples thereof include acids and amino alcohols such as propanolamine. Of these, hexamethylenediamine and ε-caprolactam are preferably used.

When polyester / polyamide or a raw material monomer for polyamide is used, a polyfunctional compound having a valence of 3 or more should be used for partial cross-linking in the molecule of the binder resin, as in the case of polyester. is necessary. In that case, a trivalent or higher carboxylic acid, an acid anhydride thereof, or a lower alkyl ester is mainly used.

In the present invention, the above-mentioned trivalent or higher valent monomer is effective for reducing the dispersed particle size of the binder resin after the reaction is completed, and is 0.5 to 0.5 with respect to the raw material monomer of the polycondensation resin. It is preferred to use 10% by weight, especially 0.5 to 5% by weight. In the present invention, when these trivalent monomers are used in the above range, the resulting binder resin becomes completely uniform and has no sea-island structure, or even if it has a sea-island structure, The average particle size of the resin dispersed phase corresponding to the structure is as small as 2 μm or less.

The above-mentioned trivalent monomer is effective for controlling the degree of polymerization of the binder resin, and unless the dispersed particle size of the binder resin is required to be small, the trivalent monomer is used with respect to the raw material monomer of the polycondensation resin. 0.2-30% by weight, especially 0.5-30% by weight
It is preferred to use.

If the amount of these trivalent monomers used is more than the above range, gelation occurs during the polymerization reaction, and if the amount used is too small, a part of the toner on the paper is fixed on the paper during heat roll fixing. It is not preferable because it is difficult to prevent the offset phenomenon that the toner adheres to the roller surface without being completely fixed and is transferred to the next paper.

Examples of raw material monomers for the vinyl resin in the present invention include styrene, o-methylstyrene,
Styrene or styrene derivatives such as m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-chlorostyrene, vinylnaphthalene; ethylene, propylene, butylene, isobutylene, etc. Ethylenically unsaturated monoolefins; eg vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, vinyl propionate, vinyl formate,
Vinyl esters such as vinyl caproate; for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate,
Isobutyl acrylate, tert-butyl acrylate,
Amyl acrylate, cyclohexyl acrylate, n-octyl acrylate, isooctyl acrylate, decyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, methoxyethyl acrylate, 2-hydroxyethyl acrylate, acrylic acid Glycidyl, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert methacrylate. −
Butyl, amyl methacrylate, cyclohexyl methacrylate, n-octyl methacrylate, isooctyl methacrylate, decyl methacrylate, lauryl methacrylate,
2-ethylhexyl methacrylate, stearyl methacrylate, methoxyethyl methacrylate, 2-methacrylic acid
Ethylenic esters such as hydroxyethyl, glycidyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; vinyl ethers such as vinyl methyl ether; vinylidene halides such as vinylidene chloride; N-vinylpyrrole , N-vinyl compounds such as N-vinylpyrrolidone.

Of these, styrene and α- are preferred.
Methylstyrene, propylene, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, methyl methacrylate, butyl methacrylate, and 2-hydroxyethyl methacrylate are used.

A polymerization initiator is used when polymerizing the raw material monomer of the vinyl resin, and examples of such a polymerization initiator include 2,2'-azobis (2,4-dimethylvaleronitrile), 2, 2'-azobisisobutyronitrile, 1,
1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, other azo or diazo polymerization initiators, benzoyl peroxide, methyl ethyl ketone per Examples thereof include peroxide-based polymerization initiators such as oxide, isopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide and dicumyl peroxide.

Two or more polymerization initiators may be mixed and used for the purpose of controlling the molecular weight and the molecular weight distribution of the polymer or the reaction time. The amount of the polymerization initiator used is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the vinyl-based monomer.

When polymerizing the raw material monomers of the vinyl resin, a crosslinking agent can be used if necessary. Examples of the cross-linking agent for vinyl monomers include divinylbenzene, divinylnaphthalene, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, diethylene glycol dimethacrylate,
Diethylene glycol diacrylate, triethylene glycol dimethacrylate, triethylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexylene glycol dimethacrylate,
Neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4-acryloxydiethoxyphenyl) propane, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetra A general crosslinking agent such as acrylate, dibromoneopentyl glycol dimethacrylate, diallyl phthalate, etc. can be appropriately used (combined with two or more if necessary).
Of these, divinylbenzene and polyethylene glycol dimethacrylate are preferably used.

