EP4499767A1 - Composition adhésive pour article verrier comprenant des moyens d'expansion et vitrage feuilleté pour automobile comprenant une telle composition - Google Patents
Composition adhésive pour article verrier comprenant des moyens d'expansion et vitrage feuilleté pour automobile comprenant une telle compositionInfo
- Publication number
- EP4499767A1 EP4499767A1 EP23715825.8A EP23715825A EP4499767A1 EP 4499767 A1 EP4499767 A1 EP 4499767A1 EP 23715825 A EP23715825 A EP 23715825A EP 4499767 A1 EP4499767 A1 EP 4499767A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- adhesive composition
- laminated glazing
- glass
- pvb
- composition according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
- C03C27/10—Joining glass to glass by processes other than fusing with the aid of adhesive specially adapted for that purpose
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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
- 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
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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
- 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
- B32B17/10614—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 comprising particles for purposes other than dyeing
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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
- 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
- B32B17/10761—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 vinyl acetal
-
- 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
- B32B17/10807—Making laminated safety glass or glazing; Apparatus therefor
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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
- B32B43/00—Operations specially adapted for layered products and not otherwise provided for, e.g. repairing; Apparatus therefor
- B32B43/006—Delaminating
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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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
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- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
-
- 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
- C09J129/00—Adhesives 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- 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
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
-
- 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
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/54—Filled microcapsules
-
- 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
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/70—Scrap or recycled material
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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
- B32B2307/412—Transparent
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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
- B32B2307/70—Other properties
- B32B2307/732—Dimensional 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
- B32B2307/70—Other properties
- B32B2307/748—Releasability
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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
- B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
- B32B2315/08—Glass
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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
- B32B2605/00—Vehicles
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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
- B32B2605/00—Vehicles
- B32B2605/08—Cars
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- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/22—Expandable microspheres, e.g. Expancel®
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- 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
- C08J2329/00—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 at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
- C08L2205/20—Hollow spheres
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
- C09J2400/10—Presence of inorganic materials
- C09J2400/14—Glass
- C09J2400/146—Glass in the pretreated surface to be joined
Definitions
- Adhesive composition for glass articles comprising expansion means and laminated glazing for automobiles comprising such a composition
- the present invention belongs to the field of disassembly and recycling of glass articles, in particular laminated glass, particularly used in the automotive field.
- Laminated glass is made up of sheets of glass, bonded together by means of an adhesive composition deposited so as to form an interlayer polymer film, typically based on poly(vinyl butyral) (PVB).
- PVB poly(vinyl butyral)
- laminated glass is today recycled by means of a grinding operation.
- the recovery materials 20% by weight of glass in the interlayer polymer (such as PVB) and 5% by weight of interlayer polymer (such as PVB) in glass.
- the present invention aims to remedy all or part of the drawbacks of the prior art, in particular those set out above, by proposing a solution which makes it possible to disassemble the interlayer polymer film formed from an adhesive composition. and the sheets of glass in laminated glazing.
- the invention relates to an adhesive composition for a glass article comprising poly(vinyl butyral) (PVB) and an expansion means.
- Such a composition according to the invention finds its interest, in particular, in the fact that it allows, in the context of its application as an interlayer fdm in laminated glazing, to weaken on demand the cohesive forces at the interfaces of PVB and glass via the expansion means it includes.
- an adhesive composition according to the invention may comprise at least one expansion means chosen from microcapsules and/or chemical expansion agents.
- microcapsules used in a composition according to the invention consist of a volatile liquid core and a polymeric shell.
- the volatile liquid core of the microcapsules vaporizes when subjected to heating, which leads to an increase in volume of the microcapsules and/or to a release of said core in the form of gas in the adhesive composition.
- microcapsules can be called “expandable microcapsules” because an increase in their volume is obtained by heating to a temperature greater than or equal to the glass transition temperature of the polymeric shell and the temperature of the vaporization temperature of the core. volatile liquid. The increase in volume due to the change in state of the core then creates sufficient pressure to deform the shell.
- microcapsules as well as their methods of obtaining are for example described in applications US 3,615,972 A; US 4,049,604 A; US 4,016,110 A; US 4,582,756 A; US 2018/0355216 Al; JP H09/019.635 A; WO 2002/096635 A1; WO 2007/142593 A1; EP 0 486 080 Al; EP 0 572 233 Al; EP 1 149 628 A1; EP 1 964 903 Al and EP 1 508 604 Al.
