TWI804680B - Adhesive composition using resin having imide bond and phosphorus compound, adhesive film using the adhesive composition, cover layer film, copper clad laminate, and flexible printed wiring board - Google Patents

Abstract

Translated fromChinese

本發明之課題係提供一種優異的黏接劑組成物，其黏接性、耐熱性、操作性、絕緣可靠性優異，適合於黏接薄膜、表覆層薄膜、覆銅疊層板等。一種黏接劑組成物，其特徵為含有具有醯亞胺鍵之樹脂及特定結構之磷化合物。The object of the present invention is to provide an excellent adhesive composition, which is excellent in adhesiveness, heat resistance, workability, and insulation reliability, and is suitable for bonding films, surface coating films, copper-clad laminates, and the like. An adhesive composition characterized by containing a resin with an imide bond and a phosphorus compound with a specific structure.

Description

Translated fromChinese

使用了具有醯亞胺鍵之樹脂及磷化合物之黏接劑組成物、使用了該黏接劑組成物之黏接薄膜、表覆層薄膜、覆銅疊層板、及撓性印刷配線板Adhesive composition using resin having imide bond and phosphorus compound, adhesive film using the adhesive composition, cover layer film, copper clad laminate, and flexible printed wiring board

本發明關於使用了具有醯亞胺鍵之樹脂及磷化合物之黏接劑組成物，並關於使用了前述黏接劑組成物之黏接薄膜、表覆層薄膜、覆銅疊層板、及撓性印刷配線板。The present invention relates to an adhesive composition using a resin having an imide bond and a phosphorus compound, and to an adhesive film, a surface coating film, a copper-clad laminate, and a flexible film using the aforementioned adhesive composition. permanent printed wiring board.

撓性印刷配線板廣泛使用在要求柔軟性、省空間性之電子設備零件，例如液晶顯示器、電漿顯示器等的顯示裝置用器件基板、行動電話、數位式照相機、攜帶型遊戲機等的基板中繼纜線、操作開關基板等，預計用途會進一步擴大。Flexible printed wiring boards are widely used in electronic equipment parts that require flexibility and space saving, such as device substrates for display devices such as liquid crystal displays and plasma displays, substrates for mobile phones, digital cameras, portable game machines, etc. Next to cables, operation switch substrates, etc., the use is expected to expand further.

撓性印刷配線板所使用之黏接劑，係使用在構成黏接薄膜、表覆層薄膜、覆銅疊層板等之撓性配線板的部位之中，要求黏接性、耐熱性、阻燃性、絕緣可靠性。Adhesives used in flexible printed wiring boards are used in the parts of flexible wiring boards such as adhesive films, surface coating films, and copper-clad laminates. Adhesiveness, heat resistance, and resistance Flammability, insulation reliability.

就撓性印刷配線板而言，伴隨近年來電子設備的輕薄短小化，配線的高密度化正進展中。為了實現配線的更高密度化，須縮短電路與電路之間的間距寬，對於撓性印刷配線板所使用之黏接劑，則要求絕緣可靠性的進一步改善。In flexible printed wiring boards, along with recent reductions in weight and size of electronic equipment, densification of wiring is progressing. In order to achieve higher wiring density, the pitch between circuits must be shortened, and further improvement in insulation reliability is required for adhesives used in flexible printed wiring boards.

作為撓性印刷配線板所使用之黏接劑，以往已使用環氧系樹脂、丙烯酸系樹脂、胺甲酸酯樹脂等，因應近年配線的高密度化、無鉛焊料，其耐熱性不足，就取代該等之具有耐熱性之黏接劑而言，正在探討聚醯亞胺系樹脂。As the adhesive used for flexible printed wiring boards, epoxy resin, acrylic resin, urethane resin, etc. have been used in the past. In response to the high density of wiring in recent years and the lack of heat resistance of lead-free solder, it has been replaced. As such heat-resistant adhesives, polyimide-based resins are being studied.

又，為了對撓性印刷配線板所使用之黏接劑賦予阻燃性，廣泛使用摻合不含溴等鹵素元素之磷化合物的方法。其中，考量耐熱性、阻燃性、相容性的觀點，廣泛使用具有通式(5)表示之化學結構(一般稱為DOP)之次膦酸衍生物。Moreover, in order to impart flame retardancy to the adhesive used for a flexible printed wiring board, the method of mixing the phosphorus compound which does not contain halogen elements, such as bromine, is widely used. Among them, from the viewpoint of heat resistance, flame retardancy, and compatibility, phosphinic acid derivatives having a chemical structure represented by general formula (5) (generally referred to as DOP) are widely used.

作為前述次膦酸衍生物之具體例，例如可列舉使用化學式(6)表示之9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、化學式(7)表示之9,10-二氫-10-苄基-9-氧雜-10-磷雜菲-10-氧化物、化學式(8)表示之10-(2,5-二羥基苯基)-10H-9-氧雜-10-磷雜菲-10-氧化物等的方法(例如，參照專利文獻1、2)。Specific examples of the aforementioned phosphinic acid derivatives include, for example, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide represented by chemical formula (6), and phosphaphenanthrene-10-oxide represented by chemical formula (7). 9,10-dihydro-10-benzyl-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9 represented by chemical formula (8) - Methods such as oxa-10-phosphaphenanthrene-10-oxide (for example, refer to Patent Documents 1 and 2).

[化8]

[chemical 8]

[先前技術文獻][Prior Art Literature][專利文獻][Patent Document]

[專利文獻1]日本專利5278785號公報[Patent Document 1] Japanese Patent No. 5278785

[專利文獻2]日本特開2011-148862號公報[Patent Document 2] Japanese Patent Laid-Open No. 2011-148862

但是，化學式(6)表示之9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物，由於分子量小，熱重量減少溫度低，其一部分未硬化而殘存的話，存在耐熱性降低的課題。又，化學式(7)表示之9,10-二氫-10-苄基-9-氧雜-10-磷雜菲-10-氧化物，由於不具有反應性官能基，存在於高溫高濕環境下容易滲出而絕緣可靠性降低的課題。另外，化學式(8)表示之10-(2,5-二羥基苯基)-10H-9-氧雜-10-磷雜菲-10-氧化物，由於對溶劑之溶解性低，存在操作性降低的課題。However, since the 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide represented by the chemical formula (6) has a small molecular weight and a low thermogravimetric reduction temperature, if a part of it remains unhardened, there is The problem of lowering heat resistance. Also, the 9,10-dihydro-10-benzyl-9-oxa-10-phosphaphenanthrene-10-oxide represented by chemical formula (7) exists in a high-temperature and high-humidity environment because it does not have a reactive functional group. It is easy to bleed out and reduce the insulation reliability. In addition, the 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide represented by the chemical formula (8) has low solubility in solvents and has operability The subject of reduction.

本發明係為了解決上述習知技術的問題而成，其目的在於提供黏接性、耐熱性、阻燃性、操作性優異，且具有高絕緣可靠性的黏接劑組成物。The present invention is made to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide an adhesive composition having excellent adhesiveness, heat resistance, flame retardancy, operability, and high insulation reliability.

本案發明人等為了達成上述目的而進行努力研究的結果，藉由組合具有醯亞胺鍵之樹脂、特定的磷化合物，而完成了本發明。As a result of diligent research by the present inventors to achieve the above object, the present invention has been accomplished by combining a resin having an imide bond and a specific phosphorus compound.

亦即，本發明係以下之構成。That is, the present invention has the following configurations.

一種黏接劑組成物，其特徵為：含有具有醯亞胺鍵之樹脂及通式(1)表示之磷化合物。An adhesive composition characterized in that it contains a resin having an imide bond and a phosphorus compound represented by the general formula (1).

通式(1)中之R₁~R₄係下列通式(2)~(4)中之任一者，R₁~R₄中之至少1個為通式(2)。通式(2)~(4)中之＊表示直接鍵結於通式(1)之芳香環的部位。通式(1)及通式(3)中之多個X各自獨立地為CH₂或C(CH₃)₂，通式(1)及通式(3)中之多個Y各自獨立地為氫或羥基。惟，通式(1)中，多個Y中之至少1個為羥基。通式(4)中之R₅為氫或碳數1~10之烷基。R₁ to R₄ in general formula (1) are any one of the following general formulas (2) to (4), and at least one of R₁ to R₄ is general formula (2). The * in general formula (2)~(4) represents the site directly bonded to the aromatic ring of general formula (1). Multiple Xs in general formula (1) and general formula (3) are each independently CH₂ or C(CH₃ )₂ , multiple Ys in general formula (1) and general formula (3) are each independently hydrogen or hydroxyl. However, in the general formula (1), at least one of the plurality of Y is a hydroxyl group. R in the general formula (₄ ) is hydrogen or an alkyl group with 1 to 10 carbons.

[化3]

[Chem 3]

前述具有醯亞胺鍵之樹脂，宜為聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醚醯亞胺樹脂、聚酯醯亞胺樹脂或聚碳酸酯醯亞胺樹脂。又，就前述具有醯亞胺鍵之樹脂之共聚成分而言，宜含有偏苯三甲酸酐或兩末端羧基改性丙烯腈丁二烯橡膠。The aforementioned resin having imide bonds is preferably polyimide resin, polyamideimide resin, polyetherimide resin, polyesterimide resin or polycarbonateimide resin. Also, the copolymerization component of the above-mentioned resin having an imide bond preferably contains trimellitic anhydride or acrylonitrile butadiene rubber modified with carboxyl groups at both terminals.

宜更含有環氧樹脂，前述環氧樹脂之性狀係於25℃為液狀，且1分子中具有2個以上之環氧基較佳。It is more preferable to contain epoxy resin. The properties of the above-mentioned epoxy resin are liquid at 25°C, and it is preferable to have more than 2 epoxy groups in one molecule.

前述任一項中之黏接劑組成物，係使用在印刷配線板用途。一種黏接薄膜，使用了前述黏接劑組成物。一種表覆層薄膜或覆銅疊層板，使用了前述黏接薄膜。一種撓性印刷配線板，使用了前述表覆層薄膜或覆銅疊層板。The adhesive composition in any one of the foregoing is used for printed wiring boards. An adhesive film using the aforementioned adhesive composition. A cover film or a copper-clad laminate using the aforementioned adhesive film. A flexible printed wiring board using the aforementioned cover film or copper-clad laminate.

根據本發明，藉由組合具有醯亞胺鍵之樹脂與特定之磷化合物，可獲得黏接性、耐熱性、阻燃性、操作性優異，且高絕緣可靠性優異的黏接劑組成物；及使用該黏接劑組成物的黏接薄膜、表覆層薄膜、覆銅疊層板、以及撓性印刷配線板。According to the present invention, by combining a resin having an imide bond and a specific phosphorus compound, an adhesive composition excellent in adhesiveness, heat resistance, flame retardancy, operability, and high insulation reliability can be obtained;And an adhesive film, a cover film, a copper-clad laminate, and a flexible printed wiring board using the adhesive composition.

<具有醯亞胺鍵之樹脂><Resin with imide bond>

本發明之黏接劑組成物中使用之具有醯亞胺鍵之樹脂，係樹脂之重複單元中具有1個以上醯亞胺鍵者，例如可列舉：聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醚醯亞胺樹脂、聚酯醯亞胺樹脂、聚碳酸酯醯亞胺樹脂等。樹脂之重複單元中宜具有2個以上之醯亞胺鍵。具有醯亞胺鍵之樹脂，宜以酸成分與二異氰酸酯成分或二胺成分作為共聚成分。以下，也將二異氰酸酯成分或二胺成分統稱為胺成分。就酸成分而言，可為具有芳香環之酸成分(芳香族酸成分)、脂肪族酸成分或脂環族酸成分中之任一者，宜為具有芳香環之多元羧酸成分。又，就胺成分(二異氰酸酯成分或二胺成分)而言，可為具有芳香環之胺成分、脂肪族胺成分、或脂環族胺成分中之任一者，宜為具有芳香環之胺成分。亦即，宜由來自具有芳香環之多元羧酸成分的構成單元與來自具有芳香環之二異氰酸酯成分或具有芳香環之二胺成分的構成單元構成。The resin having an imide bond used in the adhesive composition of the present invention has one or more imide bonds in the repeating unit of the resin, for example, polyimide resin, polyimide imide Amine resin, polyetherimide resin, polyesterimide resin, polycarbonateimide resin, etc. The repeating unit of the resin preferably has two or more imide bonds. For resins with imide bonds, acid components and diisocyanate components or diamine components are preferably used as copolymerization components. Hereinafter, diisocyanate components and diamine components are also collectively referred to as amine components. The acid component may be any of an acid component having an aromatic ring (aromatic acid component), an aliphatic acid component, or an alicyclic acid component, and is preferably a polyvalent carboxylic acid component having an aromatic ring. Also, the amine component (diisocyanate component or diamine component) may be any one of an amine component having an aromatic ring, an aliphatic amine component, or an alicyclic amine component, and is preferably an amine having an aromatic ring Element. That is, it is preferably composed of a structural unit derived from a polyvalent carboxylic acid component having an aromatic ring and a structural unit derived from a diisocyanate component having an aromatic ring or a diamine component having an aromatic ring.

本發明之黏接劑組成物中使用之具有醯亞胺鍵之樹脂，宜具有羧基或酸酐基作為反應性官能基。具有醯亞胺鍵之樹脂的酸價宜為5mgKOH/g以上，更佳為10mgKOH/g以上，尤佳為20mgKOH/g以上。又，宜為150mgKOH/g以下，更佳為120mgKOH/g以下，尤佳為100mgKOH/g以下。藉由為上述範圍內，與環氧樹脂、硬化劑的交聯點增加，熱硬化後之塗膜之交聯密度提高，可改善耐熱性。The resin having an imide bond used in the adhesive composition of the present invention preferably has a carboxyl group or an acid anhydride group as a reactive functional group. The acid value of the resin having an imide bond is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, and most preferably 20 mgKOH/g or more. Moreover, it is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, and especially preferably 100 mgKOH/g or less. By being within the above range, the crosslinking point with the epoxy resin and the hardener increases, the crosslinking density of the coating film after thermosetting increases, and heat resistance can be improved.

作為本發明之具有醯亞胺鍵之樹脂的酸成分，宜使用具有芳香環之多元羧酸成分。就具有芳香族之多元羧酸成分而言，宜為具有芳香族之多元羧酸的酸酐，具體而言，使用偏苯三甲酸酐(TMA)更佳。藉由使用偏苯三甲酸酐，除了可生成醯亞胺鍵，也可生成醯胺鍵，能改善樹脂之溶劑溶解性。令全部酸成分為100莫耳%時，偏苯三甲酸酐宜為30莫耳%以上，更佳為40莫耳%以上，尤佳為50莫耳%以上。又，上限並無限定，也可為100莫耳%，宜為90莫耳%以下，更佳為80莫耳%以下，尤佳為70莫耳%以下。As the acid component of the resin having an imide bond of the present invention, a polycarboxylic acid component having an aromatic ring is preferably used. The aromatic polycarboxylic acid component is preferably an anhydride of an aromatic polycarboxylic acid, and more specifically, trimellitic anhydride (TMA) is used. By using trimellitic anhydride, in addition to forming imide bonds, amide bonds can also be formed, which can improve the solvent solubility of the resin. When the total acid content is 100 mol%, the trimellitic anhydride is preferably at least 30 mol%, more preferably at least 40 mol%, and most preferably at least 50 mol%. Also, the upper limit is not limited, and may be 100 mol%, preferably 90 mol% or less, more preferably 80 mol% or less, and most preferably 70 mol% or less.

