JP2002194313A - Flame-retardant resin adhesive - Google Patents
Flame-retardant resin adhesiveInfo
- Publication number
- JP2002194313A JP2002194313A JP2000390892A JP2000390892A JP2002194313A JP 2002194313 A JP2002194313 A JP 2002194313A JP 2000390892 A JP2000390892 A JP 2000390892A JP 2000390892 A JP2000390892 A JP 2000390892A JP 2002194313 A JP2002194313 A JP 2002194313A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- flame
- weight
- epoxy resin
- resin adhesive
- 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
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- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、銅箔等の金属箔と
耐熱性支持材料との接着などに好適に用いられる難燃性
樹脂接着剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin adhesive suitably used for bonding a metal foil such as a copper foil to a heat-resistant support material.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】従来、
フレキシブル配線基板は、電気特性、コスト、作業性等
に優れるエポキシ樹脂接着剤が主に用いられているが、
エポキシ樹脂は難燃性が不十分なため、臭素含有エポキ
シ樹脂、３酸化アンチモン、赤リン、金属水和物等を添
加して耐熱性フィルムと銅箔とを張り合わせることによ
って製造されていることが多かった。2. Description of the Related Art
For flexible wiring boards, epoxy resin adhesives with excellent electrical properties, cost, workability, etc. are mainly used,
Since epoxy resin has insufficient flame retardancy, it must be manufactured by adding a bromine-containing epoxy resin, antimony trioxide, red phosphorus, metal hydrate, etc., and bonding a heat-resistant film and copper foil. There were many.
【０００３】しかしながら、デカブロムをはじめとする
ハロゲン（臭素）系難燃剤は、燃焼時のダイオキシン生
成が疑われ、酸化アンチモンは毒性を持つことが知られ
ているため、近年それらを添加したエポキシ樹脂接着剤
やその接着剤を用いた電子部品装置の処分法等につい
て、環境、安全面から問題になっており、使用規制の要
求が強まっている。このような状況から、種々のノンハ
ロゲン、ノンアンチモン系難燃剤が提案されている。例
えば、水酸化アルミニウム、水酸化マグネシウム、水酸
化カルシウム等の金属水和物の使用が提案され、これら
は、安全性が高く低コストであるという利点があるが、
難燃化のためには多量添加が必要で、環境加速試験時の
電気特性を損ね、かつ成膜性に劣るという問題があっ
た。[0003] However, halogen (bromine) flame retardants such as decabromide are suspected of producing dioxins during combustion, and antimony oxide is known to be toxic. There are environmental and safety issues regarding the disposal method of electronic component devices using agents and their adhesives, and the demand for use regulations is increasing. Under these circumstances, various non-halogen and non-antimony flame retardants have been proposed. For example, the use of metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide has been proposed, which has the advantage of high safety and low cost.
For the purpose of flame retardation, a large amount of addition is required, and there has been a problem that electrical properties at the time of an environmental acceleration test are impaired, and film formability is poor.
【０００４】本発明は、上記事情に鑑みなされたもの
で、十分な難燃性を示し、環境に対する安全性が高く、
電気特性が良好な難燃性樹脂接着剤を提供することを目
的とするものである。[0004] The present invention has been made in view of the above circumstances, shows sufficient flame retardancy, has high environmental safety,
It is an object of the present invention to provide a flame-retardant resin adhesive having good electric characteristics.
【０００５】[0005]
【課題を解決するための手段及び発明の実施の形態】本
発明者は、上記目的を達成するため鋭意検討を重ねた結
果、後述する一般式（１）で示される、樹脂骨格中にリ
ン成分を０．０１〜１０重量％含有するエポキシ樹脂を
他のエポキシ樹脂及びフェノール性硬化剤と併用するこ
とによって得られた難燃性樹脂接着剤が、銅箔等の各種
金属箔と耐熱性支持材料（例えば、耐熱性フィルム、無
機シートなど）との張り合わせを比較的低温で行うこと
ができると共に、前記難燃性樹脂接着剤で張り合わされ
た積層体は、接着剤層が十分な接着力を示すので、例え
ばフレキシブル配線基板、ＴＡＢ（Ｔａｐｅ Ａｕｔｏ
ｍａｔｅｄ Ｂｏｎｄｉｎｇ）用銅張基板などの製造に
使用すれば生産性が著しく向上し、かつ十分な難燃性を
示すため安全に使用することができることを知見し、本
発明をなすに至った。Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies in order to achieve the above object, and as a result, a phosphorus component in a resin skeleton represented by the following general formula (1) has been obtained. Flame-retardant resin adhesive obtained by using an epoxy resin containing 0.01 to 10% by weight in combination with another epoxy resin and a phenolic curing agent is used to form a heat-resistant supporting material with various metal foils such as a copper foil. (For example, a heat-resistant film, an inorganic sheet, or the like) can be bonded at a relatively low temperature, and in the laminate bonded with the flame-retardant resin adhesive, the adhesive layer exhibits a sufficient adhesive strength. Therefore, for example, a flexible wiring board, TAB (Tape Auto
The present inventors have found that productivity can be remarkably improved if used for manufacturing a copper-clad substrate for a mated bonding, etc., and that it can be used safely because it shows sufficient flame retardancy, and the present invention has been accomplished.
【０００６】以下、本発明につき更に詳しく説明する
と、本発明は、下記一般式（１）で示される樹脂骨格中
にリン成分を０．０１〜１０重量％含有するエポキシ樹
脂化合物１０〜１００重量部、その他のエポキシ樹脂化
合物１０〜１００重量部、フェノール性硬化剤１０〜１
００重量部を含有することを特徴とする難燃性樹脂接着
剤を提供する。Now, the present invention will be described in further detail. The present invention relates to 10 to 100 parts by weight of an epoxy resin compound containing 0.01 to 10% by weight of a phosphorus component in a resin skeleton represented by the following general formula (1). , Other epoxy resin compounds 10 to 100 parts by weight, phenolic curing agent 10 to 1
A flame-retardant resin adhesive characterized by containing 00 parts by weight.
【０００７】[0007]
【化７】 ［式中、ｋは１〜１０の数、Ｘは、Embedded image Wherein k is a number from 1 to 10, and X is
【化８】 から選ばれる基（但し、Ｒ1は水素原子又は炭素数１〜
１８の１価炭化水素基を示す）、Ｙは、下記式（ｉ）〜
（ｘｉｖ）から選ばれる基を示す。］Embedded image Wherein R 1 is a hydrogen atom or a group having 1 to 1 carbon atoms
18 represents a monovalent hydrocarbon group), and Y represents the following formulas (i) to
And a group selected from (xiv). ]
【０００８】[0008]
【化９】 Embedded image
【０００９】[0009]
【化１０】 Embedded image
【００１０】[0010]
【化１１】 （式中、Ｒ2は、互いに同一又は異なっていてもよく、
水素原子又は炭素数１〜１８の１価炭化水素基を示し、
ｍは０〜１０の数である。）Embedded image (Wherein, R 2 may be the same or different from each other;
A hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms,
m is a number from 0 to 10. )
【００１１】ここで、Ｒ1、Ｒ2の１価炭化水素基として
は、炭素数１〜１８、特に１〜１０のアルキル基、例え
ばメチル基、エチル基、プロピル基、イソプロピル基、
ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ヘ
キシル基、オクチル基、デシル基、ドデシル基等のアル
キル基や、フェニル基等のアリール基などを挙げること
ができる。Here, the monovalent hydrocarbon group for R 1 and R 2 is an alkyl group having 1 to 18 carbon atoms, especially 1 to 10 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group,
Examples include an alkyl group such as an n-butyl group, an isobutyl group, a tert-butyl group, a hexyl group, an octyl group, a decyl group, and a dodecyl group, and an aryl group such as a phenyl group.
【００１２】また、上記式において、ｋは１〜１０であ
るが、好ましくは１〜５、より好ましくは１〜３であ
り、また、ｍは０〜１０であるが、好ましくは１〜５、
より好ましくは1〜３である。In the above formula, k is 1 to 10, preferably 1 to 5, more preferably 1 to 3, and m is 0 to 10, preferably 1 to 5,
More preferably, it is 1-3.
【００１３】更に、上記式（１）の化合物は、樹脂骨格
中に０．０１〜１０重量％のリン成分（リン原子）を含
むものであるが、この量は、好ましくは０．１〜７．５
重量％、更に好ましくは１〜５重量％である。リン成分
の含有量が０．０１重量％より少ないと、十分な難燃化
を付与する効果が得られず、１０重量％を超えると、必
然的にフェノール骨格、フェニレン骨格、ナフタレン骨
格等の芳香族環ユニットが増加して、樹脂が増粘するた
め、接着剤組成物としての使用が困難となる。Furthermore, the compound of the above formula (1) contains 0.01 to 10% by weight of a phosphorus component (phosphorus atom) in the resin skeleton, and the amount is preferably 0.1 to 7.5.
