JP2010096928A - Toner resin and toner composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To develop a toner resin which satisfies both of hot offset resistance and low-temperature fixability even in the use of a toner where higher speed and energy saving are achieved. <P>SOLUTION: The toner resin includes a nonlinear polyester resin (A) having a THF-insoluble component content of 3-45 wt.%, a peak top molecular weight of a THF-soluble component by gel permeation chromatography of 3,500-25,000 and a softening point of 120-185°C, and containing 20-2,000 ppm of elementary titanium and 10-1,200 ppm of elementary nitrogen. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner resin and a toner composition used for electrophotography, electrostatic recording, electrostatic printing and the like.

The toner for developing electrostatic images used in the thermal fixing method is such that the toner does not fuse to the heat roll even at a high fixing temperature (hot offset resistance), and the toner can be fixed even at a low fixing temperature (low temperature fixing property). It has been demanded. In general, the hot offset resistance and the low-temperature fixability of toner tend to conflict with each other. As a toner excellent in balance between hot offset resistance and low-temperature fixability, a toner containing two kinds of polyesters having different glass transition temperatures as a resin for toner is disclosed (for example, see Patent Document 1). Further, it is disclosed that a toner binder containing a polycondensation polyester resin formed in the presence of a specific titanium compound is used (see Patent Document 2).
Japanese Patent Laid-Open No. 2005-221986 WO2003 / 073171 Pamphlet

  However, although the toner proposed in Patent Document 1 has a certain balance of hot offset resistance and low temperature fixability to some extent, it is compatible with both hot offset resistance and low temperature fixability at higher speed and energy saving. Then we need to improve. In addition, the toner proposed in Patent Document 2 sometimes has poor color reproducibility.

The present inventors arrived at the present invention after earnestly studying to solve these problems.
That is, the present invention includes the following [1] and [2].
[1] THF-insoluble content is 3 to 45% by weight, THF-soluble content of gel permeation chromatography peak top molecular weight is 3500 to 25000, softening point is 120 to 185 ° C., titanium element is 20 to 2000 ppm, A toner resin comprising a non-linear polyester resin (A) containing 10 to 1200 ppm of a nitrogen element.
[2] A toner composition comprising the toner resin, a colorant, and, if necessary, one or more additives selected from a release agent, a charge control agent, and a fluidizing agent.

  By using the toner resin of the present invention, a toner having excellent hot offset resistance and low-temperature fixability can be obtained, and the toner has good blocking resistance and color reproducibility.

The present invention is described in detail below.
In the present invention, from the viewpoint of color reproducibility, the non-linear polyester resin (A) contained in the toner resin of the present invention has a titanium element content of 20 to 2000 ppm, preferably 30 to 1800 ppm, more preferably. 50-1500 ppm. When the titanium element content exceeds 2000 ppm, the coloration of (A) increases, and the color reproducibility when used as a toner is deteriorated. Moreover, when titanium element content is less than 20 ppm, the time required for polycondensation when obtaining (A) may become long.
As a method of adjusting the titanium element content to the above range, a method of using one or more titanium-containing catalysts during the polycondensation reaction when obtaining (A) and adjusting the amount used is preferable.

  In the present invention, the content of titanium element in the resin is measured by a fluorescent X-ray analyzer (manufactured by PANalytical).

Moreover, nitrogen element content of a non-linear polyester resin (A) is 10-1200 ppm, Preferably it is 20-1100 ppm, More preferably, it is 30-1000 ppm. When the nitrogen element content exceeds 1200 ppm, the coloring of (A) becomes large, and the color reproducibility when used as a toner is deteriorated. Further, when the nitrogen element content is less than 10 ppm, the effect of the present invention is not achieved.
As a method for adjusting the nitrogen element content to the above range, a method using a slight amount of a compound having a nitrogen-containing group such as an amino group as a raw material of (A) can be mentioned. Preferably, when obtaining (A) In this method, a titanium-containing catalyst having one or more amino groups is used in the polycondensation reaction, and the amount used is adjusted.

  In the present invention, the nitrogen element content in the resin was measured using a trace nitrogen sulfur analyzer (ANTEK 7000, manufactured by ANTEK Co., Ltd.) (a calibration curve for the amount of nitrogen was prepared using an ethylbenzene solution of triphenylamine). is there.

In the present invention, as described above, it is preferable to use the non-linear polyester resin (A) obtained using the titanium-containing catalyst during the polycondensation reaction.
The titanium-containing catalyst is not particularly limited but is preferably represented by titanium alkoxide (titanium tetrabutoxide, titanium tetraisopropoxide, etc.), potassium titanyl oxalate, titanium terephthalate, and the following general formula (I) or (II). Titanium-containing catalyst (z), more preferably potassium titanyl oxalate, and (z), particularly preferably (z).
Ti (-X) m (-OH) n (I)
O = Ti (-X) p (-OR) q (II)
[In the formula, X is a residue obtained by removing H of one OH group from a mono- or polyalkanolamine having 2 to 12 carbon atoms, and other OH groups of the polyalkanolamine are directly bonded to the same Ti atom. An OH group may be polycondensed in the molecule to form a ring structure, or an OH group directly bonded to another Ti atom may be polycondensed between molecules to form a repeating structure. The degree of polymerization in the case of forming a repeating structure is 2-5. R is H or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds. m is an integer of 1 to 4, n is an integer of 0 to 3, and the sum of m and n is 4. p is an integer of 1 to 2, q is an integer of 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. ]

In the general formulas (I) and (II), X is a residue obtained by removing the H atom of one OH group from a mono- or polyalkanolamine having 2 to 12 carbon atoms. The total number of secondary and tertiary amino groups is usually 1 to 2, preferably 1.
Examples of the monoalkanolamine include ethanolamine and propanolamine. Polyalkanolamines include dialkanolamines (such as diethanolamine, N-methyldiethanolamine, and N-butyldiethanolamine), trialkanolamines (such as triethanolamine, and tripropanolamine), and tetraalkanolamines (N, N, N). ', N'-tetrahydroxyethylethylenediamine and the like).
In the case of polyalkanolamine, at least one OH group is present in addition to the OH group that is a residue other than H used to form a Ti—O—C bond with a Ti atom, and this is the same Ti atom. A ring structure may be formed by polycondensation with a directly bonded OH group in the molecule, or a repeating structure may be formed by polycondensation between molecules with an OH group directly bonded to another Ti atom. The degree of polymerization in the case of forming a repeating structure is 2-5. When the degree of polymerization is 6 or more, the catalytic activity is lowered and the oligomer component is increased, which causes deterioration of toner blocking properties.
Preferred as X are residues of monoalkanolamine (especially ethanolamine), dialkanolamine (especially diethanolamine) and trialkanolamine (especially triethanolamine), particularly preferred are those of triethanolamine Residue.
R is H or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds. Specific examples of the alkyl group 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 Rs, H and an alkyl group having 1 to 4 carbon atoms not containing an ether bond are preferable, and H, an ethyl group, and an isopropyl group are more preferable.

In formula (I), m is an integer of 1-4, Preferably it is an integer of 1-3. n is an integer of 0 to 3, preferably an integer of 1 to 3. The sum of m and n is 4.
In formula (II), p is an integer of 1 to 2, q is an integer of 0 to 1, and the sum of p and q is 2. When m or p is 2 or more, a plurality of Xs may be the same or different, but are preferably all the same.

Specific examples of the titanium-containing catalyst (z) represented by the general formula (I) include titanium tetrakis (monoethanolamate), titanium monohydroxytris (triethanolamate), titanium dihydroxybis (tri Ethanolaminate), titanium trihydroxytriethanolaminate, titanium dihydroxybis (diethanolamate), titanium dihydroxybis (monoethanolamate), titanium dihydroxybis (monopropanolamate), titanium dihydroxybis (N-methyldiethanolamate) ), Titanium dihydroxybis (N-butyldiethanolamate), tetrahydroxytitanium and N, N, N ′, N′-tetrahydroxyethylethylenediamm Reaction products of, and polycondensates between these intramolecular or molecule.
Examples of intramolecular or intermolecular polycondensates include at least one compound represented by the following general formula (I-1), (I-2), or (I-3).

