JP2012220661A - Manufacturing method of toner resin and toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a resin for toner, in which variation in particle size in a pulverization process at the time of toner production is suppressed, and a toner having both low-temperature fixing performance and high-temperature offset resistance performance can be obtained when converted into toner. I will provide a.
A toner for producing a toner resin by melt-kneading a resin (A) having an unsaturated polyester unit and a resin composition (B) containing a polymerization initiator, and performing a crosslinking reaction during the melt-kneading. A resin manufacturing method,
In the DSC curve measured by the polymerization initiator (b-1) and the differential scanning calorimeter (DSC), the resin composition (B) containing the polymerization initiator has a maximum endothermic peak at 50 ° C. or higher and 130 ° C. or lower. And a saturated polyester resin (b-2) having a peak temperature.
[Selection figure] None

Description

  The present invention relates to a toner resin manufacturing method and a toner used in an image forming method for developing an electrostatic image in electrophotography.

  Conventionally, a number of methods are known as electrophotographic methods. Generally, a charging process for charging an electrostatic charge image carrier using a photoconductive substance, and electrostatic charging on the charged electrostatic charge image carrier. A step of forming a latent image, a developing step of transferring the toner carried on the toner carrier onto the electrostatic latent image for visualization, and a transfer for transferring the developed image to a transfer material by a transfer means Through the process and the fixing process of heating and fixing the transferred image transferred onto the transfer material, the target fixed matter is obtained.

  Electrophotographic devices have received various demands such as high image quality, small size and light weight, high speed and high productivity, and energy saving. Among them, especially in the fixing process, further energy saving and high reliability are achieved. The development of materials that can achieve this is an important technical issue.

  In order to solve these problems, it is essential to significantly improve the toner fixing performance, and improvement in performance (low-temperature fixing performance) capable of sufficiently fixing at a lower temperature is required. On the other hand, it is also necessary to improve the performance to prevent so-called high temperature offset, in which part of the toner melted at the time of fixing is transferred to a heat roller and transferred onto a subsequent transfer paper or the like. Accordingly, both low temperature fixing performance and high temperature resistant offset performance are required.

  In order to achieve the toner performance as described above, it is necessary to improve the resin for toner, and various toner resins and methods for producing the resin have been proposed.

  Examples of the resin for toner include vinyl resins, polyester resins, polyurethane resins, epoxy resins, phenol resins, and so-called hybrid resins in which two or more of the above resins are mixed or partially reacted. . Among these, resins having a polyester unit are preferably used in recent years from the viewpoint of fixing properties.

  Conventionally, as a method for achieving both low-temperature fixing performance and high-temperature offset resistance performance of polyester resin for toner, an unsaturated group is introduced into a linear polyester resin portion having excellent low-temperature fixing properties, and a polymerization initiator is used during melt kneading of the resin. A method of crosslinking reaction has been proposed.

  Patent Document 1 proposes a technique in which an unsaturated polyester resin is subjected to a crosslinking reaction with organic peroxides. The toner using the cross-linked polyester resin obtained in this manner has the characteristics that good fixing property and back stain phenomenon do not occur. On the other hand, since organic peroxide is used in a large amount of 0.5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polyester resin, a large amount of decomposition products remain in the polyester resin, and the storage stability of the toner is increased. There was a phenomenon that it was lowered.

  In order to solve this problem, Patent Document 2 proposes that a polyester resin having an unsaturated double bond is crosslinked using a crosslinking reaction initiator dissolved or dispersed in paraffin wax as a diluent. According to this, a toner having a fixing temperature range and excellent in storage stability, durability, and material dispersibility can be obtained. On the other hand, since the polyester resin and the paraffin wax are different in composition, the paraffin wax is not sufficiently finely dispersed in the polyester resin, and localization of the crosslinked portion and the non-crosslinked portion occurs. As a result, for example, when the resin is used as a pulverized toner, in the pulverization step, it is difficult to pulverize in the cross-linked part, while in the non-cross-linked part, it tends to be excessively pulverized, resulting in a large variation in particle size distribution of the pulverized product. . As a result, the yield in the classification process or the like was lowered, and the yield at the time of toner production was lowered.

  There is also a proposal that discloses the use of a low molecular weight polyester having the same composition as the polyester resin as the diluent (see Patent Document 3). However, the molten state of the low molecular weight polyester has not been sufficiently studied, and there is still room for improvement.

Japanese Patent Laid-Open No. 3-135578 JP 2008-233396 A JP 2008-233531 A

  An object of the present invention is to provide a method for producing a resin for toner that solves the above-mentioned problems, and a toner using the same.

  That is, an object of the present invention is to suppress the variation in the particle size in the pulverization process at the time of toner production, and a toner capable of obtaining a toner having both low-temperature fixing performance and high-temperature offset resistance performance when converted into a toner. And a toner using the same.

The present invention for solving the above problems
Production of toner resin for producing toner resin by melt-kneading resin (A) having an unsaturated polyester unit and resin composition (B) containing a polymerization initiator, and performing a crosslinking reaction during the melt-kneading. A method,
In the DSC curve measured by the polymerization initiator (b-1) and the differential scanning calorimeter (DSC), the resin composition (B) containing the polymerization initiator has a maximum endothermic peak at 50 ° C. or higher and 130 ° C. or lower. And a saturated polyester resin (b-2) having a peak temperature.

  As described above, according to the present invention, it is possible to obtain a toner having both a low-temperature fixing performance and a high-temperature offset-resistant performance while obtaining a stable particle size with respect to the pulverized particles in the pulverization process at the time of toner production. .

  The inventors of the present invention provide a method for producing a resin for toner in which a resin having an unsaturated polyester unit (hereinafter sometimes referred to as an unsaturated resin (A)) is subjected to a crosslinking reaction using a polymerization initiator during melt-kneading. The inventors have intensively studied a method for dispersing the polymerization initiator more uniformly.

  First, as a first step of uniformly dispersing the polymerization initiator in the resin having an unsaturated polyester unit, it is effective to dissolve or disperse the polymerization initiator in a diluent.

  Dilution of the polymerization initiator in the unsaturated polyester unit can be suppressed by diluting the polymerization initiator with a diluent. By suppressing the unevenness of the polymerization initiator, the resin after the crosslinking reaction becomes homogeneous, and the uniformity when a material such as wax is dispersed is increased.

  As a diluent, in a DSC curve measured by a differential scanning calorimeter (DSC), a saturated polyester resin having a maximum endothermic peak at 50 ° C. or higher and 130 ° C. or lower (hereinafter referred to as a saturated resin (b-2)) It was found that the bias of the polymerization initiator can be suppressed. More preferably, it has a maximum endothermic peak at 60 ° C. or higher and 110 ° C. or lower.

  The present inventors have used a saturated polyester resin having a chemical composition close to that of a resin having an unsaturated polyester unit as a diluent for the polymerization initiator, so that the diluted polymerization initiator is an unsaturated resin ( It has been found that A) is finely dispersed uniformly. Then, by using a saturated polyester resin having a maximum endothermic peak at 50 ° C. or higher and 130 ° C. or lower, the saturated polyester resin rapidly dissolves during melt kneading, and the polymerization initiator diluted more rapidly becomes an unsaturated resin (A ) Disperse inside.

  When the maximum endothermic peak temperature of the saturated resin (b-2) is lower than 50 ° C., the difference in viscosity from the unsaturated resin (A) is large and it is difficult to maintain a finely dispersed state. Sometimes sharp melt properties cannot be obtained, and uniform dispersion of the polymerization initiator in the unsaturated resin (A) becomes difficult.

  As described above, in the present invention, the crosslinking portion is finely dispersed in the unsaturated resin (A) as the crosslinking reaction proceeds with the finely dispersed polymerization initiator as a starting point. As a result, both low temperature fixing performance and high temperature resistant offset performance can be achieved. At the same time, since the unevenness of the cross-linked portion is small, the particle size of the pulverized particles is stabilized in the pulverization process at the time of toner production. Therefore, the yield in toner production is improved.

