Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
  • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
  • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
  • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
  • B01D67/0002—Organic membrane manufacture
  • B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
  • B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
  • B01D67/0081—After-treatment of organic or inorganic membranes
  • B01D67/0093—Chemical modification
  • B01D67/00931—Chemical modification by introduction of specific groups after membrane formation, e.g. by grafting
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
  • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
  • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
  • B01D71/641—Polyamide-imides
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/20—Purification, separation
• • 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
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
  • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
• • 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
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
  • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
• • 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
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P32/00—Diffusion of dopants within, into or out of wafers, substrates or parts of devices
  • H10P32/10—Diffusion of dopants within, into or out of semiconductor bodies or layers
  • H10P32/14—Diffusion of dopants within, into or out of semiconductor bodies or layers within a single semiconductor body or layer in a solid phase; between different semiconductor bodies or layers, both in a solid phase
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P32/00—Diffusion of dopants within, into or out of wafers, substrates or parts of devices
  • H10P32/10—Diffusion of dopants within, into or out of semiconductor bodies or layers
  • H10P32/19—Diffusion sources
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2325/00—Details relating to properties of membranes
  • B01D2325/02—Details relating to pores or porosity of the membranes
  • B01D2325/021—Pore shapes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2325/00—Details relating to properties of membranes
  • B01D2325/02—Details relating to pores or porosity of the membranes
  • B01D2325/0283—Pore size
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
  • B01D61/14—Ultrafiltration; Microfiltration
• • 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
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/14—Polyamide-imides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
  • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

• the present invention relates to a purification method using a polyimide and / or polyamideimide porous membrane, a silylating agent chemical, a film forming material or a liquid as a diffusing agent composition to be purified, and a silanol group is generated by hydrolysis.
• the present invention relates to a filter medium comprising a porous membrane and a filter device including the polyimide and / or polyamideimide porous membrane.
• a silylating agent chemical for forming a protective film for imparting hydrophobicity to the substrate for example, see Patent Document 1
• a material for forming a fine film for example, see Patent Document 2
• a semiconductor substrate It is desirable that the diffusing agent composition used for the diffusion of dopants does not contain contaminating metals such as iron and zinc.
• the filter device usually includes a filter medium using a porous membrane.
• the porous film can remove fine substances such as nano particles.
• Nylon, polyethylene, polypropylene, PTFE, etc. are common as filter membranes that can remove impurities from chemicals and resin materials used in applications such as semiconductor devices. For example, by using filter membranes such as nylon, organic It is known that system impurities are also removed (for example, Patent Document 3).
• JP 2010-114414 A Japanese Patent Laying-Open No. 2005-171067 Japanese Patent No. 4637476
• the membrane made of nylon has low acid resistance, it is difficult to wash with acid, and it is difficult to remove impurities mixed in or attached to the filter itself.
• membrane which consists of polyethylene had the problem that the removal rate of impurities, such as iron and zinc which should be removed from the chemical
• Porous membranes used for filter media are required to be processed at a certain flow rate in the industry, but if the flow rate is increased, the removal performance of impurities such as metals tends to deteriorate, and both the flow rate and impurity removal performance are compatible. Was not easy.
• the present invention has been made in view of the above circumstances, and uses a polyimide and / or polyamide-imide porous film excellent in removal performance of impurities such as metals, a silylating agent chemical, a film-forming material, or a diffusing agent composition.
• a purification method using a liquid to be purified a purification method using a silicon compound-containing liquid containing a silicon compound capable of generating a silanol group by hydrolysis, a silylating agent chemical solution and a membrane using the purification method It aims at providing the manufacturing method of a forming material or a diffusing agent composition, the filter media which consist of this porous membrane, and the filter device containing this porous membrane.
• the present inventors have found that a polyimide and / or polyamide-imide porous membrane having communication holes is excellent in the performance of removing impurities such as metals due to its porous structure, and have completed the present invention.
• a first aspect of the present invention is a purification method using a liquid as a material to be purified, wherein a part or all of the liquid is transferred from one side of a polyimide and / or polyamideimide porous membrane having communication holes to the other.
• the liquid is a silylating agent chemical solution, a film-forming material, or a diffusing agent composition used for dopant diffusion into a semiconductor substrate.
• a second aspect of the present invention is a purification method using a silicon compound-containing liquid as a material to be purified, wherein a part of or all of the silicon compound-containing liquid is a polyimide and / or polyamide-imide porous membrane having communication holes. Including transmission from one side to the other by differential pressure,
• the silicon compound-containing liquid contains a silicon compound that can generate a silanol group by hydrolysis.
• the third aspect of the present invention uses a purification method using the liquid of the first aspect of the present invention as a product to be purified or a purification method using the silicon compound-containing liquid of the second aspect of the present invention as a product to be purified.
• a method for producing a silylating agent chemical, a film-forming material, or a diffusing agent composition is also included.
• the fourth aspect of the present invention is used in the purification method using the liquid of the first aspect of the present invention as the product to be purified or the purification method using the silicon compound-containing liquid of the second aspect of the present invention as the product to be purified.
• It is a filter media comprising the polyimide and / or polyamideimide porous membrane.
• the fifth aspect of the present invention is used in the purification method using the liquid of the first aspect of the present invention as a product to be purified or the purification method using the silicon compound-containing liquid of the second aspect of the present invention as a product to be purified.
• a filter device including the polyimide and / or polyamideimide porous membrane.
• a method for purifying a liquid using a polyimide and / or polyamide-imide porous membrane excellent in metal removal performance a method for producing a chemical solution or a cleaning solution using the purification method, a filter medium comprising the porous membrane, and the method
• a filter device comprising a porous membrane can be provided.
• the purification method which uses the liquid as the first aspect as the material to be purified uses a filter medium comprising the polyimide and / or polyamideimide porous membrane, or a filter device including the polyimide and / or polyamideimide porous membrane. Is preferred.
• the purification method using the silicon compound-containing liquid as the second object in the second aspect is that the silicon compound-containing liquid is partially or entirely removed from one side of the polyimide and / or polyamideimide porous membrane having communication holes. Including permeating to the other side by differential pressure, The said silicon compound containing liquid contains the silicon compound which can produce
• the purification method using the silicon compound-containing liquid as the second object in the second embodiment is a filter medium comprising the polyimide and / or polyamideimide porous membrane, or a filter device comprising the polyimide and / or polyamideimide porous membrane. Is preferably used.
• the silicon compound-containing liquid is a silylating agent chemical solution, a film-forming material, or a diffusing agent used for dopant diffusion into a semiconductor substrate.
• a composition is preferred.
• the type of the silylating agent chemical solution to be purified is not particularly limited as long as it can hydrophobize the properties of the substrate surface, and has been conventionally used for water repellency or hydrophobization of various materials.
• the silylating agent chemical solution is appropriately selected and used.
• “hydrophobization” is a concept including water repellency.
• the silylating agent chemical solution to be purified preferably contains a silicon compound that can generate a silanol group by hydrolysis, and the silicon compound is a silylating agent represented by the following general formula (1). Is more preferable.
• R a1 s each independently represent a monovalent group containing a monovalent hydrocarbon group having 1 to 18 carbon atoms in which some or all of the hydrogen atoms may be substituted with fluorine atoms.
• X 1 represents, independently of each other, a monovalent functional group in which the atom bonded to the silicon atom is nitrogen, a is an integer of 1 to 3, and b is an integer of 0 to 2. And the sum of a and b is 1 to 3.
• Suitable silylating agents also include silylating agents represented by the following general formulas (1-1) to (1-8) and cyclic silazane compounds.
• silylating agent represented by the general formulas (1-1) to (1-8) and the cyclic silazane compound will be described in order.
• R 1 , R 2 and R 3 each independently represents a hydrogen atom, a halogen atom or an organic group. The total number of carbon atoms of R 1 , R 2 and R 3 is 1 or more.
• R 4 represents a hydrogen atom or a saturated or unsaturated chain hydrocarbon group.
• R 5 represents a hydrogen atom, a saturated or unsaturated chain hydrocarbon group, a saturated or unsaturated non-aromatic cyclic hydrocarbon group, or a non-aromatic heterocyclic group.
• R 4 and R 5 may combine with each other to form a non-aromatic heterocyclic ring having a nitrogen atom.
• R 1 , R 2 and R 3 are halogen atoms, a chlorine atom, a bromine atom, an iodine atom and a fluorine atom are preferred.
• the organic group may contain a hetero atom in addition to the carbon atom.
• the type of hetero atom that the organic group may contain is not particularly limited as long as the object of the present invention is not impaired.
• the hetero atom that the organic group may contain N, O, and S are preferable.
• R 1 , R 2 and R 3 are organic groups, the sum of the number of carbon atoms and the number of heteroatoms contained in the organic group is the sum of the carbon numbers of R 1 , R 2 and R 3 As long as is 1 or more, there is no particular limitation.
• R 1 , R 2 and R 3 are organic groups
• the total number of carbon atoms and hetero atoms contained in the organic group is preferably 1 to 10, more preferably 1 to 8, 1-3 are particularly preferred.
• the organic group is preferably a saturated or unsaturated chain hydrocarbon group, an aralkyl group, and an aromatic hydrocarbon group.
• Preferred examples of the saturated or unsaturated chain hydrocarbon group include a methyl group, an ethyl group, a vinyl group, an n-propyl group, an isopropyl group, an allyl group, a 1-propenyl group, an isopropenyl group, and an n-butyl group.
• n-pentyl group isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n -Nonyl group, n-decyl group and the like.
• chain hydrocarbon groups a methyl group, an ethyl group, a vinyl group, an n-propyl group, and an allyl group are more preferable, and a methyl group, an ethyl group, and a vinyl group are particularly preferable.
• aralkyl group examples include benzyl group, phenylethyl group, phenylpropyl group, ⁇ -naphthylmethyl group, and ⁇ -naphthylmethyl group.
• aromatic hydrocarbon group examples include a phenyl group, an ⁇ -naphthyl group, and a ⁇ -naphthyl group.
• R 4 is a saturated or unsaturated chain hydrocarbon group
• the carbon number of the saturated or unsaturated chain hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired.
• the carbon number of the saturated or unsaturated chain hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, and more preferably 1 to 3 Particularly preferred.
• preferred examples include a saturated or unsaturated chain hydrocarbon group mentioned as a suitable group for R 1 , R 2 and R 3 It is the same.
• R 5 is a saturated or unsaturated chain hydrocarbon group
• the saturated or unsaturated chain hydrocarbon group is the same as R 4 .
• the carbon number of the saturated or unsaturated cyclic hydrocarbon group is not particularly limited as long as the object of the present invention is not impaired.
• the saturated or unsaturated non-aromatic cyclic hydrocarbon group preferably has 3 to 10 carbon atoms, more preferably 3 to 6, 5 or 6 is particularly preferred.
• R 5 is a saturated or cyclic hydrocarbon group
• R 5 is a non-aromatic heterocyclic group
• the hetero atom contained in the non-aromatic heterocyclic group is not particularly limited as long as the object of the present invention is not impaired.
• suitable heteroatoms contained in the non-aromatic heterocyclic group include N, O, and S.
• R 5 is a non-aromatic heterocyclic group
• the total of the number of carbon atoms and the number of hetero atoms contained in the non-aromatic heterocyclic group is particularly limited as long as the object of the present invention is not impaired.
• the total number of carbon atoms and hetero atoms contained in the non-aromatic heterocyclic group is preferably 3 to 10, more preferably 3 to 6 Preferably 5 or 6 is particularly preferred.
• R 5 is a non-aromatic heterocyclic group
• Preferred examples when R 5 is a non-aromatic heterocyclic group include pyrrolidin-1-yl, piperidin-1-yl, piperazin-1-yl, morpholin-1-yl, and thiol And a morpholin-1-yl group.
• the number of atoms contained in the non-aromatic heterocyclic group formed by combining R 4 and R 5 with each other is not particularly limited as long as the object of the present invention is not impaired.
• the non-aromatic heterocyclic group formed by combining R 4 and R 5 with each other is preferably a 3- to 10-membered ring, more preferably a 5- or 6-membered ring.
• the kind of the other hetero atom of the carbon atom contained in the non-aromatic heterocyclic group formed by combining R 4 and R 5 with each other is not particularly limited as long as the object of the present invention is not impaired.
• Suitable heteroatoms included in the non-aromatic heterocyclic group formed by combining R 4 and R 5 with each other include N, O, and S.
• Preferable examples of the non-aromatic heterocyclic ring formed by combining R 4 and R 5 with each other include pyrrolidine, piperidine, piperazine, morpholine, and thiomorpholine.
• silylating agent represented by the general formula (1-1) include N, N-dimethylaminotrimethylsilane, N, N-dimethylaminodimethylsilane, N, N-dimethylaminomonomethylsilane, N, N -Diethylaminotrimethylsilane, t-butylaminotrimethylsilane, allylaminotrimethylsilane, trimethylsilylacetamide, N, N-dimethylaminodimethylvinylsilane, N, N-dimethylaminodimethylpropylsilane, N, N-dimethylaminodimethyloctylsilane N, N-dimethylaminodimethylphenylethylsilane, N, N-dimethylaminodimethylphenylsilane, N, N-dimethylaminodimethyl-t-butylsilane, N, N-dimethylaminotrieth
• R 1 , R 2 and R 3 are the same as in general formula (1-1) above.
• R 6 represents a hydrogen atom, a methyl group, a trimethylsilyl group, or a dimethylsilyl group.
• R 7 , R 8 and R 9 each independently represents a hydrogen atom or an organic group. The total number of carbon atoms of R 7 , R 8 and R 9 is 1 or more.
• R 7 , R 8 , and R 9 are organic groups
• the organic group is the same as the organic group when R 1 , R 2, and R 3 are organic groups.
• silylating agent represented by the general formula (1-2) examples include hexamethyldisilazane, N-methylhexamethyldisilazane, 1,1,3,3-tetramethyldisilazane, 1,3- Dimethyldisilazane, 1,3-di-n-octyl-1,1,3,3-tetramethyldisilazane, 1,3-divinyl-1,1,3,3, -tetramethyldisilazane, tris (dimethyl Silyl) amine, tris (trimethylsilyl) amine, 1-ethyl-1,1,3,3,3-pentamethyldisilazane, 1-vinyl-1,1,3,3,3-pentamethyldisilazane, Propyl-1,1,3,3,3-pentamethyldisilazane, 1-phenylethyl-1,1,3,3,3-pentamethyldisilazane, 1-tert-butyl-1,1,3,3
• R 1 , R 2 and R 3 are the same as in general formula (1-1) above.
• Y represents O, CHR 11 , CHOR 11 , CR 11 R 11 , or NR 12 .
• R 10 and R 11 are each independently a hydrogen atom, a saturated or unsaturated chain hydrocarbon group, a saturated or unsaturated non-aromatic cyclic hydrocarbon group, a trialkylsilyl group, a trialkylsiloxy group, an alkoxy group, phenyl Represents a group, a phenylethyl group, or an acetyl group.
• R 12 represents a hydrogen atom, an alkyl group, or a trialkylsilyl group.
• R 10 and R 11 are a saturated or unsaturated chain hydrocarbon group or a saturated or unsaturated non-aromatic cyclic hydrocarbon group
• a saturated or unsaturated chain hydrocarbon group and a saturated Or the unsaturated non-aromatic cyclic hydrocarbon group means that R 5 in the general formula (1-1) is a saturated or unsaturated chain hydrocarbon group, or a saturated or unsaturated non-aromatic cyclic hydrocarbon group. The same as in the case of a hydrogen group.
• R 10 and R 11 are a trialkylsilyl group, a trialkylsiloxy group, or an alkoxy group
• the carbon number of the alkyl group contained in these groups is not particularly limited as long as the object of the present invention is not impaired.
• the number of carbon atoms of the alkyl group contained in these groups is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 3.
• Preferable examples of the alkyl group contained in these groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group.
• a methyl group, an ethyl group, and an n-propyl group are more preferable, and a methyl group and an ethyl group are particularly preferable.
• R 12 is an alkyl group or a trialkylsilyl group
• the number of carbon atoms of the alkyl group contained in the alkyl group or trialkylsilyl group is not particularly limited as long as the object of the present invention is not impaired.
• the number of carbon atoms of the alkyl group contained in the alkyl group or trialkylsilyl group is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 3.
• alkyl group contained in the alkyl group or trialkylsilyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n- Examples thereof include a pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, and n-decyl group.
• a methyl group, an ethyl group, and an n-propyl group are more preferable, and a methyl group and an ethyl group are particularly preferable.
• silylating agent represented by the general formula (1-3) examples include trimethylsilyl acetate, dimethylsilyl acetate, monomethylsilyl acetate, trimethylsilylpropionate, trimethylsilylbutyrate, and trimethylsilyl-2-butenoate. .
• R 1 , R 2 and R 3 are the same as in general formula (1-1) above.
• R 6 is the same as in the general formula (1-2).
• R 13 represents a hydrogen atom, a saturated or unsaturated chain hydrocarbon group, a trifluoromethyl group, or a trialkylsilylamino group.
• R 13 is a saturated or unsaturated chain hydrocarbon group
• the saturated or unsaturated chain hydrocarbon group means that R 4 in the general formula (1-1) is a saturated or unsaturated chain hydrocarbon group. The same as in the case of a hydrogen group.
• R 13 is a trialkylsilylamino group
• the alkyl group contained in the trialkylsilylamino group is such that R 10 and R 11 in the general formula (1-3) are a trialkylsilyl group, a trialkylsiloxy, Or when it is an alkoxy group, it is the same as the alkyl group contained in these groups.
• silylating agent represented by the general formula (1-4) include N, N′-bis (trimethylsilyl) urea, N-trimethylsilylacetamide, N-methyl-N-trimethylsilyltrifluoroacetamide, and N, And N-bis (trimethylsilyl) trifluoroacetamide.
• R 14 represents a trialkylsilyl group.
• R 15 and R 16 each independently represents a hydrogen atom or an organic group.
• R 14 is a trialkylsilyl group
• the alkyl group contained in the trialkylsilyl group is such that R 10 and R 11 in the general formula (1-3) are a trialkylsilyl group, a trialkylsiloxy, or an alkoxy group.
• R 10 and R 11 in the general formula (1-3) are a trialkylsilyl group, a trialkylsiloxy, or an alkoxy group.
• it is a group, it is the same as the alkyl group contained in these groups.
• R 15 and R 16 are organic groups
• the organic group is the same as the organic group in the case where R 1 , R 2 and R 3 in the general formula (1-1) are organic groups.
• silylating agent represented by the general formula (1-5) examples include 2-trimethylsiloxypentan-2-en-4-one.
• R 1 , R 2 and R 3 are the same as in general formula (1-1) above.
• R 17 represents a saturated or unsaturated chain hydrocarbon group, a saturated or unsaturated non-aromatic cyclic hydrocarbon group, or a non-aromatic heterocyclic group.
• R 18 represents —SiR 1 R 2 R 3 . p is 0 or 1.
• the saturated or unsaturated chain hydrocarbon group, saturated or unsaturated non-aromatic cyclic hydrocarbon group, or non-aromatic heterocyclic group as R 17 has the general formula (1-1 This is the same as R 5 in ).
• the organic group as R 17 is obtained by removing one hydrogen atom from the organic group when R 1 , R 2 and R 3 in the general formula (1-1) are organic groups It is a divalent group.
• silylating agent represented by the general formula (1-6) examples include 1,2-bis (dimethylchlorosilyl) ethane and t-butyldimethylchlorosilane.
• R 19 each independently represents a chain hydrocarbon group having 1 to 18 carbon atoms in which part or all of the hydrogen atoms may be substituted with fluorine atoms. q is 1 or 2.
• the carbon number of R 19 is preferably 2 to 18, and more preferably 8 to 18.
• R 19 is a chain saturated hydrocarbon group not substituted with a fluorine atom
• examples of the case where R 19 is a chain saturated hydrocarbon group not substituted with a fluorine atom include methyl group, ethyl group, n-propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl Group, isobutyl group, amyl group, isoamyl group, tert-amyl group, hexyl group, 2-hexyl group, 3-hexyl group, heptyl group, 2-heptyl group, 3-heptyl group, isoheptyl group, tert-heptyl group, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, decyl, dodecyl, tridecyl, tetradec
• R 19 is a chain unsaturated hydrocarbon group not substituted with a fluorine atom
• examples of the case where R 19 is a chain unsaturated hydrocarbon group not substituted with a fluorine atom include vinyl group, 1-propenyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group 3-butenyl group, 1,3-butadienyl group, 1-ethylvinyl group, 1-methyl-1-propenyl group, 1-methyl-2-propenyl group, 4-pentenyl group, 1,3-pentadienyl group, 2, 4-pentadienyl group, 3-methyl-1-butenyl group, 5-hexenyl group, 2,4-hexadienyl group, 6-heptenyl group, 7-octenyl group, 8-nonenyl group, 9-decenyl group, 10-undecenyl group 11-dodecenyl group, 12-tri
• R 19 is a chain hydrocarbon group substituted with a fluorine atom
• the number of substitutions and the substitution position of the fluorine atom are not particularly limited.
• the number of fluorine atoms substituted in the chain hydrocarbon group is preferably 50% or more, more preferably 70% or more, and particularly preferably 80% or more of the number of hydrogen atoms of the chain hydrocarbon group.
• R 19 is preferably a straight-chain hydrocarbon group having 1 to 18 carbon atoms in which part or all of the hydrogen atoms may be substituted with fluorine atoms because an excellent hydrophobizing effect can be easily obtained.
• R 19 is a linear saturated hydrocarbon group having 1 to 18 carbon atoms (carbon atoms) in which part or all of the hydrogen atoms may be substituted with fluorine atoms from the viewpoint of the storage stability of the silylating agent. (Alkyl group of 1 to 18) is more preferable.
• q is 1 or 2, and 1 is preferable.
• R 20 and R 21 are each independently a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.
• R 22 is a linear or branched alkylene group having 1 to 16 carbon atoms.
• r and s are each independently an integer of 0 to 2.
• R 20 and R 21 may be the same or different from each other.
• R 20 and R 21 are preferably a hydrogen atom or a linear or branched alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.
• R 20 and R 21 are linear or branched alkyl groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec- Examples include a butyl group, a tert-butyl group, and an isobutyl group.
• the compound represented by the general formula (1-8) includes a linear or branched alkylene group having 1 to 16 carbon atoms as R 22 .
• the linear or branched alkylene group as R 22 preferably has 1 to 10 carbon atoms, and more preferably 2 to 8 carbon atoms.
• the linear alkylene group is a methylene group or an ⁇ , ⁇ -linear alkylene group
• the branched alkylene group is an alkylene group other than a methylene group and an ⁇ , ⁇ -linear alkylene group.
• R 22 is preferably a linear alkylene group.
• R 22 is a linear or branched alkylene group having 1 to 16 carbon atoms
• examples of the case where R 22 is a linear or branched alkylene group having 1 to 16 carbon atoms include a methylene group, a 1,2-ethylene group, a 1,1-ethylene group, a propane-1,3-diyl group Propane-1,2-diyl group, propane-1,1-diyl group, propane-2,2-diyl group, butane-1,4-diyl group, butane-1,3-diyl group, butane-1, 2-diyl group, butane-1,1-diyl group, butane-2,2-diyl group, butane-2,3-diyl group, pentane-1,5-diyl group, pentane-1,4-diyl group, Hexane-1,6-diyl group, heptane-1,7-diyl group, o
• s and r are each independently an integer of 0 to 2.
• s and r are preferably 1 or 2, and more preferably 2, because synthesis and availability are easy.
• cyclic silazane compound As the silylating agent, a cyclic silazane compound is also preferable. Hereinafter, the cyclic silazane compound will be described.
• cyclic silazane compounds examples include 2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane, 2,2,6,6-tetramethyl-2,6-disila-1-azacyclohexane Cyclic trisilazane compounds such as 2,2,4,4,6,6-hexamethylcyclotrisilazane, 2,4,6-trimethyl-2,4,6-trivinylcyclotrisilazane, etc .; 2 , 2,4,4,6,6,8,8-octamethylcyclotetrasilazane and the like; and the like.
• cyclic disilazane compounds are preferable, and 2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane and 2,2,6,6-tetramethyl-2,6-disila- 1-azacyclohexane is more preferred.
• the cyclic disilazane compound include 5-membered ring structures such as 2,2,5,5-tetramethyl-2,5-disila-1-azacyclopentane, and 2,2,6,6-tetramethyl- There is a 6-membered ring structure such as 2,6-disila-1-azacyclohexane, but a 5-membered ring structure is more preferable.
