JP2657509B2 - Antibacterial polymer - Google Patents
Antibacterial polymerInfo
- Publication number
- JP2657509B2 JP2657509B2 JP63047750A JP4775088A JP2657509B2 JP 2657509 B2 JP2657509 B2 JP 2657509B2 JP 63047750 A JP63047750 A JP 63047750A JP 4775088 A JP4775088 A JP 4775088A JP 2657509 B2 JP2657509 B2 JP 2657509B2
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- polymer
- antibacterial
- antibacterial polymer
- reaction
- pcs
- 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
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は第四級窒素を有する抗菌性ポリマーに関し、
例えばプール、飲料水、冷却水などの殺菌剤、スライム
コントロール剤、床材、壁材、天井材などの建材一般、
農業用資材等、広範にわたつて利用することができる。The present invention relates to antimicrobial polymers having quaternary nitrogen,
For example, pools, drinking water, bactericides such as cooling water, slime control agents, floor materials, wall materials, building materials in general such as ceiling materials,
It can be used for a wide range of agricultural materials.
（従来の技術） 従来の抗菌性化合物のうち、低分子量のものは各種の
製品を構成する材料に混合して用いられているため、抗
菌性をもつ有効成分の外部への放出や内部での分離、沈
降を引きおこし、その結果、抗菌力の持続性が低下する
などの欠点を有している。(Prior art) Among conventional antimicrobial compounds, low-molecular-weight compounds are used as a mixture with materials that make up various products. It has the drawback of causing separation and sedimentation, and as a result, the persistence of antibacterial activity is reduced.
そこで、これらの問題点を解決すべく抗菌性をもつ高
分子化合物の開発が進められているが、未だ充分に目的
を達するに至つていない。In order to solve these problems, development of a polymer compound having antibacterial properties has been promoted, but its purpose has not yet been sufficiently achieved.
（発明が解決しようとする課題） 本発明の目的は優れた抗菌力を有し、且つその持続性
に優れた抗菌性ポリマーを提供することにある。(Problems to be Solved by the Invention) It is an object of the present invention to provide an antibacterial polymer having excellent antibacterial activity and excellent durability.
（課題を解決するための手段） 本発明は一般式 （式中Ａは を示し、ｌは20〜2000、X,YはBr-,Cl-,I-,NO3 -,CH3COO-
又はSO4 2-から選ばれるアニオンで同一又は異なつてい
てもよく、Ｒは炭素数６〜18のアルキル基、ｍは２〜10
の整数を示す）で表わされる抗菌性ポリマーに係る。(Means for Solving the Problems) The present invention has a general formula (Where A is Are shown, l is 20 to 2000, X, Y is Br -, Cl -, I - , NO 3 -, CH 3 COO -
Or an anion selected from SO 4 2- which may be the same or different, R is an alkyl group having 6 to 18 carbon atoms, m is 2 to 10
Which is an integer).
更に本発明は一般式 （式中Ａは を示し、X,YはBr-,Cl-,I-,NO3 -,CH3COO-又はSO4 2-から
選ばれるアニオンで同一又は異なつていてもよく、Ｒは
炭素数６〜18のアルキル基、ｍは２〜10の整数を示す）
で表わされる各モノマー単位の合計が1000以上であるポ
リマーからなる抗菌性ポリマーに係る。Further, the present invention provides a compound of the general formula (Where A is Are shown, X, Y is Br -, Cl -, I - , NO 3 -, CH 3 COO - or SO 4 may be the different from one identical or anion selected from 2-, R is C6-18 And m represents an integer of 2 to 10)
The present invention relates to an antibacterial polymer composed of a polymer having a total of each monomer unit of 1000 or more.
