WO2012133270A1 - 耐候性接着剤組成物 - Google Patents
耐候性接着剤組成物 Download PDFInfo
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- WO2012133270A1 WO2012133270A1 PCT/JP2012/057696 JP2012057696W WO2012133270A1 WO 2012133270 A1 WO2012133270 A1 WO 2012133270A1 JP 2012057696 W JP2012057696 W JP 2012057696W WO 2012133270 A1 WO2012133270 A1 WO 2012133270A1
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- WIPO (PCT)
- Prior art keywords
- adhesive composition
- polyisocyanate compound
- polyester polyol
- acid
- weather
- Prior art date
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
-
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
-
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
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- 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
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8022—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with polyols having at least three hydroxy groups
- C08G18/8025—Masked aliphatic or cycloaliphatic polyisocyanates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/712—Weather resistant
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/3154—Of fluorinated addition polymer from unsaturated monomers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
- Y10T428/31573—Next to addition polymer of ethylenically unsaturated monomer
- Y10T428/31587—Hydrocarbon polymer [polyethylene, polybutadiene, etc.]
Definitions
- the present invention relates to a weather-resistant adhesive composition suitable for outdoor industrial use and the like.
- a polyurethane-based adhesive containing a polyester polyol is known as an adhesive composition having weather resistance for outdoor industrial applications, such as building materials and solar cell panel materials.
- Patent Document 1 discloses a laminate comprising a polyester film, a specific polyurethane-based adhesive, an aluminum foil, and a polyester film, a specific polyurethane-based adhesive, and a polyvinylidene fluoride film, and has excellent long-term moisture and heat resistance.
- Patent Document 2 discloses a laminate in which three types of multilayer films are bonded together with a polyurethane-based adhesive, and is said to be excellent in weather resistance.
- the prior art is generally performed to perform an aging treatment for a long time of about 5 to 7 days at a relatively low temperature of about 50 to 60 ° C. It is preferable from the viewpoints of energy saving, improvement in workability / productivity and cost reduction if the aging temperature is set to the same level as or lower than the current level and the aging time can be shortened.
- an object of the present invention is to provide a weather-resistant adhesive that exhibits a practical level of adhesion, heat-and-moisture resistance, and weather resistance by low-temperature and short-term aging.
- an adhesive composition comprising a polyester polyol having a certain range of acid values and a polyisocyanate compound has a relatively low temperature of about 40 to 60 ° C. It was found that practical aging adhesiveness, moist heat resistance and weather resistance are exhibited by short-term aging for about 1 day. That is, the present invention (1) Weather resistance containing a polyester polyol (A) having an acid value of 30 to 150 equivalents / 10 6 g and a polyisocyanate compound (B) comprising an aliphatic polyisocyanate compound and / or an alicyclic polyisocyanate compound Adhesive composition.
- A polyester polyol
- B polyisocyanate compound
- the polyisocyanate compound (B) is an adduct of hexamethylene diisocyanate (HDI), an isocyanurate of HDI, a biuret of HDI, an adduct of isophorone diisocyanate (IPDI), an isocyanurate of IPDI, an IPDI
- the weather-resistant adhesive composition according to any one of (1) to (4), comprising at least one selected from the group consisting of biuret bodies.
- the blending ratio of the polyester polyol (A) and the polyisocyanate compound (B) is 1 to 20 parts by weight of the polyisocyanate compound (B) with respect to 100 parts by weight of the polyester polyol (A)
- a weather-resistant adhesive composition according to any one of (5) is 1 to 20 parts by weight of the polyisocyanate compound (B) with respect to 100 parts by weight of the polyester polyol (A)
- a weather-resistant adhesive composition according to any one of (5) One or two or more films made of polyester, fluorine-based polymer and polyethylene are bonded together using the weather-resistant adhesive composition described in any of (1) to (6) as an adhesive layer Laminated body.
- the weather resistant adhesive composition according to any one of (1) to (6) is applied to a film made of any one of polyester, fluorine-based polymer, and polyethylene, and any one of polyester, fluorine-based polymer, and polyethylene is applied.
- a method for producing a laminate comprising: laminating a film comprising the above and
- the adhesive composition of the present invention exhibits practical levels of adhesiveness, heat-and-moisture resistance, and weather resistance by short-term aging of about 1 day at a relatively low temperature of about 40 to 60 ° C. For this reason, it is possible to save energy, improve workability / productivity, and reduce costs.
- the adhesive composition of the present invention comprises a polyisocyanate compound (B) comprising a polyester polyol (A) having an acid value of 30 to 150 equivalents / 10 6 g and an aliphatic polyisocyanate compound and / or an alicyclic polyisocyanate compound. ).
- the polyester polyol (A) used in the present invention has a chemical structure obtained by polycondensation of a polyvalent carboxylic acid and a polyhydric alcohol.
- polycarboxylic acids include aliphatic dibasic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, brassic acid, dimer acid and hydrogenated products thereof, terephthalic acid, isophthalic acid
- dibasic acids such as aromatic dibasic acids such as acid, orthophthalic acid and naphthalenedicarboxylic acid are preferably used.
- polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, neopentyl glycol, methylpentanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, dodecanediol and other aliphatic glycols, It is preferable to use one or more glycols such as cycloaliphatic glycol such as cyclohexanediol, hydrogenated xylylene glycol, and aromatic ring-containing glycol such as xylylene glycol.
- dibasic acid copolymerized with the polyester polyol (A) used in the present invention examples include aromatic dibasic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid from the viewpoint of improving heat and humidity resistance. It is desirable to use an acid. Further, from the viewpoint of improving the weather resistance, it is preferable that isophthalic acid and / or orthophthalic acid is copolymerized in a total of 60 mol% or more. Further, keeping the copolymerization ratio of terephthalic acid low is effective in improving the weather resistance, preferably less than 40 mol%, more preferably less than 25 mol%, and less than 5 mol%. More preferably.
- the structure preferably contains a long-chain aliphatic structure.
- the long-chain aliphatic structure is preferably an aliphatic glycol having 5 or more carbon atoms, more preferably an aliphatic glycol having 6 to 12 carbon atoms, from the viewpoint of heat and humidity resistance.
- a conventionally known polymerization catalyst such as a titanium compound such as tetra-n-butyl titanate, tetraisopropyl titanate, titanium oxyacetylacetonate, tributoxyantimony, etc.
- Antimony compounds such as antimony trioxide, germanium compounds such as tetra-n-butoxygermanium, germanium oxide, and the like can be used. These catalysts may be used alone or in combination of two or more. Titanium compounds are preferred from the viewpoint of polymerization reactivity.
- the acid value of the polyester polyol (A) used in the present invention is 30 to 150 equivalent / 10 6 g, and particularly preferably 80 to 100 equivalent / 10 6 g. If the acid value is too low, there is no effect in shortening the aging time, and if the acid value is too high, the wet heat resistance of the resulting adhesive layer tends to be lowered.
- the acid value can be adjusted by introducing a carboxyl group into the polyester polyol.
- the method of introducing a carboxyl group into a polyester polyol is a method of post-adding an acid anhydride under normal pressure and nitrogen atmosphere after polymerizing the polyester polyol to give an acid value, or an oligomer state before making the polyester high molecular weight
- Aromatic carboxylic anhydrides and alicyclic carboxylic anhydrides such as -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, naphthalene-1,8: 4,5-tetracarboxylic dianhydride It is preferable that one or two or more of these can be selected and used.
- the range of the glass transition temperature of the polyester polyol (A) used in the present invention is ⁇ 20 to 20 ° C., more preferably ⁇ 10 to 10 ° C.
- a dibasic acid or glycol having a long aliphatic chain may be introduced into the composition, and an aliphatic glycol having 5 or more carbon atoms may be copolymerized in order to have heat and heat resistance. Is preferred. If the glass transition temperature is too high, the adhesive strength to the substrate tends to be low, and if the glass transition temperature is too low, the adhesive layer is too flexible and the adhesive strength / moisture heat resistance may be reduced.
- the number average molecular weight of the polyester polyol (A) used in the present invention is not particularly limited, but is preferably 5,000 to 40,000, more preferably 9,000 to 30,000. If the number average molecular weight of the polyester resin is too low, the molecular weight between crosslinks is small, so that the coating film becomes too hard and the adhesive strength may be lowered. If it is 40,000 or more, it cannot react sufficiently with the curing agent, so that the heat and humidity resistance may be lowered.
- the polyisocyanate compound (B) used in the present invention comprises an aliphatic polyisocyanate compound and / or an alicyclic polyisocyanate compound.
- Preferred examples of the aliphatic polyisocyanate compound include hexamethylene diisocyanate, and examples of the alicyclic polyisocyanate compound include isophorone diisocyanate, which are preferable in terms of improving weather resistance.
- the polyisocyanate compound may be an isocyanurate body, a biuret body, or an adduct body, and an isocyanurate body is particularly preferable.
- the blending ratio of the polyester polyol (A) and the polyisocyanate compound (B) used in the present invention is preferably 1 to 20 parts by weight of the polyisocyanate compound (B) with respect to 100 parts by weight of the polyester polyol (A). More preferably, it is 5 to 10 parts by weight. If the blending ratio of the polyisocyanate compound (B) is too low, the crosslinking density is too low, which may adversely affect the adhesion and / or wet heat resistance. If the blending ratio is too high, the crosslinking density of the adhesive layer is too high. There is a possibility of poor adhesion.
