JP6177080B2 - Toner and toner production method - Google Patents
Toner and toner production method Download PDFInfo
- Publication number
- JP6177080B2 JP6177080B2 JP2013204475A JP2013204475A JP6177080B2 JP 6177080 B2 JP6177080 B2 JP 6177080B2 JP 2013204475 A JP2013204475 A JP 2013204475A JP 2013204475 A JP2013204475 A JP 2013204475A JP 6177080 B2 JP6177080 B2 JP 6177080B2
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- pigment
- toner
- formula
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Description
本発明は、電子写真および静電印刷などの画像形成方法に用いられる静電荷像を現像するためのトナーおよびトナーの製造方法に関する。 The present invention relates to a toner for developing an electrostatic image used in an image forming method such as electrophotography and electrostatic printing, and a method for producing the toner.
複写機、プリンター、ファクシミリなどに用いられる電子写真技術は発展を続けており、従来以上に高い着色力を有したトナーが注目されている。高着色力トナーにより少ないトナー量で画像形成することで、プリンター本体の小型化、さらには省エネルギー化を達成することが提案されている。しかし、単純に顔料を増量するとトナー中の顔料分散は悪化し、高色域・高着色力の両方を満足するに至らなかった。さらには、多量の顔料を添加することにより、トナー結着樹脂の粘度が増大し、低温定着性の悪化を引き起こした。 The electrophotographic technology used for copiers, printers, facsimiles and the like continues to develop, and toner having higher coloring power than before has been attracting attention. It has been proposed to achieve downsizing and further energy saving of a printer body by forming an image with a small amount of toner using a high coloring power toner. However, simply increasing the amount of pigment deteriorated the pigment dispersion in the toner, and did not satisfy both the high color gamut and the high coloring power. Furthermore, the addition of a large amount of pigment increased the viscosity of the toner binder resin, causing deterioration in low-temperature fixability.
そこで、トナー中の顔料分散を向上させる目的で、顔料に親和性の高い部位と媒体中への分散性を付与するポリマー成分とを有する顔料分散剤が用いられてきた。また、低温定着性を満足するためにはある程度の、離型剤の添加が必須技術となっている。
例えば、トナー用顔料分散剤として、アセトアセトアニリド類の置換体を含むアゾ、またはビスアゾ発色団がポリマーに結合した顔料分散剤を用いた例が開示されている（特許文献１参照）。最近では、トナー結着樹脂と相溶性の高いポリマー成分と芳香族骨格を持った顔料と親和性のある部位有する顔料分散剤が提案されている（特許文献２参照）。
Therefore, for the purpose of improving the pigment dispersion in the toner, a pigment dispersant having a portion having a high affinity for the pigment and a polymer component imparting dispersibility in the medium has been used. In order to satisfy the low-temperature fixability, a certain amount of addition of a release agent has become an essential technique.
For example, as a toner pigment dispersant, an example using a pigment dispersant in which an azo or bisazo chromophore containing a substituted acetoacetanilide is bonded to a polymer is disclosed (see Patent Document 1). Recently, there has been proposed a pigment dispersant having a site having an affinity for a polymer having a high compatibility with a toner binder resin and a pigment having an aromatic skeleton (see Patent Document 2).
しかしながら、これらの先行技術においては近年求められる、高着色力・高色域と低温定着性および耐熱保存性の両立を満足するためには若干の課題を有していることが判った。特許文献１では顔料添加量を増大した際、粉砕トナーの中においては十分な効果を得られるが、水系媒体中で製造されるトナーには十分な顔料分散性が得られなかった。
また、特許文献２では、更なる高着色力化を達成するため、顔料を増やすことで、多量の顔料分散剤を添加しなければ十分な効果が得られず、その結果、結着樹脂と離型剤との相溶性をも高めてしまい、定着分離性に悪影響があることが判った。
However, it has been found that these prior arts have some problems in order to satisfy both of high coloring power / high color gamut, low-temperature fixability and heat-resistant storage stability, which are required in recent years. In Patent Document 1, when the pigment addition amount is increased, a sufficient effect can be obtained in the pulverized toner, but sufficient pigment dispersibility cannot be obtained in a toner manufactured in an aqueous medium.
Further, in Patent Document 2, a sufficient effect cannot be obtained unless a large amount of a pigment dispersant is added by increasing the number of pigments in order to achieve a further increase in coloring power. It was found that the compatibility with the mold agent was also increased, and the fixing separation property was adversely affected.
本発明の目的は、上記課題を解決することにある。すなわち、高着色力・高色域を達成しつつ、定着分離性に優れたトナーを提供すること、及び、トナーの製造方法を提供することにある。 An object of the present invention is to solve the above problems. That is, it is to provide a toner having excellent fixing separation property while achieving high coloring power and high color gamut, and to provide a toner manufacturing method.
本発明は、結着樹脂、顔料、離型剤および顔料分散剤を含有するトナーであって、
前記顔料が、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ３１、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １２２、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １５０およびＣ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ２６９からなる群より選ばれる１種以上の顔料であり、
前記顔料分散剤は、顔料に吸着する吸着成分と、該吸着成分と結合しているポリマー成分とで構成された顔料分散剤であり、
該吸着成分が下記式（１）で表される構造を有することを特徴とするトナーに関する。
The present invention is a toner containing a binder resin, a pigment, a release agent and a pigment dispersant,
The pigment is C.I. I. Pigment Red 31, C.I. I. Pigment Red 122, C.I. I. Pigment Red 150 and C.I. I. One or more pigments selected from the group consisting of Pigment Red 269,
The pigment dispersant, the adsorption component that adsorbs to Pigments, Ri pigment dispersant der comprised of a polymer component which is bound to the adsorption component,
The Rukoto that having a structure in which adsorption component is represented by the following formula (1) relates to a toner which is characterized.
［前記式（１）中、Ａｒ１、Ａｒ２、およびＡｒ３のいずれかは、単結合または連結基を介して、ポリマー成分と結合する部位を示し、
ポリマー成分と結合しないＡｒ１、Ａｒ２、およびＡｒ３は、アリール基を示し、
ポリマー成分と結合するＡｒ１、Ａｒ２、およびＡｒ３は、アリール基から水素を１つ脱離して形成される基を示す。
前記連結基は、アミド基、エステル基、ウレタン基、ウレア基、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ１−および−ＮＨＣＨ（ＣＨ２ＯＨ）−からなる群より選ばれる２価の連結基であり、Ｒ１は、水素原子、アルキル基、フェニル基またはアラルキル基を示す。］
[In the formula (1), any one of Ar 1 , Ar 2 , and Ar 3 represents a site bonded to the polymer component via a single bond or a linking group,
Ar 1 , Ar 2 , and Ar 3 that are not bonded to the polymer component represent an aryl group,
Ar 1 , Ar 2 , and Ar 3 bonded to the polymer component represent a group formed by removing one hydrogen from an aryl group.
The linking group is a divalent linkage selected from the group consisting of an amide group, an ester group, a urethane group, a urea group, an alkylene group, a phenylene group, —O—, —NR 1 —, and —NHCH (CH 2 OH) —. R 1 represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. ]
また、本発明は、結着樹脂、顔料、離型剤および顔料分散剤を含有するトナーの製造方法であって、
前記顔料が、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ３１、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １２２、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １５０およびＣ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ２からなる群より選ばれる１種以上の顔料であり、
前記顔料分散剤は、下記式（１）で表される構造を有する顔料に吸着する吸着成分と、ポリマー成分とで構成された顔料分散剤であり、
ｉ）重合性単量体、顔料と前記一般式（１）の化合物を含有する重合性単量体組成物を、水系媒体中にて造粒し、造粒された粒子中に含有される重合性単量体を重合することによってトナー粒子を得る工程、
または、
ｉｉ）結着樹脂、顔料と前記一般式（１）の化合物を含有するトナー組成物を、有機溶媒中に溶解または分散させた混合溶液を、水系媒体中にて造粒し、造粒された粒子中に含有される有機溶媒を除去することによってトナー粒子を得る工程
を有することを特徴とするトナーの製造方法に関する。
Further, the present invention is a method for producing a toner containing a binder resin, a pigment, a release agent, and a pigment dispersant,
The pigment is C.I. I. Pigment Red 31, C.I. I. Pigment Red 122, C.I. I. Pigment Red 150 and C.I. I. One or more pigments selected from the group consisting of Pigment Red 2;
The pigment dispersant is a pigment dispersant composed of an adsorption component that adsorbs to a pigment having a structure represented by the following formula (1), and a polymer component;
i) Polymerization containing a polymerizable monomer, a pigment and a polymerizable monomer composition containing the compound of the general formula (1) in an aqueous medium, and polymerization contained in the granulated particles. A step of obtaining toner particles by polymerizing a polymerizable monomer,
Or
ii) A mixed solution in which a toner composition containing a binder resin, a pigment and the compound of the general formula (1) was dissolved or dispersed in an organic solvent was granulated in an aqueous medium, and granulated. The present invention relates to a toner production method comprising a step of obtaining toner particles by removing an organic solvent contained in the particles.
本発明によれば、高着色力・高色域を達成しつつ、定着分離性に優れたトナーを得ること、および、該トナーの製造方法を提供することができる。 According to the present invention, it is possible to obtain a toner excellent in fixing separation property while achieving high coloring power and high color gamut, and to provide a method for producing the toner.
本発明者らは、鋭意検討を重ねた結果、以下のトナーによって上記課題を解決できることを見出した。
すなわち、結着樹脂、顔料、離型剤および顔料分散剤を含有するトナーであって、
前記顔料が、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ３１、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １２２、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １５０およびＣ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ２６９からなる群より選ばれる１種以上の顔料であり、前記顔料分散剤は、顔料に吸着する吸着成分と、該吸着成分と結合しているポリマー成分とで構成された顔料分散剤であり、該吸着成分が下記式（１）で表される構造を有することを特徴とするトナーである。
As a result of intensive studies, the present inventors have found that the above problems can be solved by the following toner.
That is, a toner containing a binder resin, a pigment, a release agent, and a pigment dispersant,
The pigment is C.I. I. Pigment Red 31, C.I. I. Pigment Red 122, C.I. I. Pigment Red 150 and C.I. I. Pigment Red 269 is at least one pigment selected from the group consisting of the pigment dispersant, the adsorption component that adsorbs to Pigments, adsorption component bound to that polymer component and the pigment dispersing agent comprised of der is, adsorption component is a toner wherein Rukoto that having a structure represented by the following formula (1).
