JP4716563B2 - Adhesive composition - Google Patents

Description

【００１１】
〔式中、Ｒ¹およびＲ²はいずれも炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基または（Ｒ´）₃ＳｉＯ‐（Ｒ´は炭素数１〜２０の１価の炭化水素基であり、３個のＲ´は同じであってもよく、異なっていてもよい）で示されるトリオルガノシロキシ基であり、Ｒ¹またはＲ²が２個以上存在するとき、それらは同じであってもよく、異なっていてもよい、Ｘは水酸基または加水分解性基であり、２個以上存在するとき、それらは同じであってもよく、異なっていてもよい。ａは０、１、２、または３、ｂは０、１または２、ただしａ＋ｍｂ≧１、またｍ個の
【００１２】
【化２】

【００１３】
におけるｂは同じである必要はない。ｍは０または１〜１９の整数〕で表わされる基があげられる。
【００１４】
前記加水分解性基の具体例としては、たとえば水素原子、ハロゲン原子、アルコキシ基、アシルオキシ基、ケトキシメート基、アミノ基、アミド基、酸アミド基、アミノオキシ基、メルカプト基、アルケニルオキシ基などの一般に使用されている基があげられる。
【００１５】
該加水分解性基や水酸基は１個のケイ素原子に１〜３個の範囲で結合することができ、（ａ＋ｍｂ）は１〜５の範囲が好ましい。加水分解性基や水酸基が反応性ケイ素基中に２個以上結合するばあいには、それらは同じであってもよく、異なっていてもよい。
【００１６】
前記反応性ケイ素基を形成するケイ素原子は１個でもよく、２個以上であってもよいが、シロキサン結合などにより連結されたケイ素原子のばあいには、２０個のものまでであるのが好ましい。とくに式（２）：
【００１７】
【化３】

【００１８】
（式中、Ｒ²、Ｘ、ａは前記と同じ）で表される反応性ケイ素基が、入手が容易であるので好ましい。
【００１９】
反応性ケイ素基は飽和炭化水素系重合体１分子中に少なくとも１個、好ましくは１.１〜５個存在する。分子中に含まれる反応性ケイ素基の数が１個未満になると、硬化性が不充分になり、良好なゴム弾性挙動を発現しにくくなる。
【００２０】
反応性ケイ素基は飽和炭化水素系重合体分子鎖の末端に存在してもよく、内部に存在してもよく、両方に存在してもよい。とくに反応性ケイ素基が分子鎖末端に存在する場合には、最終的に形成される硬化物に含まれる飽和炭化水素系重合体成分の有効網目鎖量が多くなるため、高強度で高伸びのゴム状硬化物がえられやすくなるなどの点から好ましい。また、これら反応性ケイ素基を有する飽和炭化水素系重合体は単独で使用してもよく、２個以上併用してもよい。
【００２１】
本発明に用いる反応性ケイ素基を有する飽和炭化水素系重合体の骨格をなす重合体は、（１）エチレン、プロピレン、１−ブテン、イソブチレンなどのような炭素数１〜６のオレフィン系化合物を主モノマーとして重合させる、又は（２）ブタジエン、イソプレンなどのようなジエン系化合物を単独重合させたり、上記オレフィン系とジエン系化合物とを共重合させたりしたのち水素添加するなどの方法によりうることができるが、末端に官能基を導入しやすい、また分子量を制御しやすい末端官能基の数を多くすることができるなどの点から、イソブチレン系重合体や水添ポリブタジェン系重合体であるのが好ましい。
【００２２】
なお、本明細書にいう飽和炭化水素系重合体とは、芳香環以外の炭素‐炭素不飽和結合を実質的に含有しない重合体を意味する概念である。
【００２３】
前記イソブチレン系重合体は、単量体単位のすべてがイソブチレン単位から形成されていてもよく、イソブチレンと共重合性を有する単量体単位をイソブチレン系重合体の好ましくは３０％以下、とくに好ましくは１０％以下の範囲で含有してもよい。
【００２４】
前記イソブチレンと共重合性を有する単量体としては、たとえば炭素数４〜１２のオレフィン、ビニルエーテル、芳香族ビニル化合物、ビニルシラン類、アリルシラン類などがあげられる。
【００２５】
前記水添ポリブタジエン系重合体や他の飽和炭化水素系重合体においても、上記イソブチレン系重合体のばあいと同様に、主成分となる単量体単位の他に他の単量体単位を含有してもよい。
【００２６】
また、本発明に用いる飽和炭化水素系重合体には、本発明の目的が達成される範囲でブタジエン、イソプレンのようなポリエン化合物のごとき重合後２重結合の残るような単量体単位を少量、好ましくは１０％以下、さらには５％以下、とくには１％以下の範囲で含有させてもよい。
【００２７】
前記飽和炭化水素系重合体、好ましくはイソブチレン系重合体または水添ポリブタジェン系重合体の数平均分子量は５００〜３０，０００程度であるのが好ましく、とくに１，０００〜１５，０００程度の液状物〜流動性を有するものが取扱い安いなどの点から好ましい。
【００２８】
上述した反応性ケイ素基を有する飽和炭化水素系重合体の製造方法は、特開平１−１７０６８１号公報に詳述されている。
【００２９】
また、上述した飽和炭化水素系重合体（Ａ）としては、具体的には下記式（３）に示されるＥＰＩＯＮ（鐘淵化学工業(株)製）が好適に用いられる。
【００３０】
【化４】

