JP2002037975A - Modifier for styrene-based block copolymer and adhesive composition and sealant composition each containing the modifier - Google Patents

Modifier for styrene-based block copolymer and adhesive composition and sealant composition each containing the modifier

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Publication number
JP2002037975A
JP2002037975A JP2000225275A JP2000225275A JP2002037975A JP 2002037975 A JP2002037975 A JP 2002037975A JP 2000225275 A JP2000225275 A JP 2000225275A JP 2000225275 A JP2000225275 A JP 2000225275A JP 2002037975 A JP2002037975 A JP 2002037975A
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JP
Japan
Prior art keywords
weight
block copolymer
parts
modifier
styrene
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.)
Granted
Application number
JP2000225275A
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Japanese (ja)
Other versions
JP4507036B2 (en
Inventor
Takenori Hayashi
威範 林
Takumi Okazaki
巧 岡崎
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Arakawa Chemical Industries Ltd
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Arakawa Chemical Industries Ltd
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Priority to JP2000225275A priority Critical patent/JP4507036B2/en
Publication of JP2002037975A publication Critical patent/JP2002037975A/en
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Publication of JP4507036B2 publication Critical patent/JP4507036B2/en
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  • Adhesives Or Adhesive Processes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Sealing Material Composition (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PROBLEM TO BE SOLVED: To obtain an inexpensive and easy-to-produce modifier for a styrene- based block copolymer capable of giving a composition good in color tone, high in thermal stability and weatherability and improved in heat-resistant creep. SOLUTION: This modifier for styrene-based block copolymers is a hydrogenated C9-based petroleum resin <=0.3 wt.% in olefin content, <=30% in aromatic ring hydrogenation percentage and >=100 deg.C in softening point obtained by hydrogenating a phenol-free C9-based petroleum resin. The 2nd objective adhesive composition is obtained by compounding (A) 100 pts.wt. of a styrene-based block copolymer with (B) 5-100 pts.wt. of the above modifier and (C) 20-300 pts.wt. of a tackifier. The 3rd objective sealant composition is obtained by compounding (A) 100 pts.wt. of a styrene-based block copolymer with (B) 5-100 pts.wt. of the above modifier, (C) 20-300 pts.wt. of a tackifier, and a plasticizer.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、スチレン系ブロッ
ク共重合体用改質剤ならびに該改質剤を添加した粘着剤
組成物およびシーリング材組成物に関する。The present invention relates to a modifier for a styrenic block copolymer, and a pressure-sensitive adhesive composition and a sealing material composition to which the modifier is added.

【０００２】[0002]

【従来の技術】従来、スチレン−ブタジエン−スチレン
ブロック共重合体（ＳＢＳ）やスチレン−イソプレン−
スチレンブロック共重合体（ＳＩＳ）、スチレン−エチ
レン−ブチレン−スチレンブロック共重合体（ＳＥＢ
Ｓ）、スチレン−エチレン−プロピレン−スチレンブロ
ック共重合体（ＳＥＰＳ）等のスチレン系ブロック共重
合体（ベースポリマー）に、タック、濡れ、柔軟性等を
与えるための粘着付与剤を加え、さらに可塑剤、その他
添加剤を加えた組成物が紙おむつ、生理用ナプキンなど
の衛生材料用途の粘着剤として、また、シーリング材等
として使用されている。2. Description of the Related Art Conventionally, styrene-butadiene-styrene block copolymer (SBS) and styrene-isoprene-
Styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEB)
S), a styrene-based block copolymer (base polymer) such as styrene-ethylene-propylene-styrene block copolymer (SEPS) and the like, a tackifier for imparting tack, wetness, flexibility and the like are added, and plasticization is further performed. A composition to which an agent and other additives are added has been used as an adhesive for sanitary materials such as disposable diapers and sanitary napkins, and as a sealing material.

【０００３】これらの粘着剤やシーリング材等の組成物
は一般的には、接着性、タック、保持力等のバランスが
良く、総合的な性能としては良好なものである。しかし
ながら、特に耐熱クリープ力、保持力が必要とされる用
途に関しては性能的に不十分であった。具体的には加熱
時における、粘・接着剤のはがれ、ずり落ち等が生じる
問題、また、シーリング材として使用した場合にも温水
との接触、太陽光による加熱等が原因となり、シール性
や組立物の強度が低下するという問題点があった。[0003] Compositions such as these pressure-sensitive adhesives and sealing materials generally have a good balance of adhesiveness, tackiness, holding power and the like, and have good overall performance. However, the performance was insufficient particularly for applications requiring heat creep force and holding force. Specifically, problems such as peeling and slipping off of the adhesive or adhesive during heating, and contact with warm water and heating by sunlight when used as a sealing material may cause problems such as sealability and assembly. There is a problem that the strength of the object is reduced.

【０００４】そのため、スチレン系ブロック共重合体を
ベースポリマーとする粘着剤、シーリング材等の耐熱ク
リープ力を向上させる方法として、粘着剤、シーリング
材等の組成物に軟化点の高い芳香族系オリゴマーを添加
するといった方法が知られている。具体的には軟化点１
００℃程度以上のＣ９系石油樹脂、Ｃ９系石油樹脂の低
水素化物、α−メチルスチレンオリゴマー、スチレンオ
リゴマー等のピュアモノマー樹脂、低分子量ポリスチレ
ン等を添加することにより、耐熱クリープ力向上を達成
することが可能である。[0004] Therefore, as a method for improving the heat-resistant creep force of pressure-sensitive adhesives and sealing materials using a styrenic block copolymer as a base polymer, aromatic oligomers having a high softening point have been added to compositions such as pressure-sensitive adhesives and sealing materials. Is known. Specifically, softening point 1
By adding a C9 petroleum resin having a temperature of about 00 ° C. or higher, a low hydride of the C9 petroleum resin, a pure monomer resin such as an α-methylstyrene oligomer or a styrene oligomer, a low molecular weight polystyrene, or the like, an improvement in heat creep resistance is achieved. It is possible.

