阅读说明：本技术 调色剂 (Toner and image forming apparatus ) 是由 下田卓 河村政志 丰田隆之 大久保显治 于 2020-04-22 设计创作，主要内容包括：本发明涉及调色剂。所述调色剂包括调色剂颗粒,所述调色剂颗粒包含粘结剂树脂、由式(1)表示的树脂、和蜡,其中蜡包含在100℃下相对于100.0质量份的粘结剂树脂相容5.0质量份以上的酯化合物：其中在式(1)中,P<Sup>1</Sup>表示高分子部位；L<Sup>1</Sup>表示单键或二价连接基团；R<Sup>1</Sup>至R<Sup>3</Sup>各自独立地表示氢原子、卤素原子、烷基、烷氧基、羟基、或芳基；m表示正整数；并且当m为2以上时,多个L<Sup>1</Sup>可以彼此相同或不同,多个R<Sup>1</Sup>可以彼此相同或不同,多个R<Sup>2</Sup>可以彼此相同或不同,并且多个R<Sup>3</Sup>可以彼此相同或不同,<Image he="305" wi="700" file="DDA0002461458130000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention relates to a toner. The toner includes toner particles containing a binder resin, a resin represented by formula (1), and a wax, wherein the wax contains an ester compound that is compatible at 100 ℃ by 5.0 parts by mass or more with respect to 100.0 parts by mass of the binder resin: wherein in formula (1), P 1 Represents a polymer moiety; l is 1 Represents a single bond or a divalent linking group; r 1 To R 3 Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or an aryl group; m represents a positive integer; and when m is 2 or more, a plurality of L 1 A plurality of R, which may be the same or different from each other 1 A plurality of R, which may be the same or different from each other 2 May be the same as or different from each other, and a plurality of R 3 May be the same as or different from each other,)

1. A toner comprising toner particles containing a binder resin, a resin represented by formula (1), and a wax,

it is characterized in that the preparation method is characterized in that,

the wax contains an ester compound showing compatibility of 5.0 parts by mass or more with respect to 100.0 parts by mass of the binder resin at 100 ℃:

wherein in formula (1), P¹Represents a polymer moiety; l is¹Represents a single bond or a divalent linking group; r¹To R³Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group or an aryl group; m represents a positive integer; and when m is 2 or more, a plurality of L ¹A plurality of R, which may be the same or different from each other¹A plurality of R, which may be the same or different from each other²Are the same or different from each other, and a plurality of R³The same or different from each other.

2. The toner according to claim 1, wherein R is¹To R³At least one of them represents an alkoxy group or a hydroxyl group.

3. The toner according to claim 1 or 2, wherein a content of the ester compound is 5.0 parts by mass to 30.0 parts by mass with respect to 100 parts by mass of the binder resin.

4. The toner according to claim 1 or 2, wherein the content of silicon atoms in the resin represented by formula (1) is 0.02% by mass to 10.00% by mass.

5. The toner according to claim 1 or 2, wherein

A is used as the content of the ester compound in the toner in mass%, and

b is used as the content in mass% of the resin represented by formula (1) in the toner, and the ratio of B to a is 0.10 to 10.00.

6. The toner according to claim 1 or 2, wherein the resin represented by formula (1) has a weight average molecular weight of 3000 to 100000.

7. The toner according to claim 1 or 2, wherein

The binder resin is a resin containing a styrene-acrylic acid copolymer, and

The polymeric moiety comprises a styrene-acrylic acid copolymer.

8. The toner according to claim 1 or 2, wherein

The binder resin is a resin containing a polyester moiety, and

the polymer portion includes a polyester portion.

9. The toner according to claim 1 or 2, wherein the toner particles further comprise a hydrocarbon-based wax.

10. The toner according to claim 1 or 2, wherein the ester compound is a condensate of a diol having 2 to 10 carbons and an aliphatic monocarboxylic acid having 14 to 22 carbons and has a melting point of 60 ℃ to 100 ℃.

11. A toner comprising toner particles containing a binder resin, a resin represented by formula (1), and a wax,

it is characterized in that the preparation method is characterized in that,

the wax comprises an ester compound, and

the ester compound is a condensate of a diol having 2 to 10 carbons and an aliphatic monocarboxylic acid having 14 to 22 carbons and has a melting point of 60 ℃ to 100 ℃:

wherein in formula (1), P¹Represents a polymer moiety; l is¹Represents a single bond orA divalent linking group; r¹To R³Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group or an aryl group; m represents a positive integer; and when m is 2 or more, a plurality of L ¹A plurality of R, which may be the same or different from each other¹A plurality of R, which may be the same or different from each other²Are the same or different from each other, and a plurality of R³The same or different from each other.

Technical Field

The present invention relates to a toner for forming a toner image by development of an electrostatic latent image formed by a method such as an electrophotographic method, an electrostatic recording method, and a toner jet recording method.

Background

In recent years, energy saving has been regarded as a major technical problem for copiers, printers, and facsimile machines, and therefore a drastic reduction in the amount of heat required for an image fixing apparatus is desired. Therefore, for the toner, it is highly required that the image can be fixed with less energy, that is, low temperature fixability is highly required.

General methods for improving the low-temperature fixability of a toner include, for example, lowering the glass transition temperature (Tg) of a binder resin, and reducing the molecular weight of the binder resin, in each case for the purpose of softening the binder resin used. However, for example, when a decrease in Tg of the binder resin or a decrease in molecular weight thereof is caused only by itself, the following occurs: generation of offset of the fixing member due to insufficient releasability during fixing; and a decrease in heat resistance during toner storage; and the like.

Therefore, the addition of a plasticizer is used as a method for improving the fixing property of the toner without lowering Tg of the binder resin. In order to sufficiently soften the toner during fixing, it is necessary to use a plasticizer which has high compatibility with the binder resin and exhibits large plasticizing ability.

Japanese patent No.6020458 proposes a toner using an ester wax as a plasticizer for a binder resin.

In addition, a method for improving releasability of a toner using a low-molecular weight binder resin during fixing includes: a method of mixing a silicone oil into a binder resin and a method of using a binder resin containing a siloxane compound.

Japanese patent application laid-open No. h07-239573 proposes a toner containing, as a binder resin, a vinyl-based resin provided by copolymerization of a vinyl monomer and a silane coupling agent having an unsaturated double bond and an alkoxysilyl group.

Disclosure of Invention

The toner described in japanese patent No.6020458 shows the effect of reducing the viscosity of the toner during fixing and improving low-temperature fixability by the use of a specific diester compound having excellent plasticizing performance.

However, for a fixed image obtained using this toner, the following problems were found: the diester compound becomes exposed on the surface of the fixed image with the passage of time, and the gloss exhibited by the fixed image decreases.

With the toner described in japanese patent application laid-open No. h07-239573, excellent fixing offset resistance and excellent transferability from a photosensitive member are obtained due to a mold release effect peculiar to a silicone resin as a result of a siloxane bond generated when a silane coupling agent having an alkoxysilyl group undergoes crosslinking.

However, the toner described in japanese patent application laid-open No. h07-239573 does not have satisfactory low-temperature fixability.

Further, it was found that even when the diester compound described in japanese patent No.6020458 is contained as it is in the toner described in japanese patent application laid-open No. h07-239573, the diester compound becomes exposed on the surface of the resulting fixed image with the passage of time, and the gloss is reduced.

The present invention thus provides a toner having excellent low-temperature fixability and providing a fixed image that causes less gloss reduction with the passage of time.

The present invention relates to a toner comprising toner particles containing a binder resin, a resin represented by formula (1), and a wax, wherein

The wax contains an ester compound which is compatible at 100 ℃ by 5.0 parts by mass or more with respect to 100.0 parts by mass of the binder resin:

wherein in formula (1), P¹Represents a polymer moiety; l is¹Represents a single bond or a divalent linking group; r¹To R³Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or an aryl group; m represents a positive integer; and when m is 2 or more, a plurality of L¹A plurality of R, which may be the same or different from each other¹A plurality of R, which may be the same or different from each other²May be the same as or different from each other, and a plurality of R³May be the same as or different from each other.

In addition, the present invention relates to a toner comprising toner particles containing a binder resin, a resin represented by formula (1), and a wax, wherein

The wax contains an ester compound, and

the ester compound is a condensate of a diol having 2 to 10 carbons and an aliphatic monocarboxylic acid having 14 to 22 carbons and has a melting point of 60 ℃ to 100 ℃:

Wherein in formula (1), P¹Represents a polymer moiety; l is¹Represents a single bond or a divalent linking group; r¹To R³Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or an aryl group; m represents a positive integer; and when m is 2 or more, a plurality of L¹A plurality of R, which may be the same or different from each other¹A plurality of R, which may be the same or different from each other²May be the same as or different from each other, and a plurality of R³May be the same as or different from each other.

