JP5366238B2 - Toner for electrophotography - Google Patents

Description

  The present invention relates to a binder resin for an electrophotographic toner used in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and the like, and an electrophotographic toner containing the binder resin.

  In recent years, with an increase in machine speed and energy saving, a toner having excellent low-temperature fixability has been demanded. Accordingly, a condensation polymerization resin using an aliphatic polyhydric alcohol has been proposed as a binder resin for toner, instead of the condensation polymerization resin obtained by using an aromatic polyhydric alcohol conventionally used.

  Patent Document 1 provides a toner for developing an electrostatic charge that is excellent in fixing property and anti-offset property, exhibits a stable charging behavior even when continuously printed, and has excellent durability for obtaining a good high-quality image. In addition, a polyester resin obtained by reacting an alcohol component containing 1,3-propanediol and other specific polyhydric alcohol as essential constituents with a polybasic acid component is used as a binder resin. Toner for electrostatic charge development was disclosed.

  Patent Document 2 discloses an aliphatic diol having 2 to 6 carbon atoms and having a polyol component of 30 to 100 mol% in order to provide a toner having an excellent balance between low-temperature fixability and grindability and excellent gloss after fixing. There is disclosed a polyester resin for a toner using a polyester resin having a number average molecular weight of 1000 to 9500 consisting of (at least a part of the aliphatic diol is 1,2-propylene glycol) and soluble in tetrahydrofuran.

  Patent Document 3 discloses a toner binder resin containing a crystalline polyester and an amorphous polyester resin as a binder resin for toner excellent in low-temperature fixability, environmental stability, and blocking resistance. The crystalline polyester is obtained by polycondensing an alcohol component containing 70 mol% or more of an aliphatic diol having 2 to 8 carbon atoms and a carboxylic acid component containing 70 mol% or more of an aromatic dicarboxylic acid compound. A binder resin for toner is disclosed.

Further, Patent Document 4 includes a binder resin including a composite resin having a condensation polymerization resin unit and an addition polymerization resin unit, and is an electrophotographic toner obtained by a melt pulverization method. At least two types of alkyl succinic acid having a branched chain alkyl group having 9 to 14 carbon atoms and / or at least 2 of alkenyl succinic acid having a branched chain carbon number alkenyl group having 9 to 14 An electrophotographic toner having a structural unit derived from a carboxylic acid component containing a seed and having excellent image stability under high temperature and high humidity, low temperature fixability, offset resistance, durability and the like is disclosed.
JP 2002-169331 A JP 2006-154686 A JP-A-2005-300867 JP 2008-224961 A

  However, the polyester-based resin obtained using an aliphatic polyhydric alcohol is excellent in low-temperature fixability, but is insufficient in preservability and has a high ester value, so that it is easy to absorb water under high temperature and high humidity. The charging stability under high temperature and high humidity is insufficient.

  SUMMARY OF THE INVENTION An object of the present invention is to provide an electrophotographic toner excellent in storage stability as well as charging stability under high temperature and high humidity while satisfying excellent low-temperature fixability, and a toner binder resin used for the toner. There is.

The present invention
[1] A binder resin for an electrophotographic toner comprising an amorphous resin and a crystalline resin, wherein at least one of the amorphous resin and the crystalline resin is bonded with a hydroxyl group. A resin obtained by condensation polymerization of an alcohol component containing an aliphatic polyhydric alcohol (alcohol A) having two or more secondary carbon atoms and a carboxylic acid component, wherein the amorphous resin comprises (a) Polycondensation obtained by polycondensation of a carboxylic acid component containing at least one succinic acid derivative selected from alkyl (9 to 14) succinic acid and alkenyl (9 to 14 carbon) succinic acid with an alcohol component. And (b) a binder resin for an electrophotographic toner, which is at least one resin selected from the group consisting of a composite resin comprising a condensation polymerization resin and a styrene resin, and [2] the above [1] Electricity containing a binder resin The present invention relates to a child photographic toner.

  The toner for electrophotography containing the binder resin of the present invention has the effect of being excellent in storage stability as well as charging stability under high temperature and high humidity while satisfying excellent low temperature fixability.

  The binder resin of the present invention contains an aliphatic resin and a crystalline resin, and is an aliphatic polyvalent having at least one secondary carbon atom having a hydroxyl group bonded thereto as an alcohol component. It is characterized in that alcohol is used. In general, a crystalline resin is effective in improving the low-temperature fixability. On the other hand, when used in combination with an amorphous resin, the preservability tends to be lowered due to the compatibility of both. However, in the present invention, excellent low-temperature fixability is exhibited without impairing the storage stability of the toner. This is because the alkyl group bonded to the secondary carbon to which the hydroxyl group is bonded constrains the mobility of the molecule, so that the excessive compatibility between the crystalline resin and the amorphous resin is controlled. It is estimated that one of them.

  Furthermore, since the resin using an aliphatic polyhydric alcohol has a high ester value, it is easy to absorb water under high temperature and high humidity, and the charging stability under high temperature and high humidity is insufficient. As the crystalline resin, (a) a carboxylic acid component and an alcohol component containing at least one succinic acid derivative selected from alkyl (carbon number 9 to 14) succinic acid and alkenyl (carbon number 9 to 14) succinic acid. Since the polycondensation resin obtained by condensation polymerization and (b) one or more resins selected from the group consisting of composite resins including a condensation polymerization resin and a styrene resin are used, the binding of the present invention The resin is also excellent in charging stability under high temperature and high humidity. This is because the aliphatic polyhydric alcohol having the above specific structure has an alkyl group at the terminal, thereby suppressing hydrophilicity in the vicinity of the ester group and using a polycondensation resin using a highly hydrophobic succinic acid derivative, Or, since it contains at least one of a composite resin containing a condensation polymerization resin and a highly hydrophobic styrene resin, the toner does not absorb moisture even under high temperature and high humidity, and good charge stability is maintained. This is thought to be possible.

  The crystallinity of the resin is expressed as the ratio between the softening point and the maximum peak temperature of the endotherm measured by a differential scanning calorimeter, that is, the softening point / the maximum peak temperature of the endotherm. When the ratio is less than 0.6, the crystallinity is low and there are many amorphous parts. The crystallinity of the resin can be adjusted by the type and ratio of the raw material monomers, production conditions (for example, reaction temperature, reaction time, cooling rate) and the like. In the present invention, “crystalline resin” refers to a resin having a maximum softening point / endothermic peak temperature value of 0.6 to 1.4, preferably 0.8 to 1.2, and “amorphous resin” refers to a softening point / The maximum endothermic peak temperature value is greater than 1.4 or less than 0.6, preferably greater than 1.4. The highest endothermic peak temperature refers to the temperature of the peak on the highest temperature side among the observed endothermic peaks. If the maximum peak temperature is within 20 ° C. from the softening point, the melting point is set, and the peak having a difference from the softening point exceeding 20 ° C. is a peak due to glass transition. In the present invention, the term “condensation polymerization resin” means both a crystalline condensation polymerization resin and an amorphous condensation polymerization resin.

  In the present invention, the crystalline resin is preferably a condensation polymerization resin, and more preferably a condensation polymerization resin obtained by condensation polymerization of an alcohol component containing alcohol A and a carboxylic acid component. The amorphous resin comprises: (a) an alcohol component containing alcohol A and at least one succinic acid derivative selected from alkyl (carbon number 9-14) succinic acid and alkenyl (carbon number 9-14) succinic acid. A polycondensation resin obtained by polycondensation of a carboxylic acid component containing styrene, and (b) a polycondensation resin and a styrene resin obtained by polycondensation of an alcohol component containing alcohol A and a carboxylic acid component One or more selected from the group consisting of composite resins containing

  Further, in the present invention, the amorphous resin is a carboxylic acid containing at least one succinic acid derivative selected from (a) alkyl succinic acid (carbon number 9 to 14) and alkenyl succinic acid (carbon number 9 to 14). It is at least one selected from the group consisting of a polycondensation resin obtained by polycondensation of an acid component and an alcohol component and (b) a composite resin containing a polycondensation resin and a styrene resin. A carboxylic acid component containing at least one succinic acid derivative selected from alkyl succinic acid and alkenyl succinic acid may be used as a raw material monomer of the condensation polymerization resin used.

  Further, the amorphous resin may be composed of the two types (a) and (b). The succinic acid derivative may be an alkyl (carbon number 9 to 14) succinic acid and alkenyl (carbon number 9 to 14) succinic anhydride or a lower alkyl ester having 1 to 3 carbon atoms.

The following 1-3 are mentioned as a preferable binder resin aspect of this invention, and aspect 3 is preferable.
Aspect 1: The crystalline resin is a condensation polymerization resin obtained by condensation polymerization of an alcohol component containing alcohol A and a carboxylic acid component, and the amorphous resin is (a) alkyl (carbon number 9-14) A polycondensation resin obtained by polycondensation of a carboxylic acid component containing at least one succinic acid derivative selected from succinic acid and alkenyl (9 to 14 carbon atoms) succinic acid and an alcohol component, and (b) One or more resins selected from the group consisting of a composite resin including a polymerization resin and a styrene resin.
Aspect 2: The crystalline resin is a condensation polymerization resin, and the amorphous resin is (a) an alcohol component containing alcohol A, alkyl (9 to 14 carbon atoms), succinic acid and alkenyl (9 to 14 carbon atoms). A condensation polymerization resin obtained by condensation polymerization of a carboxylic acid component containing at least one succinic acid derivative selected from succinic acid, and (b) a condensation polymerization of the alcohol component containing alcohol A and the carboxylic acid component. A composite resin comprising a condensation polymerization resin and a styrene resin obtained.
Aspect 3: The crystalline resin is a condensation polymerization resin obtained by condensation polymerization of an alcohol component containing alcohol A and a carboxylic acid component, and the amorphous resin is (a) an alcohol component containing alcohol A A polycondensation resin obtained by polycondensation of a carboxylic acid component containing at least one succinic acid derivative selected from alkyl (9 to 14 carbons) succinic acid and alkenyl (9 to 14 carbons) succinic acid And (b) A composite resin comprising a condensation polymerization resin obtained by condensation polymerization of an alcohol component containing alcohol A and a carboxylic acid component, and a styrene resin.

  Examples of the aliphatic polyhydric alcohol (alcohol A) having two or more secondary carbon atoms bonded with a hydroxyl group include 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 number of carbon atoms of alcohol A is preferably 4-8, more preferably 4-5, and even more preferably 4 from the viewpoint of increasing the ester value and enhancing the storage stability as well as the low-temperature fixability of the toner. In addition, from the viewpoint of improving the storage stability by making the main chain skeleton of the resin rigid, an aliphatic polyhydric alcohol having one or more pairs of secondary carbon atoms in which secondary carbon atoms bonded with hydroxyl groups are adjacent to each other is more suitable. preferable. From these viewpoints, secondary carbon atoms bonded with hydroxyl groups such as 2,3-butanediol, 2,3-pentanediol, 2,3-hexanediol, and 3,4-hexanediol are adjacent to each other. An aliphatic polyhydric alcohol having 4 to 8 carbon atoms and having at least one set of carbon atoms is more preferable.

  As described above, the alcohol A may be used in at least one of an amorphous resin and a crystalline resin. From the viewpoint of storage stability of the toner, the alcohol A is used in the amorphous resin. In view of the storage stability and low-temperature fixability of the toner, it is more preferably used for both the amorphous resin and the crystalline resin.

  In addition, the preferable aspect in case the alcohol A is contained in the alcohol component of an amorphous resin is as follows.

  The content of the alcohol A is preferably 10 to 100 mol%, more preferably 12 to 80 mol% in the alcohol component of the raw material monomer of the amorphous resin, from the viewpoint of storage stability and low-temperature fixability of the toner. 75 mol% is more preferable.

  In addition, the amount of alcohol A used in the condensation polymerization of the alcohol component and carboxylic acid component of the amorphous resin is alcohol A as a raw material monomer of the amorphous resin from the viewpoint of low-temperature fixability and storage stability of the toner. 6 to 100 parts by weight is preferable, 10 to 90 parts by weight is more preferable, and 15 to 80 parts by weight is more preferable with respect to 100 parts by weight of the total amount of the alcohol component and the carboxylic acid component.

  In the amorphous resin, from the viewpoint of low-temperature fixability of the toner, the alcohol component further contains an aliphatic diol (alcohol B) having 2 to 8 carbon atoms other than alcohol A, preferably 2 to 6 carbon atoms. It is preferable. As alcohol B, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-butenediol, 1,3-butanediol, neopentyl glycol and the like can be mentioned. Among these, ethylene glycol, 1,2-propanediol and 1,3-propanediol are preferable from the viewpoint of storage stability of the toner.

  The content of the alcohol B is preferably 0 to 90 mol%, more preferably 0.5 to 90 mol%, more preferably 20 to 88 mol in the alcohol component of the raw material monomer of the amorphous resin, from the viewpoint of enhancing the low-temperature fixability of the toner. % Is more preferable, and 25 to 75 mol% is still more preferable.

  The content of alcohol B relative to 1 mol of alcohol A is preferably 10 mol or less, preferably 0.1 to 5 mol, and more preferably 0.3 to 3 mol, from the viewpoint of toner storage stability and low-temperature fixability.

  Moreover, the preferable aspect in case the alcohol A is contained in the alcohol component of crystalline resin is as follows.

  The content of the alcohol A is preferably 5 to 50 mol%, more preferably 5 to 30 mol%, in the alcohol component of the raw material monomer of the crystalline resin, from the viewpoints of resin crystallinity, toner storage stability and low-temperature fixability. 7 to 25 mol% is more preferable.

  The amount of alcohol A used in the polycondensation of the alcohol component and carboxylic acid component of the crystalline resin is selected from the viewpoints of low-temperature fixability and storage stability of the toner. And 2-30 weight part is preferable with respect to 100 weight part of total amounts of a carboxylic acid component, and 3-20 weight part is more preferable.

  The alcohol component of the crystalline resin preferably further contains the alcohol B from the viewpoint of easiness in raising the crystallinity of the resin.

  The content of the alcohol B is preferably 50 to 95 mol%, more preferably 70 to 95 mol% in the alcohol component of the raw material monomer of the crystalline resin, from the viewpoint of enhancing the resin crystallinity and the low-temperature fixability of the toner. 75 to 93 mol% is more preferable.

  The content of alcohol B with respect to 1 mol of alcohol A is preferably 1 to 20 mol, more preferably 2 to 15 mol, and more preferably 5 to 15 mol from the viewpoints of resin crystallinity, toner storage stability and low-temperature fixability. .

  In common with amorphous resins and crystalline resins, alcohol components other than alcohol A and alcohol B include polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene-2,2- Formula (I), such as bis (4-hydroxyphenyl) propane:

(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 aromatic diol such as an alkylene oxide adduct of bisphenol represented by the formula: a trihydric or higher polyhydric alcohol such as glycerin.

  In the alcohol component including alcohol A, the content of the aromatic diol is preferably 10 mol% or less, more preferably 5 mol% or less in the alcohol component from the viewpoint of low-temperature fixability of the toner, It is preferable not to use it. Here, “not substantially used” means that the content is 0 mol% in the alcohol component or 1 mol% or less even if it is contained.

  In addition, in the case where the alcohol component and the carboxylic acid component are polycondensed in common with the amorphous resin and the crystalline resin, the alcohol B can be used even when the alcohol A is not included.

  The alcohol component of the crystalline resin preferably contains α, ω-linear alkanediol from the viewpoint of resin crystallinity.

  Examples of the α, ω-linear alkanediol include ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc. 2-8 diols are preferred, and 1,4-butanediol and 1,6-hexanediol are more preferred.

  The alcohol component of the amorphous resin is preferably alcohol B other than aromatic alcohol and α, ω-linear alkanediol.

  When the amorphous resin is (a), a carboxylic acid component containing at least one succinic acid derivative selected from alkyl (carbon number 9 to 14) succinic acid and alkenyl (carbon number 9 to 14) succinic acid; A polycondensation resin obtained by polycondensation with an alcohol component is used, and the carbon number of the alkyl group or alkenyl group in the alkyl succinic acid and alkenyl succinic acid depends on the low-temperature fixability, storage stability and high temperature and high humidity of the toner. From the viewpoint of improving the charging stability of the resin, it is 9 to 14, and 10 to 12 is preferable. Further, these alkyl groups and alkenyl groups may be linear or branched, but are preferably branched from the viewpoint of improving the charging stability of the toner under high temperature and high humidity.

  Furthermore, from the viewpoint of improving the low-temperature fixability of the toner and the charging stability under high temperature and high humidity, the succinic acid derivative is an alkyl succinic acid having a branched alkyl group having 9 to 14 carbon atoms and a carbon number having 9 to 14 carbon atoms. Those composed of two or more selected from the group consisting of alkenyl succinic acids having branched alkenyl groups are preferred. Therefore, the succinic acid derivative is composed of two or more kinds of alkyl succinic acid having a branched alkyl group having 9 to 14 carbon atoms, and two kinds of alkenyl succinic acid having a branched alkenyl group having 9 to 14 carbon atoms. Those composed of the above or those composed of at least one of each of the alkyl succinic acid and the alkenyl succinic acid are preferable.

  By using a succinic acid derivative having a branched alkyl group and / or alkenyl group having a different carbon number, the resulting resin has a broad endothermic peak near the glass transition point in differential scanning calorimetry (DSC). Therefore, the toner binder resin has a very wide fixing area.

  The “kind” here is derived from an alkyl group or alkenyl group, and the alkyl group or alkenyl group having different carbon number chain lengths or structural isomers are treated as different types of alkyl succinic acid or alkenyl succinic acid. .

  Specific examples of the alkyl group and alkenyl group having 9 to 14 carbon atoms having a branched chain include an isododecenyl group and an isododecyl group.

  Alkyl succinic acid and alkenyl succinic acid include compounds having an alkylene group (alkylene compounds), maleic acid, fumaric acid and It is preferably obtained from at least one selected from those acid anhydrides.

  As the alkylene compound, those having 9 to 14 carbon atoms are preferable, and specifically, those obtained from ethylene, propylene, isobutylene, normal butylene and the like, for example, trimers and tetramers thereof are preferably used. As a suitable raw material used for the synthesis of the alkylene compound, propylene having a low molecular weight is preferable from the viewpoint of increasing the number of structural isomers. In addition, the alkylene compound is a compound obtained by using a succinic acid derivative as a binder resin for toner, and has a very wide fixing region. Preferably, it has 2 or more peaks corresponding to an alkylene compound having 9 to 14 carbon atoms, more preferably 10 or more, still more preferably 20 or more, and still more preferably 30 or more.