【０００５】しかし、Ｃ９系石油樹脂を用いた場合に
は、樹脂そのものが、濃褐色であるため、得られる粘着
剤やシーリング材の外観が悪く、また臭気も強いといっ
た問題がある。従来のＣ９系石油樹脂の低水素化物を用
いた場合にも、樹脂中のフェノール類の影響で熱安定性
が悪いといった問題がある。また、ピュアモノマー樹脂
を用いた場合には、ピュアモノマー樹脂中の残存オレフ
ィンが耐候性を悪くする場合があり、さらにピュアモノ
マー樹脂は、純粋に精製したモノマーを使用するために
一般にコストが高いといった問題点を有する。低分子量
ポリスチレンを用いた場合には、低分子量ポリスチレン
の分子量が大きく、またその分子量分布も広いため、ベ
ースポリマーとの相溶性が悪く、粘着剤、シーリング材
等の組成物が濁ってしまうといった問題がある。However, when a C9 petroleum resin is used, since the resin itself is dark brown, there are problems in that the resulting adhesive and sealing material have a poor appearance and a strong odor. Even when a low hydride of a conventional C9 petroleum resin is used, there is a problem that thermal stability is poor due to the effect of phenols in the resin. Also, when a pure monomer resin is used, the residual olefin in the pure monomer resin may deteriorate the weather resistance, and the pure monomer resin is generally expensive because a pure monomer is used. Has problems. When low-molecular-weight polystyrene is used, the low-molecular-weight polystyrene has a large molecular weight and a broad molecular weight distribution, so that the compatibility with the base polymer is poor, and the composition such as an adhesive or a sealing material becomes cloudy. There is.

【０００６】[0006]

【発明が解決しようとする課題】本発明は、前述の問題
点をことごとく解決しうる新規なスチレン系ブロック共
重合体用改質剤およびその組成物を与えるものである。
すなわち、組成物の色調が良好であり、熱安定性、耐候
性に優れ、耐熱クリープ力を向上させる安価かつ製造容
易なスチレン系ブロック共重合体用改質剤を提供するも
のである。SUMMARY OF THE INVENTION The present invention provides a novel styrenic block copolymer modifier and a composition thereof which can solve all of the above-mentioned problems.
That is, the present invention provides an inexpensive and easy-to-manufacture modifier for a styrenic block copolymer, which has a good color tone of the composition, has excellent thermal stability and weather resistance, and improves the heat creep force.

【０００７】[0007]

【課題を解決するための手段】本発明者らは、前記課題
を解決すべく鋭意検討を重ねた結果、Ｃ９系石油留分を
フェノール類の不存在下に重合させて得られるＣ９系石
油樹脂を、限定された水素化率の範囲内に水素化するこ
とにより前記目的をことごとく達成しうる、水素化Ｃ９
系石油樹脂すなわち、スチレン系ブロック共重合体用改
質剤を見出すに至った。Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that a C9 petroleum resin obtained by polymerizing a C9 petroleum fraction in the absence of phenols. Can be achieved by hydrogenating C9 within a limited range of hydrogenation rate.
A petroleum-based petroleum resin, that is, a styrene-based block copolymer modifier has been found.

【０００８】すなわち本発明は、フェノール類を含有し
ないＣ９系石油樹脂を水素化することにより、オレフィ
ン含有率を０．３％以下かつ芳香環水素化率を３０％以
下とした、軟化点１００℃以上の水素化Ｃ９系石油樹脂
であることを特徴とするスチレン系ブロック共重合体用
改質剤；スチレン系ブロック共重合体（Ａ）１００重量
部に対して、該スチレン系ブロック共重合体用改質剤
（Ｂ）５〜１００重量部および粘着付与剤（Ｃ）２０〜
３００重量部を配合してなる粘着剤組成物；スチレン系
ブロック共重合体（Ａ）１００重量部に対して、該スチ
レン系ブロック共重合体用改質剤（Ｂ）５〜１００重量
部、粘着付与剤（Ｃ）２０〜３００重量部および可塑剤
（Ｄ）を０重量部を超えて２００重量部以下配合してな
る粘着剤組成物；スチレン系ブロック共重合体（Ａ）１
００重量部に対して、該スチレン系ブロック共重合体用
改質剤（Ｂ）５〜１００重量部および粘着付与剤（Ｃ）
２０〜３００重量部可塑剤を配合してなるシーリング材
組成物；スチレン系ブロック共重合体（Ａ）１００重量
部に対して、該スチレン系ブロック共重合体用改質剤
（Ｂ）５〜１００重量部、粘着付与剤（Ｃ）２０〜３０
０重量部および可塑剤（Ｄ）０重量部を超えて２００重
量部以下を配合してなるシーリング材組成物、に関す
る。That is, according to the present invention, a phenol-containing C9 petroleum resin is hydrogenated to reduce the olefin content to 0.3% or less and the aromatic ring hydrogenation rate to 30% or less. A styrene-based block copolymer modifier characterized by being a hydrogenated C9 petroleum resin described above; based on 100 parts by weight of the styrene-based block copolymer (A), Modifier (B) 5 to 100 parts by weight and tackifier (C) 20 to
A pressure-sensitive adhesive composition containing 300 parts by weight; 5 to 100 parts by weight of the styrene-based block copolymer modifier (B) per 100 parts by weight of the styrene-based block copolymer (A), Pressure-sensitive adhesive composition comprising 20 to 300 parts by weight of imparting agent (C) and 200 parts by weight or less of plasticizer (D) in an amount exceeding 0 parts by weight; styrene-based block copolymer (A) 1
5 to 100 parts by weight of the modifier (B) for the styrenic block copolymer and 100 parts by weight of the tackifier (C)
A sealing material composition containing 20 to 300 parts by weight of a plasticizer; 100 parts by weight of the styrene block copolymer (A) and 5 to 100 parts of the styrene block copolymer modifier (B) Parts by weight, tackifier (C) 20 to 30
A sealant composition comprising 0 parts by weight and 200 parts by weight or more of the plasticizer (D) in an amount of more than 0 part by weight.

