US20110073977A1 - Amino acid generator and polysiloxane composition containing the same - Google Patents

Amino acid generator and polysiloxane composition containing the same Download PDF

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Publication number
US20110073977A1
US20110073977A1 US12/993,700 US99370009A US2011073977A1 US 20110073977 A1 US20110073977 A1 US 20110073977A1 US 99370009 A US99370009 A US 99370009A US 2011073977 A1 US2011073977 A1 US 2011073977A1
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Prior art keywords
group
coating film
amino acid
polysiloxane
forming composition
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US12/993,700
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English (en)
Inventor
Taku Kato
Junpei Kobayashi
Satoko Takano
Naoki Sakumoto
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Nissan Chemical Corp
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Nissan Chemical Corp
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Assigned to NISSAN CHEMICAL INDUSTRIES, LTD. reassignment NISSAN CHEMICAL INDUSTRIES, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KATO, TAKU, KOBAYASHI, JUNPEI, SAKUMOTO, NAOKI, TAKANO, SATOKO
Publication of US20110073977A1 publication Critical patent/US20110073977A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B51/00—Introduction of protecting groups or activating groups, not provided for in the preceding groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14601—Structural or functional details thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/02—Details
    • H01L31/0216—Coatings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14601—Structural or functional details thereof
    • H01L27/1462—Coatings
    • H01L27/14621—Colour filter arrangements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14601—Structural or functional details thereof
    • H01L27/14625—Optical elements or arrangements associated with the device
    • H01L27/14627—Microlenses
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures
    • H01L27/14683—Processes or apparatus peculiar to the manufacture or treatment of these devices or parts thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Definitions

  • the present invention relates to an amino acid generator and a polysiloxane composition containing the same. More in detail, the present invention relates to: an amino acid generator in which an amino group is protected while a carboxy group remains, and by subjecting the amino acid generator to treatment such as heating, a protecting group for the amino group is eliminated to generate an amino acid; and a coating film forming composition using the amino acid generator and a polysiloxane composition containing the amino acid generator.
  • a polysiloxane is researched and developed for utilizing the polysiloxane as one member of an electronic device, particularly a solid state imaging device by taking advantage of high transparency and high heat resistance due to a Si—O bond.
  • the incorporation of the polysiloxane into an electronic device is performed through a process of coating an arbitral substrate with the polysiloxane by a wet process such as a spin coating method, and thus it is essential to prepare the polysiloxane as a polysiloxane vanish.
  • the polysiloxane after the film formation thereof is generally baked using an arbitral baking equipment.
  • thermobase generator utilizes such a property that Si—OH bonds of the polysiloxane easily cause the condensation-polymerization of each other under a basic condition, and is effective for digesting remaining Si—OH bonds.
  • thermobase generator accelerates the condensation-polymerization during baking by adding a primary amine or a secondary amine that is a moiety developing basicity in a high activity state into the thermobase generator or by adding a tertiary amine into the thermobase generator.
  • a primary amine or a secondary amine that is a moiety developing basicity in a high activity state into the thermobase generator or by adding a tertiary amine into the thermobase generator.
  • the preservation stability of a polysiloxane vanish in a frozen state, in a refrigerated state, or at room temperature is poor.
  • an acidic range of around pH 4 is a stable range for the preservation stability of a polysiloxane vanish in which the condensation-polymerization cannot be caused and a hydrolysis cannot be progressed.
  • a method of further newly adding a derivative of a carboxylic acid such as oxalic acid and maleic acid to the reaction system or similar methods are used for this adjustment.
  • thermobase generator is effective for digesting remaining Si—OH bonds, but conversely unpreferably impairs the preservation stability of a polysiloxane vanish.
  • a polysiloxane composition capable of forming a polysiloxane film in which Si—OH bonds are remarkably digested during film formation/baking while advantageously maintaining the preservation stability of a polysiloxane vanish.
  • a polysiloxane composition in which an amino acid generator is added to a polysiloxane is effective as a coating film forming composition capable of making the preservation stability of a polysiloxane vanish advantageous, accelerating the condensation-polymerization during baking of the composition, and remarkably reducing remaining Si—OH bonds.
  • the inventors of the present invention also have found that when the amino acid generator is used in an electronic material field, it develops a novel action effect.
  • the present invention provides the followings.
  • an amino acid generator includes a protecting group that is eliminated to generate an amino acid.
  • thermo amino acid generator includes a protecting group that is eliminated by heat to generate an amino acid.
  • a photo amino acid generator includes a protecting group that is eliminated by light to generate an amino acid.
  • the amino acid generator according to any one of the first aspect to the third aspect in which the amino acid generator is a compound of Formula (1):
  • the amino acid generator according to the fourth aspect in which the amino acid generator is a compound of Formula (2):
  • D is a protecting group for an amino group
  • R 1 is a hydrogen atom (when n is 0) or an alkylene group
  • R 2 is a single bond, an alkylene group, or an arylene group
  • R 1 and R 2 together with a nitrogen atom of an amino group to which R 1 and R 2 are bonded may form a cyclic structure
  • T is a single bond or a (k+2L+n+m)-valent organic group that is a C 1-10 alkyl group or C 6-40 aryl group that may contain an amino group, a thiol group, or a carbonyl group
  • k is an integer of 1 to 4
  • L is an integer of 0 to 2
  • n is an integer of 0 to 2
  • m is an integer of 1 to 4).
  • the amino acid generator according to the fourth aspect in which the protecting group D is an esterified carboxy residue having an alkoxycarbonyl structure.
  • the amino acid generator according to the fourth aspect in which the protecting group D is a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group.
  • the amino acid generator according to any one of the first aspect to the third aspect in which the amino acid generator is at least one type of compound selected from compounds of Formula (2-1) to Formula (2-22):
  • a coating film forming composition contains the amino acid generator as described in any one of the first aspect to the eighth aspect.
  • a coating film forming composition contains a component (A): the amino acid generator as described in any one of the first aspect to the eighth aspect, a component (B): a hydrolyzable silane, a hydrolysis product thereof, a hydrolysis-condensation product thereof, or a mixture thereof, and a component (C): a solvent.
  • the coating film forming composition according to the tenth aspect in which the component (B) is at least one type of hydrolyzable silane selected from a group consisting of hydrolyzable silanes of Formula (3) and Formula (4):
  • R 3 is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, a carboxy group, a phosphate group, an amide group, a nitro group, an acyl group, a sulfonic group, a cyano group, or a combination thereof, where R 3 is bonded to a silicon atom through a Si—C bond; R 4 is an alkoxy group, an acyloxy group, or a halogen atom; and a is an integer of 0 to 3)
  • R 5 is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, a carboxy group, a phosphate group, an amide group, a nitro group, an acyl group, a sulfonic group, a cyano group, or a combination thereof, where R 5 is bonded to a silicon atom through a Si—C bond; R 6 is an alkoxy group, an acyloxy group, or a halogen atom; Y is an alkylene group or an arylene group; b is an integer of 0 or 1; and c is an integer of 0 or 1), a hydrolysis product thereof, a hydrolysis-condensation product thereof, or a mixture thereof.
  • the coating film forming composition according to the eleventh aspect in which the component (B) is at least one type of hydrolyzable silane selected from a group consisting of hydrolyzable silanes of Formula (3) (where a is 0 to 2), a hydrolysis product thereof, a hydrolysis-condensation product thereof, or a mixture thereof.
  • the component (B) is at least one type of hydrolyzable silane selected from a group consisting of hydrolyzable silanes of Formula (3) (where a is 0 to 2), a hydrolysis product thereof, a hydrolysis-condensation product thereof, or a mixture thereof.
  • the coating film forming composition according to any one of the tenth aspect to the twelfth aspect, further containing a crosslinkable compound as a component (D).
  • the coating film forming composition according to the thirteenth aspect in which the component (D) contains a crosslinkable compound having in the molecule thereof, at least two functional groups of Formula (D-1):
  • R 1 is a hydrogen atom or a C 1-10 alkyl group.
  • R 6 is a hydrogen atom, a C 1-10 alkyl group, an aryl group, an aralkyl group, an alkenyl group, or a functional group of Formula (D-3):
  • R 7 is a hydrogen atom or a functional group of Formula (D-1) ⁇ ; and R 7 is a hydrogen atom or a functional group of Formula (D-1), where the crosslinkable compound of Formula (D-2) has in the molecule thereof, two to six functional groups of Formula (D-1)]
  • R 8 is a hydrogen atom or a functional group of Formula (D-1), where the crosslinkable compound of Formula (D-4) has in the molecule thereof, two to four functional groups of Formula (D-1) ⁇ .
  • an electronic device contains a film formed from the coating film forming composition as described in any one of the ninth aspect to the fifteenth aspect.
  • a solid state imaging device contains a charge coupled device (CCD) or a complementary metal oxide film semiconductor (CMOS) that contains a film formed from the coating film forming composition as described in any one of the ninth aspect to the fifteenth aspect.
  • CCD charge coupled device
  • CMOS complementary metal oxide film semiconductor
  • a solid state imaging device contains a film formed from the coating film forming composition as described in any one of the ninth aspect to the fifteenth aspect as a planarization layer on a color filter.
  • a solid state imaging device contains a film formed from the coating film forming composition as described in any one of the ninth aspect to the fifteenth aspect as a planarization layer or a conformal layer on a microlens.
  • the amino acid generator (such as a thereto amino acid generator and a photo amino acid generator) of the present invention acts as an acid component in the coating film forming composition using the polysiloxane composition containing the amino acid generator, so that the amino acid generator and the coating film forming composition have advantageous preservation stability of a polysiloxane vanish.
  • a coating film formed from the coating film forming composition using the amino acid generator and the polysiloxane composition containing the amino acid generator during baking or light irradiation thereof, unreacted Si—OH bonds are digested. Therefore, when the coating film is incorporated into an electronic device, particularly a solid state imaging device as one member thereof, it is not caused that Si—OH bonds remaining after an aging test at a high temperature of the electronic device in a post-process are condensation-polymerized again and that by dehydration of the electronic device, degasification is caused. As a result, the reliability of the electronic device can be remarkably enhanced.
  • the coating film formed from the coating film forming composition using the amino acid generator of the present invention and the polysiloxane composition containing the amino acid generator remarkably accelerates the condensation-polymerization during baking thereof, so that the coating film can shorten the baking time when arbitral baking equipment is used and can lower the baking temperature.
  • the shortening of the baking time can shorten the tact time of the film production and can enhance the throughput of the device production.
  • the lowering of the baking temperature makes possible a low temperature baking, which could not be achieved by a conventional polysiloxane composition and the coating film can be applied to a flexible base material incapable of corresponding to a high temperature baking.
  • the coating film formed from the coating film forming composition containing the amino acid generator of the present invention remarkably accelerates the condensation-polymerization during exposure thereof, so that the coating film can reduce an exposure amount when an arbitral exposing apparatus is used.
  • the reduction of the exposure amount can shorten the tact time of the film production and can enhance the throughput of the device production.
  • the polysiloxane composition containing the amino acid generator of the present invention accelerates the condensation-polymerization by the exposure, so that the polysiloxane composition can be applied to a flexible base material, which could not be achieved by a conventional high temperature curing-type polysiloxane.
  • the amino acid generator of the present invention and the polysiloxane composition containing the amino acid generator can control pH during the preparation of a polysiloxane vanish and the baking by varying the type of the amino acid generator, so that various polysiloxane compositions corresponding to the device type to be produced and various baking processes can be designed and the process margin can be enlarged.
  • the polysiloxane composition of the present invention can preferably be used as one member of an electronic device, particularly a solid state imaging device.
  • the polysiloxane composition containing an organic crosslinkable compound suppresses a sudden volume contraction of the polysiloxane obtained by the involvement of the organic crosslinkable compound in a reaction with a silanol group at a siloxane terminal to enhance the recovery rate of the film (coating film property), so that the polysiloxane composition can enhance, for example filling property in a via to enhance the reliability of a device.
  • composition containing the polysiloxane and the organic crosslinkable compound with the amino acid generator as a curing accelerator, there can be obtained both effects of accelerating the effect of the polysiloxane and preventing a slit and a crack of the resultant polysiloxane cured product.
  • the amino acid generator used in the present invention is originally a medicine intermediate mainly used for a bioactivity research, a pathogenic gene research, and the like in the medicine field, so that the supplying property thereof during the production of the amino acid generator is stable.
  • FIG. 1 is a graph showing an FT-IR spectrum of the film obtained in Example 19.
  • FIG. 2 is a graph showing an FT-IR spectrum of the film obtained in Example 20.
  • FIG. 3 is a graph showing an FT-IR spectrum of the film obtained in Example 21.
  • FIG. 4 is a graph showing an FT-IR spectrum of the film obtained in Example 22.
  • FIG. 5 is a graph showing an FT-IR spectrum of the film obtained in Example 23.
  • FIG. 6 is a graph showing an FT-IR spectrum of the film obtained in Example 24.
  • FIG. 7 is a graph showing an FT-IR spectrum of the film obtained in Example 25.
  • FIG. 8 is a graph showing an FT-IR spectrum of the film obtained in Example 26.
  • FIG. 9 is a graph showing an FT-IR spectrum of the film obtained in Example 27.
  • FIG. 10 is a graph showing an FT-IR spectrum of the film obtained in Example 28.
  • FIG. 11 is a graph showing an FT-IR spectrum of the film obtained in Example 29.
  • FIG. 12 is a graph showing an FT-IR spectrum of the film obtained in Example 30.
  • FIG. 13 is a graph showing an FT-IR spectrum of the film obtained in Example 31.
  • FIG. 14 is a graph showing an FT-IR spectrum of the film obtained in Example 32.
  • FIG. 15 is a graph showing an FT-IR spectrum of the film obtained in Example 33.
  • FIG. 16 is a graph showing an FT-IR spectrum of the film obtained in Example 34.
  • FIG. 17 is a graph showing an FT-IR spectrum of the film obtained in Example 35.
  • FIG. 18 is a graph showing an FT-IR spectrum of the film obtained in Example 36.
  • FIG. 19 is a graph showing an FT-IR spectrum of the film obtained in Example 37.
  • FIG. 20 is a graph showing an FT-IR spectrum of the film obtained in Example 38.
  • FIG. 21 is a graph showing an FT-IR spectrum of the film obtained in Example 39.
  • FIG. 22 is a graph showing an FT-IR spectrum of the film obtained in Example 40.
  • FIG. 23 is a graph showing an FT-IR spectrum of the film obtained in Example 41.
  • FIG. 24 is a graph showing an FT-IR spectrum of the film obtained in Example 42.
  • FIG. 25 is a graph showing an FT-IR spectrum of the film obtained in Example 43.
  • FIG. 26 is a graph showing an FT-IR spectrum of the film obtained in Example 44.
  • FIG. 27 is a graph showing an FT-IR spectrum of the film obtained in Example 45.
  • FIG. 28 is a graph showing an FT-IR spectrum of the film obtained in Example 46.
  • FIG. 29 is a graph showing an FT-IR spectrum of the film obtained in Example 47.
  • FIG. 30 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 21.
  • FIG. 31 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 22.
  • FIG. 32 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 23.
  • FIG. 33 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 24.
  • FIG. 34 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 25.
  • FIG. 35 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 26.
  • FIG. 36 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 27.
  • FIG. 37 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 28.
  • FIG. 38 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 29.
  • FIG. 39 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 30.
  • FIG. 40 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 31.
  • FIG. 41 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 32.
  • FIG. 42 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 33.
  • FIG. 43 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 34.
  • FIG. 44 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 35.
  • FIG. 45 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 36.
  • FIG. 46 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 37.
  • FIG. 47 is a graph showing an FT-IR spectrum of the film obtained in Example 48.
  • FIG. 48 is a graph showing an FT-IR spectrum of the film obtained in Example 49.
  • FIG. 49 is a graph showing an FT-IR spectrum of the film obtained in Example 50.
  • FIG. 50 is a graph showing an FT-IR spectrum of the film obtained in Example 51.
  • FIG. 51 is a graph showing an FT-IR spectrum of the film obtained in Example 52.
  • FIG. 52 is a graph showing an FT-IR spectrum of the film obtained in Example 53.
  • FIG. 53 is a graph showing an FT-IR spectrum of the film obtained in Example 54
  • FIG. 54 is a graph showing an FT-IR spectrum of the film obtained in Example 55.
  • FIG. 55 is a graph showing an FT-IR spectrum of the film obtained in Example 56.
  • FIG. 56 is a graph showing an FT-IR spectrum of the film obtained in Example 57.
  • FIG. 57 is a graph showing an FT-IR spectrum of the film obtained in Example 58.
  • FIG. 58 is a graph showing an FT-IR spectrum of the film obtained in Example 59.
  • FIG. 59 is a graph showing an FT-IR spectrum of the film obtained in Example 60.
  • FIG. 60 is a graph showing an FT-IR spectrum of the film obtained in Example 61.
  • FIG. 61 is a graph showing an FT-IR spectrum of the film obtained in Example 62.
  • FIG. 62 is a graph showing an FT-IR spectrum of the film obtained in Example 63.
  • FIG. 63 is a graph showing an FT-IR spectrum of the film obtained in Example 64.
  • FIG. 64 is a graph showing an FT-IR spectrum of the film obtained in Example 65.
  • FIG. 65 is a graph showing an FT-IR spectrum of the film obtained in Example 66.
  • FIG. 66 is a graph showing an FT-IR spectrum of the film obtained in Example 67.
  • FIG. 67 is a graph showing an FT-IR spectrum of the film obtained in Example 68.
  • FIG. 68 is a graph showing an FT-IR spectrum of the film obtained in Example 69.
  • FIG. 69 is a graph showing an FT-IR spectrum of the film obtained in Example 70.
  • FIG. 70 is a graph showing an FT-IR spectrum of the film obtained in Example 71.
  • FIG. 71 is a graph showing an FT-IR spectrum of the film obtained in Example 72.
  • FIG. 72 is a graph showing an FT-IR spectrum of the film obtained in Example 73.
  • FIG. 73 is a graph showing an FT-IR spectrum of the film obtained in Example 74.
  • FIG. 74 is a graph showing an FT-IR spectrum of the film obtained in Example 75.
  • FIG. 75 is a graph showing an FT-IR spectrum of the film obtained in Example 76.
  • FIG. 76 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 38.
  • FIG. 77 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 39.
  • FIG. 78 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 40.
  • FIG. 79 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 41.
  • FIG. 80 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 42.
  • FIG. 81 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 43.
  • FIG. 82 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 44.
  • FIG. 83 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 45.
  • FIG. 84 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 46.
  • FIG. 85 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 47.
  • FIG. 86 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 48.
  • FIG. 87 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 49.
  • FIG. 88 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 50.
  • FIG. 89 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 51.
  • FIG. 90 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 52.
  • FIG. 91 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 53.
  • FIG. 92 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 54.
  • FIG. 93 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 55.
  • FIG. 94 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 56.
  • FIG. 95 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 57.
  • FIG. 96 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 58.
  • FIG. 97 is a photograph showing a cross section view of a via in which the polysiloxane composition is filled by a spin coating method and the composition is cured, where the photograph shows advantageous filling property.
  • FIG. 98 is a photograph showing a cross section view of a via in which the polysiloxane composition is filled by a spin coating method and the composition is cured, where a slit is formed, so that the photograph shows undesirable filling property.
  • FIG. 99 is a graph showing an FT-IR spectrum of the film obtained in Example 84.
  • FIG. 100 is a graph showing an FT-IR spectrum of the film obtained in Example 85.
  • FIG. 101 is a graph showing an FT-IR spectrum of the film obtained in Example 86.
  • FIG. 102 is a graph showing an FT-IR spectrum of the film obtained in Comparative Example 59.
  • FIG. 103 is a graph showing an FT-IR spectrum of the film obtained in Reference Example 1.
  • an amino group is protected by a protecting group and by an action of heating or light irradiation (exposure), the protecting group is eliminated to generate an amino acid.
  • the amino acid generator examples include: a thermo amino acid generator in which by heat during heating, a protecting group is eliminated to generate an amino acid that is a curing accelerating component of a silanol; and a photo amino acid generator in which by an action of exposure or the like, a protecting group is eliminated to generate an amino acid that is a curing accelerating component of a silanol.
  • the amino acid generator is a compound of Formula (1):
  • D is a protecting group for an amino group and A is an organic group remaining after subtracting hydrogen atoms from an amino group of an amino acid.
  • the protecting group D is preferably an esterified carboxy residue having an alkoxycarbonyl structure.
  • the carboxy residue pulls hydrogen atoms out of a silanol group at a polysiloxane terminal so that an amino group is generated in the amino acid generator to generate an amino acid and the amino group causes a dehydration-condensation of silanol groups to generate a polymerized polysiloxane.
  • the protecting group D is reacted also with water generated by the dehydration-condensation or with a water content in the reaction system and the protecting group D itself is decomposed to an alcohol or a carbonic acid gas.
  • Examples of the protecting group D include C 2-21 linear or branched alkoxycarbonyl groups that may be substituted such as a 9-fluorenylmethoxycarbonyl group, a methoxycarbonyl group, a trifluoromethoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, an n-butoxycarbonyl group, a tert-butoxycarbonyl group, a sec-butoxycarbonyl group, an n-pentyloxycarbonyl group, and an n-hexyloxycarbonyl group.
  • C 2-21 linear or branched alkoxycarbonyl groups that may be substituted such as a 9-fluorenylmethoxycarbonyl group, a methoxycarbonyl group, a trifluoromethoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxy
  • tert-butoxycarbonyl group and a 9-fluorenylmethoxycarbonyl group that are bulky and easily eliminated shown below.
  • the amino acid generator is a compound of Formula (2):
  • D is a protecting group for an amino group
  • R 1 is a hydrogen atom (when n is 0) or an alkylene group
  • R 2 is a single bond, an alkylene group, or an arylene group.
  • R 1 and R 2 together with a nitrogen atom of an amino group to which R 1 and R 2 are bonded may form a cyclic structure and T is a single bond or a (k+2L+n+m)-valent organic group, where examples of the organic group include C 1-10 alkyl groups and C 6-40 aryl groups which may contain an amino group, a thiol group, or a carbonyl group.
  • T When T is a single bond, a ( ⁇ N-D) group and a (—OH) group that are directly bonded to T do not exist and a bond of T with R 2 and a carboxy group is formed.
  • k is an integer of 1 to 4
  • L is an integer of 0 to 2
  • n is an integer of 0 to 2
  • m is an integer of 1 to 4.
  • Examples of the C 1-10 alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, a cyclopentyl group, a 1-methyl-cyclobutyl group, a
  • alkylene group examples include alkylene groups corresponding to the above alkyl groups.
  • Examples of the C 6-40 aryl group include a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, an m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-fluorophenyl group, an o-methoxyphenyl group, a p-methoxyphenyl group, a p-nitrophenyl group, a p-cyanophenyl group, an ⁇ -naphthyl group, a ⁇ -naphthyl group, an o-biphenylyl group, an m-biphenylyl group, a p-biphenylyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenan
  • arylene group examples include arylene groups corresponding to the above aryl groups.
  • the amino acid generator may be in a structure containing at least one relative configuration among an L form, a D form, and a mixture of L form and D form.
  • Specific examples of the compounds of Formula (2-1) to Formula (2-22) include compounds in which one or more nitrogen atom(s) at an amine moiety contained in an amino acid is (are) substituted with a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group.
  • either a tert-butoxycarbonyl group or a 9-fluorenylmethoxycarbonyl group can function as a plurality of protecting groups, or a combination of a tent-butoxycarbonyl group and a 9-fluorenylmethoxycarbonyl group can function as a protecting group.
  • amino acid generator examples include: N- ⁇ -tert-butoxycarbonyl-L-alanine, N- ⁇ -tert-butoxycarbonyl-D-alanine, N- ⁇ -tert-butoxycarbonyl-DL-alanine, N- ⁇ -tert-butoxycarbonyl-N-methyl-L-alanine, N- ⁇ -tert-butoxycarbonyl- ⁇ -alanine, N- ⁇ , N- ⁇ 1, N- ⁇ 2-tri-tert-butoxycarbonyl-N-methyl-L-arginine, N- ⁇ , N- ⁇ -2-tri-tert-butoxycarbonyl-L-arginine, N- ⁇ -tert-butoxycarbonyl-L-arginine, N- ⁇ -tert-butoxycarbonyl-N- ⁇ 1, N- ⁇ 2-bis-carbobenzoxy-L-arginine, N- ⁇ -tert-butoxycarbonyl-N-oil, N- ⁇ 2-bis-carbobenzoxy-D-argin
  • the amino acid generator preferably has large basicity for more accelerating the condensation-polymerization of the polysiloxane when the protecting group for an amino group is eliminated by heat or light and an amino group is developed.
  • amino acid generator examples include N- ⁇ , N- ⁇ 2-tri-tert-butoxycarbonyl-N-methyl-L-arginine, N- ⁇ -tert-butoxycarbonyl-L-arginine, N- ⁇ -tert-butoxycarbonyl-N- ⁇ 1, N- ⁇ 2-bis-carbobenzoxy-L-arginine, N- ⁇ -tert-butoxycarbonyl-N- ⁇ 1, N- ⁇ 2-bis-carbobenzoxy-D-arginine, N- ⁇ -tert-butoxycarbonyl-L-histidine, N- ⁇ -tert-butoxycarbonyl-D-histidine, N- ⁇ -tert-butoxycarbonyl-L-histidine methyl ester, N- ⁇ , im-di-tert-butoxycarbonyl-L-histidine, N- ⁇ -tert-butoxycarbonyl-N- ⁇ -benzyloxymethyl-L-histidine, N-tert-butoxycarbonyl-N
  • an amino acid generator in which arginine is selected as the amino acid is effective.
  • amino acid generator examples include N- ⁇ , N- ⁇ 1, N- ⁇ 2-tri-tert-butoxycarbonyl-N-methyl-L-arginine, N- ⁇ -tert-butoxycarbonyl-L-arginine, N- ⁇ -tert-butoxycarbonyl-N- ⁇ 1, N- ⁇ 2-bis-carbobenzoxy-L-arginine, N- ⁇ -tert-butoxycarbonyl-N- ⁇ 1, N- ⁇ 2-bis-carbobenzoxy-D-arginine, N- ⁇ -(9-fluorenylmethoxycarbonyl)-N- ⁇ 1, N- ⁇ 2-di-tert-butoxycarbonyl-L-arginine, and N- ⁇ -(9-fluorenylmethoxycarbonyl)-N- ⁇ 1, N- ⁇ 2-di-tert-butoxycarbonyl-D-arginine.
  • the above amino acid generators are commercially available from, for example Watanabe Chemical Industries, Ltd. and Tokyo Chemical Industry Co., Ltd.
  • the present invention is also a coating film forming composition containing the component (A), the component (B), and the component (C):
  • Component (A) the amino acid generator
  • Component (C) a solvent.
  • the component (B) there can be used at least one type of hydrolyzable silane selected from a group consisting of hydrolyzable silanes of Formula (3) and Formula (4) below, a hydrolysis product thereof, a hydrolysis-condensation product thereof, or a mixture thereof.
  • the hydrolysis product is a product in which a hydrolyzable group of R 4 or R 6 is hydrolyzed to generate a silanol group.
  • the hydrolysis-condensation product is a product in which silanol groups in the hydrolysis product are dehydrolysis-condensed with each other to form a polysiloxane or a polyorganosiloxane, where a terminal of the hydrolysis-condensation product has a silanol group.
  • the hydrolysis-condensation product is a polysiloxane and may be a polysiloxane containing a polyorganosiloxane moiety.
  • R 3 is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, a carboxy group, a phosphate group, an amide group, a nitro group, an acyl group, a sulfonic group, a cyano group, or a combination thereof, where R 3 is bonded to a silicon atom through a Si—C bond; R 4 is an alkoxy group, an acyloxy group, or a halogen atom that is a hydrolyzable group; and a is an integer of 0 to 3)
  • R 5 is an alkyl group, an aryl group, a halogenated alkyl group, a halogenated aryl group, an alkenyl group, or an organic group having an epoxy group, an acryloyl group, a methacryloyl group, a mercapto group, an amino group, a carboxy group, a phosphate group, an amide group, a nitro group, an acyl group, a sulfonic group, a cyano group, or a combination thereof, where R 5 is bonded to a silicon atom through a Si—C bond; R 6 is an alkoxy group, an acyloxy group, or a halogen atom that is a hydrolyzable group; Y is an alkylene group or an arylene group; b is an integer of 0 or 1; and c is an integer of 0 or 1.
  • alkyl group examples include C 1-10 alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclobutyl group, a 1-methyl-cyclopropyl group, a 2-methyl-cyclopropyl group, an n-pentyl group, a 1-methyl-n-butyl group, a 2-methyl-n-butyl group, a 3-methyl-n-butyl group, a 1,1-dimethyl-n-propyl group, a 1,2-dimethyl-n-propyl group, a 2,2-dimethyl-n-propyl group, a 1-ethyl-n-propyl group, a cyclopentyl group, a 1-methyl-cyclobut
  • aryl group examples include C 6-40 aryl groups such as a phenyl group, an o-methylphenyl group, an m-methylphenyl group, a p-methylphenyl group, an o-chlorophenyl group, an m-chlorophenyl group, a p-chlorophenyl group, an o-fluorophenyl group, a p-fluorophenyl group, an o-methoxyphenyl group, a p-methoxyphenyl group, a p-nitrophenyl group, a p-cyanophenyl group, an ⁇ -naphthyl group, a ⁇ -naphthyl group, an o-biphenylyl group, an m-biphenylyl group, a p-biphenylyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group,
  • alkenyl group examples include C 2-10 alkenyl groups such as an ethenyl group, a 1-propenyl group, a 2-propenyl group, a 1-methyl-1-ethenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 2-methyl-1-propenyl group, a 2-methyl-2-propenyl group, a 1-ethyl-ethenyl group, a 1-methyl-1-propenyl group, a 1-methyl-2-propenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-n-propyl-ethenyl group, a 1-methyl-1-butenyl group, a 1-methyl-2-butenyl group, a 1-methyl-3-butenyl group, a 2-ethyl-2-propenyl group, a
  • Examples of the above organic group having an epoxy group include a glycidoxymethyl group, a glycidoxyethyl group, a glycidoxypropyl group, a glycidoxybutyl group, and an epoxycyclohexyl group.
  • Examples of the above organic group having an acryloyl group include an acryloylmethyl group, an acryloylethyl group, and an acryloylpropyl group.
  • Examples of the above organic group having a methacryloyl group include a methacryloylmethyl group, a methacryloylethyl group, and a methacryloylpropyl group.
  • Examples of the above organic group having a mercapto group include an ethylmercapto group, a butylmercapto group, a hexylmercapto group, and an octylmercapto group.
  • acyl group examples include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a benzoyl group.
  • Examples of the above organic group having a cyano group include a cyanoethyl group and a cyanopropyl group.
  • alkoxy group examples include C 1-20 alkoxy groups having a linear, branched, or cyclic alkyl part such as a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, a 1-methyl-n-butoxy group, a 2-methyl-n-butoxy group, a 3-methyl-n-butoxy group, a 1,1-dimethyl-n-propoxy group, a 1,2-dimethyl-n-propoxy group, a 2,2-dimethyl-n-propoxy group, a 1-ethyl-n-propoxy group, an n-hexyloxy group, a 1-methyl-n-pentyloxy group, a 2-methyl-n-pentyloxy group, a 3-methyl-n-pentyloxy group, a 4-methyl-n-n
  • acyloxy group examples include C 2-20 acyloxy groups such as a methylcarbonyloxy group, an ethylcarbonyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, an n-butylcarbonyloxy group, an isobutylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, an n-pentylcarbonyloxy group, a 1-methyl-n-butylcarbonyloxy group, a 2-methyl-n-butylcarbonyloxy group, a 3-methyl-n-butylcarbonyloxy group, a 1,1-dimethyl-n-propylcarbonyloxy group, a 1,2-dimethyl-n-propylcarbonyloxy group, a 2,2-dimethyl-n-propylcarbonyloxy group, a 1-ethyl-n-propylcarbonyloxy
  • Examples of the alkylene group in Formula (4) include C 1-10 alkylene groups such as a methylene group, an ethylene group, a propylene group, an isopropylene group, a butylene group, and an octylene group. Moreover, divalent organic groups derived from the above exemplified linear or branched alkyl groups may also be used as the alkylene group.
  • Examples of the arylene group in Formula (4) include C 6-20 arylene groups such as a phenylene group, a naphthylene group, and an anthralene group. Divalent organic groups derived from the above exemplified aryl groups may also be used as the arylene group.
  • hydrolyzable silane selected from a group consisting of hydrolyzable silanes of Formula (3) examples include tetramethoxysilane, tetrachlorosilane, tetraacetoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane, tetraacetoxysilane, methyltrimethoxysilane, methyltrichlorosilane, methyltriacetoxysilane, methyltripropoxysilane, methyltriacetoxysilane, methyltributoxysilane, methyltripropoxysilane, methyltriamyloxysilane, methyltriphenoxysilane, methyltribenzyloxysilane, methyltriphenethyloxysilane, glycidoxymethyltrimethoxysilane, glycidoxymethyltrieth
  • hydrolyzable silane selected from a group consisting of hydrolyzable silanes of Formula (4) examples include methylenebistrimethoxysilane, methylenebistrichlorosilane, methylenebistriacetoxysilane, ethylenebistriethoxysilane, ethylenebistrichlorosilane, ethylenebistriacetoxysilane, propylenebistriethoxysilane, butylenebistrimethoxysilane, phenylenebistrimethoxysilane, phenylenebistriethoxysilane, phenylenebismethyldiethoxysilane, phenylenebismethyldimethoxysilane, naphthylenebistrimethoxysilane, bistrimethoxydisilane, bistriethoxydisilane, bisethyldiethoxydisilane, and bismethyldimethoxydisilane.
  • component (B) there is preferably used at least one type of hydrolyzable silane selected from a group consisting of hydrolyzable silanes of Formula (3) (where a is 0 to 2), a hydrolysis product thereof, a hydrolysis-condensation product thereof, or a mixture thereof.
  • hydrolyzable silanes of Formula (3) and Formula (4) commercially available products may be used.
  • a polysiloxane produced by hydrolyzing a hydrolyzable silane of Formula (3) or hydrolyzable silanes of Formula (3) and Formula (4) and by condensing the resultant hydrolysis product has a weight average molecular weight of 1,000 to 1,000,000 or 1,000 to 100,000. These molecular weights are a molecular weight obtained by GPC analysis in terms of polystyrene.
  • Examples of the type of a hydrolysis catalyst during the synthesis of the polysiloxane include a metal chelate compound, an organic acid, an inorganic acid, an organic base, and an inorganic base.
  • metal chelate compound examples include: titanium chelate compounds such as triethoxy-mono(acetylacetonate)titanium, tri-n-propoxy-mono(acetylacetonate)titanium, tri-isopropoxy-mono(acetylacetonate)titanium, tri-n-butoxy-mono(acetylacetonate)titanium, tri-sec-butoxy-mono(acetylacetonate)titanium, tri-tert-butoxy-mono(acetylacetonate)titanium, diethoxy-bis(acetylacetonate)titanium, di-n-propoxy-bis(acetylacetonate)titanium, diisopropoxy-bis(acetylacetonate)titanium, di-n-butoxy-bis(acetylacetonate)titanium, di-sec-butoxy-bis(acetylacetonate)
  • organic acid examples include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, oxalic acid, maleic acid, methylmalonic acid, adipic acid, sebacic acid, gallic acid, butyric acid, mellitic acid, arachidonic acid, 2-ethylhexanoic acid, oleic acid, stearic acid, linolic acid, linoleic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid, malonic acid, sulfonic acid, phthalic acid, fumaric acid
  • Examples of the inorganic acid include hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, and phosphoric acid.
  • organic base examples include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, trimethylamine, triethylamine, monoethanolamine, diethanolamine, dimethylmonoethanolamine, monomethyldiethanolamine, triethanolamine, diazabicyclo-octane, diazabicyclo-nonane, diazabicyclo-undecene, tetramethylammoniumhydroxide, and 1,8-diazabicyclo[5,4,0]-7-undecene.
  • Examples of the inorganic base include ammonia, sodium hydroxide, potassium hydroxide, barium hydroxide, and calcium hydroxide.
  • hydrolysis catalysts metal chelate compounds, organic acids, and inorganic acids are preferred and these catalysts may be used individually or in combination of two or more types thereof.
  • water is used in an amount of 0.1 to 100 mol, or 0.1 to 10 mol, or 1 to 5 mol, or 2 to 3.5 mol, relative to 1 mol of the hydrolyzable group.
  • the hydrolysis catalyst may be used in an amount of 0.0001 to 10 mol, preferably 0.001 to 2 mol, relative to 1 mol of the hydrolyzable group.
  • the temperature for a reaction in which the hydrolyzable silane is hydrolyzed and the resultant hydrolysis product is condensed is usually in a range of from 20° C. (room temperature) to a reflux temperature of a solvent used for the hydrolysis under normal pressure.
  • the hydrolysis may be performed as a perfect hydrolysis or a partial hydrolysis. That is, the hydrolysis product or a monomer may remain in the hydrolysis-condensation product.
  • the method for obtaining the polysiloxane is not particularly limited. However, examples thereof include a method of heating a mixture of a silicon compound, a solvent, and oxalic acid. More specifically, the method is a method in which oxalic acid is added to an alcohol beforehand to prepare an alcohol solution of oxalic acid and the solution is mixed with a silicon compound to heat the resultant mixture. At this time, the amount of oxalic acid is generally 0.2 to 2 mol, relative to 1 mol of all alkoxy groups contained in the silicon compound. Heating in this method may be performed at 50 to 180° C.
  • the process order of the polysiloxane synthesis may be either an order that a mixture of a solvent and oxalic acid is added to a silicon compound to subject the resultant mixture to the reaction, or an order that a silicon compound is added to a mixture of a solvent and oxalic acid to subject the resultant mixture to the reaction.
  • the reaction for the synthesis of the polysiloxane may be effected at 0 to 50° C. of the reaction temperature for 24 to 2,000 hours for the purpose of stably synthesizing a homogeneous polymer.
  • organic solvent used for the hydrolysis examples include: aliphatic hydrocarbon solvents such as n-pentane, isopentane, n-hexane, isohexane, n-heptane, isoheptane, 2,2,4-trimethylpentane, n-octane, isooctane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, methylethylbenzene, n-propylbenzene, isopropylbenzene, diethylbenzene, isobutylbenzene, triethylbenzene, di-isopropylbenzene, n-amylnaphthalene, and trimethylbenzene; monoalcohol solvents such as methanol, ethanol, n-propan
  • Such an organic solvent include methanol, ethanol, propanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, n-propyl acetate, ethyl lactate, methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether, and cyclohexanone.
  • condensation product By hydrolyzing a hydrolyzable silane in a solvent and by subjecting the resultant hydrolysis product to a condensation reaction, a condensation product (polysiloxane) is obtained. Then, the condensation product is obtained as a polysiloxane vanish in which the condensation product is dissolved in a hydrolysis-solvent.
  • the obtained polysiloxane vanish may be solvent-exchanged. More specifically, in the case where as the solvent for the hydrolysis and the condensation (solvent for the synthesis), ethanol is selected, after the polysiloxane is obtained in ethanol, a solvent for exchange in the same amount as that of the solvent for the synthesis may be added to the polysiloxane vanish and the resultant mixture may be subjected to azeotropy using an evaporator to distil off the ethanol.
  • the solvent for the synthesis during the solvent-exchange is distilled off by azeotropy, so that the solvent for the synthesis preferably has a boiling point lower than that of the solvent for exchange.
  • Examples of the solvent for the hydrolysis and the condensation include methanol, ethanol, and isopropanol, and examples of the solvent for exchange include propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and cyclohexanone.
  • the solvent used for the dilution or the solvent-exchange of the polysiloxane vanish may be the same as or different from a solvent used for the hydrolysis and the condensation-polymerization of the hydrolyzable silane.
  • the solvent is not particularly limited so long as the solvent does not impair the compatibility with the polysiloxane or the amino acid generator and the solvent may be optionally selected individually or in combination of a plurality of types thereof to be used.
  • Examples of such a solvent as the component (C) include toluene, p-xylene, o-xylene, styrene, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol dimethyl ether, diethylene glycol
  • the solvent include methanol, ethanol, isopropanol, butanol, diacetone alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ethylene glycol, propylene glycol, hexylene glycol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether, cyclohexanone, methyl acetic acid ester, ethyl acetic acid ester, and ethyl lactic acid ester.
  • the amount of the amino acid generator (thermo amino acid generator) to be added to the polysiloxane vanish (that is, polysiloxane+solvent) is not particularly limited. However, from the viewpoint of the solubility and the preservation stability, it is 0.1 to 50 phr, preferably 0.5 to 10 phr. phr is expressed in the part by mass of the added component (thermo amino acid generator) relative to 100 parts by mass of the polysiloxane.
  • the amount of the added component may also be expressed in the SiO 2 solid content, and in this case, the amount of the added component is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the SiO 2 solid content in the polysiloxane.
  • the amount of the amino acid generator (photo amino acid generator) to be added to the polysiloxane vanish is not particularly limited. However, from the viewpoint of the solubility and the preservation stability, it is 0.1 to 50 phr, preferably 2.5 to 10 phr.
  • the amount of the added component is preferably 0.1 to 50 parts by mass, more preferably 2.5 to 10 parts by mass, relative to 100 parts by mass of the SiO 2 solid content in the polysiloxane.
  • the polysiloxane vanish containing an amino acid generator is adjusted at pH or pKa of preferably 3 to 7, more preferably 3 to 5.
  • the preparation method of the coating film forming composition of the present invention is not particularly limited so long as the composition is in a state in which the polysiloxane and the amino acid generator are homogeneously mixed.
  • the polysiloxane is obtained by a condensation-polymerization in a solvent, so that the coating film forming composition is obtained in a state of polysiloxane vanish in which the polysiloxane is dissolved in a solvent. Therefore, a method of using the obtained polysiloxane vanish as it is and mixing the polysiloxane vanish with an amino acid generator is convenient.
  • the polysiloxane vanish may be condensed, diluted with a solvent, or solvent-exchanged to be mixed with an amino acid generator. Further, after the polysiloxane vanish is mixed with an amino acid generator, a solvent may be added to the resultant mixture.
  • the coating film forming composition has a SiO 2 solid content-converted concentration of preferably 0.1 to 30% by mass.
  • SiO 2 solid content-converted concentration is lower than 0.5% by mass, at one application of the composition, a desired film thickness is difficult to be obtained.
  • SiO 2 solid content-converted concentration is higher than 30% by mass, the preservation stability of the solution may be impaired.
  • the SiO 2 solid content-converted concentration is more preferably in a range of 0.5 to 15% by mass.
  • the coating film forming composition of the present invention may contain besides the component (A), the component (B), and the component (C), further a crosslinkable compound as the component (D).
  • the component (D) is a crosslinkable compound having in the molecule thereof, at least two functional groups of Formula (D-1):
  • R 1 is a hydrogen atom or a C 1-40 alkyl group.
  • component (D) there can be used a crosslinkable compound of Formula (D-2):
  • R 6 is a hydrogen atom, a C 1-10 alkyl group, an aryl group, an aralkyl group, an alkenyl group, or a functional group of Formula (D-3):
  • R 7 is a hydrogen atom or a functional group of Formula (D-1) ⁇ ; and R 7 is a hydrogen atom or a functional group of Formula (D-1), where the crosslinkable compound of Formula (D-2) has in the molecule thereof, two to six functional groups of Formula (D-1)]
  • R 8 is a hydrogen atom or a functional group of Formula (D-1), where the crosslinkable compound of Formula (D-4) has in the molecule thereof, two to four functional groups of Formula (D-1) ⁇ .
  • alkyl group aryl group, and alkenyl group
  • alkyl groups there can be used the above-exemplified alkyl groups, aryl groups, and alkenyl groups.
  • aralkyl group include functional groups in which the above alkyl group is substituted with an aryl group, such as a benzyl group and a phenethyl group.
  • alkyl group in Formula (D-1) an alkyl group exemplified by the above alkyl groups can be used.
  • a methyl group, an ethyl group, and a propyl group are particularly preferred.
  • the functional group of Formula (D-1) is a hydroxymethyl group or an alkoxymethyl group and a nitrogen-containing compound having at least two amino groups substituted with such a functional group is preferred.
  • nitrogen-containing compound examples include melamine and melamine derivatives, urea, guanamine, acetoguanamine, benzoguanamine and benzoguanamine derivatives, glycoluril, succinylamide, and ethylene urea in which a hydrogen atom of the amino group is substituted with a methylol group, an alkoxymethyl group, or both of them.
  • nitrogen-containing compounds can be obtained by reacting, for example melamine, urea, guanamine, acetoguanamine, benzoguanamine, glycoluril, succinylamide, ethylene urea, or the like with formalin in boiling water to methylolate these compounds, or by further reacting the resultant methylol with a lower alcohol, specifically methanol, ethanol, n-propanol, isopropanol, n-butanol, or isobutanol to alkoxylate the methylol.
  • a lower alcohol specifically methanol, ethanol, n-propanol, isopropanol, n-butanol, or isobutanol to alkoxylate the methylol.
  • a triazine compound that is a melamine derivative and a triazine compound that is a benzoguanamine derivative are preferred.
  • a triazine compound substituted with a methoxymethyl group is particularly preferred.
  • the melamine derivative and the benzoguanamine derivative may exist as a dimer or a trimer.
  • more preferred is a triazine compound having methylol groups or alkoxymethyl groups in an average number of 3 or more and 6 or less per one triazine ring. Examples of such a triazine compound include compounds of Formula (D-2).
  • the most representative compound of Formula (D-2) is a compound of Formula:
  • R 1 is a hydrogen atom or a C 1-10 alkyl group.
  • Examples of the melamine derivative or the benzoguanamine derivative include MX-750 in which one triazine ring is substituted with methoxymethyl groups in an average number of 3.7 and MW-30 in which one triazine ring is substituted with methoxymethyl groups in an average number of 5.8 (both are trade names for commercially available products from Sanwa Chemical Co., Ltd.), methoxymethylated melamine such as CYMEL 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, hexamethoxymethylated melamine such as CYMEL 385, methoxymethylated butoxymethylated melamine such as CYMEL 235, 236, 238, 212, 253, 254, butoxymethylated melamine such as MYCOAT 506, 508 (to here, trade names for commercially available products from Mitsui Cytec Ltd.), carboxy group-containing methoxymethylated isobutoxymethylated melamine such as CYMEL 1141
  • Examples of such a glycoluril derivative include compounds of Formula (D-4).
  • the most representative compound of Formula (D-4) is a compound of Formula:
  • R 1 is a hydrogen atom or a C 1-10 alkyl group.
  • glycoluril examples include butoxymethylated glycoluril such as CYMEL 1170, methylolated glycoluril such as CYMEL 1172, and methoxymethylated glycoluril such as POWDERLINK 1174 (to here, trade names for commercially available products from Mitsui Cytec Ltd.).
  • crosslinkable compound examples include polymers produced using an acrylamide compound or a methacrylamide compound which are substituted with a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, and N-butoxymethylmethacrylamide.
  • Examples of such a polymer include poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide with styrene, a copolymer of N-hydroxymethylmethacrylamide with methylmethacrylate, a copolymer of N-ethoxymethylmethacrylamide with benzylmethacrylate, and a copolymer of N-butoxymethylacrylamide, benzylmethacrylate, and 2-hydroxypropylmethacrylate.
  • Such a polymer has a weight average molecular weight of, for example 1,000 to 500,000, or 2,000 to 200,000, or 3,000 to 150,000, or 3,000 to 50,000.
  • the present invention is a coating film forming composition in which the component (A), the component (B), and the component (D) are dissolved in the component (C).
  • a solvent used for the production of a hydrolyzable silane, a hydrolysis product thereof, a hydrolysis-condensation product thereof, or a mixture thereof as the component (B) as it is can be used as the solvent of the component (C).
  • examples of the production method of the coating film forming composition include a production method by adding the component (A) and the component (D) to the polysiloxane vanish (component (B)+component (C)).
  • the coating film forming composition in which the component (B) and the component (D) are dissolved in the composition (C) can enhance the filling property thereof in a via.
  • examples of the production method of the coating film forming composition include a production method by adding the component (D) to the polysiloxane vanish (component (B)+component (C)).
  • a crosslinkable compound as the component (D) may be added to the polysiloxane vanish (component (B)+component (C)) in a ratio of the crosslinkable compound relative to the polysiloxane of 5 to 20 phr. phr is expressed in parts by mass of the added component (crosslinkable compound) relative to 100 parts by mass of the polysiloxane.
  • the amount of the added component may also be expressed in the SiO 2 solid content, and in this case, the polysiloxane may contain the polyorganosiloxane in a content of 5 to 20 parts by mass, relative to 100 parts by mass of the SiO 2 solid content in the polysiloxane.
  • the coating film forming composition of the present invention may contain besides the amino acid generator, the polysiloxane, and the solvent, other components such as a leveling agent and a surfactant so long as the effect of the present invention is not impaired.
  • surfactant examples include: nonionic surfactants, for example polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether, polyoxyethylene alkylallyl ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether, polyoxyethylene-polyoxypropylene block copolymers, sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate,
  • surfactants may be used individually or in combination of two or more types thereof.
  • the content thereof is 0.0001 to 5 parts by mass, or 0.001 to 1 part by mass, or 0.01 to 0.5 parts by mass, relative to 100 parts by mass of the condensation product (polysiloxane).
  • the method of mixing the above other components is not particularly limited and examples of the method include: a method of adding the amino acid generator and simultaneously the other components to the polysiloxane vanish; and a method of mixing the polysiloxane vanish with the amino acid generator and mixing the resultant mixture with the other components.
  • a desired coating film By coating a substrate with the coating film forming composition of the present invention and by thermocuring or photocuring the composition, a desired coating film can be obtained.
  • the coating method a publicly known or well-known method can be adopted.
  • the coating method include a spin coating method, a dip coating method, a flow coating method, an inkjet method, a spray coating method, a bar coating method, a gravure coating method, a roll coating method, a transferring printing method, a brush coating method, a blade coating method, and an air knife coating method.
  • the used substrate include substrates containing silicon, indium tin oxide (ITO), indium zinc oxide (IZO), plastic, glass, ceramic, and the like.
  • thermocuring is not particularly limited and the composition may be baked using, for example a hot plate, an oven, and a furnace in an appropriate atmosphere such as air, an inactive gas such as nitrogen, and vacuum.
  • an inactive gas such as nitrogen
  • thermocuring there can be obtained a coating film having a homogeneous film-formed surface.
  • the baking temperature for the purpose of evaporating the solvent is not particularly limited, and baking can be performed, for example at 40 to 200° C.
  • the baking temperature for the purpose of accelerating the condensation-polymerization of the polysiloxane by heat is not particularly limited, and baking can be performed at 200 to 400° C. In these cases, for developing more highly homogeneous film formation property and progressing the reaction on the substrate, the temperature change may be divided into two or more stages.
  • the baking temperature and the baking time may be selected as conditions suitable for a process of an objective electronic device and there may be selected baking conditions under which the physical property values of the polysiloxane coating film meet required properties of the electronic device.
  • the exposure apparatus used for the photocuring is not particularly limited and the exposure may be performed, for example using a UV curing apparatus in an appropriate atmosphere such as air, an inactive gas such as nitrogen, and vacuum. Corresponding to the process of the device, there may also be performed an exposure process having two or more stages.
  • the exposure amount may be selected as a condition suitable for a process of an objective electronic device and there may be selected an exposure condition under which the physical property values of the polysiloxane coating film meet required properties of the electronic device.
  • the exposure amount may be used, for example in a range of 10 mJ/cm 2 to 10 J/cm 2 , preferably 500 mJ/cm 2 to 10 J/cm 2 (converted into energy at 250 nm).
  • the baking process may be added.
  • the baking equipment is not particularly limited and the composition may be baked using, for example a hot plate, an oven, and a furnace in an appropriate atmosphere such as air, an inactive gas such as nitrogen, and vacuum.
  • an appropriate atmosphere such as air, an inactive gas such as nitrogen, and vacuum.
  • the baking temperature for the purpose of evaporating the solvent is not particularly limited. However, baking can be performed, for example at 40 to 150° C.
  • the baking temperature and the baking time may be selected as conditions suitable for a process of an objective electronic device and there may be selected drying conditions under which the physical property values of the polysiloxane coating film meet required properties of the electronic device.
  • the thus obtained coating film formed from the coating film forming composition containing the amino acid generator of the present invention has advantageous preservation stability of a polysiloxane vanish, can develop an effect of accelerating the condensation-polymerization of remaining Si—OH bonds, and can be formed on an arbitral substrate.
  • the coating film is suitable for a gap-filling planarizing material on a photodiode, a planarizing material on a color filter, or a planarizing or conformal material on a microlens, which are for an electronic device, particularly a solid state imaging device.
  • the polysiloxane vanish uses as a component for accelerating the condensation-polymerization of the Si—OH bond, an amino acid generator that is acidic in the polysiloxane vanish and has a function of generating an amino acid exhibiting basicity higher than that before heating the composition or before irradiating the composition with light (before exposure of the composition) when the amino acid generator is heated or irradiated with light (exposed to light) and a protecting group for the amino group is eliminated, so that the polysiloxane vanish in a state of containing an amino acid generator inhibits the condensation-polymerization and has advantageous preservation stability and when the polysiloxane vanish is applied on a base material and is subjected to a thermocuring or photocuring, there is generated an amino acid accelerating a condensation-polymerization (dehydration-condensation) between silanol groups of the polysiloxane.
  • the polysiloxane vanish of the present invention When the polysiloxane vanish of the present invention is formed into a coating film and is baked or irradiated with light (exposed to light), the property of the amino acid generator is changed to a basicity accelerating the condensation-polymerization of the polysiloxane, so that even when thereafter, a baking stage is performed, the baking time can be shortened and the baking temperature can be lowered.
  • FT-IR IR absorption spectrum
  • the molecular weight measurement (hereinafter, abbreviated as “GPC”) of a polymer was performed using a molecular weight measuring apparatus (trade name: Shodex GPC-104/101 system; manufactured by Showa Denko K.K.).
  • the gas chromatography measurement (hereinafter, abbreviated as “GC”) was performed using a gas chromatography apparatus (trade name: Shimadzu GC-14B; manufactured by Shimadzu Corporation) under the following conditions.
  • FE-SEM trade name: JSM-7400F; manufactured by JEOL Ltd.; hereinafter, abbreviated as “SEM”.
  • TEOS tetraethoxysilane
  • the PSV 1 contained ethanol as the solvent, had a SiO 2 solid content-converted concentration of 12% by mass, and had molecular weights of Mw: 2,500 and Mn: 1,700 measured by GPC measurement. The PSV 1 was measured by GC and as the result, there was not detected an alkoxysilane monomer.
  • a solution mixture of 41.60 g of TEOS (0.2 mol) and 35.66 g of methyltriethoxysilane (0.2 mol, hereinafter abbreviated as “MTES”) was dropped using an inner pressure equilibrium-type dropping funnel at a constant dropping rate over 20 minutes. After the dropping, the reaction was effected under reflux for 2 hours. After the completion of the reaction, the oil bath was removed and the reaction mixture was left to be cooled down to 23° C. to obtain a polysiloxane vanish (hereinafter, abbreviated as “PSV 2”).
  • PSV 2 polysiloxane vanish
  • the PSV 2 contained ethanol as the solvent, had a SiO 2 solid content-converted concentration of 12% by mass, and had molecular weights of Mw: 2,100 and Mn: 1,700 measured by GPC measurement. The PSV 2 was measured by GC and as the result, there was not detected an alkoxysilane monomer.
  • a solution mixture of 41.60 g of TEOS (0.2 mol), 24.96 g of MTES (0.14 mol), and 8.90 g of dimethyldiethoxysilane (0.06 mol, hereinafter abbreviated as “DMDES”) was dropped using an inner pressure equilibrium-type dropping funnel at a constant dropping rate over 20 minutes. After the dropping, the reaction was effected under reflux for 2 hours. After the completion of the reaction, the oil bath was removed and the reaction mixture was left to be cooled down to 23° C. to obtain a polysiloxane vanish (hereinafter, abbreviated as “PSV 3”).
  • PSV 3 polysiloxane vanish
  • the PSV 3 contained ethanol as the solvent, had a SiO 2 solid content-converted concentration of 12% by mass, and had molecular weights of Mw: 2,200 and Mn: 1,700 measured by GPC measurement. The PSV 3 was measured by GC and as the result, there was not detected an alkoxysilane monomer.
  • the PSV 4 contained ethanol as the solvent, had a SiO 2 solid content-converted concentration of 12% by mass, and had molecular weights of Mw: 2,100 and Mn: 1,700 measured by GPC measurement. The PSV 4 was measured by GC and as the result, there was not detected an alkoxysilane monomer.
  • Boc-Arg N- ⁇ , N- ⁇ 1, N- ⁇ 2-tri-tert-butoxycarbonyl-L-arginine (hereinafter, abbreviated as “Boc-Arg”) of Formula (A-2):
  • a polysiloxane vanish containing an amino acid generator was prepared as a coating film forming composition (hereinafter, abbreviated as “PSV 1-BArg”).
  • Boc-Asp N- ⁇ -tert-butoxycarbonyl-L-aspartic acid
  • a polysiloxane vanish containing an amino acid generator was prepared as a coating film forming composition (hereinafter, abbreviated as “PSV 1-BAsp”).
  • Boc-Gly N-tert-butoxycarbonyl-glycine
  • a polysiloxane vanish containing an amino acid generator was prepared as a coating film forming composition (hereinafter, abbreviated as “PSV 1-BGly”).
  • a polysiloxane vanish containing an amino acid generator was prepared as a coating film forming composition (hereinafter, abbreviated as “PSV 1-BHis”).
  • N- ⁇ , N- ⁇ -di-tert-butoxycarbonyl-L-lysine (hereinafter, abbreviated as “Boc-Lys”) of Formula (A-6):
  • a polysiloxane vanish containing an amino acid generator was prepared as a coating film forming composition (hereinafter, abbreviated as “PSV 1-BLys”).
  • FB-Arg N- ⁇ -(9-fluorenylmethoxycarbonyl)-N- ⁇ 1, N- ⁇ 2-di-tert-butoxycarbonyl-L-arginine (hereinafter, abbreviated as “FB-Arg”) of Formula (A-7):
  • a polysiloxane vanish containing an amino acid generator was prepared as a coating film forming composition (hereinafter, abbreviated as “PSV 1-FBArg”).
  • FB-Orn N- ⁇ -tert-butoxycarbonyl-N- ⁇ -(9-fluorenylmethoxycarbonyl)-L-ornithine
  • a polysiloxane vanish containing an amino acid generator was prepared as a coating film forming composition (hereinafter, abbreviated as “PSV 1-FBOrn”).
  • a polysiloxane vanish containing an amino acid generator was prepared as a coating film forming composition (hereinafter, abbreviated as “PSV 1-FFOrn”).
  • Example 1 In the same manner as in Example 1, except that instead of the amino acid generator as a basic component, monoethanolamine (hereinafter, abbreviated as “MEA”) was used, a polysiloxane vanish was prepared as a coating film forming composition (hereinafter, abbreviated as “PSV 1-MEA”).
  • MEA monoethanolamine
  • PSV 1-MEA a coating film forming composition
  • 4-aminopyridine (hereinafter, abbreviated as “4AP”) of Formula (A-10):
  • a polysiloxane vanish was prepared as a coating film forming composition (hereinafter, abbreviated as “PSV 1-4AP”).
  • DMAP dimethylaminopyridine
  • PV 1-DMAP a coating film forming composition
  • Example 2 In the same manner as in Example 1, except that instead of the amino acid generator as an amino acid, L-alanine (hereinafter, abbreviated as “Ala”) was used, a polysiloxane vanish was prepared as a coating film forming composition (hereinafter, abbreviated as “PSV 1-Ala”).
  • the amino acid generator as an amino acid
  • Al L-alanine
  • PSV 1-Ala a polysiloxane vanish
  • Example 1 In the same manner as in Example 1, except that instead of the amino acid generator as an amino acid, L-arginine (hereinafter, abbreviated as “Arg”) was used, a polysiloxane vanish was prepared as a coating film forming composition (hereinafter, abbreviated as “PSV 1-Arg”).
  • Arg L-arginine
  • PSV 1-Arg a coating film forming composition
  • Example 1 In the same manner as in Example 1, except that instead of the amino acid generator as an amino acid, L-aspartic acid (hereinafter, abbreviated as “Asp”) was used, a polysiloxane vanish was prepared as a coating film forming composition (hereinafter, abbreviated as “PSV 1-Asp”).
  • amino acid generator as an amino acid
  • PSV 1-Asp a polysiloxane vanish
  • Example 1 In the same manner as in Example 1, except that instead of the amino acid generator as an amino acid, glycine (hereinafter, abbreviated as “Gly”) was used, a polysiloxane vanish was prepared as a coating film forming composition (hereinafter, abbreviated as “PSV 1-Gly”).
  • Gly glycine
  • PSV 1-Gly a coating film forming composition
  • Example 1 In the same manner as in Example 1, except that instead of the amino acid generator as an amino acid, L-histidine (hereinafter, abbreviated as “His”) was used, a polysiloxane vanish was prepared as a coating film forming composition (hereinafter, abbreviated as “PSV 1-His”).
  • the amino acid generator as an amino acid
  • L-histidine hereinafter, abbreviated as “His”
  • PSV 1-His a coating film forming composition
  • Example 1 In the same manner as in Example 1, except that instead of the amino acid generator as an amino acid, L-lysine (hereinafter, abbreviated as “Lys”) was used, a polysiloxane vanish was prepared as a coating film forming composition (hereinafter, abbreviated as “PSV 1-Lys”).
  • L-lysine hereinafter, abbreviated as “Lys”
  • PSV 1-Lys a coating film forming composition
  • Example 1 In the same manner as in Example 1, except that instead of the amino acid generator as an amino acid, L-ornithine (hereinafter, abbreviated as “Orn”) was used, a polysiloxane vanish was prepared as a coating film forming composition (hereinafter, abbreviated as “PSV 1-Orn”).
  • the amino acid generator as an amino acid
  • L-ornithine hereinafter, abbreviated as “Orn”
  • PSV 1-Orn a coating film forming composition
  • the coating film forming compositions of Examples 1 to 9 and Comparative Examples 1 to 10 were subjected to a preservation stability test.
  • the preservation stability test was performed by filling 50 mL of each coating film forming composition in a 50 mL of a transparent low alkali-glass vessel, by preserving the vessel in a class-1000 clean room at 23° C. and 55 RH %, and by confirming the change with time of the composition. Specifically, days from a day on which the preservation of the coating film forming composition at room temperature started to a day on which a flaw occurred in the coating film forming composition are defined as the flaw occurrence elapsed days. In the case where a flaw occurred, the condition of the flaw was recorded.
  • the PSV 1-BAla obtained in Example 1 was subjected to the preservation stability test.
  • the PSV 1-BArg obtained in Example 2 was subjected to the preservation stability test.
  • the PSV 1-BAsp obtained in Example 3 was subjected to the preservation stability test.
  • the PSV 1-BGly obtained in Example 4 was subjected to the preservation stability test.
  • the PSV 1-BHis obtained in Example 5 was subjected to the preservation stability test.
  • the PSV 1-BLys obtained in Example 6 was subjected to the preservation stability test.
  • the PSV 1-FBArg obtained in Example 7 was subjected to the preservation stability test.
  • the PSV 1-FBOrn obtained in Example 8 was subjected to the preservation stability test.
  • the PSV 1-FFOrn obtained in Example 9 was subjected to the preservation stability test.
  • the PSV 1-MEA obtained in Comparative Example 1 was subjected to the preservation stability test.
  • the PSV 1-4AP obtained in Comparative Example 2 was subjected to the preservation stability test.
  • the PSV 1-DMAP obtained in Comparative Example 3 was subjected to the preservation stability test.
  • the PSV 1-Ala obtained in Comparative Example 4 was subjected to the preservation stability test.
  • the PSV 1-Arg obtained in Comparative Example 5 was subjected to the preservation stability test.
  • the PSV 1-Asp obtained in Comparative Example 6 was subjected to the preservation stability test.
  • the PSV 1-Gly obtained in Comparative Example 7 was subjected to the preservation stability test.
  • the PSV 1-Lys obtained in Comparative Example 9 was subjected to the preservation stability test.
  • the PSV 1-Orn obtained in Comparative Example 10 was subjected to the preservation stability test.
  • Flaw composition elapsed days conditions
  • Example 10 PSV 1-BAla 60 days or more No abnormality
  • Example 11 PSV 1-BArg 60 days or more No abnormality
  • Example 12 PSV 1-BAsp 60 days or more No abnormality
  • Example 13 PSV 1-BGly 60 days or more No abnormality
  • Example 14 PSV 1-BHis 60 days or more No abnormality
  • Example 15 PSV 1-BLys 60 days or more No abnormality
  • Example 16 PSV 1-FBArg 60 days or more No abnormality
  • Example 17 PSV 1-FBOrn 60 days or more No abnormality
  • Example 18 PSV 1-FFOrn 60 days or more No abnormality Comparative PSV 1-MEA During stirring Gelled Example 11 Comparative PSV 1-4AP During stirring Gelled Example 12 Comparative PSV 1-BAP During stirring Gelled Example 13 Comparative PSV 1-Ala During stirring Slightly soluble
  • Example 14 Comparative PSV 1-Arg During stirring Slightly soluble
  • Example 15 Comparative PSV 1-Asp During stirring Slightly soluble
  • polysiloxane vanishes containing an amino acid generator have extremely advantageous solubility and even when the polysiloxane vanish was preserved at room temperature for 60 days, it could be stably preserved without deposit and gelation.
  • the amino acid generator is an additive having remarkably high solubility and excellent preservation stability and when the amino acid generator is added to the polysiloxane vanish, it generates no foreign matter.
  • a coating film forming composition was produced using a polysiloxane vanish containing an amino acid generator and there was confirmed the variation in the behavior of reducing Si—OH bonds according to the variation in the baking condition when a coating film is produced by coating a substrate with a coating film forming composition.
  • the production of a film was performed by spin-coating a substrate (base material) with a coating film forming composition under conditions of at 2,000 rpm and for 20 seconds.
  • the coating film forming composition was spin-coated and was baked in the air using a hot plate as baking equipment.
  • the film thickness was set at 500 nm.
  • As the base material a 4-inch silicon wafer was used.
  • the coating film forming composition (PSV 1-BAla) obtained in Example 1 was spin-coated and was baked at 250° C. for 5 minutes. The coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 19 In the same manner as in Example 19, except that the coating film forming composition (PSV 1-BArg) obtained in Example 2 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement by a KBr method.
  • the coating film forming composition (PSV 1-BArg) obtained in Example 2 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 19 In the same manner as in Example 19, except that the coating film forming composition (PSV 1-BAsp) obtained in Example 3 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement by a KBr method.
  • the coating film forming composition (PSV 1-BAsp) obtained in Example 3 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 19 In the same manner as in Example 19, except that the coating film forming composition (PSV 1-BGly) obtained in Example 4 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 19 In the same manner as in Example 19, except that the coating film forming composition (PSV 1-BHis) obtained in Example 5 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement by a KBr method.
  • the coating film forming composition (PSV 1-BHis) obtained in Example 5 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 19 In the same manner as in Example 19, except that the coating film forming composition (PSV 1-BLys) obtained in Example 6 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement by a KBr method.
  • the coating film forming composition (PSV 1-BLys) obtained in Example 6 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 19 In the same manner as in Example 19, except that the coating film forming composition (PSV 1-FBArg) obtained in Example 7 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement by a KBr method.
  • the coating film forming composition (PSV 1-FBArg) obtained in Example 7 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 19 In the same manner as in Example 19, except that the coating film forming composition (PSV 1-FBOrn) obtained in Example 8 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement by a KBr method.
  • the coating film forming composition (PSV 1-FBOrn) obtained in Example 8 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 19 In the same manner as in Example 19, except that the coating film forming composition (PSV 1-FFOrn) obtained in Example 9 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement by a KBr method.
  • the coating film forming composition (PSV 1-FFOrn) obtained in Example 9 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 19 In the same manner as in Example 19, except that as the coating film forming composition, the polysiloxane vanish (PSV 1) obtained in Synthesis Example 1 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement by a KBr method.
  • PSV 1 polysiloxane vanish
  • the polysiloxane vanish (PSV 1) obtained in Synthesis Example 1 and used as the coating film forming composition was spin-coated and the composition was baked at 250° C. for 120 minutes.
  • the coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish (PSV 1) obtained in Synthesis Example 1 and used as the coating film forming composition was spin-coated and the composition was baked at 300° C. for 120 minutes.
  • the coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish (PSV 1) obtained in Synthesis Example 1 and used as the coating film forming composition was spin-coated and the composition was baked at 400° C. for 120 minutes.
  • the coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the pH measurement was performed using a digital pH meter after the calibration was performed using pH standard solutions of pH 4, 7, and 9 for the calibration.
  • the pH value of the resultant solution was measured.
  • the amino acid generator an amine moiety developing basicity is protected by a protecting group and consequently, the amino acid generator exhibits property of a carboxylic acid, so that as shown in Measurement Examples 1 to 9, the pH values became between 4.11 and 2.40.
  • the pH value around 4 is in a pH range in which the polysiloxane vanish can be stably preserved, which is especially preferred.
  • the condensation-polymerization of the polysiloxane remarkably progresses in a basic range, so that the pH value of each film produced using arginine, histidine, lysine, and ornithine inclines to basicity and consequently, arginine, histidine, lysine, and ornithine are extremely preferred. Also with respect to a film produced using an amino acid generator that does not incline to basicity after the elimination of a protecting group, from the result in FIG. 3 in which a peak for an Si—OH bond decreases, it is indicated that the condensation-polymerization of the polysiloxane progresses when an amine moiety is developed.
  • the film formation was performed by a spin coating method under conditions of at 2,000 rpm and for 20 seconds.
  • the coating film forming composition was spin-coated and was baked in the air using a hot plate as baking equipment.
  • the film thickness was set to 500 nm.
  • As the base material a 4-inch silicon wafer was used.
  • the coating film forming composition (PSV 1-BArg) obtained in Example 2 was spin-coated and was baked at 100° C. for 5 minutes. The coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the coating film forming composition (PSV 1-BArg) obtained in Example 2 was spin-coated and was baked at 150° C. for 5 minutes. The coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the coating film forming composition (PSV 1-BArg) obtained in Example 2 was spin-coated and was baked at 200° C. for 5 minutes. The coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish (PSV 1) obtained in Synthesis Example 1 and used as the coating film forming composition was spin-coated and was baked at 100° C. for 5 minutes.
  • the coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish (PSV 1) obtained in Synthesis Example 1 and used as the coating film forming composition was spin-coated and was baked at 150° C. for 5 minutes.
  • the coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish (PSV 1) obtained in Synthesis Example 1 and used as the coating film forming composition was spin-coated and was baked at 200° C. for 5 minutes.
  • the coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 20 and Examples 28 to 30 are shown in FIG. 2 and FIGS. 10 to 12 and the results of Comparative Example 21 and Comparative Examples 25 to 27 are shown in FIG. 30 and FIGS. 34 to 36 .
  • Example 29 In comparison of Example 29 with Comparative Example 21, as the relative evaluation of FT-IR, substantially the same peak strength of the Si—OH bond was obtained in these Examples and it is considered that the temperature at which the amino acid generator develops basicity of an amine by heat starts from around 150° C.
  • the film formation was performed by a spin coating method under conditions of at 2,000 rpm and for 20 seconds.
  • the coating film forming composition was spin-coated and was baked in the air using a hot plate as baking equipment.
  • the film thickness was set to 500 nm.
  • As the base material a 4-inch silicon wafer was used.
  • Example 2 In the same manner as in Example 2, except that Boc-Arg was added to the polysiloxane vanish in an amount of 0.1 phr (that is, the composition contains Boc-Arg in an amount of 0.1 parts by mass relative to 100 parts by mass of SiO 2 in the polysiloxane vanish PSV 1), a coating film forming composition (hereinafter, abbreviated as “PSV 1-BArg-0.1 phr”) was prepared. The obtained coating film forming composition (PSV 1-BArg-0.1 phr) was spin-coated and was baked at 250° C. for 5 minutes. The coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • PSV 1-BArg-0.1 phr a coating film forming composition
  • Example 2 In the same manner as in Example 2, except that Boc-Arg was added to the polysiloxane vanish in an amount of 0.5 phr (that is, the composition contains Boc-Arg in an amount of 0.5 parts by mass relative to 100 parts by mass of SiO 2 in the polysiloxane vanish PSV 1), a coating film forming composition (hereinafter, abbreviated as “PSV 1-BArg-0.5 phr”) was prepared.
  • the obtained coating film forming composition (PSV 1-BArg-0.5 phr) was spin-coated and was baked at 250° C. for 5 minutes. The coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 2 In the same manner as in Example 2, except that Boc-Arg was added to the polysiloxane vanish in an amount of 1.0 phr (that is, the composition contains Boc-Arg in an amount of 0.1 parts by mass relative to 100 parts by mass of SiO 2 in the polysiloxane vanish.
  • PSV 1 a coating film forming composition
  • PSV 1-BArg-1.0 phr a coating film forming composition
  • the obtained coating film forming composition (PSV 1-BArg-1.0 phr) was spin-coated and was baked at 250° C. for 5 minutes. The coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 2 In the same manner as in Example 2, except that Boc-Arg was added to the polysiloxane vanish in an amount of 2.5 phr (that is, the composition contains Boc-Arg in an amount of 2.5 parts by mass relative to 100 parts by mass of SiO 2 in the polysiloxane vanish PSV 1), a coating film forming composition (hereinafter, abbreviated as “PSV 1-BArg-2.5 phr”) was prepared.
  • the obtained coating film forming composition (PSV 1-BArg-2.5 phr) was spin-coated and was baked at 250° C. for 5 minutes. The coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 20 The results of Example 20 and Examples 31 to 34 are shown in FIG. 2 and FIGS. 13 to 16 .
  • the film formation was performed by a spin coating method under conditions of at 2,000 rpm and for 20 seconds.
  • the coating film forming composition was spin-coated and was baked in the air using a hot plate as baking equipment.
  • the film thickness was set to 500 nm.
  • As the base material a 4-inch silicon wafer was used.
  • Boc-Arg was added to the polysiloxane vanish PSV 2 obtained in Synthesis Example 2 to prepare a coating film forming composition (hereinafter, abbreviated as “PSV 2-BArg”).
  • the coating film forming composition (PSV 2-BArg) was spin-coated and was baked at 250° C. for 5 minutes. The coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • PSV 2-BLys a coating film forming composition
  • the coating film forming composition (PSV 2-BLys) was spin-coated and was baked at 250° C. for 5 minutes. The coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • PSV 2-BHis a coating film forming composition
  • the coating film forming composition (PSV 2-BHis) was spin-coated and was baked at 250° C. for 5 minutes. The coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • Boc-Arg was added to the polysiloxane vanish PSV 3 obtained in Synthesis Example 3 to prepare a coating film forming composition (hereinafter, abbreviated as “PSV 3-BArg”).
  • the coating film forming composition (PSV 3-BArg) was spin-coated and was baked at 250° C. for 5 minutes. The coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 2 Boc-Lys was added to the polysiloxane vanish PSV 3 obtained in Synthesis Example 3 to prepare a coating film forming composition (hereinafter, abbreviated as “PSV 3-BLys”).
  • the coating film forming composition (PSV 3-BLys) was spin-coated and was baked at 250° C. for 5 minutes. The coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • PSV 3-BHis a coating film forming composition
  • the coating film forming composition (PSV 3-BHis) was spin-coated and was baked at 250° C. for 5 minutes. The coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • Boc-Arg was added to the polysiloxane vanish PSV 4 obtained in Synthesis Example 4 to prepare a coating film forming composition (hereinafter, abbreviated as “PSV 4-BArg”).
  • the coating film forming composition (PSV 4-BArg) was spin-coated and was baked at 250° C. for 5 minutes. The coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 2 Boc-Lys was added to the polysiloxane vanish PSV 4 obtained in Synthesis Example 4 to prepare a coating film forming composition (hereinafter, abbreviated as “PSV 4-BLys”).
  • the coating film forming composition (PSV 4-BLys) was spin-coated and was baked at 250° C. for 5 minutes. The coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • PSV 4-BHis a coating film forming composition
  • the coating film forming composition (PSV 4-BHis) was spin-coated and was baked at 250° C. for 5 minutes. The coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 2 obtained in Synthesis Example 2 and used as the coating film forming composition was spin-coated and was baked at 250° C. for 5 minutes.
  • the coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 2 obtained in Synthesis Example 2 and used as the coating film forming composition was spin-coated and was baked at 400° C. for 5 minutes.
  • the coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 3 obtained in Synthesis Example 3 and used as the coating film forming composition was spin-coated and was baked at 250° C. for 5 minutes.
  • the coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 3 obtained in Synthesis Example 3 and used as the coating film forming composition was spin-coated and was baked at 400° C. for 5 minutes.
  • the coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 4 obtained in Synthesis Example 4 and used as the coating film forming composition was spin-coated and was baked at 250° C. for 5 minutes.
  • the coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 4 obtained in Synthesis Example 4 and used as the coating film forming composition was spin-coated and was baked at 400° C. for 5 minutes.
  • the coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • Examples 35 to 37 and Comparative Examples 28 and 29 are shown in FIGS. 17 to 19 and FIGS. 37 and 38 ; the results of Examples 38 to 40 and Comparative Examples 30 and 31 are shown in FIGS. 20 to 22 and FIGS. 39 and 40 ; and the results of Examples 41 to 43 and Comparative Examples 32 and 33 are shown in FIGS. 23 to 25 and FIGS. 41 and 42 .
  • a film obtained from a coating film forming composition in which arginine, histidine, or lysine having particularly high ability of accelerating the condensation-polymerization of the polysiloxane as the amino acid generator was added to a polysiloxane vanish is effective for digesting the Si—OH bond also with respect to the polysiloxane vanishes PSV 2 to 4 just like with respect to PSV 1.
  • the film formation was performed by a spin coating method under conditions of at 2,000 rpm and for 20 seconds.
  • the coating film forming composition was spin-coated and was baked in the air using a hot plate as baking equipment.
  • the film thickness was set to 500 nm.
  • As the base material a 4-inch silicon wafer was used.
  • Boc-Arg was added in the same manner as in Example 1 to obtain a coating film forming composition (hereinafter, abbreviated as “PSV 1-BArg-PGMEA”).
  • the obtained coating film forming composition (PSV 1-BArg-PGMEA) was spin-coated and was baked at 250° C. for 5 minutes.
  • the coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 2 obtained in Synthesis Example 2 was subjected to the solvent-exchange to PGMEA in the same manner as in Example 44 and thereto, Boc-Arg was added.
  • the resultant coating film forming composition (hereinafter, abbreviated as “PSV 2-Boc-Arg-PGMEA”) was spin-coated and was baked at 250° C. for 5 minutes.
  • the coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 3 obtained in Synthesis Example 3 was subjected to the solvent-exchange to PGMEA in the same manner as in Example 44 and thereto, Boc-Arg was added.
  • the resultant coating film forming composition (hereinafter, abbreviated as “PSV 3-Boc-Arg-PGMEA”) was spin-coated and was baked at 250° C. for 5 minutes.
  • the coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 4 obtained in Synthesis Example 4 was subjected to the solvent-exchange to PGMEA in the same manner as in Example 44 and thereto, Boc-Arg was added.
  • the obtained coating film forming composition (hereinafter, abbreviated as “PSV 4-Boc-Arg-PGMEA”) was spin-coated and was baked at 250° C. for 5 minutes.
  • the coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the obtained coating film forming composition (hereinafter, abbreviated as “PSV 1-PGMEA) after the solvent-exchange was spin-coated and was baked at 250° C. for 5 minutes.
  • the coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 2 obtained in Synthesis Example 2 was subjected to the solvent-exchange to PGMEA in the same manner as in Comparative Example 34.
  • the obtained coating film forming composition (hereinafter, abbreviated as “PSV 2-PGMEA”) was spin-coated and was baked at 250° C. for 5 minutes.
  • the coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 3 obtained in Synthesis Example 3 was subjected to the solvent-exchange to PGMEA in the same manner as in Comparative Example 34.
  • the obtained coating film forming composition (hereinafter, abbreviated as “PSV 3-PGMEA”) was spin-coated and was baked at 250° C. for 5 minutes.
  • the coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 4 obtained in Synthesis Example 4 was subjected to the solvent-exchange to PGMEA in the same manner as in Comparative Example 34.
  • the obtained coating film forming composition (hereinafter, abbreviated as “PSV 3-PGMEA”) was spin-coated and was baked at 250° C. for 5 minutes.
  • the coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • a polysiloxane composition in which an amino acid generator is added to a polysiloxane vanish can maintain advantageous preservation stability of the polysiloxane vanish, can accelerate the condensation-polymerization during baking, and can remarkably reduce remaining Si—OH bonds, so that such a polysiloxane composition is effective as the coating film forming composition.
  • a coating film forming composition was produced using a polysiloxane vanish containing a photo amino acid generator, and the variation in the behavior of reducing Si—OH bonds according to the variation in the exposure conditions when a coating film is produced by coating a substrate with the coating film forming composition, was confirmed.
  • the production of a film was performed by spin-coating a substrate (base material) with the coating film forming composition under conditions of at 2,000 rpm and for 20 seconds.
  • the coating film forming composition was spin-coated and subjected to drying at room temperature (about 20° C.) to remove the solvent in the composition and to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the film thickness was set at 500 nm.
  • As the base material a 4-inch silicon wafer was used.
  • the coating film forming composition (PSV 1-BAla) obtained in Example 1 was spin-coated and was subjected to drying at room temperature to remove the solvent and to a 1 J/cm 2 of exposure. The coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 48 In the same manner as in Example 48, except that the coating film forming composition (PSV 1-BArg) obtained in Example 2 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement.
  • the coating film forming composition (PSV 1-BArg) obtained in Example 2 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement.
  • Example 48 In the same manner as in Example 48, except that the coating film forming composition (PSV 1-BAsp) obtained in Example 3 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement.
  • the coating film forming composition (PSV 1-BAsp) obtained in Example 3 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement.
  • Example 48 In the same manner as in Example 48, except that the coating film forming composition (PSV 1-BGly) obtained in Example 4 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement.
  • the coating film forming composition PSV 1-BGly
  • Example 48 In the same manner as in Example 48, except that the coating film forming composition (PSV 1-BHis) obtained in Example 5 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement.
  • the coating film forming composition (PSV 1-BHis) obtained in Example 5 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement.
  • Example 48 In the same manner as in Example 48, except that the coating film forming composition (PSV 1-BLys) obtained in Example 6 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement by a KBr method.
  • the coating film forming composition (PSV 1-BLys) obtained in Example 6 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 48 In the same manner as in Example 48, except that the coating film forming composition (PSV 1-FBArg) obtained in Example 7 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement.
  • the coating film forming composition (PSV 1-FBArg) obtained in Example 7 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement.
  • Example 48 In the same manner as in Example 48, except that the coating film forming composition (PSV 1-FBOrn) obtained in Example 8 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement.
  • the coating film forming composition (PSV 1-FBOrn) obtained in Example 8 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement.
  • Example 9 In the same manner as in Example 48, except that the coating film forming composition (PSV 1-FFOrn) obtained in Example 9 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement.
  • the coating film forming composition PSV 1-FFOrn
  • the polysiloxane vanish (PSV 1) obtained in Synthesis Example 1 was spin-coated and then subjected to drying at room temperature to remove the solvent and not subjected to exposure.
  • the coating film after drying was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish (PSV 1) obtained in Synthesis Example 1 and used as the coating film forming composition was spin-coated and then subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish (PSV 1) obtained in Synthesis Example 1 and used as the coating film forming composition was spin-coated and then subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 2 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish (PSV 1) obtained in Synthesis Example 1 and used as the coating film forming composition was spin-coated and then subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 5 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish (PSV 1) obtained in Synthesis Example 1 and used as the coating film forming composition was spin-coated and then subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 10 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the film formation was performed by a spin coating method under conditions of at 2,000 rpm and for 20 seconds.
  • the coating film forming composition was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus as an exposure apparatus.
  • the film thickness was set to 500 nm.
  • As the base material a 4-inch silicon wafer was used.
  • the coating film forming composition (PSV 1-BArg) obtained in Example 2 was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 100 mJ/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the coating film forming composition (PSV 1-BArg) obtained in Example 2 was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 200 mJ/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the coating film forming composition (PSV 1-BArg) obtained in Example 2 was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 500 mJ/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish (PSV 1) obtained in Synthesis Example 1 and used as the coating film forming composition was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 100 mJ/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish (PSV 1) obtained in Synthesis Example 1 and used as the coating film forming composition was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using an UV irradiation apparatus in an exposure amount of 200 mJ/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish (PSV 1) obtained in Synthesis Example 1 and used as the coating film forming composition was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using an UV irradiation apparatus in an exposure amount of 500 mJ/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 49 and Examples 57 to 59 are shown in FIG. 48 and FIGS. 56 to 58 and the results of Comparative Example 38 and Comparative Examples 43 to 45 are shown in FIG. 76 and FIGS. 81 to 83 .
  • the film formation was performed by a spin coating method under conditions of at 2,000 rpm and for 20 seconds.
  • the coating film forming composition was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus as an exposure apparatus.
  • the film thickness was set to 500 nm.
  • As the base material a 4-inch silicon wafer was used.
  • Example 2 In the same manner as in Example 2, except that Boc-Arg was added to the polysiloxane vanish in an amount of 0.1 phr (that is, the composition contains Boc-Arg in an amount of 0.1 parts by mass relative to 100 parts by mass of SiO 2 in the polysiloxane vanish PSV 1), a coating film fowling composition (hereinafter, abbreviated as “PSV 1-BArg-0.1 phr”) was prepared.
  • PSV 1-BArg-0.1 phr a coating film fowling composition
  • the obtained coating film forming composition (PSV 1-BArg-0.1 phr) was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 2 In the same manner as in Example 2, except that Boc-Arg was added to the polysiloxane vanish in an amount of 0.5 phr (that is, the composition contains Boc-Arg in an amount of 0.5 parts by mass relative to 100 parts by mass of SiO 2 in the polysiloxane vanish PSV 1), a coating film forming composition (hereinafter, abbreviated as “PSV 1-BArg-0.5 phr”) was prepared.
  • PSV 1-BArg-0.5 phr a coating film forming composition
  • the obtained coating film forming composition (PSV 1-BArg-0.5 phr) was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • a coating film forming composition (hereinafter, abbreviated as “PSV 1-BArg-1.0 phr”) was prepared.
  • the obtained coating film forming composition (PSV 1-BArg-1.0 phr) was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using an UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • a coating film forming composition (hereinafter, abbreviated as “PSV 1-BArg-2.5 phr”) was prepared.
  • the obtained coating film forming composition (PSV 1-BArg-2.5 phr) was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using an UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 49 The results of Example 49 and Examples 60 to 62 are shown in FIG. 48 and FIGS. 59 to 62 .
  • the film formation was performed by a spin coating method under conditions of at 2,000 rpm and for 20 seconds.
  • the coating film forming composition was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus as an exposure apparatus.
  • the film thickness was set to 500 nm.
  • a 4-inch silicon wafer was used.
  • a 4-inch silicon wafer was used as the base material.
  • Boc-Arg was added to the polysiloxane vanish PSV 2 obtained in Synthesis Example 2 to prepare a coating film forming composition (hereinafter, abbreviated as “PSV 2-BArg”).
  • the coating film forming composition (PSV 2-BArg) was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • PSV 2-BLys a coating film forming composition
  • the coating film forming composition (PSV 2-BLys) was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • PSV 2-BHis a coating film forming composition
  • the coating film forming composition (PSV 2-BHis) was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • Boc-Arg was added to the polysiloxane vanish PSV 3 obtained in Synthesis Example 3 to prepare a coating film forming composition (hereinafter, abbreviated as “PSV 3-BArg”).
  • the coating film forming composition (PSV 3-BArg) was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • PSV 3-BLys a coating film forming composition
  • the coating film forming composition (PSV 3-BLys) was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • PSV 3-BHis a coating film forming composition
  • the coating film forming composition (PSV 3-BHis) was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • Boc-Arg was added to the polysiloxane vanish PSV 4 obtained in Synthesis Example 4 to prepare a coating film forming composition (hereinafter; abbreviated as “PSV 4-BArg”).
  • the coating film forming composition (PSV 4-BArg) was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • PSV 4-BLys a coating film forming composition
  • the coating film forming composition (PSV 4-BLys) was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • PSV 4-BHis a coating film forming composition
  • the coating film forming composition (PSV 4-BHis) was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 2 obtained in Synthesis Example 2 and used as the coating film forming composition was spin-coated and was subjected to drying at room temperature to remove the solvent and not subjected to exposure.
  • the coating film after drying was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 3 obtained in Synthesis Example 2 and used as the coating film forming composition was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 3 obtained in Synthesis Example 2 and used as the coating film forming composition was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 5 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 4 obtained in Synthesis Example 3 and used as the coating film forming composition was spin-coated and was subjected to drying at room temperature to remove the solvent and not subjected to exposure.
  • the coating film after drying was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 4 obtained in Synthesis Example 3 and used as the coating film forming composition was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 3 obtained in Synthesis Example 3 and used as the coating film forming composition was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 5 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 4 obtained in Synthesis Example 4 and used as the coating film fowling composition was spin-coated and was subjected to drying at room temperature to remove the solvent and not subjected to exposure.
  • the coating film after drying was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 4 obtained in Synthesis Example 4 and used as the coating film forming composition was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using an UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 4 obtained in Synthesis Example 4 and used as the coating film forming composition was spin-coated and was subjected to drying at room temperature to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 5 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • Examples 64 to 66 and Comparative Examples 46 to 48 are shown in FIGS. 63 to 65 and FIGS. 84 and 86 ; the results of Examples 67 to 69 and Comparative Examples 49 to 51 are shown in FIGS. 66 to 68 and FIGS. 87 to 89 ; and the results of Examples 70 to 72 and Comparative Examples 52 to 54 are shown in FIGS. 69 to 71 and FIGS. 90 to 92 .
  • a film obtained from a coating film forming composition in which arginine having particularly high ability of accelerating the condensation-polymerization of the polysiloxane as the photo amino acid generator was added to a polysiloxane vanish is effective for digesting the Si—OH bond also with respect to the polysiloxane vanishes PSV 2 to 4 just like with respect to PSV 1.
  • the film formation was performed by a spin coating method under conditions of at 2,000 rpm and for 20 seconds.
  • the coating film forming composition was spin-coated and was subjected to drying at 150° C. for 5 minutes to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus as an exposure apparatus.
  • the film thickness was set to 500 nm.
  • baking at 150° C. for 5 minutes is a process for completely removing PGMEA as the solvent and at this time, it was confirmed that the photo amino acid generator is not decomposed. That is, under the baking conditions of at 150° C. and for 5 minutes, the condensation-polymerization of Si—OH bonds with each other is not accelerated and only during the following light irradiation, the condensation-polymerization is accelerated.
  • As the base material a 4-inch silicon wafer was used.
  • Boc-Arg was added in the same manner as in Example 1 to obtain a coating film forming composition (hereinafter, abbreviated as “PSV 1-BArg-PGMEA”).
  • the obtained coating film forming composition (PSV 1-BArg-PGMEA) was spin-coated and was subjected to drying at 150° C. for 5 minutes to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 2 obtained in Synthesis Example 2 was subjected to the solvent-exchange to PGMEA in the same manner as in Example 73 and thereto, Boc-Arg was added.
  • the obtained coating film forming composition (hereinafter, abbreviated as “PSV 2-Boc-Arg-PGMEA) was spin-coated and was subjected to drying at 150° C. for 5 minutes to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 3 obtained in Synthesis Example 3 was subjected to the solvent-exchange to PGMEA in the same manner as in Example 73 and thereto, Boc-Arg was added.
  • the obtained coating film forming composition (hereinafter, abbreviated as “PSV 3-Boc-Arg-PGMEA) was spin-coated and was subjected to drying at 150° C. for 5 minutes to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 4 obtained in Synthesis Example 4 was subjected to the solvent-exchange to PGMEA in the same manner as in Example 73 and thereto, Boc-Arg was added.
  • the obtained coating film forming composition (hereinafter, abbreviated as “PSV 4-Boc-Arg-PGMEA) was spin-coated and was subjected to drying at 150° C. for 5 minutes to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the obtained coating film forming composition (hereinafter, abbreviated as “PSV 1-PGMEA”) after the solvent-exchange was spin-coated and was subjected to drying at 150° C. for 5 minutes to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 2 obtained in Synthesis Example 2 was subjected to the solvent-exchange to PGMEA in the same manner as in Comparative Example 55.
  • the obtained coating film forming composition (hereinafter, abbreviated as “PSV 2-PGMEA) was spin-coated and was subjected to drying at 150° C. for 5 minutes to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 3 obtained in Synthesis Example 3 was subjected to the solvent-exchange to PGMEA in the same manner as in Comparative Example 55.
  • the obtained coating film forming composition (hereinafter, abbreviated as “PSV 3-PGMEA) was spin-coated and was subjected to drying at 150° C. for 5 minutes to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • the polysiloxane vanish PSV 4 obtained in Synthesis Example 4 was subjected to the solvent-exchange to PGMEA in the same manner as in Comparative Example 55.
  • the obtained coating film forming composition (hereinafter, abbreviated as “PSV 3-PGMEA”) was spin-coated and was subjected to drying at 150° C. for 5 minutes to remove the solvent, which was then subjected to exposure in the air using a UV irradiation apparatus in an exposure amount of 1 J/cm 2 (converted into energy at 250 nm).
  • the coating film after exposure was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • a polysiloxane composition in which a photo amino acid generator is added to a polysiloxane vanish can maintain advantageous preservation stability of the polysiloxane vanish, can accelerate the condensation-polymerization during baking, and can remarkably reduce remaining Si—OH bonds, so that the polysiloxane composition is effective as the coating film forming composition.
  • a via substrate was spin-coated with each of the polysiloxane vanish (PVS 2) obtained in Synthesis Example 2 and polysiloxane compositions obtained in Examples 77 to 80 as the coating film forming composition and the composition was baked in the air using a hot plate at 400° C. for 5 minutes and subjected to an SEM observation.
  • the spin-coating was performed under conditions of at 2,000 rpm and for 30 seconds.
  • a via substrate was spin-coated with the polysiloxane composition obtained in Example 78 as the coating film forming composition and the composition was baked in the air using a hot plate at 400° C. for 15 minutes, 30 minutes, or 60 minutes and subjected to an SEM observation.
  • the spin-coating was performed under conditions of at 2,000 rpm and for 30 seconds.
  • FIGS. 97 and 98 Examples of the filling property in a via substrate after baking are shown in FIGS. 97 and 98 .
  • FIG. 97 is a cross section view of a via in which filling property is advantageous and
  • FIG. 98 is a cross section view of a via in which filling was accompanied by a slit, which is not so preferred.
  • Example 81 In the same manner as in Example 81, except that as the amino acid generator, N- ⁇ , N- ⁇ -di-tert-butoxycarbonyl-L-lysine (hereinafter, abbreviated as “Boc-Lys”, where D is a protecting group for an amino group) of Formula (A-6) was used, a polysiloxane composition containing an organic crosslinkable compound and an amino acid generator was prepared as a coating film forming composition (hereinafter, abbreviated as “PSV 2-PWL-BLys”).
  • PSV 2-PWL-BLys a coating film forming composition
  • Example 81 N- ⁇ -tert-butoxycarbonyl-N- ⁇ -(9-fluorenylmethoxycarbonyl)-L-ornithine (hereinafter, abbreviated as “FB-Orn”, where D 1 and D 2 are protecting groups for an amino group) of Formula (A-8) was used, a polysiloxane composition containing an organic crosslinkable compound and an amino acid generator was prepared as a coating film forming composition (hereinafter, abbreviated as “PSV 2-PWL-FBOrn”).
  • PSV 2-PWL-FBOrn a coating film forming composition
  • a coating film forming composition was produced using a polysiloxane composition containing an amino acid generator and there was confirmed the variation in the behavior of reducing Si—OH bonds according to the variation in the baking condition when a coating film is produced by coating a substrate with the coating film forming composition.
  • the production of a film was performed by spin-coating a substrate (base material) with the coating film forming composition under conditions of at 2,000 rpm and for 20 seconds.
  • the coating film forming composition was spin-coated and was baked in the air using a hot plate as baking equipment.
  • the film thickness was set at 500 nm.
  • As the base material a 4-inch silicon wafer was used.
  • the coating film forming composition (PSV 2-PWL-BArg) obtained in Example 81 was spin-coated and was baked at 250° C. for 5 minutes. The coating film after baking was pared off and the resultant sample piece was subjected to an FT-IR spectrum measurement by a KBr method.
  • Example 84 In the same manner as in Example 84, except that the coating film forming composition (PSV 2-PWL-BLys) obtained in Example 82 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement.
  • the coating film forming composition PSV 2-PWL-BLys
  • Example 84 In the same manner as in that Example 84, except that the coating film forming composition (PSV 2-PWL-FBOrn) obtained in Example 83 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement.
  • the coating film forming composition PSV 2-PWL-FBOrn
  • Example 84 In the same manner as in Example 84, except that as the coating film forming composition, the polysiloxane vanish (PSV 2) obtained in Synthesis Example 2 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement.
  • PSV 2 polysiloxane vanish
  • Example 8 In the same manner as in Example 8, except that as the coating film forming composition, the polysiloxane vanish (PSV 2-PWL 10 phr) obtained in Example 79 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement.
  • the polysiloxane vanish (PSV 2-PWL 10 phr) obtained in Example 79 was used, the coating film was formed and a sample piece thereof was subjected to an FT-IR spectrum measurement.
  • a polysiloxane composition in which an amino acid generator is added to a polysiloxane vanish can accelerate the condensation-polymerization during baking and can remarkably reduce remaining Si—OH bonds, so that such a polysiloxane composition is effective as the coating film forming composition.
  • a polysiloxane composition in which an organic crosslinkable compound is added to a polysiloxane vanish has advantageous filling property. Further, it could also be confirmed that a polysiloxane composition in which an organic crosslinkable compound and an amino acid generator are added to a polysiloxane vanish has advantageous filling property, can accelerate the condensation-polymerization during baking, and can remarkably reduce remaining Si—OH bonds, so that such a polysiloxane composition is effective as the coating film forming composition.
  • the above polysiloxane composition can enhance filling property in a via and can remarkably reduce remaining Si—OH bonds, so that various polysiloxane compositions can be designed and the process margin can be enlarged.
  • the above polysiloxane composition can be preferably used as one member of an electronic device, particularly a solid state imaging device.
  • the coating film forming composition containing the amino acid generator of the present invention can control pH of the polysiloxane vanish during the preservation and baking or light irradiation by varying the type of the amino acid generator, so that polysiloxane compositions corresponding to device types to be produced and various baking processes can be designed and the process margin can be enlarged. Accordingly, the coating film forming composition of the present invention can preferably be used as one member of an electronic device, particularly a solid state imaging device.
  • the coating film forming composition of the present invention can be applied to a solid state imaging device containing a charge coupled device (CCD) or a complementary metal oxide film semiconductor (CMOS) that contains a film formed from the coating film forming composition of the present invention, to a solid state imaging device containing the above film as a planarization layer on a color filter, and to a solid state imaging device containing the above film as a planarization layer or a conformal layer on a microlens.
  • CCD charge coupled device
  • CMOS complementary metal oxide film semiconductor

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US9914809B2 (en) * 2013-08-30 2018-03-13 Momentive Performance Materials Inc. Moisture curable composition with amino acids
JP2016131215A (ja) * 2015-01-14 2016-07-21 日本曹達株式会社 有機薄膜トランジスタ

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