［前記式（１）中、Ａｒ１、Ａｒ２、およびＡｒ３のいずれかは、単結合または連結基を介して、ポリマー成分と結合する部位を示し、
ポリマー成分と結合しないＡｒ１、Ａｒ２、およびＡｒ３は、アリール基を示し、
ポリマー成分と結合するＡｒ１、Ａｒ２、およびＡｒ３は、アリール基から水素を１つ脱離して形成される基であり、
前記連結基は、アミド基、エステル基、ウレタン基、ウレア基、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ１−および−ＮＨＣＨ（ＣＨ２ＯＨ）−からなる群より選ばれる２価の連結基であり、Ｒ１は、水素原子、アルキル基、フェニル基またはアラルキル基を示す。］
[In the formula (1), any one of Ar 1 , Ar 2 , and Ar 3 represents a site bonded to the polymer component via a single bond or a linking group,
Ar 1 , Ar 2 , and Ar 3 that are not bonded to the polymer component represent an aryl group,
Ar 1 , Ar 2 , and Ar 3 bonded to the polymer component are groups formed by removing one hydrogen from an aryl group,
The linking group is a divalent linkage selected from the group consisting of an amide group, an ester group, a urethane group, a urea group, an alkylene group, a phenylene group, —O—, —NR 1 —, and —NHCH (CH 2 OH) —. R 1 represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. ]
本発明の効果について得られた、真因は不明ではあるが本発明者らは以下のような理由で、本発明の効果が得られていると考えている。
本発明で示すような顔料分散剤は、顔料に吸着する吸着部位と結着樹脂中に分散するポリマー成分により構成されている。この、吸着部位が顔料に吸着する機構は顔料の表面との相互作用性に大きく作用される。相互作用の種類として、吸着部位の平面性に起因するπ-π結合と吸着部位の極性に起因する水素結合による相互作用があると考えている。また、組成や結晶型など顔料のもつ特有の構造によって、どの様な相互作用が大きく作用するかが異なってきていると考えている。そのため、π‐π結合と水素結合の両方の相互作用性を有することで優れた顔料吸着性を得ることが可能になっていると考えている。このような、高い吸着性を有する吸着成分を有するポリマーを用いることで、高い顔料分散性を示し高着色力・高色域を達成できていると考えている。
Although the true cause obtained for the effect of the present invention is unknown, the present inventors consider that the effect of the present invention is obtained for the following reason.
The pigment dispersant as shown in the present invention is composed of an adsorption site adsorbed on the pigment and a polymer component dispersed in the binder resin. This mechanism by which the adsorption site adsorbs to the pigment is greatly influenced by the interaction with the surface of the pigment. It is thought that there is an interaction between the π-π bond resulting from the planarity of the adsorption site and the hydrogen bond resulting from the polarity of the adsorption site as the kind of interaction. In addition, it is considered that what kind of interaction greatly acts depends on the specific structure of the pigment such as composition and crystal type. For this reason, it is considered that it is possible to obtain excellent pigment adsorbability by having both π-π bond and hydrogen bond interactions. By using such a polymer having an adsorptive component having a high adsorptivity, it is considered that a high pigment dispersibility and a high coloring power and a high color gamut can be achieved.
また、本発明の顔料分散剤を用いた場合、定着分離性が大きく向上することが判った。これは、本発明の顔料分散剤は顔料を分散した顔料分散体の粘度を低下する効果が優れていることに由来すると考えている。そのため、この顔料分散体を結着樹脂に用いることで、結着樹脂と離型剤の分離性が良化すると推定している。その結果、定着時に離型剤の定着表面への染み出しが良化して、定着分離性が向上したと考えている。 Further, it has been found that when the pigment dispersant of the present invention is used, the fixing separation property is greatly improved. This is considered to be because the pigment dispersant of the present invention is excellent in the effect of reducing the viscosity of the pigment dispersion in which the pigment is dispersed. For this reason, it is presumed that the use of this pigment dispersion for the binder resin improves the separability of the binder resin and the release agent. As a result, it is considered that the seepage of the release agent to the fixing surface at the time of fixing is improved and the fixing separation property is improved.
次に、本発明の吸着成分について説明する。本発明の一般式（１）で示される吸着成分は、以下のような平衡状態を取りうると考えている。 Next, the adsorption component of the present invention will be described. It is considered that the adsorption component represented by the general formula (1) of the present invention can take the following equilibrium state.
上記構造中のアリール基および不飽和結合があることによって、本発明の吸着成分の分子の平面性を高め強いπ―π結合性を示し、式（１）、式（１−ａ）および式（１−ｂ）のような構造を取ることで強い水素結合性を示すと考えている。その結果、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ３１、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １２２、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １５０およびＣ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ２６９のような顔料に特異的に高い吸着性を得ることができていると考えている。 The presence of an aryl group and an unsaturated bond in the above structure increases the planarity of the molecule of the adsorption component of the present invention and exhibits strong π-π bondability. It is considered that a strong hydrogen bonding property is exhibited by taking a structure such as 1-b). As a result, C.I. I. Pigment Red 31, C.I. I. Pigment Red 122, C.I. I. Pigment Red 150 and C.I. I. It is considered that the pigment such as Pigment Red 269 can obtain a high adsorptivity specifically.
前記式（１）中、Ａｒ１、Ａｒ２、およびＡｒ３のいずれかが連結基を介して、ポリマー成分と結合する場合は、２価の連結基であれば特に限定されない。製造の容易性の観点から、ポリマー成分のカルボキシル基と、カルボン酸エステル結合もしくはカルボン酸アミド結合を介して結合することが好ましい。
前記式（１）の吸着成分が、下記式（２）で示される吸着成分であることが好ましい。
In Formula (1), when any of Ar 1 , Ar 2 , and Ar 3 is bonded to the polymer component via a linking group, there is no particular limitation as long as it is a divalent linking group. From the viewpoint of ease of production, it is preferable to bond the carboxyl group of the polymer component via a carboxylic acid ester bond or a carboxylic acid amide bond.
The adsorption component represented by the formula (1) is preferably an adsorption component represented by the following formula (2).
［前記式（２）中、Ｒ２〜Ｒ１１は、それぞれ独立して、水素原子、ＣＯＯＲ１２基、またはＣＯＮＲ１３Ｒ１４基を示す。Ｒ１２〜Ｒ１４は、それぞれ独立して、水素原子、アルキル基、フェニル基、またはアラルキル基を示す。前記式（２）中Ｌ１は連結基であり、アミド基、エステル基、ウレタン基、ウレア基、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ１−および−ＮＨＣＨ（ＣＨ２ＯＨ）−からなる群より選ばれる２価の連結基であり、Ｒ１は、水素原子、アルキル基、フェニル基またはアラルキル基を示す。］ [In the formula (2), R 2 to R 11 each independently represent a hydrogen atom, a COOR 12 group, or a CONR 13 R 14 group. R 12 to R 14 each independently represent a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group. In Formula (2), L 1 is a linking group, and includes an amide group, an ester group, a urethane group, a urea group, an alkylene group, a phenylene group, —O—, —NR 1 —, and —NHCH (CH 2 OH) —. And R 1 represents a hydrogen atom, an alkyl group, a phenyl group, or an aralkyl group. ]
これは、前記式（２）中、Ｒ２〜Ｒ１１の置換基の選択により、不飽和結合部の安定性、ひいてはアセトアセトアニリド部位の安定性を制御することができる。その結果、π-π結合性と水素結合性の強さを制御できる。そのため、吸着成分の結合性に影響が少ない、ポリマー成分との結合する連結基Ｌ１は式（２）の位置であることが好ましい。
また、上記式（２）中、連結基Ｌ１の置換位置はアゾ結合位置に対して、ｏ−位、ｍ−位、ｐ−位で置換した場合が挙げられる。これらの置換位置の違いによる顔料と吸着成分の親和性は、ｏ−位、ｍ−位、ｐ−位で同等である
In the formula (2), this can control the stability of the unsaturated bond portion, and hence the stability of the acetoacetanilide moiety, by selecting the substituents R 2 to R 11 . As a result, the strength of π-π bondability and hydrogen bondability can be controlled. Therefore, the linking group L 1 that binds to the polymer component that has little influence on the binding property of the adsorbing component is preferably at the position of the formula (2).
Further, in the above formula (2), the linking group L 1 may be substituted at the o-position, m-position, or p-position with respect to the azo bond position. The affinity of the pigment and the adsorbing component due to the difference in these substitution positions is the same at the o-position, m-position and p-position.
しかし、吸着成分とポリマー成分が連結した顔料分散剤を形成した場合、連結基Ｌ１の置換位置はアゾ結合位置に対して、ｍ−位およびｐ−位である場合は、ｏ−位である場合と比較して立体的な障害が少ないため顔料分散剤を得やすい。そのため、連結基Ｌ１の置換位置はアゾ結合位置に対してｍ−位およびｐ−位の方が好ましい。
また、π-π結合性をより高める観点から、吸着成分として一般式（３）で示される、吸着成分を含むことが好ましい。
However, when a pigment dispersant in which the adsorbing component and the polymer component are linked is formed, the substitution position of the linking group L 1 is the o-position when it is in the m-position and p-position with respect to the azo bond position. Since there are few steric obstacles compared with the case, it is easy to obtain a pigment dispersant. Therefore, the substitution position of the linking group L 1 is preferably the m-position and the p-position with respect to the azo bond position.
Moreover, it is preferable to contain the adsorption component shown by General formula (3) as an adsorption component from a viewpoint of improving (pi) -pi bondability more.
［前記式（３）中、Ａｒ４およびＡｒ５は、アリール基を示し、Ａｒ６はアリール基から水素を１つ脱離して形成される連結基Ｌ２を介して、前記ポリマー成分と結合する部位を示し、前記連結基Ｌ２は、アミド基、エステル基、ウレタン基、ウレア基、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ１５−および−ＮＨＣＨ（ＣＨ２ＯＨ）−からなる群より選ばれる２価の連結基であり、Ｒ１５は、水素原子、アルキル基、フェニル基またはアラルキル基を示す。Ｗは、−ＣＨ２−または＞Ｃ＝ＣＨ-Ａｒ７を表しＡｒ７はアリール基を示す。］ [In the formula (3), Ar 4 and Ar 5 represent an aryl group, and Ar 6 is bonded to the polymer component via a linking group L 2 formed by removing one hydrogen from the aryl group. The linking group L 2 is selected from the group consisting of an amide group, an ester group, a urethane group, a urea group, an alkylene group, a phenylene group, —O—, —NR 15 —, and —NHCH (CH 2 OH) —. R 15 is a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. W represents —CH 2 — or> C═CH—Ar 7, and Ar 7 represents an aryl group. ]
前記式（３）は、前記式（１）および式（２）よりも平面性が高く、優れたπ-π結合性を示す。また、Ａｒ４およびＡｒ５は置換基有の影響を受けにくいため分子の平面性が高い。そのため、式（１）および式（２）を水素結合性に優れた吸着成分を用いた場合などに、式（３）の吸着成分を用いることは顔料分散剤の効果を高めるために有効である。上記式（３）中、連結基Ｌ２の置換位置はピリダジン系誘導体との結合位置に対して、ｏ−位、ｍ−位、ｐ−位で置換した場合が挙げられる。これらの置換位置の違いによる顔料との親和性は、ｏ−位、ｍ−位、ｐ−位で同等である。
しかし、吸着成分とポリマー成分が連結した顔料分散剤を形成した場合、連結基Ｌ１の置換位置はアゾ結合位置に対して、ｍ−位およびｐ−位である場合は、ｏ−位である場合と比較して立体的な障害が少ないため顔料分散剤を得やすい。そのため、連結基Ｌ１の置換位置はアゾ結合位置に対してｍ−位およびｐ−位の方が好ましい。
The formula (3) has higher planarity than the formulas (1) and (2), and exhibits excellent π-π bondability. Moreover, since Ar 4 and Ar 5 are not easily affected by the presence of substituents, the planarity of the molecule is high. Therefore, when the adsorption component excellent in hydrogen bondability is used in the formulas (1) and (2), the use of the adsorption component of the formula (3) is effective for enhancing the effect of the pigment dispersant. . In the above formula (3), the linking group L 2 may be substituted at the o-position, m-position, or p-position with respect to the position of bonding with the pyridazine derivative. The affinity with the pigment due to the difference in these substitution positions is the same in the o-position, m-position and p-position.