%, More preferably 1 to 5% by weight. If the content of the phosphorus component is less than 0.01% by weight, the effect of imparting sufficient flame retardancy cannot be obtained, and if the content exceeds 10% by weight, aromatics such as phenol skeleton, phenylene skeleton, and naphthalene skeleton are inevitably. Since the number of aromatic ring units increases and the viscosity of the resin increases, it becomes difficult to use the resin as an adhesive composition.
【００１４】本発明の難燃性樹脂接着剤には、上記リン
含有エポキシ樹脂以外にリン無含有の他のエポキシ樹脂
として従来公知のエポキシ樹脂を併用する。例えば、ビ
スフェノールＡ、ビスフェノールＦ、レゾルシノール、
フェノールノボラック、クレゾールノボラック等のフェ
ノール類のグリシジルエーテル、ブタンジオール、ポリ
エチレングリコール、ポリプロピレングリコール等のア
ルコール類のグリシジルエーテル、フタル酸、イソフタ
ル酸、テトラヒドロフタル酸等のカルボン酸類のグリシ
ジルエステル、アニリン、イソシアヌール酸等の窒素原
子に結合した活性水素をグリシジル基で置換したものな
どのグリシジル型（メチルグリシジル型も含む）エポキ
シ樹脂、分子内のオレフィン結合をエポキシ化して得ら
れるビニルシクロヘキセンジエポキシド、３，４−エポ
キシシクロヘキシルメチル−３，４−エポキシシクロヘ
キサンカルボキシレート、２−（３，４−エポキシ）シ
クロヘキシル−５，５−スピロ（３，４−エポキシ）シ
クロヘキサン−ｍ−ジオキサン等の脂環型エポキシ樹
脂、パラキシリレン変性フェノール樹脂のグリシジルエ
ーテル、メタキシリレン・パラキシリレン変性フェノー
ル樹脂のグリシジルエーテル、テルペン変性フェノール
樹脂のグリシジルエーテル、ジシクロペンタジエン変性
フェノール樹脂のグリシジルエーテル、シクロペンタジ
エン変性フェノール樹脂のグリシジルエーテル、多環芳
香族変性フェノール樹脂のグリシジルエーテル、ナフタ
レン環含有フェノール樹脂のグリシジルエーテル、ビフ
ェニル型エポキシ樹脂などが挙げられ、これらは単独で
あるいは２種以上混合して用いることができる。但し、
本発明では、ハロゲン化エポキシ樹脂は配合しない。The flame-retardant resin adhesive of the present invention uses, in addition to the above-mentioned phosphorus-containing epoxy resin, a conventionally known epoxy resin as another phosphorus-free epoxy resin. For example, bisphenol A, bisphenol F, resorcinol,
Glycidyl ethers of phenols such as phenol novolak and cresol novolac, glycidyl ethers of alcohols such as butanediol, polyethylene glycol and polypropylene glycol, glycidyl esters of carboxylic acids such as phthalic acid, isophthalic acid and tetrahydrophthalic acid, aniline and isocyanurate Glycidyl type (including methyl glycidyl type) epoxy resins such as those in which active hydrogen bonded to a nitrogen atom such as an acid is substituted with a glycidyl group, vinylcyclohexene diepoxide obtained by epoxidizing an olefin bond in a molecule, 3,4 -Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxy) cyclohexyl-5,5-spiro (3,4-epoxy) cyclohexane-m Alicyclic epoxy resins such as dioxane, glycidyl ether of para-xylylene-modified phenol resin, glycidyl ether of meta-xylylene / para-xylylene-modified phenol resin, glycidyl ether of terpene-modified phenol resin, glycidyl ether of dicyclopentadiene-modified phenol resin, and cyclopentadiene-modified phenol resin Glycidyl ether, glycidyl ether of a polycyclic aromatic modified phenol resin, glycidyl ether of a naphthalene ring-containing phenol resin, and a biphenyl type epoxy resin. These can be used alone or in combination of two or more. However,
In the present invention, no halogenated epoxy resin is blended.
【００１５】この場合、リン含有のエポキシ樹脂以外の
エポキシ樹脂は、融点が１００℃以下、特に０〜８０℃
程度であるもの、あるいは、３０℃以下の温度で液状で
あるものが特に好ましい。これは、特にエポキシ樹脂の
融点が１００℃より上である場合、耐熱性フィルムと銅
箔とを張り合わせる際に著しく粘着性能に乏しいため、
作業性が低下して、本硬化に入る前の十分な仮止めが困
難となるおそれがあるためである。In this case, the epoxy resin other than the phosphorus-containing epoxy resin has a melting point of 100 ° C. or less, especially 0 to 80 ° C.
Particularly preferable are those which are in a liquid state at a temperature of 30 ° C. or lower. This is because, in particular, when the melting point of the epoxy resin is higher than 100 ° C., the adhesive performance is extremely poor when bonding the heat-resistant film and the copper foil.
This is because the workability may decrease, and it may be difficult to perform a sufficient temporary fixing before starting the main curing.
【００１６】ここで、上記式（１）のエポキシ樹脂
［Ａ］と、リン無含有の他のエポキシ樹脂とは、前者
［Ａ］が１０〜１００部（重量部、以下同じ）、後者
［Ｂ］が１０〜１００部の割合で配合するが、全エポキ
シ樹脂中、上記エポキシ樹脂［Ａ］を９０〜９１重量
％、好ましくは２０〜９０重量％、より好ましくは３０
〜８０重量％、更に好ましくは４０〜７５重量％含有す
ることが望ましい。エポキシ樹脂［Ａ］が少なすぎると
十分な難燃効果が得られず、多すぎると接着力が低下し
たり、耐湿信頼性に劣ったものとなる。Here, the epoxy resin [A] of the above formula (1) and the other phosphorus-free epoxy resin are 10 to 100 parts (parts by weight, hereinafter the same) of the former [A] and the latter [B] Is mixed at a ratio of 10 to 100 parts, and the total amount of the epoxy resin [A] is 90 to 91% by weight, preferably 20 to 90% by weight, more preferably 30 to 100% by weight.
It is desirably contained in an amount of from 80 to 80% by weight, more preferably from 40 to 75% by weight. If the amount of the epoxy resin [A] is too small, a sufficient flame-retardant effect cannot be obtained. If the amount is too large, the adhesive strength is lowered or the humidity resistance is poor.
【００１７】次に、フェノール性硬化剤としては、例え
ばフェノール、クレゾール、キシレノール、ハイドロキ
ノン、レゾルシン、カテコール、ビスフェノールＡ、ビ
スフェノールＦ等のフェノール類又はα−ナフトール、
β−ナフトール、ジヒドロキシナフタレン等のナフトー
ル類とホルムアルデヒド、アセトアルデヒド、プロピオ
ンアルデヒド、ベンズアルデヒド、サリチルアルデヒド
等のアルデヒド類とを酸性触媒下で縮合又は共縮合させ
て得られる樹脂；フェノール類とジメトキシパラキシレ
ン等から合成されるキシリレン骨格を有するフェノール
樹脂；ジシクロペンタジエン骨格を有するフェノール樹
脂；シクロペンタジエン骨格を有するフェノール樹脂；
メラミン変性フェノール樹脂；テルペン変性フェノール
樹脂；多環芳香族変性フェノール樹脂；キシリレン骨格
を有するナフトール樹脂などが挙げられ、これらを単独
又は２種類以上混合して用いることができる。これらの
中で、特に下記一般式（２）で示されるものが好まし
い。Examples of the phenolic curing agent include phenols such as phenol, cresol, xylenol, hydroquinone, resorcin, catechol, bisphenol A, bisphenol F, and α-naphthol;
Resins obtained by condensing or co-condensing naphthols such as β-naphthol and dihydroxynaphthalene with aldehydes such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde; from phenols and dimethoxyparaxylene A phenol resin having a xylylene skeleton to be synthesized; a phenol resin having a dicyclopentadiene skeleton; a phenol resin having a cyclopentadiene skeleton;
Melamine-modified phenolic resin; terpene-modified phenolic resin; polycyclic aromatic-modified phenolic resin; naphthol resin having a xylylene skeleton, and the like can be used alone or in combination of two or more. Among them, those represented by the following general formula (2) are particularly preferable.
