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WO2018193957A1 - Composé de polyisocyanate modifié par uréthane, agent de durcissement pour agent adhésif à l'uréthane durcissable en deux parties, agent adhésif et feuille protectrice arrière pour cellule solaire - Google Patents

Composé de polyisocyanate modifié par uréthane, agent de durcissement pour agent adhésif à l'uréthane durcissable en deux parties, agent adhésif et feuille protectrice arrière pour cellule solaire Download PDF

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Publication number
WO2018193957A1
WO2018193957A1 PCT/JP2018/015357 JP2018015357W WO2018193957A1 WO 2018193957 A1 WO2018193957 A1 WO 2018193957A1 JP 2018015357 W JP2018015357 W JP 2018015357W WO 2018193957 A1 WO2018193957 A1 WO 2018193957A1
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WO
WIPO (PCT)
Prior art keywords
urethane
diisocyanate
compound
polyisocyanate compound
adhesive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/015357
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English (en)
Japanese (ja)
Inventor
晃生 海野
翔 三木
高年 松尾
神山　達哉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Publication of WO2018193957A1 publication Critical patent/WO2018193957A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition

Definitions

  • the present invention is a two-component curable urethane adhesive having high adhesion to various substrates and excellent in heat and moisture resistance, a urethane-modified polyisocyanate compound that can be suitably used as a curing agent for the adhesive, and the use thereof
  • the present invention relates to a two-component curable urethane adhesive, a laminated film, and a back sheet of a solar cell.
  • Solar cells used for photovoltaic power generation constitute the heart of a photovoltaic power generation system that directly converts sunlight energy into electrical energy, and are made of semiconductors such as silicon.
  • solar cell elements are wired in series and in parallel, and various packaging is performed to protect the elements over a long period of about 20 years, and they are unitized.
  • the unit incorporated in this package is called a solar cell module, and generally has a structure in which the surface exposed to sunlight is covered with glass, the gap is filled with a filler made of thermoplastic resin, and the back surface is protected with a sealing sheet. Yes.
  • EVA resin ethylene-vinyl acetate copolymer resin
  • the back protection sheet requires various characteristics such as polyester film and polyvinyl fluoride film, and mechanical strength, weather resistance, heat resistance, moist heat resistance, light resistance, etc.
  • the adhesive constituting the sheet is required to have high adhesion to these various films, moisture and heat resistance for maintaining adhesion over a long period even in an open-air environment, and an excellent appearance.
  • Such an adhesive for a back sheet can be 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 polyester polyurethane polyol as a main agent and a trimer of isophorone diisocyanate as a curing agent is known (for example, see Patent Document 1).
  • the adhesive described in Patent Document 1 does not provide high adhesiveness that satisfies recent market demands, and is particularly poor in substrate adhesiveness under wet heat conditions.
  • isocyanate group in polyisocyanate (B) / hydroxyl group in polycarbonate urethane polyol (A) 0.5 to 10/1
  • the polycarbonate urethane polyol (A) and the polyisocyanate (B) are contained, and the polycarbonate urethane polyol (A) contains 80 to 100 mol% of a diol unit composed of a linear alkylene diol.
  • Patent Document 2 a polycarbonate urethane polyol having a number average molecular weight of 5,000 to 25,000 and a glass transition temperature of ⁇ 40 to 10 ° C., comprising polycarbonate polyol (C) and diisocyanate (D) which are liquid at 25 ° C. A), an adhesive composition is known (for example, patent document) Reference).
  • the adhesive described in Patent Document 2 has problems such as poor heat and humidity resistance and poor appearance of the laminated laminate after the substrates are bonded and cured.
  • the problem to be solved by the present invention is a two-component curable urethane adhesive having high adhesion to various substrates and excellent in heat and moisture resistance, and urethane that can be suitably used as a curing agent for the adhesive.
  • the object is to provide a modified polyisocyanate compound, a laminated film using the adhesive, and a solar cell backsheet.
