TW201835148A - Polyester polyol, reactive adhesive, and laminate - Google Patents

Polyester polyol, reactive adhesive, and laminate Download PDF

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TW201835148A
TW201835148A TW106144511A TW106144511A TW201835148A TW 201835148 A TW201835148 A TW 201835148A TW 106144511 A TW106144511 A TW 106144511A TW 106144511 A TW106144511 A TW 106144511A TW 201835148 A TW201835148 A TW 201835148A
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polyester polyol
adhesive
polyol
derivative
resin
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TW106144511A
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TWI736722B (en
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水田清嗣
松尾高年
三木翔
中村英美
海野晃生
三原崇
武田美穗
神山達哉
武井秀晃
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日商迪愛生股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—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
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/127—Acids containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C09J175/06—Polyurethanes from polyesters
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

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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)
  • Laminated Bodies (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

Provided is a reactive adhesive which can be used as an adhesive for a laminate of various substrates, exhibits strong adhesiveness, and after a lamination treatment exhibits excellent outward appearance, hydrolysis resistance and moldability. The present invention pertains to: a polyester polyol having a polybasic acid or derivative thereof and a polyhydric alcohol as essential starting materials, the polyester polyol being characterized in that the entirety of the polybasic acid or derivative starting material is a polybasic acid having an aromatic ring or a derivative thereof, and the number average molecular weight is in the range of 3,000-100,000; a reactive adhesive having as essential components thereof a polyol composition (A) that contains a polyester polyol, and a polyisocyanate composition (B); and a laminate obtained by layering an adhesive layer between a first substrate and a second substrate, wherein the adhesive layer is the abovementioned reactive adhesive.

Description

聚酯多元醇、反應型接著劑、及積層體    Polyester polyol, reactive adhesive, and laminate   

本發明係有關於反應型接著劑、為其之一成分的聚酯多元醇、及使用該反應型接著劑之積層體。 The present invention relates to a reactive adhesive, a polyester polyol as one of the components, and a laminated body using the reactive adhesive.

自昔至今，各種塑膠薄膜彼此之貼合、或者將塑膠薄膜與金屬蒸鍍薄膜或金屬箔積層(層合)而成之積層體係使用在各式各樣的用途，例如食品或醫藥品、生活用品之包裝材料、或防壁材、屋頂材、太陽能電池面板材、電池用包裝材料、窗材、屋外地板材料、照明保護材料、汽車構件、招牌、貼紙等屋外產業用途、使用於射出成形同時裝飾方法等之裝飾用途等。 Since then, various plastic films have been laminated to each other, or laminated systems formed by laminating (laminating) plastic films with metal-evaporated films or metal foils have been used in a variety of applications, such as food or medicine, living Packaging materials for supplies, or wall materials, roofing materials, solar cell surface materials, battery packaging materials, window materials, outdoor flooring materials, lighting protection materials, automotive components, signboards, stickers and other outdoor industrial applications, used for injection molding and decoration Decorative purposes such as methods.

此等積層體係視各自用途中的要求特性，而將各種之塑膠薄膜、金屬蒸鍍薄膜或者金屬箔適宜組合，並選擇因應其要求特性的接著劑。例如，若為食品或生活用品，為了保護內容物免於各式各樣的流通、冷藏等保存或加熱殺菌等處理等的影響，而要求強度或不易破裂、耐高溫殺菌性(retort resistance)、耐熱性等機能。或者在屋外產業用途，係要求用來在露天環境下亦長期維持接著性之耐候性或抗水解性。 Depending on the characteristics required in each application, these laminated systems combine various plastic films, metal vapor-deposited films, or metal foils appropriately, and select an adhesive according to their required characteristics. For example, in the case of food or daily necessities, in order to protect the contents from various distributions, refrigerated storage, or heat sterilization, it requires strength or resistance to cracking, retort resistance, Features such as heat resistance. Or for outdoor industrial applications, it is required to maintain the weatherability or hydrolysis resistance in the open-air environment for a long time.

再者，此等積層體少以片狀流通，而係例如作成將端部熱封而成的袋狀、或者有時為了熱成形用而進一步施加成形加工，而亦有要求熱封性或成形加工性的情況。 In addition, these laminated bodies seldom circulate in a sheet shape, and are formed into a bag shape in which the ends are heat-sealed, or may be further subjected to a forming process for thermoforming, and heat-sealing properties or forming are also required. Processability.

作為使用於此種層合的接著劑，向來已知有使羥基與異氰酸酯反應之反應型接著劑(亦稱二液型接著劑)。 As an adhesive used for such lamination, a reactive adhesive (also called a two-liquid adhesive) that reacts a hydroxyl group with an isocyanate has been known.

例如在食品用途中，已知有一種接著劑，其係含有具有2個羥基之二醇化合物(A)、與具有2個以上之異氰酸酯基之聚異氰酸酯(B)而成的接著劑，其中前述二醇化合物(A)的數量平均分子量(Mn)為400~3000的範圍，前述聚異氰酸酯(B)為三價以上之聚異氰酸酯化合物(b1)、與對聚酯二醇加成異氰酸酯化合物而得之二異氰酸酯化合物(b2)的混合物(例如參照專利文獻1)。 For example, in food applications, there is known an adhesive agent comprising an diol compound (A) having two hydroxyl groups and a polyisocyanate (B) having two or more isocyanate groups, wherein The number average molecular weight (Mn) of the diol compound (A) is in the range of 400 to 3000. The polyisocyanate (B) is a trivalent or higher polyisocyanate compound (b1) and is obtained by adding an isocyanate compound to a polyester diol. A mixture of the diisocyanate compound (b2) (for example, refer to Patent Document 1).

已知在電池用包裝材料的層合薄膜用之接著劑中，含有多元醇成分之數量平均分子量為5000以上且小於14000的聚胺基甲酸酯聚酯多元醇，且胺基甲酸酯鍵的含有率及異氰酸酯基的含有率之總和為特定範圍內的層合用接著劑其成形加工性或耐濕熱性優良(例如參照專利文獻2)。 It is known that in an adhesive for a laminated film of a packaging material for a battery, a polyurethane polyester polyol having a number average molecular weight of 5000 or more and less than 14,000 containing a polyol component, and a urethane bond is known. The sum of the content rate of the isocyanate group and the content rate of the isocyanate group is a laminating adhesive in a specific range, and is excellent in moldability and moisture resistance (for example, refer to Patent Document 2).

先行技術文獻Advance technical literature 專利文獻Patent literature

專利文獻1 日本特開2014-101422號公報 Patent Document 1 Japanese Patent Application Publication No. 2014-101422

專利文獻2 日本特開2016-196580號公報 Patent Document 2 Japanese Patent Application Publication No. 2016-196580

本發明所欲解決之課題在於提供一種可適用作為將各種之塑膠薄膜、金屬蒸鍍薄膜或者金屬箔適 宜組合而成的積層體用之接著劑，且兼具高接著性、與層合加工後之優良的外觀、或用來在露天環境下亦長期維持接著性之抗水解性、甚至成形加工性的反應型接著劑。 The problem to be solved by the present invention is to provide an adhesive that can be suitably used as a laminate for a laminated body formed by appropriately combining various plastic films, metal deposited films, or metal foils, and has both high adhesion and lamination processing. Reactive adhesive with excellent appearance or long-term resistance to hydrolysis, even molding processability in open air.

本案發明人等發現以下反應型接著劑可解決上述課題：其係使羥基與異氰酸酯反應之反應型接著劑，其中羥基成分係聚酯多元醇，該聚酯多元醇係以多元酸或其衍生物與多元醇為必要原料的聚酯多元醇，其中前述多元酸或其衍生物原料全為具有芳環之多元酸或其衍生物，且數量平均分子量為3000~100000的範圍。 The inventors of the present invention have found that the following type of reactive adhesive can solve the above-mentioned problem: it is a reactive adhesive that reacts a hydroxyl group with an isocyanate. Polyester polyols with polyhydric alcohols as essential raw materials, in which the aforementioned polybasic acids or their raw materials are all polybasic acids or derivatives with aromatic rings, and the number average molecular weight is in the range of 3000 to 100,000.

亦即，本發明係提供一種聚酯多元醇，其係以多元酸或其衍生物與多元醇為必要原料的聚酯多元醇，其中前述多元酸或其衍生物原料全為具有芳環之多元酸或其衍生物，且數量平均分子量為3000~100000的範圍。 That is, the present invention provides a polyester polyol, which is a polyester polyol using a polyacid or its derivative and a polyhydric alcohol as essential raw materials, wherein the aforementioned polyacid or its derivative raw materials are all polyhydric having an aromatic ring. Acid or its derivative, and the number average molecular weight is in the range of 3000 to 100,000.

又，本發明係提供一種反應型接著劑，其係以包含前述記載之聚酯多元醇的多元醇組成物(A)與聚異氰酸酯組成物(B)為必要成分。 In addition, the present invention provides a reactive-type adhesive containing a polyol composition (A) and a polyisocyanate composition (B) containing the polyester polyol described above as essential components.

又，本發明係提供一種積層體，其係至少在第一基材與第二基材之間積層接著劑層而成的積層體，其中前述接著劑層為前述記載之反應型接著劑。 The present invention also provides a laminated body, which is a laminated body in which an adhesive layer is laminated at least between a first substrate and a second substrate, wherein the adhesive layer is the reactive adhesive described in the foregoing.

藉由本發明，可獲得一種具有高接著性的反應型接著劑。本發明之反應型接著劑可適用於將各種 之塑膠薄膜、金屬蒸鍍薄膜或者金屬箔適宜組合而成的積層體用之層合用接著劑，且所得的積層體係層合加工後之外觀、用來在露天環境下亦長期維持接著性之抗水解性、甚至成形加工性皆優良。 According to the present invention, a reactive adhesive having high adhesiveness can be obtained. The reactive adhesive of the present invention can be used as a laminating adhesive for a laminated body in which various plastic films, metal vapor-deposited films or metal foils are suitably combined, and the appearance and application of the obtained laminated system after lamination are processed. In the open-air environment, it has excellent hydrolysis resistance and long molding processability.

用以實施發明之形態Forms used to implement the invention

(聚酯多元醇) (Polyester polyol)

本發明之聚酯多元醇係以多元酸或其衍生物與多元醇為必要原料的聚酯多元醇，其特徵為前述多元酸或其衍生物原料全為具有芳環之多元酸或其衍生物，且數量平均分子量為3000~100000的範圍(以下簡稱為聚酯多元醇(A))。藉由反應型接著劑之一成分為該聚酯多元醇，可兼具用來在露天環境下亦長期維持接著性之抗水解性、與成形加工性。 The polyester polyol of the present invention is a polyester polyol using a polyacid or its derivative and a polyhydric alcohol as essential raw materials, and is characterized in that the aforementioned polyacid or its derivative raw materials are all polyacids or derivatives having an aromatic ring. , And the number average molecular weight is in the range of 3,000 to 100,000 (hereinafter referred to as polyester polyol (A)). Since one of the components of the reactive adhesive is the polyester polyol, it can have both hydrolysis resistance and molding processability to maintain the adhesion for a long period of time in the open air environment.

本發明中作為聚酯多元醇(A)的原料所使用之具有芳環之多元酸或其衍生物，具體而言，可舉出鄰苯二甲酸、對苯二甲酸、間苯二甲酸、焦蜜石酸、苯偏三甲酸(trimellitic acid)、1,4-萘二甲酸、2,5-萘二甲酸、2,6-萘二甲酸、萘二甲酸、聯苯二甲酸、1,2-雙(苯氧基)乙烷-p,p’-二甲酸及此等二羧酸之酐或者酯形成性衍生物等。作為羧酸酐，具體而言，可舉出鄰苯二甲酸酐、2,3-萘二甲酸酐、苯偏三甲酸酐、焦蜜石酸酐等。作為 此等之甲基酯化合物，具體而言，可舉出對苯二甲酸二甲酯、2,6-萘二甲酸二甲酯等。此處所稱酸酐，係指1分子內具有2個以上之羧基的羧酸酐。此等可單獨使用或者併用二種以上來使用。 The polybasic acid having an aromatic ring or a derivative thereof used as a raw material of the polyester polyol (A) in the present invention, specifically, phthalic acid, terephthalic acid, isophthalic acid, and coke Tartaric acid, trimellitic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, naphthalenedicarboxylic acid, biphthalic acid, 1,2- Bis (phenoxy) ethane-p, p'-dicarboxylic acid and anhydrides or ester-forming derivatives of these dicarboxylic acids. Specific examples of the carboxylic acid anhydride include phthalic anhydride, 2,3-naphthalenedicarboxylic anhydride, trimellitic anhydride, pyromelite anhydride, and the like. Specific examples of such methyl ester compounds include dimethyl terephthalate and dimethyl 2,6-naphthalene dicarboxylate. The acid anhydride referred to here means a carboxylic acid anhydride having two or more carboxyl groups in one molecule. These can be used alone or in combination of two or more.

其中較佳為鄰苯二甲酸、間苯二甲酸、對苯二甲酸、苯偏三甲酸及其酐或其甲基酯化合物，更佳為間苯二甲酸、對苯二甲酸、苯偏三甲酸及其酸酐或其甲基酯化合物。 Among them, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and its anhydride or its methyl ester compound are preferred, and isophthalic acid, terephthalic acid, and trimellitic acid are more preferred. And its anhydride or its methyl ester compound.

本發明中作為聚酯多元醇(A)的原料所使用之多元醇，可舉出二醇或3官能以上之多元醇。 Examples of the polyol used as the raw material of the polyester polyol (A) in the present invention include a diol or a trifunctional or higher polyol.

前述二醇可舉出例如：乙二醇、二乙二醇、丙二醇、1,3-丙二醇、1,2,2-三甲基-1,3-丙二醇、2,2-二甲基-3-異丙基-1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、3-甲基-1,3-丁二醇、1,5-戊二醇、3-甲基1,5-戊二醇、新戊二醇、1,6-己二醇、1,4-雙(羥甲基)環己烷、2,2,4-三甲基-1,3-戊二醇等的脂肪族二醇；聚氧乙二醇(polyoxyethylene glycol)、聚氧丙二醇等的醚二醇；藉由前述脂肪族二醇與環氧乙烷、環氧丙烷、四氫呋喃、乙基環氧丙基醚、丙基環氧丙基醚、丁基環氧丙基醚、苯基環氧丙基醚、烯丙基環氧丙基醚等各種含有環醚鍵之化合物的開環聚合所得的改質聚醚二醇；藉由前述脂肪族二醇與乳酸內酯(lactanoid)、ε-己內酯等各種內酯類的聚縮合反應所得的內酯系聚酯多元醇； 雙酚A、雙酚F等的雙酚；對雙酚A、雙酚F等的雙酚加成環氧乙烷、環氧丙烷等所得之雙酚的環氧烷加成物(alkylene oxide)等。 Examples of the diol include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, and 2,2-dimethyl-3 -Isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3- Methyl 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis (hydroxymethyl) cyclohexane, 2,2,4-trimethyl-1,3 -Aliphatic diols such as pentanediol; ether diols such as polyoxyethylene glycol and polyoxypropylene glycol; and the aforementioned aliphatic diols and ethylene oxide, propylene oxide, tetrahydrofuran, and ethylene Ring-opening of various compounds containing cyclic ether bonds, such as propylglycidyl ether, propylglycidyl ether, butylglycidyl ether, phenylglycidyl ether, allylglycidyl ether, etc. Modified polyether diol obtained by polymerization; lactone-based polyester polyol obtained by polycondensation reaction of the aforementioned aliphatic diol with various lactones such as lactanoid and ε-caprolactone; double Bisphenols such as phenol A and bisphenol F; alkylene oxide adducts of bisphenols obtained by adding bisphenols such as bisphenol A and bisphenol F to ethylene oxide and propylene oxide (a lkylene oxide) and so on.

前述3官能以上之多元醇可舉出：三羥甲基乙烷、三羥甲基丙烷、甘油、己三醇、新戊四醇等的脂肪族多元醇；藉由前述脂肪族多元醇與環氧乙烷、環氧丙烷、四氫呋喃、乙基環氧丙基醚、丙基環氧丙基醚、丁基環氧丙基醚、苯基環氧丙基醚、烯丙基環氧丙基醚等各種含有環醚鍵之化合物的開環聚合所得的改質聚醚多元醇；藉由前述脂肪族多元醇與ε-己內酯等各種內酯類的聚縮合反應所得的內酯系聚酯多元醇等。 Examples of the tri- or higher-functional polyhydric alcohol include: trimethylolethane, trimethylolpropane, glycerol, hexanetriol, neopentyl tetraol, and the like; and through the aforementioned aliphatic polyol and cyclic Ethylene oxide, propylene oxide, tetrahydrofuran, ethylglycidyl ether, propylglycidyl ether, butylglycidyl ether, phenylglycidyl ether, allylglycidyl ether Modified polyether polyols obtained by ring-opening polymerization of various compounds containing cyclic ether bonds; lactone polyesters obtained by the polycondensation reaction of the aforementioned aliphatic polyols with various lactones such as ε-caprolactone Polyols, etc.

於本發明中，由提升層合加工後的外觀而言，作為多元醇，較佳包含分支伸烷基二醇。 In the present invention, from the standpoint of improving the appearance after lamination processing, it is preferable to include a branched alkylene glycol as the polyol.

分支伸烷基二醇，具體而言為於其分子結構內具有三級碳原子或四級碳原子的伸烷基二醇，可舉出例如1,2,2-三甲基-1,3-丙二醇、2,2-二甲基-3-異丙基-1,3-丙二醇、3-甲基-1,3-丁二醇、3-甲基-1,5-戊二醇、新戊二醇、1,4-雙(羥甲基)環己烷、2,2,4-三甲基-1,3-戊二醇等，此等可單獨使用或者併用二種類以上。又，此等當中，尤其是由可獲得抗水解性優良的聚酯多元醇(A)之觀點來看，較佳為新戊二醇。 The branched alkylene glycol is specifically an alkylene glycol having a tertiary carbon atom or a tertiary carbon atom in its molecular structure, and examples thereof include 1,2,2-trimethyl-1,3 -Propylene glycol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 3-methyl-1,3-butanediol, 3-methyl-1,5-pentanediol, new Pentylene glycol, 1,4-bis (hydroxymethyl) cyclohexane, 2,2,4-trimethyl-1,3-pentanediol, etc. can be used alone or in combination of two or more kinds. Among them, neopentyl glycol is preferred from the viewpoint of obtaining a polyester polyol (A) having excellent hydrolysis resistance.

於本發明中，前述聚酯多元醇(A)亦可為以前述多元酸或其衍生物原料全具有芳環之多元酸或其衍生物、前述多元醇、與聚異氰酸酯為必要原料的聚酯聚胺基甲酸酯多元醇。此時所使用之聚異氰酸酯，可舉出二異氰酸酯化合物、或3官能以上之聚異氰酸酯化合物。此等聚異氰酸酯可各自單獨使用，亦可併用二種類以上。 In the present invention, the polyester polyol (A) may be a polyester using the polybasic acid or its derivative having an aromatic ring as a raw material for the polybasic acid or its derivative raw materials, the aforementioned polyol, and polyisocyanate as essential raw materials. Polyurethane polyol. Examples of the polyisocyanate to be used at this time include a diisocyanate compound and a triiso or higher-functional polyisocyanate compound. These polyisocyanates may be used alone or in combination of two or more kinds.

前述二異氰酸酯化合物可舉出例如：丁烷-1,4-二異氰酸酯、六亞甲基二異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯、伸苯二甲基二異氰酸酯、間四甲基伸苯二甲基二異氰酸酯等的脂肪族二異氰酸酯；環己烷-1,4-二異氰酸酯、異佛爾酮二異氰酸酯、離胺酸二異氰酸酯、二環己基甲烷-4,4'-二異氰酸酯、1,3-雙(異氰酸基甲基)環己烷(1,3-bis(isocyanatomethyl)cyclohexane)、甲基環己烷二異氰酸酯、亞異丙基二環己基-4,4'-二異氰酸酯、降莰烷二異氰酸酯等的脂環族二異氰酸酯；1,5-伸萘基二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、4,4'-二苯基二甲基甲烷二異氰酸酯、4,4'-二苯甲基二異氰酸酯、二烷基二苯基甲烷二異氰酸酯、四烷基二苯基甲烷二異氰酸酯、1,3-伸苯基二異氰酸酯、1,4-伸苯基二異氰酸酯、甲伸苯基二異氰酸酯(tolylene diisocyanate)、伸苯二甲基二異氰酸酯、四甲基伸苯二甲基二異氰酸酯等的芳香族二異氰酸酯。 Examples of the diisocyanate compound include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethyl ether. Aliphatic hexamethylene diisocyanate, diphenylene diisocyanate, m-tetramethyl diphenylene diisocyanate, etc .; aliphatic diisocyanates; cyclohexane-1,4-diisocyanate, isophorone di diisocyanate, lysine diisocyanate, dicyclohexylmethane 4,4 '- diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane (1,3-bis (isocyanatomethyl) cyclohexane ), A cyclohexane diisocyanate, isopropylidene dicyclohexyl-4,4 '- diisocyanate, norbornane cycloaliphatic diisocyanates of the diisocyanate, and the like; naphthyl-1,5-extending diisocyanate, 4,4' - diphenylmethane diisocyanate, 4,4 '- diphenyl dimethyl methane diisocyanate, 4,4' - methyl diphenyl diisocyanate, dialkyl diphenyl methane diisocyanate, diphenyl tetraalkyl Methane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate Aromatic diisocyanates such as cyanate), phenylene diisocyanate, tetramethyl phenylene diisocyanate, and the like.

前述3官能以上之聚異氰酸酯化合物，可舉出例如分子內具有胺基甲酸酯鍵部位之加合物型聚異氰酸酯化合物、或分子內具有三聚異氰酸酯環結構之脲酸酯(nurate)型聚異氰酸酯化合物。 Examples of the tri- or more functional polyisocyanate compound include, for example, an adduct-type polyisocyanate compound having a urethane bond site in the molecule, or a urate-type polyisocyanate compound having a trimeric isocyanate ring structure in the molecule. Isocyanate compounds.

前述分子內具有胺基甲酸酯鍵部位之加合物型聚異氰酸酯化合物，例如可使二異氰酸酯化合物與多元醇反應而得。該反應所使用之二異氰酸酯化合物，可舉出例如作為前述二異氰酸酯化合物所例示的各種二異氰酸酯化合物，此等可各自單獨使用，亦可併用二種類以上。又，該反應所使用之多元醇化合物，可舉出作為前述多元醇所例示的各種多元醇化合物、或使多元醇與多元酸反應而得的聚酯多元醇等，此等可各自單獨使用，亦可併用二種類以上。 The adduct-type polyisocyanate compound having a urethane bond site in the molecule can be obtained by reacting a diisocyanate compound with a polyol, for example. Examples of the diisocyanate compound used in this reaction include various diisocyanate compounds exemplified as the aforementioned diisocyanate compound, and these may be used alone or in combination of two or more kinds. The polyhydric alcohol compounds used in this reaction include various polyhydric alcohol compounds exemplified as the polyhydric alcohol, or polyester polyols obtained by reacting polyhydric alcohols with polybasic acids, and the like. These can be used individually, Two or more types may be used in combination.

前述分子內具有三聚異氰酸酯環結構之脲酸酯型聚異氰酸酯化合物，例如可使二異氰酸酯化合物與單醇(monoalcohol)及/或二醇反應而得。該反應所使用之二異氰酸酯化合物，可舉出例如作為前述二異氰酸酯化合物所例示的各種二異氰酸酯化合物，此等可各自單獨使用，亦可併用二種類以上。又，作為該反應所使用之單醇，可舉出己醇、2-乙基己醇、辛醇、正癸醇、正十一醇、正十二醇、正十三醇、正十四醇、正十五醇、正十七醇、正十八醇、正十九醇、二十醇、5-乙基-2-壬醇、三甲基壬醇、2-己基癸醇、3,9-二乙基-6-十三醇、2-異庚基異十一醇、2-辛基十二醇、2-癸基十四醇等；作為二醇，可舉出於前述多元醇所例示的脂肪族二醇等。此等單醇或二醇可各自單獨使用，亦可併用二種類以上。 The urethane-type polyisocyanate compound having a trimeric isocyanate ring structure in the molecule can be obtained by, for example, reacting a diisocyanate compound with a monoalcohol and / or a diol. Examples of the diisocyanate compound used in this reaction include various diisocyanate compounds exemplified as the aforementioned diisocyanate compound, and these may be used alone or in combination of two or more kinds. Examples of the monoalcohol used in this reaction include hexanol, 2-ethylhexanol, octanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, and n-tetradecanol , N-pentadecyl alcohol, n-heptadecanyl alcohol, n-octadecanol, n-nonadecanol, eicosanol, 5-ethyl-2-nonanol, trimethylnonanol, 2-hexyldecanol, 3,9 -Diethyl-6-tridecanol, 2-isoheptylisoundecyl alcohol, 2-octyldodecanol, 2-decyltetradecanol, and the like; examples of the diol include the aforementioned polyols Exemplary aliphatic diols and the like. These monoalcohols or diols may be used alone or in combination of two or more kinds.

本發明之聚酯多元醇(A)的固體成分羥值，由使用於接著劑用途時的接著強度更優良，且硬化後的接著層成為適於獲得成形性、耐熱性、耐濕熱性的交聯密度而言，較佳為1.0~40.0mgKOH/g的範圍，更佳為1.0~30.0mgKOH/g，最佳為3.0~25.0mgKOH/g的範圍。 The hydroxyl value of the solid component of the polyester polyol (A) of the present invention is more excellent in the bonding strength when used in the adhesive application, and the cured bonding layer becomes a cross-link suitable for obtaining moldability, heat resistance, and heat and humidity resistance. In terms of the joint density, a range of 1.0 to 40.0 mgKOH / g is preferred, a range of 1.0 to 30.0 mgKOH / g is more preferred, and a range of 3.0 to 25.0 mgKOH / g is most preferred.

本發明之聚酯多元醇(A)的數量平均分子量(Mn)，由使用於接著劑用途時的接著強度更優良而言，較佳為3000~100000的範圍，更佳為3500~50000，再更佳為4000~20000，再更佳為5000~20000。數量平均分子量小於3000時，有層合加工後的外觀、成形加工性差的情況。 The number average molecular weight (Mn) of the polyester polyol (A) of the present invention is more preferably in the range of 3,000 to 100,000, more preferably 3500 to 50,000, since the bonding strength when used in the adhesive application is more excellent. More preferably, it is 4,000 to 20,000, and even more preferably 5,000 to 20,000. When the number average molecular weight is less than 3000, the appearance after lamination and the moldability may be poor.

另一方面，重量平均分子量(Mw)較佳為5000~300000的範圍，更佳為10000~200000的範圍。 On the other hand, the weight average molecular weight (Mw) is preferably in the range of 5,000 to 300,000, and more preferably in the range of 10,000 to 200,000.

此外，於本案發明中，重量平均分子量(Mw)、數量平均分子量(Mn)為藉由下述條件之凝膠滲透層析法(GPC)所測定的值。 In the present invention, 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.

測定裝置：TOSOH股份有限公司製HLC-8320GPC Measuring device: HLC-8320GPC manufactured by TOSOH Co., Ltd.

管柱：TOSOH股份有限公司製TSKgel 4000HXL、TSKgel 3000HXL、TSKgel 2000HXL、TSKgel 1000HXL Columns: TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL, manufactured by TOSOH Co., Ltd.

檢測器：RI(示差折射計) Detector: RI (differential refractometer)

數據處理：TOSOH股份有限公司製Multi-Station GPC-8020modelII Data processing: Multi-Station GPC-8020modelII made by TOSOH Co., Ltd.

標準：單分散聚苯乙烯 Standard: Monodisperse Polystyrene

試料：以樹脂固體成分換算為0.2質量%的四氫呋喃溶液經微過濾器過濾者(100μl) Sample: 0.2 mass% tetrahydrofuran solution converted by the solid content of the resin and filtered through a micro filter (100 μl)

本發明之聚酯多元醇(A)的固體成分酸值不特別限定，較佳為10.0mgKOH/g以下。若為5.0mgKOH/g以下，則使用於接著劑用途時的耐濕熱性更優良而較佳。更佳為2.0mgKOH/g以下。最佳的是1.8mgKOH/g以下。視用途而定，將本發明之接著劑應用於例如後述之太陽能電池的後罩板用途時更佳為1.6mgKOH/g以下。此種聚酯多元醇(A)可藉由後述之製造方法獲得。下限愈少愈佳，但由反應性觀點來看，難以對聚酯多元醇(A)的全部末端導入羥基，而一部分的末端為羧基。因此，固體成分酸值實質上為1.0mgKOH/g以上；對具有芳環之多元酸或其衍生物使用過量的多元醇來進行反應等控制而製造時，大多為0.5mgKOH/g以上。 The solid content acid value of the polyester polyol (A) of the present invention is not particularly limited, but is preferably 10.0 mgKOH / g or less. When it is 5.0 mgKOH / g or less, the moisture and heat resistance when used for an adhesive application is more excellent and preferable. It is more preferably 2.0 mgKOH / g or less. The most preferable is 1.8 mgKOH / g or less. Depending on the application, the adhesive of the present invention is more preferably 1.6 mgKOH / g or less when applied to, for example, a rear cover of a solar cell described later. Such a polyester polyol (A) can be obtained by the manufacturing method mentioned later. The lower the lower limit, the better, but from the viewpoint of reactivity, it is difficult to introduce hydroxyl groups to all the terminals of the polyester polyol (A), and some of the terminals are carboxyl groups. Therefore, the solid content acid value is substantially 1.0 mgKOH / g or more. When a polybasic acid having an aromatic ring or a derivative thereof is controlled by using an excessive amount of a polyhydric alcohol for production or the like, it is usually 0.5 mgKOH / g or more.

本發明之聚酯多元醇(A)的玻璃轉移溫度不特別限定，例如假設為接著劑用途時，為了抑制製造積層體時之乾式層合時的接著劑滲出，較佳為-30℃以上，更佳為-20℃以上，再更佳為-10℃以上。又，為了抑制乾式層合時的筋痕浮起(tunneling)，較佳為80℃以下，更佳為70℃以下，再更佳為55℃以下。 The glass transition temperature of the polyester polyol (A) of the present invention is not particularly limited. For example, in the case of an adhesive application, it is preferably -30 ° C or higher in order to suppress the bleeding of the adhesive during dry lamination when manufacturing a laminate. It is more preferably -20 ° C or more, and even more preferably -10 ° C or more. In addition, in order to suppress tunneling during dry lamination, the temperature is preferably 80 ° C or lower, more preferably 70 ° C or lower, and even more preferably 55 ° C or lower.

此外，本案發明中的玻璃轉移溫度係指如以下方式所測定的值。 The glass transition temperature in the present invention refers to a value measured in the following manner.

使用示差掃描熱量測定裝置(SII NanoTechnology股份有限公司製DSC-7000，下稱DSC)，將5mg的試料在30mL/min的氮氣氣流下由室溫以10℃/min昇溫至200℃後，以10℃/min冷卻至-80℃。再度以10℃/min昇溫至150℃，測定DSC曲線，以將第二次昇溫步驟中所觀測到的測定結果之低溫側的基線延長至高溫側所得的直線、與由玻璃轉移之階梯狀部分的曲線之梯度達最大的點所拉出的切線之交點作為玻璃轉移點，以此時的溫度作為玻璃轉移溫度。又，在第一次昇溫中係昇溫至200℃，惟其只要是可將聚酯多元醇(A)充分熔融的溫度即可，若200℃不足時則適宜調整。同樣地，冷卻溫度若-80℃不足時(玻璃轉移溫度更低時等)亦適宜調整。 Using a differential scanning calorimeter (DSC-7000 manufactured by SII NanoTechnology Co., Ltd., hereinafter referred to as DSC), 5 mg of the sample was heated from room temperature at 10 ° C / min to 200 ° C under a nitrogen gas flow of 30mL / min, and then heated at 10 ° C. C / min was cooled to -80C. The temperature was raised to 150 ° C again at 10 ° C / min, and the DSC curve was measured to extend the straight line obtained by extending the baseline of the low-temperature side of the measurement result observed in the second heating step to the high-temperature side and the stepped portion transferred from glass. The intersection of the tangent line drawn from the point where the gradient of the curve reaches the maximum is taken as the glass transition point, and the temperature at this time is taken as the glass transition temperature. The temperature was raised to 200 ° C. in the first temperature increase, but it was sufficient to melt the polyester polyol (A) sufficiently, and if 200 ° C. was insufficient, it was appropriately adjusted. Similarly, when the cooling temperature is less than -80 ° C (such as when the glass transition temperature is lower), it is also suitable to adjust.

將本發明之聚酯多元醇(A)用於接著劑用途時可提供成形性、耐熱性、及耐濕熱性優良的接著劑之理由仍不明確，惟可如下推測。亦即，藉由多元酸或其衍生物原料全為具有芳環之多元酸或其衍生物，可對聚酯多元醇中導入剛性骨架，且藉由其數量平均分子量(Mn)為3000~100000的範圍，而反應後的接著劑(接著層)具備高凝聚力，可耐受成形時的變形。又，可認為源自具有芳環之多元酸或其衍生物的剛性骨架有助於提升耐熱性、耐濕熱性。 The reason why the polyester polyol (A) of the present invention can be used to provide adhesives with excellent moldability, heat resistance, and heat and humidity resistance is still unclear, but it is estimated as follows. That is, by using the polybasic acid or its derivative raw materials as the polybasic acid or its derivative having an aromatic ring, a rigid skeleton can be introduced into the polyester polyol, and the number-average molecular weight (Mn) thereof is 3000 to 100,000. Range, and the reacted adhesive (adhesive layer) has high cohesion and can withstand deformation during molding. In addition, it is considered that a rigid skeleton derived from a polyacid or a derivative thereof having an aromatic ring contributes to improvement of heat resistance and humidity and heat resistance.

作為本發明之聚酯多元醇(A)較佳的一態樣，可舉出下述聚酯多元醇(A)：為以多元酸或其衍生物 與多元醇為必要原料的聚酯多元醇，其中前述多元酸或其衍生物原料全為具有芳環之二元酸或其衍生物，前述多元醇全為二元醇的聚酯多元醇(A)。 As a preferable aspect of the polyester polyol (A) of the present invention, the following polyester polyol (A) is mentioned: a polyester polyol using a polybasic acid or a derivative thereof and a polyol as essential raw materials The polyester polyol (A) in which the aforementioned polybasic acid or its derivative raw materials are all dibasic acids or their derivatives having an aromatic ring, and the aforementioned polyols are all glycols.

作為本發明之聚酯多元醇(A)其他較佳的一態樣，可舉出下述聚酯多元醇(A)：為以多元酸或其衍生物、多元醇與聚異氰酸酯為必要原料的聚酯聚胺基甲酸酯多元醇，其中前述多元酸或其衍生物原料全為具有芳環之二元酸或其衍生物，前述多元醇全為二元醇，且前述聚異氰酸酯全為二異氰酸酯化合物的聚酯多元醇(A)。 As another preferred aspect of the polyester polyol (A) of the present invention, the following polyester polyols (A) are mentioned: those containing polybasic acid or its derivative, polyhydric alcohol and polyisocyanate as essential raw materials Polyester polyurethane polyol, wherein the aforementioned polyacid or its derivative raw materials are all dibasic acids or derivatives thereof having aromatic rings, the aforementioned polyols are all diols, and the aforementioned polyisocyanates are all Polyester polyol (A) of an isocyanate compound.

藉由後述之多元醇組成物(A)包含此種全以2官能化合物為原料的直鏈狀聚酯多元醇(A)，而藉由多元醇組成物(A)與後述之聚異氰酸酯組成物(B)的反應來形成硬化塗膜時的硬化收縮變小，抑制基材間的變形。因此，後述之反應型接著劑成為接著強度優良者。 The polyhydric alcohol composition (A) described later includes such a linear polyester polyol (A) which is entirely composed of a bifunctional compound, and the polyhydric alcohol composition (A) and a polyisocyanate composition described later (B) The reaction reduces the curing shrinkage when forming a cured coating film, and suppresses deformation between substrates. Therefore, the reaction type adhesive agent mentioned later becomes a thing with excellent adhesive strength.

又，藉由多元醇組成物(A)包含此種聚酯多元醇(A)，而提升硬化塗膜的伸展性。因此，後述之反應型接著劑成為成形加工性特別優異者。 In addition, when the polyol composition (A) contains such a polyester polyol (A), the stretchability of the cured coating film is improved. Therefore, the reaction type adhesive agent mentioned later becomes especially excellent in molding processability.

再者，藉由多元醇組成物(A)包含此種聚酯多元醇(A)，而黏度變得較低，塗敷適性優良，亦可將反應型接著劑適用作為如後述之無溶劑型接著劑、或者固體成分濃度高的溶劑型接著劑。 Furthermore, since the polyol composition (A) contains such a polyester polyol (A), the viscosity becomes low, and the coating suitability is excellent. The reactive adhesive can also be used as a solventless type as described later. An adhesive or a solvent-based adhesive having a high solid content concentration.

此外，本說明書中所稱「全以2官能化合物為原料」，係指實質上全部使用2官能化合物作為原料。例如以工業上所製造，於純化階段無法去除乾淨而殘留單官能之醇或3官能以上之多元醇的二元醇為原料 時，相當於上述全以2官能化合物為原料的直鏈狀聚酯多元醇(A)。關於二元酸或其衍生物、二異氰酸酯化合物亦同。 In addition, the term "all bifunctional compounds are used as raw materials" in this specification means that substantially all bifunctional compounds are used as raw materials. For example, when industrially manufactured, monofunctional alcohols or diols with trifunctional or higher polyhydric alcohols cannot be removed at the purification stage as raw materials, it is equivalent to the above-mentioned linear polyesters that use bifunctional compounds as raw materials. Polyol (A). The same applies to a dibasic acid, a derivative thereof, and a diisocyanate compound.