【００３１】
（式中、ｘ，ｙは０又は１〜２０の整数、１≦ｘ＋ｙ≦２０）
【００３２】
（Ｂ）成分である前記粘着付与剤の例としては、たとえばクマロン−インデン樹脂、クマロン樹脂にナフテン樹脂、フェノール樹脂、ロジンなどを混合したものなどのクマロン系樹脂；ｐ−ｔ−ブチルフェノール−アセチレン樹脂、重合度が低く低軟化点（６０〜１００℃程度）のフェノールホルムアルデヒド樹脂、キシレン−フェノール樹脂、キシレン樹脂、粘着性のみならず接着性や耐熱性も向上させるテルペン−フェノール樹脂、テルペン樹脂などのフェノール系、テルペン系樹脂；合成ポリテルペン樹脂、芳香族炭化水素樹脂、脂肪族系炭化水素樹脂、脂肪族系環状炭化水素樹脂、水素添加炭化水素樹脂などの石油系炭化水素樹脂；ロジンやロジンのペンタエリスリトール・エステル、ロジンのグリセロール・エステル、水素添加ロジン、高度に水素添加したウッドレジン、水素添加ロジンのメチルエステル、水素添加ロジンのトリエチレングリコールエステル、水素添加ロジンのペンタエリスリトール・エステル、重合ロジン、重合ロジンのグリセロール・エステル、樹脂酸亜鉛、硬化ロジンなどのロジン誘導体；低分子量ポリスチレン、その他の特殊調合品などがあげられるが、それらに限定されるものではない。これらのなかではテルペン系樹脂、石油系炭化水素樹脂がとくに相溶性がよく、粘着性特性が良好であるので好ましい。これらの粘着付与剤は単独で使用してもよく、２種以上併用してもよい。
【００３３】
（Ｃ）成分としてのポリブテンとしては、通常のポリブテンの他に、水添ポリブテン、変性ポリブテン等を包含するが、具体的には、ＨＶ−３００（日本石油（株）製ポリブテン）等が好適に用いられる。液状テルペン重合体としては、ＹＳレジンＰＸ−２００〔ヤスハラケミカル（株）製〕等が用いられる。（Ｃ）成分としてのポリブテンと液状テルペン重合体とはそれぞれ単独で用いてもよく、また両者を混合して用いてもよい。
【００３４】
本発明の粘着剤組成物の必須成分である（Ａ）（Ｂ）（Ｃ）の配合割合は、成分（Ａ）１００重量部に対して、成分（Ｂ）２０〜８００重量部、好ましくは３０〜４００重量部及び成分（Ｃ）２０〜１５００重量部、好ましくは３０〜１０００重量部が用いられる。
【００３５】
本発明の粘着剤組成物には、上記した必須成分に加えて粘度、物性を調整するために必要に応じて硬化触媒、充填剤、可塑剤、接着付与剤、安定剤、着色剤等を配合することができる。
【００３６】
硬化触媒としては、例えば、テトラブチルチタネート、テトラプロピルチタネート等のチタン酸エステル類；ジブチル錫ジラウレート、ジブチル錫マレエート、ジブチル錫ジアセテート、オクチル酸錫、ナフテン酸錫等の有機錫化合物：オクチル酸鉛；ブチルアミン、オクチルアミン、ラウリルアミン、ジブチルアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ジエチレントリアミン、トリエチレンテトラミン、オレイルアミン、シクロヘキシルアミン、ベンジルアミン、ジエチルアミノプロピルアミン、キシリレンジアミン、トリエチレンジアミン、グアニジン、ジフェニルグアニジン、２，４，６−トリス（ジメチルアミノメチル）フェノール、モルホリン、Ｎ−メチルモルホリン、１，８−ジアザビシクロ（５．