The present invention can therefore provide a toner which has excellent low-temperature fixability, provides a fixed image causing less gloss reduction with the passage of time, and generates less image defects even when subjected to a load in a developing apparatus.

Further features of the present invention will become apparent from the following description of exemplary embodiments.

Detailed Description

The toner according to the present invention is specifically described below, but is not limited thereto.

Unless specifically stated otherwise, the expressions "from XX to YY" and "XX to YY" showing numerical ranges in the present invention mean numerical ranges including the lower limit and the upper limit as endpoints.

The monomer unit refers to a reacted form of a monomer material in a polymer or a resin.

The toner is a toner including toner particles containing a binder resin, a resin represented by formula (1), and a wax, wherein the wax contains an ester compound compatible at 5.0 parts by mass or more relative to 100.0 parts by mass of the binder resin at 100 ℃.

The present inventors have found that by employing a toner having the above-described constitution, excellent low-temperature fixability is provided, a fixed image that causes less gloss reduction with the passage of time is obtained, and less image defects are generated even when a load is applied in a developing apparatus.

The reason is presumed as follows.

In the case of a conventional toner containing a plasticizer, since the toner is heated to above the melting point of the plasticizer during fixing, fixing onto paper occurs while the melted plasticizer is made compatible with the binder resin.

During the process of discharging paper from the printer unit, the fixed image undergoes a sharp temperature drop from the fixing temperature to around room temperature. This short time interval makes it easier for the plasticizer to exist in a state compatible with the binder resin as it is, compared with the formation of nuclei and the growth of crystals at the time of phase separation from the binder resin.

The plasticizer existing in a compatible state as it is exhibits higher mobility within the fixed image than the plasticizer existing in a crystalline state, and due to this movement in the fixed image with the passage of time, the surface of the fixed image is caused to be exposed. The plasticizer exposed to the surface in this manner reduces the gloss of the fixed image.

In contrast, the toner particles of the present invention contain a resin represented by formula (1) (hereinafter also referred to as resin a).

It is considered that the high molecular site in the resin a has high affinity for the binder resin, and the silicon atom present in the resin a has high affinity for the ester group site in the ester compound.

Thus, in a state where the toner is melted during fixing and various molecules in the toner assume high mobility, silicon atoms are easily oriented to ester groups of the ester compound, and high molecular sites are easily oriented to the binder resin.

At this time, the high molecular site oriented to the binder resin has a strong interaction with the binder resin, and as a result, this makes it possible to restrict the mobility of the ester compound. It is considered that exposure of the ester compound on the surface of the fixed image with the passage of time can thereby be suppressed, thereby providing a fixed image causing less reduction in gloss.

Further, toner particles containing resin a are more resistant to cracking when subjected to a load than conventional toner particles that do not contain resin a. As described above, the silicon atom in the resin a is easily oriented to the ester group site of the ester compound, and the polymer site is easily oriented to the binder resin. It is believed that this promotes the presence of the resin a in the toner particles at the interface between the binder resin and the ester compound. When the toner is subjected to a load and the toner is subjected to deformation, the interfacial adhesiveness between the binder resin and the ester compound is improved by the resin a present at the interface, and it is considered that toner cracking is thereby suppressed. The toner cracking promotes the generation of development streaks, for example, as image defects.

As described previously, the toner having the above-described effects can be obtained by causing toner particles to contain a binder resin, a resin a, and an ester compound exhibiting specific compatibility with the binder resin.

The toner particles contain a resin represented by the following formula (1).

In formula (1), P¹Represents a polymer moiety; l is¹Represents a single bond or a divalent linking group; r¹To R³Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or an aryl group; and m represents a positive integer. When m is 2 or more, plural L¹A plurality of R, which may be the same or different from each other¹A plurality of R, which may be the same or different from each other²May be the same as or different from each other, and a plurality of R³May be the same as or different from each other.

In the resin represented by formula (1), a silicon atom (Si) is present at a side chain position or a terminal position of the resin. It is considered that the silicon atom is easily oriented to the ester group site in the ester compound due to the high affinity of the silicon atom for the ester group site.

The content of the silicon atom in the resin represented by formula (1) is preferably 0.02 to 10.00 mass%, and more preferably 0.02 to 5.00 mass%.

When the silicon atom content in the resin (resin a) represented by formula (1) is at least 0.02 mass%, the silicon atom in the resin a more easily undergoes orientation to the ester compound.

On the other hand, when the silicon atom content in the resin a is not more than 10.00 mass%, the high molecular site (for example, polymer site) in the resin a is more easily oriented to the binder resin. Further, when the silicon atom content is not more than 5.00 mass%, the high molecular site is even more likely to undergo orientation with respect to the binder resin. The method for measuring the silicon atom content in the resin a is described below.

R in the formula (1)¹To R³Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxyl group, or an aryl group.

The number of carbons in the alkyl group is preferably 1 to 4, and more preferably 1 to 3.

The number of carbons in the alkoxy group is preferably 1 to 4, and more preferably 1 to 3.

The carbon number in the aryl group is preferably 6 to 12, and more preferably 6 to 10.

In the foregoing, R in the formula (1)¹To R³At least one of them preferably represents an alkoxy group or a hydroxyl group. More preferably, R in formula (1)¹To R³Each independently represents an alkoxy group or a hydroxyl group.

The alkoxy group and the hydroxyl group have a higher affinity for an ester group site in the ester compound, and thus facilitate orientation to the ester group site to an even greater extent. It is considered that the mobility of the ester compound in the fixed image is limited to a greater extent as a result.

In order to make R in the formula (1)¹To R³At least one of which is hydroxy, for example, may be such that R is¹To R³Hydrolyzing the resin in which at least one of them is an alkoxy group to convert the alkane into an alkyl groupThe oxy group is converted to a hydroxy group.

Any method may be used for hydrolysis, and the following methods are examples.

Wherein R in formula (1)¹To R³The resin in which at least one of the alkoxy groups is dissolved or suspended in a suitable solvent (which may be a polymerizable monomer), the pH is adjusted to acidity using an acid or a base, and mixing and hydrolysis are performed.

Hydrolysis may also be performed during toner particle production.

P in the formula (1)¹Should have a high molecular site (e.g., a polymer site), but is not otherwise particularly limited. It is considered that the polymer site exhibits high affinity with the molecular chain of the binder resin, resulting in a large increase in the interaction with the molecular chain of the binder resin and an effect of suppressing the mobility of the ester compound.

The following are specific examples of the polymer site in the formula (1): a polyester site, for example, a vinyl polymer site such as a styrene-acrylic copolymer, a polyurethane site, a polycarbonate site, a phenolic resin site, and a polyolefin site.

In the foregoing, the polymer moiety preferably contains a styrene-acrylic copolymer moiety or a polyester moiety.

The presence of the styrene-acrylic acid copolymer site in the high molecular site means that the high molecular site may be composed of only a styrene-acrylic acid copolymer, or may be a block copolymer or a graft copolymer of a styrene-acrylic acid copolymer with other polymers or a mixture of the foregoing.

The styrene-acrylic copolymer herein means a copolymer of a styrenic monomer and at least one monomer selected from the group consisting of an acrylic monomer and a methacrylic monomer.

The styrenic monomer may be exemplified by styrene, α -methylstyrene, β -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2, 4-dimethylstyrene, and divinylbenzene. A single styrenic monomer may be used, or a combination of two or more selected from among styrenic monomers may be used.

The acrylic monomer may be exemplified by alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and n-nonyl acrylate; diesters of acrylic acid such as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, and 1, 6-hexanediol diacrylate; and acrylic acid.

The methacrylic monomer may be exemplified by alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, and n-nonyl methacrylate; and methacrylic acid.

A single acrylic monomer may be used or a combination of two or more selected from acrylic monomers may be used, and a single methacrylic monomer may be used or a combination of two or more selected from methacrylic monomers may be used.

The styrene-acrylic acid copolymer moiety preferably comprises a styrene-alkyl acrylate copolymer or a styrene-alkyl methacrylate copolymer.

The proportion of the styrenic monomer in the total monomers forming the styrene-acrylic acid copolymer is preferably 45 to 80 mass%. On the other hand, the proportion of at least one monomer (for example, alkyl acrylate and/or alkyl methacrylate) selected from the group consisting of acrylic monomers and methacrylic monomers is preferably 20 to 50% by mass.

