JP5106195B2 - Toner for electrophotography - Google Patents

Description

  The present invention relates to a polycondensation reaction catalyst used for the production of a polycondensation resin used in various applications such as films, sheets, fibers, and electrophotographic toner materials, a method for producing the same, and a polycondensation obtained using the catalyst. The present invention relates to a resin and an electrophotographic toner containing the resin.

  Polycondensation resins such as polyester and polyamide are used in various applications such as films, sheets, and fibers by utilizing their chemical and physical properties. Depending on the use of the resulting resin, polycondensation reaction Various types of catalysts that promote the above have been studied.

For example, as a catalyst used in the production of polyester used for a toner binder resin, various tin compounds and titanium compounds have been studied in consideration of not only catalytic activity but also influence on toner performance such as charging property. (See Patent Documents 1 and 2). Further, from the viewpoint of chargeability, it is disclosed that the chargeability can be further improved by using a combination of tin and an amide compound or a compound obtained by reacting an aromatic carboxylic acid with titanium (see Patent Documents 3 and 4). However, there is a need for more reactive catalysts.
JP 2003-186250 A JP 2003-201342 A JP 2006-350035 A JP 2005-338816 A

  An object of the present invention is to provide a polycondensation reaction catalyst having high activity and effective for shortening the reaction time, a method for producing the same, and a polycondensation resin obtained using the catalyst. An object of the present invention is to provide a condensation polymerization resin that is suitably used, and an electrophotographic toner containing the condensation polymerization resin and having good fluidity.

The present invention
[1] A catalyst for polycondensation reaction comprising a compound in which tin or titanium is bonded to a compound having a benzene ring or a cyclohexane ring in which two hydrogen atoms are substituted with a hydroxyl group,
[2] A catalyst for polycondensation reaction comprising a compound obtained by reacting a tin compound or a titanium compound with a compound having a benzene ring or a cyclohexane ring in which two hydrogen atoms are substituted with a hydroxyl group,
[3] A method for producing a catalyst for polycondensation reaction, comprising a step of reacting a tin compound or a titanium compound with a compound having a benzene ring or a cyclohexane ring in which two hydrogen atoms are substituted with a hydroxyl group,
[4] A condensation polymerization resin obtained by condensation polymerization of a raw material monomer in the presence of the condensation polymerization reaction catalyst according to [1] or [2], and [5] a condensation polymerization system according to [4]. The present invention relates to an electrophotographic toner containing a resin.

  The catalyst for polycondensation reaction of the present invention has high activity and exhibits an excellent effect that the reaction time can be shortened in the production of a polycondensation resin. Further, the condensation polymerization resin of the present invention obtained by using the condensation polymerization reaction catalyst of the present invention can be suitably used as a binder resin for toner, and an electron containing the condensation polymerization resin of the present invention. The photographic toner has an excellent effect on fluidity.

  The polycondensation reaction catalyst of the present invention comprises a compound in which tin or titanium is bonded to a compound having a benzene ring or cyclohexane ring in which two hydrogen atoms are substituted with a hydroxyl group, and has a very high catalytic activity. In the production of resin, it is extremely effective for shortening the reaction time. Since the reaction time can be shortened by using the highly active catalyst for the polycondensation reaction of the present invention, a polycondensation resin having a low thermal history is obtained, and when used as a toner binder resin, The fluidity of the toner is improved. Details of the reason why the activity of the catalyst is enhanced are unclear, but when a carboxylic acid compound is used instead of the compound having two hydroxyl groups, the catalyst activity does not increase, and the fluidity of the toner containing the resulting resin Therefore, since tin or titanium is bonded to the compound having two hydroxyl groups, it is presumed that the catalyst is stable and the catalytic activity is enhanced. In the present invention, “bond” in a compound in which tin or titanium is bonded to a compound having a benzene ring or a cyclohexane ring in which two hydrogen atoms are substituted with a hydroxyl group includes two hydrogen atoms of tin or titanium. Is coordinated to a compound having a benzene ring or a cyclohexane ring substituted with a hydroxyl group, that is, the two hydroxyl groups of a compound having a benzene ring or a cyclohexane ring in which tin or titanium has two hydrogen atoms substituted with a hydroxyl group. The state coordinated to an oxygen atom is also included.

