JP4749236B2 - Positively chargeable toner - Google Patents
Positively chargeable toner Download PDFInfo
- Publication number
- JP4749236B2 JP4749236B2 JP2006152342A JP2006152342A JP4749236B2 JP 4749236 B2 JP4749236 B2 JP 4749236B2 JP 2006152342 A JP2006152342 A JP 2006152342A JP 2006152342 A JP2006152342 A JP 2006152342A JP 4749236 B2 JP4749236 B2 JP 4749236B2
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- JP
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- Prior art keywords
- raw material
- resin
- toner
- acid
- styrene
- Prior art date
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- 239000000178 monomer Substances 0.000 claims description 87
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
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- DZNJMLVCIZGWSC-UHFFFAOYSA-N 3',6'-bis(diethylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(N(CC)CC)C=C1OC1=CC(N(CC)CC)=CC=C21 DZNJMLVCIZGWSC-UHFFFAOYSA-N 0.000 description 2
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- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
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Description
本発明は、電子写真法、静電記録法、静電印刷法等において形成される潜像の現像に用いられる正帯電性トナーに関する。 The present invention relates to a positively chargeable toner used for developing a latent image formed in an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like.
近年、電子写真システムに対する要求が高まり、より高画質化、より高速化に対応することができ、そしてさらなる高信頼性を備えたトナーが要望されている。特に、高速連続印字においても安定した画像を形成するためには、トナーの耐久性及び帯電安定性が重要となる。トナーの耐久性を高める観点からは、結着樹脂としてフマル酸を原料モノマーの一つとするポリエステル樹脂を含有したトナーが開示されている(特許文献１参照)。また、トナーの帯電安定性を高める観点からは、ニグロシン染料を含有した正帯電性トナーが開示されている(特許文献２参照)。
フマル酸を原料モノマーとして用いて得られる結着樹脂を含有するトナーは耐久性に優れ、ニグロシン染料を含有するトナーは帯電安定性に優れるが、フマル酸を原料モノマーとして用いて得られる結着樹脂とニグロシン染料を共に含有するトナーは、帯電性、特に正帯電性の安定性に劣り、画像濃度の低下やカブリの発生による画像劣化が問題となる。また、フマル酸の幾何異性体であるマレイン酸を用いた場合についても、同様の問題が生じる。このため、フマル酸及び／又はマレイン酸を原料モノマーとして用いて得られる結着樹脂とニグロシン染料を共に含有した場合でも、より安定した画像を供給することの出来る正帯電性トナーの開発が要望される。 A toner containing a binder resin obtained using fumaric acid as a raw material monomer is excellent in durability, and a toner containing a nigrosine dye is excellent in charging stability, but a binder resin obtained using fumaric acid as a raw material monomer The toner containing both the nigrosine dye and the nigrosine dye is inferior in stability of chargeability, particularly positive chargeability, and there is a problem of image deterioration due to a decrease in image density and occurrence of fog. The same problem occurs when maleic acid, which is a geometric isomer of fumaric acid, is used. For this reason, there is a demand for the development of a positively chargeable toner capable of supplying a more stable image even when both a binder resin obtained using fumaric acid and / or maleic acid as a raw material monomer and a nigrosine dye are contained. The
本発明の課題は、フマル酸及び／又はマレイン酸を原料モノマーとして用いて得られる結着樹脂とニグロシン染料を共に含有した場合でも、画像濃度が高くカブリのない画像を供給することができる正帯電性トナーを提供することにある。 An object of the present invention is to provide a positively charged image which can supply an image having a high image density and no fog even when a binder resin obtained by using fumaric acid and / or maleic acid as a raw material monomer and a nigrosine dye are contained together. It is to provide a functional toner.
本発明は、
〔１〕フマル酸及び／又はマレイン酸を原料モノマーとして用いて得られる結着樹脂、ニグロシン染料、及びスチレンを含有してなる正帯電性トナーであって、トナー中のフマル酸及びマレイン酸の総含有量が10〜500ppmであり、スチレン含有量が3〜100ppmである正帯電性トナー、及び
〔２〕スチレンの存在下でフマル酸及び／又はマレイン酸を原料モノマーとして用いて得られる結着樹脂、及びニグロシン染料を含有してなる正帯電性トナーであって、トナー中のフマル酸及びマレイン酸の総含有量が10〜500ppmであり、スチレン含有量が3〜100ppmである正帯電性トナー
に関する。
The present invention
[1] A positively chargeable toner comprising a binder resin obtained by using fumaric acid and / or maleic acid as a raw material monomer, a nigrosine dye, and styrene, and the total of fumaric acid and maleic acid in the toner Positively chargeable toner having a content of 10 to 500 ppm and a styrene content of 3 to 100 ppm, and [2] a binder resin obtained using fumaric acid and / or maleic acid as a raw material monomer in the presence of styrene And a positively chargeable toner comprising a nigrosine dye, wherein the total content of fumaric acid and maleic acid in the toner is 10 to 500 ppm, and the styrene content is 3 to 100 ppm. .
本発明の正帯電性トナーは、フマル酸及び／又はマレイン酸を原料モノマーとして用いて得られる結着樹脂とニグロシン染料を共に含有した場合でも、画像濃度が高くカブリのない画像を供給することができるという優れた効果を奏するものである。 The positively chargeable toner of the present invention can supply an image having a high image density and no fog even when the binder resin obtained by using fumaric acid and / or maleic acid as a raw material monomer and the nigrosine dye are contained together. It has an excellent effect of being able to.
フマル酸及び／又はマレイン酸を原料モノマーとして用いて得られる結着樹脂とニグロシン染料を共に含有するトナーにおいては、正帯電性の安定性が損なわれるが、これは、トナー中のフマル酸及び／又はマレイン酸がニグロシン染料の帯電供与部位に作用し、荷電制御作用を阻害するためと考えられる。本発明の正帯電性トナーは、フマル酸及び／又はマレイン酸を原料モノマーとして用いて得られる結着樹脂、ニグロシン染料、及びスチレンを含有するトナー(態様１)、及びスチレンの存在下でフマル酸及び／又はマレイン酸を原料モノマーとして用いて得られる結着樹脂及びニグロシン染料を含有するトナー(態様２)であって、それぞれのトナー中のフマル酸及びマレイン酸の総含有量が10〜500ppmであり、スチレン含有量が3〜100ppmである点に大きな特徴を有し、トナー中にフマル酸及び／又はマレイン酸とスチレンが並存することにより、その詳細なる理由は不明なるも、スチレンがフマル酸及び／又はマレイン酸に吸着する為か、フマル酸及び／又はマレイン酸によるニグロシン染料への阻害がなくなり、優れた正帯電性を示すため、高画質画像を得ることができる。なお、スチレンを含有する結着樹脂に、さらにスチレンを添加して得られるトナー、即ち、態様１と態様２のトナーを組み合わせたトナーもまた、本発明に含まれる。 In a toner containing both a binder resin obtained by using fumaric acid and / or maleic acid as a raw material monomer and a nigrosine dye, the stability of positive chargeability is impaired. This is because fumaric acid and / or Alternatively, it is considered that maleic acid acts on the charge donating site of the nigrosine dye and inhibits the charge control action. The positively chargeable toner of the present invention includes a binder resin obtained by using fumaric acid and / or maleic acid as a raw material monomer, a toner containing nigrosine dye and styrene (embodiment 1), and fumaric acid in the presence of styrene. And / or a toner (embodiment 2) containing a binder resin obtained by using maleic acid as a raw material monomer and a nigrosine dye, wherein the total content of fumaric acid and maleic acid in each toner is 10 to 500 ppm There is a great feature in that the styrene content is 3 to 100 ppm, and the detailed reason is unknown due to the coexistence of fumaric acid and / or maleic acid and styrene in the toner, but styrene is fumaric acid. In order to adsorb to maleic acid and / or to inhibit nigrosine dye by fumaric acid and / or maleic acid, and exhibit excellent positive chargeability, A quality image can be obtained. Note that a toner obtained by further adding styrene to a binder resin containing styrene, that is, a toner obtained by combining the toners of Embodiments 1 and 2, is also included in the present invention.
態様１、２のトナー中のフマル酸及びマレイン酸の総含有量は10〜500ppmであり、高い正帯電性を得る観点から、好ましくは10〜300ppmであり、より好ましくは10〜200ppmであり、さらに好ましくは10〜100ppmである。本明細書において、フマル酸及びマレイン酸の総含有量は、後述の実施例に記載の方法により測定される。 The total content of fumaric acid and maleic acid in the toner of Embodiments 1 and 2 is 10 to 500 ppm, preferably 10 to 300 ppm, more preferably 10 to 200 ppm from the viewpoint of obtaining high positive chargeability. More preferably, it is 10-100 ppm. In the present specification, the total content of fumaric acid and maleic acid is measured by the method described in Examples described later.
態様１、２のトナー中のスチレン含有量は3〜100ppmであり、帯電量低下を抑制する観点から、好ましくは3〜70ppmであり、より好ましくは3〜50ppmであり、さらに好ましくは3〜40ppmである。本明細書において、スチレンの含有量は、後述の実施例に記載の方法により測定される。 The styrene content in the toner of Embodiments 1 and 2 is 3 to 100 ppm, and from the viewpoint of suppressing a decrease in charge amount, it is preferably 3 to 70 ppm, more preferably 3 to 50 ppm, and further preferably 3 to 40 ppm. It is. In the present specification, the content of styrene is measured by the method described in Examples described later.
