JP6460757B2 - Method for producing binder resin for polyester toner - Google Patents

Description

  The present invention relates to a method for producing a polyester resin binder resin used for developing a latent image formed in an electrophotographic method, a binder resin obtained by the method, and an electrostatic image development containing the binder resin. The present invention relates to a toner.

In the field of electrophotography, with the development of an electrophotographic system, development of toner for electrophotography corresponding to higher image quality and higher speed is required.
In response to higher image quality and higher speed, polyester resin, which is easy to adjust its composition, is widely used as a binder resin for toners, especially for improving thermal properties, and its composition and manufacturing method are also adjusted. Thus, attempts have been made to optimize resin physical properties and the like.

  For example, Patent Document 1 discloses a toner binder resin containing an amorphous polyester having a furan ring for the purpose of improving low-temperature fixability and storage stability.

  Patent Document 2 discloses a raw material monomer in the presence of a tin (II) compound having no Sn—C bond and a sulfonic acid group-containing compound for the purpose of improving the charge start-up property and the charge amount level. A binder resin for electrophotographic toner containing a condensation polymerization resin obtained by condensation polymerization, and an electrophotographic toner containing the binder resin are disclosed.

  Patent Document 3 discloses a resin particle and a release agent particle containing a block copolymer having a crystalline polyester block and an amorphous polyester block for the purpose of enabling low-temperature heat fixing and obtaining a high-quality image. Production of an electrostatic charge image developing method toner comprising a step of agglomerating the resin particles and the release agent particles in a dispersion liquid to obtain aggregated particles, and a step of heating and aggregating the aggregated particles A method for producing an electrostatic charge image developing toner is disclosed, wherein the block copolymer is polymerized at 150 ° C. or less using a Bronsted acid containing a sulfur atom as a catalyst. .

JP 2012-107228 A JP 2008-70455 A JP 2007-114635 A

  In electrophotography, in order to print particularly at high speed, it is necessary to fix at low temperature, and low temperature fixability is required as a property of toner. In order to impart low-temperature fixability, a method of lowering the melting temperature by lowering the softening point or melting point of the binder resin used for the toner is used. In order to improve the gloss of printed matter, so-called gloss, it is preferable to lower the melting temperature and lower the viscosity at the time of fixing. However, the toner that is easily melted at a low temperature is likely to be partly melted by heat generated when it is rubbed with the charging blade. Furthermore, when it preserve | saves at high temperature, blocking arises and it is also inferior to what is called preservability. Accordingly, there is a need for a binder resin for toner that achieves both low-temperature fixability, gloss of printed matter, and durability and storage stability of the toner.

  The present invention relates to a method for producing a binder resin for a polyester toner capable of achieving both low-temperature fixability and gloss of printed matter obtained, and durability and storage stability of the toner, and a binder obtained by the method The present invention relates to a resin and an electrostatic image developing toner containing the binder resin.

  The inventors of the present invention have considered that the factors affecting the low-temperature fixability, durability, storage stability, and gloss of printed matter of the obtained toner are due to the molecular state of the polyester of the binder resin. As a result, an alcohol component containing an aliphatic diol and a carboxylic acid component containing a carboxylic acid compound having a furan ring are polycondensed to a certain reaction rate or higher, and an organic compound having a sulfo group is added to perform polycondensation. As a result, it was found that a binder resin capable of achieving both low-temperature fixability of toner and gloss of printed matter, and durability and storage stability of the toner was obtained, and the present invention was completed.

The present invention
[1] Obtained in Step 1 and Step 1 of polycondensing an alcohol component containing an aliphatic diol and a carboxylic acid component containing a carboxylic acid compound having a furan ring until the reaction rate reaches 70 to 99%. A method for producing a polyester-based toner binder resin, further comprising a step 2 in which an organic compound having a sulfo group is further added to the polycondensate and polycondensed.
[2] A polyester resin binder resin obtained by the production method of [1], and [3] an electrostatic charge image developing toner containing the polyester toner binder resin of [2]. .

  By the method of the present invention, it is possible to produce a polyester-based toner binder resin that can achieve both low-temperature fixability of the obtained toner and gloss of printed matter, and durability and storage stability of the toner.

The method for producing a binder resin for a polyester toner according to the present invention includes:
Step 1 of polycondensing an alcohol component containing an aliphatic diol and a carboxylic acid component containing a carboxylic acid compound having a furan ring until the reaction rate reaches 70 to 99%, and the polycondensation obtained in Step 1 Step 2 in which an organic compound having a sulfo group is further added to the product and polycondensed
Have

  The reason why the toner using the binder resin for polyester toner obtained by the method of the present invention can achieve both low-temperature fixability of the toner and gloss of printed matter, and durability and storage stability of the toner is not clear. It seems like.

  The polyester toner binder resin obtained by the method of the present invention has a structure derived from an aliphatic diol. Since the aliphatic diol has a flexible structure, it improves toner fixability and improves low-temperature fixability and gloss, but is inferior in durability and storage stability. If low molecular weight substances are reduced and the molecular weight is increased to some extent, durability and the like can be improved. However, when a strong acid such as a highly reactive sulfonic acid catalyst is used, esterification proceeds, but etherification or the like. Side reactions are also likely to occur, and low molecular weight products are easily obtained. In the production method of the present invention, after reacting until the reaction rate reaches 70% or more, an organic compound having a sulfo group is further added as an esterification catalyst, and polymerization is performed to derive an aliphatic diol. It is possible to obtain a polyester-based toner binder resin having a structure and a reduced low molecular weight product. In the present invention, a carboxylic acid compound having a furan ring is further used as the carboxylic acid component. A carboxylic acid compound having a furan ring has a structure that is difficult to bend, and it is difficult to obtain a high molecular weight polyester. From the above, by using a raw material containing a carboxylic acid compound having an aliphatic diol and a furan ring as in the present invention, by adding an organic compound having a sulfo group at a certain reaction rate or higher, a low molecular weight product It is considered that a high molecular weight material can be reduced and a toner having a sharp molecular weight distribution can be obtained, and the low-temperature fixability of the resulting toner, the gloss of printed matter, and the durability and storability of the toner can both be achieved.

