JPH0844108A - Binder resin and toner for electrostatic image development - Google Patents

Abstract

(57) [Summary] [Structure] A binder resin for toner production, which is obtained by mixing two kinds of resins (A) and (B) having different softening points as main components. ) And the resin (B), a mixture containing a raw material monomer of a polycondensation-based resin, a raw material monomer of a vinyl-based resin, and a compound capable of reacting with any of these raw material monomers in a single reaction vessel. A binder resin for toner production, which is a resin obtained by carrying out a polymerization reaction and an addition polymerization reaction in parallel, and an electrostatic image developing toner containing the binder resin. By using the binder resin of the present invention, it is possible to obtain an electrostatic image developing toner which has excellent blocking resistance and can be fixed at a low temperature in the heat roller fixing system without using an offset preventing liquid. .

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic image developing toner for developing an electrostatic latent image formed in electrophotography, electrostatic recording, electrostatic printing or the like, and a toner for producing the toner. It relates to the resin to be applied.

[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, an electrostatic image developing toner excellent in low temperature fixing property and anti-offset property, and the toner are manufactured. To provide a binder resin for

[0013]

As a result of intensive studies aimed at achieving the above-mentioned object, the inventors of the present invention have found that the binder resin is made of two kinds of resins having different softening points, both of which are the same reaction vessel. In particular, by producing a toner for electrostatic image development by using as a binder resin a resin obtained by performing a condensation polymerization reaction and an addition polymerization reaction in parallel, especially at low temperature fixability and offset resistance They have found that an excellent toner can be obtained, and have completed the present invention.

That is, the gist of the present invention is (1) a binder resin for toner production, which is obtained by mixing two kinds of resins (A) and (B) having different softening points as main components. , Both of the resin (A) and the resin (B) are a raw material monomer of a polycondensation resin, a raw material monomer of a vinyl resin,
And a resin containing a compound containing a compound capable of reacting with any of these raw material monomers, the resin being obtained by carrying out a condensation polymerization reaction and an addition polymerization reaction in parallel in the same reaction vessel. And (2) the raw material monomer of the polycondensation resin contains a trivalent or higher carboxylic acid or acid anhydride thereof, a lower alkyl ester, and / or a trivalent or higher alcohol. The binder resin described in (3), the softening point of the resin (A) is 120 to 170 ° C., and the softening point of the resin (B) is 80 to
The binder resin according to (1) or (2) above, which has a temperature of 120 ° C.
(4) Mixing weight ratio of resin (A) and resin (B) (A /
B) is 90/10 to 10/90, and (1) to
(3) The binder resin according to any one of (5), wherein the mixing weight ratio of the raw material monomer of the polycondensation resin and the raw material monomer of the vinyl resin (polycondensation system / vinyl system) is 50/50 to 95/5.
The binder resin according to any one of (1) to (4) above,
(6) The binder resin according to any one of (1) to (5) above, wherein the polycondensation resin is one or more selected from the group consisting of polyester, polyester-polyamide and polyamide, and (7) at least a binder An electrostatic image developing toner comprising a resin and a colorant, wherein the binding resin is the binding resin according to any one of (1) to (6) above. About.

The binder resin for toner production of the present invention is a binder resin for toner production obtained by mixing two kinds of resins (A) and (B) having different softening points as main components. , Both of the resin (A) and the resin (B) are a raw material monomer of a polycondensation resin, a raw material monomer of a vinyl resin,
And a resin containing a compound containing a compound capable of reacting with any of these raw material monomers, the resin being obtained by carrying out a condensation polymerization reaction and an addition polymerization reaction in parallel in the same reaction vessel. In the present specification, the resin having a higher softening point will be referred to as a resin (A), and the resin having a lower softening point will be referred to as a resin (B).

In the present invention, the resin (A) has a softening point of 120 to 170 ° C. and the resin (B) has a softening point of 80 to 170 ° C.
It is preferably 120 ° C., more preferably the softening point of the resin (A) is 130 to 160 ° C., and the resin (B) is
Has a softening point of 85 to 105 ° C. When the softening point of the resin (A) is higher than this range, the low temperature fixability tends to deteriorate, and when the softening point of the resin (A) is lower than this range, the offset resistance tends to deteriorate. On the other hand, when the softening point of the resin (B) is higher than this range, the low-temperature fixability tends to deteriorate, and when the softening point of the resin (B) is lower than this range, the offset resistance and blocking resistance are low. Tends to get worse.