【０００９】[0009]

【発明の実施の形態】以下、発明の詳細について説明す
る。本発明のスチレン系ブロック共重合体用改質剤
（Ｂ）は、フェノール類を含有しないＣ９系石油樹脂を
オレフィン含有率０．３％以下かつ芳香環水素化率３０
％以下となるように水素化した軟化点１００℃以上の水
素化Ｃ９系石油樹脂を用いるものである。DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below. The styrene-based block copolymer modifier (B) of the present invention is a phenol-free C9-based petroleum resin having an olefin content of 0.3% or less and an aromatic ring hydrogenation rate of 30.
% Hydrogenated C9 petroleum resin having a softening point of 100 ° C. or higher, which is hydrogenated so as to be not more than 100%.

【００１０】前記フェノール類を含有しないＣ９系石油
樹脂はＣ９系石油留分をフェノール類の不存在下で重合
させることにより得られる。重合方法としては特に制限
されず、ラジカル重合、カチオン重合、アニオン重合等
の公知の重合方法を採用できるが、反応制御が容易なこ
とからカチオン重合が好ましい。なお、カチオン重合を
する際の反応条件は、特に制限されず各種公知の反応条
件を採用することができる。The phenol-free C9 petroleum resin is obtained by polymerizing a C9 petroleum fraction in the absence of phenols. The polymerization method is not particularly limited, and known polymerization methods such as radical polymerization, cationic polymerization, and anionic polymerization can be employed. However, cationic polymerization is preferred because the reaction can be easily controlled. The reaction conditions for the cationic polymerization are not particularly limited, and various known reaction conditions can be employed.

【００１１】本発明で言う、フェノール類の不存在下と
は、重合触媒、重合停止剤等として重合反応系にフェノ
ール類を含有しないことを意味する。なお、ここでいう
フェノール類としてはフェノールおよびクレゾール、キ
シレノール、ｐ−tert―ブチルフェノール、ｐ−オクチ
ルフェノール、ノニルフェノール等のアルキル置換フェ
ノール類等の分子中にフェノール性水酸基を有する通常
炭素数６〜２０のものがあげられる。これらのフェノー
ル類は、重合触媒としては、例えば三弗化ホウ素−フェ
ノラート錯体のようなフェノール類錯体として用いられ
るのが一般的であり、一方、重合停止剤としては、フェ
ノール、クレゾール等をそのまま用いられるのが一般的
である。前記フェノール含有重合触媒や重合停止剤とし
てフェノール類を使用した場合は、得られた樹脂の加熱
安定性が悪くなり、好ましくない。本発明における好適
な重合触媒の具体例としては三弗化ホウ素、三弗化ホウ
素エチルエーテル錯体、三弗化ホウ素ブチルエーテル錯
体、三弗化ホウ素酢酸錯体、塩化アルミニウム、四塩化
チタン、四塩化スズ等のルイス酸、硫酸、りん酸、過塩
素酸等のプロトン酸等をあげることができる。工業的な
供給面を考慮すると、三弗化ホウ素、三弗化ホウ素エチ
ルエーテル錯体が好ましい。In the present invention, the absence of phenols means that the polymerization reaction system does not contain phenols as a polymerization catalyst, a polymerization terminator and the like. The phenols referred to here include phenol and cresol, xylenol, p-tert-butylphenol, p-octylphenol, alkyl-substituted phenols such as nonylphenol and the like having a phenolic hydroxyl group in the molecule and usually having 6 to 20 carbon atoms. Is raised. These phenols are generally used as a polymerization catalyst, for example, as a phenol complex such as boron trifluoride-phenolate complex, while as a polymerization terminator, phenol, cresol or the like is used as it is. Generally, it is done. When phenols are used as the phenol-containing polymerization catalyst or the polymerization terminator, the heat stability of the obtained resin deteriorates, which is not preferable. Specific examples of suitable polymerization catalysts in the present invention include boron trifluoride, boron trifluoride ethyl ether complex, boron trifluoride butyl ether complex, boron trifluoride acetic acid complex, aluminum chloride, titanium tetrachloride, tin tetrachloride and the like. And protic acids such as Lewis acid, sulfuric acid, phosphoric acid and perchloric acid. Considering industrial supply, boron trifluoride and boron trifluoride ethyl ether complex are preferred.