- the shell of the microcapsules is composed of at least one thermoplastic polymer having a high glass transition temperature, in particular greater than or equal to the vaporization temperature of the liquid core.
- Such polymers can be obtained from the polymerization of at least one monomer chosen from (meth)acrylic monomers, aromatic alkenyls, vinyl derivatives, acid monomers and their mixtures.
- (meth)acrylic monomers is meant the monomers of general formula CH 2 CH(R')C(O)OR WHERE
- R is chosen from a C1-C12 alkyl, a C3-C10 cycloalkyl or an aromatic group, optionally substituted by a hydroxy radical or R is a hydrogen atom, and R' is chosen from a hydrogen atom and a methyl.
- (meth)acrylic monomers suitable for the present invention mention may be made of methyl methacrylate, ethyl acrylate, propyl acrylate, butyl acrylate, butyl methacrylate, methacrylate propyl, lauryl acrylate, 2-ethylhexyl acrylate, ethyl methacrylate, isobomyl acrylate, isobomyl methacrylate, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate .
- aromatic alkenyls is meant the monomers of general formula Ar-CHCH2 where Ar represents an aromatic hydrocarbon radical, optionally substituted by a halogen.
- aromatic alkenyls mention may be made of styrene, ortho-methylstyrene, meta-methylstyrene, ara-methylstyrene, ethylstyrene, vinyl xylene, chlorostyrene, bromostyrene and styrene derivatives such as vinylbenzyl chloride and para-tert-butylstyrene.
- vinyl derivatives mention may be made of acrylonitrile, methacrylonitrile, vinyl halides, vinyl esters and vinyl ethers.
- vinyl halides mention may be made of vinyl chloride, vinyl bromide and vinylidene chloride.
- vinyl esters is meant the compounds of general formula CH 2 CHOC(O)R where R is a C1-C17 alkyl.
- vinyl ester monomers mention may be made of vinyl acetate, vinyl benzoate, vinyl butyrate, vinyl stearate, vinyl laurate, vinyl myristate and vinyl propionate.
- vinyl ethers mention may be made of methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether. , sec-butyl vinyl ether and their mixtures.
- acid monomers mention may be made of acrylic acid, methacrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid and vinylbenzoic acid.
- thermoplastic polymer of a microcapsule suitable for the invention can be obtained by the copolymerization of several of the monomers cited above. [0030] A thermoplastic polymer of a microcapsule suitable for the invention is typically obtained from acrylonitrile, acrylic ester and/or olefins.
- the microcapsules used in a composition according to the invention comprise a shell based on an acrylonitrile copolymer such as the acrylonitrile/methacrylonitrile copolymer or the acrylonitrile/methacrylonitrile copolymer /hydroxyethyl methacrylate.
- an acrylonitrile copolymer such as the acrylonitrile/methacrylonitrile copolymer or the acrylonitrile/methacrylonitrile copolymer /hydroxyethyl methacrylate.
- the microcapsules used in a composition according to the invention comprise a polymeric shell formed from monomers chosen from (meth)acrylic monomers, (meth)acrylonitriles and their mixtures.
- said shell is obtained by the polymerization of monomers chosen from methyl methacrylate, acrylonitrile and their mixtures.
- thermoplastic polymer constituting the shell of a microcapsule suitable for the invention has a light transmission greater than or equal to 70%, in particular at least 80% and preferably at least 88%. .
- the volatile liquid core of the microcapsules consists of a liquid whose vaporization temperature is low.
- a so-called “low” vaporization temperature for said liquid is less than or equal to the glass transition temperature of the polymer of the shell.
- Said liquid may have a vaporization temperature of 50°C to 200°C.
- Such a liquid may be a hydrocarbon such as pentane, neopentane, isopentane, cyclopentane, acetylene, hexane, cyclohexane, methylcyclohexane, heptane, cycloheptane, heptene, octane, isooctane, cyclooctane, octene and their mixtures.
- a hydrocarbon such as pentane, neopentane, isopentane, cyclopentane, acetylene, hexane, cyclohexane, methylcyclohexane, heptane, cycloheptane, heptene, octane, isooctane, cyclooctane, octene and their mixtures.
- alkanes that are liquid at room temperature such as pentane, neopentane, isopentane, cyclopentane, hexane, cyclohexane, methylcyclohexane, heptane, cycloheptane, octane, Iooctane and cyclooctane are preferred.
- tetraalkylsilanes such as tetramethylsilane, trimethylethylsilane, trimethylisopropylsilane and trimethyl-w-propylsilane.
- microcapsules suitable for the invention can therefore contain a liquid having a low vaporization temperature, in particular chosen from hydrocarbons, and preferably chosen from alkanes.
- the liquid core of a microcapsule suitable for the invention comprises at least one hydrocarbon, preferably chosen from isopentane, pentane, hexane, cyclohexane, methylcyclohexane, heptane, heptene and their mixtures, and more preferably chosen from isopentane and methylcyclohexane.
- microcapsules suitable for the invention may comprise from 3% to 50% by weight of volatile liquid and preferably from 5% to 30% by weight of volatile liquid relative to the total weight of a microcapsule.
- microcapsules suitable for the invention have a dimension, in particular a diameter, less than or equal to 5 pm, in particular less than or equal to 1 pm, and preferably less than or equal to 500 nm.
- the dimension discussed in the previous paragraph corresponds to the diameter of the microcapsules, in particular the average diameter of a set of particles.
- an adhesive composition comprising microcapsules of size greater than 5 ⁇ m does not have satisfactory transparency for application in automobile glazing.
- An adhesive composition according to the invention may contain from 1% to 10% by weight of microcapsules as described above relative to the total weight of the adhesive composition, in particular from 2% to 8% by weight and preferably from 3% to 7% by weight of said microcapsules.
- An adhesive composition according to the invention may also comprise, as expansion means, chemical expansion agents.
- Chemical blowing agents are compounds capable of releasing gas by thermal decomposition. These are known and typically used to form polymeric foams.
- the gas released by these chemical expansion agents makes it possible to weaken the cohesive forces at the PVB/glass interfaces and ensures easy disassembly of laminated glazing for automobiles. .
- the chemical blowing agents suitable for the invention have carbon/oxygen (CO), nitrogen (NN) and/or nitrogen/sulfur (NS) bonds capable of being broken by the addition of heat. This rupture results in the release in gaseous form of carbon dioxide (CO2), ammonia (NH3), dinitrogen (N2), sulfur dioxide (SO2) and/or water (H2O).
- the chemical blowing agents suitable for the invention can be chosen from carbonates; azo compounds, in particular hydrazides such as azodicarbonamide; hydrazine derivatives; nitroso- and/or tetrazole compounds.
- carbonates suitable for use as a chemical blowing agent according to the invention mention may be made of sodium bicarbonate, sodium carbonate and zinc carbonate.
- azobisisobutyronitrile and hydrazides such as azobicarbonamide and diisopropyl azodicarboxylate.
- hydrazine derivatives capable of being used as a chemical blowing agent according to the invention
- semicarbazide polymeric sulfonic hydrazides such as poly(methacryloyl toluenesulfonylhydrazide); and sulfonylsemicarbazides such as / /ra-tolucnc-siilfonyl semicarbazide and 4,4'-oxybis(benzenesulfonylsemicarbazide).
- tetrazoles suitable for use as a chemical expanding agent according to the invention mention may be made of 5-phenyltetrazole and 5-aminotetrazole.
- the adhesive composition according to the invention comprises a phase consisting essentially of PVB, the at least one expansion means being located alternately on the surface of the phase consisting essentially of PVB or in at minus an additional phase comprising PVB.
- composition according to the invention can take the form of different mono- or multiphasic systems.
- the composition according to the invention consists of a phase comprising PVB and at least one expansion means.
- the composition according to the invention comprises a phase consisting essentially of PVB on the surface of which is located at least one expansion means.
- Such a composition can for example be obtained by depositing a coating composed of an organic phase, in particular consisting of polymers, preferably PVB and expansion means, on the surface of the phase consisting of PVB.
- the composition according to the invention consists of a first phase comprising PVB and at least one expansion means and a second phase consisting of PVB.
- the composition according to the invention consists of a first phase comprising PVB and at least one expansion means, a second phase consisting of PVB and a third phase comprising PVB and at least one expansion means.
- a composition according to the third and fourth embodiments can for example be obtained by coextrusion of an adhesive composition according to the invention and a composition consisting of PVB.
- the second, third and fourth embodiments have the advantage of concentrating the at least one expansion means in a zone close to the interface, or even at the interface, of the adhesive composition with the support on to which it adheres, in particular a sheet of glass. This allows, during disassembly, better weakening of the cohesive forces between the PVB and the support on which it adheres, for example glass. This improvement may be characterized by the use of a lesser quantity of expansion means and/or by a reduction in the heating time required to obtain disassembly.
- the invention also relates to a process for obtaining an adhesive composition according to the invention, comprising a step of mixing PVB with a plasticizing composition comprising at least one plasticizer and at least one expansion means.
- an adhesive composition based on PVB such as an adhesive composition according to the invention
- at least one plasticizer is added so as to modify the elastic properties of the composition. adhesive, in particular its flexibility and processability.
- plasticizers are also known to those skilled in the art and are, for example, phthalates, trimelliates, adipates, sebacates, maleates, epoxidized fatty acids, sulfonamides, organophosphates, polyethers or mixtures thereof.
- plasticizers are also known to those skilled in the art and are, for example, phthalates, trimelliates, adipates, sebacates, maleates, epoxidized fatty acids, sulfonamides, organophosphates, polyethers or mixtures thereof.
- triethylene glycol di-2-ethylhexanoate (3G8) can be used as a plasticizer in adhesive compositions suitable for the invention.
- the inventors discovered that the at least one expansion means included in an adhesive composition according to the invention could be incorporated therein according to a usual process for preparing an adhesive composition based on PVB, when addition of plasticizer.
- the process for preparing an adhesive composition according to the invention may comprise an initial step of mixing at least one plasticizer with the at least one expansion means.
- phase consisting essentially of PVB we mean a phase comprising no constituents other than those usual for an adhesive composition for glass articles based on PVB.
- a phase consisting essentially of PVB is therefore likely to contain at least one plasticizer and at least one additive such as a dye or a UV ray inhibitor.
- a phase consisting essentially of PVB therefore comprises less than 1% by weight of expansion means, in particular less than 0.5% by weight and preferably less than 0.1% by weight per relative to the total weight of the phase.
- a phase consisting essentially of PVB is preferably devoid of means of expansion.
- the invention also relates to laminated glazing for automobiles comprising at least two sheets of glass and, as a lamination interlayer, a layer of adhesive composition according to the invention.
- the face Fl is the external (outer) face of the exterior glass, preferably tinted;
- - face F2 is the internal face (lamination interlayer side) of the exterior glass
- the lamination interlayer here made up of the adhesive composition according to the invention
- - face F3 is the internal face (lamination interlayer side) of the interior glass, preferably colorless and often of thickness less than or equal to that of the exterior glass;
- - face F4 is the internal face (passenger compartment side) of the interior glass.
- the laminated glazing for automobiles according to the invention comprises a layer of PVB and at least one layer of adhesive composition according to the invention, said layer(s) of adhesive composition being in contact of at least one sheet of glass.
- Such glazing can be obtained using an adhesive composition as described in the third and fourth embodiments described above.
- the expansion means are located in contact with at least one sheet of glass.
- Such glazing can be obtained using an adhesive composition as described in the second embodiment described above.
- the layer of adhesive composition and/or the expansion means is/are in contact with face F2 and/or face F3 of the laminated glazing according to the invention.
- the cohesive forces at the interfaces of the lamination interlayer and the glass can particularly be weakened on demand, while minimizing the quantity of expansion means(s) present in the lamination interlayer.
- Laminated glazing according to the invention corresponding to the particular embodiments described above are therefore particularly easily disassembled.
- the laminated glazing according to the invention may have a blur of at most 2%, in particular at most 1.5%, and preferably less than or equal to 1%.
- the adhesive composition can have a thickness of from 100 pm to 2100 pm, in particular from 300 pm to 1100 pm and preferably from 650 pm to 850 pm.
- the glass sheets can have a thickness of 0.1 mm to 6 mm, in particular 0.3 mm to 5 mm and preferably 0.7 mm. at 3mm.
- the glass sheets suitable for laminated glazing for automobiles according to the invention may consist of mineral glass, in particular chosen from soda-lime, aluminosilicate and borosilicate glass.
- the glass sheets suitable for laminated glazing for automobiles according to the invention are chosen from silico-soda-lime glasses.
- the glass sheets suitable for laminated glazing for automobiles according to the invention are preferably colorless, and have a light transmission factor of at least 85%, or even 90%, preferably within the meaning of standard EN 410. : 1998.
- the glass sheets suitable for laminated glazing for automobiles according to the invention can be clear glasses (with light transmission greater than or equal to 90% for a thickness of 4 mm), for example glasses with standard soda-lime compositions such as Planilux® from the company Saint-Gobain Glass, or extra-clear (with light transmission greater than or equal to 91.5% for a thickness of 4 mm), for example a silico-soda-lime glass with less than 0.05% by weight of Fe III or Fe20s such as Diamant® glass from Saint-Gobain Glass, or Optiwhite® from Pilkington, or B270® from Schott, or other composition described in document WO04/025334 .
- the glass sheets suitable for laminated glazing for automobiles according to the invention can also be made of Planiclear® glass from the company Saint-Gobain Glass.
- the glass sheets suitable for laminated glazing for automobiles according to the invention may also be curved and/or tempered glass, in particular thermally, preferably at a temperature greater than or equal to 450° C., or better still greater than or equal to 450° C. equal to 600°C.
- the laminated glazing for automobiles according to the invention is a windshield or a roof, in particular a windshield.
- the laminated glazing for automobiles according to the invention is a roof, it must meet current automobile specifications in particular for light transmission TL and/or energy transmission TE and/or energy reflection RE and/or again for the total transmission of TTS solar energy.
- TTS less than 30%, in particular less than 26% and preferably between 20% and 23%.
- the light transmission can be greater than or equal to 70%, in particular greater than or equal to 75% and preferably at least 80%.
- the laminated glazing for automobiles according to the invention is a windshield
- the following configuration can be provided:
- the face Fl is the external (outer) face of the exterior glass, preferably colorless with little tint
- face F2 is the internal face (lamination interlayer side) of the exterior glass
- the lamination interlayer is the adhesive composition according to the invention, if necessary tinted in order to compensate for the weak tint of the exterior glass
- - face F3 is the internal face (lamination interlayer side) of the interior glass, preferably colorless;
- - face F4 is the internal face (passenger compartment side) of the interior glass.
- Laminated glazing according to the invention is easily disassembled by heating, which provides heat to the adhesive composition comprising an expansion means, under the effect of which said expansion means increases the total volume of the adhesive composition and weakens the cohesive forces at the interfaces between the adhesive composition and the glass sheets.
- the invention therefore also relates to a method of disassembling laminated automobile glazing according to the invention, comprising a step of heating the laminated automobile glazing to a temperature of between 110°C and 260°C, in particular from 120°C to 250°C and preferably from 180°C to 220°C for a duration of 0.5 to 10 minutes, in particular 1 to 5 minutes and preferably 1.5 to 3 minutes.
- the heating step is carried out using an oven, a hot air gun, infrared rays, microwaves or by induction.
- the disassembly process according to the invention has the advantage of being easily implemented and of making it possible to recover in a short time the constituent elements of the laminated glazing for automobiles (adhesive composition and glass sheets) which are non-polluted. , that is to say in which less than 5% by weight of the other constituents of the automobile glazing remain.
