【発明の詳細な説明】
本発明は、原料油脂として本邦で容易に入手出
来る魚油を利用するハードバターの製造方法に関
するものである。
更に詳しくは、本発明は全構成脂肪酸組成中の
飽和脂肪酸（以下、飽和酸と略す）含量が10〜30
％かつ不飽和２重結合を３個以上有する高度不飽
和脂肪酸（以下、高度不飽和酸と略す）含量が10
〜30％の範囲にある単独もしくは任意の割合で配
合した２種以上の魚油を飽和酸の生成を抑制し、
トランス異性化脂肪酸（以下、異性化酸と略す）
の生成を適当に増加させるいわゆる選択的水素添
加条件下で水素添加することにより得られた水素
添加油脂（以下硬化油と略す）を分別することな
く固体脂指数（以下S.F.L.と略す）が
10℃ 50以上
20℃ 45以上
30℃ 20〜40
40℃ ０〜2.5
である、適当な固さを有し、口融け、口当りが良
好でしかもカカオバターとの配合性の良いハード
バターを製造する方法を提供するものである。
従来よりハードバターの製造方法としては、パ
ーム油、シア脂、モーラー脂等のそれ自体ハード
バター成分を比較的多量に含む特殊な油脂を分別
し、ハードバター成分を分取する方法や他の一般
的な油脂を異性化を起こさせる条件下で水素添加
し、得られた異性化酸含量の高い硬化油をカカオ
代用脂とする方法、更には、水素添加後分別によ
りハードバター成分を分取する方法等が提案され
て来た。しかしハードバターの原料油脂を特殊な
油脂にのみ依存することは、ハードバターの需要
が高まるにつれて供給、価格面で問題があり、よ
り一般的な油脂の利用が検討される様になつた。
そしてその様な一般的な油脂を利用する方法とし
ての水素添加、特に異性化を起こさせる条件下で
水素添加する方法では、高度不飽和酸を多量に含
む魚油などをハードバターとして必要な固さまで
硬化を行うと必然的に３飽和トリグリセリド等の
高融点部が副生するのを避けることが出来ずチヨ
コレートに使用する場合、口融け不良、ブルーミ
ング発生等の悪影響を及ぼしていた。
また水素添加後溶剤分別により高融点部を除去
しハードバター成分を分取する方法では単に工程
数が増え収率が低下するということだけではな
く、装置的にも簡単には行えず溶剤の使用による
安全面での問題もあり、しかもこの様にして得ら
れたハードバターはチヨコレートに使用する場合
カカオバターとの配合性が悪く、著るしい融点降
下、硬さ不足及び耐熱性の不良をもたらす場合が
あつた。
従つて単に水素添加のみでハードバターを製造
することが出来れば、製造工程の簡略化及び収率
の向上はもちろん工業的、経済的意義は極めて大
きいものとなる。
本発明の目的は、従来公知の方法によつて得ら
れるハードバターの欠点を改良するため、得られ
た硬化油を分別することなく、単に水素添加のみ
で適当な固さを有し、口融け、口当りの良好な、
しかもカカオバターとの配合性の良いハードバタ
ーの製造方法を提供するものである。
すなわち本発明の方法は、原料油脂として本邦
で容易に入手出来る魚油を利用して、例えばニツ
ケル、パラジウム等の公知の水素添加触媒を使用
して飽和酸の生成を抑制し、異性化酸の生成を適
当に増加させるいわゆる選択的水素添加条件下で
水素添加することにより、得られた硬化油を分別
することなく、適当な固さを有し、口融け、口当
りが良好でしかもカカオバターとの配合性の良い
ハードバターに適した硬化油を得るものである。
本発明に適用し得る原料油脂としては、全構成
脂肪酸組成中の飽和酸含量が10〜30％かつ高度不
飽和酸含量が10〜30％の範囲にある単独もしく
は、任意の割合で配合した２種以上の魚油を用い
ることが出来る。飽和酸含量が30％を越える魚油
は、選択的水素添加条件による水素添加を行つて
も、原料自体にすでに高融点の飽和グリセリドの
割合がかなり多く、水素添加後にその割合が一層
増加するため、製品の口融けを悪くする傾向があ
る。また、高度不飽和酸含量が30％を越える魚油
は、選択的水素添加条件による水素添加を行つて
も相対的に異性化酸の生成が多くなり、更にハー
ドバターとして必要な固さまで硬化を行うと、選
択性が悪くなり多量の飽和酸を生成するため、融
点が高くなり口融けを悪くする傾向がある。
本発明の水素添加方法は、例えばニツケル、パ
ラジウム等の公知の水素添加触媒を使用し、例え
ば温度180〜220℃で選択性を上げ、反応熱を少く
し熱収支、異性化能を改良するため、水素流量
1.0〜1.5／分／Kg（常圧換算）で水素を常圧下
又は加圧下で原料油脂と接触せしめて行うことが
出来る。水素添加は得られる生成物がヨウ素価55
〜75、融点34〜37℃、異性化酸含量40〜60％とな
るように行うのが特に好ましい。
本発明の方法によつて得られた硬化油は、チヨ
コレートに使用した場合、すぐれたカカオバター
との配合性を示し、口当り、口融けが良好で、す
ぐれた型ぬけ性と耐ブルーム性を示し、ハードバ
ターとしてすぐれたものである。
以下実施例、比較例により本発明の効果を説明
するが、本発明はこれらの実施例に限定されるも
のではない。尚、本発明の効果を明瞭にするため
実施例１〜４で得られた硬化油のS.F.I.曲線を第
１図に、比較例１〜３で得られた硬化油のS.F.I.
