JP7214322B2 - WAX POWDER OIL AND FAT COMPOSITION AND WAX COMPOSITION - Google Patents

Description

The present invention provides a powdered oil composition for wax, or a wax composition produced using the powdered oil composition, and the powdered oil, which can replace conventional waxes or can improve the physical properties of conventional waxes. The present invention relates to a wax physical property improver containing a composition.

The term "wax" means a solid ester composed of a higher fatty acid and a higher monohydric alcohol, but commonly used includes those that do not fit this definition. Examples include paraffin wax, which is a hydrocarbon.
In addition, the term "wax" chemically refers to solid esters of long-chain fatty acids and long-chain monohydric alcohols, and is different from oils and fats. Fats and oils are also widely recognized as "waxes", and can for example refer to substances that refer to waxy physical properties, i.e. water resistance, plasticity, gloss, opacity, etc., and melt between 50-90°C. Sometimes I say things. In light of this situation, it is considered that "wax" can be conventionally defined as "an organic substance that melts in a moderate temperature range from room temperature to around 100°C and has a low viscosity".

There are various applications of "wax" with the broad definition as above, such as inks, paints, electrical and electronic, architecture, construction, machinery, metals, automobiles, cutting, pharmaceuticals, and quasi-drugs. It is widely used in industrial fields such as food, cosmetics, agriculture, livestock, forestry, fisheries, food, chemicals, textiles, polymers, rubber, arts, crafts, gardening, sports equipment, and household goods.

Examples of waxes used in these various applications include plant waxes such as candelilla wax, carnauba wax, rice wax, Japan wax and jojoba oil, animal waxes such as beeswax, lanolin and spermaceti, and montan wax. , mineral waxes such as ozokerite and ceresin, paraffin wax, petroleum waxes such as microcrystalline wax and petrolatum, synthetic hydrocarbons such as Fischer-Tropsch wax, polyethylene wax, montan wax derivatives, paraffin wax derivatives, microcrystalline wax derivatives, etc. modified waxes, hydrogenated waxes such as hydrogenated castor oil, hydrogenated castor oil derivatives, fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, 12-hydroxystearic acid, lauric acid amide, stearic acid amide, oleic acid Acid amides such as amides, 12-hydroxystearic acid amides, stearic acid diethanolamides, methyl stearate, octadecyl stearate, glyceryl stearate monoester, sorbitol palmitate monoester, ethylene glycol monoester stearate, palmitic acid Esters such as sucrose esters, dextrin palmitate esters, and polyoxyethylene monoester stearates, ketones such as stearone and laurone, and blended waxes containing these may be mentioned.

It can be said that such "wax" is often added for the purpose of improving the functionality of various organic and inorganic materials. At that time, the characteristics required of the wax are that it has high hardness, maintains its shape and does not impair the characteristics of the material, and has high temperature sensitivity that allows it to melt quickly with moderate heating and change the material to the desired properties. etc. The melt viscosity of the wax is one of the important factors in adjusting the lubricity of the material, and is generally desired to be low. In addition, it is desired that the amount of volatile components generated under the usage environment be as small as possible from the viewpoint of environmental load. However, although the physical properties of wax vary depending on its composition, it is rare that wax possesses all of the above properties in a well-balanced manner. For example, a wax with high hardness has a high melting point and high viscosity, and a wax with low hardness has a low melting point and high volatility.

Therefore, various attempts have been made to improve the physical properties of waxes, but at present there is still room for further improvement. For example, hydrocarbon waxes are known as waxes that have an appropriate melting point, low viscosity, and high temperature sensitivity. This is a material that can be made to have a lower viscosity by increasing the ratio of straight-chain hydrocarbons, and to improve temperature sensitivity and hardness by narrowing the carbon number distribution. Volatilization is desired.

From a different point of view, carnauba wax is commonly used as a wax for toner used in the field of copiers and facsimiles (for example, Patent Document 1). This carnauba wax is a mixture of various different kinds of organic substances separated and refined from plants, and its complex structure functions organically to achieve high hardness. On the other hand, since this carnauba wax contains a large amount of resinous components, it has a problem of high viscosity and insufficient temperature sensitivity. In addition, although there is no problem with the current standards for the volatile components generated in the usage environment, if national regulations become stricter in the future, it cannot necessarily be said to be at a satisfactory level.
Thus, in the prior art, there has been a demand for waxes having suitable melting points and excellent physical properties such as low viscosity, low volatility, and high temperature sensitivity, depending on the various uses of waxes.

JP 2018-97184 A

Accordingly, an object of the present invention is to provide a powdered fat composition for wax that can replace conventional waxes or that can improve the physical properties of conventional waxes. More specifically, a powdered fat composition for waxes that has an appropriate melting point and can improve at least one of low viscosity, low volatility, high temperature sensitivity, and high hardness compared to conventional waxes. The task is to provide goods.

As a result of intensive research on the above-mentioned problems, the present inventors unexpectedly found that a powdered oil composition that satisfies specific conditions could replace conventional waxes or improve the physical properties of conventional waxes. found that it can be done, and completed the present invention. In addition, the inventors have found that at least one of low viscosity, low volatility, high temperature sensitivity, and high hardness can be improved compared to conventional waxes, and the present invention has been completed. . That is, the present invention can include the following aspects.

[1] A wax composition containing a powdered oil and fat composition for wax containing a powdered oil and fat composition that satisfies the following condition (a), A wax composition containing 0.1 to 100 parts by mass of the powdered oil composition.
(a) A powdered oil-fat composition containing an oil-and-fat component containing one or more XXX-type triglycerides having a fatty acid residue X with x carbon atoms at the 1- to 3-positions of glycerin, wherein the carbon number x is 10 to 22, the oil component contains a β-type oil, the particles of the powdered oil and fat composition have a plate-like shape, and the powdered oil and fat composition has a loose bulk density of 0.05 to 0.05. 6g/cm ³ is.
[2] The wax composition according to [1], wherein the fat component is a β-type fat.
[3] The wax composition according to [1] or [2], wherein the XXX-type triglyceride is contained in an amount of 50% by mass or more when the total mass of the oil and fat component is 100% by mass.
[4] The wax composition according to any one of [1] to [3], wherein the carbon number x is an integer selected from 16 to 18.
[5] The wax composition according to any one of [1] to [4], wherein the powdery oil composition has a loose bulk density of 0.1 to 0.4 g/cm3.
[6] The wax composition according to any one of [1] to [5], wherein the plate-like shape of the powdery oil composition has an aspect ratio of 1.1 or more.
[7] The wax composition according to any one of [1] to [6], wherein no α-type fat is detected in the powdery fat composition by differential scanning calorimetry.
[8] The wax composition according to any one of [1] to [7], wherein the powdery oil composition has a diffraction peak at 4.5 to 4.7 Å in X-ray diffraction measurement.
[9] The peak intensity ratio (4.6 Å peak intensity / (4.6 Å peak intensity + 4.2 Å peak intensity)) in X-ray diffraction measurement of the powdered oil and fat composition is 0.2 or more [1 ] to [8].
[10] The powdered oil-fat composition contains a β-type oil obtained by cooling and solidifying an oil-fat composition raw material containing XXX-type triglycerides at a temperature equal to or higher than the cooling temperature obtained from the following formula, [1] to [ 9] The wax composition according to any one of the above items.
Cooling temperature (°C) = carbon number x x 6.6-68
[11] The powdery fat composition contains a β-type fat obtained by cooling and solidifying an oil-fat composition raw material containing XXX-type triglycerides by keeping the temperature at a temperature equal to or higher than the melting point of the α-type fat corresponding to the β-type fat. The wax composition according to any one of [1] to [9].
[12] The wax composition according to any one of [1] to [11], wherein the powdery oil composition has an average particle size of 20 μm or less.
[13] The wax composition according to any one of [1] to [12], which is for toner.

INDUSTRIAL APPLICABILITY According to the present invention, by using a powdered fat composition for wax that satisfies specific conditions, anyone can easily produce a wax composition having further improved physical properties as compared to conventional waxes. That is, it has an appropriate melting point and can improve at least one of low viscosity, low volatility, high temperature sensitivity, and high hardness. In addition, since the powdered fat composition for wax is food grade, it is safer than the case of using a chemically synthesized agent and the like, and can be used without any limitation on the amount added. Moreover, since the powdery oil composition for wax does not have a peculiar odor or the like, it does not adversely affect the final wax composition. As such, it can be used in a wide variety of wax applications.

Fig. 3 is a photograph of the external appearance of the powdered fat composition (β-type fat) of Production Example 7 of the present invention. Fig. 3 is a photograph of the external appearance of the powdered fat composition (β-type fat) of Production Example 7 of the present invention. 1 is an appearance photograph of a fat composition (α-type fat) of Production Comparative Example 3 of the present invention. 2 is a micrograph of the powdered fat composition (β-type fat) of Production Example 7 of the present invention. 2 is a micrograph of the fat composition (α-type fat) of Comparative Production Example 3 of the present invention. Fig. 2 is an X-ray diffraction diagram of the powdered fat composition (β-type fat) of Production Example 7 of the present invention. FIG. 2 is an X-ray diffraction diagram of the fat composition (α-type fat) of Production Comparative Example 3 of the present invention.