[Wherein, Q ¹ and Q ⁶ are H, or 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 OH group H from a mono- or polyalkanolamine having 2 to 12 carbon atoms. ]
Specific examples of those represented by the general formula (II) include titanyl bis (triethanolaminate), titanyl bis (diethanolamate), titanyl bis (monoethanolamate), titanyl hydroxyethanolamate, titanylhydroxytriethanolamate, Examples include titanyl ethoxytriethanolamate, titanyl isopropoxytriethanolamate, and intramolecular or intermolecular polycondensates thereof.
Examples of intramolecular or intermolecular polycondensates include at least one compound represented by the following general formula (II-1) or (II-2).

[Wherein, Q ¹ and Q ⁶ are H, or an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group. Q < ² > -Q < ⁵ > is a C1-C6 alkylene group. ]
Among these, preferred are titanium dihydroxybis (triethanolaminate), titanium dihydroxybis (diethanolamate), titanium monohydroxytris (triethanolamate), titanium tetrakis (ethanolamate), titaniumylhydroxytriethanolamin. Nitrate, titanyl bis (triethanolaminate), titanium dihydroxybis (triethanolaminate) intramolecular or intermolecular polycondensates (below (z1) and (z3)), titanium monohydroxytris (triethanolamate) Intramolecular polycondensate [(z2) below], and combinations thereof, more preferably titanium dihydroxybis (triethanolaminate), titanium monohydroxylate Scan (triethanolaminate), in their molecular polycondensates [(z1) and (z2)], in particular (z1).

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

The addition amount of the titanium-containing catalyst is preferably 0.01 to 0.8% by weight, more preferably 0.015 to 0%, based on the weight of the polymer obtained, from the viewpoint of polymerization activity and color reproducibility. 0.7% by weight. It is preferable to use the catalyst amount because both polymerization activity and transparency can be achieved.
In addition, other esterification catalysts can be used in combination as long as the catalytic effect of the titanium-containing catalyst is not impaired. Examples of other esterification catalysts include tin-containing catalysts (eg dibutyltin oxide), antimony trioxide, zirconium-containing catalysts (eg zirconyl acetate), germanium-containing catalysts, alkali (earth) metal catalysts (eg alkali metal or alkaline earth). Metal carboxylates: lithium acetate, sodium acetate, potassium acetate, calcium acetate, sodium benzoate, potassium benzoate, etc.), and zinc acetate. The addition amount of these other catalysts is preferably 0 to 0.6% by weight with respect to the obtained polymer. When the amount is within 0.6% by weight, coloring of the polyester resin is reduced, which is preferable for use in a color toner. The content of the titanium-containing catalyst in the total added catalyst is preferably 50 to 100% by weight, and more preferably 100% by weight.

The composition of the non-linear polyester resin (A) in the toner resin of the present invention is not particularly limited. For example, one or more polyol components and one or more polycarboxylic acid components are used in one step or two steps. What was obtained by polycondensation by the above is mentioned.
(A) is preferably obtained by further reacting the terminal of the polyester resin with a carboxylic acid. The polyester resin (a) having a specific acid value and a specific hydroxyl value described below, an aliphatic carboxylic acid, Obtained by reacting with one or more carboxylic acids (b) selected from the group consisting of aromatic carboxylic acids, acid anhydrides of these carboxylic acids and lower alkyl (carbon number 1-4) esters of these carboxylic acids. More preferred.
As said (a), what was obtained by polycondensation of 1 or more types of polyol components and 1 or more types of polycarboxylic acid components is preferable.

  Among the polyol components of the raw material of the polyester resin (a), the dihydric alcohol (diol) includes an aliphatic diol having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1 , 4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2,3-pentanediol, 1,6-hexanediol, 2,3-hexanediol, 3,4-hexanediol, neopentyl Glycols, 1,7-heptanediol, and alkanediols such as dodecanediol); polyalkylene ether glycols having 4 to 36 carbon atoms (such as diethylene glycol, dipropylene glycol, polyethylene glycol, and polypropylene glycol); The aliphatic diol C2-C4 alkylene oxide (hereinafter abbreviated as AO) [ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), butylene oxide, etc.] adduct (added mole number: 2 to 30); C6-C36 alicyclic diol (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); C2-C4 AO adduct (added mole number 2-30) of the alicyclic diol; Examples thereof include AO adducts having 2 to 4 carbon atoms (2 to 30 addition moles) of bisphenols (such as bisphenol A, bisphenol F, and bisphenol S), and two or more types may be used in combination.

Among the polyol components, the polyol having 3 to 8 or more valences includes 3 to 8 or more aliphatic polyhydric alcohols having 3 to 36 carbon atoms (glycerin, triethylolethane, trimethylolpropane, pentaerythritol and sorbitol). AO adduct having 2 to 4 carbon atoms of the above aliphatic polyhydric alcohol (addition mole number 2 to 30); AO adduct having 2 to 4 carbon atoms (addition moles) of trisphenols (trisphenol PA and the like); 2-30); novolak resins (phenol novolak, cresol novolak, etc .: average degree of polymerization 3-60) carbon number 2-4 AO adduct (added mole number 2-30), and the like. You may use together.
Among these polyol components, preferably, a polyalkylene ether glycol having 2 to 6 carbon atoms, an alicyclic diol having 6 to 36 carbon atoms, or an alicyclic diol having 6 to 36 carbon atoms having 2 to 4 carbon atoms. AO adducts, AO adducts having 2 to 4 carbon atoms of bisphenols, and AO adducts of 2 to 4 carbon atoms of novolak resins, more preferably AO (EO and EO and C2) of bisphenols. And / or PO) adducts, and AO (EO and / or PO) adducts having 2 to 3 carbon atoms of novolak resins.

Among the polycarboxylic acid components of the raw material of the polyester resin (a), as aliphatic (including alicyclic) dicarboxylic acids, alkane dicarboxylic acids having 2 to 50 carbon atoms (oxalic acid, malonic acid, succinic acid, adipic acid, Rephenic acid and sebacic acid), alkene dicarboxylic acids having 4 to 50 carbon atoms (alkenyl succinic acid such as dodecenyl succinic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and glutaconic acid), etc. Can be mentioned.
Examples of the aromatic dicarboxylic acid include aromatic dicarboxylic acids having 8 to 36 carbon atoms (such as phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid).

Among the polycarboxylic acid components, trivalent to hexavalent or higher aliphatic (including alicyclic) polycarboxylic acids include aliphatic tricarboxylic acids having 6 to 36 carbon atoms (such as hexanetricarboxylic acid) and unsaturated carboxylic acids. Examples include acid vinyl polymers [number average molecular weight (hereinafter referred to as Mn, according to gel permeation chromatography (GPC)): 450 to 10,000] (α-olefin / maleic acid copolymer and the like).
Among the polycarboxylic acid components, trivalent to hexavalent or higher aromatic polycarboxylic acids include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid), and unsaturated carboxylic acids. Vinyl polymers [Mn: 450 to 10000] (such as styrene / maleic acid copolymer, styrene / acrylic acid copolymer, and styrene / fumaric acid copolymer).
As the polycarboxylic acid component, anhydrides and lower alkyl (carbon number 1 to 4) esters (methyl ester, ethyl ester, isopropyl ester, etc.) of these polycarboxylic acids may be used.

  Among these polycarboxylic acid components, preferred are alkane dicarboxylic acids having 2 to 50 carbon atoms, alkene dicarboxylic acids having 4 to 50 carbon atoms, aromatic dicarboxylic acids having 8 to 20 carbon atoms, and 9 to 20 carbon atoms. An aromatic polycarboxylic acid, more preferably adipic acid, alkenyl succinic acid having 16 to 50 carbon atoms, terephthalic acid, isophthalic acid, maleic acid, fumaric acid, trimellitic acid, pyromellitic acid, and combinations thereof Particularly preferred are adipic acid, terephthalic acid, trimellitic acid, and combinations thereof. Likewise preferred are anhydrides and lower alkyl esters of these acids.

  Moreover, as a polycarboxylic acid component, what consists of aromatic polycarboxylic acid and aliphatic polycarboxylic acid as needed, and contains 60 mol% or more of aromatic polycarboxylic acid is preferable. The content of the aromatic polycarboxylic acid is more preferably 70 to 100 mol%, particularly preferably 80 to 100 mol%. By containing 60 mol% or more of aromatic polycarboxylic acid, the resin strength increases and the low-temperature fixability is further improved.

  The polyester resin (a) can be produced in the same manner as in an ordinary polyester production method. For example, the reaction can be carried out in an inert gas (nitrogen gas or the like) atmosphere at a reaction temperature of preferably 150 to 280 ° C, more preferably 160 to 250 ° C, particularly preferably 170 to 240 ° C. The reaction time is preferably 30 minutes or longer, particularly 2 to 40 hours from the viewpoint of reliably performing the polycondensation reaction.

  The reaction ratio between the polyol component and the polycarboxylic acid component is preferably 1.4 / 1 to 1/1, more preferably 1.35 / 1 to 1 as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. 1.1 / 1, particularly preferably 1.35 / 1 to 1.2 / 1. In addition, the said reaction ratio is a ratio which excluded the part, when there exists a component removed out of a system during reaction.

The polyester resin (a) has an acid value of 6 (mg KOH / g, the same for the following acid values) or less and a hydroxyl value of 10-85 (mg KOH / g, the same for the following hydroxyl values). The acid value is preferably 5 or less, more preferably 4 or less, and the hydroxyl value is preferably 15 to 81, more preferably 20 to 60. When the acid value is 6 or less, or when the hydroxyl value is 85 or less, the polyester resin (a) is sufficiently polycondensed and has low molecular weight components, and the storage stability of the toner resin obtained using the polyester resin (a) is small. It becomes good. When the hydroxyl value is 10 or more, the reaction efficiency with the carboxylic acid (b) is good.
In order to set the acid value and hydroxyl value of the polyester resin (a) within these ranges, it is effective to adjust the reaction ratio between the polyol component and the polycarboxylic acid component.

In the above and the following, the acid value and hydroxyl value of the polyester resin are measured by the method specified in JIS K0070 (1992 version).
When the sample has a solvent-insoluble component accompanying crosslinking, the sample after melt-kneading is used as a sample by the following method.
Kneading device: Labo plast mill MODEL4M150 manufactured by Toyo Seiki Co., Ltd.
Kneading conditions: 130 ° C., 70 rpm, 30 minutes

  Regarding the molecular weight of the THF-soluble component of the polyester resin (a), the peak top molecular weight (hereinafter referred to as Mp) is preferably 1500 to 15000, and more preferably 2200 to 10,000. Further, Mn is preferably 500 to 9000, more preferably 1000 to 7000, and particularly preferably 1500 to 6000.

In the present invention, the molecular weight [Mp, Mn, and weight average molecular weight (hereinafter referred to as Mw)] of the polyester resin is measured using GPC under the following conditions.
Device (example): HLC-8120 manufactured by Tosoh Corporation
Column (example): TSK GEL GMH6 2 [Tosoh Corp.]
Measurement temperature: 40 ° C
Sample solution: 0.25 wt% THF (tetrahydrofuran) solution Solution injection amount: 100 μl
Detection device: Refractive index detector Reference material: Tosoh standard polystyrene (TSK standard POLYSYRENE) 12 points (molecular weight 1050 2800 5970 9100 18100 37900 96400 190000 355000 1090000 2890000 4480000)
The molecular weight showing the maximum peak height on the obtained chromatogram is referred to as peak top molecular weight (Mp). The molecular weight was measured by dissolving a polyester resin in THF and filtering out the insoluble matter with a glass filter.

  The non-linear polyester resin (A) is composed of a polyester resin (a), an aliphatic carboxylic acid, an aromatic carboxylic acid, an acid anhydride of these carboxylic acids, and a lower alkyl (1 to 4 carbon atoms) ester of these carboxylic acids. One or more carboxylic acids (b) selected from the group consisting of the following: the mixing ratio at the time of reaction is equivalent to OHa for the hydroxyl group derived from (a), and the equivalent of the carboxyl group derived from (b) to COOHb At this time, a product obtained by reacting at an equivalent ratio of OHa / COOHb = 0.1 to 1.0 is preferable. OHa / COOHb is more preferably 0.2 to 0.9, and particularly preferably 0.3 to 0.8. When OHa / COOHb is 0.1 or more, the molecular weight becomes sufficiently large, and the hot offset resistance at the time of toner formation is improved. When it is 1.0 or less, the fluidity of the resin becomes good, and the low-temperature fixability and glossiness at the time of toner formation are improved.

As the carboxylic acid (b), either a monocarboxylic acid or a polycarboxylic acid can be used. The ratio of the monocarboxylic acid to the polycarboxylic acid is such that the equivalent of all carboxyl groups of the carboxylic acid used in the reaction is 100. The equivalent ratio of the carboxyl group derived from the monocarboxylic acid and the carboxyl group derived from the polycarboxylic acid is preferably (0-50) / (50-100), and (0-20) / (80-100) is more preferred. preferable. When the ratio of the carboxyl derived from the monocarboxylic acid is 50 or less, the crosslinking is not insufficient and the strength of the resin is sufficiently obtained. Moreover, it is easy to adjust the acid value of the reaction product within a predetermined range.
As (b), acid anhydrides and lower alkyl (C1-4) esters (methyl esters, ethyl esters, isopropyl esters, etc.) may be used.

Among the monocarboxylic acids used as the carboxylic acid (b), the aliphatic (including alicyclic) monocarboxylic acids include alkane monocarboxylic acids having 1 to 50 carbon atoms (formic acid, acetic acid, propionic acid, butanoic acid, isobutane). Acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, etc.), C3-C50 alkene monocarboxylic acid (acrylic acid, methacrylic acid, oleic acid, linoleic acid, etc.), etc. .
Examples of the aromatic monocarboxylic acid include aromatic monocarboxylic acids having 7 to 36 carbon atoms (such as benzoic acid, methylbenzoic acid, phenylpropionic acid, and naphthoic acid).

Among the polycarboxylic acids used as (b), aliphatic (including alicyclic) dicarboxylic acids, aromatic dicarboxylic acids, trivalent to hexavalent or higher aliphatic (including alicyclic) polycarboxylic acids, and Examples of the trivalent to hexavalent or higher aromatic polycarboxylic acid include those similar to those used for the polyester resin (a).
Among these, divalent or higher aromatic carboxylic acids are preferable, trivalent to hexavalent or higher aromatic polycarboxylic acids are more preferable, and trimellitic acid and trimellitic anhydride are particularly preferable.

  The content of an aromatic polycarboxylic acid having 3 to 6 or more valences in the carboxylic acid component constituting the non-linear polyester resin (A) is preferably 1 to 30 mol%, more preferably 2 to 20 mol%. It is. When it is 30 mol% or less, the fluidity of the resin is good, and the low-temperature fixability at the time of toner formation is improved.

The non-linear polyester resin (A) is obtained by the same production method as the polyester resin (a) except that the non-linear polyester resin (A) is preferably adjusted to have an acid value, a hydroxyl value, and an acid value / hydroxyl value in the following ranges. be able to.
The acid value of (A) in the present invention is preferably 12 to 85, more preferably 13 to 80, and particularly preferably 18 to 60. The hydroxyl value is preferably 5 or more, more preferably 8 or more, particularly preferably 9 to 40, and most preferably 10 to 30.
When the acid value is 12 or more or the hydroxyl value is 5 or more, the fixing strength is improved. Further, when the acid value is 85 or less, it is hardly affected by environmental conditions and stability is improved.
In the present invention, the acid value and hydroxyl value of (A) preferably further satisfy the relationship of the following formula (1).
Acid value / hydroxyl value ≧ 1 (however, acid value = 12 to 85, hydroxyl value ≧ 5) Formula (1)
When the acid value / hydroxyl value is 1 or more, the glossiness at the glossiness expression temperature and the fixing temperature range is improved. The acid value / hydroxyl value is more preferably 1.2 to 10. In addition, in order to manufacture the polyester resin (A) which satisfy | fills Formula (1), it can achieve by adjusting the reaction ratio of a polyester resin (a) and carboxylic acid (b), for example.

  The THF-insoluble content of the non-linear polyester resin (A) is 3 to 45% by weight, preferably 3 to 36% by weight, more preferably 4 to 33% by weight, and particularly preferably 5 to 30% by weight. . If the THF-insoluble content is less than 3% by weight, the hot offset resistance is lowered, and if it exceeds 45% by weight, the low-temperature fixability is lowered.

In the above and the following, the THF-insoluble content of the polyester resin is determined by the following method.
Add 50 ml of THF to 0.5 g of the sample and stir to reflux for 3 hours. After cooling from the reflux temperature to 20 ° C., the insoluble matter is filtered off with a glass filter, and the resin content on the glass filter is dried under reduced pressure at 80 ° C. for 3 hours. The insoluble matter is calculated from the weight of the dried resin content on the glass filter and the weight ratio of the sample.

The softening point of the non-linear polyester resin (A) used in the present invention is 120 to 185 ° C., preferably 125 to 170 ° C., more preferably 130 to 160 ° C., from the viewpoint of hot offset resistance and low-temperature fixability. It is.
In the present invention, the temperature was raised at a constant speed using a flow tester under the following conditions, and the temperature at which the outflow amount was halved was defined as the softening point.
Device: Shimadzu Corporation flow tester CFT-500
Load: 20kg
Die: 1mmΦ-1mm
Temperature increase rate: 6 ° C./min.

In the present invention, it is preferable that the THF-insoluble matter and the softening point in (A) satisfy the relationship of the following formula (2).
Value representing the THF-insoluble content in weight% / Numerical value representing the softening point in ° C. ≦ 0.22
... Formula (2)
When the THF insoluble content / softening point is 0.22 or less, it is easy to achieve both low-temperature fixability and hot offset resistance, and the glossiness at the glossiness expression temperature and the fixing temperature range is improved. The THF insoluble matter / softening point is more preferably 0.01 to 0.20.
In order to produce the non-linear polyester resin (A) satisfying the formula (2), for example, after the polyester resin (a) is produced, (a) and the carboxylic acid (b) are reacted. This can be achieved by producing the polyester resin (A), in which case the hydroxyl value of (a) is 10 to 85 mgKOH / g and the reaction rate of (a) and (b) is adjusted. Specifically, when the reaction rate of (a) and (b) is lowered [that is, the amount of unreacted hydroxyl group of (a) and carboxyl group of (b) is increased], THF insoluble matter / softening On the contrary, the reaction rate of (a) and (b) is increased (that is, the amount of unreacted (a) hydroxyl group and (b) carboxyl group is decreased) and THF insoluble matter / softening The point goes up.

The molecular weight of the THF-soluble component of the non-linear polyester resin (A) is 3500 to 25000, preferably 4000 to 20000, and more preferably 4900 to 15000. Mw is preferably 20000 to 400000, more preferably 30000 to 300000, and particularly preferably 40000 to 250,000. Further, the ratio of Mw and Mn (hereinafter referred to as Mw / Mn) showing the molecular weight distribution is preferably 15 to 100, and more preferably 20 to 90.
When Mp, Mw, and Mw / Mn are within the above ranges, the balance between hot offset resistance and low-temperature fixability is good.

In the present invention, the non-linear polyester resin (A) preferably has a softening point difference of 10 ° C. or less before and after being melted by heating at 200 ° C., more preferably 5 ° C. or less. In addition, the softening point after heating and melting at 200 ° C is preferably 110 to 195 ° C, and more preferably 120 to 185 ° C.
In addition, the difference of the softening point before and behind heat-melting at 200 degreeC is measured as follows.
A test tube containing 3 g of (A) is placed in a block bath adjusted to 200 ° C., heated and dissolved for about 10 minutes, and then dissolved (A) is put into ice water together with the test tube and cooled. For the heated and melted (A) and the pre-heated and melted (A), the softening point is measured by the above method, and the difference is obtained.

In the present invention, the non-linear polyester resin (A) preferably has a change rate of Mp of the component soluble in THF before and after being heated and melted at 200 ° C. of 10% or less, and 9% or less. Further preferred. In addition, 3150-27500 are preferable and Mp after heat-melting at 200 degreeC has more preferable 3500-25000.
The method of heat-melting treatment at 200 ° C. is the same as the method described in the previous section, and Mp is the same as the Mp measurement method of the polyester resin described above.
As a method for reducing the difference in softening point before and after melting at 200 ° C. and the difference in Mp of components soluble in THF before and after melting at 200 ° C., for example, the reaction of (a) and (b) A method of cooling the non-linear polyester resin (A) after completion using a device such as a belt cooler in a shorter time can be mentioned.

The toner resin of the present invention may contain a linear polyester resin (B) together with the non-linear polyester resin (A). The toner resin of the present invention exhibits excellent fixability even with the non-linear polyester resin (A) alone, but is further improved by containing the non-linear polyester resin (A) and the linear polyester resin (B). Fixability can be obtained.
The linear polyester resin (B) is usually obtained by polycondensation of one or more polyol components and one or more polycarboxylic acid components, and the linear polyester resin (B) has a composition if it is combined and reacted so as to be linear. Is not particularly limited.

  Among the polyol components used as the raw material of (B), as the diol, the aliphatic diol having 2 to 36 carbon atoms, the polyalkylene ether glycol having 4 to 36 carbon atoms, and the carbon number 2 of the aliphatic diol having 2 to 36 carbon atoms. -4 AO adduct (addition mole number 2-30), alicyclic diol having 6-36 carbon atoms, AO adduct having 2-4 carbon atoms of alicyclic diol having 6-36 carbon atoms (addition mole number) 2 to 30), and AO adducts having 2 to 4 carbon atoms (2 to 30 addition moles) of bisphenols, and the like may be used in combination. Specific examples thereof are the same as those used for the polyester resin (a).

  Among the polyol components, the alcohol having 3 to 8 or more valences includes 3 to 8 or more aliphatic polyhydric alcohols having 3 to 36 carbon atoms, or AO having 2 to 4 carbon atoms of the aliphatic polyhydric alcohols. Adduct (addition mole number 2 to 30), trisphenol A2 adduct having 2 to 4 carbon atoms (addition mole number 2 to 30), novolak resin 2 to 4 carbon atoms AO adduct (addition mole number 2) ~ 30) and the like, and two or more of them may be used in combination. Specific examples thereof are the same as those used for the polyester resin (a).

  Among these polyol components, preferred are aliphatic diols having 2 to 6 carbon atoms, polyalkylene ether glycols having 4 to 36 carbon atoms, alicyclic diols having 6 to 36 carbon atoms, and alicyclic diols having 6 to 36 carbon atoms. AO adduct having 2 to 4 carbon atoms, an AO adduct having 2 to 4 carbon atoms of bisphenols, and an AO adduct having 2 to 4 carbon atoms of novolak resin, more preferably 2 to 6 carbon atoms. An aliphatic diol, an AO (EO and PO) adduct having 2 to 3 carbon atoms of bisphenols, and an AO (EO and PO) adduct having 2 to 3 carbon atoms of a novolak resin.

Among the polycarboxylic acid components, aliphatic (including alicyclic) dicarboxylic acid, aromatic dicarboxylic acid, 3 to 6 or more aliphatic (including alicyclic) polycarboxylic acid, and 3 to 6 valent Examples of the aromatic polycarboxylic acid higher than that include those used for the polyester resin (a).
As the polycarboxylic acid component, anhydrides and lower alkyl (C1 to C4) esters of these polycarboxylic acids may be used.
Among these polycarboxylic acid components, preferred are the same polycarboxylic acids used for the polyester resin (a).

The acid value of the linear polyester resin (B) is preferably 5 to 80, more preferably 8 to 50, and particularly preferably 10 to 30.
The hydroxyl value is preferably 60 or less, more preferably 50 or less, and particularly preferably 5 to 45.
As for the molecular weight of linear polyester resin (B), it is preferable that Mp is 3000-10000, and it is more preferable that it is 3500-9000.

  The THF-insoluble content of the linear polyester resin (B) is preferably less than 3% by weight, more preferably 2% by weight or less.

In the present invention, the polyester resin (B) can be produced in the same manner as in an ordinary polyester production method. For example, the method similar to the manufacturing method of the above-mentioned polyester resin (a) is mentioned.
The reaction ratio between the polyol component and the polycarboxylic acid component is preferably 2/1 to 1/2, more preferably 1.5 / 1 to 1/1 / as the equivalent ratio [OH] / [COOH] of the hydroxyl group to the carboxyl group. 1.3, particularly preferably 1.3 / 1 to 1 / 1.2.

  In the toner resin of the present invention, the weight ratio [(A) / (B)] of the non-linear polyester resin (A) to the linear polyester resin (B) is 100 as the sum of (A) and (B). (20-100) / (80-0) is preferred, (30-99) / (70-1) is more preferred, and (40-90) / (60-10) is particularly preferred. When the weight ratio of the non-linear polyester resin (A) is 20 or more, the resin strength increases, and the fixability in a high temperature range is good.

Further, the titanium element content of the polyester resin (B) is preferably 20 to 2000 ppm, more preferably 30 to 1800 ppm, and particularly preferably 50 to 1500 ppm. When the titanium element content is 2000 ppm or less, the coloration of (B) becomes small, and the color reproducibility when used as a toner is good. Moreover, when titanium element content is 20 ppm or more, the time required for polycondensation when obtaining (B) may be shortened.
As a method of adjusting the titanium element content to the above range, a method of using one or more titanium-containing catalysts during the polycondensation reaction when obtaining (B) and adjusting the amount used is preferable.

  The nitrogen element content of the polyester resin (B) is preferably 10 to 1200 ppm, more preferably 20 to 1100 ppm, and particularly preferably 30 to 1000 ppm. When the nitrogen element content is 1200 ppm or less, the coloring of (A) becomes small, and the color reproducibility when used as a toner becomes better. Further, when the nitrogen element content is 10 ppm or more, the effect of the present invention is more easily obtained.

The toner resin of the present invention preferably contains only the non-linear polyester resin (A) or only the non-linear polyester resin (A) and the linear polyester resin (B). Other resins may be contained as long as the above properties are not impaired. Other resins include polyester resins other than (A) and (B), vinyl resins [copolymers of styrene and alkyl (meth) acrylate, copolymers of styrene and diene monomers, etc.], epoxy resins ( Bisphenol A diglycidyl ether ring-opening polymer), urethane resin (diol and / or polyaddition product of tri- or higher valent polyol and diisocyanate, etc.).
The Mn of other resins is preferably 300 to 100,000. The content of the other resin is preferably 10% by weight or less, more preferably 8% by weight or less in the total resin for toner.

When two or more kinds of polyester resins are used in combination, and when at least one kind of polyester resin and another resin are mixed, powder mixing or melt mixing may be performed in advance, or they may be mixed at the time of toner formation.
The temperature at the time of melt mixing is preferably 80 to 180 ° C, more preferably 100 to 170 ° C, and particularly preferably 120 to 160 ° C.
If the mixing temperature is too low, sufficient mixing cannot be achieved, which may result in non-uniformity. When two or more kinds of polyester resins are mixed, if the mixing temperature is too high, averaging due to transesterification occurs, so that the resin physical properties necessary as a toner binder may not be maintained.

The mixing time in the case of melt mixing is preferably 10 seconds to 30 minutes, more preferably 20 seconds to 10 minutes, and particularly preferably 30 seconds to 5 minutes. When two or more kinds of polyester resins are mixed, if the mixing time is too long, averaging due to transesterification occurs, so that the resin physical properties necessary as a toner binder may not be maintained.
Examples of the mixing device in the case of melt mixing include a batch type mixing device such as a reaction tank and a continuous mixing device. In order to uniformly mix at an appropriate temperature in a short time, a continuous mixing device is preferable. Examples of the continuous mixing device include an extruder, a continuous kneader, and a three roll. Of these, extruders and continuous kneaders are preferred.
In the case of powder mixing, it can be mixed with normal mixing conditions and mixing equipment.
As mixing conditions in the case of powder mixing, the mixing temperature is preferably 0 to 80 ° C, more preferably 10 to 60 ° C. The mixing time is preferably 3 minutes or more, more preferably 5 to 60 minutes. Examples of the mixing apparatus include a Henschel mixer, a Nauter mixer, and a Banbury mixer. A Henschel mixer is preferable.

  The toner composition of the present invention contains the toner resin of the present invention as a binder resin, a colorant, and, if necessary, one or more additives such as a release agent, a charge control agent, and a fluidizing agent.

As the colorant, all of dyes and pigments used as toner colorants can be used. Specifically, carbon black, iron black, Sudan Black SM, First Yellow G, Benzidine Yellow, Pigment Yellow, Indian First Orange, Irgasin Red, Paranitroaniline Red, Toluidine Red, Carmine FB, Pigment Orange R, Lake Red 2G, Rhodamine FB, Rhodamine B Lake, Methyl Violet B Lake, Phthalocyanine Blue, Pigment Blue, Brilliant Green, Phthalocyanine Green, Oil Yellow GG, Kayaset YG, Orazol Brown B and Oil Pink OP, etc. Or 2 or more types can be mixed and used. Further, if necessary, magnetic powder (a powder of a ferromagnetic metal such as iron, cobalt, nickel, or a compound such as magnetite, hematite, ferrite) can also be included as a colorant. The content of the colorant is preferably 1 to 40 parts, more preferably 3 to 10 parts with respect to 100 parts of the resin for toner of the present invention. In addition, when using magnetic powder, Preferably it is 20-150 parts, More preferably, it is 40-120 parts.
Above and below, parts mean parts by weight.

  The release agent preferably has a softening point of 50 to 170 ° C., and examples thereof include polyolefin wax, natural wax, aliphatic alcohol having 30 to 50 carbon atoms, fatty acid having 30 to 50 carbon atoms, and a mixture thereof. Polyolefin waxes include (co) polymers [obtained by (co) polymerization] of olefins (for example, ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-dodecene, 1-octadecene, and mixtures thereof). And olefin (co) polymer oxides with oxygen and / or ozone, maleic acid modifications of olefin (co) polymers [eg maleic acid and its derivatives (maleic anhydride, Modified products such as monomethyl maleate, monobutyl maleate and dimethyl maleate), olefins and unsaturated carboxylic acids [such as (meth) acrylic acid, itaconic acid and maleic anhydride] and / or unsaturated carboxylic acid alkyl esters [(meta ) Alkyl acrylate (alkyl 1 to 1 carbon atoms) 8) esters and maleic acid alkyl (C1-18 alkyl) copolymers of an ester, etc.] or the like, and Sasol wax.

  Examples of natural waxes include carnauba wax, montan wax, paraffin wax, and rice wax. Examples of the aliphatic alcohol having 30 to 50 carbon atoms include triacontanol. Examples of the fatty acid having 30 to 50 carbon atoms include triacontane carboxylic acid.

  As charge control agents, nigrosine dyes, triphenylmethane dyes containing tertiary amines as side chains, quaternary 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 aromatic ring-containing polymers, and the like.

  Examples of the fluidizing agent include colloidal silica, alumina powder, titanium oxide powder, and calcium carbonate powder.

  The weight ratio of the toner composition of the present invention is preferably 30 to 97% by weight, more preferably 40 to 95% by weight, particularly preferably 45 to 92% by weight of the resin for toner of the present invention based on the toner weight. The colorant is preferably 0.05 to 60% by weight, more preferably 0.1 to 55% by weight, particularly preferably 0.5 to 50% by weight; among the additives, the release agent is preferably 0 to 30 wt%, more preferably 0.5 to 20 wt%, particularly preferably 1 to 10 wt%; the charge control agent is preferably 0 to 20 wt%, more preferably 0.1 to 10 wt%, particularly preferably 0.5 to 7.5% by weight; the fluidizing agent is preferably 0 to 10% by weight, more preferably 0 to 5% by weight, and particularly preferably 0.1 to 4% by weight. The total content of additives is preferably 3 to 70% by weight, more preferably 4 to 58% by weight, and particularly preferably 5 to 50% by weight. When the composition ratio of the toner is in the above range, a toner having good chargeability can be easily obtained.

