JPS60163902A - Stable organic peroxide composition - Google Patents
Stable organic peroxide compositionInfo
- Publication number
- JPS60163902A JPS60163902A JP1841284A JP1841284A JPS60163902A JP S60163902 A JPS60163902 A JP S60163902A JP 1841284 A JP1841284 A JP 1841284A JP 1841284 A JP1841284 A JP 1841284A JP S60163902 A JPS60163902 A JP S60163902A
- Authority
- JP
- Japan
- Prior art keywords
- organic peroxide
- composition
- content
- storage stability
- peroxide composition
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- 150000001451 organic peroxides Chemical class 0.000 title claims abstract description 28
- IUVLRIZZDUGZRK-UHFFFAOYSA-N 5-hydroperoxy-5-methyldioxolan-3-one Chemical compound OOC1(C)CC(=O)OO1 IUVLRIZZDUGZRK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000004480 active ingredient Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 229920006337 unsaturated polyester resin Polymers 0.000 abstract description 3
- 229920001567 vinyl ester resin Polymers 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000007796 conventional method Methods 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical class N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 4
- 229960001826 dimethylphthalate Drugs 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- -1 Alicyclic hydrocarbons Chemical class 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000003869 coulometry Methods 0.000 description 1
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PHILMFQVUWCHOQ-UHFFFAOYSA-N dioxolan-3-one Chemical compound O=C1CCOO1 PHILMFQVUWCHOQ-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 229940093858 ethyl acetoacetate Drugs 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polymerization Catalysts (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、５−ヒドロペルオキシ−５−メチル−１，２
−ジオキソラン−３−オンを有効成分とする貯蔵安定性
に優れた有機ペルオキシド組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention provides 5-hydroperoxy-5-methyl-1,2
The present invention relates to an organic peroxide composition containing dioxolan-3-one as an active ingredient and having excellent storage stability.
一般に、このよう麿有機ペルオキシド組成物は、不飽和
ポリエステル耐詣あるいはビニルエステル樹脂などの硬
化触媒として有用であり、それらを得る方法としては、
ジャーナル・オン・ザ・ケミカル・ソサイエテイ（Ｊｏ
ｕｒｎａｌｏｆ ｔｈｅ Ｏｈｅｍｉｃａ） ５ｏｃｉ
ｅｔｙ） （（０）＋１９６８年、２９８３頁〕および
英国特許第１２１９０８７号（以下単に英国特許という
）明細書に、アセト酢酸エステルと過酸化水素とを、ア
セト酢酸エステル１グラム分子に対して０．３５グラム
原子以上の濃度の水素イオンの存在下で反応させること
により、５−ヒドロペルオキシ−５−メチル−１，２−
ジオキソ２ンー３−オンを有効成分とする有機ペルオキ
シド組成物の得られることが記載されている。In general, such organic peroxide compositions are useful as curing catalysts for unsaturated polyester resins or vinyl ester resins, and methods for obtaining them include:
Journal on the Chemical Society (Jo
Urnalof the Ohmica) 5oci
ety) ((0)+1968, p. 2983) and British Patent No. 1219087 (hereinafter simply referred to as the British Patent), acetoacetate and hydrogen peroxide are mixed at 0.00% per gram molecule of acetoacetate. 5-hydroperoxy-5-methyl-1,2-
It is described that an organic peroxide composition containing dioxo-2-3-one as an active ingredient can be obtained.
すなわち、アセト酢酸エステルと過酸化水素との希釈剤
の存在下における酸触媒反応は、次に示す式に従って目
的の有機ペルオキシドとアルキルモノカルビノールとを
生成する。That is, the acid-catalyzed reaction of acetoacetate and hydrogen peroxide in the presence of a diluent produces the desired organic peroxide and alkyl monocarbinol according to the following formula.
（式中、Ｒはアルキル基である）
従って、得られる有機ペルオキシド組成物中ニハ、必然
的にアルキルモノカルピノ−／ｌ、（ＲＯＨ）が含まれ
る。(In the formula, R is an alkyl group.) Therefore, the resulting organic peroxide composition necessarily contains alkylmonocarpino-/l, (ROH).
そして、英国特許明細書では、上記反応式に従って得ら
れた反応液の有機層を飽和の硫酸アンモニウム水で４回
洗浄した後硫酸ナトリウムで脱水することにより、目的
とする有機ペルオキシド組成物を得ている。In the British patent specification, the desired organic peroxide composition is obtained by washing the organic layer of the reaction solution obtained according to the above reaction formula four times with saturated ammonium sulfate water and then dehydrating it with sodium sulfate. .
