TWI746812B - Polyester adhesive composition containing carboxylic acid group - Google Patents

Abstract

本發明之課題係：提供一種含有羧酸基之聚酯系黏接劑組成物，其維持對於各種塑膠薄膜、銅、鋁、不銹鋼等金屬、玻璃環氧樹脂之良好黏接性，同時也可對應於高濕度下之無鉛焊料之高程度的耐濕熱性優異，且片材壽命(sheet life)優異。該課題之解決方法為：一種黏接劑組成物，包含含有羧酸基之聚酯樹脂(A)及分子內具有2個以上之環氧丙基的化合物(B)，其特徵為：含有羧酸基之聚酯樹脂(A)的玻璃轉移溫度(Tg)為40~90℃，酸價為1~30mgKOH/g，且包含高分子多元醇(A1)、及與高分子多元醇(A1)不同的高分子多元醇(A2)以及四羧酸二酐作為共聚成分。The subject of the present invention is to provide a polyester-based adhesive composition containing carboxylic acid groups, which maintains good adhesion to various plastic films, metals such as copper, aluminum, stainless steel, and glass epoxy resin, while also being able to Corresponding to lead-free solder under high humidity, it has excellent moisture and heat resistance and excellent sheet life. The solution to this problem is: an adhesive composition comprising a polyester resin (A) containing a carboxylic acid group and a compound (B) having two or more glycidyl groups in the molecule, which is characterized by: containing a carboxyl group The glass transition temperature (Tg) of the acid-based polyester resin (A) is 40~90℃, the acid value is 1~30mgKOH/g, and it contains polymer polyol (A1) and polymer polyol (A1) Different polymer polyols (A2) and tetracarboxylic dianhydride are used as copolymerization components.

Description

含有羧酸基之聚酯系黏接劑組成物Polyester adhesive composition containing carboxylic acid group

本發明關於對於各種塑膠薄膜、銅、鋁、不銹鋼等金屬、玻璃環氧樹脂之黏接性、耐焊料性及片材壽命(sheet life)優異的黏接劑組成物、黏接片及包含該黏接片作為構成要素的印刷配線板。The present invention relates to an adhesive composition, an adhesive sheet, and an adhesive composition having excellent adhesion, solder resistance, and sheet life to various plastic films, metals such as copper, aluminum, stainless steel, and glass epoxy resins. The adhesive sheet is a printed wiring board as a component.

近年，黏接劑已使用在各種領域，因使用目的之多樣化，要求比起以往所使用之黏接劑，對於各種塑膠薄膜、金屬、玻璃環氧樹脂等之黏接性、耐濕熱性等更加高性能化。例如，對於以撓性印刷配線板(以下有時簡稱為FPC)為首之電路基板用的黏接劑，要求黏接性、加工性、電特性、保存性。以往該用途係使用環氧化物/丙烯酸丁二烯系黏接劑、環氧化物/聚乙烯醇縮丁醛系黏接劑等。In recent years, adhesives have been used in various fields. Due to the diversification of the purpose of use, it is required to compare the adhesives used in the past to various plastic films, metals, glass epoxy resins, etc., for adhesion, humidity and heat resistance, etc. Higher performance. For example, adhesives for circuit boards, including flexible printed wiring boards (hereinafter sometimes referred to as FPCs), require adhesiveness, processability, electrical properties, and storage properties. Conventionally, epoxy/acrylic butadiene-based adhesives, epoxy/polyvinyl butyral-based adhesives, etc. have been used for this application.

特別是近年考量對應於無鉛焊料、FPC之使用環境的方面，要求具有更高程度之耐熱性的黏接劑。又，考量配線之高密度化、FPC配線板之多層化、作業性的方面，強烈要求於高濕度下之耐焊料性。針對該等課題，已有人揭示以特定的聚酯、或聚酯-聚胺甲酸酯與環氧樹脂作為主成分之黏接劑用樹脂組成物。但，該等組成物在摻合後之適用期(pot life)、塗覆乾燥後之片材壽命短，有可能難以在常溫下流通(例如專利文獻1~2)。 [先前技術文獻] [專利文獻]Especially in recent years, considering the use environment of lead-free solder and FPC, adhesives with a higher degree of heat resistance are required. In addition, considering the high density of wiring, the multilayering of FPC wiring boards, and the workability, there is a strong demand for solder resistance under high humidity. In response to these issues, some people have disclosed a resin composition for an adhesive that uses a specific polyester or polyester-polyurethane and epoxy resin as the main components. However, the pot life of these compositions after blending and the sheet life after coating and drying are short, and it may be difficult to circulate at room temperature (for example, Patent Documents 1 to 2). [Prior Art Document] [Patent Document]

[專利文獻1]日本特開2010-84005號公報 [專利文獻2]日本特開2009-096939號公報[Patent Document 1] Japanese Patent Application Publication No. 2010-84005 [Patent Document 2] Japanese Patent Application Publication No. 2009-096939

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

本發明之課題旨在改良該等習知黏接劑所帶有的各種問題，並提供一種含有羧酸基之聚酯系黏接劑組成物，其維持對於各種塑膠薄膜、銅、鋁、不銹鋼等金屬、玻璃環氧樹脂之良好黏接性，同時也可對應於高濕度下之無鉛焊料之高程度的耐濕熱性(耐焊料性)優異，且片材壽命優異。 [解決課題之手段]The subject of the present invention is to improve the various problems of the conventional adhesives, and to provide a polyester-based adhesive composition containing carboxylic acid groups, which maintains resistance to various plastic films, copper, aluminum, and stainless steel It has good adhesion to other metals and glass epoxy resins, and also corresponds to the high degree of heat and humidity resistance (solder resistance) of lead-free solder under high humidity, and excellent sheet life. [Means to solve the problem]

本案發明人等進行努力研究的結果，發現藉由以下所示之手段可解決上述課題，而完成了本發明。亦即，本發明係如下列之構成。As a result of diligent research by the inventors of the present invention, they found that the above-mentioned problems can be solved by the means shown below, and completed the present invention. That is, the present invention is constituted as follows.

一種黏接劑組成物，包含含有羧酸基之聚酯樹脂(A)及分子內具有2個以上之環氧丙基的化合物(B)，其特徵為：含有羧酸基之聚酯樹脂(A)的玻璃轉移溫度(T g)為40~90℃，酸價為1~30mgKOH/g，且包含高分子多元醇(A1)、及與高分子多元醇(A1)不同的高分子多元醇(A2)以及四羧酸二酐作為共聚成分。An adhesive composition comprising a polyester resin (A) containing a carboxylic acid group and a compound (B) having two or more glycidyl groups in the molecule, and is characterized by: a polyester resin containing a carboxylic acid group ( A) The glass transition temperature (T g) is 40~90℃, the acid value is 1~30mgKOH/g, and it contains polymer polyol (A1) and polymer polyol different from polymer polyol (A1) (A2) and tetracarboxylic dianhydride as copolymerization components.

高分子多元醇(A1)及/或高分子多元醇(A2)宜為聚酯多元醇。The polymer polyol (A1) and/or the polymer polyol (A2) are preferably polyester polyols.

一種黏接片，含有前述黏接劑組成物之硬化物。一種印刷配線板，包含該黏接片作為構成要素。 [發明之效果]An adhesive sheet containing the hardened substance of the aforementioned adhesive composition. A printed wiring board includes the adhesive sheet as a constituent element. [Effects of the invention]

本發明之含有羧酸基之聚酯系黏接劑組成物，維持對於各種塑膠薄膜、銅、鋁、不銹鋼等金屬、玻璃環氧樹脂的良好黏接性，同時也可對應於高濕度下之無鉛焊料之高程度的耐濕熱性(耐焊料性)優異，且片材壽命優異。The polyester-based adhesive composition containing carboxylic acid groups of the present invention maintains good adhesion to various plastic films, metals such as copper, aluminum, stainless steel, and glass epoxy resins, and can also correspond to high humidity conditions. Lead-free solder has a high degree of heat and humidity resistance (solder resistance) and excellent sheet life.

＜高分子多元醇(A1)＞ 高分子多元醇(A1)之玻璃轉移溫度並無特別限定，宜為0℃以上，更佳為5℃以上。玻璃轉移溫度過低的話，黏接劑組成物的黏性變強，貼合時容易有氣泡夾入而變得不良。又，宜為90℃以下，更佳為80℃以下，尤佳為75℃。玻璃轉移溫度過高的話，會有塗膜變脆，脆化成為問題，或對於基材的密接性不足之疑慮。<Polymer polyol (A1)> The glass transition temperature of the polymer polyol (A1) is not particularly limited, but it is preferably 0°C or higher, and more preferably 5°C or higher. If the glass transition temperature is too low, the adhesive composition becomes more viscous, and bubbles are likely to be trapped during bonding and become defective. Furthermore, it is preferably 90°C or less, more preferably 80°C or less, and particularly preferably 75°C. If the glass transition temperature is too high, the coating film will become brittle, embrittlement will become a problem, or there will be concerns about insufficient adhesion to the substrate.

高分子多元醇(A1)的酸價(mgKOH/g)並無特別限定，宜為0.1以上，更佳為0.3以上，尤佳為1以上。過小的話，會有交聯變得不充分，耐濕熱性降低的情況。又，宜為10以下，更佳為8以下，尤佳為6以下。過大的話，會有四羧酸二酐所為之酸加成鏈延長變得無法進行的情況。因此，由於交聯密度變高，由黏接劑組成物獲得之塗膜變硬，而會有密接力降低的傾向。The acid value (mgKOH/g) of the polymer polyol (A1) is not particularly limited, but is preferably 0.1 or more, more preferably 0.3 or more, and particularly preferably 1 or more. If it is too small, crosslinking may become insufficient and the heat and humidity resistance may decrease. Moreover, it is preferably 10 or less, more preferably 8 or less, and particularly preferably 6 or less. If it is too large, the acid addition chain extension caused by tetracarboxylic dianhydride may become impossible. Therefore, as the crosslinking density becomes higher, the coating film obtained from the adhesive composition becomes hard, and there is a tendency for the adhesive force to decrease.

高分子多元醇(A1)的數量平均分子量(Mn1)並無特別限定，宜為10,000以上， 更佳為11,000以上，尤佳為12,000以上。Mn1未達10,000的話，由於交聯密度變高，由黏接劑組成物獲得之塗膜變硬，而會有密接力降低的傾向。此外，由於變得難以緩和耐加濕焊料時所產生之水蒸氣的應力，也會有耐加濕焊料性惡化的傾向。又，Mn1宜為50,000以下，為40,000以下更佳，為30,000以下尤佳。過大的話，有時會有交聯變得不充分，耐熱性降低的情況。高分子多元醇(A1)之數量平均分子量(Mn1)宜大於高分子多元醇(A2)之數量平均分子量(Mn2)、四羧酸二酐之分子量，在共聚成分中為最大更佳。The number average molecular weight (Mn1) of the polymer polyol (A1) is not particularly limited, but is preferably 10,000 or more, more preferably 11,000 or more, and particularly preferably 12,000 or more. If Mn1 is less than 10,000, the cross-linking density becomes higher, and the coating film obtained from the adhesive composition becomes hard, and the adhesive force tends to decrease. In addition, since it becomes difficult to alleviate the stress of water vapor generated when the solder is humidified, the solder resistance tends to deteriorate. In addition, Mn1 is preferably 50,000 or less, more preferably 40,000 or less, and particularly preferably 30,000 or less. If it is too large, crosslinking may become insufficient and heat resistance may decrease. The number average molecular weight (Mn1) of the polymer polyol (A1) is preferably greater than the number average molecular weight (Mn2) of the polymer polyol (A2), the molecular weight of the tetracarboxylic dianhydride, and the largest among the copolymer components is more preferred.

＜高分子多元醇(A2)＞ 高分子多元醇(A2)為與高分子多元醇(A1)不同的多元醇。與高分子多元醇(A 1)不同，係指至少組成或物性中之任一者不同。高分子多元醇(A2)的數量平均分子量(Mn2)較佳為1,000以上，更佳為1,500以上。未達1,000的話，由於高分子多元醇(A2)變得容易彼此形成鍵結，而容易成為低分子量且高酸價，會有塗膜變脆， 脆化成為問題之疑慮。又，宜為未達10,000，更佳為8,000以下，尤佳為7,000以下，特佳為5,000以下。為10,000以上時，會有四羧酸二酐所為之酸加成鏈延長變得無法進行的情況。<Polymer polyol (A2)> The polymer polyol (A2) is a polyol different from the polymer polyol (A1). Different from the polymer polyol (A 1), it means that at least one of the composition or the physical properties is different. The number average molecular weight (Mn2) of the polymer polyol (A2) is preferably 1,000 or more, more preferably 1,500 or more. If it is less than 1,000, the polymer polyol (A2) is likely to form bonds with each other, and is likely to have a low molecular weight and a high acid value, and the coating film may become brittle and embrittlement may become a problem. Also, it is preferably less than 10,000, more preferably 8,000 or less, particularly preferably 7,000 or less, and particularly preferably 5,000 or less. When it is 10,000 or more, the acid addition chain extension of tetracarboxylic dianhydride may become impossible.

高分子多元醇(A1)之數量平均分子量(Mn1)與高分子多元醇(A2)之數量平均分子量(Mn2)的差並無特別限定，宜為2,000以上，更佳為3,000以上，尤佳為4,000以上。藉由設定前述分子量的差，可達成含有羧酸基之聚酯樹脂(A)之相容性、耐焊料性的改善。亦即，藉由將高分子多元醇(A1)或(A2)中之一者作為長鏈嵌段並高分子量化，可緩和耐焊料性評價時產生的應力。又，藉由將另一者作為短鏈嵌段，可調節羧酸基量，故能賦予耐焊料性。藉此，可達成耐焊料性的改善。分子量之差的上限並無特別限定，宜為40,000以下，更佳為30,000以下，尤佳為20,000以下。The difference between the number average molecular weight (Mn1) of the polymer polyol (A1) and the number average molecular weight (Mn2) of the polymer polyol (A2) is not particularly limited, and it is preferably 2,000 or more, more preferably 3,000 or more, and particularly preferably Above 4,000. By setting the aforementioned difference in molecular weight, the compatibility and solder resistance of the carboxylic acid group-containing polyester resin (A) can be improved. That is, by using one of the polymer polyol (A1) or (A2) as a long-chain block and making it high molecular weight, the stress generated during solder resistance evaluation can be alleviated. In addition, by using the other as a short-chain block, the amount of carboxylic acid groups can be adjusted, so solder resistance can be imparted. In this way, the solder resistance can be improved. The upper limit of the difference in molecular weight is not particularly limited, but is preferably 40,000 or less, more preferably 30,000 or less, and particularly preferably 20,000 or less.

