WO2009093665A1 - エーテル組成物 - Google Patents
エーテル組成物 Download PDFInfo
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- WO2009093665A1 WO2009093665A1 PCT/JP2009/050998 JP2009050998W WO2009093665A1 WO 2009093665 A1 WO2009093665 A1 WO 2009093665A1 JP 2009050998 W JP2009050998 W JP 2009050998W WO 2009093665 A1 WO2009093665 A1 WO 2009093665A1
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- 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
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- 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
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- 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
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- 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
Definitions
- the present invention relates to an ether composition useful as a lubricant or the like.
- PFPE perfluorinated polyether compound
- Non-patent Document 1 A perfluorinated polyether compound (hereinafter referred to as PFPE) is used as a lubricant applied to the surface of a magnetic recording medium (Non-patent Document 1).
- PFPE perfluorinated polyether compound having two CH 2 OH groups at the end of the molecule has been widely used.
- PFPE useful as a lubricant or a composition thereof.
- 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 containing two types of PFPE having different molecular weights.
- the fixing property to the magnetic recording medium is high as the speed of the magnetic recording medium increases.
- the surface has a low coefficient of friction when used as a coating film in order to disperse the impact when the recording element comes into contact with the magnetic recording medium.
- the present invention provides an ether composition having a high fixability to a substrate and a low surface friction coefficient when formed into a coating film, and a lubricant containing the ether composition.
- the present invention has the gist characterized by the following. (1) having 1 to 4 groups represented by the following formula (X) and 0 to 3 groups represented by the following formula (Z), and a group represented by the formula (X):
- An ether composition comprising two or more types of ether compounds (A) in which the total number of groups represented by formula (Z) is four. HO— (CH 2 CH 2 O) a ⁇ (CH 2 CH (OH) CH 2 O) b —Q— (X), CF 3 (CF 2 ) s O (CF 2 CF 2 O) g ⁇ (Z).
- a is an integer of 0 to 100
- b is 0 or 1
- s is an integer of 0 to 19
- g is 3 to It is an integer of 200
- Q is a polyfluorinated polymethylene group or a polyfluorinated polymethylene group having an etheric oxygen atom.
- X is a group represented by the formula (X)
- Y is a perfluoroalkane-tetrayl group or a group in which an etheric oxygen atom is inserted between carbon-carbon atoms of the group and does not have the structure of the group represented by the formula (Z).
- Z is a group represented by the formula (Z).
- X is 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)
- the ether composition according to (1) or (2) above which is a group selected from the group consisting of: HOCH 2 CF 2 O (CF 2 CF 2 O) d ⁇ (X1), HOCH 2 CH (OH) CH 2 OCH 2 CF 2 O (CF 2 CF 2 O) d ⁇ (X2), HOCH 2 CH 2 CF 2 O (CF 2 CF 2 O) d ⁇ (X3), HOCH 2 CH 2 OCH 2 CF 2 O (CF 2 CF 2 O) d ⁇ (X4).
- d is an integer of 1 to 200.
- Y is a group having no CF 3 group.
- Y is a group represented by the following formula (Y-1), a group represented by the following formula (Y-2), a group represented by the following formula (Y-3), and the following formula (Y -4)
- the ether composition according to (2) or (3) above which is a group selected from the group consisting of groups represented by
- 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 compound represented by the following formula (A2-1a)
- a compound represented by the following formula (A2-1b) A compound represented by the formula (A3), a compound represented by the following formula (A3-1a), a compound represented by the following formula (A3-1b), a compound represented by the following formula (A3-1c), And a compound selected from the group consisting of compounds represented by the following formula (A3-1d):
- the compound represented by the formula (A4) is represented by the following formula (A4-1a), the following formula (A4-1b), or the following formula (A4-1a)
- X and Z in a formula show the same meaning as the above.
- the ratio of the total molar amount of CF 3 groups (CF 3 / (OH + CF 3 )) contained in the group represented by the formula (Z) is 0.01 to 0.5, the above (1) to (6)
- the ether composition of the present invention has a high fixability to a substrate and a low surface friction coefficient when used as a coating film.
- a compound represented by the formula (A1) will be referred to as a compound (A1).
- a group represented by the formula (X) is referred to as a group (X).
- Groups represented by other formulas are also described in the same manner.
- the ether composition of the present invention is an ether having 1 to 4 groups (X) and 0 to 3 groups (Z), and the total number of groups (X) and groups (Z) is 4. 2 types or more of a compound (A) are included. HO— (CH 2 CH 2 O) a ⁇ (CH 2 CH (OH) CH 2 O) b —Q— (X), CF 3 (CF 2 ) s O (CF 2 CF 2 O) g ⁇ (Z).
- a is an integer of 0 to 100, preferably an integer of 0 to 10, more preferably an integer of 0 to 2, and particularly preferably 0 or 1.
- b is 1, a is preferably 0.
- b is 0 or 1.
- — (CH 2 CH 2 O) a ⁇ (CH 2 CH (OH) CH 2 O) b The structure is represented by (CH 2 CH 2 O) units and (CH 2 CH (OH) CH 2 O) units. When each unit has one or more units, it means that the arrangement of the units is not limited. That is, when both units are present, the terminal OH group may be bonded to any unit.
- the — (CH 2 CH 2 O) a ⁇ (CH 2 CH (OH) CH 2 O) b — structure may be a block copolymer structure or a random copolymer structure. Good.
- Q is a polyfluorinated polymethylene group or a polyfluorinated polymethylene group having an etheric oxygen atom.
- the polyfluorinated polymethylene group refers to a group in which at least two hydrogen atoms in — (CH 2 ) t — (t is an integer of 2 or more) are substituted with fluorine atoms.
- Q is a group represented by — (CH 2 ) c —CF 2 O (CF 2 CF 2 O) d — (provided that Y binds to Y at the right end of the group. It is an integer, and d is an integer of 1 to 200).
- a group (X ′) is preferable. HO— (CH 2 CH 2 O) a ⁇ (CH 2 CH (OH) CH 2 O) b — (CH 2 ) c —CF 2 O (CF 2 CF 2 O) d ⁇ ... (X ′).
- a to d have the same meaning as described above.
- c is preferably an integer of 1 to 10, and more preferably 1 or 2.
- d is preferably an integer of 3 to 100, and more preferably an integer of 5 to 50.
- Groups of the same group (X) include groups having different numbers of structural units. For example, a group (X ′) having the same number of d or a group (X ′) having only a different number of d is considered to be the same group. In the number of a, b, c, and d, groups (X ′) that are different from each other in a, b, and c are considered to be different groups. When several group (X) exists in 1 molecule, it is preferable that it is the same group.
- the group (X) is preferably a group (X1), a group (X2), a group (X3) or a group (X4). From the viewpoint of ease of production and stability of the ether compound (A), the group (X1 Or a group (X2) is more preferred. HOCH 2 CF 2 O (CF 2 CF 2 O) d ⁇ (X1), HOCH 2 CH (OH) CH 2 OCH 2 CF 2 O (CF 2 CF 2 O) d ⁇ (X2), HOCH 2 CH 2 CF 2 O (CF 2 CF 2 O) d ⁇ (X3), HOCH 2 CH 2 OCH 2 CF 2 O (CF 2 CF 2 O) d ⁇ (X4).
- s is an integer of 0 to 19, preferably an integer of 0 to 15, and more preferably an integer of 0 to 5.
- g is an integer of 3 to 200, preferably an integer of 3 to 100, more preferably an integer of 3 to 70, and particularly preferably an integer of 5 to 50.
- the group (Z) is the same group means a group in which the number of s is the same and the number of g may be the same or different.
- the group (Z) preferably consists of the same group.
- the group (Z) is a group that contributes to the reduction of the friction coefficient, and preferably has a certain chain length from the viewpoint of increasing the molecular freedom of the CF 3 group, and the group (Z1), the group (Z2 Or a group (Z3) is more preferable.
- the ether composition of the present invention is preferably an ether composition comprising two or more compounds selected from the group consisting of compound (A1), compound (A2), compound (A3) and compound (A4), and compound (A1) And an ether composition comprising the compound (A2) is more preferred.
- the compounds (A1) to (A4) in the ether composition may each consist of one or more compounds, and each of the compounds (A1) to (A4) consists of one compound. Is preferred. (X-) 4 Y (A1) (X-) 3 YZ (A2), (X-) 2 Y (-Z) 2 (A3), XY (-Z) 3 (A4). However, X is group (X) and Z is group (Z).
- Y is a perfluoroalkane-tetrayl group or a group in which an etheric oxygen atom is inserted between carbon-carbon atoms of the group and does not have the structure of the group represented by the formula (Z).
- the perfluoroalkane-tetrayl group means a tetravalent saturated hydrocarbon group in which all of the hydrogen atoms are substituted with fluorine atoms.
- the quaternary carbon atom to which the CF 3 group is bonded means a carbon atom to which no fluorine atom is bonded.
- Y is for the following reasons, a group having no CF 3 group, or, it is preferred that the said CF 3 group when having CF 3 group is a group attached to the quaternary carbon, CF 3 A group having no group is preferred. That is, as a result of studying the relationship between the contradictory properties of a low friction coefficient and high fixability and the structure of PFPE, the present inventors have bonded to a secondary carbon atom (CF 2 ) or a tertiary carbon atom (CF).
- the CF 3 group was found to be a group that contributes to a reduction in the coefficient of friction (reduction in viscosity), while it is a group that inhibits fixing properties, since it has a high degree of freedom in the molecule.
- the present inventors control the ratio of CF 3 groups in the ether composition in order to achieve both a low friction coefficient and high fixability, and in order to facilitate the control, the CF 3 groups are Even if it exists only at the terminal of Z or exists in Y, it was decided to exist as a CF 3 group bonded to a quaternary carbon atom having a relatively low degree of freedom. Furthermore, from the viewpoint of availability of the compound, Y is particularly preferably a group that does not have a CF 3 group.
- Y may be a group in which an etheric oxygen atom is inserted between carbon-carbon atoms.
- the number of etheric oxygen atoms is preferably 1 to 3. Since the etheric oxygen atom exists between carbon-carbon atoms, there is no etheric oxygen atom at the end of Y bonded to X or Z.
- Y contains an etheric oxygen atom, it is preferred that there is no —OCF 2 O— structure in Y, and it is preferred that no —OCF 2 — structure be present at the terminal portion bonded to X and Z. In a compound having no such structure, the chemical stability is remarkably improved.
- Y is more preferably any of groups (Y-1) to (Y-4), and group (Y-1) is easy to synthesize, chemical stability of the compound, and low crystallinity. From the point of view, it is preferable.
- each of the compounds (A1) to (A4) is composed of two or more compounds include compounds in which Y is the same and a, b, c or d of the group (X) are different.
- the average of a in the group (X) is preferably a positive number of 0 to 2, and 0 is particularly preferable.
- the average of c is preferably 1.
- the average of d is preferably a positive number from 3 to 100.
- the average of g in the group (Z) is preferably a positive number of 3 to 100.
- the ether compound (A) preferably has no —OCF 2 O— structure from the viewpoint of chemical stability.
- the compound having no —OCF 2 O— structure means a compound in which the presence of the structure cannot be detected by a usual analysis method ( 19 F-NMR, etc.).
- the compound (A1) the compound (A11) or the compound (A12) is preferable. ⁇ HOCH 2 CF 2 O (CF 2 CF 2 O) d ⁇ 4 Y (A11), ⁇ HOCH 2 CH (OH) CH 2 OCH 2 CF 2 O (CF 2 CF 2 O) d - ⁇ 4 Y ⁇ (A12).
- the compound (A2) the compound (A21) or the compound (A22) is preferable.
- the compound (A3) the compound (A31) or the compound (A32) is preferable.
- a compound (A41) or a compound (A42) is preferable.
- the compound (A1) when Y is a group (Y-1) is preferably the compound (A1-1), and the compound (A2) is the compound (A2-1a), the compound (A2-1b), and
- a compound selected from the group consisting of the combination of compound (A2-1a) and compound (A2-1b) is preferred, and the compound (A3) is selected from the group consisting of compound (A3-1a) to compound (A3-1d).
- the compound selected is preferable, and the compound (A4) is selected from the group consisting of the compound (A4-1a), the compound (A4-1b), and the combination of the compound (A4-1a) and the compound (A4-1b).
- Compounds are preferred.
- the ether composition of the present invention is composed of two or more of each of the compounds (A1) to (A4), for example, when the compound is composed of two or more of the compound (A1), X is composed of the group (X1).
- a combination of the compound (A11) and the compound (A12) in which X is a group (X2) is preferable.
- the ether composition containing compound (A11) and compound (A12) may further contain compound (A13a), compound (A13b), or a combination of compound (A13a) and compound (A13b).
- Y in the compound (A13a) and the compound (A13b) is preferably a group (Y-1).
- the ether composition of the present invention preferably comprises an ether compound having a group (Z). Furthermore, the present inventors have found that the friction coefficient and the fixing ratio change depending on the ratio of the group (Z), and have specified a preferable range of the ratio of the group (Z). That is, in the ether composition of the present invention, the CF 3 group that the group (Z) has relative to the total amount of the CF 3 group that the group (Z) has and the total mole amount of the OH group that the group (X) has.
- the total molar amount ratio (CF 3 / (OH + CF 3 ), hereinafter referred to as CF 3 ratio) is preferably 0.01 to 0.5, more preferably 0.01 to 0.25, and 0.01 to 0.
- the ether composition of the present invention can achieve both a low friction coefficient and a high fixability at a high level. If the CF 3 ratio in the composition is too large, the bleed-out defect will increase rather than the effect of reducing the friction coefficient. If the CF 3 ratio is too low, the friction coefficient becomes large.
- the composition of the present invention composed of two or more compounds including a compound having a CF 3 terminal has an effect of lowering adhesion to other contact materials.
- the presence of a small amount of the end group CF 3 of Z significantly contributes to the increase in the fixing rate of the composition, the reduction of the friction coefficient, and the prevention of bleed out.
- Examples of the method for determining the CF 3 ratio include a method for determining the structure of a compound contained in an ether composition and determining the content, or a method for determining the composition as it is. Specifically, in the case of obtaining using NMR method, 19 F-NMR of the ether composition is measured, and the peak area of the CF 3 group is obtained. For example, the 19 F-NMR chemical shift of —OCF 3 can be observed in the vicinity of ⁇ 54.0 to ⁇ 56.0 ppm.
- the terminal when the terminal is a —CF 2 CH 2 OH group, the vicinity of ⁇ 80 to ⁇ 81.0 ppm of 19 F-NMR derived from the fluorine atom of CF 2 in the group It is obtained from the peak area.
- the terminal when the terminal is a —CF 2 CH 2 OCH 2 CH (OH) CH 2 OH group, ⁇ 75.0 to ⁇ 78.0 ppm of 19 F-NMR derived from the fluorine atom of CF 2 in the group It is obtained from the nearby peak area.
- a 19 F-NMR of about ⁇ 78.0 to ⁇ 80.0 ppm is derived from the fluorine atom of CF 2 in the group. Obtained from the peak area.
- a compound having both a hydrogen atom and a fluorine atom is used as an internal standard substance, and it can be determined from the measurement results of 19 F-NMR and 1 H-NMR.
- the internal standard substance include bistrifluoromethylbenzene.
- the terminal when the terminal is a —CF 2 CH 2 OH group, from the peak area in the vicinity of 4.0 to 4.1 ppm of 1 H-NMR derived from CH 2 in the group, —CF 2 CH 2 OCH
- it is a 2 CH (OH) CH 2 OH group or a —CF 2 CH 2 O (CH 2 CH 2 O) g —H group, 3.8 to 3 derived from CH 2 adjacent to CF 2
- It can also be determined by the ratio of the peak area around 4.0 ppm or the peak area around 3.5 ppm derived from CH 2 of the terminal CH 2 OH. It can also be determined from the peak area around 3.7 to 3.9 ppm derived from CH in the CH (OH) portion.
- the 1 H-NMR signal used for quantification of the number of OH groups overlaps.
- the group is converted into a group such as CF 3 C (O) O— or CH 3 C (O) O, and the number of OH groups from the peak area of chemical shift of 1 H-NMR or 19 F-NMR of the group Can be requested.
- the peak position of the peak derived from the OH group varies depending on the measurement environment (pH, etc.) and may overlap particularly near 3.5 to 3.8 ppm, which is important for identification. is there. Therefore, it is desirable to deuterate the hydrogen of the OH group by adding a very small amount of deuterium solvent (for example, heavy water) to the sample, and shift it to a position that does not overlap with the aforementioned peak group.
- deuterium solvent for example, heavy water
- the ether composition of the present invention preferably does not contain the compound (A5). It does not contain compound (A5) at all, or even if it is contained, the content determined by high performance liquid chromatography (hereinafter referred to as HPLC) is 2.0% by mass or less. Means. Y (-Z) 4 (A5).
- the ether composition of the present invention does not contain the compound (A5), so that bleed out can be suppressed and the fixability of the lubricant to the base material can be increased.
- the compound (A5) is preferably removed from the ether composition by a purification method described later.
- the total amount of the compounds (A1) to (A4) is preferably 95% by mass or more, and more preferably 98% by mass or more with respect to the ether composition.
- the total amount may be 100% by mass.
- the number average molecular weight (hereinafter referred to as Mn) of the ether composition is preferably 500 to 1,000,000, more preferably 500 to 100,000, and particularly preferably 1,000 to 20,000.
- the molecular weight distribution (hereinafter referred to as Mw / Mn) of the ether composition is preferably 1.01 to 1.5, more preferably 1.01 to 1.25. If Mn and Mw / Mn are in this range, the viscosity is low, the evaporation component is small, and the uniformity when dissolved in the solvent is excellent.
- Mn is measured by gel permeation chromatography (hereinafter referred to as GPC). Mw / Mn is determined from Mn and Mw (mass average molecular weight) measured by GPC.
- Method 1 A method of preparing a compound (A1) to compound (A4) and purifying them, and then blending each to prepare a composition.
- Method 2) When producing any one of compounds (A1) to (A4), a reaction product containing compounds (A1) to (A4) other than the one compound as a by-product Obtaining and purifying the reaction product to obtain a composition having a specific CF 3 ratio.
- Method 3) A method of blending two or more of the purified compositions in Method 2 to obtain a composition.
- compounds (A1) to (A4) can be produced by changing the raw materials in the method described in International Publication No. 2005/068534 to raw materials corresponding to compounds (A1) to (A4). .
- a compound having a terminal COF is obtained by esterification, liquid phase fluorination, and ester decomposition reaction described in International Publication No. 2005/068534.
- Method 1 a method in which the compound having the terminal COF is reduced by reacting with an alcohol or water to form an ester or a carboxylic acid, or (Method 1-2) the terminal A compound in which COF is COF by esterification by transesterification with alcohols, or reduction by reacting with water to form an ester or carboxylic acid after reaction with water.
- Method 2 it is preferable from the viewpoint of production efficiency to adopt the method by transesterification described in Method 1-2.
- a reaction product containing a by-product can be obtained by carrying out the reaction in the same manner as in Method 1 or by changing the reaction conditions in Method 1.
- the compound (A1) when the compound (A1) is produced by a method that undergoes a liquid phase fluorination reaction and the conditions of the liquid phase fluorination reaction are severe, a molecular end cleavage reaction occurs and has a CF 3 group at the end.
- Compounds (A2) to (A5) may be formed.
- the concentration of fluorine gas contained in the gas blown into the liquid phase is preferably 5.0 to 50% by volume, more preferably 10 to 30% by volume from the viewpoint of suppressing the formation of the compound (A5). .
- the product may contain the compound (A5).
- the compound (A5) is included, it is preferably removed by purification.
- the purification method include a method of removing metal impurities, anion impurities, and the like with an ion-adsorbing polymer, a supercritical extraction method, and column chromatography, and a combination of these methods is preferable.
- the ether composition of the present invention may be used as it is, or may be used by adding other compounds, or may be used as an additive to other compounds.
- the ether composition of the present invention may be used as it is, or the ether composition and another substance may be used in combination.
- the ether composition may be used as it is.
- PFPE other than the compounds (A1) to (A4) hereinafter referred to as other PFPE-XX
- other PFPE-XX may be added to the ether composition.
- the amount of other PFPE-XX added to the ether composition of the present invention is not limited to the total amount of the ether composition (the ether composition according to the present invention and the other PFPEs described above) in order to fully exhibit the characteristics of the present invention.
- -XX preferably 10% by mass or less, and more preferably 5% by mass or less.
- the ether composition of the present invention may be added to other PFPE-XX.
- the content of other PFPE-XX is preferably 50% by mass or less, and more preferably 30% by mass or less, based on the total amount of the ether composition.
- the CF 3 ratio in the total composition is set to 0.01 to 0.5 in order to exhibit the performance of the ether composition of the present invention. It is preferable to adjust so that it becomes 0.01 to 0.25, more preferably 0.01 to 0.15, and particularly preferably 0.01 to 0. It is particularly preferable to adjust to .05.
- the total molar amount of OH groups in the total composition includes all terminal OH groups, all CF 3 group other than CF 3 groups attached to the quaternary carbon atoms in the total molar amount of CF 3 groups included. These total molar amounts can be determined by the NMR method described above.
- other PFPE-XX those having a number average molecular weight of 1000 to 10,000 are preferably used.
- the ether composition is preferably used as a solvent composition in which the ether composition is dissolved or dispersed in a solvent.
- the solvent include perfluoroamines (perfluorotripropylamine, perfluorotributylamine, etc.), perfluoroalkanes (Bertrel XF (manufactured by DuPont), etc.) or hydrofluoroethers (AE-3000 (manufactured by Asahi Glass Co., Ltd.)).
- perfluoroamines perfluorotripropylamine, perfluorotributylamine, etc.
- perfluoroalkanes Bertrel XF (manufactured by DuPont), etc.
- hydrofluoroethers AE-3000 (manufactured by Asahi Glass Co., Ltd.)
- the solvent composition may be any of a solution, a suspension or an emulsion, and a solution is preferable.
- concentration of the ether composition of the present invention in the solvent composition is preferably 0.001 to 50% by mass, more preferably 0.01 to 20% by mass.
- Components other than the ether composition of the present invention and the solvent may be contained in the solvent composition.
- examples of other components when the solvent composition is used as a lubricant include radical scavengers (for example, X1p (manufactured by Dow Chemicals), etc.).
- examples of other components when the solvent composition is used as a surface modifier include coupling agents (silane-based, epoxy-based, titanium-based, aluminum-based, etc.). The coupling agent improves the adhesion between the substrate and the coating film.
- the solvent composition may not achieve the desired performance, it is preferable that the solvent composition does not contain metal ions, anions, moisture, low-molecular polar compounds, and the like.
- Metal ions Na, K, Ca, Al, etc.
- Anions F, Cl, NO 2 , NO 3 , PO 4 , SO 4 , C 2 O 4 etc.
- moisture may corrode the surface of the substrate. Therefore, it is preferable that each content is as follows.
- Al and Mg are preferably 1000 ppb or less, Na and K are both 20000 ppb or less, Ca is 10000 ppb or less, and Fe, Ni, Cu, and Zn are all preferably 100 ppb or less. It is preferable that F is 10,000 ppm or less, and formic acid, Cl, NO 3 , SO 4 , and oxalic acid are all 5000 ppb or less.
- the water content of the solvent composition is preferably 2000 ppm or less, particularly preferably 1000 ppm or less.
- Low molecular polar compounds may reduce the adhesion between the substrate and the coating film.
- a known method for using a lubricant can be applied.
- coating methods on the substrate surface for magnetic disks include roll coating method, casting method, dip coating method (dipping method), spin coating method, water casting method, die coating method, Langmuir project method, vacuum deposition method.
- the dip coating method, the spin coating method or the vacuum deposition method is preferable.
- the substrate include a substrate having a base layer, a recording layer, and a carbon protective film in this order on a NiP plated substrate (aluminum, glass, etc.).
- the thickness of the carbon protective film is preferably 5.0 nm or less, and the average surface roughness (Ra) of the carbon protective film is preferably 2.0 nm or less.
- adsorption treatment so that the lubricant is firmly adsorbed on the surface of the carbon protective film.
- the adsorption treatment include heat treatment, infrared irradiation treatment, ultraviolet irradiation treatment, and plasma treatment. Heat treatment or ultraviolet irradiation treatment is preferable, and heat treatment is more preferable.
- the magnetic disk after the adsorption treatment may be washed with a fluorinated solvent for the purpose of removing the deposits and excess lubricant.
- the surface of the lubricant film after the adsorption treatment has high water repellency, even if it is placed under high temperature and high humidity, it prevents moisture from penetrating into the magnetic disk and provides high lubricity over a long period of time. Can be maintained.
- the fixing rate after the adsorption treatment can be 60% or more.
- the fixing rate is more preferably 65% or more, and particularly preferably 70% or more.
- the contact angle (room temperature) of water on the surface of the magnetic disk treated with the ether composition of the present invention can be 80 ° or more.
- the contact angle is particularly preferably 85 ° or more.
- the thickness of the coating film formed from the ether composition of the present invention is preferably 5.0 nm or less, more preferably 3.0 nm or less, and more preferably 2.0 nm or less from the viewpoint of improving recording density and durability. Particularly preferred.
- the ether composition of the present invention can be applied to surfaces other than the magnetic disk substrate.
- a surface modifier that is applied to the surface of a polymer substrate to control the refractive index of the polymer substrate a surface modifier that improves the chemical resistance of the polymer substrate, a wire coating material, ink repellent Agent (for example, ink repellent for coating, ink repellent for printing equipment (inkjet, etc.)), adhesive for semiconductor elements (for example, adhesive for lead-on-chip tape, etc.), protective coat for semiconductor (for example, , Moisture-proof coating agents, anti-cracking agents for solder, etc.), additives for thin films used in the optical field (for example, pellicle film, etc.), lubricants for antireflection films for displays, antireflection films for resists, etc. Useful.
- the coating film obtained from the ether composition of the present invention is transparent, has a low refractive index, and is excellent in heat resistance or chemical resistance.
- the coating film retains high lubricity and has self-repairing properties.
- the ether composition of the present invention is also useful as a surfactant.
- it can be used as an additive for reducing the surface tension of paint, a leveling agent for paint, a leveling agent for polishing liquid, and the like.
- the addition amount of the ether composition of the present invention is preferably 0.01 to 5% by mass relative to the paint.
- HPLC analysis The composition ratio of the compounds contained in the composition was measured under the following conditions using an HPLC apparatus (Prominence, manufactured by Shimadzu Corporation). Specifically, in one cycle of analysis, the concentration of HFIP in the mobile phase is gradually increased from 0% to 100%, and the compounds contained in the composition are sequentially separated from the compound having the smallest number of OH groups. The mass ratio was analyzed.
- Analysis column normal phase silica gel column (manufactured by YMC, SIL-gel), Mobile phase: R-225 (Asahi Glass Co., Ltd., Asahi Clin AK-225G) and HFIP, Mobile phase flow rate: 1.0 mL / min, Column temperature: 37 ° C Detector: Evaporative light scattering detector.
- the contact angle on the surface of the lubricant coating was measured using a contact angle meter (Face, CA-X). Five drops of about 2 ⁇ L of water droplets or hexadecane were placed on the surface of the lubricant coating, the contact angle was measured, and the average of the five values was determined.
- the coefficient of friction of the surface of the lubricant coating was measured using a friction measuring device (Heidon, Tribogear). A SUS ball having a diameter of 10 mm was used as the contact, and measurement was performed at a load of 2 g and a rotation speed of 25 rpm.
- Adhesion test The contact surface after the friction coefficient measurement test was observed with an optical microscope. The four contact parts were confirmed, the presence or absence of lubricant adhesion was confirmed, and the following criteria were evaluated. ⁇ indicates no adhesion; ⁇ indicates adhesion at 1 to 3 locations; ⁇ indicates adhesion at 4 locations.
- Metal ion analysis The metal ion content of 1.0 g of each fraction was measured by ashing-inductively coupled plasma mass spectrometry.
- Example 1 In the method described in Example 11 of International Publication No. 2005/068534, polyoxyethylene glycerol ether (manufactured by NOF Corporation, UNIOX G1200) is converted to diglycerin-initiated polyoxyethylene glycerol ether (manufactured by Sakamoto Pharmaceutical Co., Ltd.). The reaction was carried out in the same manner except that it was changed to SC-E1500). Diglycerin-initiated polyoxyethylene glycerol ether was reacted with FCOCF (CF 3 ) OCF 2 CF (CF 3 ) O (CF 2 ) 3 F to obtain a compound (B-1) which was liquid at room temperature.
- Example 2 In the method described in Example 2-1 of Example of International Publication No. 2005/068534, R-113 is changed to CFE-419, and the concentration of fluorine gas contained in the gas blown into the liquid phase is changed from 20% by volume to 10%.
- the liquid phase fluorination reaction of compound (B-1) was carried out in the same manner except that the volume% was changed.
- the product was a composition (c-2) in which the compound (C-1) was a main component and 99.9 mol% or more of the hydrogen atoms in the compound (B-1) were substituted with fluorine atoms.
- R f in the formula (C-1) is —CF (CF 3 ) OCF 2 CF (CF 3 ) OCF 2 CF 2 CF 3 .
- the NMR spectrum measured in the composition (c-2) is as follows.
- Example 3 According to the method described in Example 3 of Example of International Publication No. 2005/068534, the composition (c-2) is subjected to ester decomposition reaction, and the composition (d- 2) was obtained.
- Example 4 [Example 4-1] According to the method described in Example 4-1 of Example in International Publication No. 2005/068534, an esterification reaction was performed by reacting the composition (d-2) with ethanol. A composition (e-2) containing the compound (E-1) as a main component was obtained. The composition (e-2) was used in the reaction of Example 5.
- Example 4-2 According to the method described in Example 4-2 of the example of International Publication No. 2005/068534, a transesterification reaction was performed by reacting the composition (d-2) with ethanol to obtain the compound (E-1) as the main component. A composition as an ingredient was obtained.
- Example 5 In the method described in Example 5 of International Publication No. 2005/068534, the composition (e-2) is subjected to a reduction reaction, and the composition (a-2) containing the compound (A11-1) as a main component Got.
- the obtained composition (a-2) contains At least one selected from the compound (A21-1a) and the compound (A21-1b) having three OH group ends and one CF 3 group end (hereinafter referred to as compound (A21-1)); At least one selected from the compound (A31-1a), the compound (A31-1b), the compound (A31-1c) and the compound (A31-1d) having two OH group ends and two CF 3 group ends (hereinafter, referred to as the following) Compound (A31-1)), and at least one compound selected from compound (A41-1a) and compound (A41-1b) having one OH group end and three CF 3 group ends (hereinafter referred to as compound (A A41-1).) Is included.
- composition (a-2) 1 H-NMR ⁇ (ppm): 3.94.
- the ratio of the OH group at the end of the molecule to the CF 3 group at the end of the molecule was determined by NMR analysis.
- CF 3 / (OH + CF 3 ) value (8 / (92 + 8)
- the ratio of the OH group at the end of the molecule to the CF 3 group at the end of the molecule was as follows: the peak area around ⁇ 54.0 ppm derived from the fluorine atom of the CF 3 group, and the CF 2 CH 2
- the Mn of the composition (a-2) obtained by GPC analysis was 2500 and Mw / M was calculated by determining the ratio to the peak area around ⁇ 80.1 ppm derived from the fluorine atom of the CF 2 group of OH group.
- Mn was 1.12
- the composition ratio (mass ratio) determined by HPLC was 1% for compound (A41-1), 3% for compound (A31-1), and 24% for compound (A21-1).
- Compound (A11-1) is 72% (A51-1) were not included.
- the composition (a-2) was purified by the following column chromatography.
- Granular silica gel (MS-Gel D75-120A manufactured by S-Tech Co., Ltd.) diluted with R-225 was packed into a column having a diameter of 150 mm and a length of 500 mm to form a silica gel packed phase having a height of 100 mm.
- fractionation operation was performed while gradually increasing the concentration of IPA in the extraction solvent using an extraction solvent (mixed solvent of R-225 and IPA).
- Fractions (p1-1) to (p1-5) were obtained.
- Table 1 shows the amount of the extraction solvent, the IPA concentration in the extraction solvent, and the fraction amount. Of these, the fraction (p1-4) was used for further purification.
- the proportions of the compound (A31-1) and the compound (A41-1) are large in the fraction with low polarity, and the compound (A11-1) and the compound (A21-1) in the fraction with high polarity IPA. ),
- the elution pattern was influenced by the number of terminal hydroxyl groups.
- the fraction (p1-4) was purified by the following supercritical extraction method. Thick stainless steel container (inner diameter ⁇ 33 mm ⁇ depth 45 mm) with inlet and outlet, supercritical carbon dioxide fluid feed pump (manufactured by JASCO Corporation, SCF-201), automatic pressure control valve (manufactured by JASCO Corporation, 880- 81), an apparatus equipped with a column oven used for ordinary column chromatography was prepared. 70 g of the fraction (p1-4) was injected into the container, and supercritical carbon dioxide was allowed to flow at a liquefied carbon dioxide equivalent flow rate of 5.0 cc / min.
- the temperature in the container was fixed at 60 ° C., the pressure in the container was changed over time, and fractionation was performed at each pressure stage to obtain fractions (p2-1) to (p2-7).
- Table 3 shows the pressure in the container, the holding time of the pressure, and the amount of fractions.
- Examples 8 to 11 (Examples)] Using carbon as a target, DLC was deposited on glass blanks for magnetic disks (2.5 "blanks, manufactured by Asahi Glass Co., Ltd.) by high-frequency magnetron sputtering in an Ar atmosphere to form a carbon protective film, and a simulated disk was produced.
- the gas pressure of Ar was 0.003 Torr
- the input power density during sputtering was 3 W / cm 2 per target area
- the thickness of the carbon protective film was 30 nm.
- the water contact angle was 40 °.
- the fraction (p2-1), fraction (p2-3), fraction (p2-4), and fraction (p2-5) obtained in Example 7 were diluted with Vertrel XF, respectively.
- a solvent composition having a concentration of 0.01% by mass was prepared.
- the simulated disk was immersed in the solvent composition for 30 seconds and pulled up at a constant speed of 6 mm / second.
- the simulated disk coated with the solvent composition was heat-treated at 100 ° C. for 1 hour in a constant temperature furnace to form a lubricant coating.
- the disk on which the lubricant film was formed was washed by immersing it in Bartrel XF for 30 seconds. Before and after cleaning, the thickness of the lubricant coating was measured with an ellipsometer to determine the fixing rate. In addition, the contact angle and coefficient of friction of the surface of the lubricant coating were measured to evaluate the adhesion. The results are shown in Table 5.
- the ether composition of the present invention is useful as a lubricant or the like. It should be noted that all of the specifications, claims and abstracts of Japanese Patent Application No. 2008-013638 filed on January 24, 2008 and Japanese Patent Application No. 2008-196371 filed on July 30, 2008 are as follows. The contents of which are hereby incorporated herein by reference.
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Abstract
Description
該潤滑剤としては、従来から分子の末端に2つのCH2OH基を有するPFPEが汎用されている。
(1)3つのCH2OH基を有するPFPE、または2つのCH2OH基と1つのCF3基とを有するPFPE(特許文献1)。
(2)分子量の異なる2種のPFPEを含むエーテル組成物(特許文献2)。
(i)磁気記録媒体の高速化に伴い、磁気記録媒体への定着性が高いこと。
(ii)磁気記録媒体に記録素子が接触した際の衝撃を分散するために、塗膜としたときの表面の摩擦係数が低いこと。
「月刊トライボロジ」、1995年、第99巻、11月号、p.37-38
(1)下式(X)で表される基の1~4個と下式(Z)で表される基の0~3個とを有し、かつ式(X)で表される基と式(Z)で表される基の総数が4個であるエーテル化合物(A)の2種以上を含む、ことを特徴とするエーテル組成物。
HO-(CH2CH2O)a・(CH2CH(OH)CH2O)b-Q- ・・・(X)、
CF3(CF2)sO(CF2CF2O)g- ・・・(Z)。
ただし、上記式(X)および式(Z)において、aは、0~100の整数であり、bは、0または1であり、sは、0~19の整数であり、gは、3~200の整数であり、Qは、ポリフルオロ化されたポリメチレン基、またはエーテル性酸素原子を有するポリフルオロ化されたポリメチレン基である。
(2)前記エーテル化合物(A)の2種以上が、下式(A1)で表される化合物、下式(A2)で表される化合物、下式(A3)で表される化合物および下式(A4)で表される化合物からなる群より選ばれる2種以上である、上記(1)に記載のエーテル組成物。
(X-)4Y ・・・(A1)
(X-)3Y-Z ・・・(A2)、
(X-)2Y(-Z)2 ・・・(A3)、
X-Y(-Z)3 ・・・(A4)。
ただし、
Xは、前記式(X)で表される基であり、
Yは、ペルフルオロアルカン-テトライル基、または該基の炭素-炭素原子間にエーテル性酸素原子が挿入された基であり、かつ式(Z)で表される基の構造を有さない基であり、
Zは、前記式(Z)で表される基である。
(3)Xが、下式(X1)で表される基、下式(X2)で表される基、下式(X3)で表される基、および下式(X4)で表される基からなる群より選ばれる基である、上記(1)または(2)に記載のエーテル組成物。
HOCH2CF2O(CF2CF2O)d- ・・・(X1)、
HOCH2CH(OH)CH2OCH2CF2O(CF2CF2O)d- ・・・(X2)、
HOCH2CH2CF2O(CF2CF2O)d- ・・・(X3)、
HOCH2CH2OCH2CF2O(CF2CF2O)d- ・・・(X4)。
ただし、dは、1~200の整数である。
(4)Yが、CF3基を有さない基である、上記(2)または(3)に記載のエーテル組成物。
(5)Yが、下式(Y-1)で表される基、下式(Y-2)で表される基、下式(Y-3)で表される基、および下式(Y-4)で表される基からなる群より選ばれる基である、上記(2)または(3)に記載のエーテル組成物。
式(A2)で表される化合物が、下式(A2-1a)で表される化合物、下式(A2-1b)で表わされる化合物、または、下式(A2-1a)で表される化合物と下式(A2-1b)で表わされる化合物の組み合わせであり、
式(A3)で表される化合物が、下式(A3-1a)で表される化合物、下式(A3-1b)で表される化合物、下式(A3-1c)で表される化合物、および下式(A3-1d)で表される化合物からなる群より選ばれる化合物であり、
式(A4)で表される化合物が、下式(A4-1a)で表される化合物、下式(A4-1b)で表される化合物、または、下式(A4-1a)で表される化合物と下式(A4-1b)で表される化合物の組み合わせである、上記(2)~(5)のいずれかに記載のエーテル組成物。
(7)エーテル組成物中に存在する式(Z)で表される基が有するCF3基の総モル量および式(X)で表される基が有するOH基の総モル量の合計量に対する式(Z)で表される基が有するCF3基の総モル量の割合(CF3/(OH+CF3))が、0.01~0.5である、上記(1)~(6)のいずれかに記載のエーテル組成物。
(8)エーテル化合物(A)が、-OCF2O-構造を有さない、上記(1)~(7)のいずれかに記載のエーテル組成物。
(9)エーテル化合物(A)の総量が、エーテル組成物に対して95質量%以上である、上記(1)~(8)のいずれかに記載のエーテル組成物。
(10)エーテル組成物の数平均分子量が、500~1000000であり、かつエーテル組成物の分子量分布が、1.01~1.5である、上記(1)~(9)のいずれかに記載のエーテル組成物。
(11)上記(1)~(10)のいずれかに記載のエーテル組成物を含む潤滑剤。
また、式(X)で表される基を基(X)と記す。他の式で表される基も同様に記す。
HO-(CH2CH2O)a・(CH2CH(OH)CH2O)b-Q- ・・・(X)、
CF3(CF2)sO(CF2CF2O)g- ・・・(Z)。
aは、0~100の整数であり、0~10の整数が好ましく、0~2の整数がより好ましく、0または1が特に好ましい。bが1である場合のaは、0が好ましい。
bは、0または1である。
HO-(CH2CH2O)a・(CH2CH(OH)CH2O)b-(CH2)c-CF2O(CF2CF2O)d- ・・・(X’)。
ただし、a~dは前記と同じ意味を示す。
cは、1~10の整数が好ましく、1または2がより好ましい。
dは、3~100の整数が好ましく、5~50の整数がより好ましい。
HOCH2CF2O(CF2CF2O)d- ・・・(X1)、
HOCH2CH(OH)CH2OCH2CF2O(CF2CF2O)d- ・・・(X2)、
HOCH2CH2CF2O(CF2CF2O)d- ・・・(X3)、
HOCH2CH2OCH2CF2O(CF2CF2O)d- ・・・(X4)。
sは、0~19の整数であり、0~15の整数が好ましく、0~5の整数がより好ましい。
gは、3~200の整数であり、3~100の整数が好ましく、3~70の整数がより好ましく、5~50の整数が特に好ましい。
基(Z)が同一の基であるとは、sの数が同一であり、gの数は同一であっても異なってもよい基をいう。基(Z)は同一の基からなるのが好ましい。
CF3O(CF2CF2O)g- ・・・(Z1)、
CF3(CF2)2O(CF2CF2O)g- ・・・(Z2)、
CF3(CF2)5O(CF2CF2O)g- ・・・(Z3)。
(X-)4Y ・・・(A1)
(X-)3Y-Z ・・・(A2)、
(X-)2Y(-Z)2 ・・・(A3)、
X-Y(-Z)3 ・・・(A4)。
ただし、Xは、基(X)であり、Zは、基(Z)である。
ペルフルオロアルカン-テトライル基とは、水素原子のすべてがフッ素原子に置換した4価の飽和の炭化水素基を意味する。また、CF3基が結合する4級炭素原子とは、フッ素原子が結合していない炭素原子を意味する。
すなわち、本発明者らは、低摩擦係数と高定着性の相反する性質と、PFPEの構造との関係を検討した結果、2級炭素原子(CF2)または3級炭素原子(CF)に結合したCF3基は、分子内での自由度が高いため、摩擦係数の低下(低粘度化)に寄与する基である一方、定着性を阻害する基であることを見出した。そこで、本発明者らは、低摩擦係数と高定着性を両立させるために、エーテル組成物におけるCF3基の割合をコントロールすること、そして該コントロールを容易にするために、CF3基は、Zの末端にのみ存在させる、またはYに存在したとしても、相対的に自由度が低い4級炭素原子に結合したCF3基として存在させることとした。さらに、化合物の入手容易性の観点からYはCF3基を有さない基であることが特に好ましい。
{HOCH2CF2O(CF2CF2O)d-}4Y ・・・(A11)、
{HOCH2CH(OH)CH2OCH2CF2O(CF2CF2O)d-}4Y ・・・(A12)。
{HOCH2CF2O(CF2CF2O)d-}3Y-(OCF2CF2)gO(CF2)sCF3 ・・・(A21)、
{HOCH2CH(OH)CH2OCH2CF2O(CF2CF2O)d-}3Y-(OCF2CF2)gO(CF2)sCF3 ・・・(A22)。
{HOCH2CF2O(CF2CF2O)d-}2Y{-(OCF2CF2)gO(CF2)sCF3}2 ・・・(A31)、
{HOCH2CH(OH)CH2OCH2CF2O(CF2CF2O)d-}2Y{-(OCF2CF2)gO(CF2)sCF3}2 ・・・(A32)。
HOCH2CF2O(CF2CF2O)d-Y{-(OCF2CF2)gO(CF2)sCF3}3 ・・・(A41)、
HOCH2CH(OH)CH2OCH2CF2O(CF2CF2O)d-Y{-(OCF2CF2)gO(CF2)sCF3}3 ・・・(A42)。
化合物(A11)および化合物(A12)を含むエーテル組成物は、さらに化合物(A13a)、化合物(A13b)、または、化合物(A13a)と化合物(A13b)の組み合わせを含んでいてもよい。化合物(A13a)および化合物(A13b)におけるYは基(Y-1)であるのが好ましい。
{HOCH2CF2O(CF2CF2O)d-}{HOCH2CH(OH)CH2OCH2CF2O(CF2CF2O)d-}3Y ・・・(A13a)、
{CF3O(CF2CF2O)d-}{HOCH2CH(OH)CH2OCH2CF2O(CF2CF2O)d-}3Y ・・・(A13b)。
具体的には、NMR法を用いて求める場合において、エーテル組成物の19F-NMRを測定し、CF3基のピーク面積を求める。たとえば、-OCF3の19F-NMRのケミカルシフトは-54.0~-56.0ppm付近に観測できる。
OH基末端の数の定量については、末端が-CF2CH2OH基である場合には、該基中のCF2のフッ素原子に由来する19F-NMRの-80~-81.0ppm付近のピーク面積から求まる。末端が、-CF2CH2OCH2CH(OH)CH2OH基である場合には、該基中のCF2のフッ素原子に由来する19F-NMRの-75.0~-78.0ppm付近のピーク面積から求まる。末端が-CF2CH2(OCH2CH2)gOH基である場合には、該基中のCF2のフッ素原子に由来する19F-NMRの-78.0~-80.0ppm付近のピーク面積から求まる。
また別の方法として、水素原子とフッ素原子を併有する化合物を内部標準物質として使用し、19F-NMRと1H-NMRの測定結果から求めることができる。内部標準物質としては、ビストリフルオロメチルベンゼン等が挙げられる。
たとえば、末端が-CF2CH2OH基である場合には、該基中のCH2に由来する1H-NMRの4.0~4.1ppm付近のピーク面積から、-CF2CH2OCH2CH(OH)CH2OH基である場合または-CF2CH2O(CH2CH2O)g-H基である場合には、CF2に隣接するCH2に由来する3.8~4.0ppm付近のピーク面積、または末端のCH2OHのCH2に由来する3.5ppm付近のピーク面積との比でも求めることができる。またCH(OH)部分のCHに由来する3.7~3.9ppm付近のピーク面積からも求めることができる。
CH2CH(OH)CH2とCH2CH2Oを併有する場合には、OH基の数の定量に用いる1H-NMRのシグナルが重複することから、該基に結合するOH基を化学修飾により、CF3C(O)O-、またはCH3C(O)O等の基に変換し、該基の1H-NMRまたは19F-NMRのケミカルシフトのピーク面積からOH基の数を求めることができる。
さらに1H-NMRの測定の際には、OH基に由来するピークは測定環境(pH等)によってピーク位置が変動し、特に同定上重要な3.5~3.8ppm付近に重複する場合がある。したがって、ごく微量の重水素溶媒(たとえば、重水。)をサンプルに加えることで、OH基の水素を重水素化し、前述したピーク群に重複しない位置にシフトさせることが望ましい。
Y(-Z)4 ・・・(A5)。
エーテル組成物の分子量分布(以下、Mw/Mnと記す。)は、1.01~1.5が好ましく、1.01~1.25がより好ましい。
MnおよびMw/Mnが該範囲にあれば、粘度が低く、蒸発成分が少なく、溶媒に溶解した際の均一性に優れる。
Mnは、ゲルパーミエーションクロマトグラフィ(以下、GPCと記す。)により測定される。Mw/Mnは、GPCにより測定されたMnおよびMw(質量平均分子量)から求める。
方法1)化合物(A1)~化合物(A4)をそれぞれ製造して精製した後に、それぞれを配合して組成物を調整する方法。
方法2)化合物(A1)~化合物(A4)のいずれか1種の化合物を製造する際に、該1種の化合物以外の化合物(A1)~(A4)を副生成物として含む反応生成物を得て、該反応生成物を精製してCF3比率が特定の比率である組成物とする方法。
方法3)方法2において精製後の組成物の2種以上を配合して組成物とする方法。
方法2による場合、方法1と同様に反応を行うことにより、または、方法1における反応条件を変更することにより副生成物を含む反応生成物が得られる。たとえば、化合物(A1)を、液相フッ素化反応を経る方法により製造する場合で、かつ液相フッ素化反応の条件が厳しい場合、分子の末端の切断反応が起こり、末端にCF3基を有する化合物(A2)~(A5)が生成することがある。液相フッ素化反応において、液相に吹き込むガスに含まれるフッ素ガス濃度は、化合物(A5)の生成を抑制する点から、5.0~50体積%が好ましく、10~30体積%がより好ましい。フッ素ガス濃度が高濃度になると、基(Z)の生成割合が高くなり、生成物中の化合物(A1)の割合は低く、化合物(A2)~化合物(A4)および化合物(A5)の生成割合が高くなる傾向がある。
化合物(A5)が含まれる場合、精製により除くことが好ましい。
精製方法としては、イオン吸着ポリマーによって金属不純物、陰イオン不純物等を除去する方法、超臨界抽出法、カラムクロマトグラフィが挙げられ、これらを組み合わせた方法が好ましい。
本発明のエーテル組成物は、これをそのまま使用、または、エーテル組成物と他の物質とを併用してもよい。たとえば、本発明のエーテル組成物を含む潤滑剤として使用する場合には、エーテル組成物をそのまま使用してもよい。
また、エーテル組成物には、化合物(A1)~(A4)以外のPFPE(以下、他のPFPE-XXという)を添加して使用してもよい。他のPFPE-XXを本発明のエーテル組成物に添加する場合の量は、本発明の特性を充分に発揮させために、エーテル組成物の全量(本発明にかかるエーテル組成物および上記他のPFPE-XX)に対して、10質量%以下とするのが好ましく、5質量%以下とするのがより好ましい。
また、他のPFPE-XXに、本発明のエーテル組成物を添加して使用してもよい。他のPFPE-XXの含有量は、エーテル組成物の全量に対して、50質量%以下が好ましく、30質量%以下がより好ましい。他のPFPE-XXに本発明のエーテル組成物を添加することにより、他のPFPE-XXの粘度調整および定着性を改善できる。
<末端にOH基を有する他のPFPE-XXの例>
FOMBLIN Z-DiOL、FOMBLIN Z-TetraOL、DEMNUM SA等。
<末端に紫外線吸収基を有する他のPFPE-XXの例>
FOMBLIN Z-DIAC、FOMBLIN Z-DEAL、FOMBLIN AM2001、FOMBLIN Z-DISOC、DEMNUM SH、MorescoA20H等。
さらに、他のPFPE-XXとしては、数平均分子量が1000~10000であるものを用いるのが好ましい。
溶媒としては、ペルフルオロアミン類(ペルフルオロトリプロピルアミン、ペルフルオロトリブチルアミン等。)、ペルフルオロアルカン類(バートレルXF(デュポン社製)等。)またはヒドロフルオロエーテル類(AE-3000(旭硝子社製)等。)が好ましく、オゾン破壊係数が低い点から、ヒドロフルオロエーテル類がより好ましい。
溶媒組成物中の本発明のエーテル組成物の濃度は、0.001~50質量%が好ましく、0.01~20質量%がより好ましい。
溶媒組成物を潤滑剤として用いる場合の他の成分としては、ラジカルスカベンジャー(たとえば、X1p(Dow Chemicals社製)等。)等が挙げられる。
溶媒組成物を表面改質剤として用いる場合の他の成分としては、カップリング剤(シラン系、エポキシ系、チタン系、アルミニウム系等。)等が挙げられる。カップリング剤は、基材と塗膜との接着性を向上させる。
金属イオン類(Na、K、Ca、Al等。)は、陰イオンと結合してルイス酸触媒を生成し、PFPEの分解反応を促進する場合がある。陰イオン類(F、Cl、NO2、NO3、PO4、SO4、C2O4等。)および水分は、基材の表面を腐食させる場合がある。よって、それぞれの含有量は次のとおりであるのが好ましい。Al、Mgはいずれも1000ppb以下、Na、Kはいずれも20000ppb以下、Caは10000ppb以下、Fe、Ni、Cu、Znはいずれも100ppb以下であるのが好ましい。Fは10000ppm以下、蟻酸、Cl、NO3、SO4、シュウ酸はいずれも5000ppb以下であるのが好ましい。溶媒組成物の含水率は、好ましくは2000ppm以下、特に好ましくは1000ppm以下が好ましい。低分子極性化合物(アルコール類;樹脂から溶出する可塑剤等。)は、基材と塗膜との接着性を低減させる場合がある。
基板としては、NiPメッキされた基板(アルミニウム、ガラス等。)上に、下地層、記録層、カーボン保護膜を順に有するものが挙げられる。
カーボン保護膜の厚さは、5.0nm以下が好ましく、カーボン保護膜の平均表面粗さ(Ra)は、2.0nm以下が好ましい。
吸着処理としては、加熱処理、赤外線照射処理、紫外線照射処理、プラズマ処理等が挙げられ、加熱処理または紫外線照射処理が好ましく、加熱処理がより好ましい。さらに、吸着処理後の磁気ディスクを、付着物の除去、余剰の潤滑剤の除去を目的に、フッ素系溶媒にて洗浄してもよい。
吸着処理後の潤滑剤塗膜の表面は、高い撥水性を有することから、たとえ高温、高湿度下に置いたとしても、水分の磁気ディスク内部への侵入が防止され、長期間にわたり高い潤滑性を維持できる。
該定着率は、65%以上がより好ましく、70%以上が特に好ましい。
また、本発明のエーテル組成物で処理した磁気ディスクの表面における水の接触角(室温)は、80°以上になりうる。該接触角は、85°以上が特に好ましい。
また、本発明のエーテル組成物は、界面活性剤としても有用である。たとえば、塗料の表面張力を低下させる添加剤、塗料のレベリング剤、研磨液のレベリング剤等として用いうる。塗料に添加する場合、本発明のエーテル組成物の添加量は、塗料に対して0.01~5質量%が好ましい。
テトラメチルシランをTMS、
CCl2FCClF2をR-113、
ジクロロペンタフルオロプロパンをR-225、
CClF2CClFCF2OCF2CClF2をCFE-419、
ヘキサフルオロイソプロピルアルコールをHFIP、
イソプロピルアルコールをIPAと略記する。
また、実施例における分析は、それぞれ室温(25℃)にて行った。
1H-NMR(300.4MHz)の基準物質としては、TMSを用いた。
19F-NMR(282.7MHz)の基準物質としては、CFCl3を用いた。
溶媒としては、特に記載しない限り、R-113を用いた。
組成物に含まれる化合物の組成比を、HPLC装置(島津製作所社製、Prominence)を用い、下記の条件にて測定した。具体的には、分析1サイクルにて、移動相中のHFIPの濃度を0%から100%に徐々に増加させ、組成物に含まれる化合物を、OH基の数の少ない化合物から順に分離し、質量比を分析した。
分析カラム:順相系シリカゲルカラム(ワイエムシー社製、SIL-gel)、
移動相:R-225(旭硝子社製、アサヒクリンAK-225G)およびHFIP、
移動相流速:1.0mL/分、
カラム温度:37℃、
検出器:蒸発光散乱検出器。
特開2001-208736号公報に記載の方法にしたがって、下記の条件にてGPCによりMnおよびMwを測定し、Mw/Mnを求めた。
移動相:R-225(旭硝子社製、アサヒクリンAK-225SECグレード1)とHFIPとの混合溶媒(R-255/HFIP=99/1体積比)、
分析カラム:PLgel MIXED-Eカラム(ポリマーラボラトリーズ社製)を2本直列に連結したもの、
分子量測定用標準試料:Mw/Mnが1.1未満であり、分子量が2000~10000のペルフルオロポリエーテルの4種およびMw/Mnが1.1以上であり、分子量が1300のペルフルオロポリエーテルの1種、
移動相流速:1.0mL/分、
カラム温度:37℃、
検出器:蒸発光散乱検出器。
潤滑剤塗膜の表面における接触角は、接触角計(Face社製、CA-X)を用いて測定した。潤滑剤塗膜の表面に、約2μLの水滴またはヘキサデカンを5滴置き、接触角を測定し、5つの値の平均値を求めた。
潤滑剤塗膜の表面の摩擦係数は、摩擦測定器(Heidon社製、Tribogear)を用いて測定した。接触子としてはφ10mmのSUS球を用い、荷重2g、回転数25rpmにて測定した。
摩擦係数測定試験後の接触子表面を光学顕微鏡で観察した。接触部4箇所を確認し、潤滑剤付着の有無を確認し、つぎの基準で評価した。○は、付着が認められない;△は、1~3箇所に付着がある;×は、4箇所に付着がある。
各画分の1.0gについて、灰化-誘導結合プラズマ質量分析法により金属イオンの含有量を測定した。
各画分の1.0gおよび超純水の30gを、あらかじめ希水酸化ナトリウム水溶液で洗浄したポリテトラフルオロエチレン製のボトルに投入し、24時間攪拌して調製した試料について、水抽出-イオンクロマトグラフィにより陰イオンの含有量を測定した。
各画分の含水率を、カールフィッシャー電量滴定法にて測定した。
国際公開第2005/068534号の実施例の例11に記載の方法において、ポリオキシエチレングリセロールエーテル(日本油脂社製、ユニオックスG1200)を、ジグリセリン開始ポリオキシエチレングリセロールエーテル(坂本薬品工業社製、SC-E1500)に変更した以外は、同様に反応を実施した。ジグリセリン開始ポリオキシエチレングリセロールエーテルに、FCOCF(CF3)OCF2CF(CF3)O(CF2)3Fを反応させ、室温で液体の化合物(B-1)を得た。NMR分析の結果、化合物(B-1)の(h+i+j+k)の平均値は37.0であり、Rfは-CF(CF3)OCF2CF(CF3)OCF2CF2CF3であり、Mnは2600であり、Mw/Mnは1.15であった。
19F-NMR(溶媒:CDCl3)δ(ppm):-76.0~-81.0,-81.0~-82.0,-82.0~-82.5,-82.5~-85.0,-128.0~-129.2,-131.1,-144.7。
国際公開第2005/068534号の実施例の例2-1に記載の方法において、R-113をCFE-419に変更し、液相に吹き込むガスに含まれるフッ素ガス濃度を20体積%から、10体積%に変更した以外は同様に化合物(B-1)の液相フッ素化反応を行った。生成物は、化合物(C-1)を主成分とし、化合物(B-1)の水素原子の99.9モル%以上がフッ素原子に置換された組成物(c-2)であった。式(C-1)のRfは-CF(CF3)OCF2CF(CF3)OCF2CF2CF3である。
組成物(c-2)において測定したNMRスペクトルは以下のとおりである。
19F-NMR δ(ppm):-55.8,-77.5~-86.0,-88.2~-92.0,-120.0~-139.0,-142.0~-146.0。
国際公開第2005/068534号の実施例の例3に記載の方法にしたがって、組成物(c-2)においてエステル分解反応を行い、化合物(D-1)を主成分とする組成物(d-2)を得た。
〔例4-1〕
国際公開第2005/068534号の実施例の例4-1に記載の方法にしたがって、組成物(d-2)とエタノールを反応させることによるエステル化反応を行った。化合物(E-1)を主成分とする組成物(e-2)を得た。該組成物(e-2)を例5の反応に用いた。
国際公開第2005/068534号の実施例の例4-2に記載の方法にしたがって、組成物(d-2)とエタノールを反応させることによるエステル交換反応を行い、化合物(E-1)を主成分とする組成物を得た。
国際公開第2005/068534号の実施例の例5に記載の方法において、組成物(e-2)の還元反応を行い、化合物(A11-1)を主成分とする組成物(a-2)を得た。
NMR分析およびHPLC分析からは、得られた組成物(a-2)中には、
3つのOH基末端と1つのCF3基末端を有する化合物(A21-1a)および化合物(A21-1b)から選ばれる少なくとも1種(以下、化合物(A21-1)と記す。)、
2つのOH基末端と2つのCF3基末端を有する化合物(A31-1a)、化合物(A31-1b)、化合物(A31-1c)および化合物(A31-1d)から選ばれる少なくとも1種(以下、化合物(A31-1)と記す。)、および
1つのOH基末端と3つのCF3基末端を有する化合物(A41-1a)および化合物(A41-1b)から選ばれる少なくとも1種(以下、化合物(A41-1)と記す。)が含まれていることが示された。
1H-NMR δ(ppm):3.94。
19F-NMR δ(ppm):-54.0,-80.1,-88.2~-90.5,-135.0~-139.0。
組成物(a-2)を下記のカラムクロマトグラフィにより精製した。
粒状シリカゲル(エスアイテック社製、MS-Gel D75-120A)をR-225で希釈したものを、直径150mm、長さ500mmのカラムに充填し、高さ100mmのシリカゲル充填相を形成した。
組成物(a-2)の300gをシリカゲル充填相に投入した後、抽出溶媒(R-225とIPAとの混合溶媒)を用い、抽出溶媒中のIPAの濃度を徐々に高めながら分画操作を行い、画分(p1-1)~(p1-5)を得た。抽出溶媒の量、抽出溶媒中のIPA濃度および画分の量を表1に示す。このうち画分(p1-4)を用いて、さらに精製を行うことにした。
画分(p1-4)を下記の超臨界抽出法により精製した。
入口および出口を有する肉厚のステンレス容器(内径φ33mm×深さ45mm)、超臨界二酸化炭素流体送液ポンプ(日本分光社製、SCF-201)、自動圧力調整弁(日本分光社製、880-81)、通常のカラムクロマトグラフィに用いるカラムオーブンを備えた装置を用意した。
画分(p1-4)の70gを容器内に注入し、超臨界二酸化炭素を液化二酸化炭素換算流量5.0cc/分で流した。容器内の温度を60℃に固定し、容器内の圧力を時間経過で変化させて、各圧力段階で分画し、画分(p2-1)~(p2-7)を得た。容器内の圧力、該圧力の保持時間および画分の量を表3に示す。
カーボンをターゲットとして用い、Ar雰囲気中で高周波マグネトロンスパッタにより、磁気ディスク用ガラスブランクス(旭硝子社製、2.5”ブランクス)にDLCを蒸着させてカーボン保護膜を製膜し、模擬ディスクを作製した。Arのガス圧は、0.003Torrであり、スパッタ中の投入電力密度は、ターゲット面積あたり3W/cm2であった。カーボン保護膜の厚さは、30nmとした。カーボン保護膜の表面の水接触角は、40゜であった。
該溶媒組成物に模擬ディスクを30秒間浸漬し、6mm/秒の一定速度で引き上げた。溶媒組成物が塗布された模擬ディスクを恒温炉にて100℃で1時間熱処理し、潤滑剤塗膜を形成した。潤滑剤塗膜が形成されたディスクをバートレルXFに30秒浸漬して洗浄した。洗浄前後において潤滑剤塗膜の厚さをエリプソメータにて測定し、定着率を求めた。また、潤滑剤塗膜の表面の接触角、摩擦係数を測定し、付着性を評価した。結果を表5に示す。
例7で得た画分(p2-6)、および化合物(F)(ソルベイ社製、FOMBLIN Z-TetraOL、Mn:3000、Mw/Mn=1.23)に変更した以外は、例8と同様にして模擬ディスクの表面に潤滑剤塗膜を形成し、例8と同様にして評価した。結果を表5に示す。該化合物のCF3比率は0である。
HOCH2CH(OH)CH2OCH2CF2O(CF2O)i(CF2CF2O)ii-CF2CH2OCH2CH(OH)CH2OH ・・・(F)。
ただし、i/ii=1.0である。
画分(p2-1)、画分(p2-3)、画分(p2-4)および画分(p2-5)について、金属イオン分析、陰イオン分析および含水率測定を行った。結果を表6に示す。
なお、2008年1月24日に出願された日本特許出願2008-013638号及び2008年7月30日に出願された日本特許出願2008-196371号の明細書、特許請求の範囲及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (11)
- 下式(X)で表される基の1~4個と下式(Z)で表される基の0~3個とを有し、かつ式(X)で表される基と式(Z)で表される基の総数が4個であるエーテル化合物(A)の2種以上を含む、ことを特徴とするエーテル組成物。
HO-(CH2CH2O)a・(CH2CH(OH)CH2O)b-Q- ・・・(X)、
CF3(CF2)sO(CF2CF2O)g- ・・・(Z)。
ただし、上記式(X)および式(Z)において、aは、0~100の整数であり、bは、0または1であり、sは、0~19の整数であり、gは、3~200の整数であり、Qは、ポリフルオロ化されたポリメチレン基、またはエーテル性酸素原子を有するポリフルオロ化されたポリメチレン基である。 - 前記エーテル化合物(A)の2種以上が、下式(A1)で表される化合物、下式(A2)で表される化合物、下式(A3)で表される化合物および下式(A4)で表される化合物からなる群より選ばれる2種以上である、請求項1に記載のエーテル組成物。
(X-)4Y ・・・(A1)
(X-)3Y-Z ・・・(A2)、
(X-)2Y(-Z)2 ・・・(A3)、
X-Y(-Z)3 ・・・(A4)。
ただし、
Xは、前記式(X)で表される基であり、
Yは、ペルフルオロアルカン-テトライル基、または該基の炭素-炭素原子間にエーテル性酸素原子が挿入された基であり、かつ式(Z)で表される基の構造を有さない基であり、
Zは、前記式(Z)で表される基である。 - Xが、下式(X1)で表される基、下式(X2)で表される基、下式(X3)で表される基、および下式(X4)で表される基からなる群より選ばれる基である、請求項1または2に記載のエーテル組成物。
HOCH2CF2O(CF2CF2O)d- ・・・(X1)、
HOCH2CH(OH)CH2OCH2CF2O(CF2CF2O)d- ・・・(X2)、
HOCH2CH2CF2O(CF2CF2O)d- ・・・(X3)、
HOCH2CH2OCH2CF2O(CF2CF2O)d- ・・・(X4)。
ただし、dは、1~200の整数である。 - Yが、CF3基を有さない基である、請求項2または3に記載のエーテル組成物。
- 式(A1)で表される化合物が、下式(A1-1)で表される化合物であり、
式(A2)で表される化合物が、下式(A2-1a)で表される化合物、下式(A2-1b)で表わされる化合物、または、下式(A2-1a)で表される化合物と下式(A2-1b)で表わされる化合物の組み合わせであり、
式(A3)で表される化合物が、下式(A3-1a)で表される化合物、下式(A3-1b)で表される化合物、下式(A3-1c)で表される化合物、および下式(A3-1d)で表される化合物からなる群より選ばれる化合物であり、
式(A4)で表される化合物が、下式(A4-1a)で表される化合物、下式(A4-1b)で表される化合物、または、下式(A4-1a)で表される化合物と下式(A4-1b)で表される化合物の組み合わせである、請求項2~5のいずれかに記載のエーテル組成物。
- エーテル組成物中に存在する式(Z)で表される基が有するCF3基の総モル量および式(X)で表される基が有するOH基の総モル量の合計量に対する式(Z)で表される基が有するCF3基の総モル量の割合(CF3/(OH+CF3))が、0.01~0.5である、請求項1~6のいずれかに記載のエーテル組成物。
- エーテル化合物(A)が、-OCF2O-構造を有さない、請求項1~7のいずれかに記載のエーテル組成物。
- エーテル化合物(A)の総量が、エーテル組成物に対して95質量%以上である、請求項1~8のいずれかに記載のエーテル組成物。
- エーテル組成物の数平均分子量が、500~1000000であり、かつエーテル組成物の分子量分布が、1.01~1.5である、請求項1~9のいずれかに記載のエーテル組成物。
- 請求項1~10のいずれかに記載のエーテル組成物を含む潤滑剤。
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CN2009801031856A CN101925655B (zh) | 2008-01-24 | 2009-01-22 | 醚组合物 |
JP2009550559A JP5499710B2 (ja) | 2008-01-24 | 2009-01-22 | エーテル組成物 |
EP09704557.9A EP2236559B1 (en) | 2008-01-24 | 2009-01-22 | Ether composition |
US12/793,212 US8410034B2 (en) | 2008-01-24 | 2010-06-03 | Ether composition |
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US (1) | US8410034B2 (ja) |
EP (1) | EP2236559B1 (ja) |
JP (1) | JP5499710B2 (ja) |
KR (1) | KR20100103577A (ja) |
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US20100240559A1 (en) * | 2008-01-24 | 2010-09-23 | Asahi Glass Company, Limited | Ether composition |
US20100240560A1 (en) * | 2007-12-19 | 2010-09-23 | Asahi Glass Company, Limited | Ether composition |
WO2011007782A1 (ja) * | 2009-07-15 | 2011-01-20 | 旭硝子株式会社 | エーテル組成物および潤滑剤 |
WO2011065312A1 (ja) * | 2009-11-26 | 2011-06-03 | 旭硝子株式会社 | エーテル化合物、これを含む潤滑剤および潤滑剤用組成物 |
US20110256424A1 (en) * | 2010-04-15 | 2011-10-20 | Hitachi Global Storage Technologies Netherlands B.V. | Perfluoropolyether lubricant and systems comprising same |
US8053538B2 (en) * | 2005-07-27 | 2011-11-08 | Asahi Glass Company, Limited | Ether composition and solution composition |
JPWO2014126107A1 (ja) * | 2013-02-13 | 2017-02-02 | 旭硝子株式会社 | 含フッ素エーテル組成物、表面改質剤、界面活性剤、液状組成物、物品 |
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CN105518054B (zh) * | 2013-08-23 | 2018-02-16 | 大金工业株式会社 | 含全氟(聚)醚基的羧酸化合物的分离方法 |
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US20100240559A1 (en) | 2010-09-23 |
US8410034B2 (en) | 2013-04-02 |
EP2236559A1 (en) | 2010-10-06 |
CN101925655A (zh) | 2010-12-22 |
EP2236559A4 (en) | 2013-09-04 |
CN101925655B (zh) | 2012-10-17 |
JPWO2009093665A1 (ja) | 2011-05-26 |
TW200940596A (en) | 2009-10-01 |
JP5499710B2 (ja) | 2014-05-21 |
KR20100103577A (ko) | 2010-09-27 |
EP2236559B1 (en) | 2016-03-30 |
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