JP5132913B2 - Binder resin for toner, method for producing the same, and toner - Google Patents

Description

  The present invention relates to a toner and a binder resin for toner used for developing an electrostatic charge image or a magnetic latent image in electrophotography, electrostatic recording method, electrostatic printing method and the like.

  In the method of obtaining an image by the electrophotographic printing method and the electrostatic charge developing method, the electrostatic charge image formed on the photoreceptor is developed with toner charged in advance by friction and then fixed. As for the fixing method, there are a heat roller method in which a toner image obtained by development is fixed using a pressurized and heated roller, and a non-contact fixing method in which fixing is performed using an electric oven or flash beam light. In order to pass through these processes without any problem, the toner needs to maintain a stable charge amount first, and then needs to have good fixability to paper. In addition, the apparatus has a fixing unit which is a heating body, and the temperature in the apparatus rises, so that it is necessary that the toner does not block. Further, even during continuous printing, it is necessary that the apparatus is not soiled or fogged on the printing surface, that is, the durability of the toner is required.

Further, in the heat roller system, the temperature of the fixing unit has been lowered from the viewpoint of energy saving, and the toner has been strongly required to have a capability of fixing onto a paper at a lower temperature, that is, a low temperature fixability. In addition, as the apparatus becomes more compact, a roller that does not apply a release agent has been used, and there is an increasing demand for toner to be peelable from the heat roller, that is, non-offset.
The binder resin for toner has a great influence on the toner characteristics as described above, and polystyrene resin, styrene-acrylic resin, polyester resin, epoxy resin, polyamide resin, and the like are known. In particular, a polyester resin which is excellent in fixing property at a low temperature and has a good performance balance has attracted attention.

  However, polyester resins tend to have a low non-offset property. In order to give releasability at the time of fixing, a release component such as wax is mixed in the toner, but the polyester resin and the wax are poorly compatible and the dispersion state of the wax component in the toner is bad. In addition to not being able to obtain a sufficient effect of peeling off the wax, it also has an adverse effect on performance such as image stability and durability. For this reason, various studies have been made on the compatibility between the polyester resin and the wax (see, for example, Patent Documents 1 to 4).

  Patent Document 1 discloses a toner having relatively good low-temperature fixability and wax dispersibility by modifying a polyester resin using a specific substance. However, the toner described in Patent Document 1 has a problem that the wax dispersibility is still insufficient, and it is difficult to use it in an energy-saving machine or a high-speed machine that requires a higher level of fixability. .

  On the other hand, Patent Document 2 discloses a polyester toner that is excellent in low-temperature fixability, wax dispersibility, and environmental stability by modifying a polyester resin using a specific substance. However, when the toner described in Patent Document 2 is used as a magnetic toner or a non-magnetic black toner, excellent fixing characteristics, image stability, and durability can be obtained. When used in the above, there is a problem that the color development and color reproducibility of the toner are impaired.

Further, Patent Documents 3 and 4 disclose a polyester resin for toner that is excellent in low-temperature fixability, blocking resistance, and offset resistance by including a modified polypropylene polymer as a polymer component of the polyester resin. However, the polyester resins described in Patent Documents 3 and 4 have a transmittance of light of 400 to 800 nm at a resin thickness of 50 μm which is not 90% or more in the whole region, and color development and color reproducibility are poor. There was a problem of being. In addition, since toners using polyester resins described in Patent Documents 3 and 4 are not sufficiently dispersible in wax, there is a problem of durability such as toner fusion to a member or fogging on a printing surface during continuous printing. Therefore, it was low in utility value as a toner binder resin.
JP-A-11-295919 JP-A-7-175263 JP 7-114209 A JP-A-7-114208

  In view of such circumstances, the present invention can provide a toner having excellent fixing performance, non-offset property, image stability, durability, and excellent color development and color reproducibility that can be used for color. An object of the present invention is to provide a toner binder resin and a toner using the same.

In the presence of the compound (X) in which at least one functional group (f) selected from a carboxyl group and a hydroxyl group is bonded to a terminal carbon of a long-chain alkyl group (r) having 30 or more carbon atoms, (A) Aromatic dicarboxylic acid is a total acid component (excluding compound (X)) 70 mol parts or more in 100 mol parts, and (B) alcohol component (however, excluding compound (X)) 105 A polyester binder resin for toner obtained by polymerizing 150 mole parts, containing 0.5 to 5.0% by mass of the compound (X), and transmitting light in a wavelength range of 400 to 800 nm at a resin thickness of 50 μm. The present invention relates to a polyester binder resin for toner having a rate of 90% or more in the entire region, and also relates to a toner containing the polyester binder resin for toner.

By using the polyester binder resin for toner of the present invention, it is possible to provide a toner having good fixability, non-offset property, image stability, durability, color development and color reproducibility, and particularly good as a color toner. Express performance.

The polyester binder resin for toner of the present invention is polymerized in the presence of a compound (X) having a functional group (f) capable of reacting with an acid or alcohol and a long-chain alkyl group (r) having 30 or more carbon atoms.
Here, in the obtained reaction product, in addition to the polyester resin (P1) having the compound (X) as a structural unit, the polyester resin (P0) not having the compound (X) as a structural unit, Compound (X) may be contained.

The functional group (f) that can react with an acid or an alcohol is a group that reacts with an acid or an alcohol to form a covalent bond. Although it does not restrict | limit especially as reaction which reacts with an acid or alcohol and produces | generates a covalent bond, For example, a condensation reaction, an addition reaction, transesterification etc. are mentioned. By these reactions, the functional group (f) of the compound (X) reacts with the acid or alcohol that is a raw material component of the polyester resin, whereby the residue of the compound (X) is incorporated as a structural unit into the polyester resin. .
Although it does not restrict | limit especially as a functional group (f) which reacts like this, A carboxyl group or its anhydride, a hydroxyl group, a glycidyl group, an alkoxy group, an isocyanate group, an ester group, etc. are mentioned. Among these, a carboxyl group or an anhydride thereof, a hydroxyl group, and an ester group are preferable.