Hereinafter, the present invention will be described in more detail.
First, the resin (A) having an unsaturated polyester unit will be described.
Unsaturation is an abbreviation for a substance having a carbon-carbon unsaturated bond (double bond, triple bond). In particular, in the present invention, the term “unsaturated” means that a carbon-carbon double bond is present.

  That is, the resin having an unsaturated polyester unit is a resin having at least a polyester unit having a carbon-carbon double bond in the main chain and / or side chain. In the present invention, the “polyester unit” means a part derived from polyester, and the resin having a polyester unit includes, for example, a polyester resin or a hybrid resin in which a polyester unit and another resin unit are bonded. Examples of other resins include vinyl resins, polyurethane resins, epoxy resins, and phenol resins. In addition, since the carbon-carbon double bond in a benzene ring has low reactivity and does not contribute to bridge | crosslinking, it is not contained in the unsaturated bond in this invention.

  In order to introduce an unsaturated double bond into the main chain and / or side chain of the polyester unit, a polycondensation reaction may be performed using an acid monomer or an alcohol monomer having an unsaturated double bond.

  Examples of acid monomers having an unsaturated double bond include, but are not limited to, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride Products, unsaturated dibasic acid anhydrides such as citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester Dimethyl maleine, unsaturated dibasic acid half esters such as citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; Unsaturated dibasic acid esters such as dimethyl fumaric acid; α, β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid and cinnamic acid; α, β-unsaturated acids such as crotonic acid anhydride and cinnamic acid anhydride Monomers having a carboxyl group such as saturated acid anhydrides, anhydrides of the α, β-unsaturated acids and lower fatty acids; alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof .

  The alcohol monomer having an unsaturated double bond is not particularly limited, and examples thereof include 1,4-dihydroxy-2-butene. Among these, it is particularly preferable to use at least one selected from fumaric acid, maleic acid, and maleic anhydride from the viewpoint of reactivity.

  The content of the unsaturated double bond in the resin having an unsaturated polyester unit is not particularly limited, but when the constituent component having an unsaturated double bond is an acid monomer, all the acid components constituting the polyester unit It is preferable that they are 1 mol% or more and 50 mol% or less. Moreover, when the structural component which has an unsaturated double bond is an alcohol monomer, it is preferable that they are 1 mol% or more and 50 mol% or less of all the alcohol components which comprise a polyester resin. Moreover, when using both together, it is preferable that the sum total in both monomers is 1 mol% or more and 50 mol% or less.

  In addition to the constituent monomer having the unsaturated double bond, a divalent acid monomer and / or alcohol monomer having no unsaturated double bond may be used as the monomer for producing the unsaturated polyester unit. good.

  The divalent acid monomer having no unsaturated double bond is not particularly limited. For example, terephthalic acid, isophthalic acid, orthophthalic acid, sebacic acid, adipic acid, succinic acid, glutaric acid, metaconic acid, citraconic acid Dicarboxylic acids such as glutaconic acid, cyclohexanedicarboxylic acid, alkenylsuccinic acid, malonic acid, linolenic acid; alkyl esters of these dicarboxylic acids (monomethyl ester, dimethyl ester, monoethyl ester, diethyl ester, monobutyl ester, dibutyl ester, etc.) ); Acid anhydrides of these dicarboxylic acids. These divalent carboxylic acid compounds can be used alone or in combination of two or more.

  Further, the divalent alcohol monomer having no unsaturated double bond is not particularly limited, and examples thereof include polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, poly Oxypropylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.2) -polyoxyethylene- (2.0) -2,2-bis (4-hydroxy) Phenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.3) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene ( 3.3) Divalent aromatic alcohols such as -2,2-bis (4-hydroxyphenyl) propane; ethylene glycol, polyethylene glycol 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, diethylene glycol, 2-methyl-1,3-propanediol, triethylene glycol, neopentyl glycol , 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, and the like; 1,2-cyclohexanedimethanol, 1,4-cyclohexane Divalent alicyclic such as dimethanol, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct and propylene oxide adduct, spiroglycol, 1,4-cyclohexanediol, cyclodecane dimethanol, tricyclodecane dimethanol List alcohol Can be, it can be used alone or in combination of two or more kinds.

  As a monomer for producing the unsaturated polyester unit, in addition to the above-mentioned acid monomer and / or alcohol monomer having an unsaturated double bond, divalent acid monomer and alcohol monomer having no unsaturated double bond, A monovalent acid monomer and / or a trivalent or higher acid monomer and / or a trivalent or higher alcohol monomer may be used.

  Examples of the monovalent acid monomer include aromatic carboxylic acids having 30 or less carbon atoms such as benzoic acid and p-methylbenzoic acid, and aliphatic carboxylic acids having 30 or less carbon atoms such as stearic acid and behenic acid.

  Examples of the monovalent alcohol monomer include aromatic alcohols having 30 or less carbon atoms such as benzyl alcohol, and aliphatic alcohols having 30 or less carbon atoms such as lauryl alcohol, cetyl alcohol, stearyl alcohol, and behenyl alcohol. It is done.

  Although it does not restrict | limit especially as a trivalent or more acid monomer, A trimellitic acid, trimellitic anhydride, pyromellitic acid, etc. are mentioned.

  Examples of the trivalent or higher alcohol monomer include trimethylolpropane, pentaerythritol, and glycerin.

  The unsaturated resin (A) only needs to have at least a resin having an unsaturated polyester unit, and may be a mixture with a resin other than the polyester resin or a hybrid resin.

  Examples of the vinyl monomer used for the synthesis of a vinyl resin that can be used as a resin other than the polyester resin include the following compounds.

  Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethyl Styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene Styrene and its derivatives such as: styrene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; halogenated such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride Vinyls: Vinyl acetate, vinyl propionate, vinyl benzoate Vinyl esters such as: methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, methacrylic acid Α-methylene aliphatic monocarboxylic acid esters such as phenyl, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-acrylate Acrylic esters such as octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl methyl ether Vinyl ethers such as vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone N-vinyl compounds such as these; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.

  Moreover, as a manufacturing method of an unsaturated polyester unit, the method of utilizing the dehydration condensation reaction from an acid monomer and an alcohol monomer, and the method of utilizing transesterification are mentioned, for example.

  The esterification or transesterification reaction can be performed using a normal esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, and magnesium acetate, if necessary.

  The resin for toner of the present invention is obtained by melt-kneading the resin (A) having the unsaturated polyester unit and the resin composition (B) containing a polymerization initiator, and performing a crosslinking reaction.

  The mode of the crosslinking reaction is not particularly limited, but for example, a reaction in which an addition reaction is carried out with a polymerization initiator between unsaturated double bonds in the resin (A) having a polyester unit, or in a resin having a polyester unit. Examples include formation of intermolecular bonds by condensation reaction, polyaddition reaction, transesterification reaction, and the like of a polyvalent carboxylic acid group, a polyhydric alcohol group, a polyvalent epoxy group, or a polyvalent isocyanate group.

  Among these, from the viewpoint of controllability of the crosslinking reaction, there is a reaction in which an addition reaction is performed with a polymerization initiator between unsaturated double bonds in the resin (A) having a polyester unit to form an intermolecular carbon-carbon bond. preferable.

Next, the resin composition (B) containing a polymerization initiator will be described.
The resin composition (B) containing the polymerization initiator has a maximum endothermic peak at 50 ° C. or higher and 130 ° C. or lower in the DSC curve measured by the polymerization initiator (b-1) and the differential scanning calorimeter (DSC). A saturated polyester resin (b-2).

  Although it does not restrict | limit especially regarding a polymerization initiator (b-1), The radical reaction initiator which can raise | generate an addition reaction between the unsaturated double bonds in an unsaturated resin (A) is preferable.