Hereinafter, the wax composition of the present invention will be described in order.
<Wax composition>
The wax composition of the present invention is not particularly limited as long as it contains the powdered oil composition for wax of the present invention. Here, the wax composition of the present invention may be obtained by blending a conventional wax with the powdered fat composition for wax of the present invention, or the powdered fat composition for wax of the present invention itself is a wax composition. It can be an object.
That is, the wax composition of the present invention may contain various waxes conventionally used as waxes, in addition to the powdered oil composition for waxes of the present invention. Such waxes include, for example, plant waxes such as candelilla wax, carnauba wax, rice wax, Japan wax and jojoba oil; animal waxes such as beeswax, lanolin and spermaceti; montan wax, ozokerite and ceresin. mineral waxes, paraffin waxes, petroleum waxes such as microcrystalline waxes and petrolatum, synthetic hydrocarbons such as Fischer-Tropsch waxes and polyethylene waxes, modified waxes such as montan wax derivatives, paraffin wax derivatives and microcrystalline wax derivatives, curing Hydrogenated waxes such as castor oil, hydrogenated castor oil derivatives, fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, 12-hydroxystearic acid, lauric acid amide, stearic acid amide, oleic acid amide, 12-hydroxy Acid amides such as stearamide, stearic acid diethanolamide, methyl stearate, octadecyl stearate, glyceryl stearate monoester, sorbitol palmitate monoester, ethylene glycol monoester stearate, sucrose palmitate, palmitin Acid dextrin esters, esters such as stearic acid polyoxyethylene monoester, ketones such as stearone and laurone, and blended waxes containing these may be mentioned.
Moreover, the wax composition of the present invention can be used for various purposes. Depending on the type of wax, for example, inks, paints, electrical/electronics, architecture, construction, machinery, metals, automobiles, cutting, pharmaceuticals, quasi-drugs, cosmetics, agriculture, livestock, forestry, fisheries, food, chemicals , textiles, polymers, rubber, arts, crafts, gardening, sporting goods, household goods, and other industrial fields.
The content of the powdered oil composition for wax in the wax composition of the present invention is arbitrary according to the application, but is preferably 0.1 to 100 mass% when the mass of the entire wax composition is 100 mass%. %, more preferably 0.5 to 99% by mass, still more preferably 1.0 to 90% by mass. In order to exhibit the desired effects of the present invention, it is preferable that the powdery fat composition for wax of the present invention is contained in an amount of 0.1% by mass or more. The above 100% by mass means that the entire wax composition is a powdered oil composition for wax, and can be exemplified as one of preferred embodiments of the wax composition of the present invention.

<Other components contained in the wax composition>
The wax composition of the present invention can optionally contain “other components” in addition to the “powder oil composition for wax” and “various waxes” described above. Other components that are usually added to wax in the prior art can be blended within a range that does not extremely impair the effects of the present invention. For example, such "other ingredients" include emulsifiers, perfumes, colorants, thickening stabilizers, antioxidants, and the like.
Moreover, in order to adjust the viscosity, melting point, etc. of the wax composition of the present invention, an "edible fat" can be added as appropriate. Specific examples of such edible fats and oils include soybean oil, rapeseed oil, cottonseed oil, safflower oil, sunflower oil, rice oil, corn oil, sesame oil, olive oil, palm oil, palm fractionated oil (palm fractionated soft oil (palm olein, palm super olein, etc.), palm mid-melting point, palm fractionated hard oil (palm stearin, etc.), shea butter, shea fractionated oil, monkey fat, monkey fractionated oil, illipe butter, cocoa butter, coconut oil, palm kernel oil, Examples include milk fat, butter, mixed oils thereof, and processed oils (hydrogenated oils, transesterified oils, fractionated oils, etc.). These edible fats and oils can be used singly or in combination of two or more.

<Powder oil composition for wax>
The present invention relates to a powdered fat composition for wax, containing a powdered fat composition (hereinafter also simply referred to as "powder fat composition") that satisfies the following condition (a).
(a) A powdered oil-fat composition containing an oil-and-fat component containing one or more XXX-type triglycerides having a fatty acid residue X with x carbon atoms at the 1- to 3-positions of glycerin, wherein the carbon number x is 10 to 22, the oil component contains a β-type oil, the particles of the powdered oil and fat composition have a plate-like shape, and the powdered oil and fat composition has a loose bulk density of 0.05 to 0.05. 6 g/cm ³ .
The powdery fat composition for wax of the present invention may optionally contain an emulsifier, a fragrance, a coloring agent, a thickening stabilizer, an antioxidant, etc., in addition to the powdery fat composition described above.
The content of the powdered fat composition satisfying the above condition (a) in the powdered fat composition for wax is, for example, 50% by mass or more, preferably 50% by mass or more, when the total mass of the powdered fat composition for wax is 100% by mass. The lower limit is 60% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, for example, 100% by mass or less, preferably 99% by mass or less, more preferably 95% by mass or less is the upper limit. 100% by mass of the powdered fat composition for wax may be a powdered fat composition that satisfies the above condition (a). One or two or more types of the powdered oil and fat composition can be used, preferably one or two types, and more preferably one type.

<Oil component>
The powdered fat composition of the present invention contains a fat component. The fat component contains at least type XXX triglycerides and optionally other triglycerides.
The fat component includes β-type fat. Here, β-type fats and oils are fats and oils that consist only of β-type crystals, which is one of the crystal polymorphs of fats and oils. Other crystalline polymorphic fats and oils include β′-type fat and α-type fat, and β′-type fat is fat composed only of β′-type crystals, which is one of the crystal polymorphs of fats and oils. The α-type fats and oils are fats and oils composed only of α-type crystals, which is one of the crystal polymorphs of fats and oils. Some fat crystals have the same composition but different sublattice structures (crystal structures), which are called polymorphs. Typically, there are hexagonal, orthorhombic, and triclinic parallel types, which are called α-type, β'-type, and β-type, respectively. In addition, the melting point of each polymorph is higher in the order of α, β', β, and the melting point of each polymorph differs depending on the type of fatty acid residue X having x carbon atoms. , trilaurin, trimyristin, tripalmitin, tristearin, triarachidin, and tribehenin. Table 1 was created based on Nissim Garti et al., "Crystallization and Polymorphism of Fats and Fatty Acids", Marcel Dekker Inc., 1988, pp.32-33. In creating Table 1, the melting point temperature (°C) was rounded off to the first decimal place. Moreover, if the composition of the fat and the melting point of each polymorph thereof are known, it is possible to detect at least whether or not the β-type fat is present in the fat.

A common technique for identifying these polymorphs is X-ray diffraction, where the diffraction conditions are given by the Bragg equation below.
2d sin θ = nλ (n = 1, 2, 3...)
A diffraction peak appears at a position that satisfies this formula. Here, d is the lattice constant, θ is the diffraction (incidence) angle, λ is the X-ray wavelength, and n is a natural number. The 2θ=16-27° of the diffraction peaks corresponding to the minor facet spacing provides information on the lateral packing (sublattice) in the crystal, allowing identification of polymorphs. In particular, in the case of triacylglycerol, β-type characteristic peaks are observed at 2θ=19, 23, 24° (around 4.6 Å, around 3.9 Å, around 3.8 Å), and α at around 21° (4.2 Å). A characteristic peak of the mold appears. The X-ray diffraction measurement is performed using, for example, an X-ray diffractometer maintained at 20° C. (Rigaku Co., Ltd., sample horizontal X-ray diffractometer UItimaIV). CuKα rays (1.54 Å) are most often used as the X-ray source.

Furthermore, the crystal polymorphism of the fats and oils can also be predicted by differential scanning calorimetry (DSC method). For example, the prediction of β-type fats and oils is based on a DSC curve obtained by heating to 100 ° C. at a heating rate of 10 ° C./min with a differential scanning calorimeter (manufactured by SII Nanotechnology Co., Ltd., product number BSC6220). This is done by predicting the crystal structure of fats and oils.

Here, the fat component contains β-type fat, or contains β-type fat as a main component (more than 50% by mass). In a more preferred embodiment, the fat component consists of β-type fat, and in a particularly preferred embodiment, the fat component consists solely of β-type fat. The case where all of the fat components are β-type fats and oils means the case where α-type fats and/or β′-type fats and oils are not detected by differential scanning calorimetry. In another preferred embodiment, the fat component (or the powdery fat composition containing the fat component) has a diffraction peak near 4.5 to 4.7 Å, preferably near 4.6 Å in X-ray diffraction measurement. However, the α-type fat and / or β'-type fat in Table 1 does not have a short plane spacing X-ray diffraction peak, especially when it does not have a diffraction peak near 4.2 Å. can be determined to be β-type fats and oils. As a further aspect of the present invention, it is preferable that all of the fat components are β-type fats and oils, but other α-type fats and β′-type fats may also be included. Here, the oil and fat component in the present invention "contains β-type oil" and the index of the relative amount of β-type oil with respect to α-type oil + β-type oil is the characteristic peak of β-type among the X-ray diffraction peaks and the characteristic peak of α-type: [intensity of characteristic peak of β-type/(intensity of characteristic peak of α-type+intensity of characteristic peak of β-type)] (hereinafter also referred to as peak intensity ratio). ). Specifically, based on the findings of the X-ray diffraction measurement described above, the peak intensity at 2θ = 19° (4.6 Å), which is the characteristic peak of the β type, and the peak intensity at 2θ = 21, which is the characteristic peak of the α type. ° (4.2 Å) peak intensity ratio: 19 ° / (19 ° + 21 °) [4.6 Å / (4.6 Å + 4.2 Å)] of the β-type fat of the above fat component It can be understood that "β-type fat is included" as an index representing the abundance. In the present invention, it is preferable that all the fat components are β-type fats (that is, peak intensity ratio=1). It is suitably 5 or more, more preferably 0.6 or more, still more preferably 0.7 or more, particularly preferably 0.75 or more, and most preferably 0.8 or more. If the peak intensity is 0.4 or more, it can be considered that the main component of the β-type fat is more than 50% by mass. The upper limit of the peak intensity ratio is preferably 1, but 0.99 or less, 0.98 or less, 0.95 or less, 0.93 or less, 0.90 or less, 0.85 or less, 0.80 or less etc. is acceptable. The peak intensity ratio can be either or any combination of the above lower limit and upper limit.

<XXX type triglyceride>
The oil-and-fat component of the present invention contains one or more XXX-type triglycerides having a fatty acid residue X with x carbon atoms at the 1-3 positions of glycerin. The XXX-type triglyceride is a triglyceride having fatty acid residues X with x carbon atoms at positions 1 to 3 of glycerol, and each fatty acid residue X is the same. Here, the carbon number x is an integer selected from 10 to 22, preferably an integer selected from 12 to 22, more preferably an integer selected from 14 to 20, more preferably selected from 16 to 18 is an integer that
Fatty acid residue X may be a saturated or unsaturated fatty acid residue. Examples of specific fatty acid residues X include, but are not limited to, residues of capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. The fatty acids are more preferably lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and behenic acid, still more preferably myristic acid, palmitic acid, stearic acid and arachidic acid, and still more preferably palmitic acid. acid and stearic acid.
The content of the XXX-type triglyceride is, for example, 50% by mass or more, preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass, when the total mass of the oil and fat component is 100% by mass. The lower limit is at least 100% by mass, and the upper limit is, for example, 100% by mass or less, preferably 99% by mass or less, and more preferably 95% by mass or less. One type or two or more types of XXX triglycerides can be used, preferably one type or two types, more preferably one type. When there are two or more types of XXX triglycerides, the total value is the content of XXX triglycerides.

