JP7430062B2 - Toner binder and toner - Google Patents

Description

The present invention relates to a toner binder and a toner.

In recent years, as electrophotographic apparatuses have become more power efficient, smaller, and faster, there has been a demand for toners with high environmental adaptability and toners with good color reproducibility. Furthermore, polyester resins produced by polycondensation reactions are widely known as toner binder resins used in toners. Conventionally, tin compounds have been used as polycondensation catalysts for synthesizing polyester resins, but since tin compounds are environmentally unfavorable, titanium compounds have recently been used.
Toners using polycondensed polyester resins using titanium-containing catalysts (for example, see Patent Document 1) are accompanied by some coloring, which may be a problem in applications where color tone and transparency are important, such as color applications. There is.

Additionally, low-temperature fixing performance is required from the viewpoint of power saving, and polyester resins obtained by polycondensing unsaturated carboxylic acid components have been reported as toners with excellent low-temperature fixing properties (for example, Patent Document (See 2-4). If a polymerization reaction occurs during polycondensation with the vinyl groups derived from unsaturated components starting from the generation of radicals due to heat, it is unfavorable in terms of performance as a toner binder, so phenolic compounds such as 4-tert-butylcatechol are used in combination. This suppresses radical polymerization reactions. However, a phenol compound having a hydroxyl group at the ortho-position of phenol forms a coordinate bond with the titanium compound of the polycondensation catalyst described above, resulting in a brown color and poor color reproducibility. Further, when Sumilizer GA-80 disclosed in Patent Document 2 is used, image strength and image conveyance properties due to image conveyance scratches deteriorate.

JP2006-284836A Japanese Patent Application Publication No. 2011-113064 Japanese Patent Application Publication No. 2016-157119 JP2018-128635A

An object of the present invention is to provide a toner binder and a toner containing the toner binder that are excellent in heat-resistant storage stability, image transportability, and color reproducibility without using a tin compound.

［式中、Ｒ^１～Ｒ^３は、それぞれ、水素原子、又は炭素数１～４のアルキル基を示し、Ｘは水素原子、水酸基又は炭素数１～４のアルキル基を示す。］

［式中、Ｒ^４～Ｒ^７は、それぞれ、水素原子又は炭素数１～４のアルキル基を示す。］ The present inventors have made extensive studies to solve these problems, and as a result, have arrived at the present invention.
That is, the present invention is a toner binder containing a polyester resin (A), a phenol compound (S), and a titanium element, wherein the phenol compound (S) is a phenol compound represented by the following general formula (1) and/or the following general formula: A toner binder which is a phenolic compound represented by (2) and has an elemental titanium content of 20 to 1000 ppm based on the total weight of the toner binder; and a toner containing the toner binder.

[In the formula, R ¹ to R ³ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. ]

[In the formula, R ⁴ to R ⁷ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

According to the present invention, it is possible to provide a toner binder and a toner that are excellent in heat-resistant storage stability, image transportability, and color reproducibility without using a tin compound.

The present invention will be explained in detail below.

The toner binder of the present invention contains polyester resin (A) as an essential component. The composition of the polyester resin (A) is not particularly limited as long as it is a polyester resin obtained by polycondensing an alcohol component and a carboxylic acid component. Examples of the polyester resin (A) include unsaturated polyester resin (A1) and saturated polyester resin (A2). It is preferable to contain an unsaturated polyester resin (A1) from the viewpoint of heat-resistant storage stability and image strength.
Further, it may be one type of polyester resin alone, a mixture of two or more types of polyester resin, or a mixture of the above polyester resin (A) and a vinyl resin (B) described below. good.

The unsaturated polyester resin (A1) is a polyester resin obtained by polycondensing a component having either an unsaturated carboxylic acid component (y) or an unsaturated alcohol component (z) as an essential component, and the above-mentioned In addition to the essential components, a saturated alcohol component (x) and a saturated carboxylic acid component (w) may be included as constituent components.
The unsaturated polyester resin (A1) may be obtained by polycondensing one type of each of these components, or may be one obtained by polycondensing a plurality of types of each component in combination.
In addition, in this specification, the bond between an aromatic ring and a heterocycle is not considered in determining whether it is an unsaturated carboxylic acid component (y) or a saturated carboxylic acid component (w).
Similarly, the bonds of aromatic rings and heterocycles are not considered in determining whether it is an unsaturated alcohol component (z) or a saturated alcohol component (x).

Further, the polyester resin (A) may be a polyester resin obtained by crosslinking an unsaturated polyester resin (A1), and the crosslinking of the unsaturated polyester resin (A1) is an unsaturated carboxylic acid (y) and/or an unsaturated alcohol. A polyester resin having a crosslinked structure due to a reaction between carbon-carbon double bonds derived from component (z) is preferable from the viewpoint of heat-resistant storage stability and image strength. As a form of crosslinking reaction, for example, unsaturated double bonds are introduced into the main chain or side chain of polyester resin, and the intermolecular carbon-carbon bonds are formed by reacting with radical addition reaction, cation addition reaction, or anion addition reaction. Examples include reactions to generate the reaction.
Note that the polyester resin that has formed a network through the crosslinking reaction cannot be dissolved in tetrahydrofuran (THF). This can be confirmed by the presence of components insoluble in THF (THF-insoluble components).

Examples of the unsaturated alcohol component (z) include unsaturated alcohols (z1) and unsaturated diols (z2).
These may be used alone or in combination of two or more.

Examples of the unsaturated alcohol (z1) include unsaturated alcohols having 2 to 30 carbon atoms, and preferred examples include 2-propen-1-ol, palmitoleyl alcohol, elaidyl alcohol, oleyl alcohol, erucyl alcohol, and methacryl alcohol. Examples include 2-hydroxyethyl acid.

Examples of the unsaturated diol (z2) include unsaturated diols having 2 to 30 carbon atoms, and a preferred example is ricinoleyl alcohol.

Examples of the saturated alcohol component (x) include saturated alcohol (x1), saturated diol (x2), and saturated polyol with a valence of 3 or more (x3).
These may be used alone or in combination of two or more.

Saturated alcohols (x1) include linear or branched alkyl alcohols having 1 to 30 carbon atoms (methanol, ethanol, isopropanol, 1-decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, and lignosyl alcohol). ceryl alcohol, etc.).

As the saturated diol (x2), alkylene glycols having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 3-methyl-1 , 5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol and 1, 12-dodecanediol, etc.) (x21), alkylene ether glycol having 4 to 36 carbon atoms (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.) (x22), carbon number 6 ~36 alicyclic diols (1,4-cyclohexanedimethanol and hydrogenated bisphenol A, etc.) (x23), (poly)alkylene oxide adducts of the above alicyclic diols (preferably 1 to 30 moles of addition) ( x24), aromatic diols [monocyclic dihydric phenols (e.g. hydroquinone, etc.) and bisphenols, etc.] (x25) and alkylene oxide adducts of the above aromatic diols (preferably number of moles added is 2 to 30) (x26), etc. Can be mentioned.
Among these saturated diols (x2), from the viewpoint of low-temperature fixability and heat-resistant storage stability, alkylene glycols having 2 to 36 carbon atoms (x21) and alkylene oxide adducts of aromatic diols (x26) are preferred; More preferred are alkylene oxide adducts.

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

HO-Ar-P-Ar-OH (a)
[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. represents a phenylene group which may be substituted with ]

Examples of 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-methylbisphenol A. , 2'-diethylbisphenol F, etc., and two or more of these can also be used in combination.

The alkylene oxide to be added to these bisphenols is preferably an alkylene oxide having 2 to 4 carbon atoms, such as ethylene oxide (hereinafter, "ethylene oxide" may be abbreviated as EO), propylene oxide (hereinafter, "ethylene oxide" may be abbreviated as EO), "Propylene oxide" may be abbreviated as PO), butylene oxide, tetrahydrofuran, and combinations of two or more thereof.

From the viewpoint of heat-resistant storage stability and low-temperature fixability, the AO constituting the AO adduct of bisphenols is preferably EO and/or PO. Further, the number of moles of AO added is preferably 2 to 30 moles, more preferably 2 to 10 moles, and still more preferably 2 to 5 moles.
Among the alkylene oxide adducts of bisphenols, preferable ones from the viewpoint of toner fixability, crushability, and heat-resistant storage stability are EO adducts of bisphenol A (the number of moles added is preferably 2 to 4, more preferably 2 to 4). 3) and/or a PO adduct (the number of moles added is preferably 2 to 4, more preferably 2 to 3).

The saturated polyol with a valence of 3 or more (x3) includes aliphatic polyhydric alcohols with a valence of 3 to 36 and a valence of 3 or more (x31), saccharides and derivatives thereof (x32), aliphatic polyhydric alcohols (average number of moles added is preferably 1 to 30) (x33), AO adduct of trisphenols (trisphenol PA, etc.) (average number of moles added is preferably 2 to 30) (x34), novolac Examples include AO adducts (average number of moles added is preferably 2 to 30) (x35) of resins (including phenol novolaks, cresol novolacs, etc., and average degree of polymerization is preferably 3 to 60).

Examples of the trivalent or higher valence aliphatic polyhydric alcohol (x31) having 3 to 36 carbon atoms include alkane polyols and intramolecular or intermolecular dehydrates thereof, such as glycerin, trimethylolethane, trimethylolpropane, Examples include pentaerythritol, sorbitol, sorbitan, polyglycerin and dipentaerythritol.

Examples of sugars and derivatives thereof (x32) include sucrose and methyl glucoside.

Among the saturated polyols (x3) with a valence of 3 or more, from the viewpoint of achieving both low-temperature fixing properties and hot offset resistance, aliphatic polyhydric alcohols with a valence of 3 or more and having 3 to 36 carbon atoms (x31 ) and novolac resins (including phenol novolacs, cresol novolaks, etc., and the average degree of polymerization is preferably 3 to 60) and AO adducts (the number of moles added is preferably 2 to 30) (x35) are preferred.

Among the saturated alcohol components (x), preferred ones from the viewpoint of achieving both low-temperature fixability, hot offset resistance, and heat-resistant storage stability are alkylene glycols having 2 to 36 carbon atoms (x21), AO adducts of bisphenols (addition The number of moles is preferably 2 to 30), a trivalent or higher valence aliphatic polyhydric alcohol having 3 to 36 carbon atoms (x31), and novolac resins (including phenol novolak and cresol novolac, etc.), and the average degree of polymerization is Preferably, it is an AO adduct (the number of moles added is preferably 2 to 30) (x35) of 3 to 60).

As the saturated alcohol component (x), more preferred are alkylene glycols having 2 to 10 carbon atoms, AO adducts of bisphenols (the number of moles added is preferably 2 to 5), and trivalent to octavalent alcohols having 3 to 36 carbon atoms. It is an AO adduct (the number of moles added is preferably 2 to 30) of an aliphatic polyhydric alcohol and a novolac resin (including phenol novolak and cresol novolak, etc., and the average degree of polymerization is preferably 3 to 60).
More preferred are alkylene glycols having 2 to 6 carbon atoms, AO adducts of bisphenol A (the number of moles added is preferably 2 to 5), and trivalent aliphatic polyhydric alcohols having 3 to 36 carbon atoms, particularly preferred. are 3-methyl-1,5-pentanediol, propylene glycol, an AO adduct of bisphenol A (the number of moles added is preferably 2 to 3), and trimethylolpropane.

