JP2615274B2 - Antibacterial calcium carbonate powder - Google Patents

Antibacterial calcium carbonate powder

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Publication number
JP2615274B2
JP2615274B2 JP8579891A JP8579891A JP2615274B2 JP 2615274 B2 JP2615274 B2 JP 2615274B2 JP 8579891 A JP8579891 A JP 8579891A JP 8579891 A JP8579891 A JP 8579891A JP 2615274 B2 JP2615274 B2 JP 2615274B2
Authority
JP
Japan
Prior art keywords
calcium carbonate
antibacterial
suspension
carbonate powder
silver
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.)
Expired - Lifetime
Application number
JP8579891A
Other languages
Japanese (ja)
Other versions
JPH0717803A (en
Inventor
亮吾 築坂
聰 近藤
孝 伊永
央朗 森田
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.)
Shiraishi Central Laboratories Co Ltd
Original Assignee
Shiraishi Central Laboratories Co Ltd
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Filing date
Publication date
Application filed by Shiraishi Central Laboratories Co Ltd filed Critical Shiraishi Central Laboratories Co Ltd
Priority to JP8579891A priority Critical patent/JP2615274B2/en
Publication of JPH0717803A publication Critical patent/JPH0717803A/en
Application granted granted Critical
Publication of JP2615274B2 publication Critical patent/JP2615274B2/en
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Expired - Lifetime legal-status Critical Current

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Description

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

【0001】[0001]

【産業上の利用分野】本発明は抗菌性を有する炭酸カル
シウム粉体に関する。本願発明の炭酸カルシウム粉体
は、無機および有機の各種媒体に配合することにより、
抗菌性の要求される多くの用途の製品を提供するもので
ある。
The present invention relates to a calcium carbonate powder having antibacterial properties. The calcium carbonate powder of the present invention, by being mixed with various inorganic and organic media,
It is intended to provide products for many applications requiring antibacterial properties.

【0002】[0002]

【従来の技術】銀、銅、亜鉛などの金属化合物が抗菌性
を示すことは古くから知られており、例えば硝酸銀溶液
は消毒剤や殺菌剤として広く利用されてきた。これら殺
菌性を示す金属化合物を各種無機担体に固着させたもの
として、例えば活性炭に銀化合物を固着させた銀活性炭
が知られている(特開昭49−61950)。さらに近年になっ
て、材料、工業製品などに細菌やカビなどの微生物によ
る被害が増大しており、これらを防ぐために抗菌性金属
を付着させた種々の抗菌剤が出現してきている。例え
ば、Ti, Mg, Alなどの酸化物担体に塩化銀を付着させた
抗菌性組成物(特開昭63−88109)、ゼオライトにそのイ
オン交換反応を利用して抗菌性金属成分を保持させた抗
菌性組成物(特開昭59−133235)、および酸化チタンの
表面に抗菌性金属を無電解メッキ法などにより付着させ
た抗菌性組成物(特開平2−6333)などが特許出願され
ている。
2. Description of the Related Art It has long been known that metal compounds such as silver, copper, and zinc exhibit antibacterial properties. For example, silver nitrate solutions have been widely used as disinfectants and disinfectants. A silver activated carbon in which a silver compound is adhered to activated carbon, for example, is known as one in which these metal compounds exhibiting bactericidal properties are fixed to various inorganic carriers (JP-A-49-61950). Further, in recent years, materials, industrial products, and the like have been increasingly damaged by microorganisms such as bacteria and fungi, and various antibacterial agents to which antibacterial metals have been attached to prevent such damage have appeared. For example, an antibacterial composition in which silver chloride is adhered to an oxide carrier such as Ti, Mg, Al or the like (JP-A-63-88109), and an antibacterial metal component is retained in zeolite by utilizing its ion exchange reaction. Patent applications have been filed for antibacterial compositions (JP-A-59-133235) and antibacterial compositions in which an antibacterial metal is deposited on the surface of titanium oxide by electroless plating or the like (JP-A-2-6333). .

【0003】[0003]

【発明が解決しようとする問題点】前述したような従来
の無機系の担体を用いた抗菌剤は銀活性炭を除いてその
殆どが他の素材、例えば、ゴム、プラスチック、塗料、
インキ、シーラントと複合化して使用されるため、これ
らを応用した製品の抗菌性、外観、物性等に悪影響を及
ぼさないことが重要である。しかしながら、従来の無機
系抗菌剤には、 銀活性炭は黒色顆粒状のため、利用範囲が限定され
る; 酸化チタンあるいはアルミナを担体として、塩化銀
や無電解メッキによって抗菌性金属を付着させたもの
は、 イ)抗菌性成分が担体粒子表面より離脱し易い; ロ)抗菌性成分の担体への保持が、単なる両者の付着に
よっているに過ぎないので、抗菌性成分の担持量に限界
がある; ハ)担体となる粒子の粒径コントロールが技術的に困難
である; ニ)ゴム、プラスチック、塗料、インキ、シーラント等
の媒体への分散が十分でない; ホ)酸化チタンの持つ隠蔽性のため塗布品や成形品の調
色性が損われる;などの欠点のために所望の製品を得難
い。 ゼオライトにイオン交換反応により抗菌性金属成分
を保持させた抗菌性ゼオライトは、前記の媒体に配合さ
れた場合、ゴムやプラスチックに配合されるその他の添
加薬品と容易に化学反応を起し、成形品の黒変や抗菌効
果の低下が起り易い; 等の欠点があり、その改善が望まれている。
Most of the antibacterial agents using the conventional inorganic carrier as described above, except for silver activated carbon, are mostly made of other materials such as rubber, plastic, paint,
Since it is used in combination with an ink or a sealant, it is important that the antibacterial property, appearance, physical properties, etc. of a product to which these are applied have no adverse effect. However, conventional inorganic antibacterial agents include silver activated carbon, which has black granules, so its use is limited. Antibacterial metal adhered by silver chloride or electroless plating using titanium oxide or alumina as a carrier B) the antimicrobial component is easily detached from the surface of the carrier particles; b) the amount of the antimicrobial component carried is limited because the retention of the antimicrobial component on the carrier is merely due to the adhesion between the two; C) It is technically difficult to control the particle size of the carrier particles; d) Insufficient dispersion in media such as rubber, plastics, paints, inks and sealants; e) Coating due to the concealing properties of titanium oxide It is difficult to obtain a desired product due to defects such as impaired toning of a product or a molded product. Antibacterial zeolite, in which zeolite retains an antibacterial metal component by an ion exchange reaction, when easily mixed with the above-mentioned medium, easily reacts with other additive chemicals mixed with rubber and plastics to form molded articles. Are liable to cause blackening and a decrease in the antibacterial effect; and their improvement is desired.

【0004】[0004]

【発明の目的】本発明の目的は、前述した従来技術の問
題点を解決し、優れた抗菌性を示す高嵩の抗菌性炭酸カ
ルシウム粉体を提供するとともに、この抗菌性粉末を各
種の媒体に配合することによって、好ましい外観や色調
の抗菌性製品を提供することである。
SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art and to provide a high-bulk antibacterial calcium carbonate powder exhibiting excellent antibacterial properties, and to provide the antibacterial powder with various media. The purpose of the present invention is to provide an antibacterial product having a favorable appearance and color tone by blending the antibacterial product.