高分子多元醇(A2)的酸價(mgKOH/g)並無特別限定，宜為0.1以上，更佳為0.3以上，尤佳為1以上。過小的話，會有耐焊料性不佳的情況。又，宜為10以下，更佳為8以下，尤佳為6以下。過高的話，會有四羧酸二酐所為之酸加成鏈延長變得無法進行的情況。The acid value (mgKOH/g) of the polymer polyol (A2) is not particularly limited, and is preferably 0.1 or more, more preferably 0.3 or more, and particularly preferably 1 or more. If it is too small, solder resistance may be poor. Moreover, it is preferably 10 or less, more preferably 8 or less, and particularly preferably 6 or less. If it is too high, the acid addition chain extension caused by tetracarboxylic dianhydride may become impossible.

高分子多元醇(A2)之玻璃轉移溫度並無特別限定，宜為-20℃以上，更佳為-10℃以上，尤佳為0℃以上，又更佳為10℃以上，特佳為20℃以上，最佳為30℃以上。玻璃轉移溫度過低的話，黏接劑組成物的黏性容易變強，貼合時容易有氣泡夾入而變得不良。又，宜為80℃以下，更佳為70℃以下。玻璃轉移溫度過高的話，會有塗膜變脆，脆化成為問題之疑慮。The glass transition temperature of the polymer polyol (A2) is not particularly limited. It is preferably -20°C or higher, more preferably -10°C or higher, particularly preferably 0°C or higher, still more preferably 10°C or higher, and particularly preferably 20°C or higher. Above ℃, preferably above 30℃. If the glass transition temperature is too low, the adhesive composition tends to become more viscous, and bubbles tend to be trapped during bonding and become defective. Moreover, it is preferably 80°C or lower, and more preferably 70°C or lower. If the glass transition temperature is too high, the coating film will become brittle and embrittlement will become a problem.

高分子多元醇(A1)及/或高分子多元醇(A2)並無特別限定，宜為聚酯多元醇。The polymer polyol (A1) and/or the polymer polyol (A2) are not particularly limited, but a polyester polyol is preferable.

＜聚酯多元醇＞ 聚酯多元醇宜為由多元羧酸成分與多元醇成分構成者。就構成聚酯多元醇之多元羧酸成分而言，令全部多元羧酸為100莫耳%時，宜含有60莫耳%以上之芳香族二羧酸。更佳為70莫耳%以上，尤佳為80莫耳%以上，亦可為100莫耳%。過少的話，會有塗膜的凝聚力變弱，對於各種基材之黏接強度降低的情況。<Polyester polyol> The polyester polyol is preferably composed of a polyvalent carboxylic acid component and a polyol component. Regarding the polycarboxylic acid components constituting the polyester polyol, when the total polycarboxylic acid is 100 mol%, it is preferable to contain 60 mol% or more of the aromatic dicarboxylic acid. It is more preferably 70 mol% or more, particularly preferably 80 mol% or more, and may also be 100 mol%. If it is too small, the cohesive force of the coating film may become weak, and the bonding strength to various substrates may decrease.

芳香族二羧酸並無特別限定，可列舉：對苯二甲酸、間苯二甲酸、鄰苯二甲酸、萘二羧酸、聯苯二羧酸、2,2’-聯苯二甲酸。又，可列舉：磺基對苯二甲酸、5-磺基間苯二甲酸、4-磺基鄰苯二甲酸、4-磺基萘-2,7-二羧酸、5-(4-磺基苯氧基)間苯二甲酸等具有磺酸基之芳香族二羧酸、以及該等的金屬鹽、銨鹽等具有磺酸鹽基之芳香族二羧酸。該等可單獨使用，亦可將2種以上倂用。其中，對苯二甲酸、間苯二甲酸、及其混合物，就提昇塗膜之凝聚力的觀點而言為特佳。The aromatic dicarboxylic acid is not particularly limited, and examples thereof include terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, and 2,2'-diphthalic acid. In addition, examples include: sulfoterephthalic acid, 5-sulfoisophthalic acid, 4-sulfophthalic acid, 4-sulfonaphthalene-2,7-dicarboxylic acid, 5-(4-sulfo (Phenoxy) isophthalic acid and other aromatic dicarboxylic acids having sulfonic acid groups, and aromatic dicarboxylic acids having sulfonate groups such as metal salts and ammonium salts. These can be used alone or in combination of two or more kinds. Among them, terephthalic acid, isophthalic acid, and mixtures thereof are particularly preferable from the viewpoint of enhancing the cohesive force of the coating film.

其他多元羧酸成分可列舉：1,4-環己烷二羧酸、1,3-環己烷二羧酸、1,2-環己烷二羧酸及其酸酐等脂環族二羧酸；琥珀酸、己二酸、壬二酸、癸二酸、十二烷二酸、二聚酸等脂肪族二羧酸。又，也可使用5-羥基間苯二甲酸、對羥基苯甲酸、對羥基苯乙醇、對羥基苯丙酸、對羥基苯乙酸、6-羥基-2-萘甲酸、4,4-雙(對羥基苯基)戊酸等於分子結構中具有羥基與羧基之羥基羧酸(oxycarboxylic acid)化合物。Examples of other polycarboxylic acid components include: 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid and its anhydrides, and other alicyclic dicarboxylic acids ; Succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, dimer acid and other aliphatic dicarboxylic acids. In addition, 5-hydroxyisophthalic acid, p-hydroxybenzoic acid, p-hydroxyphenethyl alcohol, p-hydroxyphenylpropionic acid, p-hydroxyphenylacetic acid, 6-hydroxy-2-naphthoic acid, 4,4-bis(p-hydroxyphenethyl) Hydroxyphenyl) valeric acid is equivalent to an oxycarboxylic acid compound with a hydroxyl group and a carboxyl group in the molecular structure.

就構成聚酯多元醇之多元醇成分而言，令全部多元醇為100莫耳%時，二醇成分宜為90莫耳%以上，為95莫耳%以上更佳，亦可為100莫耳%。Regarding the polyol components constituting the polyester polyol, when the total polyol is 100 mol%, the diol component is preferably 90 mol% or more, more preferably 95 mol% or more, or 100 mol% %.

二醇成分宜為脂肪族二醇、脂環族二醇、含芳香族之二醇、或含醚鍵之二醇。就脂肪族二醇之示例而言，可列舉：乙二醇、1,2-丙二醇、1,3-丙二醇、1,4-丁二醇、2-甲基-1,3-丙二醇、1,5-戊二醇、2,2-二甲基-1,3-丙二醇、1,6-己二醇、3-甲基-1,5-戊二醇、1,9-壬二醇、2-乙基-2-丁基丙二醇(DMH)、羥基三甲基乙酸新戊二醇酯、二羥甲基庚烷、2,2,4-三甲基-1,3-戊二醇等。就脂環族二醇之示例而言，可列舉：1,4-環己烷二醇、1,4-環己烷二甲醇、三環癸烷二醇、二羥甲基三環癸烷、螺二醇、氫化雙酚A、氫化雙酚A之環氧乙烷加成物及環氧丙烷加成物等。就含醚鍵之二醇之示例而言，可列舉：二乙二醇、三乙二醇、二丙二醇、聚乙二醇、聚丙二醇、聚四亞甲基二醇、新戊二醇環氧乙烷加成物、新戊二醇環氧丙烷加成物。就含芳香族之二醇之示例而言，可例示：對二甲苯二醇、間二甲苯二醇、鄰二甲苯二醇、1,4-伸苯基二醇、1,4-伸苯基二醇之環氧乙烷加成物；雙酚A、雙酚A之環氧乙烷加成物及環氧丙烷加成物等在雙酚類的2個酚性羥基上分別加成1~數莫耳之環氧乙烷或環氧丙烷而得的二醇類等。該等可單獨使用，亦可將2種以上倂用。其中，宜為脂肪族二醇，為乙二醇、2-甲基-1,3-丙二醇、1,4-丁二醇、1,5-戊二醇、2,2-二甲基-1,3-丙二醇、或1,6-己二醇更佳。The diol component is preferably an aliphatic diol, an alicyclic diol, an aromatic diol, or an ether bond-containing diol. Examples of aliphatic diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, 1, 5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol, 2 -Ethyl-2-butylpropanediol (DMH), neopentyl glycol hydroxytrimethylacetate, dimethylolheptane, 2,2,4-trimethyl-1,3-pentanediol, etc. Examples of alicyclic diols include: 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, tricyclodecanediol, dimethyloltricyclodecane, Spirodiol, hydrogenated bisphenol A, hydrogenated bisphenol A's ethylene oxide adduct and propylene oxide adduct, etc. Examples of glycols containing ether bonds include: diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, neopentyl glycol epoxy Ethane adduct, neopentyl glycol propylene oxide adduct. Examples of aromatic-containing diols include para-xylene glycol, meta-xylene glycol, o-xylene glycol, 1,4-phenylene glycol, and 1,4-phenylene glycol. Ethylene oxide adducts of glycols; bisphenol A, ethylene oxide adducts of bisphenol A, and propylene oxide adducts, etc. Add 1 to the two phenolic hydroxyl groups of bisphenols respectively Diols derived from several moles of ethylene oxide or propylene oxide, etc. These can be used alone or in combination of two or more kinds. Among them, aliphatic diols are preferred, such as ethylene glycol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1 ,3-propanediol or 1,6-hexanediol is more preferred.

為了視需要將分支骨架導入至聚酯多元醇中，亦可使多元羧酸成分及/或多元醇成分與3官能以上之成分共聚。進行共聚時，令全部多元羧酸成分及全部多元醇成分分別為100莫耳%時，3官能以上之成分宜為0.1莫耳%以上，為0.5莫耳%以上更佳，且宜為5莫耳%以下，為3莫耳%以下更佳。藉由成為上述範圍內，特別是在使其與硬化劑反應而製作硬化塗膜時，可將分支骨架導入，且可增加樹脂之末端基濃度(反應位點)，並獲得交聯密度高且具強度之塗膜。又，超過5莫耳%的話，會發生塗膜之斷裂點伸度等力學物性降低的情況，有可能在聚合中發生凝膠化。In order to introduce the branch skeleton into the polyester polyol as necessary, the polycarboxylic acid component and/or the polyol component may be copolymerized with a trifunctional or higher component. During the copolymerization, when all the polycarboxylic acid components and all the polyol components are each 100 mol%, the trifunctional or more components should preferably be 0.1 mol% or more, more preferably 0.5 mol% or more, and more preferably 5 mol% Ear% or less, preferably 3 mol% or less. By being within the above range, especially when making a hardened coating film by reacting with a hardener, the branch skeleton can be introduced, and the terminal group concentration (reaction site) of the resin can be increased, and high crosslinking density can be obtained. Strong coating film. In addition, if it exceeds 5 mol%, mechanical properties such as elongation at the breaking point of the coating film may decrease, and gelation may occur during polymerization.

就3官能以上之多元羧酸成分之示例而言，可列舉：偏苯三甲酸、均苯三甲酸、乙二醇雙(脫水偏苯三甲酸)酯、甘油參(脫水偏苯三甲酸)酯、偏苯三甲酸酐、均苯四甲酸酐(PMDA)、氧二苯二甲酸二酐(ODPA)、3,3’,4,4’-二苯甲酮四羧酸二酐(BTDA)、3,3’,4,4’-二苯基四羧酸二酐(BPDA)、3,3’,4,4’-二苯碸四羧酸二酐(DS DA)、4,4’-(六氟異亞丙基)二苯二甲酸二酐(6FDA)、2,2’-雙((二羧基苯氧基)苯基)丙烷二酐(BSAA)等化合物等。另一方面，作為3官能以上之多元醇之示例，可列舉：甘油、三羥甲基乙烷、三羥甲基丙烷、新戊四醇等。Examples of polycarboxylic acid components with more than three functions include: trimellitic acid, trimellitic acid, ethylene glycol bis(dehydrated trimellitic acid) ester, and glycerin (dehydrated trimellitic acid) ester , Trimellitic anhydride, pyromellitic anhydride (PMDA), oxydiphthalic dianhydride (ODPA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 3 ,3',4,4'-Diphenyltetracarboxylic dianhydride (BPDA), 3,3',4,4'-Diphenyl tetracarboxylic dianhydride (DS DA), 4,4'-( Compounds such as hexafluoroisopropylidene)diphthalic dianhydride (6FDA), 2,2'-bis((dicarboxyphenoxy)phenyl)propane dianhydride (BSAA), etc. On the other hand, as examples of polyhydric alcohols with more than three functions, glycerin, trimethylolethane, trimethylolpropane, neopentylerythritol, and the like can be cited.

也可將酸價導入至聚酯多元醇中。聚酯多元醇的酸價宜為10mgKOH/g以下， 為8mgKOH/g以下更佳。過高的話，會有四羧酸二酐所為之酸加成鏈延長變得無法進行的情況。又，宜為0.1mgKOH/g以上，為0.3mgKOH/g以上更佳。過低的話，會有交聯變得不充分，耐濕熱性降低的情況。The acid value can also be introduced into the polyester polyol. The acid value of the polyester polyol is preferably 10 mgKOH/g or less, more preferably 8 mgKOH/g or less. If it is too high, the acid addition chain extension caused by tetracarboxylic dianhydride may become impossible. Furthermore, it is preferably 0.1 mgKOH/g or more, and more preferably 0.3 mgKOH/g or more. If it is too low, crosslinking may become insufficient and the heat and humidity resistance may decrease.