就偏苯三甲酸酐以外之具有芳香環之多元羧酸成分而言，例如可列舉：均苯四甲酸二酐(PMDA)、3,3’,4,4’-二苯甲酮四羧酸二酐(BTDA)、3,3’,4,4’-聯苯四羧酸二酐(BPDA)、乙二醇雙脫水偏苯三甲酸酯(TMEG)、丙二醇雙脫水偏苯三甲酸酯、1,4-丁烷二醇雙脫水偏苯三甲酸酯、六亞甲基二醇雙脫水偏苯三甲酸酯、聚乙二醇雙脫水偏苯三甲酸酯、聚丙二醇雙脫水偏苯三甲酸酯等伸烷二醇雙脫水偏苯三甲酸酯；1,2,5,6-萘四羧酸二酐、1,4,5,8-萘四羧酸二酐、2,3,5,6-吡啶四羧酸二酐、3,4,9,10-苝四羧酸二酐、3,3’,4,4’-二苯基磺酸四羧酸二酐、4,4’-氧基二鄰苯二甲酸二酐、1,1,1,3,3,3-六氟-2,2-雙(2,3-或3,4-二羧基苯基)丙烷二酐、2,2-雙(2,3-或3,4-二羧基苯基)丙烷二酐、2,2-雙[4-(2,3-或3,4-二羧基苯氧基)苯基]丙烷二酐、1,1,1,3,3,3-六氟-2,2-雙[4-(2,3-或3,4-二羧基苯氧基)苯基]丙烷二酐、1,3-雙(3,4-二羧基苯基)-1,1,3,3-四甲基二矽氧烷二酐等。該等可單獨使用，亦可將多種組合使用。Examples of polycarboxylic acid components having an aromatic ring other than trimellitic anhydride include: pyromellitic dianhydride (PMDA), 3,3',4,4'-benzophenone tetracarboxylic acid di anhydride (BTDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), ethylene glycol dianhydro trimellitate (TMEG), propylene glycol dianhydro trimellitate, 1 ,4-Butanediol dianhydrotrimellitate, Hexamethylene glycol dianhydrotrimellitate, Polyethylene glycol dianhydrotrimellitate, Polypropylene glycol dianhydrotrimellitate Isokanediol dianhydrotrimellitate; 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,5,6 -Pyridine tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonic acid tetracarboxylic dianhydride, 4,4'-oxygen Diphthalic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis(2,3- or 3,4-dicarboxyphenyl)propane dianhydride, 2, 2-bis(2,3- or 3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis[4-(2,3- or 3,4-dicarboxyphenoxy)phenyl]propane Dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis[4-(2,3- or 3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 1 , 3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldisiloxane dianhydride, etc. These may be used alone or in combination of multiple types.

作為其他酸成分，可使用脂肪族或脂環族的酸酐、芳香族、脂肪族或脂環族的二羧酸。例如，可使用將前項所列舉之成分中之任一者予以氫化而得者。具體而言，可列舉：1,4-環己烷二羧酸、1,3-環己烷二羧酸、1,2-環己烷二羧酸、meso-丁烷-1,2,3,4-四羧酸二酐、戊烷-1,2,4,5-四羧酸二酐、環丁烷四羧酸二酐、環戊烷四羧酸二酐、環己-1-烯-2,3,5,6-四羧酸二酐、3-乙基環己-1-烯-3-(1,2),5,6-四羧酸二酐、1-甲基-3-乙基環己烷-3-(1,2),5,6-四羧酸二酐、1-甲基-3-乙基環己-1-烯-3-(1,2),5,6-四羧酸二酐、1-乙基環己烷-1-(1,2),3,4-四羧酸二酐、1-丙基環己烷-1-(2,3),3,4-四羧酸二酐、1,3-二丙基環己烷-1-(2,3),3-(2,3)-四羧酸二酐、二環己基-3,4,3’,4’-四羧酸二酐、雙環[2.2.1]庚烷-2,3,5,6-四羧酸二酐、1-丙基環己烷-1-(2,3),3,4-四羧酸二酐、1,3-二丙基環己烷-1-(2,3),3-(2,3)-四羧酸二酐、二環己基-3,4,3’,4’-四羧酸二酐、雙環[2.2.1]庚烷-2,3,5,6-四羧酸二酐、雙環[2.2.2]辛烷-2,3,5,6-四羧酸二酐、雙環[2.2.2]辛-7-烯-2,3,5,6-四羧酸二酐、環己烷二羧酸等。就芳香族二羧酸而言，例如可列舉：對苯二甲酸、間苯二甲酸、鄰苯二甲酸、萘二羧酸、氧基二苯甲酸、二苯乙烯二羧酸等。就脂肪族羧酸而言，例如可列舉：琥珀酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、癸烷二酸、十二烷二酸、二十烷二酸、2-甲基琥珀酸、2-甲基己二酸、3-甲基己二酸、3-甲基戊烷二羧酸、2-甲基辛烷二羧酸、3,8-二甲基癸烷二羧酸、3,7-二甲基癸烷二羧酸、9,12-二甲基二十烷二酸、富馬酸、馬來酸等。該等可單獨使用，亦可將多種組合使用。若考慮耐熱性、密接性、溶解性、成本面等，則宜為癸二酸、1,4-環己烷二羧酸或間苯二甲酸，其中，為癸二酸更佳。使用該等成分時，考量獲得之具有醯亞胺鍵之樹脂的耐熱性及阻燃性的觀點，令全部酸成分為100莫耳%時，宜為5莫耳%以上，更佳為10莫耳%以上，尤佳為20莫耳%以上。又，宜為60莫耳%以下，更佳為50莫耳%以下，尤佳為45莫耳%以下。As other acid components, aliphatic or alicyclic acid anhydrides, aromatic, aliphatic or alicyclic dicarboxylic acids can be used. For example, those obtained by hydrogenating any one of the components listed above can be used. Specifically, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid,meso-butane-1,2,3,4-tetracarboxylic dianhydride, pentane-1,2,4,5-tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic Acid dianhydride, cyclohex-1-ene-2,3,5,6-tetracarboxylic dianhydride, 3-ethylcyclohex-1-ene-3-(1,2),5,6-tetracarboxylic Acid dianhydride, 1-methyl-3-ethylcyclohexane-3-(1,2), 5,6-tetracarboxylic dianhydride, 1-methyl-3-ethylcyclohex-1-ene -3-(1,2), 5,6-tetracarboxylic dianhydride, 1-ethylcyclohexane-1-(1,2), 3,4-tetracarboxylic dianhydride, 1-propylcyclohexane Hexane-1-(2,3),3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1-(2,3),3-(2,3)-tetracarboxylic Acid dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic dianhydride, 1-propane Cyclohexane-1-(2,3),3,4-tetracarboxylic dianhydride, 1,3-dipropylcyclohexane-1-(2,3),3-(2,3)- Tetracarboxylic dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic dianhydride, bicyclo [2.2.2] Octane-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, cyclohexane Alkane dicarboxylic acid etc. Examples of aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, oxydibenzoic acid, distyryl dicarboxylic acid and the like. Examples of aliphatic carboxylic acids include: succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedioic acid, dodecanedioic acid, eicosanedioic acid, acid, 2-methylsuccinic acid, 2-methyladipic acid, 3-methyladipic acid, 3-methylpentanedicarboxylic acid, 2-methyloctanedicarboxylic acid, 3,8-di Methyldecanedicarboxylic acid, 3,7-dimethyldecanedicarboxylic acid, 9,12-dimethyleicosanedioic acid, fumaric acid, maleic acid, etc. These may be used alone or in combination of multiple types. In consideration of heat resistance, adhesion, solubility, cost, etc., sebacic acid, 1,4-cyclohexanedicarboxylic acid, or isophthalic acid is preferable, and among them, sebacic acid is more preferable. When using these components, considering the heat resistance and flame retardancy of the obtained resin with imide bonds, when the total acid component is 100 mol%, it is preferably more than 5 mol%, more preferably 10 mol%. More than mol%, preferably more than 20 mol%. Also, it is preferably not more than 60 mol%, more preferably not more than 50 mol%, and most preferably not more than 45 mol%.

作為本發明中使用之胺成分(二異氰酸酯成分或二胺成分，宜為具有芳香環之胺成分(芳香族二異氰酸酯或芳香族二胺)。就具有芳香環之二異氰酸酯而言，例如可列舉：二苯基甲烷-2,4’-二異氰酸酯、二苯基甲烷-4,4’-二異氰酸酯、3,2’-或3,3’-或4,2’-或4,3’-或5,2’-或5,3’-或6,2’-或6,3’-二甲基二苯基甲烷-2,4’-二異氰酸酯、3,2’-或3,3’-或4,2’-或4,3’-或5,2’-或5,3’-或6,2’-或6,3’-二乙基二苯基甲烷-2,4’-二異氰酸酯、3,2’-或3,3’-或4,2’-或4,3’-或5,2’-或5,3’-或6,2’-或6,3’-二甲氧基二苯基甲烷-2,4’-二異氰酸酯、二苯基甲烷-3,3’-二異氰酸酯、二苯基甲烷-3,4’-二異氰酸酯、二苯醚-4,4’-二異氰酸酯、二苯甲酮-4,4’-二異氰酸酯、二苯碸-4,4’-二異氰酸酯、甲苯-2,4-二異氰酸酯、甲苯-2,6-二異氰酸酯、間二甲苯二異氰酸酯、對二甲苯二異氰酸酯、萘-2,6-二異氰酸酯、4,4’-[2,2雙(4-苯氧基苯基)丙烷]二異氰酸酯、3,3’-或2,2’-二甲基聯苯-4,4’-二異氰酸酯、3,3’-或2,2’-二乙基聯苯-4,4’-二異氰酸酯、3,3’-二甲氧基聯苯-4,4’-二異氰酸酯、3,3’-二乙氧基聯苯-4,4’-二異氰酸酯等。作為具有芳香環之二胺成分，可列舉：對應於該等二異氰酸酯的二胺。該等可單獨使用，亦可將多種組合使用。其中，宜為二苯基甲烷-4,4’-二異氰酸酯。The amine component (diisocyanate component or diamine component) used in the present invention is preferably an amine component (aromatic diisocyanate or aromatic diamine) having an aromatic ring. As for the diisocyanate having an aromatic ring, for example, : Diphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,2'-or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethyldiphenylmethane- 2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-diethyldiphenylmethane-2,4'-diisocyanate, 3,2'- or 3,3'- or 4,2'- or 4,3'- or 5,2'- or 5,3'- or 6,2'- or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate, diphenylmethane-3,3'-diisocyanate, diphenyl Methylmethane-3,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, benzophenone-4,4'-diisocyanate, diphenylphenone-4,4'-diisocyanate, toluene- 2,4-diisocyanate, toluene-2,6-diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, naphthalene-2,6-diisocyanate, 4,4'-[2,2 bis(4- phenoxyphenyl)propane]diisocyanate, 3,3'- or 2,2'-dimethylbiphenyl-4,4'-diisocyanate, 3,3'- or 2,2'-diethyl Biphenyl-4,4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 3,3'-diethoxybiphenyl-4,4'-diisocyanate wait. As a diamine component which has an aromatic ring, the diamine corresponding to these diisocyanate is mentioned. These may be used alone or in combination of multiple types. Among them, diphenylmethane-4,4'-diisocyanate is preferable.

令全部胺成分為100莫耳%時，具有芳香環之胺成分宜為80莫耳%以上，更佳為90莫耳%以上，尤佳為95莫耳%以上，也可為100莫耳%。藉由為上述範圍內，可獲得黏接性及耐熱性優異的具有醯亞胺鍵之樹脂。作為胺成分，可單獨使用具有芳香環之二異氰酸酯成分，亦可單獨使用具有芳香環之二胺成分，也可將它們併用。其中，宜單獨使用具有芳香環之二異氰酸酯成分。When the total amine component is 100 mol%, the amine component having an aromatic ring is preferably 80 mol% or more, more preferably 90 mol% or more, especially preferably 95 mol% or more, or 100 mol% . By being in the said range, the resin which has an imide bond excellent in adhesiveness and heat resistance can be obtained. As the amine component, a diisocyanate component having an aromatic ring may be used alone, a diamine component having an aromatic ring may be used alone, or they may be used in combination. Among these, diisocyanate components having an aromatic ring are preferably used alone.

在不損及本發明之效果的範圍內，其他胺成分可使用脂肪族胺成分(脂肪族二異氰酸酯或脂肪族二胺)或脂環族胺成分(脂環族二異氰酸酯或脂環族二胺)。例如，可使用將前項所列舉之成分中之任一者予以氫化而得的二異氰酸酯或二胺。具體而言，也可列舉：異佛酮二異氰酸酯、1,4-環己烷二異氰酸酯、1,3-環己烷二異氰酸酯、4,4’-二環己基甲烷二異氰酸酯、二異氰酸伸乙酯、二異氰酸伸丙酯、二異氰酸六亞甲酯及對應於該等的二胺等。該等可單獨使用，亦可將多種組合使用。就該等成分而言，考量獲得之具有醯亞胺鍵之樹脂的耐熱性及阻燃性的觀點，令全部胺成分為100莫耳%時，宜為20莫耳%以下，更佳為10莫耳%以下，尤佳為5莫耳%以下，也可為0莫耳%。As other amine components, aliphatic amine components (aliphatic diisocyanate or aliphatic diamine) or alicyclic amine components (alicyclic diisocyanate or ). For example, diisocyanate or diamine obtained by hydrogenating any one of the components listed above can be used. Specifically, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, diisocyanate Ethylene, diisocyanatePropyl ester, hexamethylene diisocyanate, diamines corresponding to these, and the like. These may be used alone or in combination of multiple types. Regarding these components, considering the heat resistance and flame retardancy of the obtained resin having imide bonds, when the total amine component is 100 mol%, it is preferably 20 mol% or less, more preferably 10 mol%. Mole% or less, preferably less than 5 mol%, may be 0 mol%.

本發明之具有醯亞胺鍵之樹脂中，在不損及本發明之效果的範圍內，為了增加與環氧樹脂之反應點，而改善獲得之黏接劑組成物的耐熱性，可共聚具有3個以上之官能基的化合物。例如可列舉：均苯三甲酸等多官能羧酸、5-羥基間苯二甲酸等具有羥基之二羧酸、5-胺基間苯二甲酸等具有胺基之二羧酸、甘油、聚甘油等具有3個以上之羥基者、參(2-胺基乙基)胺等具有3個以上之胺基者。該等之中，考量耐熱性的觀點，宜為均苯三甲酸等多官能羧酸，就其含量而言，令全部酸成分為100莫耳%時，宜為10莫耳%以下，為5莫耳%以下更佳。超過10莫耳%的話，會有在聚合中發生凝膠化，或生成不溶物之虞。In the resin having an imide bond of the present invention, within the scope of not impairing the effect of the present invention, in order to increase the reaction point with the epoxy resin and improve the heat resistance of the obtained adhesive composition, it can be copolymerized with Compounds with more than 3 functional groups. Examples include polyfunctional carboxylic acids such as trimesic acid, dicarboxylic acids having hydroxyl groups such as 5-hydroxyisophthalic acid, dicarboxylic acids having amino groups such as 5-aminoisophthalic acid, glycerin, and polyglycerin Such as those having 3 or more hydroxyl groups, and those having 3 or more amine groups such as ginseng(2-aminoethyl)amine. Among them, from the viewpoint of heat resistance, polyfunctional carboxylic acids such as trimesic acid are preferable, and the content thereof is preferably 10 mole % or less when the total acid component is 100 mole %, which is 5 Mole% or less is better. If it exceeds 10 mol%, gelation may occur during polymerization or insoluble matter may be formed.

本發明之具有醯亞胺鍵之樹脂中，可共聚作為可撓性、黏接性賦予成分的兩末端羧基改性丙烯腈丁二烯橡膠、聚酯二醇、聚醚二醇、聚碳酸酯二醇、二聚酸、氫化二聚酸、二聚酸二醇、兩末端羧基改性聚矽氧烷、兩末端酸酐基改性聚矽氧烷、兩末端羧基改性聚丁二烯、兩末端羧基改性氫化聚丁二烯、聚丁二烯二醇、氫化聚丁二烯二醇等柔軟成分。該等之中，考量可撓性、黏接性的觀點，宜為兩末端羧基改性丙烯腈丁二烯橡膠。使用該等柔軟成分的情況下，令樹脂固體成分整體為100質量%時，宜為10質量%以上，更佳為20質量%以上。又，宜為60質量%以下，更佳為50質量%以下。藉由為上述範圍內，可賦予樹脂柔軟性，而不會損及黏接性、耐熱性、阻燃性的效果。In the resin having an imide bond of the present invention, two-terminal carboxyl group-modified acrylonitrile butadiene rubber, polyester diol, polyether diol, polycarbonate as components for imparting flexibility and adhesion can be copolymerized Diol, dimer acid, hydrogenated dimer acid, dimer acid diol, two-terminal carboxy-modified polysiloxane, two-terminal anhydride-modified polysiloxane, two-terminal carboxyl-modified polybutadiene, two Carboxy-terminal modified hydrogenated polybutadiene, polybutadiene diol, hydrogenated polybutadiene diol and other soft ingredients. Among them, acrylonitrile butadiene rubber modified with carboxyl groups at both terminals is preferable from the viewpoint of flexibility and adhesiveness. When using such a softening component, it is preferably 10 mass % or more, more preferably 20 mass % or more, when the whole resin solid content is 100 mass %. Moreover, it is preferably 60 mass % or less, more preferably 50 mass % or less. By being within the above range, flexibility can be imparted to the resin without impairing the effects of adhesiveness, heat resistance, and flame retardancy.

本發明之具有醯亞胺鍵之樹脂，可藉由如下公知的方法製造：由酸成分與二異氰酸酯成分製造的方法(異氰酸酯法)；或使酸成分與二胺成分反應而形成醯胺酸後，使其閉環的方法(直接法)；或使具有酸酐及醯氯的化合物與二胺反應的方法(醯氯法)等。在工業上，異氰酸酯法係有利。The resin having an imide bond of the present invention can be produced by the following known methods: a method of producing from an acid component and a diisocyanate component (isocyanate method); or after reacting an acid component and a diamine component to form amide acid , a method of closing the ring (direct method); or a method of reacting a compound having an acid anhydride and an acid chloride with a diamine (acyl chloride method), etc. Industrially, the isocyanate method is advantageous.

以下，針對具有醯亞胺鍵之樹脂之製造法，以異氰酸酯法為代表進行敘述，藉由使用各自對應的胺、酸-醯氯，利用上述直接法、醯氯法同樣也可製造具有醯亞胺鍵之樹脂。In the following, the production method of resins having imide bonds will be described using the isocyanate method as a representative. By using the corresponding amines and acid-acyl chlorides, the above-mentioned direct method and the acyl chloride method can also be used to manufacture resins with imide bonds. Resins with amine bonds.

本發明之具有醯亞胺鍵之樹脂的聚合反應，可如以往公知般將酸成分及二異氰酸酯成分在溶劑中於60℃~200℃邊加熱邊攪拌來實施。此時，酸成分/二異氰酸酯成分之莫耳比率宜為85/100~100/100之範圍。此外，一般而言，具有醯亞胺鍵之樹脂中之酸成分及二異氰酸酯成分之含量和聚合時之各成分的比率相同。又，為了促進反應，可使用氟化鈉、氟化鉀、甲醇鈉等鹼金屬類、三乙二胺、三乙胺、1,8-二氮雜雙環[5,4,0]-7-十一烯、1,5-二氮雜雙環[4,3,0]-5-壬烯等胺類、二月桂酸二丁基錫等觸媒。該等觸媒過少的話，無法獲得觸媒效果，過多的話，有可能發生副反應，宜使用令酸成分或異氰酸酯成分各自之莫耳數較多者為100莫耳%時為0.01~5莫耳%之觸媒，更佳為0.1~3莫耳%。The polymerization reaction of the resin having an imide bond of the present invention can be carried out by heating and stirring the acid component and the diisocyanate component in a solvent at 60° C. to 200° C. as conventionally known. At this time, the molar ratio of the acid component/diisocyanate component is preferably in the range of 85/100 to 100/100. In addition, generally, the content of the acid component and the diisocyanate component in the resin which has an imide bond is the same as the ratio of each component at the time of polymerization. Also, in order to promote the reaction, alkali metals such as sodium fluoride, potassium fluoride, sodium methoxide, triethylenediamine, triethylamine, 1,8-diazabicyclo[5,4,0]-7- Undecene, 1,5-diazabicyclo[4,3,0]-5-nonene and other amines, dibutyltin dilaurate and other catalysts. If the catalyst is too small, the catalytic effect cannot be obtained, and if it is too much, side reactions may occur. It is advisable to use 0.01~5 moles when the moles of the acid component or isocyanate component are more than 100 mole%. % catalyst, more preferably 0.1~3 mol%.

具有醯亞胺鍵之樹脂，宜於30℃具有相當於0.1~0.8(dl/g)之對數黏度的分子量，更佳為具有相當於0.2~0.7(dl/g)之對數黏度的分子量，尤佳為具有相當於0.25~0.65(dl/g)之對數黏度的分子量。藉由為上述範圍內，可展現優異的黏接性及耐熱性。Resins with imide bonds preferably have a molecular weight equivalent to a logarithmic viscosity of 0.1-0.8 (dl/g) at 30°C, more preferably a molecular weight equivalent to a logarithmic viscosity of 0.2-0.7 (dl/g), especially Preferably, it has a molecular weight corresponding to a logarithmic viscosity of 0.25 to 0.65 (dl/g). By being in the said range, excellent adhesiveness and heat resistance can be exhibited.

具有醯亞胺鍵之樹脂的玻璃轉移溫度宜為80℃以上，更佳為100℃以上，尤佳為120℃以上。又，上限並無特別限定，宜為300℃以下，更佳為290℃以下，尤佳為285℃以下。藉由為上述範圍內，可展現優異的黏接性及耐熱性。The glass transition temperature of the resin having an imide bond is preferably above 80°C, more preferably above 100°C, and most preferably above 120°C. Also, the upper limit is not particularly limited, but it is preferably 300°C or lower, more preferably 290°C or lower, and most preferably 285°C or lower. By being in the said range, excellent adhesiveness and heat resistance can be exhibited.

就本發明之具有醯亞胺鍵之樹脂的聚合中可使用的溶劑而言，例如可列舉：N-甲基-2-吡咯烷酮、γ-丁內酯、二甲基咪唑啶酮、二甲基亞碸、二甲基甲醯胺、二甲基乙醯胺、環己酮、環戊酮等，其中，考量沸點低與聚合效率良好的方面，宜為二甲基乙醯胺。又，聚合後可利用聚合所使用之溶劑或其他低沸點溶劑來稀釋以調整非揮發性成分濃度、溶液黏度。As for the solvent usable for the polymerization of the resin having an imide bond of the present invention, for example, N-methyl-2-pyrrolidone, γ-butyrolactone, dimethylimidazolidone, dimethyl Among them, ethylene oxide, dimethylformamide, dimethylacetamide, cyclohexanone, cyclopentanone, etc., are preferable in terms of low boiling point and good polymerization efficiency. In addition, after polymerization, it can be diluted with the solvent used for polymerization or other low boiling point solvents to adjust the concentration of non-volatile components and the viscosity of the solution.

作為低沸點溶劑，可列舉：甲苯、二甲苯等芳香族系溶劑；己烷、庚烷、辛烷等脂肪族系溶劑；甲醇、乙醇、丙醇、丁醇、異丙醇等醇系溶劑；丙酮、甲乙酮、甲基異丁基酮、環己酮、環戊酮等酮系溶劑；二乙醚、四氫呋喃等醚系溶劑；乙酸乙酯、乙酸丁酯、乙酸異丁酯等酯系溶劑等。Examples of low boiling point solvents include: aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane, heptane, and octane; alcoholic solvents such as methanol, ethanol, propanol, butanol, and isopropanol; Ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone; ether solvents such as diethyl ether and tetrahydrofuran; ester solvents such as ethyl acetate, butyl acetate, and isobutyl acetate, etc.

本發明之黏接劑組成物的非揮發性成分中之具有醯亞胺鍵之樹脂之含量，宜為40質量%以上，更佳為45質量%以上，尤佳為50質量%以上。又，宜為90質量%以下，更佳為80質量%以下，尤佳為70質量%以下。藉由為上述範圍內，可展現黏接劑組成物之優異的黏接性及耐熱性。The content of the resin having an imide bond in the non-volatile components of the adhesive composition of the present invention is preferably at least 40% by mass, more preferably at least 45% by mass, and most preferably at least 50% by mass. Moreover, it is preferably 90% by mass or less, more preferably 80% by mass or less, and most preferably 70% by mass or less. By being in the said range, the outstanding adhesiveness and heat resistance of an adhesive composition can be exhibited.

<通式(1)表示之磷化合物><Phosphorus compound represented by general formula (1)>

本發明之黏接劑組成物含有通式(1)表示之磷化合物(以下亦稱為通式(1)之磷化合物。)。藉由含有通式(1)之磷化合物，可獲得具有優異的黏接性、耐熱性、阻燃性及絕緣可靠性之黏接劑組成物。通式(1)中，R₁~R₄為通式(2)~(4)中之任一者，R₁~R₄中之至少1個為通式(2)。宜為2個係通式(2)，更佳為3個係通式(2)。通式(2)為2個時的理想位置並無特別限定，可為R₁與R₂，也可為R₁與R₃。通式(1)及通式(3)中，多個X各自獨立地為「＊-CH₂-＊」或「＊-C(CH₃)₂-＊」(＊係直接鍵結於通式(1)或通式(3)之芳香環的部位。以下，簡稱為CH₂或C(CH₃)₂)。宜為通式(1)或通式(3)中之任一者之X為C(CH₃)₂，更佳為通式(1)與通式(3)之X均為C(CH₃)₂。又，通式(1)及通式(3)中，多個Y各自獨立地為氫或羥基。惟，通式(1)中，多個Y中之至少1個為羥基，宜為2個Y為羥基。通式(1)中，藉由Y中之至少1個為羥基，通式(1)之磷化合物具有反應性官能基，可展現高溫高濕環境下之滲出抑制及優異的絕緣可靠性。就羥基的位置而言，可相對於X為鄰位或對位，至少1個羥基宜相對於X為對位，2個羥基均相對於X為對位更佳。通式(3)中，羥基宜為1個以上，更佳為2個。其位置相對於X可為鄰位或對位，至少1個羥基宜相對於X為對位，2個羥基均相對於X為對位更佳。通式(4)中，R₅為氫或碳數1~10之烷基。宜為碳數2~8之烷基，更佳為碳數3~5之烷基。烷基可為直鏈狀或分支狀。具體而言，可列舉：甲基、乙基、丙基(正丙基、異丙基)、丁基(正丁基、異丁基、第三丁基)、戊基、己基、庚基、辛基、壬基、癸基等，宜為丙基、丁基或戊基，更佳為丁基。通式(1)之磷化合物可為單一的化合物，也可為取代基不同的多種化合物之混合物。The adhesive composition of the present invention contains the phosphorus compound represented by the general formula (1) (hereinafter also referred to as the phosphorus compound of the general formula (1).). By containing the phosphorus compound of the general formula (1), an adhesive composition having excellent adhesiveness, heat resistance, flame retardancy and insulation reliability can be obtained. In general formula (1), R₁ to R₄ are any one of general formulas (2) to (4), and at least one of R₁ to R₄ is general formula (2). Preferably it is 2 systems of general formula (2), more preferably 3 systems of general formula (2). The ideal position when there are two general formula (2) is not particularly limited, and may be R₁ and R₂ , or R₁ and R₃ . In general formula (1) and general formula (3), multiple Xs are each independently "*-CH₂ -*" or "*-C(CH₃ )₂ -*" (* is directly bonded to the general formula (1) or the aromatic ring part of the general formula (3). Hereinafter, it is simply referred to as CH₂ or C(CH₃ )₂ ). It is preferable that X in any one of general formula (1) or general formula (3) is C(CH₃ )₂ , more preferably that X in both general formula (1) and general formula (3) is C(CH₃ )₂ . Moreover, in general formula (1) and general formula (3), some Y is each independently hydrogen or a hydroxyl group. However, in the general formula (1), at least one of the plurality of Ys is a hydroxyl group, preferably two Ys are hydroxyl groups. In the general formula (1), since at least one of Y is a hydroxyl group, the phosphorus compound of the general formula (1) has a reactive functional group, and can exhibit bleed suppression and excellent insulation reliability in a high-temperature and high-humidity environment. The position of the hydroxyl group may be in the ortho or para position with respect to X, preferably at least one of the hydroxyl groups is at the para position with respect to X, and more preferably both of the two hydroxyl groups are at the para position with respect to X. In the general formula (3), the number of hydroxyl groups is preferably one or more, more preferably two. Its position relative to X may be in the ortho or para position, preferably at least one hydroxyl group is in the para position relative to X, and more preferably both of the two hydroxyl groups are in the para position relative to X. In the general formula (4), R₅ is hydrogen or an alkyl group with 1 to 10 carbons. It is preferably an alkyl group having 2 to 8 carbon atoms, more preferably an alkyl group having 3 to 5 carbon atoms. The alkyl group may be linear or branched. Specifically, methyl, ethyl, propyl (n-propyl, isopropyl), butyl (n-butyl, isobutyl, t-butyl), pentyl, hexyl, heptyl, Octyl, nonyl, decyl, etc. are preferably propyl, butyl or pentyl, more preferably butyl. The phosphorus compound of the general formula (1) may be a single compound or a mixture of a plurality of compounds having different substituents.

通式(1)之磷化合物的含量，相對於具有醯亞胺鍵之樹脂100質量份，宜為5質量份以上，更佳為10質量份以上，尤佳為15質量份以上，特佳為20質量份以上。又，宜為100質量份以下，更佳為90質量份以下，尤佳為80質量份以下，特佳為70質量份以下。藉由為上述範圍內，可展現優異的黏接性、耐熱性、阻燃性及絕緣可靠性。The content of the phosphorus compound of the general formula (1) is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and especially preferably 15 parts by mass or more, with respect to 100 parts by mass of the resin having an imide bond. More than 20 parts by mass. Moreover, it is preferably at most 100 parts by mass, more preferably at most 90 parts by mass, particularly preferably at most 80 parts by mass, and most preferably at most 70 parts by mass. By being within the above range, excellent adhesiveness, heat resistance, flame retardancy, and insulation reliability can be exhibited.

就通式(1)之磷化合物而言，宜為具有化學式(9)~(11)表示之結構之磷化合物(以下，分別亦稱為化學式(9)~(11)之磷化合物。)中之任一者，其中，宜為化學式(9)之磷化合物。通式(1)之磷化合物中，化學式(9)~(11)之磷化合物之合計量所佔的比率宜為30質量%以上，更佳為50質量%以上，尤佳為80質量%以上，特佳為90質量%以上，也可為100質量%。藉由以上述比率含有，可展現優異的絕緣可靠性。又，化學式(9)~(11)之磷化合物合計中，化學式(9)之磷化合物所佔的比率宜為30質量%以上，更佳為50質量%以上，尤佳為80質量%以上，特佳為90質量%以上，也可為100質量%。化學式(10)之磷化合物多的話，會有黏接性降低之虞，化學式(11)之磷化合物多的話，會有阻燃性降低之虞。As far as the phosphorus compound of general formula (1) is concerned, it is preferably a phosphorus compound having a structure represented by chemical formula (9) to (11) (hereinafter also referred to as a phosphorus compound of chemical formula (9) to (11).) Any of them, among them, the phosphorus compound of chemical formula (9) is preferable. Among the phosphorus compounds of the general formula (1), the ratio of the total amount of the phosphorus compounds of the chemical formulas (9) to (11) is preferably at least 30% by mass, more preferably at least 50% by mass, and most preferably at least 80% by mass , preferably more than 90% by mass, and may be 100% by mass. Excellent insulation reliability can be exhibited by containing in the said ratio. Also, in the total of the phosphorus compounds of the chemical formulas (9) to (11), the proportion of the phosphorus compound of the chemical formula (9) is preferably 30% by mass or more, more preferably 50% by mass or more, especially preferably 80% by mass or more, Most preferably, it is 90 mass % or more, and may be 100 mass %. When the phosphorus compound of the chemical formula (10) is too much, the adhesiveness may be lowered, and if the phosphorus compound of the chemical formula (11) is too much, the flame retardancy may be lowered.

[化10]

[chemical 10]

通式(1)之磷化合物，因為對於溶劑之溶解性高，製作黏接劑組成物後操作性也良好。作為溶劑，可列舉：N-甲基-2-吡咯烷酮、γ-丁內酯、二甲基咪唑啶酮、二甲基亞碸、二甲基甲醯胺、二甲基乙醯胺、環己酮、環戊酮等。又，作為低沸點溶劑，可列舉：甲苯、二甲苯等芳香族系溶劑；己烷、庚烷、辛烷等脂肪族系溶劑；甲醇、乙醇、丙醇、丁醇、異丙醇等醇系溶劑；丙酮、甲乙酮、甲基異丁基酮、環己酮、環戊酮等酮系溶劑；二乙醚、四氫呋喃等醚系溶劑；乙酸乙酯、乙酸丁酯、乙酸異丁酯等酯系溶劑等。通式(1)之磷化合物，宜於室溫(25℃)在前述溶劑中溶解10質量%以上，更佳為20質量%以上，尤佳為30質量%以上。The phosphorus compound of the general formula (1) has high solubility in solvents, and also has good workability after making an adhesive composition. Examples of solvents include: N-methyl-2-pyrrolidone, γ-butyrolactone, dimethylimidazolidinone, dimethylsulfoxide, dimethylformamide, dimethylacetamide, cyclohexyl ketone, cyclopentanone, etc. Moreover, examples of low-boiling point solvents include aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane, heptane, and octane; alcohols such as methanol, ethanol, propanol, butanol, and isopropanol. Solvents; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone; ether solvents such as diethyl ether and tetrahydrofuran; ester solvents such as ethyl acetate, butyl acetate, and isobutyl acetate wait. The phosphorus compound of general formula (1) is suitable for indoorTemperature (25° C.) dissolves at least 10% by mass, more preferably at least 20% by mass, and most preferably at least 30% by mass in the aforementioned solvent.

在不損及本發明之效果的範圍內，可添加通式(1)之磷化合物以外之磷化合物。例如可列舉：三光(股)製的商品名BCA、HCA(註冊商標)、BzHCA、M-Acid、M-Ester、HCA-HQ、HCA-NQ等次膦酸衍生物、大八化學(股)製的商品名CR-733S、CR-741、PX-200、PX-202、ADEKA(股)製的商品名ADEKASTAB(註冊商標)FP-600、PFR等縮合型磷酸酯化合物、大塚化學(股)製的商品名SPB-100、SPE-100、SPB-100L、SPH-100、伏見製藥所(股)製的商品名FP-100、FP-110、FP-300、FP-400、FP-430、FP-500、FP-800E、FP-800H、FP-900H、FP-1000等環狀磷腈化合物、Clariant Japan(股)製的商品名Exolit(註冊商標)OP系列等磷鋁鹽化合物、日產化學(股)製的商品名PHOSMEL(註冊商標)200等三聚氰胺系化合物、ADEKA(股)製的商品名ADEKASTAB FP-2100JC、FP-2200S、FP-2500S等膨脹(Intumescent)系阻燃劑等，該等可單獨使用，亦可將多種組合使用。Phosphorus compounds other than the phosphorus compound of general formula (1) can be added within the range which does not impair the effect of this invention. For example, phosphinic acid derivatives such as BCA, HCA (registered trademark), BzHCA, M-Acid, M-Ester, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd., Daihachi Chemical Co., Ltd. Condensed phosphate ester compounds such as CR-733S, CR-741, PX-200, PX-202, ADEKA Co., Ltd. trade name ADEKASTAB (registered trademark) FP-600, PFR, Otsuka Chemical Co., Ltd. The trade names of SPB-100, SPE-100, SPB-100L, SPH-100 manufactured by Fushimi Pharmaceutical Co., Ltd., the trade names of FP-100, FP-110, FP-300, FP-400, FP-430, Cyclic phosphazene compounds such as FP-500, FP-800E, FP-800H, FP-900H, FP-1000, etc., phosphazene compounds such as Exolit (registered trademark) OP series manufactured by Clariant Japan Co., Ltd., Nissan Chemical Melamine-based compounds such as PHOSMEL (registered trademark) 200 manufactured by ADEKA Co., Ltd., and intumescent flame retardants such as ADEKASTAB FP-2100JC, FP-2200S, and FP-2500S manufactured by ADEKA Co., Ltd. etc. may be used individually or in combination of multiple types.

本發明之黏接劑組成物之非揮發性成分中之理想含磷率為1.0~5.0質量%，更佳為1.0~3.0質量%。含磷率少的話，無法獲得良好的阻燃性，反之多的話會有黏接性、耐熱性、絕緣可靠性降低的傾向。The ideal phosphorus content in the non-volatile components of the adhesive composition of the present invention is 1.0-5.0% by mass, more preferably 1.0-3.0% by mass. If the phosphorus content is low, good flame retardancy cannot be obtained, and if it is high, the adhesiveness, heat resistance, and insulation reliability tend to decrease.

在不損及本發明之效果的範圍內，可添加不含磷的阻燃劑。例如可列舉：昭和電工(股)製的商品名Higilite(註冊商標)H-42、H-42M、H-43、H-43M等氫氧化鋁、協和化學工業(股)製的商品名Kisuma(註冊商標)5、8、5Q-S、200-06H等氫氧化鎂、日產化學(股)製的商品名MC-4000、MC-4500、MC-6000等三聚氰胺氰尿酸酯化合物等，該等可單獨使用，亦可將多種組合使用。A phosphorus-free flame retardant may be added within the range not impairing the effect of the present invention. For example, aluminum hydroxides such as Showa Denko Co., Ltd. product names Higilite (registered trademark) H-42, H-42M, H-43, and H-43M, Kyowa Chemical Industry Co., Ltd. product name Kisuma ( Magnesium hydroxide such as registered trademark) 5, 8, 5Q-S, 200-06H, etc., melamine cyanurate compounds such as MC-4000, MC-4500, MC-6000 manufactured by Nissan Chemical Co., Ltd., etc. They can be used alone or in combination.

<環氧樹脂><Epoxy resin>

本發明之黏接劑組成物中可摻合環氧樹脂。環氧樹脂之含量，相對於具有醯亞胺鍵之樹脂100質量份，宜為10質量份以上，更佳為20質量份以上，尤佳為25質量份以上。又，宜為100質量份以下，更佳為80質量以下，尤佳為70質量份以下。藉由為前述上限值以下，可將具有醯亞胺鍵之樹脂之含有比例維持在一定量以上。因此，不會有環氧樹脂未硬化而殘存的情形，黏接劑組成物之硬化後之耐熱性良好。又，藉由為前述下限值以上，可與具有醯亞胺鍵之樹脂形成充分的交聯反應，黏接劑組成物之硬化後之耐熱性、絕緣可靠性良好。Epoxy resin may be blended into the adhesive composition of the present invention. The content of the epoxy resin is preferably at least 10 parts by mass, more preferably at least 20 parts by mass, and most preferably at least 25 parts by mass, based on 100 parts by mass of the resin having an imide bond. Moreover, it is preferably 100 mass parts or less, more preferably 80 mass parts or less, and especially preferably 70 mass parts or less. By being below the said upper limit, the content ratio of the resin which has an imide bond can be maintained more than fixed amount. Therefore, the epoxy resin does not remain uncured, and the heat resistance of the adhesive composition after curing is good. Moreover, when it is more than the said lower limit, sufficient crosslinking reaction can be formed with the resin which has an imide bond, and the heat resistance after hardening of an adhesive composition, and insulation reliability are favorable.

就本發明之黏接劑組成物中使用之環氧樹脂而言，於25℃為液狀、半固體或固體狀均可，宜於25℃為液狀，且1分子中具有2個以上之環氧基之環氧樹脂較佳。前述環氧樹脂可經改性，又，也可在分子骨架內含有硫原子、氮原子、磷原子等。例如可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、或將該等予以氫化而得者、苯酚酚醛清漆型環氧樹脂、萘型環氧樹脂、二環戊二烯型環氧樹脂、NBR(兩末端羧基改性丙烯腈丁二烯橡膠)改性環氧樹脂、二聚酸改性環氧樹脂、聚丁二烯改性環氧樹脂、脂肪族環氧樹脂、脂環族環氧樹脂等。作為該等的市售品，例如可列舉：三菱化學(股)製的商品名jER(註冊商標)825、jER827、jER828、YL980、DIC(股)製的商品名EPICLON(註冊商標)840、840-S、850、850-S、EXA-850CRP、850-LC、新日鐵住金化學(股)製的商品名YD-127、YD-128、YD-128G、YD-128S、YD-128CA、YD-8125、YD-825GS、YD-825GHS等雙酚A型液狀環氧樹脂、三菱化學(股)製的商品名jER806、jER806H、jER807、YL983U、DIC(股)製的商品名EPICLON830、830-S、835、EXA-830CRP、EXA-830LVP、EXA-835LV、新日鐵住金化學(股)製的商品名YDF-170、YDF-170N、YDF-8170C、YDF-870GS等雙酚F型液狀環氧樹脂、三菱化學(股)製的商品名YX8000、YX8034、新日鐵住金化學(股)製的商品名ST-3000等氫化雙酚A型液狀環氧樹脂、三菱化學(股)製的商品名jER152、DIC(股)製的商品名EPICLON N-730A等苯酚酚醛清漆型液狀環氧樹脂、DIC(股)製的商品名EPICLON HP-4032D等萘型液狀環氧樹脂、ADEKA(股)製的商品名ADEKA RESIN(註冊商標)EP-4088S、EP-4088L等二環戊二烯型液狀環氧樹脂、DIC(股)製的商品名EPICLON TSR-960、TSR-601等NBR改性環氧樹脂、三菱化學(股)製的商品名jER871、jER872、新日鐵住金化學(股)製的商品名Epotohto(註冊商標)YD-172等二聚酸改性環氧樹脂、日本曹達(股)製的商品名JP-100、JP-200、JP-400等丁二烯改性環氧樹脂、大賽璐化學工業(股)製的商品名CELLOXIDE(註冊商標)2021P、2081等脂環族環氧樹脂、日產化學工業(股)製的TEPIC(註冊商標)等異氰尿酸三環氧丙酯、Nagase ChemteX(股)製的商品名Denacol(註冊商標)EX-1000系列、Denacol L系列、Denacol DLC系列、Denarex(註冊商標)系列、EX991等，該等可單獨使用，亦可將多種組合使用。As far as the epoxy resin used in the adhesive composition of the present invention is concerned, it can be liquid, semi-solid or solid at 25°C, preferably liquid at 25°C, and has more than 2 epoxy resins in one molecule. Epoxy-based epoxy resins are preferred. The aforementioned epoxy resin may be modified, and may contain sulfur atoms, nitrogen atoms, phosphorus atoms, etc. in the molecular skeleton. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, or those obtained by hydrogenating these, phenol novolac type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type Epoxy resin, NBR (two-terminal carboxyl modified acrylonitrile butadiene rubber) modified epoxy resin, dimer acid modified epoxy resin, polybutadiene modified epoxy resin, aliphatic epoxy resin, grease Cyclic epoxy resin, etc. Such commercially available products include, for example, product names jER (registered trademark) 825, jER827, jER828, YL980 manufactured by Mitsubishi Chemical Co., Ltd., and EPICLON (registered trademark) 840, 840 manufactured by DIC Corporation. -S, 850, 850-S, EXA-850CRP, 850-LC, Nippon Steel & Sumikin Chemical Co., Ltd. product names YD-127, YD-128, YD-128G, YD-128S, YD-128CA, YD -8125, YD-825GS, YD-825GHS and other bisphenol A liquid epoxy resins, Mitsubishi Chemical Co., Ltd. product names jER806, jER806H, jER807, YL983U, DIC Co., Ltd. product names EPICLON830, 830- S, 835, EXA-830CRP, EXA-830LVP, EXA-835LV, trade name YDF-170 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.,Bisphenol F-type liquid epoxy resins such as YDF-170N, YDF-8170C, and YDF-870GS, trade names YX8000 and YX8034 manufactured by Mitsubishi Chemical Co., Ltd., and ST-3000 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Isohydrogenated bisphenol A type liquid epoxy resin, Mitsubishi Chemical Co., Ltd. product name jER152, DIC Co., Ltd. product name EPICLON N-730A and other phenol novolac type liquid epoxy resin, DIC Co., Ltd. Naphthalene-type liquid epoxy resins such as EPICLON HP-4032D manufactured by ADEKA Co., Ltd., dicyclopentadiene-type liquid epoxy resins such as ADEKA RESIN (registered trademark) EP-4088S and EP-4088L manufactured by ADEKA Co., Ltd. NBR-modified epoxy resins such as EPICLON TSR-960 and TSR-601 manufactured by DIC Co., Ltd., jER871 and jER872 manufactured by Mitsubishi Chemical Co., Ltd., and trade names manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Dimer acid-modified epoxy resins such as Epotohto (registered trademark) YD-172, butadiene-modified epoxy resins such as JP-100, JP-200, and JP-400 manufactured by Nippon Soda Co., Ltd., Daicel Cycloaliphatic epoxy resins such as CELLOXIDE (registered trademark) 2021P and 2081 manufactured by Chemical Industry Co., Ltd. Triglycidylisocyanurate such as TEPIC (registered trademark) manufactured by Nissan Chemical Industry Co., Ltd., Nagase ChemteX Denacol (registered trademark) EX-1000 series, Denacol L series, Denacol DLC series, Denarex (registered trademark) series, EX991, etc. manufactured by Co., Ltd. can be used alone or in combination.

