JP5536971B2 - Multilayer adhesive sheet, heat exchanger forming material and heat exchanger - Google Patents
Multilayer adhesive sheet, heat exchanger forming material and heat exchanger Download PDFInfo
- Publication number
- JP5536971B2 JP5536971B2 JP2006013274A JP2006013274A JP5536971B2 JP 5536971 B2 JP5536971 B2 JP 5536971B2 JP 2006013274 A JP2006013274 A JP 2006013274A JP 2006013274 A JP2006013274 A JP 2006013274A JP 5536971 B2 JP5536971 B2 JP 5536971B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- adhesive sheet
- heat exchanger
- multilayer adhesive
- thermosetting resin
- 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.)
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- 230000001070 adhesive effect Effects 0.000 title claims description 96
- 239000000853 adhesive Substances 0.000 title claims description 95
- 239000000463 material Substances 0.000 title claims description 35
- 229920005989 resin Polymers 0.000 claims description 58
- 239000011347 resin Substances 0.000 claims description 57
- 229920001187 thermosetting polymer Polymers 0.000 claims description 43
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 24
- 229910052782 aluminium Inorganic materials 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 146
- 229920000647 polyepoxide Polymers 0.000 description 41
- 239000003822 epoxy resin Substances 0.000 description 37
- 238000001723 curing Methods 0.000 description 26
- 238000011049 filling Methods 0.000 description 22
- 229920000800 acrylic rubber Polymers 0.000 description 21
- 229920000058 polyacrylate Polymers 0.000 description 21
- -1 1-heptyl group Chemical group 0.000 description 19
- 229920000459 Nitrile rubber Polymers 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 17
- 238000000576 coating method Methods 0.000 description 17
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- 239000003795 chemical substances by application Substances 0.000 description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 11
- 239000011162 core material Substances 0.000 description 10
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- 125000000217 alkyl group Chemical group 0.000 description 5
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000012790 adhesive layer Substances 0.000 description 4
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- 238000002844 melting Methods 0.000 description 4
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
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- 238000005452 bending Methods 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
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- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
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Images
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Description
本発明は、最適な形状に部品加工し、組付後、加熱硬化させることによって構造物を作製するための多層接着シート、特に複雑な形状を有する被着物表面に対し精度よく接着するために、被着物と多層接着シートとの間に発生する隙間への充填性と接着強度とを高い次元で両立した多層接着シート、熱交換器形成用材料及びそれらを用いて作製された熱交換器に関するものである。 The present invention is a multilayer adhesive sheet for producing a structure by processing a part into an optimal shape, assembling, and then heat-curing, particularly in order to adhere with high accuracy to an adherend surface having a complicated shape. A multi-layer adhesive sheet that achieves a high level of compatibility between filling properties and adhesive strength in a gap generated between an adherend and a multi-layer adhesive sheet, a heat exchanger forming material, and a heat exchanger made using them It is.
従来から、アルミニウム製熱交換器を製造する場合には、アルミニウムのシートを材料にして、ある形状に部品加工し、組み付けることが行われている。そのアルミニウムシートとしては、芯材として５００〜１０００μｍ程度の厚みのアルミニウム材料の片面若しくは両面に、芯材としてのアルミニウム材料よりも融点の低い同じアルミニウム材料をろう材として積層した構成のもの（特許文献１参照）が用いられている。 Conventionally, when manufacturing an aluminum heat exchanger, an aluminum sheet is used as a material, parts are processed into a certain shape and assembled. The aluminum sheet has a structure in which the same aluminum material having a melting point lower than that of the aluminum material as the core material is laminated as a brazing material on one or both sides of the aluminum material having a thickness of about 500 to 1000 μm as the core material (Patent Document) 1) is used.
一方、アルミニウム製のろう材の場合は、その溶融温度が通常５７７℃程度であるため、接合時にその温度あるいはそれ以上のろう付け温度（約６００℃）まで上昇させなければならず、ろう付け時に消費するエネルギーが大きいので、アルミニウム製のろう材に代えて、樹脂をコーティングした構成のアルミニウムシート（特許文献２参照）が提案されている。 On the other hand, in the case of a brazing material made of aluminum, its melting temperature is usually around 577 ° C., so it must be raised to that temperature or higher (about 600 ° C.) at the time of joining. Since the energy consumed is large, an aluminum sheet (see Patent Document 2) having a structure in which a resin is coated instead of the brazing material made of aluminum has been proposed.
近年、車載用エアコン等では特に熱交換器の軽量化が求められており、そのためには芯材であるアルミニウム材料を５００μｍ若しくはそれ以下の厚みにしなければならない。ところが、アルミニウム材料を薄くすると強度が低下するので、芯材の強度を向上させるためにマグネシウム、銅、ケイ素等の元素を添加した高強度アルミニウム合金を用いる必要がある。 In recent years, in-vehicle air conditioners and the like are particularly required to reduce the weight of heat exchangers, and for this purpose, the aluminum material that is a core material must have a thickness of 500 μm or less. However, since the strength decreases when the aluminum material is thinned, it is necessary to use a high-strength aluminum alloy to which elements such as magnesium, copper, and silicon are added in order to improve the strength of the core material.
しかしながら、それらの合金は元素添加量を増やすと、強度は向上するものの、融点が低下するなどして、ろう材を積層したアルミニウムシートにおいてはろう付け性が著しく低下するという問題がある。一方、消費エネルギーを低下させるために樹脂をコーティングしたアルミニウムシートも提案されているが、湾曲した部分での接着強度が不十分であったり、耐熱性に劣るなどの問題があり、ろう付けに変わる十分に信頼に値する接着シート材料が求められている。 However, although the strength of these alloys increases when the element addition amount is increased, there is a problem that the brazing property is remarkably lowered in the aluminum sheet laminated with the brazing material because the melting point is lowered. On the other hand, an aluminum sheet coated with a resin has also been proposed in order to reduce energy consumption, but there are problems such as insufficient adhesion strength at the curved part and poor heat resistance, and it changes to brazing. There is a need for adhesive sheet materials that are sufficiently reliable.
そこで、本出願人は、金属シートの少なくとも片面に、機能の異なる熱硬化性樹脂層を少なくとも２層有する多層接着シート、特に金属シートに接する熱硬化性樹脂層として特定の引張せん断強度、弾性率、ガラス転移温度等を有する熱硬化性樹脂層を用いたことを特徴とする多層接着シート（特許文献３参照）を提案しているが、接着剤にかかる応力が大きくなるに伴って、金属と接しない接着層部分が破壊されるという問題が生じる場合があった。 Therefore, the applicant of the present invention has a specific tensile shear strength and elastic modulus as a multilayer adhesive sheet having at least two thermosetting resin layers having different functions on at least one side of the metal sheet, particularly as a thermosetting resin layer in contact with the metal sheet. Has proposed a multilayer adhesive sheet (see Patent Document 3) characterized by using a thermosetting resin layer having a glass transition temperature or the like, but as the stress applied to the adhesive increases, In some cases, the adhesive layer portion that is not in contact is broken.
また、金属シートの片面に樹脂材料を被覆したプレコート材から熱交換器を製造する方法（特許文献４〜６参照）や、非金属材料からなる構成部材相互が接着材で接着されている熱交換器（特許文献７参照）なども知られている。しかしながら、これらの特許文献等に記載の技術においても、上記したような樹脂層破壊の問題を解決できるものではない。
本発明は、熱交換器を軽量化しようとした場合に生じる前記のような問題点に着目してなされたものである。すなわち、本発明は、厚みが５００μｍ以下のアルミニウム材料の芯材を用いても十分に信頼できる接着強度を有する多層接着シート、特に、構造が複雑な形状の場合には多層接着シートを湾曲して重ね合せなければならないが、そのような湾曲したシート部同士の薄い隙間にも接着剤が十分流動充填することによって、湾曲した部分でも浮きの発生が抑えられて接着強度の低下や硬化物の破損・破壊が生じず、また接着剤に係る応力が大きくなっても金属と接しない接着層部分が破壊されない多層接着シートを提供すること、及びその多層接着シートからなる熱交換器形成用材料とそれを用いて作製された熱交換器を提供することをその課題とする。 The present invention has been made paying attention to the above-described problems that occur when attempting to reduce the weight of a heat exchanger. That is, the present invention provides a multilayer adhesive sheet having a sufficiently reliable adhesive strength even when a core material made of an aluminum material having a thickness of 500 μm or less is used. In particular, in the case of a complicated structure, the multilayer adhesive sheet is curved. Although the adhesive must be fluidly filled into such a thin gap between the curved sheet parts, the occurrence of floating can be suppressed even in the curved part, resulting in a decrease in adhesive strength and damage to the cured product. Provided is a multilayer adhesive sheet that does not break and does not break the adhesive layer portion that does not contact the metal even when the stress on the adhesive increases, and a heat exchanger forming material comprising the multilayer adhesive sheet, and It is an object of the present invention to provide a heat exchanger manufactured using the above.
本発明者らは、前記課題を解決すべく鋭意研究を重ねた結果、金属シートの少なくとも片面に、機能の異なる熱硬化性樹脂のＡ層とＢ層とをこの順に積層し、しかもＢ層に特定の材料を配合することにより、金属シート厚を薄くしても十分な接着強度を有し、また湾曲した形状に組み付ける場合でも、浮き等が発生せずに接合することを可能にする多層接着シートを得ることができることを見出し、この知見に基づいて本発明をなすに至った。すなわち、本発明によれば、以下に示す多層接着シート、熱交換器材料、熱交換器の製造方法及び熱交換器が提供される。 As a result of intensive studies to solve the above-mentioned problems, the present inventors laminated A layer and B layer of thermosetting resins having different functions in this order on at least one side of the metal sheet, and in addition to the B layer. Multi-layer adhesion that has sufficient adhesive strength even if the metal sheet thickness is reduced by blending specific materials, and can be joined without floating even when assembled in a curved shape The present inventors have found that a sheet can be obtained, and have reached the present invention based on this finding. That is, according to the present invention, the following multilayer adhesive sheet, heat exchanger material, heat exchanger manufacturing method, and heat exchanger are provided.
