JPH0617037A - Cold storage agent composition - Google Patents

Cold storage agent composition

Info

Publication number
JPH0617037A
JPH0617037A JP4194894A JP19489492A JPH0617037A JP H0617037 A JPH0617037 A JP H0617037A JP 4194894 A JP4194894 A JP 4194894A JP 19489492 A JP19489492 A JP 19489492A JP H0617037 A JPH0617037 A JP H0617037A
Authority
JP
Japan
Prior art keywords
viscosity
water
aqueous solution
cellulose
cellulose ether
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.)
Pending
Application number
JP4194894A
Other languages
Japanese (ja)
Inventor
Kazuhisa Hayakawa
和久 早川
Masami Kawaguchi
正美 川口
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.)
Shin Etsu Chemical Co Ltd
Original Assignee
Shin Etsu Chemical Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Shin Etsu Chemical Co Ltd filed Critical Shin Etsu Chemical Co Ltd
Priority to JP4194894A priority Critical patent/JPH0617037A/en
Publication of JPH0617037A publication Critical patent/JPH0617037A/en
Pending legal-status Critical Current

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  • Medicinal Preparation (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE:To obtain a cold storage agent composition which is resistant to bacterial attack and can give an aqueous solution which is still highly viscous and behaves as a non-Newtonian fluid even when the amount of the constituent water-soluble cellulose ether problematic in storage stability is reduced. CONSTITUTION:The composition is prepared by adding 0.3-1wt.% water-soluble cellulose ether to a colloidal silica sol having a silica content of 10-40wt.% and a particle size of 100mum or below.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は医療分野における保冷、
生鮮食品の保冷、保存に使用する保冷剤組成物、とくに
は粘度安定性に優れた高粘性の保冷剤組成物に関する。
BACKGROUND OF THE INVENTION The present invention relates to cold storage in the medical field,
The present invention relates to a cold-preserving agent composition used for keeping cold and storing fresh food, and particularly to a highly viscous cold-preserving agent composition having excellent viscosity stability.

【0002】[0002]

【従来の技術】粘性のある水溶液をポリエチレン等の水
不溶性のプラスチック製袋に入れ、冷凍庫で凍結させた
ものが保冷剤として使用されている。この保冷剤は実質
的な性能が期待される5℃前後の温度域において保冷剤
溶液が適度な粘性を保ち、医療用としては保冷剤が適当
に患部に沿った形態に変化した後、その形状を概ね保ち
つつ患部の冷却効果を示すように、また生鮮食品にあっ
ては生鮮食品の形状もしくは生鮮食品容器の形状に沿っ
た形態で冷却効果を呈するように、工夫がなされてい
る。
2. Description of the Related Art A viscous aqueous solution placed in a water-insoluble plastic bag such as polyethylene and frozen in a freezer is used as a cooler. This ice pack has an appropriate viscosity in the ice pack solution in the temperature range of about 5 ° C where substantial performance is expected, and for medical use, the ice pack changes its shape appropriately along the affected area, and then its shape It is devised so that the cooling effect of the affected area is exhibited while maintaining the above-mentioned condition, and in the case of fresh food, the cooling effect is exhibited in the form of the shape of the fresh food or the shape of the fresh food container.

【0003】さらに、保冷剤は適当な粘性を持たせるこ
とによって、使用中もしくは使用後に保冷剤袋が万一損
傷しても内容物が一度に多量に漏れ出ないように工夫さ
れている。このような粘性を持つ保冷剤水溶液を調製す
るには、一般にポリビニルアルコール等の粘性を有する
水溶性ポリマーまたは吸水により粒子が肥大化して見掛
け上溶液に粘性のようなボリューム感を与える吸水ポリ
マーの微粒子が使用されている。
Further, the ice pack is designed so as to have an appropriate viscosity so that even if the ice pack bag is damaged during use or after use, a large amount of the contents will not leak out at once. In order to prepare an aqueous solution of a cooling agent having such a viscosity, generally, a water-soluble polymer having a viscosity such as polyvinyl alcohol or a particle of a water-absorbing polymer which gives a apparent volume-like feel to the solution due to water-absorbing polymer enlarges the particles. Is used.

