JPS6399082A - Synthesis of metal salts - Google Patents
Synthesis of metal saltsInfo
- Publication number
- JPS6399082A JPS6399082A JP24472086A JP24472086A JPS6399082A JP S6399082 A JPS6399082 A JP S6399082A JP 24472086 A JP24472086 A JP 24472086A JP 24472086 A JP24472086 A JP 24472086A JP S6399082 A JPS6399082 A JP S6399082A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- organic
- metal salts
- lower fatty
- metal salt
- 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
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 41
- 239000002184 metal Substances 0.000 title claims abstract description 41
- 150000003839 salts Chemical class 0.000 title claims abstract description 40
- 230000015572 biosynthetic process Effects 0.000 title description 3
- 238000003786 synthesis reaction Methods 0.000 title description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 14
- 229930195729 fatty acid Natural products 0.000 claims abstract description 14
- 239000000194 fatty acid Substances 0.000 claims abstract description 14
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 9
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims abstract description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 4
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 235000011054 acetic acid Nutrition 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 235000019253 formic acid Nutrition 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- 229910052718 tin Inorganic materials 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- -1 phosphate ester Chemical class 0.000 claims description 26
- 229910019142 PO4 Inorganic materials 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000010452 phosphate Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 15
- 230000002194 synthesizing effect Effects 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052788 barium Inorganic materials 0.000 claims description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 14
- 150000002148 esters Chemical class 0.000 abstract description 8
- 239000000490 cosmetic additive Substances 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000005456 alcohol based solvent Substances 0.000 abstract 2
- 125000000217 alkyl group Chemical group 0.000 abstract 1
- 229910052794 bromium Inorganic materials 0.000 abstract 1
- 229910052745 lead Inorganic materials 0.000 abstract 1
- 239000002304 perfume Substances 0.000 abstract 1
- 239000000516 sunscreening agent Substances 0.000 abstract 1
- 235000021317 phosphate Nutrition 0.000 description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 150000005690 diesters Chemical class 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- JRLTTZUODKEYDH-UHFFFAOYSA-N 8-methylquinoline Chemical group C1=CN=C2C(C)=CC=CC2=C1 JRLTTZUODKEYDH-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 206010042496 Sunburn Diseases 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 230000001166 anti-perspirative effect Effects 0.000 description 1
- 239000003213 antiperspirant Substances 0.000 description 1
- DXNQCJQBBZDSOA-UHFFFAOYSA-L butyl phosphate;manganese(2+) Chemical compound [Mn+2].CCCCOP([O-])([O-])=O DXNQCJQBBZDSOA-UHFFFAOYSA-L 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- UIEQMLWXCVFLPB-UHFFFAOYSA-L calcium methyl phosphate Chemical compound P(=O)(OC)([O-])[O-].[Ca+2] UIEQMLWXCVFLPB-UHFFFAOYSA-L 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- AITVUWGCWIXHDT-UHFFFAOYSA-L copper;dodecyl phosphate Chemical compound [Cu+2].CCCCCCCCCCCCOP([O-])([O-])=O AITVUWGCWIXHDT-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 1