In the catalyst of the present invention, in the compound in which tin is bonded to a compound having a benzene ring or cyclohexane ring in which two hydrogen atoms are substituted with a hydroxyl group, tin is a benzene ring in which two hydrogen atoms are substituted with a hydroxyl group. Or it is preferable that it is substituted by a part of hydrogen of the hydroxyl group of the compound having a cyclohexane ring. From the viewpoint of the reaction activity, the formula (I):
Sn (X) _p (I)
(In the formula, X is a skeleton having a benzene ring or a cyclohexane ring in which two hydrogen atoms are substituted with a hydroxyl group, and p is 1 to 2, preferably 1.)
It is preferable to be represented by

  In the formula (I), as X, a skeleton having a benzene ring or cyclohexane ring in which two hydrogen atoms are substituted with a hydroxyl group is a benzene ring or cyclohexane ring in which two hydrogen atoms are substituted with a hydroxyl group as described above. A structure in which tin is substituted for part of the hydrogen atoms of the hydroxyl group of the compound having a hydrogen atom is preferable.

On the other hand, in the catalyst of the present invention, in the compound in which titanium is bonded to a compound having a benzene ring or cyclohexane ring in which two hydrogen atoms are substituted with hydroxyl groups, titanium has two hydrogen atoms substituted with hydroxyl groups. The compound having a benzene ring or a cyclohexane ring is preferably substituted with a part of the hydrogen atom of the hydroxyl group. From the viewpoint of reaction activity, the formula (II):
Ti (X) _n (Y) _m (II)
(In the formula, X is the same as above, Y is a substituted amino group having 4 to 8 carbon atoms, an optionally substituted alkyloxy group having 2 to 28 carbon atoms, and optionally having a substituent. C2-C28 alkenyloxy group or C2-C28 acyloxy group which may have a substituent, n is an integer of 1-4, preferably 1-2, more preferably 1, m is 0 An integer of ˜3, preferably 0-2, more preferably 2.
It is preferable to be represented by

  In the formula (II), as X, a skeleton having a benzene ring or cyclohexane ring in which two hydrogen atoms are substituted with a hydroxyl group is a benzene ring or cyclohexane ring in which two hydrogen atoms are substituted with a hydroxyl group as described above. A structure in which titanium is substituted for a part of the hydrogen atoms of the hydroxyl group of the compound having a hydrogen atom is preferable.

The substituted amino group having 4 to 8 carbon atoms in the formula (II) is the same as the group described as Y ^{1 in} the formula (II-A) described later. Similarly, the optionally substituted alkyloxy group having 2 to 28 carbon atoms and the optionally substituted alkenyloxy group having 2 to 28 carbon atoms are represented by the following formula (II-A): as the Y ² or Y ³ of the formula (II-B), an acyloxy group of 2 to 28 carbon atoms which may have a substituent as Y ³ of the formula (II-B), it is described, respectively group Is the same.

  In one embodiment, the catalyst of the present invention comprises a compound obtained by reacting a tin compound or a titanium compound with a compound having a benzene ring or a cyclohexane ring in which two hydrogen atoms are substituted with a hydroxyl group.

  Examples of tin compounds include tin compounds having Sn—C bonds such as dibutyltin oxide, and tin (II) compounds having no Sn—C bonds.

  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, and among these, from the standpoint of charge rising effect and catalytic ability , (R ¹ COO) ₂ Sn (wherein R ¹ represents an alkyl group or alkenyl group having 5 to 19 carbon atoms), (R ² O) ₂ Sn (where R ² Is C 6-20 alk An alkoxytin (II) represented by SnO or a tin (II) oxide represented by SnO, and a fatty acid tin (II) and tin oxide represented by (R ¹ COO) ₂ Sn (II) is more preferable, tin (II) octoate, tin (II) 2-ethylhexanoate, tin (II) stearate and tin (II) oxide are more preferable, tin (II) octoate and 2-ethyl More preferred is tin (II) hexanoate.

As the titanium compound, as used in the preparation of the catalyst represented by the formula (II), the formula (II-A):
Ti (Y ¹ ) _n (Y ² ) _m (II-A)
(Wherein Y ¹ is a substituted amino group having 4 to 8 carbon atoms, Y ² is an optionally substituted alkyloxy group having 2 to 28 carbon atoms, and optionally having carbon atoms. 2 to 28 alkenyloxy group or optionally substituted acyloxy group having 2 to 28 carbon atoms, preferably alkyloxy group, n and m are integers of 1 to 3, and the sum of n and m is 4)
Is preferable from the viewpoints of resin reactivity and toner fluidity.

In the formula (II-A), the substituted amino group represented by Y ¹ preferably has 6 carbon atoms. The substituted amino group in the present invention is a group having a nitrogen atom that can be directly bonded to a titanium atom, an alkylamino group optionally having a hydroxyl group, or a quaternary in which an amino group is quaternized. A cationic group etc. are mentioned, Preferably it is a quaternary cationic group. Such an amino group can be generated, for example, by reacting titanium halide with an amine compound. Examples of such amine compounds include alkanolamine compounds such as monoalkanolamine compounds, dialkanolamine compounds, trialkanolamine compounds, and trialkyls. Examples include alkylamine compounds such as amines, among which alkanolamines are preferred, and trialkanolamines are more preferred.

The number of carbon atoms of the group represented by Y ² is preferably 2 to 10, more preferably 2 to 5, from the viewpoint of resin reactivity and toner fluidity.

Furthermore, from the viewpoint of the effect of the present invention, the group represented by Y ¹ preferably has a larger number of carbon atoms than the group represented by Y ² , and the difference in the number of carbon atoms is attributed to resin reactivity and toner flow. From a viewpoint of property, Preferably it is 1-6, More preferably, it is 2-4.

In the formula (II-A), the group represented by Y ² may have a substituent such as a hydroxyl group or a halogen, but from the viewpoint of resin reactivity and toner fluidity, it is unsubstituted. Alternatively, those having a hydroxyl group as a substituent are preferred, and those having no substituent are more preferred.

Specific examples of the titanium compound represented by the formula (II-A) include titanium diisopropylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₃ H ₇ O) ₂ ], titanium diisopropyl isopropylate bis diethanol aminate _{[Ti (C 4 H 10 O 2} N) 2 (C 3 H 7 O) 2 ], titanium dipentylate bis triethanolaminate _{[Ti (C 6 H 14 O 3} N) 2 (C 5 H ₁₁ O) ₂ ], titanium diethylate bistriethanolamate [Ti (C ₆ H ₁₄ O ₃ N) ₂ (C ₂ H ₅ O) ₂ ], titanium dihydroxyoctylate bistriethanolamate [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 triisopropyl rate triethanolaminate _{[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, from the viewpoint of resin reactivity and toner fluidity, titanium diisopropylate bistriethanolamate, titanium diisopropylate Bisdiethanolamate and titanium dipentylate bistriethanolamate are preferred, and these are also available as commercial products of Matsumoto Trading Co., Ltd., for example.

Further, as another titanium compound used for the preparation of the catalyst represented by the formula (II), the formula (II-B):
Ti (Y ³ ) ₄ (II-B)
(In the formula, Y ³ has an optionally substituted alkyloxy group having 2 to 28 carbon atoms, an optionally substituted alkenyloxy group having 2 to 28 carbon atoms, or a substituent. Which may be an acyloxy group having 2 to 28 carbon atoms)
In view of colorability and fogging, Y ³ is preferably an alkyloxy group having 2 to 28 carbon atoms which may have a substituent.

