JP2001059098A - Enzyme particle aggregate - Google Patents

Enzyme particle aggregate

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Publication number
JP2001059098A
JP2001059098A JP11310664A JP31066499A JP2001059098A JP 2001059098 A JP2001059098 A JP 2001059098A JP 11310664 A JP11310664 A JP 11310664A JP 31066499 A JP31066499 A JP 31066499A JP 2001059098 A JP2001059098 A JP 2001059098A
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JP
Japan
Prior art keywords
enzyme
particles
water
component
enzyme particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP11310664A
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Japanese (ja)
Other versions
JP3514677B2 (en
Inventor
Yoshinobu Imaizumi
義信 今泉
Koichi Ohori
浩一 大堀
Itsuro Tsukahara
逸朗 塚原
Hiroyuki Yamashita
博之 山下
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kao Corp
Original Assignee
Kao Corp
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Priority to JP31066499A priority Critical patent/JP3514677B2/en
Publication of JP2001059098A publication Critical patent/JP2001059098A/en
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Publication of JP3514677B2 publication Critical patent/JP3514677B2/en
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Expired - Fee Related legal-status Critical Current

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Abstract

PROBLEM TO BE SOLVED: To provide enzyme particle aggregate from which the enzymes are readily eluted out without the enzyme residue insoluble with occurrence of dusting suppressed, resisting the occurrence of classification in the detergent composition, when it is formulated to the detergent together with other components, by coagulating enzyme particles having such a structure that the water-soluble binder distributes more in the vicinity of the surface than in the core part, and provide a method for suitably producing an aggregate of enzyme particles. SOLUTION: The objective aggregate comprises (A) water-insoluble and/or slightly soluble substance, (B) a water-soluble binder and (C) enzymes and has such a structure that the component (B) distributes more in the vicinity of the surface than in the core part. The objective enzyme particle aggregate is produced by adding water or a binder aqueous solution to the enzyme particles having the above-stated structure, drying and/or cooling the mixture or by adding a molten thermoplastic binder thereto, cooling the mixture.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は洗浄剤に好適に配合
される酵素粒子凝集体とその製法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an enzyme particle aggregate suitably blended in a detergent and a method for producing the same.

【０００２】[0002]

【従来の技術】衣料用の粉末洗剤、粉末漂白剤及び自動
食器洗浄機用粉末洗浄剤等の洗浄剤には、その洗浄力を
高めるために各種の酵素が配合されることが多い。酵素
は水中に溶解して初めてその効果が発揮されるため、酵
素にはその効果の発揮までにある程度の時間を要すると
いう性質がある。そのため、酵素の性能を最大限に生か
すためには、酵素粒子から酵素を速やかに溶出させる性
質（以下、高速溶解性という）を酵素粒子が有している
かどうかが重要である。特に衣料用洗剤等に関して、洗
濯時間が短縮傾向にある現状では、その重要性はますま
す高くなっている。2. Description of the Related Art Various enzymes are often blended in detergents such as powder detergents for clothes, powder bleaching agents and powder detergents for automatic dishwashers in order to enhance the detergency. Since the effect is exhibited only when the enzyme is dissolved in water, the enzyme has a property that it takes a certain amount of time to exhibit the effect. Therefore, in order to maximize the performance of the enzyme, it is important that the enzyme particle has a property of rapidly eluting the enzyme from the enzyme particle (hereinafter, referred to as high-speed solubility). In particular, in the current situation where the washing time tends to be shortened with respect to clothing detergents and the like, the importance thereof is increasing more and more.

【０００３】更に、洗浄剤への配合を考えた場合、洗浄
終了時に酵素粒子の溶け残りがあると、溶け残り成分の
洗浄対象物への付着等の問題が生じる。従って、酵素粒
子を構成している物質がすべて洗浄時間内に分散し、溶
け残りを防ぐことが重要である。また、作業環境の安全
性を確保するためには、酵素粒子からの粉塵の発生量
（以下、発塵量という）を抑制することが重要である。
さらに粉末状の洗剤組成物へのアフターブレンドを考え
た場合、品質の面からは酵素粒子が洗剤組成物中に均一
に分布することが望ましい。そのためには、酵素粒子の
粒径及び嵩密度を洗剤組成物を構成する他の粒子に近づ
けて、他の粒子と酵素粒子とが分級されることを防ぐこ
とが重要である。また、外観の面から考えると視認性の
観点から粒径は大きい方が望ましく、粒子個数の観点か
ら嵩密度は低い方が望ましい。[0003] Further, in the case of mixing in a detergent, if enzyme particles remain undissolved at the end of washing, a problem such as adhesion of undissolved components to an object to be washed occurs. Therefore, it is important to prevent all the substances constituting the enzyme particles from being dispersed within the washing time and from remaining undissolved. Further, in order to ensure the safety of the working environment, it is important to suppress the amount of dust generated from the enzyme particles (hereinafter referred to as the amount of generated dust).
Furthermore, when considering after blending with a powdered detergent composition, it is desirable from the viewpoint of quality that the enzyme particles are uniformly distributed in the detergent composition. For that purpose, it is important to make the particle size and bulk density of the enzyme particles close to other particles constituting the detergent composition to prevent the other particles and the enzyme particles from being classified. Also, from the viewpoint of appearance, it is desirable that the particle size is large from the viewpoint of visibility, and it is desirable that the bulk density is low from the viewpoint of the number of particles.

【０００４】これらの点を考慮すると、洗剤組成物との
配合に関係なく必要とされる物性である高速溶解性及び
低発塵性を満足し、かつ洗浄剤との配合の際に重要とな
ってくる物性である粒径及び嵩密度を洗浄剤に合わせて
コントロールできる技術が重要となってくる。しかし、
これらの物性は互いに密接に関わり合っている。例え
ば、粒径を小さくすることにより溶解性は向上するもの
の、同時に発塵量は増加する傾向がある。嵩密度を高め
ることにより発塵量は低下するものの、同時に溶解性は
低下する傾向がある。このため、従来よりこれらの要求
物性を同時に満たす酵素粒子を得ることは困難であっ
た。[0004] In consideration of these points, it satisfies the required properties of high-speed solubility and low dust generation irrespective of the formulation with the detergent composition, and becomes important when blended with the detergent. A technology that can control the physical properties such as particle size and bulk density according to the detergent is important. But,
These properties are closely related to each other. For example, although the solubility is improved by reducing the particle size, the amount of dust generated tends to increase at the same time. Increasing the bulk density reduces the amount of dust, but at the same time tends to decrease solubility. For this reason, it has conventionally been difficult to obtain enzyme particles that simultaneously satisfy these required physical properties.

【０００５】例えば特公昭５０−２２５０６号公報で
は、洗剤用酵素と無機塩類が水溶性バインダー溶液中に
共存する溶液または分散液を噴霧乾燥することにより、
洗剤用酵素を含むマイクロカプセルを製造する方法が開
示されている。ここで実施されている粒径２０〜１３０
μｍの範囲のマイクロカプセルは、洗剤に配合して用い
る場合は良好な溶解性を満たすことが可能であると考え
られるものの、粒径が洗剤に比べて非常に小さいため、
粒子間に発生する分級現象の抑制が困難である。また、
この技術によって得られる酵素粒子は水溶性物質の含有
量が実質的に多いものとなるため、中空構造で強度が弱
く、発塵量を抑制することは困難であり、酵素について
の上記の要求物性を同時に満たすことはできなかった。[0005] For example, in Japanese Patent Publication No. 50-22506, a solution or dispersion in which a detergent enzyme and inorganic salts coexist in a water-soluble binder solution is spray-dried.
A method for producing microcapsules containing detergent enzymes is disclosed. Particle size 20-130 used here
Although microcapsules in the range of μm are considered to be able to satisfy good solubility when used in a detergent, since the particle size is very small compared to the detergent,
It is difficult to suppress the classification phenomenon that occurs between particles. Also,
Since the enzyme particles obtained by this technique have a substantially high content of water-soluble substances, the hollow structure has a low strength, and it is difficult to suppress the amount of dust generation. Could not be satisfied at the same time.

【０００６】特開平７−２８９２５９号公報では、洗剤
用酵素及びアルミノ珪酸塩粉末を含有する混合物を、水
溶性有機バインダーを用いて攪拌転動造粒に付して洗剤
用酵素造粒物を製造する方法が開示されている。この方
法によれば、発塵量の抑制に関して、造粒を行うことに
より解決している。しかし、粒径の増加と造粒における
粒子の圧密化のため、高速溶解性を満足することは困難
であり、この方法によっても酵素についての上記の要求
物性を同時に満たすことはできなかった。[0006] JP-A-7-289259 discloses that a mixture containing a detergent enzyme and an aluminosilicate powder is subjected to stirring tumbling granulation using a water-soluble organic binder to produce a detergent enzyme granulated product. A method for doing so is disclosed. According to this method, the suppression of the amount of generated dust is solved by performing granulation. However, it is difficult to satisfy the high-speed solubility due to the increase in particle size and the compaction of particles in granulation, and the above-mentioned required properties of the enzyme cannot be simultaneously satisfied by this method.

【０００７】[0007]

【発明が解決しようとする課題】本発明の課題は、内部
よりも表面近傍に水溶性バインダーが多く存在する構造
を有する酵素粒子を凝集させることにより酵素が速やか
に溶出し、溶け残りが無く、粉塵の発生が抑制され、か
つ他の成分と共に洗浄剤に配合された場合において、洗
浄剤組成物中で粒子間に発生する分級現象が起こりにく
い性質（以下、非分級性という）を有する酵素粒子凝集
体を提供することにある。さらに本発明の課題は酵素粒
子凝集体を好適に製造し得る方法を提供することにあ
る。An object of the present invention is to coagulate enzyme particles having a structure in which a water-soluble binder is present more in the vicinity of the surface than in the interior, whereby the enzyme is rapidly eluted, and there is no remaining undissolved. Enzyme particles having the property that the generation of dust is suppressed and that the classification phenomenon that occurs between particles in the cleaning composition does not easily occur (hereinafter, referred to as non-classifying property) when mixed with other components in the cleaning composition It is to provide an aggregate. A further object of the present invention is to provide a method capable of suitably producing an enzyme particle aggregate.

【０００８】[0008]

【課題を解決するための手段】即ち、本発明の要旨は、
〔１〕水不溶性物質及び／又は水難溶性物質（Ａ）、水
溶性バインダー（Ｂ）、及び酵素（Ｃ）を含有し、且つ
内部よりも表面近傍に前記（Ｂ）成分が多く存在する構
造を有する酵素粒子を含有する酵素粒子凝集体、並びに
〔２〕水不溶性物質及び／又は水難溶性物質（Ａ）、水
溶性バインダー（Ｂ）、及び酵素（Ｃ）を含有し、且つ
内部よりも表面近傍に前記（Ｂ）成分が多く存在する構
造を有する酵素粒子に、水若しくはバインダー水溶液を
添加して乾燥及び／又は冷却することにより、又は溶融
した熱可塑性バインダーを添加して冷却することにより
酵素粒子凝集体を得る、酵素粒子凝集体の製法、に関す
る。That is, the gist of the present invention is as follows.
[1] A structure containing a water-insoluble substance and / or a poorly water-soluble substance (A), a water-soluble binder (B), and an enzyme (C), and having a greater amount of the component (B) near the surface than inside. An enzyme particle aggregate containing enzyme particles, and [2] a water-insoluble substance and / or a poorly water-soluble substance (A), a water-soluble binder (B), and an enzyme (C), and closer to the surface than inside. By adding water or an aqueous binder solution to the enzyme particles having a structure in which the component (B) is present in a large amount and drying and / or cooling, or by adding a molten thermoplastic binder and cooling. A method for producing an aggregate of enzyme particles, which obtains an aggregate.

【０００９】[0009]

【発明の実施の形態】１．（Ａ）成分 （Ａ）成分としては水に対して溶解性を示さないか、若
しくは僅かに示す物質であって、実質的に酵素を失活さ
せず、水溶性バインダーと反応せず、かつ水中で分散す
る性質を示す物質である。これらの物質は無機物質又は
有機物質のいずれでもよいが、噴霧乾燥等の加熱を必要
とする工程が含まれる場合には熱に対する安定性が高い
方が有利なことから、無機物質がより好ましい。（Ａ）
成分の具体例としては、セルロースパウダー、ゼオライ
ト、タルク、クレー、アルミナ、カオリン、チタニア、
炭酸カルシウム、硫酸バリウム等が挙げられ、水中での
分散性が良好なゼオライトやカオリン等が好ましい。BEST MODE FOR CARRYING OUT THE INVENTION Component (A) The component (A) is a substance which does not show solubility in water or shows only a little, does not substantially inactivate enzymes, does not react with a water-soluble binder, and has no water solubility. It is a substance that exhibits the property of dispersing in. These substances may be either an inorganic substance or an organic substance. However, when a step requiring heating such as spray drying is included, an inorganic substance is more preferable because a higher heat stability is more advantageous. (A)
Specific examples of components include cellulose powder, zeolite, talc, clay, alumina, kaolin, titania,
Examples thereof include calcium carbonate and barium sulfate, and preferred are zeolite and kaolin which have good dispersibility in water.

【００１０】（Ａ）成分の大きさについては、酵素粒子
内部での分布の均一性の観点から一次粒子の平均粒径が
２０μｍ以下が好ましい。また、（Ａ）成分の一次粒子
の平均粒径が小さくなるほど酵素粒子が緻密となり、そ
の緻密化により酵素粒子の粒子強度が向上し、酵素粒子
凝集体の発塵性が抑制できることからその一次粒子の平
均粒径は１０μｍ以下がより好ましく、０．１〜５μｍ
が特に好ましい。Regarding the size of the component (A), the average particle size of the primary particles is preferably 20 μm or less from the viewpoint of uniformity of distribution inside the enzyme particles. Further, the smaller the average particle size of the primary particles of the component (A) becomes, the denser the enzyme particles become. The densification improves the particle strength of the enzyme particles and suppresses the dusting of the enzyme particle aggregates. Is more preferably 10 μm or less, and 0.1 to 5 μm
Is particularly preferred.

【００１１】酵素粒子中の（Ａ）成分の含有量は、粉塵
の発生を抑え、酵素粒子に崩壊・分散性を持たせ、酵素
の速やかな溶出を促す観点から酵素粒子の４５重量％以
上が好ましく、更に高速溶解性を高める観点から５０重
量％以上がより好ましい。一方、発塵量抑制と溶け残り
防止の観点から該含量は酵素粒子の９０重量％以下が好
ましく、８０重量％以下がより好ましく、７０重量％以
下が特に好ましい。従って、高速溶解性と低発塵性を同
時に満たし、溶け残りを防止することを考えると、該含
量は酵素粒子の４５〜９０重量％が好ましく、５０〜８
０重量％がより好ましく、５０〜７０重量％が特に好ま
しい。The content of the component (A) in the enzyme particles is preferably 45% by weight or more of the enzyme particles from the viewpoint of suppressing generation of dust, imparting disintegration and dispersibility to the enzyme particles, and promoting rapid elution of the enzyme. It is more preferably at least 50% by weight from the viewpoint of increasing the high-speed solubility. On the other hand, the content is preferably 90% by weight or less, more preferably 80% by weight or less, particularly preferably 70% by weight or less of the enzyme particles, from the viewpoints of suppressing the amount of dust generation and preventing undissolved residue. Therefore, considering simultaneously satisfying high-speed dissolution and low dust generation and preventing undissolved residue, the content is preferably 45 to 90% by weight of the enzyme particles, and 50 to 8% by weight.
0% by weight is more preferable, and 50 to 70% by weight is particularly preferable.

【００１２】また、本発明においては、（Ａ）成分は１
種以上を使用することができる。また、２種以上を組み
合わせて用いる場合、粒径の異なる粒子や形状の異なる
粒子を配合することにより、酵素粒子の構造を緻密化又
は強化して発塵性を抑制することも可能である。例えば
一次粒子の平均粒径が２〜３μｍの粒子に一次粒子の平
均粒径が１μｍ以下の粒子を組み合わせることにより、
一次粒子の平均粒径が２〜３μｍの粒子のみで構成した
場合に比べ発塵抑制が可能となる。このように異なる粒
径の粒子を組み合わせて用いる場合、小粒径粒子の割合
は発塵抑制効果の観点から（Ａ）成分中５〜６０％が好
ましく、５〜５０％がより好ましい。In the present invention, the component (A) comprises 1
More than one species can be used. When two or more kinds are used in combination, particles having different particle diameters or particles having different shapes can be blended to make the structure of the enzyme particles denser or stronger, thereby suppressing dust generation. For example, by combining particles having an average primary particle diameter of 1 μm or less with particles having an average primary particle diameter of 2 to 3 μm,
Dust generation can be suppressed as compared with a case where the average particle size of the primary particles is only 2 to 3 μm. When the particles having different particle diameters are used in combination, the proportion of the particles having a small particle diameter is preferably 5 to 60%, more preferably 5 to 50% in the component (A) from the viewpoint of the dust generation suppressing effect.

【００１３】２．（Ｂ）成分 （Ｂ）成分としては、粒子を構成する成分同士を結合さ
せる能力を持ち、実質的に酵素を失活させず、水中で速
やかに溶解する性質を有するものであれば特に限定され
ない。例えば、ポリエチレングリコール、ポリプロピレ
ングリコール、ポリオキシエチレンアルキルエーテル及
びそれらの誘導体、ポリビニルアルコール及びその誘導
体、水溶性セルロース誘導体（これらの誘導体として
は、エーテル化合物等が挙げられる）、カルボン酸系ポ
リマー、澱粉、糖類等が挙げられる。生産性、高速溶解
性の観点からは、カルボン酸系ポリマー及び糖類が好ま
しく、アクリル酸−マレイン酸コポリマーの塩、ポリア
クリル酸塩がより好ましい。塩としてはナトリウム塩、
カリウム塩、アンモニウム塩が好ましい。尚、カルボン
酸系ポリマーの分子量としては、１０００〜１００００
０が好ましく、２０００〜８００００がより好ましい。2. Component (B) The component (B) is not particularly limited as long as it has the ability to bind the components constituting the particles, does not substantially inactivate the enzyme, and has the property of rapidly dissolving in water. . For example, polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether and derivatives thereof, polyvinyl alcohol and derivatives thereof, water-soluble cellulose derivatives (these compounds include ether compounds, etc.), carboxylic acid polymers, starch, Sugars and the like. From the viewpoint of productivity and high-speed solubility, carboxylic acid polymers and saccharides are preferable, and salts of acrylic acid-maleic acid copolymers and polyacrylates are more preferable. Sodium salt,
Potassium salts and ammonium salts are preferred. The molecular weight of the carboxylic acid-based polymer is 1,000 to 10,000.
0 is preferable, and 2000 to 80000 is more preferable.

【００１４】酵素粒子中の（Ｂ）成分の含有量は、低発
塵性の観点から酵素粒子の５重量％以上が好ましく、１
５重量％以上がより好ましい。高速溶解性の観点から酵
素粒子の４０重量％以下が好ましく、３０重量％以下が
より好ましい。従って、低発塵性及び高速溶解性の観点
から該含有量は酵素粒子の５〜４０重量％が好ましく、
１５〜３０重量％がより好ましい。また、本発明で使用
する水溶性バインダーは２種以上組み合せることができ
る。２種以上の異なった効果を持つ水溶性バインダーを
組み合わせることにより、その複合効果を期待すること
もできる。例えば水中で速やかに溶解するバインダー
に、酵素の安定化能をもつバインダーをさらに用いて組
み合わせることによって、酵素粒子の安定性をさらに付
与することができる。The content of the component (B) in the enzyme particles is preferably at least 5% by weight of the enzyme particles from the viewpoint of low dust generation.
5% by weight or more is more preferable. From the viewpoint of high-speed solubility, the amount is preferably 40% by weight or less, more preferably 30% by weight or less of the enzyme particles. Therefore, the content is preferably 5 to 40% by weight of the enzyme particles from the viewpoint of low dust generation and high-speed solubility.
15-30% by weight is more preferred. The water-soluble binder used in the present invention can be used in combination of two or more. By combining two or more types of water-soluble binders having different effects, the combined effect can be expected. For example, the stability of enzyme particles can be further imparted by further combining a binder that can be rapidly dissolved in water with a binder having an enzyme stabilizing ability.

【００１５】３．（Ｃ）成分 （Ｃ）成分としては、洗浄剤へ配合して洗浄効果等を発
揮する酵素であれば特に制限されない。例えば、セルラ
ーゼ、プロテアーゼ、ペプチナーゼ、アミラーゼ、リパ
ーゼ、及びデキストラナーゼから選ばれる１種以上が好
ましく用いられる。酵素粒子中の（Ｃ）成分の含有量
は、酵素活性発現の観点から０．５重量％以上が好まし
く、２重量％がより好ましい。高速溶解性の観点から３
０重量％以下が好ましく、２５重量％以下がより好まし
い。従って、酵素活性発現及び高速溶解性の観点から該
含有量は０．５〜３０重量％が好ましく、２〜２５重量
％がより好ましい。3. Component (C) The component (C) is not particularly limited as long as it is an enzyme that exhibits a cleaning effect or the like when incorporated into a detergent. For example, one or more selected from cellulase, protease, peptinase, amylase, lipase, and dextranase are preferably used. The content of the component (C) in the enzyme particles is preferably 0.5% by weight or more, and more preferably 2% by weight, from the viewpoint of expressing the enzyme activity. 3 from the viewpoint of fast solubility
0% by weight or less is preferable, and 25% by weight or less is more preferable. Therefore, the content is preferably from 0.5 to 30% by weight, more preferably from 2 to 25% by weight, from the viewpoint of enzyme activity expression and rapid solubility.

【００１６】（Ｃ）成分の使用形態としては、例えば、
微生物により生産された酵素を含有する培養物を濾過、
濃縮した濃縮液の形で使用してもよく、濃縮液を乾燥し
て得られた酵素粉末を使用してもよい。酵素濃縮液を用
いる場合、濾過によって分離しきれない糖類、無機塩類
等が含まれていてもよい。As the use form of the component (C), for example,
Filtering the culture containing the enzyme produced by the microorganism,
It may be used in the form of a concentrated concentrate, or an enzyme powder obtained by drying the concentrate may be used. When an enzyme concentrate is used, it may contain saccharides, inorganic salts, and the like that cannot be separated by filtration.

【００１７】４．その他の水溶性物質 酵素粒子には、前記のような（Ａ）成分、（Ｂ）成分、
（Ｃ）成分以外に、必要に応じてその他の水溶性物質が
含まれていてもよい。例えば安定化剤、賦形剤として塩
化ナトリウム、塩化カルシウム、塩化マグネシウム、芒
硝等を配合することができる。その他の水溶性物質の量
は、（Ｂ）成分、（Ｃ）成分、及び該水溶性物質の含有
量の総和が酵素粒子の５５重量％を超えない範囲が好ま
しい。特に、高速溶解性及び低発塵性の観点からその他
の水溶性物質の含有量は酵素粒子の１５重量％以下が好
ましく、１０重量％以下がより好ましい。（Ａ）成分、
（Ｂ）成分及びその他の水溶性物質の好ましい組み合わ
せとしては、例えば、（Ａ）成分としてゼオライト、
（Ｂ）成分としてポリアクリル酸ナトリウムと糖類、そ
の他の水溶性物質として賦形剤である芒硝、といった組
み合わせが挙げられる。4. Other water-soluble substances Enzyme particles include the components (A), (B),
In addition to the component (C), other water-soluble substances may be contained as necessary. For example, sodium chloride, calcium chloride, magnesium chloride, sodium sulfate and the like can be blended as a stabilizer and an excipient. The amount of other water-soluble substances is preferably such that the sum of the components (B) and (C) and the content of the water-soluble substances does not exceed 55% by weight of the enzyme particles. In particular, the content of the other water-soluble substance is preferably 15% by weight or less, more preferably 10% by weight or less of the enzyme particles from the viewpoint of high-speed solubility and low dust generation. (A) component,
Preferred combinations of component (B) and other water-soluble substances include, for example, zeolite as component (A),
As the component (B), a combination of sodium polyacrylate and a saccharide, and other water-soluble substances such as sodium sulfate as an excipient may be mentioned.

【００１８】５．酵素粒子 酵素粒子は、その内部よりも表面近傍に（Ｂ）成分が多
く存在する構造である。（Ｂ）成分が表面近傍に偏在す
るため、水中でまず（Ｂ）成分が溶解した後、（Ａ）成
分に水が接触するため、粒子自体が崩壊し、水中に分散
する。そのため、（Ｃ）成分の水中への溶出が速やかに
行われる。従って、この構造を有する酵素粒子であれ
ば、粒径や嵩密度が大きくなっても速やかに酵素を溶出
させることができ、溶け残りもない。加えて、酵素粒子
表面近傍において、粒子を構成する成分同士を結合させ
るバインダーの量が多いため、更に粒子強度が向上し、
発塵抑制が可能となる。5. Enzyme Particle The enzyme particle has a structure in which the component (B) is present more near the surface than inside the enzyme particle. Since the component (B) is unevenly distributed near the surface, the component (B) first dissolves in water, and then the water comes into contact with the component (A), so that the particles themselves are disintegrated and dispersed in the water. Therefore, the elution of the component (C) into water is promptly performed. Therefore, with the enzyme particles having this structure, the enzyme can be rapidly eluted even if the particle size and bulk density become large, and there is no undissolved residue. In addition, in the vicinity of the enzyme particle surface, since the amount of the binder that binds the components constituting the particle is large, the particle strength is further improved,
Dust generation can be suppressed.

【００１９】酵素粒子の平均粒径は目標とする酵素粒子
凝集体の平均粒径によって最適な粒径が変わる為特に規
定はされないが、高速溶解性の観点からは５００μｍ以
下が好ましく、３００μｍ以下がより好ましい。又、発
塵抑制の観点からは１００μｍ以上が好ましく、１５０
μｍ以上がより好ましい。従って、高速溶解性及び発塵
抑制の観点からは１００〜５００μｍが好ましく、１０
０〜３００μｍがより好ましく、１５０〜３００μｍが
特に好ましい。The average particle size of the enzyme particles is not particularly defined because the optimum particle size varies depending on the target average particle size of the enzyme particle aggregate, but is preferably 500 μm or less, and more preferably 300 μm or less from the viewpoint of high-speed solubility. More preferred. Further, from the viewpoint of suppressing dust generation, the thickness is preferably 100 μm or more,
μm or more is more preferable. Therefore, from the viewpoint of high-speed dissolution and suppression of dust generation, the thickness is preferably 100 to 500 μm,
0 to 300 μm is more preferable, and 150 to 300 μm is particularly preferable.

【００２０】（Ｂ）成分の偏在性は、次の方法で確認す
ることができる。まず、測定対象の凝集前の酵素粒子
と、該酵素粒子をメノウ乳鉢等で十分に粉砕して均一な
状態とした酵素粒子粉砕物とを用意する。そして、酵素
粒子及び酵素粒子粉砕物の表面から約１０μｍまでの情
報が得られる条件で、両者をそれぞれフーリエ変換赤外
分光法（ＦＴ−ＩＲ）と光音響分光法（ＰＡＳ）とを併
用する方法（以下、「ＦＴ−ＩＲ／ＰＡＳ」という）に
より測定する。前者の（Ｂ）成分の量が後者の（Ｂ）成
分の量より多い場合、測定対象の酵素粒子は酵素粒子の
内部よりも表面近傍に（Ｂ）成分が多く存在する構造を
有するものである。酵素粒子及び酵素粒子粉砕物の表面
から約１０μｍまでの情報が得られる測定条件として
は、例えば、分解能８ｃｍ-1、スキャン速度０．６３ｃ
ｍ／ｓ、積算１２８回、という条件が挙げられる。使用
する装置は、例えば、赤外分光光度計としてBio-Rad La
boratories社製ＦＴＳ−６０Ａ／８９６型赤外分光光度
計が、ＰＡＳセルとしてＭＴＥＣ社製３００型光音響検
出器が挙げられる。なお、ＦＴ−ＩＲ／ＰＡＳはAPPLIE
D SPECTROSCOPY vol.47 1311-1316(1993) に記載されて
いる。The uneven distribution of the component (B) can be confirmed by the following method. First, an enzyme particle before agglutination to be measured and a crushed enzyme particle which is sufficiently crushed in an agate mortar or the like to make the enzyme particle uniform are prepared. Then, under the condition that information up to about 10 μm can be obtained from the surfaces of the enzyme particles and the crushed enzyme particles, a method using both of them together with Fourier transform infrared spectroscopy (FT-IR) and photoacoustic spectroscopy (PAS) (Hereinafter referred to as “FT-IR / PAS”). When the amount of the former component (B) is larger than the amount of the latter (B) component, the enzyme particle to be measured has a structure in which the (B) component is present more near the surface than inside the enzyme particle. . The measurement conditions for obtaining information up to about 10 μm from the surfaces of the enzyme particles and the crushed enzyme particles include, for example, a resolution of 8 cm −1 and a scan speed of 0.63 c.
m / s and a total of 128 times. The device used is, for example, Bio-Rad La as an infrared spectrophotometer.
The FTS-60A / 896 type infrared spectrophotometer manufactured by boratories, and the 300 type photoacoustic detector manufactured by MTEC are used as the PAS cell. FT-IR / PAS is APPLIE
D SPECTROSCOPY vol.47 1311-1316 (1993).

【００２１】６．酵素粒子凝集体 酵素粒子を含有する酵素粒子凝集体は、酵素粒子が凝集
した構造であればよく凝集の方法は問わないが、凝集構
造の安定性及び生産性の観点からは酵素粒子がバインダ
ー（以下（Ｄ）成分）によって凝集した酵素粒子凝集体
が好ましい。この酵素粒子凝集体は酵素粒子が元の形状
及び構造を維持しつつ数個から数十個結合した構造とな
っており、酵素粒子を圧密化することなく凝集させてい
る為、酵素粒子の持つ高速溶解性を損なうことなく、酵
素粒子単独の時と同様に酵素粒子が崩壊して水中に分散
し、酵素の水中への溶出が速やかに行われる。また、凝
集による粒径の向上が生じる為、酵素粒子の持つ発塵性
を更に抑制することが可能である。6. Enzyme particle aggregate The enzyme particle aggregate containing the enzyme particles is not limited as long as the enzyme particles have a structure in which the enzyme particles are aggregated. However, from the viewpoint of the stability and productivity of the aggregate structure, the enzyme particles are bound with a binder ( The enzyme particle aggregate aggregated by the following (D) component is preferred. This enzyme particle aggregate has a structure in which several to several tens of enzyme particles are bonded while maintaining the original shape and structure, and because the enzyme particles are aggregated without consolidation, the enzyme particles have Without impairing the high-speed solubility, the enzyme particles are disintegrated and dispersed in water in the same manner as in the case of the enzyme particles alone, and the enzyme is rapidly eluted into water. Further, since the particle size is improved by the aggregation, it is possible to further suppress the dust generation of the enzyme particles.

【００２２】酵素粒子凝集体の平均粒径としては、視認
性の観点からは１５０μｍ以上が好ましく、２００μｍ
以上がより好ましく、３００μｍ以上が特に好ましい。
又、分級抑制の観点からは２０００μｍ以下が好まし
く、１０００μｍ以下がより好ましく、７００μｍ以下
が特に好ましい。従って、視認性及び分級抑制の観点か
ら１５０〜２０００μｍが好ましく、２００〜１０００
μｍがより好ましく、３００〜１０００μｍが更に好ま
しく、３００〜７００μｍが特に好ましい。酵素粒子凝
集体の平均粒径については、酵素粒子の平均粒径と凝集
の条件によってコントロール可能である。例えば、同じ
凝集条件下で酵素粒子の平均粒径を小さくすれば、酵素
粒子凝集体の平均粒径は小さくなる。また、同じ平均粒
径の酵素粒子を用いた場合には、凝集速度を上げると酵
素粒子凝集体の平均粒径は大きくなる。The average particle size of the enzyme particle aggregate is preferably 150 μm or more from the viewpoint of visibility, and 200 μm or more.
The thickness is more preferably, and particularly preferably 300 μm or more.
Further, from the viewpoint of suppression of classification, it is preferably at most 2,000 μm, more preferably at most 1,000 μm, particularly preferably at most 700 μm. Therefore, from the viewpoint of visibility and suppression of classification, the thickness is preferably 150 to 2000 μm, and 200 to 1000 μm.
μm is more preferable, 300 to 1000 μm is further preferable, and 300 to 700 μm is particularly preferable. The average particle size of the enzyme particle aggregate can be controlled by the average particle size of the enzyme particles and the conditions for aggregation. For example, if the average particle size of the enzyme particles is reduced under the same aggregation conditions, the average particle size of the enzyme particle aggregate is reduced. When enzyme particles having the same average particle size are used, increasing the aggregation speed increases the average particle size of the enzyme particle aggregate.

【００２３】同様に嵩密度についても、酵素粒子の平均
粒径と凝集の条件によってコントロール可能である。例
えば、酵素粒子の粒径を小さくして、緩やかに凝集させ
ることにより、嵩密度が低い粒子を得ることが可能であ
る。このことから酵素粒子凝集体は洗浄剤組成物中にブ
レンドする際の分級について、凝集体の平均粒径と嵩密
度を制御することにより、分級を抑制することが可能で
ある。例えば在来型洗剤のような嵩密度の低い洗浄剤組
成物から圧密型洗剤のような嵩密度の高い洗浄剤組成物
まで幅広く配合できる。酵素粒子凝集体の形状について
は特に規定はされないが、例えば不定形とすることによ
り、洗浄剤中での分級を更に抑制することが可能であ
る。Similarly, the bulk density can be controlled by the average particle size of the enzyme particles and the conditions for aggregation. For example, it is possible to obtain particles having a low bulk density by reducing the particle size of the enzyme particles and slowly aggregating them. From this, it is possible to suppress the classification of the enzyme particle aggregates by controlling the average particle size and the bulk density of the aggregates when blending into the detergent composition. For example, it can be widely mixed from a detergent composition having a low bulk density such as a conventional detergent to a detergent composition having a high bulk density such as a compacted detergent. Although the shape of the enzyme particle aggregate is not particularly limited, for example, by making the shape irregular, classification in the detergent can be further suppressed.