<Other triglycerides>
The oil and fat component of the present invention may contain triglycerides other than the XXX triglycerides as long as the effects of the present invention are not impaired. Other triglycerides may be multiple types of triglycerides, and may be synthetic oils or natural oils. Synthetic fats and oils include glyceryl tricaprylate, glyceryl tricaprate, and the like. Examples of natural fats and oils include cocoa butter, sunflower oil, rapeseed oil, soybean oil, cottonseed oil and the like. When the total triglyceride in the oil and fat component of the present invention is 100% by mass, other triglycerides may be contained in an amount of 1% by mass or more, for example, about 5 to 50% by mass. The content of other triglycerides is, for example, 0 to 30% by mass, preferably 0 to 18% by mass, more preferably 0 to 15% by mass, still more preferably 0 to 8% by mass.

<Other ingredients>
The powdered oil-fat composition of the present invention may optionally contain other ingredients such as emulsifiers, perfumes, colorants, thickening stabilizers and antioxidants, in addition to the above-mentioned oil-and-fat components such as triglycerides. The amount of these other components can be any amount as long as it does not impair the effects of the present invention. is 0 to 65% by mass, more preferably 0 to 30% by mass. 90% by mass or more of the other components are preferably powders with an average particle size of 1000 μm or less, and more preferably powders with an average particle size of 500 μm or less. The average particle size referred to here is a value measured by a laser diffraction scattering method (ISO133201 and ISO9276-1).
However, it is preferable that the preferred powdered fat composition of the present invention consists essentially of the above fat component, and that the fat component consists essentially of triglycerides. In addition, "substantially" means that components other than the fat component contained in the fat composition or components other than the triglyceride contained in the fat component are the powdered fat composition or the fat component When 100% by mass, For example, it means 0 to 15% by mass, preferably 0 to 10% by mass, more preferably 0 to 5% by mass.

<Production of powdered oil composition>
The powdered oil-fat composition of the present invention melts an oil-fat composition raw material containing one or more XXX-type triglycerides having a fatty acid residue X with x carbon atoms at the 1- to 3-positions of glycerin, and cools it to a specific cooling temperature. By holding and cooling and solidifying, a powdery oil composition (powder oil composition) can be obtained without special processing means such as spraying or mechanical pulverization with a pulverizer such as a mill. More specifically, (a) an oil-fat composition raw material containing the above XXX-type triglyceride is prepared, optionally in step (b), the oil-fat composition raw material obtained in step (a) is heated, and the oil-fat composition is The triglyceride contained in the raw material is dissolved to obtain the melted oil and fat composition raw material; A powdered fat composition is obtained. The powdered fat composition can also be produced by applying known pulverization means such as a hammer mill and a cutter mill to the solid matter obtained after cooling.

The cooling in the step (d) is performed, for example, by cooling the melted oil-fat composition raw material to a temperature lower than the melting point of the β-type fat of the oil-fat component contained in the oil-fat composition raw material, and using the following formula:
Cooling temperature (°C) = carbon number x x 6.6 - 68
is performed at a temperature equal to or higher than the cooling temperature obtained from By cooling in such a temperature range, the β-type fat can be efficiently produced and fine crystals can be formed, so that the powdery fat composition can be easily obtained. The above-mentioned "fine" means that the primary particles (crystals with the smallest size) are, for example, 20 μm or less, preferably 15 μm or less, more preferably 10 μm. In addition, unless it is cooled in such a temperature range, the β-type fat is not produced, and a solid matter having voids with a larger volume than the raw material of the fat composition may not be produced. Furthermore, in the present invention, by cooling in such a temperature range, the β-type fat is generated in a standing state, and the particles of the powdered fat composition are formed into a plate-like shape. It is useful for specifying the powdered fat composition of the present invention. A preferred average particle size of the powdered fat composition for wax of the present invention is, for example, an average particle size of 20 μm or less. The method for measuring the average particle size is as described above. Furthermore, fine particles of 20 μm or less are difficult to perceive with human senses, so by using particles of 20 μm or less, a powdery oil composition with a high melting point can be added without giving a rough texture or touch. be able to.

Although it is not clear why the powdered oil composition for wax of the present invention can be suitably used as a wax or why the physical properties of the wax are improved, particles having a small average particle size and a plate-like shape have a strong adhesive force, so various There is a possibility that it adheres to organic or inorganic materials and assists their functions. It should be noted that this is explained for the purpose of making the principle of the present invention easy to understand, and the present invention is not bound by this principle.
In addition, as described later, it was found that the powdery fat composition of the present invention itself functions as a low-volatile wax (release agent) when used as a toner wax. From this, anyone skilled in the art can predict that adding the powdered fat composition of the present invention as part of another wax can reduce the volatility of the wax. Furthermore, as the powdered oil and fat composition of the present invention, for example, if one having an appropriate melting point is used, the melting point of the wax can be adjusted appropriately, and low viscosity, low volatility, high temperature sensitivity, and high hardness can be achieved. At least one property can be improved.

<Characteristics of powdered oil composition>
The powdered fat composition of the present invention is a powdery solid at room temperature (20°C).
The loose bulk density of the powdered fat composition of the present invention is, for example, 0.05 to 0.6 g/cm ³ , preferably 0.1 to 0.5 g/cm ³ when it consists substantially only of fat components, More preferably 0.1 to 0.4 g/cm ³ or 0.15 to 0.4 g/cm ³ , still more preferably 0.2 to 0.3 g/cm ³ . Here, the "loose bulk density" is the packing density of the powder in a state of free fall. Loose bulk density (g/cm ³ ) is measured, for example, by dropping an appropriate amount of the powdered fat composition into a graduated cylinder having an inner diameter of 15 mm×25 mL from about 2 cm above the upper open end of the graduated cylinder, and loosely filling the composition. It can be obtained by measuring the filled mass (g) and reading the volume (mL), and calculating the mass (g) of the powdered oil and fat composition per mL. The loose bulk density can also be calculated from the bulk specific gravity measured according to JIS K-6720 (or ISO 1060-1 and 2) using a bulk density measuring instrument manufactured by Kuramochi Scientific Instruments Co., Ltd. Specifically, 120 mL of a sample is dropped into a receiver (a 100 mL cylindrical container with an inner diameter of 40 mm and a height of 85 mm) from a height of 38 mm from the upper opening of the receiver. The sample that has risen from the receiver is scraped off, the mass (Ag) of the sample for the internal volume (100 mL) of the receiver is weighed, and the loosened bulk density can be obtained from the following equation.
Loose bulk density (g/mL) = A (g)/100 (mL)
It is preferable to perform the measurement three times and take the average value.

In addition, the powdered oil and fat composition of the present invention usually has a plate-like shape of particles, for example, 5 to 200 μm, preferably 10 to 150 μm, more preferably 20 to 120 μm, particularly preferably 25 to 25 μm. It has an average particle size (effective diameter) of 100 μm. Here, the average particle diameter (effective diameter) can be obtained based on the laser diffraction scattering method (ISO133201, ISO9276-1) with a particle size distribution analyzer (eg, Microtrac MT3300ExII manufactured by Nikkiso Co., Ltd.). The effective diameter means a spherical particle size when the measured diffraction pattern of the crystal to be measured matches the theoretical diffraction pattern obtained by assuming a spherical shape. In this way, in the case of the laser diffraction scattering method, the effective diameter is calculated by matching the theoretical diffraction pattern obtained assuming a spherical shape with the actually measured diffraction pattern. Even a spherical shape can be measured by the same principle. Here, the plate-like shape preferably has an aspect ratio of 1.1 or more, more preferably 1.2 or more, still more preferably 1.2 to 3.0, particularly preferably The aspect ratio is 1.3 to 2.5, particularly preferably 1.4 to 2.0. Here, the aspect ratio is defined as the ratio of the length of the long side to the length of the short side of the rectangle enclosing the particle figure in a rectangle that circumscribes it so as to minimize the area. Also, when the particles are spherical, the aspect ratio is less than 1.1. In the conventional method of dissolving and directly spraying oils and fats with a high solid fat content at room temperature such as extremely hardened oils, the particles of the powdered oil and fat composition become spherical due to surface tension, and the aspect ratio is less than 1.1. Become. Then, the aspect ratio is measured by, for example, directly observing with an optical microscope or a scanning electron microscope, and measuring the length in the long axis direction and the length in the short axis direction of arbitrarily selected particles. It can be obtained as the average value of the number of

<Method for producing powdered fat composition>
The powdered fat composition of the present invention is prepared by the following steps,
(a) a step of preparing an oil and fat composition raw material containing XXX-type triglycerides;
(b) optionally heating the oil and fat composition raw material obtained in step (a) to dissolve triglycerides contained in the oil and fat composition raw material to obtain the molten oil and fat composition raw material; (d) a step of cooling and solidifying the oil and fat composition raw material to obtain a powdery oil and fat composition containing a β-type oil and having a plate-like particle shape;
It can be manufactured by a method comprising
Also, between the above steps (b) and (d), an optional step for promoting powder formation as step (c), such as (c1) seeding step, (c2) tempering step, and/or (c3) A pre-cooling step may be included. Furthermore, the powdery fat composition obtained in the step (d) is obtained by the step (e) of pulverizing the solid obtained after cooling in the step (d) to obtain a powdery fat composition. good. The steps (a) to (e) will be described below.

(a) Raw material preparation step The oil and fat composition raw material containing XXX triglycerides prepared in step (a) is one or more XXX triglycerides having a fatty acid residue X with x carbon atoms at the 1- to 3-positions of glycerin. XXX-type triglycerides containing or can be easily obtained from the market. Here, the XXX-type triglyceride specified by the carbon number x and the fatty acid residue X is the same as that of the finally obtained fat and oil component except for the crystal polymorphism. The raw material may contain β-type fat, for example, the content of β-type fat may be 0.1% by mass or less, 0.05% by mass or less, or 0.01% by mass or less. . However, since the β-type fat disappears when the raw material is melted by heating or the like, the raw material may be a raw material in a molten state. For example, when the raw material is in a molten state, substantially not containing β-type fat means that not only XXX-type triglycerides but also substantially all fat components are not β-type fats. The presence of the type fat can be confirmed by the above-mentioned X-ray diffraction measurement, the diffraction peak attributed to the β type fat, and the confirmation of the β type fat by differential scanning calorimetry. The abundance of β-type fat in the case of “substantially free of β-type fat” is the intensity ratio between the characteristic peak of β-type and the characteristic peak of α-type among the X-ray diffraction peaks [characteristic of β-type can be estimated from the intensity of the characteristic peak/(intensity of characteristic peak of α-type+intensity of characteristic peak of β-type)] (peak intensity ratio). The peak intensity ratio of the raw material for the oil and fat composition is, for example, 0.2 or less, preferably 0.15 or less, and more preferably 0.10 or less. The oil and fat composition raw material may contain one or more XXX triglycerides as described above, preferably one or two, more preferably one.
Specifically, for example, the XXX triglyceride can be produced by direct synthesis using a fatty acid or fatty acid derivative and glycerin. Methods for directly synthesizing XXX-type triglycerides include (i) a method of directly esterifying a fatty acid having X carbon atoms and glycerin (direct ester synthesis), and (ii) a method in which the carboxyl group of fatty acid X having x carbon atoms is an alkoxyl group. (e.g., fatty acid methyl and fatty acid ethyl) combined with glycerin under basic or acidic catalytic conditions (transesterification synthesis using fatty acid alkyl), (iii) fatty acid having carbon number x A method of reacting a fatty acid halide in which the hydroxyl group of the carboxyl group of X is substituted with halogen (eg, fatty acid chloride and fatty acid bromide) with glycerin in the presence of a basic catalyst (acid halide synthesis) can be mentioned.
XXX-type triglycerides can be produced by any of the above-described methods (i) to (iii), but from the viewpoint of ease of production, (i) direct ester synthesis or (ii) transesterification synthesis using a fatty acid alkyl is preferred. Preferably, (i) direct ester synthesis is more preferred.

To produce XXX-type triglycerides by (i) direct ester synthesis, from the viewpoint of production efficiency, it is preferable to use 3 to 5 mol of fatty acid X or fatty acid Y per 1 mol of glycerin, and 3 to 4 mol is used. is more preferable.
The reaction temperature in (i) direct ester synthesis of XXX-type triglycerides may be any temperature at which the water produced by the esterification reaction can be removed out of the system. More preferably, 180° C. to 250° C. is even more preferable. By carrying out the reaction at 180 to 250° C., XXX triglycerides can be produced particularly efficiently.

In the (i) direct ester synthesis of XXX-type triglycerides, a catalyst that accelerates the esterification reaction may be used. Examples of the catalyst include acid catalysts and alkoxides of alkaline earth metals. The amount of the catalyst used is preferably about 0.001 to 1% by mass with respect to the total mass of the reaction raw materials.
In (i) direct ester synthesis of XXX-type triglycerides, after the reaction, the catalyst and unreacted raw materials are removed by performing known purification treatments such as washing with water, alkaline deacidification and/or deacidification under reduced pressure, and adsorption treatment. can do. Furthermore, the resulting reaction product can be further purified by subjecting it to decolorization/deodorization treatment.

The amount of XXX triglycerides contained in the raw material of the oil and fat composition is, for example, 100 to 50% by mass, preferably 95 to 55% by mass, when the total mass of all triglycerides contained in the raw material is 100% by mass. , more preferably 90 to 60% by mass. More preferably, it is 85 to 65% by mass.

<Other triglycerides>
Other triglycerides used as raw materials for the fat and oil composition containing XXX triglycerides may include various triglycerides in addition to the above XXX triglycerides as long as the effects of the present invention are not impaired. Other triglycerides include, for example, X2Y-type triglyceride in which one of the fatty acid residues X of the XXX-type triglyceride is substituted with fatty acid residue Y, and two of the fatty acid residues X in the XXX-type triglyceride are substituted with fatty acid residue Y. XY2-type triglycerides and the like can be mentioned.
The amount of the above other triglycerides is, for example, 0 to 100% by mass, preferably 0 to 70% by mass, more preferably 1 to 40% by mass, when the total mass of XXX type triglycerides is 100% by mass.

As the raw material for the oil and fat composition of the present invention, instead of directly synthesizing the XXX-type triglyceride, a naturally-derived triglyceride composition that has undergone hydrogenation, transesterification, or fractionation may be used. Examples of naturally derived triglyceride compositions include rapeseed oil, soybean oil, sunflower oil, high oleic sunflower oil, safflower oil, palm stearin and mixtures thereof. In particular, hydrogenated oils, partially hydrogenated oils, and extremely hydrogenated oils of these naturally-derived triglyceride compositions are preferred. More preferred are hard palm stearin, high oleic sunflower oil, extremely hardened oil, rapeseed extremely hardened oil, and soybean extremely hardened oil.

Furthermore, as the raw material for the oil and fat composition of the present invention, commercially available triglyceride compositions or synthetic oils and fats can be mentioned. Examples of triglyceride compositions include hard palm stearin (manufactured by Nisshin OilliO Group, Ltd.), highly hydrogenated rapeseed oil (manufactured by Yokozeki Oil Industry Co., Ltd.), and highly hydrogenated soybean oil (manufactured by Yokozeki Oil Industry Co., Ltd.). can. In addition, as synthetic fats and oils, tripalmitin (manufactured by Tokyo Chemical Industry Co., Ltd.), tristearin (manufactured by Sigma-Aldrich Co., Ltd.), tristearin (manufactured by Tokyo Chemical Industry Co., Ltd.), triarachidin (manufactured by Tokyo Chemical Industry Co., Ltd.), tribehenin (manufactured by Tokyo Chemical Industry Co., Ltd.) Kogyo Co., Ltd.) can be mentioned.
In addition, extremely hydrogenated palm oil has a low content of XXX-type triglycerides, so it can be used as a diluent component for triglycerides.

<Other ingredients>
In addition to the triglycerides, the raw material for the oil and fat composition may optionally contain other components such as partial glycerides, fatty acids, antioxidants, emulsifiers, and solvents such as water. The amount of these other components can be any amount as long as it does not impair the effects of the present invention. 0 to 2% by mass, more preferably 0 to 1% by mass.

When a plurality of components are contained in the raw material for the oil and fat composition, they may be mixed arbitrarily. Mixing may be performed by any known mixing method as long as a homogeneous reaction substrate can be obtained.
The said mixing may be mixed under a heating as needed. Heating is preferably carried out at the same temperature as the heating temperature in step (b) described later, for example, 50 to 120°C, preferably 60 to 100°C, more preferably 70 to 90°C, and still more preferably 80°C. will be

(b) a step of obtaining the melted oil and fat composition, if the oil and fat composition raw material prepared in the step (a) is in a melted state at the time of preparation, it is heated before the step (d); However, if it is not in a molten state at the time of preparation, it is optionally heated to melt the triglycerides contained in the oil and fat composition raw material to obtain a molten oil and fat composition raw material.
Here, the heating of the oil and fat composition raw material is performed at a temperature higher than the melting point of the triglyceride contained in the oil and fat composition raw material, particularly at a temperature at which XXX type triglyceride can be melted, for example, 70 to 200 ° C., preferably 75 to 150 ° C. , more preferably 80 to 100°C. Further, it is suitable to continue heating, for example, for 0.1 to 3 hours, preferably 0.3 to 2 hours, more preferably 0.5 to 1 hour.

(d) Step of cooling the melted fat composition to obtain a powdery fat composition The melted fat composition raw material prepared in the above step (a) or (b) is further cooled and solidified to obtain a β-type. A powdery fat composition containing fat and having a plate-like particle shape is formed.
Here, in order to "cool and solidify the melted oil-fat composition raw material", the melted oil-fat composition raw material is used as the upper limit of the cooling temperature. It is necessary to keep the temperature below the melting point of "A temperature lower than the melting point of the β-type fat of the fat component contained in the raw material of the oil-fat composition" means, for example, in the case of an XXX-type triglyceride having three stearic acid residues having 18 carbon atoms, the melting point of the β-type fat is Since it is 74° C. (Table 1), the temperature is 1 to 30° C. lower than the melting point (ie 44 to 73° C.), preferably 1 to 20° C. lower than the melting point (ie 54 to 73° C.), more preferably the 1 to 15°C below the melting point (ie 59 to 73°C), particularly preferably 1°C, 2°C, 3°C, 4°C, 5°C, 6°C, 7°C, 8°C, 9°C or 10°C below temperature.
More preferably, in order to obtain the β-type fat, it is appropriate to keep the lower limit of the cooling temperature above the cooling temperature obtained from the following formula.
Cooling temperature (°C) = carbon number x x 6.6 - 68
(Wherein, the carbon number x is the carbon number x of the XXX-type triglyceride contained in the oil and fat composition raw material)
The reason why the cooling temperature is set at or above such a temperature is that in order to obtain a β-type fat containing XXX-type triglycerides, the cooling temperature is set at the time of crystallization of the fat. This is because it is necessary to set the temperature at which crystallization does not occur. Since the cooling temperature mainly depends on the molecular size of the XXX-type triglyceride, it can be understood that there is a certain correlation between the carbon number x and the optimum lower limit of the cooling temperature.
For example, when the XXX triglyceride contained in the oil and fat composition raw material is an XXX triglyceride having three stearic acid residues with 18 carbon atoms, the lower limit of the cooling temperature is 50.8° C. or higher. Therefore, in the case of XXX-type triglycerides having three stearic acid residues with 18 carbon atoms, the temperature for "cooling and solidifying the melted oil and fat composition raw material" is more preferably 50.8 ° C. or higher and 72 ° C. or lower. Become.
Moreover, when the XXX triglyceride is a mixture of two or more kinds, the lower limit can be determined according to the cooling temperature of the one with the smaller carbon number x. For example, the XXX triglyceride contained in the oil and fat composition raw material is a mixture of XXX triglyceride having three palmitic acid residues having 16 carbon atoms and XXX triglyceride having three stearic acid residues having 18 carbon atoms. , the lower limit of the cooling temperature is 37.6° C. or higher in accordance with the smaller carbon number of 16.

In another aspect, the lower limit of the cooling temperature is suitably a temperature equal to or higher than the melting point of the α-type fat corresponding to the β-type fat of the oil-and-fat composition raw material containing the XXX-type triglyceride. For example, when the XXX-type triglyceride contained in the oil and fat composition raw material is an XXX-type triglyceride having three stearic acid residues having 18 carbon atoms, the α-type fat of the XXX-type triglyceride having three stearic acid residues Since the melting point of is 55°C (Table 1), the temperature for "cooling and solidifying the molten fat composition raw material" is preferably 55°C or higher and 72°C or lower.