しかし、英国特許明細書に示される方法で得られる有機
ペルオキシド組成物は、極めて貯蔵安定性が農いため硬
化触媒としての工業的な利用価値は低かった。However, the organic peroxide composition obtained by the method shown in the British patent specification has extremely low storage stability and has low industrial utility value as a curing catalyst.
そこで、本発明者らは、このようにして得られた有機ペ
ルオキシド組成物の貯蔵安定性を向上させる目的で、希
釈剤の種類および量、有機ペルオキシドの種類および含
有率などについて種々検討した結果、有機ペルオキシド
組成物中に含まれる成分の一つであるアルキルモノカル
ビノールが、貯蔵安定性を著しく低下させる原因物質で
あることの知見を得て本発明を完成させるに至った。Therefore, in order to improve the storage stability of the organic peroxide composition obtained in this way, the present inventors conducted various studies on the type and amount of the diluent, the type and content rate of the organic peroxide, etc. The present invention was completed based on the knowledge that alkyl monocarbinol, which is one of the components contained in an organic peroxide composition, is a substance that causes a significant decrease in storage stability.
すなわち、本発明は、５−ヒドロペルオキシ−５−メチ
ル−１，２−ジオキソラン−３−オンを有効成分とし、
アルキルモノカルビノールの含有率が０．５重量％以下
である有機ペルオキシド組成物に関する。That is, the present invention uses 5-hydroperoxy-5-methyl-1,2-dioxolan-3-one as an active ingredient,
The present invention relates to an organic peroxide composition having an alkyl monocarbinol content of 0.5% by weight or less.
このアルキルモノカルビノールの含有率が０゜５重量％
以下の場合は、３０℃で６０日間貯蔵しても、５−ヒト
四ペルオキシー５−メチル−１，２−ジオキソラン−３
−オンの分解率はわずか１３％程度であるが、含有率が
０．５重量％を超えると極めて分解率が高くなり、本発
明の目的を達し得ないので好ましくカい。The content of this alkyl monocarbinol is 0.5% by weight.
In the following cases, even if stored at 30°C for 60 days, 5-human tetraperoxy-5-methyl-1,2-dioxolane-3
The decomposition rate of -one is only about 13%, but if the content exceeds 0.5% by weight, the decomposition rate becomes extremely high and the object of the present invention cannot be achieved, so it is preferable.
本発明の有機ペルオキシド組成物は、英国特許明細書に
示された製造法のうち、反応液の有機層の洗浄液を飽和
の硫酸アンモニウム水から水に変更するか、あるいは飽
和の硫酸アンモニウム水で洗浄した後さらに水で洗浄す
ることにより得られる。また、英国特許明細書に示され
た製造法で得た有機ペルオキシド組成物を蒸発処理する
ことにより、アルキルモノカルビノールを留去すること
によっても得ることができる。The organic peroxide composition of the present invention can be produced by changing the washing liquid for the organic layer of the reaction solution from saturated ammonium sulfate water to water, or by washing it with saturated ammonium sulfate water, according to the manufacturing method shown in the British patent specification. It can be obtained by further washing with water. It can also be obtained by distilling off the alkyl monocarbinol by evaporating the organic peroxide composition obtained by the production method shown in the British patent specification.
本発明で用いられる希釈剤は、例えば、ベンゼ／、トル
エン、キシレンＡどの芳香族炭化水素；ヘキサン、ヘプ
タン、オクタン、イソオクタンなどの叫訪族炭化水素；
シクロヘキサン、ｌ、１−ジメチルシクロヘキサンなど
の脂環式炭化水素；酢酸エチル、酢酸ブチル、フタル酸
ジメチル、アセト酢酸エチル、フマル酸ジメチル、アジ
ピン酸ジオクチル、イタコン酸ジメチルなどのエステル
類などを単独であるいは組み合わせて用いることができ
る。この希釈剤の種類および含有率を変化させても、有
機ペルオキシド組成物の安定性には影響がない。The diluent used in the present invention is, for example, an aromatic hydrocarbon such as benzene, toluene, or xylene A;
Alicyclic hydrocarbons such as cyclohexane, l,1-dimethylcyclohexane; esters such as ethyl acetate, butyl acetate, dimethyl phthalate, ethyl acetoacetate, dimethyl fumarate, dioctyl adipate, dimethyl itaconate, etc. alone or Can be used in combination. Varying the type and content of this diluent does not affect the stability of the organic peroxide composition.
一方、有機ペルオキシドの含有率が、５０重量％を超え
ると、使用目的である硬化触媒としての活性が強すぎ、
また１０重量％未満であると逆に活性か弱すぎるため、
使用上極めて不便である。従って、硬化触媒として使用
する上では有機ペルオキシドの含有率は１０ないし５０
重量％の範囲が好ましい。On the other hand, if the content of organic peroxide exceeds 50% by weight, its activity as a curing catalyst, which is the intended use, will be too strong.
