Non-anhydrogenated hard butter composition

Abstract

This invention provides a non-tempered hard butter composition that exhibits good mouth-melting properties in oily pastries while suppressing the occurrence of blooming over time. This non-tempered hard butter composition satisfies the following conditions (1) to (3): Condition (1): SFC at 25°C is 27-67%. Condition (2): The content of trisaturated triglycerides constituting the triglycerides is 20-65% by mass. Condition (3): The content of mixed acid trisaturated triglycerides (LaSS) containing lauric acid residues (La) in the trisaturated triglycerides is 51-65% by mass, wherein S represents saturated fatty acid residues with 16 or more carbon atoms.

Description

Technical Field

[0001] This invention relates to a non-tempered type hard butter composition. Furthermore, this invention relates to oily pastries comprising this non-tempered type hard butter composition. Background Technology

[0002] Generally speaking, the higher the flavor intensity of cocoa, the better the chocolate and the higher its commercial value. Methods to increase the cocoa flavor intensity in chocolate include: incorporating large amounts of cocoa ingredients such as cocoa powder, cocoa mass, and cocoa butter.

[0003] On the other hand, the appearance of chocolate, like its flavor, is also a factor in enhancing its commercial value. Generally, a glossy appearance is desired in chocolate, meaning the absence of surface desaturation or white spots (hereinafter referred to as "bloom"). This requirement remains unchanged for both tempered and untempered chocolate. However, in untempered chocolate, when a large amount of cocoa is used to enhance the cocoa flavor, the low compatibility between cocoa butter and untempered hard butter can sometimes lead to bloom. It is known that bloom, primarily caused by low compatibility, is due to the combination of fats used, and therefore this phenomenon can occur even with proper temperature control during chocolate manufacturing and storage. In other words, in untempered chocolate, it is very difficult to achieve both a preferred flavor and a preferred appearance, and there is a tendency to find it difficult to obtain a well-flavored chocolate without bloom.

[0004] Previously, as one method to improve compatibility with cocoa butter, high-trans-acid hard butter containing trans-unsaturated fatty acids was proposed. However, since oils containing trans-unsaturated fatty acid residues have been identified as harmful to health, there is a need to suppress the intake of trans-unsaturated fatty acids. Therefore, worldwide, there is a tendency to avoid using high-trans-acid hard butter and use low-trans-acid hard butter instead.

[0005] Therefore, various developments have recently been undertaken to achieve a non-tempered hard butter that is less prone to blooming, has good compatibility with cocoa butter, and suppresses trans-unsaturated fatty acid residues to the lowest possible level. For example, Patent Document 1 discloses a non-tempered hard butter made by mixing a micro-hydrogenated oil rich in SUS-type triglycerides and an oil rich in SSU-type triglycerides. Furthermore, Patent Documents 2 and 3 disclose non-tempered hard butter with adjusted composition of fatty acids and triglycerides.

[0006] However, those skilled in the art know that changes in the crystallization polymorphism of the oil in chocolate containing a non-tempered hard butter composition can lead to changes in the quality of the chocolate over time. For example, Patent Document 4 proposes a method for obtaining chocolate with stable crystallization polymorphism of 2-chain β-type crystals by containing oil powder with a melting point of 50°C or higher and 2-chain β-type crystals.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: International Publication No. 2005 / 094598

[0010] Patent Document 2: Japanese Patent No. 5830582

[0011] Patent Document 3: Japanese Patent No. 6366495

[0012] Patent Document 4: Japanese Patent Application Publication No. 2019-170240 Summary of the Invention

[0013] The technical problem solved by the invention

[0014] While the technologies described in Patent Documents 1-3 have improved the suppression of blooming and cocoa butter compatibility to some extent, there is still room for improvement, such as the occurrence of blooming during long-term storage when the cocoa butter content in oily pastries is increased to more than 10%.

[0015] Furthermore, the hard butter described in Patent Document 1 contains a relatively high amount of trans-unsaturated fatty acids, which does not adequately meet the latest requirements for inhibiting the intake of trans fatty acids. Additionally, as shown in Patent Document 4, while methods that suppress the transformation of crystallization polymorphism in oils containing high-melting-point powdered oils are indeed useful from the viewpoint of suppressing blooming, when chocolate dough contains an amount of powdered oil sufficient to suppress the transformation of crystallization polymorphism, the melt-in-your-mouth properties tend to deteriorate regardless of whether there are changes in crystallization polymorphism over time.

[0016] Therefore, the technical problem of the present invention is to provide a non-tempered hard butter composition that, while suppressing the occurrence of blooming over time, produces oily pastries with good mouth-melting properties.

[0017] Technical means to solve the problem

[0018] To solve the aforementioned technical problems, the inventors conducted in-depth research and discovered that by using a non-tempered hard butter composition containing a certain amount of mixed-acid type trisaturated triglycerides with lauric acid residues within a certain range of SFC at 25°C, the structural transformation of fat crystallization can be suppressed. Furthermore, it was found that by suppressing the structural transformation of fat crystallization, the phenomenon of blooming over time can be suppressed in oily desserts obtained using the non-tempered hard butter composition of the present invention.

[0019] That is, the present invention includes the following contents.

[0020] [1] A non-tempered hard butter composition that satisfies the following conditions (1) to (3).

[0021] Condition (1): SFC at 25℃ is 27-67%.

[0022] Condition (2): The content of trisaturated triglycerides in the triglycerides is 20-65% by mass.

[0023] Condition (3): The content of mixed acid type trisaturated triglycerides (LaSS) containing lauric acid residues (La) in the trisaturated triglycerides is 51-65% by mass, where S represents saturated fatty acid residues with 16 or more carbon atoms.

[0024] [2] The non-tempered hard butter composition according to [1] also satisfies the following condition (4).

[0025] Condition (4): The amount of trilauroyl glycerol in the trisaturated triglyceride is less than 10% by mass.

[0026] [3] The non-tempered hard butter composition according to [1] or [2] contains the following fats A and fats B.

[0027] Oil A: Random transesterified oil that meets the following conditions (a-1) and (a-2).

[0028] Condition (a-1): The mass ratio of the content of lauric acid residue (La) to the sum of the contents of stearic acid residue (La) and palmitic acid residue (P) in the fatty acid composition [La / (St+P)] is 0.12 to 1.40.

[0029] Condition (a-2): The content of trisaturated triglycerides, which constitute triglycerides and have a total carbon number of 46 or less among saturated fatty acid residues, is 35-65% by mass.

[0030] Oil B: Random transesterified oil that meets the following conditions (b-1) and (b-2).

[0031] Condition (b-1): The saturated fatty acid residues that make up the fatty acid residues are essentially composed of St and P.

[0032] Condition (b-2): The content of disaturated monounsaturated triglycerides in the triglyceride composition is 40-60% by mass, and the proportion of 1,2-disaturated-3-monounsaturated triglycerides in the disaturated monounsaturated triglycerides is 55-75% by mass.

[0033] [4] An oily pastry comprising any one of the following: [1] to [3] a non-tempered hard butter composition.

[0034] The effects of the invention

[0035] According to the present invention, blooming in chocolate can be suppressed, especially blooming caused by low compatibility with cocoa butter. Furthermore, by using the non-tempered hard butter composition of the present invention to manufacture oily desserts, oily desserts with excellent mouth-melting properties can be obtained. Detailed Implementation

[0036] The present invention will now be described in detail through preferred embodiments. The present invention is not limited to the following description, and the constituent elements may be appropriately modified without departing from the spirit of the invention.

[0037] [Non-tempered hard butter composition]

[0038] The non-tempered hard butter composition of the present invention satisfies the following conditions (1) to (3).

[0039] Condition (1): SFC at 25℃ is 27-67%.

[0040] Condition (2): The content of trisaturated triglycerides in the triglycerides is 20-65% by mass.

[0041] Condition (3): The content of mixed acid type trisaturated triglycerides (LaSS) containing lauric acid residues (La) in the trisaturated triglycerides is 51-65% by mass, where S represents saturated fatty acid residues with 16 or more carbon atoms.

[0042] The following explains conditions (1) to (3).

[0043] <Condition(1)>

[0044] Condition (1) relates to the SFC (Solid Fat Contents) of the non-tempered hard butter composition at 25°C.

[0045] In the non-tempered hard butter composition of the present invention, the SFC at 25°C must be 27-67%. In combination with the conditions (2) and (3) described later, by keeping the SFC at 25°C within this range, the occurrence of blooming over time can be suppressed.

[0046] From the viewpoint of further suppressing the blooming phenomenon, the lower limit of the SFC (saturated fat content) of the non-tempered hard butter composition of the present invention at 25°C is preferably 32% or more, more preferably 35% or more, and even more preferably 38% or more. Furthermore, the upper limit is preferably 64% or less, more preferably 61% or less, and even more preferably 58% or less.

[0047] The SFC value represents the content of solid fats in oils at a given temperature and can be determined by conventional methods. In this invention, pulsed NMR (direct method) as described in AOCS official method cd16b-93 is used to determine the SFC of the sample being tested, and then the measured value is converted into an oil phase content value. That is, when a sample without an aqueous phase is tested, the measured value is directly taken as the SFC; when a sample containing an aqueous phase is tested, the measured value is converted into an oil phase content value, which is taken as the SFC. (Hereinafter, the determination of SFC is the same.)

[0048] <Condition (2)>

[0049] Condition (2) relates to the content of trisaturated triglycerides that constitute triglycerides.