As yet another aspect, the cooling of the oil and fat composition raw material in a molten state is preferably -2 to 46 ° C., more preferably 12 to 44 ° C., still more preferably when x is 10 to 12, for example. This is done by cooling to a temperature of 14-42°C. The final temperature in cooling is, for example, preferably 24 to 56°C, more preferably 32 to 54°C, still more preferably 40 to 52°C when x is 13 or 14, and when x is 15 or 16, It is preferably 36 to 66°C, more preferably 44 to 64°C, still more preferably 52 to 62°C, and when x is 17 or 18, preferably 50 to 72°C, more preferably 54 to 70°C, and further It is preferably 58 to 68°C, and when x is 19 or 20, preferably 62 to 80°C, more preferably 66 to 78°C, still more preferably 70 to 77°C, when x is 21 or 22. is preferably 66 to 84°C, more preferably 70 to 82°C, still more preferably 74 to 80°C. At the above final temperature, for example, preferably 2 hours or more, more preferably 4 hours or more, still more preferably 6 hours or more, preferably 2 days or less, more preferably 24 hours or less, still more preferably 12 hours or less, It is appropriate to let it stand still.

(c) powder formation promotion step Furthermore, before step (d), between the above steps (a) or (b) and (d), (c) as an optional step for promoting powder formation, the step ( The molten fat composition raw material used in d) may be subjected to seeding method (c1), tempering method (c2) and/or pre-cooling method (c3). Any of these optional steps (c1) to (c3) may be performed alone, or a plurality of steps may be combined. Here, between step (a) or (b) and step (d) means during step (a) or (b), after step (a) or (b) and in step (d) It is meant to include before and during step (d).
The seeding method (c1) and the tempering method (c2) are used in the production of the powdered oil and fat composition of the present invention, in order to more reliably powder the oil and fat composition raw material in a molten state, before cooling to the final temperature. Secondly, it is a method for promoting powder production in which the raw material of the oil and fat composition in a molten state is treated. Here, the seeding method (c1) is a method for promoting powderization by adding a small amount of a component that will become the nucleus (seed) of the powder when cooling the oil-fat composition raw material in a molten state. Specifically, for example, XXX-type triglyceride having the same number of carbon atoms as XXX-type triglyceride in the oil-and-fat composition raw material is added to the molten oil-and-fat composition raw material obtained in the step (b), preferably 80% by mass or more. , more preferably 90% by mass or more, is prepared as a core (seed) component. When the fat composition raw material in the molten state is cooled, the temperature of the fat composition raw material reaches, for example, the final cooling temperature ±0 to +10 ° C., preferably +5 to +10 ° C. At that time, 0.1 to 1 part by mass, preferably 0.2 to 0.8 parts by mass is added to 100 parts by mass of the oil and fat composition raw material in the molten state, thereby pulverizing the oil and fat composition. It is a way to promote.
In addition, the tempering method (c2) is a temperature lower than the cooling temperature in step (d), for example, 5 to 20 ° C., once before standing at the final cooling temperature in cooling the oil and fat composition raw material in a molten state. Cooling to a low temperature, preferably 7 to 15°C lower temperature, more preferably about 10°C lower temperature, preferably about 10 to 120 minutes, more preferably about 30 to 90 minutes, promotes pulverization of the oil and fat composition. It is a way to
Furthermore, the pre-cooling method (c3) includes the XXX-type triglyceride before cooling the melted oil-fat composition raw material obtained in the step (a) or (b) in the step (d). A method of cooling once at a temperature between the temperature when the oil and fat composition raw material is prepared and the cooling temperature when the oil and fat composition raw material is cooled, in other words, from the temperature of the molten state in step (a) or (b) It is a method of once pre-cooling at a temperature higher than the cooling temperature in step (d). (c3) After the pre-cooling method, cooling is performed at the cooling temperature for cooling the oil and fat composition raw material in step (d). The temperature higher than the cooling temperature in step (d) is, for example, 2 to 40°C higher than the cooling temperature in step (d), preferably 3 to 30°C higher, more preferably 4 to 30°C higher, More preferably, the temperature may be about 5 to 10°C higher. As the pre-cooling temperature is set lower, the main cooling time at the cooling temperature in step (d) can be shortened. That is, unlike the seeding method and the tempering method, the pre-cooling method is a method capable of promoting powderization of the oil-fat composition simply by lowering the cooling temperature in stages, and is highly advantageous in industrial production.

(e) Step of pulverizing solids to obtain a powdered fat composition The step of obtaining a powdered fat composition by cooling in the step (d) is more specifically a solid obtained by cooling in the step (d). may be performed by a step (e) of pulverizing to obtain a powdered fat composition.
To explain in detail, first, the above-described oil and fat composition raw material is melted to obtain a molten oil and fat composition, and then cooled to form a solid matter having voids and having a volume larger than that of the molten oil and fat composition raw material. . The oil-and-fat composition that has become a solid matter having voids can be pulverized by applying a light impact, and the solid matter is easily disintegrated into powder.
Here, the means for applying a light impact is not particularly specified, but it is simple and preferable to apply a light vibration (shock) by shaking, sieving, or the like to pulverize (loosen) the material.
The solid matter may be pulverized by a known pulverizing means. Examples of such pulverizing means include a hammer mill, a cutter mill, and the like.

<Method for producing wax composition>
The method for producing the wax composition of the present invention is not particularly limited as long as it includes the step of blending the above-described powdery oil composition for wax. The blending step may be any step, and for example, a machine such as a Henschel mixer may be used. In addition, in the blending step, the powdered fat composition of the present invention may be blended with various waxes, or the powdered fat composition of the present invention may be blended with various waxes. This also includes the production of the powdered fat composition of the present invention itself as a wax composition.
The content of the powdered oil composition for wax in the wax composition of the present invention is arbitrary according to its application, but is preferably 0.1 to 100% when the total weight of the wax composition is 100% by weight. % by mass, more preferably 0.5 to 99% by mass, still more preferably 1.0 to 90% by mass. In order to exhibit the desired effects of the present invention, it is preferable that the powdery fat composition for wax of the present invention is contained in an amount of 0.1% by mass or more. The 100% by mass means that the entire wax composition is a powdered oil composition for wax, and can be exemplified as one of preferred embodiments of the wax composition of the present invention.

<Wax property improver>
By the way, as described above, the powdered oil composition for waxes used in the present invention can replace conventional waxes or improve the physical properties of conventional waxes, so that it can be used as a wax physical property improver. can. That is, the present invention also relates to an agent for improving physical properties of a wax containing the powdery oil composition for wax as an active ingredient. As will be described later, when the powdery oil composition for wax of the present invention is used as a toner wax, it has lower volatility than conventional waxes. is preferred.
The wax physical property improving agent of the present invention contains the powdery oil composition for wax as an active ingredient. The wax physical property improving agent of the present invention preferably contains 60% by mass or more, more preferably 80% by mass or more, and still more preferably 100% by mass of the powdery oil composition for wax.
In addition, the wax physical property improving agent of the present invention may contain the above-mentioned powdered oil composition for wax as an active ingredient, and may also include soybean oil and rapeseed oil within a range that does not impair the effects of the present invention. edible oils and fats, dextrin, starch, and other excipients.
However, it is preferable that the wax physical property improving agent of the present invention consists essentially of the powdery oil composition for wax. Here, "substantially" means that the components other than the powdered oil composition for wax contained in the wax property improver are, for example, 0 to 15 wt%, preferably 0 to 15 wt% when the wax property improver is taken as 100 wt%. means 0 to 10% by weight, more preferably 0 to 5% by weight.

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these. Also. In the following, "%" indicates % by mass, and "parts" indicates parts by mass unless otherwise specified.
[Analysis method]
・Conditions for triglyceride composition gas chromatography analysis
DB1-ht (0.32 mm x 0.1 µm x 5 m) Agilent Technologies (123-1131)
Injection volume: 1.0 μL
Inlet: 370°C
Detector: 370°C
Split ratio: 50/1 35.1kPa Constant pressure column CT: 200°C (0min hold) ~ (15°C/min) ~ 370°C (4min hold)
・X-ray diffraction measurement Using an X-ray diffractometer Ultima IV (manufactured by Rigaku Co., Ltd.), using CuKα (λ = 1.542 Å) as a radiation source, using a Cu filter, output 1.6 kW, operating angle 0.96 ~ Measurement was performed under conditions of 30.0° and a measurement speed of 2°/min. This measurement confirmed the presence of α-type fat, β′-type fat, and β-type fat in the fat component containing XXX-type triglycerides. When there was only a peak around 4.6 Å and no peak around 4.1 to 4.2 Å, it was determined that all the fat components were β-type fats.
From the results of the X-ray diffraction measurement, the peak intensity ratio = [the intensity of the characteristic peak of the β type (2θ = 19 ° (4.6 Å)) / (the intensity of the characteristic peak of the α type (2θ = 21 ° (4.2 Å)) + the intensity of the characteristic peak of the β-type (2θ = 19° (4.6 Å)))] was measured as an index representing the abundance of β-type fat.

・ Loose bulk density The loose bulk density (g/cm ³ ) of the powdered oil and fat composition obtained in Examples etc. was measured by placing the powdered oil and fat in a graduated cylinder with an inner diameter of 15 mm × 25 mL from about 2 cm above the upper opening end of the graduated cylinder. The composition was dropped and loosely filled, the filled mass (g) was measured and the volume (mL) was read, and the mass (g) of the powdered oil and fat composition per mL was calculated.
・Crystal (micrograph)
Crystals of the obtained powdered fat composition were photographed with a 3D real surface view microscope VE-8800 (manufactured by KEYENCE CORPORATION). The micrographs obtained are shown in FIG. 4 (manufacturing example 7) and FIG. 5 (manufacturing comparative example 3).
・ Aspect ratio Direct observation with a scanning electron microscope S-3400N (manufactured by Hitachi High-Technologies Co., Ltd.) and arbitrarily selected particles using image analysis type particle size distribution measurement software (Mac-View manufactured by Mountec Co., Ltd.) The length in the major axis direction and the length in the minor axis direction were measured, and the average value of the measured number was obtained.
- Average particle diameter Measured based on the laser diffraction scattering method (ISO133201, ISO9276-1) with a particle size distribution analyzer (Microtrac MT3300ExII manufactured by Nikkiso Co., Ltd.).