However, when a pigment dispersant in which the adsorbing component and the polymer component are linked is formed, the substitution position of the linking group L 1 is the o-position when it is in the m-position and p-position with respect to the azo bond position. Since there are few steric obstacles compared with the case, it is easy to obtain a pigment dispersant. Therefore, the substitution position of the linking group L 1 is preferably the m-position and the p-position with respect to the azo bond position.
また、前記顔料分散剤に含まれる前記式（２）の吸着成分のモル数Ａ、前記式（３）のモル数Ｂとしたとき、Ａのモル分率Ａ／（Ａ＋Ｂ）は０．２以上０．８以下であることが好ましい。
０．２以上０．８以下の範囲であれば、前記式（２）単独の顔料分散剤の分散性よりも特に優れた効果が得られた。これは、上記範囲であれば、π−π結合性と水素結合性の相互作用のバランスに優れているためと考えている。
Further, when the mole number A of the adsorption component of the formula (2) contained in the pigment dispersant and the mole number B of the formula (3) are set, the mole fraction A / (A + B) of A is 0.2 or more. It is preferable that it is 0.8 or less.
In the range of 0.2 or more and 0.8 or less, an effect particularly superior to the dispersibility of the pigment dispersant of the formula (2) alone was obtained. This is considered to be because the balance of the interaction between π-π bondability and hydrogen bondability is excellent within the above range.
次に、顔料分散剤の構造について説明する。
前記ポリマー成分のサイズ排除クロマトグラフを用いて測定された数平均分子量が、３０００以上３００００以下であることが好ましい。３０００以上であれば、結着樹脂との相溶性がより優れるため、顔料分散性が向上する。また３００００以下である場合には、結着樹脂から離型剤を分離させやすくなり、定着分離性が良化する。
Next, the structure of the pigment dispersant will be described.
It is preferable that the number average molecular weight measured using the size exclusion chromatograph of the polymer component is 3000 or more and 30000 or less. If it is 3000 or more, since it is more compatible with the binder resin, the pigment dispersibility is improved. On the other hand, when it is 30000 or less, it becomes easy to separate the release agent from the binder resin, and the fixing separation property is improved.
また、顔料分散剤と結着樹脂の相溶性をさらに増す観点から、前記結着樹脂がビニル樹脂を含有する場合はポリマー成分がビニル樹脂を含有し、前記結着樹脂がポリエステル樹脂を含有する場合は、ポリマー成分がポリエステル樹脂を含有することが好ましい。
前記顔料分散剤中の吸着成分の位置は、ポリマー成分に対してランダムに点在していても、一端に１つもしくは複数のブロックを形成して偏在していてもよい。
前記顔料分散剤の１分子当りの吸着成分の個数が１以上６以下であることが好ましい。前記顔料分散剤中の吸着成分の数は、顔料分散剤一分子当り１以上あれば良いが、多すぎると非水溶性溶剤への親和性が悪化するため好ましくない。
From the viewpoint of further increasing the compatibility between the pigment dispersant and the binder resin, when the binder resin contains a vinyl resin, the polymer component contains a vinyl resin, and the binder resin contains a polyester resin. The polymer component preferably contains a polyester resin.
The position of the adsorption component in the pigment dispersant may be randomly scattered with respect to the polymer component, or may be unevenly distributed by forming one or more blocks at one end.
The number of adsorbing components per molecule of the pigment dispersant is preferably 1 or more and 6 or less. The number of adsorbing components in the pigment dispersant may be 1 or more per molecule of the pigment dispersant. However, if the amount is too large, the affinity for the water-insoluble solvent deteriorates.
本発明に係わるトナーに使用可能な離型剤成分としては、パラフィンワックス、マイクロクリスタリンワックス、ペトロラタムなどの石油系ワックスおよびその誘導体、モンタンワックスおよびその誘導体、フィッシャートロプシュ法による炭化水素系ワックスおよびその誘導体、ポリエチレン、ポリプロピレンなどのポリオレフィンワックスおよびその誘導体、カルナバワックス、キャンデリラワックスなどの天然ワックスおよびその誘導体高級脂肪族アルコール、ステアリン酸、パルミチン酸などの脂肪酸、あるいはその化合物、酸アミドワックス、エステルワックス、ケトン、硬化ヒマシ油およびその誘導体、植物系ワックス、動物性ワックス、シリコ−ン樹脂が挙げられる。
さらに、この中でもトナーを造粒する上で、ワックスの融点は５０℃以上１１０℃以下の範囲であることが好ましい。
Examples of the release agent component usable in the toner according to the present invention include petroleum wax such as paraffin wax, microcrystalline wax, and petrolatum and derivatives thereof, montan wax and derivatives thereof, and hydrocarbon waxes and derivatives thereof according to the Fischer-Tropsch method. , Polyolefin waxes such as polyethylene and polypropylene and derivatives thereof, natural waxes and derivatives thereof such as carnauba wax and candelilla wax, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, Examples include ketones, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes, and silicone resins.
Further, among them, the wax preferably has a melting point in the range of 50 ° C. or higher and 110 ° C. or lower when the toner is granulated.
さらに、定着分離性を良化するため、離型剤のトナーの表面への染み出しを良化することが適当であると考えられる。しかし、顔料分散剤は顔料と結着樹脂の相溶性のみならず、結着樹脂と極性を持った離型剤の相溶性をも高めてしまう為、定着分離性を悪化させてしまう。このような観点から、より極性の小さい炭化水素系ワックスを用いることが好ましい。特に、優れた効果を発現するために、上記融点範囲の炭化水素系ワックスが挙げられる。 Further, in order to improve the fixing and separating property, it is considered appropriate to improve the exudation of the release agent to the toner surface. However, the pigment dispersant increases not only the compatibility between the pigment and the binder resin, but also the compatibility between the binder resin and the release agent having polarity, so that the fixing separation property is deteriorated. From such a viewpoint, it is preferable to use a hydrocarbon wax having a smaller polarity. In particular, in order to express an excellent effect, a hydrocarbon wax having the above melting point range is exemplified.
次に、本発明のトナーの結着樹脂について説明する。本発明のトナーの結着樹脂としては、一般的に用いられているスチレン−メタクリル酸共重合体、スチレン−アクリル酸共重合体、ポリエステル樹脂、エポキシ樹脂、スチレン−ブタジエン共重合体が挙げられる。重合法により直接トナー粒子を得る方法においては、それらを形成するための単量体が用いられる。
これらは、単独、または理論ガラス転移温度（Ｔｇ）が、４０℃〜７５℃の範囲を示すように単量体を適宜混合して用いられる。理論ガラス転移温度が４０℃以上の場合にはトナーの保存安定性や耐久安定性の面から問題が生じにくく、一方７５℃以下の場合はトナーのフルカラー画像形成の場合において透明性が低下しにくい。
本発明のトナーにおける結着樹脂は、ポリスチレンなどの非極性樹脂にポリエステル樹脂やポリカーボネート樹脂などの極性樹脂を併用して用いることで、着色剤や電荷制御剤、ワックスなどの添加剤のトナー内分布を制御することができる。例えば、懸濁重合法などにより直接トナー粒子を製造する場合には、分散工程から重合工程に至る重合反応時に前記極性樹脂を添加する。
前記極性樹脂は、トナー粒子となる単量体単位組成物と水系媒体の極性のバランスに応じて添加する。その結果、前記極性樹脂がトナー粒子の表面に薄層を形成するなど、トナー粒子の表面から中心に向けその樹脂濃度が連続的に変化するように制御することができる。このとき、上記化合物を有する化合物、着色剤および電荷制御剤と相互作用を有するような極性樹脂を用いることによって、トナー粒子中への着色剤の存在状態を好ましい形態にすることが可能である。
Next, the toner binder resin of the present invention will be described. Examples of the binder resin of the toner of the present invention include commonly used styrene-methacrylic acid copolymers, styrene-acrylic acid copolymers, polyester resins, epoxy resins, and styrene-butadiene copolymers. In a method for directly obtaining toner particles by a polymerization method, a monomer for forming them is used.
These are used alone or by appropriately mixing monomers so that the theoretical glass transition temperature (Tg) is in the range of 40 ° C to 75 ° C. When the theoretical glass transition temperature is 40 ° C. or higher, there is little problem in terms of storage stability and durability stability of the toner, while when it is 75 ° C. or lower, the transparency is not easily lowered in the case of toner full color image formation. .
The binder resin in the toner of the present invention uses a nonpolar resin such as polystyrene in combination with a polar resin such as a polyester resin or a polycarbonate resin, so that the distribution of additives such as colorants, charge control agents, and waxes in the toner is distributed. Can be controlled. For example, when the toner particles are directly produced by suspension polymerization or the like, the polar resin is added during the polymerization reaction from the dispersion step to the polymerization step.
The polar resin is added according to the balance of the polarities of the monomer unit composition serving as toner particles and the aqueous medium. As a result, the resin concentration can be controlled to change continuously from the surface of the toner particle toward the center, for example, the polar resin forms a thin layer on the surface of the toner particle. At this time, the presence of the colorant in the toner particles can be brought into a preferred form by using a polar resin that interacts with the compound having the above compound, the colorant, and the charge control agent.
次に、本発明のトナーの着色剤について説明する。本発明の着色剤として、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ３１、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １２２、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １５０およびＣ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ２６９の群から一種以上選ばれる顔料を含んでいればよい。また、調色するために、前記群より選ばれる顔料およびまたは他の着色剤を併用しても良い。
本発明のトナーにおいて、前記化合物と顔料との好ましい重量組成比は０．１：１００〜３０：１００、さらに好ましくは０．５：１００〜１５：１００の範囲である。上記範囲であれば、優れた顔料分散性を得ることができる。
Next, the colorant of the toner of the present invention will be described. As the colorant of the present invention, C.I. I. Pigment Red 31, C.I. I. Pigment Red 122, C.I. I. Pigment Red 150 and C.I. I. Pigment Red 269 may be used as long as it contains at least one pigment selected from the group of Pigment Red 269. In order to adjust the color, a pigment selected from the above group and / or another colorant may be used in combination.