【００１８】[0018]
【化１２】 であり、Ｒ3は、互いに同一又は異なっていてもよく、
水素原子、炭素数１〜４のアルキル基、又はフェニル基
であり、ｎは０〜１０、好ましくは０〜５、より好まし
くは０〜２の数である。）Embedded image In and, R 3 may be the same or different from each other,
It is a hydrogen atom, a C1-C4 alkyl group, or a phenyl group, and n is a number of 0-10, preferably 0-5, more preferably 0-2. )
【００１９】上記フェノール性硬化剤の配合量は、上記
エポキシ樹脂［Ａ］１０〜１００部、エポキシ樹脂
［Ｂ］１０〜１００部において、１０〜１００部の割合
であるが、全エポキシ樹脂１００部に対し５０〜２００
部、好ましくは７０〜１５０部、更に好ましくは８０〜
１２０部の割合で配合することが望ましい。またこの場
合、全エポキシ樹脂と、フェノール性硬化剤とは、エポ
キシ基とフェノール性水酸基との化学当量比が、０．７
〜１．３、特に０．８〜１．２であることが好ましく、
このような範囲とすることにより、それぞれの未反応分
を少なく抑え、接着力、吸水量、電気特性等の経時劣化
を低下させるのに有効である。The mixing amount of the phenolic curing agent is 10 to 100 parts in 10 to 100 parts of the epoxy resin [A] and 10 to 100 parts of the epoxy resin [B]. 50-200 for
Parts, preferably 70-150 parts, more preferably 80-
It is desirable to mix them in a proportion of 120 parts. In this case, the total epoxy resin and the phenolic curing agent have a chemical equivalent ratio of the epoxy group to the phenolic hydroxyl group of 0.7.
To 1.3, particularly preferably 0.8 to 1.2,
By setting the content in such a range, each unreacted component is suppressed to be small, and it is effective to reduce the deterioration with time of the adhesive force, the water absorption, the electric characteristics and the like.
【００２０】なお、本発明においては、上記フェノール
性硬化剤に加え、酸無水物等の他のエポキシ樹脂の硬化
剤を、本発明の効果を阻害しない範囲で配合することは
差し支えない。In the present invention, in addition to the phenolic curing agent, a curing agent for another epoxy resin such as an acid anhydride may be blended within a range not to impair the effects of the present invention.
【００２１】本発明の難燃性樹脂接着剤には、更に硬化
促進剤を配合することが好ましい。硬化促進剤として
は、エポキシ樹脂と硬化剤との硬化反応を促進させるも
のならば特に限定されず、例えば、イミダゾール化合
物、３級アミン化合物、有機リン系化合物から選ばれる
１種又は２種以上を配合することができる。The flame retardant resin adhesive of the present invention preferably further contains a curing accelerator. The curing accelerator is not particularly limited as long as it accelerates the curing reaction between the epoxy resin and the curing agent. For example, one or more selected from imidazole compounds, tertiary amine compounds, and organic phosphorus compounds are used. Can be blended.
【００２２】ここで、イミダゾール化合物としては、２
−メチルイミダゾール、２−エチルイミダゾール、４−
メチルイミダゾール、４−エチルイミダゾール、２−フ
ェニルイミダゾール、２−フェニル−４−メチルイミダ
ゾール、２−フェニル−４−ヒドロキシメチルイミダゾ
ール、２−エチル−４−メチルイミダゾール、１−シア
ノエチル−２−メチルイミダゾール、２−フェニル−４
−メチル−５−ヒドロキシメチルイミダゾール、２−フ
ェニル−４，５−ジヒドロキシメチルイミダゾール等が
挙げられる。Here, as the imidazole compound, 2
-Methylimidazole, 2-ethylimidazole, 4-
Methylimidazole, 4-ethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-phenyl-4-hydroxymethylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 2-phenyl-4
-Methyl-5-hydroxymethylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and the like.
【００２３】また、３級アミン化合物としては、トリエ
チルアミン、ベンジルジメチルアミン、ベンジルトリメ
チルアミン、α−メチルベンジルジメチルアミン等の窒
素原子に結合する置換基としてアルキル基やアラルキル
基を有するアミン化合物、１，８−ジアザビシクロ
［５．４．０］ウンデセン−７及びそのフェノール塩、
オクチル酸塩、オレイン酸塩などのシクロアミジン化合
物やその有機酸との塩、あるいは下記式の化合物などの
シクロアミジン化合物と４級ホウ素化合物との塩又は錯
塩などが挙げられる。Examples of the tertiary amine compound include amine compounds having an alkyl group or an aralkyl group as a substituent bonded to a nitrogen atom, such as triethylamine, benzyldimethylamine, benzyltrimethylamine and α-methylbenzyldimethylamine. -Diazabicyclo [5.4.0] undecene-7 and phenol salts thereof,
Examples thereof include salts with cycloamidine compounds such as octylates and oleates and salts thereof with organic acids, and salts or complex salts of cycloamidine compounds such as compounds of the following formulas with quaternary boron compounds.
【００２４】[0024]
【化１３】 Embedded image
【００２５】また、有機リン系化合物としては、トリフ
ェニルホスフィン、トリブチルホスフィン、トリ（ｐ−
メチルフェニル）ホスフィン、トリ（ノニルフェニル）
ホスフィン、トリフェニルホスフィン・トリフェニルボ
ラン等のトリオルガノホスフィン化合物やテトラフェニ
ルホスホニウム・テトラフェニルボレート等の４級ホス
ホニウム塩などが挙げられる。The organic phosphorus compounds include triphenylphosphine, tributylphosphine, tri (p-
Methylphenyl) phosphine, tri (nonylphenyl)
Examples include triorganophosphine compounds such as phosphine and triphenylphosphine / triphenylborane, and quaternary phosphonium salts such as tetraphenylphosphonium / tetraphenylborate.
【００２６】これらの硬化促進剤の配合量は、上記エポ
キシ樹脂と硬化剤との合計１００部に対して、通常１０
部以下（０〜１０部）、望ましくは０．０１〜１０部、
より望ましくは０．５〜５部程度が好ましい。配合量が
１０部より多いと硬化性に優れるが、保存安定性が低下
する傾向となる場合がある。The amount of these curing accelerators is usually 10 parts with respect to 100 parts in total of the epoxy resin and the curing agent.
Or less (0 to 10 parts), desirably 0.01 to 10 parts,
More desirably, about 0.5 to 5 parts is preferable. If the amount is more than 10 parts, the curability is excellent, but the storage stability tends to decrease.
【００２７】本発明の難燃性樹脂接着剤には、リン含有
エポキシ樹脂以外に難燃性を補助する目的で水酸化アル
ミニウム、水酸化マグネシウム、水酸化カルシウム等の
金属水和物を成膜性に問題ない範囲で配合してもよい。
但し、ハロゲン化エポキシ樹脂、アンチモン化合物は配
合されない。The flame-retardant resin adhesive of the present invention may be formed of a metal hydrate such as aluminum hydroxide, magnesium hydroxide, or calcium hydroxide for the purpose of supporting flame retardancy in addition to the phosphorus-containing epoxy resin. You may mix | blend in the range which does not have a problem.
However, a halogenated epoxy resin and an antimony compound are not blended.
【００２８】本発明の難燃性樹脂接着剤には、上記成分
以外に柔軟性を付与する目的でシリコーンゴムやシリコ
ーンオイル、液状もしくは固体のブタジエンニトリルゴ
ムなどを成膜性に問題ない範囲で配合してもよい。The flame-retardant resin adhesive of the present invention contains, in addition to the above components, silicone rubber, silicone oil, liquid or solid butadiene nitrile rubber, etc., in order to impart flexibility, as long as there is no problem in film formability. May be.
【００２９】本発明の難燃性樹脂接着剤は、前記のリン
含有エポキシ樹脂と、他のエポキシ樹脂と、フェノール
性エポキシ樹脂硬化剤とからなる特定の組成比の樹脂成
分が、主成分として（特に好ましくは９０重量％以上、
更に好ましくは９５〜１００重量％程度）含有されてい
る難燃性樹脂接着剤であればよい。また前記の難燃性樹
脂接着剤が、粘着可能なドライフィルム又はシート状難
燃性樹脂接着剤あるいは適当な有機極性溶媒中に、特に
３〜５０重量％、更に好ましくは５〜４０重量％の濃度
で、均一に溶解されている難燃性樹脂接着剤の溶液組成
物であってもよい。The flame-retardant resin adhesive of the present invention comprises, as a main component, a resin component having a specific composition ratio of the above-mentioned phosphorus-containing epoxy resin, another epoxy resin, and a phenolic epoxy resin curing agent. Particularly preferably 90% by weight or more,
More preferably, it is a flame-retardant resin adhesive containing about 95 to 100% by weight. The flame-retardant resin adhesive is preferably used in an amount of 3 to 50% by weight, more preferably 5 to 40% by weight, in a tacky dry film or sheet-like flame-retardant resin adhesive or a suitable organic polar solvent. It may be a solution composition of a flame-retardant resin adhesive that is uniformly dissolved in concentration.
【００３０】その難燃性樹脂接着剤の溶液組成物は、そ
の溶液粘度（３０℃）が、０．１〜１０，０００ポイ
ズ、特に０．２〜５，０００ポイズ、更に１〜１，００
０ポイズ程度であることが好ましい。The solution composition of the flame-retardant resin adhesive has a solution viscosity (30 ° C.) of 0.1 to 10,000 poise, particularly 0.2 to 5,000 poise, and furthermore 1 to 1,000.
It is preferably about 0 poise.