作為本發明之聚酯多元醇(A)其他較佳的一態樣，可舉出下述聚酯多元醇(A)：為以多元酸或其衍生物與多元醇為必要原料的聚酯多元醇，其中前述多元酸或其衍生物原料全為具有芳環之多元酸或其衍生物，前述多元醇包含分支伸烷基二醇，且前述多元醇100莫耳%中之前述分支伸烷基二醇的含量為5莫耳%以上95莫耳%以下的聚酯多元醇(A)。 As another preferable aspect of the polyester polyol (A) of the present invention, the following polyester polyol (A) is mentioned: a polyester polyol using a polyacid or its derivative and a polyol as essential raw materials Alcohol, wherein the polybasic acid or its derivative raw materials are all polybasic acids or their derivatives having an aromatic ring, the polyhydric alcohol includes a branched alkylene glycol, and the branched alkylene in 100 mol% of the polyhydric alcohol The polyester polyol (A) having a diol content of 5 mol% to 95 mol%.

作為本發明之聚酯多元醇(A)其他較佳的一態樣，可舉出下述聚酯多元醇(A)：為以多元酸或其衍生物、多元醇與聚異氰酸酯為必要原料的聚酯聚胺基甲酸酯多元醇，其中前述多元酸或其衍生物原料全為具有芳環之多元酸或其衍生物，前述多元醇包含分支伸烷基二醇，且前述多元醇100莫耳%中之前述分支伸烷基二醇的含量為5莫耳%以上95莫耳%以下的聚酯多元醇(A)。 As another preferred aspect of the polyester polyol (A) of the present invention, the following polyester polyols (A) are mentioned: those containing polybasic acid or its derivative, polyhydric alcohol and polyisocyanate as essential raw materials A polyester polyurethane polyol, wherein the aforementioned polybasic acid or its derivative raw materials are all polybasic acids or their derivatives having an aromatic ring, the aforementioned polyol comprises a branched alkylene glycol, and the aforementioned polyol is 100 moles. The polyester polyol (A) in which the content of the branched alkylene glycol in the ear% is 5 mol% to 95 mol%.

藉由將分支伸烷基二醇的含量設為5莫耳%以上，而將本發明之聚酯多元醇(A)應用於後述之反應型接著劑時，變得更容易抑制乾式層合後在接著劑表面產生橘皮狀紋路等的外觀劣化。又，為了使流動性、對基材表面之濕潤性良好，並確保初始接著強度，較佳使用體積相對較小、於分子結構內不具有三級碳原子或四級碳原子的多元醇。由兼具優良的外觀與初始接著強度之觀點來看，分支伸烷基二醇的含量較佳限於95莫耳%以下。 When the content of the branched alkylene glycol is 5 mol% or more, when the polyester polyol (A) of the present invention is applied to a reactive adhesive described later, it becomes easier to suppress dry lamination. Deterioration in appearance such as orange peel-like texture is caused on the surface of the adhesive. In addition, in order to improve fluidity, wettability to the surface of the substrate, and ensure initial bonding strength, it is preferable to use a polyol having a relatively small volume and having no tertiary carbon atoms or quaternary carbon atoms in the molecular structure. From the viewpoint of having both excellent appearance and initial bonding strength, the content of the branched alkylene glycol is preferably limited to 95 mol% or less.

本發明之聚酯多元醇(A)可符合上述較佳態樣中的複數種態樣。 The polyester polyol (A) of the present invention can meet a plurality of aspects among the above-mentioned preferred aspects.

前述具有芳環之多元酸或其衍生物與前述多元醇的反應；或者具有芳環之多元酸或其衍生物、前述多元醇與前述聚異氰酸酯的反應，只要以周知之方法進行即可。 The reaction between the polyacid having an aromatic ring or a derivative thereof and the polyhydric alcohol; or the reaction between the polyacid having an aromatic ring or a derivative thereof, the polyhydric alcohol and the polyisocyanate may be performed by a known method.

例如，具有芳環之多元酸或其衍生物與前述多元醇的反應，可使用具有芳環之多元酸或其衍生物與多元醇、及聚合觸媒，以周知慣用之聚縮合反應(或酯化反應)來進行。又，前述具有芳環之多元酸或其衍生物、前述多元醇與前述聚異氰酸酯的反應，藉由使前述具有芳環之多元酸或其衍生物與前述多元醇以前述方法反應而成的聚酯多元醇與前述聚異氰酸酯，視需求而在周知慣用之胺基甲酸酯化觸媒的存在下進行鏈伸長反應，可獲得本發明之聚酯多元醇(A)。 For example, for the reaction of a polyacid having an aromatic ring or a derivative thereof with the aforementioned polyol, a polycondensation reaction (or an ester) of a polyacid having an aromatic ring or a derivative thereof with a polyhydric alcohol and a polymerization catalyst may be used. Chemical reaction). In addition, the reaction of the polyacid having an aromatic ring or a derivative thereof, the polyhydric alcohol and the polyisocyanate, is a polymer formed by reacting the polyacid having an aromatic ring or a derivative thereof with the polyhydric alcohol by the aforementioned method. The ester polyol and the aforementioned polyisocyanate are subjected to a chain elongation reaction in the presence of a well-known and commonly used urethane-forming catalyst as required to obtain the polyester polyol (A) of the present invention.

具有芳環之多元酸或其衍生物與多元醇的酯化反應，更具體而言，係將具有芳環之多元酸或其衍生物、多元醇、與聚合觸媒裝入具備攪拌機、精餾設備的反應容器中，一面攪拌，一面在常壓下予以昇溫至130℃左右。其後，一面在130~260℃之範圍的反應溫度下以1小時5~10℃的比例昇溫，一面餾去生成的水。使其進行4~12小時的酯化反應後，一面由常壓緩緩地提高減壓度至1~300torr的範圍內，一面餾去剩餘的多元醇來促進反應，藉此可製造聚酯多元醇(A)。 Esterification reaction of a polyacid having an aromatic ring or a derivative thereof with a polyhydric alcohol, more specifically, a polyacid having an aromatic ring or a derivative thereof, a polyhydric alcohol, and a polymerization catalyst are charged with a stirrer and rectified The reaction vessel of the equipment was heated to about 130 ° C under normal pressure while being stirred. After that, the temperature was raised at a reaction temperature in the range of 130 to 260 ° C. at a rate of 5 to 10 ° C. for 1 hour, and the generated water was distilled off. After the esterification reaction is performed for 4 to 12 hours, the pressure is gradually increased from normal pressure to the range of 1 to 300 torr, and the remaining polyol is distilled off to promote the reaction, thereby producing a polyester polyol. Alcohol (A).

作為用於酯化反應之聚合觸媒，較佳為包含：選自包含週期表2族、4族、12族、13族、14族、15族之群組的至少1種金屬、或該金屬之化合物的聚合觸媒。作為包含所述金屬或其金屬化合物的聚合觸媒，可舉出Ti、Sn、Zn、Al、Zr、Mg、Hf、Ge等金屬、此等金屬之化合物，更具體而言為四異丙氧化鈦、四丁氧化鈦、乙醯丙酮氧鈦(titanium oxyacetylacetonate)、辛酸錫、2-乙基己烷錫、乙醯丙酮鋅、四氯化鋯、四氯化鋯四氫呋喃錯合物、四氯化鉿、四氯化給四氫呋喃錯合物、氧化鍺、四乙氧基鍺(tetraethoxygermanium)等。 As the polymerization catalyst used for the esterification reaction, it is preferred to include at least one metal selected from the group consisting of Group 2, Group 4, Group 12, Group 13, Group 14, and Group 15 of the periodic table, or the metal Polymerization catalyst for compounds. Examples of the polymerization catalyst containing the metal or a metal compound thereof include metals such as Ti, Sn, Zn, Al, Zr, Mg, Hf, and Ge, and compounds of these metals, and more specifically, tetraisopropyl oxide Titanium, titanium tetrabutoxide, titanium oxyacetylacetonate, tin octoate, 2-ethylhexanetin, zinc acetoacetone, zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, tetrachloride Samarium, tetrahydrofuran complex, germanium oxide, tetraethoxygermanium and the like.

作為可用於酯化反應之聚合觸媒的市售品，較佳可舉出Matsumoto Fine Chemical公司製之ORGATIX TA系列、TC系列、ZA系列、ZC系列、AL系列、日東化成公司製之有機錫系觸媒、無機金屬觸媒、無機錫化合物。 As commercially available polymerization catalysts that can be used for the esterification reaction, ORGATIX TA series, TC series, ZA series, ZC series, AL series, and Nitto Kasei Corporation's organotin series manufactured by Matsumoto Fine Chemical Co., Ltd. are preferred. Catalysts, inorganic metal catalysts, inorganic tin compounds.

此等聚合觸媒的用量，只要可控制酯化反應，且可獲得品質良好的聚酯多元醇(A)則不特別限制；就其一例而言，相對於多元酸或其衍生物與多元醇的合計量為10~1000ppm，較佳為20~800ppm。為了抑制聚酯多元醇(A)的著色，更佳為30~500ppm。 The amount of these polymerization catalysts is not particularly limited as long as the esterification reaction can be controlled and a good quality polyester polyol (A) can be obtained; as an example, it is relative to the polybasic acid or its derivative and the polybasic alcohol. The total amount is 10 to 1000 ppm, preferably 20 to 800 ppm. In order to suppress the coloring of the polyester polyol (A), it is more preferably 30 to 500 ppm.

本發明所使用之聚酯多元醇(A)，為直鏈狀聚酯多元醇(A)時，較佳的是兩末端為羥基；為具備分支結構之聚酯多元醇(A)時，較佳的是全部末端為羥基。為了獲得此種聚酯多元醇(A)，只要相對於具有芳環之多元酸或其衍生物，使用過量的多元醇來進行反應即可。相 對於1.0莫耳之具有芳環之多元酸或其衍生物，只要將多元醇的裝入量設為1.0莫耳(惟不包含1.0莫耳)~1.4莫耳、更佳設為1.0莫耳(惟不包含1.0莫耳)~1.2莫耳即可。 When the polyester polyol (A) used in the present invention is a linear polyester polyol (A), it is preferred that both ends are hydroxyl groups; when it is a polyester polyol (A) having a branched structure, It is preferable that all the terminals are hydroxyl groups. In order to obtain such a polyester polyol (A), what is necessary is just to perform reaction using the polyhydric alcohol with respect to the polybasic acid or its derivative which has an aromatic ring. Relative to 1.0 mol of a polyacid or an derivative thereof having an aromatic ring, as long as the amount of the polyol is set to 1.0 mol (but not including 1.0 mol) to 1.4 mol, more preferably 1.0 mol (But does not include 1.0 mole) ~ 1.2 mole.

又，本發明所使用之聚酯聚胺基甲酸酯多元醇(A)可將以上述方法所得之聚酯多元醇(A)藉由聚異氰酸酯進行鏈伸長而得。就其具體的製造方法而言，係將聚酯多元醇(A)、聚異氰酸酯、鏈伸長觸媒、及視需求使用之聚酯多元醇(A)與聚異氰酸酯之良溶劑裝入反應容器中，以60~90℃的反應溫度加以攪拌。進行反應至源於所用之聚異氰酸酯的異氰酸酯基變得實質上不殘留為止，而得到本發明所使用之聚酯聚胺基甲酸酯多元醇(A)。 The polyester polyurethane (A) used in the present invention can be obtained by subjecting the polyester polyol (A) obtained by the method described above to chain extension of a polyisocyanate. In terms of its specific manufacturing method, a polyester polyol (A), a polyisocyanate, a chain extension catalyst, and a good solvent of the polyester polyol (A) and polyisocyanate used as required are charged into a reaction vessel. Stir at a reaction temperature of 60 to 90 ° C. The reaction is performed until the isocyanate group derived from the used polyisocyanate does not remain substantially, and the polyester polyurethane polyurethane (A) used in the present invention is obtained.

就前述鏈伸長觸媒而言，可使用作為一般的胺基甲酸酯化觸媒所使用的周知常用觸媒。具體而言，可舉出有機錫化合物、有機羧酸錫鹽、鉛羧酸鹽、鉍羧酸鹽、鈦化合物、鋯化合物等，可單獨使用或併用來使用。就前述鏈伸長觸媒的用量而言，只要是充分促進聚酯多元醇(A)與聚異氰酸酯之反應的量即可，具體而言，相對於聚酯多元醇(A)與聚異氰酸酯的合計量，較佳為5.0質量%以下。為了抑制因觸媒導致之對樹脂的水解或著色，更佳為1.0質量以下。再者，此等鏈伸長觸媒亦可考量作為後述之聚酯多元醇(A)與異氰酸酯組成物(B)的硬化觸媒之作用而使用。 As the aforementioned chain extension catalyst, a well-known common catalyst used as a general urethane catalyst can be used. Specifically, an organic tin compound, an organic tin carboxylate, a lead carboxylate, a bismuth carboxylate, a titanium compound, a zirconium compound, etc. can be mentioned, and it can be used individually or in combination. The amount of the chain elongation catalyst may be an amount that sufficiently promotes the reaction between the polyester polyol (A) and the polyisocyanate, and specifically, the total amount of the polyester polyol (A) and the polyisocyanate The amount is preferably 5.0% by mass or less. In order to suppress hydrolysis or coloration of the resin due to the catalyst, it is more preferably 1.0 mass or less. In addition, these chain extension catalysts can also be used in consideration of the function as a curing catalyst of the polyester polyol (A) and the isocyanate composition (B) described later.

作為異氰酸酯基之殘量的確認方法，可舉出：藉由紅外吸收光譜測定，而確認有無源自異氰酸酯基之在吸收光譜的2260cm-1附近所觀察到的吸收峰；或藉由滴定法來定量異氰酸酯基。 Examples of the method for confirming the residual amount of the isocyanate group include: confirming the presence or absence of an absorption peak derived from the isocyanate group in the vicinity of 2260 cm -1 of the absorption spectrum by an infrared absorption spectrum measurement; or by a titration method Quantify isocyanate groups.

作為用於聚酯聚胺基甲酸酯多元醇(A)之製造的良溶劑，可舉出乙酸乙酯、乙酸丁酯、甲基乙基酮、甲基異丁基酮、丙二醇單甲基醚乙酸酯、甲苯、二甲苯等。可單獨使用，亦可併用二種以上。 Examples of good solvents used in the production of polyester polyurethane polyols (A) include ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and propylene glycol monomethyl. Ether acetate, toluene, xylene, etc. It can be used alone or in combination of two or more.

本發明之聚酯多元醇(A)亦可於不損及本發明之效果的範圍併用其他的反應原料。 The polyester polyol (A) of the present invention may be used with other reaction raw materials within a range that does not impair the effects of the present invention.

(反應型接著劑) (Reactive Adhesive)

本發明之反應型接著劑係以包含前述聚酯多元醇(A)的多元醇組成物(A)與聚異氰酸酯組成物(B)為必要成分。 The reactive-type adhesive agent of this invention contains the polyol composition (A) and the polyisocyanate composition (B) containing the said polyester polyol (A) as an essential component.

(聚異氰酸酯組成物(B)) (Polyisocyanate composition (B))

本發明所使用之聚異氰酸酯組成物(B)包含異氰酸酯化合物(以下於本發明中稱為異氰酸酯化合物(B))。異氰酸酯化合物(B)只要是一分子中具有異氰酸酯基的化合物則不特別限定，可使用各種的化合物。具體而言，可使用前述之聚酯多元醇(A)的原料中所述之各種的二異氰酸酯化合物、使各種的二異氰酸酯化合物與二醇化合物反應所得之加合物改質二異氰酸酯化合物、此等之雙脲改質體、脲基甲酸酯改質體、或各種3官能以上之 聚異氰酸酯化合物。此等異氰酸酯化合物(B)可各自單獨使用，亦可併用二種類以上。 The polyisocyanate composition (B) used in the present invention contains an isocyanate compound (hereinafter referred to as an isocyanate compound (B) in the present invention). The isocyanate compound (B) is not particularly limited as long as it is a compound having an isocyanate group in one molecule, and various compounds can be used. Specifically, various diisocyanate compounds described in the aforementioned raw materials of the polyester polyol (A), adducts modified by reacting various diisocyanate compounds with diol compounds, and the diisocyanate compounds can be used. Such as diurea modifiers, urethane modifiers, or various trifunctional polyisocyanate compounds. These isocyanate compounds (B) may be used alone or in combination of two or more kinds.

前述各種的二異氰酸酯化合物可舉出例如：丁烷-1,4-二異氰酸酯、六亞甲基二異氰酸酯、2,2,4-三甲基六亞甲基二異氰酸酯、2,4,4-三甲基六亞甲基二異氰酸酯、伸苯二甲基二異氰酸酯、間四甲基伸苯二甲基二異氰酸酯等的脂肪族二異氰酸酯化合物；環己烷-1,4-二異氰酸酯、異佛爾酮二異氰酸酯、離胺酸二異氰酸酯、二環己基甲烷-4,4'-二異氰酸酯、1,3-雙(異氰酸基甲基)環己烷、甲基環己烷二異氰酸酯等的脂環族二異氰酸酯化合物；1,5-伸萘基二異氰酸酯、4,4'-二苯基甲烷二異氰酸酯、4,4'-二苯基二甲基甲烷二異氰酸酯、4,4'-二苯甲基二異氰酸酯、二烷基二苯基甲烷二異氰酸酯、四烷基二苯基甲烷二異氰酸酯、1,3-伸苯基二異氰酸酯、1,4-伸苯基二異氰酸酯、甲伸苯基二異氰酸酯等的芳香族二異氰酸酯化合物等。此等可各自單獨使用，亦可併用二種類以上。 Examples of the various diisocyanate compounds include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4- Aliphatic diisocyanate compounds such as trimethylhexamethylene diisocyanate, phenylene dimethyl diisocyanate, m-tetramethyl phenylene diisocyanate; cyclohexane-1,4-diisocyanate, isophor chalcone diisocyanate, lysine diisocyanate, dicyclohexylmethane 4,4 '- diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate and the like alicyclic diisocyanate compounds; 1,5 extending naphthyl diisocyanate, 4,4 '- diphenylmethane diisocyanate, 4,4' - diphenyl dimethyl methane diisocyanate, 4,4 '- Benzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, methylphenyl An aromatic diisocyanate compound such as a diisocyanate. These can be used individually or in combination of two or more types.

作為前述加合物改質聚異氰酸酯化合物之反應原料的二醇化合物，可舉出例如乙二醇、丙二醇、1,3-丙二醇、1,2,2-三甲基-1,3-丙二醇、2,2-二甲基-3-異丙基-1,3-丙二醇、1,4-丁二醇、1,3-丁二醇、3-甲基-1,3-丁二醇、1,5-戊二醇、3-甲基1,5-戊二醇、新戊二醇、1,6-己二醇、1,4-雙(羥甲基)環己烷、2,2,4-三甲基-1,3-戊二醇等。此等可各自單獨使用，亦可併用二種類以上。 Examples of the diol compound as a raw material for the reaction of the adduct-modified polyisocyanate compound include ethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1 , 5-pentanediol, 3-methyl 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis (hydroxymethyl) cyclohexane, 2,2, 4-trimethyl-1,3-pentanediol and the like. These can be used individually or in combination of two or more types.

又，前述3官能以上之聚異氰酸酯化合物，只要是一分子中具有3個以上之異氰酸酯基的化合物則不特別限定，可使用各種的化合物。具體而言，可舉出各種的二異氰酸酯化合物之三聚異氰酸酯改質聚異氰酸酯化合物、或使各種的二異氰酸酯化合物與3官能以上之多元醇化合物反應所得之加合物改質聚異氰酸酯化合物、各種的二異氰酸酯化合物之雙脲改質體、各種的二異氰酸酯化合物之脲基甲酸酯改質體等。此等聚異氰酸酯化合物可各自單獨使用，亦可併用二種類以上。 The polyisocyanate compound having three or more functions 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, triisoisocyanate-modified polyisocyanate compounds of various diisocyanate compounds, adduct-modified polyisocyanate compounds obtained by reacting various diisocyanate compounds with trifunctional or higher-functional polyol compounds, and various Bisurea modifiers of various diisocyanate compounds, uretate modifiers of various diisocyanate compounds, and the like. These polyisocyanate compounds may be used alone or in combination of two or more kinds.

(反應型接著劑 其他成分) (Reactive Adhesive Other Ingredients)

本發明之反應型接著劑，在不損及本發明之效果的範圍可併用其他成分。例如，多元醇組成物(A)中，較佳為除了前述聚酯多元醇(A)外亦含有聚碳酸酯多元醇化合物。此時，前述聚酯多元醇化合物與聚碳酸酯多元醇化合物的摻混比率，由成為對各種基材的接著性高且耐濕熱性亦優良的反應型接著劑而言，相對於兩者的合計質量，聚酯多元醇化合物較佳為30~99.5質量%的範圍，更佳為60~99質量%的範圍。 The reactive-type adhesive of the present invention may be used in combination with other components so long as the effect of the present invention is not impaired. For example, the polyol composition (A) preferably contains a polycarbonate polyol compound in addition to the polyester polyol (A). At this time, the blending ratio of the polyester polyol compound and the polycarbonate polyol compound is a reactive adhesive with high adhesion to various substrates and excellent heat and humidity resistance. The total mass of 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.

前述聚碳酸酯多元醇化合物的數量平均分子量(Mn)，由成為對各種基材的接著性高且耐濕熱性亦優良的反應型接著劑而言，較佳為300~2,000的範圍。其羥值較佳為30~250mgKOH/g的範圍，更佳為40~200mgKOH/g的範圍。又，前述聚碳酸酯多元醇化合物較佳為聚碳酸酯二醇化合物。 The number-average molecular weight (Mn) of the polycarbonate polyol compound is preferably in the range of 300 to 2,000 from the viewpoint of being a reactive adhesive having high adhesion to various substrates and excellent heat and humidity resistance. The hydroxyl value is preferably in the range of 30 to 250 mgKOH / g, and more preferably in the range of 40 to 200 mgKOH / g. The polycarbonate polyol compound is preferably a polycarbonate diol compound.

又，前述多元醇組成物(A)，較佳為除了前述聚酯多元醇化合物外亦含有聚氧伸烷基(polyoxyalkylene)改質多元醇化合物。此時，前述聚酯多元醇化合物與聚氧伸烷基改質多元醇化合物的摻混比率，由成為對各種基材的接著性高且耐濕熱性亦優良的反應型接著劑而言，相對於兩者的合計質量，聚酯多元醇化合物較佳為30~99.5質量%的範圍，更佳為60~99質量%的範圍。 The polyol composition (A) preferably contains a polyoxyalkylene modified polyol compound in addition to the polyester polyol compound. At this time, the blending ratio of the polyester polyol compound and the polyoxyalkylene modified polyol compound is a reactive type adhesive with high adhesion to various substrates and excellent heat and humidity resistance. In terms of the total mass of the two, 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.

前述聚氧伸烷基改質多元醇化合物的數量平均分子量(Mn)，由成為對各種基材的接著性高且耐濕熱性亦優良的反應型接著劑而言，較佳為300~2,000的範圍。其羥值較佳為40~250mgKOH/g的範圍，更佳為50~200mgKOH/g的範圍。又，前述聚氧伸烷基改質多元醇化合物較佳為聚氧伸烷基改質二醇化合物。 The number-average molecular weight (Mn) of the polyoxyalkylene modified polyol compound is preferably from 300 to 2,000 because it is a reactive adhesive having high adhesion to various substrates and excellent heat and humidity resistance. range. 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.

本發明所使用之前述多元醇組成物(A)，除了前述聚酯多元醇(A)外，亦可含有其他的樹脂成分。使用其他的樹脂成分時，相對於主劑的總質量，較佳以50質量%以下來使用，更佳以30質量%以下來使用。作為其他的樹脂成分的具體例，可舉出環氧樹脂。前述環氧樹脂可舉出例如：雙酚A型環氧樹脂、雙酚F型環氧樹脂等的雙酚型環氧樹脂；聯苯型環氧樹脂、四甲基聯苯型環氧樹脂等的聯苯型環氧樹脂；二環戊二烯-苯酚加成反應型環氧樹脂等。此等可各自單獨使用，亦可併用二種類以上。此等當中，由成為對各種基材的接著性高且耐濕熱性亦優良的反應型接著劑而言，較佳使用雙酚型環氧樹脂。 The polyol composition (A) used in the present invention may contain other resin components in addition to the polyester polyol (A). When other resin components are used, it is preferably used in an amount of 50% by mass or less, more preferably 30% by mass or less with respect to the total mass of the main agent. Specific examples of other resin components include epoxy resins. Examples of the epoxy resin include bisphenol epoxy resins such as bisphenol A epoxy resin and bisphenol F epoxy resin; biphenyl epoxy resin, tetramethylbiphenyl epoxy resin, and the like. Biphenyl epoxy resin; dicyclopentadiene-phenol addition reaction epoxy resin, etc. These can be used individually or in combination of two or more types. Among these, a bisphenol-type epoxy resin is preferably used because it is a reactive adhesive having high adhesiveness to various substrates and excellent in moisture and heat resistance.

前述環氧樹脂的數量平均分子量(Mn)，由成為對各種基材的接著性高且耐濕熱性亦優良的反應型接著劑而言，較佳為300~2,000的範圍。又，其環氧當量較佳為150~1000g/當量的範圍。 The number average molecular weight (Mn) of the epoxy resin is preferably in the range of 300 to 2,000 from the viewpoint of being a reactive adhesive having high adhesion to various substrates and excellent heat and humidity resistance. The epoxy equivalent is preferably in the range of 150 to 1000 g / equivalent.

使用前述環氧樹脂時，前述聚酯多元醇(A)與環氧樹脂的摻混比率，由成為對各種基材的接著性高且耐濕熱性亦優良的反應型接著劑而言，相對於兩者的合計質量，聚酯多元醇(A)較佳為30~99.5質量%的範圍，更佳為60~99質量%的範圍。 When the epoxy resin is used, the blending ratio of the polyester polyol (A) and the epoxy resin is a reactive adhesive having high adhesion to various substrates and excellent heat and humidity resistance. The total mass of the two is preferably in the range of 30 to 99.5% by mass, and more preferably in the range of 60 to 99% by mass.

本發明所使用之前述多元醇組成物(A)亦可含有增黏劑。作為增黏劑，可舉出例如松香系或松香酯系增黏劑、萜烯系或萜烯酚系增黏劑、飽和烴樹脂、苯并呋喃系增黏劑、苯并呋喃-茚系增黏劑、苯乙烯樹脂系增黏劑、二甲苯樹脂系增黏劑、酚樹脂系增黏劑、石油樹脂系增黏劑等。此等可各自單獨使用，亦可併用二種類以上。又，該增黏劑主要可藉由分子量而獲得具有各種軟化點者，由與構成前述多元醇組成物(A)的其他樹脂混合時的相溶性、色調或熱穩定性等之點而言，特佳為：軟化點為80~160℃、較佳為90~110℃的松香系樹脂及其氫化衍生物。通常，相對於100質量份之構成前述多元醇組成物(A)之樹脂的固體成分，係以1~30質量份(固體成分)的範圍使用，特佳以5~20質量份(固體成分)的範圍使用。 The aforementioned polyol composition (A) used in the present invention may also contain a tackifier. Examples of the tackifier include rosin-based or rosin ester-based tackifiers, terpene-based or terpene-phenol-based tackifiers, saturated hydrocarbon resins, benzofuran-based tackifiers, and benzofuran-indene-based tackifiers. Adhesives, styrene resin-based tackifiers, xylene resin-based tackifiers, phenol resin-based tackifiers, petroleum resin-based tackifiers, and the like. These can be used individually or in combination of two or more types. In addition, the tackifier can be obtained mainly by the molecular weight with various softening points. From the point of compatibility, color tone, and thermal stability when mixed with other resins constituting the polyol composition (A), Particularly preferred is a rosin-based resin and its hydrogenated derivative having a softening point of 80 to 160 ° C, preferably 90 to 110 ° C. Generally, it is used in the range of 1 to 30 parts by mass (solid content) with respect to 100 parts by mass of the solid content of the resin constituting the polyol composition (A), and particularly preferably 5 to 20 parts by mass (solid content) The range is used.

作為松香系或松香酯系，可舉出聚合松香、歧化松香(disproportionated rosin)、氫化松香、順丁烯二 酸酐化松香(maleated rosin)、反丁烯二酸酐化松香(fumarated rosin)、及此等之甘油酯、新戊四醇酯、甲酯、乙酯、丁酯、乙二醇酯、二乙二醇酯、三乙二醇酯等。 Examples of the rosin-based or rosin-based rosin include polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, maleated rosin, and fumarated rosin. And other glycerides, neopentaerythritol esters, methyl esters, ethyl esters, butyl esters, glycol esters, diethylene glycol esters, triethylene glycol esters, and the like.

作為萜烯系或萜烯酚系，可舉出低聚合萜烯系、α-蒎烯聚合物、β-蒎烯聚合物、萜烯酚系、芳香族改質萜烯系、氫化萜烯系等。 Examples of the terpene system or terpene phenol system include oligomeric terpene system, α-pinene polymer, β-pinene polymer, terpene phenol system, aromatic modified terpene system, and hydrogenated terpene system. Wait.

作為石油樹脂系，可例示：由戊烯、戊二烯、異戊二烯等所得之將碳數為5個的石油餾分聚合而成之石油樹脂；由茚、甲基茚、乙烯基甲苯、苯乙烯、α-甲基苯乙烯、β-甲基苯乙烯等所得之將碳數為9個的石油餾分聚合而成之石油樹脂；由前述各種單體所得之C5-C9共聚合石油樹脂及將此等氫化而成之石油樹脂；由環戊二烯、二環戊二烯所得之石油樹脂；以及此等石油樹脂之氫化物；將此等石油樹脂以順丁烯二酸酐、順丁烯二酸、反丁烯二酸、(甲基)丙烯酸、苯酚等改質而成之改質石油樹脂等。 Examples of petroleum resins include petroleum resins obtained by polymerizing petroleum fractions having 5 carbons, such as pentene, pentadiene, isoprene, and the like; from indene, methylindene, vinyltoluene, Petroleum resins obtained by polymerizing petroleum fractions with 9 carbons, such as styrene, α-methylstyrene, and β-methylstyrene; C5-C9 copolymerized petroleum resins obtained from the aforementioned various monomers, and Petroleum resins obtained by hydrogenating these; petroleum resins obtained from cyclopentadiene and dicyclopentadiene; and hydrides of these petroleum resins; these petroleum resins are prepared using maleic anhydride and maleic anhydride Modified petroleum resins such as diacid, fumaric acid, (meth) acrylic acid, and phenol.

作為酚樹脂系，可使用酚類與甲醛之縮合物。作為該酚類，可舉出苯酚、間甲酚、3,5-二甲酚、對烷基酚、間苯二酚等，可例示使此等酚類與甲醛以鹼觸媒進行加成反應而成之可溶酚醛樹脂、或以酸觸媒進行縮合反應而成之酚醛清漆樹脂等。又，亦可例示藉由對松香以酸觸媒加成酚並進行熱聚合而得之松香酚樹脂等。 As the phenol resin, a condensate of phenols and formaldehyde can be used. Examples of the phenols include phenol, m-cresol, 3,5-xylenol, p-alkylphenol, and resorcinol. Examples of the phenols include an addition reaction of formaldehyde and formaldehyde with a base catalyst. Soluble novolac resin, or novolac resin produced by condensation reaction with acid catalyst. In addition, rosin phenol resins obtained by adding phenol to rosin with an acid catalyst and performing thermal polymerization can also be exemplified.

此等當中，特佳為軟化點為80~160℃的氫化松香系；更佳為酸值為2~10mgKOH/g、羥值為5mgKOH/g以下的氫化松香系。 Among these, particularly preferred are hydrogenated rosin systems having a softening point of 80 to 160 ° C; more preferred are hydrogenated rosin systems having an acid value of 2 to 10 mgKOH / g and a hydroxyl value of 5 mgKOH / g or less.

又，本發明之多元醇組成物(A)也可含有酮樹脂。作為酮樹脂，可舉出周知慣用者，可適用甲醛樹脂、環己酮‧甲醛樹脂或酮醛縮合樹脂等。 The polyol composition (A) of the present invention may contain a ketone resin. Examples of the ketone resin include those known in the art, and formaldehyde resin, cyclohexanone · formaldehyde resin, or ketone-formaldehyde condensation resin can be applied.

使用前述酮樹脂時，前述聚酯多元醇(A)與酮樹脂的摻混比率，由成為對各種基材的接著性高且耐濕熱性亦優良的接著劑而言，相對於兩者的合計質量，聚酯多元醇(A)較佳為30~99.5質量%的範圍，更佳為60~99質量%的範圍。 When the ketone resin is used, the blending ratio of the polyester polyol (A) and the ketone resin is an adhesive with high adhesion to various substrates and excellent moisture and heat resistance, relative to the total of the two. The mass of the polyester polyol (A) is preferably in the range of 30 to 99.5% by mass, and more preferably in the range of 60 to 99% by mass.

本發明之接著劑亦可含有環醯胺化合物。當本發明之接著劑含有環醯胺化合物時，可添加於多元醇組成物(A)，亦可添加於異氰酸酯組成物(B)。也可於混合多元醇組成物(A)與異氰酸酯組成物(B)時添加。 The adhesive of the present invention may contain a cyclic amine compound. When the adhesive of the present invention contains a cyclic amide compound, it may be added to the polyol composition (A) or the isocyanate composition (B). You may add it when mixing a polyol composition (A) and an isocyanate composition (B).

藉由併用環醯胺化合物，可使耐濕熱性更良好。作為環醯胺樹脂，可舉出δ-戊內醯胺、ε-己內醯胺、ω-庚內醯胺(enantholactam)、η-辛內醯胺(capryl lactam)、β-丙內醯胺等，可單獨使用或併用二種以上。特佳使用ε-己內醯胺。 By using a cyclic amine compound in combination, the moist heat resistance can be made better. Examples of the cyclic melamine resin include δ-valerolactam, ε-caprolactam, ω-enantholactam, η-capryl lactam, and β-propiolactam Etc., It can be used individually or in combination of 2 or more types. Particularly preferred is ε-caprolactam.

使用環醯胺化合物時，其摻混量較佳為每多元醇組成物(A)與異氰酸酯組成物(B)的合計100質量份為0.1質量份以上，較佳為5質量份以下。 When a cyclic amide compound is used, the blending amount thereof is preferably 0.1 parts by mass or more, and preferably 5 parts by mass or less per 100 parts by mass of the total of the polyol composition (A) and the isocyanate composition (B).

本發明之接著劑中，作為另一良好之態樣，可併用周知之磷酸類或其衍生物。藉此，可進一步提升接著劑的初始接著性，解決筋痕浮起等問題。 In another aspect of the adhesive of the present invention, a well-known phosphoric acid or a derivative thereof may be used in combination. Thereby, the initial adhesiveness of the adhesive can be further improved, and problems such as floating of the marks can be solved.

作為此處所使用之磷酸類或其衍生物，可舉出：例如次磷酸、亞磷酸、正磷酸、連二磷酸等的磷 酸類；例如偏磷酸、焦磷酸、三聚磷酸、聚磷酸、超磷酸(ultraphosphoric acid)等的縮合磷酸類；例如正磷酸單甲酯、正磷酸單乙酯、正磷酸單丙酯、正磷酸單丁酯、正磷酸單-2-乙基己酯、正磷酸單苯酯、亞磷酸單甲酯、亞磷酸單乙酯、亞磷酸單丙酯、亞磷酸單丁酯、亞磷酸單-2-乙基己酯、亞磷酸單苯酯、正磷酸二-2-乙基己酯、正磷酸二苯酯、亞磷酸二甲酯、亞磷酸二乙酯、亞磷酸二丙酯、亞磷酸二丁酯、亞磷酸二-2-乙基己酯、亞磷酸二苯酯等之單、二酯化物、來自縮合磷酸與醇類之單、二酯化物；例如對前述之磷酸類加成例如環氧乙烷、環氧丙烷等的環氧化合物而成者；例如對脂肪族或芳香族之二環氧丙基醚加成前述之磷酸類而得之環氧磷酸酯類等。 Examples of the phosphoric acid or its derivative used herein include phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid, and diphosphoric acid; for example, metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and superphosphoric acid (ultraphosphoric acid) and other condensed phosphates; for example, monomethyl orthophosphate, monoethyl orthophosphate, monopropyl orthophosphate, monobutyl orthophosphate, mono-2-ethylhexyl orthophosphate, monobenzene orthophosphate Ester, monomethyl phosphite, monoethyl phosphite, monopropyl phosphite, monobutyl phosphite, mono-2-ethylhexyl phosphite, monophenyl phosphite, di-2-ethyl orthophosphate Hexyl hexyl ester, diphenyl orthophosphate, dimethyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, di-2-ethylhexyl phosphite, diphenyl phosphite Monoesters, diesters, etc., derived from condensed phosphoric acid and alcohols; for example, those obtained by adding an epoxy compound such as ethylene oxide, propylene oxide, etc. to the aforementioned phosphoric acid; Epoxy phosphates and the like obtained by adding a diepoxypropyl ether of an aromatic or aromatic type to the aforementioned phosphoric acid.

上述之磷酸類或其衍生物可使用一種或二種以上。作為含有其之方法，僅單純予以混入即可。 One or two or more kinds of the above-mentioned phosphoric acids or their derivatives can be used. As a method of containing it, it may be simply mixed.

又，本發明之接著劑中，亦可使用接著促進劑。接著促進劑可舉出矽烷偶合劑、鈦酸酯系偶合劑、鋁系等的偶合劑、環氧樹脂等。 Moreover, an adhesive accelerator can also be used for the adhesive agent of this invention. Examples of the subsequent accelerator include silane coupling agents, titanate-based coupling agents, aluminum-based coupling agents, and epoxy resins.

作為矽烷偶合劑，可舉出例如γ-胺丙基三乙氧基矽烷、γ-胺丙基三甲氧基矽烷、N-β(胺乙基)-γ-胺丙基三甲氧基矽烷、N-β(胺乙基)-γ-胺丙基三甲基二甲氧基矽烷、N-苯基-γ-胺丙基三甲氧基矽烷等的胺基矽烷；β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-環氧丙氧丙基三甲氧基矽烷(γ-glycidoxypropyltrimethoxysilane)、γ-環氧丙氧丙基三乙氧基矽烷等的環氧矽烷；乙烯基參(β-甲 氧乙氧基)矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、γ-甲基丙醯氧丙基三甲氧基矽烷(γ-methacryloxypropyltrimethoxysilane)等的乙烯基矽烷；六甲基二矽氮烷、γ-巰丙基三甲氧基矽烷等。 Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N -β (aminoethyl) -γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and other aminosilanes; β- (3,4-cyclo (Oxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and other epoxy silanes; vinyl Vinyl silanes such as (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, etc. ; Hexamethyldisilazane, γ-mercaptopropyltrimethoxysilane, etc .;

作為鈦酸酯系偶合劑，可舉出例如四異丙氧基鈦、四正丁氧基鈦、鈦酸丁酯二聚物、鈦酸四硬脂酯、乙醯丙酮鈦、乳酸鈦、四辛二醇鈦酸酯、四硬脂氧基鈦等。 Examples of the titanate-based coupling agent include tetraisopropoxy titanium, tetra-n-butoxy titanium, butyl titanate dimer, tetrastearate titanate, titanium acetoacetone, titanium lactate, and Octanediol titanate, titanium stearate and the like.

又，作為鋁系偶合劑，可舉出例如乙醯烷氧基二異丙醇鋁(acetoalkoxyaluminium diisopropylate)等。 Examples of the aluminum-based coupling agent include acetoalkoxyaluminium diisopropylate.

本發明之反應型接著劑中，多元醇組成物(A)與聚異氰酸酯組成物(B)的摻混比，藉由使多元醇組成物(A)所含之羥基的合計莫耳數[OH]、與聚異氰酸酯組成物(B)所含之異氰酸酯基的莫耳數[NCO]的比[NCO]/[OH]為0.5~30的範圍，而成為反應性優良的二液型接著劑。其中，[NCO]/[OH]較佳為0.8~20的範圍。 In the reactive adhesive of the present invention, the blend ratio of the polyol composition (A) and the polyisocyanate composition (B) is determined by the total mole number of the hydroxyl groups contained in the polyol composition (A) [OH ]. The ratio [NCO] / [OH] of the molar number [NCO] with the isocyanate group contained in the polyisocyanate composition (B) is in the range of 0.5 to 30, and it is a two-component adhesive with excellent reactivity. Among these, [NCO] / [OH] is preferably in the range of 0.8 to 20.

本發明之反應型接著劑可為溶劑型或無溶劑型之任一形態。此外，本發明中所稱「溶劑」，係指可溶解本發明所使用之前述多元醇組成物(A)或聚異氰酸酯組成物(B)之高溶解性的有機溶劑；所稱「無溶劑」，係指不含此等高溶解性的有機溶劑之形態，尤為不含乙酸乙酯或甲基乙基酮之形態。具體而言，可舉出例如乙酸乙酯、乙酸丁酯、乙酸賽路蘇等的酯類、丙酮、甲基乙基酮、異丁基酮、環己酮等的酮類、四氫呋喃、二 烷等的醚類、甲苯、二甲苯等的芳香族烴類、二氯甲烷、氯化乙烯等的鹵化烴類、二甲基亞碸、二甲基磺醯二胺等。此等當中，通常較佳為單獨或混合使用乙酸乙酯或甲基乙基酮。 The reactive adhesive of the present invention may be in either a solvent type or a solventless type. In addition, the "solvent" referred to in the present invention refers to a highly soluble organic solvent that can dissolve the aforementioned polyol composition (A) or polyisocyanate composition (B) used in the present invention; the so-called "solvent-free" , Refers to a form that does not contain such highly soluble organic solvents, especially a form that does not contain ethyl acetate or methyl ethyl ketone. Specific examples include esters such as ethyl acetate, butyl acetate, and celex acetate; ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone; tetrahydrofuran; Ethers such as alkane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane and ethylene chloride, dimethylsulfinium, dimethylsulfonium diamine, and the like. Among these, ethyl acetate or methyl ethyl ketone is usually preferably used alone or in combination.

為溶劑型時，溶劑亦有在前述多元醇組成物(A)或聚異氰酸酯組成物(B)的製造時作為反應介質使用，甚而於塗裝時作為稀釋劑使用的情況。 In the case of a solvent type, the solvent may be used as a reaction medium during the production of the polyol composition (A) or the polyisocyanate composition (B), or even as a diluent during painting.

本發明之反應型接著劑為溶劑型時，由於黏度可藉由溶劑稀釋而降低，因此，所用之前述多元醇組成物(A)或聚異氰酸酯組成物(B)即使黏度稍高亦可使用。另一方面，為無溶劑型時，在藉由加熱來降低黏度之特性上係重視為低黏度；作為降低黏度之手段，聚異氰酸酯組成物(B)通常使用將有助於黏度的芳香族濃度降低者。 When the reaction type adhesive of the present invention is a solvent type, since the viscosity can be reduced by dilution with a solvent, the aforementioned polyol composition (A) or polyisocyanate composition (B) can be used even if the viscosity is slightly high. On the other hand, in the case of a solvent-free type, low viscosity is emphasized on the characteristic of reducing viscosity by heating. As a means of reducing viscosity, the polyisocyanate composition (B) usually uses an aromatic concentration that contributes to viscosity. Reducer.

本發明之反應型接著劑亦可含有紫外線吸收劑、抗氧化劑、矽系添加劑、氟系添加劑、流變控制劑、脫泡劑、抗靜電劑、防霧劑、金屬減活劑、過氧化物分解劑、阻燃劑、防焰劑、補強劑、防鏽劑、螢光增白劑、無機系熱線吸收劑、脫水劑等的各種添加劑。 The reactive adhesive of the present invention may also contain an ultraviolet absorber, an antioxidant, a silicon-based additive, a fluorine-based additive, a rheology control agent, a defoaming agent, an antistatic agent, an anti-fogging agent, a metal deactivator, and a peroxide. Various additives such as decomposition agents, flame retardants, flame retardants, reinforcing agents, rust inhibitors, fluorescent whitening agents, inorganic hot-line absorbents, and dehydrating agents.

本發明之反應型接著劑可用於各式各樣物質之接著用途，作為接著對象，不僅是塑膠薄膜、金屬蒸鍍薄膜或者金屬箔，亦可適用作為紙、木材、塑膠成形品等各式各樣素材之基材的反應型接著劑。 The reactive adhesive of the present invention can be used for the bonding of various substances. As a bonding object, it is not only a plastic film, a metal vapor-deposited film, or a metal foil, but also can be applied to various kinds of paper, wood, and plastic molded products. Reactive adhesive for substrates of the same material.

上述各種成分，只要視接著用途或接著對象而適宜選擇即可。例如，本發明之反應型接著劑可適用作為後述之太陽能電池後罩板用接著劑。此時，藉由 併用環氧樹脂、聚碳酸酯多元醇化合物、增黏劑、環醯胺化合物，可使接著性、抗水解性更良好而較佳。 The above-mentioned various components may be appropriately selected depending on the application or object to be adhered. For example, the reactive-type adhesive of the present invention can be suitably used as an adhesive for a solar battery back cover sheet described later. At this time, by using an epoxy resin, a polycarbonate polyol compound, a tackifier, and a cyclic amine compound in combination, adhesion and hydrolysis resistance can be made better and more preferable.

(積層體) (Laminated body)

本發明之積層體係至少在第一基材與第二基材之間積層接著劑層而成的積層體，且為使用以上詳述之本發明之反應型接著劑作為該接著劑層而成的積層體。具體而言，作為將至少2個基材接著之接著劑，只要使用本發明之接著劑即可。積層體所具有的基材可為2個以上；此時，係例如如第一基材/接著層/第二基材/接著層/第三基材...般，接著層亦變得增加。於本發明中，只要將本發明之反應型接著劑使用於至少一接著層即可；又，亦可使用於全部的接著層，不特別限定。 The laminated system of the present invention is a laminated body formed by laminating an adhesive layer between at least a first substrate and a second substrate, and using the reactive adhesive of the present invention as the adhesive layer described in detail above. Laminated body. Specifically, as the adhesive for adhering at least two substrates, the adhesive of the present invention may be used. The laminated body may have two or more substrates; in this case, for example, the first substrate / adhesive layer / second substrate / adhesive layer / third substrate ... is similar, and the adhesive layer also increases. . In the present invention, the reactive adhesive of the present invention may be used in at least one adhesive layer; it may also be used in all the adhesive layers, and is not particularly limited.

前述積層體係至少塗布於第一基材，接著對塗布面積層第二基材，並使該接著劑層硬化而得者。 The laminated system is obtained by coating at least the first substrate, then coating the second substrate on the coating area, and curing the adhesive layer.

具體而言，可舉出將本發明之反應型接著劑，以例如輥塗機塗敷方式塗布於第一基材，隨後，若為溶劑型則經過乾燥步驟、若為無溶劑型則不經過乾燥步驟，而貼合其他基材之方法。塗敷條件於一般的輥塗機，較佳為在加熱至25℃~120℃左右的狀態下為500~2500mPa‧s左右。又，塗布量較佳為0.5~50g/m2，更佳宜以1.5~20g/m2左右來使用。 Specifically, the reactive adhesive of the present invention can be applied to a first substrate by, for example, a roll coater coating method, and then, if it is a solvent type, it undergoes a drying step, and if it is a solventless type, it does not. A method of drying and bonding other substrates. The coating conditions are in a general roll coater, and it is preferably about 500 to 2500 mPa · s when heated to about 25 ° C to 120 ° C. The coating amount is preferably from 0.5 to 50 g / m 2 , and more preferably from about 1.5 to 20 g / m 2 .

使用本發明之反應型接著劑時，層合後，在常溫或加熱下，以6~168小時使接著劑硬化，而展現實用物性。 When the reactive adhesive of the present invention is used, after lamination, the adhesive is hardened at room temperature or under heating for 6 to 168 hours, thereby exhibiting practical physical properties.

通常，接著劑硬化溫度，一般係以15~60度的範圍進行。 Usually, the curing temperature of the adhesive is generally in a range of 15 to 60 degrees.

作為前述基材，可舉出例如廣泛使用作為食品用途的聚對苯二甲酸乙二酯(PET)薄膜、聚苯乙烯薄膜、聚醯胺薄膜、聚丙烯腈薄膜、聚乙烯薄膜(LLDPE：低密度聚乙烯薄膜、HDPE：高密度聚乙烯薄膜)或聚丙烯薄膜(CPP：無延伸聚丙烯薄膜、OPP：雙軸延伸聚丙烯薄膜)等的聚烯烴薄膜、聚乙烯醇薄膜、乙烯-乙烯醇共聚物薄膜等。此等可施加延伸處理。作為延伸處理方法，一般係以擠出成膜法等將樹脂熔融擠出而作成片狀後，進行同時雙軸延伸或者逐次雙軸延伸。又，為逐次雙軸延伸時，一般係首先進行縱延伸處理，其次進行橫延伸。具體而言，大多採用將利用輥間之速度差的縱延伸與使用拉幅機之橫延伸加以組合的方法。再者，亦可使用對此等積層用之薄膜積層鋁、不鏽鋼等金屬、或者氧化矽或氧化鋁等金屬氧化物之蒸鍍層而成的薄膜。 Examples of the substrate include polyethylene terephthalate (PET) film, polystyrene film, polyamide film, polyacrylonitrile film, and polyethylene film (LLDPE: low Polyolefin films such as high density polyethylene film, HDPE: high density polyethylene film) or polypropylene film (CPP: unstretched polypropylene film, OPP: biaxially stretched polypropylene film), polyvinyl alcohol film, ethylene-vinyl alcohol Copolymer film and so on. These may be extended. As a stretching treatment method, generally, a resin is melt-extruded into a sheet shape by an extrusion film forming method or the like, and then simultaneous biaxial stretching or sequential biaxial stretching is performed. In the case of sequential biaxial stretching, the longitudinal stretching process is generally performed first, and the transverse stretching is performed second. Specifically, a method of combining a longitudinal extension using a speed difference between rolls and a transverse extension using a tenter is often adopted. In addition, a thin film for such lamination can be used, which is formed by laminating a metal such as aluminum or stainless steel, or a vapor-deposited layer of a metal oxide such as silicon oxide or aluminum oxide.

又，亦可舉出廣泛使用作為產業用途之包含聚碳酸酯、聚對苯二甲酸乙二酯、聚甲基丙烯酸甲酯、聚苯乙烯、聚酯、聚烯烴、環氧樹脂、三聚氰胺樹脂、三乙醯基纖維素樹脂、聚乙烯醇、ABS樹脂、降莰烯系樹脂、環烯烴系樹脂、聚醯亞胺樹脂、聚氟乙烯樹脂、聚偏二氟乙烯樹脂、乙烯-乙酸乙烯酯共聚物等的薄膜。 In addition, polycarbonates, polyethylene terephthalate, polymethyl methacrylate, polystyrene, polyester, polyolefins, epoxy resins, melamine resins, and the like, which are widely used as industrial applications, can also be cited. Triethyl cellulose resin, polyvinyl alcohol, ABS resin, norbornene-based resin, cycloolefin-based resin, polyimide resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, ethylene-vinyl acetate copolymerization Thin film.

又，除了薄膜以外，亦可使用紙、紙板、塗料紙、木材、皮革等的多孔質基材；此時，為了使接著劑滲透至基材中，需增加接著劑的塗布量。 In addition to a film, a porous substrate such as paper, cardboard, coated paper, wood, leather, or the like may be used. In this case, in order to penetrate the adhesive into the substrate, the application amount of the adhesive needs to be increased.

如此所得之積層體可適用作為各式各樣的用途，例如食品或醫藥品、生活用品之包裝材料、或防壁材、屋頂材、太陽能電池面板材、電池用包裝材料、窗材、屋外地板材料、照明保護材料、汽車構件、招牌、貼紙等屋外產業用途、使用於射出成形同時裝飾方法等之裝飾用片、清洗用液態清潔劑、廚房用液態清潔劑、浴用液態清潔劑、浴用液態皂、液態洗髮精、液態護髮素等包裝材料等。 The laminated body obtained in this way can be used for a variety of purposes, such as food or pharmaceutical products, packaging materials for daily necessities, or wall materials, roof materials, solar cell surface materials, battery packaging materials, window materials, and outdoor floor materials. , Lighting protection materials, automotive components, signboards, stickers and other outdoor industrial applications, decorative sheets used for injection molding and decorative methods, liquid cleaners for cleaning, liquid cleaners for kitchens, liquid cleaners for baths, liquid soaps for baths, Packaging materials such as liquid shampoo and liquid conditioner.

(太陽能電池後罩板) (Solar battery back cover)

本發明之反應型接著劑可如上述適用作為太陽能電池後罩板接著劑，其係用於製造為太陽能電池之一構件的太陽能電池後罩板。太陽能電池一般係成為：在作為受光面側透明保護構件的玻璃基板與背面側保護構件(後罩板)之間，以EVA(乙烯-乙酸乙烯酯共聚物)薄膜封裝矽發電元件等的太陽能電池單元而成之構成。此等構成材料係依受光側透明保護構件、配置於表面側的片狀封裝樹脂、太陽能電池用單元、配置於背面側的片狀封裝樹脂、及後罩板之順序積層，使其加熱真空層合而成為太陽能電池模組。 The reactive adhesive of the present invention can be applied as a solar cell back cover plate adhesive as described above, and is used for manufacturing a solar cell back cover plate as a component of a solar cell. A solar cell is generally a solar cell in which a silicon power generating element is encapsulated with an EVA (ethylene-vinyl acetate copolymer) film between a glass substrate as a transparent protective member on the light receiving surface side and a protective member on the rear side (rear cover plate). It is made up of units. These constituent materials are laminated in the order of a light-receiving transparent protective member, a sheet-like encapsulating resin disposed on the front side, a solar cell unit, a sheet-like encapsulating resin disposed on the back side, and a back cover plate in order to heat the vacuum layer. Combined into a solar cell module.

後罩板係要求機械強度、耐候性、耐熱性、耐濕熱性、耐光性等特性，而經常使用將氟系樹脂薄膜與金屬箔或聚丙烯薄膜、聚對苯二甲酸乙二酯薄膜(下稱PET薄膜)等廣用塑膠薄膜以接著劑貼合而成的積層體。此時所使用的接著劑係要求對此等各種薄膜之高接 著性、用來在露天環境下亦長期維持接著性之耐濕熱性、積層體之優良的外觀等。 The rear cover plate requires mechanical strength, weather resistance, heat resistance, heat and humidity resistance, light resistance and other characteristics. Often, fluorine resin film and metal foil or polypropylene film, polyethylene terephthalate film (under It is a laminated body made of widely used plastic films such as PET films and adhesives. Adhesives used at this time are required to have high adhesion to these various films, moist heat resistance to maintain adhesion for a long time even in an open-air environment, and excellent appearance of a laminate.

本發明之太陽能電池後罩板為上述本發明之積層體之一例，包含第一基材、第二基材、及配置於第一基材與第二基材之間且用來貼合第一基材與第二基材的接著層。此接著層為上述本發明之接著劑之硬化物(反應生成物)。亦可進一步包含其他基材。當本發明之太陽能電池後罩板除了第一基材、第二基材外亦進一步包含其他基材時，第一基材或第二基材與其他基材可使用本發明之接著劑貼合，也可不是如此。 The solar cell back cover of the present invention is an example of the laminated body of the present invention, and includes a first substrate, a second substrate, and a first substrate and a second substrate disposed between the first substrate and the second substrate and used to adhere to the first substrate. An adhesive layer between the substrate and the second substrate. This adhesive layer is a cured product (reaction product) of the adhesive of the present invention described above. It may further include other substrates. When the solar cell back cover of the present invention further includes other substrates in addition to the first substrate and the second substrate, the first substrate or the second substrate and other substrates may be bonded using the adhesive of the present invention. Or not.

作為第一基材、第二基材、其他基材，可使用例如紙、由烯烴系樹脂、丙烯腈-丁二烯-苯乙烯共聚物(ABS樹脂)、聚氯乙烯系樹脂、氟系樹脂、聚(甲基)丙烯酸系樹脂、碳酸酯系樹脂、聚醯胺系樹脂、聚醯亞胺系樹脂、聚苯醚系樹脂、聚苯硫醚系樹脂或聚酯系樹脂所得之合成樹脂薄膜、如銅箔、鋁箔之金屬箔等。 As the first substrate, the second substrate, and other substrates, for example, paper, olefin resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyvinyl chloride resin, and fluorine resin can be used. , Synthetic resin film obtained from poly (meth) acrylic resin, carbonate resin, polyamine resin, polyimide resin, polyphenylene ether resin, polyphenylene sulfide resin or polyester resin , Such as copper foil, metal foil, etc.

較佳為：第一基材與第二基材的其中一者為聚氟乙烯、聚偏二氟乙烯、聚四氟乙烯、聚氯三氟乙烯、四氟乙烯‧六氟丙烯共聚物、乙烯‧四氟乙烯共聚物等的氟系樹脂薄膜，且另一者為金屬箔或PET薄膜。為了提升基材與硬化塗膜的密接性，亦可對基材之形成硬化塗膜之一側的面進行表面處理。作為此表面處理，可舉出例如電暈處理、電漿處理、臭氧處理、火焰處理、放射線處理等。 Preferably, one of the first substrate and the second substrate is polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, polychlorotrifluoroethylene, tetrafluoroethylene hexafluoropropylene copolymer, ethylene ‧ Fluorine resin film such as tetrafluoroethylene copolymer, and the other is metal foil or PET film. In order to improve the adhesion between the substrate and the cured coating film, the surface on one side of the substrate on which the cured coating film is formed may be surface-treated. Examples of the surface treatment include corona treatment, plasma treatment, ozone treatment, flame treatment, and radiation treatment.

本發明之太陽能電池後罩板係對第一基材與第二基材的其中一者塗布本發明之接著劑，接著積層另一者，並使接著劑硬化而得。當接著劑為溶劑型時，係塗布接著劑後，經過乾燥步驟再積層另一基材。為無溶劑型時不需設置乾燥步驟。 The solar cell back cover sheet of the present invention is obtained by coating one of the first substrate and the second substrate with the adhesive of the present invention, then laminating the other, and curing the adhesive. When the adhesive is a solvent type, after the adhesive is applied, another substrate is laminated through a drying step. In the case of a solvent-free type, no drying step is required.

作為塗敷方法，可採用凹版塗布機方式、微凹版塗布機方式、反向塗布機(reverse coater)方式、棒塗布機方式、輥塗機方式、模塗布機方式等。 As a coating method, a gravure coater method, a micro gravure coater method, a reverse coater method, a bar coater method, a roll coater method, a die coater method, and the like can be adopted.

進行塗敷時，係將接著劑的黏度調整成適於塗敷的黏度。例如，使用輥塗機進行塗布時，在加熱至25℃~120℃左右的狀態下，接著劑的黏度較佳為500~2500mPa‧s左右。接著劑的塗布量較佳為5~15g/m2，更佳為5~10g/m2。 When applying, the viscosity of the adhesive is adjusted to a viscosity suitable for application. For example, when coating is performed using a roll coater, the viscosity of the adhesive is preferably about 500 to 2500 mPa · s when heated to about 25 ° C to 120 ° C. The coating amount of the adhesive is preferably 5 to 15 g / m 2 , and more preferably 5 to 10 g / m 2 .

較佳於積層後設置老化步驟。以15~60℃、6~168小時左右使接著劑硬化，而展現實用物性。 It is preferable to provide an aging step after lamination. The adhesive is hardened at 15 to 60 ° C. for about 6 to 168 hours to exhibit practical physical properties.

為了提升後罩板與後述之封裝樹脂的接著性，亦可在太陽能電池後罩板之與封裝樹脂相接的面易接著劑塗敷、硬化而成的易接著層。或者，為了提升後罩板的耐候性，亦可在露出至外部的面設置將保護用之塗覆劑塗敷、硬化而成的塗覆層。 In order to improve the adhesion between the rear cover plate and the encapsulation resin described later, an easy-adhesion layer formed by applying and curing an adhesive on the surface of the solar cell rear cover plate that is in contact with the encapsulation resin may be used. Alternatively, in order to improve the weather resistance of the rear cover plate, a coating layer formed by applying and curing a coating agent for protection may be provided on the surface exposed to the outside.

(太陽能電池模組) (Solar battery module)

本發明之太陽能電池模組包含：透明保護構件、太陽能電池用單元、被覆太陽能電池用單元整面的封裝樹脂、及後罩板。 The solar cell module of the present invention includes a transparent protective member, a solar cell unit, a packaging resin covering the entire surface of the solar cell unit, and a rear cover plate.

太陽能電池用單元係例如作成積體型太陽能電池元件，此元件係在基板上積層透明電極層、光半導體層及背面電極層，藉由分隔槽加以分隔，以形成複數個光電轉換單元，並將此等光電轉換單元電性串聯而成者。作為光半導體層中的光電轉換層，可使用矽或薄膜多晶矽等。再者，其係變得可由太陽能電池用單元向模組外部進行電輸出。 The unit for a solar cell is, for example, a built-in type solar cell element. This element is formed by stacking a transparent electrode layer, an optical semiconductor layer, and a back electrode layer on a substrate, and is separated by a separation groove to form a plurality of photoelectric conversion units. The photoelectric conversion units are electrically connected in series. As the photoelectric conversion layer in the optical semiconductor layer, silicon or thin-film polycrystalline silicon can be used. Furthermore, it becomes possible for the solar cell unit to output electric power to the outside of the module.

就作為封裝樹脂使用的樹脂而言，可使用EVA、PVB(聚乙烯縮丁醛)、PIB(聚異丁烯)、烯烴系樹脂(尤為接枝改質聚乙烯樹脂)、離子聚合物樹脂、矽樹脂等，較佳使用EVA。就EVA而言，其乙酸乙烯酯含量為10~40質量%，由確保太陽能電池模組的耐熱性、物理強度之觀點來看，較佳為藉由熱或者光等將EVA交聯而成者。 As the resin used as the sealing resin, EVA, PVB (polyvinyl butyral), PIB (polyisobutylene), olefin resin (especially graft-modified polyethylene resin), ionic polymer resin, and silicone resin can be used. Etc., preferably EVA is used. In terms of EVA, its vinyl acetate content is 10 to 40% by mass. From the viewpoint of ensuring heat resistance and physical strength of the solar cell module, it is preferable to crosslink EVA with heat or light. .

進行EVA的熱交聯時通常係使用有機過氧化物，且係使用在70℃以上的溫度下分解而產生自由基者。通常係使用半衰期10小時的分解溫度為50℃以上者，可使用2,5-二氫過氧化-2,5-二甲基己烷(2,5-dimethylhexane-2,5-dihydroperoxide)、2,5-二甲基-2,5-二(三級丁基過氧)己烷-3、過氧化二(三級丁基)、三級丁基過氧化異丙苯(tert-butyl cumyl peroxide)、2,5-二甲基-2,5-二(三級丁基過氧)己烷、過氧化二異丙苯、α,α’-雙(三級丁基過氧異丙基)苯、正丁基-4,4-雙(三級丁基過氧)戊酸酯、三級丁基過氧苯甲酸酯、過氧化苯甲醯等。 In the case of thermal crosslinking of EVA, organic peroxides are usually used, and those which decompose at a temperature of 70 ° C. or higher generate free radicals. Usually, the decomposition temperature is 50 ℃ or higher with a half-life of 10 hours, and 2,5-dihydroperoxide-2,5-dihydroperoxide, 2 , 5-dimethyl-2,5-di (tertiary butyl peroxy) hexane-3, bis (tertiary butyl), tert-butyl cumyl peroxide ), 2,5-dimethyl-2,5-di (tertiary butyl peroxy) hexane, dicumene peroxide, α, α'-bis (tertiary butyl peroxyisopropyl) Benzene, n-butyl-4,4-bis (tertiary butyl peroxy) valerate, tertiary butyl peroxybenzoate, benzoyl peroxide, and the like.

進行光硬化時係使用光敏劑，可使用為奪氫型(二分子反應型)之二苯甲酮、鄰苯甲醯基苯甲酸甲酯、4-苯甲醯基-4'-甲基二苯基硫醚、異丙基氧硫等；作為內部裂解型起始劑，可使用苯偶姻醚、苯甲基二甲基縮酮等；作為α-羥基烷基苯酮(α-hydroxyalkylphenone)型，可使用2-羥基-2-甲基-1-苯基丙烷-1-酮、1-羥基環己基苯基酮、烷基苯基乙醛酸酯(alkyl phenyl glyoxylate)、二乙氧基苯乙酮等。再者，作為α-胺基烷基苯酮型，亦可使用2-甲基-1-[4(甲硫基)苯基]-2-啉基丙烷-1、2-苯甲基-2-二甲胺基-1-(4-啉基苯基)-丁酮-1等、或醯基膦氧化物等。 A photosensitizer is used for photocuring, and benzophenone, methyl benzophenylidene benzoate, 4-benzylidene-4'-methyldiamine, which is a hydrogen abstraction type (bimolecular reaction type), can be used. Phenyl sulfide, isopropyloxysulfur Etc .; as internal cleavage initiator, benzoin ether, benzyl dimethyl ketal, etc .; as α-hydroxyalkylphenone (α-hydroxyalkylphenone) type, 2-hydroxy-2- Methyl-1-phenylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, alkyl phenyl glyoxylate, diethoxyacetophenone, and the like. Furthermore, as the α-aminoalkyl phenone type, 2-methyl-1- [4 (methylthio) phenyl] -2- Phenylpropane-1, 2-benzyl-2-dimethylamino-1- (4- Phenylphenyl) -butanone-1 and the like, or fluorenylphosphine oxide and the like.

又，考量與構成太陽能電池模組之玻璃板的接著，亦摻混矽烷偶合劑，係摻混乙烯基三乙氧基矽烷、乙烯基參(β-甲氧乙氧基)矽烷、γ-甲基丙醯氧丙基三甲氧基矽烷、乙烯基三乙醯氧基矽烷、γ-環氧丙氧丙基三甲氧基矽烷、γ-環氧丙氧丙基三乙氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-氯丙基甲氧基矽烷、乙烯基三氯矽烷、γ-巰丙基三甲氧基矽烷、γ-胺丙基三乙氧基矽烷、N-β(胺乙基)-γ-胺丙基三甲氧基矽烷等。 In addition, considering the adhesion to the glass plate constituting the solar cell module, a silane coupling agent is also blended, which is blended with vinyltriethoxysilane, vinyl ginseng (β-methoxyethoxy) silane, and γ-formaldehyde. Propoxypropyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-chloropropylmethoxysilane, vinyltrichlorosilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxy Silyl, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane and the like.

再者，以促進接著性及硬化為目的，有時也摻混含環氧基之化合物；作為含環氧基之化合物，也有摻混三環氧丙基參(2-羥乙基)三聚異氰酸酯、新戊二醇二環氧丙基醚、1,6-己二醇二環氧丙基醚、丙烯醯基環氧丙基醚、2-乙基己基環氧丙基醚、苯基環氧丙基醚、酚環氧丙基醚、對三級丁基苯基環氧丙基醚、己二酸二 環氧丙酯、鄰苯二甲酸二環氧丙酯、甲基丙烯酸環氧丙酯、丁基環氧丙基醚等的化合物、或含有環氧基之分子量為數百至數千的寡聚物或重量平均分子量為數千至數十萬的聚合物的情況。 Furthermore, for the purpose of promoting adhesion and hardening, an epoxy group-containing compound is sometimes blended; as the epoxy group-containing compound, triglycidyl (2-hydroxyethyl) trimer is also blended. Isocyanate, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, acrylfluorenyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl ring Oxypropyl ether, phenol-glycidyl ether, p-tert-butylphenyl-glycidyl ether, diglycidyl adipate, diglycidyl phthalate, glycidyl methacrylate In the case of compounds such as esters, butylglycidyl ether, or oligomers having an epoxy group molecular weight of hundreds to thousands or polymers having a weight average molecular weight of thousands to hundreds of thousands.

以提升封裝樹脂的交聯、接著性、機械強度、耐熱性、耐濕熱性、耐候性等為目的，而添加含有丙烯醯氧基、甲基丙烯醯氧基或烯丙基之化合物，最一般的為(甲基)丙烯酸衍生物，例如其烷基酯或醯胺。此時，作為烷基，除了如甲基、乙基、十二基、硬脂基、月桂基等烷基外，亦可舉出環己基、四氫糠基、胺乙基、2-羥乙基、3-羥丙基、3-氯-2-羥丙基等。又，(甲基)丙烯酸與乙二醇、三乙二醇、聚乙二醇、甘油、三羥甲基丙烷、新戊四醇等多官能醇之酯亦可同樣地使用。作為醯胺，其代表例為丙烯醯胺。又，作為含有烯丙基之化合物，係摻混三聚氰酸三烯丙酯、三聚異氰酸三烯丙酯、鄰苯二甲酸二烯丙酯、間苯二甲酸二烯丙酯、順丁烯二酸二烯丙酯等。 For the purpose of improving the cross-linking, adhesion, mechanical strength, heat resistance, heat and humidity resistance, and weather resistance of encapsulating resins, it is most common to add compounds containing acryloxy, methacryl, or allyl. Is a (meth) acrylic acid derivative, such as its alkyl ester or amidine. In this case, as the alkyl group, in addition to alkyl groups such as methyl, ethyl, dodecyl, stearyl, and lauryl, cyclohexyl, tetrahydrofurfuryl, amine ethyl, and 2-hydroxyethyl are also mentioned. Group, 3-hydroxypropyl, 3-chloro-2-hydroxypropyl and the like. Further, esters of (meth) acrylic acid and polyfunctional alcohols such as ethylene glycol, triethylene glycol, polyethylene glycol, glycerol, trimethylolpropane, and neopentyl tetraol can be used in the same manner. A typical example of amidine is acrylamide. Also, as the allyl-containing compound, triallyl tricyanate, triallyl isocyanate, diallyl phthalate, diallyl isophthalate, Diallyl maleate and the like.

再者，亦可摻混各種用來賦予阻燃性的無機化合物、或用來賦予耐候性的紫外線吸收劑、用來防止氧化劣化的抗氧化劑。亦即，構成太陽能電池模組的EVA係為了滿足作為太陽能電池模組所要求之機能，而摻混各種添加劑而成的樹脂組成物。 Furthermore, various inorganic compounds for imparting flame retardancy, ultraviolet absorbers for imparting weather resistance, and antioxidants for preventing oxidative degradation may be blended. That is, the EVA constituting the solar cell module is a resin composition obtained by mixing various additives in order to satisfy the functions required for the solar cell module.

作成太陽能電池模組而一體化之方法，作為其一例，可舉出真空層合方式。此方法係例如在加熱至100~150℃的真空層合裝置之加熱板上的仿真玻璃 (dummy glass)或金屬板上，依透明保護構件、透明保護構件側封裝樹脂、施有配線之太陽能電池用單元、後罩板側封裝樹脂、及後罩板之順序積層並予以靜置。其後，關閉真空層合裝置，開始減壓，保持此減壓狀態3~10分鐘後，自供/排氣管導入空氣，藉由壓力差而使橡膠製隔膜抵接於上述太陽能電池後罩板來進行加壓。雖隨封裝樹脂的種類而異，惟藉由保持此狀態10~40分鐘而完成加熱真空層合步驟。 A method of integrating a solar cell module as an example includes a vacuum lamination method. This method is, for example, a dummy glass or a metal plate on a heating plate of a vacuum lamination device heated to 100 to 150 ° C, a transparent protective member, a transparent protective member-side encapsulating resin, and a solar cell provided with wiring. The unit, the rear cover plate-side packaging resin, and the rear cover plate were laminated in this order and left to stand. After that, the vacuum lamination device was closed, and the pressure was reduced. After maintaining the reduced pressure for 3 to 10 minutes, air was introduced from the supply / exhaust pipe, and the rubber diaphragm was abutted against the solar battery back cover plate by the pressure difference. To pressurize. Although it varies depending on the type of the encapsulating resin, the heating and vacuum lamination step is completed by maintaining the state for 10 to 40 minutes.

此外，真空層合方式僅為一例，可應用周知之層合方式。 In addition, the vacuum lamination method is only an example, and a well-known lamination method can be applied.

藉由使用本發明之後罩板，可提升太陽能電池模組的耐久性。 By using the rear cover plate of the present invention, the durability of the solar cell module can be improved.

[實施例]     [Example]    

以下，舉出具體的合成例、實施例而更詳細地說明本發明，惟本發明不受此等實施例所限定。此外，以下各例中，「份」及「%」除非特別指明，係分別表示「質量份」及「質量%」。 Hereinafter, the present invention will be described in more detail by giving specific synthesis examples and examples, but the present invention is not limited to these examples. In addition, in the following examples, "parts" and "%" refer to "mass parts" and "mass%" respectively, unless otherwise specified.

(分子量測定方法) (Molecular weight measurement method)

此外，於本案發明中，數量平均分子量(Mn)及重量平均分子量(Mw)係藉由下述條件之凝膠滲透層析法(GPC)來測定。 In the present invention, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are measured by gel permeation chromatography (GPC) under the following conditions.

測定裝置：TOSOH股份有限公司製HLC-8320GPC Measuring device: HLC-8320GPC manufactured by TOSOH Co., Ltd.

管柱：TOSOH股份有限公司製TSKgel 4000HXL、TSKgel 3000HXL、TSKgel 2000HXL、TSKgel 1000HXL 檢測器：RI(示差折射計) Column: TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL manufactured by TOSOH Co., Ltd. Detectors: RI (differential refractometer)

數據處理：TOSOH股份有限公司製Multi-Station GPC-8020modelII Data processing: Multi-Station GPC-8020modelII made by TOSOH Co., Ltd.

標準：單分散聚苯乙烯 Standard: Monodisperse Polystyrene

試料：以樹脂固體成分換算為0.2質量%的四氫呋喃溶液經微過濾器過濾者(100μl) Sample: 0.2 mass% tetrahydrofuran solution converted by the solid content of the resin and filtered through a micro filter (100 μl)

(酸值測定方法) (Acid value measurement method)

此外，於本實施例中，酸值係以下述方法測定。 In this example, the acid value was measured by the following method.

精秤試料5.0g，添加四氫呋喃30mL使其溶解，使用0.1N氫氧化鉀溶液(醇性)進行滴定。指示劑係使用酚酞。測定結果係換算成為了中和1g的試料所需之氫氧化鉀的量，單位設為mgKOH/g。此外，當試料含有有機溶劑時，係將藉由上述測定方法直接測定的酸值，使用溶液的不揮發分值換算成固體成分酸值。 5.0 g of a fine scale sample was added, 30 mL of tetrahydrofuran was added to dissolve it, and titration was performed using a 0.1N potassium hydroxide solution (alcoholic). As the indicator, phenolphthalein was used. The measurement result was converted into the amount of potassium hydroxide required to neutralize 1 g of the sample, and the unit was mgKOH / g. In addition, when the sample contains an organic solvent, the acid value directly measured by the above-mentioned measurement method is converted into a solid content acid value using the nonvolatile content value of the solution.

(羥值測定方法) (Hydroxy value measurement method)

此外，於本實施例中，羥值係以下述方法測定。 In this example, the hydroxyl value was measured by the following method.