【0005】[0005]

【問題点を解決するための手段】炭酸カルシウムは元
来、ゴム、プラスチック、紙、塗料、シーラントなど、
多くの分野で使用されている汎用充填剤であり、前記媒
体への配合技術もすでに確立されているため、本発明の
抗菌性炭酸カルシウム粉体は、これら媒体への適用が容
易である。また、担体としての炭酸カルシウムは、製造
技術の進歩によって、製造条件をコントロールすること
により粒度や粒形の調節、さらには多孔質化等による高
嵩のものも製造可能になり、用途に応じて最適なものを
任意に選択できる。
[Means to solve the problem] Calcium carbonate is originally made of rubber, plastic, paper, paint, sealant, etc.
The antibacterial calcium carbonate powder of the present invention can be easily applied to these media because it is a general-purpose filler used in many fields, and the technology for blending it into the medium has already been established. In addition, calcium carbonate as a carrier, by the progress of manufacturing technology, by controlling the manufacturing conditions, the particle size and particle shape can be adjusted, and even a bulky material such as porous can be manufactured, depending on the application. The best one can be selected arbitrarily.

【0006】本発明者らは、炭酸カルシウム粉末の複合
素材としての高付加価値化等について研究を進めるう
ち、抗菌性無機粉体の担体として高嵩の炭酸カルシウム
粉体を適用することに着目した。そして種々検討を進め
た結果、化粧品原料基準一般試験の比容積測定法による
比容積が 1.5ml/g以上、水銀圧入法による空隙容積が
1.0ml/g以上、BET法による比表面積が8m2/g以
上である要件を満たした高嵩炭酸カルシウム粉体は、連
鎖状の微細炭酸カルシウム粒子がビード状に凝集して出
来た多孔質構造をしていることが電子顕微鏡写真によっ
てわかり(〔図1〕,〔図3〕参照)その構造を利用し
て、粒子の内部細孔とその粒子表面の凹凸部分に抗菌性
付与物質を保持させたところ、抗菌性、付着保持性に優
れ、抗菌性付与物質の溶出性コントロールと持続性を高
めることができ、さらに、前記したような各種媒体に配
合することによって、抗菌性製品の好ましい外観や色調
が得られることの知見を得た。そして、本発明の抗菌性
炭酸カルシウム粉体の比容積、空隙容積、比表面積は原
料の高嵩炭酸カルシウム粉体のものと同一であり、ま
た、水銀圧入式ポロシメーターにより測定した平均空隙
径は0.1 μm、その分布範囲は0.01〜0.5 μmであっ
た。
The inventors of the present invention have focused on applying high-bulk calcium carbonate powder as a carrier for an antibacterial inorganic powder, while conducting research on increasing the value of calcium carbonate powder as a composite material. . As a result of various studies, the specific volume was 1.5 ml / g or more based on the specific volume measurement method of the Cosmetic Ingredients Standard Test, and the void volume was
A high-bulk calcium carbonate powder satisfying the requirement that the specific surface area is 1.0 ml / g or more and the specific surface area by the BET method is 8 m 2 / g or more has a porous structure formed by agglomeration of chain-like fine calcium carbonate particles into beads. (See FIGS. 1 and 3) By using the structure, the antimicrobial substance is retained in the internal pores of the particles and the irregularities on the surface of the particles. However, the antibacterial properties, excellent adhesion retention, can improve the dissolution control and persistence of the antibacterial property imparting substance, further, by blending in various media as described above, the preferred appearance and antibacterial product The knowledge that color tone can be obtained was obtained. The specific volume, void volume and specific surface area of the antibacterial calcium carbonate powder of the present invention are the same as those of the raw material high bulk calcium carbonate powder, and the average pore diameter measured by a mercury intrusion porosimeter is 0.1. μm, and the distribution range was 0.01 to 0.5 μm.

【0007】前記粉体性質の要件を満たさない炭酸カル
シウム粉体、例えば重質炭酸カルシウムは、炭酸カルシ
ウム粒子表面への抗菌性付与物質の付着性が乏しく、そ
の電子顕微鏡写真からわかるように(〔図2〕,〔図
5〕参照)、複合粉体中に不均質な状態で抗菌性付与物
質が分布し、その抗菌効果が有効に発揮されない。すな
わち、本発明の抗菌性炭酸カルシウム粉体は、公知の水
酸化カルシウム水懸濁液と炭酸ガスとにより炭酸化して
得られる高嵩炭酸カルシウムを抗菌性付与物質で改質し
てなるものであり、前記高嵩炭酸カルシウムの炭酸化
途中の水懸濁液、または炭酸化終了後の水懸濁液、さ
らには炭酸化終了後脱水、乾燥、粉砕して炭酸カルシ
ウム粉体に仕上げたものを再水懸濁液としたもの等に抗
菌性付与物質を複合化する何れかの方法によって得られ
る。
[0007] Calcium carbonate powder which does not satisfy the above-mentioned requirements for powder properties, for example, heavy calcium carbonate, has poor adhesion of an antibacterial substance to the surface of calcium carbonate particles. 2), [FIG. 5]), the antimicrobial-imparting substance is distributed in a heterogeneous state in the composite powder, and the antimicrobial effect is not effectively exhibited. That is, the antibacterial calcium carbonate powder of the present invention is obtained by modifying a high-bulk calcium carbonate obtained by carbonation with a known aqueous solution of calcium hydroxide and carbon dioxide with an antibacterial substance. An aqueous suspension during the carbonation of the high-bulk calcium carbonate or an aqueous suspension after the completion of carbonation, and further, after the completion of the carbonation, dehydrated, dried and pulverized to finish the calcium carbonate powder. It can be obtained by any method in which an antibacterial substance is compounded with an aqueous suspension or the like.

【0008】このようにして得られた本発明の抗菌性炭
酸カルシウム粉体は、その多孔質構造内に抗菌性金属を
保持するので、従来の炭酸カルシウム粉末や酸化チタン
粉末と比較して、より多量の金属を保持することがで
き、また、金属の放出が徐々に行われるので、抗菌作用
が長期にわたって維持される。本発明において当該抗菌
性炭酸カルシウム粉体に複合化される抗菌性付与物質と
しては、銀、銅、亜鉛の金属、およびそれら金属の水不
溶性化合物から選ばれるいずれかのもの、例えば当該金
属の酸化物、水酸化物、ハロゲン化物、炭酸塩およびピ
ロリン酸塩等であり、前記炭酸カルシウム粉体の製造方
法,およびのいずれかの方法で、次のイ),ロ)
またはハ)のいずれかの方法により、抗菌性付与物質が
添加される。
[0008] The antibacterial calcium carbonate powder of the present invention thus obtained retains an antibacterial metal in its porous structure, so that it has a greater effect than conventional calcium carbonate powder or titanium oxide powder. Since a large amount of metal can be retained and the metal is gradually released, the antibacterial action is maintained for a long time. In the present invention, the antibacterial property-imparting substance complexed to the antibacterial calcium carbonate powder is a metal selected from the group consisting of silver, copper, and zinc, and water-insoluble compounds of these metals, for example, oxidation of the metal. , Hydroxides, halides, carbonates, pyrophosphates, etc., according to any one of the above-mentioned methods for producing calcium carbonate powder, and
Alternatively, the antibacterial property-imparting substance is added by any one of the methods (c) and (c).

