JP4006035B2 - Thermosetting silicone adhesive - Google Patents
Thermosetting silicone adhesive Download PDFInfo
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- JP4006035B2 JP4006035B2 JP08094696A JP8094696A JP4006035B2 JP 4006035 B2 JP4006035 B2 JP 4006035B2 JP 08094696 A JP08094696 A JP 08094696A JP 8094696 A JP8094696 A JP 8094696A JP 4006035 B2 JP4006035 B2 JP 4006035B2
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- Prior art keywords
- adhesive
- silicone
- silicone adhesive
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- Adhesives Or Adhesive Processes (AREA)
- Joining Of Glass To Other Materials (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、貼付時には粘接着剤のもつ粘着力により被着体に仮止でき、その後、加熱硬化することにより強固な接着状態を得ることができる粘接着剤に関する。更に詳しくは、加熱硬化時等の高温条件下においても黄変することがなく、例えばガラスの貼り合わせ用に用いるのに好適な熱硬化型シリコーン粘接着剤に関する。
【０００２】
【従来の技術】
従来、高温下での透明性が要求される箇所への貼付にはエポキシ系接着剤が用いられてきたが、液状であるため作業性が悪いという欠点がある。一方、粘着剤はシート加工することにより容易に貼付できるが、従来のアクリル系粘着剤では高温下では熱黄変を起こしてしまうという不都合を有していた。
【０００３】
【発明が解決しようとする課題】
本発明は、上述のような欠点を補うものとして、高温下でも熱黄変を起こさず、透明性を保つことができ、またシート加工することにより容易に貼付が可能となる粘接着剤を提供するものである。
【０００４】
【課題を解決するための手段】
本発明の熱硬化型シリコーン粘接着剤は、前記課題を解決するべく、シリコーンゴムとシリコーンレジンからなるシリコーン粘着剤に、硬化成分としてエポキシ変性シリコーンオイルを前記シリコーン粘着剤１００重量部に対して５０〜４００重量部と潜在性硬化剤を加えたことを特徴とするものである。
また、請求項２に記載の熱硬化型シリコーン粘接着剤は、前記シリコーン粘着剤を白金触媒硬化型としたことを特徴とするものである。
また、請求項３に記載の熱硬化型シリコーン粘接着剤は、前記潜在性硬化剤を金属キレート化合物としたことを特徴とするものである。
また、請求項４に記載の熱硬化型シリコーン粘接着剤は、前記金属キレート化合物をアルミ系、或いは、チタン系としたことを特徴とするものである。
また、請求項５に記載の熱硬化型シリコーン粘接着剤は、ガラス貼り合わせ用に用いることを特徴とするものである。
【０００５】
【発明の実施の形態】
前記シリコーン粘着剤は高重合度ポリオルガノシロキサンからなるゴム成分と、（ＣＨ3）3ＳｉＯ1/2単位とＳｉＯ2単位とからなる共重合体でなるレジン成分から構成されるものであるが、これらの配合割合はゴム成分３０〜７０重量部に対して、レジン成分７０〜３０重量部とするのが好適である。
このようなシリコーン粘着剤としては塩化白金酸及びそのアルコール溶液、白金−アスベスト、白金−カーボン、白金のオレフィン錯体等の白金触媒硬化型、或いは、過酸化ベンゾイル、過酸化−２，４−ジクロルベンゾイル、過酸化−ｐ−クロルベンゾイル、過酸化ジキュミル、過酸化ジ−ｔ−ブチル、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン等の過酸化物硬化系等、各種シリコーン粘着剤が使用されるが、過酸化物硬化系は密閉加圧下で硬化させる必要があるため、白金触媒硬化型のシリコーン粘着剤の使用が好ましい。
【０００６】
また、前記白金触媒としては、特に塩化白金酸が使用され、また、過酸化物触媒としては過酸化ベンゾイルが使用される。また、その添加量は粘着剤に対し白金元素として５〜２００ｐｐｍ程度とすればよい。
【０００７】
また、前記硬化成分のエポキシ変性シリコーンオイルとしては、側鎖エーテル型エポキシ、片末端エーテル型エポキシ、両末端エーテル型エポキシ等が使用される。また、その添加量は粘着剤１００重量部に対して、５０〜４００重量部とすればよい。
【０００８】
