JP2013109237A - Toner for electrostatic charge image development - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide toner for electrostatic charge image development which is excellent in low-temperature fixability and heat-resistant preservability and further satisfactory in preservability and image density of printed matter.SOLUTION: There is provide toner for electrostatic charge image development containing a binder resin which contains a crystalline polyester (1-1) obtained by using a raw material monomer which contains a diol having 8 to 12 of carbon number and a dicarboxylic acid compound having 10 to 12 of carbon number and in which the total content of both is 80 mol% or more, an alcohol component, and an amorphous hybrid resin (2-1) containing an amorphous condensation polymerization resin component and an addition polymerization resin component obtained by polymerizing a raw material monomer of an amorphous condensation polymerization resin containing a carboxylic acid component containing an aromatic dicarboxylic acid compound, a raw material of additional polymerization resin and 3 to 15 pts.wt. of a compound which react with both a raw material monomer of an amorphous condensation polymerization resin and a raw material monomer of an addition polymerization resin based on 100 pts.wt. of a raw material monomer of the addition polymerization resin.

Description

  The present invention relates to an electrostatic image developing toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.

  Due to the recent demand for energy saving, toners are required to have low-temperature fixing performance, and many reports have reported that the use of crystalline polyester is effective in improving low-temperature fixing. This is because crystalline polyester is particularly compatible with amorphous polyester and it is easy to finely disperse crystalline polyester.

  However, since the crystalline polyester finely dispersed and compatibilized in the amorphous polyester has a low crystallization speed, it does not crystallize sufficiently in a normal toner manufacturing method, and works as a plasticizer. Further, there is a problem that the glass transition temperature of the toner is lowered and the heat resistant storage stability is deteriorated.

  For this problem, it has been reported that an annealing process is introduced when toner is formed (see Patent Document 1), and introduction of a crystal nucleating agent (see Patent Documents 2 to 5) is effective. However, there are problems such as the need for new capital investment and a long process time, and the problem of crystal nuclei such as an increase in cost due to the introduction of new raw materials and an effect on coloring, glossiness and transparency. Further, in recent years, a method has been used in which a toner is given a core / shell structure so that a crystalline component is contained in the toner so that the preservability is not deteriorated.

  Also, in recent years, electrophotographic printers have become widespread and cost reductions, so they can be used as labels for cans and drums. If labels are applied at a temperature of about 60 ° C, the label and other drums stick together. There is a problem.

JP 2005-308995 A JP 2004-309517 A JP 2006-113473 A JP 2006-227539 A JP 2007-093809 A

  However, although the heat-resistant storage stability of the toner is solved by the annealing and the core / shell structure, these methods have no effect on the storage stability of the printed matter.

  Furthermore, toner containing a crystalline polyester having low compatibility with the amorphous polyester has a low dispersibility of the crystalline polyester, so that the low-temperature fixability cannot be sufficiently exhibited. It has been confirmed that there are problems such as lowering, and it is not possible to achieve both plasticization and effects by controlling compatibility alone.

  An object of the present invention is to provide a toner for developing an electrostatic charge image that is excellent in low-temperature fixability and heat-resistant storage stability, and also has good storage stability and image density of printed matter.

The present invention
[1] Crystalline polyester (1-1) obtained using a raw material monomer containing a diol having 8 to 12 carbon atoms and a dicarboxylic acid compound having 10 to 12 carbon atoms and having a total content of 80 mol% or more When,
A raw material monomer of an amorphous polycondensation resin containing an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid compound, a raw material monomer of an addition polymerization resin, and 100 parts by weight of the raw material monomer of the addition polymerization resin 3-15 parts by weight of an amorphous polycondensation resin component and an addition polycondensation resin component obtained by polymerizing a compound capable of reacting with either the addition polymerization resin material monomer Amorphous hybrid resin containing a polymeric resin component (2-1)
A toner for developing an electrostatic image comprising a binder resin comprising a weight ratio of the crystalline polyester (1-1) to the amorphous hybrid resin (2-1) (crystallinity) A toner for developing an electrostatic image in which polyester (1-1) / amorphous hybrid resin (2-1) is 1/99 to 40/60, and [2] a diol having 8 to 12 carbon atoms and a carbon number With respect to 100 parts by weight of the raw material monomer of the crystalline polyester containing 10 to 12 dicarboxylic acid compounds, and the total content of both is 80 mol% or more, the raw material monomer of the addition polymerization resin, and the raw material monomer of the addition polymerization resin 3 to 15 parts by weight of a crystalline polyester component and an addition polymerization resin component obtained by polymerizing a compound capable of reacting with either the crystalline polyester raw material monomer or the addition polymerization resin raw material monomer A crystalline hybrid resin (1-2);
A raw material monomer of an amorphous polycondensation resin containing an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid compound, a raw material monomer of an addition polymerization resin, and 100 parts by weight of the raw material monomer of the addition polymerization resin 2-15 parts by weight of an amorphous polycondensation resin component and an addition polycondensation resin component obtained by polymerizing a compound capable of reacting with any of the addition monomer monomers. Amorphous hybrid resin containing a polymeric resin component (2-2)
A toner for developing an electrostatic image comprising a binder resin comprising a weight ratio of the crystalline hybrid resin (1-2) to the amorphous hybrid resin (2-2) (crystal The present invention relates to a toner for developing an electrostatic charge image, wherein the conductive hybrid resin (1-2) / amorphous hybrid resin (2-2)) is 1/99 to 40/60.

  The toner for developing an electrostatic charge image of the present invention is excellent in low-temperature fixability and heat-resistant storage stability, and also has excellent effects such as storage of printed matter and image density.

The first aspect of the binder resin of the electrostatic image developing toner of the present invention is:
A crystalline polyester (1-1) obtained using a raw material monomer containing a diol having 8 to 12 carbon atoms and a dicarboxylic acid compound having 10 to 12 carbon atoms and having a total content of 80 mol% or more,
A raw material monomer of an amorphous polycondensation resin containing an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid compound, a raw material monomer of an addition polymerization resin, and 100 parts by weight of the raw material monomer of the addition polymerization resin 3-15 parts by weight of an amorphous polycondensation resin component and an addition polycondensation resin component obtained by polymerizing a compound capable of reacting with either the addition polymerization resin material monomer Amorphous hybrid resin containing a polymeric resin component (2-1)
It contains.

  Crystalline polyester (1-1) is obtained by using a raw material monomer with a long carbon chain, so it has high hydrophobicity and low compatibility with other polyesters, and is used in the annealing process in the toner production process. At least, it can be crystallized, and a decrease in storage stability can be suppressed.

  Also, by combining crystalline polyester (1-1) with amorphous hybrid resin (2-1) having a specific addition polymerization resin part, the dispersibility of crystalline polyester is improved and the effect of low-temperature fixability As a result, it was found that the decrease in image density was suppressed and the heat-resistant storage stability was better than when combined with amorphous polyester. This is because crystalline polyester (1-1) has low compatibility with the amorphous polycondensation resin part of the amorphous hybrid resin (2-1), but is compatible with the addition polymerization resin part. Presumed to be due to the high price. That is, since the crystalline polyester (1-1) is dispersed in the addition polymerization resin portion finely dispersed in the amorphous hybrid resin (2-1), as a result, the non-crystalline polyester (1-1) It is considered that microdispersion in the crystalline hybrid resin (2-1) becomes possible.

  In addition, the crystalline polyester (1-1) quickly crystallizes and has the property of being finely dispersed, so that the state in which crystals are finely dispersed can be maintained even after printing, and the storability of printed matter is extremely high. The effect is high. It has been found that adhesion between printed materials is suppressed even when exposed to a high temperature of 60 ° C. This is because the crystal part does not melt, and the crystal part works as a filler. It is guessed.

  In the present invention, the crystallinity of the resin is determined by the ratio between the softening point and the maximum endothermic peak temperature measured by a differential scanning calorimeter (DSC), that is, the crystallinity index defined by “softening point / maximum endothermic peak temperature”. expressed. Generally, when the crystallinity index exceeds 1.4, the resin is amorphous, and when it is less than 0.6, the crystallinity is low and there are many amorphous portions. In the present invention, the “amorphous” resin refers to a resin having a crystallinity index exceeding 1.4 or less than 0.6. On the other hand, the “crystalline” resin means a resin having a crystallinity index of 0.6 to 1.4.