[0050] In the non-tempered hard butter composition of the present invention, the content of trisaturated triglycerides constituting the triglycerides must be 20-65% by mass. In combination with the conditions described above (1) and (3) described later, by keeping the content of trisaturated triglycerides constituting the triglycerides within this range, the occurrence of blooming can be suppressed. In addition, good mouth-melting properties can also be obtained.

[0051] From the viewpoint of further suppressing the blooming phenomenon, the content of trisaturated triglycerides constituting the triglycerides in the non-tempered hard butter composition of the present invention is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more. Furthermore, the upper limit is preferably 62% by mass or less, more preferably 58% by mass or less, and even more preferably 55% by mass or less.

[0052] The analysis of triglycerides in this invention can be performed by high-performance liquid chromatography (HPLC) according to "Test Method 2.4.6.2-2013 for Standard Oil and Fat Analysis" established by the Japan Oil Chemists' Society. The triglyceride composition shown in this invention is based on values ​​obtained by high-performance liquid chromatography (HPLC) according to "Test Method 2.4.6.2-2013 for Standard Oil and Fat Analysis" established by the Japan Oil Chemists' Society, and the same applies below.

[0053] It should be noted that in the non-tempered hard butter composition of the present invention, the content of disaturated-monounsaturated triglycerides constituting the triglycerides is preferably 20 to 42% by mass. From the viewpoint of suppressing the occurrence of blooming and obtaining good mouth-melting properties, the content of disaturated-monounsaturated triglycerides constituting the triglycerides is preferably 22% by mass or more, more preferably 24% by mass or more, and most preferably 26% by mass or more. Furthermore, the upper limit of the content of disaturated-monounsaturated triglycerides constituting the triglycerides is preferably 40% by mass or less, more preferably 38% by mass or less, and even more preferably 35% by mass or less.

[0054] By ensuring that the amount of disaturated-monounsaturated triglycerides, which together with trisaturated triglycerides are crystallizing components of fats, is within the specified range, even when increasing the cocoa butter content in oily pastries (hereinafter, cocoa butter is referred to as "CB", and the cocoa butter content is referred to as "CB content"), it is preferable to suppress the occurrence of blooming over time and to obtain good mouth-melting properties.

[0055] It should be noted that the proportion of 1,2-disaturated-3-monounsaturated-triglycerides in the disaturated-monounsaturated-triglycerides is preferably 50-80% by mass, more preferably 55-75% by mass, and even more preferably 60-70% by mass.

[0056] <Condition (3)>

[0057] Condition (3) involves the content of mixed acid triglycerides containing lauric acid residues in trisaturated triglycerides.

[0058] In the non-tempered hard butter composition of the present invention, the content of mixed acid triglycerides containing lauric acid residues in the trisaturated triglycerides must be 51-65% by mass.

[0059] Here, the term "mixed-acid type trisaturated triglyceride containing lauric acid residue" in this invention refers to a trisaturated triglyceride in which one of the three saturated fatty acid residues bound to the glycerol backbone is a lauric acid residue, and the other two saturated fatty acid residues are saturated fatty acid residues with 16 or more carbon atoms. Hereinafter, mixed-acid type trisaturated triglycerides containing lauric acid residue (La) are sometimes abbreviated as LaSS. It should be noted that S represents a saturated fatty acid residue with 16 or more carbon atoms.

[0060] In combination with the conditions (1), by keeping the content of LaSS in the trisaturated triglycerides in the range of 51 to 65% by mass, even with an increased CB content, it is possible to suppress the occurrence of frost over time and obtain an oily dessert with good mouth-melting properties.

[0061] From the viewpoint of obtaining more favorable effects of the present invention, in the non-tempered hard butter composition of the present invention, the lower limit of the LaSS content in the trisaturated triglycerides is preferably 52% by mass or more, more preferably 53% by mass or more, and even more preferably 54% by mass or more. Furthermore, the upper limit is preferably 62% by mass or less, more preferably 61% by mass or less, and even more preferably 60% by mass or less.

[0062] From the viewpoint of more preferably suppressing the occurrence of blooming over time in oily desserts using the non-tempered hard butter composition of the present invention, the lauroyl-palmitoyl-stearoyl-triglyceride (hereinafter referred to as "LaPSt") in the trisaturated triglyceride is preferably 12-25% by mass. It should be noted that LaPSt refers to a trisaturated triglyceride formed by the combination of lauric acid residue (La), palmitic acid residue (P), and stearic acid residue (St) with a glycerol backbone, and it is a type of mixed-acid trisaturated triglyceride containing lauric acid residues. It should be noted that the binding sites of the fatty acid residues in LaPSt are not particularly limited.

[0063] In the non-tempered hard butter composition of the present invention, the lower limit of LaPSt in the trisaturated triglycerides is preferably 13% by mass or more, more preferably 14% by mass or more, and even more preferably 15% by mass or more. Furthermore, the upper limit is preferably 24% by mass or less, more preferably 23% by mass or less, and even more preferably 22% by mass or less.

[0064] The reason why the occurrence of blooming over time is suppressed by containing LaSS (especially LaPSt) in the non-tempered hard butter composition of the present invention is not yet clear, but it is presumed at this stage as follows.

[0065] It is known that the crystallization and solidification rates of fats and oils vary depending on their type and composition. Generally, trisaturated triglycerides have a higher melting point and crystallize and solidify earlier than other components. There is a difference in the solidification rate between trisaturated triglycerides and disaturated monounsaturated triglycerides, which are the crystallizing components of fats and oils. Trisaturated triglycerides begin to crystallize and solidify or complete their crystallization and solidification before disaturated monounsaturated triglycerides such as di-palmitoyl-mono-oleoyl-triglycerides, mono-palmitoyl-mono-stearoyl-mono-oleoyl-triglycerides, etc. Therefore, it is presumed that disaturated monounsaturated triglycerides transfer fat to the surface of non-tempered hard butter compositions or oily pastries in the form of extrusion from trisaturated triglycerides, and the substance that crystallizes directly on this surface is called bloom.

[0066] In contrast, in the presence of LaSS, it is presumed that this component hinders the alignment of crystal structures and slows down the crystallization process of high-melting-point trisaturated triglycerides. For disaturated monounsaturated triglycerides, it acts as a crystallizing agent, thereby accelerating the crystallization process. This reduces the difference in crystallization rates between the two components, thus suppressing the occurrence of blooming over time.

[0067] <Other suitable conditions>

[0068] The non-tempered hard butter composition of the present invention preferably satisfies the following condition (4) relating to the formation of triglycerides, in addition to the conditions (1) to (3) described above.

[0069] Condition (4): The amount of trilauroyl glycerol in the trisaturated triglyceride is less than 10% by mass.

[0070] Therefore, even when increasing the proportion of cocoa butter in the oil content of oily pastries, it is easy to obtain oily pastries where the blooming phenomenon is further suppressed over time.

[0071] In the non-tempered hard butter composition of the present invention, the content of trilauroyl glycerol in the trisaturated triglycerides is preferably 10% by mass or less, more preferably 9% by mass or less, and even more preferably 8% by mass or less. Furthermore, the lower limit of the trilauroyl glycerol content is not particularly limited and is 0% by mass. By keeping the trilauroyl glycerol content within the stated range, it is easy to obtain oily desserts in which the occurrence of blooming over time is suppressed.

[0072] The reason why oily pastries are prone to blooming due to the high content of trilauroyl glycerol is currently unclear, but the following assumptions are made.

[0073] First, trisaturated triglycerides containing only a single saturated fatty acid residue are more likely to interact with each other than mixed-acid trisaturated triglycerides containing multiple saturated fatty acid residues of varying lengths, and are therefore presumed to crystallize more readily. Here, since trilauroyl glycerol is a triglyceride with a relatively low melting point among the trisaturated triglycerides found in edible oils and fats, and is a trisaturated triglyceride containing only a single saturated fatty acid residue, it is presumed to crystallize more readily than other mixed-acid trisaturated triglycerides containing lauric acid residues. Because trilauroyl glycerol crystallizes before other trisaturated triglycerides, acting as a seed for oil crystallization, it is presumed to promote the crystallization of crystallizing components of oils such as trisaturated triglycerides and disaturated monounsaturated triglycerides. Therefore, in the case of using a non-tempered hard butter composition containing more than a certain amount of trilauroyl glycerol, it is presumed that blooming is more likely to occur due to the action of trilauroyl glycerol. Therefore, it is preferable to use a non-tempered hard butter composition in which the amount of trilauroyl glycerol in the trisaturated triglyceride is within the range described above.

[0074] [Method for manufacturing non-tempered hard butter composition]

[0075] The non-tempered hard butter composition of the present invention can be obtained by selecting one or more fats and oils in a manner that satisfies the conditions (1) to (3), preferably further satisfying the condition (4), and including the by-products described later as needed, and mixing them together.

[0076] Hereinafter, an example of a method for manufacturing the non-tempered hard butter composition of the present invention will be described.

[0077] <Oils that can be used in this invention>

[0078] The following describes the fats and oils that can be used in the non-tempered hard butter composition of the present invention. Examples of such fats and oils include: soybean oil, rapeseed oil, corn oil, cottonseed oil, olive oil, peanut oil, rice oil, safflower oil, sunflower seed oil, palm oil, palm kernel oil, coconut oil, salsa butter, mango butter, milk fat, beef tallow, lard, cocoa butter, fish oil, whale oil, and other various vegetable and animal fats and oils, as well as fats and oils obtained by subjecting these fats and oils to one or more physical or chemical treatments such as hydrogenation, fractionation, or transesterification. Mixtures of two or more fats and oils selected from these types of fats and oils may also be used.

[0079] In the non-tempered hard butter composition of the present invention, one or more of these fats are selected and included in such a manner as to satisfy conditions (1) to (3), preferably conditions (4) based on conditions (1) to (3).

[0080] From the viewpoint of improving cocoa butter compatibility and inhibiting blooming, this invention preferably selects and contains lauric acid-containing oils as one of the raw materials. Lauric acid-containing oils in this invention refer to coconut oil, palm kernel oil, and oils obtained by subjecting these oils to one or more physical or chemical treatments such as hydrogenation, fractionation, or transesterification, and specifically refer to oils containing lauric acid residues (12-carbon saturated fatty acid residues) constituting the fatty acid residues in a proportion of 15-65% by mass.

[0081] Furthermore, from the viewpoint of suppressing the occurrence of blooming over time and easily obtaining oily desserts with good mouth-melting properties, palm oils are preferably selected and included as one of the raw materials in this invention. Palm oils in this invention refer to palm oil, and oils obtained by subjecting these oils to one or more physical or chemical treatments such as hydrogenation, fractionation, or transesterification.

[0082] Next, the lauric acid oils and palm oils preferred for use in this invention will be described. From the viewpoint that condition (4) is preferably satisfied in addition to conditions (1) to (3), the lauric acid oils and palm oils used in this invention are preferably transesterified oils, and more preferably random transesterified oils.

[0083] By using random transesterified oils, in addition to easily satisfying the conditions (1) to (4), the formation of triglycerides becomes more complex, and even with an increased CB content, the occurrence of blooming can be preferably suppressed. It should be noted that in this invention, in addition to transesterifying oils, hydrogenated and fractionated oils are also treated as "transesterified oils". Similarly, in addition to random transesterifying oils, hydrogenated and fractionated oils are also treated as "random transesterified oils".

[0084] Hereinafter, as preferred embodiments using lauric acid oils and palm oils, lauric acid oils as random transesterification oils and palm oils as random transesterification oils will be described.

[0085] From the viewpoint of suppressing the occurrence of frost, the following oil A is preferably used as the lauric oil used in this invention, and the following oil B is preferably used as the palm oil.

[0086] • Oil A: Random transesterified oil that meets the following conditions (a-1) and (a-2).

[0087] Condition (a-1): The mass ratio of the content of lauric acid residue (La) to the sum of the contents of stearic acid residue (St) and palmitic acid residue (P) in the fatty acid composition [La / (St+P)] is 0.12 to 1.40.

[0088] Condition (a-2): The content of trisaturated triglycerides, which constitute triglycerides and have a total carbon number of 46 or less among saturated fatty acid residues, is 35-65% by mass.

[0089] • Oil B: Random transesterified oil that meets the following conditions (b-1) and (b-2).

[0090] Condition (b-1): The saturated fatty acid residues that make up the fatty acid residues are essentially composed of St and P.

[0091] Condition (b-2): The content of disaturated monounsaturated triglycerides in the triglyceride composition is 40-60% by mass, and the proportion of 1,2-disaturated-3-monounsaturated triglycerides in the disaturated monounsaturated triglycerides is 55-75% by mass.

[0092] -Fats A-

[0093] Oil A is a random transesterification oil that satisfies conditions (a-1) and (a-2). First, condition (a-1) will be explained.

[0094] --Condition(a-1)--

[0095] Condition (a-1) relates to the mass ratio of the La content in the constituent fatty acid residues to the sum of the St and P contents [La / (St+P)]. From the viewpoint of suppressing the occurrence of blooming over time, the mass ratio [La / (St+P)] is in the range of 0.12 to 1.40. The lower limit of this mass ratio is preferably 0.35 or more, more preferably 0.38 or more, and even more preferably 0.40 or more. The upper limit of this mass ratio is preferably 1.20 or less, more preferably 1.15 or less, even more preferably 1.10 or less, and even more preferably 0.75 or less or 0.55 or less. For example, the range of this mass ratio is preferably 0.35 to 1.20, more preferably 0.38 to 1.15, even more preferably 0.40 to 1.10, and even more preferably 0.40 to 0.75 or 0.40 to 0.55.

[0096] Regarding the content of fatty acid residues such as St and P in the composition of fatty acid residues, for example, you can refer to "Japan Oil Chemistry Society Standard Oil Analysis Test Method 2.4.2.3-2013", "Japan Oil Chemistry Society Standard Oil Analysis Test Method 2.4.4.3-2013", and "AOCS Method Ce-1h05", and determine it by capillary gas chromatography.

[0097] --Condition(a-2)--

[0098] Next, condition (a-2) will be explained. Condition (a-2) relates to the content of trisaturated triglycerides (hereinafter referred to as "trisaturated triglycerides with 46 or fewer carbon atoms") that constitute triglycerides and whose total number of carbon atoms in saturated fatty acid residues is 46 or less. Examples of such trisaturated triglycerides with 46 or fewer carbon atoms include lauroyl-palmitoyl-stearoyl-triglyceride and di-myristoyl-mono-stearoyl-triglyceride.

[0099] The content of trisaturated triglycerides with 46 or fewer carbon atoms is, from the viewpoint of suppressing the occurrence of blooming over time, in the range of 35 to 65% by mass. The lower limit of this content is preferably 36% by mass or more, more preferably 38% by mass or more, even more preferably 40% by mass or more, even more preferably 42% by mass or more, and the upper limit of this content is preferably 61% by mass or less, more preferably 55% by mass or less, even more preferably 52% by mass or less. For example, the range of this content is preferably 36 to 61% by mass, more preferably 38 to 55% by mass, and even more preferably 42 to 52% by mass.

[0100] In particular, the LaPSt content in trisaturated triglycerides with 46 or fewer carbon atoms is preferably 5 to 35% by mass, more preferably 10 to 32% by mass, and even more preferably 15 to 28% by mass.

[0101] It should be noted that, in the preferred oil A used in this invention, the content of trilauroyl glycerol constituting the triglyceride composition is preferably in the range of 2-12% by mass. Trilauroyl glycerol refers to a triglyceride in which all three fatty acid residues bound to the glycerol backbone are lauric acid residues. Since the total number of carbon atoms of the fatty acid residues bound to the glycerol backbone is 36, it is equivalent to a trisaturated triglyceride with 46 or fewer carbon atoms.

[0102] In this invention, from the viewpoint of improving tolerance to frost formation when the CB content is increased, the content of trilauroyl glycerol in the triglyceride of oil A is preferably 2.0 to 9.0% by mass, more preferably 2.0 to 7.0% by mass, and even more preferably 2.0 to 5.5% by mass.

[0103] It should be noted that even when the content of trilauroyl glycerol in the triglyceride is less than 2% by mass, the resistance to blooming can be improved. However, from the point of view of industrial production, it is difficult to achieve a trilauroyl glycerol content of less than 2% by mass while satisfying the preferred (a-1)(a-2) of oil A.

[0104] The reason why the resistance to blooming phenomenon when the CB content is increased can be improved by making the content of trilauroyl glycerol in the triglyceride within the range of the present invention in the manufacture of oil A is not yet clear, but is presumed at this stage as follows.

[0105] As for trilauroyl glycerol, since all the fatty acid residues it binds to are lauric acid residues, it has relatively low compatibility with the triglycerides contained in cocoa butter, and therefore easily crystallizes and precipitates at room temperature. Therefore, it can be inferred that the less of this component there is, the easier it is to inhibit the occurrence of blooming.

[0106] It should be noted that, from the viewpoint of balancing the mouth solubility of oily desserts and the inhibition of blooming, the content of trisaturated triglycerides with a total carbon number of more than 46 carbon atoms (hereinafter also simply referred to as "trisaturated triglycerides with a carbon number of more than 46") is preferably 4 to 30% by mass, more preferably 6 to 27% by mass, and even more preferably 10 to 25% by mass.

[0107] -Manufacturing method of oil A-

[0108] Here, a method for manufacturing fat A, which can preferably be used in the non-tempered hard butter composition of the present invention, will be described.

[0109] For grease A that preferably satisfies conditions (a-1) and (a-2), the following detailed description is based on the preferred method.

[0110] As oil A, it is preferred to select an oil (A-1) with a lauric acid residue content of 35-60% by mass in the fatty acid residues and an oil (A-2) with a palmitic acid residue content of 35-50% by mass and a stearic acid residue content of 45-60% by mass in the fatty acid residues.

[0111] --Fats (A-1)--

[0112] The oil (A-1) used as the raw material for oil A can be an oil with a lauric acid residue content of 35 to 60% by mass in the fatty acid residues. By using an oil with a lauric acid residue content within the aforementioned range as oil (A-1), there is a tendency to preferably satisfy the conditions (a-1) and (a-2).

[0113] Oils that can be used as fats (A-1) are any edible oils that contain 35 to 60% by mass of lauric acid residues in the fatty acid residues, without any particular limitation. Examples include palm kernel oil, coconut oil, and processed oils obtained by subjecting oil complexes containing them to one or more of the following treatments: hydrogenation, fractionation, and transesterification.

[0114] It should be noted that the content of oleic acid residues in the fatty acid residues constituting the fat (A-1) is preferably 5 to 25% by mass, more preferably 10 to 20% by mass.

[0115] It should be noted that the iodine value of the oil (A-1) is preferably 5 to 30, and more preferably 5 to 25.