  • polycarbonate diol compound (A), aliphatic diisocyanate (B), and trifunctional or higher polyisocyanate compound (C) as essential reaction raw materials. It has been found that by using a urethane-modified polyisocyanate compound as a curing agent for a two-component curable urethane-based adhesive, it becomes a two-component curable urethane-based adhesive that has high adhesion to various substrates and is excellent in moisture and heat resistance. The present invention has been completed.
  • the polycarbonate skeleton contributes to the flexibility of the coating and can be expected to adhere to the substrate.
  • Trifunctional or higher polyisocyanate compounds can be three-dimensionally crosslinked after curing and can be expected to have heat and moisture resistance.
  • the present inventors have succeeded in achieving both substrate adhesiveness and heat-and-moisture resistance by using a urethane-modified polyisocyanate compound using both of these as raw materials as a curing agent for a two-component curable urethane adhesive. did.
  • the present invention provides a urethane-modified polyisocyanate compound using a polycarbonate diol compound (A), an aliphatic diisocyanate (B), and a tri- or higher functional polyisocyanate compound (C) as essential reaction materials.
  • the present invention further provides a two-component curable urethane adhesive curing agent containing the urethane-modified polyisocyanate compound.
  • the present invention further provides a two-component curable urethane adhesive comprising the two-component curable urethane adhesive curing agent and a main agent containing a polyol compound.
  • the present invention further provides a laminated film having an adhesive layer made of the adhesive.
  • the present invention further provides a solar cell backsheet having an adhesive layer made of the adhesive.
  • the urethane-modified polyisocyanate compound of the present invention uses polycarbonate diol compound (A), aliphatic diisocyanate (B), and trifunctional or higher polyisocyanate compound (C) as essential reaction raw materials. That is, in the urethane-modified polyisocyanate compound of the present invention, the structural sites derived from the aliphatic diisocyanate (B) and the tri- or higher functional polyisocyanate compound (C) are linked via the structural site derived from the polycarbonate diol compound (A). And has a molecular structure knotted by urethane bonds.
  • the polycarbonate diol compound (A) is not particularly limited as long as it has a carbonate structure and has two or more hydroxyl groups in one molecule, and various compounds can be used. Specifically, a polycarbonate polyol compound having a polycondensation structure with a carbonylating agent such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate and the like in the molecular structure. These may be used alone or in combination of two or more.
  • a carbonylating agent such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate and the like in the molecular structure.
  • the carbonate structure derived from the polycarbonate diol compound (A) contributes to the improvement of substrate adhesion.
  • the hydroxyl value of the polycarbonate diol compound (A) is a urethane-modified polyisocyanate compound having a higher adhesive strength when used in adhesive applications, so the hydroxyl value is in the range of 40 mgKOH / g or more and less than 300 mgKOH / g. Is preferable, and the range of 40 to 280 is more preferable.
  • the number average molecular weight (Mn) of the polycarbonate diol compound (A) is preferably in the range of 400 to 3000 since it becomes a urethane-modified polyisocyanate compound having higher adhesive strength when used for adhesives.
  • the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) are values measured by gel permeation chromatography (GPC) under the following conditions.
  • Measuring device HLC-8320GPC manufactured by Tosoh Corporation Column: Tosoh Corporation TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL 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 aliphatic diisocyanate (B) is not particularly limited as long as it is an aliphatic compound having two isocyanate groups in one molecule, and various compounds can be used. Specific examples include various aliphatic diisocyanate compounds, adduct-modified diisocyanate compounds obtained by reacting various aliphatic diisocyanate compounds and aliphatic diol compounds. These diisocyanate compounds (B) may be used alone or in combination of two or more.
  • diisocyanate compounds examples include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, m-tetra Aliphatic diisocyanate compounds such as methylxylylene diisocyanate are listed. These may be used alone or in combination of two or more.
  • diol compound used as a reaction raw material for the adduct-modified polyisocyanate compound examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, and 2,2-dimethyl.
  • a diisocyanate having an isocyanate group content of 25% by mass or more as a diisocyanate compound (B) because it becomes a urethane-modified polyisocyanate compound having higher adhesive strength when used for adhesives and excellent in coating film appearance.