就環氧樹脂而言，也可使用於25℃為半固體或固體狀之環氧樹脂。於25℃為半固體或固體狀之環氧樹脂可經改性，又，也可在分子骨架內含有硫原子、氮原子、磷原子等。例如可列舉：雙酚A型環氧樹脂、雙酚F型環氧樹脂、或將該等予以氫化而得者、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、聯苯型環氧樹脂、萘型環氧樹脂、二環戊二烯型環氧樹脂、脂肪族環氧樹脂、脂環族環氧樹脂等。作為該等的市售品，例如可列舉：三菱化學(股)製的商品名jER1001、jER1004、jER1007、jER1010、新日鐵住金化學(股)製的商品名Epotohto YD-134、YD-011、YD-014、YD-017、DIC(股)製的商品名EPICLON860、1050、1055、2050、3050、4050、7050等雙酚A型環氧樹脂、三菱化學(股)製的商品名jER4004P、jER4005P、jER4007P、jER4010P、新日鐵住金化學(股)製的商品名Epotohto YDF-2001、YDF-2004等雙酚F型環氧樹脂、新日鐵住金化學(股)製的商品名ST-4000D等氫化雙酚A型環氧樹脂、三菱化學(股)製的商品名jER154、DIC(股)製的商品名EPICLON N-740、N-770、N-775、日本化藥(股)製的商品名EPPN(註冊商標)-201、EPPN-501H、EPPN-501HY、EPPN-502H、NC-2000L、陶氏化學公司製的商品名DEN-438等苯酚酚醛清漆型環氧樹脂、DIC(股)製的商品名EPICLON N-660、N-665、N-670、N-673、N-680、N-690、N-695、新日鐵住金化學(股)製的商品名Epotohto YDCN-700-7、YDCN-700-10、日本化藥(股)製的商品名EOCN(註冊商標)-1020、EOCN-102S、EOCN-103S、EOCN-104S等甲酚酚醛清漆型環氧樹脂、三菱化學(股)製的商品名YX4000、YX4000H、日本化藥(股)製的商品名NC-3000、NC-3000L、NC-3000H、NC-3100等聯苯型環氧樹脂、DIC(股)製的商品名EPICLON HP-4700、HP-4710、HP-4770、HP-5000、HP-6000、日本化藥(股)製的商品名NC-7000L、NC-7300L等萘型環氧樹脂、DIC(股)製的商品名EPICLON HP-7200L、HP-7200、HP-7200H、HP-7200HH、HP-7200HHH、日本化藥(股)製的商品名XD-1000等二環戊二烯型環氧樹脂、大賽璐化學工業(股)製的商品名EHPE(註冊商標)3150等脂環族環氧樹脂、DIC(股)製的EXA-9726等含磷環氧樹脂等，該等可單獨使用，亦可將多種組合使用。As for the epoxy resin, epoxy resins that are semi-solid or solid at 25°C can also be used. Epoxy resins that are semi-solid or solid at 25°C can be modified, and can also contain sulfur atoms, nitrogen atoms, phosphorus atoms, etc. in the molecular skeleton. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, or those obtained by hydrogenating them, phenol novolak type epoxy resin, cresol novolak type epoxy resin, biphenyl type Epoxy resins, naphthalene-type epoxy resins, dicyclopentadiene-type epoxy resins, aliphatic epoxy resins, alicyclic epoxy resins, and the like. Such commercially available products include, for example, Mitsubishi Chemical Co., Ltd. product names jER1001, jER1004, jER1007, jER1010, Nippon Steel & Sumikin Chemical Co., Ltd. product names Epotohto YD-134, YD-011, YD-014, YD-017, brand name of DIC Co., Ltd. EPICLON 860, 1050, 1055, 2050, 3050, 4050, 7050, etc. Bisphenol A type epoxy resin, brand name of Mitsubishi Chemical Co., Ltd.Bisphenol F-type epoxy resins such as jER4004P, jER4005P, jER4007P, jER4010P, Nippon Steel & Sumikin Chemical Co., Ltd. trade name Epotohto YDF-2001, YDF-2004, Nippon Steel & Sumikin Chemical Co., Ltd. trade name ST Hydrogenated bisphenol A type epoxy resin such as -4000D, Mitsubishi Chemical Co., Ltd. product name jER154, DIC Co., Ltd. product name EPICLON N-740, N-770, N-775, Nippon Kayaku Co., Ltd. Phenol novolak type epoxy resins such as EPPN (registered trademark)-201, EPPN-501H, EPPN-501HY, EPPN-502H, NC-2000L, and DEN-438 manufactured by Dow Chemical Company, DIC ( Co., Ltd.) trade name EPICLON N-660, N-665, N-670, N-673, N-680, N-690, N-695, Nippon Steel Sumikin Chemical Co., Ltd. trade name Epotohto YDCN- 700-7, YDCN-700-10, Nippon Kayaku Co., Ltd. product name EOCN (registered trademark)-1020, EOCN-102S, EOCN-103S, EOCN-104S and other cresol novolak type epoxy resins, Mitsubishi Chemical Co., Ltd. product names YX4000, YX4000H, Nippon Kayaku Co., Ltd. product names NC-3000, NC-3000L, NC-3000H, NC-3100 and other biphenyl type epoxy resins, DIC Co., Ltd. product Naphthalene-type epoxy resins such as EPICLON HP-4700, HP-4710, HP-4770, HP-5000, HP-6000, Nippon Kayaku Co., Ltd. product names NC-7000L, NC-7300L, DIC ( Dicyclopentadiene-type epoxy resins such as EPICLON HP-7200L, HP-7200, HP-7200H, HP-7200HH, HP-7200HHH, trade name XD-1000 manufactured by Nippon Kayaku Co., Ltd. Cycloaliphatic epoxy resins such as EHPE (registered trademark) 3150 manufactured by Daicel Chemical Co., Ltd., and phosphorous-containing epoxy resins such as EXA-9726 manufactured by DIC Co., Ltd. may be used alone or Various combinations are possible.

一部分環氧樹脂及磷化合物中，一般在其製造過程中會含有作為雜質的氯。但是，考量減低環境負荷的觀點，需降低鹵素量，又，已知氯，特別是水解性氯多的話，絕緣性會降低。故黏接劑組成物之非揮發性成分中之總氯量宜為500ppm以下，更佳為300ppm以下。Some epoxy resins and phosphorus compounds generally contain chlorine as an impurity during the production process. However, from the viewpoint of reducing the environmental load, it is necessary to reduce the amount of halogens, and it is known that if there is much chlorine, especially hydrolyzable chlorine, the insulating properties will be lowered. Therefore, the total chlorine content in the non-volatile components of the adhesive composition is preferably less than 500 ppm, more preferably less than 300 ppm.

本發明之黏接劑組成物中，在不損及本發明之效果的範圍內，為了提高塗覆穩定性，除了添加前述溶劑外，還可添加表面張力33dyn/cm以下之有機溶劑。例如可列舉：甲苯、二甲苯等芳香族系溶劑；己烷、庚烷、辛烷等脂肪族系溶劑；甲醇、乙醇、丙醇、丁醇、異丙醇等醇系溶劑；丙酮、甲乙酮、甲基異丁基酮、環己酮、環戊酮等酮系溶劑；二乙醚、四氫呋喃等醚系溶劑；乙酸乙酯、乙酸丁酯、乙酸異丁酯等酯系溶劑；二乙二醇單乙醚乙酸酯、二乙二醇單丁醚乙酸酯等乙酸酯系溶劑等，該等可單獨使用，亦可將多種組合使用。就溶劑的摻合量而言，只要可溶解具有醯亞胺鍵之樹脂，則無特別限定，相對於具有醯亞胺鍵之樹脂100質量份，宜為50質量份以上，更佳為100質量份以上，尤佳為200質量份以上。又，宜為2000質量份以下，更佳為1500質量份以下，尤佳為1000質量份以下。In the adhesive composition of the present invention, an organic solvent having a surface tension of 33 dyn/cm or less may be added in addition to the above-mentioned solvents in order to improve coating stability within the range that does not impair the effects of the present invention. For example, aromatic solvents such as toluene and xylene; aliphatic solvents such as hexane, heptane and octane; alcohol solvents such as methanol, ethanol, propanol, butanol and isopropanol; acetone, methyl ethyl ketone, Ketone solvents such as methyl isobutyl ketone, cyclohexanone, and cyclopentanone; ether solvents such as diethyl ether and tetrahydrofuran; ester solvents such as ethyl acetate, butyl acetate, and isobutyl acetate; diethylene glycol mono Acetate-based solvents such as diethyl ether acetate and diethylene glycol monobutyl ether acetate, etc. may be used alone or in combination. The blending amount of the solvent is not particularly limited as long as it can dissolve the resin having an imide bond, but it is preferably 50 parts by mass or more, more preferably 100 parts by mass, based on 100 parts by mass of the resin having an imide bond. More than 200 parts by mass, preferably more than 200 parts by mass. Moreover, it is preferably at most 2000 parts by mass, more preferably at most 1500 parts by mass, and most preferably at most 1000 parts by mass.

本發明之黏接劑組成物中，在不損及本發明之效果的範圍內，為了提高塗覆穩定性，可添加表面調整劑。考量黏接性的觀點，表面調整劑宜為沸點150℃以下者，更佳為沸點120℃以下者。具體而言，並無特別限定，可列舉：日信化學工業(股)製Surfynol(註冊商標)104E、104H、104A、104PA、104S、420、440、465、485、SE、SE-F、OLFINE(註冊商標)EXP.4001、4123、4200、4300等，該等可單獨使用，亦可將多種組合使用。就該等表面調整劑的摻合量而言，相對於黏接劑組成物中之具有醯亞胺鍵之樹脂與環氧樹脂的合計質量，宜為0.01~0.5質量%，更佳為0.05~0.3質量%。表面調整劑的摻合量少的話，會有難以獲得塗覆穩定性之虞，摻合量多的話，會有難以展現黏接性之虞。In the adhesive composition of the present invention, a surface conditioner may be added in order to improve coating stability within a range not impairing the effect of the present invention. From the viewpoint of adhesiveness, the surface modifier is preferably one having a boiling point of 150° C. or lower, more preferably one having a boiling point of 120° C. or lower. Specifically, it is not particularly limited, and examples thereof include Surfynol (registered trademark) 104E, 104H, 104A, 104PA, 104S, 420, 440, 465, 485, SE, SE-F, OLFINE manufactured by Nissin Chemical Industry Co., Ltd. (registered trademark) EXP. 4001, 4123, 4200, 4300, etc., can be used alone or in combination. In terms of the blending amount of these surface modifiers, it is preferably 0.01-0.5% by mass, more preferably 0.05- 0.3% by mass. If the blending amount of the surface conditioner is small, it may be difficult to obtain coating stability, and if the blending amount is large, it may be difficult to express adhesiveness.

本發明之黏接劑組成物中，在不損及本發明之效果的範圍內，為了以更高水平提升高溫高濕環境下之絕緣可靠性，可添加高耐熱性樹脂。作為高耐熱性樹脂，宜為玻璃轉移溫度為200℃以上之樹脂，更佳為250℃以上之樹脂。具體而言，並無特別限定，可列舉：聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醚醯亞胺樹脂、聚醚醚酮樹脂等。又，高耐熱樹脂宜溶解於溶劑。作為滿足該等條件者，令來自全部酸成分之構成單元為100莫耳%時具有芳香環之多元羧酸之酸酐為90莫耳%以上的樹脂較佳，其中，為聚醯胺醯亞胺樹脂最佳。關於具體的原料如前述。In the adhesive composition of the present invention, a high heat-resistant resin may be added in order to improve the insulation reliability in a high-temperature and high-humidity environment at a higher level within the range that does not impair the effects of the present invention. as high heat resistanceThe resin is preferably a resin with a glass transition temperature above 200°C, more preferably a resin above 250°C. Specifically, it is not particularly limited, and examples thereof include polyimide resins, polyamideimide resins, polyetherimide resins, and polyether ether ketone resins. Also, the high heat-resistant resin is preferably dissolved in a solvent. As those satisfying these conditions, when the constituent units derived from all the acid components are 100 mol%, the resin of polycarboxylic acid anhydride having an aromatic ring is preferably 90 mol% or more, among them, polyamideimide Resin is best. The specific raw materials are as described above.

本發明之黏接劑組成物中，在不損及本發明之效果的範圍內，為了促進硬化，除了添加前述環氧樹脂外，還可添加環氧丙胺型環氧樹脂。環氧丙胺型環氧樹脂的添加量，相對於黏接劑組成物中之具有醯亞胺鍵之樹脂與前述環氧樹脂之合計質量，宜為0.01質量%~5質量%，為0.05質量%~2質量%尤佳。環氧丙胺型環氧樹脂的摻合量少的話，會有無法獲得促進硬化的效果之虞。摻合量多的話，促進環氧基彼此之硬化的效果大，具有醯亞胺鍵之樹脂之反應性官能基與環氧基的反應無法充分進行，會有耐熱性、黏接性降低之虞。作為環氧丙胺型環氧樹脂，可列舉：三菱瓦斯化學(股)製的商品名TETRAD(註冊商標)-X、TETRAD-C、三菱化學(股)製的商品名jER630、jER604、新日鐵住金化學(股)製的商品名YH-434、YH-434L、ADEKA(股)製的商品名ADEKA RESIN EP-3950S、EP-3950L、EP-3980S、日本化藥(股)製的商品名GAN(註冊商標)、GOT(註冊商標)等，該等可單獨使用，亦可將多種組合使用。In the adhesive composition of the present invention, a glycidylamine-type epoxy resin may be added in addition to the above-mentioned epoxy resin in order to accelerate hardening within the range that does not impair the effects of the present invention. The amount of glycidylamine-type epoxy resin to be added is preferably 0.01% by mass to 5% by mass, or 0.05% by mass relative to the total mass of the resin having an imide bond in the adhesive composition and the aforementioned epoxy resin. ~2% by mass is preferred. When the compounding quantity of a glycidylamine type epoxy resin is small, the effect of accelerating hardening may not be acquired. If the blending amount is large, the effect of promoting the hardening of epoxy groups is large, and the reaction between the reactive functional groups of resins with imide bonds and epoxy groups cannot be fully carried out, and the heat resistance and adhesiveness may be reduced. . Examples of glycidylamine-type epoxy resins include: Mitsubishi Gas Chemical Co., Ltd. product names TETRAD (registered trademark)-X, TETRAD-C, Mitsubishi Chemical Co., Ltd. product names jER630, jER604, Nippon Steel Trade names YH-434, YH-434L manufactured by Sumikin Chemical Co., Ltd., trade names ADEKA RESIN EP-3950S, EP-3950L, EP-3980S manufactured by ADEKA Co., Ltd., trade name GAN manufactured by Nippon Kayaku Co., Ltd. (registered trademark), GOT (registered trademark), etc., may be used alone or in combination.