  Hereafter, each component, process, etc. used for this invention are demonstrated.

  The alcohol component contains at least an aliphatic diol.

  The aliphatic diol preferably contains an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom from the viewpoint of improving low-temperature fixability and storage stability of the obtained toner. The number of carbon atoms of the aliphatic diol having a hydroxyl group bonded to a secondary carbon atom is preferably 3 to 8, more preferably 3 to 6, from the viewpoint of improving the low-temperature fixability and storage stability of the obtained toner. ~ 5 is more preferred. Specific preferred examples include 1,2-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 2,4-pentanediol and the like. Among them, from the viewpoint of improving the low-temperature fixability, storage stability and durability of the obtained toner, 1,2-propanediol and 2,3- Butanediol is preferred, and 1,2-propanediol is more preferred.

  The content of the aliphatic diol having a hydroxyl group bonded to a secondary carbon atom is preferably 10 mol% or more, more preferably 50 mol% or more, and further preferably 60 mol% or more in the alcohol component. Further, from the viewpoint of improving the durability of the obtained toner, it is preferably 90 mol% or less, more preferably 80 mol% or less.

  The aliphatic diol preferably further contains an α, ω-aliphatic diol from the viewpoint of improving the low-temperature fixability and durability of the obtained toner.

  α, ω-aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1, Examples include 10-decanediol and 1,12-dodecanediol.

  The number of carbon atoms of the α, ω-aliphatic diol is preferably 4 or more from the viewpoint of improving the durability of the obtained toner. Further, from the viewpoint of improving the low-temperature fixability and storage stability of the obtained toner, it is preferably 25 or less, more preferably 14 or less, and even more preferably 10 or less.

  The content of the α, ω-aliphatic diol is preferably 10 mol% or more, more preferably 20 mol% or more in the alcohol component, from the viewpoint of improving the durability of the obtained toner. Further, from the viewpoint of improving the low-temperature fixability and storage stability of the obtained toner, it is preferably 50 mol% or less, and more preferably 30 mol% or less.

  Other alcohol components include aromatic diols, trihydric or higher polyhydric alcohols, and the like.

  Examples of the aromatic diol include an alkylene oxide adduct of bisphenol A.

  Examples of the trihydric or higher polyhydric alcohol include glycerin.

  The carboxylic acid component contains a carboxylic acid compound having a furan ring. As a furan ring, the formula (Ia) or (Ib):

The structure represented by these is preferable.

  Examples of the carboxylic acid compound having a furan ring include furan carboxylic acid compounds such as 2,5-furandicarboxylic acid, 2,4-furandicarboxylic acid, 2,3-furandicarboxylic acid, and 3,4-furandicarboxylic acid; Furan carboxylic acid compounds such as furan carboxylic acid and 3-furan carboxylic acid; hydroxy furan carboxylic acid compounds such as 5-hydroxymethyl-furan-2-carboxylic acid; furfuryl acetic acid compound, 3-carboxy-4-methyl-5-propyl And carboxylic acid compounds such as -2-furanpropionate.

  The carboxylic acid compound includes not only a free acid but also an anhydride that decomposes to generate an acid during the reaction and an alkyl ester having 1 to 3 carbon atoms.

  Among these, at least one selected from the group consisting of furandicarboxylic acid compounds, furancarboxylic acid compounds and hydroxyfurancarboxylic acid compounds is preferable from the viewpoint of improving the storage stability and gloss of the obtained toner. Is more preferable, and 2,5-furandicarboxylic acid is more preferable.

  The content of the carboxylic acid compound having a furan ring is preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 80 mol% or more in the carboxylic acid component. Further, from the viewpoint of improving the durability of the obtained toner, it is preferably 95 mol% or less, more preferably 90 mol% or less.

  The carboxylic acid component preferably further contains an alkenyl succinic acid compound having an alkenyl group from the viewpoint of improving the low-temperature fixability and storage stability of the obtained toner.

  As the alkenyl succinic acid compound, from the viewpoint of improving low-temperature fixability and storage stability of the obtained toner, alkenyl succinic acid having a branched chain alkenyl group having 6 to 32 carbon atoms, anhydrides of those acids, and their Examples thereof include alkyl (1 to 3 carbon atoms) esters of acids. Of these, alkenyl succinic anhydride is preferred.

  The number of carbon atoms of the alkenyl group is preferably 8 or more, more preferably 10 or more, from the viewpoint of improving the durability of the obtained toner. Further, from the viewpoint of improving the low-temperature fixability and storage stability of the obtained toner, it is preferably 26 or less, more preferably 14 or less.

  The content of the alkenyl succinic acid compound is preferably 5 mol% or more, more preferably 10 mol% or more, and from the viewpoint of improving the low-temperature fixability and storage stability of the obtained toner, 50 mol% or less is preferable, and 30 mol%. The following is more preferable, 20 mol% or less is more preferable, and 15 mol% or less is more preferable.