On the other hand, if it is less than 10% by weight, the activity will be too weak.
It is extremely inconvenient to use. Therefore, when used as a curing catalyst, the content of organic peroxide should be 10 to 50%.
A weight percent range is preferred.
以上のごとく、本発明の有機ペルオキシド組成物は貯蔵
安定性が極めて優れており、不飽和ポリエステル樹脂な
どの硬化触媒々どとして工業的利用価値が大きい。As described above, the organic peroxide composition of the present invention has extremely excellent storage stability and has great industrial utility value as a curing catalyst for unsaturated polyester resins and the like.
次に、実施例および比較例により本発明を具体的に説明
する。Next, the present invention will be specifically explained using Examples and Comparative Examples.
実施例１
５０？のアセト酢酸エチル、５０ｆの７タル酸ジメチル
およびＱ、 ｌ ｍｌの５体積％濃度の硫酸をビーカー
中で混合した。混合液を３０℃以下に保ちながら４８．
９９−の６０重量％濃度の過酸化水素水を１０分間にわ
たって添加した。さらに２時間攪拌してから０℃に冷却
した後、１３ｄの５０重量％濃度の硫酸を添加し、室温
で一夜攪拌した。反応液の有機層を飽和の硫酸アンモニ
ウム水で４回洗浄してからさらに水で３回洗浄した後、
硫酸ナトリウムで脱水して６旦、６？の有機ペルオキシ
ド組成物を得た。Example 1 50? of ethyl acetoacetate, 50f of dimethyl 7-talate and Q, l ml of 5% strength by volume sulfuric acid were mixed in a beaker. 48. While keeping the mixture below 30°C.
99-60% strength by weight hydrogen peroxide solution was added over a period of 10 minutes. After stirring for a further 2 hours and cooling to 0°C, 13d of 50% strength by weight sulfuric acid was added and stirred overnight at room temperature. After washing the organic layer of the reaction solution four times with saturated ammonium sulfate water and further washing three times with water,
Dehydrated with sodium sulfate, 6 days, 6 days? An organic peroxide composition was obtained.
この組成物中の有機ペルオキシド含有率を活性酸素量か
ら、また、エチルアルコール、フタル酸ジメチルおよび
アセト酢酸エチルの含有率をガスクロマトグラフィーに
よりそれぞれ定量した。さらに、この組成物の３０℃に
おける貯蔵安宇性を活性酸素量の経日保持率をもって示
した。その結果を第１表に示す。The organic peroxide content in this composition was determined from the amount of active oxygen, and the content of ethyl alcohol, dimethyl phthalate, and ethyl acetoacetate was determined by gas chromatography. Furthermore, the storage stability of this composition at 30°C was shown by the retention rate of active oxygen content over time. The results are shown in Table 1.
実施例２
６０重量％濃度の過酸化水素水４９ｔに５０重量％濃度
の硫酸１３ｍ／！とフタル酸ジメチル１２０１とを１０
℃で加えて混合した。次に混合液を１０℃に保ち彦がら
アセト醋酸メチル５０１を加えた後、３０℃に温めて３
時間攪拌した。Example 2 49 tons of hydrogen peroxide solution with a concentration of 60% by weight and 13 m of sulfuric acid with a concentration of 50% by weight/! and dimethyl phthalate 1201 and 10
℃ and mixed. Next, methyl acetoacetate 501 was added to the mixture while keeping it at 10°C, then warmed to 30°C and
Stir for hours.
反応液の有機層を飽和の硫酸アンモニウム水５０ｍ１で
２回洗浄し、硫酸ナトリウムで脱水した。The organic layer of the reaction solution was washed twice with 50 ml of saturated ammonium sulfate water and dehydrated with sodium sulfate.
さらに２３１１１１１ＩｆＦの減圧下、３０℃で蒸発処
理して１６０デの有機ペルオキシド組成物を得た。Further, the mixture was evaporated at 30° C. under a reduced pressure of 2311111IfF to obtain an organic peroxide composition of 160 degrees.
この組成物の各成分の定量および貯蔵安定性は、実施例
１と同様の方法で測定した。その結果を第１表に示す。The quantitative determination and storage stability of each component of this composition were measured in the same manner as in Example 1. The results are shown in Table 1.
比較例１
実施例１において水で３回洗浄すること以外は実施例１
に準じて実施し、８７．３Ｐの有機ペルオキシド組成物
を得た。Comparative Example 1 Example 1 except for washing three times with water in Example 1
An organic peroxide composition of 87.3P was obtained.
この組成物の各成分の定量および貯蔵安定性は実施例１
と同様の方法で測定した。Quantification and storage stability of each component of this composition are shown in Example 1.