- YZAOXEQRVHCALM-UHFFFAOYSA-L dodecyl phosphate;nickel(2+) Chemical compound [Ni+2].CCCCCCCCCCCCOP([O-])([O-])=O YZAOXEQRVHCALM-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- BODLRQRPIZXBHY-UHFFFAOYSA-L lead(2+);octadecyl phosphate Chemical compound [Pb+2].CCCCCCCCCCCCCCCCCCOP([O-])([O-])=O BODLRQRPIZXBHY-UHFFFAOYSA-L 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- NEUQJOOIWQYONT-UHFFFAOYSA-L magnesium;methyl phosphate Chemical compound [Mg+2].COP([O-])([O-])=O NEUQJOOIWQYONT-UHFFFAOYSA-L 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-N methyl dihydrogen phosphate Chemical compound COP(O)(O)=O CAAULPUQFIIOTL-UHFFFAOYSA-N 0.000 description 1
- CAAULPUQFIIOTL-UHFFFAOYSA-L methyl phosphate(2-) Chemical compound COP([O-])([O-])=O CAAULPUQFIIOTL-UHFFFAOYSA-L 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical compound [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- IPGDQASCXBOJCB-UHFFFAOYSA-L zinc;dodecyl phosphate Chemical class [Zn+2].CCCCCCCCCCCCOP([O-])([O-])=O IPGDQASCXBOJCB-UHFFFAOYSA-L 0.000 description 1
- UACZWEHNJDEXJP-UHFFFAOYSA-L zinc;ethyl phosphate Chemical compound [Zn+2].CCOP([O-])([O-])=O UACZWEHNJDEXJP-UHFFFAOYSA-L 0.000 description 1
- PORPEXMDRRVVNF-UHFFFAOYSA-L zinc;octadecyl phosphate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCCOP([O-])([O-])=O PORPEXMDRRVVNF-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【発明の詳細な説明】
本発明は有機リン酸エステル金属塩類の合成方法に関す
る。従来この種の化合物の合成方法としては(I)有機
リン酸エステルを水溶液中でアルカリ金属水酸化物、例
えば水酸化ナトリウム等で中和しナトリウム塩となし、
その後金属の硫酸塩又は塩化物の水溶液を加えて目的物
を得る方法。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for synthesizing organophosphate metal salts. Conventional methods for synthesizing this type of compound include (I) neutralizing an organic phosphate ester with an alkali metal hydroxide, such as sodium hydroxide, in an aqueous solution to form a sodium salt;
A method of obtaining the desired product by subsequently adding an aqueous solution of metal sulfate or chloride.
(II)特公昭42−12646に記載されている方法
で溶剤を使用せずに有機リン酸エステルと酢酸金属塩を
高温、減圧下で長時間反応させて目的物を得る方法。が
代表的な方法であった。しかしながら上記方法について
は各々欠点があった。例えば(I)の方法については低
級アルキルリン酸エステル金属塩は水溶性であるため上
記の方法では反応後の純品の分離が極めて困難であった
。即ち副生するNa2804.又はNa1lも水溶性で
あるためこれらとの分離が不可能であシ、また、高級ア
ルキルリン酸エステル金属塩の合成の場合副生するNa
2804又はNaCl等の中性無機塩が完全に除去され
ない事である。生成する高級アルキルリン酸エステル金
属塩は溶剤に極めて難溶性のものが多くそのため再結晶
、抽出、等による精製ができないため、結晶の水洗によ
る無機塩の除去といった方法をとらざるを得す、この方
法では結晶中に無機イオンが残存する。又生成する金属
塩が水に極めて難溶性のため、生成した金属塩中に有機
リン酸エステルのアルカリ金属塩がとシこまれ水溶液中
で行なう交換法では完全く交換が行なわれず、したがっ
て生成した高級アルキルリン酸エステル金属塩中に未交
換の有機リン酸エステルのアルカリ金属塩が残存する。(II) A method of obtaining the desired product by reacting an organic phosphoric acid ester and a metal acetate at high temperature and under reduced pressure for a long period of time without using a solvent, as described in Japanese Patent Publication No. 42-12646. was the typical method. However, each of the above methods had drawbacks. For example, in the method (I), since the lower alkyl phosphate metal salt is water-soluble, it is extremely difficult to separate the pure product after the reaction using the above method. That is, by-produced Na2804. Since Na1 is also water-soluble, it is impossible to separate it from these, and in the synthesis of higher alkyl phosphate metal salts, Na1l is a by-product.
Neutral inorganic salts such as 2804 or NaCl are not completely removed. Many of the higher alkyl phosphate metal salts produced are extremely poorly soluble in solvents, and therefore cannot be purified by recrystallization, extraction, etc., so it is necessary to remove inorganic salts by washing the crystals with water. In this method, inorganic ions remain in the crystal. In addition, since the metal salt produced is extremely poorly soluble in water, the alkali metal salt of the organophosphoric acid ester is incorporated into the metal salt produced, and the exchange method performed in an aqueous solution does not result in complete exchange. Unexchanged alkali metal salts of organic phosphates remain in the higher alkyl phosphate metal salts.
