JP3364248B2 - Moisture curable adhesive for polyolefin - Google Patents
Moisture curable adhesive for polyolefinInfo
- Publication number
- JP3364248B2 JP3364248B2 JP28155792A JP28155792A JP3364248B2 JP 3364248 B2 JP3364248 B2 JP 3364248B2 JP 28155792 A JP28155792 A JP 28155792A JP 28155792 A JP28155792 A JP 28155792A JP 3364248 B2 JP3364248 B2 JP 3364248B2
- Authority
- JP
- Japan
- Prior art keywords
- monomer
- acrylate
- meth
- adhesive
- 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 - Fee Related
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Description
【発明の詳細な説明】
【０００１】
【産業上の利用分野】本発明は湿気硬化性のポリオレフ
ィン用粘着剤、更に詳しくは、たとえばポリエチレンや
ポリプロピレンを被着体とする粘着テープの粘着剤とし
て有用で、特に粘着付与剤を配合しなくとも十分満足な
接着強度を得ることができ、同時に該粘着付与剤による
耐候性低下の防止を意図したアクリル系感圧粘着剤に関
する。
【０００２】
【従来の技術と発明が解決しようとする課題】従来よ
り、この種のポリオレフィン用粘着剤として、耐候性良
好なアクリル系感圧粘着剤が使用されている。このアク
リル系感圧粘着剤は、粘着性モノマーとして炭素数４〜
１４の鎖状アルキル(メタ)アクリレート、凝集性モノマ
ーとしてメチル(メタ)アクリレート、エチル(メタ)アク
リレート、スチレン、アクリロニトリル等および架橋性
モノマーとしてカルボキシル基、ヒドロキシル基または
加水分解性シリル基を含有するビニル系モノマーのアク
リル系共重合体を主成分とし、架橋性モノマーがカルボ
キシル基またはヒドロキシル基を含有するビニル系モノ
マーである場合はイソシアネート系架橋剤が配合され
る。
【０００３】しかしながら、極性が低いポリオレフィン
に対する接着強度を確保するには一般に粘着付与剤(た
とえばロジン、変性ロジン、テルペン樹脂、水添テルペ
ン樹脂、石油樹脂)を配合する必要があるが、粘着付与
剤の使用は耐候性の低下を招く結果となる。なお、本明
細書において、(メタ)アクリレートとは、アクリレート
もしくはメタクリレートを意味する。
【０００４】
【課題を解決するための手段】そこで、本発明者らは、
上記アクリル系共重合体の接着強度を向上せしめ、粘着
付与剤の配合を省略すべく鋭意検討を進めたところ、凝
集モノマーとして脂環式構造を含有する(メタ)アクリレ
ートおよび架橋性モノマーとして加水分解性シリル基を
含有するビニル系モノマーを使用し、かつ各モノマー割
合を特定化すれば、初期目的の接着強度が得られること
を見出し、本発明を完成させるに至った。
【０００５】すなわち、本発明は、接着性モノマーとし
て炭素数４〜１４の鎖状アルキル(メタ)アクリレートと
凝集モノマーとして脂環式構造を含有する(メタ)アクリ
レートの重量比５０／５０〜９５／５混合物１００部
(重量部、以下同様)に対し架橋性モノマーとして加水分
解性シリル基を含有するビニル系モノマー０.０１〜５
部を共重合して得られるアクリル系共重合体から成るこ
とを特徴とする湿気硬化性のポリオレフィン用粘着剤を
提供するものである。
【０００６】本発明で粘着性モノマーとして用いる炭素
数４〜１４の鎖状アルキル(メタ)アクリレートとして
は、たとえばブチルアクリレート、２−エチルヘキシル
アクリレート、オクチルアクリレート、イソノニルアク
リレート、ラウリルメタクリレート等が挙げられ、これ
らの少なくとも１種を使用する。
【０００７】本発明で凝集性モノマーとして用いる脂環
式構造を含有する(メタ)アクリレートとしては、たとえ
ば、式：
【化１】
（式中、ＲはＨまたはＣＨ3)(以下同様)のシクロヘキシ
ル(メタ)アクリレート、式:
【化２】
のトリシクロデカニル(メタ)アクリレート、式:
【化３】
のイソボルニル(メタ)アクリレート等が挙げられ、これ
らの少なくとも１種を使用する。
【０００８】かかる両モノマーの割合は、上記粘着性モ
ノマーと凝集性モノマーの重量比が５０／５０〜９５／
５、好ましくは６０／４０〜９０／１０となるように選
定する。凝集性モノマーの比率が５未満であると、粘着
剤の凝集力が低下して剥離時に粘着剤層が凝集破壊し、
また５０を越えると、粘着剤層の凝集力が増大して粘着
性が低下する傾向となる。
【０００９】本発明で架橋性モノマーとして用いる加水
分解性シリル基を含有するビニル系モノマーとしては、
たとえばアクリロイルアルコキシシラン、メタクリロイ
ルアルコキシシラン、ビニルアルコキシシラン等が挙げ
られ、これらの少なくとも１種を使用する。使用量は、
上記粘着性モノマーと凝集性モノマーの合計量１００部
に対し、好ましくは０.０１〜２部の範囲で選定する。
０.０１部未満では、加水分解性シリル基の架橋が不充