The temperature difference between the softening points of the resin (A) and the resin (B) is preferably 10 ° C. or more, more preferably 20 to 70 ° C. When the temperature difference of the softening point is smaller than this range, the development of the excellent properties of the resin (A) and the resin (B) is slightly suppressed, and as a result, the low temperature fixability, the offset resistance and the Either property of blocking property may be insufficient.

In the present invention, the softening point refers to that measured by a Koka type flow tester, which is outlined in JIS K 7210. In the present invention, the measurement is specifically performed as follows. That is, using a Koka type flow tester (manufactured by Shimadzu Corporation), while heating a sample of 1 cm ^{3 at} a temperature rising rate of 6 ° C./min, a load of 20 kg / cm ² was applied by a plunger to a diameter of 1 mm and a length of 1 mm. The nozzle of the plunger is pushed out, so that the plunger descent amount (flow value) -temperature curve is drawn, and the S
When the height of the curve is h, the temperature corresponding to h / 2 (the temperature at which half the resin flows out) is the softening point.

In the present invention, the weight ratio (A / B) of the resin (A) and the resin (B) is 90/10 to 10/90.
Is more preferable, and more preferably 80 / 20-
It is 20/80. When the weight ratio of the resin (A) is larger than the above range, the low temperature fixability and the smoothness of the fixing surface tend to be lowered, while when the weight ratio of the resin (A) is smaller than the above range. Has a tendency to deteriorate in offset resistance and blocking resistance.

The binder resin for toner production of the present invention is obtained by mixing two kinds of resins, resin (A) and resin (B), as a main component. Powder or pellets are simply mixed, both resins are uniformly mixed and dispersed by melt kneading, then powder or pellets are crushed, etc., or toner is already formed by a method such as melt kneading All of the embodiments up to the above are included.

Further, by mixing the resin (A) and the resin (B) in the above-mentioned weight ratio, it is not possible to obtain them simply by increasing the ratio of the polycondensation type monomer in the resin (A). A wide molecular weight distribution can be formed, and an electrostatic image developing toner having excellent low-temperature fixability and offset resistance can be obtained.

In the present invention, the glass transition points of the resin (A) and the resin (B) are both 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 (manufactured by Seiko Denshi Kogyo Co., Ltd.), the temperature was raised to 100 ° C., left at that temperature for 3 minutes, and then the temperature decrease rate was 10 ° C./mi.
Samples cooled to room temperature at n.
When measured in n., 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 defined as the glass transition point (Tg). And

In the present invention, the softening point and glass transition point of each resin can be easily adjusted by adjusting the polymerization initiator and the amount of catalyst in the raw material monomer mixture or selecting the reaction conditions. You can

Resin (A) and resin (B) in the present invention
Is a raw material monomer of a polycondensation resin, a raw material monomer of a vinyl resin, and a mixture containing a compound capable of reacting with any of these raw material monomers, and the polycondensation reaction and the addition polymerization reaction are performed in parallel in the same reaction vessel. It is obtained by doing.

In the present invention, the polycondensation resin is at least one selected from the group consisting of polyester, polyester-polyamide and polyamide. Therefore, the raw material monomer of the polycondensation resin is not particularly limited as long as these resins can be obtained by polycondensation.

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. Hereinafter, in the present specification, these raw material monomers having a valence of 3 or more are referred to as crosslinking agents.

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, 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, adipic acid, and alkenylsuccinic acid are preferably used.

Examples of the trivalent or higher carboxylic acid or its acid anhydride and lower alkyl ester include 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 and the like 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 of polyamide is used, a polyfunctional compound having a valence of 3 or more should be used for partial crosslinking 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 cross-linking agent (trivalent or higher valent monomer) is effective for reducing the dispersed particle size of the resin after the reaction is completed, and is 0. It is preferred to use 5-10% by weight, especially 0.5-5% by weight. In the present invention, when these cross-linking agents 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, it has an island structure. The average particle size of the resin dispersed phase corresponding to (2) is as small as 2 μm or less.

The above-mentioned cross-linking agent is effective for controlling the degree of polymerization of the resin, and if it is not particularly necessary to reduce the dispersed particle size of the resin, it is 0.2 with respect to the raw material monomer of the polycondensation resin.
It is preferable to use -30% by weight, especially 0.5-30% by weight.

