JP3773861B2 - Chloroprene rubber adhesive composition - Google Patents
Chloroprene rubber adhesive composition Download PDFInfo
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- JP3773861B2 JP3773861B2 JP2002026831A JP2002026831A JP3773861B2 JP 3773861 B2 JP3773861 B2 JP 3773861B2 JP 2002026831 A JP2002026831 A JP 2002026831A JP 2002026831 A JP2002026831 A JP 2002026831A JP 3773861 B2 JP3773861 B2 JP 3773861B2
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- JP
- Japan
- Prior art keywords
- chloroprene rubber
- adhesive composition
- adhesive
- toluene
- methylcyclohexane
- 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
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Description
【０００１】
【産業上の利用分野】
本発明は家具、木工、車両その他分野において使用される接着剤組成物、詳しくは室内汚染物質として指定されている溶剤のトルエンおよびキシレンを使用しないクロロプレンゴム系接着剤組成物に関する。
【０００２】
【従来の技術】
従来から、クロロプレンゴム系接着剤は各種、各様の被着剤に対する接着性能が優れるため、家具、木工、車両などの分野において広く使用されてきた。これらクロロプレンゴム系接着剤は原料ゴムのクロロプレンゴム、粘着付与剤、老化防止剤、並びに金属酸化物などをトルエン、アセトン、酢酸エチルなどの混合溶剤に溶解させたのもが採用されている。
【０００３】
しかし、近年シックハウス症候群の室内汚染物質としてもホルムアルデヒド、トルエン、キシレン等の優先取り組み物質が定められた。また、厚生労働省より、それらの指針値も公表された。また、ＰＲＴＲ法（環境への排出量の把握及び管理の改善の促進）の第一種指定化学物質にホルムアルデヒド，トルエン，キシレン，塩化メチレンなどが指定された。このような背景の中、トルエンを含有しない溶剤型クロロプレンゴム系接着剤の開発が市場より望まれるようになった。
【本発明が解決しようとする課題】
【０００４】
本発明は、従来のクロロプレンゴム系接着剤が持つ課題、即ちトルエン使用に伴う室内環境汚染をなくし、なおかつ、溶剤の乾燥が速くなり過ぎ使用途中での結露の発生によるタック低減が無く、保存性、乾燥性並びに接着性能を確保することを目的としている。
【課題を解決するための手段】
【０００５】
上記課題の解決のため鋭意検討した結果、請求項１に記載の発明は、クロロプレンゴムと、粘着付与樹脂と、メチルシクロへキサンを含み、トルエンを含まない有機溶剤と、を必須成分として含有することを特徴とするクロロプレンゴム系接着剤組成物である。請求項２に記載の発明は、有機溶剤にメチルシクロへキサンを５〜５０％使用した請求項１に記載のクロロプレンゴム系接着剤組成物である。
【０００６】
このクロロプレンゴム系接着剤組成物は、前記の室内汚染物質であるトルエンを含まず、安定性、乾燥性、タック強さ、結露防止、接着性能などを実現したものである。
【０００７】
以下に、本発明を詳細に説明する。
本発明で用いるクロロプレンゴムとは、クロロプレンモノマーを重合することにより得られたポリクロロプレンである。一般的に重合は乳化重合により行われ、得られたポリクロロプレンラテックスをさらに凝固・水洗・乾燥させチップ状にしたものを用いる。また、分子中にカルボキシル基を有したもの、好ましくは１分子中に２個以上のカルボキシル基を有するポリクロロプレンを使用しても良い。
【０００８】
本発明に用いる粘着付与樹脂とは、フェノール系樹脂、テルペン系樹脂、ロジン誘導体樹脂、石油系炭化水素樹脂、クマロン・インデン樹脂及びスチレン樹脂の少なくとも一種、もしくは複数の組合わせから選ばれたのもである。そして、その添加料は、全クロロプレンゴム１００重量部に対して、一般には１０〜１５０重量部である。粘着付与樹脂の量がこの範囲より少なくなると十分な接着強度が発揮できず、多くなると接着強度は向上するが脆くなる可能性があるからである。
【０００９】
本発明で用いるメチルシクロへキサンを含み、トルエンを含まない有機溶剤とは、メチルシクロヘキサンに、アセトンやＭＥＫ（メチルエチルケトン）などのケトン系、酢酸エチルや酢酸ブチルなどエステル系、ｎ−ヘキサンやシクロヘキサンなどの炭化水素系、メタノールやエタノールなどのアルコール系などのトルエンを含まない溶剤を混合したものである。これらの組み合わせ並びに配合割合は適宜目的に応じて調整し、クロロプレンゴムや粘着付与剤の溶解性、乾燥性、タックの発現等を調整する。そして、この有機溶剤はメチルシクロへキサンを５〜５０％使用したものである。メチルシクロヘキサンの量がこの範囲より少なくなると十分な接着強度、安定性が得られにくく、多くなると接着剤の乾燥時間が長くなる傾向があるからである。
