Classifications

• • 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
  • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
  • G03F1/62—Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
  • C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
  • C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
  • C08G65/04—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 from cyclic ethers only
  • C08G65/22—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring
  • C08G65/223—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens
  • C08G65/226—Cyclic ethers having at least one atom other than carbon and hydrogen outside the ring containing halogens containing fluorine
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
• • 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
  • G03F7/004—Photosensitive materials
  • G03F7/0046—Photosensitive materials with perfluoro compounds, e.g. for dry lithography
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24273—Structurally defined web or sheet [e.g., overall dimension, etc.] including aperture
  • Y10T428/24322—Composite web or sheet
  • Y10T428/24331—Composite web or sheet including nonapertured component
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers

Definitions

• the present invention relates to a novel pellicle having excellent transparency and durability to short-wavelength light, and a novel fluoropolymer.
• a pellicle is an optical article in which a transparent thin film (hereinafter, referred to as a pellicle film) is mounted on a frame via an adhesive, and is mounted at a fixed distance on a surface of a mask pattern.
• Pellicles are required to have transparency, durability, and mechanical strength to light used in the exposure process.
• F excimer laser light is considered as a promising candidate for wiring processing with a minimum pattern size of 0.07 m or less.
• the adhesive for bonding the pellicle film and the frame has a similar problem due to stray light or reflected light of laser light.
• pellicle materials (1) a fluorine-containing resin containing an ether bond in a portion forming a main chain in a repeating structure and not containing a cyclic structure (see Patent Document 3), 2) A substantially linear fluoropolymer having a chain of carbon atoms as a main chain (see Patent Document 4). Proposed.
• Patent Document 1 JP-A-3-39963
• Patent Document 2 JP-A-3-67262
• Patent Document 3 JP 2001-255643 A
• Patent Document 4 JP 2001-330943 A
• the fluorinated resin described in (1) is actually oily or grease-like, and it is difficult to form a self-supporting film that can be used as a pellicle film. Even when a free-standing film is produced by producing a high-molecular-weight compound, there is a problem that the film is sagged or broken by heat generated in the exposure treatment because the glass transition point is low.
• the fluoropolymer described in (2) is transparent to F excimer laser light.
• the present inventors have found that a novel fluorine-containing polymer (I) having an etheric oxygen atom in the main chain and having a ring structure containing a carbon atom in the main chain has a sufficient effect on excimer laser light. It has been found that it has durability and transparency, and has heat resistance, mechanical strength, and film forming properties. It has also been found that the polymer is useful as a pellicle film and a pellicle adhesive.
• the present invention provides the following inventions.
• the pellicle film and Z or a polymer (I) used for the adhesive are composed of the following units: A pellicle that is a polymer that requires (1).
• Unit (1) a unit containing a fluorine atom bonded to a carbon atom, wherein the chain forming the polymer main chain in the unit is composed of a carbon atom and an etheric oxygen atom, and the carbon forming the main chain is A unit in which at least one of the atoms is a carbon atom forming a ring group and at least one of the etheric oxygen atoms forming the main chain is an oxygen atom not forming a ring group;
• Unit (1) is a unit represented by the following formula (A), a unit represented by the following formula (B), and a unit represented by the following formula (C)
• one to two of the carbon atoms forming the ring may be substituted with an etheric oxygen atom.
• One or more of the hydrogen atoms bonded to the ring-forming carbon atoms may be substituted with a fluorine atom or a monovalent fluorinated organic group, and two hydrogen atoms bonded to the ring-forming carbon atoms. May together form a divalent fluorinated organic group.
• E ⁇ E 2 , E 3 , E 4 each independently, a single bond or -CF—
• the etheric oxygen atom forming the main chain present in the unit (1) is an oxygen atom bonded to a carbon atom without bonding to a hydrogen atom. Pellicle described in somewhere.
• n 1 or 2
• 1 represents a fluorine atom or a trifluoromethyl group, and represents a fluorine atom or a perfluoroalkyl group having 115 carbon atoms.
• Unit (1) is a unit represented by the following formula (A2) or a unit represented by the following formula (A3)
• the polymer (I) is composed of one or more kinds of units selected from the unit force represented by the formula (A1) and the unit force represented by the formula (A3), or the formula (A1) One unit or more selected from units represented by (A3) and one or more units selected from units other than the unit represented by (A3)
• R 2 and R 3 each independently represent a hydrogen atom, a fluorine atom, or a saturated monovalent fluorine-containing organic group. However, At least one selected from R 2 and R 3 represents a fluorine atom or a saturated monovalent fluorine-containing organic group. Or Two groups selected from R 2 and R 3 together form a divalent fluorinated organic group, and the remaining one group represents a hydrogen atom, a fluorine atom, or a saturated monovalent fluorinated organic group.
• R 4 , R 5 and R 6 each independently represent a fluorine atom or a saturated monovalent fluorinated organic group. Or two groups selected from R 4 , R 5 , and R 6 together form a divalent fluorinated organic group, and the remaining one group is a fluorine atom or a saturated monovalent fluorinated organic group. Show.
• R 7 , R 8 , R 9 , and R 1G each independently represent a hydrogen atom, a fluorine atom, or a monovalent fluorine-containing organic group.
• Q 2 represents a divalent fluorine-containing organic group.
• the polymer (I) used for the pellicle film is a polymer having no functional group
• the polymer (I) used for the adhesive is a polymer having a functional group.
• An exposure treatment method using light having a wavelength of 200 nm or less in photolithography is characterized in that a pellicle described in any one of (1) and (1) and (10) is used. Exposure processing method.
• ⁇ 13> The exposure treatment method according to ⁇ 12>, wherein the exposure power is a fluorine gas excimer laser beam having a wavelength of 200 nm or less.
• a polymer containing a monomer unit represented by the following formula (A2) or a polymer represented by the following formula (A3) Polymer containing monomer units.
• the pellicle of the present invention is a pellicle using the novel fluorine-containing polymer (I), and has high transparency to light having an oscillation wavelength of 200 nm or less (hereinafter, short-wavelength light). And durable. Since the polymer (I) forms a film having excellent heat resistance and film forming properties, the obtained pellicle is a useful pellicle excellent in these properties.
• the compound represented by the formula (al) is also referred to as lig compound (al).
• the unit represented by formula (A1) is referred to as unit (A1).
• the unit in the polymer means the largest structural unit derived from the monomer formed by polymerization of the monomer (also referred to as ⁇ ⁇ ), and the unit in the present invention is a monomer directly formed by a polymerization reaction. It may be a unit or a unit formed by chemical transformation other than the polymerization reaction (also referred to as a structural repeating unit).
• a group in which one or more of the hydrogen atoms bonded to a carbon atom has been replaced with a fluorine atom is described by adding “polyfluoro” before the name of the group. Hydrogen atoms may or may not be present in the polyfluoro group. Groups in which virtually all of the hydrogen atoms bonded to carbon atoms have been replaced with fluorine atoms are indicated with a "perfluoro" prefix before the name of the group. There are substantially no hydrogen atoms present in the perfluorinated group.
• the present invention relates to a pellicle for exposure processing in which a pellicle film is adhered to a frame via an adhesive, wherein a specific unit (1) is added to the pellicle film and Z or the adhesive. Use the required polymer (I).
• the unit (1) is a unit having a fluorine atom bonded to a carbon atom (that is, an F atom having a C-F structure).
• the carbon atom to which the fluorine atom is bonded may be a carbon atom forming a polymer main chain or a carbon atom other than the carbon atom.
• the polymer (I) is a fluorine-containing polymer having a C-F structure as an essential component.
• the polymer main chain refers to the longest chain in the polymer molecule.
