Classifications

• • 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
  • 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
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• • 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
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
  • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
  • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
  • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
  • B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
• • 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
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
  • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
  • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
  • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
  • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
• • 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
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
  • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
  • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
  • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
  • B32B17/10743—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing acrylate (co)polymers or salts thereof
• • 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
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
  • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
  • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
  • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
  • B32B17/1077—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyurethane
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
• • 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
  • C08G18/16—Catalysts
  • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
• • 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
  • C08G18/48—Polyethers
  • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene 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
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
  • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
  • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
• • 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
• • 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
  • 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
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
  • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • 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
  • C08L75/08—Polyurethanes from polyethers
• • 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
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
• • 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
  • 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
  • C09D175/08—Polyurethanes from polyethers
• • 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
  • B32B2270/00—Resin or rubber layer containing a blend of at least two different 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
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal 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
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
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• • 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
  • B32B2307/414—Translucent
• • 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
  • B32B2307/737—Dimensions, e.g. volume or area
  • B32B2307/7375—Linear, e.g. length, distance or width
  • B32B2307/7376—Thickness
• • 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
  • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2333/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • 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
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
  • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
  • C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • 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
  • C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2475/04—Polyurethanes

Definitions

• the present invention relates to a resin composition, a resin film made of the resin composition, and a glass laminate comprising the resin film.
• Resin films formed from resin compositions are used in all fields such as packaging materials for foods, base materials for adhesive tapes, and various members for vehicles.
• a resin film formed of an acrylic resin or a urethane resin is used as an interlayer film for laminated glass because of its high transparency.
• the laminated glass interlayer film is arranged between two glass plates and is used to integrate them as a laminated glass.
• Resin films are often formed from a single resin component for applications that require transparency, but many types of resins are combined to form a phase-separated structure such as a sea-island structure. It is being considered to be functional.
• a resin film containing an acrylic polymer containing at least a nitrogen-containing monomer as a monomer unit and a crosslinked urethane polymer, and forming a sea-island structure by the acrylic polymer and the urethane polymer. is disclosed. It is shown that this resin film is excellent in transparency, heat resistance, weather resistance, strength and flexibility, and has self-repairing property of self-repairing by heating.
• Patent Document 2 discloses resin particles containing a (meth) acrylic polymer containing no active hydrogen and a urethane polymer, and a phase-separated structure formed by these.
• the resin particles disclosed in Patent Document 2 have an excellent soft focus effect without impairing slipperiness and transparency by adjusting the refractive index of the resin of each phase so as to satisfy a predetermined relationship. It is shown that it is suitably used for external preparations such as cosmetics.
• the resin film formed by combining the two types of resin is multifunctional, the transparency is low, and the transparency is significantly reduced especially in the temperature range lower than room temperature, and there is room for improvement. It was. Therefore, in the present invention, in a resin composition having a continuous phase and a dispersed phase, a resin composition having excellent transparency not only at room temperature but also at low temperature, a resin film made of the resin composition, and a glass provided with the resin film. Laminated product It is an object of the present invention to provide the resin.
• the present inventors have diligently studied to solve the above problems. Then, it has a continuous phase made of a thermoplastic resin A and a dispersed phase made of a thermoplastic resin B, has a glass transition temperature of the resins A and B within a specific temperature range, and has a glass transition temperature existing in the specific temperature range.
• a resin composition in which the absolute value of the difference between the temperatures Tg1 and Tg2 is below a certain level and the haze at 23 ° C. is below a certain level, and the following invention has been completed.
• the present invention provides the following [1] to [15].
• [1] It has a phase-separated structure in which the thermoplastic resin A is a continuous phase and the thermoplastic resin B is a dispersed phase, and has a glass transition temperature of the thermoplastic resin A and the thermoplastic resin B at ⁇ 50 ° C. or higher and 50 ° C. or lower.
• the absolute value of the difference between the glass transition temperatures Tg1 and Tg2 existing at ⁇ 50 ° C. or higher and 50 ° C. or lower is 17 ° C. or lower, and the haze at 23 ° C. measured by the following method is less than 1.5%. Stuff.
• the haze of the laminated glass at 23 ° C. is measured by a method according to JIS K 6714.
• the thermoplastic resin A is a polyurethane resin.
• thermoplastic resin B is an acrylic resin
• thermoplastic resin A is a polyurethane resin
• mass ratio (A / B) of the polyurethane resin to the acrylic resin is 0.4 or more.
• the acrylic resin is an acrylic polymer (b) which is a polymer of a monomer component, and the monomer component is a hydroxy group, a carboxy group, a thiol group, an amino group, a group having an ether bond, and a urethane bond.
• a resin film comprising the resin composition according to any one of the above [1] to [10].
• the resin film according to the above [11] which has a thickness of 200 ⁇ m or more and 2000 ⁇ m or less.
• a glass laminate comprising the resin film according to the above [11] or [12] and a glass member, wherein the resin film is provided on at least one surface of the glass member.
• a glass laminate comprising a resin film made of a resin composition and a pair of opposing glass members, wherein the resin film is arranged between the pair of glass members, and the resin composition is heated. It has a phase-separated structure in which the plastic resin A is a continuous phase and the thermoplastic resin B is a dispersion layer, and has a glass transition temperature of the thermoplastic resin A and the thermoplastic resin B at -50 ° C or higher and 50 ° C or lower, and is -50.
• the resin composition of the present invention it is possible to provide a resin composition having excellent transparency at room temperature and low temperature, a resin film made of the resin composition, and a glass laminate provided with the resin film.
• the resin composition of the present invention has a phase-separated structure in which the thermoplastic resin A is a continuous phase and the thermoplastic resin B is a dispersed phase, and the glass transition temperature of the thermoplastic resins A and B is -50 ° C or higher and 50 ° C or lower.
• the absolute value of the difference between the glass transition temperatures Tg1 and Tg2 existing at ⁇ 50 ° C. or higher and 50 ° C. or lower is within 17 ° C., and the haze at 23 ° C. measured by the following method is less than 1.5.
• Such a resin composition is excellent in transparency at room temperature and low temperature.
• the transparency at a low temperature means the transparency in a temperature region lower than the room temperature (23 ° C.), and more specifically, the transparency at 0 ° C. or lower (for example, ⁇ 30 ° C.).
• thermoplastic resin A and the thermoplastic resin B have a glass transition temperature of ⁇ 50 ° C. or higher and 50 ° C. or lower.
• the transparency of the resin composition at room temperature, low temperature, or both becomes low.
• both the thermoplastic resin A and the thermoplastic resin B have a glass transition temperature of preferably 30 ° C. or lower, more preferably 20 ° C. or lower, and also have a glass transition temperature of 20 ° C. or lower. It preferably has a glass transition temperature of ⁇ 40 ° C. or higher.
• the glass transition temperature of the thermoplastic resin A and the thermoplastic resin B can be adjusted to a desired range by appropriately selecting the type of the monomer constituting each resin and the like.
• the glass transition temperature of the thermoplastic resin A and the thermoplastic resin B is a glass transition temperature obtained by independently measuring the thermoplastic resin A and the thermoplastic resin B, respectively. More specifically, the glass transition temperature of the thermoplastic resin A is the tan ⁇ peak temperature obtained by preparing a film-shaped sample made of the thermoplastic resin A and performing dynamic viscoelasticity measurement on the sample. The same applies to the glass transition temperature of the thermoplastic resin B, which is the tan ⁇ peak temperature obtained by preparing a film-shaped sample made of the thermoplastic resin B and performing dynamic viscoelasticity measurement on the sample.
• the conditions for dynamic viscoelasticity measurement are as described in Examples. A plurality of tan ⁇ peak temperatures may be confirmed.
• At least one tan ⁇ peak temperature may be present at ⁇ 50 ° C. or higher and 50 ° C. or lower.
• the glass transition temperature of the thermoplastic resin A and the thermoplastic resin B measured independently is different from the glass transition temperature of the thermoplastic resin A and the thermoplastic resin B when the resin composition of the present invention is measured. There is. This is because, in the case of the resin composition, if the thermoplastic resin A and the thermoplastic resin B have a good affinity, the glass transition temperatures of the thermoplastic resin A and the thermoplastic resin B approach each other.
• the absolute value of the difference between the glass transition temperature Tg1 and the glass transition temperature Tg2 existing at ⁇ 50 ° C. or higher and 50 ° C. or lower is 17 ° C. or lower.
• the absolute value of the difference between Tg1 and Tg2 exceeds 17 ° C., the transparency of the resin composition at low temperature decreases even if the transparency at room temperature is good.
• the absolute value of the difference between Tg1 and Tg2 is preferably 15 ° C. or lower, more preferably 10 ° C. or lower, still more preferably 3 ° C. or lower. is there.
• the reason why the transparency of the resin composition at low temperature is improved by reducing the absolute value of the difference between Tg1 and Tg2 is not clear, but it is estimated as follows.
• the refractive index of a thermoplastic resin tends to change near the glass transition temperature. Therefore, if the glass transition temperatures of the individual thermoplastic resins of the resin composition containing the plurality of thermoplastic resins are different, the difference in the refractive index at each temperature becomes large, and the transparency is also deteriorated due to this. Become.
• the glass transition temperature of each thermoplastic resin is close to the temperature, the change in the refractive index due to the temperature change is about the same, so that the difference in the refractive index between the two thermoplastic resins at a low temperature is different. It is considered that the transparency becomes good at a low temperature in combination with the fact that the haze value becomes smaller and the haze value at room temperature becomes a certain value or less.
• Tg1 and Tg2 of the resin composition are tan ⁇ peak temperatures in the dynamic viscoelasticity measurement of the resin film made of the resin composition, and among the tan ⁇ peak temperatures existing at ⁇ 50 ° C. or higher and 50 ° C. or lower, tan ⁇ on the lowest temperature side.
• the peak temperature is Tg1
• the second lowest tan ⁇ peak temperature is Tg2.
• One of Tg1 and Tg2 has a peak temperature derived from the thermoplastic resin A, and the other has a peak temperature derived from the thermoplastic resin B. Since the thermoplastic resins A and B in the present invention have a glass transition temperature of ⁇ 50 ° C. or higher and 50 ° C.
• the temperature is ⁇ 50 ° C.
• the tan ⁇ peak temperature of 50 ° C. or higher is a single peak, it means that the tan ⁇ peak temperatures overlap, and the difference between Tg1 and Tg2 is 0 ° C.
• the conditions for measuring the dynamic viscoelasticity of the resin film are as described in Examples.
• the haze of the resin composition of the present invention at 23 ° C. is less than 1.5. If the haze at 23 ° C. exceeds 1.5%, the transparency near room temperature decreases, and even if the difference between Tg1 and Tg2 is reduced as described above, the transparency at low temperature is not sufficiently improved. From the viewpoint of improving the transparency at room temperature and low temperature, the haze of the resin composition at 23 ° C. is preferably 1.3% or less, more preferably 1.0% or less. As the haze value of the resin composition at 23 ° C. and ⁇ 30 ° C.
• a predetermined laminated glass is prepared as follows, and the value measured with respect to the laminated glass is used as the haze value of the resin composition.
• a film having a thickness of 800 ⁇ m made of a resin composition and two float glasses having a thickness of 1.0 mm, a length of 75 mm, and a width of 75 mm are prepared, and a laminated glass obtained by sandwiching the film between the two float glasses is produced.
• the haze of the laminated glass at 23 ° C. or ⁇ 30 ° C. is measured by a method according to JIS K 6714.
• As the float glass a clear float plate glass conforming to JIS 3202 is used.
• thermoplastic resin The resin composition of the present invention has a phase-separated structure in which the thermoplastic resin A is a continuous phase and the thermoplastic resin B is a dispersed phase.
• the types of the thermoplastic resins A and B are not particularly limited as long as they have the above-mentioned glass transition temperature, and for example, a polyolefin resin, a polyester resin, a polyvinyl chloride resin, a polystyrene resin, a polyurethane resin, and a polyamide.
• a resin, a (meth) acrylic resin, a polyvinyl alcohol resin, an ethylene-vinyl acetate copolymer resin, an ionomer resin, an isobutylene resin, a polyvinyl acetal resin and the like may be appropriately selected from the viewpoint of exhibiting a desired function.
• the resin composition and the resin film made of the resin composition can be made multifunctional, and a resin composition having excellent low-temperature transparency can be obtained.
• the resin composition in which the dispersed phase and the continuous phase are formed by the acrylic resin and the polyurethane resin shall be used for a wide range of applications requiring transparency and adhesiveness to be adhered. Is preferable.
• the thermoplastic resin A is preferably a polyurethane resin
• the thermoplastic resin B is preferably an acrylic resin.
• the resin composition preferably contains an acrylic resin as the thermoplastic resin B.
• an acrylic resin By using an acrylic resin, the resin composition of the present invention can easily secure transparency. In addition, it becomes easy to improve the adhesiveness of the resin composition to other members such as glass. Further, when it is used for a glass laminate such as laminated glass, it becomes easy to prevent the occurrence of warpage.
• the acrylic resin is an acrylic polymer (b).
• the acrylic polymer (b) may be a polymer having a monomer component appropriately selected so that the glass transition temperature is within the above range.
• the acrylic polymer (b) is at least one functional group selected from a hydroxy group, a carboxy group, a thiol group, an amino group, a group having an ether bond, a group having a urethane bond, and a group having an amide bond. It may be a polymer of a monomer component containing an acrylic monomer (b1) having (X).
• the resin composition of the present invention is more transparent by using the acrylic monomer (b1) having these functional groups (X) to increase the compatibility and dispersibility with respect to the polyurethane resin and to reduce the dispersed phase. It becomes easier to secure sex.
• Each acrylic monomer (b1) may have only one type of functional group (X), but may have two or more types.
• the functional group (X) may be at least one selected from among the above, a hydroxy group, a carboxy group, an amino group, a group having an ether bond, a group having a urethane bond, and a group having an amide bond. preferable. Among these, at least one selected from a hydroxy group, a carboxy group, a group having an ether bond, and a group having a urethane bond is more preferable from the viewpoint of reducing the dispersed phase and further improving the transparency. Further, from the viewpoint of heat resistance, at least one selected from a hydroxy group, a group having an ether bond, and a group having a urethane bond is more preferable, and the acrylic polymer (b) is a functional group (b). It is even more preferable to include a hydroxy group as X).
• the acrylic monomer (b1) is a compound having a (meth) acryloyl group in addition to the functional group (X), and a monofunctional monomer having one (meth) acryloyl group is preferable.
• a monofunctional monomer having one (meth) acryloyl group is preferable.
• the acrylic monomer (b1) having a hydroxy group hydroxyalkyl (meth) such as 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate
• phthalic acid ester compounds such as acrylate, 2-acryloyloxyethyl-2-hydroxypropylphthalate and 2-methacryloyloxyethyl-2-hydroxypropylphthalate.
• hydroxyalkyl (meth) acrylates are preferred.
• the number of carbon atoms of the hydroxyalkyl group in the hydroxyalkyl (meth) acrylate is not particularly limited, but is, for example, 1 to 6, preferably 2 to 4.
• the hydroxyalkyl (meth) acrylate is preferably a hydroxyalkyl acrylate from the viewpoint of lowering the glass transition temperature of the acrylic polymer (b).
• “(meth) acryloyl group” means acryloyl group or methacryloyl group
• “(meth) acrylate” means acrylate or methacrylate, and other similar terms are the same.
• acrylic monomer (b1) having a carboxy group examples include acrylic acid, methacrylic acid, ⁇ -carboxy-polycaprolactone mono (meth) acrylate and the like.
• the number of repeating units of polycaprolactone in ⁇ -carboxy-polycaprolactone mono (meth) acrylate is about 2 to 5, but preferably 2 to 3.
• the carboxyl group-containing acrylic monomer is preferably ⁇ -carboxy-polycaprolactone mono (meth) acrylate.
• Examples of the acrylic monomer (b1) (ether bond-containing acrylic monomer) in which the functional group (X) has an ether bond include cyclic ether group-containing (meth) acrylate.
• the cyclic ether group-containing (meth) acrylate those having an epoxy ring, an oxetane ring, a tetrahydrofuran ring, a dioxolane ring, and a dioxane ring are used.
• a (meth) acrylate containing an epoxy ring, an oxetane ring, and a dioxolane ring is preferable, and an oxetane ring-containing (meth) acrylate is particularly preferable.
• Examples of the epoxy ring-containing (meth) acrylate include glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate glycidyl ether, 3-hydroxypropyl (meth) acrylate glycidyl ether, 4-hydroxybutyl acrylate glycidyl ether, and 5-. Examples thereof include hydroxypentyl (meth) acrylate glycidyl ether and 6-hydroxyhexyl (meth) acrylate glycidyl ether.
• Examples of the oxetane ring-containing (meth) acrylate include (3-methyloxetane-3-yl) methyl (meth) acrylate, (3-propyloxetane-3-yl) methyl (meth) acrylate, and (3-ethyloxetane-3-yl).
• Examples of the tetrahydrofuran ring-containing (meth) acrylate include tetrahydrofurfuryl (meth) acrylate, ⁇ -butyrolactone (meth) acrylate, and tetrahydrofurfuryl alcohol acrylic acid multimer ester.
• Examples of the dioxolan ring-containing (meth) acrylate include (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate and (2,2-cyclohexyl-1,3-dioxolan-4-yl).
• Methyl (meth) acrylate (2,2-dimethyl-1,3-dioxolan-4-yl) Methyl (meth) acrylate, (2-methyl-2-isobutyl-1,3-dioxolan-4-yl) Methyl (meth) acrylate and the like can be mentioned.
• dioxane ring-containing (meth) acrylate examples include (5-ethyl-1,3-dioxane-5-yl) methyl (meth) acrylate.
• the ether bond-containing acrylic monomer polyoxyalkylene-containing (meth) acrylate or the like may be used, and diethylene glycol monoethyl ether (meth) acrylate and polyethylene glycol monoethyl ether (meth) acrylate (the number of repetitions of ethylene glycol is, for example, 3 to 20). ) And the like, polyethylene glycol monoalkyl ether (meth) acrylate, and polypropylene glycol monoalkyl ether (meth) acrylate. Further, the ether bond-containing acrylic monomer may be an alkoxy-containing (meth) acrylate such as 3-methoxybutyl (meth) acrylate.
• a cyclic ether group-containing (meth) acrylate is preferable.
• Suitable specific examples of cyclic ether group-containing (meth) acrylates are glycidyl (meth) acrylates, (2-methyl-2-ethyl-1,3-dioxolane-4-yl) methyl (meth) acrylates, (3-ethyl).
• Oxetane-3-yl) methyl (meth) acrylate Of these, (3-ethyloxetane-3-yl) methyl (meth) acrylate is more preferred.
• Examples of the acrylic monomer (b1) (urethane bond-containing acrylic monomer) in which the functional group (X) has a urethane bond include 1,2-ethanediol-1- (meth) acrylate 2- (N-butylcarba). Mart).
• Examples of the amino group-containing acrylic monomer (b1) include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) methacrylate, N, N-diethylaminoethyl (meth) acrylate and the like. Can be mentioned.
• acrylic monomer (b1) (amide bond-containing acrylic monomer) in which the functional group (X) has an amide bond
• the acrylic monomer (b1) amide bond-containing acrylic monomer in which the functional group (X) has an amide bond
• examples of the acrylic monomer (b1) (amide bond-containing acrylic monomer) in which the functional group (X) has an amide bond include N, N-dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, Examples thereof include N-diethyl (meth) acrylamide and N-hydroxyethyl (meth) acrylamide.
• the acrylic monomer (b1) may be a polyfunctional monomer having two or more (meth) acryloyl groups. Specifically, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tetramethylolmethanetri (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol. Examples thereof include di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, and tetrapropylene glycol di (meth) acrylate.
• the acrylic monomer (b1) having a functional group (X) may be used alone or in combination of two or more.
• the acrylic monomer (b1) having a functional group (X) is blended with, for example, 5 parts by mass or more with respect to 100 parts by mass of the monomer component constituting the acrylic polymer (b).
• the blending amount of the acrylic monomer (b1) is preferably 10 parts by mass or more, more preferably 20 parts by mass or more, and further preferably 50 parts by mass or more.
• the acrylic polymer (b) has a viewpoint of reducing the difference in refractive index from the polyurethane resin described later, and a viewpoint of adjusting the glass transition temperature (Tg) of the acrylic polymer (b) within a desired range.
• the blending amount of the acrylic monomer (b1) is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, and 80 parts by mass with respect to 100 parts by mass of the monomer component constituting the acrylic polymer (b). The following is more preferable.
• the acrylic polymer (b) may be a polymer obtained by polymerizing a monomer component containing an acrylic monomer (b2) having no functional group (X), but in addition to the above-mentioned acrylic monomer (b1), a functional group may be used.
• a polymer obtained by polymerizing a monomer component containing an acrylic monomer (b2) that does not have (X) is preferable.
• the acrylic monomer (b2) it is preferable to use a monofunctional monomer having one (meth) acryloyloxy group. Examples of such an acrylic monomer (b2) include an alkyl (meth) acrylate, an alicyclic structure-containing (meth) acrylate, and an aromatic ring-containing (meth) acrylate.
• the acrylic monomer (b2) by using the acrylic monomer (b2), it becomes easy to reduce the difference in refractive index between the acrylic polymer (b) and the polyurethane resin described later. Therefore, in the phase separation structure described later, reflection and refraction are less likely to occur at the interface between the phases, and transparency is likely to be improved.