就導入酸價的方法而言，可列舉聚合後藉由酸加成將羧酸導入至聚酯多元醇之方法。酸加成使用單元羧酸、二羧酸、3官能以上之多元羧酸化合物的話，有可能會因酯交換而發生分子量降低，故宜使用至少具有一個羧酸酐基之化合物。羧酸酐可列舉：琥珀酸酐、馬來酸酐、鄰苯二甲酸酐、2,5-降莰烯二羧酸酐、四氫苯二甲酸酐、偏苯三甲酸酐、均苯四甲酸酐(PMDA)、氧二苯二甲酸二酐(ODP A)、3,3’,4,4’-二苯甲酮四羧酸二酐(BTDA)、3,3’,4,4’-二苯基四羧酸二酐(BPDA)、3,3’,4,4’-二苯碸四羧酸二酐(DSDA)、4,4’-(六氟異亞丙基)二苯二甲酸二酐(6FD A)、2,2’-雙((二羧基苯氧基)苯基)丙烷二酐(BSAA)等。The method of introducing the acid value includes a method of introducing carboxylic acid into the polyester polyol by acid addition after polymerization. If monocarboxylic acid, dicarboxylic acid, or trifunctional or higher polycarboxylic acid compound is used for acid addition, the molecular weight may decrease due to transesterification. Therefore, it is preferable to use a compound having at least one carboxylic anhydride group. Carboxylic anhydrides include: succinic anhydride, maleic anhydride, phthalic anhydride, 2,5-norbornene dicarboxylic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride (PMDA), Oxydiphthalic dianhydride (ODP A), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA), 3,3',4,4'-diphenyltetracarboxylic acid Acid dianhydride (BPDA), 3,3',4,4'-diphenyl tetracarboxylic dianhydride (DSDA), 4,4'-(hexafluoroisopropylene) diphthalic dianhydride (6FD A), 2,2'-bis((dicarboxyphenoxy)phenyl)propane dianhydride (BSAA), etc.

＜四羧酸二酐＞ 四羧酸二酐可列舉：芳香族四羧酸二酐、脂肪族四羧酸二酐或脂環族四羧酸二酐，宜為芳香族四羧酸二酐。具體而言，例如可列舉：均苯四甲酸酐(PMD A)、氧二苯二甲酸二酐(ODPA)、3,3’,4,4’-二苯甲酮四羧酸二酐(BTDA)、3,3’,4,4’-二苯基四羧酸二酐(BPDA)、3,3’,4,4’-二苯碸四羧酸二酐(DSDA)、4,4’-(六氟異亞丙基)二苯二甲酸二酐(6FDA)、2,2’-雙[(二羧基苯氧基)苯基]丙烷二酐(BSAA)，該等可單獨使用，亦可將2種以上倂用。其中，宜為均苯四甲酸酐。<Tetracarboxylic dianhydride> Examples of the tetracarboxylic dianhydride include aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, or alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride is preferable. Specifically, for example, pyromellitic anhydride (PMD A), oxydiphthalic dianhydride (ODPA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA ), 3,3',4,4'-diphenyltetracarboxylic dianhydride (BPDA), 3,3',4,4'-diphenyltetracarboxylic dianhydride (DSDA), 4,4' -(Hexafluoroisopropylidene)diphthalic dianhydride (6FDA), 2,2'-bis[(dicarboxyphenoxy)phenyl]propane dianhydride (BSAA), these can be used alone, or Can use more than 2 kinds. Among them, pyromellitic anhydride is preferable.

＜含有羧酸基之聚酯樹脂(A)＞ 本發明之含有羧酸基之聚酯樹脂(A)的玻璃轉移溫度需為40℃以上。較佳為45℃以上，更佳為50℃以上。玻璃轉移溫度過低的話，黏接劑組成物的黏性變強，貼合時容易有氣泡夾入而變得不良、片材壽命變得不足。又，需為90℃以下。較佳為85℃以下，更佳為80℃以下。玻璃轉移溫度過高的話，會有塗膜變脆，脆化成為問題之疑慮。<Carboxylic acid group-containing polyester resin (A)> The glass transition temperature of the carboxylic acid group-containing polyester resin (A) of the present invention must be 40°C or higher. It is preferably 45°C or higher, more preferably 50°C or higher. If the glass transition temperature is too low, the adhesive composition becomes more viscous, bubbles are likely to be trapped during bonding, and the sheet life becomes insufficient. In addition, it must be below 90°C. It is preferably 85°C or less, more preferably 80°C or less. If the glass transition temperature is too high, the coating film will become brittle and embrittlement will become a problem.

本發明之含有羧酸基之聚酯樹脂(A)的酸價需為1mgKOH/g以上。較佳為5 mgKOH/g以上，更佳為10mgKOH/g以上。又，需為30mgKOH/g以下。較佳為28 mgKOH/g以下，更佳為25mgKOH/g以下。酸價過小的話，有時會有交聯不足，無法獲得充分耐焊料性的情況，酸價過高的話，有時會有交聯密度變得過高，導致硬化塗膜變硬，黏接性降低的情況。又，有時會有如下情況：將含有羧酸基之聚酯樹脂(A)溶解於溶劑而得之清漆的保存穩定性降低，且交聯反應容易在常溫下進行，無法獲得穩定的片材壽命。The acid value of the carboxylic acid group-containing polyester resin (A) of the present invention must be 1 mgKOH/g or more. It is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more. In addition, it needs to be 30 mgKOH/g or less. It is preferably 28 mgKOH/g or less, more preferably 25 mgKOH/g or less. If the acid value is too low, there may be insufficient cross-linking and insufficient solder resistance may be obtained. If the acid value is too high, the cross-linking density may become too high, which may result in hardening of the cured coating film and adhesion. Reduced situation. In addition, there may be cases where the storage stability of the varnish obtained by dissolving the carboxylic acid group-containing polyester resin (A) in a solvent is reduced, and the crosslinking reaction is likely to proceed at room temperature, and a stable sheet cannot be obtained life.

含有羧酸基之聚酯樹脂(A)，係包含前述高分子多元醇(A1)、高分子多元醇(A2)及四羧酸二酐作為共聚成分的樹脂。較佳為含有羧酸基之聚酯樹脂(A)之數量平均分子量(Mn3)為高分子多元醇(A1)之數量平均分子量(Mn1)的1.7倍以下者。亦即Mn3/Mn1≦1.7。更佳為1.6倍以下。據認為超過1.7倍時，係分子量的差較小，或四羧酸二酐的量過剩。因此，含有羧酸基之聚酯樹脂(A)的羧酸基含量不足而導致耐焊料性降低，或硬化塗膜的彈性模量變得過高而導致黏接性容易降低。Mn3/Mn1的下限宜為0.8倍以上，更佳為0.9倍以上，尤佳為1.0倍以上。過小的話，由於有可能較常會發生僅高分子多元醇(A2)與鏈延長劑(四羧酸二酐)之反應，高分子多元醇(A1)之嵌段有可能不會與羧酸二酐充分反應，而導致耐焊料性變得不足。此外，含有羧酸基之聚酯樹脂(A)若為上述數量平均分子量(Mn3/Mn 1)之範圍內，則亦可含有僅高分子多元醇(A1)與羧酸二酐之樹脂、僅高分子多元醇(A2)與羧酸二酐之樹脂。The carboxylic acid group-containing polyester resin (A) is a resin containing the aforementioned polymer polyol (A1), polymer polyol (A2), and tetracarboxylic dianhydride as copolymer components. Preferably, the number average molecular weight (Mn3) of the carboxylic acid group-containing polyester resin (A) is 1.7 times or less the number average molecular weight (Mn1) of the polymer polyol (A1). That is, Mn3/Mn1≦1.7. More preferably, it is 1.6 times or less. It is considered that when it exceeds 1.7 times, the difference in molecular weight is small, or the amount of tetracarboxylic dianhydride is excessive. Therefore, the carboxylic acid group-containing polyester resin (A) has an insufficient carboxylic acid group content, resulting in a decrease in solder resistance, or the elastic modulus of the cured coating film becomes too high, and adhesiveness tends to decrease. The lower limit of Mn3/Mn1 is preferably 0.8 times or more, more preferably 0.9 times or more, and particularly preferably 1.0 times or more. If it is too small, the polymer polyol (A2) may react with the chain extender (tetracarboxylic dianhydride) more often, and the block of the polymer polyol (A1) may not react with the carboxylic dianhydride It reacts sufficiently, resulting in insufficient solder resistance. In addition, if the carboxylic acid group-containing polyester resin (A) is within the range of the above-mentioned number average molecular weight (Mn3/Mn 1), it may also contain only polymer polyol (A1) and carboxylic dianhydride resin, only Polymer polyol (A2) and carboxylic dianhydride resin.

含有羧酸基之聚酯樹脂(A)中之高分子多元醇(A1)與高分子多元醇(A2)的共聚比率，相對於高分子多元醇(A1)100質量份，高分子多元醇(A2)宜為5質量份以上，更佳為10質量份以上，尤佳為20質量份以上。又，宜為50質量份以下，更佳為40質量份以下，尤佳為30質量份以下，過多的話，有時會有耐加濕焊料性變得不足的情況，過少的話，有時會有可與四羧酸酐反應之末端變少，耐熱性變得不足的情況。The copolymerization ratio of the polymer polyol (A1) and the polymer polyol (A2) in the carboxylic acid group-containing polyester resin (A), relative to 100 parts by mass of the polymer polyol (A1), the polymer polyol ( A2) Preferably it is 5 parts by mass or more, more preferably 10 parts by mass or more, and particularly preferably 20 parts by mass or more. In addition, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less. When the number of terminals that can react with tetracarboxylic anhydride is reduced, and the heat resistance becomes insufficient.

含有羧酸基之聚酯樹脂(A)中之高分子多元醇(A1)與四羧酸二酐的共聚比率，相對於高分子多元醇(A1)100質量份，四羧酸二酐宜為0.5質量份以上，更佳為1質量份以上，尤佳為2質量份以上。又，宜為10質量份以下，更佳為8質量份以下，尤佳為5質量份以下，過少的話，有時會有交聯不足、耐熱性變得不足的情況，過多的話，有時會有塗膜變硬，無法獲得充分密接性的情況。The copolymerization ratio of the polymer polyol (A1) and tetracarboxylic dianhydride in the carboxylic acid group-containing polyester resin (A), relative to 100 parts by mass of the polymer polyol (A1), the tetracarboxylic dianhydride is preferably 0.5 part by mass or more, more preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more. In addition, it is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, and particularly preferably 5 parts by mass or less. There are cases where the coating film becomes hard and sufficient adhesiveness cannot be obtained.

含有羧酸基之聚酯樹脂(A)中之高分子多元醇(A1)的共聚量宜為30質量%以上，更佳為40質量%以上，尤佳為50質量%以上。藉由增加高分子多元醇(A1)的共聚量，可期待耐加濕焊料性的改善。又，宜為90重量%以下，更佳為85質量%以下，尤佳為80質量%以下。過多的話，有時會有高分子多元醇(A2)、四羧酸二酐之共聚量降低，耐焊料性、黏接性降低的情況。 含有羧酸基之聚酯樹脂(A)的製造方法並無特別限定，較佳為溶液聚合或熔融聚合，尤佳為溶液聚合。The copolymerization amount of the polymer polyol (A1) in the carboxylic acid group-containing polyester resin (A) is preferably 30% by mass or more, more preferably 40% by mass or more, and particularly preferably 50% by mass or more. By increasing the copolymerization amount of the polymer polyol (A1), an improvement in the resistance to humidified solder can be expected. Moreover, it is preferably 90% by weight or less, more preferably 85% by weight or less, and particularly preferably 80% by weight or less. If it is too much, the copolymerization amount of the polymer polyol (A2) and tetracarboxylic dianhydride may decrease, and the solder resistance and adhesiveness may decrease. The method for producing the carboxylic acid group-containing polyester resin (A) is not particularly limited, but solution polymerization or melt polymerization is preferred, and solution polymerization is particularly preferred.

＜環氧樹脂(B)＞ 環氧樹脂(B)只要是與含有羧酸基之聚酯樹脂(A)之羧基發生硬化反應並交聯者即可，並無特別限定，但宜為一分子中具有多個環氧基之多官能環氧樹脂。藉由使用多官能環氧樹脂，由黏接劑組成物獲得之硬化塗膜容易形成3維交聯，可改善耐熱性。作為多官能環氧樹脂，例如可列舉：甲酚酚醛清漆型環氧樹脂、具有二環戊二烯骨架之環氧樹脂、苯酚酚醛清漆型環氧樹脂。為甲酚酚醛清漆型環氧樹脂、苯酚酚醛清漆型環氧樹脂的話，可使硬化塗膜之交聯密度降低，並緩和剝離時之應力，因而耐焊料特性得到改善。就甲酚酚醛清漆型環氧樹脂之市售品而言，可列舉DIC公司製的YDCN-700等。另一方面，為具有二環戊二烯骨架之環氧樹脂的話，由於二環戊二烯骨架具剛直性，故硬化塗膜之吸濕性可變得極小，能使硬化塗膜之交聯密度降低，並緩和剝離時之應力。因此，耐焊料性得到改善。具有二環戊二烯骨架之環氧樹脂的市售品，可列舉DIC公司製HP7200系列。該等可單獨使用，亦可將2種以上併用。<Epoxy resin (B)> The epoxy resin (B) is not particularly limited as long as it hardens and crosslinks the carboxyl group of the polyester resin (A) containing a carboxylic acid group, but it is preferably one molecule Multifunctional epoxy resin with multiple epoxy groups in it. By using a multifunctional epoxy resin, the hardened coating film obtained from the adhesive composition can easily form three-dimensional crosslinks, which can improve heat resistance. Examples of polyfunctional epoxy resins include cresol novolac type epoxy resins, epoxy resins having a dicyclopentadiene skeleton, and phenol novolac type epoxy resins. If it is a cresol novolac type epoxy resin or a phenol novolac type epoxy resin, the crosslink density of the hardened coating film can be reduced, and the stress during peeling can be relieved, thereby improving the solder resistance. Examples of commercially available products of cresol novolac type epoxy resins include YDCN-700 manufactured by DIC Corporation. On the other hand, if it is an epoxy resin with a dicyclopentadiene skeleton, because the dicyclopentadiene skeleton is rigid, the moisture absorption of the cured coating film can be extremely small, and the cured coating film can be cross-linked The density is reduced and the stress during peeling is alleviated. Therefore, solder resistance is improved. Examples of commercially available products of epoxy resins having a dicyclopentadiene skeleton include HP7200 series manufactured by DIC Corporation. These can be used alone or in combination of two or more kinds.