The long-chain alkyl group (r) having 30 or more carbon atoms has an effect of improving the wax dispersibility of the toner when the compound (X) is incorporated as a structural unit of the polyester resin. When the compound (X) is not incorporated as a constituent component of the polyester resin, this effect is exhibited even if the toner contains a compound (X) having a long-chain alkyl group (r) having 30 or more carbon atoms. Absent.
The carbon number of the long-chain alkyl group (r) is preferably 35 or more from the viewpoint of wax dispersibility.
The upper limit of the carbon number of the long chain alkyl group (r) is not particularly limited, but is preferably 100 or less, more preferably 80 or less, from the viewpoint of easy incorporation into the polyester resin.
The long chain alkyl group (r) is not particularly limited, and may be a linear alkyl group (r1) or a branched alkyl group (r2). For example, the linear alkyl group (r1) includes a polyethylene structure having 30 or more carbon atoms, and the branched alkyl group includes a polypropylene structure having 30 or more carbon atoms. Of these, the long-chain alkyl group (r) is preferably a linear alkyl group (r1). When the long-chain alkyl group (r) is a linear alkyl group (r1), the resulting binder resin has good transparency and tends to provide a toner with good color development. The bonding position of the functional group in the compound (X) is not particularly limited, but it is preferably bonded to one end carbon of the long chain alkyl group (r) in consideration of the fixing characteristics of the toner.

The number of functional groups (f) in compound (X) is not particularly limited, but is preferably in the range of 1 to 3 ( mmol / g). When the number of functional groups (f) is 1 ( mmol / g) or more, the compound (X) tends to be incorporated into the polyester resin, and the wax dispersibility tends to be good. There is a tendency to obtain a toner with good transparency and good color development. Further, when the number of functional groups (f) is 3 ( mmol / g) or less, the wax dispersibility of the toner when the compound (X) is taken into the polyester resin tends to be good. The lower limit of the number of functional groups (f) is more preferably 1.1 ( mmol / g) or more, and particularly preferably 1.15 ( mmol / g) or more. The upper limit of the number of functional groups (f) is more preferably 2.8 ( mmol / g) or less, and particularly preferably 2.5 ( mmol / g) or less.

Specific examples of preferred forms of compound (X) include the following, and any of them can be industrially obtained.
(1) A compound having a hydroxyl group at one end of polyethylene having 30 or more carbon atoms. For example, among the Toyo Petrolite Unilin series, the number average molecular weight is 438 or more,
(2) A compound having a carboxyl group at one end of polyethylene having 30 or more carbon atoms. For example, a number average molecular weight of 438 or more in Toyo Petrolite's Unicid series .

The content of compound (X) is not particularly limited, but is 0.5 to 5 in the total amount of polyester resin (P) (total amount of polyester resin (P1), polyester resin (P0), and unreacted compound (X)). It is preferably 5% by mass. When the content of the compound (X) is 0.5% by mass or more, the dispersion of the wax added at the time of toner formation tends to be good, and when it is 5% by mass or less, the blocking resistance is good. Or the obtained binder resin has a good transparency and tends to give a toner with good color development. The lower limit of the content of the compound (X) is more preferably 1% by mass or more, and the upper limit is more preferably 4% by mass or less.
The content of compound (X) is the total amount of compound (X) and unreacted compound (X) in polyester resin (P1).

When the unreacted compound (X) remains in the polyester resin, the content of the unreacted compound (X) is the total amount of the polyester resin (P) (polyester resin (P1), polyester resin (P0), And the total amount of the unreacted compound (X)) is preferably 4.5% by mass or less. When the content of the unreacted compound (X) remaining in the polyester resin is 4.5% by mass or less, the obtained binder resin has good transparency and tends to provide a toner with good color development. As for content of unreacted compound (X), 4 mass% or less is more preferable.
Content of unreacted compound (X) can be calculated | required from the following formula | equation by measuring the endothermic amount of compound (X) in the state contained in the polyester resin.
Content of unreacted compound (X) in resin (% by mass) = {Endotherm of compound (X) contained in polyester resin (J / g)} / {Endotherm of compound (X) itself ( J / g)} × 100 (mass%)

The glass transition temperature (hereinafter referred to as Tg) of the polyester resin (P) is not particularly limited, but is preferably 45 to 65 ° C. When Tg is 45 ° C. or higher, the blocking resistance of the toner tends to be good, and when it is 65 ° C. or lower, the fixability of the toner tends to be good. As for the lower limit of Tg, 50 degreeC or more is more preferable.
The softening temperature of the polyester resin (P) is not particularly limited, but is preferably 90 to 200 ° C. When the softening temperature is 90 ° C. or higher, the non-offset property of the toner tends to be good, and when it is 200 ° C. or lower, the toner fixability tends to be good. The lower limit value of the softening temperature is more preferably 100 ° C. or higher, and the upper limit value is more preferably 180 ° C. or lower.

  The acid value of the polyester resin (P) is not particularly limited, but is preferably 20 mgKOH / g or less. When the acid value is 20 mgKOH / g or less, the image density of the toner tends to be stable. The upper limit of the acid value of the polyester resin (P) is more preferably 15 mgKOH / g or less, and particularly preferably 12 mgKOH / g or less.

The polyester binder resin for toner of the present invention has a light transmittance of 90% or more in the entire region at a wavelength of 400 to 800 nm at a resin thickness of 50 μm. When the light transmittance of the binder resin is 90% or more in the entire visible light wavelength range of 400 to 800 nm, the color developability and color reproducibility of the toner obtained using the binder resin tend to be good.
Note that the color development and color reproducibility of the toner, which is an effect of the present invention, is one of the indicators of whether or not the color of the image to be printed can be faithfully reproduced, and determines the appropriateness as a color toner. . For example, a test pattern printed on an OHP sheet is projected by an overhead projector, and the projected image clarity, the presence / absence of color dullness, etc. are visually evaluated to determine whether the color developability, color reproducibility is good or bad. be able to.

Hereinafter, a method for producing the polyester binder resin for toner of the present invention will be described.
In the presence of the compound (X) having a functional group (f) capable of reacting with an acid or alcohol and a long-chain alkyl group (r) having 30 or more carbon atoms, the polyester binder resin for toner of the present invention,
(A) 100 mol parts of acid component (however, excluding compound (X)) and (B) alcohol component (however, excluding compound (X)) are produced by polymerizing 105 to 150 mol parts. Can do.

  (A) The acid component is not particularly limited, but terephthalic acid, isophthalic acid, dimethyl terephthalate, dimethyl isophthalate, diethyl terephthalate, diethyl isophthalate, dibutyl terephthalate, dibutyl isophthalate, or esters or acid anhydrides thereof Aromatic dicarboxylic acid components such as phthalic acid; aliphatic dicarboxylic acid components such as phthalic acid, sebacic acid, isodecyl succinic acid, dodecenyl succinic acid, maleic acid, fumaric acid, adipic acid, or esters or acid anhydrides thereof; Acid, pyromellitic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,2, 7,8-octanetetracarboxylic acid or this Polyvalent carboxylic acid component such as trivalent or more such as ester or acid anhydride thereof.

As the aromatic dicarboxylic acid, terephthalic acid and isophthalic acid are preferable in terms of handling properties and cost. Trivalent or higher polyvalent carboxylic acid is preferably trimellitic acid or its acid anhydride.
In addition, when the functional group (f) capable of reacting with the acid or alcohol of the compound (X) is a carboxyl group or an anhydride or ester thereof, the compound (X) corresponds to the acid component. (A) An acid component shall mean acid components other than compound (X).

  Although the usage-amount of an aromatic dicarboxylic acid component is not restrict | limited in particular, It is preferable to use 70 mol parts or more in 100 mol parts of all the acid components (however, except compound (X)). When the amount of the aromatic dicarboxylic acid component used is 70 mol parts or more, the storage stability of the toner tends to be good and the resin strength tends to be improved. As for the lower limit of the usage-amount of an aromatic dicarboxylic acid component, 75 mol part or more is more preferable.

  When a trivalent or higher polyvalent carboxylic acid component is used, it is preferably used in an amount of 0.1 to 30 mol parts per 100 mol parts of the total acid component (excluding compound (X)). When the amount of the trivalent or higher polyvalent carboxylic acid component is 0.1 mol part or more, the non-offset property of the toner tends to be good, and when it is 30 mol part or less, the toner has blocking resistance and fixing. Tend to be good. The lower limit value of the amount of the trivalent or higher polyvalent carboxylic acid component is more preferably 1 mol part or more, and the upper limit value is more preferably 28 mol parts or less.

(B) It does not restrict | limit especially as an alcohol component, An aliphatic diol component and an aromatic diol component can be used.
The aliphatic diol component is not particularly limited, but ethylene glycol, neopentyl glycol, propylene glycol, butanediol, polyethylene glycol, 1,2-propanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1, Examples include 4-cyclohexanedimethanol.

The aromatic diol component is not particularly limited, but polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.2) -polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2 -Bis (4-hydroxyphenyl) propane, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.4) -2,2-bis (4- Aromatic diol components such as hydroxyphenyl) propane and polyoxypropylene (3.3) -2,2-bis (4-hydroxyphenyl) propane. It is.
These can be used alone or in combination of two or more, and can also be used in combination of an aliphatic diol component and an aromatic diol component.

  Further, as the (B) alcohol component, in addition to these diol components, a trihydric or higher polyhydric alcohol component can also be used. The trihydric or higher polyhydric alcohol component is not particularly limited, but sorbitol, 1,2,3,6-hexatetralol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2 , 4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methyl-1,2,3-propanetriol, 2-methyl-1,2,4-butanetriol, trimethylolpropane, 1,3 , 5-trihydroxymethylbenzene and the like. These can be used alone or in combination of two or more. Among these, pentaerythritol and trimethylolpropane are particularly preferable.

In addition, when the functional group (f) which can react with the acid or alcohol of the compound (X) is a hydroxyl group, the compound (X) corresponds to the alcohol component, but here the (B) alcohol component is And alcohol components other than compound (X).
In the present invention, the amount of the aliphatic diol component used is not particularly limited, but it is preferably 10 mol parts or more per 100 mol parts of the total acid component (excluding compound (X)). When the amount of aliphatic diol used is 10 mol parts or more, the degree of polymerization tends to increase and the non-offset property of the toner tends to be good, and polymerization is performed for a long time without using a large amount of polymerization catalyst. The polymerization degree tends to be increased even if it is not necessary, and this is preferable in terms of cost and environment. As for the usage-amount of an aliphatic diol component, 15 mol part or more is more preferable.

In the case of using a trihydric or higher polyhydric alcohol component, it is preferably contained in an amount of 0.1 to 30 mol parts per 100 mol parts of the total acid component (excluding compound (X)). This is because the non-offset property of the toner tends to be good when the content is 0.1 mol part or more, and the blocking resistance and fixing property of the toner tend to be good when the content is 30 mol parts or less. Because it is in. More preferably, it is the range of 1-28 mol part.
When a trivalent or higher polyvalent carboxylic acid component is used, it is preferably used in an amount of 0.1 to 30 mol parts per 100 mol parts of the total acid component (excluding compound (X)). When the amount of the trihydric or higher polyhydric alcohol component is 0.1 mol part or more, the non-offset property of the toner tends to be good, and when it is 30 mol part or less, the toner has anti-blocking property or fixing property. Tends to be good. The lower limit value of the amount of the trihydric or higher polyhydric alcohol component is more preferably 1 mol part or more, and the upper limit value is more preferably 28 mol parts or less.

In the present invention, in the presence of the aforementioned compound (X),
(A) 100 mol parts of acid components (however, excluding compound (X)) and (B) alcohol components (however, excluding compound (X)) of 105 to 150 mol parts are polymerized.
(B) When the amount of alcohol component (excluding compound (X)) is 105 mol parts or more per 100 mol parts of (A) acid component (excluding compound (X)) Therefore, the reaction time is shortened, the productivity is improved, the residual monomer in the resin tends to be reduced, and a resin having a high light transmittance can be obtained. As a result, it tends to provide a toner with good color development. In addition, the stability of the obtained resin image tends to be good, and the environmental dependency of charging tends to be small. Further, when the amount of the (B) alcohol component (excluding the compound (X)) is 150 mol parts or less, the chargeability of the resin tends to be good. (B) The lower limit of the amount of the alcohol component (excluding the compound (X)) is preferably 125 mol parts or more, and the upper limit is preferably 145 mol parts or less.

  The addition time of compound (X) is not particularly limited, but it is charged into the reaction vessel together with the above-mentioned (A) acid component and (B) alcohol component, and polymerized in the presence of compound (X) to produce a polyester resin. It is preferable. By polymerizing in this way, at least a part of the compound (X) reacts and is incorporated into the polyester resin. The compound (X) does not necessarily need to be completely incorporated into the polyester resin, and a part of the compound (X) may be dispersed in the polyester resin as it is without reacting. Thus, dispersibility of the externally added wax is more effectively improved by introducing the compound (X) into the reaction vessel together with the components (A) and (B) for polymerization. Further, the compound (X) is easily incorporated into the polyester resin, the resulting binder resin has good transparency, and a toner with good color development can be obtained.

In the present invention, the following six items can be mentioned as factors for obtaining a polyester binder resin for a toner having a light transmittance in a region of a wavelength of 400 to 800 nm at a resin thickness of 50 μm of 90% or more in the entire region. Meet all four items (a-1) to (a-4) or (a'-1) to (a'-4) and two items (b-1) and (b-2) Is most preferable, but it is not always necessary to satisfy all six items. Also not meet any one item, by adjusting the other five items as appropriate, for a toner polyester binder light transmittance at a wavelength region of 400~800nm in resin thickness 50μm is 90% or more in the entire region A resin can be obtained.

(A) Regarding the compound (X) to be used, in the case of the compound (X1) in which the long-chain alkyl group (r) is a linear alkyl group (r1),
(A-1) The number of functional groups is 1 ( mmol / g) or more.
(A-2) The carbon number of the long-chain alkyl group (r1) is 100 or less.
(A-3) The content of the compound (X1) is 5% by mass or less.
(A-4) Content of unreacted compound (X1) shall be 4.5 mass% or less.
(A) Regarding the compound (X) to be used, in the case of the compound (X2) in which the long-chain alkyl group (r) is a branched alkyl group (r2),
(A′-1) The number of functional groups is 1 ( mmol / g) or more.
(A′-2) The carbon number of the long-chain alkyl group (r1) is 100 or less.
(A′-3) The content of the compound (X2) is 0.5% by mass or less.
(A'-4) Content of unreacted compound (X2) shall be 0.45 mass% or less.
(B) Production formulation (b-1) The alcohol component (excluding compound (X)) is 105 mol parts or more with respect to 100 mol parts of the acid component (excluding compound (X)),
(B-2) Compound (X) is charged into the reaction vessel together with (A) the acid component and (B) the alcohol component.

  In the present invention, if necessary, a polyester resin can be polymerized by adding a release agent component together with the above components within a range not impairing the effects of the present invention. By adding a release agent component and polymerizing, the toner fixing property and wax dispersibility tend to be improved. As the release agent component, the same waxes that can be used as a toner formulation described later can be used as appropriate. For example, carnauba wax, rice wax, beeswax, polypropylene wax having no functional group (f), functional group ( Examples thereof include polyethylene waxes, synthetic ester waxes, paraffin waxes, fatty acid amides, and silicone waxes that do not have f).

The method for polymerizing the binder resin of the present invention is not particularly limited, and examples thereof include a method in which the above-described components are introduced into a reaction vessel and polymerized through an esterification reaction or a transesterification reaction and a condensation reaction.
In the polymerization of the polyester resin, for example, a polymerization catalyst such as titanium tetrabutoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium oxide or the like can be used.

  The polymerization temperature is not particularly limited, but is preferably in the range of 180 ° C to 280 ° C. When the polymerization temperature is 180 ° C. or higher, the productivity tends to be good, and when it is 280 ° C. or lower, the decomposition of the resin and the by-product of volatile components that cause odor tend to be suppressed. The lower limit of the polymerization temperature is more preferably 200 ° C. or higher, and particularly preferably 220 ° C. or higher. The upper limit of the polymerization temperature is more preferably 270 ° C. or less.

  The binder resin of the present invention is not limited to the above-described polyester resin (P) as long as the effects of the present invention are not impaired. For example, a polyester resin other than the polyester resin (P), a styrene resin, and a styrene-acrylic resin. It can also be used in combination with a resin, a cyclic olefin resin, a methacrylic acid resin, an epoxy resin, or the like. From the viewpoint of wax dispersibility, the amount of these other resins used is preferably 50% by mass or less, more preferably 40% by mass or less, and particularly preferably 30% by mass or less in the binder resin.

The toner containing the binder resin of the present invention may contain a colorant, a charge control agent, a release agent, an additive such as a flow modifier, a magnetic material, and the like as necessary.
The colorant is not particularly limited, but carbon black, nigrosine, aniline blue, phthalocyanine blue, phthalocyanine green, hansa yellow, rhodamine dye, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, monoazo And disazo dyes, condensed azo dyes or pigments. These dyes and pigments can be used alone or in admixture of two or more. In the case of a full color toner, yellow includes benzidine yellow, monoazo dyes and dyes, condensed azo dyes and the like, magenta includes quinacridone, rhodamine dyes and monoazo dyes, and cyan includes phthalocyanine blue and the like.
The content of the colorant is not particularly limited, but is preferably 2 to 10% by mass in the toner from the viewpoint of the toner color tone, image density, and thermal characteristics.