【００１０】
本発明のクロロプレンゴム系接着剤組成物には前記成分の他に、一般に用いられる金属酸化物、加硫剤、加硫促進剤、充填剤、軟化剤、可塑剤、加工助剤、老化防止剤、安定剤、補強剤、架橋剤などを適量含ませることができる。
【００１１】
【実施例】
以下、実施例によって具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
【００１２】
実施例及び比較例
表１の配合により、実施例、比較例の接着剤を調製し、試験に供した。
クロロプレンゴム（電気化学（株）製、Ａ９０）、酸化マグネシウム（マグネシア）及び酸化亜鉛（亜鉛華）を９インチロールにて２０分間混練りする。その練りゴム、フェノール樹脂（昭和高分子（株）製、ＣＫＭ−１６３４）及び老化防止剤（ジフェニルアミン系）を各種混合溶剤で溶解する。溶解はディスパーを使用し１０００ｒｐｍで１０時間行った。
【表１】
以下の実施例、比較例において得られたクロロプレンゴム系接着剤組成物の初期粘度、相分離安定性、低温安定性、乾燥時間、結露性、タックタイム、接着性能の測定は以下の方法で測定、評価した。
【００１４】
調製した各接着剤組成物の初期粘度、相分離安定性、低温安定性、乾燥時間、結露性、タックタイム、接着性能を表２に示した。表２の結果より、メチルシクロヘキサンを使用したノントルエンタイプ実施例１、２は、安定性、乾燥時間、結露性、タックタイム、接着性能についてトルエン含有タイプとほぼ同等であるのに対し、メチルシクロヘキサンを使用しないノントルエンタイプは安定性やタックタイム、結露性、接着性能について劣る結果となり、本発明のクロロプレンゴム系接着剤が有用であることがわかる。
【表２】
＜初期粘度＞
初期粘度はブルックフィールド回転型粘度計によりBM型、No.3、１２rpmの条件で測定した。
【００１６】
＜相分離安定性＞
接着剤を４０℃中で２ヶ月間保存し、粘度変化及び外観上の変化をチェックする。粘度はブルックフィールド回転型粘度計により測定する。
【００１７】
＜低温安定性＞
接着剤を−５℃中で１０日間保存後、−５℃での粘度及び外観上の変化をチェックする。
【００１８】
＜乾燥時間＞
接着剤をバーコーターにてクラフト紙上に１２０ｇ／ｍ2塗布する。２０℃中で保存し、手に接着剤が転写しなくなった時点を乾燥時間とする。
【００１９】
＜結露性＞
接着剤をバーコーターにてクラフト紙上に１２０ｇ／ｍ2塗布する。その後、クラフト紙を５０ｍｍ幅に切り出し、２０℃中、９０％ＲＨで養生、接着剤が乾燥する間の結露を目視にて評価する。
＜評価基準＞○：従来品と比較して結露無し、又は同等。
×：従来品と比較して結露多い。
【００２０】
＜タックタイム（接着可能時間）＞
接着剤をバーコーターにてクラフト紙上に１２０ｇ／ｍ2塗布する。その後、クラフト紙を５０ｍｍ幅に切り出し、２０℃中で５分ごとに貼り合わせていく。その時の圧締は５kgのローラーを転がすことにより行う。クラフト紙が材破している間をタックタイムとする。
【００２１】
＜接着性能＞
接着条件・試験項目は下記の通り。
【００２２】
【発明の効果】
以上に示したように、本発明により得られたクロロプレンゴム系接着剤組成物は、PRTR法の第一種指定化学物質に指定されるトルエンを含まず、低温時の安定性が良好であり、引張り剪断強度では初期剪断、常態剪断、耐熱剪断ともに優れており、家具、木工、建材用としてなど広範囲の材料の接着剤として好適である。
しかも、n-ヘキサン、アセトン、酢酸エチルのみで構成される一般的溶剤では乾燥が速くなり過ぎ使用途中で結露しやすくなるなどの問題がなく安心して使用できる。[0001]
[Industrial application fields]
The present invention relates to an adhesive composition used in furniture, woodworking, vehicles and other fields, and more particularly to a chloroprene rubber adhesive composition which does not use the solvents toluene and xylene which are designated as indoor pollutants.
[0002]
[Prior art]
Conventionally, chloroprene rubber adhesives have been widely used in the fields of furniture, woodworking, vehicles and the like because of their excellent adhesion performance to various types of adherends. These chloroprene rubber adhesives are obtained by dissolving raw material chloroprene rubber, tackifier, anti-aging agent, and metal oxide in a mixed solvent such as toluene, acetone, ethyl acetate and the like.
[0003]
However, in recent years, priority substances such as formaldehyde, toluene and xylene have been established as indoor pollutants for sick house syndrome. In addition, the guidelines were published by the Ministry of Health, Labor and Welfare. In addition, formaldehyde, toluene, xylene, methylene chloride, etc. were designated as the Class 1 Designated Chemical Substances under the PRTR Law (promoting improvement of management and management of environmental emissions). Against this background, development of a solvent-type chloroprene rubber-based adhesive that does not contain toluene has come to be desired from the market.
[Problems to be solved by the present invention]
[0004]
The present invention eliminates the problems of conventional chloroprene rubber adhesives, that is, the indoor environmental pollution associated with the use of toluene, and the drying of the solvent becomes too fast, and there is no tack reduction due to the occurrence of condensation during use, and storage stability It aims at ensuring drying property and adhesion performance.
[Means for Solving the Problems]
[0005]
As a result of intensive studies for solving the above problems, the invention described in claim 1 contains chloroprene rubber, tackifier resin, and an organic solvent containing methylcyclohexane and not containing toluene as essential components. A chloroprene rubber-based adhesive composition. The invention according to claim 2 is the chloroprene rubber adhesive composition according to claim 1, wherein 5 to 50% of methylcyclohexane is used as the organic solvent.
[0006]
This chloroprene rubber adhesive composition does not contain toluene, which is the indoor pollutant, and realizes stability, drying property, tack strength, anti-condensation, adhesion performance, and the like.
[0007]
The present invention is described in detail below.
The chloroprene rubber used in the present invention is polychloroprene obtained by polymerizing a chloroprene monomer. In general, the polymerization is carried out by emulsion polymerization, and the obtained polychloroprene latex is further coagulated, washed with water and dried to form a chip. Further, those having a carboxyl group in the molecule, preferably polychloroprene having two or more carboxyl groups in one molecule may be used.
[0008]
The tackifying resin used in the present invention is selected from a phenolic resin, a terpene resin, a rosin derivative resin, a petroleum hydrocarbon resin, a coumarone / indene resin, and a styrene resin, or a combination thereof. . The additive is generally 10 to 150 parts by weight with respect to 100 parts by weight of the total chloroprene rubber. This is because if the amount of the tackifying resin is less than this range, sufficient adhesive strength cannot be exhibited, and if it is increased, the adhesive strength is improved, but it may become brittle.
[0009]
The organic solvent containing methylcyclohexane and not containing toluene used in the present invention includes methylcyclohexane, ketones such as acetone and MEK (methyl ethyl ketone), esters such as ethyl acetate and butyl acetate, and n-hexane and cyclohexane. A solvent that does not contain toluene, such as hydrocarbons and alcohols such as methanol and ethanol, is mixed. These combinations and blending ratios are appropriately adjusted according to the purpose to adjust the solubility of chloroprene rubber and tackifier, the drying property, the appearance of tack, and the like. And this organic solvent uses 5 to 50% of methylcyclohexane. This is because when the amount of methylcyclohexane is less than this range, sufficient adhesive strength and stability are hardly obtained, and when the amount is larger, the drying time of the adhesive tends to be longer.
[0010]
In addition to the Ingredients in the chloroprene rubber adhesive composition of the present invention, generally a metal oxide used, vulcanizing agent, vulcanization accelerator, filler, softeners, plasticizers, processing aids, anti-aging An appropriate amount of an agent, a stabilizer, a reinforcing agent, a crosslinking agent and the like can be included.
[0011]
【Example】
Hereinafter, although an Example demonstrates concretely, this invention is not limited to these Examples.
[0012]
Examples and Comparative Examples Adhesives of Examples and Comparative Examples were prepared according to the formulations shown in Table 1 and used for the tests.
Chloroprene rubber (manufactured by Electrochemical Co., Ltd., A90), magnesium oxide (magnesia) and zinc oxide (zinc white) are kneaded for 20 minutes with a 9 inch roll. The kneaded rubber, phenol resin (manufactured by Showa Polymer Co., Ltd., CKM-1634) and anti-aging agent (diphenylamine type) are dissolved in various mixed solvents. Dissolution was performed using a disper at 1000 rpm for 10 hours.
[Table 1]
The initial viscosity, phase separation stability, low temperature stability, drying time, condensation, tack time, and adhesion performance of the chloroprene rubber adhesive compositions obtained in the following examples and comparative examples were measured by the following methods. ,evaluated.
[0014]
Table 2 shows the initial viscosity, phase separation stability, low temperature stability, drying time, condensation, tack time, and adhesive performance of each prepared adhesive composition. From the results of Table 2, the non-toluene type Examples 1 and 2 using methylcyclohexane are almost equivalent to the toluene-containing type in terms of stability, drying time, condensation, tack time, and adhesion performance, whereas methylcyclohexane The non-toluene type that does not use is inferior in terms of stability, tack time, condensation, and adhesion performance, and it can be seen that the chloroprene rubber adhesive of the present invention is useful.
[Table 2]
<Initial viscosity>
The initial viscosity was measured with a Brookfield rotary viscometer under the conditions of BM type, No. 3, and 12 rpm.
[0016]
<Phase separation stability>
The adhesive is stored at 40 ° C. for 2 months and checked for changes in viscosity and appearance. Viscosity is measured with a Brookfield rotary viscometer.
[0017]
<Low temperature stability>
The adhesive is stored at -5 ° C for 10 days and then checked for changes in viscosity and appearance at -5 ° C.
[0018]
<Drying time>
Adhesive is applied to kraft paper with a bar coater at 120 g / m 2 . Store at 20 ° C., and let the drying time be when the adhesive is no longer transferred to the hand.
[0019]
<Condensation>
Adhesive is applied to kraft paper with a bar coater at 120 g / m 2 . Thereafter, the kraft paper is cut into a width of 50 mm, and the condensation during the curing and adhesive drying at 90% RH at 20 ° C. is visually evaluated.
<Evaluation criteria> ○: No condensation or equivalent compared to conventional products.
×: More condensation than the conventional product.
[0020]
<Tack time (adhesive time)>
Adhesive is applied to kraft paper with a bar coater at 120 g / m 2 . Thereafter, the kraft paper is cut out to a width of 50 mm and pasted at 20 ° C. every 5 minutes. The pressing at that time is performed by rolling a 5 kg roller. The tack time is taken while the kraft paper is broken.
[0021]
<Adhesion performance>
Adhesion conditions and test items are as follows.
【The invention's effect】
As shown above, the chloroprene rubber-based adhesive composition obtained by the present invention does not contain toluene designated as a first-class designated chemical substance in the PRTR method, and has good stability at low temperatures, Tensile shear strength is excellent in initial shear, normal shear, and heat-resistant shear, and is suitable as an adhesive for a wide range of materials such as furniture, woodwork, and building materials.
Moreover, a general solvent composed only of n-hexane, acetone, and ethyl acetate can be used safely without problems such as excessive drying and easy condensation during use.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002026831A JP3773861B2 (en) | 2002-02-04 | 2002-02-04 | Chloroprene rubber adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002026831A JP3773861B2 (en) | 2002-02-04 | 2002-02-04 | Chloroprene rubber adhesive composition |
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| Publication Number | Publication Date |
|---|---|
| JP2003226852A JP2003226852A (en) | 2003-08-15 |
| JP3773861B2 true JP3773861B2 (en) | 2006-05-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002026831A Expired - Lifetime JP3773861B2 (en) | 2002-02-04 | 2002-02-04 | Chloroprene rubber adhesive composition |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005178637A (en) * | 2003-12-19 | 2005-07-07 | Toyo Ink Mfg Co Ltd | Interior material for automobile |
| BRPI0703285B1 (en) * | 2007-07-26 | 2017-06-20 | Oxiteno S/A Indústria e Comércio | Balanced solutions of non-toluene solvents for polychloroprene resin based contact adhesives comprising a plurality of miscible solvents |
| JP5484680B2 (en) * | 2008-02-18 | 2014-05-07 | 電気化学工業株式会社 | Method for producing chloroprene polymer composition |
| JP5295943B2 (en) | 2008-12-26 | 2013-09-18 | 花王株式会社 | Nanofiber sheet |
| JP2011132633A (en) * | 2009-12-24 | 2011-07-07 | Kao Corp | Nanofiber sheet |
| JP6057925B2 (en) | 2012-02-13 | 2017-01-11 | デンカ株式会社 | Method for producing chloroprene rubber composition, and method for producing adhesive composition using chloroprene rubber composition produced by the production method |
| JP2017155185A (en) * | 2016-03-04 | 2017-09-07 | 東ソー株式会社 | Chloroprene rubber-based adhesive |
| JP6733436B2 (en) * | 2016-05-20 | 2020-07-29 | 横浜ゴム株式会社 | Adhesive, vulcanized rubber bonding method, conveyor belt |
| JP2019140059A (en) * | 2018-02-15 | 2019-08-22 | 昭和電工パッケージング株式会社 | Power storage device exterior material and power storage device |
| WO2022255157A1 (en) | 2021-05-31 | 2022-12-08 | デンカ株式会社 | Chip, method for manufacturing chip, and adhesive composition |
| WO2023170014A1 (en) | 2022-03-11 | 2023-09-14 | Arlanxeo Deutschland Gmbh | Eco-friendly adhesive formulation containing 2-methyl tetrahydrofuran |
-
2002
- 2002-02-04 JP JP2002026831A patent/JP3773861B2/en not_active Expired - Lifetime
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| JP2003226852A (en) | 2003-08-15 |
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