JP2006152119A - Flame-retardant adhesive composition - Google Patents
Flame-retardant adhesive composition Download PDFInfo
- Publication number
- JP2006152119A JP2006152119A JP2004344600A JP2004344600A JP2006152119A JP 2006152119 A JP2006152119 A JP 2006152119A JP 2004344600 A JP2004344600 A JP 2004344600A JP 2004344600 A JP2004344600 A JP 2004344600A JP 2006152119 A JP2006152119 A JP 2006152119A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- retardant adhesive
- adhesive composition
- flame
- acrylic copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Fireproofing Substances (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、難燃性接着剤組成物に関する。 The present invention relates to a flame retardant adhesive composition.
近年、各種電子機器の小型化に伴い、電子部品の搭載密度も高くなり、それに用いられる配線板あるいは半導体パッケ−ジ等に要求される特性も多様化してきている。このような中でプリント配線板は、配線占有面積が小さくなり多層配線板化，フレキシブル配線板化（ＦＰＣ）等の要求が益々高まってきている。これらの配線板は、製造工程において種々の接着剤あるいは接着フィルムを用いているが、接着性，耐熱性及び耐電食性に優れ、かつ非ハロゲン系で難燃性を有している接着剤あるいは接着シ−トはなかった。これまでの難燃性接着剤組成物は、アンチモン系化合物及びハロゲン系化合物を併用添加することでいわゆる「フリ−ラジカルトラップ効果」やオキシハロゲン化アンチモンの脱水炭化作用を利用するものが知られているが、燃焼時の環境汚染等の問題が解決していない。 In recent years, with the miniaturization of various electronic devices, the mounting density of electronic components has increased, and the characteristics required for wiring boards or semiconductor packages used therein have also diversified. Under such circumstances, the printed wiring board has a reduced wiring occupation area, and demands for multilayer wiring boards, flexible wiring boards (FPC), and the like are increasing. These wiring boards use various adhesives or adhesive films in the manufacturing process, but are excellent in adhesiveness, heat resistance and electric corrosion resistance, and are non-halogen-based flame retardant adhesives or adhesives. There was no sheet. Conventional flame retardant adhesive compositions are known to utilize the so-called “free radical trapping effect” and the dehydration carbonization action of antimony oxyhalides by adding antimony compounds and halogen compounds together. However, problems such as environmental pollution during combustion have not been solved.
またプリント配線板関連材料としての検討では、吸湿後のはんだ耐熱性を向上させたものとして特開昭６０−２４３１８０号公報に示されるアクリル系樹脂、エポキシ樹脂、ポリイソシアネート及び無機フィラーを含む接着剤がある。また、特開昭６１−１３８６８０号公報に示されるアクリル樹脂、エポキシ樹脂、分子中にウレタン結合を有する両末端が第１級アミン化合物及び無機フィラーを含む接着剤がある。しかし、これらはプレッシャークッカーテスト（ＰＣＴ）処理等の厳しい条件下で耐湿性試験を行った場合著しく劣化する。 In addition, as a printed wiring board-related material, an adhesive containing an acrylic resin, an epoxy resin, a polyisocyanate, and an inorganic filler disclosed in JP-A-60-243180 as an improved solder heat resistance after moisture absorption. There is. Further, there are an acrylic resin, an epoxy resin, and an adhesive containing a primary amine compound and an inorganic filler at both ends having a urethane bond in the molecule as disclosed in JP-A-61-138680. However, these deteriorate significantly when the moisture resistance test is performed under severe conditions such as pressure cooker test (PCT) treatment.
これらプリント配線板関連材料の接着剤を用いて半導体チップをプリント配線板に実装する場合は、半導体チップとプリント配線板の熱膨張係数の差が大きくリフロ−テスト時にクラックが発生する。さらに、温度サイクルテスト等の厳しい条件下での耐湿熱性試験を行った場合も劣化が大きい。また、難燃性を付与させるために臭素化物等のハロゲン系難燃剤や酸化アンチモン等の金属酸化物を用いることは公知として知られているが、これらは環境に対して有害な物質であり、接着性を低下させるということがあるため、あまり多く用いることができず難燃性と接着性の両立が難しいという問題点がある。 When a semiconductor chip is mounted on a printed wiring board using an adhesive of these printed wiring board-related materials, the difference in thermal expansion coefficient between the semiconductor chip and the printed wiring board is large, and cracks occur during the reflow test. Furthermore, the degradation is large when a heat and humidity resistance test is performed under severe conditions such as a temperature cycle test. In addition, it is known to use halogenated flame retardants such as bromide and metal oxides such as antimony oxide to impart flame retardancy, but these are substances that are harmful to the environment, Since the adhesiveness may be lowered, it cannot be used so much and there is a problem that it is difficult to achieve both flame retardancy and adhesiveness.
本発明は、これらの問題を解決するものであり、アクリル系共重合体、エポキシ樹脂、エポキシ樹脂の硬化剤又は硬化促進剤、多官能型リン化合物を含有し、接着性，耐熱性に優れ、かつ非ハロゲン系で難燃性を有している難燃性接着剤組成物の提供を目的とする。 The present invention solves these problems, contains an acrylic copolymer, an epoxy resin, a curing agent or curing accelerator for an epoxy resin, a polyfunctional phosphorus compound, and has excellent adhesion and heat resistance. Another object of the present invention is to provide a flame retardant adhesive composition that is non-halogen and flame retardant.