  The “maximum endothermic peak temperature” refers to the temperature of the peak on the highest temperature side among the endothermic peaks observed under the conditions of the measurement methods described in the examples. If the maximum peak temperature is within 20 ° C of the softening point, the peak temperature is the melting point of the crystalline resin, and the peak with a difference of more than 20 ° C from the softening point is the peak due to the glass transition of the amorphous resin. And

  The crystallinity of the resin can be easily adjusted depending on the type and combination of raw material monomers used. Specifically, a carboxylic acid component or alcohol component having a branched chain structure, a trivalent or higher carboxylic acid component or alcohol component, for example, an alkyl or alkenyl succinic acid or an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom Amorphization can be promoted by using an appropriate amount of trimellitic acid, trimellitic anhydride, glycerin or the like. Further, by using an appropriate amount of α, ω-linear alkanediol as the alcohol component, crystallization of the resin can be easily promoted.

  As described above, the crystalline polyester (1-1) is obtained using raw material monomers (alcohol component and carboxylic acid component) containing a diol having 8 to 12 carbon atoms and a dicarboxylic acid compound having 10 to 12 carbon atoms.

  Examples of the diol having 8 to 12 carbon atoms include 1,8-octanediol, 1,9-nonanediol, 1,9-nonanediol, from the viewpoint of improving low-temperature fixability, heat-resistant storage stability, storage stability of printed matter, and image density. Examples thereof include 10-decanediol, 1,12-dodecanediol, 1,11-undecanediol, etc. Among these, 1,12-dodecanediol is preferable.

  As the dicarboxylic acid compound having 10 to 12 carbon atoms, from the viewpoint of improving the low-temperature fixability and image density of the toner, sevancic acid, 1,10-decanedicarboxylic acid, acid anhydrides thereof, alkyl (preferably having 1 carbon atom) ~ 6, more preferably, esters having 1 to 3 carbon atoms. Among them, sebacic acid is preferable. In the present specification, the carboxylic acid compound includes a carboxylic acid, an alkyl ester of a carboxylic acid and an alcohol having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and an acid anhydride. The carbon number of the carboxylic acid compound includes the carbon of the carboxy group, but does not include the carbon of the alkyl group of the alkyl ester.

  In addition, both diols having 8 to 12 carbon atoms and dicarboxylic acid compounds having 10 to 12 carbon atoms have functional groups (hydroxyl groups or carboxyl groups) at both ends in order to impart high crystallinity to the obtained crystalline polyester. Compounds are preferred.

  From the viewpoint of improving crystallinity, the total content of the diol having 8 to 12 carbon atoms and the dicarboxylic acid compound having 10 to 12 carbon atoms is the raw material monomer of the crystalline polyester (1-1), that is, the alcohol component and the carboxylic acid component. In the total amount, it is 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more.

  The crystalline polyester (1-1) is obtained by using an alcohol component and a carboxylic acid component as raw material monomers and subjecting them to condensation polymerization.

  Examples of alcohol components other than diols having 8 to 12 carbon atoms include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane Diol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol 1,5-hexanediol, 1,6-hexanediol, 1,4-butenediol, neopentyl glycol, 2,3-butanediol, 2,3-pentanediol, 2,4-pentanediol, 2,3 -Hexanediol, 3,4-hexanediol, 2,4-hexanediol, 2,5-hexanediol and the like.

  The content of the diol having 8 to 12 carbon atoms is more than 70 mol% in the alcohol component from the viewpoint of improving the crystallinity and improving the low-temperature fixability, heat-resistant storage stability, storage stability of printed matter and image density. Is preferable, 80 mol% or more is more preferable, and 90 mol% or more is more preferable.

  Examples of the carboxylic acid component other than the dicarboxylic acid compound having 10 to 12 carbon atoms include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, and adipic acid.

  The content of the dicarboxylic acid compound having 10 to 12 carbon atoms improves the crystallinity, and from the viewpoint of improving the low-temperature fixability of the toner, heat-resistant storage stability, storability of printed matter, and image density, It is preferably at least mol%, more preferably at least 80 mol%, still more preferably at least 90 mol%.

  Note that the raw material monomer of the crystalline polyester (1-1) is a monovalent aliphatic having 8 to 24 carbon atoms from the viewpoint of improving low-temperature fixability of toner, heat-resistant storage stability, storage of printed matter and image density. It preferably contains at least one monovalent long-chain monomer selected from the group consisting of alcohols and monovalent aliphatic carboxylic acid compounds having 8 to 24 carbon atoms. By using a monovalent long chain monomer in combination, polar groups such as a carboxyl group and a hydroxyl group at the terminal portion of the crystalline polyester (1-1) can be reduced. ), The compatibility with the amorphous polycondensation resin portion is lower and the compatibility with the addition polymerization resin portion is higher, so that the effect of finely dispersing the crystalline polyester is further enhanced.

  Examples of the monovalent aliphatic alcohol having 8 to 24 carbon atoms include 1-dodecanol, pentadecanol, hexadecanol, and octadecanol (stearyl alcohol). The number of carbon atoms of the monovalent aliphatic alcohol is preferably from 10 to 22, and more preferably from 14 to 20, from the viewpoint of improving the low temperature fixability, heat resistant storage stability and image density of the toner.

  Examples of the monovalent aliphatic carboxylic acid compound having 8 to 24 carbon atoms include decanoic acid, undecanoic acid, lauric acid, palmitic acid, stearic acid, oleic acid, behenic acid, anhydrides of these acids and alkyl (carbon number 1 -3) Esters and the like. 10-22 are preferable and, as for carbon number of the said monovalent aliphatic carboxylic acid compound, 14-20 are more preferable.

  The content of the monovalent long-chain monomer is preferably 0.1 to 10 mol% from the viewpoint of improving the low-temperature fixability, heat-resistant storage stability, storage stability of printed matter, and image density in the raw material monomer, and 2 to 6 More preferably, mol% is more preferable, and 3-6 mol% is further more preferable.

  The molar ratio of the carboxylic acid component and the alcohol component (carboxylic acid component / alcohol component) is preferably from 0.75 to 1.3, more preferably from 0.8 to 1.3, from the viewpoints of reactivity and molecular weight adjustment.

  The polycondensation of the alcohol component and the carboxylic acid component is, for example, in the presence of an esterification catalyst such as a tin compound or a titanium compound, an esterification cocatalyst, a polymerization inhibitor, and the like, preferably in an inert gas atmosphere. It is preferable to carry out at a temperature of 250 ° C., more preferably 180 to 230 ° C.

  As the tin compound, for example, dibutyltin oxide is known. However, in the present invention, tin (II) having no Sn—C bond is used from the viewpoint of good dispersibility in the condensation polymerization resin. Compounds are preferred.

  Examples of the tin (II) compound having no Sn—C bond include a tin (II) compound having a Sn—O bond, a tin (II) compound having a Sn—X (X represents a halogen atom) bond, and the like. Preferably, a tin (II) compound having a Sn-O bond is more preferable, and tin (II) 2-ethylhexanoate is more preferable.

  As the titanium compound, a titanium compound having a Ti-O bond is preferable, and a compound having an alkoxy group having 1 to 28 carbon atoms, an alkenyloxy group having 2 to 28 carbon atoms, or an acyloxy group having 1 to 28 carbon atoms in total is preferable. More preferred.

  The said tin (II) compound and titanium compound can be used 1 type or in combination of 2 or more types.

  From the viewpoint of reactivity, the amount of the esterification catalyst is preferably 0.01 to 2.0 parts by weight, more preferably 0.1 to 1.5 parts by weight, and more preferably 0.2 to 1.0 parts by weight based on 100 parts by weight of the total amount of the alcohol component and the carboxylic acid component. Part is more preferred.

