TW202113021A - Two-pack type adhesive, multilayer body, molded body and packaging material - Google Patents

Two-pack type adhesive, multilayer body, molded body and packaging material Download PDF

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TW202113021A
TW202113021A TW109126611A TW109126611A TW202113021A TW 202113021 A TW202113021 A TW 202113021A TW 109126611 A TW109126611 A TW 109126611A TW 109126611 A TW109126611 A TW 109126611A TW 202113021 A TW202113021 A TW 202113021A
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Taiwan
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resin
polyester polyol
adhesive
acid
layer
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TW109126611A
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Chinese (zh)
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小林裕季
菅野勉
村上倫康
三原崇
伊東孝之
中村英美
神山達哉
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日商Dic股份有限公司
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04Polyurethanes
    • C09J175/06Polyurethanes from polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/20Layered products comprising a layer of metal comprising aluminium or copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/34Layered products comprising a layer of synthetic resin comprising polyamides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
    • B32B7/12Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38Packaging materials of special type or form
    • B65D65/40Applications of laminates for particular packaging purposes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4213Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Secondary Cells (AREA)
  • Sealing Battery Cases Or Jackets (AREA)

Abstract

The present invention provides a two-pack type adhesive which has excellent moldability, heat resistance and wet heat resistance. A two-pack type adhesive which is characterized by containing (A) a polyol composition that contains (A1) a polyester polyol and (B) a polyisocyanate composition that contains (B1) an isocyanate compound, and which is also characterized in that: the polyester polyol (A1) is a reaction product of (a1) a polybasic acid or a derivative thereof and (a2) a polyhydric alcohol; and the polyhydric alcohol (a2) contains (a2-1) a polyhydric alcohol wherein the number of carbon atoms in a methylene chain between two hydroxy groups is an odd number from 5 to 19.

Description

二液型接著劑、積層體、成型體、包裝材Two-component adhesives, laminates, molded products, packaging materials

本發明係關於一種二液型接著劑、使用該二液型接著劑而得之積層體、成型體、包裝材。The present invention relates to a two-component adhesive, a laminate, a molded body, and a packaging material obtained by using the two-component adhesive.

在用於包裝以食品、日用品、電子元件為代表的各種收納物的包裝材料中,為了保護內容物不受流通時等受到的衝擊、氧、水分導致的劣化,要求強度、不易破裂、氣體阻隔性等功能。在對內容物進行加熱殺菌處理時,需要耐蒸煮性、耐熱性等,有時也要求透明性以能夠確認內容物。但是,難以用一種材料滿足必要的功能。例如,在藉由熱密封進行密封時使用的無拉伸之聚烯烴膜其熱加工性優異,但另一方面,氧阻隔性不足。相反地,尼龍膜雖然阻氣性優異,但熱封性差。In packaging materials used for packaging various storage items such as food, daily necessities, and electronic components, in order to protect the contents from the impact during circulation, etc., deterioration caused by oxygen and moisture, strength, resistance to breakage, and gas barrier are required. Features such as sex. When heat sterilizing the contents, retort resistance, heat resistance, etc. are required, and transparency is also required in order to be able to confirm the contents. However, it is difficult to satisfy the necessary functions with one material. For example, a non-stretched polyolefin film used when sealing by heat sealing is excellent in hot workability, but on the other hand, oxygen barrier properties are insufficient. On the contrary, although the nylon film has excellent gas barrier properties, it has poor heat-sealability.

因此,廣泛使用不同種類的聚合物材料、或將聚合物材料與金屬基材貼合而成的積層體作為包裝材料。又,有時將把積層體成型而形成一個或複數個收納部的積層體作為包裝材使用(專利文獻1-3)。形成有一個或複數個收納部的積層體藉由與形成有相同形狀的收納部之積層體、或未形成有收納部(未進行成型加工)的積層體接合而密封收納部。作為接合方法,使用有熱熔接(熱密封)。 [先前技術文獻] [專利文獻]Therefore, different types of polymer materials or laminates formed by bonding polymer materials and metal substrates are widely used as packaging materials. In addition, a laminate in which a laminate is formed to form one or a plurality of accommodating parts may be used as a packaging material (Patent Documents 1 to 3). The laminated body formed with one or a plurality of accommodating portions seals the accommodating portion by joining with a laminated body in which a accommodating portion of the same shape is formed, or a laminated body that is not formed with a accommodating portion (without molding processing). As a joining method, thermal welding (heat sealing) is used. [Prior Technical Literature] [Patent Literature]

專利文獻1:日本特開2013-199283號公報 專利文獻2:日本特表2008-535746號公報 專利文獻3:日本特開2015-082354號公報Patent Document 1: Japanese Patent Application Publication No. 2013-199283 Patent Document 2: Japanese Special Publication No. 2008-535746 Patent Document 3: Japanese Patent Application Publication No. 2015-082354

[發明所欲解決之課題][The problem to be solved by the invention]

本發明之目的在於提供一種適於此種用途的包裝材,即,提供一種具有優異之成型性、即使在為了密封收納物而進行之密封劑層彼此的熱熔接後層間之接著強度亦不會降低、不會發生層間之隆起等外觀不良的包裝材。又,其目的在於提供一種適合於製造此種包裝材的成型性、耐熱性優異之二液型接著劑、使用該接著劑之積層體、成型體。 [用以解決課題之手段]The object of the present invention is to provide a packaging material suitable for such use, that is, to provide a packaging material with excellent moldability, even after the heat fusion of the sealant layers for sealing the storage, the adhesive strength between the layers is not Packaging materials with poor appearance such as lowering and no bulging between layers. In addition, its object is to provide a two-component adhesive suitable for manufacturing such packaging materials with excellent moldability and heat resistance, a laminate and a molded body using the adhesive. [Means to solve the problem]

本發明係關於一種二液型接著劑,其特徵在於含有:包含聚酯多元醇(A1)之多元醇組成物(A)、及包含異氰酸酯化合物(B1)之聚異氰酸酯組成物(B);聚酯多元醇(A1)係多元酸或其衍生物(a1)與多羥基醇(a2)之反應產物,多羥基醇(a2)包含2個羥基間之亞甲基鏈(methylene chain)的碳原子數在5以上且19以下並且為奇數之多羥基醇(a2-1)。 [發明之效果]The present invention relates to a two-component adhesive, which is characterized by containing: a polyol composition (A) containing a polyester polyol (A1), and a polyisocyanate composition (B) containing an isocyanate compound (B1); poly Ester polyol (A1) is the reaction product of polyacid or its derivative (a1) and polyhydric alcohol (a2). Polyhydric alcohol (a2) contains the carbon atoms of the methylene chain between 2 hydroxyl groups. Polyhydric alcohols (a2-1) whose number is 5 or more and 19 or less and is an odd number. [Effects of Invention]

藉由使用本發明之二液型接著劑,可得到一種包裝材,其具有優異之成型性、即使在為了密封收納物而進行之密封劑層彼此的熱熔接後層間之接著強度亦不會降低、不會發生層間之隆起等外觀不良。By using the two-component adhesive of the present invention, a packaging material can be obtained that has excellent moldability and does not reduce the adhesive strength between the sealant layers even after the heat fusion of the sealant layers for sealing the storage. , No appearance defects such as bulging between layers will occur.

<接著劑> 本發明之接著劑係一種二液型之接著劑,以包含聚酯多元醇(A1)之多元醇組成物(A)、及包含異氰酸酯化合物(B1)之聚異氰酸酯組成物(B)作為必要成分,聚酯多元醇(A1)係多元酸或其衍生物(a1)與多羥基醇(a2)之反應產物,多羥基醇(a2)包含2個羥基間之亞甲基鏈的碳原子數為5以上且19以下並且為奇數之多羥基醇(a2-1)。<Adhesive agent> The adhesive of the present invention is a two-component adhesive, which contains a polyol composition (A) containing a polyester polyol (A1) and a polyisocyanate composition (B) containing an isocyanate compound (B1) as essential components , Polyester polyol (A1) is the reaction product of polybasic acid or its derivative (a1) and polyhydric alcohol (a2). Polyhydric alcohol (a2) contains the number of carbon atoms in the methylene chain between 2 hydroxyl groups. 5 or more and 19 or less and an odd number of polyhydric alcohols (a2-1).

(多元醇組成物(A)) (聚酯多元醇(A1)) 聚酯多元醇(A1)係多元酸或其衍生物(a1)與多羥基醇(a2)之反應產物。(Polyol composition (A)) (Polyester polyol (A1)) Polyester polyol (A1) is a reaction product of polyacid or its derivative (a1) and polyhydric alcohol (a2).

作為用作聚酯多元醇(A1)之原料之多元酸或其衍生物(a1),可列舉下述等:丙二酸、乙基丙二酸、二甲基丙二酸、琥珀酸、2,2-二甲基琥珀酸、琥珀酸酐、烯基琥珀酸酐、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、反丁烯二酸、順丁烯二酸、順丁烯二酸酐、伊康酸等脂肪族多元酸。Examples of the polybasic acid or its derivative (a1) used as the raw material of the polyester polyol (A1) include the following: malonic acid, ethylmalonic acid, dimethylmalonic acid, succinic acid, 2 ,2-Dimethylsuccinic acid, succinic anhydride, alkenyl succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid Aliphatic polybasic acids such as diacid, maleic anhydride and itaconic acid.

丙二酸二甲酯、丙二酸二乙酯、琥珀酸二甲酯、戊二酸二甲酯、己二酸二甲酯、庚二酸二乙酯、癸二酸二乙酯、反丁烯二酸二甲酯、反丁烯二酸二乙酯、順丁烯二酸二甲酯、順丁烯二酸二乙酯等脂肪族多元酸之烷基酯化物。Dimethyl malonate, diethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, diethyl pimelate, diethyl sebacate, transbutane Alkyl ester products of aliphatic polybasic acids such as dimethyl acrylate, diethyl fumarate, dimethyl maleate, and diethyl maleate.

1,1-環戊烷二羧酸、1,2-環戊烷二羧酸、1,3-環戊烷二羧酸、1,2-環己烷二羧酸、1,3-環己烷二羧酸、1,4-環己烷二羧酸、四氫鄰苯二甲酸酐、4-甲基六氫鄰苯二甲酸酐、六氫鄰苯二甲酸酐、環己烷-1,2,4-三羧酸-1,2-酐、納迪克酸酐(himic anhydride)、氯橋酸酐(het anhydride)等脂環族多元酸。1,1-cyclopentane dicarboxylic acid, 1,2-cyclopentane dicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, 1,2-cyclohexane dicarboxylic acid, 1,3-cyclohexane Alkane dicarboxylic acid, 1,4-cyclohexane dicarboxylic acid, tetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, cyclohexane-1, 2,4-Tricarboxylic acid-1,2-anhydride, himic anhydride, het anhydride and other alicyclic polybasic acids.

鄰苯二甲酸、對苯二甲酸、間苯二甲酸、鄰苯二甲酸酐、1,4-萘二羧酸、2,5-萘二羧酸、2,6-萘二羧酸、2,3-萘二羧酸酐、萘二羧酸、1,2,4-苯三甲酸、苯偏三酸酐、焦蜜石酸、焦蜜石酸二酐、聯苯二羧酸、1,2-雙(苯氧基)乙烷-p,p'-二羧酸、二苯甲酮四羧酸、二苯甲酮四羧酸二酐、間苯二甲酸-5-磺酸鈉、四氯鄰苯二甲酸酐、四溴鄰苯二甲酸酐等芳香族多元酸。Phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, 1,4-naphthalene dicarboxylic acid, 2,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 2, 3-Naphthalenedicarboxylic acid anhydride, naphthalenedicarboxylic acid, 1,2,4- trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic dianhydride, biphenyl dicarboxylic acid, 1,2-bis (Phenoxy) ethane-p,p'-dicarboxylic acid, benzophenone tetracarboxylic acid, benzophenone tetracarboxylic dianhydride, isophthalic acid-5-sodium sulfonate, tetrachlorophthalic acid Aromatic polybasic acids such as dicarboxylic anhydride and tetrabromophthalic anhydride.

對苯二甲酸二甲酯、2,6-萘二羧酸二甲酯等芳香族多元酸之甲酯化物;可將1種或2種以上組合使用。Methyl esters of aromatic polybasic acids such as dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate; one type or two or more types can be used in combination.

當中,可較佳地使用己二酸、壬二酸、癸二酸、二聚物酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、1,2,4-苯三甲酸及其酐或其甲酯化合物。又,從提高成型性、耐熱性此方面而言,多元酸或其衍生物(a1)較佳包含具有芳香族環之多元酸或其衍生物(a1-1)。較佳為鄰苯二甲酸、間苯二甲酸、對苯二甲酸、1,2,4-苯三甲酸及其酐或其甲酯化合物,更佳為間苯二甲酸、對苯二甲酸、1,2,4-苯三甲酸及其酸酐或其甲酯化合物。Among them, adipic acid, azelaic acid, sebacic acid, dimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and its Anhydride or its methyl ester compound. In addition, from the viewpoint of improving moldability and heat resistance, the polybasic acid or its derivative (a1) preferably contains an aromatic ring-containing polybasic acid or its derivative (a1-1). Preferred are phthalic acid, isophthalic acid, terephthalic acid, 1,2,4- trimellitic acid and its anhydride or its methyl ester compound, more preferably isophthalic acid, terephthalic acid, 1 ,2,4-Mellitic acid and its anhydride or its methyl ester compound.

作為多羥基醇(a2),可為二醇,亦可為3官能以上之多元醇,上述二醇例如可列舉下述等:乙二醇、二乙二醇、1,2-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-戊二醇等脂肪族二醇。As the polyhydric alcohol (a2), it may be a diol or a polyhydric alcohol having a trifunctional or higher function. Examples of the above-mentioned diol include the following: ethylene glycol, diethylene glycol, 1,2-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-hexane Aliphatic diols such as diol, 1,4-bis(hydroxymethyl)cyclohexane, and 2,2,4-trimethyl-1,3-pentanediol.

聚氧乙二醇、聚氧丙二醇等醚二醇。Polyoxyethylene glycol, polyoxypropylene glycol and other ether glycols.

藉由上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環狀醚鍵之化合物之開環聚合而獲得的改質聚醚二醇。With the above aliphatic diols and ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, and phenyl glycidyl ether , Allyl glycidyl ether and other modified polyether glycols obtained by ring-opening polymerization of various compounds containing cyclic ether bonds.

藉由上述脂肪族二醇與乳酸內酯(lactanoid)、ε-己內酯等各種內酯類之縮聚反應而獲得之內酯系聚酯多元醇。A lactone-based polyester polyol obtained by the polycondensation reaction of the aforementioned aliphatic diol with various lactones such as lactanoid and ε-caprolactone.

雙酚A、雙酚F等雙酚。Bisphenols such as bisphenol A and bisphenol F.

對雙酚A、雙酚F等雙酚加成環氧乙烷、環氧丙烷等而獲得之雙酚之環氧烷(alkylene oxide)加成物。An alkylene oxide adduct of bisphenol obtained by adding ethylene oxide and propylene oxide to bisphenols such as bisphenol A and bisphenol F.

上述3官能以上之多元醇可列舉下述等:三羥甲基乙烷、三羥甲基丙烷、甘油、己三醇、新戊四醇等脂肪族多元醇。Examples of the above-mentioned trifunctional or higher polyhydric alcohols include the following: aliphatic polyhydric alcohols such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and neopentylerythritol.

藉由上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環狀醚鍵之化合物之開環聚合而獲得之改質聚醚多元醇。With the above aliphatic polyols and ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, and phenyl glycidyl ether , Allyl glycidyl ether and other various compounds containing cyclic ether bonds to obtain modified polyether polyols obtained by ring-opening polymerization.

藉由上述脂肪族多元醇與ε-己內酯等各種內酯類之縮聚反應而獲得之內酯系聚酯多元醇等。A lactone-based polyester polyol obtained by the polycondensation reaction of the above-mentioned aliphatic polyol and various lactones such as ε-caprolactone.

於本發明中,多羥基醇(a2)包含2個羥基間之亞甲基鏈之碳原子數為5以上且19以下並且為奇數之多羥基醇(a2-1)作為必要成分。亞甲基鏈可為直鏈狀,亦可為具有側鏈之支鏈狀。於亞甲基鏈含有側鏈時,側鏈之碳原子數不包含於亞甲基鏈之碳原子數中。以下,亦將此種二醇簡稱為多羥基醇(a2-1)。In the present invention, the polyhydric alcohol (a2) contains an odd number of polyhydric alcohols (a2-1) with carbon atoms in the methylene chain between two hydroxyl groups of 5 or more and 19 or less as an essential component. The methylene chain may be linear or branched with side chains. When the methylene chain contains a side chain, the number of carbon atoms in the side chain is not included in the number of carbon atoms in the methylene chain. Hereinafter, this diol is also abbreviated as polyhydric alcohol (a2-1).

作為亞甲基鏈為直鏈狀之多羥基醇(a2-1),可列舉:1,5-戊二醇、1,7-庚二醇、1,9-壬二醇、1,11-十一烷二醇、1,13-十三烷二醇、1,15-十五烷二醇、1,17-十七烷二醇、1,19-十九烷二醇。Examples of polyhydric alcohols (a2-1) with linear methylene chains include 1,5-pentanediol, 1,7-heptanediol, 1,9-nonanediol, and 1,11- Undecanediol, 1,13-tridecanediol, 1,15-pentadecanediol, 1,17-heptadecandiol, 1,19-nonadecanediol.

作為亞甲基鏈為支鏈狀之多羥基醇(a2-1),可列舉1-甲基-1,5-戊二醇、2-甲基-1,5-戊二醇、3-甲基-1,5-戊二醇、2,4-二乙基-1,5-戊二醇、2-甲基-1,7-庚二醇、3-甲基-1,7-庚二醇、4-甲基-1,7-庚二醇、2-甲基-1,9-壬二醇、3-甲基-1,9-壬二醇、4-甲基-1,9-壬二醇、5-甲基-1,9-壬二醇等。Examples of polyhydric alcohols (a2-1) whose methylene chain is branched include 1-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, and 3-methyl 1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-methyl-1,7-heptanediol, 3-methyl-1,7-heptane Alcohol, 4-methyl-1,7-heptanediol, 2-methyl-1,9-nonanediol, 3-methyl-1,9-nonanediol, 4-methyl-1,9- Nonanediol, 5-methyl-1,9-nonanediol, etc.

藉由多羥基醇(a2)包含多羥基醇(a2-1),可使本發明之接著劑形成為接著性、成型性、耐熱性優異者。其理由推測如下。為了提高接著劑之耐熱性,較佳為將乙二醇、1,2-丙二醇、1,4-丁二醇、1,4-環己烷二甲醇、三環癸烷二甲醇、異山梨醇、琥珀酸、1,4-環己烷二羧酸、鄰苯二甲酸、間苯二甲酸、對苯二甲酸、2,6-萘二羧酸等提高聚酯多元醇之凝聚力的成分加入聚酯多元醇之主骨架中。然而,若加入此種成分,則聚酯多元醇之玻璃轉移溫度提高,接著劑之成型性或潤濕性降低。潤濕性之降低會成為接著性降低之誘因。另一方面,多羥基醇(a2-1)由於使聚酯多元醇之玻璃轉移溫度降低的效果較高,使用有多羥基醇(a2-1)之聚酯多元醇(A1)(使用有其之二液型接著劑)在維持成型性、潤濕性之同時,在其骨架中加入凝聚力高的成分,可使耐熱性提高。提高聚酯多元醇之凝聚力的成分之摻合量視與其它成分之平衡而適當地設定。作為一例,為多元酸或其衍生物(a1)及多羥基醇(a2)之總量的30莫耳%以上且90莫耳%以下。When the polyhydric alcohol (a2) contains the polyhydric alcohol (a2-1), the adhesive of the present invention can be formed to have excellent adhesiveness, moldability, and heat resistance. The reason is presumed as follows. In order to improve the heat resistance of the adhesive, it is preferable to combine ethylene glycol, 1,2-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, and isosorbide , Succinic acid, 1,4-cyclohexane dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, 2,6-naphthalene dicarboxylic acid and other components to improve the cohesive force of polyester polyols are added to the poly In the main skeleton of ester polyols. However, if such a component is added, the glass transition temperature of the polyester polyol increases, and the moldability or wettability of the adhesive decreases. The decrease in wettability will become an inducement for the decrease in adhesion. On the other hand, polyhydric alcohol (a2-1) has a higher effect of lowering the glass transition temperature of polyester polyol, so polyester polyol (A1) with polyhydric alcohol (a2-1) is used. Two-component adhesive) while maintaining moldability and wettability, adding high cohesive components to its skeleton can improve heat resistance. The blending amount of the component that improves the cohesive force of the polyester polyol is appropriately set depending on the balance with other components. As an example, it is 30 mol% or more and 90 mol% or less of the total amount of the polybasic acid or its derivative (a1) and the polyhydric alcohol (a2).

多羥基醇(a2-1)之摻合量鑑於必要之成型性(成型溫度、成型深度等)之程度來適當調整即可。從接著性、成型性、耐熱性之平衡之方面而言,作為一例,較佳為多羥基醇(a2)之10莫耳%以上,更佳為30莫耳%以上,更佳為40莫耳%以上。關於上限,並無特別限制,較佳為90莫耳%以下,更佳為85莫耳%以下,更佳為80莫耳%以下。進一步,於多羥基醇(a2-1)之亞甲基鏈的碳原子數為5以上且11以下時,較佳為多羥基醇(a2)之20莫耳%以上,較佳為90莫耳%以下,更佳為40莫耳%以上且80莫耳%以下。於多羥基醇(a2-1)之亞甲基鏈的碳原子數為13以上且19以下時,較佳為10莫耳%以上且60莫耳%以下,更佳為15莫耳%以上且40莫耳%以下。The blending amount of polyhydric alcohol (a2-1) can be adjusted appropriately in view of the necessary degree of moldability (molding temperature, molding depth, etc.). In terms of the balance of adhesion, moldability, and heat resistance, as an example, it is preferably 10 mol% or more of the polyhydric alcohol (a2), more preferably 30 mol% or more, and even more preferably 40 mol% %the above. There is no particular limitation on the upper limit, but it is preferably 90 mol% or less, more preferably 85 mol% or less, and still more preferably 80 mol% or less. Furthermore, when the number of carbon atoms in the methylene chain of the polyhydric alcohol (a2-1) is 5 or more and 11 or less, it is preferably 20 mol% or more of the polyhydric alcohol (a2), preferably 90 mol% % Or less, more preferably 40 mol% or more and 80 mol% or less. When the number of carbon atoms in the methylene chain of the polyhydric alcohol (a2-1) is 13 or more and 19 or less, it is preferably 10 mol% or more and 60 mol% or less, more preferably 15 mol% or more and Below 40 mol%.

