Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
  • C10M107/38—Lubricating compositions characterised by the base-material being a macromolecular compound containing halogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
  • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
  • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/32—Polymers modified by chemical after-treatment
  • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
  • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M147/00—Lubricating compositions characterised by the additive being a macromolecular compound containing halogen
  • C10M147/04—Monomer containing carbon, hydrogen, halogen and oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
  • C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
  • C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
  • C10M2213/04—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2213/00—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
  • C10M2213/04—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen
  • C10M2213/043—Organic macromolecular compounds containing halogen as ingredients in lubricant compositions obtained from monomers containing carbon, hydrogen, halogen and oxygen used as base material
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/04—Molecular weight; Molecular weight distribution
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
  • C10N2020/01—Physico-chemical properties
  • C10N2020/071—Branched chain compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/14—Electric or magnetic purposes
  • C10N2040/18—Electric or magnetic purposes in connection with recordings on magnetic tape or disc
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
  • C10N2050/015—Dispersions of solid lubricants
  • C10N2050/02—Dispersions of solid lubricants dissolved or suspended in a carrier which subsequently evaporates to leave a lubricant coating

Definitions

• the present invention relates to an ether composition useful as a lubricant, etc.
• PFPE perfluorinated polyether compound
• PFPE having two CH 2 OH groups at its molecular terminals has been commonly used.
• PFPE PFPE or its composition, which is useful as a lubricant, etc.
• Patent Document 1 (1) PFPE having three CH 2 OH groups, or PFPE having two CH 2 OH groups and one CF 3 group (Patent Document 1).
• Patent Document 2 An ether composition comprising two types of PFPEs different in the molecular weight
• the lubricant is required to have the following properties.
• the object of the present invention is to provide an ether composition which bonds to substrates with a high bonding ratio and forms a coating having a low friction coefficient surface and a lubricant containing the ether composition.
• the ether composition of the present invention is an ether composition comprising at least two compounds selected from the group consisting of a compound represented by the following formula (A1), a compound represented by the following formula (A2) and a compound represented by the following formula (A3), wherein the total number of moles of CF 3 groups in the group represented by the following formula (Z) in relation to the sum of the total number of moles of CF 3 groups in the group represented by the following formula (Z) and the total number of moles of OH groups in the group represented by the following formula (X) (CF 3 /(OH+CF 3 )) is at least 0.001 and at most 0.30:
• X is a group represented by the following formula (X),
• Y 3 is a perfluoroalkane-triyl group or a perfluoroalkane-triyl group having an etheric oxygen atom inserted between carbon-carbon atoms, provided that when Y 3 has a CF 3 group, the CF 3 group is bonded to a quaternary carbon,
• Z is a group represented by the following formula (Z):
• a is an integer of from 0 to 100
• b is 0 or 1
• s is an integer of from 0 to 19
• g is an integer of from 3 to 200
• Q is a polyfluorinated polymethylene group, a polyfluorinated polymethylene group having an etheric oxygen atom bonded between carbon-carbon atoms, a polyfluorinated polymethylene group having an etheric oxygen atom bonded to the terminal carbon atom bonded to Y 3 or a polyfluorinated polymethylene group having an etheric oxygen atom bonded between carbon-carbon atoms and an etheric oxygen atom bonded to the terminal carbon atom bonded to Y 3 .
• group (X) is a group selected from the group consisting of a group represented by the following formula (X1), a group represented by the following formula (X2), a group represented by the following formula (X3) and a group represented by the following formula (X4):