【００２４】酵素粒子凝集体が高速溶解性を有する為に
は、酵素粒子自身が高速溶解性を有する必要がある。ま
た、酵素粒子凝集体の発塵性は酵素粒子の発塵の影響を
強く受ける為、酵素粒子の発塵性もできる限り抑制され
ていることが望ましい。本発明において酵素粒子を
（Ｄ）成分によって凝集させる場合、（Ｄ）成分として
は、酵素粒子同士を結合させる能力を持ち、実質的に酵
素を失活させないものであれば特に限定されない。
（Ｄ）成分は（Ｂ）成分と同じものでも、（Ｂ）成分以
外のものでもよく、酵素粒子の表面近傍に多く存在する
（Ｂ）成分を用いてもよい。又、（Ｄ）成分は水不溶性
でも水溶性でもよく、２種以上を組み合わせて用いても
よい。In order for the enzyme particle aggregate to have high-speed solubility, the enzyme particles themselves need to have high-speed solubility. Further, since the dusting property of the enzyme particle aggregate is strongly affected by the dusting of the enzyme particles, it is desirable that the dusting property of the enzyme particles is also suppressed as much as possible. In the present invention, when the enzyme particles are aggregated by the component (D), the component (D) is not particularly limited as long as it has an ability to bind the enzyme particles and does not substantially deactivate the enzyme.
The component (D) may be the same as the component (B) or a component other than the component (B), and the component (B) which is present in a large amount near the surface of the enzyme particle may be used. The component (D) may be water-insoluble or water-soluble, and may be used in combination of two or more.

【００２５】高速溶解性の観点からすると（Ｄ）成分の
うち少なくとも１種は水溶性であることが好ましい。
又、水不溶性の（Ｄ）成分のみを用いる場合、高速溶解
性の観点からは、（Ｄ）成分が酵素粒子表面を完全に被
覆することなく、水中において酵素粒子表面への水分の
進入が容易であることが好ましい。水不溶性の（Ｄ）成
分としては例えば、脂肪酸、高級アルコール、硬化油等
が挙げられ、水溶性の（Ｄ）成分としては例えば、ポリ
エチレングリコール、ポリプロピレングリコール、ポリ
オキシエチレンアルキルエーテル及びそれらの誘導体、
ポリビニルアルコール及びその誘導体、ポリビニルピロ
リドン、水溶性セルロース誘導体（これらの誘導体とし
ては、エーテル化合物等が挙げられる）、カルボン酸系
ポリマー、澱粉、糖類等が挙げられる。高速溶解性及び
低発塵性の観点からはポリエチレングリコール及びその
誘導体が好ましい。ポリエチレングリコールは分子量３
０００〜３００００のものが好ましく、５０００〜１５
０００のものがより好ましい。From the viewpoint of high-speed solubility, it is preferable that at least one of the components (D) is water-soluble.
When only the water-insoluble component (D) is used, from the viewpoint of rapid solubility, the component (D) does not completely cover the enzyme particle surface, and water can easily enter the enzyme particle surface in water. It is preferred that Examples of the water-insoluble component (D) include fatty acids, higher alcohols, and hardened oils. Examples of the water-soluble component (D) include polyethylene glycol, polypropylene glycol, polyoxyethylene alkyl ether, and derivatives thereof.
Examples thereof include polyvinyl alcohol and its derivatives, polyvinylpyrrolidone, water-soluble cellulose derivatives (these compounds include ether compounds), carboxylic acid polymers, starch, and saccharides. Polyethylene glycol and its derivatives are preferred from the viewpoints of fast solubility and low dust generation. Polyethylene glycol has a molecular weight of 3
000 to 30,000 are preferred, and 5,000 to 15,
000 is more preferred.

【００２６】又、酵素粒子凝集体には、前記酵素粒子及
び（Ｄ）成分以外に、必要に応じてその他の物質が含ま
れていてもよい。酵素粒子凝集体に含まれるその他物質
としては酵素粒子凝集体の高速溶解性を損なわないもの
であれば特に限定はされず、２種以上を組み合わせて用
いてもよい。例えば嵩密度の調整の為に塩化ナトリウ
ム、塩化カルシウム、塩化マグネシウム、芒硝等を配合
することができる。In addition, the enzyme particle aggregate may contain other substances as required in addition to the enzyme particles and the component (D). The other substance contained in the enzyme particle aggregate is not particularly limited as long as it does not impair the high-speed solubility of the enzyme particle aggregate, and two or more kinds may be used in combination. For example, sodium chloride, calcium chloride, magnesium chloride, sodium sulfate and the like can be blended for adjusting the bulk density.

【００２７】７．酵素粒子の製法 酵素粒子の製法は、酵素粒子の圧密化による溶解性の低
下を防ぐために、例えば（Ａ）成分、（Ｂ）成分及び
（Ｃ）成分を含むスラリーを乾燥させて製造する方法が
好ましい。また、酵素粒子の内部よりも表面近傍に
（Ｂ）成分が多く存在する構造の粒子を得るためには、
例えば、上記スラリーを乾燥させて粒子を製造した後、
該粒子表面に（Ｂ）成分を表面被覆する方法や上記スラ
リーを噴霧乾燥する方法等が挙げられる。特に、加熱乾
燥の際、水の移動と共に表面近傍に（Ｂ）成分が多く集
まるため、容易に上記構造の粒子を得ることができる噴
霧乾燥法が好ましい。7. Method for Producing Enzyme Particles The method for producing enzyme particles involves, for example, drying a slurry containing the components (A), (B) and (C) in order to prevent a decrease in solubility due to the compaction of the enzyme particles. preferable. Further, in order to obtain particles having a structure in which the component (B) is present more near the surface than inside the enzyme particles,
For example, after drying the slurry to produce particles,
A method of coating the surface of the particles with the component (B) and a method of spray-drying the slurry are mentioned. In particular, at the time of heating and drying, a large amount of the component (B) collects in the vicinity of the surface together with the movement of water.

【００２８】噴霧乾燥法によって本発明の酵素粒子を製
造する場合、まず、各成分を含有するスラリーを調製す
る。得られる酵素粒子の各成分の含有量は、スラリーの
固形分中の各成分の含有量に対応した値となる。本明細
書において「固形分」とは、（Ａ）成分、（Ｂ）成分、
（Ｃ）成分及びその他の水溶性物質をいう。また、スラ
リー調製のための分散媒は、通常、水が用いられる。噴
霧乾燥のためのスラリーの固形分含有量を高めること
は、得られる酵素粒子の発塵性を低減することができる
ため好ましい。高速溶解性と低発塵との両立を考える
と、スラリーの固形分含有量は４０重量％以上が好まし
く、５０重量％以上がより好ましい。また、スラリー噴
霧の容易さからは、該固形分含有量は６０重量％以下が
好ましい。従って、スラリーの固形分含有量は４０〜６
０重量％が好ましく、５０〜６０重量％がより好まし
い。When producing the enzyme particles of the present invention by the spray drying method, first, a slurry containing each component is prepared. The content of each component of the obtained enzyme particles is a value corresponding to the content of each component in the solid content of the slurry. In the present specification, the “solid content” refers to the component (A), the component (B),
(C) Component and other water-soluble substances. In addition, water is usually used as a dispersion medium for preparing a slurry. It is preferable to increase the solid content of the slurry for spray drying because the dusting property of the obtained enzyme particles can be reduced. Considering compatibility between high-speed solubility and low dust generation, the solid content of the slurry is preferably 40% by weight or more, more preferably 50% by weight or more. Further, from the viewpoint of ease of spraying the slurry, the solid content is preferably 60% by weight or less. Therefore, the solid content of the slurry is between 40 and 6
0% by weight is preferable, and 50 to 60% by weight is more preferable.

【００２９】噴霧乾燥スラリーを調製する場合の（Ａ）
成分、（Ｂ）成分、（Ｃ）成分の配合順序は特に限定は
されないが、スラリー配合調製、発塵性の観点から最適
な順序があり、その順序に関しては配合物の物性によっ
て異なるため、適宜最適化を行うことができる。例えば
（Ａ）成分にゼオライト、（Ｂ）成分にポリアクリル酸
ナトリウムと糖類、賦形剤として芒硝を用いた場合に
は、酵素、芒硝、糖類、ゼオライト、ポリアクリル酸ナ
トリウムの順で配合するのが好ましい。調製されたスラ
リーを噴霧乾燥装置に供給する。供給時のスラリーの温
度については、実質的に酵素が失活しない温度であるの
が好ましい。酵素の安定性及びスラリーの製造し易さの
観点から１０〜４０℃が好ましく、２０〜３０℃がより
好ましい。噴霧乾燥時の送風温度は１２０〜２２０℃が
好ましく、１４０〜１８０℃がより好ましい。この温度
範囲で噴霧乾燥を行うことは、生産性が良好となり、実
質的に酵素が失活しないため好ましい。(A) when preparing a spray-dried slurry
There are no particular restrictions on the order in which the components, (B) and (C) are blended, but there is an optimal sequence from the viewpoint of slurry blending preparation and dust generation, and the sequence varies depending on the physical properties of the blend. Optimization can be performed. For example, when zeolite is used as the component (A), sodium polyacrylate and saccharides are used as the component (B), and sodium sulfate is used as an excipient, the enzyme, sodium sulfate, saccharide, zeolite, and sodium polyacrylate are added in this order. Is preferred. The prepared slurry is supplied to a spray dryer. The temperature of the slurry at the time of supply is preferably a temperature at which the enzyme is not substantially deactivated. From the viewpoint of enzyme stability and ease of slurry production, the temperature is preferably from 10 to 40C, more preferably from 20 to 30C. The blowing temperature during spray drying is preferably from 120 to 220 ° C, more preferably from 140 to 180 ° C. Performing spray drying in this temperature range is preferable because productivity is improved and the enzyme is not substantially deactivated.

【００３０】８．酵素粒子凝集体の製法 酵素粒子凝集体の製法としては、該酵素粒子に水又は
（Ｄ）成分を含有する水溶液を添加し、乾燥及び／又は
冷却することにより酵素粒子凝集体を得る方法（１）
や、該酵素粒子に溶融した熱可塑性の（Ｄ）成分を添加
し、冷却させることにより酵素粒子凝集体を得る方法
（２）等がある。高速溶解性及び生産性の観点からは方
法（１）が好ましい。8. Method for Producing Enzyme Particle Aggregate As a method for producing an enzyme particle aggregate, a method for obtaining an enzyme particle aggregate by adding water or an aqueous solution containing the component (D) to the enzyme particles, followed by drying and / or cooling (1) )
And a method (2) of adding a molten thermoplastic (D) component to the enzyme particles and cooling the mixture to obtain an enzyme particle aggregate. Method (1) is preferred from the viewpoint of high-speed solubility and productivity.