進一步，除了使用上述多官能環氧樹脂之外，也可使用含有氮原子之環氧樹脂。併用含有氮原子之環氧樹脂的話，會有能以相對較低溫度之加熱使黏接劑組成物之塗膜成為半硬化狀態(以下有時稱為B階段)，且可抑制B階段薄膜之流動性，並改善黏接操作中之作業性的傾向。又，可期待抑制B階段薄膜之起泡的效果，故較佳。作為含有氮原子之環氧樹脂，例如可列舉：四環氧丙基二胺基二苯甲烷、三環氧丙基對胺苯酚、四環氧丙基雙胺基甲基環己酮、N,N,N’,N’-四環氧丙基-間二甲苯二胺等環氧丙胺系等。該等含有氮原子之環氧樹脂的摻合量宜為環氧樹脂(B)全體之20質量%以下。摻合量多於20質量%的話，會有剛直性變得過高，黏接性降低的傾向，又，會有在黏接片保存時交聯反應容易進行，片材壽命降低的傾向。更佳摻合量的上限為10質量%，尤佳為5質量%。Furthermore, in addition to using the above-mentioned polyfunctional epoxy resin, an epoxy resin containing a nitrogen atom can also be used. If the epoxy resin containing nitrogen atoms is used in combination, the coating film of the adhesive composition can be heated at a relatively low temperature to become a semi-cured state (hereinafter sometimes referred to as B-stage), and the B-stage film can be suppressed. Liquidity, and improve the tendency of workability in bonding operations. In addition, the effect of suppressing the blistering of the B-stage film can be expected, which is preferable. Examples of epoxy resins containing nitrogen atoms include: tetraglycidyl diamino diphenylmethane, triglycidyl p-aminophenol, tetraglycidyl diamino methyl cyclohexanone, N, Glycidamine series such as N,N',N'-tetraglycidyl-m-xylenediamine, etc. The blending amount of the epoxy resin containing nitrogen atoms is preferably 20% by mass or less of the total epoxy resin (B). If the blending amount is more than 20% by mass, the rigidity tends to be too high and the adhesiveness tends to decrease. In addition, the crosslinking reaction tends to proceed easily when the adhesive sheet is stored, and the sheet life tends to decrease. The upper limit of the blending amount is more preferably 10% by mass, and particularly preferably 5% by mass.

亦可倂用其他環氧樹脂作為本發明中使用之環氧樹脂(B)。例如可列舉：雙酚A二環氧丙醚、雙酚S二環氧丙醚、溴化雙酚A二環氧丙醚等環氧丙醚型；六氫苯二甲酸環氧丙酯、二聚酸環氧丙酯等環氧丙酯型；異氰尿酸三環氧丙酯、甲酸-3,4-環氧環己基甲酯、環氧化聚丁二烯、環氧化大豆油等脂環族或脂肪族環氧化物等，可單獨使用一種，亦可將二種以上倂用。It is also possible to use other epoxy resins as the epoxy resin (B) used in the present invention. Examples include: glycidyl ether type such as bisphenol A diglycidyl ether, bisphenol S diglycidyl ether, and brominated bisphenol A diglycidyl ether; glycidyl hexahydrophthalate, two Glycidyl ester type such as polyglycidyl ester; triglycidyl isocyanurate, 3,4-epoxycyclohexyl methyl formate, epoxidized polybutadiene, epoxidized soybean oil and other alicyclic Or aliphatic epoxides, etc., one kind may be used alone, or two or more kinds may be used.

環氧樹脂(B)相對於含有羧酸基之聚酯樹脂(A)100質量份，宜為2質量份以上，更佳為5質量份以上。又，宜為50質量份以下，更佳為40質量份以下，尤佳為30質量份以下。過少的話，有時會有硬化變得不充分，黏接性、耐濕熱性降低的情況，過多的話，未交聯的環氧樹脂變多，耐焊料性降低。又，有時會有因羧酸與環氧基反應時所產生之羥基導致吸水率增大，耐濕熱性惡化的情況。The epoxy resin (B) is preferably 2 parts by mass or more, and more preferably 5 parts by mass or more with respect to 100 parts by mass of the carboxylic acid group-containing polyester resin (A). Moreover, it is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less. If the amount is too small, the curing may be insufficient, and the adhesiveness and heat and humidity resistance may decrease. If the amount is too large, the uncrosslinked epoxy resin may increase and the solder resistance may decrease. In addition, the water absorption rate may increase due to the hydroxyl group generated when the carboxylic acid reacts with the epoxy group, and the humidity and heat resistance may deteriorate.

本發明中，環氧樹脂(B)之硬化反應可使用硬化觸媒。例如可列舉：2-甲基咪唑、1,2-二甲基咪唑、2-乙基-4-甲基咪唑、2-苯基-4-甲基咪唑、或1-氰乙基-2-乙基-4-甲基咪唑等咪唑系化合物；三乙胺、三乙二胺、N’-甲基-N-(2-二甲基胺基乙基)哌

、1,8-二氮雜雙環(5,4,0)-十一烯-7、1,5-二氮雜雙環(4,3,0)-壬烯-5、或6-二丁基胺基-1,8-二氮雜雙環(5,4,0)-十一烯-7等三級胺類、及將該等三級胺類以苯酚、辛酸、或四級化四苯基硼酸鹽等製成胺鹽之化合物；三烯丙基鋶六氟銻酸鹽或二烯丙基錪六氟銻酸鹽等陽離子觸媒；三苯基膦等。該等中，考量熱硬化性、耐熱性、對於金屬之黏接性、及摻合後之保存穩定性的觀點，宜為1,8-二氮雜雙環(5,4,0)-十一烯-7、1,5-二氮雜雙環(4,3,0)-壬烯-5、或6-二丁基胺基-1,8-二氮雜雙環(5,4,0)-十一烯-7等三級胺類、及將該等三級胺類以苯酚、辛酸、或四級化四苯基硼酸鹽等製成胺鹽之化合物。硬化觸媒之摻合量相對於含有羧酸基之聚酯樹脂(A)100質量份，宜為0.01~1.0質量份。若為此範圍內，可進一步增加對於含有羧酸基之聚酯樹脂(A)與環氧樹脂(B)之反應的觸媒效果，獲得牢固的黏接性能。In the present invention, a curing catalyst can be used for the curing reaction of the epoxy resin (B). Examples include: 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, or 1-cyanoethyl-2- Ethyl-4-methylimidazole and other imidazole compounds; triethylamine, triethylenediamine, N'-methyl-N-(2-dimethylaminoethyl)piper

, 1,8-diazabicyclo(5,4,0)-undecene-7, 1,5-diazabicyclo(4,3,0)-nonene-5, or 6-dibutyl Amino-1,8-diazabicyclo(5,4,0)-undecene-7 and other tertiary amines, and these tertiary amines are phenol, caprylic acid, or quaternary tetraphenyl Compounds made into amine salts such as borate; cationic catalysts such as triallyl hexafluoroantimonate or diallyl hexafluoroantimonate; triphenyl phosphine, etc. Among them, considering the thermal hardenability, heat resistance, adhesion to metals, and storage stability after blending, 1,8-diazabicyclo(5,4,0)-eleven Ene-7, 1,5-diazabicyclo(4,3,0)-nonene-5, or 6-dibutylamino-1,8-diazabicyclo(5,4,0)- Tertiary amines such as undecene-7, and compounds in which these tertiary amines are made into amine salts with phenol, caprylic acid, or quaternary tetraphenyl borate. The blending amount of the hardening catalyst is preferably 0.01 to 1.0 parts by mass relative to 100 parts by mass of the carboxylic acid group-containing polyester resin (A). If it is within this range, the catalyst effect for the reaction between the carboxylic acid group-containing polyester resin (A) and the epoxy resin (B) can be further increased, and firm adhesion performance can be obtained.

＜有機溶劑＞ 本發明之黏接劑組成物可溶解於有機溶劑而製成樹脂溶液。有機溶劑只要是使含有羧酸基之聚酯樹脂(A)溶解者即可，並無特別限定，為亦使環氧樹脂(B)溶解者更佳。有機溶劑可使用：苯、甲苯、二甲苯等芳香族系烴；環己烷、環己烯、甲基環己烷、乙基環己烷等脂環族烴；甲醇、乙醇、異丙醇、丁醇、戊醇、己醇、丙二醇、苯酚等醇系溶劑；丙酮、甲基異丁酮、甲乙酮、戊酮、己酮、環己酮、異佛酮、苯乙酮等酮系溶劑；甲基賽珞蘇、乙基賽珞蘇等賽珞蘇類；乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酸甲酯、甲酸丁酯等酯系溶劑；三氯乙烯、二氯乙烯、氯苯、氯仿等鹵化烴等，該等可使用1種，亦可將2種以上倂用。其中，宜為芳香族系烴與酮系溶劑之混合溶劑，為甲苯與甲乙酮之混合溶劑更佳。<Organic solvent> The adhesive composition of the present invention can be dissolved in an organic solvent to prepare a resin solution. The organic solvent is not particularly limited as long as it dissolves the carboxylic acid group-containing polyester resin (A), and it is more preferable to also dissolve the epoxy resin (B). Organic solvents can be used: aromatic hydrocarbons such as benzene, toluene, and xylene; alicyclic hydrocarbons such as cyclohexane, cyclohexene, methylcyclohexane, and ethylcyclohexane; methanol, ethanol, isopropanol, Alcohol solvents such as butanol, pentanol, hexanol, propylene glycol, and phenol; ketone solvents such as acetone, methyl isobutyl ketone, methyl ethyl ketone, pentanone, hexanone, cyclohexanone, isophorone, and acetophenone; Cyrosu, Ethyl Cyrosu, etc.; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, methyl propionate, butyl formate, etc.; trichloroethylene, dichloroethylene, chlorine Halogenated hydrocarbons such as benzene and chloroform can be used alone or in combination of two or more. Among them, a mixed solvent of aromatic hydrocarbons and ketone solvents is preferable, and a mixed solvent of toluene and methyl ethyl ketone is more preferable.

有機溶劑量相對於含有羧酸基之聚酯樹脂(A)100質量份，宜為50質量份以上，更佳為70質量份以上，尤佳為100質量份以上。又，宜為700質量份以下，更佳為600質量份以下，尤佳為500質量份以下。過少的話，有時會有黏接劑組成物之保存穩定性降低的情況，過多的話，在工業上可能變得不利。The amount of the organic solvent is preferably 50 parts by mass or more, more preferably 70 parts by mass or more, and particularly preferably 100 parts by mass or more relative to 100 parts by mass of the carboxylic acid group-containing polyester resin (A). Furthermore, it is preferably 700 parts by mass or less, more preferably 600 parts by mass or less, and particularly preferably 500 parts by mass or less. If the amount is too small, the storage stability of the adhesive composition may decrease, and if the amount is too large, it may become industrially disadvantageous.

＜其他添加劑＞ 本發明之黏接劑組成物，在不損及本發明之效果的範圍內，可進一步摻合各種硬化性樹脂、添加劑。硬化性樹脂可列舉：苯酚系樹脂、胺基樹脂、異氰酸酯化合物、或矽烷偶聯劑等。<Other additives> In the adhesive composition of the present invention, various curable resins and additives can be further blended within a range that does not impair the effects of the present invention. Examples of the curable resin include phenol resins, amino resins, isocyanate compounds, and silane coupling agents.

苯酚系樹脂例如可列舉：烷基化苯酚類、甲酚類之甲醛縮合物。具體而言，可列舉：烷基化(例如甲基、乙基、丙基、異丙基、丁基)苯酚、對第三戊酚、4,4’-第二亞丁酚、對第三丁酚、鄰甲酚、間甲酚、對甲酚、對環己酚、4,4’-異亞丙酚、對壬酚、對辛酚、3-十五烷基酚、苯酚、苯基鄰甲酚、對苯基酚、二甲酚等之甲醛縮合物。該等可單獨使用，亦可將2種以上倂用。Examples of phenol resins include alkylated phenols and formaldehyde condensates of cresols. Specifically, examples include: alkylated (for example, methyl, ethyl, propyl, isopropyl, butyl) phenol, p-tertyl phenol, 4,4'-second butylene phenol, p-tert-butyl Phenol, o-cresol, m-cresol, p-cresol, p-cyclohexanol, 4,4'-isopropylidene, p-nonanol, p-octanol, 3-pentadecylphenol, phenol, phenyl o Formaldehyde condensates of cresol, p-phenylphenol, xylenol, etc. These can be used alone or in combination of two or more kinds.

就胺基樹脂而言，例如可列舉：尿素、三聚氰胺、苯并胍胺等之甲醛加成物，進一步可列舉該等利用碳原子數為1~6之醇而得之烷基醚化合物。具體而言可列舉：甲氧基化羥甲基尿素、甲氧基化羥甲基N,N-伸乙基尿素、甲氧基化羥甲基二氰二胺、甲氧基化羥甲基三聚氰胺、甲氧基化羥甲基苯并胍胺、丁氧基化羥甲基三聚氰胺、丁氧基化羥甲基苯并胍胺等。宜為甲氧基化羥甲基三聚氰胺、丁氧基化羥甲基三聚氰胺、及羥甲基化苯并胍胺，可分別單獨使用，亦可倂用。The amino resin includes, for example, formaldehyde adducts such as urea, melamine, and benzoguanamine, and further examples thereof include alkyl ether compounds obtained by using alcohols having 1 to 6 carbon atoms. Specifically, it can include: methoxylated hydroxymethyl urea, methoxylated hydroxymethyl N,N-ethylene urea, methoxylated hydroxymethyl dicyandiamide, methoxylated hydroxymethyl Melamine, methoxylated methylol benzoguanamine, butoxylated methylol melamine, butoxylated methylol benzoguanamine, etc. Preferably, they are methoxylated methylol melamine, butoxylated methylol melamine, and methylolated benzoguanamine, which can be used individually or independently.