態様１のトナーは、フマル酸及び／又はマレイン酸を原料モノマーとして用いて得られる結着樹脂、ニグロシン染料、及びスチレンを含有する。 The toner of aspect 1 contains a binder resin obtained by using fumaric acid and / or maleic acid as a raw material monomer, a nigrosine dye, and styrene.
フマル酸及び／又はマレイン酸を原料モノマーとして用いて得られる結着樹脂としては、ポリエステル、ポリエステル・アミド等が挙げられ、定着性及び帯電性の観点から、主成分としてポリエステルを含有する結着樹脂が好ましい。ポリエステルの含有量は、結着樹脂中、50〜100重量％が好ましく、80〜100重量％がより好ましく、実質的に100重量％が特に好ましい。 Examples of the binder resin obtained using fumaric acid and / or maleic acid as a raw material monomer include polyester, polyester amide, etc., and binder resin containing polyester as a main component from the viewpoint of fixability and chargeability. Is preferred. The content of the polyester is preferably 50 to 100% by weight, more preferably 80 to 100% by weight, particularly preferably 100% by weight in the binder resin.
ポリエステルは、特に限定されないが、2価以上のアルコールからなるアルコール成分と、フマル酸及び／又はマレイン酸を含む2価以上のカルボン酸化合物からなるカルボン酸成分を含む原料モノマーを縮重合させて得られる。 Polyester is not particularly limited, and is obtained by polycondensing a raw material monomer containing an alcohol component composed of a divalent or higher alcohol and a carboxylic acid component composed of a divalent or higher carboxylic acid compound containing fumaric acid and / or maleic acid. It is done.
2価のアルコールとしては、ポリオキシプロピレン−2，2−ビス(4−ヒドロキシフェニル)プロパン、ポリオキシエチレン−2，2−ビス(4−ヒドロキシフェニル)プロパン等のビスフェノールAのアルキレン(炭素数2又は3)オキサイド付加物(平均付加モル数1〜10)、エチレングリコール、プロピレングリコール、1，6−ヘキサンジオール、ビスフェノールA、水素添加ビスフェノールA等が挙げられる。 Examples of the divalent alcohol include alkylenes of bisphenol A such as polyoxypropylene-2,2-bis (4-hydroxyphenyl) propane and polyoxyethylene-2,2-bis (4-hydroxyphenyl) propane (carbon number 2 Or 3) Oxide adduct (average number of added moles of 1 to 10), ethylene glycol, propylene glycol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A and the like.
3価以上のアルコールとしては、ソルビトール、1，4−ソルビタン、ペンタエリスリトール、グリセロール、トリメチロールプロパン等が挙げられる。 Examples of the trihydric or higher alcohol include sorbitol, 1,4-sorbitan, pentaerythritol, glycerol, trimethylolpropane and the like.
カルボン酸成分中のフマル酸及びマレイン酸の総含有量は、トナーの靭性を高める観点から、好ましくは3〜80モル％であり、より好ましくは5〜50モル％であり、さらに好ましくは10〜30モル％である。フマル酸及びマレイン酸は、酸の無水物、及び酸のアルキルエステルとして用いられてもよい。 From the viewpoint of increasing the toughness of the toner, the total content of fumaric acid and maleic acid in the carboxylic acid component is preferably 3 to 80 mol%, more preferably 5 to 50 mol%, still more preferably 10 to 30 mol%. Fumaric acid and maleic acid may be used as acid anhydrides and alkyl esters of acids.
また、フマル酸、マレイン酸以外の2価のカルボン酸化合物としては、フタル酸、イソフタル酸、テレフタル酸等のジカルボン酸、炭素数1〜20のアルキル基又は炭素数2〜20のアルケニル基で置換されたコハク酸、これらの酸の無水物及びアルキル(炭素数1〜12)エステル等が挙げられる。 In addition, divalent carboxylic acid compounds other than fumaric acid and maleic acid are substituted with dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, alkyl groups having 1 to 20 carbon atoms, or alkenyl groups having 2 to 20 carbon atoms. Succinic acid, anhydrides of these acids and alkyl (C1-12) esters.
3価以上のカルボン酸化合物としては、1，2，4−ベンゼントリカルボン酸(トリメリット酸)及びその酸無水物、アルキル(炭素数1〜12)エステル等が挙げられる。 Examples of the trivalent or higher carboxylic acid compounds include 1,2,4-benzenetricarboxylic acid (trimellitic acid), its acid anhydride, and alkyl (C1-12) ester.
なお、アルコール成分には1価のアルコールが、カルボン酸成分には1価のカルボン酸化合物が、分子量調整や耐オフセット性向上の観点から、適宜含有されていてもよい。 The alcohol component may contain a monovalent alcohol, and the carboxylic acid component may contain a monovalent carboxylic acid compound as appropriate from the viewpoints of molecular weight adjustment and offset resistance improvement.
アルコール成分とカルボン酸成分との縮重合は、例えば、不活性ガス雰囲気中にて、要すればエステル化触媒を用いて、180〜250℃の温度で行うことができる。 The polycondensation of the alcohol component and the carboxylic acid component can be performed, for example, in an inert gas atmosphere at a temperature of 180 to 250 ° C. using an esterification catalyst if necessary.
なお、本発明において、ポリエステルは、実質的にその特性を損なわない程度に変性されたポリエステルであってもよい。変性されたポリエステルとしては、例えば、特開平１１−１３３６６８号公報、特開平１０−２３９９０３号公報、特開平８−２０６３６号公報等に記載の方法によりフェノール、ウレタン、エポキシ等によりグラフト化やブロック化したポリエステルをいう。 In the present invention, the polyester may be a polyester modified to such an extent that the characteristics are not substantially impaired. Examples of the modified polyester include grafting and blocking with phenol, urethane, epoxy and the like by the methods described in JP-A-11-133668, JP-A-10-239903, JP-A-8-20636, and the like. Polyester.
態様２のトナーは、スチレンの存在下でフマル酸及び／又はマレイン酸を原料モノマーとして用いて得られる結着樹脂及びニグロシン染料を含有する。 The toner according to Aspect 2 contains a binder resin obtained by using fumaric acid and / or maleic acid as a raw material monomer in the presence of styrene and a nigrosine dye.
スチレンの存在下でフマル酸及び／又はマレイン酸を原料モノマーとして用いて得られる結着樹脂としては、スチレンの分散性の観点から、例えば、アルコール成分とフマル酸及び／又はマレイン酸を含むカルボン酸成分とをスチレンの存在下で縮重合させて得られるポリエステル、アルコール成分とフマル酸及び／又はマレイン酸を含むカルボン酸成分とを含むポリエステルの原料モノマー及びスチレンを含む付加重合系樹脂の原料モノマーを用いて得られる複合樹脂が好ましい。 As a binder resin obtained by using fumaric acid and / or maleic acid as a raw material monomer in the presence of styrene, from the viewpoint of dispersibility of styrene, for example, a carboxylic acid containing an alcohol component and fumaric acid and / or maleic acid A polyester obtained by polycondensation of components in the presence of styrene, a raw material monomer of a polyester containing an alcohol component and a carboxylic acid component containing fumaric acid and / or maleic acid, and a raw material monomer of an addition polymerization resin containing styrene The composite resin obtained by using is preferable.
アルコール成分とフマル酸及び／又はマレイン酸を含むカルボン酸成分とをスチレンの存在下で縮重合させて得られるポリエステルは、縮重合をスチレンの存在下で行う以外は態様１と同様にして得られ、スチレンの使用量は、フマル酸及び／又はマレイン酸によるニグロシン染料への阻害を抑制する観点から、フマル酸及びマレイン酸の総重量100重量部に対して、好ましくは5〜40重量部であり、より好ましくは10〜30重量部である。 A polyester obtained by condensation polymerization of an alcohol component and a carboxylic acid component containing fumaric acid and / or maleic acid in the presence of styrene is obtained in the same manner as in Embodiment 1 except that the condensation polymerization is carried out in the presence of styrene. The amount of styrene used is preferably 5 to 40 parts by weight with respect to 100 parts by weight of the total weight of fumaric acid and maleic acid from the viewpoint of suppressing inhibition of nigrosine dye by fumaric acid and / or maleic acid. More preferably, it is 10 to 30 parts by weight.
複合樹脂としては、ポリエステルユニットとスチレンを含むビニル系樹脂等の付加重合系樹脂ユニットを有する樹脂が好ましい。なお、ポリエステルユニットとはポリエステル構造を有する部位を指す。 The composite resin is preferably a resin having an addition polymerization resin unit such as a vinyl resin containing a polyester unit and styrene. In addition, a polyester unit refers to the site | part which has a polyester structure.
ポリエステルユニットの原料モノマーとしては、態様１で挙げたアルコール成分とフマル酸及び／又はマレイン酸を含むカルボン酸成分が同様に挙げられる。 As the raw material monomer of the polyester unit, the alcohol component and the carboxylic acid component containing fumaric acid and / or maleic acid mentioned in the embodiment 1 are similarly exemplified.
