Toner and method for manufacturing toner
15 claims: 6 independent, 9 dependent
- 1顔料、樹脂A及び樹脂Bを含有するトナー粒子を含むトナーであって、 該顔料は、塩基性化合物に由来する構造を有する顔料であり、 該樹脂Aは酸性官能基を有し、 該樹脂Aの重量平均分子量(Mw)が、10000以上75000以下であり、 該樹脂Bの酸価が、2.0mgKOH/g以上であり、 該樹脂Bのガラス転移温度TgBが、50°C以上であり、 該樹脂Aの疎水性パラメータHPA、及び該樹脂Bの疎水性パラメータHPBが、下記式を満たすことを特徴とするトナー。 HPA≧0.60 HPB≦0.70 HPA-HPB 0(式中、 HPAは、該樹脂A0.01質量部、及びクロロホルム1.48質量部を含む溶液にヘプタンを添加した際の該樹脂Aの析出点におけるヘプタンの体積分率を示す。 HPBは、該樹脂B0.01質量部、及びクロロホルム1.48質量部を含む溶液にヘプタンを添加した際の該樹脂Bの析出点におけるヘプタンの体積分率を示す。)
- 2前記顔料のpKaが、4.0以上7.0以下である請求項1に記載のトナー。(pKaは、前記顔料10.0質量部、トルエン140.0質量部、及びエタノール60.0質量部を混合して得られた顔料分散液を、0.1モル/L塩酸エタノール溶液で中和試験することによって測定される塩基解離定数である。)
- 3前記顔料の塩基価が、0.9mgKOH/g以上3.0mgKOH/g以下である請求項1又は2のいずれか一項に記載のトナー。
- 4前記塩基性化合物に由来する構造を有する顔料は、塩基性部位を有する有機色素を含む顔料であり、 該塩基性部位を有する有機色素は、下記式(2)で示される構造を有する請求項1~3のいずれか1項に記載のトナー。 (式(2)中、Pは有機色素である。xは、1又は2である。yは1以上4以下の値である。R 1 、R 2 は、それぞれ独立に、水素原子、直鎖若しくは分岐のアルキル基、又はR 1 及びR 2 が結合して複素環を形成するのに必要な基を示す。)
- 5前記Pが、フタロシアニン骨格又はキナクリドン骨格を有する有機色素である請求項4に記載のトナー。
- 6前記塩基性化合物に由来する構造を有する顔料は、塩基性官能基を有する顔料であり、 該塩基性官能基が、下記式(8)で示される請求項1~3のいずれか1項に記載のトナー。 (式(8)中、*は該顔料との結合部位を表し、zは1又は2である。R 3 、R 4 は、それぞれ独立に、水素原子、直鎖若しくは分岐のアルキル基、又はR 3 とR 4 が結合して複素環を形成するのに必要な基を示す。)
- 7前記樹脂Aの酸性官能基がカルボキシ基、又はスルホ基である請求項1~6のいずれか1項に記載のトナー。
- 8前記樹脂Aは、下記式(3)で表される部分構造を有する請求項1~7のいずれか一項に記載のトナー。 式(3)中、R 4 、及びR 5 のいずれか一つは、カルボキシ基であり、該カルボキシ基以外のR 3 、R 4 、R 5 、R 6 及びR 7 は、それぞれ独立して水素原子、水酸基、アミノ基、炭素数1以上8以下のアルコキシ基又は炭素数1以上8以下のアルキル基を示す。Lは式(4)で表わされる連結基を示す。*は、前記樹脂Aの主鎖骨格に結合する部位を表す。 (式(4)中、aは0又は1であり、bは0以上4以下の整数である。Xは単結合又は-O-、-S-、若しくは-NR 8 -のいずれかで表される基である。R 8 は水素原子又は炭素数1以上4以下のアルキル基である。*は、前記樹脂Aの主鎖骨格に結合する部位を表す。)
- 9前記式(3)で表される部分構造が、下記式(5)で表される請求項8に記載のトナー。 (式(5)中、R 10 、R 11 のいずれか一方はカルボキシ基であり、もう一方は水酸基である。R 9 、R 12 及びR 13 は、それぞれ独立して、水素原子、水酸基、アミノ基、炭素数1以上4以下のアルコキシ基又は炭素数1以上4以下のアルキル基である。*は、前記樹脂Aの主鎖骨格に結合する部位を表す。)
- 10前記樹脂Aは下記式(6)で示される構造を有する請求項1から7のいずれか1項に記載のトナー。 (式(6)中、nは3以上21以下の整数である。*は前記樹脂Aの主鎖骨格に結合する部位を示す。)
- 11前記樹脂Aの含有量が、前記顔料100質量部に対して、1.0質量部以上30.0質量部以下である請求項1~10のいずれか1項に記載のトナー。
- 12前記樹脂Aの酸価が、3.0mgKOH/g以上25.0mgKOH/g以下である請求項1~11のいずれか1項に記載のトナー。
- 13前記HPAとHPBは下記式(7)を満たす請求項1~ 12 のいずれか1項に記載のトナー。 HPA-HPB≧0.05 (7)
- 14前記樹脂Aの含有量が、前記樹脂B100質量部に対して、1.0質量部以上である請求項1~ 13 のいずれか1項に記載のトナー。
- 15請求項1~ 14 のいずれか1項に記載のトナーの製造方法であって、 該製造方法が、下記(i)又は(ii)の工程:(i)ビニル系重合性単量体、前記樹脂A、前記樹脂B、及び前記顔料を含む重合性単量体組成物を水系媒体中で造粒し、該重合性単量体組成物に含まれる該ビニル系重合性単量体を重合してトナー粒子を製造する工程;(ii)有機溶媒中に前記樹脂A、前記樹脂B及び前記顔料を含む有機溶媒分散液を水系媒体中で造粒し、トナー粒子を製造する工程;を有することを特徴とするトナーの製造方法。
Independent claims15
60 paragraphs, as filed
The present invention relates to toners and toner manufacturing methods used in image forming methods such as electrophotographic, electrostatic recording, and toner jet methods.
In recent years, printers and copiers are required to be smaller and have a longer life. In addition, now that it is used in various environments, it is required to improve the storage stability at high temperature. In order to reduce the size of the device, it is effective to improve the coloring power of the toner. Since the image can be formed with a small amount of toner, the toner container can be miniaturized. In order to improve the coloring power of the toner, it is effective to finely disperse the pigment. As a means for improving the dispersibility of the pigment, a pigment with a surface treatment is used. Patent Document 1 describes an example in which a pigment with a surface treatment is used.
<p><patcit num="1"><text>Japanese Unexamined Patent Publication No. 2012-133192</text></patcit><patcit num="2"><text>Japanese Patent Application Laid-Open No. 2005-181835</text></patcit><patcit num="3"><text>JP-A-2015-125406</text></patcit></p>
<p> However, as in Patent Document 1, when only the pigment to which the surface treatment is applied is used, sufficient dispersibility cannot be obtained, and a high level of coloring power may not be obtained. Patent Document 2 suggests that a pigment dispersant utilizing an acid-base interaction may be used to obtain a higher level of coloring power. On the other hand, it is effective to improve the durability and heat-resistant storage property of the toner in order to extend the service life and store heat-resistant property. Patent Document 3 describes an example of using a polar resin having a high glass transition point, and studies have been made to improve durability and heat-resistant storage stability. However, when these techniques are combined, the polar resin may be adsorbed on the surface-treated pigment by the interaction of acid-base or the like, and the polarity of the pigment dispersion may be increased. Therefore, there are cases where the original performance of each cannot be exhibited due to the aggregation of pigments and the deterioration of the dispersibility of the polar resin. As a result, it may be difficult to achieve both high coloring power, durability and heat-resistant storage stability. Further, even when a conventional pigment dispersant is used in combination, it may be difficult to suppress the above-mentioned interaction. The present invention provides a toner that solves the above-mentioned problems. That is, an object of the present invention is to provide a toner having both high coloring power, durability and heat-resistant storage stability, and a method for producing the same.</p>
<p> The present invention is a toner containing toner particles containing a pigment, resin A and resin B, wherein the pigment is a pigment having a structure derived from a basic compound, and the resin A has an acidic functional group.<u style="single">The weight average molecular weight (Mw) of the resin A is 10,000 or more and 75,000 or less.</u> The acid value of the resin B is 2.0 mgKOH / g or more, the glass transition temperature TgB of the resin B is 50 ° C or more, the hydrophobic parameter HPA of the resin A and the hydrophobic parameter HPB of the resin B. However, the present invention relates to a toner characterized by satisfying the following formula. HPA 0.60 HPB 0.70 HPA-HPB> 0 (In the formula, HPA is the amount of heptane at the precipitation point of the resin A when heptane is added to the solution containing 0.01 part by mass of the resin A and 1.48 parts by mass of chloroform. The volume fraction is shown. HPB shows the volume fraction of heptane at the precipitation point of the resin B when heptane is added to a solution containing 0.01 part by mass of the resin B and 1.48 parts by mass of chloroform.) Further, the present invention is a method for producing the above-mentioned toner, wherein the production method is the following step (i) or (ii): (i) vinyl-based polymerizable monomer, the resin A, the resin B, And a step of granulating the polymerizable monomer composition containing the pigment in an aqueous medium and polymerizing the vinyl-based polymerizable monomer contained in the polymerizable monomer composition to produce toner particles. (Ii) Production of a toner comprising: (ii) a step of granulating an organic solvent dispersion containing the resin A, the resin B and the pigment in an organic solvent in an aqueous medium to produce toner particles; Regarding the method.</p>
<p> INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a toner having both high coloring power, durability and heat-resistant storage stability, and a method for producing the same.</p>
Hereinafter, the toner of the present invention and the method for producing the toner will be specifically described, but the present invention is not limited to the following embodiments. In the present invention, the description of " or more and XX or less" and " to XX " indicating a numerical range means a numerical range including a lower limit and an upper limit which are end points, unless otherwise specified. As a result of diligent studies, the present inventors have found that the above-mentioned toner exhibits the effects in the present invention. The mechanism of the manifestation of the effect of the present invention is considered as follows. The resin A used in the present invention has an acidic functional group, and the pigment contains a pigment having a structure derived from a basic compound. Therefore, it is considered that the acid-base interaction between the acidic resin A and the basic pigment improves the pigment dispersibility and the coloring power. Conventional pigment dispersants utilizing acid-base interactions often have a high acid value or amine value in order to improve the interaction with the pigment. When such a pigment dispersant is used, the polarity of the pigment dispersion becomes high in the toner, and the dispersion tends to cause self-aggregation. Therefore, it is difficult to improve the coloring power.
Further, when a polar resin having a high glass transition temperature (Tg) is used in combination with the above-mentioned system for the purpose of improving durability and heat-resistant storage stability, the polar resin and the highly polar pigment dispersion easily interact with each other, and the pigment. It is considered that the polar resins are unevenly distributed in the periphery and the dispersibility of the polar resins is lowered. As a result, Tg is biased inside the toner, which may cause a decrease in durability and heat resistance. On the other hand, the resin A is characterized in that it has an acidic functional group and its hydrophobicity is high. Therefore, when the resin A is used, in addition to the effect of pigment dispersion by the acidic functional group, the self-aggregation of the pigment can be suppressed by covering the pigment dispersion with the hydrophobic group, and the coloring power is improved. Conceivable. Further, in the present invention, HPA-HPB> 0. When the resin B having a low degree of hydrophobicity is used as the polar resin, it is difficult to be compatible with the resin A having a high degree of hydrophobicity and can exist independently of the pigment, so that the function of the resin B can be exhibited. It is considered that the presence of the resin B having a high Tg improved the durability and the heat-resistant storage stability. From the above, in the present invention, by using the resin A having an acidic functional group and having a high degree of hydrophobicity and the resin B having a specific acid value and having a low degree of hydrophobicity, the desired effect can be obtained. It is considered that the expression of
Hereinafter, the toner material according to the present invention will be specifically described. First, a pigment having a structure derived from the basic compound used in the present invention (hereinafter, also referred to as basic treated pigment or treated pigment) will be described. The basic treated pigment is a pigment containing an organic dye having a basic site (hereinafter, also referred to as a treatment agent) or a pigment having a basic functional group. A pigment containing an organic dye (treatment agent) having a basic moiety can be obtained, for example, by mixing a pigment with an organic dye (treatment agent) having a basic moiety. Further, a pigment having a basic functional group can be obtained, for example, by directly chemically modifying the pigment to make a part of the pigment basic. Either aspect may be used, but a pigment containing an organic dye (treatment agent) having a basic moiety is preferable because of the ease of adjusting the base value of the pigment and the ease of developing into a pigment type. The organic dye (treatment agent) having a basic moiety in the present invention preferably has a structure represented by the following formula (2). In this structure, a basic compound derived from an amino group is bonded to an organic dye via an alkylene group.
<chemistry num="1"><img file="JP6727872B2_D0001.tif" /></chemistry>
(In equation (2), P is an organic dye. X is 1 or 2. y is a value between 1 and 4. R.<sup>1</sup>, R<sup>2</sup>Are independently hydrogen atoms, linear or branched alkyl groups, or R<sup>1</sup>And R<sup>2</sup>Indicates the groups required for the bonds to form a heterocycle (preferably with 3 to 6 carbon atoms). ) P is an organic pigment, preferably a structure that can be adsorbed on the pigment. More preferably, P is an organic dye having a phthalocyanine skeleton or a quinacridone skeleton. Specific examples thereof include copper phthalocyanine, zinc phthalocyanine, 2,9-dimethylquinacridone, and quinacridone. y is the average number of basic sites bound to the organic dye (average per molecule of the organic dye), and is a value of 1 or more and 4 or less (preferably 2 or more and 4 or less). R<sup>1</sup>, R<sup>2</sup>Are independent hydrogen atoms, linear or branched alkyl groups with 1 to 4 carbon atoms, or R.<sup>1</sup>And R<sup>2</sup>It is preferable that the structure is such that steric hindrance is suppressed and the resin A is easily adsorbed. R<sup>1</sup>And R<sup>2</sup>When they are combined to form a heterocycle, the ring structure may contain a nitrogen atom or an oxygen atom in addition to N in the equation (2). ) -NR in the above equation (2)<sup>1</sup>R<sup>2</sup>Specific examples of the basic functional group corresponding to the above include an amino group as a primary amine, a monomethylamino group as a secondary amine, a monoethylamino group, a monopropylamino group, a monoisopropylamino group, and a monobutylamino group. Monoisobutylamino group, mono-tert-butylamino group, monopentylamino group, monohexylamino group, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, dibutylamino group, diisobutylamino group as tertiary amines , Di-tert-butylamino group, dipentylamino group, dihexylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, ethylpropylamino group, ethylbutylamino group, pyrrolidinyl group, piperidinyl group, piperazinyl Groups, morpholino groups, pyrrolyl groups and the like can be mentioned.
Further, the base dissociation constant (pKa) of the pigment is preferably 4.0 or more and 7.0 or less, and more preferably 4.5 or more and 6.5 or less. The above-mentioned pKa is measured by neutralizing a pigment dispersion obtained by mixing 10.0 parts by mass of the pigment, 140.0 parts by mass of toluene, and 60.0 parts by mass of ethanol with a 0.1 mol / L hydrochloric acid ethanol solution. It is a base dissociation constant. The detailed measurement method will be described later. When the pKa is 4.0 or more, the interaction between the treatment agent and the resin B is suppressed, so that the coloring power, durability, and heat-resistant storage stability are likely to be improved. When the pKa is 7.0 or less, it is more likely to be adsorbed to the resin A, so that the coloring power is likely to be improved. Furthermore, -NR in equation (2)<sup>1</sup>R<sup>2</sup>When is a tertiary amine, the pKa of the treatment agent is likely to be in the range of 4.0 or more and 7.0 or less, the interaction between the treatment agent and the resin B is suppressed, and the resin A is easily adsorbed, which is more preferable.
From the above, the treatment agent used in the present invention has a structure represented by the formula (2), and is -NR.<sup>1</sup>R<sup>2</sup>It is preferable that the basic functional group corresponding to the above has a dialkylamine structure having 1 to 4 carbon atoms or a cyclic amine structure having 3 to 6 carbon atoms. In that case, the pKa of the basic treatment pigment is controlled in a suitable range, and the adsorption of the resin A is not hindered by steric hindrance, so that the coloring power, durability, and heat-resistant storage stability are likely to be improved.
As described above, the pigment having a structure derived from the basic compound may be a pigment having a basic functional group. The basic functional group is preferably represented by the following formula (8).
<chemistry num="2"><img file="JP6727872B2_D0002.tif" /></chemistry> In formula (8), * represents the binding site with the pigment, and z is 1 or 2. R<sup>3</sup>, R<sup>4</sup>Are independently hydrogen atoms, linear or branched alkyl groups, or R<sup>3</sup>And R<sup>4</sup>Indicates the groups required for the bonds to form a heterocycle (preferably with 3 to 6 carbon atoms). R<sup>3</sup>, R<sup>4</sup>The preferred embodiment of the above R<sup>1</sup>, R<sup>2</sup>Is similar to. -NR<sup>3</sup>R<sup>4</sup>The mode for the group corresponding to the above-NR<sup>1</sup>R<sup>2</sup>It is the same as the functional group corresponding to. A pigment having a basic functional group can be obtained, for example, by directly chemically modifying the pigment to make a part of the pigment basic. As a specific method, basicized copper phthalocyanine can be obtained by reacting a phthalocyanine pigment with paraformaldehyde and phthalimide in concentrated sulfuric acid.
The pigment having a structure derived from a basic compound is preferably a pigment containing an organic dye (treatment agent) having a basic moiety. Examples of the pigment that can be used for the basic treatment pigment include the conventionally known pigments listed below. Examples of the black pigment include carbon black and the like. Examples of the yellow pigment include a condensed pigment, an isoindolinone compound, an anthraquinone compound, an azometal complex methine compound, and a compound typified by an allylamide compound. More specifically, for example, CIPigment Yellow 3, 7, 10, 12, 13, 14, 15, 17, 23, 24, 60, 62, 74, 75, 83, 93, 94, 95, 99, 100, 101, 104, 108, 109, 110, 111, 117, 123, 128, 129, 138, 139, 147, 148, 150, 155, 166, 168, 169, 177, 179, 180, 181, 183, 185, 191: 1, 191, 192, 193, 199 and the like.
Examples of magenta pigments include condensed pigments, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds and the like. More specifically, for example, CIPigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, CIPigment Violet 19 and the like. Examples of the cyan pigment include a phthalocyanine compound, a derivative of a phthalocyanine compound, an anthraquinone compound, and a basic dye lake compound. More specifically, CIPigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like can be mentioned. These pigments may be mixed with the treatment agent alone or in combination of two or more. The content of the pigment is preferably 4% by mass or more and 20% by mass or less in the toner particles.
In the present invention, the base value of the pigment is preferably 0.9 mgKOH / g or more and 3.0 mgKOH / g or less, and more preferably 1.3 mgKOH / g or more and 2.5 mgKOH / g or less. If the base value is 0.9 mgKOH / g or more, the absolute amount of the treatment agent is sufficient, so that the pigment dispersibility is improved and the coloring power is likely to be improved. Further, if it is 3.0 mgKOH / g or less, it is easy to suppress the interaction with the resin B while maintaining a sufficient coloring power, so that the durability and the heat-resistant storage stability are easily improved. The basic value of the basic treatment pigment can be controlled by adjusting the amount of the treatment agent added. The method for measuring the base value will be described later. The method for producing the treatment agent in the present invention is not particularly limited, and can be obtained by a conventionally known method. Specifically, the production method example described in Japanese Patent No. 4484171 can be applied to the production method of the treatment agent of the present invention.
Next, the resin A used in the present invention will be specifically described. The hydrophobic parameter HPA of the resin A in the present invention is 0.60 or more. When HPA is 0.60 or more, the degree of hydrophobicity is sufficiently high, so that the interaction between the resin B and the basic treated pigment can be suppressed for the reasons described above, and high coloring power, heat-resistant storage stability and durability can be obtained. It becomes easier to achieve both. HPA can be controlled mainly by changing the composition of resin A. HPA indicates the volume fraction of heptane at the precipitation point of the resin A when heptane is added to the solution containing 0.01 part by mass of the resin A and 1.48 parts by mass of chloroform. The HPA is preferably 0.65 or higher. The upper limit is not particularly limited, but is preferably 0.98 or less, and more preferably 0.95 or less.