４．０）ウンデセン−７（ＤＢＵ）等のアミン系化合物またはこれらとカルボン酸等との塩；過剰のポリアミンと多塩基酸とから得られる低分子量ポリアミド樹脂；過剰のポリアミンとエポキシ化合物との反応生成物；ｒ−アミノプロピルトリメトキシシラン、Ｎ−（β−アミノエチル）アミノプロピルメチルジメトキシシラン等のアミノ基を有するシランカップリング剤等の公知のシラノール複合触媒等が挙げられる。これらの触媒は、単独で使用してもよく、２種以上併用してもよい。
【００３７】
可塑剤としては、プロセスオイルまたは他の炭化水素類でポリマーと相溶するものであれば特に限定されるものではなく、公知各種の可塑剤が使用可能である。例えば、ジブチルフタレート、ジヘプチルフタレート、ジ（２−エチルヘキシル）フタレート、ブチルベンジルフタレート、ブチルフタリルブチルグリコレート等のフタル酸エステル類；ジオクチルアジペート、ジオクチルセバケート等の非芳香族２塩基酸エステル類；ジエチレングリコールジベンゾエート、トリエチレングリコールジベンゾエート等のポリアルキレングリコールのエステル類；トリクレジルホスフェート、トリブチルホスフェート等のリン酸エステル類；塩化パラフィン類；アルキルジフェニル；部分水添ターフェニル等の炭化水素油；プロセスオイル類；アルキルベンゼン類等が挙げられる。
【００３８】
充填剤には、例えば、通常の炭酸カルシウム、カーボンブラック、クレー、タルク、酸化チタン、生石灰、カオリン、ゼオライト、珪藻土、塩化ビニルペーストレンジ、ガラスバルーン、塩化ビニリデン樹脂バルーン、アクリロニトリル・メタクリロニトリル樹脂バルーン等が挙げられ、単独または混合して使用できる。
【００３９】
接着付与剤として、シランカップリング剤等、安定剤としてヒンダードフェノール系化合物、トリアゾール系化合物等を使用する。着色剤としては、チタンホワイト、カーボンブラック、ベンガラ等が挙げられる。
【００４０】
本発明の粘着剤組成物は、必要に応じて１液型とすることもできるし、後記する実施例６〜８に示すように２液型とすることもできる。
【００４１】
【実施例】
以下に実施例をあげて本発明をさらに具体的に説明する。
【００４２】
（実施例１〜５及び比較例１〜５）
表１に示したように、飽和炭化水素系重合体（Ａ）としてシリル末端ポリイソブチレンポリマー（鐘淵化学工業(株)製ＥＰＩＯＮ ＥＰ５０５Ｓ）、粘着付与剤（Ｂ）としてテルペン樹脂（ヤスハラケミカル(株)製ＹＳレジンＴＯ−１０５）、及び第３成分として種々の配合物質をそれぞれ所定量ずつ配合し、１２０℃まで加熱し、粘着付与剤（Ｂ）を溶解混合した。この混合物を冷却して粘着剤組成物とした。この粘着剤組成物に接着付与剤として含チッ素塩基性基含有シラン化合物（信越化学工業(株)製ＫＢＥ−６０３）及び硬化触媒として錫化合物（三共有機合成(株)製Ｎｏ.９１８）を添加して粘着剤を調製した。得られた粘着剤を５ｍｍ厚のシート状に塗布し、５０℃、８５％ＲＨ条件下にて１日養生し硬化させ、指触タックにより粘着性を確認した。その結果を表１にあわせて示した。
【００４３】
【表１】