・Softening point of binder resin Using a flow tester (Shimadzu Corporation, CFT-500D), while heating 1 g of a sample at a temperature increase rate of 6°C/min, a load of 1.96 MPa was applied with a plunger, and a diameter of 1 mm, Extrude through a 1 mm long nozzle. Plot the amount of plunger descent of the flow tester against the temperature, and take the temperature at which half of the sample flows out as the softening point of the binder resin.
-Glass transition point of binder resin Using a differential scanning calorimeter (Q-100, manufactured by TA Instruments Japan), 0.01 to 0.02 g of the sample was weighed into an aluminum pan and C., and then cooled to 0.degree. C. at a cooling rate of 10.degree. C./min. The sample was then measured at a heating rate of 10°C/min. The temperature at the intersection of the extended line of the baseline below the maximum endothermic peak temperature and the tangent line showing the maximum slope from the rising portion of the peak to the apex of the peak is defined as the glass transition point of the binder resin.
・Acid value of binder resin
Measured by the method of JIS K0070. However, only the measurement solvent is changed from the mixed solvent of ethanol and ether specified in JIS K0070 to the mixed solvent of acetone and toluene (acetone:toluene=1:1 (volume ratio)).
・Melting point and half width of release agent Using a differential scanning calorimeter (DSC Q20, manufactured by TA Instruments Japan), the temperature was raised to 200°C at a heating rate of 10°C/min, and from that temperature The sample was cooled to 10°C at a temperature decrease rate of 5°C/min and then heated to 180°C at a temperature increase rate of 10°C/min. is the melting point of
The peak width at the midpoint of the height from the base line to the peak top of the entire endothermic peak of the melting point is defined as the half width of the release agent.
・ Melt viscosity of release agent Measured using a Brookfield viscometer (LVT manufactured by ST Johnson Japan), heated the measurement sample, and measured at 100 ° C., which is a temperature above the melting temperature of the release agent. Measure.
・Volume median particle size of toner ( _D50 )
Measuring machine: Coulter Multisizer II (manufactured by Beckman Coulter)
Aperture diameter: 100 μm
Analysis software: Coulter Multisizer AccuComp version 1.19 (manufactured by Beckman Coulter)
Electrolyte: Isoton II (manufactured by Beckman Coulter)
Dispersion liquid: Emulgen 109P (manufactured by Kao Corporation, polyoxyethylene lauryl ether, HLB: 13.6)
is dissolved in the electrolytic solution to a concentration of 5% by weight.
Dispersion conditions: Add 10 mg of the measurement sample to 5 ml of the dispersion liquid and disperse it for 1 minute with an ultrasonic disperser, then add 25 ml of the electrolytic solution and further disperse it with an ultrasonic disperser for 1 minute, Prepare a sample dispersion.
Measurement conditions: To 100 ml of the electrolytic solution, the sample dispersion is added so that the particle size of 30,000 particles can be measured in 20 seconds, 30,000 particles are measured, and the volume is determined from the particle size distribution. Determine the median particle size ( _D50 ).

<raw materials>
(1) Powdered oil composition A (wax powdered oil composition)
Triglyceride having a stearic acid residue (18 carbon atoms) at positions 1 to 3 (XXX type: 79.1% by mass, rapeseed extremely hardened oil (melting point 67.3 ° C.), and the rapeseed extremely hardened oil The raw material fat is subjected to a hardening treatment under the conditions of a hydrogen pressure of 0.1 to 0.3 MPa and 160 to 230 ° C. under a nickel catalyst, and then 2 to 5% by weight of steam is blown in to achieve a pressure of 200 to 600 Pa. Under reduced pressure, a deodorizing step was performed at a temperature of 230 to 260°C for 60 to 90 minutes.) 25 g was completely melted by maintaining at 80°C for 0.5 hours, and placed in a constant temperature bath at 60°C. After cooling for 12 hours to form a voided solid with increased volume and complete crystallization, it was cooled to room temperature (25° C.). The obtained solid was mechanically pulverized to obtain a powdery crystalline composition (loose bulk density: 0.2 g/cm ³ , aspect ratio: 1.6, average particle size: 8.0 μm, X-ray diffraction measurement diffraction peak: 4.6 Å, peak intensity ratio: 0.89). This powdered fat composition A was used as wax 1 (release agent).

As wax 2 (mold release agent), carnauba wax "C1" (manufactured by Kato Yoko Co., melting point: 80 ° C.), as wax 3 (mold release agent), paraffin wax "HNP-9" (Nippon Seiro Co., Ltd. (melting point 75° C.) was used. Both carnauba wax and paraffin wax are commonly used waxes for toners.

[Production Example 1 of Binder Resin A]
Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane: 1286g, Polyoxyethylene (2.2)-2,2-bis(4-hydroxyphenyl)propane: 2218g, Terephthalic acid: 1603g, 2 -Tinn (II) ethylhexanoate: 10 g and gallic acid: 2 g were placed in a 10-liter four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer and a thermocouple, and heated to 230°C under a nitrogen atmosphere. After the reaction was carried out at 8.3 kPa until the softening point reached 108° C., Binder Resin A was obtained. Binder Resin A had a softening point of 108.9°C, a glass transition point of 67.4°C, and an acid value of 3.9 mgKOH/g. The reaction rate is defined as the amount of reaction water produced/theoretical amount of water produced×100.

[Production Example of Binder Resin B]
Polyoxypropylene (2.2)-2,2-bis(4-hydroxyphenyl)propane: 3486g, Polyoxyethylene (2.2)-2,2-bis(4-hydroxyphenyl)propane: 3240g, Terephthalic acid: 1881g, Tetra 269 g of propenyl succinic anhydride, 30 g of tin (II) 2-ethylhexanoate, and 2 g of gallic acid were placed in a 10-liter four-necked flask equipped with a nitrogen inlet tube, a dehydration tube, a stirrer, and a thermocouple. After the reaction was carried out at 230° C. in a nitrogen atmosphere until the reaction rate reached 90%, the reaction was carried out at 8.3 kPa for 1 hour. Next, the temperature was lowered to 220°C and the pressure was returned to normal pressure, 789 g of trimellitic anhydride was added, and the reaction was carried out under the conditions of 220°C and normal pressure until the softening point reached 127°C. got a B. Binder Resin B had a softening point of 126.1° C., a glass transition point of 64.5° C., and an acid value of 16.8 mgKOH/g.

[Toner manufacturing example]
Example 1 and Comparative Examples 1-3
Binder resin A: 70 parts by weight, Binder resin B: 30 parts by weight, Negative charge control agent "Bontron E-304" (manufactured by Orient Chemical Co., Ltd.): 1 part by weight, Colorant "ECB-301" (large Phthalocyanine blue (PB15:3) manufactured by Nissei Kagaku Co., Ltd.): 3.5 parts by weight and the predetermined amounts of waxes 1 to 3 listed in Table 2 were mixed for 1 minute using a Henschel mixer, and then under the conditions shown below. , melt kneaded.

A co-rotating twin-screw extruder PCM-30 (manufactured by Ikegai Iron Works Co., Ltd.) was used for the melt-kneading. The operating conditions of the co-rotating twin-screw extruder were barrel set temperature: 100°C, shaft rotation speed: 200 r/min (shaft rotation peripheral speed: 0.30 m/sec), mixture feed rate: 10 kg/hr. .

The resulting kneaded product is cooled, coarsely pulverized to 3 mm by Rotoplex (manufactured by Toa Kikai Co., Ltd.), then pulverized by a fluidized bed jet mill "AFG-400" (manufactured by Alpine Co., Ltd.), and a rotor type classifier "TTSP" (manufactured by Alpine Co., Ltd.) to obtain toner base particles having a volume-median particle size ( _D50 ) of 8.0 μm. To 100 parts by weight of the resulting toner base particles, 1.0 parts by weight of hydrophobic silica "RY50" (manufactured by Nippon Aerosil Co., Ltd.) and 0.5 parts by weight of hydrophobic silica "R972" (manufactured by Nippon Aerosil Co., Ltd.) are added to 20 parts. Mixing was performed for 1 minute at 1500 r/min (peripheral speed: 21 m/sec) using a liter Henschel mixer (manufactured by Mitsui Mining Co., Ltd.) to obtain a toner.

Test Example 1 [low-temperature fixability]
The toner was mounted on a copying machine "AR-505" (manufactured by Sharp Corporation), and an image was printed without being fixed (printing area: 2 cm x 12 cm, adhesion amount: 0.5 mg/cm ² ). The fixing machine of the copier was off-line, and the fixing temperature was increased from 90° C. to 240° C. by 5° C. in increments of 5° C., and the toner was fixed on the paper at 400 mm/sec. As the fixing paper, "CopyBond SF-70NA" (manufactured by Sharp Corporation, 75 g/m ² ) was used.
"UNICEF Cellophane" (Mitsubishi Pencil Co., width: 18 mm, JISZ-1522) was attached to the fixed image, passed through a fixing roller set at 30°C, and then the tape was peeled off. The optical reflection density before the tape was applied and after it was removed was measured using a reflection densitometer "RD-915" (manufactured by Macbeth). The lowest fixing temperature (low temperature fixability) was evaluated by the temperature of the roller. Table 2 shows the results. A smaller value indicates better low-temperature fixability.

Test Example 2 [Internal contamination resistance]
A printer "C5800" (manufactured by Oki Data Co., Ltd.), which uses an oil-less fixing method and a non-magnetic one-component development method and does not have a filter in the exhaust section, was placed in a chamber (internal volume W x H x D: 1000 x 1100 x 810 mm = 0.5 mm). 891 m ³ ), and while printing was performed for 2 hours at a printing rate of 5%, the air in the chamber was pumped through a glass fiber filter (manufactured by Pall Corporation, A/E type, 47 mmφ, pore size 1 μm). The dust was collected under the condition of 50 L/min/cm ² through the air, and the weight of the dispersed fine powder (dust) was measured to calculate the amount of scattering per hour (mg/h), that is, the resistance to in-flight contamination. Table 2 shows the results. A smaller value indicates better resistance to in-machine contamination.