［１］金属シートの少なくとも片面に、組成の異なる熱硬化性樹脂のＡ層と熱硬化性樹脂のＢ層とを有する多層接着シートであって、該Ａ層は該金属シート上に、該Ｂ層は該Ａ層上にそれぞれ設けられ、かつ該Ｂ層が、アクリルゴムを含有する多層接着シート。 [1] A multilayer adhesive sheet having a thermosetting resin layer A and a thermosetting resin layer B having different compositions on at least one side of a metal sheet, the layer A being formed on the metal sheet and the layer B multilayer adhesive sheet layers respectively provided on the a layer, and the layer B, containing a Kurirugomu.
［２］前記熱硬化性樹脂が、エポキシ系の熱硬化性樹脂である前記［１］に記載の多層接着シート。 [ 2 ] The multilayer adhesive sheet according to [1 ], wherein the thermosetting resin is an epoxy thermosetting resin.
［３］前記金属シートが、アルミニウム材料である前記［１］又は［２］に記載の多層接着シート。 [ 3 ] The multilayer adhesive sheet according to [1] or [2] , wherein the metal sheet is an aluminum material.
［４］前記［１］から［３］の何れか一項に記載の多層接着シートからなる熱交換器形成用材料。 [ 4 ] A material for forming a heat exchanger comprising the multilayer adhesive sheet according to any one of [1] to [ 3 ].
［５］前記［４］に記載の熱交換器形成用材料を接着加工することにより熱交換器を形成する熱交換器の製造方法。 [ 5 ] A method for producing a heat exchanger, wherein the heat exchanger is formed by bonding the heat exchanger forming material according to [ 4 ].
［６］前記［４］に記載の熱交換器形成用材料を接着加工することにより形成された熱交換器。 [ 6 ] A heat exchanger formed by bonding the heat exchanger forming material according to [ 4 ].
本発明の多層接着シートは、接着強度に優れるとともに、その部品の形状が複雑で積層シートを湾曲して積層しなければならない場合であっても、浮きが発生せずに強固に接着できる特性を有している。それは、その多層接着シートの湾曲部におけるシート同士の間の薄い隙間にも、熱硬化性樹脂層の熱溶融物が流動充填されるためであり、これにより、本発明の多層接着シートは、精度よく接着することができる。また、被着物表面が複雑な凹凸面を有していても、その凹凸面に沿って精度よく湾曲する特性を有している。そして、この場合、その多層接着シートの湾曲部における被着物表面と該多層接着シートとの間の薄い隙間にも、熱硬化性樹脂層の熱溶融物が流動充填されることから、本発明の多層接着シートは、表面が複雑な凹凸面を有する被着物表面に対しても精度よく接着することができる。更に、その流動した接着剤（熱硬化性樹脂層）も高強度であることから、より高い応力がかかる製品にも適用することができる。本発明の多層接着シートは、熱交換器形成材料として好適なものであり、本発明の多層接着シートを用いて従来の方法に従って接着加工することにより、軽量かつ安価な熱交換器を簡便に作製することができる。 The multilayer adhesive sheet of the present invention is excellent in adhesive strength and has a characteristic that even if the shape of the component is complicated and the laminated sheet has to be curved and laminated, it can be firmly bonded without causing floating. Have. This is because the hot melt of the thermosetting resin layer is fluidly filled in the thin gaps between the sheets in the curved portion of the multilayer adhesive sheet. Can adhere well. Moreover, even if the surface of the adherend has a complicated uneven surface, the adherend surface has a characteristic of being accurately curved along the uneven surface. In this case, since the hot melt of the thermosetting resin layer is fluidly filled in the thin gap between the adherend surface and the multilayer adhesive sheet in the curved portion of the multilayer adhesive sheet, The multilayer adhesive sheet can be adhered with high accuracy to an adherend surface having a complex uneven surface. Furthermore, since the fluidized adhesive (thermosetting resin layer) also has high strength, it can be applied to products that are subjected to higher stress. The multilayer adhesive sheet of the present invention is suitable as a heat exchanger forming material, and a lightweight and inexpensive heat exchanger can be easily produced by adhesion processing according to a conventional method using the multilayer adhesive sheet of the present invention. can do.
以下、本発明の実施の形態について具体的に説明するが、本発明は以下の形態に限定されるものではない。 Hereinafter, although an embodiment of the present invention is described concretely, the present invention is not limited to the following form.
〔１〕金属シート
本発明の多層接着シートは、芯材としての金属シートの少なくとも片面に、機能の異なる熱硬化性樹脂を少なくとも２層以上設けたものである。この場合の金属シートとしては、従来公知の各種の金属（合金を含む）を用いることができる。このようなものとしては、アルミニウム合金、銅合金、鉄合金、マグネシウム合金等からなるシートが挙げられる。金属シートは、１層のみで構成されていてもよいし、２層以上の多層構造でもよい。
[1] Metal Sheet The multilayer adhesive sheet of the present invention is obtained by providing at least two layers of thermosetting resins having different functions on at least one surface of a metal sheet as a core material. As the metal sheet in this case, various conventionally known metals (including alloys) can be used. Examples of such a sheet include a sheet made of an aluminum alloy, a copper alloy, an iron alloy, a magnesium alloy, or the like. The metal sheet may be composed of only one layer or may have a multilayer structure of two or more layers.
本発明の多層接着シートを熱交換器形成用材料として使用する場合には、金属シートは熱伝導率の高いものが用いられ、それに加えて軽量であることや耐食性の高いことが求められ、その観点からアルミニウム材料からなるものが最適である。ここでいうアルミニウム材料とは、アルミニウム合金材料のことであり、高強度化、耐食性の向上、加工性の改善等の目的で、アルミニウム金属に、マグネシウム、銅、ケイ素、マンガン、鉄、クロム、ジルコニウム、チタン等の元素を通常０．１〜１０原子％添加したものである。ＪＩＳ記号に基づき具体例を挙げれば、Ａ２０１７（Ａｌ−Ｃｕ系）、Ａ３００３（Ａｌ−Ｍｎ系）、Ａ５０５２（Ａｌ−Ｍｇ系）等がある。また、金属シートの厚みは、特に制限はないが、通常５０〜２０００μｍであり、好ましくは７０〜１０００μｍ、特に好ましくは４００〜１０００μｍである。 When the multilayer adhesive sheet of the present invention is used as a material for forming a heat exchanger, a metal sheet having a high thermal conductivity is used, and in addition to that, it is required to be lightweight and have high corrosion resistance. An aluminum material is optimal from the viewpoint. The aluminum material here is an aluminum alloy material. For the purpose of increasing the strength, improving the corrosion resistance, improving the workability, etc., the aluminum metal is replaced with magnesium, copper, silicon, manganese, iron, chromium, zirconium. In addition, an element such as titanium is usually added in an amount of 0.1 to 10 atomic%. Specific examples based on JIS symbols include A2017 (Al-Cu system), A3003 (Al-Mn system), A5052 (Al-Mg system), and the like. The thickness of the metal sheet is not particularly limited, but is usually 50 to 2000 μm, preferably 70 to 1000 μm, and particularly preferably 400 to 1000 μm.
金属シートの表面には、所望により各種表面処理を行なうことができる。この場合の表面処理としては、例えば、アルミニウム表面と樹脂層の密着性向上を目的とした処理、例えば、リン酸クロメート処理、クロム酸クロメート処理等が挙げられる。また必要に応じて焼鈍処理を施すこともできる。 Various surface treatments can be performed on the surface of the metal sheet as desired. Examples of the surface treatment in this case include treatments aimed at improving the adhesion between the aluminum surface and the resin layer, such as phosphoric acid chromate treatment and chromate chromate treatment. Moreover, an annealing process can also be performed as needed.
前記のような金属シートの少なくとも片面に、各々機能の異なる熱硬化性樹脂からなるＡ層とＢ層という少なくとも２層の熱硬化性樹脂層を、Ａ層の上方にＢ層が形成されるように順次積層することにより、本発明に係る積層構造を有する多層接着シートが得られる。 At least two thermosetting resin layers of A and B layers each having a different function are formed on at least one side of the metal sheet as described above, and the B layer is formed above the A layer. By sequentially laminating, a multilayer adhesive sheet having a laminated structure according to the present invention is obtained.