  Suitable catalysts used for the synthesis of the alkylene compound include liquid phosphoric acid, solid phosphoric acid, tungsten, boron trifluoride complex and the like. From the viewpoint of ease of control of the number of structural isomers, a method of adjusting by distillation after random polymerization is preferred.

  On the other hand, among maleic acid, fumaric acid and acid anhydrides thereof, maleic anhydride is preferable from the viewpoint of reactivity.

  Alkyl succinic acid and alkenyl succinic acid can be obtained by a known production method. For example, an alkylene compound and at least one selected from maleic acid, fumaric acid and acid anhydrides thereof are mixed and heated. Thus, it can be obtained by utilizing an ene reaction (see JP-A-48-23405, JP-A-48-23404, US Pat. No. 3,374,285, etc.).

  The content of the succinic acid derivative is preferably 3 to 50 mol%, more preferably 4 to 45 mol% in the carboxylic acid component, from the viewpoints of low-temperature fixability, storage stability, and charging stability under high temperature and high humidity. Preferably, 5-40 mol% is more preferable.

  In both the amorphous resin and the crystalline resin, a divalent carboxylic acid compound or a trivalent or higher carboxylic acid compound is preferably used as the carboxylic acid component.

  Examples of divalent carboxylic acid compounds include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid and the like; phthalic acid And aromatic dicarboxylic acids such as isophthalic acid and terephthalic acid; cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid; and anhydrides and alkyl (C1 to C3) esters of these acids. In the present invention, the above-mentioned acids, anhydrides of these acids, and alkyl esters of the acids are collectively referred to herein as carboxylic acid compounds.

  Examples of the trivalent or higher polyvalent carboxylic acid compound include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid and other aromatic carboxylic acids, and these Derivatives such as acid anhydrides and alkyl (C1-3) esters are mentioned.

  Other carboxylic acid compounds include rosin; rosin modified with fumaric acid, maleic acid, acrylic acid, and the like.

  In the present invention, the carboxylic acid component is a trivalent or higher polyvalent carboxylic acid compound, preferably a trimellitic acid compound, more preferably trimellitic anhydride, from the viewpoint of increasing the molecular weight and improving low-temperature fixability and storage stability of the toner. It is desirable to contain. The content of the trivalent or higher polyvalent carboxylic acid compound is preferably 0.1 to 30 mol%, more preferably 1 to 25 mol%, and still more preferably 5 to 25 mol% in the carboxylic acid component.

  Among these, as the carboxylic acid component of the crystalline resin, an aliphatic dicarboxylic acid compound is preferable from the viewpoint of low-temperature fixability of the toner.

  Examples of the aliphatic dicarboxylic acid compounds include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid and the like, and these acids. Anhydrides, alkyl (1 to 3 carbon atoms) esters, and the like. Among these, dicarboxylic acid compounds having 2 to 8 carbon atoms are preferable, and fumaric acid compounds are more preferable. As described above, the aliphatic dicarboxylic compound refers to an aliphatic dicarboxylic acid, an anhydride thereof, and an alkyl (C1-3) ester thereof. Among these, an aliphatic dicarboxylic acid is preferable.

  The content of the aliphatic dicarboxylic acid compound is preferably 90 to 100 mol%, and more preferably 95 to 100 mol%, in the carboxylic acid component of the raw material monomer of the crystalline resin.

  Moreover, an aromatic dicarboxylic acid compound is preferable as the carboxylic acid of the amorphous resin.

  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 of the resin and improving the offset resistance of the toner.

  In common with amorphous resins and crystalline resins, polycondensation reaction of an alcohol component and a carboxylic acid component can be carried out, for example, in the presence of an esterification catalyst such as a tin compound or a titanium compound, a polymerization inhibitor, etc. It can be performed in an atmosphere, and the temperature condition is preferably 180 to 250 ° C. for an amorphous resin and 120 to 230 ° C. for a crystalline resin.

  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.

Examples of tin (II) compounds having Sn-O bonds include tin (II) oxalate, tin (II) acetate, tin (II) octoate, tin (II) 2-ethylhexanoate, and tin (II) laurate. , Tin (II) carboxylate having a carboxylic acid group having 2 to 28 carbon atoms such as tin (II) stearate, tin (II) oleate; octyloxy tin (II), lauroxy tin (II), stearoxy tin (II) ), Alkoxytin (II) having an alkoxy group having 2 to 28 carbon atoms such as oleyloxytin (II); tin (II) oxide; tin (II) sulfate, Sn—X (X represents a halogen atom) Examples of the tin (II) compound having a bond include tin (II) halides such as tin (II) chloride and tin (II) bromide. Among these, from the viewpoint of catalytic ability, (R ¹ COO) ₂ Sn (wherein R ¹ represents an alkyl group or alkenyl group having 5 to 19 carbon atoms), fatty acid tin (II), (R ² O) ₂ Sn (where R ² is carbon number 6) ~ 20 alkyl or alkenyl groups Alkoxy tin (II) and tin oxide represented by SnO (II) is preferably represented by the be), (R ¹ COO) is more preferably a fatty acid tin represented by ₂ Sn (II) and tin oxide (II) Further preferred are tin (II) octoate, tin (II) 2-ethylhexanoate, tin (II) stearate and tin (II) oxide.

  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.

Specific examples of titanium compounds include titanium diisopropylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₃ H ₇ O) ₂ ], titanium diisopropylate bisdiethanolamate [Ti (C ₄ H ₁₀ O ₂ N) ₂ (C ₃ H ₇ O) ₂ ], titanium dipentylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₅ H ₁₁ O) ₂ ], titanium diety rate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 2 H 5 O) 2 ], titanium dihydroxy octylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (OHC 8 H ₁₆ O) ₂ ], titanium distearate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₁₈ H ₃₇ O) ₂ ], titanium triisopropylate triethanolamate [Ti (C ₆ H ₁₄ O ₃ N) (C ₃ H ₇ O) ₃ ], titanium monopropylate tris (triethanolaminate) [Ti (C ₆ H ₁₄ O ₃ N) ₃ (C ₃ H ₇ O)] and the like, among these, titanium diisopropylate bistri Ethanolaminate, titanium diisopropylate bisdiethanolamate and titanium dipentylate bistriethanolamate are preferred, and these are also available as commercial products of Matsumoto Trading Co., Ltd., for example.