In the toner of the present invention, the preferred weight composition ratio of the compound and the pigment is in the range of 0.1: 100 to 30: 100, more preferably 0.5: 100 to 15: 100. Within the above range, excellent pigment dispersibility can be obtained.
上記式（１）、式（２）および式（３）の化合物は、公知の方法にしたがって合成することができる。例えば、上記化合物を合成する具体的な方法としては、まず、アセチルアセトン誘導体とアミノフェノールなどから得られるジアゾニウム塩との反応により中間体１を得る。この中間体１と、ベンズアルデヒド類との反応より吸着成分となる中間体２が得られる。この中間体２とポリマー成分との連結を行うことで、上記式（１）および式（２）の化合物を得ることが可能である。
また、中間体１と、ベンズアルデヒド類との反応より吸着成分となる中間体２との反応条件によっては、上記式（３）の化合物の吸着成分となる中間体３も同時に合成される。この中間体３と同様にポリマー成分と連結させることによって、上記式（３）の化合物を得ることが可能である。
The compounds of formula (1), formula (2) and formula (3) can be synthesized according to known methods. For example, as a specific method for synthesizing the above compound, first, intermediate 1 is obtained by a reaction between an acetylacetone derivative and a diazonium salt obtained from aminophenol or the like. The intermediate 2 which becomes an adsorbing component is obtained by the reaction between the intermediate 1 and benzaldehydes. By connecting the intermediate 2 and the polymer component, it is possible to obtain the compounds of the above formulas (1) and (2).
Depending on the reaction conditions of intermediate 1 and intermediate 2 which becomes an adsorbing component from the reaction with benzaldehydes, intermediate 3 which is an adsorbing component of the compound of formula (3) is also synthesized at the same time. It is possible to obtain the compound of the above formula (3) by linking with a polymer component in the same manner as this intermediate 3.
次に本発明のトナーの製造方法について説明する。
結着樹脂、顔料、離型剤および顔料分散剤を含有するトナーの製造方法であって、
前記顔料が、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ３１、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １２２、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １５０およびＣ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ２からなる群より選ばれる１種以上の顔料であり、
前記顔料分散剤は、前記式（１）で示される構造を有する顔料に吸着する吸着成分と、ポリマー成分とで構成された顔料分散剤であり、
ｉ）重合性単量体、顔料と前記式（１）の化合物を含有する重合性単量体組成物を、水系媒体中にて造粒し、造粒された粒子中に含有される重合性単量体を重合することによってトナー粒子を得る工程、
または
ｉｉ）結着樹脂、顔料と前記式（１）の化合物を含有するトナー組成物を、有機溶媒中に溶解または分散させた混合溶液を、水系媒体中にて造粒し、造粒された粒子中に含有される有機溶媒を除去することによってトナー粒子を得る工程
を有することを特徴とするトナーの製造方法である。
Next, a method for producing the toner of the present invention will be described.
A method for producing a toner containing a binder resin, a pigment, a release agent, and a pigment dispersant,
The pigment is C.I. I. Pigment Red 31, C.I. I. Pigment Red 122, C.I. I. Pigment Red 150 and C.I. I. One or more pigments selected from the group consisting of Pigment Red 2;
The pigment dispersant is a pigment dispersant composed of an adsorption component that adsorbs to the pigment having the structure represented by the formula (1), and a polymer component;
i) A polymerizable monomer, a pigment and a polymerizable monomer composition containing the compound of the formula (1) are granulated in an aqueous medium, and the polymerizability contained in the granulated particles. Obtaining toner particles by polymerizing monomers;
Or ii) A mixed solution in which a toner composition containing a binder resin, a pigment, and the compound of the formula (1) is dissolved or dispersed in an organic solvent is granulated in an aqueous medium and granulated. A toner production method comprising a step of obtaining toner particles by removing an organic solvent contained in the particles.
本発明の顔料分散剤は有機溶媒中において顔料を分散するものにおいて、優れた効果を発揮するものである。そのため、上記ｉ）またはｉｉ）の製造方法によって、得られるトナーによって優れた効果を発揮するものである。
また、前記トナーの製造方法が、ｉ）の方法であって、
前記ポリマー成分が、下記式（４）で示される単量体単位を含むポリマー成分であることが好ましい。
The pigment dispersant of the present invention exhibits an excellent effect in dispersing a pigment in an organic solvent. Therefore, the toner obtained by the method i) or ii) exhibits an excellent effect.
The toner production method is the method i),
The polymer component is preferably a polymer component containing a monomer unit represented by the following formula (4).
上記単量体成分を用いることで、顔料分散性と定着時の定着分離性がさらに優れたものを得ることができる。
By using the monomer component, it is possible to obtain a pigment having excellent pigment dispersibility and fixing separation at the time of fixing.
次に本発明を、実施例を挙げてさらに具体的に説明するが、本発明はこれらに限定されない。なお、文中の「部」および「％」は特に断りのない限り質量基準である。
以下に本実施例で用いられる測定方法について示す。
EXAMPLES Next, although an Example is given and this invention is demonstrated further more concretely, this invention is not limited to these. In the text, “part” and “%” are based on mass unless otherwise specified.
The measurement method used in this example will be described below.
（１）分子量測定
本実施例におけるポリマー成分、吸着成分および顔料分散剤の分子量は、サイズ排除クロマトグラフィー（ＳＥＣ）によって、ポリスチレン換算で算出される。ＳＥＣによる分子量の測定は以下に示すように行った。サンプル濃度が１．０質量％になるようにサンプルを下記溶離液に加え、室温で２４時間静置した溶液を、ポア径が０．２μｍの耐溶剤性メンブレンフィルターで濾過したものをサンプル溶液とし、以下の条件で測定した。
(1) Molecular weight measurement The molecular weights of the polymer component, the adsorbing component and the pigment dispersant in this example are calculated in terms of polystyrene by size exclusion chromatography (SEC). Measurement of molecular weight by SEC was performed as follows. The sample was added to the eluent below so that the sample concentration was 1.0% by mass, and the solution that was allowed to stand at room temperature for 24 hours was filtered through a solvent-resistant membrane filter with a pore diameter of 0.2 μm as the sample solution. The measurement was performed under the following conditions.
また、試料の分子量の算出にあたっては、標準ポリスチレン樹脂［東ソー（株）製ＴＳＫスタンダード ポリスチレン Ｆ−８５０、Ｆ−４５０、Ｆ−２８８、Ｆ−１２８、Ｆ−８０、Ｆ−４０、Ｆ−２０、Ｆ−１０、Ｆ−４、Ｆ−２、Ｆ−１、Ａ−５０００、Ａ−２５００、Ａ−１０００、Ａ−５００］により作成した分子量校正曲線を使用した。 In calculating the molecular weight of the sample, standard polystyrene resin [TSO Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, manufactured by Tosoh Corporation] F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500] were used.
（２）組成分析
本実施例におけるポリマー成分、吸着成分および顔料分散剤の構造決定は以下の装置を用いて行った。
ブルカー社製ＦＴ−ＮＭＲ ＡＶＡＮＣＥ−６００（使用溶剤 重クロロホルム）
なお、１３Ｃ ＮＭＲはクロム（ＩＩＩ）アセチルアセトナートを緩和試薬として用いた逆ゲートデカップリング法により定量化し組成分析を行った。
(2) Composition analysis The structure of the polymer component, the adsorbing component and the pigment dispersant in this example was determined using the following apparatus.
FT-NMR AVANCE-600 manufactured by Bruker (solvent heavy chloroform)
13 C NMR was quantified by a reverse gate decoupling method using chromium (III) acetylacetonate as a relaxation reagent and subjected to composition analysis.
（３）顔料分散剤中のポリマー成分の数平均分子量算出
本実施例の顔料分散剤中のポリマー成分の数平均分子量Ｍｎｐは以下の手順により算出した。まず、上記手法に基づき顔料分散剤の吸着基の組成式、顔料分散剤中の個数Ｎおよび顔料分散剤の数平均分子量Ｍｎを決定した。次に、顔料分散剤の吸着成分の組成式より吸着成分の分子量ｍを決定した。そして、下記式に示すように、顔料分散剤の数平均分子量Ｍｎから、吸着成分の分子量ｍと吸着成分の個数Ｎとを掛けた値を減じて算出した。
Ｍｎｐ（ポリマー成分の分子量）＝Ｍｎ（顔料分散剤の分子量）-［ｍ（吸着成分の分子量）×Ｎ（顔料分散剤中の吸着成分の個数）］
(3) Calculation of number average molecular weight of polymer component in pigment dispersant The number average molecular weight Mn p of the polymer component in the pigment dispersant of this example was calculated according to the following procedure. First, the composition formula of the adsorption group of the pigment dispersant, the number N in the pigment dispersant, and the number average molecular weight Mn of the pigment dispersant were determined based on the above method. Next, the molecular weight m of the adsorbing component was determined from the composition formula of the adsorbing component of the pigment dispersant. Then, as shown in the following formula, the value was calculated by subtracting the value obtained by multiplying the number average molecular weight Mn of the pigment dispersant by the molecular weight m of the adsorbing component and the number N of the adsorbing component.
Mn p (molecular weight of polymer component) = Mn (molecular weight of pigment dispersant) − [m (molecular weight of adsorption component) × N (number of adsorption components in pigment dispersant)]
下記のようにして合成して本実施例で規定した構造の化合物を得たが、得られた中間体、アセチルアセトン誘導体の分子構造は、ＮＭＲ（核磁気共鳴装置、ＥＣＡ４００、日本電子（株）製）を使用して確認した。 The compound having the structure defined in this example was obtained by synthesis as described below, and the molecular structure of the obtained intermediate and acetylacetone derivative was NMR (nuclear magnetic resonance apparatus, ECA400, manufactured by JEOL Ltd.). ).
＜吸着成分Ａ−１の製造方法＞
以下のスキームにしたがい吸着成分Ａ−１を得た。
<Method for Producing Adsorption Component A-1>
Adsorption component A-1 was obtained according to the following scheme.
まず、４−アミノフェノール１１．０部（０．１００モル）に希塩酸１４０部を加えて温度５℃以下に冷却した。この溶液に、１９．０％−亜硝酸ナトリウム水溶液３７．０部（０．１００モル）を氷冷しながら滴下し、ジアゾニウム塩溶液を調製した。次に、アセチルアセトン１０．０部（０．１００モル）に、エタノール２３７部、および３６．５％−酢酸ナトリウム水溶液１２６部（０．５６０モル）を加えて攪拌し、温度５℃以下に冷却した。
この溶液に、先程調製したジアゾニウム塩溶液をゆっくり滴下し、氷冷下で３０分、さらに室温で１時間撹拌した。その後、生成した析出物を濾取し、水洗、乾燥して中間体ａを得た（収率９８％）。
First, 140 parts of dilute hydrochloric acid was added to 11.0 parts (0.100 mol) of 4-aminophenol and cooled to a temperature of 5 ° C. or lower. To this solution, 37.0 parts (0.100 mol) of a 19.0% aqueous sodium nitrite solution was added dropwise with ice cooling to prepare a diazonium salt solution. Next, 237 parts of ethanol and 126 parts (0.560 mol) of 36.5% -sodium acetate aqueous solution were added to 10.0 parts (0.100 mol) of acetylacetone and stirred, and the temperature was cooled to 5 ° C. or lower. .