付加重合系樹脂ユニットの原料モノマーとしては、スチレン、α-メチルスチレン等のスチレン化合物；エチレン、プロピレン等のエチレン性不飽和モノオレフィン類；ブタジエン等のジオレフィン類；塩化ビニル等のハロビニル類；酢酸ビニル、プロピオン酸ビニル等のビニルエステル類；(メタ)アクリル酸のアルキル(炭素数1〜18)エステル、(メタ)アクリル酸ジメチルアミノエチル等のエチレン性モノカルボン酸のエステル；ビニルメチルエーテル等のビニルエーテル類；ビニリデンクロリド等のビニリデンハロゲン化物；Ｎ-ビニルピロリドン等のＮ-ビニル化合物類等が挙げられ、これらの中では、スチレン以外に、定着性及びガラス転移点の調整の観点から、(メタ)アクリル酸のアルキルエステルが好ましく、２-エチルヘキシルアクリレート、ブチルアクリレート及びアクリル酸の長鎖アルキル(炭素数12〜18)エステルがより好ましい。スチレンの含有量は、ビニル系樹脂の原料モノマー中、50〜90重量％が好ましく、75〜90重量％がより好ましい。スチレンの(メタ)アクリル酸のアルキルエステルに対するモノマー比(スチレン／(メタ)アクリル酸のアルキルエステル)は、50/50〜95/5が好ましく、70/30〜95/5がより好ましい。 Raw material monomers for addition polymerization resin units include styrene compounds such as styrene and α-methylstyrene; ethylenically unsaturated monoolefins such as ethylene and propylene; diolefins such as butadiene; halovinyls such as vinyl chloride; Vinyl esters such as vinyl and vinyl propionate; alkyl (1 to 18 carbon atoms) esters of (meth) acrylic acid, esters of ethylenic monocarboxylic acids such as dimethylaminoethyl (meth) acrylate; vinyl methyl ether, etc. Vinyl ethers; vinylidene halides such as vinylidene chloride; N-vinyl compounds such as N-vinyl pyrrolidone, and the like. Among these, in addition to styrene, (meta) Preferred are alkyl esters of acrylic acid. 2-ethylhexyl acrylate DOO, long chain alkyl (having 12 to 18 carbon atoms) of butyl acrylate and acrylic acid esters are more preferable. The content of styrene is preferably 50 to 90% by weight and more preferably 75 to 90% by weight in the raw material monomer of the vinyl resin. The monomer ratio of styrene to the alkyl ester of (meth) acrylic acid (styrene / (meth) acrylic acid alkyl ester) is preferably 50/50 to 95/5, and more preferably 70/30 to 95/5.
なお、付加重合系樹脂ユニットの原料モノマーの付加重合には、重合開始剤、架橋剤等を必要に応じて使用してもよい。 In addition, a polymerization initiator, a crosslinking agent, etc. may be used as needed for the addition polymerization of the raw material monomer of the addition polymerization resin unit.
本発明においては、ポリエステルユニットの付加重合系樹脂ユニットに対する重量比、即ちポリエステルユニットの原料モノマーの付加重合系樹脂ユニットの原料モノマーに対する重量比(ポリエステルユニットの原料モノマー／付加重合系樹脂ユニットの原料モノマー)は、連続相がポリエステルユニットであり、分散相が付加重合系樹脂ユニットであることが好ましいことから、50/50〜95/5が好ましく、60/40〜95/5がより好ましい。 In the present invention, the weight ratio of the polyester unit to the addition polymerization resin unit, that is, the weight ratio of the raw material monomer of the polyester unit to the raw material monomer of the addition polymerization resin unit (the raw material monomer of the polyester unit / the raw material monomer of the addition polymerization resin unit). ) Is preferably 50/50 to 95/5, more preferably 60/40 to 95/5 since the continuous phase is preferably a polyester unit and the dispersed phase is preferably an addition polymerization resin unit.
本発明において、複合樹脂は、ポリエステルユニットの原料モノマーと付加重合系樹脂ユニットの原料モノマーに加えて、さらにポリエステルユニットの原料モノマー及び付加重合系樹脂ユニットの原料モノマーのいずれとも反応し得る化合物(両反応性モノマー)を用いて得られる樹脂(ハイブリッド樹脂)であることが好ましい。 In the present invention, the composite resin is a compound capable of reacting with both the raw material monomer of the polyester unit and the raw material monomer of the addition polymerization resin unit, as well as both the raw material monomer of the polyester unit and the raw material monomer of the addition polymerization resin unit (both A resin (hybrid resin) obtained using a reactive monomer) is preferable.
両反応性モノマーとしては、分子内に、水酸基、カルボキシル基、エポキシ基、第１級アミノ基及び第２級アミノ基からなる群より選ばれた少なくとも１種の官能基と、エチレン性不飽和結合とを有する化合物が好ましく、このような両反応性モノマーを用いることにより、分散相となる樹脂の分散性をより一層向上させることができる。両反応性モノマーの具体例としては、例えば、アクリル酸、フマル酸、メタクリル酸、シトラコン酸、マレイン酸、(メタ)アクリル酸２-ヒドロキシエチル、(メタ)アクリル酸グリシジル、及びこれらのカルボン酸の無水物、アルキル(炭素数1〜2)エステル等の誘導体等が挙げられ、これらのなかでは反応性の観点からアクリル酸、メタクリル酸、フマル酸、マレイン酸及びこれらのカルボン酸の誘導体が好ましい。 As the both reactive monomers, at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, a primary amino group and a secondary amino group in the molecule, and an ethylenically unsaturated bond A compound having the above formula is preferred, and by using such a bireactive monomer, the dispersibility of the resin to be the dispersed phase can be further improved. Specific examples of the both reactive monomers include, for example, acrylic acid, fumaric acid, methacrylic acid, citraconic acid, maleic acid, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, and carboxylic acids thereof. Derivatives such as anhydrides, alkyl (1 to 2 carbon atoms) esters and the like can be mentioned, and among these, acrylic acid, methacrylic acid, fumaric acid, maleic acid and derivatives of these carboxylic acids are preferable from the viewpoint of reactivity.
本発明において、両反応性モノマーのうち、官能基を２個以上有するモノマー(ポリカルボン酸等)及びその誘導体はポリエステルユニットの原料モノマーとして、官能基を１個有するモノマー(モノカルボン酸等)及びその誘導体は付加重合系樹脂ユニットの原料モノマーとして扱う。両反応性モノマーの使用量は、両反応性モノマーを除く付加重合系樹脂ユニットの原料モノマー100モルに対して、1〜30モルが好ましく、より付加重合系樹脂ユニットの分散性をさらに高める観点から、1.5〜20モルがより好ましく、2〜10モルがさらに好ましい。 In the present invention, among the two reactive monomers, a monomer having two or more functional groups (polycarboxylic acid or the like) and a derivative thereof are used as a raw material monomer for the polyester unit as a monomer having one functional group (monocarboxylic acid or the like) and The derivative is treated as a raw material monomer for the addition polymerization resin unit. The amount of the both reactive monomers used is preferably 1 to 30 moles per 100 moles of the raw material monomer of the addition polymerization resin unit excluding the both reactive monomers, from the viewpoint of further increasing the dispersibility of the addition polymerization resin unit. 1.5 to 20 mol is more preferable, and 2 to 10 mol is more preferable.
本発明において、複合樹脂は、縮重合反応と付加重合反応を同一反応容器中で並行して行うことにより得られるが、縮重合反応と付加重合反応の進行及び完結は、時間的に同時である必要はなく、それぞれの反応機構に応じて反応温度及び時間を適当に選択し、反応を進行、完結させればよい。 In the present invention, the composite resin is obtained by performing the condensation polymerization reaction and the addition polymerization reaction in parallel in the same reaction vessel, but the progress and completion of the condensation polymerization reaction and the addition polymerization reaction are simultaneous in time. It is not necessary, and the reaction temperature and time may be appropriately selected according to each reaction mechanism to advance and complete the reaction.
なお、縮重合反応は、例えば、態様１と同様にして行うことができ、付加重合反応は、例えば、重合開始剤、架橋剤等の存在下、有機溶媒存在下又は無溶媒下で、常法により行うことができるが、例えば、温度条件は、好ましくは110〜200℃、より好ましくは140〜170℃である。また、付加重合反応は、ワックスの存在下で行ってもよい。 The polycondensation reaction can be performed, for example, in the same manner as in Embodiment 1, and the addition polymerization reaction is performed in the usual manner, for example, in the presence of a polymerization initiator, a crosslinking agent, or the like, in the presence of an organic solvent, or in the absence of a solvent. However, for example, the temperature condition is preferably 110 to 200 ° C, more preferably 140 to 170 ° C. The addition polymerization reaction may be performed in the presence of wax.
ワックスとしては、低分子量ポリプロピレン、低分子量ポリエチレン、低分子量ポリプロピレンポリエチレン共重合体、マイクロクリスタリンワックス、パラフィンワックス、フィッシャートロプシュワックス等の脂肪族炭化水素系ワックス及びそれらの酸化物、カルナウバワックス、モンタンワックス、サゾールワックス及びそれらの脱酸ワックス等のエステル系ワックス、脂肪酸アミド類、脂肪酸類、高級アルコール類、脂肪酸金属塩等が挙げられ、これらのなかでは、離型性及び安定性の観点から、脂肪族炭化水素系ワックスが好ましい。 Examples of the wax include aliphatic hydrocarbon waxes such as low molecular weight polypropylene, low molecular weight polyethylene, low molecular weight polypropylene polyethylene copolymer, microcrystalline wax, paraffin wax, and Fischer-Tropsch wax, and oxides thereof, carnauba wax, and montan wax. , Ester waxes such as sazol wax and their deoxidized wax, fatty acid amides, fatty acids, higher alcohols, fatty acid metal salts, etc., among these, from the viewpoint of releasability and stability, Aliphatic hydrocarbon waxes are preferred.