Specific examples of other preferable titanium compounds include tetra-n-butyl titanate [Ti (C ₄ H ₉ O) ₄ ], tetrapropyl titanate [Ti (C ₃ H ₇ O) ₄ ], tetrastearyl titanate [Ti ( C ₁₈ H ₃₇ O) ₄ ], tetramyristyl titanate [Ti (C ₁₄ H ₂₉ O) ₄ ], tetraoctyl titanate [Ti (C ₈ H ₁₇ O) ₄ ], dioctyl dihydroxyoctyl titanate [Ti (C ₈ H ₁₇ O) ₂ (OHC ₈ H ₁₆ O) ₂ ], dimyristyl dioctyl titanate [Ti (C ₁₄ H ₂₉ O) ₂ (C ₈ H ₁₇ O) ₂ ] and the like. Among these, tetrastearyl titanate, tetra Myristyl titanate, tetraoctyl titanate and dioctyl dihydroxy octyl titanate are preferred. These can be obtained, for example, by reacting a titanium halide with a corresponding alcohol, or can be obtained as a commercial product such as Nisso.

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

  The abundance of the esterification catalyst is preferably 0.05 to 1 part by weight, more preferably 0.2 to 0.7 part by weight, based on 100 parts by weight of the total amount of the alcohol component and the carboxylic acid component.

  Examples of the condensation polymerization resin include polyester and polyester / polyamide from the viewpoint of low-temperature fixability of the toner. From the viewpoint of toner durability and charge stability, polyester is preferable.

  In addition, polyester modified | denatured to such an extent that the characteristic is not impaired substantially may be sufficient. Examples of the modified polyester include grafting and blocking with phenol, urethane, epoxy and the like by the methods described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, and the like. Polyester.

  When the amorphous resin is a composite resin containing the condensation polymerization resin (b) and a styrene resin, the raw material monomer of the condensation polymerization resin is the raw material monomer of the amorphous resin as described above. The preferred raw material monomers and preferred amounts thereof are the same, and succinic acid derivatives are preferably used as the carboxylic acid component.

  Styrene derivatives such as styrene, α-methylstyrene, vinyltoluene and the like are used as raw material monomers for the styrene resin.

  The content of the styrene derivative is preferably 50% by weight or more, more preferably 70% by weight or more, and further preferably 80% by weight or more in the raw material monomer of the styrene resin.

  Examples of raw material monomers for styrene resins that can be used in addition to 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-vinyl And N-vinyl compounds such as pyrrolidone. 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 low-temperature fixability and charge stability 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 (Meth) acrylate, (iso) octyl (meth) acrylate, (iso) decyl (meth) acrylate, (iso) stearyl (meth) acrylate, and the like. "(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 preferably 50% by weight or less, more preferably 30% by weight or less in the raw material monomer of the styrene resin from the viewpoint of low-temperature fixability, storage stability and charge stability of the toner. 20% by weight or less is more preferable.

  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 styrenic resin can be performed by a conventional method in the presence of a polymerization initiator, a crosslinking agent, or the like, in the presence of an organic solvent or in the absence of a solvent. 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 amount of the organic solvent used is preferably about 10 to 50 parts by weight with respect to 100 parts by weight of the styrene resin raw material monomer.

  The composite resin in the present invention only needs to contain a condensation polymerization resin and a styrene resin, and may be a mixture of the condensation polymerization resin and the styrene resin. A resin obtained by polymerizing a raw material monomer of a styrene resin is preferred. 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.

  From the viewpoint of improving the low-temperature fixability of the toner and the charging stability under high temperature and high humidity, the composite resin in the present invention is added to the raw material monomer of the condensation polymerization resin and the raw material monomer of the styrene resin, and any of them. A hybrid resin obtained by using a compound (both reactive monomers) capable of reacting with each other is preferable. Therefore, when the raw material monomer of the condensation polymerization resin and the raw material monomer of the styrene resin are polymerized to obtain the composite 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 styrene resin are partially bonded via the both reactive monomers, and the condensation polymerization resin component has a finer styrene resin component, and It will be 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, fumaric acid, maleic acid and maleic anhydride, but from the viewpoint of reactivity, acrylic acid, methacrylic acid and Fumaric acid is more preferred.

  The content of both reactive monomers is preferably 1 to 20 mol% and more preferably 2 to 15 mol% in the total amount of the alcohol component and the carboxylic acid component of the condensation polymerization resin. In the present invention, when calculating the content of the bireactive monomer and the content of the alcohol A relative to the total amount of the alcohol component and the carboxylic acid component other than the alcohol A, the amount of the bireactive monomer is an amorphous resin. The raw material monomer is included in the total amount of the alcohol component and the carboxylic acid component.

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 condensation polymerization resin is mixed with the mixture containing the raw material monomer of the condensation polymerization resin. It can also be made to react by dripping.

  Moreover, when the composite resin is a hybrid resin obtained using an amphoteric monomer, the amphoteric monomer is preferably used together with a raw material monomer for a styrene resin.

  In the present invention, the weight ratio of the condensation polymerization resin to the styrene resin, that is, the weight ratio of the raw material monomer of the condensation polymerization resin to the raw material monomer of the styrene resin (the raw material monomer of the condensation polymerization resin / the raw material monomer of the styrene resin). ) Is preferably a polycondensation resin in the continuous phase and a styrene resin in the dispersed phase, preferably 55/45 to 95/5, more preferably 60/40 to 95/5, and 70 / 30 to 90/10 is more preferable.

  In the present invention, the melting point of the crystalline resin is preferably 70 to 140 ° C., more preferably 80 to 120 ° C., and still more preferably 90 to 115 ° C., from the viewpoint of low-temperature fixability of the toner. The melting point of the crystalline resin can be determined as the maximum peak temperature of the endothermic resin described later.

  The softening point of the crystalline resin is preferably 60 to 130 ° C, more preferably 70 to 125 ° C, and still more preferably 85 to 120 ° C, from the viewpoint of low-temperature fixability of the toner. The melting point and softening point of the crystalline resin can be easily adjusted by adjusting the raw material monomer composition, the polymerization initiator, the molecular weight, the catalyst amount, etc., or selecting the reaction conditions.