就異氰酸酯化合物而言，有芳香族、或脂肪族之二異氰酸酯、3價以上之多異氰酸酯，為低分子化合物、高分子化合物中之任意者均可。例如可列舉：四亞甲基二異氰酸酯、六亞甲基二異氰酸酯、甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、氫化二苯基甲烷二異氰酸酯、二甲苯二異氰酸酯、氫化二甲苯二異氰酸酯、異佛酮二異氰酸酯或該等異氰酸酯化合物之3聚物。進一步可列舉使過量的該等異氰酸酯化合物、與低分子活性氫化合物或高分子活性氫化合物反應而獲得之含有末端異氰酸酯基之化合物，該低分子活性氫化合物例如為：乙二醇、丙二醇、三羥甲基丙烷、甘油、山梨糖醇、乙二胺、單乙醇胺、二乙醇胺、或三乙醇胺等；該高分子活性氫化合物例如為：各種聚酯多元醇類、聚醚多元醇類、聚醯胺類等。The isocyanate compound includes aromatic or aliphatic diisocyanate, trivalent or higher polyisocyanate, and can be either a low molecular compound or a high molecular compound. Examples include: tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylene diisocyanate, hydrogenated xylene diisocyanate, isophor Ketone diisocyanate or 3-mer of these isocyanate compounds. Further examples include compounds containing terminal isocyanate groups obtained by reacting excess of these isocyanate compounds with low molecular active hydrogen compounds or high molecular active hydrogen compounds. The low molecular active hydrogen compounds are, for example, ethylene glycol, propylene glycol, tris Methylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, or triethanolamine, etc.; the polymer active hydrogen compound is, for example, various polyester polyols, polyether polyols, and polyols Amines and so on.

異氰酸酯化合物也可為封端化異氰酸酯。就異氰酸酯封端化劑而言，例如可列舉：苯酚、硫代苯酚、甲基硫代苯酚、甲酚、二甲酚、間苯二酚、硝基酚、氯酚等苯酚類；丙酮肟、甲乙酮肟、環己酮肟等肟類；甲醇、乙醇、丙醇、丁醇等醇類；2-氯乙醇、1,3-二氯-2-丙醇等經鹵素取代之醇類；第三丁醇、第三戊醇等三級醇類；ε-己內醯胺、δ-戊內醯胺、γ-丁內醯胺、β-丙內醯胺等內醯胺類。其他也可列舉：芳香族胺類、醯亞胺類、乙醯丙酮、乙醯乙酸酯、丙二酸乙酯等活性亞甲基化合物；硫醇類、亞胺類、尿素類、二芳基化合物類亞硫酸氫鈉等。封端化異氰酸酯可藉由以往習知的適當方法使上述異氰酸酯化合物與異氰酸酯化合物及異氰酸酯封端化劑進行加成反應而獲得。The isocyanate compound may also be a blocked isocyanate. Examples of isocyanate blocking agents include phenols such as phenol, thiophenol, methyl thiophenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol; acetoxime, Methyl ethyl ketoxime, cyclohexanone oxime and other oximes; methanol, ethanol, propanol, butanol and other alcohols; 2-chloroethanol, 1,3-dichloro-2-propanol and other halogen-substituted alcohols; third Tertiary alcohols such as butanol and tertiary amyl alcohol; internal amines such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactin. Other examples include: aromatic amines, imines, acetone, acetone, ethyl malonate and other active methylene compounds; mercaptans, imines, ureas, diaromatics Base compounds such as sodium bisulfite, etc. The blocked isocyanate can be obtained by an addition reaction of the above-mentioned isocyanate compound, an isocyanate compound, and an isocyanate blocking agent by a conventionally known appropriate method.

本發明之黏接劑組成物中，也可視需要摻合矽烷偶聯劑。藉由摻合矽烷偶聯劑，對於金屬之黏接性、耐熱性之特性得到改善，故非常理想。矽烷偶聯劑並無特別限定，可列舉：具有不飽和基者、具有環氧丙基者、具有胺基者等。具有不飽和基之矽烷偶聯劑可列舉：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等。具有環氧丙基之矽烷偶聯劑可列舉：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、β-(3,4-環氧環己基)乙基三乙氧基矽烷等。具有胺基之矽烷偶聯劑可列舉：N-β-(胺基乙基)-γ-胺基丙基三甲氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基甲基二甲氧基矽烷、N-苯基-γ-胺基丙基三甲氧基矽烷等。該等中，考量耐熱性的觀點，宜為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、或β-(3,4-環氧環己基)乙基三乙氧基矽烷等具有環氧丙基之矽烷偶聯劑。矽烷偶聯劑之摻合量相對於含羧酸基之聚酯樹脂(A)100質量份，宜為0.5~20質量份。矽烷偶聯劑之摻合量未達0.5質量份的話，會有獲得之黏接劑組成物之耐熱性變得不良的情況，超過20質量份的話，會有變成耐熱性不良、黏接性不良的情況。The adhesive composition of the present invention may also be blended with a silane coupling agent as needed. By blending the silane coupling agent, the adhesion to metals and the characteristics of heat resistance are improved, so it is very ideal. The silane coupling agent is not particularly limited, and examples thereof include those having an unsaturated group, those having a glycidyl group, and those having an amine group. Examples of the silane coupling agent having an unsaturated group include vinyl ginseng (β-methoxyethoxy) silane, vinyl triethoxy silane, vinyl trimethoxy silane, and the like. Silane coupling agents with glycidyl groups include: γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3 , 4-epoxycyclohexyl) ethyl triethoxy silane, etc. Silane coupling agents with amino groups include: N-β-(aminoethyl)-γ-aminopropyl trimethoxysilane, N-β-(aminoethyl)-γ-aminopropyl Methyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, etc. Among them, in consideration of heat resistance, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, or β-(3 , 4-epoxycyclohexyl) ethyl triethoxy silane and other silane coupling agents with glycidyl groups. The blending amount of the silane coupling agent is preferably 0.5-20 parts by mass relative to 100 parts by mass of the carboxylic acid group-containing polyester resin (A). If the blending amount of the silane coupling agent is less than 0.5 parts by mass, the heat resistance of the obtained adhesive composition may become poor. If it exceeds 20 parts by mass, the heat resistance and adhesion may be poor. Case.

本發明之黏接劑組成物中，可視需要適當摻合溴系、磷系、氮系、金屬氫氧化化合物等阻燃劑、調平劑、顏料、染料等添加劑。In the adhesive composition of the present invention, additives such as bromine-based, phosphorus-based, nitrogen-based, and metal hydroxide compounds, such as flame retardants, leveling agents, pigments, and dyes, can be appropriately blended as needed.

＜黏接片＞ 本發明中，黏接片係指含有使本發明之黏接劑組成物硬化而得的黏接劑組成物之塗膜(以下亦稱為黏接劑層)者。黏接片具有藉由黏接劑層使基材黏接於被黏接材之功能。黏接片之基材在黏接後作為被黏接材之保護層而發揮功能。又，使用脫模基材的話，可將脫模基材脫模，再將黏接劑層轉印至另外的被黏接材。黏接片可藉由將黏接劑組成物塗布於基材或脫模基材，並進行乾燥、硬化而獲得。具體的構成可列舉：基材/黏接劑層、脫模基材/黏接劑層、脫模基材/黏接劑層/基材、脫模基材/黏接劑層/脫模基材等。又，視情況也可為剝離脫模基材後的黏接劑層本身。又，黏接片中亦可含有微量或少量的有機溶劑。<Adhesive sheet> In the present invention, an adhesive sheet refers to a coating film (hereinafter also referred to as an adhesive layer) of an adhesive composition obtained by curing the adhesive composition of the present invention. The adhesive sheet has the function of bonding the base material to the material to be bonded through the adhesive layer. The base material of the adhesive sheet functions as a protective layer of the material to be bonded after bonding. In addition, if a release substrate is used, the release substrate can be released, and then the adhesive layer can be transferred to another material to be bonded. The adhesive sheet can be obtained by coating the adhesive composition on the base material or the release base material, and drying and hardening. Specific constitutions include: base material/adhesive layer, release base material/adhesive layer, release base material/adhesive layer/substrate, release base material/adhesive layer/release base Materials and so on. Moreover, it may be the adhesive layer itself after peeling off the mold release base material as appropriate. In addition, a trace or a small amount of organic solvent may be contained in the adhesive sheet.

就黏接片而言，可藉由將本發明之黏接劑組成物依常法塗布於各種基材，並將溶劑之至少一部分去除並使其乾燥而獲得。又，將溶劑之至少一部分去除並乾燥後，將脫模基材貼附於黏接劑層的話，能在不造成朝基材轉移的情況下進行捲繞，操作性優異，且黏接劑層也受到保護，故保存性優異，使用也容易。又，塗布於脫模基材並乾燥後，視需要貼附另外的脫模基材的話，也可將黏接劑層本身轉印至其他基材。As for the adhesive sheet, it can be obtained by applying the adhesive composition of the present invention to various substrates in a usual manner, removing at least a part of the solvent, and drying it. In addition, after removing at least a part of the solvent and drying it, the release base material is attached to the adhesive layer, it can be wound without causing transfer to the base material, and the handling is excellent, and the adhesive layer It is also protected, so it has excellent storage properties and is easy to use. In addition, after coating on a release substrate and drying, if another release substrate is attached as necessary, the adhesive layer itself may be transferred to another substrate.

基材並無特別限定，可列舉：薄膜狀樹脂、金屬板、金屬箔、紙類等。薄膜狀樹脂可例示：聚酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、烯烴系樹脂等。金屬板及金屬箔之材料可例示：SUS、銅、鋁、鐵、鋅等各種金屬、及各自的合金、鍍敷品等，紙類可例示：優質紙、牛皮紙、捲紙、玻璃紙等。又，複合材料可例示玻璃環氧樹脂等。考量基材與黏接劑組成物之黏接力、耐久性，宜為聚酯樹脂、聚醯胺樹脂、聚醯亞胺樹脂、聚醯胺醯亞胺樹脂、SUS鋼板、銅箔、鋁箔、玻璃環氧樹脂。The base material is not particularly limited, and examples thereof include film-like resins, metal plates, metal foils, papers, and the like. Examples of film-like resins include polyester resins, polyamide resins, polyimide resins, polyimide resins, and olefin resins. Examples of materials for metal plates and metal foils include various metals such as SUS, copper, aluminum, iron, zinc, and their respective alloys, plating products, etc. Examples of paper include high-quality paper, kraft paper, roll paper, cellophane, etc. In addition, as a composite material, glass epoxy resin and the like can be exemplified. Considering the adhesion and durability of the substrate and the adhesive composition, polyester resin, polyamide resin, polyimide resin, polyimide resin, SUS steel plate, copper foil, aluminum foil, and glass are suitable Epoxy resin.

脫模基材並無特別限定，例如可列舉：於優質紙、牛皮紙、捲紙、玻璃紙等紙的兩面設置黏土、聚乙烯、聚丙烯等填平劑之塗布層，進一步在其各塗布層上塗布聚矽氧系、氟系、醇酸系脫模劑而成者。又，可列舉：聚乙烯、聚丙烯、乙烯-α-烯烴共聚物、丙烯-α-烯烴共聚物等各種烯烴薄膜本身、及將上述脫模劑塗布於聚對苯二甲酸乙二醇酯等薄膜上而成者。考量脫模基材與黏接劑層之脫模力、聚矽氧會對電特性造成不良影響等理由，宜使用於優質紙之兩面進行聚丙烯填平處理並於其上使用醇酸系脫模劑而成者、或於聚對苯二甲酸乙二醇酯上使用醇酸系脫模劑而成者。The mold release substrate is not particularly limited. For example, it can be exemplified: coating layers of clay, polyethylene, polypropylene and other fillers are provided on both sides of paper such as high-quality paper, kraft paper, roll paper, cellophane, etc., and further on each of the coating layers Coated with silicone-based, fluorine-based, and alkyd-based release agents. In addition, various olefin films themselves such as polyethylene, polypropylene, ethylene-α-olefin copolymer, propylene-α-olefin copolymer, etc., and application of the above-mentioned mold release agent to polyethylene terephthalate, etc. Those made on the film. Considering the demolding force of the mold release substrate and the adhesive layer, and the adverse effects of polysiloxane on the electrical characteristics, it is appropriate to use polypropylene filling treatment on both sides of high-quality paper and use alkyd on it. Those made from a molding agent, or those made by using an alkyd-based mold release agent on polyethylene terephthalate.

將黏接劑組成物塗覆於基材或脫模基材上之方法並無特別限定，可列舉缺角輪塗布、逆向輥塗等。或可視需要直接或以轉印法將黏接劑層設置於係印刷配線板構成材料之壓延銅箔、或聚醯亞胺薄膜上。乾燥後之黏接劑層的厚度可視需要適當地變更，宜為5~200μm之範圍內。黏接劑層之厚度未達5μm時，有時會有黏接強度變得不充分的情況。超過200μm時，可列舉因乾燥不充分導致殘留溶劑變多，印刷配線板製造之壓製時發生膨起之問題。乾燥條件並無特別限定，乾燥後之殘留溶劑率宜為4質量%以下，為1質量%以下更佳。大於4質量%的話，會有如下問題發生的情況：在印刷配線板壓製時，殘留溶劑起泡而發生膨起。The method of applying the adhesive composition to the substrate or the release substrate is not particularly limited, and examples include chipped wheel coating, reverse roll coating, and the like. Or, if necessary, the adhesive layer can be directly or by a transfer method to be placed on the rolled copper foil or the polyimide film which is the constituent material of the printed wiring board. The thickness of the adhesive layer after drying can be appropriately changed as needed, and should be within the range of 5~200μm. When the thickness of the adhesive layer is less than 5μm, the adhesive strength may become insufficient. When the thickness exceeds 200 μm, the residual solvent increases due to insufficient drying, and the problem of swelling during the pressing of the printed wiring board manufacturing can be cited. The drying conditions are not particularly limited, and the residual solvent ratio after drying is preferably 4% by mass or less, and more preferably 1% by mass or less. If it is more than 4% by mass, the following problem may occur: When the printed wiring board is pressed, the residual solvent may foam and swell.