【００４４】
表１における各配合物質の配合量は重量部で示され、（＊１〜＊８）は次の通りである。
＊１：シリル末端ポリイソブチレンポリマー（鐘淵化学工業（株）製 ＥＰＩＯＮ ＥＰ５０５Ｓ）
＊２：テルペン樹脂（ヤスハラケミカル（株）製 ＹＳレジンＴＯ−１０５）
＊３：日本石油（株）製ＨＶ−３００
＊４：ヤスハラケミカル（株）製ＹＳレジン ＰＸ−２００
＊５：出光興産（株）製ＰＳ−３２
＊６：出光興産（株）製ＮＰ−２４
＊７：シラン化合物（信越化学工業（株）製ＫＢＥ−６０３）
＊８：錫化合物（三共有機合成（株）製Ｎｏ．９１８）
【００４５】
表１における粘着性の評価は次の通りである。
○：強粘着性、△：弱粘着性、×：粘着性なし。
【００４６】
表１に示した結果から添加物質としてポリブテン（実施例１〜４）及び液状テルペン重合体（実施例５）を配合した場合には粘着性が極めて向上して強粘着性を示すが、添加物としてプロセスオイル（パラフィン系）（比較例１）及びプロセスオイル（ナフテン系）（比較例２）を配合した場合には粘着性はあまり向上せず弱粘着性を示すに過ぎず、またＤＯＰ（ジオクチルフタレート）（比較例３）及びＤＯＡ（ジオクチルアジペート）（比較例４）を配合した場合には粘着性は発現されなかった。また、添加物を配合しない場合（比較例５）にも弱粘着性を示すのみであった。以上の結果から、飽和炭化水素系重合体（Ａ）及び粘着付与剤（Ｂ）に対してＣ成分としてポリブテン及び／又は液状テルペン重合体を配合することによって強粘着性の接着剤が得られることが判明した。
【００４７】
（実施例６〜８）
表２に示したように、飽和炭化水素重合体（Ａ）としてシリル末端ポリイソブチレンポリマー（鐘淵化学工業（株）製 ＥＰＩＯＮ ＥＰ５０５Ｓ）、粘着付与剤（Ｂ）としてテルペン樹脂（ヤスハラケミカル（株）製 ＹＳレジンＴＯ−１０５）、ポリブテン（日本石油（株）製 ＨＶ−３００）を所定量配合し、１２０℃まで加熱し、粘着付与剤（Ｂ）を溶解混合した。冷却後充填剤を攪拌混合し、主剤とし、硬化剤は所定量混合した。所定の配合量で主剤と硬化剤を混合し、５０℃条件下にて１日養生し硬化させ、指触タックにより粘着性を確認した。表２に示したようにいずれの実施例においても粘着性は極めて向上し、強粘着性であった。
【００４８】
【表２】