  Although it does not restrict | limit especially as a radical reaction initiator, An azo compound and an organic peroxide can be used. Among these, organic peroxides that have stable charging performance and are easy to obtain a toner having excellent developability during durability are preferable.

  The organic peroxide is not particularly limited, and examples thereof include benzoyl peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, α, α-bis (t-butyl peroxy). Diisopropylbenzene, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di-t-butylperoxy Hexin-3, acetyl peroxide, isobutyryl peroxide, octaninol peroxide, decanolyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, m-toluyl peroxide, t-butyl peroxide Oxyisobutyrate, t-butylperoxyneodecanoate, cumylperoxyneodecano Ate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxy 3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butyl Examples include peroxyisopropyl carbonate and t-butyl peroxyacetate.

  The kind of the polymerization initiator is used alone or in combination with reference to the 10-hour half-life temperature. From the viewpoint of controllability of the crosslinking reaction, a polymerization initiator having a 10-hour half-life temperature of 90 ° C. or higher and 120 ° C. or lower is preferable.

  Next, the saturated polyester resin (b-2) having a maximum endothermic peak at 50 ° C. or higher and 130 ° C. or lower in the DSC curve will be described.

  Since the saturated polyester resin (b-2) is mixed with a polymerization initiator, the presence of an unsaturated double bond may cause an addition reaction. Therefore, it is necessary to be a saturated resin having no unsaturated double bond.

  Moreover, the saturated polyester resin (b-2) of the present invention has a peak temperature of the maximum endothermic peak in the range of 50 ° C. or higher and 130 ° C. or lower in the DSC curve. Such a resin is instantaneously melted at its peak temperature.

  Examples of the saturated polyester resin having such characteristics include a crystalline polyester resin. The crystalline polyester is a polyester in which molecules are regularly arranged to exhibit crystal characteristics.

  The peak temperature of the maximum endothermic peak in the differential scanning calorimetry (DSC) measurement of the crystalline polyester can be adjusted, for example, by appropriately selecting the type and molecular weight of the monomer used.

  The crystalline polyester can be obtained by a reaction between a divalent or higher polyvalent carboxylic acid having no double bond and a diol. Among these, a polyester mainly composed of an aliphatic diol and an aliphatic dicarboxylic acid is preferable because the degree of crystallinity tends to be high.

  In particular, in the present invention, a polyester synthesized by using an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms in a monomer at 50 mol% or more is preferable. Preferably it is 70 mol% or more. The reason is not clear, but by using a combination of an aliphatic diol having 2 to 22 carbon atoms and an aliphatic dicarboxylic acid having 2 to 22 carbon atoms, the order of the molecular arrangement can be improved and crystallization can be achieved. It is thought that it becomes easy to raise the degree.

  The ratio (molar basis) between the acid monomer and the alcohol monomer component used in the synthesis of the saturated resin (b-2) is preferably acid monomer: alcohol monomer = 60: 40 to 40:60.

  The aliphatic diol having 2 or more and 22 or less carbon atoms (more preferably 2 or more and 12 or less carbon atoms) is not particularly limited, but is preferably a linear (more preferably linear) aliphatic diol. . Examples of chain aliphatic diols include ethylene glycol, diethylene glycol, triethylene glycol, 1,4-butanediol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol , Decamethylene glycol, neopentyl glycol and the like. Among these, linear aliphatic α, ω-diols such as ethylene glycol, diethylene glycol and 1,4-butanediol are particularly preferred.

  Of the alcohol monomers, preferably 50 mass% or more, more preferably 70 mass% or more is an alcohol selected from aliphatic diols having 2 to 22 carbon atoms.

  In addition, a polyhydric alcohol monomer other than the aliphatic diol can be used to the extent that the characteristics of the crystalline polyester are not impaired. Furthermore, monovalent alcohol may be used to such an extent that the characteristics of the crystalline polyester are not impaired.

  On the other hand, the aliphatic dicarboxylic acid having 2 or more and 22 or less carbon atoms (more preferably 4 or more and 14 or less carbon atoms) is not particularly limited, but is a chain (more preferably linear) aliphatic dicarboxylic acid. Preferably there is. Specific examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid , Dodecanedicarboxylic acid, and these acid anhydrides.

  Of the carboxylic acid monomers, preferably 50% by mass or more, more preferably 70% by mass or more is a carboxylic acid selected from aliphatic dicarboxylic acids having 2 to 22 carbon atoms.

  Moreover, polyvalent carboxylic acid other than the said aliphatic dicarboxylic acid may be included to such an extent that the characteristic of crystalline polyester is not impaired. Furthermore, you may contain monovalent carboxylic acid to such an extent that the characteristic of crystalline polyester is not impaired.

  The crystalline polyester in the present invention can be produced according to an ordinary polyester synthesis method. For example, the above-mentioned acid monomer and alcohol monomer can be esterified or transesterified, and then subjected to polycondensation reaction under reduced pressure or by introducing nitrogen gas to obtain a desired crystalline polyester. it can. The esterification or transesterification reaction can be performed using a normal esterification catalyst or transesterification catalyst such as sulfuric acid, titanium butoxide, dibutyltin oxide, manganese acetate, and magnesium acetate, if necessary.

  Moreover, it is preferable that the number average molecular weights of crystalline polyester (b-2) are 1,000 or more and 20,000 or less. By controlling the number average molecular weight within the above range, it is possible to contribute to improvement of fixing performance.

  Although the resin composition (B) containing a polymerization initiator is a resin having a polymerization initiator (b-1) and a saturated polyester resin (b-2), the preparation method is not particularly limited, but heating A method of mixing the polymerization initiator (b-1) with the saturated polyester resin (b-2) in a molten state is preferable. In this case, the mixing temperature is not less than the maximum endothermic peak temperature of the saturated resin (b-2) and the polymerization initiator (b-1) is half an hour from the viewpoint of suppressing decomposition of the polymerization initiator. It is preferable that it is below an initial temperature. By controlling to this temperature range, the polymerization initiator (b-1) is easily dispersed uniformly in the saturated polyester resin (b-2), and the deactivation of the polymerization initiator (b-1) is suppressed. be able to.

  The mixing ratio of the polymerization initiator (b-1) and the saturated polyester resin (b-2) is 0.01% by mass or more as the content of the polymerization initiator (b-1) in the resin composition (B). 50 mass% or less, more preferably 0.1 mass% or more and 10 mass% or less. When the mixing ratio of the polymerization initiator is within the above range, the crosslinking reaction can be controlled more easily.

Next, the crosslinking reaction will be described.
The present invention is characterized in that a resin (A) having an unsaturated polyester unit and a resin composition (B) containing a polymerization initiator are melt-kneaded and a crosslinking reaction is carried out during the melt-kneading. Moreover, it is preferable to perform a crosslinking reaction after the polymerization of the resin (A) having an unsaturated polyester unit.

  The crosslinking reaction apparatus is not particularly limited, but a melt kneader is preferable from the viewpoint that the reaction can be performed uniformly. As the melt kneader, a known kneader such as a closed kneader, a single or biaxial extruder, and a continuous open roll type kneader can be used. Among these, a biaxial extrusion kneader capable of performing the crosslinking reaction more uniformly is preferable.

  Further, regarding the temperature condition of the crosslinking reaction, it is preferably not less than the 10-hour half-life temperature of the polymerization initiator (b-1), more preferably from the 10-hour half-life temperature of the polymerization initiator (b-1). It is preferable to carry out the reaction at a temperature of 50 ° C. or higher.

  The content ratio of the unsaturated resin (A) and the resin composition (B) is such that the resin composition (B) is 0.5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the unsaturated resin (A). Preferably there is. By setting the resin (B) containing a polymerization initiator within the above range, the performance of (A) as a toner resin can be efficiently exhibited.