The charge control agent is not particularly limited, and examples of the positive charge control agent include quaternary ammonium salts and basic or electron-donating organic substances. Negative charge control agents include metal chelates, metal-containing dyes, and acidic substances. Or an electron withdrawing organic substance etc. are mentioned. In the case of color toners, it is important that the charge control agent is colorless or light color and does not cause any color tone problems on the toner. Examples include metal salts, metal complexes, amides of salicylic acid or alkylsalicylic acid with chromium, zinc, aluminum, etc. A compound, a phenol compound, a naphthol compound, etc. are mentioned. Furthermore, a vinyl polymer having a styrene, acrylic acid, methacrylic acid or sulfonic acid group may be used as the charge control agent.
The content of the charge control agent is not particularly limited, but is preferably 0.5 to 5% by mass in the toner. When the content of the charge control agent is 0.5% by mass or more, the charge amount of the toner tends to be a sufficient level, and when the content is 5% by mass or less, a decrease in the charge amount due to aggregation of the charge control agent is suppressed. It tends to be.

The release agent is not particularly limited, and examples thereof include carnauba wax, rice wax, beeswax, polypropylene wax, polyethylene wax, synthetic ester wax, paraffin wax, fatty acid amide, and silicone wax.
The content of the releasing agent is not particularly limited, but it is preferably 0.3 to 15% by mass in the toner because it affects the releasing effect, storage stability, fixing property, color developing property and the like of the toner. The lower limit of the content of the release agent is more preferably 1% by mass or more, and particularly preferably 2% by mass or more. Further, the upper limit value of the content of the release agent is more preferably 13% by mass or less, and particularly preferably 10% by mass or less.

Additives such as flow modifiers are not particularly limited, but fine powder silica, alumina, titania and other fluidity improvers, magnetite, ferrite, cerium oxide, strontium titanate, conductive titania and other inorganic fine powders , Resistance adjusting agents such as styrene resin and acrylic resin, lubricants and the like, and these are used as an internal additive or an external additive.
The content of these additives is not particularly limited, but is preferably 0.05 to 10% by mass in the toner. When the content of these additives is 0.05% by mass or more, a toner performance-modifying effect tends to be sufficiently obtained, and when it is 10% by mass or less, the image stability of the toner tends to be good. is there.

The toner of the present invention can be used as any one of a magnetic one-component developer, a non-magnetic one-component developer, and a two-component developer.
When used as a magnetic one-component developer, it contains a magnetic substance. Examples of the magnetic substance include ferromagnetic alloys including iron, cobalt, nickel, etc., including ferrite, magnetite, etc. Alloys that do not contain magnetic elements but exhibit ferromagnetism by appropriate heat treatment, such as so-called Heusler alloys containing manganese and copper, such as manganese-copper-aluminum, manganese-copper-tin, and chromium dioxide Is mentioned.
The content of the magnetic substance is not particularly limited, but is preferably 3 to 70% by mass in the toner because it greatly affects the pulverizability of the toner. When the content of the magnetic material is 3% by mass or more, the charge amount of the toner tends to be at a sufficient level, and when it is 70% by mass or less, the fixability and grindability of the toner tend to be good. The lower limit of the content of the magnetic substance is more preferably 3% by mass or more, and particularly preferably 3% by mass or more. Further, the upper limit of the content of the magnetic material is more preferably 60% by mass or less, and particularly preferably 50% by mass or less.

  When used as a two-component developer, it is used in combination with a carrier. As the carrier, a known material such as a magnetic substance such as iron powder, magnetite powder, or ferrite powder, a resin coating on the surface thereof, or a magnetic carrier can be used. As coating resins for resin coating carriers, generally known styrene resins, acrylic resins, styrene acrylic copolymer resins, silicone resins, modified silicone resins, fluorine resins, mixtures of these resins, etc. Can be used.

  The method for producing the toner containing the binder resin of the present invention is not particularly limited, but after mixing the above-mentioned binder resin and the compound, melt-kneading with a twin screw extruder or the like, coarse pulverization, fine pulverization, classification If necessary, a method of producing inorganic particles by external addition treatment (pulverization method), dissolving and dispersing the binder resin and compound described above in a solvent, granulating in an aqueous medium, and then adding the solvent Examples of the method include a method (chemical method) in which toner particles are obtained by removing, washing, and drying and externally adding inorganic particles as necessary.

Although the Example of this invention is shown below, the embodiment of this invention is not limited to this. The evaluation methods for the resin and toner shown in this example are as follows.
(1) Analysis method of compound (X) 1) Endotherm (J / g)
Using a differential differential calorimeter DSC-60 manufactured by Shimadzu Corporation, the temperature was increased at a rate of 5 ° C./min. From the endothermic peak area on the DSC chart, the endothermic amount of compound (X) itself ( J / g).

(2) Binder resin evaluation method 1) Visible light transmittance
A resin film having a thickness of 50 μm was prepared using a heat press, and light transmittance was measured at a wavelength of 400 to 800 nm using an ultraviolet-visible spectrophotometer “UV-2400” manufactured by Shimadzu Corporation. Subsequently, the visible light transmittance was evaluated from the measurement results according to the following criteria.
○: The light transmittance is 90% or more at all wavelengths.
X: The light transmittance is less than 90% at all or some wavelengths.
2) Glass transition temperature (Tg)
The temperature at the intersection of the base line of the chart and the tangent line of the endothermic curve near the glass transition temperature when measured at a heating rate of 5 ° C./min using a differential differential calorimeter DSC-60 manufactured by Shimadzu Corporation Asked.

