JP2022102326A - Toner for electrostatic charge image development - Google Patents

Abstract

To provide a toner for electrostatic charge image development, excellent in low temperature fixability, hot offset resistance, crushability and durability.SOLUTION: A toner for electrostatic charge image development is provided, containing an amorphous resin H with a softening point of 140°C to 160°C inclusive, an amorphous resin M with a softening point of 105°C to 130°C inclusive, an amorphous rein L with a softening point of 85°C or higher and less than 105°C, and a crystalline material. The amorphous resin H is an amorphous polyester resin containing a constituent derived from polyethylene terephthalate, the amorphous resin M is an amorphous composite resin in which an amorphous polyester resin and a styrene resin are combined, the amorphous resin L is an amorphous polyester resin, and the crystalline material contains 60 mass% or more of a crystalline material with a solubility parameter of 9.0 or less.SELECTED DRAWING: None

Description

The present invention relates to a toner for static charge image development used for developing a latent image formed in, for example, an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like.

Patent Document 1 contains polyester H having a softening point of 140 ° C. or higher and 170 ° C. or lower, polyester M having a softening point of 115 ° C. or higher and lower than 140 ° C., and polyester L having a softening point of 80 ° C. or higher and lower than 115 ° C. In the binder resin composition for toner, the difference between the softening point of polyester H and the softening point of polyester M is 10 ° C. or more, and the difference between the softening point of polyester M and the softening point of polyester L is 20 ° C. or more. , A binder resin composition for a polyester-based toner, wherein the acid value of the entire binder resin composition is 30 mgKOH / g or more and 80 mgKOH / g or less is disclosed.

Patent Document 2 describes a toner containing a binder resin and a colorant, wherein the binder resin contains two types of resins having different softening points of 10 ° C. or higher, and has a higher softening point. Disclosed as a toner for static charge image development, which is a polyester obtained by reacting polyethylene terephthalate or modified polyethylene terephthalate with an alcohol component and a carboxylic acid component, or a hybrid resin containing the polyester as one of the resin components. Has been done.

Patent Document 3 describes a polyester resin obtained by polycondensing a polycondensable monomer containing a carboxylic acid component and an alcohol component and polyethylene terephthalate, and a vinyl resin obtained by addition polymerization of an addition-polymerizable monomer. A polyethylene containing an amorphous composite resin chemically bonded via a bireactive monomer capable of reacting with both a polycondensable monomer and the addition-polymerizable monomer, and having an IV value of 0.40 or more and 0.75 or less of the polyethylene terephthalate. A binder resin composition for a toner, which comprises a terephthalate, is disclosed.

Patent Document 4 describes a toner having toner particles containing a hybrid resin composition, an amorphous polyester resin, and a crystalline material, wherein the hybrid resin composition has a polyester moiety and a vinyl copolymer moiety. It contains a hybrid resin, the content of the polyester moiety in the hybrid resin is 85% by mass or more and 98% by mass or less, and the solubility parameter of the amorphous polyester resin is 10.20 (cal / cm ³ ) ¹ . A toner characterized by being ^{/ 2} or more and 12.34 (cal / cm ³ ) ^1/2 or less is disclosed.

Japanese Unexamined Patent Publication No. 2015-75580 Japanese Unexamined Patent Publication No. 2004-28084 Japanese Unexamined Patent Publication No. 2018-13523 Japanese Unexamined Patent Publication No. 2019-215402

From the viewpoint of widening the fixing temperature range of toner, the combined use of binder resins having different softening points is being studied.

However, since it is difficult to uniformly knead the resin having a high softening point and the resin having a low softening point due to the difference in viscosity between them, it is difficult to obtain the desired fixing temperature range expansion effect, and the resin having a high softening point can be used. By using it, the pulverizability is lowered. Further, when used in combination with a crystalline material such as a crystalline resin or a crystalline wax, the fixing property in a low temperature range is improved, but the durability is lowered.

The present invention relates to a toner for developing an electrostatic charge image, which is excellent in low temperature fixing property, hot offset resistance, pulverization property, and durability.

In the present invention, an amorphous resin H having a softening point of 140 ° C. or higher and 160 ° C. or lower, an amorphous resin M having a softening point of 105 ° C. or higher and 130 ° C. or lower, and an amorphous resin having a softening point of 85 ° C. or higher and lower than 105 ° C. A toner for static charge image development containing L and a crystalline material, wherein the amorphous resin H is an amorphous polyester resin containing a component derived from polyethylene terephthalate, and the amorphous resin. M is an amorphous composite resin in which an amorphous polyester resin and a styrene resin are bonded, the amorphous resin L is an amorphous polyester resin, and the crystalline material has a solubility parameter of 9.0 or less. The present invention relates to a toner for developing an electrostatic charge image, which contains 60% by mass or more of the crystalline material of the above.

The toner for developing an electrostatic charge image of the present invention has excellent effects in low temperature fixing property, hot offset resistance, pulverization property, and durability.

The toner for developing an electrostatic charge image of the present invention is
Amorphous resin H with a softening point of 140 ° C or higher and 160 ° C or lower,
Amorphous resin M with a softening point of 105 ° C or higher and 130 ° C or lower,
The amorphous resin H is an amorphous polyester resin containing an amorphous resin L having a softening point of 85 ° C. or higher and lower than 105 ° C. and a crystalline material, and the amorphous resin H is a component derived from polyethylene terephthalate, and is amorphous. The quality resin M is an amorphous composite resin in which an amorphous polyester resin and a styrene resin are bonded, the amorphous resin L is an amorphous polyester resin, and the crystalline material is an SP value (solubility parameter). It is characterized by containing a crystalline material having a value of 9.0 or less. Although the details are unknown, it is presumed that the effect of the present invention is exerted by the following mechanism.

Amorphous resin with a high softening point (140 to 160 ° C) can be expected to improve hot offset resistance. Further, since the amorphous resin having a high softening point contains a component derived from hydrophilic polyethylene terephthalate (PET), the bleeding property of the crystalline material such as wax is improved and the fixing property is improved. Even at the high softening point, it is considered that the polyester resin has good pulverizability because an interface exists between the polyester resin and the PET resin which is a dissimilar resin.
Further, when the SP value of the crystalline material is 9.0 or less, the bleeding property for the hydrophilic high softening point resin is further improved, so that the hot offset resistance can be expected to be improved, and the SP value of the crystalline material is increased. As the proportion of components of 9.0 or less increases, the effect of improving hot offset resistance increases.
On the other hand, the high softening point resin has a large viscosity difference from the low softening point resin, which is effective for low temperature fixing, and therefore has poor kneadability. Further, since it contains a component derived from PET, the SP value is high and the dispersibility of the crystalline material tends to decrease. Therefore, the softening point is between the high softening point resin and the low softening point resin, and by using the composite resin as the resin having an intermediate viscosity, the dispersibility of the crystalline material is improved, and the low softening point resin and the high softening point resin are highly softened. Since the kneadability with the point resin is also improved, it is considered that the durability and fixability are improved.

In the present invention, the SP value means the solubility parameter by the method of Fedors, and is obtained based on the following formula described in [Robert F. Fedors, Polymer Engineering and Science, 14, 147-154 (1974)]. The given value δ.
Fedors formula: δ = (ΣΔei / ΣΔvi) ^1/2
[Unit: (cal / cm ³ ) ^1/2 ]
[Here, Δei: evaporation energy of atoms and atomic groups (cal / mol), Δvi: molar volume (cm ³ / mol). ]

The softening point of the amorphous resin H is 140 ° C. or higher, preferably 145 ° C. or higher from the viewpoint of hot offset resistance, and 160 ° C. or lower, preferably 155 ° C. or higher from the viewpoint of pulverizability and low temperature fixability. It is as follows.