In the formula (II-B), the number of carbon atoms of the group represented by Y ³ is preferably 8 to 22, and more preferably 16 to 20 from the viewpoints of colorability and fog.

Further, the groups represented by Y ³ may be the same or different, but from the viewpoint of reaction activity and hydrolysis resistance, all four types are preferably the same group.

In the formula (II-B), the group represented by Y ³ may have a substituent such as a hydroxyl group or a halogen, but is preferably unsubstituted or substituted with a hydroxyl group as a substituent. Are more preferred.

Specific examples of the titanium compound represented by the formula (II-B) include tetra-n-butyl titanate [Ti (C ₄ H ₉ O) ₄ ] and tetraisobutyl 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 dihydroxy octyl 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 which tetrastearyl titanate, tetramyristyl titanate, tetraoctyl titanate and dioctyl dihydroxyoctyl titanate are preferred, for example, reacting a titanium halide with the corresponding alcohol. By Rukoto may, but also available as marketed products of Nisso, or the like.

  Examples of the compound having a benzene ring or cyclohexane ring in which two hydrogen atoms are substituted with a hydroxyl group include divalent phenols such as hydroquinone, and phenolic compounds having a substituent at least in the ortho position with respect to the hydroxyl group (hereinafter, hindered). Phenol), 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and the like. Among these, from the viewpoint of catalytic activity, two hydrogen atoms are hydroxyl groups. A compound having a substituted benzene ring is preferred. From the same point of view, a compound having a benzene ring or a cyclohexane ring in which two hydroxyl groups are adjacent to each other is preferable. Therefore, a compound having a benzene ring in which two hydroxyl groups are adjacent to each other is more preferable.

  The divalent phenol means a compound in which two OH groups are bonded to a benzene ring and has no other substituent, and hydroquinone is preferred.

Hindered phenol, t - butyl catechol, 2,5-di -t- butyl hydroquinone, 2,5-di -t- amyl hydroperoxide quinones, and the like. Among these, t- butyl catechol is preferred .

  The amount ratio of the compound having a benzene ring or cyclohexane ring in which two hydrogen atoms to be subjected to reaction are substituted with a hydroxyl group and a tin compound or a titanium compound is a molar ratio (benzene in which two hydrogen atoms are substituted with a hydroxyl group). Compound having a ring or cyclohexane ring / tin compound or titanium compound), from the viewpoint of catalytic activity, 0.1 to 10 is preferable, 0.5 to 5 is more preferable, and 1.0 to 3 is more preferable.

  Reaction of a tin compound or a titanium compound with a compound having a benzene ring or a cyclohexane ring in which two hydrogen atoms are substituted with hydroxyl groups is carried out by using an alkylene oxide adduct of bisphenol A such as polypropylene glycol and a propylene oxide adduct of bisphenol A ( It is preferably carried out at 100 to 250 ° C., more preferably at 150 to 250 ° C., and even more preferably at 200 to 250 ° C. in an alcohol solvent such as an average added mole number of 2.0 to 4.0).

  Further, the catalyst of the present invention is a method of reacting tin halide or titanium halide with a compound having a benzene ring or cyclohexane ring in which two hydrogen atoms are substituted with a hydroxyl group, an existing tin or titanium alkoxide compound or acid. It can also be obtained by a method such as ligand exchange between a coordination compound and a part of a ligand of a compound in which a metal is bonded to a compound having a benzene ring or a cyclohexane ring in which two hydrogen atoms are substituted with a hydroxyl group. it can.

  As the condensation polymerization reaction in which the catalyst of the present invention can be used, a polyester unit having an ester bond (-COO-) by dehydration condensation of a carboxyl group and a hydroxyl group, an amide bond (-CONH-) by dehydration condensation of a carboxyl group and an amino group In the formation of a polycondensation resin unit having an ester bond, such as a reaction for forming a polycondensation resin unit such as a polyamide unit having an ester bond and a polyester polyamide unit having both an ester bond and an amide bond. The effect of is exhibited more remarkably. In the present invention, not only the reaction between different raw material monomers, but also the reaction of producing polylactic acid by dehydration condensation from a monomer having different functional groups in one molecule, for example, lactic acid having a hydroxyl group and a carboxyl group. Included in the polymerization reaction.

