JP3773906B2 - Linear polyester resin for toner and toner - Google Patents

Description

【００４７】
実施例１
上記で得られた樹脂１を用いて、トナー化を行った。トナーの配合には、樹脂１を９３質量部、キナクリドン顔料（クラリアント社製Ｅ０２）を３質量部、カルナバワックス（東洋ペトロライド社製）３質量部、負帯電性の荷電制御剤（オリエント化学社製Ｅ−８４）１質量部を使用し、ヘンシェルミキサーで３０分間混合した。次いで、得られた混合物を２軸混練機で２回溶融混練した。溶融混練は内温を樹脂の軟化温度に設定して行った。混練後、冷却してトナー魂を得、ジェットミル微粉砕機で微粉砕し、分級機でトナーの粒径を整え、粒径を５μｍとした。得られた微粉末に対して、０．２５％のシリカ（日本アエロジル社製Ｒ−９７２）を加え、ヘンシェルミキサーで混合して付着させ、トナーを得た。得られたトナーについて前述の評価方法を用いてトナー評価を行った。これらの評価結果を表２に示す。
【００４８】
得られたトナーは、低温定着性、１４５℃定着性は非常に良好で、耐ブロッキング性も良好であり、耐ＨＯＳ性は使用可能レベルで性能バランスの良いトナーであった。
【００４９】
実施例２〜４、比較例１〜４
樹脂分を樹脂２〜８に変更した以外は実施例１と同様にしてトナーを製造した。評価結果を表２に示す。
【００５０】
実施例２、３のトナーは低温定着性が非常に優れ、性能バランスの良いトナーであった。実施例４のトナーは使用可能レベルのトナーであった。比較例１、２、３のトナーは１４５℃定着性が劣り、比較例４のトナーは耐ＨＯＳ性、耐ブロッキング性が劣っていた。
【００５１】
【表２】

【００５２】
実施例５
トナーの配合に、樹脂１を７４．４重量部、ポリエステルＡ（テレフタル酸（５７モル部）／イソフタル酸（４０モル部）／アジピン酸（３モル部）／エチレングリコール（８５モル部）／１，４−シクロヘキサンジメタノール（１５モル部）からなる、軟化温度１７０℃、Ｍｗ４１，０００、Ｔｇ５９．１℃、酸価２．１ｍｇＫＯＨ／ｇの線状ポリエステル樹脂）を１８．６重量部、キナクリドン顔料（クラリアント社製Ｅ０２）を３重量部、カルナバワックス（東洋ペトロライド社製）３重量部、負帯電性の荷電制御剤（オリエント化学社製Ｅ−８４）１重量部を使用した以外は実施例１と同様にしてトナーを製造した。評価結果を表３に示す。
【００５３】
得られたトナーは、低温定着性、１４５℃定着性は非常に良好で、耐ＨＯＳ性、耐ブロッキング性も良好な、性能バランスの非常に良いトナーであった。
【００５４】
実施例６〜１４、比較例５〜７
トナー中の樹脂分を表３に記載した内容とした以外は実施例５と同様にしてトナーを製造した。樹脂成分中、ポリエステルＢはテレフタル酸（９７モル部）／アジピン酸（３モル部）／エチレングリコール（８５モル部）／１，４−シクロヘキサンジメタノール（１５モル部）からなる、軟化温度１６３℃、Ｍｗ３４，０００、Ｔｇ５６．６℃、酸価１．０ｍｇＫＯＨ／ｇの線状ポリエステル樹脂であり、ポリエステルＣはテレフタル酸（６２モル部）／イソフタル酸（２０モル部）／トリメリット酸（１８モル部）／ポリオキシプロピレン（２．３）−２，２−ビス（４−ヒドロキシフェニル）プロパン（６０モル部）／ポリオキシエチレン（２．３）−２，２−ビス（４−ヒドロキシフェニル）プロパン（２０モル部）／エチレングリコール（３０モル部）からなる、軟化温度１２５℃、Ｔｇ６２．０℃、酸価８．０ｍｇＫＯＨ／ｇの非線状ポリエステル樹脂であり、ポリエステルＤはテレフタル酸（６２モル部）／イソフタル酸（２０モル部）／トリメリット酸（１８モル部）／ポリオキシプロピレン（２．３）−２，２−ビス（４−ヒドロキシフェニル）プロパン（６０モル部）／ポリオキシエチレン（２．３）−２，２−ビス（４−ヒドロキシフェニル）プロパン（２０モル部）／エチレングリコール（２５モル部）からなる、軟化温度１４１℃、Ｔｇ６３．１℃、酸価７．５ｍｇＫＯＨ／ｇの非線状ポリエステル樹脂であり、Ｓｔ／Ａｃ樹脂はスチレン（８０重量部）／ｎ−ブチルアクリレート（２０重量部）からなる、軟化温度１２７℃、Ｔｇ６０．０℃、酸価０．２ｍｇＫＯＨ／ｇの樹脂であり、環状オレフィンは軟化温度１２６℃、Ｔｇ６７．０℃、酸価０ｍｇＫＯＨ／ｇの樹脂である。評価結果を表３に示す。
【００５５】
実施例７、８、９のトナーは低温定着性または１４５℃定着性が非常に良好で性能バランスの良いトナーであった。実施例６、１０のトナーは、低温定着性が良好で性能バランスが良く、実施例１１、１２のトナーは低温定着性が使用可能レベルであった。さらに、ポリエステル以外の樹脂成分を含有する実施例１３、１４においても低温定着性の良好なトナーが得られた。一方、線状ポリエステル樹脂を含有しない比較例５のトナーは、低温定着性、１４５℃定着性が劣り、本発明における特定のジオール成分を有しない線状ポリエステル樹脂を用いた比較例６、７のトナーは、比較例６のトナーでは耐ＨＯＳ性が劣り、比較例７のトナーでは１４５℃定着性が劣っており、性能バランスの良いトナーとはならなかった。