また(II)の方法にりいては溶剤を使用せず高温で長
時間反応さぜるため原料物質である有機リン酸エステル
及び目的物質である有機リン酸エステル金属塩の変質、
劣化、分解が避けられず、そのため収率が悪く、生成物
が褐色に着色し高純度の目的物が得られなかった。In addition, in the method (II), since the reaction is carried out at high temperature for a long time without using a solvent, the organic phosphate ester as the raw material and the organic phosphate metal salt as the target substance are deteriorated.
Deterioration and decomposition were unavoidable, resulting in a poor yield and a brown coloration of the product, making it impossible to obtain a highly pure target product.
一方本願物質は種々の用途に使用され、多方面に可能性
があるが、現在の所純品を得る方法がなく、アルカリ金
属イオン及びハロゲンイオン、硫酸イオン等の強電解性
イオンの混入と着色性を恐れる分野ではその性能等が評
価できなかった。そこで本発明者らは強電解性イオンを
不純物として含有せず高純度の有機リン酸エステル金属
塩を合成するため鋭意研究を進めた結果本発明に到達し
た。On the other hand, although the claimed substance is used for various purposes and has many possibilities, there is currently no way to obtain a pure product, and it is susceptible to contamination with strong electrolytic ions such as alkali metal ions, halogen ions, and sulfate ions, and coloration. Its performance could not be evaluated in fields where sexuality is feared. Therefore, the present inventors conducted extensive research to synthesize a highly pure organic phosphate metal salt that does not contain strong electrolytic ions as impurities, and as a result, the present invention was achieved.
1Bの飽和又は不飽和アルキル基を表わす。)で示され
る有機リン酸エステルと有機低級脂肪酸金属塩とをアル
コール系溶剤中で反応させる事を特徴とする有機リン酸
エステル金属塩類の合成方法であって、その金属として
はマグネシウム、カルシウム、ストロンチウム、バリウ
ム、銅、亜鉛。1B represents a saturated or unsaturated alkyl group. ) is a method for synthesizing organic phosphate ester metal salts, which is characterized by reacting an organic phosphate ester shown in , barium, copper, zinc.
カドミウム、アルミニウム、錫、鉛、アンチモン。Cadmium, aluminum, tin, lead, antimony.
ビスマス、マンガン、鉄、コバルト、ニッケルである。These are bismuth, manganese, iron, cobalt, and nickel.
また有機低級脂肪酸成分としてはギ酸、酢酸、プロピオ
ン酸、酪酸である。Organic lower fatty acid components include formic acid, acetic acid, propionic acid, and butyric acid.
本発明によって得られる金属塩類は化粧品添加剤、香料
担持剤9日焼は防止剤、汗止め剤、湿潤剤、4i1脂添
加剤、紫外線吸収剤、耐候性改良剤。The metal salts obtained according to the present invention can be used as cosmetic additives, fragrance carriers, sunburn inhibitors, antiperspirants, humectants, 4I1 fat additives, ultraviolet absorbers, and weather resistance improvers.
高分子重合触媒、潤滑油添加剤、燃料添加剤、消火薬剤
、難燃剤、滑剤、離1型剤等として極めて有用な物質で
ある。It is an extremely useful substance as a polymer polymerization catalyst, lubricating oil additive, fuel additive, fire extinguishing agent, flame retardant, lubricant, mold release agent, etc.
次に本発明における実施の概略について述べる。Next, an outline of the implementation of the present invention will be described.
即ち、相当する有機リン酸エステルと有機低級脂肪酸金
属塩とを溶剤中で常温から150℃で80分から5時間
反応を行なった後濾過、&浄、又は濃縮、乾燥等の操作
を行なって目的物を得る。That is, the corresponding organic phosphoric acid ester and organic lower fatty acid metal salt are reacted in a solvent at room temperature to 150°C for 80 minutes to 5 hours, and then filtered, purified, concentrated, dried, etc. to obtain the desired product. get.
なお有機リン酸エステルと有機低級脂肪酸金属塩との反
応割合は有機リン酸エステルについては全酸価を求め、
これによシ上起原料金属塩類の添加量を決定すれば良い
。反応を完全にするためには原料金属塩が有機リン酸エ
ステルに当量か又はそれ以下が良い。望ましくは有機リ
ン酸エステルの全酸価に対して1.0当量から0.5当
景の原料金属塩が添加される。The reaction rate between organic phosphate ester and organic lower fatty acid metal salt is determined by calculating the total acid value for organic phosphate ester,
Based on this, the amount of the starting material metal salt to be added can be determined. In order to complete the reaction, it is preferable that the raw metal salt be used in an amount equivalent to or less than the amount of the organic phosphoric acid ester. Desirably, 1.0 equivalent to 0.5 equivalent of the raw metal salt is added to the total acid value of the organic phosphate ester.