• d is an integer of from 1 to 200.
• Y 3 is a group selected from the group consisting of a group represented by the following formula (Y 3 -1), a group represented by the following formula (Y 3 -2) and a group represented by the following formula (Y 3 -3).
• the compound represented by the formula (A1) is a compound represented by the following formula (A1-1)
• the compound represented by the formula (A2) is a compound represented by the following formula (A2-1a), a compound represented by the following formula (A2-1b) or a combination of a compound represented by the following formula (A2-1a) and a compound represented by the following formula (A2-1b)
• the compound represented by the formula (A3) is a compound represented by the following formula (A3-1a), a compound represented by the following formula (A3-1b) or a combination of a compound represented by the following formula (A3-1a) and a compound represented by the following formula (A3-1b).
• the compound represented by the formula (A1), the compound represented by the formula (A2) and the compound represented by the formula (A3) have no —OCF 2 O— structure.
• the he total amount of the compound represented by the formula (A1), the compound represented by the formula (A2) and the compound represented by the formula (A3) is at least 95 mass % in relation to the ether composition.
• the ether composition has a number average molecular weight of from 500 to 1,000,000 and a molecular weight distribution (mass average molecular weight/number average molecular weight) of from 1.01 to 1.5.
• the ether composition is preferably used to form a lubricant containing the ether composition.
• the ether composition of the present invention bonds firmly to substrates, forms a coating having a surface with a low coefficient of friction and is useful as a lubricant to be applied on the surface of magnetic recording media.
• the ether composition of the present invention is an ether composition comprising at least two compounds selected from the compound (A1), the compound (A2) and the compound (A3), and preferably comprises the compound (A1) and the compound (A2), or the compounds (A1) to (A3).
• Each of the compounds (A1) to (A3) in the ether composition may consist of one or at least two compounds and preferably consists of one compound.
• X is a group (X).
• the notation of the structure —(CH 2 CH 2 O) a .(CH 2 CH(OH)CH 2 O) b — means that when at least one unit is present with respect to each of the (CH 2 CH 2 O) unit and the (CH 2 CH(OH)CH 2 O) unit, their arrangement is not particularly limited. Namely, in a case where one unit is present with respect to both units, the unit which is bonded to the terminal hydroxyl group may be either of them. Further, the structure —(CH 2 CH 2 O) a .(CH 2 CH(OH)CH 2 O) b — may be a block copolymer or a random copolymer.
• Q is a polyfluorinated polymethylene group, a polyfluorinated polymethylene group having an etheric oxygen atom bonded between carbon-carbon atoms, a polyfluorinated polymethylene group having an etheric oxygen atom bonded to the terminal carbon atom bonded to Y 3 or a polyfluorinated polymethylene group having an etheric oxygen atom bonded between carbon-carbon atoms and an etheric oxygen atom bonded to the terminal carbon atom bonded to Y 3 .
• the polyfluorinated polymethylene group means a group having at least two hydrogen atoms in —(CH 2 ) t — (wherein t is an integer of at least 2) substituted by fluorine atoms.
• Q is preferably a group represented by the formula —(CH 2 ) c —CF 2 O(CF 2 CF 2 O) d — (wherein the right hand side terminal of the group is bonded to Y 3 , c is an integer of from 1 to 100, and d is an integer of from 1 to 200).
• a is an integer of from 0 to 100, preferably an integer of from 0 to 10, more preferably an integer of from 0 to 2, particularly preferably 0 or 1.
• b is 1, a is preferably 0.
• b is preferably 0 or 1.
• the group (X) is preferably a group (X′).
• c is preferably an integer of from 1 to 10, more preferably 1 or 2.
• d is preferably an integer of from 3 to 100, more preferably from an integer of from 5 to 50.
• groups (X) When two or more groups (X) are present in one molecule, they may be the same or different. Groups (X) having different numbers of structural units may be categorized as the same. For example, the same groups may have the same d or may be different only in d. With respect to the numbers other than d, groups (X′) which are different in a, b or c are considered as different groups. When two or more groups (X) are in the same molecule, it is preferred that they are the same groups.