  In addition, the resin (A) having an unsaturated polyester unit of the present invention includes a high softening point resin (a-1) having a softening point of 120 ° C. or higher and 170 ° C. or lower, and a low softening having a softening point of 70 ° C. or higher and lower than 120 ° C. It is preferable to contain point resin (a-2).

  It is preferable to use a high softening point resin and a low softening point resin together and to cause cross-linking between the two, so that it is easy to achieve both low-temperature fixing performance and high-temperature offset resistance performance.

Next, a toner containing a toner resin having the above characteristics will be described.
The toner of the present invention can be used as any one of magnetic one-component toner, non-magnetic one-component toner, and non-magnetic two-component toner.

  The toner of the present invention contains a colorant. The following can be illustrated as a coloring agent.

  As the black pigment, for example, carbon black such as furnace black, channel black, acetylene black, thermal black and lamp black is used, and magnetic powder such as magnetite and ferrite is also used.

  As a colorant suitable for the yellow toner, a pigment or a dye can be used. Specifically, examples of the pigment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 17, 23, 62, 65, 73, 74, 81, 83, 93, 94, 95, 97, 98, 109, 110, 111, 117, 120, 127, 128, 129, 137, 138, 139, 147, 151, 154, 155, 167, 168, 173, 174, 176, 180, 181, 183 191, C.I. I. Bat yellow 1,3,20 can be illustrated. Examples of the dye include C.I. I. Solvent yellow 19, 44, 77, 79, 81, 82, 93, 98, 103, 104, 112, 162 can be exemplified. And these may be used independently and may be used together.

  As a colorant suitable for the cyan toner, a pigment or a dye can be used. I. Pigment Blue 1,7,15,15: 1,15: 2,15: 3,15: 4,16,17,60,62,66, C.I. I. Bat Blue 6, C.I. I. Acid blue 45 can be exemplified. Examples of the dye include C.I. I. Solvent blue 25,36,60,70,93,95 can be illustrated. And these may be used independently and may be used together.

  As a colorant suitable for the magenta toner color, a pigment or a dye can be used. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 2, 48: 3, 48: 4, 49, 50, 51, 52, 53, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 81: 1, 83, 87, 88, 89, 90, 112, 114, 122, 123, 144, 146, 150, 163, 166, 169, 177, 184, 185, 202, 206, 207, 209, 220, 221, 238, 254, C.I. I. Pigment violet 19, C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35 can be exemplified. Examples of the magenta dye include C.I. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 30, 49, 52, 58, 63, 81, 82, 83, 84, 100, 109, 111, 121, 122, C.I. I. Disper thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I. I. Disperse Violet 1, C.I. I. Basic Red 1, 2, 9, 12, 13, 14, 15, 17, 18, 22, 23, 24, 27, 29, 32, 34, 35, 36, 37, 38, 39, 40, C.I. I. Basic violet 1,3,7,10,14,15,21,25,26,27,28 can be illustrated. And these may be used independently and may be used together.

  In the present invention, a release agent (wax) can be used as necessary to give the toner releasability. As the release agent, hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax are preferably used because of easy dispersion in toner particles and high releasability. . Moreover, you may use together 1 type, or 2 or more types of wax as needed.

  Examples of the release agent that can be used in combination include the following. Oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; waxes based on fatty acid esters such as carnauba wax, sazol wax, and montanate ester wax; deacidified carnauba Deoxidized part or all of fatty acid esters such as wax. Furthermore, the following are mentioned. Saturated linear fatty acids such as palmitic acid, stearic acid and montanic acid; unsaturated fatty acids such as pracidic acid, eleostearic acid and valinalic acid; stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauvyl alcohol, seryl alcohol, Saturated alcohols such as sil alcohols; long-chain alkyl alcohols; polyhydric alcohols such as sorbitol; fatty acid amides such as linoleic acid amide, oleic acid amide, lauric acid amide; methylene bis stearic acid amide, ethylene biscapric acid amide Saturated fatty acid bisamides such as ethylene bislauric acid amide and hexamethylene bis stearic acid amide; ethylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N′-dioleyl adipine Amides, unsaturated fatty acid amides such as N, N′-dioleyl sebacic acid amides; aromatic bisamides such as m-xylene bisstearic acid amide and N, N-distearylisophthalic acid amides; calcium stearate, calcium laurate , Fatty acid metal salts such as zinc stearate and magnesium stearate (commonly referred to as metal soap); waxes grafted to aliphatic hydrocarbon waxes using vinyl monomers such as styrene and acrylic acid; A partially esterified product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol; a methyl ester compound having a hydroxyl group obtained by hydrogenation of vegetable oil.

  Examples of the release agent particularly preferably used in the present invention include aliphatic hydrocarbon waxes. Examples of such aliphatic hydrocarbon waxes include the following. Low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or Ziegler catalyst under low pressure; alkylene polymer obtained by thermally decomposing high molecular weight alkylene polymer; synthesis containing carbon monoxide and hydrogen Synthetic hydrocarbon waxes obtained from the distillation residue of hydrocarbons obtained from the gas by the age method and synthetic hydrocarbon waxes obtained by hydrogenating them; press sweating method, solvent method, vacuum Wax separated by use of distillation or fractional crystallization.

  Examples of the hydrocarbon as the matrix of the aliphatic hydrocarbon wax include the following. Carbonization synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often a multi-component system of two or more types) (for example, the Gintor method, Hydrocol method (using a fluidized catalyst bed)) Hydrogen compounds); hydrocarbons having up to about several hundred carbon atoms obtained by the age method (using an identified catalyst bed) in which a large amount of waxy hydrocarbons can be obtained; hydrocarbons obtained by polymerizing alkylene such as ethylene with a Ziegler catalyst. Among such hydrocarbons, in the present invention, it is preferable that the hydrocarbon is a linear hydrocarbon having a small number of branches and a long saturation, and particularly a hydrocarbon synthesized by a method not based on polymerization of alkylene has a molecular weight distribution. Is also preferable.

  Specific examples that can be used include the following. Biscol (registered trademark) 330-P, 550-P, 660-P, TS-200 (Sanyo Chemical Industries); high wax 400P, 200P, 100P, 410P, 420P, 320P, 220P, 210P, 110P (Mitsui Chemicals) Sazol H1, H2, C80, C105, C77 (Sazol); HNP-1, HNP-3, HNP-9, HNP-10, HNP-11, HNP-12 (Nippon Seiwa Co., Ltd.), Unilin (registered trademark) 350, 425, 550, 700, Unicid (registered trademark) 350, 425, 550, 700 (Toyo Petrolite Co., Ltd.); wood wax, beeswax, rice wax, candelilla wax, carnauba wax (Co., Ltd.) Celerica NODA).

  The timing of adding the release agent may be added at the time of melt-kneading during the production of toner particles, or may be at the time of production of a resin for toner, and is appropriately selected from existing methods.

  The release agent is preferably added in an amount of 1 part by mass to 20 parts by mass with respect to 100 parts by mass of the binder resin. If it is in said range, favorable dispersion | distribution in resin will be possible, the contamination with respect to a peripheral member can be suppressed, and the mold release effect will fully be acquired.

  A charge control agent can be used for the toner in order to stabilize the triboelectric chargeability. The charge control agent varies depending on the type and physical properties of other toner particle constituent materials, but is preferably contained in an amount of 0.1 parts by weight or more and 10.0 parts by weight or less per 100 parts by weight of the binder resin. More preferably, it is contained in an amount of not less than 5.0 parts by mass. As such charge control agents, there are known ones that control the toner to be negatively charged and those that control the toner to be positively charged, and various types can be used depending on the type and use of the toner. .

  Examples of toners that are negatively charged include the following. Organometallic complexes (monoazo metal complexes; acetylacetone metal complexes); metal complexes or metal salts of aromatic hydroxycarboxylic acids or aromatic dicarboxylic acids. In addition, examples of toners that are negatively charged include aromatic mono- and polycarboxylic acids and their metal salts and anhydrides; phenol derivatives such as esters and bisphenol. Among these, in particular, a metal complex or metal salt of an aromatic hydroxycarboxylic acid capable of obtaining stable charging performance is preferably used.