• the chain forming the polymer main chain in the unit (1) refers to a chain having the smallest number of atoms among the chains separating the bonds extending from the monomer unit. If two or more chains having the same number of atoms exist, all of them become the polymer main chain.
• the chains forming the polymer main chain in the unit (1) are an etheric oxygen atom (ie, O-) and a carbon atom. At least one of the etheric oxygen atoms forming the main chain is an oxygen atom which does not form a ring group. Due to the presence of an etheric oxygen atom which does not form a ring group, the polymer (I) of the present invention has properties such as transparency and durability to light used for exposure treatment (particularly, ultraviolet light of 200 ⁇ m or less). Can be high. [0051] At least one carbon atom forming the main chain of the polymer (I) is a carbon atom forming a ring group.
• All of the carbon atoms forming the main chain may be carbon atoms forming a ring group, or some may be carbon atoms forming a ring group, and the remaining may be carbon atoms forming no ring group. Become good. In the present invention, it is preferable that one or two of the carbon atoms forming the main chain are also the carbon atoms forming the ring group.
• the ring group containing the main chain is preferably a 5- or 6-membered ring group described below. Since the carbon atoms forming the polymer main chain also become the carbon atoms forming the ring group, a part of the polymer main chain is included in the ring group.
• the presence of the ring group containing the polymer main chain suppresses crystallization of the polymer (I) and increases the transparency of the polymer (I).
• the ring group can increase the glass transition temperature to suppress the molecular motion of the polymer main chain.
• a hydrogen atom is present in the polymer (I)! /, Or! /.
• a hydrogen atom is present in the polymer (I)
• it is preferably a hydrogen atom bonded to a tertiary carbon atom.
• a carbon atom is bonded to the tertiary carbon atom (hereinafter, the carbon atom is connected to another carbon atom!)
• a hydrogen atom is not bonded to the other carbon atom.
• a fluorine atom or a perfluorinated organic group is bonded to the other carbon atoms.
• the hydrogen atom that can be present in the polymer (I) is a hydrogen atom bonded to a tertiary carbon atom
• the bonding of the hydrogen atom and the carbon atom is strengthened, and the extraction of the hydrogen atom during exposure can be prevented.
• the presence of the hydrogen atom breaks the hyperconjugation of the lone pair of electrons of the fluorine atom, thereby producing a polymer (I) exhibiting high transparency, high transparency and light resistance.
• the etheric oxygen atom in the polymer (I) is preferably an oxygen atom bonded to a carbon atom to which a hydrogen atom is not bonded, and particularly the etheric oxygen atom present in the main chain is hydrogen. It is preferably an oxygen atom bonded to a carbon atom to which the atom is not bonded.
• the etheric oxygen atom in the unit (1) is preferably an oxygen atom bonded to a carbon atom to which a hydrogen atom is not bonded.
• the etheric oxygen atom forming the main chain is not bonded to a hydrogen atom.
• an oxygen atom bonded to a carbon atom Preferably an oxygen atom bonded to a carbon atom.
• the carbon atom bonded to the etheric oxygen atom is preferably a carbon atom replaced by a fluorine atom or a divalent fluorinated organic group. This is because when a carbon atom to which an etheric oxygen atom is bonded is replaced by a fluorine atom or a fluorine-containing organic group, Since the lone pair is stabilized, the polymer (I) can exhibit excellent light resistance to ultraviolet light having a short wavelength.
• Examples of the unit (1) essential to the polymer (I) in the present invention include the following unit (A), the following unit (B), the following unit (C), or the following unit (D): No.
• the unit (1) is preferably a unit represented by the following formula (A), a unit represented by the following formula (C), or a unit represented by the following formula (D).
• one to two of the carbon atoms forming the ring may be replaced by an etheric oxygen atom.
• One or more of the hydrogen atoms bonded to the ring-forming carbon atoms may be substituted with a fluorine atom or a monovalent fluorinated organic group, or two hydrogen atoms bonded to the ring-forming carbon atoms. May together form a divalent fluorinated organic group.
• the monovalent fluorine-containing organic group a perfluoroalkyl group or a perfluoroalkyl group containing an etheric oxygen atom, which has a carbon number of 116, is particularly preferable.
• the divalent fluorinated organic group those having 2 to 6 carbon atoms, which are more preferable than perfluoroalkylene groups and perfluoroalkylene groups containing etheric oxygen atoms, are particularly preferable.
• the branched portion may be a perfluoroalkyl group or a perfluoroalkyl group. It is preferably a alkoxy group or a perfluoro (alkoxyalkyl) group, particularly preferably a group having 114 carbon atoms.
• ⁇ 2, ⁇ 3, ⁇ 4 each independently, Omicron or CF O
• Each of E 1 to E 4 being a single bond means that a bond extending from the ring group is directly bonded to another unit or terminal structure.
• E 1 — E 4 is a single bond and K 1 -K 4 is -0- are preferred.
• unit (A) and the unit (D) include the following units in addition to the unit (A1) described below.
• Examples of the unit (1) other than the above include the following unit (El) and a monomer unit obtained by polymerizing the following compound (e2).
• a polymerization reaction between CF and CF groups may also occur.
• the cyclic group essential for the unit (1) of the present invention is preferably a 5-membered or 6-membered ring group preferably containing these ether-containing oxygen atoms (1o-). Particularly preferred, and especially preferred are those ring groups that are saturated. O— in the ring group preferably exists as an oxygen atom without forming a polymer main chain. Further, it is preferable that the unit (1) has one essential ring group, and it is preferable that the etheric oxygen atom forming the main chain is one.
• the following unit (A1) the following unit (A3): The following units (A1) in which one or more units are preferred are particularly preferred.
• the unit (A1) the following unit (A3):
• the polymer having at least one selected unit is a novel polymer containing an ether bond and a saturated ring structure in the polymer main chain.
• n is 1 or 2, and is preferably 1 from the viewpoint of the stability of the ring structure.
• R F1 is a fluorine atom or a trifluoromethyl group, and from the viewpoint of availability of raw materials, a fluorine atom is preferred!
• R F2 is a fluorine atom or a perfluoroalkyl group having 115 carbon atoms. When R F2 is a perfluoroalkyl group, it may be linear or branched.
• R F2 is a fluorine atom, triflate Ruo Russia methyl or signaling fluorine atom preferred penta full O Roe ethyl group, it is particularly preferred.
• unit (A1) examples include a unit represented by the following formula.
• the polymer (I) in the present invention is a polymer having the unit (1) as an essential component. Even if the polymer (I) is a polymer composed of only one or more units (1), the unit (1) A polymer containing a unit other than the unit (1) (hereinafter, referred to as another unit) together with at least one of the above is also preferable.
• the arrangement of the units includes a block shape, a graft shape, and a random shape. Among these, from the viewpoint of the usefulness of the polymer (I), the arrangement of the units is preferably random.
• the polymer (I) is a polymer essentially including one or more units whose units (A1) and (A3) are also selected, a polymer substantially having the unit power, or One or more units and the other Unit force
• a polymer having unit (A1) force, a polymer having unit (A2) force, or a polymer comprising unit (A3) is preferable.
• the latter polymer (I) is composed of a polymer having a strength equal to one kind of the unit (A1) and one or more kinds selected from the other units, and a unit (A2) and one or more kinds selected from the other unit strengths.
• a polymer or a polymer having at least one unit selected from the unit (A3) and another unit force is preferable.
• the ratio of the unit (1) to all units of the polymer (I) can be appropriately changed depending on the use of the polymer (I).
• the proportion of units in the polymer (1) is usually, each 0.5 0001- 100 mole 0/0 preferably instrument 0. 01- 100 mole 0/0 are particularly preferred.
