WO2011055609A1 - ポリフルオロアルキルホスホン酸塩乳化剤およびこれを有効成分とする離型剤 - Google Patents
ポリフルオロアルキルホスホン酸塩乳化剤およびこれを有効成分とする離型剤 Download PDFInfo
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- WO2011055609A1 WO2011055609A1 PCT/JP2010/067616 JP2010067616W WO2011055609A1 WO 2011055609 A1 WO2011055609 A1 WO 2011055609A1 JP 2010067616 W JP2010067616 W JP 2010067616W WO 2011055609 A1 WO2011055609 A1 WO 2011055609A1
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- release agent
- emulsion
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- solution
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- 238000000926 separation method Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 description 1
- QOPBTFMUVTXWFF-UHFFFAOYSA-N tripropyl phosphite Chemical compound CCCOP(OCCC)OCCC QOPBTFMUVTXWFF-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/14—Derivatives of phosphoric acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/007—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
Definitions
- the present invention relates to a polyfluoroalkyl phosphonate emulsifier and a release agent containing the same as an active ingredient. More particularly, it relates to a polyfluoroalkyl phosphonate emulsifier which is effectively used as an emulsifier or the like in forming an emulsion of perfluoropolyether oil or perfluorocarbon compound, and a release agent containing the same as an active ingredient.
- a mold release agent such as silicone oil, wax, talc, mica or tetrafluoroethylene resin is used.
- silicone oil, wax and the like exhibit good releasability, since the release agent is transferred to the molded article, uniform paintability, secondary processability, etc. are impaired, and those lacking in durability are also obtained. is there.
- tetrafluoroethylene resin is satisfactory in terms of durability of mold release effect and secondary processability, it is necessary to carry out film-like baking treatment on the mold surface of the mold at the time of mold release treatment. In addition, the same process is required even at the time of reprocessing, resulting in an increase in the number of operation steps.
- a mold release agent having a polyfluoroalkyl group-containing phosphoric acid ester having 4 to 20 carbon atoms as one of the active ingredients has been proposed (see Patent Documents 1 to 3). Although these mold release agents exhibit good mold release properties and are considered to have a long mold release life as compared with the conventional ones, these mold release agents are still used as mold release agents with the recent complication of molded article shapes. Further improvement in performance is required.
- polyfluoroalkyl phosphonic acid esters are also widely used as synthetic materials for mold release agents.
- the mold release performance when used as a mold release agent is most easily expressed in a compound having 8 to 12 carbon atoms of a perfluoroalkyl group, and in particular, CF 3 (CF 2 ), which is a phosphonic acid ester compound having a perfluorooctyl group.
- CF 3 CF 2
- 7 CH 2 CH 2 P (O) (OC 2 H 5 ) 2 Is preferably used for this type of application (see Patent Documents 4 to 7).
- telomer compounds having a perfluoroalkyl group having 8 to 12 carbon atoms are biodegraded in the environment to be converted to compounds having relatively high bioaccumulation ability and environmental concentration, There are concerns about exposure and waste from the environment, emission from the treatment substrate, etc. to the environment, and diffusion. Further, compounds having a carbon number of 14 or more of the perfluoroalkyl group are very difficult to handle due to their physical and chemical properties, and in practice, they are hardly used.
- telomer compounds having a perfluoroalkyl group having a carbon number of 8 or more can not avoid generation and contamination of highly bioaccumulative perfluorooctanoic acids in the production process. Therefore, manufacturers of such telomer compounds are making progress in withdrawal from their production and substitution to compounds having a perfluoroalkyl group having 6 or less carbon atoms.
- the orientation on the surface of the treated substrate is significantly reduced, and the melting point, the glass transition point Tg, etc. are significantly lower than the compound having 8 carbon atoms. It will be greatly affected by operating environment conditions such as temperature, humidity, stress, contact of organic solvents and the like. Therefore, the required performance can not be obtained, and the durability is also affected.
- perfluoropolyether oil widely used as a lubricant is often used as an emulsion in order to be used for medicines and cosmetics etc.
- emulsifier in that case, at the time of emulsion polymerization, suspension polymerization
- Ammonium pentadecafluorooctanoate C 7 F 15 COONH 4 is particularly excellent in emulsifying performance and price, but due to environmental concerns, the direction in which its use is suppressed in terms of the carbon number of the perfluoroalkyl group It is in.
- An object of the present invention is a compound having a perfluoroalkyl group having a carbon number of 6 or less which is said to have low bioaccumulation ability, and an emulsifier having an emulsification performance comparable to that of ammonium pentadecafluorooctanoate excellent in emulsification performance and this
- the present invention is to provide a release agent containing as an active ingredient.
- the object of the present invention is to use the general formula C n F 2 n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c P (O) (OM 1 ) (OM 2 ) [I ] (Wherein, M 1 is a hydrogen atom, an alkali metal, an ammonium base or an organic amine base, M 2 is an alkali metal, an ammonium base or an organic amine base, n is an integer of 1 to 6 and a is 1 to 4) Is an integer of 1 to 3, and c is an integer of 1 to 3) is achieved by the emulsifier containing the polyfluoroalkyl phosphonate represented by the following as an active ingredient and the release agent containing the same as an active ingredient .
- the emulsifier is prepared as an aqueous solution or an organic solvent solution, and is effectively used for the emulsification of perfluoropolyether oil or perfluorocarbon compound.
- the polyfluoroalkyl phosphonate emulsifier according to the present invention is a compound having a perfluoroalkyl group having a carbon number of 6 or less which is said to have low bioaccumulation ability, and is pentadecafluorooctane excellent in emulsifying performance. It has an emulsification performance comparable to that of ammonium acid, and an emulsion comprising an aqueous solution or an organic solvent solution of this emulsifier and a perfluoropolyether oil or perfluorocarbon compound can form a stable emulsion. The emulsion stability is well maintained even after standing at room temperature or for 1 month at 40 ° C.
- Emulsions with perfluoropolyether oils are suitably used for applications such as surface treatment agents, especially mold release agents and cosmetic raw materials, while maintaining their good emulsion stability. Further, since the perfluorocarbon compound can dissolve and transport oxygen in a large amount, the emulsion of the perfluorocarbon compound emulsified with this emulsifier can be effectively used as an oxygen carrier medium or organ preservation solution.
- a release agent for example, even when prepared as an aqueous or organic solvent-based release agent at a concentration of about 0.1% by weight or less, it is effective when applied to a release object, such as a molding die. It produces excellent effects such as achieving good mold release performance. This is due to the fact that polyfluoroalkyl phosphonates exhibit very good solvent solubility and are far superior to conventional mold release agents prepared to account for 0.5 wt% solids concentration A mold release agent exhibiting mold release property can be obtained at a solid content concentration of about 0.1% by weight or less.
- polyfluoroalkyl phosphonates are problematic with conventional mold release agents because they have good solvent solubility and therefore readily form uniform concentration mold release solutions when diluted with diluents. It is characterized in that no precipitation occurs and storage stability is also good.
- the releasing agent according to the present invention preferably an emulsion-type releasing agent, exhibits the following excellent effects. (1) It has excellent film-forming properties and can form a uniform coating film even on molded articles of complicated shapes. (2) Since the film forming property to the mold surface and the adhesion to the mold surface by the ionic group are excellent, the mold release performance and the mold life can be remarkably improved. (3) Since mold releasability and durability are exhibited even at dilution as low as about 0.1% by weight, mold stain caused by the mold release agent is reduced. (4) Since the transferability of the release agent to the molded product is small, the quality of the molded product after molding is not adversely affected, and the dimensional accuracy of the molded product is improved.
- the polyfluoroalkyl phosphonic acid used as an emulsifier after forming a salt has the general formula C n F 2 n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c P (O) (OH) 2 [II] (Where n is an integer of 1 to 6; a is an integer of 1 to 4; b is an integer of 1 to 3; c is an integer of 1 to 3); n F 2 n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c P (O) (OR) 2 [III] It is produced by hydrolyzing a polyfluoroalkyl phosphonic acid diester represented by (wherein R is an alkyl group having 1 to 4 carbon atoms).
- polyfluoroalkyl phosphonic acid diester [III] used as the starting material for this reaction is polyfluoroalkyl iodide C n F 2 n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c I [IV] And trialkyl phosphite P (OR) 3 to obtain.
- Polyfluoroalkyl iodides [IV] are known compounds and are described in Patent Document 8.
- polyfluoroalkyl iodides [IV] include trialkyl phosphites such as trialkyl phosphite P having an alkyl group having 1 to 4 carbon atoms such as trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite and the like.
- the polyfluoroalkyl phosphonic acid diester [III] which is a raw material, can be obtained by reacting (OR) 3 and performing a de-RI reaction.
- the hydrolysis reaction of the polyfluoroalkylphosphonic acid diester [III] is easily carried out by stirring at about 90 to 100 ° C. in the presence of an acidic catalyst such as an inorganic acid represented by concentrated hydrochloric acid.
- the reaction mixture can be filtered under reduced pressure, washed with water, filtered, washed with acetone, filtered, etc. to obtain the target polyfluoroalkylphosphonic acid [II] with a good yield of about 90%. .
- Polyfluoroalkylphosphonates used as emulsifiers C n F 2 n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c P (O) (OM 1 ) (OM 2 ) [ I]
- Is a polyfluoroalkyl phosphonic acid C n F 2 n + 1 (CH 2 CF 2 ) a (CF 2 CF 2 ) b (CH 2 CH 2 ) c P (O) (OH) 2 [II]
- alkali metal hydroxide for example, sodium hydroxide, potassium hydroxide and the like are preferably used.
- organic amines include monoethylamine, monoisopropylamine, diethylamine, diisopropanolamine, dicyclohexylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, triethanolamine, tris (2-hydroxyethyl) amine, pyridine, morpholine or derivatives thereof Etc. are preferred.
- the alkali metal hydroxide, ammonia or organic amine forms a mono salt when used in equimolar amount with respect to the polyfluoroalkyl phosphonic acid, and forms a di salt when used twice as much. Let Generally, when it is used in the required theoretical molar number or more and used in an equimolar amount or more and less than 2 times the molar amount, a mixture of a mono salt and a di salt is formed.
- the polyfluoroalkyl phosphonate is used as an aqueous solution dissolved in an aqueous medium which is water or an aqueous solution of a water-soluble organic solvent or an organic solvent solution dissolved in an organic solvent.
- organic solvent include alcohols such as methanol, ethanol and isopropanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, aprotic polarides such as acetonitrile, dimethylformamide, diethylformamide, dimethylacetamide and N-methyl-2-pyrrolidone.
- a solvent is used.
- the emulsifying ability of polyfluoroalkyl phosphonate is, for example, in the case of an aqueous solution of ammonium 2- (perfluorohexyl) ethyl phosphonate, its critical micelle concentration [CMC] is found at around an emulsifier concentration of about 0.8% by weight, and the emulsifier concentration is about A constant low surface tension is exhibited at 1.0 wt% or more.
- the aqueous solution of the emulsifier or the organic solvent solution is added to the perfluoropolyether oil in a proportion of about 0.01 to 30 parts by weight, preferably about 0.1 to 15 parts by weight of the active ingredient per 100 parts by weight of the perfluoropolyether oil And emulsified to form a perfluoropolyether oil emulsion. If the emulsifier is used in a higher proportion, the properties of the perfluoropolyether oil itself will not be fully exhibited.
- the emulsification treatment is pre-emulsification at a rotation speed of about 500 to 10,000 rpm using a homogenizer or the like, and further emulsification treatment is performed at a pressure of about 100 to 800 kgf / cm 2 (about 10 to 80 MPa) using a high pressure homogenizer. To be done.
- the perfluoropolyether oils are emulsified, formula RfO (C 3 F 6 O) p (C 2 F 4 O) q (CF 2 O) r Rf ' [XI]
- Rf and Rf ' are perfluoro lower alkyl groups having 1 to 5 carbon atoms such as perfluoromethyl group and perfluoroethyl group, C 3 F 6 O group, C 2 F 4 O group and CF 2 O
- Specific examples of such perfluoropolyether oils represented by the general formula are as follows.
- m is 2 to 200, which is obtained by completely fluorinating a precursor formed by photooxidation polymerization of hexafluoropropene, or anionically polymerizing hexafluoropropene oxide in the presence of a cesium fluoride catalyst. And the obtained acid fluoride compound having a terminal —CF (CF 3 ) COF group is obtained by fluorine gas treatment.
- Perfluoropolyether oils other than those represented by the above general formula can also be used, and for example, the following perfluoropolyether oils are used.
- n is 2 to 100, and this is obtained by anionically polymerizing 2,2,3,3-tetrafluorooxetane in the presence of a cesium fluoride catalyst, and the obtained fluorinated polyether (CH 2 CF 2 CF 2 O) n is obtained by fluorine gas treatment under ultraviolet irradiation at 160 to 300 ° C.
- perfluoropolyether oils mentioned above as specific examples may be used alone or in combination, but from the viewpoint of cost performance, the perfluoropolyethers of the above [XIa] or [XIb], particularly [XIa] Ether oil is preferably used.
- the perfluoropolyether [XIa] one in which m is an integer of 2 to 100 and the number average molecular weight Mn is about 300 to 50000, preferably about 500 to 20000 is used.
- perfluoropolyether oils having a kinematic viscosity of any value can be used, 5 to 2000 mm 2 / s (40 ° C.) as a lubricant, preferably 100 in consideration of use under high temperature conditions.
- the thing of -1500 mm 2 / s (40 ° C.) is used. That is, the amount of evaporation is about 5 mm 2 / s or less, and the condition of 1.5% or less of the amount of evaporation specified in JIS grease for rolling bearings, which is a standard for heat-resistant grease, is not satisfied.
- the perfluoropolyether oil emulsion may further be an aqueous solution or an organic solution diluted with an aqueous solution or an organic solvent so that the solid concentration thereof accounts for about 0.01 to 30% by weight, preferably about 0.05 to 10% by weight.
- a solvent solution it is also used as a surface treatment agent such as a water and oil repellent agent, an anti-tack agent, and a mold release agent while maintaining good emulsion stability.
- a mold release agent it is applied to the molding die surface, and when it is applied onto a substrate such as a molded article, it is used as an anti-sticking agent.
- the emulsion When the emulsion is used as a release agent, it is used after being diluted with water or an organic solvent.
- organic solvent to be used, alcohols such as methanol, ethanol, n-propanol and isopropanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as diethyl ether, diisopropyl ether, dioxane and tetrahydrofuran, ethyl acetate, Esters such as butyl acetate, polyhydric alcohol derivatives such as methyl cellosolve, ethyl cellosolve, methyl carbitol, ethyl carbitol, carbon tetrachloride, methylene chloride, trichloroethylene, perchloroethylene, trichloroethane, trichlorofluoromethane, tetrachlorodifluor
- the application of the release agent solution to the mold can be carried out by any commonly used method such as dipping, spraying, brushing, aerosol spraying, application with an impregnated cloth, and the like.
- resins such as polyurethane, polycarbonate, epoxy resin, phenol resin, polyimide resin, vinyl chloride resin, natural rubber, chloroprene rubber, fluororubber And rubbers.
- perfluorocarbon compounds capable of dissolving and transporting large amounts of oxygen can be effectively utilized as an oxygen-carrying medium and an isolated organ preservation solution (see Patent Document 9) as an emulsion containing a polyfluoroalkyl phosphonate. .
- perfluorocarbon compounds include perfluorocycloalkanes such as perfluorocyclohexane, perfluorodecalin, perfluorotrimethylcyclohexane, perfluoroisopropylcyclohexane, perfluoromethyldecalin, and perfluoroalkyl derivatives thereof.
- perfluorocycloalkanes such as perfluorocyclohexane, perfluorodecalin, perfluorotrimethylcyclohexane, perfluoroisopropylcyclohexane, perfluoromethyldecalin, and perfluoroalkyl derivatives thereof.
- Reference Example 1 (1) In a 1-L four-necked flask equipped with a thermometer and a low-boiling receiver, CF 3 (CF 2) 3 ( CH 2 CF 2) (CF 2 CF 2) 2 (CH 2 CH 2) I (99GC%) 500 g (0.78 mol) and 181 g (1.56 mol) of triethyl phosphite P (OC 2 H 5 ) 3 were charged and stirred at 155 ° C. At this time, in order to remove the by-product ethyl iodide from the reaction system, nitrogen gas was bubbled into the reaction solution using a capillary.
- reaction solution was collected for gas chromatography analysis to confirm the remaining amount of triethyl phosphite, and then 91 g (0.78 mol) of triethyl phosphite was added four times at a time, and the mixture was stirred for a total of 18 hours. .
- the reaction mixture After completion of the reaction, the reaction mixture is subjected to vacuum single distillation under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 160 to 170 ° C and an overhead temperature of 150 to 155 ° C, the distilled fraction is washed with water, and the purified reaction product (96 GC% ) (Yield 78%) was obtained.
- reaction solution was collected for gas chromatography analysis to confirm the remaining amount of triethyl phosphite, and then 107 g (0.92 mol) of triethyl phosphite was added once at a time for 4 times and stirred for a total of 18 hours. .
- the reaction mixture is subjected to simple distillation under reduced pressure under the conditions of internal pressure 0.2 kPa, internal temperature 145-155 ° C., overhead temperature 138-142 ° C., the distilled fraction is washed with water, and the purified reaction product (98 GC% ) (Yield 79%) was obtained.
- reaction solution was taken for gas chromatography analysis to confirm the remaining amount of triethyl phosphite, and then triethyl phosphite was further added to 88 g (0.76 mol) at a time for 4 times, and stirred for a total of 18 hours. .
- the reaction mixture After completion of the reaction, the reaction mixture is subjected to vacuum single distillation under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 160 to 170 ° C and an overhead temperature of 150 to 155 ° C, the distilled fraction is washed with water, and the purified reaction product (96 GC% ) (Yield 77%) was obtained.
- reaction solution was collected for gas chromatography analysis to confirm the remaining amount of triethyl phosphite, and then 104 g (0.90 mol) of triethyl phosphite was added once at a time for 4 times and stirred for a total of 18 hours. .
- reaction mixture After completion of the reaction, the reaction mixture is subjected to vacuum single distillation under the conditions of internal pressure 0.2 kPa, internal temperature 145 to 155 ° C., overhead temperature 138 to 141 ° C., and the distilled fraction is washed with water to obtain a purified reaction product (97 GC% ) (Yield 78%) was obtained.
- reaction solution was collected for gas chromatography analysis to confirm the remaining amount of triethyl phosphite, and then 104 g (0.90 mol) of triethyl phosphite was added once at a time for 4 times and stirred for a total of 18 hours. .
- reaction mixture After completion of the reaction, the reaction mixture is subjected to vacuum single distillation under the conditions of internal pressure 0.2 kPa, internal temperature 145 to 155 ° C., overhead temperature 140 to 142 ° C., and the distilled fraction is washed with water to obtain a purified reaction product (97 GC% ) (Yield 79%) was obtained.
- reaction solution was fractionated and subjected to gas chromatography analysis to confirm the remaining amount of triethyl phosphite, and then triethyl phosphite was further added once at 130 g (1.12 mol) four times and stirred for a total of 18 hours .
- the reaction mixture After completion of the reaction, the reaction mixture is subjected to vacuum single distillation under the conditions of an internal pressure of 0.2 kPa, an internal temperature of 130 to 140 ° C., and an overhead temperature of 128 to 131 ° C., and the distilled fraction is washed with water to obtain a purified reaction product (98 GC% ) (Yield 79%) was obtained.
- Example 1 In a reactor equipped with a stirrer and a dropping device, 53.2 g of water heated to 40 ° C. was charged while keeping it warm, and 5 g (8.4 mmol) of the polyfluoroalkylphosphonic acid [IIa] obtained in Reference Example 1 After the addition of 15.4 g (12.7 mmol) of an aqueous ammonia solution having a concentration of 1.4% by weight, stirring was continued for 1 hour to carry out a neutralization reaction. As a result, an aqueous solution of polyfluoroalkylphosphonic acid ammonium salt of pH 8 (active ingredient concentration: 7.0% by weight) was obtained [Emulsifier aqueous solution I].
- the emulsifier aqueous solution I was added little by little to water, and the surface tension of the aqueous solution was measured.
- the critical micelle concentration [CMC] was 0.8% by weight, and the surface tension at a concentration of 2.0% by weight was 17 mN / m.
- the surface tension was measured by the maximum bubble method at 20 ° C. using a dynamic surface tension meter made by SITA.
- Example 1 when the polyfluoroalkyl phosphonic acid [IIa] is stirred for 1 hour without adding an aqueous ammonia solution, the added polyfluoroalkyl phosphonic acid [IIa] is separated without being dissolved in water, and the aqueous solution is Was not obtained.
- Example 2 In Example 1, the amount of water and the concentration of 1.4% by weight aqueous ammonia solution were respectively changed to predetermined amounts, and instead of polyfluoroalkylphosphonic acid [IIa], the same amount (5 g) of the poly obtained in Reference Examples 2 to 6 Using fluoroalkylphosphonic acids [IIb] to [IIf], their aqueous solutions (active ingredient concentration: 7.0% by weight) were obtained [Emulsifier aqueous solutions II to VI].
- Example 7 In Example 1, the amount of water is changed to 66.4 g, and 5 g of pentadecafluorooctanoic acid ammonium salt C 7 F 15 COONH 4 (DIEMCO product F-top EF 204) instead of polyfluoroalkyl phosphonic acid [IIa] and aqueous ammonia solution Using (11.6 mmol), an aqueous solution thereof (active ingredient concentration 7.0% by weight) was obtained [Emulsifier aqueous solution VII].
- the surface tension of the emulsifier aqueous solution VII was similarly measured, and its CMC was 0.8% by weight, and the surface tension at a concentration of 2.0% by weight was 18 mN / m.
- Example 7 In a 1,000 ml reactor equipped with a stirrer and a dropper, 186 g of water heated to 40 ° C. is charged while being kept warm, and 214 g of an aqueous emulsifier solution I and a general formula C 3 F 7 O [CF (CF 3 CF 3 ) CF 2 O] m C 2 F 5 (m: 2 to 100) After adding 100 g (total amount of 500 g) of perfluoropolyether oil (NOK Kruber product BARRIERTA J 25 FLUID; dynamic viscosity (40 ° C) 25 mm 2 / s) represented by ( 2 ) at a rotation speed of 3000 rpm using a homogenizer The mixture is pre-emulsified for 1 minute and further emulsified using a high pressure homogenizer (Nippon Seiki Co., Ltd.) under a pressure of 600 kgf / cm 2 (58.8 MPa) to 100 parts by weight of perfluoropolyether oil
- the average particle size of the obtained perfluoropolyether oil emulsion A was 150 nm.
- the average particle diameter is measured, and values of 152 nm and 157 nm are obtained, respectively, and it is shown that stable emulsions are formed in each case. confirmed.
- the measurement of the average particle diameter was performed by the dynamic light scattering method using Nikkiso make Micro Drag particle size distribution analyzer UPA150.
- Example 7 the same amount (214 g) of an aqueous emulsifier solution VII was used instead of the aqueous emulsifier solution I to obtain 482 g (96% recovery) of a perfluoropolyether oil emulsion J.
- the average particle diameter of this emulsion J was 131 nm, the average particle diameter after 1 month of room temperature was 136 nm, and the average particle diameter of 1 month after 40 ° C. was 140 nm, and a stable emulsion was formed.
- Example 7 the same amount (214 g) of the aqueous emulsifier solution I or the alternative aqueous emulsifier solutions II to VI are used, and perfluoropolyether oils J25, J100, J400 or perfluorodecalin represented by the same general formula are used. The same amount (100 g) of C 10 F 18 was used to obtain perfluoropolyether oil emulsions B to I.
- Perfluoropolyether oil J25 As described above Perfluoropolyether oil J100: NOK Crew bar product BARRIERTA Dynamic viscosity (40 ° C.) 95 mm 2 / sec Perfluoropolyether oil J400: NOK Kruber product BARRIERTA J400 FLUID; dynamic viscosity (40 ° C) 390 mm 2 / Seconds
- the average particle size is measured at initial (d 0 ), after 1 month of room temperature (d 1 ) and after 1 month of 40 ° C. (d 2 ), and the particle size increase rate (d 1 -d) 0 ) / d 0 ⁇ 100 (%) and (d 2 ⁇ d 0 ) / d 0 ⁇ 100 (%) were calculated.
- the results obtained are shown in the following Table 2 together with the nature of the emulsion. The measured values in Example 7 are also described.
- Example 16 To 98 parts by weight of ion-exchanged water, 2 parts by weight of perfluoropolyether oil emulsion A was added while stirring to dilute, and a releasing agent emulsion was prepared.
- a release test at the time of urethane rubber molding using this release agent emulsion was carried out as follows.
- An aluminum cup having a diameter of 45 mm and a depth of 50 mm was used as a mold, and the mold was heated to 80 ° C., and then a release agent was applied and dried at 80 ° C. 100 parts by weight of a urethane prepolymer (Nippon Polyurethane Products Coronate 4090) heated to 80 ° C. and a methylene bis (o-chloroaniline) curing agent heated to 120 ° C. (Ihara Chemical Iharacuamine) 10 g of a mixture with 12.8 parts by weight of MT) was injected and heat cured at 120 ° C. for 1 hour.
- a urethane prepolymer Nippon Polyurethane Products Coronate 4090
- a methylene bis (o-chloroaniline) curing agent heated to 120 ° C.
- a hook for taking out a cured molded product is placed at the center of the injection part, and after the curing, the hook is pulled to determine the load at the time of removing the molded product from the mold using a spring balance located above.
- a value (mold release performance) was obtained.
- a value of 5 times was obtained by measuring the number of times mold release can be performed with a mold release load of 50 N or less after applying the mold release agent once at first.
- Example 16 the type and addition amount (parts by weight) of the perfluoropolyether oil emulsion used for preparation of the releasing agent emulsion, the type of dilution liquid (water: ion exchanged water, EtOH: ethanol, IPA: isopropanol) and The amounts used (parts by weight) were changed as shown in the following table.
- the obtained release performance and release life measurement values are shown in the following Table 3 together with the measurement values of Example 16.
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Abstract
Description
CF3(CF2)7CH2CH2P(O)(OC2H5)2
が、この種の用途に好んで使用されている(特許文献4~7参照)。
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)(OM1)(OM2) 〔I〕
(ここで、M1は水素原子、アルカリ金属、アンモニウム塩基または有機アミン塩基であり、M2はアルカリ金属、アンモニウム塩基または有機アミン塩基であり、nは1~6の整数、aは1~4の整数、bは1~3の整数、cは1~3の整数である)で表わされるポリフルオロアルキルホスホン酸塩を有効成分とする乳化剤およびこれを有効成分とする離型剤によって達成される。
(1) すぐれた造膜性を有し、複雑な形状の成形品に対しても均一な塗膜を形成させることができる。
(2) 金型面に対する造膜性およびイオン基による金型面への密着性にすぐれているため、離型性能および離型寿命の著しい向上が図られる。
(3) 約0.1重量%程度の低濃度の希釈でもすぐれた離型性および持続性が発揮されるため、離型剤による型汚れが低減される。
(4) 離型剤の成形品への移行性が小さいため、成形後の成形品の品質に悪影響を及ぼすことが少なく、成形品の寸法精度が向上する。
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)(OH)2 〔II〕
(ここで、nは1~6の整数、aは1~4の整数、bは1~3の整数、cは1~3の整数である)で表わされ、この化合物は、一般式
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)(OR)2 〔III〕
(ここで、Rは炭素数1~4のアルキル基である)で表わされるポリフルオロアルキルホスホン酸ジエステルを加水分解反応させることによって製造される。
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cI 〔IV〕
とトリアルキルホスファイトP(OR)3を反応させることにより得られる。ポリフルオロアルキルアイオダイド〔IV〕は、公知の化合物であり、特許文献8に記載されている。
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)(OM1)(OM2) 〔I〕
は、ポリフルオロアルキルホスホン酸
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)(OH)2 〔II〕
に、アルカリ金属水酸化物水溶液、アンモニア水溶液または有機アミンを反応させることにより得られる。
RfO(C3F6O)p(C2F4O)q(CF2O)rRf′ 〔XI〕
で表わされるものが使用される。ここで、Rf、Rf′はパーフルオロメチル基、パーフルオロエチル基等の炭素数1~5のパーフルオロ低級アルキル基であり、C3F6O基、C2F4O基およびCF2O基はランダムに結合しており、p+q+r=2~200で、p,qまたはrは0であり得る。このような一般式で表わされるパーフルオロポリエーテル油の具体例としては、以下のようなものがある。
ここで、mは2~200で、これはヘキサフルオロプロペンの光酸化重合で生成した先駆体を完全にふっ素化することにより、あるいはふっ化セシウム触媒の存在下にヘキサフルオロプロペンオキシドをアニオン重合させ、得られた末端-CF(CF3)COF基を有する酸フロリド化合物をふっ素ガス処理することにより得られる。
ここで、CF(CF3)CF2O基およびCF2O基はランダムに結合しており、m+n=3~200、m:n=(10:90)~(90:10)であり、これはヘキサフルオロプロペンの光酸化重合で生成した先駆体を完全にふっ素化することにより得られる。
ここで、m+n=3~200であり、m:n=(10:90)~(90:10)であり、これはテトラフルオロエチレンの光酸化重合で生成した先駆体を完全にふっ素化することにより得られる。
F(CF2CF2CF2O)nCF2CF3 〔XII〕
ここでn=2~100であり、これはふっ化セシウム触媒の存在下に2,2,3,3-テトラフルオロオキセタンをアニオン重合させ、得られた含ふっ素ポリエーテル(CH2CF2CF2O)nを160~300℃の紫外線照射下でふっ素ガス処理することにより得られる。
(1) 温度計および低沸物除去用レシーバーを備えた容量1Lの四口フラスコ中に、
CF3(CF2)3(CH2CF2)(CF2CF2)2(CH2CH2)I (99GC%)
500g(0.78モル)およびトリエチルホスファイトP(OC2H5)3 181g(1.56モル)を仕込み、155℃で攪拌した。このとき、副生成物であるヨウ化エチルを反応系から除去するために、細管を使用して反応液中に窒素ガスをバブリングした。反応液を微量分取してガスクロマトグラフィー分析を行い、トリエチルホスファイトの残量を確認した後、さらにトリエチルホスファイトを1回に91g(0.78モル)宛4回分添し、合計18時間攪拌した。
CF3(CF2)3(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OCH2CH3)2
CF3(CF2)3(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OCH2CH3)2 (96GC%)
300g(0.44モル)および約35%濃塩酸300gを仕込み、100℃で12時間攪拌した。冷却後、減圧ロ過して、固形分276gを回収した。この固形分を水洗して再びロ過し、さらにアセトンで洗浄してロ過し、目的物242g(0.41モル、収率92%)を得た。
CF3(CF2)3(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OH)2 〔IIa〕
(1) 温度計および低沸物除去用レシーバーを備えた容量1Lの四口フラスコ中に、
CF3(CF2)3(CH2CF2)(CF2CF2)(CH2CH2)I (99GC%)
500g(0.92モル)およびトリエチルホスファイトP(OC2H5)3 213g(1.84モル)を仕込み、155℃で攪拌した。このとき、副生成物であるヨウ化エチルを反応系から除去するために、細管を使用して反応液中に窒素ガスをバブリングした。反応液を微量分取してガスクロマトグラフィー分析を行い、トリエチルホスファイトの残量を確認した後、さらにトリエチルホスファイトを1回に107g(0.92モル)宛4回分添し、合計18時間攪拌した。
CF3(CF2)3(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OCH2CH3)2
CF3(CF2)3(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OCH2CH3)2 (96GC%)
300g(0.53モル)および約35%濃塩酸300gを仕込み、100℃で12時間攪拌した。冷却後、減圧ロ過して、固形分287gを回収した。この固形分を水洗して再びロ過し、さらにアセトンで洗浄してロ過し、目的物240g(0.49モル、収率93%)を得た。
CF3(CF2)3(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OH)2 〔IIb〕
(1) 温度計および低沸物除去用レシーバーを備えた容量1Lの四口フラスコ中に、
CF3(CF2)(CH2CF2)(CF2CF2)3(CH2CH2)I (97GC%)
500g(0.76モル)およびトリエチルホスファイトP(OC2H5)3 176g(1.52モル)を仕込み、155℃で攪拌した。このとき、副生成物であるヨウ化エチルを反応系から除去するために、細管を使用して反応液中に窒素ガスをバブリングした。反応液を微量分取してガスクロマトグラフィー分析を行い、トリエチルホスファイトの残量を確認した後、さらにトリエチルホスファイトを1回に88g(0.76モル)宛4回分添し、合計18時間攪拌した。
CF3(CF2)(CH2CF2)(CF2CF2)3(CH2CH2)P(O)(OCH2CH3)2
CF3(CF2)(CH2CF2)(CF2CF2)3(CH2CH2)P(O)(OCH2CH3)2 (96GC%)
300g(0.44モル)および約35%濃塩酸300gを仕込み、100℃で12時間攪拌した。冷却後、減圧ロ過して、固形分276gを回収した。この固形分を水洗して再びロ過し、さらにアセトンで洗浄してロ過し、目的物237g(0.40モル、収率90%)を得た。
CF3(CF2)(CH2CF2)(CF2CF2)3(CH2CH2)P(O)(OH)2 〔IIc〕
(1) 温度計および低沸物除去用レシーバーを備えた容量1Lの四口フラスコ中に、
CF3(CF2)(CH2CF2)(CF2CF2)2(CH2CH2)I (97GC%)
500g(0.90モル)およびトリエチルホスファイトP(OC2H5)3 208g(1.80モル)を仕込み、155℃で攪拌した。このとき、副生成物であるヨウ化エチルを反応系から除去するために、細管を使用して反応液中に窒素ガスをバブリングした。反応液を微量分取してガスクロマトグラフィー分析を行い、トリエチルホスファイトの残量を確認した後、さらにトリエチルホスファイトを1回に104g(0.90モル)宛4回分添し、合計18時間攪拌した。
CF3(CF2)(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OCH2CH3)2
CF3(CF2)(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OCH2CH3)2 (95GC%)
300g(0.52モル)および約35%濃塩酸300gを仕込み、100℃で12時間攪拌した。冷却後、減圧ロ過して、固形分271gを回収した。この固形分を水洗して再びロ過し、さらにアセトンで洗浄してロ過し、目的物235g(0.48モル、収率92%)を得た。
CF3(CF2)(CH2CF2)(CF2CF2)2(CH2CH2)P(O)(OH)2 〔IId〕
(1) 温度計および低沸物除去用レシーバーを備えた容量1Lの四口フラスコ中に、
CF3(CF2)(CH2CF2)(CF2CF2)2(CH2CH2)2I (97GC%)
500g(0.88モル)およびトリエチルホスファイトP(OC2H5)3 204g(1.76モル)を仕込み、155℃で攪拌した。このとき、副生成物であるヨウ化エチルを反応系から除去するために、細管を使用して反応液中に窒素ガスをバブリングした。反応液を微量分取してガスクロマトグラフィー分析を行い、トリエチルホスファイトの残量を確認した後、さらにトリエチルホスファイトを1回に104g(0.90モル)宛4回分添し、合計18時間攪拌した。
CF3(CF2)(CH2CF2)(CF2CF2)2(CH2CH2)2P(O)(OCH2CH3)2
CF3(CF2)(CH2CF2)(CF2CF2)2(CH2CH2)2P(O)(OCH2CH3)2 (97GC%)
300g(0.51モル)および約35%濃塩酸300gを仕込み、100℃で12時間攪拌した。冷却後、減圧ロ過して、固形分269gを回収した。この固形分を水洗して再びロ過し、さらにアセトンで洗浄してロ過し、目的物240g(0.46モル、収率90%)を得た。
CF3(CF2)(CH2CF2)(CF2CF2)2(CH2CH2)2P(O)(OH)2 〔IIe〕
(1) 温度計および低沸物除去用レシーバーを備えた容量1Lの四口フラスコ中に、
CF3(CF2)(CH2CF2)(CF2CF2)(CH2CH2)I (98GC%)
500g(1.12モル)およびトリエチルホスファイトP(OC2H5)3 259g(2.24モル)を仕込み、155℃で攪拌した。このとき、副生成物であるヨウ化エチルを反応系から除去するために、細管を使用して反応液中に窒素ガスをバブリングした。反応液を微量分取してガスクロマトグラフィー分析を行い、トリエチルホスファイトの残量を確認した後、さらにトリエチルホスファイトを1回に130g(1.12モル)宛4回分添し、合計18時間攪拌した。
CF3(CF2)(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OCH2CH3)2
CF3(CF2)(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OCH2CH3)2 (94GC%)
300g(0.63モル)および約35%濃塩酸300gを仕込み、100℃で12時間攪拌した。冷却後、減圧ロ過して、固形分262gを回収した。この固形分を水洗して再びロ過し、さらにアセトンで洗浄してロ過し、目的物229g(0.59モル、収率93%)を得た。
CF3(CF2)(CH2CF2)(CF2CF2)(CH2CH2)P(O)(OH)2 〔IIf〕
攪拌装置および滴下装置を備えた容量200mlに反応装置内に、40℃に加熱された水53.2gを保温しながら仕込み、参考例1で得られたポリフルオロアルキルホスホン酸〔IIa〕5g(8.4ミリモル)を加えた後、濃度1.4重量%のアンモニア水溶液15.4g(12.7ミリモル)を加え、1時間攪拌を続けて中和反応を行った。これにより、pH8のポリフルオロアルキルホスホン酸アンモニウム塩の水溶液(有効成分濃度7.0重量%)が得られた〔乳化剤水溶液I〕。
実施例1において、ポリフルオロアルキルホスホン酸〔IIa〕に、アンモニア水溶液を加えることなく1時間攪拌した場合には、添加したポリフルオロアルキルホスホン酸〔IIa〕は水に溶解せずに分離し、水溶液は得られなかった。
実施例1において、水量および濃度1.4重量%アンモニア水溶液量をそれぞれ所定量に変更し、またポリフルオロアルキルホスホン酸〔IIa〕の代りに同量(5g)の参考例2~6で得られたポリフルオロアルキルホスホン酸〔IIb〕~〔IIf〕をそれぞれ用い、それらの水溶液(有効成分濃度7.0重量%)を得た〔乳化剤水溶液II~VI〕。
実施例1において、水量を66.4gに変更し、またポリフルオロアルキルホスホン酸〔IIa〕およびアンモニア水溶液の代りに、ペンタデカフルオロオクタン酸アンモニウム塩C7F15COONH4(ジエムコ製品エフトップEF204)5g(11.6ミリモル)を用い、それの水溶液(有効成分濃度7.0重量%)を得た〔乳化剤水溶液VII〕。
攪拌装置および滴下装置を備えた容量1,000mlの反応装置内に、40℃に加熱された水186gを保温しながら仕込み、そこに乳化剤水溶液I 214gおよび一般式
C3F7O〔CF(CF3)CF2O〕mC2F5 (m:2~100)
で表わされるパーフルオロポリエーテル油(NOKクリューバー製品BARRIERTA J 25 FLUID;動粘度(40℃)25mm2/秒)100g(以上合計量500g)を加えた後、ホモジナイザを用いて回転数3000rpmで2分間の予備乳化を行い、さらに高圧ホモジナイザ(日本精機製)を用いて圧力600kgf/cm2(58.8MPa)で乳化処理し、パーフルオロポリエーテル油エマルジョンA(パーフルオロポリエーテル油100重量部に対して、ポリフルオロアルキルホスホン酸アンモニウム塩は15.0重量部)を485g(回収率97%)得た。
実施例7において、水量を385gに変更し、また乳化剤水溶液Iの代りにポリフルオロアルキルホスホン酸〔IIa〕15gを用いると、混合液は直ちに液-液分離を起こしてしまい、エマルジョンは形成されなかった。
実施例7において、乳化剤水溶液Iの代りに同量(214g)の乳化剤水溶液VIIが用いられ、パーフルオロポリエーテル油エマルジョンJを482g(回収率96%)得た。このエマルジョンJの平均粒子径は131nm、室温1ヶ月経過後の平均粒子径は136nm、40℃1ヶ月経過後の平均粒子径は140nmであり、安定なエマルジョンが形成された。
実施例7において、いずれも同量(214g)の乳化剤水溶液Iまたはそれに代る乳化剤水溶液II~VIが用いられ、また同じ一般式で表わされるパーフルオロポリエーテル油J25、J100、J400またはパーフルオロデカリンC10F18がいずれも同量(100g)用いられ、パーフルオロポリエーテル油エマルジョンB~Iを得た。
パーフルオロポリエーテル油J25:前記
パーフルオロポリエーテル油J100:NOKクリューバー製品BARRIERTA
J100 FLUID;動粘度(40℃)95mm2/秒
パーフルオロポリエーテル油J400:NOKクリューバー製品BARRIERTA
J400 FLUID;動粘度(40℃)390mm2/
秒
イオン交換水98重量部に、攪拌しながらパーフルオロポリエーテル油エマルジョンA 2重量部を添加して希釈し、離型剤乳液を調製した。
実施例16において、離型剤乳液調製に用いられたパーフルオロポリエーテル油エマルジョンの種類および添加量(重量部)、希釈液の種類(水:イオン交換水、EtOH:エタノール、IPA:イソプロパノール)および使用量(重量部)が、それぞれ次の表に示すように変更された。得られた離型性能および離型寿命の測定値は、実施例16の測定値と共に、次の表3に示される。
表3
エマルジョン 希釈液 離型 離型
例 種類 添加量 水 EtOH IPA 性能(N) 寿命(回)
実施例16 A 2 98 - - 9 5
〃 17 B 2 98 - - 9 5
〃 18 B 0.5 99.5 - - 12 4
〃 19 C 2 98 - - 10 5
〃 20 D 2 98 - - 12 5
〃 21 E 2 98 - - 13 4
〃 22 F 2 98 - - 15 3
〃 23 G 2 98 - - 16 2
〃 24 H 2 98 - - 16 2
〃 25 B 2 83 15 - 9 5
〃 26 B 2 83 - 15 8 6
実施例16において、離型剤乳液を塗布しないで、離型性能および離型寿命の測定を行ったが、成形品が金型から剥がれず、測定不能であり、したがって離型寿命は0回という結果であった。
Claims (16)
- 一般式
CnF2n+1(CH2CF2)a(CF2CF2)b(CH2CH2)cP(O)(OM1)(OM2) 〔I〕
(ここで、M1は水素原子、アルカリ金属、アンモニウム塩基または有機アミン塩基であり、M2はアルカリ金属、アンモニウム塩基または有機アミン塩基であり、nは1~6の整数、aは1~4の整数、bは1~3の整数、cは1~3の整数である)で表わされるポリフルオロアルキルホスホン酸塩を有効成分とする乳化剤。 - 水性溶液または有機溶媒溶液として調製された請求項1記載の乳化剤。
- 請求項2記載の乳化剤溶液およびパーフルオロポリエーテル油またはパーフルオロカーボン化合物よりなるエマルジョン。
- パーフルオロポリエーテル油が、一般式
RfO(C3F6O)p(C2F4O)q(CF2O)rRf′ 〔XI〕
(ここで、Rf、Rf′は炭素数1~5のパーフルオロ低級アルキル基であり、C3F6基、C2F4O基およびCF2O基はランダムに結合しており、p+q+rは2~200の整数で、p、qまたはrは0であり得る)または一般式