本発明は、上記目的を達成するために、次のように構成される。
（１）（Ａ）アクリル系共重合体、（Ｂ）エポキシ樹脂、（Ｃ）硬化剤又は硬化促進剤、（Ｄ）多官能型リン化合物を含有してなる難燃性接着剤組成物であって、（Ａ）アクリル系共重合体が、ニトリル基又はエポキシ基を含有する（メタ）アクリレ−トモノマ−を含む重合性モノマ−を重合してなる（Ａ）アクリル系共重合体である難燃性接着剤組成物。
（２）ニトリル基又はエポキシ基を含有する（メタ）アクリレ−トモノマ−が、アクリロニトリル及びグリシジル（メタ）アクリレ−トであり、かつ重合性モノマ−の樹脂固形分中アクリロニトリルを１５〜３５重量％、グリシジル（メタ）アクリレ−トを０．５〜４重量％含む項（１）記載の難燃性接着剤組成物。
（３）（Ａ）アクリル系共重合体の重量平均分子量が５０万以上、３００万以下であり，かつ（Ａ）アクリル系共重合体のガラス転移点温度が−５℃以下である項（１）又は（２）に記載の難燃性接着剤組成物。
（４）（Ａ）アクリル系共重合体７０〜９０重量部、（Ｂ）エポキシ樹脂７〜２０重量部、（Ｃ）硬化剤又は硬化促進剤３〜１０重量部を含み、かつ（Ａ）と（Ｂ）と（Ｃ）の総量１００重量部に対して（Ｄ）多官能型リン化合物０．３〜６０重量部を含む項（１）〜（３）いずれかに記載の難燃性接着剤組成物。
（５）（Ｄ）多官能型リン化合物が、下記一般式（１）で示される（Ｄ）多官能型リン化合物である請求項１〜４いずれかに記載の難燃性接着剤組成物。
In order to achieve the above object, the present invention is configured as follows.
(1) A flame retardant adhesive composition comprising (A) an acrylic copolymer, (B) an epoxy resin, (C) a curing agent or curing accelerator, and (D) a polyfunctional phosphorus compound. (A) A flame retardant which is an (A) acrylic copolymer obtained by polymerizing a polymerizable monomer containing a (meth) acrylate monomer containing a nitrile group or an epoxy group. Adhesive composition.
(2) The (meth) acrylate monomer containing a nitrile group or an epoxy group is acrylonitrile and glycidyl (meth) acrylate, and 15 to 35% by weight of acrylonitrile in the resin solid content of the polymerizable monomer, The flame retardant adhesive composition according to item (1), comprising 0.5 to 4% by weight of glycidyl (meth) acrylate.
(3) The term (1) wherein the weight average molecular weight of the (A) acrylic copolymer is 500,000 or more and 3 million or less, and the glass transition temperature of the (A) acrylic copolymer is −5 ° C. or less. ) Or the flame retardant adhesive composition according to (2).
(4) (A) 70-90 parts by weight of an acrylic copolymer, (B) 7-20 parts by weight of an epoxy resin, (C) 3-10 parts by weight of a curing agent or curing accelerator, and (A) The flame-retardant adhesive according to any one of items (1) to (3), comprising (D) 0.3 to 60 parts by weight of a polyfunctional phosphorus compound with respect to 100 parts by weight of the total amount of (B) and (C) Composition.
(5) The flame-retardant adhesive composition according to any one of claims 1 to 4, wherein (D) the polyfunctional phosphorus compound is (D) a polyfunctional phosphorus compound represented by the following general formula (1).
本発明の難燃性接着剤組成物は、接着性、はんだ耐熱性に優れ、かつ非ハロゲン系の難燃性を有する。 The flame retardant adhesive composition of the present invention is excellent in adhesiveness and solder heat resistance, and has non-halogen flame retardant properties.
本発明の難燃性接着剤組成物は、（Ａ）アクリル系共重合体、（Ｂ）エポキシ樹脂、（Ｃ）硬化剤又は硬化促進剤、（Ｄ）多官能型リン化合物を含有してなる難燃性接着剤組成物であって、（Ａ）アクリル系共重合体が、ニトリル基又はエポキシ基を含有する（メタ）アクリレ−トモノマ−を含む重合性モノマ−を重合してなる（Ａ）アクリル系共重合体である。本発明に用いられる重合性モノマ−としては、ニトリル基又はエポキシ基を含有する（メタ）アクリレ−トモノマ−を含んでいればよいが、他の重合性モノマ−を含んでいてもよい。ニトリル基又はエポキシ基を含有する（メタ）アクリレ−トモノマ−としては、アクリロニトリルやグリシジル（メタ）アクリレ−ト等が挙げられる。 The flame retardant adhesive composition of the present invention comprises (A) an acrylic copolymer, (B) an epoxy resin, (C) a curing agent or curing accelerator, and (D) a polyfunctional phosphorus compound. A flame retardant adhesive composition, wherein (A) an acrylic copolymer is obtained by polymerizing a polymerizable monomer containing a (meth) acrylate monomer containing a nitrile group or an epoxy group (A) Acrylic copolymer. The polymerizable monomer used in the present invention may contain a (meth) acrylate monomer containing a nitrile group or an epoxy group, but may contain other polymerizable monomers. Examples of the (meth) acrylate monomer containing a nitrile group or an epoxy group include acrylonitrile and glycidyl (meth) acrylate.