- the adhesive composition used in the present invention has terminal groups such as a carbodiimide compound, an oxazoline compound, and an epoxy compound in order to block a carboxyl group generated when hydrolysis occurs in the polyester component constituting the adhesive composition. You may mix
- carbodiimide compound examples include N, N′-di-o-toluylcarbodiimide, N, N′-diphenylcarbodiimide, N, N′-di-2,6-dimethylphenylcarbodiimide, N, N′-bis (2, 6-diisopropylphenyl) carbodiimide, N, N′-dioctyldecylcarbodiimide, N-triyl-N′-cyclohexylcarbodiimide, N, N′-di-2,2-di-tert- butylphenylcarbodiimide, N-triyl-N '-Phenylcarbodiimide, N, N'-di-p-nitrophenylcarbodiimide, N, N'-di-p-aminophenylcarbodiimide, N, N'-di- p -hydroxyphenylcarbodiimide, N, N'-
- oxazoline compound examples include monooxazoline compounds such as 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, and 2,4-diphenyl-2-oxazoline.
- monooxazoline compounds such as 2-oxazoline, 2-methyl-2-oxazoline, 2-phenyl-2-oxazoline, 2,5-dimethyl-2-oxazoline, and 2,4-diphenyl-2-oxazoline.
- 2,2 ′-(1,4 And dioxazoline compounds such as -butylene) -bis (2-oxazoline) and 2,2 '-(1,4-phenylene) -bis (2-oxazoline).
- epoxy epoxy compound examples include diglycidyl ethers of aliphatic diols such as 1,6-hexanediol, neopentyl glycol, and polyalkylene glycol, sorbitol, sorbitan, polyglycerol, pentaerythritol, diglycerol, glycerol, and trimethylol.
- Aliphatic or aromatic such as polyglycidyl ether of aliphatic polyol such as propane, polyglycidyl ether of alicyclic polyol such as cyclohexanedimethanol, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, trimellitic acid, adipic acid, sebacic acid Diglycidyl ester or polyglycidyl ester, resorcinol, bis- (p-hydroxyphenyl) methane, 2,2-bis- (p-hydroxyl) Diglycidyl ethers or polyglycidyl ethers of polyhydric phenols such as phenyl) propane, tris- (p-hydroxyphenyl) methane, 1,1,2,2-tetrakis (p-hydroxyphenyl) ethane, N, N-diglycidyl N-glycidyl derivatives of amines such as aniline, N, N-diglycidyl toluid
- the adhesive composition of the present invention may contain known additives such as ultraviolet absorbers and antioxidants, and may further improve weather resistance and wet heat resistance.
- a laminate can be obtained by laminating one or more films made of any one of polyester, fluoropolymer and polyethylene.
- the laminate may be a film / adhesive layer / film three-layer laminate, a film / adhesive layer / film / adhesive layer / film five-layer laminate, or a laminate having more layers. good.
- each film constituting the laminate may be made of the same kind of material or different kinds of material.
- polyester constituting the polyester film examples include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), and polycyclohexanedimethanol-terephthalate (PCT).
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PBT polybutylene terephthalate
- PCT polycyclohexanedimethanol-terephthalate
- the fluorinated polymer constituting the film made of the fluorinated polymer is, for example, a fluorinated polyolefin and a polyolefin-fluorinated polyolefin copolymer, and specifically, polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF), Polychlorotrifluoroethylene (PCTFE), polyethylene tetrafluoroethylene (ETFE), polytetrafluoroethylene (PTFE), tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer ( FEP).
- PVDF polyvinyl fluoride
- PVDF polyvinylidene fluoride
- PCTFE Polychlorotrifluoroethylene
- ETFE polyethylene tetrafluoroethylene
- PTFE polytetrafluoroethylene
- PFA tetrafluor
- Examples of the polyethylene constituting the polyethylene film include polyethylene, ultrahigh molecular weight polyethylene, and those obtained by adding various additives to these.
- the base material used in the present invention is preferably subjected to a surface treatment such as corona treatment, flame treatment, or plasma treatment for the purpose of improving adhesion on the coated surface and the adhesive surface.
- a surface treatment such as corona treatment, flame treatment, or plasma treatment for the purpose of improving adhesion on the coated surface and the adhesive surface.
- the thickness (after drying) of the adhesive layer made of the adhesive composition of the present invention is generally 5 to 30 microns, but is not limited to this range.
- polyester composition The composition and composition ratio of the polyester resin were determined by 1 H-NMR measurement (proton nuclear magnetic resonance spectroscopy) with a resonance frequency of 400 MHz.
- the measuring apparatus was an NMR apparatus 400-MR manufactured by VARIAN, and deuterated chloroform was used as a solvent.
- Glass transition temperature Tg This was measured by a differential scanning calorimeter (SII, DSC-200). As a sample, 5 mg of a sample was placed in an aluminum-suppressed lid-type container, sealed, cooled to ⁇ 50 ° C. using liquid nitrogen, and then heated to 150 ° C. at 20 ° C./min. In the endothermic curve obtained in the process, the temperature at the intersection of the base line before the endothermic peak and the tangent line toward the endothermic peak was defined as the glass transition temperature (Tg, unit: ° C).
- a 0.2 g sample was precisely weighed and dissolved in 40 ml of chloroform, and titrated with an ethanol solution of 0.01 N potassium hydroxide. Phenolphthalein was used as an indicator. The measured value was converted to the equivalent per 10 6 g of the sample, and the unit was equivalent / 10 6 g.
- Polyester Polyol (1) In a reaction vessel equipped with a stirrer, a condenser and a thermometer, 464 parts of isophthalic acid, 179 parts of orthophthalic acid, 4 parts of trimellitic anhydride, 100 parts of neopentyl glycol, 1,6-hexanediol 598 Part, tetra-n-butyl titanate (hereinafter sometimes abbreviated as TBT) as a catalyst was charged in an amount of 0.03 mol% based on the total acid components, and the ester exchange reaction was carried out from 160 ° C. to 230 ° C. over 4 hours. It was.
- TBT tetra-n-butyl titanate
- Neopentyl glycol / 1,6-hexanediol 10/90.
- the number average molecular weight was 18,000, the glass transition temperature was 0 ° C., and the acid value was 40 equivalents / 10 6 g.
- the number average molecular weight was 18,000, the glass transition temperature was 0 ° C., and the acid value was 10 equivalents / 10 6 g.
- Polyester resins (2) to (14) according to the production examples of the polyester resin (1) except that the types and blending ratios of the raw materials are changed. , (16) was produced. The results are shown in Table 1.
- TPA terephthalic acid residue IPA: isophthalic acid residue
- OPA orthophthalic acid residue
- SA sebacic acid residue
- TMA trimellitic acid residue
- EG ethylene glycol residue
- NPG neopentyl glycol residue
- HD 1,6- Hexanediol residue
- TMEG Ethylene glycol bisanhydro trimellitate residue
- Main agents (1) to (16) Resin solution having a solid content of 30% by weight obtained by dissolving polyester polyols (1) to (16) in ethyl acetate.
- Curing agent 1 A solution having a solid content of 50% by weight obtained by dissolving a polyisocyanate compound HDI isocyanurate body “Desmodur N3300 manufactured by Sumika Bayer” in ethyl acetate.
- Curing agent 2 A solution having a solid content of 50% by weight obtained by dissolving a polyisocyanate compound HDI buret body “Desmodule N3200 manufactured by Sumika Bayer” in ethyl acetate.
- Curing agent 3 A solution having a solid content of 50% by weight obtained by dissolving a polyisocyanate compound HDI adduct “Sumijoule HT manufactured by Sumika Bayer” in ethyl acetate.
- Curing agent 4 A solution having a solid content of 50% by weight obtained by dissolving polyisocyanate compound IPDI isocyanurate body "Desmodur Z4470 manufactured by Sumika Bayer” in ethyl acetate.
- Curing agent 5 A solution having a solid content of 50% by weight obtained by dissolving a polyisocyanate compound TDI isocyanurate body “Desmodur IL 1351 manufactured by Sumika Bayer” in ethyl acetate.
- Additive 1 An antioxidant (manufactured by BASF, Irganox 1010) dissolved in ethyl acetate to a solid content of 10% by weight.
- Additive 2 A UV absorber (manufactured by BASF, Tinuvin 234) dissolved in ethyl acetate to a solid content of 10% by weight.
- Example 1 Manufacture of adhesive (1) 10 parts of the main agent (1), 0.6 part of the curing agent 1, 0.15 part of the additive 1 and 0.3 part of the additive 2 were mixed and mixed to obtain an adhesive (1).
- the adhesive (1) was applied to the substrate A with an applicator so that the dry film thickness was 10 ⁇ m, and the solvent was volatilized. Then, the substrate B was pressure-bonded using a dry laminator. The dry lamination was performed at a roll temperature of 120 ° C., a roll load of 3 kg / cm, and a speed of the object to be bonded of 1 m / min. Next, the adhesive was cured by aging at 40 ° C. for 1 day to obtain a base material A / adhesive layer / base material B laminate. In Example 1, a polyester film (manufactured by Toyobo, Shine Beam Q1210, thickness 125 ⁇ m) was used for both the base A and the base B.
- the substrate A / adhesive layer / substrate B laminate after aging is cut into a strip of 15 mm in width, and the peel strength between the substrate A and the substrate B is measured with Tensilon (Toyo Sokki Co., Ltd., UTM-IV). (T-peel peeling, pulling speed 50 mm / min) was measured and used as the initial adhesive strength.
- the evaluation results are shown in Table 3. Evaluation criteria: ⁇ : 800 g / 15 mm or more ⁇ : 600 g / 15 mm or more and less than 800 g / 15 mm ⁇ : 400 g / 15 mm or more and less than 600 g / 15 mm ⁇ : less than 400 g / 15 mm
- the substrate A / adhesive layer / substrate B laminate after aging was subjected to an environmental load of 105 ° C., 100% RH, 192 hours using a retort tester (ES-315 manufactured by Tommy Industries Co., Ltd.). After giving, it was cut into a strip shape with a width of 15 mm, and the peel strength (T-peel peel, pulling speed 50 mm / min) between the base A and the base B was measured.
- the retention of peel strength was calculated from the following formula and used as an index of heat and humidity resistance. The retention rate indicated that the higher the value, the better the heat and humidity resistance.
- Retention rate (%) (Peel strength after wet heat test / Peel strength before wet heat test) ⁇ 100 Evaluation criteria: ⁇ : 80% or more ⁇ : 60% or more and less than 80% ⁇ : 40% or more and less than 60% ⁇ : Less than 40%
- An adhesive (1) was applied to a polyester film (Toyobo E5101, thickness 50 ⁇ m, corona-treated surface) with an applicator so that the dry film thickness was 10 ⁇ m, and the solvent was evaporated, and then a polypropylene film (Toyobo P2161, thickness) 50 ⁇ m, non-corona-treated surface) was pressure-bonded using a dry laminator.
- the dry lamination was performed at a roll temperature of 120 ° C., a roll load of 3 kg / cm, and a speed of the object to be bonded of 1 m / min.
- aging was performed at 40 ° C. for 24 hours to cure the adhesive, and the polypropylene film was peeled off to obtain a polyester film / adhesive laminate.
- Adhesive (1) is applied to a polyester film (Toyobo, Shine Beam Q1210, thickness 50 ⁇ m) to a dry film thickness of 20 microns, the solvent is evaporated, and then a polypropylene film (Toyobo P2161, thickness 50 ⁇ m, non-corona) The treated surface) was pressure-bonded using a dry laminator.
- the dry lamination was performed at a roll temperature of 120 ° C., a roll load of 3 kg / cm, and a speed of the object to be bonded of 1 m / min.
- aging was performed at 40 ° C. for 24 hours to cure the adhesive, and the polypropylene film was peeled off to obtain a polyester film / adhesive laminate.
- Ultraviolet rays were irradiated from the adhesive side of the polyester film / adhesive laminate after the aging.
- Ultraviolet irradiation is performed using a UV irradiation tester (Iwasaki Electric Co., Ltd., iSuper UV Tester, SUV-W151).
- the irradiation conditions are 60 ° C. (black panel temperature), relative humidity 60%, and irradiation only.
- the irradiation time was 24 hours at an irradiation intensity of 100 mW / cm 2 .
- the Cob value of the polyester film / adhesive laminate before and after UV irradiation was measured using a color difference meter (ZE2000 manufactured by Nippon Denshoku Co., Ltd.), and the difference before and after UV irradiation was used as an indicator of weather resistance. The larger the value, the greater the degree of yellowing, indicating poorer weather resistance.
- the evaluation results are shown in Table 3. Evaluation criteria: ⁇ : Less than +10 ⁇ : +10 or more and less than +15 ⁇ : +15 or more
- Adhesives (2) to (20) were produced in accordance with the adhesive (1) of Example 1 except that the main agent and the curing agent were changed to the formulation shown in Table 2. Next, the adhesive and the base material were changed as shown in Table 3, and the same evaluation as in Example 1 was performed. The evaluation results are shown in Table 3.
- PET Polyester film (Toyobo, Shine Beam Q1210, thickness 125 ⁇ m)
- PVF Polyvinyl fluoride film (DuPont, Tedlar, thickness 25 ⁇ m)
- PE Polyethylene film (thickness 50 ⁇ m)
- aging treatment for a long time of about 5 to 7 days at a relatively low temperature of about 50 to 60 ° C. is generally performed. It is preferable from the viewpoints of energy saving, improvement in workability / productivity and cost reduction if the aging temperature is set to the same level as or lower than the current level and the aging time can be shortened.
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Abstract
Description
(1) 酸価が30~150当量/106gであるポリエステルポリオール(A)と、脂肪族ポリイソシアネート化合物及び/または脂環族ポリイソシアネート化合物からなるポリイソシアネート化合物(B)を含有する耐候性接着剤組成物。
(2) 前記ポリエステルポリオール(A)が、ポリエステルポリオールを構成する全酸成分に対して、イソフタル酸および/またはオルトフタル酸を合計60モル%以上含有するものである、(1)に記載の耐候性接着剤組成物。
(3) 前記ポリエステルポリオール(A)が、炭素数5以上の脂肪族グリコールを含有するものである(1)または(2)に記載の耐候性接着剤組成物。
(4) 前記ポリエステルポリオール(A)のガラス転移温度が-20~20℃であり、数平均分子量が5000~40000である(1)~(3)のいずれかに記載の耐候性接着剤組成物。
(5) 前記ポリイソシアネート化合物(B)が、ヘキサメチレンジイソシアネート(HDI)のアダクト体、HDIのイソシアヌレート体、HDIのビウレット体、イソホロンジイソシアネート(IPDI)のアダクト体、IPDIのイソシアヌレート体、IPDIのビウレット体からなる群より選択される、少なくとも1つ以上含有することを特徴とする、(1)~(4)のいずれかに記載の耐候性接着剤組成物。
(6) ポリエステルポリオール(A)とポリイソシアネート化合物(B)の配合比が、ポリエステルポリオール(A)100重量部に対してポリイソシアネート化合物(B)1~20重量部であることを特徴とする(1)~(5)のいずれかに記載する耐候性接着剤組成物。
(7) ポリエステル、フッ素系ポリマー及びポリエチレンのいずれかからなるフィルムの1種または2種以上を、(1)~(6)のいずれかに記載する耐候性接着剤組成物を接着層とし貼り合わせた積層体。
(8) (1)~(6)のいずれかに記載の耐候性接着剤組成物をポリエステル、フッ素系ポリマー及びポリエチレンのいずれかからなるフィルムに塗布し、ポリエステル、フッ素系ポリマー及びポリエチレンのいずれかからなるフィルムとドライラミネートで積層した後、40℃~70℃でゲル分率が40重量%以上となるまでエージングする、積層体の製造方法。
ポリエステル樹脂の組成及び組成比の決定は共鳴周波数400MHzの1H-NMR測定(プロトン型核磁気共鳴分光測定)にて行った。測定装置はVARIAN社製NMR装置400-MRを用い、溶媒には重クロロホルムを用いた。
試料4mgを、4mlのテトラヒドロフラン(テトラブチルアンモニウムクロライド5mM添加)に溶解した後、0.2μmのメンブランフィルターでろ過した試料溶液のゲル浸透クロマトグラフィー分析を行った。装置はTOSOH HLC-8220で示差屈折率検出器を用い、40℃で測定した。数平均分子量は標準ポリスチレン換算値とし、分子量1000未満に相当する部分を省いて算出した。
示差走査型熱量計(SII社、DSC-200)により測定した。サンプルは試料5mgをアルミニウム抑え蓋型容器に入れ密封し、液体窒素を用いて-50℃まで冷却、次いで150℃まで20℃/分にて昇温させた。その過程にて得られる吸熱曲線において、吸熱ピークが出る前のベースラインと、吸熱ピークに向かう接線との交点の温度をもって、ガラス転移温度(Tg、単位:℃)とした。
試料0.2gを精秤しクロロホルム40mlに溶解し、0.01Nの水酸化カリウムのエタノール溶液で滴定を行った。指示薬にはフェノールフタレインを用いた。測定値を試料106gあたりの当量に換算し、単位は当量/106gとした。
攪拌機、コンデンサー、温度計を具備した反応容器にイソフタル酸464部、オルトフタル酸179部、無水トリメリット酸4部、ネオペンチルグリコール100部、1、6-ヘキサンジオール598部、触媒としてテトラ-n-ブチルチタネート(以下、TBTと略記する場合がある)を全酸成分に対して0.03モル%仕込み、160℃から230℃まで4時間かけてエステル交換反応を行った。次いで系内を徐々に減圧していき、20分かけて5mmHgまで減圧し、さらに0.3mmHg以下の真空下、260℃にて90分間重縮合反応を行った。窒素気流下、220℃まで冷却し、無水トリメリット酸を4部投入し、30分間反応を行った。得られたポリエステルポリオール(1)はNMRによる組成分析の結果、酸成分がモル比でイソフタル酸/オルトフタル酸/トリメリット酸=69.5/30/0.5であり、グリコール成分がモル比でネオペンチルグリコール/1,6-ヘキサンジオール=10/90であった。また、数平均分子量は18,000、ガラス転移温度は0℃、酸価は40当量/106g、であった。
攪拌機、コンデンサー、温度計を具備した反応容器にイソフタル酸464部、オルトフタル酸179部、無水トリメリット酸4部、ネオペンチルグリコール100部、1、6-ヘキサンジオール598部、触媒としてTBTを全酸成分に対して0.03モル%仕込み、160℃から230℃まで4時間かけてエステル交換反応を行った。次いで系内を徐々に減圧していき、20分かけて5mmHgまで減圧し、さらに0.3mmHg以下の真空下、260℃にて90分間重縮合反応を行った。得られたポリエステルポリオール(15)はNMRによる組成分析の結果、モル比でイソフタル酸/オルトフタル酸/トリメリット酸//ネオペンチルグリコール/1,6-ヘキサンジオール=69.5/30/0.5//10/90であった。また、数平均分子量は18,000、ガラス転移温度は0℃、酸価は10当量/106g、であった。
ポリエステル樹脂(1)の製造例に準じて、但し、原料の種類と配合比率を変更して、ポリエステル樹脂(2)~(14)、(16)を製造した。結果を表1に記す。
IPA:イソフタル酸残基
OPA:オルソフタル酸残基
SA:セバシン酸残基
TMA:トリメリット酸残基