反応は、アルコール系溶剤中で行なう事が必須条件でア
シ、溶剤としてはメタノール、エタノール、nプロピル
アルコール、イソプロピルアルコール、n−ブチルアル
コール等があげられる。アセトン、メチルエチルケトン
等のケトン系、n−ヘキサン、石油エーテル、ベンゼン
、トルエン。It is essential that the reaction be carried out in an alcoholic solvent, and examples of the solvent include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, and n-butyl alcohol. Ketones such as acetone and methyl ethyl ketone, n-hexane, petroleum ether, benzene, and toluene.
キシレン等の炭化水素系、その他ハロゲン系炭化水素等
と上記アルコール系溶剤との混合溶剤でも良い。なお反
応の溶剤を選択する場合、反応原料である有機リン酸エ
ステルと低級脂肪酸金属塩及び反応生成物である有機リ
ン酸エステル金属塩のいずれか少なくとも一つが使用す
る。溶剤に室温もしくは加熱時溶解することが望ましい
。A mixed solvent of a hydrocarbon such as xylene or another halogenated hydrocarbon and the above-mentioned alcohol solvent may also be used. When selecting a solvent for the reaction, at least one of the organic phosphate ester and lower fatty acid metal salt which are the reaction raw materials, and the organic phosphate ester metal salt which is the reaction product is used. It is desirable to dissolve it in a solvent at room temperature or when heated.
溶剤としてアルコール系溶剤を使用した理由は反応進行
によって遊離生成する低級脂肪酸が該溶剤のアルコール
と反応し、エステルが生成するため反応が促進されるた
めである。The reason why an alcoholic solvent was used as the solvent is that the lower fatty acids that are liberated as the reaction progresses react with the alcohol of the solvent to produce esters, thereby accelerating the reaction.
本願の原料に使用される有機リン酸エステル化金物とは
公知の方法即ち無水リン酸とアルコール類の反応によっ
てモノエステルとジエステルの混合物あるいはオキシ塩
化リンとアルコール類のエステル反応の後精製工程を経
た高純度のモノエステル又はジエステルである。又一方
本願のもう一つの原料である有機低級脂肪酸金属塩とし
ては、マグネシウム、カルシウム、ストロンチウム、バ
リウム、銅、亜鉛、カドミウム、アルミニウム。The organic phosphate esterified metal used as the raw material of this application is a mixture of monoester and diester obtained by a known method, that is, the reaction of phosphoric anhydride and alcohol, or the ester reaction of phosphorus oxychloride and alcohol, followed by a purification process. High purity monoester or diester. On the other hand, the organic lower fatty acid metal salts which are another raw material of the present application include magnesium, calcium, strontium, barium, copper, zinc, cadmium, and aluminum.
i、鉛、アンチモン、ビスマス、マンガン、鉄。i, lead, antimony, bismuth, manganese, iron.
コバルト、ニッケルのギ酸塩又は酢酸塩又はプロピオン
酸塩もしくは酪酸塩である。Cobalt, nickel formate or acetate, propionate or butyrate.
これらは無水塩のみならず、通常工業的に得られる水利
塩を使用してもよい。As these salts, not only anhydrous salts but also commonly industrially obtained aqueous salts may be used.
また本願の上記原料金属塩は反応中に生成する場合も含
まれる。即ち上記金属の酸化物及び水酸化物、炭酸塩等
に有機低級脂肪酸を加えて、それらの脂肪酸金属塩を生
成せしめ、これを単離せず、これに該有機リン酸エステ
ルを加えて、アルコール系溶剤中で有機リン酸エステル
金属塩を合成する方法も本願の合成方法に含まれる。本
発明の方法によりて得られる代表的な生成物の物性を第
1表に示す。Further, the case where the raw material metal salt of the present application is generated during the reaction is also included. That is, organic lower fatty acids are added to the oxides, hydroxides, carbonates, etc. of the above metals to produce fatty acid metal salts, which are not isolated, but the organic phosphoric acid ester is added thereto to form an alcohol-based A method of synthesizing an organic phosphate metal salt in a solvent is also included in the synthesis method of the present application. Table 1 shows the physical properties of typical products obtained by the method of the present invention.
但し表中 nは金属の原子価でMは金属を示す。However, in the table n represents the valence of the metal, and M represents the metal.
(以下余白)
なお、参考のため本発明の方法および先に述べた従来法
で合成したn−ドデシルリン酸エステル亜鉛塩の物性を
第2表に記述する。(The following is a blank space) For reference, the physical properties of n-dodecyl phosphate zinc salts synthesized by the method of the present invention and the conventional method described above are described in Table 2.
(以下余白)
但し
■原料n−ドデシルリン酸エステルはジエスチル:モノ
エステル= 1.0 : 1.1 (モル比)、全酸価
241のものを使用した。これを使用して得られる亜鉛
塩のZn(%)= 12.4 (計算値)
■合成方法
木発明二エタノールを溶剤とし原料脂肪酸金属塩は酢酸
亜鉛を使用して合成
した。(The following is a blank space) However, (1) The raw material n-dodecyl phosphate used was diethyl:monoester=1.0:1.1 (mole ratio) and a total acid value of 241. Zn (%) of the zinc salt obtained using this = 12.4 (calculated value) ② Synthesis method The raw fatty acid metal salt was synthesized using zinc acetate and ethanol was used as a solvent.
(1):有機リン酸エステルを水酸化ナトリウム水溶液
にて中和し、これに硫酸亜鉛水溶液を加えて合成した。(1): Organic phosphoric acid ester was neutralized with an aqueous sodium hydroxide solution, and an aqueous zinc sulfate solution was added thereto for synthesis.
(■):有機リン酸エステルに酢酸亜鉛を加えて150
〜200℃にて減圧下6時間反応させた。(■): 150 by adding zinc acetate to organic phosphate ester
The reaction was carried out at ~200°C under reduced pressure for 6 hours.
次に合成方法の実施の態様を実施例によって説明する。Next, embodiments of the synthesis method will be explained using examples.
実施例1
メチルリン酸エステル〔ジエステルニモノエステル=
1.0 : 1.0 (モル比)全酸価677〕19.
7gr をエタノール100m1!に溶解しこれにMg
(CHg C00) 2 ・4H2025,5gr
を加えて70〜80℃にて2時間加熱還流を行なった
。Example 1 Methyl phosphate ester [diester nimonoester=
1.0 : 1.0 (mole ratio) Total acid value 677] 19.
7gr in 100ml of ethanol! Mg
(CHg C00) 2 ・4H2025,5gr
was added and heated under reflux at 70 to 80°C for 2 hours.
反応後減圧濃縮し、乾燥を行なって22.1gr(収率
98.7%)の白色結晶メチルリン酸エステルマグネシ
ウム塩を得た。また上記減圧濃縮した溜出物中にエステ
ル成分である酢酸エチルをガスクロマトグラフィにて確
認した。After the reaction, the reaction mixture was concentrated under reduced pressure and dried to obtain 22.1 gr (yield: 98.7%) of white crystalline methyl phosphate magnesium salt. Furthermore, ethyl acetate, which is an ester component, was confirmed in the distillate concentrated under reduced pressure by gas chromatography.
実施例2
実施例1で使用したメチルリン酸エステル24.5 g
r ヲメタ/−ルにt o o mzに溶解しこれに0
a(HOOO)219.2grを加えて60〜70℃に
で8時間加熱還流を行なった。反応後減圧濃縮し乾燥を
行なって29.9gr(収率99.0%)の白色結晶メ
チルリン酸エステルカルシウム塩を得た。Example 2 24.5 g of methyl phosphate used in Example 1
r Dissolve in t o o mz in wometa/-le and add 0 to this.
219.2 gr of a(HOOO) was added and heated under reflux at 60 to 70°C for 8 hours. After the reaction, the reaction mixture was concentrated under reduced pressure and dried to obtain 29.9 gr (yield: 99.0%) of white crystalline methyl phosphate calcium salt.
実施例8
メチルリン酸エステル〔ジエステル:モノエステル=
1.0 : 1.0 (そル比)全酸価677〕15.
6gr をイソプロピルアル、コール100m1!に溶
解し、これにcd(CzHsOOO)2・2H2027
,7grを加えて90〜100℃にて8時間加熱した。Example 8 Methyl phosphate ester [diester: monoester=
1.0 : 1.0 (Sol ratio) Total acid value 677] 15.
6gr isopropyl alcohol, coal 100ml! Dissolve in and add cd(CzHsOOO)2.2H2027 to this.
, 7 gr was added thereto and heated at 90 to 100°C for 8 hours.
反応後減圧濃縮し、乾燥を行なって25.8gr(収率
97.8%)の淡黄色結晶メチルリン酸エステルカドミ
ウム塩を得た。After the reaction, the reaction mixture was concentrated under reduced pressure and dried to obtain 25.8 gr (yield: 97.8%) of pale yellow crystalline methyl phosphoric acid ester cadmium salt.
実施例4
エチルリン酸エステル〔ジエステル:モノエステル=
1.0 : 1.2 (モル比)全酸価599]9.2
grをエタノール50m/に溶解し、これにZn(C!
HsCOO)g2H2010,8gr を加えて25
〜80℃にて8時間かきまぜた後減圧濃縮によυ水を溜
去し乾燥を行なって12.tgr(収率98.4%)の
白色結晶エチルリン酸エステル亜鉛塩を得た。Example 4 Ethyl phosphate ester [diester: monoester=
1.0: 1.2 (mole ratio) total acid value 599] 9.2
gr was dissolved in 50ml of ethanol, and Zn(C!
Add HsCOO)g2H2010,8gr and make 25
After stirring at ~80°C for 8 hours, water was distilled off by vacuum concentration and drying was performed.12. A white crystalline ethyl phosphate zinc salt of tgr (yield 98.4%) was obtained.
実施例5
n−ブチルリン酸エステル〔ジエステル:モノエステル
= 1.0 : 1.0 (モル比)全酸価442〕1
1.5grをn−プロピルアルコール25m1!に溶解
しこれにMn(CIIsOOO)2・4%go 11
.tgrを加えて70〜80℃にて1時間加熱還流を行
なった後室温まで冷却しp別乾燥を行なって12.9g
r(収率92.8%)の白色結晶n−ブチルリン酸エス
テルマンガン塩を得た。Example 5 n-butyl phosphate ester [diester: monoester = 1.0: 1.0 (mole ratio) total acid value 442] 1
1.5gr to 25ml of n-propyl alcohol! Mn(CIIsOOOO) 2.4% go 11
.. After adding TGR and heating under reflux at 70 to 80°C for 1 hour, it was cooled to room temperature and dried separately to give 12.9 g.
A white crystalline n-butyl phosphate manganese salt of r (yield 92.8%) was obtained.
実施例6
n−ドデシルリン酸エステル〔ジエステル:モノエステ
ル=1.0=1.1(モル比)、全酸価241〕11.
5grをイソプロピルアルコール50 mlに溶解しこ
れに0u(OHaCoo)s+ ・H2O4,9grを
加えて100〜110℃にて8時間加熱かくはんを行な
った。反応終了後室温まで冷却し濾過乾燥を行なって1
1.5gr(収率88.5%)の淡青色結晶n−ドデシ
ルリン酸エステル銅塩を得た。Example 6 n-dodecyl phosphate ester [diester: monoester = 1.0 = 1.1 (mole ratio), total acid value 241] 11.
5gr was dissolved in 50ml of isopropyl alcohol, 0u(OHaCoo)s+ .H2O4, 9gr was added thereto, and the mixture was heated and stirred at 100 to 110°C for 8 hours. After the reaction is complete, cool to room temperature, filter and dry.
1.5 gr (yield: 88.5%) of pale blue crystalline n-dodecyl phosphate copper salt was obtained.
実施例7
実施例かで使用したn−ドデシルリン酸エステル15.
6grをエタノール501Mに溶解しこれにN’xCH
COO)25.Ogr を7J+えて70〜80℃にて
5時間加熱還流を行なった。反応終了後室温まで冷却し
濾過乾燥を行なって17.tgr(収率96.1%)の
淡青色結晶n−ドデシルリン酸エステルニッケル塩を得
た。Example 7 n-dodecyl phosphate ester used in Example 15.
