JPS63115838A - Novel polymerizable halogen compound - Google Patents
Novel polymerizable halogen compoundInfo
- Publication number
- JPS63115838A JPS63115838A JP26312986A JP26312986A JPS63115838A JP S63115838 A JPS63115838 A JP S63115838A JP 26312986 A JP26312986 A JP 26312986A JP 26312986 A JP26312986 A JP 26312986A JP S63115838 A JPS63115838 A JP S63115838A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- halogen compound
- formula
- expressed
- present
- 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
Links
- 150000002366 halogen compounds Chemical class 0.000 title claims abstract description 13
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 11
- 229940121375 antifungal agent Drugs 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003429 antifungal agent Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 3
- 230000000843 anti-fungal effect Effects 0.000 abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 239000011734 sodium Substances 0.000 abstract description 3
- 229910052708 sodium Inorganic materials 0.000 abstract description 3
- 241001465754 Metazoa Species 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract description 2
- 230000005012 migration Effects 0.000 abstract description 2
- 238000013508 migration Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- YMCIJACRUUPRKK-UHFFFAOYSA-N 1,2,3,4,5-pentachloro-6-(3-phenylprop-2-enoxy)benzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1OCC=CC1=CC=CC=C1 YMCIJACRUUPRKK-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 8
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- -1 sheets Substances 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- HCJLVWUMMKIQIM-UHFFFAOYSA-M sodium;2,3,4,5,6-pentachlorophenolate Chemical compound [Na+].[O-]C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl HCJLVWUMMKIQIM-UHFFFAOYSA-M 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 239000000417 fungicide Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002062 proliferating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000014347 soups Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は防黴剤として好適な新規な重合性ハロゲン化合
物に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a novel polymerizable halogen compound suitable as a fungicide.
（従来の技術）
製品や備品等に黴が生えるのを防止するために、「防国
防微の化学」 （堀口博著、三共出版、昭和５７年）に
紀αされている様な防黴剤を添加したり、予め防黴剤を
添加した塗料等によるコーティング処理が行われている
。防黴剤としては人畜に無害で、黴にはよ（効き、製品
に容易に溶解または分散し水には難溶でかつ不運発であ
るものが理想的であるが、現実にはこの様なものはまだ
見出されておらず、製品中での凝集、マイグレーション
等によって効力が失われるのが通常である。(Prior art) In order to prevent mold from growing on products and equipment, anti-mold agents such as those described in "Chemistry of Defense Microchemistry" (written by Hiroshi Horiguchi, published by Sankyo Publishing, 1982) are used. Coating treatment is carried out using paints or the like to which antifungal agents have been added. The ideal antifungal agent would be one that is harmless to humans and livestock, effective against mold, easily dissolved or dispersed in products, poorly soluble in water, and non-proliferative, but in reality, such agents are No such substance has been found yet, and efficacy is usually lost due to aggregation, migration, etc. in products.
（発明が解決しようとする問題）
本発明は前記従来の欠点の解消された、即ち人畜に無害
で、不揮発性、水にＪｌｌｔｔｊ性かつ製品中で効力が
失われる問題点を解消した防黴剤として好適な重合性ハ
ロゲン化合物を提供せんとするものである。(Problems to be Solved by the Invention) The present invention provides an anti-mold agent which eliminates the above-mentioned drawbacks of the prior art, namely, is harmless to humans and animals, is non-volatile, is resistant to water, and eliminates the problems of loss of efficacy in products. It is an object of the present invention to provide a polymerizable halogen compound suitable as a polymerizable halogen compound.
（問題点を解決するための手段）
本発明者等はこれらの問題点を解決すべく説き研究の結
果本発明に到達した。本発明は下記一般式で表わされる
防黴剤としてを効な新規な重合性ハロゲン化合物である
。(Means for Solving the Problems) The present inventors have arrived at the present invention as a result of their preaching and research in order to solve these problems. The present invention is a novel polymerizable halogen compound represented by the following general formula that is effective as a fungicide.
本発明の重合性ハロゲン化合物は臭素または塩素のハロ
ゲン原子を含むが好ましくは塩素であり、上記一般式で
示される式中のｎは１〜５であるが最も好ましいのはｎ
＝５のペンタクロロ化合物である。The polymerizable halogen compound of the present invention contains a halogen atom of bromine or chlorine, preferably chlorine, and n in the above general formula is 1 to 5, but most preferably n
=5 pentachloro compound.
本発明の重合性ハロゲン化合物はクロロメチルスチレン
（ｍ／Ｐ混合体でも、Ｐ単独体でもよい）に防黴性化合
物のナトリウムクロロフェネート等を反応させて得るこ
とができる。この反応は適当な育機溶媒の存在下で実施
することができる。この反応は例えばナトリウムペンタ
クロロフェネートを用いた場合の反応は下記の反応式で
示される。The polymerizable halogen compound of the present invention can be obtained by reacting chloromethylstyrene (either an m/P mixture or P alone) with an antifungal compound such as sodium chlorophenate. This reaction can be carried out in the presence of a suitable growth solvent. This reaction, for example when sodium pentachlorophenate is used, is shown by the reaction formula below.
＋
ａＣ１
本発明の重合性ハロゲン化合物はシート、フィルム、容
器、繊維等の成形物にその成形前あるいは成形後に単量
体あるいは重合体の形で用いて防黴性を付与することが
できる。+ aC1 The polymerizable halogen compound of the present invention can be used in the form of a monomer or polymer to impart mold resistance to molded products such as sheets, films, containers, fibers, etc. before or after molding.
単ｎ体で用いる場合は成形物内でｍ合させることが望ま
しく、重合体で用いる場合はポリマーブレンドや成形物
に塗布する方法などがある。When used as a single n substance, it is desirable to perform m-combination within a molded product, and when used as a polymer, there are methods such as a polymer blend or coating on a molded product.
以下実施例により本発明を説明するが、これにより本発
明が限定されるものではない。なお、実施例中における
徴抵抗性試験は下記の方法によった。The present invention will be explained below with reference to Examples, but the present invention is not limited thereto. In addition, the resistance test in the examples was carried out by the following method.
微抵抗試験（ＪＩＳ−Ｚ−２９１１）
無機塩のみを含有したシャーレに試験に用いる化合物を
各々分散させた液体培地を流し込み、培地が同化後、指
定された９１４株の胞子懸濁液を噴霧し後２７±１℃で
１０日間培養した。なお、培養試験後の数紙抗性の判定
は次によった。Microresistance test (JIS-Z-2911) A liquid medium in which each of the compounds used for the test was dispersed was poured into a petri dish containing only inorganic salts, and after the medium had assimilated, a spore suspension of the designated strain 914 was sprayed. Afterwards, the cells were cultured at 27±1°C for 10 days. In addition, the determination of paper resistance after the culture test was as follows.
以 下 余 白
実施例１
撹拌機、二度肝、窒素ガス吹込み管を備えた５００璽ｔ
の４０フラスコ中でエタ／−ル５０ＩＱにクロロメチル
スチレン（■Ｉｐ＝ ００／４０）２５ ｇ（０。Below is the margin Example 1 500 liters equipped with a stirrer, double liver, and nitrogen gas blowing pipe
25 g of chloromethylstyrene (Ip = 00/40) in ethanol 50IQ in a 40 flask (0.
１６１モル）を室温で溶解した後、ナトリウムベンタク
ロロフェネー） （以下、Ｎａ−ＰＣＰと略記’）４９
ｇ （０，１７０モル）を水／エタノール（１／１）混
合溶媒２５０ｍ１に溶解した溶液を徐々に滴下し、滴下
終了後、５０℃で１時間反応させた。冷却後沈殿物を濾
別し、濾液をロータリーエバボレータープ濃縮した。次
いでＯ相液にｎ−ヘ牛すン２５０−党、純水１００ｍｔ
を加え振とうし後水層を除去し、さらに純水１００ｍｆ
ｆ１を加え同様な保作をくり返し未反応のＮａ−ＰＣＰ
を除去した。後ｎ−へキサ７層をロータリーエバポレー
ターで蒸発した。次いで残香の固形分をアセトン中で再
結晶した。その結果融点が１１３〜１１５℃である白色
の針状結晶を得た。収率は８５％であった。After dissolving 161 mol) at room temperature, sodium bentachlorophene) (hereinafter abbreviated as Na-PCP')49
A solution of g (0,170 mol) dissolved in 250 ml of a water/ethanol (1/1) mixed solvent was gradually added dropwise, and after the dropwise addition was completed, the reaction was carried out at 50° C. for 1 hour. After cooling, the precipitate was filtered off, and the filtrate was concentrated using a rotary evaporator. Next, 250 tons of n-beef soup and 100 mt of pure water were added to the O phase liquid.
After shaking, remove the aqueous layer and add 100 mf of pure water.
Add f1 and repeat the same retention process to remove unreacted Na-PCP.
was removed. The 7 layers of n-hex were then evaporated using a rotary evaporator. The solid content of the residual aroma was then recrystallized in acetone. As a result, white needle-shaped crystals with a melting point of 113-115°C were obtained. The yield was 85%.
実施例２
クロロメチルスチレン（２体）を用いて実施例１と同様
に合成し融点が１４３〜１４５℃である白色の針伏結晶
を得た。収率は８３％であった。Example 2 White needle crystals having a melting point of 143 to 145° C. were synthesized in the same manner as in Example 1 using chloromethylstyrene (two bodies). The yield was 83%.