本発明における他の重合性モノマ−としては、（メタ）アクリル酸メチル，（メタ）アクリル酸エチル，（メタ）アクリル酸ブチル，（メタ）アクリル酸イソブチル，（メタ）アクリル酸２−エチルヘキシル，（メタ）アクリル酸ラウリル，（メタ）アクリル酸シクロヘキシル等の（メタ）アクリル酸アルキルエステルや（メタ）アクリル酸シクロアルキルエステル、グリシジル基を含有する（メタ）アクリル酸グリシジルアルキルエステル、水酸基を含有する（メタ）アクリル酸ヒドロキシアルキルエステル等、カルボキシル基を含有する（メタ）アクリル酸、アミド基を含有する（メタ）アクリルアミド等が挙げられる。以上において、（メタ）アクリル酸とはアクリル酸及びメタクリル酸を意味する。 Other polymerizable monomers in the present invention include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( (Meth) acrylic acid alkyl ester such as (meth) acrylic acid lauryl, (meth) acrylic acid cyclohexyl, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid glycidyl alkyl ester containing glycidyl group, hydroxyl group ( Examples include (meth) acrylic acid hydroxyalkyl esters, (meth) acrylic acid containing a carboxyl group, (meth) acrylamide containing an amide group, and the like. In the above, (meth) acrylic acid means acrylic acid and methacrylic acid.
重合性モノマ−は、ニトリル基又はエポキシ基を含有する（メタ）アクリレ−トモノマ−としてアクリロニトリル及びグリシジル（メタ）アクリレ−トを含むことが好ましい。そして重合性モノマ−は、樹脂固形分中、アクリロニトリルを１５〜３５重量％、グリシジル（メタ）アクリレ−トを０．５〜４重量％含むことが好ましい。アクリロニトリルの配合量は、重合性モノマ−の樹脂固形分中の１５〜３５重量％で好ましく、２０〜３０重量％がより好ましい。１５重量％未満では耐熱性が低下しやすく、また３５重量％を超えると接着力が低下する。 The polymerizable monomer preferably contains acrylonitrile and glycidyl (meth) acrylate as a (meth) acrylate monomer containing a nitrile group or an epoxy group. The polymerizable monomer preferably contains 15 to 35% by weight of acrylonitrile and 0.5 to 4% by weight of glycidyl (meth) acrylate in the resin solids. The blending amount of acrylonitrile is preferably 15 to 35% by weight in the resin solid content of the polymerizable monomer, and more preferably 20 to 30% by weight. If it is less than 15% by weight, the heat resistance tends to be lowered, and if it exceeds 35% by weight, the adhesive strength is lowered.
重合性モノマ−の樹脂固形分中のグリシジル（メタ）アクリレ−トの配合量は、０．５〜４．０重量％で好ましく、１．０〜３．０重量％がより好ましい。０．５重量％未満では、はんだ耐熱性が低下しやすく、また４重量％を超えると接着力が低下する。 The blending amount of glycidyl (meth) acrylate in the resin solid content of the polymerizable monomer is preferably 0.5 to 4.0% by weight, more preferably 1.0 to 3.0% by weight. If it is less than 0.5% by weight, the solder heat resistance tends to decrease, and if it exceeds 4% by weight, the adhesive strength decreases.
（Ａ）アクリル系共重合体は、前記の重合性モノマ−を公知のラジカル重合法によって溶液（有機溶剤）重合することにより得られる。この場合、有機溶剤としてトルエン，キシレン等の芳香族系溶剤，メチルエチルケトン，メチルイソブチルケトン等のケトン系溶剤，酢酸エチル，酢酸ブチル等のエステル系溶剤に溶解して使用できる。また、重合開始剤としては、ベンゾイルパーオキサイド，ジクミルパーオキサイド，ジブチルパーオキサイド，ｔ−ブチルパーオキサイド，オキシベンゾエート等の有機過酸化物，アゾビスイソブチルニトリル，アゾビスイソバレロニトリル等のアゾビス系が使用できる。 (A) The acrylic copolymer can be obtained by solution (organic solvent) polymerization of the above polymerizable monomer by a known radical polymerization method. In this case, the organic solvent can be used by dissolving in an aromatic solvent such as toluene or xylene, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, or an ester solvent such as ethyl acetate or butyl acetate. As polymerization initiators, organic peroxides such as benzoyl peroxide, dicumyl peroxide, dibutyl peroxide, t-butyl peroxide, oxybenzoate, and azobis-based compounds such as azobisisobutylnitrile and azobisisovaleronitrile Can be used.