分となり、また２部を越えると、架橋密度が増大して粘
着性が低下する傾向となる。
【００１０】本発明におけるアクリル系共重合体は、上
記所定割合の粘着性モノマー、凝集性モノマーおよび架
橋性モノマーを、通常の溶液重合、乳化重合、活性エネ
ルギー線重合などの方法で共重合することにより製造さ
れる。
【００１１】本発明に係る湿気硬化性のポリオレフィン
用粘着剤は、上記で製造されるアクリル系共重合体を主
成分とする。
【００１２】
【発明の効果】以上の構成から成る本発明粘着剤は、特
殊な凝集性モノマーを使用したことにより、ポリオレフ
ィンに対し優れた接着強度を発揮でき、従来より必要で
あった粘着付与剤の配合を省略することができる。この
ため、粘着付与剤による耐候性低下の問題が解決され
る。
【００１３】
【実施例】次に実施例および比較例を挙げて、本発明を
より具体的に説明する。
実施例１〜５および比較例１〜９
(１)アクリル系共重合体の製造
下記表１に示す部数の各モノマーを、窒素雰囲気下、酢
酸エチル中、アゾビスイソブチロニトリルの存在下で７
５℃にて２４時間溶液重合を行って、アクリル系共重合
体溶液(７０％溶液)を得る。
【００１４】
【表１】
【００１５】(２)粘着剤の調製
実施例１〜５または比較例１〜９のアクリル系共重合体
溶液をさらに４０％濃度に希釈した溶液１００部にジブ
チルチンジラウレート(硬化触媒)０.０５部を加えて、
湿気硬化性の粘着剤とする。
【００１６】(３)接着試験
ＰＥＴフィルムの表面をサンドペーパー＃２８０でサン
ディングし、次いでトルエンワイプを行った後、イソシ
アネート系プライマー[サンスター技研(株)製、プライ
マーＰＰ２]を塗布し、２０℃,６５％ＲＨで１時間室温
乾燥する。これに上記(２)の粘着剤を乾燥膜厚５０μに
て塗布し、１００℃で９０秒間乾燥してから、４０℃で
１日間養生を行う。一方、ポリプロピレン(ＰＰ)板また
は上記と同様に表面サンディングしたステンレス板(Ｓ
ＵＳ３０４)をトルエンワイプしてから、これらを上記
のＰＥＴフィルムへ粘着剤を介して重ね合せ、次いで圧
締(２kgローラー、１往復)し、３０分後に剥離強度(g／
１０mm)を測定する(引張速度３００mm／分、１８０゜
角)。結果を下記表２に示す。
【００１７】
【表２】
【００１８】なお、比較例１の粘着剤(４０％溶液)１０
０部に下記の粘着付与剤８部を配合したものを上述の接
着試験に供したところ、ＰＰ板およびＳＵＳ３０４に対
してそれぞれ、下記の剥離強度(g／１０mm)が得られた
が、これらを耐候促進試験(アイスーパー試験機使用、
特定波長ＵＶ２４時間照射)に供したところ、いずれも
黄変が観察された。なお、実施例１〜５のものは、黄変
変色もなし、耐候性の低下は認められなかった。
【表３】
剥離強度
ＳＵＳ
粘着付与剤 ＰＰ板 ３０４
水添テルペンフェノール樹脂 ６７０ ７５０
水添テルペン樹脂 ６００ ６００
Ｃ6石油系樹脂 ５７０ ６３０
Ｃ9石油系樹脂 ６００ ６５０
ロジン変性フェノール樹脂 ７３０ ８００Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a moisture-curable pressure-sensitive adhesive for polyolefins, and more particularly, to a pressure-sensitive adhesive comprising, for example, polyethylene or polypropylene as an adherend. The present invention relates to an acrylic pressure-sensitive adhesive which is useful as a pressure-sensitive adhesive for a tape, can provide a sufficiently satisfactory adhesive strength without particularly including a tackifier, and is intended to prevent a decrease in weather resistance due to the tackifier. 2. Description of the Related Art Conventionally, an acrylic pressure-sensitive adhesive having good weather resistance has been used as this kind of polyolefin adhesive. This acrylic pressure-sensitive adhesive has 4 to 4 carbon atoms as an adhesive monomer.