When the amount of these cross-linking agents used is too much over this range, gelation occurs during the polymerization reaction, and when the amount used is too small, a part of the toner completely adheres to the paper during heat roll fixing. It is not preferable because it is difficult to prevent the offset phenomenon in which the toner adheres to the roller surface without sticking to the roller and transfers 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, preferably styrene and α-
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 kinds of 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 1 part by weight based on 100 parts by weight of the raw material monomer of the vinyl resin.
0 parts by weight.

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]

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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 both the methods for producing the resin (A) and the resin (B) 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 a raw material monomer of polyamide under a temperature condition suitable for addition polymerization reaction, a raw material monomer of vinyl resin, a cross-linking agent, and initiation of polymerization. A step of partially conducting a polycondensation reaction in parallel with the addition polymerization reaction by dropping a mixture of agents, and a step of maintaining the temperature of the obtained mixture under the above conditions to complete only the addition polymerization reaction,
Then, the reaction temperature is raised to increase the polymerization degree 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. When the ratio of the raw material monomers of the polycondensation resin is smaller than this range, the vinyl resin tends to be difficult to disperse in the polycondensation resin. If the ratio of the raw material monomer of the polycondensation resin is larger than this range, the characteristics of the vinyl resin cannot be utilized and the charging stability of the toner tends to be impaired.

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, polypropylene and the like, and those having a relatively low molecular weight, particularly those having a molecular weight of 3,000 to 1,500 by a vapor permeation method.
0 is preferable. The softening point by the ring and ball method is 70
˜150 ° C., especially 120 to 150 ° C. is preferable.

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, ferrite, magnetite and other iron, cobalt, nickel and other ferromagnets or alloys showing ferromagnetism, compounds containing these elements, or containing no ferromagnetism elements, an appropriate heat treatment is applied. Examples thereof include alloys that exhibit ferromagnetism, such as manganese-copper-aluminum, manganese-copper-tin, and other types of alloys called Heusler alloys containing manganese and copper, or chromium dioxide. A compound containing a ferromagnetic element is preferably used, and magnetite is particularly preferably 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. And its content is 20 per 100 parts by weight of binder resin.
˜70 parts by weight, preferably 30 to 70 parts by weight.

[0070]

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

Production Examples of Resins (A) and (B) The raw materials of the condensation polymerization type resin shown in Table 1 and Table 2 were prepared in 3 liters equipped with a thermometer, a stainless stir bar, a down flow type condenser and a nitrogen introducing tube. The mixture was placed in a 4-necked flask, and a mixture of the vinyl resin raw materials was mixed in advance in a mantle heater in a nitrogen atmosphere at a temperature of 135 ° C., and the mixture was added dropwise from a dropping funnel over 4 hours. While maintaining the temperature at 135 ° C, the mixture was aged for 5 hours, heated to 230 ° C and reacted. The degree of polymerization was traced from the softening point according to ASTM E28-67, the reaction was terminated when the softening point reached a predetermined value, the container was taken out from the container, cooled, and then pulverized. Table 3 shows the softening point and glass transition point of the obtained resin.

[0072]

[Table 1]

[0073]

[Table 2]

BPA / PO: Polyoxyprophylene (2.2) -2,2-bis (4-human oxyphenyl) proton BPA / EO: Polyoxyethylene (2.2) -2,2-hice (4-human phenoxyphenyl) fluor FA : Fumaric acid (bi-reactive compound) AA: acrylic acid (bi-reactive compound) i-DSA: isododecenyl succinic anhydride TPA: terephthalic acid TMA: anhydrous 1,2,4-benzenetricarboxylic acid HMDA: hexamethylenediamine DBO: Dibutyltin oxide St: Styrene EHA: 2-Ethylhexyl acrylate AIBN: Azobisisobutyronitrile DCP: Dicumyl peroxide

[0075]

[Table 3]

Examples 1 to 7 and Comparative Examples 1 to 4 In each of the Examples and Comparative Examples, a total of 100 parts by weight of the binder resin having the combination and blending amount shown in Table 4 and carbon black "Mogal L" (Cabot) were used. 7 parts by weight) and low molecular weight polypropylene "Viscor 660"
P ”(softening point: 130 ° C., manufactured by Sanyo Kasei Co., Ltd.) and 2 parts by weight of charge control agent“ Bontron S-34 ”(manufactured by Orient Chemical Co., Ltd.) are premixed, and then biaxially extruded. After melt-kneading with a machine and cooling, an untreated toner having an average particle diameter of 10 μm was manufactured through usual pulverization and classification steps.

