WO2012144329A1 - 樹脂組成物、2液型ラミネート用接着剤、積層フィルム及び太陽電池のバックシート - Google Patents
樹脂組成物、2液型ラミネート用接着剤、積層フィルム及び太陽電池のバックシート Download PDFInfo
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- WO2012144329A1 WO2012144329A1 PCT/JP2012/059338 JP2012059338W WO2012144329A1 WO 2012144329 A1 WO2012144329 A1 WO 2012144329A1 JP 2012059338 W JP2012059338 W JP 2012059338W WO 2012144329 A1 WO2012144329 A1 WO 2012144329A1
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/40—High-molecular-weight compounds
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/4216—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from mixtures or combinations of aromatic dicarboxylic acids and aliphatic dicarboxylic acids and dialcohols
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/4219—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from aromatic dicarboxylic acids and dialcohols in combination with polycarboxylic acids and/or polyhydroxy compounds which are at least trifunctional
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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
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- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- 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
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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- 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
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
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- 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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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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
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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
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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
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Definitions
- the present invention relates to a resin composition excellent in substrate adhesiveness under wet heat conditions, a two-component laminating adhesive, a laminated film, and a solar cell backsheet.
- the back sheet installed on the back of the solar cell module is a member for protecting the power generation mechanism such as cells and wiring from the external environment and maintaining insulation, and various functional films are bonded together with adhesives. It consists of a laminate. Adhesives used for such backsheets include high adhesion to various films with different characteristics, such as polyester film and polyvinyl fluoride film, and moisture resistance to maintain long-term adhesion even in open-air environments. A high level of heat is required.
- a polyester obtained by reacting a polyester polyol obtained by reacting neopentyl glycol, 1,6-hexanediol, ethylene glycol, isophthalic acid, and sebacic acid with isophorone diisocyanate As such a backsheet adhesive, a polyester obtained by reacting a polyester polyol obtained by reacting neopentyl glycol, 1,6-hexanediol, ethylene glycol, isophthalic acid, and sebacic acid with isophorone diisocyanate.
- a two-component polyurethane adhesive using a polyurethane polyol as a main component and a trimer of isophorone diisocyanate as a curing agent is known (see Patent Document 1).
- Patent Document 1 A two-component polyurethane adhesive using a polyurethane polyol as a main component and a trimer of isophorone diisocyanate as a curing agent.
- the problem to be solved by the present invention is a resin composition excellent in substrate adhesion under wet heat conditions, a two-component laminating adhesive containing the resin composition, and a layer comprising the adhesive It is providing the laminated sheet and solar cell backsheet which have these.
- the present inventors have a branched structure in the molecule, a weight average molecular weight (Mw) in the range of 25,000 to 200,000, and a molecular weight distribution.
- Mw weight average molecular weight
- Mn polyester polyurethane polyol
- the present invention has a branched structure in the molecule, the weight average molecular weight (Mw) is in the range of 25,000 to 200,000, and the molecular weight distribution (Mw / Mn) is 2.5 or more.
- the present invention relates to a resin composition comprising a polycarbonate resin (C) and a polyisocyanate (D) as essential components.
- the present invention further relates to a two-component laminating adhesive containing the resin composition.
- the present invention further relates to a laminated film having a layer made of the two-component laminating adhesive.
- the present invention further relates to a solar cell backsheet having a layer comprising the two-component laminating adhesive.
- the resin composition of the present invention has a branched structure in the molecule, the weight average molecular weight (Mw) is in the range of 25,000 to 200,000, and the molecular weight distribution (Mw / Mn) is 2.5.
- a polyester polyurethane polyol (A) in the range of ⁇ 25 is contained as an essential component.
- the polyester polyurethane polyol (A) has a branched structure in the molecule, the final cured product has a high crosslink density, so that it does not swell even under wet heat conditions and maintains high adhesiveness. it can.
- the polyester polyurethane polyol (A) has a weight average molecular weight (Mw) in the range of 25,000 to 200,000.
- Mw weight average molecular weight
- the cured product exhibits high strength, and the resin composition is excellent in initial adhesive strength.
- the resin composition has a viscosity suitable for coating.
- the weight average molecular weight (Mw) is less than 25,000, the initial adhesive strength is lowered, and the viscosity is low, so that the resin composition is difficult to apply uniformly.
- the weight average molecular weight (Mw) is in the range of 30,000 to 100,000 in that a resin composition having high initial adhesive strength and excellent base material adhesion under wet heat conditions can be obtained. It is preferable.
- the molecular weight distribution (Mw / Mn) of the polyester polyurethane polyol (A) is 2.5 or more.
- the molecular weight distribution (Mw / Mn) is within the above range, the effect of improving the adhesion to the substrate due to the low molecular weight component and the effect of increasing the strength of the cured product due to the high molecular weight component are simultaneously achieved. Since it is exhibited, it becomes a resin composition having excellent base material adhesion under wet heat conditions and high initial adhesive strength.
- the molecular weight distribution (Mw / Mn) is less than 2.5, the initial adhesive strength is lowered.