As the saturated alcohol component (x), a saturated diol (x2) and a saturated polyol (x3) having a valence of 3 or more can be used together. When used together, the molar ratio [(x2)/(x3)] of the saturated diol (x2) and the saturated polyol (x3) having a valence of 3 or more is preferably 99/1 to 80/20 from the viewpoint of low temperature fixability. , 98/2 to 90/10 are more preferred.

Examples of the unsaturated carboxylic acid component (y) include unsaturated monocarboxylic acids (y1), unsaturated dicarboxylic acids (y2), anhydrides and lower alkyl esters of these acids.
These may be used alone or in combination of two or more.

The unsaturated monocarboxylic acid (y1) includes unsaturated monocarboxylic acids having 2 to 30 carbon atoms, specifically acrylic acid, methacrylic acid, propiolic acid, 2-butyric acid, crotonic acid, isocrotonic acid, 3-butenoic acid, angelic acid, tiglic acid, 4-pentenoic acid, 2-ethyl-2-butenoic acid, 10-undecenoic acid, 2,4-hexadienoic acid, myristoleic acid, palmitoleic acid, sapienoic acid, oleic acid, Examples include elaidic acid, vaccenic acid, gadoleic acid, erucic acid, and nervonic acid.

Unsaturated dicarboxylic acids (y2) include alkenedicarboxylic acids having 4 to 50 carbon atoms, specifically alkenylsuccinic acids such as dodecenylsuccinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, Examples include glutaconic acid.

Among these unsaturated carboxylic acid components (y), from the viewpoint of achieving both low-temperature fixing properties and hot offset resistance, unsaturated monocarboxylic acids having 2 to 10 carbon atoms and alkenedicarboxylic acids having 4 to 18 carbon atoms are preferred. More preferred are acrylic acid, methacrylic acid, alkenyl succinic acids such as dodecenyl succinic acid, maleic acid and fumaric acid.
More preferred are acrylic acid, methacrylic acid, maleic acid, fumaric acid, and combinations thereof. Furthermore, anhydrides and lower alkyl esters of these acids are also preferred.

Examples of the saturated carboxylic acid component (w) include aromatic carboxylic acids and aliphatic carboxylic acids. One type of saturated carboxylic acid component (w) may be used, or two or more types may be used in combination.

Examples of aromatic carboxylic acids include aromatic monocarboxylic acids having 7 to 37 carbon atoms (benzoic acid, paramethylbenzoic acid, toluic acid, 4-ethylbenzoic acid, 4-propylbenzoic acid, etc.), and 8 to 36 carbon atoms. aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, etc.), trivalent or higher aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, etc.), etc. .
Examples of aliphatic carboxylic acids include aliphatic monocarboxylic acids having 2 to 50 carbon atoms (acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid). acids, palmitic acid, margaric acid, stearic acid, behenic acid, etc.), aliphatic dicarboxylic acids with 2 to 50 carbon atoms (oxalic acid, malonic acid, succinic acid, adipic acid, reparginic acid, sebacic acid, etc.), 6 carbon atoms -36 aliphatic tricarboxylic acids (hexanetricarboxylic acid, etc.).
In addition, as the saturated carboxylic acid component (w), anhydrides and lower alkyl (carbon atoms 1 to 4) esters (methyl ester, ethyl ester, isopropyl ester, etc.) of these carboxylic acids may be used, and these It may be used in combination with carboxylic acid.

Among these saturated carboxylic acid components (w), preferred are aromatic monocarboxylic acids having 7 to 37 carbon atoms and aliphatic dicarboxylic acids having 2 to 50 carbon atoms from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability. , aromatic dicarboxylic acids having 8 to 20 carbon atoms, and trivalent or higher aromatic polycarboxylic acids having 9 to 20 carbon atoms, more preferably benzoic acid, adipic acid, alkylsuccinic acid, terephthalic acid, isophthalic acid, Trimellitic acid, pyromellitic acid, and combinations thereof are preferred, and more preferred are adipic acid, terephthalic acid, isophthalic acid, trimellitic acid, and combinations thereof. Further, anhydrides and lower alkyl esters of these acids may also be used.

From the viewpoint of heat-resistant storage stability and image strength, the unsaturated polyester resin (A1) has an unsaturated alcohol component (z) and an unsaturated carboxylic acid component (y) based on the total number of moles of the alcohol component and the carboxylic acid component. It is preferably 3 to 40 mol%, more preferably 5 to 30 mol%, and particularly preferably 7 to 25 mol%.

The saturated polyester resin (A2) is a polyester resin obtained by polycondensing components that do not contain either an unsaturated carboxylic acid component (y) or an unsaturated alcohol component (z), and a saturated carboxylic acid component ( A polyester resin obtained by polycondensing w) and a saturated alcohol component (x) is preferable.

Examples of the saturated alcohol component (x) of the saturated polyester resin (A2) include those similar to the saturated alcohol component (x) of the unsaturated polyester resin (A1).
Among these saturated alcohol components (x), preferred ones from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability are alkylene glycols having 2 to 6 carbon atoms, AO adducts of bisphenol A (the number of moles added is preferably 2 -5), more preferably an AO adduct of propylene glycol and bisphenol A (the number of moles added is preferably 2 to 3).

Examples of the saturated carboxylic acid component (w) of the saturated polyester resin (A2) include those similar to the saturated carboxylic acid component (w) of the unsaturated polyester resin (A1).
Among these saturated carboxylic acid components (w), those preferred from the viewpoint of achieving both low-temperature fixability and heat-resistant storage stability are aromatic carboxylic acids having 7 to 37 carbon atoms, aliphatic dicarboxylic acids having 2 to 50 carbon atoms, Aromatic dicarboxylic acids having 8 to 20 carbon atoms and aromatic polycarboxylic acids having 9 to 20 carbon atoms, more preferably benzoic acid, adipic acid, alkylsuccinic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyro Mellitic acid and a combination thereof. Further, anhydrides and lower alkyl esters of these acids may also be used.

In the toner binder of the present invention, the unsaturated polyester (A1) and the saturated polyester resin (A2) can be produced in the same manner as known polyesters.
For example, it can be carried out by reacting the constituent components in an inert gas (nitrogen gas, etc.) atmosphere at a reaction temperature of preferably 150 to 280°C, more preferably 160 to 250°C, even more preferably 170 to 235°C. can. In addition, the reaction time is preferably 30 minutes or more, more preferably 2 to 40 hours, from the viewpoint of ensuring the polycondensation reaction. It is also effective to reduce the pressure in order to improve the reaction rate at the final stage of the reaction.

Total charging ratio of saturated alcohol component (x) and unsaturated alcohol component (z) to unsaturated carboxylic acid component (y) and saturated carboxylic acid component (w) of unsaturated polyester (A1) and saturated polyester resin (A2) is preferably 1/2 to 2/1, more preferably 1/1.3 to 1.5/1, and even more preferably 1/2 as the equivalent ratio of hydroxyl group to carboxyl group ([OH]/[COOH]). It is 1.2 to 1.4/1.

The polyester resin (A) is a polyester resin obtained by crosslinking an unsaturated polyester resin (A1), and the crosslinking of the unsaturated polyester resin (A1) is derived from an unsaturated carboxylic acid component (y) and/or an unsaturated alcohol component (z). Preferred production methods for crosslinking carbon-carbon double bonds include the following methods.
First, at least one of the unsaturated carboxylic acid component (y) and the unsaturated alcohol component (z) and, if necessary, the saturated carboxylic acid component (w) and/or the saturated alcohol component (x) are subjected to a condensation reaction as constituent components. An unsaturated polyester resin (A1) having a carbon-carbon double bond in the molecule is obtained. Next, a radical reaction initiator (c) is made to act on the unsaturated polyester resin (A1), and the radicals generated from the radical reaction initiator (c) are used to reduce the unsaturated content in the unsaturated polyester resin (A1). Carbon-carbon double bonds caused by the carboxylic acid component (y) and/or the unsaturated alcohol component (z) are bonded together by a crosslinking reaction. Thereby, polyester resin (A) can be manufactured. This method is preferable because the crosslinking reaction can be made uniform in a short time.

The radical reaction initiator (c) used for the crosslinking reaction of the unsaturated polyester resin (A1) is not particularly limited, and includes inorganic peroxides (c1), organic peroxides (c2), and azo compounds (c3). etc. Further, these radical reaction initiators may be used in combination.

Examples of the inorganic peroxide (c1) include, but are not limited to, hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate.

The organic peroxide (c2) is not particularly limited, but examples include benzoyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α,α-bis(t-butyl peroxy) diisopropylbenzene, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di-t- Butyl peroxyhexine-3, acetyl peroxide, isobutyryl peroxide, octaninol peroxide, decanolyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, m-tolyl peroxide, t -Butylperoxyisobutyrate, t-butylperoxyneodecanoate, cumylperoxyneodecanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5 -trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxybenzoate, t-butyl peroxyisopropyl monocarbonate, and t-butyl peroxy acetate.

The azo compound (c3) is not particularly limited, but examples include 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2 '-azobisisobutyronitrile, 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, etc. can be mentioned.

Among these, organic peroxides (c2) are preferred because they have high initiator efficiency and do not produce toxic byproducts such as cyanide compounds.
Furthermore, since the crosslinking reaction proceeds efficiently and the amount used is small, reaction initiators with high hydrogen abstraction ability are more preferable, such as benzoyl peroxide, di-t-butyl peroxide, t-butylcumyl peroxide, t-Butylperoxyisopropyl monocarbonate, dicumyl peroxide, α,α-bis(t-butylperoxy)diisopropylbenzene, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane and More preferred are radical reaction initiators with high hydrogen abstraction ability such as di-t-hexyl peroxide.

The amount of the radical reaction initiator (c) used is not particularly limited, but the amount of the unsaturated carboxylic acid component (y) and unsaturated alcohol component (z) used in the polymerization reaction to obtain the unsaturated polyester resin (A1) is not particularly limited. 0.1 to 50% by weight, based on the total weight, is preferred.
When the amount of the radical reaction initiator used is 0.1% by weight or more, the crosslinking reaction tends to proceed easily, and when it is 50% by weight or less, the odor tends to be good. The amount used is more preferably 30% by weight or less, even more preferably 20% by weight or less, particularly preferably 10% by weight or less.

The toner binder of the present invention contains 20 to 1000 ppm of titanium element based on the total weight of the toner binder from the viewpoints of environmental friendliness, image transportability, and color reproducibility. When the content of titanium element is 20 ppm or more, the strength of the toner binder increases, resulting in good image conveyance, and when it is 1000 ppm or less, color reproducibility becomes good. The reason why the image transportability is good is that when the viscosity of the molten resin increases as it cools after fixing, the presence of titanium element in the molten resin that coordinates with the polyester resin promotes the increase in viscosity. Conceivable. In addition, the reason why the color reproducibility is good is that the titanium element is colored when it coordinates with the phenol compound (S), so by limiting the amount of titanium element, the coloring that affects the color reproducibility can be suppressed. It will be done. The content of titanium element in the toner binder is measured by fluorescent X-ray analysis. In addition, from the viewpoint of reactivity when producing the polyester resin (A), the titanium element is preferably derived from a titanium-containing esterification catalyst, and the polyester resin (A) is A polyester resin obtained by polycondensing an alcohol component and a carboxylic acid component is preferable. When a titanium-containing esterification catalyst is used, the content of titanium element in the polyester resin (A) is preferably 70 to 1000 ppm.
Examples of titanium-containing esterification catalysts include titanium halides (E1), titanium diketone enolates (E2), titanium carboxylates (E3), titanyl carboxylates (E4), titanium carboxylates (E5), and carboxylic acids. Examples include a titanyl salt (E6), a titanium-containing compound (E7) represented by the following general formulas (3) to (4), and a titanium-containing compound (E8) represented by the following formula (5).
Ti(-X)m(-OH)n (3)
O=Ti(-X)p(-OR ¹ )q(4)
[In formulas ( ³ ) and (4), It is an alkyl group of 1 to 8. m is an integer from 1 to 4, n is an integer from 0 to 3, and the sum of m and n is 4. p is an integer from 1 to 2, q is an integer from 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, each X may be the same or different. ]
Ti(-Z)r( ^-OR2 )s(5)
[In formula (5), R ² is a hydrogen atom or an alkyl group having 1 to 24 carbon atoms. Z is a residue obtained by removing one hydrogen atom of a carboxyl group from an aromatic carboxylic acid, r=1 to 3, s=1 to 3, and the sum of r and s is 4. ]

The amount of the titanium-containing esterification catalyst used is not particularly limited, but the lower limit is preferably 0.05% based on the total weight of the alcohol component and carboxylic acid component used to obtain the polyester resin. The upper limit is preferably 1.5%, more preferably 0.8%. When it is 0.05% or more, the action as a polycondensation catalyst is sufficiently obtained, and when it is 1.5% or less, image conveyance properties and color reproducibility are good.

Among the titanium-containing esterification catalysts, examples of the titanium halide (E1) include dichlorotitanium, trichlorotitanium, tetrachlorotitanium, trifluorotitanium, tetrafluorotitanium, and tetrabromotitanium.

Examples of the titanium diketone enolate (E2) include titanium acetylacetonate, titanium diisopropoxide bisacetylacetonate, and titanyl acetylacetonate. Among these (E2), titanium acetylacetonate is preferred.

Examples of the titanium carboxylate (E3) include titanium aliphatic carboxylates having 1 to 32 carbon atoms (E3-1) and titanium aromatic carboxylates having 7 to 38 carbon atoms (E3-2). In the case of titanium polycarboxylic acid having a valence of two or more, the number of carboxyl groups coordinated to titanium may be one or two or more, and free carboxyl groups may be present without being coordinated to titanium.

(E3-1) includes, for example, titanium aliphatic monocarboxylate (E3-1a), titanium aliphatic dicarboxylate (E3-1b), titanium aliphatic tricarboxylate (E3-1c), and aliphatic titanium having a valence of 4 or more. Examples include titanium polycarboxylate (E3-1d).
Examples of (E3-1a) include titanium formate, titanium acetate, titanium propionate, and titanium octoate. Examples of (E3-1b) include titanium oxalate, titanium succinate, titanium maleate, titanium adipate, and titanium sebacate. Examples of (E3-1c) include titanium hexanetricarboxylate and titanium isooctanetricarboxylate. Examples of (E3-1d) include titanium octanetetracarboxylate and titanium decanetetracarboxylate.

Examples of (E3-2) include aromatic titanium monocarboxylate (E3-2a), titanium aromatic dicarboxylate (E3-2b), titanium aromatic tricarboxylate (E3-2c), and tetravalent or higher aromatic titanium Examples include titanium polycarboxylate (E3-2d).
Examples of (E3-2a) include titanium benzoate. Examples of (E3-2b) include titanium phthalate, titanium terephthalate, titanium isophthalate, titanium 1,3-naphthalene dicarboxylate, titanium 4,4-biphenyldicarboxylate, titanium 2,5-toluene dicarboxylate, and titanium anthracene dicarboxylate. Examples include titanium dicarboxylate. Examples of (E3-2c) include titanium trimellitate and titanium 2,4,6-naphthalenetricarboxylate. Examples of (E3-2d) include titanium pyromellitate and titanium 2,3,4,6-naphthalenetetracarboxylate.

Among these (E3), (E3-2) is preferred from the viewpoint of catalytic activity, and (E3-2b) is more preferred.

Examples of the titanyl carboxylate (E4) include titanyl aliphatic carboxylates having 1 to 32 carbon atoms (E4-1) and titanyl aromatic carboxylates having 7 to 38 carbon atoms (E4-2). In the case of titanyl polycarboxylate having a valence of two or more, the number of carboxyl groups coordinated to titanium may be one or two or more, and free carboxyl groups may be present without being coordinated to titanium.
(E4-1) includes, for example, aliphatic titanyl monocarboxylate (E4-1a), aliphatic titanyl dicarboxylate (E4-1b), aliphatic tricarboxylic acid titanyl (E4-1c), and tetravalent or higher aliphatic titanyl Examples include titanyl polycarboxylate (E4-1d).
Examples of (E4-1a) include titanyl formate, titanyl acetate, titanyl propionate, titanyl octoate, and the like. Examples of (E4-1b) include titanyl oxalate, titanyl succinate, titanyl maleate, titanyl adipate, and titanyl sebacate. Examples of (E4-1c) include titanyl hexanetricarboxylate and titanyl isooctanetricarboxylate. Examples of (E4-1d) include titanyl octanetetracarboxylate and titanyl decanetetracarboxylate.

Examples of (E4-2) include titanyl aromatic monocarboxylate (E4-2a), titanyl aromatic dicarboxylate (E4-2b), titanyl aromatic tricarboxylate (E4-2c), and aromatic titanyl having a valence of 4 or more. Examples include titanyl polycarboxylate (E4-2d).
(E4-2a) includes, for example, titanyl benzoate. Examples of (E4-2b) include titanyl phthalate, titanyl terephthalate, titanyl isophthalate, titanyl 1,3-naphthalene dicarboxylate, titanyl 4,4-biphenyl dicarboxylate, titanyl 2,5-toluene dicarboxylate, and titanyl anthracene dicarboxylate. Examples include titanyl dicarboxylate. Examples of (E4-2c) include titanyl trimellitate and titanyl 2,4,6-naphthalenetricarboxylate. Examples of (E4-2d) include titanyl pyromellitate and titanyl 2,3,4,6-naphthalenetetracarboxylate.

The carboxylic acid titanium salt (E5) is not particularly limited, but includes, for example, aliphatic titanium dicarboxylate, titanium aliphatic tricarboxylate, titanium tetravalent or higher aliphatic polycarboxylate, titanium aromatic dicarboxylate, and titanium aromatic tricarboxylate. and alkali metal (lithium, sodium, potassium, etc.) salts or alkaline earth metal (magnesium, calcium, barium, etc.) salts of titanium carboxylates listed in titanium tetravalent or higher aromatic polycarboxylic acids. Among the above titanium carboxylic acid salts, from the viewpoint of catalytic activity, aromatic carboxylic acid titanium salts are preferred, and aromatic dicarboxylic acid titanium salts are more preferred.

The carboxylic acid titanyl salt (E6) is not particularly limited, but includes, for example, aliphatic titanyl dicarboxylate, aliphatic titanyl tricarboxylate, aliphatic titanyl polycarboxylate, aromatic titanyl dicarboxylate, aromatic titanyl tricarboxylate, or aromatic titanyl dicarboxylate. Alkali metal (lithium, sodium, potassium, etc.) salts or alkaline earth metal (magnesium, calcium, barium, etc.) salts of the titanyl carboxylates listed in titanyl polycarboxylate may be used. Among the titanyl carboxylate salts, from the viewpoint of catalytic activity, aliphatic dicarboxylic acid titanyl salts are preferred, and titanyl maleate and titanyl oxalate are preferred.

Examples of the titanium-containing compound (E7) include titanium-containing compounds represented by the above formula (3) or (4). X represented by the above formula (3) or (4) is a residue obtained by removing one hydrogen atom of an OH group from a mono- or polyalkanolamine having 2 to 12 carbon atoms, and the number of nitrogen atoms, i.e., The total number of primary, secondary, and tertiary amino groups is usually 1 to 2, preferably 1.
Examples of the monoalkanolamine include ethanolamine and propanolamine. Examples of polyalkanolamines include dialkanolamines (diethanolamine, N-methyldiethanolamine, N-butyldiethanolamine, etc.), trialkanolamines (triethanolamine, tripropanolamine, etc.), and tetraalkanolamines (N,N , N',N'-tetrahydroxyethylethylenediamine, etc.).
In the case of polyalkanolamines, there is one or more OH groups other than the OH group that is the residue excluding the hydrogen atom used to form the Ti-OC bond with the Ti atom, and it is the same Ti atom. It may be intramolecularly polycondensed with an OH group directly bonded to another Ti atom to form a ring structure, or it may be intermolecularly polycondensed with an OH group directly bonded to another Ti atom to form a repeating structure. From the viewpoint of heat-resistant storage stability, the degree of polymerization is preferably 2 to 5 when forming a repeating structure.
X is preferably a monoalkanolamine (especially ethanolamine), a dialkanolamine (especially diethanolamine) residue, or a trialkanolamine (especially triethanolamine) residue, more preferably a triethanolamine residue. It is.
R ¹ is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Specific examples of alkyl groups having 1 to 8 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-hexyl group, n-octyl group, β-methoxyethyl group, and Examples include β-ethoxyethyl group. Among these R ¹ , a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is preferred, and a hydrogen atom, an ethyl group, and an isopropyl group are more preferred.

Among the titanium-containing compounds (E7), specific examples of those represented by formula (3) include titanium tetrakis (monoethanolaminate), titanium monohydroxytris (triethanolaminate), and titanium dihydroxybis (triethanolaminate). titanium diisopropoxybis(triethanolaminate), titanium trihydroxytriethanolaminate, titanium dihydroxybis(diethanolaminate), titanium dihydroxybis(monoethanolaminate), titanium dihydroxybis(monopropanolaminate) , titanium dihydroxybis(N-methyldiethanolaminate), titanium dihydroxybis(N-butyldiethanolaminate), reaction products of tetrahydroxytitanium and N,N,N',N'-tetrahydroxyethylethylenediamine, and these. Examples include intramolecular or intermolecular polycondensates.
Examples of intramolecular or intermolecular polycondensates include compounds represented by the following formulas (3-1), (3-2), and (3-3).

［式中、Ｑ^１及びＱ^６は水素原子、炭素数１～４のアルキル基又はヒドロキシアルキル基である。Ｑ^２～Ｑ^５及びＱ^７～Ｑ^９は炭素数１～６のアルキレン基である。Ｘは炭素数２～１２のモノ又はポリアルカノールアミンから１個のＯＨ基の水素原子を除いた残基である。］

[Wherein, Q ¹ and Q ⁶ are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group. Q ² to Q ⁵ and Q ⁷ to Q ⁹ are alkylene groups having 1 to 6 carbon atoms. X is a residue obtained by removing one hydrogen atom of an OH group from a mono- or polyalkanolamine having 2 to 12 carbon atoms. ]

Specific examples of those represented by formula (4) include titanyl bis(triethanolaminate), titanyl bis(diethanolaminate), titanyl bis(monoethanolaminate), titanyl hydroxyethanolaminate, titanyl hydroxytriethanolaminate, titanyl Examples include ethoxytriethanolaminate, titanyl isopropoxytriethanolaminate, and intramolecular or intermolecular polycondensates thereof.
Examples of intramolecular or intermolecular polycondensates include compounds represented by the following formulas (4-1) and (4-2).