【００５６】
【表３】

【００５７】
【発明の効果】
本発明によれば、樹脂中に特定のジオール成分を有することによって、低温定着性に優れたトナーを提供できるトナー用線状ポリエステル樹脂を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a linear polyester resin for toner and a toner containing the same. In particular, the present invention can be used for development of an electrostatic charge image or a magnetic latent image in electrophotography, electrostatic recording method, electrostatic printing method, etc., and can provide a toner having a good balance of physical properties and particularly excellent in low-temperature fixability. The present invention relates to a linear polyester resin for toner and a toner containing this resin.
[0002]
[Prior art]
In the method of obtaining an image by the electrophotographic printing method and the electrostatic charge developing method, the electrostatic image formed on the photosensitive member is developed with toner charged in advance by friction, and then fixed by heat roller pressing at the fixing portion. The method is common. In order to pass through these processes without problems, the toner needs to have various performances such as charge amount stability, blocking resistance, and non-offset properties. In recent years, from the viewpoint of low energy, there has been a strong demand for a toner having good fixing property to paper and having a wide fixing temperature range even when the temperature of the heat roller is lower.
[0003]
Binder resin for toner has a great influence on the toner characteristics as described above, and as such resin, polystyrene resin, styrene acrylic resin, polyester resin, epoxy resin, polyamide resin, etc. are known. In particular, a polyester resin which is essentially excellent in fixability has attracted attention.
[0004]
As the polyester toner resin, a non-linear polyester resin using a tri- or higher functional monomer is generally used. However, a resin excellent in fixability at a lower temperature is strongly desired, and various studies have been made. It was.