  • the compound (B1) is preferably used, and more preferably 50% by mass or more of the diisocyanate compound (B) is the diisocyanate compound (B1) having an isocyanate group content of 25% by mass or more.
  • the trifunctional or higher polyisocyanate compound (C) is not particularly limited as long as it is a compound having three or more isocyanate groups in one molecule, and various compounds can be used. Specifically, isocyanurate-modified polyisocyanate compounds of various diisocyanate compounds, adduct-modified polyisocyanate compounds obtained by reacting various diisocyanate compounds with trifunctional or higher polyol compounds, and biuret-modified products of various diisocyanate compounds. And allophanate-modified products of various diisocyanate compounds. These polyisocyanate compounds (C) may be used alone or in combination of two or more.
  • the use of the trifunctional or higher polyisocyanate compound (C) as an essential reaction raw material improves the heat and moisture resistance, but this is presumed to give a cross-linked structure when used as a two-component adhesive. It is estimated that it contributes to improvement in thermal properties.
  • diisocyanate compounds examples include butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate.
  • An aliphatic diisocyanate compound An aliphatic diisocyanate compound
  • Cycloaliphatic diisocyanate compounds such as cyclohexane diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate;
  • 1,5-naphthylene diisocyanate 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate
  • aromatic diisocyanate compounds such as 1,4-phenylene diisocyanate and tolylene diisocyanate.
  • Examples of the trifunctional or higher functional polyol compound used as a reaction raw material for the adduct-modified polyisocyanate compound include trifunctional or higher functional compounds among the compounds exemplified as the polyol compound (A), and each compound is used alone. Or two or more types may be used in combination.
  • an isocyanurate-modified polyisocyanate compound is preferable because it is a urethane-modified polyisocyanate compound that has higher adhesive strength when used for adhesives and is excellent in heat and moisture resistance.
  • 50% by mass or more in the polyisocyanate compound (C) is preferably the isocyanurate-modified polyisocyanate compound, and 80% by mass or more is more preferably the isocyanurate-modified polyisocyanate compound.
  • the urethane-modified polyisocyanate compound of the present invention uses the polycarbonate diol compound (A), the aliphatic diisocyanate (B), and the trifunctional or higher polyisocyanate compound (C) as essential reaction raw materials.
  • Other reaction raw materials may be used in combination depending on the desired performance.
  • the polycarbonate diol compound (based on the total mass of the reaction raw materials of the urethane-modified polyisocyanate compound is sufficiently exerted by the effect of the present invention excellent in adhesiveness and heat-and-moisture resistance.
  • the total of A), the aliphatic diisocyanate (B), and the trifunctional or higher polyisocyanate compound (C) is preferably 70% by mass, and more preferably 80% by mass or more.
  • examples of the diol or polyol compound include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, and 2,2-dimethyl-3.
  • Aliphatic diol compounds such as diol, neopentyl glycol, 1,6-hexanediol, 1,4-bis (hydroxymethyl) cyclohexane, 2,2,4-trimethyl-1,3-pentanediol;
  • Trifunctional or higher functional aliphatic polyol compounds such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, pentaerythritol, ditrimethylolpropane, dipentaerythritol;
  • Aromatic diol compounds such as dihydroxybenzene, dihydroxynaphthalene, biphenyl and bisphenol
  • Trifunctional or higher aromatic polyol compounds such as benzenetriol
  • Polyoxyalkylene-modified polyol having a ring-opening polymerization structure of various cyclic ether compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether in the molecular structure Compound;
  • Lactone-modified polyol compound having a ring-opening polymerization structure of various lactone compounds such as ⁇ -caprolactone in the molecular structure;
  • cycloaliphatic diisocyanates such as cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatemethyl) cyclohexane, methylcyclohexane diisocyanate and the like.
  • 1,5-naphthylene diisocyanate 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate
  • aromatic diisocyanate compounds such as 1,4-phenylene diisocyanate and tolylene diisocyanate. Each of these compounds may be used alone or in combination of two or more.