【００１２】また、Ｃ９系石油留分とは、ナフサのクラ
ッキングにより得られたものをいい、重合性モノマーと
して、例えばスチレン、ビニルトルエン、α−メチルス
チレン、インデン類、その他高沸点の化合物等を含有し
ている。一般的なＣ９系石油留分は、通常、ビニルトル
エン、インデンをそれぞれ３０〜４０重量％程度含有
し、残り２０〜４０重量％程度がスチレン、α−メチル
スチレン及びその他の成分からなる。本発明においては
上述のＣ９系石油留分を用いて製造したＣ９系石油樹脂
を特定の水素化率の範囲に水素化することで、本発明の
目的を十分達成しうる水素化樹脂を得ることが出来る
が、以下に述べる精製Ｃ９系石油留分を使用することに
より、更に、得られる水素化石油樹脂の耐候性を向上す
ることもできる。精製Ｃ９系石油留分とは、通常は上述
した一般的なＣ９系石油留分を蒸留することにより、Ｃ
９系石油留分中のインデン類や高沸点の化合物等を除去
し、重合性モノマー中のビニルトルエン含有量を５０重
量％以上、インデンの含有量を２５重量％以下としたも
のである。ビニルトルエン含有量は、好ましくは５５重
量％以上であり、インデンの含有量は好ましくは２０重
量％以下である。なお、ビニルトルエンの含有量が多
く、インデン成分が少なくなるほど耐候性が良好になる
が、ビニルトルエン成分が多くなり、インデン成分が少
なくなると軟化点が低下する傾向にある。得られる精製
Ｃ９系石油樹脂の軟化点が１００℃程度以上になるよ
う、本発明の範囲内で任意に調整して良い。通常、軟化
点が１２０℃の樹脂では、ビニルトルエンの含有量は５
０〜５５重量％程度、インデン含有量は２０重量％程度
である。なお、本発明の精製Ｃ９系石油留分を調製する
にあたってはビニルトルエン等各種成分を配合する方法
も採用できる。The C9 petroleum fraction refers to one obtained by cracking of naphtha. Examples of the polymerizable monomer include styrene, vinyltoluene, α-methylstyrene, indene, and other compounds having a high boiling point. Contains. A general C9 petroleum fraction generally contains about 30 to 40% by weight of vinyl toluene and about 40% by weight of indene, respectively, and the remaining about 20 to 40% by weight is composed of styrene, α-methylstyrene and other components. In the present invention, a hydrogenated resin capable of sufficiently achieving the object of the present invention is obtained by hydrogenating a C9 petroleum resin produced using the above-mentioned C9 petroleum fraction to a specific hydrogenation rate range. However, by using a refined C9 petroleum fraction described below, the weatherability of the resulting hydrogenated petroleum resin can be further improved. The refined C9 petroleum fraction is generally obtained by distilling the above-mentioned general C9 petroleum fraction to obtain a C9-based petroleum fraction.
The indene and high-boiling compounds in the ninth petroleum fraction are removed, and the content of vinyltoluene in the polymerizable monomer is 50% by weight or more and the content of indene is 25% by weight or less. The vinyl toluene content is preferably at least 55% by weight, and the indene content is preferably at most 20% by weight. The weather resistance becomes better as the content of vinyltoluene is higher and the indene component is lower, but the softening point tends to be lower when the vinyltoluene component is higher and the indene component is lower. The softening point of the obtained refined C9 petroleum resin may be arbitrarily adjusted within the range of the present invention so as to be about 100 ° C. or higher. Usually, for a resin having a softening point of 120 ° C., the content of vinyltoluene is 5
About 0 to 55% by weight, and the indene content is about 20% by weight. In preparing the refined C9 petroleum fraction of the present invention, a method of blending various components such as vinyltoluene can be adopted.

【００１３】このようにして得られたフェノール類を含
有しないＣ９系石油樹脂を、公知の方法により、オレフ
ィン含有率を０．３％以下かつ芳香環の水素化率が３０
％以下となるように、水素化触媒の存在下に、条件を適
宜調整して水素化を行なう。The phenol-free C9 petroleum resin thus obtained is prepared by a known method so that the olefin content is 0.3% or less and the aromatic ring hydrogenation rate is 30%.
% Or less in the presence of a hydrogenation catalyst by appropriately adjusting the conditions.

【００１４】水素化触媒としては、ニッケル、パラジウ
ム、白金、コバルト、ロジウム、ルテニウム、モリブデ
ン等の金属またはこれらの酸化物、硫化物等の金属化合
物等の各種のものを使用できる。かかる水素化触媒は多
孔質で表面積の大きなアルミナ、シリカ（ケイソウ
土）、カーボン、チタニア等の担体に担持して使用して
もよい。本発明ではこれら触媒の中でも、水素化率を前
記範囲内に調整し易いことや費用面からニッケル−シリ
カ（ケイソウ土）触媒を使用するのが好ましい。触媒の
使用量は特に限定されないが、原料樹脂であるＣ９系石
油樹脂の０．０１〜３．０重量％程度、好ましくは０．
１〜１．０重量％である。一般的にＣ９系石油樹脂に含
まれる硫黄不純物の量が増えると触媒量を多くしなけれ
ば水素化が進行しにくくなる傾向にあるため触媒量を多
くする必要がある。As the hydrogenation catalyst, various catalysts such as metals such as nickel, palladium, platinum, cobalt, rhodium, ruthenium and molybdenum and metal compounds such as oxides and sulfides thereof can be used. Such a hydrogenation catalyst may be supported on a porous carrier having a large surface area, such as alumina, silica (diatomaceous earth), carbon, or titania. In the present invention, among these catalysts, it is preferable to use a nickel-silica (diatomaceous earth) catalyst from the viewpoint of easy adjustment of the hydrogenation ratio within the above range and cost. The amount of the catalyst used is not particularly limited, but is preferably about 0.01 to 3.0% by weight, preferably 0.1% by weight of the C9 petroleum resin as the raw material resin.
1 to 1.0% by weight. In general, if the amount of sulfur impurities contained in the C9 petroleum resin increases, the hydrogenation tends to be difficult to proceed unless the amount of the catalyst is increased, so that the amount of the catalyst needs to be increased.