〔２〕熱硬化性樹脂層
前記Ａ層及びＢ層を構成する熱硬化性樹脂としては、その硬化温度が常温以上、３００℃以下のものが好ましい。硬化温度が常温よりも低いと、接着シートとしての保存安定性が悪くなるため、常温以下の低温で保存しなければならず、また、部品加工、取付けも常温以下の低温で行わなければならず、取扱い性が悪くなる。逆に、硬化温度が３００℃より高いと、加熱硬化させるのに３００℃より高い温度にする必要があり、接合作業性が悪くなる。とりわけ芯材として使用可能なアルミニウム材料が耐熱性の観点から制約を受けることになり、熱交換器の軽量化に求められる金属シートの薄肉化が困難になる。また、樹脂の分解等の可能性もあり、好ましくない。硬化温度が常温以上、３００℃以下の熱硬化性樹脂としては、従来公知の各種のものを用いることができる。このようなものには、ポリエステル樹脂、フェノール樹脂、レゾルシノール樹脂、キシレン樹脂、アミノ樹脂、ポリウレタン、不飽和ポリエステル樹脂、エポキシ樹脂等が包含される。
[2] Thermosetting resin layer As the thermosetting resin constituting the A layer and the B layer, those having a curing temperature of normal temperature or higher and 300 ° C. or lower are preferable. If the curing temperature is lower than room temperature, the storage stability of the adhesive sheet will deteriorate, so it must be stored at a low temperature below room temperature, and parts processing and mounting must also be performed at a low temperature below room temperature. , Handling becomes worse. On the other hand, if the curing temperature is higher than 300 ° C., it is necessary to set the temperature higher than 300 ° C. for heat-curing, resulting in poor bonding workability. In particular, an aluminum material that can be used as a core material is restricted from the viewpoint of heat resistance, and it is difficult to reduce the thickness of a metal sheet that is required for reducing the weight of a heat exchanger. Also, there is a possibility of decomposition of the resin, which is not preferable. As the thermosetting resin having a curing temperature of normal temperature or higher and 300 ° C. or lower, various conventionally known resins can be used. Such materials include polyester resins, phenol resins, resorcinol resins, xylene resins, amino resins, polyurethanes, unsaturated polyester resins, epoxy resins and the like.
〔２−１〕Ａ層
本発明においては、Ａ層の熱硬化性樹脂としては、特にエポキシ樹脂の使用が好ましい。エポキシ樹脂としては、通常よく知られているビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、環式脂肪族エポキシ樹脂、特殊多官能型エポキシ樹脂などがあるが、それらを単独で、若しくは組合せて用いることができる。
[2-1] A layer In the present invention, it is particularly preferable to use an epoxy resin as the thermosetting resin of the A layer. As the epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, cyclic type are well known. There are aliphatic epoxy resins and special polyfunctional epoxy resins, and these can be used alone or in combination.
前記エポキシ樹脂は硬化剤で硬化させてもよい。硬化剤としては、従来公知のものが用いられ、特に制約はされないが、例えば、通常の低級アミンや、脂肪族ポリアミン、芳香族ポリアミン、複素環状ポリアミン、ポリアミドアミン、ジシアンジアミド及びその誘導体、イミダゾール系化合物等のアミン系硬化剤や、カルボン酸無水物系硬化剤の他、ルイス酸錯化合物等が挙げられる。該硬化剤の使用割合は、エポキシ樹脂１００質量部当り、２〜３０質量部、好ましくは３〜２０質量部である。 The epoxy resin may be cured with a curing agent. As the curing agent, conventionally known ones are used and are not particularly limited. For example, ordinary lower amines, aliphatic polyamines, aromatic polyamines, heterocyclic polyamines, polyamidoamines, dicyandiamide and derivatives thereof, and imidazole compounds In addition to amine-based curing agents such as carboxylic acid anhydride-based curing agents, Lewis acid complex compounds and the like can be mentioned. The use ratio of the curing agent is 2 to 30 parts by mass, preferably 3 to 20 parts by mass, per 100 parts by mass of the epoxy resin.
また、前記エポキシ樹脂を用いる場合には、エポキシ樹脂用硬化促進剤を添加することができる。エポキシ樹脂用硬化促進剤としては、常温において実質上エポキシ化合物と反応を示さないものであれば従来公知の各種のものを用いることができる。このような硬化促進剤としては、例えば、トリフェニルホスフィン、オクチル酸スズ、ジシアンジアミド、三塩化ホウ素／第３級アミン錯塩、三フッ化ホウ素／アミン錯塩、イミダゾールや第３級アミン等の含窒素化合物を変成してその表面に不活性膜を形成した微粉末状物質等が挙げられる。エポキシ樹脂用硬化促進剤の配合割合は特に制約されないが、一般には、エポキシ樹脂１００質量部に対し、０．０１〜５質量部、好ましくは０．０２〜３質量部の割合である。 Moreover, when using the said epoxy resin, the hardening accelerator for epoxy resins can be added. As the curing accelerator for epoxy resin, various conventionally known ones can be used as long as they do not substantially react with the epoxy compound at room temperature. Examples of such a curing accelerator include triphenylphosphine, tin octylate, dicyandiamide, boron trichloride / tertiary amine complex, boron trifluoride / amine complex, nitrogen-containing compounds such as imidazole and tertiary amine. The fine powdery substance etc. which modified | denatured and formed the inactive film | membrane on the surface are mentioned. The mixing ratio of the epoxy resin curing accelerator is not particularly limited, but is generally 0.01 to 5 parts by mass, preferably 0.02 to 3 parts by mass with respect to 100 parts by mass of the epoxy resin.
Ａ層には、前記熱硬化性樹脂及び所望により用いられる硬化剤や硬化促進剤のほかに、補助成分として、例えば、シリカやアルミナ、水酸化アルミニウム、炭酸カルシウム、酸化チタン、マイカ、タルク等の充填剤や顔料、染料、シランカップリング剤、可とう性付与剤、消泡剤を適量添加することができる。 In addition to the thermosetting resin and optionally used curing agents and curing accelerators, the A layer includes, for example, silica, alumina, aluminum hydroxide, calcium carbonate, titanium oxide, mica, talc and the like as auxiliary components. Appropriate amounts of fillers, pigments, dyes, silane coupling agents, flexibility imparting agents, and antifoaming agents can be added.
〔２−２〕Ｂ層
本発明の多層接着シートは、金属シートの少なくとも片面に前記Ａ層を設け、その上にＢ層を設けたものである。
Ｂ層はアクリルゴム及び／又はアクリロニトリルブタジエンゴムを含有するものである。このようにＢ層中にアクリルゴム及び／又はアクリロニトリルブタジエンゴムを含有させると、多層接着シートのＢ層の引張り強度や隙間充填性を所望の範囲に調整し易くなり、その結果、Ｂ層に亀裂（破損や破壊）が派生するのを防止できるので、信頼性の高い製品（例えば熱交換器）を得ることができる。
[2-2] B layer In the multilayer adhesive sheet of the present invention, the A layer is provided on at least one side of a metal sheet, and the B layer is provided thereon.
The B layer contains acrylic rubber and / or acrylonitrile butadiene rubber. When the acrylic rubber and / or acrylonitrile butadiene rubber is contained in the B layer in this way, it becomes easy to adjust the tensile strength and gap filling property of the B layer of the multilayer adhesive sheet to a desired range. As a result, the B layer is cracked. Since it is possible to prevent the occurrence of (breakage or destruction), a highly reliable product (for example, a heat exchanger) can be obtained.
前記Ｂ層に含有されるアクリルゴムとは、アルキル基がエステル結合された（メタ）アクリル酸エステルの重合、またはそれを主体とする共重合により得られるゴム状弾性体である。 The acrylic rubber contained in the B layer is a rubber-like elastic body obtained by polymerization of (meth) acrylic acid ester in which an alkyl group is ester-bonded or copolymerization based on it.
本明細書において「（メタ）アクリル酸」とは、アクリル酸又はメタクリル酸を意味し、「（メタ）アクリル酸エステル」とは、アクリル酸エステル又はメタクリル酸エステルを意味する。また、アルキル基がエステル結合された（メタ）アクリル酸エステルは、（メタ）アクリル酸のアルキルエステルである。 In this specification, “(meth) acrylic acid” means acrylic acid or methacrylic acid, and “(meth) acrylic acid ester” means acrylic acid ester or methacrylic acid ester. Moreover, the (meth) acrylic acid ester in which the alkyl group is ester-bonded is an alkyl ester of (meth) acrylic acid.
前記アルキル基がエステル結合された(メタ)アクリル酸エステルのアルキル基としては、１−プロピル基（ｎ−プロピル基）、１−メチルエチル基（ｉｓｏ−プロピル基）、１−ブチル基（ｎ−ブチル基）、２−メチルプロピル基（ｉｓｏ−ブチル基）、１−メチルプロピル基（ｓｅｃ−ブチル基）、１，１−ジメチルエチル基（ｔｅｒｔ−ブチル基）等が挙げられる。１−ヘキシル基（ｎ−ヘキシル基）、１−ヘプチル基（ｎ−ヘプチル基）、１−オクチル基（ｎ−オクチル基）、６−メチルヘプチル基（ｉｓｏ−オクチル基）、２−エチルヘキシル基等が挙げられる。従って、アルキル基がエステル結合された（メタ）アクリル酸エステルモノマーとしては、（メタ）アクリル酸のメチルエステル、エチルエステル、１−プロピルエステル（ｎ−プロピルエステル）、１−メチルエチルエステル（ｉｓｏ−プロピルエステル）、１−ブチルエステル（ｎ−ブチルエステル）、２−メチルプロピルエステル（ｉｓｏ−ブチルエステル）、１−メチルプロピルエステル（ｓｅｃ−ブチルエステル）、１，１−ジメチルエチルエステル（ｔｅｒｔ−ブチルエステル）、アクリル酸又はメタクリル酸の１−ヘキシルエステル（ｎ−ヘキシルエステル）、１−ヘプチルエステル（ｎ−ヘプチルエステル）、１−オクチルエステル（ｎ−オクチルエステル）、６−メチルヘプチルエステル（ｉｓｏ−オクチルエステル）、２−エチルヘキシルエステル等が挙げられる。 Examples of the alkyl group of the (meth) acrylic acid ester to which the alkyl group is bonded include 1-propyl group (n-propyl group), 1-methylethyl group (iso-propyl group), 1-butyl group (n- Butyl group), 2-methylpropyl group (iso-butyl group), 1-methylpropyl group (sec-butyl group), 1,1-dimethylethyl group (tert-butyl group) and the like. 1-hexyl group (n-hexyl group), 1-heptyl group (n-heptyl group), 1-octyl group (n-octyl group), 6-methylheptyl group (iso-octyl group), 2-ethylhexyl group, etc. Is mentioned. Accordingly, (meth) acrylic acid ester monomers having an alkyl group ester-linked include (meth) acrylic acid methyl ester, ethyl ester, 1-propyl ester (n-propyl ester), 1-methylethyl ester (iso-). Propyl ester), 1-butyl ester (n-butyl ester), 2-methylpropyl ester (iso-butyl ester), 1-methylpropyl ester (sec-butyl ester), 1,1-dimethylethyl ester (tert-butyl) Ester), 1-hexyl ester (n-hexyl ester) of acrylic acid or methacrylic acid, 1-heptyl ester (n-heptyl ester), 1-octyl ester (n-octyl ester), 6-methylheptyl ester (iso- Octyl ester), - ethylhexyl ester and the like.