The amount of these crosslinking agents used is 0.001 to 15% by weight, preferably 0.1 to 10% by weight, based on the raw material monomer of the vinyl resin. If the amount of these cross-linking agents used is more than 15% by weight, the gelation reaction will proceed rapidly, which makes it difficult to control the reaction and makes the toner difficult to melt due to heat, resulting in poor fixing.

In the present invention, a compound capable of reacting with both of the raw material monomers of the polycondensation resin and the vinyl resin (hereinafter sometimes abbreviated as "both reactive compound") is used. For example, the following general formula (I)
And those represented by (II). Some of these bireactive compounds partially overlap with the above-mentioned raw material monomers.

[0045]

Embedded image

[In the formula, R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom, a hydroxyl group, an optionally substituted alkyl group, an alkoxy group, an aryl group or a vinyl group or a halogen atom. As shown, these may together form a ring. A and B are the same or different and each represents an alkylene group represented by the general formula (III) or a general formula (IV).
A phenylene group represented by

[0047]

Embedded image

(R ⁴ , R ⁵ and R ⁶ are the same or different and represent a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group, an aryl group or a vinyl group or a halogen atom. May together form a ring. M represents a number from 0 to 5 and n represents a number from 0 to 2.)
And X and Y are the same or different and each represents -COOR ⁷ or -OR ⁸ (R ⁷ and R ⁸ represent a hydrogen atom or a lower alkyl group which may have a substituent).

Here, it is necessary that these compounds can react with both of the two raw material monomers of the polymerization system, but in the case where there are two or more kinds of the raw material monomers of one polymerization system, at least one of them is used. It only needs to be able to react with one.

Among the groups represented by R ^{1 to} R ⁶ in the general formulas (I) and (II), the alkyl group is a straight or branched chain having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms. Are preferred, for example, methyl group, ethyl group, n-propyl group, i-
Examples thereof include a propyl group, an n-butyl group and a tert-butyl group. These alkyl groups may be substituted with a phenyl group, a naphthyl group, a hydroxyl group or the like. Examples of the alkoxy group include methoxy group, ethoxy group, n-
Examples thereof include a propoxy group, an i-propoxy group, a t-butoxy group and the like, and these groups may be substituted with a hydroxyl group, a carboxyl group or the like. Examples of the aryl group include a phenyl group, a naphthyl group and a benzyl group, and these groups may be substituted with a methyl group, an ethyl group, a methoxy group, an ethoxy group, a carboxyl group, a hydroxyl group or the like. Moreover, the vinyl group may be substituted with a hydroxyl group, a phenyl group, an alkyl group, an alkoxy group, a carboxyl group, or the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom and a bromine atom are particularly preferable. Further, the lower alkyl group represented by R ⁷ and R ⁸ has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group and the like, and these groups are substituted with a hydroxyl group or the like. Good.

Typical examples of the bireactive compounds represented by the general formulas (I) and (II) include the following compounds (1) to (36).

[0052]

[Chemical 3]

[0053]

[Chemical 4]

[0054]

[Chemical 5]

Further, the lower alkyl ester of the above-mentioned ethylenic monocarboxylic acid and the anhydride or lower alkyl ester of the above-mentioned ethylenic dicarboxylic acid can be mentioned.

The amount of these both-reactive compounds used is usually 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the total raw material monomers. If the amount used is less than this range, the two polymerization systems will not be compatible with each other and a resin having a large sea-island structure will tend to be formed, resulting in poor dispersion of the colorant and causing scumming and uneven printing. Therefore, it is not preferable.

In the method for producing a binder resin using the above raw materials, the polycondensation reaction and the addition polymerization reaction are carried out in parallel in the same reaction vessel. In such a method, the progress and completion of the two polymerization reactions do not have to be simultaneous in time, and the reaction temperature and time are appropriately selected according to the respective reaction mechanisms to allow the reactions to proceed and complete. Good.

Specifically, the polymerization reaction is carried out, for example, in a mixture of polyester, polyester / polyamide or polyamide raw material monomers under a temperature condition suitable for addition polymerization reaction, a vinyl resin raw material monomer, a crosslinking agent, and polymerization initiation. The step of dropping the mixture of the agents and partially carrying out the polycondensation reaction in parallel with the addition polymerization reaction in the presence of the bireactive compound, and the addition polymerization while maintaining the temperature of the obtained mixture under the above conditions. It is carried out by a method consisting of a step of completing only the reaction and then a step of raising the reaction temperature to raise the degree of polymerization of the polycondensation reaction.