[0116] --Fats (A-2)--

[0117] The oil (A-2) used as the raw material for oil A can be an oil with a palmitic acid residue content of 35-50% by mass and a stearic acid residue content of 45-60% by mass in the fatty acid residues.

[0118] As for the oil that can be used as an oil (A-2), if the content of palmitic acid residue and stearic acid residue in the fatty acid residues is satisfied respectively, any edible oil can be used, preferably extremely hydrogenated oil of palm oil, palm oil extract, palm super oil extract, etc., and more preferably extremely hydrogenated oil of palm oil.

[0119] It should be noted that when using highly hydrogenated oil as the fat (A-2), from the viewpoint of not containing trans fatty acids, an iodine value of 3 or less is preferred (more preferably an iodine value of 1 or less).

[0120] When oil A is produced by random transesterification, from the viewpoint of preferably satisfying the conditions (a-1) and (a-2), the oil complex of oil (A-1) and oil (A-2) before transesterification preferably contains 40% by mass or more of oil (A-1), more preferably 45% by mass or more. It should be noted that oil (A-2) occupies the remaining portion.

[0121] It should be noted that, from the viewpoint of the compatibility of the oil phase A of the non-tempered hard butter composition of the present invention with edible oils other than oil A containing oil B described later, the content of oil (A-1) in the oil complex is preferably 85% by mass or less.

[0122] The method for obtaining a random transesterified oil for use as oil A can be carried out by conventional methods, such as using chemical catalysts like sodium methoxide, or by using enzymes such as lipases derived from the genera *Alcaligenes*, *Rhizopus*, *Aspergillus*, *Mucor*, and *Penicillium*. It should be noted that the lipase can be immobilized on ion exchange resins or supports such as diatomaceous earth or ceramics, and used as an immobilized lipase, or it can be used in powder form.

[0123] -Fats B-

[0124] Oil B is a random transesterification oil that satisfies conditions (b-1) and (b-2). First, condition (b-1) will be explained.

[0125] --Condition (b-1)--

[0126] Condition (b-1) involves that the saturated fatty acid residues constituting the fatty acid composition residues are substantially composed of stearic acid residues (St) and palmitic acid residues (P). In this invention, "substantially composed of stearic acid residues (St) and palmitic acid residues (P)" means that, for the composition of the fatty acid residues constituting fat B used in the non-tempered hard butter composition of this invention, the sum of the contents of St and P constituting the saturated fatty acid residues is 90% by mass or more. This sum of contents is preferably 92% by mass or more, and more preferably 95% by mass or more.

[0127] It should be noted that, regarding the composition of fatty acid residues in oil B, the content of saturated fatty acid residues with 14 or fewer carbon atoms in the saturated fatty acid residues is preferably less than 5% by mass.

[0128] By making the saturated fatty acid residues in the fatty acid residues of the oil B preferred in this invention substantially composed of St and P, and when used in combination with oil A, the occurrence of blooming can be suppressed, and oily desserts with excellent mouth-melting properties can be easily obtained.

[0129] It should be noted that, in the non-tempered hard butter composition of the present invention, if the mass ratio (St / P) of St to P constituting fatty acid residues in the fat B preferably contained therein is 0.05 to 7.0, then when the product of the present invention is used in the manufacture of oily pastries, it is easy to obtain oily pastries with good aroma release, and therefore preferred.

[0130] For example, when the CB content in the oil phase of an oily pastry is increased, from the viewpoint of making the cocoa flavor more intense from the middle to the end, St / P is preferably 0.1 to 3.0, more preferably 0.3 to 2.0, and even more preferably 0.5 to 1.5.

[0131] --Condition (b-2)--

[0132] Condition (b-2) involves: the content of disaturated monounsaturated triglycerides in the triglycerides is 40-60% by mass, and the proportion of 1,2-disaturated-3-monounsaturated triglycerides in the disaturated monounsaturated triglycerides is 55-75% by mass.

[0133] By using fats B with the content of disaturated monounsaturated triglycerides constituting the triglycerides and the proportion of 1,2-disaturated-3-monounsaturated triglycerides in the disaturated monounsaturated triglycerides within the range described above, it is easy to achieve good mouth-melting properties in oily desserts using the non-tempered hard butter composition of the present invention. The lower limit of the content of disaturated monounsaturated triglycerides constituting the triglycerides is preferably 43% by mass or more, preferably 45% by mass or more, and the upper limit is preferably 57% by mass or less, preferably 55% by mass or less. For example, the range of this content is preferably 43 to 57% by mass, more preferably 45-55% by mass. The lower limit of the proportion of 1,2-disaturated-3-monounsaturated triglycerides in the disaturated monounsaturated triglycerides is preferably 57% by mass or more, preferably 60% by mass or more, and the upper limit is preferably 73% by mass or less, more preferably 70% by mass or less. For example, the range of this proportion is preferably 57 to 73% by mass, more preferably 60 to 70% by mass.

[0134] It should be noted that, from the viewpoint of improving compatibility with cocoa butter and obtaining oily desserts with good mouth-melting properties, the amount of palmitoyl-stearyl-oleoyl-triglyceride (hereinafter referred to as "PStO"), a so-called mixed-acid type triglyceride among disaturated monounsaturated triglycerides, is preferably 40 to 65% by mass, more preferably 42 to 62% by mass, and even more preferably 45 to 57% by mass. It should be noted that PStO is a triglyceride formed by the combination of palmitic acid, stearic acid, and oleic acid at any one of the 1 to 3 positions with the three OH groups of glycerol.

[0135] Furthermore, from the viewpoint of achieving a balance between suppressing the occurrence of blooming and good oral solubility, it is preferable that the content of trisaturated triglycerides in the triglycerides of oil B is 1.0 to 5.0% by mass, more preferably 1.5 to 4.0% by mass, and even more preferably 2.0 to 3.5% by mass.

[0136] -Method for manufacturing oil B-

[0137] Here, conditions (b-1) and (b-2) are preferably satisfied, and the method for manufacturing fat B, which is preferably used in the non-tempered hard butter composition of the present invention, will be described in detail below according to a preferred manner.

[0138] The preferred oil B used in this invention is obtained by fractionating randomly transesterified oils.

[0139] First, a fat complex is prepared in which the sum of the contents of palmitic acid residue (P) and stearic acid residue (St) constituting the fatty acid residues is 95% by mass or more, and the mass ratio of P to St (St / P) is preferably 0.05 to 8, more preferably 0.2 to 2.0, and even more preferably 0.3 to 1.5.

[0140] There are no particular restrictions on the oils used to obtain such oil complexes. For example, one or more of the following can be selected from various vegetable oils and animal oils, such as soybean oil, rapeseed oil, corn oil, cottonseed oil, olive oil, peanut oil, rice oil, safflower oil, sunflower seed oil, palm oil, palm kernel oil, coconut oil, salsa seed resin, mango oil, milk fat, beef tallow, lard, cocoa butter, fish oil, whale oil, etc., as well as oils obtained by performing one or more physical or chemical treatments such as hydrogenation, fractionation, transesterification, etc., on these oils and then mixed together as the oil complex.

[0141] In particular, from the viewpoint of increasing the content of St and P in the constituent fatty acid residues, adjusting the St / P ratio to the preferred range, and reducing or inhibiting the increase of trans fatty acid content, it is preferable to include highly hydrogenated oils in the oil complex.

[0142] It should be noted that examples of highly hydrogenated oils include: highly hydrogenated palm oil, highly hydrogenated soybean oil, highly hydrogenated rapeseed oil, and highly hydrogenated sunflower oil.

[0143] Furthermore, when using highly hydrogenated oils, from the viewpoint that they do not substantially contain trans fatty acids, it is preferable to use highly hydrogenated oils with an iodine value of 3 or less, and even more preferable to use highly hydrogenated oils with an iodine value of 1 or less.

[0144] When extremely hydrogenated oil is used as one of the raw materials for oil B, it can be used in any amount within the range where oil B preferably satisfies the conditions (b-1) and (b-2). The content of extremely hydrogenated oil in the oil complex is preferably 32 to 52% by mass, more preferably 37 to 47% by mass.

[0145] Next, the prepared oil complex is subjected to random transesterification. Random transesterification can be performed using either a chemical catalyst or an enzyme. The random transesterification can be carried out in the same manner as described in the method for manufacturing oil A.

[0146] It should be noted that, in the fractionation process described later, from the viewpoint of efficient fractionation, when the SFC value of the randomly transesterified oil complex at 30°C is set to 1, the SFC value at 20°C is preferably 1.0 to 2.5, more preferably 1.0 to 2.4, and even more preferably 1.0 to 2.3.

[0147] As described above, the oil complex that has undergone random transesterification is fractionated by solvent fractionation or crystallization as detailed below. Furthermore, the resulting low-melting-point or medium-melting-point fraction is preferably included in the non-tempered hard butter composition of the present invention as oil B satisfying conditions (b-1) and (b-2).

[0148] It should be noted that, in order to obtain the low-melting-point fraction or the medium-melting-point fraction of the random transesterified oil that meets the conditions (b-1) and (b-2), multiple fractionation operations can be performed. In this case, the conditions can be changed to perform two or more stages of solvent fractionation, or the conditions can be changed to perform two or more stages of crystallization, or a combination of solvent fractionation and crystallization can be used.

[0149] The fractionation method can be chosen arbitrarily. When the St / P of the oil to be fractionated is less than 0.4, solvent fractionation is preferred. Otherwise, fractionation by crystallization is preferred.