［式中、Ｑ^１及びＱ^６は水素原子、炭素数１～４のアルキル基又はヒドロキシアルキル基である。Ｑ^２～Ｑ^５は炭素数１～６のアルキレン基である。］

[Wherein, Q ¹ and Q ⁶ are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group. Q ² to Q ⁵ are alkylene groups having 1 to 6 carbon atoms. ]

Among these (E7), titanium dihydroxybis(triethanolaminate), titanium diisopropoxybis(triethanolaminate), titanium dihydroxybis(diethanolaminate), titanium monohydroxytris(triethanolaminate) are preferable. , titanium tetrakis (ethanolaminate), titanyl hydroxytriethanolaminate, titanyl bis(triethanolaminate), titanium dihydroxybis (triethanolaminate) intramolecular polycondensates, and combinations thereof, more preferably, These are titanium dihydroxybis(triethanolaminate), titanium monohydroxytris(triethanolaminate), titanium diisopropoxybis(triethanolaminate), and intramolecular polycondensates thereof.

These titanium-containing compounds (E7) can be stably obtained by, for example, reacting commercially available titanium dialkoxybis(alcohol amines) (manufactured by Dupont, etc.) at 70 to 90°C in the presence of water. I can do it. Further, the polycondensate can be obtained by further distilling off the condensed water under reduced pressure at 100°C.

Examples of the titanium-containing compound (E8) include the titanium-containing compound represented by the above formula (5). In the titanium-containing compound (E8) represented by the above formula (5), R ² is a hydrogen atom or an alkyl group having 1 to 24 carbon atoms. The alkyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.
Specific examples of the alkyl group having 1 to 24 carbon atoms include aliphatic hydrocarbon groups (for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, n-hexyl group, and n-octyl group). etc.) and aromatic hydrocarbon groups (for example, phenyl group, etc.).
Of these R ² , preferred are alkyl groups having 1 to 6 carbon atoms, more preferred are ethyl, n-propyl, isopropyl, n-butyl, and n-hexyl groups, and even more preferred are , n-propyl group, isopropyl group, and n-butyl group.

Z is a residue obtained by removing one carboxyl group hydrogen atom from an aromatic carboxylic acid, and in the case of an aromatic dicarboxylic acid or an aromatic polycarboxylic acid, Z is a residue other than the one bonded to a Ti atom to form a residue. The carboxyl group is an ^OR2 group in the same molecule {a hydroxyl group directly bonded to a Ti atom (when R ² is a hydrogen atom), or a hydroxyl group when R ² is a hydrocarbon group containing 1 to 2 hydroxyl groups} may be intramolecularly polycondensed with to form a ring structure, and intermolecularly polycondensed with OR ² groups (same as above) of another molecule of the titanium-containing compound represented by the above formula (5), A repeating structure containing a plurality of Ti atoms may be formed.
Examples of the aromatic carboxylic acid include those similar to those exemplified as the saturated carboxylic acid component (w) of the unsaturated polyester resin (A1).
In the case of aromatic dicarboxylic acid or aromatic polycarboxylic acid, as described above, the plural carboxyl groups may form a repeating structure containing plural Ti atoms, and in this case, the number of Ti atoms in one molecule is preferably 2 to 5 from the viewpoint of catalytic activity.
Preferred as Z are residues of aromatic dicarboxylic acids having 8 to 36 carbon atoms (such as phthalic acid, isophthalic acid, and terephthalic acid), and residues of aromatic monocarboxylic acids having 7 to 37 carbon atoms (benzoic acid and paramethylbenzoic acid). etc.), and more preferred are residues of phthalic acid, isophthalic acid and terephthalic acid.

In formula (5), r=1 to 3, s=1 to 3, and the sum of r and s, that is, the bond valence of the Ti atom, is 4. Preferably, r=1-2 and s=2-3. When r is 2 or less, the catalytic activity is good, and when s is 3 or less, the hydrolysis resistance is good, both of which are preferable for polyester production. When the bond number of Ti atoms is 4, it is preferable because the catalytic activity is good and side reactions are less likely to occur.

Specific examples of the compound represented by formula (5) include titanium triisopropoxybenzene carboxylate, titanium tributoxybenzene carboxylate, titanium triisopropoxy terephthalate, titanium tributoxy terephthalate, titanium triisopropoxy isophthalate, and titanium triisopropoxy benzene carboxylate. Isopropoxy phthalate, titanium diisopropoxy dibenzene carboxylate, titanium dibutoxy dibenzene carboxylate, titanium diisopropoxy diterephthalate, titanium dibutoxy diterephthalate, titanium diisopropoxy diisophthalate, titanium diisopropoxy diphthalate, titanium Examples include dihydroxydibenzene carboxylate, titanium dihydroxy diterephthalate, titanium dihydroxy diisophthalate, titanium dihydroxy diphthalate, and intramolecular or intermolecular polycondensates thereof.

From the viewpoint of catalytic activity during polyester polycondensation, the titanium-containing compound (E8) preferably has a solubility in water at 30°C of [5 g/100 mL] or less, more preferably [2 g/100 mL] or less. Preferably, it is particularly preferably at most [1 g/100 mL]. When the solubility is [5 g/100 mL] or less, the catalyst is less susceptible to hydrolysis during the polymerization reaction, which is preferable from the viewpoint of sustainability of catalyst activity.

These titanium-containing compounds (E8) can be obtained, for example, by reacting a commercially available titanium tetraalkoxide with an aromatic carboxylic acid in ethyl acetate at 70 to 90°C.

Among these titanium-containing esterification catalysts, titanium diketone enolate (E2), titanium carboxylate (E3), titanyl carboxylate salt (E6), titanium-containing compound (E7) and titanium-containing compound (E8) are preferred. More preferred are titanium carboxylate (E3), titanium-containing compound (E7) and titanium-containing compound (E8), and even more preferred are titanium-containing compound (E7) and titanium-containing compound (E8).

The toner binder of the present invention contains the phenol compound (S) represented by the above formula (1) and/or (2) from the viewpoint of image transportability and color reproducibility. By containing the phenol compound (S), coloring of the toner binder and toner of the present invention is reduced, and when the phenol compound (S) is included during the condensation reaction of the unsaturated polyester resin (A1), the unsaturated By suppressing the addition polymerization reaction of the components, low-temperature fixability, charge retention, and image strength become better. When the phenol compound (S) is present in the toner binder, image conveyance properties are improved. Although the reason is not clear, the viscosity of the toner binder melted on the fixing medium by heating during heat fixing increases rapidly due to the presence of the phenol compound (S), which causes the viscosity and storage modulus of the image surface to increase while passing through the roller. It is presumed that this is due to the increased strength against upward roller pressure.

In formula (1), R ¹ to R ³ are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, and an n- Examples include propyl group, isopropyl group, n-butyl group, and tert-butyl group.
X is a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms, and examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, and n-butyl group. , tert-butyl and the like.

Specific examples of the phenol compound (S) satisfying the above formula (1) include 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylphenol, and 2,6-di-tert-butylphenol. -Butyl-4-ethylphenol, 2,6-di-tert-butyl-4-isopropylphenol, 2,4,6-tri-tert-butylphenol, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone 2,6-di-tert-butyl-4-methylphenol and tert-butylhydroquinone are preferred.

In formula (2), R ⁴ to R ⁷ are each a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, and an n- Examples include propyl group, isopropyl group, n-butyl group, and tert-butyl group.

Specific examples of the phenol compound (S) satisfying the above formula (2) include 4-methoxyphenol, 2-tert-butyl-4-methoxyphenol, and 2,6-di-tert-butyl-4-methoxyphenol. 4-methoxyphenol is preferred.

The amount of the phenolic compound (S) contained in the toner binder of the present invention is preferably 0.02 to 2.00% by weight, more preferably 0.02 to 1.2% by weight based on the weight of the toner binder. Weight%. When the content of the phenolic compound (S) is 0.02% by weight or more, the image transportability and image strength when used as a toner are good, and when it is 2% by weight or less, low-temperature fixing properties and charging when used as a toner are improved. The retention rate and color reproducibility are improved.

In the present invention, the glass transition temperature (Tg) of the polyester resin (A) is preferably -35 to 70°C. When the glass transition temperature is 70°C or lower, low-temperature fixing properties are good, and when it is -35°C or higher, heat-resistant storage stability is good.
Further, the glass transition temperature of the unsaturated polyester resin (A1) is preferably -35 to 55°C, and the glass transition temperature of the saturated polyester resin (A2) is preferably 59 to 66°C.
Note that the glass transition temperature (Tg) can be measured by the method specified in ASTM D3418-82 (DSC method) using, for example, DSC Q20 manufactured by TA Instruments.

In the present invention, the peak top molecular weight of the polyester resin (A) in gel permeation chromatography (GPC) is preferably 2,000 to 30,000.
Further, the peak top molecular weight of the unsaturated polyester resin (A1) is preferably 7,000 to 15,000, and the peak top molecular weight of the saturated polyester resin (A2) is preferably 4,800 to 6,400. .

Here, a method for calculating the peak top molecular weight will be explained.
First, a calibration curve is prepared using a standard polystyrene sample by gel permeation chromatography (GPC). Next, the sample is separated by GPC, and the number of counts of the separated sample at each retention time is measured.
Next, a chart of the molecular weight distribution of the sample is created from the logarithmic value of the calibration curve and the obtained counts. The maximum peak value in the molecular weight distribution chart is the peak top molecular weight.
In addition, when there are multiple peaks in the chart of molecular weight distribution, the maximum value among those peaks is taken as the peak top molecular weight.

In the present invention, the acid value of the polyester resin (A) is preferably 20 mgKOH/g or less, more preferably 1 to 19 mgKOH/g.
Further, the acid value of the unsaturated polyester resin (A1) is preferably 5 mgKOH/g or less, and the acid value of the saturated polyester resin (A2) is preferably 5 to 10 mgKOH/g.

In the present invention, ΔE indicating coloring of the polyester resin (A) is preferably 70 or less from the viewpoint of color reproducibility, more preferably 50 or less, still more preferably 30 or less, particularly preferably 20 or less. It is.
Note that ΔE, which indicates coloration, can be measured using, for example, OME-2000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.).

The toner binder of the present invention may contain a vinyl resin (B). The vinyl resin (B) is not particularly limited as long as it is a known vinyl resin. Furthermore, when vinyl resin (B) is contained, the weight ratio of polyester resin (A) to vinyl resin (B) [(A):(B)] is preferably 15:85 to 60:40.
From the viewpoint of low-temperature fixability, the vinyl resin (B) is preferably a polymer having the monomer (a) as a constituent monomer, and the monomer in the monomers constituting the vinyl resin (B) The weight proportion of (a) is preferably 15 to 99% by weight, more preferably 20 to 60% by weight, based on the weight of vinyl resin (B).