The diazonium salt solution prepared earlier was slowly added dropwise to this solution, and the mixture was stirred for 30 minutes under ice-cooling and further for 1 hour at room temperature. Thereafter, the produced precipitate was collected by filtration, washed with water and dried to obtain an intermediate a (yield 98%).
上記で得た中間体ａの１５．６部（０．０７０モル）を、メタノール８０．６部に溶解し、さらに２Ｎ−水酸化ナトリウム水溶液８６．０部を加えて温度５℃以下に冷却した。この溶液に、ベンズアルデヒドを３０．５部（０．２９０モル）とエタノール２０．５部を混合したものを滴下し、氷冷下で３時間反応させた後、冷蔵庫で一晩静置した。静置後、反応液を冷水５００部に投入して、酢酸で中和し、生成した析出物を分取して、シリカゲルカラムクロマトグラフィーを用いて精製し、吸着成分Ａ−１を得た（収率８６％）。表２に吸着成分Ａ−１の構造を示す。 15.6 parts (0.070 mol) of the intermediate a obtained above was dissolved in 80.6 parts of methanol, and further 86.0 parts of 2N sodium hydroxide aqueous solution was added and cooled to a temperature of 5 ° C. or lower. . To this solution, a mixture of 30.5 parts (0.290 mol) of benzaldehyde and 20.5 parts of ethanol was added dropwise, reacted for 3 hours under ice cooling, and then allowed to stand overnight in a refrigerator. After standing, the reaction solution was poured into 500 parts of cold water, neutralized with acetic acid, the produced precipitate was collected and purified using silica gel column chromatography to obtain an adsorbing component A-1 ( Yield 86%). Table 2 shows the structure of the adsorption component A-1.
＜吸着成分Ａ−２の製造方法＞
以下のスキームにしたがい吸着成分Ａ−２を得た。
<Method for producing adsorption component A-2>
Adsorption component A-2 was obtained according to the following scheme.
上記で得た吸着成分Ａ−１の１４．４部（０．０４０モル）を、ピリジン１７０部に溶解した後、温度５℃以下に冷却した。この溶液に、メタクリロイルクロリド４．２１部（０．０４０モル）をピリジン３０．０部に溶解したものを滴下して１時間撹拌した。その後、水２００部を添加して反応を停止させ、クロロホルムによる抽出、水洗および濃縮を行なって、吸着成分Ａ−２を得た（収率９０％）。表２に吸着成分Ａ−２の構造を示す。 After 14.4 parts (0.040 mol) of the adsorption component A-1 obtained above was dissolved in 170 parts of pyridine, the temperature was cooled to 5 ° C. or lower. To this solution, 4.21 parts (0.040 mol) of methacryloyl chloride dissolved in 30.0 parts of pyridine was added dropwise and stirred for 1 hour. Thereafter, 200 parts of water was added to stop the reaction, and extraction with chloroform, washing with water and concentration were performed to obtain an adsorbing component A-2 (yield 90%). Table 2 shows the structure of the adsorption component A-2.
＜吸着成分Ａ−３の製造方法＞
以下のスキームにしたがい、吸着成分Ａ−１の製造方法において、４-ヒドロキシアニリンを用いたところをアニリンに代えて中間体ｂ−１を得て、ベンズアルデヒドを用いたところを４-ヒドロキシベンズアルデヒドに代えて中間体ｂ−２を得た。そして、中間体ａを用いたところを中間体ｂ−２に代えて、メタクリロイルクロリド（０．０４０モル）を用いたところをアクリロイルクロリド（０．０８０モル）に代えた以外は、吸着成分Ａ−２の製造方法と同様にして吸着成分Ａ−３を得た。
<Method for producing adsorption component A-3>
According to the following scheme, in the production method of the adsorbing component A-1, an intermediate b-1 was obtained by replacing aniline with 4-hydroxyaniline and replacing with 4-hydroxybenzaldehyde with benzaldehyde. Intermediate b-2 was obtained. And the place where intermediate a was used was changed to intermediate b-2, and the place where methacryloyl chloride (0.040 mol) was used was changed to acryloyl chloride (0.080 mol), adsorbing component A- Adsorption component A-3 was obtained in the same manner as in Production Method 2.
＜吸着成分Ａ−４の製造方法＞
以下のスキームにしたがって吸着成分Ａ−４を得た。
<Method for Producing Adsorption Component A-4>
Adsorption component A-4 was obtained according to the following scheme.
まず、４−アミノフェノールの代わりに４−ニトロアニリンを用いた以外は、吸着成分Ａ-１の製造方法と同様にして、中間体ｃ-２を得た。次に、Ｎ，Ｎ−ジメチルホルムアミド１５０部に中間体ｃ−２を７.５部およびパラジウム−活性炭素（パラジウム５％）を０．４部加えて、水素ガス雰囲気下（反応圧力０．１〜０．４ＭＰａ）、温度４０℃で３時間撹拌した。反応終了後、溶液を濾別し、濃縮して吸着成分Ａ-４を得た。
表２に吸着成分Ａ−４の構造を示す。
First, an intermediate c-2 was obtained in the same manner as in the production method of the adsorption component A-1, except that 4-nitroaniline was used instead of 4-aminophenol. Next, 7.5 parts of intermediate c-2 and 0.4 part of palladium-activated carbon (palladium 5%) were added to 150 parts of N, N-dimethylformamide, and the reaction was performed under a hydrogen gas atmosphere (reaction pressure 0.1). And stirred at a temperature of 40 ° C. for 3 hours. After completion of the reaction, the solution was filtered and concentrated to obtain an adsorbing component A-4.
Table 2 shows the structure of the adsorption component A-4.
＜吸着成分Ａ−５の製造方法＞
以下のスキームにしたがい、ベンズアルデヒドを用いる代わりに、４-エトキシベンズアルデヒドを用いた以外は吸着成分Ａ−４の製造方法と同様にして吸着成分Ａ−５を得た。
<Method for producing adsorption component A-5>
According to the following scheme, an adsorbing component A-5 was obtained in the same manner as the adsorbing component A-4 except that 4-ethoxybenzaldehyde was used instead of benzaldehyde.
＜吸着成分Ｂ-１の製造方法＞
以下のスキームにしたがい吸着成分Ｂ−１を得た。
<Method for producing adsorption component B-1>
Adsorption component B-1 was obtained according to the following scheme.
まず、中間体ａを２．２１部（１０．０ミリモル）と、ベンズアルデヒド２．２３部（２１．０ミリモル）とを氷酢酸５２．５部に溶解し、酢酸ナトリウム１５．０部を加えて２４時間還流した。還流後、氷冷し冷水５００部に投入して、生成した析出物を濾取し、水洗、乾燥させた。アルミナカラムクロマトグラフィーを用いて精製し、吸着成分Ｂ-１を得た（収率５０％）。
表２に吸着成分Ｂ−１の構造を示す。
First, 2.21 parts (10.0 mmol) of intermediate a and 2.23 parts (21.0 mmol) of benzaldehyde were dissolved in 52.5 parts of glacial acetic acid, and 15.0 parts of sodium acetate were added. Refluxed for 24 hours. After refluxing, the mixture was ice-cooled and poured into 500 parts of cold water, and the produced precipitate was collected by filtration, washed with water and dried. Purification was performed using alumina column chromatography to obtain the adsorbing component B-1 (yield 50%).
Table 2 shows the structure of the adsorption component B-1.
＜吸着成分Ｂ-２の製造方法＞
以下のスキームにしたがい、吸着成分Ａ−５の製造方法と同様にして中間体ｃ−１を得た。次に、中間体ａの代わりに中間体ｃ−１を用い、ベンズアルデヒドの代わりに４-エトキシベンズアルデヒドを用いた以外は吸着成分Ｂ-１の製造方法と同様にすることで吸着成分Ｂ−２を得た。
<Method for producing adsorption component B-2>
According to the following scheme, intermediate c-1 was obtained in the same manner as in the production method of adsorption component A-5. Next, the adsorbing component B-2 was prepared in the same manner as the adsorbing component B-1, except that the intermediate c-1 was used instead of the intermediate a and 4-ethoxybenzaldehyde was used instead of benzaldehyde. Obtained.
＜化合物１の製造方法＞
プロピレングリコールモノメチルエーテル５０部を窒素置換しながら加熱し液温１２０℃以上で還流させ、そこへ、下記の材料を混合したものを３時間かけて滴下した。
<Method for Producing Compound 1>
50 parts of propylene glycol monomethyl ether was heated while being purged with nitrogen and refluxed at a liquid temperature of 120 ° C. or higher, and a mixture of the following materials was dropped therein over 3 hours.
滴下終了後、溶液を３時間撹拌した後、液温１７０℃まで昇温しながら常圧蒸留し、液温１７０℃到達後は１ｈＰａで減圧下１時間蒸留して脱溶剤し、樹脂固形物を得た。前記固形物をテトラヒドロフランに溶解し、ｎ−ヘキサンで再沈殿させて析出した固体を濾別することでポリマー成分を得た。 After completion of the dropwise addition, the solution was stirred for 3 hours and then distilled at atmospheric pressure while raising the liquid temperature to 170 ° C. After reaching the liquid temperature of 170 ° C., it was distilled for 1 hour under reduced pressure at 1 hPa to remove the solvent. Obtained. The solid matter was dissolved in tetrahydrofuran, reprecipitated with n-hexane, and the precipitated solid was separated by filtration to obtain a polymer component.
次に、クロロホルム３５０部にポリマー成分５０部を溶解させ、オキサリルクロライドを５．０部を氷冷して温度１０℃以下で３０分間かけて滴下した。そのまま室温で５時間静置した。
この溶液に吸着成分Ａ−１を５．０部加えて温度１０℃以下に氷冷し、同温度で３０分反応させた。さらに、トリエチルアミン３.０部を加え、さらにメタノール１５部を加え、温度６０℃で５時間反応させた。これをクロロホルムで抽出し、濃縮、精製して、化合物１を得た。表６に化合物１の製造で使用した材料の混合量と物性を示す。
Next, 50 parts of the polymer component was dissolved in 350 parts of chloroform, and 5.0 parts of oxalyl chloride was ice-cooled and added dropwise at a temperature of 10 ° C. or less over 30 minutes. It was allowed to stand at room temperature for 5 hours.