曲線を第２図に示す。
実施例 １
魚油（ヨウ素価142.0、飽和酸含量18.2％、高
度不飽和酸含量21.9％）900ｇ、市販５％パラジ
ウム触媒1.8ｇを1.5オートクレーブ中に入れ、
温度180〜190℃、水素圧力２Kg／cm2（ゲージ
圧）、水素流量1.3／min（常圧換算）、撹拌速
度800r.p.m.で水素添加を行つた。得られた硬化
油のヨウ素価、融点、異性化酸含量及びS.F.I.は
以下の通りであつた。
ヨウ素価 69.9
融 点 35.7℃
異性化酸含量 57.4％
S.F.I.
10℃ 20℃ 25℃ 30℃ 35℃ 40℃
53.3 47.5 39.6 27.7 12.1 1.5
実施例 ２
魚油（ヨウ素価142.0、飽和酸含量18.2％、高
度不飽和酸含量21.9％）900ｇ、市販ニツケル触
媒（ニツケル含量23％）7.2ｇ〜220℃、水素圧力
２Kg／cm2（ゲージ圧）、水素流量1.0／min（常
圧換算）、撹拌速度800r.p.m.で水素添加を行つ
た。得られた硬化油のヨウ素価、融点、異性化酸
含量及びS.F.I.は以下の通りであつた。
ヨウ素価 66.1
融 点 35.9℃
異性化酸含量 50.3％
S.F.I.
10℃ 20℃ 25℃ 30℃ 35℃ 40℃
50.7 45.1 36.9 25.9 10.6 0.4
実施例 ３
原料油脂を魚油（ヨウ素価150.5、飽和酸含量
22.5％、高度不飽和酸含量25.9％）に変えた以外
は、実施例２と同様にして水素添加を行つた。得
られた硬化油のヨウ素価、融点、異性化酸含量及
びS.F.I.は以下の通りであつた。
ヨウ素価 66.3
融 点 36.2℃
異性化酸含量 52.7％
S.F.I.
10℃ 20℃ 25℃ 30℃ 35℃ 40℃
54.4 49.5 42.5 33.7 16.3 2.0
実施例 ４
原料油脂を魚油（ヨウ素価133.0、飽和酸含量
26.0％、高度不飽和酸含量20.9％）に変えた以外
は実施例２と同様にして水素添加を行つた。得ら
れた硬化油のヨウ素価、融点、異性化酸含量及び
S.F.I.は以下の通りであつた。
ヨウ素価 57.5
融 点 35.8℃
異性化酸含量 44.1％
S.F.I.
10℃ 20℃ 25℃ 30℃ 35℃ 40℃
62.5 53.4 44.8 33.5 15.9 ０
比較例 １
魚油（ヨウ素価165.5、飽和酸含量30.7％、高
度不飽和酸含量31.1％）900ｇ、市販ニツケル触
媒7.2ｇを1.5オートクレーブ中に入れ温度210
〜220℃、水素圧力２Kg／cm2（ゲージ圧）、水素流
量1.0／min（常圧換算）、撹拌速度800r.p.m.で
水素添加を行つた。得られた硬化油のヨウ素価、
融点、異性化酸含量及びS.F.I.は以下の通りであ
つた。
ヨウ素価 68.8
融 点 36.2℃
異性化酸含量 47.4％
S.F.I.
10℃ 20℃ 25℃ 30℃ 35℃ 40℃
49.6 36.5 30.6 23.7 16.5 5.7
比較例 ２
魚油（ヨウ素価142.0、飽和酸含量18.2％、高
度不飽和酸含量21.9％）900ｇ、市販ニツケル触
媒3.15ｇを1.5オートクレーブ中に入れ、温度
210〜220℃、水素圧力２Kg／cm2（ゲージ圧）、水
素流量1.8／min（常圧換算）、撹拌速度800r.p.
m.で水素添加を行つた。得られた硬化油のヨウ
素価、融点、異性化酸含量及びS.F.I.は以下の通
りであつた。
ヨウ素価 64.2
融 点 35.4℃
異性化酸含量 45.6％
S.F.I.
10℃ 20℃ 25℃ 30℃ 35℃ 40℃
53.9 37.4 30.1 22.4 15.3 4.3
比較例 ３
魚油（ヨウ素価142.0、飽和酸含量18.2％、高
度不飽和酸含量21.9％）900ｇ、市販ニツケル触
媒4.5ｇ、DL−メチオニン0.135ｇを1.5オート
クレーブ中に入れ、温度210〜220℃、水素圧力２
Kg／cm2（ゲージ圧）、水素流量0.65／min（常
圧換算）、撹拌速度800r.p.m.で水素添加を行つ
た。得られた硬化油のヨウ素価、融点、異性化酸
含量及びS.F.I.は以下の通りであつた。
ヨウ素価 72.5
融 点 35.1℃
異性化酸含量 56.2％
S.F.I.
10℃ 20℃ 25℃ 30℃ 35℃ 40℃
48.6 35.4 27.4 20.7 12.3 3.1
実施例１と比較例１で得た硬化油の冷却曲線を
第３図に示す。
チヨコレートテスト
実施例１〜４と比較例１で得た硬化油を精製
し、下記の配合でチヨコレートを試作し、食感、
型ぬけ性、耐ブルーム性のテストを行つた。結果
を表１に示す。
砂 糖 40％
油 脂 25％
カカオマス 20％
全脂粉乳 15％
レシチン 0.3％
食感；10名のパネラーにより試食し口当り、口融
けを判定した。
型ぬけ性；チヨコレートを35℃でモールドし５℃
で冷却して15分、20分後の型ぬけ性を見た。
耐ブルーム性；20℃、30℃にそれぞれ12時間保
ち、24時間を１サイクルとしてブルームの発
生を調べた。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing hard butter that uses fish oil, which is easily available in Japan, as a raw material fat. More specifically, the present invention has a saturated fatty acid (hereinafter abbreviated as saturated acid) content in the total fatty acid composition of 10 to 30
% and the content of highly unsaturated fatty acids (hereinafter abbreviated as highly unsaturated acids) having 3 or more unsaturated double bonds is 10
~30% of fish oil alone or in any ratio of two or more fish oils to suppress the production of saturated acids,
Trans isomerized fatty acids (hereinafter abbreviated as isomerized acids)
Hydrogenated fats and oils (hereinafter referred to as hydrogenated oil) obtained by hydrogenation under so-called selective hydrogenation conditions that appropriately increase the production of hydrogen have a solid fat index (hereinafter referred to as SFL) of 10℃ without fractionation. 50 or above 20°C 45 or above 30°C 20-40 40°C 0-2.5 This is what we provide. Traditional methods for producing hard butter include separating special oils and fats that themselves contain relatively large amounts of hard butter components, such as palm oil, shea butter, and Molar butter, and separating the hard butter components, as well as other general methods. A method of hydrogenating standard oils and fats under conditions that cause isomerization and using the resulting hardened oil with a high isomerized acid content as a cacao substitute fat.Furthermore, a method of separating hard butter components by fractionation after hydrogenation. Methods have been proposed. However, relying solely on special oils and fats as the raw material for hard butter poses problems in terms of supply and price as the demand for hard butter increases, and the use of more general oils and fats is being considered.
Hydrogenation, which is a common method of using such oils and fats, especially hydrogenation under conditions that cause isomerization, is a method that allows fish oils containing a large amount of highly unsaturated acids to reach the consistency required for hard butter. When hardening is carried out, it is impossible to avoid the production of high melting point parts such as trisaturated triglycerides, which causes negative effects such as poor melting in the mouth and occurrence of blooming when used in thiokolate. In addition, the method of removing high melting point parts and separating hard butter components by solvent fractionation after hydrogenation not only increases the number of steps and lowers the yield, but also cannot be carried out easily in terms of equipment and requires the use of solvents. Moreover, when the hard butter obtained in this way is used in thiokolate, it has poor compatibility with cocoa butter, resulting in a significant drop in melting point, lack of hardness, and poor heat resistance. The situation was ripe. Therefore, if hard butter could be produced simply by hydrogenation, it would not only simplify the production process and improve the yield, but would also have extremely great industrial and economic significance. The purpose of the present invention is to improve the drawbacks of hard butter obtained by conventionally known methods, and to achieve suitable hardness and melt-in-the-mouth consistency by simply hydrogenating the obtained hardened oil without fractionating it. , good texture,
Furthermore, the present invention provides a method for producing hard butter that is compatible with cocoa butter. That is, the method of the present invention utilizes fish oil, which is easily available in Japan, as a raw material oil and fat, suppresses the production of saturated acids using a known hydrogenation catalyst such as nickel or palladium, and suppresses the production of isomerized acids. By hydrogenating the hydrogenated oil under so-called selective hydrogenation conditions that appropriately increase A hydrogenated oil suitable for hard butter with good blendability is obtained. The raw material fats and oils that can be used in the present invention include two oils or fats that have a saturated acid content of 10 to 30% and a highly unsaturated acid content of 10 to 30% in the total fatty acid composition, or two that are blended in any proportion. Fish oil of seeds or more can be used. Fish oil with a saturated acid content of more than 30%, even if hydrogenated under selective hydrogenation conditions, already has a large proportion of saturated glycerides with a high melting point in the raw material itself, and this proportion increases even more after hydrogenation. It tends to make the product less melt in the mouth. In addition, fish oil with a highly unsaturated acid content of more than 30% will generate a relatively large amount of isomerized acid even if hydrogenated under selective hydrogenation conditions, and will harden to the consistency required for hard butter. In this case, the selectivity deteriorates and a large amount of saturated acid is produced, which tends to increase the melting point and worsen the melting in the mouth. The hydrogenation method of the present invention uses a known hydrogenation catalyst such as nickel or palladium, and increases selectivity at a temperature of 180 to 220°C, reduces reaction heat, and improves heat balance and isomerization ability. , hydrogen flow rate
This can be carried out by bringing hydrogen into contact with the raw material oil under normal pressure or pressurization at a rate of 1.0 to 1.5/min/Kg (converted to normal pressure). Hydrogenation produces a product with an iodine value of 55
It is particularly preferable to carry out the reaction so that the melting point is 34 to 37°C and the isomerized acid content is 40 to 60%. When the hydrogenated oil obtained by the method of the present invention is used in thiokolate, it exhibits excellent compatibility with cocoa butter, has good mouth feel and melts in the mouth, and exhibits excellent mold release properties and bloom resistance. , is an excellent hard butter. The effects of the present invention will be explained below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In order to clarify the effects of the present invention, the SFI curves of the hydrogenated oils obtained in Examples 1 to 4 are shown in Figure 1, and the SFI curves of the hydrogenated oils obtained in Comparative Examples 1 to 3 are shown in Figure 1.
The curve is shown in Figure 2. Example 1 900 g of fish oil (iodine value 142.0, saturated acid content 18.2%, highly unsaturated acid content 21.9%) and 1.8 g of commercially available 5% palladium catalyst were placed in a 1.5 autoclave.
Hydrogenation was carried out at a temperature of 180 to 190°C, a hydrogen pressure of 2 Kg/cm 2 (gauge pressure), a hydrogen flow rate of 1.3/min (converted to normal pressure), and a stirring speed of 800 rpm. The iodine value, melting point, isomerized acid content, and SFI of the obtained hardened oil were as follows. Iodine value 69.9 Melting point 35.7℃ Isomerized acid content 57.4% SFI 10℃ 20℃ 25℃ 30℃ 35℃ 40℃ 53.3 47.5 39.6 27.7 12.1 1.5 Example 2 Fish oil (iodine value 142.0, saturated acid content 18.2%, highly unsaturated Acid content 21.9%) 900g, commercially available nickel catalyst (nickel content 23%) 7.2g to 220℃, hydrogen pressure 2Kg/cm 2 (gauge pressure), hydrogen flow rate 1.0/min (converted to normal pressure), stirring speed 800r.pm. Hydrogenation was performed. The iodine value, melting point, isomerized acid content, and SFI of the obtained hardened oil were as follows. Iodine value 66.1 Melting point 35.9°C Isomerized acid content 50.3% SFI 10°C 20°C 25°C 30°C 35°C 40°C 50.7 45.1 36.9 25.9 10.6 0.4 Example 3 Raw material oil was converted to fish oil (iodine value 150.5, saturated acid content
Hydrogenation was carried out in the same manner as in Example 2, except that the content of highly unsaturated acids was changed to 22.5% and 25.9%. The iodine value, melting point, isomerized acid content, and SFI of the obtained hardened oil were as follows. Iodine value 66.3 Melting point 36.2°C Isomerized acid content 52.7% SFI 10°C 20°C 25°C 30°C 35°C 40°C 54.4 49.5 42.5 33.7 16.3 2.0 Example 4 The raw oil was converted to fish oil (iodine value 133.0, saturated acid content
Hydrogenation was carried out in the same manner as in Example 2 except that the content of highly unsaturated acid was changed to 26.0% and 20.9%. Iodine value, melting point, isomerized acid content and
The SFI was as follows. Iodine value 57.5 Melting point 35.8℃ Isomerized acid content 44.1% SFI 10℃ 20℃ 25℃ 30℃ 35℃ 40℃ 62.5 53.4 44.8 33.5 15.9 0 Comparative example 1 Fish oil (iodine value 165.5, saturated acid content 30.7%, highly unsaturated 900 g of acid content (31.1%) and 7.2 g of commercially available nickel catalyst were placed in a 1.5 autoclave at a temperature of 210.
Hydrogenation was carried out at ~220°C, hydrogen pressure of 2 Kg/cm 2 (gauge pressure), hydrogen flow rate of 1.0/min (converted to normal pressure), and stirring speed of 800 rpm. The iodine value of the obtained hydrogenated oil,
The melting point, isomerized acid content, and SFI were as follows. Iodine value 68.8 Melting point 36.2℃ Isomerized acid content 47.4% SFI 10℃ 20℃ 25℃ 30℃ 35℃ 40℃ 49.6 36.5 30.6 23.7 16.5 5.7 Comparative example 2 Fish oil (iodine value 142.0, saturated acid content 18.2%, highly unsaturated 900 g (acid content 21.9%) and 3.15 g of commercially available nickel catalyst were placed in a 1.5 autoclave, and the temperature
210-220℃, hydrogen pressure 2Kg/cm 2 (gauge pressure), hydrogen flow rate 1.8/min (converted to normal pressure), stirring speed 800r.p.
Hydrogenation was carried out at m. The iodine value, melting point, isomerized acid content, and SFI of the obtained hardened oil were as follows. Iodine value 64.2 Melting point 35.4℃ Isomerized acid content 45.6% SFI 10℃ 20℃ 25℃ 30℃ 35℃ 40℃ 53.9 37.4 30.1 22.4 15.3 4.3 Comparative example 3 Fish oil (iodine value 142.0, saturated acid content 18.2%, highly unsaturated 900 g of acid content (21.9%), 4.5 g of commercially available nickel catalyst, and 0.135 g of DL-methionine were placed in a 1.5 autoclave at a temperature of 210 to 220°C and a hydrogen pressure of 2.
Hydrogenation was carried out at Kg/cm 2 (gauge pressure), hydrogen flow rate of 0.65/min (converted to normal pressure), and stirring speed of 800 rpm. The iodine value, melting point, isomerized acid content, and SFI of the obtained hardened oil were as follows. Iodine value 72.5 Melting point 35.1℃ Isomerized acid content 56.2% SFI 10℃ 20℃ 25℃ 30℃ 35℃ 40℃ 48.6 35.4 27.4 20.7 12.3 3.1 The cooling curves of the hardened oils obtained in Example 1 and Comparative Example 1 are shown in the third example. As shown in the figure. Thiyocolate test The hydrogenated oils obtained in Examples 1 to 4 and Comparative Example 1 were purified, and a prototype of Thiyocolate was made with the following formulation.
Tests were conducted for mold removal and bloom resistance. The results are shown in Table 1. Sugar: 40% Oil: 25% Cacao mass: 20% Whole milk powder: 15% Lecithin: 0.3% Texture: Ten panelists tasted the product and judged its mouthfeel and melt-in-the-mouth texture. Mold removability: Mold Chiyokolate at 35℃ and mold at 5℃
The mold release properties were checked after 15 and 20 minutes of cooling. Bloom resistance: The samples were kept at 20°C and 30°C for 12 hours each, and one cycle of 24 hours was used to examine the occurrence of bloom. 【table】
【図面の簡単な説明】[Brief explanation of the drawing]
第１図は実施例１〜４で得られた硬化油のS.F.
I.曲線、第２図は比較例１〜３で得られた硬化油
のS.F.I.曲線であり、第３図は実施例１と比較例
１で得た硬化油の冷却曲線である。
Figure 1 shows the SF of hydrogenated oil obtained in Examples 1 to 4.
I. Curve, FIG. 2 is the SFI curve of the hardened oils obtained in Comparative Examples 1 to 3, and FIG. 3 is the cooling curve of the hardened oils obtained in Example 1 and Comparative Example 1.