The toner composition of the present invention may be obtained by any conventionally known method such as a kneading and pulverizing method, an emulsion phase inversion method, or a polymerization method. For example, when a toner is obtained by a kneading and pulverizing method, the components constituting the toner excluding the fluidizing agent are dry blended, and then melt-kneaded, then coarsely pulverized, and finally atomized using a jet mill pulverizer or the like. Further, by further classifying, the volume average particle diameter (D50) is preferably 5 to 20 μm and then mixed with a fluidizing agent. The particle size (D50) is measured using a Coulter counter [for example, trade name: Multisizer III (manufactured by Coulter)].
When the toner is obtained by the emulsion phase inversion method, the components constituting the toner excluding the fluidizing agent are dissolved or dispersed in an organic solvent, and then emulsified by adding water, etc., and then separated and classified. it can. The volume average particle diameter of the toner is preferably 3 to 15 μm.

  The toner composition of the present invention is electrically mixed with carrier particles such as ferrite coated on the surface with iron powder, glass beads, nickel powder, ferrite, magnetite and resin (acrylic resin, silicone resin, etc.) as necessary. Used as a latent image developer. The weight ratio of toner to carrier particles is usually 1/99 to 100/0. In addition, instead of carrier particles, it can be rubbed with a member such as a charging blade to form an electrical latent image.

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

  EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

Production Example 1
[Synthesis of titanium-containing catalyst]
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube capable of bubbling in the liquid, 1000 parts of titanium tetraisopropoxide after substitution with nitrogen, and then a mixture of triethanolamine / ion-exchanged water = 1050 parts / 150 parts. The mixture was gradually heated to 90 ° C. under nitrogen bubbling and reacted at 90 ° C. for 4 hours. Furthermore, the reaction (dehydration condensation) was performed at 100 ° C. under reduced pressure for 2 hours to obtain the intramolecular polycondensate (z1).

Example 1
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 50 parts (0.15 mole) of bisphenol A · PO2 mole adduct, 480 parts (1.19 mole) of bisphenol A · PO3 mole adduct, phenol 8.5 parts (0.01 mol) of EO adduct of novolak (average functional group number 5.6), 170 parts (1.02 mol) of terephthalic acid, and 4 parts of titanium-containing catalyst (z1) as a condensation catalyst, The reaction was carried out for 5 hours at 230 ° C. while distilling off the water produced under a nitrogen stream. Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, it was taken out, cooled to room temperature, pulverized and granulated. This is designated as polyester resin (a1).
The acid value of the polyester resin (a1) was 1.7, the hydroxyl value was 54, Mn was 2000, and Mp was 4800.

650 parts of polyester resin (a1), 45 parts (0.23 mol) of trimellitic anhydride, and 2 parts of a titanium-containing catalyst (z1) as a catalyst in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe After replacing the gas phase in the system with nitrogen, reacting at 180 ° C. for 2 hours under sealed at atmospheric pressure, then reacting at 220 ° C. under reduced pressure of 500 to 700 mmHg, and when the softening point becomes 135 ° C. It was taken out through a cooler and pulverized into particles. OHa / COOHb at the time of reaction was 0.89. This is designated as polyester resin (A1).
The polyester resin (A1) has an acid value of 26, a hydroxyl value of 12, Mw of 110000, Mp of 10700, a softening point of 136 ° C., and a THF-insoluble content of 9% by weight, that is, the left side of the formula (1) is 2. 2. The left side of the formula (2) was 0.07, the titanium element content was 1110 ppm, and the nitrogen element content was 719 ppm. The softening point when (A1) was heated and melted at 200 ° C. and then cooled with ice water was 134 ° C. (difference in softening point before and after heating and melting: −2 ° C.).

In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 340 parts (1.08 mol) of bisphenol A · EO 2 mol adduct, 370 parts (1.08 mol) of bisphenol A · PO 2 mol adduct, bisphenol A · PO 3 mol adduct 140 parts (0.35 mol), terephthalic acid 332 parts (2.00 mol) and titanium-containing catalyst (z1) 4 parts as a condensation catalyst, water produced at 230 ° C. under a nitrogen stream The reaction was allowed to proceed for 5 hours while distilling off. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg. When the acid value became 2 or less, the mixture was cooled to 180 ° C., added with 40 parts (0.21 mol) of trimellitic anhydride, and reacted for 2 hours under sealed at atmospheric pressure. The sample was taken out and taken out through a belt cooler, and pulverized into particles. This is designated as polyester resin (B1).
The acid value of the polyester resin (B1) was 20, the hydroxyl value was 36, Mn was 2100, Mp was 4400, the THF-insoluble content was 0% by weight, the titanium element content was 470 ppm, and the nitrogen element content was 268 ppm.

  700 parts of the polyester resin (A1) and 300 parts of the polyester resin (B1) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature, pulverized with a pulverizer, and pulverized to obtain a toner resin (1) of the present invention.

Example 2
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 30 parts (0.09 mol) of bisphenol A · EO 2 mol adduct, 70 parts (0.20 mol) of bisphenol A · PO 2 mol adduct, bisphenol 320 parts (0.80 moles) of A.PO3 mole adduct, 10 parts (0.07 moles) of adipic acid, 25 parts (0.03 moles) of EO moles of phenol novolac (average functional group number 5.6), 150 parts (0.90 mol) of terephthalic acid and 3 parts of a titanium-containing catalyst (z1) as a condensation catalyst were added and reacted at 230 ° C. for 5 hours while distilling off the water generated in a nitrogen stream. Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, it was taken out, cooled to room temperature, pulverized and granulated. This is designated as polyester resin (a2).
The acid value of the polyester resin (a2) was 1.2, the hydroxyl value was 39, Mn was 3500, and Mp was 6900.

550 parts of polyester resin (a2), 30 parts (0.16 mol) of trimellitic anhydride, and 1 part of a titanium-containing catalyst (z1) as a catalyst in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe After replacing the gas phase in the system with nitrogen, reacting at 180 ° C. for 2 hours under sealed at atmospheric pressure, then reacting at 220 ° C. under reduced pressure of 500 to 700 mmHg, and when the softening point becomes 135 ° C. It was taken out through a cooler and pulverized into particles. OHa / COOHb at the time of reaction was 0.81. This is designated as polyester resin (A2).
The acid value of the polyester resin (A2) is 32, the hydroxyl value is 11, Mw is 80000, Mp is 7500, the softening point is 134 ° C., and the THF-insoluble matter is 27% by weight, that is, the left side of the formula (1) is 2. 9. The left side of the formula (2) was 0.20, the titanium element content was 884 ppm, and the nitrogen element content was 572 ppm. The softening point when (A2) was heated and melted at 200 ° C. and then cooled with ice water was 134 ° C. (difference in softening point before and after heating and melting: 0 ° C.).

  700 parts of the polyester resin (A2) and 300 parts of the polyester resin (B1) were melt-mixed with a continuous kneader at a jacket temperature of 150 ° C. and a residence time of 3 minutes. The molten resin was cooled to room temperature, pulverized by a pulverizer, and pulverized to obtain a toner resin (2) of the present invention.

Example 3
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 200 parts (0.63 mol) of bisphenol A · EO 2 mol adduct, 150 parts (0.44 mol) of bisphenol A · PO 2 mol adduct, bisphenol A. PO 3 mol adduct 320 parts (0.80 mol), phenol novolac (average functional group number 5.6) PO adduct 4 parts (0.01 mol), terephthalic acid 166 parts (1.00 mol), and 2 parts of a titanium-containing catalyst (z1) was added as a condensation catalyst, and the reaction was carried out at 230 ° C. for 5 hours while distilling off the water produced in a nitrogen stream. Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, it was taken out, cooled to room temperature, pulverized and granulated. This is designated as polyester resin (a3).
The acid value of the polyester resin (a3) was 1.4, the hydroxyl value was 49, Mn was 2200, and Mp was 5000.