5.0 parts of adsorbing component A-1 was added to this solution, and the mixture was ice-cooled to a temperature of 10 ° C. or lower and reacted at the same temperature for 30 minutes. Further, 3.0 parts of triethylamine was added, 15 parts of methanol was further added, and the mixture was reacted at a temperature of 60 ° C. for 5 hours. This was extracted with chloroform, concentrated and purified to obtain Compound 1. Table 6 shows the mixing amount and physical properties of the materials used in the production of Compound 1.
＜化合物２〜１０の製造方法＞
表６のように材料の混合量を変更した以外は、化合物１の製造方法と同様にして化合物２〜１０を得た。表６に化合物２〜１０の製造で使用した材料の混合量と物性を示す。
＜化合物１１の製造方法＞
化合物１の製造方法で、「メタノール１５部を加え、温度６０℃で５時間反応させた」ところを、「ｎ-オクタデカノール３．４部加え温度６０℃で３時間反応させた後、さらにメタノール１５部加えて５時間反応させた」以外は同様にして化合物１１を得た。表６に化合物１１の製造で使用した材料の混合量と物性を示す。
<Method for producing compounds 2 to 10>
Compounds 2 to 10 were obtained in the same manner as in the production method of Compound 1 except that the mixing amount of the materials was changed as shown in Table 6. Table 6 shows the mixing amounts and physical properties of the materials used in the production of compounds 2 to 10.
<Method for Producing Compound 11>
In the production method of Compound 1, “15 parts of methanol was added and reacted at a temperature of 60 ° C. for 5 hours” was changed to “3.4 parts of n-octadecanol and reacted at a temperature of 60 ° C. for 3 hours. Compound 11 was obtained in the same manner except that 15 parts of methanol was added and reacted for 5 hours. Table 6 shows the mixing amount and physical properties of the materials used in the production of Compound 11.
＜化合物１２の製造方法＞
スチレン８４．４部とアクリル酸ｎ-ブチル１５．６部を窒素置換しながら加熱し液温１２０℃以上で還流させ、そこへ下記の材料を混合したものを３時間かけて滴下した。
<Method for Producing Compound 12>
84.4 parts of styrene and 15.6 parts of n-butyl acrylate were heated while being purged with nitrogen and refluxed at a liquid temperature of 120 ° C. or higher, and a mixture of the following materials was added dropwise over 3 hours.
滴下終了後、溶液を３時間撹拌した後、液温１７０℃まで昇温しながら常圧蒸留し、液温１７０℃到達後は１ｈＰａで減圧下１時間蒸留して脱溶剤し、樹脂固形物を得た。これをクロロホルムで抽出し、濃縮、精製して、化合物１２を得た。表６に化合物１２の製造で使用した材料の混合量と物性を示す。 After completion of the dropwise addition, the solution was stirred for 3 hours and then distilled at atmospheric pressure while raising the liquid temperature to 170 ° C. After reaching the liquid temperature of 170 ° C., it was distilled for 1 hour under reduced pressure at 1 hPa to remove the solvent. Obtained. This was extracted with chloroform, concentrated and purified to obtain Compound 12. Table 6 shows the mixing amount and physical properties of the materials used in the production of Compound 12.
＜化合物１３〜１７の製造方法＞
化合物１２の製造方法で表６のように混合量を変更した以外は、同様にして化合物１３〜１７を得た。表６に化合物１３〜１７の製造で使用した材料の混合量と物性を示す。
<Method for Producing Compounds 13-17>
Compounds 13 to 17 were obtained in the same manner except that the mixing amount was changed as shown in Table 6 in the production method of Compound 12. Table 6 shows the amounts and physical properties of the materials used in the production of compounds 13-17.
＜化合物１８の製造方法＞
減圧装置、水分離装置、窒素ガス導入装置、温度測定装置、撹拌装置を備えたオートクレープ中に下記の材料を混合し、窒素雰囲気下、常圧下、温度２２０℃で７．５時間反応を行った。
<Method for Producing Compound 18>
The following materials are mixed in an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, and the reaction is carried out at a temperature of 220 ° C. for 7.5 hours under a nitrogen atmosphere and normal pressure It was.
さらに２５〜３５ｍｍＨｇの減圧下で２．５時間反応させ、ポリマー成分を得た。
次に、クロロホルム５００部にポリマー成分１００部を溶解させ、オキサリルクロライドを５．０部を氷冷して温度１０℃以下で３０分間かけて滴下した。そのまま室温で５時間静置した。
この溶液に吸着成分Ａ−１を１０.０部加えて温度１０℃以下に氷冷し、同温度で３０分反応させた。さらに、トリエチルアミン５.０部を加え温度６０℃で５時間反応させた。これをクロロホルムで抽出し、濃縮、精製して、化合物１８を得た。表６に化合物１８の製造で使用した材料の混合量と物性を示す。
Furthermore, it was made to react under reduced pressure of 25-35 mmHg for 2.5 hours, and the polymer component was obtained.
Next, 100 parts of a polymer component was dissolved in 500 parts of chloroform, 5.0 parts of oxalyl chloride was ice-cooled and added dropwise at a temperature of 10 ° C. or less over 30 minutes. It was allowed to stand at room temperature for 5 hours.
To this solution, 10.0 parts of adsorbing component A-1 was added, and the mixture was ice-cooled to a temperature of 10 ° C. or lower and reacted at the same temperature for 30 minutes. Furthermore, 5.0 parts of triethylamine was added and reacted at a temperature of 60 ° C. for 5 hours. This was extracted with chloroform, concentrated and purified to obtain compound 18. Table 6 shows the mixing amount and physical properties of the materials used in the production of Compound 18.
＜比較用化合物１の製造方法＞
化合物１の製造方法で吸着成分Ａ−１を５．０部用いたところ、中間体ａを２．７部用いた以外は同様にして比較用化合物１を得た。表６に比較用化合物１の製造で使用した材料の混合量と物性を示す。
<Method for Producing Compound 1 for Comparison>
When 5.0 parts of the adsorption component A-1 was used in the production method of Compound 1, Comparative Compound 1 was obtained in the same manner except that 2.7 parts of Intermediate a was used. Table 6 shows the mixing amount and physical properties of the materials used in the production of Comparative Compound 1.
＜ポリエステル樹脂１の製造例＞
<Example of production of polyester resin 1>
減圧装置、水分離装置、窒素ガス導入装置、温度測定装置および撹拌装置を備えたオートクレーブ中に上記単量体をエステル化触媒とともに混合し、窒素雰囲気下、減圧しながら、常法にしたがって温度２１０℃でＴｇが６３℃になるまで反応を行った。トリメリット酸無水物をここへ、１２．４部（０．０３モル％）加え、１時間反応させポリエステル樹脂１を得た。得られたポリエステル樹脂の物性値は以下のとおりであった。 The above monomer is mixed with an esterification catalyst in an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, and the temperature is 210 according to a conventional method while decompressing in a nitrogen atmosphere. The reaction was carried out until the Tg reached 63 ° C. To this, 12.4 parts (0.03 mol%) of trimellitic anhydride was added and reacted for 1 hour to obtain polyester resin 1. The physical property values of the obtained polyester resin were as follows.
＜ポリエステル樹脂２の製造例＞ <Example of production of polyester resin 2>
減圧装置、水分離装置、窒素ガス導入装置、温度測定装置および撹拌装置を備えたオートクレーブ中に上記単量体をエステル化触媒とともに混合した。そして、窒素雰囲気下、減圧しながら、常法にしたがって温度２１０℃でＴｇが５８℃になるまで反応を行い、ポリエステル樹脂２を得た。得られたポリエステル樹脂の物性値は以下のとおりであった。 The said monomer was mixed with the esterification catalyst in the autoclave provided with the pressure reduction device, the water separator, the nitrogen gas introducing device, the temperature measuring device, and the stirring device. Then, while reducing the pressure in a nitrogen atmosphere, the reaction was performed at a temperature of 210 ° C. until the Tg reached 58 ° C. according to a conventional method, whereby a polyester resin 2 was obtained. The physical property values of the obtained polyester resin were as follows.
＜ポリエステル樹脂３の製造例＞ <Example of production of polyester resin 3>
上記単量体をエステル化触媒とともにオートクレーブに混合し、減圧装置、水分離装置、窒素ガス導入装置、温度測定装置および撹拌装置をオートクレーブに装着し、窒素雰囲気下、減圧しながら、常法にしたがって温度２１０℃で反応を行った。サンプリングを行い重量平均分子量が所望の分子量になったことを確認して反応を終了し、ポリエステル樹脂３を得た。
得られたポリエステル樹脂３の物性値は以下のとおりであった。
The above monomers are mixed with an esterification catalyst in an autoclave, and a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device are attached to the autoclave and are decompressed under a nitrogen atmosphere according to a conventional method. The reaction was performed at a temperature of 210 ° C. Sampling was performed to confirm that the weight average molecular weight reached the desired molecular weight, and the reaction was terminated to obtain polyester resin 3.
The physical property values of the obtained polyester resin 3 were as follows.
＜スチレン系ビニル樹脂１の製造例＞ <Example of production of styrene-based vinyl resin 1>
撹拌機、コンデンサー、温度計、窒素導入管を備えた反応容器に、上記材料を投入し、１，１，３，３−テトラメチルブチルパーオキシ２−エチルヘキサノエートの７０％トルエン溶液２５部を溶解する。次いでトリメチロールプロパントリス（３−メルカプトプロピオネート）［堺化学（株）製］（β−メルカプトプロピオン酸類）を０．１０部添加して、窒素雰囲気下温度８５℃に昇温して、４時間重合を行った。その後、減圧して脱溶剤したのちハンマーミルにて２ｍｍ以下に粗粉砕し、スチレン系ビニル樹脂１を得た。 Into a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, the above materials were charged and 25 parts of a 70% toluene solution of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate Dissolve. Next, 0.10 parts of trimethylolpropane tris (3-mercaptopropionate) [manufactured by Sakai Chemical Co., Ltd.] (β-mercaptopropionic acids) was added, and the temperature was raised to 85 ° C. under a nitrogen atmosphere. Time polymerization was performed. Thereafter, the solvent was removed under reduced pressure, and then coarsely pulverized to 2 mm or less with a hammer mill to obtain a styrene-based vinyl resin 1.
＜トナー１の製造例＞
[マスターバッチ調製工程]
<Production Example of Toner 1>
[Master batch preparation process]
上記材料をアトライター（日本コークス工業（株）製）に導入し、半径２．５ｍｍのジルコニアビーズ（５００部）を用いて２００ｒｐｍ、温度２５℃で３００分間撹拌を行い、マスターバッチを調製した。 The above materials were introduced into an attritor (manufactured by Nippon Coke Kogyo Co., Ltd.), and stirred at 200 rpm and a temperature of 25 ° C. for 300 minutes using zirconia beads (500 parts) having a radius of 2.5 mm to prepare a master batch.