3) Softening temperature When using a flow tester CFT-500 manufactured by Shimadzu Corporation with a nozzle of 1 mmφ × 10 mm and measuring with a load of 294 N (30 Kgf) and a heating rate of 3 ° C./min, a sample The temperature at which 1/2 of 1.0 g flowed out was determined.
4) Acid value (AV)
About 0.2 g of the sample was precisely weighed in a branch Erlenmeyer flask (A (g)), 10 ml of benzyl alcohol was added, and the mixture was heated in a nitrogen atmosphere for 15 minutes with a heater at 230 ° C. to dissolve the resin. After allowing to cool to room temperature, 10 ml of benzyl alcohol, 20 ml of chloroform and several drops of phenolphthalein were added, and titrated with a 0.02 N KOH solution (titrate = B (ml), titer of KOH solution = p). A blank measurement was performed in the same manner (titer amount = C (ml)), and calculation was performed according to the following formula.
Acid value (mgKOH / g) = (BC) × 0.02 × 56.11 × p ÷ A
5) Endothermic amount of unreacted compound (X) in the polyester resin (J / g)
Using the same apparatus as in 2), measurement was performed under the same conditions, and the endothermic peak in the DSC chart was determined from the area from the baseline.
In addition, about content of the unreacted compound (X) in resin, it can obtain | require from the following formula | equation.
Content of unreacted compound (X) in resin (% by mass) = {Endotherm of compound (X) contained in polyester resin (J / g)} / {Endotherm of compound (X) itself ( J / g)} × 100 (mass%)

(3) Toner Evaluation Method 1) Non-offset property Using a printer having a fixing roller not coated with silicone oil and capable of changing the temperature set to a roller speed of 100 mm / s, a test pattern of 0.5 mg / A solid image of 4.5 cm × 15 cm was printed at a toner density of cm ² and the non-offset property was evaluated. Further, the minimum temperature at which the toner moves to the fixing roller due to a hot offset phenomenon at the time of fixing is defined as an offset generation temperature, and the non-offset property is determined using the following criteria.
◎ (Good): Offset generation temperature is 200 ° C or higher ○ (Usable): Offset generation temperature is 180 ° C or higher and lower than 200 ° C x (Inferior): Offset generation temperature is lower than 180 ° C

2) Fixability Using the non-offset evaluation equipment, the above test pattern image fixed with the fixing roller temperature set at 145 ° C. at the same fixing speed was rubbed 9 times with a JIS 512 sand eraser, The image density before and after the test was measured with an image densitometer manufactured by Macbeth Co., and the fixing rate was calculated by the following formula and evaluated according to the following criteria.
Fixing rate = image density after test / image density before test × 100 (%)
◎ (Very good): Fixing rate of 80% or more ○ (Good): Fixing rate of 75% or more and less than 80% △ (Available): Fixing rate of 70% or more and less than 75% × (Inferior): Less than 70% Fixation rate or cold offset phenomenon occurs at 145 ° C and cannot be measured

3) Blocking resistance Approximately 5 g of the toner was weighed and put into a sample bottle, which was left in a dryer kept at 50 ° C. for about 24 hours, and the degree of aggregation of the toner was evaluated as an index of blocking resistance. . The evaluation criteria were as follows.
◎ (Good): Dispersed simply by inverting the sample bottle.
○ (Available): Disperse the sample bottle upside down and tap it 2-3 times.
X (Inferior): Dispersed when the sample bottle is turned upside down and tapped 4 to 5 times or more.

4) Image stability When 10,000 sheets were printed under the same conditions as the non-offset evaluation method, the image stability was evaluated based on the toner charge amount.
A (very good): There is no change in the initial charge amount and the final charge amount.
○ (Good): The amount of charge is slightly changed, but the image density is less affected.
Δ (usable): The charge amount (image density) varies, but can be improved by additives.
X (Inferior): Image density greatly changes.

5) Durability After 10,000 sheets were printed by the same method as image stability, durability was evaluated based on fusion to a member and fogging of the printed surface.
A (very good): No fusion or fogging to the member is observed.
○ (Good): Only slight adhesion or fogging to the parts can be seen.
Δ (Available): Fusing and fogging are slightly observed on the member, but can be improved by additives.
X (Inferior): Fusing and fogging on the member are greatly observed.

6) Color development / color reproducibility A test pattern image was printed on an OHP sheet using a non-offset evaluation facility. The image was projected with an overhead projector, and the image projected on the screen was visually evaluated for vividness and color dullness. The suitability of each color toner as a color toner having a multilayer structure is determined.
A (good): The projected image is clear and no color dullness is observed. Color developability and color reproducibility are good.
○ (Available): The projected image is almost clear and only a slight color dullness is observed. The color developability and color reproducibility are at a usable level.
X (Inferior): The projected image is unclear, color dullness is observed, and color developability and color reproducibility are unusable.

Example 1
1500 ppm of antimony trioxide is charged into a reaction vessel equipped with a distillation column with respect to the acid component, alcohol component, compound (X), and total acid component (excluding compound (X)) of the charge composition shown in Table 1. did. Subsequently, the rotation speed of the stirring blade in the reaction vessel was kept at 120 rpm, temperature increase was started, and the temperature in the reaction system was heated to 265 ° C., and this temperature was maintained. Water was distilled from the reaction system to start the esterification reaction. Subsequently, the temperature in the reaction system was lowered and maintained at 235 ° C., the pressure in the reaction vessel was reduced over about 40 minutes, the degree of vacuum was set to 133 Pa, and a condensation reaction was performed while distilling the diol component from the reaction system. The viscosity of the reaction system increased with the reaction, the degree of vacuum was increased with the increase of the viscosity, and the condensation reaction was carried out until the torque of the stirring blade reached a value indicating a desired softening temperature. Then, stirring was stopped when a predetermined torque was exhibited, the reaction system was returned to normal pressure, pressurized with nitrogen, and the reaction product was taken out over about 40 minutes to obtain polyester resin 1.
Table 1 shows the total reaction time, which was the time required from the start of the esterification reaction (water distillation start time) to the end of the condensation reaction (stirring stop time). The characteristic values of the obtained resin are also shown in Table 1.