  Examples of the esterification promoter include gallic acid. From the viewpoint of reactivity, the amount of esterification promoter used is preferably 0.001 to 0.5 parts by weight, more preferably 0.01 to 0.1 parts by weight, based on 100 parts by weight of the total amount of alcohol component and carboxylic acid component.

  The softening point of the crystalline polyester (1-1) is preferably 50 to 150 ° C., more preferably 60 to 120 ° C., from the viewpoint of improving the low-temperature fixability of the toner, heat-resistant storage stability, storage stability of printed matter and image density. Preferably, 70 to 110 ° C is more preferable, 80 to 100 ° C is even more preferable, and 80 to 95 ° C is even more preferable.

  The melting point of the crystalline polyester (1-1) is preferably 60 to 170 ° C., more preferably 70 to 120 ° C., from the viewpoint of improving the low temperature fixability of the toner, heat resistant storage stability, storage of printed matter and image density. 75 to 95 ° C is more preferable.

  The acid value of the crystalline polyester (1-1) is preferably 2 to 20 mgKOH / g, more preferably 3 to 15 mgKOH / g, from the viewpoint of improving the productivity of the toner.

  The melting point of the crystalline polyester (1-1) can be easily adjusted by adjusting the raw material monomer composition, the polymerization initiator, the molecular weight, the catalyst amount, etc., or by selecting the reaction conditions. For example, the condensation polymerization reaction can be promoted and the melting point can be increased by increasing the reaction temperature of the condensation polymerization, increasing the reaction time, increasing the amount of catalyst, or using a cocatalyst together.

  Crystalline polyester (1-1) refers to a resin containing a crystalline polyester unit by condensation polymerization of an alcohol component and a carboxylic acid component, and is modified not only to a crystalline polyester but also to a level that does not substantially impair its properties. Crystalline polyester may be used.

  The amorphous hybrid resin (2-1) comprises a raw material monomer of a condensation polymerization resin containing an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid compound, a raw material monomer of an addition polymerization resin, and a bireactive monomer. A resin containing an amorphous polycondensation resin component and an addition polymerization resin component obtained by polymerization.

  Amorphous polycondensation resins include amorphous polyesters and polyester / polyamides from the viewpoint of low-temperature fixability of the toner. From the viewpoints of toner durability and charge stability, the amorphous polycondensation resins are amorphous. Polyester is preferred.

  Examples of the raw material monomer for forming the amide component include various known polyamines, aminocarboxylic acids, amino alcohols and the like.

  Examples of the raw material monomer for forming the amorphous polyester include a raw material monomer containing an alcohol component and a carboxylic acid component.

  In the amorphous hybrid resin (2-1), the carboxylic acid component used as a raw material monomer of the amorphous polycondensation resin component is an aromatic dicarboxylic acid component from the viewpoint of the glass transition temperature of the polyester, that is, the toner storage property. including.

  Examples of the aromatic dicarboxylic acid compound include phthalic acid, isophthalic acid, terephthalic acid, acid anhydrides thereof, and alkyl (preferably having 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms) esters.

  The content of the aromatic dicarboxylic acid compound is preferably 10 to 80 mol% in the carboxylic acid component from the viewpoint of improving the low-temperature fixability of the toner, heat-resistant storage stability, storage stability of printed matter, and image density, and is preferably 20 to 60 mol%. Mole% is more preferable, and 25 to 45 mol% is more preferable.

  The carboxylic acid component preferably further contains fumaric acid from the viewpoint of improving the dispersibility of the crystalline polyester, that is, the low-temperature fixability of the toner, the heat-resistant storage stability, the storability of the printed matter, and the image density.

  The content of fumaric acid is preferably 10 to 70 mol%, and preferably 20 to 60 mol% in the carboxylic acid component, from the viewpoint of improving the low-temperature fixability, heat-resistant storage stability, storage stability of printed matter, and image density. More preferably, 30-50 mol% is further more preferable.

  In the present invention, the carboxylic acid component is a trivalent or higher polyvalent carboxylic acid compound, preferably a trimellitic acid compound, from the viewpoints of increasing the molecular weight of the resin, low-temperature fixability of the toner, heat-resistant storage stability, and storage of printed matter. More preferably, it contains trimellitic anhydride. The content of the trivalent or higher polyvalent carboxylic acid compound is preferably 0.1 to 30 mol%, more preferably 1 to 30 mol%, and further preferably 5 to 30 mol% in the carboxylic acid component of the condensation polymerization resin.

  As other carboxylic acid compounds, oxalic acid, malonic acid, maleic acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, their acid anhydrides, alkyl (1 to 6 carbon atoms) ) Aliphatic dicarboxylic acid compounds other than fumaric acid such as esters; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; rosin; rosin modified with fumaric acid, maleic acid, acrylic acid, or the like.

  As the alcohol component, from the viewpoint of improving the low-temperature fixability of toner, heat-resistant storage stability, storage stability of printed matter and image density, formula (I):

(In the formula, RO and OR are oxyalkylene groups, R is an ethylene and / or propylene group, x and y indicate the number of added moles of alkylene oxide, each being a positive number, and the sum of x and y. 1 to 16 is preferable, 1 to 8 is more preferable, and 1.5 to 4 is more preferable)
An alkylene oxide adduct of bisphenol A represented by

  Specific examples of the alkylene oxide adduct of bisphenol A represented by the formula (I) include a polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxy). And an alkylene oxide adduct of bisphenol A such as a polyoxyethylene adduct of phenyl) propane.

  The content of the alkylene oxide adduct of bisphenol A is 80% in the alcohol component from the viewpoint of low-temperature fixability of toner, heat-resistant storage stability, storage stability of printed matter and image density, and promotion of resin amorphization. More preferably, it is 90 mol% or more, more preferably 95 mol% or more, and still more preferably 100 mol%.

  Examples of the alcohol component other than the alkylene oxide adduct of bisphenol A include aliphatic alcohols used as an alcohol component of ordinary polyester.

  The alcohol component may contain a monovalent alcohol, and the carboxylic acid component may contain a monovalent carboxylic acid compound as appropriate from the viewpoint of adjusting the molecular weight and improving offset resistance.

  The molar ratio of the carboxylic acid component to the alcohol component (carboxylic acid component / alcohol component) is preferably 0.7 to 1.5, more preferably 0.7 to 1.4, and still more preferably 0.8 to 1.1, from the viewpoint of reactivity and molecular weight adjustment.

  The polycondensation reaction between the alcohol component and the carboxylic acid component can be performed in an inert gas atmosphere in the presence of an esterification catalyst such as a tin compound, a titanium compound, an esterification cocatalyst, a polymerization inhibitor, and the like. The temperature condition is preferably 180 to 250 ° C.

  As the esterification catalyst and the esterification co-catalyst, those similar to the crystalline polyester (1-1) are used.

  On the other hand, as an addition polymerization resin, the dispersibility is improved by improving the compatibility with the crystalline polyester, thereby improving the low-temperature fixing property of the toner, the heat-resistant storage property, the storage property of the printed matter, and the image density. Therefore, a styrene resin is preferable. Therefore, styrene derivatives such as styrene, α-methylstyrene, vinyltoluene and the like are preferable as suitable raw material monomers for addition polymerization resins.

  The content of the styrene derivative is preferably 50 to 100% by weight in the raw material monomer of the addition polymerization resin, from the viewpoint of improving the low-temperature fixability of the toner, heat-resistant storage stability, storage stability of printed matter, and image density. 100% by weight is more preferred, 80 to 100% by weight is more preferred, and 80 to 90% by weight is even more preferred.

  Raw material monomers for addition polymerization resins other than styrene derivatives include (meth) acrylic acid alkyl esters; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; and halovinyls such as vinyl chloride. Vinyl esters such as vinyl acetate and vinyl propionate; esters of ethylenic monocarboxylic acids such as dimethylaminoethyl (meth) acrylate; vinyl ethers such as vinyl methyl ether; vinylidene halides such as vinylidene chloride; N- N-vinyl compounds such as vinylpyrrolidone and the like can be mentioned. In the present specification, “(meth) acrylic acid” means acrylic acid and / or methacrylic acid.