本発明の（Ａ）アクリル系共重合体の重量平均分子量（ゲルパ−ミエ−ションクロマトグラフィ法（ＧＰＣ）で測定し、標準ポリスチレンによる検量線を用いて換算した値）は、５０万以上、３００万以下が好ましく、６０万〜１００万がより好ましい。５０万未満では、可とう性や強度が低下する。また３００万を超えると粘度が高くなり作業性が低下する。重量平均分子量は、溶液重合開始時の重合性モノマ−濃度、重合開始剤の種類、重合温度により決定される。本発明の（Ａ）アクリル系共重合体のガラス転移点温度は、−５℃以下が好ましく、−１０〜−３０℃がより好ましい。−５℃を超えると接着性が低下する。 The weight average molecular weight of the (A) acrylic copolymer of the present invention (measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve) is 500,000 or more and 3 million. The following are preferable, and 600,000 to 1,000,000 are more preferable. If it is less than 500,000, flexibility and strength are lowered. Moreover, when it exceeds 3 million, a viscosity will become high and workability | operativity will fall. The weight average molecular weight is determined by the polymerizable monomer concentration at the start of solution polymerization, the type of polymerization initiator, and the polymerization temperature. The glass transition temperature of the (A) acrylic copolymer of the present invention is preferably −5 ° C. or lower, more preferably −10 to −30 ° C. Adhesiveness will fall when it exceeds -5 ° C.
本発明における（Ｂ）エポキシ樹脂は、二官能以上のエポキシ樹脂が好ましく、更に分子量が５０００未満のエポキシ樹脂がより好ましい。また例えば、（Ｂ）エポキシ樹脂としては、ビスフェノ−ルＡ型、ビスフェノ−ルＦ型等の液状エポキシ樹脂、フェノ−ルノボラック型、クレゾ−ルノボラック型等の多官能エポキシ樹脂を用いることができ、油化シェルエポキシ株式会社の商品名エピコ−ト８０７，エピコ−ト８２７，エピコ−ト８２８、ダウケミカル日本株式会社の商品名Ｄ．Ｅ．Ｒ．３３０，Ｄ．Ｅ．Ｒ．３３１，Ｄ．Ｅ．Ｒ．３６１、東都化成株式会社の商品名ＹＤ１２８，ＹＤＦ１７０、日本化薬株式会社の商品名ＥＰＰＮ−２０１，ＥＯＣＮ−１０１２，ＥＯＣＮ１０２５、住友化学工業株式会社の商品名ＥＳＣＮ−００１，ＥＳＣＮ−１９５が使用できる。また、エポキシ樹脂と相溶性のあるフェノキシ樹脂を難燃性接着剤組成物に併用してもよい。フェノキシ樹脂としては、例えば、東都化成株式会社の商品名フェノト−ト−４０，フェノト−トＹＰ−５０，フェノト−トＹＰ−６０が使用できる。 The (B) epoxy resin in the present invention is preferably a bifunctional or higher functional epoxy resin, and more preferably an epoxy resin having a molecular weight of less than 5,000. Further, for example, as the (B) epoxy resin, a liquid epoxy resin such as bisphenol A type or bisphenol F type, a polyfunctional epoxy resin such as phenol novolac type or cresol novolac type can be used, and oil Trade name Epicote 807, Epicote 827, Epicote 828, and Dow Chemical Japan Co., Ltd. E. R. 330, D.E. E. R. 331, D. E. R. 361, Toto Kasei Co., Ltd. trade names YD128, YDF170, Nippon Kayaku Co., Ltd. trade names EPPN-201, EOCN-1012, EOCN1025, Sumitomo Chemical Co., Ltd. trade names ESCN-001, ESCN-195 can be used. Moreover, you may use together a phenoxy resin compatible with an epoxy resin with a flame-retardant adhesive composition. As the phenoxy resin, for example, phenototo-40, phenototo YP-50, phenototo YP-60 manufactured by Toto Kasei Co., Ltd. can be used.
本発明における（Ｃ）硬化剤又は硬化促進剤としては、特に限定されるものではないが、エポキシ樹脂の硬化剤、エポキシ樹脂の硬化促進剤であることが好ましい。例えば、（Ｃ）硬化剤又は硬化促進剤としては、無水ヘキサヒドロフタル酸、無水メチルヘキサヒドロフタル酸、無水メチルテトラヒドロフタル酸等の酸無水物、ビスフェノールＡ、テトラブロモビスフェノールＡ、トリメチロールアリルオキシフェノール、フェノールノボラック樹脂，クレゾ−ルノボラック樹脂、ブチル化フェノール樹脂等のフェノール類、脂肪族ポリアミン、芳香族ポリアミン、２級又は３級アミン、メラミン、トリアジン化合物、有機酸、イミダゾール類、ジシアンジアミド、トリフェニルフォスフィン、ポリメルカプタン等が使用できる。これらは、単独あるいは複数混合し適量使用できる。 Although it does not specifically limit as (C) hardening | curing agent or hardening accelerator in this invention, It is preferable that they are a hardening | curing agent of an epoxy resin, and a hardening accelerator of an epoxy resin. For example, (C) a curing agent or a curing accelerator includes acid anhydrides such as hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, bisphenol A, tetrabromobisphenol A, trimethylol allyloxy. Phenols such as phenol, phenol novolac resin, cresol novolac resin, butylated phenol resin, aliphatic polyamine, aromatic polyamine, secondary or tertiary amine, melamine, triazine compound, organic acid, imidazoles, dicyandiamide, triphenyl Phosphine, polymercaptan, etc. can be used. These can be used alone or in combination.