The resin A in the present invention has an acidic functional group. When the resin A has an acidic functional group, the acidic functional group interacts with the structure derived from the basic compound and exhibits high adsorptivity to the pigment, thereby achieving both high coloring power, heat storage stability and durability. Is possible. As the acidic functional group, a carboxy group, a sulfo group, a phosphoric acid group, a phenolic hydroxyl group and the like can be used. Among these acidic functional groups, it is preferable to use a carboxy group, a sulfo group or a phosphoric acid group because they have high acidity and are advantageous for adsorption to a basic treatment pigment. Among them, a carboxy group or a sulfo group is more preferable from the viewpoint of ease of production and stability of the resin. The resin A of the present invention preferably has a partial structure represented by the following formula (3).
<chemistry num="3"><img file="JP6727872B2_D0003.tif" /></chemistry>
(In equation (3), R<sup>4</sup>, And R<sup>5</sup>Any one of them is a carboxy group. R other than the carboxy group<sup>3</sup>, R<sup>4</sup>, R<sup>5</sup>, R<sup>6</sup>And R<sup>7</sup>Independently indicate a hydrogen atom, a hydroxyl group, an amino group, an alkoxy group having 1 or more and 8 or less carbon atoms, or an alkyl group having 1 or more and 8 or less carbon atoms. L represents a linking group represented by the formula (4). * Represents a site that binds to the main clavicle of resin A. )
<chemistry num="4"><img file="JP6727872B2_D0004.tif" /></chemistry>
(In equation (4), a is 0 or 1, b is an integer greater than or equal to 0 and less than or equal to 4. X is a single bond or -O-, -S-, or -NR.<sup>8</sup>It is a group represented by any of-. R<sup>8</sup>Is a hydrogen atom or an alkyl group having 1 or more and 4 or less carbon atoms. * Represents a site that binds to the main clavicle of resin A. ) The carboxy group in the formula (3) is the adsorption site with the pigment having the structure derived from the above-mentioned basic compound, and is R.<sup>4</sup>, And R<sup>5</sup>It is preferable to be one of. R<sup>4</sup>, And R<sup>5</sup>In the case of any of the above, since the distance from the main clavicle is large, the steric hindrance at the time of adsorption can be reduced, so that the adsorption property is likely to be improved. When a group other than the carboxy group uses an alkoxy group having 1 or more and 8 or less carbon atoms or an alkyl group having 1 or more and 8 or less carbon atoms, an alkoxy group having 1 or more and 4 or less carbon atoms or an alkoxy group having 1 or more carbon atoms or 4 or less carbon atoms is used from the viewpoint of steric hindrance during adsorption. It is more preferable to use an alkyl group having 1 or more and 4 or less carbon atoms. It is more preferable that a in the equation (4) is 1. When a is 1, the distance between the adsorption site and the main clavicle can be appropriately controlled, so that the adsorption property to the pigment is likely to be improved. For the same reason, b is more preferably 1 or more and 4 or less. Further, when X is -O-, in addition to the acid-base interaction, the interaction by hydrogen bonds is likely to work, so that the adsorptivity is likely to be improved. The partial structure represented by the formula (3) is preferably a partial structure represented by the following formula (5).
<chemistry num="5"><img file="JP6727872B2_D0005.tif" /></chemistry>
In equation (5), R<sup>10</sup>, R<sup>11</sup>One of them is a carboxy group and the other is a hydroxyl group. R<sup>9</sup>, R<sup>12</sup>And R<sup>13</sup>Are independently hydrogen atoms, hydroxyl groups, amino groups, alkoxy groups having 1 or more and 4 or less carbon atoms, or alkyl groups having 1 or more and 4 or less carbon atoms. * Represents a site that binds to the main clavicle of the resin A. The resin A preferably has a partial structure represented by the formula (3) (preferably the formula (5)) in the side chain. When the partial structure represented by the above formula (3) is the partial structure represented by the formula (5), the adsorptivity to a pigment having a structure derived from a basic compound is likely to be improved for the above-mentioned reason. It becomes easy to achieve both high coloring power, heat storage stability, and durability.
The main chain skeleton of the resin A may be any polymer. Examples thereof include vinyl-based polymers, polyester-based polymers, polyamide-based polymers, polyurethane-based polymers, and polyether-based polymers. Among these, a vinyl polymer or a polyester polymer is preferable from the viewpoint of ease of production. Furthermore, a vinyl polymer is more preferable from the viewpoint of ease of controlling hydrophobic parameters. When a vinyl-based polymer is used as the resin A in the present invention, for example, a method obtained by copolymerizing a compound having a polymerizable functional group as represented by the following formula (A) with a vinyl-based monomer, or a method for obtaining the resin A. There is a method of introducing an acidic functional group into a polymer obtained by copolymerizing a monomer derived from the main chain skeleton in advance.
<chemistry num="6"><img file="JP6727872B2_D0006.tif" /></chemistry>
When a vinyl polymer is used as the resin A, for example, the partial structure represented by the formula (3) is preferably represented by the following formula (3-1).
<chemistry num="7"><img file="JP6727872B2_D0007.tif" /></chemistry>
[In the above equation (3-1), R<sup>9</sup>~ R<sup>13</sup>Is the same as above. R<sup>14</sup>Represents a hydrogen atom or a methyl group. ]
The vinyl-based monomer used for the resin A is not particularly limited. The following vinyl-based polymer is preferably used as the monomer for the main chain skeleton of the resin A. Specifically, aromatic vinyl monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene and α-methylstyrene; ethylene unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene. System monomers; Vinyl halide monomers such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride; Vinyl esteric acid monomers such as vinyl acetate, vinyl propionate, vinyl benzoate; Acrylic acid , Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, dodecyl acrylate, stearyl acrylate, behenyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate Acrylic acid-based monomers such as glycidyl acrylate and benzyl acrylate; methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, methacrylic acid. Examples thereof include methacrylic acid-based monomers such as dodecyl, stearyl methacrylate, behenyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, glycidyl methacrylate, and benzyl methacrylate. One of the above monomers can be used alone or in combination of two or more.
The main chain skeleton of the resin A may be a composite polymer having a polyester structure and a vinyl-based copolymer structure. Specific examples thereof include a composite polymer in which a vinyl-based polymer structure is grafted on a polyester main chain, or a composite polymer having a structure in which a polyester structure and a vinyl-based polymer structure are bonded by a block. The resin A in the present invention preferably further has an alkoxycarbonyl group represented by the following formula (6). This makes it easier to control the HPA to 0.60 or higher.
<chemistry num="8"><img file="JP6727872B2_D0008.tif" /></chemistry>
At this time, n is preferably 3 or more and 21 or less. When n is 3 or more, the effect of increasing the hydrophobicity of the resin A is high, so that the coloring power, durability, and heat resistance are likely to be improved. Further, when n is 21 or less, the adsorption of the resin A to the basic treatment pigment is not inhibited, so that the coloring power, durability and heat resistance are easily improved. * Represents a site that binds to the main clavicle of resin A. As the monomer containing an alkoxycarbonyl group from which the structure of the formula (6) is derived, an alkyl ester of acrylic acid or methacrylic acid having 3 to 21 carbon atoms is preferable. For example, butyl acrylate, stearyl acrylate, behenyl acrylate, butyl methacrylate, stearyl methacrylate, behenyl methacrylate and the like can be mentioned. The content of the monomer unit containing the structure of the formula (6) is preferably 2 mol% or more and 12 mol% or less based on all the monomer units of the resin A.
The weight average molecular weight (Mw) of the resin A in the present invention is preferably 10,000 or more and 75,000 or less, and more preferably 10,000 or more and 55,000 or less. When Mw is 10000 or more, the excluded volume effect works sufficiently, so that the pigment is well dispersed and the coloring power is likely to be improved. When Mw is 75,000 or less, the adsorptivity to the pigment is not hindered, so that the coloring power, heat-resistant storage stability, and durability are likely to be improved. The Mw of the resin A can be controlled by changing the reaction temperature at the time of polymerization, the reaction time, the charging ratio of the monomer, the amount of the initiator, and the like.
The acid value of the resin A in the present invention is preferably 3.0 mgKOH / g or more and 25.0 mgKOH / g or less, and more preferably 5.0 mgKOH / g or more and 20.0 mgKOH / g or less. When the acid value is 3.0 mgKOH / g or more, the pigment having a structure derived from a basic compound has more points to be adsorbed, so that the coloring power, heat-resistant storage stability, and durability are likely to be improved. When the acid value is 25.0 mgKOH / g or less, the cross-linking between pigments can be suppressed, so that the coloring power is improved. The acid value of resin A can be controlled by changing the composition and molecular weight.
The content of the resin A in the present invention is preferably 1.0 part by mass or more and 30.0 parts by mass or less, and more preferably 5.0 parts by mass or more and 25.0 parts by mass or less with respect to 100 parts by mass of the pigment. When the amount is 1.0 part by mass or more, a sufficient amount of resin A can be adsorbed on the pigment, so that the coloring power, heat-resistant storage stability, and durability are likely to be improved. When it is 30.0 parts by mass or less, the polarity of the system is increased by the component that is not adsorbed on the pigment, and it is possible to suppress the cause of pigment aggregation, so that the coloring power is likely to be improved.
Next, the resin B will be specifically described. The resin B in the present invention is characterized by having an acid value of 2.0 mgKOH / g or more. When the acid value is 2.0 mgKOH / g or more, phase separation from wax and other resins during toner production is likely to occur, and it is considered that the dispersibility inside the toner is improved. In addition, when granulating in an aqueous medium to form particles, it is suggested that the particles are likely to be distributed near the surface layer. Therefore, it is considered that durability and heat-resistant storage stability are improved. The acid value of the resin B is preferably 2.5 mgKOH / g or more. The upper limit is not particularly limited, but is preferably 30.0 mgKOH / g or less, and more preferably 25.0 mgKOH / g or less. The acid value of the resin B can be controlled by changing the composition of the resin B. Further, the glass transition temperature TgB of the resin B in the present invention is 50 ° C. or higher. When TgB is 50 ° C or higher, durability and heat resistance are improved. The upper limit is not particularly limited, but is preferably 120 ° C or lower, more preferably 100 ° C or lower. TgB can be controlled by changing the molecular weight, composition, and the like. Further, the hydrophobic parameter HPB of the resin B in the present invention is 0.70 or less. When HPB is 0.70 or less, it is considered that the coloring power, durability, and heat-resistant storage stability are improved because the interaction with the pigment can be suppressed for the above-mentioned reason. HPB is preferably 0.60 or less. The lower limit is not particularly limited, but is preferably 0.30 or more, and more preferably 0.40 or more. HPB can be controlled mainly by changing the composition of resin B. HPB indicates the volume fraction of heptane at the precipitation point of the resin B when heptane is added to the solution containing 0.01 part by mass of the resin B and 1.48 parts by mass of chloroform. ) The resin B of the present invention is preferably used within a range that does not significantly impair other electrophotographic properties such as low temperature fixability, and is preferably used at 0.50% by mass or more and 30.0% by mass or less with respect to the total mass of the toner particles.