從成型性、耐熱性的兼顧更為優異此點而言,較佳為多羥基醇(a2-1)之亞甲基鏈為直鏈狀。又,更佳為亞甲基鏈之碳原子數為7以上且15以下,更佳為9以上且13以下。From the point that it is more excellent in the balance between moldability and heat resistance, it is preferable that the methylene chain of the polyhydric alcohol (a2-1) is linear. Moreover, it is more preferable that the number of carbon atoms of the methylene chain is 7 or more and 15 or less, and more preferably 9 or more and 13 or less.

多羥基醇(a2)較佳為進一步包含選自由具有支鏈伸烷基結構之多羥基醇(a2-2)、具有環狀結構之多羥基醇(a2-3)所組成之群中至少一種。以下,亦將具有支鏈伸烷基結構之多羥基醇(a2-2)稱作多羥基醇(a2-2),將具有環狀結構之多羥基醇(a2-3)稱作多羥基醇(a2-3)。The polyhydric alcohol (a2) preferably further includes at least one selected from the group consisting of polyhydric alcohols having a branched alkylene structure (a2-2) and polyhydric alcohols having a cyclic structure (a2-3) . Hereinafter, the polyhydric alcohol (a2-2) with a branched alkylene structure is also referred to as polyhydric alcohol (a2-2), and the polyhydric alcohol (a2-3) with cyclic structure is also referred to as polyhydric alcohol. (A2-3).

多羥基醇(a2-2)係於分子結構内具有3級或4級碳原子之多羥基醇,例如可列舉:1,2-丙二醇、2-甲基-1,3-丙二醇、新戊二醇、2,2-二乙基-1,3-丙二醇、2-甲基-2-丙基-1,3-丙二醇、2-丁基-2-乙基-1,3-丙二醇、2,2-異丁基-1,3-丙二醇、2,2-異戊基-1,3-丙二醇、1,3-丁二醇、2,3-丁二醇、3-甲基-1,3-丁二醇、2,4-戊二醇、2-甲基-2,4-戊二醇、2,4-二甲基-2,4-戊二醇、2,2,4-三甲基-1,3-戊二醇、1,2-己二醇、2,5-己二醇、2,5-二甲基-2,5-己二醇、1,2-辛二醇、2-甲基-1,8-辛二醇等支鏈烷基二醇;三羥甲基乙烷、三羥甲基丙烷、新戊四醇等3官能以上之含支鏈烷基結構之多官能醇;可單獨使用或將二種以上併用。該等之中,就可獲得耐濕熱性尤其優異之聚酯多元醇(A1)之觀點而言,較佳為新戊二醇。Polyhydric alcohols (a2-2) are polyhydric alcohols with three-level or four-level carbon atoms in the molecular structure. Examples include: 1,2-propanediol, 2-methyl-1,3-propanediol, and neopentyl alcohol Alcohol, 2,2-Diethyl-1,3-Propanediol, 2-Methyl-2-Propyl-1,3-Propanediol, 2-Butyl-2-Ethyl-1,3-Propanediol, 2, 2-isobutyl-1,3-propanediol, 2,2-isopentyl-1,3-propanediol, 1,3-butanediol, 2,3-butanediol, 3-methyl-1,3 -Butanediol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,4-dimethyl-2,4-pentanediol, 2,2,4-trimethyl 1,3-pentanediol, 1,2-hexanediol, 2,5-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,2-octanediol, 2-methyl-1,8-octanediol and other branched chain alkyl diols; trimethylolethane, trimethylolpropane, neopentylerythritol and other tri-functional or more branched alkyl structures Functional alcohol; can be used alone or in combination of two or more. Among these, from the viewpoint that a polyester polyol (A1) having particularly excellent heat and humidity resistance can be obtained, neopentyl glycol is preferred.

多羥基醇(a2-3)係於分子結構内具有環狀結構之多羥基醇。環狀結構可為單環,亦可為多環,可為芳香環式,亦可為脂環式。亦可為雜環。作為此種多羥基醇(a2-3),可列舉;1,3-環戊二醇、1,2-環己二醇、1,3-環己二醇、1,4-環己二醇、4-(羥甲基)環己醇、4-(2-羥乙基)環己醇、1,4-環己烷二甲醇、4,4’-雙環己醇、1,3-金剛烷二醇、1,3,5-金剛烷三醇、3-(羥甲基)-1-金剛烷醇、三環[5.2.1.02.6 ]-癸二甲醇、1,2-苯二甲醇、1,4-苯二甲醇、4,4-二羥基雙酚、4,4’-雙苯基二甲醇、2,2’-亞甲基二苯酚、2,4’-亞甲基二苯酚、4,4’-亞甲基二苯酚、4,4’-亞乙基雙酚A、雙酚A、1,4-萘二醇、1,5-萘二醇、1,6-萘二醇、1,7-萘二醇、2,3-萘二醇、2,6-萘二醇、2,7-萘二醇等。Polyhydric alcohols (a2-3) are polyhydric alcohols with a cyclic structure in the molecular structure. The cyclic structure may be monocyclic, polycyclic, aromatic or alicyclic. It can also be a heterocyclic ring. Examples of such polyhydric alcohols (a2-3) include; 1,3-cyclopentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, and 1,4-cyclohexanediol , 4-(hydroxymethyl)cyclohexanol, 4-(2-hydroxyethyl)cyclohexanol, 1,4-cyclohexanedimethanol, 4,4'-dicyclohexanol, 1,3-adamantane Diol, 1,3,5-adamantanol, 3-(hydroxymethyl)-1-adamantanol, tricyclo[5.2.1.0 2.6 ]-decane dimethanol, 1,2-benzenedimethanol, 1 ,4-Benzene dimethanol, 4,4-dihydroxy bisphenol, 4,4'-bisphenyl dimethanol, 2,2'-methylene diphenol, 2,4'-methylene diphenol, 4 ,4'-methylene diphenol, 4,4'-ethylene bisphenol A, bisphenol A, 1,4-naphthalenediol, 1,5-naphthalenediol, 1,6-naphthalenediol, 1,7-naphthalenediol, 2,3-naphthalenediol, 2,6-naphthalenediol, 2,7-naphthalenediol, etc.

隨著多羥基醇(a2-1)之摻合量增加,有時聚酯多元醇(A1)對有機溶劑之溶解性降低,或與後述之聚異氰酸酯組成物(B)的硬化塗膜(接著劑層)之彈性率降低。如果對有機溶劑之溶解性降低,則將本發明之二液型接著劑製成溶劑型時,保存穩定性降低,如果硬化塗膜之彈性率降低,則成型加工時有可能引起接著劑層之破壞,但藉由多羥基醇(a2)包含選自由多羥基醇(a2-2)及多羥基醇(a2-3)所組成之群中至少一種、即聚酯多元醇(A1)具備源自多羥基醇(a2-2)、(a2-3)之結構,能夠防止保存穩定性、彈性率之降低。進一步,多羥基醇(a2-2)、(a2-3)也可以期待提高硬化塗膜之耐水解性之效果。As the blending amount of the polyhydric alcohol (a2-1) increases, the solubility of the polyester polyol (A1) in organic solvents may decrease, or it may combine with the cured coating film of the polyisocyanate composition (B) described later (following The elastic modulus of the agent layer is reduced. If the solubility in organic solvents is reduced, the storage stability of the two-component adhesive of the present invention is reduced when it is made into a solvent type. If the elastic modulus of the cured coating film is reduced, it may cause the adhesive layer to change during the molding process. Damage, but because the polyhydric alcohol (a2) contains at least one selected from the group consisting of polyhydric alcohols (a2-2) and polyhydric alcohols (a2-3), that is, polyester polyol (A1) is derived from The structure of polyhydric alcohols (a2-2) and (a2-3) can prevent the decrease in storage stability and elasticity. Furthermore, polyhydric alcohols (a2-2) and (a2-3) can also be expected to improve the hydrolysis resistance of the cured coating film.

多羥基醇(a2-2)及多羥基醇(a2-3)之合計摻合量視與其它成分之平衡而適當調整,作為一例,較佳為10莫耳%以上且90莫耳%以下。更佳為15莫耳%以上且70莫耳%以下、20莫耳%以上且60莫耳%以下。The total blending amount of the polyhydric alcohol (a2-2) and the polyhydric alcohol (a2-3) is appropriately adjusted depending on the balance with other components. As an example, it is preferably 10 mol% or more and 90 mol% or less. More preferably, it is 15 mol% or more and 70 mol% or less, and 20 mol% or more and 60 mol% or less.

多羥基醇(a2)在不損害本發明之效果的範圍內,亦可含有多羥基醇(a2-1)~(a2-3)以外之多羥基醇(a-4)。The polyhydric alcohol (a2) may contain polyhydric alcohols (a-4) other than the polyhydric alcohols (a2-1) to (a2-3) within a range that does not impair the effects of the present invention.

於本發明中,聚酯多元醇(A1)可為以多元酸或其衍生物(a1)、多羥基醇(a2)、及聚異氰酸酯作為必需原料之聚酯聚胺酯多元醇(polyester polyurethane polyol)。此種情形時所使用之聚異氰酸酯可列舉二異氰酸酯化合物、或3官能以上之聚異氰酸酯化合物。該等聚異氰酸酯可分別單獨使用,亦可將兩種以上併用。In the present invention, the polyester polyol (A1) can be a polyester polyurethane polyol (polyester polyurethane polyol) using a polyacid or its derivative (a1), a polyhydric alcohol (a2), and a polyisocyanate as essential raw materials. As the polyisocyanate used in this case, a diisocyanate compound or a polyisocyanate compound with three or more functions can be mentioned. These polyisocyanates may be used individually, respectively, and may use 2 or more types together.

二異氰酸酯化合物例如可列舉下述者: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、伸茬基二異氰酸酯、間四甲基伸茬基二異氰酸酯、離胺酸二異氰酸酯等脂肪族二異氰酸酯。Examples of the diisocyanate compound include the following: butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-tri Aliphatic diisocyanates such as methyl hexamethylene diisocyanate, stubborn diisocyanate, m-tetramethyl stubborn diisocyanate, and lysine diisocyanate.

環己烷-1,4-二異氰酸酯、異佛酮二異氰酸酯、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、亞異丙基二環己基-4,4'-二異氰酸酯、降莰烷二異氰酸酯等脂環族二異氰酸酯。Cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methyl ring Alicyclic diisocyanates such as hexane diisocyanate, isopropylidene dicyclohexyl-4,4'-diisocyanate, norbornane diisocyanate.

1,5-萘二異氰酸酯、2,2'-二苯甲烷二異氰酸酯、2,4'-二苯甲烷二異氰酸酯、4,4'-二苯甲烷二異氰酸酯、4,4'-二苯基二甲基甲烷二異氰酸酯、4,4'-二苄基二異氰酸酯、二烷基二苯甲烷二異氰酸酯、四烷基二苯甲烷二異氰酸酯、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芳香族二異氰酸酯。1,5-Naphthalene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl diisocyanate Methylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate Aromatic diisocyanates such as phenyl diisocyanate and tolylene diisocyanate.

3官能以上之聚異氰酸酯化合物例如可列舉:二異氰酸酯之寡聚物、分子內具有胺酯鍵部位之加成物型聚異氰酸酯化合物、分子內具有異氰尿酸酯(isocyanurate)環結構之尿酸酯(nurate)型聚異氰酸酯化合物。Examples of polyisocyanate compounds with more than three functions include diisocyanate oligomers, adduct type polyisocyanate compounds having urethane bond sites in the molecule, and uric acid having an isocyanurate ring structure in the molecule. Ester (nurate) type polyisocyanate compound.

分子內具有胺酯鍵部位之加成物型聚異氰酸酯化合物例如可使二異氰酸酯化合物與多羥基醇反應而獲得。該反應中所使用之二異氰酸酯化合物例如可列舉上述作為二異氰酸酯化合物所例示之各種二異氰酸酯化合物,該等可分別單獨使用,亦可將兩種以上併用。又,該反應中所使用之多元醇化合物可列舉上述作為多羥基醇(a2)所例示之各種多元醇化合物、或使多羥基醇與多元酸反應而獲得之聚酯多元醇等,該等可分別單獨使用,亦可將兩種以上併用。The adduct type polyisocyanate compound having a amine ester bond site in the molecule can be obtained by, for example, reacting a diisocyanate compound with a polyhydric alcohol. Examples of the diisocyanate compound used in this reaction include the various diisocyanate compounds exemplified above as the diisocyanate compound, and these may be used alone, or two or more of them may be used in combination. In addition, the polyol compound used in the reaction may include various polyol compounds exemplified as the polyhydric alcohol (a2) above, or polyester polyols obtained by reacting a polyhydric alcohol with a polybasic acid, etc. These may They can be used alone, or two or more of them can be used in combination.

分子內具有異氰尿酸酯環結構之尿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及/或二醇反應而獲得。該反應中所使用之二異氰酸酯化合物例如可列舉上述作為二異氰酸酯化合物所例示之各種二異氰酸酯化合物,該等可分別單獨使用,亦可將兩種以上併用。又,作為該反應中所使用之單醇,可列舉: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,可列舉上述多羥基醇中所例示之脂肪族二醇等。該等單醇或二醇可分別單獨使用,亦可將兩種以上併用。The urate-type polyisocyanate compound having an isocyanurate ring structure in the molecule can be obtained, for example, by reacting a diisocyanate compound with a monool and/or a diol. Examples of the diisocyanate compound used in this reaction include the various diisocyanate compounds exemplified above as the diisocyanate compound, and these may be used alone, or two or more of them may be used in combination. In addition, as the monoalcohol used in this reaction, hexanol, 2-ethylhexanol, octanol, n-decyl alcohol, n-undecyl alcohol, n-dodecanol, n-tridecanol, n-tetradecyl alcohol, Alcohol, n-pentadecanol, n-heptadecanol, n-octadecyl alcohol, n-nonadecanol, eicosanol, 5-ethyl-2-nonanol, trimethylnonanol, 2-hexyldecanol, 3, 9-diethyl-6-tridecanol, 2-isoheptylisoundecyl alcohol, 2-octyldodecanol, 2-decyltetradecyl alcohol, etc. As the diol, the above-mentioned polyhydric alcohols can be cited The aliphatic diols exemplified. These monoalcohols or diols may be used alone, or two or more of them may be used in combination.

本發明中使用之聚酯多元醇(A1)係多元酸或其衍生物(a1)與多羥基醇(a2)之反應產物,且多元酸或其衍生物(a1)中之具有芳香族環之多元酸或其衍生物(a1-1)之比例較佳為30莫耳%以上。藉此,可製成保存穩定性優異之接著劑。進而,就成型性、耐熱性提昇之方面而言,多元酸或其衍生物(a1)中之具有芳香族環之多元酸或其衍生物(a1-1)之比例更佳為50莫耳%以上,更佳為70莫耳%以上,更佳為96莫耳%以上。亦可多元酸或其衍生物(a1)全部為具有芳香族環之多元酸或其衍生物(a1-1)。The polyester polyol (A1) used in the present invention is a reaction product of a polybasic acid or its derivative (a1) and a polyhydric alcohol (a2), and the polybasic acid or its derivative (a1) has an aromatic ring The ratio of the polybasic acid or its derivative (a1-1) is preferably 30 mol% or more. Thereby, an adhesive agent with excellent storage stability can be made. Furthermore, in terms of improving moldability and heat resistance, the ratio of the polybasic acid or its derivative (a1) with the aromatic ring-containing polybasic acid or its derivative (a1-1) is more preferably 50 mol% Above, more preferably 70 mol% or more, and even more preferably 96 mol% or more. The polybasic acid or its derivative (a1) may all be a polybasic acid or its derivative (a1-1) having an aromatic ring.

或者是,本發明中使用之聚酯多元醇(A1)亦可為多元酸或其衍生物(a1)、多羥基醇(a2)、及聚異氰酸酯之反應產物,且多元酸或其衍生物(a1)中之具有芳香族環之多元酸或其衍生物(a1-1)之比例較佳為30莫耳%以上。藉此,可製成保存穩定性優異之接著劑。進而,就成型性、耐熱性提昇之方面而言,多元酸或其衍生物(a1)中之具有芳香族環之多元酸或其衍生物(a1-1)之比例更佳為50莫耳%以上,更佳為70莫耳%以上,更佳為96莫耳%以上。亦可多元酸或其衍生物(a1)全部為具有芳香族環之多元酸或其衍生物(a1-1)。Alternatively, the polyester polyol (A1) used in the present invention may also be a reaction product of a polyacid or its derivative (a1), a polyhydric alcohol (a2), and a polyisocyanate, and the polyacid or its derivative ( The ratio of the polybasic acid or its derivative (a1-1) with an aromatic ring in a1) is preferably 30 mol% or more. Thereby, an adhesive agent with excellent storage stability can be made. Furthermore, in terms of improving moldability and heat resistance, the ratio of the polybasic acid or its derivative (a1) with the aromatic ring-containing polybasic acid or its derivative (a1-1) is more preferably 50 mol% Above, more preferably 70 mol% or more, and even more preferably 96 mol% or more. The polybasic acid or its derivative (a1) may all be a polybasic acid or its derivative (a1-1) having an aromatic ring.

關於本發明中使用之聚酯多元醇(A1)之羥值,就接著強度更優異之方面而言,較佳為1~40 mgKOH/g之範圍,更佳為3 mgKOH/g以上,且為30 mgKOH/g以下。Regarding the hydroxyl value of the polyester polyol (A1) used in the present invention, it is preferably in the range of 1-40 mgKOH/g, more preferably 3 mgKOH/g or more, in terms of more excellent adhesive strength. Below 30 mgKOH/g.

關於本發明中使用之聚酯多元醇(A1)之數量平均分子量(Mn),就用於接著劑用途時之接著強度更優異之方面而言,較佳為2,000~100,000之範圍,更佳為2,000~50,000。於數量平均分子量未達2,000之情形時,存在硬化塗膜中之交聯密度過高而導致積層體之外觀、成型性變差之情況。 另一方面,重量平均分子量(Mw)較佳為5,000~300,000之範圍,更佳為10,000~200,000之範圍。Regarding the number average molecular weight (Mn) of the polyester polyol (A1) used in the present invention, it is preferably in the range of 2,000 to 100,000, more preferably 2,000~50,000. When the number average molecular weight is less than 2,000, the crosslinking density in the cured coating film may be too high, which may result in deterioration of the appearance and moldability of the laminate. On the other hand, the weight average molecular weight (Mw) is preferably in the range of 5,000 to 300,000, more preferably in the range of 10,000 to 200,000.

再者,於本案發明中,重量平均分子量(Mw)、數量平均分子量(Mn)係藉由下述條件之凝膠滲透層析法(GPC)所測得之值。Furthermore, 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股份有限公司製造HLC-8320GPC 管柱:Tosoh股份有限公司製造 TSKgel 4000HXL、TSKgel 3000HXL、TSKgel 2000HXL、TSKgel 1000HXL 檢測器:RI(示差折射計) 資料處理:Tosoh股份有限公司製造 Multi Station GPC-8020modelII 測定條件:管柱溫度 40℃ 溶劑 四氫呋喃 流速 0.35 ml/分鐘 標準:單分散聚苯乙烯 試樣:將以樹脂固形物成分換算計0.2質量%之四氫呋喃溶液利用微過濾器進行過濾所得者(100 μl)Measuring device: HLC-8320GPC manufactured by Tosoh Co., Ltd. Column: manufactured by Tosoh Co., Ltd. TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL Detector: RI (differential refractometer) Data processing: Multi Station GPC-8020modelII manufactured by Tosoh Co., Ltd. Measurement conditions: column temperature 40℃ Solvent Tetrahydrofuran Flow rate 0.35 ml/min Standard: Monodisperse Polystyrene Sample: 0.2% by mass of the tetrahydrofuran solution converted to the solid content of the resin is filtered with a microfilter (100 μl)

本發明中使用之聚酯多元醇(A1)之固形物成分酸值並無特別限定,較佳為10.0 mgKOH/g以下。若為5.0 mgKOH/g以下,則耐濕熱性更優異,故而較佳。又,關於固形物成分酸值之下限,並無特別限制,作為一例,為0.5 mgKOH/g以上。亦可為0 mgKOH/g。The solid component acid value of the polyester polyol (A1) used in the present invention is not particularly limited, but it is preferably 10.0 mgKOH/g or less. If it is 5.0 mgKOH/g or less, the moisture and heat resistance is more excellent, so it is preferable. In addition, there is no particular limitation on the lower limit of the acid value of the solid content, but as an example, it is 0.5 mgKOH/g or more. It can also be 0 mgKOH/g.

本發明中使用之聚酯多元醇(A1)之玻璃轉移溫度較佳為-30℃以上且20℃以下。藉由使聚酯多元醇(A1)之玻璃轉移溫度處於該範圍,而在與下述之樹脂(A2)併用時,可製成接著強度、成型性、耐熱性、耐濕熱性優異之接著劑。聚酯多元醇(A1)之玻璃轉移溫度更佳為-20℃以上,更佳為15℃以下。The glass transition temperature of the polyester polyol (A1) used in the present invention is preferably -30°C or more and 20°C or less. By setting the glass transition temperature of the polyester polyol (A1) in this range, when used in combination with the following resin (A2), an adhesive with excellent bonding strength, moldability, heat resistance, and moisture and heat resistance can be made . The glass transition temperature of the polyester polyol (A1) is more preferably -20°C or higher, and more preferably 15°C or lower.

再者,本案發明中之玻璃轉移溫度係指以如下方式所測得之值。 使用示差掃描熱量測定裝置(SII NanoTechnology股份有限公司製造之DSC-7000,以下稱為DSC),使試樣5 mg於30 mL/分鐘之氮氣氣流下以10℃/分鐘自室溫升溫至200℃,其後,以10℃/分鐘冷卻至-80℃。使之再次以10℃/分鐘升溫至150℃並測定DSC曲線,將使第二次升溫步驟中所觀測到之測定結果中之低溫側之基線延長至高溫側的直線、與在玻璃轉移之階梯狀部分之曲線之斜率成為最大之點所劃的切線之交點作為玻璃轉移點,將此時之溫度作為玻璃轉移溫度。又,雖於第一次升溫中升溫至200℃,但其只要為聚酯多元醇(A1)充分地熔融之溫度即可,於在200℃不充分之情形時進行適當調整。同樣地,關於冷卻溫度,於在-80℃不充分之情形時(低於玻璃轉移溫度之情形時等)亦進行適當調整。Furthermore, the glass transition temperature in the present invention refers to the value measured in the following manner. Using a differential scanning calorimetry device (DSC-7000 manufactured by SII NanoTechnology Co., Ltd., hereinafter referred to as DSC), 5 mg of the sample was heated from room temperature to 200°C at 10°C/min under a nitrogen flow of 30 mL/min. After that, it was cooled to -80°C at 10°C/min. Make it rise again at 10°C/min to 150°C and measure the DSC curve to extend the baseline on the low temperature side of the measurement result observed in the second heating step to the straight line on the high temperature side, and the step in the glass transition The intersection of the tangent line drawn by the point where the slope of the curve of the shape portion becomes the maximum is regarded as the glass transition point, and the temperature at this time is regarded as the glass transition temperature. In addition, although the temperature is raised to 200°C in the first temperature rise, it is sufficient as long as it is a temperature at which the polyester polyol (A1) is sufficiently melted. When 200°C is insufficient, it is appropriately adjusted. Similarly, about the cooling temperature, when it is insufficient at -80°C (when it is lower than the glass transition temperature, etc.), it is also adjusted appropriately.