  The carboxylic acid component preferably further contains a trivalent or higher polyvalent carboxylic acid compound from the viewpoint of improving the durability of the resulting toner.

  Examples of the trivalent or higher polyvalent carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, anhydrides of these acids, and the like. An alkyl (1 to 3 carbon atoms) ester of the above acid can be used, and among these, trimellitic anhydride is preferable from the viewpoint of improving the low-temperature fixability, storage stability and durability of the obtained toner.

  The content of the trivalent or higher polyvalent carboxylic acid compound is preferable from the viewpoint of improving the durability of the obtained toner, and is preferably 0.5 mol% or more, more preferably 3 mol% or more in the carboxylic acid component. Further, from the viewpoint of improving the durability of the obtained toner, it is preferably 16 mol% or less, more preferably 8 mol% or less.

  Other carboxylic acid components include aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid and adipic acid. Examples thereof include dicarboxylic acids, anhydrides of these acids, alkyl esters having 1 to 3 carbon atoms, and the like.

  The alcohol component may contain a monovalent alcohol, and the carboxylic acid component may contain a monovalent carboxylic acid compound as appropriate.

  The polycondensation of the alcohol component and the carboxylic acid component in step 1 is preferably performed in the presence of an esterification catalyst.

  As the esterification catalyst, a tin catalyst or a titanium catalyst is preferable from the viewpoint of reactivity, and a tin catalyst is preferable from the viewpoint of promptly reaching the target reaction rate and suppressing coloring.

  Examples of the tin catalyst include dibutyltin oxide and tin (II) 2-ethylhexanoate. From the viewpoints of reactivity, molecular weight adjustment, and resin physical property adjustment, tin (II) having no Sn—C bond is used. ) Compounds are preferred.

  As the tin (II) compound having no Sn-C bond, a tin (II) compound having no Sn-C bond and having a Sn-O bond, Sn-X (X represents a halogen atom) ) A tin (II) compound having a bond is preferable, and 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 Alkoxy tin (II) and tin oxide represented by SnO (II) is preferably represented by a group or an alkenyl group), (R ¹ COO) fatty tin represented by ₂ Sn (II) and tin oxide ( II) is more preferred, tin (II) octoate, tin (II) 2-ethylhexanoate, tin (II) stearate and tin (II) oxide are more preferred, tin (II) 2-ethylhexanoate and oxidation Even more preferred is tin (II).

  As the titanium catalyst, 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. More preferred is titanium diisopropylate bistriethanolamate.

  The amount of the esterification catalyst used is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and further preferably 0.2 parts by mass or more with respect to 100 parts by mass as a total of the alcohol component and the carboxylic acid component. Moreover, 2.0 mass parts or less are preferable with respect to 100 mass parts of total amounts of an alcohol component and a carboxylic acid component, 1.5 mass parts or less are more preferable, and 1.0 mass part or less are more preferable.

  In Step 1, a compound having a benzene ring in which hydrogen atoms bonded to three adjacent carbon atoms are substituted with a hydroxyl group may be used as a co-catalyst together with the esterification catalyst.

  In Step 1, a radical polymerization inhibitor may be used from the viewpoint of preventing side reactions other than polycondensation. As the radical polymerization inhibitor, 4-tert-butylcatechol is preferable.

  In step 1, polycondensation is preferably performed in an inert gas atmosphere, and the reaction temperature is preferably 160 to 250 ° C, more preferably 180 to 240 ° C, from the viewpoint of reactivity and thermal decomposability of the monomer. .

  In step 1, polycondensation is performed to reach a predetermined reaction rate. The reaction rate is 70% or more, preferably 80% or more, from the viewpoint of improving the low-temperature fixability, storage stability and durability of the obtained toner. In order to promote the polymerization in the subsequent step 2, it is 99% or less, preferably 90% or less, more preferably 85% or less. The reaction rate in the present invention refers to a value of product reaction water amount (mol) / theoretical product water amount (mol) × 100.

  In the subsequent step 2, an organic compound having a sulfo group is added to the polycondensate obtained in step 1 (reaction system in step 1) to perform polycondensation.

  The organic compound having a sulfo group in the present invention may be an aromatic compound or an aliphatic compound, but is aromatic from the viewpoint of dispersibility in a resin, compatibility with polyester, and charging characteristics. A compound is preferred.

  Examples of aromatic compounds having a sulfo group include p-toluenesulfonic acid, isotoluenesulfonic acid, metatoluenesulfonic acid, benzenesulfonic acid, p-xylene-2-sulfonic acid, naphthalene-1-sulfonic acid, and naphthalene-2-sulfone. Acid, aminobenzenesulfonic acid, 2-aminotoluene-5-sulfonic acid, 8-amino-2-naphthalenesulfonic acid, 4-biphenylsulfonic acid, benzene-1,3-sulfonic acid, para-toluenesulfonic acid-2 butynyl, P-Toluenesulfonic acid-3butynyl, p-toluenesulfonic acid-2chloroethyl, p-toluenesulfonic acid cyclohexyl, 2,5-dimethylbenzenesulfonic acid, dodecylbenzenesulfonic acid, ethyl benzenesulfonate, ethyl p-toluenesulfonate, bis- ethylene glycol p-toluenesulfonate, isobutyl p-toluenesulfonate, Methyl sulfonate, 1,3,6-naphthalene trisulfonic acid, 1-naphthol-2-sulfonic acid, salts of these compounds (sodium salt, potassium salt, etc.), hydrates, methyl ester compounds, etc. . Among these, alkylbenzenesulfonic acid in which an alkyl group is substituted on the benzene ring is preferable from the viewpoint of improving the reactivity of the polyester monomer and improving the low-temperature fixability, storage stability and durability of the resulting toner. The number of carbon atoms of the alkyl group substituted on the benzene ring is preferably 1 to 22, preferably 1 to 14 from the viewpoint of improving the reactivity of the polyester monomer and improving the low-temperature fixability and storage stability and durability of the resulting toner. More preferred is 1-6.

  Examples of the aliphatic compound having a sulfo group include ethanesulfonic acid, 1,2-ethanedisulfonic acid, hydroxyamine-O-sulfonic acid, methanesulfonic acid, ethyl methanesulfonate, trifluoromethanesulfonic acid, 1-butanesulfonic acid, 1-decanesulfonic acid, 1-heptanesulfonic acid, 1-hexanesulfonic acid, 3-hydroxypropanesulfonic acid, 1-nonanesulfonic acid, 1-octanesulfonic acid, 1-pentanesulfonic acid, 1,3-propanedisulfonic acid 1-dodecanesulfonic acid, 1-hexadecanesulfonic acid, 1-propanesulfonic acid, vinylsulfonic acid and its salts, hydrates, and the like.

  The amount of the sulfo group-containing compound used is 0.01 parts by mass or more with respect to 100 parts by mass of the total amount of the alcohol component and carboxylic acid component used in Step 1 from the viewpoint of improving the low-temperature fixability and durability of the obtained toner. Preferably, 0.05 mass part or more is more preferable. Further, from the viewpoint of improving the storage stability of the obtained toner, 0.5 part by mass or less is preferable and 0.2 part by mass or less is more preferable with respect to 100 parts by mass of the total amount of the alcohol component and carboxylic acid component used in Step 1.

  When using a tin catalyst or a titanium catalyst in step 1, the mass ratio of the tin catalyst or titanium catalyst and the organic compound having a sulfo group used in step 2 (tin catalyst or titanium catalyst / an organic compound having a sulfo group) is: From the viewpoint of improving the low-temperature fixability, storage stability, and durability of the obtained toner, 1/2 to 50/1 is preferable, and 1/1 to 20/1 is more preferable.

  Also in step 2, polycondensation is preferably performed in an inert gas atmosphere. From the viewpoint of reactivity and thermal decomposition of the monomer, the reaction temperature is preferably 160 ° C. or higher from the viewpoint of reactivity. More preferably, the temperature is higher than or equal to ° C. Further, from the viewpoint of thermal decomposability of the polyester produced in step 1, 240 ° C. or lower is preferable, and 230 ° C. or lower is more preferable.

  The polyester resin binder resin obtained by the method of the present invention is preferably amorphous.

  The crystallinity of the resin is represented by the ratio between the softening point and the maximum endothermic peak temperature measured by a differential scanning calorimeter, that is, the crystallinity index defined by the value of [softening point / maximum endothermic peak temperature]. Amorphous resins are resins of greater than 1.4, less than 0.6, preferably greater than 1.5, or 0.5 or less. 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. The highest endothermic peak temperature refers to the temperature of the peak on the highest temperature side among the observed endothermic peaks. The maximum peak temperature is the melting point if the difference from the softening point is within 20 ° C., and the peak due to the glass transition if the difference from the softening point exceeds 20 ° C.

  In order to make the polyester resin binder resin amorphous, it is preferable to adjust the amount of α, ω-aliphatic diol in the alcohol component. The amount of α, ω-aliphatic diol in the alcohol component for making the polyester toner binder resin amorphous is preferably 60 mol% or less, more preferably 40% or less.

  The softening point of the binder resin for polyester toner is preferably 90 ° C. or higher, more preferably 110 ° C. or higher, from the viewpoint of improving the storage stability of the obtained toner. Further, from the viewpoint of improving the low-temperature fixability of the obtained toner, the temperature is preferably 160 ° C. or lower, and more preferably 140 ° C. or lower.

  The glass transition temperature of the binder resin for polyester toner is preferably 40 ° C. or higher, more preferably 60 ° C. or higher, from the viewpoint of improving the storage stability of the obtained toner. Further, from the viewpoint of improving the low-temperature fixability of the obtained toner, 90 ° C. or lower is preferable, and 70 ° C. or lower is more preferable.

  The acid value of the binder resin for polyester toner is preferably 0.5 mgKOH / g or more, and more preferably 2 mgKOH / g or more, from the viewpoint of improving the storage stability of the obtained toner. Further, from the viewpoint of improving the durability of the obtained toner, it is preferably 10 mgKOH / g or less, more preferably 8 mgKOH / g or less.

  The hydroxyl value of the binder resin for the polyester toner is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, from the viewpoint of improving the low-temperature fixability of the obtained toner. Further, from the viewpoint of improving the storage stability and durability of the obtained toner, it is preferably 40 mgKOH / g or less, more preferably 20 mgKOH / g or less, and further preferably 15 mgKOH / g or less.

  The number average molecular weight of the binder resin for polyester toner is preferably 3000 or more, more preferably 4500 or more in terms of polystyrene, from the viewpoint of improving the low-temperature fixability, storage stability and durability of the toner. Further, from the viewpoint of improving the storage stability, durability and gloss of the obtained toner, it is preferably 10000 or less, more preferably 7000 or less, further preferably 5500 or less, and further preferably 5000 or less.

  The toner for developing an electrostatic charge image of the present invention contains a binder resin for toner obtained by the method of the present invention, and achieves both low temperature fixability and gloss of printed matter, and durability and storage stability of the toner. To do.

  In the toner of the present invention, known resins other than the binder resin composition for toner may be used in combination as long as the effects of the present invention are not impaired. The content is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and still more preferably 100% by mass in the total binder resin composition in the toner.

  In addition, the toner for developing an electrostatic charge image of the present invention preferably contains two types of binder resins having different softening points from the viewpoint of improving the durability of the obtained toner, and improves the durability of the obtained toner. In view of the above, at least the binder resin having a higher softening point is preferably the binder resin for toner of the present invention, and improves the storage stability and durability of the obtained toner, the low-temperature fixability, and the gloss of the printed matter. From the viewpoint, it is more preferable that both resins are the binder resin for toner of the invention.

  The difference in softening point between the two types of binder resins is preferably 10 ° C. or higher, and more preferably 15 ° C. or higher.

  The softening point of the resin having the lower softening point is preferably 80 ° C or higher, more preferably 85 ° C or higher, preferably lower than 120 ° C, and more preferably 110 ° C or lower. The softening point of the resin having the higher softening point is preferably 120 ° C or higher, more preferably 130 ° C or higher, preferably 170 ° C or lower, and more preferably 150 ° C or lower.

  The mass ratio of the resin having the higher softening point and the resin having the lower softening point (the resin having the higher softening point / the resin having the lower softening point) is preferably 50/50 to 90/10, 60/40 ~ 80/20 is more preferred.

  The toner of the present invention includes a colorant, a release agent, a charge control agent, a charge control resin, magnetic powder, a fluidity improver, a conductivity modifier, a reinforcing filler such as a fibrous substance, an antioxidant, and a cleaning property. Additives such as improvers may be contained, and it is preferred that a colorant, a release agent and a charge control agent are contained.

  As the colorant, all of the 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, Disazo Yellow and the like can be used, and the toner of the present invention may be either a black toner or a color toner. The content of the colorant is preferably 1 part by mass or more and more preferably 2 parts by mass or more with respect to 100 parts by mass of the binder resin from the viewpoint of improving the toner image density and low-temperature fixability. Moreover, 40 mass parts or less are preferable, and 10 mass parts or less are more preferable.

  As the release agent, low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax and oxides thereof, carnauba wax, Examples include ester waxes such as montan wax, sazol wax and their deoxidized wax, fatty acid ester wax, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts, and the like. It can be used by mixing.

  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 parts by mass or more with respect to 100 parts by mass of the binder resin from the viewpoint of low-temperature fixability and offset resistance of the toner and dispersibility in the binder resin. More preferably, it is more preferably 1.5 parts by mass or more. Moreover, 10 mass parts or less are preferable, 8 mass parts or less are more preferable, and 7 mass parts or less are further more preferable.

  The charge control agent is not particularly limited, and may contain either a positively chargeable charge control agent or a negatively chargeable charge control agent.

  Examples of positively chargeable charge control agents include nigrosine dyes such as “Nigrosine Base EX”, “Oil Black BS”, “Oil Black SO”, “Bontron N-01”, “Bontron N-04”, “Bontron N-07 ”,“ Bontron N-09 ”,“ Bontron N-11 ”(manufactured by Orient Chemical Co., Ltd.), etc .; triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds such as“ Bontron ” P-51 "(manufactured by Orient Chemical Industries), cetyltrimethylammonium bromide," COPY CHARGE PX VP435 "(manufactured by Clariant), etc .; polyamine resins such as" AFP-B "(manufactured by Orient Chemical Industries); imidazole derivatives Examples thereof include “PLZ-2001”, “PLZ-8001” (manufactured by Shikoku Kasei Co., Ltd.) and the like; styrene-acrylic resins such as “FCA-701PT” (manufactured by Fujikura Kasei Co., Ltd.) and the like.

  In addition, as the negatively chargeable charge control agent, metal-containing azo dyes such as “Varifast Black 3804”, “Bontron S-31” (made by Orient Chemical Co., Ltd.), “T-77” (Hodogaya Chemical Industry) Bontron S-32, Bontron S-34, Bontron S-36 (above, Orient Chemical Industry Co., Ltd.), Eisenspiron Black TRH (Hodogaya Chemical Co., Ltd.), etc. A metal compound of a benzylic acid compound, for example, “LR-147”, “LR-297” (manufactured by Nippon Carlit Co., Ltd.); a metal compound of a salicylic acid compound, for example, “Bontron E-81”, “Bontron E-84” ", Bontron E-88", "E-304" (manufactured by Orient Chemical Co., Ltd.), "TN-105" (Hodogaya Chemical Co., Ltd.); copper phthalocyanine dyes; quaternary ammonium salts such as "COPY" CHARGE NX VP434 "(manufactured by Clariant), nitroimidazole derivative; organometallic Thing, for example, "TN105" (commercially available from Hodogaya Chemical Co., Ltd.), and the like.

  The content of the charge control agent is preferably 0.01 parts by mass or more, more preferably 0.3 parts by mass or more, further preferably 0.5 parts by mass or more, with respect to 100 parts by mass of the binder resin, from the viewpoint of charging stability of the toner. 1 part by mass or more is more preferable, 10 parts by mass or less is preferable, 5 parts by mass or less is more preferable, 3 parts by mass or less is further preferable, and 2 parts by mass or less is further preferable.

  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 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 hermetically sealed kneader, a single or twin screw extruder It can be produced by melt-kneading with an open roll kneader or the like, cooling, pulverizing and classifying.

  In the toner of the present invention, an external additive is preferably used in order to improve transferability, and inorganic fine particles are preferably used as the external additive. Examples of the inorganic fine particles include silica, alumina, titania, zirconia, tin oxide and zinc oxide, and silica is preferable.

  Silica is preferably hydrophobic silica that has been subjected to a hydrophobic treatment, from the viewpoint of toner transferability.

  Examples of the hydrophobizing agent for hydrophobizing the surface of silica particles include hexamethyldisilazane (HMDS), dimethyldichlorosilane (DMDS), silicone oil, octyltriethoxysilane (OTES), and methyltriethoxysilane. Of these, hexamethyldisilazane is preferred.

  The average particle diameter of the external additive is preferably 10 nm or more, and more preferably 15 nm or more, from the viewpoint of the chargeability, fluidity, and transferability of the toner. Further, it is preferably 250 nm or less, more preferably 200 nm or less, and further preferably 90 nm or less.

  The content of the external additive is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, and further preferably 0.3 parts by mass or more with respect to 100 parts by mass of the toner before being processed with the external additive. Moreover, 5 mass parts or less are preferable, and 3 mass parts or less are more 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. When the toner is treated with an external additive, the volume median particle size of the toner particles before being treated with the external additive is defined as the volume median particle size of the toner.

  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.

  In relation to the above-described embodiments, the present invention further discloses a method for producing a polyester-based toner binder resin, a binder resin obtained by the method, and an electrostatic charge image developing toner containing the binder resin.

<1> Obtained in Step 1 and Step 1 of polycondensing an alcohol component containing an aliphatic diol and a carboxylic acid component containing a carboxylic acid compound having a furan ring until the reaction rate reaches 70 to 99%. A method for producing a polyester-based toner binder resin, comprising a step 2 in which an organic compound having a sulfo group is further added to the polycondensate and polycondensed.

<2> The production method according to <1>, wherein step 1 is performed in the presence of a tin catalyst or a titanium catalyst.
<3> Said <1> or <2> description whose usage-amount of the organic compound which has a sulfo group is 0.01-0.5 mass part with respect to 100 mass parts of total amounts of the alcohol component and carboxylic acid component which are provided to the process 1. Manufacturing method.
<4> The production method according to any one of <1> to <3>, wherein the reaction temperature in step 2 is 160 to 240 ° C.
<5> The method according to any one of <1> to <4>, wherein the organic compound having a sulfo group is alkylbenzenesulfonic acid.
<6> The method according to any one of <1> to <5>, wherein the carboxylic acid compound having a furan ring is furandicarboxylic acid.
<7> The production method according to any one of <1> to <6>, wherein the aliphatic diol contains an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom.
<8> The mass ratio of the tin catalyst or titanium catalyst used in step 1 and the organic compound having a sulfo group used in step 2 (tin catalyst or titanium catalyst / organic compound having a sulfo group) is 1/2 to 50 / The production method according to any one of <2> to <7>, which is 1.
<9> The production method according to any one of <2> to <8>, wherein the tin catalyst or the titanium catalyst is a tin catalyst.
<10> The production method according to any one of <2> to <9>, wherein the tin catalyst is a tin (II) compound having no Sn-C bond.
<11> The method according to any one of <7> to <10>, wherein the aliphatic diol having a hydroxyl group bonded to a secondary carbon atom has 3 to 5 carbon atoms.
<12> The method according to any one of <1> to <11>, wherein the alcohol component further contains an α, ω-aliphatic diol having 4 to 25 carbon atoms.
<13> The method according to any one of <1> to <12>, wherein the carboxylic acid component contains a trivalent or higher polyvalent carboxylic acid compound.
<14> The production method according to any one of <1> to <13>, wherein the carboxylic acid component contains an alkenyl succinic acid compound having an alkenyl group having 8 to 26 carbon atoms.
<15> A polyester-based toner binder resin obtained by the production method according to any one of <1> to <14>.
<16> The polyester resin binder resin according to <15>, wherein the number average molecular weight of the polyester toner binder resin is 3000 or more and 10,000 or less.
<17> The polyester toner binder resin according to <15> or <16>, wherein the polyester toner binder resin is amorphous.
<18> The polyester resin binder resin according to any one of <15> to <17>, wherein the glass transition temperature of the polyester toner binder resin is 40 to 90 ° C.
<19> The polyester resin binder resin according to any one of <15> to <18>, wherein the softening point of the polyester toner binder resin is 90 to 160 ° C.
<20> An electrostatic charge image developing toner comprising the polyester resin binder resin according to any one of <15> to <19>.

  The physical properties of the resin and the like were measured by the following method.

[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 load of 1.96 MPa 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 (Q-100 Japan, Q-100), weigh 0.01 to 0.02 g of the sample into an aluminum pan and cool it from room temperature to 0 ° C at a rate of 10 ° C / min. And let it stand for 1 minute. Thereafter, the measurement is performed at a heating rate of 50 ° C./min. Among the observed endothermic peaks, the temperature of the peak on the highest temperature side is defined as the highest endothermic peak temperature.

[Glass transition temperature 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 baseline extension below the endothermic peak temperature and the tangent that indicates the maximum slope from the peak rise to the peak apex. The glass transition temperature is assumed.

[Acid value of the resin]
Measured according to the method of JIS K0070. However, only the measurement solvent is 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)).

[Hydroxyl value of the resin]
Measured according to the method of JIS K0070.

[Number average molecular weight of resin]
The molecular weight distribution is measured by the gel permeation chromatography (GPC) method according to the following method to determine the number average molecular weight.
(1) Preparation of sample solution Dissolve the sample in tetrahydrofuran at 25 ° C so that the concentration is 0.5 g / 100 ml. Next, this solution is filtered using a fluororesin filter (manufactured by ADVANTEC, DISMIC-25JP) having a pore size of 0.2 μm to remove insoluble components, thereby obtaining a sample solution.
(2) Molecular weight measurement Using the following measuring device and analytical column, tetrahydrofuran is flowed as an eluent at a flow rate of 1 ml / min, and the column is stabilized in a constant temperature bath at 40 ° C. Measurement is performed by injecting 100 μl of the sample solution. The molecular weight of the sample is calculated based on a calibration curve prepared in advance. At this time, several types of monodisperse polystyrene (A-500 (5.0 × 10 ² ), A-1000 (1.01 × 10 ³ ), A-2500 (2.63 × 10 ³ ), A- 5000 (5.97 × 10 ³ ), F-1 (1.02 × 10 ⁴ ), F-2 (1.81 × 10 ⁴ ), F-4 (3.97 × 10 ⁴ ), F-10 (9.64 × 10 ⁴ ), F- 20 (1.90 × 10 ⁵ ), F-40 (4.27 × 10 ⁵ ), F-80 (7.06 × 10 ⁵ ), F-128 (1.09 × 10 ⁶ )) prepared as standard samples are used.
Measuring device: HLC-8220GPC (manufactured by Tosoh Corporation)
Analytical column: GMHXL + G3000HXL (manufactured by Tosoh Corporation)

[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).

[Average particle diameter of external additive]
The average particle diameter refers to the number average particle diameter and refers to the average value of the particle diameters of 500 particles measured from a scanning electron microscope (SEM) photograph of the external additive. When there is a major axis and a minor axis, the major axis is indicated.

[Production of resin]
Resin Production Example 1 [Resin 1-9]
The raw material monomer and the esterification catalyst 1 shown in Tables 1 and 2 are placed in a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen inlet tube, and in a mantle heater in a nitrogen atmosphere. Then, the temperature was raised to 180 ° C. and then raised to 210 ° C. over 5 hours. Thereafter, it was confirmed that the reaction rate reached 70% or higher at 210 ° C., and the esterification catalyst 2 was added. Then, it heated up to 220 degreeC and it reacted until it reached the softening point shown in Table 1, 2 at 8.0 kPa, and amorphous polyester (resin 1-9) was obtained. The reaction rate means a value of the amount of produced reaction water / theoretical product water amount × 100.

Resin Production Example 2 [Resin 10, 11]
The raw material monomer and the esterification catalyst 1 shown in Table 2 were put into a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen introduction tube, and in a mantle heater in a nitrogen atmosphere. After raising the temperature to 180 ° C, the temperature was raised to 210 ° C over 5 hours. Thereafter, the temperature was raised to 220 ° C., and the reaction was carried out at 8.0 kPa until the softening point shown in Table 2 was reached to obtain amorphous polyesters (resins 10 and 11).

Resin Production Example 3 [Resin 12]
The raw material monomer and the esterification catalyst 1 shown in Table 2 were put into a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen introduction tube, and in a mantle heater in a nitrogen atmosphere. After raising the temperature to 180 ° C, the temperature was raised to 210 ° C over 5 hours. Thereafter, at a stage before the reaction rate reached 70% at 210 ° C., the esterification catalyst 2 was added. Thereafter, the temperature was raised to 220 ° C., and the reaction was performed at 8.0 kPa until the softening point shown in Table 2 was reached, to obtain an amorphous polyester (resin 12).

Resin Production Example 4 [Resin 13]
The raw material monomer, esterification catalyst 1 and esterification catalyst 2 shown in Table 2 were put into a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen inlet tube, and the atmosphere was put into a nitrogen atmosphere. In the mantle heater, the temperature was raised to 180 ° C. and then raised to 210 ° C. over 5 hours. Thereafter, the temperature was raised to 220 ° C., and the reaction was performed at 8.0 kPa until the softening point shown in Table 2 was reached, to obtain an amorphous polyester (resin 13).

Resin Production Example 5 [Resin 14]
The raw material monomers shown in the table and the esterification catalyst 1 were placed in a 5-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen inlet tube, and in a mantle heater in a nitrogen atmosphere. After raising the temperature to 180 ° C, the temperature was raised to 210 ° C over 5 hours. Thereafter, the reaction was carried out at 8.0 kPa until the reaction rate shown in Table 2 was reached. Thereafter, the pressure was returned to normal pressure (atmospheric pressure), the esterification catalyst 2 was added, the temperature was raised to 220 ° C., and the reaction was performed for 1 hour. Then, it reacted until it reached the softening point shown in Table 2 at 8.0 kPa, and amorphous polyester (resin 14) was obtained.

[Manufacture of toner for developing electrostatic image]
Examples 1 to 10 and Comparative Examples 1 to 3
100 parts by weight of binder resin shown in Table 3, 5 parts by weight of colorant “Regal 330R” (Cabot, carbon black), release agent “Mitsui High Wax NP055” (Mitsui Chemicals, polypropylene wax, melting point: 125 ℃) 2 parts by mass, and 1 part by mass of negatively chargeable charge control agent `` Bontron E-81 '' (made by Orient Chemical Industry Co., Ltd.) were thoroughly mixed with a Henschel mixer, and then rotated in the same direction using a twin screw extruder. Melt kneading was performed at a speed of 200 r / min and a heating temperature of 80 ° C. in the roll. The obtained melt-kneaded product was cooled and coarsely pulverized, then pulverized with a jet mill and classified to obtain toner particles having a volume median particle size (D ₅₀ ) of 8 μm.