  Of these, (meth) acrylic acid alkyl esters are preferred from the viewpoint of improving the low-temperature fixability, heat-resistant storage stability, storage of printed matter, and image density of the toner. From the above viewpoint, the number of carbon atoms of the alkyl group in the (meth) acrylic acid alkyl ester is preferably 1 to 22, and more preferably 8 to 18. In addition, carbon number of this alkyl ester says carbon number derived from the alcohol component which comprises ester. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (iso or tertiary) butyl (meth) acrylate, 2-ethylhexyl Examples include (meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, (iso) stearyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate is preferred. "(Iso or tertiary)", "(iso)" means including both present and absent groups, and when these groups are not present, Indicates normal. Further, “(meth) acrylate” indicates that both acrylate and methacrylate are included.

  The content of the (meth) acrylic acid alkyl ester is 50% by weight or less in the raw material monomer of the addition polymerization resin from the viewpoint of improving the low temperature fixability of the toner, heat resistant storage stability, storage stability of printed matter and image density. It is preferably 30% by weight or less, and more preferably 20% by weight or less.

  A resin obtained by addition polymerization of a raw material monomer containing a styrene derivative and a (meth) acrylic acid alkyl ester is also referred to as a styrene- (meth) acrylic resin.

  The addition polymerization reaction of the raw material monomer of the addition polymerization resin can be carried out in the usual manner, for example, in the presence of a polymerization initiator, a crosslinking agent, etc., in the presence of an organic solvent or in the absence of a solvent. From a viewpoint of property, 110-200 degreeC is preferable and 140-170 degreeC is more preferable.

  Examples of the organic solvent used in the addition polymerization reaction include xylene, toluene, methyl ethyl ketone, and acetone. The use amount of the organic solvent is preferably about 10 to 50 parts by weight with respect to 100 parts by weight of the raw material monomer of the addition polymerization resin from the viewpoint of reactivity.

  The hybrid resin is a kind of composite resin obtained by polymerizing the raw material monomer of the condensation polymerization resin and the raw material monomer of the addition polymerization resin. Such a composite resin can be obtained, for example, by performing a condensation polymerization reaction with a raw material monomer of a condensation polymerization resin and an addition polymerization reaction with a raw material monomer of an addition polymerization resin in parallel or sequentially in the same reaction vessel. it can. The progress and completion of the polycondensation reaction and the addition polymerization reaction do not need to be simultaneous in time, and the reaction temperature and time may be appropriately selected according to each reaction mechanism to advance and complete the reaction.

  In addition to the raw material monomer of the condensation polymerization resin and the raw material monomer of the addition polymerization resin, a resin obtained by using a compound (both reactive monomers) capable of reacting with any of them is a hybrid resin. Therefore, when the composite monomer is obtained by polymerizing the raw material monomer of the condensation polymerization resin and the raw material monomer of the addition polymerization resin, the condensation polymerization reaction and the addition polymerization reaction are preferably performed in the presence of both reactive monomers. As a result, the composite resin becomes a hybrid resin in which the condensation polymerization resin and the addition polymerization resin are partially bonded via the both reactive monomers, and the addition polymerization resin component becomes finer in the condensation polymerization resin component. And uniformly dispersed.

  As the both reactive monomers, in the molecule, at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, a primary amino group and a secondary amino group, preferably a hydroxyl group and / or A compound having a carboxyl group, more preferably a carboxyl group, and an ethylenically unsaturated bond is preferred. By using such a bireactive monomer, the dispersibility of the resin that becomes the dispersed phase can be further improved. . Both reactive monomers are preferably at least one selected from the group consisting of acrylic acid, methacrylic acid, maleic acid and maleic anhydride, but acrylic acid and methacrylic acid are more preferable from the viewpoint of reactivity. Fumaric acid is also a kind of compound that can function with both reactive monomers, but when fumaric acid is used as the carboxylic acid component of the amorphous polycondensation resin component, fumaric acid is excluded from both reactive monomers. .

  The amount of both reactive monomers used is 100% by weight of the raw material monomer of the addition polymerization resin component of the amorphous hybrid resin (2-1), preventing excessive dispersion, heat-resistant storage stability of the toner, and low-temperature fixing. From the viewpoint of improving the properties and image density, it is 3 parts by weight or more, preferably 3.5 parts by weight or more, and more preferably 4 parts by weight or more. Further, from the viewpoint of preventing poor dispersion and improving low-temperature fixability, heat-resistant storage stability and printed matter storage stability of the toner, it is 15 parts by weight or less, preferably 10 parts by weight or less, and more preferably 7 parts by weight or less. From these viewpoints, the amount of the both reactive monomers used is 3 to 15 parts by weight, preferably 3.5 to 10 parts by weight, more preferably 4 to 4 parts by weight based on 100 parts by weight of the raw material monomer of the addition polymerization resin component. 7 parts by weight. In addition, when the polymerization initiator is used, the amount of the raw material monomer of the addition polymerization resin component, which serves as a reference for the usage amount of both reaction monomers, includes the amount of the polymerization initiator.

As a specific manufacturing method of the composite resin,
(i) a method of performing a step (B) of performing an addition polymerization reaction after the step (A) of performing the condensation polymerization reaction;
(ii) After the step (A) for carrying out the condensation polymerization reaction, the step (B) for carrying out the addition polymerization reaction is carried out, and after the step (B), the reaction temperature is raised again to become a crosslinking agent if necessary. A method in which a raw material monomer of a polycondensation resin having a value equal to or higher than that is added to the polymerization system to further advance the polycondensation reaction in step (A);
(iii) The step (A) for performing the condensation polymerization reaction and the step (B) for performing the addition polymerization reaction are performed in parallel under a temperature condition suitable for the addition polymerization reaction, and the reaction temperature is maintained under the above-described conditions. After completing the step (B), the reaction temperature is raised, and if necessary, a raw material monomer of a trivalent or higher polycondensation resin serving as a crosslinking agent is added to the polymerization system, and the polycondensation reaction of the step (A) And a method of further proceeding. In the methods (i) and (ii), a prepolymerized polycondensation resin may be used instead of the step (A) in which the polycondensation reaction is performed. In the method (iii), when the step (A) and the step (B) are performed in parallel, a mixture containing the raw material monomer of the addition polymerization resin in the mixture containing the raw material monomer of the condensation polymerization resin It can also be made to react by dripping.

  Further, in the production of a hybrid resin in which a composite resin is obtained using an amphoteric monomer, the amphoteric monomer is preferably used together with a raw material monomer for an addition polymerization resin.

  In addition, when fumaric acid is used as the carboxylic acid component of the amorphous hybrid resin (2-1), fumaric acid has a carboxyl group and an ethylenically unsaturated bond in the molecule. Therefore, it is preferable to add to the reaction system after completion of the addition polymerization reaction and use it for the condensation polymerization reaction. The condensation polymerization reaction after the step (B) of performing the addition polymerization reaction is a reaction of both reactive monomers. It is preferable to carry out at a temperature of 190 to 220 ° C. from the viewpoint of improving the volatile organic compound (VOC) generation due to the property and monomer decomposition, low-temperature fixability of the toner, heat-resistant storage stability, storage stability of printed matter and image density. .

  In the present invention, the weight ratio of the raw material monomer of the amorphous condensation polymerization resin to the raw material monomer of the addition polymerization resin (amorphous condensation polymerization resin raw material monomer / addition polymerization resin raw material monomer) is Is an amorphous polycondensation resin, and the dispersed phase is preferably an addition polymerization resin, from the viewpoint of improving the low-temperature fixability of toner, heat-resistant storage stability, storability of printed matter, and image density. / 35 to 97/3 is preferred, 70/30 to 90/10 is more preferred, and 75/25 to 85/15 is even more preferred. Here, the amount of the raw material monomer of the amorphous polymerization resin includes the amount of the both reactive monomers, and the amount of the raw material monomer of the addition polymerization resin includes the amount of the polymerization initiator.