於聚酯多元醇(A1)之合成時,多元酸或其衍生物與多羥基醇之反應、或者多元酸或其衍生物、多羥基醇及聚異氰酸酯之反應只要利用公知之方法進行即可。In the synthesis of the polyester polyol (A1), the reaction of the polybasic acid or its derivative with the polyhydric alcohol, or the reaction of the polybasic acid or its derivative, the polyhydric alcohol, and the polyisocyanate may be performed by a known method.

例如多元酸或其衍生物與上述多羥基醇之反應可利用縮聚反應來進行。又,關於多元酸或其衍生物、上述多羥基醇及上述聚異氰酸酯之反應,可藉由使利用上述方法使多元酸或其衍生物與上述多羥基醇反應而得之聚酯多元醇與上述聚異氰酸酯,視需要於公知慣用的胺酯化觸媒之存在下反應,而獲得本發明之聚酯多元醇(A1)。For example, the reaction of a polybasic acid or its derivative with the above-mentioned polyhydric alcohol can be carried out by a condensation polymerization reaction. In addition, with regard to the reaction of the polybasic acid or its derivative, the polyhydric alcohol and the polyisocyanate, the polyester polyol obtained by reacting the polyhydric acid or its derivative with the polyhydric alcohol and the polyisocyanate can be If necessary, the polyisocyanate is reacted in the presence of a well-known and customary aminating catalyst to obtain the polyester polyol (A1) of the present invention.

多元酸或其衍生物與多羥基醇之酯化反應係將多元酸或其衍生物、多羥基醇、及聚合觸媒添加於具備攪拌機、精餾設備之反應容器,攪拌並同時於常壓升溫至130℃左右。其後,於130~260℃之範圍之反應溫度以1小時5~10℃之比例進行升溫並同時蒸餾去除所生成之水。進行4~12小時酯化反應後,自常壓直至1~300 torr之範圍內緩慢地提高減壓度並同時蒸餾去除殘餘之多羥基醇,促進反應,藉此能夠製造聚酯多元醇(A1)。The esterification reaction of polybasic acid or its derivatives and polyhydric alcohol is to add polybasic acid or its derivatives, polyhydric alcohol, and polymerization catalyst to a reaction vessel equipped with agitator and rectification equipment, stir and raise the temperature at normal pressure at the same time To about 130°C. Thereafter, the reaction temperature in the range of 130 to 260°C was increased in a ratio of 5 to 10°C for 1 hour while distilling off the generated water. After the esterification reaction is carried out for 4-12 hours, the pressure is gradually increased from normal pressure to the range of 1 to 300 torr and the residual polyhydric alcohol is distilled off at the same time to promote the reaction, thereby making it possible to produce polyester polyol (A1 ).

作為酯化反應中使用之聚合觸媒,較佳為由選自由週期表之第2族、第4族、第12族、第13族、第14族、第15族所組成之群中至少1種金屬、或該金屬之化合物構成之聚合觸媒。作為由該金屬或其金屬化合物構成之聚合觸媒,可列舉Ti、Sn、Zn、Al、Zr、Mg、Hf、Ge等金屬、該等金屬之化合物,更具體而言,可列舉四異丙氧鈦、四丁氧鈦、氧基乙醯丙酮鈦、辛酸錫、2-乙基己酸錫、乙醯丙酮鋅、四氯化鋯、四氯化鋯四氫呋喃錯合物、四氯化鉿、四氯化鉿四氫呋喃錯合物、氧化鍺、四乙氧基鍺等。The polymerization catalyst used in the esterification reaction is preferably at least 1 selected from the group consisting of Group 2, Group 4, Group 12, Group 13, Group 14 and Group 15 of the periodic table A polymerization catalyst composed of a metal or a compound of the metal. Examples of the polymerization catalyst composed of the metal or its metal compound include metals such as Ti, Sn, Zn, Al, Zr, Mg, Hf, Ge, and compounds of these metals, and more specifically, tetraisopropyl Titanium oxide, titanium tetrabutoxide, titanium oxyacetone acetonate, tin octoate, tin 2-ethylhexanoate, zinc acetone acetone, zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, Hafnium tetrachloride tetrahydrofuran complex, germanium oxide, tetraethoxy germanium, etc.

作為酯化反應中可使用之聚合觸媒之市售品,可較佳地列舉Matsumoto Fine Chemica公司製造之ORGATIX TA series、TC series、ZA series、ZC series、AL series;日東化成公司製造之有機錫系觸媒、無機金屬觸媒、無機錫化合物。Commercially available polymerization catalysts that can be used in the esterification reaction include ORGATIX TA series, TC series, ZA series, ZC series, and AL series manufactured by Matsumoto Fine Chemica, and organotin manufactured by Nitto Chemical Co., Ltd. Department of catalysts, inorganic metal catalysts, inorganic tin compounds.

關於該等聚合觸媒之使用量,只要能夠控制酯化反應且可獲得良好品質之聚酯多元醇(A1),則無特別限制,作為一例,相對於多元酸或其衍生物與多羥基醇之合計量為10~1000 ppm,較佳為20~800 ppm。為了抑制聚酯多元醇(A1)之著色,進而較佳為30~500 ppm。Regarding the amount of these polymerization catalysts used, as long as the esterification reaction can be controlled and a good quality polyester polyol (A1) can be obtained, there is no particular limitation. As an example, compared to the polybasic acid or its derivative and the polyhydric alcohol The total amount is 10-1000 ppm, preferably 20-800 ppm. In order to suppress the coloration of the polyester polyol (A1), it is more preferably 30 to 500 ppm.

又,本發明中使用之聚酯聚胺酯多元醇可將藉由上述方法而獲得之聚酯多元醇利用聚異氰酸酯進行鏈延長而獲得。作為具體之製造方法,將聚酯多元醇、聚異氰酸酯、鏈延長觸媒、及視需要而使用之聚酯多元醇與聚異氰酸酯之良溶劑添加於反應容器,並於60~90℃之反應溫度進行攪拌。進行反應直至源自所使用之聚異氰酸酯之異氰酸基實質上不殘存,而獲得本發明中使用之聚酯聚胺酯多元醇。In addition, the polyester polyurethane polyol used in the present invention can be obtained by chain extension of the polyester polyol obtained by the above method using polyisocyanate. As a specific manufacturing method, add polyester polyol, polyisocyanate, chain extension catalyst, and if necessary a good solvent of polyester polyol and polyisocyanate to the reaction vessel, and at a reaction temperature of 60-90°C Stir. The reaction is carried out until the isocyanate group derived from the polyisocyanate used does not substantially remain, and the polyester polyurethane polyol used in the present invention is obtained.

作為鏈延長觸媒,可使用通常用作胺酯化觸媒之公知常用之觸媒。具體而言,可列舉有機錫化合物、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。作為上述鏈延長觸媒之使用量,只要為充分地促進聚酯多元醇與聚異氰酸酯之反應之量即可,具體而言,較佳為相對於聚酯多元醇與聚異氰酸酯之合計量為5.0質量%以下。為了抑制由觸媒引起之對樹脂之水解或著色,更佳為1.0質量%以下。進而該等鏈延長觸媒亦可考慮作為下述之多元醇(A)與異氰酸酯組成物(B)之硬化觸媒的作用而使用。As the chain extension catalyst, well-known and commonly used catalysts generally used as amine esterification catalysts can be used. Specifically, organic tin compounds, organic tin carboxylates, lead carboxylates, bismuth carboxylates, titanium compounds, zirconium compounds, etc. can be cited, and they can be used alone or in combination. The use amount of the above-mentioned chain extension catalyst may be an amount that sufficiently promotes the reaction between the polyester polyol and the polyisocyanate. Specifically, it is preferably 5.0 relative to the total amount of the polyester polyol and the polyisocyanate. Less than mass%. In order to suppress the hydrolysis or coloring of the resin caused by the catalyst, it is more preferably 1.0% by mass or less. Furthermore, these chain extension catalysts can also be considered for use as a curing catalyst for the following polyol (A) and isocyanate composition (B).

作為異氰酸基之剩餘量之確認方法,可列舉藉由紅外吸收光譜測定來確認有無源自異氰酸基之吸收光譜即於2260 cm-1 附近所觀察到之吸收波峰,或藉由滴定法對異氰酸基進行定量。As a method of confirming the remaining amount of isocyanate groups, the presence or absence of an absorption spectrum derived from isocyanate groups, that is, the absorption peak observed near 2260 cm -1, can be confirmed by infrared absorption spectrometry, or by titration Method for quantification of isocyanate groups.

作為聚酯聚胺酯多元醇之製造所使用之良溶劑,可列舉乙酸乙酯、乙酸丁酯、甲基乙基酮、甲基異丁基酮、丙二醇單甲醚乙酸酯、甲苯、二甲苯等。可單獨使用,亦可將兩種以上併用。Good solvents used in the production of polyester polyurethane polyols include ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, toluene, xylene, etc. . It can be used alone, or two or more of them can be used in combination.

(樹脂(A2)) 從可形成為接著性、成型性、耐熱性更良好者此方面而言,本發明之多元醇組成物(A)較佳含有玻璃轉移溫度為50℃以上且110℃以下之樹脂(A2)。認為此種樹脂(A2)難以與聚酯多元醇(A1)相溶,在硬化塗膜中形成海島結構,發揮出聚酯多元醇(A1)對基材的優異之潤濕性、接著性、成型性,並且即便於在高溫、高濕下硬化塗膜之源自聚酯多元醇(A1)之部位的黏彈性降低之情形時,源自樹脂(A2)之部位亦會模擬地發揮出如填料之作用,因此接著層不易軟化,顯示良好之接著性、耐熱性。(Resin (A2)) The polyol composition (A) of the present invention preferably contains a resin (A2) having a glass transition temperature of 50° C. or more and 110° C. or less in terms of being able to be formed into better adhesiveness, moldability, and heat resistance. It is believed that this resin (A2) is difficult to dissolve with the polyester polyol (A1), forming a sea-island structure in the cured coating film, and exerting the polyester polyol (A1)'s excellent wettability, adhesiveness, and adhesion to the substrate. Moldability, and even when the viscoelasticity of the polyester polyol (A1)-derived part of the hardened coating film is reduced under high temperature and high humidity, the resin (A2)-derived part will simulate the performance as The role of filler, so the adhesive layer is not easy to soften, showing good adhesiveness and heat resistance.

樹脂(A2)只要其玻璃轉移溫度為50℃以上且110℃以下,則可無特別限制地使用,作為一例,可列舉:聚酯樹脂、聚胺酯樹脂、聚脲樹脂、丙烯酸樹脂、聚醯胺樹脂、聚醯亞胺樹脂、環氧樹脂、松香改質環氧樹脂等。為了使接著性、成型性、耐熱性良好,較佳為樹脂(A2)與聚酯多元醇(A1)不完全相溶,較佳為在測定「向聚酯多元醇(A1)50質量份與樹脂(A2)質量份添加甲苯二異氰酸酯之三羥甲基丙烷加成物30質量份而得之組成物」的動態黏彈性時的損耗正切(tanδ)中,可確認到源自於聚酯多元醇(A1)之波峰及源自於樹脂(A2)之波峰。樹脂(A2)可以具備或不具備羥基、羧基、胺基、醯胺基、硫醇基、縮水甘油基等官能基。The resin (A2) can be used without particular limitation as long as the glass transition temperature is 50°C or higher and 110°C or lower. As an example, polyester resins, polyurethane resins, polyurea resins, acrylic resins, and polyamide resins can be mentioned. , Polyimide resin, epoxy resin, rosin modified epoxy resin, etc. In order to achieve good adhesion, moldability, and heat resistance, it is preferable that the resin (A2) and the polyester polyol (A1) are not completely compatible, and it is preferable to measure "to 50 parts by mass of the polyester polyol (A1) and The composition obtained by adding 30 parts by mass of the trimethylolpropane adduct of toluene diisocyanate to the resin (A2) by mass" shows that the loss tangent (tanδ) at the time of dynamic viscoelasticity is derived from polyester multi-component The peak of alcohol (A1) and the peak derived from resin (A2). The resin (A2) may or may not have functional groups such as a hydroxyl group, a carboxyl group, an amino group, an amide group, a thiol group, and a glycidyl group.

於樹脂(A2)具備羥基時,較佳為2級或3級羥基。樹脂(A2)之羥值就接著強度更優異之方面而言,較佳為1~40 mgKOH/g之範圍,更佳為3 mgKOH/g以上、30 mgKOH/g以下。又,樹脂(A2)之羥值較佳為在聚酯多元醇(A1)之羥值以下。When the resin (A2) has a hydroxyl group, it is preferably a secondary or tertiary hydroxyl group. The hydroxyl value of the resin (A2) is preferably in the range of 1-40 mgKOH/g, and more preferably 3 mgKOH/g or more and 30 mgKOH/g or less in terms of more excellent adhesive strength. In addition, the hydroxyl value of the resin (A2) is preferably below the hydroxyl value of the polyester polyol (A1).

於樹脂(A2)具備羧基時,樹脂(A2)之固形物成分酸值並無特別限制,較佳為10.0 mgKOH/g以下。若為5.0 mgKOH/g以下,則耐濕熱性更為優異,而較佳。又,關於固形物成分酸值之下限,並無特別限制,作為一例,為0.5 mgKOH/g以上。When the resin (A2) has a carboxyl group, the solid content acid value of the resin (A2) is not particularly limited, and it is preferably 10.0 mgKOH/g or less. If it is 5.0 mgKOH/g or less, the moisture and heat resistance is more excellent, which is preferable. In addition, there is no particular limitation on the lower limit of the acid value of the solid content, but as an example, it is 0.5 mgKOH/g or more.

樹脂(A2)之玻璃轉移溫度為50℃以上且110℃以下。藉由使樹脂(A2)之玻璃轉移溫度處於該範圍,在與聚酯多元醇(A1)併用時能夠製成接著強度、成型性、耐熱性、耐濕熱性優異之接著劑。樹脂(A2)之玻璃轉移溫度更佳為60℃以上,更佳為65℃以上。又,樹脂(A2)之玻璃轉移溫度更佳為100℃以下,更佳為90℃以下。The glass transition temperature of the resin (A2) is 50°C or more and 110°C or less. By setting the glass transition temperature of the resin (A2) in this range, when used in combination with the polyester polyol (A1), it is possible to form an adhesive with excellent adhesive strength, moldability, heat resistance, and moisture and heat resistance. The glass transition temperature of the resin (A2) is more preferably 60°C or higher, and more preferably 65°C or higher. In addition, the glass transition temperature of the resin (A2) is more preferably 100°C or lower, and more preferably 90°C or lower.

樹脂(A2)之摻合量視必要之耐熱性的程度來適當調整,因此並無特別限定,相對聚酯多元醇(A1)與樹脂(A2)之合計100質量份,較佳設為90質量份以下。更佳為3質量份以上且65質量份以下,再更佳為5質量份以上且50質量份以下。藉此,可更確實地提高接著性、成型性、耐熱性、耐濕熱性。The blending amount of the resin (A2) is appropriately adjusted depending on the degree of necessary heat resistance, so it is not particularly limited. It is preferably set to 90 mass parts relative to the total of 100 parts by mass of the polyester polyol (A1) and the resin (A2) Servings or less. It is more preferably 3 parts by mass or more and 65 parts by mass or less, and still more preferably 5 parts by mass or more and 50 parts by mass or less. Thereby, the adhesiveness, moldability, heat resistance, and humidity and heat resistance can be improved more reliably.

(聚異氰酸酯組成物(B)) 本發明中使用之聚異氰酸酯組成物(B)包含異氰酸酯化合物(B)。異氰酸酯化合物(B)只要為一分子中具有2個以上異氰酸基之化合物,則並無特別限定,可使用各種化合物。具體而言,可使用上述聚酯多元醇(A1)、聚酯多元醇(A2)之原料中所述之各種二異氰酸酯化合物、二異氰酸酯化合物之寡聚物、各種使二異氰酸酯化合物與二醇化合物反應而獲得之加成物改質二異氰酸酯化合物、該等之縮二脲改質體、脲甲酸酯改質體、或各種3官能以上之聚異氰酸酯化合物。該等異氰酸酯化合物(B)可分別單獨使用,亦可將兩種以上併用。(Polyisocyanate composition (B)) The polyisocyanate composition (B) used in the present invention contains an isocyanate compound (B). The isocyanate compound (B) is not particularly limited as long as it is a compound having two or more isocyanate groups in one molecule, and various compounds can be used. Specifically, various diisocyanate compounds, oligomers of diisocyanate compounds, various diisocyanate compounds and diol compounds described in the raw materials of the above-mentioned polyester polyol (A1) and polyester polyol (A2) can be used. The adducts obtained by the reaction are modified diisocyanate compounds, these biuret modified bodies, allophanate modified bodies, or various polyisocyanate compounds with three or more functions. These isocyanate compounds (B) may be used alone, respectively, or two or more of them may be used in combination.

(接著劑 其它成分) 本發明之接著劑在不損害本發明之效果的範圍內,可併用其它成分。例如,多元醇組成物(A)亦可含有不等同於聚酯多元醇(A1)、樹脂(A2)之聚酯多元醇(A3)。聚酯多元醇(A3)可使用作為「多元酸或其衍生物與多羥基醇之反應產物」的聚酯多元醇、或作為「多元酸或其衍生物、與多羥基醇、與聚異氰酸酯之反應產物」的聚酯聚胺酯多元醇。又,用於聚酯多元醇(A3)之合成的多元酸或其衍生物、多羥基醇、聚異氰酸酯可使用與聚酯多元醇(A1)相同者。(Adhesive and other ingredients) In the adhesive of the present invention, other components may be used in combination within a range that does not impair the effects of the present invention. For example, the polyol composition (A) may also contain a polyester polyol (A3) that is not equivalent to the polyester polyol (A1) and the resin (A2). Polyester polyol (A3) can be used as the "reaction product of polybasic acid or its derivatives and polyhydric alcohol", or as "polybasic acid or its derivatives, polyhydric alcohol, and polyisocyanate". The reaction product" is a polyester polyurethane polyol. In addition, the polybasic acid or its derivative, polyhydric alcohol, and polyisocyanate used in the synthesis of the polyester polyol (A3) can be the same as the polyester polyol (A1).

聚酯多元醇(A3)較佳為多元酸或其衍生物中之具有芳香族環之多元酸或其衍生物的比例為30莫耳%以上之聚酯多元醇、聚酯聚胺酯多元醇。藉此,可形成為保存穩定性優異之接著劑。進一步,從提高成型性、耐熱性之方面而言,多元酸或其衍生物中之具有芳香族環之多元酸或其衍生物的比例更佳為50莫耳%以上,更佳為70莫耳%以上,更佳為96莫耳%。亦可為全部的多元酸或其衍生物為具有芳香族環之多元酸或其衍生物。The polyester polyol (A3) is preferably a polyester polyol or a polyester polyurethane polyol in which the ratio of a polybasic acid or a polybasic acid or a derivative thereof having an aromatic ring in the polybasic acid or its derivatives is 30 mol% or more. Thereby, it can be formed as an adhesive agent excellent in storage stability. Furthermore, from the viewpoint of improving moldability and heat resistance, the ratio of the polybasic acid or its derivatives having an aromatic ring in the polybasic acid or its derivatives is more preferably 50 mol% or more, and more preferably 70 mol% % Or more, more preferably 96 mol%. All polybasic acids or derivatives thereof may be polybasic acids or derivatives thereof having an aromatic ring.

關於聚酯多元醇(A3)之羥值,從接著強度更優異之方面而言,較佳為1~40 mgKOH/g之範圍,更佳為3 mgKOH/g以上、30 mgKOH/g以下。The hydroxyl value of the polyester polyol (A3) is preferably in the range of 1 to 40 mgKOH/g, more preferably 3 mgKOH/g or more, and 30 mgKOH/g or less from the viewpoint of more excellent adhesive strength.

關於聚酯多元醇(A3)之數量平均分子量(Mn),從用於接著劑用途時之接著強度更優異之方面而言,較佳為2,000~100,000之範圍,更佳為2,000~50,000。於數量平均分子量未達2,000時,硬化塗膜中之交聯密度變得過高,而有積層體之外觀、成型性惡化之情況。 另一方面,重量平均分子量(Mw)較佳為5,000~300,000之範圍,更佳為10,000~200,000之範圍。The number average molecular weight (Mn) of the polyester polyol (A3) is preferably in the range of 2,000 to 100,000, more preferably in the range of 2,000 to 50,000, from the viewpoint of more excellent adhesive strength when used in adhesive applications. When the number average molecular weight is less than 2,000, the crosslink density in the cured coating film becomes too high, and the appearance and moldability of the laminate may deteriorate. On the other hand, the weight average molecular weight (Mw) is preferably in the range of 5,000 to 300,000, more preferably in the range of 10,000 to 200,000.

聚酯多元醇(A3)之固形物成分酸值並無特別限定,較佳為10.0 mgKOH/g以下。若為5.0 mgKOH/g以下,則耐濕熱性更為優異而較佳。又,關於固形物成分酸值之下限,並無特別限制,作為一例,為0.5 mgKOH/g以上。亦可為0 mgKOH/g。聚酯多元醇(A3)之玻璃轉移溫度較佳為-30℃以上且20℃以下,更佳為-20℃以上,更佳為15℃以下。The solid content acid value of the polyester polyol (A3) is not particularly limited, but it is preferably 10.0 mgKOH/g or less. If it is 5.0 mgKOH/g or less, the moisture and heat resistance is more excellent and preferable. In addition, there is no particular limitation on the lower limit of the acid value of the solid content, but as an example, it is 0.5 mgKOH/g or more. It can also be 0 mgKOH/g. The glass transition temperature of the polyester polyol (A3) is preferably -30°C or higher and 20°C or lower, more preferably -20°C or higher, and more preferably 15°C or lower.

聚酯多元醇(A3)之摻合量並無特別限定,相對於聚酯多元醇(A1)、聚酯多元醇(A3)之合計100質量份,較佳設為90質量份以下。更佳為3質量份以上且65質量份以下,再更佳為3質量份以上且50質量份以下。又,於多元醇組成物含有聚酯多元醇(A1)、樹脂(A2)、與聚酯多元醇(A3)時,較佳為相對於其等合計100質量份,樹脂(A2)之摻合量為3質量份以上且65質量份以下。The blending amount of the polyester polyol (A3) is not particularly limited, but it is preferably 90 parts by mass or less with respect to 100 parts by mass of the total of the polyester polyol (A1) and the polyester polyol (A3). It is more preferably 3 parts by mass or more and 65 parts by mass or less, and still more preferably 3 parts by mass or more and 50 parts by mass or less. In addition, when the polyol composition contains polyester polyol (A1), resin (A2), and polyester polyol (A3), it is preferable to blend the resin (A2) with respect to 100 parts by mass in total. The amount is 3 parts by mass or more and 65 parts by mass or less.