  As the raw material monomer for the polyester unit, an alcohol component and a carboxylic acid component are usually used.

  Examples of the alcohol component include polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane, which are represented by the formula (III):

(Wherein R ³ O and OR ³ are oxyalkylene groups, R ³ is an ethylene and / or propylene group, x and y indicate the number of moles of alkylene oxide added, each being a positive number, The average value of the sum of y and y is preferably 1 to 16, more preferably 1 to 8, and even more preferably 1.5 to 4)
Aromatic diols such as alkylene oxide adducts of bisphenol represented by: ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -Aliphatic diols such as hexanediol, 1,4-butenediol, 1,3-butanediol and neopentyl glycol, and trihydric or higher polyhydric alcohols such as glycerin.

  Examples of carboxylic acid components include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, n-dodecyl succinic acid, n-dodecenyl succinic acid, etc. Aliphatic dicarboxylic acids; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; trivalent or higher polyvalent carboxylic acids such as trimellitic acid and pyromellitic acid; And anhydrides of these acids, alkyl (1 to 3 carbon atoms) esters; rosins; rosins modified with fumaric acid, maleic acid, acrylic acid, and the like. Such acids, anhydrides of these acids, and alkyl esters of these acids are collectively referred to herein as carboxylic acid compounds.

  In addition, a monovalent alcohol is used for the alcohol component, and a monovalent carboxylic acid compound is used for the carboxylic acid component. The molecular weight of the resin obtained by the condensation polymerization reaction is adjusted, and the offset resistance of the electrophotographic toner containing the resin From the viewpoint of improvement, it may be contained as appropriate.

  Furthermore, examples of the raw material monomer for forming an amide bond in the polyester polyamide unit and the polyamide unit include various known polyamines, aminocarboxylic acids, aminoalcohols, etc., preferably hexamethylenediamine and ε-caprolactam.

  The above raw material monomers also include those normally classified as ring-opening polymerization monomers, but these are hydrolyzed by condensation due to the presence of water or the like produced by the condensation polymerization reaction of other monomers. Therefore, it is considered to be included in the raw material monomer of the condensation polymerization resin in a broad sense.

  The amount of the catalyst of the present invention used in the polycondensation reaction is preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the raw material monomer subjected to the polycondensation reaction, from the viewpoint of catalytic activity. Preferably, 0.3 to 1.5 parts by weight is more preferable, and 0.3 to 1 part by weight is more preferable. Here, the amount of catalyst used means the total amount of catalyst used in the condensation polymerization reaction.

  The polycondensation reaction is preferably performed at a temperature of 180 to 250 ° C. in an inert gas atmosphere in the presence of the catalyst of the present invention. The catalyst may be added as a mixture with a carboxylic acid component or an alcohol component. The catalyst may be added to the reaction system either before the start of the reaction or during the reaction. In a two-stage reaction, etc., addition in the first stage, the second stage, etc. is possible. It may be added before the vacuum reaction in a reaction of two or more stages by pressure reaction or vacuum reaction. In the present invention, from the viewpoint of obtaining a higher effect on the promotion of the polycondensation reaction, the time is preferably before the reaction temperature is reached, and more preferably before the start of the reaction. In the present invention, “before starting the reaction” means a state in which water or a solution accompanying the condensation polymerization reaction is not generated.

  The polycondensation resin of the present invention contains the above-mentioned polycondensation reaction catalyst, and the polycondensation resin of the present invention is obtained by polycondensing a raw material monomer in the presence of the polycondensation reaction catalyst of the present invention. can get. By using the highly active catalyst for the polycondensation reaction of the present invention, the reaction time can be shortened, so that a polycondensation resin with a low thermal history can be obtained, and an increase in low molecular weight components and volatile organic components is prevented. can do.