[0005]
For example, Japanese Patent Laid-Open Nos. 4-362956 and 8-320593 disclose attempts to improve low-temperature fixability by mixing non-linear polyester with a low-melting linear polyester. Further, in Japanese Patent Laid-Open Nos. 10-339969, 10-268558, 2000-305316, etc., studies using linear polyesters are made. Furthermore, in Japanese Patent Laid-Open Nos. 4-313760 and 2002-287427, a toner composed of two kinds of polyester resins having a defined softening point is studied.
[0006]
[Patent Document 1]
Japanese Patent Laid-Open No. 4-36295 [Patent Document 2]
JP-A-8-320593 [Patent Document 3]
Japanese Patent Laid-Open No. 10-339969 [Patent Document 4]
Japanese Patent Laid-Open No. 10-268558 [Patent Document 5]
JP 2000-305316 A [Patent Document 6]
JP-A-4-313760 [Patent Document 7]
JP-A-2002-287427 [0007]
[Problems to be solved by the invention]
Resin for toner with improved fixing performance has been developed by the above-mentioned technology, etc., but the market demand for fixing performance has become more severe. With the above-mentioned technology, blocking resistance, non-offset property, etc. However, the development of a resin having a low-temperature fixability that can satisfy market requirements while maintaining the necessary physical properties has not been achieved.
[0008]
An object of the present invention is to solve the problems of the prior art as described above, and to provide a linear polyester resin for toner excellent in low-temperature fixability and a toner containing the same.
[0009]
[Means for Solving the Problems]
As a result of diligent research on the linear polyester resin for toner, the present inventors have found that the above-described problems can be solved by adopting the following constitution, and have completed the present invention.
[0010]
That is, the present invention is a linear polyester resin comprising a dicarboxylic acid component and a diol component in order to solve the above-mentioned problems, and the dicarboxylic acid component is an aromatic dicarboxylic acid component in a total carboxylic acid component of 50 mol% or more. And an aliphatic diol having 4 to 8 carbon atoms in an amount of 60 mol parts or more based on 100 mol parts of the total carboxylic acid component, and the mass average molecular weight (Mw) of the polyester resin is in the range of 4,000 to 10,000. And a linear polyester resin for toner having a glass transition temperature in the range of 40 to 70 ° C and a softening temperature in the range of 90 to 120 ° C.
[0011]
The present invention also provides a toner comprising the toner linear polyester resin in an amount of 5% by mass or more.
[0012]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, preferred embodiments of the present invention will be described.
[0013]
The linear polyester resin for toner of the present invention is characterized by comprising a dicarboxylic acid component and a diol component. Here, the linear polyester refers to a polyester composed of a linear main chain or a polyester having a structure composed of a linear main chain and a relatively short side chain bonded thereto. By using a linear polyester resin, it is possible to obtain a resin that can provide a toner having a smooth fixing surface and good fixing properties.
[0014]
In the present invention, aromatic dicarboxylic acid is used as the dicarboxylic acid component in an amount of 50 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more in the total carboxylic acid component. This is because by setting the aromatic dicarboxylic acid component to 50 mol% or more, the resulting resin tends to have a good balance of physical properties such as fixability and blocking resistance.
[0015]
Examples of the aromatic dicarboxylic acid component include components from terephthalic acid, isophthalic acid, or lower alkyl esters thereof. These components can be used alone or in combination of two or more.
[0016]
Other dicarboxylic acid components that can be used in the present invention include phthalic acid, sebacic acid, isodecyl succinic acid, dodecenyl succinic acid, maleic acid, fumaric acid, adipic acid, or their monomethyl, monoethyl, dimethyl, diethyl esters or their Ingredients from acid anhydrides. Since these dicarboxylic acid components are related to basic characteristics such as toner fixing properties and anti-blocking properties, they can be appropriately used according to the required performance within a range not impairing the object of the present invention.