• the silylating agent chemical used in the present invention may contain other components other than the silylating agent described above as long as the object of the present invention is not impaired.
• the other components are not particularly limited, and examples thereof include organic solvents.
• the silylating agent is not liquid, it is preferable to contain an organic solvent, but the silylating agent can be exposed to the substrate surface. If it exists, it may not contain an organic solvent.
• the organic solvent that can be contained in the silylating agent chemical solution is not particularly limited, but an organic solvent that does not have a functional group that reacts with the silylating agent is preferable.
• An organic solvent may be used individually by 1 type, and 2 or more types may be mixed and used for it.
• preferred organic solvents include sulfoxides such as dimethyl sulfoxide; sulfones such as dimethyl sulfone, diethyl sulfone, bis (2-hydroxyethyl) sulfone, and tetramethylene sulfone; N, N-dimethylformamide.
• Amides such as N-methylformamide, N, N-dimethylacetamide, N-methylacetamide, N, N-diethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-propyl-2 Lactams such as pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone; 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1 Imidazoles such as 1,3-diisopropyl-2-imidazolidinone Non-types; Dialkyl glycol ethers such as dimethyl glycol, dimethyl diglycol, dimethyl triglycol, methyl ethyl diglycol, and diethyl glycol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether
• propylene glycol monomethyl ether acetate PEMEA
• linear, branched or cyclic hydrocarbons terpenes such as p-menthane, diphenylmenthane, limonene, terpinene, bornane, norbornane and pinane are preferred.
• the silylating agent chemical solution (treated silylating agent chemical solution) obtained by the purification method according to the first or second aspect or the manufacturing method according to the third aspect reduces the concentration of metal impurities as described above. Therefore, it can be suitably used as a substrate surface treatment liquid, and is particularly suitable as a substrate surface treatment liquid used in the production of semiconductor devices and the like.
• the film-forming material as the material to be purified contains a silicon compound capable of generating a silanol group by hydrolysis, and the silicon compound is represented by the following general formula (2) or (3) It is more preferable that The silicon compound represented by the following general formula (2) or (3) is particularly highly active against hydrolysis, and in the heating and baking when forming a film on the substrate surface, the conventional film forming material is used. In addition, the temperature can be reduced, and a film can be formed on the substrate surface without heat treatment.
• R a2 4-n2 SiX n2 (2) (In the formula (2), R a2 is a hydrogen atom or a monovalent hydrocarbon group.
• X is a linear or branched alkoxy group having 1 to 5 carbon atoms, an isocyanate group, and a halogen atom.
• a group selected from the group, n2 is an integer of 1 to 4)
• X is preferably an isocyanate group, and n2 is preferably 4.
• R a3 4-n3- Si (NCO) n3 (3) (In Formula (3), R a3 is a hydrogen atom or a monovalent hydrocarbon group, and n3 is 2 to 4.)
• the said silicon compound may be used individually by 1 type, and may be used in combination of 2 or more type.
• R a3 in the formula (3) is a hydrogen atom or a monovalent hydrocarbon group.
• the hydrocarbon group as R a3 is not particularly limited as long as the object of the present invention is not impaired, and an aliphatic hydrocarbon group having 1 to 12 carbon atoms is preferable.
• Preferable examples of the aliphatic hydrocarbon group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, and tert-butyl group.
• N-pentyl group isopentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-cycloheptyl group, n-octyl group, n-cyclooctyl group, n-nonyl group, Examples include an n-decyl group, an n-undecyl group, and an n-dodecyl group. More preferred is an aliphatic hydrocarbon group having 1 to 5 carbon atoms.
• a methyl group and an ethyl group are more preferable, and a methyl group is particularly preferable.
• tetraisocyanate silane methyl triisocyanate silane
• ethyl triisocyanate silane are preferable.
• the content of the silicon compound in the film forming material is not particularly limited as long as a uniformly dissolved film forming material can be prepared.
• the content of the silicon compound in the film-forming material is preferably 0.01 to 50% by mass, more preferably 0.01 to 10% by mass, further preferably 0.01 to 5% by mass, and 0.01 to 1% by mass is particularly preferred. By containing the silicon compound in such a content, there is a tendency that a film can be formed more conformally as a film.
• the film-forming material may contain any metal alkoxide from the viewpoint of film-forming properties. Only one metal alkoxide may be used, or a plurality of metal alkoxides may be used simultaneously.
• the content of the metal alkoxide is not particularly limited and is preferably 0.01 to 20% by mass, more preferably 0.01 to 5% by mass, further preferably 0.01 to 1% by mass, and 0.1 to 0.5% by mass. Mass% is most preferred.
• the film forming material contains the metal alkoxide in such a content, the strength of the formed film tends to be improved.
• various characteristics can be given by containing a metal alkoxide. For example, optical properties such as refractive index and solubility in acids and bases can be changed.
• the film forming material may further contain an organic solvent.
• the solvent include the organic solvents described above as specific examples and preferable examples of the organic solvent that can be contained in the silylating agent chemical.
• An organic solvent may be used independently and may be used in combination of 2 or more type.
• the content of the organic solvent in the film-forming material is usually a residual amount relative to the total amount of the content of the silicon compound, the content of the metal alkoxide, and the content of other components described below.
• the film forming material may contain various additives together with the silicon compound and the metal alkoxide as long as the object of the present invention is not impaired.
• additives include surfactants, viscosity modifiers, antifoaming agents, and the like.
• the film forming material is prepared by uniformly mixing and dissolving the above-described silicon compound described above and other components as necessary.
• the film forming material obtained by the purification method according to the first or second aspect or the production method according to the third aspect is preferably a monomolecular film forming material.
• a film such as a SiO 2 film is formed on the substrate by hydrolysis condensation of the silicon compound. It can be easily formed on the surface.
• the hydroxyl group can be changed regardless of the material of the substrate.
• the metal oxide film which has abundant can be formed.
• a tungsten substrate, a titanium nitride substrate, a silicon nitride substrate, a copper substrate, a gold substrate, and the like may be difficult to be modified with a silylating agent by a conventionally known method.
• the method for forming a film on the surface of the substrate using the film forming material described above is not particularly limited. Hereinafter, the film forming method will be described.
• the material of the substrate on which the film is to be formed is not particularly limited, and is selected from various inorganic substrates and organic substrates.
• a surface treatment with a silylating agent is performed after forming a film on the substrate surface using the film forming material described above, such as a tungsten substrate, a titanium nitride substrate, a silicon nitride substrate, a copper substrate, and a gold substrate, Even a substrate that is difficult to be surface-modified by a conventionally known method can be surface-modified well.
• the method of forming a film on the surface of the substrate using the film forming material is a method in which the film forming material can be applied to the surface of the substrate and can cause hydrolysis reaction of the silicon compound on the surface of the substrate. If there is no particular limitation.
• the method for applying the film forming material to the substrate surface is not particularly limited.
• the silicon compound is used as a solution, the amount of the silicon compound applied to the substrate surface can be easily adjusted by adjusting the thickness of the coating film to be formed.
• a coating film may be formed on the substrate surface by hydrolysis condensation between the silicon compounds.
• the substrate surface is in an untreated state. It is preferable to be hydrophilized. Whether the substrate surface is hydrophilized can be confirmed by measuring the degree of hydrophilicity of the substrate surface by a known method such as measuring the contact angle of water on the substrate surface before and after the treatment. By confirming that the surface of the substrate is hydrophilized, it can be confirmed that a large amount of hydroxyl groups have been introduced to the surface of the substrate by forming a film. If a large number of hydroxyl groups are introduced on the surface of the substrate, the silylating agent tends to bind to the surface of the coating formed by condensation of the silicon compound.
• a film made of an inorganic oxide on the surface of the substrate can be confirmed, for example, by spin-coating a solution-like film forming material on a substrate of a desired material. Specifically, after the film forming material is applied on the substrate in the air, the substrate is rotated to uniformly apply the film forming material on the substrate, and then spin-dried to blow off the solvent. A film is formed. At this time, moisture in the atmosphere and the silicon compound such as Si (NCO) 4 undergo a hydrolysis reaction, and then polycondensate to form a film made of an inorganic oxide.
• the thickness of the coating made of an inorganic oxide depends on the concentration of the silicon compound, the number of rotations during spin coating, humidity, and the like. The presence / absence and film thickness of the coating formed by the above method on the substrate can be confirmed by, for example, an ellipsometer or nanospec.
• the method for applying the film forming material to the substrate surface is not particularly limited, and a known application method can be applied.
• suitable coating methods include spraying, spin coating, dip coating, roll coating, and the like.
• the natural oxide film on the substrate surface may be removed before the treatment with the film forming material.
• the film formed on the substrate surface by using the film forming material has various excellent properties such as high etching resistance and high reactivity with a surface treatment agent such as a silylating agent.
• the film-forming material obtained by the purification method according to the first or second aspect or the production method according to the third aspect can be used to form a planarization film. Since the film-forming material obtained by the purification method according to the first or second aspect or the production method according to the third aspect contains the silicon compound having self-reactivity, firing when forming a film The temperature can be made lower than that of a conventional silica-based film forming composition. For this reason, it is suitable as a film-forming material for forming a flattening film used for applications in which high-temperature firing is not preferred.
• the film forming material obtained by the purification method according to the first or second aspect or the production method according to the third aspect can form an insulating film by containing the silicon compound.
• the film forming material obtained by the purification method according to the first or second aspect or the production method according to the third aspect can be used as a resin layer for imprinting.
• the film forming material obtained by the purification method according to the first or second aspect or the production method according to the third aspect can transfer a finer pattern with high accuracy, and a conformal fine pattern. Can be used to form a resin layer for room temperature imprinting.
• the film forming material obtained by the purification method according to the first or second aspect or the production method according to the third aspect can be used for forming an etching mask.
• the film forming material obtained by the purification method according to the first or second aspect or the production method according to the third aspect has a compound having a self-reactive property, and the firing temperature at the time of forming the coating film is conventional. Therefore, it can be suitably used as a composition for forming an etching mask.
• the film forming material obtained by the purification method according to the first or second aspect or the production method according to the third aspect was formed by patterning using a printing method such as an ink jet method or a screen printing method.
• the pattern can be used as an etching mask.
• a pattern obtained by coating the surface of a pattern such as a resist pattern with the composition of the present invention can also be used as an etching mask.
• a double pattern can also be formed by coating the surface of a pattern such as a resist pattern with the film forming material of the present invention and etching the upper part of the pattern.
• the film forming material obtained by the purification method according to the first or second aspect or the production method according to the third aspect can be used for forming a high refractive index film.
• an optical element such as a photoelectric integrated circuit, an optical integrated circuit, a CCD sensor, or a CMOS sensor, and processing the surface by etching or the like, An optical waveguide having a high refractive index can be formed.
• the film forming material obtained by the purification method according to the first or second aspect or the manufacturing method according to the third aspect is excellent in coating property and strength, pattern formation by lithography and planarization are possible. It can be suitably used for forming a film, an insulating film, a high refractive index film, an imprinting resin layer, an etching mask, or the like.
• the diffusing agent composition contains a dopant (impurity diffusion component) and is used for dopant diffusion into a semiconductor substrate.
• the diffusing agent composition to be purified preferably contains a silicon compound capable of generating a silanol group by hydrolysis represented by the general formula (2), and the silicon compound is represented by the following general formula (4). It is more preferable that it is a silicon compound represented by these.
• R a4 4-n4 Si (NCO) n4 (4) (In Formula (4), R a4 is a hydrocarbon group, and n4 is an integer of 3 or 4.)
• R a4 is preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an aromatic hydrocarbon group having 1 to 12 carbon atoms, or an aralkyl group having 1 to 12 carbon atoms.
• Preferable examples of the aliphatic hydrocarbon group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, and tert-butyl group.
• N-pentyl group isopentyl group, neopentyl group, cyclopentyl group, n-hexyl group, cyclohexyl group, n-heptyl group, n-cycloheptyl group, n-octyl group, n-cyclooctyl group, n-nonyl group, Examples include an n-decyl group, an n-undecyl group, and an n-dodecyl group.
• aromatic hydrocarbon group having 1 to 12 carbon atoms include phenyl group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group. Group, 4-ethylphenyl group, ⁇ -naphthyl group, ⁇ -naphthyl group, and biphenylyl group.
• Preferable examples of the aralkyl group having 1 to 12 carbon atoms include benzyl group, phenethyl group, ⁇ -naphthylmethyl group, ⁇ -naphthylmethyl group, 2- ⁇ -naphthylethyl group, and 2- ⁇ -naphthylethyl group. Is mentioned.
• a methyl group and an ethyl group are preferable, and a methyl group is more preferable.
• tetraisocyanate silane methyl triisocyanate silane, and ethyl triisocyanate silane are preferable, and tetraisocyanate silane is more preferable.
• the dopant is not particularly limited as long as it is a component conventionally used for doping a semiconductor substrate, and may be an n-type dopant or a p-type dopant.
• the n-type dopant include simple substances such as phosphorus, arsenic, and antimony, and compounds containing these elements.
• the p-type dopant include simple substances such as boron, gallium, indium, and aluminum, and compounds containing these elements.
• a phosphorus compound, a boron compound, or an arsenic compound is preferable because it is easily available and easy to handle.
• Preferred phosphorus compounds include phosphoric acid, phosphorous acid, diphosphorous acid, polyphosphoric acid, and diphosphorus pentoxide, phosphites, phosphate esters, trisphosphite (trialkylsilyl), and A tris (trialkylsilyl) phosphate etc. are mentioned.
• Preferred boron compounds include boric acid, metaboric acid, boronic acid, perboric acid, hypoboric acid, diboron trioxide, and trialkyl borate.
• Preferred arsenic compounds include arsenic acid and trialkyl arsenate.
• phosphite esters As the phosphorus compound, phosphite esters, phosphate esters, tris phosphite (trialkylsilyl), and tris phosphate (trialkylsilyl) are preferable, and among them, trimethyl phosphate, triethyl phosphate, phosphorus phosphite Trimethyl phosphate, triethyl phosphite, tris phosphate (trimethoxysilyl), and tris phosphite (trimethoxysilyl) are preferred, trimethyl phosphate, trimethyl phosphite, and tris phosphate (trimethylsilyl) are more preferred, Trimethyl phosphate is particularly preferred.
• trimethoxyboron, triethoxyboron, trimethylboron, and triethylboron are preferable.
• arsenic compound arsenic acid, triethoxyarsenic, and tri-n-butoxyarsenic are preferable.
• the content of the dopant in the diffusing agent composition is not particularly limited.
• the content of the dopant in the diffusing agent composition is the amount of the element (mol) that acts as a dopant in a semiconductor substrate such as phosphorus, arsenic, antimony, boron, gallium, indium, and aluminum contained in the dopant. ) Is preferably 0.01 to 5 times, more preferably 0.05 to 3 times the number of moles of Si contained in the silicon compound.
• the content of the silicon compound in the diffusing agent composition is preferably 0.001 to 3.0% by mass, more preferably 0.01 to 1.0% by mass, as the Si concentration.
• the diffusing agent composition contains the silicon compound at such a concentration, the external diffusion of the dopant from the thin coating film formed by using the diffusing agent composition is satisfactorily suppressed, and the dopant is favorably and uniformly formed. It can be diffused into the semiconductor substrate.
• the product to be purified does not contain a dopant, and the diffusing agent composition purified by the purification method of the present invention It is preferable to contain a dopant.
• the diffusing agent composition may further contain an organic solvent.
• the solvent include the organic solvents described above as specific examples and preferable examples of the organic solvent that can be contained in the silylating agent chemical.
• An organic solvent may be used independently and may be used in combination of 2 or more type.
• diffusion agent composition does not contain water substantially, when the said silicon compound is included.
• the fact that the diffusing agent composition does not substantially contain water means that the diffusing agent composition does not contain an amount of water that is hydrolyzed to such an extent that the silicon compound inhibits the object of the present invention. .
• the diffusing agent composition may contain various additives such as a surfactant, an antifoaming agent, a pH adjusting agent, and a viscosity adjusting agent as long as the object of the present invention is not impaired.
• the diffusing agent composition may contain a binder resin for the purpose of improving coating properties and film forming properties.
• Various resins can be used as the binder resin, and an acrylic resin is preferable.
• the polyimide and / or polyamide-imide porous membrane used in the purification method using the liquid according to the first aspect as a product to be purified has communication holes.
• the communication holes may be formed by individual pores (hereinafter, simply referred to as “pores”) that impart a porous property to the polyimide and / or polyamideimide porous membrane.
• the hole is preferably a hole having a curved surface on the inner surface described later, and more preferably a substantially spherical hole described later.
• a portion where such individual holes are formed adjacent to each other serves as a communication hole, and has a structure in which such holes communicate with each other.
• a plurality of such holes are connected.
• the “flow channel” is usually formed by a series of individual “holes” and / or “communication holes”. It can be said that the individual holes are holes formed by removing individual fine particles present in the polyimide resin-fine particle composite film in a later step in the method for producing a polyimide resin porous film described later.
• the communication hole is formed by removing the fine particles in a post-process at a portion where the individual fine particles existing in the polyimide resin-fine particle composite membrane are in contact with each other in the method for producing the polyimide resin porous membrane described later. It can also be said that the adjacent holes are formed by.
• the polyimide and / or polyamideimide porous membrane preferably has a communicating hole having an opening on the outer surface of the porous membrane that communicates with the inside of the porous membrane and is located on the outside (back side) of the porous membrane.
• the surface has an opening so as to ensure a fluid flow path through which the porous membrane passes.
• That the polyimide and / or polyamideimide porous membrane in the present invention has such a communication hole can be represented by, for example, Gurley air permeability, and the Gurley air permeability can be, for example, 30 to 1000 seconds. .
• the Gurley air permeability of the polyimide and / or polyamideimide porous membrane can be, for example, within 1000 seconds, preferably within 600 seconds, more preferably within 500 seconds, and most preferably within 300 seconds.
• the lower limit is not particularly set since it is preferably as low as possible. However, for example, 30 seconds or more may be used in order to efficiently perform a process such as metal removal while maintaining a relatively high flow rate of the fluid passing through the polyimide and / or polyamideimide porous membrane. preferable. If the Gurley air permeability is within 1000 seconds, the degree of porosity is sufficiently high, so that the effect of liquid purification can be enhanced in the present invention.
• the polyimide and / or polyamideimide porous membrane preferably includes a communication hole having a pore diameter of 1 to 200 nm.
• the diameter of the communication hole is preferably 3 to 180 nm, more preferably 5 to 150 nm, and still more preferably 10 to 130 nm.
• the diameter of the communication hole is the diameter of the communication hole. Since one communicating hole is usually formed from two adjacent particles by the manufacturing method described later, the diameter is, for example, a direction in which two individual holes constituting the communicating hole are continuous in the longitudinal direction. The diameter may be in a direction perpendicular to the longitudinal direction.
• the pore diameter of the communication hole is such that the pore diameter distribution of the individual holes imparting porosity to the polyimide and / or polyamideimide porous membrane is broader, and the individual holes are formed adjacent to each other.
• the porosity of the porous film is, for example, in the range of 60 to 90%, preferably 60 to 80%, and more preferably about 70%. It is. Further, even when the imide bond ring-opening step described later is not performed, the diameter of the communication hole tends to be small.
• the polyimide and / or polyamideimide porous membrane has communication holes, when the fluid is passed through the porous membrane, the fluid can pass through the porous membrane.
• the polyimide and / or polyamide-imide porous membrane preferably has a flow path in which individual pores having curved surfaces on the inner surface are continuous by communication holes, so that fluid can only pass through the inside of the porous membrane.
• the contact area with respect to the inner surface of the hole increases, and fine substances such as metal particles existing in the fluid are easily adsorbed to the hole in the porous film. It is considered a thing.
• the polyimide and / or polyamideimide porous membrane is preferably a porous membrane containing pores having a curved surface on the inner surface, and many (preferably substantially all) pores in the porous membrane. Is more preferably formed of a curved surface.
• “having a curved surface on the inner surface” means that at least an inner surface of the hole that provides the porosity has a curved surface on at least a part of the inner surface.
• substantially spherical hole means a hole whose inner surface forms a substantially spherical space. It can be said that the substantially spherical hole is preferably a hole formed when fine particles used in the method for producing a polyimide resin porous film described later are substantially spherical.
• substantially spherical is a concept including a true sphere, but is not necessarily limited to a true sphere, and is a concept including a substantially spherical shape.
• substantially spherical means that the sphericity defined by the sphericity represented by the value obtained by dividing the major axis of the particle by the minor axis is within 1 ⁇ 0.3. means.
• the substantially spherical pore of the polyimide and / or polyamide-imide porous membrane in the present invention preferably has a sphericity of 1 ⁇ 0.1 or less, and more preferably 1 ⁇ 0.05 or less.
• the pores in the porous membrane have a curved surface on the inner surface, so that when the fluid is passed through the polyimide and / or polyamideimide porous membrane, the fluid sufficiently spreads inside the pores in the porous membrane, and on the inner surface of the pores. It may be possible to make sufficient contact and possibly cause convection along the curved surface of the inner surface. In this way, it is considered that minute substances such as metal particles existing in the fluid are easily adsorbed to the pores in the porous film of the present invention or the concave portions that may be present on the inner surfaces of the pores.
• the substantially spherical hole may further have a recess on the inner surface.
• the concave portion may be formed by a hole having an opening on the inner surface of the substantially spherical hole and having a smaller hole diameter than the substantially spherical hole.
• the polyimide and / or polyamideimide porous membrane may be, for example, a porous membrane having an average pore size of 100 to 2000 nm, and the average pore size is preferably 200 to 1000 nm, more preferably 300 to 900 nm.
• the average pore diameter is a value obtained by calculating the size of the average communication hole by a porometer and performing the chemical etching treatment described later, and obtaining the actual average pore diameter from that value.
• the average particle diameter of the fine particles used in the production of the porous film can be set as the average pore diameter.
• the polyimide and / or polyamideimide porous membrane preferably includes a structure in which substantially spherical pores having an average spherical diameter of 50 to 2000 nm communicate with each other.
• the average spherical diameter of the substantially spherical hole is preferably 100 to 1000 nm, more preferably 200 to 800 nm.
• the average spherical diameter of the substantially spherical pores can be obtained by the same method as the average pore diameter in the porous membrane described above.
• the polyimide and / or polyamideimide porous membrane may be a porous membrane having a porosity of 50 to 90% by mass, preferably 55 to 80% by mass, determined by the method described below.
• the polyimide and / or polyamide-imide porous membrane used in the purification method using the liquid according to the first aspect as a material to be purified contains a resin, and may consist essentially of a resin, Specifically, 95% by mass or more, preferably 98% by mass or more, more preferably 99% by mass or more is the resin.
• a resin contained in the polyimide and / or polyamide-imide porous membrane in the present invention polyimide and / or polyamide-imide is preferable, a resin containing polyimide is more preferable, and only polyimide may be used.
• polyimide and / or polyamideimide may be referred to as “polyimide resin”.
• the polyimide and / or polyamideimide contained in the polyimide and / or polyamideimide porous membrane is a carboxy group, It may have at least one selected from the group consisting of a salt-type carboxy group and an —NH— bond.
• the polyimide and / or polyamideimide preferably has a carboxy group, salt-type carboxy group and / or —NH— bond other than the main chain terminal of the polyimide and / or polyamideimide.
• the “salt-type carboxy group” means a group in which a hydrogen atom in a carboxy group is substituted with a cation component.
• the “cationic component” may be a cation itself that is in a completely ionized state, or a cation component that is ionically bonded to —COO 2 — and is in an essentially uncharged state. It may be a cation component having a partial charge which is an intermediate state between the two.
• the “cation component” is an M ion component composed of an n-valent metal M
• the cation itself is represented as M n +
• the cation component is represented by “M” in “ ⁇ COOM 1 / n ”. Element.
• the “cation component” includes a cation when a compound mentioned as a compound contained in a chemical etching solution described later is ionically dissociated, and typically includes an ionic component or an organic alkali ion component.
• the alkali metal ion component is a sodium ion component
• the cation itself is a sodium ion (Na + )
• the cation component is an element represented by “Na” in “—COONa”.
• the charged cation component is Na ⁇ + .
• the cation component is not particularly limited, and may be any of inorganic components, organic components such as NH 4 + , N (CH 3 ) 4 +, and the like.
• Examples of the inorganic component include metal elements such as alkali metals such as Li, Na, and K, and alkaline earth metals such as Mg and Ca.
• Examples of the organic component, especially the organic alkali ion component include quaternary ammonium cations represented by NH 4 + , for example, NR 4 + (four Rs are the same or different and each represents an organic group). It is done.
• the organic group as R is preferably an alkyl group, more preferably an alkyl group having 1 to 6 carbon atoms.
• Examples of the quaternary ammonium cation include N (CH 3 ) 4 + .
• the state of the “salt-type carboxy group” and the “cationic component” is not particularly limited, and is usually in an environment where polyimide and / or polyamideimide exists, for example, in an aqueous solution. It may depend on whether it is in an organic solvent, dried, etc.
• the cation component is a sodium ion component, for example, if it is in an aqueous solution, it may be dissociated into —COO 2 — and Na +, and if it is in an organic solvent or dried, There is a high possibility that COONa is not dissociated.
• the polyimide and / or polyamideimide may have at least one selected from the group consisting of a carboxy group, a salt-type carboxy group, and an —NH— bond, and when having at least one of these, Usually, it has both a carboxy group and / or a salt-type carboxy group and an —NH— bond.
• the polyimide and / or the polyamide-imide may have only a carboxy group, or may have only a salt-type carboxy group, or a carboxy group and a salt type. You may have both of a carboxy group.
• the ratio of the carboxy group and the salt-type carboxy group possessed by the polyimide and / or polyamide imide varies depending on the environment in which the polyimide and / or polyamide imide is present, even for the same polyimide and / or polyamide imide. It is also affected by the concentration of the cation component.
• the total number of moles of the carboxy group and the salt-type carboxy group possessed by the polyimide and / or polyamideimide is usually equimolar to the —NH— bond.
• the method for producing a polyimide porous film described later In the case of forming a carboxy group and / or a salt-type carboxy group from a part of the imide bond in the polyimide, a —NH— bond is also formed at substantially the same time, and the total number of moles of the formed carboxy group and the salt-type carboxy group Is equimolar to the —NH— bond formed.
• the total number of carboxy groups and salt-type carboxy groups in the polyamideimide is not necessarily equimolar with the —NH— bond, but depends on the conditions of the imide bond ring opening step such as chemical etching described later.
• the polyimide and / or polyamideimide may have at least one selected from the group consisting of structural units represented by the following formulas (3) to (6).
• it When it is a polyimide, it may have a structural unit represented by the following formula (3) and / or (4), and when it is a polyamideimide, it is represented by the following formula (5) and / or (6). It may have a structural unit.
• X is the same or different and is a hydrogen atom or a cation component.
• Ar is an aryl group, and Ar is bonded to a carbonyl group in each of the repeating unit represented by the formula (1) constituting the polyamic acid described later or the repeating unit represented by the formula (2) constituting the aromatic polyimide. It may be the same as the aryl group represented by Y is a divalent residue excluding the amino group of the diamine compound, and the repeating unit represented by the formula (1) constituting the polyamic acid described later or the repeating represented by the formula (2) constituting the aromatic polyimide. It may be the same as the aryl group represented by Ar to which N is bonded in each unit.
• the polyimide and / or polyamideimide is partially opened by a part of the imide bond ([—C ( ⁇ O)] 2 —N—) of general polyimide and / or polyamideimide.
• the structural unit represented by (3) and / or (4) and polyamideimide the structural unit represented by the above formula (5) may be included.
• the object of the present invention can be achieved only by having an amide bond (—NH—C ( ⁇ O) —) originally possessed without opening the imide bond of general polyamide-imide. We have found that this can be achieved.
• it is preferable that a part of the imide bond originally possessed by the polyamideimide is ring-opened to have the structural unit represented by the above (5).
• the polyimide and / or polyamideimide is a polyimide and / or polyamide having at least one selected from the group consisting of a carboxy group, a salt-type carboxy group, and an —NH— bond by opening a part of the imide bond. It is good also as an imide porous membrane.
• the rate of change in the case where a part of the imide bond is opened is determined as follows.
• the area of the peak representing the imide bond measured by a Fourier transform infrared spectroscopy (FT-IR) apparatus is the same as the peak representing the benzene measured by the FT-IR apparatus.
• a value (X2) represented by a value divided by the area is obtained.
• Unchangeable rate (%) (X2) ⁇ (X1) ⁇ 100
• the invariant rate is preferably 60% or more, more preferably 70% to 99.5%, and more preferably 80 to 99%. Further preferred.
• the peak area representing the imide bond measured by a Fourier transform infrared spectroscopy (FT-IR) apparatus is also the same as the FT-IR.
• FT-IR Fourier transform infrared spectroscopy
• the imidization ratio in the case of polyimide, (X2) in the above description is preferably 1.2 or more, and preferably 1.2 to 2. More preferred are those of 1.3 to 1.6, even more preferred are 1.30 to 1.55, and particularly preferred is 1.35 to less than 1.5.
• the imidation ratio indicates that the larger the number, the greater the number of imide bonds, that is, the smaller the above-mentioned ring-opened imide bonds.
• the polyimide and / or polyamideimide porous membrane is a step of forming a carboxy group and / or a salt-type carboxy group from a part of the imide bond in the polyimide and / or polyamideimide (hereinafter referred to as “imide bond ring-opening step”).
• imide bond ring-opening step Can be produced by a method comprising: In the imide bond ring-opening step, as described above, when a carboxy group and / or a salt-type carboxy group is formed from a part of the imide bond, in theory, these groups are theoretically equimolar with —NH— bond. Is also formed.
• the imide bond ring-opening step is preferably performed by chemical etching described later.
• the resin contained in the polyimide and / or polyamide-imide porous membrane is substantially made of polyamide-imide, it already has —NH— bonds even without the imide bond ring-opening step, and has good adsorption power.
• the imide bond ring-opening step is not necessarily required in order to achieve the object of the present invention. It is preferable to perform a ring-opening step.
• the manufacturing method of the said polyimide and / or a polyamide-imide porous membrane includes the process (imide bond ring-opening process) which forms a carboxy group and / or a salt-type carboxy group from a part of imide bond in a polyimide and / or a polyamideimide. It may be a thing.
• membrane which has a polyimide and / or a polyamide imide as a main component
• it may abbreviate as a "polyimide and / or a polyamide-imide shaping
• the polyimide and / or polyamide-imide molded film that is the subject of the imide bond ring-opening step may be porous or non-porous, and its shape is not particularly limited.
• the polyimide and / or polyamideimide molded membrane is preferably porous, and / or a thin shape such as a membrane, in that the degree of porosity in the obtained polyimide and / or polyamideimide porous membrane can be increased. It is preferable that
• the polyimide and / or polyamide-imide molded film may be non-porous when the imide bond ring-opening step is performed.
• the polyimide and / or polyamide-imide molded film may be made porous after the imide bond ring-opening step.
• a method for making a polyimide and / or polyamideimide molded film porous before or after the imide bond ring-opening step a composite film of polyimide and / or polyamideimide and fine particles (hereinafter referred to as “ A method including a fine particle removing step of removing the fine particles from the polyimide-based resin-fine particle composite film) and making them porous is preferable.
• a polyimide and / or polyamideimide / fine particle composite membrane may be subjected to an imide bond ring opening step before the fine particle removal step.
• the polyimide and / or polyamideimide molded film made porous by the step may be subjected to an imide bond ring-opening step, but the resulting polyimide and / or polyamideimide porous
• the latter method (b) is preferred in that the degree of porosity in the membrane can be increased.
• the production method of the polyimide and / or polyamide-imide porous film will be described in detail mainly by taking the form of a film (porous film) as a preferred embodiment.
• the membrane can be suitably manufactured using varnish.
• the varnish is produced by mixing an organic solvent in which fine particles are dispersed in advance with polyamic acid, polyimide or polyamideimide in an arbitrary ratio, or by polymerizing tetracarboxylic dianhydride and diamine in an organic solvent in which fine particles are dispersed in advance. It can be produced by using polyamic acid or further imidized to form polyimide, and the viscosity is preferably 300 to 2000 cP, and more preferably in the range of 400 to 1800 cP. If the viscosity of the varnish is within this range, it is possible to form a film uniformly.
• the fine particle / polyimide resin ratio is 1 to 4 (mass ratio) when the fine particles are fired (or dried if firing is optional) to form a polyimide resin-fine particle composite film.
• the resin fine particles can be mixed with polyamic acid or polyimide or polyamideimide, and the ratio of fine particles / polyimide resin is preferably 1.1 to 3.5 (mass ratio).
• the fine particles and polyamic acid or polyimide or polyamideimide may be mixed so that the volume ratio of fine particles / polyimide resin is 1.1 to 5.
• the ratio of fine particles / polyimide resin is more preferably 1.1 to 4.5 (volume ratio).
• volume% and volume ratio are values at 25 ° C.
• the material of the fine particles used in the present invention is not particularly limited as long as it is insoluble in the organic solvent used for the varnish and can be selectively removed after film formation.
• inorganic materials include silica (silicon dioxide), titanium oxide, alumina (Al 2 O 3 ), metal oxides such as calcium carbonate, and organic materials include high molecular weight olefins (polypropylene, polyethylene, etc.), polystyrene, acrylic Organic polymer fine particles (resin fine particles) such as epoxy resins (methyl methacrylate, isobutyl methacrylate, polymethyl methacrylate (PMMA), etc.), epoxy resins, cellulose, polyvinyl alcohol, polyvinyl butyral, polyester, polyether, polyethylene, etc. .
• Preferred examples of the inorganic material that can be used in the production of the polyimide resin porous membrane include silica such as colloidal silica or organic polymer fine particle PMMA. Among these, it is preferable to select these spherical particles in order to form minute holes having a curved surface on the inner surface.
• the resin fine particles can be selected from, for example, ordinary linear polymers and known depolymerizable polymers without particular limitation depending on the purpose.
• a normal linear polymer is a polymer in which polymer molecular chains are randomly cut during thermal decomposition
• a depolymerizable polymer is a polymer in which the polymer is decomposed into monomers during thermal decomposition. Any of them can be removed from the polyimide resin film by decomposition to a monomer, a low molecular weight substance, or CO 2 at the time of heating.
• the decomposition temperature of the resin fine particles used is preferably 200 to 320 ° C., more preferably 230 to 260 ° C. When the decomposition temperature is 200 ° C.
• film formation can be performed even when a high boiling point solvent is used for the varnish, and the range of selection of the baking conditions for the polyimide resin is widened. If the decomposition temperature is 320 ° C. or lower, only the resin fine particles can be lost without causing thermal damage to the polyimide resin.
• methyl methacrylate or isobutyl methacrylate alone (polymethyl methacrylate or polyisobutyl methacrylate) having a low thermal decomposition temperature, or a copolymer having a main component thereof is preferable for handling during pore formation. .
• the fine particles are preferably those having a high sphericity in that they tend to have curved surfaces on the inner surfaces of the pores in the porous film to be formed.
• the particle size (average diameter) of the fine particles to be used for example, those having a particle size of 50 to 2000 nm, preferably 200 to 1000 nm can be used.
• the polyimide resin porous membrane obtained by removing the fine particles allows the fluid to uniformly contact the inner surface of the pores in the porous membrane when passing the fluid as a separating material or adsorbent, the metal contained in the fluid Adsorption of minute substances such as particles can be performed efficiently, which is preferable.
• the particle size distribution index (d25 / 75) may be 1 to 6, preferably 1.6 to 5, and more preferably 2 to 4.
• d25 and d75 are values of particle diameters in which the cumulative frequency of the particle size distribution is 25% and 75%, respectively, and in this specification, d25 is the larger particle diameter.
• the fine particles (B1) used for the first varnish and the fine particles (B2) used for the second varnish are the same. A thing different from each other may be used.
• the fine particles of (B1) preferably have a smaller or the same particle size distribution index as the fine particles of (B2).
• the fine particles of (B1) it is preferable that the fine particles of (B1) have a smaller sphericity or the same as the fine particles of (B2).
• the fine particles of (B1) preferably have a smaller particle size (average diameter) than the fine particles of (B2), and in particular, (B1) is 100 to 1000 nm (more preferably 100 to 600 nm), (B2 ) Is preferably 500 to 2000 nm (more preferably 700 to 2000 nm).
• (B2) is 100 to 1000 nm (more preferably 100 to 600 nm)
• (B2 ) Is preferably 500 to 2000 nm (more preferably 700 to 2000 nm).
• a dispersant may be further added together with the fine particles.
• the dispersant By adding the dispersant, the polyamic acid, polyimide or polyamideimide and the fine particles can be mixed more uniformly, and furthermore, the fine particles in the formed or formed precursor film can be uniformly distributed.
• the front and back surfaces of the porous membrane are made efficient so that dense openings are provided on the surface of the finally obtained polyimide resin porous membrane and the air permeability of the polyimide resin porous membrane is improved. It is possible to form a communication hole that communicates well.
• the dispersant used in the present invention is not particularly limited, and known ones can be used.
• Anionic surfactants such as nate salt, isopropyl phosphate, polyoxyethylene alkyl ether phosphate salt, polyoxyethylene allyl phenyl ether phosphate salt; oleylamine acetate, lauryl pyridinium chloride, cetyl pyridinium chloride, lauryl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride , Behenyltrimethylammonium
• polyamic acid used in the present invention those obtained by polymerizing any tetracarboxylic dianhydride and diamine can be used without any particular limitation.
• the amount of tetracarboxylic dianhydride and diamine used is not particularly limited, but 0.50 to 1.50 mol of diamine is preferably used relative to 1 mol of tetracarboxylic dianhydride, and 0.60 to 1. It is more preferable to use 30 mol, and it is particularly preferable to use 0.70 to 1.20 mol.
• the tetracarboxylic dianhydride can be appropriately selected from tetracarboxylic dianhydrides conventionally used as raw materials for polyamic acid synthesis.
• the tetracarboxylic dianhydride may be an aromatic tetracarboxylic dianhydride or an aliphatic tetracarboxylic dianhydride. From the viewpoint of the heat resistance of the resulting polyimide resin, the aromatic tetracarboxylic dianhydride may be used. Preference is given to using carboxylic dianhydrides. Tetracarboxylic dianhydride may be used in combination of two or more.
• aromatic tetracarboxylic dianhydride examples include pyromellitic dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxy Phenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′- Biphenyltetracarboxylic dianhydride, 2,2,6,6-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2 , 3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2
• Examples of the aliphatic tetracarboxylic dianhydride include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane tetracarboxylic dianhydride, 1, Examples include 2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, and the like. Among these, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride and pyromellitic dianhydride are preferable from the viewpoints of price and availability. These tetracarboxylic dianhydrides can be used alone or in combination of two or more.
• the diamine can be appropriately selected from diamines conventionally used as a raw material for synthesizing polyamic acid.
• This diamine may be an aromatic diamine or an aliphatic diamine, but an aromatic diamine is preferred from the viewpoint of the heat resistance of the resulting polyimide resin.
• These diamines may be used in combination of two or more.
• aromatic diamines include diamino compounds in which one or about 2 to 10 phenyl groups are bonded. Specifically, phenylenediamine and derivatives thereof, diaminobiphenyl compounds and derivatives thereof, diaminodiphenyl compounds and derivatives thereof, diaminotriphenyl compounds and derivatives thereof, diaminonaphthalene and derivatives thereof, aminophenylaminoindane and derivatives thereof, diaminotetraphenyl Compounds and derivatives thereof, diaminohexaphenyl compounds and derivatives thereof, and cardo-type fluorenediamine derivatives.
• Phenylenediamine is m-phenylenediamine, p-phenylenediamine, etc., and phenylenediamine derivatives include diamines to which alkyl groups such as methyl group and ethyl group are bonded, such as 2,4-diaminotoluene, 2,4-triphenylene. Diamines and the like.
• the diaminobiphenyl compound is a compound in which two aminophenyl groups are bonded to each other.
• the diaminobiphenyl compound is a compound in which two aminophenyl groups are bonded to each other.
• the diaminodiphenyl compound is a compound in which two aminophenyl groups are bonded to each other via other groups.
• the bond is an ether bond, a sulfonyl bond, a thioether bond, a bond by alkylene or a derivative group thereof, an imino bond, an azo bond, a phosphine oxide bond, an amide bond, a ureylene bond, or the like.
• the alkylene bond has about 1 to 6 carbon atoms, and the derivative group has one or more hydrogen atoms in the alkylene group substituted with halogen atoms or the like.
• diaminodiphenyl compounds include 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl ketone 3,4′-diaminodiphenyl ketone, 2,2-bis (p-aminophenyl) propane, 2,2′-bis (p-aminophenyl) hexafluor
• p-phenylenediamine p-phenylenediamine, m-phenylenediamine, 2,4-diaminotoluene, and 4,4'-diaminodiphenyl ether are preferable from the viewpoint of price and availability.
• the diaminotriphenyl compound is one in which two aminophenyl groups and one phenylene group are bonded via another group, and the other groups are the same as those of the diaminodiphenyl compound.
• Examples of diaminotriphenyl compounds include 1,3-bis (m-aminophenoxy) benzene, 1,3-bis (p-aminophenoxy) benzene, 1,4-bis (p-aminophenoxy) benzene, and the like. be able to.
• diaminonaphthalene examples include 1,5-diaminonaphthalene and 2,6-diaminonaphthalene.
• aminophenylaminoindane examples include 5 or 6-amino-1- (p-aminophenyl) -1,3,3-trimethylindane.
• diaminotetraphenyl compounds examples include 4,4′-bis (p-aminophenoxy) biphenyl, 2,2′-bis [p- (p′-aminophenoxy) phenyl] propane, 2,2′-bis [ and p- (p′-aminophenoxy) biphenyl] propane, 2,2′-bis [p- (m-aminophenoxy) phenyl] benzophenone, and the like.
• cardo-type fluorenediamine derivatives include 9,9-bisaniline fluorene.
• the aliphatic diamine preferably has about 2 to 15 carbon atoms, and specific examples include pentamethylene diamine, hexamethylene diamine, and heptamethylene diamine.
• a compound in which the hydrogen atom of these diamines is substituted with at least one substituent selected from the group such as a halogen atom, a methyl group, a methoxy group, a cyano group, and a phenyl group may be used.
• the means for producing the polyamic acid used in the present invention is not particularly limited, and for example, a known method such as a method of reacting an acid and a diamine component in an organic solvent can be used.
• the reaction between tetracarboxylic dianhydride and diamine is usually carried out in an organic solvent.
• the organic solvent used for the reaction of the tetracarboxylic dianhydride and the diamine is particularly capable of dissolving the tetracarboxylic dianhydride and the diamine and not reacting with the tetracarboxylic dianhydride and the diamine. It is not limited. An organic solvent can be used individually or in mixture of 2 or more types.
• organic solvents used in the reaction of tetracarboxylic dianhydride with diamine include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N Nitrogen-containing polar solvents such as N, diethylformamide, N-methylcaprolactam, N, N, N ′, N′-tetramethylurea; ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone Lactone polar solvents such as ⁇ -caprolactone and ⁇ -caprolactone; dimethyl sulfoxide; acetonitrile; fatty acid esters such as ethyl lactate and butyl lactate; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dioxane, tetrahydrofuran, methyl cellosolve acetate,
• organic solvents can be used alone or in admixture of two or more. Among these, a combination of the nitrogen-containing polar solvent and the lactone polar solvent is preferable.
• the amount of the organic solvent used is not particularly limited, but it is desirable that the content of the polyamic acid to be produced is 5 to 50% by mass.
• N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N- Nitrogen-containing polar solvents such as diethylformamide, N-methylcaprolactam, N, N, N ′, N′-tetramethylurea are preferred.
• it may be a mixed solvent to which a lactone polar solvent such as ⁇ -butyrolactone is added, and is preferably added in an amount of 1 to 20% by mass with respect to the whole organic solvent. % Is more preferable.
• the polymerization temperature is generally ⁇ 10 to 120 ° C., preferably 5 to 30 ° C.
• the polymerization time varies depending on the raw material composition used, but is usually 3 to 24 Hr (hour).
• the intrinsic viscosity of the polyamic acid solution obtained under such conditions is preferably in the range of 1000 to 100,000 cP (centipoise), and more preferably in the range of 5000 to 70000 cP.
• the polyimide used in the present invention is not limited to its structure and molecular weight as long as it is a soluble polyimide that can be dissolved in the organic solvent used in the varnish according to the present invention.
• a polyimide you may have a functional group which accelerates
• a monomer to introduce a flexible bending structure into the main chain in order to obtain a polyimide soluble in an organic solvent for example, ethylenediamine, hexamethylenediamine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, Aliphatic diamines such as 4,4'-diaminodicyclohexylmethane; 2-methyl-1,4-phenylenediamine, o-tolidine, m-tolidine, 3,3'-dimethoxybenzidine, 4,4'-diaminobenzanilide, etc.
• an organic solvent for example, ethylenediamine, hexamethylenediamine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, Aliphatic diamines such as 4,4'-diaminodicyclohexylmethane; 2-methyl-1,4-phenylenediamine
• Aromatic diamines such as polyoxyethylene diamine, polyoxypropylene diamine and polyoxybutylene diamine; polysiloxane diamines; 2,3,3 ′, 4′-oxydiphthalic anhydride, 3,4,3 ′ , 4'-oxydiphthalic anhydride, 2,2-bis (4- Hydroxyphenyl) propane dibenzoate-3,3 ', use of such 4,4'-tetracarboxylic dianhydride is valid.
• a monomer having a functional group that improves the solubility in an organic solvent for example, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2-trifluoromethyl-1,4 It is also effective to use a fluorinated diamine such as phenylenediamine.
• a monomer having a functional group that improves the solubility in an organic solvent for example, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2-trifluoromethyl-1,4
• a fluorinated diamine such as phenylenediamine.
• the same monomers as those described in the column for the polyamic acid can be used in combination as long as the solubility is not inhibited.
• polyimide which can be melt
• well-known methods such as the method of making a polyamic acid chemically imidate or heat imidize, and making it melt
• polyimide include aliphatic polyimide (total aliphatic polyimide), aromatic polyimide and the like, and aromatic polyimide is preferable.
• the aromatic polyimide is obtained by thermally or chemically obtaining a polyamic acid having a repeating unit represented by the formula (1) by a ring-closing reaction or by dissolving a polyimide having a repeating unit represented by the formula (2) in a solvent.
• Ar represents an aryl group.
• any known polyamide-imide can be used as long as it is a soluble polyamide-imide that can be dissolved in the organic solvent used in the varnish according to the present invention without being limited to its structure and molecular weight.
• the polyamideimide may have a functional group capable of condensing such as a carboxy group in the side chain or a functional group that promotes a crosslinking reaction or the like during firing.
• the polyamideimide used in the present invention is obtained by reacting any trimellitic anhydride and diisocyanate, or a precursor polymer obtained by reacting any reactive trimellitic anhydride derivative with diamine. Those obtained by imidization can be used without any particular limitation.
• trimellitic anhydride halides such as trimellitic anhydride and trimellitic anhydride chloride, trimellitic anhydride ester, and the like.
• optional diisocyanate examples include metaphenylene diisocyanate, p-phenylene diisocyanate, o-tolidine diisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, 4,4′-oxybis (phenylisocyanate), and 4,4′-diisocyanate.
• Diphenylmethane bis [4- (4-isocyanatophenoxy) phenyl] sulfone, 2,2'-bis [4- (4-isocyanatophenoxy) phenyl] propane, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate 4,4′-diphenylmethane diisocyanate, 3,3′-dimethyldiphenyl-4,4′-diisocyanate, 3,3′-diethyldiphenyl-4,4′-diisocyanate, isophor Diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, m- xylene diisocyanate, p- xylene diisocyanate, naphthalene diisocyanate, and the like.
• Examples of the arbitrary diamine include those similar to those exemplified in the description of the polyamic acid.
• Organic solvent used for the varnish is not particularly limited as long as it can dissolve the polyamic acid and / or the polyimide-based resin and does not dissolve the fine particles.
• the reaction between the tetracarboxylic dianhydride and the diamine What was illustrated as a solvent to be used is mentioned.
• a solvent may be used independently and may be used in combination of 2 or more type.
• the content of the mixed solvent (S) is preferably 50 to 95% by mass, more preferably 60 to 85% by mass.
• the solid content concentration in the varnish is preferably 5 to 50% by mass, more preferably 15 to 40% by mass.
• the volume ratio of the polyamic acid, polyimide or polyamideimide (A1) and fine particles (B1) in the first varnish is set to It is preferably 19:81 to 45:65. If the volume of the fine particles is 65 or more when the total volume is 100, the particles are uniformly dispersed, and if the volume is within 81, the particles are dispersed without agglomeration. The holes can be formed uniformly.
• the volume ratio of polyamic acid, polyimide or polyamideimide (A2) and fine particles (B2) is preferably 20:80 to 50:50.
• the fine particle volume is 50 or more when the total volume is 100, the single particles are uniformly dispersed, and if they are within 80, the particles do not aggregate with each other, and cracks and the like may occur on the surface. Therefore, it is possible to stably form a polyimide-based resin porous film having good mechanical properties such as stress and elongation at break.
• a 2nd varnish is a thing with a fine particle content ratio lower than said 1st varnish, and by satisfy
• fine-particles are in a polyamic acid, a polyimide, or a polyamideimide. Even if highly filled, the strength and flexibility of the unfired composite film, the polyimide resin-fine particle composite film, and the polyimide resin porous film can be ensured. Further, by providing a layer having a low fine particle content ratio, it is possible to reduce the manufacturing cost.
• antistatic agents In addition to the above components, antistatic agents, flame retardants, chemical imidizing agents, condensing agents, mold release agents, surfaces for the purpose of antistatic, imparting flame retardancy, low-temperature firing, releasability, coatability, etc.
• a known component such as a regulator can be appropriately contained as necessary.
• the above varnish is applied to the substrate, and 0 to 120 ° C. (preferably 0 to 100 ° C.), more preferably 60 to 95 ° C. (more preferably 65 to 90 ° C.) under normal pressure.
• the coating thickness is, for example, 1 to 500 ⁇ m, preferably 5 to 200 ⁇ m, and more preferably 5 to 50 ⁇ m.
• a release layer may be provided on the substrate as necessary.
• the release layer can be produced by applying a release agent on a substrate and drying or baking.
• a release agent known release agents such as alkyl phosphate ammonium salt, fluorine-based or silicone can be used without particular limitation.
• the release agent remains slightly on the peeled surface of the unfired composite film. Since this remaining mold release agent can affect the wettability of the polyimide-based resin porous membrane surface and mixing of impurities, it is preferable to remove this.
• the cleaning method can be selected from known methods such as a method of removing the unfired composite film after immersing it in the cleaning liquid, and a method of shower cleaning. Furthermore, in order to dry the unfired composite film after washing, the known method such as air-drying the washed unfired composite film at room temperature or heating to an appropriate set temperature in a thermostatic bath is not limited. Applicable. For example, a method of preventing deformation by fixing the end of the unfired composite film to a SUS formwork or the like can also be adopted.
• the above-mentioned release layer forming step and the unfired composite film cleaning step can be omitted.
• the first varnish is applied as it is on a substrate such as a glass substrate, and 0 to 120 ° C. (preferably 0 to 90 ° C.) under normal pressure or vacuum. At a normal pressure of 10 to 100 ° C. (more preferably 10 to 90 ° C.) to form a first unfired composite film having a thickness of 1 to 40 ⁇ m.
• the second varnish is applied onto the formed first unfired composite film, and similarly, 0 to 80 ° C. (preferably 0 to 50 ° C.), more preferably normal pressure 10 to 80 ° C. ( More preferably, drying is performed at 10 to 30 ° C. to form a second unfired composite film having a film thickness of 5 to 150 ⁇ m to obtain a two-layer unfired composite film.
• the dried unfired composite film (or two-layer unfired composite film, hereinafter the same) is subjected to post-treatment (baking) by heating to form a composite film comprising polyimide resin and fine particles (polyimide resin-fine particle composite film) ).
• baking post-treatment
• the varnish contains polyamic acid
• a baking process is an arbitrary process. In particular, when polyimide or polyamideimide is used for the varnish, the firing step may not be performed.
• the firing temperature varies depending on the structure of the polyamic acid or polyimide resin contained in the unfired composite film or the presence or absence of a condensing agent, but is preferably 120 to 400 ° C, more preferably 150 to 375 ° C.
• the thickness of the completed polyimide resin-particle composite film can be obtained, for example, by measuring the thickness of a plurality of locations with a micrometer or the like and averaging. What average thickness is preferable depends on the use of the polyimide resin-fine particle composite membrane or the polyimide resin porous membrane. For example, when used for a separation material, an adsorbent, etc., the thinner one is preferable. For example, it may be 1 ⁇ m or more, preferably 5 to 500 ⁇ m, and more preferably 8 to 100 ⁇ m.
• a polyimide resin porous film having fine pores can be produced with good reproducibility.
• the polyimide resin-fine particle composite film can be made porous by dissolving and removing silica with a low concentration of hydrogen fluoride water (HF) or the like.
• HF hydrogen fluoride water
• the resin fine particles can be removed by heating to a temperature not lower than the thermal decomposition temperature of the resin fine particles as described above and lower than the thermal decomposition temperature of the polyimide resin.
• the method for producing a polyimide-based resin porous membrane in the present invention may include an imide bond ring-opening step as described above, and specifically, (a) a polyimide-based resin before the fine particle removing step. -Applying an imide bond ring-opening step to the fine particle composite film, or (b) After performing the fine particle removal step, applying a imide bond ring-opening step to the polyimide resin molded film made porous by the step It can be carried out.
• the imide bond existing on the outer surface of the polyimide-based resin molded film and in the vicinity thereof can be opened, and the object of the present invention is achieved.
• the latter (b) is preferred in that the degree of porosity in the resulting polyimide resin porous membrane can be increased.
• the imide bond ring-opening step can be performed by a chemical etching method, a physical removal method, or a combination thereof. It does not specifically limit as a chemical etching method, For example, a conventionally well-known method can be used.
• Examples of the chemical etching method include treatment with a chemical etching solution such as an inorganic alkali solution or an organic alkali solution.
• a chemical etching solution such as an inorganic alkali solution or an organic alkali solution.
• Inorganic alkaline solutions are preferred.
• examples of inorganic alkaline solutions include hydrazine solutions containing hydrazine hydrate and ethylenediamine, solutions of alkali metal hydroxides such as potassium hydroxide, sodium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia solutions, alkali hydroxides And an etching solution mainly containing hydrazine and 1,3-dimethyl-2-imidazolidinone.
• Organic alkaline solutions include primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethylamine; dimethylethanolamine And alcohol amines such as triethanolamine; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; and alkaline solutions such as cyclic amines such as pyrrole and pihelidine.
• primary amines such as ethylamine and n-propylamine
• secondary amines such as diethylamine and di-n-butylamine
• tertiary amines such as triethylamine and methyldiethylamine
• dimethylethanolamine And alcohol amines such as triethanolamine
• quaternary ammonium salts such as tetra
• the solvent of each solution pure water and alcohols can be selected as appropriate. Moreover, what added a suitable amount of surfactant can also be used.
• the alkali concentration is, for example, 0.01 to 20% by mass.
• plasma oxygen, argon, etc.
• dry etching by corona discharge, etc. can be used.
• the above-described method is preferable because it can be applied to any imide bond ring-opening step before or after the fine particle removal step.
• it is easy to form the communicating hole inside a polyimide resin porous membrane, and can improve a hole area rate.
• a part or all of the liquid is transferred from one side of the polyimide-based resin porous membrane to the other.
• the permeation of the liquid can be usually performed by filtering part or all of the liquid using a polyimide resin porous membrane as a separating material or adsorbing material.
• the polyimide resin porous membrane used as a separating material or adsorbing material may be incorporated in a filter device described later.
• the planar or polyimide resin porous membrane relative A pipe shape with matching sides is mentioned. It is preferable that the pipe-shaped polyimide resin porous membrane is further formed into a pleated shape because the area in contact with the supply liquid increases. The polyimide resin porous membrane is appropriately sealed so that the supply liquid and the filtrate are not mixed as described later.
• Purification of the liquid or silicon compound-containing liquid can be performed by using the above-mentioned polyimide resin porous membrane without differential pressure, that is, by natural filtration by gravity, but is preferably performed by differential pressure.
• the differential pressure is not particularly limited as long as a pressure difference is provided between one side and the other side of the polyimide resin porous membrane, but usually one side of the polyimide resin porous membrane (supply) Pressure (positive pressure) for applying pressure to the liquid side), reduced pressure (negative pressure) for making one side (filtrate side) of the polyimide-based resin porous membrane negative, and the like are preferred, and pressurization is preferred.
• Pressurization is performed on the side of the polyimide resin porous membrane (supply liquid) where there is a liquid or a silicon compound-containing liquid (which may be referred to as “supply liquid” in this specification) prior to permeation through the polyimide resin porous film.
• supply liquid a liquid or a silicon compound-containing liquid
• the pressure is preferably applied by using the flowing liquid pressure generated by circulating or feeding the supply liquid or by using the positive pressure of the gas.
• the fluid pressure can be generated by an active fluid pressure application method such as a pump (liquid feed pump, circulation pump, etc.), and specifically, a rotary pump, a diaphragm pump, a metering pump, a chemical pump, A plunger pump, a bellows pump, a gear pump, a vacuum pump, an air pump, a liquid pump, etc. are mentioned.
• the flowing liquid pressure is, for example, a pressure applied to the polyimide resin porous membrane by the liquid or silicon compound-containing liquid when allowing the liquid or silicon compound-containing liquid to permeate the polyimide resin porous membrane only according to gravity.
• pressure is applied by the above-described positive fluid pressure application method.
• the gas used for pressurization is preferably a gas that is inert or non-reactive with respect to the supply liquid, and specifically includes nitrogen or a rare gas such as helium or argon.
• pressurization is preferred.
• the side that collects the liquid that has permeated the polyimide resin porous membrane or the silicon compound-containing liquid may be at atmospheric pressure that does not depressurize. Is preferably positive pressure by gas.
• a pressurization valve, a pressurization valve, or a three-way valve may be used.
• Depressurization is to depressurize the side (filtrate side) that collects the liquid or silicon compound-containing liquid that has passed through the polyimide resin porous membrane.
• it may be depressurization by a pump, but depressurize to vacuum. Is preferred.
• the pump is usually disposed between the supply liquid tank (or the circulation tank) and the polyimide resin porous membrane.
• the pressurization may utilize both the flowing liquid pressure and the positive gas pressure.
• the differential pressure may be a combination of pressurization and depressurization, for example, those using both flow pressure and depressurization, those using both positive and depressurization of gas, flow pressure and You may utilize the positive pressure and pressure reduction of gas.
• the combination of the fluid flow pressure and the positive gas pressure, and the combination of the fluid flow pressure and the reduced pressure are preferable in terms of simplification of production.
• a polyimide resin porous membrane is used, even if it is one method such as a positive pressure by gas as a method for providing a differential pressure, purification with excellent impurity removal performance can be performed. .
• the pressure difference applied before and after the polyimide resin porous membrane is the film thickness, porosity or average pore diameter of the polyimide resin porous membrane to be used, or the desired degree of purification, flow rate, flow rate, Alternatively, it may be set as appropriate depending on the concentration or viscosity of the supply liquid.
• the pressure is, for example, 3 MPa or less.
• a dead end system a supply liquid is allowed to flow so as to intersect the polyimide resin porous membrane
• a lower limit is not specifically limited, For example, it is 10 Pa.
• a part or all of the liquid or silicon compound-containing liquid is applied from one side of the polyimide resin porous membrane.
• a liquid or a silicon compound containing liquid contains a solute, you may dilute a supply liquid suitably with a diluent.
• the polyimide-based porous resin membrane is washed or improved in wettability with respect to the supply liquid.
• a solution such as alcohol, methanol, ethanol, isopropyl alcohol, etc., ketone, water, a solvent contained in the supply liquid, or a mixture thereof for adjusting the surface energy of the polyimide resin porous membrane and the supply liquid May be made to contact with a polyimide resin porous membrane and let it pass therethrough.
• the polyimide resin porous membrane In contacting the polyimide resin porous membrane with the solution before allowing the supply liquid to permeate, the polyimide resin porous membrane may be impregnated or immersed in the solution, and the polyimide resin porous membrane is contacted with the solution. By doing so, for example, the solution can be infiltrated into the pores inside the polyimide resin porous membrane.
• Contact between the solution and the polyimide-based resin porous membrane before allowing the supply liquid to permeate may be performed by the above-described differential pressure, particularly when the solution penetrates into the pores in the polyimide-based resin porous membrane. Alternatively, it may be performed under pressure.
• the polyimide-based resin porous membrane in the present invention may have at least one selected from the group consisting of a carboxy group, a salt-type carboxy group, and an —NH— bond, and is mainly composed of polyimide and / or polyamideimide. Since it is a porous membrane having a high degree of porosity as described above, it can be suitably used as a separating material and an adsorbing material.
• the polyimide-based resin porous membrane in the present invention is a porous membrane having a communication hole, and as described above, preferably a porous film having a communication hole in which a hole having a curved surface is formed on the inner surface, More preferably, since it is a porous film having communication holes including a structure in which substantially spherical holes communicate with each other, when liquid is permeated through the porous film, it is solid at room temperature contained in the liquid or the silicon compound-containing liquid Part or all of the impurities containing these elements can be removed from the liquid or silicon compound-containing liquid.
• elements that are solid at room temperature mean elements that constitute a single substance that is solid at room temperature, for example, room temperature, specifically, 20 ° C.
• the element when the element is Fe, iron as a metal, which is a simple element of the Fe element, is solid at room temperature, and thus corresponds to the “element that is solid at room temperature” in the present invention.
• elements that are solid at room temperature usually include metal elements, metalloid elements, and some nonmetal elements.
• the metal element examples include alkali metals such as Li, Na, and K; alkaline earth metals such as Be, Mg, Ca, and Ba; and periodic tables such as Cr, Mn, Fe, Co, Ni, Cu, and Zn Examples include transition metals belonging to Group 3 to 11; metals belonging to Groups 12 to 15 of the periodic table such as Zn, Al, Ga and Sn.
• the metalloid element examples include B, Si, Ge, As, Sb, Te, Po, and the like. Some non-metallic elements include C, P, S, I and the like.
• “elements that are solid at room temperature” are preferably metal elements and metalloid elements, more preferably metal elements, and even more preferably iron and / or zinc.
• the “impurity containing an element that is solid at normal temperature” means an impurity that includes the above-mentioned “element that is solid at normal temperature”, and may be a single element of the element or a plurality of elements including the element.
• the compound which consists of elements may be sufficient.
• the purification method using the liquid or the silicon compound-containing liquid according to the first aspect and the second aspect as a product to be purified has a high need for removal from a silylating agent chemical liquid in the field of manufacturing electronic materials such as semiconductors.
• the impurity is a metal impurity containing a metal element, it can be particularly preferably applied.
• minute substances such as metal particles present in the liquid before treatment or the silicon compound-containing liquid are adsorbed in the pores and / or communication holes of the porous membrane. It is considered easy.
• the polyimide resin porous membrane in the present invention may further have at least one selected from the group consisting of a carboxy group, a salt-type carboxy group, and an —NH— bond, and these groups are It is easy to suck metal particles, for example, metal ions or metal aggregates (for example, metal oxide aggregates, metal-organic aggregates) contained in the fluid by the charge or Coulomb force provided, It is considered that the adsorption to the porous membrane can be promoted, and that it can also function as an ion exchange membrane.
• metal particles for example, metal ions or metal aggregates (for example, metal oxide aggregates, metal-organic aggregates) contained in the fluid by the charge or Coulomb force provided.
• the polyimide resin porous membrane has a high degree of porosity as described above, and has a porous hole. Since it is a porous membrane, it is considered that a part or all of impurities including elements that are solid at room temperature are removed from the liquid before treatment by separation and / or adsorption.
• “separation” may include at least one selected from the group consisting of filtration, isolation, removal, capture, purification, and sieving, and can be used for, for example, wastewater treatment. .
• the purification method using the liquid or the silicon compound-containing liquid according to the first aspect and the second aspect as a material to be purified is performed by adsorbing a minute substance in the pores and / or the communication pores of the polyimide resin porous membrane. Also, it can be suitably used for a process in which both separation and adsorption are performed, such as a process of separating the minute substance from the liquid containing the minute substance.
• the polyimide-based resin porous membrane in the present invention is preferably a porous membrane containing pores having an average pore diameter of several hundreds of nanometers. It can be adsorbed or trapped in pores and / or communication holes in the membrane. Therefore, the purification method using the polyimide-based resin porous membrane according to the first aspect and the second aspect or the silicon compound-containing liquid as an object to be purified is an electronic material that requires very precise impurity removal. In particular, it can also be applied in the field of semiconductor manufacturing, for example, suitably applied to various purification methods for separating and / or adsorbing impurities from various liquids such as silylating agent chemicals used in semiconductor manufacturing or silicon compound-containing liquids. can do.
• the polyimide resin porous membrane can be used as, for example, a filter medium or other filter medium, Specifically, it may be used alone, or may be used as a filter medium to provide another functional layer (membrane), or may be used as a membrane to be combined with another filter medium, such as a filter device. It can also be used as a membrane used in the above.
• the functional layer that can be used in combination with the polyimide resin porous membrane in the present invention is not particularly limited.
• nylon membrane polytetrafluoroethylene (PTFE) membrane, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer
• PTFE polytetrafluoroethylene
• tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer examples thereof include a (PFA) film or a film having a chemical or physicochemical function such as a film obtained by modifying these.
• the polyimide resin porous membrane is used as a filter medium such as a metal filter used in the field of semiconductor manufacturing, for example. It can also be used as a laminate including the filter media and other filter media, and can also be used as a filter device. Although it does not specifically limit as a filter device, In a filter device, a polyimide resin porous membrane is arrange
• the polyimide-based resin porous film in the present invention may be bonded by light (UV) curing or heat bonding (including adhesion by an anchor effect (such as heat welding)), if necessary), or It may be processed by adhesion using an adhesive or the like, or the polyimide-based resin porous membrane in the present invention and another filter medium (filter) can be adhered and used by, for example, an incorporation method, etc.
• the resin porous membrane is further provided in an outer container made of a thermoplastic resin such as polyethylene, polypropylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), polyethersulfone (PES), polyimide, polyamideimide and the like. Can be used.
• a thermoplastic resin such as polyethylene, polypropylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), polyethersulfone (PES), polyimide, polyamideimide and the like. Can be used.
• the filter media according to the fourth aspect described above is a polyimide and / or polyamide-imide porous membrane used in a purification method using the liquid according to the first aspect and the second aspect or a silicon compound-containing liquid as a product to be purified.
• a filter device comprising a filter medium and a polyimide and / or polyamideimide porous membrane is also one aspect of the present invention.
• the purification method using the liquid or silicon compound-containing liquid according to the first aspect and the second aspect as a product to be purified is suitable for removing the metal contained in the above-mentioned silylating agent chemical liquid used in the semiconductor manufacturing field.
• the metal the removal rate of iron and zinc is particularly high, and the metal removal rate described later is, for example, 90% or more, preferably 95% or more, more preferably 97% or more, even more about iron.
• it may be 98% or more, and for zinc, for example, 45% or more, preferably 50% or more, more preferably 60% or more, but for zinc contained in pure water, for example, 80% Or more, preferably 85% or more, more preferably 90% or more, and when using a polyimide resin porous membrane that has undergone an imide bond ring-opening step, for example, 95% or more Preferably it may be 98% or more.
• the upper limit of the metal removal rate is not particularly set because it is preferably as high as possible. However, for iron, for example, less than 100%, usually 99.5% or less when the liquid is an organic solvent, and 99% or less when the liquid is pure water.
• zinc for example, it can be 100% or less, and in some cases it can be 99% or less.
• the purification method using the liquid or silicon compound-containing liquid according to the first aspect and the second aspect as a material to be purified includes impurities such as metals contained in the above-described silylating agent chemical liquid used in the semiconductor manufacturing field.
• impurities can be removed while maintaining a high flow rate of a fluid such as a silylating agent chemical.
• the flow rate in this case is not particularly limited, but for example, it is applied at 0.08 MPa at room temperature.
• the flow rate of pure water when pressed is 1 ml / min or more, preferably 3 ml / min or more, more preferably 5 ml / min or more, and particularly preferably 10 ml / min or more.
• An upper limit is not specifically limited, For example, it can be 50 ml / min or less.
• the purification method using the liquid or silicon compound-containing liquid according to the first aspect and the second aspect as a product to be purified can maintain a high removal rate of impurities while maintaining a high flow rate.
• the purification method using the liquid or silicon compound-containing liquid according to the first aspect and the second aspect as a material to be purified uses a polyimide resin porous film mainly composed of polyimide and / or polyamideimide, a chemical solution, etc.
• the fluid can be maintained at a high flow rate, and can be suitably applied to circulation-type purification in which a liquid such as a chemical solution is constantly circulated and permeated through the polyimide resin porous membrane.
• the polyimide resin porous membrane of the present invention is excellent in mechanical properties such as stress and elongation at break.
• the stress is preferably 10 MPa or more, more preferably 15 MPa or more, and further preferably 15 to 50 MPa.
• the elongation at break can be, for example, 10% GL or more, preferably 15% GL or more.
• the upper limit of the breaking elongation can be, for example, 50% GL, preferably 45% GL, and more preferably 40% GL.
• the breaking elongation tends to increase.
• the method for producing the diffusing agent composition used for diffusing the silylating agent chemical, the film-forming material, or the dopant into the semiconductor substrate, which is the third aspect, is the liquid or silicon of the first aspect and the second aspect.
• a purification method using a compound-containing solution as a product to be purified is used. Since the purification method using the liquid or silicon compound-containing liquid according to the first aspect and the second aspect as a product to be purified is a method having an excellent purification effect as described above, the liquid or silicon compound-containing liquid is used as the product to be purified.
• the manufacturing method of the third aspect using the purification method is to use a silylating agent chemical solution having a reduced impurity content, a film-forming material, or a diffusing agent composition used for dopant diffusion into a semiconductor substrate.
• the silylating agent chemical, the film forming material, or the manufacturing method of the diffusing agent composition used for the dopant diffusion to the semiconductor substrate includes the silylating agent chemical, the film forming material, or the diffusion.
• a silylating agent chemical solution, a film-forming material or a diffusing agent composition, which is a product to be purified, is added to the liquid or silicon compound-containing liquid of the first embodiment and the second embodiment. Purification by a purification method to be purified.
• the particle size distribution index of silica (1) is about 3.3, and the particle size distribution index of silica (2) is about 1.5.
• Tetracarboxylic acid dianhydride pyromellitic dianhydride ⁇ Diamine: 4,4′-diaminodiphenyl ether ⁇ Polyamide acid solution: Reaction product of pyromellitic dianhydride and 4,4′-diaminodiphenyl ether (solid content) 21.9% by mass (organic solvent: N, N-dimethylacetamide)) Organic solvent (1): N, N-dimethylacetamide (DMAc) Organic solvent (2): gamma butyrolactone Dispersant: polyoxyethylene secondary alkyl ether dispersant Fine particle: silica (1): silica with an average particle size of 700 nm Silica (2): silica with an average particle size of 300 nm Etching Liquid (1): 1.1% by mass NaOH of a mixed solution of methanol: water (mass ratio 3: 7)
• silica dispersion 23.1 parts by mass of silica (1) or silica (2) having an average particle size shown in Table 1 is added to a mixture of 23.1 parts by mass of organic solvent (1) and 0.1 part by mass of a dispersing agent, followed by stirring. Thus, a silica dispersion was prepared.
• the varnish was formed into a film using an applicator on a PET film as a base material. Prebaking was performed at 90 ° C. for 5 minutes to produce an unfired composite film having a thickness of 40 ⁇ m. After being immersed in water for 3 minutes, the unfired composite film was pressed through the unfired composite film between two rolls. At that time, the roll holding pressure was 3.0 kg / cm 2 , the roll temperature was 80 ° C., and the moving speed of the unfired composite film was 0.5 m / min. The green composite film was peeled from the substrate to obtain a green composite film.
• Comparative Example 1 Porous Membrane of Other Resin As Comparative Example 1, a polyamide (nylon) porous membrane (pore size: about 10 nm or less, film thickness of about 75 ⁇ m) was prepared.
• each example had a metal removal rate generally superior to that of the comparative example, and in particular, far superior to that of Comparative example 1 using a nylon porous membrane. Since each example has a higher removal rate with a thinner film thickness than the comparative example, when using a polyimide-based resin porous film for a filter media or a filter device, the media is thinned or the device is miniaturized. In addition, when the polyimide-based resin porous membrane is processed into a pleat shape, it is possible to create a filter device having higher removal performance because the pleat can be repeatedly formed. From Example 1 and Example 2, Example 3 and Example 4, it was found that the metal removal rate was improved by performing chemical etching as the imide bond ring-opening step.

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