• the group (X) is preferably a group (X1), a group (X2), a group (X3) or a group (X4), and a group (X1) or a group (X2) is more preferred in view of easy production and stability of the compounds (A1) to (A3).
• Y 3 is a perfluoroalkane-triyl group or a perfluoroalkane-triyl group having an etheric oxygen atom inserted between carbon-carbon atoms, and when Y 3 has a CF 3 group, the CF 3 group is bonded only to a quaternary carbon.
• a perfluoroalkane-triyl group means a trivalent saturated hydrocarbon group having all hydrogen atoms substituted by fluorine atoms, and a quaternary carbon atom which is not bonded to a fluorine atom may be bonded to a CF 3 group.
• Y 3 is restricted to a group having no CF 3 groups or having only a CF 3 group bonded to a quaternary carbon atom for the following reason.
• the present inventors studied the effect of the structure of PFPEs on their low friction coefficient and firm bonding, which are incompatible with each other, and found that a CF 3 group bonded to a secondary carbon atom (CF 2 ) or a tertiary carbon atom (CF) has a high degree of freedom in the molecule and hence contributes to decrease in friction coefficient (decrease in viscosity), while inhibiting firm bonding.
• CF 2 secondary carbon atom
• CF tertiary carbon atom
• the present inventors decided that the proportion of CF 3 groups in an ether composition should be controlled to attain both a low friction coefficient and firm bonding and that PFPE should have a CF 3 group which is present only at the terminal of Z and may have another CF 3 group attached to a quaternary carbon atom with a relatively low degree of freedom in Y 3 .
• Y 3 may be a group having an etheric oxygen atom inserted between carbon-carbon atoms.
• the number of etheric oxygen atoms, if present, is preferably 1 to 3. Because an etheric oxygen atom is present between carbon-carbon atoms, no etheric oxygen atom can be present at the terminal of Y 3 bonded to X or Z.
• Y 3 contains an etheric oxygen atom, it is preferred that Y 3 contains no —OCF 2 O— structure and has no —OCF 2 — structure at the terminal bonded to X or Z. Compounds having neither structure have a remarkably improved chemical stability.
• Y 3 is preferably a group having no etheric oxygen atom, particularly preferably a group (Y 3 -1), a group (Y 3 -2) or a group (Y 3 -3).
• Z is a group (Z).
• s is an integer of from 0 to 19, preferably an integer of from 0 to 15, particularly preferably an integer of from 0 to 5.
• g is an integer of from 3 to 200, preferably an integer of from 3 to 100, more preferably an integer of from 3 to 70, particularly preferably an integer of from 5 to 50.
• Groups (Z) in which s is the same are considered to be the same, irrespective of whether g is the same or different.
• the groups (Z) are preferably the same.
• the group (Z) contributes to decrease in friction coefficient and is preferred to have a certain length in view of increasing the freedom of the CF 3 group in the molecule.
• the group (Z) is preferably a group (Z1), a group (Z2) or a group (Z3).
• Each of the compounds (A1) to (A3) may be a combination of two or more compounds which preferably have the same Y 3 but differ in a, b, c or d in the group (X).
• the average of a is preferably a positive number of from 0 to 2, particularly preferably 0.
• the average of c is preferably 1
• the average of d is preferably a positive number of from 3 to 100.
• the average of g is preferably a positive number of from 3 to 100.
• the compounds (A1) to (A3) have no —OCF 2 O— structure in view of chemical stability.
• a compound having no —OCF 2 O— structure means a compound in which the presence of the structure cannot be detected by a conventional analytical means (such as 19 F-NMR).
• the compound (A1) a compound (A11) or a compound (A12) is preferred.
• a compound (A21) or a compound (A22) is preferred.
• a compound (A31) or a compound (A32) is preferred.
• the compound (A1) is preferably a compound (A1-1)
• the compound (A2) is preferably a compound represented by the following formula (A2-1a), a compound represented by the following formula (A2-1b) or a combination of a compound represented by the following formula (A2-1a) and a compound represented by the following formula (A2-1b)
• the compound (A3) is preferably a compound represented by the following formula (A3-1a), a compound represented by the following formula (A3-1b) or a combination of a compound represented by the following formula (A3-1a) and a compound represented by the following formula (A3-1b).
• the present inventors found that the friction coefficient and the bonding ratio vary depending on the proportion of groups (Z) and therefore decided that the ratio of groups (Z) is within a specific range.
• the total number of moles of CF 3 groups in the group (Z) in relation to the sum of the total number of moles of CF 3 groups in the group (Z) and the total number of moles of OH groups in the group (X) (CF 3 /(OH+CF 3 ), hereinafter referred to as CF 3 ratio) is at least 0.001 and at most 0.30.
• CF 3 ratio is preferably at least 0.01 and at most 0.30.
• the composition of the present invention having a low CF 3 ratio and more than two compounds has such an effect that it is unlikely to adhere to other substances in contact with it.
• the CF 3 ratio can be determined by identifying the structures of the compounds in the ether composition and then measuring their contents, or directly from the ether composition.
• the ether composition is analyzed by 19 F-NMR, and the peak area for CF 3 groups is determined.
• the chemical shift of —OCF 3 is observed around ⁇ 54.0 to ⁇ 56.0 ppm.
• the number of terminal OH groups is determined from the area of the peak attributed to the fluorine atoms in CF 2 around ⁇ 80 to ⁇ 81.0 ppm in the 19 F-NMR spectrum when the terminal groups are —CF 2 CH 2 OH, from the area of the peak attributed to the fluorine atoms in CF 2 around ⁇ 75.0 to ⁇ 78.0 ppm in the 19 F-NMR spectrum when the terminal groups are —CF 2 CH 2 OCH 2 CH(OH)CH 2 OH, or from the area of the peak attributed to the fluorine atoms in CF 2 around ⁇ 78.0 to ⁇ 80.0 ppm in the 19 F-NMR spectrum when the of terminal groups are —CF 2 CH 2 (OCH 2 CH 2 ) g OH.
• the number of terminal OH groups can also be determined by measuring —OCF 3 by 19 F-NMR and 1 H-NMR using a compound having both hydrogen and fluorine atoms such as bistrifluoromethylbenzene as an internal control.
• the peak attributed to OH groups can shift and overlap with the zone important for identification around 3.5 to 3.8 ppm, depending on the measurement environment (such as pH). Therefore, it is preferred to deutrate the hydrogen in OH groups by adding a trace amount of a deuterated solvent (such as heavy water) to a sample to shift the peak attributed to OH groups so that the peak does not overlap with the previously mentioned peaks.
• a deuterated solvent such as heavy water
• the ether composition of the present invention does not contain a compound (A4).
• a compound (A4) By not containing the compound (A4), it is means that the compound (A4) is not contained at all, or even if present, its content measured by high performance liquid chromatography (hereinafter referred to as HPLC) is at most 2.0 mass %.
• HPLC high performance liquid chromatography
• the total amount of the compounds (A1) to (A3) is preferably at least 95 mass % in relation to the ether composition, more preferably at least 98 mass %.
• the mass ratios (mass %) of the compound (A1) and the compound (A2) in the ether composition is from 50 to 95 for the compound (A1) and from 5 to 50 for the compound (A2), preferably from 60 to 80 for the compound (A1) and from 20 to 40 for the compound (A2).
• the ratios (mass %) of the compound (A1), the compound (A2) and the compound (A3) in the ether composition are from 50 to 90 for the compound (A1), from 5 to 50 for the compound (A2) and from 1 to 25 for the compound (A3), preferably from 60 to 80 for the compound (A1), from 10 to 20 for the compound (A2) and from 5 to 10 for the compound (A3).
• the number average molecular weight (hereinafter referred to as Mn) of the ether composition is preferably from 500 to 1,000,000, more preferably from 500 to 100,000, particularly preferably from 1,000 to 20,000.
• the molecular weight distribution (hereinafter referred to as Mw/Mn) of the ether composition is preferably from 1.01 to 1.5, more preferably from 1.01 to 1.25.
• Mw is the mass average molecular weight.
• the ether composition has a low viscosity, contains a small amount of evaporative components and dissolves homogeneously in a solvent.
• the Mn can be measured by gel permeation chromatography (hereinafter referred to as GPC).
• GPC gel permeation chromatography
• the ether composition of the present invention may be prepared by the following methods.
• Method 1 Prepare and purify the compounds (A1) to (A3) respectively and formulate them into a composition.
• Method 2 Prepare the compounds (A1) to the compound (A3) so that the resulting reaction product also contains the other two as by-products, and purify the reaction product to a certain CF 3 ratio to obtain a composition.
• Method 3 Mix two or more compositions obtained after purification in the method 2 into a single composition.
• the compound (A1) can be prepared in accordance with the method disclosed in Patent Document 1
• the compounds (A2) and (A3) can be prepared in accordance with the method disclosed in Patent Document 1 by carrying out the reaction by using starting materials for the compounds (A2) and the compound (A3) instead of the starting material for the compound (A1).
• a reaction product containing by-products can be obtained by carrying out a reaction in the same manner as in the method 1 or under modified reaction conditions.
• the compounds (A2) to (A4) having terminal CF 3 groups can be formed by cleavage of molecular terminals.
• the fluorine gas concentration in the gas blown into the liquid phase is preferably from 5.0 to 50 vol %, more preferably from 10 to 30 vol % in view of suppression of formation of the compound (A4).
• the product of the liquid phase fluorination may contain the compound (A4). If contained, the compound (A4) is preferred to be removed by purification.
• the ether composition of the present invention may be used as it is, after addition of other compounds or as an additive for other compounds.
• the ether composition of the present invention may be used as it is or in combination with other substances.
• the composition may be used as it is.
• PFPE other than the compounds (A1) to (A3) may be added to the ether composition.
• PFPE-XX PFPE other than the compounds (A1) to (A3)
• its amount is preferably at most 10 mass %, more preferably at most 5 mass % in relation to the total amount of the ether composition (the ether composition of the present invention and the PFPE-XX) so that the present invention can show its characteristics sufficiently.
• the ether composition of the present invention may be added to PFPE-XX.
• the content of the PFPE-XX is preferably at most 50 mass %, more preferably at most 30 mass %, in relation to the total amount of the ether composition.
• FOMBLIN Z-DiOL FOMBLIN Z-TetraOL
• DEMNUM SA DEMNUM SA and the like.
• FOMBLIN Z-DIAC FOMBLIN Z-DEAL
• FOMBLIN AM2001 FOMBLIN Z-DISOC
• DEMNUM SH MorescoA20H and the like.
• an ether compound (A 4 ) having from 1 to 4 groups (X) and from 0 to 3 groups (Z) and having at least 4 groups (X) and (Z) in total may be mentioned.
• the ether compound (A 4 ) is preferably at least one member selected from a compound (A 4 1), a compound (A 4 2), a compound (A 4 3) and a compound (A 4 4).
• X is a group (X)
• Y4 is a perfluoroalkane-tetrayl group or a perfluoroalkane-triyl group having an etheric oxygen atom inserted between carbon-carbon atoms and having no structure of the group (Z)
• Z is a group (Z).
• the group (X) is preferably the group (X1), the group (X2), the group (X3) or the group (X4), and the group (X1) or the group (X2) is more preferred in view of the ease of production of the compounds (A 4 1) to (A 4 4) and their stability.
• Y 4 is preferred to have no CF 3 group.
• Y 4 is preferably any one of the groups (Y 4 -1) to (Y 4 -4), and the group (Y 4 -1) is particularly preferred because these compounds are easy to synthesize, are chemically stable and have low crystallinity.
• the CF 3 ratio in the whole composition is preferably adjusted to at least 0.001 and at most 0.30 in order for the ether composition of the present invention to exert its performance.
• the PFPE-XX is preferred not to contain a PFPE having only CF 3 groups at the terminals. In this case, the total number of moles of OH groups covers all the terminal OH groups, and the total number of moles of CF 3 groups covers all the CF 3 groups other than those attached to a quaternary carbon atom. These total numbers of moles can be determined by NMR as previously described.
• PFPE-XX having a number average molecular weight of from 1,000 to 10,000 as the PFPE-XX.
• the ether composition of the present invention is preferably used as a solvent composition by dissolving or dispersing the ether composition in a solvent.
• the solvent is preferably a perfluoroamine (such as perfluorotripropylamine or perfluorotributylamine), a perfluoroalkane (such as Vertrel XF (manufactured by DuPont)) or a hydrofluoroether (such as AE-3000 (manufactured by Asahi Glass Company, Limited)), and a hydrofluoroether is more preferred in view of its low ozone depleting potential.
• a perfluoroamine such as perfluorotripropylamine or perfluorotributylamine
• a perfluoroalkane such as Vertrel XF (manufactured by DuPont)
• a hydrofluoroether such as AE-3000 (manufactured by Asahi Glass Company, Limited)
• a hydrofluoroether is more preferred in view of its low ozone depleting potential.
• the solvent composition may be a solution, a suspension or an emulsion and is preferably a solution.
• the concentration of the ether composition of the present invention in the solvent composition is preferably from 0.001 to 50 mass %, more preferably from 0.01 to 20 mass %.
• the solvent composition may contain or may not contain an additional component other than the ether composition of the present invention and the solvent (hereinafter referred to additional component).
• additional component may be a radical scavenger (such as X1p (manufactured by Dow Chemicals)) or the like.
• the additional component may be a coupling agent (of a silane, epoxy, titanium or aluminum type).
• a coupling agent improves adhesion between a substrate and a coating.
• the solvent composition does not contain metal ions, anions, water, low molecular weight polar compounds or the like because otherwise, the solvent composition would not show the intended performance.
• Ions of metals can form Lewis acid catalysts with anions which catalyze decomposition of PFPEs.
• Anions of F, Cl, NO 2 , NO 3 , PO 4 , SO 4 , C 2 O 4 and the like
• water can corrode the surface of a substrate. Therefore, the water content of the solvent composition is preferably at most 2,000 ppm.
• Low molecular weight polar compounds such as alcohols, plasticizers eluted from resins
• the ether composition of the present invention is used as a lubricant for magnetic disks, it is used in the same manner as conventional lubricants. For example, it is applied to the surface of a substrate for a magnetic disk by roll coating casting, dip coating (dipping), spin coating, water casting, die coating, Langmuir-Blodgett film formation or vacuum vapor deposition, and dip coating, spin coating or vacuum vapor deposition is preferred.
• the substrate may be a NiP-plated substrate (aluminum, glass or the like) having a primer layer, a recording layer and a carbon protective layer in this order.
• the carbon protective layer is preferably at most 5.0 mm thick and preferably has an average surface roughness (Ra) of at most 2.0 mm.
• a magnetic disk having a lubricant layer is preferably subjected to adsorption treatment so that the lubricant is adsorbed onto the surface of the carbon protective layer.
• the adsorption treatment may be heat treatment, infrared treatment, UV treatment or plasma treatment, and is preferably heat treatment or UV treatment, more preferably heat treatment. Further, after adsorption treatment, the magnetic disk may be washed with a fluorine-containing solvent for the purpose of removal of contaminants and an excess of the lubricant.
• the surface of the lubricant coating after the adsorption treatment has good water repellency enough to keep the inside the magnetic disk off water and shows good lubricity for a long time.
• the bonding ratio of the ether composition of the present invention after adsorption treatment can be at least 60%. It is preferably at least 65%, particularly preferably at least 70%.
• the contact angle of water (at room temperature) on the surface of a magnetic disk treated with the ether composition of the present invention can be at least 80°. It is preferably at 85°.
• the preferred thickness of a coating formed of the ether composition of the present invention is at most 5.0 nm, more preferably at most 3.0 nm, particularly preferably at most 2.0 nm, in view of improvement of recording density and durability.
• the ether composition of the present invention can be applied to surfaces other than those of magnetic disk substrates.
• a surface modifier to be applied to the surfaces of polymer substrates for control of the refractive indices of the substrates, as a surface modifier for improvement in the chemical resistance of polymer substrates by surface modification, as an additive to be added to a wire coating material, an ink repellent (for example, for coating or for a printer such as an ink jet printer), an adhesive for semiconductor devices (such as an adhesive for lead on chip tape, a protective coating for semiconductor (such as a moistureproof coating agent or an ascent inhibitor for soldering) or a thin membrane (such as a pellicle membrane) to be used in optical field, a lubricant for an antireflection film for displays and an antireflection film for resists.