Further description is provided for the embodiment in the case where the polymeric site comprises a polyester site; however, this should not be construed as limiting thereof.

The polyester moiety is a polymer moiety having an ester bond (-CO-O-) in a repeating unit of the main chain. Examples here are polycondensate structures between polyols (alcohol components) and polycarboxylic acids (carboxylic acid components). Specific examples are the following polymeric moieties: wherein a structure represented by the following formula (6) (a structure derived from a dicarboxylic acid) and at least one structure selected from the group consisting of the formulae (7) to (9) given below (a structure derived from a diol) are bonded to form an ester bond. It may be a polymer moiety as follows: wherein a structure represented by formula (10) given below (a structure derived from a compound having a carboxyl group and a hydroxyl group in 1 molecule) is bonded to form an ester bond.

(in the formula (6), R⁹Represents an alkylene group, an alkenylene group, or an arylene group. )

(in the formula (7), R¹⁰Represents an alkylene group or a phenylene group. )

(in the formula (8), R¹⁸Represents an ethylene group or a propylene group. x and y are each integer values equal to or greater than 0, and the average value of x + y is 2 to 10. )

(in the formula (10), R¹¹Represents an alkylene group or an alkenylene group. )

R in formula (6) ⁹The alkylene groups (preferably having 1 to 12 carbons) represented may be exemplified by the following:

methylene, ethylene, trimethylene, propylene, tetramethylene, hexamethylene, neopentylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, 1, 3-cyclopentylene, 1, 3-cyclohexylene, and 1, 4-cyclohexylene.

R in formula (6)⁹The alkenylene group (preferably having 2 to 4 carbons) represented may be exemplified by vinylene, propenylene, and 2-butenylene.

R in formula (6)⁹The arylene group (preferably having 6 to 12 carbons) represented may be exemplified by 1, 4-phenylene, 1, 3-phenylene, 1, 2-phenylene, 2, 6-naphthylene, 2, 7-naphthylene, and 4, 4' -biphenylene.

R in the formula (6)⁹May be substituted by a substituent. Examples of the substituent in such a case are a methyl group, a halogen atom, a carboxyl group, a trifluoromethyl group, and a combination thereof.

R in formula (7)¹⁰The alkylene groups (preferably having 1 to 12 carbons) represented may be exemplified by the following:

methylene, ethylene, trimethylene, propylene, tetramethylene, hexamethylene, neopentylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, 1, 3-cyclopentylene, 1, 3-cyclohexylene, and 1, 4-cyclohexylene.

R in formula (7)¹⁰The phenylene group represented may be exemplified by 1, 4-phenylene, 1, 3-phenylene, and 1, 2-phenylene.

R in the formula (7)¹⁰May be substituted by a substituent. Examples of the substituent in such a case are a methyl group, an alkoxy group, a hydroxyl group, a halogen atom, and a combination thereof.

R in the formula (10)¹¹The alkylene groups (preferably having 1 to 12 carbons) represented may be exemplified by the following:

methylene, ethylene, trimethylene, propylene, tetramethylene, hexamethylene, neopentylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, and 1, 4-cyclohexylene.

R in the formula (10)¹¹The alkenylene group (preferably having 2 to 40 carbons) represented may be exemplified by the following:

vinylidene, propenylene, butenylene, butadienylene, pentenylene, hexenylene, hexadienylene, heptenylene, octenylene, decenylene, octadecenylene, eicosenylene, and triacontenylene.

These alkenylene groups may have any of the following structures: linear, branched, and cyclic. The position of the double bond may be anywhere, and at least one or more double bonds may be present.

R in the formula (10)¹¹May be substituted by a substituent. Examples of the substituent in such a case are an alkyl group, an alkoxy group, a hydroxyl group, a halogen atom, and a combination of the foregoing.

On the other hand, polycarboxylic acids (carboxylic acid components) may be exemplified by the following carboxylic acids:

dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaric acid, phthalic acid, isophthalic acid, terephthalic acid, 2, 6-naphthalenedicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, and malonic acid. Preferred among these are maleic acid, fumaric acid, and terephthalic acid.

The tri or more carboxylic acids may be exemplified by the following:

1,2, 4-benzenetricarboxylic acid, 2,5, 7-naphthalenetricarboxylic acid, 1,2, 4-butanetricarboxylic acid, 1,2, 5-hexanetricarboxylic acid, 1, 3-dicarboxy-2-methyl-2-methylenecarboxypropane, 1,2, 4-cyclohexanetricarboxylic acid, tetra (methylenecarboxy) methane, 1,2,7, 8-octanetetracarboxylic acid, pyromellitic acid, and Empol trimer acid and the anhydrides and lower alkyl esters of the foregoing.

One kind of these dicarboxylic acids alone or two or more kinds thereof may be used in combination, and one kind of these tribasic or higher carboxylic acids alone or two or more kinds thereof may be used in combination.

When the polymer site of formula (1) and the binder resin have the same structure, the affinity between the polymer site and the binder resin is strong.

Therefore, when the binder resin is a resin containing a styrene-acrylic acid copolymer and the high-molecular site contains a styrene-acrylic acid copolymer, or

When the binder resin is a resin containing a polyester site and the high molecular site contains a polyester site, the above-described affinity becomes even greater, and thereby the movement of the ester compound in the fixed image can be more thoroughly suppressed.

L¹Represents a single bond or a divalent linking group. The divalent linking group is not particularly limited, but may be exemplified by alkylene groups, phenylene groups, and structures given by the following formulae (2), (3), (4), and (5). In addition, the divalent linking group is preferably a structure represented by the following formula (2), (3), (4) or (5).

The alkylene group and the phenylene group may be substituted with a substituent. Such substituents may be exemplified by methyl groups, alkoxy groups, hydroxyl groups, halogen atoms, and combinations of the foregoing. The alkylene group preferably has 1 to 12 carbons and more preferably 1 to 4 carbons.

(in the formula (2) (. alpha.) represents a group represented by formula (I) and P¹Denotes a bonding site with a silicon atom (Si), and R ⁵Represents a single bond, alkylene, or arylene. )

(in the formula (3) (. alpha.) represents a group represented by formula (I) and P¹Denotes a bonding site with a silicon atom (Si), and R⁶Represents a single bond, alkylene, or arylene. )

For R⁵And R⁶The number of carbons in the alkylene group is preferably 1 to 12 and more preferably 1 to 3.

The carbon number in the arylene group is preferably 6 to 12 and more preferably 6 to 10.

R in (formulae (4) and (5)⁷And R⁸Each independently represents a single bond, alkylene, arylene, or a substituted or unsubstituted alkylene,Or an oxyalkylene group. (. sup.) represents P in the formula (1)¹And (×) represents a bonding site with a silicon atom (Si) in formula (1). )

For R⁷And R⁸The number of carbons in the alkylene group is preferably 1 to 12 and more preferably 1 to 3.

The carbon number in the arylene group is preferably 6 to 12 and more preferably 6 to 10.

The carbon number in the oxyalkylene group is preferably 1 to 12 and more preferably 1 to 3.

The structure represented by formula (2) is a divalent linking group comprising an amide bond.

The linking group is not limited to the case of being formed by reaction. In the case where a linking group is formed by the reaction to produce the resin represented by formula (1), for example, a compound having a carboxyl group may be reacted with an aminosilane compound (for example, a compound containing an amino group and an alkoxysilyl group, a compound containing an amino group and an alkylsilyl group, and the like).

The aminosilane compound is not particularly limited, but may be exemplified by gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-phenyl-gamma-aminopropyltriethoxysilane, n-phenyl-gamma-aminopropyltrimethoxysilane, N-beta- (aminoethyl) -gamma-aminopropyltriethoxysilane, N-6- (aminohexyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethylsilane, and 3-aminopropylsilicone.

R in the formula (2)⁵The alkylene group contained may be an alkylene group containing an-NH-group.

The structure given by formula (3) is a divalent linking group having a urethane bond.

The linking group is not limited to the case of being formed by reaction. In the case where the linking group is formed by the reaction to produce the resin represented by formula (1), for example, the formation may be performed by reacting a compound having a hydroxyl group with an isocyanatosilane compound (for example, a compound containing an isocyanate group and an alkoxysilyl group, a compound containing an isocyanate group and an alkylsilyl group, and the like).

The isocyanatosilane compound is not particularly limited, but may be exemplified by 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyldimethylmethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, 3-isocyanatopropyldimethylethoxysilane, and 3-isocyanatopropyltrimethylsilane.

The structures represented by formulae (4) and (5) are divalent linking groups comprising a bond of an ester bond grafted into a polymer.