  • the ratio between the aliphatic diisocyanate (B) and the tri- or higher functional polyisocyanate compound (C) sufficiently exhibits the effects of the present invention in terms of adhesiveness and moist heat resistance.
  • the ratio [(B) / (C)] is preferably in the range of 1/10 to 10/1, and more preferably in the range of 1/5 to 5/1.
  • the polycarbonate diol compound (A), the aliphatic diisocyanate (B), and the trifunctional or higher polyisocyanate compound (C) may be reacted by, for example, the number of moles of hydroxyl groups contained in the polycarbonate diol compound (A). In contrast, the reaction is performed in a temperature range of 20 to 120 ° C. using both of the aliphatic diisocyanate (B) and the trifunctional or higher polyisocyanate compound (C) in a condition where the total number of isocyanate groups is excessive. The method of letting it be mentioned.
  • a known and usual urethane catalyst such as zinc octylate may be used as necessary.
  • the solvent include ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, cyclic ether solvents such as tetrahydrofuran and dioxolane, ester solvents such as methyl acetate, ethyl acetate, and butyl acetate, and aromatic hydrocarbon solvents such as toluene and xylene.
  • alcohol solvents 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 reaction ratio of the polycarbonate diol compound (A), the aliphatic diisocyanate (B), and the trifunctional or higher polyisocyanate compound (C) is not particularly limited, depending on the desired molecular weight and isocyanate group content. Adjust as appropriate. Among these, since the urethane-modified polyisocyanate compound has higher adhesive strength when used for adhesives and is excellent in heat and moisture resistance, the resulting urethane-modified polyisocyanate compound has an isocyanate content of 2.0 to 10.0. It is preferable to make it react in the ratio used as the range of the mass%.
  • the reaction end point of the polycarbonate diol compound (A), the aliphatic diisocyanate (B), and the tri- or higher functional polyisocyanate compound (C) can be confirmed, for example, by the rate of change with time of the isocyanate group content in the reaction mixture. it can.
  • the two-component curable urethane adhesive curing agent of the present invention contains the urethane-modified polyisocyanate compound of the present invention, and may contain other polyisocyanate compounds.
  • examples of other polyisocyanate compounds include the various diisocyanate compounds described above, isocyanurate-modified products, adduct-modified products, biuret-modified products, and allophanate-modified products. These may be used alone or in combination of two or more.
  • the urethane modified polyisocyanate compound of the present invention and the other polyisocyanate compound are sufficiently exhibited because the effects of the present invention, which are excellent in adhesiveness and heat-and-moisture resistance, are exhibited.
  • the urethane-modified polyisocyanate compound of the present invention is preferably 10% by mass or more, and more preferably 20% by mass with respect to the total mass.
  • the two-component curable urethane adhesive of the present invention is composed of the two-component curable urethane adhesive curing agent containing the urethane-modified polyisocyanate compound of the present invention and a main component containing a polyol compound.
  • the polyol compound contained in the main agent is a compound having two or more hydroxyl groups in one molecule, and is particularly limited as long as it reacts with the curing agent for the two-component curable urethane adhesive and can be cured.
  • various compounds can be used, specifically, various polyol compounds exemplified as the polyol compound (A), polyester polyurethane compounds which are reaction products of these polyol compounds and polyisocyanate compounds, and hydroxyl group-containing acrylics. Examples thereof include resins, and each may be used alone or in combination of two or more.
  • polyester polyol compound as an essential component of the main component because it becomes a two-component curable urethane adhesive having high adhesion to various substrates and excellent heat and heat resistance.
  • the polyester polyol compound is more preferably a polyester polyol compound having a branched structure using a trifunctional or higher functional polyol or polybasic acid as a part of the reaction raw material.
  • the hydroxyl value of the polyester polyol compound is preferably in the range of 1 to 50 mg KOH / g because it is a two-component curable urethane adhesive having high adhesion to various substrates and excellent heat and moisture resistance. A range of 1 to 30 mg KOH / g is more preferable. Moreover, it is preferable that the acid value is 5 mgKOH / g or less.