Next, the polyester resin 1 obtained above was used to form a toner. For blending the toner, 93% by mass of polyester resin 1, 3% by mass of quinacridone pigment (HOSTAARM PINK E, CI No .: Pigment Red 122 manufactured by Clariant), polyethylene wax (manufactured by Sanyo Chemical Industries, Sunwax) 171-P) 3% by mass and 1% by mass of a negatively chargeable charge control agent (E-84 manufactured by Orient Chemical Co., Ltd.) were used and mixed for 5 minutes with a Henschel mixer. Next, the obtained mixture was melt-kneaded with a biaxial kneader. The melt kneading was performed by setting the internal temperature to the softening temperature of the resin. After kneading, the toner soul was obtained by cooling, finely pulverized to 10 μm or less with a jet mill fine pulverizer, and fine particles of 3 μm or less were cut with a classifier to adjust the particle size. To 100 parts by mass of the fine powder obtained, 0.25 part by mass of silica (R-972 manufactured by Nippon Aerosil Co., Ltd.) was added, mixed and adhered with a Henschel mixer, and finally a toner was obtained.
The obtained toner was evaluated for toner using the aforementioned evaluation method. The evaluation results are shown in Table 1.

Example 2-4 and Comparative Examples 1, 3, 4, and 7
(A) Acid resin, (B) Alcohol component, and Compound (X) are changed as shown in Table 1 and Table 2 in the same manner as in Example 1 for polyester resins 2 to 4 , polyester resin A, Polyester resin C, polyester resin D, and polyester resin F were obtained.
Tables 1 and 2 show the total reaction time and the characteristic values of the obtained resin.
Next, a toner was obtained in the same manner as in Example 1 except that polyester resins 2 to 4 , polyester resin A, polyester resin C, polyester resin D, and polyester resin F were used in place of polyester resin 1, respectively. .
The obtained toner was evaluated for toner using the aforementioned evaluation method. The evaluation results are shown in Table 1 or Table 2.

Synthesis Example 1 (Example of production of polyester resin a)
Distillation tower is equipped with 75 mol parts of terephthalic acid as acid component, 20 mol parts of isophthalic acid and 5 mol parts of adipic acid, 15 mol parts of cyclohexanedimethanol as alcohol component and 125 mol parts of ethylene glycol, and 1500 ppm antimony trioxide as catalyst. The reaction vessel was charged. Subsequently, the rotation speed of the stirring blade in the reaction vessel was kept at 120 rpm, temperature increase was started, and the temperature in the reaction system was heated to 265 ° C., and this temperature was maintained. Water was distilled from the reaction system to start the esterification reaction. Subsequently, the temperature in the reaction system was raised and maintained at 280 ° C., the pressure in the reaction vessel was reduced over about 40 minutes, the degree of vacuum was set to 133 Pa, and a condensation reaction was performed while distilling the diol component from the reaction system. Stirring was stopped when the torque of the stirring blade showed a desired value, the reaction system was returned to normal pressure, pressurized with nitrogen, and the reaction product was taken out over about 40 minutes to obtain polyester resin a. The softening temperature of the polyester resin a was 175 ° C., the Tg was 58.1 ° C., and the acid value was 5.1 mgKOH / g.

Examples 5 to 7 and Comparative Example 2
The same method as in Example 1 except that (A) the acid component, (B) the alcohol component, and compound (X) used in the production of the polyester resin of Example 1 are changed as shown in Table 1 or Table 2. Polyester resins 5 to 7 and polyester resin B were obtained. The total reaction time and the characteristic values of the obtained resin are shown in Table 1 or Table 2.
Next, in place of the polyester resin 1, the polyester resins 5 to 7 , the polyester resin B, and the polyester resin a obtained in Synthesis Example 1 were used except that they were used in the ratios shown in Table 1 or Table 2. A toner was obtained in the same manner as above.
The obtained toner was evaluated for toner using the aforementioned evaluation method. The evaluation results are shown in Table 1 or Table 2.

Example 8
45 parts by mass of the polyester resin 1 obtained in Example 1, 1.5 parts by mass of quinacridone pigment (HOSTAARM PINK E, CI No .: Pigment Red 122 manufactured by Clariant), polyethylene wax (manufactured by Sanyo Chemical Industries) , Sunwax 171-P) 3 parts by weight, 0.5 parts by weight of a negatively chargeable charge control agent (E-84 manufactured by Orient Chemical Co., Ltd.) are dissolved and dispersed in 50 parts by weight of methyl ethyl ketone, and mixed with a solid content of 50% by weight. A liquid was obtained. Next, 80 parts by mass of the mixed solution, 6 parts by mass of methyl ethyl ketone, 5 parts by mass of isopropyl alcohol, and 2.7 parts by mass of an aqueous 1N sodium hydroxide solution were charged into a 1 L round bottom flask, and the liquid temperature was 30 ° C. while stirring at 350 rpm. It was. While maintaining the stirring speed and the liquid temperature, 30 parts by mass of deionized water was added dropwise over 10 minutes to carry out phase inversion emulsification. After holding for 10 minutes, the stirring rotation speed was reduced to 150 rpm, and 50 parts by mass of deionized water was added.
Next, the liquid temperature was raised, methyl ethyl ketone was removed by distillation operation, and an aqueous medium toner particle dispersion was obtained.
The obtained dispersion is washed with filtered water, and then the toner powder is redispersed in deionized water, 1N hydrochloric acid is added to adjust the pH to about 3, and the filtered water is washed twice to sufficiently wash the toner cake. Got. The obtained toner cake was sufficiently dried by a vacuum dryer at 50 ° C.
To 100 parts by mass of the fine powder obtained, 0.25 part by mass of silica (R-972 manufactured by Nippon Aerosil Co., Ltd.) was added, mixed and adhered with a Henschel mixer, and finally a toner was obtained.
The obtained toner was evaluated for toner using the aforementioned evaluation method. The evaluation results are shown in Table 1.