- the molecular weight distribution (Mw / Mn) is preferably in the range of 3 to 25 and preferably in the range of 4 to 15 in that a resin composition that is more excellent in substrate adhesion under wet heat conditions can be obtained. More preferably, the range of 6 to 10 is particularly preferable.
- the number average molecular weight (Mn) of the polyester polyurethane polyol (A) is 3,000 to 20 in that it is excellent in substrate adhesion under wet heat conditions and becomes a resin composition having a viscosity suitable for coating. Is preferably in the range of 5,000 to 10,000, more preferably in the range of 5,000 to 10,000, and particularly preferably in the range of 5,500 to 8,000.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) under the following conditions.
- Measuring device HLC-8220GPC manufactured by Tosoh Corporation Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation + Tosoh Corporation TSK-GEL SuperHZM-M ⁇ 4 Detector: RI (differential refractometer)
- Data processing Multi-station GPC-8020model II manufactured by Tosoh Corporation Measurement conditions: Column temperature 40 ° C Solvent Tetrahydrofuran Flow rate 0.35 ml / min Standard; Monodisperse polystyrene Sample; Filtered 0.2% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 ⁇ l)
- the hydroxyl value of the polyester polyurethane polyol (A) is preferably in the range of 5 to 30 mgKOH / g, more preferably in the range of 7 to 15 mgKOH / g, from the viewpoint of excellent substrate adhesion under wet heat conditions. It is more preferable.
- the polyester polyurethane polyol (A) can be obtained, for example, by reacting a polybasic acid (E), a polyhydric alcohol (F), and a polyisocyanate (G).
- a polybasic acid (E), a polyhydric alcohol (F), and a polyisocyanate (G) in order to introduce a branched structure into the molecule of the polyester polyurethane polyol (A), any one or more raw material components of the polybasic acid (E), the polyhydric alcohol (F), and the polyisocyanate (G) are used.
- a trifunctional or higher functional compound is used.
- polybasic acid (E) examples include a dibasic acid (E1) and a tribasic or more polybasic acid (E2).
- dibasic acid (E1) examples include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and tetradecanedioic acid.
- Aliphatic dibasic acids such as pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, icosanedioic acid;
- Aliphatic dibasic acids such as tetrahydrophthalic acid, maleic acid, maleic anhydride, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, and anhydrides thereof;
- Alicyclic dibasic acids such as hexahydrophthalic acid and 1,4-cyclohexanedicarboxylic acid;
- aromatics such as phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, and orthophthalic acid include basic acids and anhydrides thereof.
- the trifunctional or higher polybasic acid (E2) is an aliphatic tribasic acid such as 1,2,5-hexanetricarboxylic acid or 1,2,4-cyclohexanetricarboxylic acid;
- aromatic tribasic acids such as trimellitic acid, trimellitic anhydride, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, and anhydrides thereof.
- a branched structure can be introduced into the molecule of the polyester polyurethane polyol (A) of the present invention by using the tribasic or higher polybasic acid (E2).
- polybasic acids (E) may be used alone or in combination of two or more.
- the content of the aliphatic polybasic acid in the total polybasic acid component is preferably in the range of 20 to 50 mol%, more preferably in the range of 25 to 40 mol%.
- the aliphatic polybasic acid is adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid in that it becomes a resin composition that is more excellent in substrate adhesion under wet heat conditions.
- Acid tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, icosanedioic acid, 1,2,5-hexanetricarboxylic acid, 1,2,4- Preferred are those having 6 to 20 carbon atoms, such as cyclohexanetricarboxylic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, 1,2,5-hexanetricarboxylic acid More preferred are those having 8 to 13 carbon atoms such as 1,2,4-cyclohexanetricarboxylic acid.
- methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexane are used as raw materials for the polyester polyurethane polyol (A).
- Monocarboxylic acids such as acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid and benzoic acid may be used.
- polyhydric alcohol (F) examples include a diol (F1) and a trifunctional or higher functional polyol (F2).
- diol (F1) examples include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, and 2,2-dimethyl-3-isopropyl-1.
- Aliphatic diols such as glycol, 1,6-hexanediol, 1,4-bis (hydroxymethyl) cyclohesan, 2,2,4-trimethyl-1,3-pentanediol;
- Ether glycols such as polyoxyethylene glycol and polyoxypropylene glycol
- a lactone polyester polyol obtained by a polycondensation reaction between the aliphatic diol and various lactones such as ⁇ -caprolactone;
- Bisphenols such as bisphenol A and bisphenol F;
- Examples include bisphenol alkylene oxide adducts obtained by adding ethylene oxide, propylene oxide, and the like to bisphenols such as bisphenol A and bisphenol F.
- the trifunctional or higher functional polyol (F2) is an aliphatic polyol such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol;
- Examples include lactone polyester polyols obtained by a polycondensation reaction between the aliphatic polyol and various lactones such as ⁇ -caprolactone.
- polyhydric alcohols (F) may be used alone or in combination of two or more.
- the content of the aliphatic polyhydric alcohol in the total polyhydric alcohol component is preferably 50 mol% or more and 80 mol% or more in that the resin composition is excellent in coatability. Is more preferable.
- the polyhydric alcohol (F) to contain is preferable.
- the said aliphatic polyol is the said aliphatic diol at the point from which the resin composition which is more excellent in the base-material adhesiveness on wet heat conditions is obtained.
- polyisocyanate (G) examples include a diisocyanate compound (G1) and a tri- or higher functional polyisocyanate compound (G2).
- diisocyanate compound (G1) examples include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, m- Aliphatic diisocyanates such as tetramethylxylylene diisocyanate;
- Cyclohexane-1,4-diisocyanate isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate, isopropylidene dicyclohexyl-4,4′-diisocyanate, Alicyclic diisocyanates such as norbornane diisocyanate;
- Aromatic diisocyanates such as 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate and the like.
- Examples of the trifunctional or higher polyisocyanate compound (G2) include adduct type polyisocyanate compounds having a urethane bond site in the molecule and nurate type polyisocyanate compounds having an isocyanurate ring structure in the molecule.
- the adduct type polyisocyanate compound having a urethane bond site in the molecule can be obtained, for example, by reacting a diisocyanate compound with a polyhydric alcohol.
- the diisocyanate compound used in the reaction include various diisocyanate compounds exemplified as the diisocyanate compound (G1). These may be used alone or in combination of two or more.
- the polyol compound used in the reaction include various polyol compounds exemplified as the polyhydric alcohol (F), polyester polyols obtained by reacting a polyhydric alcohol and a polybasic acid, and the like. You may use independently and may use 2 or more types together.
- the nurate type polyisocyanate compound having an isocyanurate ring structure in the molecule is obtained, for example, by reacting a diisocyanate compound with a monoalcohol and / or a diol.
- the diisocyanate compound used in the reaction include various diisocyanate compounds exemplified as the diisocyanate compound, and these may be used alone or in combination of two or more.
- Monoalcohols used in the reaction include hexanol, 2-ethylhexanol, octanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n- Heptadecanol, n-octadecanol, n-nonadecanol, eicosanol, 5-ethyl-2-nonanol, trimethylnonyl alcohol, 2-hexyldecanol, 3,9-diethyl-6-tridecanol, 2-isoheptylisoundecanol 2-octyldodecanol, 2-decyltetradecanol and the like, and examples of the diol include aliphatic diols exemplified for the polyhydric alcohol (F). These mono
- a branched structure can be introduced into the molecule of the polyester polyurethane polyol (A) of the present invention.
- polyisocyanates (G) may be used alone or in combination of two or more.
- the trifunctional or higher polyisocyanate compound (G2) is preferable, and a nurate polyisocyanate compound is more preferable in that a resin composition excellent in adhesive strength under wet heat conditions is obtained.
- the mass ratio [(G1) / (G2)] of the two is 50/50 in terms of providing a resin composition having excellent substrate adhesion under wet heat conditions and exhibiting a viscosity suitable for coating. Is preferably in the range of ⁇ 5 / 95, more preferably in the range of 40/60 to 10/90, and particularly preferably in the range of 30/70 to 15/85.
- the trifunctional or higher functional component used in producing the polyester polyurethane polyol (A) may be any of the polybasic acid (E2), the polyol (F2), and the polyisocyanate compound (G2).
- the polyisocyanate compound (G2) is preferably used in that a resin composition having excellent adhesive strength under wet heat conditions can be obtained and the polyester polyurethane polyol (A) can be easily produced in a shorter time.
- the method for producing the polyester polyurethane polyol (A) includes, for example, reacting the polybasic acid (E) and the polyhydric alcohol (F) in a temperature range of 150 to 270 ° C. in the presence of an esterification catalyst.
- Examples thereof include a method of reacting the polyester polyol with the polyisocyanate (G) in the presence of a urethanization catalyst in a temperature range of 50 to 100 ° C. after obtaining the polyester polyol.
- the resin composition of the present invention contains a hydroxyl group-containing epoxy resin (B) having a number average molecular weight (Mn) in the range of 300 to 5,000, so that fluorine such as a PVF film or a PVDF film having generally low adhesion is generally used. High adhesiveness can also be expressed with respect to the base material.
- Mn number average molecular weight
- the resin of the present invention Solubility in the composition is reduced.
- those having a number average molecular weight (Mn) in the range of 400 to 2,000 are more preferable in that they are more excellent in solubility in the resin composition of the present invention and substrate adhesion under wet heat conditions.
- the epoxy resin preferably has a hydroxyl group in the molecular structure because a resin composition having better curability can be obtained.
- the hydroxyl value is preferably in the range of 30 to 160 mgKOH, and more preferably in the range of 50 to 150 mgKOH / g.
- Examples of the hydroxyl group-containing epoxy resin (B) include bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin; biphenyl type epoxy resins such as biphenyl type epoxy resin and tetramethylbiphenyl type epoxy resin; Examples thereof include a pentadiene-phenol addition reaction type epoxy resin. These may be used alone or in combination of two or more. Among these, a bisphenol type epoxy resin is preferable in that a resin composition excellent in base material adhesion under wet heat conditions and initial adhesive strength can be obtained.
- the resin composition of the present invention comprises a hydroxyl group-containing polycarbonate resin (C) having a number average molecular weight (Mn) in the range of 300 to 3,000, thereby providing excellent resin adhesion on a substrate under wet heat conditions. It becomes a thing. When the number average molecular weight (Mn) is less than 300, sufficient adhesive strength cannot be obtained, and when the number average molecular weight (Mn) exceeds 3,000, the solubility in the resin composition of the present invention is lowered. To do. Among them, those having a number average molecular weight (Mn) in the range of 400 to 2,000 are more preferable in that they are more excellent in solubility in the resin composition of the present invention and substrate adhesion under wet heat conditions.
- the hydroxyl group-containing polycarbonate resin (C) preferably has a hydroxyl value in the range of 20 to 300 mgKOH / g, more preferably in the range of 40 to 250 mgKOH / g, from the viewpoint that it becomes a resin composition with more excellent curability. More preferred. Moreover, it is preferable that it is polycarbonate diol at the point which is excellent in the base-material adhesiveness on wet heat conditions.
- the hydroxyl group-containing polycarbonate resin (C) can be produced, for example, by a method of polycondensation reaction between a polyhydric alcohol and a carbonylating agent.
- Examples of the polyhydric alcohol used in the production of the hydroxyl group-containing polycarbonate resin (C) include various polyhydric alcohols exemplified as the polyhydric alcohol (F). Polyhydric alcohols may be used alone or in combination of two or more.
- Examples of the carbonylating agent used in the production of the hydroxyl group-containing polycarbonate resin (C) include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate and the like. These may be used alone or in combination of two or more.
- the resin composition of the present invention comprises the polyester polyurethane polyol (A), the hydroxyl group-containing epoxy resin (B), and the hydroxyl group-containing polycarbonate resin (C) with respect to 100 parts by mass of the polyester polyurethane polyol (A).
- the hydroxyl group-containing epoxy resin (B) in a range of 5 to 20 parts by mass
- the hydroxyl group-containing polycarbonate resin (C) in a range of 5 to 20 parts by mass
- the polyisocyanate (D) in the resin composition of the present invention is a curing agent that reacts with the hydroxyl groups contained in the polyester polyurethane polyol (A), the hydroxyl group-containing epoxy resin (B), and the hydroxyl group-containing polycarbonate resin (C). work.
- Examples of the polyisocyanate (D) include various polyisocyanates listed as the polyisocyanate (G). These polyisocyanate (D) may be used individually by 1 type, and may use 2 or more types together.
- the aliphatic diisocyanate compound is preferable in that the adhesive coating film is hardly yellowed.
- mold polyisocyanate compound is preferable at the point which is excellent in the base-material adhesiveness on wet heat conditions.
- the resin composition of the present invention contains the polyester polyurethane polyol (A), the hydroxyl group-containing epoxy resin (B), the hydroxyl group-containing polycarbonate resin (C), and the polyisocyanate (D) as essential components. .
- the ratio [OH] / [NCO] between [OH] and the number of moles [NCO] of isocyanate groups contained in the polyisocyanate compound (D) is preferably in the range of 1/1 to 1/2, A range of 1 / 1.05 to 1 / 1.5 is more preferable.
- the resin composition of the present invention may contain a hydroxyl group-containing compound other than the polyester polyurethane polyol (A), the hydroxyl group-containing epoxy resin (B), and the hydroxyl group-containing polycarbonate resin (C).
- a hydroxyl group-containing compound has, for example, a number average molecular weight (Mw) obtained by reacting a polyester polyol, polybasic acid, polyhydric alcohol and polyisocyanate obtained by reacting a polybasic acid with a polyhydric alcohol.
- the resin composition of the present invention contains a hydroxyl group-containing compound other than the polyester polyurethane polyol (A), the hydroxyl group-containing epoxy resin (B), and the hydroxyl group-containing polycarbonate resin (C), it adheres to various substrates. Since a resin composition that is excellent in properties and can maintain high substrate adhesion even under wet heat conditions is obtained, its content is 5 to 20 masses per 100 mass parts of the polyester polyurethane polyol (A). The ratio is preferably in the range of parts.
- the resin composition of this invention contains hydroxyl-containing compounds other than the said polyester polyurethane polyol (A), the said hydroxyl-containing epoxy resin (B), and the said hydroxyl-containing polycarbonate resin (C), it is excellent in sclerosis
- the resin composition of the present invention may further contain various solvents.
- the solvent include ketone compounds such as acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone, cyclic ether compounds such as tetrahydrofuran (THF) and dioxolane, and ester compounds such as methyl acetate, ethyl acetate and butyl acetate.
- Aromatic compounds such as toluene and xylene, and alcohol compounds such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether. These may be used alone or in combination of two or more.
- the resin composition of the present invention further contains various additives such as an ultraviolet absorber, an antioxidant, a silicon-based additive, a fluorine-based additive, a rheology control agent, a defoaming agent, an antistatic agent, and an antifogging agent. You may do it.
- the resin composition of the present invention can be suitably used as a two-component laminating adhesive for adhering various plastic films.
- the various plastic films include, for example, polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, polyvinyl alcohol, ABS resin, norbornene resin, cyclic olefin resin, Examples include films made of polyimide resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, and the like.
- the two-pack type laminating adhesive of the present invention exhibits high adhesion to films made of polyvinyl fluoride resin or polyvinylidene fluoride resin, which are particularly difficult to bond among the various films.
- the amount of the two-component laminating adhesive of the present invention is preferably in the range of 2 to 10 g / m 2 .
- a laminated film obtained by adhering a plurality of films using the two-component laminating adhesive of the present invention has a high adhesive property even under wet heat conditions, and has a characteristic that the films are difficult to peel off. Accordingly, the two-component laminating adhesive of the present invention can be suitably used for laminated film applications used in harsh environments such as outdoors, and as such applications, for example, a solar cell backsheet is manufactured. For example, an adhesive may be used.
- the number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC) under the following conditions.
- Measuring device HLC-8220GPC manufactured by Tosoh Corporation Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation + Tosoh Corporation TSK-GEL SuperHZM-M ⁇ 4 Detector: RI (differential refractometer)
- Data processing Multi-station GPC-8020model II manufactured by Tosoh Corporation Measurement conditions: Column temperature 40 ° C Solvent Tetrahydrofuran Flow rate 0.35 ml / min Standard; Monodisperse polystyrene Sample; Filtered 0.2% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 ⁇ l)
- the reaction was stopped when the acid value became 1.0 mgKOH / g or less, and after cooling to 100 ° C., it was diluted with ethyl acetate so that the solid content became 80% by mass.
- 36 parts by mass of an isocyanurate modified form of hexamethylene diisocyanurate (“Sumijour N3300” manufactured by Sumitomo Bayer Urethane Co., Ltd.) and 7.4 parts by mass of hexamethylene diisocyanate were charged, and dry nitrogen was allowed to flow into the flask and stirred. While being heated to 70 to 80 ° C., the urethanization reaction was carried out.
- the reaction was stopped when the isocyanate content became 0.3% by mass or less, and a weight average molecular weight (Mw) of 50,000, a number average molecular weight (Mn) of 6,300, a molecular weight distribution (Mw / Mn) of 7.9, A polyester polyurethane polyol (A1) having a hydroxyl value of 10 mgKOH / g was obtained. This was diluted with ethyl acetate to a solid content of 62% by mass to obtain a polyester polyurethane polyol (A1) solution.
- Mw weight average molecular weight
- Mn number average molecular weight
- Mw / Mn molecular weight distribution
- Production Example 2 Production of Polyester Polyurethane Polyol (A2) Solution
- a flask having a stirrer, a temperature sensor, and a rectifying tube 311 parts by mass of neopentyl glycol, 215 parts by mass of isophthalic acid, 99.7 parts by mass of phthalic anhydride, 156 parts by mass of sebacic acid
- 5.8 parts by mass of trimellitic anhydride and 0.02 parts by mass of an organic titanium compound were charged, and dry nitrogen was flowed into the flask and heated to 230 to 250 ° C. with stirring to conduct an esterification reaction.
- the reaction was stopped when the acid value became 1.0 mgKOH / g or less, cooled to 100 ° C., and diluted to 80% solid content with ethyl acetate.
- 25 parts by mass of an isocyanurate modified form of hexamethylene diisocyanurate (“Sumijour N3300” manufactured by Sumitomo Bayer Urethane Co., Ltd.) and 13.1 parts by mass of hexamethylene diisocyanate were charged, and dry nitrogen was allowed to flow into the flask and stirred. While being heated to 70 to 80 ° C., the urethanization reaction was carried out.
- the reaction was stopped when the isocyanate content became 0.3% by mass or less, and the weight average molecular weight (Mw) 40,000, the number average molecular weight (Mn) 6,000, the molecular weight distribution (Mw / Mn) 6.7, A polyester polyurethane polyol (A2) having a hydroxyl value of 10 mgKOH / g was obtained. This was diluted with ethyl acetate to a solid content of 62% by mass to obtain a polyester polyurethane polyol (A2) solution.
- Comparative production example 1 Production of polyester polyurethane polyol (a1) In a flask having a stirrer, a temperature sensor and a rectifying tube, 282.6 parts by mass of neopentyl glycol, 275.1 parts by mass of 1,6-hexanediol, and 112.8 parts by mass of ethylene glycol In addition, 634.5 parts by mass of isophthalic acid, 368.7 parts by mass of sebacic acid and 0.02 parts by mass of an organic titanium compound as an esterification catalyst were added, and dry nitrogen was flowed into the flask and heated to 230 to 250 ° C. with stirring. An esterification reaction was performed.
- the reaction was stopped when the acid value became 1.0 mgKOH / g or less, cooled to 100 ° C., and diluted to 80% solid content with ethyl acetate.
- 68.7 parts by mass of isophorone diisocyanate was charged, dry nitrogen was flowed into the flask, and heated to 80 to 90 ° C. with stirring to conduct a urethanization reaction.
- the reaction was stopped when the isocyanate content became 0.3% or less, the weight average molecular weight was 37,000, the number average molecular weight (Mn) was 8,000, the molecular weight distribution (Mw / Mn) was 4.6, and the hydroxyl value was A 10 mg KOH / g polyester polyurethane polyol (a1) was obtained. This was diluted with ethyl acetate to a solid content of 62% to obtain a polyester polyurethane polyol (a1) solution.
- Epoxy resin (B1) bisphenol A type epoxy resin having a number average molecular weight (Mn) of 470, an epoxy equivalent of 245 g / eq, and a hydroxyl value of 54 mgKOH / g (“Epiclon 860” manufactured by DIC Corporation)
- Epoxy resin (B2) bisphenol A type epoxy resin having a number average molecular weight (Mn) of 900, an epoxy equivalent of 475 g / eq, and a hydroxyl value of 125 mgKOH / g (“JER1001” manufactured by Mitsubishi Chemical Corporation)
- the hydroxyl value of the epoxy resin (B) is determined by measuring the abundance ratio of epoxy resins having different degrees of polymerization present in the epoxy resin (B) by GPC. It is a value calculated from the value with the theoretical hydroxyl value.
- Polycarbonate resin (C) used in Examples and Comparative Examples of the present invention is shown below.
- Polycarbonate polyol (C1) polycarbonate diol having a number average molecular weight (Mn) of 1,000 and a hydroxyl value of 110 mgKOH / g (“Placcel CD210” manufactured by Daicel Chemical Industries)
- polyisocyanate (D) used in Examples and Comparative Examples of the present invention is shown below.
- -Polyisocyanate (D1) a hexamethylene diisocyanate nurate modified product ("Sumijour N3300" manufactured by Sumitomo Bayer Urethane Co., Ltd.)
- Example 1 100 parts by mass of the polyester polyurethane polyol (A1) solution obtained in Production Example 1, 10 parts by mass of the epoxy resin (B1), 15 parts by mass of the polycarbonate polyol (C1) and 15 parts by mass of the polyisocyanate (D1) are mixed. Thus, a resin composition was obtained, an evaluation sample was prepared in the following manner, and evaluation was performed by the following method. The results are shown in Table 1.
- Example 1 Preparation of Evaluation Sample Using a 125 ⁇ m-thick PET film (“X10S” manufactured by Toray Industries, Inc.) as a base material, the resin composition obtained in Example 1 above has a solid mass of 5 to 6 g / m 2 after solvent drying. Then, a 25 ⁇ m-thick fluorine film (“Aflex 25PW” manufactured by Asahi Glass Co., Ltd.) was bonded to obtain a laminated film. This was aged at 50 ° C. for 72 hours to obtain an evaluation sample.
- X10S 125 ⁇ m-thick PET film
- X10S manufactured by Toray Industries, Inc.
- a 25 ⁇ m-thick fluorine film (“Aflex 25PW” manufactured by Asahi Glass Co., Ltd.) was bonded to obtain a laminated film. This was aged at 50 ° C. for 72 hours to obtain an evaluation sample.
- Evaluation 1 Measurement of adhesive strength under wet heat conditions
- a tensile tester (“AGS500NG” manufactured by SHIMADZU) was used and T was peeled off at a peeling speed of 300 mm / min and N / 15 mm. A mold peeling test was conducted, and the strength was evaluated as an adhesive force. The initial adhesive strength of the evaluation sample and the adhesive strength of each sample after exposure for 25 hours, 50 hours, and 75 hours in an environment of 121 ° C. and 100% humidity were measured.
- Evaluation 2 Evaluation of heat-and-moisture resistance
- the initial adhesion force of the evaluation sample measured in the above-mentioned evaluation 1 was compared with the adhesion force of the sample after exposure for 75 hours in an environment of 121 ° C. and 100% humidity.
- the case where the force was 60% or more of the initial adhesive force was evaluated as ⁇
- the case where the force was 40% or more and less than 60% was evaluated as ⁇
- the case where it was less than 40% was evaluated as ⁇ .
- Examples 2 to 11 An evaluation sample was prepared and evaluated in the same manner as in Example 1 except that the composition of the resin composition was changed as shown in Table 1. The evaluation results are shown in Table 1.
- Comparative Examples 1 to 3 An evaluation sample was prepared and evaluated in the same manner as in Example 1 except that the composition of the resin composition was changed as shown in Table 2. The evaluation results are shown in Table 2.
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Abstract
Description
カラム ;東ソー株式会社製 TSK-GUARDCOLUMN SuperHZ-L
+東ソー株式会社製 TSK-GEL SuperHZM-M×4
検出器 ;RI(示差屈折計)
データ処理;東ソー株式会社製 マルチステーションGPC-8020modelII
測定条件 ;カラム温度 40℃
溶媒 テトラヒドロフラン
流速 0.35ml/分
標準 ;単分散ポリスチレン
試料 ;樹脂固形分換算で0.2質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(100μl)
カラム ;東ソー株式会社製 TSK-GUARDCOLUMN SuperHZ-L
+東ソー株式会社製 TSK-GEL SuperHZM-M×4
検出器 ;RI(示差屈折計)
データ処理;東ソー株式会社製 マルチステーションGPC-8020modelII
測定条件 ;カラム温度 40℃
溶媒 テトラヒドロフラン
流速 0.35ml/分
標準 ;単分散ポリスチレン
試料 ;樹脂固形分換算で0.2質量%のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの(100μl)
ポリエステルポリウレタンポリオール(A1)溶液の製造
攪拌棒、温度センサー、精留管を有するフラスコに、ネオペンチルグリコール311質量部、イソフタル酸215質量部、無水フタル酸99.7質量部、セバシン酸156質量部、無水トリメリット酸5.8質量部及びエステル化触媒として有機チタン化合物0.02質量部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら230~250℃に加熱しエステル化反応を行った。酸価が1.0mgKOH/g以下となったところで反応を停止し、100℃まで冷却した後、酢酸エチルで固形分が80質量%となるように希釈した。次いで、ヘキサメチレンジイソシアヌレートのイソシアヌレート変性体(住友バイエルウレタン株式会社製「スミジュールN3300」)36質量部、ヘキサメチレンジイソシアネート7.4質量部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら70~80℃に加熱しウレタン化反応を行った。イソシアネート含有率が0.3質量%以下となったところで反応を停止し、重量平均分子量(Mw)50,000、数平均分子量(Mn)6,300、分子量分布(Mw/Mn)7.9、水酸基価10mgKOH/gのポリエステルポリウレタンポリオール(A1)を得た。これを酢酸エチルで固形分が62質量%となるように希釈し、ポリエステルポリウレタンポリオール(A1)溶液とした。
ポリエステルポリウレタンポリオール(A2)溶液の製造
攪拌棒、温度センサー、精留管を有するフラスコに、ネオペンチルグリコール311質量部、イソフタル酸215質量部、無水フタル酸99.7質量部、セバシン酸156質量部、無水トリメリット酸5.8質量部及び有機チタン化合物0.02質量部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら230~250℃に加熱しエステル化反応を行った。酸価が1.0mgKOH/g以下となったところで反応を停止し、100℃まで冷却後、酢酸エチルで固形分80%に希釈した。次いで、ヘキサメチレンジイソシアヌレートのイソシアヌレート変性体(住友バイエルウレタン株式会社製「スミジュールN3300」)25質量部、ヘキサメチレンジイソシアネート13.1質量部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら70~80℃に加熱しウレタン化反応を行った。イソシアネート含有率が0.3質量%以下となったところで反応を停止し、重量平均分子量(Mw)40,000、数平均分子量(Mn)6,000、分子量分布(Mw/Mn)6.7、水酸基価10mgKOH/gのポリエステルポリウレタンポリオール(A2)を得た。これを酢酸エチルで固形分が62質量%となるように希釈し、ポリエステルポリウレタンポリオール(A2)溶液とした。
ポリエステルポリウレタンポリオール(a1)の製造
攪拌棒、温度センサー、精留管を有するフラスコに、ネオペンチルグリコール282.6質量部、1,6-ヘキサンジオール275.1質量部、エチレングリコール112.8質量部、イソフタル酸634.5質量部、セバシン酸368.7質量部及びエステル化触媒として有機チタン化合物0.02質量部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら230~250℃に加熱しエステル化反応を行った。酸価が1.0mgKOH/g以下となったところで反応を停止し、100℃まで冷却した後、酢酸エチルで固形分80%に希釈した。次いで、イソホロンジイソシアネート68.7質量部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら80~90℃に加熱してウレタン化反応を行った。イソシアネート含有率が0.3%以下となったところで反応を停止し、重量平均分子量が37,000、数平均分子量(Mn)8,000、分子量分布(Mw/Mn)4.6、水酸基価が10mgKOH/gのポリエステルポリウレタンポリオール(a1)を得た。これを酢酸エチルで固形分62%に希釈し、ポリエステルポリウレタンポリオール(a1)溶液とした。
・エポキシ樹脂(B1):数平均分子量(Mn)470、エポキシ当量245g/eq、水酸基価54mgKOH/gのビスフェノールA型エポキシ樹脂(DIC株式会社製「エピクロン860」)
・エポキシ樹脂(B2):数平均分子量(Mn)900、エポキシ当量475g/eq、水酸基価125mgKOH/gのビスフェノールA型エポキシ樹脂(三菱化学社製「JER1001」)
・ポリカーボネートポリオール(C1):数平均分子量(Mn)1,000、水酸基価110mgKOH/gのポリカーボネートジオール(ダイセル化学社製「プラクセルCD210」)
・ポリイソシアネート(D1):ヘキサメチレンジイソシアネートのヌレート変性体(住友バイエルウレタン社製「スミジュールN3300」)
・ポリイソシアネート(D2):ヘキサメチレンジイソシアネート(DIC株式会社製「バーノックDN955S」)