It was measured in the same manner as.
その結果を第１表に示す。The results are shown in Table 1.
比較例２
実施例２において２３１１Ｈ５’の減圧下、３０℃で蒸
発処理すること以外は実施例２に準じて実施し、１６３
ｙ−の有機ペルオキシド組成物を得た。Comparative Example 2 The procedure of Example 2 was followed except that the evaporation treatment was carried out at 30°C under reduced pressure of 2311H5', and 163
An organic peroxide composition of y- was obtained.
との組成物の各成分の電量および貯蔵安定性は、実施例
１と同様の方法で測定した。The coulometric capacity and storage stability of each component of the composition were measured in the same manner as in Example 1.
第１表に示した結果から、本発明の有機ペルオキシド組
成物の貯蔵安定性は、有機ペルオキシド含有率および希
釈剤（フタル酸ジメチルおよびアセト酢酸エステル）含
有率に影響されないことが明らかである。From the results shown in Table 1, it is clear that the storage stability of the organic peroxide compositions of the present invention is not affected by the organic peroxide content and the diluent (dimethyl phthalate and acetoacetate) content.
さらに、組成物中のアルキルモノカルビノールの含有率
が０，５重量％以下の場合（実施例１．２）では極めて
良好な貯蔵安定性を示しているのに対して、０．５重量
％を超える場合（比較例１．２）は、３０℃における６
０日後の活性酸素量の保持率が初めの３０％以下となっ
て貯蔵安定性が極めて悪いことが明白でおる。Furthermore, when the content of alkyl monocarbinol in the composition was 0.5% by weight or less (Example 1.2), it showed extremely good storage stability; 6 at 30°C (Comparative Example 1.2)
It is clear that the retention rate of active oxygen amount after 0 days is less than 30% of the initial amount, and the storage stability is extremely poor.
特許出願人 日本油脂株式会社 代理人弁理士 漫 野 豐 司Patent applicant: NOF Corporation Representative Patent Attorney Tsukasa Manno
Claims (1)
ラン−３−オンを有効成分とし、アルキルモノカルビノ
ールの含有率が０．５重量％以下である有機ペルオキシ
ド組成物An organic peroxide composition containing 5-hydroperoxy-5-methyl-1,2-dioxolan-3-one as an active ingredient and having an alkyl monocarbinol content of 0.5% by weight or less
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1841284A JPS60163902A (en) | 1984-02-06 | 1984-02-06 | Stable organic peroxide composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1841284A JPS60163902A (en) | 1984-02-06 | 1984-02-06 | Stable organic peroxide composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60163902A true JPS60163902A (en) | 1985-08-26 |
| JPH0564148B2 JPH0564148B2 (en) | 1993-09-14 |
Family
ID=11970935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1841284A Granted JPS60163902A (en) | 1984-02-06 | 1984-02-06 | Stable organic peroxide composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60163902A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0589418U (en) * | 1992-05-07 | 1993-12-07 | 大 遠江 | Riding helmet |
| US11839213B2 (en) | 2008-11-20 | 2023-12-12 | Armis Biopharma, Inc. | Antimicrobial, disinfecting, and wound healing compositions and methods for producing and using the same |
| US11969399B2 (en) | 2017-07-07 | 2024-04-30 | Armis Biopharma, Inc. | Compositions and methods for remediating chemical warfare agent exposed skin |
| US12702655B2 (en) | 2017-07-07 | 2026-08-11 | Armis Biopharma, Inc. | Antimicrobial, disinfecting and wound healing compositions and methods for producing and using same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3639425A (en) * | 1967-04-05 | 1972-02-01 | Laporte Chemical | Peroxygen compound |
-
1984
- 1984-02-06 JP JP1841284A patent/JPS60163902A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3639425A (en) * | 1967-04-05 | 1972-02-01 | Laporte Chemical | Peroxygen compound |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0589418U (en) * | 1992-05-07 | 1993-12-07 | 大 遠江 | Riding helmet |
| US11839213B2 (en) | 2008-11-20 | 2023-12-12 | Armis Biopharma, Inc. | Antimicrobial, disinfecting, and wound healing compositions and methods for producing and using the same |
| US11969399B2 (en) | 2017-07-07 | 2024-04-30 | Armis Biopharma, Inc. | Compositions and methods for remediating chemical warfare agent exposed skin |
| US12440462B2 (en) | 2017-07-07 | 2025-10-14 | Armis Biopharma, Inc. | Compositions and methods for remediating chemical warfare agent exposed skin |
| US12702655B2 (en) | 2017-07-07 | 2026-08-11 | Armis Biopharma, Inc. | Antimicrobial, disinfecting and wound healing compositions and methods for producing and using same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0564148B2 (en) | 1993-09-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |