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WO2025074731A1 - Organopolysiloxane ramifié, composition le contenant et utilisation associée - Google Patents

Organopolysiloxane ramifié, composition le contenant et utilisation associée Download PDF

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Publication number
WO2025074731A1
WO2025074731A1 PCT/JP2024/028238 JP2024028238W WO2025074731A1 WO 2025074731 A1 WO2025074731 A1 WO 2025074731A1 JP 2024028238 W JP2024028238 W JP 2024028238W WO 2025074731 A1 WO2025074731 A1 WO 2025074731A1
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Prior art keywords
group
branched organopolysiloxane
branched
formula
acid
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Japanese (ja)
Inventor
聞斌 梁
琢哉 小川
立易 談
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Dow Toray Co Ltd
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Dow Toray Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds

Definitions

  • the present invention relates to a branched organopolysiloxane whose solubility in an alkaline aqueous solution is improved by irradiation with high-energy rays such as ultraviolet rays (including extreme ultraviolet rays and far ultraviolet rays) or electron beams, and a composition containing the same.
  • the branched organopolysiloxane of the present invention has a low molecular weight and a narrow molecular weight distribution, and forms a coating film with good alkali solubility by irradiation with high-energy rays.
  • silicone resins have high heat resistance and excellent chemical stability, they have traditionally been used as coating agents, potting agents, and insulating materials for electronic and electrical devices.
  • the present invention has been made to solve the above-mentioned problems, and was completed based on the discovery that a branched organopolysiloxane which has hydrophilic groups protected by acid-decomposable functional groups bonded to silicon atoms in the molecule, which has silsesquioxane units (so-called T units) as its main constituent units, and which has a weight-average molecular weight and polydispersity of not more than predetermined values, exhibits high solubility in an aqueous alkaline developer when irradiated with high-energy rays, and is useful as a resist material.
  • the branched organopolysiloxane can form a coating film that is highly transparent and has sufficient mechanical strength for practical use.
  • the branched organopolysiloxane is preferably a relatively small molecule with a low polydispersity, and from the viewpoint of technical effect, it is particularly preferred that the branched organopolysiloxane has a cage molecular structure, including a complete cage structure.
  • a composition containing the above-mentioned branched organopolysiloxane undergoes a chemical reaction by irradiation with high-energy rays such as ultraviolet rays, thereby controlling the solubility in an alkaline aqueous solution.
  • high-energy rays such as ultraviolet rays
  • any means capable of initiating a chemical reaction may be employed in addition to or instead of the above-mentioned high-energy ray irradiation.
  • the branched organopolysiloxane of the present invention is represented by the following average unit formula (1), and has a weight average molecular weight, calculated in terms of standard polystyrene, of 2,000 or less and a polydispersity of 1.30 or less, as measured by gel permeation chromatography.
  • the number of siloxane units having a hydrophilic group protected by the acid-decomposable functional group may be more than 20 mol% of the total number of siloxane units.
  • the hydrophilic group protected with the acid-decomposable functional group may be a group represented by the following formula (2).
  • R1 is a divalent hydrocarbon group which may have a carbonyl group.
  • R2 is a monovalent hydrocarbon group having 1 to 4 carbon atoms or a trialkylsilyl group. * is a bonding site to a silicon atom on the organopolysiloxane.
  • R 2 may be a tert-butyl group.
  • the hydrophilic group protected with the acid-decomposable functional group may be a group represented by the following formula (2-A).
  • R3 is a divalent hydrocarbon group having 2 to 6 carbon atoms.
  • R4 is a monovalent hydrocarbon group having 1 to 4 carbon atoms or a trialkylsilyl group. * is a bonding site to a silicon atom on the organopolysiloxane.
  • R 4 may be a tert-butyl group.
  • the hydrophilic group protected with the acid-decomposable functional group may be a phenol ether group represented by the following formula (2-B).
  • R5 is a monovalent branched saturated hydrocarbon group or trialkylsilyl group having 3 to 4 carbon atoms
  • * is a bonding site to a silicon atom on the organopolysiloxane.
  • R 5 may be a tert-butyl group.
  • the weight average molecular weight of the above-mentioned component (A) may be 1,500 or less. Furthermore, component (A) may have a cage molecular structure. The polydispersity of component (A) may be 1.20 or less.
  • the above-mentioned component (A) may contain an unsubstituted or fluorine-substituted monovalent hydrocarbon group as the substituent R.
  • the substituent R may be a monovalent hydrocarbon group having 1 to 3 carbon atoms.
  • the substituent R may also be a phenyl group.
  • e may satisfy 0 ⁇ e ⁇ 0.05.
  • the average number of silicon atoms per molecule of the above-mentioned component (A) may be 12 or less.
  • the branched organopolysiloxane composition of the present invention may be a composition in which, when the composition is applied onto a glass plate so as to have a thickness of 0.5 ⁇ m after application, a coating film containing no organic solvent is prepared by heat treatment at 100° C. for 1 minute, the coating film is irradiated with high-energy rays including light with a wavelength of 254 nm so as to be 40 mJ/ cm2 in terms of the amount of light at a wavelength of 254 nm, and then heat-treated (post-exposure bake, PEB) at 120° C.
  • PEB post-exposure bake
  • the coating film made of the branched organopolysiloxane has a mass reduction rate of 90 mass % or more.
  • the present invention provides an insulating coating agent containing the branched organopolysiloxane composition described above.
  • the present invention also provides a resist material containing the branched organopolysiloxane composition described above.
  • the present invention provides a method for using the branched organopolysiloxane composition described above as an insulating coating layer.
  • the present invention further provides a display device, such as a liquid crystal display, an organic electroluminescence display, or an organic electroluminescence flexible display, that includes a layer made of the branched organopolysiloxane composition described above.
  • a display device such as a liquid crystal display, an organic electroluminescence display, or an organic electroluminescence flexible display, that includes a layer made of the branched organopolysiloxane composition described above.
  • a branched organopolysiloxane that exhibits good alkali solubility upon irradiation with high-energy rays and can be used as a resist material, a composition containing the same, and uses thereof. More specifically, irradiation with high-energy rays induces a deprotection reaction of the hydrophilic groups protected by acid-decomposable functional groups in the branched organopolysiloxane of the present invention, and therefore the solubility of a coating film made of a composition containing the branched organopolysiloxane in an alkaline aqueous solution increases when irradiated with high-energy rays.
  • the branched organopolysiloxane of the present invention has a low weight average molecular weight and a low polydispersity, it is possible to achieve highly accurate patterning in a simple process in the lithography process carried out to form a pattern of a desired shape. Furthermore, the branched organopolysiloxane composition of the present invention has good coatability on various substrates.
  • the coating film formed from the composition of the present invention has the advantage that it is optically transparent and can be designed in a wide range of hardness, etc. Therefore, the composition of the present invention is useful as a resist material that utilizes a wide range of light sources, particularly short wavelength light sources.
  • the composition of the present invention is also useful as a material for an insulating layer for electronic devices, particularly thin display devices such as OLEDs, particularly as a patterning material and a coating material.
  • the branched organopolysiloxane of the present invention is an organopolysiloxane that contains a hydrophilic group protected with an acid-decomposable functional group and has a specific structure.
  • the branched organopolysiloxane composition of the present invention contains, as essential components, component (A), a branched organopolysiloxane having the above-mentioned specific structure, (B) a photoacid generator, and (C) an organic solvent.
  • Component (A) in the composition of the present invention has at least one hydrophilic group protected by an acid-decomposable functional group, and is converted by irradiation with high-energy rays into an organopolysiloxane having good solubility in an aqueous alkaline solution (sometimes referred to as "alkali-soluble" in this specification).
  • alkaline aqueous solution used as the developer basic aqueous solutions such as sodium hydroxide (NaOH), potassium hydroxide (KOH), and quaternary ammonium salts are well known.
  • NaOH sodium hydroxide
  • KOH potassium hydroxide
  • TMAH tetramethylammonium hydroxide
  • alkali-soluble means soluble in an aqueous TMAH solution.
  • branched organopolysiloxane that has been irradiated with high-energy rays is "alkali-soluble" can be confirmed by the following method. That is, a test mixture containing the branched organopolysiloxane of the present invention and an organic solvent is applied to a glass plate to a thickness of 0.5 ⁇ m, a coating film containing no organic solvent is prepared by heat treatment at 100° C.
  • the coating film is irradiated with high-energy rays containing light with a wavelength of 254 nm so that the amount of light converted to 40 mJ/cm 2 at a wavelength of 254 nm is then subjected to heat treatment (post-exposure bake, PEB) at 120° C. for 2 minutes, and the resulting light-irradiated coating film is immersed in a 2.38 mass% aqueous solution of TMAH for 1 minute and then washed with water.
  • PEB post-exposure bake
  • the mass reduction rate of the coating film made of the organopolysiloxane is 90 mass% or more, it can be judged that the branched organopolysiloxane has exhibited sufficiently excellent alkali solubility due to irradiation with high-energy rays.
  • the mass reduction rate of the coating film made of the branched organopolysiloxane is 95 mass% or more or 98 mass% or more when evaluated by the above method, it can be said that the alkali solubility is very excellent.
  • the method for applying a composition containing a branched organopolysiloxane onto a glass plate is generally spin coating, after which it is necessary to remove the organic solvent by drying, etc.
  • the water washing step generally involves immersion in a water bath at about room temperature (25° C.) or washing with running water at a flow rate similar to that of household tap water for about 10 to 15 seconds, so as not to adversely affect the formed pattern or the substrate.
  • the branched organopolysiloxane of the present invention has a low weight average molecular weight and a small polydispersity, and therefore tends to have improved alkali solubility after irradiation with high-energy rays, as compared with medium to high molecular weight organopolysiloxanes similarly composed of silsesquioxane units.
  • the alkali solubility of a coating film made of a branched organopolysiloxane is evaluated by the above-mentioned method for evaluating alkali solubility, it is particularly preferable that the mass loss rate of the coating film obtained after irradiation with high-energy rays is 98% by mass or more. If the mass loss rate is 98% by mass or more, it can be said that a branched organopolysiloxane having particularly excellent alkali solubility and a coating film made thereof have been obtained.
  • Branched Organopolysiloxane Branched Organopolysiloxane>
  • the branched organopolysiloxane which is component (A) of the present invention is represented by the following average unit formula (1).
  • R is independently a group selected from the group consisting of unsubstituted or fluorine-substituted monovalent hydrocarbon groups, alkoxy groups, hydroxyl groups, and hydrophilic groups protected by acid-decomposable functional groups.
  • Z is a hydrogen atom or an alkyl group.
  • a, b, c, and d represent the ratio (based on the amount of substance) of the number of each siloxane unit to the number of all siloxane units when the number of all siloxane units contained in the branched organopolysiloxane is 1.
  • e represents the ratio (based on the amount of substance) of the number of (O 1/2 Z) to the number of all siloxane units when the number of all siloxane units is 1.
  • the branched organopolysiloxane represented by the average unit formula (1) has, in the molecule, at least one hydrophilic group protected by an acid-decomposable functional group.
  • the four siloxane units described in the following average unit formula (1) may each be of one type or two or more types, i.e., component (A) may contain, for example, one type of siloxane unit corresponding to (RSiO3 /2 ), or may contain two or more types.
  • the molecular weight of component (A) of the present invention must be 2,000 or less as the weight average molecular weight converted into standard polystyrene, measured by gel permeation chromatography (hereinafter sometimes referred to as "GPC"). This characteristic makes it easy to design a material that has excellent alkali solubility after high-energy radiation irradiation and enables high-precision patterning.
  • the preferred weight average molecular weight (Mw) value of component (A) is 1,800 or less, 1,500 or less, and more preferably in the range of 1,000 to 1,800, 1,000 to 1,600, 1,000 to 1,500, or 1,000 to 1,200.
  • the polydispersity (hereinafter sometimes referred to as "PDI") of component (A) of the present invention is a value defined as the value of "Mw/Mn” using the number average molecular weight (Mn) and weight average molecular weight (Mw) calculated by the GPC method in terms of standard polystyrene.
  • Mw/Mn number average molecular weight
  • Mw weight average molecular weight
  • the polydispersity value of component (A) must be 1.30 or less. This characteristic enables high-precision patterning using component (A) of the present invention and the composition of the present invention containing it, and in particular reduces the nonuniformity of the line width.
  • the polydispersity value of component (A) of the present invention is preferably 1.20 or less, and is particularly preferably in the range of 1.00 to 1.30, and more preferably in the range of 1.00 to 1.15.
  • component (A) of the present invention has a weight-average molecular weight of 2,000 or less and a polydispersity of 1.30 or less. If the weight-average molecular weight or polydispersity exceeds the respective upper limits, the composition of the present invention may lose either or both of its alkali solubility after high-energy radiation irradiation and its high-precision patterning properties (including coatability). Such a composition cannot be suitably used as a patterning material.
  • the average number of silicon atoms per molecule is preferably 12 or less. That is, the branched organopolysiloxane of the present invention may be a branched organopolysiloxane having a single number of silicon atoms, or may be a mixture of two or more branched organopolysiloxanes having different numbers of silicon atoms, but it is preferable that the average number of silicon atoms in all molecules of these branched organopolysiloxanes is 12 or less.
  • the average number of silicon atoms per molecule is preferably 10 or less, more preferably 8 or less. And the average number of silicon atoms per molecule is preferably in the range of 4 to 8, and particularly preferably 5 to 8. This characteristic also affects the possibility of high-precision patterning. In the branched organopolysiloxane of the present invention, it is preferable that the average number of silicon atoms is small, and it is also preferable that the deviation is small.
  • the branched organopolysiloxane, component (A) of the present invention preferably has a cage molecular structure.
  • a cage molecular structure refers to a so-called polyhedral cluster structure or a structure close to it.
  • a branched organopolysiloxane having a cage molecular structure is also called a polyhedral oligomeric silsesquioxane, and the compound has a symmetrical molecular structure or a molecular structure close to it.
  • Well-known polyhedral oligomeric silsesquioxanes include a regular hexahedral structure with 8 silicon atoms, a pentagonal prism structure with 10 silicon atoms, and a heptahedral structure with 12 silicon atoms.
  • component (A) of the present invention is a branched organopolysiloxane having a cage molecular structure in which the (RSiO 3/2 ) c unit of formula (1) above, i.e., the silsesquioxane unit, is the main constituent unit.
  • c satisfies the condition 0.8 ⁇ c, and naturally also satisfies the condition 0.8 ⁇ c ⁇ 1.0.
  • the a, b and d are 0.
  • e may be and is preferred to be 0.
  • the branched organopolysiloxane of the present invention represented by the above formula (1) is a branched organopolysiloxane having a cage structure consisting only of (RSiO3 /2 ) c units, i.e., silsesquioxane units.
  • the number of silicon atoms derived from the (RSiO3 /2 ) c units corresponds to the number of silicon atoms in the molecule.
  • the (O 1/2 Z) e unit in the above formula ( 1 ) represents a Si-OH and/or Si -O -alkyl group that remains after a part of the condensation reaction is not completed when a branched organopolysiloxane having a cage molecular structure, which has (RSiO 3/2 ) c units as the main constituent units and may optionally contain (R 2 SiO 2/2 ) b units and (SiO 4/2 ) d units, is formed. That is, each Z is independently a hydrogen atom or an alkyl group. Specific examples of the alkyl group constituting Z include alkyl groups having 1 to 20 carbon atoms.
  • the alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably a methyl group, an ethyl group, or an isopropyl group.
  • e is preferably 15% or less (e ⁇ 0.15) relative to a+b+c+d, more preferably 10% or less (e ⁇ 0.1), and even more preferably 5% or less (e ⁇ 0.05), and it is particularly preferable that the branched organopolysiloxane has a complete cage structure.
  • Specific examples of the complete cage structure and partial cleavage structure of branched organopolysiloxane are shown in, for example, paragraphs [0047] to [0049] of JP-T-2010-515778.
  • the branched polyorganosiloxane of the present invention represented by the above average unit formula (1) is characterized in that it has, in its molecule, at least one hydrophilic group protected by an acid-decomposable functional group.
  • the hydrophilicity of the functional group is suppressed by the protecting group before irradiation with high-energy rays.
  • irradiation with high-energy rays causes a deprotection reaction of the hydrophilic group, and therefore, after irradiation with high-energy rays, the hydrophilicity derived from the functional group is expressed, and the solubility of the coating film made of the branched polyorganosiloxane in an alkaline aqueous solution is increased.
  • all of the substituents R in the branched polyorganosiloxane represented by the above average unit formula (1) may be hydrophilic groups protected with acid-decomposable functional groups.
  • the substituent R other than the hydrophilic group protected by the acid-decomposable functional group in the above average unit formula (1) is a group selected from a monovalent hydrocarbon group, an alkoxy group, and a hydroxyl group, which are unsubstituted or substituted with fluorine.
  • the branched polyorganosiloxane has these groups (i.e., at least one group selected from the group consisting of a monovalent hydrocarbon group, an alkoxy group, and a hydroxyl group, which are unsubstituted or substituted with fluorine).
  • the unsubstituted or fluorine-substituted monovalent hydrocarbon group which may constitute the substituent R include unsubstituted alkyl, cycloalkyl, alkenyl, arylalkyl, and aryl groups having 1 to 20 carbon atoms, as well as monovalent organic groups in which at least a portion of the hydrogen atoms of these groups have been substituted with fluorine.
  • the unsubstituted monovalent hydrocarbon group that can constitute the substituent R is preferably a monovalent hydrocarbon group having 1 to 3 carbon atoms.
  • Examples of the unsubstituted alkyl group having 1 to 20 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, sec-butyl, pentyl, hexyl, octyl, etc. Among these, the methyl group and the hexyl group are particularly preferred.
  • Examples of unsubstituted cycloalkyl groups having 1 to 20 carbon atoms include cyclopentyl, cyclohexyl, and other groups.
  • Examples of the unsubstituted alkenyl group having 1 to 20 carbon atoms include vinyl, allyl, 1-butenyl, 1-hexenyl, etc.
  • the vinyl group and the hexenyl group are particularly preferred.
  • unsubstituted arylalkyl groups having 1 to 20 carbon atoms include benzyl, phenylethyl, and the like groups.
  • unsubstituted aryl group having 1 to 20 carbon atoms include phenyl and naphthyl groups.
  • the phenyl group is particularly preferred.
  • the monovalent hydrocarbon group substituted with fluorine include 3,3,3-trifluoropropyl and 3,3,4,4,5,5,6,6,6-nonafluorohexyl groups, among which the 3,3,3-trifluoropropyl group is preferred.
  • component (A) of the present invention has a hydrophilic group protected by an acid-decomposable functional group in the molecule, and specifically, it is necessary that at least one of the substituents R in the average unit formula (1) is a hydrophilic group protected by an acid-decomposable functional group.
  • the hydrophilic group protected with an acid-decomposable functional group may be a group represented by the following formula (2).
  • *-R 1 -O-R 2 (2)
  • R2 is a monovalent hydrocarbon group having 1 to 4 carbon atoms or a trialkylsilyl group. * is a bonding site to a silicon atom on the organopolysiloxane.
  • the number of carbon atoms in the divalent hydrocarbon group which may have a carbonyl group and which constitutes the linking group R1 in formula (2) is not particularly limited, and can be, for example, from 2 to 7, or from 3 to 6.
  • the carbonyl group may be located at either end of the divalent hydrocarbon group, or may be located between two adjacent carbon atoms which constitute the divalent hydrocarbon group.
  • R2 in formula (2) is a monovalent hydrocarbon group or trialkylsilyl group having 1 to 4 carbon atoms, and may be a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, or a monovalent branched saturated hydrocarbon group having 3 to 4 carbon atoms.
  • suitable groups for R2 include a tert-butyl group (tertiary butyl group) and a trimethylsilyl group. Among these, a tert-butyl group is more preferable as R2 .
  • the hydrophilic group protected with an acid-decomposable functional group is preferably a carboxylate-containing group represented by the following formula (2-A).
  • R3 is a divalent hydrocarbon group having 2 to 6 carbon atoms.
  • R4 is a monovalent saturated hydrocarbon group or trialkylsilyl group having 1 to 4 carbon atoms.
  • * is a bonding site to a silicon atom on the organopolysiloxane.
  • the divalent hydrocarbon group having 2 to 6 carbon atoms constituting the linking group R3 in formula (2-A) may be linear or branched.
  • R3 include an ethylene group, a propylene group, a 2-methylethylene group, a butylene group, a pentylene group, and a hexylene group, with a propylene group being preferred.
  • R4 which is an ester moiety in formula (2-A), is a monovalent hydrocarbon group or trialkylsilyl group having 1 to 4 carbon atoms, and may be a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, or a monovalent branched saturated hydrocarbon group having 3 to 4 carbon atoms.
  • suitable groups for R4 include a tert-butyl group (tertiary butyl group) and a trimethylsilyl group. Among these, a tert-butyl group is more preferable as R4 .
  • the hydrophilic group protected by the acid-decomposable functional group is preferably a phenol ether group represented by the following formula (2-B).
  • component (A) having a phenol ether group represented by the following formula (2-B) the heat resistance of the resulting coating film can be improved.
  • R5 is a monovalent branched saturated hydrocarbon group or trialkylsilyl group having 3 to 4 carbon atoms
  • * is a bonding site to a silicon atom on the organopolysiloxane.
  • R5 in formula (2-B) is a monovalent branched saturated hydrocarbon group or trialkylsilyl group having 3 to 4 carbon atoms, and specific examples of suitable groups include a tert-butyl group (tertiary butyl group) and a trimethylsilyl group. Among these, a tert-butyl group is more preferable as R5 .
  • the number of siloxane units having a hydrophilic group protected by an acid-decomposable functional group in component (A) is preferably more than 20 mol%, more preferably more than 20 mol% but less than 80 mol%, and even more preferably more than 20 mol% but less than 60 mol%, relative to the total number of siloxane units (100 mol%).
  • the number of siloxane units having a hydrophilic group protected by an acid-decomposable functional group in component (A) may be 21 mol% or more and 39 mol% or less, or 22 mol% or more and 37 mol% or less, relative to the total number of siloxane units (100 mol%).
  • component (A) may be used alone or in any combination of two or more types in any ratio. That is, component (A) in the present invention may be a branched organopolysiloxane having a single number of hydrophilic groups protected by an acid-decomposable functional group, or may be a mixture of any combination of two or more branched organopolysiloxanes having different numbers of hydrophilic groups protected by acid-decomposable functional groups.
  • the average number of hydrophilic groups protected by acid-decomposable functional groups contained in one molecule of component (A) of the present invention is preferably from 2 to 6, and more preferably from 3 to 6. If the average number of protected hydrophilic groups per molecule is within the above-mentioned range, the surface tack after coating and solvent removal is controlled, and furthermore, component (A) after high-energy radiation irradiation can exhibit even better alkali solubility.
  • any R in the average unit formula (1) can be a "hydrophilic group protected by an acid-decomposable functional group"
  • formula (1) satisfies the above formula: 0.8 ⁇ c, and that the average number of protected hydrophilic groups per molecule is preferably 2 or more, it is preferable that all or a part of the R in the monoorganosiloxy unit (RSiO3 /2 ) c is a hydrophilic group protected by an acid-decomposable functional group.
  • a method for producing component (A) of the present invention there is no particular limitation on the method for producing component (A) of the present invention.
  • a method for producing component (A) for example, the following production method 1) or 2) can be used.
  • 1) Using one or more alkoxysilanes, a reactive (e.g., silicon-bonded hydrogen-functional) branched organopolysiloxane having a predetermined molecular weight and a small polydispersity is produced by a controlled hydrolysis/condensation reaction, and then a compound containing a hydrophilic group protected by an acid-decomposable functional group is introduced into the obtained branched organopolysiloxane by a chemical reaction (e.g., a hydrosilylation reaction); 2)
  • a branched organopolysiloxane having a predetermined molecular weight and a small polydispersity is produced by a controlled hydrolysis/condensation reaction between a pre-prepared alkoxysilane containing
  • the manufacturing method 2) can be preferably applied.
  • the purity can be increased by purifying the intermediate alkoxysilanes containing hydrophilic groups protected by acid-decomposable functional groups.
  • This operation can also minimize the risk of heavy metals such as platinum atoms being contained in the final product, the branched organopolysiloxane. This characteristic is important when applied to electronic materials, particularly electronic materials in the semiconductor field, and offers a great advantage.
  • a hydrosilylation reaction can be carried out between a compound containing both a reactive carbon-carbon double bond-containing organic group (e.g., a vinyl group) and a hydrophilic group protected with an acid-decomposable functional group and a trialkoxysilane, to produce a trialkoxysilane having a hydrophilic group protected with an acid-decomposable functional group.
  • the product can then be purified by a method such as reduced pressure distillation to obtain a functional trialkoxysilane that is free of heavy metal impurities.
  • the mixture of the trialkoxysilane (preferably trimethoxysilane) having a hydrophilic group protected by an acid-decomposable functional group obtained above and other trialkoxysilanes (preferably trimethoxysilane) that are optionally used is subjected to a controlled hydrolysis/condensation reaction in the presence of a basic catalyst to produce a reactive branched organopolysiloxane with a small polydispersity.
  • the molecular weight of the product can be controlled by the type and amount of the solvent used during the reaction and the amount of water used. It is particularly preferable that the reactive branched organopolysiloxane at this stage has the cage molecular structure described above.
  • Component (B) is a component that catalyzes the decomposition reaction of component (A) by high-energy radiation, and generally, a group of compounds known as photoacid generators for cationic polymerization can be used.
  • Known photoacid generators include compounds that can generate a Bronsted acid or Lewis acid by irradiation with high-energy radiation.
  • the photoacid generator used in the branched organopolysiloxane composition of the present invention can be selected from those known in the art and is not limited to any particular one. Strong acid generating compounds such as diazonium salts, sulfonium salts, iodonium salts, and phosphonium salts are known as photoacid generators, and these can be used. One type of photoacid generator may be used alone, or two or more types may be used in combination in any ratio.
  • photoacid generators include bis(4-tert-butylphenyl)iodonium hexafluorophosphate, cyclopropyldiphenylsulfonium tetrafluoroborate, dimethylphenacylsulfonium tetrafluoroborate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroarsenate, diphenyliodonium tetrafluoromethanesulfonate, 2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, and 4-isopropyl-4'-methyldiphenyliodonium.
  • Tetrakis(pentafluorophenyl)borate 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 4-nitrobenzenediazonium tetrafluoroborate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium bromide, tri-p-tolylsulfonium hexafluorophosphate, tri-p-tolylsulfonium trifluoromethanesulfonate, triarylsulfonium tetrakis(pentafluorophenyl)borate, diphenyliodonium tri
  • Omnicat registered trademark 250
  • Omnicat 270 both manufactured by IGM Resins BV
  • CPI-310B both manufactured by San-Apro Co., Ltd.
  • IK-1 both manufactured by San-Apro Co., Ltd.
  • DTS-200 Midori Chemical Co., Ltd.
  • TS-01 both manufactured by Sanwa Chemical Co., Ltd.
  • Irgacure registered trademark 290
  • the amount of photoacid generator added to the branched organopolysiloxane composition of the present invention is not particularly limited as long as the desired photodecomposition reaction occurs.
  • the content of component (B) in the branched organopolysiloxane composition is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, even more preferably 0.5 to 10 parts by mass, and particularly preferably 1 to 10 parts by mass, relative to 100 parts by mass of component (A) of the present invention.
  • the branched organopolysiloxane composition of the present invention contains an organic solvent as component (C) for the purpose of improving the coatability of the branched organopolysiloxane, adjusting the thickness of the coating film, improving the dispersibility of the photoacid generator, etc.
  • an organic solvent any organic solvent that has been conventionally blended in various insulating coating materials and resist materials can be used without any particular limitation.
  • the organic solvent may be used alone or in combination of two or more kinds in any ratio, taking into consideration the miscibility with the above-mentioned components (A) and (B).
  • organic solvent examples include: (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, and dipropylene glycol mono-n-butyl ether; (poly)alkylene glycol monoalkyl ether acetates such as
  • the content of the organic solvent in the branched organopolysiloxane composition of the present invention is not particularly limited and can be appropriately set depending on the miscibility with the branched organopolysiloxane (A), the thickness of the coating film formed from the composition, etc.
  • the content of component (B) in the branched organopolysiloxane composition can be, for example, 10 parts by mass or more and 5,000 parts by mass or less per 100 parts by mass of the branched organopolysiloxane of component (A) of the present invention.
  • the solute concentration of the branched organopolysiloxane, component (A), is preferably 2% by mass or more and 90% by mass or less, and more preferably 2% by mass or more and 50% by mass or less.
  • the coating film obtained from the branched organopolysiloxane composition of the present invention has the desired physical properties depending on the molecular structure of component (A), the chemical structure of the hydrophilic group protected by an acid-decomposable functional group, the chemical structure of the other substituents, and the number of hydrophilic groups protected by an acid-decomposable functional group per molecule.
  • the viscosity of the composition can be designed to a desired value depending on the amount of component (C) added.
  • the coating film obtained by irradiating the branched organopolysiloxane composition of the present invention with high-energy rays can be designed to have a desired viscosity depending on the molecular structure and amount of component (B) in addition to the structure and amount of the above components, and further has the desired physical properties.
  • the shape of the coating film obtained from the composition of the present invention is not particularly limited, and may be a thin-film coating layer or a sheet-shaped molded product, and may be used as a sealant or intermediate layer for laminates or display devices.
  • the coating film obtained from the composition of the present invention is preferably in the form of a thin-film coating layer, and is particularly preferably a thin-film insulating coating layer or resist layer.
  • the branched organopolysiloxane composition of the present invention is suitable for use as a coating agent, particularly as an insulating coating agent for electronic devices and electrical devices. It is also suitable for use as a resist material that uses short-wavelength light such as an excimer laser as a light source.
  • additives may be added to the composition of the present invention as desired.
  • additives include, but are not limited to, the following.
  • the other additives may be used alone or in combination of two or more in any ratio.
  • An adhesion promoter can be added to the branched organopolysiloxane composition of the present invention in order to improve adhesion or adhesion to a substrate in contact with the composition.
  • an adhesion promoter to the composition of the present invention.
  • any known adhesion promoter can be used as long as it does not inhibit the decomposition reaction of the composition of the present invention in the presence of an acid.
  • adhesion promoters examples include: Organosilanes having trialkoxysiloxy groups (e.g., trimethoxysiloxy groups, triethoxysiloxy groups) and/or trialkoxysilylalkyl groups (e.g., trimethoxysilylethyl groups, triethoxysilylethyl groups), and hydrosilyl groups and/or alkenyl groups (e.g., vinyl groups, allyl groups); an organosiloxane oligomer having a linear, branched or cyclic structure and containing about 4 to 20 silicon atoms, which has a trialkoxysiloxy group and/or a trialkoxysilylalkyl group, and a hydrosilyl group and/or an alkenyl group; Organosilanes having a trialkoxysiloxy group and/or a trialkoxysilylalkyl group, and a methacryloxyalkyl group (for example
  • adhesion promoters include, but are not limited to, vinyltrimethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, hydrogentriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 1,6-bis(trimethoxysilyl)hexane, 1,6-bis(triethoxy ...
  • the amount of adhesion promoter added to the composition of the present invention is not particularly limited, but from the viewpoint of not promoting the decomposition reaction of the composition or discoloration of the branched organopolysiloxane, it is preferably in the range of 0.01 to 5 parts by mass, or 0.01 to 2 parts by mass, per 100 parts by mass of component (A).
  • additives In addition to the adhesion promoter described above, or instead of the adhesion promoter, other additives may be added to the composition of the present invention as desired. Examples of additives that can be used include leveling agents, silane coupling agents not included in the adhesion promoters described above, high energy ray absorbers, antioxidants, polymerization inhibitors, fillers (functional fillers such as reinforcing fillers, insulating fillers, and thermally conductive fillers), and the like. If necessary, appropriate additives can be added to the composition of the present invention. In addition, if necessary, a thixotropic agent may be added to the composition of the present invention, especially when used as a sealing material.
  • the method for producing a coating film using the branched polyorganosiloxane composition of the present invention is not particularly limited.
  • a known lithography process can be applied to the production of the coating film, and a patterned coating film can also be produced, which is preferable.
  • a typical method for producing a patterned coating film is as follows: 1) forming a coating film of the branched organopolysiloxane composition on a substrate; 2) A step of heating the obtained coating film for a short period of time at a temperature of about 120° C. or less to remove the solvent (organic solvent); 3) site-selectively exposing the coating to light; and 4) developing the exposed coating to obtain a patterned coating; If necessary, a short heating step can be inserted between 3) and 4).
  • the substrate is not particularly limited, and various substrates such as a glass substrate, a silicon substrate, and a glass substrate coated with a transparent conductive film can be used.
  • a coating device such as a spin coater, roll coater, bar coater, or slit coater can be used.
  • the applied composition is usually heated and dried to remove the solvent.
  • Typical methods include a method of drying on a hot plate or in an oven at a temperature of 80° C. to 120° C., preferably 90° C. to 100° C., for 1 to 2 minutes, a method of leaving the composition at room temperature for several hours, and a method of heating the composition in a hot air heater or infrared heater for several tens of minutes to several hours.
  • the position-selective exposure of the coating film is usually carried out through a photomask or the like using a high-energy ray light source such as a high-pressure mercury lamp, a metal halide lamp, or an LED lamp, a laser light source such as an excimer laser, or a known active energy ray light source including UEV.
  • a high-energy ray light source such as a high-pressure mercury lamp, a metal halide lamp, or an LED lamp, a laser light source such as an excimer laser, or a known active energy ray light source including UEV.
  • a negative or positive photomask can be used.
  • the amount of energy radiation to be irradiated depends on the structure of the curable composition, but is typically about 3 to 1,000 mJ/ cm2 .
  • the composition coating film after exposure can be subjected to a heat treatment (post-exposure bake) to increase the decomposition reaction yield. The conditions for this are usually 100°C or higher and 150°C or lower for 1 to 2
  • alkaline aqueous solutions suitable as the developer include aqueous solutions of basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts, and an aqueous solution of tetramethylammonium hydroxide (TMAH) is particularly preferred.
  • TMAH tetramethylammonium hydroxide
  • the branched organopolysiloxane of the present invention and compositions containing it as a main component have good coatability, while also exhibiting remarkably excellent alkali solubility after exposure to high-energy rays.
  • This has the advantage that, particularly when subjected to a development process using an aqueous alkaline solution, patterns can be formed easily and with high precision, and the resulting coating film has excellent mechanical strength and transparency.
  • a coating film of branched organopolysiloxane can be formed that is patterned into the desired shape.
  • the branched organopolysiloxane composition of the present invention is particularly useful as a material for forming an insulating layer and a resist material for various articles, particularly electronic devices and electric devices.
  • the composition of the present invention is also suitable as a material for forming an insulating layer of a display device such as a touch panel and a display, since the coating film obtained from the composition has good transparency.
  • the insulating layer may be formed into any desired pattern as described above, if necessary.
  • a display device such as a touch panel and a display, which includes an insulating layer obtained by irradiating the branched organopolysiloxane composition of the present invention with high energy rays or without irradiation, is also an embodiment of the present invention.
  • an insulating coating layer (insulating film) can be formed by coating an article with the composition of the present invention and then removing the organic solvent. Therefore, the composition of the present invention can be used as an insulating coating agent. In addition, a coating film formed by removing the organic solvent from the composition of the present invention can also be used as an insulating coating layer.
  • the insulating film formed from the composition of the present invention can be used for various applications other than the display device.
  • it can be used as a component of an electronic device, or as a material used in the process of manufacturing an electronic device.
  • Electronic devices include electronic devices such as semiconductor devices and magnetic recording heads.
  • the composition of the present invention can be used as an insulating film for semiconductor devices such as LSIs, system LSIs, DRAMs, SDRAMs, RDRAMs, D-RDRAMs, and multi-chip module multilayer wiring boards, an interlayer insulating film for semiconductors, an etching stopper film, a surface protective film, a buffer coat film, a passivation film in LSIs, a cover coat for flexible copper-clad boards, a solder resist film, and a surface protective film for optical devices.
  • semiconductor devices such as LSIs, system LSIs, DRAMs, SDRAMs, RDRAMs, D-RDRAMs, and multi-chip module multilayer wiring boards
  • an interlayer insulating film for semiconductors such as LSIs, system LSIs, DRAMs, SDRAMs, RDRAMs, D-RDRAMs, and multi-chip module multilayer wiring boards
  • an interlayer insulating film for semiconductors such as LSIs, system LSIs
  • a photoacid generator (B1) to the branched organopolysiloxane (solution state) shown below in the mass ratio shown in Tables 1 and 2 below was visually observed to evaluate the appearance including transparency.
  • A1 Branched organopolysiloxane obtained in Example 1
  • A2 Branched organopolysiloxane obtained in Example 2
  • A3 Branched organopolysiloxane obtained in Example 3
  • A4 Branched organopolysiloxane obtained in Synthesis
  • Example 2 A5: Branched organopolysiloxane obtained in Synthesis
  • Example 3 A6: Branched organopolysiloxane obtained in Example 7
  • A7 Branched organopolysiloxane obtained in Example 8
  • A8 Branched organopolysiloxane obtained in Synthesis
  • Example 4 B1 Sulfonium-based photoacid generator manufactured by BASF: triarylsulfonium tetrakis(pentafluorophenyl)borate (product name: Irgacure 290)
  • the branched organopolysiloxane composition was spin-coated on an optical glass substrate to a thickness of about 0.5 ⁇ m, and heated (pre-baked) at 100° C. for 1 minute using a hot plate to form a coating film (coating film X).
  • the total light transmittance of the resulting coating film at 25° C. was measured using a haze meter SH7000 manufactured by Nippon Denshoku Industries Co., Ltd.
  • the formed coating film was irradiated with light (high-energy ray irradiation) at a wavelength of 254 nm equivalent to 40 mJ/cm 2 using a high-pressure mercury lamp, and then subjected to PEB at 120° C. for 2 minutes.
  • the total light transmittance of the coating film (coating film Y) obtained by this operation at 25° C. was measured using the same method.
  • Coating film X and coating film Y each having a thickness of about 0.2 ⁇ m and formed in the same manner as above, were developed at 25° C. using a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 1 minute, and then immersed and washed in a water bath at room temperature (25° C.). The washing time was 15 seconds. After washing and drying to remove moisture, the glass substrate was visually observed, and the solubility (developability) in an alkaline aqueous solution was evaluated according to the following criteria. A: Completely dissolved: The coating film is completely removed. B: Almost dissolved: A small amount (5% or less of the plan view area) of remaining coating film (scum) is observed. C: Insoluble.
  • TMAH tetramethylammonium hydroxide
  • Synthesis Example 1 Synthesis of tert-butoxycarbonylpropyltrimethoxysilane (M1) 74.6 g of tert-butyl-3-butenate and a toluene solution of Karstedt catalyst in an amount equivalent to 100 ppm of platinum were added to a 300 mL three-neck flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, and the mixture was thoroughly stirred. A mixture of 65.5 g of trimethoxysilane and 1.0 g of acetic acid was slowly dripped into the solution under a nitrogen atmosphere, and then the mixture was stirred at room temperature for 90 minutes. The product was distilled under reduced pressure to obtain 116 g of the desired silane (M1) (83% isolated yield). The structure of the product was confirmed by 13 C NMR spectroscopy.
  • Example 1 Synthesis of tert-butoxycarbonylpropyl and phenyl functional branched organopolysiloxane (A1) 20.0 g of the silane (M1) obtained in Synthesis Example 1, 45.0 g of phenyltrimethoxysilane, and 310 g of tetrahydrofuran were added to a 500 mL three-neck flask equipped with a thermometer, a stirrer, and a nitrogen inlet tube, and stirred thoroughly. A mixed solution of 1.0 g of potassium hydroxide and 8.4 g of water was added to the resulting solution, and stirred at 60° C. for 6 hours.
  • the resulting reaction solution was cooled to room temperature, and 7.0 g of an alkali adsorbent Kyoward (registered trademark) 700PL was added, and stirred at room temperature for 30 minutes. A white solid was filtered out from the reaction solution after stirring, and most of the volatile matter was removed to obtain a concentrated solution of functional branched organopolysiloxane (solid content of 70% by mass or more). 100 mL of PGMEA was added to this solution, low boiling components were removed, and this process was repeated to obtain a 20 mass % PGMEA solution of the product.
  • Kyoward registered trademark
  • the average unit formula of the branched organopolysiloxane (A1) can be expressed as follows: (RSiO 3/2 ) 0.25 ((C 6 H 5 )SiO 3/2 ) 0.75 (O 1/2 Z) ⁇ 0.01
  • the Mn, Mw, and PDI of the branched organopolysiloxane (A1) calculated based on standard polystyrene by the GPC method, were 1,000, 1,100, and 1.10, respectively.
  • the average number of silicon atoms per molecule was 7.
  • Example 2 Synthesis of tert-butoxycarbonylpropyl and cyclohexyl functional branched organopolysiloxane (A2)
  • the amount of silane (M1) was changed to 21.6 g
  • cyclohexyltrimethoxysilane was used instead of 45.0 g of phenyltrimethoxysilane
  • the amount of tetrahydrofuran was changed to 300 g
  • the amount of potassium hydroxide was changed to 2.2 g
  • the amount of water was changed to 9.1 g
  • the amount of Kyoward 700PL was changed to 14.0 g, but the reaction was carried out in the same manner as in Example 1 to obtain a 20 mass % PGMEA solution of the product.
  • the average unit formula of the branched organopolysiloxane (A2) can be expressed as follows: (RSiO 3/2 ) 0.25 ((C 6 H 11 )SiO 3/2 ) 0.75 (O 1/2 Z) 0.09
  • Example 3 Synthesis of tert-butoxycarbonylpropyl and methyl functional branched organopolysiloxane (A3)
  • the amount of silane (M1) was changed to 15.0g, methyltrimethoxysilane was used instead of 45.0g of phenyltrimethoxysilane, the amount of tetrahydrofuran was changed to 180g, the amount of potassium hydroxide was changed to 0.75g, the amount of water was changed to 6.3g, and the amount of Kyoward 700PL was changed to 5.0g, and the reaction was carried out in the same manner as in Example 1 to obtain a 25% by mass PGMEA solution of the product.
  • silane (M1) was changed to 15.0g
  • methyltrimethoxysilane was used instead of 45.0g of phenyltrimethoxysilane
  • the amount of tetrahydrofuran was changed to 180g
  • the amount of potassium hydroxide was changed to 0.75g
  • the amount of water was changed
  • the average unit formula of the branched organopolysiloxane (A6) can be expressed as follows: (( CH3 )SiO3 /2 ) 0.50 (RSiO3 /2 ) 0.50 (O1 / 2Z) 0.01
  • R is a tert-butoxyphenyl group (-C 6 H 5 -O-C(CH 3 ) 3 ).
  • the average unit formula of the branched organopolysiloxane (A7) can be expressed as follows: ((C 3 H 7 )SiO 3/2 ) 0.25 (RSiO 3/2 ) 0.75 (O 1/2 Z) ⁇ 0.01
  • R is a tert-butoxyphenyl group (-C 6 H 5 -O-C(CH 3 ) 3 ).
  • the average number of silicon atoms per molecule was 8.
  • Examples 4 to 6 and Comparative Examples 1 and 2 Evaluation of Branched Organopolysiloxanes
  • the evaluation results of the branched organopolysiloxanes of the present invention are summarized in Table 1.
  • the unit of the numerical values of each component in Table 1 is "parts by mass” unless otherwise specified (particularly, the units other than C1, which is the organic solvent, are solid content equivalents).
  • the coating films (Examples 4 to 6) formed from the branched organopolysiloxanes of the present invention (Examples 1 to 3: A1 to A3) exhibited high transparency, and the coating films after high-energy radiation and PEB showed excellent alkali solubility.
  • the coating film (Comparative Example 1) formed from a branched organopolysiloxane that does not have a hydrophilic group protected by an acid-decomposable functional group exhibited high transparency, but did not exhibit alkali solubility, regardless of whether or not it was exposed to high-energy radiation or the PEB process.
  • the coating film (Comparative Example 2) formed from a branched organopolysiloxane that has a hydrophilic group protected by an acid-decomposable functional group but has a large molecular weight and PDI was insoluble in an alkaline aqueous solution even after high-energy radiation and PEB.
  • Examples 9 to 10 and Comparative Example 3 Evaluation of Branched Organopolysiloxanes
  • the evaluation results of the branched organopolysiloxanes of the present invention are summarized in Table 2.
  • the unit of the numerical values of each component in Table 2 is "parts by mass” unless otherwise specified (particularly, the units other than C1, which is the organic solvent, are solid content equivalents).
  • the coating film (Comparative Example 3) formed from the branched organopolysiloxane that does not have a hydrophilic group protected by an acid-decomposable functional group exhibited high transparency, but did not exhibit alkali solubility, regardless of whether or not it was exposed to high-energy radiation or subjected to the PEB process.
  • the branched organopolysiloxane having hydrophilic groups protected by acid-decomposable functional groups and the composition containing the same as the main component according to the present invention have good coatability on various substrates.
  • the composition is improved in hydrophilicity of the coating film after high-energy radiation exposure by deprotection of the hydrophilic groups and subsequent heat treatment (PEB), and the solubility in an alkaline aqueous solution is increased.
  • PEB hydrophilicity of the coating film after high-energy radiation exposure by deprotection of the hydrophilic groups and subsequent heat treatment
  • the solubility in an alkaline aqueous solution is increased.
  • the molecular weight and polydispersity of the branched polysiloxane are low, high-precision patterning is possible in a simple process in the lithography process performed to form a pattern of a desired shape.
  • the coating film formed from the branched organopolysiloxane composition of the present invention has the advantage that it is optically transparent and can be designed in a wide range of hardness, etc.
  • the composition according to the present invention is useful as a resist material that utilizes a wide range of light sources, particularly short-wavelength light sources. It is also useful as a material for insulating layers for electronic devices, particularly thin display devices such as OLEDs, particularly patterning materials and coating materials.

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Abstract

Le but de la présente invention est de fournir un nouveau matériau qui présente une bonne solubilité alcaline par irradiation avec des rayons à haute énergie et qui peut être utilisé en tant que matériau de réserve. Le nouveau matériau selon la présente invention est un organopolysiloxane ramifié représenté par la formule unitaire moyenne (1), et ayant un poids moléculaire moyen en poids de 2000 ou moins, une polydispersité de 1,30 ou moins, et un groupe hydrophile protégé par un groupe fonctionnel décomposable par un acide dans une molécule de celui-ci. Formule (1) : (R3SiO1/2)a(R2SiO2/2)b(RSiO3/2)c(SiO4/2)d(O1/2Z)eDans la formule, R est un groupe choisi parmi un groupe hydrocarboné monovalent ou similaire et un groupe hydrophile protégé par un groupe fonctionnel pouvant être décomposé par un acide, et a, b, c, d et e sont des nombres satisfaisant les conditions suivantes : 0 ≤ a ; 0 ≤ b ; 0,8 ≤ c ; 0 ≤ d ; 0 ≤ e ; et a + b + c + d = 1.
PCT/JP2024/028238 2023-10-04 2024-08-07 Organopolysiloxane ramifié, composition le contenant et utilisation associée Pending WO2025074731A1 (fr)

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TRAN HOANG V, HUNG RAYMOND J, LOY DOUGLAS A, WHEELER DAVID R, BYERS JEFFREY, CONLEY WILL, WILLSON C GRANT, : "SYNTHESIS OF SILOXANES AND SILSESQUIOXANES FOR 157 NM MICROLITHOGRAPHY", POLYMERIC MATERIALS: SCIENCE & ENGINEERING, 1 January 2001 (2001-01-01), pages 1 - 1, XP093300763 *

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