【００４９】
表２における各配合物質の配合量は重量部で示され、（＊１〜＊３、＊７及び＊８）は表１と同じであり、（＊９〜＊１１）は次の通りである。また、粘着性の評価も表１と同様である。
＊９：表面処理炭酸カルシウム（丸尾カルシウム（株）製 シーレッツ２００）
＊１０：ラウリルアミン（花王（株）製 ファーミン２０Ｄ）
＊１１：錫化合物（日東化成（株）製 ネオスタンＵ−２８）
【００５０】
【発明の効果】
上述したごとく、本発明によれば、（Ａ）ケイ素原子に結合した水酸基または加水分解性基を有し、シロキサン結合を形成することにより架橋しうるケイ素含有基を少なくとも１個有する飽和炭化水素系重合体および、（Ｂ）粘着付与剤を含有してなる粘着剤組成物に特定の物質を添加することによって、耐熱性、耐光性や耐候性に優れている上、タックの低下もないという特性を維持しつつ、極めて強い粘着性を有する粘着剤組成物を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a pressure-sensitive adhesive composition, in particular, a strong pressure-sensitive adhesive composition.
[0002]
[Related technologies]
An adhesive is a viscoelastic body with an adhesive tack that does not require a change of state from liquid to solid when used like a normal adhesive, and has the property of exhibiting adhesive strength that can withstand practical use as soon as it is bonded. Have. This pressure-sensitive adhesive can be directly applied to and adhered to an adherend in the same manner as the adhesive, and is used for pressure-sensitive adhesive tapes, pressure-sensitive adhesive sheets, pressure-sensitive adhesive labels and the like, as with other normal pressure-sensitive adhesives.
[0003]
In general, the pressure-sensitive adhesive is composed of a rubber-based pressure-sensitive adhesive mainly composed of natural rubber, synthetic rubber or a block copolymer, and an acrylic pressure-sensitive adhesive mainly composed of a copolymer of an acrylic monomer and a functional group-containing monomer. Divided into two. The former has insufficient heat resistance, light resistance, weather resistance and the like, while the latter has excellent weather resistance, but there is a problem that a decrease in tack cannot be avoided.
[0004]
Therefore, as a pressure-sensitive adhesive composition that solves the problems of rubber pressure-sensitive adhesive and acrylic pressure-sensitive adhesive at once, (A) having a hydroxyl group or hydrolyzable group bonded to a silicon atom and forming a siloxane bond A pressure-sensitive adhesive composition comprising a saturated hydrocarbon polymer having at least one crosslinkable silicon-containing group and (B) a tackifier has been proposed (Japanese Patent Laid-Open No. 1-170681). This pressure-sensitive adhesive composition has excellent properties such as excellent heat resistance, light resistance, and weather resistance, and does not cause a decrease in tack.
[0005]
The present inventors have made various studies on the tackiness of the above-mentioned pressure-sensitive adhesive composition, and the tackiness of this pressure-sensitive adhesive composition varies greatly depending on the substance blended as the third component, and a specific substance is blended. It has been found that the adhesiveness can be greatly improved by doing so, and the present invention has been completed.
[0006]
[Problems to be solved by the invention]
The present invention provides (A) a saturated hydrocarbon polymer having a hydroxyl group or hydrolyzable group bonded to a silicon atom and having at least one silicon-containing group that can be crosslinked by forming a siloxane bond, and (B ) By blending a specific substance into a pressure-sensitive adhesive composition containing a tackifier, it has excellent heat resistance, light resistance and weather resistance, while maintaining the characteristics that there is no decrease in tack, It aims at providing the adhesive composition which has strong adhesiveness.
[0007]
[Means for Solving the Problems]
In order to solve the above problems, the pressure-sensitive adhesive composition of the present invention, (A) has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, molecule a silicon-containing group capable of crosslinking by forming a siloxane bond A saturated hydrocarbon polymer having a number average molecular weight of 500 to 30,000, having at least one chain end , (B) a tackifier, and (C) a polybutene and / or a liquid terpene polymer , The (A) saturated hydrocarbon polymer has a liquid or fluidity, and the component (B) is 20 to 800 parts by weight and the component (C) is 20 to 1500 with respect to 100 parts by weight of the component (A). It is characterized by blending parts by weight .
The production method of the pressure-sensitive adhesive composition of the present invention comprises (A) a silicon-containing group having a hydroxyl group or a hydrolyzable group bonded to a silicon atom and capable of crosslinking by forming a siloxane bond at the molecular chain end. Production of a pressure-sensitive adhesive composition containing a saturated hydrocarbon polymer having a number average molecular weight of 500 to 30,000, (B) a tackifier, and (C) a polybutene and / or a liquid terpene polymer. It is a method, Comprising : Said (A) saturated hydrocarbon type polymer has a liquid substance or fluidity | liquidity, and component (B) 20-800 weight part with respect to 100 weight part of component (A), and component ( C) The pressure-sensitive adhesive composition is produced by blending 20 to 1500 parts by weight , heating, dissolving and mixing.
[0008]
In the present invention, the component (A) has a hydroxyl group or a hydrolyzable group bonded to a silicon atom, and a silicon-containing group that can be cross-linked by forming a siloxane bond, that is, a saturated group having at least one reactive silicon group. A hydrocarbon polymer (hereinafter sometimes referred to as a saturated hydrocarbon polymer (A)) is used.
[0009]
As a representative example of the reactive silicon group, the general formula (1):
[0010]
[Chemical 1]