  In the present invention, the polycondensation resin refers to a resin containing a polycondensation resin unit, not only a resin comprising a polycondensation resin unit such as polyester, polyester polyamide, and polyamide obtained by the polycondensation reaction, A hybrid resin having two or more kinds of resin components including a condensation polymerization resin unit, for example, a hybrid resin in which a condensation polymerization resin unit and an addition polymerization resin unit are partially chemically bonded is also included.

  Further, the condensation polymerization resin may be modified to such an extent that the properties are not substantially impaired. For example, the modified polyester may be grafted or blocked with phenol, urethane, epoxy or the like by the method described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, etc. Polyester.

  By using the highly active catalyst for the polycondensation reaction of the present invention, a reaction time can be shortened and a polycondensation resin having a small heat history can be obtained. Therefore, a toner containing the polycondensation resin of the present invention as a binder resin for an electrophotographic toner exhibits good chargeability.

  The softening point of the binder resin is preferably 90 to 160 ° C., more preferably 95 to 155 ° C., and further preferably 98 to 150 ° C. from the viewpoints of toner fixability, storage stability and durability. From the same viewpoint, the glass transition point is preferably 45 to 85 ° C, more preferably 50 to 80 ° C. From the viewpoint of chargeability and environmental stability, the acid value is preferably 1 to 90 mgKOH / g, more preferably 5 to 90 mgKOH / g, and still more preferably 5 to 88 mgKOH / g.

  The present invention further provides an electrophotographic toner containing the condensation polymerization resin of the present invention. In the toner, a known binder resin, for example, a vinyl resin such as styrene-acrylic resin, an epoxy resin, a polycarbonate, a polyurethane, or the like may be used in combination as long as the effects of the present invention are not impaired. However, the content of the condensation polymerization resin of the present invention is preferably 70% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight or more, and substantially 100% by weight in the binder resin. More preferably.

  The toner further includes a colorant, a release agent, a charge control agent, a magnetic powder, a fluidity improver, a conductivity modifier, an extender, a reinforcing filler such as a fibrous substance, an antioxidant, an anti-aging agent, Additives such as a cleaning property improving agent may be appropriately contained.

  As the colorant, all of dyes and pigments used as toner colorants can be used, such as carbon black, 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, and the toner of the present invention 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.

  The toner for electrophotography 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 a melt kneading method is preferred. In the case of pulverized toner by the melt-kneading method, for example, a raw material such as a binder resin, a colorant, and a charge control agent is uniformly mixed with a mixer such as a Henschel mixer, and then a hermetic kneader, a single-screw or twin-screw extruder It can be produced by melt-kneading with an open roll 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. An external additive such as hydrophobic silica may be added to the surface of the toner.

The volume median particle size (D ₅₀ ) of the toner 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 obtained toner can be used as a one-component developing toner or as a two-component developer by mixing with a carrier.

[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.

[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)).

[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).

[Preparation of catalyst]
Example A-1
In a 2-liter four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer, and thermocouple, in a nitrogen atmosphere, polypropylene glycol (molecular weight 700, diol type, reagent, manufactured by Wako Pure Chemical Industries, Ltd.) 1000 g, 2 -202 g (0.5 mol) of tin (II) ethylhexanoate and 83 g (0.5 mol) of tert-butylcatechol (TBC) were added, stirred at 200 ° C. for 4 hours, filtered and washed to obtain catalyst S1. .

Example A-2
In a 2-liter four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer, and thermocouple, in a nitrogen atmosphere, polypropylene glycol (molecular weight 700, diol type, reagent, manufactured by Wako Pure Chemical Industries, Ltd.) 1000 g, 2 -202 g (0.5 mol) of tin (II) ethylhexanoate and 110 g (1 mol) of hydroquinone (HQ) were added, stirred at 200 ° C. for 4 hours, filtered and washed to obtain catalyst S2.