• the proportion of other units, 0 99. 9999 mole 0/0 force transducer preferred, 0- 99.99 mole 0/0 are particularly preferred.
• the unit (A1) - proportion of the units (A3) is preferably 1 one 9 7 mole 0/0 device proportion of 5 95 mole 0/0 are particularly preferred instrument other units preferably are 3- 99 mole 0/0 device 5 95 mol% is particularly preferred.
• the mass average molecular weight of the polymer (I) is particularly preferably 500 to 10000 force, and 500 to 500,000 force is particularly preferable.
• the weight average molecular weights of the polymer (A1), the polymer (A2), and the polymer (A3) are each 500 to 1,000,000.
• the other units are particularly preferably the following units (Ml) to (M5), which are preferably units having a fluorine atom as an essential unit.
• R 1 —R 1C) and Q 2 have the same meaning as described above. Preferred embodiments of these groups will be described later.
• the method for producing the polymer (I) in the present invention includes a method by a polymerization reaction of a monomer (method 1), a method by a combination of a polymerization reaction of a monomer and a reaction other than the polymerization reaction (method 2), or a polymerization reaction It is preferable to use the method 1 or the method 2 in which a method using a reaction other than (Method 3) is preferred.
• Method 2 there is a method in which a monomer having a structure that can be converted by a chemical conversion other than the polymerization reaction is obtained, and the monomer is polymerized, and then a chemical conversion other than the polymerization reaction is performed.
• Method 3 a method for producing a polymer containing the unit (A1) by fluorinating a polymer having a carbon skeleton corresponding to the unit (A1) and a hydrogen atom bonded to a carbon atom of the carbon skeleton. Is mentioned.
• the production method is as follows: A method of polymerizing one or more of (al) (where n, R F1 and R F2 have the same meanings as described above) is particularly preferred.
• the production method is a method of polymerizing the following compound (a2), which is preferable in method 1. Is particularly preferred.
• the production method is a method of polymerizing the following compound (a3), which is preferred in method 1. Is particularly preferred. The method for obtaining the compound (a1) will be described later. [0074] [Formula 17]
• Method 1 or Method 2 is preferable. These methods can be appropriately changed depending on the structure of other units.
• the method for producing the polymer (A1) includes a method of polymerizing the compound (al), a compound (al), and a monomer copolymerizable with the compound (al) (hereinafter, the monomer is referred to as a comonomer). Or a method in which a polymer obtained by polymerizing the compound (al) and a comonomer is then chemically converted.
• the comonomer is a monomer other than the compound (al) copolymerized with the compound (al).
• the comonomer may be a compound containing a fluorine atom or a compound containing no fluorine atom, from the viewpoint of the usefulness of the polymer (A1) and the polymerization of the compound (al). From the viewpoint of properties, the compound is preferably a compound containing a fluorine atom.
• the comonomer which can be used for the production of the polymer (A1) -polymer (A3) includes the following compound (ml) which is a comonomer capable of directly forming the unit (Ml)-(M5) by a polymerization reaction. — (M3) is preferred! / ,.
• R 1 —R 1C> and Q 2 have the same meaning as described above.
• R 1 —R 1G is a monovalent fluorine-containing organic group
• the group is a monovalent group having at least one fluorine atom and at least one carbon atom!
• a saturated monovalent fluorinated organic group which may be a saturated group or an unsaturated group, is preferred.
• R 1 — R 1C> are each linear It may have a structure or a branched structure.
• the saturated monovalent fluorine-containing organic group a polyfluoroalkyl group having 16 carbon atoms, which is preferably a polyfluoroalkyl group, is particularly preferable, and a perfluoroalkyl group having 116 carbon atoms is particularly preferable. Trifluoromethyl and pentafluoroethyl are even more preferred!
• R 1 —R 1G and Q 2 are each a divalent fluorine-containing organic group
• the group is a divalent organic group having one or more fluorine atoms and one or more carbon atoms.
• a saturated divalent fluorine-containing organic group which may be a saturated group or an unsaturated group, is preferred.
• the saturated divalent fluorine-containing organic group those groups having 2 to 6 carbon atoms, which are preferably a perfluoroalkylene group containing an etheric oxygen atom, are particularly preferred.
• the branched portion is preferably a trifluoromethyl group or a pentafluoroethyl group. ,.
• the compound (ml) is a comonomer that forms a unit (Ml) by a polymerization reaction.
• the compound (ml) a compound having 2 or 3 carbon atoms (for example, butyl fluoride, 1,2-difluoroethylene, bi-lidene fluoride, trifluoroethylene, etc.), the following compound (ml) —1) and the compound (ml-2), and preferably bi-lidene fluoride, butyl fluoride, trifluoroethylene, the compound (ml-1) and the compound (ml-2).
• the unit where the compound (ml-1) is polymerized is the following unit (Ml-1), and the unit where the compound (ml-2) is polymerized is the following unit (Ml-2).
• the compound (m2) is a comonomer that forms a unit (M2) by a polymerization reaction.
• the compound (m2) include perfluoroolefins such as tetrafluoroethylene and hexafluoropropylene; perfluoro (methyl vinyl ether), Alkyl monobutyl ethers); cyclic compounds such as the following compound (m2-1), the following compound (m2-2), and the following compound (m2-3) Mer; c etc.
• R 11 to R 17 each independently represent a fluorine atom or a saturated monovalent fluorinated organic group.
• R 11 and R 12 may together form a divalent fluorinated organic group (Q 1 ).
• Q 3 represents an etheric oxygen atom or a difluoromethylene group.
• Q 1 when R 11 and R 12 in formula (m @ 2-l) to form a bivalent fluorinated organic group (Q 1), it heteroatom (etheric oxygen atom to the carbon-carbon-carbon bond
• Preferable is a fluorinated alkylene group containing two or more structures in which U) is inserted.
• the group may have a straight-chain structure or a branched structure having a perfluoroalkyl group as a branch portion.
• the compound (m2-1) includes the following compounds, and is preferably compound (m2-10), compound (m2-11), compound (m2-12), or compound (m2-13).
• R 17 , n, R F1 and R F2 have the same meaning as described above.
• the compound (m2), tetrafluoroethylene, the compound (m2-1), or the tetrafluoroethylene preferred by the compound (m2-3), the compound (m2-10), the compound (m2) m2-11), the compound (m2-12), the compound (m2-13) or the compound (m2-30) are particularly preferred.
• Specific examples of the monomer unit derived from the preferred compound (m2) include CF
• M2-10 the following units (M2-11), the following units (M2-12), the following units (M2-13), and the following units (M2-30).
• the compound (m3) is a comonomer capable of forming each of the above-mentioned units (M3) (M5) by a polymerization reaction.
• R 7 to R 9 in the units (M3) to (M5) are each independently preferably a hydrogen atom or a fluorine atom.
• R 9 is preferably a hydrogen atom or a fluorine atom
• R 9 is a hydrogen atom or a fluorine atom.
• R 1G is particularly preferably a fluorine atom which is preferably a fluorine atom, a trifluoromethyl group or a pentafluoroethyl group.
• Q 2 is preferably a perfluoroalkylene group which may contain an etheric oxygen atom having a total carbon number of 110.
• the carbon atom to which R 9 is bonded, Q 2 when the distance between the shortest atom of atomic Q 2 'connecting the carbon atom to which R 1G is bound distance is 2-4 atom.
• Q 2 preferably has a linear structure or a branched structure.
• Q 2 are pel full O b alkylene group having a carbon number of 1 one 3 having a terminal ether oxygen atom bonded to the carbon atom to which R 1C> are attached, having both ends etheric oxygen atom
• a perfluoroalkylene group having 1 to 2 carbon atoms or a perfluoroalkylene group having 1 to 4 carbon atoms is preferable.