EG:エチレングリコール残基
NPG:ネオペンチルグリコール残基
HD:1,6-ヘキサンジオール残基
TMEG:エチレングリコールビスアンヒドロトリメリテート残基
主剤(1)~(16):ポリエステルポリオール(1)~(16)を酢酸エチルに溶解させて得られた固形分30重量%の樹脂溶液。
硬化剤1:ポリイソシアネート化合物HDIイソシアヌレート体「住化バイエル製 デスモジュールN3300」を酢酸エチルに溶解させて得られた固形分50重量%の溶液。
硬化剤2:ポリイソシアネート化合物HDIビューレット体「住化バイエル製 デスモジュールN3200」を酢酸エチルに溶解させて得られた固形分50重量%の溶液。
硬化剤3:ポリイソシアネート化合物HDIアダクト体「住化バイエル製 スミジュールHT」を酢酸エチルに溶解させて得られた固形分50重量%の溶液。
硬化剤4:ポリイソシアネート化合物IPDIイソシアヌレート体「住化バイエル製 デスモジュールZ4470」を酢酸エチルに溶解させて得られた固形分50重量%の溶液。
硬化剤5:ポリイソシアネート化合物TDIイソシアヌレート体「住化バイエル製 デスモジュールIL 1351」を酢酸エチルに溶解させて得られた固形分50重量%の溶液。
添加剤1:酸化防止剤(BASF製、イルガノックス1010)を酢酸エチルに溶解させて固形分10重量%にしたもの。
添加剤2:紫外線吸収剤(BASF製、チヌビン234)を酢酸エチルに溶解させて固形分10重量%にしたもの。
(接着剤(1)の製造)
主剤(1)を10部、硬化剤1を0.6部、添加剤1を0.15部、添加剤2を0.3部配合し混合させたものを接着剤(1)とした。
基材Aに接着剤(1)をドライ膜厚が10μmになるようにアプリケーターで塗布し、溶剤を揮発させたあと、基材Bをドライラミネーターをもちいて圧着させた。ドライラミーションは、ロール温度120℃、ロール荷重3kg/cm、被圧着物速度1m/分、で行った。次いで、40℃、1日のエージングを行なって接着剤を硬化させ、基材A/接着層/基材B積層体を得た。なお、実施例1においては、基材A、基材Bともにポリエステルフィルム(東洋紡製、シャインビームQ1210、厚み125μm)を用いた。
評価基準: ◎:800g/15mm以上
○:600g/15mm以上800g/15mm未満
△:400g/15mm以上600g/15mm未満
×:400g/15mm未満
保持率(%)=(耐湿熱試験後の剥離強度/耐湿熱試験前の剥離強度)×100
評価基準: ◎:80%以上
○:60%以上80%未満
△:40%以上60%未満
×:40%未満
ポリエステルフィルム(東洋紡製E5101、厚み50μm、コロナ処理面)に接着剤(1)をドライ膜厚が10μmになるようにアプリケーターで塗布し、溶剤を揮発させたあと、ポリプロピレンフィルム(東洋紡製P2161、厚み50μm、非コロナ処理面)をドライラミネーターをもちいて圧着させた。ドライラミーションは、ロール温度120℃、ロール荷重3kg/cm、被圧着物速度1m/分、で行った。次いで、40℃、24時間のエージングを行なって接着剤を硬化させ、更にポリプロピレンフィルムを剥離させ、ポリエステルフィルム/接着剤積層体を得た。
硬化度(%)={(B-C)/(A-C)}×100
評価基準: ◎:80%以上
○:40%以上80%未満
×:40%未満
ポリエステルフィルム(東洋紡製、シャインビームQ1210、厚み50μm)に接着剤(1)をドライ膜厚20ミクロンになるように塗布し、溶剤を揮発させたあとポリプロピレンフィルム(東洋紡製P2161、厚み50μm、非コロナ処理面)を、ドライラミネーターを用いて圧着させた。ドライラミーションは、ロール温度120℃、ロール荷重3kg/cm、被圧着物速度1m/分、で行った。次いで、40℃、24時間のエージングを行なって接着剤を硬化させ、更にポリプロピレンフィルムを剥離させ、ポリエステルフィルム/接着剤積層体を得た。
評価基準: ◎:+10未満
○:+10以上+15未満
×:+15以上
実施例1の接着剤(1)に準じ、但し、主剤と硬化剤を表2の配合に変更して、接着剤(2)~接着剤(20)を製造した。次いで、接着剤および基材を表3に記載のように変更し、実施例1同様の評価を行った。評価結果を表3に示した。
PVF:ポリフッ化ビニルフィルム(デュポン製、テドラー、厚み25μm)
PE:ポリエチレンフィルム(厚み50μm)
Claims (8)
- 酸価が30~150当量/106gであるポリエステルポリオール(A)と、脂肪族ポリイソシアネート化合物及び/または脂環族ポリイソシアネート化合物からなるポリイソシアネート化合物(B)を含有する耐候性接着剤組成物。
- 前記ポリエステルポリオール(A)が、ポリエステルポリオールを構成する全酸成分に対して、イソフタル酸および/またはオルトフタル酸を合計60モル%以上含有するものである、請求項1に記載の耐候性接着剤組成物。
- 前記ポリエステルポリオール(A)が、炭素数5以上の脂肪族グリコールを含有するものである請求項1または2に記載の耐候性接着剤組成物。
- 前記ポリエステルポリオール(A)のガラス転移温度が-20~20℃であり、数平均分子量が5000~40000である請求項1~3のいずれかに記載の耐候性接着剤組成物。
- 前記ポリイソシアネート化合物(B)が、ヘキサメチレンジイソシアネート(HDI)のアダクト体、HDIのイソシアヌレート体、HDIのビウレット体、イソホロンジイソシアネート(IPDI)のアダクト体、IPDIのイソシアヌレート体、IPDIのビウレット体からなる群より選択される、少なくとも1つ以上含有することを特徴とする、請求項1~4のいずれかに記載の耐候性接着剤組成物。
- ポリエステルポリオール(A)とポリイソシアネート化合物(B)の配合比が、ポリエステルポリオール(A)100重量部に対してポリイソシアネート化合物(B)1~20重量部であることを特徴とする請求項1~5のいずれかに記載する耐候性接着剤組成物。