In the present invention, HPA and HPB preferably satisfy the following formula (7). HPA-HPB 0.05 (7) When HPA and HPB satisfy the above formula (7), the difference in hydrophobicity between resin A and resin B is large, so the interaction can be further suppressed, and thus the coloring power and durability. , Heat resistance storage stability is easy to improve. HPA-HPB is more preferably 0.10 or more. The upper limit is not particularly limited, but is preferably 0.50 or less, more preferably 0.40 or less.
The content of the resin A is preferably 1.0 part by mass or more, and more preferably 5.0 parts by mass or more and 70.0 parts by mass or less with respect to 100 parts by mass of the resin B. When the amount is 1.0 part by mass or more, the interaction of the resin B with the pigment is easily suppressed, so that the coloring power, durability, and heat-resistant storage stability are easily improved. As the resin B, any resin may be used as long as it is within the above-specified range. Examples thereof include vinyl-based resins, polyester resins, polyamide-based polymers, polyurethane-based polymers, and polyether-based polymers. Among these, vinyl-based resin or polyester resin is preferable from the viewpoint of ease of production and ease of adjusting various parameters.
The vinyl-based resin is a resin obtained by polymerizing a vinyl-based polymerizable monomer capable of radical polymerization. Specifically, the following monomers can be used. Vinyl-based monomers include styrene, α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, and p-tert. -Stylized derivatives such as butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, and p-phenyl styrene; methyl acrylate, ethyl Acrylic, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl Acrylic polymerizable monomers such as acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, and 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate. , N-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate , Dibutyl phosphate ethyl methacrylate, and methacrylic polymerizable monomers such as dibutyl phosphate ethyl methacrylate;
Examples of the polyfunctional polymerizable monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and tripropylene glycol. Diacrylate, Polypropylene Glycol Diacrylate, 2,2'-Bis (4- (Acryloxidiethoxy) phenyl) Propane, Trimethylol Propane Triacrylate, Tetramethylolmethane Tetraacrylate, Ethylene Glycol Dimethacrylate, Diethylene Glycol Dimethacrylate, Triethylene Glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (Methyloxydiethoxy) phenyl) propane, 2,2'-bis (4- (methacryloxypolyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethanetetramethacrylate, divinylbenzene, divinylnaphthalin, And divinyl ether. These can be used alone or in combination of two or more.
The polyester resin is obtained by condensing a polyvalent carboxylic acid and a polyhydric alcohol. Specifically, the following polyvalent carboxylic acids and polyhydric alcohols can be used. Examples of polyvalent carboxylic acids include oxalic acid, glutaric acid, succinic acid, maleic acid, adipic acid, β-methyladipic acid, azelaic acid, sebacic acid, nonandicarboxylic acid, decandicarboxylic acid, undecandicarboxylic acid, dodecandicarboxylic acid, and fumal. Acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1,2-carboxylic acid, hexahydroterephthalic acid, malonic acid, pimelliic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, chlorophthalic acid Acid, nitrophthalic acid, p-carboxyphenylacetic acid, p-phenylene diacetic acid, m-phenylenediglycolic acid, p-phenylenediglycolic acid, o-phenylenediglycolic acid, diphenylacetic acid, diphenyl-p, p'-dicarboxylic acid , Naphthalene-1,4-dicarboxylic acid, naphthalene-1,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, anthracenedicarboxylic acid, cyclohexanedicarboxylic acid and the like. Examples of the polyvalent carboxylic acid other than the dicarboxylic acid include trimellitic acid, pyromellitic acid, naphthalenetricarboxylic acid, naphthalenetetracarboxylic acid, pyrentricarboxylic acid and pyrenetetracarboxylic acid.
Examples of polyols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, and 1,5-pentane. Diol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, sorbitol, 1,2,3,6-hexanetetrol, 1,4- Solbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butane Triol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydride bisphenol A, hydride bisphenol A ethylene oxide adduct Examples include bisphenol hydride A propylene oxide adducts.
The toner of the present invention can be produced by a conventionally known method. Preferably, for example, a polymerizable monomer containing a polymerizable monomer for obtaining a binder resin, resin A and resin B, a pigment dispersion containing a basic treatment pigment, and a mold release agent if necessary. Suspension polymerization method in which the composition is suspended and granulated in an aqueous medium to polymerize the polymerizable monomer contained in the polymerizable monomer composition; various toners containing a basic treatment pigment, resin A and resin B. Kneading and crushing method in which the constituent materials are kneaded, crushed, and classified; a dispersion liquid in which the binder resin is emulsified and dispersed, a pigment dispersion liquid containing resin A and a basic treated pigment, and a dispersion liquid containing resin B are required. A dispersion method in which a dispersion such as a mold release agent is mixed, aggregated and heat-fused to obtain toner particles; a dispersion formed by emulsifying and polymerizing a polymerizable monomer constituting a binder resin. , A pigment dispersion containing resin A and a basic treated pigment, a dispersion containing resin B, and a dispersion such as a mold release agent, if necessary, are mixed, aggregated, and heat-fused to form toner particles. Obtaining emulsification polymerization aggregation method; Organic solvent dispersion liquid containing a binder resin, resin A and resin B, a pigment dispersion liquid containing a basic treated pigment, and a solution such as a release agent, if necessary, in an organic solvent. Can be used as a dissolution / suspension method in which the material is suspended in an aqueous medium for granulation. It is preferable to add the resin A in the step of producing the pigment dispersion liquid because the adsorptivity with the pigment tends to increase and the pigment dispersibility tends to improve. In particular, in the case of a production method having a step of uniformly mixing the toner composition in the oil phase, the resin A, the resin B and the pigment are uniformly mixed, so that the dispersibility of the pigment in the toner is improved. Therefore, the suspension polymerization method or the dissolution suspension method is preferable. That is, in the present invention, a production method including the following steps (i) or (ii) is preferable. (i) A polymerizable monomer composition containing a vinyl-based polymerizable monomer, the resin A, the resin B, and the pigment is granulated in an aqueous medium and contained in the polymerizable monomer composition. Step of polymerizing vinyl-based polymerizable monomer to produce toner particles (ii) An organic solvent dispersion containing the resin A, the resin B and the pigment is granulated in an aqueous medium in an organic solvent. Process of manufacturing toner particles
The toner of the present invention may contain a mold release agent. As the release agent, fatty acid hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystallin wax, paraffin wax; oxides of fatty acid hydrocarbon waxes such as polyethylene oxide wax; fatty acid hydrocarbon waxes. Block copolymer; wax containing fatty acid ester as main component such as carnauba wax, sazole wax, montanic acid ester wax; and deoxidized fatty acid ester such as carnauba wax partially or completely deoxidized, behenic acid Partial esterifications of fatty acids such as monoglycerides and polyhydric alcohols; methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable fats and oils. The content of the release agent is preferably 3% by mass or more and 12% by mass or less in the toner particles.
The toner of the present invention may contain a charge control agent. As the charge control agent used for the toner of the present invention, a conventionally known charge control agent can be used. As a negative charge control agent, for example, a metal compound of an aromatic carboxylic acid such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid; a polymer having a sulfonic acid group, a sulfonic acid base or a sulfonic acid ester group, or Copolymers; metal salts or metal complexes of azo dyes or azo pigments; boron compounds, silicon compounds, calix arenes. Examples of the positive charge control agent include a quaternary ammonium salt and a polymer compound having a quaternary ammonium salt in the side chain; a guanidine compound; a niglosin compound; and an imidazole compound. Examples of the polymer or copolymer having a sulfonic acid base or a sulfonic acid ester group include styrene sulfonic acid, 2-acrylamide-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, vinylsulfonic acid, and the like. It is possible to use a homopolymer of a sulfonic acid group-containing vinyl-based monomer such as methacrylsulfonic acid, or a copolymer of the vinyl-based monomer and the sulfonic acid group-containing vinyl-based monomer. The content of the charge control agent is preferably 0.1% by mass or more and 5% by mass or less in the toner particles.
In the present invention, an external additive may be externally added to the toner particles in order to improve the image quality of the toner. As the external additive, inorganic fine powder such as silica fine powder, titanium oxide fine powder, or aluminum oxide fine powder is preferably used. These inorganic fine powders are preferably hydrophobized with a silane coupling agent, silicone oil, or a hydrophobizing agent of a mixture thereof. Further, the toner of the present invention may be mixed with an external additive other than the above with the toner particles, if necessary.
The toner of the present invention may contain a resin (binding resin) for binding various materials in addition to the above-mentioned materials. As the binder resin used in the toner of the present invention, known resins such as vinyl resins, maleic acid copolymers, polyester resins, and epoxy resins can be used. Of these, vinyl resins and polyester resins are preferable from the viewpoint of ease of manufacture. As the monomer of the vinyl resin and the polyester resin, the above-mentioned resin B can be used.
Hereinafter, a method for measuring various physical properties according to the present invention will be described. <Measurement method of hydrophobic parameters HPA and HPB> Hydrophobic parameters HPA and HPB are measured as follows. Take 0.01 g of resin A in an 8 ml sample bottle, dissolve in 1.48 g (1.0 ml) of chloroform, and measure the initial mass (W1). Put a stirrer in a sample bottle, add 100 mg of (a) heptane while stirring with a magnetic stirrer, and continue stirring for 20 seconds. (b) Visually check if it is cloudy. If it is not cloudy, repeat steps (a) and (b). Stop the operation at the point where cloudiness is confirmed (precipitation point), and measure the mass (W2). All measurements are performed at 25 ° C and normal pressure (1 atm). Calculate HPA according to the following formula. The specific density of heptane at 25 ° C and 1 atm is 0.684, and the specific density of chloroform is 1.48. HP = {(W2-W1) /0.684}/{(W2-W1)/0.684)+1} Perform the same measurement three times, and let the average value be HPA. HPB is also measured in the same manner except that the resin A is changed to the resin B in the above measurement method.