本発明に係る抗菌性ポリマーの構造式中Ｒの長鎖アル
キル基は炭素数が６〜18の範囲のものが用いられるが、
抗菌力の観点から、8,10,12がより好ましい。尚、アニ
オンについては特に限定されず、Br-,Cl-,I-,NO3 -,CH3C
OO-及びSO4 2-などを含む。ｌは20〜2000、ｍは２〜10の
整数が好ましい。The long-chain alkyl group R in the structural formula of the antibacterial polymer according to the present invention has a carbon number in the range of 6 to 18,
From the viewpoint of antibacterial activity, 8, 10, and 12 are more preferable. Incidentally, there is no particular limitation on the anion, Br -, Cl -, I -, NO 3 -, CH 3 C
OO - and SO 4 2-like. 1 is preferably an integer of 20 to 2000, and m is preferably an integer of 2 to 10.
本発明の抗菌性ポリマーは第四級窒素原子と主鎖との
スペースを考慮したこと、不溶性であること及び抗菌力
が強いことを特徴としている。The antibacterial polymer of the present invention is characterized by considering the space between the quaternary nitrogen atom and the main chain, being insoluble, and having a strong antibacterial activity.
更に本発明の抗菌性ポリマーは粒度２μｍ〜10mmφ、
特に３μｍ〜1mmφの球状のものが好ましく、利用形態
として、そのままカラム充填しての使用、水に懸濁させ
ての使用、或いは他のポリマーへの混練によるシート化
による使用などを挙げることができる。Further, the antibacterial polymer of the present invention has a particle size of 2 μm to 10 mmφ,
In particular, a spherical shape having a diameter of 3 μm to 1 mmφ is preferred, and examples of the form of use include use as it is in a column packed, use in suspension in water, or use as a sheet by kneading with another polymer. .
本発明に係る抗菌性ポリマーはグラム陽性菌、グラム
陰性菌に対し広い抗菌スペクトルを示す。又、カビに対
しても増殖阻害効果が認められた。The antibacterial polymer according to the present invention shows a broad antibacterial spectrum against Gram-positive bacteria and Gram-negative bacteria. In addition, a growth inhibitory effect was also observed against mold.
以下に本発明に係る抗菌性ポリマー製造の一例を反応
式で示す。Hereinafter, an example of the production of the antibacterial polymer according to the present invention is shown by a reaction formula.
上記（１）において化合物（Ｐ）は化合物（Ｈ）に対
して通常約1.0〜2.5倍モル、好ましくは約1.1〜2.1倍モ
ル反応させるのが良い。反応は有機溶媒中で行うのが好
ましく、一般に約60〜110℃の反応温度が好適である。
生成物（Ｂ）は濃縮、蒸留、再結晶などの方法により精
製することができる。反応式（２）の重合は通常の懸濁
重合、溶液重合、塊重合などの方法で行なうことがで
き、得られたポリマーは再沈殿、洗浄等の方法で精製す
ることができる。反応式（３）の反応においては、化合
物（PCS）又は（PCSDB）の塩素１当量に対して化合物
（Ｂ）を通常約0.02〜0.15当量、好ましくは約0.05〜0.
10当量反応させるのが好ましい。反応は有機溶媒中で行
うのが好ましく、一般に約60〜100℃の反応温度が好適
である。生成物（PCS−Ｂ）又は（PCSDB−Ｂ）は再沈
殿、洗浄などの方法により精製することができる。Ａが
上記以外の化合物も同様の反応により製造することがで
きる。 In the above (1), the compound (P) is usually reacted in an amount of about 1.0 to 2.5 times, preferably about 1.1 to 2.1 times, the mole of the compound (H). The reaction is preferably performed in an organic solvent, and a reaction temperature of about 60 to 110 ° C is generally suitable.
The product (B) can be purified by a method such as concentration, distillation, and recrystallization. The polymerization of the reaction formula (2) can be carried out by a usual method such as suspension polymerization, solution polymerization or bulk polymerization, and the obtained polymer can be purified by a method such as reprecipitation and washing. In the reaction of the reaction formula (3), the compound (B) is usually used in an amount of about 0.02 to 0.15 equivalent, preferably about 0.05 to 0.1 equivalent to 1 equivalent of chlorine of the compound (PCS) or (PCSDB).