The above monomer (a) is a (meth)acrylate having a chain hydrocarbon group and having 21 to 40 carbon atoms. When the number of carbon atoms is 21 or more, the heat-resistant storage stability will be good, and when the number of carbon atoms is 40 or less, the low-temperature fixability will be good.
As the monomer (a), (meth)acrylates having a linear alkyl group (18 to 36 carbon atoms) [octadecyl (meth)acrylate, nonadecyl (meth)acrylate, eicosyl (meth)acrylate, heneicosanyl (meth)acrylate , behenyl (meth)acrylate, lignoceryl (meth)acrylate, seryl (meth)acrylate, montanyl (meth)acrylate, triaconta(meth)acrylate, dotriaconta(meth)acrylate, etc.] and branched alkyl groups (carbon numbers 18 to 36) Examples include (meth)acrylates [2-decyltetradecyl (meth)acrylate, etc.] having the following.
Among these, (meth)acrylates having a linear alkyl group (18 to 36 carbon atoms) are preferred from the viewpoint of toner heat-resistant storage stability, low-temperature fixing properties, hot offset resistance, crushability, and image strength. (Meth)acrylates having a straight chain alkyl group (18 to 30 carbon atoms) are more preferred, and (meth)acrylates having a straight chain alkyl group (20 to 30 carbon atoms) are more preferred. , particularly preferably behenyl acrylate. In the present invention, "(meth)acrylic" means "acrylic" and/or "methacrylic".
Monomer (a) may be used alone or in combination of two or more.

From the viewpoint of heat-resistant storage stability, the monomer (b) may be contained as a constituent monomer in addition to the above-mentioned monomer (a). Monomers (b) include styrene monomers (for example, styrene, etc.), (meth)acrylic acid ester monomers [for example, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-hydroxylethyl (meth)acrylate; ) acrylate, etc.], carboxyl group-containing vinyl monomers [e.g. (meth)acrylic acid, etc.], nitrile monomers (e.g. acrylonitrile, methacrylonitrile, etc.), and vinyl ester monomers (e.g. vinyl acetate, vinyl propionate, etc.). The monomer (b) may be used alone or in combination of two or more. Among the above monomers (b), styrene, acrylonitrile, methacrylonitrile, vinyl acetate, acrylic The acid is 2-hydroxyethyl methacrylate.

The vinyl resin (B) can be obtained by a known polymerization method such as solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization using the above monomer and a radical polymerization initiator.
Among these polymerization methods, solution polymerization is preferred from the viewpoint of production stability.

Examples of the radical reaction initiator include those similar to the above radical reaction initiator (c).
Among these, preferred are 2,2'-azobis-(2,4-dimethylvaleronitrile), 2,2'-azobis(2-methylbutyronitrile), and di-t-butyl peroxide.
The amount of the radical reaction initiator used is preferably 0.01 to 5% by weight, more preferably 0.05 to 4% by weight, based on the total amount of monomers.

Solvents for solution polymerization include cycloalkane solvents with 5 to 12 carbon atoms (cyclohexane, methylcyclohexane, etc.), aromatic solvents with 6 to 12 carbon atoms (benzene, toluene, xylene, ethylbenzene, cumene, etc.), and ester solvents. (ethyl acetate, butyl acetate, etc.) and ether solvents (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.) are used.
Among these, preferred are aromatic solvents having 6 to 12 carbon atoms, more preferred are toluene, xylene and ethylbenzene.

The endothermic peak top temperature of the vinyl resin (B) is preferably 40 to 70° C. from the viewpoint of low-temperature fixability.

The acid value of the vinyl resin (B) is preferably 0 to 36 mgKOH/g from the viewpoint of heat-resistant storage stability.

From the viewpoint of heat-resistant storage stability, the hydroxyl value of the vinyl resin (B) is preferably 0 to 42 mgKOH/g.

The weight average molecular weight of the vinyl resin (B) is preferably 11,000 to 33,000 from the viewpoint of heat-resistant storage stability.

ΔE, which indicates the coloring of the vinyl resin (B), is preferably 70 or less from the viewpoint of color reproducibility, more preferably 50 or less, still more preferably 30 or less, particularly preferably 20 or less.

In the toner binder of the present invention, a polyester resin (A) containing a phenol compound (S) and 20 to 1000 ppm of titanium element may be used as it is, or when it contains a vinyl resin (B), a polyester resin The resin (A) and the vinyl resin (B) may be mixed and used by the method described below, and the unsaturated polyester (A1) is mixed with the unsaturated polyester (A1) and the vinyl resin (B). It is preferable to crosslink the carbon-carbon double bonds derived from the unsaturated carboxylic acid component (y) and/or the unsaturated alcohol component (z). The toner binder obtained by this method is preferable from the viewpoint of achieving a uniform crosslinking reaction of the polyester resin (A) in a short time and achieving both low-temperature fixability, hot offset resistance, and heat-resistant storage stability.
Note that the toner binder of the present invention may contain resins other than the polyester resin (A) and vinyl resin (B) and known additives (such as a release agent).

In the present invention, the endothermic peak top temperature of the toner binder is preferably 40 to 100°C, more preferably 58 to 62°C. When the peak top temperature is within the above range, the toner binder has good low-temperature fixability. This is because the toner binder rapidly melts at the endothermic peak top temperature (Tm) and its viscosity decreases.

In the present invention, the toner binder preferably has at least one inflection point in the temperature range of -25°C to 58°C.

In the present invention, the acid value of the toner binder is preferably 1 to 31 mgKOH/g or less.

In the present invention, ΔE indicating coloration of the toner binder is preferably 70 or less from the viewpoint of color reproducibility, more preferably 50 or less, still more preferably 30 or less, particularly preferably 20 or less.

The toner binder of the present invention may contain a THF-insoluble component.
The content (wt%) of THF-insoluble matter in the toner binder of the present invention is preferably 55 wt% or less, more preferably 9 to 55 wt%, from the viewpoint of low-temperature fixability.

The content (% by weight) of THF-insoluble matter in the toner binder of the present invention was determined by the following method.
Add 50 mL of THF to 0.5 g of sample, and stir and reflux for 3 hours. After cooling, undissolved components are filtered off using a glass filter, and the resin components on the glass filter are dried under reduced pressure at 80° C. for 3 hours. The weight of the dried resin on the glass filter is taken as the weight of the THF-insoluble part, and the weight of the sample minus the weight of the THF-insoluble part is taken as the weight of the THF-soluble part. Calculate the weight percent of the minute.

A method for manufacturing a toner binder will be explained.
The toner binder is not particularly limited as long as it contains a polyester resin (A), a phenol compound (S), a titanium element, and for example, the above-mentioned polyester resin (A), a phenol compound (S), a titanium element, and a vinyl resin used if necessary. The mixing method for mixing (B) and the additive may be a commonly used known method, and examples of the mixing method include powder mixing, melt mixing, and solvent mixing. The phenol compound and the titanium element may be mixed during the production of the polyester resin (A), and the titanium element is preferably mixed as a titanium-containing esterification catalyst. Further, the polyester resin (A), the phenol compound (S), the titanium element, and the vinyl resin (B) and additives used if necessary may be mixed at the same time when producing the toner. Among these methods, melt mixing is preferred, as it provides uniform mixing and does not require solvent removal.

Examples of mixing devices for powder mixing include Henschel mixer, Nauta mixer, and Banbury mixer. A Henschel mixer is preferred.
Examples of the mixing device for melt-mixing include batch-type mixing devices such as a reaction tank and continuous-type mixing devices. A continuous mixing device is preferred in order to mix uniformly at an appropriate temperature in a short time. Examples of continuous mixing devices include static mixers, extruders, continuous kneaders, three rolls, and the like.

Among these, an unsaturated polyester resin (A1) is produced in the presence of a phenolic compound (S) and a titanium-containing esterification catalyst, and the unsaturated polyester resin (A1) is further melt-mixed with a vinyl resin (B) and an unsaturated polyester resin (A1). A method of crosslinking the polyester resin (A1) is preferred, and a specific method for performing this melt mixing is to inject a mixture of the unsaturated polyester (A1) and the vinyl resin (B) into a twin screw extruder at a constant speed. There is a method in which the radical reaction initiator (c) is simultaneously injected at a constant rate and the reaction is carried out while kneading and conveying at a temperature of 100 to 200°C.

At this time, the unsaturated polyester resin (A1) and vinyl resin (B), which are reaction raw materials to be charged or injected into the twin-screw extruder, are directly injected into the extruder as they are from the resin reaction solution without cooling. Alternatively, the resin may be cooled once produced, pulverized, and then fed to a twin-screw extruder.

In addition, the method of melting and mixing is not limited to these specifically exemplified methods; for example, an appropriate method such as a method of charging the raw materials into a reaction vessel, heating them to a temperature at which they become a solution, and mixing them, etc. It can be carried out.

The toner of the present invention contains the toner binder of the present invention.

In addition to the toner binder of the present invention, the toner of the present invention may optionally contain one or more known additives selected from colorants, release agents, charge control agents, fluidizing agents, and the like.

As the colorant, all dyes, pigments, etc. used as colorants for toners can be used. For example, 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. Examples include FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orazole Brown B, and Oil Pink OP, and these colorants may be used alone. or a mixture of two or more. Further, if necessary, magnetic powder (ferromagnetic metal powder such as iron, cobalt, nickel, etc., or compound such as magnetite, hematite, ferrite, etc.) may be included to also function as a coloring agent.
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, the amount is preferably 20 to 150 parts by weight, more preferably 40 to 120 parts by weight.

As mold release agents, natural waxes (beeswax, carnauba wax, montan wax, etc.), petroleum waxes (paraffin wax, microcrystalline wax, petrolatum, etc.), synthetic waxes (Fischer-Tropsch wax, polyethylene wax, polypropylene wax, oxidized polyethylene wax, etc.) can be used. wax and oxidized polypropylene wax, etc.), and synthetic ester waxes (fatty acid esters synthesized from fatty acids with 10 to 30 carbon atoms and alcohols with 10 to 30 carbon atoms, etc.), and from the group consisting of these mold release agents. It is preferable to contain one or more selected types. The content of the release agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, and still more preferably 1 to 10% by weight, based on 100 parts by weight of the toner binder of the present invention.

The melting point of the release agent is preferably 40 to 90°C, more preferably 45 to 85°C from the viewpoint of low-temperature fixability.

The charge control agent may contain either a positively chargeable charge control agent or a negatively chargeable charge control agent, such as nigrosine dye, triphenylmethane dye containing a tertiary amine as a side chain, class ammonium salts, polyamine resins, imidazole derivatives, quaternary ammonium base-containing polymers, metal-containing azo dyes, copper phthalocyanine dyes, salicylic acid metal salts, boron complexes of benzylic acid, sulfonic acid group-containing polymers, fluorine-containing polymers, halogen-substituted aromatics Examples include ring-containing polymers. The content of the charge control agent may be 0 to 20% by weight, preferably 0.1 to 10% by weight, more preferably 0.5 to 7.5% by weight, based on 100 parts by weight of the toner binder of the present invention. Weight%.

Examples of the fluidizing agent include silica, titania, alumina, fatty acid metal salts, silicone resin particles, and fluororesin particles, and two or more types may be used in combination. Silica is preferred from the viewpoint of toner chargeability. Further, the silica is preferably hydrophobic silica from the viewpoint of toner transferability. The content of the fluidizing agent may be 0 to 10% by weight, preferably 0 to 5% by weight, and more preferably 0.1 to 4% by weight, based on 100 parts by weight of the toner binder of the present invention. .