[0017]
The diol component used in the present invention contains an aliphatic diol having 4 to 8 carbon atoms in an amount of 60 mol parts or more per 100 mol parts of the total carboxylic acid component. This is because crystallization of the polyester resin can be suppressed by using 60 mol parts or more of the component having 4 or more carbon atoms, and tends to be effective for transparency and glossiness. This is because the flexibility of the resulting resin increases and the toner fixing property tends to be good. The content of the aliphatic diol having 4 to 8 carbon atoms is preferably 70 mol parts or more.
[0018]
Examples of the diol constituting the aliphatic diol component having 4 to 8 carbon atoms in the present invention include neopentyl glycol, butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5. -Pentanediol and the like. Among these, neopentyl glycol is particularly preferable because it has a high affinity with paper and a resin having excellent low-temperature fixability can be obtained. In addition, an alicyclic diol is not contained in a C4-C8 aliphatic diol component used by this invention.
[0019]
Examples of other diol components that can be used in the present invention include aliphatic diols having 3 or less carbon atoms such as ethylene glycol, propylene glycol, and 1,3-propanediol, and alicyclic compounds such as 1,4-cyclohexanedimethanol. Examples include components from diols and the like. These can be used as appropriate as long as the object of the present invention is not impaired.
[0020]
The linear polyester resin for toner in the present invention can be obtained by polymerizing these dicarboxylic acid component and diol component by a known method through esterification reaction or transesterification reaction and condensation reaction.
[0021]
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. Alternatively, polymerization may be performed in the presence of a release agent component to disperse or react the resin and the release agent component.
[0022]
The thus obtained linear polyester resin for toner of the present invention needs to have a mass average molecular weight (Mw) in the range of 4,000 to 10,000. This is because the strength of the resin tends to be sufficient when Mw is 4,000 or more. Preferably, it is 5,000 or more. Moreover, it is because low temperature fixability tends to be good by setting Mw to 10,000 or less. Preferably, it is 8,000 or less.
[0023]
Furthermore, the linear polyester resin for toner of the present invention needs to have a softening temperature in the range of 90 to 120 ° C. This is because setting the softening temperature to 90 ° C. or more tends to improve the blocking resistance of the toner. Preferably, it is 95 ° C. or higher. Moreover, it is because the low temperature fixability of the toner tends to be improved by setting the softening temperature to 120 ° C. or less. Preferably, it is 110 degrees C or less.
[0024]
The polyester resin for toner of the present invention needs to have a glass transition temperature in the range of 40 to 70 ° C. This is because setting the glass transition temperature to 40 ° C. or higher tends to improve the blocking resistance of the toner. Preferably, it is 50 ° C. or higher. Moreover, it is because the low temperature fixability of the toner tends to be improved by setting the glass transition temperature to 70 ° C. or less. Preferably it is 65 degrees C or less.
[0025]
Furthermore, the polyester resin for toner of the present invention preferably has an acid value in the range of 0.5 to 30 mgKOH / g. This is because a resin having an acid value of less than 0.5 mgKOH / g tends to have low productivity. More preferably, it is 1 mgKOH / g or more. Further, when the acid value exceeds 30 mgKOH / g, the stability of the obtained toner image tends to be lowered. More preferably, it is 25 mgKOH / g or less.
[0026]
The linear polyester resin for toner of the present invention is used as a binder resin, and a toner can be obtained by blending a colorant, a release agent, a charge control agent, a flow modifier, a magnetic substance, and the like. . As the binder resin, one or a combination of two or more of the resins of the present invention can be used, and a resin component other than the polyester resin of the present invention may be used in combination.
[0027]
Examples of other resin components that can be used when the toner is produced using the linear polyester resin for toner obtained in the present invention include known non-linear polyester resins, linear polyester resins, cyclic olefins, A styrene acrylic resin, an acrylic resin, etc. are mentioned. One or more of these resins can be selected and used, and the low temperature fixability of known resins can be improved by using a mixture of these resins and the polyester resin of the present invention. .