  The softening point of the amorphous hybrid resin (2-1) is preferably 90 to 160 ° C., and 95 to 155 ° C. from the viewpoint of improving the low-temperature fixability of toner, heat-resistant storage stability, storage stability of printed matter and image density. Is more preferable, 115 to 150 ° C is more preferable, and 125 to 145 ° C is even more preferable.

  The glass transition temperature of the amorphous hybrid resin (2-1) is preferably 45 to 85 ° C., and preferably 50 to 80 from the viewpoint of improving low-temperature fixability of toner, heat-resistant storage stability, storage stability of printed matter, and image density. ° C is more preferred, 58-75 ° C is more preferred, and 58-70 ° C is even more preferred.

  The maximum endothermic peak temperature of the amorphous hybrid resin (2-1) is preferably 50 to 100 ° C. from the viewpoint of improving the low-temperature fixability of the toner, heat-resistant storage stability, storability of printed matter, and image density. -75 degreeC is more preferable and 60-70 degreeC is further more preferable.

  The acid value of the amorphous hybrid resin (2-1) is preferably 1 to 90 mgKOH / g, more preferably 5 to 90 mgKOH / g, and further preferably 5 to 88 mgKOH / g, from the viewpoint of improving toner productivity. 15-30 mg KOH / g is even more preferred.

  The weight ratio of crystalline polyester (1-1) to amorphous hybrid resin (2-1) (crystalline polyester (1-1) / amorphous hybrid resin (2-1)) 1/99 or more from the viewpoint of preventing defects and improving toner low-temperature fixability and printed matter storage, improving toner low-temperature fixability, heat-resistant storage, improving image density, and printed matter storage From the viewpoint, it is 40/60 or less. From these viewpoints, the weight ratio of crystalline polyester (1-1) and amorphous hybrid resin (2-1) (crystalline polyester (1-1) / amorphous hybrid resin (2-1)) 1/99 to 40/60, preferably 3/97 to 35/65, more preferably 10/90 to 30/70, and still more preferably 15/85 to 25/75.

Further, in the toner of the present invention, instead of the crystalline polyester (1-1), a crystalline hybrid resin containing a raw material monomer for forming the crystalline polyester (1-1) as a component is used. The component 1-1) can be selectively dispersed in the addition polymerization resin component of the amorphous hybrid resin (2-2). Therefore, the second aspect of the binder resin of the toner of the present invention is:
A raw material monomer of a crystalline polyester containing a diol having 8 to 12 carbon atoms and a dicarboxylic acid compound having 10 to 12 carbon atoms, the total content of which is 80 mol% or more, a raw material monomer of an addition polymerization resin, and the addition polymerization Crystalline polyester obtained by polymerizing 3 to 15 parts by weight of crystalline polyester raw material monomer and addition polymerization resin raw material monomer with respect to 100 parts by weight of raw resin monomer A crystalline hybrid resin (1-2) comprising a component and an addition polymerization resin component;
A raw material monomer of an amorphous polycondensation resin containing an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid compound, a raw material monomer of an addition polymerization resin, and 100 parts by weight of the raw material monomer of the addition polymerization resin 2-15 parts by weight of an amorphous polycondensation resin component and an addition polycondensation resin component obtained by polymerizing a compound capable of reacting with any of the addition monomer monomers. Amorphous hybrid resin containing a polymeric resin component (2-2)
It contains.

  For the crystalline hybrid resin (1-2), the raw material monomer of the crystalline polyester (1-1) described in the first embodiment is used instead of the raw material monomer of the amorphous condensation polymerization resin, that is, addition polymerization. The raw material monomer, the bireactive monomer, and the production method of the resin are the same as those of the amorphous hybrid resin (2-1).

  The softening point of the crystalline polyester (1-2) is preferably from 50 to 150 ° C., more preferably from 60 to 120 ° C., from the viewpoint of improving the low-temperature fixability of toner, heat-resistant storage stability, storage of printed matter and image density. Preferably, 70 to 110 ° C is more preferable, 70 to 100 ° C is even more preferable, and 70 to 95 ° C is still more preferable.

  The melting point of the crystalline hybrid resin (1-2) is preferably from 50 to 170 ° C., more preferably from 60 to 120 ° C., from the viewpoint of improving low-temperature fixability of toner, heat-resistant storage stability, storage stability of printed matter, and image density. Preferably, 65 to 90 ° C is more preferable.

  The acid value of the crystalline hybrid resin (1-2) is preferably from 2 to 20 mgKOH / g, more preferably from 3 to 15 mgKOH / g, from the viewpoint of storage of printed matter.

  The melting point of the crystalline hybrid resin (1-2) can be easily adjusted by adjusting the raw material monomer composition, the polymerization initiator, the molecular weight, the catalyst amount, etc., or by selecting the reaction conditions. For example, the condensation polymerization reaction can be promoted and the melting point can be increased by increasing the reaction temperature of the condensation polymerization, increasing the reaction time, increasing the amount of catalyst, or using a cocatalyst together.

  Further, the amorphous hybrid resin (2-2) is an amorphous hybrid resin comprising the alcohol component and the carboxylic acid component containing the aromatic dicarboxylic acid compound of the amorphous hybrid resin (2-1) of the first aspect. 2-15 weight parts instead of 3-15 parts by weight of both reactive monomers, based on 100 parts by weight of the raw material monomer of the polycondensation polymerization resin, the raw material monomer of the addition polymerization resin and the raw material monomer of the addition polymerization resin In other words, the raw material monomer of the amorphous polycondensation resin, the raw material monomer of the addition polymerization resin, the bireactive monomer and the production method are amorphous hybrid resin (2-1) It is the same.

  The amount of both reactive monomers used is 100% by weight of the raw material monomer of the addition polymerization resin component of the amorphous hybrid resin (2-2), preventing excessive dispersion, heat-resistant storage stability of the toner, and low-temperature fixing. Is 2 parts by weight or more from the viewpoint of improvement in image quality, image density, and storage stability of printed matter, and 15 weights from the viewpoint of preventing poor dispersion and improving low-temperature fixing property of toner, heat-resistant storage property, and storage property of printed matter. Or less. From these viewpoints, the amount of the both reactive monomers used is 2 to 15 parts by weight, preferably 3 to 15 parts by weight, more preferably 100 parts by weight of the raw material monomer of the addition polymerization resin component. 3.5 to 10 parts by weight, more preferably 4 to 7 parts by weight, even more preferably 4 to 6 parts by weight. In addition, when the polymerization initiator is used, the amount of the raw material monomer of the addition polymerization resin component, which serves as a reference for the usage amount of both reaction monomers, includes the amount of the polymerization initiator.

  The softening point of the amorphous hybrid resin (2-2) is preferably 90 to 160 ° C., and 95 to 155 ° C. from the viewpoint of improving low-temperature fixability of toner, heat-resistant storage stability, storage stability of printed matter and image density. Is more preferable, 115 to 150 ° C is more preferable, and 125 to 145 ° C is even more preferable.

  The glass transition temperature of the amorphous hybrid resin (2-2) is preferably 45 to 85 ° C., and preferably 50 to 80 from the viewpoint of improving the low-temperature fixability of the toner, heat-resistant storage stability, storage stability of printed matter, and image density. ° C is more preferred, 58-75 ° C is more preferred, and 58-70 ° C is even more preferred.

  The maximum endothermic peak temperature of the amorphous hybrid resin (2-2) is preferably 50 to 100 ° C. from the viewpoint of improving the low-temperature fixability of toner, heat-resistant storage stability, storage stability of printed matter, and image density. -75 degreeC is more preferable and 60-70 degreeC is further more preferable.

  The acid value of the amorphous hybrid resin (2-2) is preferably 1 to 90 mgKOH / g, more preferably 5 to 90 mgKOH / g, still more preferably 5 to 88 mgKOH / g, from the viewpoint of improving the productivity of the toner. 15-30 mg KOH / g is more preferred.