  To 100 parts by mass of the toner particles obtained, 1.0 part by mass of hydrophobic silica “NAX-50” (manufactured by Nippon Aerosil Co., Ltd., hydrophobizing agent: HMDS, average particle size: 30 nm) is added and mixed with a Henschel mixer. Thus, a toner was obtained.

Test Example 1 [low temperature fixability]
Toner was installed in a machine that improved the fixing machine of the copier “AR-505” (manufactured by Sharp Corporation) so that it can be fixed outside the machine, and paper manufactured by Sharp Corporation [CopyBond SF-70NA ( 75 g / m ² )] on the paper in an unfixed state. Using a fixing machine (fixing speed 390mm / sec) adjusted so that the total fixing pressure is 40kgf, the temperature of the fixing roller is gradually increased from 100 ° C to 240 ° C in 10 ° C increments. A fixing test was conducted. “UNICEF Cellophane” (Mitsubishi Pencil Co., Ltd., width: 18 mm, JISZ-1522) was pasted on the fixed image, passed through a fixing roller set at 30 ° C., and then the tape was peeled off. The optical reflection density before and after the tape was peeled off was measured using a reflection densitometer “RD-915” (manufactured by Macbeth), and the ratio between the two (after peeling / before sticking × 100) was initially 90%. The fixing roller temperature exceeding the minimum fixing temperature was used, and the low temperature fixing property was evaluated. The results are shown in Table 3.

Test Example 2 [Preservation]
4 g of toner was left for 72 hours in an environment at a temperature of 55 ° C. and a humidity of 60%. After standing, the degree of toner aggregation occurrence was visually observed every 24 hours, and storage stability was evaluated according to the following evaluation criteria. The results are shown in Table 3.

〔Evaluation criteria〕
A: Aggregation is not observed even after 72 hours.
B: Aggregation is observed after 72 hours.
C: Aggregation is observed after 48 hours.
D: Aggregation is observed after 24 hours

Test Example 3 [Durability]
“Page Presto N-4” (manufactured by Casio Computer Co., Ltd., fixing: contact fixing method, development: non-magnetic one-component development method, developing roll diameter: 2.3 cm) with toner mounted, temperature 32 ° C, humidity 85% Underneath, an oblique stripe pattern with a blackening rate of 5.5% was continuously printed. In the middle, a black solid image was printed every 500 sheets, and the presence or absence of streaks on the image was confirmed. Printing was stopped when streaks occurred on the image, and printing was performed up to 6000 sheets. The number of prints until the time when the streaks were visually observed on the image was defined as the number of streaks due to the fusion and fixing of the toner on the developing roll, and the durability was evaluated. In other words, it can be determined that the greater the number of sheets where no streaking occurs, the higher the durability of the toner. The results are shown in Table 3.

Test Example 4 [Gloss]
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 an external fixing device modified from the oilless fixing method DL-2300 (manufactured by Konica Minolta), the fixing roll rotation speed is set to 265 mm / sec and the fixing roll temperature in the fixing device is set to 170 ° C. Setting and fixing processing were performed to obtain a fixed image. The glossiness was measured using the fixed image. Glossiness was measured by using a gloss meter “PG-1” (Nippon Denshoku Industries Co., Ltd.) with a light source set at 60 ° to measure gloss. The results are shown in Table 3. The larger the gloss value, the better the gloss.

  From the above results, it can be seen that the toners of the examples are all excellent in low-temperature fixability, durability, storage stability and gloss of printed matter as compared with the toners of the comparative examples.

  The polyester-based toner binder resin obtained by the method of the present invention is suitably used for toners used for developing latent images formed in electrophotography, electrostatic recording, electrostatic printing, and the like. is there.

Claims (6)

Step 1 of polycondensing an alcohol component containing an aliphatic diol and a carboxylic acid component containing a carboxylic acid compound having a furan ring until the reaction rate reaches 70 to 99%, and the polycondensation obtained in Step 1 A method for producing a polyester-based toner binder resin , further comprising a step 2 of adding an organic compound having a sulfo group to the product and performing polycondensation , wherein the organic compound having a sulfo group has an alkyl group having 1 carbon atom. A method for producing a binder resin for a polyester-based toner, which is an alkylbenzenesulfonic acid of ˜22 .   The manufacturing method of Claim 1 which performs the process 1 in presence of a tin catalyst or a titanium catalyst.   The manufacturing method of Claim 1 or 2 whose usage-amount of the organic compound which has a sulfo group is 0.01-0.5 mass part with respect to 100 mass parts of total amounts of the alcohol component and carboxylic acid component with which the process 1 is provided.   The manufacturing method in any one of Claims 1-3 whose reaction temperature of the process 2 is 160-240 degreeC. The production method according to any one of claims 1 to 4 , wherein the aliphatic diol contains an aliphatic diol having a hydroxyl group bonded to a secondary carbon atom. The mass ratio of the tin catalyst or titanium catalyst used in step 1 to the organic compound having a sulfo group used in step 2 (tin catalyst or titanium catalyst / organic compound having a sulfo group) is 1/2 to 50/1. claim 2-5 the method according to any one.