In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 500 parts of a polyester resin (a3), 30 parts (0.16 mol) of trimellitic anhydride, and 2 parts of a titanium-containing catalyst (z1) as a catalyst. After replacing the gas phase in the system with nitrogen, reacting at 180 ° C. for 2 hours under sealed at atmospheric pressure, then reacting at 220 ° C. under reduced pressure of 500 to 700 mmHg, and when the softening point becomes 135 ° C. It was taken out through a cooler and pulverized into particles. OHa / COOHb at the time of reaction was 0.93. This is designated as polyester resin (A3).
The polyester resin (A3) has an acid value of 13, a hydroxyl value of 10, Mw of 90000, Mp of 6400, a softening point of 137 ° C., and a THF-insoluble content of 7% by weight, that is, the left side of the formula (1) is 1. 3. The left side of the formula (2) was 0.05, the titanium element content was 966 ppm, and the nitrogen element content was 672 ppm. The softening point when (A3) was heated and melted at 200 ° C. and then cooled with ice water was 135 ° C. (difference in softening point before and after heating and melting: −2 ° C.).

  700 parts of a polyester resin (A3) and 300 parts of a polyester resin (B1) were mixed with a V-type mixer to obtain a toner resin (3) of the present invention.

Example 4
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 1,2-propylene glycol (hereinafter referred to as propylene glycol) 900 parts (11.84 mol), terephthalic acid 432 parts (2.60 mol), 24 parts (0.16 mol) of adipic acid and 4 parts of a titanium-containing catalyst (z1) as a condensation catalyst were placed in a nitrogen stream at 180 ° C. and reacted for 8 hours while distilling off generated water and propylene glycol. It was. Next, while gradually raising the temperature to 230 ° C., the reaction is carried out for 4 hours while distilling off the water and propylene glycol generated under a nitrogen stream, and further the reaction is carried out under a reduced pressure of 5 to 20 mmHg, so that the softening point becomes 95 ° C. It was taken out when it became. The taken out resin was cooled to room temperature and then pulverized into particles. This is designated as polyester resin (a4). The acid value of the polyester resin (a4) was 1.0, the hydroxyl value was 43, Mn was 2500, and Mp was 5100.

In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 500 parts of a polyester resin (a4), 40 parts (0.21 mol) of trimellitic anhydride, and 2 parts of a titanium-containing catalyst (z1) as a catalyst. After replacing the gas phase in the system with nitrogen, reacting at 180 ° C. for 2 hours under sealed at atmospheric pressure, then reacting at 220 ° C. under reduced pressure of 5 to 20 mmHg, and when the softening point becomes 158 ° C. It was taken out through a cooler and pulverized into particles. It was OHa / COOHb = 0.61 at the time of reaction. This is designated as polyester resin (A4).
The acid value of the polyester resin (A4) is 28, the hydroxyl value is 5, Mw is 154000, Mp is 8400, the softening point is 160 ° C., the THF insoluble matter is 17% by weight, that is, the left side of the formula (1) is 5. 6. The left side of Formula (2) was 0.11, the titanium element content was 1144 ppm, and the nitrogen element content was 846 ppm. The softening point when (A4) was heated and melted at 200 ° C. and then cooled with ice water was 158 ° C. (difference in softening point before and after heating and melting: −2 ° C.).

  700 parts of a polyester resin (A4) and 300 parts of a polyester resin (B1) were mixed with a V-type mixer to obtain a toner resin (4) of the present invention.

Example 5
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 20 parts (0.06 mol) of bisphenol A · EO 2 mol adduct, 300 parts (0.87 mol) of bisphenol A · PO 2 mol adduct, bisphenol A. PO 3 mol adduct 20 parts (0.50 mol), phenol novolac (average functional group number 5.6) EO adduct 20 parts (0.02 mol), terephthalic acid 166 parts (1.00 mol) and condensation 2 parts of a titanium-containing catalyst (z1) was added as a catalyst, and the reaction was performed at 230 ° C. for 5 hours while distilling off the water generated in a nitrogen stream. Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, it was taken out, cooled to room temperature, pulverized and granulated. This is designated as polyester resin (a5).
The acid value of the polyester resin (a5) was 1.4, the hydroxyl value was 81, Mn was 1000, and Mp was 2200.

In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, 500 parts of a polyester resin (a5), 50 parts (0.26 mol) of trimellitic anhydride, and 1 part of a titanium-containing catalyst (z1) as a catalyst. After replacing the gas phase in the system with nitrogen and reacting at 180 ° C. for 2 hours under sealed at normal pressure, the reaction was carried out at 200 ° C. under reduced pressure (10-50 mmHg) and under normal pressure (760 mmHg). When it reached 0 ° C., it was taken out through a belt cooler and pulverized into particles. OHa / COOHb at the time of reaction was 0.92. This is designated as polyester resin (A5).
The acid value of the polyester resin (A5) is 35, the hydroxyl value is 30, Mw is 56000, Mp is 4900, the softening point is 136 ° C., the THF-insoluble matter is 30% by weight, that is, the left side of the formula (1) is 1. 2. The left side of the formula (2) was 0.22, the titanium element content was 444 ppm, and the nitrogen element content was 396 ppm. The softening point when (A5) was heated and melted at 200 ° C. and then cooled with ice water was 133 ° C. (difference in softening point before and after heating and melting: −2 ° C.).

  450 parts of the polyester resin (A5) and 550 parts of the polyester resin (B1) were mixed with a V-type mixer to obtain the toner resin (5) of the present invention.

Example 6
The polyester resin (A2) was used as the toner resin (6) of the present invention.

Comparative Example 1
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 572 parts (1.4 moles) of bisphenol A / PO3 mole adduct, 22 parts of EO adduct of phenol novolac (average functional group number 5.6) ( 0.03 mol), 166 parts (1.0 mol) of terephthalic acid, and 3 parts of tetrabutoxytitanate as a condensation catalyst were allowed to react at 230 ° C. for 5 hours while distilling off the water produced in a nitrogen stream. Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, it was taken out, cooled to room temperature, pulverized and granulated. This is designated as polyester resin (c1).
The acid value of the polyester resin (c1) was 1.9, the hydroxyl value was 76, Mn was 1000, and Mp was 2500.

Into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 724 parts of polyester resin (c1), 83 parts (0.43 mol) of trimellitic anhydride, and 3 parts of tetrabutoxy titanate as a catalyst were added. After replacing the gas phase inside with nitrogen, after reacting at 180 ° C. for 2 hours under sealed at atmospheric pressure, react at 220 ° C. under reduced pressure of 10-50 mmHg, and when the softening point is 125 ° C., take it out to room temperature. After cooling, it was pulverized into particles. OHa / COOHb at the time of reaction was 0.76. This is designated as polyester resin (C1).
The polyester resin (C1) has an acid value of 25, a hydroxyl value of 23, Mw of 15000, Mp of 5000, a softening point of 135 ° C., and a THF-insoluble content of 35% by weight, that is, the left side of the formula (1) is 1. 1. The left side of the formula (2) was 0.26, the titanium element content was 1240 pm, and the nitrogen element content was 0.
The softening point when (C1) was heated and melted at 200 ° C. and then cooled with ice water was 123 ° C. (difference in softening point before and after heating and melting: −12 ° C.).

  700 parts of a polyester resin (C1) and 300 parts of a polyester resin (B1) were mixed with a V-type mixer to obtain a comparative toner resin (7).

Comparative Example 2
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen introduction tube, 480 parts (1.19 moles) of bisphenol A / PO3 mole adduct, 22 parts of EO adduct of phenol novolac (average functional group number 5.6) ( 0.03 mol), 166 parts (1.00 mol) of terephthalic acid, and 3 parts of tetrabutoxy titanate as a condensation catalyst were allowed to react at 230 ° C. for 5 hours while distilling off the water produced in a nitrogen stream. Next, the reaction was carried out under a reduced pressure of 5 to 20 mmHg, and when the acid value became 2 or less, it was taken out, cooled to room temperature, pulverized and granulated. This is designated as polyester resin (c2).
The acid value of the polyester resin (c2) was 1.8, the hydroxyl value was 46, Mn was 2600, and Mp was 5000.