※結着樹脂100重量部に対する重量部
※1 「カルナウバワックスC1」（加藤洋行社製、融点:80℃）
※2 「HNP-9」（日本精蝋社製、融点75℃）

*Parts by weight per 100 parts by weight of binding resin *1 “Carnauba Wax C1” (Made by Kato Yoko Co., melting point: 80°C)
*2 “HNP-9” (manufactured by Nippon Seiro Co., Ltd., melting point 75°C)

From the results in Table 2, it was found that the toner of Example 1 is equally excellent in low-temperature fixability as compared with the toners of Comparative Examples 1 and 2. Further, it was found that the toner of Example 1 is remarkably superior to the toners of Comparative Examples 1 and 2 in terms of resistance to soiling inside the machine. As a result, it was confirmed that the powdered oil-and-fat composition of the present invention has a moderate melting point as a wax and low volatility as compared with conventional waxes. Further, according to the results in Table 2, when the powdered oil composition of the present invention is blended as part of carnauba wax, which is a conventionally known wax, excellent physical properties such as low volatility can be imparted. , the physical properties of the wax can be improved.

Furthermore, production examples of the powdered fat composition of the present invention are shown below. The powdery compositions obtained in these production examples can also be used as a powdery oil composition for waxes in the same manner as in the above examples.
(Production Example 1): x = 16
25 g of a triglyceride (XXX type: 89.7% by mass, tripalmitin, manufactured by Tokyo Chemical Industry Co., Ltd.) having a palmitic acid residue (16 carbon atoms) at positions 1 to 3 was maintained at 80 ° C. for 0.5 hours. and cooled in a 50° C. constant temperature bath for 12 hours to form a solid with increased volume and voids, complete crystallization, and then cooled to room temperature (25° C.). The resulting solid was loosened to give a powdery crystalline composition (loose bulk density: 0.2 g/cm ³ , aspect ratio: 2.0, average particle diameter: 119 μm, X-ray diffraction measurement diffraction peak: 4.0 μm). 6 Å, peak intensity ratio: 0.90).

(Production Example 2): x = 16
25 g of triglyceride (XXX type: 69.9% by mass, hard palm stearin, manufactured by Nisshin OilliO Group Co., Ltd.) having palmitic acid residues (16 carbon atoms) at positions 1 to 3 at 80 ° C. for 0.5 hours Maintained and completely melted, cooled in a 50 ° C constant temperature bath for 12 hours to form a solid with voids with increased volume, complete crystallization, and then cooled to room temperature (25 ° C). By loosening the obtained solid, a powdery crystal composition (loose bulk density: 0.3 g/cm ³ , aspect ratio: 1.4, average particle size: 99 μm, X-ray diffraction measurement diffraction peak: 4.6 Å , peak intensity ratio: 0.88).

(Production Example 3): x = 16, (c2) Tempering method Triglyceride having palmitic acid residues (16 carbon atoms) at positions 1 to 3 (XXX type: 89.7% by mass, tripalmitin, Tokyo Chemical Industry Co., Ltd. Co., Ltd.) 15 g is maintained at 80 ° C. for 0.5 hours to completely melt, cooled in a 30 ° C. After forming a solid with increased porosity and complete crystallization, it was cooled to room temperature (25° C.). By loosening the obtained solid, a powdery crystal composition (loose bulk density: 0.2 g/cm ³ , aspect ratio: 2.0, average particle size: 87 μm, X-ray diffraction measurement diffraction peak: 4.6 Å , peak intensity ratio: 0.89).

(Production Example 4): x = 16, (c1) Seeding method Triglyceride having palmitic acid residues (16 carbon atoms) at positions 1 to 3 (XXX type: 89.7% by mass, tripalmitin, Tokyo Kasei Kogyo Co., Ltd.) was maintained at 80°C for 0.5 hours to completely melt, cooled in a 60°C constant temperature bath until the product temperature reached 60°C, and then added tripalmitin oil powder to the raw oil. 0.1% by mass was added and allowed to stand in a constant temperature bath at 60° C. for 2 hours to form a solid substance having voids with an increased volume. cooled. By loosening the obtained solid, a powdery crystal composition (loose bulk density: 0.2 g/cm ³ , aspect ratio: 2.0, average particle size: 92 μm, X-ray diffraction measurement diffraction peak: 4.6 Å , peak intensity ratio: 0.89).

(Production Example 5): x = 18
3 g of a triglyceride (XXX type: 99.6% by mass, tristearin, manufactured by Sigma-Aldrich) having a stearic acid residue (18 carbon atoms) at positions 1 to 3 is maintained at 80 ° C. for 0.5 hours to complete It was melted and cooled in a 60° C. constant temperature bath for 12 hours to form a voided solid with an increased volume, complete crystallization, and then cooled to room temperature (25° C.). By loosening the obtained solid, a powdery crystal composition (loose bulk density: 0.2 g/cm ³ , aspect ratio: 2.0, average particle size: 30 μm, X-ray diffraction measurement diffraction peak: 4.6 Å , peak intensity ratio: 0.93).

(Production Example 6): x = 18
25 g of a triglyceride (XXX type: 96.0% by mass, tristearin, manufactured by Tokyo Chemical Industry Co., Ltd.) having a stearic acid residue (18 carbon atoms) at positions 1 to 3 was maintained at 80 ° C. for 0.5 hours. and cooled in a 55° C. constant temperature bath for 12 hours to form a solid with increased volume and voids, complete crystallization, and then cooled to room temperature (25° C.). By loosening the obtained solid, a powdery crystal composition (loose bulk density: 0.2 g/cm ³ , aspect ratio: 2.0, average particle size: 31 μm, X-ray diffraction measurement diffraction peak: 4.6 Å , peak intensity ratio: 0.88).

(Production Example 7): x = 18
Triglyceride having a stearic acid residue (18 carbon atoms) at positions 1 to 3 (XXX type: 79.1% by mass, extremely hydrogenated rapeseed oil, manufactured by Yokozeki Oil Industry Co., Ltd.) 25 g at 80 ° C. for 0.5 hours The mixture was maintained and completely melted, cooled in a 55° C. constant temperature bath for 12 hours to form a voided solid with increased volume, complete crystallization, and then cooled to room temperature (25° C.). By loosening the obtained solid, a powdery crystal composition (loose bulk density: 0.2 g/cm ³ , aspect ratio: 1.6, average particle size: 54 μm, X-ray diffraction measurement diffraction peak: 4.6 Å , peak intensity ratio: 0.89).

(Production Example 8): x = 18
Triglyceride (XXX type: 66.7% by mass, extremely hydrogenated soybean oil, manufactured by Yokozeki Oil Industry Co., Ltd.) having a stearic acid residue (18 carbon atoms) at 1-3 positions at 80 ° C. for 0.5 hours After maintaining and completely melting, cooling in a 55° C. constant temperature bath for 12 hours to form a voided solid with increased volume to complete crystallization, and then cooled to room temperature (25° C.). By loosening the obtained solid, a powdery crystal composition (loose bulk density: 0.3 g/cm ³ , aspect ratio: 1.4, average particle size: 60 μm, X-ray diffraction measurement diffraction peak: 4.6 Å , peak intensity ratio: 0.91).

(Production Example 9): x=18
Triglyceride having a stearic acid residue (18 carbon atoms) at positions 1 to 3 (XXX type: 84.1% by mass, Nisshin sunflower oil (S) (high oleic sunflower oil), manufactured by Nisshin OilliO Group Co., Ltd. ) was subjected to a complete hydrogenation treatment by a conventional method to obtain a hydrogenated product (XXX type: 83.9% by mass). 25 g of the obtained high oleic sunflower oil extremely hydrogenated oil was kept at 80° C. for 0.5 hours to completely melt, and cooled in a 55° C. constant temperature bath for 12 hours to obtain a solid matter having voids with an increased volume. After formation and crystallization was complete, it was cooled to room temperature (25° C.). By loosening the obtained solid, a powdery crystal composition (loose bulk density: 0.2 g/cm ³ , aspect ratio: 1.6, average particle size: 48 μm, X-ray diffraction measurement diffraction peak: 4.6 Å , peak intensity ratio: 0.89).

(Production Example 10): x=18
Triglyceride having a stearic acid residue (18 carbon atoms) at positions 1 to 3 (XXX type: 66.7% by mass, extremely hydrogenated soybean oil, manufactured by Yokozeki Oil Industry Co., Ltd.) 18.75 g, and another 1 position ~ Triglyceride having a stearic acid residue (18 carbon atoms) at the 3-position (XXX type: 11.1% by mass, extremely hardened palm oil, manufactured by Yokozeki Oil Industry Co., Ltd.) 6.25 g was mixed to make a raw oil (XXX mold: 53.6% by weight). The raw material fat is maintained at 80°C for 0.5 hours to completely melt, and cooled in a 55°C constant temperature bath for 12 hours to form a voided solid with increased volume and complete crystallization. , cooled to room temperature (25° C.). By loosening the obtained solid, a powdery crystal composition (loose bulk density: 0.3 g/cm ³ , aspect ratio: 1.4, average particle size: 63 μm, X-ray diffraction measurement diffraction peak: 4.6 Å , peak intensity ratio: 0.78). In addition, since the content of XXX-type triglyceride is extremely low, the extremely hydrogenated palm oil was used as a diluent component (hereinafter the same).

(Production Example 11): x = 18, (c1) Seeding method Triglyceride having a stearic acid residue (18 carbon atoms) at positions 1 to 3 (XXX type: 96.0% by mass, Tristearin, Tokyo Kasei Kogyo Co., Ltd.) was maintained at 80°C for 0.5 hours to completely melt, cooled in a 70°C constant temperature bath until the product temperature reached 70°C, and then tristearin oil powder was added to the raw oil. 0.1% by mass was added and left for 12 hours in a constant temperature bath at 70° C. to form a solid substance having voids with an increased volume. cooled. By loosening the obtained solid, a powdery crystal composition (loose bulk density: 0.2 g/cm ³ , aspect ratio: 2.0, average particle size: 36 μm, X-ray diffraction measurement diffraction peak: 4.6 Å , peak intensity ratio: 0.88).

(Production Example 12): x = 18, (c2) Tempering method Triglyceride having a stearic acid residue (18 carbon atoms) at positions 1 to 3 (XXX type: 79.1% by mass, extremely hydrogenated rapeseed oil, Yokozeki (manufactured by Yushi Kogyo Co., Ltd.) was completely melted by maintaining at 80 ° C. for 0.5 hours, cooled in a 50 ° C. A voided solid with increased volume was formed, and after crystallization was completed, it was cooled to room temperature (25° C.). By loosening the obtained solid, a powdery crystal composition (loose bulk density: 0.2 g/cm ³ , aspect ratio: 1.6, average particle size: 50 μm, X-ray diffraction measurement diffraction peak: 4.6 Å , peak intensity ratio: 0.90).