Comparative Example 5
In a reaction vessel equipped with a distillation tower, 1500 ppm of antimony trioxide with respect to (A) acid component, (B) alcohol component and total acid component (excluding compound (X)) of the charge composition shown in Table 2 was used. I put it in. Subsequently, the rotation speed of the stirring blade in the reaction vessel was kept at 120 rpm, temperature increase was started, and the temperature in the reaction system was heated to 265 ° C., and this temperature was maintained. Water was distilled from the reaction system to start the esterification reaction. Subsequently, the temperature in the reaction system was lowered and maintained at 235 ° C., the pressure in the reaction vessel was reduced over about 40 minutes, the degree of vacuum was set to 133 Pa, and a condensation reaction was performed while distilling the diol component from the reaction system. The viscosity of the reaction system increased with the reaction, the degree of vacuum was increased with the increase of the viscosity, and the condensation reaction was carried out until the torque of the stirring blade reached a value indicating a desired softening temperature. And when the predetermined torque was shown, the reaction system was returned to normal pressure and the compound (X) was added. After 30 minutes, stirring was stopped, the reaction product was taken out over about 40 minutes by pressurizing with nitrogen, and polyester resin E was obtained. The total reaction time and the characteristic values of the obtained resin are shown in Table 2.
Next, a toner was obtained in the same manner as in Example 1 except that the polyester resin 1 was changed to the polyester resin E.
The obtained toner was evaluated for toner using the aforementioned evaluation method. The evaluation results are shown in Table 2.

Comparative Example 6
(A) Acid component, (B) Alcohol component, other components having the charge composition shown in Table 2, and 1500 ppm of antimony trioxide with respect to the total acid component were charged into a reaction vessel equipped with a distillation column. Subsequently, the rotation speed of the stirring blade in the reaction vessel was kept at 120 rpm, temperature increase was started, and the temperature in the reaction system was heated to 265 ° C., and this temperature was maintained. Water was distilled from the reaction system to start the esterification reaction, but the polyethylene added as the other component was decomposed by heat, and the oil was distilled with water. Although the distillation of water ceased and the esterification reaction was completed, the reaction vessel was extremely contaminated with decomposition products, and the condensation reaction that was to be carried out next had to be stopped, resulting in no polyester resin.

From the above examples and comparative examples, the following was found.
(1) In the toner using the binder resin containing the polyester resin (P) containing the compound (X) of Examples 1 to 8 , the dispersibility of the wax added at the time of toner formation is improved, and the non-offset property and the fixing property are improved. In addition, a toner with good balance of image quality and durability, and excellent color development and color reproducibility was obtained.
(2) In Examples 1, 2, and 8 using the polyester resin (P) containing the compound (X) having a long-chain alkyl group having 48 carbon atoms, the dispersibility of the wax added at the time of toner formation is better. Therefore, the toner using this alone was particularly excellent in non-offset property and durability.
(3) Polymerization was carried out using 135 mol parts of (B) alcohol component (excluding compound (X)) per 100 mol parts of (A) acid component (excluding compound (X)). Resins 1 and 2 have a shorter total reaction time compared to resin 3 using 120 mole parts of (B) alcohol component (excluding compound (X)), and toners using these have image stability. Was excellent.

(4) (A) Acid component (excluding compound (X)) Resins 1 and 2 polymerized using an alcohol component containing 50 moles of aliphatic diol per 100 moles are aliphatic The total reaction time was shorter than that of Resin 4 using 5 mol parts of diol, and the toner using these had excellent image stability.
(5) Examples 5 to 7 are used in combination with other resins, but exhibit well-balanced toner performance. Resins 5 and 6 polymerized using 108 mol parts of (B) alcohol component (excluding compound (X)) are 102 mol parts of (B) alcohol component (excluding compound (X)). As compared with the polymerized resin 7 , the total reaction time was short.

(6) A toner obtained from a resin containing no compound (X) or containing a compound having an alkyl group having a carbon number smaller than that of the compound (X) has insufficient dispersibility of the wax added at the time of toner formation. Therefore, durability was inferior (Comparative Examples 1 and 4).
(7) A toner using a resin with poor visible light transmittance is inferior in toner color development and color reproducibility, and has low utility value for color toners (Comparative Examples 2, 3, 5, and 7). ).
(8) When a compound (polyethylene) having no functional group (f) capable of reacting with an acid or alcohol was used instead of the compound (X), a polyester resin could not be obtained (Comparative Example 6). .

About the Example and comparative example which were described in Table 1 and Table 2, the material described below was used.
Diol A: 2.3 mol adduct of bisphenol A propylene oxide Diol B: 2.0 mol adduct of bisphenol A ethylene oxide Compound A: Toyo Petrolite Co., Ltd. Unilin 700
Compound B: Toyo Petrolite Co., Ltd. Unicid 700
Compound D: NS Chemical Rice Wax
Compound E: based on polypropylene having 140 carbon atoms and one end modified with maleic acid

Claims (3)

In the presence of the compound (X) in which at least one functional group (f) selected from a carboxyl group and a hydroxyl group is bonded to the terminal carbon of the long-chain alkyl group (r) having 30 or more carbon atoms,
(A) Aromatic dicarboxylic acid is a total acid component (excluding compound (X)) 70 mol parts or more in 100 mol parts, and (B) alcohol component (however, excluding compound (X)) 105 A polyester binder resin for toner obtained by polymerizing 150 mol parts , comprising 0.5 to 5.0% by mass of the compound (X),
A polyester binder resin for toner having a light transmittance of 90% or more in the entire region in a wavelength range of 400 to 800 nm at a resin thickness of 50 μm. In the presence of the compound (X) in which at least one functional group (f) selected from a carboxyl group and a hydroxyl group is bonded to the terminal carbon of the long-chain alkyl group (r) having 30 or more carbon atoms,
(A) Aromatic dicarboxylic acid is a total acid component (excluding compound (X)) 70 mol parts or more in 100 mol parts, and (B) alcohol component (however, excluding compound (X)) 105 The method for producing a polyester binder resin for toner according to claim 1, wherein 150 mol parts are polymerized. A toner containing the polyester binder resin for toner according to claim 1.