また、硬化成分の潜在性硬化剤としては、アルミ、チタン、鉄、スズ、亜鉛等の金属キレート化合物、リン、ホウ素、アンチモンの錯体化合物、またはジシアンジアミド、アミンイミド、有機酸ジヒドラジド、第三アミン塩、イミダゾール塩、ブレンステッド酸の脂肪族スルホニウム塩等が使用されるが、保存時の安定性の観点から、特に金属キレート化合物の使用が好ましい。更に好ましくは、アルミ系、或いは、チタン系キレート化合物の使用が好ましい。また、その添加量はエポキシ変性シリコーンに対して０．１〜１０重量部程度とすればよい。
【０００９】
このように構成される本願発明の熱硬化型シリコーン粘接着剤は高温下でも熱黄変を起こさず、透明性を保つことができ、またシート加工することにより容易に貼付が可能である。また、ガラスとの接着性にも優れるため、ガラスの貼り合わせ用に用いるのに好適である。
【００１０】
【実施例】
次に本発明の実施例を比較例と共に説明する。
実施例１
粘着成分として、シリコーン粘着剤（商品名 ＳＤ４５８４ 東レ・ダウコーニングシリコーン株式会社製）１００重量部に、白金系硬化触媒（商品名 ＳＲＸ２１２ 東レ・ダウコーニングシリコーン株式会社製）を０．９重量部加えたものに、硬化成分としてエポキシ変性シリコーンオイル（商品名 Ｘ−２２−１６３Ｃ 信越化学工業株式会社製）１００重量部と、アルミニウムトリス（アセチルアセトネート）１０％トルエン溶液１重量部を添加したものをＰＥＴフィルムに乾燥後の厚みが約３０μｍになるように塗布し、１３０℃で２分間乾燥したのち、剥離フィルムと貼り合わせて粘接着シートを得た。また、この組成のものについて剥離フィルムを貼り合わせた両面テープも得た。
【００１１】
この粘接着シートと両面テープを用いて下記の特性につき試験し、その測定結果乃至評価を下記表１に示した。
尚、測定方法並びに測定結果の評価は次のようにした。
粘着力（ｇ／２５ｍｍ）
被着体（ガラス）に粘接着シートを貼付後 ＪＩＳ Ｋ ６８５４に基づき、１８０゜角剥離試験により測定。
硬化後剪断力（ｋｇ／ｃｍ2）
被着体（ＳＵＳ ３０４）を両面テープで貼り合わせ、２６０℃で３０分間加熱した後、ＪＩＳ Ｋ ６８５０に基づき測定。
保存安定性
一週間放置後、フィルム状の粘接着剤層の粘着性を指感にて評価。
○ 良好
× 硬化（非粘着）
熱黄変性
粘接着シートを１００℃雰囲気中に３日間放置して、熱黄変性を目視にて評価。
○ 良好
△ やや黄変
× 黄変が発生
【００１２】
比較例１
粘着成分であるアクリル系粘着剤（ブチルアクリレート）９０重量部とアクリル酸１０重量部の共重合体１００重量部に対し、硬化成分としてエポキシ樹脂（商品名 エピコート１００１ 油化シエルエポキシ社製）３０重量部及びエポキシ樹脂（商品名 エピコート８２８ 油化シエルエポキシ社製）７０重量部及びジシアンジアミド４重量部をアセトンと水の混合溶液１００重量部に溶解したものを添加した。これをＰＥＴフィルムに乾燥後の厚みが約３０μｍになるように塗布し、剥離フィルムと貼り合わせて粘接着シートを得た。また、この組成のものについて剥離フィルムを貼り合わせた両面テープを得た。
この粘接着シートと両面テープを用いて実施例１と同様にして測定乃至評価して、その結果を下記表１に示した。
【００１３】
比較例２
エポキシ系接着剤としてビスフェノールＡ型のエポキシ樹脂（商品名 エピコート８２８ 油化シエルエポキシ社製）１００重量部に、硬化剤として一級アミン化合物５重量部を添加したものをＰＥＴフィルムに乾燥後の厚みが約３０μｍになるように塗布し、１日放置したところ、硬化が進み、粘着性の測定を試みたが測定不可であった。
【００１４】
【表１】
上記表１から明らかなように、本発明の熱硬化型シリコーン粘接着剤は、高温下でも熱黄変を起こさないタイプの粘接着剤であり、ガラスの貼り合わせ用等、高温下での透明性を要求される箇所への貼付時の使用が可能である。
【００１６】
【発明の効果】
以上説明した通り、本発明の熱硬化型シリコーン変性シリコーン粘接着剤は、高温下でも熱黄変を起こさないタイプの粘接着剤であり、ガラスの貼り合わせ用等、高温下での透明性を要求される箇所への貼付時の使用が可能である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a pressure-sensitive adhesive that can be temporarily fixed to an adherend by the adhesive force of the pressure-sensitive adhesive at the time of application, and can obtain a strong adhesive state by heat-curing thereafter. More specifically, the present invention relates to a thermosetting silicone adhesive that is suitable for use in, for example, bonding of glass without yellowing even under high temperature conditions such as heat curing.
[0002]
[Prior art]
Conventionally, epoxy adhesives have been used for application to places where transparency at high temperatures is required, but there is a disadvantage that workability is poor because it is liquid. On the other hand, the pressure-sensitive adhesive can be easily applied by sheet processing, but the conventional acrylic pressure-sensitive adhesive has a disadvantage that it causes thermal yellowing at a high temperature.
[0003]
[Problems to be solved by the invention]
The present invention compensates for the above-mentioned drawbacks by providing an adhesive that does not cause thermal yellowing even at high temperatures, can maintain transparency, and can be easily applied by sheet processing. It is to provide.
[0004]
[Means for Solving the Problems]
In order to solve the above problems, the thermosetting silicone adhesive of the present invention is prepared by adding an epoxy-modified silicone oil as a curing component to 100 parts by weight of the silicone adhesive. 50 to 400 parts by weight and a latent curing agent are added.
The thermosetting silicone adhesive according to claim 2 is characterized in that the silicone pressure-sensitive adhesive is a platinum catalyst curable type.
The thermosetting silicone adhesive according to claim 3 is characterized in that the latent curing agent is a metal chelate compound.
The thermosetting silicone adhesive according to claim 4 is characterized in that the metal chelate compound is made of aluminum or titanium.
Moreover, the thermosetting silicone adhesive of Claim 5 is used for glass bonding.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The silicone adhesive is composed of a rubber component composed of a polyorganosiloxane having a high degree of polymerization and a resin component composed of a copolymer composed of (CH 3 ) 3 SiO 1/2 units and SiO 2 units. These blending ratios are preferably 70 to 30 parts by weight of the resin component with respect to 30 to 70 parts by weight of the rubber component.
Examples of such silicone pressure-sensitive adhesives include chloroplatinic acid and its alcohol solution, platinum-asbestos, platinum-carbon, platinum olefin complexes such as platinum olefin complexes, or benzoyl peroxide and 2,4-dichloro peroxide. Peroxide curing systems such as benzoyl, peroxide-p-chlorobenzoyl, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, etc. Various silicone pressure-sensitive adhesives are used. Since the peroxide curing system needs to be cured under closed pressure, the use of a platinum catalyst-curing type silicone pressure-sensitive adhesive is preferable.
[0006]
Further, chloroplatinic acid is particularly used as the platinum catalyst, and benzoyl peroxide is used as the peroxide catalyst. Moreover, the addition amount should just be about 5-200 ppm as a platinum element with respect to an adhesive.
[0007]
Moreover, as the epoxy-modified silicone oil of the curing component, side chain ether type epoxy, one terminal ether type epoxy, both terminal ether type epoxy or the like is used. Moreover, the addition amount should just be 50-400 weight part with respect to 100 weight part of adhesives.
[0008]
In addition, as the latent curing agent of the curing component, metal chelate compounds such as aluminum, titanium, iron, tin, and zinc, complex compounds of phosphorus, boron, and antimony, or dicyandiamide, amine imide, organic acid dihydrazide, tertiary amine salt, Imidazole salts, aliphatic sulfonium salts of Bronsted acid, and the like are used, and from the viewpoint of stability during storage, use of a metal chelate compound is particularly preferable. More preferably, use of an aluminum-based or titanium-based chelate compound is preferable. Moreover, the addition amount should just be about 0.1-10 weight part with respect to epoxy-modified silicone.
[0009]
The thus configured thermosetting silicone adhesive of the present invention does not cause yellowing even at high temperatures, can maintain transparency, and can be easily applied by sheet processing. Moreover, since it is excellent also in adhesiveness with glass, it is suitable for using for bonding of glass.
[0010]
【Example】
Next, examples of the present invention will be described together with comparative examples.
Example 1
As an adhesive component, 0.9 parts by weight of a platinum-based curing catalyst (trade name: SRX212, manufactured by Toray Dow Corning Silicone Co., Ltd.) was added to 100 parts by weight of a silicone adhesive (trade name: SD4584, manufactured by Toray Dow Corning Silicone Co., Ltd.). PET with 100 parts by weight of epoxy-modified silicone oil (trade name: X-22-163C, Shin-Etsu Chemical Co., Ltd.) and 1 part by weight of aluminum tris (acetylacetonate) 10% toluene solution as a curing component The film was coated on the film so that the thickness after drying was about 30 μm, dried at 130 ° C. for 2 minutes, and then bonded to the release film to obtain an adhesive sheet. Moreover, the double-sided tape which bonded the peeling film about the thing of this composition was also obtained.
[0011]
The following properties were tested using this adhesive sheet and double-sided tape, and the measurement results and evaluations are shown in Table 1 below.
The measurement method and the evaluation of the measurement results were as follows.
Adhesive strength (g / 25mm)
After sticking an adhesive sheet on the adherend (glass), measured by 180 ° angle peel test based on JIS K 6854.
Shear force after curing (kg / cm 2 )
The adherend (SUS 304) was bonded with a double-sided tape, heated at 260 ° C. for 30 minutes, and then measured according to JIS K 6850.
Storage stability After standing for 1 week, the tackiness of the film-like adhesive layer was evaluated by finger feeling.
○ Good × Curing (non-adhesive)
The heat yellowing adhesive sheet was left in an atmosphere of 100 ° C. for 3 days to visually evaluate the heat yellowing.
○ Good △ Slightly yellowing × yellowing occurs.
Comparative Example 1
30 parts by weight of an epoxy resin (trade name: Epicoat 1001 manufactured by Yuka Shell CELL Epoxy Co., Ltd.) as a curing component with respect to 100 parts by weight of a copolymer of 90 parts by weight of acrylic adhesive (butyl acrylate) and 10 parts by weight of acrylic acid, And 70 parts by weight of epoxy resin (trade name: Epicoat 828, Yuka Shell Epoxy Co., Ltd.) and 4 parts by weight of dicyandiamide dissolved in 100 parts by weight of a mixed solution of acetone and water were added. This was applied to a PET film so that the thickness after drying was about 30 μm, and bonded to a release film to obtain an adhesive sheet. Moreover, the double-sided tape which bonded the peeling film about the thing of this composition was obtained.
The adhesive sheet and the double-sided tape were used for measurement and evaluation in the same manner as in Example 1, and the results are shown in Table 1 below.
[0013]
Comparative Example 2
The thickness after drying a PET film with 100 parts by weight of a bisphenol A type epoxy resin (trade name: Epicoat 828, Yuka Shell Shell Epoxy Co., Ltd.) added as an epoxy adhesive and 5 parts by weight of a primary amine compound as a curing agent. When it was applied to a thickness of about 30 μm and allowed to stand for 1 day, curing proceeded and an attempt was made to measure tackiness, but measurement was impossible.
[0014]
[Table 1]
As is clear from Table 1 above, the thermosetting silicone adhesive of the present invention is a type of adhesive that does not cause thermal yellowing even at high temperatures. It can be used when sticking to places where transparency is required.
[0016]
【The invention's effect】
As described above, the thermosetting silicone-modified silicone adhesive of the present invention is a type of adhesive that does not cause thermal yellowing even at high temperatures, and is transparent at high temperatures such as for laminating glass. It can be used when affixed to places that require sexuality.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08094696A JP4006035B2 (en) | 1996-03-08 | 1996-03-08 | Thermosetting silicone adhesive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08094696A JP4006035B2 (en) | 1996-03-08 | 1996-03-08 | Thermosetting silicone adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09241607A JPH09241607A (en) | 1997-09-16 |
| JP4006035B2 true JP4006035B2 (en) | 2007-11-14 |
Family
ID=13732670
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08094696A Expired - Fee Related JP4006035B2 (en) | 1996-03-08 | 1996-03-08 | Thermosetting silicone adhesive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4006035B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3875859B2 (en) | 2001-06-27 | 2007-01-31 | ソニーケミカル＆インフォメーションデバイス株式会社 | Curing agent particles, method for producing curing agent particles, and adhesive |
| JP4505649B2 (en) * | 2006-03-23 | 2010-07-21 | フジコピアン株式会社 | Fixed sheet |
| JP6126436B2 (en) * | 2013-03-29 | 2017-05-10 | リンテック株式会社 | Baseless silicone double-sided tape |
| JP6601921B2 (en) * | 2015-04-27 | 2019-11-06 | 株式会社寺岡製作所 | Release adhesive tape |
| KR102072100B1 (en) * | 2019-11-01 | 2020-03-02 | 방인란 | Silicon wappen with flocking layer and manufacturing method thereof |
-
1996
- 1996-03-08 JP JP08094696A patent/JP4006035B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09241607A (en) | 1997-09-16 |
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