アクリルゴムを構成する成分が、前記アルキル基がエステル結合された（メタ）アクリル酸エステルを主体とする共重合体である場合、その共重合成分としては、２−クロロエチルビニルエーテルやメチルビニルケトン等が挙げられる。このものの配合割合は、５０質量％未満が好ましい。 In the case where the component constituting the acrylic rubber is a copolymer mainly composed of (meth) acrylic acid ester in which the alkyl group is ester-bonded, examples of the copolymer component include 2-chloroethyl vinyl ether and methyl vinyl ketone. Is mentioned. The blending ratio of this is preferably less than 50% by mass.
また、アクリロニトリルブタジエンゴムとは、少なくともアクリロニトリルとブタジエンとを構成単位とする共重合体である。アクリロニトリルブタジエンゴムは、前記アクリロニトリルとブタジエンとの配合割合はアクリロニトリルが５０質量％未満、好ましくは３５〜１０質量％の範囲とするのがよい。また、アクリロニトリルブタジエンゴムは、前記２つの構成単位を含んでいれば、これを共重合可能な他の構成単位を含んでいても良い。この共重合可能な他の構成単位としては、カルボキシル基含有単量体やイソプレン、スチレン等が挙げられる。他の構成単位の配合割合は、０〜１０質量％程度である。 The acrylonitrile butadiene rubber is a copolymer having at least acrylonitrile and butadiene as structural units. In the acrylonitrile butadiene rubber, the blending ratio of the acrylonitrile and butadiene is less than 50% by mass of acrylonitrile, preferably 35 to 10% by mass. Moreover, the acrylonitrile butadiene rubber may contain the other structural unit which can copolymerize this, as long as the said 2 structural unit is included. Examples of other copolymerizable structural units include a carboxyl group-containing monomer, isoprene, and styrene. The blending ratio of other structural units is about 0 to 10% by mass.
前記アクリルゴム及び／又はアクリロニトリルブタジエンゴムの配合割合は、熱硬化性樹脂層を形成する熱硬化性樹脂１００質量部に対し、１〜１０質量部の範囲とすることが好ましい。この範囲よりもアクリルゴム及び／又はアクリロニトリルブタジエンゴムの配合量が少なくなると、多層接着シートとして引張り応力の調整性の面で不利であり、例えば多層接着シートを用いて熱交換器を製造した時に十分信頼性のある熱交換器を得ることが困難となり、また、アクリルゴム及び／又はアクリロニトリルブタジエンゴムの配合量がこの範囲を超えると、隙間充填性が低下するので好ましくない。引張り応力の調整性と隙間充填性の面から特に好ましいアクリルゴム及び／又はアクリロニトリルブタジエンゴムの配合割合は、１〜１０質量部、更に好ましい配合割合は４〜７質量部である。 The blending ratio of the acrylic rubber and / or acrylonitrile butadiene rubber is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the thermosetting resin forming the thermosetting resin layer. If the blending amount of acrylic rubber and / or acrylonitrile butadiene rubber is less than this range, it is disadvantageous in terms of adjusting the tensile stress as a multilayer adhesive sheet. For example, it is sufficient when a heat exchanger is manufactured using a multilayer adhesive sheet. It becomes difficult to obtain a reliable heat exchanger, and when the blending amount of acrylic rubber and / or acrylonitrile butadiene rubber exceeds this range, the gap filling property is lowered, which is not preferable. The blending ratio of acrylic rubber and / or acrylonitrile butadiene rubber is particularly preferably 1 to 10 parts by weight, and more preferably 4 to 7 parts by weight from the viewpoints of tensile stress adjustment and gap filling.
前記アクリルゴム及び／又はアクリロニトリルブタジエンゴムの好ましい形状は球状もしくは粒子状である。その際の粒径は平均粒径で１μｍ以下、好ましくは５００ｎｍ以下、特に樹脂強度の面から３００ｎｍ以下のものを用いるのが好ましい。
また、前記アクリルゴム及び／又はアクリロニトリルブタジエンゴムは、あらかじめエポキシ樹脂等に均一に分散させたものを用いるのが引張り応力の調整性に優れ、しかも精度の高い接着シートが得られるので好ましい。なお、この場合、用いられるエポキシ樹脂は、前記Ａ層やＢ層で用いられるエポキシ樹脂から選択してもよいし、他のものを用いてもよい。
A preferable shape of the acrylic rubber and / or acrylonitrile butadiene rubber is spherical or particulate. In this case, the average particle size is 1 μm or less, preferably 500 nm or less, and particularly preferably 300 nm or less in terms of resin strength.
Further, it is preferable to use the acrylic rubber and / or acrylonitrile butadiene rubber that is uniformly dispersed in an epoxy resin or the like in advance because it is excellent in adjusting the tensile stress and a highly accurate adhesive sheet can be obtained. In this case, the epoxy resin used may be selected from the epoxy resins used in the A layer and the B layer, or other ones may be used.
本発明では、このＢ層に含有する前記アクリルゴム及び／又はアクリロニトリルブタジエンゴムの一部として、フェノール性水酸基含有芳香族ポリアミド−ポリブタジエン−アクリロニトリル共重合体を用いることができる。フェノール性水酸基含有芳香族ポリアミド−ポリブタジエン−アクリロニトリル共重合体を用いることにより、Ｂ層の引張り応力を５０ＭＰａ以上に調整しやすくなり、その結果、Ｂ層に亀裂（破損や破壊）が発生するのを防止できるので、信頼性の高い製品、例えば熱交換器等を得ることができ好ましい。 In the present invention, a phenolic hydroxyl group-containing aromatic polyamide-polybutadiene-acrylonitrile copolymer can be used as a part of the acrylic rubber and / or acrylonitrile butadiene rubber contained in the B layer. By using a phenolic hydroxyl group-containing aromatic polyamide-polybutadiene-acrylonitrile copolymer, it becomes easy to adjust the tensile stress of the B layer to 50 MPa or more, and as a result, cracks (breakage or destruction) occur in the B layer. Therefore, a highly reliable product such as a heat exchanger can be obtained, which is preferable.
このようなフェノール性水酸基含有芳香族ポリアミド−ポリブタジエン−アクリロニトリル共重合体は、フェノール性水酸基を有するジカルボン酸成分、例えば、５−ヒドロキシイソフタル酸、４−ヒドロキシイソフタル酸、２−ヒドロキシフタル酸、３−ヒドロキシフタル酸、２−ヒドロキシテレフタル酸、フェノール性水酸基を有しないジカルボン酸としては、フタル酸、イソフタル酸、テレフタル酸、ジカルボキシルナフタレン、コハク酸、フマル酸、グルタル酸、アジピン酸、１，３−シクロヘキサンジカルボン酸、４，４’−ジフェニルジカルボン酸、３，３’−メチレン二安息香酸等に対して、ジアミン、例えば、３，３’−ジアミン−４，４’−ジヒドロキシフェニルメタン、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）ヘキサフロロプロパン、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）ジフロロメタン、３，４−ジアミノ−１，５−ベンゼンジオール、３，３’−ジヒドロキシ−４，４’−ジアミノビスフェニル、３，３’−ジアミノ−４，４’−ジヒドロキシビフェニル、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）ケトン、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）スルフィド、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）エーテル、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）スルホン、２，２−ビス（３−アミノ−４−ヒドロキシフェニル）プロパン、２，２−ビス（３−ヒドロキシ−４−アミノフェニル）プロパン、２，２−ビス（３−ヒドロキシ−４−アミノフェニル）メタン等、フェノール性水酸基を含有しないジアミンとして、３，３’−ジアミノジフェニルエーテル、３，４’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルエーテル、ジアミノナフタレン、ピペラジン、ヘキサネチレンジアミン、テトラメチレンジアミン、ｍ−キシレンジアミン、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノベンゾフェノン、２，２’−ビス（４−アミノフェニル）プロパン、３，３’−ジアミノジフェニルスルホン、３，３’−ジアミノジフェニル等を加え、これらを例えば、亜リン酸エステルとピリジン誘導体の存在下で縮合剤を使用して、Ｎ−メチル−２−ピロリドンによって代表される有機溶媒中で窒素等の不活性雰囲気下にて加熱攪拌、縮合反応を行って、フェノール性水酸基を含有するポリアミド−ポリブタジエン−アクリロニトリル共重合体を生成させることにより得られる。中でも下記式（１）で示される共重合体を使用するのが好ましい。 Such a phenolic hydroxyl group-containing aromatic polyamide-polybutadiene-acrylonitrile copolymer is a dicarboxylic acid component having a phenolic hydroxyl group, such as 5-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 2-hydroxyphthalic acid, 3- Hydroxyphthalic acid, 2-hydroxyterephthalic acid, and dicarboxylic acids having no phenolic hydroxyl group include phthalic acid, isophthalic acid, terephthalic acid, dicarboxyl naphthalene, succinic acid, fumaric acid, glutaric acid, adipic acid, 1,3- For cyclohexanedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 3,3′-methylenedibenzoic acid, etc., diamines such as 3,3′-diamine-4,4′-dihydroxyphenylmethane, 2,2 -Bis (3-amino-4-hydroxyphen L) Hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) difluoromethane, 3,4-diamino-1,5-benzenediol, 3,3'-dihydroxy-4,4'-diaminobis Phenyl, 3,3′-diamino-4,4′-dihydroxybiphenyl, 2,2-bis (3-amino-4-hydroxyphenyl) ketone, 2,2-bis (3-amino-4-hydroxyphenyl) sulfide 2,2-bis (3-amino-4-hydroxyphenyl) ether, 2,2-bis (3-amino-4-hydroxyphenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) Propane, 2,2-bis (3-hydroxy-4-aminophenyl) propane, 2,2-bis (3-hydroxy-4-aminophenyl) methane, etc. Diamines containing no phenolic hydroxyl groups include 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, diaminonaphthalene, piperazine, hexanetylenediamine, tetramethylenediamine, and m-xylene. Diamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminobenzophenone, 2,2′-bis (4-aminophenyl) propane, 3,3′-diaminodiphenylsulfone, 3,3′-diaminodiphenyl, etc. In addition, these are heated and stirred under an inert atmosphere such as nitrogen in an organic solvent represented by N-methyl-2-pyrrolidone using a condensing agent in the presence of a phosphite ester and a pyridine derivative, for example. , Containing a phenolic hydroxyl group by performing a condensation reaction It is obtained by forming a polyamide-polybutadiene-acrylonitrile copolymer. Among them, it is preferable to use a copolymer represented by the following formula (1).
（式中、ｘ、ｙ、ｚ、ｌ、ｍ及びｎは、それぞれ平均重合度であって、ｘ＝３〜７、ｙ＝１〜４、ｚ＝５〜１５、ｌ＋ｍ＝２〜２００の整数をそれぞれ示し、ｍ／（ｌ＋ｍ）≧０．０４である。）
このフェノール性水酸基を含有するポリアミド−ポリブタジエン−アクリロニトリル共重合体の配合割合は、隙間充填特性を１５ｍｍ以上とする範囲で適宜選択されるが、通常前記アクリルゴム及び／又はアクリロニトリルブタジエンゴムの使用量の５０質量％未満の範囲である。
(Wherein, x, y, z, l, m and n are average polymerization degrees, and x = 3 to 7, y = 1 to 4, z = 5 to 15, and l + m = 2 to 200 integers. And m / (l + m) ≧ 0.04.)
The blending ratio of the polyamide-polybutadiene-acrylonitrile copolymer containing the phenolic hydroxyl group is appropriately selected within a range in which the gap filling characteristic is 15 mm or more. The range is less than 50% by mass.
Ｂ層は、前記アクリルゴム及び／又はアクリロニトリルブタジエンゴムのほか、前述の熱硬化性樹脂及び所望により用いられる硬化剤や硬化促進剤及び他の添加剤等を組み合わせた層である。
なお、前記Ａ層にもＢ層に含有するアクリルゴム及び／又はアクリロニトリルブタジエンゴム、所望により用いられるフェノール性水酸基含有芳香族ポリアミド−ポリブタジエン−アクリロニトリル共重合体を含有することができる。
The B layer is a layer combining the above-mentioned acrylic rubber and / or acrylonitrile butadiene rubber, the above-mentioned thermosetting resin, and a curing agent, a curing accelerator and other additives used as required.
The A layer may also contain acrylic rubber and / or acrylonitrile butadiene rubber contained in the B layer, and optionally used phenolic hydroxyl group-containing aromatic polyamide-polybutadiene-acrylonitrile copolymer.
〔３〕多層接着シート
本発明の多層接着シートは、前記金属シート、Ａ層及びＢ層とをこの順に積層したものであるが、特に前記Ｂ層の厚さ１０〜１００μｍの隙間充填特性が１５ｍｍ以上でしかも引張り応力が５０ＭＰａ以上とするのが好ましい。
また、Ａ層に用いる熱硬化性樹脂において、その硬化後のガラス転移温度（Ｔｇ）は１２０℃以上、３００℃以下であることが好ましい。１２０℃未満では耐熱性が悪く、特に車載用エアコンにおいては、外気温の高い夏場や、平均気温の高い南国の使用に耐えることができないし、また、３００℃超では、耐熱性は十分に満足できるが、樹脂の強靭性がなくなって脆くなってしまい、せん断強度が低下してしまうので好ましくない。加えて、本発明のＡ層に用いる熱硬化性樹脂において、その硬化後の８０℃における弾性率は１×１０８Ｐａ以上、１×１０１０Ｐａ以下であるのが好ましい。１×１０８Ｐａ未満では、樹脂が柔らかく、接着層が凝集破壊しやすくなり、一方、１×１０１０Ｐａ超では、靭性がなくなり、接着層が脆くなるので好ましくない。
[3] Multilayer adhesive sheet The multilayer adhesive sheet of the present invention is a laminate of the metal sheet, the A layer and the B layer in this order. In particular, the gap filling property of the B layer having a thickness of 10 to 100 μm is 15 mm. In addition, the tensile stress is preferably 50 MPa or more.
Moreover, in the thermosetting resin used for A layer, it is preferable that the glass transition temperature (Tg) after the hardening is 120 degreeC or more and 300 degrees C or less. Heat resistance is poor at temperatures below 120 ° C, and in particular, automotive air conditioners cannot withstand use in summer when the outside temperature is high or in southern countries where the average temperature is high, and heat resistance is sufficiently satisfactory at temperatures above 300 ° C. However, it is not preferable because the toughness of the resin is lost and the resin becomes brittle and the shear strength decreases. In addition, in the thermosetting resin used for the A layer of the present invention, the elastic modulus at 80 ° C. after the curing is preferably 1 × 10 8 Pa or more and 1 × 10 10 Pa or less. If it is less than 1 × 10 8 Pa, the resin is soft and the adhesive layer tends to cohesively break, whereas if it exceeds 1 × 10 10 Pa, the toughness is lost and the adhesive layer becomes brittle.
前記Ｂ層の隙間充填特性としては、特に厚さ１０〜１００μｍでの隙間充填特性が１５ｍｍ以上、６０ｍｍ以下の特性を有する樹脂層であることが好ましい。ここでいうところの隙間充填特性とは、図１に示す長方形のテストピースを用い形成された接点を有する隙間を充填する能力を長さで表したものであり、１５ｍｍ未満では、多層接着シートを部品加工し、多層に重ね合せて取り付け後、加熱硬化させる際に、特に湾曲した部分の狭い隙間に十分に樹脂が充填されずに、浮きが発生したり、湾曲部分での接着強度が不十分になってしまう。一方、６０ｍｍ超では、加熱硬化させる際にＢ層の樹脂層が流れやすすぎて、樹脂の流失が生じて、安定して積層するのが難しくなり、作業性が著しく低下する。なお、隙間充填特性の具体的な評価（測定）方法については、後述の実施例において詳しく説明する。 As the gap filling characteristics of the B layer, a resin layer having a gap filling characteristic of 15 mm or more and 60 mm or less particularly at a thickness of 10 to 100 μm is preferable. The gap filling property referred to here is a length representing the ability to fill a gap having a contact formed using the rectangular test piece shown in FIG. When parts are processed, stacked and mounted, and then heat-cured, the resin does not fill the narrow gaps of the curved part sufficiently, causing floating and insufficient adhesive strength at the curved part Become. On the other hand, if it exceeds 60 mm, the resin layer of the B layer is too easy to flow at the time of heat curing, causing the resin to flow out, making it difficult to stably laminate, and the workability is remarkably lowered. In addition, the specific evaluation (measurement) method of the gap filling characteristics will be described in detail in examples described later.
また、Ｂ層の引張り応力とは、下記引張り試験により測定させるものである。
引張り試験：
最表層の熱硬化性樹脂層を形成する材料からＡＳＴＭ Ｄ−６３８ タイプＩ型に基づく試験片を作成し、これを引張り試験用の試験片とする。この試験片を用いて、ＪＩＳ Ｋ ７１１３に準拠し、試験速度５ｍｍ／ｍｉｎの条件で引張り応力を測定する。
Further, the tensile stress of the B layer is measured by the following tensile test.
Tensile test:
A test piece based on ASTM D-638 Type I is prepared from the material forming the outermost thermosetting resin layer, and this is used as a test piece for a tensile test. Using this test piece, tensile stress is measured under the condition of a test speed of 5 mm / min according to JIS K7113.
この引張り応力は３０ＭＰａ以上、特に５０ＭＰａ以上が好ましい。この引張り応力が５０ＭＰａ未満であると、この多層接着シートを成形後、冷媒やエアー等の応力によりＢ層に亀裂（破損や破壊）が発生してしまう。しかも、このＢ層の亀裂はＡ層の破損や破壊を引き起こすため、Ａ層と金属シートとの界面付近で剥離が発生し、結果的に信頼性の高い製品、例えば熱交換器を得ることができないので好ましくない。好ましい引張り応力は５５ＭＰａ以上、更に好ましくは６５ＭＰａ以上である。 This tensile stress is preferably 30 MPa or more, particularly preferably 50 MPa or more. When this tensile stress is less than 50 MPa, after forming this multilayer adhesive sheet, cracks (breakage or breakage) occur in the B layer due to stresses such as refrigerant and air. Moreover, since the cracks in the B layer cause damage and destruction of the A layer, peeling occurs near the interface between the A layer and the metal sheet, resulting in a highly reliable product such as a heat exchanger. It is not preferable because it cannot be done. A preferred tensile stress is 55 MPa or more, more preferably 65 MPa or more.
また、本発明の多層接着シートの更に他の態様は、前記態様と同様に、各々機能の異なる熱硬化性樹脂からなるＡ層とＢ層という少なくとも２層の熱硬化性樹脂層を順次積層することにより得られるもので、この多層接着シートを構成するＢ層の下記引張り試験による引張り応力は５０ＭＰａ以上である。 Further, in another aspect of the multilayer adhesive sheet of the present invention, as in the above aspect, at least two thermosetting resin layers of A layer and B layer made of thermosetting resins each having different functions are sequentially laminated. The tensile stress by the following tensile test of B layer which comprises this multilayer adhesive sheet is 50 Mpa or more.
本発明の多層接着シートの好ましい態様は、図２に示すように、芯材である金属シート１の少なくとも片面に、これら機能の異なる熱硬化性樹脂をＡ層、Ｂ層として設けたものである。多層接着シートを用いて、部品加工、組付後、加熱硬化させて、熱交換器を製造する際に、その積層構造体の湾曲部分においても十分な接着強度を持たせるためには、引張せん断強度の高い熱硬化性樹脂を湾曲部分の隙間に十分に充填させることが重要である。ところが、芯材である金属シートに熱硬化性樹脂を１層のみ設けた構成のものでは、引張せん断強度を高めようとすると、隙間充填性が低下し、反対に隙間充填性を高めようとすると引張せん断強度が低下する。つまり、引張せん断強度と隙間充填性とは相反する性質がある。
A preferred embodiment of the multilayer adhesive sheet of the present invention is one in which thermosetting resins having different functions are provided as an A layer and a B layer on at least one surface of a
そこで、従来は、これら相反する特性を有する熱硬化性樹脂層をＡ層、Ｂ層として積層することで、両方の特性を満足し、引張せん断強度の高い熱硬化性樹脂を湾曲部分の隙間に十分に充填させることを可能としたが（特許文献３参照）、Ｂ層はＡ層に比べ硬化後の強度が低いため、Ｂ層同士を接着・硬化させた場合、引張力や衝撃によりＢ層に亀裂（破損又は破壊）が発生し、それによりＡ層にも亀裂（破損又は破壊）が発生して、その結果金属シートとＡ層との界面付近で剥離してしまう場合がある。 Therefore, conventionally, by laminating these thermosetting resin layers having contradictory properties as the A layer and the B layer, both properties are satisfied, and a thermosetting resin having a high tensile shear strength is placed in the gaps between the curved portions. Although it was possible to sufficiently fill (see Patent Document 3), the B layer has a lower strength after curing than the A layer. Therefore, when the B layers are bonded to each other and cured, the B layer is caused by tensile force or impact. Cracks (breakage or destruction) occur in the A layer, and cracks (breakage or destruction) also occur in the A layer. As a result, there are cases where separation occurs near the interface between the metal sheet and the A layer.
本発明においては、この点を改善し、最表層であるＢ層の引張り応力を５０ＭＰａ以上とすることにより、Ｂ層の硬化後の強度を向上させ、その結果、金属シートとＡ層と間、Ａ層内部、Ａ層とＢ層との間及びＢ層内部のいずれにおいても層間剥離や層破壊の発生がない多層接着シートとすることができた。 In the present invention, this point is improved, and by making the tensile stress of the outermost layer B layer 50 MPa or more, the strength after curing of the B layer is improved. As a result, between the metal sheet and the A layer, A multilayer adhesive sheet in which no delamination or layer breakage occurred within the A layer, between the A layer and the B layer, or inside the B layer could be obtained.
Ａ層とＢ層の厚さは任意に定めることができるが、それらを合せた全体の厚みは、当該多層接着シートを熱交換器の作製に用いた場合における熱交換器の軽量化と、そのための多層接着シートの薄膜化という観点から、１０μｍ以上、２００μｍ以下とすることが好ましく、１５μｍ以上、１５０μｍ以下とすることがより好ましい。その範囲の中で、要求される引張せん断強度と隙間充填性のバランスを考えて、Ａ層とＢ層の厚さの比を変化させることができる。つまり、湾曲の程度が穏やかで、引張せん断強度を重視する場合には、Ａ層の厚みの比を高くし、反対に湾曲の程度が大きく、その隙間が複雑な形状になっているような場合には、隙間充填性を重視して、Ｂ層の厚みの比を高くすることができる。一般的には、Ａ層に対するＢ層の厚さの比（Ｂ／Ａ）は０．５以上、２０以下が好ましい The thicknesses of the A layer and the B layer can be arbitrarily determined, but the total thickness of the A layer and the B layer is the weight reduction of the heat exchanger when the multilayer adhesive sheet is used for the production of the heat exchanger. From the viewpoint of thinning the multilayer adhesive sheet, it is preferably 10 μm or more and 200 μm or less, and more preferably 15 μm or more and 150 μm or less. Within that range, the ratio of the thicknesses of the A layer and the B layer can be changed in consideration of the balance between the required tensile shear strength and gap filling property. In other words, when the degree of bending is moderate and the tensile shear strength is important, the thickness ratio of layer A is increased, and conversely, the degree of bending is large and the gap is in a complicated shape. Therefore, it is possible to increase the ratio of the thickness of the B layer with an emphasis on gap filling properties. Generally, the ratio of the thickness of the B layer to the A layer (B / A) is preferably 0.5 or more and 20 or less.
また、本発明の接着シートの引張せん断強度が、常温で５ＭＰａ以上である樹脂層であることが好ましい。５ＭＰａ未満では、部品加工、取り付け後、加熱硬化させて作製した構造物としての強度が低下してしまうので好ましくない。好ましくは８ＭＰａ以上が好ましい。 Moreover, it is preferable that it is a resin layer whose tensile shear strength of the adhesive sheet of this invention is 5 Mpa or more at normal temperature. If it is less than 5 MPa, the strength as a structure produced by heat-curing after parts processing and attachment is lowered, which is not preferable. Preferably it is 8 MPa or more.
次に、本発明による図２に示した構成の多層接着シートの製造方法の一例について述べる。これは、金属シートの両面にＡ層とＢ層を積層した構造の多層接着シートであるが、他の構成のものも同様の方法で製造することができる。 Next, an example of the manufacturing method of the multilayer adhesive sheet having the configuration shown in FIG. 2 according to the present invention will be described. This is a multilayer adhesive sheet having a structure in which an A layer and a B layer are laminated on both surfaces of a metal sheet, but other configurations can be manufactured by the same method.
Ａ層用の熱硬化性樹脂組成物からなるＡ層形成塗工液と、Ｂ層用の熱硬化性樹脂組成物からなるＢ層形成塗工液とを次の手順で調製し、先ず始めに、ロールコーター、コンマコーター、バーコーター等を用いて、Ａ層形成塗工液を前記の金属シートの片面に要望する塗布厚さになるように塗布する。これをドライヤーを通して８０〜１２０℃で１〜５分間加熱処理し、熱硬化性樹脂組成物中の溶剤を除去して乾燥させ、Ａ層を形成する。次に、この反対面にも同様の方法でＡ層を形成させ、両面塗工品を作製する。次いで、各Ａ層の上に、Ｂ層形成塗工液をＡ層の場合と同様の方法で塗布して乾燥させ、金属シートの両面に各Ａ、Ｂ２層ずつの熱硬化性樹脂を有する両面構成の多層接着シートを作製する。 First, an A layer forming coating solution composed of a thermosetting resin composition for A layer and a B layer forming coating solution composed of a thermosetting resin composition for B layer are prepared by the following procedure. Using a roll coater, comma coater, bar coater or the like, the A layer forming coating solution is applied to one side of the metal sheet so as to have a desired coating thickness. This is heat-treated at 80 to 120 ° C. for 1 to 5 minutes through a dryer, and the solvent in the thermosetting resin composition is removed and dried to form the A layer. Next, a layer A is formed on the opposite surface in the same manner to produce a double-side coated product. Next, on each A layer, a B layer forming coating solution is applied and dried in the same manner as in the case of the A layer, and both sides of the metal sheet have thermosetting resins of the A and B layers. A multilayer adhesive sheet having the structure is prepared.
＜塗工液の調製＞
（１）予め、エポキシ樹脂を所望する粘度になるように溶剤で希釈しておいた樹脂液に、無機フィラーからなる充填剤、エラストマーからなる可とう性付与剤、シランカップリング剤を添加し攪拌する。
（２）前記（１）の液に硬化剤及び硬化促進剤を添加し、更に混合する。
<Preparation of coating solution>
(1) Add a filler made of an inorganic filler, a flexibility-imparting agent made of an elastomer, and a silane coupling agent to a resin solution that has been diluted with a solvent so that the epoxy resin has a desired viscosity in advance. To do.
(2) A curing agent and a curing accelerator are added to the liquid of (1) and further mixed.
本発明の多層接着シートは、そのシートからプレス加工等により、所定の寸法・形状の部品を成形し、その部品を互いに積層し組み付け、そのＡ層及びＢ層の溶融温度に加熱して接着するようにして使用される。本発明の多層接着シートは、その部品の形状が複雑な場合には、多層接着シートを湾曲して積層しなければならないが、そういう薄い隙間が多数発生する構造であっても、接着剤が流動充填することによって、湾曲した部分でも浮きが発生せずに接着させることができる。 The multilayer adhesive sheet of the present invention is formed by molding parts of a predetermined size and shape from the sheet by pressing or the like, and laminating and assembling the parts together and heating them to the melting temperature of the A layer and the B layer to bond them. Used as such. In the multilayer adhesive sheet of the present invention, when the shape of the component is complicated, the multilayer adhesive sheet must be curved and laminated. However, even if such a thin gap is generated, the adhesive flows. By filling, even a curved portion can be bonded without causing floating.
本発明の多層接着シートは、熱交換器形成用材料として有利に用いられる。図３に、本発明の多層接着シートで形成した熱交換器の１つの実施例についてその断面の一部を模式図で示す。図３において、１１は熱交換器を示し、１２、１３は本発明の多層接着シートを示す。山形をしたより狭い空間部分Ｘは冷媒オイル、水、ＬＬＣ等の液体が流れる部分であり、他のより広い空間部分Ｙは空気が流動する部分である。 The multilayer adhesive sheet of the present invention is advantageously used as a material for forming a heat exchanger. FIG. 3 schematically shows a part of a cross section of one embodiment of a heat exchanger formed of the multilayer adhesive sheet of the present invention. In FIG. 3, 11 shows a heat exchanger, 12 and 13 show the multilayer adhesive sheet of this invention. The narrower space portion X having a mountain shape is a portion through which liquids such as refrigerant oil, water, and LLC flow, and the other wider space portion Y is a portion through which air flows.
この熱交換器を用いて２つの流体（液体、気体）間の熱交換を行うには、本発明の多層接着シート１２、１３を介して、図３に示すように、液体と空気を交流させる。
In order to perform heat exchange between two fluids (liquid and gas) using this heat exchanger, the liquid and air are made to exchange with each other through the multilayer
次に、実施例により本発明を更に詳細に説明するが、本発明はこれらの例によって何ら限定されるものではない。なお、多層接着シートの物性は、次に示す方法に従って評価した。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples. The physical properties of the multilayer adhesive sheet were evaluated according to the following methods.
［引張せん断強度］
金属シート（アルミニウム板）の片面に、Ａ層形成塗工液を乾燥後の厚みが所定の厚みになるようにバーコーターで塗布し、熱風ドライヤーに入れて、１００℃で３分間加熱乾燥させ、Ａ層を形成した。次に、そのＡ層上に、Ｂ層形成塗工液を乾燥後の厚みが所定の厚みになるようにＡ層の場合と同様に塗布・乾燥させてＢ層を形成し、引張せん断強度測定用の多層接着シートのサンプルを作製した。次いで、こうして作製したサンプルをＪＩＳ Ｋ ６８５０に準拠した試験片の形状、大きさに加工し、多層接着シート同士を最表層の熱硬化性樹脂層（Ｂ層）の面が互いに相対するように重ね合わせ、１．５ｍｍのアルミニウム板で挟みピンチコックで締め付けた状態で、熱風ドライヤーに入れて２００℃で３０分間、加熱硬化させた。このようにして作製した引張せん断強度測定用の試験片を用いて、ＪＩＳ Ｋ ６８５０に準拠し、引張速度５ｍｍ／分の条件で引張せん断強度を測定した。
[Tensile shear strength]
On one side of the metal sheet (aluminum plate), the A layer forming coating solution is applied with a bar coater so that the thickness after drying becomes a predetermined thickness, put in a hot air dryer, and heated and dried at 100 ° C. for 3 minutes. A layer was formed. Next, on the A layer, the B layer forming coating solution is applied and dried in the same manner as in the case of the A layer so that the thickness after drying becomes a predetermined thickness, and the B layer is formed, and the tensile shear strength is measured. Samples of multilayer adhesive sheets for use were prepared. Next, the sample thus prepared was processed into the shape and size of a test piece in accordance with JIS K 6850, and the multilayer adhesive sheets were stacked so that the surfaces of the outermost thermosetting resin layer (B layer) face each other. In a state of being sandwiched between 1.5 mm aluminum plates and tightened with a pinch cock, they were placed in a hot air dryer and cured by heating at 200 ° C. for 30 minutes. Using the test piece for tensile shear strength measurement thus prepared, the tensile shear strength was measured under the condition of a tensile speed of 5 mm / min according to JIS K 6850.
［Ｂ層の引張り応力］
Ｂ層形成塗工液からＡＳＴＭ Ｄ−６３８ タイプＩ型に基づく試験片を作製した。
次に、この試験片を用いて、ＪＩＳ Ｋ ７１１３に準拠し、試験速度５ｍｍ／ｍｉｎの条件で引張り応力を測定した。
[Tensile stress of layer B]
A test piece based on ASTM D-638 Type I was prepared from the B layer forming coating solution.
Next, using this test piece, tensile stress was measured in accordance with JIS K 7113 at a test speed of 5 mm / min.
［隙間充填特性］
図２に示すように、引張せん断強度測定用サンプルと同一の方法で作製した１つの多層接着シートサンプルＳ１（厚さ１．０ｍｍ、幅２５ｍｍ、長さ５５ｍｍ）を垂直にして、水平にしたもう一つの多層接着シートサンプルＳ２（厚さ１．０ｍｍ、幅２５ｍｍ、長さ６０ｍｍ）の上に置き、多層接着シートサンプルＳ１の片側を多層接着シートサンプルＳ２に接触させ、他の側にスペーサーロッド（直径１．５ｍｍ）を介在させて組み付けた後、硬化温度２００℃で３０分間加熱し、両者を接着させた。接着加熱後、多層接着シートサンプルＳ１と多層接着シートサンプルＳ２との隙間に溶融して流動充填された接着剤のサンプル長手方向における長さ（隙間充填長さ）を測定し、隙間充填特性とした。
[Gap filling characteristics]
As shown in FIG. 2, one multilayer adhesive sheet sample S1 (thickness 1.0 mm, width 25 mm, length 55 mm) prepared by the same method as the sample for measuring tensile shear strength was made vertical and horizontal. It is placed on one multilayer adhesive sheet sample S2 (thickness 1.0 mm, width 25 mm, length 60 mm), one side of the multilayer adhesive sheet sample S1 is brought into contact with the multilayer adhesive sheet sample S2, and the spacer rod ( After assembling with a diameter of 1.5 mm, it was heated at a curing temperature of 200 ° C. for 30 minutes to bond them together. After bonding and heating, the length (gap filling length) in the sample longitudinal direction of the adhesive melted and fluidly filled in the gap between the multilayer adhesive sheet sample S1 and the multilayer adhesive sheet sample S2 was measured to obtain gap filling characteristics. .
実施例１
［Ａ層形成塗工液の調製］
フェノール・ジシクロペンタジエン型エポキシ樹脂（大日本インキ化学工業（株）製、商品名：ＨＰ７２００−Ｌ）（固形分７０％トルエン溶液品）７１．４質量部に、ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン（株）製、商品名：エピコート８２８）５０．０質量部を攪拌混合し溶解させ、エポキシ樹脂溶液を作製した。次に、この中に可とう性付与剤として、フェノール性水酸基含有芳香族ポリアミド−ポリブタジエン−アクリロニトリル共重合体（日本化薬（株）製、商品名：ＢＰ−４０Ｄ）（固形分４０％ＤＭＦ溶液品）１２５．０質量部、充填剤として酸化チタン（石原産業（株）製、商品名：タイペークＲ−５８０）１００．０質量部、シランカップリング剤（チッソ（株）製、商品名：サイラエースＳ−５１０）１．０質量部を加え、ホモジナイザーで混合した。更にその後、その中に硬化剤（ジャパンエポキシレジン（株）製、商品名：エピキュアＤＩＣＹ１５）５．９質量部、硬化促進剤としてトリフェニルホスフィン０．５質量部を加え、Ａ層の熱硬化性樹脂組成物からなるＡ層形成塗工液を調製した。
Example 1
[Preparation of A layer forming coating solution]
Phenolic dicyclopentadiene type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: HP7200-L) (solid content 70% toluene solution product) 71.4 parts by mass, bisphenol A type epoxy resin (Japan epoxy) 50.0 parts by mass of Resin Co., Ltd., trade name: Epicoat 828) was mixed with stirring and dissolved to prepare an epoxy resin solution. Next, as a flexibility imparting agent, a phenolic hydroxyl group-containing aromatic polyamide-polybutadiene-acrylonitrile copolymer (manufactured by Nippon Kayaku Co., Ltd., trade name: BP-40D) (solid content 40% DMF solution) Product) 125.0 parts by mass, titanium oxide (made by Ishihara Sangyo Co., Ltd., trade name: Typek R-580) as a filler, 100.0 parts by mass, silane coupling agent (produced by Chisso Corporation, trade name: Sila Ace) S-510) 1.0 part by mass was added and mixed with a homogenizer. Further thereafter, 5.9 parts by mass of a curing agent (trade name: Epicure DICY15, manufactured by Japan Epoxy Resin Co., Ltd.) and 0.5 parts by mass of triphenylphosphine as a curing accelerator were added, and the thermosetting property of the A layer was added. A layer formation coating liquid consisting of a resin composition was prepared.
［Ｂ層形成塗工液の調製］
次に、フェノール・ジシクロペンタジエン型エポキシ樹脂（大日本インキ化学工業（株）製、商品名：ＨＰ７２００−Ｌ）（固形分７０％トルエン溶液品）１４２．９質量部に、硬化剤（ジャパンエポキシレジン（株）製、商品名：エピキュアＤＩＣＹ１５）５．２質量部、硬化促進剤としてトリフェニルホスフィン０．５質量部、アクリルゴム含有エポキシ樹脂〔球状アクリルゴム（ガラス転移温度−３０℃、質量平均粒径３００ｎｍ）６質量部をエポキシ樹脂（ジャパンエポキシレジン（株）製、商品名：エピコート８０７）２４質量部に均一に分散したもの〕３０質量部を加え、ホモジナイザーで混合して、Ｂ層用の熱硬化性樹脂組成物からなる塗工液Ｂを調製した。
[Preparation of B layer forming coating solution]
Next, phenol dicyclopentadiene type epoxy resin (manufactured by Dainippon Ink & Chemicals, Inc., trade name: HP7200-L) (solid content 70% toluene solution product) 142.9 parts by mass, a curing agent (Japan epoxy Resin Co., Ltd., trade name: Epicure DICY15) 5.2 parts by mass, curing accelerator 0.5 parts by mass of triphenylphosphine, acrylic rubber-containing epoxy resin [spherical acrylic rubber (glass transition temperature-30 ° C., mass average 6 parts by mass of particle size 300 nm) uniformly dispersed in 24 parts by mass of epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name: Epicoat 807) 30 parts by mass is added and mixed with a homogenizer, for layer B The coating liquid B which consists of a thermosetting resin composition was prepared.
［多層接着シートの作製］
Ａ層形成塗工液を、厚さ１００μｍのアルミニウム板の片面に塗布して乾燥（１００℃、３分間）させ、膜厚５μｍのＡ層を設けた。次に、その反対面にも同様の方法で膜厚５μｍのＡ層を設けた。次いで、Ｂ層形成塗工液を、前記のように設けたＡ層の上に塗布して乾燥（１００℃、３分間）させ、膜厚７５μｍのＢ層を設けた。次に、その反対面にも同様の方法で膜厚７５μｍのＢ層を設け、こうして本発明による機能の異なる熱硬化性樹脂層を両面に２層有する多層接着シートを作製した。このものの物性を表１に示す。
[Production of multilayer adhesive sheet]
The A layer forming coating solution was applied to one side of an aluminum plate having a thickness of 100 μm and dried (100 ° C., 3 minutes) to provide an A layer having a thickness of 5 μm. Next, an A layer having a film thickness of 5 μm was provided on the opposite surface in the same manner. Next, the B layer forming coating solution was applied on the A layer provided as described above and dried (100 ° C., 3 minutes) to provide a B layer having a thickness of 75 μm. Next, a B layer having a film thickness of 75 μm was provided on the opposite surface in the same manner, and thus a multilayer adhesive sheet having two thermosetting resin layers having different functions according to the present invention on both sides was produced. The physical properties of this product are shown in Table 1.
参考例１
実施例１において、Ｂ層形成塗工液で用いるアクリルゴム含有エポキシ樹脂に代え、アクリロニトリルブタジエンゴム含有エポキシ樹脂〔粒子状アクリロニトリルブタジエンゴム（ガラス転移温度−３０℃、一次粒子径７０ｎｍ、二次粒子径２００〜３００ｎｍ）６質量部をエポキシ樹脂（ジャパンエポキシレジン（株）製、商品名：エピコート８０７）２４質量部に均一に分散したもの〕３０質量部を用いた以外は全て実施例１と同様にして多層接着シートを作製した。このものの物性を表１に示す。
Reference example 1
In Example 1, instead of the acrylic rubber-containing epoxy resin used in the B layer forming coating solution, an acrylonitrile butadiene rubber-containing epoxy resin [particulate acrylonitrile butadiene rubber (glass transition temperature -30 ° C, primary particle diameter 70 nm, secondary particle diameter 200-300 nm) 6 parts by mass of epoxy resin (Japan Epoxy Resin Co., Ltd., trade name: Epicoat 807) uniformly dispersed in 24 parts by mass] All the same as in Example 1 except that 30 parts by mass was used. A multilayer adhesive sheet was prepared. The physical properties of this product are shown in Table 1.
実施例２
実施例１において、アクリルゴム含有エポキシ樹脂３０質量部に代え、アクリルゴム含有エポキシ樹脂１５質量部、フェノール性水酸基含有芳香族ポリアミド−ポリブタジエン−アクリロニトリル共重合体を７．５質量部用いた以外は全て実施例１と同様にして多層接着シートを作製した。このものの物性を表１に示す。
Example 2
In Example 1, instead of 30 parts by mass of the acrylic rubber-containing epoxy resin, 15 parts by mass of the acrylic rubber-containing epoxy resin and 7.5 parts by mass of the phenolic hydroxyl group-containing aromatic polyamide-polybutadiene-acrylonitrile copolymer were used. A multilayer adhesive sheet was produced in the same manner as in Example 1. The physical properties of this product are shown in Table 1.
参考例２
実施例１において、アクリルゴム含有エポキシ樹脂３０質量部に代え、アクリロニトリルブタジエンゴム含有エポキシ樹脂を１５質量部、フェノール性水酸基含有芳香族ポリアミド−ポリブタジエン−アクリロニトリル共重合体を７．５質量部用いた以外は全て実施例１と同様にして多層接着シートを作製した。このものの物性を表１に示す。
Reference example 2
In Example 1, instead of 30 parts by mass of the acrylic rubber-containing epoxy resin, 15 parts by mass of the acrylonitrile butadiene rubber-containing epoxy resin and 7.5 parts by mass of the phenolic hydroxyl group-containing aromatic polyamide-polybutadiene-acrylonitrile copolymer were used. Were produced in the same manner as in Example 1 to produce a multilayer adhesive sheet. The physical properties of this product are shown in Table 1.
実施例３
実施例１でアクリルゴム含有エポキシ樹脂を１５質量部とした以外は全て実施例１と同様にして多層接着シートを作製した。このものの物性を表１に示す。
Example 3
A multilayer adhesive sheet was prepared in the same manner as in Example 1 except that the acrylic rubber-containing epoxy resin was changed to 15 parts by mass in Example 1. The physical properties of this product are shown in Table 1.
参考例３
参考例１において、アクリロニトリルブタジエンゴム含有エポキシ樹脂を１５質量部とした以外は全て参考例１と同様にして多層接着シートを作製した。このものの物性を表１に示す。
Reference example 3
A multilayer adhesive sheet was produced in the same manner as in Reference Example 1 except that in Example 1 , the acrylonitrile butadiene rubber-containing epoxy resin was changed to 15 parts by mass. The physical properties of this product are shown in Table 1.
比較例１
実施例１において、Ｂ層形成塗工液としてアクリルゴム含有エポキシ樹脂を用いなかった以外は全て実施例１と同様にして多層接着シートを作製した。このものの物性を表１に示す。
Comparative Example 1
In Example 1, a multilayer adhesive sheet was produced in the same manner as in Example 1 except that the epoxy resin containing acrylic rubber was not used as the B layer forming coating solution. The physical properties of this product are shown in Table 1.
表１より、本発明の多層接着シート（実施例１〜３）は、比較例１に比べて引張り応力が高いものであることが分かる。また、実施例１〜３のものは比較例１に比べ、高い引張り応力と良好な隙間充填性を有すること、すなわち引張り応力と隙間充填特性とのバランスのよい接着特性を呈していることが分かる。 From Table 1, it can be seen that the multilayer adhesive sheets (Examples 1 to 3 ) of the present invention have a higher tensile stress than Comparative Example 1. Further, it can be seen that Examples 1 to 3 have higher tensile stress and better gap filling properties than Comparative Example 1, that is, exhibit adhesive properties with a good balance between tensile stress and gap filling properties. .
本発明は、軽量で高強度な熱交換器の作製等に好適に利用することができる。 The present invention can be suitably used for production of a lightweight and high-strength heat exchanger.
１：芯材
Ａ：Ａ層
Ｂ：Ｂ層
Ｓ1、Ｓ２：多層接着シートサンプル
１１：熱交換器
1: Core material A: A layer B: B layer S1, S2: Multilayer adhesive sheet sample 11: Heat exchanger
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| WO2015019667A1 (en) * | 2013-08-06 | 2015-02-12 | 千住金属工業株式会社 | Conductive bonding agent and soldered joint |
| FR3010513B1 (en) * | 2013-09-09 | 2015-10-16 | Fives Cryo | COLLEGE HEAT EXCHANGER ARRAY AND METHOD OF BONDING THE SAME |
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| JPH07224252A (en) * | 1994-02-10 | 1995-08-22 | Hitachi Chem Co Ltd | Bonded insulating material sheet, copper-clad bonded insulating material sheet, their production, and production of multilayer circuit board from them |
| JPH10112576A (en) * | 1996-10-04 | 1998-04-28 | Nitsukan Kogyo Kk | Flexible printed wiring board |
| JP4418182B2 (en) * | 2003-06-25 | 2010-02-17 | ソマール株式会社 | HEAT EXCHANGER FORMING MATERIAL, HEAT EXCHANGER MANUFACTURING METHOD USING THE SAME, AND HEAT EXCHANGER |
| JP2005132860A (en) * | 2003-10-28 | 2005-05-26 | Fujikura Ltd | Nonhalogen flame-retardant adhesive resin mixture, metal-clad laminate for flexible printed circuit, cover lay film and flexible printed circuit |
| US8058565B2 (en) * | 2004-04-23 | 2011-11-15 | Nec Corporation | Wiring board, semiconductor device, and method for manufacturing wiring board |
| JP2007045923A (en) * | 2005-08-09 | 2007-02-22 | Somar Corp | Multilayer adhesion sheet, heat exchanger and molding material for forming the same |
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