実施例１．２で得られた結晶を用いて行った元素分析、
赤外線分析（ＩＲ）、核磁気共鳴試ｇｉｌｔ（１３Ｃ−
ＮＭＲ）の結果は表−１、第１図〜第４図の如くであっ
た。それらの結果からいずれも（２，３，４，５，８−
ペンタクロロフェニールオキシ）メチルスチレンである
ことが同定された。Elemental analysis performed using the crystal obtained in Example 1.2,
Infrared analysis (IR), nuclear magnetic resonance gilt (13C-
The results of NMR were as shown in Table 1 and Figures 1 to 4. From those results, (2, 3, 4, 5, 8-
It was identified as pentachlorophenyloxy)methylstyrene.
表 −１
実施例−３
実施例−１、−２に示した本発明の（２，３゜４．５．
ｅ−べ／タクロロフェニールオキシ）メチルスチレンを
、比較例として用いたジンクオマ■
ジン 、Ｎａ−ＰＣＰの化合物を用いてＪＩＳ−Ｚ−２
９１１に基づく微抵抗試験を行った。その結果を表−２
に示した。Table-1 Example-3 The present invention shown in Examples-1 and -2 (2.3°4.5.
e-be/tachlorophenyloxy)methylstyrene was used as a comparative example.
A microresistance test based on 911 was conducted. Table 2 shows the results.
It was shown to.
以 下 余 白
表 −２
表−２から明らかな様に、本発明の化合物は比較例の公
知の防黴性化合物と比較し、何ら効力の低下が見られな
い。本発明の化合物は「ａ！溶媒中で２．２′−アゾビ
ス−１ｓｏ−ブチロニトリルを触媒としていずれも重合
できたことから、すぐれた重合性単量体として広範囲に
工業的利用が可能である。Margin Table 2 As is clear from Table 2, the compound of the present invention shows no decrease in efficacy compared to the known antifungal compound of the comparative example. The compounds of the present invention can be polymerized in a solvent using 2,2'-azobis-1so-butyronitrile as a catalyst, and therefore can be widely used industrially as excellent polymerizable monomers.
（発明の効果）
本発明によるハロゲン化合物はプラスチックシート、フ
ィルム、容器、繊維等の成形物に防黴性を付与する化合
物として好適で特に重合体として用いると不揮発性であ
るので毒性がなく耐久性に優れた防黴効果を付与するこ
とができる。(Effect of the invention) The halogen compound according to the present invention is suitable as a compound that imparts mold resistance to molded products such as plastic sheets, films, containers, fibers, etc. Especially when used as a polymer, it is non-volatile and therefore non-toxic and durable. It can provide excellent anti-mildew effect.
第１図及び第学図は実施例１で得られたｍ合性ハロゲン
化合物： （２，３，４，５，６−ベンタクロロフエ二
−ルオキシ）メチルスチレンの赤外吸収スペクトル及び
核磁気共鳴スペクトルであハロゲン化合物： （２，３
，４，５，６−ペタンクロロフエニールオキシ）メチル
スチレンの赤外吸収スペクトル及び核磁気共鳴スペクト
ルである。Figures 1 and 1 show the infrared absorption spectrum and nuclear magnetic resonance of the m-component halogen compound obtained in Example 1: (2,3,4,5,6-bentachlorophenyloxy)methylstyrene. Halogen compound in the spectrum: (2,3
, 4,5,6-petanechlorophenyloxy)methylstyrene.
Claims (1)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61263129A JP2640100B2 (en) | 1986-11-04 | 1986-11-04 | Antifungal agent using antifungal polymer obtained from polymerizable halogen compound |
| KR1019870011736A KR950004028B1 (en) | 1986-10-24 | 1987-10-22 | Novel polymeritable compound and polymer thereof |
| US07/268,956 US4956431A (en) | 1986-10-24 | 1988-11-09 | Novel polymerizable compound having mildew resistance and polymer thereof |
| US08/086,905 US5583230A (en) | 1986-10-24 | 1993-07-07 | Polymerizable compound having mildew resistance and polymer thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61263129A JP2640100B2 (en) | 1986-11-04 | 1986-11-04 | Antifungal agent using antifungal polymer obtained from polymerizable halogen compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63115838A true JPS63115838A (en) | 1988-05-20 |
| JP2640100B2 JP2640100B2 (en) | 1997-08-13 |
Family
ID=17385219
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61263129A Expired - Fee Related JP2640100B2 (en) | 1986-10-24 | 1986-11-04 | Antifungal agent using antifungal polymer obtained from polymerizable halogen compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2640100B2 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3058953A (en) * | 1959-05-27 | 1962-10-16 | Dow Chemical Co | Vinylbenzylhalophenylether and polymers and method of making the same |
| JPS5990846A (en) * | 1982-11-16 | 1984-05-25 | Toray Ind Inc | Radiosensitive material |
-
1986
- 1986-11-04 JP JP61263129A patent/JP2640100B2/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3058953A (en) * | 1959-05-27 | 1962-10-16 | Dow Chemical Co | Vinylbenzylhalophenylether and polymers and method of making the same |
| JPS5990846A (en) * | 1982-11-16 | 1984-05-25 | Toray Ind Inc | Radiosensitive material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2640100B2 (en) | 1997-08-13 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |