JPH0381383A - Film adhesive - Google Patents
Film adhesiveInfo
- Publication number
- JPH0381383A JPH0381383A JP1217273A JP21727389A JPH0381383A JP H0381383 A JPH0381383 A JP H0381383A JP 1217273 A JP1217273 A JP 1217273A JP 21727389 A JP21727389 A JP 21727389A JP H0381383 A JPH0381383 A JP H0381383A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- film adhesive
- film
- pts
- strength
- 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
- 239000000853 adhesive Substances 0.000 title claims abstract description 35
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 35
- 239000005011 phenolic resin Substances 0.000 claims abstract description 29
- 239000003822 epoxy resin Substances 0.000 claims abstract description 24
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 24
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 15
- 238000000465 moulding Methods 0.000 claims abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 5
- 239000004677 Nylon Substances 0.000 claims abstract description 4
- 229920001778 nylon Polymers 0.000 claims abstract description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims abstract description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 19
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 14
- 239000011342 resin composition Substances 0.000 claims description 8
- 239000011134 resol-type phenolic resin Substances 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 16
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 15
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 19
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000011162 core material Substances 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 235000013405 beer Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、接着強度、耐熱性及び難燃特性に優れたフィ
ルム接着剤に係り、さらに詳しくは高度の強度及び難燃
性が要求される航空機内装材、車両等の内装パネルある
いはビル等の建築物の内壁材に用いられるサンドイッチ
パネル等の接着に好適なフィルム接着剤に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a film adhesive having excellent adhesive strength, heat resistance, and flame retardant properties, and more specifically to film adhesives that require a high degree of strength and flame retardancy. The present invention relates to a film adhesive suitable for adhering aircraft interior materials, interior panels of vehicles, etc., and sandwich panels used for interior wall materials of buildings such as buildings.
従来より、軽量、高剛性を特色とするサンドイッチパネ
ルは、航空機内装材、車両等の内装パネルあるいは建築
物の内壁材に広く用いられている。2. Description of the Related Art Sandwich panels, which are characterized by their light weight and high rigidity, have been widely used as interior materials for aircraft, interior panels for vehicles, and interior wall materials for buildings.
従来のサンドイッチパネルの構造は、紙、金属等ででき
ているハニカム、樹脂発泡シート等の軽量芯材の両面あ
るいは片面に、繊維強化プラスチック（以下、ＦＲＰと
略す）あるいは金属製の板を張り付けたものである。ま
た、建築物の内壁材にはそのどちらか一方あるいは両面
に石材の薄板を張り付けたストーンパネルの構造を有す
るものも使用されている。Conventional sandwich panels have a structure in which fiber-reinforced plastic (hereinafter abbreviated as FRP) or metal plates are attached to both or one side of a lightweight core material such as a honeycomb or resin foam sheet made of paper or metal. It is something. In addition, the interior wall materials of buildings have a stone panel structure in which thin stone plates are attached to one or both sides of the walls.
これらのサンドイッチパネルを製造する際、スキン材と
芯材の接着には、シート状のフィルム接着剤を用いる方
法が一般的である。サンドイッチパネルに曲げ荷重がか
かった場合の耐荷重は、スキン材とコア材の接着強度が
充分でないとスキン材の強度が充分に生かせないため、
用いるフィルム接着剤としては充分な接着強度を有する
ことが要求されると共に、ハニカムあるいは発泡芯材を
用いる場合でも、接着面積が充分でないため、樹脂のフ
ローをコントロールしてスキン材とコア材の接触部分に
フィレットと称する樹脂溜まりの部分ができるような変
性を加える必要がある。このため、従来のフィルム接着
剤としては、接着強度に優れ、変性の自由度が大きいエ
ポキシ樹脂が広く用いられてきた。When manufacturing these sandwich panels, a sheet-like film adhesive is generally used to bond the skin material and the core material. When a sandwich panel is subjected to a bending load, the strength of the skin material cannot be fully utilized unless the adhesive strength between the skin material and the core material is sufficient.
The film adhesive used is required to have sufficient adhesive strength, and even when using honeycomb or foam core materials, the adhesive area is insufficient, so the flow of resin is controlled to ensure contact between the skin material and the core material. It is necessary to modify the part so that a resin pocket called a fillet is formed. For this reason, as conventional film adhesives, epoxy resins have been widely used because they have excellent adhesive strength and a large degree of freedom in modification.
一方、近年火災時の安全性の観点から、多人数が集まる
場所での内装に用いる材料の難燃規制が強化されつつあ
り、この動きは先ず航空機の内装材に始まり、次第に車
両等の内装パネルや建築物の内壁材にも広がりつつある
。このため、航空機の内装材においては、今まで広範に
使用されてきた難燃エポキシ樹脂を用いたスキン材ある
いはフィルム接着剤でも、燃焼時の発煙、発熱の点で今
後はその使用が難しくなり、材料の代替が必要になって
きた。その結果、古くから難燃特性が良いことで知られ
ているフェノール樹脂の使用が着目される用になってき
た。しかしながら、このフェノール樹脂は、確かに難燃
特性においてはエポキシ樹脂を凌駕し、熱硬化性樹脂と
しては最高の特性を有しているが、力学的特性において
エポキシ樹脂に及ばず、いわゆる脆い樹脂であるため、
スキン材においては強化繊維の強度を充分発現し得す、
また、接着剤として使用した場合でもその接着強度が低
いという問題があった。すなわち、フェノール樹脂を使
用した場合には、その難燃特性は良好であるが、強度が
低く、エポキシ樹脂と同等の強度を得るためには補強材
が余計に必要になり、サンドイッチパネルにすることに
よる軽量効果が充分に発揮されないという問題があった
。さらに、フェノール樹脂は、溶剤を含んでいるために
フィルム接着剤に加工するのが難しく、しかも、フロー
コントロールのための変性の自由度が小さいという問題
がある。On the other hand, in recent years, from the perspective of safety in the event of a fire, flame-retardant regulations have been tightened for materials used for interior decoration in places where large numbers of people gather. It is also spreading to interior wall materials of buildings. For this reason, skin materials or film adhesives made of flame-retardant epoxy resins, which have been widely used until now, will become difficult to use in aircraft interior materials due to the smoke and heat generated during combustion. There is a need for alternative materials. As a result, the use of phenolic resins, which have long been known for their good flame retardant properties, has been attracting attention. However, although this phenolic resin certainly surpasses epoxy resin in flame retardant properties and has the best properties as a thermosetting resin, it is not as good as epoxy resin in mechanical properties and is a so-called brittle resin. Because there is
In skin materials, the strength of reinforcing fibers can be fully expressed.
Furthermore, even when used as an adhesive, there was a problem that the adhesive strength was low. In other words, when phenolic resin is used, its flame retardant properties are good, but its strength is low, and extra reinforcing material is required to obtain the same strength as epoxy resin, making it difficult to use sandwich panels. There was a problem in that the lightweight effect of Furthermore, since phenolic resins contain solvents, it is difficult to process them into film adhesives, and furthermore, there are problems in that the degree of freedom in modification for flow control is small.
本発明の目的は、フェノール樹脂の持つ優れた難燃特性
を保持しつつ、エポキシ樹脂並みの力学的特性、接着強
度を備えたフィルム接着剤を提供することにある。An object of the present invention is to provide a film adhesive that has mechanical properties and adhesive strength comparable to epoxy resins while retaining the excellent flame retardant properties of phenolic resins.
すなわち、本発明は、少なくともフェノール樹脂とこの
フェノール樹脂に対して相溶性を有する熱可塑性樹脂と
を含む樹脂組成物を薄いシート状に成形してなるフィル
ム接着剤である。That is, the present invention is a film adhesive formed by molding into a thin sheet a resin composition containing at least a phenol resin and a thermoplastic resin that is compatible with the phenol resin.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明で使用されるフェノール樹脂は、一般に知られて
いるノボラック型フェノール樹脂及びレゾール型フェノ
ール樹脂のいずれでもよいが、フィルム加工の容易さや
フィルムの取扱い易さの点から、液状のレゾール型フェ
ノール樹脂が好適に使用される。また、このフェノール
樹脂については、イソシアネートと反応させたウレタン
変性フェノール樹脂もその難燃性をあまり悪化させない
範囲で使用できる。The phenolic resin used in the present invention may be any of the generally known novolak type phenolic resins and resol type phenolic resins, but from the viewpoint of ease of film processing and film handling, liquid resol type phenolic resins are preferred. is preferably used. Regarding this phenol resin, urethane-modified phenol resins reacted with isocyanate can also be used as long as their flame retardance is not significantly deteriorated.