  • the polyester polyol compound has a weight average molecular weight (Mw) in the range of 5,000 to 100,000 because it is a two-component curable urethane adhesive having high adhesion to various substrates and excellent heat and heat resistance. It is preferable that The molecular weight distribution (Mw / Mn) is preferably 2 or more, and more preferably in the range of 2.5-6.
  • the polyol compound preferably contains a polycarbonate polyol compound in addition to the polyester polyol compound.
  • the blending ratio of the polyester polyol compound and the polycarbonate polyol compound is a two-component curable urethane adhesive having high adhesion to various base materials and excellent moisture and heat resistance.
  • the polyester polyol compound is preferably in the range of 30 to 99.5% by mass, more preferably in the range of 60 to 99% by mass.
  • the number average molecular weight (Mn) of the polycarbonate polyol compound is in the range of 300 to 2,000 because it is a two-component curable urethane adhesive having high adhesion to various base materials and excellent heat and moisture resistance. It is preferable.
  • the hydroxyl value is preferably in the range of 30 to 250 mg KOH / g, and more preferably in the range of 40 to 200 mg KOH / g.
  • the polycarbonate polyol compound is preferably a polycarbonate diol compound.
  • the polyol compound preferably contains a polyoxyalkylene-modified polyol compound in addition to the polyester polyol compound.
  • the blending ratio of the polyester polyol compound and the polyoxyalkylene-modified polyol compound is a two-part curable urethane adhesive having high adhesion to various substrates and excellent in heat and moisture resistance.
  • the polyester polyol compound is preferably in the range of 30 to 99.5% by mass and more preferably in the range of 60 to 99% by mass with respect to the total mass.
  • the number average molecular weight (Mn) of the polyoxyalkylene-modified polyol compound is a two-component curable urethane adhesive having high adhesion to various substrates and excellent heat and moisture resistance. A range is preferable.
  • the hydroxyl value is preferably in the range of 40 to 250 mgKOH / g, and more preferably in the range of 50 to 200 mgKOH / g.
  • the polyoxyalkylene-modified polyol compound is preferably a polyoxyalkylene-modified diol compound.
  • the main agent used in the present invention may contain other resin components in addition to the polyol compound. When other resin components are used, it is preferably used at 50% by mass or less, more preferably 30% by mass or less, based on the total mass of the main agent. Specific examples of other resin components include epoxy resins.
  • the epoxy resin 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; dicyclopentadiene-phenol addition reaction Type epoxy resin and the like. These may be used alone or in combination of two or more. Among these, it is preferable to use a bisphenol-type epoxy resin because it becomes a two-component curable urethane-based adhesive having high adhesion to various base materials and excellent moisture and heat resistance.
  • the number average molecular weight (Mn) of the epoxy resin is in the range of 300 to 2,000 because it is a two-component curable urethane adhesive that has high adhesion to various substrates and is excellent in heat and moisture resistance. Is preferred.
  • the epoxy equivalent is preferably in the range of 150 to 1000 g / equivalent.
  • the blending ratio of the polyester polyol compound and the epoxy resin is a two-component curable urethane adhesive that has high adhesion to various substrates and is excellent in heat and moisture resistance.
  • the polyester polyol compound is preferably in the range of 30 to 99.5% by mass and more preferably in the range of 60 to 99% by mass with respect to the total mass.
  • the main agent used in the present invention may contain a tackifier.
  • the tackifier include rosin or rosin ester tackifier, terpene or terpene phenol tackifier, saturated hydrocarbon resin, coumarone tackifier, coumarone indene tackifier, and styrene resin.
  • examples include tackifiers, xylene resin tackifiers, phenol resin tackifiers, and petroleum resin tackifiers. These may be used alone or in combination of two or more.
  • the tackifier can be obtained mainly with various softening points depending on the molecular weight, but the softening point is in view of compatibility, color tone and thermal stability when mixed with other resins constituting the main agent.
  • Particularly preferred are rosin resins and hydrogenated derivatives thereof at 80 to 160 ° C., preferably 90 to 110 ° C.
  • it is used in the range of 10 to 30 parts by mass (solid content), particularly in the range of 10 to 20 parts by mass (solid content) with respect to 100 parts by mass of the solid content of the resin constituting the main agent.
  • rosin or rosin ester examples include polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, fumarized rosin, and glycerin esters, pentaerythritol ester, methyl ester, ethyl ester, butyl ester, ethylene glycol Examples thereof include esters, diethylene glycol esters, and triethylene glycol esters.
  • terpene series or terpene phenol series examples include low-polymerized terpene series, ⁇ -pinene polymer, ⁇ -pinene polymer, terpene phenol series, aromatic modified terpene series, and hydrogenated terpene series.
  • Examples of petroleum resins include petroleum resins obtained by polymerizing petroleum fractions of 5 carbon atoms obtained from pentene, pentadiene, isoprene, etc., indene, methylindene, vinyltoluene, styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, etc.
  • Examples thereof include hydrogenated products of these petroleum resins; modified petroleum resins obtained by modifying these petroleum resins with maleic anhydride, maleic acid, fumaric acid, (meth) acrylic acid, phenol, and the like.
  • phenol resin system a condensate of phenols and formaldehyde can be used.
  • the phenols include phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcin, and the like. These phenols and formaldehyde are subjected to a condensation reaction with an acid catalyst or an acid catalyst. The novolak obtained by this can be illustrated.
  • the rosin phenol resin etc. which are obtained by adding phenol to an rosin with an acid catalyst and heat-polymerizing can also be illustrated.
  • a hydrogenated rosin type having a softening point of 80 to 160 ° C. is particularly preferable, and a hydrogenated rosin type having an acid value of 2 to 10 mgKOH / g and a hydroxyl value of 5 mgKOH / g or less is more preferable. .
  • the mixing ratio of the main agent and the curing agent is such that the total number of moles of hydroxyl groups contained in the main agent [OH] and the number of moles of isocyanate groups contained in the curing agent [NCO].
  • the ratio [OH] / [NCO] is preferably in the range of 1/1 to 1/2.
  • the main agent and the curing agent constituting the two-component curable urethane adhesive of the present invention may 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 main component and the curing agent constituting the two-component curable urethane adhesive of the present invention are an ultraviolet absorber, an antioxidant, a silicon-based additive, a fluorine-based additive, a rheology control agent, a defoaming agent, an antistatic agent, Various additives such as an antifogging agent may be contained.
  • the two-part curable urethane-based adhesive of the present invention can be used for bonding various substances, and examples of bonding targets include paper, wood, plastic film, plastic molded product, metal, etc. It can be suitably used as an adhesive for bonding various plastic films to obtain a laminated film.
  • 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-component curable urethane-based 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 curable urethane adhesive of the present invention is preferably in the range of 2 to 10 g / m 2 .
  • the laminated film obtained by adhering a plurality of films to the two-component curable urethane adhesive of the present invention has a high adhesive property even under wet heat conditions, and the films are difficult to peel off. Therefore, the two-component curable urethane-based adhesive of the present invention can be suitably used for laminated film applications used in harsh environments such as outdoors. As such applications, for example, a solar cell backsheet is manufactured. For example, an adhesive may be used.
  • the method for producing a solar battery back sheet using the two-component curable urethane adhesive of the present invention is, for example, by applying the two-component curable urethane adhesive of the present invention to a plastic film and then applying another
  • An example is a method in which a plastic substrate is stacked and then cured at a temperature of 25 to 80 ° C.
  • the apparatus for applying the two-component curable urethane adhesive of the present invention to a plastic film includes a comma coater, a roll knife coater, a die coater, a roll coater, a bar coater, a gravure roll coater, a reverse roll coater, a blade coater, and a gravure. Examples thereof include a coater and a micro gravure coater.
  • the amount of the two-component curable urethane adhesive applied to the plastic substrate is preferably about 1 to 50 ⁇ m in terms of dry film thickness.
  • plastic film and adhesive layer There may be a plurality of the above-described plastic film and adhesive layer. Further, a structure may be employed in which a gas barrier layer such as a metal vapor deposition film is provided on the surface of the plastic film, the two-component curable urethane adhesive is applied thereon, and another plastic film is laminated. Furthermore, in order to improve adhesiveness with the sealing material which seals a solar cell element, the easily bonding layer may be provided in the sealing material side surface of this solar cell backsheet.
  • a gas barrier layer such as a metal vapor deposition film is provided on the surface of the plastic film, the two-component curable urethane adhesive is applied thereon, and another plastic film is laminated.
  • the easily bonding layer may be provided in the sealing material side surface of this solar cell backsheet.
  • This easy-adhesion layer can form irregularities on the surface of the easy-adhesion layer, and is composed of fine metal particles such as TiO 2 , SiO 2 , CaCO 3 , SnO 2 , ZrO 2 and MgCO 3 and a binder in order to improve adhesion. It is preferable that it is a thing.
  • a solar cell module using such a back sheet for a solar cell includes an ethylene vinyl acetate resin (EVA) sheet, a plurality of solar cells, an ethylene vinyl acetate resin (EVA) sheet on the cover glass plate, It can be manufactured by disposing a back sheet, heating while evacuating, and melting the EVA sheet to seal the solar cell element. At this time, the plurality of solar cell elements are joined in series by the interconnector.
  • the solar cell element include a single crystal silicon solar cell element, a polycrystalline silicon solar cell element, a single junction type, an amorphous silicon solar cell element composed of a tandem structure type, gallium arsenide (GaAs), and the like.
  • III-V compound semiconductor solar cell elements such as indium phosphorus (InP), II-VI compound semiconductor solar cell elements such as cadmium tellurium (CdTe), copper / indium / selenium (CIS), copper / indium / gallium / Selenium-based (CIGS-based), copper / indium / gallium / selenium / sulfur-based (CIGS-based) I-III-VI group compound semiconductor solar cell elements, dye-sensitized solar cell elements, organic solar cell elements, etc. Can be mentioned.
  • indium phosphorus InP
  • II-VI compound semiconductor solar cell elements such as cadmium tellurium (CdTe), copper / indium / selenium (CIS), copper / indium / gallium / Selenium-based (CIGS-based), copper / indium / gallium / selenium / sulfur-based (CIGS-based)
  • I-III-VI group compound semiconductor solar cell elements dye-sensitized solar cell elements,
  • the number average molecular weight (Mn), the weight average molecular weight (Mw), and the molecular weight distribution (Mw / Mn) were measured by gel permeation chromatography (GPC) under the following conditions.
  • Measuring device HLC-8320GPC manufactured by Tosoh Corporation Column: Tosoh Corporation TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL 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)
  • Synthesis Example 2 [Synthesis of urethane-modified polyisocyanate compound (A2)] While allowing dry nitrogen to flow into a flask equipped with a stir bar, temperature sensor, and cooling tube, 87 parts of Sumidur N-3300 (isocyanurate of hexamethylene diisocyanate / Suicide Bayer Urethane), 91 parts of hexamethylene diisocyanate and ethyl acetate 234 parts were charged and heated until the internal temperature of the flask reached 60 ° C.
  • Sumidur N-3300 isocyanurate of hexamethylene diisocyanate / Suicide Bayer Urethane
  • 91 parts of hexamethylene diisocyanate and ethyl acetate 234 parts were charged and heated until the internal temperature of the flask reached 60 ° C.
  • Synthesis Example 3 Synthesis of urethane-modified polyisocyanate compound (A3)] While allowing dry nitrogen to flow into a flask equipped with a stir bar, temperature sensor, and cooling tube, 89 parts of Sumidur N-3300 (isocyanurate of hexamethylene diisocyanate / Suicide Bayer Urethane), 91 parts of hexamethylene diisocyanate and ethyl acetate 258 parts were charged and heated until the internal temperature of the flask reached 60 ° C.
  • Sumidur N-3300 isocyanurate of hexamethylene diisocyanate / Suicide Bayer Urethane
  • 91 parts of hexamethylene diisocyanate and ethyl acetate 258 parts were charged and heated until the internal temperature of the flask reached 60 ° C.