精秤試料4.0g，添加包含乙酸酐/吡啶(容量比1/19)的乙醯化劑25mL，予以密閉而以100℃加熱1小時。乙醯化後，添加離子交換水10mL與四氫呋喃100mL，使用0.5N氫氧化鉀溶液(醇性)進行滴定。指示劑係使用酚 酞。測定結果係換算成為了中和使1g的試料乙醯化時所生成的乙酸所需之氫氧化鉀的量，單位設為mgKOH/g。此外，當試料含有有機溶劑時，係將藉由上述測定方法直接測定的羥值，使用溶液的不揮發分值換算成固體成分羥值。 4.0 g of a fine-scale sample was added, and 25 mL of an acetating agent containing acetic anhydride / pyridine (capacity ratio 1/19) was added, sealed, and heated at 100 ° C. for 1 hour. After acetylation, 10 mL of ion-exchanged water and 100 mL of tetrahydrofuran were added, and titration was performed using a 0.5N potassium hydroxide solution (alcoholic). As the indicator, phenolphthalein was used. The measurement result was converted to the amount of potassium hydroxide required to neutralize the acetic acid produced when 1 g of the sample was acetylated, and the unit was mgKOH / g. In addition, when the sample contains an organic solvent, the hydroxyl value directly measured by the above-mentioned measurement method is converted into the hydroxyl value of the solid content using the nonvolatile value of the solution.

(玻璃轉移溫度測定法) (Glass transition temperature measurement method)

將5mg的試料，使用DSC，在30mL/min的氮氣氣流下由室溫以10℃/min昇溫至200℃後，以10℃/min冷卻至-80℃，再度以10℃/min昇溫至150℃，測定DSC曲線。以在第二次昇溫步驟所觀測到的測定結果中，將低溫側的基線延長至高溫側所得的直線、與由玻璃轉移之階梯狀部分的曲線之梯度達最大的點所拉出的切線之交點作為玻璃轉移點，以此時的溫度作為玻璃轉移溫度。 5 mg of the sample was heated from room temperature to 10 ° C./min to 200 ° C. under a nitrogen gas flow of 30 mL / min using DSC, and then cooled to −80 ° C. at 10 ° C./min, and again heated to 150 ° C. at 10 ° C./min. ℃, DSC curve was measured. Based on the measurement results observed in the second heating step, the straight line obtained by extending the baseline on the low temperature side to the high temperature side, and the tangent line drawn at the point where the gradient of the curve of the stepped portion from the glass transition reaches the maximum The intersection point is the glass transition point, and the temperature at this time is the glass transition temperature.

(製造例1)聚酯多元醇(A-1)的合成 (Production Example 1) Synthesis of polyester polyol (A-1)

對具有攪拌棒、溫度感測器、精餾管的燒瓶裝入間苯二甲酸(MITSUBISHI GAS CHEMICAL股份有限公司製)790.8重量份、對苯二甲酸(三井化學股份有限公司製)339.4重量份、苯偏三甲酸酐(MITSUBISHI GAS CHEMICAL股份有限公司製)20.0重量份、1,6-己二醇(BASF公司製)738.0重量份、新戊二醇(MITSUBISHI GAS CHEMICAL股份有限公司製)107.4重量份及有機鈦化合物(Matsumoto Fine Chemical股份有限公司製「ORGATIX TC-100」)4.0重量份，一面攪拌一面使乾燥 氮氣流入燒瓶內，一面餾去生成的水一面昇溫至240℃。其後，一面提高真空度至30torr一面進行酯化反應，在樹脂酸值成為1.50mgKOH/g以下的時間點使反應中止。將所得的聚酯多元醇以乙酸乙酯稀釋成樹脂固體成分58%，而得到數量平均分子量(Mn)為7,000、重量平均分子量(Mw)為23,500、樹脂羥值(固體成分換算)為22.4mgKOH/g、樹脂酸值(固體成分換算)為1.26mgKOH/g、玻璃轉移溫度(Tg)為2.1℃的聚酯多元醇(A-1)。 A flask having a stir bar, a temperature sensor, and a rectification tube was charged with 790.8 parts by weight of isophthalic acid (manufactured by MITSUBISHI GAS Chemical Co., Ltd.), 339.4 parts by weight of terephthalic acid (manufactured by Mitsui Chemicals Co., Ltd.), and benzene. 20.0 parts by weight of trimellitic anhydride (manufactured by MITSUBISHI GAS CHEMICAL Co., Ltd.), 738.0 parts by weight of 1,6-hexanediol (manufactured by BASF), 107.4 parts by weight of neopentyl glycol (manufactured by MITSUBISHI GAS CHEMICAL Co., Ltd.) and organic 4.0 parts by weight of a titanium compound ("ORGATIX TC-100" manufactured by Matsumoto Fine Chemical Co., Ltd.) was heated to 240 ° C while the dry nitrogen flowed into the flask while being stirred, and the generated water was distilled off. After that, the esterification reaction was performed while increasing the vacuum degree to 30 torr, and the reaction was stopped when the resin acid value became 1.50 mgKOH / g or less. The obtained polyester polyol was diluted with ethyl acetate to a resin solid content of 58% to obtain a number average molecular weight (Mn) of 7,000, a weight average molecular weight (Mw) of 23,500, and a resin hydroxyl value (solid content conversion) of 22.4 mgKOH. / g, polyester polyol (A-1) having a resin acid value (in terms of solid content) of 1.26 mgKOH / g and a glass transition temperature (Tg) of 2.1 ° C.

(製造例2)聚酯多元醇(A-2)的合成 (Production Example 2) Synthesis of polyester polyol (A-2)

對具有攪拌棒、溫度感測器、冷凝器的燒瓶裝入前述聚酯多元醇(A-1)75.9重量份、乙酸乙酯22.9重量份、六亞甲基二異氰酸酯(Sumika Covestro Urethane股份有限公司製「Desmodur H」)1.1重量份及有機錫化合物(日東化成股份有限公司製「NEOSTANN U-130」)0.01重量份，使乾燥氮氣流入燒瓶內，一面攪拌一面加熱至75~78℃而進行鏈伸長反應。在異氰酸酯重量%成為0.05%以下的時間點將反應中止，使用甲基乙基酮以成為樹脂固體成分35%的方式進行稀釋，而得到數量平均分子量(Mn)為14,500、重量平均分子量(Mw)為117,500、樹脂羥值(固體成分換算)為5.2mgKOH/g、樹脂酸值(固體成分換算)為1.75mgKOH/g、玻璃轉移溫度(Tg)為10.0℃的聚酯多元醇(A-2)。 A flask having a stir bar, a temperature sensor, and a condenser was charged with 75.9 parts by weight of the polyester polyol (A-1), 22.9 parts by weight of ethyl acetate, and hexamethylene diisocyanate (Sumika Covestro Urethane Co., Ltd. 1.1 parts by weight of "Desmodur H") and 0.01 parts by weight of organotin compounds ("NEOSTANN U-130" manufactured by Nitto Kasei Co., Ltd.). Dry nitrogen was flowed into the flask, and the chain was heated to 75-78 ° C while stirring. Elongation response. When the isocyanate weight% became 0.05% or less, the reaction was stopped, and methyl ethyl ketone was used to dilute it to 35% of the resin solid content to obtain a number average molecular weight (Mn) of 14,500 and a weight average molecular weight (Mw) of 117,500, polyester polyol (A-2) having a resin hydroxyl value (solid content conversion) of 5.2 mgKOH / g, a resin acid value (solid content conversion) of 1.75 mgKOH / g, and a glass transition temperature (Tg) of 10.0 ° C.

(製造例3)聚酯多元醇(A-3)的合成 (Production Example 3) Synthesis of polyester polyol (A-3)

對具有攪拌棒、溫度感測器、冷凝器的燒瓶裝入前述聚酯多元醇(A-1)75.4重量份、乙酸乙酯23.2重量份、異佛爾酮二異氰酸酯(Evonic公司製)1.4重量份及有機錫化合物0.01重量份，使乾燥氮氣流入燒瓶內，一面攪拌一面加熱至75~78℃而進行鏈伸長反應。在異氰酸酯重量%成為0.05%以下的時間點將反應中止，使用甲基乙基酮以成為樹脂固體成分35%的方式進行稀釋，而得到數量平均分子量(Mn)為13,900、重量平均分子量(Mw)為101,700、樹脂羥值(固體成分換算)為4.9mgKOH/g、樹脂酸值(固體成分換算)為1.57mgKOH/g、玻璃轉移溫度(Tg)為12.8℃的聚酯多元醇(A-3)。 A flask having a stir bar, a temperature sensor, and a condenser was charged with 75.4 parts by weight of the polyester polyol (A-1), 23.2 parts by weight of ethyl acetate, and 1.4 weight by isophorone diisocyanate (manufactured by Evonic Corporation). Parts and 0.01 parts by weight of an organotin compound, dry nitrogen was allowed to flow into the flask, and the mixture was heated to 75 to 78 ° C. while undergoing a chain extension reaction. When the isocyanate weight% became 0.05% or less, the reaction was stopped, and methyl ethyl ketone was used to dilute it to 35% of the resin solid content to obtain a number average molecular weight (Mn) of 13,900 and a weight average molecular weight (Mw) of 101,700, polyester polyol (A-3) having a resin hydroxyl value (solid content conversion) of 4.9 mgKOH / g, a resin acid value (solid content conversion) of 1.57 mgKOH / g, and a glass transition temperature (Tg) of 12.8 ° C.

(製造例4)聚酯多元醇(A-4)的合成 (Production Example 4) Synthesis of polyester polyol (A-4)

對具有攪拌棒、溫度感測器、冷凝器的燒瓶裝入前述聚酯多元醇(A-1)74.9重量份、乙酸乙酯23.4重量份、4,4-二苯基甲烷二異氰酸酯(TOSOH股份有限公司製「Lupranate MT」)1.7重量份及有機錫化合物0.01重量份，使乾燥氮氣流入燒瓶內，一面攪拌一面加熱至75~78℃而進行鏈伸長反應。在異氰酸酯重量%成為0.05%以下的時間點將反應中止，使用甲基乙基酮以成為樹脂固體成分35%的方式進行稀釋，而得到數量平均分子量(Mn)為12,000、重量平均分子量(Mw)為168,900、羥值(固體成分換算)為6.8mgKOH/g、酸值(固體成分換算)為1.34mgKOH/g、玻璃轉移溫度(Tg)為14.9℃的聚酯多元醇(A-4)。 A flask having a stir bar, a temperature sensor, and a condenser was charged with 74.9 parts by weight of the polyester polyol (A-1), 23.4 parts by weight of ethyl acetate, and 4,4-diphenylmethane diisocyanate (TOSOH Corporation). "Lupranate MT" (manufactured by Co., Ltd.), 1.7 parts by weight and 0.01 parts by weight of an organotin compound, dry nitrogen was allowed to flow into the flask, and heated to 75 to 78 ° C while stirring to perform a chain extension reaction. When the isocyanate weight% became 0.05% or less, the reaction was stopped, and methyl ethyl ketone was used to dilute it to 35% of the resin solid content to obtain a number average molecular weight (Mn) of 12,000 and a weight average molecular weight (Mw) of 168,900, a polyester polyol (A-4) having a hydroxyl value (solid content conversion) of 6.8 mgKOH / g, an acid value (solid content conversion) of 1.34 mgKOH / g, and a glass transition temperature (Tg) of 14.9 ° C.

(製造例5)聚酯多元醇(A-5)的合成 (Production Example 5) Synthesis of polyester polyol (A-5)

對具有攪拌棒、溫度感測器、冷凝器的燒瓶裝入前述聚酯多元醇(A-1)75.8重量份、乙酸乙酯23.0重量份、甲伸苯基二異氰酸酯(TOSOH股份有限公司製「COSMONATE T-80」)1.2重量份及有機錫化合物0.01重量份，使乾燥氮氣流入燒瓶內，一面攪拌一面加熱至75~78℃而進行鏈伸長反應。在異氰酸酯重量%成為0.05%以下的時間點將反應中止，使用甲基乙基酮以成為樹脂固體成分35%的方式進行稀釋，而得到數量平均分子量(Mn)為8,900、重量平均分子量(Mw)為120,000、羥值(固體成分換算)為6.8mgKOH/g、酸值(固體成分換算)為1.34mgKOH/g、玻璃轉移溫度(Tg)為15.4℃的聚酯多元醇(A-5)。 A flask having a stir bar, a temperature sensor, and a condenser was charged with 75.8 parts by weight of the polyester polyol (A-1), 23.0 parts by weight of ethyl acetate, and methylenephenyl diisocyanate (manufactured by TOSOH Corporation " COSMONATE T-80 ") 1.2 parts by weight and 0.01 parts by weight of an organotin compound. Dry nitrogen was allowed to flow into the flask and heated to 75 to 78 ° C while stirring to perform a chain extension reaction. When the isocyanate weight% became 0.05% or less, the reaction was stopped, and methyl ethyl ketone was used to dilute it to 35% of the resin solid content to obtain a number average molecular weight (Mn) of 8,900 and a weight average molecular weight (Mw) of Polyester polyol (A-5) having a hydroxyl value (solid content conversion) of 6.8 mgKOH / g, an acid value (solid content conversion) of 1.34 mgKOH / g, and a glass transition temperature (Tg) of 15.4 ° C.

(製造例6)聚酯多元醇(AH-1)的合成 (Production Example 6) Synthesis of polyester polyol (AH-1)

對具有攪拌棒、溫度感測器、精餾管的燒瓶裝入癸二酸310重量份、間苯二甲酸420重量份、鄰苯二甲酸酐212重量份、苯偏三甲酸酐11.1重量份、新戊二醇610重量份及有機鈦化合物0.7重量份，一面攪拌一面使乾燥氮氣流入燒瓶內，一面餾去生成的水一面昇溫至240℃。其後，一面提高真空度至30torr一面進行酯化反應，在酸值成為2.00mgKOH/g以下的時間點將反應中止，冷卻至150℃後，使用乙酸乙酯以成為樹脂固體成分62.0%的方式進行稀釋，而得到數量平均分子量(Mn)為 6,000、重量平均分子量(Mw)為17,000、樹脂羥值(固體成分換算)為14.6mgKOH/g、樹脂酸值(固體成分換算)為1.94mgKOH/g、玻璃轉移溫度(Tg)為6.0℃的聚酯多元醇(AH-1)。 A flask with a stir bar, a temperature sensor, and a rectification tube were charged with 310 parts by weight of sebacic acid, 420 parts by weight of isophthalic acid, 212 parts by weight of phthalic anhydride, 11.1 parts by weight of trimellitic anhydride, and 610 parts by weight of pentanediol and 0.7 parts by weight of the organic titanium compound were heated to 240 ° C. while the dry nitrogen was allowed to flow into the flask while being stirred, and the generated water was distilled off. Thereafter, the esterification reaction was performed while increasing the vacuum to 30 torr. The reaction was stopped at a time when the acid value became 2.00 mgKOH / g or less. After cooling to 150 ° C, ethyl acetate was used to make the resin solid content 62.0%. Diluted to obtain a number average molecular weight (Mn) of 6,000, a weight average molecular weight (Mw) of 17,000, a resin hydroxyl value (solid content conversion) of 14.6 mgKOH / g, a resin acid value (solid content conversion) of 1.94 mgKOH / g, Polyester polyol (AH-1) having a glass transition temperature (Tg) of 6.0 ° C.

(接著劑的配方1) (Adhesive Formulation 1)

依循表1~3所示配方，將多元醇組成物與聚異氰酸酯組成物一起混合來調製反應型接著劑。此外，表中的摻混量為固體成分質量份。 According to the formulas shown in Tables 1 to 3, the polyol composition and the polyisocyanate composition are mixed together to prepare a reactive adhesive. Moreover, the compounding quantity in a table | surface is a solid content mass part.

惟，表中的[NCO]/[OH]係表示聚異氰酸酯組成物所含之異氰酸酯基的莫耳數[NCO]、與前述多元醇組成物所含之羥基的莫耳數[OH]的比[NCO]/[OH]。 However, the [NCO] / [OH] in the table indicates the ratio of the molar number [NCO] of the isocyanate group contained in the polyisocyanate composition to the molar number [OH] of the hydroxyl group contained in the polyol composition [NCO] / [OH].

(評價方法1) (Evaluation method 1)

(評價1-1：層合外觀) (Evaluation 1-1: laminated appearance)

以125μm厚的PET薄膜(TORAY股份有限公司製「Lumirror X10S」)為基材，將上述之反應型接著劑塗裝成4~6g/m2(乾燥質量)，將作為貼合用薄膜之30μm厚的白色聚偏二氟乙烯薄膜(Arkema公司製「Kyner」)積層，而得到評價試樣。評價試樣係以40℃、72小時進行老化後，供予評價。 A 125 μm-thick PET film ("Lumirror X10S" manufactured by TORAY Co., Ltd.) is used as a substrate, and the above-mentioned reactive adhesive is coated to 4 to 6 g / m 2 (dry mass), and it will be used as a 30 μm film for bonding. A thick white polyvinylidene fluoride film ("Kyner" manufactured by Arkema) was laminated to obtain an evaluation sample. The evaluation sample was subjected to aging at 40 ° C for 72 hours and then subjected to evaluation.

對前述評價試樣，由白色聚偏二氟乙烯薄膜側目視評價層合外觀。 About the said evaluation sample, the laminated appearance was visually evaluated from the white polyvinylidene fluoride film side.

○：薄膜表面平滑 ○: Film surface is smooth

△：薄膜表面存在少許凹坑(凹陷) △: There are a few pits (dents) on the film surface

×：薄膜表面存在多數凹坑(凹陷) ×: Many pits (dents) exist on the film surface

(評價1-2：接著力) (Evaluation 1-2: Adherence)

以30μm厚的鋁箔(Toyo Aluminium股份有限公司製「1N30」)為基材，對鋁箔的無光澤面側，將上述之反應型接著劑塗裝成4~6g/m2(乾燥質量)，將作為貼合用薄膜之70μm厚的CPP薄膜(TORAY ADVANCED FILM股份有限公司製「ZK-93KM」)積層，而得到評價試樣。評價試樣係以40℃、72小時進行老化後，供予評價。 A 30 μm-thick aluminum foil ("1N30" manufactured by Toyo Aluminium Co., Ltd.) was used as a base material, and the above-mentioned reactive adhesive was applied to 4 to 6 g / m 2 (dry mass) on the matte side of the aluminum foil. A 70 μm-thick CPP film (“ZK-93KM” manufactured by TORAY ADVANCED FILM Co., Ltd.), which is a bonding film, was laminated to obtain an evaluation sample. The evaluation sample was subjected to aging at 40 ° C for 72 hours and then subjected to evaluation.

用前述評價試樣，以拉伸試驗機(島津製作所股份有限公司製「Auograph AGS-J」)評價剝離速度100mm/min下的強度(N/15mm、180°剝離)作為接著力。 Using the aforementioned evaluation sample, a tensile tester ("Auograph AGS-J" manufactured by Shimadzu Corporation) was used to evaluate the strength (N / 15 mm, 180 ° peeling) at a peeling speed of 100 mm / min as the adhesive force.