【００３１】方法（１）のうち、水を添加する方法とし
て、（イ）酵素粒子を乾燥しつつ、水を噴霧することに
より、酵素粒子表面の（Ｂ）成分を一部溶解させ付着凝
集させた後、更に乾燥する方法、（ロ）スラリーを噴霧
乾燥することにより酵素粒子を製造する場合、水分含有
量１０重量％以上で酵素粒子の乾燥を止め、その後、静
置或いは流動等により酵素粒子表面の（Ｂ）成分を一部
溶解させ付着凝集させた後に乾燥する方法、等が有る。
方法（１）のうち、（Ｄ）成分を含有する水溶液を添加
する方法としては（ハ）酵素粒子を乾燥しつつ、（Ｄ）
成分を水溶液として噴霧することにより、水溶液により
一部溶解した酵素粒子表面の（Ｂ）成分と噴霧した
（Ｄ）成分とにより付着凝集させた後、更に乾燥及び／
又は冷却する方法、等が有る。発塵抑制及び粒径制御の
観点から（ハ）の方法が好ましい。方法（２）として
は、（ニ）酵素粒子を流動しつつ、溶融した熱可塑性の
（Ｄ）成分を噴霧し、酵素粒子表面に付着させた後、冷
却によって（Ｄ）成分を固化させて凝集させる方法等が
有る。In the method (1), water is added by (a) spraying water while drying the enzyme particles, thereby partially dissolving the component (B) on the surface of the enzyme particles to cause adhesion and aggregation. (B) When the enzyme particles are produced by spray-drying the slurry, the drying of the enzyme particles is stopped when the water content is 10% by weight or more, and then the enzyme particles are allowed to stand or flow. There is a method in which the component (B) on the surface is partially dissolved, adhered and aggregated, and then dried.
In the method (1), the method of adding the aqueous solution containing the component (D) includes (c) drying the enzyme particles while drying the enzyme particles.
By spraying the component as an aqueous solution, the component (B) on the surface of the enzyme particles partially dissolved by the aqueous solution and the sprayed component (D) are adhered and aggregated, and then further dried and / or dried.
Alternatively, there is a method of cooling. The method (c) is preferred from the viewpoints of dust generation suppression and particle size control. In the method (2), (d) the molten thermoplastic (D) component is sprayed while the enzyme particles are flowing and adhered to the surface of the enzyme particles, and then the component (D) is solidified by cooling and aggregated. There is a method to make it.

【００３２】凝集操作としては、酵素粒子が圧密化を抑
制しつつ付着凝集される方法であれば、特に規定はされ
ないが、例えば静置による方法や流動による方法があ
る。このうち、粒径制御及び生産性の観点から流動によ
る付着凝集が好ましい。流動化の方法としては例えば、
攪拌転動造粒装置による方法、流動層による方法等があ
るが、粒径制御の観点からは流動層による方法が好まし
い。従って、酵素粒子凝集体の製法としては、発塵抑
制、粒径制御及び生産性の観点から、酵素粒子を流動乾
燥しつつ、（Ｄ）成分を水溶液として噴霧することによ
り、水溶液により一部溶解した酵素粒子表面の（Ｂ）成
分と噴霧した（Ｄ）成分により付着凝集させた後、更に
乾燥する方法が好ましく、発塵抑制及び粒径制御の観点
から、酵素粒子を流動層を用いて流動乾燥しつつ、
（Ｄ）成分を水溶液として噴霧することにより、水溶液
により一部溶解した酵素粒子表面の（Ｂ）成分と噴霧し
た（Ｄ）成分により付着凝集させた後、更に乾燥する方
法がより好ましい。The aggregating operation is not particularly limited as long as the enzyme particles are adhered and agglomerated while suppressing the compaction. For example, there are a method of standing and a method of flowing. Of these, adhesion and aggregation by flow are preferred from the viewpoint of particle size control and productivity. As a method of fluidization, for example,
There are a method using an agitating tumbling granulator, a method using a fluidized bed, and the like, and a method using a fluidized bed is preferable from the viewpoint of particle size control. Therefore, as a method for producing the enzyme particle aggregate, from the viewpoints of dust generation suppression, particle size control and productivity, the component (D) is sprayed as an aqueous solution while the enzyme particles are fluidized and dried, so that the enzyme particle is partially dissolved in the aqueous solution. It is preferable that the enzyme particles are adhered and coagulated by the component (B) and the sprayed component (D) on the surface of the enzyme particles, and then further dried. While drying
A more preferred method is to spray the component (D) as an aqueous solution so that the component (B) on the surface of the enzyme particles partially dissolved by the aqueous solution and the sprayed component (D) are adhered and aggregated, and then further dried.

【００３３】酵素粒子凝集体を上記方法（１）で製造す
る場合、乾燥温度は酵素が実質的に失活しない温度であ
れば特に規定はされないが、生産性の観点からは乾燥温
度は高い方がよく、３０℃以上が好ましく５０℃以上が
より好ましい。一方、酵素活性の観点から、乾燥温度は
低い方がよく、１００℃以下が好ましく、７０℃以下が
より好ましい。従って、生産性と酵素活性の観点から、
３０〜１００℃が好ましく、５０〜７０℃がより好まし
い。また、酵素粒子凝集体を上記方法（１）で製造する
際、（Ｄ）成分としてポリエチレングリコール等の熱可
塑性物質を選んだ場合、装置内部への付着を抑制する観
点から、（Ｄ）成分が溶融する温度以下で乾燥を行うこ
とが好ましい。酵素粒子の凝集に用いられる（Ｄ）成分
としては前述６項記載のものが挙げられる。また、添加
する（Ｄ）成分の量は特に規定されず、（Ｂ）成分を用
いる場合等には添加しなくてもよい。（Ｄ）成分を添加
する場合、高速溶解性の観点から酵素粒子凝集体の２０
重量％以下が好ましく、１０重量％以下がより好まし
く、５重量％以下が特に好ましい。一方、低発塵性の観
点からは１重量％以上が好ましく、３重量％以上がより
好ましい。従って、高速溶解性及び低発塵性の観点から
該添加量は酵素粒子凝集体の１〜２０重量％が好まし
く、１〜１０重量％がより好ましく、３〜５重量％が更
に好ましい。また、（Ｄ）成分を水溶液の形で用いる場
合、（Ｄ）成分は水溶性でも水不溶性でもよいが、酵素
粒子への分散性の観点からは（Ｄ）成分が溶解もしくは
均一分散していることが好ましい。その（Ｄ）成分の濃
度は、酵素粒子への分散性の観点から５〜６０重量％が
好ましく、１０〜５０重量％がより好ましい。When the enzyme particle aggregate is produced by the above method (1), the drying temperature is not particularly limited as long as the enzyme does not substantially deactivate the enzyme, but from the viewpoint of productivity, the drying temperature is higher. The temperature is preferably 30 ° C. or higher, more preferably 50 ° C. or higher. On the other hand, from the viewpoint of enzyme activity, the drying temperature is preferably lower, preferably 100 ° C or lower, more preferably 70 ° C or lower. Therefore, from the viewpoint of productivity and enzyme activity,
30-100 degreeC is preferable and 50-70 degreeC is more preferable. In addition, when a thermoplastic substance such as polyethylene glycol is selected as the component (D) when the enzyme particle aggregate is produced by the above method (1), the component (D) is used from the viewpoint of suppressing adhesion to the inside of the device. Drying is preferably performed at a temperature lower than the melting temperature. As the component (D) used for the aggregation of the enzyme particles, those described in the above item 6 can be mentioned. The amount of the component (D) to be added is not particularly limited, and may not be added when the component (B) is used. When the component (D) is added, from the viewpoint of rapid solubility, 20
% By weight, preferably 10% by weight or less, more preferably 5% by weight or less. On the other hand, from the viewpoint of low dust generation, 1% by weight or more is preferable, and 3% by weight or more is more preferable. Therefore, from the viewpoint of high-speed solubility and low dust generation, the amount is preferably 1 to 20% by weight, more preferably 1 to 10% by weight, even more preferably 3 to 5% by weight of the enzyme particle aggregate. When the component (D) is used in the form of an aqueous solution, the component (D) may be water-soluble or water-insoluble, but from the viewpoint of dispersibility in the enzyme particles, the component (D) is dissolved or uniformly dispersed. Is preferred. The concentration of the component (D) is preferably 5 to 60% by weight, more preferably 10 to 50% by weight, from the viewpoint of dispersibility in the enzyme particles.

【００３４】９．酵素粒子凝集体の着色 酵素粒子凝集体は着色されてもよい。酵素粒子凝集体以
外の成分や粒子への色移りや、衣料等への染着性を抑制
する観点から、顔料よりも染料を用いることが好まし
い。染料による着色方法としては、例えば、染料を分散
させた（Ｄ）成分を用いて付着凝集を行い着色酵素粒子
凝集体を得る方法、酵素粒子に流動乾燥を行いつつ、染
料及び（Ｄ）成分を分散させた水溶液を噴霧して被覆し
着色酵素粒子凝集体を得る方法、及び（Ａ）成分、
（Ｂ）成分及び（Ｃ）成分を含むスラリーを乾燥させて
酵素粒子を製造する方法において、スラリー中に染料を
配合して酵素粒子を着色し、着色酵素粒子凝集体を得る
方法等が挙げられ、染料を配合したスラリーを乾燥して
酵素粒子を着色し、着色酵素粒子凝集体を得る方法が好
ましい。この方法では、染料をスラリー中に配合するた
め、スラリー中で染料を容易に均一に分散させることが
でき、その結果、染料の着色性が高い粒子を得ることが
できる。染料を含有するスラリーを実質的に酵素が失活
しない温度で噴霧乾燥させて酵素粒子を着色し、着色酵
素粒子凝集体を得る方法が特に好ましい。このことによ
り、得られる酵素粒子及び酵素粒子凝集体が、その表面
近傍に水溶性バインダーや染料が多く存在する構造を有
することとなる。従って、この方法により酵素粒子凝集
体以外の成分や粒子への色移りが抑えられ、着色性の更
に良好な酵素粒子凝集体を得ることができる。9. Coloring of enzyme particle aggregates The enzyme particle aggregates may be colored. It is preferable to use a dye rather than a pigment from the viewpoint of suppressing color transfer to components and particles other than the enzyme particle aggregates and suppressing dyeing to clothing and the like. Examples of the coloring method using a dye include a method of obtaining a colored enzyme particle aggregate by performing adhesion and aggregation using the component (D) in which the dye is dispersed, and a method of applying the dye and the component (D) while fluid-drying the enzyme particles. A method of spraying and coating the dispersed aqueous solution to obtain a colored enzyme particle aggregate, and (A) a component,
In a method for producing enzyme particles by drying a slurry containing the component (B) and the component (C), there is a method in which a dye is added to the slurry to color the enzyme particles to obtain a colored enzyme particle aggregate. It is preferable to dry the slurry containing the dye to color the enzyme particles to obtain a colored enzyme particle aggregate. In this method, since the dye is blended in the slurry, the dye can be easily and uniformly dispersed in the slurry, and as a result, particles having high coloring properties of the dye can be obtained. Particularly preferred is a method in which the slurry containing the dye is spray-dried at a temperature at which the enzyme is not substantially inactivated, thereby coloring the enzyme particles to obtain a colored enzyme particle aggregate. As a result, the resulting enzyme particles and enzyme particle aggregates have a structure in which a large amount of a water-soluble binder or dye exists near the surface. Therefore, color transfer to components and particles other than the enzyme particle aggregate can be suppressed by this method, and an enzyme particle aggregate having better coloring properties can be obtained.

【００３５】使用する染料については、水に対する溶解
性の高い物質であれば特に限定されない。かかる染料は
いずれのものでもよいが、噴霧乾燥等の加熱を必要とす
る製法に使用される場合には熱に対する安定性が高い方
が好ましい。染料としては赤色１０６号、赤色２２７
号、青色１号、青色２号、緑色３号、黄色２０３号等を
用いることができる。染料の配合量については、着色性
の観点から酵素粒子に対して０．０１重量％以上が好ま
しい。また、染料の分散性の観点から、酵素粒子の１．
０重量％以下が好ましく、０．００１〜０．５重量％が
より好ましい。また、本発明においては、２種以上の染
料を用いてもよい。２種以上の染料を混合することによ
って、色相の調整が容易に可能である。The dye to be used is not particularly limited as long as it is a substance having high solubility in water. Such a dye may be any dye, but when used in a production method that requires heating such as spray drying, it is preferable that the dye has high heat stability. As dyes, Red No. 106, Red 227
No. 1, Blue No. 1, Blue No. 2, Green No. 3, Yellow No. 203, etc. can be used. The amount of the dye is preferably 0.01% by weight or more based on the enzyme particles from the viewpoint of colorability. Further, from the viewpoint of dispersibility of the dye, 1.
0 wt% or less is preferable, and 0.001 to 0.5 wt% is more preferable. In the present invention, two or more dyes may be used. The hue can be easily adjusted by mixing two or more dyes.