  The softening point of the amorphous resin is preferably 90 to 160 ° C., more preferably 95 to 155 ° C., and further preferably 115 to 150 ° C. from the viewpoint of low-temperature fixability and storage stability of the toner. The glass transition point is preferably 45 to 85 ° C., more preferably 50 to 80 ° C., and still more preferably 58 to 75 ° C. from the viewpoint of low-temperature fixability and storage stability of the toner. The glass transition point is a physical property peculiar to an amorphous resin, and is distinguished from the maximum peak temperature of endotherm.

  The acid value of the amorphous resin is preferably from 1 to 90 mgKOH / g, more preferably from 5 to 90 mgKOH / g, and even more preferably from 5 to 88 mgKOH / g, from the viewpoints of chargeability and environmental stability of the toner.

  In the binder resin of the present invention, the weight ratio of the crystalline resin to the amorphous resin (crystalline resin / amorphous resin) is preferably 10/90 to 40/60, and 20/80 to 30/70. More preferred.

  By using the binder resin of the present invention, the electrophotographic toner of the present invention is excellent in both low-temperature fixability and storage stability, which are mutually contradictory properties, and has good charging stability even under high temperature and high humidity. can get.

  In the toner of the present invention, a known binder resin other than the binder resin of the present invention, for example, a vinyl resin such as polyester, styrene-acrylic resin, an epoxy resin, a polycarbonate, A resin such as polyurethane may be used in combination, but the content of the binder resin of the present invention is preferably 30% by weight or more, more preferably 50% by weight or more, and 70% by weight or more in the total binder resin. More preferably, 80% by weight or more is more preferable, 90% by weight or more is further preferable, and substantially 100% by weight is further 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.

  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 and more preferably 0.5 to 7 parts by weight with respect to 100 parts by weight of the binder resin.

  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, jojoba Plant waxes such as oils; animal waxes such as beeswax; waxes such as mineral and petroleum waxes such as montan wax, ozokerite, ceresin, microcrystalline wax, and Fischer-Tropsch wax, which are used alone or in combination of two or more 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 from the viewpoint of productivity and dispersibility of the colorant, A pulverized toner obtained by melt kneading is preferred. In the case of pulverized toner by the melt-kneading method, for example, after a raw material such as a binder resin, a colorant, a charge control agent, and a release agent is uniformly mixed with a mixer such as a Henschel mixer, a sealed kneader, uniaxial or 2 It can be manufactured by melt-kneading with a shaft extruder, open roll type kneader or the like, cooling, pulverizing and classifying. On the other hand, from the viewpoint of reducing the particle size of the toner, a toner by a polymerization method is preferable.

The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably 3 to 15 μm, more preferably 3 to 10 μm. 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.

  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.

  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 processed with the external additive.

[Analysis of alkylene compounds by mass spectrometry gas chromatography]
Install the CI ion source and the following analytical column on the mass spectrometry gas chromatograph (GC / MS) and start up. In addition, CI reaction gas (methane) is flowed, and tuning is performed after 24 hours from the evacuation work of the MS section.

(1) GC
Gas chromatograph: Agilent HP6890N
Analytical column: HP Ultra1 (column length 50m, inner diameter 0.2mm, film thickness 0.33μm)
GC oven temperature rising condition: Initial temperature 100 ℃ (0min)
First stage heating rate 1 ° C / min (up to 150 ° C)
Second stage heating rate 10 ° C / min (up to 300 ° C)
Final temperature 300 ℃ (10min)
Sample injection volume: 1 μL
Inlet condition: Injection mode Split method
Split ratio 50: 1
Inlet temperature 300 ° C
Carrier gas: gas helium
Flow rate 1ml / min (constant flow mode)

(2) Detector Mass spectrometer: 5973N MSD manufactured by Agilent
Ionization method: Chemical ionization method Reaction gas: Isobutane Temperature setting: Quadrupole 150 ° C
Ion source 250 ℃
Detection condition: Scan Scan range: m / z 75-300
Detector ON time: 5 min
Calibration (mass calibration and sensitivity adjustment)
: Reaction gas Methane
Calibrant PFDTD (Perfluoro-5,8-dimethyl
-3,6,9-trioxidedecane)
Tuning method Auto tuning

(3) Sample preparation Propylene tetramer is dissolved in isopropyl alcohol at a concentration of 5% by weight.

(Data processing method)
For the alkene component of each carbon number in the range of 9 to 14 carbon atoms, extract the mass chromatogram by the mass number corresponding to each molecular ion, under the condition of S / N (signal / noise ratio)> 3, Integration is performed according to the integration conditions for each component. From the detection results shown in Tables 1 to 5, the ratio of the specific alkyl chain length component is calculated by the following formula.

(4) Integration condition C ₉ H ₁₈

C ₁₀ H ₂₀

C ₁₁ H ₂₂ , C ₁₂ H ₂₄ and C ₁₃ H ₂₆

C ₁₄ H ₂₈

  In the present invention, an alkylene compound corresponding to 9 to 14 carbon atoms refers to a peak corresponding to a molecular ion in gas chromatography mass spectrometry.

[Softening point of resin]
Using a flow tester (Shimadzu Corporation, CFT-500D), a 1 g sample is heated at a heating rate of 6 ° C / min, and a 1.96 MPa load is 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]
Using a differential scanning calorimeter (DSC Q20, manufactured by TA Instruments Japan), the sample was heated to 200 ° C and cooled to 0 ° C at a temperature decrease rate of 10 ° C / min. Increase the temperature at 10 ° C / min to obtain the maximum endothermic peak temperature.

[Glass transition point of resin]
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), weigh 0.01 to 0.02 g of the sample into an aluminum pan, raise the temperature to 200 ° C, and from that temperature to 0 ° C at a rate of 10 ° C / min. The temperature of the cooled sample is raised at a heating rate of 10 ° C / min, and the temperature at the intersection of the base line extension below the maximum peak temperature of endotherm and the tangent that indicates the maximum slope from the peak rise to the peak apex To do.

[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 (Seiko Denshi Kogyo Co., Ltd., DSC210), the temperature was raised to 200 ° C, and the sample was cooled to 0 ° C at a temperature drop rate of 10 ° C / min. 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).