Example A-3
In a 2-liter four-necked flask equipped with a nitrogen inlet tube, dehydration tube, stirrer, and thermocouple, in a nitrogen atmosphere, polypropylene glycol (molecular weight 700, diol type, reagent, manufactured by Wako Pure Chemical Industries, Ltd.) 1000 g, 2 -202 g (0.5 mol) of tin (II) ethylhexanoate and 55 g (0.5 mol) of hydroquinone (HQ) were added, and the mixture was stirred, filtered and washed at 200 ° C for 4 hours to obtain catalyst S3.

Example A-4
In a 2-liter four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer, and thermocouple, under a nitrogen atmosphere, 1000 g of polypropylene glycol (molecular weight 700, diol type, reagent, manufactured by Wako Pure Chemical Industries, Ltd.) 170 g (0.5 mol) of isobutyl titanate and 83 g (0.5 mol) of tert-butylcatechol (TBC) were added, and the mixture was stirred, filtered and washed at 200 ° C. for 4 hours to obtain catalyst T1.

Example A-5
In a 2-liter four-necked flask equipped with a nitrogen introduction tube, dehydration tube, stirrer, and thermocouple, in a nitrogen atmosphere, polypropylene glycol (molecular weight 700, diol type, reagent, manufactured by Wako Pure Chemical Industries, Ltd.) 1000 g, titanium Add 290 g of diisopropylate bistriethanolamate (0.5 mol (0.5 mol (290 × purity 80% / molecular weight 462.5))) and 83 g (0.5 mol) of tert-butylcatechol (TBC) at 200 ° C. for 4 hours. The catalyst T2 was obtained by stirring, filtering and washing.

  The measurement conditions of NMR and ICP (high frequency induction plasma emission analysis) used for the analysis of the catalyst are shown below.

[NMR]
Equipment: Mercury-400 (manufactured by VARIAN)
Observation nucleus: ¹ H
Observation range: 6410.3Hz
Number of data points: 65536
Pulse width: 45 ° (4.5μs)
Wait time: 10s
Integration count: 128 times Measurement temperature: room temperature Measurement solvent: 0.1 N DCl / D ₂ O solution
0.1N NaOD / D ₂ O solution sample concentration: 1%

[ICP]
(1) Preparation of sample solution Accurately extract 0.1 g of sample and wet decompose it with concentrated sulfuric acid, nitric acid and hydrogen peroxide to completely decompose organic matter. This solution is diluted to a constant volume with pure water to obtain a measurement solution.
(2) Measurement
Using a 0.1 to 20 ppm tin or titanium aqueous solution prepared by diluting 1000 ppm tin or titanium standard aqueous solution with pure water as a calibration curve, the content of tin or titanium is quantified using the following ICP emission spectrometer.

ICP emission analyzer: JY238ULTRACE (Horiba)
<Measurement conditions>
Plasma output: 1.0kW
Plasma gas: 18L / min
Nebulizer gas flow rate: 0.2L / min
Carrier gas pressure: 1.0bar
Auxiliary gas: 1.6L / min
Sheath gas: 0.1L / min
Measurement wavelength Sn: 189.989nm
Ti: 334.941nm

[Preparation of polyester]
Examples B-1 to B-7 and Comparative Examples B-1 to B-3
After putting the alcohol component, carboxylic acid component of the raw material monomer composition A shown in Table 2 and the catalyst shown in Table 3 into a 10-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple Under a nitrogen atmosphere, a polycondensation reaction was performed at 235 ° C. until the acid value reached 15 mg KOH / g, and the reaction was further continued at 8 kPa until the desired softening point was reached, thereby obtaining a polyester. The reaction time taken is shown in Table 3.

Examples B-8, B-9 and Comparative Examples B-4, B-5
Four 10-liter capacities equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple, the alcohol component and carboxylic acid component of raw material monomer composition B shown in Table 2, the catalyst shown in Table 3 and 2 g of t-butylcatechol. The polyester was put into a neck flask and subjected to a condensation polymerization reaction at 200 ° C. in a nitrogen atmosphere until the acid value reached 20 mgKOH / g, and further reacted at 8 kPa until the desired softening point was reached to obtain a polyester. The reaction time taken is shown in Table 3.