フェノール樹脂に添加される熱可塑性樹脂は、ベースの
フェノール樹脂に対して相溶性を有することが必要であ
り、また、その添加方法については特に制限があるもの
ではなく、ホットメルトによる方法でも、また、溶剤に
溶解してから添加する方法でもよい。特に好適に使用さ
れる熱可塑性樹脂としては、アルコール可溶性の共重合
ナイロン、ポリビニルホルマール、ポリビニルアセクー
ル、ポリビニルブチラール、ダイマー酸ポリアミド等が
挙げられる。これらの熱可塑性樹脂は、フェノール樹脂
に対して優れた相溶性を有するばかりでなく、それ自体
が揮発分を含んでいないため、樹脂組成物を薄く引き延
ばしフィルム状に成形した場合、ある程度の強度としな
やかさを兼ね備えた非常に使い勝手の良いフィルムとな
り、大変好ましいものである。また、熱可塑性樹脂自体
が非常に靭性の高いものであるため、大きな靭性改良効
果が発揮され、同時にフェノール樹脂のフローをコント
ロールするため、ハニカムサンドイッチパネルのフィル
ム接着剤として使用した場合に良好なフィレットを形成
し、エポキシ樹脂並みの接着強度を得ることができる。The thermoplastic resin added to the phenolic resin must be compatible with the base phenolic resin, and there are no particular restrictions on the method of addition; Alternatively, it may be added after being dissolved in a solvent. Particularly preferably used thermoplastic resins include alcohol-soluble copolymerized nylon, polyvinyl formal, polyvinyl acecool, polyvinyl butyral, dimer acid polyamide, and the like. These thermoplastic resins not only have excellent compatibility with phenolic resins, but also contain no volatile matter, so when the resin composition is stretched thin and formed into a film, it has a certain degree of strength and strength. The film is extremely flexible and easy to use, which is very desirable. In addition, since the thermoplastic resin itself is extremely tough, it exhibits a large toughness improvement effect, and at the same time controls the flow of the phenolic resin, resulting in a good fillet when used as a film adhesive for honeycomb sandwich panels. It forms an adhesive strength comparable to that of epoxy resin.
これらの熱可塑性樹脂の使用量は、フェノール樹脂１０
０重量部に対して１０〜４００重量部、好ましくは１０
〜２５０重量部である。これより少ないと靭性向上、フ
ローコントロール性及びフィルム加工性に問題が生じ、
また、これより多くなると難燃性の低下が問題になる。The amount of these thermoplastic resins used is 10% of the phenolic resin.
10 to 400 parts by weight, preferably 10 parts by weight
~250 parts by weight. If the amount is less than this, there will be problems in improving toughness, flow control and film processability.
Moreover, if the amount exceeds this range, a decrease in flame retardancy becomes a problem.
本発明の樹脂組成物において、熱可塑性樹脂の相溶性、
フィルム加工性、硬化物靭性等を改良するために、エポ
キシ樹脂を添加して変性することも好ましい態様である
。添加されるエポキシ樹脂は、添加効果に応じて種々使
い分けられるが、基本的にはどのようなエポキシ樹脂で
も使用可能である。−例を示すならば、エピコート８２
８．１００１．１００７ （油化シェルエポキシ■社製
）のような液状または固形状のビスフェノールＡ型エポ
キシ樹脂や、ＤＥＮ４３１（ダウケミカル日本一社製）
のようなフェノールノボラック型エポキシ樹脂や、ＥＣ
Ｎ１２７３（日本チバガイギー味社製）のようなりレゾ
ールノボラック型エポキシ樹脂や、エビクロン８３０（
大日本インキ工業−社製）のようなビスフェノールＦ型
エポキシ樹脂や、ＥＬＭ−４３４、ＥＬＭ−１２０（住
友化学工業■社製）のようなグリシジルアミン型エポキ
シ樹脂のほか、臭素化エポキシ樹脂、グリシジルエステ
ル型エポキシ樹脂、脂環式エポキシ樹脂等を挙げること
ができる。このエポキシ樹脂の添加量は、最終硬化物特
性のバランスを考慮して決定されるが、ベースのフェノ
ール樹脂１００重量部に対し、通常０〜５０重量部、好
ましくは０〜３０重量部の範囲である。In the resin composition of the present invention, the compatibility of the thermoplastic resin,
In order to improve film processability, cured product toughness, etc., it is also a preferred embodiment to add and modify an epoxy resin. Various epoxy resins can be used depending on the effect of addition, but basically any epoxy resin can be used. - To give an example, Epicote 82
Liquid or solid bisphenol A type epoxy resin such as 8.1001.1007 (manufactured by Yuka Shell Epoxy ■) or DEN431 (manufactured by Dow Chemical Nippon Ichi)
Phenol novolak type epoxy resin such as EC
Resol novolac type epoxy resin such as N1273 (manufactured by Nippon Ciba Geigy Aji Co., Ltd.), Evicron 830 (
In addition to bisphenol F-type epoxy resins such as Dainippon Ink Industries (manufactured by Dainippon Ink Industries, Ltd.) and glycidylamine-type epoxy resins such as ELM-434 and ELM-120 (manufactured by Sumitomo Chemical Industries, Ltd.), brominated epoxy resins, glycidyl Examples include ester type epoxy resins and alicyclic epoxy resins. The amount of this epoxy resin added is determined by considering the balance of the properties of the final cured product, but it is usually in the range of 0 to 50 parts by weight, preferably 0 to 30 parts by weight, based on 100 parts by weight of the base phenolic resin. be.
その他、特性を悪化させない範囲で、難燃材、フィラー
、染料、硬化促進剤、反応遅延剤等の各種の添加剤を添
加することもできる。In addition, various additives such as flame retardants, fillers, dyes, curing accelerators, reaction retarders, etc. can also be added within a range that does not deteriorate the properties.
フィルム加工には二つの方法が考えられる。先ず、ベー
スのフェノール樹脂、熱可塑性樹脂及びその他の添加剤
を含んだ樹脂組成物溶液を調製し、表面をシリコン離型
加工した紙等の上にこの樹脂組成物溶液を塗布し、次い
で溶剤を除去してフィルムを得る方法であり、また、ベ
ースのフェノール樹脂に熱可塑性樹脂を加熱溶解させ、
次いで添加剤を添加し、常温で使いやすい粘度になるま
でフェノール樹脂中の揮発分を除去した後、適当な温度
に加熱し離型紙上に薄く塗布してフィルムを得る方法で
ある。There are two possible methods for film processing. First, a resin composition solution containing a base phenolic resin, a thermoplastic resin, and other additives is prepared, and this resin composition solution is applied onto paper, etc. whose surface has been treated with silicone mold release, and then a solvent is removed. This is a method to obtain a film by removing the thermoplastic resin.
Next, additives are added and the volatile matter in the phenol resin is removed until the viscosity becomes easy to use at room temperature, then heated to an appropriate temperature and coated thinly on release paper to obtain a film.
これら両方法を比較すると、前者は熱可塑性樹脂の含有
率が高く、高粘度の樹脂をフィルム状にするのに適して
おり、設備も比較的簡単なもので製造可能であり、また
、後者の方法は、設備が複雑になり高価になってしまい
、また使用可能な樹脂粘度の範囲が狭いという問題があ
るが、厚みや重量の精密なコントロールが可能である。Comparing these two methods, the former has a high content of thermoplastic resin and is suitable for making a high viscosity resin into a film, and can be manufactured with relatively simple equipment, while the latter Although this method requires complicated and expensive equipment and has a narrow range of usable resin viscosities, it allows precise control of thickness and weight.
これら両方法は、目的のプリプレグ接着剤の品質、要求
特性、樹脂組成にあわせて使い分けるのがよい。Both of these methods are preferably used depending on the quality, required characteristics, and resin composition of the target prepreg adhesive.
以上のようにして作成されたフェノール樹脂フィルムは
、成形時に芯材とスキン材の間に置き、プレス成形機あ
るいはオートクレーブ等によって加熱成形することによ
り、サンドイッチパネルとすることができる。その際、
スキン材となるプリプレグは、予め成形済のものでも、
また、Ｂ−ステージの状態でフィルム接着剤と同時に硬
化してもよい。The phenolic resin film produced as described above can be made into a sandwich panel by placing it between a core material and a skin material during molding and heat-forming it using a press molding machine, an autoclave, or the like. that time,
The prepreg used as the skin material may be pre-formed,
Further, the film adhesive may be cured simultaneously in the B-stage state.
以下、実施例及び比較例に基づいて、本発明を具体的に
説明する。The present invention will be specifically described below based on Examples and Comparative Examples.
実施例１
（１）フィルム接着剤の製造
クレゾールを用いたレゾール型フェノール樹脂（大日本
インキ化学工業社製ニブライオ−フェンＪ３２６Ｋ、固
形分濃度：６１．２ｗｔＸ、 ２５℃粘度：１１３ｃｐ
ｓ 、 １５０℃ゲル化時間：２分、使用溶剤：メタノ
ール）３０重量部に対し、共重合ナイロン（東し■社製
： ＣＭ−６０００） ７０重量部、エポキシ樹脂（油
化シェルエポキシ社製：エピコート１００１） １０
重量部、及び、難燃剤として三酸化アンチセフ１０重量
部を、エタノール：塩化メチレン＝１００＝５の混合溶
剤に投入し、均一になるまで攪拌し、さらに室温で３０
分間攪拌した後、樹脂溶液をナイフコーターを使用して
離型紙上に薄く塗布した。Example 1 (1) Production of film adhesive Resol-type phenolic resin using cresol (Nibryophen J326K manufactured by Dainippon Ink Chemical Industries, Ltd., solid content concentration: 61.2 wtX, 25°C viscosity: 113 cp)
s, 150°C gelation time: 2 minutes, solvent used: 30 parts by weight of methanol, 70 parts by weight of copolymerized nylon (manufactured by Toshi ■ Co., Ltd.: CM-6000), epoxy resin (manufactured by Yuka Shell Epoxy Company: Epicote 1001) 10
Parts by weight and 10 parts by weight of anticeph trioxide as a flame retardant were added to a mixed solvent of ethanol: methylene chloride = 100 = 5, stirred until homogeneous, and further stirred at room temperature for 30 minutes.
After stirring for a minute, the resin solution was thinly applied onto release paper using a knife coater.
その後、室温で４時間放置して溶剤を揮発させた。その
結果、厚さ３５湘、目付４０ ｇ／ｒｒｒのしなやかで
強靭なフィルム接着剤が得られた。Thereafter, the solution was allowed to stand at room temperature for 4 hours to evaporate the solvent. As a result, a flexible and strong film adhesive having a thickness of 35 cm and a basis weight of 40 g/rrr was obtained.
（２）サンドイッチパネルの成形
ガラスクロス（クラークシューベル社製、７７８１タイ
プ、８枚朱子織、日付３０４ｇ／ｒｒｒ；）にフェノー
ル樹脂を含浸させたガラスクロスプリプレグ（新日鐵化
学■製： Ｌ−５２５、樹脂含有率３６ｗｔＸ） ２プ
ライと上記（１）で作成したフィルム接着剤１プライと
を重ね合わせ、ノーメックスハニカムコア（昭和飛行機
社製： ５ＡＨＩ／８−３．０ ）の両側にフィルム接
着剤がハニカム側になるようにして貼り合わせ、熱プレ
スを使用して１３５℃Ｘ６０分間、３ ｋｇ ／ ｃＴ
ｌの条件でハニカムサンドイッチパネルを成形した。(2) Glass cloth prepreg (manufactured by Nippon Steel Chemical Co., Ltd.: L-525) made by impregnating phenolic resin with molded glass cloth for the sandwich panel (manufactured by Clark Schubel Co., Ltd., 7781 type, 8-ply satin weave, date 304 g/rrr;) , resin content 36 wt Laminate with the honeycomb side facing up, and use a heat press to press at 135℃ for 60 minutes at 3 kg/cT.
A honeycomb sandwich panel was molded under the following conditions.
このパネルのドラムビール強度を測定した結果、１１．
５ｋｇ・インチ／３インチの剥離強度であった。また、
燃焼特性を評価するためにＯ８Ｕ試験を行った結果、２
分間のトータル熱量は４２ｋｗ・ｍｉｎ／ｒｒｒ、 ５
分間までの発熱量のピークは４５ｋｗ／ｄであって良好
な難燃特性を有していた。As a result of measuring the drum beer strength of this panel, 11.
The peel strength was 5 kg·inch/3 inches. Also,
As a result of O8U test to evaluate combustion characteristics, 2
Total heat amount per minute is 42kw・min/rrr, 5
The peak of the calorific value within minutes was 45 kW/d, and it had good flame retardant properties.
比較例１
フィルム接着剤を用いなかったこと以外は実施例１と全
く同じ方法でハニカムサンドイッチパネルを成形し、得
られたパネルのドラムビール強度を測定した結果、５．
３ｋｇ・インチ／３インチと非常に低い剥離強度であっ
た。また、このパネルについて実施例１と同様にＯ８Ｕ
試験を行った結果、２分間のトータル熱量は３９ ｋｗ
−ｍｉｎ／ｒｒｒ、５分間までの発熱量のピークは４１
ｋｗ／ｒｒ？であって、良好な難燃特性を示した。Comparative Example 1 A honeycomb sandwich panel was formed in exactly the same manner as in Example 1 except that no film adhesive was used, and the drum beer strength of the resulting panel was measured.
The peel strength was very low at 3 kg·inch/3 inches. Also, regarding this panel, as in Example 1, O8U
As a result of the test, the total heat amount for 2 minutes was 39 kW.
-min/rrr, peak calorific value up to 5 minutes is 41
kw/rr? It showed good flame retardant properties.
比較例２
実施例１で作成したフェノール樹脂及び熱可塑性樹脂主
成分のフィルム接着剤に代えて、エポキシ樹脂フィルム
接着剤（アメリカンシアナミド社製：ＦＭ−１２３−２
、目付１５０ ｇ／ｒｒｒ）を使用した以外は、実施例
１と全く同様にしてハニカムサンドイッチパネルを成形
した。Comparative Example 2 An epoxy resin film adhesive (manufactured by American Cyanamid Co., Ltd.: FM-123-2) was used instead of the film adhesive mainly composed of phenolic resin and thermoplastic resin prepared in Example 1.
A honeycomb sandwich panel was molded in exactly the same manner as in Example 1, except that a honeycomb sandwich panel was used.
このパネルのドラムビール強度を測定した結果、１３．
３ｋｇ・インチ／３インチと非常に高い剥離強度を示し
た。また、このパネルについて実施例１と同様にＯ８Ｕ
試験を行った結果、２分間のトータル熱量は７４ ｋｗ
−ｍｉｎ／ｒｒｒ、 ５分間までの発熱量のピークは８
１ｋｗ／ｒｒｌ’であって、難燃特性の点で劣っていた
。As a result of measuring the drum beer strength of this panel, 13.
It exhibited a very high peel strength of 3 kg·inch/3 inches. Also, regarding this panel, as in Example 1, O8U
As a result of the test, the total heat amount for 2 minutes was 74 kW.
-min/rrr, the peak of calorific value up to 5 minutes is 8
1kw/rrl', and was inferior in terms of flame retardant properties.
実施例２
クレゾールを用いたレゾール型フェノール樹脂（大日本
インキ化学工業社製ニブライオ−フェンＪ３２６に、固
形分濃度＋６１．２ｗｔＸ、 ２５℃粘度＝１１３ｃｐ
ｓ 、 １５０℃ゲル化時間：２分、使用溶剤：メタノ
ール）３０重量部に対し、ポリビニルホルマール（電気
化学工業社製：＃２０）、７０重量部、エポキシ樹脂（
油化シェルエポキシ社製：エピコート１００１） １
０重量部、及び、難燃剤として三酸化アンチセフ１０重
量部を、エタノール：塩化メチレン＝１００：５の混合
溶剤に投入し、均一になるまで攪拌し、さらに室温で３
０分間攪拌した後、樹脂溶液をナイフコーターを使用し
て離型紙上に薄く塗布した。その後、室温にて４時間放
置し溶剤を揮発させ、厚さ４５湘、日付６０ｇ／ｒｒ１
′のしなやかで強靭なフィルム接着剤を得た。Example 2 A resol-type phenolic resin using cresol (Nibryophen J326 manufactured by Dainippon Ink Chemical Industries, Ltd., solid content concentration + 61.2 wtX, 25°C viscosity = 113 cp)
s, 150°C gelation time: 2 minutes, solvent used: 30 parts by weight of methanol, 70 parts by weight of polyvinyl formal (manufactured by Denki Kagaku Kogyo Co., Ltd.: #20), epoxy resin (
Manufactured by Yuka Shell Epoxy Co., Ltd.: Epicoat 1001) 1
0 parts by weight and 10 parts by weight of anticeph trioxide as a flame retardant were added to a mixed solvent of ethanol:methylene chloride = 100:5, stirred until homogeneous, and further stirred at room temperature for 3.