[0150] (solvent fractionation)

[0151] For the solvent used for solvent fractionation, any solvent that dissolves the transesterified fats used for fractionation is acceptable, with no particular limitation. From the viewpoint that the obtained fractionated fats are for consumption, acetone or hexane is preferred.

[0152] There is no particular limitation on the amount of solvent used. From an industrial production point of view, it is preferable to add more than 50 parts by mass of solvent relative to 100 parts by mass of the transesterified oil used for fractionation, more preferably 100 to 1000 parts by mass, and even more preferably 200 to 500 parts by mass.

[0153] It should be noted that when dissolving the oil in the solvent, the high-melting-point fraction to be removed by fractionation needs to be temporarily and fully dissolved; therefore, heating to 30–70°C is preferred. The temperature at which the oil dissolved in the solvent is cooled and maintained (cooling temperature) varies depending on the type of organic solvent; 0–30°C is preferred when using acetone, and -10°C–20°C is preferred when using hexane.

[0154] It should be noted that, from the viewpoint that the high melting point portion is obtained by full precipitation, the holding time at the cooling temperature (cooling time) is preferably 0.1 hours to 100 hours, and more preferably 0.5 hours to 50 hours.

[0155] Regarding the cooling rate, from the viewpoint of preventing the mixing of the target low-melting-point and medium-melting-point portions into the crystallization while allowing the high-melting-point portions to precipitate efficiently, a rate of 20°C / hour or less is preferred; from the viewpoint of industrial production, a rate of 0.1 to 15°C / hour is preferred.

[0156] It should be noted that cooling can be performed using a jacketed cooling system or a heat exchanger. Cooling can be done by allowing the system to stand still or by stirring. From the viewpoint of maintaining good dispersion of the precipitated crystals and uniformly cooling the entire system, stirring is preferred. It should also be noted that the addition of a crystallizer can be chosen selectively, and if added, it can be added at any time. Regarding fractionation, using conventional methods, only the high-melting-point crystals produced by cooling are filtered, and the solvent is removed by heating to obtain the low-melting-point and medium-melting-point fractions.

[0157] (Separation based on crystallization)

[0158] Crystallization refers to the process of cooling and crystallizing molten oils, causing the crystalline portion to precipitate out and separating it into the crystalline portion and the liquid portion.

[0159] It should be noted that there is no particular limitation on the method of cooling crystallization. For example, the following methods can be used: (1) cooling crystallization while stirring; (2) cooling crystallization while standing; (3) cooling crystallization while stirring and then cooling crystallization while standing; (4) fluidization by mechanical stirring after cooling crystallization while standing. From the viewpoint of obtaining a crystallized slurry in which the crystalline part and the liquid part can be easily separated, any one of the methods (1), (3), and (4) is preferred, and the method (1) is more preferred.

[0160] Regarding the crystallization temperature, it is preferable to carry out the crystallization at a temperature where the proportion of crystalline portions in the crystallization slurry, i.e., the SFC (solid fat content) of the transesterified fat at the crystallization temperature, is within the following range: Specifically, the SFC (solid fat content) at the crystallization temperature is preferably 10–70%, more preferably 30–60%, and even more preferably 35–55%. When the solid fat content (SFC) is outside this range, it may be necessary to reduce the efficiency of selectively separating the useful fat components of fat B used in the non-tempered hard butter composition of the present invention.

[0161] Regarding the cooling temperature and time, any conditions within the range specified for the transesterified oil SFC are acceptable and there are no particular limitations. Starting from a state where the transesterified oil is completely dissolved, after 30 minutes to 30 hours, cool to 25 to 60°C, preferably 30 to 50°C, and maintain at this temperature for 30 minutes to 80 hours, preferably 1 to 70 hours, thereby preferably satisfying the SFC within the specified range.

[0162] Furthermore, in the crystallization process of the present invention, when the completely dissolved transesterified oil is cooled to the SFC range described above, it may be rapid cooling, slow cooling, or a combination thereof, adjusted to the SFC range described above. However, in order to facilitate the separation of the crystalline portion and the liquid portion of the obtained crystallized slurry and to improve the yield of the obtained liquid portion, it is preferable to perform slow cooling below the temperature range of crystallization precipitation of the transesterified oil.

[0163] It should be noted that, in this invention, when rapidly cooling the transesterification oil, the cooling rate is preferably 5°C / hour or more, more preferably 5 to 20°C / hour, and when slowly cooling, the cooling rate is preferably 0.3 to 3.5°C / hour, more preferably 0.5 to 3.0°C / hour.

[0164] Here, below the temperature range where transesterified oils crystallize, from the viewpoint of increasing the yield of oil B, it is preferable to perform a maturation process of crystallization by cooling and precipitation once or twice during the cooling process to the preferred SFC temperature within the aforementioned range. The crystallization maturation process in this invention refers to an operation that further crystallizes while making the crystals more uniform, resulting in a crystalline state where the crystalline and liquid portions are easily filtered, thereby improving the yield.

[0165] Specifically, the curing process can be carried out at any temperature between 25 and 60°C, preferably 30 to 50°C, under constant temperature conditions for 30 minutes to 80 hours. It should be noted that there is no particular limit to the number of curing cycles, but it is usually 5 times, preferably 4 times.

[0166] The crystallization conditions are appropriately adjusted according to the composition of the transesterified oil used for crystallization. Preferred crystallization conditions include, for example, crystallization conditions in which the oil is rapidly cooled from a completely dissolved state to 44-50°C over 1-2 hours, and then subjected to one or more aging processes at any temperature during the process of obtaining a crystallized slurry at 32-43°C. It should be noted that the temperature transition between each aging process is preferably achieved through slow cooling.

[0167] As a method for separating the crystalline and liquid portions, natural filtration, suction filtration, press filtration, centrifugation, and combinations thereof can be used. For ease of separation and high efficiency, press filtration using a filter press, belt press, or similar equipment is preferred. During the crystallization of transesterified oils, the solid fat content is high at the crystallization temperature, resulting in a high-viscosity crystallized slurry, or when observed as a blocky substance. Press filtration is particularly suitable because the slurry is slurried due to pressure during the process.

[0168] The preferred pressure for fractionation via pressing and filtration is 0.2 MPa or higher, more preferably 0.5 to 5 MPa. It should be noted that the pressing pressure preferably increases gradually from the beginning to the end of pressing, with an increase rate of 1 MPa / min or less, preferably 0.5 MPa / min or less, and more preferably 0.1 MPa / min or less. A pressurization rate greater than 1 MPa / min may reduce the yield of oil B.

[0169] As described above, solvent extraction or crystallization is performed to obtain fat B, which can be preferably used in the non-tempered hard butter composition of the present invention.

[0170] The oils used in this invention preferably contain one or more of lauric acid oils and palm oils, and more preferably contain lauric acid oils and palm oils.

[0171] Next, the content of lauric acid oils and palm oils in the non-tempered hard butter composition of the present invention will be explained.

[0172] Regarding the content of lauric acid oils, any amount can be used if it meets the range of conditions (1) to (3). However, from the viewpoint that condition (4) is preferred in addition to conditions (1) to (3), it is preferred to be 25 to 85% by mass of the oil contained in the non-tempered hard butter composition of the present invention, preferably 35 to 80% by mass, and more preferably 45 to 80% by mass.

[0173] Similarly, for the content of palm oil, any amount can be used if it meets the range of conditions (1) to (3), but from the viewpoint that it is preferable to meet condition (4) in addition to conditions (1) to (3), it is preferred to be 15 to 75% by mass of the oil contained in the non-tempered hard butter component of the present invention, preferably 20 to 65% by mass, and more preferably 20 to 55% by mass.

[0174] Here, from the viewpoint of preferably satisfying the conditions (1) to (4), it is preferable to contain both lauric acid oil and palm oil. In this case, it is preferable to contain a total of more than 80% lauric acid oil and palm oil, more preferably more than 87% by mass, further preferably more than 95% by mass, and even more preferably 100% by mass.

[0175] Furthermore, from the viewpoint of preferably satisfying the conditions (1) to (4), when both lauric acid oil and palm oil are contained, it is preferable that the content of lauric acid oil when the sum of the contents of lauric acid oil and palm oil is set to 100% by mass is 25 to 85% by mass, more preferably 35 to 80% by mass, and even more preferably 45 to 80% by mass.

[0176] Regarding the amount of fat in the non-tempered hard butter composition of the present invention, from the viewpoint of fully obtaining the effects of the present invention, it is preferably 80% by mass or more, more preferably 85% by mass or more, and even more preferably 90% by mass or more. It should be noted that the upper limit of the amount of fat in the non-tempered hard butter composition of the present invention is 100%.

[0177] The non-tempered hard butter composition of the present invention preferably does not contain water, and the water content is preferably 5% or less, more preferably 3% by mass or less. It should be noted that the water content of the present invention includes not only water but also the water content of the by-products contained in the non-tempered hard butter composition of the present invention, which will be described later.

[0178] The non-tempered hard butter composition of the present invention may contain any secondary ingredients, except for the fats that satisfy the conditions (1) to (3), preferably further satisfying the condition (4), within the range that does not impair the function of the non-tempered hard butter composition of the present invention or within the range that does not impair the flavor and texture of the oily pastry containing the non-tempered hard butter composition of the present invention.

[0179] As a by-product that may be included in the non-tempered hard butter composition of the present invention, examples include: emulsifiers, antioxidants, colorants, flavorings, etc.