［トナー組成物溶解液調製工程］ [Toner composition solution preparation step]
上記材料を混合して温度６５℃に加温し、ＴＫ式ホモミキサー（特殊機化工業製）を用いて、５，０００ｒｐｍにて６０分間均一に溶解し分散し、トナー組成物溶解液を得た。 The above materials are mixed and heated to a temperature of 65 ° C., and uniformly dissolved and dispersed at 5,000 rpm for 60 minutes using a TK homomixer (manufactured by Tokushu Kika Kogyo) to obtain a toner composition solution. It was.
［トナー粒子製造工程］
一方、高速撹拌装置ＴＫ−ホモミキサーを備えた２リットルの四つ口フラスコ中に、イオン交換水１２００部に０．１Ｍ−Ｎａ３ＰＯ４水溶液７００部を投入後、ＴＫ式ホモミキサーを１２，０００ｒｐｍに調整して温度６０℃に加温した。その後、１．０Ｍ−ＣａＣｌ２水溶液３８．５部を徐々に添加してリン酸カルシウム化合物を含む水系媒体を得た。
次に、トナー組成物溶解液へ重合開始剤１，１，３，３−テトラメチルブチルパーオキシ２−エチルヘキサノエートの７０％トルエン溶液２５．０重量部を溶解し、十分に混合したのち上記水系媒体へ投入した。これを、温度６５℃、Ｎ2雰囲気下において、ＴＫ式ホモミキサーにて１２，０００ｒｐｍで１０分間撹拌して重合性単量体組成物を造粒した。その後、パドル撹拌翼で撹拌しつつ温度７５℃に昇温し、５時間重合を行った。その後、昇温速度１℃／分で８５℃に昇温し１時間反応させ重合反応を終了した。次いで、減圧下でトナー粒子の残存モノマーを留去し、水系媒体を冷却しトナー粒子の分散液を得た。
[Toner particle production process]
On the other hand, in a 2 liter four-necked flask equipped with a high-speed stirrer TK-homomixer, 700 parts of 0.1M Na 3 PO 4 aqueous solution was added to 1200 parts of ion-exchanged water, The temperature was adjusted to 000 rpm and heated to 60 ° C. Thereafter, 38.5 parts of 1.0 M CaCl 2 aqueous solution was gradually added to obtain an aqueous medium containing a calcium phosphate compound.
Next, after dissolving 25.0 parts by weight of a 70% toluene solution of a polymerization initiator 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate in the toner composition solution, and mixing them well. It poured into the said aqueous medium. This was stirred at 12,000 rpm for 10 minutes with a TK homomixer at a temperature of 65 ° C. in an N 2 atmosphere to granulate the polymerizable monomer composition. Thereafter, the temperature was raised to 75 ° C. while stirring with a paddle stirring blade, and polymerization was carried out for 5 hours. Then, it heated up at 85 degreeC with the temperature increase rate of 1 degree-C / min, and was made to react for 1 hour, and the polymerization reaction was complete | finished. Next, the residual monomer of the toner particles was distilled off under reduced pressure, and the aqueous medium was cooled to obtain a toner particle dispersion.
トナー粒子の分散液に塩酸を加えｐＨを１．４にし、１時間撹拌することでリン酸カルシウム塩を溶解させた。これを加圧濾過器にて、０．４Ｍｐａの圧力下で固液分離を行い、トナーケーキを得た。次に、イオン交換水を加圧濾過器に満水になるまで加え、０．４Ｍｐａの圧力で洗浄した。この洗浄操作を、三度繰り返したのち乾燥し、トナー粒子を得た。
トナー粒子１００質量部へ、ヘキサメチルジシラザンで表面処理された疎水性シリカ微粉体を１.５質量部（数平均一次粒子径：１０ｎｍ）添加し、ヘンシェルミキサー（日本コークス工業（株）製）で３００秒間混合工程を行いトナー１を得た。トナー１の製造で用いた材料について表１６に示す。
Hydrochloric acid was added to the toner particle dispersion to adjust the pH to 1.4, and the mixture was stirred for 1 hour to dissolve the calcium phosphate salt. This was subjected to solid-liquid separation with a pressure filter under a pressure of 0.4 Mpa to obtain a toner cake. Next, ion-exchanged water was added to the pressure filter until the water became full, and washing was performed at a pressure of 0.4 Mpa. This washing operation was repeated three times and then dried to obtain toner particles.
1.5 parts by mass (number average primary particle size: 10 nm) of hydrophobic silica fine powder surface-treated with hexamethyldisilazane is added to 100 parts by mass of toner particles, and a Henschel mixer (manufactured by Nippon Coke Industries Co., Ltd.). The toner 1 was obtained by performing a mixing process for 300 seconds. Table 16 shows materials used in the production of the toner 1.
＜トナー２〜２８および比較トナー１〜４の製造例＞
トナー１の製造例で、表１６のように材料を変更した以外同様にして、トナー２〜２８および比較トナー１〜４を得た。
<Production Examples of Toners 2-28 and Comparative Toners 1-4>
Toner 1 to toner 28 and comparative toners 1 to 4 were obtained in the same manner as in the production example of toner 1 except that the materials were changed as shown in Table 16.
＜トナー２９の製造例＞
[マスターバッチ調製工程]
<Production Example of Toner 29>
[Master batch preparation process]
上記材料をアトライター（日本コークス工業（株）製）に導入し、半径２．５ｍｍのジルコニアビーズ（５００部）を用いて２００ｒｐｍ、温度２５℃で３００分間撹拌を行い、マスターバッチを調製した。 The above materials were introduced into an attritor (manufactured by Nippon Coke Kogyo Co., Ltd.), and stirred at 200 rpm and a temperature of 25 ° C. for 300 minutes using zirconia beads (500 parts) having a radius of 2.5 mm to prepare a master batch.
［トナー組成物溶解液調製工程］ [Toner composition solution preparation step]
上記材料を混合して３０℃に恒温しながら、ＴＫ式ホモミキサー（特殊機化工業製）を用いて、５，０００ｒｐｍにて６０分間均一に溶解し分散し、トナー組成物溶解液を得た。 While mixing the above materials and keeping the temperature constant at 30 ° C., a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) was used to uniformly dissolve and disperse at 5,000 rpm for 60 minutes to obtain a toner composition solution. .
［トナー粒子製造工程］
交換水１２００部に０．１Ｍ−Ｎａ３ＰＯ４水溶液７００部を投入後、ＴＫ式ホモミキサーを１２，０００ｒｐｍに調整して６０℃に加温した。その後、１．０Ｍ−ＣａＣｌ２水溶液３８．５部を徐々に添加してリン酸カルシウム化合物を含む水系媒体を得た。
上記分散液を高速撹拌装置へ投入し、撹拌下において温度６５℃で回転数１０，０００ｒｐｍを維持しつつ３０分間造粒した。その後、高速撹拌装置から通常のプロペラ撹拌装置に変更し、撹拌装置の回転数を１５０ｒｐｍに維持し、内温を９５℃に昇温して３時間保持して分散液から溶剤を除去し、トナー粒子の分散液を調製した。
[Toner particle production process]
After introducing 0.1M-Na 3 PO 4 aqueous solution 700 parts exchanged water 1200 parts, was warmed TK homomixer to adjust to 60 ° C. to 12,000 rpm. Thereafter, 38.5 parts of 1.0 M CaCl 2 aqueous solution was gradually added to obtain an aqueous medium containing a calcium phosphate compound.
The dispersion was put into a high-speed stirring device, and granulated for 30 minutes while maintaining a rotation speed of 10,000 rpm at a temperature of 65 ° C. under stirring. Thereafter, the high-speed stirrer is changed to a normal propeller stirrer, the rotation speed of the stirrer is maintained at 150 rpm, the internal temperature is raised to 95 ° C. and held for 3 hours to remove the solvent from the dispersion, and the toner A dispersion of particles was prepared.
上記トナー粒子分散液を１０Ｌ容量の加圧濾過器にて、０．４Ｍｐａの圧力下で固液分離を行い、トナーケーキを得た。その後、イオン交換水を加圧濾過器に満水になるまで加え、０．４Ｍｐａの圧力で洗浄した。これを、イオン交換水１０００質量部に０．５質量部のアニオン性界面活性剤（ドデシルベンゼンスルホン酸ナトリウム）と０．１質量部の非イオン性界面活性剤１を溶解した水溶液中に再分散した。２４時間静置して、アニオン性界面活性剤および非イオン性界面活性剤をトナー粒子に浸透させた。
上記分散液を再び１０Ｌ容量の加圧濾過器にて、０．４Ｍｐａの圧力下で固液分離したのち、温度４５℃で流動層乾燥を行い、トナー粒子を得た。
このトナー粒子１００質量部に対し、ＢＥＴ比表面積の値が１３０（ｍ２／ｇ）の疎水性シリカ１．８質量部を撹拌混合してトナー２９を得た。トナー２９の製造条件については表１９に示す。
The toner particle dispersion was subjected to solid-liquid separation with a 10 L pressure filter under a pressure of 0.4 Mpa to obtain a toner cake. Thereafter, ion-exchanged water was added to the pressure filter until the water became full, and washing was performed at a pressure of 0.4 Mpa. This was redispersed in an aqueous solution in which 0.5 parts by mass of an anionic surfactant (sodium dodecylbenzenesulfonate) and 0.1 parts by mass of the nonionic surfactant 1 were dissolved in 1000 parts by mass of ion-exchanged water. did. The toner particles were allowed to stand for 24 hours to allow the anionic surfactant and nonionic surfactant to penetrate into the toner particles.
The dispersion was again subjected to solid-liquid separation under a pressure of 0.4 Mpa using a 10 L capacity pressure filter, and then fluidized bed drying was performed at a temperature of 45 ° C. to obtain toner particles.
Toner 29 was obtained by stirring and mixing 1.8 parts by mass of hydrophobic silica having a BET specific surface area of 130 (m 2 / g) with 100 parts by mass of the toner particles. Table 19 shows the manufacturing conditions of the toner 29.
＜トナー３０〜３２および比較用トナー５の製造例＞
トナー２９の製造例で、表１９のように材料を変更した以外は同様にして、トナー３０〜３２および比較用トナー５を得た。
<Production Examples of Toners 30 to 32 and Comparative Toner 5>
In the production example of toner 29, toners 30 to 32 and comparative toner 5 were obtained in the same manner except that the material was changed as shown in Table 19.
上記トナーについてトナー着色力と定着分離性を評価した。評価方法を以下に示す。 The toner was evaluated for toner coloring power and fixing separability. The evaluation method is shown below.
＜トナー着色力の評価方法＞
市販のカラーレーザープリンタＳａｔｅｒａ ＬＢＰ５０５０（キヤノン（株）製）を一部改造して評価を行った。改造は定着機を外し、未定着画像を出力できるように変更し、コントローラーにより画像濃度を調節可能にした。さらに、一色のプロセスカートリッジだけの装着でも作動するよう改良した。市販のカートリッジから中に入っているトナーを抜き取り、エアーブローにて内部を清掃した後、試験トナー（３０ｇ）を充填した。
<Evaluation method of toner coloring power>
A commercially available color laser printer, Satera LBP5050 (manufactured by Canon Inc.) was partially modified and evaluated. In remodeling, the fixing machine was removed and changed so that unfixed images could be output, and the image density could be adjusted by the controller. Furthermore, it has been improved so that it can operate even when only one color process cartridge is installed. The toner contained inside was removed from a commercially available cartridge, the interior was cleaned by air blow, and then the test toner (30 g) was filled.