本発明における（Ｄ）多官能型リン化合物として、ＯＰ９３０（クラリアント社製商品名、リン含有量２３．５重量％）、ＨＣＡ−ＨＱ（三光株式会社製商品名、リン含有量９．６重量％）、ポリリン酸メラミンＰＭＰ−１００（リン含有量１３．８重量％）ＰＭＰ−２００（リン含有量９．３重量％）ＰＭＰ−３００（リン含有量９．８重量％）以上日産化学株式会社製商品名等が使用できる。また、（Ｄ）多官能型リン化合物として、前記一般式（１）で示される多官能型リン化合物が好ましく、これとしてＨＣＡ−ＨＱ（三光株式会社製商品名）が例示できる。 As the (D) polyfunctional phosphorus compound in the present invention, OP930 (trade name, manufactured by Clariant, phosphorus content 23.5% by weight), HCA-HQ (trade name, manufactured by Sanko Co., Ltd., phosphorus content 9.6% by weight) ), Melamine polyphosphate PMP-100 (phosphorus content 13.8 wt%) PMP-200 (phosphorus content 9.3 wt%) PMP-300 (phosphorus content 9.8 wt%) or more manufactured by Nissan Chemical Co., Ltd. Product names can be used. Moreover, as the (D) polyfunctional phosphorus compound, the polyfunctional phosphorus compound represented by the general formula (1) is preferable, and examples thereof include HCA-HQ (trade name, manufactured by Sanko Co., Ltd.).
また、本発明の難燃性接着剤組成物は、結晶水を含有する無機充填剤として水酸化アルミニウムや水酸化マグネシウムを併用してもよい。また上記各成分の他に必要に応じて、従来より公知の、カップリング剤、顔料、レベリング剤、消泡剤、イオントラップ剤等を適宜配合しても良い。 Moreover, the flame retardant adhesive composition of the present invention may use aluminum hydroxide or magnesium hydroxide in combination as an inorganic filler containing crystal water. In addition to the above components, conventionally known coupling agents, pigments, leveling agents, antifoaming agents, ion trapping agents and the like may be appropriately blended as necessary.
本発明の難燃性接着剤組成物は、（Ａ）アクリル系共重合体７０〜９０重量部、（Ｂ）エポキシ樹脂７〜２０重量部、（Ｃ）硬化剤又は硬化促進剤３〜１０重量部を含み、かつ（Ａ）と（Ｂ）と（Ｃ）の総量１００重量部に対して（Ｄ）多官能型リン化合物０．３〜６０重量部を含むことが好ましい。すなわち（Ａ）アクリル系共重合体７０〜９０重量部に対し、（Ｂ）エポキシ樹脂の配合量は、７〜２０重量部が好ましく、１０〜１５重量部がより好ましい。７重量部未満では、はんだ耐熱性が低下し、２０重量部を超えると接着性が低下する。また（Ａ）アクリル系共重合体７０〜９０重量部に対し、（Ｃ）硬化剤又は硬化促進剤の配合量は、３〜１０重量部が好ましい。３重量部未満では、はんだ耐熱性，耐熱接着性が低下し、１０重量部を超えると接着性が低下する。また本発明における（Ｄ）多官能リン化合物の配合量は、（Ａ）＋（Ｂ）＋（Ｃ）成分の総量１００重量部に対して０．３〜６０重量部が好ましい。０．３重量部未満では、難燃性の効果が低く、６０重量部を超えると接着性が低下する。 The flame-retardant adhesive composition of the present invention comprises (A) 70 to 90 parts by weight of an acrylic copolymer, (B) 7 to 20 parts by weight of an epoxy resin, and (C) a curing agent or a curing accelerator 3 to 10 parts by weight. It is preferable that 0.3 to 60 parts by weight of (D) polyfunctional phosphorus compound is included with respect to 100 parts by weight of the total amount of (A), (B) and (C). That is, the blending amount of the (B) epoxy resin is preferably 7 to 20 parts by weight and more preferably 10 to 15 parts by weight with respect to 70 to 90 parts by weight of the (A) acrylic copolymer. If the amount is less than 7 parts by weight, the solder heat resistance is lowered, and if it exceeds 20 parts by weight, the adhesiveness is lowered. Moreover, 3-10 weight part is preferable with respect to (A) acrylic copolymer 70-90 weight part, and the compounding quantity of (C) hardening | curing agent or a hardening accelerator is. If the amount is less than 3 parts by weight, the solder heat resistance and the heat-resistant adhesiveness are deteriorated. The blending amount of the polyfunctional phosphorus compound (D) in the present invention is preferably 0.3 to 60 parts by weight with respect to 100 parts by weight of the total amount of the components (A) + (B) + (C). If it is less than 0.3 parts by weight, the flame retardancy effect is low, and if it exceeds 60 parts by weight, the adhesiveness is lowered.
以下実施例により本発明を具体的に説明するが、本発明はこれに限定されるものではない。なお以下の記載における配合量は、重量部で表す。
（（Ａ）アクリル系共重合体Ａ〜Ｄの製造法）
混合機及び冷却器を備え付けた反応器に表１に示す配合物ａを入れ、８０℃〜８５℃に加熱し、表１に示す配合物ｂを添加し、４〜８時間保温し、重合率で２０〜４０％反応させた（Ａ）アクリル系共重合体を得る。冷却後メタノ−ルを加え（Ａ）アクリル系共重合体を沈殿させ、上澄み液を取り除く。（Ａ）アクリル系共重合体中に残ったメタノ−ルを乾燥させ、続いて樹脂固形分が１５重量％になるようにメチルエチルケトンを加えた。表１の配合量は重量部を示す。
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In addition, the compounding quantity in the following description is represented by a weight part.