本發明之黏接劑組成物中，在不損及本發明之效果的範圍內，可添加環氧樹脂之硬化劑、硬化促進劑。作為硬化劑，只要是會與環氧樹脂反應之化合物，則無特別限制，例如可列舉：胺系硬化劑、具有苯酚性羥基之化合物、具有羧酸之化合物、具有酸酐之化合物等。作為硬化觸媒，只要是會促進環氧樹脂與具有醯亞胺鍵之樹脂及上述硬化劑之反應者，則無特別限制，例如可列舉：四國化成工業(股)製的商品名2MZ、2E4MZ、C11Z、C17Z、2PZ、1B2MZ、2MZ-CN、2E4MZ-CN、C11Z-CN、2PZ-CN、2PHZ-CN、2MZ-CNS、2E4MZ-CNS、2PZ-CNS、2MZ-AZINE、2E4MZ-AZINE、C11ZAZINE、2MA-OK、2P4MHZ、2PHZ、2P4BHZ等咪唑衍生物、乙醯胍胺(acetoguanamine)、苯并胍胺等胍胺類、二胺基二苯基甲烷、間苯二胺、間二甲苯二胺、二胺基二苯碸、二氰二胺(dicyandiamide)、脲、脲衍生物、三聚氰胺、多元醯肼等多元胺類、它們的有機酸鹽及/或環氧加成物、三氟化硼之胺錯合物、乙基二胺基-S-三

、2,4-二胺基-S-三

、2,4-二胺基-6-二甲苯基-S-三

等三

衍生物類、三甲胺、三乙醇胺、N,N-二甲基辛胺、N-苄基二甲胺、吡啶、N-甲基

啉、六(N-甲基)三聚氰胺、2,4,6-參(二甲基胺基苯酚)、四甲基胍、DBU(1,8-二氮雜雙環[5,4,0]-7-十一烯)、DBN(1,5-二氮雜雙環[4,3,0]-5-壬烯)等三級胺類、它們的有機酸鹽及/或四苯基硼酸鹽、聚乙烯基苯酚、聚乙烯基苯酚溴化物、三丁基膦、三苯基膦、參-2-氰基乙基膦等有機膦類、三-正丁基(2,5-二羥基苯基)溴化鏻、十六烷基三丁基氯化鏻、四苯基硼酸四苯基鏻等四級鏻鹽類、苄基三甲基氯化銨、苯基三丁基氯化銨等四級銨鹽類、前述多元羧酸酐、四氟硼酸二苯基錪、六氟銻酸三苯基鋶、2,4,6-三苯基硫吡喃六氟磷酸鹽、Irgacure 261(Ciba Specialty Chemicals(股)製)、Optomer-SP-170(ADEKA(股)製)等光陽離子聚合觸媒、苯乙烯-馬來酸酐樹脂、異氰酸苯酯與二甲胺之等莫耳反應產物、甲苯二異氰酸酯、異佛酮二異氰酸酯等有機聚異氰酸酯與二甲胺之等莫耳反應產物等。該等可單獨使用，亦可將多種組合使用。In the adhesive composition of the present invention, a curing agent and a curing accelerator for epoxy resin may be added within the range not impairing the effect of the present invention. The curing agent is not particularly limited as long as it is a compound that reacts with the epoxy resin, and examples thereof include amine-based curing agents, compounds having phenolic hydroxyl groups, compounds having carboxylic acids, and compounds having acid anhydrides. The curing catalyst is not particularly limited as long as it promotes the reaction between the epoxy resin, the resin having an imide bond, and the above-mentioned curing agent. 2E4MZ, C11Z, C17Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ-CN, 2PHZ-CN, 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C11ZAZINE, 2MA-OK, 2P4MHZ, 2PHZ, 2P4BHZ and other imidazole derivatives, acetoguanamine, benzoguanamine and other guanamines, diaminodiphenylmethane, m-phenylenediamine, m-xylene di Amines, diaminodiphenylene, dicyandiamide, urea, urea derivatives, melamine, polyhydrazines and other polyamines, their organic acid salts and/or epoxy adducts, trifluoride Boron amine complexes, ethyldiamine-S-tri

, 2,4-diamino-S-tri

, 2,4-diamino-6-xylyl-S-tri

wait three

Derivatives, trimethylamine, triethanolamine, N,N-dimethyloctylamine, N-benzyldimethylamine, pyridine, N-methyl

Phyloline, hexa(N-methyl)melamine, 2,4,6-paraffin(dimethylaminophenol), tetramethylguanidine, DBU(1,8-diazabicyclo[5,4,0]- 7-undecene), DBN (1,5-diazabicyclo[4,3,0]-5-nonene) and other tertiary amines, their organic acid salts and/or tetraphenyl borates, Polyvinylphenol, polyvinylphenol bromide, tributylphosphine, triphenylphosphine, ginseng-2-cyanoethylphosphine and other organic phosphines, tri-n-butyl (2,5-dihydroxyphenyl ) phosphonium bromide, hexadecyl tributyl phosphonium chloride, tetraphenyl phosphonium tetraphenyl borate and other quaternary phosphonium salts, benzyl trimethyl ammonium chloride, phenyl tributyl ammonium chloride and other four Grade ammonium salts, the aforementioned polycarboxylic anhydrides, diphenyliodonium tetrafluoroborate, triphenylconium hexafluoroantimonate, 2,4,6-triphenylthiopyran hexafluorophosphate, Irgacure 261 (Ciba Specialty Chemicals Co., Ltd.), photocationic polymerization catalysts such as Optomer-SP-170 (manufactured by ADEKA Co., Ltd.), styrene-maleic anhydride resin, equimolar reaction product of phenyl isocyanate and dimethylamine, toluene Molar reaction products of organic polyisocyanates such as diisocyanate and isophorone diisocyanate with dimethylamine, etc. These may be used alone or in combination of multiple types.

本發明之黏接劑組成物中，在不損及本發明之效果的範圍內，為了改善黏接性，可添加矽烷偶聯劑。矽烷偶聯劑只要是以往公知者，則無特別限定。作為其具體例，可列舉：胺基矽烷、巰基矽烷、乙烯基矽烷、環氧矽烷、甲基丙烯酸基矽烷、異氰酸酯矽烷、酮亞胺矽烷或它們的混合物或反應產物、或藉由該等與聚異氰酸酯之反應而獲得的化合物等。作為如此之矽烷偶聯劑，例如可列舉：3-胺基丙基三甲氧基矽烷、3-胺基丙基三乙氧基矽烷、3-胺基丙基甲基二甲氧基矽烷、3-胺基丙基乙基二乙氧基矽烷、雙三甲氧基矽基丙基胺、雙三乙氧基矽基丙基胺、雙甲氧基二甲氧基矽基丙基胺、雙乙氧基二乙氧基矽基丙基胺、N-2-(胺基乙基)-3-胺基丙基三甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基甲基二甲氧基矽烷、N-2-(胺基乙基)-3-胺基丙基三乙氧基矽烷、N-2-(胺基乙基)-3-胺基丙基乙基二乙氧基矽烷等胺基矽烷、γ-巰基丙基三甲氧基矽烷、γ-巰基丙基三乙氧基矽烷、γ-巰基丙基甲基二甲氧基矽烷、γ-巰基丙基甲基二乙氧基矽烷、γ-巰基丙基乙基二乙氧基矽烷等巰基矽烷、乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、參-(2-甲氧基乙氧基)乙烯基矽烷等乙烯基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基二甲基乙氧基矽烷、γ-環氧丙氧基丙基甲基二乙氧基矽烷、β-(3,4-環氧環己基)乙基甲基二甲氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷等環氧矽烷、3-甲基丙烯醯氧丙基甲基二甲氧基矽烷、3-甲基丙烯醯氧丙基三甲氧基矽烷、3-甲基丙烯醯氧丙基甲基二乙氧基矽烷、3-甲基丙烯醯氧丙基三乙氧基矽烷等甲基丙烯酸基矽烷、異氰酸酯丙基三乙氧基矽烷、異氰酸酯丙基三甲氧基矽烷等異氰酸酯矽烷、酮亞胺化丙基三甲氧基矽烷、酮亞胺化丙基三乙氧基矽烷等酮亞胺矽烷，該等可單獨使用，亦可將多種組合使用。該等矽烷偶聯劑之中，環氧矽烷具有反應性環氧基，因此可與具有醯亞胺鍵之樹脂反應，考量改善耐熱性、耐濕熱性的觀點係較佳。又，矽烷偶聯劑的添加量，相對於樹脂劑組成物之非揮發性成分，宜為0~3質量%，更佳為0.1~2質量%。摻合量多的話，會有耐熱性降低之虞。In the adhesive composition of the present invention, a silane coupling agent may be added in order to improve the adhesiveness within the range that does not impair the effects of the present invention. The silane coupling agent is not particularly limited as long as it is conventionally known. Specific examples thereof include: aminosilane, mercaptosilane, vinylsilane, epoxysilane, methylacrylicAcrylic silanes, isocyanate silanes, ketimino silanes, their mixtures or reaction products, or compounds obtained by reacting these with polyisocyanate, etc. As such a silane coupling agent, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, -Aminopropylethyldiethoxysilane, bistrimethoxysilylpropylamine, bistriethoxysilylpropylamine, bismethoxydimethoxysilylpropylamine, bisethyl Oxydiethoxysilylpropylamine, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyl Methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylethyl Diethoxysilane and other aminosilanes, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyl Methyldiethoxysilane, γ-mercaptopropylethyldiethoxysilane and other mercaptosilanes, vinyltrimethoxysilane, vinyltriethoxysilane, ginseng-(2-methoxyethoxy ) vinyl silane and other vinyl silanes, γ-glycidoxypropyl trimethoxysilane, γ-glycidoxypropyl dimethylethoxysilane, γ-glycidoxypropyl methyl Diethoxysilane, β-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4- Epoxycyclohexyl)ethyltrimethoxysilane and other epoxysilanes, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methyl Acryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane and other methacrylsilanes, isocyanatepropyltriethoxysilane, isocyanatepropyltrimethoxy Isocyanate silanes such as silane, ketimino silanes such as ketiminated propyltrimethoxysilane, and ketiminated propyltriethoxysilane may be used alone or in combination. Among these silane coupling agents, epoxy silane has a reactive epoxy group, so it can react with a resin having an imide bond, and is preferable from the viewpoint of improving heat resistance and heat and humidity resistance. Also, the amount of the silane coupling agent added is preferably 0 to 3% by mass, more preferably 0.1 to 2% by mass, based on the non-volatile components of the resin composition. When there is much compounding quantity, there exists a possibility that heat resistance may fall.

本發明之黏接劑組成物中，在不損及本發明之效果的範圍內，為了改善焊料耐熱性，可添加有機、無機填料。作為有機填料，可列舉係耐熱性樹脂之聚醯亞胺、聚醯胺醯亞胺等粉末。又，作為無機填料，例如可列舉：二氧化矽(SiO₂)、氧化鋁(Al₂O₃)、氧化鈦(TiO₂)、氧化鉭(Ta₂O₅)、氧化鋯(ZrO₂)、氮化矽(Si₃N₄)、鈦酸鋇(BaO．TiO₂)、碳酸鋇(BaCO₃)、鈦酸鉛(PbO．TiO₂)、鋯鈦酸鉛(PZT)、鋯鈦酸鑭鉛(PLZT)、氧化鎵(Ga₂O₃)、尖晶石(MgO．Al₂O₃)、多鋁紅柱石(mullite)(3Al₂O₃．2SiO₂)、堇青石(cordierite)(2MgO．2Al₂O₃．5SiO₂)、滑石(3MgO．4SiO₂．H₂O)、鈦酸鋁(TiO₂-Al₂O₃)、含氧化釔之氧化鋯(Y₂O₃-ZrO₂)、矽酸鋇(BaO．8SiO₂)、氮化硼(BN)、碳酸鈣(CaCO₃)、硫酸鈣(CaSO₄)、氧化鋅(ZnO)、鈦酸鎂(MgO．TiO₂)、硫酸鋇(BaSO₄)、有機皂土、黏土、雲母、氫氧化鋁、氫氧化鎂等，其中，考量分散的容易性、耐熱性改善效果的方面，宜為二氧化矽。該等可單獨使用，亦可將多種組合使用。又，該等有機、無機填料的添加量，相對於黏接劑組成物之非揮發性成分，宜為1~30質量%，更佳為3~15質量%。摻合量多的話，黏接劑塗膜會脆化，摻合量少的話，會有無法獲得充分的耐熱性改善效果之虞。In the adhesive composition of the present invention, organic and inorganic fillers may be added in order to improve the heat resistance of the solder within the range that does not impair the effects of the present invention. Examples of the organic filler include powders of heat-resistant resins such as polyimide and polyamideimide. Moreover, examples of inorganic fillers include silicon dioxide (SiO₂ ), aluminum oxide (Al₂ O₃ ), titanium oxide (TiO₂ ), tantalum oxide (Ta₂ O₅ ), zirconium oxide (ZrO₂ ), Silicon nitride (Si₃ N₄ ), barium titanate (BaO.TiO₂ ), barium carbonate (BaCO₃ ), lead titanate (PbO.TiO₂ ), lead zirconate titanate (PZT), lead lanthanum zirconate titanate (PLZT), gallium oxide (Ga₂ O₃ ), spinel (MgO.Al₂ O₃ ), mullite (3Al₂ O₃ .2SiO₂ ), cordierite (2MgO. 2Al₂ O₃ .5SiO₂ ), talc (3MgO.4SiO₂ .H₂ O), aluminum titanate (TiO₂ -Al₂ O₃ ), zirconia containing yttrium oxide (Y₂ O₃ -ZrO₂ ), Barium silicate (BaO.8SiO₂ ), boron nitride (BN), calcium carbonate (CaCO₃ ), calcium sulfate (CaSO₄ ), zinc oxide (ZnO), magnesium titanate (MgO.TiO₂ ), barium sulfate ( BaSO₄ ), bentonite, clay, mica, aluminum hydroxide, magnesium hydroxide, etc. Among them, silicon dioxide is preferable in consideration of the ease of dispersion and the effect of improving heat resistance. These may be used alone or in combination of multiple types. Moreover, the addition amount of these organic and inorganic fillers is preferably 1-30% by mass, more preferably 3-15% by mass, relative to the non-volatile components of the adhesive composition. If the blending amount is large, the adhesive coating film will become brittle, and if the blending amount is small, there may be a possibility that a sufficient effect of improving heat resistance cannot be obtained.

針對本發明之黏接劑組成物之製造方法之一例進行說明。將具有醯亞胺鍵之樹脂之溶劑溶液(以下，亦稱為具有醯亞胺鍵之樹脂清漆。)、環氧樹脂之溶劑溶液(以下，亦稱為環氧樹脂清漆。)、通式(1)之磷化合物等予以摻合，攪拌至體系均勻。使用填料時，添加利用上述溶劑製成漿液狀者作為填料並進行攪拌。藉此，可獲得本發明之黏接劑組成物。又，獲得黏接劑組成物時，可視需要添加用以調整黏度之稀釋溶劑、硬化促進劑等。An example of the production method of the adhesive composition of the present invention will be described. A solvent solution of a resin having an imide bond (hereinafter also referred to as a resin varnish having an imide bond.), a solvent solution of an epoxy resin (hereinafter also referred to as an epoxy resin varnish.), the general formula ( 1) Phosphorus compounds etc. are blended and stirred until the system is uniform. When using a filler, what was made into the slurry form with the said solvent is added as a filler, and it stirs. Thereby, the adhesive composition of the present invention can be obtained. In addition, when obtaining an adhesive composition, a diluent solvent for adjusting viscosity, a hardening accelerator, etc. may be added as needed.

本發明之黏接劑組成物可用作適合撓性印刷配線板之黏接劑組成物。將黏接劑組成物塗布在薄膜等基材，使其乾燥後之黏接劑組成物的層稱為黏接劑層，撓性印刷配線板中使用由黏接劑組成物構成之黏接劑的部位，可列舉：補強板用途之黏接薄膜、層間用途之黏接薄膜、表覆層薄膜、覆銅疊層板。The adhesive composition of the present invention can be used as an adhesive composition suitable for flexible printed wiring boards. The adhesive composition is coated on a substrate such as a film, and the layer of the adhesive composition after drying is called an adhesiveLayer, the part where the adhesive composed of the adhesive composition is used in the flexible printed wiring board, examples include: adhesive film for reinforcing board, adhesive film for interlayer use, surface layer film, copper clad laminate plate.