ワックスの添加量は、結着樹脂の製造に用いられる樹脂単量体の総量100重量部に対して、20重量部以下が好ましく、10重量部以下がより好ましい。 The amount of the wax added is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less with respect to 100 parts by weight of the total amount of resin monomers used in the production of the binder resin.
ワックスの添加時期は特に限定されず、重合開始当初であっても、重合反応途中であってもよい。 The addition timing of the wax is not particularly limited, and may be at the beginning of the polymerization or in the middle of the polymerization reaction.
複合樹脂がさらに両反応性モノマーを用いて得られるハイブリッド樹脂である場合には、ポリエステルユニットの原料モノマー及び付加重合系樹脂ユニットの原料モノマーの混合物と両反応性モノマーを混合し、縮重合反応と付加重合反応を同一反応容器中で並行して行うことにより得られる樹脂であることが好ましい。 In the case where the composite resin is a hybrid resin obtained by further using an amphoteric monomer, a mixture of the raw material monomer of the polyester unit and the raw material monomer of the addition polymerization resin unit and the amphoteric monomer are mixed, and a condensation polymerization reaction is performed. A resin obtained by performing addition polymerization reaction in parallel in the same reaction vessel is preferable.
また、複合樹脂は、残存スチレンを適度な範囲に調整する観点から、スチレンを含む付加重合系樹脂単量体を付加重合反応させる工程(Ａ)、(Ａ)の途中及び／又は終了後に、工程(Ａ)で生じる反応混合物と水とを混合する工程(Ｂ)、並びに工程(Ａ)及び工程(Ｂ)の前、中及び後の少なくともいずれかの時点で、さらにポリエステル単量体を前記の反応系に存在させて縮重合反応させる工程(Ｃ)を経て得ることもできる。 In addition, from the viewpoint of adjusting the residual styrene to an appropriate range, the composite resin is a step (A) in which an addition polymerization resin monomer containing styrene is subjected to an addition polymerization reaction. The step (B) of mixing the reaction mixture produced in (A) and water, and at least at any time before, during and after the steps (A) and (B), further add the polyester monomer as described above. It can also be obtained through a step (C) in which it is present in the reaction system and subjected to a condensation polymerization reaction.
水の混合量は、樹脂の物性への影響を制御する観点から、付加重合系樹脂単量体100重量部に対して、0.1〜50重量部が好ましく、0.5〜40重量部がより好ましく、1〜35重量部がさらに好ましい。 The mixing amount of water is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 40 parts by weight with respect to 100 parts by weight of the addition polymerization resin monomer, from the viewpoint of controlling the influence on the physical properties of the resin. More preferred is ~ 35 parts by weight.
工程(Ａ)で生じる反応混合物と水とを混合する際の温度は、水の蒸発効率及び反応混合物の粘度の観点から、100〜300℃が好ましく、130〜250℃がより好ましく、150〜240℃がさらに好ましい。 The temperature at which the reaction mixture produced in step (A) is mixed with water is preferably 100 to 300 ° C, more preferably 130 to 250 ° C, more preferably 150 to 240, from the viewpoints of water evaporation efficiency and the viscosity of the reaction mixture. More preferably.
工程(Ａ)で生ずる反応混合物と水とを混合する方法は特に限定されないが、水との共沸効果により、スチレン量を効率よく調整する観点から、かかる反応混合物に水を滴下したり、蒸気を添加したりする方法が好ましい。水は、混合後蒸発するが、樹脂中の含水量は、トナーの帯電特性の観点から、0.2重量％以下が好ましく、含水量を低減する方法としては、水の混合後、100℃以上で保持する、又は減圧により除去する等の方法が好ましい。 The method of mixing the reaction mixture produced in the step (A) and water is not particularly limited, but water is added dropwise to the reaction mixture from the viewpoint of efficiently adjusting the amount of styrene due to the azeotropic effect with water. The method of adding is preferable. Although water evaporates after mixing, the water content in the resin is preferably 0.2% by weight or less from the viewpoint of the charging characteristics of the toner. As a method of reducing the water content, the water content is maintained at 100 ° C. or higher after mixing. Or a method such as removing by reduced pressure is preferable.
工程(Ａ)と工程(Ｂ)は、それぞれ別々に行う必要はなく、両工程を一部並行して行ってもよい。従って、反応混合物と水とを混合する時期は、工程(Ａ)における付加重合反応の終了後であっても、付加重合反応の途中であってもよいが、本発明では、水と樹脂との混合性の観点から、水と混合する工程（Ａ）により生ずる付加重合系樹脂の重量平均分子量は2000〜100000が好ましく、工程(Ａ)における付加重合反応が終了した後に水を添加することが好ましい。付加重合反応の進行度は、使用した開始剤の半減期、反応熱量等から予測、確認することができる。 The step (A) and the step (B) do not have to be performed separately, and both steps may be partially performed in parallel. Therefore, the timing of mixing the reaction mixture and water may be after the addition polymerization reaction in step (A) or in the middle of the addition polymerization reaction. From the viewpoint of mixing properties, the weight average molecular weight of the addition polymerization resin produced in the step (A) mixed with water is preferably 2000 to 100,000, and it is preferable to add water after the addition polymerization reaction in the step (A) is completed. . The progress of the addition polymerization reaction can be predicted and confirmed from the half-life of the initiator used, the heat of reaction, and the like.
複合樹脂の製造方法における、工程の手順としては、
ｉ）縮重合反応を行う工程（Ｃ）の後に、工程（Ａ）を行う方法、
ii）縮重合反応を行う工程（Ｃ）を、工程（Ａ）に先立って開始し、工程（Ａ）の後に、再度反応温度を上昇させ、必要に応じて架橋剤となる３価以上の縮重合系樹脂単量体を重合系に添加し、工程（Ｃ）の縮重合反応をさらに進める方法、
iii)付加重合反応に適した温度条件下で付加重合反応を行う工程（Ａ）と縮重合反応を行う工程（Ｃ）を並行して行い、反応温度を前記条件下で保持して工程（Ａ）を完結させた後、反応温度を上昇させ、必要に応じて架橋剤となる３価以上の縮重合系樹脂単量体を重合系に添加し、工程（Ｃ）の縮重合反応をさらに進める方法、
等が挙げられる。これらの方法において、工程（Ｂ）の実施は前記のように工程（Ａ）の開始後であればよいが、工程（Ａ）の終了後であることが好ましく、工程（Ａ）及び工程（Ｃ）の終了後であることがより好ましい。また、iii)の方法において、工程（Ａ）と工程（Ｃ）を並行して行う際には、縮重合系樹脂単量体を含有した混合物中に、付加重合系樹脂単量体を含有した混合物を滴下して反応させることが好ましい。このように反応容器中で独立した２つの重合反応を並行して進行させる方法により２種類の樹脂成分が効果的に混合分散した複合樹脂を得ることができる。
As a procedure of the process in the manufacturing method of the composite resin,
i) a method of performing the step (A) after the step (C) of performing the condensation polymerization reaction;
ii) The step (C) for conducting the polycondensation reaction is started prior to the step (A), and after the step (A), the reaction temperature is increased again, and if necessary, a trivalent or higher polycondensation that becomes a crosslinking agent is performed. A method in which a polymerization resin monomer is added to the polymerization system, and the condensation polymerization reaction in the step (C) is further advanced,
iii) The step (A) for carrying out the addition polymerization reaction under the temperature conditions suitable for the addition polymerization reaction and the step (C) for carrying out the condensation polymerization reaction are carried out in parallel, and the reaction temperature is maintained under the above conditions. ) Is completed, the reaction temperature is increased, and if necessary, a tri- or higher polycondensation resin monomer serving as a cross-linking agent is added to the polymerization system to further advance the polycondensation reaction in step (C). Method,
Etc. In these methods, the step (B) may be performed after the start of the step (A) as described above, but is preferably after the end of the step (A), and the steps (A) and (C) More preferably after the end of). In the method iii), when the step (A) and the step (C) are performed in parallel, the addition polymerization resin monomer is contained in the mixture containing the condensation polymerization resin monomer. It is preferable that the mixture is dropped and reacted. In this way, a composite resin in which two types of resin components are effectively mixed and dispersed can be obtained by a method in which two independent polymerization reactions proceed in parallel in a reaction vessel.
また、複合樹脂が両反応性モノマーを用いて得られるハイブリッド樹脂である場合にも、上記工程（Ａ）〜（Ｃ）を経て得ることができる。 Moreover, also when a composite resin is a hybrid resin obtained using an both-reactive monomer, it can obtain through the said process (A)-(C).
態様２の結着樹脂は、本発明の効果を損なわない範囲で、さらに、エポキシ樹脂、ポリカーボネート、ポリウレタン、スチレン−アクリル樹脂等の他の結着樹脂を含有していてもよい。 The binder resin of aspect 2 may further contain other binder resins such as epoxy resin, polycarbonate, polyurethane, and styrene-acrylic resin as long as the effects of the present invention are not impaired.
態様１及び２の結着樹脂の軟化点は、定着性及び耐久性の観点から、好ましくは110〜160℃、より好ましくは120〜150℃であり、ガラス転移点は55〜65℃が好ましい。また、酸価は1〜10mgKOH／gが好ましい。 The softening point of the binder resin of Embodiments 1 and 2 is preferably 110 to 160 ° C., more preferably 120 to 150 ° C., and the glass transition point is preferably 55 to 65 ° C. from the viewpoints of fixability and durability. The acid value is preferably 1 to 10 mgKOH / g.