((A) Method for producing acrylic copolymers A to D)
The compound a shown in Table 1 is put into a reactor equipped with a mixer and a cooler, heated to 80 ° C. to 85 ° C., compound b shown in Table 1 is added, and the mixture is kept warm for 4 to 8 hours. (A) Acrylic copolymer reacted at 20 to 40% is obtained. After cooling, methanol is added (A) to precipitate the acrylic copolymer, and the supernatant is removed. (A) The methanol remaining in the acrylic copolymer was dried, and then methyl ethyl ketone was added so that the resin solid content was 15% by weight. The blending amounts in Table 1 indicate parts by weight.
この（Ａ）アクリル系共重合体Ａ〜Ｄの重量平均分子量は、ゲルパ−ミエ−ションクロマトグラフィ−法（ＧＰＣ）により標準ポリスチレンによる検量線を用いて、以下に示す条件で測定した。
（ＧＰＣ条件）
・使用機器：日立６３５型ＨＰＬＣ（株式会社日立製作所製）
・カラム：ゲルパックＲ４４０＋Ｒ４５０＋Ｒ４００Ｍ（日立化成工業株式会社製商品名）
・溶離液：テトラヒドロフラン
・測定温度：４０℃
・流量：２．０ｍｌ／ｍｉｎ
・検出器：示差屈折計
重量平均分子量測定結果及びガラス転移点温度を表１に示した。なお、ガラス転移点温度は、計算値であり、その計算方法は、１／Ｔｇ＝ｗ１／Ｔｇ１＋ｗ２/Ｔｇ（ＧｏｒｄｏｎーＴａｙｌｏｒの式）である（参考デ−タ；塗料用合成樹脂入門，北岡協三著）。
The weight average molecular weights of these (A) acrylic copolymers A to D were measured by the gel permeation chromatography method (GPC) using a standard polystyrene calibration curve under the following conditions.
(GPC conditions)
-Equipment used: Hitachi 635 HPLC (manufactured by Hitachi, Ltd.)
Column: Gel pack R440 + R450 + R400M (trade name, manufactured by Hitachi Chemical Co., Ltd.)
-Eluent: Tetrahydrofuran-Measurement temperature: 40 ° C
・ Flow rate: 2.0ml / min
Detector: differential refractometer Table 1 shows the results of measuring the weight average molecular weight and the glass transition temperature. The glass transition temperature is a calculated value, and the calculation method is 1 / Tg = w1 / Tg1 + w2 / Tg (Gordon-Taylor formula) (reference data; introduction to synthetic resins for paints, Kitaoka Kyokai) Three).
（実施例１〜６、比較例１〜３）
得られた（Ａ）アクリル系共重合体（樹脂固形分：１５重量％）に対して、下記に示す材料を加え難燃性接着剤組成物のワニスを得た。また、表２に材料の配合を示した。得られた難燃性接着剤組成物ワニスをポリイミドフィルム（厚さ３５μｍ）に乾燥後の膜厚が７０μｍになるように塗布し、１４０℃で５分間乾燥して接着剤（難燃性接着剤組成物）付ポリイミドフィルムを作製した。
（Ｂ）エポキシ樹脂として、ビスフェノ−ルＡ型エポキシ樹脂エピコ−ト８２８（油化シェルエポキシ株式会社製商品名）、
（Ｃ）硬化剤として、フェノ−ル樹脂プライオ−フェンＬＦ２８２２（大日本インキ化学工業株式会社製商品名）、
（Ｃ）硬化促進剤として、イミダゾ−ル系硬化促進剤キュアゾ−ル２ＰＺ−ＣＮ（四国化成工業株式会社製商品名）、
（Ｄ）多官能リン化合物として、ＨＣＡ―ＨＱ（三光株式会社製商品名）、
フェノキシ樹脂として、フェノト−トＹＰ−５０（東都化成株式会社製商品名）、
アクリロニトリルブタジエンゴムとして、ＰＮＲ−１（ジェイエスア−ル株式会社製商品名）。
(Examples 1-6, Comparative Examples 1-3)
The material shown below was added to the obtained (A) acrylic copolymer (resin solid content: 15% by weight) to obtain a varnish of a flame retardant adhesive composition. Table 2 shows the composition of the materials. The obtained flame retardant adhesive composition varnish was applied to a polyimide film (thickness 35 μm) so that the film thickness after drying was 70 μm, and dried at 140 ° C. for 5 minutes to form an adhesive (flame retardant adhesive) A polyimide film with a composition) was prepared.
