WO2019194281A1 - フォトクロミック接着性組成物、フォトクロミック積層体、及び該フォトクロミック積層体を用いた光学物品 - Google Patents
フォトクロミック接着性組成物、フォトクロミック積層体、及び該フォトクロミック積層体を用いた光学物品 Download PDFInfo
- Publication number
- WO2019194281A1 WO2019194281A1 PCT/JP2019/014976 JP2019014976W WO2019194281A1 WO 2019194281 A1 WO2019194281 A1 WO 2019194281A1 JP 2019014976 W JP2019014976 W JP 2019014976W WO 2019194281 A1 WO2019194281 A1 WO 2019194281A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- photochromic
- resin
- group
- component
- adhesive composition
- Prior art date
Links
- 0 *C(*)(C=C1)Oc2c1c(*)c(*)c1c2cc(*)c(*)c1 Chemical compound *C(*)(C=C1)Oc2c1c(*)c(*)c1c2cc(*)c(*)c1 0.000 description 5
- VAUDSXPKVOEUNI-UHFFFAOYSA-N CC(C)(c1ccccc1-1)c2c-1c(cccc1)c1c1c2C=CC(c(cc2)ccc2OC)(c(cc2)ccc2OC)O1 Chemical compound CC(C)(c1ccccc1-1)c2c-1c(cccc1)c1c1c2C=CC(c(cc2)ccc2OC)(c(cc2)ccc2OC)O1 VAUDSXPKVOEUNI-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/02—Polyureas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
- B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
- B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B23/08—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
- B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/757—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the cycloaliphatic ring by means of an aliphatic group
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
- C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/02—Polyureas
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/02—Polyureas
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
-
- 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
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/23—Photochromic filters
-
- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
- G02C7/10—Filters, e.g. for facilitating adaptation of the eyes to the dark; Sunglasses
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/712—Weather resistant
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/748—Releasability
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2551/00—Optical elements
-
- 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
- C08G2170/00—Compositions for adhesives
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0041—Optical brightening agents, organic pigments
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/22—Presence of unspecified polymer
- C09J2400/228—Presence of unspecified polymer in the pretreated surface to be joined
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2469/00—Presence of polycarbonate
- C09J2469/008—Presence of polycarbonate in the pretreated surface to be joined
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2475/00—Presence of polyurethane
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- 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
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
-
- G—PHYSICS
- G02—OPTICS
- G02C—SPECTACLES; SUNGLASSES OR GOGGLES INSOFAR AS THEY HAVE THE SAME FEATURES AS SPECTACLES; CONTACT LENSES
- G02C7/00—Optical parts
- G02C7/10—Filters, e.g. for facilitating adaptation of the eyes to the dark; Sunglasses
- G02C7/102—Photochromic filters
Definitions
- the present invention relates to a novel photochromic adhesive composition having adhesiveness.
- the present invention relates to a novel photochromic adhesive composition capable of firmly bonding optical sheets, particularly optical sheets made of organic resins, even at high temperatures and exhibiting excellent photochromic properties. Furthermore, it is related with the novel photochromic laminated body obtained using this photochromic adhesive composition, and a novel optical article.
- the urethane (urea) resin includes both a urethane resin having only a urethane bond and a urethane urea resin including both the urethane bond and the urea bond.
- plastic photochromic sunglasses that can adjust the antiglare property by changing the transmittance according to the surrounding brightness by combining with the photochromic dye are rapidly gaining popularity. .
- plastic photochromic sunglasses is not always easy.
- a photochromic paint in which a photochromic agent is added to an acrylate copolymer see Patent Document 1
- Patent Document 1 a photochromic paint in which a photochromic agent is added to an acrylate copolymer
- Patent Document 1 a photochromic paint in which a photochromic agent is added to an acrylate copolymer
- a polycarbonate resin is injection-molded in a mold in which a composite film having a photochromic film made of the paint formed on the polycarbonate film surface is mounted.
- it is considered to be due to the properties of the acrylate copolymer, but the adhesion to the polycarbonate film is insufficient, and it was difficult to obtain sunglasses having good photochromic properties.
- the following methods are known as methods for producing a synthetic resin laminate having good photochromic properties. Specifically, first, a resin layer having photochromic properties is continuously applied to one side of a transparent synthetic resin layer such as a polycarbonate sheet that moves continuously. Next, after the resin layer is dried (the resin layer becomes an adhesive layer), a method of pasting another transparent sheet is proposed (see Patent Document 2 and Patent Document 3).
- the resin composition specifically, polyurethane resin composition
- the resin composition is When applied to a polycarbonate sheet or the like, the transparent sheet may be dissolved. As a result, there has been a problem that an appearance defect occurs, or that the photochromic characteristics are deteriorated by the synthetic resin eluted in the urethane resin.
- Patent Document 1 there is a method of using “a laminated sheet in which a polycarbonate sheet is bonded by a polyurethane resin adhesive layer containing a photochromic dye” instead of the composite film (Patent Document 4 and Patent Document). 5).
- the adhesion and heat resistance of the polycarbonate sheet in the laminated sheet were insufficient.
- the resulting optical article may be peeled off or optical distortion may occur. There was a problem.
- Patent Documents 6 and 7 show that a photochromic adhesive composition having high heat resistance is also progressing. These methods consist of an adhesive mainly composed of a urethane resin, but have good heat resistance by crosslinking a prepolymer having a reactive group at the terminal or by crosslinking the main polymer chain with a polyisocyanate compound.
- the photochromic adhesive layer is used.
- the object of the present invention is, first of all, a photochromic adhesive composition having excellent adhesion and heat resistance and exhibiting excellent photochromic properties when used as an adhesive layer when bonding optical sheets. Is to provide.
- the second object of the present invention is a photochromic laminate including a laminated structure in which an optical sheet is bonded by an adhesive layer having photochromic properties, and has excellent adhesion, excellent heat resistance, and excellent photochromic properties. It is providing the photochromic laminated body which has this.
- a third object of the present invention is to provide an optical article using the above-mentioned photochromic laminate and having excellent adhesion and photochromic properties.
- the inventors of the present invention made extensive studies to solve the above problems. Various combinations of the structure of the photochromic compound and the structure of the urethane (urea) resin were studied. As a result, it has been found that the above-mentioned problems can be solved by combining a specific urethane (urea) adhesive resin and a photochromic compound having a specific structure into a photochromic adhesive composition having a specific softening point. The present invention has been completed.
- the first aspect of the present invention is (A) a photochromic compound having a molecular chain having a molecular weight of 300 or more as a substituent (hereinafter sometimes referred to simply as “component (A)”), and (B) an adhesive urethane (urea) resin (hereinafter simply referred to as “component”). “(B) component”).
- component (A) a photochromic compound having a molecular chain having a molecular weight of 300 or more as a substituent
- component (B) an adhesive urethane (urea) resin
- component A photochromic adhesive composition having a softening point of 140 to 220 ° C.
- the second aspect of the present invention is a photochromic laminate including a laminate structure in which two (D) optical sheets facing each other are joined via an adhesive layer obtained from the photochromic adhesive composition.
- a polyester resin a polyamide resin, an allyl resin, a (meth) acrylic resin, a polyurethane resin, a polyurethane urea resin, a polythiourethane resin, or a polyepoxy resin on at least one outer surface of the photochromic laminate.
- E An optical article in which a synthetic resin layer made of a resin selected from a polythioepoxy resin and a polycarbonate resin is laminated.
- a photochromic adhesive composition that can firmly bond optical sheets to each other even at high temperatures and exhibits excellent photochromic properties is obtained. Therefore, the photochromic laminate in which the optical sheet is bonded with the adhesive layer made of the photochromic adhesive composition of the present invention is formed such as peeling even if a relatively high temperature resin is laminated thereon by injection molding or the like. It is difficult to cause sexual defects. In addition, the obtained optical article exhibits excellent photochromic properties.
- thermomechanical analysis Thermal Mechanical Analysis measurement figure at the time of measuring the softening point of the photochromic adhesive composition (adhesion layer) used in Example 15.
- the present invention is a photochromic adhesive composition
- a photochromic adhesive composition comprising (A) a photochromic compound and (B) an adhesive urethane (urea) resin.
- the (A) photochromic compound has a molecular chain having a molecular weight of 300 or more as a substituent, and (B) comprising an adhesive urethane (urea) resin,
- It is a photochromic adhesive composition having a heat resistance of a softening point of 140 to 220 ° C.
- the measuring method of a softening point is the value measured by the method as described in an Example.
- the photochromic adhesive composition of the present invention is particularly excellent in adhesiveness with an optical sheet.
- the photochromic compound (A) used in the present invention has a molecular chain having a molecular weight of 300 or more as a substituent, any one can be appropriately selected from known compounds without particular limitation. Since the molecular chain having a molecular weight of 300 or more has a high molecular weight, when producing a photochromic compound, it may have a plurality of types of molecular chains instead of one type of molecular chain. In that case, the molecular weight of the molecular chain may be an average value. Moreover, this average value should just be a number average molecular weight.
- This molecular weight can be confirmed by the kind of raw material at the time of production of the photochromic compound, and when confirmed from the product, it can be confirmed by known means such as NMR, IR, and mass spectrometry.
- required from the used raw material is employ
- (A) It is thought that a high photochromic characteristic can be exhibited also in (B) component explained in full detail below which has high heat resistance because a component has a molecular chain of molecular weight 300 or more.
- the molecular weight of the molecular chain is preferably from 300 to 25,000, more preferably from 400 to 20,000, taking into account photochromic properties, its blending amount, and the productivity of the component (A) itself. More preferably 15,000, A range of 500 to 10,000 is particularly preferred.
- the molecular weight of the molecular chain is preferably 700 to 5,000, More preferably, it is 1,000 to 3,000.
- the number of the molecular chains is preferably at least 0.5 with respect to one molecule of the photochromic compound. That is, even when the number of molecular chains is the smallest, it is preferable to have a structure in which two photochromic compounds are bonded by the molecular chains.
- the upper limit of the number of molecular chains is preferably 4 for one molecule of the photochromic compound, preferably 2 in consideration of the balance with the molecular weight of the molecular chain and the photochromic characteristics.
- the component (A) preferably has a molecular structure that exhibits photochromic properties, and a portion of the molecule is cleaved by light irradiation to develop a color, and the cleaved portion recolors by recombination. Therefore, in order for a photochromic compound to reversibly repeat color development and color fading, the existence of free space (degree of molecular freedom) that does not hinder the movement of molecules when cleavage and recombination occur is very important. In the case of a compound having such a molecular structure, it is considered that the effect of the molecular chain is particularly exerted.
- Examples of such component (A) include International Publication No. 2000-015630, International Publication No. 2004-041961, International Publication No. 2005-105874, International Publication No. 2005-105875, International Publication No. 2006-022825. International Publication No. 2009-146509, International Publication No. 2010-20770, International Publication No. 2012-122414, International Publication No. 2012-149599, International Publication No. 2012-162725, International Publication No. 2012-176918, The photochromic compound having the molecular chain described in International Publication No. 2013-078086 and the like can be used.
- the preferred component (A) is at least one photochromic compound selected from the following formulas (1) and (2).
- L and L ′ are each a divalent organic group containing at least one group selected from a polyoxyalkylene chain, a (thio) ester group, and a (thio) amide group, and L and L ′ are May be the same or different
- Chain is a monovalent or divalent organic group containing at least one chain selected from a polysiloxane chain and a polyoxyalkylene chain
- the total molecular weight of L and Chain, or L, L ′ and Chain corresponds to the molecular weight of the molecular chain. That is, L and Chain in Formula (1), or L, L ′, and Chain in Formula (2) correspond to molecular chains.
- PC and PC ′ are each selected from compounds having a basic skeleton represented by the following formulas (3) to (7).
- the molecular structure in parentheses is the basic skeleton of PC or PC ', and the line indicates that L or L' is bonded.
- the preferred component (A) preferably has the basic skeleton.
- the basic skeleton one of the carbon atoms or nitrogen atoms that can have a substituent is directly bonded to L and Chain, or L, L ′, and Chain (molecular chain), and the other atoms are , Other substituents, or a hydrogen atom.
- a suitable component (A) is a carbon atom or a nitrogen atom that can have a substituent, one atom is bonded to the molecular chain via the substituent, and the other atom is another substituent, Alternatively, it preferably has a hydrogen atom.
- PC and PC ′ may be the same or different.
- the PC or PC ′ is preferably selected from compounds having a basic skeleton represented by the following formulas (3 ′) to (7 ′).
- ⁇ Basic skeleton represented by formula (3 ′) (preferred basic skeleton of formula (3))>
- a preferable basic skeleton is a structure represented by the following formula (3 ′).
- the molecular structure in parentheses is PC or the basic skeleton of PC', and the line indicates L or L '.
- R 1 and R 2 > R 1 and R 2 in Formula (3 ′) are each a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an optionally substituted carbon.
- R 3 and R 4 > R 3 and R 4 in the formula (3 ′) are each a hydrogen atom, an aryl group having 6 to 20 carbon atoms which may have a substituent, or 3 to 3 carbon atoms which may have a substituent. 20 heteroaryl groups.
- the substituent that the aryl group or the heteroaryl group has is A hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group, a heterocyclic group, a cyano group, Halogen atoms, Examples thereof include a substituent selected from an alkylthio group having 1 to 6 carbon atoms and an arylthio group having 6 to 10 carbon atoms which may have a substituent.
- R 5 and R 6 > R 5 and R 6 in the formula (3 ′) are a hydrogen atom, a halogen atom, a carboxyl group, an acetyl group, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 1 to 10 carbon atoms.
- An alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with an alkoxy group having 1 to 10 carbon atoms, an aminoalkyl group having 1 to 10 carbon atoms, and 3 to 20 carbon atoms A cycloalkyl group, an aryl group having 6 to 20 carbon atoms which may have a substituent, an alkoxycarbonyl group having 2 to 15 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms which may have a substituent, etc. Is mentioned.
- the substituent of the group which may have a substituent may be a “molecular chain”.
- the alkyl group may have a molecular chain via one substituent of R 1 to R 6 (excluding a hydrogen atom).
- R 1 to R 6 excluding a hydrogen atom
- the alkyl groups of R 1 to R 6 are of course an alkylene group.
- R 1 and R 2 are preferably a hydrogen atom, the alkyl group, the alkoxy group, the heterocyclic group, the aryl group, or the arylthio group.
- R 3 and R 4 are the alkyl group, the alkoxy group, the substituted amino group, the heterocyclic group, or an aryl group having 6 to 20 carbon atoms which may have a substituent.
- R 5 and R 6 are the alkyl group, the alkenyl group, the alkoxy group, the aryl group, the alkoxycarbonyl group, or the heteroaryl group. Further, it is preferable that at least one group is-(L-Chain) or-(L-Chain-L ')-described in detail below.
- the molecular chain is preferably substituted with any of R 3 , R 4 , R 5 , or R 6 .
- ⁇ Basic skeleton represented by formula (4 ′) (preferred basic skeleton of formula (4))>
- a preferable basic skeleton is a structure represented by the following formula (4 ′).
- R 8 and R 9 > R 8 and R 9 in the formula (4 ′) are each a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 6 carbon atoms, or an optionally substituted carbon.
- R 8 and R 9 in the above formula (4 ′) are an aliphatic ring having 3 to 20 ring carbon atoms, together with the carbon atom at the 13-position to which they are bonded,
- a condensed polycycle may be formed, provided that these rings may have a substituent.
- a heterocyclic ring having 3 to 20 member atoms, or a condensed polycyclic group in which an aromatic hydrocarbon ring or an aromatic heterocyclic ring is condensed to the heterocyclic ring may be formed.
- the substituent of a group that may have a substituent may be a “molecular chain”.
- R 1 to R 4 and R 7 to R 9 may have a molecular chain through one substituent of R 1 to R 4 and R 7 to R 9 (excluding a hydrogen atom).
- R 1 , R 2 , R 3 , R 4 are the same as the preferable group shown in the formula (3 ′), and R 7 is a hydrogen atom, the alkoxy group, the heterocyclic group, or the aryl.
- R 8 and R 9 preferably form a ring with the 13-position carbon atom to which the hydroxyl group, the alkyl group, the alkoxy group, R 8 and R 9 are bonded.
- the molecular chain is preferably substituted with any of R 3 , R 4 and R 7 to R 9 .