【００３１】なお、本発明の難燃性樹脂接着剤は、未硬
化の樹脂成分のみの組成物の軟化点（熱板上で軟化が開
始する温度）が、１５０℃以下、特に１２０℃以下、更
に好ましくは１００℃以下であることが好ましい。本発
明の難燃性樹脂接着剤は、１３０〜２５０℃、更に好ま
しくは１４０〜１８０℃の硬化温度に加熱することによ
って熱硬化することができるものであることが好まし
い。この難燃性樹脂接着剤の軟化点が１５０℃を超える
場合、耐熱性フィルムと銅箔とを張り合わせる際に著し
く粘着性能に乏しいため、作業性が低下して、本硬化に
入る前の十分な仮止めが困難となるおそれがあるためで
ある。また、１３０℃未満の熱硬化温度の場合、低温硬
化のため著しく硬化に時間がかかるか、非常に保存安定
性の悪いものとなってしまうおそれがある。また、反応
温度が２５０℃を超える場合、銅箔が酸化されてしま
い、張り合わせたフレキシブル銅基板が使用不能となっ
てしまうおそれがある。The flame-retardant resin adhesive of the present invention has a softening point (temperature at which softening starts on a hot plate) of an uncured resin component alone of 150 ° C. or lower, particularly 120 ° C. or lower. More preferably, the temperature is 100 ° C. or lower. The flame-retardant resin adhesive of the present invention is preferably one that can be thermally cured by heating to a curing temperature of 130 to 250 ° C, more preferably 140 to 180 ° C. When the softening point of the flame-retardant resin adhesive is higher than 150 ° C., the adhesive property is extremely poor when bonding the heat-resistant film and the copper foil. This is because it may be difficult to perform temporary fixing. If the heat curing temperature is lower than 130 ° C., the curing may take a long time due to the low temperature curing, or the storage stability may be extremely poor. If the reaction temperature exceeds 250 ° C., the copper foil may be oxidized, and the bonded flexible copper substrate may not be used.
【００３２】本発明の難燃性樹脂接着剤は、前述の樹脂
成分の全てが有機極性溶媒に均一に溶解されている難燃
性樹脂接着剤の溶液組成物を、適当な金属箔、芳香族ポ
リイミドフィルムなどの耐熱性フィルム面、又は、ポリ
エステルやポリエチレンなどの熱可塑性樹脂のフィルム
面上に塗布し、その塗布層を６０〜１４０℃、特に８０
〜１３０℃の温度で２０秒〜１００分間、特に３０〜６
０分間乾燥することによって、実質的に溶媒が除去され
た（好ましくは溶媒残存割合が１重量％以下、特に０．
５重量％以下である）未硬化状態の難燃性樹脂接着剤の
薄膜（厚さが約１〜２００μｍであるドライフィルム又
はシート）を形成することができる。The flame-retardant resin adhesive of the present invention is prepared by mixing a solution composition of the flame-retardant resin adhesive in which all of the above-mentioned resin components are uniformly dissolved in an organic polar solvent with a suitable metal foil, aromatic resin, A heat-resistant film surface such as a polyimide film, or a film of a thermoplastic resin such as polyester or polyethylene is applied on the film surface, and the coating layer is applied at 60 to 140 ° C, particularly 80 ° C.
20 to 100 minutes at a temperature of ~ 130 ° C, especially 30 ~ 6
By drying for 0 minutes, the solvent was substantially removed (preferably the solvent remaining ratio was 1% by weight or less, particularly 0.1% by weight.
It is possible to form a thin film (dry film or sheet having a thickness of about 1 to 200 μm) of an uncured flame-retardant resin adhesive (not more than 5% by weight).
【００３３】前述のようにして製造された未硬化の難燃
性樹脂接着剤の薄膜は、好適な柔軟性を有しており、細
管などに巻きつけが可能である。また、打ち抜き法など
の穴開け加工をすることもでき、更に、例えば、前記の
耐熱性又は熱可塑性フィルム上に未硬化の透明かつ難燃
性樹脂接着剤の薄層が形成されている積層シートと、転
写先用の金属箔又は耐熱性フィルムなどとを重ね合わせ
て、約２０〜１４０℃、特に３０〜１３０℃の温度に加
熱された一対のロール（ラミネートロール）間を通すこ
とによって転写先用の金属箔又は耐熱性フィルム上に転
写することも可能である。The uncured flame-retardant resin adhesive thin film produced as described above has suitable flexibility and can be wound around a thin tube or the like. It is also possible to perform a punching process such as a punching method, and further, for example, a laminated sheet in which a thin layer of an uncured transparent and flame-retardant resin adhesive is formed on the heat-resistant or thermoplastic film. And a metal foil or a heat-resistant film or the like for the transfer destination are overlapped and passed between a pair of rolls (lamination rolls) heated to a temperature of about 20 to 140 ° C., particularly 30 to 130 ° C. It is also possible to transfer onto a metal foil or a heat-resistant film for use.
【００３４】本発明の難燃性樹脂接着剤を使用して耐熱
性フィルムと金属箔などとを接合させて銅張基板などの
積層体を形成するには、例えば、前述のように形成され
た薄膜状の難燃性樹脂接着剤を介して、耐熱性フィルム
と金属箔とを８０〜１８０℃、特に１００〜１７０℃の
温度でラミネート（張り合わせ）して、更に、そのラミ
ネートされたものを、８０〜２５０℃の温度で３０分〜
４０時間、特に１〜３０時間加熱して、前記難燃性の接
着剤層を加熱硬化させることによって、前述の積層体を
何らの支障もなく容易に連続的に製造することができ
る。In order to form a laminate such as a copper-clad substrate by bonding a heat-resistant film and a metal foil using the flame-retardant resin adhesive of the present invention, for example, the above-described method is used. A heat-resistant film and a metal foil are laminated (laminated) at a temperature of 80 to 180 ° C., particularly 100 to 170 ° C., via a thin-film flame-retardant resin adhesive. 30 minutes at 80-250 ° C
By heating and curing the flame-retardant adhesive layer by heating for 40 hours, especially for 1 to 30 hours, the above-mentioned laminate can be easily and continuously manufactured without any trouble.
【００３５】本発明の難燃性樹脂接着剤は、芳香族ポリ
イミドフィルム、ポリアミドフィルム、ポリエーテルエ
ーテルケトン、ＰＥＥＫフィルム、ポリエーテルスルホ
ンフィルムなどの耐熱性フィルムと、銅箔などの適当な
金属箔と接合するために好適に使用されるほかに、ビル
トアップ基板用の樹脂接着剤として有効に使用すること
ができる。The flame-retardant resin adhesive of the present invention comprises a heat-resistant film such as an aromatic polyimide film, a polyamide film, a polyetheretherketone, a PEEK film, a polyethersulfone film, and a suitable metal foil such as a copper foil. Besides being suitably used for bonding, it can be effectively used as a resin adhesive for a built-up substrate.
【００３６】[0036]
【発明の効果】本発明の難燃性樹脂接着剤によれば、ノ
ンハロゲン、ノンアンチモンで環境に対する安全性を有
し、かつ十分な難燃性を示し、電気特性が良好なもので
ある。According to the flame-retardant resin adhesive of the present invention, it is non-halogen, non-antimony, has environmental safety, shows sufficient flame retardancy, and has good electric characteristics.
【００３７】[0037]
【実施例】以下、合成例、及び実施例と比較例を示し、
本発明を具体的に説明するが、本発明は下記の実施例に
制限されるものではない。なお、下記の例において部は
重量部を示す。EXAMPLES The following shows synthesis examples, examples and comparative examples,
The present invention will be specifically described, but the present invention is not limited to the following examples. In addition, in the following examples, a part shows a weight part.
【００３８】［合成例１］ビスフェノールＡ（新日本理
化社製）４５６部とトルエン（関東化学社製）６００部
の氷冷した混合溶液に、エチルジクロロホスファイト
（Ａｌｄｒｉｃｈ社製）１６２部を温度が２０〜３０℃
に保たれるようにゆっくりと滴下する。滴下後３時間撹
拌する。ここに４８重量％のＮａＯＨ水溶液を２００部
添加して、トルエン相を分液ロートで分離して、生成し
た塩酸を取り除く。この作業を３度繰り返して、完全に
塩酸を取り除く。ここで得られたトルエン相を減圧下で
加熱し、トルエンを除去して淡黄色の固体を取り出す。
ここで得られた淡黄色固体５８０部をエピクロロヒドリ
ン（Ａｌｄｒｉｃｈ社製）４６０部に撹拌溶解させ、反
応系内を１５０ｍｍＨｇの圧力に調節した後、温度を６
８℃に昇温した。これに４８重量％の水酸化ナトリウム
水溶液７５部を連続的に滴下しながら３．５時間反応さ
せた。この間反応により生成する水及び水酸化ナトリウ
ム水溶液の水を水−エピクロロヒドリン共沸混合物の還
流により分離し、反応系外へ連続的に除去した。反応終
了後、反応系を常圧にもどし、１１０℃の温度まで昇温
して反応系の水を完全に除去した。過剰のエピクロロヒ
ドリンを常圧下に蒸発除去し、更に１５ｍｍＨｇの減圧
下に１４０℃で蒸発を行った。生成した樹脂及び塩化ナ
トリウムの混合物に２−ブタノン１７５部及び１０重量
％の水酸化ナトリウム水溶液２４部を加え、８０〜８５
℃の温度で１．５時間反応を行った。反応終了後、２−
ブタノン３５０部及び水２００部を加え、下層の塩化ナ
トリウム水溶液を分液除去した。２−ブタノン溶液層に
水１００部を加えて洗浄し、リン酸で中和し、水層を分
離したのち、更に水１００部で洗浄し、水層を分離し
た。２−ブタノン樹脂溶液は常圧下に大半の２−ブタノ
ンを蒸発させて除去した後、５ｍｍＨｇの減圧下に１４
０℃の温度で蒸発乾燥を行い、リン含量４．２％、エポ
キシ当量３５２ｇ／ｅｑの下記リン含有エポキシ樹脂を
得ることができた。[Synthesis Example 1] 162 parts of ethyldichlorophosphite (manufactured by Aldrich) was added to an ice-cooled mixed solution of 456 parts of bisphenol A (manufactured by Nippon Rika Co., Ltd.) and 600 parts of toluene (manufactured by Kanto Chemical Co., Ltd.). Is 20-30 ° C
Drop slowly so that it is maintained at Stir for 3 hours after dropping. Here, 200 parts of a 48% by weight aqueous NaOH solution is added, and the toluene phase is separated by a separating funnel to remove generated hydrochloric acid. This operation is repeated three times to completely remove the hydrochloric acid. The toluene phase obtained here is heated under reduced pressure to remove toluene and take out a pale yellow solid.
580 parts of the pale yellow solid obtained here was stirred and dissolved in 460 parts of epichlorohydrin (manufactured by Aldrich), and the pressure in the reaction system was adjusted to 150 mmHg.
The temperature was raised to 8 ° C. The mixture was reacted for 3.5 hours while continuously adding 75 parts of a 48% by weight aqueous sodium hydroxide solution dropwise thereto. During this time, water generated by the reaction and water of an aqueous sodium hydroxide solution were separated by refluxing a water-epichlorohydrin azeotrope, and continuously removed outside the reaction system. After completion of the reaction, the reaction system was returned to normal pressure, and the temperature was raised to 110 ° C. to completely remove water from the reaction system. Excess epichlorohydrin was removed by evaporation under normal pressure, and evaporation was further performed at 140 ° C. under a reduced pressure of 15 mmHg. To a mixture of the resulting resin and sodium chloride, 175 parts of 2-butanone and 24 parts of a 10% by weight aqueous sodium hydroxide solution were added, and 80 to 85%
The reaction was performed at a temperature of 150C for 1.5 hours. After the reaction, 2-
350 parts of butanone and 200 parts of water were added, and the lower layer aqueous sodium chloride solution was separated and removed. The 2-butanone solution layer was washed by adding 100 parts of water and neutralized with phosphoric acid, and after separating the aqueous layer, further washing with 100 parts of water and separating the aqueous layer. After removing most of the 2-butanone by evaporating the 2-butanone resin solution under normal pressure, the 2-butanone resin solution was removed under reduced pressure of 5 mmHg.
By evaporating and drying at a temperature of 0 ° C., the following phosphorus-containing epoxy resin having a phosphorus content of 4.2% and an epoxy equivalent of 352 g / eq was obtained.
【００３９】[0039]
【化１４】 Embedded image
【００４０】［合成例２］ビスフェノールＡ（新日本理
化社製）６８０部とトルエン（関東化学社製）６００部
の氷冷した混合溶液に、エチルジクロロホスフェート
（Ａｌｄｒｉｃｈ社製）１７８部を温度が２０〜３０℃
に保たれるようにゆっくりと滴下する。滴下後３時間撹
拌する。ここに４８重量％のＮａＯＨ水溶液を２００部
添加して、トルエン相を分液ロートで分離して、生成し
た塩酸を取り除く。この作業を３度繰り返して、完全に
塩酸を取り除く。ここで得られたトルエン相を減圧下で
加熱し、トルエンを除去して淡黄色の固体を取り出す。
ここで得られた淡黄色固体５８０部をエピクロロヒドリ
ン（Ａｌｄｒｉｃｈ社製）４６０部に撹拌溶解させ、反
応系内を１５０ｍｍＨｇの圧力に調節した後、温度を６
８℃に昇温した。これに４８重量％の水酸化ナトリウム
水溶液７５部を連続的に滴下しながら３．５時間反応さ
せた。この間反応により生成する水及び水酸化ナトリウ
ム水溶液の水を水−エピクロロヒドリン共沸混合物の還
流により分離し、反応系外へ連続的に除去した。反応終
了後、反応系を常圧にもどし、１１０℃の温度まで昇温
して反応系の水を完全に除去した。過剰のエピクロロヒ
ドリンを常圧下に蒸発除去し、更に１５ｍｍＨｇの減圧
下に１４０℃で蒸発を行った。生成した樹脂及び塩化ナ
トリウムの混合物に２−ブタノン１７５部及び１０重量
％の水酸化ナトリウム水溶液２４部を加え、８０〜８５
℃の温度で１．５時間反応を行った。反応終了後、２−
ブタノン３５０部及び水２００部を加え、下層の塩化ナ
トリウム水溶液を分液除去した。２−ブタノン溶液層に
水１００部を加えて洗浄し、リン酸で中和し、水層を分
離したのち、更に水１００部で洗浄し、水層を分離し
た。２−ブタノン樹脂溶液は常圧下に大半の２−ブタノ
ンを蒸発させて除去した後、５ｍｍＨｇの減圧下に１４
０℃の温度で蒸発乾燥を行い、リン含量４．１％、エポ
キシ当量３６５ｇ／ｅｑの下記リン含有エポキシ樹脂を
得ることができた。[Synthesis Example 2] A mixture of 680 parts of bisphenol A (manufactured by Nippon Rika) and 600 parts of toluene (manufactured by Kanto Chemical Co.) was ice-cooled and mixed with 178 parts of ethyldichlorophosphate (manufactured by Aldrich) at a temperature of 178 parts. 20-30 ° C
Drop slowly so that it is maintained at Stir for 3 hours after dropping. Here, 200 parts of a 48% by weight aqueous NaOH solution is added, and the toluene phase is separated by a separating funnel to remove generated hydrochloric acid. This operation is repeated three times to completely remove the hydrochloric acid. The toluene phase obtained here is heated under reduced pressure to remove toluene and take out a pale yellow solid.
580 parts of the pale yellow solid obtained here was stirred and dissolved in 460 parts of epichlorohydrin (manufactured by Aldrich), and the pressure in the reaction system was adjusted to 150 mmHg.
The temperature was raised to 8 ° C. The mixture was reacted for 3.5 hours while continuously adding 75 parts of a 48% by weight aqueous sodium hydroxide solution dropwise thereto. During this time, water generated by the reaction and water of an aqueous sodium hydroxide solution were separated by refluxing a water-epichlorohydrin azeotrope, and continuously removed outside the reaction system. After completion of the reaction, the reaction system was returned to normal pressure, and the temperature was raised to 110 ° C. to completely remove water from the reaction system. Excess epichlorohydrin was removed by evaporation under normal pressure, and evaporation was further performed at 140 ° C. under a reduced pressure of 15 mmHg. To a mixture of the resulting resin and sodium chloride, 175 parts of 2-butanone and 24 parts of a 10% by weight aqueous sodium hydroxide solution were added, and 80 to 85%
The reaction was performed at a temperature of 150C for 1.5 hours. After the reaction, 2-
350 parts of butanone and 200 parts of water were added, and the lower layer aqueous sodium chloride solution was separated and removed. The 2-butanone solution layer was washed by adding 100 parts of water and neutralized with phosphoric acid, and after separating the aqueous layer, further washing with 100 parts of water and separating the aqueous layer. After removing most of the 2-butanone by evaporating the 2-butanone resin solution under normal pressure, the 2-butanone resin solution was removed under reduced pressure of 5 mmHg.
By evaporating and drying at a temperature of 0 ° C., the following phosphorus-containing epoxy resin having a phosphorus content of 4.1% and an epoxy equivalent of 365 g / eq was obtained.
【００４１】[0041]
【化１５】 Embedded image
【００４２】［合成例３］フェノールノボラック樹脂Ｔ
Ｄ−２１３１（大日本インキ社製、フェノール性水酸基
当量１１０ｇ／ｅｑ）２２０部とトルエン（関東化学社
製）６００部の氷冷した混合溶液に、エチルジクロロホ
スファイト（Ａｌｄｒｉｃｈ社製）１６２部を温度が２
０〜３０℃に保たれるようにゆっくりと滴下する。滴下
後３時間撹拌する。ここに４８重量％のＮａＯＨ水溶液
を２００部添加して、トルエン相を分液ロートで分離し
て、生成した塩酸を取り除く。この作業を３度繰り返し
て、完全に塩酸を取り除く。ここで得られたトルエン相
を減圧下で加熱し、トルエンを除去して淡黄色の固体を
取り出す。ここで得られた淡黄色固体５８０部をエピク
ロロヒドリン（Ａｌｄｒｉｃｈ社製）４６０部に撹拌溶
解させ、反応系内を１５０ｍｍＨｇの圧力に調節した
後、温度を６８℃に昇温した。これに４８重量％の水酸
化ナトリウム水溶液７５部を連続的に滴下しながら３．
５時間反応させた。この間反応により生成する水及び水
酸化ナトリウム水溶液の水を水−エピクロロヒドリン共
沸混合物の還流により分離し、反応系外へ連続的に除去
した。反応終了後、反応系を常圧にもどし、１１０℃の
温度まで昇温して反応系の水を完全に除去した。過剰の
エピクロロヒドリンを常圧下に蒸発除去し、更に１５ｍ
ｍＨｇの減圧下に１４０℃で蒸発を行った。生成した樹
脂及び塩化ナトリウムの混合物に２−ブタノン１７５部
及び１０重量％の水酸化ナトリウム水溶液２４部を加
え、８０〜８５℃の温度で１．５時間反応を行った。反
応終了後、２−ブタノン３５０部及び水２００部を加
え、下層の塩化ナトリウム水溶液を分液除去した。２−
ブタノン溶液層に水１００部を加えて洗浄し、リン酸で
中和し、水層を分離したのち、更に水１００部で洗浄
し、水層を分離した。２−ブタノン樹脂溶液は常圧下に
大半の２−ブタノンを蒸発させて除去した後、５ｍｍＨ
ｇの減圧下に１４０℃の温度で蒸発乾燥を行い、リン含
量３．２％、エポキシ当量２８０ｇ／ｅｑの下記リン含
有エポキシ樹脂を得ることができた。[Synthesis Example 3] Phenol novolak resin T
162 parts of ethyldichlorophosphite (manufactured by Aldrich) was added to an ice-cooled mixed solution of 220 parts of D-2131 (manufactured by Dainippon Ink and phenolic hydroxyl equivalent 110 g / eq) and 600 parts of toluene (manufactured by Kanto Kagaku). Temperature 2
Add dropwise slowly to keep the temperature between 0 and 30 ° C. Stir for 3 hours after dropping. Here, 200 parts of a 48% by weight aqueous NaOH solution is added, and the toluene phase is separated by a separating funnel to remove generated hydrochloric acid. This operation is repeated three times to completely remove the hydrochloric acid. The toluene phase obtained here is heated under reduced pressure to remove toluene and take out a pale yellow solid. 580 parts of the obtained pale yellow solid was dissolved under stirring in 460 parts of epichlorohydrin (manufactured by Aldrich), the pressure in the reaction system was adjusted to 150 mmHg, and the temperature was raised to 68 ° C. 2. While continuously dropping 75 parts of a 48% by weight aqueous sodium hydroxide solution,
The reaction was performed for 5 hours. During this time, water generated by the reaction and water of an aqueous sodium hydroxide solution were separated by refluxing a water-epichlorohydrin azeotrope, and continuously removed outside the reaction system. After the completion of the reaction, the reaction system was returned to normal pressure, and the temperature was raised to 110 ° C. to completely remove water from the reaction system. The excess epichlorohydrin is removed by evaporation under normal pressure, and a further 15 m
Evaporation was carried out at 140 ° C. under a reduced pressure of mHg. 175 parts of 2-butanone and 24 parts of a 10% by weight aqueous sodium hydroxide solution were added to the resulting mixture of the resin and sodium chloride, and the mixture was reacted at a temperature of 80 to 85 ° C. for 1.5 hours. After completion of the reaction, 350 parts of 2-butanone and 200 parts of water were added, and the lower layer aqueous sodium chloride solution was separated and removed. 2-
The butanone solution layer was washed by adding 100 parts of water, neutralized with phosphoric acid, separated from the aqueous layer, and further washed with 100 parts of water to separate the aqueous layer. After removing most of the 2-butanone under normal pressure by evaporating the 2-butanone resin solution, 5 mmH
The evaporative drying was carried out at 140 ° C. under a reduced pressure of g to obtain the following phosphorus-containing epoxy resin having a phosphorus content of 3.2% and an epoxy equivalent of 280 g / eq.
【００４３】[0043]
【化１６】 Embedded image
【００４４】［合成例４］フェノールノボラック樹脂Ｔ
Ｄ−２１３１（大日本インキ社製、フェノール性水酸基
当量１１０ｇ／ｅｑ）２２０部とトルエン（関東化学社
製）６００部の氷冷した混合溶液に、エチルジクロロホ
スフェート（Ａｌｄｒｉｃｈ社製）１７８部を温度が２
０〜３０℃に保たれるようにゆっくりと滴下する。滴下
後３時間撹拌する。ここに４８重量％のＮａＯＨ水溶液
を２００部添加して、トルエン相を分液ロートで分離し
て、生成した塩酸を取り除く。この作業を３度繰り返し
て、完全に塩酸を取り除く。ここで得られたトルエン相
を減圧下で加熱し、トルエンを除去して淡黄色の固体を
取り出す。ここで得られた淡黄色固体５８０部をエピク
ロロヒドリン（Ａｌｄｒｉｃｈ社製）４６０部に撹拌溶
解させ、反応系内を１５０ｍｍＨｇの圧力に調節した
後、温度を６８℃に昇温した。これに４８重量％の水酸
化ナトリウム水溶液７５部を連続的に滴下しながら３．
５時間反応させた。この間反応により生成する水及び水
酸化ナトリウム水溶液の水を水−エピクロロヒドリン共
沸混合物の還流により分離し、反応系外へ連続的に除去
した。反応終了後、反応系を常圧にもどし、１１０℃の
温度まで昇温して反応系の水を完全に除去した。過剰の
エピクロロヒドリンを常圧下に蒸発除去し、更に１５ｍ
ｍＨｇの減圧下に１４０℃で蒸発を行った。生成した樹
脂及び塩化ナトリウムの混合物に２−ブタノン１７５部
及び１０重量％の水酸化ナトリウム水溶液２４部を加
え、８０〜８５℃の温度で１．５時間反応を行った。反
応終了後、２−ブタノン３５０部及び水２００部を加
え、下層の塩化ナトリウム水溶液を分液除去した。２−
ブタノン溶液層に水１００部を加えて洗浄し、リン酸で
中和し、水層を分離したのち、更に水１００部で洗浄
し、水層を分離した。２−ブタノン樹脂溶液は常圧下に
大半の２−ブタノンを蒸発させて除去した後、５ｍｍＨ
ｇの減圧下に１４０℃の温度で蒸発乾燥を行い、リン含
量３．０％、エポキシ当量２９０ｇ／ｅｑの下記リン含
有エポキシ樹脂を得ることができた。[Synthesis Example 4] Phenol novolak resin T
178 parts of ethyldichlorophosphate (manufactured by Aldrich) was added to an ice-cooled mixed solution of 220 parts of D-2131 (manufactured by Dainippon Ink, phenolic hydroxyl equivalent 110 g / eq) and 600 parts of toluene (manufactured by Kanto Kagaku). Is 2
Add dropwise slowly to keep the temperature between 0 and 30 ° C. Stir for 3 hours after dropping. Here, 200 parts of a 48% by weight aqueous NaOH solution is added, and the toluene phase is separated by a separating funnel to remove generated hydrochloric acid. This operation is repeated three times to completely remove the hydrochloric acid. The toluene phase obtained here is heated under reduced pressure to remove toluene and take out a pale yellow solid. 580 parts of the pale yellow solid obtained here was stirred and dissolved in 460 parts of epichlorohydrin (manufactured by Aldrich), the pressure in the reaction system was adjusted to 150 mmHg, and the temperature was raised to 68 ° C. 2. While continuously dropping 75 parts of a 48% by weight aqueous sodium hydroxide solution,
The reaction was performed for 5 hours. During this time, water generated by the reaction and water of an aqueous sodium hydroxide solution were separated by refluxing a water-epichlorohydrin azeotrope, and continuously removed outside the reaction system. After completion of the reaction, the reaction system was returned to normal pressure, and the temperature was raised to 110 ° C. to completely remove water from the reaction system. The excess epichlorohydrin is removed by evaporation under normal pressure, and a further 15 m
Evaporation was carried out at 140 ° C. under a reduced pressure of mHg. 175 parts of 2-butanone and 24 parts of a 10% by weight aqueous sodium hydroxide solution were added to the resulting mixture of the resin and sodium chloride, and the mixture was reacted at a temperature of 80 to 85 ° C. for 1.5 hours. After completion of the reaction, 350 parts of 2-butanone and 200 parts of water were added, and the lower layer aqueous sodium chloride solution was separated and removed. 2-
The butanone solution layer was washed by adding 100 parts of water, neutralized with phosphoric acid, separated from the aqueous layer, and further washed with 100 parts of water to separate the aqueous layer. After removing most of the 2-butanone by evaporation under normal pressure, the 2-butanone resin solution is 5 mmH
By evaporating and drying at 140 ° C. under a reduced pressure of g, a phosphorus-containing epoxy resin having a phosphorus content of 3.0% and an epoxy equivalent of 290 g / eq was obtained.