F(CF2CF2CF2O)nCF2CF3 〔XII〕
(ここで、nは2~100の整数である)で表わされるパーフルオロポリエーテル油である請求項3記載のエマルジョン。 - パーフルオロポリエーテル油〔X〕として、一般式
RfO〔CF(CF3)CF2O〕mRf′
(ここで、mは2~200の整数である)で表わされるパーフルオロポリエーテル油〔XIa〕が用いられた請求項4記載のエマルジョン。 - 請求項1記載の乳化剤を有効成分とする離型剤。
- ポリフルオロアルキルホスホン酸がアンモニウム塩として用いられた請求項6記載の離型剤。
- ポリフルオロアルキルホスホン酸塩の水性溶液または有機溶媒溶液として調製された請求項6記載の離型剤。
- 請求項8記載のポリフルオロアルキルホスホン酸塩溶液およびパーフルオロエーテル油よりなるエマルジョン型離型剤。
- パーフルオロポリエーテル油が、一般式
RfO(C3F6O)p(C2F4O)q(CF2O)rRf′ 〔XI〕
(ここで、Rf、Rf′は炭素数1~5のパーフルオロ低級アルキル基であり、C3F6基、C2F4O基およびCF2O基はランダムに結合しており、p+q+rは2~200の整数で、p、qまたはrは0であり得る)または一般式
F(CF2CF2CF2O)nCF2CF3 〔XII〕
(ここで、nは2~100の整数である)で表わされるパーフルオロポリエーテル油である請求項9記載のエマルジョン型離型剤。 - 一般式
RfO〔CF(CF3)CF2O〕mRf′
(ここで、mは2~200の整数である)で表わされるパーフルオロポリエーテル油〔XIa〕が用いられた請求項10記載のエマルジョン型離型剤。 - 請求項9記載のエマルジョン型離型剤が水性媒体または有機溶媒でさらに希釈され、その固形分濃度を0.01~30重量%とした水性溶液または有機溶媒溶液よりなる離型剤。
- 成形用金型に塗布して用いられる請求項12記載の離型剤。
- 請求項3記載のパーフルオロポリエーテル油エマルジョンを水性媒体または有機溶媒でさらに希釈した水性溶液または有機溶媒溶液よりなる表面処理剤。
- 撥水撥油剤または粘着防止剤として用いられる請求項14記載の表面処理剤。
- 請求項3記載のパーフルオロカーボン化合物エマルジョンよりなる酸素運搬媒体または摘出臓器保存液。
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US13/508,124 US8361215B2 (en) | 2009-11-04 | 2010-10-07 | Polyfluoroalkylphosphonic acid salt emulsifier and mold-releasing agent comprising the same as active ingredient |
KR1020127011162A KR101374596B1 (ko) | 2009-11-04 | 2010-10-07 | 폴리플루오로알킬포스폰산염 유화제 및 이것을 유효성분으로 하는 이형제 |
EP10828169.2A EP2497566B1 (en) | 2009-11-04 | 2010-10-07 | Polyfluoroalkyl phosphonate salt emulsifying agent and mold release agent comprising same as active ingredient |
CN201080050684.6A CN102596382B (zh) | 2009-11-04 | 2010-10-07 | 聚氟烷基膦酸盐乳化剂和以该乳化剂作为有效成分的脱模剂 |
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JP2009-252620 | 2009-11-04 | ||
JP2009252620A JP4715958B2 (ja) | 2009-11-04 | 2009-11-04 | ポリフルオロアルキルホスホン酸塩乳化剤 |
JP2009266189A JP4735756B2 (ja) | 2009-11-24 | 2009-11-24 | 離型剤 |
JP2009-266189 | 2009-11-24 |
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US (1) | US8361215B2 (ja) |
EP (1) | EP2497566B1 (ja) |
KR (1) | KR101374596B1 (ja) |
CN (1) | CN102596382B (ja) |
WO (1) | WO2011055609A1 (ja) |
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WO2020137080A1 (ja) * | 2018-12-27 | 2020-07-02 | 東ソー・ファインケム株式会社 | 不飽和結合を有する含フッ素化合物及びこれを用いた離型剤 |
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US9610634B2 (en) * | 2009-09-17 | 2017-04-04 | Unimatec Co., Ltd. | Emulsion and mold-releasing agent using the same |
JP4858628B2 (ja) * | 2010-05-25 | 2012-01-18 | ユニマテック株式会社 | 含フッ素ポリマー水性分散液 |
CN103877909B (zh) * | 2014-03-19 | 2015-07-08 | 中国科学院上海有机化学研究所 | 一种阴离子型氟碳表面活性剂及其制备方法 |
US20170015805A1 (en) | 2015-07-17 | 2017-01-19 | Ppg Industries Ohio, Inc. | Composition for Preparing Molded Polymeric Article |
WO2017061235A1 (ja) * | 2015-10-09 | 2017-04-13 | 信越化学工業株式会社 | フルオロオキシアルキレン基含有ポリマー変性ホスホン酸誘導体及び該誘導体を含む表面処理剤、該表面処理剤を用いた表面処理方法 |
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WO2020137080A1 (ja) * | 2018-12-27 | 2020-07-02 | 東ソー・ファインケム株式会社 | 不飽和結合を有する含フッ素化合物及びこれを用いた離型剤 |
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CN102596382B (zh) | 2014-09-17 |
EP2497566A1 (en) | 2012-09-12 |
EP2497566A4 (en) | 2017-05-10 |
EP2497566B1 (en) | 2019-01-30 |
KR101374596B1 (ko) | 2014-03-17 |
US8361215B2 (en) | 2013-01-29 |
KR20120091165A (ko) | 2012-08-17 |
CN102596382A (zh) | 2012-07-18 |
US20120214148A1 (en) | 2012-08-23 |
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