- ⁇ Basic skeleton represented by formula (5 ′) (preferred basic skeleton of formula (5))>
- a preferable basic skeleton has a structure represented by the following formula (5 ′).
- the molecular structure in parentheses is PC or the basic skeleton of PC', and the line indicates L or L '.
- the substituent of a group that may have a substituent may be a “molecular chain”.
- ⁇ Basic skeleton represented by formula (6 ′) (Suitable basic skeleton of formula (6))>
- a preferable basic skeleton has a structure represented by the following formula (6 ′).
- the molecular structure in parentheses is PC or the basic skeleton of PC ′, and the line indicates L or L ′.
- R 16 > R 16 in the formula (6 ′) is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 5 carbon atoms, a dihaloalkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms.
- Trihaloalkyl group, cycloalkyl group which may have a substituent having 3 to 20 carbon atoms, bicycloalkyl group which may have a substituent having 6 to 20 carbon atoms, carbon number which may have a substituent Examples include 6 to 20 aryl groups.
- R 14 and R 15 > Examples of R 14 and R 15 in the formula (6 ′) include a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an optionally substituted cycloalkyl group having 3 to 20 carbon atoms, and the like. It is done.
- the substituent of a group that may have a substituent may be a “molecular chain”.
- ⁇ Basic skeleton represented by formula (7 ′) (preferred basic skeleton of formula (7))>
- a preferable basic skeleton is a structure represented by the following formula (7 ′).
- the molecular structure in parentheses is PC or the basic skeleton of PC', and the line indicates that L or L 'is bonded.
- the substituent of a group which may have a substituent may be a “molecular chain”.
- R 13 to R 15 and R 18 to R 21 may have a molecular chain through one substituent of R 13 to R 15 and R 18 to R 21 (excluding a hydrogen atom).
- L or L ′ which is a suitable divalent organic group>
- L or L ′ is a divalent linking group containing at least one group selected from a polyoxyalkylene chain, a (thio) ester group, and a (thio) amide group. It is preferable that
- a divalent organic group represented by the following formula (8) is preferable.
- R 22 is a divalent group, a linear or branched alkylene group having 1 to 20 carbon atoms, or a cycloalkyl group optionally having a substituent having 3 to 12 carbon atoms forming a ring
- R 23 is a divalent group, a linear or branched alkylene group having 1 to 20 carbon atoms, or a cycloalkyl group that may have a substituent having 3 to 12 carbon atoms to form a ring
- R 24 is a divalent group, a linear or branched alkylene group having 1 to 20 carbon atoms, or a cycloalkyl group optionally having a substituent having 3 to
- L and L ′ may be the same or different from each other, and the dotted line portion represents the bond with the photochromic site.
- the photochromic site means PC or PC ′.
- d is preferably 0, and e, e ′, f and g are each independently an integer of 0 to 2, and two e may be the same. May be different.
- X1 and X2 are preferably O (oxygen atom).
- R 23 , R 23 ′ , R 24 and R 27 are preferably each independently a linear or branched alkylene group having 1 to 5 carbon atoms.
- the “Chain” moiety is a monovalent group including at least one chain selected from a polyalkylene oxide chain, a polyester chain, a polyester polyether chain, and a polysiloxane chain, or 2 It is preferably a valent group.
- a chain having a repeating unit represented by the following formulas (9a) to (9d) is preferable.
- R 25 is a linear or branched alkylene group having 1 to 20 carbon atoms. When a plurality of R 25 are contained in the same molecule, R 25 may be the same or different from each other. Often, n represents the repeating unit of the oligomer chain group, and is an integer of 3 to 200, and the divalent groups of a plurality of repeating units may be the same as or different from each other.
- R 26 is a linear or branched alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 14 carbon atoms, and when R 26 includes a plurality of R 26 in the same molecule, R 26 They may be the same or different. ⁇ It is group shown by these.
- a photochromic compound having the following combination is one selected from the naphthopyran skeletons of the formulas (3 ′), (4 ′), and (5 ′), and L and L ′ are the formulas (8).
- the “Chain” portion is one selected from the formulas (9a) to (9d).
- the adhesive urethane (urea) resin as the component (B) will be described.
- the adhesive urethane (urea) resin mainly determines the softening point of the photochromic adhesive composition.
- the component (B) must satisfy the softening point of 140 to 220 ° C. of the photochromic adhesive composition containing the component (A) and the component (B). Therefore, although not particularly limited, the softening point of the component (B) is 140 to 220 ° C. when the component (C) is not used in order to exhibit particularly excellent effects.
- the temperature is preferably 150 to 200 ° C, more preferably 160 to 190 ° C.
- the softening point of the component (B) alone is preferably 120 to 220 ° C. 130 to 200 ° C is more preferable, 140 to 190 ° C is further preferable, and 140 to 170 ° C is particularly preferable.
- the softening point of the urethane (urea) resin obtained by crosslinking the component (B) with the component (C) is preferably 140 to 220 ° C., and preferably 150 to 200. More preferably, the temperature is 155 to 195 ° C, more preferably 160 to 190 ° C.
- the softening point refers to a photochromic adhesive composition.
- This softening point corresponds to the softening point of the adhesive layer containing the photochromic compound that forms the photochromic laminate described in detail below. That is, (D) the softening point of the adhesive layer made of the photochromic adhesive composition that joins the optical sheet.
- this softening point is a softening point of the adhesive layer containing a photochromic compound, it is considered that the photochromic compound hardly affects the softening point. Therefore, the softening point of the component (B) or the reaction product of the component (B) and the component (C) (urethane (urea) resin) is preferably 140 to 220 ° C, and preferably 150 to 200 ° C. Is more preferably 155 to 195 ° C, particularly preferably 160 to 190 ° C.
- a photochromic adhesive composition having a softening point of 140 to 220 ° C. can be easily obtained by using a urethane (urea) adhesive resin cross-linked with the component (B) or the component (C) having a softening point as described above. Can be manufactured.
- urea urethane
- the component (B) is at least selected from (B1) a polycarbonate polyol having a number average molecular weight of 400 to 3000 having two or more hydroxyl groups in the molecule, and a polycaprolactone polyol from the viewpoint of adhesiveness and photochromic properties.
- component (B1) a polycarbonate polyol having a number average molecular weight of 400 to 3000 having two or more hydroxyl groups in the molecule
- component (B2) polyisocyanate compound having two or more isocyanate groups in the molecule
- component (B2) polyisocyanate compound having two or more isocyanate groups in the molecule
- (B1) Component; Polyol Compound As the polyol compound used for the urethane (urea) resin, a polyol compound such as polyether polyol, polycarbonate polyol, polycaprolactone polyol, polyester polyol and the like can be used. Of these, polycarbonate polyol and polycaprolactone polyol are preferably used from the viewpoints of heat resistance, adhesion, photochromic properties, and the like.
- the number average molecular weight of the polyol compound is preferably 400 to 3000. Among these, from the viewpoint of heat resistance and photochromic properties, the number average molecular weight is preferably 400 to 2500, and more preferably 400 to 2000.
- polyisocyanate compound As the polyisocyanate compound used for the urethane (urea) resin, an aliphatic polyisocyanate compound or an alicyclic polyisocyanate compound is preferably used from the viewpoint of weather resistance.
- aliphatic such as tetramethylene-1,4-diisocyanate, hexamethylene-1,6-diisocyanate, octamethylene-1,8-diisocyanate, 2,2,4-trimethylhexane-1,6-diisocyanate
- Polyisocyanate compounds cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate, 2,4-methylcyclohexyl diisocyanate, 2,6-methylcyclohexyl diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 4,4'-methylenebis (cyclohexyl) Isocyanate) isomer mixture, hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate, hexahydrophenylene-1,
- the adhesive urethane (urea) resin (B) in the present invention has a molecular weight of 50 to 50 in addition to the above components (B1) and (B2), and (B3) a group capable of reacting with two or more isocyanate groups in the molecule. It is also possible to use 300 active hydrogen-containing compounds (hereinafter sometimes simply referred to as component (B3)).
- component (B3) will be described below.
- the active hydrogen-containing compound used in the urethane (urea) resin functions as a chain extender or a crosslinking agent when the (B) urethane (urea) resin is synthesized.
- a compound having a molecular weight of 50 to 300 it is preferable to use a compound having a molecular weight of 50 to 300. Specifically, amino group-containing compounds such as diamine compounds and triamine compounds, and hydroxyl group-containing compounds such as diol compounds and triol compounds can be used.
- amino group-containing compound examples include isophorone diamine, ethylene diamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,2-diaminobutane, 1,3- Diaminobutane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, piperazine, N, N-bis- (2-aminoethyl) piperazine, bis- (4-aminocyclohexyl) methane, Bis- (4-amino-3-butylcyclohexyl) methane, 1,2-, 1,3- and 1,4-diaminocyclohexane, norbornanediamine, hydrazine, dihydrazine adipate, phenylenediamine, 4,4'-diphenylmethane Diamine, N, N'-diethylethylenediamine, N, N
- the amino group-containing compound has two amino groups in the molecule, and the alicyclic compound is preferable. Specifically, it is preferable to use isophoronediamine, bis- (4-aminocyclohexyl) methane, or norbornanediamine.
- the compound preferably used as the hydroxyl group-containing compound include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, 1,5-dihydroxypentane, 1,6-dihydroxyhexane, 1, 7-dihydroxyheptane, 1,8-dihydroxyoctane, 1,9-dihydroxynonane, 1,10-dihydroxydecane, 1,11-dihydroxyundecane, 1,12-dihydroxydodecane, neopentyl glycol, glycerin, trimethylo- Examples include luethane, trimethylolpropane, di (trimellirolpropane), butanetriol, 1,2-methylglucoside, pentaerythritol, dipentaerythritol, tripentaerythritol and the like.
- a hydroxyl group-containing compound having two or more hydroxyl groups in the molecule and having a molecular weight of 50 to 300 (g / mol) is preferable.
- ethylene glycol, propylene glycol, and 1,4 butanediol are mentioned as those having two hydroxyl groups.
- the compound having three or more hydroxyl groups include trimellilol propane and di (trimelliol propane).
- the component (B) may be a reactive group such as an isocyanate group at the end, but when the component (C) described in detail below is used, It is preferable that the terminal is a non-reactive group.
- the component (B) when the component (C) is blended, the component (B) is a known monofunctional substance having an active hydrogen group that can react with the isocyanate group remaining at the molecular terminal (reaction termination).
- reaction termination it is preferable to use a non-reactive agent that has been reacted with the agent (hereinafter sometimes referred to simply as component (B4)).
- component (B4) As a reaction terminator, amine, alcohol, thiol, and carboxylic acid can be used.
- the functionality-imparting compound can be introduced into the polyurethane-urea resin and at the same time the terminal isocyanate group can be inactivated. it can.
- the quantity ratio of the components (B1), (B2), and (B3) is the urethane (urea) ) From the viewpoint of the balance of the heat resistance and adhesive strength of the resin, the following ratio is preferable.
- the total number of moles of hydroxyl groups contained in the component (B1) is n1
- the total number of moles of isocyanate groups contained in the component (B2) is n2
- the above n1 to n3 can be determined as the product of the number of moles of the compound used as each component and the number of groups present in one molecule of the compound.
- n1: n2: n3: n4 0.2 to 0.8: 1.0: 0.2 to 0.8: 0.01 to 0.2
- n1: n2: n3: n4 A quantitative ratio of 0.3 to 0.7: 1.0: 0.3 to 0.7: 0.01 to 0.18 is more preferable.
- the reaction between the component (B1) and the component (B2) is carried out at a temperature of 25 to 120 ° C. in an inert gas atmosphere such as nitrogen or argon in the presence or absence of a solvent. What is necessary is just to make it react for 24 hours.
- organic solvents such as methyl ethyl ketone, diethyl ketone, toluene, hexane, heptane, ethyl acetate, dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF) can be used.
- reaction in order to avoid a reaction between an isocyanate group in the diisocyanate compound and water as an impurity, it is preferable that various reaction reagents and solvents are subjected to dehydration in advance and sufficiently dried.
- a catalyst such as octane may be used.
- the addition amount when using the catalyst is preferably 0.001 to 1 part by mass with respect to 100 parts by mass as a total of the component B.
- the reaction between the obtained urethane prepolymer and the component (B3) is carried out at 0.5 to 24 at ⁇ 10 to 100 ° C. in an inert gas atmosphere such as nitrogen or argon in the presence or absence of a solvent. What is necessary is just to make it react for hours.
- a solvent methanol, ethanol, isopropyl alcohol, t-butanol, 2-butanol, n-butanol, methyl ethyl ketone, diethyl ketone, toluene, hexane, heptane, ethyl acetate, DMF, DMSO, THF and the like can be used.
- component (B3) when a compound having a trifunctional or higher functional active hydrogen group is used as the component (B3), in order to form a crosslinked structure that does not dissolve in a general organic solvent, in the production of the photochromic laminate described later, (B1) By mixing the prepolymer obtained by reacting the component with the component (B2) and the component (B3) to form a photochromic laminate, the prepolymer and the component (B3) are reacted by heat treatment, A method of forming the component (B) is preferable.
- the photochromic adhesive composition of the present invention comprises the component (A), and the (B) adhesive urethane (urea) resin.
- the softening point must be 140-220 ° C. That is, it is necessary to use the component (A) having a specific molecular chain, to contain the (B) adhesive urethane (urea) resin, and to adjust the softening point to 140 to 220 ° C.
- the softening point of the photochromic adhesive composition is less than 140 ° C., the photochromic properties are good, but in the process of manufacturing the optical article described later, defects due to the softening of the adhesive layer made of the component (B) occur. This is not preferable because of the tendency to On the other hand, when the softening point exceeds 220 ° C., the photochromic characteristics are lowered, and the adhesion to the optical sheet tends to be lowered. Normally, it is considered that the higher the softening point, the higher the heat resistance and the higher the adhesion at high temperatures.
- the softening point of the photochromic adhesive composition is 140 to 220 ° C. It was found that the photochromic characteristics cannot be exhibited.
- the softening point of the photochromic adhesive composition is more preferably 150 to 200 ° C, further preferably 155 to 195 ° C, and more preferably 160 to 190 ° C. It is particularly preferred.
- the softening point of the photochromic adhesive composition can be adjusted by the heat resistance of the component (B), the composition and blending amount of the component (A), and the blending of the component (C) described in detail below.
- the photochromic adhesive composition of this invention can be manufactured by mixing the said (A) component, (B) component, and another component.
- the order in which the components are mixed is not particularly limited.
- each component can be melt-kneaded and pelletized as a photochromic adhesive composition, or it can be molded into a sheet as it is.
- a photochromic adhesive composition can be obtained by dissolving each component in an organic solvent.
- the photochromic adhesive composition of the present invention thus obtained can be suitably used particularly as a photochromic adhesive for joining optical sheets.
- a photochromic laminated body can be obtained by mutually bonding an optical sheet through the contact bonding layer which consists of a photochromic adhesive composition of this invention.
- the blending amount of the photochromic compound is preferably 0.1 to 20.0 parts by mass with respect to 100 parts by mass of the component (B) from the viewpoint of photochromic properties.
- the amount is too small, sufficient color density and durability tend not to be obtained.
- the uniformity of the composition tends to decrease, and the adhesive strength (adhesion) is also reduced. There is also a tendency to decline.
- the addition amount of the photochromic compound is 0.5 to 20.0 mass with respect to 100 mass parts of the total amount of the resin components. More preferably, the content is 1.0 to 15.0 parts by mass.
- component (C) an isocyanate compound having at least one isocyanate group in the molecule (hereinafter sometimes referred to simply as “component (C)”) is blended, and (B) component is partially crosslinked. It can also be set as a photochromic adhesive composition. Next, the component (C) will be described.
- the photochromic adhesive composition of the present invention even if the softening point of the adhesive urethane (urea) resin that is the component (B) is less than 140 ° C., the photochromic adhesive composition can be obtained by blending the component (C).
- the softening point of an object can also be 140 degreeC or more. This is because the isocyanate group of the (C) component acts on the urethane (urea) bond in the urethane (urea) resin of the (B) component to partially increase the molecular weight or form a crosslinked structure.
- the softening point of the adhesive composition can be in the range of 140 to 220 ° C.
- the photochromic adhesive composition containing the component (C) is presumed to have improved adhesion to the optical sheet and heat resistance.