Here, the temperature condition suitable for the addition polymerization reaction depends on the kind of the polymerization initiator used, but it is 50 to 1
It is usually carried out in the temperature range of 80 ° C. The optimum temperature range for increasing the polymerization degree of the polycondensation reaction is usually 190 to
270 ° C. As described above, a binder resin in which two kinds of resins are effectively mixed and dispersed can be obtained by a method of allowing two independent reactions to proceed in parallel in a reaction vessel.

In the present invention, the weight ratio (polycondensation type / vinyl type) of the raw material monomer of the polycondensation type resin and the raw material monomer of the vinyl type resin is 50 when the polymerization reaction is carried out in parallel.
It is preferably / 50 to 95/5, and more preferably 70/30 to 90/10. If the proportion of the vinyl-based resin exceeds this range, the fixing becomes poor, and if it is less than this range, the stability of the image against the environment becomes poor, which is not preferable.

The electrostatic image developing toner of the present invention is characterized in that the above-mentioned binder resin is used in the electrostatic image developing toner comprising at least a binder resin and a colorant. To manufacture such a toner, for example, the binder resin, a colorant, and if necessary, a charge control agent, a magnetic material, etc. are used.

As the colorant used in the present invention, various carbon blacks produced by the thermal black method, acetylene black method, channel black method, lamp black method and the like, and grafts obtained by coating the surface of carbon black with a resin. Carbon Black, Nigrosine Dye, Phthalocyanine Blue, Permanent Brown FG,
Brilliant First Scarlet, Pigment Green B, Rhodamine-B Base, Solvent Red 49,
Solvent Red 146, Solvent Blue 35 and the like and mixtures thereof can be mentioned, and it is usually preferable to use about 1 to 15 parts by weight per 100 parts by weight of the binder resin.

As the charge control agent used as necessary, either positive or negative charge control agents can be used. The specific examples of the positive charge control agent are not particularly limited, and examples thereof include a nigrosine dye "Nigrosine Base E".
"X", "Oil Black BS", "Oil Black S"
O "," Bontron N-01 "," Bontron N-0 "
7 "," Bontron N-11 "(above, manufactured by Orient Chemical Co., Ltd.)" Copy Blue PR "(manufactured by Hoechst)
Etc .; triphenylmethane dye containing a tertiary amine as a side chain, quaternary ammonium salt compound, for example, "Bontron P-51" (manufactured by Orient Chemical Co.), cetyltrimethylammonium bromide, "COPY CHARGE PXVP435".
(Manufactured by Hoechst) and the like; polyamine resins such as "AFP
-B "(manufactured by Orient Chemical Co., Ltd.), imidazole derivative,
For example, "PLZ-2001", "PLZ-8001"
(The above is manufactured by Shikoku Kasei Co., Ltd.) and the like. Preferably, Bontron N-07 can be used.

Specific examples of the negative charge control agent include:
Without being particularly limited, for example, metal-containing azo dyes such as “Varifast Black 3804” and “Bontron S
-31 "(above, manufactured by Orient Chemical Co., Ltd.)," T-77 "
(Manufactured by Hodogaya Chemical Co., Ltd.), "Bontron S-32", "Bontron S-34", "Bontron S-36" (above,
Orient Chemical Co., Ltd.), "Aizen Spyron Black T
RH "(manufactured by Hodogaya Chemical Co., Ltd.); copper phthalocyanine dye, metal complex of alkyl derivative of salicylic acid, for example," Bontron E-81 "," Bontron E-82 ",
"Bontron E-84", "Bontron E-85" (above, Orient Chemical Co., Ltd. make); Quaternary ammonium salt, for example, "COPY CHARGE NX VP434" (Hoechst Co. make), a nitro imidazole derivative etc. can be mentioned. Preferably, Bontron S-34, T-77, and Eisenspiron Black TRH can be used. The above charge control agent is 0.1 to 8.0% by weight, preferably 0.1% to the binder resin.
Use 2 to 5.0% by weight.

Further, it is preferable to use a wax such as polyolefin as the offset preventing agent.
It is preferable to use 1 to 5 parts by weight with respect to 00 parts by weight.
Here, examples of the polyolefin include polyethylene and polypropylene, and those having a relatively low molecular weight, particularly those having a molecular weight of 600 to 15,000 as measured by the vapor permeation method.
Are preferred. Further, the softening point by the ring and ball method is 70 to
It is preferably 150 ° C., particularly 120 to 150 ° C.

In conventional toners, it was difficult to blend these waxes because of poor compatibility,
In the present invention, they can be easily blended, and by blending them, the low temperature fixing property becomes more excellent.

Further, when a toner is produced, a characteristic improver such as a fluidity improver such as hydrophobic silica may be added. However, when the binder resin of the present invention is used, these are added. It is not necessary to add the property improving agent, and even when it is added, the addition amount may be small.

The binder resin obtained by the present invention, the colorant, and optionally the property improving agent are uniformly dispersed, and then melt-kneaded, cooled, pulverized and classified by a known method to give an average particle diameter of 5 to 5. 15 μm toner can be obtained. The toner may be a non-magnetic one-component developer, or by mixing a magnetic powder, that is, an iron oxide-based carrier, a spherical iron oxide-based carrier or a ferrite-based carrier as it is, or by mixing it with a resin or the like. , A dry two-component developer can be used.

In order to produce a magnetic toner, magnetic particles may be added to the binder resin obtained by the present invention. As the magnetic particles, for example, powder of a metal exhibiting ferromagnetism such as iron, cobalt and nickel, or an alloy or compound containing an element exhibiting ferromagnetism such as ferrite, hematite and magnetite can be used. These magnetic materials are uniformly dispersed in the core material in the form of fine powder having an average particle size of 0.1 to 1 μm. The content thereof is 20 to 70 parts by weight, preferably 30 to 70 parts by weight, based on 100 parts by weight of the binder resin.

[0070]

EXAMPLES The present invention will be described in more detail with reference to production examples, examples and comparative examples, but the present invention is not limited to these examples. The softening point and glass transition point of the obtained binder resin were measured by the methods described above.

[Measurement of Molecular Weight Distribution by GPC] Preparation of Sample Solution The binder resin is dissolved in chloroform to a concentration of 0.05 to 0.5% by weight. Next, this solution was added to a Teflon filter with a pore size of 2 μm (manufactured by Sumitomo Electric Industries, Ltd.,
(FP-200) was used to remove insoluble components by filtration to obtain a sample solution. Measurement of molecular weight distribution Chloroform was run as an eluent at a flow rate of 1 ml / min and 4
The column was stabilized in a constant temperature bath at 0 ° C. The measurement was performed by injecting 100 μl of the sample solution therein. The molecular weight of the sample is
It was calculated based on a calibration curve prepared in advance. The calibration curve at this time was prepared by using several kinds of monodisperse polystyrene as standard samples. Analytical column GMHLX + G3000HXL (manufactured by Tosoh Corporation)

[Measurement of Insoluble Content in Chloroform] The sample was finely ground in a coffee mill until it passed through a 20 mesh sieve, and after collecting 5.00 g, a radio light was added.
Along with 00 g, the mixture was put in a 150 cc mayonnaise bottle, 100 g of chloroform was added, and the mixture was placed on a ball mill stand and rotated at 25 ° C. for 5 hours or more to sufficiently dissolve it. A 7 cmφ filter paper (No. 2) was placed in the pressure filter, and 5.00 g of radiolite was uniformly pre-coated on the filter paper, and a small amount of chloroform was added for close contact. The solution prepared by the above procedure is poured into a pressure filter.
The deposit in the mayonnaise bottle was thoroughly washed with 100 ml of chloroform, poured into a filter, and the upper lid was tightly closed. Pressure filtration (up to 4 kg / cm ² ) was performed, and when the outflow of chloroform stopped, the lid was opened and 100 ml of chloroform was added, the contents were thoroughly washed at 25 ° C., and pressure filtration was further performed. After the filtration was completed, the filter paper, the residue on the filter paper, and the radiolite were placed on an aluminum foil and dried in a vacuum dryer. (80-100 ° C / 100mmHg, 10H
r. ) All dry solids were weighed. Based on the weight, the insoluble content was calculated by the following formula. Insoluble matter (%) = (total weight of dry solid-weight of filter paper-radiolite (10.00)) / sample amount (5.00) x 100

Production Example 1 As a vinyl resin monomer, styrene (665 g), 2-
127 g of ethylhexyl acrylate and 32 g of dicumyl peroxide as a polymerization initiator are placed in a dropping funnel. 1444 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 40 g of fumaric acid, 47 g of isododecenyl succinic anhydride, 378 g of terephthalic acid, 135 g of 1,2,4-benzenetricarboxylic acid, and dibutyl 5 g of tin oxide was placed in a glass 5 liter 4-necked flask, equipped with a thermometer, a stainless stir bar, a downflow condenser and a nitrogen inlet tube, while stirring at a temperature of 160 ° C. in a nitrogen atmosphere in a mantle heater. The vinyl resin monomer and the polymerization initiator were dropped from the dropping funnel over 1 hour. 160 ° C
The mixture was aged for 2 hours while being kept at, and the temperature was raised to 230 ° C. for reaction. The degree of polymerization was traced from the softening point according to ASTM E28-67, and the reaction was terminated when the softening point reached 130 ° C.

The glass transition temperature (Tg) of the obtained resin was 62.5 ° C. with one peak and the acid value was 8.5 KOHmg.
/ G. Also, the chloroform insoluble content of this resin was measured by the above-mentioned method, and it was 22.5% by weight.
On the other hand, the chloroform-soluble matter was subjected to GPC measurement by the above-mentioned method and found to contain 5 × 10 ^{3 to} 5 × 1 including the main peak.
Two maximum peaks were observed in the range of 0 ⁴ . The obtained resin is referred to as Binder Resin A.

Production Example 2 480 g of styrene, 85 g of butyl acrylate, 20 g of acrylic acid, and 23 g of dicumyl peroxide as a polymerization initiator were placed in a dropping funnel as the vinyl resin monomer. Polyoxypropylene (2.2) -2,2-
980 g of bis (4-hydroxyphenyl) propane, 228 g of polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 200 g of isododecenyl succinic anhydride, 248 g of terephthalic acid, 1,2,2.
144 g of 4-benzenetricarboxylic acid and 5 g of dibutyltin oxide were placed in a glass 5-liter 4-necked flask, equipped with a thermometer, a stainless stir bar, a flow-down condenser and a nitrogen inlet tube, and under a nitrogen atmosphere in a mantle heater. , Stirred at a temperature of 160 ° C. The following operation was the same as in Production Example 1, and the reaction was terminated when the softening point reached 118 ° C.

The glass transition temperature (Tg) of the obtained resin was 59.5 ° C. with one peak and the acid value was 21.3 KOH.
It was mg / g. Also, the chloroform insoluble content of this resin was measured by the above method to be 25.0% by weight,
In the GPC measurement of the chloroform-soluble content, two local maximum peaks were observed in the range of 5 × 10 ^{3 to} 5 × 10 ⁴ , including the main peak. The obtained resin is referred to as Binder Resin B.

Production Example 3 (for comparison) 350 g of styrene, 150 g of butyl methacrylate, and 25 g of dicumyl peroxide as a polymerization initiator were placed in a dropping funnel as a vinyl-based resin monomer. 780 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 76 g of 1,2,4-benzenetricarboxylic acid, 240 g of isophthalic acid, and 2 g of dibutyltin oxide were added to 5 liter of glass. It was placed in a four-necked flask and equipped with a thermometer, a stainless stir bar, a flow-down condenser and a nitrogen introduction tube. The following operations were performed under the same polymerization conditions as in Production Example 1.

The resin thus obtained was evaluated in the same manner as in Production Example 1. As a result, the glass transition temperature of the resin was 6 with one peak.
The temperature was 2 ° C., and the acid value was 9.3 KOH mg / g. The chloroform-insoluble content of this resin was 20.4% by weight, and in the GPC measurement of the chloroform-soluble content, the main peak was included in the range of 5 × 10 ^{3 to} 5 × 10 ⁴ , including the main peak. The maximum peak of the book was recognized. The obtained resin is referred to as a binder resin C.

Production Example 4 (for comparison) 550 g of xylene was placed in a 2-liter glass four-necked flask equipped with a thermometer, a stainless stir bar, a flow-down condenser and a nitrogen inlet tube, and the temperature was raised to 135 ° C. after replacement with nitrogen. did. Styrene 700g, butyl methacrylate 3
00g and dicumyl peroxide 5 as a polymerization initiator
Place 0 g in the dropping funnel and add dropwise over 1 hour.
It was aged for 2 hours at 35 ° C. After that, the temperature is raised to 200 ° C., xylene is distilled off under reduced pressure, and the mixture is extracted into a vat
After cooling, it was ground. The softening point according to ASTM E28-67 was 110 ° C, and the glass transition temperature was 66 ° C. The obtained resin is referred to as Binder Resin D.

500 g of the above resin D, 800 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 15 g of fumaric acid, 1,2,4
-60 g of benzene tricarboxylic acid, 250 of isophthalic acid
g and 2 g of dibutyltin oxide were placed in a glass 5 liter 4-necked flask, and a thermometer, a stainless steel stirring rod,
A downflow condenser and a nitrogen introduction tube were attached, and the reaction was carried out in a mantle heater at 230 ° C. under a nitrogen atmosphere.
The degree of polymerization was traced from the softening point according to ASTM E28-67, and the reaction was terminated when the softening point reached 120 ° C.

The glass transition temperature of the obtained resin was 63 ° C.
It shows two peaks at 66 ° C and an acid value of 9.7 KOHmg /
g. Also, the chloroform insoluble content of this resin is 5
% By weight, and in GPC measurement of chloroform-soluble content,
No maximum peak was observed in the range of 5 × 10 ^{3 to} 5 × 10 ⁴ . The obtained resin is referred to as Binder Resin E.

Production Example 5 (for comparison) Polyoxypropylene (2.2) used in Production Example 1
2,2-bis (4-hydroxyphenyl) propane 14
44 g, fumaric acid 40 g, isododecenyl succinic anhydride 24 g, terephthalic acid 378 g, 1,2,4-benzenetricarboxylic acid 135 g, and dibutyltin oxide 5 g
Was homopolymerized. The degree of polymerization is ASTM E28-67.
The softening point was followed according to the above, and the reaction was terminated when the softening point reached 110 ° C.

The resin thus obtained was evaluated in the same manner as in Production Example 1. As a result, the glass transition temperature of the resin was 63 ° C. The acid value was 15.0 KOHmg / g. 780 g of the above resin is used in the same manner as in Production Example 1 made of 2 liter glass 4
It was put in a necked flask, 250 g of xylene was added to dissolve the resin, and then the temperature was raised to 135 ° C. Next, as a monomer of the vinyl resin used in Production Example 1, styrene 665 was used.
g, 2-ethylhexyl acrylate 127 g and dicumyl peroxide 32 g as a polymerization initiator were placed in a dropping funnel and added dropwise over 1 hour, followed by aging for 2 hours. After that, the temperature was raised to 200 ° C., xylene was distilled off under reduced pressure, and when the softening point reached 120 ° C., it was taken out into a vat, cooled, and ground.

The glass transition temperature of the obtained resin shows two peaks at 63 ° C. and 65 ° C., and the acid value is 9.0 KOHmg /
g. In addition, the chloroform insoluble content of this resin is 9
% By weight, and in GPC measurement of chloroform-soluble content,
No maximum peak was observed in the range of 5 × 10 ^{3 to} 5 × 10 ⁴ . The obtained resin is referred to as a binder resin F.

Production Example 6 (Comparative) Polyoxypropylene (2.2) used in Production Example 1
2,2-bis (4-hydroxyphenyl) propane 14
44 g, fumaric acid 40 g, isododecenyl succinic anhydride 47 g, terephthalic acid 378 g, 1,2,4-benzenetricarboxylic acid 135 g, and dibutyltin oxide 5 g
Was placed in a glass 5-liter four-necked flask, equipped with a thermometer, a stainless stir bar, a downflow condenser and a nitrogen inlet tube, and homopolymerized while stirring at a temperature of 230 ° C. in a nitrogen atmosphere in a mantle heater. .

The resin thus obtained was evaluated in the same manner as in Production Example 1. As a result, the softening point of the resin was 130 ° C and the glass transition temperature was 60.3 ° C. The acid value is 15.0KOH
It was mg / g. The obtained resin is referred to as a binder resin G.

Production Example 7 (Comparative) 200 g of styrene, 86 g of butyl methacrylate, and 14 g of dicumyl peroxide as a polymerization initiator were placed in a dropping funnel as the vinyl resin monomer. 780 g of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, 100 g of isododecenyl succinic anhydride, 280 g of terephthalic acid, 1,2,4-
75 g of benzenetricarboxylic acid and 2 g of dibutyltin oxide were placed in a glass 5 liter 4-neck flask,
A thermometer, a stainless stirrer, a downflow condenser and a nitrogen introduction tube were attached, and the mixture was stirred in a mantle heater under a nitrogen atmosphere at a temperature of 160 ° C. The following operation was the same as in Production Example 1, and the reaction was terminated when the softening point reached 115 ° C.

The resin thus obtained was evaluated in the same manner as in Production Example 1. As a result, when the glass transition temperature of the resin was determined by DSC, one peak was 63.5 ° C., and the acid value was 3
It was 4.5 KOHmg / g. The chloroform-insoluble content of this resin was 7% by weight, and two maximum peaks were observed in the range of 5 × 10 ^{3 to} 5 × 10 ⁴ in the GPC measurement of the chloroform-soluble content. The obtained resin is referred to as a binder resin H.

Production Example 8 (for comparison) 480 g of styrene, 85 g of butyl acrylate, 20 g of acrylic acid, and 23 g of dicumyl peroxide as a polymerization initiator were placed in a dropping funnel as the vinyl resin monomer. Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 980 g, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 228 g, isododecenyl succinic anhydride 200 g, terephthalic acid 248 g, 1,2,4
-Add 144 g of benzenetricarboxylic acid and 5 g of dibutyltin oxide into a glass 5 liter 4-necked flask,
A thermometer, a stainless stirrer, a downflow condenser and a nitrogen introduction tube were attached, and the mixture was stirred in a mantle heater under a nitrogen atmosphere at a temperature of 160 ° C. The following operations were the same as in Example 1, and the reaction was terminated when the softening point reached 130 ° C. The glass transition temperature (T
g) has one peak at 61.5 ° C. and an acid value of 15.7.
It was KOH mg / g. The chloroform insoluble content of this resin was 32.1% by weight, and in the GPC measurement of the chloroform soluble content, 5 × 10 ³ to 5 including the main peak was measured.
Two maximum peaks were recognized in the range of 5 × 10 ⁴ .
The obtained resin is referred to as Binder Resin I.

Examples 1 to 3 and Comparative Examples 1 to 6 Materials having the compositions shown in Table 1 were premixed with a Henschel mixer, melt-kneaded with a twin-screw extruder, cooled, and then subjected to normal pulverization.
Untreated toners 1 to 9 having an average particle size of 11 μm through a classification process
Was manufactured.

[0091]

[Table 1]

Untreated toners 1 to 3 and 4 to 9 thus obtained
To 100 parts by weight of hydrophobic silica "H-
2000 "(manufactured by Wacker Chemical Co., Ltd.) was mixed and attached using a Henschel mixer to obtain toners 1 to 3 and comparative toners 1 to 6, respectively. 39 parts by weight of each of the above toners and spherical ferrite powder coated with styrene / methyl methacrylate resin (average particle size 100 μm
m) 1261 parts by weight was mixed to prepare a developer, and a commercially available electrophotographic copying machine (FT-4080 manufactured by Ricoh) was improved (amorphous selenium was used as the photoconductor, and the rotation speed of the fixing roller was 255 mm). / Sec, the temperature of the heat roller in the fixing device was made variable, and the image was printed using an oil coating device removed), and the printing durability and the fixing property were evaluated by the following methods.

(1) The charge amount was measured by a blow-off type charge amount measuring device described below, that is, a specific charge measuring device equipped with a Faraday cage, a condenser and an electrometer. The measurement method is as follows. First, the developer prepared above is mixed with W (g) (0.15 to 0.20 g)
It is put in a brass measuring cell equipped with a stainless steel mesh of 00 mesh (the size of which does not allow carrier particles to pass). Next, after sucking for 5 seconds from the suction port, the atmospheric pressure regulator shows 0.6 kg / cm ²
Blow for 2 seconds to remove only toner from the cell.

At this time, the voltage of the electrometer 2 seconds after the start of the blow is set to V (volt). If the electric capacity of the condenser is C (μF), the specific charge of this toner is Q /
m is calculated by the following equation. Q / m (μC / g) = C × V / m Here, m is the weight of the toner contained in the developer in W (g), and the weight of the toner in the developer is T (g). When the weight of the developer is D (g), the toner concentration of the sample is expressed as T / D × 100 (%), and m is calculated by the following formula. m (g) = W × (T / D)

The developer was used in the copying machine, and continuous copies of 100,000 sheets were made under normal environment (23 ° C., 50% R).
H) under high temperature and high humidity (35 ° C., 85% RH) to evaluate the change in charge amount and the occurrence of background stain during the printing durability test. Table 2 shows the above results.

