JP3221978B2 - Cushion material for hot press molding, method for producing the same, heat-resistant heat-sensitive adhesive sheet for cushion material for hot press molding, and method for producing the same - Google Patents
Cushion material for hot press molding, method for producing the same, heat-resistant heat-sensitive adhesive sheet for cushion material for hot press molding, and method for producing the sameInfo
- Publication number
- JP3221978B2 JP3221978B2 JP14531593A JP14531593A JP3221978B2 JP 3221978 B2 JP3221978 B2 JP 3221978B2 JP 14531593 A JP14531593 A JP 14531593A JP 14531593 A JP14531593 A JP 14531593A JP 3221978 B2 JP3221978 B2 JP 3221978B2
- Authority
- JP
- Japan
- Prior art keywords
- heat
- resistant
- adhesive sheet
- unvulcanized
- sensitive 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.)
- Expired - Lifetime
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B30—PRESSES
- B30B—PRESSES IN GENERAL
- B30B15/00—Details of, or accessories for, presses; Auxiliary measures in connection with pressing
- B30B15/06—Platens or press rams
- B30B15/061—Cushion plates
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Description
【０００１】[0001]
【産業上の利用分野】この発明は、電気、電子、機械、
建築、自動車、航空機その他の各種工業における耐熱性
を要求される部材に接着材としてあるいは表層材として
使用することのできる耐熱性感熱接着シート（以下、耐
熱性感熱接着シートは単に「接着シート」と記載するこ
と有）及びその製造方法に関する。また、この発明は、
このような耐熱性接着シートを使用した熱プレス成形用
クッション材をはじめとする耐熱性積層材に関する。The present invention relates to electric, electronic, mechanical,
A heat-resistant heat-sensitive adhesive sheet that can be used as an adhesive or as a surface material for members requiring heat resistance in construction, automobiles, aircraft, and various other industries (hereinafter, the heat-resistant heat-sensitive adhesive sheet is simply called an “adhesive sheet” To be described) and a method for producing the same. In addition, the present invention
The present invention relates to a heat-resistant laminated material including a cushion material for hot press molding using such a heat-resistant adhesive sheet.
【０００２】[0002]
【従来の技術】例えば、化粧合板、プリント基板等のシ
ート状物を熱プレスで成形する場合、成形材料を熱盤と
熱盤との間に挟み込んで一定の圧力と熱をかける方法が
一般に用いられている。このようなプレス成形は、通常
被成形物と直接接触する面に金属鏡面板を配置する一
方、被成形物の全面に均等な圧力と熱を加えるために、
熱盤と鏡面板との間に平板状のクッション材を介在させ
た状態で行われている。従って、このようなクッション
材には、クッション性、耐熱性、耐久性等に優れている
ことが要求される。2. Description of the Related Art For example, when a sheet-like material such as a decorative plywood or a printed board is formed by a hot press, a method of sandwiching a molding material between a hot platen and applying a constant pressure and heat is generally used. Have been. Such press molding is usually to place a metal mirror plate on the surface in direct contact with the molded object, while applying uniform pressure and heat to the entire surface of the molded object,
This is performed with a flat cushion material interposed between the hot platen and the mirror plate. Therefore, such a cushioning material is required to have excellent cushioning properties, heat resistance, durability and the like.
【０００３】ところで、このようなクッション材として
は、一般的に、芳香族ポリアミド繊維、ガラス繊維等の
有機あるいは無機の耐熱性繊維からなる織布あるいは不
織布の層や、耐熱性合成ゴム層など、種々の層を被成形
物品の種類、プレス条件等に応じて適宜選択し、組み合
せて積層一体化した積層材が用いられており、材質や組
み合せの異なる数多くの種類のものが提供されている。[0003] By the way, as such a cushioning material, a woven or nonwoven fabric layer made of organic or inorganic heat-resistant fiber such as aromatic polyamide fiber or glass fiber, a heat-resistant synthetic rubber layer, or the like is generally used. Various layers are appropriately selected in accordance with the type of the article to be molded, pressing conditions, and the like, and a laminated material obtained by combining and laminating them is used. Many types of materials having different materials and combinations are provided.
【０００４】図７に、一般的な熱プレス成形用クッショ
ン材の構成の一例を示す。図において、（１）は耐熱性
繊維層、（２）は接着材層、（３）は表面離型層であ
る。そして、接着材層（２）としては、エポキシ樹脂を
ガラスクロスに含浸し、プリプレグ化したいわゆるガラ
スエポキシ系の感熱接着材が従来用いられていた。FIG. 7 shows an example of the structure of a general cushioning material for hot press molding. In the figure, (1) is a heat-resistant fiber layer, (2) is an adhesive layer, and (3) is a surface release layer. As the adhesive layer (2), a so-called glass epoxy-based heat-sensitive adhesive obtained by impregnating a glass cloth with an epoxy resin and forming a prepreg has conventionally been used.
【０００５】[0005]
【発明が解決しようとする課題】ところが、ガラスエポ
キシ系の接着材は耐熱性、強度において優れた特性を示
す反面、硬質の接着材であるため、圧縮力を受けた時の
被着体の形状変化に追従できず、ガラスクロスの破損を
引き起こし、被着体との間に早期に剥離が生じるという
問題があった。However, while the glass epoxy adhesive exhibits excellent properties in heat resistance and strength, it is a hard adhesive, so the shape of the adherend when subjected to compressive force. There was a problem that the glass cloth could not be followed, causing breakage of the glass cloth and peeling off early with the adherend.
【０００６】一方、ゴム系接着剤は柔軟性があり、形状
変化に追従することができるため、剥離、衝撃、振動、
くり返し圧縮、曲げ応力等に対する耐久性に優れている
ことが知られている。しかし、ゴム系接着剤として一般
的に用いられているものは、天然ゴム、ＳＢＲ、ＮＢ
Ｒ、ＣＲ、ＩＩＲ、再生ゴムなどであり、いずれも耐熱
性に劣るという欠点があった。On the other hand, the rubber-based adhesive is flexible and can follow the shape change, so that peeling, impact, vibration,
It is known that it has excellent durability against repeated compression and bending stress. However, those commonly used as rubber adhesives include natural rubber, SBR, NB
R, CR, IIR, reclaimed rubber, etc., all of which had the drawback of poor heat resistance.
【０００７】この発明の目的は、耐熱性に優れ、しかも
ゴム系接着剤の長所を備えた耐熱性感熱接着シート及び
その製造方法を提供することにある。また、この発明の
目的は、耐熱性や、剥離、衝撃、振動、くり返し圧縮、
曲げ応力等に対する耐久性の要求される用途に好適な熱
プレス成形用クッション材をはじめとする耐熱性積層材
を提供することにある。An object of the present invention is to provide a heat-resistant heat-sensitive adhesive sheet having excellent heat resistance and having the advantages of a rubber-based adhesive, and a method for producing the same. Further, the object of the present invention is heat resistance, peeling, impact, vibration, repeated compression,
An object of the present invention is to provide a heat-resistant laminated material including a cushion material for hot press molding suitable for applications requiring durability against bending stress and the like.
【０００８】[0008]
【課題を解決するための手段】上記目的を達成するた
め、本発明者はふっ素ゴムを接着剤として用いようと試
み、研究を重ねた。ふっ素ゴムは、耐熱性に優れている
反面、溶液の貯蔵安定性が悪いために従来は接着剤とし
て使用することが困難であった。つまり、接着機能をも
たせるためには充分に加硫する必要があるために、活性
度の高い加硫剤及び促進剤を配合しなければならない。
しかも、ふっ素ゴムの中でも耐熱性に優れているポリオ
ール加硫系又はアミン加硫系のふっ素ゴムはイオン反応
により加硫が進められるため、一般的なふっ素ゴムの溶
剤であるメチルエチルケトン（ＭＥＫ）を用いた場合に
は、貯蔵中や塗工中に加硫が進み、ゲル化が発生してし
まう。本発明者は研究を重ねた結果、溶剤の比誘電率と
ふっ素ゴム溶液の貯蔵安定性との間に密接な関係がある
ことを見い出し、ふっ素ゴム溶液の貯蔵安定性を改良す
ることによってこの発明を完成させるに至った。In order to achieve the above object, the present inventors have tried to use fluororubber as an adhesive, and have made repeated studies. Conventionally, fluororubber has excellent heat resistance, but it has been difficult to use it as an adhesive because of poor storage stability of a solution. That is, since it is necessary to sufficiently vulcanize in order to have an adhesive function, a vulcanizing agent and an accelerator having high activity must be blended.
Moreover, among the vulcanized rubbers, the vulcanization of a polyol vulcanization system or an amine vulcanization system, which is excellent in heat resistance, is promoted by an ionic reaction, so that methyl ethyl ketone (MEK), which is a common fluororubber solvent, is used. In such a case, vulcanization proceeds during storage or coating, and gelation occurs. As a result of repeated studies, the present inventor has found that there is a close relationship between the relative dielectric constant of the solvent and the storage stability of the fluororubber solution, and by improving the storage stability of the fluororubber solution, the present invention was improved. Was completed.
【０００９】以下、この発明の課題を解決するための手
段を、耐熱性感熱接着シート、耐熱性感熱接着シートの
製造方法、耐熱性積層材に分けて説明する。Hereinafter, means for solving the problems of the present invention will be described separately for a heat-resistant heat-sensitive adhesive sheet, a method for producing a heat-resistant heat-sensitive adhesive sheet, and a heat-resistant laminated material.
【００１０】（熱プレス成形用クッション材の耐熱性感
熱接着シート） この発明による熱プレス成形用クッション材の耐熱性感
熱接着シートは、耐熱性材料からなるシート状の基材の
両面に未加硫ふっ素ゴムを塗布し、さらにその上から片
面に耐熱塗料を塗布したものである。(Heat-resistant heat-sensitive adhesive sheet of cushioning material for hot press molding) The heat-resistant heat-sensitive adhesive sheet of cushioning material for hot press molding according to the present invention comprises a sheet-like base material made of a heat-resistant material and uncured on both surfaces. Fluoro rubber is applied, and a heat-resistant paint is applied on one side from above.
【００１１】ここで、基材の形態としては、薄板、フィ
ルム、織布、不織布、紙といったシート状のものであれ
ばいずれでもよく、また、その材質も特に限定されな
い。しかし、作業の容易性、基材とふっ素ゴムとの接着
性、耐熱性、強度、形状安定性、柔軟性等を考慮すれ
ば、耐熱性繊維の織布を基材に用いるのが最も好まし
い。このような耐熱性繊維としては、ポリアミド繊維、
芳香族ポリアミド繊維、ポリイミド繊維、ポリアミドイ
ミド繊維、ポリエステル繊維、芳香族ポリエステル繊
維、ポリアリレート繊維、ふっ素繊維、アクリル繊維、
ポリビニルアルコール繊維等の有機繊維や、ガラス繊
維、カーボン繊維、スラグ・ロック繊維、セラミックス
繊維、金属繊維等の無機繊維を挙げることができる。The substrate may be in any form as long as it is in the form of a sheet, such as a thin plate, a film, a woven fabric, a nonwoven fabric, and a paper, and the material is not particularly limited. However, in consideration of ease of operation, adhesion between the base material and the fluororubber, heat resistance, strength, shape stability, flexibility, and the like, it is most preferable to use a woven fabric of heat-resistant fibers as the base material. As such heat resistant fibers, polyamide fibers,
Aromatic polyamide fiber, polyimide fiber, polyamide imide fiber, polyester fiber, aromatic polyester fiber, polyarylate fiber, fluorine fiber, acrylic fiber,
Examples thereof include organic fibers such as polyvinyl alcohol fibers, and inorganic fibers such as glass fibers, carbon fibers, slag / rock fibers, ceramic fibers, and metal fibers.
【００１２】この発明に従った熱プレス成形用クッショ
ン材の耐熱性感熱接着シートでは、耐熱塗料を塗布して
いるので、表面の耐熱性と離型性を向上させることがで
きる。In the heat-resistant and heat-sensitive adhesive sheet of the cushioning material for hot press molding according to the present invention, since the heat-resistant paint is applied, the heat resistance and the releasability of the surface can be improved.
【００１３】耐熱塗料としては、ふっ素樹脂系、芳香族
樹脂系、フェノール樹脂系、メラミン樹脂系、エポキシ
樹脂系、不飽和ポリエステル樹脂系、シリコーン樹脂
系、ポリイミド樹脂系、熱硬化性アクリル樹脂系、水素
化ＮＢＲ系、ふっ素ゴム系、ＥＰＭ系、ＥＰＤＭ系等の
有機系耐熱塗料や、アルカリシリケート系、コロイダル
シリカ系、酸性金属リン酸塩系、重クロム酸リン酸系、
ほうろう系等の無機系耐熱塗料、およびアルキルシリケ
ート系、アルキルチタネート系、ボロンシロキサン系等
の有機・無機複合系耐熱塗料を挙げることができ、それ
ぞれ単独で、又はブレンド系で、又は共重合体として用
いることができる。Examples of the heat-resistant paint include fluorine resin, aromatic resin, phenol resin, melamine resin, epoxy resin, unsaturated polyester resin, silicone resin, polyimide resin, thermosetting acrylic resin, Organic heat-resistant paints such as hydrogenated NBR, fluoro rubber, EPM, EPDM, etc., alkali silicate, colloidal silica, acidic metal phosphate, dichromic phosphate,
Inorganic heat-resistant paints such as enamels, and alkyl silicate-based, alkyl titanate-based, organic and inorganic composite heat-resistant paints such as boron siloxane-based can be mentioned, each alone, or in a blend system, or as a copolymer Can be used.
【００１４】ふっ素ゴムは高価であるため、塗布量を必
要以上に多くすることは好ましくないが、塗布量が少な
すぎると十分な接着力が得られない。好ましいふっ素ゴ
ムの塗布量は、その乾燥時の厚みが片面につき３〜３０
０μｍとなる程度である。[0014] Since fluoro rubber is expensive, it is not preferable to increase the coating amount more than necessary. However, if the coating amount is too small, sufficient adhesive strength cannot be obtained. The preferred amount of the applied fluororubber is such that the thickness when dried is 3 to 30 per side.
It is about 0 μm.
【００１５】（熱プレス成形用クッション材の耐熱性感
熱接着シートの製造方法） この発明に従った熱プレス成形用クッション材の耐熱性
感熱接着シートの製造方法では、比誘電率（ε）が１７
以下の溶剤中に未加硫ふっ素ゴムのコンパウンド１００
重量部および酸０．５〜５重量部を溶かし、この溶液を
耐熱性材料からなるシート状の基材に塗布した後、ふっ
素ゴムを未加硫のまま乾燥させることを特徴としてい
る。より好ましい溶剤の比誘電率は１２以下である。(Method for Producing Heat-Resistant Heat-Sensitive Adhesive Sheet for Cushion Material for Hot Press Molding) In the method for producing a heat-resistant heat-sensitive adhesive sheet for cushion material for hot press molding according to the present invention, the relative dielectric constant (ε) is 17
Compound 100 of unvulcanized fluoro rubber in the following solvent
After dissolving a weight part and an acid of 0.5 to 5 parts by weight, applying this solution to a sheet-like substrate made of a heat-resistant material, the fluororubber is dried without being vulcanized. More preferable solvent has a relative dielectric constant of 12 or less.
【００１６】ここで、溶剤は、比誘電率（ε）が１７以
下のものを単独で用いるだけでなく、単独では比誘電率
（ε）が１７より大きいものでも、２種以上の溶剤を混
合し、比誘電率（ε）を１７以下に調整すれば用いるこ
とができる。As the solvent, not only a solvent having a relative dielectric constant (ε) of 17 or less alone is used, but also a solvent having a relative dielectric constant (ε) of more than 17 alone is mixed with two or more solvents. However, it can be used if the relative dielectric constant (ε) is adjusted to 17 or less.
【００１７】溶剤の比誘電率（ε）は、図８に示すよう
な主電極（Ｌ）、対電極（Ｈ）、ガード電極（Ｇ）から
なる平行円板型の三端子電極を用いて電極間を溶剤
（Ｘ）で満たした時の電気容量（Ｃ′）を１ＭＨｚで測
定し、式１に代入することにより求めることができる。The relative dielectric constant (ε) of the solvent is determined by using a parallel disk type three-terminal electrode composed of a main electrode (L), a counter electrode (H), and a guard electrode (G) as shown in FIG. The electric capacity (C ′) when the space is filled with the solvent (X) is measured at 1 MHz, and can be obtained by substituting into the equation (1).
【００１８】[0018]
【数１】 (Equation 1)
【００１９】ここで、三端子電極の真空容量（Ｃ）は式
２で与えられる。Here, the vacuum capacity (C) of the three-terminal electrode is given by equation (2).
【００２０】[0020]
【数２】 (Equation 2)
【００２１】なお、三端子電極による電気容量（Ｃ′）
の測定については、「新実験化学講座５−基礎技術４電
気」（（社）日本化学会編、昭和５１年丸善（株）発
行）の２７９頁〜２８０頁及び同２９７頁〜２９８頁に
詳しい説明がある。The electric capacity (C ') of the three-terminal electrode
For details of the measurement, see pages 279 to 280 and 297 to 298 of "New Experimental Chemistry Course 5-Basic Technology 4 Electric" (edited by The Chemical Society of Japan, published in 1976 by Maruzen Co., Ltd.). There is an explanation.
【００２２】単独で比誘電率（ε）が１７以下の溶剤と
その比誘電率（ε）を例示するならば、メチルｎ−プロ
ピルケトン（ＭＰＫ；ε＝１５．１）、メチルｎ−ブチ
ルケトン（ＭＢＫ；ε＝１２．２）、メチルイソブチル
ケトン（ＭＩＢＫ；ε＝１３．３）、メチルｎ−アミル
ケトン（ＭＡＫ；ε＝９．８）、ジエチルケトン（ＤＥ
Ｋ；ε＝１７．０）、ギ酸メチル（ε＝８．５）、ギ酸
エチル（ε＝９．１）、ギ酸プロピル（ε＝７．７）、
ギ酸アミル（ε＝６．５）、酢酸メチル（ε＝７．
０）、酢酸エチル（ε＝６．０）、酢酸ｎ−プロピル
（ε＝５．７）、酢酸ｎ−ブチル（ε＝５．２）、酢酸
イソブチル（ε＝５．２）、酢酸ｎ−アミル（ε＝４．
８）、酢酸イソアミル（ε＝４．６）、テトラヒドロフ
ラン（ＴＨＦ；ε＝７．６）等を挙げることができる。If a solvent having a relative dielectric constant (ε) of 17 or less alone and its relative dielectric constant (ε) are exemplified, methyl n-propyl ketone (MPK; ε = 15.1), methyl n-butyl ketone ( MBK; ε = 12.2), methyl isobutyl ketone (MIBK; ε = 13.3), methyl n-amyl ketone (MAK; ε = 9.8), diethyl ketone (DE
K; ε = 17.0), methyl formate (ε = 8.5), ethyl formate (ε = 9.1), propyl formate (ε = 7.7),
Amyl formate (ε = 6.5), methyl acetate (ε = 7.
0), ethyl acetate (ε = 6.0), n-propyl acetate (ε = 5.7), n-butyl acetate (ε = 5.2), isobutyl acetate (ε = 5.2), n-acetic acid Amyl (ε = 4.
8), isoamyl acetate (ε = 4.6), tetrahydrofuran (THF; ε = 7.6) and the like.
【００２３】また、溶剤には必要に応じて０．５〜５重
量部の酸を添加することができるが、この場合の酸は、
乾燥時に溶剤と一緒に蒸発するものを用いる。このよう
な酸としては、ギ酸、酢酸、無水酢酸、氷酢酸、酪酸、
無水酪酸等が挙げられる。If necessary, 0.5 to 5 parts by weight of an acid can be added to the solvent.
One that evaporates together with the solvent during drying is used. Such acids include formic acid, acetic acid, acetic anhydride, glacial acetic acid, butyric acid,
Butyric anhydride and the like.
【００２４】基材への未加硫ふっ素ゴムの塗布は、ナイ
フコート方式、ロールコート方式、又は浸せきによって
行うことができる。ふっ素ゴム溶液の粘度が低い場合は
ロールコート方式や浸せきが適しており、この場合は基
材の表面にふっ素ゴムが付着するとともに、基材の全体
に、あるいは部分的にふっ素ゴムが含浸されることとな
る。一方、被着体と接着シートとの強固な接着力を得た
い場合には、基材の表面に付着させるふっ素ゴムの固形
分を多くすることが好ましいため、ふっ素ゴム溶液の粘
度を高くし、ナイフコート方式で塗工するのが好まし
い。The application of the unvulcanized fluoro rubber to the substrate can be performed by a knife coating method, a roll coating method, or dipping. When the viscosity of the fluororubber solution is low, the roll coating method or dipping is suitable.In this case, the fluororubber adheres to the surface of the base material, and the entire or partial base material is impregnated with the fluororubber. It will be. On the other hand, if it is desired to obtain a strong adhesive force between the adherend and the adhesive sheet, it is preferable to increase the solid content of the fluororubber to be adhered to the surface of the base material, so that the viscosity of the fluororubber solution is increased, It is preferable to apply by a knife coat method.
【００２５】ふっ素ゴム溶液の粘度は、高すぎる場合は
塗工しづらくなる。逆に、低すぎる場合は固形分濃度が
低いために塗工回数を増やさなければならなくなり、作
業に手間がかかる。また、基材に織布を用いる場合に
は、織目の大きさにもよるが、粘度が低すぎると溶液が
織目を通過してしまい、うまく塗布できなくなる。この
ような理由から、ふっ素ゴム溶液の粘度は３００〜４
０，０００ｃｐに保つことが好ましく、さらに好ましい
粘度は２，０００〜２０，０００ｃｐである。If the viscosity of the fluororubber solution is too high, it becomes difficult to apply the solution. Conversely, if it is too low, the solid content concentration is low, so the number of coatings must be increased, and the work is troublesome. Further, when a woven fabric is used as the base material, depending on the size of the weave, if the viscosity is too low, the solution passes through the weave and the coating cannot be performed well. For these reasons, the viscosity of the fluororubber solution is 300 to 4
It is preferable to keep the viscosity at 000 cp, and more preferable viscosity is 2,000 to 20,000 cp.
【００２６】（熱プレス成形用クッション材）この発明
の１つの局面に従った熱プレス成形用クッション材は、
耐熱性材料か らなり、少なくとも一方の面に不織布層を有する被着体
と、耐熱性材料からなるシート状の基材の両面に未加硫
ふっ素ゴムを塗布し、さらにその上から片面に耐熱性塗
料を塗布した耐熱性感熱接着シートとを備え、被着体の
不織布層と、接着シートの未加硫ふっ素ゴムとを当接さ
せ、圧力と熱を加えて未加硫ふっ素ゴムを加硫して被着
体と接着シートとを接着一体化したものである。この発
明の他の局面に従った熱プレス成形用クッション材は、
耐熱性材料からなり、上下の面に不織布を有する第１の
被着体と、上下の面に不織布を有する第２の被着体と
を、耐熱性材料からなるシート状の基材の両面に未加硫
ふっ素ゴムを塗布してなる第１の耐熱性感熱接着シート
を介して積層し、さらに第１の被着体上および第２の被
着体上に、被着体側に向く面に未加硫ふっ素ゴムを塗布
した第２および第３の耐熱性感熱接着シートを積層し、
第２および第３の耐熱性感熱接着シートの他方の面に未
加硫ふっ素ゴムを塗布し、さらにその上に耐熱性塗料を
塗布し、圧力と熱を加えて未加硫ふっ素ゴムを加硫する
と同時に全体を接着一体化したものである。被着体は単
層構造であってもよく、多層構造であってもよい。 （熱プレス成形用クッション材の製造方法） この発明の１つの局面に従った熱プレス成形用クッショ
ン材の製造方法では、比誘電率（ε）が１７以下の溶剤
中に未加硫ふっ素ゴムのコンパウンド１００重量部およ
び酸０．５〜５重量部を溶かし、この溶液を耐熱性材料
からなるシート状の基材の少なくとも一方の面に塗布し
た後、ふっ素ゴムを未加硫のまま乾燥させて耐熱性感熱
接着シートを作成し、少なくとも一方の面に不織布層を
有する被着体と、前記接着シートの未加硫ふっ素ゴムと
を当接させ、圧力と熱を加えて未加硫ふっ素ゴムを加硫
すると同時に全体を接着一体化する。(Cushioning material for hot press molding) The cushioning material for hot press molding according to one aspect of the present invention comprises:
A non-vulcanized fluoroelastomer is applied to both sides of an adherend made of a heat-resistant material and having a nonwoven fabric layer on at least one surface, and a sheet-shaped substrate made of a heat-resistant material. A heat-resistant heat-sensitive adhesive sheet coated with a heat-resistant paint, the non-woven fabric layer of the adherend is brought into contact with the unvulcanized fluoro rubber of the adhesive sheet, and pressure and heat are applied to vulcanize the unvulcanized fluoro rubber. Then, the adherend and the adhesive sheet are bonded and integrated. The cushioning material for hot press molding according to another aspect of the present invention,
A first adherend made of a heat-resistant material and having a nonwoven fabric on upper and lower surfaces and a second adherend having a nonwoven fabric on the upper and lower surfaces are provided on both surfaces of a sheet-like base made of a heat-resistant material. Laminated via a first heat-resistant heat-sensitive adhesive sheet coated with unvulcanized fluoro rubber, and further, on the first adherend and the second adherend, the surface facing the adherend has an uncoated surface. Laminating the second and third heat-resistant heat-sensitive adhesive sheets coated with the vulcanized fluoro rubber,
An unvulcanized fluoro rubber is applied to the other surface of the second and third heat resistant heat-sensitive adhesive sheets, and a heat resistant paint is further applied thereon, and pressure and heat are applied to vulcanize the unvulcanized fluoro rubber. At the same time, the whole is bonded and integrated. The adherend may have a single-layer structure or a multilayer structure. (Manufacturing Method of Cushion Material for Hot Press Molding) According to the manufacturing method of the cushion material for hot press molding according to one aspect of the present invention, the unvulcanized fluoro rubber is dissolved in a solvent having a relative dielectric constant (ε) of 17 or less. After dissolving 100 parts by weight of the compound and 0.5 to 5 parts by weight of the acid and applying this solution to at least one surface of a sheet-like substrate made of a heat-resistant material, the fluororubber is dried without being vulcanized. A heat-resistant heat-sensitive adhesive sheet is prepared, and an adherend having a nonwoven fabric layer on at least one surface is brought into contact with the unvulcanized fluoro rubber of the adhesive sheet, and pressure and heat are applied to unvulcanized fluoro rubber. At the same time as vulcanization, the whole is bonded and integrated.
【００２７】被着体は、耐熱性繊維、耐熱性合成樹脂、
耐熱性合成ゴム、金属、セラミックス等の種々の物質の
単体または複合体を、板、フィルム、織布、不織布、紙
といった種々の形態で用いることができる。少なくとも
１つの被着体は、耐熱性感熱接着シート側に向く面に不
織布層を有する。The adherend is made of heat-resistant fiber, heat-resistant synthetic resin,
A simple substance or a composite of various substances such as heat-resistant synthetic rubber, metal, and ceramics can be used in various forms such as a plate, a film, a woven fabric, a nonwoven fabric, and paper. At least one adherend has a nonwoven fabric layer on a surface facing the heat-resistant heat-sensitive adhesive sheet side.
【００２８】上記耐熱性繊維としては、ポリアミド繊
維、芳香族ポリアミド繊維、ポリイミド繊維、ポリアミ
ドイミド繊維、ポリエステル繊維，芳香族ポリエステル
繊維、ポリアリレート繊維、ふっ素繊維、アクリル繊
維、ポリビニルアルコール繊維等の有機繊維や、ガラス
繊維、カーボン繊維、スラグ・ロック繊維、セラミック
ス繊維、金属繊維等の無機繊維が挙げられる。The heat-resistant fibers include organic fibers such as polyamide fibers, aromatic polyamide fibers, polyimide fibers, polyamide imide fibers, polyester fibers, aromatic polyester fibers, polyarylate fibers, fluorine fibers, acrylic fibers, and polyvinyl alcohol fibers. And inorganic fibers such as glass fibers, carbon fibers, slag / rock fibers, ceramic fibers, and metal fibers.
【００２９】上記耐熱性合成樹脂としては、フェノール
樹脂、メラミン樹脂、ふっ素樹脂、エポキシ樹脂、不飽
和ポリエステル樹脂、シリコーン樹脂、ポリイミド樹
脂、熱硬化性アクリル樹脂、フラン樹脂、ユリア樹脂、
ジアリルフタレート樹脂、ポリウレタン樹脂等の単体ま
たはブレンド系または共重合体が挙げられる。Examples of the heat-resistant synthetic resin include a phenol resin, a melamine resin, a fluororesin, an epoxy resin, an unsaturated polyester resin, a silicone resin, a polyimide resin, a thermosetting acrylic resin, a furan resin, a urea resin,
A simple substance such as a diallyl phthalate resin and a polyurethane resin, or a blend or a copolymer may be used.
【００３０】上記耐熱性合成ゴムとしては、水素化ＮＢ
Ｒ、ふっ素ゴム、ＥＰＭ、ＥＰＤＭ等の単体又はブレン
ド系又は共重合体が挙げられる。As the heat-resistant synthetic rubber, hydrogenated NB is used.
R, fluorine rubber, EPM, EPDM, and other simple or blended or copolymers.
【００３１】[0031]
【作用】この発明で用いるふっ素ゴムの溶剤は、比誘電
率（ε）が１７以下、好ましくは１２以下であるため、
ふっ素ゴム溶液の加硫反応を遅らせることができ、溶液
の貯蔵安定性が向上する。The fluororubber used in the present invention has a relative dielectric constant (ε) of 17 or less, preferably 12 or less.
The vulcanization reaction of the fluororubber solution can be delayed, and the storage stability of the solution is improved.
【００３２】図９に、溶剤の比誘電率（ε）とふっ素ゴ
ム溶液のゲル化日数との関係についての測定結果を示
す。測定を行ったふっ素ゴム溶液の配合は、表１の通り
である。FIG. 9 shows the results of measurement on the relationship between the relative dielectric constant (ε) of the solvent and the number of days of gelation of the fluororubber solution. The composition of the fluororubber solution subjected to the measurement is as shown in Table 1.
【００３３】[0033]
【表１】 [Table 1]
【００３４】この測定において、ふっ素ゴムコンパウン
ドはポリオール加硫系のものを用いた。また、酸（酢
酸）１重量部と加硫促進剤（水酸化カルシウム）５重量
部とを添加した。上記配合で、溶剤の異なる種々のふっ
素ゴム溶液を作成し、温度条件を４０°Ｃに保って密閉
保存しながら溶液の粘度変化を測定した。そして、溶液
の粘度が１００，０００ｃｐに達するまでの日数をゲル
化日数とした。In this measurement, a fluorine rubber compound of a polyol vulcanization type was used. Further, 1 part by weight of an acid (acetic acid) and 5 parts by weight of a vulcanization accelerator (calcium hydroxide) were added. With the above composition, various fluororubber solutions having different solvents were prepared, and a change in the viscosity of the solution was measured while keeping the temperature condition at 40 ° C. in a sealed state. The number of days until the viscosity of the solution reached 100,000 cp was defined as the number of gelation days.
【００３５】この測定結果から、溶剤の比誘電率（ε）
とふっ素ゴムのゲル化日数との間には密接な関係があ
り、比誘電率（ε）が１７以下の溶剤を用いれば、ふっ
素ゴム溶液の貯蔵安定性が良くなることが判る。そし
て、特に比誘電率（ε）が１２以下の溶剤を用いた場合
には貯蔵安定性は著しく向上することが判る。From the measurement results, the relative dielectric constant (ε) of the solvent
And the number of days of gelation of the fluororubber are closely related to each other, and it is found that the storage stability of the fluororubber solution is improved by using a solvent having a relative dielectric constant (ε) of 17 or less. In particular, it is found that the storage stability is significantly improved when a solvent having a relative dielectric constant (ε) of 12 or less is used.
【００３６】次に、溶剤に酸を添加した場合の作用につ
いて述べる。溶剤に酸を添加することによって、加硫反
応を更に遅らせ、ふっ素ゴム溶液の貯蔵安定性を向上さ
せることができる。また、酸を添加することによって、
溶剤の粘度を増大させる作用もあることが実験により判
った。酸を添加する場合の添加量は、ふっ素ゴムコンパ
ウンド１００重量部に対して０．５〜５重量部とし、好
ましくは１〜３重量部とする。０．５重量部より少ない
場合は、酸を添加する効果があまり現れない。５部より
多い場合、溶液粘度が上がり過ぎて塗工が困難となり、
また乾燥後の酸の残留率が多くなるために後の加硫に悪
影響を及ぼし好ましくない。Next, the operation when an acid is added to the solvent will be described. By adding an acid to the solvent, the vulcanization reaction can be further delayed, and the storage stability of the fluororubber solution can be improved. Also, by adding an acid,
Experiments have shown that it also has the effect of increasing the viscosity of the solvent. When the acid is added, the amount is 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight, per 100 parts by weight of the fluororubber compound. When the amount is less than 0.5 part by weight, the effect of adding the acid is not so much exhibited. If the amount is more than 5 parts, the solution viscosity becomes too high and coating becomes difficult,
Further, since the residual ratio of the acid after drying is increased, the vulcanization afterwards is adversely affected, which is not preferable.
【００３７】図１０に、酢酸の添加量とふっ素ゴム溶液
のゲル化日数及び溶液粘度との関係についての測定結果
を示す。測定を行ったふっ素ゴム溶液の配合は、表２の
通りである。FIG. 10 shows the measurement results of the relationship between the amount of acetic acid added and the number of gelation days and the solution viscosity of the fluororubber solution. The composition of the fluororubber solution subjected to the measurement is as shown in Table 2.
【００３８】[0038]
【表２】 [Table 2]
【００３９】この測定においては、溶剤はふっ素ゴムに
用いられる代表的な溶剤であるメチルエチルケトン（Ｍ
ＥＫ）を用いた。ふっ素ゴムコンパウンドはポリオール
加硫系のものを用いた。また、加硫促進剤として、水酸
化カルシウムを添加した。そして、この配合で酢酸の添
加量の異なる多数のふっ素ゴム溶液を作成し、初期の溶
液粘度と、温度条件を４０゜Ｃに保って密閉保存したと
きのゲル化日数とを測定した。なお、ゲル化日数は、前
記同様溶液の粘度が１００，０００ｃｐに達するまでの
日数とした。In this measurement, the solvent was methyl ethyl ketone (M
EK) was used. As the fluorine rubber compound, a polyol vulcanization type was used. Calcium hydroxide was added as a vulcanization accelerator. Then, a large number of fluororubber solutions having different amounts of acetic acid were prepared in this formulation, and the initial solution viscosity and the number of gelation days when the temperature was kept at 40 ° C. and sealed and stored were measured. The number of gelation days was the number of days until the viscosity of the solution reached 100,000 cp in the same manner as described above.
【００４０】[0040]
【実施例】以下、この発明の実施例について説明する。Embodiments of the present invention will be described below.
【００４１】１．（ふっ素ゴムコンパウンドの作成） 表３に示すふっ素ゴム及び各配合剤をニーダーで混練り
した後、２本のロールによって未加硫ふっ素ゴムのリボ
ンを作成した。そして、これをペレタイザーでペレット
状に粉砕した。1. (Preparation of Fluoro Rubber Compound) After kneading the fluoro rubber and each compounding agent shown in Table 3 with a kneader, an unvulcanized fluoro rubber ribbon was prepared by two rolls. Then, this was pulverized into a pellet with a pelletizer.
【００４２】[0042]
【表３】 [Table 3]
【００４３】２．（ふっ素ゴム溶液の作成） 表４に示す各材料を用いて未加硫ふっ素ゴム溶液を作成
した。ここで用いた溶剤は、酢酸ｎ−ブチル（ε＝５．
２）とメチルイソブチルケトン（ＭＩＢＫ；ε＝１３．
３）とメチルエチルケトン（ＭＥＫ；ε＝１８．８）と
の３種類の混合溶剤であり、この混合溶剤の比誘電率
は、ε＝１１．１であった。2. (Preparation of Fluorine Rubber Solution) An unvulcanized fluoro rubber solution was prepared using each material shown in Table 4. The solvent used here was n-butyl acetate (ε = 5.
2) and methyl isobutyl ketone (MIBK; ε = 13.
3) and three kinds of mixed solvents of methyl ethyl ketone (MEK; ε = 18.8), and the relative permittivity of the mixed solvent was ε = 11.1.
【００４４】まず、上記３種類の混合溶剤を全て撹拌槽
に投入し、次に酢酸を投入して攪拌した。その後、上記
作成済のペレット状のふっ素ゴムコンパウンドを攪拌し
ながら投入した。なお、溶解温度は５０°Ｃ以下で実施
し、溶解終了後、一昼夜熟成した。First, all of the above three types of mixed solvents were charged into a stirring tank, and then acetic acid was charged and stirred. Thereafter, the prepared fluororubber compound in the form of pellets was charged with stirring. The dissolution was carried out at a temperature of 50 ° C. or lower.
【００４５】[0045]
【表４】 [Table 4]
【００４６】３．（耐熱性感熱接着シートの作成） 上記ふっ素ゴム溶液を主剤とし、これと硬化剤とを表５
に示す配合で混合した。そして、この混合溶液をナイフ
コート方式で基材に塗布し、乾燥室で溶剤を揮発させて
ふっ素ゴムを未加硫のまま乾燥させ、実施例１および２
の接着シートを作成した。なお、塗工中は、随時トルエ
ンを追加することによってふっ素ゴム混合溶液の粘度を
１０，０００〜２０，０００ｃｐに保った。3. (Preparation of Heat-Resistant Heat-Sensitive Adhesive Sheet)
Was mixed according to the formula shown in Table 1. Then, this mixed solution was applied to a substrate by a knife coating method, the solvent was evaporated in a drying chamber, and the fluororubber was dried without being vulcanized.
Was prepared. During the coating, the viscosity of the fluororubber mixed solution was kept at 10,000 to 20,000 cp by adding toluene as needed.
【００４７】[0047]
【表５】 [Table 5]
【００４８】〔実施例１〕図１に、実施例１による接着
シート（４）の構成を示す。この実施例では、厚み約１
７０μｍのガラスクロス（ユニチカ株式会社製；ユーエ
ムグラスＨ２０１ＳＤ）からなる基材の両面に上記混合
溶液を３回ずつ塗り重ねて両面接着用の接着シートとし
た。出来上がった接着シートは、ガラスクロスからなる
基材（５）の両面に未加硫ふっ素ゴム（６）、（６）を
塗布してなる構成である。なお、この接着シート（４）
の全体厚みは２１０μｍであった。Embodiment 1 FIG. 1 shows the structure of an adhesive sheet (4) according to Embodiment 1. In this embodiment, the thickness is about 1
The above mixed solution was applied three times on both surfaces of a substrate made of a 70 μm glass cloth (manufactured by Unitika Ltd .; UMG Glass H201SD) three times to obtain an adhesive sheet for double-sided bonding. The finished adhesive sheet has a configuration in which unvulcanized fluoro rubbers (6) and (6) are applied to both surfaces of a substrate (5) made of glass cloth. The adhesive sheet (4)
Had a total thickness of 210 μm.
【００４９】〔実施例２〕図２に、実施例２による接着
シート（７）の構成を示す。この実施例では、実施例１
で用いたガラスクロスからなる基材の片面には上記混合
溶液を３回塗り重ねた。そして、他面には上記混合溶液
を１回だけ塗り付け、更にその上から耐熱性塗料として
芳香族アクリル樹脂液をナイフコート方式で１回塗り付
けた。このようにして表層用接着シートとした。出来上
がった接着シートは、ガラスクロスからなる基材（５）
の両面に未加硫ふっ素ゴム（６）、（６）を塗布し、更
にその上から片面に芳香族アクリル樹脂系の耐熱塗料
（８）を塗布してなる構成である。なお、この接着シー
ト（７）の全体厚みは２００μｍであった。Embodiment 2 FIG. 2 shows the structure of an adhesive sheet (7) according to Embodiment 2. In this embodiment, the first embodiment
The above mixed solution was applied three times on one side of the substrate made of the glass cloth used in the above. Then, the above mixed solution was applied only once on the other surface, and an aromatic acrylic resin liquid was further applied thereon as a heat-resistant paint once by knife coating. Thus, a surface layer adhesive sheet was obtained. The finished adhesive sheet is a substrate made of glass cloth (5)
Are coated with unvulcanized fluororubbers (6) and (6) on both sides, and an aromatic acrylic resin-based heat-resistant paint (8) is coated on one side from above. The overall thickness of the adhesive sheet (7) was 200 μm.
【００５０】〔従来例〕従来例として、実施例１で用い
たガラスクロスからなる基材にエポキシ樹脂を含浸して
プリプレグ化し、ガラスエポキシ系の両面接着用接着シ
ートとした。[Conventional Example] As a conventional example, the base material made of the glass cloth used in Example 1 was impregnated with an epoxy resin to prepare a prepreg, thereby obtaining a glass epoxy adhesive sheet for double-sided adhesion.
【００５１】４．（耐熱性積層材の作成） 〔実施例３〕図３に、実施例３による耐熱性積層材の積
層構成を示す。この実施例では、被着体Ａを多層構造で
構成し、内層として用いた。被着体Ａは、芳香族ポリア
ミド繊維よりなる紙にエポキシ樹脂系プリプレグ粉末を
内添したシート（９）の両面にスラグ・ロック繊維を主
成分とする抄造紙にエポキシ樹脂系プリプレグ粉末を内
添したシート（１０）、（１０）を積層し、更にその両
面に上記従来例によるガラスエポキシ系の接着シート
（１１）、（１１）を積層し、更にその両面に芳香族ポ
リアミド繊維（帝人株式会社製；コーネックス▲Ｒ▼）
よりなる基布補強ニードルパンチ不織布（１２）、（１
２）を積層したものである。また、被着体Ｂは、４ふっ
化エチレン−６ふっ化プロピレン共重合体樹脂（ＦＥ
Ｐ）からなるふっ素樹脂フィルム（ダイキン工業株式会
社製；ネオフロン▲Ｒ▼ＦＥＰ）（１３）、（１３）
を、表層として用いた。4. (Preparation of Heat Resistant Laminate) Example 3 FIG. 3 shows a laminated structure of a heat resistant laminate according to Example 3. In this example, the adherend A was formed in a multilayer structure and used as an inner layer. The adherend A was prepared by internally adding epoxy resin-based prepreg powder to paper made mainly of slag and rock fibers on both sides of a sheet (9) in which epoxy resin-based prepreg powder was internally added to paper made of aromatic polyamide fiber. The sheets (10) and (10) thus obtained are laminated, and the glass epoxy adhesive sheets (11) and (11) according to the above-mentioned conventional example are further laminated on both sides thereof, and aromatic polyamide fibers (Teijin Co., Ltd.) are further laminated on both sides thereof. Made by Conex®R )
(12), (1)
2) are laminated. Further, the adherend B is made of ethylene tetrafluoride-6-propylene copolymer resin (FE).
Fluorine resin film made of P) (manufactured by Daikin Industries, Ltd .; Neoflon ▲ R ▼ FEP) (13) , (13)
Was used as a surface layer.
【００５２】まず、多層に積層した被着体Ａの両面に実
施例１の両面接着用接着シート（４）、（４）を積層
し、更にその両面に被着体Ｂ（１３）、（１３）を積層
し、これらを温度１８０°Ｃ、面圧２０ｋｇ／ｃｍ２で
７０分間プレスして未加硫ふっ素ゴムを加硫すると同時
に全体を接着一体化した。このようにして得られた耐熱
性積層材は、特に熱プレス成形用クッション材として好
適である。First, the double-sided adhesive sheets (4) and (4) of Example 1 are laminated on both surfaces of the multi-layer adherend A, and the adherends B (13) and (13) are further laminated on both surfaces. ) Were laminated and pressed at a temperature of 180 ° C. and a surface pressure of 20 kg / cm 2 for 70 minutes to vulcanize the unvulcanized fluoro rubber and simultaneously bond and integrate the whole. The heat-resistant laminated material thus obtained is particularly suitable as a cushion material for hot press molding.
【００５３】〔実施例４〕図４に、実施例４による耐熱
性積層材の積層構成を示す。この実施例では、被着体Ｃ
として芳香族ポリアミド繊維（帝人株式会社製；コーネ
ックス▲Ｒ▼）よりなる基布補強ニードルパンチ不織布
（１４）を３枚用いた。Fourth Embodiment FIG. 4 shows a laminated structure of a heat-resistant laminated material according to a fourth embodiment. In this embodiment, the adherend C
Aromatic polyamide fibers (manufactured by Teijin Ltd .; Conex ▲ R ▼) as three of more becomes the base fabric reinforced needlepunched nonwoven (14) was used.
【００５４】まず、被着体Ｃ（１４）、（１４）、（１
４）を実施例１の両面接着用接着シート（４）、（４）
を介して３層積層し、更にその両面に実施例２の表層用
接着シート（７）、（７）を積層し、これらを温度１８
０°Ｃ、面圧２０ｋｇ／ｃｍ２で７０分間プレスして未
加硫ふっ素ゴムを加硫すると同時に全体を接着一体化し
た。このようにして得られた耐熱性積層材は、特に熱プ
レス成形用クッション材として好適である。First, the adherends C (14), (14), (1)
4) is a double-sided adhesive sheet (4), (4) of Example 1.
, And the surface-side adhesive sheets (7) and (7) of Example 2 were further laminated on both surfaces thereof, and these were heated at a temperature of 18
The unvulcanized fluoro rubber was vulcanized by pressing at 0 ° C. and a surface pressure of 20 kg / cm 2 for 70 minutes, and the whole was bonded and integrated. The heat-resistant laminated material thus obtained is particularly suitable as a cushion material for hot press molding.
【００５５】〔比較例１〕図５に、比較例１による耐熱
性積層材の積層構成を示す。比較例１では、実施例３に
おいて、実施例１の接着シート（４）、（４）に代えて
従来例の接着シート（１１）、（１１）を用いた。つま
り、実施例３で用いた被着体Ａの両面に従来例の接着シ
ート（１１）、（１１）を積層し、更にその両面に実施
例３で用いた被着体Ｂ（１３）、（１３）を積層し、こ
れらを温度１８０゜Ｃ、面圧２０ｋｇ／ｃｍ２で７０分
間プレスしてガラスエポキシ系プリプレグを硬化させる
と同時に接着一体化した。Comparative Example 1 FIG. 5 shows a laminated structure of a heat-resistant laminated material according to Comparative Example 1. In Comparative Example 1, the conventional adhesive sheets (11) and (11) were used instead of the adhesive sheets (4) and (4) of Example 1 in Example 3. That is, the adhesive sheets (11) and (11) of the conventional example are laminated on both surfaces of the adherend A used in Example 3, and the adherends B (13) and ( 13) were laminated, and these were pressed at a temperature of 180 ° C. and a surface pressure of 20 kg / cm 2 for 70 minutes to cure the glass epoxy prepreg and simultaneously bond and integrate.
【００５６】〔比較例２〕図６に、比較例２による耐熱
性積層材の積層構成を示す。比較例２では、実施例４で
用いた被着体Ｃ（１４）、（１４）、（１４）を従来例
の接着シート（１１）、（１１）を介して３層積層し、
更にその両面に従来例の接着シート（１１）、（１１）
を介して実施例３で用いた被着体Ｂ（１３）、（１３）
を積層し、これらを温度１８０°Ｃ、面圧２０ｋｇ／ｃ
ｍ２で７０分間プレスしてガラスエポキシ系プリプレグ
を硬化させると同時に接着一体化した。Comparative Example 2 FIG. 6 shows a laminated structure of a heat-resistant laminated material according to Comparative Example 2. In Comparative Example 2, three adherends C (14), (14), and (14) used in Example 4 were laminated via the conventional adhesive sheets (11) and (11).
Further, the conventional adhesive sheets (11) and (11) are provided on both sides thereof.
Adherends B (13) and (13) used in Example 3 through
Are laminated at a temperature of 180 ° C. and a surface pressure of 20 kg / c.
pressed for 70 minutes at m 2 was bonded and integrated at the same time curing the glass epoxy prepreg.
【００５７】５．（耐熱性の比較） 実施例１、２の接着シートに用いたふっ素ゴムの加硫ゴ
ム及び従来例に用いたエポキシ樹脂の硬化物の熱分解温
度を、示差熱熱重量同時測定装置（セイコー電子工業株
式会社製；ＳＳＣ５２００Ｈ）によって測定した。その
結果を図１１に示す。図１１において、横軸は温度（゜
Ｃ）であり、縦軸は重量減少度（％）である。この図か
ら、実施例１、２のふっ素ゴムは、従来例のエポキシ樹
脂に比べて約２０〜４０°Ｃ耐熱性に優れていることが
判る。5. (Comparison of heat resistance) The thermal decomposition temperature of the vulcanized rubber of the fluoro rubber used for the adhesive sheets of Examples 1 and 2 and the cured product of the epoxy resin used for the conventional example were measured by a differential thermogravimetric simultaneous measuring device (Seiko Electronics Co., Ltd.). (Manufactured by Kogyo Co., Ltd .; SSC5200H). The result is shown in FIG. In FIG. 11, the horizontal axis represents temperature (° C.), and the vertical axis represents the degree of weight loss (%). From this figure, it can be seen that the fluororubbers of Examples 1 and 2 are more excellent in heat resistance of about 20 to 40 ° C. than the conventional epoxy resin.
【００５８】６．（耐久性の比較） 実施例３、４及び比較例１、２の積層材について、加熱
温度２２０°Ｃ×加圧力１２０ｋｇ／ｃｍ２の熱プレス
試験を、加熱時間６０分間、冷却時間１５分間のプレス
サイクルでくり返し行ない、積層材の耐久性を比較し
た。その結果を表６に示す。6. (Comparison of durability) The laminated materials of Examples 3 and 4 and Comparative Examples 1 and 2 were subjected to a heat press test at a heating temperature of 220 ° C and a pressure of 120 kg / cm 2 for a heating time of 60 minutes and a cooling time of 15 minutes. The cycle was repeated in a press cycle, and the durability of the laminated materials was compared. Table 6 shows the results.
【００５９】[0059]
【表６】 [Table 6]
【００６０】比較例１及び２の積層材は、５０回のプレ
スによって、内層には異常はなかったが、表層に剥離が
生じた。また、比較例２の積層材は、１００回のプレス
で内層にも剥離が生じた。これに対して実施例３及び４
の積層材は、３００回のプレスを行なっても、内層、外
層共に剥離を生じることがなかった。The laminates of Comparative Examples 1 and 2 did not show any abnormality in the inner layer, but peeled off on the surface layer after 50 times of pressing. In the laminate of Comparative Example 2, peeling occurred in the inner layer by pressing 100 times. In contrast, Examples 3 and 4
The laminated material of No. did not cause peeling of both the inner layer and the outer layer even after pressing 300 times.
【００６１】[0061]
【発明の効果】以上、詳しく説明したとおり、この発明
による熱プレス成形用クッション材の耐熱性感熱接着シ
ートは、ふっ素ゴムを使用しているために従来のガラス
エポキシ系の耐熱性感熱接着剤と比較しても優れた耐熱
性を有しており、しかも、剥離、振動、繰返し圧縮、曲
げ応力等に対する優れた耐久性を同時に兼ね備えてい
る。特に表面に耐熱性塗料を塗布しているので、表面の
耐熱性と離型性とを向上させることができる。また、そ
の製造方法としては、ふっ素ゴムの溶剤として比誘電率
（ε）が１７以下のものを用いているため、ふっ素ゴム
溶液の貯蔵安定性を向上させることができる。特に、こ
のふっ素ゴム溶液中に、ふっ素ゴムコンパウンド１００
重量部に対して０．５〜５重量部の酸を添加しているの
で、ふっ素ゴム溶液の貯蔵安定性をさらに向上させるこ
とができる。このように貯蔵安定性の向上したふっ素ゴ
ム溶液は基材に容易に塗布することができるため、ふっ
素ゴムを耐熱性材料からなるシート状の基材に塗布して
上記耐熱性感熱接着シートを製造することが容易とな
る。さらに、この発明による熱プレス成形用クッション
材では、被着体表面の不織布層と耐熱性感熱接着シート
の未加硫ふっ素ゴムとを当接させて、圧力と熱を加えて
未加硫ふっ素ゴムを加硫して被着体と接着シートとを接
着一体化させている。ふっ素ゴムを使用した接着シート
は、優れた耐熱性を有しており、しかも不織布層の形状
変化に追従することができるので、加熱、加圧が繰返さ
れる熱プレス成形用クッション材の使用条件において
も、被着体と接着シートとの間の良好な接着を長期にわ
たって維持でき、層間剥離が生じない。また、ふっ素ゴ
ムを使用した接着シートは不織布層の形状変化に追従す
ることができるので、不織布層のクッション性を十分に
生かすことができる。したがって、この発明に従った熱
プレス成形用クッション材は、クッション性、耐熱性お
よび耐久性に優れたものとなる。この発明に従った熱プ
レス成形用クッション材の製造方法によれば、接着シー
トに使用するふっ素ゴムの溶剤として比誘電率（ε）が
１７以下のものを用いるので、ふっ素ゴム溶液の貯蔵安
定性が向上し、ふっ素ゴムを使用した耐熱性感熱接着シ
ートの作成が容易であり、さらに被着体の不織布層と耐
熱性感熱接着シートのふっ素ゴム層とを接着させるの
で、クッション性、耐熱性および耐久性に優れた熱プレ
ス成形用クッション材が得られる。As described in detail above, the heat-resistant heat-sensitive adhesive sheet of the cushioning material for hot press molding according to the present invention uses a conventional glass-epoxy heat-resistant heat-sensitive adhesive because it uses fluorine rubber. It has excellent heat resistance even in comparison, and at the same time has excellent durability against peeling, vibration, repeated compression, bending stress and the like. In particular, since the heat-resistant paint is applied to the surface, the heat resistance and the releasability of the surface can be improved. In addition, in the production method, since the fluororubber having a relative dielectric constant (ε) of 17 or less is used, the storage stability of the fluororubber solution can be improved. In particular, in this fluoro rubber solution, the fluoro rubber compound 100
Since 0.5 to 5 parts by weight of the acid is added to the parts by weight, the storage stability of the fluororubber solution can be further improved. Since the fluororubber solution with improved storage stability can be easily applied to a base material, the fluororubber is applied to a sheet-like base material made of a heat-resistant material to produce the heat-resistant heat-sensitive adhesive sheet. It becomes easy to do. Further, in the cushioning material for hot press molding according to the present invention, the non-vulcanized fluoro rubber is brought into contact with the non-vulcanized fluoro rubber of the heat-resistant heat-sensitive adhesive sheet by bringing the non-vulcanized fluoro rubber into contact with the non-woven fabric layer on the surface of the adherend. And the adherend and the adhesive sheet are bonded and integrated. Adhesive sheets using fluoro rubber have excellent heat resistance and can follow the shape change of the non-woven fabric layer. However, good adhesion between the adherend and the adhesive sheet can be maintained for a long time, and no delamination occurs. In addition, since the adhesive sheet using fluororubber can follow the shape change of the nonwoven fabric layer, the cushioning properties of the nonwoven fabric layer can be fully utilized. Therefore, the cushioning material for hot press molding according to the present invention is excellent in cushioning property, heat resistance and durability. According to the method for producing a cushioning material for hot press molding according to the present invention, since the solvent for the fluororubber used for the adhesive sheet has a relative dielectric constant (ε) of 17 or less, the storage stability of the fluororubber solution is improved. Is improved, and it is easy to prepare a heat-resistant heat-sensitive adhesive sheet using fluororubber.Furthermore, since the nonwoven fabric layer of the adherend is bonded to the fluororubber layer of the heat-resistant heat-sensitive adhesive sheet, cushioning, heat resistance and A cushioning material for hot press molding having excellent durability can be obtained.
【図１】実施例１による耐熱性感熱接着シートの構成を
示す断面図。FIG. 1 is a cross-sectional view showing a configuration of a heat-resistant heat-sensitive adhesive sheet according to Example 1.
【図２】実施例２による耐熱性感熱接着シートの構成を
示す断面図。FIG. 2 is a cross-sectional view illustrating a configuration of a heat-resistant heat-sensitive adhesive sheet according to Example 2.
【図３】実施例３による耐熱性積層材の積層構成を示す
断面図。FIG. 3 is a cross-sectional view illustrating a laminated structure of a heat-resistant laminated material according to a third embodiment.
【図４】実施例４による耐熱性積層材の積層構成を示す
断面図。FIG. 4 is a cross-sectional view illustrating a laminated structure of a heat-resistant laminated material according to a fourth embodiment.
【図５】比較例１による耐熱性積層材の積層構成を示す
断面図。FIG. 5 is a cross-sectional view illustrating a laminated structure of a heat-resistant laminated material according to Comparative Example 1.
【図６】比較例２による耐熱性積層材の積層構成を示す
断面図。FIG. 6 is a cross-sectional view showing a laminated structure of a heat-resistant laminated material according to Comparative Example 2.
【図７】一般的な熱プレス成形用クッション材の構成の
一例を示す断面図。FIG. 7 is a sectional view showing an example of the configuration of a general cushioning material for hot press molding.
【図８】平行円板型の三端子電極を示す図。FIG. 8 is a view showing a parallel disk type three-terminal electrode.
【図９】溶剤の比誘電率（ε）とふっ素ゴムのゲル化日
数との関係についての測定結果を示す図。FIG. 9 is a graph showing measurement results of a relationship between the relative dielectric constant (ε) of a solvent and the number of gelling days of fluororubber.
【図１０】酢酸の添加量とふっ素ゴム溶液のゲル化日数
及び溶液粘度との関係についての測定結果を示す図。FIG. 10 is a graph showing the results of measurement on the relationship between the amount of acetic acid added, the number of gelation days of the fluororubber solution, and the solution viscosity.
【図１１】ふっ素ゴム及びエポキシ樹脂の熱分解曲線を
示す図。FIG. 11 is a view showing a thermal decomposition curve of a fluororubber and an epoxy resin.
１ 耐熱性繊維層 ２ 接着材層 ３ 表面離型層 ４ 耐熱性感熱接着シート（実施例１） ５ 基材：ガラスクロス ６ 未加硫ふっ素ゴム ７ 耐熱性感熱接着シート（実施例２） ８ 耐熱塗料 ９ 芳香族ポリアミド繊維よりなる紙にエポキシ樹脂
系プリプレグ粉末を内添したシート １０ スラグ・ロック繊維を主成分とする抄造紙にエポ
キシ樹脂系プリプレグ粉末を内添したシート １１ ガラスエポキシ系の接着シート １２ 基布補強ニードルパンチ不織布 １３ ふっ素樹脂フィルム １４ 基布補強ニードルパンチ不織布DESCRIPTION OF SYMBOLS 1 Heat resistant fiber layer 2 Adhesive layer 3 Surface release layer 4 Heat resistant heat sensitive adhesive sheet (Example 1) 5 Base material: Glass cloth 6 Unvulcanized fluoro rubber 7 Heat resistant heat sensitive adhesive sheet (Example 2) 8 Heat resistance Paint 9 A sheet in which epoxy resin-based prepreg powder is internally added to paper made of aromatic polyamide fiber 10 A sheet in which epoxy resin-based prepreg powder is internally added to paper made mainly of slag / rock fiber 11 A glass epoxy adhesive sheet 12 Non-woven fabric of needle-punched reinforced needle punch 13 Fluorine resin film 14 Non-woven fabric of needle-punched non-woven fabric
フロントページの続き (56)参考文献 特開 昭60−3131（ＪＰ，Ａ) 特開 昭62−263272（ＪＰ，Ａ) 特開 昭63−199785（ＪＰ，Ａ) 特開 昭54−45386（ＪＰ，Ａ) 特開 昭57−70174（ＪＰ，Ａ) 実開 昭58−7646（ＪＰ，Ｕ) 特公 昭46−19800（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.7，ＤＢ名) C09J 7/02 B29C 43/00 B30B 15/28 B32B 7/10 B32B 25/14 Continuation of the front page (56) References JP-A-60-3131 (JP, A) JP-A-62-263272 (JP, A) JP-A-63-199785 (JP, A) JP-A-54-45386 (JP) JP-A-57-70174 (JP, A) JP-A-58-7646 (JP, U) JP-B-46-19800 (JP, B1) (58) Fields investigated (Int. Cl. 7 , DB Name) C09J 7/02 B29C 43/00 B30B 15/28 B32B 7/10 B32B 25/14
Claims (6)
面に未加硫ふっ素ゴムを塗布し、さらにその上から片面
に耐熱性塗料を塗布してなる熱プレス成形用クッション
材の耐熱性感熱接着シート。An unvulcanized fluoro rubber is applied to both sides of a sheet-like substrate made of a heat-resistant material, and a heat-resistant paint is applied on one side from above. Thermal adhesive sheet.
求項１に記載の熱プレス成形用クッション材の耐熱性感
熱接着シート。2. The heat-resistant heat-sensitive adhesive sheet for a cushioning material for hot press molding according to claim 1, wherein the base material is a woven fabric of heat-resistant fibers.
加硫ふっ素ゴムのコンパウンド１００重量部および酸
０．５〜５重量部を溶かし、この溶液を耐熱性材料から
なるシート状の基材に塗布した後、ふっ素ゴムを未加硫
のまま乾燥させることを特徴とする、熱プレス成形用ク
ッション材の耐熱性感熱接着シートの製造方法。3. A solution of 100 parts by weight of an unvulcanized fluoro rubber compound and 0.5 to 5 parts by weight of an acid in a solvent having a relative dielectric constant (ε) of 17 or less. A method for producing a heat-resistant heat-sensitive adhesive sheet for a cushioning material for hot press molding, wherein the fluororubber is dried in an unvulcanized state after being applied to the base material.
面に不織布層を有する被着体と、耐熱性材料からなるシ
ート状の基材の両面に未加硫ふっ素ゴムを塗布し、さら
にその上から片面に耐熱性塗料を塗布した耐熱性感熱接
着シートとを備え、前記被着体の不織布層と、前記接着
シートの未加硫ふっ素ゴムとを当接させ、圧力と熱を加
えて未加硫ふっ素ゴムを加硫して被着体と接着シートと
を接着一体化した、熱プレス成形用クッション材。4. An unvulcanized fluoroelastomer is applied to both sides of an adherend made of a heat-resistant material and having a nonwoven fabric layer on at least one surface, and a sheet-like substrate made of a heat-resistant material. A heat-resistant heat-sensitive adhesive sheet coated with a heat-resistant paint on one side, and the non-woven fabric layer of the adherend is brought into contact with the unvulcanized fluororubber of the adhesive sheet, and pressure and heat are applied to the non-vulcanized rubber sheet. A cushioning material for hot press molding, in which an adherend and an adhesive sheet are bonded and integrated by vulcanizing fluorosulfur rubber.
を有する第１の被着体と、上下の面に不織布を有する第
２の被着体とを、耐熱性材料からなるシート状の基材の
両面に未加硫ふっ素ゴムを塗布してなる第１の耐熱性感
熱接着シートを介して積層し、さらに前記第１の被着体
上および前記第２の被着体上に、被着体側に向く面に未
加硫ふっ素ゴムを塗布した第２および第３の耐熱性感熱
接着シートを積層し、前記第２および第３の耐熱性感熱
接着シートの他方の面に未加硫ふっ素ゴムを塗布し、さ
らにその上に耐熱性塗料を塗布し、圧力と熱を加えて未
加硫ふっ素ゴムを加硫すると同時に全体を接着一体化し
てなる、熱プレス成形用クッション材。5. A sheet-like sheet made of a heat-resistant material, comprising a first adherend made of a heat-resistant material and having a nonwoven fabric on upper and lower surfaces and a second adherend having a nonwoven fabric on the upper and lower surfaces. Laminated via a first heat-resistant heat-sensitive adhesive sheet formed by applying unvulcanized fluoro rubber to both surfaces of the base material, and further applied on the first adherend and the second adherend. Laminating second and third heat-resistant heat-sensitive adhesive sheets coated with unvulcanized fluoro rubber on the surface facing the body, and unvulcanized fluorine on the other surface of the second and third heat-resistant heat-sensitive adhesive sheets A rubber material for hot press molding, which is made by applying rubber, further applying a heat-resistant paint thereon, applying pressure and heat to vulcanize the unvulcanized fluoro rubber, and simultaneously bonding and integrating the whole.
加硫ふっ素ゴムのコンパウンド１００重量部および酸
０．５〜５重量部を溶かし、この溶液を耐熱性材料から
なるシート状の基材の少なくとも一方の面に塗布した
後、ふっ素ゴムを未加硫のまま乾燥させて耐熱性感熱接
着シートを作成し、少なくとも一方の面に不織布層を有
する被着体と、前記接着シートの未加硫ふっ素ゴムとを
当接させ、圧力と熱を加えて未加硫ふっ素ゴムを加硫す
ると同時に全体を接着一体化する、熱プレス成形用クッ
ション材の製造方法。6. A solvent having a relative dielectric constant (ε) of 17 or less is prepared by dissolving 100 parts by weight of an unvulcanized fluoro rubber compound and 0.5 to 5 parts by weight of an acid. After applying to at least one surface of the base material, the fluororubber is dried in an unvulcanized state to prepare a heat-resistant heat-sensitive adhesive sheet, an adherend having a nonwoven fabric layer on at least one surface, and the adhesive sheet A method for producing a cushioning material for hot press molding, in which the unvulcanized fluororubber is brought into contact with the rubber material, and pressure and heat are applied to vulcanize the unvulcanized fluororubber and simultaneously bond and integrate the whole.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14531593A JP3221978B2 (en) | 1993-05-11 | 1993-05-11 | Cushion material for hot press molding, method for producing the same, heat-resistant heat-sensitive adhesive sheet for cushion material for hot press molding, and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14531593A JP3221978B2 (en) | 1993-05-11 | 1993-05-11 | Cushion material for hot press molding, method for producing the same, heat-resistant heat-sensitive adhesive sheet for cushion material for hot press molding, and method for producing the same |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9050678A Division JP2916435B2 (en) | 1997-03-05 | 1997-03-05 | Cushion material for hot press molding, method for manufacturing the same, and method for manufacturing printed circuit board |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06322326A JPH06322326A (en) | 1994-11-22 |
| JP3221978B2 true JP3221978B2 (en) | 2001-10-22 |
Family
ID=15382323
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14531593A Expired - Lifetime JP3221978B2 (en) | 1993-05-11 | 1993-05-11 | Cushion material for hot press molding, method for producing the same, heat-resistant heat-sensitive adhesive sheet for cushion material for hot press molding, and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3221978B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012169011A1 (en) | 2011-06-07 | 2012-12-13 | ヤマウチ株式会社 | Surface layer material for cushioning material and cushioning material for hot-pressing |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4183558B2 (en) | 2003-05-26 | 2008-11-19 | ヤマウチ株式会社 | Heat press sheet |
| JP2006249674A (en) * | 2005-03-08 | 2006-09-21 | Nippo Corporation:Kk | Vibration reducing sheet for asphalt pavement body and its manufacturing method |
| DE202017003635U1 (en) * | 2017-07-11 | 2017-08-22 | Rolf Espe | Press pads with higher thermal conductivity and improved recovery properties for the coating of wood-based panels in hydraulic single and multi-floor heating presses |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6039015B2 (en) * | 1977-09-16 | 1985-09-04 | 旭硝子株式会社 | composite laminate |
| JPS603131A (en) * | 1983-06-20 | 1985-01-09 | Nitto Electric Ind Co Ltd | Adhesive film for fixation of semiconductor element |
| JPS62263272A (en) * | 1986-05-09 | 1987-11-16 | Nok Corp | Vulcanizable adhesive blend |
| DE3864160D1 (en) * | 1987-02-10 | 1991-09-19 | Ciba Geigy Ag | ADHESIVE FILM. |
-
1993
- 1993-05-11 JP JP14531593A patent/JP3221978B2/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012169011A1 (en) | 2011-06-07 | 2012-12-13 | ヤマウチ株式会社 | Surface layer material for cushioning material and cushioning material for hot-pressing |
| KR20150126066A (en) | 2011-06-07 | 2015-11-10 | 야마우치 가부시키가이샤 | Surface layer material for cushioning material and cushioning material for hot-pressing |
| US9410284B2 (en) | 2011-06-07 | 2016-08-09 | Yamauchi Corporation | Cushioning-material surface layer and hot-press cushioning material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06322326A (en) | 1994-11-22 |
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