【0009】イ)当該抗菌性金属の水可溶性塩水溶液を
,あるいはのいずれかの方法で、炭酸カルシウム
水懸濁液に添加後、金属の沈殿剤水溶液を先の添加工程
に続いて添加し、炭酸カルシウム懸濁液中で抗菌性付与
物質としての当該金属の水不溶性化合物沈殿を析出さ
せ、保持させる方法;
A) After adding the water-soluble salt aqueous solution of the antibacterial metal to the aqueous calcium carbonate suspension by any one of the following methods, an aqueous solution of the metal precipitant is added following the previous addition step; A method of precipitating and retaining a water-insoluble compound precipitate of the metal as an antibacterial agent in a suspension of calcium carbonate;

【0010】ロ)当該抗菌性金属の水可溶性塩水溶液と
当該抗菌性金属の沈殿剤水溶液を混合して、予め当該金
属の水不溶性化合物を沈殿析出させた後、前記,あ
るいはのいずれかの方法で該沈殿を炭酸カルシウム水
懸濁液に添加し保持させる方法;
(B) An aqueous solution of a water-soluble salt of the antimicrobial metal and an aqueous solution of a precipitant of the antimicrobial metal are mixed to previously precipitate a water-insoluble compound of the metal, and then any one of the above-mentioned methods or Adding the precipitate to an aqueous calcium carbonate suspension and keeping the precipitate;

【0011】ハ)抗菌性金属の水可溶性塩水溶液を、前
記の方法炭酸化途中の水懸濁液に添加し、当該抗菌性
金属イオンを共在させた状態で炭酸化して、炭酸カルシ
ウムと当該抗菌性金属炭酸塩との共晶を含む炭酸カルシ
ウムを得る方法。 また、イ)およびロ)の方法で製造された抗菌性炭酸カ
ルシウム粉体を、更に炭酸カルシウムの分解温度以下で
焼成するか、還元雰囲気中に曝らすことによって、当該
金属の還元金属を保持させることもできる。
(C) An aqueous solution of a water-soluble salt of an antibacterial metal is added to the aqueous suspension in the course of carbonation in the above-described method, and carbonation is carried out in the presence of the antibacterial metal ion, thereby obtaining calcium carbonate and the calcium carbonate. A method for obtaining calcium carbonate containing a eutectic with an antibacterial metal carbonate. Further, the antibacterial calcium carbonate powder produced by the methods a) and b) is further calcined at a temperature lower than the decomposition temperature of calcium carbonate or exposed to a reducing atmosphere to retain the reduced metal of the metal. It can also be done.

【0012】前期製造方法によって得られた抗菌性炭酸
カルシウム粉体は、微粒子の炭酸カルシウムと微粒子の
当該金属あるいはその水不溶性化合物、またさらには当
該金属との共晶粒子とからなる、抗菌性を有する高嵩多
孔質粒子である。前記の抗菌性金属の水可溶性塩として
は、硝酸銀、硝酸銅、酢酸銅、塩化銅、硫酸銅、酢酸亜
鉛、臭化亜鉛、塩化亜鉛、ヨウ化亜鉛、硝酸亜鉛、硫酸
亜鉛等が挙げられる。また、前記の沈殿剤としては、炭
酸カリウム、炭酸ナトリウム、水酸化カリウム、水酸化
ナトリウム、水酸化カルシウム、水酸化グネシウム等
のアルカリ剤 ピロリン酸ナトリウムおよび水可溶性の
塩素、臭素、ヨウ素化合物等のハロゲン化物等が挙げら
れる。
The antibacterial calcium carbonate powder obtained by the above-mentioned production method has an antibacterial property comprising fine particles of calcium carbonate and fine particles of the metal or a water-insoluble compound thereof, and furthermore, eutectic particles of the metal. High bulk porous particles. Examples of the water-soluble salt of the antibacterial metal include silver nitrate, copper nitrate, copper acetate, copper chloride, copper sulfate, zinc acetate, zinc bromide, zinc chloride, zinc iodide, zinc nitrate, and zinc sulfate. Further, examples of the precipitating agent, potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, calcium hydroxide, alkali agents, sodium pyrophosphate and water-soluble chlorine such as hydroxide magnesium, bromine, such as iodine compounds Halides and the like.

【0013】前記の抗菌性炭酸カルシウム粉体に含まれ
る抗菌性付与物質の割合は、抗菌性炭酸カルシウムの重
量に対して、金属分として 0.001〜10.0重量%、好まし
くは0.01〜5.0 重量%である。含有量が前記範囲の 0.0
01重量%より少な過ぎると抗菌効果が期待できず、ま
た、前記範囲の10.0重量%より多過ぎると分散性、色調
性などが損なわれ易くなり、コスト的にも不利である。
The proportion of the antibacterial substance imparted to the antibacterial calcium carbonate powder is 0.001 to 10.0% by weight, preferably 0.01 to 5.0% by weight, as a metal component, based on the weight of the antibacterial calcium carbonate. . The content is 0.0
If the amount is less than 01% by weight, an antibacterial effect cannot be expected. If the amount is more than 10.0% by weight in the above range, dispersibility, color tone and the like are liable to be impaired, which is disadvantageous in cost.

【0014】本発明の抗菌性炭酸カルシウム粉体は、各
種菌類の抗菌に対して有用なものであり、飲料水の浄水
材として使用した場合には抗菌作用とカルシウムイオン
補給という両面で役立つものである。前記菌類としては
一般細菌、種々のグラム陽性菌、グラム陰性菌等の細菌
類、真菌類等が挙げられ、本発明の抗菌性炭酸カルシウ
ム粉体はこれらの菌類に対して優れた抗菌能を示す。
The antibacterial calcium carbonate powder of the present invention is useful for antibacterial activity of various fungi, and when used as a water purifying material for drinking water, is useful for both antibacterial activity and calcium ion replenishment. is there. Examples of the fungi include general bacteria, various gram-positive bacteria, bacteria such as gram-negative bacteria, fungi, and the like, and the antibacterial calcium carbonate powder of the present invention exhibits excellent antibacterial activity against these fungi. .

【0015】[0015]

【発明の効果】本発明の抗菌性炭酸カルシウム粉体は長
期間にわたって優れた抗菌作用を有し、無機および有機
の各種媒体へ配合することにより、例えば浄水器、空調
器などのフィルター材、床材、壁材、タイルの目地材、
シーリング材、塗料、切削油、配水パイプ、電気洗濯機
材、トイレタリー製品、食品用器材、医療用品、包装
紙、プラスチックフィルム等へ防細菌、防カビ、防藻、
さらには飲料水の浄水材としての利用では抗菌作用とカ
ルシウムイオン補給を目的として衣食住全般に渡って利
用することができて、極めて有用な抗菌製品である。
The antibacterial calcium carbonate powder of the present invention has an excellent antibacterial action over a long period of time, and can be mixed with various inorganic and organic media to produce, for example, filter materials for water purifiers and air conditioners, floors, etc. Materials, wall materials, tile joint materials,
Sealing materials, paints, cutting oils, water distribution pipes, electric washing equipment, toiletry products, food equipment, medical supplies, wrapping paper, plastic films, etc.
Furthermore, when used as a water purification material for drinking water, it can be used throughout the clothing, food and shelter for the purpose of antibacterial action and calcium ion supplementation, and is a very useful antibacterial product.