【００４５】[0045]
【化１７】 Embedded image
【００４６】［実施例１〜８、比較例１〜５］ガラス製
フラスコに、表１及び２に示すように合成例１〜４で得
られたリン含有エポキシ樹脂、ビスフェノールＡ型エポ
キシ樹脂（日本化薬社製、商品名：ＲＥ３１０）、フェ
ノール性エポキシ樹脂硬化剤（ビフェニルアラルキルフ
ェノール樹脂、明和化成社製、商品名：ＭＥＨ−７８０
０ＳＳ）、低応力化剤として反応性液状合成ゴム（宇部
興産（株）製、商品名：ＣＴＢＮ１３００ｘ８）、トル
エンと２−ブタノンを仕込み、フラスコ内温８０℃で、
約２時間撹拌して均一な溶液を作製後に、トリフェニル
ホスフィン（北興化学社製、商品名：ＴＰＰ）を添加し
て、難燃性樹脂接着剤の溶液組成物を調製した。この溶
液組成物は、室温に１週間放置しても均一な溶液の状態
を保持していた。[Examples 1 to 8, Comparative Examples 1 to 5] As shown in Tables 1 and 2, the phosphorus-containing epoxy resin and bisphenol A type epoxy resin (Japanese Chemical product name: RE310), phenolic epoxy resin curing agent (biphenyl aralkylphenol resin, Meiwa Kasei Co., Ltd., product name: MEH-780)
0SS), a reactive liquid synthetic rubber (manufactured by Ube Industries, Ltd., trade name: CTBN1300x8), toluene and 2-butanone as a low-stressing agent, and a flask inner temperature of 80 ° C.
After stirring for about 2 hours to produce a uniform solution, triphenylphosphine (trade name: TPP, manufactured by Hokuko Chemical Co., Ltd.) was added to prepare a solution composition of a flame-retardant resin adhesive. This solution composition maintained a uniform solution state even when left at room temperature for one week.
【００４７】[0047]
【表１】 [Table 1]
【００４８】[0048]
【表２】 [Table 2]
【００４９】［比較例６，７］容量２リットルのボール
ミルに、表３に示すように臭素含有エポキシ樹脂（日本
化薬社製、商品名：ＡＥＲ−８０４９）、ビスフェノー
ルＡ型エポキシ樹脂（日本化薬社製、商品名：ＲＥ３１
０）、フェノール性エポキシ樹脂硬化剤（ビフェニルア
ラルキルフェノール樹脂、明和化成社製、商品名：ＭＥ
Ｈ−７８００ＳＳ）、３酸化アンチモン（三菱化学社
製、商品名：３酸化アンチモンＲＸ）、低応力化剤とし
て反応性液状合成ゴム（宇部興産（株）製、商品名：Ｃ
ＴＢＮ１３００ｘ８）、トルエンと２−ブタノンを仕込
み、アルミナ製ボールを２ｋｇ加えて４５ｒｐｍで約８
時間撹拌して均一な溶液を作製後にトリフェニルホスフ
ィン（北興化学社製、商品名：ＴＰＰ）を添加して、難
燃性樹脂接着剤の溶液組成物を調製した。この溶液組成
物は、室温に１週間放置しても均一な溶液の状態を保持
していた。Comparative Examples 6 and 7 A bromine-containing epoxy resin (trade name: AER-8049, manufactured by Nippon Kayaku Co., Ltd.) and a bisphenol A type epoxy resin (Nippon Kagaku Product name: RE31, manufactured by Yakusha
0), phenolic epoxy resin curing agent (biphenylaralkylphenol resin, manufactured by Meiwa Kasei Co., Ltd., trade name: ME
H-7800SS) antimony trioxide (manufactured by Mitsubishi Chemical Corporation, trade name: antimony trioxide RX), a reactive liquid synthetic rubber as a low-stressing agent (trade name: C, manufactured by Ube Industries, Ltd.)
TBN 1300x8), toluene and 2-butanone were added, 2 kg of alumina balls were added, and about 8 rpm at 45 rpm.
After stirring for an hour to prepare a uniform solution, triphenylphosphine (trade name: TPP, manufactured by Hokuko Chemical Co., Ltd.) was added to prepare a solution composition of the flame-retardant resin adhesive. This solution composition maintained a uniform solution state even when left at room temperature for one week.
【００５０】[0050]
【表３】 [Table 3]
【００５１】このようにして調製した難燃性樹脂接着剤
の溶液組成物を剥離強度、難燃性（ＪＩＳ Ｃ ６４７
１に準拠）、半田耐熱、線間絶縁抵抗の試験に供した。
以下の実験において、耐熱性フィルム基材としては東レ
・デュポン社製ポリイミドフィルム「カプトン１００
Ｖ」厚み２５μｍ、銅箔としてはジャパンエナジー社製
圧延銅箔「ＢＨＹ２２ＢＴ」厚み３５μｍを用いた。接
着強度は、島津社製の引張り試験機を用いて、剥離速度
５０ｍｍ／分で測定した結果である。The solution composition of the flame-retardant resin adhesive prepared as described above was peeled off and the flame-retardant (JIS C 647).
1), solder heat resistance, and insulation resistance between wires.
In the following experiments, a polyimide film “Kapton 100” manufactured by Du Pont-Toray Co., Ltd. was used as a heat-resistant film substrate.
V "25 μm thick, and a rolled copper foil“ BHY22BT ”manufactured by Japan Energy Co., Ltd. having a thickness of 35 μm was used as the copper foil. The adhesive strength is a result of measurement at a peeling speed of 50 mm / min using a tensile tester manufactured by Shimadzu Corporation.
【００５２】［難燃性樹脂接着剤による接着試験用積層
体の製造］前述の難燃性樹脂接着剤の溶液組成物をポリ
イミドフィルム上にドクターブレードで３０μｍの厚さ
で塗布し、次いで、その塗布層を６０℃で５分間、８０
℃で５分間、更に、１００℃で５分間加熱して乾燥し、
ポリイミドフィルム上に厚さ約１５μｍの難燃性樹脂接
着剤層を形成した。[Production of Laminate for Adhesion Test Using Flame-Retardant Resin Adhesive] The solution composition of the above-described flame-retardant resin adhesive was applied on a polyimide film with a doctor blade to a thickness of 30 μm. Apply the coating layer at 60 ° C for 5 minutes, 80
5 minutes at 100 ° C, and further dried by heating at 100 ° C for 5 minutes.
A flame-retardant resin adhesive layer having a thickness of about 15 μm was formed on the polyimide film.
【００５３】この難燃性樹脂接着剤層を有するポリイミ
ドフィルムと銅箔とを重ね合わせて、１１５℃に加熱し
たラミネートロール間を２回、圧力をかけながら通過さ
せることにより圧着し、この圧着した積層体を８０℃で
３時間、１２０℃で２時間、１５０℃で２時間、１８０
℃で３時間、窒素気流中、加熱処理して難燃性樹脂接着
剤層を硬化させ、積層体を製造した。得られた積層体の
銅箔をエッチングして、ＪＩＳ Ｃ ６４７１に準拠し
た試験片を作製して接着強度を測定した。９０度方向の
引き剥がしに関しては回転ドラム型支持金具を用いた。The polyimide film having the flame-retardant resin adhesive layer and the copper foil were overlaid and pressed twice by applying pressure between laminate rolls heated to 115 ° C. while applying pressure. The laminate was heated at 80 ° C. for 3 hours, 120 ° C. for 2 hours, 150 ° C. for 2 hours, 180 °
C. for 3 hours in a nitrogen stream to heat-treat the flame-retardant resin adhesive layer to produce a laminate. The copper foil of the obtained laminate was etched to prepare a test piece in accordance with JIS C6471, and the adhesive strength was measured. For peeling in the 90-degree direction, a rotating drum-type support was used.
【００５４】［難燃性試験片の製造］前述の接着試験用
積層体の製造と同様に、難燃性樹脂接着剤の溶液組成物
を１２．７×１２５ｍｍのポリイミドフィルム上に２６
μｍの厚さで塗布し、次いで、その塗布層を６０℃で５
分間、８０℃で５分間、更に、１００℃で５分間加熱し
て乾燥し、ポリイミドフィルム上に厚さ約１３μｍの難
燃性樹脂接着剤層を形成した。[Production of Flame-Retardant Test Specimen] In the same manner as in the production of the laminate for adhesion test described above, a solution composition of a flame-retardant resin adhesive was applied on a 12.7 × 125 mm polyimide film to form a film.
