WO2017217442A1 - 転写パターンを有する被転写物の製造方法 - Google Patents
転写パターンを有する被転写物の製造方法 Download PDFInfo
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- WO2017217442A1 WO2017217442A1 PCT/JP2017/021901 JP2017021901W WO2017217442A1 WO 2017217442 A1 WO2017217442 A1 WO 2017217442A1 JP 2017021901 W JP2017021901 W JP 2017021901W WO 2017217442 A1 WO2017217442 A1 WO 2017217442A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
- B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
- B29C59/04—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing using rollers or endless belts
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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
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0822—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using IR radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
- B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
- B29C35/0805—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
- B29C2035/0827—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using UV radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2071/00—Use of polyethers, e.g. PEEK, i.e. polyether-etherketone or PEK, i.e. polyetherketone or derivatives thereof, as moulding material
Definitions
- the present invention relates to a method for producing a transfer object having a transfer pattern.
- the mold release agent is used for the purpose of improving the releasability between a mold (mold) and a polymer resin to be processed in general machining.
- a release agent silicone oil and fluororesin solution are conventionally known.
- silicon oil or fluororesin solution is used as a mold release agent for imprint molds (molds for imprint processing)
- the groove width and depth dimensions of the concave portions of the fine pattern of the mold are micron. Since it is a unit, it enters into the groove portion of the recess, and there is a problem that a normal pattern cannot be transferred by pressing.
- Patent Document 1 an imprint mold formed by coating with a perfluoropolyether having a functional group that chemically reacts with a mold material.
- the present invention has been made in view of the above situation, and is a method for manufacturing a transfer object having a transfer pattern.
- the transfer object is peeled off from a substrate or adhered to a mold even if transfer is repeatedly performed. It aims at providing the manufacturing method which is hard to carry out.
- the present invention includes a step (1) of applying a composition containing a fluoropolyether to the mold release layer of the mold having a concavo-convex pattern on which a mold release layer is formed, and pressing the mold against a transfer object.
- the transferred material preferably contains an ultraviolet curable resin.
- the mold is pressed against the transfer object and the transfer object is irradiated with ultraviolet rays.
- composition preferably further contains a solvent.
- the transferred object is hardly peeled off from the substrate or attached to the mold, so that the transferred object having a transfer pattern can be obtained with high productivity and at low cost. Can be manufactured.
- the production method of the present invention includes steps (1) to (3). Each step will be described below.
- a composition containing a fluoropolyether is applied to the mold release layer of the mold having a concavo-convex pattern on which the mold release layer is formed.
- the concavo-convex pattern may be a fine concavo-convex pattern in nanometer units. That is, the production method of the present invention can produce a nanoimprint film.
- the material of the mold can be appropriately selected according to the purpose and necessity.
- a metal resin, a metal oxide, a polymer resin such as quartz or silicone, a semiconductor, an insulator, or a composite thereof. can be mentioned.
- the shape of the mold is not particularly limited and may be a roll shape or a flat plate shape, but is preferably a roll shape because continuous transfer is possible.
- the mold in which the release layer is formed preferably has a water contact angle of 80 ° or more, more preferably 100 ° or more, and preferably 180 ° or less.
- the water contact angle can be measured with a contact angle meter.
- the water contact angle is a water contact angle that the mold has before application of the composition.
- the release layer preferably contains a compound having a hydrolyzable group because the adhesiveness between the release layer and the mold is excellent.
- the “hydrolyzable group” as used herein means a group capable of leaving from the main skeleton of a compound by a hydrolysis reaction. Examples of the hydrolyzable group include —OR, —OCOR, —O—N ⁇ CR 2 , —NR 2 , —NHR, halogen (in these formulas, R is a substituted or unsubstituted carbon atom having 1 to 4 carbon atoms). And the like, and —OR (that is, an alkoxy group) is preferable.
- R examples include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group.
- an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
- R 1 represents a hydrolyzable group
- R 2 represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms
- n1 is an integer of 1 to 3. It is preferable that the compound which has group represented by these is included.
- the release layer contains a perfluoro (poly) ether group-containing silane compound because it is further excellent in releasability and is excellent in adhesion between the release layer and the mold.
- the release layer has the following general formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2):
- PFPE has the formula: -(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d-
- a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d
- R 1 represents, independently at each occurrence, a hydrolyzable group;
- R 2 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
- R 11 independently represents a hydrogen atom or a halogen atom at each occurrence;
- R 12 independently represents a hydrogen atom or a
- perfluoro (poly) ether group-containing silane compounds represented by the above formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) explain.
- PFPE is — (OC 4 F 8 ) a — (OC 3 F 6 ) b — (OC 2 F 4 ) c — (OCF 2 ) d — and corresponds to a perfluoro (poly) ether group To do.
- a, b, c and d are each independently 0 or an integer of 1 or more, and the sum of a, b, c and d is at least 1.
- a, b, c and d are each independently an integer of 0 to 200, for example, an integer of 1 to 200, more preferably an integer of 0 to 100.
- the sum of a, b, c and d is 5 or more, more preferably 10 or more, for example 10 or more and 100 or less.
- the order of presence of each repeating unit in parentheses with the suffix a, b, c or d is arbitrary in the formula.
- — (OC 4 F 8 ) — represents — (OCF 2 CF 2 CF 2 CF 2 ) —, — (OCF (CF 3 ) CF 2 CF 2 ) —, — (OCF 2 CF (CF 3 ) CF 2 )-,-(OCF 2 CF 2 CF (CF 3 ))-,-(OC (CF 3 ) 2 CF 2 )-,-(OCF 2 C (CF 3 ) 2 )-,-(OCF (CF 3 ) CF (CF 3 ))-,-(OCF (C 2 F 5 ) CF 2 )-and-(OCF 2 CF (C 2 F 5 ))-may be used, but preferably — (OCF 2 CF 2 CF 2 CF 2 ) —.
- -(OC 3 F 6 )- is any of-(OCF 2 CF 2 CF 2 )-,-(OCF (CF 3 ) CF 2 )-and-(OCF 2 CF (CF 3 ))- Preferably, it is — (OCF 2 CF 2 CF 2 ) —.
- — (OC 2 F 4 ) — may be any of — (OCF 2 CF 2 ) — and — (OCF (CF 3 )) —, preferably — (OCF 2 CF 2 ) —. is there.
- PFPE is — (OC 3 F 6 ) b — (wherein b is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200),
- — (OCF 2 CF 2 CF 2 ) b — (wherein b is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200) or — (OCF (CF 3 ) CF 2 ) b — (wherein b is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200), more preferably — (OCF 2 CF 2 CF 2 ) b- (wherein b is an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200).
- PFPE has the following structure:-(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d- (wherein a and b are each independently And c and d are each independently an integer of 1 to 200, preferably 5 to 200, more preferably 10 to 200, and the subscripts a, b, c Or the order of presence of each repeating unit in parentheses with d attached is arbitrary in the formula), preferably — (OCF 2 CF 2 CF 2 CF 2 ) a — (OCF 2 CF 2 CF 2 ) b- (OCF 2 CF 2 ) c- (OCF 2 ) d- .
- PFPE is — (OC 2 F 4 ) c — (OCF 2 ) d — (wherein c and d are each independently 1 or more and 200 or less, preferably 5 or more and 200 or less, more preferably Is an integer of 10 or more and 200 or less, and the order of presence of each repeating unit in parentheses with the subscript c or d is arbitrary in the formula).
- PFPE is a group represented by — (OC 2 F 4 —R 8 ) f —.
- R 8 is a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 , or a combination of 2 or 3 groups independently selected from these groups is there.
- the combination of 2 or 3 groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited.
- OC 2 F is an integer of 2 to 100, preferably an integer of 2 to 50.
- OC 2 F 4 , OC 3 F 6 and OC 4 F 8 may be either linear or branched, preferably linear.
- the PFPE is preferably — (OC 2 F 4 —OC 3 F 6 ) f — or — (OC 2 F 4 —OC 4 F 8 ) f —.
- Rf represents an alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms.
- alkyl group having 1 to 16 carbon atoms in the alkyl group having 1 to 16 carbon atoms which may be substituted with one or more fluorine atoms may be linear or branched. Preferably, it is a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 3 carbon atoms, and more preferably a linear alkyl group having 1 to 3 carbon atoms.
- Rf is preferably an alkyl group having 1 to 16 carbon atoms substituted by one or more fluorine atoms, more preferably a CF 2 H—C 1-15 fluoroalkylene group, and still more preferably Is a perfluoroalkyl group having 1 to 16 carbon atoms.
- the perfluoroalkyl group having 1 to 16 carbon atoms may be linear or branched, and preferably has 1 to 6 carbon atoms, particularly 1 to 6 carbon atoms. 3 perfluoroalkyl group, more preferably a linear perfluoroalkyl group having 1 to 3 carbon atoms, specifically —CF 3 , —CF 2 CF 3 , or —CF 2 CF 2 CF 3 . .
- R 1 is independently at each occurrence, represents a hydrolyzable group.
- each R 2 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
- hydrolyzable group as used herein means a group capable of leaving from the main skeleton of a compound by a hydrolysis reaction.
- hydrolyzable group examples include —OR, —OCOR, —O—N ⁇ CR 2 , —NR 2 , —NHR, halogen (in these formulas, R is a substituted or unsubstituted carbon atom having 1 to 4 carbon atoms). And the like, and —OR (that is, an alkoxy group) is preferable.
- R examples include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group.
- an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
- R 11 independently represents a hydrogen atom or a halogen atom at each occurrence.
- the halogen atom is preferably an iodine atom, a chlorine atom or a fluorine atom, more preferably a fluorine atom.
- R 12 each independently represents a hydrogen atom or a lower alkyl group.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
- n1 is an integer of 0 to 3, preferably 1 to 3, more preferably 3, independently for each (-SiR 1 n1 R 2 3-n1 ) unit. However, in the formula, all n1 are not 0 at the same time. In other words, at least one R 1 is present in the formula.
- each X 1 independently represents a single bond or a divalent to 10-valent organic group.
- the X 1 is a perfluoropolyether part (ie, Rf-PFPE part or -PFPE-part) mainly providing water repellency and surface slipperiness in the compounds represented by the formulas (A1) and (A2).
- a silane moiety that is, a group parenthesized with ⁇ that provides the binding ability to the base material. Therefore, X 1 may be any organic group as long as the compounds represented by formulas (A1) and (A2) can exist stably.
- ⁇ is an integer of 1 to 9
- ⁇ ′ is an integer of 1 to 9.
- These ⁇ and ⁇ ′ can vary depending on the valence of X 1 .
- the sum of ⁇ and ⁇ ′ is the same as the valence of X 1 .
- X 1 is a 10-valent organic group
- the sum of ⁇ and ⁇ ′ is 10, for example, ⁇ is 9 and ⁇ ′ is 1, ⁇ is 5 and ⁇ ′ is 5, or ⁇ is 1 and ⁇ 'Can be nine.
- ⁇ and ⁇ ′ are 1.
- alpha is a value obtained by subtracting 1 from the valence of X 1.
- X 1 is preferably 2 to 7 valent, more preferably 2 to 4 valent, and still more preferably a divalent organic group.
- X 1 is a divalent to tetravalent organic group
- ⁇ is 1 to 3
- ⁇ ′ is 1.
- X 1 is a divalent organic group
- ⁇ is 1
- ⁇ ′ is 1.
- the formulas (A1) and (A2) are represented by the following formulas (A1 ′) and (A2 ′).
- Examples of X 1 are not particularly limited, but for example, the following formula: -(R 31 ) p ' -(X a ) q'- [Where: R 31 represents a single bond, — (CH 2 ) s ′ — or o-, m- or p-phenylene group, preferably — (CH 2 ) s ′ — s ′ is an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2.
- X a represents-(X b ) l ' - X b is independently at each occurrence —O—, —S—, o—, m- or p-phenylene, —C (O) O—, —Si (R 33 ) 2 —, — ( Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 —, —CONR 34 —, —O—CONR 34 —, —NR 34 — and — (CH 2 ) n ′ —
- R 33 each independently represents a phenyl group, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a phenyl group or a C 1-6 alkyl group, and more preferably a methyl group.
- R 34 each independently represents a hydrogen atom, a phenyl group or a C 1-6 alkyl group (preferably a methyl group) at each occurrence;
- m ′ is independently an integer of 1 to 100, preferably an integer of 1 to 20, at each occurrence,
- n ′ is independently an integer of 1 to 20, preferably an integer of 1 to 6, more preferably an integer of 1 to 3, at each occurrence.
- R 31 and X a are one or more selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group It may be substituted with a substituent.
- X 1 is — (R 31 ) p ′ — (X a ) q ′ —R 32 —.
- R 32 represents a single bond, — (CH 2 ) t ′ — or o-, m- or p-phenylene group, and preferably — (CH 2 ) t ′ —.
- t ′ is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably an integer of 2 to 3.
- R 32 (typically a hydrogen atom of R 32 ) is substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group and a C 1-3 fluoroalkyl group. It may be.
- X 1 is A C 1-20 alkylene group, -R 31 -X c -R 32- , or -X d -R 32- [Wherein, R 31 and R 32 are as defined above. ] It can be.
- said X 1 is A C 1-20 alkylene group, -(CH 2 ) s' -X c- , -(CH 2 ) s ' -X c- (CH 2 ) t'- -X d- , or -X d- (CH 2 ) t ' - [Wherein, s ′ and t ′ are as defined above]. ] It is.
- X c is -O-, -S-, -C (O) O-, -CONR 34 -, -O-CONR 34 -, -Si (R 33 ) 2- , -(Si (R 33 ) 2 O) m ' -Si (R 33 ) 2- , —O— (CH 2 ) u ′ — (Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 —, —O— (CH 2 ) u ′ —Si (R 33 ) 2 —O—Si (R 33 ) 2 —CH 2 CH 2 —Si (R 33 ) 2 —O—Si (R 33 ) 2 —, —O— (CH 2 ) u ′ —Si (OCH 3 ) 2 OSi (OCH 3 ) 2 —, —CONR 34 — (CH 2 ) u ′ — (Si (Si (OC
- X d is -S-, -C (O) O-, -CONR 34 -, —CONR 34 — (CH 2 ) u ′ — (Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 —, —CONR 34 — (CH 2 ) u ′ —N (R 34 ) —, or —CONR 34 — (o-, m- or p-phenylene) -Si (R 33 ) 2 — [Wherein each symbol is as defined above. ] Represents.
- X 1 is A C 1-20 alkylene group, — (CH 2 ) s ′ —X c — (CH 2 ) t ′ —, or —X d — (CH 2 ) t ′ — [Wherein each symbol is as defined above. ] It can be.
- said X 1 is A C 1-20 alkylene group, — (CH 2 ) s ′ —O— (CH 2 ) t ′ —, - (CH 2) s' - (Si (R 33) 2 O) m '-Si (R 33) 2 - (CH 2) t' -, — (CH 2 ) s ′ —O— (CH 2 ) u ′ — (Si (R 33 ) 2 O) m ′ —Si (R 33 ) 2 — (CH 2 ) t ′ —, or — (CH 2 ) s′— O— (CH 2 ) t ′ —Si (R 33 ) 2 — (CH 2 ) u ′ —Si (R 33 ) 2 — (C v H 2v ) —
- R 33 , m ′, s ′, t ′ and u ′ are as defined above, and v is
- — (C v H 2v ) — may be linear or branched.
- the X 1 group is substituted with one or more substituents selected from a fluorine atom, a C 1-3 alkyl group, and a C 1-3 fluoroalkyl group (preferably a C 1-3 perfluoroalkyl group). May be.
- examples of X 1 groups include the following groups:
- each R 41 independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group;
- D is —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 —, —CF 2 O (CH 2 ) 3 —, -(CH 2 ) 2- , -(CH 2 ) 3- , - (CH 2) 4 -, -CONH- (CH 2 ) 3- , -CON (CH 3 )-(CH 2 ) 3- , —CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl), and
- each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group.
- a group selected from E is — (CH 2 ) n — (n is an integer of 2 to 6)); D binds to PFPE of the molecular backbone, and E binds to the opposite group of PFPE.
- X 1 include, for example: —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 —, —CH 2 O (CH 2 ) 6 —, —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —, -CH 2 O (CH 2) 3 Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -, -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- , —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH
- X 1 is a group represented by the formula: — (R 16 ) x — (CFR 17 ) y — (CH 2 ) z —.
- x, y and z are each independently an integer of 0 to 10, the sum of x, y and z is 1 or more, and the order in which each repeating unit enclosed in parentheses is in the formula Is optional.
- R 16 is independently an oxygen atom, phenylene, carbazolylene, —NR 26 — (wherein R 26 represents a hydrogen atom or an organic group) or a divalent organic group at each occurrence. is there.
- R 16 is an oxygen atom or a divalent polar group.
- the “divalent polar group” is not particularly limited, but —C (O) —, —C ( ⁇ NR 27 ) —, and —C (O) NR 27 — (in these formulas, R 27 is Represents a hydrogen atom or a lower alkyl group).
- the “lower alkyl group” is, for example, an alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl, n-propyl, and these may be substituted with one or more fluorine atoms.
- R 17 is each independently a hydrogen atom, a fluorine atom or a lower fluoroalkyl group, preferably a fluorine atom, at each occurrence.
- the “lower fluoroalkyl group” is, for example, a fluoroalkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, A pentafluoroethyl group, more preferably a trifluoromethyl group.
- X 1 is preferably of the formula: — (O) x — (CF 2 ) y — (CH 2 ) z —, wherein x, y and z are as defined above
- x, y and z are as defined above
- the order in which each repeating unit is included is arbitrary in the formula).
- Examples of the group represented by the above formula: — (O) x — (CF 2 ) y — (CH 2 ) z — include, for example, — (O) x ′ — (CH 2 ) z ′′ —O — [(CH 2) z '''-O-] z "", and - (O) x' - ( CF 2) y "- (CH 2) z” -O - [(CH 2) z '''-O- Z ′′ ′′ (wherein x ′ is 0 or 1, y ′′, z ′′ and z ′ ′′ are each independently an integer of 1 to 10, and z ′′ ′′ is 0 or 1) These groups are bonded at the left end to the PFPE side.
- X 1 is —O—CFR 13 — (CF 2 ) e —.
- Each R 13 independently represents a fluorine atom or a lower fluoroalkyl group.
- the lower fluoroalkyl group is, for example, a fluoroalkyl group having 1 to 3 carbon atoms, preferably a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably a trifluoromethyl group, a pentafluoroethyl group, still more preferably a trifluoromethyl group. It is.
- Each e is independently 0 or 1.
- R 13 is a fluorine atom and e is 1.
- examples of X 1 groups include the following groups:
- Each R 41 is independently a hydrogen atom, a phenyl group, an alkyl group having 1 to 6 carbon atoms, or a C 1-6 alkoxy group, preferably a methyl group;
- any some of T are attached to the PFPE of the molecular backbone: —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 —, —CF 2 O (CH 2 ) 3 —, -(CH 2 ) 2- , -(CH 2 ) 3- , - (CH 2) 4 -, -CONH- (CH 2 ) 3- , -CON (CH 3 )-(CH 2 ) 3- , —CON (Ph) — (CH 2 ) 3 — (wherein Ph represents phenyl), or
- each R 42 independently represents a hydrogen atom, a C 1-6 alkyl group or a C 1-6 alkoxy group, preferably a methyl group or a methoxy group, more preferably a methyl group.
- T is a group opposite to PFPE of the molecular main chain (that is, a carbon atom in the formulas (A1), (A2), (D1) and (D2)), and a formula ( B1), (B2), (C1) and (C2) are bonded to Si atoms)-(CH 2 ) n " -(n" is an integer of 2 to 6).
- Each may independently be a methyl group, a phenyl group, a C 1-6 alkoxy group, or a radical scavenging group or an ultraviolet absorbing group.
- the radical scavenging group is not particularly limited as long as it can capture radicals generated by light irradiation.
- benzophenones benzotriazoles, benzoates, phenyl salicylates, crotonic acids, malonic esters, organoacrylates , Hindered amines, hindered phenols, or triazine residues.
- the ultraviolet absorbing group is not particularly limited as long as it can absorb ultraviolet rays.
- benzotriazoles, hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid or salicylic acid compounds, acrylates or alkoxycinnamates, oxamides examples include residues of oxanilides, benzoxazinones, and benzoxazoles.
- preferred radical scavenging groups or ultraviolet absorbing groups include Is mentioned.
- X 1 can be each independently a trivalent to 10 valent organic group.
- t is each independently an integer of 1 to 10. In a preferred embodiment, t is an integer from 1-6. In another preferred embodiment, t is an integer from 2 to 10, preferably an integer from 2 to 6.
- X 2 independently represents a single bond or a divalent organic group at each occurrence.
- X 2 is preferably an alkylene group having 1 to 20 carbon atoms, and more preferably — (CH 2 ) u — (wherein u is an integer of 0 to 2).
- Preferred compounds represented by formulas (A1) and (A2) are represented by the following formulas (A1 ′) and (A2 ′):
- Each PFPE is independently of the formula: -(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d-
- a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d
- R 1 represents, independently at each occurrence, a hydrolyzable group;
- R 2 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
- R 11 independently represents a hydrogen atom or a halogen atom at each occurrence;
- R 12 independently represents a hydrogen atom
- the compounds represented by the above formulas (A1) and (A2) are obtained by introducing, for example, —CH 2 CR 12 (X It can be obtained by reacting a vinyl monomer corresponding to 2- SiR 1 n1 R 2 3-n1 ) —.
- Rf, PFPE, R 1 , R 2 and n1 are the same as those described for the above formulas (A1) and (A2).
- X 5 each independently represents a single bond or a divalent to 10-valent organic group.
- the X 5 are the formula (B1) and in the compounds represented by (B2), mainly perfluoropolyether unit for providing water repellency and surface slipperiness, etc. (Rf-PFPE unit or -PFPE- parts) It is understood as a linker that connects a silane moiety (specifically, —SiR 1 n1 R 2 3-n1 ) that provides the binding ability to the substrate. Therefore, X 5 may be any organic group as long as the compounds represented by formulas (B1) and (B2) can exist stably.
- ⁇ is an integer of 1 to 9
- ⁇ ′ is an integer of 1 to 9.
- ⁇ and ⁇ ′ are determined according to the valence of X 3
- the sum of ⁇ and ⁇ ′ is the same as the valence of X 5 .
- X 5 is a 10-valent organic group
- the sum of ⁇ and ⁇ ′ is 10, for example, ⁇ is 9 and ⁇ ′ is 1, ⁇ is 5 and ⁇ ′ is 5, or ⁇ is 1 and ⁇ 'Can be nine.
- ⁇ and ⁇ ′ are 1.
- beta is a value obtained by subtracting 1 from the valence of the value of X 5.
- X 5 is preferably a divalent organic group having 2 to 7 valences, more preferably 2 to 4 valences, and even more preferably a divalent organic group.
- X 5 is a divalent to tetravalent organic group
- ⁇ is 1 to 3
- ⁇ ′ is 1.
- X 5 is a divalent organic group
- ⁇ is 1
- ⁇ ′ is 1.
- the formulas (B1) and (B2) are represented by the following formulas (B1 ′) and (B2 ′).
- Examples of X 5 are not particularly limited, and examples thereof include those similar to those described for X 1 .
- preferable specific X 5 is —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 —, —CH 2 O (CH 2 ) 6 —, —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —, -CH 2 O (CH 2) 3 Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -, -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- , —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2
- Preferred compounds represented by formulas (B1) and (B2) are represented by the following formulas (B1 ′) and (B2 ′):
- Each PFPE is independently of the formula: -(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d-
- a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d
- R 1 represents, independently at each occurrence, a hydrolyzable group;
- R 2 independently represents a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence;
- n1 is an integer from 1 to 3, preferably 3;
- X 5 is —CH 2 O (CH 2 ) 2 —
- the compounds represented by the above formulas (B1) and (B2) can be produced by a known method, for example, the method described in Patent Document 1 or an improved method thereof.
- the compounds represented by the formulas (B1) and (B2) are represented by the following formulas (B1-4) or (B2-4):
- Each PFPE is independently of the formula: -(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d-
- a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d
- Each X 5 ′ independently represents a single bond or a divalent to 10-valent organic group; each ⁇ is independently an integer from 1 to 9; each ⁇ ′ is independently an integer from 1 to 9; R 92 is a single bond or a divalent organic group.
- R 1 is each independently a halogen atom
- R 1 is each independently a hydrolyzable group at each occurrence
- R 2 is independently a hydrogen atom or an alkyl group having 1 to 22 carbon atoms at each occurrence, and the halogen atom is converted to R 1 or R 2 as necessary.
- PFPE, Rf, X 5 ′ , ⁇ , ⁇ ′ and R 92 are as defined above; n1 is an integer of 0 to 3. ] It can obtain as a compound represented by these.
- Rf and PFPE are the same as those described for the above formulas (A1) and (A2).
- X 7 each independently represents a single bond or a divalent to 10-valent organic group.
- the X 7 is a formula (C1) and in the compounds represented by (C2), mainly perfluoropolyether unit for providing water repellency and surface slipperiness, etc. (Rf-PFPE unit or -PFPE- parts) It is understood as a linker that connects a silane moiety (specifically, —SiR a k1 R b 11 R c m1 group) that provides the binding ability to the substrate. Therefore, X 7 may be any organic group as long as the compounds represented by formulas (C1) and (C2) can exist stably.
- ⁇ is an integer of 1 to 9
- ⁇ ′ is an integer of 1 to 9.
- ⁇ and ⁇ ′ are determined according to the valence of X 7
- the sum of ⁇ and ⁇ ′ is the same as the valence of X 7 .
- X 7 is a 10-valent organic group
- the sum of ⁇ and ⁇ ′ is 10, for example, ⁇ is 9 and ⁇ ′ is 1, ⁇ is 5 and ⁇ ′ is 5, or ⁇ is 1 and ⁇ .
- gamma is a value obtained by subtracting 1 from the valence of the values of X 7.
- X 7 is preferably a divalent organic group having 2 to 7 valences, more preferably 2 to 4 valences, and even more preferably a divalent organic group.
- X 7 is a divalent to tetravalent organic group, ⁇ is 1 to 3, and ⁇ ′ is 1.
- X 7 is a divalent organic group, ⁇ is 1 and ⁇ ′ is 1.
- the formulas (C1) and (C2) are represented by the following formulas (C1 ′) and (C2 ′).
- Examples of X 7 are not particularly limited, and examples thereof include those similar to those described for X 1 .
- preferable specific X 7 is —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 —, —CH 2 O (CH 2 ) 6 —, —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —, -CH 2 O (CH 2) 3 Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -, -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- , —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2
- R a independently represents —Z 1 —SiR 71 p1 R 72 q1 R 73 r1 at each occurrence.
- Z 1 represents an oxygen atom or a divalent organic group independently at each occurrence.
- Z 1 is preferably a divalent organic group, and forms a siloxane bond with the Si atom (Si atom to which R a is bonded) at the end of the molecular main chain in formula (C1) or formula (C2). Does not include what to do.
- Z 1 is preferably a C 1-6 alkylene group, — (CH 2 ) g —O— (CH 2 ) h — (wherein g is an integer of 1 to 6, and h is 1 to 6 is an integer of 6) or -phenylene- (CH 2 ) i- (wherein i is an integer of 0 to 6), and more preferably a C 1-3 alkylene group.
- These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
- R 71 represents R a ′ independently at each occurrence.
- R a ′ has the same meaning as R a .
- R a the maximum number of Si linked in a straight chain via the Z 1 group is 5. That is, in the above R a , when at least one R 71 is present, there are two or more Si atoms linearly linked through the Z 1 group in R a , but through the Z 1 group, The maximum number of Si atoms connected in a straight line is five.
- the phrase "through the Z 1 group in R a number of Si atoms linearly linked" is equal to the repetition number of -Z 1 -Si- being linearly linked in a R a Become.
- Z Z 1 group
- * means a site bonded to Si of the main chain, and ... means that a predetermined group other than ZSi is bonded, that is, all three bonds of Si atoms are ... In this case, it means the end point of ZSi repetition.
- the number on the right shoulder of Si means the number of appearances of Si connected in a straight line through the Z group counted from *.
- the chain in which ZSi repetition is completed in Si 2 has “the number of Si atoms linearly linked through Z 1 group in R a ”, and similarly, Si 3 , Si
- the chains in which the ZSi repetition is terminated with 4 and Si 5 have “number of Si atoms connected in a straight chain via the Z 1 group in R a ” being 3, 4 and 5, respectively.
- the number of Si atoms connected linearly via the Z 1 group in R a is 1 (left formula) or 2 (Right type).
- the number of Si atoms connected in a straight chain via the Z 1 group in R a is 1 or 2, preferably 1.
- R 72 represents a hydrolyzable group independently at each occurrence.
- hydrolyzable group as used herein means a group capable of undergoing a hydrolysis reaction.
- hydrolyzable groups include —OR, —OCOR, —O—N ⁇ C (R) 2 , —N (R) 2 , —NHR, halogen (wherein R is substituted or unsubstituted Represents an alkyl group having 1 to 4 carbon atoms), preferably —OR (alkoxy group).
- R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group.
- an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
- R 72 is —OR (wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group).
- R 73 independently represents a hydrogen atom or a lower alkyl group at each occurrence.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
- '(if R a' is absent, R a) terminal of R a in R a in the above q1 is preferably 2 or more, for example 2 or 3, more preferably 3.
- At least one of the terminal portions of R a is —Si (—Z 1 —SiR 72 q R 73 r ) 2 or —Si (—Z 1 —SiR 72 q R 73 r ) 3 , preferably — Si (—Z 1 —SiR 72 q R 73 r ) 3
- - the unit of (Z 1 -SiR 72 q R 73 r) is preferably (-Z 1 -SiR 72 3).
- the terminal portions of R a may be all —Si (—Z 1 —SiR 72 q R 73 r ) 3 , preferably —Si (—Z 1 —SiR 72 3 ) 3 .
- R b represents a hydrolyzable group independently at each occurrence.
- R b is preferably —OR, —OCOR, —O—N ⁇ C (R) 2 , —N (R) 2 , —NHR, halogen (in these formulas, R is a substituted or unsubstituted carbon) Represents an alkyl group of 1 to 4, and is preferably —OR.
- R includes an unsubstituted alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, and an isobutyl group; and a substituted alkyl group such as a chloromethyl group.
- R b is —OR (wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably a methyl group).
- R c independently represents a hydrogen atom or a lower alkyl group at each occurrence.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
- the compounds represented by the above formulas (C1) and (C2) have, for example, a perfluoropolyether derivative corresponding to the Rf-PFPE- moiety as a raw material, a hydroxyl group introduced at the terminal, and then an unsaturated bond at the terminal A group is introduced, the group having an unsaturated bond is reacted with a silyl derivative having a halogen atom, a hydroxyl group is further introduced into the terminal of the silyl group, and the introduced group having an unsaturated bond is reacted with the silyl derivative.
- Preferred compounds represented by the formulas (C1) and (C2) are represented by the following formulas (C1 ′′) and (C2 ′′):
- Each PFPE is independently of the formula: -(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d-
- a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d
- X 7 represents —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 — or —CH 2 O (CH 2 ) 6 —;
- R a independently represents at each occurrence —Z 1 —SiR 71 p1 R 72 q1 R 73
- the compounds represented by the above formulas (C1) and (C2) can be produced, for example, as follows.
- Each PFPE is independently of the formula: -(OC 4 F 8 ) a- (OC 3 F 6 ) b- (OC 2 F 4 ) c- (OCF 2 ) d-
- a, b, c and d are each independently an integer of 0 to 200, and the sum of a, b, c and d is at least 1, and the subscripts a, b, c or d
- Each X 7 ′ independently represents a single bond or a divalent to 10-valent organic group; each ⁇ is independently an integer from 1 to 9; each ⁇ ′ is independently an integer from 1 to 9; R 92 is a single bond or a divalent organic group.
- the obtained compound represented by the formula (C1-6) or (C2-6) is converted into HSiM 3 (wherein M is independently a halogen atom, R 72 or R 73 , and R 72 is Each independently at each occurrence represents a hydrolyzable group, and R 73 each independently at each occurrence represents a hydrogen atom or a lower alkyl group).
- the halogen atom is converted to R 72 or R 73 to give the formula (C1 ′ ′′) or (C2 ′ ′′):
- Rf, PFPE, R 72 , R 73 , R 92 , R 94 , R b , R c , ⁇ , ⁇ ′, X 7 ′ , k1, l1 and m1 are as defined above; q1 is independently an integer of 1 to 3 at each occurrence; r1 is an integer of 0 to 2 independently at each occurrence. ] Can be obtained.
- Rf and PFPE are the same as those described for the above formulas (A1) and (A2).
- X 9 each independently represents a single bond or a divalent to 10-valent organic group.
- the X 9 is a perfluoropolyether part (ie, Rf-PFPE part or -PFPE-part) mainly providing water repellency and surface slipperiness in the compounds represented by the formulas (D1) and (D2). It is understood that this is a linker that connects a moiety that provides a binding ability to the substrate (that is, a group that is bracketed with ⁇ ). Therefore, X 9 may be any organic group as long as the compounds represented by formulas (D1) and (D2) can exist stably.
- ⁇ is an integer of 1 to 9
- ⁇ ′ is an integer of 1 to 9.
- [delta] and [delta] ' may vary depending on the valence of X 9.
- the sum of [delta] and [delta] ' is the same as the valence of X 9.
- X 9 is a 10-valent organic group
- the sum of ⁇ and ⁇ ′ is 10, for example, ⁇ is 9 and ⁇ ′ is 1, ⁇ is 5 and ⁇ ′ is 5, or ⁇ is 1 and ⁇ .
- ⁇ can be nine.
- ⁇ and ⁇ ′ are 1.
- [delta] is a value obtained by subtracting 1 from the valence of X 9.
- X 9 is preferably divalent to 7-valent, more preferably 2- to 4-valent, and still more preferably a divalent organic group.
- X 9 is a divalent to tetravalent organic group, ⁇ is 1 to 3, and ⁇ ′ is 1.
- X 9 is a divalent organic group, ⁇ is 1 and ⁇ ′ is 1.
- the formulas (D1) and (D2) are represented by the following formulas (D1 ′) and (D2 ′).
- Examples of X 9 are not particularly limited, and examples thereof include those similar to those described with respect to X 1 .
- preferable specific X 9 is —CH 2 O (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 —, —CH 2 O (CH 2 ) 6 —, —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 OSi (CH 3 ) 2 (CH 2 ) 2 —, -CH 2 O (CH 2) 3 Si (CH 3) 2 OSi (CH 3) 2 OSi (CH 3) 2 (CH 2) 2 -, -CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 2 Si (CH 3 ) 2 (CH 2 ) 2- , —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2 ) 2 —, —CH 2 O (CH 2 ) 3 Si (CH 3 ) 2 O (Si (CH 3 ) 2 O) 3 Si (CH 3 ) 2 (CH 2
- R d independently represents —Z 2 —CR 81 p2 R 82 q2 R 83 r2 at each occurrence.
- Z 2 independently represents an oxygen atom or a divalent organic group at each occurrence.
- Z 2 is preferably a C 1-6 alkylene group, — (CH 2 ) g —O— (CH 2 ) h — (wherein g is an integer of 0 to 6, for example, an integer of 1 to 6). And h is an integer from 0 to 6, for example an integer from 1 to 6, or -phenylene- (CH 2 ) i- (where i is an integer from 0 to 6), and more A C 1-3 alkylene group is preferred. These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
- R 81 independently represents R d ′ at each occurrence.
- R d ′ has the same meaning as R d .
- R d the maximum number of C linked in a straight chain via the Z 2 group is 5. That is, the in R d, when R 81 is present at least one, but Si atoms linked in R d in Z 2 group via a linear there are two or more, via such Z 2 group The maximum number of C atoms connected in a straight line is five.
- the phrase "through the Z 2 group in R d number of C atoms linearly linked" is equal to the number of repetitions of -Z 2 -C- being linearly linked in a R d Become. This is the same as the description regarding R a in the formulas (C1) and (C2).
- the “number of C atoms connected in a straight chain via a Z 2 group in R d ” is 1 (left formula) or 2 (right formula) in all chains.
- the number of C atoms linked in a straight chain via a Z 2 group in R d is 1 or 2, preferably 1.
- R 82 represents —Y—SiR 85 n2 R 86 3-n2 .
- Y represents a divalent organic group independently at each occurrence.
- Y is a C 1-6 alkylene group, — (CH 2 ) g ′ —O— (CH 2 ) h ′ — (wherein g ′ is an integer from 0 to 6, for example from 1 to 6 Is an integer, h ′ is an integer from 0 to 6, for example, an integer from 1 to 6, or —phenylene- (CH 2 ) i ′ — (where i ′ is an integer from 0 to 6) ).
- These groups may be substituted with, for example, one or more substituents selected from a fluorine atom, a C 1-6 alkyl group, a C 2-6 alkenyl group, and a C 2-6 alkynyl group. .
- Y can be a C 1-6 alkylene group, —O— (CH 2 ) h ′ — or —phenylene- (CH 2 ) i ′ —.
- Y is a group as described above, light resistance, particularly ultraviolet light resistance can be further increased.
- R 85 represents a hydrolyzable group independently at each occurrence.
- hydrolyzable group as used herein means a group capable of undergoing a hydrolysis reaction.
- hydrolyzable groups include —OR, —OCOR, —O—N ⁇ C (R) 2 , —N (R) 2 , —NHR, halogen (wherein R is substituted or unsubstituted Represents an alkyl group having 1 to 4 carbon atoms), preferably —OR (alkoxy group).
- R include unsubstituted alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group and isobutyl group; substituted alkyl groups such as chloromethyl group.
- an alkyl group, particularly an unsubstituted alkyl group is preferable, and a methyl group or an ethyl group is more preferable.
- R 85 is —OR (wherein R represents a substituted or unsubstituted C 1-3 alkyl group, more preferably an ethyl group or a methyl group, particularly a methyl group).
- R 86 represents a hydrogen atom or a lower alkyl group independently at each occurrence.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
- n2 independently represents an integer of 1 to 3, preferably 2 or 3, more preferably 3, for each (-Y-SiR 85 n2 R 86 3-n2 ) unit.
- R 83 represents a hydrogen atom or a lower alkyl group independently at each occurrence.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
- p2 is independently an integer from 0 to 3 at each occurrence; q2 is independently an integer from 0 to 3 at each occurrence; and r2 is independently at each occurrence. And an integer from 0 to 3. However, the sum of p2, q2 and r2 is 3.
- '(if R d' is absent, R d) end of R d in R d in the above q2 is preferably 2 or more, for example 2 or 3, more preferably 3.
- At least one of the terminal ends of R d is —C (—Y—SiR 85 q2 R 86 r2 ) 2 or —C (—Y—SiR 85 q2 R 86 r2 ) 3 , preferably —C ( may be -Y-SiR 85 q2 R 86 r2 ) 3.
- (- Y-SiR 85 q2 R 86 r2) units is preferably (-Y-SiR 85 3).
- the terminal portions of R d may be all —C (—Y—SiR 85 q2 R 86 r2 ) 3 , preferably —C (—Y—SiR 85 3 ) 3 .
- R e independently represents —Y—SiR 85 n2 R 86 3-n2 at each occurrence.
- Y, R 85 , R 86 and n2 are as defined in R 82 above.
- R f independently represents a hydrogen atom or a lower alkyl group at each occurrence.
- the lower alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and still more preferably a methyl group.
- k2 is independently an integer of 0 to 3 at each occurrence; l2 is independently an integer of 0 to 3 at each occurrence; and m2 is independently at each occurrence. And an integer from 0 to 3. However, the sum of k2, l2, and m2 is 3.
- At least one k2 is 2 or 3, preferably 3.
- k2 is 2 or 3, preferably 3.
- l2 is 2 or 3, preferably 3.
- At least one q2 is 2 or 3, or at least one l2 is 2 or 3. That is, there are at least two —Y—SiR 85 n2 R 86 3-n2 groups in the formula.
- the perfluoro (poly) ether group-containing silane compound represented by the formula (D1) or the formula (D2) can be produced by combining known methods.
- the compound represented by the formula (D1 ′) in which X is divalent is not limited, but can be produced as follows.
- a group containing a double bond preferably a polyhydric alcohol represented by HO—X—C (YOH) 3 (wherein X and Y are each independently a divalent organic group)) Is allyl), and halogen (preferably bromo), and Hal—X—C (Y—O—R—CH ⁇ CH 2 ) 3 (where Hal is halogen, eg Br, R is A double bond-containing halide represented by a valent organic group such as an alkylene group.
- R PFPE —OH a perfluoropolyether group-containing alcohol represented by R PFPE —OH (wherein R PFPE is a perfluoropolyether group-containing group), and R PFPE ⁇ O—X—C (Y—O—R—CH ⁇ CH 2 ) 3 is obtained.
- the terminal —CH ⁇ CH 2 is then reacted with HSiCl 3 and alcohol or HSiR 85 3 to give R PFPE —O—X—C (Y—O—R—CH 2 —CH 2 —SiR 85 3 ) 3 Can be obtained.
- the perfluoro (poly) ether group-containing silane compounds represented by the above formulas (A1), (A2), (B1), (B2), (C1), (C2), (D1) and (D2) may have a number average molecular weight of 5 ⁇ 10 2 to 1 ⁇ 10 5 .
- the number average molecular weight is preferably 2,000 to 30,000, more preferably 3,000 to 10,000, and still more preferably 3,000 to 8,000.
- the “number average molecular weight” is measured by GPC (gel permeation chromatography) analysis.
- the number average molecular weight of the PFPE moiety in the perfluoro (poly) ether group-containing silane compound is not particularly limited, but is preferably 1,500 to 30,000, more preferably 2,500 to 10,000, More preferably, it may be 3,000 to 8,000.
- the method for forming the release layer a method of immersing the mold in a composition containing the hydrolyzable group-containing compound or the perfluoro (poly) ether group-containing silane compound and a solvent, vapor of the composition And a method of exposing the mold to vapor deposition, a method of printing the composition on the mold, a method of applying the composition to the mold using an inkjet, and the like. You may dry after the said immersion, the said vapor deposition, the said printing, and the said application
- the composition containing the fluoropolyether is applied to the release layer, but the application method is not particularly limited, and the release layer is applied to the composition containing the fluoropolyether.
- a method of immersing the mold on which is formed, a method of spraying a composition containing the fluoropolyether onto the release layer, and a method of depositing a composition containing the fluoropolyether on the release layer can be used.
- the fluoropolyether easily adheres to the transferred material during transfer. Therefore, when the transfer is repeated, it is preferable to supplement the fluoropolyether consumed by adhering to the transfer object.
- the region in contact with the transferred object is a part of the mold, and therefore the fluoropolyether is continuously or in an area not in contact with the transferred object. By applying intermittently, the fluoropolyether can be smoothly replenished.
- the fluoropolyether preferably does not have the hydrolyzable group described above. If the fluoropolyether does not have the hydrolyzable group, it does not chemically bond to the mold and the release layer, and adheres to the release layer or in the release layer. Soak up. Therefore, the mold release layer can be protected without impairing the mold release property of the mold release layer and without deforming the concavo-convex pattern. In addition, when the fine concavo-convex pattern is transferred, the perfluoropolyether compound is transferred onto the surface of the transfer object, thereby imparting water repellency, oil repellency, and antifouling properties.
- R 111- (R 112 O) m -R 113 R 111 and R 113 are independently F, an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, a fluorinated alkyl group having 1 to 16 carbon atoms, or a fluorinated group having 1 to 16 carbon atoms.
- R 114 is a single bond or a divalent organic group, X 111 is —NH 2 , —OH, —COOH, —CH ⁇ CH 2 , —OCH 2 CH ⁇ CH 2 , halogen; , Phosphoric acid, phosphoric acid ester, carboxylic acid ester, thiol, thioether, alkyl ether (which may be substituted with fluorine), aryl, aryl ether or amide), R 112 is a fluorinated alkylene group having 1 to 4 carbon atoms , M is an integer of 2 or more).
- the divalent organic group include an alkylene group, a fluorinated alkylene group, or a group having an oxygen atom bonded to the terminal thereof.
- the number of carbon atoms of the divalent organic group is not particularly limited, but may be 1 to 16, for example.
- R 111 and R 113 are independently F, an alkyl group having 1 to 3 carbon atoms, a fluorinated alkyl group having 1 to 3 carbon atoms, or —R 114 —X 111 (where R 114 and X 111 are as described above). F, a fully fluorinated alkyl group having 1 to 3 carbon atoms, or —R 114 —X 111 (R 114 and X 111 are as described above) is more preferable.
- n an integer of 300 or less is preferable, and an integer of 100 or less is more preferable.
- R 112 is preferably a fully fluorinated alkylene group having 1 to 4 carbon atoms.
- R 112 O— for example, Formula: — (CX 112 2 CF 2 CF 2 O) n111 (CF (CF 3 ) CF 2 O) n112 (CF 2 CF 2 O) n113 (CF 2 O) n114 (C 4 F 8 O) n115 ⁇ (N111, n112, n113, n114 and n115 are independently 0 or an integer of 1 or more, X 112 is H, F or Cl, and the order of the repeating units is arbitrary in a) those represented by, Formula:-(OC 2 F 4 -R 118 ) f- (R 118 is a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 , and f is an integer of 2 to 100).
- n111 to n115 are each preferably an integer of 0 to 200. n111 to n115 are preferably 1 or more in total, more preferably from 5 to 300, still more preferably from 10 to 200, and particularly preferably from 10 to 100.
- R 118 is a group selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 , or a combination of 2 or 3 groups independently selected from these groups.
- the combination of 2 or 3 groups independently selected from OC 2 F 4 , OC 3 F 6 and OC 4 F 8 is not particularly limited.
- OC 2 F is an integer of 2 to 100, preferably an integer of 2 to 50.
- OC 2 F 4 , OC 3 F 6 and OC 4 F 8 may be either linear or branched, preferably linear.
- the formula: — (OC 2 F 4 —R 118 ) f — preferably represents the formula: — (OC 2 F 4 —OC 3 F 6 ) f — or the formula: — (OC 2 F 4 —OC 4 F 8 ) f ⁇ .
- the fluoropolyether preferably has a weight average molecular weight of 500 to 100,000, more preferably 50,000 or less, still more preferably 10,000 or less, and particularly preferably 6,000 or less.
- the weight average molecular weight can be measured by gel permeation chromatography (GPC).
- fluoropolyether examples include demnum (manufactured by Daikin Industries), fomblin (manufactured by Solvay Specialty Polymers Japan), varielta (manufactured by NOK Kluber), and Krytox (manufactured by DuPont). Can be mentioned.
- the composition may contain only the fluoropolyether. However, since it has a low surface free energy and is easy to apply, the composition preferably contains a solvent (excluding the fluoropolyether), and a fluorine-based solvent (excluding the fluoropolyether). ) Is more preferable.
- the fluorine-based solvent include perfluorohexane, perfluoromethylcyclohexane, perfluoro-1,3-dimethylcyclohexane, dichloropentafluoropropane, hydrofluoroether (HFE), hexafluorometaxylene, Zeolora H (manufactured by Nippon Zeon). Etc.), and the above HFE is preferable.
- the amount of the fluoropolyether is preferably 10 to 0.0001% by mass based on the composition. It is more preferably 1 to 0.001% by mass, and still more preferably 0.1 to 0.001% by mass.
- the amount of the fluoropolyether is also preferably 0.01% by mass or more with respect to the composition. When the amount of the fluoropolyether is within the above range, the application is easy.
- the hydrofluoroether (HFE) is represented by Rf 21 —O—R 21 (Rf 21 is a fluorinated alkyl group having 1 to 10 carbon atoms, R 21 is a non-fluorinated alkyl group having 1 to 3 carbon atoms).
- the compound is preferably C 3 F 7 OCH 3 , C 4 F 9 OCH 3 , C 4 F 9 OC 2 H 5 , C 2 F 5 CF (OCH 3 ) C 3 F 7, and the like.
- step (2) the mold obtained in step (1) is pressed against an object to be transferred to transfer the uneven pattern.
- the mold can be pressed against the transfer object and the transfer object can be heated, or the transfer object can be irradiated with light to cure the transfer object.
- the manufacturing method may include a step of heating the transferred material after the step (3) or curing the transferred material by irradiating the transferred material with light. it can.
- the transferred object when the mold is pressed against the transferred object and the transferred object is irradiated with ultraviolet rays to cure the transferred object, the transferred object may be peeled off from the substrate or the transferred object. There was a problem that the transferred material adhered to the mold. However, since the manufacturing method includes the step (1), it is possible to avoid peeling and adhesion of the transfer object. Therefore, in the step (2), a manufacturing method in which the mold is pressed against the transfer object and the transfer object is irradiated with ultraviolet rays is also a preferred aspect of the present invention.
- the transfer object may be provided on a substrate.
- the material of the base material include silicon, synthetic resin, glass, metal, ceramic, and the like. However, since the material has flexibility and can press a roll-shaped mold, synthetic resin is preferable.
- the synthetic resin examples include cellulose resins such as triacetyl cellulose (TAC), polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymer, and ethylene-vinyl acetate copolymer (EVA), cyclic polyolefin, and modified polyolefin.
- TAC triacetyl cellulose
- EVA ethylene-vinyl acetate copolymer
- cyclic polyolefin cyclic polyolefin
- modified polyolefin modified polyolefin.
- Polyolefin polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polyimide, polyamideimide, polycarbonate, poly- (4-methylpentene-1), ionomer, acrylic resin, polymethyl methacrylate, acrylic-styrene copolymer (AS Resin), butadiene-styrene copolymer, ethylene-vinyl alcohol copolymer (EVOH), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polycyclohexane terephthalate Polyester such as PCT, polyether, polyetherketone (PEK), polyetheretherketone (PEEK), polyetherimide, polyacetal (POM), polyphenylene oxide, modified polyphenylene oxide, polyarylate, aromatic polyester (liquid crystal Polymer), polytetrafluoroethylene, polyvinylidene fluoride, other fluororesins, styrene, polyolefin
- the transferred material preferably includes a curable resin or a curable monomer, and more preferably includes the curable resin.
- the curable resin may be either a photocurable resin or a thermosetting resin, and is not particularly limited as long as it has heat resistance and strength, but a photocurable resin is preferable, and an ultraviolet curable resin is preferable. More preferred.
- curable resin examples include acrylic polymers, polycarbonate polymers, polyester polymers, polyamide polymers, polyimide polymers, polyethersulfone polymers, cyclic polyolefin polymers, fluorine-containing polyolefin polymers (PTFE, etc.), Fluorine-containing cyclic amorphous polymer (Cytop (registered trademark), Teflon (registered trademark) AF, etc.) and the like.
- a resin having transparency is preferable.
- curable resin or the monomer constituting the curable resin include alkyl vinyl ethers such as cyclohexyl methyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, and ethyl vinyl ether, glycidyl vinyl ether, vinyl acetate, vinyl pivalate, and various types (meth).
- alkyl vinyl ethers such as cyclohexyl methyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, and ethyl vinyl ether, glycidyl vinyl ether, vinyl acetate, vinyl pivalate, and various types (meth).
- Acrylates Phenoxyethyl acrylate, benzyl acrylate, stearyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, allyl acrylate, 1,3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate , Trimethylol, propane triacrylate, pentaaerythritol triacrylate, dipentaerythritol Hexahexaacrylate, ethoxyethyl acrylate, methoxyethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, diethylene glycol diacrylate, neopentyl glycol diacrylate, polyoxyethylene glycol diacrylate, tripropylene glycol diacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl
- the curable monomer may be either a photocurable monomer or a thermosetting monomer, but an ultraviolet curable monomer is preferable.
- the curable monomer include (a) urethane (meth) acrylate, (b) epoxy (meth) acrylate, (c) polyester (meth) acrylate, (d) polyether (meth) acrylate, and (e) silicon. (Meth) acrylate, (f) (meth) acrylate monomer, etc. are mentioned.
- curable monomer examples include the following.
- urethane (meth) acrylate examples include poly [(meth) acryloyloxyalkyl] isocyanurate represented by tris (2-hydroxyethyl) isocyanurate diacrylate and tris (2-hydroxyethyl) isocyanurate triacrylate.
- B Epoxy (meth) acrylate is obtained by adding a (meth) acryloyl group to an epoxy group, and generally uses bisphenol A, bisphenol F, phenol novolak, and an alicyclic compound as starting materials.
- Polyesters constituting the polyester part of the polyester (meth) acrylate include ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, trimethylolpropane, dipropylene glycol, polyethylene glycol,
- Examples of the polybasic acid include phthalic acid, adipic acid, maleic acid, trimellitic acid, itaconic acid, succinic acid, terephthalic acid, and alkenyl succinic acid.
- Examples of the (d) polyether (meth) acrylate include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polyethylene glycol-polypropylene glycol di (meth) acrylate and the like.
- (E) Silicon (meth) acrylate is obtained by modifying one end of dimethylpolysiloxane having a molecular weight of 1,000 to 10,000, or both ends with a (meth) acryloyl group. Illustrated.
- (F) (Meth) acrylate monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate , Sec-butyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, 3-methylbutyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethyl-n-hexyl (meth) ) Acrylate, n-octyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-
- curable resins and curable monomers the following are preferable examples that can be obtained from the market.
- curable resin examples include silicon resins PAK-01, PAK-02 (manufactured by Toyo Gosei Chemical), nanoimprint resin NIF series (manufactured by Asahi Glass Co., Ltd.), nanoimprint resin OCNL series (manufactured by Tokyo Ohka Kogyo Co., Ltd.), NIAC 2310 (Daicel). Chemical Industries), epoxy acrylate resins EH-1001, ES-4004, EX-C101, EX-C106, EX-C300, EX-C501, EX-0202, EX-0205, EX-5000, etc.
- silicone acrylate resins include Silaplane FM-0611, Silaplane FM-0621, Silaplane FM-0625, Dual-end (meth) acrylic Silaplane FM-7711, Silaplane.
- Polyfunctional acrylates include A-9300, A-9300-1CL, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A -TMPT, A-TMMT (manufactured by Shin-Nakamura Kogyo Co., Ltd.) and the like.
- Examples of polyfunctional methacrylates include TMPT (manufactured by Shin-Nakamura Kogyo Co., Ltd.).
- alkoxysilane group-containing (meth) acrylates include 3- (meth) acryloyloxypropyltrichlorosilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropyltriethoxysilane, 3- ( (Meth) acryloyloxypropyl triisopropoxysilane (also known as (triisopropoxysilyl) propyl methacrylate (abbreviation: TISMA) and (triisopropoxysilyl) propyl acrylate), 3- (meth) acryloxyisobutyltrichlorosilane, 3- (meta ) Acryloxyisobutyltriethoxysilane, 3- (meth) acryloxyisobutyltriisopropoxy 3- (meth) acryloxyisobutyltrimethoxysilane silane and the like.
- TISMA triisopropoxysi
- the transferred material contains a crosslinking catalyst.
- the crosslinking catalyst include radical polymerization initiators and acid generators.
- the radical polymerization initiator is a compound that generates radicals by heat or light, and examples thereof include a radical thermal polymerization initiator and a radical photopolymerization initiator. In the present invention, the radical photopolymerization initiator is preferable.
- radical thermal polymerization initiator examples include diacyl peroxides such as benzoyl peroxide and lauroyl peroxide, dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide, diisopropyl peroxydicarbonate, Peroxycarbonates such as bis (4-t-butylcyclohexyl) peroxydicarbonate, peroxide compounds such as alkyl peresters such as t-butylperoxyoctoate and t-butylperoxybenzoate, and azobisiso Examples include radical-generating azo compounds such as butyronitrile.
- radical photopolymerization initiator examples include -diketones such as benzyl and diacetyl, acyloins such as benzoin, acyloin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, thioxanthone, 2,4- Thioxanthones such as diethylthioxanthone and thioxanthone-4-sulfonic acid, benzophenones, benzophenones such as 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, acetophenone, 2- (4- Toluenesulfonyloxy) -2-phenylacetophenone, p-dimethylaminoacetophenone, 2,2′-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [
- IRGACURE 651 2,2-dimethoxy-1,2-diphenylethane-1-one
- IRGACURE 184 1-hydroxy-cyclohexyl-phenyl-ketone
- IRGACURE 2959 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one
- IRGACURE 127 2-Hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl ⁇ -2-methyl-propan-1-one
- IRGACURE 907 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one
- IRGACURE 369 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1
- IRGACURE 379 2- (dimethylamino) -2-[(4
- a radical photopolymerization initiator When a radical photopolymerization initiator is used as the crosslinking catalyst, diethylthioxanthone, isopropylthioxanthone, or the like can be used in combination as a sensitizer, and DAROCUR EDB (ethyl-4-dimethylaminobenzoate) can be used as a polymerization accelerator. ), DAROCUR EHA (2-ethylhexyl-4-dimethylaminobenzoate) or the like may be used in combination.
- the amount of the sensitizer is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable resin or the curable monomer. More preferably, it is 0.1 to 2 parts by mass.
- the blending amount of the polymerization accelerator is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the curable resin or the curable monomer. More preferably, it is 0.1 to 2 parts by mass.
- the acid generator is a material that generates an acid by applying heat or light, and examples thereof include a thermal acid generator and a photoacid generator.
- a photoacid generator is preferred.
- the thermal acid generator include benzoin tosylate, nitrobenzyl tosylate (particularly 4-nitrobenzyl tosylate), and other organic sulfonic acid alkyl esters.
- the photoacid generator is composed of a chromophore that absorbs light and an acid precursor that becomes an acid after decomposition. By irradiating the photoacid generator having such a structure with light of a specific wavelength, The acid generator is excited and acid is generated from the acid precursor portion.
- the photoacid generator include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, CF 3 SO 3 , p-CH 3 PhSO 3 , and p-NO 2 PhSO 3 (where Ph is a phenyl group). Examples thereof include salts, organic halogen compounds, orthoquinone-diazide sulfonyl chloride, and sulfonic acid esters.
- photoacid generators include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds, 2-trihalomethyl-5-aryl-1,3,4-oxadiazole compounds, 2-trihalo Also included are methyl-5-hydroxyphenyl-1,3,4-oxadiazole compounds.
- the organic halogen compound is a compound that forms hydrohalic acid (for example, hydrogen chloride).
- WPAG-145 bis (cyclohexylsulfonyl) diazomethane
- WPAG-170 bis (t-butylsulfonyl) diazomethane
- WPAG-199 bis (p-toluenesulfonyl) diazomethane
- WPAG-281 manufactured by Wako Pure Chemical Industries, Ltd.
- TME-triazine [2- [2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (tri-chloromethyl) -s-triazine] MP-triazine [2- (Methoxyphenyl) -4,6-bis (trichloromethyl) -s-to Azine, dimethoxy [2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (tri - chloromethyl) -s-triazine.
- the blending amount of the crosslinking catalyst is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the curable resin or the curable monomer. In such a range, a sufficient cured product can be obtained.
- the blending amount of the crosslinking catalyst is more preferably 0.3 to 5 parts by mass, still more preferably 0.5 to 2 parts by mass.
- the acid scavenger is not particularly limited, but a basic compound such as an amine (particularly an organic amine), a basic ammonium salt, or a basic sulfonium salt is preferable. Among these acid scavengers, organic amines are more preferable because of excellent image performance.
- the acid scavenger examples include 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4- Diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4,4'-diaminodiphenyl ether, pyridinium p-toluenesulfonate 2,4,6-trimethylpyridinium p-toluenesulfonate, tetramethylammonium p-toluenesulfonate, tetrabutylammonium lactate, triethylamine, tributylamine and the like.
- Organic amines such as octane, 4-dimethylaminopyridine, 1-naphthylamine, piperidine, hexamethylenetetramine, imidazoles, hydroxypyridines, pyridines, 4,4′-diaminodiphenyl ether, triethylamine, and tributylamine are preferred.
- the amount of the acid scavenger is preferably 20 parts by mass or less, more preferably 0.1 to 10 parts by mass, and still more preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the acid generator. 5 parts by mass.
- step (3) the mold is released from the transfer object to obtain the transfer object having a transfer pattern.
- the transfer object has a transfer pattern in which the uneven pattern of the mold is reversed.
- FIG. 1 shows an embodiment of the production method of the present invention.
- a concavo-convex pattern provided on a roll-shaped mold can be transferred to a transferred material continuously or intermittently using a transferred material containing a photocurable resin.
- the mold 3 shown in FIG. 1 has an uneven pattern on the surface, and further has a release layer on the surface.
- the transferred object 1 fed in the direction of the arrow reaches the roll-shaped mold 3 coated with the fluoropolyether (FPE) via the roll 2a. Thereafter, the rotating mold 3 is pressed against the transfer object 1, and the uneven pattern is transferred to the transfer object 1.
- light such as ultraviolet rays is irradiated to cure the transfer object 1.
- the transfer object 1 having the transfer pattern is sent to the next step via the roll 2b. As shown in FIG. 1, light may be irradiated again as necessary.
- the mold 3 has a region in contact with the transferred object 1 and a region not in contact with the transferred object 1, and the mold 3 is not in contact with the transferred object 1.
- FPE is applied in the area. Thereby, FPE can be apply
- the release layer is always protected by FPE, so that high releasability is maintained even when repeated transfer or repeated light irradiation is performed.
- the transferred material can be used as it is for the following purposes, or can be used as a replica mold.
- the replica mold When the transfer object is used as the replica mold, the replica mold has a good releasability because the fluoropolyether is attached to the surface.
- the electronic device can be used for an integrated circuit such as a transistor, a memory, a light emitting diode (EL), a laser, or a solar cell.
- a film having a regular concavo-convex structure such as a sunlight collecting film and a liquid crystal polarizing plate can be produced. From these devices, flexible displays, wireless tags, wearable computers and the like are manufactured.
- Optical devices include display pixels such as color filters for liquid crystal displays and organic EL, optical memories, light modulation elements, optical shutters, second harmonic (SHG) elements, polarizing elements, photonic crystals, lens arrays, etc.
- the magnetic device can be used for a next-generation hard disk drive (discrete track) and the next-generation hard disk drive (patterned media), and the medical device can be used for biochips such as DNA arrays and protein arrays.
- the chemical analysis device can be used for a microchemical chip such as a microchemical plant or a microchemical analysis system.
- PFPE polyfluoropolyether
- Both-end hydroxymethyl formula HOH 2 CF 2 CF 2 CO— (CF 2 CF 2 CF 2 O) n —CF 2 CF 2 CH 2 OH
- the compound represented by (n is an integer of 1 or more) is referred to as “demnum dimethyl alcohol”.
- a compound represented by (n is an integer of 1 or more) is referred to as “demnum carboxylic acid”.
- the static contact angle and water falling angle were measured by the following method using a fully automatic contact angle meter DropMaster 700 (manufactured by Kyowa Interface Science).
- the static contact angle was determined by dropping 2 ⁇ L of water or n-hexadecane from a microsyringe onto a horizontally placed substrate and taking a still image 1 second after dropping with a video microscope.
- the water falling angle was calculated
- Experimental example 1 ⁇ Mold processing method with demnam oil>
- the quartz slide glass treated with the fluorine surface was immersed in this treatment liquid and dried at 60 ° C. for 10 minutes to obtain a mold.
- Comparative Example 1 is a quartz slide glass whose surface is fluorine-coated with Optool DSX (registered trademark), a fluorine-based surface treatment agent, and Comparative Example 2 is a non-treated quartz slide glass (water contact angle 16 °).
- the surface of the obtained mold was analyzed, and the mold resin material was peeled off after being cured from the silicon substrate, and the adhesion of the mold resin after hardening to the mold was observed.
- the peelability was evaluated in two steps as follows.
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Abstract
Description
本発明は、上記現状に鑑みてなされたものであり、転写パターンを有する被転写物の製造方法であって、繰り返し転写を行っても、被転写物が基板から剥がれたり、モールドに付着したりしにくい製造方法を提供することを目的とする。
-SiR1 n1R2 3-n1
(式中、R1は、加水分解可能な基を表し;
R2は、水素原子または炭素数1~22のアルキル基を表し;
n1は、1~3の整数である。)
で表される基を有する化合物を含むことが好ましい。
上記離型層は、下記一般式(A1)、(A2)、(B1)、(B2)、(C1)、(C2)、(D1)および(D2):
PFPEは、各出現においてそれぞれ独立して、式:
-(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)d-
(式中、a、b、cおよびdは、それぞれ独立して、0~200の整数であって、a、b、cおよびdの和は少なくとも1であり、添字a、b、cまたはdを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。)
で表される基であり;
Rfは、各出現においてそれぞれ独立して、1個またはそれ以上のフッ素原子により置換されていてもよい炭素数1~16のアルキル基を表し;
R1は、各出現においてそれぞれ独立して、加水分解可能な基を表し;
R2は、各出現においてそれぞれ独立して、水素原子または炭素数1~22のアルキル基を表し;
R11は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し;
R12は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し;
n1は、(-SiR1 n1R2 3-n1)単位毎に独立して、0~3の整数であり;
ただし、式(A1)、(A2)、(B1)および(B2)において、少なくとも1つのn1が、1~3の整数であり;
X1は、それぞれ独立して、単結合または2~10価の有機基を表し;
X2は、各出現においてそれぞれ独立して、単結合または2価の有機基を表し;
tは、各出現においてそれぞれ独立して、1~10の整数であり;
αは、それぞれ独立して、1~9の整数であり;
α’は、それぞれ独立して、1~9の整数であり;
X5は、それぞれ独立して、単結合または2~10価の有機基を表し;
βは、それぞれ独立して、1~9の整数であり;
β’は、それぞれ独立して、1~9の整数であり;
X7は、それぞれ独立して、単結合または2~10価の有機基を表し;
γは、それぞれ独立して、1~9の整数であり;
γ’は、それぞれ独立して、1~9の整数であり;
Raは、各出現においてそれぞれ独立して、-Z1-SiR71 p1R72 q1R73 r1を表し;
Z1は、各出現においてそれぞれ独立して、酸素原子または2価の有機基を表し;
R71は、各出現においてそれぞれ独立して、Ra’を表し;
Ra’は、Raと同意義であり;
Ra中、Z1基を介して直鎖状に連結されるSiは最大で5個であり;
R72は、各出現においてそれぞれ独立して、加水分解可能な基を表し;
R73は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し;
p1は、各出現においてそれぞれ独立して、0~3の整数であり;
q1は、各出現においてそれぞれ独立して、0~3の整数であり;
r1は、各出現においてそれぞれ独立して、0~3の整数であり;
ただし、式(C1)および(C2)において、少なくとも1つのq1が1~3の整数であり;
Rbは、各出現においてそれぞれ独立して、加水分解可能な基を表し;
Rcは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し;
k1は、各出現においてそれぞれ独立して、1~3の整数であり;
l1は、各出現においてそれぞれ独立して、0~2の整数であり;
m1は、各出現においてそれぞれ独立して、0~2の整数であり;
ただし、γを付して括弧でくくられた単位において、k1、l1およびm1の和は3であり;
X9は、それぞれ独立して、単結合または2~10価の有機基を表し;
δは、それぞれ独立して、1~9の整数であり;
δ’は、それぞれ独立して、1~9の整数であり;
Rdは、各出現においてそれぞれ独立して、-Z2-CR81 p2R82 q2R83 r2を表し;
Z2は、各出現においてそれぞれ独立して、酸素原子または2価の有機基を表し;
R81は、各出現においてそれぞれ独立して、Rd’を表し;
Rd’は、Rdと同意義であり;
Rd中、Z2基を介して直鎖状に連結されるCは最大で5個であり;
R82は、各出現においてそれぞれ独立して、-Y-SiR85 n2R86 3-n2を表し;
Yは、各出現においてそれぞれ独立して、2価の有機基を表し;
R85は、各出現においてそれぞれ独立して、加水分解可能な基を表し;
R86は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し;
n2は、(-Y-SiR85 n2R86 3-n2)単位毎に独立して、1~3の整数を表し;
ただし、式(C1)および(C2)において、少なくとも1つのn2は1~3の整数であり;
R83は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し;
p2は、各出現においてそれぞれ独立して、0~3の整数であり;
q2は、各出現においてそれぞれ独立して、0~3の整数であり;
r2は、各出現においてそれぞれ独立して、0~3の整数であり;
Reは、各出現においてそれぞれ独立して、-Y-SiR85 n2R86 3-n2を表し;
Rfは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し;
k2は、各出現においてそれぞれ独立して、0~3の整数であり;
l2は、各出現においてそれぞれ独立して、0~3の整数であり;
m2は、各出現においてそれぞれ独立して、0~3の整数であり;
ただし、式(D1)および(D2)において、少なくとも1つのq2は2または3であるか、あるいは、少なくとも1つのl2は2または3である。ただし、k2、l2およびm2の和は3である。]
のいずれかで表される少なくとも1種のパーフルオロ(ポリ)エーテル基含有シラン化合物を含むことが好ましい。
-(R31)p’-(Xa)q’-
[式中:
R31は、単結合、-(CH2)s’-またはo-、m-もしくはp-フェニレン基を表し、好ましくは-(CH2)s’-であり、
s’は、1~20の整数、好ましくは1~6の整数、より好ましくは1~3の整数、さらにより好ましくは1または2であり、
Xaは、-(Xb)l’-を表し、
Xbは、各出現においてそれぞれ独立して、-O-、-S-、o-、m-もしくはp-フェニレン基、-C(O)O-、-Si(R33)2-、-(Si(R33)2O)m’-Si(R33)2-、-CONR34-、-O-CONR34-、-NR34-および-(CH2)n’-からなる群から選択される基を表し、
R33は、各出現においてそれぞれ独立して、フェニル基、C1-6アルキル基またはC1-6アルコキシ基を表し、好ましくはフェニル基またはC1-6アルキル基であり、より好ましくはメチル基であり、
R34は、各出現においてそれぞれ独立して、水素原子、フェニル基またはC1-6アルキル基(好ましくはメチル基)を表し、
m’は、各出現において、それぞれ独立して、1~100の整数、好ましくは1~20の整数であり、
n’は、各出現において、それぞれ独立して、1~20の整数、好ましくは1~6の整数、より好ましくは1~3の整数であり、
l’は、1~10の整数、好ましくは1~5の整数、より好ましくは1~3の整数であり、
p’は、0、1または2であり、
q’は、0または1であり、
ここに、p’およびq’の少なくとも一方は1であり、p’またはq’を付して括弧でくくられた各繰り返し単位の存在順序は任意である]
で表される2価の基が挙げられる。ここに、R31およびXa(典型的にはR31およびXaの水素原子)は、フッ素原子、C1-3アルキル基およびC1-3フルオロアルキル基から選択される1個またはそれ以上の置換基により置換されていてもよい。
C1-20アルキレン基、
-R31-Xc-R32-、または
-Xd-R32-
[式中、R31およびR32は、上記と同意義である。]
であり得る。
C1-20アルキレン基、
-(CH2)s’-Xc-、
-(CH2)s’-Xc-(CH2)t’-
-Xd-、または
-Xd-(CH2)t’-
[式中、s’およびt’は、上記と同意義である。]
である。
-O-、
-S-、
-C(O)O-、
-CONR34-、
-O-CONR34-、
-Si(R33)2-、
-(Si(R33)2O)m’-Si(R33)2-、
-O-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-O-(CH2)u’-Si(R33)2-O-Si(R33)2-CH2CH2-Si(R33)2-O-Si(R33)2-、
-O-(CH2)u’-Si(OCH3)2OSi(OCH3)2-、
-CONR34-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-CONR34-(CH2)u’-N(R34)-、または
-CONR34-(o-、m-またはp-フェニレン)-Si(R33)2-
[式中、R33、R34およびm’は、上記と同意義であり、
u’は1~20の整数、好ましくは2~6の整数、より好ましくは2~3の整数である。]を表す。Xcは、好ましくは-O-である。
-S-、
-C(O)O-、
-CONR34-、
-CONR34-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-、
-CONR34-(CH2)u’-N(R34)-、または
-CONR34-(o-、m-またはp-フェニレン)-Si(R33)2-
[式中、各記号は、上記と同意義である。]
を表す。
C1-20アルキレン基、
-(CH2)s’-Xc-(CH2)t’-、または
-Xd-(CH2)t’-
[式中、各記号は、上記と同意義である。]
であり得る。
C1-20アルキレン基、
-(CH2)s’-O-(CH2)t’-、
-(CH2)s’-(Si(R33)2O)m’-Si(R33)2-(CH2)t’-、
-(CH2)s’-O-(CH2)u’-(Si(R33)2O)m’-Si(R33)2-(CH2)t’-、または
-(CH2)s’-O-(CH2)t’-Si(R33)2 -(CH2)u’-Si(R33)2-(CvH2v)-
[式中、R33、m’、s’、t’およびu’は、上記と同意義であり、vは1~20の整数、好ましくは2~6の整数、より好ましくは2~3の整数である。]
である。
Dは、
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CF2O(CH2)3-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-CONH-(CH2)3-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、および
から選択される基であり、
Eは、-(CH2)n-(nは2~6の整数)であり、
Dは、分子主鎖のPFPEに結合し、Eは、PFPEと反対の基に結合する。]
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CONH-(CH2)3-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CONH-(CH2)6-、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
R41は、それぞれ独立して、水素原子、フェニル基、炭素数1~6のアルキル基、またはC1-6アルコキシ基、好ましくはメチル基であり;
各X1基において、Tのうち任意のいくつかは、分子主鎖のPFPEに結合する以下の基:
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CF2O(CH2)3-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-CONH-(CH2)3-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、または
であり、別のTのいくつかは、分子主鎖のPFPEと反対の基(即ち、式(A1)、(A2)、(D1)および(D2)においては炭素原子、また、下記する式(B1)、(B2)、(C1)および(C2)においてはSi原子)に結合する-(CH2)n”-(n”は2~6の整数)であり、存在する場合、残りは、それぞれ独立して、メチル基、フェニル基、C1-6アルコキシ基またはラジカル捕捉基もしくは紫外線吸収基であり得る。
PFPEは、それぞれ独立して、式:
-(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)d-
(式中、a、b、cおよびdは、それぞれ独立して、0~200の整数であって、a、b、cおよびdの和は少なくとも1であり、添字a、b、cまたはdを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。)
で表される基であり;
Rfは、各出現においてそれぞれ独立して、1個またはそれ以上のフッ素原子により置換されていてもよい炭素数1~16のアルキル基を表し;
R1は、各出現においてそれぞれ独立して、加水分解可能な基を表し;
R2は、各出現においてそれぞれ独立して、水素原子または炭素数1~22のアルキル基を表し;
R11は、各出現においてそれぞれ独立して、水素原子またはハロゲン原子を表し;
R12は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し;
n1は、1~3の整数であり、好ましくは3であり;
X1は、-O-CFR13-(CF2)e-であり;
R13は、フッ素原子または低級フルオロアルキル基であり;
eは、0または1であり;
X2は、-(CH2)u-であり;
uは、0~2の整数であり(uが0の場合X2は単結合である);
tは、1~10の整数である。]
で表される化合物である。
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CONH-(CH2)3-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CONH-(CH2)6-、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
PFPEは、それぞれ独立して、式:
-(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)d-
(式中、a、b、cおよびdは、それぞれ独立して、0~200の整数であって、a、b、cおよびdの和は少なくとも1であり、添字a、b、cまたはdを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。)
で表される基であり;
Rfは、各出現においてそれぞれ独立して、1個またはそれ以上のフッ素原子により置換されていてもよい炭素数1~16のアルキル基を表し;
R1は、各出現においてそれぞれ独立して、加水分解可能な基を表し;
R2は、各出現においてそれぞれ独立して、水素原子または炭素数1~22のアルキル基を表し;
n1は、1~3の整数であり、好ましくは3であり;
X5は、-CH2O(CH2)2-、-CH2O(CH2)3-または-CH2O(CH2)6-である]
で表される化合物である。
PFPEは、それぞれ独立して、式:
-(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)d-
(式中、a、b、cおよびdは、それぞれ独立して、0~200の整数であって、a、b、cおよびdの和は少なくとも1であり、添字a、b、cまたはdを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。)
で表される基であり;
Rfは、各出現においてそれぞれ独立して、1個またはそれ以上のフッ素原子により置換されていてもよい炭素数1~16のアルキル基を表し;
X5’は、それぞれ独立して、単結合または2~10価の有機基を表し;
βは、それぞれ独立して、1~9の整数であり;
β’は、それぞれ独立して、1~9の整数であり;
R92は、単結合または2価の有機基である。]
で表される化合物を、HSiM3(式中、Mは、それぞれ独立して、ハロゲン原子、R1またはR2であり、R1は、各出現においてそれぞれ独立して、加水分解可能な基であり、R2は、各出現においてそれぞれ独立して、水素原子または炭素数1~22のアルキル基である)と反応させて、必要に応じて、上記ハロゲン原子を、R1またはR2に変換して、式(B1”)または(B2”):
n1は、0~3の整数である。]
で表される化合物として得ることができる。
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CONH-(CH2)3-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CONH-(CH2)6-、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
PFPEは、それぞれ独立して、式:
-(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)d-
(式中、a、b、cおよびdは、それぞれ独立して、0~200の整数であって、a、b、cおよびdの和は少なくとも1であり、添字a、b、cまたはdを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。)
で表される基であり;
Rfは、各出現においてそれぞれ独立して、1個またはそれ以上のフッ素原子により置換されていてもよい炭素数1~16のアルキル基を表し;
X7は、-CH2O(CH2)2-、-CH2O(CH2)3-または-CH2O(CH2)6-を表し;
Raは、各出現においてそれぞれ独立して、-Z1-SiR71 p1R72 q1R73 r1を表し;
Z1は、C1-6アルキレン基を表し;
R71は、各出現においてそれぞれ独立して、Ra’を表し;
Ra’は、Raと同意義であり;
Ra中、Z1基を介して直鎖状に連結されるSiは最大で5個であり;
R72は、各出現においてそれぞれ独立して、加水分解可能な基を表し;
R73は、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し;
p1は、各出現においてそれぞれ独立して、0~2の整数であり;
q1は、各出現においてそれぞれ独立して、1~3の整数、好ましくは3であり;
r1は、各出現においてそれぞれ独立して、0~2の整数であり;
ただし、一のRaにおいて、p1、q1およびr1の和は3である。]
で表される化合物である。
PFPEは、それぞれ独立して、式:
-(OC4F8)a-(OC3F6)b-(OC2F4)c-(OCF2)d-
(式中、a、b、cおよびdは、それぞれ独立して、0~200の整数であって、a、b、cおよびdの和は少なくとも1であり、添字a、b、cまたはdを付して括弧でくくられた各繰り返し単位の存在順序は式中において任意である。)
で表される基であり;
Rfは、各出現においてそれぞれ独立して、1個またはそれ以上のフッ素原子により置換されていてもよい炭素数1~16のアルキル基を表し;
X7’は、それぞれ独立して、単結合または2~10価の有機基を表し;
γは、それぞれ独立して、1~9の整数であり;
γ’は、それぞれ独立して、1~9の整数であり;
R92は、単結合または2価の有機基である。]
で表される化合物を、HSiR93 k1Rb l1Rc m1(式中、R93はハロゲン原子、例えばフッ素原子、塩素原子、臭素原子またはヨウ素原子、好ましくは塩素原子であり、Rbは、各出現においてそれぞれ独立して、加水分解可能な基を表し、Rcは、各出現においてそれぞれ独立して、水素原子または低級アルキル基を表し、k1は1~3の整数であり、l1およびm1は、それぞれ独立して、0~2の整数であり、k1、l1およびm1の和は3である。)で表される化合物と反応させて、式(C1-5)または(C2-5):
q1は、各出現においてそれぞれ独立して、1~3の整数であり;
r1は、各出現においてそれぞれ独立して、0~2の整数である。]
で表される化合物を得ることができる。
-CH2O(CH2)2-、
-CH2O(CH2)3-、
-CH2O(CH2)6-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CH2O(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-CH2OCF2CHFOCF2-、
-CH2OCF2CHFOCF2CF2-、
-CH2OCF2CHFOCF2CF2CF2-、
-CH2OCH2CF2CF2OCF2-、
-CH2OCH2CF2CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF2CF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CF2CF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF2-、
-CH2OCH2CHFCF2OCF2CF2-、
-CH2OCH2CHFCF2OCF2CF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2-、
-CH2OCH2CHFCF2OCF(CF3)CF2OCF2CF2CF2-、
-CH2OCH2(CH2)7CH2Si(OCH3)2OSi(OCH3)2(CH2)2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)3-、
-CH2OCH2CH2CH2Si(OCH3)2OSi(OCH3)2(CH2)2-、
-CH2OCH2CH2CH2Si(OCH2CH3)2OSi(OCH2CH3)2(CH2)2-、
-(CH2)2-、
-(CH2)3-、
-(CH2)4-、
-(CH2)5-、
-(CH2)6-、
-(CH2)2-Si(CH3)2-(CH2)2-、
-CONH-(CH2)3-、
-CON(CH3)-(CH2)3-、
-CON(Ph)-(CH2)3-(式中、Phはフェニルを意味する)、
-CONH-(CH2)6-、
-CON(CH3)-(CH2)6-、
-CON(Ph)-(CH2)6-(式中、Phはフェニルを意味する)、
-CONH-(CH2)2NH(CH2)3-、
-CONH-(CH2)6NH(CH2)3-、
-CH2O-CONH-(CH2)3-、
-CH2O-CONH-(CH2)6-、
-S-(CH2)3-、
-(CH2)2S(CH2)3-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2OSi(CH3)2OSi(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)2Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)3Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)10Si(CH3)2(CH2)2-、
-CONH-(CH2)3Si(CH3)2O(Si(CH3)2O)20Si(CH3)2(CH2)2-、
-C(O)O-(CH2)3-、
-C(O)O-(CH2)6-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)2-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-(CH2)3-、
-CH2-O-(CH2)3-Si(CH3)2-(CH2)2-Si(CH3)2-CH(CH3)-CH2-、
-OCH2-、
-O(CH2)3-、
-OCFHCF2-、
式:R111-(R112O)m-R113