Dissolve 6gr in ethanol 501M and add N'xCH to this.
COO)25. The mixture was heated under reflux at 70 to 80° C. for 5 hours with 7 J+ of Ogr added. After the reaction is completed, cool to room temperature, filter and dry.17. A pale blue crystalline n-dodecyl phosphate nickel salt of tgr (yield 96.1%) was obtained.
実五例8
n−オクタデシルリン酸エステル〔ジエステルj:モノ
エステル= i、o : 1.8 (モル比)、全酸価
220’:180.5grをエタ)−ル100m/に加
熱溶解しこれにZn(CHs(300)22Hz01B
、17g
grを加えて←牟0〜ト40℃にて8時間加熱還流を行
なった。反応終了後濾過し、戸別した結晶を乾燥しal
、5gr(収率91.8%)の白色結晶n−オクタデシ
ルリン酸エステル亜鉛塩を得た。Example 8 N-octadecyl phosphate ester [diester j: monoester = i, o: 1.8 (mole ratio), total acid value 220': 180.5gr was heated and dissolved in 100ml of ethanol) Zn(CHs(300)22Hz01B
, 17 g gr were added thereto, and the mixture was heated under reflux at 0 to 40°C for 8 hours. After the reaction is completed, filter and dry the crystals separated from each other.
, 5g (yield 91.8%) of white crystalline n-octadecyl phosphate zinc salt was obtained.
また戸液中に酢酸エチルの存在をガスクロマトグラフィ
ーにて確認した。The presence of ethyl acetate in the solution was also confirmed by gas chromatography.
実施例9
n−オクタデシルリン酸エステル〔ジエステル:モノエ
ステル= 1.0 : 1.8 (モル比)、全酸価2
20)26.8grをエタノール100m1Vc溶解し
これにPb(CalllI7000)2 19.7 g
r を加えて70〜80℃にで8時間加熱還流を行な
った。Example 9 n-octadecyl phosphate ester [diester: monoester = 1.0: 1.8 (mole ratio), total acid value 2
20) Dissolve 26.8gr in 100ml 1Vc of ethanol and add 19.7g of Pb(Call I7000)2 to this.
r was added and heated under reflux at 70 to 80°C for 8 hours.
反応終了後室温まで冷却し濾過、戸別した結晶をよくエ
タノールにて洗浄し続いて乾燥を行なって84、tgr
(収率92.4%)の白色結晶n−オクタデシルリン酸
エステル鉛塩を得た。After the reaction was completed, it was cooled to room temperature, filtered, and the separated crystals were thoroughly washed with ethanol and then dried to obtain 84, tgr.
A white crystalline n-octadecyl phosphate lead salt was obtained (yield 92.4%).
特許出願人 大阪香料株式会社 手 続 hli 正 書昭和。Patent applicant: Osaka Fragrance Co., Ltd. Continuation of the book from the Showa era.
2年!2月 2日2 years! February 2nd
Claims (1)
および ▲数式、化学式、表等があります▼ (但し式中Rは炭素数1〜18の飽和又は不飽和のアル
キル基を表わす。)で示される有機リン酸エステルと有
機低級脂肪酸金属塩とをアルコール系溶剤中で反応させ
る事を特徴とする有機リン酸エステル金属塩類の合成方
法。 2、有機リン酸エステル金属塩類の金属がマグネシウム
、カルシウム、ストロンチウム、バリウム、銅、亜鉛、
カドミウム、アルミニウム、錫、鉛、アンチモン、ビス
マス、マンガン、鉄、コバルト、ニッケルである特許請
求範囲第1項記載の金属塩類の合成方法。 3、有機低級脂肪酸金属塩の有機低級脂肪酸成分として
はギ酸、酢酸、プロピオン酸、酪酸である特許請求の範
囲第1項記載の金属塩類の合成方法。[Claims] 1. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or /
and ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, in the formula, R represents a saturated or unsaturated alkyl group having 1 to 18 carbon atoms.) An organic phosphoric acid ester represented by the formula and an organic lower fatty acid metal salt are combined with alcohol. A method for synthesizing organic phosphate ester metal salts, which is characterized by reaction in a system solvent. 2. The metals of the organic phosphate metal salts are magnesium, calcium, strontium, barium, copper, zinc,
A method for synthesizing metal salts according to claim 1, which are cadmium, aluminum, tin, lead, antimony, bismuth, manganese, iron, cobalt, and nickel. 3. The method for synthesizing metal salts according to claim 1, wherein the organic lower fatty acid component of the organic lower fatty acid metal salt is formic acid, acetic acid, propionic acid, or butyric acid.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24472086A JPS6399082A (en) | 1986-10-14 | 1986-10-14 | Synthesis of metal salts |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP24472086A JPS6399082A (en) | 1986-10-14 | 1986-10-14 | Synthesis of metal salts |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6399082A true JPS6399082A (en) | 1988-04-30 |
JPH0529357B2 JPH0529357B2 (en) | 1993-04-30 |
Family
ID=17122899
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP24472086A Granted JPS6399082A (en) | 1986-10-14 | 1986-10-14 | Synthesis of metal salts |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6399082A (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03178987A (en) * | 1989-02-27 | 1991-08-02 | Kao Corp | Monoalkylphosphoric acid zinc alkali metal salt, preparation thereof and cosmetic containing the same |
EP0629630A1 (en) * | 1993-06-15 | 1994-12-21 | Kao Corporation | Novel phosphoric diesters which absorb UV rays, method of preparing the same, and cosmetic compositions containing the same |
EP1988110A1 (en) * | 2006-02-23 | 2008-11-05 | Mitsui Chemicals, Inc. | Internal mold release agent for production of polythiourethane optical material |
WO2011099195A1 (en) * | 2010-02-12 | 2011-08-18 | Jx日鉱日石エネルギー株式会社 | Lubricant additive composition |
JP2015151527A (en) * | 2014-02-19 | 2015-08-24 | 株式会社オートネットワーク技術研究所 | Adhesive composition and composite material using the same |
JP2015151532A (en) * | 2014-02-19 | 2015-08-24 | 株式会社オートネットワーク技術研究所 | Adhesive composition and composite material using the same |
WO2015125578A1 (en) * | 2014-02-19 | 2015-08-27 | 株式会社オートネットワーク技術研究所 | Adhesive composition and composite material using same |
-
1986
- 1986-10-14 JP JP24472086A patent/JPS6399082A/en active Granted
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03178987A (en) * | 1989-02-27 | 1991-08-02 | Kao Corp | Monoalkylphosphoric acid zinc alkali metal salt, preparation thereof and cosmetic containing the same |
EP0629630A1 (en) * | 1993-06-15 | 1994-12-21 | Kao Corporation | Novel phosphoric diesters which absorb UV rays, method of preparing the same, and cosmetic compositions containing the same |
EP1988110A1 (en) * | 2006-02-23 | 2008-11-05 | Mitsui Chemicals, Inc. | Internal mold release agent for production of polythiourethane optical material |
EP1988110A4 (en) * | 2006-02-23 | 2012-03-28 | Mitsui Chemicals Inc | Internal mold release agent for production of polythiourethane optical material |
WO2011099195A1 (en) * | 2010-02-12 | 2011-08-18 | Jx日鉱日石エネルギー株式会社 | Lubricant additive composition |
JP2011162723A (en) * | 2010-02-12 | 2011-08-25 | Jx Nippon Oil & Energy Corp | Additive composition for lubricating oil |
JP2015151527A (en) * | 2014-02-19 | 2015-08-24 | 株式会社オートネットワーク技術研究所 | Adhesive composition and composite material using the same |
JP2015151532A (en) * | 2014-02-19 | 2015-08-24 | 株式会社オートネットワーク技術研究所 | Adhesive composition and composite material using the same |
WO2015125578A1 (en) * | 2014-02-19 | 2015-08-27 | 株式会社オートネットワーク技術研究所 | Adhesive composition and composite material using same |
CN106029814A (en) * | 2014-02-19 | 2016-10-12 | 株式会社自动网络技术研究所 | Adhesive composition and composite material using same |
Also Published As
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JPH0529357B2 (en) | 1993-04-30 |
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