JPH05179053A - Water-absorbing resin - Google Patents

Water-absorbing resin

Info

Publication number
JPH05179053A
JPH05179053A JP35901291A JP35901291A JPH05179053A JP H05179053 A JPH05179053 A JP H05179053A JP 35901291 A JP35901291 A JP 35901291A JP 35901291 A JP35901291 A JP 35901291A JP H05179053 A JPH05179053 A JP H05179053A
Authority
JP
Japan
Prior art keywords
water
ion
absorbent resin
antibacterial
phosphate
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
JP35901291A
Other languages
Japanese (ja)
Other versions
JP2734852B2 (en
Inventor
Miyuki Yamada
みゆき 山田
Yukari Kato
ゆかり 加藤
Minoru Okada
岡田  稔
Hideki Kato
秀樹 加藤
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.)
Toagosei Co Ltd
Original Assignee
Toagosei 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 Toagosei Co Ltd filed Critical Toagosei Co Ltd
Priority to JP3359012A priority Critical patent/JP2734852B2/en
Publication of JPH05179053A publication Critical patent/JPH05179053A/en
Application granted granted Critical
Publication of JP2734852B2 publication Critical patent/JP2734852B2/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Abstract

PURPOSE:To provide a water-absorbing resin containing a specific phosphoric acid salt, effective for preventing ill-odor, having high safety and useful for sanitary material, etc., such as paper diaper. CONSTITUTION:The objective water-absorbing resin is produced e.g. by incorporating a water-absorbing resin such as poly(meth)acrylic acid salt with preferably 0.05-2% of a phosphoric acid salt expressed by formula (M<1> is one or more univalent metal ion selected from silver, copper, zinc, tin, mercury, lead, iron, cobalt, nickel, manganese, arsenic, antimony, bismuth, barium, cadmium and chromium; A is one or more m-valent ion selected from alkali metal ion, alkaline earth metal ion, ammonium ion and hydrogen ion; M<2> is tetravalent metal; (n) is 0-6; (a) and (b) are positive numbers; a+mb is 1 or 2; c is 2 and d is 3 when a+mb=1, and c is 1 and d is 2 when a+mb=2).

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、防かび及び防藻効
果を有する特定の燐酸塩系化合物を含有する抗菌性のあ
る吸水性樹脂に関するものであり、特に乳幼児や寝たき
り老人、病人などの排尿の処理に使用する紙おむつや生
理用ナプキン等の衛生材料に使用され、人体に長時間接
触している際の、あるいは使用後の有害な菌の繁殖を抑
制し、悪臭を防止することができる吸水性樹脂に関する
ものであり、更に農業用の保水剤として土壌に添加され
た際には、植物に有害な病原菌から根を守ることが出来
る吸水性樹脂に関するものであり、広く各種産業で利用
されるものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial water-absorbing resin containing a specific phosphate compound having antibacterial, antifungal and antialgal effects, and particularly to infants, bedridden elderly people, sick people, etc. It is used for sanitary materials such as disposable diapers and sanitary napkins used for treating urination, and can suppress the growth of harmful bacteria when in contact with the human body for a long time or after use, and can prevent foul odors. It relates to a water-absorbent resin, and when added to soil as a water retention agent for agriculture, it relates to a water-absorbent resin capable of protecting roots from pathogens harmful to plants, and is widely used in various industries. It is something.

【0002】[0002]

【従来の技術】従来から、無機系の抗菌剤として銀や銅
等の抗菌性を示す金属を活性炭、ハイドロキシアパタイ
ト及びゼオライト等に担持させたものが知られている。
これらは有機系の抗菌剤と比較して安全性が高いうえ、
揮発及び分解等を起こさないため抗菌効果の持続性が長
く、しかも耐熱性に優れる特徴を有している。そのた
め、各種天然紙及び合成紙に加工し抗菌紙を作るなどの
試みがなされ効果を発揮している。また吸水性樹脂に銀
イオンを含む水溶性ガラスを担持させて吸水性樹脂に抗
菌性・防臭性を担持させる方法等も提案されている(特
開平1−153748)。
2. Description of the Related Art Conventionally, as an inorganic antibacterial agent, there has been known an antibacterial metal such as silver or copper supported on activated carbon, hydroxyapatite or zeolite.
These are more safe than organic antibacterial agents,
Since it does not cause volatilization or decomposition, it has a long-lasting antibacterial effect and has excellent heat resistance. For this reason, various natural papers and synthetic papers have been processed to make antibacterial papers, which have been effective. Also proposed is a method in which a water-absorbent resin is loaded with water-soluble glass containing silver ions so that the water-absorbent resin is loaded with antibacterial and deodorant properties (JP-A-1-153748).

【0003】しかし、無機系抗菌剤に担持される抗菌性
金属は不安定な場合が多く、それらの無機系抗菌剤の添
加されたものは加工時或いは加工後に変色が認められ、
外観の上から商品価値の高いものを作るには不適なもの
であった。また、これらの無機系抗菌剤は抗菌性金属を
保持する骨格構造が弱く、安定に保持する力も弱いた
め、長期に渡っての使用に際し、永続的な抗菌効果が得
られ難いという問題点がある。さらに、従来の抗菌剤は
その粒度の問題から他の様々な物質と混合し併用する際
に、細かい物質には静電的に付着できなかったり、面に
対しても均一に付着できなかったり、付着後に脱落する
ことが多く問題となっている。
However, the antibacterial metal carried by the inorganic antibacterial agent is often unstable, and those to which the inorganic antibacterial agent is added are discolored during or after processing,
It was unsuitable for making products with high commercial value from the appearance. In addition, since these inorganic antibacterial agents have a weak skeleton structure for holding antibacterial metal, and also have a weak ability to hold them stably, there is a problem that it is difficult to obtain a permanent antibacterial effect when used for a long period of time. .. Furthermore, conventional antibacterial agents cannot be electrostatically attached to fine substances or cannot be evenly attached to surfaces when mixed and used in combination with various other substances due to their particle size problem. It often becomes a problem that it comes off after being attached.

【0004】1価の銀イオンを含む水ガラスを吸水性樹
脂と共に使用し吸収液に接触した際に銀イオンを溶出さ
せる方法は、抗菌効果に優れているものの、効果の発現
時間が比較的短時間で永久効果に乏しいうえに、アクリ
ル酸等を主成分とする吸水性樹脂にとって陽イオンの存
在は吸水能力を阻害する大きなマイナス要因となるとい
う問題点を有している。
A method of using water glass containing monovalent silver ions together with a water-absorbent resin and eluting silver ions when brought into contact with an absorbing solution has an excellent antibacterial effect, but the time for which the effect is exhibited is relatively short. In addition to having a poor permanent effect over time, the water-absorbent resin containing acrylic acid as a main component has the problem that the presence of cations is a major negative factor that impairs the water-absorbing ability.

【0005】また、紙おむつ等に用いられている不織布
等を抗菌紙で代替えすると、抗菌剤は皮膚に直接接触す
ることになり、人体に有用な菌まで抑制することになり
好ましいことではない。
Further, when the non-woven fabric or the like used in a paper diaper or the like is replaced with an antibacterial paper, the antibacterial agent comes into direct contact with the skin, and it is not preferable since it also suppresses bacteria useful to the human body.

【0006】[0006]

【本発明が解決しようとする課題】本発明は、経時的な
変色がなく、かつ永続的に抗菌、防かび及び防藻効果を
有し、本来の特性である高い吸水能力をも有し、紙おむ
つ等に使用された際、適度な抗菌効果と廃棄後の悪臭を
防止することが可能な吸水性樹脂を求めるべくしてなさ
れたものである。
DISCLOSURE OF THE INVENTION The present invention has no discoloration over time, has a permanent antibacterial, antifungal and antialgal effect, and also has a high water absorption capacity which is an original characteristic. It was made in order to obtain a water-absorbent resin which, when used in a paper diaper or the like, has an appropriate antibacterial effect and can prevent a bad odor after disposal.

【0007】[0007]

【課題を解決するための手段】本発明者らは上記課題を
解決するために鋭意検討した結果、銀イオン等の抗菌性
金属を含有する特定の燐酸塩系化合物を含有する吸水性
樹脂がそれらの問題点を解消することを見いだし、本発
明を完成するに至ったのである。即ち、本発明は下記一
般式〔1〕で示される燐酸塩を含有することを特徴とす
る吸水性樹脂に関するものである。 M1 ab2 c(PO4d・nH2O 〔1〕 (M1は銀、銅、亜鉛、錫、水銀、鉛、鉄、コバルト、
ニッケル、マンガン、砒素、アンチモン、ビスマス、バ
リウム、カドミウム及びクロムからなる群より選ばれる
少なくとも1種のl価の金属イオンであり、Aはアルカ
リ金属イオン、アルカリ土類金属イオン、アンモニウム
イオン及び水素イオンからなる群より選ばれる少なくと
も1種のm価のイオンであり、M2は4価金属であり、
nは0≦n≦6を満たす数であり、a及びbはいずれも
正数であり、la+mb=1又はla+mb=2であ
り、c及びdはla+mb=1の時、c=2、d=3で
あり、la+mb=2の時、c=1、d=2である。)
Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that water-absorbent resins containing a specific phosphate compound containing an antibacterial metal such as silver ion are The inventors have found that the problem of (1) is solved and completed the present invention. That is, the present invention relates to a water absorbent resin containing a phosphate represented by the following general formula [1]. M 1 a Ab M 2 c (PO 4 ) d · nH 2 O [1] (M 1 is silver, copper, zinc, tin, mercury, lead, iron, cobalt,
At least one monovalent metal ion selected from the group consisting of nickel, manganese, arsenic, antimony, bismuth, barium, cadmium and chromium, A is an alkali metal ion, an alkaline earth metal ion, an ammonium ion and a hydrogen ion. M 2 is at least one m-valent ion selected from the group consisting of
n is a number satisfying 0 ≦ n ≦ 6, a and b are both positive numbers, la + mb = 1 or la + mb = 2, and c and d are la + mb = 1, and c = 2 and d = 3, and when la + mb = 2, c = 1 and d = 2. )

【0008】以下、本発明について詳細に説明する。本
発明において抗菌剤として用いられる化合物は上記一般
式〔1〕で示される抗菌性のある燐酸塩である。上記一
般式〔1〕で示される化合物は、la+mb=1の時、
c=2、d=3の各係数を有し、アモルファス又は空間
群R3cに属する結晶性化合物であり、各構成イオンが3
次元網目状構造を作る化合物であり、la+mb=2の
時、c=1、d=2の各係数を有し、アモルファス又は
各構成イオンが層状構造を作る化合物である。本発明に
おける燐酸塩としては、容易に微粒子状として得ること
ができる点及び日光に暴露したときの変色が少なく耐候
性に優れることから、 la+ mb=1でc=2、d=3
である3次元網目状構造を有する結晶性化合物が好まし
い。
The present invention will be described in detail below. The compound used as the antibacterial agent in the present invention is the antibacterial phosphate represented by the above general formula [1]. When the compound represented by the general formula [1] is la + mb = 1,
Amorphous or crystalline compound having a coefficient of c = 2 and d = 3 and belonging to the space group R3c, in which each constituent ion is 3
It is a compound that forms a dimensional network structure, has a coefficient of c = 1 and d = 2 when la + mb = 2, and is a compound in which amorphous or each constituent ion forms a layered structure. The phosphate in the present invention can be easily obtained in the form of fine particles and has little discoloration when exposed to sunlight and has excellent weather resistance. Therefore, la = mb = 1, c = 2, d = 3.
Which is a crystalline compound having a three-dimensional network structure.

【0009】上記一般式〔1〕におけるM1は、いずれ
も抗菌性及び防カビ性を示す金属として知られたもので
あり、これらの中で銀は、安全性の他、抗菌性を顕著に
高めることができる金属として特に有効であり、好まし
いものである。
M 1 in the above general formula [1] is known as a metal exhibiting antibacterial and antifungal properties, and among them, silver has remarkable antibacterial properties in addition to safety. It is particularly effective and preferable as a metal that can be increased.

【0010】上記一般式〔1〕におけるAは、アルカリ
金属イオン、アルカリ土類金属イオン、アンモニウムイ
オン又は水素イオンであり、アルカリ金属イオン及びア
ルカリ土類金属イオンの好ましい具体例には、リチウ
ム、ナトリウム、カリウム、マグネシウム及びカルシウ
ム等のイオンがあり、これらの中では、化合物の安定性
及び安価に入手できる点から、リチウム、ナトリウム、
アンモニウムイオンおよび水素イオンが好ましいイオン
である。
A in the above general formula [1] is an alkali metal ion, an alkaline earth metal ion, an ammonium ion or a hydrogen ion. Preferred specific examples of the alkali metal ion and the alkaline earth metal ion are lithium and sodium. , Potassium, magnesium, and calcium, among these, among these, from the viewpoint of the stability of the compound and low availability, lithium, sodium,
Ammonium ions and hydrogen ions are the preferred ions.

【0011】上記一般式〔1〕におけるM2は、4価金
属であり、好ましい具体例には、ジルコニウム、チタン
又は錫があり、化合物の安全性を考慮すると、ジルコニ
ウムが特に好ましい金属である。
M 2 in the above general formula [1] is a tetravalent metal, and preferable specific examples thereof include zirconium, titanium or tin. Considering the safety of the compound, zirconium is a particularly preferable metal.

【0012】上記一般式〔1〕の燐酸塩の具体例とし
て、以下のものがある。 Ag0.005Li0.995Zr2(PO43 Ag0.01(NH40.99Zr2(PO43 Ag0.05Na0.95Zr2(PO43 Ag0.20.8Ti2(PO43 Ag0.10.9Zr2(PO43 及び化合物1モル当たりの銀イオンの電荷量と同じ電荷
量になるようにしながら、上記各式におけるAgの一部
又は全部をZn、Mn、Ni、Pb、Hg、Sn、また
はCuと置換した化合物、 Ag0.001Li1.999Zr(PO42 Ag0.01Na1.99Zr(PO42 Ag0.011.99Sn(PO42・1.2H2O Ag0.1(NH41.9Ti(PO42・4H2O Ag0.021.98(PO42・1.7H2O 及び化合物1モル当たりの銀イオンの電荷量と同じ電荷
量になるようにしながら、上記各式におけるAgの一部
又は全部をZn、Mn、Ni、Pb、Hg、Sn、また
はCuと置換した化合物。
The following are specific examples of the phosphate represented by the general formula [1]. Ag 0.005 Li 0.995 Zr 2 (PO 4 ) 3 Ag 0.01 (NH 4 ) 0.99 Zr 2 (PO 4 ) 3 Ag 0.05 Na 0.95 Zr 2 (PO 4 ) 3 Ag 0.2 K 0.8 Ti 2 (PO 4 ) 3 Ag 0.1 H 0.9 Zr 2 (PO 4 ) 3 and some of the Ag in each of the above formulas are replaced with Zn, Mn, Ni, Pb, Hg while maintaining the same charge amount as that of silver ions per mol of the compound. Compound substituted with Sn or Cu, Ag 0.001 Li 1.999 Zr (PO 4 ) 2 Ag 0.01 Na 1.99 Zr (PO 4 ) 2 Ag 0.01 K 1.99 Sn (PO 4 ) 2 1.2H 2 O Ag 0.1 (NH 4 ) 1.9 Ti (PO 4 ) 2 .4H 2 O Ag 0.02 H 1.98 (PO 4 ) 2 .1.7H 2 O and the amount of silver ion per 1 mol of the compound, while adjusting the charge amount to the same value as above. Part or all of Ag in the formula is Zn, Mn, Ni Pb, Hg, Sn, or compounds substituted with Cu,.

【0013】本発明における燐酸塩を合成する方法に
は、焼成法、湿式法及び水熱法等があり、例えば以下の
様にして容易に得ることができる。 ○網目状構造リン酸塩の合成 焼成法により合成する場合、炭酸リチウム(Li2CO3)又
は炭酸ナトリウム(Na2CO3)等のアルカリ金属を含有す
る化合物、酸化ジルコニウム(ZrO2)等のジルコニウム
を含有する化合物及びリン酸二水素アンモニウム(NH4H
2PO4)等のリン酸基を含有する化合物を、モル比で約
1:4:6となるように混合し、これを1100〜1400℃で
焼成することにより、一般式〔2〕で示される化合物を
得る。 Ax Zr2(PO43 〔2〕 (Aは上記と同じ意味であり、xはAが1価であるとき
は1であり、Aが2価であるときは1/2である) 一般式〔2〕で示される化合物を、室温〜100 ℃におい
て、適当な濃度で銀イオンを含有する水溶液中に浸漬す
ることにより、一般式〔1〕で示される化合物が得られ
る。
The method for synthesizing the phosphate in the present invention includes a calcination method, a wet method and a hydrothermal method, which can be easily obtained, for example, as follows. ○ Synthesis of network structure phosphate When synthesizing by phosphate method, compounds containing alkali metal such as lithium carbonate (Li 2 CO 3 ) or sodium carbonate (Na 2 CO 3 ), zirconium oxide (ZrO 2 ) etc. Compounds containing zirconium and ammonium dihydrogen phosphate (NH 4 H
2 PO 4 ) and other compounds having a phosphoric acid group are mixed in a molar ratio of about 1: 4: 6, and the mixture is baked at 1100-1400 ° C. to give a compound represented by the general formula [2]. To obtain the compound. A x Zr 2 (PO 4 ) 3 [2] (A has the same meaning as above, x is 1 when A is monovalent, and is 1/2 when A is divalent) The compound represented by the general formula [1] is obtained by immersing the compound represented by the general formula [2] in an aqueous solution containing silver ions at an appropriate concentration at room temperature to 100 ° C.

【0014】また、湿式法により合成する場合、オキシ
硝酸ジルコニウム及び硝酸ナトリウムの水溶液を攪拌し
ながら、この中にシュウ酸を加え、さらにリン酸を加え
る。苛性ソーダ水溶液にて反応液のpHを3.5に調整
し、78時間加熱還流後、沈澱物を濾過、水洗、乾燥、
粉砕し、網目状リン酸ジルコニウム[NaZr2(P
43]を得る。これを適当な濃度で抗菌性金属を含有
する水溶液中に浸漬することにより、一般式〔1〕で示
される化合物が得られる。
In the case of synthesizing by a wet method, oxalic acid and phosphoric acid are added to an aqueous solution of zirconium oxynitrate and sodium nitrate while stirring. The pH of the reaction solution was adjusted to 3.5 with an aqueous solution of caustic soda, the mixture was heated under reflux for 78 hours, and the precipitate was filtered, washed with water and dried,
Crushed and reticulated zirconium phosphate [NaZr 2 (P
O 4 ) 3 ] is obtained. By dipping this in an aqueous solution containing an antibacterial metal at an appropriate concentration, the compound represented by the general formula [1] can be obtained.

【0015】水熱法により合成する場合は例えば以下の
様に合成すれば良い。硫酸ジルコニウムの水溶液に、攪
拌しながら燐酸二水素アンモニウムを徐々に加え、沈澱
物を生成する。その後、苛性ソーダ水溶液にて反応液の
pH値を2に調整し、130℃に保持した密閉容器中、
飽和蒸気圧下で32時間沈澱物を加熱した後、沈澱物を
濾過、水洗、乾燥、粉砕し、結晶質リン酸ジルコニウム
NH4Zr2(PO43を得る。さらに、この結晶質リン
酸ジルコニウムを適当な濃度の硝酸銀水溶液中に加え、
攪拌することにより、平均粒径が1μm以下の抗菌性燐
酸塩AgX(NH41-XZr2(PO43を得る(xは0
〜1の数である。)。
In the case of synthesizing by the hydrothermal method, it may be synthesized as follows, for example. Ammonium dihydrogen phosphate is gradually added to an aqueous solution of zirconium sulfate with stirring to form a precipitate. Then, adjust the pH value of the reaction solution to 2 with a caustic soda aqueous solution, and in a closed container kept at 130 ° C,
After heating the precipitate for 32 hours under saturated vapor pressure, the precipitate is filtered, washed with water, dried and ground to obtain crystalline zirconium phosphate NH 4 Zr 2 (PO 4 ) 3 . Furthermore, this crystalline zirconium phosphate was added to an aqueous solution of silver nitrate having an appropriate concentration,
By stirring, an antibacterial phosphate Ag x (NH 4 ) 1-x Zr 2 (PO 4 ) 3 having an average particle size of 1 μm or less is obtained (x is 0).
Is a number from one to one. ).

【0016】○層状構造リン酸塩の合成 濃厚なリン酸水溶液中に、オキシ塩化ジルコニウム、オ
キシ塩化チタン或いはオキシ塩化スズ等のジルコニウ
ム、チタン或いはスズ等の4価金属を構成元素とするオ
キシ塩化物を添加し、24時間加熱還流後、沈澱物を濾
過、水洗、乾燥、粉砕し、リン酸ジルコニウム〔Zr(HPO
4)2・H2O〕等のリン酸塩を得、これをアルカリ金属等の
硝酸塩水溶液に添加し、攪拌、水洗、乾燥及び粉砕する
ことにより、一般式〔3〕で示される化合物を得る。 A2xZr(PO42・nH2O 〔3〕 (A、x及びnは上記と同じ意味である。) 一般式〔3〕で示される化合物を適当な濃度で抗菌性金
属を含有する水溶液中に浸漬することにより、一般式
〔1〕で示される化合物を得る。
Synthesis of Layered Structure Phosphate An oxychloride containing a tetravalent metal such as zirconium oxychloride, titanium oxychloride or tin oxychloride, or a tetravalent metal such as titanium or tin in a concentrated aqueous solution of phosphoric acid. Was added, and the mixture was heated under reflux for 24 hours, and the precipitate was filtered, washed with water, dried and pulverized, and zirconium phosphate [Zr (HPO
4 ) 2 · H 2 O] or the like is obtained, and this is added to an aqueous solution of a nitrate such as an alkali metal, and the mixture is stirred, washed with water, dried and pulverized to obtain a compound represented by the general formula [3]. .. A 2x Zr (PO 4 ) 2 · nH 2 O [3] (A, x and n have the same meanings as above.) The compound represented by the general formula [3] contains an antibacterial metal at an appropriate concentration. By dipping in an aqueous solution, the compound represented by the general formula [1] is obtained.

【0017】なお、一般式〔1〕におけるaの値は、上
記一般式〔2〕又は〔3〕で表される化合物を浸漬する
水溶液における銀の濃度、その水溶液に一般式〔2〕又
は〔3〕で表される化合物を浸漬する時間又は温度等を
調整することにより、必要とする特性及び使用条件等に
応じて、適宜調整することができる。
The value of a in the general formula [1] is the concentration of silver in the aqueous solution in which the compound represented by the general formula [2] or [3] is immersed, the general formula [2] or [ 3] By adjusting the time, temperature, or the like for immersing the compound represented by the formula [3], it can be appropriately adjusted according to the required characteristics, use conditions, and the like.

【0018】抗菌性を発揮させるには、一般式〔1〕に
おけるaの値は大きい方がよいが、aの値が0.001以
上であれば充分に抗菌性及び防カビ性を発揮させること
ができる。しかし、aの値が0.001未満であると、抗
菌性を長時間発揮させることが困難となる恐れがあるの
で、aの値を0.01以上の値とすることが好ましい。
又、経済性を考慮すると、aの値は0.5以下が適当であ
る。
In order to exert the antibacterial property, it is preferable that the value of a in the general formula [1] is large, but if the value of a is 0.001 or more, the antibacterial property and the antifungal property should be sufficiently exhibited. You can However, if the value of a is less than 0.001, it may be difficult to exert the antibacterial property for a long time. Therefore, it is preferable to set the value of a to 0.01 or more.
In consideration of economy, the value of a is suitably 0.5 or less.

【0019】本発明に用いられる燐酸塩の平均粒径は、
樹脂への均一な分散のために、1μm以下であるのが好
ましく、均一で微粒子の化合物を使用することによっ
て、吸水性樹脂に添加することが容易になり、吸水性樹
脂の粒子表面に均一に付着させることが可能になり、抗
菌剤としての特性と吸水性樹脂の特性を効果的に発揮さ
せることが出来る。
The average particle size of the phosphate used in the present invention is
For uniform dispersion in the resin, it is preferably 1 μm or less, and by using a compound of uniform and fine particles, it becomes easy to add to the water absorbent resin, and it is evenly distributed on the particle surface of the water absorbent resin. It becomes possible to attach them, and the properties as an antibacterial agent and the properties of the water absorbent resin can be effectively exhibited.

【0020】上記の燐酸塩は熱及び光の暴露に対して安
定であり、500℃以上、場合に依っては800℃での
加熱であっても構造及び組成が全く変化せず、紫外線の
照射に依っても何等変色を起こさない。また、液体状態
にある水と接触したり、酸性溶液中でも骨格構造の変化
がみられない。このように本発明で用いる燐酸塩系化合
物は化学的及びに物理的に安定であり、各種の加工及び
保存、さらには使用時において、耐酸性や遮光条件等の
制約を受けることがない。
The above-mentioned phosphates are stable to exposure to heat and light, their structure and composition do not change at all even when heated at 500 ° C. or higher, and in some cases 800 ° C., and they are exposed to ultraviolet rays. It does not cause any discoloration. Moreover, it does not come into contact with water in a liquid state or change in skeleton structure even in an acidic solution. As described above, the phosphate compound used in the present invention is chemically and physically stable, and is free from restrictions such as acid resistance and light-shielding conditions during various kinds of processing and storage and during use.

【0021】これらの燐酸塩は上記した方法で製造して
使用することも出来るが、市販品(ノバロンAG−30
0:商品名/東亞合成化学工業株式会社製)もあり、そ
れを使用することも出来る。
These phosphates can be produced and used by the above-mentioned method, but they are commercially available products (Novalon AG-30).
0: trade name / manufactured by Toagosei Chemical Industry Co., Ltd.), which can also be used.

【0022】上記の燐酸塩が適用される吸水性樹脂に格
別の限定はなく、重合体中に結晶構造あるいは架橋構造
を有することによって、水と接触した際に速やかにこれ
を吸収し、膨潤する能力のある重合体からなるものであ
ればよく、具体的にはポリ(メタ)アクリル酸塩、ポリ
ビニルアルコール、ポリエチレンオキシド、ポリスルホ
ン酸塩、ポリ(メタ)アクリルアミド、カルボキシメチ
ルセルロース、ビニルアルコール/アクリル酸塩共重合
体、アクリル酸塩/アクリルアミド共重合体を主成分と
する合成高分子化合物、寒天、コンニャクマンナン、ア
ルギン酸、カラギナン等の天然高分子に上記合成高分子
化合物がグラフトされているもの等が挙げられ、これら
の吸水性樹脂に上記の燐酸塩が添加されて、抗菌性を有
する吸水性樹脂となる。吸水性樹脂としては単独のもの
であっても2種以上の混合物であっても差し支えない。
ができる。
There is no particular limitation on the water-absorbent resin to which the above-mentioned phosphate is applied. Since the polymer has a crystal structure or a cross-linking structure, when it comes into contact with water, it quickly absorbs and swells. Any polymer capable of being used may be used, and specifically, poly (meth) acrylate, polyvinyl alcohol, polyethylene oxide, polysulfonate, poly (meth) acrylamide, carboxymethyl cellulose, vinyl alcohol / acrylate. Examples thereof include copolymers, synthetic polymer compounds having an acrylate / acrylamide copolymer as a main component, and natural polymer such as agar, konjak mannan, alginic acid, and carrageenan, which are grafted with the above synthetic polymer compounds. The above-mentioned phosphate is added to these water-absorbent resins to obtain a water-absorbent resin having antibacterial properties. That. The water absorbent resin may be a single resin or a mixture of two or more kinds.
You can

【0023】燐酸塩の吸水性樹脂に対する添加量は、効
果と経済性の面から、吸水性樹脂の粉末に対し0.000
1〜5%が好ましく、より好ましくは0.05〜2%であ
る。燐酸塩の添加量が0.0001%よりも少ないと抗菌
効果が十分に発揮されず、5%よりも多くしても添加の
割合に応じた効果の向上はみとめられず経済的に問題が
あるうえに、吸水性樹脂の吸水速度やサラット感などの
点で吸水性樹脂単独の場合に比べてやや劣る様になり、
さらに添加された吸水性樹脂表面から燐酸塩が脱落する
恐れが生じる。また、周囲の条件にもよるが、燐酸塩の
添加量が吸水性樹脂の粉末に対しておよそ0.5%未満の
ときには燐酸塩は菌の増殖を防止するだけにとどまり、
それ以上では周囲の菌を殺菌・滅菌する効果を現す。
The amount of the phosphate added to the water-absorbent resin is 0.000 based on the powder of the water-absorbent resin from the viewpoints of effect and economy.
It is preferably 1 to 5%, more preferably 0.05 to 2%. If the amount of phosphate added is less than 0.0001%, the antibacterial effect is not sufficiently exerted, and if it is more than 5%, the improvement of the effect depending on the ratio of addition is not found and there is an economical problem. In addition, it becomes slightly inferior to the case of the water absorbent resin alone in terms of the water absorption speed of the water absorbent resin and the feeling of salat.
Furthermore, there is a risk that the phosphate will fall off from the surface of the added water-absorbent resin. Also, depending on the ambient conditions, when the amount of phosphate added is less than about 0.5% of the water-absorbent resin powder, the phosphate only prevents the growth of bacteria,
If it is more than that, it shows the effect of sterilizing and sterilizing the surrounding bacteria.

【0024】吸水性樹脂に燐酸塩を添加する方法として
は、圧力で接合する方法、接着剤等のバインダーを使用
して接着する方法、単に混合する方法などいろいろ考え
られ、いずれの場合も十分な効力を発揮できるが、経済
性、作業性、効果の速攻性等を考慮すれば、以下の様に
吸水性樹脂の表面処理段階において添加することが好ま
しい。
As a method for adding a phosphate to the water-absorbent resin, various methods such as a method of joining by pressure, a method of adhering by using a binder such as an adhesive, and a method of simply mixing can be considered. Although the effect can be exerted, it is preferable to add it in the surface treatment step of the water-absorbent resin as described below in consideration of economical efficiency, workability, quickness of effect, and the like.

【0025】 吸水性樹脂粉末に少量の水を添加し
(あらかじめ3%以上の水を含有している樹脂をそのま
ま使用することも可能である)、樹脂表面の吸着性を良
くしたうえで、適量の本発明の燐酸塩及び必要に応じた
他の添加剤を加え良く攪拌する。この際、攪拌と同時に
加熱乾燥することも、攪拌後に加熱乾燥することも可能
である。
A small amount of water is added to the water-absorbent resin powder (a resin containing 3% or more of water in advance can be used as it is) to improve the adsorptivity of the resin surface, and then an appropriate amount. Of the present invention and other optional additives are added, and the mixture is stirred well. At this time, it is possible to heat-dry at the same time as stirring or heat-dry after stirring.

【0026】 吸水性樹脂粉末に少量の水と多官能性
架橋剤、本発明の燐酸塩及び必要に応じて他の添加剤を
加え攪拌しながら加熱する。この際使用する多官能性架
橋剤とは、ジグリシジルエーテル系化合物、多価金属
塩、ハロエポキシ化合物、アルデヒド系化合物、イソシ
アネート系化合物などの吸水性樹脂中のカルボン酸基、
水酸基、スルホン酸基、アミノ基等と反応し得る2個以
上の官能基を有する架橋剤である。
A small amount of water, a polyfunctional crosslinking agent, the phosphate of the present invention and, if necessary, other additives are added to the water-absorbent resin powder and heated with stirring. The polyfunctional crosslinking agent used at this time, a diglycidyl ether compound, a polyvalent metal salt, a haloepoxy compound, an aldehyde compound, a carboxylic acid group in a water-absorbent resin such as an isocyanate compound,
It is a cross-linking agent having two or more functional groups capable of reacting with a hydroxyl group, a sulfonic acid group, an amino group and the like.

【0027】[0027]

【作用】銀イオン等の抗菌性金属を含有する特定の燐酸
塩系化合物は、吸水性樹脂に配合されて、吸水性樹脂の
特性を損なうことなく、該樹脂に抗菌性を付与するとい
う作用を奏するのである。
[Function] A specific phosphate compound containing an antibacterial metal such as silver ion is added to a water-absorbent resin to impart an antibacterial property to the resin without impairing the properties of the water-absorbent resin. To play.

【0028】[0028]

【実施例】以下に、本発明の吸水性樹脂の奏する優れた
効果を明白にするため実施例及び評価試験を用いて説明
する。 実施例1 蒸留水に対する吸水能がおよそ300倍であるアクリル
酸ナトリウム系吸水性樹脂粉末100重量部に20重量
部の水を添加し、良く攪拌しながら抗菌性燐酸塩(ノバ
ロンAG−300:商品名/東亞合成化学工業株式会社
製)を0.05重量部加えた。その後120℃でおよそ2
時間乾燥して本発明の吸水性樹脂を得た。該樹脂の吸水
能を測定したところおよそ300倍で殆ど能力の低下は
認められなかった。
[Examples] In order to clarify the excellent effects of the water absorbent resin of the present invention, examples and evaluation tests will be described below. Example 1 20 parts by weight of water was added to 100 parts by weight of a sodium acrylate-based water absorbent resin powder having a water absorption capacity of about 300 times that of distilled water, and the antibacterial phosphate (Novalon AG-300: product (Name: Toagosei Chemical Industry Co., Ltd.) was added in an amount of 0.05 part by weight. Then at 120 ℃ for about 2
After drying for an hour, the water absorbent resin of the present invention was obtained. When the water absorption capacity of the resin was measured, it was about 300 times, and almost no decrease in the capacity was recognized.

【0029】実施例2 蒸留水に対する吸水能がおよそ300倍であるアクリル
酸ナトリウム系吸水性樹脂粉末100重量部に30重量
部の水、1重量部の抗菌性燐酸塩(ノバロンAG−30
0:商品名/東亞合成化学工業株式会社製)及びポリエ
チレングリコールジグリシジルエーテル系化合物0.5重
量部を加え、加熱攪拌した後120℃でおよそ2時間乾
燥して本発明の吸水性樹脂を得た。該樹脂の吸水能を測
定したところおよそ300倍で殆ど能力の低下は認めら
れなかった。
Example 2 100 parts by weight of a sodium acrylate-based water-absorbent resin powder having a water absorption capacity of about 300 times against distilled water, 30 parts by weight of water, and 1 part by weight of an antibacterial phosphate (Novalon AG-30).
0: trade name / manufactured by Toagosei Kagaku Kogyo Co., Ltd.) and 0.5 part by weight of polyethylene glycol diglycidyl ether compound, heated and stirred, and then dried at 120 ° C. for about 2 hours to obtain the water absorbent resin of the present invention. It was When the water absorption capacity of the resin was measured, it was about 300 times, and almost no decrease in the capacity was recognized.

【0030】比較例1〜2 蒸留水に対する吸水能がおよそ300倍であるアクリル
酸ナトリウム系吸水性樹脂粉末100重量部に、30重
量部の水と銀イオンを含む水ガラス1重量部を加え、良
く混合したのち乾燥粉砕して抗菌性のある吸水性樹脂
(比較例1)を得た。該樹脂の吸水能を測定したところ
約50倍に低下していた。又、比較になにも処理してい
ない蒸留水に対する吸水能がおよそ300倍であるアク
リル酸ナトリウム系吸水性樹脂(比較例2)を用いた。
Comparative Examples 1 and 2 To 100 parts by weight of a sodium acrylate-based water absorbent resin powder having a water absorption capacity of about 300 times with respect to distilled water, 1 part by weight of water glass containing 30 parts by weight of water and silver ions was added, After thoroughly mixed, the mixture was dried and pulverized to obtain an antibacterial water absorbent resin (Comparative Example 1). The water absorption capacity of the resin was measured and found to be reduced by about 50 times. Further, for comparison, a sodium acrylate-based water absorbent resin (Comparative Example 2) having a water absorption capacity of about 300 times that of untreated distilled water was used.

【0031】評価試験1 試料0.1gに、滅菌水で調製した106cells/mlの大腸
菌株を有する菌液10mlを加え、膨潤させた。37℃で
6時間培養後一部を寒天培地にとり、18時間培養した
後の生存菌の数を測定した。
Evaluation test 1 To 0.1 g of a sample, 10 ml of a bacterial solution containing 10 6 cells / ml of E. coli strain prepared with sterile water was added and swollen. After culturing at 37 ° C. for 6 hours, a part thereof was placed on an agar medium, and after culturing for 18 hours, the number of surviving bacteria was measured.

【0032】評価試験2 試料0.1gに、滅菌生理食塩水で調製した106cells/
mlの大腸菌株を有する菌液10mlを加え膨潤させた。3
7℃で6時間培養後生存菌の数を測定した。
Evaluation test 2 0.1 g of a sample was added to 10 6 cells / prepared with sterile physiological saline.
10 ml of a bacterial solution containing ml of E. coli strain was added and swollen. Three
After culturing at 7 ° C for 6 hours, the number of surviving bacteria was measured.

【0033】評価試験3 黄色ブドウ球菌、大腸菌、緑膿菌の各株をニュートリエ
ントブロス培地で4時間培養して得られた菌液を、寒天
培地に0.5%(v/v)加え、シャーレに10ml分注し
て固化させた。ここに、試料0.1gに滅菌生理食塩水4
mlを加えて膨潤させたものをのせ18時間培養し、試料
の回りの菌株発育状態を観察した。
Evaluation test 3 Strains of Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa were cultured in a nutrient broth medium for 4 hours, and 0.5% (v / v) of the bacterial solution was added to the agar medium. 10 ml was poured into a petri dish and solidified. Here, 0.1 g of the sample is sterilized with saline 4
After swelling the solution by adding ml, it was placed and cultured for 18 hours, and the growth state of the strain around the sample was observed.

【0034】評価試験4 試料0.05gを滅菌生理食塩水20mlに入れて膨潤さ
せ、滅菌生理食塩水で調製した106cells/mlの大腸菌
液1mlを加え、振盪培養し、1.5、3、6、24時間後
の生菌数を測定した。
Evaluation test 4 0.05 g of the sample was put into 20 ml of sterile physiological saline to swell, 1 ml of E. coli solution of 10 6 cells / ml prepared with sterile physiological saline was added, and the mixture was shake-cultured for 1.5 and 3 times. The viable cell count was measured after 6 and 24 hours.

【0035】以上の評価試験の結果を〔表1〕に表示し
たが、これらの結果から本発明の吸水性樹脂が本来の特
性である吸水能を有し抗菌性にも優れていることが明ら
かである。尚、表中○印は菌が発育しなかったことを示
し、×印は発育したことを示している。
The results of the above evaluation tests are shown in [Table 1], and it is clear from these results that the water-absorbent resin of the present invention has the original water-absorbing ability and excellent antibacterial properties. Is. In the table, a circle indicates that the bacterium did not grow, and a cross indicates that the bacterium did grow.

【0036】[0036]

【表1】 [Table 1]

【0037】[0037]

【発明の効果】本発明の吸水性樹脂は、特定の燐酸塩系
化合物を存在により優れた抗菌性を有するとともに吸水
性樹脂としても優れたものであるため、乳幼児や寝たき
り老人、病人などの排尿の処理に使用する紙おむつや生
理用ナプキン等の衛生材料に使用され、人体に長時間接
触している際の、あるいは使用後の有害な菌の繁殖を抑
制し、悪臭を防止することができ、また農業用の保水剤
として土壌に添加された際には、植物に有害な病原菌か
ら根を守ることが出来るという優れた効果を奏するもの
である。
EFFECTS OF THE INVENTION The water-absorbent resin of the present invention has excellent antibacterial properties due to the presence of a specific phosphate compound and is also excellent as a water-absorbent resin. Therefore, urination of infants, bedridden elderly people, sick people, etc. It is used for sanitary materials such as paper diapers and sanitary napkins used for the treatment of, and suppresses the growth of harmful bacteria when in contact with the human body for a long time or after use, and can prevent a bad smell, Further, when added to soil as a water retention agent for agriculture, it has an excellent effect of being able to protect roots from pathogenic bacteria harmful to plants.

フロントページの続き (72)発明者 加藤 秀樹 愛知県名古屋市港区船見町1番地の1東亞 合成化学工業株式会社名古屋総合研究所内Front Page Continuation (72) Inventor Hideki Kato 1 Toago Synthetic Chemical Industry Co., Ltd. Nagoya Research Institute, 1 Funami-cho, Minato-ku, Aichi

Claims (1)

【特許請求の範囲】[Claims] 【請求項1】 下記一般式〔1〕で示される燐酸塩を含
有することを特徴とする吸水性樹脂。 M1 ab2 c(PO4d・nH2O 〔1〕 (M1は銀、銅、亜鉛、錫、水銀、鉛、鉄、コバルト、
ニッケル、マンガン、砒素、アンチモン、ビスマス、バ
リウム、カドミウム及びクロムからなる群より選ばれる
少なくとも1種のl価の金属イオンであり、Aはアルカ
リ金属イオン、アルカリ土類金属イオン、アンモニウム
イオン及び水素イオンからなる群より選ばれる少なくと
も1種のm価のイオンであり、M2は4価金属であり、
nは0≦n≦6を満たす数であり、a及びbはいずれも
正数であり、la+mb=1又はla+mb=2であ
り、c及びdはla+mb=1の時、c=2、d=3で
あり、la+mb=2の時、c=1、d=2である。)
1. A water absorbent resin containing a phosphate represented by the following general formula [1]. M 1 a Ab M 2 c (PO 4 ) d · nH 2 O [1] (M 1 is silver, copper, zinc, tin, mercury, lead, iron, cobalt,
At least one monovalent metal ion selected from the group consisting of nickel, manganese, arsenic, antimony, bismuth, barium, cadmium and chromium, A is an alkali metal ion, an alkaline earth metal ion, an ammonium ion and a hydrogen ion. M 2 is at least one m-valent ion selected from the group consisting of
n is a number satisfying 0 ≦ n ≦ 6, a and b are both positive numbers, la + mb = 1 or la + mb = 2, and c and d are la + mb = 1, and c = 2 and d = 3, and when la + mb = 2, c = 1 and d = 2. )
JP3359012A 1991-12-27 1991-12-27 Water absorbent resin Expired - Lifetime JP2734852B2 (en)

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Application Number Priority Date Filing Date Title
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Publications (2)

Publication Number Publication Date
JPH05179053A true JPH05179053A (en) 1993-07-20
JP2734852B2 JP2734852B2 (en) 1998-04-02

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ID=18462291

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* Cited by examiner, † Cited by third party
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JPH08208414A (en) * 1994-11-01 1996-08-13 Toray Ind Inc Resin composition and antimicrobial and antifungal methods
US5981668A (en) * 1996-10-31 1999-11-09 Sanyo Chemical Industries, Ltd. Anti-bacterial water absorbing agent and anti-bacterial water absorbent material
KR100348859B1 (en) * 2000-04-14 2002-08-17 김정섭 Carbon dioxide and moisture absorbable polymer powder, manufacturing method thereof and high absorbing good make use of them
US7183345B2 (en) 2001-06-29 2007-02-27 Stockhausen Gmbh Superabsorbent carboxyl-containing polymers with odor control properties and method for preparation
US7595428B2 (en) 2000-11-22 2009-09-29 Nippon Shokubai Co., Ltd. Water-absorbing agent composition and method for production thereof, absorptive article and absorbing material
US7825169B2 (en) 2002-06-06 2010-11-02 Nippon Shokubai Co. Ltd. Water-absorbent composition, process for production thereof, absorbent and absorbing product
US8026294B2 (en) 2007-10-10 2011-09-27 Nippon Shokubai Co., Ltd. Water absorbent resin composition and method for producing the same
WO2013073614A1 (en) 2011-11-15 2013-05-23 株式会社日本触媒 Water absorbent composition and method for producing same, as well as storage and stocking method for same

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JPH0338504A (en) * 1989-07-03 1991-02-19 Shinagawa Nenryo Kk Improving method of antibacterial property of silver-containing compound

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0338504A (en) * 1989-07-03 1991-02-19 Shinagawa Nenryo Kk Improving method of antibacterial property of silver-containing compound

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08208414A (en) * 1994-11-01 1996-08-13 Toray Ind Inc Resin composition and antimicrobial and antifungal methods
US5981668A (en) * 1996-10-31 1999-11-09 Sanyo Chemical Industries, Ltd. Anti-bacterial water absorbing agent and anti-bacterial water absorbent material
KR100348859B1 (en) * 2000-04-14 2002-08-17 김정섭 Carbon dioxide and moisture absorbable polymer powder, manufacturing method thereof and high absorbing good make use of them
US7595428B2 (en) 2000-11-22 2009-09-29 Nippon Shokubai Co., Ltd. Water-absorbing agent composition and method for production thereof, absorptive article and absorbing material
US7183345B2 (en) 2001-06-29 2007-02-27 Stockhausen Gmbh Superabsorbent carboxyl-containing polymers with odor control properties and method for preparation
US7825169B2 (en) 2002-06-06 2010-11-02 Nippon Shokubai Co. Ltd. Water-absorbent composition, process for production thereof, absorbent and absorbing product
US8026294B2 (en) 2007-10-10 2011-09-27 Nippon Shokubai Co., Ltd. Water absorbent resin composition and method for producing the same
WO2013073614A1 (en) 2011-11-15 2013-05-23 株式会社日本触媒 Water absorbent composition and method for producing same, as well as storage and stocking method for same
US10363339B2 (en) 2011-11-15 2019-07-30 Nippon Shokubai Co., Ltd. Water absorbent agent composition and method for producing same, as well as storage and stocking method for same

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