It is preferable to react 10 equivalents. The reaction is preferably carried out in an organic solvent, and a reaction temperature of about 60 to 100 ° C is generally suitable. The product (PCS-B) or (PCSDB-B) can be purified by a method such as reprecipitation and washing. Compounds in which A is other than those described above can be produced by a similar reaction.
（発明の効果） 本発明の抗菌性ポリマーは分子鎖中にカチオンが２つ
のバイカチオン化合物を有するもので、優れた抗菌力と
広い抗菌スペクトルを生かして、プール、飲料水、冷却
水などの抗菌剤、或いはスライムコントロール剤として
有効に利用することができる。又、合成樹脂等への添加
によつて建材、農業用資材などの防菌防黴にも有効に利
用することができる。(Effect of the Invention) The antibacterial polymer of the present invention has a bicationic compound having two cations in the molecular chain. The antibacterial polymer of the pool, drinking water, cooling water, etc., has excellent antibacterial activity and a broad antibacterial spectrum. It can be effectively used as an agent or a slime control agent. In addition, by adding it to synthetic resins and the like, it can be effectively used for germicidal and fungicidal protection of building materials and agricultural materials.
（実 施 例） 以下に実施例及び試験例を挙げて詳しく説明する。(Examples) Hereinafter, examples and test examples will be described in detail.
実施例１ 撹拌機、還流コンデンサー、窒素導入管及び滴下ロー
トをつけた300ml丸底フラスコにエチルアルコール100ml
及び4,4′−ビピリジル31.2g（0.2モル）を仕込んだ
後、乾燥窒素を導入しつつ、90℃の油浴上で加熱しなが
ら滴下ロートより、ラウリルブロマイド24.9g（0.1モ
ル）を２時間かけて滴下した。18時間加熱撹拌した後、
溶媒を除去し、メタノール：アセトン系より再結晶し
た。55gの臭化Ｎ−ラウリル−4,4′−ピリジルピリジニ
ウム（以下Ｂと略す）が得られた。他のアルキルハライ
ドに対しても同様に反応せしめた。Example 1 100 ml of ethyl alcohol was placed in a 300 ml round bottom flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a dropping funnel.
After charging 31.2 g (0.2 mol) of 4,4'-bipyridyl, 24.9 g (0.1 mol) of lauryl bromide was added from a dropping funnel while heating on a 90 ° C. oil bath while introducing dry nitrogen for 2 hours. It dripped over. After heating and stirring for 18 hours,
The solvent was removed and recrystallized from a methanol: acetone system. 55 g of N-lauryl-4,4'-pyridylpyridinium bromide (hereinafter abbreviated as B) was obtained. The same reaction was performed for other alkyl halides.
次いで常法の懸濁重合により、ｐ−クロロメチルスチ
レン（CSと略す）のホモポリマー（以下PCSと略す）を
重合反応で生成した。得られたポリマーは熱アセトンで
洗浄し、未反応のモノマーを除去した。Next, a homopolymer of p-chloromethylstyrene (abbreviated as CS) (hereinafter abbreviated as PCS) was produced by a polymerization reaction by a conventional suspension polymerization. The obtained polymer was washed with hot acetone to remove unreacted monomers.
得られた（Ｂ）10gをポリマーPCS（200g）にメチルア
ルコール（800ml）中、60℃で50時間反応させた結果、
抗菌性ポリマー（PCS−Ｂ）208.3gが得られた。As a result of reacting 10 g of the obtained (B) with polymer PCS (200 g) in methyl alcohol (800 ml) at 60 ° C. for 50 hours,
208.3 g of an antibacterial polymer (PCS-B) was obtained.