[0011]
[Wherein R ¹ and R ² are all alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, aralkyl groups having 7 to 20 carbon atoms, or (R ′) ₃ SiO— (R ′ is A trivalent siloxy group having 1 to 20 carbon atoms, and three R's may be the same or different, and R ¹ or R ² is When two or more are present, they may be the same or different. X is a hydroxyl group or a hydrolyzable group. When two or more are present, they may be the same or different. It may be. a is 0, 1, 2, or 3, b is 0, 1 or 2, provided that a + mb ≧ 1, and m
[Chemical 2]

[0013]
The b in need not be the same. m is 0 or an integer of 1 to 19].
[0014]
Specific examples of the hydrolyzable group generally include, for example, a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Examples of the groups used are listed.
[0015]
The hydrolyzable group or hydroxyl group can be bonded to one silicon atom in the range of 1 to 3, and (a + mb) is preferably in the range of 1 to 5. When two or more hydrolyzable groups or hydroxyl groups are bonded to the reactive silicon group, they may be the same or different.
[0016]
The number of silicon atoms forming the reactive silicon group may be one or two or more, but in the case of silicon atoms connected by a siloxane bond or the like, the number is up to 20. preferable. In particular, formula (2):
[0017]
[Chemical 3]

[0018]
A reactive silicon group represented by the formula (wherein R ² , X and a are the same as described above) is preferable because it is easily available.
[0019]
At least one, preferably 1.1 to 5, reactive silicon groups are present in one molecule of the saturated hydrocarbon polymer. When the number of reactive silicon groups contained in the molecule is less than one, the curability becomes insufficient, and good rubber elastic behavior is hardly exhibited.
[0020]
The reactive silicon group may exist at the terminal of the saturated hydrocarbon polymer molecular chain, may exist inside, or may exist in both. In particular, when a reactive silicon group is present at the molecular chain end, the amount of the effective network chain of the saturated hydrocarbon polymer component contained in the finally formed cured product increases, so that the high strength and high elongation are achieved. This is preferable from the viewpoint that a rubber-like cured product is easily obtained. Further, these saturated hydrocarbon polymers having a reactive silicon group may be used alone or in combination of two or more.
[0021]
The polymer constituting the skeleton of the saturated hydrocarbon polymer having a reactive silicon group used in the present invention is (1) an olefinic compound having 1 to 6 carbon atoms such as ethylene, propylene, 1-butene, isobutylene and the like. It can be obtained by polymerizing as a main monomer, or (2) by homopolymerizing a diene compound such as butadiene or isoprene, or by copolymerizing the olefin and diene compounds and then hydrogenating them. However, isobutylene polymers and hydrogenated polybutadiene polymers are preferred because they can easily introduce functional groups at the terminals and increase the number of terminal functional groups whose molecular weight can be easily controlled. preferable.
[0022]
In addition, the saturated hydrocarbon polymer referred to in this specification is a concept that means a polymer that does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring.
[0023]
In the isobutylene polymer, all of the monomer units may be formed from isobutylene units, and the monomer units copolymerizable with isobutylene are preferably 30% or less of the isobutylene polymer, particularly preferably. You may contain in 10% or less of range.
[0024]
Examples of the monomer copolymerizable with isobutylene include olefins having 4 to 12 carbon atoms, vinyl ethers, aromatic vinyl compounds, vinyl silanes, and allyl silanes.
[0025]
The hydrogenated polybutadiene polymer and other saturated hydrocarbon polymers also contain other monomer units in addition to the main monomer unit as in the case of the isobutylene polymer. May be.
[0026]
In addition, the saturated hydrocarbon polymer used in the present invention contains a small amount of monomer units such as polyene compounds such as butadiene and isoprene, in which double bonds remain after polymerization, within the range in which the object of the present invention is achieved. Preferably, it may be contained within a range of 10% or less, further 5% or less, and particularly 1% or less.
[0027]
The saturated hydrocarbon polymer, preferably an isobutylene polymer or hydrogenated polybutadiene polymer, preferably has a number average molecular weight of about 500 to 30,000, particularly a liquid of about 1,000 to 15,000. -What has fluidity | liquidity is preferable from points, such as cheap handling.
[0028]
A method for producing the above-mentioned saturated hydrocarbon polymer having a reactive silicon group is described in detail in JP-A-1-170681.
[0029]
As the above-mentioned saturated hydrocarbon polymer (A), specifically, EPION (manufactured by Kaneka Chemical Industry Co., Ltd.) represented by the following formula (3) is preferably used.
[0030]
[Formula 4]

