JP6732851B2 - Toner binder and toner composition - Google Patents

Description

The present invention relates to toner binders and toner compositions.

In recent years, there has been an increasing need for environmental load reduction (energy saving) for copying machines, printers, etc. As a toner that meets this need, the development of a toner that can achieve both low-temperature fixing property and heat-resistant storage stability is required. ing.
As one of means for improving the low temperature fixability of the toner, there is a method using a wax. However, because the compatibility of wax and polyester resin is poor, the wax is not evenly dispersed in the toner, and lumps of wax bleed out on the toner surface, resulting in poor heat-resistant storage stability of the toner. There is a problem that the effect of improving the fixability is reduced.
As a measure for improving the dispersibility of wax, Patent Document 1 discloses a toner containing alkylsuccinic acid or/and alkenylsuccinic acid having a limited number of carbons and a structure as a monomer of a polyester resin. Although a certain degree of effect has been obtained with respect to both heat resistance and storage stability, the image quality stability during continuous copying is not sufficient, and further improvement in performance is desired.

JP, 2016-38449, A

An object of the present invention is to provide a toner binder and a toner composition capable of achieving both low-temperature fixability and heat-resistant storage stability and having excellent image stability during continuous copying.

The present inventors have arrived at the present invention as a result of extensive studies to solve these problems. That is, the present invention is the following two inventions.
A toner binder containing a polyester resin (A) which is a reaction product of a polyol component (x) and a polycarboxylic acid component (y), wherein the polycarboxylic acid component (y) has a branched alkyl group (r1). , (R1) having a carbon number of 15 to 32, alkylsuccinic acid (y10), and a branched alkyl group (r2), and (r2) having a carbon number of 15 to 32, alkylsuccinic anhydride (y11), branched. An alkenyl succinic acid having an alkenyl group (r3), a alkenyl succinic acid (y20) having 15 to 32 carbon atoms in (r3) and a branched alkenyl group (r4), and having 15 to 32 carbon atoms in (r4). From the acid anhydride (y21), the mono or diester of the above (y10) and an aliphatic monoalcohol having 1 to 4 carbon atoms, and the mono or diester of the above (y20) and an aliphatic monoalcohol having 1 to 4 carbon atoms. At least one selected from the group consisting of (r1), (r2), (r3) and (r4) each having two or more methyl groups, and (y10), (y11), (y20) and (y10). A toner composition containing a toner binder in which the total number of moles of y21) is 3 to 50 mol% based on the total number of moles of (y), and the toner binder and a colorant.

According to the present invention, it is possible to provide both low temperature fixability and heat resistant storage stability, and to provide a toner binder and a toner composition that are excellent in image quality stability during continuous copying.

Hereinafter, the present invention will be described in detail.
The polyester resin (A) used in the present invention is a reaction product of the polyol component (x) and the polycarboxylic acid component (y).

Examples of the polyol component (x) include diols and polyols having 3 to 8 valences or 9 valences or more.
As the diol, an alkylene glycol having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1, 9-nonane diol, 1,10-decane diol, 1,12-dodecane diol, 1,18-octadecane diol, 1,22-docosane diol, 1,30-triacontane diol, etc.), having 4 to 36 carbon atoms. Alkylene ether glycols (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.), alicyclic diols having 6 to 36 carbon atoms (1,4-cyclohexanedimethanol and hydrogenated bisphenol) A), an alkylene oxide adduct of the alicyclic diol (preferably having an addition mole number of 1 to 30), an aromatic diol [monocyclic dihydric phenol (hydroquinone, etc.) and bisphenol], and an alkylene of the aromatic diol. Examples thereof include oxide adducts (preferably 2 to 30 moles added).
Of these, alkylene glycols and aromatic diols having 2 to 36 carbon atoms are preferable, and alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols are more preferable, from the viewpoints of low temperature fixability and heat resistant storage stability.
In the alkylene oxide, the number of carbon atoms of the alkylene group is preferably 2 to 4, and as the alkylene oxide, ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 2,3-, 1, 3- or iso-butylene oxide, tetrahydrofuran and the like are preferable.

The alkylene oxide adduct of bisphenols is obtained by adding alkylene oxide (hereinafter, "alkylene oxide" may be abbreviated as AO) to bisphenols. Examples of the bisphenols include those represented by the following general formula (1).

HO-Ar-P-Ar-OH (1)
[In the formula, P represents an alkylene group having 1 to 3 carbon atoms, —SO ₂ —, —O—, —S— or a direct bond, and Ar is a halogen atom or an alkyl group having 1 to 30 carbon atoms. It represents a phenylene group which may be substituted. ]

Specific examples of the bisphenols include bisphenol A, bisphenol F, bisphenol B, bisphenol AD, bisphenol S, trichlorobisphenol A, tetrachlorobisphenol A, dibromobisphenol F, 2-methylbisphenol A, 2,6-dimethylbisphenol A and 2,2′-diethylbisphenol F and the like can be mentioned, and these can be used in combination of two or more kinds.

As the alkylene oxide to be added to these bisphenols, an alkylene oxide having 2 to 4 carbon atoms is preferable, and specifically, ethylene oxide (hereinafter, "ethylene oxide" may be abbreviated as EO) and propylene oxide. (Hereinafter, "propylene oxide" may be abbreviated as PO), 1,2-, 2,3-, 1,3- or iso-butylene oxide, tetrahydrofuran (hereinafter sometimes referred to as THF), and Combinations of two or more of these may be mentioned. Of these, EO and/or PO is preferable. The number of moles of AO added is preferably 2 to 30 moles, more preferably 2 to 10 moles.

Among the alkylene oxide adducts of bisphenols, preferred are EO and/or PO adducts of bisphenol A (average addition mole number is preferably 2 to 4, more preferably 2 to 3) from the viewpoint of toner fixability. is there.

Examples of the 3- to 8-valent polyols include 3- to 8-valent aliphatic polyhydric alcohols having 3 to 36 carbon atoms (alkane polyol and its intramolecular or intermolecular dehydrated product [glycerin, trimethylolethane, trimethylolpropane, pentaerythritol. , Sorbitol, sorbitan, polyglycerin and dipentaerythritol, etc.]), saccharides and derivatives thereof (sucrose and methylglucoside, etc.), and alkylene oxide adducts of the above aliphatic polyhydric alcohols (AO addition mole number is preferably 1 to 30), alkylene oxide adducts of trisphenols (trisphenol PA, etc.) (preferably 2 to 30 as the number of moles of addition of AO), novolac resins (phenol novolac, cresol novolac, etc.) are included, and the average degree of polymerization is 3 ~60) alkylene oxide adduct (preferably 2 to 30 as the number of moles of addition of AO).

Examples of the polyol having 9 or more valences include aliphatic polyhydric alcohols having 3 to 36 carbon atoms and having 9 valences or more (alkane polyol and its intramolecular or intermolecular dehydration product [glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol , Sorbitan, polyglycerin, dipentaerythritol, etc.]), saccharides and derivatives thereof (sucrose, methyl glucoside, etc.), and alkylene oxide adducts of the above aliphatic polyhydric alcohols (preferably 1 to 30 as the number of moles of AO added). , Alkylene oxide adducts of trisphenols (trisphenol PA, etc.) (preferably 2 to 30 as the number of moles of addition of AO), novolac resins (phenol novolac and cresol novolac, etc. are included, and the average degree of polymerization is 3 to 60. )) alkylene oxide adduct of () (preferably 2 to 30 as the number of moles of addition of AO) and the like.

Among the polyol components (x), those which are preferable from the viewpoint of achieving both low-temperature fixability and hot offset resistance are preferably alkylene glycols having 2 to 12 carbon atoms, alkylene oxide adducts of bisphenols (number of moles of addition of AO of 2 to 30). ) With an alkylene oxide adduct of an aliphatic polyhydric alcohol having 3 to 8 valences or 9 valences or higher (2 to 30 moles of AO added) and an alkylene oxide adduct of novolak resin (2 to 30 moles of AO added). There are more preferable alkylene glycols having 2 to 10 carbon atoms, alkylene oxide adducts of bisphenols (2 to 5 moles of AO added), 3 to 8 valent aliphatic polyhydric alcohols and alkylene oxides of novolak resins. It is an adduct (the number of moles of addition of AO is 2 to 30), and particularly preferably, an alkylene glycol having 2 to 6 carbon atoms, an alkylene oxide adduct of bisphenol A (the number of moles of addition of AO of 2 to 5), and a trivalent fat. Group polyhydric alcohols, most preferably ethylene glycol, propylene glycol, alkylene oxide adducts of bisphenol A (additional mole number of AO 2-3) and trimethylolpropane.

The polycarboxylic acid component (y) of the polyester resin (A) used in the present invention is
Alkyl succinic acid (y10) having a branched alkyl group (r1) and having a carbon number of 15 to 32 in (r1), having a branched alkyl group (r2), and having a carbon number of 15 to 32 in (r2) A succinic anhydride (y11), a branched alkenyl group (r3), an alkenylsuccinic acid (y20) having 15 to 32 carbon atoms in (r3) and a branched alkenyl group (r4), Alkenyl succinic anhydride having 15 to 32 carbon atoms (y21), mono- or diester of the above (y10) and aliphatic monoalcohol having 1 to 4 carbon atoms, and (y20) and fat having 1 to 4 carbon atoms. Containing at least one member selected from the group consisting of mono- or diesters with group monoalcohols, and (r1), (r2), (r3) and (r4) each have two or more methyl groups, and (y10) above. , (Y11), (y20) and (y21) are 3 to 50 mol% based on the total number of mols of (y).

Examples of (y10) and (y20) include compounds represented by the following general formula (2), and examples of (y11) and (y21) include the following general formula (3). And the like. R ¹ in the general formulas (2) and (3) is an alkyl group or an alkenyl group having two or more methyl groups and having 15 to 32 carbon atoms.

Examples of the mono- or diester of the (y10) and the aliphatic monoalcohol having 1 to 4 carbon atoms and the mono- or diester of the (y20) and the aliphatic monoalcohol having 1 to 4 carbon atoms include, for example, the following general formulas: The compound etc. which are represented by (4) are mentioned. The mono- or diesters of (y10) and (y20) used (y10) and (y20) by removing the aliphatic monoalcohol having 1 to 4 carbon atoms after the transesterification reaction with the polyol component (x). The same polyester resin (A) as in the case can be obtained, and the same effect can be obtained. R ¹ in the general formula (4) is an alkyl group or an alkenyl group having 15 to 32 carbon atoms and containing two or more methyl groups, and R ² and R ^{3 in} the general formula (4) have 1 to 4 carbon atoms. It is an alkyl group.

The number of methyl groups contained in the alkyl group contained in (y10) and (y11) and the alkenyl group contained in (y20) and (y21) is 2 or more from the viewpoint of heat resistant storage stability, and preferably 3 to It is 4. From the viewpoint of low-temperature fixability and heat-resistant storage stability, R ¹ in the general formulas (2), (3) and (4) is preferably an alkyl group or an alkenyl group having 15 to 25 carbon atoms, and More preferably, it is an alkyl group or an alkenyl group of the number 15-18. When the number of carbon atoms of the alkyl group contained in (y10) and (y11) and the alkenyl group contained in (y20) and (y21) is less than 15, low temperature fixability is deteriorated, and when it exceeds 32, heat resistant storage stability is high. Becomes worse.
The reason for this effect is not clear, but alkylsuccinic acid (y10), alkylsuccinic anhydride (y11), alkenylsuccinic acid (y20) or alkenylsuccinic anhydride used as a monomer in the polyester (A) of the present invention. It is presumed to be derived from the aliphatic carbon chain of (y21). The (y10), (y11), (y20) and (y21) having a carbon chain according to claim 1 have an affinity between the polyester (A) and the wax due to the bulky and highly sterically hindered structure of the carbon chain. Can be increased. Therefore, it is considered that the bleed-out of the wax can be prevented, and the low temperature fixing property, the heat resistant storage property and the image quality stability during continuous copying are improved.

The average number of methyl groups contained in R ¹ in the general formulas (2), (3) and (4) is the same as the above (y10), (y11), (y20) and (y21) under the following conditions. NMR is calculated by calculating the ratio of the peak area (δ=0.8 to 0.9) derived from the methyl group to the total peak area derived from other than the methyl group (methylene group and methine group). It can be obtained by the method described in the calculation method.
< ¹ H-NMR measurement conditions>
Device: Bruker BioSpin "AVANCE300"
Number of integrations: 16 times Sample amount: 10 mg
Solvent: DMSO-d6

<Calculation method of methyl number>
(1) ¹ H-NMR measurement is performed under the above conditions, and the measured integrated intensity ratio [(peak area derived from methyl group)/(total peak area other than methyl group)] is determined from the measurement result.
(2) The obtained measured integrated intensity ratio is compared with the theoretical integrated intensity ratio when the number of methyl groups is X and X+1 to determine the number X of methyl groups that satisfies the following inequality 1. Note that X is an integer.
Theoretical integrated intensity ratio when the number of methyl groups is X <Measured integrated intensity ratio <Theoretical integrated intensity ratio when the number of methyl groups is X+1 (Inequality 1)
(3) The measured integrated intensity ratio and the number X of methyl groups are substituted into the following formula (1) to obtain the number of methyl groups.
Number of methyl groups=(measured integrated intensity ratio−theoretical integrated intensity ratio in the case of methyl group number X)/(theoretical integrated intensity ratio in the case of methyl group number X+1−theoretical integrated intensity ratio in the case of methyl group number X)+X (Calculation formula 1 )

From the viewpoint of steric hindrance, the above (y10), (y11), (y20) and (y21) are preferably reaction products of at least one selected from maleic acid and fumaric acid with an alkylene compound. Examples of the alkylene compound include those having 15 to 32 carbon atoms having two or more methyl groups, and those obtained by synthesizing ethylene, propylene, isobutylene, normal butylene and the like, and preferably tetramers thereof. A pentamer, a hexamer, etc. can be used. As a method for synthesizing these alkylene compounds, the methods described in JP-A-2015-34294, JP-A-2005-15383 and JP-A-1994-65110 can be used.
The alkylene compounds obtained by the methods described in JP-A-2015-34294, JP-A-2005-15383 and JP-A-1994-65110 have two or more methyl groups, and these alkylene compounds are reacted with maleic acid or fumaric acid. By this, a branched alkylene succinic acid having two or more methyl groups or an anhydride thereof can be obtained.
The method of reacting at least one selected from maleic acid and fumaric acid with an alkylene compound is not particularly limited, and a known method can be used. From the viewpoint of ease of production, a method obtained by mixing the alkylene compound with maleic acid or fumaric acid and heating the mixture is preferable. For the reaction conditions, reference can be made to JP-A 2004-175804 and the like.

Preferred as (y10) is a product obtained by adding hydrogen to a reaction product of propylene pentamer, propylene hexamer, butylene pentamer, hexene pentamer or hexentrimer and maleic anhydride, and preferred as (y11). Is an anhydride which is preferable as the above (y10). Preferred as (y20) is a reaction product of propylene pentamer, propylene hexamer, butylene pentamer, hexene pentamer or hexentrimer and maleic anhydride, and preferred as (y21) is (y20). ), which is preferable as an anhydride.

The polycarboxylic acid component (y) of the polyester resin (A) used in the present invention contains a polycarboxylic acid component other than the above (y10), (y11), (y20) and (y21). Examples of polycarboxylic acid components other than (y10), (y11), (y20) and (y21) include dicarboxylic acids and polycarboxylic acids having a valence of 3 to 6 or 7 or more. As the polycarboxylic acid component (y), one type may be used, or two or more types may be used in combination.

Examples of the dicarboxylic acid include alkanedicarboxylic acid having 2 to 50 carbon atoms (oxalic acid, malonic acid, succinic acid, adipic acid, leparginic acid, sebacic acid, etc.), alkene dicarboxylic acid having 4 to 50 carbon atoms (maleic acid, fumaric acid). , Citraconic acid, mesaconic acid, itaconic acid, glutaconic acid, etc.), aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.), and vinyl polymers of unsaturated carboxylic acids ( Α-olefin/maleic acid copolymers having a number average molecular weight of 450 to 10,000) and the like.

Examples of the polycarboxylic acid having 3 to 6 valences or 7 valences or more include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid and pyromellitic acid, etc.) and aliphatic tricarboxylic acids having 6 to 36 carbon atoms (hexane tricarboxylic acid). Acids, etc.), vinyl polymers of unsaturated carboxylic acids (styrene/maleic acid copolymers having a number average molecular weight of 450 to 10,000, styrene/acrylic acid copolymers, styrene/fumaric acid copolymers, etc.) Can be mentioned.
As the polycarboxylic acid component (y) other than the above (y10), (y11), (y20) and (y21), anhydrides, lower alkyl (C1 to C4) esters (methyl) of these polycarboxylic acids are used. Ester, ethyl ester, isopropyl ester, etc.) may be used.

Among the polycarboxylic acid components other than (y10), (y11), (y20), and (y21), preferred are those having 2 to 50 carbon atoms from the viewpoint of achieving both low-temperature fixability and hot offset resistance. Dicarboxylic acids, alkene dicarboxylic acids having 4 to 50 carbon atoms, aromatic dicarboxylic acids having 8 to 20 carbon atoms and aromatic polycarboxylic acids having 9 to 20 carbon atoms, and more preferably adipic acid and 16 to 50 carbon atoms. Alkenyl succinic acid, terephthalic acid, isophthalic acid, maleic acid, fumaric acid, trimellitic acid, pyromellitic acid and combinations thereof, particularly preferably adipic acid, terephthalic acid, isophthalic acid, trimellitic acid and these It is a combination. The anhydrides and lower alkyl esters of these acids are likewise preferred.

The total number of moles of (y10), (y11), (y20) and (y21) contained in the polycarboxylic acid component (y) is 3 to 50% by mole based on the total number of moles of (y). And preferably 8 to 40 mol %, and more preferably 13 to 30 mol %. When the total number of moles of (y10), (y11), (y20) and (y21) is less than 3 mol% based on the total number of moles of (y), the low temperature fixability deteriorates, and 50 If it exceeds mol %, the hot offset property deteriorates.

In the present invention, the polyester resin (A) is obtained by polycondensing the polyol component (x) and the polycarboxylic acid component (y). The production method of the above (A) is not particularly limited, and a known polyester production method can be used.
For example, the reaction can be carried out in an inert gas (nitrogen gas or the like) atmosphere at a reaction temperature of preferably 150 to 240°C, more preferably 160 to 225°C, and particularly preferably 170 to 220°C.

An esterification catalyst can be used if necessary during the production of the polyester resin. Esterification catalysts include tin-containing catalysts (dibutyltin oxide, etc.), antimony trioxide, titanium-containing catalysts [titanium alkoxide, potassium oxalate titanate, titanium terephthalate, titanium terephthalate alkoxide, titanium dihydroxybis (triethanolaminate). , Titanium monohydroxytris (triethanolaminate), titanyl bis (triethanolaminate), tantributoxy terephthalate, titanium triisopropoxy terephthalate and titanium diisopropoxy diterephthalate), zirconium-containing catalysts (zirconyl acetate etc.) and Examples thereof include zinc acetate. Of these, a titanium-containing catalyst is preferable. It is also effective to reduce the pressure in order to improve the reaction rate in the final stage of the reaction.

The reaction ratio of the polyol component (x) and the polycarboxylic acid component (y) is preferably 2/1 to 1/2, more preferably 1. 1 as the equivalent ratio [OH]/[COOH] of the hydroxyl group and the carboxyl group. It is 4/1 to 1/1.2.

The polyester resin (A) used in the present invention preferably has a softening point (hereinafter, also referred to as Tm) of 90 to 150° C., more preferably 100 from the viewpoint of hot offset resistance and low temperature fixability. ˜140° C., more preferably 110˜130° C.
The Tm of the above (A) can be adjusted by the molecular weight of the above (A), and can be adjusted to the above preferable range by adjusting the following peak top molecular weight of the THF-soluble component to a preferable range.

In the present invention, the Tm of the polyester resin (A) can be measured by the following method.
<Method of measuring Tm of polyester resin (A)>
Using a Koka type flow tester (for example, CFT-500D manufactured by Shimadzu Corporation), a load of 1.96 MPa is applied by a plunger while heating 1 g of a measurement sample at a temperature rising rate of 6° C./min. Extrude from a nozzle with a diameter of 1 mm and a length of 1 mm to draw a graph of "plunger drop (flow value)" and "temperature", and graph the temperature corresponding to 1/2 of the maximum plunger drop. The value (temperature when half of the measured sample flows out) is read as Tm.

The acid value of the polyester resin (A) is preferably 7 to 21 mgKOH/g, more preferably 8 to 13 mgKOH/g. When the acid value is 7 to 21 mgKOH/g, the emulsifiability becomes better when the above (A) is used as a material for the chemical toner.
The acid value of (A) can be adjusted by the charging ratio of the raw materials [reaction ratio of the polyol component (x) and the polycarboxylic acid component (y)] and the reaction time. For example, when it is desired to increase the acid value, the charging ratio of the polycarboxylic acid component (y) is increased or the reaction time is shortened.
The acid value of (A) is measured by the method specified in JIS K0070 (1992 version).

The hydroxyl value of the polyester resin (A) is preferably 0 to 50 mgKOH/g, more preferably 5 to 40 mgKOH/g, and particularly preferably 10 to 30 mgKOH/g. The hydroxyl value of (A) can be measured by the method specified in JIS K0070 (1992 version).

The glass transition temperature (hereinafter sometimes referred to as Tg) of the polyester resin (A) is preferably 45 to 75°C. When the Tg of (A) is 75°C or lower, the low-temperature fixability is further improved, and when it is 45°C or higher, the preservability is further improved.
In addition, Tg can be measured by the method (DSC method) prescribed in ASTM D3418-82 using DSC20 and SSC/580 manufactured by Seiko Instruments Inc.

The peak top molecular weight (hereinafter sometimes referred to as Mp) of the THF-soluble component of the polyester resin (A) is preferably 2,000 to 15,000 from the viewpoint of compatibility of toner durability and low-temperature fixability. , And more preferably 6,000 to 12,000.

In the present invention, the peak top molecular weight, the number average molecular weight (hereinafter sometimes referred to as Mn), and the weight average molecular weight (hereinafter sometimes referred to as Mw) of a resin such as a polyester resin are determined by gel permeation chromatography. It can be measured under the following conditions using (GPC).

Apparatus (one example): Tosoh Corp. HLC-8120
Column (one example): TSK GEL GMH6 2 [manufactured by Tosoh Corporation]
Measurement temperature: 40℃
Sample solution: 0.25 wt% THF solution Injection volume of solution: 100 μl
Detector: Refractive index detector Reference substance: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (molecular weight 500 1,050 2,800 5,970 9,100 100,18,100 37,900 96,400 190,000) 355,000 1,090,000 2,890,000)
The molecular weight is measured by dissolving the polyester resin in THF and filtering the insoluble matter with a glass filter to obtain a sample solution.

The toner composition of the present invention contains a toner binder containing the polyester resin (A) and a colorant.
As the colorant, all of the dyes and pigments used as the colorant for toner can be used. Specifically, carbon black, iron black, Sudan black SM, first yellow G, benzidine yellow, pigment yellow, India first orange, irgasin red, paranitroaniline red, toluidine red, carmine FB, pigment orange R, lake red. 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orazol Brown B, Oil Pink OP, etc., and these are used alone. Alternatively, two or more kinds can be mixed and used. If necessary, magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt, nickel or a compound such as magnetite, hematite, ferrite) can be contained also as a colorant.
The content of the colorant is preferably 1 to 40 parts by weight, more preferably 3 to 10 parts by weight, based on 100 parts by weight of the toner binder of the present invention. When magnetic powder is used, it is preferably 20 to 150 parts by weight, more preferably 40 to 120 parts by weight.

A wax may be added to the toner composition of the present invention in order to improve low temperature fixability.

As the wax to be added, a hydrocarbon wax (w) having a melting point of 60 to 120° C. and a polyolefin wax having a melting point of 120 to 170° C. can be used, and a hydrocarbon wax (w) having a melting point of 60 to 120° C. is preferable.

Examples of the hydrocarbon wax (w) having a melting point of 60 to 120° C. include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, carnauba wax, montan wax, rice wax and low molecular weight polyethylene.

The content of wax in the toner binder is preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight, and further preferably 1 to 10% by weight.

The toner composition of the present invention may further contain additives such as a charge control agent and a fluidizing agent.

As the charge control agent, a nigrosine dye, a triphenylmethane dye containing a tertiary amine as a side chain, a quaternary ammonium salt, a polyamine resin, an imidazole derivative, a quaternary ammonium salt group-containing polymer, a metal-containing azo dye, a copper phthalocyanine dye , A salicylic acid metal salt, a benzylic acid boron complex, a sulfonic acid group-containing polymer, a fluorine-containing polymer, and a halogen-substituted aromatic ring-containing polymer.

The content of the charge control agent in the toner binder is preferably 0 to 20% by weight, more preferably 0.1 to 10% by weight, still more preferably 0.5 to 7.5% by weight.

Examples of the fluidizing agent include colloidal silica, alumina powder, titanium oxide powder, calcium carbonate powder and the like.
The content of the fluidizing agent in the toner binder is preferably 0 to 10% by weight, more preferably 0 to 5% by weight, still more preferably 0.1 to 4% by weight.

The method for producing the toner composition of the present invention is not particularly limited, and known production methods can be used. For example, it can be obtained by dry-blending the components of the above-mentioned toner excluding the fluidizing agent, and then melt-kneading them using a continuous kneader or the like.

The toner composition of the present invention can be made into a toner by roughly pulverizing it, atomizing it using a jet mill pulverizer, and then classifying it, and mixing a fluidizing agent. The volume average particle diameter (D50) of the toner is preferably 5 to 20 μm. The volume average particle diameter (D50) of the toner can be measured using a Coulter counter [trade name: Multisizer III (manufactured by Coulter)].
The obtained toner is mixed with carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with a resin (acrylic resin, silicone resin, etc.), if necessary, to form an electrical latent image. Used as a developer. The weight ratio of the toner to the carrier particles is preferably 1/99 to 100/0. It is also possible to form an electrical latent image by rubbing with a member such as a charging blade instead of the carrier particles.

The toner composition of the present invention is fixed on a support (paper, polyester film or the like, preferably paper) by a copying machine, a printer or the like to be used as a recording material. As a method for fixing to the support, a known heat roll fixing method, flash fixing method, or the like can be applied.

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto. In addition, Example 10 is Reference Example 1 and Example 11 is Reference Example 2.

<Preparation Example 1, Preparation of Fluorinated Zeolite Activator Carrier Used for Synthesis of Octene Oligomer Used for Alkenylsuccinic Acid>
The fluorinated zeolite activator carrier used during the synthesis of the alkylene compound was prepared. First, fluorination was performed by impregnating the zeolite "SYLOBEAD(R) [WR Grace] with ammonium fluoride corresponding to 10% by weight [Wako Pure Chemical Industries] by the incipient wetness method. The material was dried in a vacuum oven for 8 hours at 100° C. 10 g of the dried fluorinated zeolite was placed in a 4.45 cm quartz glass tube attached to the bottom of a sintered quartz disk and the disk was blown dry. The temperature of the quartz glass tube was raised to a final temperature of about 450° C. at a rate of about 400° C./hour using an electric furnace to dry the zeolite in dry air. The by-produced ammonia was removed while fluorinating for 3 hours, and then the zeolite was recovered, stored under dry nitrogen, and used without being exposed to the atmosphere.

<Production Example 2, Synthesis of alkylene compound (octene oligomer) used for alkenylsuccinic acid>
A solid addition funnel filled with 29.5 g of the fluorinated zeolite activator carrier obtained in Production Example 1 in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe (the same applies to the reaction baths used in the following Production Examples). Attached. Next, this reaction tank was purged with nitrogen, and thoroughly dried by washing with a 16 wt% tri-isobutylaluminum hexane solution (TIBA) [Tokyo Kasei Kogyo]. After removing the washed TIBA, 1.1 kg of 1-octene [Wako Pure Chemical Industries] was introduced into the reaction vessel through a cannula. The 1-octene was then heated to 95°C. Thereafter, 40.0 g of a 16% by weight TIBA hexane solution and then 230 mg of 1,1′-dibutylzirconocene dichloride [Tokyo Kasei Kogyo] dissolved in a minimum amount of 1-octene were added to the reaction tank. Then, when the whole amount of the fluorinated zeolite activator carrier was added with stirring, heat of reaction was generated. Next, the reaction mixture was heated to 95° C. and reacted for 6 hours. Then, TIBA was neutralized with 1.74 g of water. Next, this product was filtered, charged into an empty reaction tank, and fractionated under reduced pressure. The reaction tank was heated to 150° C., stirring was started, and the pressure reduction degree was gradually lowered to 0.7 kPa so as not to bump. Thereafter, the temperature was gradually raised, and a fraction at 180 to 200°C was recovered as an octene trimer and a fraction at 220 to 240°C was recovered as an octene tetramer.

<Production Example 3, Synthesis of alkenylsuccinic acid (y2-1)>
A reaction tank was charged with 163 parts by weight of maleic anhydride [Mitsui Chemicals] and 837 parts by weight of the octene trimer obtained in Production Example 2, and pressurized nitrogen substitution was repeated twice to 0.2 MPa. After the temperature was raised to 60° C., stirring was started, the temperature was raised to 215° C. over 3 hours, and then the reaction was carried out for 7 hours. After completion of the reaction, the temperature was lowered to 150° C., and the pressure reduction degree was gradually lowered to 0.7 kPa so as not to bump. After that, the temperature was gradually raised, and vacuum distillation was performed at 0.7 kPa. The fraction up to 200° C. or lower was recovered as an alkylene compound, and the fraction 215° C. or higher was recovered as (y2-1), and the measured number of methyl groups and carbon chain length are shown in Table 1.

<Production Example 4, Synthesis of alkenylsuccinic acid (y2-2)>
127 parts by weight of maleic anhydride and 873 parts by weight of the octene tetramer obtained in Production Example 2 were charged into a reaction tank, and pressurized nitrogen substitution was repeated twice to 0.2 MPa. After the temperature was raised to 60° C., stirring was started, the temperature was raised to 215° C. over 3 hours, and then the reaction was carried out for 7 hours. After completion of the reaction, the temperature was lowered to 150° C., and the pressure reduction degree was gradually lowered to 0.7 kPa so as not to bump. After that, the temperature was gradually raised, and vacuum distillation was performed at 0.7 kPa. The fraction up to 210°C was recovered as an alkylene compound, and the fraction up to 215°C was recovered as (y2-2).

<Production Example 5, Synthesis of alkenylsuccinic acid (y2-3)>
A reaction tank was charged with 237 parts by weight of maleic anhydride and 763 parts by weight of propylene pentamer [Parchem Fine & Chemicals], and pressurized nitrogen substitution was repeated twice to 0.2 MPa. After the temperature was raised to 60° C., stirring was started, the temperature was raised to 215° C. over 3 hours, and then the reaction was carried out for 7 hours. After completion of the reaction, the temperature was lowered to 150° C., and the pressure reduction degree was gradually lowered to 0.7 kPa so as not to bump. After that, the temperature was gradually raised, and vacuum distillation was performed at 0.7 kPa. A fraction up to 195°C or lower was recovered as an alkylene compound, and a fraction up to 195 to 210°C was recovered as (y2-3).

<Production Example 6, Synthesis of alkylsuccinic acid (y1-1)>
To the reaction layer, 250 parts by weight of alkenylsuccinic acid (y2-3) obtained in Production Example 5 and 750 parts by weight of acetone were charged, and 12.5 parts by weight of Raney nickel (NDHT-90 manufactured by Kawaken Fine Chemical Co., Ltd.) was added. Then, hydrogen gas was blown thereinto up to 0.3 MPa. The temperature was raised to 70° C. with stirring, and the reaction was performed for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, the degree of reduced pressure was gradually reduced to 0.7 kPa so as not to bump, and acetone was distilled off by reducing the pressure at 0.7 kPa for 4 hours or more to give alkylsuccinic acid (y1-1). Got

<Production Example 7, Synthesis of alkenylsuccinic acid (y2-5)>
The reaction layer was charged with 237 parts by weight of maleic acid [Mitsui Chemicals] and 763 parts by weight of propylene pentamer, and pressurized nitrogen substitution was repeated twice to 0.2 MPa. After the temperature was raised to 60° C., stirring was started, the temperature was raised to 215° C. over 3 hours, and then the reaction was carried out for 7 hours. After completion of the reaction, the temperature was lowered to 150° C., and the pressure reduction degree was gradually lowered to 0.7 kPa so as not to bump. After that, the temperature was gradually raised, and vacuum distillation was performed at 0.7 kPa. The fraction up to 195°C or lower was recovered as an alkylene compound, and the fraction up to 195 to 210°C was recovered as (y2-5).

<Production Example 8, Synthesis of alkylsuccinic acid (y1-2)>
To the reaction layer, 250 parts by weight of alkenylsuccinic acid (y2-5) obtained in Production Example 7 and 750 parts by weight of acetone were charged, and 12.5 parts by weight of Raney nickel (NDHT-90 manufactured by Kawaken Fine Chemical Co., Ltd.) was added. Then, hydrogen gas was blown thereinto up to 0.3 MPa. The temperature was raised to 70° C. with stirring, and the reaction was performed for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, the pressure reduction degree was gradually reduced to 0.7 kPa so as not to bump, and acetone was distilled off by reducing the pressure at 0.7 kPa for 4 hours or more to give alkylsuccinic acid (y1-2). Got

Of the alkenyl succinic acid (y2-1) to (y2-3), (y2-5) and alkyl succinic acid (y1-1) to (y1-2) obtained in Production Examples and the following compounds used in Examples: Table 1 shows the number of methyl groups and the carbon chain length.
・Isooctadecenyl succinic anhydride (y2-4) [Tokyo Chemical Industry]
-Ricacid DDSA (y2'-1) [Nippon Rika, 3-dodecenyl succinic anhydride]
・Ricacid OSA (y2'-2) [Nippon Rika, octenyl succinic anhydride]

<Example 1> [Synthesis of polyester A1]
In a reaction tank equipped with a cooling pipe, a stirrer, and a nitrogen introducing pipe (the same applies to the reaction tanks used in the following production examples), the raw materials were charged at the compounding ratio shown in Example 1 in Table 2, and the temperature was raised to 180°C. Then, the reaction was carried out at normal pressure for 1 hour. Then, the temperature was raised to 215° C. and the reaction was performed under a reduced pressure of 0.5 to 2.5 kPa. After reaching 215° C., the reaction was carried out as it was under reduced pressure, and when the Tm reached a target value, the reaction product was taken out to obtain polyester A1. The Tm, acid value, hydroxyl value, Tg, Mw, and Mp of the obtained polyester were measured by the methods described below, and the values are shown in Table 2.

<Example 2> [Synthesis of polyester A2]
Polyester A2 was obtained in the same manner as in <Polyester Production Example 1> except that the raw materials described in Example 2 in Table 2 were used. Table 2 shows Tm, acid value, hydroxyl value, Tg, Mw, and Mp of the obtained polyester.

<Example 3> [Synthesis of polyester A3]
Polyester A3 was obtained in the same manner as in <Polyester Production Example 1> except that the raw materials described in Example 3 in Table 2 were used. Table 2 shows Tm, acid value, hydroxyl value, Tg, Mw, and Mp of the obtained polyester.

<Example 4> [Synthesis of polyester A4]
Polyester A4 was obtained in the same manner as in <Polyester Production Example 1> except that the raw materials described in Example 4 of Table 2 were used. Table 2 shows Tm, acid value, hydroxyl value, Tg, Mw, and Mp of the obtained polyester.

<Example 5> [Synthesis of polyester A5]
Polyester A5 was obtained in the same manner as in <Polyester Production Example 1> except that the raw materials described in Example 5 of Table 2 were used. Table 2 shows Tm, acid value, hydroxyl value, Tg, Mw, and Mp of the obtained polyester.

<Example 6> [Synthesis of polyester A6]
Polyester A6 was obtained in the same manner as in <Polyester Production Example 1> except that the raw materials described in Example 6 in Table 2 were used. Table 2 shows Tm, acid value, hydroxyl value, Tg, Mw, and Mp of the obtained polyester.

<Example 7> [Synthesis of polyester A7]
Polyester A7 was obtained in the same manner as in <Polyester Production Example 1> except that the raw materials described in Example 7 of Table 2 were used. Table 2 shows Tm, acid value, hydroxyl value, Tg, Mw, and Mp of the obtained polyester.

<Example 8> [Synthesis of polyester A8]
Polyester A8 was obtained in the same manner as in <Polyester Production Example 1> except that the raw materials described in Example 8 of Table 2 were used. Table 2 shows Tm, acid value, hydroxyl value, Tg, Mw, and Mp of the obtained polyester.

<Example 9> [Synthesis of polyester A9]
Polyester A9 was obtained in the same manner as in <Polyester Production Example 1> except that the raw materials described in Example 9 in Table 2 were used. Table 2 shows Tm, acid value, hydroxyl value, Tg, Mw, and Mp of the obtained polyester.

<Example 10> [Synthesis of polyester A10]
Polyester A10 was obtained in the same manner as in <Polyester Production Example 1> except that the raw materials described in Example 10 in Table 2 were used. Table 2 shows Tm, acid value, hydroxyl value, Tg, Mw, and Mp of the obtained polyester.

<Example 11> [Synthesis of polyester A11]
Polyester A11 was obtained in the same manner as in <Polyester Production Example 1> except that the raw materials described in Example 11 in Table 2 were used. Table 2 shows Tm, acid value, hydroxyl value, Tg, Mw, and Mp of the obtained polyester.

<Example 12> [Synthesis of polyester A12]
Polyester A12 was obtained in the same manner as in <Polyester Production Example 1> except that the raw materials described in Example 12 of Table 2 were used. Table 2 shows Tm, acid value, hydroxyl value, Tg, Mw, and Mp of the obtained polyester.

<Example 13> [Synthesis of polyester A13]
Polyester A13 was obtained in the same manner as in <Polyester Production Example 1> except that the raw materials described in Example 13 in Table 2 were used. Table 2 shows Tm, acid value, hydroxyl value, Tg, Mw, and Mp of the obtained polyester.

<Example 14> [Synthesis of polyester A14]
Polyester A14 was obtained in the same manner as in <Polyester Production Example 1> except that the raw materials described in Example 14 in Table 2 were used. Table 2 shows Tm, acid value, hydroxyl value, Tg, Mw, and Mp of the obtained polyester.

<Example 15> [Synthesis of polyester A15]
Polyester A15 was obtained in the same manner as in <Polyester Production Example 1> except that the raw materials described in Example 15 in Table 2 were used. Table 2 shows Tm, acid value, hydroxyl value, Tg, Mw, and Mp of the obtained polyester.

<Comparative Example 1> [Synthesis of polyester A'1]
Polyester A′1 was obtained in the same manner as in <Polyester Production Example 1> except that the raw materials described in Comparative Example 1 in Table 2 were used. Table 2 shows Tm, acid value, hydroxyl value, Tg, Mw, and Mp of the obtained polyester.

<Comparative Example 2> [Synthesis of polyester A'2]
Polyester A′2 was obtained in the same manner as in <Polyester Production Example 1> except that the raw materials described in Comparative Example 2 in Table 2 were used. Table 2 shows Tm, acid value, hydroxyl value, Tg, Mw, and Mp of the obtained polyester.

<Comparative Example 3> [Synthesis of polyester A'3]
Polyester A′3 was obtained in the same manner as in <Polyester Production Example 1> except that the raw materials described in Comparative Example 3 in Table 2 were used. Table 2 shows Tm, acid value, hydroxyl value, Tg, Mw, and Mp of the obtained polyester.

The raw materials used for the production of polyester are as follows.
・Bisphenol A/PO2 mol addition product (BP-2P) [Sanyo Kasei]
・Bisphenol A/PO3 mol adduct (BP-3P) [Sanyo Chemical Industries]
・Bisphenol A/EO 2 mol adduct (BPE-20) [Sanyo Kasei]
・Trimethylolpropane (TMP) [Mitsubishi Gas Chemical]
・Terephthalic acid [Mitsui Chemicals]
・Isophthalic acid [Mitsubishi Gas Chemical]
・Trimellitic anhydride [Hyakukawa Chemical Co., Ltd.]
・Titanium diisopropoxy bistriethanol aminate [Matsumoto Fine Chemicals Organix TC-400]

<Method of measuring Tm of polyester resin (A)>
Using a Koka type flow tester [CFT-500D (manufactured by Shimadzu Corp.)], a load of 1.96 MPa was applied by a plunger while heating 1 g of a measurement sample at a temperature rising rate of 6° C./min. Extrude from a 1mm, 1mm long nozzle, draw a graph of "plunger drop (flow value)" and "temperature", and find the temperature corresponding to 1/2 of the maximum plunger drop from the graph. This value (the temperature at which half of the measurement sample flows out) was read and taken as Tm.

<Method for measuring acid value and hydroxyl value of polyester resin (A)>
It was measured by the method specified in JIS K0070 (1992 version).

<Method of measuring Tg of polyester resin (A)>
It was measured by a method (DSC method) specified in ASTM D3418-82 using Seiko Instruments Inc. DSC20, SSC/580.

<Measurement method of Mp and Mw of polyester resin (A)>
Apparatus (one example): Tosoh Corp. HLC-8120
Column (one example): TSK GEL GMH6 2 [manufactured by Tosoh Corporation]
Measurement temperature: 40℃
Sample solution: 0.25 wt% THF solution Injection volume of solution: 100 μl
Detector: Refractive index detector Reference substance: Standard polystyrene (TSK standard POLYSTYRENE) 12 points (molecular weight 500 1,050 2,800 5,970 9,100 100,18,100 37,900 96,400 190,000) 355,000 1,090,000 2,890,000)
The molecular weight was measured by dissolving the polyester resin in THF and filtering the insoluble matter with a glass filter to obtain a sample solution.

The polyesters A1 to A15 obtained in the examples and the A'1 to A'3 obtained in the comparative examples were made into toner by the following procedure and evaluated.

First, 100 parts of polyester, 6 parts of colorant, 7 parts of wax, and 3 parts of wax dispersant were premixed using a sample mill, and then kneaded with a twin-screw kneader [PCM-30 manufactured by Ikegai Co., Ltd.]. Then, after finely pulverizing using a supersonic jet crusher Lab Jet [manufactured by Nippon Pneumatic Mfg. Co., Ltd.], it was classified by an air stream classifier [MDS-I manufactured by Japan Pneumatic Mfg. Co., Ltd.] to obtain a particle size D50. 7 μm toner particles were obtained. Next, 0.5 part by weight of colloidal silica [Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.] was mixed with 100 parts by weight of the toner particles in a sample mill to obtain a toner composition for evaluation of each polyester.

The colorants, waxes and wax dispersants used in the preparation of the toner composition are as follows.
Colorant: "Carbon Black MA-100" [Mitsubishi Chemical]
Wax: "FNP0090" [Nippon Seiwa]
Wax dispersant: "Haimer WDA-1BE" [Sanyo Chemical Co., Ltd.]

The toner composition obtained by the above method was evaluated for low-temperature fixability, hot offset resistance, heat resistant storage stability, and image stability during continuous copying by the following methods. The evaluation results are shown in Table 2.

[Evaluation method]
[1] Low-temperature fixing property An unfixed image developed using a commercially available copying machine (AR5030; manufactured by Sharp) using the above toner composition was evaluated using a fixing machine of a commercially available copying machine (AR5030; manufactured by Sharp). did. The minimum fixing temperature was defined as the fixing roll temperature at which the residual ratio of the image density measured using a Macbeth reflection densitometer RD-191 (manufactured by Macbeth) after rubbing the fixed image with a pad was 70% or more. The lower the minimum fixing temperature, the better the low temperature fixing property.
[Judgment criteria]
◯: Minimum fixing temperature 120° C. or lower Δ: Minimum fixing temperature 120° C. to 130° C.
X: Minimum fixing temperature of 130°C or higher

[2] Hot offset resistance The fixing was evaluated in the same manner as in the evaluation method of the low temperature fixing property, and the presence or absence of hot offset on the fixed image was visually evaluated. The fixing roll temperature at which hot offset occurred was defined as the hot offset occurrence temperature. The higher the hot offset generation temperature, the better the hot offset resistance.
[Judgment criteria]
◯: Hot offset generation temperature 180° C. or higher Δ: Hot offset generation temperature 160° C. to 180° C.
×: Hot offset generation temperature 160°C or less

[3] Heat-resistant storage stability The toner was left standing in an atmosphere of 45°C for 24 hours, the degree of blocking was visually determined, and the heat-resistant storage stability was evaluated according to the following criteria.
[Judgment criteria]
◯: No blocking occurred.
Δ: Blocking occurs in part.
X: Blocking occurs on the whole.

[3] Image stability during continuous copying 30 g of a toner composition and 800 g of a ferrite carrier (f-150 manufactured by Powder Tech Co., Ltd.) were uniformly mixed to prepare a two-component developer. An unfixed image developed using a commercially available copying machine [AR5030, manufactured by Sharp Corporation] using this developer is fixed using a fixing unit of a commercially available full color copying machine [LBP-2160, manufactured by Canon Inc.]. , And was fixed at a process speed of 80 mm/sec.

[Evaluation criteria]
○: Good image quality after continuous copying of 8,000 sheets △: Slight deterioration of image quality (white background stain) after continuous copying of 8,000 sheets ×: Addition to white background stain after continuous copying of 8,000 sheets , The image quality is clearly deteriorated such as white stripes in the image

As is clear from the evaluation results of Table 2, all the toners of the examples of the present invention were excellent in all performance evaluations. On the other hand, the polyester (A'1) of Comparative Example 1 using alkenylsuccinic acid having a carbon chain length of 12 has poor low-temperature fixability, and the polyester of Comparative Example 2 using alkenylsuccinic acid having a branch number of 1 is used. The polyester (A'3) of Comparative Example 3 (A'3) has poor low-temperature fixability, heat-resistant storage stability, and image stability during continuous copying, and has a molar ratio of alkenylsuccinic acid in carboxylic acid of 55%. In (), the hot offset property, heat resistant storage property, and image quality stability during continuous copying were poor.

INDUSTRIAL APPLICABILITY The toner binder and toner composition of the present invention are capable of achieving both low-temperature fixability and heat-resistant storage stability, and are excellent in image stability during continuous copying, such as electrophotographic toner, electrostatic recording toner, and electrostatic printing toner. Can be provided.

Claims (3)

A toner binder containing a polyester resin (A) which is a reaction product of a polyol component (x) and a polycarboxylic acid component (y),
The polycarboxylic acid component (y) has a branched alkyl group (r1), an alkylsuccinic acid (y10) having a carbon number of 15 to 32 in (r1), a branched alkyl group (r2), and (r2) Having an alkylsuccinic anhydride (y11) having 15 to 32 carbon atoms and a branched alkenyl group (r3), and having (r3) an alkenylsuccinic acid (y20) having 15 to 32 carbon atoms and a branched alkenyl group (r4). ), and (r4) has 15 to 32 carbon atoms of alkenylsuccinic anhydride (y21), a mono- or diester of (y10) and an aliphatic monoalcohol having 1 to 4 carbon atoms, and (y20) ) And at least one selected from the group consisting of mono- or diesters of aliphatic monoalcohols having 1 to 4 carbon atoms, and (r1), (r2), (r3) and (r4) each have a methyl group of 3 Have one or more,
A toner binder in which the total number of moles of (y10), (y11), (y20), and (y21) is 3 to 50 mole% based on the total number of moles of (y). The toner binder according to claim 1, wherein the polyester resin (A) has a softening point of 90 to 150°C and an acid value of 7 to 21 mgKOH/g. A toner composition comprising the toner binder according to claim 1 and a colorant.