[0028]
When the linear polyester resin for toner of the present invention and other resins are mixed and used as a binder resin, the blending amount is adjusted so that the linear polyester resin for toner of the present invention is contained in an amount of 5% by mass or more of the toner. It is preferable to do. This is because the intended effect can be exhibited by using it in an amount of 5% by mass or more. Preferably it is 10 mass% or more, More preferably, it is 20 mass% or more.
[0029]
Examples of colorants that can be used in the toner of the present invention include carbon black, nigrosine, aniline blue, phthalocyanine blue, phthalocyanine green, hansa yellow, rhodamine dyes, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dyes. Monoazo, disazo, condensed azo dyes or pigments, and these dyes and pigments can be used alone or in admixture of two or more. In the case of a full-color toner, benzidine yellow, monoazo dyes and condensed azo dyes are used as yellow, quinacridone, rhodamine dyes, and monoazo dyes are used as magenta, and phthalocyanine blue is used as cyan. The colorant is preferably used in an amount of 2 to 10% by mass in the toner from the viewpoint of toner color tone, image density, and thermal characteristics.
[0030]
Examples of the release agent component that can be used in the toner of the present invention include rice wax, carnauba wax, paraffin wax, beeswax, polypropylene wax, polyethylene wax, synthetic ester wax, paraffin wax, fatty acid amide, silicone wax, and the like. These may be used alone or in combination of two or more. These release agent components are preferably contained in the toner in an amount of 0.1 to 10% by mass. This is because the non-offset property of the toner tends to be good when the content of the release agent component is 0.1% by mass or more, and more preferably 0.5% by mass or more. Further, when the amount is 10% by mass or less, the glossiness and image stability of the toner tend to be good, and more preferably 8% by weight or less.
[0031]
Examples of the charge control agent that can be used in the toner of the present invention include a quaternary ammonium salt and a basic or electron-donating organic substance as a positive charge control agent, and metal chelates, metal-containing dyes as a negative charge control agent, Examples include acidic or electron-withdrawing organic substances. In the case of color toners, it is important that the charge control agent is colorless or light color and does not impair the color tone of the toner. Metal salts, metal complexes, amide compounds of salicylic acid or alkylsalicylic acid with chromium, zinc, aluminum, etc. , Phenol compounds, naphthol compounds and the like. These charge control agents are preferably used in an amount of 0.5 to 5% by mass in the toner. This is because when the charge control agent is 0.5% by mass or more, the charge amount of the toner becomes a sufficient level, and when it is 5% by mass or less, a decrease in the charge amount due to aggregation of the charge control agent tends to be suppressed. Because it is in.
[0032]
Examples of additives that can be used in the toner of the present invention include flow improvers such as fine powdered silica, alumina, and titania, magnetite, ferrite, cerium oxide, strontium titanate, and conductive titania. Inorganic fine powders, resistance modifiers such as styrene resin and acrylic resin, lubricants, and the like, and these are used as an internal additive or an external additive. These additives can be used in the toner in an amount of 0.05 to 10% by mass. When the amount of these additives used is 0.05% by mass or more, the toner performance-modifying effect tends to be sufficiently obtained, and when the amount is 10% by mass or less, the image stability of the toner is good. It is because it tends to become.
[0033]
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 a ferromagnetic alloy containing iron, cobalt, nickel, etc., including ferrite, magnetite, etc. Alloys that do not contain a ferromagnetic element but exhibit ferromagnetism by appropriate heat treatment, for example, so-called Heusler alloys containing manganese and copper, such as manganese-copper-aluminum, manganese-copper-tin, and chromium dioxide Etc. These magnetic materials can be used in the toner in the range of 40 to 60% by mass. This is because when the amount of the magnetic material used is 40% by mass or more, the charge amount of the toner tends to be a sufficient level, and when it is 60% by mass or less, the fixability of the toner tends to be good. . When used as a two-component developer, it is used in combination with a carrier. As the carrier, known materials such as magnetic materials such as iron powder, magnetite powder, and ferrite powder, those whose surfaces are coated with a resin coating, and magnetic carriers 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.