• the glass transition temperature (Tg) can be easily adjusted within a desired range.
• alkyl (meth) acrylate examples include an alkyl (meth) acrylate having an alkyl group having 1 to 18 carbon atoms. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl.
• alkyl (meth) acrylates having an alkyl group having 1 to 12 carbon atoms are preferable, and the alkyl group has 1 carbon atom from the viewpoint of facilitating the adjustment of the glass transition temperature (Tg) within a desired range.
• Alkyl acrylates of ⁇ 12 are more preferable.
• an alkyl acrylate having an alkyl group having 4 to 12 carbon atoms is preferable, and an alkyl acrylate having 4 to 8 carbon atoms is more preferable.
• Examples of the alicyclic structure-containing (meth) acrylate include cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and dicyclopentanyl (meth) acrylate.
• Examples of the aromatic ring-containing (meth) acrylate include benzyl (meth) acrylate.
• a polyfunctional monomer having two or more (meth) acryloyloxy groups may be used.
• examples of such a polyfunctional monomer include trimetyl propanetri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tetramethylol propanetetra (meth) acrylate, and ethylene glycol di (meth).
• the acrylic monomer (b2) is transparent with respect to 100 parts by mass of the monomer component constituting the acrylic polymer (b) from the viewpoint of facilitating the adjustment of the glass transition temperature and reducing the refractive difference from the polyurethane resin described later. From the viewpoint of improving the properties, it is preferably blended in an amount of 10 parts by mass or more, more preferably 15 parts by mass or more, and further preferably 20 parts by mass or more. Further, in order to contain a certain amount or more of the structural unit derived from the acrylic monomer (b1), the acrylic monomer (b2) is, for example, with respect to 100 parts by mass of the monomer component constituting the acrylic polymer (b). It is blended in an amount of 95 parts by mass or less, preferably 90 parts by mass or less, and more preferably 80 parts by mass or less.
• the alkyl (meth) acrylate is particularly preferably an alkyl acrylate.
• the blending amount of the alkyl (meth) acrylate constituting the acrylic polymer (b) is preferably 10 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the monomer component constituting the acrylic polymer (b). It is more preferably 15 parts by mass or more and 60 parts by mass or less, and further preferably 20 parts by mass or more and 50 parts by mass or less.
• the acrylic monomer (b2) it is preferable to contain an aromatic ring-containing (meth) acrylate in addition to the alkyl (meth) acrylate.
• the content of the aromatic ring-containing (meth) acrylate is preferably 1 part by mass or more and 20 parts by mass or less, and more preferably 2 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the monomer component constituting the acrylic polymer (b). It is less than a part by mass.
• an alicyclic structure-containing (meth) acrylate may be used as the acrylic monomer (b2).
• the content of the alicyclic structure-containing (meth) acrylate is preferably 5 parts by mass or more and 60 parts by mass or less, more preferably 60 parts by mass, based on 100 parts by mass of the monomer component constituting the acrylic polymer (b). It is 10 parts by mass or more and 40 parts by mass or less.
• the acrylic polymer (b) may be polymerized in combination with a vinyl monomer other than the above-mentioned acrylic monomer, but it is preferably polymerized using only the above-mentioned acrylic monomer.
• the acrylic polymer (b) may be polymerized by a solution polymerization method, a suspension polymerization method, or the like, but as described later, it is preferably polymerized by irradiating with active energy rays.
• the polyurethane resin used in the present invention is a thermoplastic polyurethane resin.
• the thermoplastic polyurethane resin is usually obtained by reacting a long-chain polyol component, an isocyanate component, and a short-chain diol component.
• the polyurethane resin of the present invention is a resin containing a structural unit derived from a long-chain polyol component, a structural unit derived from an isocyanate component, and a structural unit derived from a short-chain diol component.
• the polyurethane resin has a structure in which a soft segment formed by the reaction of a long-chain polyol and an isocyanate and a hard segment formed by a reaction of a short-chain diol and an isocyanate are mutually bonded.
• the long-chain polyol component contained in the polyurethane resin is a polyol having a molecular weight of 250 or more.
• the molecular weight of the long-chain polyol is preferably 500 or more, more preferably 650 or more.
• the glass transition temperature of the polyurethane resin is likely to be lowered.
• the glass transition temperature of the acrylic resin is adjusted to be low, the difference between Tg1 and Tg2 is different. It becomes easy to reduce the absolute value. Further, the softness of the polyurethane resin is increased, and the transparency of the polyurethane resin itself tends to be improved.
• the molecular weight of the long-chain polyol is preferably 2000 or less from the viewpoint of preventing the mechanical strength of the resin composition from being excessively lowered.
• the molecular weight of the long-chain polyol is a standard polystyrene-equivalent number average molecular weight measured by gel permeation chromatography (GPC).
• the type of long-chain polyol contained in the polyurethane resin is not particularly limited, and examples thereof include polyether-based polyols and polyester-based polyols. From the viewpoint of suppressing hydrolysis of the resin composition and improving moist heat resistance. , Polyester-based polyols are preferable.
• polyether polyol examples include polyethylene ether glycol, polypropylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and the like. Of these, polytetramethylene ether glycol is preferable.
• polyester-based polyol examples include compounds obtained by a condensation reaction between a polyhydric alcohol and a dibasic acid.
• the polyhydric alcohol include ethylene glycol, propylene glycol, butanediol, butenediol, hexanediol, pentanediol, neopentyldiol, and pentanediol.
• the dibasic acid include adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, maleic acid, aromatic carboxylic acid and the like.
• the isocyanate component contained in the polyurethane resin is not particularly limited, and examples thereof include aliphatic isocyanates, alicyclic isocyanates, and aromatic isocyanates.
• aliphatic isocyanate examples include hexamethylene diisocyanate, tetramethylene diisocyanate, dodecamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexanediisocyanate and the like.
• alicyclic isocyanate examples include alicyclic isocyanate having two or more ring structures such as dicyclohexylmethane 4,4-diisocyanate and 2,2-bis (4-isocyanatecyclohexyl) methane, 1-methyl-2, Single ring structure such as 4-diisocyanate cyclohexane, (1,4-cyclohexanediyl) bisisocyanate, 1-methyl-2,6-diisocyanatecyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, etc.
• An alicyclic isocyanate having the above can be mentioned.
• aromatic isocyanate examples include toluene diisocyanate, diphenylmethane diisocyanate, polypeptide MDI, p-phenylenediocyanate, naphthalene diisocyanate and the like.
• alicyclic isocyanate is preferable from the viewpoint of obtaining a resin composition having excellent transparency and yellowing resistance. Further, since the glass transition temperature can be lowered when the number of ring structures is small among the alicyclic isocyanates, the number of ring structures may be determined according to the glass transition temperature of the acrylic resin described above.
• the short chain diol contained in the polyurethane resin is a diol having a molecular weight of less than 250.
• Examples of the short chain diol include diols having 2 or more and 10 or less carbon atoms. Among them, a diol having a large number of carbon atoms is preferable from the viewpoint of obtaining a polyurethane resin having a low glass transition temperature, and therefore a diol having 4 or more and 10 or less carbon atoms is preferable. Further, as the short chain diol, a saturated aliphatic diol is preferable.
• short chain diol examples include ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,3-butanediol, and 2-methyl-1,3-.
• the hard segment mass ratio (%) is the mass C of isocyanate, the mass D of short-chain diol, the mass E of long-chain polyol, and the hydroxyl mass F of long-chain polyol, (C + D + F) ⁇ (C + D + E) ) ⁇ 100.
• the hard segment mass ratio of the thermoplastic polyurethane resin is preferably 30% or more and 55% or less, more preferably 35% or more and 52% or less, and further preferably 38% or more and 50% or less. When the hard segment mass ratio is not more than these upper limit values, the ratio of hard segments in the polyurethane resin is reduced, so that the transparency of the polyurethane resin is improved.
• the handleability of the interlayer film becomes good.
• the composition of the polyurethane resin can be quantitatively analyzed for isocyanates, long-chain polyols, and short-chain diols using, for example, pyrolysis gas chromatography, NMR, and FT-IR. Based on these compositions, the hard segment mass ratio can be calculated using the above formula.
• the polyurethane resin has, for example, a glass transition temperature of 50 ° C. or lower, preferably 30 ° C. or lower, more preferably 20 ° C. or lower, but more preferably 10 ° C. or lower. Has a glass transition temperature of. By setting the glass temperature to be equal to or lower than these upper limit values, the adhesiveness to organic glass such as polycarbonate resin is improved.
• the polyurethane resin may be manufactured by the prepolymer method or the one-shot method, but it is preferably manufactured by the prepolymer method. By using the polyurethane resin produced by the prepolymer method, it becomes easy to adjust the glass transition temperature of the polyurethane resin to be low.
• the prepolymer method is a method in which a long-chain polyol is reacted with isocyanate in advance to produce an isocyanate group-containing prepolymer, and the prepolymer is reacted with a short-chain diol to produce a polyurethane resin.
• the one-shot method is a method for producing a polyurethane resin by simultaneously reacting a long-chain polyol, an isocyanate, and a short-chain diol.
• the polyurethane resin is preferably produced in the presence of a polyurethane production catalyst.
• the type of polyurethane production catalyst is not particularly limited, and conventionally known catalyst systems can be preferably used. Specifically, for example, organometallic compounds such as tin-based, lead-based, iron-based, and titanium-based compounds and amine-based compounds are exemplified.
• the mass ratio (A / B) of the thermoplastic resin A to the thermoplastic resin B is preferably 0.4 or more, more preferably 1 or more, and further preferably 1.5 or more.
• the amount of the thermoplastic resin A which is a continuous phase is large and the mass ratio (A / B) is as described above, light scattering at the interface between the continuous phase and the dispersed phase can be suppressed and the transparency at a low temperature is improved. Can be made to.
• the thermoplastic resin A is a polyurethane resin and the thermoplastic resin B is an acrylic resin
• the adhesiveness of the resin composition to organic glass such as polycarbonate can be improved by adjusting the mass ratio (A / B) as described above. Become good.
• the resin composition can be suitably used as a glass laminate such as laminated glass.
• the mass ratio (A / B) is preferably 5.0 or less from the viewpoint of keeping the amount of the dispersed phase above a certain level and preventing deterioration of the physical properties of the resin composition.
• the resin composition of the present invention may have a resin component other than the thermoplastic resin A and the thermoplastic resin B as long as the effects of the present invention are exhibited.
• the resin component is preferably small.
• the resin composition does not contain a resin component other than the thermoplastic resin A and the thermoplastic resin B.
• the total amount of the thermoplastic resin A and the thermoplastic resin B is preferably 90% by mass or more based on the total amount of the resin contained in the resin composition. When the content is 90% by mass or more, the adhesiveness of the resin film formed from the resin composition is improved, and the transparency is easily ensured.
• the total amount of the thermoplastic resin A and the thermoplastic resin B is more preferably 95% by mass or more, further preferably 97% by mass or more, and most preferably 100% by mass based on the total amount of the resin.
• the resin composition of the present invention may appropriately contain a known additive used in combination with a thermoplastic resin.
• a known additive used in combination with a thermoplastic resin include ultraviolet absorbers, infrared absorbers, antioxidants, light stabilizers, adhesive strength modifiers, pigments, dyes, fluorescent whitening agents, crystal nucleating agents, compatibilizers and the like.
• a polymerization initiator or the like used when polymerizing the acrylic polymer (b) or the like may remain in the resin composition.
• a compatibilizer a graft copolymer or a block copolymer composed of the components of the thermoplastic resin A and the thermoplastic resin B can be used. By using a compatibilizer, the dispersed phase becomes smaller and transparency can be easily ensured.
• the resin composition of the present invention may be diluted with a solvent and used in the form of a diluted solution.
• the solvent used when synthesizing the acrylic polymer (b) and the like may be used as a part or all of the diluting solvent.
• the resin composition when used by laminating it on glass such as an interlayer film for laminated glass, it often contains a plasticizer to ensure flexibility, but the resin plasticizer B is an acrylic resin.
• the thermoplastic resin A is a polyurethane resin
• the resin composition of the present invention can secure flexibility even if it does not contain a plasticizer.
• the resin composition does not contain a plasticizer, even if it is used by being laminated on an organic material such as organic glass, it is possible to prevent the plasticizer from migrating and causing fogging on the resin material such as organic glass.
• the resin composition of the present invention has a continuous phase composed of the thermoplastic resin A and a dispersed phase composed of the thermoplastic resin B, and forms a phase-separated structure.
• the phase-separated structure may be any structure, but a sea-island structure is preferable.
• the average major axis of the dispersed phase made of the thermoplastic resin B is preferably 10 nm or more and 100 ⁇ m or less, more preferably 30 nm or more and 3 ⁇ m or less, further preferably 40 nm or more and 1 ⁇ m or less, and 50 nm or more and 500 nm or less. It is particularly preferable to have.
• the size of the dispersed phase is made relatively small in this way, reflection and refraction are less likely to occur at the interface between the phases, and the transparency of the resin composition is improved.
• the aspect ratio represented by the average major axis with respect to the average minor axis of the dispersed phase is not particularly limited, but is, for example, 1 or more and 500 or less, more preferably 5 or more and 300 or less, and further preferably 15 or more and 200 or less. is there.
• the major axis and the minor axis are measured by osmium-staining a sample made of a resin composition, preparing an ultrathin section by a cryomicrotome, and using a transmission electron microscope.
• the major axis is the length of the longest part of each island in microscopic observation, and the minor axis is the length of the islands when measured perpendicular to the major axis.
• the average major axis and the average minor axis are average values when any 20 islands are measured.
• the resin composition preferably has a ratio (E / F) of haze (E) at ⁇ 30 ° C. to haze (F) at 0 ° C. of 2 or less.
• E haze
• F haze
• the resin composition has excellent transparency and a small change in transparency in the range from low temperature to room temperature. From such a viewpoint, the E / F is more preferably 1.8 or less.
• the method for preparing the resin composition of the present invention may be prepared, for example, by mixing a thermoplastic resin A and a thermoplastic resin B synthesized in advance (hereinafter, also referred to as “first method”). Further, the thermoplastic resin B may be prepared by synthesizing the thermoplastic resin B in the presence of the thermoplastic resin A. That is, the thermoplastic resin A and the monomer component for forming the thermoplastic resin B are mixed to obtain a mixture thereof, and then the monomer component is polymerized in the mixture to synthesize the thermoplastic resin B. (Hereinafter, also referred to as "second method").
• thermoplastic resin A is a polyurethane resin
• thermoplastic resin B is an acrylic resin
• the acrylic resin and the polyurethane resin are in an appropriate mixed state, so that a relatively fine phase-separated structure can be easily formed and the transparency can be easily improved.
• the monomer component for forming the thermoplastic resin B may be polymerized in the presence of a polymerization initiator.
• the thermoplastic resin B (for example, an acrylic resin) is not particularly limited, but can be synthesized by polymerizing a monomer component by a free radical polymerization method, a living radical polymerization method, or the like.
• the polymerization initiator an organic peroxide-based polymerization initiator, an azo-based polymerization initiator, or the like may be used in the free radical polymerization method.
• an organic tellurium polymerization initiator or the like may be used.
• a chain transfer agent may be used in addition to the polymerization initiator.
• polymerization may be carried out by irradiating with active energy rays, and in that case, a photopolymerization initiator may be used as the polymerization initiator.
• the thermoplastic resin B may be polymerized by a solution polymerization method, a suspension polymerization method or the like, or may be polymerized by an active energy ray as described above, but may be polymerized by a solution polymerization method or an active energy ray.
• the solution polymerization method is preferable, and the solution polymerization method is particularly preferable. Therefore, in the second method, the thermoplastic resin B can be synthesized by polymerizing the monomer component for forming the thermoplastic resin B and the monomer component in a state where the thermoplastic resin A is dissolved in a solvent. preferable.
• the solvent is not particularly limited, but includes aliphatic hydrocarbon solvents such as n-pentane, n-hexane, n-heptane, and cyclohexane, aromatic hydrocarbon solvents such as toluene, ethyl acetate, n-butyl acetate, and the like.
• aliphatic hydrocarbon solvents such as n-pentane, n-hexane, n-heptane, and cyclohexane
• aromatic hydrocarbon solvents such as toluene, ethyl acetate, n-butyl acetate, and the like.
• ester solvents acetone, methyl ethyl ketone (MEK), ketone solvents such as cyclohexanone, ether solvents such as tetrahydrofuran, dimethylformamide (DMF), N-methylpyrrolidone and the like.
• MEK methyl ethy
• the monomer component is preferably polymerized by free radical polymerization using an organic peroxide-based polymerization initiator.
• organic peroxide-based polymerization initiator include cumene hydroperoxide, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, stearoyl peroxide, o-chlorobenzoyl peroxide, acetyl peroxide, t-butyl hydroperoxide, and t-butyl peroxide.
• the blending amount of the polymerization initiator is preferably 0.05 parts by mass or more and 6 parts by mass or less, and more preferably 0.2 parts by mass or more and 4 parts by mass with respect to 100 parts by mass of the monomer component for constituting the thermoplastic resin B. It is less than a part.
• the polymerization temperature and polymerization time in the free radical polymerization are not particularly limited, but are, for example, 1 to 24 hours at 40 to 110 ° C., preferably 3 to 12 hours at 60 to 85 ° C.
• the resin composition of the present invention contains at least one of a resin component other than the thermoplastic resin A and the thermoplastic resin B, and an additive, these contain the thermoplastic resin A and the thermoplastic resin B (at which stage. Alternatively, it may be mixed with the monomer component for forming the thermoplastic resin B).
• the thermoplastic resin A, the resin component other than the thermoplastic resin B component, and the additive are combined with the monomer component for forming the thermoplastic resin B before synthesizing the thermoplastic resin B. It may be mixed with the mixture of the thermoplastic resin A, or may be mixed with the mixture of the thermoplastic resin A and the thermoplastic resin B after synthesis.
• the thermoplastic resin A and the thermoplastic resin B may be mixed by ultra-high speed kneading or the like in order to reduce the dispersed phase and improve the transparency.
• the resin composition of the present invention may be used in any form, but it is preferably used in the form of a film. That is, the present invention provides, as a preferred embodiment, a resin film made of the above-mentioned resin composition.
• the resin film is broadly referred to as a resin film not only when it is a single resin film but also when it is laminated or coated on another member to form a layered or film-like form.
• the thickness of the resin film made of the resin composition of the present invention may be appropriately selected depending on the intended use, for example, 200 ⁇ m or more and 2000 ⁇ m or less.
• the thickness of the resin film is preferably 250 ⁇ m or more and 900 ⁇ m or less. By setting the thickness of the resin film within such a range, it can be suitably used as an interlayer film for laminated glass or the like.
• the resin film of the present invention may be composed of a single layer, but may be composed of a multilayer film.
• the multilayer film may have at least one layer of the resin film of the present invention described above. That is, the multilayer film is preferably a laminate of the resin film having the above-mentioned resin composition of the present invention and the resin film having a composition other than the resin composition of the present invention. Further, the multilayer film may be a laminate having two or more layers of the resin film composed of the resin composition of the present invention described above, and even in that case, the laminate is a resin having a composition other than the resin composition of the present invention. You may have a film.
• the resin film of the present invention may be used in applications that require transparency, light transmission, and the like.
• it is used for a transparent protective film used to protect an optical member, a film for an optical member forming a part of an optical member, a resin film for glass used for glass, an adhesive film, an adhesive film, and the like.
• it is preferable to use it as a resin film for glass.
• the resin film of the present invention may be provided on at least one surface of glass.
• the resin film of the present invention is composed of a single layer, and the single-layer resin film may be laminated on the glass surface, or may be laminated on the glass surface as a multilayer film. In the case of a multilayer film, it is preferable that the resin film of the present invention is arranged at a position where it comes into contact with the glass and is directly laminated on the glass, but it is not necessary to be directly laminated.
• the resin film of the present invention is particularly preferably used as an interlayer film for laminated glass. That is, the resin film of the present invention and the multilayer film having the resin film of the present invention are preferably arranged between a pair of glass members and used as an interlayer film for adhering the pair of glass members. Further, as described above, the resin composition of the present invention may be used in a form other than the film.
• the resin film of the present invention may be produced by extrusion molding, press molding or the like of the above-mentioned resin composition. Further, the resin film of the present invention may be produced by a method of molding by applying the above-mentioned resin composition or a diluted solution thereof on a release sheet or the like and drying the film. Further, when the resin film is molded by coating or the like, if the thickness is insufficient by one film molding, a plurality of films are prepared, the plurality of films are overlapped, and the resin film is integrated by pressure bonding or the like. It may be converted into a single resin film.
• the resin film may be molded while synthesizing the thermoplastic resin B by polymerizing the monomer components for forming the thermoplastic resin B.
• a mixture containing a polyurethane resin and a monomer component for forming an acrylic resin is formed into a film, and in the state of being formed into a film, the mixture is cured by polymerizing the monomer component to cure the polyurethane resin and the acrylic resin.
• a resin film made of a resin composition containing and may be formed.
• a plurality of films containing the resin film of the present invention may be laminated and integrated by pressure bonding or the like to form one multilayer film, but the multilayer film may be formed by any other method. You may make it.
• the resin film of the present invention is preferably used for glass as described above, that is, the present invention also provides, as a preferred embodiment, a glass laminate including a glass member and a resin film.
• the glass member is selected from inorganic glass and organic glass as described later.
• the glass laminate of the present invention may include at least one glass member and the resin film of the present invention described above, and the resin film may be provided on at least one surface of the glass member.
• the resin film of the present invention is composed of a single layer as described above, and the single-layer resin film may be laminated on the glass member, or the multilayer film having the resin film of the present invention may be laminated on the glass member. Good.
• the resin film of the present invention is arranged at a position where it comes into contact with the glass member and is directly laminated on the glass member, but it does not have to be directly laminated. Since the resin composition of the present invention can have good adhesiveness to glass, it can be laminated on a glass member with high adhesive force. Further, the glass member can be adhered to another member via the resin film laminated on the glass member or the multilayer film.
• the glass laminate is preferably laminated glass.
• the laminated glass includes a resin film and a pair of opposing glass members, and the resin film is arranged between the pair of glass members.
• the resin film provided in the glass laminate is made of a resin composition.
• the resin composition has a phase-separated structure in which the above-mentioned thermoplastic resin A is a continuous phase and the thermoplastic resin B is a dispersed phase.
• the glass transition temperature of the thermoplastic resin A and the thermoplastic resin B is -50 ° C or higher and 50 ° C or lower, and the absolute difference between the glass transition temperatures Tg1 and Tg2 existing at -50 ° C or higher and 50 ° C or lower is absolute.
• the value is 17 ° C. or lower.
• the haze of the glass laminate at 23 ° C. is less than 1.5.
• a glass laminate satisfying such a requirement has a low haze at ⁇ 30 ° C. and is excellent in transparency at a low temperature.
• the ratio (E / F) of the haze (E) at ⁇ 30 ° C. to the haze (F) at 0 ° C. is preferably 2 or less. When it is 2 or less, a glass laminate having excellent transparency and a small change in transparency can be obtained in the region from low temperature to room temperature. From such a viewpoint, the E / F is more preferably 1.8 or less.
• the haze value of the glass laminate at 23 ° C. or ⁇ 30 ° C. the value obtained by measuring the glass laminate itself in accordance with JIS K 6714 is adopted.
• the resin film may have a single-layer structure between the pair of glass members, and in this case, the pair of glass members may be bonded and integrated by the resin film. Further, the resin film may form the above-mentioned multilayer film between the pair of glass members. In this case, the pair of glass members may be bonded and integrated by a multilayer film. Further, the resin film is arranged at a position in contact with the glass member and may or may not be directly laminated on the glass member, but is preferably directly laminated.
• the glass member in the glass laminate is selected from inorganic glass and organic glass.
• the pair of glass members is selected from either inorganic glass or organic glass, respectively.
• the pair of glass members in the laminated glass is preferably inorganic glass or organic glass, more preferably both inorganic glass, but one may be inorganic glass and the other may be organic glass.
• the inorganic glass is not particularly limited, but for example, float plate glass, toughened glass, colored glass, polished plate glass, template glass, meshed plate glass, lined plate glass, ultraviolet absorber glass, infrared reflector glass, infrared absorber glass, etc. Examples include various glass plates such as green glass. Inorganic glass may be surface-treated.
• the thickness of the inorganic glass is not particularly limited, but is preferably 0.1 mm or more, more preferably 1.0 mm or more, and preferably 5.0 mm or less, further preferably 3.2 mm or less.
• the organic glass is not particularly limited, but is not particularly limited, but is a methacrylate plate such as a polycarbonate plate or a polymethyl methacrylate plate, an acrylonitrile styrene copolymer plate, an acrylonitrile butadiene styrene copolymer plate, a polyester plate, a fluororesin plate, or a polychloride.
• methacrylate plate such as a polycarbonate plate or a polymethyl methacrylate plate
• an acrylonitrile styrene copolymer plate an acrylonitrile butadiene styrene copolymer plate
• polyester plate a fluororesin plate
• fluororesin plate or a polychloride
• Examples thereof include various organic glass plates such as vinyl plates, chlorinated polyvinyl chloride plates, polypropylene plates, polystyrene plates, polysulphon plates, epoxy resin plates, phenol resin plates, unsaturated polyester resin plates,
• a polycarbonate plate is preferable from the viewpoint of excellent transparency, impact resistance, and combustion resistance
• a methacrylate plate such as a polymethylmethacrylate plate is preferable from the viewpoint of high transparency, weather resistance, and mechanical strength.
• a polycarbonate plate is preferable.
• the specific thickness of the organic glass is not particularly limited, but is preferably 0.1 mm or more, more preferably 0.3 mm or more, and preferably 5.0 mm or less, further preferably 3.0 mm or less. ..
• the glass laminate and laminated glass of the present invention can be used in various fields. Specifically, it is used for windows of various vehicles such as automobiles and trains, ships and airplanes, and various buildings such as buildings, condominiums, detached houses, halls and gymnasiums.
• the resin film or the multilayer film of the present invention described above is arranged on the surface of the glass member and adhered to the glass member by thermal pressure bonding or the like. It is good to manufacture it.
• the laminated glass can be manufactured by arranging a resin film prepared in advance between a pair of glass members and thermocompression bonding or the like.
• the multilayer film may be prepared in advance and the multilayer film may be arranged between the pair of glass members.
• thermocompression bonding In the production of the laminated glass, after arranging a resin film, a multilayer film or a plurality of resin films between a pair of glass members, and before thermocompression bonding, if necessary, between the pair of glass members.
• the residual air may be degassed.
• the method of degassing is not particularly limited, but it may be carried out by passing it through a pressing roll or putting it in a rubber bag and sucking it under reduced pressure.
• temporary bonding may be performed before thermocompression bonding.
• Temporary adhesion may be performed, for example, by arranging a resin film, a multilayer film, or a plurality of resin films between a pair of glass members and pressing them with a relatively low pressure while heating them as necessary.
• Temporary bonding may be performed, for example, with a vacuum laminator.
• the temporary adhesion may be performed after degassing or may be performed together with degassing.
• the method of thermocompression bonding is not particularly limited, but it is preferable to apply pressure while heating the resin films or the like placed between the pair of glass members.
• the heating temperature is preferably 60 ° C. or higher and 150 ° C. or lower, and more preferably 70 ° C. or higher and 120 ° C. or lower.
• the pressure is preferably 0.4 MPa or more and 1.5 MPa or less, and more preferably 0.5 MPa or more and 1.3 MPa or less.
• the pressure here is an absolute pressure.
• the thermocompression bonding may be performed by using an autoclave, a method of performing by a heating press, or the like, but it is preferable to perform the thermocompression bonding by using an autoclave.
• thermoplastic resin A is the polyurethane resin used in each Example and Comparative Example
• thermoplastic resin B is an acrylic resin synthesized with the same monomer components and the same monomer ratio as in each Example and Comparative Example.
• the synthesis conditions for synthesizing the acrylic resin were the same as those in each of the examples and comparative examples except that the urethane resin was not added.
• a film-shaped sample made of each thermoplastic resin is prepared, and each sample is cut out with a width of 5 mm and a length of 4 cm, and a dynamic viscoelasticity measuring device (manufactured by IT Measurement Control Co., Ltd., trade name "DVA-200").