【００３６】[0036]

【実施例】本発明における高速溶解性、低発塵性、平均
粒径、嵩密度、非分級性、染着性については、以下の方
法にて測定される。 〔高速溶解性〕本発明において、高速溶解性を有する酵
素粒子とは、溶出率が７０％以上、かつ溶解率が８５％
以上の酵素粒子を言う。溶出率は酵素粒子から酵素が溶
出し、その性能を発現するまでの時間に、そして溶解率
は溶け残りの防止の程度にそれぞれ対応する。高速溶解
性を満足する酵素粒子は、酵素が速やかに作用するだけ
でなく、溶け残りもなくなるため、極めて好ましい。EXAMPLES The fast dissolving property, low dusting property, average particle size, bulk density, non-classifying property and dyeing property in the present invention are measured by the following methods. [Fast solubility] In the present invention, the enzyme particles having fast solubility have an elution rate of 70% or more and a dissolution rate of 85%.
The above enzyme particles are referred to. The dissolution rate corresponds to the time required for the enzyme to elute from the enzyme particles and exhibit its performance, and the dissolution rate corresponds to the degree of prevention of undissolved residue. Enzyme particles satisfying high-speed solubility are extremely preferable because not only the enzyme acts quickly, but also there is no undissolved residue.

【００３７】酵素の溶出率は次のようにして求めた。酵
素粒子１００ｍｇを１００ｍＬビーカー（内径１０５ｍ
ｍ）に取り、２０℃、硬度４゜ＤＨの水１００ｍＬを入
れてマグネチックスターラー（長さ３５ｍｍ、直径８ｍ
ｍ）（２００ｒ．ｐ．ｍ．）で攪拌し、酵素溶液を得
た。この酵素溶液について、式（１）で算出される値を
酵素の溶出率とした。 溶出率（％）＝〔Ａ×１００〕／Ｂ ・・・（１） Ａ：上記攪拌条件にて３０秒間攪拌して得られる酵素溶
液の酵素活性値 Ｂ：上記攪拌条件にて酵素溶液の酵素活性値を経時的に
測定していった場合に定常となったときの酵素活性値The elution rate of the enzyme was determined as follows. 100 mg of enzyme particles in a 100 mL beaker (105 m inner diameter)
m), put 100 mL of water having a temperature of 20 ° C. and a hardness of 4 ° DH, and add a magnetic stirrer (length 35 mm, diameter 8 m).
m) (200 rpm) to obtain an enzyme solution. With respect to this enzyme solution, the value calculated by the formula (1) was defined as the enzyme elution rate. Elution rate (%) = [A × 100] / B (1) A: Enzyme activity value of enzyme solution obtained by stirring for 30 seconds under the above stirring conditions B: Enzyme of enzyme solution under the above stirring conditions Enzyme activity value when it becomes steady when the activity value is measured over time

【００３８】尚、酵素活性値の測定方法についてはそれ
ぞれの酵素に適した測定方法を用いればよい。例えば、
セルラーゼの場合、次に示すＣＭＣ活性測定法を用いる
ことができる。２．５重量％カルボキシメチルセルロー
ス（ＣＭＣ）水溶液０．４ｍＬ、０．５Ｍグリシン緩衝
液（ｐＨ９．０）０．２ｍＬ、及び脱イオン水０．３ｍ
Ｌからなる基質溶液に、酵素溶液０．１ｍＬを加えて混
合し、該混合液を４０℃で２０分間保温した。次いで、
次に示す３，５−ジニトロサリチル酸（ＤＮＳ）法を利
用して還元糖の定量を行った。即ち、保温後の混合液１
ｍＬに対してＤＮＳ試薬１ｍＬを加え、５分間、１００
℃で加熱した。次いで冷却した後４ｍＬの脱イオン水を
該混合液に加えて希釈した。そして５３５ｎｍの吸光度
を測定して還元糖を定量した。この条件で測定した場合
において、１分間でグルコース換算で１μｍｏｌの還元
糖を遊離させる酵素量を１単位とした。As to the method for measuring the enzyme activity value, a method suitable for each enzyme may be used. For example,
In the case of cellulase, the following CMC activity measurement method can be used. 0.4 mL of 2.5% by weight carboxymethylcellulose (CMC) aqueous solution, 0.2 mL of 0.5 M glycine buffer (pH 9.0), and 0.3 m of deionized water
To the substrate solution consisting of L, 0.1 mL of the enzyme solution was added and mixed, and the mixture was kept at 40 ° C. for 20 minutes. Then
The reducing sugar was quantified using the following 3,5-dinitrosalicylic acid (DNS) method. That is, the mixture 1 after the heat retention
Add 1 mL of the DNS reagent to the mL, and add 100 mL for 5 minutes.
Heated at ° C. Then, after cooling, 4 mL of deionized water was added to the mixture to dilute it. The reducing sugar was quantified by measuring the absorbance at 535 nm. When measured under these conditions, the amount of enzyme that releases 1 μmol of reducing sugar in terms of glucose per minute was defined as one unit.

【００３９】また、プロテアーゼの場合、次に示すカゼ
イン法を用いることができる。カゼインを１重量％含む
５０ｍＭホウ酸−水酸化ナトリウム緩衝液（ｐＨ１０．
０）１ｍＬを０．１ｍＬの酵素溶液と混合し、４０℃で
１０分間保温した。次いで、この混合液に反応停止液
（０．１２３Ｍトリクロロ酢酸−０．２４６Ｍ酢酸ナト
リウム−０．３６９Ｍ酢酸）２ｍＬを加えて、３０℃で
２０分間保温した。次いで、この液を濾紙（ワットマン
社製、Ｎｏ．２）を用いて濾過し、濾液中のタンパク質
分解物を改良ファーリンローリー法によって測定した。
この条件で測定した場合において、１分間で１ｍｍｏｌ
のチロシンを遊離させる酵素量を１単位とした。In the case of a protease, the following casein method can be used. 50 mM boric acid-sodium hydroxide buffer solution containing 1% by weight of casein (pH 10.
0) 1 mL was mixed with 0.1 mL of the enzyme solution and kept at 40 ° C for 10 minutes. Next, 2 mL of a reaction stop solution (0.123 M trichloroacetic acid-0.246 M sodium acetate-0.369 M acetic acid) was added to the mixture, and the mixture was kept at 30 ° C. for 20 minutes. Next, this solution was filtered using a filter paper (manufactured by Whatman, No. 2), and the protein degradation product in the filtrate was measured by a modified Farin Lowry method.
When measured under these conditions, 1 mmol per minute
The amount of the enzyme that releases tyrosine was defined as 1 unit.

【００４０】酵素粒子の溶解率は次のようにして求め
た。５℃、硬度４゜ＤＨ の水１Ｌを１Ｌビーカー（内
径１０５ｍｍ）に取り、酵素粒子１ｇを入れてマグネチ
ックスターラー（長さ３５ｍｍ、直径８ｍｍ）（８００
ｒ．ｐ．ｍ．）で６０秒間攪拌した。得られた水溶液に
ついて、式（２）で算出される値を酵素粒子の溶解率と
した。 溶解率（％）＝｛１−（Ｄ／Ｃ）｝×１００ ・・・（２） Ｃ：酵素粒子の投入重量（ｇ） Ｄ：上記攪拌条件にて得られた水溶液をＪＩＳ Ｚ ８
８０１規定の標準篩（目開き７４μｍ）に供した後、篩
上に残存する酵素粒子の乾燥重量（ｇ） （乾燥条件：１０５℃の温度下に１時間保持した後、シ
リカゲルを入れたデシケータ（２５℃）内で３０分間保
持した。）The dissolution rate of the enzyme particles was determined as follows. 1 L of water having a temperature of 5 ° C. and a hardness of 4 ° DH is placed in a 1 L beaker (inside diameter: 105 mm), and 1 g of enzyme particles are put therein, and a magnetic stirrer (length: 35 mm, diameter: 8 mm) (800)
r. p. m. ) For 60 seconds. With respect to the obtained aqueous solution, the value calculated by the formula (2) was defined as the dissolution rate of the enzyme particles. Dissolution rate (%) = {1− (D / C)} × 100 (2) C: input weight of enzyme particles (g) D: aqueous solution obtained under the above stirring conditions is JIS Z8
After being passed through a standard 801 standard sieve (opening of 74 μm), the dry weight (g) of the enzyme particles remaining on the sieve (drying conditions: held at a temperature of 105 ° C. for 1 hour, and then placed in a desiccator containing silica gel ( (25 ° C.) for 30 minutes.)

【００４１】〔低発塵性〕本発明における低発塵性と
は、発塵量が１０００ｍｇ以下のものを言う。この発塵
量は低い値であることが望ましく、５００ｍｇ以下がよ
り好ましく、１００ｍｇ以下が更に好ましい。また、発
塵量の基準値は酵素の種類によっても変化する。例え
ば、人体に対する影響の強いプロテアーゼ等の発塵量は
１００ｍｇ以下が好ましく、２０ｍｇ以下がより好まし
い。発塵量とは、上方が収束した形状をもつ直径６．０
ｃｍの円筒中に直径２．０ｃｍ、重量３２．２ｇの粉砕
ボール１を４個内蔵し、粉砕ボールを回転数４４ｒ．
ｐ．ｍ．で回転させつつ、空気導入口３から空気排出口
４に向かって乾燥空気を２０Ｌ／ｍｉｎで通気して、気
流に同伴される粒子を上方収束部においてフィルター２
で捕集する回転式ダストメータに、酵素粒子２０ｇを入
れ、２０分間測定を行ったときの粉塵量とした。フィル
ター２は直径５．０ｃｍ、捕集粒径０．５μｍ、通気速
度５ｃｍ／ｓ時の圧力損失が０．４２ｋＰａのものを用
いた。測定に用いる回転式ダストメータは特に限定はさ
れないが、図１に示す構造を持つような回転式ダストメ
ータ、例えばホイバッハ社製ダストメーターＴＹＰＥ．
III を使用することができる。[Low dusting property] The low dusting property in the present invention means that the amount of dusting is 1000 mg or less. This dust generation amount is desirably a low value, more preferably 500 mg or less, and still more preferably 100 mg or less. In addition, the reference value of the amount of generated dust varies depending on the type of the enzyme. For example, the amount of dust generated by proteases and the like that strongly affect the human body is preferably 100 mg or less, and more preferably 20 mg or less. The amount of dust generation is a diameter 6.0 having a shape converging upward.
cm., four grinding balls 1 having a diameter of 2.0 cm and a weight of 32.2 g are incorporated in a cylinder having a diameter of 44 cm.
p. m. The dry air is passed through the air inlet 3 toward the air outlet 4 at a rate of 20 L / min while being rotated by the
20 g of the enzyme particles were placed in a rotary dust meter that was collected by the method described above, and the amount of dust was measured when measurement was performed for 20 minutes. The filter 2 used had a diameter of 5.0 cm, a trapped particle diameter of 0.5 μm, and a pressure loss of 0.42 kPa at a ventilation speed of 5 cm / s. The rotary dust meter used for the measurement is not particularly limited, but a rotary dust meter having a structure shown in FIG. 1, for example, a dust meter TYPE.
III can be used.