【0016】[0016]

【実施例】以下に、実施例および比較例によって本発明
を更に具体的に説明する。なお、下記において、部およ
び%は特に明示しない限り、重量部および重量%を示
す。 実施例1
The present invention will be described more specifically below with reference to examples and comparative examples. In the following, parts and% indicate parts by weight and% by weight, respectively, unless otherwise specified. Example 1

【0017】濃度5wt%、温度30℃に調整した水酸化カ
ルシウム水懸濁液(石灰乳)1000kgを反応容器に入れ、
これに濃度10wt%に調製したニトリロトリ酢酸ナトリウ
ム水溶液 3.5kgを加えて混合してから、濃度30v%の炭
酸ガスを水酸化カルシウム1kg当り流速35l/分で吹込
み、炭酸化率80%まで炭酸化する。次いで濃度10wt%に
調製したニトリロトリ酢酸ナトリウム水溶液 1.5kgを加
えて、濃度30v%の炭酸ガスを水酸化カルシウム1kg当
り20l/分で吹込み、炭酸化反応を懸濁液のpHが7.0 と
なるまで行なった。この時点で、 0.1規定に調製した硝
酸銀水溶液337.5lと 0.2規定に調製した塩化ナトリウム
水溶液337.5lとを添加して、懸濁液中で塩化銀の沈殿を
析出させ、炭酸カルシウムと塩化銀との高嵩凝集粒子を
生成させた。この抗菌性炭酸カルシウム懸濁液はプレス
脱水機により母液を分離し、次いで乾燥、粉砕して、本
発明の抗菌性炭酸カルシウム粉体70kgを得た。 実施例2
1000 kg of a calcium hydroxide aqueous suspension (milk of lime) adjusted to a concentration of 5 wt% and a temperature of 30 ° C. is placed in a reaction vessel,
After adding and mixing 3.5 kg of an aqueous solution of sodium nitrilotriacetate adjusted to a concentration of 10 wt%, carbon dioxide gas having a concentration of 30 v% is blown at a flow rate of 35 l / min per kg of calcium hydroxide, and the carbonation rate is increased to 80%. I do. Then, 1.5 kg of an aqueous solution of sodium nitrilotriacetate adjusted to a concentration of 10 wt% is added, and carbon dioxide gas having a concentration of 30 v% is blown in at 20 l / min per 1 kg of calcium hydroxide. Done. At this point, 337.5 l of an aqueous solution of silver nitrate prepared in 0.1 N and 337.5 l of an aqueous solution of sodium chloride prepared in 0.2 N were added, and a precipitate of silver chloride was precipitated in the suspension. High bulk agglomerated particles were produced. The antibacterial calcium carbonate suspension was separated from the mother liquor by a press dehydrator, then dried and pulverized to obtain 70 kg of the antibacterial calcium carbonate powder of the present invention. Example 2

【0018】濃度7wt%、温度25℃に調整した水酸化カ
ルシウム水懸濁液(石灰乳)1000kgを反応容器に入れ、
これに濃度10wt%に調製したリンゴ酸ナトリウム水溶液
35kgを加え混合してから、濃度30容量%の炭酸ガスを水
酸化カルシウム1kg当り流速40l/分で吹込み、炭酸化
率88%まで炭酸化する。この時点で 0.1規定に調製した
硝酸銀水溶液47.3lを加えて混合し、炭酸カルシウム、
銀イオンおよび水酸化カルシウムの共存状態でさらに濃
度10重量%に調製したクエン酸水溶液14kgを加えて、濃
度30容量%の炭酸ガスを水酸化カルシウム1kg当り25l
/分で吹込み、炭酸化反応を懸濁液のpHが7.5 となるま
で行ない、炭酸カルシウムと炭酸銀との共晶粒子からな
る高嵩凝集粒子を生成させた。この抗菌性炭酸カルシウ
ム懸濁液はプレス脱水機により母液を分離し、次いで乾
燥、粉砕して、本発明の抗菌性炭酸カルシウム粉体93kg
を得た。 実施例3
1000 kg of a calcium hydroxide aqueous suspension (milk of lime) adjusted to a concentration of 7 wt% and a temperature of 25 ° C. is placed in a reaction vessel,
Sodium malate aqueous solution adjusted to a concentration of 10 wt%
After adding and mixing 35 kg, carbon dioxide gas having a concentration of 30% by volume is blown in at a flow rate of 40 l / min per kg of calcium hydroxide to carbonate to a carbonation rate of 88%. At this time, 47.3 l of a 0.1 N aqueous silver nitrate solution was added and mixed, and calcium carbonate,
In the coexistence state of silver ion and calcium hydroxide, 14 kg of an aqueous citric acid solution further adjusted to a concentration of 10% by weight is added, and carbon dioxide gas having a concentration of 30% by volume is added in an amount of 25 l per kg of calcium hydroxide.
Per minute, and the carbonation reaction was carried out until the pH of the suspension became 7.5, thereby producing high bulk aggregated particles composed of eutectic particles of calcium carbonate and silver carbonate. This antibacterial calcium carbonate suspension was separated from the mother liquor by a press dehydrator, and then dried and pulverized to obtain 93 kg of the antibacterial calcium carbonate powder of the present invention.
I got Example 3

【0019】濃度15wt%、温度20℃に調整した水酸化カ
ルシウム水懸濁液(石灰乳)1000kgを反応容器に入れ、
これに濃度10wt%に調製したクエン酸水溶液 150kgを加
えて混合してから、濃度30v%の炭酸ガスを水酸化カル
シウム1kg当り流速80l/分で吹込み、炭酸化率93%ま
で炭酸化する。この時点で別の容器で予め混合して用意
しておいた 0.1規定に調製した硝酸銀水溶液1013lと
0.2規定に調製した塩化ナトリウム水溶液1013lとの混
合によて析出した塩化銀の沈殿を含む懸濁液の全量を化
合中の懸濁液中に添加し、混合する。次いで濃度10重量
%に調製したイミノジ酢酸ナトリウム水溶液を45kg加え
て、濃度30容量%の炭酸ガスを水酸化カルシウム1kg当
り20l/分で吹込み、炭酸化反応を懸濁液のpHが8.2 と
なるまで行ない、炭酸カルシウムと塩化銀との高嵩凝集
粒子を生成させた。この抗菌性炭酸カルシウム懸濁液は
プレス脱水機により母液を分離し、次いで乾燥、粉砕し
て、本発明の抗菌性炭酸化カルシウム粉体 210kgを得
た。 実施例4
1000 kg of an aqueous suspension of calcium hydroxide (milk of lime) adjusted to a concentration of 15 wt% and a temperature of 20 ° C. is placed in a reaction vessel,
After adding and mixing 150 kg of a citric acid aqueous solution adjusted to a concentration of 10 wt%, carbon dioxide gas having a concentration of 30 v% is blown in at a flow rate of 80 l / min per kg of calcium hydroxide to carbonate to a carbonation rate of 93%. At this time, it was mixed with 1013 l of a 0.1 N aqueous silver nitrate solution prepared in advance by mixing in another container.
The entire amount of the suspension containing the silver chloride precipitate precipitated by mixing with 1013 l of a 0.2 N aqueous sodium chloride solution is added to the suspension during compounding and mixed. Next, 45 kg of an aqueous solution of sodium iminodiacetate adjusted to a concentration of 10% by weight was added, and carbon dioxide gas having a concentration of 30% by volume was blown in at a rate of 20 l / min per kg of calcium hydroxide. To produce high bulk aggregated particles of calcium carbonate and silver chloride. The antibacterial calcium carbonate suspension was separated from the mother liquor by a press dehydrator, then dried and pulverized to obtain 210 kg of the antibacterial calcium carbonate powder of the present invention. Example 4