[0031]
(Wherein, x and y are 0 or an integer of 1 to 20, 1 ≦ x + y ≦ 20)
[0032]
Examples of the tackifier as component (B) include coumarone resins such as coumarone-indene resin, coumarone resin mixed with naphthene resin, phenol resin, rosin, etc .; pt-butylphenol-acetylene resin Such as phenol formaldehyde resin, xylene-phenol resin, xylene resin, terpene-phenol resin, terpene resin, etc. which improve not only tackiness but also adhesion and heat resistance, with low polymerization degree and low softening point (about 60-100 ° C.) Phenolic, terpene resins; synthetic polyterpene resins, aromatic hydrocarbon resins, aliphatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, hydrogenated hydrocarbon resins and other petroleum hydrocarbon resins; rosin and rosin penta Erythritol ester, rosin glycerol ester, hydrogenated Highly hydrogenated wood resin, methyl ester of hydrogenated rosin, triethylene glycol ester of hydrogenated rosin, pentaerythritol ester of hydrogenated rosin, polymerized rosin, glycerol ester of polymerized rosin, zinc resinate, cured Examples include, but are not limited to, rosin derivatives such as rosin; low molecular weight polystyrene, and other special preparations. Among these, terpene resins and petroleum hydrocarbon resins are particularly preferable because they have good compatibility and good adhesive properties. These tackifiers may be used alone or in combination of two or more.
[0033]
The polybutene as the component (C) includes hydrogenated polybutene, modified polybutene, etc. in addition to ordinary polybutene, and specifically, HV-300 (polybutene manufactured by Nippon Oil Corporation) is preferred. Used. As the liquid terpene polymer, YS resin PX-200 (manufactured by Yasuhara Chemical Co., Ltd.) or the like is used. The (C) component polybutene and liquid terpene polymer may be used alone or in combination.
[0034]
The blending ratio of (A), (B) and (C), which is an essential component of the pressure-sensitive adhesive composition of the present invention, is 20 to 800 parts by weight, preferably 30 with respect to 100 parts by weight of component (A). ~ 400 parts by weight and component (C) 20-1500 parts by weight, preferably 30-1000 parts by weight are used.
[0035]
In addition to the above-described essential components, the pressure-sensitive adhesive composition of the present invention contains a curing catalyst, a filler, a plasticizer, an adhesion-imparting agent, a stabilizer, a colorant and the like as necessary to adjust viscosity and physical properties can do.
[0036]
Examples of the curing catalyst include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate; organotin compounds such as dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, tin octylate and tin naphthenate: lead octylate Butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, triethylenediamine, guanidine, diphenyl Guanidine, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 1,8-diazabicycle (5.4.0) amine compounds such as undecene-7 (DBU) or salts thereof with carboxylic acids, etc .; low molecular weight polyamide resins obtained from excess polyamines and polybasic acids; excess polyamines and epoxy compounds Reaction products of the above and known silanol composite catalysts such as silane coupling agents having an amino group such as r-aminopropyltrimethoxysilane and N- (β-aminoethyl) aminopropylmethyldimethoxysilane. These catalysts may be used alone or in combination of two or more.
[0037]
The plasticizer is not particularly limited as long as it is a process oil or other hydrocarbon compatible with the polymer, and various known plasticizers can be used. For example, phthalic acid esters such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate and butyl phthalyl butyl glycolate; non-aromatic dibasic acid esters such as dioctyl adipate and dioctyl sebacate Esters of polyalkylene glycols such as diethylene glycol dibenzoate and triethylene glycol dibenzoate; phosphate esters such as tricresyl phosphate and tributyl phosphate; chlorinated paraffins; alkyl diphenyls; hydrocarbon oils such as partially hydrogenated terphenyls; Process oils; alkylbenzenes and the like.
[0038]
Examples of the filler include normal calcium carbonate, carbon black, clay, talc, titanium oxide, quicklime, kaolin, zeolite, diatomaceous earth, vinyl chloride paste range, glass balloon, vinylidene chloride resin balloon, acrylonitrile / methacrylonitrile resin balloon. Can be used alone or in combination.
[0039]
A silane coupling agent or the like is used as an adhesion-imparting agent, and a hindered phenol compound or a triazole compound is used as a stabilizer. Examples of the colorant include titanium white, carbon black, and bengara.
[0040]
The pressure-sensitive adhesive composition of the present invention can be a one-component type as required, or can be a two-component type as shown in Examples 6 to 8 described later.
[0041]
【Example】
The present invention will be described more specifically with reference to the following examples.
[0042]
(Examples 1-5 and Comparative Examples 1-5)
As shown in Table 1, as a saturated hydrocarbon polymer (A), a silyl-terminated polyisobutylene polymer (EPION EP505S manufactured by Kaneka Chemical Co., Ltd.) and a terpene resin (Yasuhara Chemical Co., Ltd.) as a tackifier (B) YS Resin TO-105) and various blended substances as the third component were blended in predetermined amounts, heated to 120 ° C., and the tackifier (B) was dissolved and mixed. This mixture was cooled to obtain a pressure-sensitive adhesive composition. In this pressure-sensitive adhesive composition, a nitrogen-containing basic group-containing silane compound (KBE-603, manufactured by Shin-Etsu Chemical Co., Ltd.) as an adhesion-imparting agent and a tin compound (No. 918, manufactured by Sansha Co., Ltd.) as a curing catalyst Was added to prepare an adhesive. The obtained pressure-sensitive adhesive was applied to a sheet having a thickness of 5 mm, cured and cured for one day under conditions of 50 ° C. and 85% RH, and the tackiness was confirmed by finger touch tack. The results are shown in Table 1.
[0043]
[Table 1]