【００４２】〔平均粒径〕平均粒径はＪＩＳ Ｚ ８８
０１の標準篩を用いて５分間振動させた後、篩目のサイ
ズによる重量分率から求めた。[Average particle size] The average particle size is JIS Z88.
After shaking for 5 minutes using the standard sieve No. 01, the weight fraction was determined from the size of the sieve size.

【００４３】〔嵩密度〕嵩密度は、ＪＩＳ Ｋ ３３６
２により規定された方法で測定した。[Bulk density] The bulk density is determined according to JIS K336.
The measurement was carried out according to the method specified in 2.

【００４４】〔非分級性〕着色した酵素粒子６ｇを洗浄
剤組成物（平均粒径４００μｍ、嵩密度７５０ｇ／Ｌ）
５９４ｇと混合した後、容器（縦９ｃｍ、横１５ｃｍ、
高さ１１ｃｍ）に充填したのち、封をしてトラックの荷
台に乗せ１０００ｋｍの輸送を行った。その後、開封し
目視によって分級発生の有無を判断した。[Non-classifying property] 6 g of the colored enzyme particles were mixed with a detergent composition (average particle size: 400 μm, bulk density: 750 g / L).
After mixing with 594 g, the container (length 9 cm, width 15 cm,
(11 cm in height), sealed, put on a truck bed, and transported 1000 km. Thereafter, the package was opened and the presence or absence of classification was visually determined.

【００４５】〔染着性〕着色した酵素粒子０．１ｇを洗
浄剤組成物（平均粒径４００μｍ、嵩密度７５０ｇ／
Ｌ）１０ｇと混合した。、試験布（２５ｃｍ×１６ｃ
ｍ）をバットに広げ、２０℃、硬度４゜ＤＨの水をその
試験布が浸る程度までバットに注いだ。次いで、その試
験布上に、さらに別の試験布を重ね、布全体が浸る程度
までさらに水を静かに注いだ。その後室温を３０℃に維
持して一晩放置した。試験布の濯ぎを行った後、プレス
乾燥を行った。乾燥した試験布に染着しているかを目視
によって判断した。尚、試験布にはポリエステル及び木
綿を用いた。[Dyeing property] 0.1 g of the colored enzyme particles was added to a detergent composition (average particle diameter: 400 μm, bulk density: 750 g /
L) 10 g. , Test cloth (25cm × 16c
m) was spread over the bat, and water having a temperature of 20 ° C. and a hardness of 4 ° DH was poured into the bat until the test cloth was soaked. Then, another test cloth was placed on the test cloth, and water was gently poured into the test cloth until the whole cloth was soaked. Thereafter, the temperature was kept at 30 ° C. and the mixture was left overnight. After rinsing the test cloth, press drying was performed. It was visually determined whether or not the dyed test cloth had been dyed. In addition, polyester and cotton were used for the test cloth.

【００４６】実施例１ 表１に示す原料と水から固形分含有量５５重量％の噴霧
乾燥スラリーを調製した。加圧式のスプレーノズルを用
いて、噴霧圧２．５ＭＰａで噴霧乾燥スラリーを噴霧し
た。向流式の噴霧乾燥塔（直径３ｍ、塔高１０ｍ）に
て、送風量１００ｍ3 ／ｍｉｎ、送風温度１５０℃、ス
ラリー噴霧量２００ｋｇ／Ｈｒで噴霧乾燥を行った。得
られた粒子から篩を用いて１４１０μｍ以上の粒子を取
り除き、水分値４．２重量％の酵素粒子を得た。この酵
素粒子０．９６ｋｇを流動層（底面積０．１９ｍ2 、塔
高１ｍ）にて送風量６０ｍ3 ／Ｈｒ、送風温度６０℃に
て流動乾燥させつつ、２００ｇの水を１５ｇ／ｍｉｎの
速度で粉体層上部から噴霧し、噴霧終了後１０分間乾燥
させ、酵素粒子凝集体を得た。尚、表１におけるセルラ
ーゼは、特開平６−３４３４６１号公報記載のアルカリ
セルラーゼであり、また、プロテアーゼは、特開平５−
２５４９２号公報記載のアルカリプロテアーゼＫ−１６
である。糖類としてはマルトリッチ（昭和産業（株）
製、ＭＲ−２５）を用いた。Example 1 A spray-dried slurry having a solid content of 55% by weight was prepared from the raw materials and water shown in Table 1. The spray-dried slurry was sprayed at a spray pressure of 2.5 MPa using a pressurized spray nozzle. Spray-drying was carried out in a countercurrent spray-drying tower (diameter: 3 m, tower height: 10 m) at a blowing rate of 100 m 3 / min, a blowing temperature of 150 ° C., and a slurry spray rate of 200 kg / Hr. Using a sieve, particles having a particle size of 1410 μm or more were removed from the obtained particles to obtain enzyme particles having a water content of 4.2% by weight. While 0.96 kg of the enzyme particles are fluidized and dried at a blowing rate of 60 m 3 / Hr and a blowing temperature of 60 ° C. in a fluidized bed (bottom area: 0.19 m 2 , tower height: 1 m), 200 g of water is flowed at a rate of 15 g / min. And sprayed from the upper part of the powder layer, and dried for 10 minutes after the spraying was completed to obtain an enzyme particle aggregate. The cellulase in Table 1 is an alkaline cellulase described in JP-A-6-343461.
No. 25492, Alkaline protease K-16
It is. Maltrich (Showa Sangyo Co., Ltd.)
And MR-25).

【００４７】[0047]

【表１】 [Table 1]

【００４８】実施例２ 実施例１の酵素粒子０．９６ｋｇ、流動層（同装置、同
条件）を用い、流動乾燥させつつ、ポリエチレングリコ
ール（分子量６０００）４０ｇを１６０ｇの水に溶解さ
せた水溶液を１５ｇ／ｍｉｎの速度で粉体層上部から噴
霧し、噴霧終了後１０分間乾燥させた後常温まで冷却
し、酵素粒子凝集体を得た。Example 2 An aqueous solution obtained by dissolving 40 g of polyethylene glycol (molecular weight: 6000) in 160 g of water while flowing and drying using 0.96 kg of the enzyme particles of Example 1 and a fluidized bed (same apparatus under the same conditions) was used. It was sprayed from the upper part of the powder layer at a rate of 15 g / min, dried for 10 minutes after the spraying was completed, and then cooled to room temperature to obtain an enzyme particle aggregate.

【００４９】実施例３ 実施例１の酵素粒子０．９６ｋｇ、流動層（同装置、同
条件）を用い、流動させつつ、ポリエチレングリコール
（分子量６０００）４０ｇを８０℃に昇温し溶融状態と
なった液を３ｇ／ｍｉｎの速度で粉体層上部から噴霧
し、噴霧終了後常温まで冷却し、酵素粒子凝集体を得
た。EXAMPLE 3 0.96 kg of the enzyme particles of Example 1 and 40 g of polyethylene glycol (molecular weight: 6000) were heated to 80.degree. The sprayed liquid was sprayed from the upper part of the powder layer at a rate of 3 g / min. After the spraying was completed, the solution was cooled to room temperature to obtain an enzyme particle aggregate.

【００５０】実施例４ 表１に示す原料と水から固形分含有量５０重量％の噴霧
乾燥スラリーを調製した。スラリー噴霧量を１８０ｋｇ
／Ｈｒとし、それ以外の条件については実施例１と同条
件にて噴霧乾燥を行った。次いで、篩を用いて１４１０
μｍ以上の粒子を取り除き、水分値４．５重量％の酵素
粒子を得た。得られた酵素粒子０．９５ｋｇを流動層
（底面積０．１９ｍ2 、塔高１ｍ）にて送風量６０ｍ3
／Ｈｒ、送風温度６０℃にて流動乾燥させつつ、ポリエ
チレングリコール（分子量６０００）５０ｇを１１７ｇ
の水に溶解させた水溶液を１０ｇ／ｍｉｎの速度で粉体
層下部から噴霧し、噴霧終了後１０分間乾燥させ、酵素
粒子凝集体を得た。Example 4 A spray-dried slurry having a solid content of 50% by weight was prepared from the raw materials and water shown in Table 1. 180kg slurry spray amount
/ Hr and spray drying was performed under the same conditions as in Example 1. Then, using a sieve, 1410
Particles having a particle size of μm or more were removed to obtain enzyme particles having a water content of 4.5% by weight. 0.95 kg of the obtained enzyme particles was sent in a fluidized bed (bottom area: 0.19 m 2 , tower height: 1 m) at a blowing rate of 60 m 3.
/ Hr, 117 g of 50 g of polyethylene glycol (molecular weight: 6000) while fluid-drying at a blowing temperature of 60 ° C.
Was sprayed from the lower part of the powder layer at a rate of 10 g / min from the lower part of the powder layer, and dried for 10 minutes after the spraying was completed to obtain an enzyme particle aggregate.

【００５１】実施例５ 表１に示す原料と水から固形分含有量４５重量％の噴霧
乾燥スラリーを調製した。スラリー噴霧量を１６０ｋｇ
／Ｈｒとし、それ以外の条件については実施例１と同条
件にて噴霧乾燥を行った。次いで、篩を用いて１４１０
μｍ以上の粒子を取り除き、水分値３．４重量％の酵素
粒子を得た。得られた酵素粒子０．９５ｋｇを流動層
（底面積０．１９ｍ2 、塔高１ｍ）にて送風量６０ｍ3
／Ｈｒ、送風温度６０℃にて流動乾燥させつつ、ポリエ
チレングリコール（分子量６０００）５０ｇを２００ｇ
の水に溶解させた水溶液を１５ｇ／ｍｉｎの速度で粉体
層上部から噴霧し、噴霧終了後１０分間乾燥させ、酵素
粒子凝集体を得た。Example 5 A spray-dried slurry having a solid content of 45% by weight was prepared from the raw materials and water shown in Table 1. 160kg slurry spray amount
/ Hr and spray drying was performed under the same conditions as in Example 1. Then, using a sieve, 1410
Particles having a particle size of μm or more were removed to obtain enzyme particles having a water content of 3.4% by weight. 0.95 kg of the obtained enzyme particles was sent in a fluidized bed (bottom area: 0.19 m 2 , tower height: 1 m) at a blowing rate of 60 m 3.
/ Hr, 200 g of 50 g of polyethylene glycol (molecular weight: 6000) while fluid-drying at a blowing temperature of 60 ° C.
Aqueous solution dissolved in water was sprayed from the upper part of the powder layer at a rate of 15 g / min, and dried for 10 minutes after the spraying was completed to obtain an enzyme particle aggregate.

【００５２】実施例６ 表１に示す原料と水から固形分含有量５５重量％の噴霧
乾燥スラリーを調製し、実施例１と同条件にて噴霧乾燥
を行った。次いで、篩を用いて１４１０μｍ以上の粒子
を取り除き、水分値４．３重量％の酵素粒子を得た。得
られた酵素粒子０．９５ｋｇを流動層（底面積０．１９
ｍ2 、塔高１ｍ）にて送風量６０ｍ3 ／Ｈｒ、送風温度
６０℃にて流動乾燥させつつ、ポリエチレングリコール
（分子量６０００）５０ｇを１１７ｇの水に溶解させた
水溶液を１０ｇ／ｍｉｎの速度で粉体層下部から噴霧
し、噴霧終了後１０分間乾燥させ、酵素粒子凝集体を得
た。Example 6 A spray-dried slurry having a solid content of 55% by weight was prepared from the raw materials and water shown in Table 1, and spray-dried under the same conditions as in Example 1. Next, particles having a size of 1410 μm or more were removed by using a sieve to obtain enzyme particles having a water content of 4.3% by weight. 0.95 kg of the obtained enzyme particles was placed in a fluidized bed (bottom area 0.19).
m 2, column high 1m) at the blast volume 60 m 3 / Hr, while fluidized drying at blast temperature 60 ° C., an aqueous solution prepared by dissolving polyethylene glycol (molecular weight 6000) 50 g of water 117g at a rate of 10 g / min It was sprayed from the lower part of the powder layer and dried for 10 minutes after the spraying was completed to obtain an enzyme particle aggregate.

【００５３】実施例１〜６において得られた酵素粒子凝
集体の溶出率、溶解率、平均粒径、嵩密度、発塵量、非
分級性を表２に示す。本発明品は、高速溶解性、発塵量
抑制、非分級性に優れた酵素粒子凝集体であった。これ
らの酵素粒子を前出のＦＴ−ＩＲ／ＰＡＳによって測定
したところ、すべての酵素粒子においてその内部より表
面近傍に（Ｂ）成分が多く存在するという偏在性が確認
された。実施例４のＦＴ−ＩＲ／ＰＡＳによる測定結果
を図２に示す。Table 2 shows the dissolution rate, dissolution rate, average particle size, bulk density, amount of dust generation, and non-classification of the enzyme particle aggregates obtained in Examples 1 to 6. The product of the present invention was an enzyme particle aggregate excellent in high-speed solubility, suppression of dust generation, and non-classification. When these enzyme particles were measured by the above-mentioned FT-IR / PAS, it was confirmed that all of the enzyme particles had the component (B) present nearer to the surface than inside the enzyme particles. FIG. 2 shows the measurement results of Example 4 by FT-IR / PAS.

【００５４】[0054]

【表２】 [Table 2]

【００５５】実施例７ 実施例２の組成においてスラリー中の固形分１００重量
部に対して、染料の青色１号を０．１重量部、スラリー
調製時に配合してスラリーを得た。該スラリーを実施例
２と同条件にて噴霧乾燥及び凝集操作を行い、青色に均
一に着色された酵素粒子凝集体を得た。得られた酵素粒
子凝集体の溶出率、溶解率、平均粒径、嵩密度、発塵
量、非分級性は、実施例２における酵素粒子凝集体のそ
れらとほぼ同じであった。この酵素粒子には染着性は見
られなかった。また、酵素粒子凝集体を洗剤組成物中に
配合して色移りを調べたところ、この酵素粒子凝集体に
は色移りも見られなかった。Example 7 In the composition of Example 2, 0.1 part by weight of the dye No. 1 of blue was added to 100 parts by weight of the solid content in the slurry at the time of preparing the slurry to obtain a slurry. The slurry was spray-dried and aggregated under the same conditions as in Example 2 to obtain an enzyme particle aggregate uniformly colored blue. The elution rate, dissolution rate, average particle size, bulk density, dust generation amount, and non-classification of the obtained enzyme particle aggregate were almost the same as those of the enzyme particle aggregate in Example 2. No dyeing property was observed in the enzyme particles. When the enzyme particle aggregate was blended in the detergent composition and color transfer was examined, no color transfer was observed in the enzyme particle aggregate.

【００５６】比較例１ 実施例１にて得られた凝集前の酵素粒子の溶出率、溶解
率、平均粒径、嵩密度、発塵量、非分級性を表２に示
す。Comparative Example 1 Table 2 shows the elution rate, dissolution rate, average particle size, bulk density, dust generation amount, and non-classification of the enzyme particles obtained in Example 1 before aggregation.

【００５７】比較例２ 実施例４にて得られた凝集前の酵素粒子の溶出率、溶解
率、平均粒径、嵩密度、発塵量、非分級性を表２に示
す。Comparative Example 2 Table 2 shows the elution rate, dissolution rate, average particle size, bulk density, amount of dust generation, and non-classification of the enzyme particles obtained in Example 4 before aggregation.

【００５８】比較例３ 実施例５にて得られた凝集前の酵素粒子の溶出率、溶解
率、平均粒径、嵩密度、発塵量、非分級性を表２に示
す。Comparative Example 3 Table 2 shows the elution rate, dissolution rate, average particle size, bulk density, amount of dust generation, and non-classification of the enzyme particles obtained in Example 5 before aggregation.

【００５９】比較例４ 実施例６にて得られた凝集前の酵素粒子の溶出率、溶解
率、平均粒径、嵩密度、発塵量、非分級性を表２に示
す。Comparative Example 4 Table 2 shows the elution rate, dissolution rate, average particle size, bulk density, dust generation amount, and non-classification of the enzyme particles obtained in Example 6 before aggregation.

【００６０】[0060]

【発明の効果】本発明により、高速溶解性、発塵抑制、
非分級性等の効果を有する酵素粒子凝集体が提供され
る。According to the present invention, high-speed dissolution, suppression of dust generation,
An enzyme particle aggregate having an effect such as non-classification is provided.

【図面の簡単な説明】[Brief description of the drawings]

【図１】図１は、本発明において発塵量の測定に用いる
回転式ダストメータの概略構成図である。図１の上図は
正面図を、下図はＡ−Ａ線断面図をそれぞれ示す。FIG. 1 is a schematic configuration diagram of a rotary dust meter used for measuring a dust generation amount in the present invention. The upper diagram of FIG. 1 shows a front view, and the lower diagram shows a cross-sectional view taken along line AA.

【図２】図２は、実施例４で得られた酵素粒子のＦＴ−
ＩＲ／ＰＡＳによる測定結果を示す図である。細線はそ
のままの状態の酵素粒子のデータであり、太線は均一に
すりつぶした状態の酵素粒子のデータである。FIG. 2 is a graph showing the FT-activity of the enzyme particles obtained in Example 4.
It is a figure showing the measurement result by IR / PAS. The thin line is the data of the enzyme particles in the as-is state, and the thick line is the data of the enzyme particles in the uniformly ground state.

【符号の説明】[Explanation of symbols]

１ 粉砕ボール ２ フィルター ３ 空気導入口 ４ 空気排出口 ５ 回転軸 DESCRIPTION OF SYMBOLS 1 Grinding ball 2 Filter 3 Air inlet 4 Air outlet 5 Rotary shaft

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ１１Ｄ 17/06 Ｃ１１Ｄ 17/06 (72)発明者 塚原 逸朗 和歌山市湊1334番地 花王株式会社研究所 内 (72)発明者 山下 博之 和歌山市湊1334番地 花王株式会社研究所 内 Ｆターム(参考） 4H003 BA09 DA01 EA12 EA28 EB30 EB36 EB41 EC02 EC03 FA32 FA40 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI theme coat ゛ (Reference) C11D 17/06 C11D 17/06 (72) Inventor Itsuro Tsukahara 1334 Minato, Wakayama 72) Inventor Hiroyuki Yamashita 1334 Minato, Wakayama-shi Kao Research Laboratory F-term (reference) 4H003 BA09 DA01 EA12 EA28 EB30 EB36 EB41 EC02 EC03 FA32 FA40

Claims (6)

【特許請求の範囲】[Claims] 【請求項１】 水不溶性物質及び／又は水難溶性物質
（Ａ）、水溶性バインダー（Ｂ）、及び酵素（Ｃ）を含
有し、且つ内部よりも表面近傍に前記（Ｂ）成分が多く
存在する構造を有する酵素粒子を含有する酵素粒子凝集
体。1. A composition comprising a water-insoluble substance and / or a poorly water-soluble substance (A), a water-soluble binder (B), and an enzyme (C), and the component (B) is present more in the vicinity of the surface than in the interior. An enzyme particle aggregate containing an enzyme particle having a structure. 【請求項２】 平均粒径が１５０〜２０００μｍである
請求項１記載の酵素粒子凝集体。2. The enzyme particle aggregate according to claim 1, wherein the average particle size is 150 to 2000 μm. 【請求項３】 酵素粒子の平均粒径が１００〜５００μ
ｍである請求項１又は２記載の酵素粒子凝集体。3. An enzyme particle having an average particle size of 100 to 500 μm.
3. The enzyme particle aggregate according to claim 1, wherein m is m. 【請求項４】 染料で着色されてなる請求項１〜３いず
れか記載の酵素粒子凝集体。4. The enzyme particle aggregate according to claim 1, which is colored with a dye. 【請求項５】 酵素粒子が染料で着色されてなる請求項
１〜４いずれか記載の酵素粒子凝集体。5. The enzyme particle aggregate according to claim 1, wherein the enzyme particles are colored with a dye. 【請求項６】 水不溶性物質及び／又は水難溶性物質
（Ａ）、水溶性バインダー（Ｂ）、及び酵素（Ｃ）を含
有し、且つ内部よりも表面近傍に前記（Ｂ）成分が多く
存在する構造を有する酵素粒子に、水若しくはバインダ
ー水溶液を添加して乾燥及び／又は冷却することによ
り、又は溶融した熱可塑性バインダーを添加して冷却す
ることにより酵素粒子凝集体を得る、酵素粒子凝集体の
製法。6. It contains a water-insoluble substance and / or a poorly water-soluble substance (A), a water-soluble binder (B), and an enzyme (C), and the component (B) is present more in the vicinity of the surface than in the inside. An enzyme particle aggregate obtained by adding water or a binder aqueous solution to an enzyme particle having a structure and drying and / or cooling, or by adding a molten thermoplastic binder and cooling to obtain an enzyme particle aggregate. Manufacturing method.
JP31066499A 1999-06-15 1999-11-01 Enzyme particle aggregate Expired - Fee Related JP3514677B2 (en)

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JP16784099 1999-06-15
JP31066499A JP3514677B2 (en) 1999-06-15 1999-11-01 Enzyme particle aggregate

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009540858A (en) * 2006-07-07 2009-11-26 ザ プロクター アンド ギャンブル カンパニー Detergent composition
US7740412B2 (en) 2005-01-28 2010-06-22 S.C. Johnson & Son, Inc. Method of cleaning using a device with a liquid reservoir and replaceable non-woven pad
US7891898B2 (en) 2005-01-28 2011-02-22 S.C. Johnson & Son, Inc. Cleaning pad for wet, damp or dry cleaning
US7976235B2 (en) 2005-01-28 2011-07-12 S.C. Johnson & Son, Inc. Cleaning kit including duster and spray
US8893347B2 (en) 2007-02-06 2014-11-25 S.C. Johnson & Son, Inc. Cleaning or dusting pad with attachment member holder
US8999912B2 (en) 2007-07-09 2015-04-07 The Procter & Gamble Company Detergent compositions

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7740412B2 (en) 2005-01-28 2010-06-22 S.C. Johnson & Son, Inc. Method of cleaning using a device with a liquid reservoir and replaceable non-woven pad
US7891898B2 (en) 2005-01-28 2011-02-22 S.C. Johnson & Son, Inc. Cleaning pad for wet, damp or dry cleaning
US7976235B2 (en) 2005-01-28 2011-07-12 S.C. Johnson & Son, Inc. Cleaning kit including duster and spray
US8657515B2 (en) 2005-01-28 2014-02-25 S.C. Johnson & Son, Inc. Cleaning kit including duster and spray
JP2009540858A (en) * 2006-07-07 2009-11-26 ザ プロクター アンド ギャンブル カンパニー Detergent composition
US8893347B2 (en) 2007-02-06 2014-11-25 S.C. Johnson & Son, Inc. Cleaning or dusting pad with attachment member holder
US8999912B2 (en) 2007-07-09 2015-04-07 The Procter & Gamble Company Detergent compositions

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