【0020】濃度7wt%、温度33℃に調整した水酸化カ
ルシウム水懸濁液(石灰乳)1000kgを反応容器に入れ、
これに濃度10wt%に調製したエチレンジアミン四酢酸・
ニナトリウム塩水溶液21kgを加えて混合してから、濃度
30v%の炭酸ガスを水酸化カルシウム1kg当り流速50l
/分で吹込み、炭酸化率78%まで炭酸化し、この時点
で、 0.1規定に調製した硝酸銀水溶液 236lと 0.2規定
に調製した水酸化ナトリウム水溶液 118lとを添加し
て、懸濁液中で水和酸化銀の沈殿を析出させる。次いで
濃度10wt%に調製したトリポリリン酸ナトリウム水溶液
7kgを加え、濃度30v%の炭酸ガスを水酸化カルシウム
1kg当り15l/分で吹込み、炭酸化反応を懸濁液のpHが
8.0 となるまで行ない、炭酸カルシウムと水和酸化銀と
の高嵩凝集粒子を生成させた。この抗菌性炭酸カルシウ
ム懸濁液はプレス脱水機により母液を分離し、次いで乾
燥、粉砕して、本発明の抗菌性炭酸化カルシウム粉体95
kgを得た。 実施例5
1000 kg of a calcium hydroxide aqueous suspension (milk of lime) adjusted to a concentration of 7 wt% and a temperature of 33 ° C. is placed in a reaction vessel,
Ethylenediaminetetraacetic acid adjusted to a concentration of 10 wt%
Add 21 kg of disodium salt aqueous solution and mix.
30 v% carbon dioxide gas flow rate 50 l per kg of calcium hydroxide
At a carbonation rate of 78%. At this point, 236 liters of a 0.1 N aqueous silver nitrate solution and 118 liters of a 0.2 normal aqueous sodium hydroxide solution were added, and water was added to the suspension. A precipitate of silver oxide is deposited. Next, 7 kg of an aqueous solution of sodium tripolyphosphate adjusted to a concentration of 10 wt% was added, and carbon dioxide gas having a concentration of 30 v% was blown in at a rate of 15 l / min per 1 kg of calcium hydroxide, and the pH of the suspension was adjusted to the carbonation reaction.
8.0 until high bulk agglomerated particles of calcium carbonate and hydrated silver oxide were formed. This antibacterial calcium carbonate suspension was separated from the mother liquor by a press dehydrator, then dried and pulverized to obtain the antibacterial calcium carbonate powder 95 of the present invention.
kg gained. Example 5

【0021】濃度5wt%、温度30℃に調整した水酸化カ
ルシウム水懸濁液(石灰乳)1000kgを反応容器に入れ、
これに濃度10wt%に調製したニトリロトリ酢酸ナトリウ
ム水溶液 3.5kgを加えて混合してから、濃度30v%の炭
酸ガスを水酸化カルシウム1kg当り流速35l/分で吹込
み、炭酸化率80%まで炭酸化する。次いで濃度10wt%に
調製したリトリロトリ酢酸ナトリウム水溶液 1.5kgを加
えて、濃度30v%の炭酸ガスを水酸化カルシウム1kg当
り20l/分の吹込み、炭酸化反応を懸濁液のpHが7.0 と
なるまで行なった。この時点で、 0.1規定に調製した硫
酸銅水溶液 266lと 0.2規定に調製した水酸化ナトリウ
ム水溶液 266lとを添加して、懸濁液中で水酸化銅の沈
殿を析出させ、炭酸カルシウムと水酸化銅との高嵩凝集
粒子を生成させた。この炭酸カルシウム懸濁液はプレス
脱水機により母液を分離し、次いで乾燥、粉砕して、本
発明の抗菌性炭酸化カルシウム粉体65kgを得た。 実施例6
1000 kg of a calcium hydroxide aqueous suspension (milk of lime) adjusted to a concentration of 5 wt% and a temperature of 30 ° C. is placed in a reaction vessel,
After adding and mixing 3.5 kg of an aqueous solution of sodium nitrilotriacetate at a concentration of 10 wt%, carbon dioxide gas having a concentration of 30 v% was blown in at a flow rate of 35 l / min per kg of calcium hydroxide, and the carbonation rate was increased to 80%. I do. Subsequently, 1.5 kg of an aqueous solution of sodium ritrilotriacetate adjusted to a concentration of 10 wt% is added, and carbon dioxide gas having a concentration of 30 v% is blown in at 20 l / min per kg of calcium hydroxide, and the carbonation reaction is performed until the pH of the suspension becomes 7.0. Done. At this time, 266 l of a 0.1 N aqueous copper sulfate solution and 266 l of a 0.2 N aqueous sodium hydroxide solution were added to precipitate copper hydroxide precipitate in the suspension, and calcium carbonate and copper hydroxide were added. And high bulk aggregated particles were produced. The mother liquor was separated from the calcium carbonate suspension by a press dehydrator, and then dried and pulverized to obtain 65 kg of the antibacterial calcium carbonate powder of the present invention. Example 6

【0022】下記参考例1で得た結晶核炭酸カルシウム
を濃度5%で含有し、温度20℃に調整した水懸濁液1400
kgを撹拌機付容器に入れ、これに濃度 7.5%、温度20℃
に調整した水酸カルシウム水懸濁液 293kg(上記結晶核
炭酸カルシウム 100部当りCa(OH)2 として31部)を加
え、撹拌、混合し水懸濁液を得る。次いで、該水懸濁液
を炭酸ガス反応器に入れ、液温20〜25℃で、濃度30容量
%炭酸ガス含有気体を毎分 250lとなる流速で吹込み、
反応混合物のpHが7.0 なるまで炭酸化反応を行なった。
この時点で、 0.1規定に調製した硫酸亜鉛水溶液1525l
と 0.2規定に調製した水酸化ナトリウム水溶液1525lと
を添加して、懸濁液中で水酸化亜鉛の沈殿を析出させ、
炭酸カルシウムと水酸化亜鉛との高嵩凝集粒子を生成さ
せた。この炭酸カルシウム懸濁液はプレス脱水機により
母液を分離し、次いで乾燥、粉砕して、本発明の抗菌性
炭酸カルシウム粉体 112kgを得た。 参考例1
An aqueous suspension 1400 containing the crystal core calcium carbonate obtained in the following Reference Example 1 at a concentration of 5% and adjusted to a temperature of 20 ° C.
kg into a vessel equipped with a stirrer, into which a concentration of 7.5% and a temperature of 20 ° C
293 kg (31 parts of Ca (OH) 2 per 100 parts of the above-mentioned crystal nucleus calcium carbonate) is added, stirred and mixed to obtain an aqueous suspension. Next, the aqueous suspension was put into a carbon dioxide gas reactor, and a gas containing 30% by volume of carbon dioxide was blown at a flow rate of 250 l / min at a liquid temperature of 20 to 25 ° C.
Carbonation reaction was carried out until the pH of the reaction mixture reached 7.0.
At this point, 1525 l of an aqueous solution of zinc sulfate prepared at 0.1 N
And 1525 l of an aqueous sodium hydroxide solution prepared at 0.2 N were added to precipitate zinc hydroxide in the suspension,
High bulk aggregated particles of calcium carbonate and zinc hydroxide were produced. This calcium carbonate suspension was separated into mother liquor by a press dehydrator, then dried and pulverized to obtain 112 kg of the antibacterial calcium carbonate powder of the present invention. Reference Example 1

【0023】濃度20重量%、温度20℃に調整した水酸化
カルシウム水懸濁液1000kgを反応容器に入れ、これに塩
化ストロンチウムを水酸化カルシウム1モル当り0.03モ
ルの割合で添加し、炭酸ガス濃度30容量%の炭酸ガス含
有気体を、水酸化カルシウム1kg当り毎分30lとなるよ
うな流速で導入して炭酸化反応を行ない、アラゴナイト
針柱状炭酸カルシウム結晶含量95重量%の結晶核炭酸カ
ルシウム 270kgを得た。
1000 kg of an aqueous suspension of calcium hydroxide adjusted to a concentration of 20% by weight and a temperature of 20 ° C. was placed in a reaction vessel, and strontium chloride was added thereto at a ratio of 0.03 mol per mol of calcium hydroxide. Carbonation gas containing 30% by volume of carbon dioxide gas was introduced at a flow rate of 30 l / min per 1 kg of calcium hydroxide to carry out a carbonation reaction, and 270 kg of aragonite needle columnar calcium carbonate crystal content of 270 kg of crystal nucleus calcium carbonate having a content of 95 wt% was obtained. Obtained.

【0024】電子顕微鏡観察によれば、上記結晶核炭酸
カルシウム中に含まれているアラゴナイト質針柱状炭酸
カルシウム結晶の寸法は、長径 0.5〜1.0 μm、短径0.
05〜0.1 μm、アスペクト比5〜20であった。 実施例7 ユニバー70(高嵩炭酸カルシウム、白石工業製品)粉体
100kgと水 400kgとを撹拌機付の容器に入れ、撹拌混合
して20%の炭酸カルシウム水懸濁液を準備した。次い
で、該水懸濁液中に撹拌しながら 0.1規定に調製した硝
酸銀水溶液47.3lと 0.1規制に調製した硫酸亜鉛水溶液
152.5l、 0.2規定に調製した水酸化ナトリウム水溶液
176lとを添加して、懸濁液中で水和酸化銀と水酸化亜
鉛の沈殿を析出させ、炭酸カルシウムと水和酸化銀と水
酸化亜鉛との高嵩凝集体を生成させた。この抗菌性炭酸
カルシウム懸濁液はプレス脱水機により母液を分離し、
次いで乾燥、粉砕して、本発明の抗菌性炭酸カルシウム
粉体 100kgを得た。 実施例8
According to electron microscopic observation, the size of the aragonite needle-shaped columnar calcium carbonate crystal contained in the crystal nucleus calcium carbonate is 0.5 to 1.0 μm in the major axis and 0.5 in the minor axis.
05 to 0.1 μm, aspect ratio 5 to 20. Example 7 Univer 70 (high bulk calcium carbonate, Shiraishi industrial product) powder
100 kg and 400 kg of water were put in a container equipped with a stirrer, and mixed by stirring to prepare a 20% calcium carbonate aqueous suspension. Then, while stirring the aqueous suspension, 47.3 l of an aqueous solution of silver nitrate adjusted to 0.1 N and an aqueous solution of zinc sulfate adjusted to 0.1 regulation
152.5 l, 0.2N aqueous sodium hydroxide solution
176 l was added to precipitate a precipitate of hydrated silver oxide and zinc hydroxide in the suspension to form a high bulk aggregate of calcium carbonate, hydrated silver oxide and zinc hydroxide. This antibacterial calcium carbonate suspension separates mother liquor with a press dehydrator,
Then, it was dried and pulverized to obtain 100 kg of the antibacterial calcium carbonate powder of the present invention. Example 8

【0025】実施例4で得られた抗菌性炭酸カルシウム
粉体10kgを電気炉に入れ、 400℃で4時間焼成して、炭
酸カルシウム・水和酸化銀からなる複合体を還元して炭
酸カルシウム・銀複合体を生成させ、本発明の抗菌性炭
酸カルシウム粉体 9.9kgを得た。 比較例1 実施例1の製法に依るが、前記,およびのいずれ
かの方法においても、抗菌性金属化合物を添加しなかっ
た以外は実施1と同様にして、以下のようにして炭酸カ
ルシウム粉体を得た。
10 kg of the antibacterial calcium carbonate powder obtained in Example 4 was placed in an electric furnace and calcined at 400 ° C. for 4 hours to reduce a complex composed of calcium carbonate and hydrated silver oxide to obtain calcium carbonate. A silver complex was formed, and 9.9 kg of the antibacterial calcium carbonate powder of the present invention was obtained. Comparative Example 1 According to the production method of Example 1, calcium carbonate powder was produced in the same manner as in Example 1 except that the antibacterial metal compound was not added in either of the above methods and the following method. I got

【0026】濃度5wt%、温度30℃に調整した水酸化カ
ルシウム水懸濁液(石灰乳)1000kgを反応容器に入れ、
これに濃度10wt%に調製したニトリロトリ酢酸ナトリウ
ム水容器 3.5kgを加えて混合してから、濃度30v%の炭
酸ガスを水酸化カルシウム1kg当り流速35l/分で吹込
み、炭酸化率80%まで炭酸化する。次いで濃度10wt%に
調製したニトリロトリ酢酸ナトリウム筈溶液 1.5kgを加
えて、濃度30v%の炭酸ガスを水酸化カルシウム1kg当
り20l/分で吹込み、炭酸化反応を懸濁液のpHが7.0 と
なるまで行ない、高嵩凝集粒子を生成させた。この炭酸
カルシウム懸濁液はプレス脱水機により母液を分離し、
次いで乾燥、粉砕して、炭酸化カルシウム粉体65kgを得
た。 比較例2
In a reaction vessel, 1000 kg of a calcium hydroxide aqueous suspension (milk of lime) adjusted to a concentration of 5 wt% and a temperature of 30 ° C. is placed.
To this, 3.5 kg of an aqueous sodium nitrilotriacetate container adjusted to a concentration of 10 wt% was added and mixed, and then carbon dioxide gas having a concentration of 30 v% was blown in at a flow rate of 35 l / min per kg of calcium hydroxide, and the carbonation rate was increased to 80%. Become Then, 1.5 kg of a sodium nitrilotriacetate solution adjusted to a concentration of 10 wt% is added, and carbon dioxide gas having a concentration of 30 v% is blown in at 20 l / min per 1 kg of calcium hydroxide, so that the pH of the suspension in the carbonation reaction becomes 7.0. To produce high bulk aggregated particles. This calcium carbonate suspension separates mother liquor by a press dehydrator,
Then, it was dried and pulverized to obtain 65 kg of calcium carbonate powder. Comparative Example 2

【0027】天然の石灰石粉末(商品名、ホワイトンP
30、東洋ファインケミカル(株)製品)680gと水
道水9300gとを内容積301のステンレス製容器に
採取し、撹拌機で混合、撹拌して炭酸カルシウム懸濁液
とする。次いで撹拌を続けながら0.1規定に調整した
硝酸銀水液3.41と0.2規定に調整した塩化ナト
リウム水溶液3.41とを添加して、懸濁液中で塩化銀
の沈殿を析出させ、炭酸カルシウムと塩化銀とが混合し
た懸濁液とした後、この懸濁液をヌッチェで吸引濾過し
て分離し、次いで乾燥、粉砕して、抗菌性炭酸カルシウ
ム粉末690gを得た。 比較例3
Natural limestone powder (trade name, Whiten P
30, 680 g of Toyo Fine Chemical Co., Ltd.) and 9300 g of tap water are collected in a stainless steel container having an inner volume of 301, mixed with a stirrer and stirred to form a calcium carbonate suspension. Then added the aqueous sodium chloride solution 3.41 adjusted silver nitrate aqueous solvent solution 3.41 was adjusted to 0.1 N with continued stirring and the 0.2N, a precipitate of silver chloride in suspension Then, a suspension in which calcium carbonate and silver chloride were mixed was formed. The suspension was separated by suction filtration with a Nutsche filter, and then dried and pulverized to obtain 690 g of antibacterial calcium carbonate powder. Comparative Example 3

【0028】軽微性炭酸カルシウム粉末(商品名;シル
バーW、白石工業製品) 680gと水道水9300gとを内容
積30lのステンレス製容器に採り、撹拌機で混合、撹拌
して炭酸カルシウム懸濁液とする。次いで、撹拌を続け
ながら 0.1規定に調製した硝酸銀水溶液 3.4lと 0.2規
定に調製した塩化ナトリウム水溶液 3.4lとを添加し
て、懸濁液中で塩化銀の沈殿を析出させ、炭酸カルシウ
ムと塩化銀とが混合した懸濁液とした後、この懸濁液を
ヌッチェで吸引濾過して分離し、次いで乾燥、粉砕し
て、抗菌性炭酸カルシウム粉末 695gを得た。以上の実
施例1〜8ならびに比較例1〜3で得た抗菌性炭酸カル
シウム粉末の抗菌金属含量(%)、石山式による嵩(ml
/g)、ポロシメーターによる空隙容積(ml/g)、B
ET比表面積(m2/g)および小倉法による吸油量(ml
/100g)の試験結果を表−1および表−2にまとめて示
す。
680 g of light calcium carbonate powder (trade name: Silver W, Shiraishi Kogyo) and 9300 g of tap water are placed in a 30-liter stainless steel container, mixed with a stirrer and stirred to form a calcium carbonate suspension. I do. Then, while stirring, 3.4 l of an aqueous solution of silver nitrate prepared in 0.1 N and 3.4 l of an aqueous solution of sodium chloride prepared in 0.2 N were added to precipitate silver chloride in the suspension, and calcium carbonate and silver chloride were added. After the suspension was separated by suction filtration with a Nutsche, then dried and pulverized to obtain 695 g of antibacterial calcium carbonate powder. The antibacterial metal content (%) of the antibacterial calcium carbonate powder obtained in Examples 1 to 8 and Comparative Examples 1 to 3 and the bulk (ml) according to Ishiyama formula
/ G), Porosimeter void volume (ml / g), B
ET specific surface area (m 2 / g) and oil absorption by Ogura method (ml
/ 100 g) are summarized in Tables 1 and 2 .

【0029】[0029]

【表1】 [Table 1]

【0030】[0030]

【表1】 [Table 1]

【0031】このようにして得られた実施例1〜8で得
た抗菌性炭酸カルシウム粉体および比較例1〜3で得た
抗菌性金属無添加炭酸カルシウム粉体と抗菌性炭酸カル
シウム粉体について、それぞれ無機抗菌剤としての特性
を評価した。まず、各粉体について、以下の試験方法
(i)および(ii)により、一般細菌およびカビに対す
る抗菌能を調べた結果を表−に示す。表−から明ら
かなように、本発明に係る抗菌性炭酸カルシウム粉体の
実施例1〜8の抗菌性炭酸カルシウム粉体は、比較例の
1〜3の抗菌性金属無添加炭酸カルシウム粉体と抗菌性
炭酸カルシウム粉体に比べ、一般細菌およびカビに対す
る抗菌能が極めて優れたものであった。
The antibacterial calcium carbonate powder obtained in Examples 1 to 8 thus obtained, and the antibacterial metal-free calcium carbonate powder and antibacterial calcium carbonate powder obtained in Comparative Examples 1 to 3 The properties of each as an inorganic antibacterial agent were evaluated. First, the results of examining the antibacterial activity of each powder against general bacteria and mold by the following test methods (i) and (ii) are shown in Table- 3 . As is apparent from Table 3, the antibacterial calcium carbonate powders of Examples 1 to 8 of the antibacterial calcium carbonate powder according to the present invention are the antibacterial metal-free calcium carbonate powders of Comparative Examples 1 to 3. The antibacterial activity against general bacteria and mold was extremely excellent as compared with the antibacterial calcium carbonate powder.

【0032】[0032]

【表3】 [Table 3]

【0033】(i)抗細菌性試験方法:日本製薬(株)
製のSCDLP寒天培地(細菌用)を処方に従って溶解
した後、45℃に保温しながら一般雑菌を含む生活汚水を
溶解培地 100ml当り2ml添加した培地を準備する。内径
8.5cmのシャーレ中に実施例試料および比較例試料の各
々所定量を計りとり、そこへ上記の調製剤培地10mlを注
ぎ入れ、コンラージ棒でよくかぎ混ぜる。培地が固まっ
てからシャーレに蓋をし、裏返しにした状態で細菌を培
養(30℃×4日間)する。 (ii)抗カビ性試験方法:日本製薬(株)製のGPLP
寒天培地(真菌用)を処方に従って溶解後、45℃に保温
しながら、浴室内のカビから採取したカビ胞子懸濁水を
溶解培地 100ml当て2ml添加した培地を準備する。内径
8.5cmのシャーレ中に実施例試料および比較例試料を各
々所定量を計りとり、そこへ上記の調製済培地を注ぎ入
れ、コンラージ棒でよくかき混ぜる。培地が固まってか
らシャーレに蓋をし、裏返しにした状態でカビを培養
(30℃×4日間)する。
(I) Antibacterial test method : Nippon Pharmaceutical Co., Ltd.
After dissolving the SCDLP agar medium (for bacteria) manufactured according to the prescription, a medium is prepared by adding 2 ml of living sewage containing general bacteria per 100 ml of the lysis medium while keeping the temperature at 45 ° C. Inside diameter
A predetermined amount of each of the sample of the example and the sample of the comparative example is measured in an 8.5 cm petri dish, 10 ml of the above-mentioned preparation medium is poured into the dish, and mixed well with a conical rod. After the medium is solidified, the dish is covered with a lid, and the bacteria are cultured (30 ° C. × 4 days) in a state where the medium is turned over. (Ii) Antifungal test method : GPLP manufactured by Nippon Pharmaceutical Co., Ltd.
After dissolving the agar medium (for fungi) according to the prescription, while keeping the temperature at 45 ° C., a medium is prepared by adding 2 ml of the spore suspension water collected from the mold in the bathroom to 100 ml of the lysis medium. Inside diameter
A predetermined amount of each of the sample of the example and the sample of the comparative example is weighed in an 8.5 cm petri dish, and the prepared medium is poured into the sample and stirred well with a conical rod. After the medium has solidified, cover the petri dish and invert the mold to culture the mold (30 ° C. × 4 days).

【0034】次に、本発明に得られた実施例試料1およ
び比較例1〜2試料の粉体について、PP樹脂に配合し
たときの応用面での抗カビ能を、以下の試験方法(iii
)により調べた結果を表−に示す。表−から明ら
かなように、本発明に係る抗菌性炭酸カルシウム粉体P
P樹脂応用品の抗カビ能は極めて優れたものであった。
Next, the powdery resistance of the sample of Example 1 and Comparative Examples 1 and 2 obtained in the present invention was evaluated for the antifungal ability in terms of application when blended with PP resin by the following test method (iii).
Table 4 shows the results of the examination according to (1). As is apparent from Table 4, the antibacterial calcium carbonate powder P according to the present invention is used.
The antifungal ability of the P resin-applied product was extremely excellent.

【0035】[0035]

【表4】 [Table 4]

【0036】(iii )PP樹脂成形品の抗カビ性試験方
: イ)PP樹脂成形品試料(形状:板) 実施例1試料板:実施例1試料2%/PP樹脂配合品 比較例1 〃 :比較例1試料2%/PP樹脂配合品 〃 2 〃 : 〃 2 〃 /PP樹脂配合品 比較(ブランク):試料無添加PP樹脂 ロ)抗カビ性試験 試料の樹脂成形板をほうろうバットの底に並べ、その表
面の一部と周囲が浸るように(ii)の試験で準備したと
同じ方法により溶解GPLP寒天培地を調製して注ぎ入
れ、培地が固まってから通気性を持たせた状態で蓋を
し、4週間培養(湿度90%、温度30℃の室内)した。
(Iii) Test method for anti-mold property of PP resin molded product
Method : a) PP resin molded product sample (shape: plate) Example 1 sample plate: Example 1 sample 2% / PP resin blended product Comparative Example 1 :: Comparative Example 1 sample 2% / PP resin blended product {2} : {2} / PP resin blended product Comparison (blank): PP resin without sample added b) Place the resin mold plate of the anti-mold test sample on the bottom of the enamel bat so that a part of the surface and the surroundings are immersed ( A dissolved GPLP agar medium was prepared and poured by the same method as that prepared in the test of ii), and after the medium was solidified, covered with air permeability, and cultured for 4 weeks (humidity 90%, temperature 30 ° C.) Indoors).