[0180] Examples of emulsifiers include: glycerol fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, glycerol organic acid fatty acid esters, polyglycerol fatty acid esters, polyglycerol condensed ricinoleate, calcium stearoyl lactylate, sodium stearoyl lactylate, polyoxyethylene fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and lecithin. In this invention, one or more of glycerol fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, and lecithin are preferably used. When using the emulsifiers, the content of the emulsifier in the non-tempered hard butter composition is preferably in the range of 0.01 to 5% by mass, more preferably 0.03 to 3% by mass.

[0181] As an antioxidant, there are no limitations as long as it does not compromise the flavor; tocopherol or tea extract are preferred.

[0182] Here, the non-tempered hard butter composition of the present invention obtained as described above preferably contains β-prime-type crystals from the viewpoint of suppressing the occurrence of blooming in oily pastries. Whether the fat crystals contain β-prime-type crystals can be determined by an X-ray diffraction apparatus. Specifically, the short plane interval of the fat crystals is set to 2θ: measured within the range of 15 to 30 degrees. The peak detected at 19.5 degrees indicates the presence of β-type fat crystals, and the peak detected at 21 degrees indicates the presence of β-prime-type fat crystals. It should be noted that if two peaks are detected, it is determined that both β-type and β-prime-type fat crystals are present.

[0183] From the viewpoint of obtaining a non-tempered hard butter composition with high resistance to blooming, it is preferable that the ratio of the peak intensity of the peak detected at 19.5 degrees (hereinafter referred to as "peak intensity A") to the peak intensity of the peak detected at 21 degrees (hereinafter referred to as "peak intensity B") is 0 to 50%, more preferably 0 to 10%.

[0184] Peak intensity ratio = Peak intensity A / (Peak intensity A + Peak intensity B) × 100 (%)

[0185] Furthermore, in the non-tempered hard butter composition of the present invention, when the total amount of its constituting fatty acids is set to 100% by mass, the content of trans fatty acids is preferably less than 5% by mass, more preferably less than 3% by mass, less than 2% by mass, or less than 1.5% by mass. The non-tempered hard butter composition of the present invention is preferred because it exhibits sufficient compatibility with cocoa butter even in such a low trans fatty acid system.

[0186] [Oily snacks]

[0187] The non-tempered hard yellow fat composition of the present invention can be used to manufacture oily pastries. The present invention also provides such oily pastries.

[0188] The oily pastries of the present invention comprise the non-tempered hard butter composition of the present invention. There are no particular limitations on the oily pastries of the present invention; examples include chocolate-based and cream-based pastries.

[0189] The following describes the chocolate-type oily confectionery as an example of the present invention. The chocolate-type oily confectionery of the present invention includes the non-tempered hard butter composition of the present invention as a fat constituting the chocolate-type confectionery. In the present invention, "chocolate-type" includes not only chocolate and quasi-chocolate as defined by the National Chocolate Fair Trade Council, but also processed foods such as raw chocolate, white chocolate, and colored chocolate made using cocoa blocks, cocoa butter, and cocoa. It refers to a substance obtained by mixing raw materials selected from various powdered foods such as cocoa blocks, cocoa powder, and milk powder, fats, sugars, emulsifiers, flavorings, and colorings in any proportion, and then subjecting them to conventional methods of rolling and mixing.

[0190] The content of the non-tempered hard butter composition in the chocolate-based oily confectionery of the present invention varies depending on the amount of cocoa butter contained in the chocolate-based confectionery, and is preferably 60 to 95% by mass, more preferably 65 to 95% by mass, and even more preferably 75 to 90% by mass of the oil contained in the chocolate-based confectionery.

[0191] The non-tempered hard butter composition of the present invention has good compatibility with cocoa butter. Therefore, in chocolates containing the non-tempered hard butter composition of the present invention, the cocoa butter content in the oil can be increased to more than 20% by mass without the formation of bloom.

[0192] In order to obtain chocolates with good flavor and texture without the formation of bloom, the oil content of the chocolates containing the non-tempered hard butter composition of the present invention preferably contains 5 to 28% by weight of cocoa butter, more preferably 10 to 25% by weight, and even more preferably 15 to 25% by weight.

[0193] Furthermore, in the case where the chocolate of the present invention contains milk fat derived from dairy products, from the viewpoint of achieving both shape retention at room temperature and mouth melting properties, the milk fat content in the oil content of the chocolate is preferably 20% by mass or less, more preferably 15% by mass or less.

[0194] The cream-based confectionery of the present invention will be described. The cream-based confectionery of the present invention is a substance obtained by using the non-tempered hard butter composition of the present invention in part or all of the oil phase of a cream-based confectionery such as butter cream or frosting cream, in which the oil phase is the continuous phase.

[0195] Here, the hard butter composition of the present invention, as described above, has good compatibility with cocoa butter. Therefore, the creams of the present invention using this composition, even those containing more cocoa butter, can suppress the occurrence of graininess over time, and creams with improved shelf life can be obtained.

[0196] The amount of the non-tempered hard butter composition used in the cream of the present invention is preferably 20 to 100% by mass of the oil contained in the cream, more preferably 30 to 70% by mass.

[0197] The hard butter composition of the present invention has good compatibility with cocoa butter. Therefore, in creams containing the hard butter composition of the present invention, the cocoa butter content in the oil can be increased to more than 20% by mass without blooming.

[0198] In order to obtain good flavor and texture, when the cream of the present invention contains cocoa butter, it is preferable to include 5 to 28% by mass of cocoa butter in the oil content of the cream, more preferably 10 to 25% by mass, and even more preferably 15 to 25% by mass.

[0199] The creams of the present invention, except that they use the non-tempered hard butter composition of the present invention as raw materials, can be manufactured by conventional methods based on the type of cream, etc.

[0200] Example

[0201] The present invention will be specifically described below with reference to specific embodiments. However, the present invention is not limited to the embodiments shown below. It should be noted that, unless otherwise specified, "parts" and "%" in the following text refer to "parts by mass" and "% by mass," respectively.

[0202] <Determination of the oil phase composition of non-tempered hard butter compositions>

[0203] -Determination of fatty acid composition-

[0204] The fatty acid composition of the oil phase of the non-tempered hard butter compositions manufactured in the Examples and Comparative Examples was determined by capillary gas chromatography according to the AOCS method "Ce-1h05".

[0205] The various measurement conditions are as follows.

[0206] (Injection Method) Flow Distribution Method

[0207] (Detector) FID Detector

[0208] (Carrier gas) Helium 1 ml / min

[0209] (Chromatographic column) SUPELCO "SP-2560" (0.25mm, 0.20μm, 100m)

[0210] (Column temperature) 180℃

[0211] (Analysis time) 60 minutes

[0212] (Injection port temperature) 250℃

[0213] (Detector temperature) 250℃

[0214] (Split ratio) 100:1

[0215] -Determination of Triglyceride Composition-

[0216] According to the "Standard Oil Analysis Test Method 2.4.6.2-2013" established by the Japan Oil Chemistry Society, the triglyceride (triacylglycerol) composition of the oil phase of the non-tempered hard butter compositions manufactured in the examples and comparative examples was determined by high performance liquid chromatography (HPLC).

[0217] The various measurement conditions are as follows.

[0218] (Detector): Differential Refraction Detector

[0219] (Chromatographic column): Docosyl column (DCS)

[0220] (Mobile phase): Acetone: Acetonitrile = 65:35 (volume ratio)

[0221] (Flow rate): 1 ml / min

[0222] (Column temperature): 40℃

[0223] (Back pressure): 3.8MPa

[0224] -Determination of the crystallization form of fats and oils-

[0225] The crystallinity of the fats contained in the non-tempered hard butter compositions manufactured in the examples and comparative examples was determined by X-ray diffraction apparatus (RINT2000 manufactured by RIGAKU).

[0226] The various measurement conditions are as follows.

[0227] (Short plane interval for oil crystallization) 2θ = 15–30 degrees

[0228] (Sampling width) 0.02

[0229] (Scanning speed) 6.00θ / min

[0230] (Diverging slit) 1 degree

[0231] (Diverging longitudinal limiting slit) 5mm

[0232] (scattering slit) 1 degree

[0233] (Light-emitting slit) 0.3mm

[0234] The following describes the manufacture of the greases used in the examples.

[0235] <Manufacturing Example 1> (Manufacturing of IE-1)

[0236] 75 parts of palm kernel oil (equivalent to oil (A-1); containing 50.1% lauric acid residue (La) in the fatty acid residues) and 25 parts of extremely hydrogenated palm oil (equivalent to oil (A-2); containing 0.2% La, 44.6% palmitic acid residue (P), and 53.6% stearic acid residue (St) in the fatty acid residues) that has been hydrogenated to make the iodine value less than 1 were mixed in a molten state to obtain an oil complex.

[0237] The oil complex was placed in a four-necked flask and heated under vacuum at 100°C for 30 minutes. Then, sodium methoxide, a random transesterification catalyst, was added at a ratio of 0.2% relative to the oil, and the mixture was heated under vacuum for 1 hour to carry out the random transesterification reaction. Citric acid was then added to neutralize the sodium methoxide. Next, bleaching was performed with bleaching clay (3% relative to the oil, treatment temperature 85°C). After filtering the bleaching clay, deodorization was carried out (250°C, 60 minutes, water vapor blowing in at 3% relative to the oil) to obtain the random transesterified oil (hereinafter referred to as "IE-1").