【００１５】水素化反応の条件は、特に限定されない。
一般的には、水素化圧力は通常３〜３０ＭＰａ程度の範
囲、反応温度は通常１５０〜３００℃程度の範囲で行
う。好ましくは水素化圧力は１０〜２０ＭＰａであり、
反応温度は２００〜２８０℃である。水素化圧力が３Ｍ
Ｐａに満たない場合または反応温度が１５０℃に満たな
い場合には水素化が進み難く、水素化圧力が３０ＭＰａ
を超える場合または反応温度が３００℃を超える場合に
は分解が起こり軟化点が低下する傾向がある。また反応
時間は通常１〜７時間程度、好ましくは２〜７時間であ
る。前記水素化反応はＣ９系石油樹脂を溶融して、また
は溶剤に溶解した状態で行う。溶剤としては、シクロヘ
キサン、ｎ−ヘキサン、ｎ−ヘプタン、デカリン等を使
用できる。The conditions for the hydrogenation reaction are not particularly limited.
Generally, the hydrogenation pressure is usually in the range of about 3 to 30 MPa, and the reaction temperature is usually in the range of about 150 to 300 ° C. Preferably the hydrogenation pressure is between 10 and 20 MPa,
The reaction temperature is 200-280 ° C. Hydrogenation pressure is 3M
If the pressure is less than Pa or the reaction temperature is less than 150 ° C., the hydrogenation is difficult to proceed, and the hydrogenation pressure is 30 MPa.
When the reaction temperature exceeds 300 ° C. or when the reaction temperature exceeds 300 ° C., decomposition occurs and the softening point tends to decrease. The reaction time is generally about 1 to 7 hours, preferably 2 to 7 hours. The hydrogenation reaction is carried out while melting the C9 petroleum resin or dissolving it in a solvent. As the solvent, cyclohexane, n-hexane, n-heptane, decalin and the like can be used.

【００１６】なお、触媒の使用量および反応時間につい
ては、反応形式として回分式を採用した場合について説
明したが、反応形式としては流通式（固定床式、流動床
式等）を採用することもできる。The use amount of the catalyst and the reaction time have been described in the case where a batch system is employed as the reaction system. However, a flow system (fixed bed system, fluidized bed system, etc.) may be employed as the reaction system. it can.

【００１７】このようにして得られた水素化Ｃ９系石油
樹脂の軟化点は通常１００℃以上、好ましくは１１５℃
以上である。軟化点が１００℃未満では、スチレン相の
補強効果は小さくなり、耐熱クリープ力の向上が起こら
ない。また得られた水素化Ｃ９系石油樹脂の数平均分子
量（ゲルパーミエーションクロマトグラフィー（ＧＰ
Ｃ）法によるポリスチレン換算値）は３００〜２０００
程度が好ましい。数平均分子量が３００より小さくなる
と軟化点が低くなるため、耐熱クリープ力が低下する傾
向がある。また、数平均分子量が２０００を超える場合
にはスチレン系ブロック共重合体との相溶性が劣ること
となり、目的とした性能が十分に発現せず、また組成物
が濁るおそれがある。The hydrogenated C9 petroleum resin thus obtained has a softening point of usually 100 ° C. or higher, preferably 115 ° C.
That is all. When the softening point is lower than 100 ° C., the effect of reinforcing the styrene phase is reduced, and the heat creep force is not improved. In addition, the number average molecular weight of the obtained hydrogenated C9 petroleum resin (gel permeation chromatography (GP
C) (polystyrene conversion value) is 300 to 2000.
The degree is preferred. When the number average molecular weight is less than 300, the softening point is lowered, and the heat creep force tends to decrease. When the number average molecular weight exceeds 2,000, the compatibility with the styrenic block copolymer becomes inferior, and the intended performance is not sufficiently exhibited, and the composition may become cloudy.