【0004】しかしながら、これらのポリマーを添加し
て冷却し、実際の効能が期待される5℃前後の状態とし
た時に、必要な形状変化を行い、その形状維持に必要な
溶液流動性として500cps以上の粘度があり、僅かに非ニ
ュートン流動するような水溶液を調製しようとする場合
には、少なくとも各種ポリマーを1%以上混合する必要
があった。例えば、ポリビニルアルコールのように粘度
発現性の低い水溶性高分子の場合は十数%を超える濃度
にして使用しなければならず、また吸水ポリマーでは比
較的低添加量で使用時の所望の硬さに変化できるもの
の、本来の粘性のような流動性はなく、非ニュートン流
動性が見掛け上大きい流動性となるので、冷却しようと
する部分へのフィット性が悪いという問題があった。
However, when these polymers are added and cooled to be in a state of about 5 ° C. at which the actual efficacy is expected, a necessary shape change is performed, and the solution fluidity necessary for maintaining the shape is 500 cps or more. In order to prepare an aqueous solution having a viscosity of 7 and having a slight non-Newtonian flow, it was necessary to mix at least 1% or more of various polymers. For example, in the case of a water-soluble polymer having a low viscosity developing property such as polyvinyl alcohol, it is necessary to use it at a concentration of more than tens of percent, and for a water-absorbing polymer, a relatively low addition amount is required to obtain a desired hardness. However, since there is no fluidity such as the original viscosity and non-Newtonian fluidity is apparently large fluidity, there is a problem that the fitting property to the part to be cooled is poor.

【0005】これに対してカルボキシメチルセルロー
ス、メチルセルロース、ヒドロキシプロピルメチルセル
ロース、ヒドロキシエチルセルロース、ヒドロキシプロ
ピルセルロース、ヒドロキシエチルエチルセルロースな
どの水溶性セルロースエーテル類は、比較的低粘度で高
粘性が得られ、流動性の面でも優れた水溶性高分子とし
て使用され、とりわけカルボキシメチルセルロース等は
安価で、低濃度でも高粘性が発現するものとして使われ
ている。しかし、カルボキシメチルセルロース等の安価
な水溶性セルロースエーテルは、天然セルロースに対す
るエーテル置換度が低く、バクテリア等に侵され易く、
使用後の保冷剤を放置するとバクテリア等の作用で分解
されて粘性が低下するほか、カビ状物が発生する等の問
題があった。
On the other hand, water-soluble cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxypropylmethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose and hydroxyethyl ethyl cellulose have relatively low viscosities and high viscosities, and have a fluidity. However, it is used as an excellent water-soluble polymer. Particularly, carboxymethyl cellulose and the like are inexpensive and are used as those exhibiting high viscosity even at low concentration. However, inexpensive water-soluble cellulose ethers such as carboxymethyl cellulose have a low degree of ether substitution with respect to natural cellulose and are easily attacked by bacteria and the like,
If the cold insulator after use is left to stand, it is decomposed by the action of bacteria and the like to lower the viscosity, and there are problems such as generation of mold.

【0006】[0006]

【発明が解決しようとする課題】したがって、本発明の
目的は、保存安定性に問題のある水溶性セルロースエー
テルの使用量を節減してもなお、高い粘度を示すと共に
非ニュートン流動を行う水溶液が得られ、しかもバクテ
リア等に侵されることのない保冷剤組成物を提供しよう
とするものである。
SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an aqueous solution which exhibits a high viscosity and a non-Newtonian flow even when the amount of the water-soluble cellulose ether having a problem of storage stability is reduced. The present invention is intended to provide a cold-preserving composition which is obtained and is not attacked by bacteria and the like.

【0007】[0007]

【課題を解決するための手段】本発明者らは上記課題の
解決のため鋭意検討の結果、水溶性セルロース誘導体水
溶液に、粒子径 100μm 以下のコロイダルシリカを添加
した場合、粘性がセルロース誘導体の僅かな非ニュート
ン流動特性を維持しつつ水溶液の粘度を数倍以上に増加
できること、また、この系が5℃前後に冷却されると溶
液粘度が増加し、高粘性を発揮すること、保存安定性に
問題がある水溶性セルロースエーテル含有量を極力少な
くした保冷剤を得ることができ、保存安定性も向上でき
ることを見出し、本発明を完成した。
Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that when a colloidal silica having a particle diameter of 100 μm or less is added to an aqueous solution of a water-soluble cellulose derivative, the viscosity of the cellulose derivative is small. The viscosity of the aqueous solution can be increased more than several times while maintaining the excellent non-Newtonian flow characteristics. Also, when this system is cooled to around 5 ° C, the solution viscosity increases and exhibits a high viscosity, and storage stability is improved. The present invention has been completed based on the finding that a cold-preserving agent having a problematic water-soluble cellulose ether content as low as possible can be obtained and storage stability can be improved.

【0008】本発明に使用されるコロイダルシリカは、
例えばケイ酸ナトリウム成分を水中に水和させ、イオン
交換樹脂にて系を酸性とし、分散装置内で微量のアルカ
リ成分の添加によりゾルを安定化して、作られるような
シリカゾルを使用する。シリカが安定してゾルになって
いれば、本発明に使用するコロイダルシリカゾルとして
使用できるが、実際には1〜 100μm の粒径より細かい
シリカ粒子や細かい粒子を安定したゾルとして存在させ
ることは工業的に困難であり、本発明ではコロイダルシ
リカとして粒径1〜 100μm のものが使用される。コロ
イダルシリカの粒子濃度についても40重量%以上にする
と凝集を起こし易いので40重量%以下とし、セルロース
エーテルとの混合により必要な粘性を得るのに最低限必
要な濃度として10重量%以上のシリカ濃度が用いられ
る。
The colloidal silica used in the present invention is
For example, a silica sol is used in which a sodium silicate component is hydrated in water, the system is made acidic with an ion exchange resin, and the sol is stabilized by adding a trace amount of an alkaline component in a dispersing device. If the silica is a stable sol, it can be used as the colloidal silica sol used in the present invention. Actually, it is industrially necessary to make silica particles finer than 1 to 100 μm and fine particles exist as a stable sol. However, colloidal silica having a particle size of 1 to 100 μm is used in the present invention. The particle concentration of colloidal silica is 40% by weight or less because if it is 40% by weight or more, aggregation is likely to occur, and the minimum concentration required to obtain the required viscosity by mixing with cellulose ether is 10% by weight or more. Is used.

【0009】本発明で使用する水溶性セルロースエーテ
ルとしては、カルボキシメチルセルロース、メチルセル
ロース、ヒドロキシプロピルメチルセルロース、ヒドロ
キシエチルセルロース、ヒドロキシプロピルセルロー
ス、ヒドロキシエチルエチルセルロースなど、すべての
水溶性セルロースエーテルが対象となるが、これらはで
きるかぎり粘度の高い(すなわち、重合度が高い)もの
を用いるのが使用量を少なくする意味で好ましく、その
粘度としては2%水溶液の20℃における測定粘度で100c
ps以上のものが用いられる。また、セルロースエーテル
の添加量は極力少なくするのが望ましいが、一般には
0.3〜1重量%の範囲で使用するのが望ましい。
The water-soluble cellulose ether used in the present invention includes all water-soluble cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxyethyl ethyl cellulose, and the like. It is preferable to use as high viscosity as possible (that is, high degree of polymerization) in order to reduce the amount used, and the viscosity should be 100c as measured at 20 ° C in a 2% aqueous solution.
Those of ps or more are used. In addition, it is desirable to minimize the amount of cellulose ether added, but in general,
It is preferably used in the range of 0.3 to 1% by weight.

【0010】[0010]

【作用】水溶性セルロースエーテル溶液にコロイダルシ
リカが混合することで、その溶液粘度が増加し、溶液の
流動性も大きく変化しない作用を示す。機構としては水
溶性セルロースエーテル分子の一部がコロイダルシリカ
表面に吸着して、そこが架橋点のような状況となって粘
度を増すためと考えられる。実際に、このようにして増
粘したものにセルロースエーテルの脱着剤としてジオキ
サンを添加してみると、この溶液の粘度はほとんどコロ
イダルシリカを添加していない濃度のセルロースエーテ
ルの粘度になることからもコロイダルシリカに対するセ
ルロースエーテルの吸着が作用しているものと考えられ
る。
When the colloidal silica is mixed with the water-soluble cellulose ether solution, the solution viscosity is increased and the fluidity of the solution is not significantly changed. It is considered that the mechanism is that a part of the water-soluble cellulose ether molecule is adsorbed on the surface of the colloidal silica, and the state becomes a cross-linking point to increase the viscosity. Actually, when dioxane was added to the thus thickened product as a desorbent of cellulose ether, the viscosity of this solution was almost the same as that of cellulose ether at a concentration where colloidal silica was not added. It is considered that the adsorption of cellulose ether on the colloidal silica is acting.

【0011】[0011]

【実施例】以下、本発明の具体的態様を実施例および比
較例を挙げて説明するが、本発明はこれらの記載に限定
されるものではない。 実施例1〜7、比較例1〜5 表1に示す種類と量で、コロイダルシリカ(日産化学工
業社製、スノーテックス)溶液に、下記の水溶性セルロ
ース誘導体、水溶性ポリマーまたは吸水ポリマーを混合
して溶液を調製し、各溶液の20℃における粘度と5℃に
冷却したときの粘度と、20℃で2週間放置したときの当
初粘度からの粘度低下率(%)とを、B型回転粘度計に
よりローター No.4、回転数 30rpmで測定した。また、
各温度における粘度測定においてローター回転数を変え
て粘度を測定し、測定回転数に対する測定粘度値を両対
数グラフにプロットし、各点を結んだ直線の負の傾きを
tanθとして求めた。なお、 tanθが大きいほど測定溶
液の非ニュートン性が高く、冷却しようとする物に対す
るフィット感が悪くなる傾向にある。以上の結果を表1
に示した。
EXAMPLES Hereinafter, specific embodiments of the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to these descriptions. Examples 1 to 7 and Comparative Examples 1 to 5 In the types and amounts shown in Table 1, a colloidal silica (Nissan Chemical Co., Ltd. Snowtex) solution was mixed with the following water-soluble cellulose derivative, water-soluble polymer or water-absorbing polymer. To prepare solutions, and measure the viscosity of each solution at 20 ° C, the viscosity when cooled to 5 ° C, and the viscosity decrease rate (%) from the initial viscosity when left at 20 ° C for 2 weeks. It was measured with a viscometer at rotor No. 4 and a rotation speed of 30 rpm. Also,
In the viscosity measurement at each temperature, the rotor rotation speed was changed to measure the viscosity, and the measured viscosity value against the measurement rotation speed was plotted on a log-log graph, and the negative slope of the straight line connecting the points was calculated.
It was calculated as tan θ. It should be noted that the larger the tan θ, the higher the non-Newtonian property of the measurement solution and the worse the fit to the object to be cooled. The above results are shown in Table 1.
It was shown to.

【0012】なお、表中の略号は下記を意味する。 ・MC-1:メチルセルロース−1(信越化学工業社製、SM
-100、2%水溶液粘度:100cps) ・HPMC:ヒドロキシプロピルメチルセルロース(同前、
90SH-10万、2%水溶液粘度:100cps) ・HEMC:ヒドロキシエチルメチルセルロース(同前、 S
EB-30T、2%水溶液粘度:32000cps) ・CMC :カルボキシメチルセルロース(ダイセル化学工
業社製、2%水溶液粘度:8000cps ) ・HEC :ヒドロキシエチルセルロース(同前、SP-900、
2%水溶液粘度:85000cps) ・HPC :ヒドロキシプロピルセルロース(信越化学工業
社製、 M-P、2%水溶液粘度:6500cps ) ・HEEC:ヒドロキシエチルエチルセルロース(ベロール
社製、E481FQ、2%水溶液粘度:76500cps) ・PVA :ポリビニルアルコール(信越化学工業社製、 P
A20S) ・MC-2:メチルセルロース−2(同前、 SM-15、2%水
溶液粘度: 15cps) ・吸水ポリマー:アクリル酸ソーダ系重合体(住友化学
工業社製、スミカゲル N-100)
The abbreviations in the table mean the following.・ MC-1: Methylcellulose-1 (Shin-Etsu Chemical Co., Ltd., SM
-100, 2% aqueous solution viscosity: 100 cps ・ HPMC: hydroxypropylmethyl cellulose (same as above,
90SH-100,000, 2% aqueous solution viscosity: 100cps ・ HEMC: Hydroxyethylmethylcellulose (Same as above, S
EB-30T, 2% aqueous solution viscosity: 32000cps) -CMC: carboxymethyl cellulose (manufactured by Daicel Chemical Industries, 2% aqueous solution viscosity: 8000cps) -HEC: hydroxyethyl cellulose (same as above, SP-900,
2% aqueous solution viscosity: 85000cps) -HPC: hydroxypropylcellulose (Shin-Etsu Chemical Co., Ltd., MP, 2% aqueous solution viscosity: 6500cps) -HEEC: hydroxyethylethylcellulose (Berol, E481FQ, 2% aqueous solution viscosity: 76500cps)- PVA: Polyvinyl alcohol (Shin-Etsu Chemical Co., Ltd., P
A20S) ・ MC-2: Methylcellulose-2 (Same as above, SM-15, 2% aqueous solution viscosity: 15cps) ・ Water-absorbing polymer: Sodium acrylate polymer (Sumikagel N-100, manufactured by Sumitomo Chemical Co., Ltd.)