実施例２ 実施例１と同様にしてCSとジビニルベンゼン（DBと略
す）のコポリマー（PCSDBと略す）を重合反応で生成し
た。得られたポリマーは熱アセトンで洗浄し、未反応の
モノマーを除去した。Example 2 In the same manner as in Example 1, a copolymer (abbreviated as PCSDB) of CS and divinylbenzene (abbreviated as DB) was produced by a polymerization reaction. The obtained polymer was washed with hot acetone to remove unreacted monomers.
（Ｂ）5gをPCSDB（200g）にエチルアルコール（800m
l）中、70℃で20時間反応させた結果、抗菌性ポリマー
（PCSDB−Ｂと略す）204.5gが得られた。抗菌性ポリマ
ーをブロムフエノールブルー（BPB）のメタノール溶液
で定量したところ、いずれも四級化率は約90％であつ
た。(B) 5 g of PCSDB (200 g) in ethyl alcohol (800 m
As a result of reaction at 70 ° C. for 20 hours in l), 204.5 g of an antibacterial polymer (abbreviated as PCSDB-B) was obtained. When the antibacterial polymer was quantified with a solution of bromphenol blue (BPB) in methanol, the quaternization rate was about 90% in all cases.
実施例３ 撹拌機、還流コンデンサー、窒素導入管及び滴下ロー
トをつけた300ml丸底フラスコにニトロメタン290g（4.8
モル）及び2,2′−ビピリジル13.5g（0.086モル）を仕
込んだ後、乾燥窒素を導入しつつ、110℃の油浴上で加
熱しながら滴下ロートよりラウリルブロマイド44.7g
（0.18モル）を２時間かけて滴下した。Example 3 In a 300 ml round bottom flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube and a dropping funnel, 290 g of nitromethane (4.8 g) was added.
Mol) and 13.5 g (0.086 mol) of 2,2′-bipyridyl, and then 44.7 g of lauryl bromide from a dropping funnel while heating on a 110 ° C. oil bath while introducing dry nitrogen.
(0.18 mol) was added dropwise over 2 hours.
５時間加熱攪拌した後、溶媒を除去し、エタノール：
アセトン系より再結晶した。12gの臭化Ｎ−ラウリル−
2,2′−ピリジルピリジニウム（以下2,2′−BPQ−C12と
略す）が得られた。他のアルキルハライドに対しても同
様に反応せしめた。After heating and stirring for 5 hours, the solvent was removed, and ethanol:
It was recrystallized from acetone. 12 g of N-lauryl bromide
2,2' pyridyl pyridinium (hereinafter abbreviated as 2,2'-BPQ-C 12) was obtained. The same reaction was performed for other alkyl halides.
次いで実施例１で得られたポリマーPCS（200g）に2,
2′−BPQ−C12（10g）を、メタノール800ml中、60℃で5
0時間反応させた結果、抗菌性ポリマー（2,2′−BPCQ−
C12）207.2gが得られた。Then, 2,2 g was added to the polymer PCS (200 g) obtained in Example 1.
2′-BPQ-C 12 (10 g) was dissolved in 800 ml of methanol at 60 ° C. for 5 hours.
After reacting for 0 hours, the antibacterial polymer (2,2'-BPCQ-
C 12 ) 207.2 g were obtained.
試験例１ 抗菌性ポリマー（PCSDB−Ｂ）を20mg用いて抗菌スペ
クトルを測定した。測定条件は菌懸濁液100ml（菌数６
×108cells）、温度30℃である。結果を第１表に示す。Test Example 1 An antibacterial spectrum was measured using 20 mg of an antibacterial polymer (PCSDB-B). The measurement conditions were 100 ml of bacterial suspension (the number of bacteria was 6).
× 10 8 cells) at a temperature of 30 ° C. The results are shown in Table 1.