(評價1-3：成形加工性) (Evaluation 1-3: Formability)

以30μm厚的鋁箔(Toyo Aluminium股份有限公司製「1N30」)為基材，對鋁箔的無光澤面側，將上述之反應型接著劑塗裝成4~6g/m2(乾燥質量)，將作為貼合用薄膜之25μm厚的延伸聚醯胺薄膜(UNITIKA股份有限公司製「EMBLEM ONBC」積層。其次，對鋁箔的光澤面亦將反應型接著劑塗裝成4~6g/m2(乾燥質量)，同樣地積層延伸聚醯胺薄膜，而得到評價試樣。評價試樣係以40℃、72小時進行老化後，切成寬1.5cm×長23cm的長條狀而供予評價。 A 30 μm-thick aluminum foil ("1N30" manufactured by Toyo Aluminium Co., Ltd.) was used as a base material, and the above-mentioned reactive adhesive was applied to 4 to 6 g / m 2 (dry mass) on the matte side of the aluminum foil. A 25 μm-thick stretched polyimide film (“EMBLEM ONBC” manufactured by UNITIKA Co., Ltd.) as a laminating film. Next, the reactive surface of the aluminum foil was coated with 4 to 6 g / m 2 (dried). Mass), and similarly stretched the polyamide film to obtain an evaluation sample. The evaluation sample was aged at 40 ° C for 72 hours, and then cut into a strip shape having a width of 1.5 cm and a length of 23 cm for evaluation.

將前述評價試樣，以夾頭間距離成為10cm的方式保持於拉伸試驗機(A&D股份有限公司「Tensilon萬能試驗機RTG-1210」)，並以移動速度500mm/min拉伸至夾頭間距離成為12cm，而將評價試樣進行成形加工。 The aforementioned evaluation sample was held in a tensile tester (A & D Co., Ltd. "Tensilon Universal Tester RTG-1210") so that the distance between the chucks became 10 cm, and was stretched to the chuck at a moving speed of 500 mm / min The distance was 12 cm, and the evaluation sample was subjected to a forming process.

由經成形加工之評價試樣的聚醯胺薄膜側目視判定外觀。 The appearance was judged visually from the side of the polyurethane film of the evaluation sample subjected to the forming process.

○：薄膜表面平滑 ○: Film surface is smooth

△：薄膜表面存在斑點狀圖案、或者在評價試樣的端部產生微小龜裂 △: A spot-like pattern is present on the surface of the film, or a minute crack is generated at the end of the evaluation sample

×：聚醯胺薄膜剝離、或者評價試樣破裂 ×: The polyamide film was peeled off or the evaluation sample was cracked

(評價1-4：接著劑的抗水解性) (Evaluation 1-4: hydrolysis resistance of the adhesive)

以PTFE薄膜(日東電工股份有限公司製「NITOFLON Films No.900UL」)為基材，以施用器(applicator)塗裝上述之反應型接著劑。使溶劑揮發後，以40℃、72小時進行老化，而得到評價試樣。 The above-mentioned reactive adhesive was coated with a PTFE film ("NITOFLON Films No. 900UL" manufactured by Nitto Denko Corporation) as a base material and an applicator. After the solvent was evaporated, the sample was aged at 40 ° C. for 72 hours to obtain an evaluation sample.

將評價試樣在高度加速壽命試驗裝置(ESPEC股份有限公司製「EMS-221M」)中於121℃、100%RH保持48小時，來進行濕熱處理。 The evaluation sample was held in a highly accelerated life tester ("EMS-221M" manufactured by ESPEC Corporation) at 121 ° C and 100% RH for 48 hours to perform a wet heat treatment.

藉由下述所示方法，測定初始(老化後)及濕熱處理後之接著劑的凝膠分率，算出濕熱處理後之凝膠分率相對於初始之凝膠分率的保持率，來評價反應型接著劑的抗水解性。 The gel fraction of the adhesive after initial (after aging) and wet heat treatment was measured by the following method, and the retention rate of the gel fraction after wet heat treatment relative to the initial gel fraction was calculated and evaluated Hydrolytic resistance of reactive adhesives.

◎：保持率為80%以上(實用上特別優良) ◎: Retention rate is 80% or more (especially excellent in practical use)

○：保持率為50%以上~小於80%(實用上優良) ○: Retention rate is 50% or more and less than 80% (excellent in practical use)

△：保持率為20%以上~小於50%(實用範圍) △: Retention rate is 20% or more and less than 50% (practical range)

×：保持率為0%以上~小於20% ×: Retention rate is from 0% to less than 20%

前述反應型接著劑的凝膠分率係藉由以下所說明的測定方法來算出。 The gel fraction of the reactive adhesive is calculated by a measurement method described below.

由評價試樣採取約0.2g的接著劑層，置入多孔質之茶包中，而製作待測試樣。其次，測定待測試樣的質量而作為浸漬前質量。 About 0.2 g of an adhesive layer was taken from the evaluation sample and placed in a porous tea bag to prepare a test sample. Next, the mass of the sample to be tested is determined as the mass before immersion.

接著，將待測試樣置入裝滿甲基乙基酮的70ml容器中，於23℃保存24小時。其後，由容器中取出待測試樣，在120℃的乾燥機中乾燥1小時而去除甲基乙基酮。其次，測定去除甲基乙基酮之待測試樣的質量而作為浸漬後質量。 Next, the sample to be tested was placed in a 70 ml container filled with methyl ethyl ketone, and stored at 23 ° C. for 24 hours. Thereafter, the sample to be tested was taken out of the container, and dried in a dryer at 120 ° C. for 1 hour to remove methyl ethyl ketone. Next, the mass of the test sample from which methyl ethyl ketone was removed was measured as the mass after immersion.

其後，由下述式算出接著劑的凝膠分率。 Thereafter, the gel fraction of the adhesive was calculated from the following formula.

凝膠分率(質量%)=(A-B)/(C-B)×100 Gel fraction (% by mass) = (A-B) / (C-B) × 100

(上述式中，A為浸漬後質量，B為茶包的質量，C為浸漬前質量)。 (In the above formula, A is the mass after immersion, B is the mass of the tea bag, and C is the mass before immersion).

將結果示於表1~3。 The results are shown in Tables 1 to 3.

各表中的簡稱如下： The abbreviations in the tables are as follows:

聚異氰酸酯B-1：Sumika Covestro Urethane股份有限公司製「Sumidur N3300」 Polyisocyanate B-1: "Sumidur N3300" manufactured by Sumika Covestro Urethane Co., Ltd.

六亞甲基二異氰酸酯之三聚異氰酸酯體 Trimeric isocyanate body of hexamethylene diisocyanate

NCO基含有率21.8%，固體成分100質量% NCO group content rate 21.8%, solid content 100% by mass

聚異氰酸酯B-2：Sumika Covestro Urethane股份有限公司製「Desmodur L75」 Polyisocyanate B-2: "Desmodur L75" manufactured by Sumika Covestro Urethane Co., Ltd.

甲伸苯基二異氰酸酯之加合物，NCO基含有率13% Adduct of methylphenyl diisocyanate, 13% NCO group content

乙酸乙酯稀釋物，固體成分75質量% Ethyl acetate dilution, 75% by mass of solids

環氧樹脂A：DIC股份有限公司製「EPICLON 860-80SE」 Epoxy resin A: "EPICLON 860-80SE" manufactured by DIC Corporation

雙酚A型環氧樹脂 環氧當量250g/eq， Bisphenol A epoxy resin, epoxy equivalent 250g / eq,

乙酸乙酯稀釋物，固體成分80質量% Ethyl acetate dilution, solid content 80% by mass

其結果，顯然使用本發明之聚酯多元醇(A)的反應型接著劑係層合外觀、接著力、成形加工性、抗水解性均優良。 As a result, it is apparent that the reactive adhesive system using the polyester polyol (A) of the present invention is excellent in laminated appearance, adhesion, molding processability, and hydrolysis resistance.

(接著劑的配方2) (Adhesive Formulation 2)

使用上述合成之聚酯多元醇，如以下方式評價作為太陽能電池後罩板用接著劑之適性。 Using the synthesized polyester polyol, the suitability as an adhesive for a solar cell back cover was evaluated in the following manner.

(實施例2-1) (Example 2-1)

對100份的聚酯多元醇(A-1)添加7.6份之作為聚異氰酸酯(B-1)的脲酸酯型六亞甲基二異氰酸酯(Sumika Covestro Urethane公司製「Sumidur N3300」)，並以不揮發分成為35%的方式添加乙酸乙酯且充分攪拌，而製作太陽能電池後罩板用接著劑。 To 100 parts of the polyester polyol (A-1), 7.6 parts of a urethane-type hexamethylene diisocyanate ("Sumidur N3300" manufactured by Sumika Covestro Urethane Co., Ltd.) as a polyisocyanate (B-1) was added. Ethyl acetate was added so that the nonvolatile matter became 35%, and the mixture was sufficiently stirred to prepare an adhesive for a solar cell back cover.

(實施例2-2)~(實施例2-4) (Example 2-2) ~ (Example 2-4)

以表4所記載之配方，與實施例2-1同樣地進行，製作太陽能電池後罩板用接著劑。 Using the formulation described in Table 4, it was performed in the same manner as in Example 2-1 to produce an adhesive for a solar cell back cover.

(比較例2-1) (Comparative Example 2-1)

以表5所記載之配方，與實施例2-1同樣地進行，製作太陽能電池後罩板用接著劑。 Using the formulations described in Table 5, the same procedure as in Example 2-1 was performed to produce an adhesive for a solar cell back cover.

此外，表中的摻混量為固體成分質量比。 In addition, the compounding quantity in a table | surface is a solid content mass ratio.

(評價方法2) (Evaluation method 2)

(評價2-1：層合外觀) (Evaluation 2-1: laminated appearance)

以125μm厚的PET薄膜(TORAY股份有限公司製「Lumirror X10S」)為基材，對PET薄膜，將上述之太陽能電池後罩板用接著劑塗裝成10g/m2(乾燥質量)並使溶劑揮發後，將作為貼合用薄膜之30μm厚的白色聚偏二氟乙烯薄膜(Arkema公司製「Kyner」)積層。其後，以40℃、72小時進行老化，而得到評價試樣。 A 125 μm-thick PET film ("Lumirror X10S" manufactured by TORAY Co., Ltd.) was used as a base material. The PET film was coated with the above-mentioned adhesive for a solar cell back cover to 10 g / m 2 (dry mass) and a solvent. After volatilization, a 30 μm-thick white polyvinylidene fluoride film (“Kyner” manufactured by Arkema) was laminated as a film for bonding. Then, it aged at 40 degreeC for 72 hours, and obtained the evaluation sample.

對前述評價試樣，由白色聚偏二氟乙烯薄膜側目視評價層合外觀。 About the said evaluation sample, the laminated appearance was visually evaluated from the white polyvinylidene fluoride film side.

○：薄膜表面平滑 ○: Film surface is smooth

△：薄膜表面存在少許凹坑(凹陷) △: There are a few pits (dents) on the film surface

×：薄膜表面存在多數凹坑(凹陷) ×: Many pits (dents) exist on the film surface

(評價2-2：接著力) (Evaluation 2-2: Adherence)

以125μm厚的PET薄膜(TORAY股份有限公司製「Lumirror X10S」)為基材，對PET薄膜，將上述之太陽能電池後罩板用接著劑塗裝成10g/m2(乾燥質量)並使溶劑揮發後，將作為貼合用薄膜之30μm厚的白色聚偏二氟乙烯薄膜(Arkema公司製「Kyner」)積層。其後，以40℃、72小時進行老化，而得到評價試樣。 A 125 μm-thick PET film ("Lumirror X10S" manufactured by TORAY Co., Ltd.) was used as a base material. The PET film was coated with the above-mentioned adhesive for a solar cell back cover to 10 g / m 2 (dry mass) and a solvent. After volatilization, a 30 μm-thick white polyvinylidene fluoride film (“Kyner” manufactured by Arkema) was laminated as a film for bonding. Then, it aged at 40 degreeC for 72 hours, and obtained the evaluation sample.

將評價試樣以拉伸試驗機(島津製作所股份有限公司製「Autograph AGS-J」)評價剝離速度100mm/min下的強度(N/15mm、180°剝離)作為接著力。測定初始(老化 後)的接著力及在高度加速壽命試驗裝置(ESPEC股份有限公司製「EMS-221M」)中於121℃、100%RH保持48小時進行濕熱處理後的接著力。 The evaluation sample used a tensile tester ("Autograph AGS-J" manufactured by Shimadzu Corporation) to evaluate the strength (N / 15 mm, 180 ° peeling) at a peeling speed of 100 mm / min as the adhesive force. The initial (after aging) adhesive force and the adhesive force after being subjected to wet heat treatment at 121 ° C and 100% RH for 48 hours in a highly accelerated life tester ("EMS-221M" manufactured by ESPEC Corporation) were measured.

(評價2-3：接著劑的抗水解性) (Evaluation 2-3: Hydrolytic resistance of the adhesive)

以PTFE薄膜(日東電工股份有限公司製「NITOFLON Films No.900UL」)為基材，以施用器塗裝上述之太陽能電池後罩板用接著劑。使溶劑揮發後，以40℃、72小時進行老化，而得到評價試樣。 Using the PTFE film ("NITOFLON Films No. 900UL" manufactured by Nitto Denko Corporation) as a base material, the above-mentioned adhesive for a solar cell back cover was coated with an applicator. After the solvent was evaporated, the sample was aged at 40 ° C. for 72 hours to obtain an evaluation sample.

將評價試樣在上述高度加速壽命試驗裝置中於121℃、100%RH保持48小時，來進行濕熱處理。 The evaluation sample was held in a highly accelerated life test apparatus at 121 ° C. and 100% RH for 48 hours to perform a wet heat treatment.

藉由下述所示方法，測定初始(老化後)及濕熱處理後之接著劑的凝膠分率，算出濕熱處理後之凝膠分率相對於初始之凝膠分率的保持率，來評價太陽能電池後罩板用接著劑的抗水解性。 The gel fraction of the adhesive after initial (after aging) and wet heat treatment was measured by the method shown below, and the retention rate of the gel fraction after wet heat treatment with respect to the initial gel fraction was calculated and evaluated Hydrolytic resistance of adhesives for solar cell backsheets.

◎：保持率為80%以上(實用上特別優良) ◎: Retention rate is 80% or more (especially excellent in practical use)

○：保持率為50%以上~小於80%(實用上優良) ○: Retention rate is 50% or more and less than 80% (excellent in practical use)

△：保持率為20%以上~小於50%(實用範圍) △: Retention rate is 20% or more and less than 50% (practical range)

×：保持率為0%以上~小於20% ×: Retention rate is from 0% to less than 20%

上述之太陽能電池後罩板用接著劑的凝膠分率係藉由以下所說明的測定方法來算出。由評價試樣採取約0.2g的接著劑層，置入多孔質茶包中，而製作待測試樣。其次，測定待測試樣的質量而作為浸漬前質量。接著，將待測試樣置入裝滿甲基乙基酮的70ml容器中， 於23℃保存24小時。其後，由容器中取出待測試樣，在120℃的乾燥機中乾燥1小時而去除甲基乙基酮。其次，測定去除甲基乙基酮之待測試樣的質量而作為浸漬後質量。其後，由下述式算出接著劑的凝膠分率。 The gel fraction of the above-mentioned adhesive for a solar cell back cover is calculated by the measurement method described below. About 0.2 g of an adhesive layer was taken from the evaluation sample and placed in a porous tea bag to prepare a test sample. Next, the mass of the sample to be tested is determined as the mass before immersion. Next, the sample to be tested was placed in a 70 ml container filled with methyl ethyl ketone, and stored at 23 ° C. for 24 hours. Thereafter, the sample to be tested was taken out of the container, and dried in a dryer at 120 ° C. for 1 hour to remove methyl ethyl ketone. Next, the mass of the test sample from which methyl ethyl ketone was removed was measured as the mass after immersion. Thereafter, the gel fraction of the adhesive was calculated from the following formula.

凝膠分率(質量%)=(A-B)/(C-B)×100 Gel fraction (% by mass) = (A-B) / (C-B) × 100

(上述式中，A為浸漬後質量，B為茶包的質量，C為浸漬前質量)。 (In the above formula, A is the mass after immersion, B is the mass of the tea bag, and C is the mass before immersion).

將結果示於表4、表5。 The results are shown in Tables 4 and 5.

由實施例、比較例可知，本發明之太陽能電池後罩板用接著劑係層合外觀、接著力、抗水解性優良。 As can be seen from the examples and comparative examples, the adhesive system for a solar cell back cover sheet of the present invention is excellent in laminated appearance, adhesion, and hydrolysis resistance.

Claims (9)

一種聚酯多元醇，其係以多元酸或其衍生物與多元醇為必要原料的聚酯多元醇，其特徵為該多元酸或其衍生物原料全為具有芳環之多元酸或其衍生物，且數量平均分子量為3000~100000的範圍。     A polyester polyol, which is a polyester polyol using a polyacid or its derivative and a polyhydric alcohol as an essential raw material, characterized in that the polyacid or its derivative is all a polyacid or a derivative thereof having an aromatic ring , And the number average molecular weight is in the range of 3000 ~ 100,000.     如請求項1之聚酯多元醇，其中該多元醇原料係包含分支伸烷基二醇。     The polyester polyol of claim 1, wherein the polyol raw material comprises a branched alkylene glycol.     如請求項1或2之聚酯多元醇，其中該聚酯多元醇係以多元酸或其衍生物、多元醇與聚異氰酸酯為必要原料。     The polyester polyol according to claim 1 or 2, wherein the polyester polyol is based on a polyacid or a derivative thereof, a polyol and a polyisocyanate as essential raw materials.     如請求項1至3中任一項之聚酯多元醇，其中該聚酯多元醇為以多元酸或其衍生物與多元醇為必要原料的聚酯多元醇與聚異氰酸酯之反應生成物。     The polyester polyol according to any one of claims 1 to 3, wherein the polyester polyol is a reaction product of a polyester polyol and a polyisocyanate using a polyacid or a derivative thereof and a polyol as necessary raw materials.     一種反應型接著劑，其特徵為以包含如請求項1至4中任一項之聚酯多元醇的多元醇組成物(A)與聚異氰酸酯組成物(B)為必要成分。     A reactive type adhesive, characterized in that the polyol composition (A) and the polyisocyanate composition (B) containing the polyester polyol according to any one of claims 1 to 4 are essential components.     一種太陽能電池後罩板用接著劑，其係如請求項1至5中任一項所記載。     An adhesive for a solar cell back cover sheet, as described in any one of claims 1 to 5.     一種積層體，其係至少在第一基材與第二基材之間積層接著劑層而成的積層體，其特徵為該接著劑層為如請求項5之反應型接著劑。     A laminated body is a laminated body in which an adhesive layer is laminated at least between a first substrate and a second substrate, and is characterized in that the adhesive layer is a reactive adhesive as in claim 5.     一種太陽能電池後罩板，其特徵為包含如請求項7之積層體。     A solar cell back cover is characterized by including a laminated body as claimed in claim 7.     一種太陽能電池模組，其係將如請求項8之太陽能電池後罩板與太陽能電池單元經由封裝材貼合而成。     A solar battery module is formed by bonding a solar battery back cover plate and a solar battery unit according to claim 8 through a packaging material.    
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CN110036053B (en) 2022-02-15
WO2018117082A1 (en) 2018-06-28

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