[0044]
The amount of each compounding substance in Table 1 is shown in parts by weight, and (* 1 to * 8) are as follows.
* 1: Silyl-terminated polyisobutylene polymer (EPION EP505S manufactured by Kaneka Chemical Co., Ltd.)
* 2: Terpene resin (YS Resin TO-105 manufactured by Yasuhara Chemical Co., Ltd.)
* 3: Nippon Oil Co., Ltd. HV-300
* 4: YS Resin PX-200 manufactured by Yasuhara Chemical Co., Ltd.
* 5: Idemitsu Kosan Co., Ltd. PS-32
* 6: NP-24 manufactured by Idemitsu Kosan Co., Ltd.
* 7: Silane compound (KBE-603 manufactured by Shin-Etsu Chemical Co., Ltd.)
* 8: Tin compound (No. 918, Sansha Kikai Co., Ltd.)
[0045]
The evaluation of tackiness in Table 1 is as follows.
○: Strong tackiness, Δ: Weak tackiness, ×: No tackiness
[0046]
From the results shown in Table 1, when polybutene (Examples 1 to 4) and a liquid terpene polymer (Example 5) are blended as additive substances, the tackiness is extremely improved and exhibits strong tackiness. When process oil (paraffin type) (Comparative Example 1) and process oil (naphthene type) (Comparative Example 2) are blended, the tackiness is not improved so much but only weak tackiness is exhibited. When phthalate) (Comparative Example 3) and DOA (dioctyl adipate) (Comparative Example 4) were blended, no tackiness was expressed. Further, even when no additive was blended (Comparative Example 5), only weak adhesiveness was exhibited. From the above results, a highly tacky adhesive can be obtained by blending polybutene and / or liquid terpene polymer as a C component with respect to the saturated hydrocarbon polymer (A) and the tackifier (B). There was found.
[0047]
(Examples 6 to 8)
As shown in Table 2, a silyl-terminated polyisobutylene polymer (EPION EP505S manufactured by Kaneka Chemical Co., Ltd.) as a saturated hydrocarbon polymer (A), and a terpene resin (manufactured by Yasuhara Chemical Co., Ltd.) as a tackifier (B) YS resin TO-105) and polybutene (HV-300 manufactured by Nippon Oil Co., Ltd.) were mixed in predetermined amounts, heated to 120 ° C., and the tackifier (B) was dissolved and mixed. After cooling, the filler was stirred and mixed to form a main agent, and a predetermined amount of the curing agent was mixed. The main agent and the curing agent were mixed at a predetermined blending amount, cured and cured for one day under 50 ° C. condition, and the tackiness was confirmed by finger touch tack. As shown in Table 2, in any of the examples, the tackiness was extremely improved and the tackiness was strong.
[0048]
[Table 2]

[0049]
The amount of each compounding substance in Table 2 is shown in parts by weight, (* 1 to * 3, * 7 and * 8) are the same as in Table 1, and (* 9 to * 11) are as follows. . Also, the evaluation of adhesiveness is the same as in Table 1.
* 9: Surface treated calcium carbonate (Sealet 200 manufactured by Maruo Calcium Co., Ltd.)
* 10: Laurylamine (Farmin 20D manufactured by Kao Corporation)
* 11: Tin compound (Neostan U-28 manufactured by Nitto Kasei Co., Ltd.)
[0050]
【The invention's effect】
As described above, according to the present invention, (A) a saturated hydrocarbon system having a hydroxyl group or hydrolyzable group bonded to a silicon atom and having at least one silicon-containing group that can be crosslinked by forming a siloxane bond. By adding a specific substance to a polymer and a pressure-sensitive adhesive composition containing a (B) tackifier, it has excellent heat resistance, light resistance and weather resistance, and also has no deterioration in tack While maintaining the above, it is possible to obtain a pressure-sensitive adhesive composition having extremely strong adhesiveness.

Claims (2)

(A) having a hydroxyl group or hydrolyzable group bonded to a silicon atom, and having at least one silicon-containing group which can be crosslinked by forming a siloxane bond at the molecular chain terminal , the number average molecular weight is 500 to 30,000 A saturated hydrocarbon polymer,
(B) a tackifier, and (C) a polybutene and / or a liquid terpene polymer,
The (A) saturated hydrocarbon polymer has a liquid or fluidity,
A pressure-sensitive adhesive composition comprising 20 to 800 parts by weight of component (B) and 20 to 1500 parts by weight of component (C) with respect to 100 parts by weight of component (A) . (A) having a hydroxyl group or hydrolyzable group bonded to a silicon atom, and having at least one silicon-containing group which can be crosslinked by forming a siloxane bond at the molecular chain terminal , the number average molecular weight is 500 to 30,000 A saturated hydrocarbon polymer,
(B) a tackifier, and (C) a polybutene and / or a liquid terpene polymer,
A method for producing a pressure-sensitive adhesive composition containing
The (A) saturated hydrocarbon polymer has liquid or fluidity,
The pressure-sensitive adhesive composition is produced by blending 20 to 800 parts by weight of component (B) and 20 to 1500 parts by weight of component (C) with 100 parts by weight of component (A) , heating, and dissolving and mixing. A method for producing a pressure-sensitive adhesive composition.