試験例２ 抗菌性ポリマー（PCS−Ｂ）を用いて、下記第２表に
示す配合で （ａ）ミキシングロール;D＝10in.16rpm （ｂ）ロール温度×時間;140〜145℃×５分 （ｃ）シート厚み;0.5mm の条件で混練してシートを作成し、このシートを用いて
JIS Z2911に従つて、かびの抗菌性試験を行つた。結果
を第３表に示す。 Test Example 2 Using an antibacterial polymer (PCS-B), the composition shown in Table 2 below was used: (a) mixing roll; D = 10 in. 16 rpm (b) roll temperature × time; 140-145 ° C. × 5 minutes ( c) A sheet is prepared by kneading under the condition of a sheet thickness of 0.5 mm.
According to JIS Z2911, an antibacterial test of mold was conducted. The results are shown in Table 3.
第３表においてNo.1〜５はそれぞれPVCに対して（PCS
−Ｂ）の含量が0,0.067,0.100,0.133及び0.200wt％の場
合に相当する。 In Table 3, Nos. 1 to 5 correspond to PVC (PCS
-B) corresponding to the contents 0, 0.067, 0.100, 0.133 and 0.200 wt%.
また＋は菌糸着生、 ｓは胞子付着生、 −は変化なしを示す。 In addition, + indicates hyphae formation, s indicates spore adherence, and-indicates no change.
試験例３ 試験例１と同様に抗菌性ポリマー（2,2′−BPCQ−
C12）を10mg用いて抗菌力を測定した。結果を第４表に
示す。Test Example 3 An antibacterial polymer (2,2'-BPCQ-
The C 12) were measured antibacterial activity using 10 mg. The results are shown in Table 4.
Claims (2)
又はSO4 2-から選ばれるアニオンで同一又は異なつてい
てもよく、Ｒは炭素数６〜18のアルキル基、ｍは２〜10
の整数を示す）で表わされる抗菌性ポリマー。(1) General formula (Where A is Are shown, l is 20 to 2000, X, Y is Br -, Cl -, I - , NO 3 -, CH 3 COO -
Or an anion selected from SO 4 2- which may be the same or different, R is an alkyl group having 6 to 18 carbon atoms, m is 2 to 10
An antimicrobial polymer represented by the following formula:
選ばれるアニオンで同一又は異なつていてもよく、Ｒは
炭素数６〜18のアルキル基、ｍは２〜10の整数を示す）
で表わされる各モノマー単位の合計が1000以上であるポ
リマーからなる抗菌性ポリマー。2. The general formula (Where A is Are shown, X, Y is Br -, Cl -, I - , NO 3 -, CH 3 COO - or SO 4 may be the different from one identical or anion selected from 2-, R is C6-18 And m represents an integer of 2 to 10)
An antibacterial polymer comprising a polymer having a total of 1000 or more of each monomer unit represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63047750A JP2657509B2 (en) | 1987-04-17 | 1988-02-29 | Antibacterial polymer |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62-96042 | 1987-04-17 | ||
| JP9604287 | 1987-04-17 | ||
| JP63047750A JP2657509B2 (en) | 1987-04-17 | 1988-02-29 | Antibacterial polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6426610A JPS6426610A (en) | 1989-01-27 |
| JP2657509B2 true JP2657509B2 (en) | 1997-09-24 |
Family
ID=26387921
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63047750A Expired - Lifetime JP2657509B2 (en) | 1987-04-17 | 1988-02-29 | Antibacterial polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2657509B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3004442B2 (en) * | 1992-01-27 | 2000-01-31 | サンスター株式会社 | Oral composition |
| JP2686581B2 (en) * | 1992-02-20 | 1997-12-08 | 大塚化学 株式会社 | Vinyl-based copolymer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6230249A (en) * | 1985-07-09 | 1987-02-09 | Fuji Photo Film Co Ltd | Polymer mordant |
-
1988
- 1988-02-29 JP JP63047750A patent/JP2657509B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6426610A (en) | 1989-01-27 |
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