多元醇組成物(A)較佳為含有聚碳酸酯多元醇化合物。此時,關於聚酯多元醇(A1)及樹脂(A2)之總量與聚碳酸酯多元醇化合物之摻合比率,就成為對各種基材之接著性較高、耐濕熱性亦優異之接著劑之方面而言,相對於兩者之合計質量,聚酯多元醇(A1)及樹脂(A2)之總質量較佳為30~99.5質量%之範圍,較佳為60~99質量%之範圍。The polyol composition (A) preferably contains a polycarbonate polyol compound. At this time, regarding the blending ratio of the total amount of polyester polyol (A1) and resin (A2) and the polycarbonate polyol compound, it becomes an adhesive with high adhesion to various substrates and excellent moisture and heat resistance. In terms of the agent, the total mass of the polyester polyol (A1) and the resin (A2) is preferably in the range of 30-99.5 mass%, preferably in the range of 60-99 mass%, relative to the total mass of the two. .

關於聚碳酸酯多元醇化合物之數量平均分子量(Mn),就成為對各種基材之接著性較高、耐濕熱性亦優異之接著劑之方面而言,較佳為300~2,000之範圍。其羥值較佳為30~250 mgKOH/g之範圍,更佳為40~200 mgKOH/g之範圍。又,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 in terms of high adhesion to various substrates and excellent moisture and heat resistance. The hydroxyl value is preferably in the range of 30 to 250 mgKOH/g, more preferably in the range of 40 to 200 mgKOH/g. Furthermore, the polycarbonate polyol compound is preferably a polycarbonate diol compound.

又,多元醇組成物(A)較佳為含有聚氧伸烷基改質多元醇化合物。此時,關於聚酯多元醇(A1)及樹脂(A2)之總量與聚氧伸烷基改質多元醇化合物之摻合比率,就成為對各種基材之接著性較高、耐濕熱性亦優異之接著劑之方面而言,相對於兩者之合計質量,聚酯多元醇(A1)及樹脂(A2)之總質量較佳為30~99.5質量%之範圍,較佳為60~99質量%之範圍。In addition, the polyol composition (A) preferably contains a polyoxyalkylene-modified polyol compound. At this time, the blending ratio of the total amount of the polyester polyol (A1) and the resin (A2) and the polyoxyalkylene modified polyol compound has high adhesion to various substrates and high humidity and heat resistance. In terms of an excellent adhesive, the total mass of the polyester polyol (A1) and the resin (A2) is preferably in the range of 30-99.5 mass%, preferably 60-99 relative to the total mass of the two. The range of mass%.

關於聚氧伸烷基改質多元醇化合物之數量平均分子量(Mn),就成為對各種基材之接著性較高、耐濕熱性亦優異之接著劑之方面而言,較佳為300~2,000之範圍。其羥值較佳為40~250 mgKOH/g之範圍,更佳為50~200 mgKOH/g之範圍。又,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。Regarding the number average molecular weight (Mn) of the polyoxyalkylene-modified polyol compound, it is preferably 300-2,000 in terms of high adhesion to various substrates and excellent moisture and heat resistance. The scope. The hydroxyl value is preferably in the range of 40 to 250 mgKOH/g, more preferably in the range of 50 to 200 mgKOH/g. In addition, the polyoxyalkylene-modified polyol compound is preferably a polyoxyalkylene-modified diol compound.

多元醇組成物(A)除聚酯多元醇(A1)、樹脂(A2)以外,亦可含有其它樹脂成分。於使用其它樹脂成分之情形時,較佳為相對於主劑之總質量以50質量%以下而使用,較佳為以30質量%以下而使用。作為其它樹脂成分之具體例,可列舉環氧樹脂。環氧樹脂例如可列舉:雙酚A型環氧樹脂、雙酚F型環氧樹脂等雙酚型環氧樹脂;聯苯型環氧樹脂、四甲基聯苯型環氧樹脂等聯苯型環氧樹脂;二環戊二烯-苯酚加成反應型環氧樹脂等。該等可分別單獨使用,亦可將兩種以上併用。該等之中,就成為對各種基材之接著性較高、耐濕熱性亦優異之接著劑之方面而言,較佳為使用雙酚型環氧樹脂。The polyol composition (A) may contain other resin components in addition to the polyester polyol (A1) and the resin (A2). When using other resin components, it is preferably used at 50% by mass or less with respect to the total mass of the main agent, and preferably used at 30% by mass or less. As a specific example of other resin components, epoxy resin is mentioned. Examples of the epoxy resin include: bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin; and biphenyl type epoxy resins such as biphenyl type epoxy resin and tetramethylbiphenyl type epoxy resin. Epoxy resin; dicyclopentadiene-phenol addition reaction type epoxy resin, etc. These may be used alone, or two or more of them may be used in combination. Among these, it is preferable to use a bisphenol-type epoxy resin in terms of becoming an adhesive having high adhesiveness to various substrates and excellent moisture and heat resistance.

關於環氧樹脂之數量平均分子量(Mn),就成為對各種基材之接著性較高、耐濕熱性亦優異之接著劑之方面而言,較佳為300~2,000之範圍。又,其環氧當量較佳為150~1000 g/當量之範圍。Regarding the number average molecular weight (Mn) of the epoxy resin, it is preferably in the range of 300 to 2,000 in terms of high adhesion to various substrates and excellent moisture and heat resistance. In addition, the epoxy equivalent is preferably in the range of 150 to 1000 g/equivalent.

於使用環氧樹脂之情形時,關於聚酯多元醇(A1)及樹脂(A2)之總量與環氧樹脂之摻合比率,就成為對各種基材之接著性較高、耐濕熱性亦優異之接著劑之方面而言,相對於兩者之合計質量,聚酯多元醇(A1)及樹脂(A2)之總質量較佳為30~99.5質量%之範圍,較佳為60~99質量%之範圍。In the case of using epoxy resin, the blending ratio of the total amount of polyester polyol (A1) and resin (A2) and epoxy resin becomes higher adhesion to various substrates, and also has high moisture and heat resistance. In terms of an excellent adhesive, the total mass of the polyester polyol (A1) and the resin (A2) is preferably in the range of 30-99.5 mass%, preferably 60-99 mass relative to the total mass of the two % Range.

本發明中使用之多元醇組成物(A)亦可含有黏著賦予劑。作為黏著賦予劑,例如可列舉:松香系或松香酯系黏著賦予劑、萜系或萜酚系黏著賦予劑、飽和烴樹脂、苯并呋喃系黏著賦予劑、苯并呋喃茚系黏著賦予劑、苯乙烯樹脂系黏著賦予劑、二甲苯樹脂系黏著賦予劑、酚樹脂系黏著賦予劑、石油樹脂系黏著賦予劑、酮樹脂系黏著賦予劑等。較佳為酮樹脂系黏著賦予劑、松香系或松香酯系黏著賦予劑,更佳為酮樹脂系黏著賦予劑。該等可分別單獨使用,亦可將兩種以上併用。於使用黏著賦予劑之情形時,相對於聚酯多元醇(A1)、樹脂(A2)、與黏著賦予劑之合計質量,聚酯多元醇(A1)與樹脂(A2)之總質量較佳為80~99.99質量%,更佳為85~99.9質量%。The polyol composition (A) used in the present invention may also contain an adhesion imparting agent. Examples of adhesion-imparting agents include rosin-based or rosin ester-based adhesion-imparting agents, terpene-based or terpene-phenol-based adhesion-imparting agents, saturated hydrocarbon resins, coumarone-based adhesion-imparting agents, coumarone-based adhesion-imparting agents, Styrene resin-based adhesive imparting agent, xylene resin-based adhesive imparting agent, phenol resin-based adhesive imparting agent, petroleum resin-based adhesive imparting agent, ketone resin-based adhesive imparting agent, etc. It is preferably a ketone resin-based adhesive imparting agent, a rosin-based or rosin ester-based adhesive imparting agent, and more preferably a ketone resin-based adhesive imparting agent. These may be used alone, or two or more of them may be used in combination. In the case of using an adhesion-imparting agent, the total mass of polyester polyol (A1) and resin (A2) is preferably relative to the total mass of polyester polyol (A1), resin (A2), and adhesion-imparting agent 80 to 99.99% by mass, more preferably 85 to 99.9% by mass.

作為松香系或松香酯系,可列舉:聚合松香、歧化松香、氫化松香、順丁烯二醯化松香、反丁烯二醯化松香、及該等之甘油酯、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 rosin-based or rosin ester-based rosins include polymerized rosin, disproportionated rosin, hydrogenated rosin, maleated rosin, fumarated rosin, and these glycerides, neopentyl erythritol esters, and methyl esters. Esters, ethyl esters, butyl esters, glycol esters, diethylene glycol esters, triethylene glycol esters, etc.

作為萜系或萜酚系,可列舉低聚合萜系、α-蒎烯聚合物、β-蒎烯聚合物、萜酚系、芳香族改質萜系、氫化萜系等。Examples of the terpene type or terpene phenol type include oligomerized terpene type, α-pinene polymer, β-pinene polymer, terpene phenol type, aromatic modified terpene type, hydrogenated terpene type, and the like.

作為石油樹脂系,可例示:使由戊烯、戊二烯、異戊二烯等獲得之碳數5個之石油餾分進行聚合而得之石油樹脂;使由茚、甲基茚、乙烯基甲苯、苯乙烯、α-甲基苯乙烯、β-甲基苯乙烯等獲得之碳數9個之石油餾分進行聚合而得之石油樹脂;由上述各種單體獲得之C5-C9共聚石油樹脂及使該等氫化而得之石油樹脂;由環戊二烯、二環戊二烯而獲得之石油樹脂;以及該等石油樹脂之氫化物;將該等石油樹脂利用順丁烯二酸酐、順丁烯二酸、反丁烯二酸、(甲基)丙烯酸、苯酚等進行改質而得之改質石油樹脂等。Examples of petroleum resins include: petroleum resins obtained by polymerizing petroleum fractions with 5 carbon atoms obtained from pentene, pentadiene, isoprene, etc.; and petroleum resins derived from indene, methyl indene, and vinyl toluene , Styrene, α-methylstyrene, β-methylstyrene, etc., petroleum resins obtained by polymerization of petroleum fractions with 9 carbons; C5-C9 copolymerized petroleum resins obtained from the above-mentioned various monomers and used Hydrogenated petroleum resins; petroleum resins obtained from cyclopentadiene and dicyclopentadiene; and hydrogenated products of these petroleum resins; these petroleum resins use maleic anhydride and maleic acid Modified petroleum resin obtained by modification of diacid, fumaric acid, (meth)acrylic acid, phenol, etc.

作為酚樹脂系,可使用苯酚類與甲醛之縮合物。作為該苯酚類,可列舉:苯酚、間甲酚、3,5-二甲苯酚、對烷苯酚、間苯二酚等,可例示利用鹼觸媒使該等苯酚類與甲醛進行加成反應而得之可溶酚醛樹脂、或利用酸觸媒進行縮合反應而得之酚醛清漆等。又,亦可例示藉由利用酸觸媒對松香加成苯酚並進行熱聚合而獲得之松香酚樹脂等。As the phenol resin system, a condensate of phenols and formaldehyde can be used. Examples of the phenols include phenol, m-cresol, 3,5-xylenol, p-alkylphenol, resorcinol, and the like. Examples of such phenols include the addition reaction of these phenols with formaldehyde using an alkali catalyst. Resol resin obtained, or novolac obtained by condensation reaction using acid catalyst, etc. In addition, rosin phenol resin obtained by adding phenol to rosin using an acid catalyst and thermally polymerizing it can also be exemplified.

作為酮樹脂,可列舉公知慣用者,但可較佳地使用甲醛樹脂、環己酮-甲醛樹脂,又,酮醛縮合樹脂等。As the ketone resin, known and commonly used ones can be cited, but formaldehyde resins, cyclohexanone-formaldehyde resins, and ketone-aldehyde condensation resins can be preferably used.

關於黏著賦予劑,可獲得具有各種軟化點者,就在與構成多元醇組成物(A)之其它樹脂混合之情形時之相容性、色調或熱穩定性等方面而言,較佳為軟化點為70~160℃,較佳為80~100℃之酮樹脂系黏著賦予劑、或者軟化點為80~160℃,較佳為90~110℃之松香系樹脂及其氫化衍生物,更佳為軟化點為70~160℃,較佳為80~100℃之酮樹脂系黏著賦予劑。又,較佳為酸值為2~20 mgKOH/g、羥值為10 mgKOH/g以下之酮樹脂系黏著賦予劑、氫化松香系黏著賦予劑,更佳為酸值為2~20 mgKOH/g、羥值為10 mgKOH/g以下之酮樹脂系黏著賦予劑。Regarding the adhesion imparting agent, those having various softening points can be obtained. In terms of compatibility, color tone, and thermal stability when mixed with other resins constituting the polyol composition (A), softening is preferred. A ketone resin-based adhesive imparting agent with a temperature of 70-160°C, preferably 80-100°C, or a rosin-based resin and its hydrogenated derivatives with a softening point of 80-160°C, preferably 90-110°C, more preferably It is a ketone resin-based adhesive agent having a softening point of 70 to 160°C, preferably 80 to 100°C. Also, a ketone resin-based adhesive imparting agent and a hydrogenated rosin-based adhesive imparting agent having an acid value of 2-20 mgKOH/g and a hydroxyl value of 10 mgKOH/g or less are preferable, and an acid value of 2-20 mgKOH/g is more preferable. 、A ketone resin adhesive agent with a hydroxyl value of 10 mgKOH/g or less.

於本發明之接著劑中,作為進而又一良好之態樣,可併用公知之磷酸類或其衍生物。藉此,接著劑之初期接著性進一步提昇,能夠消除穿隧等困擾。In the adhesive of the present invention, as yet another good aspect, known phosphoric acids or derivatives thereof can be used in combination. In this way, the initial adhesion of the adhesive is further improved, and the troubles such as tunneling can be eliminated.

作為此處所使用之磷酸類或其衍生物,可列舉例如次磷酸、亞磷酸、正磷酸、低磷酸等磷酸類;例如偏磷酸、焦磷酸、三聚磷酸、多磷酸、過磷酸等縮合磷酸類;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、亞磷酸二苯酯等單、二酯化物、來自縮合磷酸與醇類之單、二酯化物;例如對上述磷酸類加成例如環氧乙烷、環氧丙烷等環氧化合物而成者;例如對脂肪族或芳香族之二環氧丙基醚加成上述磷酸類而得之環氧磷酸酯類等。Examples of phosphoric acids or derivatives thereof used here include phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid, and low phosphoric acid; for example, condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and superphosphoric acid. ; For example, monomethyl orthophosphate, monoethyl orthophosphate, monopropyl orthophosphate, monobutyl orthophosphate, mono-2-ethylhexyl orthophosphate, monophenyl orthophosphate, monomethyl phosphite, Monoethyl phosphate, monopropyl phosphite, monobutyl phosphite, mono-2-ethylhexyl phosphite, monophenyl phosphite, di-2-ethylhexyl orthophosphate, diphenyl orthophosphate , Dimethyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, di-2-ethylhexyl phosphite, diphenyl phosphite and other mono- and diester compounds, from condensation Mono- and diester compounds of phosphoric acid and alcohols; for example, the addition of epoxy compounds such as ethylene oxide and propylene oxide to the above-mentioned phosphoric acid; for example, the addition of aliphatic or aromatic diglycidyl ether Epoxy phosphates etc. obtained from the above-mentioned phosphoric acid.

上述磷酸類或其衍生物可使用一種或兩種以上。作為含有上述磷酸類或其衍生物之方法,只需混入即可。One kind or two or more kinds of the above-mentioned phosphoric acids or derivatives thereof may be used. As a method of containing the above-mentioned phosphoric acid or its derivatives, it is only necessary to mix them.

又,於本發明之接著劑中亦可使用接著促進劑。關於接著促進劑,可列舉矽烷偶合劑、鈦酸酯系偶合劑、鋁系等之偶合劑、環氧樹脂等。In addition, an adhesion promoter can also be used in the adhesive of the present invention. Examples of the adhesion promoter include silane coupling agents, titanate coupling agents, aluminum coupling agents, epoxy resins, and the like.

作為矽烷偶合劑,例如可列舉:γ-胺基丙基三乙氧基矽烷、γ-胺基丙基三甲氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基三甲基二甲氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷等胺基矽烷;β-(3,4-環氧基環己基)乙基三甲氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基三乙氧基矽烷等環氧矽烷;乙烯基參(β-甲氧基乙氧基)矽烷、乙烯基三乙氧基矽烷、乙烯基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷等乙烯基矽烷;六甲基二矽氮烷、γ-巰基丙基三甲氧基矽烷等。Examples of the silane coupling agent include: γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethyl Aminosilanes such as oxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, etc.; β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxy propyl trimethoxy silane, γ-glycidoxy propyl triethoxy silane, etc. Oxysilane; vinyl ginseng (β-methoxyethoxy) silane, vinyl triethoxy silane, vinyl trimethoxy silane, γ-methacryloxy propyl trimethoxy silane and other vinyl groups Silane; hexamethyldisilazane, γ-mercaptopropyl trimethoxysilane, etc.

作為鈦酸酯系偶合劑,例如可列舉: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、乙醯丙酮酸鈦、乳酸鈦、四辛二醇鈦酸酯、乳酸鈦、四硬脂氧基鈦等。As the titanate coupling agent, for example, titanium tetraisopropoxide, titanium tetra-n-butoxide, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, Tetraoctanediol titanate, titanium lactate, titanium tetrastearyl oxide, etc.

又,作為鋁系偶合劑,例如可列舉乙醯烷氧基二異丙氧基鋁等。In addition, as an aluminum-based coupling agent, for example, acetalkoxy aluminum diisopropoxide and the like can be cited.

作為接著促進劑,較佳為使用矽烷偶合劑。又,接著促進劑之含量(固形物成分)相對於多元醇組成物(A)之固形物成分100質量份,較佳為0.1質量份以上,更佳為0.3質量份以上,更佳為0.5質量份以上,進而較佳為0.7質量份以上。又,接著促進劑之含量(固形物成分)相對於多元醇組成物(A)之固形物成分100質量份,較佳為10質量份以下,更佳為8質量份以下,進而較佳為5質量份以下。As the adhesion promoter, a silane coupling agent is preferably used. In addition, the content of the accelerator (solid content) relative to 100 parts by mass of the solid content of the polyol composition (A) is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, more preferably 0.5 parts by mass Parts or more, more preferably 0.7 parts by mass or more. In addition, the content of the accelerator (solid content) relative to 100 parts by mass of the solid content of the polyol composition (A) is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and still more preferably 5 Parts by mass or less.

於本發明之接著劑中,關於多元醇組成物(A)與聚異氰酸酯組成物(B)之摻合比,較佳為將多元醇組成物(A)所包含之羥基的合計莫耳數[OH]與聚異氰酸酯組成物(B)所包含之異氰酸基的莫耳數[NCO]的比[NCO]/[OH]設為1.5~15.0之範圍。藉此,成為成型性、耐熱性、耐濕熱性優異之二液型接著劑。In the adhesive of the present invention, the blending ratio of the polyol composition (A) and the polyisocyanate composition (B) is preferably the total number of moles of hydroxyl groups contained in the polyol composition (A) [ The ratio [NCO]/[OH] of the molar number [NCO] of the isocyanate group contained in the OH] and the polyisocyanate composition (B) is set in the range of 1.5 to 15.0. Thereby, it becomes a two-component adhesive with excellent moldability, heat resistance, and moisture and heat resistance.

二液型接著劑所存在之過量之異氰酸酯化合物會濕氣硬化而成為具有脲鍵之聚合物、寡聚物,認為有助於硬化塗膜之耐熱性、耐濕熱性提昇。因此,於[NCO]/[OH]比相對較小之情形時,例如若為1.5左右,則存在耐熱性、耐濕熱性不充分之情況,此時例如能夠藉由增加多元醇組成物(A)中之樹脂(A2)之摻合量來應對。又,於[NCO]/[OH]比相對較高之情形時,例如若為15.0左右,則存在因交聯密度或具有脲鍵之聚合物、寡聚物之影響而使塗膜過硬從而導致成型性降低之情況。此時,能夠藉由增加多元醇組成物(A)中之聚酯多元醇(A1)之摻合量來應對。為了確保二液型接著劑之設計自由度並且確實地提昇耐熱性、耐濕熱性,更佳為[NCO]/[OH]比為2.0~10、更佳為2.5~8.0。Excessive isocyanate compounds in the two-component adhesive will harden with moisture to become polymers and oligomers with urea bonds, which are believed to contribute to the improvement of heat resistance and moisture resistance of the cured coating film. Therefore, when the [NCO]/[OH] ratio is relatively small, for example, if it is about 1.5, the heat resistance and humidity resistance may be insufficient. In this case, for example, the polyol composition (A ) In the resin (A2) blending amount to deal with. In addition, when the [NCO]/[OH] ratio is relatively high, for example, if it is about 15.0, the coating film may become too hard due to the influence of the crosslinking density or the polymer or oligomer with urea bonds. The formability is reduced. In this case, it can be dealt with by increasing the blending amount of the polyester polyol (A1) in the polyol composition (A). In order to ensure the design freedom of the two-component adhesive and reliably improve the heat resistance and humidity resistance, the [NCO]/[OH] ratio is more preferably 2.0-10, and more preferably 2.5-8.0.

本發明之接著劑可為溶劑型或無溶劑型之任一形態。再者,本發明中所謂「溶劑型」之接著劑係指用於以下方法,即所謂乾式層壓法之形態:將接著劑塗佈至基材後,利用烘箱等進行加熱而使塗膜中之有機溶劑揮發,其後,與其它基材貼合。多元醇組成物(A)及聚異氰酸酯組成物(B)之任一者、或兩者包含能夠使本發明中使用之上述多元醇組成物(A)或聚異氰酸酯組成物(B)溶解的溶解性較高之有機溶劑。於溶劑型之情形時,於多元醇組成物(A)或聚異氰酸酯組成物(B)之構成成分之製造時用作反應介質之有機溶劑有時亦進而於塗裝時用作稀釋劑。作為溶解性較高之有機溶劑,例如可列舉:乙酸乙酯、乙酸丁酯、乙酸賽璐蘇等酯類;丙酮、甲基乙基酮、異丁基酮、環己酮等酮類;四氫呋喃、二

Figure 109126611-A0304-12-0059-1
烷等醚類;甲苯、二甲苯等芳香族烴類;二氯甲烷、二氯乙烷等鹵代烴類;二甲亞碸、二甲基磺醯胺等。The adhesive of the present invention may be either a solvent type or a solventless type. Furthermore, the so-called "solvent type" adhesive in the present invention refers to the form used in the following method, the so-called dry lamination method: after the adhesive is applied to the substrate, it is heated in an oven or the like to make the coating film The organic solvent evaporates, and then it is bonded with other substrates. Either or both of the polyol composition (A) and the polyisocyanate composition (B) include a dissolution capable of dissolving the polyol composition (A) or the polyisocyanate composition (B) used in the present invention Organic solvents with higher performance. In the case of the solvent type, the organic solvent used as the reaction medium in the production of the constituent components of the polyol composition (A) or the polyisocyanate composition (B) may also be used as a diluent during coating. Examples of organic solvents with relatively high solubility include esters such as ethyl acetate, butyl acetate, and cellulose acetate; ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone; and tetrahydrofuran ,two
Figure 109126611-A0304-12-0059-1
Ethers such as alkanes; aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as methylene chloride and dichloroethane; dimethyl sulfide, dimethyl sulfonamide, etc.