To 100 parts by weight of the obtained untreated toner, 0.3 parts by weight of hydrophobic silica "H-2000" (manufactured by Wacker Chemical Co., Ltd.) was mixed and attached using a Henschel mixer, and toners 1 to 7 were obtained. And comparative toners 1 to 4.

39 parts by weight of each of the above toners and 1261 parts by weight of styrene / methyl methacrylate resin-coated ferrite powder (average particle size 100 μm) were mixed to obtain a developer.

Test Example A modified two-component dry copying machine (FT-4080, manufactured by Ricoh Co., Ltd.), which is commercially available, is used for this developer (the rotation speed of the fixing roller is set to 255 mm / sec, and the temperature of the heat roller in the fixing device is set. (Variable and oil-applying device removed) was used to obtain an initial image, and its performance was evaluated by the following method.

(1) Fixability The fixability of the toner was evaluated by the minimum fixing temperature. Here, the minimum fixing temperature means that the bottom surface is 15 mm × 7.
A load of 500 g was placed on a 5 mm sand eraser, the image fixed through the fixing device was rubbed 5 times back and forth, and the optical reflection density was measured by a reflection densitometer of Macbeth before and after rubbing,
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 between 100 and 240 ° C. to evaluate the fixing property.

(2) Hot Offset Occurrence Temperature In accordance with the measurement of the above-mentioned minimum fixing temperature, the toner image is transferred and the fixing process is carried out by the above-mentioned fixing roller, and then the blank transfer paper is subjected to the same conditions under the same fixing roller. Send to
The operation of visually observing whether or not toner stains are generated is repeated with the set temperature of the fixing roller being sequentially increased, and the lowest set temperature at which toner stains are generated is defined as the hot offset generation temperature.

(3) Blocking resistance 10 g of toner was placed in a 100 ml glass bottle and the temperature was adjusted to 5
The sample was left for 2 weeks under an environmental condition of 0 ° C. and a relative temperature of 26%, and evaluated according to the following criteria. ◯: No blocking is observed at all. Δ: Soft caking state. X: Hard caked. The above results are also shown in Table 4.

[0085]

[Table 4]

As can be understood from the above results, each of Toners 1 to 7 of the present invention has excellent offset resistance, excellent low-temperature fixability, and excellent blocking resistance, and particularly the thermal characteristics. An excellent toner can be obtained. On the other hand, Comparative Toner 1 has a softening point of resin (A) of 1
Since it is less than 20 ° C., it is inferior in offset resistance and blocking resistance. Comparative toner 2 has a low-temperature fixability because the softening point of the resin (B) is 120 ° C. or higher. Since Comparative Toner 3 uses only the resin (B), it is inferior in offset resistance and blocking resistance. Since the comparative toner 4 uses only the resin (A), the low temperature fixability is poor.

[0087]

By using the binder resin of the present invention, it is possible to obtain an electrostatic image developing toner which is excellent in blocking resistance and can be fixed at a low temperature in a heat roller fixing system without using an offset preventing liquid. You can

Claims (7)

[Claims] 1. A resin (A) and a resin (B) having different softening points.
A binder resin for producing a toner, which is obtained by mixing two kinds of resins as main components described above, wherein the resin (A) and the resin (B)
All of the above, using a mixture of a raw material monomer of a polycondensation resin, a raw material monomer of a vinyl resin, and a compound capable of reacting with any of these raw material monomers, a polycondensation reaction and an addition polymerization reaction in the same reaction vessel. A binder resin for toner production, which is a resin obtained by carrying out in parallel. 2. The raw material monomer of the polycondensation resin contains a trivalent or higher carboxylic acid or an acid anhydride thereof, a lower alkyl ester, and / or a trivalent or higher alcohol. Binder resin. 3. The softening point of the resin (A) is 120 to 170 ° C.
The binder resin according to claim 1 or 2, wherein the softening point of the resin (B) is 80 to 120 ° C. 4. The mixing weight ratio (A / B) of the resin (A) and the resin (B) is 90/10 to 10/90.
Binder resin according to any one of 3 to 3. 5. The mixing 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 50/50 to 95/5. Binder resin. 6. The binder resin according to claim 1, wherein the polycondensation resin is one or more selected from the group consisting of polyester, polyester-polyamide and polyamide. 7. An electrostatic image developing toner containing at least a binder resin and a colorant, wherein the binder resin is the binder resin according to any one of claims 1 to 6. Toner for electrographic development.