[0238] IE-1 is a random transesterified fat with a La content of 37.6% in its constituent fatty acid residues, equivalent to "lauric acid fat". Furthermore, as shown in Table 1, since it satisfies conditions (a-1) and (a-2), IE-1 is equivalent to "Fat A" in this invention. It should be noted that the various compositional values ​​of IE-1 are shown in Table 1.

[0239] <Manufacturing Example 2> (Manufacturing of IE-2)

[0240] 45 parts of palm kernel oil (equivalent to oil (A-1); with a La content of 50.1% in the fatty acid residues) and 55 parts of palm stearin (equivalent to oil (A-2); with a La content of 0.4%, a P content of 62.4%, and a St content of 4.6% in the fatty acid residues) were mixed in a molten state to obtain an oil complex. This oil complex was subjected to a random transesterification reaction using sodium methoxide as a catalyst and a bleaching-deodorization purification process, similar to that in Manufacturing Example 1, to obtain a random transesterified oil (hereinafter referred to as "IE-2").

[0241] IE-2 is a random transesterified fat, with a La content of 22.5% in its constituent fatty acid residues, equivalent to a "lauric acid fat". It should be noted that the various compositional values ​​of IE-2 are shown in Table 1.

[0242] <Manufacturing Example 3> (Manufacturing of IE-3)

[0243] 50 parts of palm kernel oil (equivalent to oil (A-1); with a La content of 50.1% in the fatty acid residues) and 50 parts of extremely hydrogenated palm oil (equivalent to oil (A-2); with a La content of 0.2%, a P content of 44.6%, and a St content of 53.6% in the fatty acid residues) that has been hydrogenated to a level where the iodine value is below 1 were mixed in a molten state to obtain an oil complex. This oil complex was subjected to a random transesterification reaction using sodium methoxide as a catalyst and a bleaching-deodorization purification process, similar to that in Manufacturing Example 1, to obtain a random transesterified oil (hereinafter referred to as "IE-3").

[0244] IE-3 is a random transesterified fat with a La content of 25.2% in its constituent fatty acid residues, equivalent to a "lauric acid fat". Furthermore, as shown in Table 1, since it satisfies conditions (a-1) and (a-2), IE-3 is equivalent to "Fat A" in this invention. It should be noted that the various compositional values ​​of IE-3 are shown in Table 1.

[0245] <Manufacturing Example 4> (Manufacturing of IE-4)

[0246] First, 42 parts of extremely hydrogenated palm oil (which has been hydrogenated to a level where the iodine value is below 1), 27.5 parts of palm oil, and 30.5 parts of palm fractionated soft oil (iodine value 65) were stirred and mixed in a separately molten state to obtain an oil complex.

[0247] The oil complex was placed in a four-necked flask and the liquid temperature was adjusted to 90°C. Sodium methoxide was added at a ratio of 0.2 parts per 100 parts of the oil complex, and the mixture was heated and stirred under vacuum for 1 hour. Then, citric acid was added to neutralize the sodium methoxide, and the mixture was purified by conventional methods to obtain transesterified oil E-1 (hereinafter referred to as "E-1") as a random transesterification oil.

[0248] The E-1 was placed in a jacketed glass crystallization tank and rapidly cooled to 46°C at 7.0°C / h while stirring at 50 rpm. After reaching 46°C, it underwent a maturation process for 5 hours, followed by slow cooling to 35°C at 2.2°C / h. After reaching 35°C, it underwent a maturation process for 11 hours to obtain a crystallized slurry. This crystallized slurry was then subjected to filtration, fractionation, and pressing to obtain the fractionated soft oil, which was designated as random transesterification oil IE-4. It should be noted that IE-4 is the low-melting-point fraction of transesterification oil E-1.

[0249] IE-4 is a random transesterified oil and is equivalent to "palm oil". Furthermore, as shown in Table 2, since conditions (b-1) and (b-2) are satisfied, IE-4 is equivalent to "oil B" in this invention. It should be noted that the various compositional values ​​of IE-4 are shown in Table 2.

[0250] <Manufacturing Example 5> (Manufacturing of IE-5)

[0251] First, 45 parts of extremely hydrogenated palm oil, which had been hydrogenated to a level where the iodine value was below 1, and 55 parts of palm oil were stirred together in a molten state to obtain an oil complex. This oil complex was then subjected to a random transesterification reaction using sodium methoxide as a catalyst and purified using conventional methods, similar to that in Manufacturing Example 4, to obtain transesterified oil E-2 (hereinafter also referred to as "E-2"), which is a random transesterified oil.

[0252] The E-2 was placed in a jacketed glass crystallization tank and, starting from a completely dissolved state, rapidly cooled to an oil temperature of 45°C at 8.3°C / h while stirring at 40 rpm. After a maturation process at 45°C for 3 hours, a crystallized slurry was obtained at 39.5°C. It should be noted that the temperature transition from 45°C to 39.5°C was achieved through slow cooling at 1°C / h. This crystallized slurry was then subjected to filtration, fractionation, and pressing, yielding a fractionated soft oil as random transesterification oil IE-5. It should be noted that IE-5 represents the low-melting-point fraction of transesterification oil E-2.

[0253] IE-5 is a random transesterified oil and is equivalent to "palm oil". Furthermore, as shown in Table 2, since conditions (b-1) and (b-2) are satisfied, IE-5 is equivalent to "oil B" in this invention. It should be noted that the various compositional values ​​of IE-5 are shown in Table 2.

[0254] [Table 1]

[0255] (Table 1)

[0256]

[0257] [Table 2]

[0258] (Table 2)

[0259]

[0260] Using the IE-1 to IE-5 and palm kernel oil (iodine value 23) as a lauric acid oil, a non-tempered hard butter composition was prepared according to the formulations shown in Table 3. The various composition values ​​of the palm kernel oil are shown in Table 1.

[0261] It should be noted that the non-tempered hard butter compositions of Examples 1 to 7 and Comparative Examples 1 to 7 are sometimes referred to as HB-1 to 14 as shown in Table 3.

[0262] [Table 3]

[0263]

[0264] <Methods for manufacturing non-tempered hard butter compositions of Examples 1-7 and Comparative Examples 1-7>

[0265] First, IE-1 to IE-5 and palm kernel oil were heated to 65°C while stirring to dissolve the fats. Next, the dissolved fats were mixed and stirred according to the formulations shown in Table 3 to obtain HB-1 to 14 as non-tempered hard butter compositions. Details of the obtained HB-1 to 14 are shown in Table 4.

[0266] [Table 4]

[0267]

[0268] <Experiment 1>

[0269] Using HB-1 to 14 obtained as described above, the transformation of oil crystals during storage was first evaluated.

[0270] First, 80 parts by weight of HB-1~14 and 20 parts by weight of cocoa butter were mixed while heated and melted. Each mixture was filled into a plastic cup in 10-gram portions, rapidly cooled and solidified at 5°C for 30 minutes, and then stabilized at 20°C for 24 hours to prepare a sample for supplying to an oil X-ray diffraction apparatus.

[0271] The prepared samples were stored in a programmable constant temperature bath with a set temperature of 15℃ for 12 hours and 25℃ for 12 hours to confirm the crystallization of the oil at 1 week and 1 month.

[0272] It should be noted that, in the following text, including Table 5, the peak intensity ratio shown by the following formula for the peak intensity detected at 19.5 degrees (peak intensity A) and the peak intensity detected at 21 degrees (peak intensity B) is 0-10% when it represents "β' type crystallization (referred to as "β'" in Table 5), 11-50% when it represents "β'+β type crystallization (referred to as "β'+β" in Table 5)", and 51-100% when it represents "β type crystallization (referred to as "β" in Table 5)".

[0273] Peak intensity ratio = Peak intensity A / (Peak intensity A + Peak intensity B) × 100 (%)

[0274] [Table 5]

[0275]

[0276] According to the experiment, in samples that meet conditions (1) to (3), crystallization transformation over time is not likely to occur, and a tendency to maintain β'-type crystals over time was observed. In addition, in samples that do not meet conditions (1) to (3), a transformation of the crystal type to β'+β-type crystals was observed one week after the start of storage, and a tendency to transform to β-type crystals over time was observed.

[0277] <Experiment 2>

[0278] Next, oily pastries were prepared, and the occurrence of blooming and mouth-melting properties of the oily pastries over time were evaluated.

[0279] In the non-tempered hard butter composition evaluated in Experiment 1, oily desserts (non-tempered chocolates) were prepared in the following order using HB-2, HB-4, HB-7, HB-11 as examples and HB-1, HB-5, HB-6, HB-10 as comparative examples.

[0280] In detail, 4 parts by weight of cocoa mass and 3.6 parts by weight of cocoa butter were heated to approximately 55°C to dissolve. 13 parts by weight of cocoa powder and 50 parts by weight of sugar were added and mixed. Within the hardness range suitable for a roller mill, a portion of a non-tempered hard butter composition was dissolved and added, and the mixture was further mixed. After roller milling, 0.4 parts by weight of lecithin and the remaining non-tempered hard butter composition were added and kneaded to obtain chocolate dough. This chocolate dough was poured into a mold and cooled and solidified at 5°C for 30 minutes to obtain an oily pastry. The oily pastry was evaluated using the following two evaluation criteria. The evaluation results are shown in Table 6.