These linking groups are not limited to those formed by reaction. In the case where a linking group is formed by reaction to produce the resin represented by formula (1), for example, the formation may be performed by an insertion reaction of a silane compound having an epoxy group. The insertion reaction of the silane compound having an epoxy group is the reaction described below.

Here, the step of performing an insertion reaction of an epoxy group of the silane compound having an epoxy group into an ester bond present in the polymer main chain is included.

The insertion reactions mentioned here are, for example, the reactions described in "Addition reactions of Epoxy Compounds with Esters and their use in Polymer synthesis" (Addition Reaction of Epoxy Compounds with Esters and Its use for Polymer synthesis) ", Journal of Synthetic Organic Chemistry, Japan, Vol.49, No. 3, p.218, 1991.

The following formula (a) shows the mechanism of this reaction as a simple model formula.

(in the formula (A), D and E represent constituent parts of a polymer, and F represents a constituent part except an epoxy part of a silane compound having an epoxy group.)

Two kinds of compounds caused by α -scission and β -scission in ring opening of an epoxy group in formula (a) are possible, but both represent a manner in which an epoxy group is inserted into an ester bond in a polymer, that is, a manner in which a constituent portion other than an epoxy portion of a silane compound having an epoxy group is grafted into a polymer portion.

The silane compound having an epoxy group is not particularly limited, but may be exemplified by β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, γ -glycidoxypropyltrimethoxysilane, γ -glycidoxypropylmethyldiethoxysilane, and 5, 6-epoxyhexyltrimethylsilane.

The resin represented by formula (1) may be contained singly or in combination of two or more.

The weight average molecular weight (Mw) of the resin having formula (1) is preferably 3000 to 100000 and more preferably 5000 to 30000.

When the weight average molecular weight is 3000 or more, the polymer site (P) in formula (1) is satisfactorily represented ¹) Affinity with the molecular chain of the binder resin, and exposure of the ester compound to the surface of the fixed image in the fixed image can be more suppressed.

On the other hand, when the weight average molecular weight is 100000 or less, the orientation of the silicon atom in the formula (1) in the fixed image to the ester group site in the ester compound can be further improved. The method for measuring the weight average molecular weight (Mw) is described below.

The content of the resin represented by formula (1) in the total resin in the toner particles is preferably 0.4% by mass or more, or 0.9% by mass or more, or 6.0% by mass or more. The content is preferably 20.0% by mass or less, or 35.0% by mass or less, or 50.0% by mass or less, or 95.0% by mass or less. Any combination of these numerical ranges may be used.

The toner particles contain a binder resin. The binder resin is a resin component other than the resin represented by formula (1) in the toner particles. The content of the binder resin in the total resin of the toner particles is preferably 5.0 mass% or more, or 50.0 mass% or more, or 65.0 mass% or more, or 80.0 mass% or more. The content is preferably 94.0% by mass or less, or 99.1% by mass or less, or 99.6% by mass or less. Any combination of these numerical ranges may be used.

The binder resin is not particularly limited, and hitherto known binder resins can be used.

The binder resin is preferably a resin containing a styrene-acrylic acid copolymer, or preferably a resin containing a polyester moiety, from the viewpoint of developing characteristics and durability of the toner.

The resin containing a styrene-acrylic copolymer, if it has a styrene-acrylic copolymer, may be a resin composed of only the styrene-acrylic copolymer, or may be a block copolymer or a graft copolymer of the styrene-acrylic copolymer with other polymers, or a mixture of the foregoing.

The styrene-acrylic copolymer herein means a copolymer of a styrenic monomer and at least one monomer selected from the group consisting of an acrylic monomer and a methacrylic monomer.

The styrenic monomer may be exemplified by styrene, α -methylstyrene, β -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2, 4-dimethylstyrene, and divinylbenzene. A single styrenic monomer may be used, or a combination of two or more selected from among styrenic monomers may be used.

The acrylic monomer may be exemplified by alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and n-nonyl acrylate; diesters of acrylic acid such as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, and 1, 6-hexanediol diacrylate; and acrylic acid.

The methacrylic monomer may be exemplified by alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate and n-nonyl methacrylate; and methacrylic acid.

A single acrylic monomer may be used or a combination of two or more selected from among acrylic monomers may be used, and a single methacrylic monomer may be used or a combination of two or more selected from among methacrylic monomers may be used.

The resin containing a styrene-acrylic acid copolymer preferably contains a styrene-alkyl acrylate copolymer or a styrene-alkyl methacrylate copolymer.

The proportion of the styrenic monomer in the total monomers forming the styrene-acrylic acid copolymer is preferably 45 to 80 mass%. On the other hand, the proportion of at least one monomer (for example, alkyl acrylate and/or alkyl methacrylate) selected from the group consisting of acrylic monomers and methacrylic monomers is preferably 20 to 50% by mass.

As the resin containing a polyester site, a polycondensate of a carboxylic acid component with an alcohol component exemplified below may be used. The carboxylic acid component may be exemplified by terephthalic acid, isophthalic acid, phthalic acid, fumaric acid, maleic acid, cyclohexanedicarboxylic acid, and trimellitic acid. The alcohol component may be exemplified by bisphenol a, hydrogenated bisphenol, ethylene oxide adduct of bisphenol a, propylene oxide adduct of bisphenol a, glycerin, trimethylolpropane, and pentaerythritol.

In addition, the polyester site may be a polyester containing urea groups. Preferably, the carboxyl groups of the polyester, e.g. in the terminal positions, are not end-capped.

The content of the styrene-acrylic copolymer-containing resin or the polyester site-containing resin in the binder resin is preferably 50.0 to 100.0 mass%, and more preferably 80.0 to 100.0 mass%. When the content is within the foregoing range, then the plasticizing effect on the binder resin by means of the following ester compound is satisfactory, and excellent low-temperature fixability is exhibited. These binder resins may be used alone or in a mixture.

The binder resin may contain a crosslinking agent. The elasticity of the toner can be increased by including a crosslinking agent. It is considered that when the elasticity of the toner is sufficiently high, even when the binder resin is compatible with the ester compound and the plasticizing effect of the binder resin is large, the effect of suppressing the plasticized toner from adhering to the fixing roller can be expected and the low-temperature fixing property will be further improved.

As the crosslinking agent, a compound having two or more polymerizable double bonds is mainly used.

Examples are aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds, such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1, 3-butanediol dimethacrylate, and 1, 6-hexanediol diacrylate; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone; and compounds having three or more vinyl groups.

A single one of these may be used, or a mixture of two or more may be used. The content of the crosslinking agent is preferably 0.001 parts by mass to 15.000 parts by mass with respect to 100 parts by mass of the binder resin.

The toner particles contain wax. The wax contains an ester compound which is compatible at 100 ℃ by 5.0 parts by mass or more per 100 parts by mass of the binder resin.

The compatible amount at 100 ℃ with respect to 100 parts by mass of the binder resin is hereinafter also referred to as saturated phase capacity.

The saturated phase capacity is a value indicating how much ester compound can be compatible in the binder resin, and is considered to indicate compatibility between the binder resin and the ester compound.

An ester compound having a larger saturated phase capacity will have a greater effect on low temperature fixability for the same amount of ester compound present in the toner particles.

The saturated phase capacity of the ester compound is 5.0 parts by mass or more and preferably 9.0 parts by mass or more, more preferably 14.0 parts by mass or more, and still more preferably 25.0 parts by mass or more. On the other hand, the upper limit of the saturated phase capacity is not particularly limited, but is preferably 100.0 parts by mass or less, more preferably 50.0 parts by mass or less, and still more preferably 45.0 parts by mass or less. Any combination of these numerical ranges may be used.

When the saturated phase capacity satisfies the above conditions, then a satisfactory plasticizing effect of the ester compound on the binder resin is obtained, and excellent low-temperature fixability will be exhibited.

The saturation phase capacity can be adjusted using the solubility parameter (SP value) of the ester compound and using its molecular weight.

Using SP_WAs the SP value of the ester compound, SP is used_CSP value as a binder resin and Mw as a weight average molecular weight of the ester compound, the SP_W、SP_CAnd Mw preferably satisfies the relationship of the following formula (I) (wherein the unit of the solubility parameter is (cal/cm)³)^1/2)。

[(SP_C-SP_W)²×Mw]≤960 (I)

[(SP_C-SP_W)²×Mw]More preferably 370 or more, or 390 or more, or 420 or more, or 440 or more, and more preferably 950 or less, or 800 or less, or 720 or less, or 536 or less. Any combination of these numerical ranges may be used. For example, 370 ≦ [ (SP)_C-SP_W)²×Mw]≤960。

The unit of solubility parameter (SP value) is (cal/cm)³)^1/2。

By using [ (SP)_C-SP_W)²×Mw]An ester compound satisfying the above range can give satisfactory compatibility of the ester compound with the binder resin. The method of measuring the saturated phase capacity, the method of calculating the SP value, and the method of measuring the weight average molecular weight are described below.

The melting point of the ester compound is preferably 55 ℃ to 100 ℃, more preferably 60 ℃ to 100 ℃, and still more preferably 60 ℃ to 90 ℃. When the melting point of the ester compound is 55 ℃ or more, the occurrence of winding at the fixing roller during fixing is suppressed; satisfactory low-temperature fixability can be obtained at 100 ℃ or lower.

As long as the ester compound satisfies the above conditions, it is not particularly limited, and a known ester compound may be used. For example, ester compounds as condensates of an alcohol component and a carboxylic acid component are preferable because they are excellent in compatibility with a styrene-acrylic acid copolymer or a polyester site present in the binder resin.

The ester compound may be exemplified by the following: a condensate of an aliphatic monohydric alcohol having 18 to 22 carbons and an aliphatic monocarboxylic acid having 18 to 22 carbons, a condensate of an aliphatic monohydric alcohol having 18 to 22 carbons and an aliphatic dicarboxylic acid or an aromatic dicarboxylic acid having 6 to 10 carbons, a condensate of an aliphatic diol having 2 to 10 carbons and an aliphatic monocarboxylic acid having 14 to 22 carbons, and a condensate of diethylene glycol and an aliphatic monocarboxylic acid having 18 to 22 carbons.

Among the foregoing, a condensate of an aliphatic diol having 2 to 10 carbons and an aliphatic monocarboxylic acid having 14 to 22 carbons is preferable, and a condensate of a diol having 2 to 6 carbons and an aliphatic monocarboxylic acid having 14 to 22 carbons is more preferable.

The diol having 2 to 6 carbons may be exemplified by ethylene glycol, diethylene glycol, 1, 3-propanediol, 1, 4-butanediol, and 1, 6-hexanediol.

The aliphatic monocarboxylic acid having 14 to 22 carbons may be exemplified by myristic acid, palmitic acid, stearic acid, and behenic acid.

Ethylene glycol distearate as an ester compound of ethylene glycol and stearic acid is particularly preferred.

The carbon number of the diol component of the ester compound and the carbon number of the monocarboxylic acid may be determined by analyzing the toner particles by pyrolysis GC/MS. If necessary, the analysis can be facilitated by prior derivatization using, for example, a methylating agent.

The content of the ester compound is preferably 5.0 parts by mass to 30.0 parts by mass, more preferably 7.0 parts by mass to 30.0 parts by mass, and still more preferably 7.0 parts by mass to 20.0 parts by mass with respect to 100.0 parts by mass of the binder resin.

When the ester compound content is within the above range, a better plasticizing effect on the binder resin is provided, and excellent low-temperature fixability is exhibited. Further, since the plasticizing effect on the binder resin is not excessive and the viscosity of the binder resin during fixing is not subjected to excessive reduction, the adherence to paper is excellent and the occurrence of curl during fixing is suppressed. The ester compound content may be determined by a method in which toner particles are dissolved using a solvent such as deuterated chloroform ¹³C-NMR analysis.

Using a as the content by mass% of the ester compound in the toner and B as the content by mass% of the resin represented by formula (1) in the toner, the ratio of B to a (B/a) is preferably 0.10 to 10.00, and more preferably 0.10 to 2.00. When B/a is within the above range, the ester compound can be more completely suppressed from being exposed to the surface of the fixed image. In addition, the ester compound can plasticize the binder resin better, and can further improve low-temperature fixability. The method of calculating B/A is described below.

In order to bring about an improvement in releasability from paper, the toner particles may optionally contain a wax other than the aforementioned ester compound. The wax is not particularly limited, and the following waxes may be exemplified:

aliphatic hydrocarbon-based waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, fischer-tropsch wax, and paraffin wax; oxides of aliphatic hydrocarbon-based waxes such as oxidized polyethylene wax, and block copolymers thereof; saturated straight-chain fatty acids such as palmitic acid, stearic acid, and montanic acid; unsaturated fatty acids such as brassidic acid, eleostearic acid, and stearidonic acid; saturated alcohols such as stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnauba alcohol, ceryl alcohol, and myricyl alcohol; polyols, such as sorbitol; fatty acid amides such as linoleamide, oleamide, and lauramide; saturated fatty acid bisamides such as methylene bisstearamide, ethylene bisdecanamide, ethylene bislauramide, and hexamethylene bisstearamide; unsaturated fatty acid amides such as ethylenebisoleamide, hexamethylenebisoleamide, N '-dioleyladipamide, and N, N' -dioleylsebactamide; aromatic bisamides such as m-xylene bisstearamide, and N, N' -distearyl isophthalamide; fatty acid metal salts (generally referred to as metal soaps) such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate; waxes provided by grafting an aliphatic hydrocarbon wax with a vinyl monomer such as styrene or acrylic acid. A single one of these waxes may be used, or a combination of two or more may be used.

Among the above, it is preferable to contain a hydrocarbon wax.

The content of the wax other than the ester compound is preferably 0.5 to 20.0 parts by mass with respect to 100.0 parts by mass of the binder resin.

The toner particles may contain a colorant. The colorant is not particularly limited, and for example, the following known colorants can be used.

Examples of the yellow pigment include yellow iron oxides such as navel orange yellow, naphthol yellow S, hansa yellow G, hansa yellow 10G, benzidine yellow GR, quinoline yellow lake, permanent yellow NCG, and tartrazine lake, condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specific examples are shown below.

Pigment yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, 180.

Examples of orange pigments are shown below.

Permanent Orange GTR, pyrazolone Orange, warken Orange (Vulcan Orange), benzidine Orange G, indanthrene bright Orange RK, and indanthrene bright Orange GK.

Examples of Red pigments include indian Red, such as permanent Red 4R, lithol Red, pyrazolone Red, reddish calcium salt (Watching Red calcium salt), lake Red C, lake Red D, brilliant carmine 6B, brilliant carmine 3B, eosin lake, rhodamine lake B, alizarin lake and like condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds. Specific examples are shown below.

C.i. pigment red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254.

Examples of the blue pigment include copper phthalocyanine compounds and derivatives thereof such as alkali blue lake, victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partial chloride, fast sky blue, indanthrene blue BG, and the like; an anthraquinone compound; and basic dye lake compounds and the like. Specific examples are shown below.

C.i. pigment blue 1, 7, 15:1, 15:2, 15:3, 15:4, 60, 62, 66.

Examples of violet pigments include fast violet B and methyl violet lake.

Examples of green pigments include pigment green B, malachite green lake, and finally yellow green G. Examples of the white pigment include zinc white, titanium oxide, antimony white, and zinc sulfide.

Examples of the black pigment include carbon black, aniline black, nonmagnetic ferrite, magnetite, and those toned black by using the above-described yellow-based colorant, red-based colorant, and blue-based colorant. These colorants may be used alone or in a mixture, or in the form of a solid solution.

The colorant may be surface-treated if necessary.

The amount of the colorant is preferably 1.0 part by mass to 15.0 parts by mass with respect to 100.0 parts by mass of the binder resin.

The toner particles may contain a charge control agent. Known charge control agents can be used as the charge control agent. In particular, a charge control agent which provides a fast charging speed and can stably maintain a certain amount of charge is preferable. When the toner particles are produced by a direct polymerization method, a charge control agent which hardly has an ability to inhibit polymerization and is substantially free from a substance soluble in an aqueous medium is particularly preferable.

Examples of the charge control agent that controls the toner particles to be negatively chargeable are as follows:

organometallic compounds and chelate compounds such as monoazo metal compounds, acetylacetone/metal compounds, and metal compounds of aromatic hydroxycarboxylic acids, aromatic dicarboxylic acids, hydroxycarboxylic acids, and dicarboxylic acids. In addition, aromatic hydroxycarboxylic acids, and aromatic mono-and polycarboxylic acids and their metal salts, anhydrides and esters; further, phenol derivatives such as bisphenol are also included. Other examples are urea derivatives, metal-containing salicylic acid-based compounds, metal-containing naphthoic acid-based compounds, boron compounds, quaternary ammonium salts, and calixarenes.

On the other hand, charge control agents that control toner particles to be positively charged are exemplified by the following:

nigrosine and nigrosine-modified products such as fatty acid metal salts; a guanidine compound; an imidazole compound; quaternary ammonium salts such as tributylbenzyl-1-hydroxy-4-naphthalenesulfonic acid ammonium salt and tetrabutyltetrafluoroboric acid ammonium salt and onium salts such as phosphonium salt as analogs thereof, and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (examples of laking agents are phosphotungstic acid, phosphomolybdic acid, phosphotungstomolybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, and ferrocyanide); metal salts of higher fatty acids; and a resin-based charge control agent.

These charge control agents may be contained singly, or may be contained in combination of two or more kinds. The amount of the charge control agent is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the binder resin.

The toner particles may also be used as toner as they are, but in order to improve, for example, fluidity, charging performance and cleanability, the toner particles may be made into toner by adding so-called external additives such as a fluidizing agent and a cleaning assistant.

The external additive may be exemplified by inorganic oxide fine particles such as silica fine particles, alumina fine particles, and titania fine particles; fine particles of inorganic/stearic acid compounds, such as aluminum stearate fine particles and zinc stearate fine particles; and fine particles of inorganic titanic acid compounds such as strontium titanate and zinc titanate. A single one of these may be used, or a combination of two or more may be used.

In order to improve heat-resistant storage stability and improve environmental stability, the inorganic fine particles may be surface-treated with, for example, a silane coupling agent, a titanium coupling agent, a higher fatty acid, and silicone oil. The BET specific surface area of the external additive is preferably 10m²G to 450m²/g。

The BET specific surface area can be determined using a low-temperature gas adsorption method based on a dynamic constant pressure method according to a BET method (preferably, a BET multipoint method). For example, using a specific surface area analyzer (product name: Gemini 2375Ver.5.0, Shimadzu corporation), the BET specific surface area (m) can be calculated by adsorbing nitrogen gas to the sample surface and measuring using the BET multipoint method²/g)。

As for the amount of these various external additives, the sum of them is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, with respect to 100 parts by mass of the toner particles. A combination of various external additives may be used as the external additive.

The toner according to the present invention may be used as a magnetic or non-magnetic one-component developer, but may also be used as a two-component developer by being mixed with a carrier.

As the carrier, a magnetic body containing a known material such as, for example, a metal such as iron, ferrite or magnetite, or an alloy of such a metal with a metal such as aluminum or lead can be used. Among them, the use of ferrite particles is preferable. In addition, a coated carrier provided by coating the surface of a magnetic body with a coating agent such as a resin or a resin dispersion type carrier provided by dispersion of magnetic fine particles in a binder resin may be used as the carrier.

The volume average particle diameter of the carrier is preferably 15 μm to 100 μm and more preferably 25 μm to 80 μm.

Known means can be used for the method of producing toner particles. For example, a dry production method, i.e., a kneading and pulverizing method, or a wet production method may be used. From the viewpoint of shape controllability and realization of a more uniform particle diameter, it is preferable to use a wet production method. The wet production method may be exemplified by a suspension polymerization method, a dissolution suspension method, an emulsion polymerization aggregation method, and an emulsion aggregation method.

For example, when toner particles are produced by a kneading pulverization method, a binder resin, a resin represented by formula (1), a wax, and optionally a colorant, a charge control agent, and other additives are sufficiently mixed using a mixer such as a henschel mixer and a ball mill. Thereafter, melt-kneading is performed by using a heating kneader such as a heating roller, a kneader, or an extruder to disperse or dissolve various materials, and toner particles are obtained by a cooling solidification step, a pulverization step, a classification step, and an optional surface treatment step.

In the pulverizing step, known pulverizing apparatuses such as a mechanical impact type system and a jet type system can be used. With respect to the order of the classification step and the surface treatment step, either may be performed before the other. The classification step preferably uses a multistage classifier in view of production efficiency.

The production of toner particles by means of a suspension polymerization method as a wet production method is described below.

The following describes the respective steps in the example of toner particle production using the suspension polymerization method, but this should not be construed as limiting the present invention.

Process for producing polymerizable monomer composition

In the suspension polymerization method, first, a polymerizable monomer composition is obtained; this is performed by dissolving or dispersing the following to be uniform using a dispersing machine such as a ball mill or an ultrasonic dispersing machine: a polymerizable monomer for forming a binder resin, a resin represented by formula (1), a wax, and optionally a colorant, a charge control agent, a crosslinking agent, a polymerization initiator, and other additives. The polymerizable monomer herein may be exemplified by the monomers provided as examples of the monomers for forming the aforementioned styrene-acrylic acid copolymer.

Dispersing step (granulating step) of polymerizable monomer composition

This polymerizable monomer composition is then put into an aqueous medium prepared in advance, and droplets of the polymerizable monomer composition are granulated using a disperser or stirrer that generates high shear force to provide a desired toner particle size (granulation step).

The aqueous medium in the granulating step preferably contains a dispersion stabilizer in order to control the particle diameter of the toner particles, sharpen the particle size distribution thereof, and suppress coalescence (aggregation) of the toner particles during the production process.

The dispersion stabilizer can be roughly classified into a high molecule which generally exhibits repulsive force by steric hindrance, and a sparingly water-soluble inorganic compound which supports dispersion stabilization by electrostatic repulsive force.

Fine particles of the poorly water-soluble inorganic compound are preferably used because they can be dissolved by an acid or a base, because they can be easily removed by dissolution by washing with an acid or a base after polymerization.

As the dispersion stabilizer of the inorganic compound which is hardly soluble in water, a dispersion stabilizer containing magnesium, calcium, barium, zinc, aluminum, or phosphorus is preferably used. More preferably, the dispersion stabilizer contains magnesium, calcium, aluminum or phosphorus. Specific examples are as follows:

magnesium phosphate, tricalcium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, and hydroxyapatite.

When such a poorly water-soluble inorganic dispersant is used, it may be used as it is, or in order to obtain even finer particles, inorganic dispersant particles produced in an aqueous medium may be used. Using tricalcium phosphate as an example, an aqueous sodium phosphate solution may be mixed with an aqueous calcium chloride solution under high speed agitation to produce a water insoluble calcium phosphate, thereby enabling more uniform and finer dispersion.

An organic compound such as polyvinyl alcohol, gelatin, methyl cellulose, methylhydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, or starch may be used in combination with the dispersion stabilizer. The dispersion stabilizer is preferably used in an amount of 0.1 to 20.0 parts by mass relative to 100 parts by mass of the polymerizable monomer.

In order to miniaturize the dispersion stabilizer, a surfactant may be used in combination in an amount of 0.1 to 10.0 parts by mass per 100 parts by mass of the polymerizable monomer. Specifically, commercially available nonionic, anionic or cationic surfactants can be used. Examples are sodium lauryl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, and calcium oleate.

(polymerization step)

After the granulating step or while the granulating step is being performed, it is preferable to set the temperature to 50 ℃ to 90 ℃, and polymerize the polymerizable monomer present in the polymerizable monomer composition to obtain the toner particle dispersion liquid.

The stirring operation may be performed during the polymerization step to provide a uniform temperature distribution within the vessel. When the polymerization initiator is added, it may be carried out using any timing and at a desired time. In addition, the temperature may be increased in the latter half of the polymerization reaction in order to obtain a desired molecular weight distribution. In order to remove, for example, unreacted polymerizable monomer and by-products from the system, a part of the aqueous medium may be distilled off in the latter half of the reaction or by a distillation operation after the completion of the reaction. The distillation operation may be carried out at normal pressure or under reduced pressure.

The half-life of the polymerization initiator used in the suspension polymerization method in the polymerization reaction is preferably 0.5 to 30 hours. When the polymerization reaction is carried out using an addition amount of 0.5 to 20 parts by mass relative to 100 parts by mass of the polymerizable monomer, a polymer having a molecular weight of between 5000 and 50000 can be obtained with a maximum value.

Oil-soluble initiators are generally used as polymerization initiators, and examples are as follows:

azo compounds such as 2,2 '-azobisisobutyronitrile, 2' -azobis-2, 4-dimethylvaleronitrile, 1 '-azobis (cyclohexane-1-carbonitrile), and 2, 2' -azobis-4-methoxy-2, 4-dimethylvaleronitrile; and peroxide-based initiators such as acetyl cyclohexyl sulfonyl peroxide, diisopropyl peroxycarbonate, decanoyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, tert-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, tert-butyl peroxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, tert-butyl peroxypivalate, and cumene hydroperoxide.

As the polymerization initiator, a water-soluble initiator may be used in combination as needed, and examples are as follows: ammonium persulfate, potassium persulfate, 2 '-azobis (N, N' -dimethyleneisobutyramidine) hydrochloride, 2 '-azobis (2-amidinopropane) hydrochloride, azobis (isobutylamidine) hydrochloride, sodium 2, 2' -azobisisobutyronitrile sulfonate, ferrous sulfate, and hydrogen peroxide.

Either one of these polymerization initiators alone or a combination of these polymerization initiators may be used, and, for example, a chain transfer agent and a polymerization initiator may also be added and used to control the degree of polymerization of the polymerizable monomer.

A solid-liquid separation step, a washing step and a drying step

The toner particle dispersion liquid may be treated with an acid or an alkali in order to remove the dispersion stabilizer adhering to the surface of the toner particles.

This solid-liquid separation for recovering toner particles from the obtained toner particle dispersion liquid can be performed using a common filtration method. It is preferable to subsequently perform additional washing using repulping and water washing to remove foreign matters that may not be completely removed from the surfaces of the toner particles. After sufficient washing has been carried out, additional solid-liquid separation is then carried out to obtain a toner cake. Thereafter, drying may be performed by a known drying means, and a group of particles having a particle diameter other than the specified particle diameter may be separated by classification as necessary to obtain toner particles. When this is done, the separated particle group having a particle diameter other than the specification can be reused to improve the final yield.

Step of external addition

External additives may optionally be added to the resulting toner particles. The external addition step is performed by introducing the external additive and the toner particles into a mixing apparatus equipped with an impeller rotating at high speed and performing sufficient mixing.

When toner particles are obtained by the dissolution suspension method, a resin solution is prepared by dissolving or dispersing the following in an organic solvent to be uniform: binder resin, resin having formula (1), wax, and other optional materials such as colorant and charge control agent, and the like. The resulting resin solution is granulated by dispersing in an aqueous medium, and the organic solvent present in the particles provided by the granulation is removed to obtain toner particles having a desired particle diameter.

The obtained toner particles may be subjected to a solid-liquid separation step, a washing step, a drying step, and an external addition step as needed using the same method as in the above-described suspension polymerization method.

The organic solvent used for the resin solution in the dissolution suspension method is not particularly limited as long as the organic solvent is compatible with raw materials for toner particles such as a binder resin, a resin having formula (1), and a wax; however, from the viewpoint of solvent removal, an organic solvent that exhibits a certain amount of vapor pressure even at a boiling point of water or less is preferable.

For example, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like can be used.

To obtain toner particles using the emulsion aggregation method, first, fine particles of a binder resin, fine particles of a resin having formula (1), fine particles of a wax, and optionally fine particles of other materials such as a colorant and a charge control agent are dispersed and mixed in an aqueous medium containing a dispersion stabilizer. A surfactant may also be added to the aqueous medium. Aggregation to a desired toner particle diameter is then initiated by adding a known aggregating agent, and melt adhesion between the resin fine particles is performed after aggregation or while aggregation. Shape adjustment by heating may be optionally performed.

The obtained toner particles may be subjected to a solid-liquid separation step, a washing step, a drying step, and an external addition step as needed using the same method as in the suspension polymerization method. In the washing step, impurities in the toner particles can be removed by repeated washing and filtration of the obtained particles. Specifically, it is preferable that the toner particles are washed using an aqueous solution containing a chelating agent such as ethylenediaminetetraacetic acid (EDTA) or a Na salt thereof, and additionally washed with pure water a plurality of times.

The particle diameter of the toner particles is preferably 3.0 μm to 10.0 μm in weight average particle diameter from the viewpoint of obtaining a high-definition and high-resolution image. The weight average particle diameter of the toner can be measured using a pore resistance method. For example, the measurement can be performed using "Coulter Countermultisizer 3" (Beckman Coulter, Inc.).

Methods for measuring various physical properties with respect to the toner are described below.

Separation of external additives from toner

For a toner having an external additive on the surface of toner particles, toner particles are obtained by separating toner particles from the external additive using the following method.

A sucrose syrup was prepared by adding 160g of sucrose (Kishida Chemical co., Ltd.) to 100mL of deionized water and dissolving while heating in a water bath. 31g of this sucrose syrup and 6mL of Contaminon N (10 mass% aqueous solution of a neutral detergent for precision measuring instrument cleaning having pH 7 comprising a nonionic surfactant, an anionic surfactant and an organic builder, Wako Pure Chemical Industries, Ltd.) were introduced into a tube for centrifugation (50mL volume) to prepare a dispersion. To this dispersion, 1.0g of toner was added, and the toner agglomerates were pulverized using, for example, a doctor blade (spatula).

The tube was shaken for 20 minutes with a shaker (shaker) at 350 strokes per minute (spm). After shaking, the solution was transferred to a glass tube for a swing rotor (50mL volume) and separated in a centrifuge (H-9R, kokusanco., Ltd.) using conditions of 3500rpm and 30 minutes. The toner particles are separated from the external additive that is exfoliated by this operation. Satisfactory separation of the toner from the aqueous solution was visually checked, and the toner particles separated into the uppermost layer were recovered with, for example, a blade. The recovered toner particles were filtered on a vacuum filter and then dried in a dryer for 1 hour or more to obtain toner particles. This operation is performed a plurality of times to secure a required amount of toner particles.

Method for extracting resin having formula (1) from toner particles

The extraction of the resin having formula (1) in the toner particles is performed by separating the obtained extract by solvent gradient elution using Tetrahydrofuran (THF). The preparation method is given below.

10.0g of toner particles were weighed out and introduced into cylindrical filter paper (extraction thible) (No.84, Toyo Roshi Kaisha, Ltd.), and placed in a Soxhlet extractor. Extraction was performed using 200mL of THF as a solvent for 20 hours, and then the solvent was removed from the extract to obtain a solid, which was a THF-soluble substance. The resin having formula (1) is contained in a THF-soluble substance. This operation was performed a plurality of times to obtain the required amount of THF-soluble matter.

Gradient preparative HPLC (LC-20AP high pressure gradient preparative system, Shimadzu Corporation;

SunFere preparative columns, Waters Corporation) were used for solvent gradient elution procedures. The following were used: the column temperature is 30 ℃; the flow rate is 50 mL/min; a good solvent for use in the mobile phase is appropriately selected from THF, chloroform and toluene; the poor solvent is appropriately selected from acetonitrile, acetone, methanol and n-hexane. 0.02g of the aforementioned THF-soluble substance dissolved in 1.5mL of a good solvent was loaded as a sample on the gradient preparative HPLC. A composition with 100% poor solvent was used for the starting mobile phase; then, when 5 minutes passed after the sample injection, the percentage of the good solvent was increased by 4% per minute; and the mobile phase composition at 25 minutes became 100% good solvent. The resin having the formula (1) is obtained by drying the obtained fraction to cure. The fractional interval of the resin having formula (1) can be determined by measuring the silicon atom content and¹³C-NMR measurement. By repeating the solvent ladder as requiredElution to obtain the desired amount of resin having formula (1).

Method for measuring silicon atom content in resin having formula (1)

For the silicon atom content in the resin having formula (1), an "Axios" wavelength dispersive x-ray fluorescence analyzer (PANalytical b.v.) was used. The attached "SuperQ version 4.0F" (PANalytical b.v.) software was used to set the measurement conditions and analyze the measurement data.

Rh was used as the x-ray tube anode, and 24kV and 100mA were used as the acceleration voltage and current value, respectively.

Vacuum was used as the measuring atmosphere; 27mm was used as the measurement diameter (collimator diameter); and 10 seconds was used as the measurement time. A Proportional Counter (PC) was used as the detector. The measurement was performed using PET for analyzing the crystal; measuring a count rate (unit: cps) of Si — K α rays observed at a diffraction angle (2 θ) ═ 109.08 °; and determined using a calibration curve as described below.

The resin having formula (1) may be used as it is as a measurement sample, or a resin extracted from toner particles using the aforementioned extraction method may be used as a measurement sample.

A "BRE-32" tablet forming compressor (Maekawa Testing Machine mfg. co., Ltd.) was used to obtain the measurement pellets. 4g of the measurement sample was introduced into a special aluminum compacting ring and flattened, and pellets were produced by forming into a thickness of 2mm and a diameter of 39mm by pressing at 20MPa for 60 seconds, and used as measurement pellets.

Regarding the constructed pellets of the calibration curve for content determination, the amount of the binder [ product name: spectro Blend, composition: c81.0, O2.9, H13.5, N2.6 (mass%), formula: c ₁₉H₃₈ON, form: powder (44 μm) from Rigaku Corporation]0.50 part by mass of SiO₂(hydrophobic fumed silica) [ product name: AEROSIL NAX50, specific surface area: 40 +/-10 (m)²Per g), carbon content: 0.45% to 0.85% from nippon aerosil co.](ii) a Mixing thoroughly in a coffee mill; and preparing the pellets by pellet forming. 5.00 parts by mass and 10.00 parts by mass respectivelyAnd 15.00 parts by mass of SiO₂The same mixing and pellet forming operations were used to prepare the pellets.

Calibration curves in the form of linear functions were obtained by placing the obtained x-ray count rates on the vertical axis and placing each calibration curve on the horizontal axis with the Si addition concentration in the sample.

Then, the same operation was also used for the measurement sample to measure the count rate of Si — K α rays. The silicon atom content (% by mass) was determined from the calibration curve which had been prepared.

(R) structural determination of the resin represented by the formula (1)¹To R³)

R in the resin represented by the formula (1)¹To R³Is constructed by²⁹Si-NMR (solid state) measurement and¹³C-NMR (solid state) measurements. The measurement conditions are given below. As a measurement sample, a resin raw material having formula (1) or a resin extracted from toner particles by the above-described extraction method is used.

“²⁹Measurement conditions of Si-NMR (solid State gas chromatography) "

The instrument comprises the following steps: JNM-ECX500II, JEOL Resonance, Inc.

Sample tube:

sample amount: 150mg of

Measuring the temperature: at room temperature

Pulse mode: CP/MAS

Measuring the nuclear frequency: 97.38 MHz: (²⁹Si)

Reference substance: DSS (external standard: 1.534ppm)

Sample rotation rate: 10kHz

Contact time: 10ms

Delay time: 2s

The scanning times are as follows: 2000 to 8000

This measurement makes it possible to obtain the presence ratio by peak separation/integration by curve fitting for a plurality of silane components depending on the number of oxygen atoms bonded to Si. In this way make it possible toTo confirm R in the resin represented by the formula (1)¹To R³The valence of the alkoxy group or the hydroxyl group with respect to the silicon atom.

¹³Measurement conditions for C-NMR (solid State) analysis

The instrument comprises the following steps: JNM-ECX500II, JEOL Resonance, Inc.

Sample tube:

sample amount: 150mg of

Measuring the temperature: at room temperature

Pulse mode: CP/MAS

Measuring the nuclear frequency: 123.25 MHz: (¹³C)

Reference substance: adamantane (external standard: 29.5ppm)

Sample rotation rate: 20kHz

Contact time: 2ms

Delay time: 2s

The scanning times are as follows: 1024

By this measurement, according to R in the formula (1)¹To R³Is separated into various peaks and each identified to determine R¹To R³The structure of (1).

(P) structural determination of the resin represented by the formula (1)¹And L¹)

P in the resin represented by the formula (1)¹And L¹Can be constructed by¹³C-NMR (solid state) measurement. Measurement conditions are as defined above in¹³Measurement conditions for C-NMR (solid state) are the same. As a measurement sample, a resin raw material having formula (1) or a resin extracted from toner particles by the above-described extraction method is used.

Using the preceding measurement by measuring according to P in formula (1)¹And L¹Separation into individual peaks and identification of each peak to determine P¹And L¹The structure of (1).

Method for measuring weight average molecular weight (Mw)

The weight average molecular weight (Mw) of the polymer, resin or toner particles was measured using Gel Permeation Chromatography (GPC) as follows.

First, the sample was dissolved in Tetrahydrofuran (THF) at room temperature for 24 hours. The obtained solution was filtered using a solvent-resistant membrane filter "sample pretreatment cartridge" (Tosoh Corporation) having a pore size of 0.2 μm to obtain a sample solution. The sample solution was adjusted to a concentration of the THF soluble component of 0.8 mass%. The measurement was performed under the following conditions using the sample solution.

The instrument comprises the following steps: HLC8120 GPC (detector: RI) (Tosoh Corporation)

Column: 7-column columns of Shodex KF-801, 802, 803, 804, 805, 806 and 807 (Showa Denko Kabushiki Kaisha)

Eluent: tetrahydrofuran (THF)

Flow rate: 1.0 mL/min

Oven temperature: 40.0 deg.C

Sample injection amount: 0.10mL

A molecular weight calibration curve constructed using standard polystyrene resins (product names "TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500", Tosohcorporation) was used to determine the molecular weight of the sample.

Method for measuring saturated phase capacity

The saturated compatible amount of the ester compound at 100 ℃ with respect to 100 parts by mass of the binder resin is measured as follows.

The binder resin is first extracted from the toner particles.

The binder resin is obtained by a separation operation using the aforementioned solvent gradient elution method. Alternatively, using known analytical methods, e.g.¹H-NMR analysis,¹³C-NMR analysis, FT-IR analysis, GC-MS analysis, GPC analysis, and the like to determine the kind and structure of the binder resin in the toner particles, and then synthesizing the binder resin alone.

On the other hand, the ester compound is extracted from the toner particles.

The extraction of the ester compound in the toner particles is performed by separating the extract obtained using THF by means of a solvent gradient elution method. The same operation as in the aforementioned method for extracting the resin having formula (1) from toner particles is used to obtain a required amount of THF-soluble matter. The ester compound is present in the THF-soluble matter.

The ester compound is obtained using the same operation as in the aforementioned method for extracting the resin having formula (1) from toner particles and appropriately selecting a good solvent for the mobile phase and appropriately selecting acetone or methanol for a poor solvent from THF, chloroform, and toluene and drying the fractions to solidify. The fractionation interval of the ester compound can be determined by a known analytical method such as¹H-NMR analysis,¹³C-NMR analysis, FT-IR analysis, GC-MS analysis, GPC analysis, etc. The ester compound can also be obtained by identifying the kind and structure of the ester compound in the toner particles using these analysis methods and synthesizing the ester compound alone.

1.00g of the binder resin obtained by the foregoing operation was weighed in a 30mL vial, and heated to 100 ℃. The ester compound was then added to the vial, mixed well at 100 ℃, and visually observed.

Regarding the presence/absence of compatibility, when transparency was seen by visual observation, compatibility was judged to occur.

The ester compound was added in 0.005g increments (0.5 parts by mass relative to 100 parts by mass of the binder resin), and the maximum amount at the time of evaluation as compatible without clouding was determined.

Method for calculating B/A

The content a of the ester compound in the toner may be determined using a step of extracting the ester compound from the toner.

The content "a" of the ester compound in the toner in mass% may be calculated from the weighed mass of the toner and the mass of the ester compound obtained from the toner as obtained in the aforementioned method of measuring the saturated phase capacity.

The content B of the resin having formula (1) in the toner may be determined using a step of extracting the resin having formula (1) from the toner.

The content "B" in mass% of the resin having formula (1) in the toner may be calculated from the mass of the weighed toner obtained as in the aforementioned method for extracting the resin having formula (1) from the toner particles and the mass of the resin having formula (1) obtained from the toner.

The obtained values of A and B are then used to calculate the ratio of B to A (B/A).

Method for calculating solubility parameter (SP value)

The solubility parameter (SP value) was determined using the Fedors equation given in the following formula (II).

For the values of Δ ei and Δ vi, refer to the evaporation energies and molar volumes (25 ℃) of atoms and atomic groups in tables 3 to 9 of "Basic Coating Science of coatings" (pages 54 to 57, 1986 (Maki Shoten Publishing)).

The SP value is expressed in units of (cal/cm)³)^1/2However, 1 (cal/cm) may be used³)^1/2＝2.046×10³(J/m³)^1/2Converting it into (J/m)³)^1/2Units.

i＝(Ev/V)^1/2＝(Δei/Δvi)^1/2(II)

In formula (II), Ev represents the evaporation energy, V represents the molar volume, Δ ei represents the evaporation energy of the atoms or radicals of component i, and Δ vi represents the molar volume of the atoms or radicals of component i.

Method for measuring melting point

The melting point of, for example, an ester compound or the like is measured based on ASTM D3418-82 using a "Q1000" differential scanning calorimeter (TA Instruments).

The melting points of indium and zinc were used for temperature correction of the detection portion of the instrument, and the heat of fusion of indium was used for heat correction.

Specifically, 5mg of the sample was weighed out accurately and introduced into a silver pan; empty silver discs were used for reference. A single measurement was made at a temperature rise rate of 10 deg.c/min from a measurement start temperature of 20 deg.c to a measurement end temperature of 180 deg.c. The peak temperature of the maximum endothermic peak in the DSC curve during this first temperature increase was determined in the range of 20 ℃ to 180 ℃. The peak temperature of the maximum endothermic peak was taken as the melting point (. degree. C.).