The softening point of the amorphous resin M is 105 ° C. or higher, preferably 110 ° C. or higher from the viewpoint of improving kneadability, and 130 ° C. or lower from the viewpoint of pulverizability and kneadability with the amorphous resin L. It is preferably 125 ° C. or lower.

The softening point of the amorphous resin L is 85 ° C. or higher, preferably 90 ° C. or higher, from the viewpoint of kneadability with the amorphous resin H and the amorphous resin M, and from the viewpoint of low temperature fixability. It is less than 105 ° C, preferably 100 ° C or less.

The difference between the softening points of the amorphous resin H and the amorphous resin L is preferably 50 ° C. or higher, more preferably 55 ° C. or higher, and preferably 70 ° C. or lower, more preferably 60 ° C. or lower.

The difference between the softening points of the amorphous resin H and the amorphous resin M is preferably 20 ° C. or higher, more preferably 25 ° C. or higher, and preferably 40 ° C. or lower, more preferably 35 ° C. or lower.

The difference between the softening points of the amorphous resin M and the amorphous resin L is preferably 10 ° C. or higher, more preferably 15 ° C. or higher, and preferably 30 ° C. or lower, more preferably 28 ° C. or lower.

The crystallinity of the resin is represented by the crystallinity index defined by the ratio of the softening point to the maximum endothermic temperature by the differential scanning calorimeter, i.e., the value of [softening point / maximum endothermic temperature]. The crystalline resin is a resin having a crystallinity index of 0.6 or more, preferably 0.7 or more, more preferably 0.9 or more, and 1.4 or less, preferably 1.2 or less, more preferably 1.1 or less.
On the other hand, the amorphous resin is a resin having a crystallinity index of more than 1.4, preferably more than 1.5, more preferably 1.6 or more, or less than 0.6, if no endothermic peak is observed or if it is observed. A resin of 0.5 or less is preferable.
The crystallinity of the resin can be adjusted by the type and ratio of the raw material monomers, the production conditions (for example, reaction temperature, reaction time, cooling rate) and the like. The maximum endothermic temperature refers to the temperature of the peak with the largest endothermic area among the observed endothermic peaks. In the crystalline resin, the maximum peak temperature of endothermic is taken as the melting point.

Amorphous resin H is an amorphous polyester resin containing a component derived from polyethylene terephthalate. In the present invention, examples of the amorphous polyester resin include an amorphous polyester resin, an amorphous composite resin in which an amorphous polyester resin and a styrene resin are bonded, and the like, but the amorphous resin H is amorphous. Quality Polyester resin is preferred.

Therefore, the amorphous resin H is preferably an amorphous polyester resin HP which is a polycondensate of an alcohol component, a carboxylic acid component, and polyethylene terephthalate.

The alcohol component preferably contains an alkylene oxide adduct of bisphenol A from the viewpoint of fixability.

As an alkylene oxide adduct of bisphenol A, the formula (I):

(In the formula, OR and RO are oxyalkylene groups, R is an ethylene group and / or a propylene group, and x and y indicate the average number of moles of alkylene oxide added, which are positive numbers, respectively, and x and y. The value of the sum of is 1 or more, preferably 1.5 or more, and 16 or less, preferably 8 or less, more preferably 6 or less, still more preferably 4 or less).
The compound represented by is preferable. Examples of the alkylene oxide adduct of bisphenol A represented by the formula (I) include a polyoxypropylene adduct of 2,2-bis (4-hydroxyphenyl) propane and 2,2-bis (4-hydroxyphenyl) propane. Examples include polyoxyethylene adducts. It is preferable to use one or more of these.

The content of the alkylene oxide adduct of bisphenol A represented by the formula (I) is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 90 mol% or more in the alcohol component. It is 95 mol% or more, more preferably 100 mol%.

Other alcohol components include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,4-butene. Examples thereof include aliphatic diols such as diol, 1,3-butanediol and neopentyl glycol, and trihydric or higher alcohols such as glycerin.

As the carboxylic acid component, at least one selected from the group consisting of an aromatic dicarboxylic acid-based compound, an aliphatic dicarboxylic acid-based compound, and a carboxylic acid-based compound having a valence of 3 or more is preferable, and from the viewpoint of storage stability, the aromatic dicarboxylic acid component is preferable. It is more preferable to contain an acid-based compound.

Examples of the aromatic dicarboxylic acid-based compound include phthalic acid, isophthalic acid, terephthalic acid, anhydrates of these acids, and alkyl esters having 1 or more and 3 or less carbon atoms in the alkyl group. Among these, terephthalic acid or isophthalic acid is preferable, and terephthalic acid is more preferable, from the viewpoint of low-temperature fixability.

The content of the aromatic dicarboxylic acid-based compound is preferably 25 mol% or more, more preferably 30 mol% or more, and preferably 50 mol% or less, more preferably 40 mol% or less in the carboxylic acid component. be.

Examples of the aliphatic dicarboxylic acid compound include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and succinic acid which may be substituted with an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Examples thereof include aliphatic dicarboxylic acids such as adipic acid, anhydrides of these acids, and alkyl esters having 1 or more and 3 or less carbon atoms in the alkyl group.

Examples of trivalent or higher carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, and anhydrides and alkyl groups of these acids. Examples thereof include alkyl esters having 1 or more and 3 or less carbon atoms, and among these, trimellitic acid-based compounds are preferable.

The content of the carboxylic acid-based compound having a valence of 3 or more is preferably 30 mol% or more, more preferably 35 mol% or more from the viewpoint of durability in the carboxylic acid component, and from the viewpoint of low temperature fixability. It is preferably 50 mol% or less, more preferably 45 mol% or less.

A monohydric alcohol may be appropriately contained in the alcohol component, and a monovalent carboxylic acid compound may be appropriately contained in the carboxylic acid component.

The equivalent ratio of the carboxylic acid component to the alcohol component (COOH group / OH group) is preferably 0.6 or more, more preferably 0.7 or more, still more preferably 0.75 or more, and more preferably 0.75 or more, from the viewpoint of adjusting the softening point of the polyester resin. It is preferably 1.2 or less, more preferably 1.15 or less.

As the polyethylene terephthalate (PET), those produced according to a conventional method by polycondensation of ethylene glycol with terephthalic acid, dimethyl terephthalate and the like can be used.

In the polycondensation reaction, PET reacts with an alcohol component and a carboxylic acid component and is incorporated into the structure of the resin, which may be accompanied by depolymerization of PET.
Therefore, in the present invention, the PET is preferably a PET having a relatively low IV value, that is, a PET having a low molecular weight as compared with the PET conventionally used. In the present invention, by introducing PET having a low IV value (low molecular weight) into the polyester resin, the depolymerization of PET proceeds more uniformly.

From the above viewpoint, the IV value of PET is preferably 0.40 or more, more preferably 0.45 or more, further preferably 0.50 or more, still more preferably 0.55 or more, and from the viewpoint of low temperature fixability and homogenization of depolymerization. It is preferably 0.85 or less, more preferably 0.80 or less, still more preferably 0.75 or less, still more preferably 0.70 or less, still more preferably 0.65 or less. The IV value is an intrinsic viscosity and is an index of molecular weight. The IV value of PET can be adjusted by the polycondensation time and the like.

As commercial products of PET with IV value of 0.40 or more and 0.80 or less, RAMAPET L1 (manufactured by Indorama Ventures, IV value: 0.60), RAMAPET BF3067 (manufactured by Indorama Ventures, IV value: 0.65), RAMAPET N2G (manufactured by Indorama Ventures) , IV value: 0.75), TRN-NTJ (Teijin Co., Ltd., IV value: 0.53), TRN-RTJC (Teijin Co., Ltd., IV value: 0.64), RAMAPET S1 (Indorama Ventures), IV value: 0.84) etc. can be mentioned.

The content of PET having a low IV value is preferably 90% by mass or more, more preferably 95% by mass or more, still more preferably 98% by mass or more, still more preferably 100% by mass, based on the total amount of PET subjected to polycondensation. Is.

The PET in the raw material is preferably 5 mol or more, more preferably 15 mol or more, still more preferably 20 mol or more, and further, with respect to a total of 100 mol of the alcohol component and the ethylene glycol unit in the PET, from the viewpoint of pulverizability. It is preferably polycondensed with the carboxylic acid component and the alcohol component in an amount of preferably 30 mol or more, preferably less than 60 mol, more preferably 55 mol or less.
In PET, the unit of terephthalic acid-ethylene glycol (Mw: 192) is converted as 1 mol. Therefore, the number of moles of PET = the number of moles of ethylene glycol unit = the number of moles of terephthalic acid unit.

The polycondensation reaction between the alcohol component, the carboxylic acid component, and PET is carried out, for example, in an inert gas atmosphere, preferably in the presence of an esterification catalyst, and if necessary, an esterification auxiliary catalyst, a polymerization inhibitor, or the like. In the presence, it can be carried out preferably at a temperature of about 180 ° C. or higher and 250 ° C. or lower. Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and tin (II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropyrate bistriethanol aminated. Of these, tin compounds such as tin (II) 2-ethylhexanoate are preferred. The amount of the esterification catalyst used is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and preferably 1.5 part by mass with respect to 100 parts by mass of the total amount of the alcohol component, the carboxylic acid component, and PET. Parts or less, more preferably 1.0 part by mass or less. Examples of the esterification co-catalyst include gallic acid and the like. The amount of the esterification co-catalyst used is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and preferably 0.5 part by mass with respect to 100 parts by mass of the total amount of the alcohol component, the carboxylic acid component, and PET. By mass or less, more preferably 0.1 parts by mass or less. Examples of the polymerization inhibitor include tert-butylcatechol and the like. The amount of the polymerization inhibitor used is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and preferably 0.5 part by mass with respect to 100 parts by mass of the total amount of the alcohol component, the carboxylic acid component, and PET. Parts or less, more preferably 0.1 parts by mass or less.

In the present invention, the polyester resin may be a polyester resin modified to such an extent that its characteristics are not substantially impaired. Examples of the modified polyester resin include grafting and blocking with phenol, urethane, epoxy and the like by the methods described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636 and the like. Examples thereof include a modified polyester resin, and among the modified polyester resins, a urethane-modified polyester resin obtained by urethane-stretching the polyester resin with a polyisocyanate compound is preferable.

The glass transition temperature of the amorphous resin H is preferably 55 ° C. or higher, more preferably 60 ° C. or higher from the viewpoint of storage stability, and preferably 70 ° C. or lower, more preferably 65 ° C. or higher from the viewpoint of pulverizability. It is below ° C.

The acid value of the amorphous resin H is preferably 5 mgKOH / g or more, more preferably 15 mgKOH / g or more, and preferably 45 mgKOH / g or less, more preferably 40 mgKOH / g or less, from the viewpoint of chargeability. be.

The SP value of the amorphous resin H is preferably 11.0 or more, more preferably 11.2 or more, and preferably 11.7 or less, more preferably 11.7 or less, from the viewpoint of hot offset resistance. Is less than 11.5.

The content of the amorphous resin H is preferably 40% by mass or more, more preferably 50% by mass or more, and preferably 80% by mass or less, more preferably 70% by mass, based on the total amount of the amorphous resin. % Or less.

The amorphous resin M is an amorphous composite resin MC in which an amorphous polyester resin and a styrene resin are bonded.

Even if the amorphous polyester resin is a polycondensate of an alcohol component and a carboxylic acid component (amorphous polyester resin MP), the alcohol component, the carboxylic acid component, and polyethylene terephthalate can be obtained in the same manner as the amorphous polyester resin HP. Although it may be a polycondensate, the latter is preferable from the viewpoint of pulverizability.

The alcohol component of the amorphous polyester resin MP preferably contains an alkylene oxide adduct of bisphenol A.

As the alkylene oxide adduct of bisphenol A, the compound represented by the above formula (I) is preferable.

The content of the alkylene oxide adduct of bisphenol A represented by the formula (I) is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 90 mol% or more in the alcohol component. It is 95 mol% or more, more preferably 100 mol%.

The carboxylic acid component of the amorphous polyester resin MP preferably contains an aromatic dicarboxylic acid-based compound, and more preferably contains terephthalic acid.

The content of the aromatic dicarboxylic acid-based compound is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, still more preferably 100 mol% in the carboxylic acid component.

The content of the carboxylic acid-based compound having a valence of 3 or more is preferably 5 mol% or less, more preferably 3 mol% or less, still more preferably 1 mol% or less, still more preferably 1 mol% or less, from the viewpoint of kneading property in the carboxylic acid component. It is 0.5 mol% or less, more preferably 0 mol%.

Examples of the alcohol component and the carboxylic acid component other than the above are the same as those described for the amorphous polyester resin HP.

The amorphous polyester resin has, for example, an alcohol component and a carboxylic acid component in an inert gas atmosphere, preferably in the presence of an esterification catalyst, and if necessary, in the presence of an esterification co-catalyst, a polymerization inhibitor, or the like. It is obtained by polycondensation at a temperature of preferably 130 ° C. or higher, more preferably 170 ° C. or higher, and preferably 250 ° C. or lower, more preferably 240 ° C. or lower.

Examples of the esterification catalyst include tin compounds such as dibutyltin oxide and tin (II) 2-ethylhexanoate, and titanium compounds such as titanium diisopropyrate bistriethanolaminate, and tin compounds are preferable. The amount of the esterification catalyst used is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and preferably 1.5 parts by mass or less, based on 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. It is preferably 1 part by mass or less. Examples of the esterification co-catalyst include gallic acid and the like. The amount of the esterification co-catalyst used is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and preferably 0.5 part by mass or less, based on 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. More preferably, it is 0.1 part by mass or less. Examples of the polymerization inhibitor include tert-butylcatechol and the like. The amount of the polymerization inhibitor used is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more, and preferably 0.5 part by mass or less, based on 100 parts by mass of the total amount of the alcohol component and the carboxylic acid component. It is preferably 0.1 parts by mass or less.

The polycondensate of the alcohol component, the carboxylic acid component and the polyethylene terephthalate is the same as the amorphous polyester resin MP for the alcohol component and the carboxylic acid component, and the amorphous polyester resin HP for the polyethylene terephthalate.

The styrene-based resin is an addition polymer of a raw material monomer containing at least styrene or a styrene derivative such as α-methylstyrene or vinyltoluene (hereinafter, styrene and styrene derivative are collectively referred to as “styrene compound”).

The content of the styrene compound, preferably styrene, is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more in the raw material monomer of the styrene resin from the viewpoint of durability and storage stability. , More preferably 95% by mass or more, still more preferably 100% by mass.

Further, the styrene resin may contain a (meth) acrylic acid alkyl ester having an alkyl group having 7 or more carbon atoms as a raw material monomer. Examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid (iso) octyl, (meth) acrylic acid (iso) decyl, and (meth) acrylic acid (iso) stearyl. Can be mentioned. It is preferable to use one or more of these. In addition, in this specification, "(iso)" means to include both the case where this group is present and the case where this group is not present, and it is normal when these groups are not present. Show that. Further, "(meth) acrylic acid" indicates acrylic acid, methacrylic acid, or both.

The carbon number of the alkyl group in the (meth) acrylic acid alkyl ester as the raw material monomer of the styrene resin is preferably 7 or more, more preferably 8 or more, and preferably 8 or more, from the viewpoint of improving the low temperature fixability of the toner. Is 12 or less, more preferably 10 or less. The carbon number of the alkyl ester means the number of carbon atoms derived from the alcohol component constituting the ester.

Raw material monomers for styrene-based resins include raw material monomers other than styrene compounds and (meth) acrylic acid alkyl esters, for example, ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; vinyl chloride and the like. Halovinyls; Vinyl esters such as vinyl acetate and vinyl propionate; Ethylene monocarboxylic acid esters such as dimethylaminoethyl (meth) acrylate; Vinyl ethers such as methyl vinyl ethers; Vinylidene halides such as vinylidene chloride; N-vinyl N-vinyl compounds such as pyrrolidone may be contained.

The addition polymerization reaction of the raw material monomer of the styrene resin shall be carried out by a conventional method in the presence of, for example, a polymerization initiator such as dicumyl peroxide, a polymerization inhibitor, a cross-linking agent, etc., in the presence of an organic solvent or in the absence of a solvent. However, the temperature conditions are preferably 110 ° C. or higher, more preferably 140 ° C. or higher, and preferably 200 ° C. or lower, more preferably 170 ° C. or lower.

When an organic solvent is used in the addition polymerization reaction, xylene, toluene, methyl ethyl ketone, acetone and the like can be used. The amount of the organic solvent used is preferably 10 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the raw material monomer of the styrene resin.

The mass ratio of the amorphous polyester resin to the styrene resin (amorphous polyester resin / styrene resin) in the composite resin is preferably 60/40 or more, more preferably 70/30 or more, from the viewpoint of low temperature fixability. It is more preferably 80/20 or more, and from the viewpoint of pulverizability, it is preferably 98/2 or less, more preferably 95/5 or less, still more preferably 90/10 or less. In the above calculation, the mass of the polyester resin is the amount obtained by subtracting the amount of reaction water (calculated value) dehydrated by the polycondensation reaction from the mass of the raw material monomer of the polyester resin used, and is a bireactive monomer. Is included in the amount of raw material monomer of the polyester resin. The amount of the styrene resin is the total amount of the raw material monomer of the styrene resin and the polymerization initiator.

The composite resin is more preferably a resin chemically bonded by a covalent bond via both reactive monomers capable of reacting with both the raw material monomer of the polyester resin and the raw material monomer of the styrene resin.

The bireactive monomer contains at least one functional group selected from the group consisting of a hydroxyl group, a carboxy group, an epoxy group, a primary amino group and a secondary amino group, preferably a hydroxyl group and / or a carboxy group. A compound having a group, more preferably a carboxy group and an ethylenically unsaturated bond is preferable, and at least one selected from the group consisting of acrylic acid, methacrylic acid, fumaric acid, maleic acid and maleic anhydride is more preferable. From the viewpoint of the reactivity of the polycondensation reaction and the addition polymerization reaction, at least one selected from the group consisting of acrylic acid, methacrylic acid and fumaric acid is more preferable. However, when used together with a polymerization inhibitor, a polyvalent carboxylic acid compound having an ethylenically unsaturated bond such as fumaric acid functions as a raw material monomer for a polyester resin. In this case, fumaric acid or the like is not a bireactive monomer but a raw material monomer for a polyester resin.

Further, the bireactive monomer may be one or more (meth) acrylic acid alkyl esters selected from acrylic acid alkyl esters and methacrylic acid alkyl esters having an alkyl group having 6 or less carbon atoms. ..

The (meth) acrylic acid alkyl ester is preferably a (meth) acrylic acid alkyl ester from the viewpoint of reactivity to transesterification, and the alkyl group has preferably 2 or more carbon atoms, more preferably 3 or more carbon atoms, and It is preferably 6 or less, more preferably 4 or less. The alkyl group may have a substituent such as a hydroxyl group.

Specific examples of the (meth) acrylic acid alkyl ester include (meth) acrylic acid ethyl, (meth) acrylic acid (iso) propyl, (meth) acrylic acid 2-hydroxyethyl, and (meth) acrylic acid (iso or). Examples thereof include tertiary) butyl and (meth) hexyl acrylate. In addition, "(iso or tertiary)" means to include both the case where these groups are present and the case where these groups are not present, and when these groups are not present, it is normal. Is shown.

In the present invention, the acrylic acid ester is preferably an acrylic acid alkyl ester having an alkyl group having 2 or more and 6 or less carbon atoms, more preferably butyl acrylate, and the methacrylic acid ester is preferably having an alkyl group having 2 or more carbon atoms. Alkyl methacrylate ester having 2 or more and 6 or less, more preferably butyl methacrylate.

The amount of the bireactive monomer used is preferably from the viewpoint of low temperature fixability, with respect to a total of 100 mol of the alcohol component of the polyester resin, or with respect to a total of 100 mol of the alcohol component and PET when PET is used. Is 1 mol or more, more preferably 2 mol or more, and is preferably 30 mol or less, more preferably 20 mol, from the viewpoint of increasing the dispersibility between the styrene resin and the polyester resin and improving the durability of the toner. Below, it is more preferably 15 mol or less.

Specifically, the amorphous composite resin is preferably produced by the following method. Both reactive monomers are preferably used in the addition polymerization reaction together with the raw material monomer of the styrene resin from the viewpoint of improving the durability of the toner, the low temperature fixability of the toner and the heat-resistant storage stability.

(i) A method of performing a polycondensation reaction step (A) using a polyester resin raw material monomer and then an addition polymerization reaction (B) using a styrene resin raw material monomer and a bireactive monomer. In this method, a polycondensation reaction is performed. The step (A) is carried out under the reaction temperature condition suitable for the above, the reaction temperature is lowered, and the step (B) is carried out under the temperature condition suitable for the polycondensation reaction. The raw material monomer of the styrene resin and the bireactive monomer are preferably added into the reaction system at a temperature suitable for the addition polymerization reaction. Both reactive monomers undergo an addition polymerization reaction and also react with a polyester resin.
After the step (B), the reaction temperature is raised again, and if necessary, a raw material monomer of a polyester resin having a valence of 3 or more as a cross-linking agent is added to the polymerization system, and the polycondensation reaction and both reactions in the step (A) are performed. The reaction with the sex monomer can be further advanced.

(ii) A method in which a step (A) of a polycondensation reaction using a raw material monomer of a polyester resin is carried out after a step (B) of an addition polymerization reaction using a raw material monomer of a styrene resin and a bireactive monomer. The step (B) is carried out under the reaction temperature conditions suitable for the above, the reaction temperature is raised, and the polycondensation reaction of the step (A) is carried out under the temperature conditions suitable for the polymerization reaction. Both reactive monomers are involved in the polycondensation reaction as well as the addition polymerization reaction.
The raw material monomer of the polyester resin may be present in the reaction system during the addition polymerization reaction, or may be added to the reaction system under temperature conditions suitable for the polycondensation reaction. In the former case, the progress of the polycondensation reaction can be regulated by adding an esterification catalyst at a temperature suitable for the polycondensation reaction.

(iii) The reaction is carried out under the condition that the polycondensation reaction step (A) using the polyester resin raw material monomer and the polycondensation reaction step (B) using the styrene resin raw material monomer and both reactive monomers proceed in parallel. Method of performing In this method, the step (A) and the step (B) are carried out in parallel under the reaction temperature condition suitable for the polycondensation reaction, the reaction temperature is raised, and the temperature condition suitable for the polycondensation reaction is obtained. If necessary, it is preferable to add a raw material monomer of a trivalent or higher valent polyester resin as a cross-linking agent to the polymerization system to further carry out the polycondensation reaction in the step (A). At that time, under temperature conditions suitable for the polycondensation reaction, a polymerization inhibitor may be added to proceed only with the polycondensation reaction. Both reactive monomers are involved in the polycondensation reaction as well as the addition polymerization reaction.

In the method (i) above, a prepolymerized polycondensation resin may be used instead of the step (A) for carrying out the polycondensation reaction. In the method (iii) above, when the reaction is carried out under the condition that the step (A) and the step (B) proceed in parallel, the raw material monomer of the styrene resin is contained in the mixture containing the raw material monomer of the polyester resin. It is also possible to drop and react the mixture containing the above.

The above methods (i) to (iii) are preferably performed in the same container.

The glass transition temperature of the amorphous resin M is preferably 50 ° C. or higher, more preferably 55 ° C. or higher from the viewpoint of storage stability, and preferably 70 ° C. or lower, more preferably 65 ° C. or higher from the viewpoint of pulverizability. It is below ° C.

The acid value of the amorphous resin M is preferably 2 mgKOH / g or more, more preferably 5 mgKOH / g or more, and preferably 20 mgKOH / g or less, more preferably 10 mgKOH / g or less, from the viewpoint of chargeability. be.

The SP value of the amorphous resin M is preferably 10.8 or more from the viewpoint of compatibility with the amorphous resin H and the amorphous resin L, and is preferably 10.8 or more from the viewpoint of the dispersibility of the crystalline material. 11.2 or less, more preferably 11.0 or less.

The content of the amorphous resin M is preferably 3% by mass or more, more preferably 5% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass, based on the total amount of the amorphous resin. % Or less.

The amorphous resin L is an amorphous polyester resin, and is preferably an amorphous polyester resin LP which is a polycondensate of an alcohol component and a carboxylic acid component.

The alcohol component and the carboxylic acid component of the amorphous polyester resin LP, and their polycondensations are the same as those described for the amorphous polyester resin MP.

The glass transition temperature of the amorphous resin L is preferably 45 ° C. or higher, more preferably 50 ° C. or higher from the viewpoint of storage stability, and preferably 65 ° C. or lower, more preferably 60 ° C. or higher from the viewpoint of pulverizability. It is below ° C.

The acid value of the amorphous resin L is preferably 1 mgKOH / g or more, more preferably 3 mgKOH / g or more from the viewpoint of chargeability, and preferably 10 mgKOH / g or less, more preferably from the viewpoint of pulverizability. Is less than 6 mgKOH / g.

The SP value of the amorphous resin L is preferably 10.5 or more, more preferably 10.8 or more from the viewpoint of compatibility with the amorphous resin M, and preferably 11.2 or less, more preferably from the viewpoint of fixability. It is preferably 11.0 or less.

The content of the amorphous resin L is preferably 15% by mass or more, more preferably 20% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass, based on the total amount of the amorphous resin. % Or less.

The contents of the amorphous resin H, the amorphous resin M, and the amorphous resin L are preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 90% by mass or more, based on the total amount of the amorphous resins. It is 95% by mass or more, more preferably 100% by mass.

The toner may contain a resin used as a binder resin for toner other than the amorphous resin H, the amorphous resin M, and the amorphous resin L. Examples of other resins include vinyl-based resins such as styrene acrylic resins, epoxy resins, polycarbonates, polyurethanes, and composite resins containing two or more of these resins. The content of these resins is preferably 5 parts by mass or less, more preferably 2 parts by mass or less, based on 100 parts by mass of the total of amorphous resin H, amorphous resin M, and amorphous resin L. It is more preferably 1 part by mass or less, still more preferably 0 part by mass.

Examples of the crystalline material include crystalline polyester resin, nylon 6, polyamide resin, crystalline resin such as polyacetal resin, and crystalline wax.

The crystalline polyester resin is preferably a polycondensate of an alcohol component containing an aliphatic diol and a carboxylic acid component containing an aliphatic dicarboxylic acid-based compound.

The aliphatic diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol. , 1,8-octanediol, neopentyl glycol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, etc. , Two or more may be used together.

From the viewpoint of low-temperature fixability, the aliphatic diol is preferably an α, ω-aliphatic diol having a hydroxyl group at the end of the carbon chain, and more preferably an α, ω-linear alkane diol. ..

The carbon number of the aliphatic diol is preferably 6 or more from the viewpoint of dispersibility of the colorant, and preferably 14 or less, more preferably 12 or less, still more preferably 8 or less from the viewpoint of storage stability. be.

The content of the aliphatic diol is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more in the alcohol component.

Examples of other alcohol components include aromatic diols such as alkylene oxide adducts of bisphenol A, and trihydric or higher alcohols such as sorbitol, pentaerythritol, glycerin, and trimethylolpropane.

Examples of the aliphatic dicarboxylic acid compound include succinic acid (carbon number: 4), fumaric acid (carbon number: 4), adipic acid (carbon number: 6), suberic acid (carbon number: 8), and azelaic acid (carbon number: 8). : 9), sebacic acid (carbon number: 10), dodecanedioic acid (carbon number: 12), tetradecanedioic acid (carbon number: 14), succinic acid having an alkyl group or alkenyl group in the side chain, of these acids Examples thereof include anhydrides and alkyl esters having 1 or more and 3 or less carbon atoms of these acids.

The aliphatic dicarboxylic acid-based compound preferably has 4 or more carbon atoms, and preferably 14 or less, more preferably 12 or less.

The content of the aliphatic dicarboxylic acid-based compound is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more in the carboxylic acid component.

Examples of other carboxylic acid components include aromatic dicarboxylic acid-based compounds, aliphatic dicarboxylic acid-based compounds, and trivalent or higher-valent carboxylic acid-based compounds.

A monohydric alcohol may be appropriately contained in the alcohol component, and a monovalent carboxylic acid compound may be appropriately contained in the carboxylic acid component.

The equivalent ratio (COOH group / OH group) of the carboxylic acid component and the alcohol component is preferably 0.8 or more, more preferably 0.9 or more from the viewpoint of storage stability, and preferably 1.2 or less from the viewpoint of low temperature fixability. , More preferably 1.1 or less.

The softening point of the crystalline polyester resin is preferably 100 ° C. or higher, more preferably 105 ° C. or higher from the viewpoint of storage stability, and preferably 130 ° C. or lower, more preferably 120 ° C. or higher from the viewpoint of low temperature fixability. It is below ° C.

The melting point of the crystalline polyester resin is preferably 100 ° C. or higher, more preferably 105 ° C. or higher from the viewpoint of storage stability, and preferably 130 ° C. or lower, more preferably 120 ° C. or higher from the viewpoint of low temperature fixability. It is as follows.

In the wax, the wax having a melting point, that is, the wax having an endothermic peak in the differential scanning calorimetry is a crystalline wax.

Most of the waxes used as a mold release agent for toner are crystalline waxes having a melting point, and the crystalline waxes include polypropylene wax, polyethylene wax, polypropylene polyethylene copolymer wax, microcrystallin wax, paraffin wax, and the like. Hydrocarbon waxes such as Fisher Tropsch wax and their oxides; ester waxes such as carnauba wax, montan wax and their deoxidizing waxes, fatty acid ester waxes; fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts Among these, the hydrocarbon wax is preferable from the viewpoint of bleed-out property with respect to the polyester resin.

The melting point of the crystalline wax is preferably 100 ° C. or higher, more preferably 110 ° C. or higher, still more preferably 120 ° C. or higher from the viewpoint of hot offset resistance, and preferably 160 ° C. from the viewpoint of low temperature fixability. Below, it is more preferably 155 ° C. or lower, still more preferably 150 ° C. or lower.

The crystalline material includes a crystalline material X having an SP value of 9.0 or less.
The SP value of the crystalline material X is 9.0 or less, preferably 8.8 or less, more preferably 8.6 or less, and from the viewpoint of dispersibility, it is preferably 8.2 or more, more preferably 8.3 or more.

The difference in SP value between the crystalline material X and the amorphous resin H is preferably 2.5 or more, more preferably 2.8 or more from the viewpoint of hot offset resistance, and from the viewpoint of the dispersibility of the crystalline material X. It is preferably 3.5 or less, more preferably 3.2 or less.

The content of the crystalline material X is 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass in the crystalline material. As mentioned above, it is more preferably 100% by mass.

The crystalline material may be contained in the toner mixed with the amorphous resin or may be internally added to the amorphous resin, but when the crystalline material is a crystalline wax. Is preferably added internally from the viewpoint of durability. When the crystalline material is internally added to the amorphous resin, it is preferably added to the amorphous resin M.

When the crystalline wax is internally added to the amorphous resin, it is preferable that the amorphous resin is produced in the presence of the crystalline wax. For example, in the case of an amorphous polyester resin, polycondensation of an alcohol component and a carboxylic acid component is performed in the presence of a crystalline wax, and in the case of an amorphous composite resin, a crystalline wax is applied together with a raw material monomer of the polyester resin. It is preferable to use it.

The content of the crystalline material is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, and crystalline with respect to 100 parts by mass of the total amount of the amorphous resin. From the viewpoint of dispersibility of the material, it is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and further preferably 3 parts by mass or less.

In addition to the amorphous resin and crystalline material, the toner for static charge image development of the present invention is reinforced and filled with a colorant, a charge control agent, a magnetic powder, a fluidity improver, a conductivity adjusting agent, a fibrous substance, and the like. Additives such as an agent, an antioxidant, and a cleaning property improving agent may be contained.

As the colorant, dyes, pigments, magnetic materials and the like used as colorants for toner can be used. For example, Carbon Black, Phthalocyanine Blue, Permanent Brown FG, Brilliant First Scarlet, Pigment Red 122, Pigment Green B, Rhodamine-B Base, Solvent Red 49, Solvent Red 146, Solvent Blue 35, Quinacridone, Carmin 6B, Isoindoline, Disazoero And so on. In the present invention, the toner may be either black toner or color toner.

The content of the colorant is preferably 1 part by mass or more, more preferably 2 parts by mass or more, and more preferably 2 parts by mass or more with respect to 100 parts by mass of the amorphous resin from the viewpoint of improving the image concentration and low temperature fixability of the toner. It is preferably 40 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 10 parts by mass or less.

The charge control agent is not particularly limited and may contain either a positive charge control agent or a negative charge control agent.

Positive charge control agents include niglosin dyes such as "niglocin base EX", "oil black BS", "oil black SO", "bontron N-01", "bontron N-04", and "bontron N-07". , "Bontron N-09", "Bontron N-11" (all manufactured by Orient Chemical Industry Co., Ltd.), etc .; Triphenylmethane dyes containing a tertiary amine as a side chain; A quaternary ammonium salt compound, for example. "Bontron P-51" (manufactured by Orient Chemical Industry Co., Ltd.), cetyltrimethylammonium bromide, "COPY CHARGE PX VP435" (manufactured by Clariant), etc .; (Manufactured by), etc .; imidazole derivatives such as "PLZ-2001", "PLZ-8001" (all manufactured by Shikoku Kasei Kogyo Co., Ltd.), etc .; styrene-acrylic resin, for example, "FCA-701PT", "FCA-201-" PS ”(manufactured by Fujikura Kasei Co., Ltd.) and the like.

Examples of the negative charge control agent include metal-containing azo dyes such as "Varifast Black 3804", "Bontron S-31", "Bontron S-32", "Bontron S-34", and "Bontron S-36". (The above is manufactured by Orient Chemical Industry Co., Ltd.), "Eisenspiron Black TRH", "T-77" (manufactured by Hodoya Chemical Industry Co., Ltd.), etc .; Metal compounds of benzylic acid compounds, for example, "LR-" 147 ”,“ LR-297 ”(above, manufactured by Nippon Carlit Co., Ltd.), etc .; Metal compounds of salicylic acid compounds, for example,“ Bontron E-81 ”,“ Bontron E-84 ”,“ Bontron E-88 ”,“ Bontron E-304 "(above, manufactured by Orient Chemical Industry Co., Ltd.)," TN-105 "(manufactured by Hodoya Chemical Industry Co., Ltd.), etc .; copper phthalocyanine dye; quaternary ammonium salt, for example," COPY CHARGE NX VP434 " (Manufactured by Clariant), nitroimidazole derivatives, etc .; Examples thereof include organic metal compounds.

The content of the charge control agent is preferably 0.01 part by mass or more, more preferably 0.2 part by mass or more, and preferably 10 parts by mass with respect to 100 parts by mass of the amorphous resin from the viewpoint of charge stability of the toner. By mass or less, more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, still more preferably 2 parts by mass or less.

The toner of the present invention may be a toner obtained by any conventionally known method such as a melt-kneading method, an emulsification phase inversion method, a polymerization method, etc. Therefore, crushed toner by the melt-kneading method is preferable. In the case of crushed toner by the melt-kneading method, for example, raw materials such as an amorphous resin, a crystalline material, a colorant, and a charge control agent are uniformly mixed with a mixer such as a Henshell mixer, and then a closed kneader, a single shaft, or the like. It can be manufactured by melt-kneading with a twin-screw extruder, an open roll type kneader, etc., cooling, crushing, and classifying.

It is preferable to use an external additive for the toner of the present invention in order to improve the transferability. Examples of the external additive include inorganic fine particles such as silica, alumina, titania, zirconia, tin oxide, and zinc oxide, and organic fine particles such as resin particles such as melamine-based resin fine particles and polytetrafluoroethylene resin fine particles. The above may be used together. Among these, silica is preferable, and from the viewpoint of toner transferability, hydrophobicized silica is more preferable.

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

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

From the viewpoint of the chargeability, fluidity, and transferability of the toner, the content of the external additive is preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass, based on 100 parts by mass of the toner before being treated with the external additive. More than parts, more preferably 0.3 parts by mass or more, and preferably 5 parts by mass or less, more preferably 3 parts by mass or less.

The volume median particle size (D ₅₀ ) of the toner of the present invention is preferably 3 μm or more, more preferably 4 μm or more, and preferably 15 μm or less, more preferably 10 μm or less. In the present specification, the volume median particle size (D ₅₀ ) means a particle size in which the cumulative volume frequency calculated by the volume fraction is 50% calculated from the smaller particle size. When the toner is treated with an external additive, the volume median particle diameter of the toner particles before the toner is treated with the external additive is defined as the volume median particle diameter of the toner.

The toner of the present invention can be used as it is as a toner for one-component development or as a toner for two-component development used by mixing with a carrier, respectively, in a one-component development method or a two-component development method image forming apparatus.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. The physical characteristics of the resin and the like can be measured by the following methods.

[IV value of PET]
It can be obtained by dissolving in a mixed solvent having a phenol / tetrachloroethane (mass ratio) of 60/40 at a concentration of 4 g / L, measuring with an Ubbelohde viscometer, and calculating according to the following formula.
IV = (-1 + √ (1 + 4kη)) / (2kC)
[In the formula, k = 0.33, C = 0.004 g / mL, and η = (t1 / t0) -1 (t0: number of seconds for solvent only to fall, t1: number of seconds for sample solution to fall). ]

[Plastic softening point]
Using the flow tester "CFT-500D" (manufactured by Shimadzu Corporation), while heating a 1 g sample at a heating rate of 6 ° C / min, a load of 1.96 MPa was applied by a plunger, and the diameter was 1 mm and the length was 1 mm. Extrude from the nozzle of. The amount of plunger drop of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is used as the softening point.

[Maximum endothermic temperature of resin]
Using the differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.01 to 0.02 g of the sample in an aluminum pan, and cool down from room temperature to 10 ° C / min. Cool to 10 ° C and hold for 1 minute. Next, the sample was heated to 200 ° C. at a heating rate of 10 ° C./min and cooled to -30 ° C. from that temperature at a temperature decreasing rate of 10 ° C./min. Next, the sample is heated at a heating rate of 10 ° C./min, and the temperature of the peak with the largest peak area among the observed endothermic peaks is set as the maximum endothermic temperature.

[Resin glass transition temperature]
Using the differential scanning calorimeter "Q-20" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.01 to 0.02 g of the sample in an aluminum pan, raise the temperature to 200 ° C, and then start from that temperature. Cool to 0 ° C at a temperature lowering rate of 10 ° C / min. Next, the sample is heated at a heating rate of 10 ° C./min, and the endothermic peak is measured. The temperature at the intersection of the extension of the baseline below the maximum endothermic temperature and the tangent showing the maximum slope from the rising portion of the peak to the peak of the peak is defined as the glass transition temperature.

[Acid value of resin]
Measure based on the method of JIS K 0070: 1992. However, only the measurement solvent is changed from the mixed solvent of ethanol and ether specified in JIS K 0070: 1992 to the mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).

[Melting point of wax]
Using the differential scanning calorimeter "Q-100" (manufactured by TA Instruments Japan Co., Ltd.), weigh 0.02 g of the sample into an aluminum pan, raise the temperature to 200 ° C, and then lower the temperature from 200 ° C. Cool to 0 ° C at a rate of 10 ° C / min. Next, the sample is heated at a heating rate of 10 ° C./min, and the amount of heat is measured. The peak temperature of the obtained endothermic is taken as the melting point.

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

[Medium particle size of toner]
-Measuring device: "Coulter Multisizer (registered trademark) III" (manufactured by Beckman Coulter Co., Ltd.)
・ Aperture diameter: 50 μm
-Analysis software: "Coulter Multisizer (registered trademark) III version 3.51" (manufactured by Beckman Coulter Co., Ltd.)
-Electrolytic solution: "Isoton (registered trademark) II" (manufactured by Beckman Coulter Co., Ltd.)
-Dispersion: "Emulgen (registered trademark) 109P" [Polyoxyethylene lauryl ether, manufactured by Kao Corporation, HLB (Hydrophile-Lipophile Balance, Griffin method): 13.6] was dissolved in the electrolytic solution, and the concentration was 5% by mass. To obtain a dispersion of.
-Dispersion conditions: Add 10 mg of the measurement sample to 5 mL of the dispersion, disperse with an ultrasonic disperser (machine name: US-1, SND Co., Ltd., output: 80 W) for 1 minute, and then 25 mL of electrolyte. Is added, and the mixture is further dispersed in an ultrasonic disperser for 1 minute to prepare a sample dispersion.
-Measurement conditions: In a beaker, the sample dispersion is added to 100 mL of the electrolytic solution to adjust the particle size of 30,000 particles to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured. Then, the volume median particle size (D ₅₀ ) is obtained from the obtained particle size distribution.

Amorphous resin production example 1
The alcohol components, terephthalic acid, PET, esterification catalyst, and esterification auxiliary catalyst shown in Table 1 are placed in a 10-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser, and a nitrogen inlet tube. The temperature was raised to 235 ° C. in a mantle heater in a nitrogen atmosphere. After that, it was confirmed that the reaction rate reached 95% or more at 235 ° C, and the mixture was cooled to 190 ° C. Then, adipic acid was added, the temperature was raised to 230 ° C. over 2 hours, and then the reaction was carried out at 26.7 kPa for 1 hour. Then, after cooling to 190 ° C., trimellitic anhydride is added, the mixture is kept at 210 ° C. for 30 minutes, and the reaction is carried out under a reduced pressure of 80 kPa until the softening point shown in Table 1 is reached, and the amorphous polyester resin (resin). H1 to H3) were obtained. The reaction rate in the present invention means the value of the amount of produced reaction water (mol) / the theoretical amount of produced water (mol) × 100.

Amorphous resin production example 2
The alcohol components, terephthalic acid, esterification catalyst, and esterification auxiliary catalyst shown in Table 1 were placed in a 10-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser, and a nitrogen introduction tube. The temperature was raised to 235 ° C. in a mantle heater in a nitrogen atmosphere. After that, it was confirmed that the reaction rate reached 95% or more at 235 ° C, and the mixture was cooled to 190 ° C. Then, adipic acid was added, the temperature was raised to 230 ° C. over 2 hours, and then the reaction was carried out at 26.7 kPa for 1 hour. Then, after cooling to 190 ° C., trimellitic anhydride is added, the mixture is kept at 210 ° C. for 30 minutes, and the reaction is carried out under a reduced pressure of 80 kPa until the softening point shown in Table 1 is reached, and the amorphous polyester resin (resin). H4) was obtained.

Amorphous resin production example 3
The raw material monomer of the polyester resin and the crystalline material C1 (“High Wax NP-055”, manufactured by Mitsui Kagaku Co., Ltd., polypropylene wax, SP value: 8.4, melting point: 136 ° C, 145 ° C) shown in Table 2 were used with a thermometer. It was placed in a 10-liter four-necked flask equipped with a stainless steel stirring rod, a flow-down condenser equipped with a dehydration tube, and a nitrogen introduction tube, and the temperature was raised to 160 ° C. in a mantle heater under a nitrogen atmosphere. A mixture of a raw material monomer of a styrene resin, a bireactive monomer, and a polymerization initiator was added dropwise thereto to carry out polymerization. Then, after aging at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C. and the reaction was carried out at 8.0 kPa for 1 hour. Then, an esterification catalyst and an esterification co-catalyst were added, polycondensed at 235 ° C., and then reacted under a reduced pressure of 8 kPa until the softening point shown in Table 2 was reached. Resins (resins M1 and M2) were obtained.

Amorphous resin production example 4
Place the polyester resin raw material monomers shown in Table 2 in a 10-liter four-necked flask equipped with a thermometer, a stainless stir bar, a flow-down condenser equipped with a dehydration tube, and a nitrogen introduction tube, and place them in a nitrogen atmosphere. The temperature was raised to 160 ° C in the mantle heater. A mixture of a raw material monomer of a styrene resin, a bireactive monomer, and a polymerization initiator was added dropwise thereto to carry out polymerization. Then, after aging at 160 ° C. for 30 minutes, the temperature was raised to 200 ° C. and the reaction was carried out at 8 kPa for 1 hour. Then, an esterification catalyst and an esterification co-catalyst were added, polycondensed at 235 ° C., and then reacted under a reduced pressure of 8 kPa until the softening point shown in Table 2 was reached, and the amorphous composite resin (resin M3) was reacted. , M4) was obtained.

Amorphous resin production example 5
The raw material monomer of the polyester resin shown in Table 2, the esterification catalyst and the esterification auxiliary catalyst are placed in a 10-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen introduction tube, and nitrogen is placed. After raising the temperature to 235 ° C in a mantle heater in an atmosphere, it was confirmed that the reaction rate reached 95% or more at 235 ° C. Then, the reaction was carried out under a reduced pressure of 8 kPa until the softening point shown in Table 2 was reached to obtain an amorphous polyester resin (resin M5).

Amorphous resin production example 6
Place the polyalcohol component, carboxylic acid component, esterification catalyst and esterification auxiliary catalyst shown in Table 3 in a 10-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen introduction tube. After raising the temperature to 235 ° C in a mantle heater under a nitrogen atmosphere, it was confirmed that the reaction rate reached 95% or more at 235 ° C. Then, the reaction was carried out under a reduced pressure of 8 kPa until the softening point shown in Table 3 was reached to obtain amorphous polyester resins (resins L1 and L2).

Production example of crystalline resin The raw material monomer shown in Table 4 is placed in a 10-liter four-necked flask equipped with a thermometer, a stainless steel stirring rod, a flow-down condenser and a nitrogen introduction tube, and a mantle heater is placed in a nitrogen atmosphere. The temperature was raised from 130 ° C. to 200 ° C. over 8 hours, then reacted at 200 ° C. for 2 hours, and then an esterification catalyst and a polymerization inhibitor were added, and the softening shown in Table 4 was performed under a reduced pressure of 8 kPa. The reaction was carried out until the point was reached, and a crystalline polyester resin (resin C) was obtained.

Examples 1 to 6 and Comparative Examples 1 to 5
100 parts by mass of the binder resin and 1 part by mass of the crystalline material shown in Table 5, 1 part by mass of the negative charge control agent "Bontron E-81" (manufactured by Orient Chemical Industries Co., Ltd.), and the colorant "Regal 330R". (Carbon Black manufactured by Cabot) After thoroughly mixing 5 parts by mass with a Henshell mixer, a roll rotation speed of 200r / using a co-rotating twin-screw extruder with a total length of 1560 mm, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm. It was melt-kneaded in min at a heating temperature of 100 ° C in the roll. The obtained melt-kneaded product is cooled and roughly pulverized, then finely pulverized by an I-2 type pulverizer (manufactured by Nippon Pneumatic Co., Ltd.), classified, and a toner having a medium volume particle size (D ₅₀ ) of 6.5 μm. Obtained particles.
The pulverization pressure (MPa) when pulverized by an I-2 type pulverizer (manufactured by Nippon Pneumatic Co., Ltd.) was measured to evaluate the pulverizability of the toner. The lower the crushing pressure, the better the crushing property.

To 100 parts by mass of the obtained toner particles, 2.0 parts by mass of the external additive "Aerosil R-972" (hydrophobic silica, manufactured by Nippon Aerosil Co., Ltd., hydrophobic treatment agent: DMDS, average particle size: 16 nm) is added. Then, using a Henshell mixer, mixing was performed at 3600 r / min for 5 minutes to perform an external addition treatment, and toner was obtained.

Test Example 1
Toner is mounted on the non-magnetic one-component developing device "OKI MICROLINE 5400" (manufactured by Oki Data Corporation), the toner adhesion amount is adjusted to 0.48 ± 0.03 mg / cm ² , and a solid image of 4.1 cm x 13.0 cm is displayed as "J". Printed on "paper" (manufactured by Fuji Xerox Office Supply Co., Ltd.). A solid image was taken out before passing through the fixing machine to obtain an unfixed image. The obtained unfixed image was fixed at a fixing speed of 240 mm / sec by setting the temperature of the fixing roll to 100 ° C with an external fixing machine modified from the fixing machine of "Microline 3010" (manufactured by Oki Data Corporation). After that, the fixing roll temperature was set to 105 ° C., and the same operation was performed. While raising this to 240 ° C. by 5 ° C., the unfixed image was fixed at each temperature to obtain a fixed image. Then, the low temperature fixing property and the hot offset resistance were evaluated by the following methods. The results are shown in Table 6.

[Low temperature fixability]
After attaching a mending tape (manufactured by Sumitomo 3M) to the image fixed at each temperature, the tape was sufficiently attached to the fixed image by placing a weight stone on a 600 g cylinder. Then, the mending tape was slowly peeled off from the fixed image, and the optical reflection density of the image after the tape peeling was measured using a reflection densitometer "RD-915" (manufactured by Macbeth). The optical reflection density is also measured for the image before the tape is applied in advance, and the ratio to the value ([reflection density after tape peeling / reflection density before tape application] x 100) first exceeds 90% for fixing. The low temperature fixing property was evaluated by setting the roll temperature as the minimum fixing temperature.

[Hot offset resistance]
After image output is performed at each fixing temperature, a blank transfer paper is continuously sent to the fixing roller under the same conditions, and the temperature of the fixing roller at which toner stains first on the blank paper is used as the hot offset generation temperature to withstand the resistance. The hot offset property was evaluated.

Test Example 2 [Durability]
Toner is mounted on the laser printer "Page Presto N-4" (manufactured by Casio Computer Co., Ltd., fixing: contact fixing method, development: non-magnetic one-component development method, development roll diameter: 2.3 cm), temperature 40 ° C, relative Printing was performed with a diagonal stripe pattern with a blackening rate of 5.5% under the condition of a humidity of 85%. On the way, a solid black image was printed every 500 sheets, and the presence or absence of streaks on the image caused by the fusion and sticking of toner to the developing roll was confirmed. Durability was evaluated from the number of printed sheets up to the time when the occurrence of streaks was visually observed. The larger the number of prints, the better the durability of the toner. The results are shown in Table 6.

From the above results, it can be seen that, in comparison with Comparative Examples 1 to 5, in Examples 1 to 6, the low temperature fixing property, the hot offset resistance, the pulverization property, and the durability are all good. Among them, from the comparison between Examples 1 and 4, the amorphous resin M uses PET, so that the pulverizability is improved from the comparison between Examples 1 and 6, and the crystalline material is changed to the amorphous resin M. It can be seen that the durability is improved by being added internally.

The toner for developing an electrostatic charge image of the present invention is suitably used for developing a latent image formed by an electrophotographic method, an electrostatic recording method, an electrostatic printing method, or the like.

Claims (6)

Amorphous resin H with a softening point of 140 ° C or higher and 160 ° C or lower, amorphous resin M with a softening point of 105 ° C or higher and 130 ° C or lower, amorphous resin L with a softening point of 85 ° C or higher and lower than 105 ° C, and crystals. The amorphous resin H is an amorphous polyester resin containing a component derived from polyethylene terephthalate, and the amorphous resin M is a non-amorphous resin M, which is a toner for static charge image development containing a sex material. It is an amorphous composite resin in which a crystalline polyester resin and a styrene resin are bonded, the amorphous resin L is an amorphous polyester resin, and the crystalline material is a crystalline material having a solubility parameter of 9.0 or less. , 60% by mass or more, a toner for developing an electrostatic charge image. The toner for developing an electrostatic charge image according to claim 1, wherein the crystalline material contains a hydrocarbon wax. The toner for developing an electrostatic charge image according to claim 1 or 2, wherein the solubility parameter of the amorphous resin M is 10.8 or more and 11.2 or less. The toner for static charge image development according to any one of claims 1 to 3, wherein the difference between the softening points of the amorphous resin H and the amorphous resin L is 50 ° C. or higher and 70 ° C. or lower. The toner for static charge image development according to any one of claims 1 to 4, wherein the difference between the softening points of the amorphous resin H and the amorphous resin M is 20 ° C. or higher and 40 ° C. or lower. The toner for static charge image development according to any one of claims 1 to 5, wherein the difference between the softening points of the amorphous resin M and the amorphous resin L is 10 ° C. or higher and 30 ° C. or lower.