[0096]

[Table 2]

(2) The fixing property of the toner was evaluated by the minimum fixing temperature. Here, the minimum fixing temperature is a reflection densitometer of Macbeth Inc. before and after rubbing 5 times on the image fixed through a fixing machine, placing a load of 500 g on a sand eraser with a bottom surface of 15 mm × 7.5 mm, and rubbing. The optical reflection density is measured according to the following, and it means the temperature of the fixing roller when the fixing rate exceeds 70% according to the following definition. Fixing rate (%) = [(image density after rubbing) / (image density before rubbing)] × 100

The fixing roller temperature was controlled within the range of 100 to 240 ° C., and the above fixing property was evaluated.

(3) Regarding the offset resistance,
It was evaluated by measuring the low temperature offset extinction temperature and the high temperature offset generation temperature. That is, the temperature of the heat roller surface was raised in the range of 70 to 240 ° C. to perform a copy test, and the adhesion of the toner on the heat roller surface was visually evaluated at each temperature. (4) Regarding image density, no offset occurs,
The image fixed in the temperature range for sufficient fixing was measured with a reflection densitometer manufactured by Macbeth. The above results are shown in Table 3.

[0100]

[Table 3]

As is clear from Table 2, toners 1 to 3 are
Has little change in charge amount under normal environment and high temperature and high humidity, and has good image quality, so that it can be used under severe environmental conditions. Further, as is clear from Table 3, the toners 1 to 3 have low minimum fixing temperature, high high temperature offset generation temperature, and excellent low temperature fixing property and anti-offset property. On the other hand, Comparative Toner 1 using the binder resin (binder resin C) obtained without using the bireactive compound
However, since the dispersibility of the resin was poor, the change in the charge amount under high temperature and high humidity was large, and soiling occurred. Further, in the comparative toner 5 using the vinyl resin (binder resin D) and the polyester (binder resin G) as the binder resin, the change in the charge amount under high temperature and high humidity is large, and the ground stain is generated, and the high temperature offset is caused. The generation temperature was low. Further, in Comparative Toners 2 to 4 using binder resins (binder resins E, F, and H) having a chloroform-insoluble content of less than 10% by weight, the change in charge amount is large, soiling occurs, and the minimum fixing temperature is high. The high temperature offset generation temperature was low. On the other hand, in Comparative Toner 6 using the binder resin (binder resin I) having a chloroform insoluble content of more than 30% by weight, the minimum fixing temperature was high and the low temperature offset generation temperature was also high.

[0102]

The toner for developing an electrostatic image of the present invention is particularly excellent in low-temperature fixing property and anti-offset property, and its charge amount and image quality are not affected by environment. Therefore, in the heat roller fixing method, fixing can be performed at a low temperature without using the offset prevention liquid.

Claims (6)

[Claims] 1. In an electrostatic image developing toner containing at least a binder resin and a colorant, the binder resin is any one of a raw material monomer of a polycondensation resin, a raw material monomer of a vinyl resin, and these raw material monomers. A resin obtained by performing a polycondensation reaction and an addition polymerization reaction in parallel in the same reaction vessel using a mixture containing a compound capable of reacting with each other, wherein the binder resin has a chloroform-insoluble content at 25 ° C. 10
And 30% by weight, and the chloroform-soluble component has at least one maximum peak between 5 × 10 ^{3 and} 5 × 10 ⁴ in molecular weight distribution measurement by gel permeation chromatography. Toner for image development. 2. The electrostatic image developing according to claim 1, wherein the raw material monomer of the polycondensation resin contains a carboxylic acid having a valence of 3 or more, an acid anhydride thereof, a lower alkyl ester, and / or an alcohol having a valence of 3 or more. toner. 3. A weight ratio (polycondensation type / vinyl type) of the raw material monomer of the polycondensation type resin and the raw material monomer of the vinyl type resin.
Is 50/50 to 95/5, and the electrostatic image developing toner according to claim 1 or 2. 4. The toner for electrostatic image development according to claim 1, wherein the polycondensation resin is one or more selected from the group consisting of polyester, polyester-polyamide, and polyamide. 5. The toner for developing an electrostatic image according to claim 1, wherein the binder resin has an acid value of less than 30 KOHmg / g. 6. The chloroform-soluble matter is 5 × 1 as measured by molecular weight distribution measurement by gel permeation chromatography.
The electrostatic image developing toner according to any one of claims 1 to 5, which has a maximum peak serving as a main peak between 0 ^{3 and} 5 × 10 ⁴ .