上記カートリッジをプリンターに装着し、転写材の左上部・右上部・中央・左下部・右下部の５点へ１ｃｍ×１ｃｍのパッチ画像を出力し、コントローラーで各パッチのトナー載り量が０．４０ｇ／ｍ２になるように調節した。その後、定着機を取り付け、上記パッチ画像の定着画像を出力した。このパッチ画像の５つのパッチ部の画像濃度によりトナー着色力を評価した。１．３０以上であれば実用上問題ないと判断した。
なお、画像濃度の測定には「マクベス反射濃度計 ＲＤ９１８」（マクベス社製）を用いて、原稿濃度が０．００の白下地部分のプリントアウト画像に対する相対濃度を測定した。５つのＡ４サイズのＣＳ-８１４用紙（キヤノン（株）製、８１．４ｇ／ｍ２）を用いた。
The above cartridge is installed in the printer, and a 1cm x 1cm patch image is output to the upper left, upper right, center, lower left, and lower right of the transfer material. The amount of toner on each patch is 0.40g using the controller. It was adjusted to / m 2. Thereafter, a fixing device was attached, and a fixed image of the patch image was output. The toner coloring power was evaluated based on the image density of the five patch portions of the patch image. If it was 1.30 or more, it was judged that there was no problem in practical use.
For measurement of the image density, a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.) was used to measure a relative density with respect to a printout image of a white background portion having a document density of 0.00. Five A4 size CS-814 papers (manufactured by Canon Inc., 81.4 g / m 2 ) were used.
＜定着分離性の評価方法＞
上記本体を用いて、上端部に３．０ｍｍ余白を設けた、トナー載り量が０．６０ｍｇ／ｃｍ２の全面ベタ画像を未定着で作成した。
次に、ヒューレッドパッカード社製カラーレーザービームプリンタＨＰ Ｃｏｌｏｒ ＬａｓｅｒＪｅｔ Ｅｎｔｅｒｐｒｉｓｅ ＣＰ４５２５ｄｎレーザービームプリンタの定着ユニットを改造し、改造定着機を作製した。改造定着機は、未定着画像を定着でき、定着温度とプロセススピードが調整できた。改造定着機によってプロセススピ−ド３００ｍｍ／秒で、上記未定着画像を定着した。
定着分離性の評価は、２００℃から５℃ずつ定着温度を低下させ、巻き付きが発生した温度に５℃加えた温度を定着下限温度とした。
定着画像の転写材は、Ａ４サイズのＧＦ-６００用紙（キヤノン（株）製、６０ｇ／ｍ２）を用いた。評価基準は以下のとおりである。１７０℃未満であれば実用上問題ないと判断した。
<Method for evaluating fixing separation>
Using the above-mentioned main body, an entire solid image having a toner loading of 0.60 mg / cm 2 and having a 3.0 mm margin at the upper end was prepared.
Next, the fixing unit of the color laser beam printer HP Color Laser Jet Enterprise CP4525dn laser beam printer manufactured by Hured Packard was modified to produce a modified fixing machine. The modified fixing machine was able to fix unfixed images, and the fixing temperature and process speed could be adjusted. The unfixed image was fixed by a modified fixing machine at a process speed of 300 mm / sec.
In the evaluation of the fixing separation property, the fixing temperature was decreased from 200 ° C. by 5 ° C., and the temperature obtained by adding 5 ° C. to the temperature at which the winding occurred was defined as the minimum fixing temperature.
A4 size GF-600 paper (manufactured by Canon Inc., 60 g / m 2 ) was used as the transfer material for the fixed image. The evaluation criteria are as follows. If it was less than 170 degreeC, it was judged that there was no problem practically.
＜実施例１〜３２＞
トナー１〜３２について、上記評価基準に基づいて評価した。その結果、いずれの項目も良好な結果であった。評価結果の詳細を表２２および表２３に示す。
<Examples 1-32>
The toners 1 to 32 were evaluated based on the above evaluation criteria. As a result, all items were good results. Details of the evaluation results are shown in Table 22 and Table 23.
＜比較例１〜５＞
比較用トナー１〜５について上記評価基準に基づいて評価した。その結果、比較用トナー１〜３および５は着色力の点で実用上問題のあるレベルであった。また、比較用トナー１〜５のいずれも定着分離性で実用上問題があるレベルであった。評価結果の詳細を表２３に示す。
<Comparative Examples 1-5>
Comparative toners 1 to 5 were evaluated based on the above evaluation criteria. As a result, Comparative toners 1 to 3 and 5 were practically problematic levels in terms of coloring power. In addition, all of the comparative toners 1 to 5 were at a level having a practical problem in terms of fixing separation. Details of the evaluation results are shown in Table 23.
Claims (10)
前記顔料が、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ３１、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １２２、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １５０およびＣ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ２６９からなる群より選ばれる１種以上の顔料であり、
前記顔料分散剤は、顔料に吸着する吸着成分と、該吸着成分と結合しているポリマー成分とで構成された顔料分散剤であり、
該吸着成分が下記式（１）で表される構造を有することを特徴とするトナー。
ポリマー成分と結合しないＡｒ１、Ａｒ２、およびＡｒ３は、アリール基を示し、
ポリマー成分と結合するＡｒ１、Ａｒ２、およびＡｒ３は、アリール基から水素を１つ脱離して形成される基を示す。
前記連結基は、アミド基、エステル基、ウレタン基、ウレア基、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ１−および−ＮＨＣＨ（ＣＨ２ＯＨ）−からなる群より選ばれる２価の連結基であり、Ｒ１は、水素原子、アルキル基、フェニル基またはアラルキル基を示す。］ A toner containing a binder resin, a pigment, a release agent, and a pigment dispersant,
The pigment is C.I. I. Pigment Red 31, C.I. I. Pigment Red 122, C.I. I. Pigment Red 150 and C.I. I. One or more pigments selected from the group consisting of Pigment Red 269,
The pigment dispersant, the adsorption component that adsorbs to Pigments, Ri pigment dispersant der comprised of a polymer component which is bound to the adsorption component,
Toner according to claim Rukoto that having a structure in which adsorption component is represented by the following formula (1).
Ar 1 , Ar 2 , and Ar 3 that are not bonded to the polymer component represent an aryl group,
Ar 1 , Ar 2 , and Ar 3 bonded to the polymer component represent a group formed by removing one hydrogen from an aryl group.
The linking group is a divalent linkage selected from the group consisting of an amide group, an ester group, a urethane group, a urea group, an alkylene group, a phenylene group, —O—, —NR 1 —, and —NHCH (CH 2 OH) —. R 1 represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. ]
前記結着樹脂がポリエステル樹脂を含有する場合は、前記ポリマー成分がポリエステル樹脂を含有する請求項１〜４のいずれか１項に記載のトナー。 When the binder resin contains a vinyl resin, the polymer component contains a vinyl resin,
The toner according to any one of claims 1 to 4, wherein when the binder resin contains a polyester resin, the polymer component contains a polyester resin.
前記式（２）中、Ｌ１は、前記ポリマー成分と結合するための２価の連結基を示す。］ The toner according to claim 1, wherein the adsorption component represented by the formula (1) is an adsorption component represented by the following formula (2).
In the formula (2), L 1 represents a divalent linking group for bonding with the polymer component. ]
前記顔料が、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ３１、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １２２、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １５０およびＣ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ２からなる群より選ばれる１種以上の顔料であり、
前記顔料分散剤は、顔料に吸着する吸着成分と、該吸着成分と結合しているポリマー成分とで構成された顔料分散剤であり、
該吸着成分が下記式（１）で表される構造を有し、
ポリマー成分と結合しないＡｒ １ 、Ａｒ ２ 、およびＡｒ ３ は、アリール基を示し、
ポリマー成分と結合するＡｒ １ 、Ａｒ ２ 、およびＡｒ ３ は、アリール基から水素を１つ脱離して形成される基を示す。
前記連結基は、アミド基、エステル基、ウレタン基、ウレア基、アルキレン基、フェニレン基、−Ｏ−、−ＮＲ １ −および−ＮＨＣＨ（ＣＨ ２ ＯＨ）−からなる群より選ばれる２価の連結基であり、Ｒ １ は、水素原子、アルキル基、フェニル基またはアラルキル基を示す。］
ｉ）重合性単量体、顔料と前記式（１）の化合物を含有する重合性単量体組成物を、水系媒体中にて造粒し、造粒された粒子中に含有される重合性単量体を重合することによってトナー粒子を得る工程、
または
ｉｉ）結着樹脂、顔料と前記式（１）の化合物を含有するトナー組成物を、有機溶媒中に溶解または分散させた混合溶液を、水系媒体中にて造粒し、造粒された粒子中に含有される有機溶媒を除去することによってトナー粒子を得る工程
を有することを特徴とするトナーの製造方法。 A method for producing a toner containing a binder resin, a pigment, a release agent, and a pigment dispersant,
The pigment is C.I. I. Pigment Red 31, C.I. I. Pigment Red 122, C.I. I. Pigment Red 150 and C.I. I. One or more pigments selected from the group consisting of Pigment Red 2;
The pigment dispersant, the adsorption component that adsorbs to the Pigments are pigment dispersant which is composed of a polymer component which is bound to the adsorption component,
The adsorbing component has a structure represented by the following formula (1):
Ar 1 , Ar 2 , and Ar 3 that are not bonded to the polymer component represent an aryl group,
Ar 1 , Ar 2 , and Ar 3 bonded to the polymer component represent a group formed by removing one hydrogen from an aryl group.
The linking group is a divalent linkage selected from the group consisting of an amide group, an ester group, a urethane group, a urea group, an alkylene group, a phenylene group, —O—, —NR 1 —, and —NHCH (CH 2 OH) —. R 1 represents a hydrogen atom, an alkyl group, a phenyl group or an aralkyl group. ]
i) A polymerizable monomer, a pigment and a polymerizable monomer composition containing the compound of the formula (1) are granulated in an aqueous medium, and the polymerizability contained in the granulated particles. Obtaining toner particles by polymerizing monomers;
Or ii) A mixed solution in which a toner composition containing a binder resin, a pigment, and the compound of the formula (1) is dissolved or dispersed in an organic solvent is granulated in an aqueous medium and granulated. A method for producing toner, comprising a step of obtaining toner particles by removing an organic solvent contained in the particles.
前記ポリマー成分が、下記式（４）で示される単量体単位を含むポリマー成分である請求項９に記載のトナーの製造方法。
The toner production method is the method i),
The method for producing a toner according to claim 9, wherein the polymer component is a polymer component including a monomer unit represented by the following formula (4).
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