μm in thickness and then the coated layer is
And then dried at 80 ° C. for 5 minutes and further at 100 ° C. for 5 minutes to form a flame-retardant resin adhesive layer having a thickness of about 13 μm on the polyimide film.
【００５５】この難燃性樹脂接着剤層を有するポリイミ
ドフィルムを８０℃で３時間、１２０℃で２時間、１５
０℃で２時間、１８０℃で３時間、窒素気流中、加熱処
理して難燃性樹脂接着剤層を硬化させ、接着剤層を有す
るポリイミドフィルムを製造した。得られた試験片をＪ
ＩＳ Ｃ ６４７１に準拠して、３秒間接炎時の５サン
プルの合計燃焼時間を測定した。The polyimide film having the flame-retardant resin adhesive layer was cured at 80 ° C. for 3 hours, at 120 ° C. for 2 hours,
Heat treatment was performed in a nitrogen stream at 0 ° C. for 2 hours and at 180 ° C. for 3 hours to cure the flame-retardant resin adhesive layer, thereby producing a polyimide film having an adhesive layer. The obtained test piece is J
According to IS C6471, the total burning time of 5 samples during a 3-second indirect flame was measured.
【００５６】［半田耐熱試験片の製造］前述の接着試験
用積層体の製造と同様に、難燃性樹脂接着剤の溶液組成
物を２０．０×２０．０ｍｍのポリイミドフィルム上に
３０μｍの厚さで塗布し、次いで、その塗布層を６０℃
で５分間、８０℃で５分間、更に、１００℃で５分間加
熱して乾燥し、ポリイミドフィルム上に厚さ約１５μｍ
の難燃性樹脂接着剤層を形成した。[Production of Solder Heat Specimen] In the same manner as in the production of the laminate for adhesion test described above, a solution composition of a flame-retardant resin adhesive was applied on a 20.0 × 20.0 mm polyimide film to a thickness of 30 μm. And then apply the applied layer at 60 ° C.
For 5 minutes, at 80 ° C. for 5 minutes, and then at 100 ° C. for 5 minutes for drying.
Was formed.
【００５７】表４及び５に実施例１〜８、比較例１〜７
の剥離強度、難燃性（ＪＩＳ Ｃ６４７１に準拠）、半
田耐熱、線間絶縁抵抗の試験結果を示す。ここに示すよ
うに、本発明で得られた難燃性樹脂接着剤は、難燃性、
接着強度、半田耐熱、線間絶縁抵抗と環境に対する安全
性に優れることがわかった。Tables 4 and 5 show Examples 1 to 8 and Comparative Examples 1 to 7.
4 shows test results of peel strength, flame retardancy (according to JIS C6471), solder heat resistance, and line insulation resistance. As shown here, the flame-retardant resin adhesive obtained in the present invention has flame retardancy,
It was found to be excellent in adhesive strength, solder heat resistance, line insulation resistance and environmental safety.
【００５８】[0058]
【表４】 [Table 4]
【００５９】[0059]
【表５】 [Table 5]
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4J036 AA01 AA02 AA05 AD22 AF13 AJ20 DB05 FB07 JA06 JA08 4J040 EB021 EB022 EB081 EB082 EB091 EB092 EC021 EC022 EC091 EC092 EC161 EC162 EC181 EC182 EC251 EC252 GA26 JA01 JA09 JB02 KA16 LA08 MA02 MA10 MB03 NA20 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4J036 AA01 AA02 AA05 AD22 AF13 AJ20 DB05 FB07 JA06 JA08 4J040 EB021 EB022 EB081 EB082 EB091 EB092 EC021 EC022 EC091 EC092 EC161 EC162 EC181 EC182 EC251 EC08 GA02 MA03 MA09
Claims (3)
にリン成分を０．０１〜１０重量％含有するエポキシ樹
脂化合物１０〜１００重量部、その他のエポキシ樹脂化
合物１０〜１００重量部、フェノール性硬化剤１０〜１
００重量部を含有することを特徴とする難燃性樹脂接着
剤。 【化１】 ［式中、ｋは１〜１０の数、Ｘは、 【化２】 から選ばれる基（但し、Ｒ1は水素原子又は炭素数１〜
１８の１価炭化水素基を示す）、Ｙは、下記式（ｉ）〜
（ｘｉｖ）から選ばれる基を示す。］ 【化３】 【化４】 【化５】 （式中、Ｒ2は、互いに同一又は異なっていてもよく、
水素原子又は炭素数１〜１８の１価炭化水素基を示し、
ｍは０〜１０の数である。）1 to 10 parts by weight of an epoxy resin compound containing 0.01 to 10% by weight of a phosphorus component in a resin skeleton represented by the following general formula (1), 10 to 100 parts by weight of another epoxy resin compound, Phenolic curing agent 10-1
A flame-retardant resin adhesive characterized by containing 00 parts by weight. Embedded image Wherein k is a number from 1 to 10, and X is Group selected from (wherein, R 1 is 1 a hydrogen atom or a carbon atoms
18 represents a monovalent hydrocarbon group), and Y represents the following formulas (i) to
And a group selected from (xiv). ] Embedded image Embedded image (Wherein, R 2 may be the same or different from each other;
A hydrogen atom or a monovalent hydrocarbon group having 1 to 18 carbon atoms,
m is a number from 0 to 10. )
（２） 【化６】 であり、Ｒ3は、互いに同一又は異なっていてもよく、
水素原子、炭素数１〜４のアルキル基、又はフェニル基
を示し、ｎは０〜１０の数である。）で示されるもので
ある請求項１記載の難燃性樹脂接着剤。2. The phenolic curing agent is represented by the following general formula (2): R 3 may be the same or different from each other;
It represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group, and n is a number of 0 to 10. The flame-retardant resin adhesive according to claim 1, which is represented by the following formula:
合物９〜９１重量％を含有するエポキシ樹脂１００重量
部に対してフェノール性硬化剤を５〜２００重量部含有
することを特徴とする請求項１又は２記載の難燃性樹脂
接着剤。3. A phenolic curing agent is contained in an amount of 5 to 200 parts by weight based on 100 parts by weight of an epoxy resin containing 9 to 91% by weight of an epoxy resin compound represented by the general formula (1). Item 3. The flame-retardant resin adhesive according to Item 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000390892A JP2002194313A (en) | 2000-12-22 | 2000-12-22 | Flame-retardant resin adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000390892A JP2002194313A (en) | 2000-12-22 | 2000-12-22 | Flame-retardant resin adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002194313A true JP2002194313A (en) | 2002-07-10 |
Family
ID=18857163
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000390892A Pending JP2002194313A (en) | 2000-12-22 | 2000-12-22 | Flame-retardant resin adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002194313A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100108368A1 (en) * | 2007-03-20 | 2010-05-06 | Mitsui Mining & Smelting Co., Ltd. | Resin composition for forming insulating layer of printed wiring board |
| US20140205832A1 (en) * | 2013-01-22 | 2014-07-24 | Frx Polymers, Inc. | Phosphorus containing epoxy compounds and compositions therefrom |
| JP2015040289A (en) * | 2013-08-23 | 2015-03-02 | 三菱化学株式会社 | Epoxy resin, epoxy resin composition, cured product and laminate for electric/electronic circuit |
| JP2018090815A (en) * | 2018-01-30 | 2018-06-14 | 三菱ケミカル株式会社 | Epoxy resin, epoxy resin composition, cured product and laminate for electric/electronic circuit |
-
2000
- 2000-12-22 JP JP2000390892A patent/JP2002194313A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100108368A1 (en) * | 2007-03-20 | 2010-05-06 | Mitsui Mining & Smelting Co., Ltd. | Resin composition for forming insulating layer of printed wiring board |
| US8431224B2 (en) * | 2007-03-20 | 2013-04-30 | Mitsui Mining & Smelting Co., Ltd. | Resin composition for forming insulating layer of printed wiring board |
| US20140205832A1 (en) * | 2013-01-22 | 2014-07-24 | Frx Polymers, Inc. | Phosphorus containing epoxy compounds and compositions therefrom |
| CN104981474A (en) * | 2013-01-22 | 2015-10-14 | Frx聚合物股份有限公司 | Phosphorus containing epoxy compounds and compositions therefrom |
| US10167377B2 (en) * | 2013-01-22 | 2019-01-01 | Frx Polymers, Inc. | Phosphorus containing epoxy compounds and compositions therefrom |
| JP2015040289A (en) * | 2013-08-23 | 2015-03-02 | 三菱化学株式会社 | Epoxy resin, epoxy resin composition, cured product and laminate for electric/electronic circuit |
| JP2018090815A (en) * | 2018-01-30 | 2018-06-14 | 三菱ケミカル株式会社 | Epoxy resin, epoxy resin composition, cured product and laminate for electric/electronic circuit |
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