Production Example of Alkylene Compound An alkylene compound A was obtained by fractional distillation under heating conditions of 183 to 208 ° C. using propylene tetramer (trade name: light tetramer) manufactured by Nippon Oil Corporation. The resulting alkylene compound A had 40 peaks in gas chromatography mass spectrometry. The distribution of the alkylene compound was C9: 0.5 wt%, C10: 4 wt%, C11: 20 wt%, C12: 66 wt%, C13: 9 wt%, C14: 0.5 wt%.

Example of production of alkenyl succinic anhydride A 1 L Nitto High Pressure autoclave was charged with 542.4 g of alkylene compound A, 157.2 g of maleic anhydride, 0.4 g of Chelex-O (manufactured by Sakai Chemical Industry Co., Ltd.), and 0.1 g of butyl hydroquinone. Pressurized nitrogen substitution (0.2 MPaG) was repeated three times. After starting stirring at 60 ° C., the temperature was raised to 230 ° C. over 1 hour and the reaction was carried out for 6 hours. The pressure when the reaction temperature was reached was 0.3 MPaG. After completion of the reaction, the mixture was cooled to 80 ° C., returned to normal pressure (101.3 kPa), and transferred to a 1 L four-necked flask. The temperature was raised to 180 ° C. with stirring, and the remaining alkylene compound was distilled off at 1.3 kPa over 1 hour. Subsequently, after cooling to room temperature (25 ° C.), the pressure was returned to normal pressure (101.3 kPa) to obtain 406.1 g of the target alkenyl succinic anhydride A. The average molecular weight (Mw) of alkenyl succinic anhydride determined from the acid value was 268.

Production Example 1 of Amorphous Hybrid Resin [Resin H1, H2, H3]
Polyester raw material monomers other than trimellitic anhydride and esterification catalyst shown in Table 6 were equipped with a nitrogen introduction tube, a dehydration tube equipped with a fractionation tube through which hot water of 100 ° C. was passed, a stirrer and a thermocouple. In a 4-liter flask with a volume of 1 liter, kept at 180 ° C. for 1 hour in a nitrogen atmosphere, then heated from 180 ° C. to 230 ° C. at a rate of 10 ° C./hr, and then subjected to a condensation polymerization reaction at 230 ° C. for 10 hours. The reaction was performed at ° C and 8.0 kPa for 1 hour. After cooling to 160 ° C., a mixture of acrylic acid (both reactive monomers), a styrene resin raw material monomer and a polymerization initiator shown in Table 6 was added dropwise with a dropping funnel over 1 hour. After the dropwise addition, the addition polymerization reaction was aged for 1 hour while maintaining the temperature at 160 ° C, and then the temperature was raised to 210 ° C. Then, trimellitic anhydride shown in Table 6 was added, and the reaction was performed at 210 ° C for 2 hours. The reaction was carried out at 210 ° C. and 10 kPa until a desired softening point was reached to obtain an amorphous hybrid resin.

Production Example 2 of Amorphous Hybrid Resin [Resin H4]
The raw material monomer of polyester other than trimellitic anhydride and the esterification catalyst shown in Table 6 were put into a 5-liter four-necked flask equipped with a dehydration tube equipped with a nitrogen introduction tube, a stirrer and a thermocouple, and a nitrogen atmosphere. The temperature was raised to 160 ° C. Thereafter, a mixture of acrylic acid (both reactive monomers), a raw material monomer of vinyl resin and a polymerization initiator shown in Table 6 was added dropwise over 1 hour with a dropping funnel. After dropping, the addition polymerization reaction was aged for 1 hour while maintaining the temperature at 160 ° C., followed by condensation polymerization reaction at 230 ° C. for 10 hours, and further reaction at 230 ° C. and 8.0 kPa for 1 hour. Furthermore, trimellitic anhydride shown in Table 6 was added and reacted at 210 ° C. for 2 hours. The reaction was performed at 210 ° C. and 10 kPa until a desired softening point was reached to obtain an amorphous hybrid resin. .

Production Example 1 of Amorphous Polyester [Resin A1, A2, A4]
Polyester raw material monomers and esterification catalysts other than trimellitic anhydride shown in Table 7 were equipped with a nitrogen introduction tube, a dehydration tube equipped with a fractionating tube through which 100 ° C. hot water was passed, a stirrer and a thermocouple. Place in a liter four-necked flask, incubate at 180 ° C for 1 hour in a nitrogen atmosphere, then increase the temperature from 180 ° C to 230 ° C at 10 ° C / hr, then subject to condensation polymerization reaction at 230 ° C for 10 hours. The trimellitic anhydride shown in No. 7 was added, reacted at 210 ° C., and reacted at 10 kPa until the desired softening point was reached to obtain an amorphous polyester.

Production Example 2 of Amorphous Polyester [Resin A3, A5]
The raw material monomer of polyester other than trimellitic anhydride and the esterification catalyst shown in Table 7 were put into a 5-liter four-necked flask equipped with a dehydration tube equipped with a nitrogen introduction tube, a stirrer and a thermocouple, and a nitrogen atmosphere Then, a condensation polymerization reaction was carried out at 230 ° C. for 10 hours, and further a reaction was carried out at 230 ° C. and 8.0 kPa for 1 hour. Further, trimellitic anhydride shown in Table 7 was added, reacted at 210 ° C., and reacted at 10 kPa until a desired softening point was reached to obtain an amorphous polyester.

Production Example 1 of Crystalline Polyester [Resin C1, C2]
Raw material monomers other than trimellitic anhydride shown in Table 8, esterification catalyst, and polymerization inhibitor were placed in a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, and 160 ° C. For 5 hours and then heated to 200 ° C. Further, trimellitic anhydride shown in Table 8 was added and reacted for 20 minutes to obtain a crystalline polyester.

Examples 1-13 and Comparative Examples 1-6
100 parts by weight of binder resin shown in Table 9, 4 parts by weight of carbon black “MOGUL L” (manufactured by Cabot), 1 part by weight of negative charge control agent “Bontron S-34” (manufactured by Orient Chemical Industries) and polypropylene 2 parts by weight of wax “NP-105” (Mitsui Chemicals, melting point: 140 ° C.) are thoroughly mixed with a Henschel mixer, and then heated in the roll at a roll rotation speed of 200 r / min using a co-rotating twin screw extruder. Melt kneading was performed at a temperature of 80 ° C. The obtained melt-kneaded product was cooled, coarsely pulverized, then pulverized by a jet mill, and classified to obtain toner particles having a volume median particle size (D ₅₀ ) of 8.0 μm.