【００１８】水素化Ｃ９系石油樹脂をスチレン系ブロッ
ク共重合体用改質剤として用いるためには、オレフィン
含有率を０．３％以下かつ芳香環水素化率を３０％以下
にすることが必要である。オレフィン含有率が０．３％
を超える場合には得られるスチレン系ブロック共重合体
用改質剤の耐候性が低下するため好ましくない。また芳
香環の水素化率が３０％を超える場合には、耐熱クリー
プ力が低下するため好ましくない。オレフィン含有率は
水素化Ｃ９系石油樹脂のＮＭＲスペクトル測定により得
られる全プロトンのスペクトル面積に対する、５.０〜
６.５ｐｐｍに認められるオレフィン二重結合に由来す
るプロトンのスペクトル面積により算出できる。すなわ
ち、オレフィン含有率＝（５．０〜６．５ｐｐｍに認め
られるオレフィン二重結合に由来するプロトンのスペク
トル面積／樹脂の全プロトンのスペクトル面積の和）×
１００（％）で表される。芳香環水素化率は、Ｃ９系石
油樹脂及び得られた水素化Ｃ９系石油樹脂のＮＭＲスペ
クトル７ｐｐｍ付近に現れる芳香環由来のプロトンのス
ペクトルの面積から算出できる。すなわち、水素化率＝
｛１−（水素化Ｃ９系石油樹脂の芳香環由来スペクトル
面積／Ｃ９系石油樹脂の芳香環由来スペクトル面積）｝
×１００（％）により導き出せる。本発明のスチレン系
ブロック共重合体用改質剤（Ｂ）には、さらに必要に応
じて酸化防止剤、紫外線吸収剤等の添加剤を加えること
ができる。In order to use a hydrogenated C9 petroleum resin as a modifier for a styrenic block copolymer, it is necessary to make the olefin content 0.3% or less and the aromatic ring hydrogenation rate 30% or less. It is. 0.3% olefin content
It is not preferred that the styrene-based block copolymer has a weather resistance lower than the above. On the other hand, when the hydrogenation ratio of the aromatic ring exceeds 30%, the heat creep force decreases, which is not preferable. The olefin content is 5.0 to 5.0 with respect to the total proton spectrum area obtained by NMR spectrum measurement of the hydrogenated C9 petroleum resin.
It can be calculated from the spectral area of the proton derived from the olefin double bond observed at 6.5 ppm. That is, olefin content = (sum of spectral areas of protons derived from olefin double bond observed at 5.0 to 6.5 ppm / sum of spectral areas of all protons of resin) ×
It is represented by 100 (%). The aromatic ring hydrogenation rate can be calculated from the area of the aromatic ring-derived proton spectrum which appears around 7 ppm of the NMR spectrum of the C9 petroleum resin and the obtained hydrogenated C9 petroleum resin. That is, hydrogenation rate =
{1- (Spectral area derived from aromatic ring of hydrogenated C9 petroleum resin / Spectral area derived from aromatic ring of C9 petroleum resin)}
It can be derived from × 100 (%). The styrenic block copolymer modifier (B) of the present invention may further contain, if necessary, additives such as an antioxidant and an ultraviolet absorber.

【００１９】本発明の粘着剤組成物に用いられるスチレ
ン系ブロック共重合体（Ａ）とは、スチレン、メチルス
チレン等のスチレン類とブタジエン、イソプレン等の共
役ジエン類を、使用目的に応じて適宜に選択して共重合
したブロック共重合体である。通常、スチレン類／共役
ジエン類の重量比は、１０／９０〜５５／４５である。
このようなブロック共重合体の好ましい具体例として
は、たとえばスチレン（Ｓ）／ブタジエン（Ｂ）の重量
比が１０／９０〜５５／４５の範囲にあるＳＢＳ型ブロ
ック共重合体、スチレン（Ｓ）／イソプレン（Ｉ）の重
量比が１０／９０〜３０／７０の範囲にあるＳＩＳ型ブ
ロック共重合体等があげられる。また、本発明のスチレ
ン系ブロック共重合体としては、前記スチレン系ブロッ
ク共重合体の共役ジエン成分を水素化したものも含まれ
る。スチレン系ブロック共重合体の共役ジエン成分を水
素化したものの具体例としては、いわゆるＳＥＢＳ型ブ
ロック共重合体、ＳＥＰＳ型ブロック共重合体などがあ
げられる。またこれらの他にＳＢＳ、ＳＩＳ、ＳＥＢＳ
およびＳＥＰＳの変性物も使用できる。The styrenic block copolymer (A) used in the pressure-sensitive adhesive composition of the present invention may be a styrene such as styrene or methylstyrene and a conjugated diene such as butadiene or isoprene. Is a block copolymer selected and copolymerized. Usually, the weight ratio of styrenes / conjugated dienes is from 10/90 to 55/45.
Preferred specific examples of such a block copolymer include, for example, an SBS type block copolymer having a weight ratio of styrene (S) / butadiene (B) in the range of 10/90 to 55/45, and styrene (S). And SIS type block copolymers having a weight ratio of / isoprene (I) in the range of 10/90 to 30/70. Further, the styrene-based block copolymer of the present invention includes those obtained by hydrogenating a conjugated diene component of the styrene-based block copolymer. Specific examples of the styrene-based block copolymer obtained by hydrogenating the conjugated diene component include a so-called SEBS block copolymer and a SEPS block copolymer. In addition to these, SBS, SIS, SEBS
And modified SEPS.