[Manufacture of toner]
Examples C-1 to C-9 and Comparative Examples C-1 to C-5
100 parts by weight of binder resin shown in Table 3, 4 parts by weight of carbon black “MOGUL L” (Cabot), 1 part by weight of negatively chargeable charge control agent “Bontron S-34” (Orient Chemical) and polyethylene After thoroughly mixing 2 parts by weight of the wax “SP-105” (manufactured by Sazol, melting point: 105 ° C.) with a Henschel mixer, a co-rotating twin-screw extruder with a total length of 1560 mm, screw diameter of 42 mm and barrel inner diameter of 43 mm Used and melt-kneaded at a roll rotation speed of 200 r / min and a heating temperature of 80 ° C. in the roll. The feed rate of the mixture was 20 kg / hr and the average residence time was about 18 seconds. The obtained melt-kneaded product was cooled, coarsely pulverized, then pulverized with a jet mill, and classified to obtain a powder having a volume median particle size (D ₅₀ ) of 7.5 μm.

  To 100 parts by weight of the obtained powder, 0.5 parts by weight of hydrophobic silica “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 (fluidity)
After storing ² g of toner at 30 ° C. and a pressure of 40 g / cm ² for 24 hours, the degree of aggregation of the toner was measured by the following method using a powder tester (manufactured by Hosokawa Micron), and the fluidity was evaluated according to the evaluation criteria. . The results are shown in Table 3. The agglomeration degree is an index representing powder fluidity, and the lower the numerical value, the higher the fluidity of the powder.

[Method of measuring degree of aggregation]
Set 3 different sieve openings (250μm, 149μm, 74μm) in the order of 250μm, middle 149μm, lower 74μm on the powder tester's shaking table, place 2g of toner on the upper sieve, and shake 1mm. Vibrate for 60 seconds in width and measure the weight (g) of toner remaining on each sieve.

The measured toner weight is applied to the following equation to calculate the degree of aggregation (% by weight).
Aggregation degree (% by weight) = a + b + c
a = (weight of toner remaining on the upper screen) / 2 × 100
b = (weight of toner remaining on the sieve in the middle) / 2 × 100 × (3/5)
c = (weight of toner remaining on the screen in the lower stage) / 2 × 100 × (1/5)

[Evaluation criteria for liquidity]
A: Aggregation degree is less than 20% by weight B: Aggregation degree is not less than 20% by weight and less than 40% by weight C: Aggregation degree is not less than 40% by weight

  From the above results, the reaction time can be shortened by producing the condensation polymerization resin using the catalyst of the example, and the toner containing the obtained resin is excellent in fluidity. I understand.

  The catalyst for condensation polymerization reaction of the present invention is suitably used for the production of condensation polymerization resins used for various applications such as films, sheets, fibers, toner materials for electrophotography and the like.

Claims (3)

Tin or titanium, which consists of a compound in which two hydrogen atoms are bonded to a compound having a benzene ring or cyclohexane ring in which a hydroxyl group is substituted, is obtained by polycondensing a raw material monomer in the presence of a polycondensation reaction catalyst. An electrophotographic toner comprising a condensation polymerization resin composition . In the presence of a polycondensation reaction catalyst comprising a compound obtained by reacting a tin compound or a titanium compound with a compound having a benzene ring or a cyclohexane ring in which two hydrogen atoms are substituted with hydroxyl groups, the raw material monomer is condensed. An electrophotographic toner comprising a condensation polymerization resin composition obtained by polymerization.   The molar ratio of the compound having a benzene ring or cyclohexane ring in which two hydrogen atoms are substituted with a hydroxyl group and the tin compound or titanium compound is a molar ratio (a benzene ring or cyclohexane in which two hydrogen atoms are substituted with a hydroxyl group. The toner for electrophotography according to claim 2, wherein the compound is a compound having a ring / tin compound or titanium compound) of 0.1 to 10.