• a coating formed from the ether composition of the present invention is transparent, has a low refractive index, and is excellent in heat resistance and chemical resistance. Further, the coating has high lubricity and has self-replenishing property.
• the ether composition of the present invention is also useful as a surfactant.
• it may be used as an additive to lower the surface tension of paint, a leveling agent for paint or a leveling agent for a polishing liquid.
• it is preferably added in an amount of from 0.01 to 5 mass % in relation to the paint.
• TMS tetramethylsilane
• CCl 2 FCClF 2 is abbreviated as R-113,
• CClF 2 CClFCF 2 OCF 2 CClF 2 is abbreviated as CFE-419,
• hexafluoroisopropyl alcohol is abbreviated as HFIP, and
• Isopropyl alcohol is abbreviated as IPA.
• TMS was used as a standard substance for 1 H-NMR (300.4 MHz), and CFCl 3 was used as a standard substance for 19 F-NMR (282.7 MHz). R-113 was used as a solvent for NMR, unless otherwise specified.
• the ratios of the compounds in the composition were determined with a HPLC analyzer (Prominence, manufactured by Shimadzu Corporation) under the following conditions. Specifically, in each run, the HPFIP concentration in the mobile phase was gradually increased from 0% to 100%, and the mass ratios of compounds in the composition eluted in descending order of the number of OH groups were determined.
• Analytical column normal phase silica gel column (SIL-gel, manufactured by YMC Co., Ltd.)
• Detector evaporative light scattering detector
• Mn and Mw were measured by GPC in accordance with JP-A-2001-208736 under the following conditions, and Mw/Mn was determined.
• Detector evaporative light scattering detector
• the friction coefficient on the surface of each lubricant coating was measured with a friction meter (Tribogear, manufactured by Heidon) using a SUS ball with a diameter of 10 mm as a contactor under a load 2 kg load at 25 rpm.
• the surface of the contactor was inspected under an optical microscope for lubricant transfer at the four contact points and rated as ⁇ when no lubricant transfer was observed, as ⁇ when lubricant transfer was observed at 1 to 3 contact points and as x when lubricant transfer was observed at all the four contact points.
• the metal ion content in 1.0 g of each fraction was determined by ashing-inductively coupled plasma-mass spectroscopy.
• Liquid phase fluorination was carried out in the same manner as in Example 2-1 in Patent Document 1 except that R-113 was replaced with CFE-419, and the compound (D3-1) was replaced with the compound (B-1) to obtain a composition (c-1).
• the composition (c-1) contained a compound (C-1) as a main component, and in the composition, at least 99.9 mol % of the hydrogen atoms in the compound (B-1) had been replaced by fluorine atoms.
• Liquid phase fluorination was carried out in the same manner as in Example 2 except that the fluorine gas concentration in the gals blown into the liquid phase was changed from 20 vol % to 10 vol % to obtain a composition (c-2).
• Liquid phase fluorination was carried out in the same manner as in Example 2 except that the fluorine gas concentration in the gals blown into the liquid phase was changed from 20 vol % to 50 vol % to obtain a composition (c-3).
• Example 3 in Patent Document 1 was followed except that the compound (D4-1) was replaced with the composition (c-1), with the composition (c-2) and with the composition (c-3), to obtain a composition (d-1), a composition (d-2) and a composition (d-3) each containing a compound (D-1) as a main component.
• Example 4-1 in Patent Document 1 was followed except that the compound (D5-1) was replaced with the composition (d-1), with the composition (d-2) and with the composition (d-3), to obtain a composition (e-1), a composition (e-2) and a composition (e-3) each containing a compound (E-1) as a main component.
• Example 5 in Patent Document 1 was followed except that the compound (D7-1) was replaced with the composition (e-1), with the composition (e-2) and with the composition (e-3), to obtain a composition (a-1), a composition (a-2) and a composition (a-3) each containing a compound (A11-1) as a main component.