  • N-3300 Isocyanurate-modified product of hexamethylene diisocyanate, isocyanate group content 21.8% by mass
  • T5651 polycarbonate diol having a hydroxyl value of 110 mg KOH / g
  • EPICLON860 bisphenol A type epoxy resin having a number average molecular weight (Mn) of 470 and an epoxy equivalent of 245 g / equivalent
  • N-3300 Isocyanurate-modified product of hexamethylene diisocyanate, isocyanate group content 21.8% by mass (“Sumijour N-3300” manufactured by Sumika Bayer Urethane Co., Ltd.)
  • Adhesive strength Initially, the strength (N / 15 mm, 180 ° peeling) when the above-described evaluation sample was pulled with a tensile tester (manufactured by SHIMADZU; AGS-100NG) at a peeling speed of 100 mm / min was used as an adhesive force, and Measurements were made after exposure for 24 hours, 48 hours, and 96 hours in a 100% environment at 121 ° C.
  • Wet and heat resistance Evaluated from the retention rate of adhesive strength after 96 hours at 121 ° C. and 121 ° C. relative to the initial adhesive strength.
  • Adhesive strength The initial adhesive strength was evaluated as ⁇ : 6 N / 15 mm or more, ⁇ : 4.5 N / 15 mm or more and less than 6 N / 15 mm, x: less than 4.5 N / 15 mm.
  • Wet heat resistance The retention rate of adhesive strength after 96 hours at 121 ° C. with respect to the initial adhesive strength was evaluated as ⁇ : 80% or more, ⁇ : 65% or more and less than 80%, and X: less than 65%. The results are shown in Table 1.
  • the two-component curable urethane adhesives of Examples 1 to 4 were excellent in adhesion strength and excellent in heat and humidity resistance even after 48 hours.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne : un agent adhésif à l'uréthane durcissable en deux parties qui présente une adhérence élevée à divers matériaux de base, et une excellente résistance à la chaleur humide ; un composé polyisocyanate modifié par uréthane qui peut être utilisé de préférence comme agent de durcissement pour l'agent adhésif ; et un film stratifié et une feuille protectrice arrière pour une cellule solaire utilisant l'agent adhésif. Ce composé polyisocyanate modifié par uréthane contient, en tant que matières premières de réaction essentielles, un composé polycarbonate diol (A), un diisocyanate aliphatique (B), et un composé polyisocyanate ayant trois groupes fonctionnels ou plus (C). Cet agent de durcissement pour un agent adhésif à l'uréthane durcissable en deux parties contient le composé polyisocyanate modifié par uréthane. Cet agent adhésif à l'uréthane durcissable en deux parties comprend l'agent de durcissement pour un agent adhésif à l'uréthane durcissable en deux parties, et un agent principal contenant un composé polyol. Ce film stratifié et cette feuille protectrice arrière pour une cellule solaire ont une couche adhésive comprenant l'agent adhésif.
PCT/JP2018/015357 2017-04-21 2018-04-12 Composé de polyisocyanate modifié par uréthane, agent de durcissement pour agent adhésif à l'uréthane durcissable en deux parties, agent adhésif et feuille protectrice arrière pour cellule solaire Ceased WO2018193957A1 (fr)

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US20200207143A1 (en) * 2018-12-27 2020-07-02 Riso Kagaku Corporation Adhesive for heat-sensitive screen master, heat-sensitive screen master, and method for producing heat-sensitive screen master
CN115003771A (zh) * 2020-02-06 2022-09-02 东洋纺株式会社 基材粘接性良好的聚氨酯树脂及使用其的粘接剂、油墨粘合剂或涂布剂用组合物

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TWI841121B (zh) * 2022-12-15 2024-05-01 辰展股份有限公司 二劑型金屬接著劑、金屬接著件
CN116751558A (zh) * 2023-06-21 2023-09-15 杭州之江有机硅化工有限公司 一种动力电池用高耐热双组分聚氨酯结构胶及其制备方法

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