• these groups have a branch, those groups in which the branched portion is a perfluoroalkyl group having 13 to 13 carbon atoms (a trifluoromethyl group is preferable! / ⁇ ) are preferable.
• Specific examples of the compound (m3) include the following compound (m3-1), the following compound (m3-2), and the following compound (m3-3).
• Q 4 , Q 5 and Q 6 each independently represent a perfluoroalkylene group having 13 to 13 carbon atoms.
• R 18 , R 19 and R 2G each independently represent a fluorine atom or a hydrogen atom.
• Specific examples of the compound (m3-1) include the following compounds.
• Specific examples of the compound (m3-3) include the following compounds.
• CH CHOC (CF 3)
• the compound (m3) the compound (m3-1) or the compound (m3-20), the compound (m3-21), or the compound (m3-22), which is preferred by the compound (m3-2), is used. Particularly preferred.
• These monomers form a unit having an essential cyclic structure by a cyclopolymerization reaction.
• specific examples of the monomer unit (M3) derived from the compound (m3) include a unit formed by cyclopolymerization of the compound (m3).
• the following three units may be mentioned as units obtained by cyclopolymerization of the compound (m3-22).
• the polymer (A2) and the polymer (A3) can be produced in the same manner as the polymer (A1) by polymerizing the corresponding compound (a2) and compound (a3).
• the compound (a2) is copolymerized with another compound, the same monomer as the monomer copolymerizable with the compound (al) can be used.
• the compound (al) is preferably obtained by a method represented by the following formula.
• n represents 1 or 2.
• R 3 represents a hydrogen atom, a fluorine atom, or a methyl group.
• R 31 represents a hydrogen atom, a fluorine atom, or an alkyl group having 115 carbon atoms.
• R F may have an etheric oxygen atom, represents a perfluoroalkyl group, and is preferably a perfluoroalkyl group having an etheric oxygen atom.
• one -C (OH) group is converted back to a keto group by a dehydration reaction.
• R 17 is a fluorine atom in the compound (m2-10) (m2- 10F) were used compound obtained by the above method of (al), the following production route (Where n, R F1 and R F2 have the same meanings as described above).
• R F COF represents a perfluoroalkyl group which may contain an etheric oxygen atom.
• FC CF FC one ⁇
• the polymer (I) in the present invention the polymer (Al) — (A3) is particularly preferable,
• polymers (A1)-(A3) are homopolymers in which only one compound selected from compounds (al)-(a3) is selected, and copolymers of the selected one compound and comonomer. Is preferred. Particularly preferred is a homopolymer in which only one kind of the compound (al) is used or a copolymer of the compound (a1) and a comonomer.
• a copolymer preferred examples are compound (al) and bi-lidene fluoride, compound (al) and vinyl fluoride, compound (al) and trifluoroethylene, compound (al) And compound (m1-1), compound (al) and tetrafluoroethylene, compound (al) and compound (m2-10), compound (al) and compound (m2-11), compound (al) And a copolymer obtained by copolymerizing the compound (m2-12), the compound (al) and the compound (m2-13), and the compound (al) and the compound (m2-30).
• a copolymer having a unit force obtained by cyclopolymerizing the unit of the compound (al) and the compound (m3-20), and a copolymer having a unit force obtained by cyclopolymerizing the unit of the compound (al) and the compound (m3-21) A copolymer in which the unit force of the compound (al) and the compound (m3-22) is also cyclopolymerized, or a copolymer in which the unit of the compound (al) and the compound (m3-23) are also a cyclopolymerized unit force Polymers are also included.
• the method for obtaining the polymer (A1) by the polymerization reaction of the compound (al) and the method for obtaining the polymer (A2) by the polymerization reaction of the compound (a2) in the present invention are based on novel findings. . That is, CF COCF, which is a fluorine-containing acyclic ketone conjugate, and bilidene fluoride are radicals.
• CFO (CF) Contains the following unit (CI) by the cyclopolymerization reaction of the compound represented by COCF
• a method for producing a polymer and a method for producing a polymer containing the unit (A3) by polymerizing the compound (a3) are exemplified.
• the method of obtaining a polymer by polymerizing the compound (a3) is a novel finding.
• a polymer containing the following unit (y7) is obtained, and then a polymer containing the following unit (y8) is obtained by esterification.
• the polymer is fluorinated by a technique such as liquid phase fluorination to obtain a polymer containing the following unit (y9), and the polymer is polymerized containing the unit (A4) by a method such as a fluorination treatment described later.
• RF has the same meaning as described above.
• the polymerization reaction in Method 1 or 2 can be carried out by ionic polymerization such as aion polymerization / cationic polymerization or radical polymerization, and is preferably carried out by radical polymerization.
• examples of the polymerization method include bulk polymerization, suspension polymerization, and solution polymerization.
• the polymerization reaction of compound (a3) is preferably performed by ion polymerization.
• Radical polymerization is preferably performed using a polymerization initiator.
• the polymerization initiator is selected from the viewpoint of avoiding the formation of a CH-chain derived from the polymerization initiator at a terminal group of the polymer.
• a perfluoro compound having a polyether structure is preferably used.
• the polymerization initiator include the following compounds. However, in the following formula, the structure of the perfluoroalkyl group portion having 3 or more carbon atoms may be a straight-chain structure or a branched structure.
• the polymerization reaction is preferably performed in the presence of a solvent from the viewpoint of suppressing the decomposition of the monomer such as the compound (al) due to abnormal polymerization or rapid heat generation.
• a solvent from the viewpoint of suppressing the decomposition of the monomer such as the compound (al) due to abnormal polymerization or rapid heat generation.
• the fluorine-containing monomer such as the compound (al)
• an aprotic organic solvent from the viewpoint that chlorine atoms in the solvent remaining in the polymer (I) impair the durability of the polymer (I) to short-wavelength light, an aprotic organic solvent containing no chlorine atom Organic solvents are preferred.
• aprotic organic solvents include polyfluoroalkanes such as perfluorooctane, perfluorodecane, 2H, 3H-perfluoropentane, and 1H-perfluorohexane. ; Methyl perfluoroisopropyl ether, methyl perfluorobutyl ether
• polyfluoroethers such as methinole (hexanolene hexinolemethinole) ether, methinole dinolefnoroleoctynoleatel, and ethyl perfluorobutyl ether.
• the reaction temperature in the polymerization is preferably from -10 ° C to + 150 ° C, and particularly preferably from 0 ° C to + 120 ° C.
• the reaction temperature is too high, the arrangement of the monomer units tends to be block-shaped.
• the reaction temperature is too low, the yield of the polymer tends to be extremely reduced.
• the reaction pressure in the polymerization may be any of reduced pressure, increased pressure, and atmospheric pressure.
• atmospheric pressure-1 MPa gauge pressure
• atmospheric pressure-IMPa gauge pressure
• a functional group may be introduced into the polymer (I) in the present invention.
• the functional groups include a carboxyl group, a sulfonic acid group, an alkoxycarbyl group, an acyloxy group, an alcohol group, a hydrolyzable silyl group, a hydroxyl group, a maleimide group, an amino group, a cyano group, and an isocyanate. Groups.
• the polymer (I) is used as an adhesive for a pellicle or the like, it is preferable to introduce a functional group into the polymer (I).
• the ratio of the functional group in the polymer (I) is 0.0001-0.0010 monole / g force! / ⁇ .