【００２０】本発明に用いられる粘着付与剤（Ｃ）とし
ては特に限定されず、公知のものを使用することができ
る。具体的にはロジン系樹脂、石油系樹脂、テルペン系
樹脂等が挙げられる。ロジン系樹脂としてはガムロジ
ン、ウッドロジン、トール油ロジンといったロジン類、
これらロジン類を（無水）マレイン酸（無水マレイン酸
および／またはマレイン酸を表す。）やフマル酸、（メ
タ）アクリル酸（メタクリル酸および／またはアクリル
酸を表す。）等の不飽和脂肪酸やフェノールで変性した
変性ロジン類、前記ロジン類を水素化した水素化ロジン
や不均化ロジン、重合ロジンといったものがあげられる
（ロジン類、変性ロジン類、水素化ロジン、不均化ロジ
ン、重合ロジンなどを以後ロジン化合物という）。ま
た、これらロジン化合物をグリセリンやペンタエリスリ
トール、エチレングリコール等の各種アルコールと反応
させたロジンエステル類も使用することができる。石油
系樹脂としてはＣ５系石油留分から得られるＣ５系石油
樹脂、Ｃ９系石油留分から得られるＣ９系石油樹脂やジ
シクロペンタジエンを原料とするジシクロペンタジエン
系石油樹脂、クマロン・インデン系樹脂の他これらの水
素化物があげられる。また、テルペン系樹脂としてはテ
レピン油に含まれるα−ピネンやβ−ピネン、柑橘類の
果皮より得られるリモネン等を単独または数種をフリー
デル・クラフト触媒で重合させて得られるテルペン樹脂
の他、テルペンフェノール樹脂、芳香族モノマーと共重
合させた芳香族変性テルペン樹脂、前記各種テルペン樹
脂を水素化した水添テルペン樹脂等が上げられる。これ
ら粘着付与剤は単独で用いてもよく２種以上を併用して
もよい。これら粘着付与樹脂の中では、組成物の初期色
調、耐候性を考慮するのであれば、石油系樹脂の水素化
物が好ましい。The tackifier (C) used in the present invention is not particularly limited, and any known tackifier can be used. Specific examples include rosin-based resins, petroleum-based resins, terpene-based resins, and the like. Rosins such as gum rosin, wood rosin, tall oil rosin,
Unsaturated fatty acids such as maleic anhydride (representing maleic anhydride and / or maleic acid), fumaric acid, and (meth) acrylic acid (representing methacrylic acid and / or acrylic acid) and phenol are used as rosins. And modified rosins, hydrogenated rosins, disproportionated rosins, and polymerized rosins obtained by hydrogenating the rosins (rosins, modified rosins, hydrogenated rosins, disproportionated rosins, polymerized rosins, etc.). Is hereinafter referred to as a rosin compound). Also, rosin esters obtained by reacting these rosin compounds with various alcohols such as glycerin, pentaerythritol, and ethylene glycol can be used. Examples of the petroleum resin include C5 petroleum resin obtained from C5 petroleum fraction, C9 petroleum resin obtained from C9 petroleum fraction, dicyclopentadiene petroleum resin derived from dicyclopentadiene, and cumarone / indene resin. These hydrides are mentioned. Further, as the terpene resin, α-pinene and β-pinene contained in turpentine oil, limonene obtained from citrus peel, etc. alone or in addition to terpene resin obtained by polymerizing several kinds with Friedel-Crafts catalyst, Examples include terpene phenol resins, aromatic modified terpene resins copolymerized with aromatic monomers, and hydrogenated terpene resins obtained by hydrogenating the above various terpene resins. These tackifiers may be used alone or in combination of two or more. Among these tackifying resins, a hydride of a petroleum resin is preferable in consideration of the initial color tone and weather resistance of the composition.

【００２１】また、本発明の粘着剤組成物には必要に応
じて可塑剤（Ｄ）を使用することができる。可塑剤は、
粘着付与樹脂のみでは粘着剤組成物の可塑化が不充分な
場合に使用する。可塑剤（Ｄ）としては、たとえば、炭
化水素系可塑剤等があげられる。炭化水素系可塑剤の具
体例としては、流動パラフィン、ポリブテン、液状ポリ
ブタジエン等を例示できる。また、フタル酸エステル、
脂肪族二塩基酸エステル、グリコールエステル、りん酸
エステル、エポキシ系可塑剤等の各種公知の可塑剤があ
げられる。Further, the pressure-sensitive adhesive composition of the present invention may optionally contain a plasticizer (D). The plasticizer is
It is used when the pressure-sensitive adhesive composition alone does not sufficiently plasticize the pressure-sensitive adhesive composition. Examples of the plasticizer (D) include hydrocarbon plasticizers. Specific examples of the hydrocarbon plasticizer include liquid paraffin, polybutene, and liquid polybutadiene. Also, phthalates,
Various known plasticizers such as an aliphatic dibasic acid ester, a glycol ester, a phosphate ester, and an epoxy plasticizer are exemplified.

【００２２】本発明における粘着剤組成物の配合比は、
スチレン系ブロック共重合体（Ａ）１００重量部に対し
て、スチレン系ブロック共重合体用改質剤（Ｂ）５〜１
００重量部程度、粘着付与剤（Ｃ）２０〜３００重量部
程度、可塑剤（Ｄ）０重量部を超えて２００重量部以下
とするのが好ましく、さらに好ましくは、（Ａ）１００
重量部に対して、（Ｂ）５〜１００重量部程度、粘着付
与剤（Ｃ）５０〜２５０重量部程度および可塑剤（Ｄ）
５〜１５０重量部程度である。The mixing ratio of the pressure-sensitive adhesive composition in the present invention is as follows:
Styrene block copolymer (A) 100 parts by weight, styrene block copolymer modifier (B) 5-1
The amount is preferably about 00 parts by weight, about 20 to 300 parts by weight of the tackifier (C), and more than 0 part by weight and not more than 200 parts by weight of the plasticizer (D).
(B) about 5 to 100 parts by weight, tackifier (C) about 50 to 250 parts by weight, and plasticizer (D) based on parts by weight.
It is about 5 to 150 parts by weight.