In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 716 parts of a polyester resin (c2), 50 parts (0.26 mol) of trimellitic anhydride, and 3 parts of tetrabutoxy titanate as a catalyst were added. After replacing the gas phase inside with nitrogen, after reacting at 180 ° C. for 2 hours under sealed at atmospheric pressure, react at 220 ° C. under reduced pressure of 500 to 700 mmHg, and when the softening point becomes 130 ° C., take it out to room temperature. Cooled and pulverized into particles. OHa / COOHb at the time of reaction was 0.75. This is designated as polyester resin (C2).
The acid value of the polyester resin (C2) is 17, the hydroxyl value is 37, the Mw is 25500, the Mp is 5700, the softening point is 142 ° C., the THF insoluble matter is 19% by weight, that is, the left side of the formula (1) is 0. 5. The left side of the formula (2) was 0.13, the titanium element content was 1524 ppm, and the nitrogen element content was 0.
The softening point when (C2) was heated and melted at 200 ° C. and then cooled with ice water was 131 ° C. (difference in softening point before and after heating and melting: −11 ° C.).

  700 parts of the polyester resin (C2) and 300 parts of the polyester resin (B1) were mixed with a V-type mixer to obtain a comparative toner resin (8).

Examples [7-12] and Comparative Examples [3, 4]
Toner resins (1) to (6) of the present invention and comparative toner resins (7) and (8), 100 parts each, 5 parts carnauba wax and yellow pigment [toner yellow HG manufactured by Clariant Co., Ltd. VP2155] or 4 parts of a colorant [carbon black MA-100, manufactured by Mitsubishi Chemical Corporation] was premixed using a Henschel mixer [FM10B manufactured by Mitsui Miike Chemical Co., Ltd.], and then a twin-screw kneader [( Kneading with Ikegai PCM-30]. Then, after finely pulverizing using a supersonic jet crusher lab jet [manufactured by Nippon Pneumatic Industry Co., Ltd.], it is classified by an airflow classifier [MDS-I manufactured by Nippon Pneumatic Industry Co., Ltd.], and the particle size D50 is 7 μm toner particles were obtained. Next, 100 parts of toner particles are mixed with 0.5 part of colloidal silica (Aerosil R972: manufactured by Nippon Aerosil Co., Ltd.) in a sample mill, and the toner compositions (T1) to (T6) of the present invention and a comparative toner composition are used. Products (T7) and (T8) were obtained.
The evaluation results evaluated by the following evaluation methods are shown in Table 1.

[Developer preparation]
30 parts of toner and 800 parts of ferrite carrier (F-150, manufactured by Powdertech Co., Ltd.) were uniformly mixed to obtain a two-component developer.
[Evaluation methods]
[1] Minimum fixing temperature (MFT)
An unfixed image developed with a commercial copier (AR5030; manufactured by Sharp) using the above two-component developer is modified to a fixing unit of a commercial full-color copier (LBP-2160, manufactured by Canon Inc.) and the heat roller temperature is adjusted. Fixing was performed at a process speed of 110 mm / sec using a variable fixing machine. The minimum fixing temperature (MFT) was defined as the fixing roll temperature at which the residual ratio of the image density after rubbing the fixed image with a pad was 70% or more.
[2] Hot offset generation temperature (HOT)
The fixing was evaluated in the same manner as the MFT, and the presence or absence of hot offset on the fixed image was visually evaluated. The temperature at which the hot offset occurred was defined as the hot offset occurrence temperature (HOT).
[3] Toner blocking resistance test The toner composition was tested at 50 ° C. and 85% R.V. H. Was conditioned for 48 hours in a high temperature and high humidity environment. Under the same environment, the blocking state of the developer was visually determined, and the image quality when copying with a commercially available copying machine (AR5030: manufactured by Sharp) was observed.
Criteria A: There is no toner blocking, and the image quality after copying 3000 sheets is good.
○: There is no toner blocking, but a slight disturbance is observed in the image quality after copying 3000 sheets.
(Triangle | delta): The blocking of toner can be visually observed and disorder is observed in the image quality after 3000 copies.
X: Toner blocking is visible, and no image is produced by 3000 sheets.
[4] Color Reproducibility The above toner composition was printed on an OHP sheet using a commercially available copying machine (AR5030: manufactured by Sharp). This was projected on the screen with an OHP projector. The sharpness of the projected image and the color haze were visually evaluated.
A: The projected image is clear. No color dullness.
○: The projected image is clear. Slightly dull in color.
Δ: Projected image is slightly unclear. Slightly dull in color.
X: Projection image is unclear. There is a dull color.

  The toner composition and toner resin of the present invention are useful as an electrostatic charge image developing toner and a toner resin excellent in low-temperature fixability, hot offset resistance and developability.

Claims (10)

  The THF-insoluble content is 3 to 45% by weight, the THF-soluble content of gel permeation chromatography has a peak top molecular weight of 3500 to 25000, the softening point is 120 to 185 ° C., the titanium element is 20 to 2000 ppm, and the nitrogen element is A toner resin comprising a non-linear polyester resin (A) containing 10 to 1200 ppm. The toner resin according to claim 1, wherein the non-linear polyester resin (A) is a polyester resin satisfying the following formulas (1) and (2).
Acid value / hydroxyl value ≧ 1 (however, acid value = 12 to 85 mgKOH / g, hydroxyl value ≧ 5 mgKOH / g) Formula (1)
Value representing the THF-insoluble content in weight% / Numerical value representing the softening point in ° C. ≦ 0.22
... Formula (2)   Non-linear polyester resin (A) is a polyester resin (a) having an acid value of 6 mgKOH / g or less and a hydroxyl value of 10 to 85 mgKOH / g, an aliphatic carboxylic acid, an aromatic carboxylic acid, and acid anhydrides of these carboxylic acids. 3. The toner resin according to claim 1, which is a polyester resin obtained by reacting a carboxylic acid (b) selected from the group consisting of a carboxylic acid and a lower alkyl (carbon number 1 to 4) ester of these carboxylic acids. resin.   The resin for toner according to claim 1, wherein the non-linear polyester resin (A) has a weight average molecular weight of 20,000 to 400,000.   The resin for toner according to claim 1, wherein the difference in softening point between before and after the non-linear polyester resin (A) is heated and melted at 200 ° C. is 10 ° C. or less.   The resin for toner according to any one of claims 1 to 5, further comprising a linear polyester resin (B) in addition to the non-linear polyester resin (A).   When the weight ratio [(A) / (B)] of the non-linear polyester resin (A) and the linear polyester resin (B) is 100, the total of (A) and (B) is (20 to 100) The resin for toner according to claim 6, which is / (80 to 0).   The resin for toner according to claim 6 or 7, wherein the linear polyester resin (B) contains 20 to 2000 ppm of titanium element and 10 to 1200 of nitrogen element. The non-linear polyester resin (A) and / or the linear polyester resin (B) is formed in the presence of at least one titanium-containing catalyst (z) represented by the following general formula (I) or (II). The toner resin according to claim 1, which is a polyester resin.
Ti (-X) m (-OH) n (I)
O = Ti (-X) p (-OR) q (II)
[In the formula, X is a residue obtained by removing H of one OH group from a mono- or polyalkanolamine having 2 to 12 carbon atoms, and other OH groups of the polyalkanolamine are directly bonded to the same Ti atom. An OH group may be polycondensed in the molecule to form a ring structure, or an OH group directly bonded to another Ti atom may be polycondensed between molecules to form a repeating structure. The degree of polymerization in the case of forming a repeating structure is 2-5. R is H or an alkyl group having 1 to 8 carbon atoms which may contain 1 to 3 ether bonds. m is an integer of 1 to 4, n is an integer of 0 to 3, and the sum of m and n is 4. p is an integer of 1 to 2, q is an integer of 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. ]   A toner composition comprising the toner resin according to claim 1, a colorant, and, if necessary, one or more additives selected from a release agent, a charge control agent, and a fluidizing agent.