• each of the resulting compositions contained compounds having two terminal OH groups (A21-1a) and (A21-1b) (hereinafter the compounds (A21-1a) and (A21-1b) are collectively referred to as (A21-1)) and compounds having one terminal OH group (A31-1a) and (A31-1b) (hereinafter the compounds (A31-1a) and (A31-1b) are collectively referred to as (A31-1)).
• the ratio of terminal OH groups to terminal CF 3 groups in the molecule were calculated from the ratio of the area of the peak attributed to the fluorine atoms in CF 3 groups around ⁇ 54.0 ppm to the area of the peak attributed to the fluorine atoms in CF 2 groups in CF 2 CH 2 OH groups around ⁇ 80.1 ppm.
• composition (a-3) was purified by column chromatography as follows.
• a slurry of a particulate silica gel (MS-Gel D75-120A, manufactured by S. I. Tech Co., Ltd.) in R-225 was packed into a column with a diameter of 150 mm and a length of 500 mm to form a silica gel bed with a height of 100 mm.
• the fraction (p1-3) was purified by supercritical extraction as follows.
• a thick-walled stainless steel vessel (inner diameter ⁇ 33 mm ⁇ depth 45 mm) having an inlet and an outlet, a supercritical carbon dioxide delivery pump (SCF-210, manufactured by JASCO Corporation), an automatic back pressure regulator (880-01, manufactured by JASCO Corporation) and an ordinary chromatographic column oven were assembled into an apparatus.
• SCF-210 supercritical carbon dioxide delivery pump
• automatic back pressure regulator 880-01, manufactured by JASCO Corporation
• a carbon protective layer was formed on glass blanks for magnetic disks (2.5′′ blanks, manufactured by Asahi Glass Company, Limited) by depositing DLC (diamond-like carbon) by radio-frequency magnetron sputtering using a carbon target to obtain stimulant disks.
• the Ar gas pressure was 0.003 Torr, and the input power density on the target was 3 W/cm 2 .
• the carbon protective layers were 30 nm thick.
• the water contact angle on the carbon protective layers was 40°.
• fractions (p2-2), (p2-3) and (p2-5) were diluted with Vertrel XF to obtain solvent compositions having a fraction concentration of 0.01 mass %.
• the stimulant disks were dipped in the solvent compositions for 30 seconds and pulled out at a constant rate of 6 mm/sec.
• the stimulant disks coated with the solvent compositions were subjected to heat treatment in a thermostatic oven at 100° C. for 1 hour to form lubricant coatings.
• the disks having lubricant coatings were rinsed with Vertrel XF for 30 seconds by dipping.
• the thicknesses of the lubricant coatings were measured with an ellipsometer before and after rinsing to determine the bonding ratios.
• the contact angles and friction coefficients on the surfaces of the lubricant coatings were measured. After measurement of friction coefficients, the surface of the contactor was inspected under an optical microscope for lubricant transfer. The results are shown in Table 6.
• the CF 3 ratio in the compound is 0.
• Lubricant coatings were formed on stimulant disks in the same manner as in Example 10 except that the fraction (p2-2) was replaced with the fraction (p2-6) or (p2-7) and evaluated in the same manner as in Example 10. The results are shown in Table 6.
• Examples 10 to 12 indicate that a composition comprising PFPEs having three terminal groups having specific structures at the molecular terminals can provide a surface with a high bonding ratio, a large contact angle and a small friction coefficient, when the OH/CH 3 ratio is more than 2 and at most 100.
• the ether composition of the present invention shows a high bonding ratio, forms a coating having a low friction coefficient surface and is useful as a lubricant to be applied on the surface of magnetic recording media.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Lubricants (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polyethers (AREA)

Applications Claiming Priority (5)

Related Parent Applications (1)

Publications (1)

Family

ID=40795596

Family Applications (1)

Country Status (6)

Cited By (5)

Families Citing this family (4)

Citations (35)

Family Cites Families (1)

• 2008
  • 2008-12-19 JP JP2009546304A patent/JP5152199B2/ja not_active Expired - Fee Related
  • 2008-12-19 CN CN2008801221589A patent/CN101903467B/zh not_active Expired - Fee Related
  • 2008-12-19 TW TW097149800A patent/TW200948894A/zh unknown
  • 2008-12-19 KR KR1020107011730A patent/KR20100094484A/ko not_active Withdrawn
  • 2008-12-19 WO PCT/JP2008/073225 patent/WO2009078485A1/fr not_active Ceased
• 2010
  • 2010-06-04 US US12/793,757 patent/US20100240560A1/en not_active Abandoned

Patent Citations (41)

Also Published As

Similar Documents

Legal Events