  Examples of controlling the toner to be positively charged include the following. Modified products with nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like; onium salts such as phosphonium salts and These lake pigments: triphenylmethane dyes and these lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanic acid, ferrocyanic compound Etc.); metal salts of higher fatty acids. In the present invention, these can be used alone or in combination. Of these, charge control agents such as nigrosine compounds and quaternary ammonium salts are particularly preferably used.

  Specific examples that can be used include the following. For negative charging, Spiron Black TRH, T-77, T-95, TN-105 (Hodogaya Chemical Co., Ltd.); BONTRON (registered trademark) S-34, S-44, E-84, E-88 ( Orient Chemical Co., Ltd.). Examples of positive charging include the following. TP-302, TP-415 (Hodogaya Chemical Co., Ltd.); BONTRON (registered trademark) N-01, N-04, N-07, P-51 (Orient Chemical Co., Ltd.); Copy Blue PR (Clariant) ).

  In addition, as the charge control agent, a charge control resin can be used, and the charge control agent can be used in combination.

  Further, in the toner, it is preferable that silica fine powder is externally added in order to improve charging stability, developability, fluidity, and durability.

The fine silica powder used in the present invention has a good result when the specific surface area by the BET method by nitrogen adsorption is 30 m ² / g or more (particularly 50 m ² / g or more and 400 m ² / g or less). It is preferable to add 0.01 parts by weight or more and 8.00 parts by weight or less of silica fine powder, more preferably 0.10 parts by weight or more and 5.00 parts by weight with respect to 100 parts by weight of toner base particles (particles before external addition). It is below mass parts. The BET specific surface area of the silica fine powder is silica using, for example, a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics), GEMINI 2360/2375 (manufactured by Micrometric), or Tristar 3000 (manufactured by Micrometric). Nitrogen gas is adsorbed on the surface of the fine powder, and calculation can be performed using the BET multipoint method.

  In addition, the silica fine powder used in the present invention is optionally modified with an unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane cups for the purpose of hydrophobization and tribocharging control. It is also preferable to treat with a treating agent such as a ring agent, a silane compound having a functional group, or another organosilicon compound, or in combination with various treating agents.

  Furthermore, you may add another external additive to the toner of this invention as needed. Examples of such external additives include charging aids, conductivity-imparting agents, fluidity-imparting agents, anti-caking agents, mold release agents at the time of heat roller fixing, lubricants, abrasives, etc. An inorganic fine powder is mentioned.

  For example, examples of the lubricant include polyfluorinated ethylene powder, zinc stearate powder, and polyvinylidene fluoride powder.

  Examples of the abrasive include cerium oxide powder, silicon carbide powder, and strontium titanate powder. Of these, strontium titanate powder is preferable.

In order to produce the toner according to the present invention, a toner resin, a colorant, and if necessary, a release agent, a charge control agent, and other additives are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill. Disperse the mold release agent, magnetic iron oxide particles and metal-containing compound while melting and kneading them using a thermal kneader such as a twin-screw kneading extruder, heating roll, kneader, and extruder to make the resins compatible with each other. Alternatively, the toner particles can be obtained by dissolving, cooling and solidifying and then pulverizing and classifying. Further, if necessary, the external additive can be sufficiently mixed by a mixer such as a Henschel mixer to obtain a toner.
The physical property measuring method according to the present invention is as follows.

<Maximum endothermic peak of saturated polyester resin (b-2)>
The endothermic peak of the saturated polyester resin (b-2) DSC curve in the present invention is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).
Details of the measurement are shown below.

  The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.

  Specifically, about 2 mg of resin is precisely weighed, placed in an aluminum pan, an empty aluminum pan is used as a reference, the measurement temperature range is 30 to 200 ° C., and the rate of temperature increase is 10 Measurement is performed at ° C / min. In the measurement, the temperature is once raised to 200 ° C., subsequently lowered to 30 ° C. at a temperature lowering rate of 10 ° C./min, and then the temperature is raised again. The peak temperature of the maximum endothermic peak in the present invention is obtained from the DSC curve obtained in the second temperature raising process.

<Number average molecular weight of saturated polyester resin (b-2)>
The number average molecular weight of the saturated polyester resin (b-2) is determined by the GPC method. The specific measurement procedure is as follows.
(I) 0.03 g of the resin to be measured is dispersed and dissolved in 10 ml of o-dichlorobenzene.
(Ii) The obtained solution is shaken on a shaker at 135 ° C. for 24 hours.
(Iii) The shaken solution is filtered through a filter having an opening of 0.2 μm.
(Iv) Using the obtained filtrate as a sample, measurement is performed under the following analysis conditions.

[Analysis conditions]
Separation column: Shodex (TSK GMHHR-H HT20) × 2
Column temperature: 135 ° C
Mobile phase solvent: o-dichlorobenzene Mobile phase flow rate: 1.0 ml / min
Sample concentration: about 0.3%
Injection volume: 300 μl
Detector: Differential refractive index detector Shodex RI-71
Further, in calculating the molecular weight of the sample, a molecular weight calibration curve prepared with a standard polystyrene resin is used. As standard polystyrene resin, Tosoh Corporation TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F- 2, F-1, A-5000, A-2500, A-1000, A-500.

<Measurement of softening point Tm of resin>
The softening point of the resin is measured by using a constant load extrusion type capillary rheometer “flow characteristic evaluation device Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the device. In this device, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the piston drop amount at this time A flow curve showing the relationship between temperature and temperature can be obtained.

  In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is defined as the softening point Tm. The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax at the time when the outflow ends and the piston lowering amount Smin at the time when the outflow starts is obtained (this is X. X = (Smax−Smin) / 2). And the temperature of the flow curve when the amount of piston descent in the flow curve is the sum of X and Smin is the melting temperature Tm in the 1/2 method.

  As a measurement sample, about 1.0 g of a sample is compression-molded at about 10 MPa using a tablet molding compressor (for example, NT-100H, manufactured by NPA System) in an environment of 25 ° C. for about 60 seconds. A cylindrical shape having a diameter of about 8 mm is used.

The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 50 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

<Glass transition temperature of resin>
The glass transition temperature of the resin is obtained from a DSC curve obtained under the same conditions as those for measuring the peak temperature of the maximum endothermic peak using the resin to be measured as a sample. In the DSC curve, the point of intersection between the DSC curve and the midpoint of the baseline before and after the specific heat change is the glass transition temperature Tg.

<Measurement of shape and average primary particle diameter of magnetic iron oxide particles>
The average primary particle diameter was determined by observing magnetic iron oxide particles with a scanning electron microscope (magnification 40000 times), measuring the ferret diameter of 200 particles, and determining the number average particle diameter. Further, the shape of the magnetic iron oxide particles was judged from the observed image. In this example, S-4700 (manufactured by Hitachi, Ltd.) was used as the scanning electron microscope.

<Measurement of magnetic properties of magnetic iron oxide particles>
Using a vibrating sample magnetometer VSM-P7 manufactured by Toei Industry Co., Ltd., measurement was performed at a sample temperature of 25 ° C. and an external magnetic field of 795.8 kA / m.

<Measurement of weight average particle diameter (D4) of toner pulverized sample and toner particles>
The toner pulverized sample and the weight average particle diameter (D4) of the toner particles are calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

Prior to measurement and analysis, the dedicated software was set as follows.
On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.
The specific measurement method is as follows.

  (1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.

  (2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.

  (3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.

  (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.

  (5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner particles are added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.

  (6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.