<Measurement method of weight average molecular weight and number average molecular weight of resin A and resin> Weight average molecular weight (Mw) and number average molecular weight (Mn) are measured by gel permeation chromatography (GPC) as follows. To do. First, resin A or resin B is dissolved in tetrahydrofuran (THF) at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Myshori Disc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is 0.8% by mass. This sample solution is used for measurement under the following conditions. Equipment: High-speed GPC equipment "HLC-8220GPC" [manufactured by Tosoh Corporation]
Column: 2 series of LF-604 [manufactured by Showa Denko KK]
Eluent: THF Flow velocity: 0.6 mL / min Oven temperature: 40 ° C Sample injection volume: 0.020 mL Standard polystyrene resin (for example, trade name "TSK Standard Polystyrene F-850, F-450," was used to calculate the molecular weight of the sample. 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- Use the molecular weight calibration curve created using "500" (manufactured by Tosoh Corporation).
<Measurement method of glass transition temperature (Tg)> The glass transition temperature (Tg) is measured according to ASTM D3418-82 using a differential scanning calorimeter "Q1000" (manufactured by TA Instruments). The melting points of indium and zinc are used for temperature correction of the device detector, and the heat of fusion of indium is used for the correction of calorific value. Specifically, 2 mg of a measurement sample such as resin B is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the measurement range is between 0 ° C and 150 ° C. Temperature rise rate The temperature rises at a rate of 10 ° C / min. Hold at 100 ° C for 15 minutes, then cool between 100 ° C and 0 ° C at a cooling rate of 10 ° C / min. Hold at 0 ° C for 10 minutes, then measure between 0 ° C and 100 ° C at a heating rate of 10 ° C / min. The curve of the stepwise change part of the glass transition and the straight line at the same distance in the vertical axis direction from the extended straight line of each baseline before and after the specific heat change of the specific heat change curve in this second temperature rise process. Let the temperature at the intersection of be the glass transition temperature (Tg).
<Method of measuring the weight average particle size (D4) of toner particles and toner> The weight average particle size (D4) of toner particles and toner is measured by the precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, Beckman Coulter). Measure using (manufactured by the company). The measurement is performed under the following conditions. Number of effective measurement channels: 25,000 channels Total number of control motors: 50,000 Aperture: 100 μm Current: 1600 μA Gain; 2 Kd value is the value obtained using "Standard particle 10.0 μm" (manufactured by Beckman Coulter). Measure. The measurement data is analyzed with the dedicated software attached to the device, and the weight average particle size (D4) is calculated. The "average diameter" of the "analysis / volume statistical value (arithmetic mean)" screen when the graph / volume% is set with the above-mentioned dedicated software is the weight average particle diameter (D4).
<Pigment structure> The structure of the pigment, for example, the average number of basic sites bound to the organic dye, is obtained by nuclear magnetic resonance spectroscopy.<sup>1</sup>H-NMR). Measuring device: JNM-EX400 (manufactured by JEOL Ltd.) Measuring frequency: 400MHz Pulse condition: 5.0μs Frequency range: 10500Hz Number of integrations: 1024 times Measuring solvent: DMSO-d6 Dissolve the sample as much as possible and measure under the above conditions. .. From the chemical shift value and proton ratio of the obtained spectrum, the structure of the treatment agent and the average amount introduced into the maternal skeleton are calculated.
<Measurement method of base value and pKa of pigment> The base value of the pigment is the number of mg of hydrochloric acid and equivalent potassium hydroxide required to neutralize the base contained in 1 g of the sample. The basic value of the pigment is measured according to the following procedure. Titration is performed using a 0.1 mol / L ethanol hydrochloride solution. The above 0.1 mol / L hydrochloric acid used is prepared in accordance with JIS K 8001-1998. The measurement conditions for base titer measurement are shown below. Titration device: Potentiometric titrator AT-510 (manufactured by Kyoto Denshi Kogyo Co., Ltd.) Electrode: Composite glass electrode Double junction type (manufactured by Kyoto Denshi Kogyo Co., Ltd.) Control software for titrator: AT-WIN Titration analysis software: Tview The titration parameters and control parameters in the above are as follows. Titration parameters Titration mode: Blank Titration Titration style: Total titration Maximum titration Quantification: 20 ml Wait time before titration: 30 seconds Titration direction: Automatic control parameter End point judgment potential: 30dE End point judgment potential value: 50dE / dmL End point detection judgment: Not set Control rate mode: Standard gain: 1 Data collection potential: 4 mV Data collection Titration: 0.1 ml This test; 200.0 g of a mixed solution of 10.0 g of pigment, 140.0 g of toluene and 60.0 g of ethanol (7: 3) and 250 g of 0.8 mm glass beads were placed in a pressure-resistant container and dispersed for 5 hours using a paint shaker (manufactured by Toyo Seiki Seisakusho Co., Ltd.). To obtain a pigment dispersion. Weigh 100.0 g of this pigment dispersion into a tall beaker. Titration is performed using the above-mentioned potentiometric titrator and the above-mentioned hydrochloric acid ethanol solution. Blank test; Perform the same titration as above, except that no sample is used (ie, only a mixed solution of 140.0 g of toluene and 60.0 g of ethanol). Calculation of base value; Substitute the obtained result into the following formula to calculate the base value. BV = [(CB) × f × 5.611] / S (in the formula, BV: base value (mgKOH / g), B: addition amount of ethanol solution in blank test (ml), C: ethanol solution in hydrochloric acid in this test Addition amount (ml), f: Factor of potassium hydroxide solution, S: Sample (g).) Determination of pKa; The point where the slope of the pH change is the largest from the titration curve obtained during the base titer measurement is defined as the neutralization point. The pKa of the pigment is calculated as follows. The pH at half the amount of 0.1 mol / l hydrochloric acid / ethanol solution required up to the neutralization point is read from the titration curve, and the read pH value is taken as pKa. However, if the base value is less than 0.1 and it is difficult to determine the neutralization point, the pH at the start of titration is pKa.
<Method of measuring acid value> Acid value is the number of mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample. The acid value of resin A is measured according to JIS K 0070-1992, but specifically, it is measured according to the following procedure. (1) Preparation of reagents Dissolve 1.0 g of phenolphthalein in 90 ml of ethanol (95% by volume) and add ion-exchanged water to make 100 ml to obtain a phenolphthalein solution. Dissolve 7 g of special grade potassium hydroxide in 5 ml of water and add ethanol (95% by volume) to make 1 L. Put it in an alkali-resistant container so as not to come into contact with carbon dioxide, leave it for 3 days, and then filter it to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. As for the factor of the potassium hydroxide solution, take 25 ml of 0.1 mol / L hydrochloric acid in a triangular flask, add a few drops of the phenolphthaline solution, titrate with the potassium hydroxide solution, and neutralize the potassium hydroxide solution. Obtained from the amount of. The 0.1 mol / l hydrochloric acid used is prepared in accordance with JIS K 8001-1998. (2) Operation (A) This test Weigh 2.0 g of resin B into a 200 ml Erlenmeyer flask, add 100 ml of a mixed solution of toluene / ethanol (2: 1), and dissolve over 5 hours. Then, a few drops of the phenolphthalein solution are added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of the titration is when the light red color of the indicator continues for about 30 seconds. (B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used). (3) Substitute the obtained result into the following formula to calculate the acid value. A = [(CB) × f × 5.61] / S where A: acid value (mgKOH / g), B: amount of potassium hydroxide solution added in the blank test (ml), C: potassium hydroxide in this test Addition amount of solution (ml), f: Potassium hydroxide solution factor, S: Sample (g).
<p> Hereinafter, the present invention will be described in more detail with reference to Examples. The present invention is not limited by the following examples. Unless otherwise specified, "parts" and "%" in Examples and Comparative Examples are all based on mass.</p><p><Manufacture of Basic Treated Pigment> A basic treated pigment was manufactured according to the manufacturing method described in Japanese Patent No. 4484171.</p><p><Manufacturing of treatment agent 1> In a reaction vessel set with a stirring blade, condenser, thermometer, and nitrogen introduction tube, 40 parts of 98% sulfuric acid, 36.7 parts of 25% fuming sulfuric acid, 6.3 parts of diethylamine, and 2.8 parts of 92% paraformaldehyde. Prepared at ° C. After stirring at 40 ° C. for 30 minutes, 8.0 parts of copper phthalocyanine was slowly added. After the addition, the temperature of the reaction solution was raised, and the reaction was carried out at 80 ° C. for 5 hours. After completion of the reaction, the reaction solution was cooled to room temperature, taken out into 750 parts of water, the slurry was filtered, washed with water, and dried to obtain a treatment agent 1 into which a diethylaminomethyl group was introduced. As a result of NMR analysis of the obtained treatment agent 1, 2.1 diethylaminomethyl groups were introduced on average. Table 1 shows the physical characteristics of the treatment agent 1.</p><p><Production of treatment agents 2 to 5> The treatment agents 2 to 5 shown in Table 1 were produced by the same method as the production of treatment agent 1 except that the structure of the amine compound and the maternal skeleton were changed.</p><p><tables num="1"><img file="JP6727872B2_D0009.tif" /></tables> In Table 1, CuPc of the structure shows copper phthalocyanine and Qd shows 2,9-dimethylquinacridone.</p><p><Production of Basic Treatment Pigment 1> 2.0 parts by mass of Treatment Agent 1 was added to CIPigmentBlue 15: 3 (100.0 parts by mass) and mixed by shaking for 24 hours to prepare Basic Treatment Pigment 1. Table 2 shows the physical characteristics of the obtained basic treated pigment 1. <Manufacturing of basic treated pigments 2 to 10> The basics shown in Table 2 below are produced by the same method as for the production of basic treated pigment 1, except that the treatment agent type, pigment type and mixing ratio of each are appropriately changed. Treated pigments 2-10 were produced.</p><p><tables num="2"><img file="JP6727872B2_D0010.tif" /></tables> In the table, PB15: 3 stands for PigmentBlue15: 3, CB stands for carbon black, and PR122 stands for PigmentRed122.</p><p><Synthesis of resin A> Resin A was synthesized according to the following procedure. <Synthesis example of compound C1> 78.6 g of 2,4-dihydroxybenzoic acid was dissolved in 400 mL of methanol, 152.0 g of potassium carbonate was added, and the mixture was heated to 60 ° C. A solution prepared by mixing and dissolving 87.9 g of 4- (chloromethyl) styrene and 100 ml of methanol was added dropwise to this reaction solution, and the mixture was reacted at 60 ° C. for 2.5 hours. The obtained reaction solution was cooled, filtered, and washed with methanol. The obtained precipitate was dispersed in 1 L of water having a pH of 1 with hydrochloric acid. Then, it was washed with filtered water and dried at 80 ° C., and 55.7 g of the compound C1 represented by the following formula was obtained.</p><p><chemistry num="9"><img file="JP6727872B2_D0011.tif" /></chemistry></p><p><Example of Synthesis of Compound C2> 100.0 g of 2,5-dihydroxybenzoic acid was dissolved in 2000 mL of methanol, 88.3 g of potassium carbonate was added, and the mixture was heated to 67 ° C. 102.0 g of 4- (chloromethyl) styrene was added dropwise to this reaction solution over 22 minutes, and the reaction was carried out at 67 ° C. for 12 hours. After cooling the obtained reaction solution, methanol was distilled off under reduced pressure, washed with hexane, and filtered. The residue was dissolved in methanol, further added dropwise to water for reprecipitation, and the precipitate was filtered. This reprecipitation operation was repeated twice, and the residue was dried at 80 ° C. for 48 hours to obtain 48.7 g of compound C2 represented by the following formula.</p><p><chemistry num="10"><img file="JP6727872B2_D0012.tif" /></chemistry></p><p><Example of Synthesis of Compound C3> (Step 1) 100 g of 2,5-dihydroxybenzoic acid and 1441 g of 80% sulfuric acid were heated and mixed at 50 ° C. 144 g of tert-butyl alcohol was added to this dispersion, and the mixture was stirred at 50 ° C. for 30 minutes. Then, 144 g of tert-butyl alcohol was added to this dispersion, and the mixture was stirred for 30 minutes three times. The reaction was cooled to room temperature and slowly poured into 1 kg of ice water. The precipitate was filtered, washed with water, and then washed with hexane. This precipitate was dissolved in 200 mL of methanol and reprecipitated in 3.6 L of water. After filtration, it was dried at 80 ° C. to obtain 74.9 g of a salicylic acid intermediate represented by the following formula.</p><p><chemistry num="11"><img file="JP6727872B2_D0013.tif" /></chemistry></p><p>(Step 2) Compound C3 represented by the following formula was obtained in the same manner as in the synthesis example of compound C2 except that 2,5-dihydroxybenzoic acid was changed to 25.0 g of the salicylic acid intermediate of the above formula.</p><p><chemistry num="12"><img file="JP6727872B2_D0014.tif" /></chemistry></p><p><Example of Synthesis of Compound C4> A salicylic acid intermediate was obtained by the same method as in the synthesis of compound C3 (step 1) except that 144 g of tert-butyl alcohol was changed to 253 g of 2-octanol. Compound C4 of the following formula was obtained by the same method as in the synthesis example of compound C3 (step 2) except that 32 g of the salicylic acid intermediate obtained here was used.</p><p><chemistry num="13"><img file="JP6727872B2_D0015.tif" /></chemistry></p><p><Synthesis example of compound C5> 53.9 g of 2,3-dihydroxybenzoic acid was dissolved in 280 mL of methanol, and K was dissolved in this.<sub>2</sub>CO<sub>3</sub>106 g was added and the mixture was stirred at 65 ° C for 30 minutes. To this, 61.7 g of 4-chloromethylstyrene was added dropwise over 1 hour. After reacting under reflux for 3 hours, the mixture was allowed to cool to room temperature, and the precipitate was filtered and washed with methanol. Methanol in the filtrate was removed under reduced pressure to obtain a brown semi-solid. This brown semi-solid was dispersed in ethyl acetate and water, and the pH was adjusted to 1 with hydrochloric acid. The ethyl acetate layer was washed with saturated brine, dried over magnesium sulfate, and the solvent was removed under reduced pressure to obtain 124.3 g of a pale yellow solid. This pale yellow solid was recrystallized from toluene to obtain 54.5 g of compound C5 of the following formula.</p><p><chemistry num="14"><img file="JP6727872B2_D0016.tif" /></chemistry></p><p><Synthesis Example of Compound C6> Compound C6 of the following formula was synthesized by the method described in JP-A-63-270060.</p><p><chemistry num="15"><img file="JP6727872B2_D0017.tif" /></chemistry></p><p><Compound C7> 2-acrylamide-2-methylpropansulfonic acid was used as compound C7. <Compound C8> Vinyl sulfonic acid was used as compound C8.</p><p><Example of Synthesis of Resin A1> 60.0 parts of toluene was charged in a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube, and refluxed under a nitrogen stream. Next, the following raw materials and solvents were mixed to prepare a monomer mixed solution. Styrene 100.0 parts Compound C1 8.6 parts Stearyl methacrylate 25.3 parts Toluene 60.0 parts 10.0 parts of t-butylperoxyisopropyl monocarbonate (75% hydrocarbon solvent diluted product) was further mixed with this monomer mixed solution as a polymerization initiator, and the mixture was added dropwise to the above-mentioned reaction vessel over 30 minutes. The mixture was stirred at 125 ° C. and cooled to room temperature when the desired molecular weight was obtained. The obtained polymer-containing composition was added dropwise to a mixed solution of 1400 parts of methanol and 10 parts of acetone under stirring for 10 minutes to precipitate and crystallize the resin composition. The obtained resin composition was filtered and rinsed twice with 200 parts of methanol. The obtained resin powder was dried under reduced pressure at 60 ° C. for 10 hours to obtain resin A1. The obtained resin A1 had a hydrophobic parameter HPA of 0.75, a weight average molecular weight (Mw) of 25,000, and an acid value of 15.1 mgKOH / g.</p><p><Synthesis Examples of Resins A2 to A26> The same method as in the synthesis examples of Resin A1 except that the types and amounts of the monomers used, the polymerization temperature and the amount of the initiator were appropriately changed according to the composition shown in Table 3. Resins A2 to A26 were synthesized. Table 4 shows the analysis results of each of the synthesized resins A. In addition, n in the said formula (6) is propyl methacrylate (n = 2), butyl methacrylate (n = 3), stearyl methacrylate (n = 17), behenyl methacrylate (n = 21).</p><p><Resin A27> DISPERS BYK (registered trademark) -102 (manufactured by BYK Additives & Instruments) was used as the resin A27. The acid value of resin A27 was 101 mgKOH / g, and the HPA was 0.40.</p><p><tables num="3"><img file="JP6727872B2_D0018.tif" /></tables></p><p><tables num="4"><img file="JP6727872B2_D0019.tif" /></tables></p><p><Synthesis of resin B1> Add 100 parts of a mixture of raw material monomers at the mol ratio shown in Table 5-1 to a reaction vessel equipped with a stirrer, thermometer, nitrogen introduction tube, dehydration tube, and decompression device. The mixture was heated to a temperature of 130 ° C with stirring. Then, 0.52 parts of di (2-ethylhexanoic acid) tin was added as an esterification catalyst, the temperature was raised to 200 ° C., and polycondensation was performed until the desired molecular weight was obtained to obtain resin B1. The physical characteristics of the obtained resin B1 are shown in Table 5-1.</p><p><Synthesis of Resins B2 and B4> Resins B2 and B4 were synthesized by the same method as that of the above-mentioned resin B1 except that the raw material monomer species and the amount charged were changed as shown in Table 5-1. The analysis results of the obtained resins B2 and B4 are shown in Table 5-1.</p><p><Production example of resin B3> 200 parts of xylene was placed in a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube. 75% toluene of 100 parts of the mixture of the raw material monomers mixed in the mol ratio shown in Table 5-2 and the polymerization initiator 1,1,3,3-tetramethylbutylperoxy2-ethylhexanoate 13.7 parts of the solution was mixed and added dropwise to the reaction vessel with stirring. The reaction was stopped by heating and stirring at 65 ° C. and cooling the reaction solution when the desired molecular weight was reached. The reaction mixture was purified by solid-liquid separation in methanol and then dried under reduced pressure at 40 ° C. to obtain resin B3. The molecular weight and acid value were analyzed by the method described above. The physical characteristics of the obtained resin B3 are shown in Table 5-2.</p><p><Examples of Synthesis of Resins B5 to B8> Resins B5 to B8 were synthesized by the same method as that of the above-mentioned resin B3, except that the raw material monomer species and the amount charged were changed as shown in Table 5-2. The analysis results of the obtained resins B5 to B8 are shown in Table 5-2.</p><p><tables num="5-1"><img file="JP6727872B2_D0020.tif" /></tables> In Table 5-1 TPA is terephthalic acid, IPA is isophthalic acid, TMA is trimellitic acid, CHDA is cyclohexanedicarboxylic acid, BPA-PO is propylene oxide 2 mol adduct of bisphenol A, and BPA-EO is ethylene of bisphenol A. Represents a 2 mol adduct of oxide.</p><p><tables num="5-2"><img file="JP6727872B2_D0021.tif" /></tables> In Table 5-2, St stands for styrene, MMA stands for methyl methacrylate, STMA stands for stearyl methacrylate, MAA stands for methacrylic acid, and HEMA stands for 2-hydroxyethyl methacrylate.</p><p><Manufacturing of Styrene Acrylic Resin 1> 200 parts of xylene was placed in a reaction vessel equipped with a stirrer, a condenser, a thermometer, and a nitrogen introduction tube. Mix 75 parts of styrene, 25 parts of n-butyl acrylate, and 10.0 parts of a 75% toluene solution of the polymerization initiator 1,1,3,3-tetramethylbutylperoxy2-ethylhexanoate, and stir in the reaction vessel. While dripping. The reaction was stopped by heating and stirring at 65 ° C. and cooling the reaction solution when the desired molecular weight was reached. The reaction mixture was purified by solid-liquid separation in methanol and then dried under reduced pressure at 40 ° C. to obtain a styrene acrylic resin 1. The obtained styrene acrylic resin 1 had an Mn of 14000 and a Mw of 35000.</p><p><Manufacturing of polyester resin 1> 100 parts of bisphenol A-PO 2 molar adduct, 21.7 parts of terephthalic acid, 23.5 parts of sebacic acid in a reaction vessel equipped with a stirrer, thermometer, nitrogen introduction tube, dehydration tube, and decompression device. Was added and heated to a temperature of 130 ° C. with stirring. Then, 0.52 parts of di (2-ethylhexanoic acid) tin was added as an esterification catalyst, the temperature was raised to 200 ° C., and polycondensation was performed until a desired molecular weight was obtained to obtain a polyester resin 1. The obtained polyester resin 1 had Mn of 8000 and Mw of 27000.</p><p><Manufacturing example of toner 1> Styrene 216.0 parts Basically treated pigment 1 36.0 parts Resin A1 3.6 parts The above material was introduced into the Attritor (manufactured by Mitsui Miike Machinery Co., Ltd.), and zirconia beads (180 parts) with a radius of 2.5 mm were introduced. ) Was stirred at 250 rpm and 25 ° C for 180 minutes to prepare a masterbatch dispersion (MB) 1. Masterbatch dispersion 1 191.7 parts Styrene monomer 116.1 parts n-butyl acrylate monomer 92.7 parts Hydrocarbon wax 31.5 parts (HNP-9 manufactured by Nippon Seiko Co., Ltd.) Resin B1 18.0 parts The mixture was mixed and heated to 65 ° C., and uniformly dissolved and dispersed at 3500 rpm for 60 minutes using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain a toner composition solution. On the other hand, in a 2-liter four-necked flask equipped with a TK homomixer, 0.1 mol / L-Na in 1000.0 parts of ion-exchanged water.<sub>3</sub>PO<sub>4</sub>After adding 480.0 parts of the aqueous solution, the TK homomixer was adjusted to 10,000 rpm and heated to 60 ° C. Then 1.0 mol / L-CaCl<sub>2</sub>71.9 parts of an aqueous solution and 3.9 parts of 10% hydrochloric acid were gradually added to obtain an aqueous medium containing a calcium phosphate compound. Next, 13.7 parts of a 75% toluene solution of the polymerization initiator 1,1,3,3-tetramethylbutylperoxy2-ethylhexanoate was dissolved in the toner composition solution, and after thoroughly mixing, the above aqueous medium was used. I put it in. This is at a temperature of 65 ° C, N<sub>2</sub>In the atmosphere, the polymerizable monomer composition was granulated by stirring with a TK homomixer at 10,000 rpm for 10 minutes. Then, the temperature was raised to 75 ° C. while stirring with a paddle stirring blade, and polymerization was carried out for 5 hours. Then, the temperature was raised to 85 ° C at a heating rate of 1 ° C / min. And reacted for 1 hour to complete the polymerization reaction. Then, the residual monomer of the toner particles was distilled off under reduced pressure, and the aqueous medium was cooled to obtain a dispersion liquid of the toner particles. Hydrochloric acid was added to the dispersion of toner particles 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 under a pressure of 0.4 Mpa with a pressure filter to obtain a toner cake. Next, ion-exchanged water was added to the pressure filter until it was full, and the mixture was washed at a pressure of 0.4 Mpa. This washing operation was repeated three times and then dried to obtain toner particles 1. The weight average particle size (D4) of the obtained toner particles was 5.7 μm. To 100 parts by mass of toner particles 1, 1.5 parts by mass (number average primary particle diameter: 10 nm) of hydrophobic silica fine powder surface-treated with hexamethyldisilazane was added, and Mitsui Henchel Mixer (Mitsui Miike Machinery Co., Ltd.) Toner 1 was obtained by performing a mixing step for 300 seconds.</p><p><Production Examples of Toners 2 to 40> Toners 2 to 40 were obtained in the same manner except that the materials of the toner particles were changed as shown in Tables 6-1 and 6-2 in the production examples of toner 1. The obtained toners 2 to 40 are shown in Tables 6-1 and 6-2.</p><p><Production example of comparison toners 1 to 5> In the production example of toner 1, comparison toners 1 to 5 are obtained in the same manner except that the material of the toner particles is changed as shown in Tables 6-1 and 6-2. It was. Tables 6-1 and 6-2 show the obtained comparative toners 1 to 5.</p><p><tables num="6-1"><img file="JP6727872B2_D0022.tif" /></tables></p><p><tables num="6-2"><img file="JP6727872B2_D0023.tif" /></tables></p><p><Manufacturing example of toner 41> Methyl ethyl ketone 144.0 parts Basically treated pigment 1 36.0 parts Resin A1 3.6 parts Introduce the above material into the attritor and use zirconia beads (180 parts) with a radius of 2.5 mm at 250 rpm, 25 ° C. The masterbatch dispersion 41 was prepared by stirring with the mixture for 180 minutes. Masterbatch dispersion 41 96.4 parts Methyl ethyl ketone 59.4 parts Styrene acrylic resin 1 259.6 parts Hydrocarbon wax 18.9 parts (HNP-9 manufactured by Nippon Seiko Co., Ltd.) Resin B1 15.8 parts Mix the above materials at 75 ° C Was uniformly dissolved and dispersed at 5000 rpm for 60 minutes using a TK homomixer to obtain a toner composition solution. On the other hand, in a 2-liter four-necked flask equipped with a TK homomixer, 0.1 mol / L-Na in 1000.0 parts of ion-exchanged water.<sub>3</sub>PO<sub>4</sub>After adding 480.0 parts of the aqueous solution, the TK homomixer was adjusted to 10,000 rpm and heated to 60 ° C. Then 1.0 mol / L-CaCl<sub>2</sub>71.9 parts of an aqueous solution and 3.9 parts of 10% hydrochloric acid were gradually added to obtain an aqueous medium containing a calcium phosphate compound. Next, the toner composition solution was charged into the aqueous medium. This was stirred at a temperature of 75 ° C. and a TK homomixer at 13,000 rpm for 30 minutes to granulate the toner composition solution. Then, the temperature was raised to 85 ° C. while stirring with a paddle stirring blade, and distillation was carried out under normal pressure for 5 hours. Then, after further distilling off the residual solvent under reduced pressure, the aqueous medium was cooled to obtain a dispersion of toner particles. Hydrochloric acid was added to the dispersion of toner particles 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 under a pressure of 0.4 Mpa with a pressure filter to obtain a toner cake. Next, ion-exchanged water was added to the pressure filter until it was full, and the mixture was washed at a pressure of 0.4 Mpa. This washing operation was repeated three times and then dried to obtain toner particles 41. The weight average particle size (D4) of the obtained toner particles was 6.2 μm. Toner 41 was obtained by adding hydrophobic silica fine powder surface-treated with hexamethyldisilazane in the same manner as toner particles 1. The obtained toner 41 is shown in Tables 7-1 and 7-2.</p><p><tables num="7-1"><img file="JP6727872B2_D0024.tif" /></tables></p><p><tables num="7-2"><img file="JP6727872B2_D0025.tif" /></tables></p><p><Manufacturing example of toner 42> Manufacturing example of toner Methyl ethyl ketone 120.0 parts Basically treated pigment 1 30.0 parts Resin A1 3.0 parts Introducing the above material into the attritor and using zirconia beads (180 parts) with a radius of 2.5 mm at 250 rpm , Stirred at 25 ° C. for 180 minutes to prepare a masterbatch dispersion 42. Polyester resin 1 (124.1 parts) was put into a twin-screw kneader (PCM-30 type, manufactured by Ikegai Corp.) set at a temperature of 120 ° C, and the masterbatch dispersion liquid 42 (143.7 parts) was further divided into three times. The solvent was removed by adding and kneading. Polyester resin 1 289.6 parts Resin B1 18.8 parts Hydrocarbon wax 24.8 parts (HNP-9 manufactured by Nippon Seiro Co., Ltd.) Next, the above materials were added and kneaded. The obtained kneaded product was cooled and coarsely pulverized to 1 mm or less with a hammer mill to obtain a coarsely crushed product. The obtained pyroclastic material was finely pulverized with a mechanical crusher (T-250, manufactured by Turbo Industries, Ltd.). Further, classification was performed using a rotary classifier (200TSP, manufactured by Hosokawa Micron Co., Ltd.) to obtain toner particles 42. The operating conditions of the rotary classifier (200TSP, manufactured by Hosokawa Micron) are that the classifying rotor speed is 50.0s.<sup>-1</sup>Classified at. The weight average particle size (D4) of the obtained toner particles 42 was 6.3 μm. Toner 42 was obtained by adding hydrophobic silica fine powder surface-treated with hexamethyldisilazane in the same manner as toner particles 1. In the toner 42, HPA-HPB is 0.16, and the amount of resin A with respect to 100 parts of resin B is 15.0 parts.</p><p><Production example of toner 43> <Production example of colorant particle dispersion 1> Methyl ethyl ketone 240.0 parts, basic treatment pigment 1 60.0 parts, resin A1 6.0 parts The above materials were introduced into the attritor and zirconia beads (180) with a radius of 2.5 mm. The masterbatch dispersion 43 was prepared by stirring at 250 rpm and 25 ° C for 180 minutes. 5 parts of anionic surfactant (Neogen R, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was mixed and dissolved in 250.0 parts of ion-exchanged water. The masterbatch dispersion liquid 43 was added dropwise thereto, and the mixture was emulsified and dispersed with a homogenizer (Ultratarax manufactured by IKA), and the entire amount was added and then dispersed for another 10 minutes. This dispersion was distilled off under normal temperature and reduced pressure until the solid content reached 25%, and then dispersed by an ultrasonic bath for 30 minutes to obtain a colorant particle dispersion 1 having a center diameter of 200 nm and a solid content of 25%. ..</p><p><Production example of resin particle dispersion 1> Methyl ethyl ketone 200.0 parts Polyester resin 1 280.2 parts Put the above materials into a reactor equipped with a stirrer, dissolve at 70 ° C for 60 minutes, mix, and then bring to 95 ° C. A neutralizing aqueous solution prepared by dissolving 5.0 parts of sodium dodecylbenzene sulfonate and 3.0 parts of a 1N NaOH aqueous solution in 1200 parts of heated ion-exchanged water was put into a flask and emulsified with a homogenizer (Ultratalax) for 5 minutes. The solvent was distilled off under a reduced pressure of 60 ° C. until the solid content reached 20%, the mixture was dispersed by an ultrasonic bath for 30 minutes, and the flask was cooled with water at room temperature (25 ° C.). As a result, a resin particle dispersion liquid 1 having a median diameter of 250 nm and a solid content of 20% by mass was obtained.</p><p><Production example of mold release agent particle dispersion 1> 0.8 parts of anionic surfactant (Neogen R, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 350.0 parts of ion-exchanged water 40.0 parts of hydrocarbon wax (HNP-9) (Manufactured by Nippon Seiko Co., Ltd.) The above components were mixed, heated to 120 ° C., and dispersed with a pressure-discharging Gorin homogenizer to obtain a 20% by mass release agent particle dispersion liquid 1 having a volume average particle diameter of 170 nm. .. </p><p><Production example of coated resin particle dispersion liquid 1> Methyl ethyl ketone 100.0 parts Resin B1 70.6 parts Put the above materials into a reactor equipped with a stirrer, dissolve and mix at 70 ° C for 60 minutes, and then bring to 95 ° C. A neutralizing aqueous solution prepared by dissolving 1.4 parts of sodium dodecylbenzene sulfonate and 3.0 parts of a 1N NaOH aqueous solution in 350 parts of heated ion-exchanged water was put into a flask and emulsified with a homogenizer (Ultratalax) for 5 minutes. The solvent was distilled off under a reduced pressure of 60 ° C. until the solid content reached 20%, the mixture was dispersed by an ultrasonic bath for 30 minutes, and the flask was cooled with water at room temperature (25 ° C.). As a result, a coated resin particle dispersion liquid 1 having a median diameter of 240 nm and a solid content of 20% by mass was obtained.</p><p>(Preparation of toner particles 43) Resin particle dispersion liquid 1 1660.0 parts Colorant particle dispersion liquid 1 105.6 parts Anionic surfactant 25.0 parts (Dowfax 2A1 20% aqueous solution) Release agent particle dispersion liquid 1: 112.9 parts First, among the above raw materials, resin particle dispersion 1, anionic surfactant, and 250 parts of ion-exchanged water were placed in a polymerization kettle equipped with a pH meter, stirring blades, and a thermometer, and the mixture was stirred at 130 rpm for 15 minutes. , Surfactant was applied to the resin particle dispersion liquid 1. A colorant particle dispersion 1 and a release agent dispersion 1 were added thereto and mixed, and then a 0.3 mol / L nitric acid aqueous solution was added to this raw material mixture to adjust the pH to 4.8. Then, while applying a shearing force at 3000 rpm with Ultratarax, 20.0 parts of a 10% nitric acid aqueous solution of aluminum sulfate was added dropwise as a coagulant. Since the viscosity of the raw material mixture increases during the dropping of the coagulant, the dropping speed was slowed down when the viscosity increased so that the coagulant was not biased to one place. When the dropping of the coagulant was completed, the rotation speed was further increased to 5000 rpm and the mixture was stirred for 5 minutes to sufficiently mix the coagulant and the raw material mixture. Then, the raw material mixture was stirred at 500 rpm while being heated to 25 ° C. with a mantle heater. After confirming the formation of the primary particle size, the temperature was raised to 43 ° C at 0.1 ° C / min to grow the agglomerated particles. The growth of agglomerated particles was confirmed at any time, and the agglomeration temperature and the number of rotations of stirring were changed according to the agglomeration rate. When the agglomerated particles grew to 5.2 μm in the above agglomeration step, the coating resin particle dispersion liquid 1 was added and held for 20 minutes with stirring. Then, in order to stop the growth of the coated agglomerated particles, 1 mol / L aqueous sodium hydroxide solution was added to control the pH of the raw material mixture to 7.6. Then, in order to fuse the agglomerated particles, the temperature was raised to 85 ° C at a heating rate of 1 ° C / min while adjusting the pH to 7.6. After reaching 85 ° C, adjust the pH to 7.6 or less to promote the fusion, confirm that the aggregated particles have fused with an optical microscope, and then add ice water to stop the growth of the particle size. It was injected and rapidly cooled at a temperature lowering rate of 10 ° C / min. The resulting particles were then sieved once with a 15 μm mesh for the purpose of washing. Then, about 10 times the amount of ion-exchanged water (30 ° C) was added to the solid content, and the mixture was stirred for 20 minutes and then filtered once. Further, the solid content remaining on the filter paper was dispersed in the slurry, washed repeatedly with ion-exchanged water at 30 ° C. four times, and dried to obtain toner particles 43. The weight average particle size (D4) of the obtained toner particles 43 was 5.9 μm. Toner 43 was obtained by adding hydrophobic silica fine powder surface-treated with hexamethyldisilazane in the same manner as toner particles 1. The weight average particle size (D4) of the obtained toner was 5.9 μm. In the toner 43, HPA-HPB is 0.16, and the amount of resin A with respect to 100 parts of resin B is 15.0 parts.</p><p><Production example of comparison toners 6 to 8> In the production example of toner 41, comparison toners 6 to 8 are obtained in the same manner except that the material of the toner particles is changed as shown in Tables 7-1 and 7-2. It was. The obtained comparative toners 6 to 8 are shown in Tables 7-1 and 7-2.</p><p><Examples 1 to 43, Comparative Examples 1 to 8> The coloring power, durability, and heat resistance of the toners 1 to 43 and the comparison toners 1 to 8 were evaluated as follows. <Evaluation of coloring power> Remove the toner contained in the cartridge for the commercially available color laser printer Satera LBP7700C (manufactured by Canon Inc.), clean the inside with an air blow, and then apply the test toner (150 g). Filled. In addition, the fixing machine of the color laser printer was removed and changed so that an unfixed image could be output, so that the image density could be adjusted. Furthermore, it was modified so that it would work even if only one color cartridge was installed. The removed fixing machine was improved so that it could operate as a single fixing machine, and further modified as an external fixing machine so that the process speed and temperature could be controlled. The above cartridge was attached to the printer, and after a 30 mm blank above the transfer material, a band image of 150 mm in width × 30 mm in length was created. Furthermore, the amount of toner on the band image is 0.35 mg / cm.<sup>2</sup>It was set to be. The transfer material is A4 size GF-C081 (manufactured by Canon, 81.4 g / m).<sup>2</sup>) Was used. Ten of these band images were output and fixed at a process speed of 230 mm / sec and 150 ° C using an external fixing machine of the color laser printer LBP7700C. The coloring power was evaluated by measuring the image density of the obtained fixed image. The image density was measured using a "Macbeth reflection densitometer RD918" (manufactured by Macbeth). Measure the relative density of the white background part with a document density of 0.00 with respect to the printout image, measure each of the left, center, and right parts for each fixed image, and evaluate with the arithmetic mean value of 10 fixed images. did. The evaluation criteria are as follows. In the present invention, C or higher is defined as the level at which the effect of the present invention can be obtained. The evaluation results are shown in Table 8. A: Image density is 1.40 or more and B: Image density is 1.35 or more and less than 1.40 C: Image density is 1.30 or more and less than 1.35 D: Image density is 1.25 or more and less than 1.30 E: Image density is less than 1.25</p><p><Durability evaluation> A commercially available color laser printer (HP Color LaserJet 3525dn, manufactured by HP) was modified and evaluated so that it would work even if only one color process cartridge was installed. The toner contained in the cyan cartridge mounted on this color laser printer was extracted, the inside was cleaned with an air blow, and then 200 g of test toner was filled. Canon office planner (64g / m) as image receiving paper under normal temperature and humidity (23 ° C, 60% RH)<sup>2</sup>) Was used to continuously print 20,000 1% print rate charts. After the image was drawn, a halftone image was further output, and the presence or absence of vertical streaks in the paper ejection direction in the halftone image was observed. Durability was evaluated according to the following criteria, and in the present invention, C or higher was set to the level at which the effect of the present invention can be obtained. The evaluation results are shown in Table 8. A: There are no vertical streaks or one streak on the image. B: There are 2 or 3 vertical stripes on the image. C: There are 4 vertical stripes on the image. D: There are 5 vertical stripes on the image. E: There are 6 or more vertical stripes on the image.</p><p><Heat-resistant storage (blocking)> 5 g of each toner was placed in a 50 cc polycup and left for 72 hours in two environments with a temperature of 50 ° C / humidity of 10% RH and a temperature of 55 ° C / humidity of 10% RH. The presence or absence of agglomerates of the left toner was examined and evaluated. In the present invention, C or higher is defined as the level at which the effect of the present invention can be obtained. The evaluation results are shown in Table 8. (Evaluation criteria) A: No agglutination occurs B: Minor agglutination occurs but collapses when pressed lightly with a finger C: Agglutination occurs but collapses when lightly pressed with a finger D: Completely agglutinates, finger Does not collapse even if you press hard with</p><p><tables num="8"><img file="JP6727872B2_D0026.tif" /></tables></p>
32 sheets
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| Event | Code | |
|---|---|---|
| First payment of annual fees (during grant procedure)JAPANESE INTERMEDIATE CODE: A61A61 | A61 | |
| Written notification of patent or utility model registrationJAPANESE INTERMEDIATE CODE: R151R151 | R151 | |
| Written decision to grant a patent or to grant a registration (utility model)JAPANESE INTERMEDIATE CODE: A01A01 | A01 | |
| Decision of grant or rejection writtenTRDD | TRDD | |
| Written amendmentJAPANESE INTERMEDIATE CODE: A523A521 | A521 | |
| Notification of reasons for refusalJAPANESE INTERMEDIATE CODE: A131A131 | A131 | |
| Report on retrievalJAPANESE INTERMEDIATE CODE: A971007A977 | A977 | |
| Written request for application examinationJAPANESE INTERMEDIATE CODE: A621A621 | A621 | |
| Notification of acceptance of power of attorneyJAPANESE INTERMEDIATE CODE: A7422RD02 | RD02 |
Numbers
- Publication
- 6727872
- Publication, DOCDB
- 6727872
- Publication, EPODOC
- JP6727872B
- Application
- 55236
- Application, DOCDB
- 2016055236
- Application, EPODOC
- JP20160055236
Titles2
- Japanese
- トナー及びトナーの製造方法
- English
- Toner and toner manufacturing method
Classification
- CPC, 16
- G03G9/0924
- G03G9/08728
- G03G9/08791
- G03G9/08795
- G03G9/08797
- G03G9/09
- G03G9/0926
- G03G9/0806
- G03G9/08726
- G03G9/0918
- G03G9/092
- G03G9/0804
- G03G9/0819
- G03G9/08711
- G03G9/08755
- G03G9/09733
- IPC, 2
- G03G9 087
- G03G9 08