- the invention finally relates to a process for obtaining laminated glazing for automobiles according to the invention, comprising a step of applying an adhesive composition according to the invention to one side of a sheet of glass then a step of placing a second sheet of glass on the adhesive composition.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Ceramic Engineering (AREA)
- Joining Of Glass To Other Materials (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR2202862A FR3134107B1 (fr) | 2022-03-30 | 2022-03-30 | Composition adhésive pour article verrier comprenant des moyens d’expansion et vitrage feuilleté pour automobile comprenant une telle composition |
| PCT/EP2023/057999 WO2023186893A1 (fr) | 2022-03-30 | 2023-03-28 | Composition adhésive pour article verrier comprenant des moyens d'expansion et vitrage feuilleté pour automobile comprenant une telle composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4499767A1 true EP4499767A1 (fr) | 2025-02-05 |
Family
ID=81648276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP23715825.8A Pending EP4499767A1 (fr) | 2022-03-30 | 2023-03-28 | Composition adhésive pour article verrier comprenant des moyens d'expansion et vitrage feuilleté pour automobile comprenant une telle composition |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20250206998A1 (fr) |
| EP (1) | EP4499767A1 (fr) |
| CN (1) | CN117157368A (fr) |
| FR (1) | FR3134107B1 (fr) |
| WO (1) | WO2023186893A1 (fr) |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3615972A (en) | 1967-04-28 | 1971-10-26 | Dow Chemical Co | Expansible thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same |
| US4049604A (en) | 1969-03-10 | 1977-09-20 | The Dow Chemical Company | Emulsion polymerization method for preparing aqueous dispersions of organic polymer particles |
| US4016110A (en) | 1972-07-26 | 1977-04-05 | The Dow Chemical Company | Process for the preparation of expandable microspheres |
| JPS6019033A (ja) | 1983-07-12 | 1985-01-31 | Matsumoto Yushi Seiyaku Kk | 中空マイクロバル−ンおよびその製法 |
| SE9003600L (sv) | 1990-11-12 | 1992-05-13 | Casco Nobel Ab | Expanderbara termoplastiska mikrosfaerer samt foerfarande foer framstaellning daerav |
| JP3186835B2 (ja) | 1992-05-28 | 2001-07-11 | 松本油脂製薬株式会社 | 熱膨張性マイクロカプセルおよびその製法と膨張方法 |
| JP2894990B2 (ja) | 1996-06-14 | 1999-05-24 | 松本油脂製薬株式会社 | 耐熱性と耐溶剤性に優れた熱膨張性マイクロカプセル |
| EP1149628A1 (fr) | 2000-04-28 | 2001-10-31 | Akzo Nobel N.V. | Produit chimique et procédé |
| CA2447273A1 (fr) | 2001-05-25 | 2002-12-05 | Apache Products Company | Microspheres expansibles pour isolation mousse et procedes correspondants |
| JP4393377B2 (ja) | 2002-05-24 | 2010-01-06 | 松本油脂製薬株式会社 | 熱膨張性マイクロカプセルおよびその利用 |
| FR2844364B1 (fr) | 2002-09-11 | 2004-12-17 | Saint Gobain | Substrat diffusant |
| EP1964903B1 (fr) | 2005-12-19 | 2017-03-22 | Kureha Corporation | Microspheres thermo-expansibles, leur procede de production et leurs utilisations |
| PL2026902T3 (pl) | 2006-06-08 | 2017-02-28 | Akzo Nobel N.V. | Mikrosfery |
| JPWO2010122942A1 (ja) * | 2009-04-21 | 2012-10-25 | 日東電工株式会社 | 加熱膨張型再剥離性アクリル系粘着テープ又はシート |
| KR101603870B1 (ko) * | 2015-04-03 | 2016-03-15 | 영원주식회사 | 폴리비닐부티랄 박리제 및 이를 이용한 폴리비닐부티랄 점착 필름의 박리 방법 |
| CN107267103A (zh) * | 2016-04-08 | 2017-10-20 | 卢斌 | 一种含气凝胶的透明隔热防火胶及其制备方法和隔热防火玻璃 |
| KR20180136029A (ko) | 2017-06-13 | 2018-12-24 | 삼성디스플레이 주식회사 | 열박리형 접착 부재 및 이를 포함하는 표시 장치 |
-
2022
- 2022-03-30 FR FR2202862A patent/FR3134107B1/fr active Active
-
2023
- 2023-03-28 US US18/852,049 patent/US20250206998A1/en active Pending
- 2023-03-28 EP EP23715825.8A patent/EP4499767A1/fr active Pending
- 2023-03-28 CN CN202380009983.2A patent/CN117157368A/zh active Pending
- 2023-03-28 WO PCT/EP2023/057999 patent/WO2023186893A1/fr not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| CN117157368A (zh) | 2023-12-01 |
| US20250206998A1 (en) | 2025-06-26 |
| FR3134107A1 (fr) | 2023-10-06 |
| WO2023186893A1 (fr) | 2023-10-05 |
| FR3134107B1 (fr) | 2025-06-20 |
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