  (7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) is calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

<Production Example of High Softening Point Resin (a-1-1) Having Unsaturated Polyester Unit>
・ Terephthalic acid 39.5mol%
・ Fumaric acid 10.0 mol%
・ Trimellitic acid 0.5 mol%
・ 1,4-cyclohexanedimethanol 30.0 mol%
・ Ethylene glycol 20.0 mol%
The above monomer and 0.03% by mass of tetra-n-butyl titanate with respect to the total acid component were added and reacted while stirring at 220 ° C. in a nitrogen stream. The reaction time was adjusted so as to obtain a desired softening point, and a high softening point resin (a-1-1) having an unsaturated polyester unit was obtained. The obtained high softening point resin (a-1-1) had a glass transition point of 55 ° C and a softening point of 130 ° C.

<Production Example of High Softening Point Resin (a-1-2) Having Unsaturated Polyester Unit>
In the production example of the high softening point resin (a-1-1), a high softening point resin (a-1-2) having an unsaturated polyester unit is obtained in the same manner except that the reaction temperature is changed to 210 ° C. It was. The obtained high softening point resin (a-1-2) had a glass transition point of 60 ° C. and a softening point of 142 ° C.

<Production Example of High Softening Point Resin (a-1-3) Having Unsaturated Polyester Unit>
・ Terephthalic acid 40.0mol%
・ Fumaric acid 9.5 mol%
・ Trimellitic acid 0.5 mol%
・ Propylene oxide adduct of bisphenol A (average addition mol number: 2.2 mol) 35.0 mol%
・ Ethylene glycol 15.0 mol%
The above monomer and 0.03% by mass of tetra-n-butyl titanate with respect to the total acid component were added, and the reaction was carried out while stirring at 230 ° C. under a nitrogen stream. The reaction time was adjusted so as to obtain a desired softening point, and a high softening point resin (a-1-3) having an unsaturated polyester unit was obtained. The obtained high softening point resin (a-1-3) had a glass transition point of 68 ° C and a softening point of 120 ° C.

<Production Example of High Softening Point Resin (a-1-4) Having Unsaturated Polyester Unit>
・ Terephthalic acid 40.0mol%
・ Fumaric acid 7.5mol%
・ Trimellitic acid 2.5mol%
・ 1,4-cyclohexanedimethanol 30.0 mol%
・ Ethylene glycol 20.0 mol%
The said monomer and 0.01 mass% tetra- n-butyl titanate with respect to all the acid components were added, and it was made to react, stirring at 200 degreeC under nitrogen stream. The reaction time was adjusted so as to obtain a desired softening point, and a high softening point resin (a-1-4) having an unsaturated polyester unit was obtained. The obtained high softening point resin (a-1-4) had a glass transition point of 73 ° C. and a softening point of 170 ° C.

<Production Example of High Softening Point Resin (a-1-5) Having Unsaturated Polyester Unit>
In the production example of the high softening point resin (a-1-4), the high softening point resin (a-1-5) having an unsaturated polyester unit is obtained by lengthening the reaction time and slowing out the resin. Obtained. The obtained high softening point resin (a-1-5) had a glass transition point of 73 ° C. and a softening point of 171 ° C.

<Production Example of Low Softening Point Resin (a-2-1) Having Unsaturated Polyester Unit>
・ Terephthalic acid 47.5mol%
・ Fumaric acid 2.5mol%
・ 1,4-butanediol 35.0 mol%
・ Neopentyl glycol 15.0mol%
The above monomer and 0.03% by mass of tetra-n-butyl titanate with respect to the total acid component were added and reacted while stirring at 210 ° C. in a nitrogen stream. The reaction time was adjusted so as to obtain a desired softening point, and a low softening point resin (a-2-1) having an unsaturated polyester unit was obtained. The obtained low softening point resin (a-2-1) had a glass transition point of 43 ° C and a softening point of 85 ° C.

<Production Example of Low Softening Point Resin (a-2-2) Having Unsaturated Polyester Unit>
・ Terephthalic acid 47.5mol%
・ Fumaric acid 2.5mol%
・ Ethylene glycol 32.5mol%
・ Neopentyl glycol 20.0mol%
The above monomer and 0.03% by mass of tetra-n-butyl titanate with respect to the total acid component were added and reacted while stirring at 210 ° C. in a nitrogen stream. The reaction time was adjusted so as to obtain a desired softening point, and a low softening point resin (a-2-2) having an unsaturated polyester unit was obtained. The obtained low softening point resin (a-2-2) had a glass transition point of 48 ° C. and a softening point of 91 ° C.

<Production Example of Low Softening Point Resin (a-2-3) Having Unsaturated Polyester Unit>
・ Terephthalic acid 47.5mol%
・ Fumaric acid 2.5mol%
・ Ethylene glycol 30.0 mol%
-Ethylene oxide adduct of bisphenol A (average addition mol number: 2.2 mol) 10.0 mol%
・ Propylene oxide adduct of bisphenol A (average addition mol number: 2.2 mol) 10.0 mol%
The above monomer and 0.03% by mass of tetra-n-butyl titanate with respect to the total acid component were added, and the reaction was carried out while stirring at 230 ° C. under a nitrogen stream. The reaction time was adjusted so as to obtain a desired softening point, and a low softening point resin (a-2-3) having an unsaturated polyester unit was obtained. The obtained low softening point resin (a-2-3) had a glass transition point of 40 ° C. and a softening point of 70 ° C.

<Production Example of Low Softening Point Resin (a-2-4) Having Unsaturated Polyester Unit>
・ Terephthalic acid 47.5mol%
・ Fumaric acid 2.5mol%
・ Ethylene glycol 27.5mol%
・ Neopentyl glycol 22.0mol%
・ Trimellitic acid 0.5 mol%
The above monomer and 0.02% by mass of tetra-n-butyl titanate with respect to the total acid component were added and reacted while stirring at 220 ° C. in a nitrogen stream. The reaction time was adjusted so as to obtain a desired softening point to obtain a low softening point resin (a-2-4) having an unsaturated polyester unit. The obtained low softening point resin (a-2-4) had a glass transition point of 68 ° C. and a softening point of 119 ° C.

<Production Example of Low Softening Point Resin (a-2-5) Having Unsaturated Polyester Unit>
In the production example of the low softening point resin (a-2-3), the resin was taken out in a short reaction time to obtain a low softening point resin (a-2-5) having an unsaturated polyester unit. The obtained low softening point resin (a-2-5) had a glass transition point of 40 ° C. and a softening point of 69 ° C.

<Production Example of Resin (A-1) Having Unsaturated Polyester Unit>
30 parts by mass of a high softening point resin (a-1-1) having an unsaturated polyester unit and 70 parts by mass of a low softening point resin (a-2-1) having an unsaturated polyester unit are mixed into a biaxial kneader (PCM). The residence time was controlled so that the temperature of the kneaded resin was 150 ° C. The obtained kneaded product was cooled and pulverized to obtain a resin (A-1) having an unsaturated polyester unit.

<Production Examples of Resin (A-2) to (A-4), (A-6), (A-7) Having Unsaturated Polyester Unit>
Resin (A-2) thru | or (A-) which has an unsaturated polyester unit in the manufacture example of resin (A-1) which has an unsaturated polyester unit except having changed into the prescription and conditions of Table 1 similarly. 4), (A-6), and (A-7) were prepared.

<Production Example of Resin (A-5) Having Unsaturated Polyester Unit>
・ Terephthalic acid 40.0mol%
・ Fumaric acid 9.0mol%
・ Trimellitic acid 1.0 mol%
・ 1,4-cyclohexanedimethanol 25.0mol%
・ Ethylene glycol 25.0mol%
The monomer and 0.02% by mass of tetra-n-butyl titanate with respect to the total acid component were added and reacted while stirring at 210 ° C. in a nitrogen stream. The reaction time was adjusted so as to obtain a desired softening point, and a resin (A-5) having an unsaturated polyester unit was obtained. The obtained resin (A-5) had a glass transition point of 58 ° C and a softening point of 143 ° C.