The composition ratio of the toner containing the toner binder is such that the toner binder of the present invention is preferably 30 to 97% by weight, more preferably 40 to 95% by weight, and still more preferably 45 to 92% by weight, based on the weight of the toner. The colorant is preferably 0.05 to 60% by weight, more preferably 0.1 to 55% by weight, and even more preferably 0.5 to 50% by weight, and the colorant is preferably 0.05 to 60% by weight, and even more preferably 0.5 to 50% by weight, and the amount of the colorant is Among additives such as curing agents, the mold release agent is preferably 0 to 30% by weight, more preferably 0.5 to 20% by weight, and even more preferably 1 to 10% by weight, and the charge control agent is preferably is 0 to 20% by weight, more preferably 0.1 to 10% by weight, even more preferably 0.5 to 7.5% by weight, and the fluidizing agent is preferably 0 to 10% by weight, more preferably 0 ~5% by weight, more preferably 0.1~4% by weight. Further, the total content of additives is preferably 3 to 70% by weight, more preferably 4 to 58% by weight, even more preferably 5 to 50% by weight.

The method for manufacturing the toner containing the toner binder of the present invention is not particularly limited, and may include the known kneading and pulverization method, emulsion phase inversion method, emulsion polymerization method, Japanese Patent Publication No. 36-10231, Japanese Patent Application Laid-Open No. 59-53856, Suspension polymerization method, dissolution suspension method described in JP-A-59-61842, emulsion aggregation method described in JP-A-62-106473 and JP-A-63-186253, etc. It may be obtained by any known method.
For example, when obtaining a toner by a kneading and pulverizing method, the components constituting the toner except for the fluidizing agent are dry blended using a Henschel mixer, a Nauta mixer, a Banbury mixer, etc., and then a twin-screw kneader, an extruder, a continuous kneader, etc. The mixture is melt-kneaded using a continuous mixing device such as a three-roll mill, then roughly pulverized using a mill, etc., and finally pulverized using an air-flow pulverizer, etc., and then the particle size distribution is determined using a classifier such as an elbow jet. By adjusting, toner particles [preferably particles having a volume average particle diameter (D50) of 5 to 20 μm] can be produced by mixing a fluidizing agent.
Incidentally, the volume average particle diameter (D50) is measured using a Coulter counter [eg, trade name: Multisizer III (manufactured by Coulter Inc.)].

The toner containing the toner binder of the present invention is mixed with carrier particles such as iron powder, glass beads, nickel powder, ferrite, magnetite, and ferrite whose surface is coated with resin (acrylic resin, silicone resin, etc.) as necessary. It is used as a developer for electrical latent images. When carrier particles are used, the weight ratio of toner to carrier particles is preferably 1/99 to 99/1. Furthermore, an electrical latent image can also be formed by friction with a member such as a charging blade instead of the carrier particles.
Note that the toner containing the toner binder of the present invention does not need to contain carrier particles.

A toner containing the toner binder of the present invention is fixed to a support (paper, polyester film, etc.) using a copying machine, printer, etc., and is used as a recording material. As a method for fixing to the support, known hot roll fixing methods, flash fixing methods, etc. can be applied.

A toner prepared using the toner binder of the present invention is used for developing an electrostatic image or a magnetic latent image in electrophotography, electrostatic recording, electrostatic printing, or the like. More specifically, it is used for developing electrostatic images or magnetic latent images suitable for full-color printing.

The present invention will be further explained below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, "parts" refer to parts by weight unless otherwise specified.

Physical property values of the polyester resin (A), vinyl resin (B), toner binder, toner, etc. were measured by the following method.

[Measuring method]
<Glass transition temperature>
It was measured using a differential scanning calorimeter (manufactured by TA Instruments Co., Ltd., DSC Q20) according to the method specified in ASTM D3418-82 (DSC method).
The measurement conditions for glass transition temperature are as follows: (1) Heating from 30°C to 150°C at 20°C/min (2) Holding at 150°C for 10 minutes (3) Cooling to -35°C at 20°C/min (4) ) Hold at −35° C. for 10 minutes (5) Raise the temperature to 150° C. at 20° C./min (6) The differential scanning calorimetry curve measured in the process of (5) was analyzed to determine the glass transition temperature.

<Weight average molecular weight and peak top molecular weight>
The resin was dissolved in tetrahydrofuran (THF), filtered through a membrane filter, and a sample solution was measured using gel permeation chromatography (GPC) under the following conditions.
Equipment: HLC-8120 [manufactured by Tosoh Corporation]
Column: TSK GEL GMH6 2 pieces [manufactured by Tosoh Corporation]
Measurement temperature: 40℃
Sample solution: 0.25% by weight THF solution filtered through a membrane filter Solution injection amount: 100μL
Detection device: Refractive index detector Reference material: 12 points of standard polystyrene (TSK standard POLYSTYRENE) (molecular weight 500 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000) [Manufactured by Tosoh Corporation]

<Acid value and hydroxyl value>
It was measured by the method specified in JIS K0070. However, the solvent for measuring the acid value was a mixed solvent of acetone, methanol, and toluene (acetone:methanol:toluene=12.5:12.5:75), and the solvent for measuring the hydroxyl value was THF.

<Titanium element content>
Measurement was performed using a fluorescent X-ray analyzer (Axios, manufactured by Malvern Panalytical). Place a sample molding frame (made of PVC, diameter 3.5 cm, thickness 0.4 cm) on a press stand, put 5 g of the sample finely pulverized to 20 μm or less into the frame, mold it with a press pressure of 10 tons, and then mold the molded product. Measurement was performed at 50 kV, 40 mA, and total element determination method (FP method).

<Endothermic peak top temperature (Tm)>
Using a differential scanning calorimeter (manufactured by TA Instruments Co., Ltd., DSC Q20), the temperature was raised for the first time from 20°C to 150°C at 10°C/min, and then from 150°C at 10°C/min. When the temperature is cooled to 0℃ under the following conditions, and then the temperature is raised a second time from 0℃ to 150℃ under the conditions of 10℃/min, the temperature that indicates the top of the endothermic peak in the second heating process is called endothermic. It was taken as the peak top temperature.

<THF insoluble matter>
Add 50 mL of THF to 0.5 g of sample, and stir and reflux for 3 hours. After cooling, undissolved components are filtered off using a glass filter, and the resin components on the glass filter are dried under reduced pressure at 80° C. for 3 hours. The weight of the dried resin on the glass filter is taken as the weight of the THF-insoluble part, and the weight of the sample minus the weight of the THF-insoluble part is taken as the weight of the THF-soluble part. % by weight was calculated.

<Coloring of resin>
ΔE was measured using a petroleum product measuring device OME-2000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.). 2 g of the sample was dissolved in 8 g of toluene, and after removing insoluble matter by centrifugation, it was placed in a cell with an optical path length of 10 mm, and ΔL, Δa, and Δb were measured by Saybolt colorimetry, and ΔE was calculated. The average value of three measurements was taken as the measured value.

<Toner volume average particle size (D50) (μm), number average particle size (μm), particle size distribution (volume average particle size/number average particle size)>
Measurement was performed using a Coulter counter [trade name: Multisizer III (manufactured by Beckman Coulter, Inc.)].
First, 0.1 to 5 mL of a surfactant (alkylbenzene sulfonate) as a dispersant was added to 100 to 150 mL of ISOTON-II (manufactured by Beckman Coulter), which is an electrolytic aqueous solution. Furthermore, 2 to 20 mg of the measurement sample was added, and the electrolyte in which the sample was suspended was dispersed for about 1 to 3 minutes using an ultrasonic disperser. The number was measured and the volume distribution and number distribution were calculated. From the obtained distribution, the volume average particle diameter (D50) (μm), number average particle diameter (μm), and particle size distribution (volume average particle diameter/number average particle diameter) of the toner were determined.

<Production Example 1> [Production of unsaturated polyester resin (A1-1)]
In a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 770 parts of bisphenol A/EO 2 mole adduct as the saturated alcohol component (x), 110 parts of terephthalic acid as the saturated carboxylic acid component (w), and adipine were placed. 118 parts of acid, 30 parts of trimellitic anhydride, and 2.5 parts of titanium diisopropoxy bis(triethanolaminate) as a catalyst were added, and 2. Allowed time to react. Next, after reacting for 5 hours under reduced pressure of 0.5 to 2.5 kPa, the temperature was lowered to 180°C. 2 parts of 2,6-di-tert-butyl-4-methylphenol was added as a phenol compound, and 38 parts of fumaric acid as an unsaturated carboxylic acid component (y) was added, and the mixture was heated under reduced pressure of 0.5 to 2.5 kPa. After reacting for 8 hours, the mixture was taken out to obtain an unsaturated polyester resin (A1-1).
The glass transition temperature of the unsaturated polyester resin (A1-1) measured by the above method was 36° C., the peak top molecular weight was 8400, the acid value was 1 mgKOH/g, the titanium element content was 350 ppm, and ΔE was 15.

<Production Example 2> [Production of unsaturated polyester resin (A1-2)]
In a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 489 parts of 3-methyl-1,5-pentanediol and 32 parts of trimethylolpropane, which are the saturated alcohol component (x), and a saturated carboxylic acid component (w) were placed. ), 413 parts of terephthalic acid and 81 parts of adipic acid, and 7.1 parts of titanium diisopropoxy bis(triethanolaminate) as a catalyst were added, and the water produced was distilled off at 230°C under a nitrogen stream. The reaction was allowed to proceed for 2 hours. Next, after reacting for 5 hours under reduced pressure of 0.5 to 2.5 kPa, the temperature was lowered to 180°C. 5 parts of tert-butylhydroquinone was added as a phenol compound, and 128 parts of fumaric acid as an unsaturated carboxylic acid component (y) was added. After reacting for 8 hours under a reduced pressure of 0.5 to 2.5 kPa, the unsaturated carboxylic acid component was taken out. A saturated polyester resin (A1-2) was obtained.
The glass transition temperature of the unsaturated polyester resin (A1-2) measured by the above method was -25°C, the peak top molecular weight was 7000, the acid value was 1 mgKOH/g, the titanium element content was 990 ppm, and ΔE was 20.

<Production Example 3> [Production of unsaturated polyester resin (A1-3)]
In a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 517 parts of bisphenol A/EO 2 mol adduct, 220 parts of bisphenol A/PO 2 mol adduct, and 8 parts of trimethylolpropane, which are saturated alcohol components (x). , 280 parts of terephthalic acid as a saturated carboxylic acid component (w), and 2.5 parts of titanium diisopropoxy bis(triethanolaminate) as a catalyst were added, and the produced water was distilled at 230°C under a nitrogen stream. The mixture was allowed to react for 2 hours while being removed. Next, after reacting for 5 hours under reduced pressure of 0.5 to 2.5 kPa, the temperature was lowered to 180°C. 1 part of 4-methoxyphenol was added as a phenol compound, and 49 parts of fumaric acid as an unsaturated carboxylic acid component (y) was added. After reacting for 8 hours under a reduced pressure of 0.5 to 2.5 kPa, the unsaturated carboxylic acid component (y) was removed. A saturated polyester resin (A1-3) was obtained.
The glass transition temperature of the unsaturated polyester resin (A1-3) measured by the above method was 55° C., the peak top molecular weight was 15,000, the acid value was 2 mgKOH/g, the titanium element content was 350 ppm, and ΔE was 20.