態様１及び２の結着樹脂中のフマル酸及びマレイン酸の総含有量は、トナーを正帯電性にする観点から、好ましくは10〜500ppmであり、より好ましくは10〜200ppmであり、さらに好ましくは10〜100ppmである。本明細書において、フマル酸及びマレイン酸の総含有量は、後述の実施例に記載の方法により測定される。 From the viewpoint of making the toner positively chargeable, the total content of fumaric acid and maleic acid in the binder resin of Embodiments 1 and 2 is preferably 10 to 500 ppm, more preferably 10 to 200 ppm, and still more preferably Is 10-100 ppm. In the present specification, the total content of fumaric acid and maleic acid is measured by the method described in Examples described later.
態様２の結着樹脂中のスチレン含有量は、トナーを正帯電性にする観点から、好ましくは3〜100ppmであり、より好ましくは3〜50ppmであり、さらに好ましくは4〜50ppmである。本明細書において、スチレンの含有量は、後述の実施例に記載の方法により測定される。 From the viewpoint of making the toner positively chargeable, the styrene content in the binder resin of Embodiment 2 is preferably 3 to 100 ppm, more preferably 3 to 50 ppm, and further preferably 4 to 50 ppm. In the present specification, the content of styrene is measured by the method described in Examples described later.
本発明におけるニグロシン染料は正帯電性荷電制御剤として、高い帯電性を有しており、かつ黒色を呈しているため、着色剤の黒色度を補い、トナーの正の帯電性の調整と帯電安定性に寄与する。 The nigrosine dye in the present invention has a high chargeability as a positively chargeable charge control agent and has a black color. Therefore, the blackness of the colorant is compensated for, and the positive chargeability of the toner is adjusted and the charge is stabilized. Contributes to sex.
ニグロシン染料は、一般に金属触媒存在下でのニトロベンゼンとアニリンとの縮重合により得られる多数の成分からなる黒色の混合物であり、その構造は十分に明らかにされていないが、樹脂酸等による変成品も含めて、市販のニグロシン染料としては、「ニグロシンベースEX」、「オイルブラックBS」、「オイルブラックSO」、「ボントロンN-01」、「ボントロンN-04」、「ボントロンN-07」、「ボントロンN-09」、「ボントロンN-11」、「ボントロンN-21」(以上、オリエント化学工業社製)、「ニグロシン」(池田化学社製)、「スピリットブラックNo.850」、「スピリットブラックNo.900」(以上、住友化学社製)等が挙げられる。なお、結着樹脂として、ポリエステルと併用する場合は、分散性の観点から、樹脂酸により変性されたニグロシン染料が好ましく、このような市販品としては、上記市販品のうち、「ボントロンN-04」、「ボントロンN-21」(以上、オリエント化学工業社製)等が挙げられる。 Nigrosine dye is a black mixture consisting of a large number of components generally obtained by condensation polymerization of nitrobenzene and aniline in the presence of a metal catalyst, and its structure has not been fully clarified, but it is a modified product by resin acid, etc. , Including Nigrosine Base EX, Oil Black BS, Oil Black SO, Bontron N-01, Bontron N-04, Bontron N-07, Bontron N-09, Bontron N-11, Bontron N-21 (above, Orient Chemical Industry Co., Ltd.), Nigrosine (Ikeda Chemical Co., Ltd.), Spirit Black No.850, Spirit Black No. 900 ”(manufactured by Sumitomo Chemical Co., Ltd.). In addition, when used in combination with polyester as the binder resin, a nigrosine dye modified with a resin acid is preferable from the viewpoint of dispersibility, and such a commercially available product includes “Bontron N-04” among the above-mentioned commercially available products. "Bontron N-21" (manufactured by Orient Chemical Industry Co., Ltd.) and the like.
ニグロシン染料の含有量は、結着樹脂100重量部に対して、0.2〜10重量部が好ましく、0.5〜8重量部がより好ましい。 The content of the nigrosine dye is preferably 0.2 to 10 parts by weight and more preferably 0.5 to 8 parts by weight with respect to 100 parts by weight of the binder resin.
さらに、本発明のトナーは、本発明の効果を損なわない範囲で、ニグロシン染料以外の他の荷電制御剤を含有していてもよい。他の荷電制御剤としては、3級アミンを側鎖として含有するトリフェニルメタン系染料、4級アンモニウム塩化合物、ポリアミン樹脂、イミダゾール誘導体等の正帯電性荷電制御剤及び含金属アゾ染料、銅フタロシアニン染料、サリチル酸のアルキル誘導体の金属錯体、ベンジル酸のホウ素錯体等の負帯電性荷電制御剤が挙げられるが、本発明の目的である高い正帯電性を得るためには、荷電制御剤中のニグロシン染料の含有量は、70重量％以上が好ましく、80重量％以上がより好ましく、90重量％がさらに好ましく、実質的に100重量％であることがさらに好ましい。 Furthermore, the toner of the present invention may contain a charge control agent other than the nigrosine dye as long as the effects of the present invention are not impaired. Other charge control agents include triphenylmethane dyes containing tertiary amines as side chains, quaternary ammonium salt compounds, polyamine resins, imidazole derivatives and other positively chargeable charge control agents and metal-containing azo dyes, copper phthalocyanine Examples include negatively chargeable charge control agents such as dyes, metal complexes of alkyl derivatives of salicylic acid, boron complexes of benzyl acid, etc. In order to obtain the high positive chargeability that is the object of the present invention, nigrosine in the charge control agent The content of the dye is preferably 70% by weight or more, more preferably 80% by weight or more, further preferably 90% by weight, and further preferably substantially 100% by weight.
本発明のトナーには、さらに離型剤、着色剤、流動性向上剤、導電性調整剤、体質顔料、繊維状物質等の補強充填剤、酸化防止剤、老化防止剤、クリーニング性向上剤等の添加剤が適宜含有されていてもよい。 The toner of the present invention further includes a release agent, a colorant, a fluidity improver, a conductivity modifier, an extender pigment, a reinforcing filler such as a fibrous substance, an antioxidant, an antiaging agent, and a cleaning property improving agent. These additives may be contained as appropriate.
離型剤としては、カルナウバワックス、ライスワックス等の天然エステル系ワックス、パラフィンワックス、ポリプロピレンワックス、ポリエチレンワックス、フィッシャートロプッシュ等の合成ワックス、モンタンワックス等の石炭系ワックス、アルコール系ワックス等のワックスが挙げられるが、定着性及び無機微粒子の埋め込み防止の観点から、パラフィンワックスが好ましい。これらは単独で又は2種以上を混合して含有されていても良い。離型剤の含有量は、結着樹脂100重量部に対して、0.1〜20重量部が好ましく、0.5〜10重量部がより好ましい。離型剤は分散性向上の観点から、結着樹脂製造時に樹脂の原料モノマーと共に用いられ、結着樹脂に内添されていてもよい。 Mold release agents include natural ester waxes such as carnauba wax and rice wax, synthetic waxes such as paraffin wax, polypropylene wax, polyethylene wax and Fischer Tropu, coal waxes such as montan wax, and waxes such as alcohol waxes. However, paraffin wax is preferable from the viewpoint of fixing property and prevention of embedding of inorganic fine particles. These may be contained alone or in admixture of two or more. The content of the release agent is preferably 0.1 to 20 parts by weight and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the binder resin. From the viewpoint of improving dispersibility, the release agent may be used together with the resin raw material monomer during the production of the binder resin, and may be internally added to the binder resin.
着色剤としては、トナー用着色剤として用いられている染料、顔料等のすべてを使用することができ、カーボンブラック、フタロシアニンブルー、パーマネントブラウンFG、ブリリアントファーストスカーレット、ピグメントグリーンB、ローダミン−Bベース、ソルベントレッド49、ソルベントレッド146、ソルベントブルー35、キナクリドン、カーミン6B、ジスアゾエロー等が挙げられ、これらは単独で又は2種以上を混合して用いることができ、本発明のトナーは黒トナー、カラートナーのいずれであってもよい。着色剤の含有量は、結着樹脂100重量部に対して、1〜40重量部が好ましく、3〜10重量部がより好ましい。 As the colorant, all of dyes and pigments used as toner colorants can be used, such as carbon black, phthalocyanine blue, permanent brown FG, brilliant first scarlet, pigment green B, rhodamine-B base, Solvent Red 49, Solvent Red 146, Solvent Blue 35, Quinacridone, Carmine 6B, Disazo Yellow and the like can be used alone or in combination of two or more. The toner of the present invention is a black toner or a color toner. Any of these may be used. The content of the colorant is preferably 1 to 40 parts by weight and more preferably 3 to 10 parts by weight with respect to 100 parts by weight of the binder resin.
本発明のトナーは、結着樹脂、ニグロシン染料、態様１においてはさらにスチレン等を含む原料を、混練粉砕法、転相乳化法、乳化分散法、懸濁重合法等の従来公知のいずれの方法により製造してもよいが、製造が容易なことから、混練粉砕法により製造することが好ましい。例えば、混練粉砕法による場合、結着樹脂等の原料をヘンシェルミキサー等の混合機で均一に混合した後、密閉式ニーダー又は1軸もしくは2軸の押出機等で溶融混練し、冷却、粉砕、分級して製造することができる。特に、混練粉砕方法の場合、溶融混練温度の調整により、結着樹脂の熱分解等によりトナー中のスチレンの含有量が調整できるために、本発明のトナーの製造方法として有効である。さらに、必要に応じて外添剤により表面処理する工程を経て得ることもできる。 The toner of the present invention is prepared by using a binder resin, a nigrosine dye, and, in Embodiment 1, a raw material further containing styrene and the like, and any conventionally known method such as a kneading pulverization method, a phase inversion emulsification method, an emulsion dispersion method, or a suspension polymerization method However, since it is easy to manufacture, it is preferably manufactured by a kneading and pulverizing method. For example, in the case of the kneading and pulverizing method, the raw materials such as the binder resin are uniformly mixed with a mixer such as a Henschel mixer, and then melt-kneaded with a closed kneader or a single-screw or twin-screw extruder, etc. Can be classified and manufactured. In particular, the kneading and pulverizing method is effective as the method for producing the toner of the present invention because the content of styrene in the toner can be adjusted by adjusting the melt kneading temperature by thermal decomposition of the binder resin or the like. Furthermore, it can also obtain through the process of surface-treating with an external additive as needed.
本発明のトナーの体積中位粒径(D50)は、高画質を得る観点から2〜7μmが好ましく、3〜6μmがより好ましい。なお、本明細書において、体積中位粒径(D50)とは、体積分率で計算した累積体積頻度が粒径の小さい方から計算して50％になる粒径を意味する。 The volume median particle size (D 50 ) of the toner of the present invention is preferably 2 to 7 μm, more preferably 3 to 6 μm from the viewpoint of obtaining high image quality. In the present specification, the volume median particle size (D 50 ) means a particle size at which the cumulative volume frequency calculated by the volume fraction is 50% when calculated from the smaller particle size.
本発明のトナーは、そのまま一成分現像用トナーとして、又はキャリアと混合して二成分現像剤として用いることができる。 The toner of the present invention can be used as a one-component developing toner as it is or as a two-component developer by mixing with a carrier.
〔樹脂の軟化点〕
フローテスター(島津製作所、CFT-500D)を用い、1gの試料を昇温速度6℃／分で加熱しながら、プランジャーにより1.96MPaの荷重を与え、直径1mm、長さ1mmのノズルから押出した。温度に対し、フローテスターのプランジャー降下量をプロットし、試料の半量が流出した温度を軟化点とする。
[Softening point of resin]
Using a flow tester (Shimadzu Corporation, CFT-500D), a 1 g sample was heated at a heating rate of 6 ° C / min, and a load of 1.96 MPa was applied by a plunger and extruded from a nozzle with a diameter of 1 mm and a length of 1 mm. . The amount of plunger drop of the flow tester is plotted against the temperature, and the temperature at which half of the sample flows out is taken as the softening point.
〔樹脂のガラス転移点〕
示差走査熱量計(セイコー電子工業社製、DSC210)を用いて200℃まで昇温し、その温度から降温速度10℃／分で0℃まで冷却したサンプルを昇温速度10℃／分で昇温し、吸熱の最高ピーク温度以下のベースラインの延長線とピークの立ち上がり部分からピークの頂点までの最大傾斜を示す接線との交点の温度とする。
[Glass transition point of resin]
Using a differential scanning calorimeter (Seiko Denshi Kogyo Co., Ltd., DSC210), the temperature was raised to 200 ° C, and the sample was cooled to 0 ° C at a temperature drop rate of 10 ° C / min. The temperature at the intersection of the extended line of the baseline below the maximum peak temperature of endotherm and the tangent line indicating the maximum slope from the peak rising portion to the peak apex.
〔樹脂の酸価〕
JIS K0070の方法に基づき測定する。但し、測定溶媒のみJIS K0070の規定のエタノールとエーテルの混合溶媒から、アセトンとトルエンの混合溶媒(アセトン:トルエン＝1:1(容量比))に変更した。
[Acid value of the resin]
Measured according to the method of JIS K0070. However, only the measurement solvent was changed from the mixed solvent of ethanol and ether specified in JIS K0070 to the mixed solvent of acetone and toluene (acetone: toluene = 1: 1 (volume ratio)).
〔トナーの体積中位粒径（D50）〕
測定機：コールターマルチサイザーII（ベックマンコールター社製）
アパチャー径：100μm
解析ソフト：コールターマルチサイザーアキュコンプ バージョン 1.19（ベックマンコールター社製）
電解液：アイソトンII（ベックマンコールター社製）
分散液：エマルゲン109Ｐ（花王社製、ポリオキシエチレンラウリルエーテル、HLB：13.6）を5重量％の濃度となるよう前記電解液に溶解させて分散液を得る。
分散条件：前記分散液5mLに測定試料10mgを添加し、超音波分散機にて1分間分散させ、その後、電解液25mLを添加し、さらに、超音波分散機にて1分間分散させて、試料分散液を調製する。
測定条件：前記試料分散液を前記電解液100mLに加えることにより、3万個の粒子の粒径を20秒で測定できる濃度に調整した後、3万個の粒子を測定し、その粒度分布から体積中位粒径（D50）を求める。
[Volume-median particle size of toner (D 50 )]
Measuring machine: Coulter Multisizer II (Beckman Coulter, Inc.)
Aperture diameter: 100μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (Beckman Coulter)
Electrolyte: Isoton II (Beckman Coulter, Inc.)
Dispersion: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6) is dissolved in the electrolytic solution to a concentration of 5% by weight to obtain a dispersion.
Dispersion conditions: 10 mg of a measurement sample is added to 5 mL of the above dispersion, and dispersed for 1 minute with an ultrasonic disperser, then 25 mL of electrolyte is added, and further dispersed for 1 minute with an ultrasonic disperser. Prepare a dispersion.
Measurement conditions: By adding the sample dispersion to 100 mL of the electrolytic solution, the particle size of 30,000 particles is adjusted to a concentration that can be measured in 20 seconds, and then 30,000 particles are measured, Determine the volume-median particle size (D 50 ).
〔フマル酸及びマレイン酸の含有量〕
フマル酸及びマレイン酸の含有量は、液体クロマトグラフ/紫外可視吸光度測定(LC/UVD)法により測定する。
(1) 測定装置
HPLC：8020シリーズ(東ソー株式会社製)
(2) HPLC測定条件
検出器：UVD 210nm
カラム：L-カラム ODS (平均細孔径：120Å、平均粒子径5μm、4.6mmID×150mm、財団法人化学物質評価研究機構製)
ガードカラム：L-カラム ガードカラム(平均細孔径：120Å、平均粒子径5μm、4.0mmID×10mm、財団法人化学物質評価研究機構製)
カラム温度：40℃
溶離液：50mmol/L リン酸緩衝液(pH2.5)
流速：1.0mL／min
注入量：20μL
分析時間：10分
(3) 検量線の作成
マレイン酸、フマル酸を各0.1ｇずつ精密に量り、イオン交換水で正確に100mLとする。さらにイオン交換水にて順次希釈し、1，5，10，15mg／Lの検量線溶液を作成する。これらの溶液の測定結果より、検量線を作成する。
(4) フマル酸及び／又はマレイン酸の定量
試料0.2ｇを精密に量り、トルエンで正確に20mLとする。その2mLを蓋付き試験管(10mL)に正確にとり、続いてイオン交換水5mLを正確に加えて、蓋をしてタッチミキサーで十分に混合する。その後、遠心分離機を用いて分相させ、下層(水層)を試料溶液とする。試料溶液の測定結果から、検量線を用いてフマル酸及びマレイン酸の含有量を算出する。
[Contents of fumaric acid and maleic acid]
The contents of fumaric acid and maleic acid are measured by a liquid chromatograph / ultraviolet visible absorbance measurement (LC / UVD) method.
(1) Measuring equipment
HPLC: 8020 series (manufactured by Tosoh Corporation)
(2) HPLC measurement conditions Detector: UVD 210nm
Column: L-column ODS (average pore size: 120 mm, average particle size 5 μm, 4.6 mm ID × 150 mm, manufactured by the Chemical Substance Evaluation Research Organization)
Guard column: L-column Guard column (average pore size: 120 mm, average particle size 5 μm, 4.0 mm ID × 10 mm, manufactured by Chemical Substances Research Institute)
Column temperature: 40 ° C
Eluent: 50mmol / L phosphate buffer (pH2.5)
Flow rate: 1.0mL / min
Injection volume: 20μL
Analysis time: 10 minutes
(3) Preparation of calibration curve Weigh accurately 0.1 g each of maleic acid and fumaric acid and make exactly 100 mL with ion-exchanged water. Further dilute sequentially with ion-exchanged water to prepare calibration curve solutions of 1, 5, 10, and 15 mg / L. A calibration curve is created from the measurement results of these solutions.
(4) Quantitative determination of fumaric acid and / or maleic acid Weigh accurately 0.2 g of sample and make exactly 20 mL with toluene. Take 2 mL of the solution accurately into a test tube with a lid (10 mL), then add exactly 5 mL of ion-exchanged water, close the lid, and mix well with a touch mixer. Thereafter, phase separation is performed using a centrifuge, and the lower layer (aqueous layer) is used as a sample solution. From the measurement results of the sample solution, the contents of fumaric acid and maleic acid are calculated using a calibration curve.
〔スチレン含有量〕
スチレンの含有量は、加熱脱着−ガスクロマトグラフ−質量分析(TD-GC/MS)を用いて、以下の方法により測定する。
[Styrene content]
The styrene content is measured by the following method using heat desorption-gas chromatography-mass spectrometry (TD-GC / MS).
テナックスＴＡ入りチューブに標品 「10」mg/L 重トルエン／メタノール溶液を5μＬ注入し、試料「5」mgを秤量して、TD−GC/MS測定を行った。 5 μL of a standard “10” mg / L deuterated toluene / methanol solution was injected into a tube containing Tenax TA, a sample “5” mg was weighed, and TD-GC / MS measurement was performed.
＜TDの測定条件＞
装置：Perkin Elmer社製のTurbo Matrix ATD（自動加熱脱着(ATD)装置）
<TD measurement conditions>
Equipment: Turbo Matrix ATD (automatic thermal desorption (ATD) equipment) manufactured by Perkin Elmer
「出口スプリット使用」
分析モード：2段階脱着
注入：2回
"Using exit split"
Analysis mode: 2-stage desorption injection: 2 times
チューブからの加熱脱着条件：120℃で1時間
トラップ管への吸着条件：-30℃で50分
トラップ管からの脱着条件：-30℃から開始し、40℃／minで300℃まで昇温
Heat desorption condition from tube: 1 hour at 120 ° C Adsorption condition to trap tube: 50 minutes at -30 ° C Desorption condition from trap tube: Start at -30 ° C and heat up to 300 ° C at 40 ° C / min
パージ時間 1分
バルブ温度 150℃、トランスファー温度 160℃
カラム圧力 150kPa
入口スプリット 50(mL/min)
出口スプリット 5(mL/min)
脱着 50(mL/min)
Purge time 1 minute Valve temperature 150 ° C, Transfer temperature 160 ° C
Column pressure 150kPa
Inlet split 50 (mL / min)
Outlet split 5 (mL / min)
Desorption 50 (mL / min)
＜GC/MSの測定条件＞
GC装置：Agilent Technologies社製の6890N
MS装置：Agilent Technologies社製の5973N
<Measurement conditions for GC / MS>
GC system: 6890N made by Agilent Technologies
MS equipment: 5973N manufactured by Agilent Technologies
オーブン：40℃で3分間保持、2℃/minで70℃まで昇温、5℃/minで150℃まで昇温、10℃/minで300℃まで昇温
カラム：HP5-MS（60m×250μm×0．25μm）
Constant pressure 150kPa（ATDから制御）
MS：scan range m/z＝40〜460
Initial Area Reject：0
Initial Peak Width：0.097
Shoulder Detection：off
Initial Threshold：12.0
なお、「10」mg／L 重トルエン／メタノール溶液による1点検量で定量を行う。重トルエンはm/z=98、スチレンはm/z=104のマスククロマトグラムの面積より求める。
Oven: Hold at 40 ° C for 3 minutes, heat up to 70 ° C at 2 ° C / min, heat up to 150 ° C at 5 ° C / min, heat up to 300 ° C at 10 ° C / min Column: HP5-MS (60m × 250μm × 0.25μm)
Constant pressure 150kPa (Controlled from ATD)
MS: scan range m / z = 40 to 460
Initial Area Reject: 0
Initial Peak Width: 0.097
Shoulder Detection: off
Initial Threshold: 12.0
Quantify with a single inspection amount of “10” mg / L deuterated toluene / methanol solution. It is determined from the area of the mask chromatogram of m / z = 98 for heavy toluene and m / z = 104 for styrene.
樹脂製造例１
表１に示すフマル酸及び無水トリメリット酸以外のポリエステル単量体の原料モノマー及びエステル化触媒としてオクチル酸スズ40gを、窒素導入管、脱水管、攪拌器及び熱電対を装備した10リットル容の四つ口フラスコに入れ、230℃でテレフタル酸の粒が確認できなくなるまで縮重合反応させた。さらに、8kPaで1時間反応させ、パラフィンワックス「HNP-9」(日本精鑞社製)を添加し、160℃に冷却後、表１に示すビニル系樹脂単量体の原料モノマー及び重合開始剤の混合物を滴下ロートにより1時間かけて滴下した。滴下後、160℃に保持したまま、1時間付加重合反応を熟成させた後、210℃に昇温し、8kPaで0.5時間保持した。その後、180℃に冷却し、表１に示すフマル酸とハイドロキノン5gを加えて、10℃／時間で昇温しながら210℃まで反応させた。更に表１に示す無水トリメリット酸を加えて、架橋反応を所定の軟化点に達するまで行い樹脂Ａを得た。なお、樹脂Ａにおける、ポリエステル単量体とビニル系樹脂単量体の重量比(ポリエステル単量体／ビニル系樹脂単量体の重量比)は70/30である。
Resin production example 1
As a raw material monomer of polyester monomers other than fumaric acid and trimellitic anhydride shown in Table 1, and 40 g of tin octylate as an esterification catalyst, a 10-liter capacity equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple It was put into a four-necked flask and subjected to a condensation polymerization reaction at 230 ° C. until no terephthalic acid particles could be confirmed. Further, the reaction is carried out at 8 kPa for 1 hour, paraffin wax “HNP-9” (manufactured by Nippon Seiki Co., Ltd.) is added, and after cooling to 160 ° C., the raw material monomers and polymerization initiators of the vinyl resin monomers shown in Table 1 The mixture was added dropwise using a dropping funnel over 1 hour. After the dropwise addition, the addition polymerization reaction was aged for 1 hour while maintaining the temperature at 160 ° C, and then the temperature was raised to 210 ° C and maintained at 8 kPa for 0.5 hours. Then, it cooled to 180 degreeC, the fumaric acid shown in Table 1 and 5 g of hydroquinone were added, and it was made to react to 210 degreeC, heating up at 10 degreeC / hour. Further, trimellitic anhydride shown in Table 1 was added, and a crosslinking reaction was performed until a predetermined softening point was reached, thereby obtaining a resin A. In the resin A, the weight ratio of the polyester monomer to the vinyl resin monomer (weight ratio of the polyester monomer / vinyl resin monomer) is 70/30.
樹脂製造例２
表１に示すフマル酸及び無水トリメリット酸以外のポリエステル単量体の原料モノマー及びエステル化触媒としてオクチル酸スズ40gを、窒素導入管、脱水管、攪拌器及び熱電対を装備した10リットル容の四つ口フラスコに入れ、230℃でテレフタル酸の粒が確認できなくなるまで縮重合反応させた。さらに、8kPaで1時間反応させ、パラフィンワックス「HNP-9」(日本精鑞社製)を添加し、160℃に冷却後、表１に示すビニル系樹脂単量体の原料モノマー及び重合開始剤の混合物を滴下ロートにより1時間かけて滴下した。滴下後、160℃に保持したまま、1時間付加重合反応を熟成させた後、210℃に昇温し、8kPaで0.5時間保持した。次いで、210℃で40kPaにおいて攪拌しながら、2時間かけて140℃の蒸気を800g(付加重合系樹脂単量体の総量100重量部に対して、31重量部)／時間の速度で樹脂中に添加した。その後、180℃に冷却し、表１に示すフマル酸とハイドロキノン5gを加えて、10℃／時間で昇温しながら210℃まで反応させた。更に表１に示す無水トリメリット酸を加えて、架橋反応を所定の軟化点に達するまで行い樹脂Ｂを得た。なお、樹脂Ｂにおける、ポリエステル単量体とビニル系樹脂単量体の重量比(ポリエステル単量体／ビニル系樹脂単量体の重量比)は70/30である。
Resin production example 2
As a raw material monomer of polyester monomers other than fumaric acid and trimellitic anhydride shown in Table 1, and 40 g of tin octylate as an esterification catalyst, a 10-liter capacity equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple It was put into a four-necked flask and subjected to a condensation polymerization reaction at 230 ° C. until no terephthalic acid particles could be confirmed. Further, the reaction is carried out at 8 kPa for 1 hour, paraffin wax “HNP-9” (manufactured by Nippon Seiki Co., Ltd.) is added, and after cooling to 160 ° C., the raw material monomers and polymerization initiators of the vinyl resin monomers shown in Table 1 The mixture was added dropwise using a dropping funnel over 1 hour. After the dropwise addition, the addition polymerization reaction was aged for 1 hour while maintaining the temperature at 160 ° C, and then the temperature was raised to 210 ° C and maintained at 8 kPa for 0.5 hours. Next, with stirring at 210 ° C. and 40 kPa, steam at 140 ° C. over 2 hours is added to the resin at a rate of 800 g (31 parts by weight with respect to 100 parts by weight of the total amount of addition polymerization resin monomer) / hour. Added. Then, it cooled to 180 degreeC, the fumaric acid shown in Table 1 and 5 g of hydroquinone were added, and it was made to react to 210 degreeC, heating up at 10 degreeC / hour. Further, trimellitic anhydride shown in Table 1 was added, and a crosslinking reaction was carried out until a predetermined softening point was reached to obtain a resin B. In the resin B, the weight ratio of polyester monomer to vinyl resin monomer (weight ratio of polyester monomer / vinyl resin monomer) is 70/30.
樹脂製造例３
表１に示すフマル酸及び無水トリメリット酸以外の原料モノマー及びエステル化触媒としてオクチル酸スズ40gを、窒素導入管、脱水管、攪拌器及び熱電対を装備した10リットル容の四つ口フラスコに入れ、230℃で8時間縮重合反応させた。さらに、8.3kPaで1時間反応させた後、180℃に冷却し、表１に示すフマル酸、無水トリメリット酸及びハイドロキノン5gを添加し、10℃／時間で昇温しながら210℃まで反応させた後、40kPaにて所望の軟化点に達するまで反応を行い、樹脂Ｃを得た。
Resin production example 3
Raw material monomers other than fumaric acid and trimellitic anhydride shown in Table 1 and 40 g of tin octylate as an esterification catalyst were placed in a 10-liter four-necked flask equipped with a nitrogen inlet tube, a dehydrating tube, a stirrer and a thermocouple. And the polycondensation reaction was carried out at 230 ° C. for 8 hours. Further, after reacting at 8.3 kPa for 1 hour, cool to 180 ° C., add fumaric acid, trimellitic anhydride and 5 g of hydroquinone shown in Table 1, and react to 210 ° C. while raising the temperature at 10 ° C./hour. Thereafter, the reaction was carried out at 40 kPa until the desired softening point was reached, whereby Resin C was obtained.
樹脂製造例４
表１に示すフマル酸及び無水トリメリット酸以外のポリエステルの原料モノマー、スチレン及びエステル化触媒としてオクチル酸スズ40gを、窒素導入管、脱水管、攪拌器及び熱電対を装備した10リットル容の四つ口フラスコに入れ、230℃で8時間縮重合反応させた。さらに、8.3kPaで1時間反応させた後、180℃に冷却し、表１に示すフマル酸、無水トリメリット酸及びハイドロキノン5gを添加し、10℃／時間で昇温しながら210℃まで反応させた後、40kPaにて所望の軟化点に達するまで反応を行い、樹脂Ｄを得た。
Resin production example 4
Polyester raw materials other than fumaric acid and trimellitic anhydride shown in Table 1, styrene, and 40 g of tin octylate as an esterification catalyst, and 10 liters of 4 liters equipped with nitrogen introduction tube, dehydration tube, stirrer and thermocouple The mixture was placed in a two-necked flask and subjected to condensation polymerization reaction at 230 ° C. for 8 hours. Further, after reacting at 8.3 kPa for 1 hour, cool to 180 ° C., add fumaric acid, trimellitic anhydride and 5 g of hydroquinone shown in Table 1, and react to 210 ° C. while raising the temperature at 10 ° C./hour. After that, the reaction was carried out at 40 kPa until the desired softening point was reached, whereby Resin D was obtained.
樹脂製造例５
表１に示す無水トリメリット酸以外の原料モノマー及びエステル化触媒としてオクチル酸スズ40gを、窒素導入管、脱水管、攪拌器及び熱電対を装備した10リットル容の四つ口フラスコに入れ、220℃で8時間縮重合反応させた。さらに、8.3kPaで1時間反応させた後、210℃に冷却し、表１に示す無水トリメリット酸を添加し、所望の軟化点に達するまで反応を行い、樹脂Ｅを得た。
Resin production example 5
Raw material monomers other than trimellitic anhydride shown in Table 1 and 40 g of tin octylate as an esterification catalyst were placed in a 10-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple. The polycondensation reaction was carried out at 8 ° C for 8 hours. Furthermore, after reacting at 8.3 kPa for 1 hour, the mixture was cooled to 210 ° C., trimellitic anhydride shown in Table 1 was added, and the reaction was performed until the desired softening point was reached.
実施例１〜３及び比較例１〜３
表２に示すトナー原料をヘンシェルミキサーにて攪拌混合後、混練部分の全長1560mm、スクリュー径42mm、バレル内径43mmの同方向回転二軸押出機を用いて溶融混練した。ロールの回転速度は200r／min、ロール内の加熱温度は120℃であり、混合物の供給速度は10kg／時間、平均滞留時間は約18秒であった。得られた混練物を冷却ローラーで圧延冷却した後、ジェットミルで粉砕し、分級して、体積中位粒径(D50)4.5μmのトナーを得た。
Examples 1-3 and Comparative Examples 1-3
The toner materials shown in Table 2 were stirred and mixed with a Henschel mixer, and then melt-kneaded using a co-rotating twin screw extruder having a total kneading part length of 1560 mm, a screw diameter of 42 mm, and a barrel inner diameter of 43 mm. The rotation speed of the roll was 200 r / min, the heating temperature in the roll was 120 ° C., the feed rate of the mixture was 10 kg / hour, and the average residence time was about 18 seconds. The obtained kneaded product was rolled and cooled with a cooling roller, then pulverized with a jet mill and classified to obtain a toner having a volume-median particle size (D 50 ) of 4.5 μm.
試験例１〔画像濃度〕
表２のトナー39重量部と、フッ素・アクリル樹脂で被覆された、飽和磁化が60Am2／kgのフェライトキャリア(平均粒子径：110μm)1261重量部とをナウターミキサーで混合し、二成分現像剤を得た。
Test Example 1 [Image density]
Two-component development is carried out by mixing 39 parts by weight of the toner shown in Table 2 and 1261 parts by weight of a ferrite carrier (average particle size: 110 μm) coated with fluorine / acrylic resin and having a saturation magnetization of 60 Am 2 / kg. An agent was obtained.
得られた二成分現像剤を「LS-1550」(京セラ(株)製、感光体：アモルファスシリコン、正帯電性トナー用二成分現像方式画像形成機)に実装し、Xerox社製50g紙に、印字率5％の画像を30枚印字した後、5cm四方のベタ画像の印刷を行った。得られた画像について、印字濃度を反射型画像濃度計「MacbethRD918」(Macbeth社製)を用いて測定し、以下の評価基準に従って画像濃度を評価した。結果を表２に示す。 The obtained two-component developer was mounted on “LS-1550” (manufactured by Kyocera Corporation, photoconductor: amorphous silicon, two-component development type image forming machine for positively chargeable toner), and on 50 g paper made by Xerox, After printing 30 images with a printing rate of 5%, a solid image of 5 cm square was printed. With respect to the obtained image, the print density was measured using a reflection type image densitometer “MacbethRD918” (manufactured by Macbeth), and the image density was evaluated according to the following evaluation criteria. The results are shown in Table 2.
〔画像濃度の評価基準〕
◎：印字濃度が1.3以上
○：印字濃度が1.2以上、1.3未満
×：印字濃度が1.2未満
[Image density evaluation criteria]
◎: Print density is 1.3 or more ○: Print density is 1.2 or more, less than 1.3 ×: Print density is less than 1.2
試験例２〔カブリ〕
得られたトナーでXerox社製50g紙に、印字率5％の画像を30枚印字した後、感光体を取り出した。感光体表面に残存しているトナーをメンディングテープに移しとった。かかるメンディングテープと未使用のメンディングテープとをそれぞれ白紙に貼り付け、両者の画像濃度をミノルタ社製色彩色差計「CR-300色差計」のL*a*b*モードで測定し、ΔEを求めた。同様に、さらに印字率5％で1000枚印字した後にも、色彩色差計でΔEを求め、ΔEの比(1000枚印字後のΔE／30枚印字後のΔE)を算出し、以下の評価基準に従ってカブリを評価した。結果を表２に示す。
Test Example 2 [Fog]
After printing 30 images with a printing rate of 5% on Xerox 50 g paper with the obtained toner, the photoreceptor was taken out. The toner remaining on the photoreceptor surface was transferred to a mending tape. Affix the mending tape and unused mending tape to blank paper, and measure the image density of both in the L * a * b * mode of the Minolta color difference meter “CR-300 color difference meter”. Asked. Similarly, even after printing 1000 sheets at a printing rate of 5%, ΔE is calculated with a color difference meter, and the ratio of ΔE (ΔE after printing 1000 sheets / ΔE after printing 30 sheets) is calculated. The fog was evaluated as follows. The results are shown in Table 2.
〔カブリの評価基準〕
〇：ΔEの比が2未満
×：ΔEの比が2以上
[Evaluation criteria for fogging]
◯: Ratio of ΔE is less than 2 ×: Ratio of ΔE is 2 or more
以上の結果から、フマル酸とスチレンを原料モノマーとして用いて得られる結着樹脂及びニグロシン染料を含有する実施例１〜３のトナーは、画像濃度も良好で、カブリの少ないものであることが分かる。一方、スチレンを使用していない結着樹脂を含有する比較例１のトナーは画像濃度が低く、フマル酸を使用した結着樹脂を含有しない比較例２のトナーはカブリが発生し、フマル酸とスチレンを原料モノマーとして用いて得られる結着樹脂とスチレンを使用していない結着樹脂との混合物を含有する比較例３のトナーは、残存スチレン量が低いため、画像濃度が低く、いずれも画像安定性に劣るものであった。また、実施例１及び２のトナーは、結着樹脂及びトナーの組成は同じであり、結着樹脂の製造方法の若干の違いにより残存スチレン量が33、7ppmと異なるのみで、画像濃度に差が認められたことから、フマル酸との併用によるスチレンの効果が示唆されるものであった。 From the above results, it can be seen that the toners of Examples 1 to 3 containing a binder resin and nigrosine dye obtained using fumaric acid and styrene as raw material monomers have good image density and low fog. . On the other hand, the toner of Comparative Example 1 containing a binder resin not using styrene has a low image density, and the toner of Comparative Example 2 containing no binder resin using fumaric acid is fogged. The toner of Comparative Example 3 containing a mixture of a binder resin obtained using styrene as a raw material monomer and a binder resin not using styrene has a low residual styrene content, and therefore has a low image density. It was inferior in stability. Further, the toners of Examples 1 and 2 have the same binder resin and toner composition, and the residual styrene amount differs from 33 and 7 ppm due to slight differences in the method of manufacturing the binder resin. From these results, the effect of styrene in combination with fumaric acid was suggested.
本発明の正帯電性トナーは、電子写真法、静電記録法、静電印刷法等において形成される潜像の現像等に用いられる。
The positively chargeable toner of the present invention is used for development of a latent image formed in electrophotography, electrostatic recording method, electrostatic printing method and the like.
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