＜印刷配線板＞ 本發明中之印刷配線板係包含黏接片作為構成要素，更詳細而言，係包含由形成導體電路之金屬箔與樹脂基材形成的疊層體(金屬箔/黏接劑層/樹脂基材)作為構成要素。印刷配線板例如使用覆金屬疊層體並利用減去法等，以往習知的方法進行製造。視需要將利用金屬箔形成的導體電路，部分或整面地使用覆蓋薄膜、網版印刷印墨等予以被覆而成為統稱所謂撓性電路板(FPC)、扁平纜線、 捲帶式自動接合(TAB)用之電路板等。<Printed Wiring Board> The printed wiring board in the present invention includes adhesive sheets as constituent elements, and more specifically, includes a laminate (metal foil/adhesive (Agent layer/resin base material) as a constituent element. The printed wiring board uses, for example, a metal-clad laminate and is manufactured by a conventionally known method such as a subtraction method. If necessary, the conductor circuit formed by the metal foil may be partially or entirely covered with a cover film, screen printing ink, etc., to be collectively referred to as a so-called flexible circuit board (FPC), flat cable, and tape-type automatic bonding ( TAB) used circuit boards, etc.

本發明之印刷配線板可製成能用作印刷配線板的任意疊層結構。例如可製成由基材薄膜層、金屬箔層、黏接劑層、及覆蓋薄膜層之4層構成的印刷配線板。又，例如可製成由基材薄膜層、黏接劑層、金屬箔層、黏接劑層、及覆蓋薄膜層之5層構成的印刷配線板。印刷配線板有時會視需要以補強材進行補強，此時， 補強材、黏接劑層係設置於基材薄膜層之下方。The printed wiring board of the present invention can be made into any laminated structure that can be used as a printed wiring board. For example, it can be made into a printed wiring board composed of four layers of a base film layer, a metal foil layer, an adhesive layer, and a cover film layer. In addition, for example, a printed wiring board composed of five layers of a base film layer, an adhesive layer, a metal foil layer, an adhesive layer, and a cover film layer can be produced. The printed wiring board may be reinforced with a reinforcing material as necessary. In this case, the reinforcing material and the adhesive layer are arranged under the base film layer.

進一步，也可視需要製成將2個或3個以上之上述印刷配線板予以疊層而成之結構。Furthermore, it can also be made into the structure which laminated|stacked 2 or 3 or more of the said printed wiring boards as needed.

本發明之黏接劑組成物可理想地使用於印刷配線板之各黏接劑層。特別是將本發明之黏接劑組成物作為黏接劑使用的話，對於構成印刷配線板之基材具有高黏接性，且可賦予能對應於無鉛焊料之高程度的耐熱性。特別是在評價耐焊料性之高溫區域，由於以良好的平衡賦予樹脂與樹脂之化學交聯及樹脂與無機填充材之物理交聯，可緩和應力，而不會因加濕狀態下之耐焊料性試驗中的水分蒸發所致之衝擊導致膨起、變形。因此，適於金屬箔層與覆蓋薄膜層之間的黏接劑、及基材薄膜層與補強材層之間的黏接。特別是使用如SUS板、鋁板之金屬補強材時，在加濕狀態下進行焊接時，由於水分無法從補強材側蒸發，對基材薄膜層與補強材層之間之黏接劑層的衝擊特別強，適合作為該情況下之黏接所使用的黏接劑組成物。The adhesive composition of the present invention can be ideally used in each adhesive layer of a printed wiring board. In particular, when the adhesive composition of the present invention is used as an adhesive, it has high adhesiveness to a substrate constituting a printed wiring board, and can impart a high degree of heat resistance that can be compatible with lead-free solder. Especially in the high temperature area where solder resistance is evaluated, due to the good balance of chemical cross-linking between resin and resin and physical cross-linking between resin and inorganic filler, stress can be relieved without the solder resistance in humidified state The impact caused by the evaporation of water in the test results in swelling and deformation. Therefore, it is suitable for the adhesive between the metal foil layer and the cover film layer, and the adhesion between the base film layer and the reinforcing material layer. Especially when using metal reinforcing materials such as SUS plates and aluminum plates, when welding is carried out in a humidified state, the moisture cannot evaporate from the reinforcing material side, which impacts the adhesive layer between the base film layer and the reinforcing material layer. Particularly strong, suitable as an adhesive composition for bonding in this case.

本發明所使用之無機填充材並無特別限定，例如可使用：氧化鋁、二氧化矽、氧化鈦、氧化鉭、氧化鋯、氮化矽、鈦酸鋇、碳酸鋇、鈦酸鉛、鋯鈦酸鉛、鋯鈦酸鉛鑭、氧化鎵、尖晶石、莫來石、堇青石、滑石、氫氧化鋁、氫氧化鎂、鈦酸鋁、含氧化釔之氧化鋯、矽酸鋇、氮化硼、碳酸鈣、硫酸鈣、氧化鋅、硼酸鋅、鈦酸鎂、硼酸鎂、硫酸鋇、有機膨潤土、碳等，該等可單獨使用，亦可將二種以上併用。考量黏接劑組成物之透明性、機械特性、耐熱性的觀點，宜為二氧化矽，為採取三維網狀結構之煙霧狀二氧化矽特佳。又，在賦予疏水性方面，經以單甲基三氯矽烷、二甲基二氯矽烷、六甲基二矽氮烷、辛基矽烷、矽油等進行處理之疏水性二氧化矽較理想。使用煙霧狀二氧化矽作為無機填充材時，一次粒子之平均粒徑宜為30nm以下，更佳為25nm以下。一次粒子之平均粒徑超過30nm的話，會有粒子間、與樹脂之交互作用降低且耐熱性降低的傾向。此外，此處所稱一次粒子之平均粒徑，係指從使用掃描式電子顯微鏡獲得之一次粒子圖像中隨機挑選出的100個粒子之相當於圓之直徑的平均值。The inorganic filler used in the present invention is not particularly limited. For example, aluminum oxide, silicon dioxide, titanium oxide, tantalum oxide, zirconium oxide, silicon nitride, barium titanate, barium carbonate, lead titanate, zirconium titanium can be used. Lead acid, lead lanthanum zirconate titanate, gallium oxide, spinel, mullite, cordierite, talc, aluminum hydroxide, magnesium hydroxide, aluminum titanate, yttria-containing zirconia, barium silicate, nitride Boron, calcium carbonate, calcium sulfate, zinc oxide, zinc borate, magnesium titanate, magnesium borate, barium sulfate, organic bentonite, carbon, etc., can be used alone or in combination of two or more. Considering the transparency, mechanical properties, and heat resistance of the adhesive composition, silica is preferred, and aerosol-like silica with a three-dimensional network structure is particularly preferred. In addition, in terms of imparting hydrophobicity, hydrophobic silica treated with monomethyltrichlorosilane, dimethyldichlorosilane, hexamethyldisilazane, octylsilane, silicone oil, etc., is preferable. When aerosol silica is used as the inorganic filler, the average particle size of the primary particles is preferably 30nm or less, more preferably 25nm or less. If the average particle size of the primary particles exceeds 30 nm, the interaction between the particles and the resin will decrease, and the heat resistance will tend to decrease. In addition, the average particle diameter of the primary particles referred to herein refers to the average value of the diameter of a circle of 100 particles randomly selected from the image of the primary particles obtained by using a scanning electron microscope.

無機填充材之摻合量相對於含羧酸基之聚酯樹脂(A)100質量份，宜為10質量份以上，更佳為13質量份以上，尤佳為15質量份以上。未達10質量份的話，有時會有不發揮使耐熱性改善之效果的情況。又，宜為50質量份以下，更佳為45質量份以下，尤佳為40質量份以下。超過50質量份的話，會有無機填充材發生分散不良，或溶液黏度變得過高而對作業性造成不便，或黏接性降低之虞。The blending amount of the inorganic filler relative to 100 parts by mass of the carboxylic acid group-containing polyester resin (A) is preferably 10 parts by mass or more, more preferably 13 parts by mass or more, and particularly preferably 15 parts by mass or more. If it is less than 10 parts by mass, the effect of improving heat resistance may not be exhibited. Furthermore, it is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, and particularly preferably 40 parts by mass or less. If it exceeds 50 parts by mass, poor dispersion of the inorganic filler may occur, or the viscosity of the solution may become too high, which may cause inconvenience to workability, or may decrease the adhesiveness.

本發明之印刷配線板中，就基材薄膜而言，可使用自以往既已作為印刷配線板之基材使用的任意樹脂薄膜。基材薄膜之樹脂可使用含有鹵素之樹脂，也可使用不含鹵素之樹脂。考量環境問題的觀點，宜為不含鹵素之樹脂，但考量阻燃性的觀點，也可使用含有鹵素之樹脂。基材薄膜宜為聚醯亞胺薄膜或聚醯胺醯亞胺薄膜。In the printed wiring board of the present invention, as the base film, any resin film that has been conventionally used as a base material of a printed wiring board can be used. The resin of the base film can be a halogen-containing resin or a halogen-free resin. From the viewpoint of environmental issues, halogen-free resins are preferable, but from the viewpoint of flame retardancy, halogen-containing resins can also be used. The substrate film is preferably a polyimide film or a polyimide film.

就本發明所使用之金屬箔而言，可使用能用於電路基板之任意以往習知的導電性材料。材質例如可使用：銅箔、鋁箔、鋼箔、及鎳箔等，也可使用將該等複合而得的複合金屬箔、以鋅、鉻化合物等其他金屬進行處理而得的金屬箔。較佳為銅箔。As for the metal foil used in the present invention, any conventionally known conductive material that can be used for circuit substrates can be used. As the material, for example, copper foil, aluminum foil, steel foil, nickel foil, etc. can be used, and composite metal foils obtained by combining these, and metal foils treated with other metals such as zinc and chromium compounds can also be used. Preferably it is copper foil.

金屬箔之厚度並無特別限定，宜為1μm以上，更佳為3μm以上，尤佳為10μm以上。又，宜為50μm以下，更佳為30μm以下，尤佳為20μm以下。厚度過薄時，有時會有電路難以獲得足夠電性能的情況，另一方面，厚度過厚時，有時會有製作電路時之加工效率等降低的情況。The thickness of the metal foil is not particularly limited, and is preferably 1 μm or more, more preferably 3 μm or more, and particularly preferably 10 μm or more. Moreover, it is preferably 50 μm or less, more preferably 30 μm or less, and particularly preferably 20 μm or less. When the thickness is too thin, it may be difficult for the circuit to obtain sufficient electrical performance. On the other hand, when the thickness is too thick, the processing efficiency when making the circuit may be reduced.

金屬箔通常係以輥狀之形態提供。製造本發明之印刷配線板時所使用之金屬箔的形態並無特別限定。使用輥狀之形態的金屬箔時，其長度並無特別限定。又，其寬度亦無特別限定，宜為約250~1000mm。Metal foil is usually provided in the form of a roll. The form of the metal foil used when manufacturing the printed wiring board of this invention is not specifically limited. When the metal foil in the form of a roll is used, its length is not particularly limited. Also, the width is not particularly limited, but it is preferably about 250 to 1000 mm.

覆蓋薄膜可使用作為印刷配線板用之絕緣薄膜係習知的任意絕緣薄膜。例如可使用：由聚醯亞胺、聚酯、聚苯硫醚、聚醚碸、聚醚醚酮、聚芳醯胺、聚碳酸酯、聚芳酯、聚醯亞胺、聚醯胺醯亞胺等各種聚合物製得的薄膜。更佳為聚醯亞胺薄膜或聚醯胺醯亞胺薄膜，尤佳為聚醯亞胺薄膜。As the cover film, any insulating film known as an insulating film for printed wiring boards can be used. For example, it can be used: from polyimide, polyester, polyphenylene sulfide, polyether ether, polyether ether ketone, polyaramide, polycarbonate, polyarylate, polyimide, polyimide Films made of various polymers such as amines. It is more preferably a polyimide film or a polyimide film, and particularly preferably a polyimide film.

覆蓋薄膜之材料樹脂可使用含有鹵素之樹脂，亦可使用不含鹵素之樹脂。考量環境問題的觀點，宜為不含鹵素之樹脂，但考量阻燃性的觀點，也可使用含有鹵素之樹脂。The material resin of the cover film can be a halogen-containing resin or a halogen-free resin. From the viewpoint of environmental issues, halogen-free resins are preferable, but from the viewpoint of flame retardancy, halogen-containing resins can also be used.

本發明之印刷配線板除使用上述各層之材料以外，可使用以往習知的任意製程進行製造。The printed wiring board of the present invention can be manufactured using any conventionally known process in addition to using the materials of the above-mentioned layers.

較佳實施態樣中，係製造將黏接劑層疊層於覆蓋薄膜層而成的半成品(以下稱為「覆蓋薄膜側半成品」)。另一方面，製造將金屬箔層疊層於基材薄膜層並形成期望之電路圖案而成的半成品(以下稱為「基材薄膜側2層半成品」)或將黏接劑層疊層於基材薄膜層，於其上疊層金屬箔層並形成期望之電路圖案而成的半成品(以下稱為「基材薄膜側3層半成品」；以下將基材薄膜側2層半成品與基材薄膜側3層半成品合稱為「基材薄膜側半成品」)。藉由將以此種方式獲得之覆蓋薄膜側半成品與基材薄膜側半成品予以貼合，可獲得4層或5層之印刷配線板。In a preferred embodiment, a semi-finished product (hereinafter referred to as "cover-film-side semi-finished product") in which an adhesive layer is laminated on the cover film layer is manufactured. On the other hand, it manufactures a semi-finished product in which a metal foil is laminated on a base film layer and a desired circuit pattern is formed (hereinafter referred to as a "base film side two-layer semi-finished product") or an adhesive is laminated on the base film Layer, a semi-finished product made by laminating a metal foil layer on it and forming a desired circuit pattern (hereinafter referred to as "3-layer semi-finished product on the base film side"; hereinafter the two-layer semi-finished product on the substrate film side and the 3-layer semi-finished product on the substrate film side The semi-finished products are collectively referred to as "substrate film side semi-finished products"). By bonding the semi-finished product on the cover film side and the semi-finished product on the base film side obtained in this way, a 4-layer or 5-layer printed wiring board can be obtained.

基材薄膜側半成品可利用例如包括下列步驟之製造方法獲得：(A)將待成為基材薄膜之樹脂之溶液塗布於前述金屬箔，並將塗膜進行初步乾燥；(B)將(A)中獲得之金屬箔與初步乾燥塗膜之疊層物進行熱處理、乾燥(以下稱為「熱處理、脫溶劑步驟」)。The semi-finished product on the substrate film side can be obtained by, for example, a manufacturing method including the following steps: (A) apply a solution of the resin to be the substrate film on the aforementioned metal foil, and perform preliminary drying of the coating film; (B) (A) The laminate of the metal foil and the preliminarily dried coating film obtained in the process is heat-treated and dried (hereinafter referred to as "heat treatment and solvent removal step").

金屬箔層中之電路的形成可使用以往習知的方法。可使用加成法，亦可使用減去法。較佳為減去法。The formation of the circuit in the metal foil layer can use conventionally known methods. Additive or subtractive methods can be used. The subtraction method is preferred.

獲得之基材薄膜側半成品可直接使用於與覆蓋薄膜側半成品之貼合，也可在貼合脫模薄膜並保存後，使用於與覆蓋薄膜側半成品之貼合。The obtained semi-finished product on the substrate film side can be used directly for bonding with the semi-finished product on the cover film side, or it can be used for bonding with the semi-finished product on the cover film side after bonding the release film and storing it.

就覆蓋薄膜側半成品而言，係例如將黏接劑塗布於覆蓋薄膜而製造。可視需要實施經塗布之黏接劑中的交聯反應。較佳實施態樣中係使黏接劑層半硬化。The semi-finished product on the cover film side is manufactured by applying an adhesive to the cover film, for example. The cross-linking reaction in the coated adhesive can be implemented as needed. In a preferred embodiment, the adhesive layer is semi-hardened.

獲得之覆蓋薄膜側半成品可直接使用於與基材薄膜側半成品之貼合，也可在貼合脫模薄膜並保存後，使用於與基材薄膜側半成品之貼合。The obtained cover film side semi-finished product can be directly used for bonding with the base film side semi-finished product, or after the release film is bonded and stored, it can be used for bonding with the base film side semi-finished product.

基材薄膜側半成品與覆蓋薄膜側半成品，係分別以例如輥的形態保存後，經貼合而製造印刷配線板。就貼合的方法而言，可使用任意方法，例如可使用壓製或輥等進行貼合。又，亦可藉由加熱壓製、或使用加熱輥裝置等之方法，邊進行加熱邊將兩者貼合。The semi-finished product on the base film side and the semi-finished product on the cover film side are stored in the form of a roll, for example, and then laminated to manufacture a printed wiring board. As for the bonding method, any method can be used, and for example, pressing or a roll can be used for bonding. In addition, it is also possible to bond the two together while heating by a method such as heating and pressing, or using a heating roller device.

基材薄膜側半成品、覆蓋薄膜側半成品、補強材側半成品均屬本發明中之印刷配線板用疊層體。The semi-finished product on the base film side, the semi-finished product on the cover film side, and the semi-finished product on the reinforcing material side all belong to the laminate for printed wiring boards in the present invention.

本發明之黏接劑組成物可理想地使用於印刷配線板之各黏接劑層，對於各種基材之密接性、耐濕熱性優異，故除了可使用在印刷配線板以外，也可藉由使其含有金屬粉等導電粉末，而能使用在：電磁波屏蔽用途；觸控面板、電子零件之電路形成用途；端子、導線之導電性黏接劑等用途。 [實施例]The adhesive composition of the present invention can be ideally used in each adhesive layer of a printed wiring board. It has excellent adhesion to various substrates and excellent humidity and heat resistance. Therefore, it can be used in addition to printed wiring boards, but also by It contains conductive powders such as metal powder, and can be used in: electromagnetic wave shielding purposes; circuit formation purposes for touch panels and electronic parts; conductive adhesives for terminals and wires. [Example]

為了更加詳細地說明本發明，以下列舉實施例、比較例，但本發明並不受實施例任何限定。此外，實施例、比較例記載之各測定值係利用下列方法測得。又，除非另有說明，否則「份」意指「質量份」，「%」意指「質量%」。In order to describe the present invention in more detail, examples and comparative examples are listed below, but the present invention is not limited by the examples at all. In addition, each measured value described in the Examples and Comparative Examples was measured by the following method. Also, unless otherwise specified, "parts" means "parts by mass", and "%" means "mass%".

[高分子多元醇(A1-1)之聚合例] 於配備有攪拌機、溫度計、餾出用冷卻器之反應罐內，加入對苯二甲酸90份、間苯二甲酸358份、偏苯三甲酸酐5份、2-甲基-1,3-丙二醇319份、1,4-環己烷二醇172份、鈦酸四丁酯0.2份，緩慢升溫至250℃，邊將餾出的水排除到系統外，邊進行酯化反應。酯化反應結束後，邊緩慢減壓至10mmHg邊進行初始聚合，同時將溫度升溫至250℃，進一步在1mmHg以下進行後期聚合直到成為預定的扭矩。之後，利用氮氣恢復到常壓，投入偏苯三甲酸酐5份，並於220℃使其反應30分鐘，藉此獲得高分子多元醇(A1-1)。以此種方式獲得之高分子多元醇(A1-1)的組成、特性值顯示於表1。各測定評價項目依照前述方法。[Polymerization example of polymer polyol (A1-1)] Add 90 parts of terephthalic acid, 358 parts of isophthalic acid, and trimellitic anhydride to a reaction tank equipped with a stirrer, a thermometer, and a cooler for distillation 5 parts, 319 parts of 2-methyl-1,3-propanediol, 172 parts of 1,4-cyclohexanediol, 0.2 parts of tetrabutyl titanate, slowly increase the temperature to 250°C, and drain the distilled water to Outside the system, the esterification reaction is carried out. After the esterification reaction is completed, the initial polymerization is performed while gradually reducing the pressure to 10 mmHg, and the temperature is raised to 250° C., and the subsequent polymerization is further performed below 1 mmHg until the predetermined torque is reached. After that, the pressure was returned to normal pressure with nitrogen, 5 parts of trimellitic anhydride was added, and reacted at 220° C. for 30 minutes, thereby obtaining a polymer polyol (A1-1). The composition and characteristic values of the polymer polyol (A1-1) obtained in this way are shown in Table 1. Each measurement evaluation item is in accordance with the aforementioned method.

[高分子多元醇(A2-1)之聚合例] 於配備有攪拌機、溫度計、餾出用冷卻器之反應罐內，加入對苯二甲酸390份、間苯二甲酸390份、乙二醇367份、2,2-二甲基-1,3-丙二醇362份、鈦酸四丁酯0.2份，緩慢升溫至250℃，邊將餾出的水排除到系統外，邊進行酯化反應。酯化反應結束後，邊緩慢減壓至10mmHg邊進行初始聚合，同時將溫度升溫至250℃，進一步在1mmHg以下進行後期聚合直到成為預定的扭矩，藉此獲得高分子多元醇(A2-1)。以此種方式獲得之高分子多元醇(A2-1)的組成、特性值顯示於表1。各測定評價項目依照前述方法。[Polymerization example of polymer polyol (A2-1)] Add 390 parts of terephthalic acid, 390 parts of isophthalic acid, and 367 parts of ethylene glycol to a reaction tank equipped with a stirrer, a thermometer, and a cooler for distillation Part, 362 parts of 2,2-dimethyl-1,3-propanediol, 0.2 part of tetrabutyl titanate, slowly increase the temperature to 250°C, and proceed the esterification reaction while draining the distilled water out of the system. After the esterification reaction is completed, the initial polymerization is performed while slowly reducing the pressure to 10mmHg, and the temperature is raised to 250°C, and the subsequent polymerization is further performed below 1mmHg until the predetermined torque is reached, thereby obtaining a polymer polyol (A2-1) . The composition and characteristic values of the polymer polyol (A2-1) obtained in this way are shown in Table 1. Each measurement evaluation item is in accordance with the aforementioned method.

利用與高分子多元醇(A1-1)同樣的方法獲得高分子多元醇(A1-2~A1-5)。又， 利用與高分子多元醇(A2-1)同樣的方法獲得高分子多元醇(A2-2)。該等的特性值顯示於表1。The polymer polyol (A1-2~A1-5) is obtained by the same method as the polymer polyol (A1-1). In addition, the polymer polyol (A2-2) was obtained by the same method as the polymer polyol (A2-1). The characteristic values of these are shown in Table 1.

【表1】

【Table 1】

(1) 含有羧酸基之聚酯樹脂(A)的組成 將含有羧酸基之聚酯樹脂(A)溶解於氘代氯仿，並利用¹ H-NMR分析求出各成分之莫耳比。(1) Composition of carboxylic acid group-containing polyester resin (A) The carboxylic acid group-containing polyester resin (A) was dissolved in deuterated chloroform, and the molar ratio of each component was determined ^{by 1 H-NMR analysis.}

(2) 數量平均分子量(Mn) 將試樣(含有羧酸基之聚酯樹脂(A)、高分子多元醇(A1)或高分子多元醇(A2))溶解於四氫呋喃或以四氫呋喃稀釋，使試樣濃度成為約0.5質量%，並將利用孔徑0.5μm之聚四氟乙烯製膜過濾器進行過濾而得者作為測定用試樣。利用以四氫呋喃作為移動相，以差示折射計作為檢測器之凝膠滲透層析儀測定數量平均分子量。流速設定為1mL/分鐘，管柱溫度設定為30℃。管柱使用昭和電工製KF- 802、804L、806L。分子量標準使用單分散聚苯乙烯。惟，試樣不溶解於四氫呋喃時，使用N,N-二甲基甲醯胺替換四氫呋喃。數量平均分子量未達1000之低分子化合物(低聚物等)不列入計數而省略。(2) Number average molecular weight (Mn) Dissolve the sample (polyester resin (A) containing carboxylic acid group, polymer polyol (A1) or polymer polyol (A2)) in tetrahydrofuran or dilute with tetrahydrofuran to make The sample concentration was about 0.5% by mass, and the sample was filtered with a membrane filter made of polytetrafluoroethylene with a pore size of 0.5 μm as a sample for measurement. The number average molecular weight is measured by a gel permeation chromatograph with tetrahydrofuran as the mobile phase and a differential refractometer as the detector. The flow rate is set to 1 mL/min, and the column temperature is set to 30°C. The column uses Showa Denko KF-802, 804L, 806L. The molecular weight standard uses monodisperse polystyrene. However, when the sample does not dissolve in tetrahydrofuran, use N,N-dimethylformamide instead of tetrahydrofuran. Low-molecular compounds (oligomers, etc.) whose number average molecular weight is less than 1,000 are not included in the count and omitted.

(3) 玻璃轉移溫度 利用Seiko電子工業(股)公司製的差示掃描熱量分析計「DSC220型」，將測定試樣5mg放入鋁盤，按壓蓋子並密封，於250℃保持5分鐘一次後，以液態氮進行快速冷卻，之後以20℃/min之升溫速度從-150℃升溫至250℃並進行測定。將獲得之曲線的反曲點作為玻璃轉移溫度。另外，有2個以上反曲點時，視為係嵌段共聚，讀取各反曲點，視為具有多數個玻璃轉移溫度。(3) The glass transition temperature uses a differential scanning calorimeter "DSC220" manufactured by Seiko Electronics Co., Ltd., put 5 mg of the measurement sample into the aluminum pan, press the lid and seal it, and keep it at 250°C for 5 minutes once. , Use liquid nitrogen for rapid cooling, and then increase the temperature from -150°C to 250°C at a temperature increase rate of 20°C/min and perform the measurement. The inflection point of the obtained curve is regarded as the glass transition temperature. In addition, when there are two or more inflection points, it is regarded as a block copolymerization, and each inflection point is read, and it is regarded as having a plurality of glass transition temperatures.

(4) 酸價 將試樣(含有羧酸基之聚酯樹脂(A)、高分子多元醇(A1)或高分子多元醇(A2)) 0.2g溶解於20ml之氯仿，使用酚酞作為指示劑，以0.1N之氫氧化鉀乙醇溶液進行滴定。由該滴定量，將中和所耗之KOH之mg數換算成每1g樹脂的量，而算出酸價(mgKOH/g)。(4) Acid value Dissolve 0.2 g of the sample (polyester resin containing carboxylic acid group (A), polymer polyol (A1) or polymer polyol (A2)) in 20 ml of chloroform, and use phenolphthalein as an indicator , Titrate with 0.1N potassium hydroxide ethanol solution. From this titration amount, the mg number of KOH consumed for neutralization was converted into the amount per 1 g of resin, and the acid value (mgKOH/g) was calculated.