於本說明書中,「無溶劑型」之接著劑係指以下接著劑之形態:多元醇組成物(A)及聚異氰酸酯組成物(B)實質上不含如上述之溶解性較高之有機溶劑,尤其是乙酸乙酯或甲基乙基酮,用於將接著劑塗佈至基材後,不歷經利用烘箱等進行加熱使溶劑揮發之步驟而與其它基材貼合之方法即所謂無溶劑層壓法。於多元醇組成物(A)或聚異氰酸酯組成物(B)之構成成分、或其原料之製造時用作反應介質之有機溶劑未被完全去除,而於多元醇組成物(A)或聚異氰酸酯組成物(B)中殘留有微量有機溶劑的情形時,理解為實質上不含有機溶劑。又,於多元醇組成物(A)包含低分子量醇之情形時,由於低分子量醇與聚異氰酸酯組成物(B)反應而成為塗膜之一部分,故而於塗佈後無需使其揮發。因此,此種形態亦視作無溶劑型接著劑。In this specification, the "solvent-free" adhesive refers to the form of the following adhesive: the polyol composition (A) and the polyisocyanate composition (B) are substantially free of organic solvents with higher solubility as mentioned above , Especially ethyl acetate or methyl ethyl ketone, is used to apply the adhesive to the substrate without going through the step of heating the solvent to volatilize the solvent in an oven, etc., and the method of bonding with other substrates is so-called solvent-free Laminating method. The organic solvent used as the reaction medium in the production of the constituent components of the polyol composition (A) or polyisocyanate composition (B) or its raw materials is not completely removed, and the polyol composition (A) or polyisocyanate When a trace amount of organic solvent remains in the composition (B), it is understood that the organic solvent is not substantially contained. In addition, when the polyol composition (A) contains a low-molecular-weight alcohol, the low-molecular-weight alcohol reacts with the polyisocyanate composition (B) to become a part of the coating film, so there is no need to volatilize it after coating. Therefore, this form is also regarded as a solvent-free adhesive.

於本發明之接著劑為溶劑型之情形時,由於黏度能夠藉由溶劑稀釋而降低,故而即便所使用之上述多元醇組成物(A)或聚異氰酸酯組成物(B)之黏度稍高,亦能夠使用。另一方面,於無溶劑型之情形時,於藉由加溫來降低黏度之特性上低黏度受到重視,作為降低黏度之手段,聚異氰酸酯組成物(B)多使用降低了作為黏度上升之誘因的芳香族濃度者。When the adhesive of the present invention is a solvent type, since the viscosity can be reduced by dilution with the solvent, even if the viscosity of the polyol composition (A) or polyisocyanate composition (B) used is slightly higher, can be used. On the other hand, in the case of the solvent-free type, low viscosity is valued in terms of the characteristics of reducing the viscosity by heating. As a means of reducing the viscosity, polyisocyanate composition (B) is mostly used as an inducement to increase the viscosity. The concentration of aromatics.

本發明之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、消泡劑、抗靜電劑、防霧劑等各種添加劑。The adhesive of the present invention may also contain various additives such as ultraviolet absorbers, antioxidants, silicon-based additives, fluorine-based additives, rheology control agents, defoamers, antistatic agents, and antifogging agents.

本發明之接著劑之用途並無特別限定,由於接著強度、成型性、耐濕熱性、耐熱性優異,故而作為一例,可較佳地用於電池用包裝材。The use of the adhesive of the present invention is not particularly limited, and since it is excellent in adhesive strength, moldability, moisture and heat resistance, and heat resistance, as an example, it can be preferably used as a battery packaging material.

<積層體> 本發明之積層體係使用本發明之接著劑並利用乾式層壓法或無溶劑層壓法將複數基材進行貼合而獲得。作為基材,可列舉由紙、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而獲得之合成樹脂膜、銅箔、鋁箔之類的金屬箔等。<Laminated body> The laminated system of the present invention uses the adhesive of the present invention and is obtained by laminating a plurality of substrates by a dry lamination method or a solvent-free lamination method. Examples of substrates include paper, olefin resins, acrylonitrile-butadiene-styrene copolymers (ABS resins), polyvinyl chloride resins, fluorine resins, poly(meth)acrylic resins, and carbonates. Synthetic resin films, copper foils, aluminum foils and other metal foils obtained from synthetic resins, polyamide resins, polyimide resins, polyphenylene ether resins, polyphenylene sulfide resins, or polyester resins .

基材之膜厚並無特別限制,例如可自10~400 μm進行選擇。為了提昇基材與接著劑之密接性,亦可對基材之供塗佈接著劑之面進行表面處理。作為該表面處理,可列舉電暈處理、電漿處理、臭氧處理、火焰處理、放射線處理等。The film thickness of the substrate is not particularly limited, and can be selected from 10 to 400 μm, for example. In order to improve the adhesion between the substrate and the adhesive, the surface of the substrate on which the adhesive is applied can also be surface-treated. Examples of the surface treatment include corona treatment, plasma treatment, ozone treatment, flame treatment, radiation treatment, and the like.

<電池用包裝材> 關於將本發明之積層體成型而得之成型體,作為一例,可合適地用作電池用包裝材。如圖1所示,電池用包裝材係由至少依序積層外層側基材層1、接著層2、金屬層3、及密封劑層4而成之積層體構成。於本發明之電池用包裝材中,外層側基材層1成為最外層,密封劑層4成為最內層。即,於電池之組裝時,藉由使位於電池元件之周緣之密封劑層4彼此熱熔接而將電池元件密封,可將電池元件密封。本發明之接著劑係用於接著層2。又,如圖2所示,本發明之電池用包裝材亦可於金屬層3與密封劑層4之間視需要而設置接著層5以提高該等之接著性。<Packaging materials for batteries> Regarding the molded body obtained by molding the laminate of the present invention, as an example, it can be suitably used as a battery packaging material. As shown in FIG. 1, the battery packaging material is composed of a laminate in which at least the outer layer side base material layer 1, the adhesive layer 2, the metal layer 3, and the sealant layer 4 are laminated in this order. In the battery packaging material of the present invention, the outer layer side base material layer 1 becomes the outermost layer, and the sealant layer 4 becomes the innermost layer. That is, when assembling the battery, the battery element can be sealed by thermally fusing the sealant layers 4 located on the periphery of the battery element to each other. The adhesive of the present invention is used for the adhesive layer 2. In addition, as shown in FIG. 2, the battery packaging material of the present invention can also be provided with an adhesive layer 5 between the metal layer 3 and the sealant layer 4 as necessary to improve the adhesion.

(外層側基材層1) 於本發明之電池用包裝材中,外層側基材層1係形成最外層之層。關於形成外層側基材層1之素材,只要為具備絕緣性者,則並無特別限制,可列舉聚酯樹脂、聚醯胺樹脂、環氧樹脂、丙烯酸樹脂、氟樹脂、聚胺酯樹脂、矽樹脂、酚樹脂、及該等之混合物或共聚物等之樹脂膜。該等之中,較佳為聚酯樹脂、聚醯胺樹脂,更佳為雙軸延伸聚酯樹脂、雙軸延伸聚醯胺樹脂。作為聚酯樹脂,具體而言,可列舉:聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯、聚萘二甲酸丁二酯、共聚聚酯、聚碳酸酯等。又,作為聚醯胺樹脂,具體而言,可列舉:尼龍6、尼龍6,6、尼龍6與尼龍6,6之共聚物、尼龍6,10、聚己二醯間苯二甲胺(MXD6)等。(Outer layer side base material layer 1) In the battery packaging material of the present invention, the outer layer side base material layer 1 forms the outermost layer. There are no particular restrictions on the material forming the outer substrate layer 1 as long as it is insulating, and examples include polyester resins, polyamide resins, epoxy resins, acrylic resins, fluororesins, polyurethane resins, and silicone resins. , Phenolic resins, and resin films such as mixtures or copolymers of these. Among these, polyester resins and polyamide resins are preferred, and biaxially stretched polyester resins and biaxially stretched polyamide resins are more preferred. Specific examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate, copolyester, Polycarbonate etc. In addition, as the polyamide resin, specifically, nylon 6, nylon 6,6, a copolymer of nylon 6 and nylon 6,6, nylon 6,10, polyhexamethylene diamide (MXD6 )Wait.

外層側基材層1可由1層樹脂膜形成,但為了提昇耐針孔性或絕緣性,亦可由2層以上樹脂膜所形成。於由多層樹脂膜形成外層側基材層1之情形時,樹脂膜彼此只要經由接著劑或接著性樹脂等接著成分進行積層即可,關於所使用之接著成分之種類或量等,與下述之接著層2或接著層5之情形相同。再者,作為使2層以上樹脂膜積層之方法,並無特別限制,可採用公知之方法,例如可列舉乾式層壓法、夾層層壓法等,較佳可列舉乾式層壓法。於藉由乾式層壓法進行積層之情形時,較佳為使用接著劑作為接著層。此時,作為接著層之厚度,例如為0.5~10 μm左右。The outer base material layer 1 may be formed of a single resin film, but in order to improve pinhole resistance or insulation, it may be formed of two or more resin films. When the outer base material layer 1 is formed of multiple resin films, the resin films can be laminated via adhesive or adhesive resin and other components. The types and amounts of the components used are as follows: The situation of the bonding layer 2 or the bonding layer 5 is the same. In addition, the method of laminating two or more resin films is not particularly limited, and a known method can be used, for example, dry lamination, sandwich lamination, etc., preferably dry lamination. In the case of lamination by a dry lamination method, it is preferable to use an adhesive as the adhesive layer. At this time, the thickness of the adhesive layer is, for example, about 0.5 to 10 μm.

關於外層側基材層1之厚度,只要電池用包裝材滿足上述物性,則並無特別限制,例如為10~50 μm左右,較佳為15~35 μm左右。於使用聚酯膜之情形時,厚度較佳為9 μm~50 μm,於使用聚醯胺膜之情形時,厚度較佳為10 μm~50 μm。作為包裝材,可確保充分的強度,並且可減小拉伸成型時或抽製成形時之應力,可使成形性提高。The thickness of the outer layer-side base material layer 1 is not particularly limited as long as the battery packaging material satisfies the above-mentioned physical properties. For example, it is about 10-50 μm, preferably about 15-35 μm. When a polyester film is used, the thickness is preferably 9 μm-50 μm, and when a polyamide film is used, the thickness is preferably 10 μm-50 μm. As a packaging material, it can ensure sufficient strength, and can reduce the stress during stretch molding or extraction molding, and improve formability.

(金屬層3) 於電池用包裝材中,金屬層3係除提昇電池用包裝材之強度以外,亦作為用以防止水蒸氣、氧、光等侵入至電池內部之障壁層而發揮功能之層。作為構成金屬層3之金屬,具體而言,可列舉鋁、不鏽鋼、鈦等,較佳為鋁。金屬層3可藉由金屬箔或金屬蒸鍍等而形成,較佳為藉由金屬箔而形成,進而較佳為藉由鋁箔而形成。又,為了接著之穩定化、防止溶解或腐蝕等,金屬層3較佳為至少一面,較佳為兩面進行過化學處理。此處,化學處理係指於金屬層之表面形成耐酸性皮膜之處理。(Metal layer 3) In the battery packaging material, the metal layer 3 not only enhances the strength of the battery packaging material, but also functions as a barrier layer for preventing water vapor, oxygen, light, etc. from entering the battery. As the metal constituting the metal layer 3, specifically, aluminum, stainless steel, titanium, etc. can be cited, and aluminum is preferred. The metal layer 3 can be formed by metal foil or metal vapor deposition, etc., is preferably formed by metal foil, and more preferably is formed by aluminum foil. Furthermore, in order to stabilize the bonding, prevent dissolution or corrosion, etc., the metal layer 3 preferably has at least one side, and preferably both sides have been chemically treated. Here, the chemical treatment refers to the treatment of forming an acid-resistant film on the surface of the metal layer.

關於金屬層3之厚度,只要電池用包裝材滿足上述物性,則並無特別限制,例如可設為10~50 μm左右,較佳為25~45 μm左右。The thickness of the metal layer 3 is not particularly limited as long as the battery packaging material satisfies the above-mentioned physical properties. For example, it can be about 10-50 μm, preferably about 25-45 μm.

(密封劑層4) 於本發明之電池用包裝材中,密封劑層4相當於最內層,係於電池之組裝時密封劑層彼此熱熔接而將電池元件密封之層。(Sealant layer 4) In the battery packaging material of the present invention, the sealant layer 4 corresponds to the innermost layer, and is a layer for sealing the battery elements by thermally fusing the sealant layers to each other when the battery is assembled.

關於密封劑層4所使用之樹脂成分,只要能夠熱熔接,則並無特別限制,例如可列舉聚烯烴、環狀聚烯烴、羧酸改質聚烯烴、羧酸改質環狀聚烯烴。The resin component used in the sealant layer 4 is not particularly limited as long as it can be thermally welded, and examples thereof include polyolefin, cyclic polyolefin, carboxylic acid-modified polyolefin, and carboxylic acid-modified cyclic polyolefin.

作為上述聚烯烴,具體而言,可列舉:低密度聚乙烯、中密度聚乙烯、高密度聚乙烯、線狀低密度聚乙烯等聚乙烯;均聚丙烯、聚丙烯之嵌段共聚物(例如丙烯與乙烯之嵌段共聚物)、聚丙烯之無規共聚物(例如丙烯與乙烯之無規共聚物)等聚丙烯;乙烯-丁烯-丙烯之三元共聚物等。該等聚烯烴之中,較佳可列舉聚乙烯及聚丙烯。As the above-mentioned polyolefins, specifically, polyethylenes such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, and linear low-density polyethylene; homopolypropylene and block copolymers of polypropylene (for example, Block copolymers of propylene and ethylene), random copolymers of polypropylene (such as random copolymers of propylene and ethylene) and other polypropylenes; ethylene-butene-propylene terpolymers, etc. Among these polyolefins, polyethylene and polypropylene are preferable.

上述環狀聚烯烴係烯烴與環狀單體之共聚物,關於作為上述環狀聚烯烴之構成單體之烯烴,例如可列舉乙烯、丙烯、4-甲基-1-戊烯、苯乙烯、丁二烯、異戊二烯等。又,關於作為上述環狀聚烯烴之構成單體之環狀單體,例如可列舉降莰烯等環狀烯;具體而言,可列舉環戊二烯、二環戊二烯、環己二烯、降莰二烯等環狀二烯等。該等聚烯烴之中,較佳可列舉環狀烯,進而較佳可列舉降莰烯。The above-mentioned cyclic polyolefin-based copolymer of an olefin and a cyclic monomer. Regarding the olefin as the constituent monomer of the above-mentioned cyclic polyolefin, for example, ethylene, propylene, 4-methyl-1-pentene, styrene, Butadiene, isoprene, etc. In addition, the cyclic monomers as the constituent monomers of the cyclic polyolefins include, for example, cyclic olefins such as norbornene; specifically, cyclopentadiene, dicyclopentadiene, and cyclohexadiene can be cited. Cyclic dienes such as alkenes, norbornadiene, etc. Among these polyolefins, cyclic olefins are preferred, and norbornene is more preferred.

上述羧酸改質聚烯烴係藉由利用羧酸使上述聚烯烴進行嵌段聚合或接枝聚合而改質而成之聚合物。作為改質所使用之羧酸,例如可列舉順丁烯二酸、丙烯酸、伊康酸、巴豆酸、順丁烯二酸酐、伊康酸酐等。The carboxylic acid-modified polyolefin is a polymer modified by block polymerization or graft polymerization of the polyolefin using carboxylic acid. Examples of the carboxylic acid used for modification include maleic acid, acrylic acid, itaconic acid, crotonic acid, maleic anhydride, and itaconic anhydride.

上述羧酸改質環狀聚烯烴係藉由以α,β-不飽和羧酸或其酐代替構成環狀聚烯烴之單體之一部分來進行共聚、或藉由使α,β-不飽和羧酸或其酐對環狀聚烯烴進行嵌段聚合或接枝聚合而獲得之聚合物。關於供羧酸改質之環狀聚烯烴,與上述相同。又,作為改質所使用之羧酸,與上述酸改質環烯烴共聚物之改質所使用者相同。The carboxylic acid-modified cyclic polyolefin is copolymerized by substituting α,β-unsaturated carboxylic acid or its anhydride for a part of the monomers constituting the cyclic polyolefin, or by making α,β-unsaturated carboxylic acid A polymer obtained by block polymerization or graft polymerization of an acid or its anhydride on a cyclic polyolefin. Regarding the cyclic polyolefin for carboxylic acid modification, it is the same as the above. In addition, the carboxylic acid used for the modification is the same as the one used for the modification of the acid-modified cycloolefin copolymer.

密封劑層4可由1種樹脂成分單獨地形成,又,亦可藉由將2種以上樹脂成分組合而成之摻合聚合物而形成。進而,密封劑層4可僅由1層而形成,亦可藉由相同或不同之樹脂成分由2層以上而形成。The sealant layer 4 may be formed by one type of resin component alone, or may be formed by a blended polymer obtained by combining two or more types of resin components. Furthermore, the sealant layer 4 may be formed of only one layer, or may be formed of two or more layers with the same or different resin components.

又,作為密封劑層4之厚度,只要電池用包裝材滿足上述物性,則並無特別限制,例如為10~100 μm左右,較佳為20~90 μm左右。The thickness of the sealant layer 4 is not particularly limited as long as the battery packaging material satisfies the above-mentioned physical properties. For example, it is about 10 to 100 μm, preferably about 20 to 90 μm.

(接著層5) 於本發明之電池用包裝材中,接著層5係為了使金屬層3與密封劑層4牢固地接著而於該等之間視需要而設置之層。(Next to layer 5) In the battery packaging material of the present invention, the adhesive layer 5 is a layer provided as necessary between the metal layer 3 and the sealant layer 4 in order to firmly adhere them.

接著層5係藉由能夠使金屬層3與密封劑層4接著之接著劑而形成。作為接著層5所使用之接著層,例如可使用將聚烯烴樹脂與多官能異氰酸酯組合而成之接著劑、將多元醇與多官能異氰酸酯組合而成之接著劑、改質聚烯烴樹脂、含有雜環狀化合物及硬化劑之接著劑。或者亦可將酸改質聚丙烯等接著劑利用T字模擠出機熔融擠出至金屬層上而形成接著層5,於上述接著層5重疊密封劑層4,而將金屬層3與密封劑層4貼合。 於接著層2及接著層5兩者必須老化之情形時,可一併老化。再者,藉由將老化溫度設為室溫~90℃,於2天~2週內完成硬化,而表現出成型性。The adhesive layer 5 is formed by an adhesive capable of adhering the metal layer 3 and the sealant layer 4. As the adhesive layer used for the adhesive layer 5, for example, an adhesive composed of a combination of polyolefin resin and polyfunctional isocyanate, an adhesive composed of a combination of polyol and polyfunctional isocyanate, modified polyolefin resin, and heterogeneous Adhesive for cyclic compounds and hardeners. Alternatively, an adhesive such as acid-modified polypropylene can be melt-extruded onto the metal layer using a T-die extruder to form the adhesive layer 5. The sealant layer 4 is superimposed on the adhesive layer 5, and the metal layer 3 and the sealant Layer 4 is attached. When both the adhesive layer 2 and the adhesive layer 5 must be aged, they can be aged together. Furthermore, by setting the aging temperature to room temperature to 90°C, curing is completed in 2 days to 2 weeks, thereby exhibiting moldability.

關於接著層5之厚度,只要電池用包裝材滿足上述物性,則並無特別限制,例如為0.5~50 μm左右,較佳為2~30 μm左右。The thickness of the adhesive layer 5 is not particularly limited as long as the battery packaging material satisfies the above-mentioned physical properties. For example, it is about 0.5-50 μm, preferably about 2-30 μm.

(塗佈層6) 於本發明之電池用包裝材中,為了提昇設計性、耐電解液性、耐摩擦性、成型性等,亦可視需要於外層側基材層1之上(外層側基材層1之與金屬層3相反之側)設置塗佈層6。塗佈層6係於組裝電池時位於最外層之層。(Coating layer 6) In the battery packaging material of the present invention, in order to improve design, electrolyte resistance, abrasion resistance, moldability, etc., it can also be placed on the outer layer side substrate layer 1 (the outer layer side substrate layer 1 and the metal The side opposite to layer 3) is provided with a coating layer 6. The coating layer 6 is the outermost layer when the battery is assembled.

塗佈層6例如可藉由聚偏二氯乙烯、聚酯樹脂、胺酯樹脂、丙烯酸樹脂、環氧樹脂等形成,較佳為藉由二液硬化型樹脂形成。作為形成塗佈層6之二液硬化型樹脂,例如可列舉二液硬化型胺酯樹脂、二液硬化型聚酯樹脂、二液硬化型環氧樹脂等。又,於塗佈層6中亦可摻合消光劑(matting agent)。The coating layer 6 can be formed of, for example, polyvinylidene chloride, polyester resin, urethane resin, acrylic resin, epoxy resin, etc., and is preferably formed of a two-component curing resin. Examples of the two-component curing resin for forming the coating layer 6 include two-component curing urethane resin, two-component curing polyester resin, and two-component curing epoxy resin. In addition, a matting agent may be blended in the coating layer 6.