黏接薄膜係由「保護薄膜/黏接劑層」或「保護薄膜/黏接劑層/保護薄膜」構成的薄膜。有時也會在黏接劑層之中設置絕緣性薄膜層，其構成為「保護薄膜/黏接劑層/絕緣薄膜/黏接劑層/保護薄膜層」。在撓性印刷配線板中，大多用作補強板用途之黏接薄膜、層間用途之黏接薄膜。The adhesive film is a film composed of "protective film/adhesive layer" or "protective film/adhesive layer/protective film". In some cases, an insulating film layer is provided in the adhesive layer, and the composition is "protective film/adhesive layer/insulating film/adhesive layer/protective film layer". In flexible printed wiring boards, it is mostly used as an adhesive film for reinforcing boards and an adhesive film for interlayer applications.

絕緣性薄膜係由聚醯亞胺、聚醯胺醯亞胺、聚酯、聚苯硫醚、聚醚碸、聚醚醚酮、聚芳醯胺、聚碳酸酯、聚芳酯等塑膠構成的厚度1~200μm之薄膜，也可疊層選自該等之中的多個薄膜。The insulating film is made of polyimide, polyamideimide, polyester, polyphenylene sulfide, polyether sulfide, polyether ether ketone, polyaramid, polycarbonate, polyarylate and other plastics. A film with a thickness of 1 to 200 μm can also be laminated with a plurality of films selected from these.

作為保護薄膜，只要不損害黏接劑的特性並可剝離，則無特別限制，例如可列舉：聚乙烯、聚丙烯、聚烯烴、聚酯、聚甲基戊烯、聚氯乙烯、聚偏二氟乙烯、聚苯硫醚等塑膠薄膜、及將該等經聚矽氧或氟化物或其他脫模劑塗覆處理之薄膜、將該等予以層合而得的紙、含浸或塗覆有剝離性的樹脂而得的紙等。The protective film is not particularly limited as long as it can be peeled without impairing the properties of the adhesive. Examples include: polyethylene, polypropylene, polyolefin, polyester, polymethylpentene, polyvinyl chloride, polyvinylidene Plastic films such as vinyl fluoride and polyphenylene sulfide, films coated with polysiloxane or fluoride or other release agents, papers obtained by laminating them, impregnated or coated with release Paper etc. made of permanent resin.

表覆層薄膜係由「絕緣性薄膜/黏接劑層」或「絕緣性薄膜/黏接劑層/保護薄膜」構成的薄膜。The cover layer film is a film composed of "insulating film/adhesive layer" or "insulating film/adhesive layer/protective film".

覆銅疊層板係由「銅箔/黏接劑層/絕緣性薄膜」或「銅箔/黏接劑層/絕緣性薄膜/黏接劑層/銅箔」構成的疊層板。銅箔並無特別限制，可使用以往用於撓性印刷配線板之壓延銅箔、電解銅箔。A copper-clad laminate is a laminate composed of "copper foil/adhesive layer/insulating film" or "copper foil/adhesive layer/insulating film/adhesive layer/copper foil". Copper foil is not particularly limited, and rolled copper foil and electrolytic copper foil conventionally used for flexible printed wiring boards can be used.

在上述任意用途中，均可藉由將將黏接劑組成物塗布在成為基材之薄膜或銅箔上，進行溶劑乾燥，與被黏體熱壓接，並實施熱硬化處理而獲得。黏接薄膜及表覆層薄膜中，為了調整熱壓接時之黏接劑組成物之流動性，也會在溶劑乾燥後進行加熱處理，使具有醯亞胺鍵之樹脂及包含通式(1)之磷化合物的具反應基之磷化合物和環氧樹脂發生部分反應。又，熱壓接前之狀態稱為B階段。In any of the above applications, it can be obtained by coating the adhesive composition on a film or copper foil as a base material, drying it with a solvent, bonding it to an adherend by thermocompression, and performing a thermosetting treatment. Adhesive thinIn the film and the cover layer film, in order to adjust the fluidity of the adhesive composition during thermocompression bonding, heat treatment is also carried out after the solvent is dried, so that the resin having an imide bond and the resin containing the general formula (1) Phosphorus compounds with reactive groups partially react with epoxy resins. Also, the state before thermocompression bonding is referred to as a B stage.

在上述任意用途中，熱硬化後均要求黏接性、耐熱性、及絕緣可靠性，進一步具有阻燃性較佳。又，在黏接薄膜及表覆層薄膜中，通常於B階段狀態進行捲繞、保存、切割、沖壓等加工，也需要於B階段狀態之柔軟性。另一方面，在覆銅疊層板中，通常於B階段狀態形成後立即進行熱壓接及熱硬化，不像表覆層薄膜及黏接薄膜般需要於B階段狀態之柔軟性。In any of the above-mentioned applications, adhesiveness, heat resistance, and insulation reliability are required after thermosetting, and it is better to have flame retardancy. In addition, in the adhesive film and the cover layer film, processes such as winding, storage, cutting, and punching are usually performed in the B-stage state, and flexibility in the B-stage state is also required. On the other hand, in copper-clad laminates, thermocompression bonding and thermosetting are usually performed immediately after the formation of the B-stage state, and the flexibility of the B-stage state is not required like the surface layer film and the adhesive film.

本發明之黏接薄膜及表覆層薄膜，於B階段狀態之黏接劑層中之殘留溶劑量宜未達1.5質量%。更佳為1.0質量%以下。殘留溶劑係在B階段化步驟中未完全除去的黏接劑組成物中所使用之溶劑，組合使用多種溶劑時，較高沸點之溶劑會殘留。殘留溶劑量多的話，有時會有絕緣可靠性降低的情況，故就殘留溶劑量而言，如上述，於B階段狀態之黏接劑層中之殘留溶劑量宜未達1.5質量%，更佳為1.0質量%以下。In the adhesive film and the cover layer film of the present invention, the amount of residual solvent in the adhesive layer in the B-stage state is preferably less than 1.5% by mass. More preferably, it is 1.0 mass % or less. The residual solvent is the solvent used in the adhesive composition that was not completely removed in the step of B-staging, and when multiple solvents are used in combination, a solvent with a relatively high boiling point will remain. If the amount of residual solvent is large, the insulation reliability may sometimes be lowered. Therefore, in terms of the amount of residual solvent, as mentioned above, the amount of residual solvent in the adhesive layer in the B-stage state is preferably less than 1.5% by mass. Preferably, it is 1.0% by mass or less.

本發明之含有具有醯亞胺鍵之樹脂與通式(1)之磷化合物的黏接劑組成物，其黏接性、耐熱性、阻燃性、及絕緣可靠性優異。又，由於通式(1)之磷化合物的溶劑溶解性優異，故操作性優異。另外，通式(1)之磷化合物與具有醯亞胺鍵之樹脂的相容性優異，且具有反應性官能基，故藉由熱硬化而參與交聯，具有在高溫高濕環境下不易滲出之性質。因此，本發明之含有具有醯亞胺鍵之樹脂與通式(1)之磷化合物的黏接劑組成物展現出高絕緣可靠性。The adhesive composition of the present invention comprising a resin having an imide bond and a phosphorus compound of the general formula (1) has excellent adhesiveness, heat resistance, flame retardancy, and insulation reliability. Moreover, since the phosphorus compound of general formula (1) is excellent in solvent solubility, it is excellent in handleability. In addition, the phosphorus compound of the general formula (1) has excellent compatibility with resins having imide bonds, and has reactive functional groups, so it participates in crosslinking by thermosetting, and is not easy to bleed out in high temperature and high humidity environments. of the nature. Therefore, the adhesive composition of the present invention comprising a resin having an imide bond and a phosphorus compound of the general formula (1) exhibits high insulation reliability.

[實施例][Example]

以下，藉由實施例來實證本發明之效果，但本發明並不限定於該等。此外，實施例中之特性的評價係依以下之方法實施。實施例中及比較例中簡稱「份」時係表示質量份。Hereinafter, the effects of the present invention will be demonstrated by examples, but the present invention is not limited thereto. In addition, the evaluation of the characteristic in an Example was implemented by the following method. When abbreviated as "part" in an Example and a comparative example, it means a mass part.

對數黏度；logarithmic viscosity;

將具有醯亞胺鍵之樹脂溶解在N-甲基-2-吡咯烷酮中，使聚合物濃度成為0.5g/dl。於30℃利用烏氏型黏度管測定獲得之溶液的溶液黏度及溶劑黏度，根據下列算式計算對數黏度。A resin having an imide bond was dissolved in N-methyl-2-pyrrolidone so that the polymer concentration was 0.5 g/dl. Measure the solution viscosity and solvent viscosity of the obtained solution at 30°C with an Ubbelohde-type viscosity tube, and calculate the logarithmic viscosity according to the following formula.

對數黏度(dl/g)=[ln(V2/V1)]/V3Logarithmic viscosity (dl/g)=[ln(V2/V1)]/V3

上述式中，V1表示利用烏氏型黏度管測得之樹脂溶液黏度，V2表示利用烏氏型黏度管測得之溶劑黏度。V1及V2係由樹脂溶液及溶劑(N-甲基-2-吡咯烷酮)通過黏度管之毛細管的時間求得。又，V3為樹脂濃度(g/dl)。In the above formula, V1 represents the viscosity of the resin solution measured with an Ubbelohde-type viscosity tube, and V2 represents the viscosity of the solvent measured with an Ubbelohde-type viscosity tube. V1 and V2 are obtained from the time for the resin solution and solvent (N-methyl-2-pyrrolidone) to pass through the capillary of the viscosity tube. Also, V3 is the resin concentration (g/dl).

酸價；acid value;

將具有醯亞胺鍵之樹脂0.1g溶解在20ml之N-甲基-2-吡咯烷酮中，以百里酚酞作為指示劑，用0.1N之KOH乙醇溶液進行滴定，測定每10⁶g樹脂之羧基當量(eq/ton)，並根據下列算式計算酸價。Dissolve 0.1 g of resin with imide bond in 20 ml of N-methyl-2-pyrrolidone, use thymolphthalein as indicator, titrate with 0.1 N KOH ethanol solution, and measure the carboxyl group per 10⁶ g of resin Equivalent (eq/ton), and calculate the acid value according to the following formula.

酸價(mgKOH/g)=[羧基當量(eq/ton)×56.12]/1000Acid value (mgKOH/g)=[Carboxyl equivalent (eq/ton)×56.12]/1000

玻璃轉移溫度：Glass transition temperature:

將具有醯亞胺鍵之樹脂之溶液塗布在銅箔的光澤面，並在140℃於熱風乾燥機中乾燥3分鐘。之後，於250℃氮氣環境下乾燥30分鐘，而得到附有樹脂之銅箔。之後，將銅箔進行蝕刻，藉此製作厚度20μm之樹脂薄膜。利用TMA(熱機械分析裝置)拉伸法以荷重50mN、升溫速度10℃/分鐘之條件測定以此種方式製作之樹脂薄膜的玻璃轉移點。Coat the solution of the resin with imide bonds on the glossy surface of the copper foil, and dry it in a hot air dryer at 140°C for 3 minutes. Afterwards, it was dried for 30 minutes under a nitrogen atmosphere at 250° C. to obtain a resin-attached copper foil. Thereafter, the copper foil was etched to produce a resin film with a thickness of 20 μm. Using TMA (thermomechanicalAnalyzer) Tensile method The glass transition point of the resin film produced in this way was measured under the conditions of a load of 50 mN and a heating rate of 10° C./min.

黏接性；adhesiveness;

將黏接劑組成物之溶液塗布於聚醯亞胺(PI)薄膜(Kaneka製APICAL(註冊商標)12.5NPI)，使黏接劑層之乾燥後厚度成為20μm，於140℃在熱風循環式乾燥器中乾燥3分鐘，獲得B階段狀態之樣品(PI薄膜/黏接劑層)。將該B階段狀態之樣品(PI薄膜/黏接劑層)的黏接劑塗布面與壓延銅箔(JX金屬製BHY-13F-T：厚度18μm)，使用真空壓製層合機於160℃、20kgf、60秒減壓下進行熱壓接。之後，在170℃加熱硬化3小時。針對硬化後之樣品(PI薄膜/黏接劑層/壓延銅箔)，使用拉伸試驗機(島津製Autograph AG-X plus)在25℃之環境下將聚醯亞胺薄膜沿90°之方向以50mm/min之速度進行剝離，並測定黏接強度。Coat the solution of the adhesive composition on a polyimide (PI) film (APICAL (registered trademark) 12.5NPI manufactured by Kaneka) so that the thickness of the adhesive layer becomes 20 μm after drying, and dry at 140°C with hot air circulation Dry in the oven for 3 minutes to obtain a sample in the B-stage state (PI film/adhesive layer). The adhesive-coated surface of the sample (PI film/adhesive layer) in the B-stage state and the rolled copper foil (BHY-13F-T made by JX Metal: thickness 18μm) were placed at 160°C, Thermocompression bonding was performed under reduced pressure of 20kgf and 60 seconds. Thereafter, it was heated and hardened at 170° C. for 3 hours. For the hardened sample (PI film/adhesive layer/calendered copper foil), use a tensile tester (Shimadzu Autograph AG-X plus) to test the polyimide film in a 90° direction at 25°C Peel off at a speed of 50mm/min, and measure the adhesive strength.

◎：黏接強度為0.7N/mm以上或聚醯亞胺薄膜材破◎: The adhesive strength is above 0.7N/mm or the polyimide film material is broken

○：黏接強度為0.5N/mm以上且未達0.7N/mm○: Adhesive strength is more than 0.5N/mm and less than 0.7N/mm

×：黏接強度未達0.5N/mm×: Adhesive strength is less than 0.5N/mm

焊料耐熱性；Solder heat resistance;

與黏接性的評價同樣地製作經加熱硬化的樣品(PI薄膜/黏接劑層/壓延銅箔)，將其裁切成20mm見方，在300℃之焊料浴中使聚醯亞胺面朝上漂浮1分鐘。進行外觀評價。Prepare heat-hardened samples (PI film/adhesive layer/rolled copper foil) in the same manner as the evaluation of adhesion, cut it into 20mm squares, and place the polyimide side in a solder bath at 300°C Float for 1 minute. Appearance evaluation was performed.

○：無隆起、剝落○: No swelling or peeling

×：有隆起或剝落×: There is swelling or peeling

阻燃性；Flame retardancy;

將黏接劑組成物之溶液塗布於聚醯亞胺薄膜(Kaneka製APICAL12.5NPI)，使黏接劑層之乾燥後厚度成為20μm，於140℃在熱風循環式乾燥器中乾燥3分鐘，獲得B階段狀態之樣品(PI薄膜/黏接劑層)。將該B階段狀態之樣品(PI薄膜/黏接劑層)的黏接劑塗布面與聚醯亞胺薄膜(Kaneka製APICAL12.5NPI)，使用真空壓製層合機，於160℃、20kgf、60秒減壓下進行熱壓接。之後，在170℃加熱硬化3小時。依據UL-94VTM規格評價硬化後之樣品(PI薄膜/黏接劑層/PI薄膜)的阻燃性。The solution of the adhesive composition was coated on a polyimide film (APICAL12.5NPI manufactured by Kaneka) so that the thickness of the adhesive layer became 20 μm after drying, and dried in a hot air circulation dryer at 140°C for 3 minutes to obtain Sample in B-stage state (PI film/adhesive layer). The adhesive-coated surface of the sample in the B-stage state (PI film/adhesive layer) and the polyimide film (APICAL12.5NPI manufactured by Kaneka) were placed at 160°C, 20kgf, 60°C using a vacuum press laminator. Thermocompression bonding under reduced pressure in seconds. Thereafter, it was heated and hardened at 170° C. for 3 hours. The flame retardancy of the hardened samples (PI film/adhesive layer/PI film) was evaluated according to UL-94VTM standard.