- the urethane (urea) resin is a non-reactive urethane (urea) resin having no reactive group at the molecular end
- the component (B4) is blended to make the terminal a non-reactive group
- the softening point of the component (B) is less than 140 ° C.
- the softening point of the finally obtained photochromic adhesive composition satisfies the range of 140 to 220 ° C.
- the component (B) having a softening point of 140 ° C. or higher and the component (C) can be used in combination.
- component (C) examples include 4,4′-methylenebis (cyclohexyl isocyanate) isomer mixture, cyclobutane-1,3-diisocyanate, cyclohexane-1,3-diisocyanate, cyclohexane-1,4- A trimer of diisocyanate, hexahydrotoluene-2,4-diisocyanate, hexahydrotoluene-2,6-diisocyanate, hexahydrophenylene-1,3-diisocyanate, hexahydrophenylene-1,4-diisocyanate, and isophorone diisocyanate ( Isocyanurate compound), hexamethylene diisocyanate biuret compound, hexamethylene diisocyanate isocyanurate compound, hexamethylene diisocyanate adduct compound, and the like.
- Isocyanurate compound hexam
- the blending ratio of the component (C) may be appropriately determined depending on the urethane (urea) resin to be used, but is 4 with respect to 100 parts by mass of the adhesive urethane (urea) resin component (component (B)). It is preferably 0 to 20 parts by mass. When the amount is too small, sufficient adhesiveness and heat resistance cannot be improved. When the amount is too large, the urethane (urea) resin tends to become cloudy, decrease in adhesiveness, and the like.
- blending a component may form partially the crosslinked structure which does not melt
- the photochromic characteristics can be exhibited. That is, it is considered that the photochromic compound is likely to move (ring-opening / ring-closing, etc.) because the softening point of the base component (B) is low. And while taking advantage of this situation, it is considered that the photochromic properties are enhanced by partially crosslinking with the component (C) to increase the softening point.
- the softening point of (B) adhesive urethane (urea) resin is preferably 120 to 150 ° C., more preferably 120 to 140 ° C.
- the softening point of the (B) adhesive urethane (urea) resin is preferably lower than the softening point of the photochromic adhesive composition of the present invention, and the difference between them (the softening point of the photochromic adhesive composition ⁇ (B )
- the softening point of the adhesive urethane (urea) resin) is preferably 5 to 30 ° C, more preferably 10 to 25 ° C. When the difference is 5 to 30 ° C., the fading speed of the molded article (eg, optical article) obtained can be increased, and the photochromic characteristics can be improved.
- the photochromic adhesive composition includes a surfactant, a hindered amine light stabilizer, a hindered phenol antioxidant, a phenol radical scavenger, a sulfur antioxidant, in addition to the components that impart photochromic properties.
- Additives such as phosphorus antioxidants, UV stabilizers, UV absorbers, mold release agents, anti-coloring agents, antistatic agents, fluorescent dyes, dyes, pigments, fragrances, and plasticizers can also be blended.
- known compounds are used without any limitation, and these may be used as a mixture of two or more. These additives may be mixed when producing the photochromic adhesive composition.
- the additive amount of the additive can be blended within a range that does not impair the effects of the present invention. Specifically, the total amount of additives is preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of component (B).
- the contact bonding layer obtained from a photochromic adhesive composition can be formed once using the solution which mixed the mixture of each component which comprises this photochromic adhesive composition, and the organic solvent. That is, in the presence of an organic solvent, in order to constitute the photochromic adhesive composition, a mixture of each component is sufficiently mixed, and the coating layer is formed using the solution. Then, the adhesive layer which consists of a photochromic adhesive composition can be formed by removing an organic solvent from this coating film layer.
- the softening point of the photochromic adhesive composition (adhesive layer) containing no organic solvent may be 140 to 220 ° C.
- a photochromic compound component (A)
- a urethane (urea) resin component (B)
- other components added as necessary Easy to mix.
- the uniformity of a photochromic adhesive composition can be improved.
- the viscosity of the photochromic adhesive composition or the mixture of each component which comprises this photochromic adhesive composition can be adjusted moderately.
- coating to an optical sheet and the uniformity of an application layer thickness can also be made high.
- problems such as poor appearance or reduced photochromic properties may occur. Can be avoided by adopting a method described later.
- the photochromic adhesive composition, or a mixture of the respective components, as described later since various types of solvents can be used, it is possible to select the solvent that does not easily attack the optical sheet as the solvent. Problems can be prevented from occurring.
- organic solvents examples include methanol, ethanol, n-propanol, i-propanol, 2-pentanol, 3-pentanol, 3-methyl-2-butanol, 4-methyl-2-pentanol, n- Alcohols such as butanol, t-butanol, 2-butanol, t-pentyl alcohol 2,2,2-trifluoroethanol; ethylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n -Propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol-n- Polyhydric alcohol derivatives such as til ether and ethylene glycol dimethyl ether; diacetone alcohol; ketones such as methyl ethyl ether
- the component (B) may be appropriately selected and used according to the type of component (B) and the material of the optical sheet.
- the component (B) may contain an isocyanate group, It is more preferable to use an organic solvent that does not contain a reactive group.
- organic solvents include ketones such as methyl ethyl ketone, diethyl ketone, n-propyl methyl ketone, methyl isobutyl ketone, diisopropyl ketone, n-butyl methyl ketone, ethyl acetate, 2-methoxyethyl acetate, acetic acid- Acetates such as 2-ethoxyethyl; DMF; DMSO; THF; cyclopentanone, cyclohexanone; chloroform;
- the amount of the organic solvent used is not particularly limited, but is preferably 100 to 500 parts by mass with respect to 100 parts by mass of the adhesive urethane (urea) resin component (component (B)).
- component (B) the photochromic laminate will be described.
- the photochromic laminate includes a laminate structure in which two optical sheets facing each other are bonded via an adhesive layer made of the photochromic adhesive composition of the present invention.
- FIG. 1 shows a cross-sectional view of a suitable layer structure of the photochromic laminate. If it demonstrates using FIG. 1, it is preferable that the photochromic laminated body 1 has a laminated structure where the optical sheets 2 and 4 are joined through the contact bonding layer 3 which consists of a photochromic adhesive composition. In the present invention, the softening point of the adhesive layer needs to be 140 to 220 ° C. An optical sheet that can be used for this photochromic laminate will be described.
- the (D) optical sheet can be used without particular limitation as long as it is a light-transmitting sheet, but a resin-made one is used from the viewpoints of availability and ease of processing. Is preferred.
- the resin suitable as the raw material for the optical sheet (D) include polycarbonate resin, polyester resin, cellulose resin, polyamide resin, (meth) acrylic resin, polyurethane resin, polyurethane urea resin, epoxy resin, polyimide resin, polyolefin resin. And polyvinyl alcohol resin.
- polycarbonate resin and polyamide resin are particularly preferable because of good adhesiveness and high applicability to the injection molding method.
- the film thickness of the (D) optical sheet is preferably 20 to 1000 ⁇ m, and more preferably 50 to 500 ⁇ m from the viewpoint of processability of the resulting photochromic laminate.
- the surface (upper surface and lower surface) of the (D) optical sheet of the present invention is a physical treatment such as chemical treatment using a chemical solution such as an alkaline solution or an acid solution, polishing treatment, corona discharge treatment, plasma discharge treatment, UV ozone treatment, etc. Surface treatment may be performed.
- the coating layer comprises a water-dispersible polymer such as water-dispersed polyurethane resin, water-dispersed polyester resin, water-dispersed acrylic resin, water-dispersed polyurethane / acrylic resin; among the water-dispersible polymers, a polymer having a carbonyl group and a hydrazide compound A crosslinked product of a water-soluble polymer such as polyvinyl alcohol; a polymerizable monomer having a (meth) acrylic group and / or an epoxy group, a (meth) acrylic group, a vinyl group, an amino group, and a mercapto group.
- a water-dispersible polymer such as water-dispersed polyurethane resin, water-dispersed polyester resin, water-dispersed acrylic resin, water-dispersed polyurethane / acrylic resin
- a polymer having a carbonyl group and a hydrazide compound A crosslinked product of a water-soluble polymer such as polyvinyl alcohol;
- thermosetting resin optical substrate
- thermosetting resin optical substrate
- the photochromic laminate of the present invention is produced by joining two optical sheets facing each other via an adhesive layer made of the photochromic adhesive composition of the present invention.
- the thickness of the adhesive layer is preferably 5 to 100 ⁇ m, more preferably 10 to 60 ⁇ m, from the viewpoint of the color density of the photochromic compound, weather resistance, and adhesive strength.
- the adhesive layer can be obtained by the following method.
- a mixture obtained by blending a solvent with the photochromic adhesive composition of the present invention is adjusted to an appropriate viscosity, the mixture is applied onto one optical sheet, and if necessary (heating) After drying, another optical sheet may be (heated) pressure bonded.
- the photochromic adhesive composition of the present invention and a mixture containing an organic solvent (I) the organic solvent is removed by drying after spreading the mixture on a smooth substrate, Thereafter, the substrate is peeled off to produce a photochromic adhesive sheet, and then (II) the two optical sheets are joined with the photochromic adhesive sheet interposed between the two optical sheets facing each other.
- the photochromic laminate of the present invention can also be produced.
- the photochromic adhesive composition may be a mixture of components constituting the photochromic adhesive composition.
- an adhesive layer made of a photochromic adhesive composition can also be formed.
- the material for the smooth base material those which are resistant to the solvent used in the present invention and those in which the adhesive layer is easy to peel off are preferable. Specifically, glass, stainless steel, Teflon (registered trademark) , Polyethylene terephthalate, polypropylene, and a plastic film on which a coating layer for improving the peelability such as silicon or fluorine is laminated.
- a photochromic adhesive composition when manufacturing a photochromic adhesive composition, it has a urethane (urea) prepolymer composed of the component (A), the component (B1), and the component (B2), and an active hydrogen group having three or more functions ( B3)
- the component is mixed with an organic solvent, and the resulting mixture is applied to a smooth substrate, and then the organic solvent is removed by drying, and has a urethane (urea) prepolymer and a trifunctional or higher functional hydrogen group.
- the component (B3) is reacted to obtain the component (B).
- the photochromic laminate of the present invention is another type of urethane (urea) resin not containing a photochromic compound on both sides of an adhesive layer made of a photochromic adhesive composition for the purpose of further improving the adhesiveness to the optical sheet.
- a photochromic laminate formed by laminating an adhesive layer (second adhesive layer) and joining two optical sheets may be used. That is, the laminate is a laminate in which an optical sheet, a second adhesive layer, an adhesive layer made of a photochromic adhesive composition, a second adhesive layer, and an optical sheet are laminated in this order.
- the second adhesive layer can use the component (B) as it is.
- n1: n2: n3: n4 0.30 to 0.89: 1.0: 0.10 to 0.69: 0.01 to 0.20.
- the same compound can be used for the same reason as described for the component (B), and suitable compounds are also the same.
- the component (B) forming the second adhesive layer that is, the second adhesive layer itself, preferably has a softening point of 140 to 220 ° C.
- the second adhesive layer preferably has a softening point of 150 to 200 ° C, more preferably 160 to 190 ° C. Since the second adhesive layer does not contain a photochromic compound, the softening point of the urethane (urea) resin (second adhesive layer) obtained without using the component (C) is 140 to 220 ° C.
- the thickness of the second adhesive layer is not particularly limited, but is preferably 5 to 15 ⁇ m. In addition, it is preferable to provide a 2nd contact bonding layer in both of two optical sheets.
- the ratio of the total thickness of the second adhesive layer to the thickness of the adhesive layer made of the photochromic adhesive composition may be 0.1 to 0.9. Preferably, it is 0.3 to 0.7.
- optical article In this invention, it can be set as the optical article which laminated
- stacked synthetic resin layers such as a plastic optical base material
- an optical article is obtained by integrating the photochromic laminate and an optical substrate such as a plastic lens body.
- the raw material for the optical substrate include the same materials as those for the optical sheet.
- a method of integrating for example, after mounting the photochromic laminate of the present invention in a mold, a method of injection molding a thermoplastic resin for constituting an optical substrate (for example, a lens body) (hereinafter, Simply referred to as an injection molding method), and a method of attaching a photochromic laminate to the surface of an optical substrate with an adhesive or the like.
- an injection molding method a method of injection molding a thermoplastic resin for constituting an optical substrate
- the photochromic laminated body can also be embed
- the optical article may be one in which the photochromic laminate is laminated on a plastic optical substrate made of a thermoplastic resin or a thermosetting resin, or is embedded in the plastic optical substrate. It may be.
- the synthetic resin layer such as the plastic optical substrate, polyester resin, polyamide resin, allyl resin, (meth) acrylic resin, polyurethane resin, polyurethane urea resin, polythiourethane resin, polyepoxy resin, polythioepoxy resin, and Known resins such as polycarbonate resin can be listed.
- the photochromic laminate of the present invention can be processed into a lens-like spherical shape by performing bending before being integrated with the optical substrate.
- Examples of the method of bending the photochromic laminate into a spherical shape include hot press processing, pressure processing, and vacuum suction processing.
- the temperature at the time of bending may be appropriately determined according to the type of optical sheet used in the photochromic laminate, but it is preferably carried out at a temperature exceeding 120 ° C. and not exceeding 200 ° C.
- the bent photochromic laminate may be mounted in a mold of an injection molding machine, and the optical substrate and the photochromic laminate may be integrated by injection molding.
- injection molding a general injection molding machine, injection compression molding machine, or the like is used.
- the molding conditions for injection molding may be appropriately determined according to the type and physical properties of the resin forming the optical substrate.
- the resin temperature in the molding machine is 180 to 330 ° C., preferably 200 to 320 ° C.
- the injection pressure is 50 to 1700 kg / cm 2 , preferably 70 kg / cm 2 to 1500 kg / cm 2 .
- PC1 Synthesis of Photochromic Compound ⁇ PC1>
- the following formula (PC1) used in the examples can be produced with reference to, for example, the production method described in International Publication No. 2009-146509.
- WO2009-146509 it can be produced by reacting a naphthopyran compound having a 2-hydroxy-ethoxycarbonyl group with polydimethylsiloxane having carboxyl groups at both ends.
- the (average) molecular weight of the molecular chain is 1350.
- the PC1 is a photochromic compound having a molecular chain as a substituent.
- the PC3 and PC4 are photochromic compounds having no molecular chain.
- PL2 Duranol manufactured by Asahi Kasei Chemicals Corporation (polycarbonate polyol using 1,5-pentanediol and hexanediol as raw materials, number average molecular weight 800).
- PL3 Duranol (polycarbonate polyol using 1,5-pentanediol and hexanediol as raw materials, number average molecular weight 1000) manufactured by Asahi Kasei Chemicals Corporation.
- PL4 Duranol (polycarbonate polyol using 1,5-pentanediol and hexanediol as raw materials, number average molecular weight 2000) manufactured by Asahi Kasei Chemicals Corporation.
- PL5 Daicel Chemical Industries, Ltd. Plaxel (polycaprolactone polyol, number average molecular weight 830).
- PL6 Plaxel (polycaprolactone polyol, number average molecular weight 1000) manufactured by Daicel Chemical Industries, Ltd.
- Component (B2) Polyisocyanate compound NCO1: 4,4′-methylenebis (cyclohexyl isocyanate) isomer mixture. NCO2: isophorone diisocyanate.
- Component (B3) Active hydrogen-containing compound H1: 1,4-butanediol. H2: Isophoronediamine. H3: Bis- (4-aminocyclohexyl) methane. H4: trimethylolpropane. H5: Di (trimethylolpropane).
- Component (B4) Reaction stopper HA1: 1,2,2,6,6-pentamethyl-4-aminopiperidine.
- HA2 n-butylamine.
- Component C1 An isomer mixture of 4,4′-methylenebis (cyclohexyl isocyanate).
- C2 A trimer of hexamethylene diisocyanate (manufactured by Asahi Kasei Chemicals Corporation, product name Duranate 24A-100).
- L1 Ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] (Irganox 245, manufactured by Ciba Specialty Chemicals).
- L2 DOW CORNING TORAY L-7001 (manufactured by Toray Dow Corning Co., Ltd., surfactant).
- reaction solution was cooled to around 30 ° C. and dissolved in 1632 g of THF, and then 31.5 g of 1,4-butanediol (component (B3) component: H1) as a chain extender was added dropwise at 25 ° C. It was made to react for 1 hour and the THF solution of the urethane resin (U1) was obtained.
- component (B3) component: H1 1,4-butanediol
- Urethane urea resin (synthesis of (UU2 to UU11)) Polyol compound (component (B1)), polyisocyanate compound (component (B2)), active hydrogen-containing compound (component (B3)) shown in Table 2, and reaction terminator ( Using the component (B4), UU2 to UU11 were synthesized in the same manner as the UU1 synthesis method described above.
- Table 2 summarizes B1, B2, and B3 of UU1 to UU11, the types of components, and the molar mixing ratio.
- Table 2 shows the softening points of the separately prepared components (B) (that is, UU1 to UU11). The softening point was measured according to the method described in Example 1.
- urethane urea resin (W1) for second adhesive layer 225 g of polycarbonate diol ((B1) component: PL3) having a number average molecular weight of 1000 in a three-necked flask having a stirring blade, a cooling tube, a thermometer, and a nitrogen gas introduction tube 100 g of isophorone diisocyanate (component (B2): NCO2) was charged and reacted at 100 ° C. for 8 hours in a nitrogen atmosphere to synthesize a prepolymer. The end point of the reaction was confirmed by the back titration method of isocyanate group.
- reaction solution was cooled to around 30 ° C., dissolved in 2057 g of propylene glycol monomethyl ether, and then 36 g of isophoronediamine (((B3) component: H2)) as a chain extender was added dropwise at 25 ° C. Then, 2 g of n-butylamine (component (B4): HA2)) as a reaction terminator was added dropwise and reacted at 25 ° C. for 1 hour to give a urethane urea resin (W1) for the second adhesive layer. A solution was obtained. Moreover, the softening point of the separately produced component (W1) (second adhesive layer) was 170 ° C. The softening point was measured according to the method described in Example 1.
- Example 1 Preparation of Photochromic Adhesive Composition 10 g of THF solution of urethane resin (U1), 75 mg of photochromic compound (PC1), 30 mg of trimethylolpropane (component (B3): H4) as a crosslinking agent, and ethylenebis (oxyethylene) as an antioxidant ) 25 mg of bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] and 3 mg of DOW CORNING TORAY L-7001 as a surfactant were added, stirred and mixed at room temperature, and photochromic adhesiveness A mixture for constituting the composition was obtained. Table 3 shows the blending ratio of each component.
- the above mixture containing an organic solvent was applied to a PET (polyethylene terephthalate) film (Purex film manufactured by Teijin DuPont Films Co., Ltd.) and dried at 80 ° C. for 5 minutes.
- the photochromic adhesive sheet having a thickness of about 40 ⁇ m was obtained by peeling off.
- the obtained photochromic adhesive sheet was sandwiched between two polycarbonate sheets having a thickness of 300 ⁇ m and allowed to stand at 40 ° C. under vacuum for 24 hours. Thereafter, heat treatment is performed at 70 ° C. for 70 hours, and then humidification treatment is performed at 60 ° C. and 80% RH for 24 hours.
- a laminate was obtained.
- the photochromic adhesive sheet after performing the above treatment becomes an adhesive layer made of the photochromic adhesive composition.
- the color density as a photochromic property was 0.9, and the fading speed was 40 seconds.
- the peel strength was 140 N / 25 mm in a 23 ° C. atmosphere and 20 N / 25 mm in a 150 ° C. atmosphere.
- the softening point of this photochromic adhesive composition was measured as follows, the softening point was 190 degreeC.
- Table 3 shows the film thickness of the adhesive layer made of the photochromic adhesive composition and the presence / absence / thickness of use of the second adhesive layer.
- the softening point of the photochromic adhesive composition is the softening point of the adhesive layer made of the photochromic adhesive composition, and was measured using a sample prepared by the following method. Separately from the laminate, a sample was prepared and measured. Specifically, a mixture (including an organic solvent) constituting the same photochromic adhesive composition as that used in each example and comparative example was applied between two PET films, and then at 80 ° C. for 5 minutes. Dried. Thereafter, the PET film is peeled off, heat-treated at 70 ° C. for 70 hours, then humidified at 60 ° C. and 80% RH for 24 hours, and finally allowed to stand at 40 ° C. under vacuum for 24 hours. Adhesive sheet (adhesive layer) was obtained.
- the softening point of the obtained photochromic adhesive sheet means a softening temperature measured under the following conditions using a thermomechanical measurement device (manufactured by Seiko Instruments Inc., TMA120C).
- the method for obtaining the softening point was according to the method described in JIS K7196. [Measurement Conditions] Temperature rising rate: 10 ° C./min, measurement temperature range: 30 to 250 ° C., probe: needle-inserted probe with a tip diameter of 0.5 mm. The results are shown in Table 3.
- ⁇ max The maximum absorption wavelength after color development determined by a spectrophotometer (instant multichannel photo director MCPD1000) manufactured by Otsuka Electronics Co., Ltd. The maximum absorption wavelength is related to the color tone at the time of color development.
- the obtained photochromic laminate was used as a test piece having an adhesive part of 25 ⁇ 100 mm, mounted on a testing machine (Autograph AGS-500NX, manufactured by Shimadzu Corporation), and subjected to a tensile test at a crosshead speed of 100 mm / min.
- the peel strengths 1) to 2) below were measured.
- the obtained photochromic laminate was bent into a spherical shape by thermoforming using a bending machine (CPL32 manufactured by LEMA).
- a photochromic laminate having a diameter of 8 cm was placed in a concave mold having a suction port, and heated at 140 ° C. for 2 minutes while suctioning.
- a photochromic laminate processed into a spherical shape was obtained by removing it from the mold.
- Appearance evaluation in bending workability was performed by irradiating the surface of a photochromic laminate obtained by bending a high-pressure mercury lamp, and visually observing the projection to confirm whether bubbles were generated in the photochromic laminate.
- a bent photochromic laminate having no bubbles was regarded as a good product, and a bent photochromic laminate having one or more bubbles was regarded as defective.
- Table 7 shows the number of defects.
- Appearance evaluation in injection moldability Appearance evaluation is performed by irradiating a photochromic spectacle lens with a high-pressure mercury lamp and visually observing the projection to determine whether there is an injection failure due to melting of the adhesive urethane (urea) resin and bubbles are generated. confirmed.
- Photochromic spectacle lens that does not have poor appearance due to melting of adhesive urethane (urea) resin and no generation of bubbles, and has poor appearance due to melting of adhesive urethane (urea) resin, or photochromic with one or more bubbles generated The sexual spectacle lens was considered defective. Table 7 shows the number of defects.
- Example 2 Preparation of Photochromic Adhesive Composition A mixture constituting the same photochromic adhesive composition was obtained in the same manner as the preparation of the photochromic adhesive composition (adhesive layer) in Example 1. Table 3 shows the formulation.
- Adjustment of adhesive for second adhesive layer 2.5 mg of DOW CORNING TORAY L-7001 as a surfactant was added to 25 g of a propylene glycol monomethyl ether solution of urethane urea resin (W1) for second adhesive layer, and stirred at room temperature. -It mixed and obtained the adhesive agent for 2nd contact bonding layers.
- the second adhesive layer adhesive was applied onto a 300 ⁇ m thick polycarbonate sheet and dried at 110 ° C. for 10 minutes to obtain a polycarbonate sheet having a 10 ⁇ m thick second adhesive layer.
- the mixture constituting the photochromic adhesive composition was applied to a PET film (Purex film manufactured by Teijin DuPont Films Ltd., with silicone coating), dried at 80 ° C. for 10 minutes, and then the PET film was peeled off.
- a photochromic adhesive sheet having a thickness of about 40 ⁇ m was obtained.
- the obtained photochromic adhesive sheet was sandwiched between two polycarbonate sheets having the above-mentioned second adhesive layer, allowed to stand at 40 ° C. under vacuum for 24 hours, and then heat-treated at 70 ° C. for 70 hours, Next, a humidification treatment was performed at 60 ° C. and 80% RH for 24 hours, and finally, the mixture was allowed to stand for 24 hours at 40 ° C.
- the photochromic adhesive sheet after performing the above treatment becomes an adhesive layer made of the photochromic adhesive composition.
- the color density as a photochromic property was 0.9, and the fading speed was 40 seconds.
- the peel strength was 180 N / 25 mm in a 23 ° C. atmosphere and 40 N / 25 mm in a 150 ° C. atmosphere.
- the softening point of the photochromic adhesive sheet produced separately by the same method was 190 ° C.
- Table 3 shows the film thickness of the adhesive layer made of the photochromic adhesive composition and the presence / absence / thickness of use of the second adhesive layer.
- the thickness of the 2nd contact bonding layer in Table 3 is the thickness on one sheet
- the obtained photochromic laminate was evaluated in the same manner as in Example 1.
- Table 5 shows the photochromic properties and peel strength
- Table 7 shows the bending process and injection moldability.
- Examples 3-14 A photochromic adhesive composition was prepared in the same manner as in Example 2 except that (A) photochromic compound, (B) adhesive urethane (urea) resin, and (B3) active hydrogen-containing compound shown in Table 3 were used. .
- the softening point of the obtained photochromic adhesive composition was measured by the same method as in Examples 1 and 2 and shown in Table 3.
- a photochromic laminate was produced using each photochromic adhesive composition according to the same method as in Example 1 (without the second adhesive layer) or Example 2 (with the second adhesive layer).
- Table 3 shows the film thickness of the adhesive layer made of the photochromic adhesive composition and the presence / absence / thickness of use of the second adhesive layer.
- the obtained photochromic laminate was evaluated in the same manner as in Example 1.
- Table 5 shows photochromic properties and peel strength, and Table 7 shows bending and injection moldability.
- Comparative Examples 1 to 4 A photochromic adhesive composition was prepared in the same manner as in Example 1 except that (A) photochromic compound and (B) adhesive urethane (urea) resin shown in Table 3 were used. The softening point of the obtained photochromic adhesive composition was measured by the same method as in Examples 1 and 2 and shown in Table 3.
- a photochromic laminate was produced using each photochromic adhesive composition according to the same method as in Example 1 (without the second adhesive layer) or Example 2 (with the second adhesive layer).
- Table 3 shows the film thickness of the adhesive layer made of the photochromic adhesive composition and the presence / absence / thickness of use of the second adhesive layer.
- the obtained photochromic laminate was evaluated in the same manner as in Example 1.
- Table 5 shows photochromic properties and peel strength, and Table 7 shows bending and injection moldability.
- Example 15 Preparation of photochromic adhesive composition 10 g of THF solution of urethane urea resin (UU1), 82 mg of photochromic compound (PC1), isomer mixture of 4,4′-methylenebis (cyclohexyl isocyanate) (component (C); C1) 250 mg, and 28 mg of ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] as an antioxidant and 3 mg of DOW CORNING TORAY L-7001 as a surfactant were added at room temperature. Stirring and mixing were performed to obtain a mixture constituting the photochromic adhesive composition. The blending ratio of each component is shown in Table 4. The softening point is also shown in Table 4.
- photochromic laminate After applying the mixture containing the organic solvent to a PET (polyethylene terephthalate) film (Purex film manufactured by Teijin DuPont Films Ltd., with a silicon coating film) and drying at 80 ° C. for 5 minutes, The PET film was peeled off to obtain a photochromic adhesive sheet having a thickness of about 40 ⁇ m. Next, the obtained photochromic adhesive sheet was sandwiched between two polycarbonate sheets having a thickness of 300 ⁇ m, left to stand at 40 ° C. under vacuum for 24 hours, and then heat-treated at 100 ° C.
- PET polyethylene terephthalate
- the photochromic adhesive sheet after performing the above treatment becomes an adhesive layer made of the photochromic adhesive composition.
- the color density as a photochromic property was 0.9, and the fading speed was 45 seconds.
- the peel strength was 120 N / 25 mm in a 23 ° C. atmosphere and 15 N / 25 mm in a 150 ° C. atmosphere.
- the softening point of the photochromic adhesive sheet produced separately by the same method was 180 ° C.
- Table 4 shows the film thickness of the adhesive layer made of the photochromic adhesive composition and the presence / absence / thickness of use of the second adhesive layer.
- the thickness of the 2nd contact bonding layer in Table 4 is the thickness on one sheet
- the obtained photochromic laminate was evaluated in the same manner as in Example 1.
- Table 6 shows the photochromic properties and peel strength
- Table 7 shows the bending work and injection moldability.
- Example 16 Preparation of Photochromic Adhesive Composition A mixture constituting the same photochromic adhesive composition was obtained in the same manner as the preparation of the photochromic adhesive composition in Example 15. Table 4 shows the composition.
- Adjustment of adhesive for second adhesive layer 2.5 mg of DOW CORNING TORAY L-7001 as a surfactant was added to 25 g of a propylene glycol monomethyl ether solution of urethane urea resin (W1) for second adhesive layer, and stirred at room temperature. -It mixed and obtained the adhesive agent for 2nd contact bonding layers.
- the second adhesive layer adhesive was applied onto a 300 ⁇ m thick polycarbonate sheet and dried at 110 ° C. for 10 minutes to obtain a polycarbonate sheet having a 10 ⁇ m thick second adhesive layer.
- the above mixture containing an organic solvent was applied to a PET (polyethylene terephthalate) film (Purex film manufactured by Teijin DuPont Films Co., Ltd.) and dried at 80 ° C. for 5 minutes.
- the photochromic adhesive sheet having a thickness of about 40 ⁇ m was obtained by peeling off.
- the obtained photochromic adhesive sheet was sandwiched between two polycarbonate sheets having a thickness of 300 ⁇ m, left to stand at 40 ° C. under vacuum for 24 hours, and then heat-treated at 100 ° C. for 1 hour, and then at 60 ° C., 80 A humidification treatment was performed with% RH for 24 hours, and the mixture was allowed to stand at 40 ° C.
- the photochromic adhesive sheet after performing the above treatment becomes an adhesive layer made of the photochromic adhesive composition.
- the color density as a photochromic property was 0.9, and the fading speed was 45 seconds.
- the peel strength was 200 N / 25 mm in a 23 ° C. atmosphere and 60 N / 25 mm in a 150 ° C. atmosphere.
- the softening point of the photochromic adhesive sheet produced separately by the same method was 180 ° C.
- Table 4 shows the film thickness of the adhesive layer made of the photochromic adhesive composition and the presence / absence / thickness of use of the second adhesive layer.
- the obtained photochromic laminate was evaluated in the same manner as in Example 1.
- Table 6 shows photochromic properties and peel strength
- Table 7 shows bending and injection moldability.
- Examples 17-33 A photochromic adhesive composition was prepared in the same manner as in Examples 15 and 16 except that (A) photochromic compound, (B) adhesive urethane (urea) resin, and (C) component shown in Table 4 were used.
- the softening point of the obtained photochromic adhesive composition was measured in the same manner as in Examples 15 and 16, and is shown in Table 4.
- a photochromic laminate was prepared using each photochromic adhesive composition according to the same method as in Example 15 (without the second adhesive layer) or Example 16 (with the second adhesive layer).
- Table 4 shows the film thickness of the adhesive layer made of the photochromic adhesive composition and the presence / absence / thickness of use of the second adhesive layer. Further, the obtained photochromic laminate was evaluated in the same manner as in Example 1.
- Table 6 shows photochromic properties and peel strength, and Table 7 shows bending workability and injection moldability.
- a photochromic adhesive composition was prepared in the same manner as in Examples 15 and 16 except that (A) photochromic compound, (B) adhesive urethane (urea) resin, and C component shown in Table 4 were used.
- the softening point of the obtained photochromic adhesive composition was measured in the same manner as in Examples 15 and 16, and is shown in Table 4.
- a photochromic laminate was prepared using each photochromic adhesive composition according to the same method as in Example 15 (without the second adhesive layer) or Example 16 (with the second adhesive layer).
- Table 4 shows the film thickness of the adhesive layer made of the photochromic adhesive composition and the presence / absence / thickness of use of the second adhesive layer.
- the obtained photochromic laminate was evaluated in the same manner as in Example 1.
- Table 6 shows the photochromic properties and peel strength, and Table 7 shows the bending work and injection moldability.