• Table 1 shows the glass transition temperatures confirmed at ⁇ 50 ° C. or higher and 50 ° C. or lower. When a plurality of glass transition temperatures were confirmed at ⁇ 50 ° C. or higher and 50 ° C. or lower, the glass transition temperature on the lowest temperature side was described.
• Measurement condition Deformation mode: tensile mode, measurement temperature: -50 ° C to 200 ° C, temperature rise rate: 5 ° C / min, measurement frequency: 1Hz, strain: 0.08%
• a measurement sample was prepared by the following first to third steps, and the cross peeling test of the measurement sample was performed to determine the adhesive force of the resin film to polycarbonate.
• First step A resin film having a length of 15 mm and a width of 15 mm for each of the resin films of Examples and Comparative Examples, a clear float plate glass having a thickness of 1.8 mm, a length of 25 mm, and a width of 100 mm according to JIS 3202, and JIS.
• the clear float plate glass and the polycarbonate plate glass were cross-aligned via the resin film.
• Second step Using a spacer having the same thickness as the resin film so that the thickness of the resin film is constant, the clear float plate glass and the polycarbonate plate glass laminated via the resin film are placed at 80 ° C. in a vacuum laminator. Temporarily crimped for 3 minutes under the condition of 0.1 MPa.
• Third step The temporarily crimped clear float plate glass and the polycarbonate plate glass were subjected to main crimping under the conditions of 80 ° C. and 0.5 MPa for 1 hour.
• Cross peeling test Measure the maximum load (N) when the polycarbonate plate glass is peeled from the clear float plate glass in the direction perpendicular to the adhesive surface at a speed of 10 mm / min at 23 ° C., and bond the maximum load (N). It was evaluated as a force based on the following criteria.
• thermoplastic resin A polyurethane resin
• H12MDI Dicyclohexylmethane 4,4-diisocyanate
• H6XDI 1,3-bis (isocyanatomethyl) cyclohexane
• IPDI Isophorone diisocyanate
• thermoplastic resin B (acrylic resin)> (Acrylic monomer (b1)) H-ABEI: 1,2-ethanediol-1-acrylate-2- (N-butylcarbamate): Product name "Viscoat # 216", manufactured by Osaka Organic Chemical Industry Co., Ltd., CAS No. : 63225-53-6 OXE-30: (3-ethyloxetane-3-yl) methyl acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd.
• 4-HBA 4-hydroxybutyl acrylate, manufactured by Nihon Kasei Corporation M5300: ⁇ -carboxy-polycaprolactone monoacrylate, Product name "M-5300", manufactured by Toa Synthetic Co., Ltd.
• (acrylic monomer (b2)) BzA benzyl acrylate, manufactured by Wako Pure Chemical Industries, Ltd. BA: butyl acrylate, manufactured by Nippon Shokubai Co., Ltd. LA: lauryl acrylate, manufactured by Nichiyu Co., Ltd.
• IBOA isobornyl acrylate, manufactured by Nippon Shokubai Co., Ltd. 2-EHA: 2-ethylhexyl acrylate, Nippon Shokubai Co., Ltd.
• CHA Cyclohexyl acrylate, Osaka Organic Chemical Industry Co., Ltd.
• MA Methyl acrylate, Nippon Shokubai Co., Ltd.
• NVP N-Vinylpyrrolidone, manufactured by Nippon Shokubai Co., Ltd.
• Example 1 (Preparation of resin composition) A 400 mL separable flask equipped with a stirrer, a cooling pipe, a nitrogen inlet pipe, a thermometer, and an initiator supply port was prepared and arranged in a hot water bath. The hot water bath was set to 80 ° C., and a polyurethane resin (AG8451) dissolved in ethyl acetate was put into a separable flask. The concentration of the polyurethane resin (AG8451) in the ethyl acetate solution was 25% by mass.
• the monomer component (acrylic monomer) for forming the acrylic resin mixed at the blending ratio shown in Table 1 was put into the reactor, nitrogen flow was performed for 30 minutes, and the inside of the container was subjected to nitrogen flow. Oxygen was removed. At this time, the blending amount was adjusted so that the mass ratio (A / B) of the acrylic resin obtained from the monomer component and the polyurethane resin was the ratio shown in Table 1.
• the reaction was carried out at 70 ° C. for 6 hours while adding the ethyl acetate solution of the polymerization initiator to the reaction vessel in several portions. The polymerization initiator was sequentially added at the start of the reaction and every hour thereafter.
• the total amount of the polymerization initiator added was 0.77 parts by mass with respect to 100 parts by mass of the monomer component constituting the acrylic resin.
• the temperature of the hot water bath was raised and the reaction solution was kept in a boiling state for 1 hour to completely decompose the polymerization initiator of the reaction system.
• ethyl acetate was added to the reaction vessel, the temperature was lowered to 23 ° C., and the polymer solution was recovered.
• the obtained polymer solution was passed through a filter cloth to remove suspended matter and the like.
• the solution was adjusted to give a dilution of the resin composition.
• the PET release film (trade name "PET50 ⁇ 1-C", manufactured by Nippers) was brought into close contact with the upper surface of the coated glass with ethyl acetate so that the release treatment surface was facing up. After applying the diluted solution of the resin composition obtained above on the release-treated surface of the PET release film to a predetermined thickness, it is 20 minutes at 30 ° C, 20 minutes at 50 ° C, and 20 at 80 ° C. The solvent was removed by drying while gradually increasing the temperature at 110 ° C. for 20 minutes, and a film made of the resin composition was formed on the PET release film.
• PET50 ⁇ 1-C manufactured by Nippers
• the molded film was peeled off from the PET release film, and a plurality of sheets were laminated to obtain a resin film having a thickness of 800 ⁇ m.
• the resin composition constituting the resin film has a sea-island structure (phase-separated structure in the present invention), and the average minor axis of the islands (dispersed phase).
• the average major axis was 1.2 ⁇ m, and the aspect ratio was 24.
• Examples 2 to 4 Comparative Examples 1 to 2
• a resin film was obtained in the same manner as in Example 1 except that the types and compounding ratios of the monomer components for constituting the acrylic resin were changed as shown in Table 1.
• Example 5 instead of the polyurethane resin used in Example 1, a polyurethane resin synthesized by using each component shown in Table 1 below is used, and the types and compounding ratios of the monomer components for constituting the acrylic resin are shown in the table. A resin film was obtained in the same manner as in Example 1 except that the changes were made as described in 1.
• Examples 6 to 7, Comparative Example 3 The resin film is the same as in Example 5, except that the types and compounding ratios of various components for synthesizing the polyurethane resin and the types and compounding ratios of the monomer components for forming the acrylic resin are changed as shown in Table 1.
• the glass transition temperature of the thermoplastic resins A and B was ⁇ 50 ° C. or higher and 50 ° C. or lower, the absolute value of Tg1-Tg2 was 17 ° C. or lower, and the haze value at 23 ° C. was 1. Since it is less than 5%, it is a resin composition that satisfies each requirement of the present invention.
• the resin composition had a small haze value at ⁇ 30 ° C., was excellent in transparency not only at room temperature but also at low temperature, and had good adhesive strength to polycarbonate.
• the resin compositions of Comparative Examples 1 to 3 which did not satisfy all the requirements of the present invention had a large haze value at ⁇ 30 ° C. and were inferior in transparency at low temperatures.

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