JP2005194388A - Silicone and method for producing the same - Google Patents

Abstract

[式（１）において、Ｒ¹は互いに独立にＣ１〜１０の脂肪族基、脂環式基、アリール基、アラルキル基、及びフッ素置換アルキル基からなる群より選択される基であり、
Ｒ²は下記式（２）で表されるヒドロキシ残基であり、

（ここで、ａ及びｂは、夫々、０≦ａ≦２６及び １≦ｂ≦２６の整数であり、 １５≦ａ＋ｂ≦２７を満たし、Ｒ³はＣ２４〜Ｃ３４の直鎖脂肪族基である）
Ｘは下記式（３）で表される基であり、

（ここで、Ｒ⁴は式（１）のＲ²と結合され、Ｃ３〜Ｃ１２の脂肪族基もしくは脂環式基であり、Ｒ⁵はＣ１〜Ｃ４の脂肪族基、もしくはＲ⁵はＲ⁴と結合されてＣ７〜Ｃ１２の架橋環式基を形成している）
ｍ及びｎは、夫々、０≦ｍ≦１５０及び０≦ｎ≦３０の整数であり、ｆは０≦ｆ≦３の整数である]
【選択図】 なしA novel silicone suitable for toner and a method for producing the same are provided.
[Solution]
Silicone represented by the following general formula (1).

[In Formula (1), R ¹ is a group independently selected from the group consisting of a C1-10 aliphatic group, an alicyclic group, an aryl group, an aralkyl group, and a fluorine-substituted alkyl group;
R ² is a hydroxy residue represented by the following formula (2),

(Where a and b are 0 ≦ a ≦ 26 and 1 ≦ b ≦ 26 is an integer, 15 ≦ a + b ≦ 27 is satisfied, and R ³ is a C24-C34 linear aliphatic group)
X is a group represented by the following formula (3),

(Here, R ⁴ is bonded to R ² of formula (1) and is a C3 to C12 aliphatic group or alicyclic group, R ⁵ is a C1 to C4 aliphatic group, or R ⁵ is R ^4. To form a C7-C12 bridged cyclic group)
m and n are integers of 0 ≦ m ≦ 150 and 0 ≦ n ≦ 30, respectively, and f is an integer of 0 ≦ f ≦ 3]
[Selection figure] None

Description

The present invention relates to silicone and a method for producing the same. The silicone is suitable for addition to the toner.

  Silicone wax having a long-chain aliphatic group is used as a wax to be added to toner used in PPC copying machines, printers and the like. In order to introduce a long-chain aliphatic group into silicone, there are methods of reacting various natural or synthetic fatty acids or their esters with silicone. As one of them, the present inventor obtained a wax by reacting carnauba wax with silicone (Patent Document 1).

JP 2003-155449 A

  However, the toner containing the silicone wax has a problem of causing aggregation during storage. In addition, there is a problem that the toner is transferred to the heating roller during the process of fixing the toner to the paper. Therefore, an object of the present invention is to provide a silicone wax free from the above problems and a method for producing the same.

[式（１）において、Ｒ¹は互いに独立にＣ１〜１０の脂肪族基、脂環式基、アリール基、アラルキル基、及びフッ素置換アルキル基からなる群より選択される基であり、
Ｒ²は下記式（２）で表されるヒドロキシ残基であり、

（ここで、ａ及びｂは、夫々、０≦ａ≦２６及び １≦ｂ≦２６の整数であり、 １５≦ａ＋ｂ≦２７を満たし、Ｒ³はＣ２４〜Ｃ３４の直鎖脂肪族基である）
Ｘは下記式（３）で表される基であり、及び、

（ここで、Ｒ⁴は式（１）のＲ²と結合され、Ｃ３〜Ｃ１２の脂肪族基もしくは脂環式基であり、Ｒ⁵はＣ１〜Ｃ４の脂肪族基、もしくはＲ⁵はＲ⁴と結合されてＣ７〜Ｃ１２の架橋環式基を形成している）
ｍ及びｎは、夫々、０≦ｍ≦１５０及び０≦ｎ≦３０の整数であり、ｆは０≦ｆ≦３の整数である]
上記本発明の好ましい態様は、以下のとおりである。
Ｒ1がメチル基であり、Ｒ4がプロピレン基であり、及び、Ｒ５がメチレン基であることを特徴とする上記シリコーン。
示差熱分析計を用いて１０℃／分で昇温して得られる吸熱ピークの先端の温度が７８〜８８℃の範囲内であることを特徴とする上記シリコーン。
また、本発明は、シリコーンとカルナウバワックスを反応させてシリコーンワックスを製造する方法において、環状酸無水物基を含有するシリコーンとカルナウバワックスを反応させることを特徴とする方法である。好ましくは、カルナウバワックスが、ＪＩＳＫ８００４に従い測定されるアセチル価５１〜６０を有する。
さらに、本発明は、上記シリコーン又は上記方法により得られるシリコーンワックスを含むトナー用ワックスである。 That is, the present invention is a silicone represented by the following general formula (1).

[In Formula (1), R ¹ is a group independently selected from the group consisting of a C1-10 aliphatic group, an alicyclic group, an aryl group, an aralkyl group, and a fluorine-substituted alkyl group;
R ² is a hydroxy residue represented by the following formula (2),

(Where a and b are 0 ≦ a ≦ 26 and 1 ≦ b ≦ 26 is an integer, 15 ≦ a + b ≦ 27 is satisfied, and R ³ is a C24-C34 linear aliphatic group)
X is a group represented by the following formula (3), and

(Here, R ⁴ is bonded to R ² of formula (1) and is a C3 to C12 aliphatic group or alicyclic group, R ⁵ is a C1 to C4 aliphatic group, or R ⁵ is R ^4. To form a C7-C12 bridged cyclic group)
m and n are integers of 0 ≦ m ≦ 150 and 0 ≦ n ≦ 30, respectively, and f is an integer of 0 ≦ f ≦ 3]
The preferred embodiments of the present invention are as follows.
The above silicone, wherein R1 is a methyl group, R4 is a propylene group, and R5 is a methylene group.
The silicone described above, wherein the temperature at the tip of the endothermic peak obtained by heating at 10 ° C./min using a differential thermal analyzer is in the range of 78 to 88 ° C.
Further, the present invention is a method for producing silicone wax by reacting silicone with carnauba wax, and reacting silicone containing a cyclic acid anhydride group with carnauba wax. Preferably, the carnauba wax has an acetyl value of 51 to 60 measured according to JISK8004.
Further, the present invention is a toner wax containing the silicone or the silicone wax obtained by the method.

  The toner containing the silicone of the present invention does not aggregate during storage and has excellent offset resistance. Moreover, according to the production method of the present invention, a high-purity silicone wax with little unreacted silicone can be obtained. Furthermore, the silicone of the present invention can also be used as a car wax, a release agent, and a lubricity-imparting agent.

式（１）において、Ｒ¹は互いに独立にＣ１〜１０の脂肪族基、脂環式基、アリール基、アラルキル基、及びフッ素置換アルキル基からなる群より選択される基であり、好ましくは脂肪族基、より好ましくはメチル基である。また、ｍ及びｎは、夫々、０≦ｍ≦１５０、好ましくは５≦ｍ≦２０、０≦ｎ≦３０、好ましくは０≦ｎ≦５、の整数であり、及びｆは０≦ｆ≦３の整数であり、好ましくはｎ＝０のときにｆ＝２、ｎ＝１〜５のときにｆ＝２又は３である。 The silicone of the present invention is represented by the following general formula (1).

In the formula (1), R ¹ is a group independently selected from the group consisting of a C1-10 aliphatic group, an alicyclic group, an aryl group, an aralkyl group, and a fluorine-substituted alkyl group, A group, more preferably a methyl group. M and n are integers of 0 ≦ m ≦ 150, preferably 5 ≦ m ≦ 20, 0 ≦ n ≦ 30, preferably 0 ≦ n ≦ 5, respectively, and f is 0 ≦ f ≦ 3. Preferably, f = 2 when n = 0, and f = 2 or 3 when n = 1-5.

ここで、ａ及びｂは、夫々、０≦ａ≦２６及び１≦ｂ≦２６の整数であり、及び１５≦ａ＋ｂ≦２７を満たし、Ｒ³はＣ２４〜Ｃ３４の直鎖脂肪族基である。 In the formula (1), R ² is a hydroxy residue represented by the following formula (2).

Here, a and b are integers of 0 ≦ a ≦ 26 and 1 ≦ b ≦ 26, respectively, satisfy 15 ≦ a + b ≦ 27, and R ³ is a C24-C34 linear aliphatic group.

式（３）において、Ｒ⁴が式（１）のＲ²と結合され、カルボニル基が式（１）のＳｉ原子と結合される。Ｒ⁴はＣ３〜Ｃ１２の脂肪族基もしくは脂環式基であり及びＲ⁵はＣ１〜Ｃ４の脂肪族基もしくは、Ｒ⁵はＲ⁴と結合されていて、Ｒ⁴と一緒にＣ７〜Ｃ１２の架橋環式基を形成している。好ましいＸとしては、Ｒ⁴がプロピレン基であり且つＲ⁵がメチレン基であるもの、及び、下記式（４）で示される種々のものが例示される。

In the formula (1), X is a group represented by the following formula (3).

In Formula (3), R ⁴ is bonded to R ^{2 of} Formula (1), and a carbonyl group is bonded to the Si atom of Formula (1). R ⁴ is an aliphatic group or cycloaliphatic group C3~C12 and R ⁵ C1~C4 aliphatic group or of, R ⁵ is optionally joined with R ^4, a C7~C12 together with R ⁴ A crosslinked cyclic group is formed. Preferred examples of X include those in which R ⁴ is a propylene group and R ⁵ is a methylene group, and various compounds represented by the following formula (4).

The silicone of the present invention has a melting point of about 78 to 88 ° C, preferably 80 to 85 ° C. The melting point is the temperature at the end of an endothermic peak obtained by increasing the temperature at 10 ° C./min using a differential thermal analyzer. The silicone of the present invention gives a toner that is significantly superior in offset resistance and blocking resistance as compared to the wax described in Patent Document 1, as shown in the Examples below. The offset resistance represents the adhesive strength of toner to paper. A toner having high offset resistance has a wide temperature range and the toner is not transferred to the heating roller in the fixing step. Further, the anti-blocking property represents the difficulty of toner aggregation. Details of these measurement methods are described in the Examples section.

The silicone of the present invention can be prepared by reacting a silicone containing a cyclic acid anhydride group with carnauba wax. Since the reactivity of the cyclic acid anhydride group is high, it reacts with carnauba wax with high efficiency, and there is little unreacted silicone. In Patent Document 1 described above, an acid anhydride is reacted with carnauba wax and then reacted with silicone. In the same document, it is considered preferable to use a silicone oil having an acid anhydride group, but there is no detailed description.

ここで、ＹはＣ６〜Ｃ１６の、末端に環状酸無水物基を含有する脂肪族基、脂環式基、もしくは芳香族基である。また、環状酸無水物基は、典型的には５員環であるが、それ以上の大きさの環であってもよい。Ｒ¹は互いに独立にＣ１〜Ｃ１０の脂肪族基、脂環式基、アリール基、アラルキル基、及びフッ素置換アルキル基からなる群より選択される基であり、好ましくは脂肪族基、より好ましくはメチル基である。また、ｍ及びｎは、シリコーン（５）の２５℃における粘度が５〜5000 ｍPa・ｓ、好ましくは10〜3000ｍPa・ｓになるような整数であり、典型的には、夫々、０≦ｍ≦１５０及び０≦ｎ≦３０の整数である。ｆは０≦ｆ≦３の整数であり、好ましくはｎ＝０のときにｆ＝２、ｎ＝１〜５のときにｆ＝２又は３である。 Examples of silicones containing cyclic acid anhydride groups used in the method of the present invention are those of the following formula (5).

Here, Y is a C6-C16 aliphatic group, alicyclic group, or aromatic group containing a cyclic acid anhydride group at the terminal. The cyclic acid anhydride group is typically a 5-membered ring, but may be a larger ring. R ¹ is a group selected from the group consisting of a C1-C10 aliphatic group, an alicyclic group, an aryl group, an aralkyl group, and a fluorine-substituted alkyl group independently of each other, preferably an aliphatic group, more preferably It is a methyl group. M and n are integers such that the viscosity of the silicone (5) at 25 ° C. is 5 to 5000 mPa · s, preferably 10 to 3000 mPa · s, and typically 0 ≦ m ≦ It is an integer of 150 and 0 ≦ n ≦ 30. f is an integer of 0 ≦ f ≦ 3, preferably f = 2 when n = 0, and f = 2 or 3 when n = 1-5.

 The silicone containing a cyclic acid anhydride group is obtained by addition reaction of hydrogen silicone and a cyclic acid anhydride compound containing a double bond at the terminal in the presence of a platinum-based catalyst such as chloroplatinic acid. Can do. Preferably, the cyclic acid anhydride is used in such an amount that the double bond becomes an excess mole (1.05 to 1.4 mole) with respect to 1 mole of SiH group (hydrosilyl group).

As the hydrogen silicone, those in which Y is H in the formula (5) can be used. R1, m, n, and f are the same as those described for the expression (5).

Examples of the cyclic acid anhydride containing a double bond at the terminal include maleic anhydride derivatives having an alkenyl group, such as a vinyl group, an allyl group, a butenyl group, or a pentenyl group, and dicyclohexane as shown in the following formula (6). Pentadiene derivatives are preferred. More preferably, allyl succinic anhydride is used because it has a low boiling point and can be easily removed by heating from the reaction product under reduced pressure after completion of the reaction.

（ａ、ｂは、夫々、０≦ａ≦２６の整数、１≦ｂ≦２６の整数、及び１５≦ａ＋ｂ≦２７を満たす） The carnauba wax used in the present invention is collected from the leaves of carnauba palm. Carnauba wax is based on two types of polymer esters. The first type is an ester of a hydroxy-n-alkanoic acid having 18 to 30 carbon atoms and an n-aliphatic alcohol having 24 to 34 carbon atoms shown below.

(A and b satisfy an integer of 0 ≦ a ≦ 26, an integer of 1 ≦ b ≦ 26, and 15 ≦ a + b ≦ 27, respectively)

The second type is an ester of an n-alkanoic acid having 18 to 30 carbon atoms and an n-aliphatic alcohol having 24 to 34 carbon atoms shown below.
CH ₃ (CH ₂ ) _c COOH
(16 ≦ c ≦ 28 integer)

In the carnauba wax used in the present invention, 70 to 80% by mass of the total mass is the first type of wax and has many hydroxyl groups. The typical physical property values are as follows. Carnauba wax having these physical properties can be obtained from Hiroyuki Kato Co., Ltd., Noda Wax Co., Ltd. and the like.
Melting point (° C.) 80-86, acid value 2-10, saponification value 78-88, iodine value 7-14, and acetyl value 51-60.
The amount of carnauba wax to be reacted with the silicone (5) can be set according to the acetyl value. The acetyl value is measured according to JIS K8004-1963.

The reaction between carnauba wax and silicone (5) is carried out at a temperature of 50 ° C to 200 ° C, preferably 100 ° C to 160 ° C. The solvent may or may not be used. When a solvent is used, an aromatic solvent such as xylene or toluene is preferable. In the reaction, tertiary amines such as triethylamine and tributylamine, and fatty acid alkali metal salts such as potassium acetate and sodium acetate may be used as a catalyst. In the method of the present invention, 95% or more of the silicone (5) reacts with the carnauba wax, so that the reaction product can be added to the toner over time without any treatment other than solvent stripping. The toner does not aggregate. In addition to the toner, the silicone wax of the present invention can be used as a surface modifier such as car wax, various release agents, and a lubricity-imparting agent.

Hereinafter, the present invention will be described with reference to examples. Unless otherwise specified,% is% by mass.
Cyclic anhydride group-containing silicone synthesis example 1
726 g (1 mol) of hydrogen silicone having the following average structural formula and 1000 g of xylene were weighed into a flask and dehydrated at 145 ° C. for 30 minutes.
HMe2SiO (Me2SiO) 8SiMe2H
(Me is a methyl group)
Next, 4 g of a 0.5% chloroplatinic acid toluene solution was added at 100 ° C., and 364 g (2.6 mol) of allyl succinic anhydride was added dropwise. After completion of the dropwise addition, the reaction was allowed to proceed for 5 hours under reflux of xylene. From the measurement of the amount of hydrogen generated by adding alkaline water, it was confirmed that 98% of the SiH groups had reacted. Stripping xylene and excess allyl succinic anhydride by vacuum distillation yielded 986 g of product. The product was confirmed to be the following cyclic acid anhydride group-containing silicone (1) by IR spectrum shown in FIG. In FIG. 1, peaks at about 1780 cm ⁻¹ and about 1860 cm ⁻¹ represent acid anhydride groups.

次に１００℃で、０．５％塩化白金酸トルエン溶液を４ｇ加え、アリルコハク酸無水物２７３ｇ(１.９５モル)を滴下した。滴下終了後、キシレン還流下で５時間反応させたところ、ＳｉＨの９７％が反応したことが確認された。キシレンと過剰のアリルコハク酸無水物をストリップすることにより、環状酸無水物基含有シリコーン(2)８８９ｇを得た。
Cyclic anhydride group-containing silicone synthesis example 2
726 g (0.5 mol) of hydrogen silicone having the following average structural formula and 1000 g of xylene were weighed into a flask and dehydrated at 145 ° C. for 30 minutes.
Me ₃ SiO (Me ₂ SiO) ₁₅ (MeHSiO) ₃ SiMe ₃

Next, 4 g of a 0.5% chloroplatinic acid toluene solution was added at 100 ° C., and 273 g (1.95 mol) of allyl succinic anhydride was added dropwise. After completion of the dropwise addition, the reaction was performed for 5 hours under reflux of xylene. As a result, it was confirmed that 97% of SiH had reacted. By stripping xylene and excess allyl succinic anhydride, 889 g of a cyclic acid anhydride group-containing silicone (2) was obtained.

  Carnauba wax having an acetyl value of 51 was weighed in a flask with 1100 g (corresponding to 1 mol of OH group) and 1500 g of xylene, and dehydrated at 145 ° C. for 1 hour. Next, 453 g (about 0.45 mol) of the cyclic acid anhydride group-containing silicone (1) and 18.5 g (0.1 mol) of tributylamine were added at 140 ° C. Reacted for hours. When the IR spectrum of the reaction product was measured, the acid anhydride group had disappeared. Subsequently, 1522 g of carnauba silicone (A) was obtained by stripping xylene under reduced pressure. The IR spectrum is shown in FIG. 2, and the H-NMR spectrum is shown in FIG. In FIG. 2, it can be seen that there is no peak of the acid anhydride group confirmed in FIG. 1, and it is an ester group or a carboxylic acid group. Further, in FIG. 3, since no H peak of the —CH—OH structure of carnauba wax is observed in the vicinity of 3.5 ppm, it can be seen that almost all OH groups of carnauba wax have reacted. Carnauba silicone (A) was transparent in the molten state. Further, the melting point by DSC was 79 to 85 ° C., and the peak temperature was 83 ° C.

Carnauba wax having an acetyl value of 51, 1100 g (corresponding to 1 mol with OH) and 1500 g of xylene were weighed into a flask and dehydrated at 145 ° C. for 1 hour. Next, 562 g (0.3 mol) of the cyclic acid anhydride group-containing silicone (2) and 0.1 g of potassium acetate were introduced into the flask at 140 ° C., followed by reaction for 5 hours under reflux of xylene. . When the IR spectrum of the reaction product was measured, the acid anhydride group had disappeared. Subsequently, 1612 g of carnauba silicone (B) was obtained by stripping xylene under reduced pressure. Carnauba silicone (B) was transparent in the molten state. Moreover, melting | fusing point measured by DSC was 78-85 degreeC.

Comparative Example 1
Carnauba wax having an acetyl value of 51, 1100 g (corresponding to 1 mol with OH) and 1500 g of xylene were weighed into a flask and dehydrated at 145 ° C. for 1 hour. Next, 2388 g (0.9 mol) of an isocyanate functional silicone having the following average structural formula was added dropwise at 100 ° C. and reacted at the same temperature for 5 hours. When the IR spectrum of the reaction product was measured, the isocyanate group had disappeared. Subsequently, 3420 g of carnauba silicone (C) was obtained by stripping xylene under reduced pressure. The melting point measured by DSC was 79-85 ° C.

Comparative Example 2
Carnauba wax having an acetyl value of 51, 1100 g (corresponding to 1 mol with OH) and 1500 g of xylene were weighed into a flask and dehydrated at 145 ° C. for 1 hour. Next, 95 g (1 mol) of succinic anhydride and 18.5 g (0.1 mol) of tributylamine were added at 140 ° C., and the reaction was allowed to proceed for 4 hours to convert the carnauba hydroxyl group into a carboxy group. Next, 378 g (0.45 mol) of an amine functional silicone having the following average structural formula was added at 140 ° C., and the reaction was carried out under reflux of xylene while separating water with an ester adapter. The reaction was stopped after a theoretical amount of water separated after 3 hours. Subsequently, 1520 g of carnauba silicone (D) was obtained by stripping xylene under reduced pressure. The melting point measured by DSC was 82-90 ° C.

(ここで、Ωはシクロヘキセンエポキシドを表す)
Comparative Example 3
Carnauba wax having an acetyl value of 51, 1100 g (corresponding to 1 mol with OH) and 1500 g of xylene were weighed into a flask and dehydrated at 145 ° C. for 1 hour. Next, 95 g (1 mol) of succinic anhydride and 18.5 g (0.1 mol) of tributylamine were added at 140 ° C., and the reaction was carried out for 4 hours. Next, 438 g (0.45 mol) of an epoxy functional silicone having the following average structural formula was added at 140 ° C., and the reaction was performed for 4 hours under reflux of xylene. It was confirmed by IR analysis that the epoxy group disappeared after 4 hours. Subsequently, 1600 g of carnauba silicone (E) was obtained by stripping xylene under reduced pressure. The melting point by DSC was 79-87 ° C.

(Where Ω represents cyclohexene epoxide)

Comparative Example 4
Carnauba wax having an acetyl value of 51, 1100 g (corresponding to 1 mol with OH) and 1500 g of xylene were weighed into a flask and dehydrated at 145 ° C. for 1 hour. Next, 95 g (1 mol) of succinic anhydride and 18.5 g (0.1 mol) of tributylamine were added at 140 ° C., and the reaction was carried out for 4 hours. Next, 248 g (2 moles) of vinylcyclohexene epoxide was added at 140 ° C., and the carboxy group and the epoxy group were reacted at the same temperature for 3 hours. Xylene was stripped. After adding 1500 g of xylene, adding 4 g of 0.5% toluene solution of chloroplatinic acid and 660 g (0.45 mol) of hydrogen silicone having the following structure, after reacting at 120 ° C. for 5 hours, all SiH groups were removed. It was confirmed that the reaction occurred. By stripping xylene, 1960 g of carnauba silicone (F) was obtained. The melting point measured by DSC was 80-87 ° C.

Preparation of toner by pulverization method 100 parts by weight of styrene-acrylic resin (Hymer TB-9000; manufactured by Sanyo Chemical Co., Ltd.) having a glass transition point of 68 ° C., 5 parts by weight of carbon black (MA-600; manufactured by Mitsubishi Chemical Corporation), methyltriphenyl After 1 part by weight of phosphonium tosylate (charge control agent) and 5 parts by weight of each of the above carnauba silicones were dispersed and mixed, they were melt-kneaded using a twin screw extruder. The kneaded product was cooled and pulverized with a hammer mill, and further pulverized with a supersonic jet mill pulverizer. The obtained powder was classified with a classifier to obtain a fine powder black toner having an average particle size of about 10 μm.

Evaluation Method of Offset Resistance and Blocking Resistance (1) Offset recording resistance A recording paper carrying an unfixed toner image was prepared. The recording paper was passed through a fixing nip roller via a heating roller set to a predetermined surface temperature in a range from 100 ° C. to 210 ° C., and the fixing state was visually observed. The temperature range of the heating roller at which toner transfer to the heating roller does not occur was defined as the fixing temperature range.
(2) 10 g of anti-blocking developing toner was put into a cylindrical container having an inner diameter of about 5 cm, and a weight of 20 g was applied through a disk having the inner diameter as a diameter, and left for 1 day in an environment of 50 ° C. Thereafter, the toner was taken out of the container and judged according to the following criteria.
A: No aggregation B: Aggregates to form a lump, and the lump does not collapse even when a weight is applied.

The results of evaluating the offset resistance and blocking resistance of each toner are shown in Table 1 below.

カルナウバシリコーン（Ａ）及び（Ｂ）は本発明のシリコーンであり、（Ｃ）〜（Ｆ）は特許文献１記載のシリコーンである。シリコーン（Ｃ）は、イソシアネート変性シリコーンとカルナウバワックスとを反応させて得られたものであり、（Ｄ）は酸無水物変性カルナウバワックスとアミノシリコーンを反応させて得られたものであり、（Ｅ）はエポキシ変性シリコーンとカルナウバワックスとを反応させて得られたものであり、（Ｆ）は二重結合を持たせたカルナウバワックスとハイドロジェンシリコーンとを反応させて得られたものである。表１から分かるように、本発明のシリコーン（Ａ）及び（Ｂ）は、定着温度領域が広く、紙との接着性に優れる。また、荷重による凝集も無く、耐ブロッキング性に優れる。シリコーン（Ｅ）及び（Ｆ）の耐ブロッキング性が悪いのは、シリコーン（Ｅ）の調製において、エポキシ基が反応系内の水分と反応してしまうために、また、シリコーン（Ｆ）の調製において、カルナウバワックスの水酸基とヒドロシリル基との脱水素反応も起こるために、カルナウバワックスと結合していないシリコーンが多いためであると考えられる。

Carnauba silicones (A) and (B) are the silicones of the present invention, and (C) to (F) are the silicones described in Patent Document 1. Silicone (C) is obtained by reacting isocyanate-modified silicone with carnauba wax, and (D) is obtained by reacting acid anhydride-modified carnauba wax with aminosilicone. (E) is obtained by reacting epoxy-modified silicone with carnauba wax, and (F) is obtained by reacting carnauba wax with a double bond with hydrogen silicone. It is. As can be seen from Table 1, the silicones (A) and (B) of the present invention have a wide fixing temperature range and are excellent in adhesion to paper. In addition, there is no aggregation due to load, and the blocking resistance is excellent. Silicone (E) and (F) have poor blocking resistance because, in the preparation of silicone (E), epoxy groups react with moisture in the reaction system, and in the preparation of silicone (F). This is probably because the dehydrogenation reaction between the hydroxyl group and the hydrosilyl group of carnauba wax occurs, so that there are many silicones that are not bonded to carnauba wax.

The silicone of the present invention is useful for preparing a toner that has excellent adhesion to paper over a wide temperature range and does not block during storage. It can also be used as a surface modifier such as car wax, a mold release agent for various uses, and a slipperiness imparting agent.

3 is an IR spectrum of a cyclic acid anhydride group-containing silicone (1). 2 is an IR spectrum of silicone (A) in Example 1. 2 is an H-NMR spectrum of silicone (A) in Example 1.

Claims (7)

Silicone represented by the following general formula (1).

[In Formula (1), R ¹ is a group independently selected from the group consisting of a C1-10 aliphatic group, an alicyclic group, an aryl group, an aralkyl group, and a fluorine-substituted alkyl group;
R ² is a hydroxy residue represented by the following formula (2),

(Where a and b are 0 ≦ a ≦ 26 and 1 ≦ b ≦ 26 is an integer, 15 ≦ a + b ≦ 27 is satisfied, and R ³ is a C24-C34 linear aliphatic group)
X is a group represented by the following formula (3), and

(Here, R ⁴ is bonded to R ² of formula (1) and is a C3 to C12 aliphatic group or alicyclic group, R ⁵ is a C1 to C4 aliphatic group, or R ⁵ is R ^4. To form a C7-C12 bridged cyclic group)
m and n are integers of 0 ≦ m ≦ 150 and 0 ≦ n ≦ 30, respectively, and f is an integer of 0 ≦ f ≦ 3] The silicone according to claim 1, wherein R ¹ is a methyl group, R ⁴ is a propylene group, and R ⁵ is a methylene group.    The silicone according to claim 1 or 2, wherein the temperature of the end of the endothermic peak obtained by raising the temperature at 10 ° C / min using a differential thermal analyzer is in the range of 78 to 88 ° C. A method for producing a silicone wax by reacting silicone with carnauba wax, comprising reacting silicone containing a cyclic acid anhydride group with carnauba wax. The method according to claim 4, wherein the carnauba wax has an acetyl value of 51 to 60 measured according to JIS K8004. A toner wax comprising the silicone according to claim 1. A toner wax comprising a silicone wax obtained by the method according to claim 4.

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