- ポリエステル、フッ素系ポリマー及びポリエチレンのいずれかからなるフィルムの1種または2種以上を、請求項1~6のいずれかに記載する耐候性接着剤組成物を接着層とし貼り合わせた積層体。
- 請求項1~6のいずれかに記載の耐候性接着剤組成物をポリエステル、フッ素系ポリマー及びポリエチレンのいずれかからなるフィルムに塗布し、ポリエステル、フッ素系ポリマー及びポリエチレンのいずれかからなるフィルムとドライラミネートで積層した後、40℃~70℃でゲル分率が40重量%以上となるまでエージングする、積層体の製造方法。
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CN201280015957.2A CN103443237B (zh) | 2011-03-28 | 2012-03-26 | 耐候性粘合剂组合物 |
US13/981,676 US8974906B2 (en) | 2011-03-28 | 2012-03-26 | Weather-resistant adhesive composition |
EP12763023.4A EP2692812B1 (en) | 2011-03-28 | 2012-03-26 | Weather resistant adhesive composition |
JP2012515839A JP5900330B2 (ja) | 2011-03-28 | 2012-03-26 | 耐候性接着剤組成物 |
KR1020137021992A KR101879009B1 (ko) | 2011-03-28 | 2012-03-26 | 내후성 접착제 조성물 |
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013027609A1 (ja) * | 2011-08-24 | 2013-02-28 | Dic株式会社 | 板状無機化合物を含有する接着剤用樹脂組成物、および接着剤 |
WO2015033857A1 (ja) * | 2013-09-06 | 2015-03-12 | Dic株式会社 | ポリエステルポリオール、ラミネート接着剤用ポリオール剤、樹脂組成物、硬化性樹脂組成物、ラミネート用接着剤、及び太陽電池用バックシート |
US9777149B2 (en) | 2012-12-26 | 2017-10-03 | Dic Corporation | Polyester resin composition, adhesive and film |
WO2019017366A1 (ja) * | 2017-07-19 | 2019-01-24 | 東洋紡株式会社 | 接着剤組成物 |
JPWO2019198473A1 (ja) * | 2018-04-12 | 2021-05-20 | 東洋紡株式会社 | 耐候性接着剤組成物 |
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EP3247759B1 (en) * | 2015-01-21 | 2021-05-05 | 3M Innovative Properties Company | Chemical resistant polyurethane adhesive |
WO2018160350A1 (en) | 2017-02-28 | 2018-09-07 | 3M Innovative Properties Company | Polyurethane adhesive with chemical resistant |
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CN111783922B (zh) * | 2020-06-09 | 2024-04-09 | 苏州赛伍应用技术股份有限公司 | 一种射频标签、其制备方法及光伏组件 |
EP4155333A1 (en) * | 2021-09-23 | 2023-03-29 | Bostik SA | Adhesive compositions, layered articles and photovoltaic sheets |
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JP7306380B2 (ja) | 2018-04-12 | 2023-07-11 | 東洋紡エムシー株式会社 | 耐候性接着剤組成物 |
Also Published As
Publication number | Publication date |
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US8974906B2 (en) | 2015-03-10 |
US20130309504A1 (en) | 2013-11-21 |
TW201245371A (en) | 2012-11-16 |
CN103443237A (zh) | 2013-12-11 |
JP5900330B2 (ja) | 2016-04-06 |
JPWO2012133270A1 (ja) | 2014-07-28 |
CN103443237B (zh) | 2016-03-02 |
KR101879009B1 (ko) | 2018-07-16 |
KR20140012647A (ko) | 2014-02-03 |
EP2692812A4 (en) | 2014-09-17 |
TWI496862B (zh) | 2015-08-21 |
EP2692812A1 (en) | 2014-02-05 |
EP2692812B1 (en) | 2018-01-10 |
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