After stirring for 0 minutes, the resin solution was thinly applied onto release paper using a knife coater. After that, it was left at room temperature for 4 hours to volatilize the solvent, and the thickness was 45 cm and the date was 60 g/rr1.
A flexible and tough film adhesive was obtained.
次に、上記実施例１と全く同様にしてハニカムサンドイ
ッチパネルを成形した。このパネルのドラムビール強度
を測定したところ１２．２ｋｇ・インチ／３インチの剥
離強度であった。また、燃焼特性評価のためのＯ８Ｕ試
験の結果、２分間のトータル熱量は４６ ｋｗ−ｍｉｎ
／ｒｒ＋’、 ５分間までの発熱量のピークは４９ｋｗ
／ｒｒｒであり、良好な難燃特性を有していることが判
明した。Next, a honeycomb sandwich panel was molded in exactly the same manner as in Example 1 above. When the drum beer strength of this panel was measured, it was found to have a peel strength of 12.2 kg·inch/3 inches. In addition, as a result of the O8U test to evaluate combustion characteristics, the total heat amount for 2 minutes was 46 kW-min.
/rr+', peak calorific value up to 5 minutes is 49kW
/rrr, and was found to have good flame retardant properties.
本発明のフィルム接着剤は、これを用いて成形されるサ
ンドイッチパネルが剥離強度に優れ、しかも、フェノー
ル樹脂のもつ難燃性を備えているため、従来のエポキシ
樹脂を用いて形成されるパネルに比べてその燃焼時の発
熱、発煙が大幅に減少し、特に燃焼、軽量、高強度とい
った特性が要求される航空機内装材、車両等の内装パネ
ルあるいは建築物の内壁材の用途に有用である。The film adhesive of the present invention has excellent peel strength in sandwich panels formed using it, and also has the flame retardant properties of phenolic resin, making it superior to panels formed using conventional epoxy resin. Compared to this, heat generation and smoke generation during combustion are significantly reduced, and it is particularly useful for applications such as aircraft interior materials, vehicle interior panels, and building interior wall materials that require characteristics such as combustion, light weight, and high strength.
Claims (4)
に対して相溶性を有する熱可塑性樹脂とを含む樹脂組成
物を薄いシート状に成形してなるフィルム接着剤。(1) A film adhesive formed by molding into a thin sheet a resin composition containing at least a phenol resin and a thermoplastic resin that is compatible with the phenol resin.
樹脂を含有する請求項１記載のフィルム接着剤。(2) The film adhesive according to claim 1, wherein the resin composition contains an epoxy resin as one of its constituent components.
る請求項１又は２記載のフィルム接着剤。(3) The film adhesive according to claim 1 or 2, wherein the phenolic resin is a resol type phenolic resin.
マール及びポリビニルブチラールから選択された１種又
は２種以上の混合物である請求項１〜３のいずれかに記
載のフィルム接着剤。(4) The film adhesive according to any one of claims 1 to 3, wherein the thermoplastic resin is one or a mixture of two or more selected from copolymerized nylon, polyvinyl formal, and polyvinyl butyral.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1217273A JPH0381383A (en) | 1989-08-25 | 1989-08-25 | Film adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1217273A JPH0381383A (en) | 1989-08-25 | 1989-08-25 | Film adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0381383A true JPH0381383A (en) | 1991-04-05 |
Family
ID=16701558
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1217273A Pending JPH0381383A (en) | 1989-08-25 | 1989-08-25 | Film adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0381383A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007157758A (en) * | 2005-11-30 | 2007-06-21 | Sumitomo Bakelite Co Ltd | Adhesive film for semiconductor and semiconductor device using the same |
| JP2008063441A (en) * | 2006-09-07 | 2008-03-21 | Sumitomo Bakelite Co Ltd | Liquid phenolic resin composition |
-
1989
- 1989-08-25 JP JP1217273A patent/JPH0381383A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007157758A (en) * | 2005-11-30 | 2007-06-21 | Sumitomo Bakelite Co Ltd | Adhesive film for semiconductor and semiconductor device using the same |
| JP2008063441A (en) * | 2006-09-07 | 2008-03-21 | Sumitomo Bakelite Co Ltd | Liquid phenolic resin composition |
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