【0037】さらに、本発明で得られた実施例1試料お
よび比較例1試料の粉体について、浄水材用にビード状
成形体としたものを作製して、その抗菌効果を、以下の
試験方法(iv)により調べた結果を表−に示す。表−
から明らかなように、本発明に係る抗菌性炭酸カルシ
ウム粉体を応用した浄水材用ビードの示す抗菌効果は極
めて顕著であった。
Further, the powders of the sample of Example 1 and the sample of Comparative Example 1 obtained by the present invention were formed into a bead-shaped molded body for a water purification material, and the antibacterial effect was evaluated by the following test method. Table 5 shows the results of the examination according to (iv). Table-
As is clear from FIG. 5, the antibacterial effect of the bead for water purification material to which the antibacterial calcium carbonate powder according to the present invention was applied was extremely remarkable.

【0038】[0038]

【表5】 [Table 5]

【0039】(iv)浄水材用ビードの抗菌性試験方法 イ)ビードの作製 実施例1試料ビード:食品添加物用炭酸カルシウム(ポ
アカルーA、白石中央研究所K.K.製) 100重量部と
実施例1試料粉体 7.5重量部とアルギン酸ナトリウム2
重量部と水 300重量部から成る懸濁液を、カルシウムイ
オンを含む水浴中に滴下し、ビード状に固形化後、水
洗、乾燥し、径4mmのビードを得た。 比較例1試料ビード:実施例1試料粉体を比較例1試料
粉体に代える以外は、実施例1試料ビードと同じ様にし
て製造した。 ロ)抗菌性試験方法 日本製薬(株)製のGPLP寒天培地を処方に従って溶
解後、45℃に保温しながら、カビ胞子懸濁水と生活汚水
を溶解培地 100ml当りそれぞれ2mlを添加した培地を準
備する。内径 8.5cmのシャーレ中央にビード7個を並
べ、そこへビードが浸るように上記調製済培地を注ぎ入
れ、培地が固まってかたシャーレに蓋をし、30℃×4日
間は培養する。
(Iv) Test method for antibacterial activity of bead for water purification material a) Preparation of bead Example 1 Sample bead: 100 parts by weight of calcium carbonate for food additive (Poakalu A, manufactured by Shiraishi Central Research Institute KK) Example 1 7.5 parts by weight of sample powder and sodium alginate 2
A suspension composed of 300 parts by weight of water and 300 parts by weight of water was dropped into a water bath containing calcium ions, solidified into beads, washed with water and dried to obtain beads having a diameter of 4 mm. Comparative Example 1 Sample Bead: Example 1 was prepared in the same manner as the sample bead except that the sample powder was replaced with the sample powder of Comparative Example 1. B) Antibacterial test method After dissolving GPLP agar medium manufactured by Nippon Pharmaceutical Co., Ltd. according to the prescription, prepare a culture medium containing 2 ml of mold spore suspension water and domestic wastewater added to each 100 ml of lysis medium while keeping the temperature at 45 ° C. . Seven beads are arranged in the center of a Petri dish with an inner diameter of 8.5 cm, the prepared medium is poured into the Petri dish so that the beads are immersed therein, and the Petri dish where the medium solidifies is covered, and cultured at 30 ° C for 4 days.

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

【図1】本発明による抗菌性炭酸カルシウム粉体の粒子
構造を示す電子顕微鏡写真。
FIG. 1 is an electron micrograph showing the particle structure of an antibacterial calcium carbonate powder according to the present invention.

【図2】従来の炭酸カルシウム粉体の粒子構造を示す電
子顕微鏡写真。
FIG. 2 is an electron micrograph showing the particle structure of a conventional calcium carbonate powder.

【図3】本発明の実施例1で得られた抗菌性炭酸カルシ
ウム粉体の粒子構造を示す電顕写真。
FIG. 3 is an electron micrograph showing the particle structure of the antibacterial calcium carbonate powder obtained in Example 1 of the present invention.

【図4】本発明の実施例1試料表面のX線マイクロアナ
ライザー分析結果を示す図。
FIG. 4 is a view showing an X-ray microanalyzer analysis result of the sample surface of Example 1 of the present invention.

【図5】比較例2で得られた抗菌性炭酸カルシウム粉体
の粒子を示す電子顕微鏡写真。
FIG. 5 is an electron micrograph showing particles of the antibacterial calcium carbonate powder obtained in Comparative Example 2.

【図6】比較例2試料表面のX線マイクロアナライザー
分析結果を示す図。
FIG. 6 is a diagram showing an X-ray microanalyzer analysis result of a sample surface of Comparative Example 2;

Claims (2)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 銀、銅、亜鉛のいずれかの抗菌性を有す
る金属を含有し、かつ連鎖状の微細粒子がビード状に凝
集した多孔質構造を有し、比容積が 1.5ml/g以上、水
銀圧入法による空隙容積が 1.0ml/g以上、BET法に
よる比表面積が8m 2 /g以上であることを特徴とする
高嵩の抗菌性炭酸カルシウム抗菌剤。
An antibacterial property of any of silver, copper and zinc
Chained fine particles containing metal
Having a porous structure with a specific volume of 1.5 ml / g or more and water
The void volume by silver intrusion method is 1.0ml / g or more.
Characterized by having a specific surface area of at least 8 m 2 / g
High bulk antibacterial calcium carbonate antibacterial agent.
【請求項2】 連鎖状の微細粒子がビード状に凝集した
多孔質構造を有し、比容積が 1.0ml/g以上、BET法
による比表面積が8m 2 /g以上である高嵩の炭酸カル
シウム粉体に、銀、銅、亜鉛の金属およびこれらの金属
の水不溶性化合物から選ばれるいずれかを炭酸カルシウ
ム粉体の重量に対して、金属成分として0.001 〜10.0重
量%の量で、多孔質構造内に保持した炭酸カルシウム抗
菌剤。
2. A chain of fine particles aggregated in a bead shape.
BET method with porous structure, specific volume of 1.0ml / g or more
Bulk calcium carbonate with a specific surface area of at least 8 m 2 / g
Silver, copper, zinc metals and these metals
Any of the water-insoluble compounds of calcium carbonate
0.001 to 10.0 weight as metal component with respect to weight of powder
The amount of calcium carbonate contained in the porous structure
Fungicide.
JP8579891A 1991-03-27 1991-03-27 Antibacterial calcium carbonate powder Expired - Lifetime JP2615274B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP8579891A JP2615274B2 (en) 1991-03-27 1991-03-27 Antibacterial calcium carbonate powder

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP8579891A JP2615274B2 (en) 1991-03-27 1991-03-27 Antibacterial calcium carbonate powder

Publications (2)

Publication Number Publication Date
JPH0717803A JPH0717803A (en) 1995-01-20
JP2615274B2 true JP2615274B2 (en) 1997-05-28

Family

ID=13868904

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
JP (1) JP2615274B2 (en)

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