(Production Example 13): x = 18, (c2) Tempering method Triglyceride having a stearic acid residue (18 carbon atoms) at positions 1 to 3 (XXX type: 79.1% by mass, extremely hydrogenated rapeseed oil, Yokozeki (manufactured by Yushi Kogyo Co., Ltd.) was completely melted by maintaining at 80 ° C. for 0.5 hours, cooled in a 40 ° C. , to form a voided solid with increased volume, complete the crystallization, and then cool to room temperature (25° C.). By loosening the obtained solid, a powdery crystal composition (loose bulk density: 0.2 g/cm ³ , aspect ratio: 1.6, average particle size: 52 μm, X-ray diffraction measurement diffraction peak: 4.6 Å , peak intensity ratio: 0.89).

(Production Example 14): x = 18, (c3) Pre-cooling method Triglyceride having stearic acid residues (18 carbon atoms) at positions 1 to 3 (XXX type: 79.1% by mass, rapeseed extremely hardened oil, Yokozeki Oil Industry Co., Ltd.) 25 g is maintained at 80 ° C. for 0.5 hours to completely melt, and the raw fat is kept in a 70 ° C. After cooling to form a voided solid with increased volume and complete crystallization, it was cooled to room temperature (25° C.). By loosening the obtained solid, a powdery crystal composition (loose bulk density: 0.2 g/cm ³ , aspect ratio: 1.6, average particle size: 60 μm, X-ray diffraction measurement diffraction peak: 4.6 Å , peak intensity ratio: 0.89).

(Production Example 15): x=20
10 g of a triglyceride (XXX type: 99.5% by mass, triarachidin, manufactured by Tokyo Chemical Industry Co., Ltd.) having an arachidic acid residue (20 carbon atoms) at positions 1 to 3 was maintained at 90 ° C. for 0.5 hours. It was completely melted and cooled in a constant temperature bath at 72° C. for 12 hours to form a voided solid with increased volume, complete crystallization, and then cooled to room temperature (25° C.). By loosening the obtained solid, a powdery crystal composition (loose bulk density: 0.2 g/cm ³ , aspect ratio: 2.0, average particle size: 42 μm, X-ray diffraction measurement diffraction peak: 4.6 Å , peak intensity ratio: 0.92).

(Preparation Example 16): x=22
10 g of a triglyceride (XXX type: 97.4% by mass, tribehenin, manufactured by Tokyo Chemical Industry Co., Ltd.) having a behenic acid residue (22 carbon atoms) at positions 1 to 3 was maintained at 90 ° C. for 0.5 hours. It was completely melted and cooled in a 79° C. constant temperature bath for 12 hours to form a voided solid with increased volume, complete crystallization, and then cooled to room temperature (25° C.). By loosening the obtained solid, a powdery crystal composition (loose bulk density: 0.2 g/cm ³ , aspect ratio: 2.0, average particle size: 52 μm, X-ray diffraction measurement diffraction peak: 4.6 Å , peak intensity ratio: 0.93).

(Preparation Example 17): x=16, 18
12.5 g of triglyceride (XXX type: 89.7% by mass, tripalmitin, manufactured by Tokyo Chemical Industry Co., Ltd.) having a palmitic acid residue (16 carbon atoms) at positions 1 to 3, and stearin at positions 1 to 3 12.5 g of a triglyceride having an acid residue (18 carbon atoms) (XXX type: 96.0% by mass, tristearin, Tokyo Chemical Industry Co., Ltd.) was mixed to obtain a raw material oil (XXX type: 93.8%). . The raw material fat is maintained at 80°C for 0.5 hours to completely melt, cooled in a 55°C constant temperature bath for 16 hours to form a solid with increased volume and voids, and then loosened to form a powder. (loose bulk density: 0.2 g/cm ³ , aspect ratio: 1.6, average particle size: 74 μm, X-ray diffraction measurement diffraction peak: 4.6 Å, peak intensity ratio: 0.90). rice field.

(Preparation Example 18): x=16, 18
12.5 g of triglyceride (XXX type: 69.9% by mass, hard palm stearin, manufactured by Nisshin Oillio Group Co., Ltd.) having palmitic acid residues (16 carbon atoms) at positions 1 to 3, and positions 1 to 3 12.5 g of a triglyceride (XXX type: 79.1% by mass, rapeseed extremely hardened oil, manufactured by Yokozeki Oil Industry Co., Ltd.) having a stearic acid residue (18 carbon atoms) was mixed to obtain a raw material fat (XXX type: 75.3%). The raw material fat is maintained at 80°C for 0.5 hours to completely melt, cooled in a 55°C constant temperature bath for 16 hours to form a solid with increased volume and voids, and then loosened to form a powder. (loose bulk density: 0.3 g/cm ³ , aspect ratio: 1.4, average particle diameter: 77 μm, X-ray diffraction measurement diffraction peak: 4.6 Å, peak intensity ratio: 0.88). rice field.

(Production Comparative Example 1): x = 16
25 g of a triglyceride (XXX type: 89.7% by mass, tripalmitin, manufactured by Tokyo Chemical Industry Co., Ltd.) having palmitic acid residues (16 carbon atoms) at positions 1 to 3 was maintained at 80 ° C. for 0.5 hours. and cooled in a constant temperature bath at 25° C. for 4 hours, it completely solidified (X-ray diffraction measurement diffraction peak: 4.1 Å, peak intensity ratio: 0.10), and a powdery crystalline composition did not reach

(Production Comparative Example 2): x = 16, 18
12.5 g of triglyceride (XXX type: 69.9% by mass, hard palm stearin, manufactured by Nisshin Oillio Group Co., Ltd.) having palmitic acid residues (16 carbon atoms) at positions 1 to 3, and positions 1 to 3 12.5 g of a triglyceride (XXX type: 11.1% by mass, extremely hardened palm oil, manufactured by Yokozeki Oil Industry Co., Ltd.) having a stearic acid residue (18 carbon atoms) was mixed to obtain a raw material fat (XXX type: 39.6% by mass). The raw material fat was kept at 80°C for 0.5 hours to completely melt and cooled in a constant temperature bath at 40°C for 12 hours to completely solidify (X-ray diffraction measurement diffraction peak: 4.2 Å, peak intensity ratio: 0.12), which did not lead to a powdery crystalline composition.

(Production Comparative Example 3): x = 18
Triglyceride having a stearic acid residue (18 carbon atoms) at positions 1 to 3 (XXX type: 79.1% by mass, extremely hydrogenated rapeseed oil, manufactured by Yokozeki Oil Industry Co., Ltd.) 25 g at 80 ° C. for 0.5 hours It was completely melted while maintaining and cooled in a constant temperature bath at 40° C. for 3 hours, whereupon it completely solidified (X-ray diffraction measurement diffraction peak: 4.1 Å, peak intensity ratio: 0.11) and powdered crystals. A composition was not reached.

(Production Comparative Example 4): x = 18
Triglyceride having a stearic acid residue (18 carbon atoms) at positions 1 to 3 (XXX type: 66.7% by mass, extremely hydrogenated soybean oil, manufactured by Yokozeki Oil Industry Co., Ltd.) 12.5 g, and another 1st to 12.5 g of a triglyceride having a stearic acid residue (18 carbon atoms) at the 3-position (XXX type: 11.1% by mass, extremely hardened palm oil, manufactured by Yokozeki Oil Industry Co., Ltd.) was mixed to obtain a raw material fat (XXX mold: 39.7% by weight). The raw material fat was kept at 80°C for 0.5 hours to completely melt, and cooled in a 55°C constant temperature bath for 12 hours to completely solidify (X-ray diffraction measurement diffraction peak: 4.2 Å, peak intensity ratio: 0.12), which did not lead to a powdery crystalline composition.

Table 3 summarizes the results of the above production examples and production comparative examples.

Claims (13)

A wax composition containing a powdered fat composition for wax containing a powdered fat composition that satisfies the following condition (a), wherein the powdered fat composition is added to 100 parts by mass of the wax composition. A wax composition containing 0.1 to 100 parts by mass of the composition.
(a) A powdered oil-fat composition containing an oil-and-fat component containing one or more XXX-type triglycerides having a fatty acid residue X with x carbon atoms at the 1- to 3-positions of glycerin, wherein the carbon number x is 10 to 22, the oil component contains a β-type oil, the particles of the powdered oil and fat composition have a plate-like shape, and the powdered oil and fat composition has a loose bulk density of 0.05 to 0.05. 6g/cm ³ is. 2. The wax composition according to claim 1, wherein said fat component comprises a β-type fat. 3. The wax composition according to claim 1, wherein the XXX triglyceride is contained in an amount of 50% by mass or more when the total mass of the fat and oil component is 100% by mass. The wax composition according to any one of claims 1 to 3, wherein the carbon number x is an integer selected from 16-18. The wax composition according to any one of claims 1 to 4, wherein the loose bulk density of the powdered fat composition is 0.1 to 0.4 g/cm3. The wax composition according to any one of claims 1 to 5, wherein the plate-like shape of the powdered fat composition has an aspect ratio of 1.1 or more. The wax composition according to any one of claims 1 to 6, wherein no α-type fat is detected in the powdery fat composition by differential scanning calorimetry. The wax composition according to any one of claims 1 to 7, wherein the powdery oil composition has a diffraction peak at 4.5 to 4.7 Å in X-ray diffraction measurement. Claims 1 to 8, wherein the peak intensity ratio (4.6 Å peak intensity/(4.6 Å peak intensity + 4.2 Å peak intensity)) in X-ray diffraction measurement of the powdered oil and fat composition is 0.2 or more. The wax composition according to any one of . Any one of claims 1 to 9, wherein the powdered oil and fat composition contains a β-type oil and fat obtained by cooling and solidifying an oil and fat composition raw material containing XXX triglycerides at a temperature equal to or higher than the cooling temperature obtained from the following formula: 2. The wax composition according to item 1.
Cooling temperature (°C) = carbon number x x 6.6-68 The powdered fat composition contains a β-type fat obtained by cooling and solidifying an oil-fat composition raw material containing XXX-type triglycerides at a temperature equal to or higher than the melting point of the α-type fat corresponding to the β-type fat. 10. The wax composition according to any one of items 1 to 9. The wax composition according to any one of claims 1 to 11, wherein the powdered oil composition has an average particle size of 20 µm or less. The wax composition according to any one of claims 1 to 12, which is for toner.

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