  The weight ratio of crystalline hybrid resin (1-2) to amorphous hybrid resin (2-2) (crystalline hybrid resin (1-2) / amorphous hybrid resin (2-2)) is crystalline polyester. 1/99 or more from the viewpoint of preventing poor dispersion of toner and improving low-temperature fixability of toner and storage stability of printed matter, improving low-temperature fixability of toner, heat-resistant storage stability, image density and storage stability of printed matter From the viewpoint, it is 40/60 or less. From these viewpoints, the weight ratio of crystalline hybrid resin (1-2) to amorphous hybrid resin (2-2) (crystalline hybrid resin (1-2) / amorphous hybrid resin (2-2)) Is 1/99 to 40/60, preferably 3/97 to 35/65, more preferably 10/90 to 30/70, and still more preferably 15/85 to 25/75.

  In the first embodiment, the binder resin of the toner of the present invention is a known resin other than the crystalline polyester (1-1) and the amorphous hybrid resin (2-1) as long as the effects of the present invention are not impaired. In the second embodiment, a known binder resin other than the crystalline hybrid resin (1-2) and the amorphous hybrid resin (2-2), for example, an amorphous polyester may be used in combination. In that case, the content of the amorphous hybrid resin (2-1) or the amorphous hybrid resin (2-2) is preferably 15% by weight or more in the total amount of the amorphous resin, more preferably 20% by weight or more. Preferably, 50% by weight or more is further preferred, 80% by weight or more is further preferred, 95% by weight or more is further preferred, and substantially 100% by weight is even more preferred. Examples of resins other than amorphous polyesters include polyesters other than those mentioned above, vinyl resins such as styrene-acrylic resins, and resins such as epoxy resins, polycarbonates, and polyurethanes. The content of the binder resin of the present invention is preferably 70% by weight or more, more preferably 80% by weight or more, based on the total binder resin, from the viewpoint of improving low-temperature fixability, heat-resistant storage stability, printability and image density. Is more preferable, 90% by weight or more is further preferable, 95% by weight or more is further preferable, and substantially 100% by weight is even more preferable.

  The toner of the present invention further includes a colorant, a release agent, a charge control agent, a magnetic powder, a fluidity improver, a conductivity modifier, an extender pigment, a reinforcing filler such as a fibrous substance, an antioxidant, and an aging agent. Additives such as an inhibitor and a cleaning property improver may be appropriately contained.

  As the colorant, all of dyes and pigments used as toner colorants can be used. Carbon black, black pigment, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine- B base, Solvent Red 49, Solvent Red 146, Solvent Blue 35, Quinacridone, Carmine 6B, Isoindoline, Disazo yellow and the like can be used alone or in combination of two or more. The toner may be either black toner or color toner.

  The content of the colorant is preferably 1 to 40 parts by weight and more preferably 2 to 10 parts by weight with respect to 100 parts by weight of the binder resin from the viewpoint of improving the image quality.

  Examples of the charge control agent include chromium-based azo dyes, iron-based azo dyes, aluminum azo dyes, salicylic acid metal complexes, and the like, and these can be used alone or in admixture of two or more.

  The content of the charge control agent is preferably 0.1 to 8 parts by weight, more preferably 0.5 to 7 parts by weight with respect to 100 parts by weight of the binder resin, from the viewpoint of improving the image quality.

  Release agents include polyolefin wax, paraffin wax, silicones; fatty acid amides such as oleic acid amide, erucic acid amide, ricinoleic acid amide, stearic acid amide; carnauba wax, rice wax, candelilla wax, wood wax, Plant waxes such as jojoba oil; animal waxes such as beeswax; waxes such as montan wax, ozokerite, ceresin, microcrystalline wax, Fischer-Tropsch wax, etc. These may be used alone or in combination The above can be mixed and used.

  The melting point of the release agent is preferably 60 to 160 ° C., more preferably 60 to 150 ° C., from the viewpoints of low-temperature fixability and offset resistance of the toner.

  The content of the release agent is preferably 0.5 to 10 parts by weight, more preferably 1 to 8 parts by weight, and more preferably 1.5 to 7 parts by weight from the viewpoint of dispersibility in the binder resin with respect to 100 parts by weight of the binder resin. Part by weight is more preferred.

  The toner of the present invention may be a toner obtained by any conventionally known method such as a melt-kneading method, an emulsion phase inversion method, or a polymerization method, but the crystalline polyester (1-1) and the crystalline hybrid From the viewpoint of the dispersibility of the resin (1-2) (chargeability of the toner), at least the crystalline polyester (1-1) and the amorphous hybrid resin (2-1), or the crystalline hybrid resin (1-2 ) And an amorphous hybrid resin (2-2) are preferably obtained by a method including a step of melt-kneading, and a pulverized toner obtained by a method including a step of pulverizing the obtained melt-kneaded product. More preferably. In the case of pulverized toner, for example, raw materials such as a binder resin, a colorant, and a charge control agent are uniformly mixed with a mixer such as a Henschel mixer, and then a sealed kneader, a single or twin screw extruder, an open roll type After melt-kneading with a kneader or the like, cooling and pulverization, classification can be performed as appropriate.

The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably from 3 to 15 μm, more preferably from 3 to 10 μm, from the viewpoint of improving image quality. In the present specification, the volume-median particle size (D ₅₀ ) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size.

  An external additive may be added to the surface of the toner. Examples of the external additive include inorganic fine particles such as silica, alumina, titanium oxide, zirconia, tin oxide, and zinc oxide, and organic fine particles such as resin fine particles. It may be given. The addition amount of the external additive is preferably 0.05 to 5 parts by weight with respect to 100 parts by weight of the toner particles before being treated with the external additive from the viewpoint of improving the storage stability.

  The toner of the present invention can be used as a one-component developing toner or as a two-component developer mixed with a carrier.

[Softening point of resin]
Using a flow tester (Shimadzu Corporation, CFT-500D), a 1 g sample was heated at a heating rate of 6 ° C / min, and a 1.96 MPa load was applied by a plunger and extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. . The amount of plunger drop of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is taken as the softening point.

[Maximum peak temperature of resin endotherm]
Use a differential scanning calorimeter (Q-100 Japan, Q-100) to cool 0.01 to 0.02 g of the sample weighed in an aluminum pan from room temperature to 0 ° C at a rate of 10 ° C / min. Let stand for 1 minute. Thereafter, the measurement is performed at a heating rate of 50 ° C./min. Among the observed endothermic peaks, the temperature of the peak on the highest temperature side is defined as the highest endothermic peak temperature. If the maximum peak temperature is within 20 ° C of the softening point, the peak temperature is taken as the melting point.

[Glass transition temperature of resin]
Using a differential scanning calorimeter (manufactured by TA Instruments Japan Co., Ltd., Q-100), the sample weighed in an aluminum pan was heated from 0.01 to 0.02 g to 200 ° C, and the temperature drop rate was 10 A sample cooled to 0 ° C at 0 ° C / min is heated at a rate of temperature increase of 10 ° C / min, and shows the extension of the baseline below the endothermic peak temperature and the maximum slope from the peak rising part to the peak apex. The temperature at the intersection with the tangent line.

[Acid value of the resin]
Measured according to the method of JIS K0070. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K0070 to the mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Melting point of release agent]
Using a differential scanning calorimeter (Q-100 Japan, Q-100), the temperature was raised to 200 ° C, and the sample was cooled to 0 ° C at a rate of 10 ° C / min. The temperature is raised at a rate of 10 ° C./min, and the maximum peak temperature of heat of fusion is taken as the melting point.

[Volume-median particle diameter of toner (D ₅₀ )]
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 50μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter)
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) 5% electrolyte dispersion condition: 10 mg of measurement sample is added to 5 ml of dispersion, and dispersed for 1 minute with an ultrasonic disperser. Then, 25 ml of the electrolytic solution is added, and further dispersed with an ultrasonic disperser for 1 minute.
Measurement conditions: Add 100 ml of electrolyte and dispersion in a beaker, measure 30,000 particles at a concentration that can measure the particle size of 30,000 particles in 20 seconds, and determine the volume-median particle size ( determine the D _50).

Resin production example 1 [resins A to M, U, V]
Raw material monomers of crystalline polyester other than sebacic acid and 1,10-decanedicarboxylic acid shown in Tables 1 to 3 are placed in a 10 L four-necked flask equipped with a nitrogen introducing tube, a dehydrating tube, a stirrer, and a thermocouple, Heated to 120 ° C. At 120 ° C., 1.5 kg of sebacic acid or 1,10-decanedicarboxylic acid shown in Tables 1 to 3 was added, further heated to 160 ° C., and reacted for 6 hours.
Then, the raw material monomer and amphoteric monomer of styrene resin shown in Tables 1-3 were dripped over 1 hour with the dropping funnel. After aging the addition polymerization reaction for 1 hour while maintaining at 160 ° C., the raw material monomer of the styrene resin was removed at 8.3 kPa for 1 hour.
Further, the remaining sebacic acid or 1,10-decanedicarboxylic acid was added, and the temperature was raised to 200 ° C. over 8 hours and reacted at 8.3 kPa for 30 minutes.
Further, 20 g of tin (II) 2-ethylhexanoate and 2 g of gallic acid were added and reacted at 200 ° C. for 1 hour, and then reacted at 8.3 kPa for 1 hour to obtain a crystalline hybrid resin.

Resin production example 2 [resins N to R, T]
The raw material monomers for the crystalline polyester shown in Tables 2 and 3 were placed in a 10 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, and heated to 140 ° C. The mixture was further heated to 200 ° C. and reacted for 10 hours, and then reacted at 8.3 kPa for 30 minutes.
Further, 20 g of tin (II) 2-ethylhexanoate and 2 g of gallic acid were added, reacted at 200 ° C. for 1 hour, and then reacted at 8.3 kPa for 1 hour to obtain a crystalline polyester.

Resin Production Example 3 [Resin S]
Raw material monomer of crystalline polyester shown in Table 3 and tertiary butyl catechol 5g, 2-ethylhexanoic acid tin (II) 40g 10L capacity four-necked flask equipped with nitrogen introduction tube, dehydration tube, stirrer and thermocouple And heated to 140 ° C. Furthermore, it heated to 200 degreeC and made it react for 10 hours. Thereafter, the mixture was reacted at 8.3 kPa for 1 hour to obtain a crystalline polyester.

Resin production example 4 [resins AA to AJ]
Raw material monomers of amorphous polyester other than fumaric acid and trimellitic anhydride shown in Tables 4 and 5, 40 g of tin (II) 2-ethylhexanoate and 1 g of gallic acid were introduced into a nitrogen introduction tube, dehydration tube, stirrer and thermocouple Was put into a 10 L four-necked flask equipped with a reaction, followed by reaction at 230 ° C. for 8 hours and then at 8.3 kPa for 1 hour.
The temperature was lowered to 170 ° C., and the raw material monomer of styrene resin, the bireactive monomer, and dicumyl peroxide were added dropwise over 1 hour using a dropping funnel. After aging the addition polymerization reaction for 1 hour while maintaining at 170 ° C, the temperature was raised to 210 ° C, the raw material monomer of the styrene resin was removed at 8.3 kPa for 1 hour, and the reaction of both reactive monomers and the polyester part was performed. went.
Furthermore, 5 g of trimellitic anhydride, fumaric acid and tertiary butyl catechol were added at 210 ° C., and the reaction was carried out until the desired softening point was reached to obtain an amorphous hybrid resin.

Resin Production Example 4 [Resin AK]
Raw material monomer of amorphous polyester other than fumaric acid and trimellitic anhydride shown in Table 5, 40 g of 2-ethylhexanoic acid tin (II) and 1 g of gallic acid are equipped with nitrogen introduction tube, dehydration tube, stirrer and thermocouple The resultant was placed in a 10 L four-necked flask, reacted at 230 ° C. for 8 hours, and then reacted at 8.3 kPa for 1 hour.
The temperature was lowered to 170 ° C., and the raw material monomer of styrene resin, the bireactive monomer, and dicumyl peroxide were added dropwise over 1 hour using a dropping funnel. The addition polymerization reaction was aged for 1 hour while maintaining at 170 ° C., then the temperature was raised to 180 ° C., and the raw material monomer of the styrene resin was removed at 8.3 kPa for 1 hour.
Furthermore, 5 g of trimellitic anhydride, fumaric acid and tertiary butylcatechol were added at 180 ° C., and the reaction was carried out until the softening point reached 137.1 ° C. to obtain an amorphous hybrid resin.

Resin Production Example 4 [Resin AL]
Raw material monomer of amorphous polyester other than trimellitic acid shown in Table 5, 40 g of tin (II) 2-ethylhexanoate and 2 g of gallic acid were added in a 10 L capacity equipped with a nitrogen introduction tube, dehydration tube, stirrer and thermocouple. The mixture was placed in a four-necked flask, reacted at 230 ° C. for 12 hours, and then reacted at 8.3 kPa for 1 hour.
The temperature was lowered to 160 ° C., and the raw material monomer of styrene resin, the bireactive monomer, and dicumyl peroxide were added dropwise over 1 hour using a dropping funnel. After aging the addition polymerization reaction for 1 hour while maintaining at 160 ° C., the temperature was raised to 210 ° C., and the raw material monomer of the styrene resin was removed at 8.3 kPa for 1 hour.
Furthermore, trimellitic anhydride was added at 210 ° C., and the reaction was carried out until the softening point reached 134.5 ° C. to obtain an amorphous hybrid resin.

Resin Production Example 4 [Resin AM]
Raw material monomer of amorphous polyester other than fumaric acid and trimellitic anhydride shown in Table 5, 40 g of 2-ethylhexanoic acid tin (II) and 1 g of gallic acid are equipped with nitrogen introduction tube, dehydration tube, stirrer and thermocouple The reaction was carried out at 230 ° C. for 8 hours. After the reaction, the mixture was reacted at 8.3 kPa for 1 hour.
Further, the temperature was lowered to 210 ° C., 5 g of trimellitic anhydride, fumaric acid and tertiary butyl catechol were added, and the reaction was carried out until the softening point reached 138.1 ° C. to obtain an amorphous polyester.

Examples 1-43 and Comparative Examples 1-11
100 parts by weight of a binder resin in which a crystalline resin and an amorphous resin shown in Tables 6 and 7 are mixed, 5 parts by weight of a coloring agent “ECB-301” (manufactured by Dainichi Seika Co., Ltd., CI Pigment Blue 15: 3), negative 1 part by weight of chargeable charge control agent “LR-147” (manufactured by Nippon Carlit Co., Ltd.), 1 part by weight of mold release agent “Carnauba Wax C1” (manufactured by Kato Yoko Co., Ltd., melting point: 83 ° C.) After 1 part by weight of Flint H105 (Sazol Wax, melting point: 110 ° C) was thoroughly stirred in a Henschel mixer, a co-rotating twin screw extruder with a kneading part length of 1560mm, screw diameter of 42mm and barrel inner diameter of 43mm was used. Used and melt-kneaded. The rotation speed of the roll was 200 r / min, the heating temperature in the roll was 120 ° C., the feed rate of the mixture was 10 kg / hr, and the average residence time was about 18 seconds. The obtained kneaded product was rolled and cooled with a cooling roller, and then a powder with a volume-median particle size (D ₅₀ ) of 6.5 μm was obtained with a jet mill.

To 100 parts by weight of the obtained powder, 1.0 part by weight of external additive `` Aerosil R-972 '' (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd.) and 1.0 part by weight of `` SI-Y '' (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd.) Then, the mixture was mixed with a Henschel mixer at 3600 r / min for 5 minutes to perform external additive treatment, thereby obtaining a toner having a volume-median particle size (D ₅₀ ) of 6.5 μm.

Test Example 1 [Heat resistant storage stability]
10 g of toner was put into a cylindrical container having a radius of 12 mm, and a weight of 100 g was placed on the top, and kept for 72 hours in an environment of 50 ° C. and 60% relative humidity. In order from the top, a powder tester (manufactured by Hosokawa Micron Co., Ltd.) is installed with three sieves of sieve A (aperture 250 μm), sieve B (aperture 150 μm), and sieve C (aperture 75 μm). A toner (10 g) was placed on A and vibrated for 60 seconds. The toner weight WA (g) remaining on the sieve A, the toner weight WB (g) remaining on the sieve B, and the toner weight WC (g) remaining on the sieve C are measured and calculated according to the following formulas. The heat-resistant storage stability was evaluated based on the value (α). The closer the value (α) is to 100, the better the heat resistant storage stability. The results are shown in Tables 6 and 7.