＜含有羧酸基之聚酯樹脂(A-1)之合成例＞ 於配備有攪拌機、溫度計、回流管之反應罐內，加入高分子多元醇(A1)160份、高分子多元醇(A2)40份、均苯四甲酸酐5.2份、甲苯200份，邊緩慢升溫至80℃邊使其溶解於甲苯。溶解完成後，添加三乙胺0.1份作為反應觸媒後，緩慢升溫至105℃，使其反應24小時。利用IR確認反應結束後，以甲苯108份進行稀釋，藉此獲得含有羧酸基之聚酯樹脂(A-1)之固體成分濃度40%的溶解液。以此種方式獲得之含有羧酸基之聚酯樹脂(A-1)的組成、特性值顯示於表2。各測定評價項目依照前述方法。<Synthesis example of carboxylic acid group-containing polyester resin (A-1)> Add 160 parts of polymer polyol (A1) and polymer polyol (A2) to a reaction tank equipped with a stirrer, thermometer, and reflux tube 40 parts, 5.2 parts of pyromellitic anhydride, and 200 parts of toluene were dissolved in toluene while slowly raising the temperature to 80°C. After the dissolution was completed, 0.1 part of triethylamine was added as a reaction catalyst, and the temperature was gradually raised to 105° C. and allowed to react for 24 hours. After confirming the completion of the reaction by IR, it was diluted with 108 parts of toluene to obtain a solution with a solid content of 40% of the carboxylic acid group-containing polyester resin (A-1). The composition and characteristic values of the carboxylic acid group-containing polyester resin (A-1) obtained in this way are shown in Table 2. Each measurement evaluation item is in accordance with the aforementioned method.

＜含有羧酸基之聚酯樹脂之合成例(A-2)~(A-13)＞ 與含有羧酸基之聚酯樹脂之合成例(A-1)同樣獲得含有羧酸基之聚酯樹脂(A-2)~(A-13)。<Synthesis examples of carboxylic acid group-containing polyester resin (A-2)~(A-13)> The same as the synthesis example (A-1) of carboxylic acid group-containing polyester resin to obtain carboxylic acid group-containing polyester Resin (A-2)~(A-13).

【表2】

【Table 2】

＜實施例1＞ 於含有羧酸基之聚酯樹脂(A-1)之固體成分100份中，加入作為環氧樹脂之新日鐵住金化學(股)製YDCN-700-10(酚醛清漆型環氧樹脂)9份與三菱瓦斯化學(股)製TETRAD(註冊商標)-X(N,N,N’,N’-四環氧丙基-間二甲苯二胺)0.1份，用甲乙酮進行調整使固體成分濃度成為35%，獲得黏接劑組成物。利用下列所示之方法對獲得之黏接劑組成物進行評價。<Example 1> To 100 parts of solid content of carboxylic acid group-containing polyester resin (A-1), Nippon Steel & Sumikin Chemical Co., Ltd. product YDCN-700-10 (novolac type) was added as an epoxy resin Epoxy resin) 9 parts and Mitsubishi Gas Chemical Co., Ltd. TETRAD (registered trademark)-X (N,N,N',N'-tetraepoxypropyl-m-xylene diamine) 0.1 part, with methyl ethyl ketone The solid content concentration was adjusted to 35% to obtain an adhesive composition. The adhesive composition obtained was evaluated by the method shown below.

＜實施例2~12、比較例1~6＞ 將含有羧酸基之聚酯樹脂、環氧樹脂變更成表3所示者，利用與實施例1同樣的方法，變更成表3所示之各摻合量，進行實施例2~12、比較例1~6。結果顯示於表3。<Examples 2 to 12, Comparative Examples 1 to 6> The carboxylic acid group-containing polyester resin and epoxy resin were changed to those shown in Table 3, and the same method as in Example 1 was used to change them to those shown in Table 3. For each blending amount, Examples 2 to 12 and Comparative Examples 1 to 6 were performed. The results are shown in Table 3.

(5) 剝離強度、耐焊料性、片材壽命 (5)-1 剝離強度(黏接性) 將實施例或比較例中獲得之黏接劑組成物塗布於厚度12.5μm之聚醯亞胺薄膜(Kaneka(股)公司製，APICAL(註冊商標))，使乾燥後之厚度成為25μm，於130℃乾燥5分鐘，獲得黏接性薄膜(B階段品)。以使黏接性薄膜之黏接劑層面與20μm之壓延銅箔之光澤面接觸的方式進行貼合，於160℃在30kgf/cm² 之加壓下壓製30秒鐘，進行黏接。然後於140℃熱處理4小時使其硬化，獲得評價用樣品。(5) Peel strength, solder resistance, and sheet life (5)-1 Peel strength (adhesion) The adhesive composition obtained in the examples or comparative examples is applied to a polyimide film with a thickness of 12.5 μm (Kaneka Co., Ltd., APICAL (registered trademark)), the thickness after drying becomes 25 μm, and it is dried at 130°C for 5 minutes to obtain an adhesive film (B-stage product). The adhesive layer of the adhesive film is bonded with the glossy surface of the 20μm rolled copper foil, and pressed at 160°C under a ^{pressure of 30kgf/cm 2} for 30 seconds to bond. Then, it was heat-treated at 140°C for 4 hours to harden, and a sample for evaluation was obtained.

剝離強度：將評價用樣品於25℃以拉伸速度50mm/min拉動薄膜，以實施180°剝離試驗，測定剝離強度。該試驗係顯示於常溫之剝離強度。考慮實用上的性能的話，宜為3.5N/cm以上，更佳為5N/cm以上。 -評價基準- ◎：10N/cm以上 ○：5N/cm以上、未達10N/cm △：3.5N/cm以上、未達5N/cm ×：未達3.5N/cmPeel strength: The sample for evaluation was pulled at 25°C at a tensile speed of 50 mm/min to perform a 180° peel test to measure the peel strength. This test shows the peel strength at room temperature. In consideration of practical performance, it is preferably 3.5 N/cm or more, and more preferably 5 N/cm or more. -Evaluation criteria- ◎: 10N/cm or more ○: 5N/cm or more, less than 10N/cm △: 3.5N/cm or more, less than 5N/cm ×: less than 3.5N/cm

(5)-2 耐焊料性 耐焊料性(乾燥)：將評價用樣品於120℃之環境下放置30分鐘後，使其漂浮於已加熱的焊料浴中1分鐘，以10℃間隔測定不發生膨起的上限溫度。該試驗中， 測定值越高表示具有良好的耐熱性。考慮實用上的性能的話，宜為350℃以上，更佳為360℃以上。 -評價基準- ◎：即使於360℃以上亦無膨起。 ○：於350℃以上未達360℃無膨起。 △：於340℃以上未達350℃無膨起。 ×：於未達340℃有膨起。(5)-2 Solder resistance Solder resistance (drying): After placing the sample for evaluation in an environment of 120°C for 30 minutes, let it float in the heated solder bath for 1 minute, and measure it at intervals of 10°C. The upper limit temperature of bulging. In this test, the higher the measured value, the better the heat resistance. In consideration of practical performance, it is preferably 350°C or higher, and more preferably 360°C or higher. -Evaluation Criteria- ◎: No swelling even at 360°C or higher. ○: No swelling above 350°C but below 360°C. △: No swelling above 340°C and below 350°C. ×: There is swelling below 340°C.

耐焊料性(加濕)：將評價用樣品於40℃、80%加濕下放置3天後，使其漂浮於已加熱的焊料浴中1分鐘，以10℃間隔測定不發生膨起的上限溫度。該試驗中， 雖然測定值越高表示具有良好的耐熱性，但也需抑制各基材、黏接劑層中所含之水蒸氣蒸發所致之衝擊，要求比起乾燥狀態更為嚴格的耐熱性。考慮實用上的性能的話，宜為260℃以上，更佳為270℃以上。 -評價基準- ◎：即使於270℃以上亦無膨起。 ○：於260℃以上未達270℃無膨起。 △：於250℃以上未達260℃無膨起。 ×：於未達250℃有膨起。Solder resistance (humidification): After leaving the sample for evaluation at 40°C and 80% humidification for 3 days, let it float in the heated solder bath for 1 minute, and measure the upper limit of no swelling at 10°C intervals temperature. In this test, although the higher the measured value, the better the heat resistance, but the impact caused by the evaporation of water vapor contained in each substrate and adhesive layer must also be suppressed, and more stringent heat resistance is required than in the dry state. sex. In consideration of practical performance, it is preferably 260°C or higher, and more preferably 270°C or higher. -Evaluation Criteria- ◎: No swelling even at 270°C or higher. ○: No swelling above 260°C and below 270°C. △: No swelling above 250°C and below 260°C. ×: There is swelling below 250°C.

(5)-3 片材壽命的評價 片材壽命測定用樣品的製作：將實施例或比較例中獲得之黏接劑組成物塗布於厚度12.5μm之聚醯亞胺薄膜(Kaneka(股)公司製，APICAL(註冊商標))，使乾燥後之厚度成為25μm，於130℃乾燥5分鐘，獲得黏接性薄膜(B階段品)。將該B階段品於40℃×80%之環境下放置2週。以使黏接性薄膜之黏接劑層面與20μm之壓延銅箔之光澤面接觸的方式貼合該B階段品，於160℃在30kgf/cm² 之加壓下壓製30秒鐘，進行黏接。然後於140℃熱處理4小時使其硬化，獲得評價用樣品。利用上述方法同樣製作剝離強度、耐焊料性之評價樣品。(5)-3 Evaluation of sheet life. Preparation of samples for sheet life measurement: The adhesive composition obtained in the examples or comparative examples was applied to a polyimide film with a thickness of 12.5 μm (Kaneka Co., Ltd.) Made, APICAL (registered trademark)), the thickness after drying becomes 25μm, and it is dried at 130°C for 5 minutes to obtain an adhesive film (B-stage product). Place the B-stage product in an environment of 40°C×80% for 2 weeks. Laminate the B-stage product so that the adhesive layer of the adhesive film is in contact with the glossy surface of the 20μm rolled copper foil, ^{and press it at 160°C under a pressure of 30kgf/cm 2} for 30 seconds to bond . Then, it was heat-treated at 140°C for 4 hours to harden, and a sample for evaluation was obtained. The evaluation samples of peel strength and solder resistance were similarly produced by the above method.

【表3】

【table 3】

根據表3之實施例可知，本發明之黏接劑組成物的初始剝離強度、耐焊料性、 片材壽命均優異。According to the examples in Table 3, the adhesive composition of the present invention has excellent initial peel strength, solder resistance, and sheet life.

為比較例1~6之黏接劑組成物的話，剝離強度、耐焊料性、片材壽命等性能不足。 [產業上利用性]In the case of the adhesive composition of Comparative Examples 1 to 6, the properties such as peel strength, solder resistance, and sheet life are insufficient. [Industrial Utilization]

本發明之黏接劑組成物，其對於各種塑膠薄膜、銅、鋁、不銹鋼等金屬、玻璃環氧樹脂之黏接性、耐焊料性及片材壽命優異。因此，作為以FPC為首之電路基板用之黏接劑係尤其有用。The adhesive composition of the present invention has excellent adhesiveness, solder resistance and sheet life to various plastic films, metals such as copper, aluminum, stainless steel, and glass epoxy resin. Therefore, it is particularly useful as an adhesive system for circuit boards such as FPC.

Claims (4)

一種黏接劑組成物，包含含有羧酸基之聚酯樹脂(A)及環氧樹脂(B)，其特徵為：含有羧酸基之聚酯樹脂(A)的玻璃轉移溫度(Tg)為40~90℃，酸價為1~30mgKOH/g，且包含高分子多元醇(A1)、及與高分子多元醇(A1)不同的高分子多元醇(A2)以及四羧酸二酐作為共聚成分，含有羧酸基之聚酯樹脂(A)中之高分子多元醇(A1)的共聚量為30質量%以上且90重量%以下，含有羧酸基之聚酯樹脂(A)中之高分子多元醇(A1)與高分子多元醇(A2)的共聚比率，相對於高分子多元醇(A1)100質量份，高分子多元醇(A2)為5質量份以上且50質量份以下，含有羧酸基之聚酯樹脂(A)中之高分子多元醇(A1)與四羧酸二酐的共聚比率，相對於高分子多元醇(A1)100質量份，四羧酸二酐為0.5質量份以上且10質量份以下，環氧樹脂(B)相對於含有羧酸基之聚酯樹脂(A)100質量份，為2質量份以上且50質量份以下。 An adhesive composition comprising a polyester resin (A) containing a carboxylic acid group and an epoxy resin (B), characterized in that the glass transition temperature (Tg) of the polyester resin (A) containing a carboxylic acid group is 40~90℃, acid value 1~30mgKOH/g, and contains polymer polyol (A1), polymer polyol (A2) which is different from polymer polyol (A1) and tetracarboxylic dianhydride as copolymer Ingredients, the copolymerization amount of the polymer polyol (A1) in the carboxylic acid group-containing polyester resin (A) is 30% by mass or more and 90% by weight or less, which is higher than that in the carboxylic acid group-containing polyester resin (A) The copolymerization ratio of molecular polyol (A1) and polymer polyol (A2), relative to 100 parts by mass of polymer polyol (A1), polymer polyol (A2) is 5 parts by mass or more and 50 parts by mass or less, containing The copolymerization ratio of the polymer polyol (A1) and the tetracarboxylic dianhydride in the carboxylic polyester resin (A) is 0.5 mass parts of the tetracarboxylic dianhydride relative to 100 parts by mass of the polymer polyol (A1) Part or more and 10 parts by mass or less, the epoxy resin (B) is 2 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the carboxylic acid group-containing polyester resin (A). 如申請專利範圍第1項之黏接劑組成物，其中，高分子多元醇(A1)及/或高分子多元醇(A2)為聚酯多元醇。 For example, the adhesive composition of item 1 in the scope of patent application, wherein the polymer polyol (A1) and/or the polymer polyol (A2) are polyester polyols. 一種黏接片，包含如申請專利範圍第1或2項之黏接劑組成物之硬化物。 An adhesive sheet, which contains the hardened material of the adhesive composition as described in item 1 or 2 of the scope of patent application. 一種印刷配線板，包含如申請專利範圍第3項之黏接片作為構成要素。 A printed wiring board that includes the adhesive sheet as described in item 3 of the scope of patent application as a constituent element.