<Production Example of Resin (A-8) Having Unsaturated Polyester Unit>
・ Terephthalic acid 40.0mol%
・ Fumaric acid 10.0 mol%
・ Ethylene glycol 24.0 mol%
・ 1,4-cyclohexanedimethanol 26.0 mol%
The monomer was charged into a four-necked flask together with the esterification catalyst, and equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, and stirred at 135 ° C. in a nitrogen atmosphere. A vinyl copolymerization monomer (styrene: 83 mol% and 2 ethylhexyl acrylate: 15 mol%) and a mixture of benzoyl peroxide 2 mol% as a polymerization initiator were dropped from the dropping funnel over 4 hours. In addition, the mixing ratio of the polyester monomer and the vinyl copolymer monomer was polyester monomer: vinyl copolymer monomer = 8: 2 on a mass basis. Then, after reacting at 135 ° C. for 7 hours, the reaction temperature was raised to 220 ° C. to perform a condensation polymerization reaction. After completion of the reaction, the reaction mixture was taken out from the container, cooled and pulverized to obtain a resin (A-8) having an unsaturated polyester unit as a hybrid resin. The obtained unsaturated polyester unit resin (A-8) had a glass transition point of 60 ° C and a softening point of 135 ° C.

<Method for Producing Saturated Polyester Resin (b-2-1)>
In an autoclave equipped with a decompression device, water separation device, nitrogen gas introduction device, temperature measurement device, and stirring device,
・ 1,10-decanedicarboxylic acid 51.0 mol%
・ Triethylene glycol 49.0 mol%
The above monomer and 0.30% by mass of tetraisopropyl titanate with respect to the total acid component were added and reacted at 200 ° C. under normal pressure in a nitrogen atmosphere. The reaction time was adjusted so as to obtain the desired softening point, and a saturated polyester resin (b-2-1) was obtained. Table 2 shows the physical properties of the obtained saturated polyester resin (b-2-1).

<Method for producing saturated polyester resin (b-2-2)>
In an autoclave equipped with a decompression device, water separation device, nitrogen gas introduction device, temperature measurement device, and stirring device,
・ Adipic acid 62.0mol%
・ Triethylene glycol 38.0 mol%
The above monomer and 0.30% by mass of tetraisopropyl titanate with respect to the total acid component were added and reacted at 200 ° C. under normal pressure in a nitrogen atmosphere. The reaction time was adjusted so as to obtain the desired softening point, and a saturated polyester resin (b-2-2) was obtained. Table 2 shows the physical properties of the obtained saturated polyester resin (b-2-2).

<Method for producing saturated polyester resin (b-2-3)>
In an autoclave equipped with a decompression device, water separation device, nitrogen gas introduction device, temperature measurement device, and stirring device,
・ 1,10-decanedicarboxylic acid 43.0 mol%
・ Dimethyl 1,10-decanedicarboxylate 9.0 mol%
・ Triethylene glycol 48.0mol%
The above monomer and 0.20% by mass of tetraisopropyl titanate with respect to the total acid component were added and reacted at 200 ° C. under normal pressure in a nitrogen atmosphere. Saturated polyester resin (b-2-3) was obtained by adjusting the reaction time so as to obtain a desired softening point. Table 2 shows the physical properties of the obtained saturated polyester resin (b-2-3).

<Method for producing saturated polyester resin (b-2-4)>
In an autoclave equipped with a decompression device, water separation device, nitrogen gas introduction device, temperature measurement device, and stirring device,
-Succinic acid 54.0 mol%
-Hexamethylene glycol 46.0 mol%
The above monomer and 0.50% by mass of tetraisopropyl titanate with respect to the total acid component were added and reacted at 200 ° C. under normal pressure in a nitrogen atmosphere. The reaction time was adjusted so as to obtain the desired softening point, to obtain a saturated polyester resin (b-2-4). Table 2 shows the physical properties of the saturated polyester resin (b-2-4) obtained.

<Method for producing saturated polyester resin (b-2-5)>
In an autoclave equipped with a decompression device, water separation device, nitrogen gas introduction device, temperature measurement device, and stirring device,
Adipic acid 50.0 mol%
・ Diethylene glycol 50.0 mol%
The above monomer and 0.34% by mass of tetraisopropyl titanate with respect to the total acid component were added and reacted at 200 ° C. under normal pressure in a nitrogen atmosphere. The reaction time was adjusted so as to obtain the desired softening point, and a saturated polyester resin (b-2-5) was obtained. Table 2 shows the physical properties of the obtained saturated polyester resin (b-2-5).

<Method for Producing Saturated Polyester Resin (b-2-6)>
In an autoclave equipped with a decompression device, water separation device, nitrogen gas introduction device, temperature measurement device, and stirring device,
・ Succinic acid 50.0 mol%
・ 1,6-hexanediol 50.0 mol%
The above monomer and 0.34% by mass of tetraisopropyl titanate with respect to the total acid component were added and reacted at 200 ° C. under normal pressure in a nitrogen atmosphere. The reaction time was adjusted so as to obtain the desired softening point, to obtain a saturated polyester resin (b-2-6). Table 2 shows the physical properties of the obtained saturated polyester resin (b-2-6).

<Method for producing saturated polyester resin (b-2-7)>
In an autoclave equipped with a decompression device, water separation device, nitrogen gas introduction device, temperature measurement device, and stirring device,
Adipic acid 50.0 mol%
・ Diethylene glycol 50.0 mol%
The above monomer and 0.50% by mass of tetraisopropyl titanate with respect to the total acid component were added and reacted at 200 ° C. under normal pressure in a nitrogen atmosphere. The reaction time was adjusted so as to obtain the desired softening point, and a saturated polyester resin (b-2-7) was obtained. Table 2 shows the physical properties of the obtained saturated polyester resin (b-2-7).

<Method for Producing Saturated Polyester Resin (b-2-8)>
In an autoclave equipped with a decompression device, water separation device, nitrogen gas introduction device, temperature measurement device, and stirring device,
・ Succinic acid 50.0 mol%
・ 1,6-hexanediol 50.0 mol%
The above monomer and 0.25% by mass of tetraisopropyl titanate with respect to the total acid component were added and reacted at 200 ° C. under normal pressure in a nitrogen atmosphere. The reaction time was adjusted so as to obtain the desired softening point, and a saturated polyester resin (b-2-8) was obtained. Table 2 shows the physical properties of the obtained saturated polyester resin (b-2-8).

<Method for producing saturated polyester resin (b-2-9)>
In an autoclave equipped with a decompression device, water separation device, nitrogen gas introduction device, temperature measurement device, and stirring device,
・ Terephthalic acid 50.0mol%
・ Ethylene glycol 45.0mol%
・ 2,2-dimethylpropane-1,3diol 5.0 mol%
The above monomer and 0.50% by mass of tetraisopropyl titanate with respect to the total acid component were added and reacted at 200 ° C. under normal pressure in a nitrogen atmosphere. The reaction time was adjusted so as to obtain the desired softening point, to obtain a saturated polyester resin (b-2-9). Table 2 shows the physical properties of the obtained saturated polyester resin (b-2-9).

<Production Example of Resin Composition (B-1) Containing Polymerization Initiator>
A kneader mixer was charged with 98 parts by weight of a saturated polyester resin (b-2-1), heated to 100 ° C. and melted, and a polymerization initiator “Perhexa 25B (manufactured by NOF Corporation, 10 hours half-life temperature: 117.9 ° C.) ”2 parts by weight was added and mixed. The obtained mixture was cooled and pulverized to obtain a resin composition (B-1) containing a polymerization initiator.

<Production example of resin compositions (B-2) to (B-11) containing a polymerization initiator>
Polymerization was performed in the same manner as the resin (B-1) containing a polymerization initiator except that the saturated polyester resin described in Table 2 and the polymerization initiator described in Table 3 were used under the conditions described in Table 4. Resin compositions (B-2) to (B-11) containing an initiator were obtained.