(B) As an epoxy resin, bisphenol A type epoxy resin epicoat 828 (trade name, manufactured by Yuka Shell Epoxy Co., Ltd.),
(C) As a curing agent, phenol resin prio-phen LF2822 (trade name, manufactured by Dainippon Ink & Chemicals, Inc.),
(C) As a curing accelerator, an imidazole-based curing accelerator, Cuazole 2PZ-CN (trade name, manufactured by Shikoku Kasei Kogyo Co., Ltd.),
(D) As a polyfunctional phosphorus compound, HCA-HQ (trade name, manufactured by Sanko Co., Ltd.),
As phenoxy resin, Phenoto-YP-50 (trade name, manufactured by Toto Kasei Co., Ltd.),
As an acrylonitrile butadiene rubber, PNR-1 (trade name, manufactured by GS AAL Co., Ltd.).
得られた接着剤（難燃性接着剤組成物）付ポリイミドフィルムを用いて接着性，はんだ耐熱性，難燃性を調べた。以下に示す方法で前記特性を調べた。その結果を表２に示した。 Using the obtained polyimide film with an adhesive (a flame retardant adhesive composition), the adhesion, solder heat resistance, and flame resistance were examined. The characteristics were examined by the following method. The results are shown in Table 2.
（接着性）
接着剤（難燃性接着剤組成物）付ポリイミドフィルムの接着剤面を、圧延銅箔の光沢面に、１２０℃で加熱しながらロ−ルラミネ−トし、１７０℃で２時間加熱硬化させ試験用試料とした。また接着剤（難燃性接着剤組成物）付ポリイミドフィルムの接着剤面を、ポリイミドフィルム（カプトン：東レ・デュポン株式会社製商品名）に、１２０℃で加熱しながらロ−ルラミネ−トし、１７０℃で２時間加熱硬化させ試験用試料とした。この試験用試料の１８０°ピ−ル剥離強度を２３℃で測定した。
(Adhesiveness)
The adhesive surface of the polyimide film with an adhesive (flame retardant adhesive composition) was roll-laminated while being heated at 120 ° C on the glossy surface of the rolled copper foil, and heat cured at 170 ° C for 2 hours for testing. A sample was prepared. In addition, the adhesive surface of the polyimide film with an adhesive (a flame retardant adhesive composition) is roll laminated to a polyimide film (Kapton: product name manufactured by Toray DuPont Co., Ltd.) while heating at 120 ° C. A test sample was cured by heating at 170 ° C. for 2 hours. The 180 ° peel peel strength of this test sample was measured at 23 ° C.
（はんだ耐熱性）
接着剤（難燃性接着剤組成物）付ポリイミドフィルムを前記と同様圧延銅箔に１２０℃で加熱しながらラミネ−トし、１８０℃で２時間加熱硬化させ試験用試料とした。この試験用試料を各温度（２００〜３５０℃、１０℃毎）の溶融したはんだ浴に３分間浸漬した。外観に変化（剥離，フクレ，変色等）が生じた温度を求めた。
(Solder heat resistance)
A polyimide film with an adhesive (a flame retardant adhesive composition) was laminated to a rolled copper foil while heating at 120 ° C. in the same manner as described above, and heat cured at 180 ° C. for 2 hours to obtain a test sample. This test sample was immersed in a molten solder bath at each temperature (200 to 350 ° C., every 10 ° C.) for 3 minutes. The temperature at which changes in appearance (peeling, blistering, discoloration, etc.) occurred was determined.
（難燃性）
接着剤（難燃性接着剤組成物）付ポリイミドフィルムを１８０℃で２時間加熱硬化させ試験用試料とした。この試験用試料を用い、ＵＬ−９４規格の難燃性試験方法に準じて、難燃性を評価した。
(Flame retardance)
A polyimide film with an adhesive (a flame retardant adhesive composition) was heat-cured at 180 ° C. for 2 hours to obtain a test sample. Using this test sample, the flame retardancy was evaluated according to the flame retardancy test method of the UL-94 standard.
実施例１〜６に示したように、接着性（ピ−ル剥離強度）は、圧延銅箔の光沢面に対しは、１．０ＫＮ／ｍ以上、ポリイミドフィルム（カプトン）に対しは、０．９ＫＮ／ｍ以上であり、またはんだ耐熱性に関しては、少なくとも３１０℃まで試験用試料の外観に変化（剥離，フクレ，変色等）はなく、また難燃性に関しても良好（Ｖ−０）であった。それに対し、（Ａ）アクリル系共重合体を含まない比較例１、２は、接着性（ピ−ル剥離強度）、はんだ耐熱性、難燃性とも実施例と比べ劣り、また（Ｄ）多官能リン化合物を含まない比較例３は、難燃性が著しく劣ることがわかった。
As shown in Examples 1 to 6, the adhesion (peel peel strength) was 1.0 KN / m or more for the glossy surface of the rolled copper foil, and 0. 0 for the polyimide film (Kapton). 9KN / m or more, or with regard to heat resistance, there was no change (exfoliation, blistering, discoloration, etc.) in the appearance of the test sample up to at least 310 ° C, and good flame retardancy (V-0). It was. On the other hand, (A) Comparative Examples 1 and 2, which do not contain an acrylic copolymer, are inferior to the Examples in terms of adhesion (peel peel strength), solder heat resistance, and flame retardancy, and (D) many It turned out that the comparative example 3 which does not contain a functional phosphorus compound is remarkably inferior in flame retardance.
