# US 11,111,337 B2 · Polyorganosilsesquioxane, hard coat film, adhesive sheet, and laminate > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,111,337 B2 - Document ID: US11111337B2 - Status: Granted - Kind: B2 - Application number: 16/000,313 - Filed: 2018-06-05 - Published: 2018-10-04 - Granted: 2021-09-07 - Earliest claimed: 2013-12-13 - Assignees: Daicel Corporation - Applicants: Daicel Corporation - Inventors: Akihiro Kuwana; Nobuhiko Harada; Maya Masui; Ichiro Takase; Shinji Maetani; Naoko Tsuji - Web page: https://patentgrep.com/patent/US11111337B2 ## CPC - C08G 77/14: containing silicon bound to oxygen-containing groups - B32B 7/12: using interposed adhesives or interposed materials with bonding properties - B32B 9/005: {comprising one layer of ceramic material, e.g. porcelain, ceramic tile (layered products with at least two ceramic layers composed mainly of ceramic B32B18/00)} - B32B 9/045: {of synthetic resin} - B32B 15/08: of synthetic resin - B32B 21/08: of synthetic resin - B32B 27/08: of synthetic resin - B32B 27/10: of paper or cardboard - B32B 27/28: comprising synthetic resins not wholly covered by any one of the sub-groups {B32B27/30 - B32B27/42} - B32B 27/281: {comprising polyimides} - B32B 27/283: {comprising polysiloxanes} - B32B 27/285: {comprising polyethers} - B32B 27/30: comprising vinyl {(co)polymers; comprising acrylic (co)polymers} - B32B 27/302: {comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers} - B32B 27/304: {comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF} - B32B 27/308: {comprising acrylic (co)polymers} - B32B 27/325: {comprising polycycloolefins} - B32B 27/34: comprising polyamides - B32B 27/36: comprising polyesters - B32B 27/365: {comprising polycarbonates} - B32B 27/38: comprising epoxy resins - B32B 27/42: comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines - B32B 29/00: Layered products comprising {a layer of} paper or cardboard - C08G 59/02: Polycondensates containing more than one epoxy group per molecule - C08G 59/24: carbocyclic - C08G 59/3281: {containing silicon} - C08G 59/4064: {sulfur containing compounds (C08G59/4021, C08G59/4028 take precedence)} - C08J 7/0427: {with only one layer of a composition containing a polymer binder (with more layers C08J7/042)} - C08J 7/043: Improving the adhesiveness of the coatings per se, e.g. forming primers (adhesives in the form of films or foils characterised by the primer layers between the polymer carriers and the adhesives C09J7/50) - C08J 7/048: Forming gas barrier coatings - C08K 5/5415: containing at least one Si—O bond - C08L 63/00: Compositions of epoxy resins; Compositions of derivatives of epoxy resins - C08L 83/06: containing silicon bound to oxygen-containing groups (C08L83/12 takes precedence) - C09D 163/00: Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins - C09D 183/06: containing silicon bound to oxygen-containing groups (C09D183/12 takes precedence) - C09J 7/20: characterised by their carriers - C09J 7/30: characterised by the adhesive composition - C09J 183/04: Polysiloxanes - C09J 183/06: containing silicon bound to oxygen-containing groups (C09J183/12 takes precedence) - B32B 2250/02: 2 layers - B32B 2250/03: 3 layers - B32B 2250/04: 4 layers - B32B 2250/05: 5 or more layers - B32B 2255/26: Polymeric coating - B32B 2307/306: Resistant to heat - B32B 2307/412: Transparent - B32B 2307/536: Hardness - B32B 2307/546: Flexural strength; Flexion stiffness - B32B 2307/732: Dimensional properties - B32B 2405/00: Adhesive articles, e.g. adhesive tapes - B32B 2457/208: Touch screens - C08J 2483/06: containing silicon bound to oxygen-containing groups (C08J2483/12 takes precedence) - C08K 5/549: containing silicon in a ring - C09J 2483/00: Presence of polysiloxane - Y10T 428/31504: Composite [nonstructural laminate] - Y10T 428/31663: As siloxane, silicone or silane - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM - C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29) - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) - C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06) - 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 (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) - C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H) - Y10T: TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION ## Abstract Provided is a polyorganosilsesquioxane capable of forming, when cured, a cured product that offers high surface hardness and good heat resistance, is highly flexible, and has excellent processability. The present invention relates to a polyorganosilsesquioxane including a constitutional unit represented by Formula (1). The polyorganosilsesquioxane includes a constitutional unit represented by Formula (I) and a constitutional unit represented by Formula (II) in a mole ratio of the constitutional unit represented by Formula (I) to the constitutional unit represented by Formula (II) of 5 or more. The polyorganosilsesquioxane has a total proportion of the constitutional unit represented by Formula (1) and a constitutional unit represented by Formula (4) of 55% to 100% by mole based on the total amount (100% by mole) of all siloxane constitutional units. The polyorganosilsesquioxane has a number-average molecular weight of 1,000 to 3,000 and a molecular-weight dispersity (weight-average molecular weight to number-average molecular weight ratio) of 1.0 to 3.0. [R1SiO3/2] (1) [Chem. 2] [RaSiO3/2] (I) [Chem. 3] [RbSiO(ORc)] (II) [Chem. 4] [R1SiO(ORc)] (4). ## Claims ### Claim 1 A hard coat layer comprising a cured product of a curable composition comprising a polyorganosilsesquioxane, the polyorganosilsesquioxane comprising: a constitutional unit represented by Formula (I); and a constitutional unit represented by Formula (II), in a mole ratio of the constitutional unit represented by Formula (I) to the constitutional unit represented by Formula (II) of from 5 to 18, a constitutional unit represented by Formula (2), and an optional constitutional unit represented by Formula (5), the polyorganosilsesquioxane having a total proportion of the constitutional unit represented by Formula (I) and a constitutional unit represented by Formula (II) of 95% to 99% by mole based on a total amount (100% by mole) of all siloxane constitutional units, the polyorganosilsesquioxane having a total proportion of the constitutional unit represented by Formula (2) and a constitutional unit represented by Formula (5) of 1% to 5% by mole based on a total amount (100% by mole) of all siloxane constitutional units, the polyorganosilsesquioxane having a number-average molecular weight of 1100 to 2600 and a molecular-weight dispersity (weight-average molecular weight to number-average molecular weight ratio) of 1.1 to 2.0, Formulae (I), (II), (2), and (5) expressed as follows: [RaSiO3/2] (I) wherein Ra is selected from: a group represented by Formula (1a); a group represented by Formula (1d), Formulae (1a) and (1d) expressed as follows: wherein R1a represents an ethylene group, wherein R1d represents an ethylene group, [RbSiO(ORc)] (II) wherein Rb is selected from: a group represented by Formula (1a); and a group represented by Formula (1d), Formulae (1a) and (1d) expressed as follows: wherein R1a represents an ethylene group, wherein R1d represents an ethylene group; and Rc is selected from a hydrogen atom and a C1-C4 alkyl group, [R2SiO3/2] (2) wherein R2 is an unsubstituted phenyl group, and [R2SiO(ORc)] (5) wherein R2 is as defined in Formula (2); and Rc is as defined in Formula (II). ### Claim 2 (depends on 1) The hard coat layer according to claim 1, the curable composition further comprising a curing catalyst. ### Claim 3 (depends on 2) The hard coat layer according to claim 2, wherein the curing catalyst comprises a cationic photoinitiator. ### Claim 4 (depends on 2) The hard coat layer according to claim 2, wherein the curing catalyst comprises a cationic thermal initiator. ### Claim 5 (depends on 1) The hard coat layer according to claim 1, the curable composition further comprising a vinyl ether compound. ### Claim 6 (depends on 1) The hard coat layer according to claim 1, the curable composition further comprising a vinyl ether compound containing a hydroxy group in molecule. ### Claim 7 (depends on 1) A hard coat film comprising: a substrate; and the hard coat layer according to claim 1 disposed on or over at least one side of the substrate. ### Claim 8 (depends on 7) The hard coat film according to claim 7, wherein the hard coat layer has a thickness of 1 to 200 μm. ### Claim 9 (depends on 7) The hard coat film according to claim 7, wherein the hard coat film is produced by a roll-to-roll process. ### Claim 10 (depends on 7) The hard coat film according to claim 7, further comprising a surface-protecting film on or over the hard coat layer. ### Claim 11 A method for producing a hard coat film, the method comprising the step of: (B) applying a curable composition to at least one side of a substrate, and curing the applied curable composition to form a hard coat layer on the substrate to thereby give a hard coat film, the curable composition comprising a polyorganosilsesquioxane, the polyorganosilsesquioxane comprising: a constitutional unit represented by Formula (I); and a constitutional unit represented by Formula (II), in a mole ratio of the constitutional unit represented by Formula (I) to the constitutional unit represented by Formula (II) of from 5 to 18, the polyorganosilsesquioxane comprising a constitutional unit represented by Formula (2), and an optional constitutional unit represented by Formula (5), the polyorganosilsesquioxane having a total proportion of the constitutional unit represented by Formula (I) and a constitutional unit represented by Formula (II) of 95% to 99% by mole based on a total amount (100% by mole) of all siloxane constitutional units, the polyorganosilsesquioxane having a total proportion of the constitutional unit represented by Formula (2) and a constitutional unit represented by Formula (5) of 1% to 5% by mole based on a total amount (100% by mole) of all siloxane constitutional units, the polyorganosilsesquioxane having a number-average molecular weight of 1100 to 2600 and a molecular-weight dispersity (weight-average molecular weight to number-average molecular weight ratio) of 1.1 to 2.0, Formulae (I), (II), (2), and (5) expressed as follows: [RaSiO3/2] (I) wherein Ra is selected from: a group represented by Formula (1a); a group represented by Formula (1d), Formulae (1a) and (1d) expressed as follows: wherein R1a represents an ethylene group, wherein R1d represents an ethylene group, [RbSiO(ORc)] (II) wherein Rb is selected from: a group represented by Formula (1a); and a group represented by Formula (1d), Formulae (1a) and (1d) expressed as follows: wherein R1a represents an ethylene group, wherein R1d represents an ethylene group; and Rc is selected from a hydrogen atom and a C1-C4 alkyl group, [R2SiO3/2] (2) wherein R2 is an unsubstituted phenyl group, and [R2SiO(ORc)] (5) wherein R2 is as defined in Formula (2); and Rc is as defined in Formula (II). ### Claim 12 (depends on 11) The method for producing a hard coat film according to claim 11, the method further comprising the step of: (A) unwinding a wound, rolled substrate, the steps (A) and (B) being performed successively. ### Claim 13 (depends on 12) The method for producing a hard coat film according to claim 12, the method further comprising the step of: (C) rewinding the hard coat film into a roll, the steps (A), (B), and (C) being performed successively.