• a method for introducing a functional group into the polymer (I) a method of polymerizing a comonomer having a functional group (according to the above method 1), or a method using a comonomer having a group capable of introducing a functional group is used. And a method of introducing a functional group after the polymerization reaction (according to the above-mentioned method 2). These methods can be carried out according to known methods (for example, JP-A-4-189880, JP-A-4-226177, JP-A-6-220232, etc .;).
• Method 4 A method of copolymerizing the compound (al) with a comonomer having a functional group.
• Method 5 A method of converting a functional group derived from a polymerization initiator and Z or a chain transfer agent, or a functional group which can be derived from the functional group into a desired functional group.
• Method 6 A method in which the compound (al) is copolymerized with a comonomer containing a group that can be converted into a functional group, and the group that is converted into a functional group is converted.
• Method 7 A method of subjecting a polymer to a high temperature treatment in an oxygen gas atmosphere to partially decompose and decompose a side chain and Z or a terminal group into a carboxyl group.
• method 5 or method 7 is particularly preferable because the reaction operation is easy.
• examples of the group that can be converted into a functional group include an alkoxycarbol group. This group can be converted to a carboxyl group by a hydrolysis reaction or the like.
• the polymer (I) When the polymer (I) is produced by a polymerization reaction, it is preferable to convert the terminal group of the polymer chain by performing a process of contacting with fluorine gas.
• the temperature at which the treatment is carried out is preferably 250 ° C or lower, particularly preferably 240 ° C or lower, particularly preferably 50 ° C or lower.
• the treatment may be performed on the polymer (I) in a solid state or on the polymer (I) in a solution state. By this treatment, the polymer (I) becomes a more durable polymer in which an unsuitable polymer chain terminal or unsaturated bond which can be generated by polymerization is substituted and Z or added by a fluorine atom.
• the terminal group can be converted into a —CF CF group and a Z or —CF CF H group.
• fluorine gas when introducing a functional group into the polymer (I), it is preferable not to perform the treatment with fluorine gas.
• the polymer (I) of the present invention is a novel conjugate.
• the polymer (I) can be oily or liquid depending on the molecular weight, structure, or use conditions. Such a polymer can also be used as an oil when performing an exposure treatment by an immersion exposure method (an immersion method).
• an immersion exposure method an immersion method
• the polymer (I) can be supplied and used between a projection lens and a resist-coated wafer. It can also be used for exposure treatment using ultraviolet light having a wavelength of 200 nm or less.
• the molecular weight of the polymer (I) which can be used for the immersion exposure method is preferably a polymer having a force of 7000 or less, which can be appropriately changed depending on the structure of other units, and particularly preferably a polymer having a molecular weight of 500 to 7000.
• the polymer (I) in the present invention can be used as a solution, usually in a solid state or in a solid state.
• the polymer (I) of the present invention is in a solid state, since the saturated ring structure based on the unit (A1) is bulky, the motion of the polymer main chain is restricted, and the polymer may have a high glass transition temperature. .
• the polymer (I) in the present invention has high transparency and durability against all rays, particularly short wavelength light.
• the polymer (I) in the present invention is excellent in low refractive index, low dielectric constant, low water absorption, low surface energy, heat resistance, and chemical resistance. Therefore, the polymer (I) can be usefully used as a functional material in a field where these properties are required.
• Examples of uses of the coating film that also forms the polymer (I) force include, besides the pellicle film described below, an ophthalmic lens, an optical lens, an optical cell, a DVD disk, a photodiode, a show window II, and a showcase.
• Solar cells surface protective films for various displays (for example, PDP, LCD, FED, organic EL, and projection TV), and protective films for semiconductor devices (for example, interlayer insulating films, buffer coat films, noisy film films, Examples include a line shielding film, a device sealing material, an interlayer insulating film for a high-density mounting substrate, and a moisture-proof film for a high-frequency device (for example, a moisture-proof film for an RF circuit device, a GaAs device, an InP device, and the like).
• protective films for semiconductor devices for example, interlayer insulating films, buffer coat films, noisy film films, Examples include a line shielding film, a device sealing material, an interlayer insulating film for a high-density mounting substrate, and a moisture-proof film for a high-frequency device (for example, a moisture-proof film for an RF circuit device, a GaAs device, an InP device, and the like).
• Polymer (I) Force Examples of uses of the molded article include a core material or a clad material of an optical fiber, a core material or a clad material of an optical waveguide, and the like.
• the polymer (I) may be used as a film or a film obtained by combining the polymer (I) with another material. It is also useful as lum (for example, a film laminated with a thermoplastic resin such as polyimide). The polymer (I) is also useful as a water / oil repellent, a semiconductor adhesive (for example, for LOC, die bonding, etc.), and an optical adhesive.
• a film or a film obtained by combining the polymer (I) with another material It is also useful as lum (for example, a film laminated with a thermoplastic resin such as polyimide).
• the polymer (I) is also useful as a water / oil repellent, a semiconductor adhesive (for example, for LOC, die bonding, etc.), and an optical adhesive.
• the polymer (I) may be used as a solution composition in which the polymer (I) is dissolved in an organic solvent!
• the organic solvent it is preferable to use one or more kinds of fluorine-containing solvents.
• the amount of the polymer (I) in the composition is preferably 0.1 to 25% by mass relative to the organic solvent, from the viewpoint of compatibility with the organic solvent. From the viewpoints of the film thickness of the coating film for the above application and the stability of the solution composition, it is particularly preferred that the content is 5 to 15% by mass.
• the organic solvent that can be used for forming the solution composition is not particularly limited, and may be a polymer.
• the fluorinated organic solvent having high solubility of (I) is preferable.
• Examples of the fluorinated organic solvent include the following.
• Polyfluoroaromatic compounds such as perfluorobenzene, pentafluorobenzene, and 1,3-bis (trifluoromethyl) benzene.
• Polyfluoro (trialkylamine) compounds such as perfluoro (tributylamine) and perfluoro mouth (tripropylamine).
• Polyfluorocycloalkane compounds such as perfluorodecalin and perfluorocyclohexane.
• Polyfluoro cyclic ether conjugates such as perfluoro (2-butyltetrahydrofuran).
• Polyfluoroalkanes such as perfluorooctane, perfluorodecane, 2H, 3H-perfluoropentane and 1H perfluorohexane.
• Polyfluoroethers such as ether.
• the solution composition of the present invention is also useful as a surface treatment agent for imparting the properties of the polymer (I) to the substrate surface.
• a treatment method when the solution composition is used as a surface treatment agent a method in which the solution composition is applied to a substrate and then dried is preferable.
• a method for applying the solution composition to the substrate a known method can be adopted, and a roll coating method, a casting method, a dipping method, a spin coating method, a water casting method, a die coating method, and a Langmuir method are used. Examples include a jet method. Of these methods, the pellicle membrane From the viewpoint of strict film thickness formation, it is preferable to employ a spin coating method.
• the substrate is preferably a substrate having a flat surface (silicon wafer, quartz, etc.).
• the polymer (I), particularly the polymer (A1) in the present invention can be particularly usefully used as a material for a pellicle.
• the pellicle material include a pellicle film and Z or an adhesive in a pellicle for exposure processing in which a pellicle film is adhered to a frame via an adhesive. That is, the present invention relates to a pellicle for exposure treatment in which a pellicle film is bonded to a frame via an adhesive, wherein the pellicle film and Z or the pellicle in which the adhesive is required to be a polymer (I). provide.
• Pellicles using the polymer (I) for the pellicle film include a pellicle film having the polymer (I) as an essential component and a pellicle having a frame strength.
• the pellicle in which the polymer (I) is applied to the adhesive is a pellicle in which the pellicle film is adhered to the frame via an adhesive that requires the polymer (I).