○：相當於VTM-0○: Equivalent to VTM-0

×：不符合VTM-0×: Does not comply with VTM-0

絕緣可靠性；Insulation reliability;

將黏接劑組成物之溶液塗布於聚醯亞胺薄膜(Kaneka製APICAL12.5NPI)，使黏接劑層之乾燥後厚度成為20μm，於140℃在熱風循環式乾燥器中乾燥3分鐘，獲得B階段狀態之樣品(PI薄膜/黏接劑層)。將該B階段狀態之樣品(PI薄膜/黏接劑層)的黏接劑塗布面與蝕刻加工成L/S=50/50μm之梳子型圖案的單面覆銅疊層板(使用新日鐵住金化學(股)製的商品名Espanex(註冊商標)MC12-25-00CEM)，使用真空壓製層合機於160℃、20kgf、60秒減壓下進行熱壓接。之後，在170℃加熱硬化3小時。對硬化後之樣品(PI薄膜/黏接劑層/單面覆銅疊層板)，在溫度85℃、濕度85%之環境下施加200V之電壓250小時。The solution of the adhesive composition was coated on a polyimide film (APICAL12.5NPI manufactured by Kaneka) so that the thickness of the adhesive layer became 20 μm after drying, and dried in a hot air circulation dryer at 140°C for 3 minutes to obtain Sample in B-stage state (PI film/adhesive layer). The adhesive-coated surface of the sample (PI film/adhesive layer) in the B-stage state was etched into a single-sided copper-clad laminate with a comb-shaped pattern of L/S=50/50 μm (using Nippon Steel The product name Espanex (registered trademark) MC12-25-00CEM) manufactured by Sumikin Chemical Co., Ltd. was thermocompression-bonded at 160° C., 20 kgf, and reduced pressure for 60 seconds using a vacuum press laminator. Thereafter, it was heated and hardened at 170° C. for 3 hours. For the hardened sample (PI film/adhesive layer/single-sided copper-clad laminate), apply a voltage of 200V for 250 hours in an environment with a temperature of 85°C and a humidity of 85%.

◎：250小時後之電阻值為1×10¹⁰Ω以上，且無樹狀突起◎: After 250 hours, the resistance value is above 1×10¹⁰ Ω, and there are no dendrites

○：250小時後之電阻值為1×10⁹Ω以上且未達1×10¹⁰Ω，且無樹狀突起產生○: After 250 hours, the resistance value is above 1×10⁹ Ω and less than 1×10¹⁰ Ω, and there is no dendrite

×：250小時後之電阻值未達1×10⁹Ω或有樹狀突起產生×: After 250 hours, the resistance value does not reach 1×10⁹ Ω or there are dendrites

××：在250小時以內短路××: short circuit within 250 hours

合成例1；Synthesis example 1;

在配備有攪拌機、具冷卻管之溶劑回收裝置、氮氣導入管及溫度計的4口燒瓶中，加入三光(股)製的商品名HCA(9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物)558.3g及Allnex(股)製的商品名Phenodur(註冊商標)PR411(丁醇中固體成分濃度75%)391.6g，邊攪拌並通入氮氣，邊歷時180分鐘將燒瓶內溫升溫至199℃。在此過程中，藉由溶劑回收裝置餾出原料中含有的丁醇及反應生成的丁醇。之後，在200℃保持20分鐘，餾出殘留在反應產物中之揮發性成分。從燒瓶取出獲得之固體，得到磷化合物A。磷化合物A具有化學式(9)之結構。In a 4-neck flask equipped with a stirrer, a solvent recovery device with a cooling tube, a nitrogen gas introduction tube, and a thermometer, add HCA (9,10-dihydro-9-oxa-10-phosphorus) manufactured by Sanko Co., Ltd. Miscellaneous phenanthrene-10-oxide) 558.3g and Allnex (stock) trade name Phenodur (registered trademark) PR411 (solid content concentration 75% in butanol) 391.6g, while stirring and passing into nitrogen gas, lasted 180 minutes while stirring The inner temperature of the flask was raised to 199°C. During this process, the butanol contained in the raw material and the butanol produced by the reaction are distilled out by the solvent recovery device. After that, it was kept at 200° C. for 20 minutes, and the volatile components remaining in the reaction product were distilled off. The obtained solid was taken out from the flask to obtain phosphorus compound A. Phosphorus compound A has the structure of chemical formula (9).

具有醯亞胺鍵之樹脂1~2的聚合；Polymerization of resins 1~2 with imide bonds;

依表1所示之原料之樹脂組成(莫耳%)，進行具有醯亞胺鍵之樹脂的聚合。具體而言，如下述般進行聚合。According to the resin composition (mole %) of the raw materials shown in Table 1, the polymerization of the resin having imide bonds was carried out. Specifically, polymerization was performed as follows.

具有醯亞胺鍵之樹脂1的聚合Polymerization of resin 1 with imide bonds

在配備有攪拌機、冷卻管、氮氣導入管及溫度計之4口可拆式燒瓶中，加入TMA(偏苯三甲酸酐)110.47g(0.575莫耳)、癸二酸80.90g(0.40莫耳)、NBR(兩末端羧基改性丙烯腈丁二烯橡膠)87.5g(0.025莫耳)、MDI(二苯基甲烷-4,4’-二異氰酸酯)250.25g(1.00莫耳)及使脫羧後之樹脂成分濃度成為40質量%的二甲基乙醯胺714.50g，在氮氣下升溫至100℃使其反應2小時，再進一步升溫至150℃並使其反應5小時。之後，加入二甲基乙醯胺396.94g進行稀釋，使樹脂成分之濃度成為30質量%，獲得具有醯亞胺鍵之樹脂1之溶液。In a 4-necked detachable flask equipped with a stirrer, a cooling tube, a nitrogen inlet tube and a thermometer, add 110.47 g (0.575 mol) of TMA (trimellitic anhydride), 80.90 g (0.40 mol) of sebacic acid, and NBR (Carboxyl-modified acrylonitrile butadiene rubber at both ends) 87.5g (0.025 mol), MDI (diphenylmethane-4,4'-diisocyanate) 250.25g (1.00 mol) and the resin component after decarboxylation 714.50 g of dimethylacetamide having a concentration of 40% by mass was heated up to 100° C. and reacted for 2 hours under nitrogen gas, and then further heated up to 150° C. and reacted for 5 hours. Thereafter, 396.94 g of dimethylacetamide was added and diluted so that the concentration of the resin component became 30% by mass, and a solution of resin 1 having an imide bond was obtained.

具有醯亞胺鍵之樹脂2的聚合Polymerization of resin 2 with imide bonds

在配備有攪拌機、冷卻管、氮氣導入管及溫度計之4口可拆式燒瓶中，加入偏苯三甲酸酐192.13g(1.00莫耳)、二苯基甲烷-4,4’-二異氰酸酯225.23g(0.90莫耳)及使脫羧後之樹脂成分之濃度成為40質量%的N-甲基-2-吡咯烷酮494.05g，在氮氣下升溫至100℃並使其反應2小時，再進一步升溫至150℃並使其反應5小時。之後，加入二甲基乙醯胺117.63g進行稀釋，使樹脂成分之濃度成為35質量%，獲得具有醯亞胺鍵之樹脂2之溶液。In a 4-necked detachable flask equipped with a stirrer, a cooling tube, a nitrogen inlet tube and a thermometer, 192.13 g (1.00 mol) of trimellitic anhydride and 225.23 g of diphenylmethane-4,4'-diisocyanate ( 0.90 mol) and 494.05 g of N-methyl-2-pyrrolidone whose decarboxylated resin concentration is 40% by mass, heated up to 100°C under nitrogen and allowed to react for 2 hours, then further raised to 150°C and It was allowed to react for 5 hours. Thereafter, 117.63 g of dimethylacetamide was added and diluted so that the concentration of the resin component became 35% by mass, and a solution of resin 2 having an imide bond was obtained.

TMA：偏苯三甲酸酐TMA: trimellitic anhydride

NBR：兩末端羧基改性丙烯腈丁二烯橡膠NBR: two-terminal carboxyl modified acrylonitrile butadiene rubber

MDI：二苯基甲烷-4,4’-二異氰酸酯MDI: diphenylmethane-4,4'-diisocyanate

黏接劑組成物之溶液的製作；Preparation of solution of adhesive composition;

依表2所示之黏接劑摻合(固體成分(質量%))製作實施例1~7及比較例1~4之黏接劑組成物的二甲基乙醯胺溶液或N-甲基-2-吡咯烷酮溶液，並進行上述特性的評價。According to the adhesive blending (solid content (mass %)) shown in Table 2, the dimethylacetamide solution or N-methyl -2-pyrrolidone solution, and carry out the evaluation of the above characteristics.

由表2可知，符合本發明之條件的實施例1~7之黏接劑組成物，在黏接性、焊料耐熱性、阻燃性、絕緣可靠性顯示出優異的結果，反觀不含磷化合物之比較例1、不含通式(1)之磷化合物的比較例2及比較例3、以及不含具有醯亞胺鍵之樹脂的比較例4中，所有特性均為不令人滿意的結果。It can be seen from Table 2 that the adhesive compositions of Examples 1 to 7 that meet the conditions of the present invention show excellent results in adhesiveness, solder heat resistance, flame retardancy, and insulation reliability. On the contrary, they do not contain phosphorus compounds RatioIn Comparative Example 1, Comparative Example 2 and Comparative Example 3 not containing the phosphorus compound of the general formula (1), and Comparative Example 4 not containing the resin having an imide bond, all properties were unsatisfactory.

UR3500：東洋紡(股)製 聚酯胺甲酸酯樹脂UR3500: Polyester urethane resin manufactured by Toyobo Co., Ltd.

jER152：三菱化學(股)製 苯酚酚醛清漆型環氧樹脂(液狀)jER152: Mitsubishi Chemical Co., Ltd. Phenol Novolak Type Epoxy Resin (Liquid)

YDF8170C：新日鐵住金化學(股)製 雙酚F型環氧樹脂(液狀)YDF8170C: Bisphenol F epoxy resin (liquid) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.

YDCN700-7：新日鐵住金化學(股)製 甲酚酚醛清漆型環氧樹脂(固狀)YDCN700-7: Nippon Steel & Sumikin Chemical Co., Ltd. cresol novolak type epoxy resin (solid state)

磷化合物A：合成例(1)中獲得之磷化合物※含有化學式(9)Phosphorus compound A: Phosphorus compound obtained in Synthesis Example (1) * Contains chemical formula (9)

HCA：三光(股)製 次膦酸衍生物※含有化學式(6)HCA: Sanko Co., Ltd. phosphinic acid derivative * Contains chemical formula (6)

BCA：三光(股)製 次膦酸衍生物※含有化學式(7)BCA: Sanko Co., Ltd. phosphinic acid derivative * Contains chemical formula (7)

[產業上利用性][industrial availability]

本發明之黏接劑組成物，藉由組合具有醯亞胺鍵之樹脂與特定之磷化合物，黏接性、耐熱性、阻燃性、操作性、絕緣可靠性優異，適合於黏接薄膜、表覆層薄膜、覆銅疊層板等，極為有用。The adhesive composition of the present invention is excellent in adhesiveness, heat resistance, flame retardancy, operability, and insulation reliability by combining a resin having an imide bond and a specific phosphorus compound, and is suitable for bonding films, It is extremely useful for surface coating films, copper clad laminates, etc.

Claims (11)

Translated fromChinese

一種黏接劑組成物，其特徵為：含有具有醯亞胺鍵之樹脂及通式(1)表示之磷化合物；

通式(1)中之R₁~R₄係下列通式(2)~(4)中之任一者，R₁~R₄中之至少1個為通式(2)；通式(2)~(4)中之＊表示直接鍵結於通式(1)之芳香環的部位；通式(1)及通式(3)中之多個X各自獨立地為CH₂或C(CH₃)₂，通式(1)及通式(3)中之多個Y各自獨立地為氫或羥基；惟，通式(1)中，多個Y中之至少1個為羥基；通式(4)中之R₅為氫或碳數1~10之烷基；

An adhesive composition characterized by: containing a resin having an imide bond and a phosphorus compound represented by general formula (1);

R₁ ~ R₄ in general formula (1) is any one of the following general formulas (2) ~ (4), at least one of R₁ ~ R₄ is general formula (2); general formula (2 * in )~(4) represents the position directly bonded to the aromatic ring of general formula (1); multiple Xs in general formula (1) and general formula (3) are each independently CH₂ or C(CH₃ )₂ , multiple Ys in general formula (1) and general formula (3) are independently hydrogen or hydroxyl; however, in general formula (1), at least one of multiple Ys is hydroxyl; general formula R in (₄ ) is hydrogen or an alkyl group with 1 to 10 carbons;

如申請專利範圍第1項之黏接劑組成物，其中，該具有醯亞胺鍵之樹脂為聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、聚醚醯亞胺樹脂、聚酯醯亞胺樹脂或聚碳酸酯醯亞胺樹脂。Such as the adhesive composition of claim 1, wherein the resin having imide bond is polyimide resin, polyamideimide resin, polyetherimide resin, polyesterimide resin Amine resin or polycarbonate imide resin.如申請專利範圍第1或2項之黏接劑組成物，其中，該具有醯亞胺鍵之樹脂之共聚成分含有偏苯三甲酸酐。As in the adhesive composition of claim 1 or 2, wherein the copolymerization component of the resin having an imide bond contains trimellitic anhydride.如申請專利範圍第1或2項之黏接劑組成物，其中，該具有醯亞胺鍵之樹脂之共聚成分含有兩末端羧基改性丙烯腈丁二烯橡膠。As in the adhesive composition of Claim 1 or 2 of the patent application, wherein the copolymerization component of the resin having an imide bond contains carboxyl-modified acrylonitrile butadiene rubber at both ends.如申請專利範圍第1或2項之黏接劑組成物，更含有環氧樹脂。For example, the adhesive composition of item 1 or 2 of the scope of the patent application further contains epoxy resin.如申請專利範圍第5項之黏接劑組成物，該環氧樹脂之性狀係於25℃為液狀，且1分子中具有2個以上之環氧基。For the adhesive composition in item 5 of the scope of the patent application, the epoxy resin is liquid at 25°C and has more than two epoxy groups in one molecule.如申請專利範圍第1或2項之黏接劑組成物，係使用在印刷配線板用途。For example, the adhesive composition in item 1 or 2 of the scope of the patent application is used for printed wiring boards.一種黏接薄膜，使用了如申請專利範圍第1至7項中任一項之黏接劑組成物。An adhesive film using the adhesive composition according to any one of items 1 to 7 of the patent application.一種表覆層薄膜，使用了如申請專利範圍第8項之黏接薄膜。A surface coating film using the adhesive film described in item 8 of the scope of the patent application.一種覆銅疊層板，使用了如申請專利範圍第8項之黏接薄膜。A copper-clad laminate using the adhesive film described in item 8 of the scope of the patent application.一種撓性印刷配線板，使用了如申請專利範圍第9項之表覆層薄膜、或如申請專利範圍第10項之覆銅疊層板。A flexible printed wiring board using the surface coating film as in item 9 of the patent application, or the copper-clad laminate as in item 10 of the patent application.