14 chain alkyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, styrene, acrylonitrile, etc. as a cohesive monomer and vinyl containing a carboxyl group, a hydroxyl group or a hydrolyzable silyl group as a crosslinkable monomer When the crosslinkable monomer is a vinyl monomer having a carboxyl group or a hydroxyl group, the isocyanate crosslinker is blended when the acrylic copolymer of the monomer is a main component. However, in order to secure the adhesive strength to polyolefins having low polarity, it is generally necessary to incorporate a tackifier (eg, rosin, modified rosin, terpene resin, hydrogenated terpene resin, petroleum resin). Use results in a decrease in weather resistance. In addition, in this specification, (meth) acrylate means acrylate or methacrylate. [0004] Accordingly, the present inventors have proposed:
Improving the adhesive strength of the acrylic copolymer and intensively studying to omit the compounding of the tackifier, the (meth) acrylate containing an alicyclic structure as an aggregation monomer and hydrolysis as a crosslinkable monomer. A reactive silyl group
The present inventors have found that if the contained vinyl monomer is used and the ratio of each monomer is specified, it is possible to obtain an initial desired adhesive strength, and have completed the present invention. That is, according to the present invention, a weight ratio of a chain alkyl (meth) acrylate having 4 to 14 carbon atoms as an adhesive monomer and a (meth) acrylate having an alicyclic structure as an aggregation monomer is 50/50 to 95/95. 100 parts of 5 mixture
(Parts by weight, hereinafter the same) vinyl containing as a crosslinking monomer pressurized hydrolyzable silyl group to a monomer 0.01-5
It is intended to provide a moisture-curable pressure-sensitive adhesive for polyolefin, comprising an acrylic copolymer obtained by copolymerizing parts. Examples of the chain alkyl (meth) acrylate having 4 to 14 carbon atoms used as the adhesive monomer in the present invention include butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, isononyl acrylate, lauryl methacrylate and the like. At least one of these is used. The (meth) acrylate having an alicyclic structure used as a cohesive monomer in the present invention includes, for example, a compound represented by the following formula: (Wherein R is H or CH 3 ) (the same applies hereinafter) cyclohexyl (meth) acrylate, having the formula: Of tricyclodecanyl (meth) acrylate of the formula: And at least one of these is used. The ratio of the two monomers is such that the weight ratio of the adhesive monomer and the cohesive monomer is 50/50 to 95/95.
5, preferably 60/40 to 90/10. When the ratio of the cohesive monomer is less than 5, the cohesive force of the pressure-sensitive adhesive is reduced and the pressure-sensitive adhesive layer is cohesively broken at the time of peeling,
On the other hand, when it exceeds 50, the cohesive force of the pressure-sensitive adhesive layer increases and the tackiness tends to decrease. [0009] As the vinyl monomer containing a pressurized hydrolysis silyl group Ru used as the crosslinking monomer in the present invention,
For example A methacryloyl alkoxysilane, methacryloyl alkoxysilane, vinyl alkoxysilanes, and the like, using at least one of these. The amount used is
The total amount 100 parts of cohesion monomer with the adhesive monomer, good Mashiku is selected in the range of 0.01 to 2 parts.
If the amount is less than 0.01 part, crosslinking of the hydrolyzable silyl group becomes insufficient, and if it exceeds 2 parts, the crosslinking density increases and the tackiness tends to decrease. The acrylic copolymer in the present invention is obtained by copolymerizing the above-mentioned predetermined ratio of the tacky monomer, cohesive monomer and crosslinkable monomer by a method such as ordinary solution polymerization, emulsion polymerization and active energy ray polymerization. It is manufactured by The moisture-curable pressure-sensitive adhesive for polyolefin according to the present invention contains the acrylic copolymer produced as described above as a main component . The pressure-sensitive adhesive of the present invention having the above constitution can exhibit excellent adhesive strength to a polyolefin by using a special cohesive monomer, and is a tackifier conventionally required. Can be omitted. Therefore, the problem collapsed determine the weather resistance decreases due tackifier. The present invention will be described more specifically with reference to examples and comparative examples. Examples 1 to 5 and Comparative Examples 1 to 9 (1) Production of Acrylic Copolymer In the presence of azobisisobutyronitrile in ethyl acetate, under a nitrogen atmosphere, each monomer in the number shown in Table 1 was used. 7
Solution polymerization is performed at 5 ° C. for 24 hours to obtain an acrylic copolymer solution (70% solution). [Table 1] (2) Preparation of pressure-sensitive adhesive Dibutyltin dilaurate (curing catalyst) 0.05 was added to 100 parts of a solution obtained by further diluting the acrylic copolymer solution of Examples 1 to 5 or Comparative Examples 1 to 9 to a concentration of 40%. part by the addition of,
A moisture-curable adhesive. (3) Adhesion test The surface of the PET film was sanded with sandpaper # 280, and toluene wipe was performed. Then, an isocyanate-based primer [Primer PP2, manufactured by Sunstar Giken Co., Ltd.] was applied, and the resultant was coated at 20 ° C. , 65% RH for 1 hour at room temperature. The pressure-sensitive adhesive of the above (2) is applied thereto with a dry film thickness of 50 μm, dried at 100 ° C. for 90 seconds, and then cured at 40 ° C. for 1 day. On the other hand, a polypropylene (PP) plate or a stainless steel plate (S
US304) was toluene wiped, and these were superimposed on the above PET film via an adhesive, and then pressed (2 kg roller, one reciprocation), and after 30 minutes, the peel strength (g / g) was obtained.
10 mm) (tensile speed 300 mm / min, 180 ° square). The results are shown in Table 2 below. [Table 2] The pressure-sensitive adhesive (40% solution) 10 of Comparative Example 1 was used.
When the above-mentioned adhesion test was conducted on a mixture obtained by mixing 8 parts of the following tackifier with 0 parts, the following peel strength (g / 10 mm) was obtained for the PP plate and SUS304, respectively. Weather resistance acceleration test (using an eye super tester,
(Irradiation with specific wavelength UV for 24 hours), yellowing was observed in each case. In Examples 1 to 5 , no yellowing or discoloration was observed, and no decrease in weather resistance was observed. [Table 3] Peel strength SUS tackifier PP plate 304 hydrogenated terpene phenolic resin 670 750 hydrogenated terpene resin 600 600 C 6 petroleum-based resin 570 630 C 9 petroleum-based resin 600 650 rosin-modified phenolic resin 730 800
フロントページの続き (56)参考文献 特開 平１−98679（ＪＰ，Ａ) 特開 昭58−194966（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C09J 133/08 C09J 175/04 Continuation of the front page (56) References JP-A-1-98679 (JP, A) JP-A-58-194966 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C09J 133 / 08 C09J 175/04
Claims (1)
鎖状アルキル(メタ)アクリレートと凝集モノマーとして
脂環式構造を含有する(メタ)アクリレートの重量比５０
／５０〜９５／５混合物１００重量部に対し架橋性モノ
マーとして加水分解性シリル基を含有するビニル系モノ
マー０.０１〜５重量部を共重合して得られるアクリル
系共重合体から成ることを特徴とする湿気硬化性のポリ
オレフィン用粘着剤。(57) [Claims 1] A C 4-14 carbon atom as an adhesive monomer.
Weight ratio of chain alkyl (meth) acrylate to (meth) acrylate containing an alicyclic structure as an aggregation monomer is 50.
Made of an acrylic copolymer obtained / 50-95 / 5 mixture vinyl monomer 0.01-5 parts by weight as a cross-linking monomer containing a pressurized hydrolyzable silyl group per 100 parts by weight of copolymerizing A moisture-curable pressure-sensitive adhesive for polyolefins.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28155792A JP3364248B2 (en) | 1992-10-20 | 1992-10-20 | Moisture curable adhesive for polyolefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28155792A JP3364248B2 (en) | 1992-10-20 | 1992-10-20 | Moisture curable adhesive for polyolefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06128544A JPH06128544A (en) | 1994-05-10 |
| JP3364248B2 true JP3364248B2 (en) | 2003-01-08 |
Family
ID=17640849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28155792A Expired - Fee Related JP3364248B2 (en) | 1992-10-20 | 1992-10-20 | Moisture curable adhesive for polyolefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3364248B2 (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5616670A (en) * | 1993-11-10 | 1997-04-01 | Minnesota Mining And Manufacturing Company | Pressure sensitive adhesives with good oily surface adhesion |
| US5683798A (en) * | 1993-11-10 | 1997-11-04 | Minnesota Mining And Manufacturing Company | Tackified pressure sensitive adhesives |
| US5654387A (en) * | 1993-11-10 | 1997-08-05 | Minnesota Mining And Manufacturing Company | Pressure sensitive adhesives |
| US5602221A (en) * | 1993-11-10 | 1997-02-11 | Minnesota Mining And Manufacturing Company | Pressure sensitive adhesives with good low energy surface adhesion |
| JP3486698B2 (en) * | 1994-10-04 | 2004-01-13 | 一方社油脂工業株式会社 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive product |
| ES2145995T3 (en) * | 1995-02-16 | 2000-07-16 | Minnesota Mining & Mfg | ARTICLES INCORPORATING PRESSURE SENSITIVE ADHESIVES WITH IMPROVED ADHESION TO PLASTIFIED POLY- (VINYL CHLORIDE). |
| US5905099A (en) * | 1995-11-06 | 1999-05-18 | Minnesota Mining And Manufacturing Company | Heat-activatable adhesive composition |
| US5817426A (en) * | 1996-12-04 | 1998-10-06 | Avery Dennison Corporation | Acrylic pressure-sensitive adhesives for low-energy surfaces and corrugated board |
| US20040076785A1 (en) * | 2000-05-09 | 2004-04-22 | Richards Corlyss J. | Water-whitening resistant latex emulsion pressure sensitive adhesive and its production |
| JP4498138B2 (en) * | 2002-08-22 | 2010-07-07 | 三菱レイヨン株式会社 | Primer composition for paint |
| JP4521520B2 (en) * | 2003-08-06 | 2010-08-11 | 綜研化学株式会社 | Adhesive for low polarity film |
| DE102004063330A1 (en) * | 2004-12-23 | 2006-07-06 | Tesa Ag | Adhesive tape, in particular for covering window flanges |
| WO2012128294A1 (en) * | 2011-03-24 | 2012-09-27 | リンテック株式会社 | Pressure sensitive adhesive and pressure sensitive adhesive sheet |
| JP5607565B2 (en) * | 2011-03-28 | 2014-10-15 | リンテック株式会社 | Adhesive and adhesive sheet |
-
1992
- 1992-10-20 JP JP28155792A patent/JP3364248B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06128544A (en) | 1994-05-10 |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| LAPS | Cancellation because of no payment of annual fees |