- a softening point comprising a photochromic compound having a molecular chain having a molecular weight of 300 or more as a substituent
- an adhesive urethane (urea) resin By using a photochromic adhesive composition having a temperature of 140 to 220 ° C., it can be seen that it has excellent photochromic properties, peel strength (adhesion), bending workability, and injection moldability.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Ophthalmology & Optometry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- General Health & Medical Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Laminated Bodies (AREA)
- Optical Filters (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
Description
(A)分子量が300以上の分子鎖を置換基として有するフォトクロミック化合物(以下、単に「(A)成分」とする場合もある。)、及び
(B)接着性ウレタン(ウレア)樹脂(以下、単に「(B)成分」とする場合もある。)を含み、
軟化点が140~220℃となるフォトクロミック接着性組成物である。
前記(A)フォトクロミック化合物が、分子量が300以上の分子鎖を置換基として有するものであり、かつ、
前記(B)接着性ウレタン(ウレア)樹脂を含んでなり、
軟化点が140~220℃の耐熱性を有するフォトクロミック接着性組成物である。なお、軟化点の測定方法は、実施例に記載の方法で測定した値である。本発明のフォトクロミック接着性組成物は、特に、光学シートとの接着性に優れる。
本発明に使用するフォトクロミック化合物(A)は、分子量が300以上の分子鎖を置換基として有するものであれば、特に制限無く公知の化合物の中から、任意のものを適宜選択し使用できる。分子量が300以上の分子鎖は、高分子量のものであるため、フォトクロミック化合物を製造する際に、1種類の分子鎖ではなく、複数種類の分子鎖を有するものとなる場合がある。その場合、該分子鎖の分子量は、平均値をとればよい。また、この平均値は、数平均分子量であればよい。この分子量は、フォトクロミック化合物の製造時の原料の種類により確認できるし、製造物から確認する場合には、NMR、IR、質量分析等の公知の手段により確認できる。本発明においては、使用した原料から求めた分子量を採用している。
500~10,000であることが特に好ましい。さらに、高いフォトクロミック特性、接着層等中における(A)成分の分散性、および(A)成分自体の生産性を考慮すると、該分子鎖の分子量は、700~5,000であることが好ましく、1,000~3,000であることがより好ましい。
本発明において、好適な(A)成分は、下記式(1)、及び(2)から選択される、少なくとも1種のフォトクロミック化合物である。
PC-(L-Chain) (1)
PC-(L-Chain-L’)-PC’ (2)
L、およびL'は、それぞれ、ポリオキシアルキレン鎖、(チオ)エステル基、(チオ)アミド基から選択される少なくとも1種の基を含む2価の有機基であり、LとL'とは、同一でも異なっていてもよく、
Chainは、ポリシロキサン鎖、ポリオキシアルキレン鎖から選択される少なくとも1種の鎖を含む1価または2価の有機基であり、
LおよびChain、またはL、L’およびChainの合計の分子量が前記分子鎖の分子量に該当する。つまり、式(1)におけるLおよびChain、または式(2)におけるL、L’およびChainの部分が分子鎖に該当する。
PC、又はPC’は、それぞれ、下記式(3)~(7)で示される基本骨格を有する化合物から選ばれる。
置換基を有することができる炭素原子又は窒素原子の内、1つの原子が2価の有機基であるL又はL’と直接結合し、その他の原子は他の置換基を有してもよく、又は
置換基を有することができる炭素原子又は窒素原子の内、1つの原子が置換基を介して2価の有機基であるL又はL’と結合し、その他の原子は他の置換基を有してもよい。
前記式(3)で示される基本骨格において、好ましい基本骨格は、下記式(3’)で示される構造である。
前記式(3’)におけるR1、およびR2は、それぞれ、水素原子、ヒドロキシル基、炭素数1~6のアルキル基、炭素数1~6のハロアルキル基、置換基を有してもよい炭素数3~8のシクロアルキル基、炭素数1~6のアルコキシ基、アミノ基、置換アミノ基、置換基を有してもよい複素環基、シアノ基、ハロゲン原子、炭素数1~6のアルキルチオ基、置換基を有してもよい炭素数6~10のアリールチオ基、ニトロ基、ホルミル基、ヒドロキシカルボニル基、炭素数2~7のアルキルカルボニル基、炭素数2~7のアルコキシカルボニル基、置換基を有してもよい炭素数7~11のアラルキル基、置換基を有してもよい炭素数7~11のアラルコキシ基、置換基を有してもよい炭素数6~12のアリールオキシ基、置換基を有してもよい炭素数6~12のアリール基、置換基を有してもよい炭素数3~12のヘテロアリール基、チオール基、炭素数2~9のアルコキシアルキルチオ基、炭素数1~6ハロアルキルチオ基、又は置換基を有してもよい炭素数3~8のシクロアルキルチオ基などが挙げられる。
前記式(3’)におけるR3、およびR4は、それぞれ、水素原子、置換基を有してもよい炭素数6~20のアリール基、又は置換基を有してもよい炭素数3~20のヘテロアリール基である。
ヒドロキシル基、炭素数1~6のアルキル基、炭素数1~6のハロアルキル基、炭素数3~8のシクロアルキル基、炭素数1~6のアルコキシ基、アミノ基、複素環基、シアノ基、ハロゲン原子、
炭素数1~6のアルキルチオ基、置換基を有してもよい炭素数6~10のアリールチオ基から選ばれる置換基が挙げられる。
前記式(3’)におけるR5、およびR6は、水素原子、ハロゲン原子、カルボキシル基、アセチル基、炭素数1~10のアルキル基、炭素数2~10のアルケニル基、炭素数1~10のアルコキシ基、炭素数1~10のヒドロキシアルキル基、炭素数1~10のアルコキシ基で置換された炭素数1~10のアルキル基、炭素数1~10のアミノアルキル基、炭素数3~20のシクロアルキル基、置換基を有してもよい炭素数6~20のアリール基、炭素数2~15のアルコキシカルボニル基、又は置換基を有してもよい炭素数3~20ヘテロアリール基などが挙げられる。
前記式(3’)で示される基本骨格が有する分子鎖は、R1~R6の一つが結合手となって、直接、基本骨格と結合することができる。つまり、R1~R6の一つが下記に詳述する-(L-Chain)、または-(L-Chain-L’)-となってもよい(R1~R6の一つが分子鎖となることができる。)。なお、R1~R6は、R1、R2、R3、R4、R5、R6をまとめて示している。以下、R1~R6を使用した場合にはこれに従うものとする。
以上のような基の中でも、得られたフォトクロミック化合物の発色濃度、発色色調等を考慮すると、前記式(3’)における、好適なR1~R6は、以下の通りである。
前記式(4)で示される基本骨格において、好ましい基本骨格は、下記式(4’)で示される構造である。
前記式(4’)におけるR1~R4は、前記式(3’)の<式(3’);R1、およびR2>、<式(3’);R3、およびR4>で説明した基と同じ基が挙げられる。
前記式(4’)におけるR7は、前記式(3’)の<式(3’);R1、およびR2>で説明した基と同じ基が挙げられる。
前記式(4’)におけるR8、およびR9は、それぞれ、水素原子、ヒドロキシル基、炭素数1~6のアルキル基、炭素数1~6のハロアルキル基、置換基を有してもよい炭素数3~8のシクロアルキル基、炭素数1~6のアルコキシ基、アミノ基、置換アミノ基、置換基を有してもよい複素環基、シアノ基、ニトロ基、炭素数1~6のアルコキシアルキル基、ホルミル基、ヒドロキシカルボニル基、炭素数2~7のアルキルカルボニル基、炭素数2~7のアルコキシカルボニル基、ハロゲン原子、置換基を有してもよい炭素数7~11のアラルキル基、置換基を有してもよい炭素数7~11のアラルコキシ基、置換基を有してもよい炭素数6~12のアリール基、チオール基、炭素数1~6のアルキルチオ基、炭素数3~8のシクロアルキルチオ基、置換基を有していてもよい複素環基、または置換基を有してもよい炭素数6~10のアリールチオ基である。
前記式(4’)で示される基本骨格が有する分子鎖は、R1~R4、R7~R9の一つが結合手となって、直接、基本骨格と結合することができる。つまり、R1~R4、R7~R9の一つが下記に詳述する-(L-Chain)、または-(L-Chain-L’)-となってもよい(R1~R4、R7~R9の一つが分子鎖となることができる。)。
前記式(4’)における、好適なR1~R4、R7~R9は、以下の通りである。
前記式(5)で示される基本骨格において、好ましい基本骨格は、下記式(5’)で示される構造である。
前記式(5’)におけるR3、およびR4は、前記式(3’)の<式(3’);R3、およびR4>で説明した基と同じ基が挙げられる。
前記式(5’)におけるR10~R12は、前記式(3’)の<式(3’);R1、およびR2>で説明した基と同じ基が挙げられる。
前記式(5’)で示される基本骨格が有する分子鎖は、R3、R4、R10~R12の一つが結合手となって、直接、基本骨格と結合することができる。つまり、R3、R4、R10~R12の一つが下記に詳述する-(L-Chain)、または-(L-Chain-L’)-となってもよい(R3、R4、R10~R12の一つが分子鎖となることができる。)。
前記式(6)で示される基本骨格において、好ましい基本骨格は、下記式(6’)で示される構造である。
前記式(6’)におけるR13、R17、R18、およびR19は、前記式(3’)の<式(3’);R1、およびR2>で説明した基と同じ基が挙げられる。
前記式(6’)におけるR16は水素原子、ハロゲン原子、炭素数1~20のアルキル基、炭素数1~5のハロアルキル基、炭素数1~5のジハロアルキル基、炭素数1~5のトリハロアルキル基、炭素数3~20の置換基を有してもよいシクロアルキル基、炭素数6~20の置換基を有してもよいビシクロアルキル基、置換基を有してもよい炭素数6~20のアリール基が挙げられる。
前記式(6’)におけるR14、およびR15は、水素原子、ハロゲン原子、炭素数1~10のアルキル基、置換基を有してもよい炭素数3~20のシクロアルキル基等が挙げられる。
前記式(6’)で示される基本骨格が有する分子鎖は、R13~R19の一つが結合手となって、直接、基本骨格と結合することができる。つまり、R13~R19の一つが下記に詳述する-(L-Chain)、または-(L-Chain-L’)-となってもよい(R13~R19の一つが分子鎖となることができる。)。
前記式(7)で示される基本骨格において、好ましい基本骨格は、下記式(7’)で示される構造である。
前記式(7’)におけるR13、R18、およびR19は、前記式(6’)の<式(6’);R13、R17、R18、およびR19)>((<式(3’);R1、およびR2>))で説明した基と同じ基が挙げられる。
前記式(7’)におけるR14、およびR15は、前記式(6’)の<式(6’);R14、およびR15>で説明した基と同じ基が挙げられる。
前記式(7’)におけるR20、およびR21は、前記式(6’)の<式(6’);R14、およびR15>((<式(7’);R14、およびR15>))で説明した基と同じ基が挙げられる。
前記式(7’)で示される基本骨格が有する分子鎖は、R13~R15、およびR18~R21の一つが結合手となって、直接、基本骨格と結合することができる。つまり、R13~R15、およびR18~R21の一つが下記に詳述する-(L-Chain)、または-(L-Chain-L’)-となってもよい(R13~R15、およびR18~R21の一つが分子鎖となることができる。)。
前記式(1)、および(2)において、L、又はL’は、ポリオキシアルキレン鎖、(チオ)エステル基、(チオ)アミド基から選ばれる少なくとも1種の基を含む2価の結合基であることが好ましい。
R22は、2価の基であり、炭素数が1~20の直鎖状若しくは分岐鎖状アルキレン基、環を形成する炭素数が3~12の置換基を有してもよいシクロアルキル基、環を形成する炭素数が6~12の置換基を有してもよいアリール基、又は環を形成する原子の数が3~12である置換基を有してもよい複素環基であり、
R23は、2価の基であり、炭素数が1~20の直鎖状若しくは分岐鎖状アルキレン基、環を形成する炭素数が3~12の置換基を有してもよいシクロアルキル基、又は環を形成する炭素数が6~12の置換基を有してもよいアリール基であり、
R24は、2価の基であり、炭素数が1~20の直鎖状若しくは分岐鎖状アルキレン基、環を形成する炭素数が3~12の置換基を有してもよいシクロアルキル基、又は環を形成する炭素数が6~12の置換基を有してもよいアリール基であり、
R27は、2価の基であり、炭素数が1~20の直鎖状若しくは分岐鎖状アルキレン基、環を形成する炭素数が3~12の置換基を有してもよいシクロアルキル基、環を形成する炭素数が6~12の置換基を有してもよいアリール基、又は環を形成する原子の数が3~12である置換基を有してもよい複素環基であり、
X1、およびX2は、2価の基であり、それぞれ独立に、直結、O、S、アミノ基、置換アミノ基、(チオ)アミド基、又は(チオ)エステル基であり、
R23’は、2価の基であり、炭素数が1~20の直鎖状若しくは分岐鎖状アルキレン基、環を形成する炭素数が3~12の置換基を有してもよいシクロアルキル基、又は環を形成する炭素数が6~12の置換基を有してもよいアリール基であり、
dは0~50の整数であり、eは0~50の整数であり、e’は0~50の整数であり、fは0~50の整数であり、gは0~50の整数であり、2つのeは同一でも異なっていてもよく、
dが2以上の場合、複数あるR22は、互いに同一であっても異なっていてもよく、
eが2以上の場合、複数あるeの単位の2価の基は、互いに同一であっても異なっていてもよく、
e’が2以上の場合、複数あるe’の単位の2価の基は、互いに同一であっても異なっていてもよく、
fが2以上の場合、複数あるfの単位の2価の基は、互いに同一であっても異なっていてもよく、
gが2以上の場合、複数あるgの単位の2価の基は、互いに同一であっても異なっていてもよい。
前記式(1)、および(2)において、「Chain」部分は、ポリアルキレンオキシド鎖、ポリエステル鎖、ポリエステルポリエーテル鎖、及びポリシロキサン鎖から選ばれる少なくとも1種の鎖を含む1価、または2価の基であることが好ましい。中でも、下記式(9a)~(9d)で示される繰り返し単位を有する鎖となることが好ましい。
R25は、炭素数1~20の直鎖状又は分岐鎖状のアルキレン基であり、同一分子内に複数のR25を含む場合は、R25は、互いに同一であっても異なっていてもよく、
nは、前記オリゴマー鎖基の繰り返し単位を指すものであり、3~200の整数であり、複数ある繰り返し単位の2価の基は、互いに同一であっても異なっていてもよい。
R26は、炭素数1~20の直鎖状又は分岐鎖状のアルキル基、または炭素数6~14のアリール基であり、同一分子内に複数のR26を含む場合は、R26は、互いに同一であっても異なっていてもよい。}
で示される基である。
本発明において、優れた効果を発揮するためには、前記(A)成分としては、下記組み合わせのフォトクロミック化合物を使用することが好ましい。つまりは、PC、又はPC’が前記式(3’)、(4’)、及び(5’)のナフトピラン骨格の中から選ばれる一つであり、L、L’が前記式(8)であり、「Chain」部分が前記式(9a)~(9d)の中から選ばれる一つである。
次に、(B)成分である接着性ウレタン(ウレア)樹脂について説明する。
本発明において、(B)接着性ウレタン(ウレア)樹脂がフォトクロミック接着性組成物の軟化点を主に決定する。(A)成分、および(B)成分を含むフォトクロミック接着性組成物の軟化点が140~220℃を満足するような(B)成分でなければならない。そのため、特に制限されるものではないが、(B)成分の軟化点は、特に優れた効果を発揮するためには、(C)成分を使用しない場合には、140~220℃であることが好ましく、150~200℃であることがより好ましく、160~190℃であることがさらに好ましい。また、下記に詳述する(C)成分を使用する場合には、(C)成分による架橋効果が望まれるため、(B)成分単独での軟化点は、120~220℃であることが好ましく、130~200℃であることがより好ましく、140~190℃であることさらに好ましく、140~170℃であることが特に好ましい。なお、(C)成分を使用した場合には、この(C)成分で該(B)成分を架橋したウレタン(ウレア)樹脂の軟化点が、140~220℃であることが好ましく、150~200℃であることがより好ましく、155~195℃であることがさらに好ましく、160~190℃であることが特に好ましい。
該ウレタン(ウレア)樹脂に使用されるポリオール化合物としては、ポリエーテルポリオール、ポリカーボネートポリオール、ポリカプロラクトンポリオール、ポリエステルポリオールなどのポリオール化合物を使用することできる。中でも、耐熱性、密着性、フォトクロミック特性などの観点から、ポリカーボネートポリオール、ポリカプロラクトンポリオールを使用することが好ましい。該ポリオール化合物の数平均分子量は、400~3000であることが好ましい。中でも、耐熱性、フォトクロミック特性の観点から、数平均分子量は400~2500であることが好ましく、400~2000であることがより好ましい。
該ウレタン(ウレア)樹脂に使用されるポリイソシアネート化合物としては、耐候性の観点から脂肪族ポリイソシアネート化合物、または脂環式ポリイソシアネート化合物を用いることが好ましい。具体的には、テトラメチレン-1,4-ジイソシアネート、ヘキサメチレン-1,6-ジイソシアネート、オクタメチレン-1,8-ジイソシアネート、2,2,4-トリメチルヘキサン-1,6-ジイソシアネートなどの脂肪族ポリイソシアネート化合物、シクロヘキサン-1,3-ジイソシアネート、シクロヘキサン-1,4-ジイソシアネート、2,4-メチルシクロヘキシルジイソシアネート、2,6-メチルシクロヘキシルジイソシアネート、イソホロンジイソシアネート、ノルボルネンジイソシアネート、4,4’-メチレンビス(シクロヘキシルイソシアネート)の異性体混合物、ヘキサヒドロトルエン-2,4-ジイソシアネート、ヘキサヒドロトルエン-2,6-ジイソシアネート、ヘキサヒドロフェニレン-1,3-ジイソシアネート、ヘキサヒドロフェニレン-1,4-ジイソシアネートなどの脂環式ポリイソシアネート化合物を挙げることができ、特に耐熱性の観点から、イソホロンジイソシアネート、4,4’-メチレンビス(シクロヘキシルイソシアネート)の異性体混合物、ノルボルネンジイソシアネートを用いることが好ましい。
該ウレタン(ウレア)樹脂に使用される活性水素含有化合物は、(B)ウレタン(ウレア)樹脂を合成する際の鎖延長剤、または架橋剤として機能するものであり、得られるウレタン(ウレア)樹脂の耐熱性、フォトクロミック特性の観点から、分子量50~300の化合物を使用することが好ましい。具体的には、ジアミン化合物、トリアミン化合物などのアミノ基含有化合物、ジオール化合物、トリオール化合物などの水酸基含有化合物を使用できる。
本発明において、(B)成分は、末端がイソシアネート基等の反応性基であってもよいが、下記に詳述する(C)成分を使用する場合には、末端が非反応性基となっていることが好ましい。具体的には、(C)成分を配合する場合には、(B)成分は、分子末端に残存するイソシアネート基を、イソシアネート基と反応しうる活性水素基を有する公知の単官能物質(反応停止剤;以下、単に(B4)成分とする場合もある。)と反応させ、非反応性にしたものを使用することが好ましい。反応停止剤としては、アミン、アルコール、チオール、及びカルボン酸を用いることができる。具体的には、ノルマルブチルアミン、sec-ブチルアミン、tert-ブチルアミン、ジブチルアミン、ジイソプロピルアミン、メタノール、エタノール、イソプロパノール、ノルマルブタノール、sec-ブタノール、tert-ブタノール、酢酸等を挙げることができる。また、酸化防止機能性付与化合物、光安定性機能性付与化合物を反応停止剤として使用することにより、ポリウレタン-ウレア樹脂に機能性付与化合物を導入すると同時に末端のイソシアネート基を不活性化することができる。
本発明のフォトクロミック接着性組成物における接着性ウレタン(ウレア)樹脂(B成分)を構成する上記各成分、即ち(B1)成分、(B2)成分の量比は、ウレタン(ウレア)樹脂を使用する用途等を勘案して適宜決定すればよいが、得られるウレタン(ウレア)樹脂の耐熱性、接着力などのバランスの観点から、次のような量比とすることが好ましい。すなわち、(B1)成分に含まれる水酸基の総モル数をn1とし、(B2)成分に含まれるイソシアネート基の総モル数をn2としたときに、n1:n2=0.2~0.8:1.0となる量比が好ましく、n1:n2=0.3~0.7:1.0となる量比がより好ましい。また、(B1)、(B2)成分に加えて、(B3)成分を構成成分に使用した場合、(B1)成分、(B2)成分、(B3)成分の量比は、得られるウレタン(ウレア)樹脂の耐熱性、接着力などのバランスの観点から、次のような量比とすることが好ましい。すなわち、(B1)成分に含まれる水酸基の総モル数をn1とし、(B2)成分に含まれるイソシアネート基の総モル数をn2とし、(B3)成分に含まれる活性水素基の総モル数をn3としたときに、n1:n2:n3=0.2~0.8:1.0:0.2~0.8となる量比が好ましく、特にn1:n2:n3=0.3~0.7:1.0:0.3~0.7となる量比とすることが好ましい。ここで、上記n1~n3は、各成分として用いる化合物の使用モル数と該化合物1分子中に存在する各基の数の積として求めることができる。
n1:n2:n3:n4=0.2~0.8:1.0:0.2~0.8:0.01~0.2とする量比が好ましく、n1:n2:n3:n4=0.3~0.7:1.0:0.3~0.7:0.01~0.18とする量比がより好ましい。そして、(B4)成分を使用する場合には、n2=n1+n3+n4=1.0となる。
上記(B1)成分、(B2)成分を反応させて、(B)成分を得る場合には、たとえば次のような方法によって好適に(B)成分を得ることができる。
(B1)成分と(B2)成分とを反応さてウレタンプレポリマーを得、次いで該ウレタンプレポリマーと、(B3)成分を反応性させることにより、(B)成分となる接着性ウレタン(ウレア)樹脂を合成することができる。
本発明のフォトクロミック接着性組成物は、前記(A)成分、及び前記(B)接着性ウレタン(ウレア)樹脂を含んでなり、
軟化点が140~220℃とならなければならない。すなわち、特定の分子鎖を有する前記(A)成分を使用し、前記(B)接着性ウレタン(ウレア)樹脂を含み、かつ、軟化点を140~220℃に調整しなければならない。
本発明のフォトクロミック接着性組成物は、上記(A)成分、(B)成分、及びその他の成分を混合することにより製造することができる。各成分を混合する順序は、特に制限されるものではない。
本発明において、フォトクロミック化合物の配合量は、フォトクロミック特性の観点から、(B)成分100質量部に対して、0.1~20.0質量部とすることが好ましい。上記配合量が少なすぎる場合には、十分な発色濃度や耐久性が得られない傾向がある。一方、多すぎる場合には、フォトクロミック化合物の種類にもよるが、フォトクロミック接着性組成物に溶解しにくくなり、組成物の均一性が低下する傾向があるばかりでなく、接着力(密着力)が低下する傾向もある。発色濃度や耐久性といったフォトクロミック特性を維持したまま、接着性を十分に保持するためには、フォトクロミック化合物の添加量は、樹脂成分合計量100質量部に対して、0.5~20.0質量部とすることがより好ましく、1.0~15.0質量部とすることがさらに好ましい。
本発明のフォトクロミック接着性組成物において、(B)成分である接着性ウレタン(ウレア)樹脂の軟化点が140℃未満の場合であっても、(C)成分を配合することでフォトクロミック接着性組成物の軟化点を140℃以上とすることもできる。この理由は、(B)成分のウレタン(ウレア)樹脂中のウレタン(ウレア)結合に(C)成分のイソシアネート基が作用し、部分的に高分子量化、又は架橋構造を形成すると考えられ、フォトクロミック接着性組成物の軟化点を140~220℃の範囲とすることができる。その結果、(C)成分を含むフォトクロミック接着性組成物は、光学シートとの密着性、耐熱性が向上するものと推測される。その中でも、該ウレタン(ウレア)樹脂が分子末端に反応性基を有さない非反応性ウレタン(ウレア)樹脂である場合、特に(B4)成分を配合して末端を非反応性基とした(B)成分を用いた場合に、(C)成分を併用することで優れた効果を発揮する。また、前記説明では、(B)成分の軟化点が140℃未満である場合の説明をしたが、最終的に得られるフォトクロミック接着性組成物の軟化点が140~220℃の範囲を満足するのであれば、当然、軟化点が140℃以上の(B)成分と(C)成分とを組み合わせて使用することもできる。
本発明において、フォトクロミック接着性組成物には、フォトクロミック特性を付与する成分以外に、界面活性剤、ヒンダードアミン光安定剤、ヒンダードフェーノール酸化防止剤、フェノール系ラジカル補足剤、イオウ系酸化防止剤、リン系酸化防止剤、紫外線安定剤、紫外線吸収剤、離型剤、着色防止剤、帯電防止剤、蛍光染料、染料、顔料、香料、可塑剤等の添加剤を配合することもできる。これら添加剤としては、公知の化合物が何ら制限なく使用され、これらは2種以上を混合して使用してもよい。これら添加剤は、フォトクロミック接着性組成物を製造する際に、混合すればよい。上記添加剤の添加量は、本発明の効果を阻害しない範囲で配合することができる。具体的には、(B)成分100質量部に対して、添加剤の合計量が0.001~10質量部の範囲となることが好ましい。
より具体的に説明すると、有機溶媒を使用することにより、フォトクロミック化合物((A)成分)、ウレタン(ウレア)樹脂((B)成分)、さらには、必要に応じて添加されるその他の成分が混合しやすくなる。そして、フォトクロミック接着性組成物の均一性を向上させることができる。また、フォトクロミック接着性組成物、又は該フォトクロミック接着性組成物を構成する各成分の混合物の粘度を適度に調整することができる。そして、光学シートに塗布するときの操作性および塗布層厚の均一性を高くすることもできる。なお、光学シートとして有機溶媒に侵され易い材質のものを使用した場合には、外観不良が生じたり、フォトクロミック特性が低下したりするという問題が発生することが懸念されるが、このような問題は、後述する方法を採用することにより回避することができる。また、フォトクロミック接着性組成物、又は該各成分の混合物においては、後述するように、様々な種類の溶媒が使用できるので、溶媒として光学シートを侵し難い溶媒を選択して使用することによっても上記問題の発生を防止することができる。
有機溶媒の使用量は、特に制限されるものではないが、接着性ウレタン(ウレア)樹脂成分((B)成分) 100質量部に対して、100~500質量部が好ましい。
以下、フォトクロミック積層体について説明する。
フォトクロミック積層体は、互いに対向する2枚の光学シートが本発明のフォトクロミック接着組成物からなる接着層を介して接合された積層構造を含む。図1に、該フォトクロミック積層体の好適な層構成の断面図を示した。図1を用いて説明すると、フォトクロミック積層体1は、光学シート2、4が、フォトクロミック接着性組成物からなる接着層3を介して接合されてなる積層構造を有することが好ましい。本発明においては、この接着層の軟化点が140~220℃となる必要がある。このフォトクロミック積層体に使用できる光学シートについて説明する。
本発明において、(D)光学シートとしては、光透過性を有するシートであれば、特に制限なく使用できるが、入手の容易性および加工のし易さなどの観点から樹脂製のものを使用することが好適である。該(D)光学シートの原料として好適な樹脂を例示すれば、ポリカーボネート樹脂、ポリエステル樹脂、セルロース樹脂、ポリアミド樹脂、(メタ)アクリル樹脂、ポリウレタン樹脂、ポリウレタンウレア樹脂、エポキシ樹脂、ポリイミド樹脂、ポリオレフィン樹脂及びポリビニルアルコール樹脂などが挙げられる。その中でも、接着性が良好で射出成形法に対する適用性が高いという理由からポリカーボネート樹脂、ポリアミド樹脂が特に好ましい。
本発明のフォトクロミック積層体は、互いに対向する2枚の光学シートを、本発明のフォトクロミック接着性組成物からなる接着層を介して接合させることにより製造される。なお、該接着層の厚さは、フォトクロミック化合物の発色濃度、耐候性および接着強度などの観点から、5~100μm、特に10~60μmとすることが好ましい。
また、本発明のフォトクロミック接着性組成物、および有機溶媒を含む混合物を使用する場合には、(I)平滑な基材上に該混合物を延展せしめた後に乾燥することにより有機溶媒を除去し、その後、基材を剥がして、フォトクロミック性接着シートを作製し、次いで(II)互いに対向する2枚の光学シートの間に上記フォトクロミック性接着シートを介在させて該2枚の光学シートを接合することにより、本発明のフォトクロミック積層体を製造することもできる。最終的な処理を終えて得られたフォトクロミック積層体において、フォトクロミック性接着シートの部分が接着層となる。なお、前記フォトクロミック接着性組成物は、該フォトクロミック接着性組成物を構成する各成分の混合物であってもよい。有機溶媒を含む該混合物を接着層とする際に、フォトクロミック接着性組成物からなる接着層を形成することもできる。
上記平滑な基材の材質としては、本発明で使用する溶剤に耐性があるもの、また該接着層が剥離しやすいものが好ましく、具体的に例示すれば、ガラス、ステンレス、テフロン(登録商標)、ポリエチレンテレフタレート、ポリプロピレン、さらにはシリコン系やフッ素系などの剥離性を向上させるコート層を積層させたプラスチックフィルムなどが挙げられる。
また、第二接着層の膜厚は、特に制限されるものではないが、5~15μmとすることが好ましい。なお、2枚の光学シートの両方に第二接着層を設けることが好ましい。そして、フォトクロミック接着性組成物からなる接着層の厚みに対する、第二接着層の合計厚みの比(第二接着層の合計厚み/接着層の厚み)が0.1~0.9となることが好ましく、0.3~0.7となることがより好ましい。
本発明においては、フォトクロミック積層体の少なくとも一方の外表面に、プラスチック光学基材等の合成樹脂層を積層した光学物品とすることができる。
例えば、本発明においては、前記フォトクロミック積層体と、プラスチックレンズ本体などの光学基材とを一体化することにより光学物品を得る。この光学基材の原料としては、前記光学シートの原料と同様のものが挙げられる。一体化する方法としては、例えば、上記本発明のフォトクロミック積層体を金型内に装着した後に、光学基材(例えば、レンズ本体)を構成するための熱可塑性樹脂を射出成形する方法(以下、単に射出成形法ともいう。)、光学基材の表面に接着剤などによりフォトクロミック積層体を貼付する方法などを挙げることができる。また、光学基材を形成できる重合性モノマー中にフォトクロミック積層体を浸漬した後、該重合性モノマーを硬化させることにより、光学基材中にフォトクロミック積層体を埋設させて一体化することもできる。そのため、上記光学物品は、熱可塑性樹脂、又は熱硬化性樹脂よりなるプラスチック光学基材上に、上記フォトクロミック積層体を積層したものであってもよいし、該プラスチック光学基材中に埋設したものであってもよい。該プラスチック光学基材などの合成樹脂層としては、ポリエステル樹脂、ポリアミド樹脂、アリル樹脂、(メタ)アクリル樹脂、ポリウレタン樹脂、ポリウレタンウレア樹脂、ポリチオウレタン樹脂、ポリエポキシ樹脂、ポリチオエポキシ樹脂、及びポリカーボネート樹脂などの公知の樹脂を挙げることができる。
以下に、実施例及び比較例で各成分として使用した化合物等の略号を纏める。
<PC1>の合成
実施例に使用した下記式(PC1)は、例えば、国際公開第2009-146509号に記載の製造方法を参考にして製造できる。例えば、国際公開第2009-146509号において、2-ヒドロキシ-エトキシカルボニル基を有するナフトピラン化合物とカルボキシル基を両末端に有するポリジメチルシロキサンとを反応させることにより、製造できる。分子鎖の(平均)分子量は、1350である。該PC1は、分子鎖を置換基として有するフォトクロミック化合物である。
前記式(PC1)で示されるフォトクロミック化合物と同様に、国際公開第2009-146509号に記載の方法を参考にして、それに対応するナフトピラン化合物反応させて合成した。分子鎖の(平均)分子量は1438である。該PC2は、分子鎖を置換基として有するフォトクロミック化合物である。
PL1:旭化成ケミカルズ株式会社製デュラノール(1,5-ペンタンジオールとヘキサンジオールを原料とするポリカーボネートポリオール、数平均分子量500)。
PL2:旭化成ケミカルズ株式会社製デュラノール(1,5-ペンタンジオールとヘキサンジオールを原料とするポリカーボネートポリオール、数平均分子量800)。
PL3:旭化成ケミカルズ株式会社製デュラノール(1,5-ペンタンジオールとヘキサンジオールを原料とするポリカーボネートポリオール、数平均分子量1000)。
PL4:旭化成ケミカルズ株式会社製デュラノール(1,5-ペンタンジオールとヘキサンジオールを原料とするポリカーボネートポリオール、数平均分子量2000)。
PL5:ダイセル化学工業株式会社製プラクセル(ポリカプロラクトンポリオール、数平均分子量830)。
PL6:ダイセル化学工業株式会社製プラクセル(ポリカプロラクトンポリオール、数平均分子量1000)。
NCO1:4,4’-メチレンビス(シクロヘキシルイソシアネート)の異性体混合物。
NCO2:イソホロンジイソシアネート。
H1:1,4-ブタンジオール。
H2:イソホロンジアミン。
H3:ビス-(4-アミノシクロヘキシル)メタン。
H4:トリメチロールプロパン。
H5:ジ(トリメチロールプロパン)。
HA1:1,2,2,6,6-ペンタメチル-4-アミノピペリジン。
HA2:n-ブチルアミン。
C1:4,4’-メチレンビス(シクロヘキシルイソシアネート)の異性体混合物。
C2:ヘキサメチレンジイソシアネートの3量体(旭化成ケミカルズ株式会社製、製品名デュラネート24A-100)。
・L1:エチレンビス(オキシエチレン)ビス[3-(5-tert-ブチル-4-ヒドロキシ-m-トリル)プロピオネート](チバ・スペシャルティ・ケミカルズ社製、Irganox245)。
・L2:DOW CORNING TORAY L-7001(東レ・ダウコーニング株式会社製、界面活性剤)。
D1:THF(テトラヒドロフラン)。
D2:プロピレングリコール-モノメチルエーテル。
ウレタン樹脂(U1;(B)成分の前駆体)の合成
撹拌羽、冷却管、温度計、窒素ガス導入管を有する三つ口フラスコに、数平均分子量500のポリカーボネートジオール((B1)成分:PL1)250g、4,4’-メチレンビス(シクロヘキシルイソシアネート)((B2)成分:NCO1)262.4gを仕込み、窒素雰囲気下、100℃で8時間反応させ、プレポリマーを合成した。反応の終点はイソシアネート基の逆滴定法により確認した。反応終了後、反応液を30℃付近まで冷却し、THF1632gに溶解させ、次いで、鎖延長剤である1,4-ブタンジオール((B3)成分:H1)31.5gを滴下し、25℃で1時間反応させ、ウレタン樹脂(U1)のTHF溶液を得た。
表1に示すポリオール化合物((B1)成分)、ポリイソシアネート化合物((B2)成分)、活性水素含有化合物((B3)成分)を用い、前述のU1の合成方法と同様にして、U2~U13を合成した。U1~U13の(B1)、(B2)、(B3)成分の種類、モル配合割合を表1にまとめた。
撹拌羽、冷却管、温度計、窒素ガス導入管を有する三つ口フラスコに、数平均分子量500のポリカーボネートジオール((B1)成分:PL1)350g、イソホロンジイソシアネート((B2)成分:NCO2)222.3gを仕込み、窒素雰囲気下、100℃で8時間反応させ、プレポリマーを合成した。反応の終点はイソシアネート基の逆滴定法により確認した。反応終了後、反応液を30℃付近まで冷却し、THF2190gに溶解させ、次いで、鎖延長剤であるビス-(4-アミノシクロヘキシル)メタン((B3)成分:H3)53gを滴下し、25℃で1時間反応させ、その後さらに、1,2,2,6,6-ペンタメチル-4-アミノピペリジン((B4)成分:HA1)10.5gを滴下し、25℃で1時間反応させ、ウレタンウレア樹脂(UU1)のTHF溶液を得た。
表2に示すポリオール化合物((B1)成分)、ポリイソシアネート化合物((B2)成分)、活性水素含有化合物((B3)成分)、および反応停止剤((B4)成分)を用い、前述のUU1の合成方法と同様にして、UU2~UU11を合成した。
以上、UU1~UU11のB1、B2、B3、成分の種類、モル配合割合を表2にまとめた。また、別途、作製した各(B)成分(すなわち、UU1~UU11)の軟化点を表2に示した。軟化点は、実施例1に記載の方法に従って測定した。
第二接着層用ウレタンウレア樹脂(W1)の合成
撹拌羽、冷却管、温度計、窒素ガス導入管を有する三つ口フラスコに、数平均分子量1000のポリカーボネートジオール((B1)成分:PL3)225g、イソホロンジイソシアネート((B2)成分:NCO2)100gを仕込み、窒素雰囲気下、100℃で8時間反応させ、プレポリマーを合成した。反応の終点はイソシアネート基の逆滴定法により確認した。反応終了後、反応液を30℃付近まで冷却し、プロピレングリコール-モノメチルエーテル2057gに溶解させ、次いで、鎖延長剤であるイソホロンジアミン(((B3)成分:H2))36gを滴下し、25℃で1時間反応させ、その後さらに、反応停止剤であるn-ブチルアミン((B4)成分:HA2))2gを滴下し、25℃で1時間反応させ、第二接着層用ウレタンウレア樹脂(W1)溶液を得た。また、別途、作製した(W1)成分(第二接着層)の軟化点は、170℃であった。軟化点は、実施例1に記載の方法に従って測定した。
フォトクロミック接着性組成物の調製
ウレタン樹脂(U1)のTHF溶液10g、フォトクロミック化合物(PC1)75mg、架橋剤としてトリメチロールプロパン((B3)成分:H4)30mg、さらに酸化防止剤としてエチレンビス(オキシエチレン)ビス[3-(5-tert-ブチル-4-ヒドロキシ-m-トリル)プロピオネート] 25mg、界面活性剤としてDOW CORNING TORAY L-7001 3mgを添加し、室温で攪拌・混合を行い、フォトクロミック接着性組成物を構成するための混合物を得た。各成分の配合割合を表3に示した。
フォトクロミック特性としての発色濃度は0.9であり、退色速度は40秒であった。また、剥離強度は23℃雰囲気下で140N/25mm、150℃雰囲気で20N/25mmあった。また、該フォトクロミック接着性組成物の軟化点を以下のように測定したところ、軟化点は190℃であった。フォトクロミック接着性組成物からなる接着層の膜厚、第二接着層の使用の有無・膜厚について表3に示した。
次にこれらの評価方法、およびフォトクロミック積層体の評価方法について説明する。
フォトクロミック接着性組成物の軟化点は、フォトクロミック接着性組成物からなる接着層の軟化点であり、以下の方法により作製した試料を用いて測定した。上記積層体とは別に、試料を作製して測定した。具体的には、2枚のPET製フィルム間に各実施例及び比較例で用いたものと同じフォトクロミック接着性組成物を構成する混合物(有機溶媒を含む)を塗布した後、80℃で5分間乾燥させた。その後、PET製フィルムを剥がし、70℃で70時間加熱処理し、次いで60℃、80%RHで24時間の加湿処理を行い、最後に40℃、真空下で24時間静置することにより、フォトクロミック性接着シート(接着層)を得た。
〔測定条件〕 昇温速度:10℃/分、測定温度範囲:30~250℃、プローブ:先端径0.5mmの針入プローブ。この結果を表3に示した。
得られたフォトクロミック積層体を試料とし、これに、(株)浜松ホトニクス製のキセノンランプL-2480(300W)SHL-100を、エアロマスフィルター(コーニング社製)を介して23℃、フォトクロミック積層体表面でのビーム強度365nm=2.4mW/cm2、245nm=24μW/cm2で300秒間照射して発色させ、フォトクロミック積層体のフォトクロミック特性を測定した。
これら結果を表5に示した。
得られたフォトクロミック積層体を、25×100mmの接着部分を有する試験片とし、試験機(オートグラフAGS-500NX、島津製作所製)に装着し、クロスヘッドスピード100mm/minで引張り試験を行い、それぞれ下記1)~2)の剥離強度を測定した。
得られたフォトクロミック積層体を曲げ加工機(LEMA社製CPL32)を用いて、熱成型により、球面形状に曲げ加工を行った。吸引口を有する凹型の金型に、φ8cmのフォトクロミック積層体を設置し、吸引しながら140℃で2分加熱した。金型から取り外すことで球面形状に加工されたフォトクロミック積層体を得た。曲げ加工したフォトクロミック積層体を20枚作製し、外観評価を行ったところ、外観不良は確認されず、収率は100%であった。これら結果を表7に示した
なお、上記外観評価は、以下の方法により実施した。
外観評価は、高圧水銀灯を曲げ加工したフォトクロミック積層体表面に照射し、その投影を目視で観察し、フォトクロミック積層体に気泡が発生しているかを確認した。気泡の発生が全くない曲げ加工したフォトクロミック積層体を良品とし、気泡が1個以上発生した曲げ加工したフォトクロミック積層体を不良とした。表7に不良枚数を記載した。
得られた曲げ加工したフォトクロミック積層体を球面形状の金型に設置し、100℃に加熱した。射出成型機に120℃、5時間の予備加熱を行ったポリカーボネート樹脂のペレット(帝人化成製パンライト)を充填し、300℃、60rpmで加熱溶融し、射出圧力1400kg/cm2でフォトクロミック積層体を設置した金型に射出することで、ポリカーボネート樹脂と一体化し、ポリカーボネートからなる、フォトクロミック性眼鏡レンズを製造した。フォトクロミック性眼鏡レンズの外観評価を行ったところ、外観不良は確認されず、(熱)曲げ加工を含めたトータル収率は100%であった。なお、射出成型性の確認には、前記(熱)曲げ加工で良品と判断した曲げ加工したフォトクロミック積層体のみを使用した。これら結果を表7に示した
なお、上記外観評価は、以下の方法により実施した。
外観評価は、高圧水銀灯をフォトクロミック性眼鏡レンズに照射し、その投影を目視で観察し、接着性ウレタン(ウレア)樹脂の溶融による射出不良、及び気泡が発生しているかを確認した。接着性ウレタン(ウレア)樹脂の溶融による外観不良、及び気泡の発生が全くないフォトクロミック性眼鏡レンズを良品とし、接着性ウレタン(ウレア)樹脂の溶融による外観不良、又は気泡が1箇所以上発生したフォトクロミック性眼鏡レンズを不良とした。表7に不良枚数を記載した。
フォトクロミック接着性組成物の調製
実施例1におけるフォトクロミック接着性組成物(接着層)の調製と同じ方法で同じフォトクロミック接着性組成物を構成する混合物を得た。表3に配合を示した。
第二接着層用ウレタンウレア樹脂(W1)のプロピレングリコール-モノメチルエーテル溶液25gに、界面活性剤としてDOW CORNING TORAY L-7001 2.5mgを添加し、室温で攪拌・混合を行い、第二接着層用接着剤を得た。
第二接着層用接着剤を厚み300μmのポリカーボネートシート上に塗布し、110℃で10分間乾燥させることにより、膜厚10μmの第二接着層を有するポリカーボネートシートを得た。
フォトクロミック特性としての発色濃度は0.9であり、退色速度は40秒であった。また、剥離強度は23℃雰囲気下で180N/25mm、150℃雰囲気で40N/25mmあった。また、別途、同様の方法で作製したフォトクロミック接着性シートの軟化点は、190℃であった。フォトクロミック接着性組成物からなる接着層の膜厚、第二接着層の使用の有無・膜厚について表3に示した。なお、表3における第二接着層の厚みは、一方のシート上の厚みである。そのため、2枚のシートを接合する場合には、第二接着層の合計厚みは、表3の値の倍となる。
表3に示す(A)フォトクロミック化合物、(B)接着性ウレタン(ウレア)樹脂、(B3)活性水素含有化合物を用いた以外は、実施例2と同様の方法でフォトクロミック接着性組成物を調整した。得られたフォトクロミック接着性組成物の軟化点を実施例1、2と同様の方法で測定し、表3に示した。
表3に示す(A)フォトクロミック化合物、(B)接着性ウレタン(ウレア)樹脂を用いた以外は、実施例1と同様の方法でフォトクロミック接着性組成物を調整した。得られたフォトクロミック接着性組成物の軟化点を実施例1、2と同様の方法で測定し、表3に示した。
フォトクロミック接着性組成物の調製
ウレタンウレア樹脂(UU1)のTHF溶液10g、フォトクロミック化合物(PC1)82mg、4,4’-メチレンビス(シクロヘキシルイソシアネート)の異性体混合物((C)成分;C1)250mg、さらに酸化防止剤としてエチレンビス(オキシエチレン)ビス[3-(5-tert-ブチル-4-ヒドロキシ-m-トリル)プロピオネート] 28mg、界面活性剤としてDOW CORNING TORAY L-7001 3mgを添加し、室温で攪拌・混合を行い、フォトクロミック接着性組成物を構成する混合物を得た。各成分の配合割合を表4に示した。軟化点も表4に示した。
上記有機溶媒を含む混合物を、PET(ポリエチレンテレフタレート)製フィルム(帝人デュポンフィルム株式会社製ピューレックスフィルム、シリコン塗膜付)に塗布し、80℃で5分間乾燥させた後、PET製フィルムを剥がして厚み約40μmのフォトクロミック性接着シートを得た。次いで、得られたフォトクロミック性接着シートを、厚み300μmのポリカーボネートシート2枚の間に挟み、40℃、真空下で24時間静置した後、100℃で1時間加熱処理し、次いで60℃、80%RHで24時間の加湿処理を行い、最後に40℃、真空下で24時間静置することにより、目的のフォトクロミック特性を有するフォトクロミック積層体を得た。以上のような処理を行った後のフォトクロミック性接着シートが、フォトクロミック接着性組成物からなる接着層となる。
フォトクロミック特性としての発色濃度は0.9であり、退色速度は45秒であった。また、剥離強度は23℃雰囲気下で120N/25mm、150℃雰囲気で15N/25mmあった。また、別途、同様の方法で作製したフォトクロミック接着性シートの軟化点は、180℃であった。フォトクロミック接着性組成物からなる接着層の膜厚、第二接着層の使用の有無・膜厚について表4に示した。なお、表4における第二接着層の厚みは、一方のシート上の厚みである。そのため、2枚のシートを接合する場合には、第二接着層の合計厚みは、表4の値の倍となる。
また、得られたフォトクロミック積層体は、実施例1と同様の評価を行い、フォトクロミック特性・剥離強度は表6、曲げ加工、射出成形性は表7に示した。
フォトクロミック接着性組成物の調製
実施例15におけるフォトクロミック接着性組成物の調製と同じ方法で同じフォトクロミック接着性組成物を構成する混合物を得た。表4に配合を示した。
第二接着層用ウレタンウレア樹脂(W1)のプロピレングリコール-モノメチルエーテル溶液25gに、界面活性剤としてDOW CORNING TORAY L-7001 2.5mgを添加し、室温で攪拌・混合を行い、第二接着層用接着剤を得た。
第二接着層用接着剤を厚み300μmのポリカーボネートシート上に塗布し、110℃で10分間乾燥させることにより、膜厚10μmの第二接着層を有するポリカーボネートシートを得た。
フォトクロミック特性としての発色濃度は0.9であり、退色速度は45秒であった。また、剥離強度は23℃雰囲気下で200N/25mm、150℃雰囲気で60N/25mmあった。また、別途、同様の方法で作製したフォトクロミック接着性シートの軟化点は、180℃であった。フォトクロミック接着性組成物からなる接着層の膜厚、第二接着層の使用の有無・膜厚について表4に示した。
表4に示す(A)フォトクロミック化合物、(B)接着性ウレタン(ウレア)樹脂、(C)成分を用いた以外は、実施例15、16と同様の方法でフォトクロミック接着性組成物を調整した。
表4に示す(A)フォトクロミック化合物、(B)接着性ウレタン(ウレア)樹脂、C成分を用いた以外は、実施例15、16と同様の方法でフォトクロミック接着性組成物を調整した。
2 光学シート
3 フォトクロミック接着性組成物からなる接着層
4 光学シート
Claims (9)
- (A)分子量が300以上の分子鎖を置換基として有するフォトクロミック化合物、及び
(B)接着性ウレタン(ウレア)樹脂を含んでなり、
軟化点が140~220℃となるフォトクロミック接着性組成物。 - 前記(B)接着性ウレタン(ウレア)樹脂が、
(B1)分子内に2つ以上の水酸基を有する数平均分子量400~3000のポリカーボネートポリオール、及びポリカプロラクトンポリオールから選ばれる少なくとも1種のポリオール化合物、及び
(B2)分子内に2つ以上のイソシアネート基を有するポリイソシアネート化合物を反応して得られるウレタン(ウレア)樹脂である請求項1に記載のフォトクロミック接着性組成物。 - 前記(B)接着性ウレタン(ウレア)樹脂が、前記(B1)成分、及び(B2)成分に加えて、
(B3)分子内に2つ以上のイソシアネート基と反応しうる基を有する分子量50~300の活性水素含有化合物とを反応して得られるウレタン(ウレア)樹脂である請求項2に記載のフォトクロミック接着性組成物。 - 更に、(C)分子内に少なくとも1つのイソシアネート基を有するイソシアネート化合物を含んでなることを特徴とする請求項1~3のいずれかに記載のフォトクロミック接着性組成物。
- 前記(A)フォトクロミック化合物が、下記式(1)、及び下記式(2)から選ばれる少なくとも1種類であることを特徴とする請求項1~4のいずれかに記載のフォトクロミック接着性組成物。
PC-(L-Chain) (1)
PC-(L-Chain-L’)-PC’ (2)
{式(1)または式(2)中、
PC、又はPC’は、それぞれ、下記式(3)~(7)で示される基本骨格を有する化合物から選ばれ、
該基本骨格において、置換基を有することができる炭素原子又は窒素原子の内、1つの原子が2価の有機基であるL又はL’と直接結合し、その他の原子は他の置換基を有してもよく、又は
置換基を有することができる炭素原子又は窒素原子の内、1つの原子が置換基を介して2価の有機基であるL又はL’と結合し、その他の原子は他の置換基を有してもよく、
さらに、PCとPC'とは、同一でも異なっていてもよく、
L、およびL'は、それぞれ、ポリオキシアルキレン鎖、(チオ)エステル基、(チオ)アミド基から選択される少なくとも1種の基を含む2価の有機基であり、LとL'とは、同一でも異なっていてもよく、
Chainは、ポリシロキサン鎖、ポリオキシアルキレン鎖から選択される少なくとも1種の鎖を含む1価または2価の有機基であり、
LおよびChain、またはL、L’およびChainの合計の分子量が前記分子鎖の分子量に該当する。}。
- 互いに対向する2枚の(D)光学シートが請求項1~6のいずれかに記載のフォトクロミック接着性組成物から得られる接着層を介して接合される積層構造を含むフォトクロミック積層体。
- 前記(D)光学シートが、ポリカーボネート樹脂、ポリエステル樹脂、セルロース樹脂、ポリアミド樹脂、(メタ)アクリル樹脂、ポリウレタン樹脂、ポリウレタンウレア樹脂、エポキシ樹脂、ポリイミド樹脂、ポリオレフィン樹脂及びポリビニルアルコール樹脂から選ばれる樹脂からなることを特徴とする請求項7に記載のフォトクロミック積層体。
- 請求項7、または8に記載のフォトクロミック積層体の少なくとも一方の外表面上に、
ポリエステル樹脂、ポリアミド樹脂、アリル樹脂、(メタ)アクリル樹脂、ポリウレタン樹脂、ポリウレタンウレア樹脂、ポリチオウレタン樹脂、ポリエポキシ樹脂、ポリチオエポキシ樹脂、及びポリカーボネート樹脂
から選ばれる樹脂からなる(E)合成樹脂層を積層した光学物品。
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MX2020010481A MX2020010481A (es) | 2018-04-05 | 2019-04-04 | Composicion adhesiva fotocromica, cuerpo en capas fotocromico y articulo optico usando el cuerpo en capas fotocromico. |
EP19781870.1A EP3779530A4 (en) | 2018-04-05 | 2019-04-04 | PHOTOCHROMIC ADHESIVE COMPOSITION, PHOTOCHROMIC LAMINATE BODY AND OPTICAL ARTICLE USING THIS PHOTOCHROMIC LAMINATE BODY |
CN201980037032.XA CN112204437B (zh) | 2018-04-05 | 2019-04-04 | 光致变色粘接性组合物、光致变色层叠体和使用了该光致变色层叠体的光学物品 |
KR1020207028409A KR20200140819A (ko) | 2018-04-05 | 2019-04-04 | 포토크로믹 접착성 조성물, 포토크로믹 적층체, 및 해당 포토크로믹 적층체를 사용한 광학 물품 |
JP2020512322A JP7045446B2 (ja) | 2018-04-05 | 2019-04-04 | フォトクロミック接着性組成物、フォトクロミック積層体、及び該フォトクロミック積層体を用いた光学物品 |
BR112020020189-8A BR112020020189A2 (pt) | 2018-04-05 | 2019-04-04 | Composição adesiva fotocrômica, laminado fotocrômico, e, artigo óptico. |
US17/045,384 US20210155830A1 (en) | 2018-04-05 | 2019-04-04 | Photochromic adhesive composition, photochromic layered body, and optical article using said photochromic layered body |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018073508 | 2018-04-05 | ||
JP2018-073508 | 2018-04-05 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2019194281A1 true WO2019194281A1 (ja) | 2019-10-10 |
Family
ID=68100794
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2019/014976 WO2019194281A1 (ja) | 2018-04-05 | 2019-04-04 | フォトクロミック接着性組成物、フォトクロミック積層体、及び該フォトクロミック積層体を用いた光学物品 |
Country Status (8)
Country | Link |
---|---|
US (1) | US20210155830A1 (ja) |
EP (1) | EP3779530A4 (ja) |
JP (1) | JP7045446B2 (ja) |
KR (1) | KR20200140819A (ja) |
CN (1) | CN112204437B (ja) |
BR (1) | BR112020020189A2 (ja) |
MX (1) | MX2020010481A (ja) |
WO (1) | WO2019194281A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022030557A1 (ja) * | 2020-08-06 | 2022-02-10 | 株式会社トクヤマ | フォトクロミック化合物、フォトクロミック硬化性組成物、硬化体、レンズ及び眼鏡 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI652508B (zh) | 2011-06-13 | 2019-03-01 | 尼康股份有限公司 | 照明方法 |
CN114031594B (zh) * | 2021-09-10 | 2023-06-20 | 江苏视科新材料股份有限公司 | 一种双苯并色烯类化合物及其应用 |
Citations (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS615910A (ja) | 1984-06-21 | 1986-01-11 | Mitsubishi Gas Chem Co Inc | フオトクロミツク性に優れた合成樹脂成形品の製法 |
WO2000015630A1 (en) | 1998-09-11 | 2000-03-23 | Ppg Industries Ohio, Inc. | Polyalkoxylated naphthopyrans |
JP2002196103A (ja) | 2000-12-25 | 2002-07-10 | Mitsubishi Gas Chem Co Inc | フォトクロミック特性を有する合成樹脂積層体の製造方法 |
WO2002099513A1 (fr) | 2001-06-01 | 2002-12-12 | Mitsubishi Gas Chemical Company, Inc. | Produit en plastique moule a caracteristiques photochromiques et/ou polarisantes |
JP2003519398A (ja) | 1999-12-30 | 2003-06-17 | バイエル・コーポレーシヨン | ホトクロミックレンズの製造方法 |
US20040096666A1 (en) | 2002-11-14 | 2004-05-20 | Knox Carol L. | Photochromic article |
WO2004041961A1 (en) | 2002-11-04 | 2004-05-21 | Polymers Australia Pty Limited | Photochromic compositions and light transmissible articles |
WO2005105874A1 (en) | 2004-04-30 | 2005-11-10 | Polymers Australia Pty Limited | Photochromic compositions and articles comprising polyether oligomer |
WO2006022825A1 (en) | 2004-07-30 | 2006-03-02 | Transitions Optical, Inc. | Photochromic materials |
WO2009146509A1 (en) | 2008-06-05 | 2009-12-10 | Advanced Polymerik Pty Ltd | Photochromic polymer and composition comprising photochromic polymer |
WO2010020770A1 (en) | 2008-08-18 | 2010-02-25 | James Robinson Limited | Polydialkylsiloxane-bridged bi-photochromic molecules |
US20110190455A1 (en) * | 2008-08-18 | 2011-08-04 | Vivimed Labs Europe Ltd. | Polydialkylsiloxane-bridged bi-photochromic molecules |
WO2012121414A1 (ja) | 2011-03-08 | 2012-09-13 | 株式会社トクヤマ | クロメン化合物 |
WO2012141250A1 (ja) * | 2011-04-13 | 2012-10-18 | 株式会社トクヤマ | フォトクロミック組成物 |
WO2012149599A1 (en) | 2011-05-03 | 2012-11-08 | Advanced Polymerik Pty Ltd | Photochromic polymer |
WO2012162725A1 (en) | 2011-06-03 | 2012-12-06 | Advanced Polymerik Pty Ltd | Photochromic polymers |
WO2012176918A1 (ja) | 2011-06-23 | 2012-12-27 | 株式会社トクヤマ | クロメン化合物 |
WO2013078086A1 (en) | 2011-11-22 | 2013-05-30 | Transitions Optical, Inc. | Photochromic compounds having at least two photochromic moieties |
WO2013099640A1 (ja) | 2011-12-26 | 2013-07-04 | 株式会社トクヤマ | フォトクロミック組成物 |
US20170327736A1 (en) | 2013-01-09 | 2017-11-16 | Vision Ease, Lp | Photochromic Polyurethane Laminate |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2002952454A0 (en) * | 2002-11-04 | 2002-11-21 | Polymers Australia Pty Limited | Photochromic compositions and light transmissible particles |
KR101878016B1 (ko) * | 2011-07-11 | 2018-07-12 | 가부시끼가이샤 도꾸야마 | 포토크로믹 경화성 조성물 |
CN108351539B (zh) * | 2015-12-28 | 2022-01-14 | 株式会社德山 | 层叠体及使用该层叠体的光学物品 |
-
2019
- 2019-04-04 CN CN201980037032.XA patent/CN112204437B/zh active Active
- 2019-04-04 WO PCT/JP2019/014976 patent/WO2019194281A1/ja active Application Filing
- 2019-04-04 EP EP19781870.1A patent/EP3779530A4/en active Pending
- 2019-04-04 JP JP2020512322A patent/JP7045446B2/ja active Active
- 2019-04-04 MX MX2020010481A patent/MX2020010481A/es unknown
- 2019-04-04 BR BR112020020189-8A patent/BR112020020189A2/pt unknown
- 2019-04-04 US US17/045,384 patent/US20210155830A1/en active Pending
- 2019-04-04 KR KR1020207028409A patent/KR20200140819A/ko not_active Application Discontinuation
Patent Citations (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS615910A (ja) | 1984-06-21 | 1986-01-11 | Mitsubishi Gas Chem Co Inc | フオトクロミツク性に優れた合成樹脂成形品の製法 |
WO2000015630A1 (en) | 1998-09-11 | 2000-03-23 | Ppg Industries Ohio, Inc. | Polyalkoxylated naphthopyrans |
JP2003519398A (ja) | 1999-12-30 | 2003-06-17 | バイエル・コーポレーシヨン | ホトクロミックレンズの製造方法 |
JP2002196103A (ja) | 2000-12-25 | 2002-07-10 | Mitsubishi Gas Chem Co Inc | フォトクロミック特性を有する合成樹脂積層体の製造方法 |
WO2002099513A1 (fr) | 2001-06-01 | 2002-12-12 | Mitsubishi Gas Chemical Company, Inc. | Produit en plastique moule a caracteristiques photochromiques et/ou polarisantes |
WO2004041961A1 (en) | 2002-11-04 | 2004-05-21 | Polymers Australia Pty Limited | Photochromic compositions and light transmissible articles |
US20040096666A1 (en) | 2002-11-14 | 2004-05-20 | Knox Carol L. | Photochromic article |
WO2005105874A1 (en) | 2004-04-30 | 2005-11-10 | Polymers Australia Pty Limited | Photochromic compositions and articles comprising polyether oligomer |
WO2005105875A1 (en) | 2004-04-30 | 2005-11-10 | Polymers Australia Pty Limited | Photochromic compositions and articles comprising siloxane, alkylene or substituted alkylene oligomers |
WO2006022825A1 (en) | 2004-07-30 | 2006-03-02 | Transitions Optical, Inc. | Photochromic materials |
WO2009146509A1 (en) | 2008-06-05 | 2009-12-10 | Advanced Polymerik Pty Ltd | Photochromic polymer and composition comprising photochromic polymer |
WO2010020770A1 (en) | 2008-08-18 | 2010-02-25 | James Robinson Limited | Polydialkylsiloxane-bridged bi-photochromic molecules |
US20110190455A1 (en) * | 2008-08-18 | 2011-08-04 | Vivimed Labs Europe Ltd. | Polydialkylsiloxane-bridged bi-photochromic molecules |
WO2012121414A1 (ja) | 2011-03-08 | 2012-09-13 | 株式会社トクヤマ | クロメン化合物 |
WO2012141250A1 (ja) * | 2011-04-13 | 2012-10-18 | 株式会社トクヤマ | フォトクロミック組成物 |
WO2012149599A1 (en) | 2011-05-03 | 2012-11-08 | Advanced Polymerik Pty Ltd | Photochromic polymer |
US20140042377A1 (en) * | 2011-05-03 | 2014-02-13 | Vivimed Labs Europe Ltd | Photochromic Polymer |
WO2012162725A1 (en) | 2011-06-03 | 2012-12-06 | Advanced Polymerik Pty Ltd | Photochromic polymers |
WO2012176918A1 (ja) | 2011-06-23 | 2012-12-27 | 株式会社トクヤマ | クロメン化合物 |
WO2013078086A1 (en) | 2011-11-22 | 2013-05-30 | Transitions Optical, Inc. | Photochromic compounds having at least two photochromic moieties |
WO2013099640A1 (ja) | 2011-12-26 | 2013-07-04 | 株式会社トクヤマ | フォトクロミック組成物 |
US20170327736A1 (en) | 2013-01-09 | 2017-11-16 | Vision Ease, Lp | Photochromic Polyurethane Laminate |
Non-Patent Citations (1)
Title |
---|
See also references of EP3779530A4 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022030557A1 (ja) * | 2020-08-06 | 2022-02-10 | 株式会社トクヤマ | フォトクロミック化合物、フォトクロミック硬化性組成物、硬化体、レンズ及び眼鏡 |
Also Published As
Publication number | Publication date |
---|---|
US20210155830A1 (en) | 2021-05-27 |
CN112204437B (zh) | 2022-12-20 |
MX2020010481A (es) | 2020-10-22 |
JPWO2019194281A1 (ja) | 2021-04-22 |
JP7045446B2 (ja) | 2022-03-31 |
EP3779530A1 (en) | 2021-02-17 |
BR112020020189A2 (pt) | 2021-01-05 |
EP3779530A4 (en) | 2022-01-05 |
CN112204437A (zh) | 2021-01-08 |
KR20200140819A (ko) | 2020-12-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6049638B2 (ja) | フォトクロミック組成物 | |
JP6755887B2 (ja) | 積層体、及び該積層体を用いた光学物品 | |
JP5743616B2 (ja) | フォトクロミック組成物 | |
WO2019194281A1 (ja) | フォトクロミック接着性組成物、フォトクロミック積層体、及び該フォトクロミック積層体を用いた光学物品 | |
JP6885953B2 (ja) | 接着性組成物、積層体、及び該積層体を用いた光学物品 | |
JP6579938B2 (ja) | フォトクロミック組成物、及び該組成物からなる積層体、及び該積層体を用いた物品 | |
WO2012018070A1 (ja) | フォトクロミック組成物 | |
WO2012141250A1 (ja) | フォトクロミック組成物 | |
JP5863317B2 (ja) | フォトクロミック組成物 | |
JP2016132696A (ja) | スプレーコート用フォトクロミック組成物、及びフォトクロミック特性を有する光学物品の製造方法 | |
JP5967877B2 (ja) | フォトクロミック組成物、および光学物品 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 19781870 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2020512322 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112020020189 Country of ref document: BR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2019781870 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2019781870 Country of ref document: EP Effective date: 20201105 |
|
ENP | Entry into the national phase |
Ref document number: 112020020189 Country of ref document: BR Kind code of ref document: A2 Effective date: 20201001 |