Claims (5)
The flame retardant adhesive composition according to any one of claims 1 to 4, wherein (D) the polyfunctional phosphorus compound is (D) a polyfunctional phosphorus compound represented by the following general formula (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004344600A JP2006152119A (en) | 2004-11-29 | 2004-11-29 | Flame-retardant adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004344600A JP2006152119A (en) | 2004-11-29 | 2004-11-29 | Flame-retardant adhesive composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2006152119A true JP2006152119A (en) | 2006-06-15 |
Family
ID=36630792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004344600A Pending JP2006152119A (en) | 2004-11-29 | 2004-11-29 | Flame-retardant adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2006152119A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100104864A1 (en) * | 2007-04-05 | 2010-04-29 | Tesa Se | Thermally crosslinking polyacrylates and method for producing the same |
| WO2011111534A1 (en) * | 2010-03-12 | 2011-09-15 | リンテック株式会社 | Flame resistant adhesive composition, flame resistant adhesive tape and flame resistant adhesive sheet |
| JP2011225853A (en) * | 2010-03-29 | 2011-11-10 | Hitachi Chem Co Ltd | Phosphorus-containing acrylic resin and method for producing the same, acrylic resin composition, resin film, prepreg, metal foil with resin, metal foil-clad laminate, and printed wiring board |
| DE102014101564B4 (en) | 2013-02-15 | 2023-07-06 | Sanko Co., Ltd. | (Meth)acrylate compound based on phosphorus and process for its preparation |
-
2004
- 2004-11-29 JP JP2004344600A patent/JP2006152119A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100104864A1 (en) * | 2007-04-05 | 2010-04-29 | Tesa Se | Thermally crosslinking polyacrylates and method for producing the same |
| US8802777B2 (en) * | 2007-04-05 | 2014-08-12 | Tesa Se | Thermally crosslinking polyacrylates and method for producing the same |
| WO2011111534A1 (en) * | 2010-03-12 | 2011-09-15 | リンテック株式会社 | Flame resistant adhesive composition, flame resistant adhesive tape and flame resistant adhesive sheet |
| JP4812907B1 (en) * | 2010-03-12 | 2011-11-09 | リンテック株式会社 | Flame retardant adhesive composition, flame retardant adhesive tape, and flame retardant adhesive sheet |
| JP2011225853A (en) * | 2010-03-29 | 2011-11-10 | Hitachi Chem Co Ltd | Phosphorus-containing acrylic resin and method for producing the same, acrylic resin composition, resin film, prepreg, metal foil with resin, metal foil-clad laminate, and printed wiring board |
| DE102014101564B4 (en) | 2013-02-15 | 2023-07-06 | Sanko Co., Ltd. | (Meth)acrylate compound based on phosphorus and process for its preparation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4691365B2 (en) | Adhesive composition for semiconductor device and adhesive sheet for semiconductor device | |
| JP5150381B2 (en) | Thermosetting resin composition | |
| JP5082373B2 (en) | Resin composition for printed wiring board, prepreg, substrate, metal foil-clad laminate, metal foil with resin, and printed wiring board | |
| JP4600640B2 (en) | Acrylic adhesive sheet | |
| JP7287432B2 (en) | Resin composition, prepreg, resin-coated metal foil, laminate, printed wiring board, and method for producing resin composition | |
| KR20080104983A (en) | Flame retardant adhesive composition, and coverlay film using same | |
| US20060069201A1 (en) | Acrylic flame retardant adhesive composition and acrylic flame retardant adhesive sheet | |
| JP2009167396A (en) | Adhesive composition, copper-clad laminate plate using the same, cover-lay film and adhesive sheet | |
| JP5632887B2 (en) | Thermosetting resin composition for interlayer insulating material of multilayer printed wiring board | |
| JP2000256635A (en) | Substrate with adhesive layer using acrylic resin and adhesive film | |
| JP2004115612A (en) | Adhesive composition | |
| JP2003105167A (en) | Flame-retardant resin composition and adhesive sheet for semiconductor device using the same, cover lay film and flexible printed circuit board | |
| JP4434569B2 (en) | Halogen-free flame-retardant adhesive composition and coverlay film | |
| JP4584619B2 (en) | Flame-retardant adhesive composition and adhesive sheet using the same | |
| JP2006152119A (en) | Flame-retardant adhesive composition | |
| JPH11166019A (en) | Acryl resin, adhesive and using the same, and production of acryl resin | |
| JPH10330696A (en) | Adhesive film for multilayer printed circuit board | |
| JP2004136631A (en) | Adhesive composition for laminating flexible printed wiring boards, and adhesive film | |
| JP5056099B2 (en) | Curable resin composition, resin-impregnated base material, prepreg, substrate, metal foil with adhesive layer and printed wiring board | |
| JP2003082034A (en) | Acrylic resin, adhesive and adhesive film each using the same | |
| JP2836942B2 (en) | Coverlay film | |
| JP2004307627A (en) | Acrylic resin, flame-retardant adhesive using the same and adhesive film | |
| JP2000248026A (en) | Acrylic resin, adhesive and adhesive film using the same and production of acrylic resin | |
| JP2008266513A (en) | Curable resin composition, prepreg, laminate, metal foil with adhesive layer, film sheet, and printed wiring board using these materials | |
| JP2005139391A (en) | Acrylic adhesive sheet |