(R111及びR113は、独立に、F、炭素数1~16のアルキル基、炭素数1~16のアルコキシ基、炭素数1~16のフッ素化アルキル基、炭素数1~16のフッ素化アルコキシ基、-R114-X111(R114は単結合又は二価の有機基、X111は-NH2、-OH、-COOH、-CH=CH2、-OCH2CH=CH2、ハロゲン、リン酸、リン酸エステル、カルボン酸エステル、チオール、チオエーテル、アルキルエーテル(フッ素で置換されていてもよい)、アリール、アリールエーテル又はアミド)、R112は炭素数1~4のフッ素化アルキレン基、mは2以上の整数)で表される化合物がより好ましい。撥水性、撥油性、防汚性付与の観点から、X111としては、-OH、-COOH、チオール(-SH)、-CH=CH2及び-OCH2CH=CH2からなる群より選択される少なくとも1種が好ましい。上記二価の有機基としては、アルキレン基、フッ素化アルキレン基、又は、それらの末端に酸素原子が結合した基等が挙げられる。上記二価の有機基の炭素数は特に限定されないが、例えば、1~16であってよい。
式:-(CX112 2CF2CF2O)n111(CF(CF3)CF2O)n112(CF2CF2O)n113(CF2O)n114(C4F8O)n115-
(n111、n112、n113、n114及びn115は、独立に、0又は1以上の整数、X112はH、F又はCl、各繰り返し単位の存在順序は任意である)で表されるもの、
式:-(OC2F4-R118)f-
(R118は、OC2F4、OC3F6およびOC4F8から選択される基であり、fは、2~100の整数である)で表されるもの
等が挙げられる。
また、上記製造方法は、工程(3)を実施した後に、上記被転写物を加熱するか、又は、上記被転写物に光を照射して、上記被転写物を硬化させる工程を含むこともできる。
しかし、上記製造方法は、工程(1)を含むことから、上記被転写物の剥離や付着を回避し得る。従って、工程(2)において、上記モールドを上記被転写物に押し付けるとともに、上記被転写物に紫外線を照射する製造方法も、本発明の好適な態様の1つである。
上記硬化性モノマーとしては、例えば、(a)ウレタン(メタ)アクリレート、(b)エポキシ(メタ)アクリレート、(c)ポリエステル(メタ)アクリレート、(d)ポリエーテル(メタ)アクリレート、(e)シリコン(メタ)アクリレート、(f)(メタ)アクリレートモノマーなどが挙げられる。
(a)ウレタン(メタ)アクリレートとしては、トリス(2-ヒドロキシエチル)イソシアヌレートジアクリレート、トリス(2-ヒドロキシエチル)イソシアヌレートトリアクリレートに代表されるポリ〔(メタ)アクリロイルオキシアルキル〕イソシアヌレートが挙げられる。
(b)エポキシ(メタ)アクリレートはエポキシ基に(メタ)アクリロイル基を付加したものであり、出発原料としてビスフェノールA、ビスフェノールF、フェノールノボラック、脂環化合物を用いたものが一般的である。
(c)ポリエステル(メタ)アクリレートのポリエステル部を構成する多価アルコールとしては、エチレングリコール、1,4-ブタンジオール、1,6-ヘキサンジオール、ジエチレングリコール、トリメチロールプロパン、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ペンタエリスリトール、ジペンタエリスリトールなどが挙げられ、多塩基酸としては、フタル酸、アジピン酸、マレイン酸、トリメリット酸、イタコン酸、コハク酸、テレフタル酸、アルケニルコハク酸などが挙げられる。
(d)ポリエーテル(メタ)アクリレートとしては、ポリエチレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、ポリエチレングリコール-ポリプロピレングリコールジ(メタ)アクリレートなどが挙げられる。
(e)シリコン(メタ)アクリレートは、分子量1,000~10,000のジメチルポリシロキサンの片末端、あるいは、両末端を(メタ)アクリロイル基で変性したものであり、例えば、以下の化合物などが例示される。
多官能アクリレート類としては、A-9300、A-9300-1CL、A-GLY-9E、A-GLY-20E、A-TMM-3、A-TMM-3L、A-TMM-3LM-N、A-TMPT、A-TMMT(新中村工業社製)等が挙げられる。
多官能メタクリレート類としてTMPT(新中村工業社製)等が挙げられる。
アルコキシシラン基含有(メタ)アクリレートとしては、3-(メタ)アクリロイルオキシプロピルトリクロロシシラン、3-(メタ)アクリロイルオキシプロピルトリメトキシシラン、3-(メタ)アクリロイルオキシプロピルトリエトキシシラン、3-(メタ)アクリロイルオキシプロピルトリイソプロポキシシラン(別名(トリイソプロポキシシリル)プロピルメタクリレート(略称:TISMA)および(トリイソプロポキシシリル)プロピルアクリレート)、3-(メタ)アクリルオキシイソブチルトリクロロシラン、3-(メタ)アクリルオキシイソブチルトリエトキシシラン、3-(メタ)アクリルオキシイソブチルトリイソプロポキ3-(メタ)アクリルオキシイソブチルトリメトキシシランシシラン等が挙げられる。
上記ラジカル重合開始剤は、熱や光によりラジカルを発生する化合物であり、ラジカル熱重合開始剤、ラジカル光重合開始剤が挙げられる。本発明においては、上記ラジカル光重合開始剤が好ましい。
IRGACURE 651:2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、
IRGACURE 184:1-ヒドロキシ-シクロヘキシル-フェニル-ケトン、
IRGACURE 2959:1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、
IRGACURE 127:2-ヒロドキシ-1-{4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]フェニル}-2-メチル-プロパン-1-オン、
IRGACURE 907:2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン、
IRGACURE 369:2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1、
IRGACURE 379:2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル]-1-[4-(4-モルホリニル)フェニル]-1-ブタノン、
IRGACURE 819:ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド、
IRGACURE 784:ビス(η5-2,4-シクロペンタジエン-1-イル)-ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)-フェニル)チタニウム、
IRGACURE OXE 01:1,2-オクタンジオン,1-[4-(フェニルチオ)-,2-(O-ベンゾイルオキシム)]、
IRGACURE OXE 02:エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(0-アセチルオキシム)、
IRGACURE261、IRGACURE369、IRGACURE500、
DAROCUR 1173:2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、
DAROCUR TPO:2,4,6-トリメチルベンゾイル-ジフェニル-フォスフィンオキサイド、
DAROCUR1116、DAROCUR2959、DAROCUR1664、DAROCUR4043、
IRGACURE 754 オキシフェニル酢酸:2-[2-オキソ-2-フェニルアセトキシエトキシ]エチルエステルとオキシフェニル酢酸、2-(2-ヒドロキシエトキシ)エチルエステルの混合物、
IRGACURE 500:IRGACURE 184とベンゾフェノンとの混合物(1:1)、
IRGACURE 1300:IRGACURE 369とIRGACURE 651との混合物(3:7)、
IRGACURE 1800:CGI403とIRGACURE 184との混合物(1:3)、
IRGACURE 1870:CGI403とIRGACURE 184との混合物(7:3)、
DAROCUR 4265:DAROCUR TPOとDAROCUR 1173との混合物(1:1)。
なお、IRGACUREはチバ・スペシャルティ・ケミカルズ社製であり、DAROCURはメルクジャパン社製である。
また、上記重合促進剤を用いる場合の重合促進剤の配合量としては、上記硬化性樹脂若しくは上記硬化性モノマー100質量部に対して、0.1~5質量部であることが好ましい。より好ましくは、0.1~2質量部である。
上記熱酸発生剤としては、例えば、ベンゾイントシレート、ニトロベンジルトシレート(特に、4-ニトロベンジルトシレート)、他の有機スルホン酸のアルキルエステル等が挙げられる。
上記光酸発生剤としては、例えば、ジアゾニウム塩、ホスホニウム塩、スルホニウム塩、ヨードニウム塩、CF3SO3、p-CH3PhSO3、p-NO2PhSO3(ただし、Phはフェニル基)等の塩、有機ハロゲン化合物、オルトキノン-ジアジドスルホニルクロリド、またはスルホン酸エステル等が挙げられる。その他、光酸発生剤として、2-ハロメチル-5-ビニル-1,3,4-オキサジアゾール化合物、2-トリハロメチル-5-アリール-1,3,4-オキサジアゾール化合物、2-トリハロメチル-5-ヒドロキシフェニル-1,3,4-オキサジアゾール化合物なども挙げられる。
なお、上記有機ハロゲン化合物は、ハロゲン化水素酸(例えば、塩化水素)を形成する化合物である。
和光純薬工業社製のWPAG-145[ビス(シクロヘキシルスルホニル)ジアゾメタン]、WPAG-170[ビス(t-ブチルスルホニル)ジアゾメタン]、WPAG-199[ビス(p-トルエンスルホニル)ジアゾメタン]、WPAG-281[トリフェニルスルホニウム トリフルオロメタンスルホネート]、WPAG-336[ジフェニル-4-メチルフェニルスルホニウム トリフルオロメタンスルホネート]、WPAG-367[ジフェニル-2,4,6-トリメチルフェニルスルホニウム p-トルエンスルホネート]、チバ・スペシャルティ・ケミカルズ社製のIRGACURE PAG103[(5-プロピルスルホニルオキシミノ-5H-チオフェン-2-イリデン)-(2-メチルフェニル)アセトニトリル]、IRGACURE PAG108[(5-オクチルスルホニルオキシミノ-5H-チオフェン-2-イリデン)-(2-メチルフェニル)アセトニトリル)]、IRGACURE PAG121[(5-p-トルエンスルホニルオキシミノ-5H-チオフェン-2-イリデン)-(2-メチルフェニル)アセトニトリル]、IRGACURE PAG203、CGI725、三和ケミカル社製のTFE-トリアジン[2-[2-(フラン-2-イル)エテニル]-4,6-ビス(トリクロロメチル)-s-トリアジン]、TME-トリアジン[2-[2-(5-メチルフラン-2-イル)エテニル]-4,6-ビス(トリ-クロロメチル)-s-トリアジン]MP-トリアジン[2-(メトキシフェニル)-4,6-ビス(トリクロロメチル)-s-トリアジン]、ジメトキシ[2-[2-(3,4-ジメトキシフェニル)エテニル]-4,6-ビス(トリ-クロロメチル)-s-トリアジン]。
上記酸捕捉剤としては、特に制限されないが、アミン(特に、有機アミン)、塩基性のアンモニウム塩、塩基性のスルホニウム塩などの塩基性化合物が好ましい。これらの酸捕捉剤の中でも、有機アミンが、画像性能が優れる点でより好ましい。
式:F3CF2CO-(CF2CF2CF2O)nCF2CF2CH2NH2
(nは1以上の整数)で表される化合物を、「デムナムメチルアミン」と称する。
式:H2NH2CF2CF2CO-(CF2CF2CF2O)nCF2CF2CH2NH2
(nは1以上の整数)で表される化合物を、「デムナムジメチルアミン」と称する。
式:F3CF2CO-(CF2CF2CF2O)n-CF2CF3
(nは1以上の整数)で表される化合物を、「デムナムオイル」と称する。
片末端がヒドロキシメチル(CH2OH)の
式:F3CF2CO-(CF2CF2CF2O)n-CF2CF2CH2OH
(nは1以上の整数)で表される化合物を、を「デムナムメチルアルコール」と称する。
両末端ヒドロキシメチルの
式:HOH2CF2CF2CO-(CF2CF2CF2O)n-CF2CF2CH2OH
(nは1以上の整数)で表される化合物を、「デムナムジメチルアルコール」と称する。
片末端がカルボン酸(COOH)の
式:F3CF2CO-(CF2CF2CF2O)n-CF2CF2COOH
(nは1以上の整数)で表される化合物を「デムナムカルボン酸」と称する。
両末端がカルボン酸(COOH)の
式:HOOCF2CF2CO-(CF2CF2CF2O)n-CF2CF2COOH
(nは1以上の整数)で表される化合物を「デムナムジカルボン酸」と称する。
片末端がCH2OCH2CH=CH2の
式:F3CF2CO-(CF2CF2CF2O)n-CF2CF2CH2OCH2CH=CH2
(nは1以上の整数)で表される化合物を「デムナムアリルエーテル」と称する。
両末端がCH2OCH2CH=CH2の
式:H2C=CHCH2OCH2CF2CF2CO-(CF2CF2CF2O)nCH2OCH2CH=CH2
(nは1以上の整数)で表される化合物を「デムナムジアリルエーテル」とする。
静的接触角は、水平に置いた基板にマイクロシリンジから水又はn-ヘキサデカンを2μL滴下し、滴下1秒後の静止画をビデオマイクロスコープで撮影することにより求めた。
<デムナムオイルによるモールド処理方法>
表面をフッ素系表面処理剤のオプツールDSX(登録商標、ダイキン工業社製、パーフルオロ(ポリ)エーテル基含有シラン化合物)でフッ素表面処理した石英スライドグラスの対水接触角を測定すると113°であった。デムナムオイル(Mw=2000)をHFE7300にて0.1質量%の濃度の処理液を調製した。この処理液に前記フッ素表面処理した石英スライドグラスを浸漬させ60℃で10分乾燥しモールドとした。
<デムナムメチルアルコールによるモールド処理方法>
実験例1のデムナムオイル(Mw=2000)をデムナムメチルアルコール(Mw=2000)に変えた以外は同様に処理を行いモールドとした。
<デムナムメチルアミンによるモールド処理方法>
実験例1のデムナムオイル(Mw=2000)をデムナムメチルアミン(Mw=2000)に変えた以外は同様に処理を行いモールドとした。
<デムナムカルボン酸によるモールド処理方法>
実験例1のデムナムオイル(Mw=2000)をデムナムカルボン酸(Mw=4000)に変えた以外は同様に処理を行いモールドとした。
<デムナムアリルエーテルによるモールド処理方法>
実験例1のデムナムオイル(Mw=2000)をデムナムアリルエーテル(Mw=4000)に変えた以外は同様に処理を行いモールドとした。
表面をフッ素系表面処理剤のオプツールDSX(登録商標)でフッ素コートした石英スライドグラスを比較例1とし、処理なし石英スライドガラス(対水接触角16°)を比較例2とした。
PAK-02(東洋合成化学社製)6.0gに光重合開始剤としてイルガキュア907(チバ・スペシャルティ・ケミカルズ社製)120mg(PAK-02に対して2.0質量%)を加え、遮光下回転ミキサーにて12時間攪拌し、モールド樹脂材料とした。
A:硬化後モールド樹脂材料の剥がれは観測されなかった
B:硬化後モールド樹脂材料の剥がれが観測された
a:モールドへの硬化後モールド樹脂材料の付着は観測されなかった
b:モールドへの硬化後モールド樹脂材料の付着が観測された
得られた結果を表2に示す。
2a、2b ロール
3 モールド
Claims (4)
- 離型層が形成された凹凸パターンを表面に有するモールドの前記離型層にフルオロポリエーテルを含む組成物を塗布する工程(1)、
前記モールドを、被転写物に押し付けて、前記凹凸パターンを転写する工程(2)、及び、
前記被転写物から前記モールドを離型して、転写パターンを有する前記被転写物を得る工程(3)
を含むことを特徴とする被転写物の製造方法。 - 前記被転写物が紫外線硬化性樹脂を含む請求項1記載の製造方法。
- 工程(2)において、前記モールドを前記被転写物に押し付けるとともに、前記被転写物に紫外線を照射する請求項1又は2記載の製造方法。
- 前記組成物は、更に、溶剤を含む請求項1、2又は3記載の製造方法。
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