<Production Example of Resin Composition (B-12) Containing Polymerization Initiator>
A kneader-type mixer is charged with 95 parts by mass of a release agent (SP-0160 manufactured by Nippon Seiki Co., Ltd., peak temperature of maximum endothermic peak), which is a crystalline component, and heated to 80 ° C. to melt and polymerize. 5 parts by weight of an initiator “Perhexa 25B (manufactured by NOF Corporation, 10 hour half-life temperature: 117.9 ° C.)” is added, and the resulting mixture is cooled and ground to contain a polymerization initiator. A resin composition (B-12) was obtained.

<Example of production of resin (C-1) for toner>
100 parts by mass of the resin (A-1) having an unsaturated polyester unit and 5 parts by mass of the resin composition (B-1) containing a polymerization initiator are mixed, and a biaxial kneader (PCM-30 (Ikegai Iron Works) is mixed. A resin for toner (C-1) was obtained by carrying out a crosslinking reaction at a resin temperature of 180 ° C. and a residence time of about 3 minutes.

<Production Examples of Toner Resins (C-2) to (C-12)>
Toner resins (C-2) to (C-12) were obtained in the same manner as in the production examples of toner resin (C-1) except that the conditions described in Table 5 were changed.

<Example of production of resin for toner (C-13)>
100 parts by mass of the resin (A-1) having an unsaturated polyester unit and 5 parts by mass of the polymerization initiator (b-1-3) described in Table 3 were mixed, and a biaxial kneader (PCM-30 (Ikegai Iron Works) was mixed. The resin temperature was 180 ° C., and a crosslinking reaction was carried out with a residence time of about 3 minutes to obtain a toner resin (C-13).

<Example 1>
Resin for toner (C-1) 100 parts by mass 90 parts by mass of magnetic iron oxide particles (number average particle diameter 0.20 μm, Hc = 11.5 kA / m, σs = 85 Am ² / kg, σr = 16 Am ² / kg )
-2 parts by mass of the charge control agent-1 shown below

After pre-mixing the above materials with a Henschel mixer, using a twin-screw kneader (PCM-30 (manufactured by Ikekai Iron Works Co., Ltd.)), setting the temperature so that the melt temperature at the discharge port is 150 ° C, Melt kneaded. The obtained kneaded product was cooled, coarsely pulverized with a hammer mill, and then pulverized under the following conditions using a turbo mill T250 (manufactured by Turbo Kogyo Co., Ltd.). The cold air temperature is −15 ° C., the flow rate of the suction blower is 3 m ³ / min, and the supply amount of the material to be crushed is 25 kg / hr. The weight average of the crushed sample 10 minutes after the start of the supply of the material to be crushed The rotation speed was adjusted so that the diameter (D4) was 7.0 ± 0.1 μm. Thereafter, the pulverization was continued with the adjusted rotation speed kept constant, sampling was performed 6 times every 10 minutes, the weight average particle diameter (D4) of the obtained pulverized sample was measured, and the standard deviation was obtained.

The obtained standard deviation was evaluated according to the following criteria. The results are shown in Table 6.
A (very good): less than 0.20 B (good): 0.20 or more and less than 0.50 C (normal): 0.50 or more and less than 0.80 D (bad): 0.80 or more Thereafter, the sixth time The finely pulverized powder obtained in the above was classified using a multi-division classifier utilizing the Coanda effect to obtain magnetic toner particles having a weight average particle diameter (D4) of 6.8 μm.

Next, with respect to 100 parts by mass of magnetic toner particles, hydrophobic silica fine powder having a BET specific surface area of 150 m ² / g (30 parts of hexamethyldisilazane (HMDS) and dimethyl silicone oil with respect to 100 parts of silica base before treatment) 1.0 part by mass of 10 parts hydrophobized) and 3.0 parts by mass of strontium titanate fine powder (volume-based 50% particle size (D50): 1.0 μm) are externally added and mixed. The toner (D-1) was obtained by sieving with a mesh having an opening of 150 μm. The obtained toner (D-1) was evaluated as follows.

<Fixability evaluation>
The fixing device of the commercially available copying machine iR5075N (manufactured by Canon Inc.) was removed, and it was modified so that the fixing roller temperature, the process speed, and the pressing force can be arbitrarily set by operating outside the copying machine. Using this fixing device, the low-temperature fixability and high-temperature offset resistance of the toner (D-1) were evaluated.

First, an unfixed halftone image formed on 90 g / m ² paper was passed through the fixing device under the conditions of a process speed of 450 mm / sec, a roller temperature of 150 ° C., and a pressure of 2940 kPa. The obtained fixed image was rubbed 5 times with sylbon paper applied with a pressure of 4.9 kPa (50 g / cm ² ), and the reduction rate (%) of the image density before and after rubbing was measured. The image density was measured using a Macbeth densitometer (manufactured by Macbeth), which is a reflection densitometer, using an SPI filter. The reduction rate of the image density was less than 5%, and it was confirmed that the image had good low-temperature fixability.

Next, an unfixed image formed on 50 g / m ² paper and having an image area ratio of about 5% was passed through the fixing device under the conditions of a process speed of 50 mm / sec, a roller temperature of 240 ° C., and a pressure of 4903 kPa. . When the high temperature offset resistance was evaluated by observing the stain on the obtained fixed image, the stain was not observed, and it was confirmed that the film had good offset resistance.

<Development evaluation>
For the obtained toner (D-1), a commercially available digital copying machine iR5075N (manufactured by Canon Inc.) was used, and a test chart having a printing ratio of 5% was used in a high temperature and high humidity environment (30 ° C., 80% RH). 100,000 continuous prints were made. The developability was evaluated by comparing the image densities of the 100th sheet and the fixed image after the endurance of 100,000 sheets. For the measurement of the image density, a reflection density meter using a Macbeth densitometer (manufactured by Macbeth, using an SPI filter) was used to measure the reflection density of a 5 mm round solid black image. The evaluation criteria are shown below. The evaluation results are shown in Table 6.
A (very good): Decreasing rate of less than 3% B (good): Decreasing rate of 3% or more and less than 6% C (normal): Decreasing rate of 6% or more and less than 10% D (bad): Decreasing rate of 10 % Or more <Examples 2 to 8, Comparative Examples 1 to 5>
Toners (D-2) to (D-13) were prepared in the same manner as in Example 1 except that the toner resin shown in Table 6 was used.

  The toner obtained was evaluated in the same manner as in Example 1. In any toner, the low-temperature fixability and the offset resistance were good. Table 6 shows the results of evaluation of grinding stability and developability.

  As shown from the evaluation results, the resin for toner obtained in Examples 2 to 8 has a uniform particle size at the time of pulverization in the production process, and has excellent characteristics in terms of fixability when converted into a toner. It was a thing.

Claims (4)

Production of toner resin for producing toner resin by melt-kneading resin (A) having an unsaturated polyester unit and resin composition (B) containing a polymerization initiator, and performing a crosslinking reaction during the melt-kneading. A method,
In the DSC curve measured by the polymerization initiator (b-1) and the differential scanning calorimeter (DSC), the resin composition (B) containing the polymerization initiator has a maximum endothermic peak at 50 ° C. or higher and 130 ° C. or lower. A method for producing a resin for toner, comprising a saturated polyester resin (b-2) having a peak temperature.   The resin (A) having the unsaturated polyester unit includes a high softening point resin (a-1) having a softening point of 120 ° C. or higher and 170 ° C. or lower, and a low softening point resin (a) having a softening point of 70 ° C. or higher and lower than 120 ° C. -2). The method for producing a resin for toner according to claim 1, wherein:   The method for producing a resin for toner according to claim 1, wherein the polymerization initiator (b-1) is an organic peroxide.   A toner containing at least a toner resin and a colorant, wherein the toner resin is a toner resin produced by the method for producing a toner resin according to claim 1. Features toner.