• the polymer (I) it is preferable to use the polymer (I) having no functional group from the viewpoint of transparency and durability against short-wavelength light.
• the polymer (I) is used for the adhesive, the polymer having a functional group is preferred from the viewpoint of adhesiveness.
• (I) a carboxyl group having good adhesion at low temperatures and having storage stability is preferable.
• the adhesive it is preferable to use a composition comprising the polymer (I) having a functional group and the above-mentioned fluorinated organic solvent. Further, a silane-based, epoxy-based, titanium-based, aluminum-based coupling agent may be further added to the composition in order to improve adhesiveness.
• the polymer (I) having no functional group is used as the adhesive, the pellicle film and the frame can be firmly adhered by blending the coupling agent.
• a material for forming the frame a material having durability against short-wavelength light used for exposure treatment, which is preferably used for a metal material in terms of strength, is particularly preferable.
• the material include aluminum, 18-8 stainless steel, nickel, synthetic quartz, calcium fluoride, and barium fluoride.
• Aluminum or synthetic quartz is preferred as the material from the viewpoints of environmental resistance, strength, and specific gravity.
• a known method can be applied to a method for producing a pellicle in which the polymer (I) is a pellicle film.
• the composition is applied to a substrate.
• the solvent is volatilized to obtain a treated substrate having the polymer (I) thin film formed on the substrate.
• an adhesive is applied to the frame, and the frame is heated (preferably at 100 to 200 ° C.).
• a method of obtaining a pellicle by bonding the treated base material to the surface of the frame to which the adhesive has been applied, and then peeling the base material from the treated base material can be used.
• the thickness of the pellicle film is usually preferably 0.01 to 50111.
• the polymer (I) for both the pellicle film and the adhesive, but it is also possible to use a material other than the polymer (I) for one.
• the polymer film other than the polymer (I) and the adhesive other than the polymer (I) include materials described in JP-A-2001-330943 and WO2001 / 37044.
• propylene Z-vinylidene fluoride Z-tetrafluoroethylene copolymer for example, propylene Z-vinylidene fluoride Z-tetrafluoroethylene copolymer, bi-lidene fluoride Z-hexafluoropropylene copolymer, and bi-lidene fluoride Or a polymer obtained by introducing a functional group into the selected polymer by the method described above.
• the pellicle of the present invention can be used as a pellicle for exposure processing using various oscillation wavelengths as a light source. Particularly preferred as a pellicle for exposure processing using short-wavelength light is particularly preferred as a pellicle for exposure processing using F2 excimer laser light.
• the present invention also provides an exposure processing method for performing exposure processing using the pellicle.
• the polymer (I) in the present invention has high transparency to short-wavelength light. Although the reason is not clear, it is considered that the polymer (I) contains an oxygen atom based on an ether bond in the main chain and a cyclic group structure containing the oxygen atom, and cannot form a long electronic conjugate in the main chain. Can be Further, the polymer (I) in the present invention has high durability against short-wavelength light. Although the reason is not clear, the polymer (I) contains an oxygen atom based on an ether bond in the main chain, and the electronic conjugation of the main chain is disrupted. Is considered to be a polymer containing the ring group structure with a small distortion in the main chain and hardly cleaving the main chain.
• M is the mass average molecular weight
• M is the number average molecular weight
• T glass transition point
• T the gel permeation
• M and M were measured by the GPC method.
• the measurement method is described in JP-A-2000-74892 w n
• a mixed solution with H (volume ratio: 99: 1) was used as an analytical column, and a column in which two P Lgel MIXED-C (7.5 mm in diameter, 30 cm in length) manufactured by Polymer Laboratories were connected in series was used.
• Polymethyl methacrylate having a molecular weight of 1000-2,000,000 (manufactured by Polymer Laboratories) was used.
• the mobile phase flow rate was 1. Oml / min and the column temperature was 37 ° C.
• An evaporative light scattering detector was used as the detector.
• M and M are molecular weights in terms of polymethyl methacrylate
• Example 11 Example of synthesizing a mixture of compound (y2-1) and compound (z2-1)
• the internal liquid was circulated by the pump (flow rate 300 LZh) to obtain a circulating liquid.
• a heat exchanger was installed in a part of the circulation line extending from the pump discharge side to the autoclave top plate to maintain the temperature of the circulating fluid at 25 ° C.
• An indicator (stainless steel) was installed in the middle of the circulation line so that gas could be sucked into the circulating fluid.
• a raw material supply pipe and a discharge pipe are installed between the injector and the pump so that the mixture obtained in Example 11 as a raw material and the crude reaction liquid generated by the reaction can be taken in and out of the autoclave at any time. I made it.
• Example 1-1 Nitrogen gas was blown into the autoclave through the injector for 2.0 hours, and then fluorine gas diluted to 50% with nitrogen gas (hereinafter referred to as 50% diluted gas) was supplied at a flow rate of 113.2 LZh for 1.5 hours. I blew it. Next, the mixture obtained in Example 1-1 was continuously supplied from the raw material supply pipe into the circulating liquid without diluting (50 gZh in average supply amount) while blowing 50% diluted fluorine gas at the same flow rate. 4800g of raw materials were charged.
• 50% diluted gas nitrogen gas
• the crude reaction solution was analyzed by 19 F-NMR. As a result, the yield of compound (y3-1) from compound (y2-1) was 57.5%, and compound (z2-1) was more powerful than compound (z3-1). — The yield of 1) is 81%, and the rest is confirmed to be mainly composed of F (CF) OCF (CF) CF OCF (CF) COF as circulating fluid. I accepted. The obtained crude reaction solution was used for the next reaction as it was.
• the reaction crude liquid (3575.6 g) obtained in Example 12 was charged into a round-bottom flask (2 L in internal volume) together with KF powder (15.7 g). At the top of the round-bottom flask, a cooler whose temperature was controlled at 20 ° C. and a round-bottom flask cooled to 78 ° C. were connected in series. Next, the round bottom flask charged with the reaction crude liquid was heated to 90 ° C. for 5 hours in an oil bath with vigorous stirring, and the fraction was collected in a round bottom flask cooled to 78 ° C.
• the temperature of the oil bath was set to 100 ° C, and the mixture was heated and stirred for about 1 hour to complete the thermal decomposition. The obtained fraction was directly used for the next reaction.
• the compound (Z4-COOH) was 75% based on the compound (z4-l). The obtained reaction solution was used as it was in the next reaction.
• HO CH CH Cl (40.5 g) was slowly added dropwise to the round bottom flask containing the product obtained in Example 1-3 while cooling to ⁇ 78 ° C. and stirring. Drop all of HOCH CH C1 and stir
• a high-pressure mercury lamp was placed in the center, and a nitrogen gas was replaced in a flask (internal volume 2 L) equipped with a dry ice condenser, a chlorine gas inlet, and a thermocouple thermometer in the side tube, and the flask was obtained in Example 2-1.
• a colorless and transparent liquid (76 g) and R-113 (540 g) were charged.
• the temperature inside the flask was maintained at 10 ° C and the mercury lamp was turned on.
• the temperature in the flask was set to 30 ° C., and the introduction of chlorine gas into the flask was started slowly.
• the flask was then heated and kept constant at 45-50 ° C. Unreacted chlorine gas was refluxed into the flask by a dry ice condenser to conduct the reaction. The reaction was terminated when the consumption of chlorine ceased, and the total amount of chlorine charged in the flask was 90.5 g.
