JPH0827453A - Flame-retardant adhesive - Google Patents
Flame-retardant adhesiveInfo
- Publication number
- JPH0827453A JPH0827453A JP16247494A JP16247494A JPH0827453A JP H0827453 A JPH0827453 A JP H0827453A JP 16247494 A JP16247494 A JP 16247494A JP 16247494 A JP16247494 A JP 16247494A JP H0827453 A JPH0827453 A JP H0827453A
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- flame
- parts
- weight
- adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
- H05K3/386—Improvement of the adhesion between the insulating substrate and the metal by the use of an organic polymeric bonding layer, e.g. adhesive
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は難燃性接着剤の改良に関
する。FIELD OF THE INVENTION This invention relates to improvements in flame retardant adhesives.
【０００２】[0002]
【従来の技術】近年、電子機器には小型化、軽量化、省
スペース化が要求されている。かような要求に対応し、
電子機器には軽量でコンパクトでしかも折り曲げもでき
るフレキシブルプリント配線板、フラットケーブル等が
組み込まれている。そして、例えば、フレキシブルプリ
ント配線板では絶縁フィルム上にプリント回路を接着剤
により接着させているように、接着剤が多用されてい
る。2. Description of the Related Art In recent years, electronic devices have been required to be compact, lightweight and space-saving. In response to such requests,
Electronic devices include flexible printed wiring boards, flat cables, etc. that are lightweight, compact, and can be bent. Then, for example, in a flexible printed wiring board, an adhesive is often used such that a printed circuit is adhered to the insulating film by the adhesive.
【０００３】かような用途に使用する接着剤としては耐
熱性や難燃性が必須とされることが多く、例えば、飽和
共重合ポリエステル樹脂を主成分とし、これに臭素化有
機難燃剤および無機充填剤を加え、これら成分を有機溶
剤に溶解させたものが提案されている（特開昭６２−９
６５８０号公報）。Heat resistance and flame retardancy are often essential for adhesives used in such applications. For example, a saturated copolyester resin is used as a main component, and a brominated organic flame retardant and an inorganic flame retardant are used. It has been proposed to add a filler and dissolve these components in an organic solvent (JP-A-62-9).
6580).
【０００４】この接着剤における臭素化有機難燃剤とし
てはデカブロモジフェニルオキサイド、ヘキサブロモベ
ンゼン、トリス（２，３−ジブロモプロピル）イソシア
ヌレート、２，２−ビス（４−ヒドロキシ−３，５−ジ
ブロモフェニル）プロパンあるいは２，２−ビス（４−
ヒドロキシエトキシ−３，５−ジブロモフェニル）プロ
パン等が用いられ、無機充填剤としては三酸化アンチモ
ン、炭酸カルシウム、ケイ酸アルミニウム、フッ化カル
シウム、水酸化アルミニウム、二酸化ケイ素、酸化チタ
ン等が用いられている。Brominated organic flame retardants in this adhesive include decabromodiphenyl oxide, hexabromobenzene, tris (2,3-dibromopropyl) isocyanurate, and 2,2-bis (4-hydroxy-3,5-dibromo). Phenyl) propane or 2,2-bis (4-
Hydroxyethoxy-3,5-dibromophenyl) propane or the like is used, and as the inorganic filler, antimony trioxide, calcium carbonate, aluminum silicate, calcium fluoride, aluminum hydroxide, silicon dioxide, titanium oxide or the like is used. There is.
【０００５】[0005]
【発明が解決しようとする課題】ところで、電子機器に
対する性能向上の要求は厳しく、そのため、該機器に用
いる接着剤も同様に耐熱性、難燃性の向上が望まれてい
る。従って、本発明は耐熱性、難燃性のより向上した難
燃性接着剤を提供することを目的とするものである。By the way, there is a severe demand for improving the performance of electronic devices, and therefore, the adhesives used in the devices are also required to have improved heat resistance and flame retardancy. Therefore, an object of the present invention is to provide a flame-retardant adhesive having improved heat resistance and flame retardancy.
【０００６】[0006]
【課題を解決するための手段】本発明者は上記要求に応
えるため鋭意研究の結果、難燃剤として従来とは全く異
なる含臭素エポキシ樹脂および低分子量のポリテトラフ
ルオロエチレン（以下、「ＰＴＦＥ」という）を配合す
ることにより耐熱性および困難燃性を向上できることを
見出し、本発明を完成するに至った。Means for Solving the Problems As a result of intensive studies to meet the above requirements, the present inventor has found that a completely different bromine-containing epoxy resin and low molecular weight polytetrafluoroethylene (hereinafter referred to as “PTFE”) as a flame retardant. It was found that the heat resistance and flame retardancy can be improved by blending (4), and the present invention has been completed.
【０００７】即ち、本発明に係る難燃性接着剤は、熱可
塑性高分子量ポリエステル１００重量部に対し、低分子
量ＰＴＦＥ２０〜１００重量部および含臭素エポキシ樹
脂１〜２０重量部を配合して成るものである。That is, the flame-retardant adhesive according to the present invention comprises 20 to 100 parts by weight of a low molecular weight PTFE and 1 to 20 parts by weight of a bromine-containing epoxy resin to 100 parts by weight of a thermoplastic high molecular weight polyester. Is.
【０００８】本発明おいて用いる熱可塑性高分子量ポリ
エステルはジカルボン酸とジオールの縮重合により得ら
れる線状の飽和ポリエステルであり、その分子量は、通
常、約１万〜３万である。上記のジカルボン酸としては
テレフタル酸、イソフタル酸等のような芳香族ジカルボ
ン酸やアジピン酸、セバチン酸等のような脂肪族ジカル
ボン酸を、ジオールとしてはエチレングリコール、１，
４−ブタンジオール、ジエチレングリコール、ネオペン
チルグリコール等を用いることができる。The thermoplastic high molecular weight polyester used in the present invention is a linear saturated polyester obtained by polycondensation of a dicarboxylic acid and a diol, and its molecular weight is usually about 10,000 to 30,000. The above-mentioned dicarboxylic acid is an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid, or an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, and the diol is ethylene glycol, 1,
4-Butanediol, diethylene glycol, neopentyl glycol and the like can be used.
【０００９】かような熱可塑性高分子量ポリエステル
は、例えば、東洋紡績株式会社からバイロン３０Ｐ、バ
イロン９００、バイロン９９０、住友化学工業株式会社
からＶＣ−４０、ＶＣ−６０等の商品名で既に市販され
ているので、これらを入手して使用することができる。Such thermoplastic high molecular weight polyesters are already commercially available, for example, under the trade names of Byron 30P, Byron 900, Byron 990 from Sumitomo Chemical Co., Ltd., and VC-40, VC-60 by Sumitomo Chemical Co., Ltd. Therefore, these can be obtained and used.
【００１０】本発明においては上記熱可塑性高分子量ポ
リエステル１００重量部に対し、低分子量ＰＴＦＥが２
０〜１００重量部配合される。この低分子量ＰＴＦＥは
難燃性付与剤であり、その分子量が６０万以下好ましく
は５０００〜５０万の低分子量のものを使用する。低分
子量ＰＴＦＥの配合量が２０重量部未満では優れた難燃
性が付与できず、１００重量部を越えるような多量配合
は接着性の低下を生ずるので好ましくない。なお、この
低分子量ＰＴＦＥは、ダイキン工業株式会社からルブロ
ンＬ−２、Ｌ−５等の商品名で市販されている。In the present invention, 100 parts by weight of the thermoplastic high molecular weight polyester has 2 parts of low molecular weight PTFE.
0 to 100 parts by weight is compounded. This low molecular weight PTFE is a flame retardant-imparting agent, and a low molecular weight PTFE having a molecular weight of 600,000 or less, preferably 5,000 to 500,000 is used. If the blending amount of low molecular weight PTFE is less than 20 parts by weight, excellent flame retardancy cannot be imparted, and blending in a large amount such as more than 100 parts by weight causes a decrease in adhesiveness, which is not preferable. The low molecular weight PTFE is commercially available from Daikin Industries, Ltd. under the trade name of Lubron L-2, L-5 and the like.
【００１１】本発明においては更に接着付与剤として含
臭素エポキシ樹脂が、熱可塑性高分子量ポリエステル１
００重量部に対し、１〜２０重量部の割合で配合され
る。含臭素エポキシ樹脂を上記範囲で配合することによ
り、難燃性を維持したまま充分な接着性を付与できるの
であり、配合量が上記範囲を逸脱すると接着性が低下す
るので好ましくない。In the present invention, a bromine-containing epoxy resin is further used as an adhesion-imparting agent in the form of a thermoplastic high molecular weight polyester 1.
It is mixed in a proportion of 1 to 20 parts by weight with respect to 00 parts by weight. By blending the bromine-containing epoxy resin within the above range, sufficient adhesiveness can be imparted while maintaining flame retardancy, and if the blending amount deviates from the above range, the adhesiveness will decrease, such being undesirable.
【００１２】この含臭素エポキシ樹脂は分子内に臭素を
含むエポキシ樹脂であり、分子内にエポキシ基を２個以
上有するものがより好適である。かような臭素含有エポ
キシ樹脂も大日本インキ化学工業株式会社からエピクロ
ン１５２、１５３、１５３−６０Ｔ、１５３−６０Ｍ、
１６０、１６５の商品名で、油化シェルエポキシ株式会
社からエピコート５０４５Ｂ８０、５０４６Ｂ８０、５
０４８Ｂ７０、５０４９Ｂ７０、５０５０Ｔ６０、５０
５０、５０５１の商品名で市販されている。This bromine-containing epoxy resin is an epoxy resin containing bromine in the molecule, and it is more preferable that it has two or more epoxy groups in the molecule. Such bromine-containing epoxy resin is also available from Dainippon Ink and Chemicals, Inc. in Epicron 152, 153, 153-60T, 153-60M,
Epicort 5045B80, 5046B80, 5 from Yuka Shell Epoxy Co., Ltd. under the trade name of 160, 165.
048B70, 5049B70, 5050T60, 50
It is commercially available under the trade names of 50 and 5051.
【００１３】なお、本発明においては所望により炭酸カ
ルシウム、ケイ酸アルミニウム、フッ化カルシウム、二
酸化ケイ素、酸化アルミニウム、水酸化アルミニウム、
三酸化アンチモン、酸化マグネシウム、酸化アルミニウ
ム、酸化チタン、シリカ等の無機充填剤、安定剤（銅、
鉄等）、酸化防止剤、老化防止剤、着色剤等の添加剤を
適量配合することもできる。In the present invention, if desired, calcium carbonate, aluminum silicate, calcium fluoride, silicon dioxide, aluminum oxide, aluminum hydroxide,
Inorganic fillers such as antimony trioxide, magnesium oxide, aluminum oxide, titanium oxide and silica, stabilizers (copper,
Additives such as iron, etc.), antioxidants, antioxidants, colorants and the like can also be added in appropriate amounts.
【００１４】本発明に係る難燃性接着剤は、熱可塑性高
分子量ポリエステル、低分子量ＰＴＦＥおよび含臭素エ
ポキシ樹脂を混合した粉末あるいはペレットとして使用
でき、また、これら成分を含むフィルム状物として使用
することもできる。The flame-retardant adhesive according to the present invention can be used as powder or pellets in which thermoplastic high molecular weight polyester, low molecular weight PTFE and bromine-containing epoxy resin are mixed, and also as a film-like product containing these components. You can also
【００１５】[0015]
【実施例】以下、実施例により本発明を更に詳細に説明
する。The present invention will be described in more detail with reference to the following examples.
【００１６】実施例１ ジカルボン酸としてテレフタル酸およびセバチン酸、ジ
オールとしてエチレングリコールおよびネオペンチルグ
リコールを用い、これらを縮重合して得られる分子量３
００００の熱可塑性高分子量ポリエステル（東洋紡績株
式会社製、商品名バイロンＧＭ９９０）を用意する。Example 1 Using terephthalic acid and sebacic acid as dicarboxylic acids and ethylene glycol and neopentyl glycol as diols, a molecular weight 3 obtained by polycondensing these
0000 thermoplastic high molecular weight polyester (manufactured by Toyobo Co., Ltd., trade name Byron GM990) is prepared.
【００１７】そして、この熱可塑性高分子量ポリエステ
ル１００重量部に対し、分子量５０万の低分子量ＰＴＦ
Ｅ（ダイキン工業株式会社製、商品名ルブロンＬ−５）
２０重量部、ビスフェノールＡ型含臭素エポキシ樹脂
（油化シェルエポキシ株式会社製、商品名エピコート５
０５１）１重量部、および老化防止剤（チバ・ガイギー
株式会社製、商品名イルガノックス１０１０）２重量部
を均一に混合する。次に、この混合物を温度１８０℃で
フィルム状（厚さ６０μｍ）に押し出し、難燃性接着剤
（試料１）を得た。Then, with respect to 100 parts by weight of this thermoplastic high molecular weight polyester, a low molecular weight PTF having a molecular weight of 500,000 is used.
E (manufactured by Daikin Industries, Ltd., trade name Lubron L-5)
20 parts by weight, bisphenol A type bromine-containing epoxy resin (Yukaka Shell Epoxy Co., Ltd., trade name Epicoat 5
051) 1 part by weight and 2 parts by weight of an anti-aging agent (manufactured by Ciba Geigy Co., Ltd., trade name Irganox 1010) are uniformly mixed. Next, this mixture was extruded at a temperature of 180 ° C. into a film (thickness: 60 μm) to obtain a flame-retardant adhesive (Sample 1).
【００１８】実施例２ 熱可塑性高分子量ポリエステル、低分子量ＰＴＦＥ、含
臭素エポキシ樹脂および老化防止剤の配合量（重量部）
を表１のように設定すること以外は実施例１と同様に作
業し、２種類（試料２および３）のフィルム状難燃性接
着剤を得た。Example 2 Blending amount (parts by weight) of thermoplastic high molecular weight polyester, low molecular weight PTFE, bromine-containing epoxy resin and antioxidant
In the same manner as in Example 1 except that the values were set as in Table 1, two types (Samples 2 and 3) of film-like flame-retardant adhesives were obtained.
【００１９】なお、表１においては配合成分である熱可
塑性高分子量ポリエステルを「Ａ」、低分子量ＰＴＦＥ
を「Ｂ」、含臭素エポキシ樹脂を「Ｃ」、老化防止剤を
「Ｄ」と表示した。In Table 1, the thermoplastic high molecular weight polyester as a compounding ingredient is "A", and low molecular weight PTFE.
Is indicated as "B", the bromine-containing epoxy resin as "C", and the antioxidant as "D".
【００２０】試験例 上記実施例１および２により得たフィルム状の難燃性接
着剤を厚さ５０μｍのポリエチレンテレフタレートフィ
ルムの片面に温度８０℃でラミネートして、接着剤層付
きフィルムとする。Test Example The film-shaped flame-retardant adhesive obtained in Examples 1 and 2 is laminated on one side of a polyethylene terephthalate film having a thickness of 50 μm at a temperature of 80 ° C. to obtain a film with an adhesive layer.
【００２１】次に、この接着剤層付きフィルムを銅箔
（厚さ１００μｍ）の片面に重ね合わせ、一対の圧着ロ
ール間を通して接着させる。なお、圧着ロールの表面温
度は表面温度１６０℃、線圧２０ｋｇ／ｃｍ2 に調整し
た。Next, the film with the adhesive layer is superposed on one side of a copper foil (thickness: 100 μm), and is bonded through a pair of pressure-bonding rolls. The surface temperature of the pressure bonding roll was adjusted to a surface temperature of 160 ° C. and a linear pressure of 20 kg / cm 2 .
【００２２】そして、この接着体の常態接着力および１
３５℃で７日間熱劣化させた後の接着力をＩＰＣＦＣ２
４０−Ａ規格により測定した結果を表１に示す。接着力
の単位は「ｋｇ／１ｃｍ幅」である。また、表１にはこ
の接着体の難燃性をＵＬ９４に規定される方法により測
定した結果を併記する。Then, the normal adhesive force of this adhesive and 1
The adhesive strength after heat deterioration at 35 ° C. for 7 days is IPCFC2.
The results measured according to the 40-A standard are shown in Table 1. The unit of the adhesive force is "kg / 1 cm width". In addition, Table 1 also shows the results of measuring the flame retardancy of this adhesive by the method specified in UL94.
【００２３】[0023]
【表１】 [Table 1]
【００２４】比較例１ 熱可塑性高分子量ポリエステル、低分子量ＰＴＦＥ、含
臭素エポキシ樹脂および老化防止剤の配合量（重量部）
を表２のようにすること以外は実施例１と同様に作業し
て５種類のフィルム状接着剤（試料４〜７）を得た。こ
れらフィルム状接着剤を上記と同様に試験して得た結果
を表２に示した。Comparative Example 1 Blending amount (parts by weight) of thermoplastic high molecular weight polyester, low molecular weight PTFE, bromine-containing epoxy resin and antioxidant
Was carried out in the same manner as in Example 1 except that as shown in Table 2 to obtain 5 kinds of film adhesives (Samples 4 to 7). The results obtained by testing these film adhesives in the same manner as above are shown in Table 2.
【００２５】[0025]
【表２】 [Table 2]
【００２６】比較例２ ＰＴＦＥとして分子量５００万のものを用いること以外
は試料１と同様にしてフィルム状接着剤を得た。この接
着剤について試験したところ、常態接着力は１．５４ｋ
ｇ／１ｃｍ幅、劣化後接着力は０．７７ｋｇ／１ｃｍ
幅、難燃性はＶＴＭ−０であった。Comparative Example 2 A film adhesive was obtained in the same manner as in Sample 1 except that PTFE having a molecular weight of 5,000,000 was used. When tested with this adhesive, the normal adhesive strength is 1.54k.
g / 1cm width, adhesive strength after deterioration is 0.77kg / 1cm
The width and flame retardancy were VTM-0.
【００２７】比較例３ 熱可塑性高分子量ポリエステル（東洋紡績株式会社製、
商品名バイロン３００）１００重量部に対し、デカブロ
モジフェニルオキサイド５０重量部、三酸化アンチモン
２５重量部および老化防止剤（イルガノックス１０１
０）２重量部をトルエン２００重量部に溶解して難燃性
接着剤を得た。Comparative Example 3 Thermoplastic high molecular weight polyester (manufactured by Toyobo Co., Ltd.,
With respect to 100 parts by weight of the product name Byron 300), 50 parts by weight of decabromodiphenyl oxide, 25 parts by weight of antimony trioxide and an antioxidant (IRGANOX 101)
0) 2 parts by weight was dissolved in 200 parts by weight of toluene to obtain a flame-retardant adhesive.
【００２８】この難燃性接着剤を厚さ５０μｍのポリエ
チレンテレフタレートフィルムの片面に塗布し、１３０
℃で５分間加熱して接着剤層付きフィルムを得た。これ
を上記と同様に試験したところ、常態接着力は２．３４
ｋｇ／１ｃｍ幅、劣化後接着力は１．３７ｋｇ／１ｃｍ
幅、難燃性はＶＴＭ−０であった。This flame-retardant adhesive was applied to one side of a polyethylene terephthalate film having a thickness of 50 μm,
It heated at 5 degreeC for 5 minutes, and obtained the film with an adhesive layer. When tested in the same manner as above, the normal adhesive strength was 2.34.
kg / 1cm width, adhesive strength after deterioration is 1.37kg / 1cm
The width and flame retardancy were VTM-0.
【００２９】[0029]
【発明の効果】本発明は上記したように熱可塑性高分子
量ポリエステルに低分子量ＰＴＦＥおよび含臭素エポキ
シ樹脂を配合したので、難燃性、耐熱性に優れており、
種々の物品の接着に有用である。Industrial Applicability As described above, since the thermoplastic high molecular weight polyester is blended with the low molecular weight PTFE and the bromine-containing epoxy resin as described above, it has excellent flame retardancy and heat resistance.
It is useful for bonding various articles.
Claims (2)
量部に対し、低分子量ポリテトラフルオロエチレン２０
〜１００重量部および含臭素エポキシ樹脂１〜２０重量
部を配合して成る難燃性接着剤。1. A low molecular weight polytetrafluoroethylene 20 per 100 parts by weight of a thermoplastic high molecular weight polyester.
~ 100 parts by weight and 1 to 20 parts by weight of a bromine-containing epoxy resin are mixed to provide a flame-retardant adhesive.
接着剤。2. The flame-retardant adhesive according to claim 1, which is in the form of a film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16247494A JPH0827453A (en) | 1994-07-14 | 1994-07-14 | Flame-retardant adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16247494A JPH0827453A (en) | 1994-07-14 | 1994-07-14 | Flame-retardant adhesive |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0827453A true JPH0827453A (en) | 1996-01-30 |
Family
ID=15755316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16247494A Pending JPH0827453A (en) | 1994-07-14 | 1994-07-14 | Flame-retardant adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0827453A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006057043A (en) * | 2004-08-23 | 2006-03-02 | Toyobo Co Ltd | Adhesive composition and laminated body using the same |
| GB2462824A (en) * | 2008-08-18 | 2010-02-24 | Crombie 123 Ltd | Printed circuit board encapsulation |
| US9648720B2 (en) | 2007-02-19 | 2017-05-09 | Semblant Global Limited | Method for manufacturing printed circuit boards |
| US11786930B2 (en) | 2016-12-13 | 2023-10-17 | Hzo, Inc. | Protective coating |
-
1994
- 1994-07-14 JP JP16247494A patent/JPH0827453A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006057043A (en) * | 2004-08-23 | 2006-03-02 | Toyobo Co Ltd | Adhesive composition and laminated body using the same |
| JP4715130B2 (en) * | 2004-08-23 | 2011-07-06 | 東洋紡績株式会社 | Adhesive composition and laminate using the same |
| US9648720B2 (en) | 2007-02-19 | 2017-05-09 | Semblant Global Limited | Method for manufacturing printed circuit boards |
| GB2462824A (en) * | 2008-08-18 | 2010-02-24 | Crombie 123 Ltd | Printed circuit board encapsulation |
| US11786930B2 (en) | 2016-12-13 | 2023-10-17 | Hzo, Inc. | Protective coating |
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