前記製造例1で得たポリエステルポリウレタンポリオール(A1)溶液100質量部、前記エポキシ樹脂(B1)10質量部、前記ポリカーボネートポリオール(C1)15質量部及び前記ポリイソシアネート(D1)15質量部を混合して樹脂組成物を得、下記の要領で評価サンプルを作成し、以下に示す方法で評価を行った。結果を表1に示す。
125μm厚のPETフィルム(東レ株式会社製「X10S」)を基材とし、上記実施例1で得た樹脂組成物を、溶剤乾燥後の固形分の質量が5~6g/m2の範囲となるように塗装した後、25μm厚のフッ素フィルム(旭硝子株式会社製「アフレックス25PW」)を貼合して積層フィルムを得た。これを、50℃で72時間エージングし、評価サンプルを得た。
前記方法で作成した評価サンプルについて、引っ張り試験機(SHIMADZU社製「AGS500NG」)を用い、剥離速度スピード300mm/min、N/15mmの条件下でT型剥離試験を行い、その強度を接着力として評価した。評価サンプルの初期の接着力と、121℃、湿度100%環境下で25時間、50時間、75時間暴露した後のそれぞれのサンプルの接着力を測定した。
前記評価1で測定した評価サンプルの初期の接着力と、121℃、湿度100%環境下で75時間暴露した後のサンプルの接着力とを比較し、暴露後の接着力が初期の接着力の60%以上であったものを○、40%以上60%未満であったものを△、40%未満であったものを×として評価した。
樹脂組成物の配合を表1に示したように変えた以外は、実施例1と同様にして評価サンプルを作成し、評価した。評価結果を表1に示す。
樹脂組成物の配合を表2に示したように変えた以外は、実施例1と同様にして評価サンプルを作成し、評価した。評価結果を表2に示す。
Claims (10)
- 分子内に分岐構造を有し、重量平均分子量(Mw)が25,000~200,000の範囲であり、かつ、分子量分布(Mw/Mn)が2.5以上であるポリエステルポリウレタンポリオール(A)と、数平均分子量(Mn)が300~5,000の範囲である水酸基含有エポキシ樹脂(B)と、数平均分子量(Mn)が300~3,000の範囲である水酸基含有ポリカーボネート樹脂(C)と、ポリイソシアネート(D)とを必須の成分として含有することを特徴とする樹脂組成物。
- 前記ポリエステルポリウレタンポリオール(A)が、3官能以上のポリイソシアネート化合物(G2)を必須の成分として反応させて得られるものである請求項1記載の樹脂組成物。
- 前記ポリエステルポリウレタンポリオール(A)が、多塩基酸(E)と、多価アルコール(F)と、3官能以上のポリイソシアネート化合物(G2)とを必須の成分として反応させて得られるものである請求項1記載の樹脂組成物。
- 前記ポリエステルポリウレタンポリオール(A)が、ジイソシアネート化合物(G1)と3官能以上のポリイソシアネート化合物(G2)とを、両者の質量比[(G1)/(G2)]が50/50~5/95となる範囲で含有するポリイソシアネート(G)を必須の成分として反応させて得られるポリエステルポリウレタンポリオールである請求項1記載の樹脂組成物。
- 前記ポリエステルポリウレタンポリオール(A)の水酸基価が、5~30mgKOH/gの範囲である請求項1記載の樹脂組成物。
- 前記ポリエステルポリウレタンポリオール(A)100質量部に対し、前記エポキシ樹脂(B)を5~20質量部の範囲で含有し、かつ、前記ポリカーボネート樹脂(C)を5~20質量部の範囲で含有する請求項1記載の樹脂組成物。
- 前記ポリエステルポリウレタンポリオール(A)、前記エポキシ樹脂(B)及び前記ポリカーボネート樹脂(C)に含まれる水酸基の合計モル数[OH]と、前記ポリイソシアネート化合物(D)に含まれるイソシアネート基のモル数[NCO]との比[OH]/[NCO]が1/1~1/2の範囲である請求項1記載の樹脂組成物。
- 請求項1~7のいずれか1つに記載の樹脂組成物を含有する2液型ラミネート用接着剤。
- ポリエステルフィルム、フッ素フィルム、ポリオレフィンフィルム、金属箔からなる群から選ばれる1種類以上のフィルムと、請求項8記載の接着剤からなる接着層とを有する積層フィルム。
- 請求項9記載の接着剤からなる接着層を有する太陽電池のバックシート。
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US14/113,030 US8734943B2 (en) | 2011-04-22 | 2012-04-05 | Resin composition, two-pack type adhesive for laminates, multilayer film, and back sheet for solar cells |
DE112012001841.9T DE112012001841B4 (de) | 2011-04-22 | 2012-04-05 | Harzzusammensetzung, deren Verwendung in einem zweiteiligen Laminatkleber und Verwendung des Laminatklebers in einer Klebeschicht in einer laminierten Folie und einer Rückseite für Solarzellen |
CN201280019818.7A CN103492444B (zh) | 2011-04-22 | 2012-04-05 | 树脂组合物、双组分型层压用粘接剂、层压薄膜以及太阳能电池的背板 |
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DE112012001841B4 (de) | 2015-08-13 |
DE112012001841T5 (de) | 2014-01-23 |
CN103492444A (zh) | 2014-01-01 |
KR101429578B1 (ko) | 2014-08-12 |
KR20130102636A (ko) | 2013-09-17 |
JP5170349B2 (ja) | 2013-03-27 |
JPWO2012144329A1 (ja) | 2014-07-28 |
TWI526465B (zh) | 2016-03-21 |
TW201247727A (en) | 2012-12-01 |
US8734943B2 (en) | 2014-05-27 |
CN103492444B (zh) | 2015-02-25 |
US20140050919A1 (en) | 2014-02-20 |
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