作為消光劑,例如可列舉粒徑為0.5 nm~5 μm左右之微粒子。關於消光劑之材質,並無特別限制,例如可列舉金屬、金屬氧化物、無機物、有機物等。又,關於消光劑之形狀,亦無特別限制,例如可列舉球狀、纖維狀、板狀、不定形、氣球狀等。作為消光劑,具體而言,可列舉:滑石、二氧化矽(silica)、石墨、高嶺土、膠嶺石(montmorilloide)、蒙脫石、合成雲母、菱水鎂鋁石、矽膠、沸石、氫氧化鋁、氫氧化鎂、氧化鋅、氧化鎂、氧化鋁、氧化釹、氧化銻、氧化鈦、氧化鈰、硫酸鈣、硫酸鋇、碳酸鈣,矽酸鈣、碳酸鋰、苯甲酸鈣,草酸鈣,硬脂酸鎂、碳黑、奈米碳管類、高熔點尼龍、交聯丙烯酸、交聯苯乙烯、交聯聚乙烯、苯胍𠯤、金、鋁、銅、鎳等。該等消光劑可單獨使用,亦可將2種以上組合使用。該等消光劑之中,就分散穩定性或成本等之觀點而言,較佳為二氧化矽、硫酸鋇、氧化鈦。又,關於消光劑,亦可對表面實施絕緣處理、高分散性處理等各種表面處理。As the matting agent, for example, fine particles having a particle diameter of about 0.5 nm to 5 μm can be cited. The material of the matting agent is not particularly limited, and examples thereof include metals, metal oxides, inorganic substances, and organic substances. In addition, the shape of the matting agent is not particularly limited, and examples thereof include spherical, fibrous, plate-shaped, amorphous, and balloon-shaped. Specific examples of matting agents include talc, silica, graphite, kaolin, montmorilloide, montmorillonite, synthetic mica, magnesia, silica gel, zeolite, and hydroxide Aluminum, magnesium hydroxide, zinc oxide, magnesium oxide, aluminum oxide, neodymium oxide, antimony oxide, titanium oxide, cerium oxide, calcium sulfate, barium sulfate, calcium carbonate, calcium silicate, lithium carbonate, calcium benzoate, calcium oxalate, Magnesium stearate, carbon black, carbon nanotubes, high melting point nylon, cross-linked acrylic, cross-linked styrene, cross-linked polyethylene, benzoguanidine, gold, aluminum, copper, nickel, etc. These matting agents may be used alone or in combination of two or more kinds. Among these matting agents, from the viewpoint of dispersion stability and cost, silicon dioxide, barium sulfate, and titanium oxide are preferred. In addition, regarding the matting agent, various surface treatments such as insulation treatment and high-dispersibility treatment may be applied to the surface.

作為形成塗佈層6之方法,並無特別限制,例如可列舉將形成塗佈層6之二液硬化型樹脂塗佈於外層側基材層1之一表面上的方法。於摻合消光劑之情形時,只要於二液硬化型樹脂添加消光劑並混合後進行塗佈即可。The method of forming the coating layer 6 is not particularly limited. For example, a method of applying the two-liquid hardening resin for forming the coating layer 6 to one surface of the outer layer side base material layer 1 can be cited. In the case of blending a matting agent, it is only necessary to add a matting agent to the two-component hardening resin and mix it and apply it.

(電池用包裝材之製造方法) 關於本發明之電池用包裝材之製造方法,只要可獲得使特定組成之各層積層而成之積層體,則並無特別限制,例示以下方法。(Method of manufacturing battery packaging materials) There are no particular limitations on the method of manufacturing the battery packaging material of the present invention as long as a laminate obtained by laminating each layer of a specific composition can be obtained, and the following methods are exemplified.

首先,形成依序積層外層側基材層1、接著層2、及金屬層3而成之積層體(以下,有時亦標記為「積層體A」)。關於積層體A之形成,具體而言,可藉由以下之乾式層壓法而進行:於外層側基材層1上或視需要而表面經化學處理之金屬層3上利用擠出法、凹版塗佈法、輥塗法等塗佈方法塗佈本發明之接著劑並乾燥後,使該金屬層3或外層側基材層1積層並使接著層2硬化。First, a laminate (hereinafter, sometimes referred to as "Laminate A") in which the outer layer side base material layer 1, the adhesive layer 2, and the metal layer 3 are sequentially laminated is formed. Regarding the formation of the laminate A, specifically, it can be carried out by the following dry lamination method: on the outer layer side base material layer 1 or on the metal layer 3 whose surface is chemically treated as necessary, using an extrusion method or a gravure After coating and drying the adhesive of the present invention by coating methods such as coating method and roll coating method and drying, the metal layer 3 or the outer layer side base material layer 1 is laminated and the adhesive layer 2 is cured.

繼而,使密封劑層4積層於積層體A之金屬層3上。於使密封劑層4直接積層於金屬層3上之情形時,只要藉由凹版塗佈法、輥塗法等方法於積層體A之金屬層3上塗佈構成密封劑層4之樹脂成分即可。又,於在金屬層3與密封劑層4之間設置接著層5之情形時,例如可列舉以下方法:藉由於積層體A之金屬層3上共擠壓接著層5及密封劑層4而進行積層(共擠壓層壓法);另外形成積層接著層5與密封劑層4而成之積層體,藉由熱層壓法將其積層於積層體A之金屬層3上;於積層體A之金屬層3上將用以形成接著層5之接著劑藉由擠出法或於溶液塗佈之高溫進行乾燥並進而進行燒接之方法進行積層,並藉由熱層壓法將預先製膜為片狀之密封劑層4積層於該接著層5上;使已熔融之接著層5流入至積層體A之金屬層3與預先製膜為片狀之密封劑層4之間,並且經由接著層5將積層體A與密封劑層4貼合(夾層層壓法)等。Then, the sealant layer 4 is laminated on the metal layer 3 of the laminate A. When the sealant layer 4 is directly laminated on the metal layer 3, it is only necessary to coat the resin component constituting the sealant layer 4 on the metal layer 3 of the laminate A by a method such as a gravure coating method or a roll coating method. can. Moreover, when the adhesive layer 5 is provided between the metal layer 3 and the sealant layer 4, for example, the following method can be cited: by co-extruding the adhesive layer 5 and the sealant layer 4 on the metal layer 3 of the laminate A Laminate (co-extrusion lamination method); in addition, a laminate of the laminate adhesive layer 5 and the sealant layer 4 is formed, and the laminate is laminated on the metal layer 3 of the laminate A by the thermal lamination method; in the laminate On the metal layer 3 of A, the adhesive used to form the adhesive layer 5 is laminated by an extrusion method or a method of drying at a high temperature of solution coating and then sintering, and prefabricated by a thermal lamination method The sheet-shaped sealant layer 4 is laminated on the adhesive layer 5; the melted adhesive layer 5 flows between the metal layer 3 of the laminate A and the sealant layer 4 previously formed into a sheet-like film, and passes through Next, in the layer 5, the laminated body A and the sealant layer 4 are bonded together (sandwich lamination method) and the like.

於設置塗佈層6之情形時,於外層側基材層1之與金屬層3相反之側之表面積層塗佈層6。塗佈層6例如將形成塗佈層6之上述樹脂塗佈於外層側基材層1之表面而形成。再者,於外層側基材層1之表面積層金屬層3之步驟與在外層側基材層1之表面積層塗佈層6之步驟的順序並無特別限制。例如,亦可於外層側基材層1之表面形成塗佈層6後,於外層側基材層1之與塗佈層6相反之側之表面形成金屬層3。When the coating layer 6 is provided, the surface area layer coating layer 6 on the side opposite to the metal layer 3 of the outer layer side base material layer 1. The coating layer 6 is formed, for example, by coating the above-mentioned resin forming the coating layer 6 on the surface of the outer layer side base material layer 1. Furthermore, the order of the step of the surface area layer metal layer 3 of the outer layer side base material layer 1 and the step of the surface area layer coating layer 6 of the outer layer side base material layer 1 is not particularly limited. For example, after the coating layer 6 is formed on the surface of the outer substrate layer 1, the metal layer 3 may be formed on the surface of the outer substrate layer 1 opposite to the coating layer 6.

以上述方式形成由視需要而設置之塗佈層6/外層側基材層1/接著層2/視需要表面經化學處理之金屬層3/視需要而設置之接著層5/密封劑層4構成之積層體,為了加強接著層2及視需要而設置之接著層5之接著性,亦可進而供於熱輥接觸式、熱風式、近或遠紅外線式等之加熱處理。作為此種加熱處理之條件,例如可列舉於80~250℃且1~5分鐘。In the above manner, the coating layer 6/outer layer side base material layer 1/adhesive layer 2 provided as needed/metal layer with chemically treated surface as required 3/adhesive layer 5 provided as needed/sealant layer 4 In order to strengthen the adhesiveness of the adhesive layer 2 and the adhesive layer 5 provided as needed, the laminated body constituted may be further subjected to heating treatments such as a heat roller contact type, a hot air type, a near or far infrared type, and the like. As a condition of such a heat treatment, 80-250 degreeC and 1 to 5 minutes are mentioned, for example.

於本發明之電池用包裝材中,關於構成積層體之各層,為了使製膜性、積層化加工、最終產品2次加工(袋化、壓紋成型)適性等提昇或穩定化,亦可視需要實施電暈處理、噴砂處理、氧化處理、臭氧處理等表面活化處理。In the battery packaging material of the present invention, regarding each layer constituting the laminate, in order to improve or stabilize the film-forming properties, layering processing, and the suitability of the final product for secondary processing (bagging, embossing), etc., it may be possible to improve or stabilize it. Perform surface activation treatments such as corona treatment, sandblasting treatment, oxidation treatment, and ozone treatment.

<電池用容器> 本發明之電池用容器可使用上述電池用包裝材,以外層側基材層1構成凸面、密封劑層4構成凹面之方式進行成型而獲得。 再者,作為凹部之成型方法,有如下方法。 ・加熱壓空成型法:將電池用包裝材夾於具有供給高溫、高壓之空氣的孔之下模與具有袋形狀之凹部之上模,使之加熱軟化並同時供給空氣而形成凹部之方法。 ・預熱器平板式壓空成型法:使電池用包裝材加熱軟化後,將之夾於具有供給高壓之空氣的孔之下模與具有袋形狀之凹部之上模,供給空氣而形成凹部之方法。 ・滾筒式真空成型法:將電池用包裝材利用加熱滾筒局部加熱軟化後,對具有袋形狀之凹部的滾筒之該凹部進行抽真空以成型凹部之方法。 ・銷釘(pin)成型法:將底材片加熱軟化後利用袋形狀之凹凸模具進行壓接之方法。 ・預熱器助壓塞(plug assist)壓空成型法:其係使電池用包裝材加熱軟化後,將其夾於具有供給高壓之空氣的孔之下模與具有袋形狀之凹部之上模,供給空氣以形成凹部的方法,且於成型時使凸形狀之塞(plug)上升及下降以輔助成型。<Battery container> The battery container of the present invention can be obtained by using the above-mentioned battery packaging material, and molding the outer layer side base material layer 1 to form a convex surface and the sealant layer 4 to form a concave surface. Furthermore, as a method of forming the recess, there are the following methods. ・Heat and air pressure molding method: A method in which battery packaging materials are sandwiched between a lower mold with holes for supplying high-temperature and high-pressure air and an upper mold with a pocket-shaped recess, which is heated and softened while supplying air to form a recess. ・Preheater plate-type compression molding method: After heating and softening the battery packaging material, it is clamped between the lower mold with a hole for supplying high-pressure air and the upper mold with a pocket-shaped concave portion, and the air is supplied to form the concave portion. method. ・Drum-type vacuum forming method: The battery packaging material is locally heated and softened by a heating roller, and then the recessed portion of the roller with a pocket-shaped recess is vacuumed to form the recessed portion. ・Pin molding method: A method in which the substrate sheet is heated and softened and then crimped by a bag-shaped concave-convex mold. ・Preheater plug assist (plug assist) compression molding method: This is a method of heating and softening the battery packaging material, and then sandwiching it between a lower mold with a hole for supplying high-pressure air and an upper mold with a pocket-shaped recess , The method of supplying air to form the concave part, and raising and lowering the convex plug during molding to assist the molding.

其中,作為加熱真空成型法之預熱器助壓塞壓空成型法就可均勻地獲得成型後之底材之厚度之方面而言較佳。Among them, the preheater-assisted plug-in-air molding method as a heating vacuum molding method is preferable in terms of uniformly obtaining the thickness of the molded substrate.

(電池用包裝材之用途) 本發明之電池用包裝材係用作密封正極、負極、電解質等電池元件並進行收容之電池用容器。(Use of packaging materials for batteries) The battery packaging material of the present invention is used as a battery container for sealing and accommodating battery elements such as positive electrodes, negative electrodes, and electrolytes.

具體而言,利用本發明之電池用包裝材以與上述正極及負極各者連接之金屬端子向外側突出之狀態,並以能夠於電池元件之周緣形成凸緣部(密封劑層彼此接觸之區域)之方式,被覆至少具備正極、負極、及電解質之電池元件,將上述凸緣部之密封劑層彼此進行熱封以進行密封,藉此提供使用電池用包裝材之電池。再者,於使用本發明之電池用包裝材來收容電池元件之情形時,係以本發明之電池用包裝材之密封劑部分成為內側(與電池元件相接之面)之方式而使用。Specifically, the battery packaging material of the present invention is used in a state where the metal terminals connected to each of the above-mentioned positive electrode and negative electrode protrude outward, and a flange portion (a region where the sealant layers contact each other) can be formed on the periphery of the battery element In the method of ), a battery element with at least a positive electrode, a negative electrode, and an electrolyte is covered, and the sealant layers of the flange portion are heat-sealed to seal each other, thereby providing a battery using a battery packaging material. Furthermore, when the battery packaging material of the present invention is used to house battery elements, it is used in such a way that the sealant part of the battery packaging material of the present invention becomes the inner side (the surface in contact with the battery element).

本發明之電池用包裝材可用於一次電池、二次電池之任一者,較佳為可用於二次電池。關於應用本發明之電池用包裝材之二次電池之種類,並無特別限制,例如可列舉:鋰離子電池、鋰離子聚合物電池、鉛蓄電池、鎳-氫蓄電池、鎳-鎘蓄電池、鎳-鐵蓄電池、鎳-鋅蓄電池、氧化銀-鋅蓄電池、金屬空氣電池、多價陽離子電池、蓄電器(condenser)、電容器(capacitor)等。該等二次電池之中,作為本發明之電池用包裝材之較佳之應用對象,可列舉鋰離子電池及鋰離子聚合物電池。The battery packaging material of the present invention can be used for either primary batteries or secondary batteries, and is preferably used for secondary batteries. Regarding the type of secondary battery to which the battery packaging material of the present invention is applied, there is no particular limitation. Examples include: lithium ion batteries, lithium ion polymer batteries, lead storage batteries, nickel-hydrogen storage batteries, nickel-cadmium storage batteries, and nickel- Iron batteries, nickel-zinc batteries, silver oxide-zinc batteries, metal-air batteries, multivalent cation batteries, condensers, capacitors, etc. Among these secondary batteries, as a preferable application target of the battery packaging material of the present invention, lithium ion batteries and lithium ion polymer batteries can be cited.

<積層體、成型體之其它用途> 本發明之積層體、積層體之成型體之用途並不限於電池用包裝材。本發明之積層體亦可使用作為以保護食品或醫藥品、日用品為目的之多層包裝材料。使用作為多層包裝材料時,其層構成可根據内容物或使用環境、使用形態來變化。<Other uses of laminated body and molded body> The use of the laminated body and the molded body of the laminated body of the present invention is not limited to battery packaging materials. The laminate of the present invention can also be used as a multilayer packaging material for the purpose of protecting food, medicines, and daily necessities. When used as a multilayer packaging material, its layer structure can be changed according to the content, use environment, and use form.

作為包裝材料的一種形式,可列舉:將積層體之密封劑膜之面對向地疊合後,熱密封其周邊端部而得者。作為製袋方法,可列舉以下方法:將本發明之積層體折彎或重疊,使其内層之面(密封劑膜之面)對向,將其周邊端部例如以側面密封型、二方密封型、三方密封型、四方密封型、信封貼附密封型、合掌貼附密封型、帶褶密封型、平底密封型、方底密封型、角撐型、其它熱密封型等形態進行熱密封。本發明之包裝材可根據内容物或使用環境、使用形態而採用各種形態。亦可為自立性包裝材(自立袋)等。作為熱密封之方法,可以桿密封、回轉輥密封、帶式密封、脈衝密封、高頻密封、超音波密封等公知的方法來進行。As one form of the packaging material, there may be mentioned a laminate obtained by laminating the sealant films of the laminate face to face, and then heat sealing the peripheral ends thereof. As a method of making a bag, the following method can be cited: bending or overlapping the laminate of the present invention so that the inner layer surface (the surface of the sealant film) faces each other, and the peripheral ends thereof are, for example, side-sealed or two-way sealed Type, three-sided sealing type, square sealing type, envelope attaching seal type, folding palm attaching seal type, pleated seal type, flat bottom seal type, square bottom seal type, gusset type, other heat seal types and other forms for heat sealing. The packaging material of the present invention can adopt various forms according to the content, use environment, and use form. It can also be self-supporting packaging materials (self-supporting bags), etc. As a method of heat sealing, it can be performed by known methods such as rod sealing, rotary roll sealing, belt sealing, pulse sealing, high frequency sealing, ultrasonic sealing, and the like.

作為包裝材料之其它形態,可列舉:泡鼓包裝(亦稱為擠壓包裝或PTP)。泡鼓包裝係藉由將形成有一個或複數收納部之積層體與覆蓋膜接合來密封收納部。本發明之積層體由於成型性優異,因此可用作形成收納部之積層體,亦可用作覆蓋膜。As other forms of packaging materials, blister packaging (also known as squeeze packaging or PTP) can be cited. The blister package seals the storage portion by joining a laminate in which one or a plurality of storage portions are formed and a cover film. Since the laminated body of this invention is excellent in moldability, it can be used as a laminated body which forms a storage part, and can also be used as a cover film.

本發明亦可用於包裝材以外之用途,作為一例,可列舉裝飾成型密封之基材,但並不限定於此。可合適地使用於需要成型性、耐熱性、耐濕熱性之任一功能或複數功能的用途。 [實施例]The present invention can also be used for applications other than packaging materials. As an example, a base material for decorative molding and sealing can be cited, but it is not limited to this. It can be suitably used for applications requiring any function or multiple functions of moldability, heat resistance, and moisture and heat resistance. [Example]

以下,列舉具體之合成例、實施例而更詳細地說明本發明,但本發明並不限定於該等實施例。再者,於以下之例中,關於「份」及「%」,只要無特別表明,則分別表示「質量份」及「質量%」。Hereinafter, specific synthesis examples and examples are given to explain the present invention in more detail, but the present invention is not limited to these examples. Furthermore, in the following examples, as for "parts" and "%", unless otherwise specified, they represent "parts by mass" and "% by mass", respectively.

<聚酯多元醇之製備> (合成例1)聚酯多元醇(A1-1)之合成 使用間苯二甲酸300.3份、對苯二甲酸300.3份、新戊二醇37.7份、乙二醇101.0份、1,9-壬二醇260.7份,按照慣用方法合成聚酯多元醇。將所獲得之聚酯多元醇利用乙酸乙酯稀釋至樹脂固形物成分60%,獲得數量平均分子量(Mn)為3000、重量平均分子量(Mw)為16,000、樹脂羥值(固形物成分換算)為19.2 mgKOH/g、樹脂酸值(固形物成分換算)為0.55 mgKOH/g、玻璃轉移溫度(Tg)為10.7℃之聚酯多元醇(A1-1)。<Preparation of polyester polyol> (Synthesis example 1) Synthesis of polyester polyol (A1-1) Using 300.3 parts of isophthalic acid, 300.3 parts of terephthalic acid, 37.7 parts of neopentyl glycol, 101.0 parts of ethylene glycol, and 260.7 parts of 1,9-nonanediol, the polyester polyol was synthesized according to a conventional method. The obtained polyester polyol is diluted with ethyl acetate to 60% of the resin solid content, and the number average molecular weight (Mn) is 3000, the weight average molecular weight (Mw) is 16,000, and the resin hydroxyl value (calculated as solid content) is 19.2 mgKOH/g, resin acid value (conversion of solid content) of 0.55 mgKOH/g, glass transition temperature (Tg) of 10.7 ℃ polyester polyol (A1-1).

(合成例2)聚酯多元醇(A1-2)之合成 使用間苯二甲酸424.8份、對苯二甲酸182.0份、新戊二醇57.1份、1,6-己二醇215.8份、乙二醇34.0份、3-甲基-1,5-戊二醇86.3份,按照慣用方法合成聚酯多元醇。將所獲得之聚酯多元醇利用乙酸乙酯稀釋至樹脂固形物成分60%,獲得數量平均分子量(Mn)為11,200、重量平均分子量(Mw)為25,900、樹脂羥值(固形物成分換算)為10.8 mgKOH/g、樹脂酸值(固形物成分換算)為2.2 mgKOH/g、玻璃轉移溫度(Tg)為15.8℃之聚酯多元醇(A1-2)。(Synthesis example 2) Synthesis of polyester polyol (A1-2) Used 424.8 parts of isophthalic acid, 182.0 parts of terephthalic acid, 57.1 parts of neopentyl glycol, 215.8 parts of 1,6-hexanediol, 34.0 parts of ethylene glycol, 3-methyl-1,5-pentanediol 86.3 parts, synthetic polyester polyol according to the usual method. The obtained polyester polyol is diluted with ethyl acetate to 60% of the resin solid content, and the number average molecular weight (Mn) is 11,200, the weight average molecular weight (Mw) is 25,900, and the resin hydroxyl value (calculated as solid content) is 10.8 mgKOH/g, resin acid value (conversion of solid content) of 2.2 mgKOH/g, glass transition temperature (Tg) of 15.8 ℃ polyester polyol (A1-2).

(合成例3)聚酯多元醇(A1-3)之合成 使用間苯二甲酸387.5份、對苯二甲酸166.1份、新戊二醇52.1份、1,6-己二醇167.4份、1,9-壬二醇227.0份,按照慣用方法合成聚酯多元醇。將所獲得之聚酯多元醇利用乙酸乙酯稀釋至樹脂固形物成分60%,獲得數量平均分子量(Mn)為3,050、重量平均分子量(Mw)為19,640、樹脂羥值(固形物成分換算)為13.8 mgKOH/g、樹脂酸值(固形物成分換算)為1.1 mgKOH/g、玻璃轉移溫度(Tg)為-3.6℃之聚酯多元醇(A1-3)。(Synthesis example 3) Synthesis of polyester polyol (A1-3) Using 387.5 parts of isophthalic acid, 166.1 parts of terephthalic acid, 52.1 parts of neopentyl glycol, 167.4 parts of 1,6-hexanediol, and 227.0 parts of 1,9-nonanediol, the polyester polyol was synthesized according to the usual method . The obtained polyester polyol was diluted with ethyl acetate to a resin solid content of 60%, and the number average molecular weight (Mn) was 3,050, the weight average molecular weight (Mw) was 19,640, and the resin hydroxyl value (in terms of solid content) was Polyester polyol (A1-3) with 13.8 mgKOH/g, resin acid value (calculated as solid content) of 1.1 mgKOH/g, and glass transition temperature (Tg) of -3.6°C.

(合成例4)聚酯多元醇(A1-4)之合成 使用間苯二甲酸303.3份、對苯二甲酸303.3份、新戊二醇37.7份、乙二醇101.0份、1,9-壬二醇260.7份,按照慣用方法合成聚酯多元醇。將所獲得之聚酯多元醇利用乙酸乙酯稀釋至樹脂固形物成分60%,獲得數量平均分子量(Mn)為1,980、重量平均分子量(Mw)為19,920、樹脂羥值(固形物成分換算)為13.8 mgKOH/g、樹脂酸值(固形物成分換算)為0.46 mgKOH/g、玻璃轉移溫度(Tg)為22.5℃之聚酯多元醇(A1-4)。(Synthesis example 4) Synthesis of polyester polyol (A1-4) Using 303.3 parts of isophthalic acid, 303.3 parts of terephthalic acid, 37.7 parts of neopentyl glycol, 101.0 parts of ethylene glycol, and 260.7 parts of 1,9-nonanediol, the polyester polyol was synthesized according to the usual method. The obtained polyester polyol was diluted with ethyl acetate to a resin solid content of 60%, and the number average molecular weight (Mn) was 1,980, the weight average molecular weight (Mw) was 19,920, and the resin hydroxyl value (calculated as solid content) was Polyester polyol (A1-4) with 13.8 mgKOH/g, resin acid value (calculated as solid content) of 0.46 mgKOH/g, and glass transition temperature (Tg) of 22.5°C.

(合成例5)聚酯多元醇(A1-5)之合成 使用間苯二甲酸303.3份、對苯二甲酸303.3份、新戊二醇37.7份、乙二醇101.0份、1,9-壬二醇260.7份,按照慣用方法合成聚酯多元醇。將所獲得之聚酯多元醇利用乙酸乙酯稀釋至樹脂固形物成分60%,獲得數量平均分子量(Mn)為2,600、重量平均分子量(Mw)為11,000、樹脂羥值(固形物成分換算)為30.7 mgKOH/g、樹脂酸值(固形物成分換算)為0.51 mgKOH/g、玻璃轉移溫度(Tg)為7.3℃之聚酯多元醇(A1-5)。(Synthesis example 5) Synthesis of polyester polyol (A1-5) Using 303.3 parts of isophthalic acid, 303.3 parts of terephthalic acid, 37.7 parts of neopentyl glycol, 101.0 parts of ethylene glycol, and 260.7 parts of 1,9-nonanediol, the polyester polyol was synthesized according to the usual method. The obtained polyester polyol was diluted with ethyl acetate to 60% of the resin solid content, and the number average molecular weight (Mn) was 2,600, the weight average molecular weight (Mw) was 11,000, and the resin hydroxyl value (calculated as solid content) was Polyester polyol (A1-5) with 30.7 mgKOH/g, resin acid value (calculated as solid content) of 0.51 mgKOH/g, and glass transition temperature (Tg) of 7.3°C.

(合成例6)聚酯多元醇(A1-6)之合成 使用間苯二甲酸365.7份、對苯二甲酸156.7份、新戊二醇49.1份、1,9-壬二醇428.4份,按照慣用方法合成聚酯多元醇。將所獲得之聚酯多元醇利用乙酸乙酯稀釋至樹脂固形物成分60%,獲得數量平均分子量(Mn)為2,300、重量平均分子量(Mw)為18,220、樹脂羥值(固形物成分換算)為16.8 mgKOH/g、樹脂酸值(固形物成分換算)為0.71 mgKOH/g、玻璃轉移溫度(Tg)為-11.0℃之聚酯多元醇(A1-6)。(Synthesis example 6) Synthesis of polyester polyol (A1-6) Using 365.7 parts of isophthalic acid, 156.7 parts of terephthalic acid, 49.1 parts of neopentyl glycol, and 428.4 parts of 1,9-nonanediol, the polyester polyol was synthesized according to the usual method. The obtained polyester polyol was diluted with ethyl acetate to 60% of the resin solid content, and the number average molecular weight (Mn) was 2,300, the weight average molecular weight (Mw) was 18,220, and the resin hydroxyl value (in terms of solid content) was Polyester polyol (A1-6) with 16.8 mgKOH/g, resin acid value (calculated as solid content) of 0.71 mgKOH/g, and glass transition temperature (Tg) of -11.0°C.

(合成例7)聚酯多元醇(A1-7)之合成 使用間苯二甲酸261.2份、對苯二甲酸261.2份、新戊二醇49.1份、1,9-壬二醇428.4份,按照慣用方法合成聚酯多元醇。將所獲得之聚酯多元醇利用乙酸乙酯稀釋至樹脂固形物成分60%,獲得數量平均分子量(Mn)為3,000、重量平均分子量(Mw)為25,160、樹脂羥值(固形物成分換算)為10.0 mgKOH/g、樹脂酸值(固形物成分換算)為0.93 mgKOH/g、玻璃轉移溫度(Tg)為-9.1℃之聚酯多元醇(A1-7)。(Synthesis example 7) Synthesis of polyester polyol (A1-7) Using 261.2 parts of isophthalic acid, 261.2 parts of terephthalic acid, 49.1 parts of neopentyl glycol, and 428.4 parts of 1,9-nonanediol, the polyester polyol was synthesized according to the usual method. The obtained polyester polyol is diluted with ethyl acetate to 60% of the resin solid content, and the number average molecular weight (Mn) is 3,000, the weight average molecular weight (Mw) is 25,160, and the resin hydroxyl value (calculated as solid content) is Polyester polyol (A1-7) with 10.0 mgKOH/g, resin acid value (calculated as solid content) of 0.93 mgKOH/g, and glass transition temperature (Tg) of -9.1°C.

(合成例8)聚酯多元醇(A1-8)之合成 使用間苯二甲酸273.9份、對苯二甲酸273.9份、新戊二醇51.5份、乙二醇30.7份、1,9-壬二醇370.0份,按照慣用方法合成聚酯多元醇。將所獲得之聚酯多元醇利用乙酸乙酯稀釋至樹脂固形物成分60%,獲得數量平均分子量(Mn)為5,440、重量平均分子量(Mw)為26,220、樹脂羥值(固形物成分換算)為16.0 mgKOH/g、樹脂酸值(固形物成分換算)為1.2 mgKOH/g、玻璃轉移溫度(Tg)為-3.0℃之聚酯多元醇(A1-8)。(Synthesis example 8) Synthesis of polyester polyol (A1-8) Using 273.9 parts of isophthalic acid, 273.9 parts of terephthalic acid, 51.5 parts of neopentyl glycol, 30.7 parts of ethylene glycol, and 370.0 parts of 1,9-nonanediol, the polyester polyol was synthesized according to a conventional method. The obtained polyester polyol is diluted with ethyl acetate to 60% of the resin solid content, and the number average molecular weight (Mn) is 5,440, the weight average molecular weight (Mw) is 26,220, and the resin hydroxyl value (calculated as solid content) is Polyester polyol (A1-8) with 16.0 mgKOH/g, resin acid value (calculated as solid content) of 1.2 mgKOH/g, and glass transition temperature (Tg) of -3.0°C.

(合成例9)樹脂(A2)之合成 使用對苯二甲酸697.2份、乙二醇72.9份、1,2-丙二醇229.9份,按照慣用方法獲得聚酯多元醇。將所獲得之聚酯多元醇利用甲基乙基酮稀釋至樹脂固形物成分30%,獲得數量平均分子量(Mn)為8,400、重量平均分子量(Mw)為61,300、樹脂羥值(固形物成分換算)為5.0 mgKOH/g、樹脂酸值(固形物成分換算)為4.0 mgKOH/g、玻璃轉移溫度為84℃之聚酯多元醇。將此聚酯多元醇用作為樹脂(A2)。(Synthesis example 9) Synthesis of resin (A2) Using 697.2 parts of terephthalic acid, 72.9 parts of ethylene glycol, and 229.9 parts of 1,2-propylene glycol, polyester polyol was obtained according to a conventional method. Dilute the obtained polyester polyol with methyl ethyl ketone to 30% of the resin solid content to obtain a number average molecular weight (Mn) of 8,400, weight average molecular weight (Mw) of 61,300, and resin hydroxyl value (converted to solid content) ) Is a polyester polyol with 5.0 mgKOH/g, resin acid value (in terms of solid content) of 4.0 mgKOH/g, and glass transition temperature of 84°C. This polyester polyol is used as the resin (A2).

(合成例10)聚酯多元醇(A3-1)之合成 使用間苯二甲酸170.2份、對苯二甲酸407.8份、苯偏三酸酐11.1份、新戊二醇47.8份、1,6-己二醇363.1份,按照慣用方法合成聚酯多元醇。將所獲得之聚酯多元醇利用乙酸乙酯稀釋至樹脂固形物成分58%,獲得數量平均分子量(Mn)為6,200、重量平均分子量(Mw)為18,500、樹脂羥值(固形物成分換算)為21.9 mgKOH/g、樹脂酸值(固形物成分換算)為0.74 mgKOH/g、玻璃轉移溫度(Tg)為7.3℃之聚酯多元醇(A3-1)。(Synthesis example 10) Synthesis of polyester polyol (A3-1) Using 170.2 parts of isophthalic acid, 407.8 parts of terephthalic acid, 11.1 parts of trimellitic anhydride, 47.8 parts of neopentyl glycol, and 363.1 parts of 1,6-hexanediol, the polyester polyol was synthesized according to the usual method. The obtained polyester polyol was diluted with ethyl acetate to 58% of the resin solid content, and the number average molecular weight (Mn) was 6,200, the weight average molecular weight (Mw) was 18,500, and the resin hydroxyl value (in terms of solid content) was Polyester polyol (A3-1) with 21.9 mgKOH/g, resin acid value (conversion of solid content) of 0.74 mgKOH/g, and glass transition temperature (Tg) of 7.3°C.

(合成例11)聚酯多元醇(A3-2)之合成 使用聚酯多元醇(A3-1)900份、環己烷二異氰酸酯13.5份,按照慣用方法進行鏈伸長反應從而合成聚酯聚胺酯多元醇。將所獲得之聚酯聚胺酯多元醇利用乙酸乙酯稀釋至樹脂固形物成分40%,獲得數量平均分子量(Mn)為14,500、重量平均分子量(Mw)為117,500、樹脂羥值(固形物成分換算)為5.2 mgKOH/g、樹脂酸值(固形物成分換算)為1.8 mgKOH/g、玻璃轉移溫度(Tg)為10.0℃之聚酯多元醇(A3-2)。(Synthesis example 11) Synthesis of polyester polyol (A3-2) Using 900 parts of polyester polyol (A3-1) and 13.5 parts of cyclohexane diisocyanate, a chain extension reaction was carried out according to a conventional method to synthesize polyester polyurethane polyol. Dilute the obtained polyester polyurethane polyol with ethyl acetate to a resin solid content of 40%, and obtain a number average molecular weight (Mn) of 14,500, a weight average molecular weight (Mw) of 117,500, and a resin hydroxyl value (calculated as solid content) It is a polyester polyol (A3-2) of 5.2 mgKOH/g, resin acid value (calculated as solid content) of 1.8 mgKOH/g, and glass transition temperature (Tg) of 10.0°C.

(比較合成例1)聚酯多元醇(AH-1)之合成 使用間苯二甲酸316.4份、對苯二甲酸316.4份、新戊二醇59.5份、1,6-己二醇225.0份、乙二醇82.7份,按照慣用方法合成聚酯多元醇。將所獲得之聚酯多元醇利用乙酸乙酯稀釋至樹脂固形物成分60%,獲得數量平均分子量(Mn)為7,700、重量平均分子量(Mw)為17,900、樹脂羥值(固形物成分換算)為18.3 mgKOH/g、樹脂酸值(固形物成分換算)為1.5 mgKOH/g、玻璃轉移溫度(Tg)為25.3℃之聚酯多元醇(AH-1)。(Comparative Synthesis Example 1) Synthesis of polyester polyol (AH-1) Using 316.4 parts of isophthalic acid, 316.4 parts of terephthalic acid, 59.5 parts of neopentyl glycol, 225.0 parts of 1,6-hexanediol, and 82.7 parts of ethylene glycol, the polyester polyol was synthesized according to a conventional method. The obtained polyester polyol is diluted with ethyl acetate to a resin solid content of 60%, and the number average molecular weight (Mn) is 7,700, the weight average molecular weight (Mw) is 17,900, and the resin hydroxyl value (calculated as solid content) is 18.3 mgKOH/g, resin acid value (conversion of solid content) is 1.5 mgKOH/g, glass transition temperature (Tg) is 25.3 ℃ polyester polyol (AH-1).

(比較合成例2)聚酯多元醇(AH-2)之合成 使用間苯二甲酸395.4份、對苯二甲酸179.7份、癸二酸29.2份、1,6-己二醇362.2份、乙二醇33.6份,按照慣用方法合成聚酯多元醇。將所獲得之聚酯多元醇利用乙酸乙酯稀釋至樹脂固形物成分60%,獲得數量平均分子量(Mn)為9,200、重量平均分子量(Mw)為20,600、樹脂羥值(固形物成分換算)為17.2 mgKOH/g、樹脂酸值(固形物成分換算)為0.9 mgKOH/g、玻璃轉移溫度(Tg)為-0.7℃之聚酯多元醇(AH-2)。(Comparative Synthesis Example 2) Synthesis of polyester polyol (AH-2) Using 395.4 parts of isophthalic acid, 179.7 parts of terephthalic acid, 29.2 parts of sebacic acid, 362.2 parts of 1,6-hexanediol, and 33.6 parts of ethylene glycol, polyester polyol was synthesized according to a conventional method. The obtained polyester polyol is diluted with ethyl acetate to 60% of the resin solid content, and the number average molecular weight (Mn) is 9,200, the weight average molecular weight (Mw) is 20,600, and the resin hydroxyl value (calculated as solid content) is 17.2 Polyester polyol (AH-2) with mgKOH/g, resin acid value (conversion of solid content) of 0.9 mgKOH/g, and glass transition temperature (Tg) of -0.7°C.

將合成例1-11、比較合成例1、2中所獲得之聚酯多元醇之物性以如下方式進行測定,彙整於表1、2。再者,表中之多羥基醇(a2-1)之摻合量、多羥基醇(a2-2)及多羥基醇(a2-3)之摻合量係使用於聚酯多元醇之合成之多羥基醇(a)中所佔的個別之比例。 又,針對聚酯多元醇(A1-1)、(A1-3)、(A1-5)~(A1-8)各者,測定聚酯多元醇(A1)50份、樹脂(A2)50份、甲苯二異氰酸酯之三羥甲基丙烷加成物30份之組成物的動態黏彈性,確認到於損耗正切(tanδ)中存在源自聚酯多元醇(A1)之波峰及源自樹脂(A2)之波峰。 (分子量測定法) 測定裝置:Tosoh股份有限公司製造HLC-8320GPC 管柱:Tosoh股份有限公司製造TSKgel 4000HXL、TSKgel 3000HXL、TSKgel 2000HXL、TSKgel 1000HXL 檢測器:RI(示差折射計) 資料處理:Tosoh股份有限公司製造 Multi Station GPC-8020modelII 測定條件:管柱溫度 40℃ 溶劑 四氫呋喃 流速 0.35 ml/分鐘 標準:單分散聚苯乙烯 試樣:將以樹脂固形物成分換算計0.2質量%之四氫呋喃溶液利用微過濾器進行過濾所得者(100 μl)The physical properties of the polyester polyols obtained in Synthesis Examples 1-11 and Comparative Synthesis Examples 1 and 2 were measured as follows, and are summarized in Tables 1 and 2. Furthermore, the blending amount of polyhydric alcohol (a2-1), the blending amount of polyhydric alcohol (a2-2) and polyhydric alcohol (a2-3) in the table are used in the synthesis of polyester polyol The proportion of individual polyhydric alcohols (a). In addition, 50 parts of polyester polyol (A1) and 50 parts of resin (A2) were measured for each of polyester polyol (A1-1), (A1-3), (A1-5) to (A1-8) , The dynamic viscoelasticity of the composition of 30 parts of the trimethylolpropane adduct of toluene diisocyanate has confirmed that there are peaks derived from polyester polyol (A1) and resin (A2) in the loss tangent (tanδ). ) Of the crest. (Molecular weight determination method) Measuring device: HLC-8320GPC manufactured by Tosoh Co., Ltd. Column: TSKgel 4000HXL, TSKgel 3000HXL, TSKgel 2000HXL, TSKgel 1000HXL manufactured by Tosoh Co., Ltd. Detector: RI (differential refractometer) Data processing: Multi Station GPC-8020modelII manufactured by Tosoh Co., Ltd. Measurement conditions: column temperature 40℃ Solvent Tetrahydrofuran Flow rate 0.35 ml/min Standard: Monodisperse Polystyrene Sample: 0.2% by mass of the tetrahydrofuran solution converted to the solid content of the resin is filtered with a microfilter (100 μl)

(酸值測定法) 準確稱量試樣5.0 g,加入中性溶劑30 mL以使之溶解,使用0.1 mol/L氫氧化鉀溶液(甲醇性)進行滴定。指示劑係使用酚酞。測定結果係換算為中和1 g試樣所需要之氫氧化鉀之量,單位設為mgKOH/g。(Acid value determination method) Accurately weigh 5.0 g of the sample, add 30 mL of neutral solvent to dissolve it, and titrate with 0.1 mol/L potassium hydroxide solution (methanol-based). The indicator system uses phenolphthalein. The measurement result is converted into the amount of potassium hydroxide required to neutralize 1 g sample, and the unit is mgKOH/g.

(羥值測定法) 準確稱量試樣4.0 g(固形物成分換算),加入由乙酸酐/吡啶(容量比1/19)構成之乙醯化劑25 mL,進行密閉並以100℃加熱1小時。乙醯化後,加入離子交換水10 mL及四氫呋喃100 mL,使用0.5 mol/L氫氧化鉀溶液(醇性)進行滴定。指示劑係使用酚酞。測定結果係換算為對使1 g試樣乙醯化時所產生之乙酸進行中和所需要之氫氧化鉀之量,單位設為mgKOH/g。(Hydroxyl value determination method) Accurately weigh 4.0 g of the sample (calculated as solid content), add 25 mL of an acetylating agent composed of acetic anhydride/pyridine (volume ratio 1/19), seal it and heat it at 100°C for 1 hour. After acetylation, add 10 mL of ion-exchanged water and 100 mL of tetrahydrofuran, and use 0.5 mol/L potassium hydroxide solution (alcoholic) for titration. The indicator system uses phenolphthalein. The measurement result is converted to the amount of potassium hydroxide required to neutralize the acetic acid produced when 1 g of the sample is acetylated, and the unit is mgKOH/g.

(玻璃轉移溫度測定法) 使用DSC,使試樣5 mg於30 mL/分鐘之氮氣氣流下自室溫以10℃/分鐘升溫至200℃,其後,以10℃/分鐘冷卻至-80℃,再次以10℃/分鐘升溫至150℃,而測定DSC曲線。於第二次升溫步驟中所觀測到之測定結果中,將使低溫側之基線延長至高溫側的直線與在玻璃轉移之階梯狀部分的曲線之斜率成為最大之點所劃的切線之交點作為玻璃轉移點,將此時之溫度作為玻璃轉移溫度。(Glass transition temperature measurement method) Using DSC, heat 5 mg of the sample from room temperature at 10°C/min to 200°C under a nitrogen flow of 30 mL/min, then cool it down to -80°C at 10°C/min, and then heat it up again at 10°C/min To 150°C, and measure the DSC curve. In the measurement results observed in the second heating step, the intersection of the straight line extending the baseline on the low temperature side to the high temperature side and the tangent line drawn at the point where the slope of the stepped part of the glass transition becomes the largest The glass transition point is the temperature at this time as the glass transition temperature.

[表1]    A1-1 A1-2 A1-3 A1-4 A1-5 A1-6 A1-7 多羥基醇(a2-1)之摻合量(莫耳%) 45 20 42.5 45 45 85 85 多羥基醇(a2-2)及 多羥基醇(a2-3)之摻合量(莫耳%) 10 15 15 10 10 15 15 玻璃轉移溫度(℃) 10.7 15.8 -3.6 22.5 7.3 -11.0 -9.1 酸值(mgKOH/g) 0.55 2.2 1.1 0.46 0.51 0.71 0.93 羥值(mgKOH/g) 19.2 10.8 13.8 13.8 30.7 16.8 10.0 數量平均分子量 3000 11200 3050 1980 2600 2300 3000 重量平均分子量 16000 25900 19640 19920 11000 18220 25160 [Table 1] A1-1 A1-2 A1-3 A1-4 A1-5 A1-6 A1-7 Blending amount of polyhydric alcohol (a2-1) (mol%) 45 20 42.5 45 45 85 85 Blending amount of polyhydric alcohol (a2-2) and polyhydric alcohol (a2-3) (mol%) 10 15 15 10 10 15 15 Glass transition temperature (℃) 10.7 15.8 -3.6 22.5 7.3 -11.0 -9.1 Acid value (mgKOH/g) 0.55 2.2 1.1 0.46 0.51 0.71 0.93 Hydroxyl value (mgKOH/g) 19.2 10.8 13.8 13.8 30.7 16.8 10.0 Number average molecular weight 3000 11200 3050 1980 2600 2300 3000 Weight average molecular weight 16000 25900 19640 19920 11000 18220 25160

[表2]    A1-8 A2 A3-1 A3-2 AH-1 AH-2 多羥基醇(a2-1)之摻合量(莫耳%) 70 0 0 多羥基醇(a2-2)及 多羥基醇(a2-3)之摻合量(莫耳%) 15 15 0 玻璃轉移溫度(℃) -3.0 84 7.3 10.0 25.3 -0.7 酸值(mgKOH/g) 1.2 4.0 0.74 1.8 1.5 0.9 羥值(mgKOH/g) 16.0 5.0 21.9 5.2 18.3 17.2 數量平均分子量 5440 8400 6200 14500 7700 9200 重量平均分子量 26220 61300 18500 117500 17900 20600 [Table 2] A1-8 A2 A3-1 A3-2 AH-1 AH-2 Blending amount of polyhydric alcohol (a2-1) (mol%) 70 - - - 0 0 Blending amount of polyhydric alcohol (a2-2) and polyhydric alcohol (a2-3) (mol%) 15 - - - 15 0 Glass transition temperature (℃) -3.0 84 7.3 10.0 25.3 -0.7 Acid value (mgKOH/g) 1.2 4.0 0.74 1.8 1.5 0.9 Hydroxyl value (mgKOH/g) 16.0 5.0 21.9 5.2 18.3 17.2 Number average molecular weight 5440 8400 6200 14,500 7700 9200 Weight average molecular weight 26220 61300 18500 117500 17,900 20600

<接著劑組成物之製備> (實施例1) 聚酯多元醇(A1-1)之樹脂固形物成分為100.0份之溶液中加入KBM-403(信越化學公司製造之矽烷偶合劑 不揮發成分:100%)1.6份,並充分攪拌直至KBM-403完全溶解。以不揮發成分量成為30.3份之方式向其中加入KW-75(DIC公司製造之異氰酸酯 不揮發成分:75% NCO%:13.3),進而以不揮發成分成為25%之方式加入乙酸乙酯並充分攪拌,而製作實施例1之接著劑。<Preparation of adhesive composition> (Example 1) Add 1.6 parts of KBM-403 (Non-volatile content of silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd.: 100%) to a solution containing 100.0 parts of resin solid content of polyester polyol (A1-1), and stir well until KBM-403 completely dissolved. Add KW-75 (non-volatile isocyanate made by DIC company: 75% NCO%: 13.3) so that the non-volatile content becomes 30.3 parts, and then add ethyl acetate so that the non-volatile content becomes 25% and fully Stir to prepare the adhesive of Example 1.