[0281] <Evaluation of the frost phenomenon in oily desserts>

[0282] For the manufactured oil-based confectionery, the bloom phenomenon test is carried out in the following order to evaluate the bloom phenomenon. Specifically, in a programmable thermostat set to a temperature cycle condition of repeating 12 hours at 15°C and then 12 hours at 25°C, the sample (oil-based confectionery) is stored statically for 120 days from the date of its manufacture. Then, on the 30th day, 60th day, 90th day, and 120th day from the date of manufacture, the surface of the sample is observed visually, and the bloom phenomenon is evaluated according to the following evaluation criteria. It should be noted that products (scored as ± or +) without the bloom phenomenon at the 120th day are qualified products.

[0283] Bloom phenomenon evaluation criteria:

[0284] +: There is no bloom phenomenon on the surface of the sample, and it is shiny.

[0285] ±: There is no bloom phenomenon on the surface of the sample, and it has no luster.

[0286] -: A bloom phenomenon appears on a part of the surface of the sample.

[0287] --: An obvious bloom phenomenon appears on the surface of the sample.

[0288] <Evaluation of the mouth solubility of oil-based confectionery>

[0289] For the manufactured oil-based confectionery, a sensory evaluation is carried out by a professional panel of 10 people according to the following evaluation criteria. Then, the total score of the 10-person professional panel is calculated. When the total score is 45 - 50, it is +++, when it is 38 - 44, it is ++, when it is 30 - 37, it is +, when it is 14 - 29, it is -, and when it is 0 - 13, it is --. The results are shown in Table 3. It should be noted that before the evaluation, the sensory degree corresponding to each score is coordinated in the professional panel. It should be noted that products with a score of “+” or above are qualified products.

[0290] Mouth solubility evaluation criteria:

[0291] 5 points: Excellent

[0292] 3 points: Good

[0293] 1 point: Somewhat poor

[0294] 0 point: Poor

[0295] [Table 6]

[0296]

[0297] When comparing the oil-based confectionery using HB-1 and the oil-based confectionery using HB-2, the non-tempered hard butter composition used in the manufacture of the oil-based confectionery satisfies the above conditions (1) to (3), and the occurrence of the bloom phenomenon of the obtained oil-based confectionery is suppressed.

[0298] Furthermore, when comparing oily pastries made with various non-tempered hard butter compositions using HB-2, HB-4, and HB-5, the oily pastries using HB-5 showed similar suppression of blooming as those using HB-2 and HB-4. However, they also exhibited poor mouth-melting properties. Therefore, from the viewpoint of obtaining oily pastries with particularly good mouth-melting properties, the SFC at 25°C and the content of trisaturated triglycerides in the triglycerides are important.

[0299] Furthermore, in each of the non-tempered hard butter compositions of HB-6 and HB-7, the results of Experiment 1 showed that when the butter formed β'+β type crystals one month after manufacturing, a comparison of the oily pastries using these compositions revealed that a blooming phenomenon occurred over time in the oily pastries using HB-6. Regarding the SFC and trisaturated triglyceride content at 25°C, all non-tempered hard butter compositions met conditions (1) and (2), and it was found that condition (3) was required to meet the requirement of the content of mixed acid trisaturated triglycerides (LaSS) containing lauric acid residues in the trisaturated triglycerides.

[0300] Furthermore, when comparing oily pastries using HB-4 and oily pastries using HB-11, no blooming was observed in either case. However, in oily pastries using HB-11, the reduction in gloss occurred earlier. The reduction in gloss is known as a precursor to the over-term blooming phenomenon in oily pastries. All conditions (1) to (3) were met, with the differences being the content of trilauroyl glycerol and the content of lauroyl-palmitoyl-stearoyl-triglyceride. Based on the comparison between oily pastries using HB-4 and oily pastries using HB-11, it is presumed that keeping these contents within a specific range can preferably suppress the occurrence of blooming.

Claims

1. A non-tempered hard butter composition comprising fat A and fat B, and satisfying the following conditions (1) to (3), Condition (1): SFC at 25℃ is 27~67%, Condition (2): The content of trisaturated triglycerides in the triglycerides is 20-65% by mass. Condition (3): The content of the mixed acid type tri-saturated glyceride LaSS containing lauric acid residue La in the tri-saturated glyceride is 51 to 65 mass%, and S represents a saturated fatty acid residue with 16 or more carbon atoms. Oil A: A random transesterified oil that meets the following conditions (a-1) and (a-2). Condition (a-1): The mass ratio of the content of lauric acid residue La to the sum of the contents of stearic acid residue St and palmitic acid residue P in fatty acid residues [La / (St+P)] is 0.40~1.

40. Condition (a-2): The content of trisaturated triglycerides with a total carbon number of 46 or less among the saturated fatty acid residues is 35-65% by mass. Oil B: Randomly transesterified oils that meet the following conditions (b-1) and (b-2), Condition (b-1): The saturated fatty acid residues in the fatty acid residues are essentially composed of St and P. Condition (b-2): The content of disaturated monounsaturated triglycerides in the triglycerides is 40-60% by mass, and the proportion of 1,2-disaturated-3-monounsaturated triglycerides in the disaturated monounsaturated triglycerides is 55-75% by mass.

2. The non-tempered hard butter composition according to claim 1, wherein, In condition (1), the SFC at 25°C is above 32%.

3. The non-tempered hard butter composition according to claim 1, wherein, In condition (1), the SFC at 25°C is above 35%.

4. The non-tempered hard butter composition according to claim 1, wherein, In condition (1), the SFC at 25°C is above 38%.

5. The non-tempered hard butter composition according to claim 1, wherein, In condition (1), the SFC at 25°C is below 64%.

6. The non-tempered hard butter composition according to claim 1, wherein, In condition (2), the content of trisaturated triglycerides in the triglycerides is 30% by mass or more.

7. The non-tempered hard butter composition according to claim 1, wherein, In condition (2), the content of trisaturated triglycerides in the triglycerides is 35% by mass or more.

8. The non-tempered hard butter composition according to claim 1, wherein, In condition (2), the content of trisaturated triglycerides in the triglycerides is less than 62% by mass.

9. The non-tempered hard butter composition according to claim 1, wherein, In condition (3), the content of LaSS in the trisaturated triglyceride is 52% by mass or more.

10. The non-tempered hard butter composition according to claim 1, wherein, In condition (3), the content of LaSS in the trisaturated triglyceride is less than 62% by mass.

11. The non-tempered hard butter composition according to claim 1, wherein, The content of lauroyl-palmitoyl-stearoyl-triglyceride (LaPSt) in trisaturated triglycerides is 12-25% by mass.

12. The non-tempered hard butter composition according to claim 11, wherein, The content of LaPSt in trisaturated triglycerides is more than 15% by mass.

13. The non-tempered hard butter composition according to claim 1, further satisfying the following condition (4), Condition (4): The amount of trilauroyl glycerol in the trisaturated triglyceride is less than 10% by mass.

14. The non-tempered hard butter composition according to claim 13, wherein, In condition (4), the content of trilauroyl glycerol in the trisaturated triglyceride is less than 8% by mass.

15. The non-tempered hard butter composition according to claim 1, wherein, In condition (a-1), the mass ratio [La / (St+P)] is less than 1.

20.

16. The non-tempered hard butter composition according to claim 1, wherein, In condition (a-1), the mass ratio [La / (St+P)] is less than 0.

75.

17. The non-tempered hard butter composition according to claim 1, wherein, In condition (a-2), the content of trisaturated triglycerides with a total carbon number of 46 or less among the saturated fatty acid residues is 40% by mass or more.

18. The non-tempered hard butter composition according to claim 1, wherein, In condition (a-2), the content of trisaturated triglycerides with a total carbon number of 46 or less among the saturated fatty acid residues is 61% by mass or less.

19. The non-tempered hard butter composition according to claim 1, wherein, In condition (a-2), the content of trisaturated triglycerides with a total carbon number of 46 or less among the saturated fatty acid residues is 55% by mass or less.

20. The non-tempered hard butter composition according to claim 1, wherein, In oil B, the mass ratio of St to P in fatty acid residues (St / P) is 0.05~7.

0.

21. The non-tempered hard butter composition according to claim 1, wherein, In oil B, the mass ratio of St to P (St / P) of fatty acid residues is 0.1~3.

0.

22. The non-tempered hard butter composition according to claim 1, wherein, In condition (b-2), the content of disaturated monounsaturated triglycerides in the triglycerides is 45% by mass or more.

23. The non-tempered hard butter composition according to claim 1, wherein, In condition (b-2), the content of disaturated monounsaturated triglycerides in the triglycerides is less than 55% by mass.

24. The non-tempered hard butter composition according to claim 1, wherein, In condition (b-2), the proportion of 1,2-disaturated-3-monounsaturated triglycerides in the disaturated monounsaturated triglycerides is more than 60% by mass.

25. The non-tempered hard butter composition according to claim 1, wherein, In condition (b-2), the proportion of 1,2-disaturated-3-monounsaturated triglycerides in the disaturated monounsaturated triglycerides is less than 70% by mass.

26. The non-tempered hard butter composition according to claim 1, wherein, In oil B, the content of palmitoyl-stearyl-oleoyl-triglyceride PStO in disaturated monounsaturated triglycerides is 40~65% by mass.

27. The non-tempered hard butter composition according to claim 1, wherein, In oil B, the content of palmitoyl-stearyl-oleoyl-triglyceride PStO in disaturated monounsaturated triglycerides is 45-57% by mass.

28. An oily pastry, comprising: The non-tempered hard butter composition according to any one of claims 1 to 27.

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