<Production Example 4> [Production of unsaturated polyester resin (A1-4)]
In a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 729 parts of bisphenol A/EO 2 mole adduct, which is a saturated alcohol component (x), and 12 parts of trimethylolpropane, and a saturated carboxylic acid component (w) are placed. 192 parts of terephthalic acid, 123 parts of adipic acid, and 5.0 parts of titanium diisopropoxy bis(triethanolaminate) were added as a catalyst, and the mixture was heated at 230°C under a nitrogen stream for 2 hours while distilling off the water produced. Made it react. Next, after reacting for 5 hours under reduced pressure of 0.5 to 2.5 kPa, the temperature was lowered to 180°C. 20 parts of 2,6-di-tert-butyl-4-methylphenol as a phenol compound were added, and 19 parts of fumaric acid as an unsaturated carboxylic acid component (y) were added, and the mixture was heated under reduced pressure of 0.5 to 2.5 kPa. After reacting for 8 hours, the mixture was taken out to obtain an unsaturated polyester resin (A1-4).
The glass transition temperature of the unsaturated polyester resin (A1-4) measured by the above method was 44° C., the peak top molecular weight was 12,000, the acid value was 5 mgKOH/g, the titanium element content was 700 ppm, and ΔE was 17.

<Production Example 5> [Production of unsaturated polyester resin (A1-5)]
In a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 755 parts of bisphenol A/EO 2 mole adduct, which is a saturated alcohol component (x), and 13 parts of trimethylolpropane, and a saturated carboxylic acid component (w) are placed. 153 parts of terephthalic acid, 118 parts of adipic acid, and 0.5 part of titanium diisopropoxy bis(triethanolaminate) were added as a catalyst, and the mixture was heated at 230°C under a nitrogen stream for 2 hours while distilling off the water produced. Made it react. Next, after reacting for 5 hours under reduced pressure of 0.5 to 2.5 kPa, the temperature was lowered to 180°C. 5 parts of tert-butylhydroquinone was added as a phenol compound, and 40 parts of acrylic acid as an unsaturated carboxylic acid component (y) was added. After reacting for 8 hours under reduced pressure of 0.5 to 2.5 kPa, the unsaturated carboxylic acid component (y) was taken out. A saturated polyester resin (A1-5) was obtained.
The glass transition temperature of the unsaturated polyester resin (A1-5) measured by the above method was 25° C., the peak top molecular weight was 8500, the acid value was 2 mgKOH/g, the titanium element content was 70 ppm, and ΔE was 18.

<Production Example 6> [Production of unsaturated polyester resin (A1-6)]
In a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 770 parts of bisphenol A/EO 2 mole adduct as the saturated alcohol component (x), 110 parts of terephthalic acid as the saturated carboxylic acid component (w), and adipine were placed. 118 parts of acid, 30 parts of trimellitic anhydride, and 2.5 parts of titanium terephthalate as a catalyst were added, and the mixture was reacted for 2 hours at 230° C. under a nitrogen stream while distilling off the produced water. Next, after reacting for 5 hours under reduced pressure of 0.5 to 2.5 kPa, the temperature was lowered to 180°C. 2 parts of 2,6-di-tert-butyl-4-methylphenol was added as a phenol compound, and 38 parts of fumaric acid as an unsaturated carboxylic acid component (y) was added, and the mixture was heated under reduced pressure of 0.5 to 2.5 kPa. After reacting for 8 hours, the mixture was taken out to obtain an unsaturated polyester resin (A1-6).
The glass transition temperature of the unsaturated polyester resin (A1-6) measured by the above method was 36° C., the peak top molecular weight was 8300, the acid value was 1 mgKOH/g, the titanium element content was 320 ppm, and ΔE was 10.

<Comparative Production Example 1> [Production of unsaturated polyester resin (A1'-1)]
In a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 770 parts of bisphenol A/EO 2 mole adduct as the saturated alcohol component (x), 110 parts of terephthalic acid as the saturated carboxylic acid component (w), and adipine were placed. 118 parts of acid, 30 parts of trimellitic anhydride, and 2.5 parts of titanium diisopropoxy bis(triethanolaminate) as a catalyst were added, and 2. Allowed time to react. Next, after reacting for 5 hours under reduced pressure of 0.5 to 2.5 kPa, the temperature was lowered to 180°C. Add 2 parts of 4-tert-butylcatechol as a phenol compound, then add 38 parts of fumaric acid as an unsaturated carboxylic acid component (y), react under reduced pressure of 0.5 to 2.5 kPa for 8 hours, and then take out. , an unsaturated polyester resin (A1'-1) containing no phenol compound (S) was obtained.
The unsaturated polyester resin (A1'-1) had a glass transition temperature of 36° C., a peak top molecular weight of 8300, an acid value of 1 mgKOH/g, a titanium element content of 350 ppm, and a ΔE of 105.

<Comparative Production Example 2> [Production of unsaturated polyester resin (A1'-2)]
In a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 770 parts of bisphenol A/EO 2 mole adduct as the saturated alcohol component (x), 110 parts of terephthalic acid as the saturated carboxylic acid component (w), and adipine were placed. 118 parts of acid, 30 parts of trimellitic anhydride, and 2 parts of dibutyltin oxide as a catalyst were added, and the mixture was reacted at 230° C. under a nitrogen stream for 2 hours while distilling off the produced water. Next, after reacting for 5 hours under reduced pressure of 0.5 to 2.5 kPa, the temperature was lowered to 180°C. 2 parts of 2,6-di-tert-butyl-4-methylphenol was added as a phenol compound, and 38 parts of fumaric acid as an unsaturated carboxylic acid component (y) was added, and the mixture was heated under reduced pressure of 0.5 to 2.5 kPa. After reacting for 8 hours, the resin was taken out to obtain an unsaturated polyester resin (A1'-2) containing no titanium element.
The unsaturated polyester resin (A1'-2) had a glass transition temperature of 36°C, a peak top molecular weight of 8500, an acid value of 1 mgKOH/g, a titanium element content of 0 ppm, and a ΔE of 15.

<Production Example 7> [Production of saturated polyester resin (A2-1)]
In a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 363 parts of bisphenol A/EO 2 mol adduct, which is the saturated alcohol component (x), 386 parts of bisphenol A/PO 2 mol adduct, and the saturated carboxylic acid component ( w) 273 parts of terephthalic acid and 2.5 parts of titanium diisopropoxy bis(triethanolaminate) as a catalyst were added and reacted at 230°C under a nitrogen stream for 2 hours while distilling off the water produced. I let it happen. Next, after reacting for 5 hours under reduced pressure of 0.5 to 2.5 kPa, the temperature was lowered to 180°C. 34 parts of trimellitic anhydride was added, reacted for 1 hour, and then taken out to obtain a saturated polyester resin (A2-1).
The saturated polyester resin (A2-1) had a glass transition temperature of 59° C., a peak top molecular weight of 4800, an acid value of 19 mgKOH/g, a titanium element content of 350 ppm, and a ΔE of 17.

<Production Example 8> [Production of saturated polyester resin (A2-2)]
In a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 762 parts of bisphenol A/PO 2 molar adduct as a saturated alcohol component (x), 290 parts of terephthalic acid as a saturated carboxylic acid component (w), and adipine were placed. 1 part of acid and 7.1 parts of titanium diisopropoxy bis(triethanolaminate) as a catalyst were added, and the mixture was reacted for 2 hours at 230° C. under a nitrogen stream while distilling off the produced water. Next, after reacting for 5 hours under reduced pressure of 0.5 to 2.5 kPa, the temperature was lowered to 180°C. 9 parts of trimellitic anhydride was added, reacted for 1 hour, and then taken out to obtain a saturated polyester resin (A2-2).
The saturated polyester resin (A2-2) had a glass transition temperature of 66° C., a peak top molecular weight of 5900, an acid value of 5 mgKOH/g, a titanium element content of 990 ppm, and a ΔE of 18.

<Production Example 9> [Production of saturated polyester resin (A2-3)]
In a reaction tank equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 49 parts of bisphenol A/PO 2 molar adduct as a saturated alcohol component (x) and 581 parts of propylene glycol, and terephthal as a saturated carboxylic acid component (w) were placed. Add 625 parts of acid, 8 parts of adipic acid, 49 parts of benzoic acid, 58 parts of trimellitic anhydride, and 2 parts of titanium diisopropoxy bis(triethanolaminate) as a catalyst, and generate at 230°C under a nitrogen stream. The reaction was allowed to proceed for 2 hours while distilling off water and propylene glycol. Next, after reacting for 5 hours under reduced pressure of 0.5 to 2.5 kPa, the temperature was lowered to 180°C. 17 parts of trimellitic anhydride was added, reacted for 1 hour, and then taken out to obtain a saturated polyester resin (A2-3). The amount of propylene glycol distilled out was 234 parts.
The saturated polyester resin (A2-3) had a glass transition temperature of 63° C., a peak top molecular weight of 6400, an acid value of 10 mgKOH/g, a titanium element content of 280 ppm, and a ΔE of 20.

<Production Example 10> [Production of vinyl resin (B-1)]
After charging 138 parts of xylene into an autoclave and purging the autoclave with nitrogen, the temperature was raised to 170° C. in a closed state while stirring. 450 parts of behenyl acrylate [manufactured by NOF Corporation, the same hereinafter], 150 parts of styrene [manufactured by Idemitsu Kosan Co., Ltd., the same hereinafter], 150 parts of acrylonitrile [manufactured by Nacalai Teks Co., Ltd., the same hereinafter], G-t- A mixed solution of 1.5 parts of butyl peroxide [Perbutyl D, manufactured by NOF Corporation] and 100 parts of xylene was added dropwise over 3 hours to carry out polymerization while controlling the temperature inside the autoclave at 170°C. After dropping, the dropping line was cleaned with 12 parts of xylene. The polymerization was further maintained at the same temperature for 1 hour to complete the polymerization. The solvent was removed at 170° C. for 6 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain a vinyl resin (B-1). The composition is listed in Table 3.
Vinyl resin (B-1) had an endothermic peak top temperature of 60° C., an acid value of 0 mgKOH/g, a hydroxyl value of 0 mgKOH/g, a weight average molecular weight of 28,000, and a ΔE of 57.

<Production Example 11> [Production of vinyl resin (B-2)]
An autoclave was charged with 150 parts of toluene and 75 parts of vinyl acetate, and after the autoclave was purged with nitrogen, the temperature was raised to 60° C. in a closed state while stirring. 300 parts of behenyl acrylate, 51 parts of styrene, 25 parts of acrylonitrile, 25 parts of vinyl acetate, 5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.], and A mixed solution of 325 parts of toluene was added dropwise over 3 hours to carry out polymerization while controlling the temperature inside the autoclave at 60°C. After dropping, the dropping line was washed with 25 parts of toluene and aged at the same temperature for 1 hour. After aging, the temperature was raised to 80°C over 1 hour, and after reaching 80°C, the temperature was maintained for 1 hour to complete polymerization. The solvent was removed at 120° C. for 8 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain a vinyl resin (B-2). The composition is listed in Table 3.
The endothermic peak top temperature of the vinyl resin (B-2) was 63° C., the acid value was 36 mgKOH/g, the hydroxyl value was 0 mgKOH/g, the weight average molecular weight was 33,000, and ΔE was 28.

<Production Example 12> [Production of vinyl resin (B-3)]
150 parts of xylene was charged into an autoclave, the autoclave was purged with nitrogen, and then the temperature was raised to 96° C. in a closed state while stirring. 200 parts of behenyl acrylate, 80 parts of acrylonitrile, 45 parts of methacrylonitrile, 125 parts of vinyl acetate, 50 parts of 2-hydroxyethyl methacrylate, 2,2'-azobis(2-methylbutyronitrile) [V-59, Wako Pure Chemical Industries, Ltd. Co., Ltd.] and 325 parts of xylene was added dropwise over 3 hours to carry out polymerization while controlling the temperature inside the autoclave at 96°C. After dropping, the dropping line was washed with 25 parts of xylene and aged at the same temperature for 2 hours to complete polymerization. The solvent was removed at 170° C. for 6 hours under a reduced pressure of 0.5 to 2.5 kPa to obtain a vinyl resin (B-3). The composition is listed in Table 3.
The endothermic peak top temperature of the vinyl resin (B-3) was 62° C., the acid value was 1 mgKOH/g, the hydroxyl value was 42 mgKOH/g, the weight average molecular weight was 11,000, and ΔE was 40.

<Example 1> [Manufacture of toner binder (C-1)]
30 parts of unsaturated polyester resin (A1-1) and 70 parts of vinyl resin (B-1) were mixed and fed to a twin-screw kneader [manufactured by Kurimoto Iron Works Co., Ltd., S5KRC kneader] at a rate of 52 kg/hour, and at the same time As a radical reaction initiator (c), 2.0 parts of t-butylperoxyisopropyl monocarbonate (c-2) was supplied at a rate of 0.52 kg/hour, and the mixture was kneaded and extruded at 90 rpm for 7 minutes at 160° C. to perform a crosslinking reaction. Further, the mixture was mixed while removing the organic solvent by reducing the pressure at 10 kPa from the vent port. By cooling the mixture obtained, a toner binder (C-1) according to Example 1 was obtained.

<Examples 2 to 10> [Production of toner binders (C-2) to (C-10)]
The parts by weight of unsaturated polyester resin (A1), saturated polyester resin (A2) or vinyl resin (B) shown in Table 4 are mixed and fed to a twin-screw kneader, and at the same time a radical reaction initiator (c) is fed. Then, the crosslinking reaction and removal of the organic solvent were carried out in the same manner as in Example 1, to obtain toner binders (C-2) to (C-10) according to Examples 2 to 10.
In addition, the radical reaction initiators (c) in Tables 2 and 3 are as follows.
(c-1): di-t-butyl peroxide (c-2): t-butyl peroxyisopropyl monocarbonate

<Example 11> [Manufacture of toner binder (C-11)]
A toner binder (C-11) according to Example 11 was obtained by mixing the unsaturated polyester resin (A1-3) and the saturated polyester resin (A2-1) in the parts by weight shown in Table 4 without crosslinking reaction. .

<Comparative Examples 1 to 2> [Manufacture of toner binders (C'-1) to (C'-2)]
The unsaturated polyester resin (A1') in the weight parts shown in Table 4 and the vinyl resin (B) were mixed and fed to a twin-screw kneader in the same manner as in Example 1, and at the same time the radical reaction initiator (c) was added. The toner binders (C'-1) and (C'-2) according to Comparative Examples 1 and 2 were obtained by supplying and carrying out a crosslinking reaction.

<Example 12> [Manufacture of toner (T-1)]
To 88 parts of the toner binder (C-1) according to Example 1, 7 parts of carbon black as a pigment [manufactured by Mitsubishi Chemical Corporation, MA-100], 3 parts of carnauba wax as a release agent, and a charge control agent [ 1 part of T-77 (manufactured by Hodogaya Chemical Industry Co., Ltd.) was added to form a toner in the following manner.
First, the mixture was premixed using a Henschel mixer (manufactured by Nippon Coke Kogyo Co., Ltd., FM10B), and then kneaded with a twin-screw kneader (manufactured by Ikegai Co., Ltd., PCM-30). Then, after finely pulverizing using a supersonic jet crusher Labo Jet [manufactured by Kurimoto Iron Works Co., Ltd., KJ-25], an elbow jet classifier [manufactured by Matsubo Co., Ltd., model EJ-L-3 (LABO)] was used. ] to obtain toner particles having a volume average particle diameter D50 of 8 μm.
Next, 1 part of hydrophobic silica [Aerosil R972, manufactured by Nippon Aerosil Co., Ltd.] as a fluidizing agent was mixed with 100 parts of the toner particles in a sample mill to obtain a toner (T-1) according to Example 12. .

<Examples 13 to 22> [Production of toners (T-2) to (T-11)]
Toners were produced in the same manner as in Example 12 using the blended numbers of raw materials listed in Table 5 to obtain toners (T-2) to (T-11) according to Examples 13 to 22.

<Comparative Examples 3 to 4> [Manufacture of toners (T'-1) to (T'-2)]
Toners were produced in the same manner as in Example 12 using the blended numbers of raw materials listed in Table 5 to obtain toners (T'-1) and (T'-2) according to Comparative Examples 3 and 4.

[Evaluation method]
Below, methods for measuring the low temperature fixability, heat resistant storage stability, environmental friendliness and color reproducibility of the obtained toners (T-1) to (T-11) and (T'-1) to (T'-2) are described below. and evaluation methods, including judgment criteria.

<Low temperature fixability>
The toner was uniformly placed on the paper surface at a concentration of 1.00 mg/cm ² . At this time, the powder was placed on the paper using a printer without a heat fixing device.
This paper was passed through a soft roller at a fixing speed (peripheral speed of the heating roller) of 213 mm/sec and a temperature of the heating roller in the range of 90 to 200°C in 5°C increments.
Next, the presence or absence of cold offset on the fixed image was visually observed, and the temperature at which cold offset occurred (MFT) was measured.
The lower the temperature at which cold offset occurs, the better the low-temperature fixing properties are.
Under these evaluation conditions, the MFT is generally preferably 130° C. or lower.

<Heat-resistant storage stability>
1 g of toner was placed in a sealed container and allowed to stand for 24 hours in an atmosphere with a temperature of 50° C. and a humidity of 50%, and the degree of blocking was visually determined, and heat-resistant storage stability was evaluated using the following criteria.

[Judgment criteria]
○: No blocking occurred at all, and excellent heat-resistant storage stability.
△: Blocking occurs in some parts, and heat-resistant storage stability is poor.
×: Blocking occurs throughout, and heat-resistant storage stability is greatly inferior.

<Charge maintenance rate>
0.5 g of toner and 20 g of ferrite carrier (manufactured by Powder Tech Co., Ltd., F-150) were placed in a 50 mL glass bottle, and the bottle was conditioned at 23° C. and a relative humidity of 50% for 8 hours or more. Thereafter, the mixture was friction stirred at 50 rpm for 10 minutes and 60 minutes using a Turbler shaker mixer, and the amount of charge at each time was measured. A blow-off charge measuring device [manufactured by Kyocera Chemical Co., Ltd.] was used for the measurement.
"Amount of charge after 60 minutes of friction time/Amount of charge after 10 minutes of friction time" was calculated, and this was taken as the charging stability index. It means that the larger the charge stability index is, the better the charge retention rate is. Under these evaluation conditions, it is preferable that it is 0.7 or more.

<Image transportability>
As a two-component developer, a commercially available monochrome copying machine [AR5030, manufactured by Sharp Corporation] was used to create a solid image on the entire surface of the paper, and the degree of image transport scratches caused by the paper ejection roller was compared with a ranked sample. Image transportability was evaluated using the following criteria.
The rank sample is arranged in ranks 1 to 5, from most to least image conveyance flaws, and the higher the score, the fewer image conveyance flaws.
[Evaluation criteria]
◎: Rank 5 (no image transport scratches)
○: Rank 3 to 4 (image transport flaws can be seen when magnifying 10 to 30 times)
△: Rank 2 (image transport flaws can be partially confirmed)
×: Rank 1 (image transport flaws can be seen throughout)

<Image intensity>
The image fixed in the low-temperature fixability evaluation above was subjected to a scratch hardness test in accordance with JIS K5600 using a manual scratching method with a 10 g load applied from directly above a pencil fixed at a 45-degree angle. Image strength was evaluated based on the pencil hardness that did not stick.
The higher the pencil hardness, the better the image strength. Generally, it is preferable that it is HB or more.

<Environmental>
It was confirmed whether the toner contained a tin compound or not using a fluorescent X-ray analyzer (manufactured by PANalytical, Axios). Place a sample molding frame (made of PVC, diameter 3.5 cm, thickness 0.4 cm) on a press stand, put 5 g of the sample finely pulverized to 20 μm or less into the frame, mold it with a press pressure of 10 tons, and then mold the molded product. Measurement was performed at 50 kV, 40 mA, and total element determination method (FP method).
○: Tin content is 30 ppm or less.
×: Tin content is more than 30 ppm.

<Color reproducibility (image density)>
The image density of the image fixed at a heat roller temperature of 180° C. used for evaluation of low-temperature fixability was measured using a Macbeth reflection densitometer RD-191 (manufactured by Macbeth Co., Ltd.).
○: ID1.4 or more △: ID1.3 or more and less than 1.4 ×: ID less than 1.3

As is clear from the evaluation results in Table 5, toners (T-1) to (T-11) according to Examples 12 to 22 had excellent results in all performance evaluations.
On the other hand, the toners (T'-1) and (T'-2) according to Comparative Examples 3 and 4 were poor in performance items such as environmental friendliness and color reproducibility.

The toner binder and toner of the present invention do not use tin compounds and have excellent low-temperature fixability, heat-resistant storage stability, charge retention rate, image transportability, image strength, and color reproducibility, and are suitable for use in electrophotography, electrostatic recording, and electrostatic recording. It can be suitably used as a toner binder and toner for electrostatic image development used in electronic printing and the like.
Furthermore, it is suitable for use as additives for paints, additives for adhesives, particles for electronic paper, etc.

Claims (6)

A toner binder containing a polyester resin (A), a phenol compound (S), and a titanium element,
The polyester resin (A) contains a polyester resin crosslinked with an unsaturated polyester resin (A1), and the unsaturated polyester resin (A1) has a glass transition temperature of -35 to 55°C,
The phenol compound (S) is a phenol compound represented by the following general formula (1) and/or a phenol compound represented by the following general formula (2),
A toner binder having an elemental titanium content of 20 to 1000 ppm based on the total weight of the toner binder.

[In the formula, R ¹ to R ³ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and X represents a hydrogen atom, a hydroxyl group, or an alkyl group having 1 to 4 carbon atoms. ]

[In the formula, R ⁴ to R ⁷ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ] The toner binder according to claim 1, wherein the phenol compound (S) is 0.02 to 2.00% by weight based on the weight of the toner binder. Claim 1 or 2, wherein the phenol compound (S) is at least one compound selected from the group consisting of 2,6-di-tert-butyl-4-methylphenol, 2-tert-butylhydroquinone, and 4-methoxyphenol. Toner binder described in. The toner binder according to any one of claims 1 to 3, wherein the polyester resin (A) is an unsaturated polyester resin (A1). The polyester resin (A) is a polyester resin obtained by crosslinking an unsaturated polyester resin (A1),
The unsaturated polyester resin (A1) is an unsaturated polyester resin obtained by polycondensing a component having either an unsaturated carboxylic acid component (y) or an unsaturated alcohol component (z) as an essential component,
Any one of claims 1 to 3, wherein the crosslinking of the unsaturated polyester resin (A1) is achieved by a reaction between carbon-carbon double bonds derived from the unsaturated carboxylic acid component (y) and/or the unsaturated alcohol component (z). The toner binder according to item 1. A toner containing the toner binder according to any one of claims 1 to 5 .