(實施例2)~(實施例12) 將接著劑之製備所使用之材料、摻合調整為表3、表4中記載之值,除此之外,以與實施例1相同之方式製造實施例2~實施例12之接著劑。(Example 2) ~ (Example 12) Except adjusting the materials and blending used in the preparation of the adhesive to the values described in Table 3 and Table 4, the adhesives of Examples 2 to 12 were produced in the same manner as in Example 1.

(比較例1)、(比較例2) 將接著劑之製備所使用之材料、摻合調整為表5中記載之值,除此之外,以與實施例1相同之方式製造比較例1、比較例2之接著劑。 再者,表3~表5中記載之值為固形物成分量(不揮發成分量)。(Comparative example 1), (Comparative example 2) The adhesives of Comparative Example 1 and Comparative Example 2 were produced in the same manner as in Example 1, except that the materials and blending used in the preparation of the adhesive were adjusted to the values described in Table 5. In addition, the values described in Tables 3 to 5 are the amount of solid content (the amount of non-volatile content).

<積層體之製造 圖2之構成> (實施例1) 於作為金屬層3之厚度40 μm之鋁箔之無光澤面,將實施例1之接著劑以成為塗佈量:4 g/平方米之量藉由乾式貼合機進行塗佈以作為接著層2,使溶劑揮散後,積層作為外層側基材層1之厚度25 μm之延伸聚醯胺膜。 繼而,於所獲得之積層膜之金屬層3之鋁箔的光澤面,將接著層5用之接著劑以成為塗佈量:4 g/平方米之量藉由乾式貼合機進行塗佈,使溶劑揮散後,積層作為密封劑層4之厚度40 μm之未延伸聚丙烯膜,其後,進行60℃、5天之硬化(老化),使接著劑硬化而獲得實施例1之積層體。<Production of laminated body Figure 2 constitution> (Example 1) On the matte surface of the 40 μm thick aluminum foil as the metal layer 3, the adhesive of Example 1 was applied in an amount of 4 g/m² with a dry laminator as the adhesive layer 2. After the solvent is volatilized, a 25 μm-thick stretched polyamide film is laminated as the outer base layer 1. Then, on the glossy surface of the aluminum foil of the metal layer 3 of the obtained laminated film, the adhesive used for the adhesive layer 5 was applied to a coating amount: 4 g/m² by a dry laminator to make After the solvent was evaporated, an unstretched polypropylene film with a thickness of 40 μm was laminated as the sealant layer 4, and then cured (aging) at 60° C. for 5 days to cure the adhesive to obtain the laminate of Example 1.

(實施例2)~(實施例12) 以與實施例1相同之方式使用實施例2~12之接著劑作為接著層2,獲得實施例2~實施例12之積層體。(Example 2) ~ (Example 12) In the same manner as in Example 1, the adhesives of Examples 2 to 12 were used as the adhesive layer 2 to obtain laminates of Examples 2 to 12.

(比較例1)、(比較例2) 以與實施例1相同之方式使用比較例1、2之接著劑作為接著層2,獲得比較例1、2之積層體。(Comparative example 1), (Comparative example 2) In the same manner as in Example 1, the adhesives of Comparative Examples 1 and 2 were used as the adhesive layer 2 to obtain laminates of Comparative Examples 1 and 2.

積層體之評價係以如下方式進行。將結果示於表3~表5。 <接著強度> 使用島津製作所股份有限公司之「Autograph AGS-J」,以剝離速度100 mm/分鐘、剝離寬度15 mm、剝離形態180°剝離之條件,對實施例或比較例之積層體之外層側基材層1與金屬層3之界面的接著強度進行評價。數值越高,表示作為接著劑越佳。The evaluation of the laminate was performed as follows. The results are shown in Table 3 to Table 5. <Adhesion strength> Using the "Autograph AGS-J" of Shimadzu Corporation, the peeling speed is 100 mm/min, the peeling width is 15 mm, and the peeling shape is peeled at 180°. The adhesion strength of the interface between 1 and the metal layer 3 was evaluated. The higher the value, the better as an adhesive.

<成型性> 使用山岡製作所股份有限公司之「1 ton桌上伺服壓力機(SBN-1000)」,將實施例或比較例之積層體切割成60×60 mm之大小,而製成空白樣品(被成型材、素材)。對上述空白樣品,以鋁箔無光澤面成為凸側之方式,於23℃±5℃、利用無成型高度之直型模具(straight mold)將成型高度自4.5 mm改變至6.5 mm來進行拉伸成型,藉由不會產生鋁箔之斷裂、或各層間之隆起之最大成型高度對成型性進行評價。<Formability> Using Yamaoka Seisakusho Co., Ltd. "1 ton desktop servo press (SBN-1000)", the laminated body of the embodiment or the comparative example was cut into a size of 60×60 mm, and a blank sample (formed material, material). For the above blank samples, stretch the molding height from 4.5 mm to 6.5 mm by using a straight mold with no molding height at 23°C±5°C in such a way that the matte side of the aluminum foil becomes a convex side. , Evaluate the moldability by the maximum molding height that does not cause the fracture of the aluminum foil or the bulge between each layer.

再者,所使用之模具之衝頭形狀為一邊30 mm之正方形且角R 2mm、衝頭肩R 1mm。所使用之模具之模孔形狀為一片34 mm之正方形且模孔角R 2mm、模孔肩R:1 mm,衝頭與模孔之間隙為單側0.3 mm。因上述間隙而產生與成型高度對應之梯度。視成型之高度進行以下3個等級之評價。 ◎:5.5mm以上(實用上特別優異) 〇:5.0mm以上(實用上優異) △:4.5mm(實用區域) ×:於4.5mm時產生鋁箔之斷裂、或各層間之隆起Furthermore, the punch shape of the die used is a square with a side of 30 mm with an angle R of 2mm and a punch shoulder R of 1mm. The die hole shape of the die used is a 34 mm square with die hole angle R 2mm, die hole shoulder R: 1 mm, and the gap between the punch and the die hole is 0.3 mm on one side. Due to the above gap, a gradient corresponding to the molding height is generated. According to the height of the molding, the following 3 levels are evaluated. ◎: 5.5mm or more (excellent practically) 〇: 5.0mm or more (excellent practically) △: 4.5mm (practical area) ×: Break of aluminum foil or bulge between layers at 4.5mm

<耐熱性> 使用山岡製作所股份有限公司之「1 ton桌上伺服壓力機(SBN-1000)」,將實施例或比較例之積層體切割成60×60 mm之大小,以鋁箔無光澤面成為外側之方式,利用無成型高度之直型模具以成型高度5.0 mm進行拉伸成型。以所獲得之30 mm方型托盤之凸緣部與側壁部相接之方式,以190℃3秒、210℃3秒此2條件分別緊貼熱封桿,確認凸緣部與側壁部之邊界部附近15個地方之外觀,評價於延伸聚醯胺膜與鋁箔之間是否產生隆起。 ◎:於210℃ 3秒無隆起(實用上特別優異) 〇:於190℃ 3秒無隆起(實用上優異) △:於190℃ 3秒產生隆起,但在3個地方以下(實用區域) ×:於190℃ 3秒產生在4個地方以上產生隆起<Heat resistance> Using Yamaoka Manufacturing Co., Ltd.’s "1 ton desktop servo press (SBN-1000)", the laminated body of the example or comparative example was cut into a size of 60×60 mm, and the matte surface of the aluminum foil became the outside. A straight mold with no molding height is used for stretch molding with a molding height of 5.0 mm. The flange part of the obtained 30 mm square pallet is connected to the side wall part, and the heat-sealing rod is closely adhered to the heat-sealing rod under the two conditions of 190°C for 3 seconds and 210°C for 3 seconds to confirm the boundary between the flange part and the side wall part. The appearance of 15 places near the part was evaluated whether swelling occurred between the stretched polyamide film and the aluminum foil. ◎: No swelling at 210°C for 3 seconds (excellent practically) 〇: No swelling at 190°C for 3 seconds (excellent for practical use) △: Swelling occurs at 190°C for 3 seconds, but less than 3 places (practical area) ×: Protrusion occurs in more than 4 places at 190℃ for 3 seconds

<耐濕熱性> 使用山岡製作所股份有限公司之「1 ton桌上伺服壓力機(SBN-1000)」,將實施例或比較例之積層體切割成60×60 mm之大小,以鋁箔無光澤面成為外側之方式,利用無成型高度之直型模具以成型高度5.0 mm進行拉伸成型。將所獲得之30 mm方型之托盤放入至85℃、85%RH環境下之恆溫恆濕槽中並靜置。自恆溫恆濕槽中取出上述托盤,確認凸緣部與側壁部之邊界部附近15個地方之外觀,評價於延伸聚醯胺膜與鋁箔之間是否產生隆起。 ◎:靜置168小時後無隆起(實用上特別優異) 〇:靜置72小時候無隆起(實用上優異) △:靜置72小時候產生隆起,但在3個地方以下(實用區域) ×:靜置72小時候在4個地方以上產生隆起<Damp and heat resistance> Using Yamaoka Manufacturing Co., Ltd.’s "1 ton desktop servo press (SBN-1000)", the laminated body of the example or comparative example was cut into a size of 60×60 mm, and the matte surface of the aluminum foil became the outside. A straight mold with no molding height is used for stretch molding with a molding height of 5.0 mm. Put the obtained 30 mm square tray into a constant temperature and humidity tank at 85°C and 85% RH and let it stand still. Take out the above-mentioned tray from the constant temperature and humidity tank, check the appearance of 15 places near the boundary between the flange part and the side wall part, and evaluate whether swelling occurs between the stretched polyamide film and the aluminum foil. ◎: No swelling after 168 hours of standing (excellent practically) 〇: No swelling when left for 72 hours (excellent for practical use) △: Uplift occurred when left for 72 hours, but less than 3 places (practical area) ×: Uplifts occurred in more than 4 places when left for 72 hours

[表3]    實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 聚酯多元醇(A1-1) 100          87.1    聚酯多元醇(A1-2)    100             聚酯多元醇(A1-3)       100       84.9 聚酯多元醇(A1-4)          100       聚酯多元醇(A1-5)                   聚酯多元醇(A1-6)                   聚酯多元醇(A1-7)                   聚酯多元醇(A1-8)                   樹脂(A2)             12.9 15.1 聚酯多元醇(A3-1)                   聚酯多元醇(A3-2)                   聚酯多元醇(AH-1)                   聚酯多元醇(AH-2)                   KBM-403 1.6 1.0 1.0 1.9 1.6 0.8 KW-75 30.3 20.2 19.2 19.5 27.7 19.2 Lupranate MI             3.4    NCO當量比 [NCO]/[OH] 2.9 5.5 3.3 3.4 3.5 3.6 接著強度(N/15 mm) 6.9 5.2 5.5 8.3 8.1 7.8 成型性 耐熱性 耐濕熱性 [table 3] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Polyester polyol (A1-1) 100 87.1 Polyester polyol (A1-2) 100 Polyester polyol (A1-3) 100 84.9 Polyester polyol (A1-4) 100 Polyester polyol (A1-5) Polyester polyol (A1-6) Polyester polyol (A1-7) Polyester polyol (A1-8) Resin (A2) 12.9 15.1 Polyester polyol (A3-1) Polyester polyol (A3-2) Polyester polyol (AH-1) Polyester polyol (AH-2) KBM-403 1.6 1.0 1.0 1.9 1.6 0.8 KW-75 30.3 20.2 19.2 19.5 27.7 19.2 Lupranate MI 3.4 NCO equivalent ratio [NCO]/[OH] 2.9 5.5 3.3 3.4 3.5 3.6 Adhesion strength (N/15 mm) 6.9 5.2 5.5 8.3 8.1 7.8 Formability Heat resistance Humidity and heat resistance

[表4]    實施例7 實施例8 實施例9 實施例10 實施例11 實施例12 聚酯多元醇(A1-1)                   聚酯多元醇(A1-2)                   聚酯多元醇(A1-3)                   聚酯多元醇(A1-4)             51.4    聚酯多元醇(A1-5) 91.5             33.9 聚酯多元醇(A1-6)    85.1             聚酯多元醇(A1-7)       85.1          聚酯多元醇(A1-8)          84.9       樹脂(A2) 8.5 14.9 14.9 15.1    9.4 聚酯多元醇(A3-1)                56.7 聚酯多元醇(A3-2)             48.6    聚酯多元醇(AH-1)                   聚酯多元醇(AH-2)                   KBM-403 1.6 0.8 0.8 0.8 1.9 1.8 KW-75 21.0 18.9 18.9 19.1 36.2 23.1 Lupranate MI 4.2             4.6 NCO當量比 [NCO]/[OH] 2.4 3.0 4.8 3.2 8.9 3.4 接著強度(N/15 mm) 4.6 8.6 7.6 7.8 7.1 4.6 成型性 耐熱性 耐濕熱性 [Table 4] Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Polyester polyol (A1-1) Polyester polyol (A1-2) Polyester polyol (A1-3) Polyester polyol (A1-4) 51.4 Polyester polyol (A1-5) 91.5 33.9 Polyester polyol (A1-6) 85.1 Polyester polyol (A1-7) 85.1 Polyester polyol (A1-8) 84.9 Resin (A2) 8.5 14.9 14.9 15.1 9.4 Polyester polyol (A3-1) 56.7 Polyester polyol (A3-2) 48.6 Polyester polyol (AH-1) Polyester polyol (AH-2) KBM-403 1.6 0.8 0.8 0.8 1.9 1.8 KW-75 21.0 18.9 18.9 19.1 36.2 23.1 Lupranate MI 4.2 4.6 NCO equivalent ratio [NCO]/[OH] 2.4 3.0 4.8 3.2 8.9 3.4 Adhesion strength (N/15 mm) 4.6 8.6 7.6 7.8 7.1 4.6 Formability Heat resistance Humidity and heat resistance

[表5]    比較例1 比較例2 聚酯多元醇(A1-1)       聚酯多元醇(A1-2)       聚酯多元醇(A1-3)       聚酯多元醇(A1-4)       聚酯多元醇(A1-5)       聚酯多元醇(A1-6)       聚酯多元醇(A1-7)       聚酯多元醇(A1-8)       樹脂(A2)       聚酯多元醇(A3-1)       聚酯多元醇(A3-2)       聚酯多元醇(AH-1) 100    聚酯多元醇(AH-2)    100 KBM-403 1.0 0.8 KW-75 20.3 18.9 Lupranate MI       NCO當量比 [NCO]/[OH] 2.6 2.6 接著強度(N/15mm) 6.3 7.2 成型性 × 耐熱性 耐濕熱性 × [table 5] Comparative example 1 Comparative example 2 Polyester polyol (A1-1) Polyester polyol (A1-2) Polyester polyol (A1-3) Polyester polyol (A1-4) Polyester polyol (A1-5) Polyester polyol (A1-6) Polyester polyol (A1-7) Polyester polyol (A1-8) Resin (A2) Polyester polyol (A3-1) Polyester polyol (A3-2) Polyester polyol (AH-1) 100 Polyester polyol (AH-2) 100 KBM-403 1.0 0.8 KW-75 20.3 18.9 Lupranate MI NCO equivalent ratio [NCO]/[OH] 2.6 2.6 Next strength (N/15mm) 6.3 7.2 Formability X Heat resistance Humidity and heat resistance X

根據本結果明確得知:藉由使用本發明之接著劑,能夠獲得一種包裝材,其具有優異之成型性,即便於為了密封收納物而進行之密封劑層彼此之熱熔接後,進而於高溫高濕下之長期耐久性試驗中,亦無層間之接著強度之降低,層間之隆起等外觀不良得到抑制。According to the results, it is clear that by using the adhesive of the present invention, a packaging material can be obtained that has excellent moldability even after the heat fusion of the sealant layers for sealing the storage, and then at high temperature In the long-term durability test under high humidity, there was no decrease in the adhesive strength between the layers, and the appearance defects such as bulging between the layers were suppressed.

1:外層側基材層 2:接著層 3:金屬層 4:密封劑層 5:接著層1: Outer layer side substrate layer 2: Next layer 3: Metal layer 4: Sealant layer 5: Next layer

[圖1]係本發明之依序積層外層側基材層1、接著層2、金屬層3、及密封劑層4而成之積層體的具體態樣之一例。 [圖2]係本發明之依序積層外層側基材層1、接著層2、金屬層3、接著層5、及密封劑層4而成之積層體的具體態樣之一例。[FIG. 1] It is an example of the specific aspect of the laminated body which laminated|stacked the outer layer side base material layer 1, the adhesive layer 2, the metal layer 3, and the sealant layer 4 of this invention in order. [FIG. 2] It is an example of the specific aspect of the laminated body which laminated|stacked the outer layer side base material layer 1, the adhesive layer 2, the metal layer 3, the adhesive layer 5, and the sealant layer 4 of this invention in order.

1:外層側基材層 1: Outer layer side substrate layer

2:接著層 2: Next layer

3:金屬層 3: Metal layer

4:密封劑層 4: Sealant layer

Claims (15)

一種二液型接著劑,含有: 包含聚酯多元醇(A1)之多元醇組成物(A)、及 包含異氰酸酯化合物(B1)之聚異氰酸酯組成物(B); 上述聚酯多元醇(A1)係多元酸或其衍生物(a1)與多羥基醇(a2)之反應產物,上述多羥基醇(a2)包含2個羥基間之亞甲基鏈之碳原子數為5以上且19以下並且為奇數之多羥基醇(a2-1)。A two-component adhesive containing: Polyol composition (A) containing polyester polyol (A1), and Polyisocyanate composition (B) containing isocyanate compound (B1); The polyester polyol (A1) is a reaction product of a polyacid or its derivative (a1) and a polyhydric alcohol (a2). The polyhydric alcohol (a2) contains the number of carbon atoms in the methylene chain between the two hydroxyl groups. It is a polyhydric alcohol (a2-1) that is 5 or more and 19 or less and is an odd number. 如請求項1之二液型接著劑,其中,上述多元醇組成物(A)包含玻璃轉移溫度為50℃以上且110℃以下之樹脂(A2)。The two-component adhesive of claim 1, wherein the polyol composition (A) includes a resin (A2) having a glass transition temperature of 50° C. or more and 110° C. or less. 如請求項1或2之二液型接著劑,其中,上述樹脂(A2)係選自由聚酯樹脂、聚胺酯樹脂(polyurethane resin)、聚脲樹脂、丙烯酸樹脂、聚醯胺樹脂、聚醯亞胺樹脂、環氧樹脂、松香改質環氧樹脂所組成之群中至少一種。The two-component adhesive of claim 1 or 2, wherein the resin (A2) is selected from polyester resins, polyurethane resins, polyurea resins, acrylic resins, polyamide resins, and polyimides At least one of the group consisting of resin, epoxy resin, and rosin-modified epoxy resin. 如請求項1至3中任一項之二液型接著劑,其中,上述樹脂(A2)具備選自由羥基、羧基、胺基、醯胺基、硫醇基、縮水甘油基所組成之群中至少1種官能基。The two-component adhesive according to any one of claims 1 to 3, wherein the resin (A2) is selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, an amide group, a thiol group, and a glycidyl group At least one functional group. 如請求項4之二液型接著劑,其中,上述官能基係選自2級羥基、3級羥基中至少1種。The two-component adhesive of claim 4, wherein the functional group is at least one selected from the group consisting of a secondary hydroxyl group and a tertiary hydroxyl group. 如請求項2至5中任一項之二液型接著劑,其中,上述樹脂(A2)相對於上述聚酯多元醇(A1)與上述樹脂(A2)之合計100質量份的摻合量為90質量份以下。The two-component adhesive of any one of claims 2 to 5, wherein the blending amount of the resin (A2) with respect to 100 parts by mass of the polyester polyol (A1) and the resin (A2) in total is 90 parts by mass or less. 如請求項1或2之二液型接著劑,其中,上述多羥基醇(a2)包含選自由具有支鏈伸烷基結構之多羥基醇(a2-2)、具有環狀結構之多羥基醇(a2-3)所組成之群中至少一種。The two-component adhesive of claim 1 or 2, wherein the above-mentioned polyhydric alcohol (a2) comprises polyhydric alcohols (a2-2) having a branched alkylene structure and polyhydric alcohols having a cyclic structure (A2-3) At least one of the group consisting of. 如請求項1至7中任一項之二液型接著劑,其中,上述多羥基醇(a2)中之上述多羥基醇(a2-1)之摻合量為10莫耳%以上且90莫耳%以下。The two-component adhesive of any one of claims 1 to 7, wherein the blending amount of the polyhydric alcohol (a2-1) in the polyhydric alcohol (a2) is 10 mol% or more and 90 mol% Ear% or less. 如請求項7或8之二液型接著劑,其中,上述多羥基醇(a2)中之上述具有支鏈伸烷基結構之多羥基醇(a2-2)及上述具有環狀結構之多羥基醇(a2-3)的合計摻合量為10莫耳%以上且90莫耳%以下。The two-component adhesive of claim 7 or 8, wherein the above-mentioned polyhydric alcohol (a2-2) having a branched alkylene structure in the above-mentioned polyhydric alcohol (a2) and the above-mentioned polyhydric alcohol having a cyclic structure The total blending amount of alcohol (a2-3) is 10 mol% or more and 90 mol% or less. 如請求項1至9中任一項之二液型接著劑,其中,上述多元酸或其衍生物(a1)包含具有芳香族環之多元酸或其衍生物(a1-1),上述多元酸或其衍生物(a1)中之上述具有芳香族環之多元酸或其衍生物(a1-1)的摻合量為30莫耳%以上。The two-component adhesive of any one of claims 1 to 9, wherein the polybasic acid or its derivative (a1) comprises a polybasic acid or its derivative (a1-1) having an aromatic ring, and the polybasic acid The blending amount of the above-mentioned aromatic ring-containing polybasic acid or its derivative (a1-1) in its derivative (a1) is 30 mol% or more. 如請求項1至10中任一項之二液型接著劑,其中,聚異氰酸酯組成物(B)之異氰酸基與多元醇組成物(A)所具有之羥基之比[NCO]/[OH]為1.5以上且15.0以下。The two-component adhesive of any one of claims 1 to 10, wherein the ratio of the isocyanate group of the polyisocyanate composition (B) to the hydroxyl group of the polyol composition (A) [NCO]/[ OH] is 1.5 or more and 15.0 or less. 如請求項1至11中任一項之二液型接著劑,其用於電池用包裝材。Such as the two-component adhesive of any one of claims 1 to 11, which is used as a packaging material for batteries. 一種電池用包裝材,其至少依序積層有外層側基材層1、接著層2、金屬層3、及密封劑層4而成,且上述接著層2為請求項1至12中任一項之二液型接著劑之硬化物。A packaging material for a battery comprising at least an outer layer side base material layer 1, an adhesive layer 2, a metal layer 3, and a sealant layer 4 laminated in this order, and the adhesive layer 2 is any one of claims 1 to 12 The hardened substance of the two-component adhesive. 一種電池用容器,其係將請求項13之電池用包裝材成型而成。A battery container formed by molding the battery packaging material of claim 13. 一種電池,其係使用請求項14之電池用容器而成。A battery using the battery container of claim 14.
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