【0013】[0013]

【表1】 [Table 1]

【0014】[0014]

【発明の効果】本発明の保冷剤組成物によれば、溶液系
の非ニュートン性を大きくすることなく必要な粘度であ
る500cps以上が発現し、とくに低温度域において高粘性
を発揮すると共に、放置時の粘度低下も少なくできる。
EFFECTS OF THE INVENTION According to the cooling agent composition of the present invention, the required viscosity of 500 cps or more is developed without increasing the non-Newtonian property of the solution system, and in addition to exhibiting a high viscosity particularly in a low temperature range, It also reduces the decrease in viscosity when left standing.

Claims (2)

【特許請求の範囲】[Claims] 【請求項1】シリカ含有量が10〜40重量%で、粒子の大
きさが 100μm 以下のコロイダルシリカゾルに対して、
水溶性セルロースエーテルを 0.3〜1重量%添加してな
る保冷剤組成物。
1. A colloidal silica sol having a silica content of 10 to 40% by weight and a particle size of 100 μm or less,
A cooling agent composition comprising 0.3 to 1% by weight of a water-soluble cellulose ether.
【請求項2】水溶性セルロースエーテルが、2%水溶液
の20℃における測定粘度で100cps以上のものである請求
項1記載の保冷剤組成物。
2. The ice pack composition according to claim 1, wherein the water-soluble cellulose ether has a viscosity of 100 cps or more as measured at 20 ° C. in a 2% aqueous solution.
JP4194894A 1992-06-29 1992-06-29 Cold storage agent composition Pending JPH0617037A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP4194894A JPH0617037A (en) 1992-06-29 1992-06-29 Cold storage agent composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP4194894A JPH0617037A (en) 1992-06-29 1992-06-29 Cold storage agent composition

Publications (1)

Publication Number Publication Date
JPH0617037A true JPH0617037A (en) 1994-01-25

Family

ID=16332102

Family Applications (1)

Application Number Title Priority Date Filing Date
JP4194894A Pending JPH0617037A (en) 1992-06-29 1992-06-29 Cold storage agent composition

Country Status (1)

Country Link
JP (1) JPH0617037A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09208440A (en) * 1996-01-29 1997-08-12 Shin Etsu Chem Co Ltd Capsule of waterborne solution and production of the same
WO2021049833A1 (en) * 2019-09-11 2021-03-18 오씨아이 주식회사 Environment-friendly cold insulator composition and cold insulating pack comprising same
WO2023090698A1 (en) * 2021-11-18 2023-05-25 오씨아이 주식회사 Eco-friendly cold insulator composition and cold insulation pack comprising same
WO2023090696A1 (en) * 2021-11-18 2023-05-25 오씨아이 주식회사 Eco-friendly cold insulator composition and cold insulation pack comprising same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09208440A (en) * 1996-01-29 1997-08-12 Shin Etsu Chem Co Ltd Capsule of waterborne solution and production of the same
WO2021049833A1 (en) * 2019-09-11 2021-03-18 오씨아이 주식회사 Environment-friendly cold insulator composition and cold insulating pack comprising same
KR20210031575A (en) * 2019-09-11 2021-03-22 오씨아이 주식회사 Eco-friendly Cold insulation composition and cold insulation pack including the same
WO2023090698A1 (en) * 2021-11-18 2023-05-25 오씨아이 주식회사 Eco-friendly cold insulator composition and cold insulation pack comprising same
WO2023090696A1 (en) * 2021-11-18 2023-05-25 오씨아이 주식회사 Eco-friendly cold insulator composition and cold insulation pack comprising same

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