      α = 100- (WA + WB × 0.6 + WC × 0.2) / 10 × 100

Test Example 2 [low temperature fixability]
A toner was mounted on a copying machine “AR-505” (manufactured by Sharp), and an image was taken out in an unfixed state (printing area: 2 cm × 12 cm, adhesion amount: 0.5 mg / cm ² ). The fixing machine of the copying machine was fixed on paper at 400 mm / sec while increasing the fixing temperature from 90 ° C. to 240 ° C. in 5 ° C. increments. As the fixing paper, “CopyBond SF-70NA” (manufactured by Sharp Corporation, 75 g / m ² ) was used.

  “UNICEF Cellophane” (Mitsubishi Pencil Co., Ltd., width: 18 mm, JISZ-1522) was pasted on the fixed image, passed through a fixing roller set at 30 ° C., and then the tape was peeled off. The optical reflection density before and after the tape was peeled off was measured using a reflection densitometer “RD-915” (made by Gretag Macbeth), and the ratio between the two (after peeling / before sticking) first exceeded 90%. The temperature of the fixing roller was defined as the minimum fixing temperature, which was used as an index for low-temperature fixability. The results are shown in Tables 6 and 7.

Test Example 3 [Image density]
A toner was mounted on a copying machine “AR-505” (manufactured by Sharp), and an image was taken out in an unfixed state (printing area: 2 cm × 12 cm, adhesion amount: 0.5 mg / cm ² ). The fixing machine of the copying machine was fixed on paper at 160 ° C. and 200 mm / sec offline. As the fixing paper, “CopyBond SF-70NA” (manufactured by Sharp Corporation, 75 g / m ² ) was used.

  The image density of the fixed image was measured using a transmission densitometer “TR-927” (manufactured by Gretag Macbeth). The results are shown in Tables 6 and 7. Note that the transmission densitometer used to measure image density is saturated immediately when the density exceeds a certain level in the reflection densitometer, whereas the transmission densitometer is sensitive to the dispersion of the colorant. It is to do.

Test Example 4 [printed material storage property]
For each toner, one unfixed image of Test Example 1 was fixed at a temperature of minimum fixing temperature + 10 ° C. 100 sheets of paper were placed on the fixed image, and a 2 kg weight was placed on the paper, placed on a hot plate at 60 ° C., and left under three conditions of 5 minutes, 10 minutes, and 20 minutes. From the degree of fusion of the fixed image to the paper, the printed matter storability after high-temperature exposure for a short period was evaluated according to the following evaluation criteria. The results are shown in Tables 6 and 7.

〔Evaluation criteria〕
A: Even if left for 20 minutes, it was not fused.
B: Although it was not fused when left for 10 minutes, it was partly fused when left for 20 minutes.
C: Although it was not fused after being left for 5 minutes, it was partially fused after being left for 10 minutes.
D: Fused partially after standing for 5 minutes.
E: The film was completely fused after being left for 5 minutes, and the paper did not peel off.

  From the above results, it can be seen that the toners of Examples 1 to 43 are superior in storage stability and low-temperature fixability as compared with the toners of Comparative Examples 1 to 11, and also have good image density and print storage stability.

  The toner for developing an electrostatic charge image of the present invention is suitably used for developing a latent image formed in electrophotography, electrostatic recording method, electrostatic printing method and the like.

Claims (8)

A crystalline polyester (1-1) obtained using a raw material monomer containing a diol having 8 to 12 carbon atoms and a dicarboxylic acid compound having 10 to 12 carbon atoms and having a total content of 80 mol% or more,
A raw material monomer of an amorphous polycondensation resin containing an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid compound, a raw material monomer of an addition polymerization resin, and 100 parts by weight of the raw material monomer of the addition polymerization resin 3-15 parts by weight of an amorphous polycondensation resin component and an addition polycondensation resin component obtained by polymerizing a compound capable of reacting with either the addition polymerization resin material monomer Amorphous hybrid resin containing a polymeric resin component (2-1)
A toner for developing an electrostatic image comprising a binder resin comprising a weight ratio of the crystalline polyester (1-1) to the amorphous hybrid resin (2-1) (crystallinity) A toner for developing electrostatic images, in which polyester (1-1) / amorphous hybrid resin (2-1) is 1/99 to 40/60. A raw material monomer of a crystalline polyester containing a diol having 8 to 12 carbon atoms and a dicarboxylic acid compound having 10 to 12 carbon atoms, the total content of which is 80 mol% or more, a raw material monomer of an addition polymerization resin, and the addition polymerization Crystalline polyester obtained by polymerizing 3 to 15 parts by weight of crystalline polyester raw material monomer and addition polymerization resin raw material monomer with respect to 100 parts by weight of raw resin monomer A crystalline hybrid resin (1-2) comprising a component and an addition polymerization resin component;
A raw material monomer of an amorphous polycondensation resin containing an alcohol component and a carboxylic acid component containing an aromatic dicarboxylic acid compound, a raw material monomer of an addition polymerization resin, and 100 parts by weight of the raw material monomer of the addition polymerization resin 2-15 parts by weight of an amorphous polycondensation resin component and an addition polycondensation resin component obtained by polymerizing a compound capable of reacting with any of the addition monomer monomers. Amorphous hybrid resin containing a polymeric resin component (2-2)
A toner for developing an electrostatic image comprising a binder resin comprising a weight ratio of the crystalline hybrid resin (1-2) to the amorphous hybrid resin (2-2) (crystal Toner for developing electrostatic images, wherein the conductive hybrid resin (1-2) / amorphous hybrid resin (2-2) is 1/99 to 40/60.   A carboxylic acid component of an amorphous polycondensation resin component of the amorphous hybrid resin (2-1) or a carboxylic acid component of an amorphous polycondensation resin component of the amorphous hybrid resin (2-2), The toner for developing an electrostatic charge image according to claim 1, comprising fumaric acid.   In the amorphous hybrid resin (2-1) or the amorphous hybrid resin (2-2), the weight ratio of the raw material monomer of the amorphous condensation polymerization resin to the addition monomer of the addition polymerization resin (amorphous condensation polymerization) The toner for developing an electrostatic charge image according to any one of claims 1 to 3, wherein the raw material monomer of the resin based resin / the raw material monomer of the addition polymerization resin) is 65/35 to 97/3. The alcohol component of the amorphous polycondensation resin component of the amorphous hybrid resin (2-1) or the alcohol component of the amorphous polycondensation resin component of the amorphous hybrid resin (2-2) is represented by the formula (I ):

(In the formula, RO and OR are oxyalkylene groups, R is an ethylene and / or propylene group, x and y indicate the number of added moles of alkylene oxide, each being a positive number, and the sum of x and y. Is preferably 1 to 16)
The toner for developing an electrostatic image according to claim 1, comprising 80 mol% or more of an alkylene oxide adduct of bisphenol A represented by the formula:   The raw material monomer of the crystalline polyester (1-1) or the crystalline polyester of the crystalline hybrid resin (1-2) is a monovalent aliphatic alcohol having 8 to 24 carbon atoms and 1 having 8 to 24 carbon atoms. The electrostatic image development according to any one of claims 1 to 5, comprising 0.1 to 10 mol% of at least one monovalent long-chain monomer selected from the group consisting of divalent aliphatic carboxylic acid compounds. toner.   Including a step of melt-kneading at least crystalline polyester (1-1) and amorphous hybrid resin (2-1) or crystalline hybrid resin (1-2) and amorphous hybrid resin (2-2) The toner for developing an electrostatic charge image according to claim 1, which is obtained by a method.   The toner for developing an electrostatic charge image according to claim 7, further comprising a step of pulverizing the obtained melt-kneaded product.