• Example 2-2 A dry four-necked flask equipped with a reflux condenser, stirrer, dropping funnel, and thermocouple thermometer was charged, charged with antimony trifluoride (61.6 g), and vacuum pumped at 25 ° C using a vacuum pump. It dried under reduced pressure for 12 hours. Thereafter, the fraction obtained in Example 2-2 (100. Og) and the antimony 5 salt (18. Og) were added dropwise from a dropping funnel, and the flask was heated to reflux while stirring. Next, the reflux condenser was replaced with a simple distillation apparatus, and vacuum distillation was performed to obtain a colorless and transparent liquid (87.6 g) as a fraction. As a result of 19 F-NMR analysis of the liquid, it was determined that the liquid was a compound (y6-F) It was confirmed.
• Example 2-3 Place zinc powder (42.lg) and dimethylformamide (12 Og) in a four-necked flask (500 mL in volume, made of glass) equipped with a mechanical stirrer, dropping funnel, thermocouple thermometer, and distillation tower. To 40 ° C. Then, 1,2-dibromoethane (16.lg) was dropped into the system. After the end of the intense heat generation, the temperature inside the flask was kept at 55 ° C, and the colorless and transparent liquid (77. Og) obtained in Example 2-3 was slowly dropped into the flask.
• Lil (127 g) was charged into a three-necked flask (with an internal volume of 500 mL), and then the fraction obtained in Example 3-2 (390 g) was charged without stirring the inside of the flask. Next, the oil bath was heated to 100 ° C, the solution in the flask was heated under reflux for 1.5 hours, and then cooled to 25 ° C.
• Example 3 Example of manufacturing ICF CF OCFC1CF CI
• the liquid A (290 g) obtained in Example 3-3 was charged into an autoclave (internal volume 1 L, manufactured by Hastelloy) immersed in an oil bath. When the oil bath was heated to 200 ° C, the internal pressure of the autoclave continued to increase for 3 hours. Next, the internal temperature of the autoclave was maintained at 25 ° C., and the solution in the autoclave was extracted to obtain a crude reaction solution (270 g). Next, the reaction crude liquid was washed sequentially with an aqueous sodium sulfite solution (50 mL), water (50 mL), and saturated saline (50 mL) to obtain a crude product.
• an aqueous sodium sulfite solution 50 mL
• water 50 mL
• saturated saline 50 mL
• Example 3-5 Example of manufacturing ICF CH CF CF OCFC1CF CI
• gaseous CH CF is injected into the autoclave at a flow rate of 10.4 gZh.
• reaction crude liquid was washed with an aqueous solution of sodium sulfite (100 mL), water (100 mL), and saturated saline (100 mL) in this order to obtain a crude product.
• the crude product was analyzed by GC, and the formation of the title compound (40% yield) was confirmed. It was recovered by unreacted ICF CF OCFC1CF C1 (26% yield).
• the crude product was further rectified to obtain a product having a purity of 99% as determined by GC.
• reaction crude liquid After stirring and dropping, the mixture was further stirred for 12 hours to obtain a reaction crude liquid. As a result of analyzing the reaction crude liquid by GC, formation of the title compound was confirmed. After the reaction crude liquid was distilled off under reduced pressure, the residue was washed with saturated saline (500 mL) to obtain a reaction liquid. Analysis of the reaction mixture by GC revealed a 98% yield.
• FC CF FC8—CF
• Example 5-2 Production Example of Compound (yl3) R-113 (312 g) was added to an autoclave (500 mL, made of nickel), stirred, and kept at 25 ° C.
• a cooler kept at 20 ° C, a packed bed of NaF pellets, and a cooler kept at -10 ° C were installed in series.
• a liquid return line for returning the aggregated liquid from the cooler kept at -10 ° C to the autoclave was installed.
• fluorine gas diluted to 20% with nitrogen gas hereinafter referred to as 20% fluorine gas
• the benzene inlet of the autoclave and the outlet of the autoclave were closed, the pressure in the autoclave was increased to 0.20 MPa, and then the fluorine gas inlet valve of the autoclave was closed, and the mixture was stirred for 0.4 hours.
• 6 mL of the above benzene solution was injected while the pressure was adjusted to normal pressure, and the temperature in the reactor was maintained at 40 ° C, the benzene inlet of the autoclave was closed, and the outlet valve of the autoclave was closed.
• the pressure reached MPa the fluorine gas inlet valve of the autoclave was closed, and stirring was continued for 0.4 hour.
• the same operation was repeated three times.
• the total injection amount of benzene was 0.33 g, and the total injection amount of R-113 was 33 mL.
• Example 6 Example of production of polymer (Al-1) by copolymerization reaction of compound (al-1) with compound (m3-22)
• Example 13 The atmosphere was replaced with nitrogen gas.
• the autoclave was cooled to 78 ° C. in a dry ice / ethanol bath, and the product (8-1 Og) containing the compound (al-1) obtained in Example 13 was charged.
• the autoclave is pressurized to 0.2 MPa (gauge pressure) with nitrogen gas, and then heated to 100 ° C.
• polymerization was carried out for 66 hours, and the mixture was further heated at 120 ° C. for 24 hours to obtain a polymer (A1-1) (7.lg).
• the polymer (A1-1) results were analyzed by 1H-NMR and 19 F- NMR and a peak of fluorine atoms bonded to carbon atoms constituting an unsaturated bond in the polymer (A1- 1) is completely Since it disappeared and the 6-membered ring structure was retained, it was confirmed that a polymer containing a unit (Al-1) and a unit (M3-22) and the like was produced.
• the ratio of the unit (A1-1) to the total unit of the polymer (A1-1) is 12 mol%, and the ratio of the unit (M3-22) to which the compound (m3-22) is cyclopolymerized is expressed.
• the polymer (Al-1) has a tough, transparent glassy weight at 25 ° C.
• Example 1-3 After the reactor was cooled to 78 ° C. in a dry ice'ethanol bath, the product (12. Og) containing the compound (al-1) obtained in Example 1-3 was charged. Next, the inside of the autoclave is pressurized to 0.2 MPa (gauge pressure) with nitrogen gas, and then heated to 110 ° C for polymerization for 15 hours, and further heated to 130 ° C for 10 hours to perform polymerization. (A1-3) (4.3 g) was obtained.
• the polymer (A1-2) obtained by the method of Example 7 was charged in a hot air oven, treated at 300 ° C for 2 hours in an oxygen gas atmosphere, and then immersed in pure water at 100 ° C for 24 hours. The polymer was further dried under vacuum at 100 ° C. for 24 hours to obtain a polymer. Since absorption corresponding to a carboxyl group was confirmed in the IR spectrum of the polymer, it was confirmed that a polymer (A1-20) having a carboxyl group introduced into the polymer (A1-2) was formed. did.
• a polymer was obtained in the same manner as in Example 9 except that the polymer (A1-3) obtained in Example 8 was used and the temperature for vacuum drying was 80 ° C. IR spectrum of the polymer The formation of a polymer (A1-5) having a carboxyl group introduced into the polymer (A1-3) was confirmed. Polymer (A1-5 )) was 0.0005 mol Zg.
• the calcium fluoride substrate on which the polymer (A1-4) film (thickness: 1 ⁇ m) was formed had a transmittance of 90% or more for light having a wavelength of 157 nm.
• the glass pressure-resistant reactor was replaced with nitrogen gas.
• the glass pressure-resistant reactor was cooled to 78 ° C. in a dry ice / ethanol bath, and the product (16.5 g) containing the i-conjugated product (al-1) obtained in Example 1-3 was added. I charged.
• the inside of the system was frozen and degassed with liquid nitrogen, it was heated to 110 ° C. and polymerized for 18 hours. As a result, a polymer (A1-6) (8.4 g) was obtained.
• the 19 F-NMR measurement of the polymer (A1-6) showed that the carbon atom Since the peak of the bonding fluorine atom completely disappeared and the 6-membered ring structure was retained, it was confirmed that the polymer was a polymer containing the unit (A1-1) and the unit (M3-23). .
• the ratio of the unit (A1-1) to the total unit of the polymer (A1-6) was 34 mol%, and was derived from the compound (m3-23) obtained by cyclopolymerizing the compound (m3-23)
• the ratio of units (M3-23) and the like was 66 mol%.
• M of the polymer (A1-6) was 9,900 and T was 55 ° C. Heavy wg
• the combined product (A1-3) was a white powdery polymer at 25 ° C.
• the calcium fluoride substrate on which the polymer (A1-7) film (film thickness: 1 ⁇ m) was formed had a transmittance of 95% or more for light having a wavelength of 157 nm.
• Example 14 Example of production of polymer (Al-8) by copolymerization reaction of compound (al-1) with compound (m3-21)
• the intrinsic viscosity of the polymer (A1-8) in perfluoro (2-butyltetrahydrofuran) at 30 ° C was 0.13 (dLZg), and T was 97 ° C.
• the polymer (A1-8) is a tough, transparent glassy g at 25 ° C.
• the transmittance of the substrate made of calcium fluoride on which the polymer (A1-8) film (film thickness l / zm) was formed to light having a wavelength of 157 nm was 5% or less.
• the NMR of the polymer (A1-9) confirmed the presence of the signal of the 6-membered ring derived from the compound (al-1) and the presence of a signal (-60 ppm) based on the one- (OCF) -structure, so that the unit (Al—
• the proportion of units to total units of the polymer (A1- 9) (A1- 1) is 33 mol%, hydrofluoric mold - the proportion of isopropylidene of motor Nomar unit was 67 mol 0/0.
• M of the polymer (A1-9) was 46000, and T wg was 6 ° C.
• the polymer (A1-9) was a transparent glassy polymer having a large elongation at 10 ° C.
• the transmittance of the polymer (Al-9) in the form of a film (thickness: 1 ⁇ m) to light having a wavelength of 157 nm was 98% or more.
• the ratio of the unit (M3-21) and the like was 60 mol% and 10 mol%.
• Mw of the polymer (A1-10) was 70,000 and T was 21 ° C.
• the polymer (A1-10) is transparent and
• the calcium fluoride substrate on which the polymer (A1-10) film (thickness l / zm) is formed has a transmittance of 70% or more for light at a wavelength of 157 nm.
• the ratio of 30 mol%, unit (M2-11), etc. was 60 mol%.
• M w of the polymer (A1-11) was 151000 and T was 88 ° C.
• the polymer (A1-11) is transparent at 25 ° C and g
• the transmittance of the formed calcium fluoride substrate for light having a wavelength of 157 nm was 97% or more.
• NMR of the polymer (A2-1) confirmed the presence of a 5-membered ring signal derived from the compound (a2) and a signal (-59 ppm) based on the (OCF) -structure.
• the ratio of the monomer units of H was 67 mol%.
• M of polymer (A2-1) is 42000
• the polymer (A2-1) is a transparent glassy polymer at 20 ° C. g
• the calcium fluoride substrate on which the polymer (A3-1) coating (film thickness l / zm) was formed had a transmittance of 65% or more for light having a wavelength of 157 nm.
• the temperature inside the flask was stirred at 30 ° C for 19 hours, then at 20 ° C for 12 hours, and further stirred at —10 ° C for 26 hours, and further added at 0 ° C for 60 hours.
• the polymerization was carried out with stirring.
• the polymer (A3-2) has a M force of S11000 and a T force of 6 w g
• the polymer (A3-2) was a transparent polymer at 25 ° C.
• the calcium fluoride substrate on which the polymer (A3-1) coating (film thickness: 1 ⁇ m) was formed had a transmittance of light having a wavelength of 157 nm of 65% or more.
• the light transmittance of the film to light having a wavelength of 157 nm was 40% or more.
• the polymer (A1-1) (2 g) obtained in Example 6 and perfluoro (triptylamine) (18 g) were made of glass.
• the mixture was charged in a flask and heated and stirred at 40 ° C. for 24 hours to obtain a colorless and transparent solution.
• This solution was spin-coated on a polished quartz substrate at a spin speed of 500 rpm for 10 seconds, and further spin-coated at 700 rpm for 20 seconds, and a polymer (Al-1) was applied to the surface of the quartz substrate.
• a substrate was obtained.
• the treated substrate was heated at 80 ° C. for 1 hour, and further heated at 180 ° C. for 1 hour and dried, and the substrate (A1) having a uniform and transparent polymer (A1-1) film formed on the surface (A1 -1).
• Example 22 Production example of pellicle using polymer (A1-21) for adhesive and polymer (A1-1) — (A1-3) for pellicle film
• the polymer (A1-21) (2 g) obtained in Example 10 and perfluoro (2-butyltetrahydrofuran) (38 g) were charged into a flask (glass), and the mixture was heated and stirred at 40 ° C. for 24 hours.
• a colorless and transparent solution was used as an adhesive.
• the solution was applied to the surface of the frame (made of aluminum) to which the pellicle film adheres, and then dried at 25 ° C. for 2 hours. Further, the frame was placed on a hot plate at 120 ° C such that the surface on which the adhesive was applied faced upward. Next, it was heated at 120 ° C. for 10 minutes.
• the coated surface of the substrate (A1-1) obtained in Example 20 was brought into contact with the adhesive surface of the frame, pressed and bonded, and heated at 120 ° C for 10 minutes to form the frame and the coated surface.
• the quartz substrate was peeled off from the substrate (A1-1).
• a pellicle (Al-1) having a uniform free-standing film (1 ⁇ m thick) of the polymer (A1-1) adhered to the frame via the polymer (A1-21) was obtained.
• a pellicle (A1-2) in which a uniform self-supporting film (1 ⁇ m thick) of the polymer (A1-2) adhered to the frame via the polymer (Al-21) was used. Obtained.
• a pellicle (A1-3) was obtained in which a uniform free-standing film (1 ⁇ m thick) of the polymer (A1-3) was adhered to the frame via the polymer (A1-21).
• the transmittance of the F excimer laser with a wavelength of 157 nm is pellicle (Al-1) power 3 ⁇ 40% or more
• Example 21 Using the F excimer laser having the intensity of 0.05 mjZ pulse, the perimeter obtained in Example 21 was used.
• the irradiation test is performed at 200 Hz cycle using each of the CuAl (Al-1) and (A1-3). Pellicles (Al-1)-(A1-3) show good durability with little decrease in transmittance of the film after 600,000 pulses. Further, each pellicle film and frame are firmly adhered via a polymer (A1-21).
• the polymer (A1-6) (8 g) obtained in Example 18 and perfluoro (tributylamine) (92 g) were placed in a glass flask and heated and stirred at 40 ° C. for 24 hours. As a result, a colorless, transparent, turbid, homogeneous solution was obtained. This solution was spin-coated on a Si substrate at 500 rpm for 10 seconds and then at 100 rpm for 20 seconds, and then heat-treated at 80 ° C for 1 hour and 180 ° C for 1 hour. As a result, a uniform and transparent film was obtained on the Si substrate.
• the fluorine-containing polymer (I) of the present invention is suitable for short-wavelength light (particularly, F excimer laser).
• novel polymer with excellent transparency and durability.
• the novel polymer (I) is useful as a pellicle film, an adhesive and the like. With a pellicle using the fluoropolymer of the present invention, an exposure process for manufacturing a semiconductor device or a liquid crystal display panel can be performed with a high yield, and a useful semiconductor device or a liquid crystal display panel is provided. Further, according to the present invention, a novel compound useful as a monomer, a novel polymer, and a method for producing the same can be provided.

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