[0034]
The toner of the present invention is, for example, mixed with the above-described polyester resin for toner and other resin components, a colorant, a charge control agent, a flow modifier, a magnetic material, and the like, and then melt-kneaded with a twin screw extruder or the like. , Coarse pulverization, fine pulverization, classification, and external addition treatment of inorganic particles as necessary. In particular, in the kneading step, it is preferable that the temperature in the cylinder of the extruder is kneaded at a temperature higher than the softening temperature of the polyester resin. Further, in the above process, a treatment such as making the toner particles spherical after fine pulverization to classification may be performed.
[0035]
【Example】
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.
[0036]
Resin evaluation method 1) Mass average molecular weight (Mw)
It is a measured value by gel permeation chromatography, measured by Tosoh HCL-8020 composed of three TSKgel / GMH _XL columns (Tosoh Corp.), and calculated by polystyrene conversion.
[0037]
2) Softening temperature When measured using a flow tester CFT-500 manufactured by Shimadzu Corporation with a nozzle of 1 mmφ × 10 mm under a load of 294 N (30 Kgf) at a constant heating rate of 3 ° C./min. The temperature at which 1/2 in 1.0 g of the sample flowed out was defined as the softening temperature.
[0038]
3) After melt quenching the glass transition temperature sample, using a differential differential calorimeter, when measured at a heating rate of 5 ° C./min, the chart baseline and the tangent to the endothermic curve near the glass transition temperature The temperature at the intersection of these was the glass transition temperature.
[0039]
Toner evaluation method 4) Evaluation method of low-temperature fixability, HOS (hot offset) resistance, and 145 ° C. fixability Fix an unfixed image on paper using a fixing roller whose temperature can be changed at a roller speed of 100 mm / sec. And evaluated.
[0040]
-Low temperature fixability The lowest roller temperature at which no cold offset occurs was set as the fixing start temperature, and the low temperature fixability was judged according to the following criteria.
[0041]
◎ (very good): fixing start temperature is 125 ° C. or less ○ (good): fixing start temperature exceeds 125 ° C. and 135 ° C. or less Δ (can be used): fixing start temperature exceeds 135 ° C. and 145 ° C. or less × (Inferior): Fixing start temperature exceeds 145 ° C./HOS resistance The minimum roller temperature at which the toner moves to the fixing roller was defined as the HOS generation temperature, and the HOS resistance was judged using the following criteria.
[0042]
◎ (very good): HOS generation temperature is 200 ° C. or higher ○ (good): HOS generation temperature is 185 ° C. or higher and lower than 200 ° C. Δ (can be used): HOS generation temperature is 175 ° C. or higher and lower than 185 ° C. x (inferior): The HOS generation temperature is less than 175 ° C. and 145 ° C. The fixing roller temperature is set to 145 ° C., and the fixed image is rubbed 9 times with JIS 512 sand eraser. The image density before and after the test is the image density manufactured by Macbeth Measured with a meter, fixing rate is image density after test / image density before test x 100 (%)
And evaluated according to the following criteria.
[0043]
◎ (Very good): Fixing rate of 80% or more ○ (Good): Fixing rate of 75% or more and less than 80% Δ (Available): Fixing rate of 70% or more and less than 75% x (Inferior): Less than 70% 5) About 5 g of anti-blocking toner is weighed and put into a sample bottle, and this is left in a drier kept at 50 ° C. for about 24 hours. The degree of aggregation was evaluated and used as an index of blocking resistance. The evaluation criteria were as follows.
[0044]
◎ (very good): disperse just by inverting the sample bottle ○ (good): disperse when the sample jar is inverted and tapped once or twice △ (available): invert the sample jar, 3 Dispersion when tapped 4 x (Inferior): Synthetic synthesis example 1 of linear polyester resin for toner which is dispersed when tapped 5 times or more
A monomer component having the charge composition shown in Table 1 and 500 ppm of antimony trioxide with respect to the total acid component were charged into a reaction vessel equipped with a distillation tower. 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 260 ° C., and this temperature was maintained. Water was distilled from the reaction system, and about 8 hours after the start of the esterification reaction, the water was not distilled and the reaction was completed. Next, the temperature in the reaction system was lowered and maintained at 230 ° C., the pressure in the reaction vessel was reduced over about 40 minutes, the degree of vacuum was 1.0 mmHg, and a condensation reaction was performed while distilling the diol component from the reaction system. . The condensation reaction was carried out until the viscosity of the reaction system increased with the reaction, and the softening temperature of the resin in the reaction system was traced to reach a value indicating the desired softening temperature. When the predetermined softening temperature is exhibited, the reaction system is returned to normal pressure, heating is stopped, the pressure is increased with nitrogen, the reaction product is taken out over about 2 hours, and gradually cooled over 2 hours. 1 was obtained. Table 1 also shows the results of composition analysis of the obtained resin by liquid gas chromatography and the physical properties of the resin.
[0045]
Synthesis Examples 2-8
Resins 2 to 8 were obtained in the same manner as in Synthesis Example 1 except that the monomer component and the charged composition were changed to those described in Table 1. The resin composition and characteristic values are also shown in Table 1.
[0046]
[Table 1]

[0047]
Example 1
Using the resin 1 obtained above, toner was formed. To blend the toner, 93 parts by weight of resin 1, 3 parts by weight of quinacridone pigment (E02 manufactured by Clariant), 3 parts by weight of carnauba wax (manufactured by Toyo Petrolide), a negatively chargeable charge control agent (manufactured by Orient Chemical Co., Ltd.) E-84) 1 part by mass was mixed with a Henschel mixer for 30 minutes. Subsequently, the obtained mixture was melt-kneaded twice 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 and pulverized with a jet mill pulverizer, and the particle size of the toner was adjusted with a classifier to make the particle size 5 μm. To the obtained fine powder, 0.25% of silica (R-972, manufactured by Nippon Aerosil Co., Ltd.) was added, mixed and adhered with a Henschel mixer to obtain a toner. The obtained toner was evaluated for toner using the aforementioned evaluation method. These evaluation results are shown in Table 2.
[0048]
The obtained toner had very good low-temperature fixability, 145 ° C. fixability, good blocking resistance, and HOS resistance was a usable level with good performance balance.
[0049]
Examples 2-4, Comparative Examples 1-4
A toner was produced in the same manner as in Example 1 except that the resin content was changed to resins 2 to 8. The evaluation results are shown in Table 2.
[0050]
The toners of Examples 2 and 3 were very excellent in low-temperature fixability and had a good performance balance. The toner of Example 4 was a usable toner level. The toners of Comparative Examples 1, 2, and 3 have poor 145 ° C. fixability, and the toner of Comparative Example 4 has poor HOS resistance and blocking resistance.
[0051]
[Table 2]

[0052]
Example 5
In the blending of the toner, 74.4 parts by weight of Resin 1 and polyester A (terephthalic acid (57 mol parts) / isophthalic acid (40 mol parts) / adipic acid (3 mol parts) / ethylene glycol (85 mol parts) / 1 , 4-cyclohexanedimethanol (15 mol parts), 18.6 parts by weight of a linear polyester resin having a softening temperature of 170 ° C., Mw of 41,000, Tg of 59.1 ° C., and an acid value of 2.1 mgKOH / g), quinacridone pigment Example 1 except that 3 parts by weight (E02 manufactured by Clariant), 3 parts by weight carnauba wax (manufactured by Toyo Petrolide), and 1 part by weight of a negatively chargeable charge control agent (E-84 manufactured by Orient Chemical Co., Ltd.) were used. In the same manner, a toner was produced. The evaluation results are shown in Table 3.
[0053]
The obtained toner was a toner having a very good performance balance, having a very low temperature fixability and a 145 ° C. fixability, a good HOS resistance and a blocking resistance.
[0054]
Examples 6-14, Comparative Examples 5-7
A toner was produced in the same manner as in Example 5 except that the resin content in the toner was as described in Table 3. In the resin component, polyester B is composed of terephthalic acid (97 mol parts) / adipic acid (3 mol parts) / ethylene glycol (85 mol parts) / 1,4-cyclohexanedimethanol (15 mol parts), softening temperature 163 ° C. , Mw 34,000, Tg 56.6 ° C., acid value 1.0 mg KOH / g linear polyester resin, polyester C is terephthalic acid (62 mol parts) / isophthalic acid (20 mol parts) / trimellitic acid (18 mol) Part) / polyoxypropylene (2.3) -2,2-bis (4-hydroxyphenyl) propane (60 mol parts) / polyoxyethylene (2.3) -2,2-bis (4-hydroxyphenyl) Made of propane (20 mol parts) / ethylene glycol (30 mol parts), softening temperature 125 ° C., Tg 62.0 ° C., acid value 8.0 mgKOH / g Polyester D is a non-linear polyester resin, and polyester D is terephthalic acid (62 mol parts) / isophthalic acid (20 mol parts) / trimellitic acid (18 mol parts) / polyoxypropylene (2.3) -2,2-bis. (4-hydroxyphenyl) propane (60 mol parts) / polyoxyethylene (2.3) -2,2-bis (4-hydroxyphenyl) propane (20 mol parts) / ethylene glycol (25 mol parts), A non-linear polyester resin having a softening temperature of 141 ° C., a Tg of 63.1 ° C., and an acid value of 7.5 mgKOH / g, and the St / Ac resin is composed of styrene (80 parts by weight) / n-butyl acrylate (20 parts by weight). It is a resin having a softening temperature of 127 ° C., a Tg of 60.0 ° C., and an acid value of 0.2 mgKOH / g. The cyclic olefin has a softening temperature of 126 ° C., a Tg of 67.0 ° C., and an acid value of 0. It is a resin of gKOH / g. The evaluation results are shown in Table 3.
[0055]
The toners of Examples 7, 8, and 9 were toners having very good low temperature fixability or 145 ° C. fixability and good performance balance. The toners of Examples 6 and 10 had good low-temperature fixability and good performance balance, and the toners of Examples 11 and 12 had low-temperature fixability at a usable level. Further, in Examples 13 and 14 containing a resin component other than polyester, a toner having good low-temperature fixability was obtained. On the other hand, the toner of Comparative Example 5 containing no linear polyester resin is inferior in low-temperature fixability and 145 ° C. fixability, and in Comparative Examples 6 and 7 using the linear polyester resin having no specific diol component in the present invention. The toner of Comparative Example 6 was inferior in HOS resistance, and the toner of Comparative Example 7 was inferior in 145 ° C. fixability, so that the toner did not have a good performance balance.
[0056]
[Table 3]

[0057]
【The invention's effect】
According to the present invention, a linear polyester resin for toner that can provide a toner having excellent low-temperature fixability can be obtained by having a specific diol component in the resin.

Claims (3)

A linear polyester resin comprising a dicarboxylic acid component and a diol component, wherein the aromatic dicarboxylic acid is 50 mol% or more in the total carboxylic acid component and neopentyl glycol is 60 mol part or more with respect to 100 mol parts of the total carboxylic acid component. The polyester resin has a weight average molecular weight (Mw) in the range of 4,000 to 10,000, a glass transition temperature in the range of 40 to 70 ° C, and a softening temperature in the range of 90 to 120 ° C. Linear polyester resin for toner. The linear polyester resin for toner according to claim 1, wherein the acid value is in the range of 0.5 to 30 mg KOH / g. Toner in an amount of more than 5 mass% in the toner for toner linear polyester resin according to claim 1 or 2.