  To 100 parts by weight of the obtained toner particles, 1.0 part by weight of “Aerosil R-972” (manufactured by Nippon Aerosil Co., Ltd.) as an external additive was added and mixed with a Henschel mixer to obtain a toner.

Test Example 1 [low temperature fixability]
Toner was mounted in an apparatus in which the fixing machine of the copier “AR-505” (manufactured by Sharp Corporation) was modified so that fixing was possible outside the apparatus, and an unfixed image was obtained. Using a fixing machine (fixing speed 390mm / sec) adjusted so that the total fixing pressure is 40kgf, the temperature of the fixing roll is gradually increased from 100 ° C to 240 ° C by 10 ° C. A fixing test was conducted. “UNICEF Cellophane” (Mitsubishi Pencil Co., Ltd., width: 18 mm, JISZ-1522) was attached to the fixed image, passed through a fixing roll 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” (manufactured by Macbeth), and the ratio between the two (after peeling / before sticking × 100) was initially 90%. The fixing roll temperature exceeding the minimum fixing temperature was used, and the low-temperature fixing property was evaluated according to the following evaluation criteria. The results are shown in Table 9. The paper used in the fixing test was CopyBond SF-70NA (75 g / m ² ) manufactured by Sharp Corporation.

〔Evaluation criteria〕
A: The minimum fixing temperature is less than 140 ° C.
B: The minimum fixing temperature is 140 ° C. or higher and lower than 150 ° C.
C: The minimum fixing temperature is 150 ° C. or higher and lower than 170 ° C.
D: The minimum fixing temperature is 170 ° C. or higher.

Test Example 2 [Preservation]
4 g of toner was placed in a 20 ml container (diameter: about 3 cm) and left for 72 hours in an environment of 55 ° C. and 60% humidity. After standing, the degree of occurrence of toner aggregation was visually observed, and storage stability was evaluated according to the following evaluation criteria. The results are shown in Table 9.

〔Evaluation criteria〕
A: Aggregation is not observed at all after 48 hours and 72 hours.
B: Aggregation is not observed after 48 hours, but slight aggregation is observed after 72 hours.
C: Aggregation is not observed after 48 hours, but aggregation is clearly observed after 72 hours.
D: Aggregation is observed within 48 hours.

Test Example 3 [Charging stability under high temperature and high humidity]
Put a toner 32g at a temperature of 32 ° C and a relative humidity of 85% toner 0.6g and a silicone ferrite carrier (Kanto Denka Kogyo Co., Ltd., average particle size: 90μm) 19.4g into a 50ml plastic bottle and mix at 250r / min using a ball mill. The toner charge amount was measured using a Q / M meter (EPPING) by the following method.

  After a specified mixing time, a specified amount of toner and carrier mixture is put into the cell attached to the Q / M meter, and only the toner is sucked for 90 seconds through a 32 μm sieve (stainless steel, twill, wire diameter: 0.0035 mm). did. The change in voltage on the carrier generated at that time was monitored, and the value of [total amount of electricity after 90 seconds (μC) / amount of attracted toner (g)] was defined as the charge amount (μC / g). Calculate the ratio of the charge amount after 60 seconds mixing time and the charge amount after 600 seconds mixing time (charge amount after 60 seconds mixing time / charge amount after 600 seconds mixing time) and charge stability according to the following evaluation criteria Evaluated. The results are shown in Table 9.

〔Evaluation criteria〕
A: 0.9 or more B: 0.6 or more, less than 0.9 C: less than 0.6

  From the above results, the toners of Examples 1 to 13 are superior to the toners of Comparative Examples 1 to 6 in all of the low-temperature fixability, storage stability, and charging stability under high temperature and high humidity. I understand.

  The electrophotographic toner 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 (6)

A binder resin for an electrophotographic toner comprising an amorphous resin and a crystalline resin, wherein at least one of the amorphous resin and the crystalline resin is a secondary resin having a hydroxyl group bonded thereto. A resin obtained by polycondensation of an alcohol component containing an aliphatic polyhydric alcohol (alcohol A) having two or more carbon atoms and a carboxylic acid component, wherein the amorphous resin comprises (a) a carbon number at least one condensation of a carboxylic acid component and an alcohol component containing succinic acid derivative selected succinate and carbon atoms containing an alkyl group is a 9-14 from succinic acids containing alkenyl groups is 9 to 14 A binder resin for an electrophotographic toner, which is one or more resins selected from the group consisting of a condensation polymerization resin obtained by polymerization and (b) a composite resin comprising a condensation polymerization resin and a styrene resin.   The alcohol A is an aliphatic polyhydric alcohol having 4 to 8 carbon atoms and having one or more pairs of secondary carbon atoms in which secondary carbon atoms bonded with hydroxyl groups are adjacent to each other. The binder resin described.   The binder resin according to claim 1 or 2, wherein the alcohol component containing alcohol A further contains an aliphatic diol having 2 to 8 carbon atoms other than alcohol A.   The crystalline resin is a condensation polymerization resin obtained by condensation polymerization of an alcohol component containing alcohol A and a carboxylic acid component, and the content of alcohol A is 5% in the alcohol component of the raw material monomer of the crystalline resin. The binder resin according to claim 1, which is ˜50 mol%. Amorphous resin, selected from the succinic acid containing an alkenyl group is a succinic acid and carbon number 9-14 containing an alkyl group is an alcohol component and a carbon number 9 to 14 which contains (a) an alcohol A Obtained by polycondensation of a carboxylic acid component containing at least one succinic acid derivative, and (b) obtained by polycondensation of an alcohol component containing alcohol A and a carboxylic acid component. It is at least one selected from the group consisting of a composite resin including a condensation polymerization resin and a styrene resin, and the content of alcohol A is 10 to 100 mol% in the alcohol component of the raw material monomer of the amorphous resin. The binder resin according to any one of claims 1 to 4.   An electrophotographic toner comprising the binder resin according to claim 1.