【００２３】前記スチレン系ブロック共重合体用改質剤
（Ｂ）の配合量が、スチレン系ブロック共重合体（Ａ）
１００重量部に対して、５部未満では耐熱クリープ力向
上効果が十分ではなく、逆に１００部を超えて配合する
と、粘着剤組成物が硬くなり、タック、接着力が低下す
る傾向がある。The amount of the styrenic block copolymer modifier (B) to be blended with the styrenic block copolymer (A)
If the amount is less than 5 parts per 100 parts by weight, the effect of improving the heat creep resistance is not sufficient. If the amount is more than 100 parts, the pressure-sensitive adhesive composition tends to be hard, and the tack and the adhesive strength tend to be reduced.

【００２４】前記粘着付与剤（Ｃ）の配合量が、スチレ
ン系ブロック共重合体（Ａ）１００重量部に対して、２
０部未満ではタック、接着力が十分ではなく、逆に３０
０部を超えて配合すると、粘着剤組成物が柔らかくなる
ため、耐熱クリープ力が低下する傾向にあり、前記スチ
レン系ブロック共重合体用改質剤（Ｂ）の改質効果が発
揮されない可能性がある。The amount of the tackifier (C) is 2 parts per 100 parts by weight of the styrene block copolymer (A).
If it is less than 0 parts, tack and adhesive strength are not sufficient, and conversely 30
If the amount exceeds 0 parts, the pressure-sensitive adhesive composition becomes soft, so that the heat-resistant creep force tends to decrease, and the modifying effect of the styrene-based block copolymer modifier (B) may not be exhibited. There is.

【００２５】前記可塑剤（Ｄ）を用いる場合には配合量
が、スチレン系ブロック共重合体（Ａ）１００重量部に
対して、２００部を超えて配合すると、粘着剤組成物が
柔らかくなり、組成物の強度、耐熱クリープ力が低下す
る傾向がある。なお、可塑剤（Ｄ）を５部以上用いるこ
とで粘着剤組成物の溶融粘度を適度に保つことができる
ため好ましい。When the plasticizer (D) is used in an amount exceeding 200 parts by weight per 100 parts by weight of the styrene block copolymer (A), the pressure-sensitive adhesive composition becomes soft, The strength and the heat creep resistance of the composition tend to decrease. In addition, it is preferable to use 5 parts or more of the plasticizer (D) because the melt viscosity of the pressure-sensitive adhesive composition can be appropriately maintained.

【００２６】なお、本発明の粘着剤組成物には、さらに
必要に応じて、充填剤、酸化防止剤、紫外線吸収剤等の
添加剤を加えることができる。The pressure-sensitive adhesive composition of the present invention may further contain, if necessary, additives such as a filler, an antioxidant and an ultraviolet absorber.

【００２７】本発明のシーリング材組成物の配合比は、
スチレン系ブロック共重合体（Ａ）１００重量部に対し
て、スチレン系ブロック共重合体用改質剤（Ｂ）５〜１
００重量部程度、粘着付与剤（Ｃ）２０〜３００重量部
程度、可塑剤（Ｄ）０重量部を超えて２００重量部以下
とするのが好ましく、特に好ましい配合は、スチレン系
ブロック共重合体（Ａ）１００重量部に対して、スチレ
ン系ブロック共重合体用改質剤（Ｂ）５〜１００重量部
程度、粘着付与剤（Ｃ）５０〜２５０重量部程度および
可塑剤（Ｄ）５〜１５０重量部程度である。ここで、ク
リアシーリング材用途など特に耐候性、透明性を重視す
る用途においては、スチレン系ブロック共重合体（Ａ）
として、ＳＥＢＳ、ＳＥＰＳ等のスチレン−共役ジエン
系ブロック共重合体の水素化物やこれらの変性物が好ま
しく、さらに耐候性を重視する場合には粘着付与剤
（Ｃ）として水素化石油樹脂や水素化テルペン樹脂等を
用いることが好ましい。The compounding ratio of the sealing material composition of the present invention is as follows:
Styrene block copolymer (A) 100 parts by weight, styrene block copolymer modifier (B) 5-1
The amount is preferably about 00 parts by weight, about 20 to 300 parts by weight of the tackifier (C), and more than 0 part by weight and not more than 200 parts by weight of the plasticizer (D). Particularly preferred composition is a styrene-based block copolymer. (A) 100 parts by weight, modifier for styrene block copolymer (B) about 5 to 100 parts by weight, tackifier (C) about 50 to 250 parts by weight, and plasticizer (D) 5 to 5 parts by weight. It is about 150 parts by weight. Here, in applications where importance is placed on weather resistance and transparency, such as in the case of clear sealing materials, the styrene-based block copolymer (A)
Preferred are hydrogenated products of styrene-conjugated diene-based block copolymers such as SEBS and SEPS and modified products thereof. Further, when importance is placed on weather resistance, hydrogenated petroleum resins and hydrogenated It is preferable to use a terpene resin or the like.

【００２８】前記スチレン系ブロック共重合体用改質剤
（Ｂ）の配合量が、スチレン系ブロック共重合体（Ａ）
１００重量部に対して、５部未満では耐熱クリープ力向
上効果が十分ではなく、逆に１００部を超えて配合する
と、粘着剤組成物が硬くなり、タック、接着力が低下す
る傾向がある。The amount of the styrenic block copolymer modifier (B) to be blended with the styrenic block copolymer (A)
If the amount is less than 5 parts per 100 parts by weight, the effect of improving the heat creep resistance is not sufficient. If the amount is more than 100 parts, the pressure-sensitive adhesive composition tends to be hard, and the tack and the adhesive strength tend to be reduced.

【００２９】前記粘着付与剤（Ｃ）の配合量が、スチレ
ン系ブロック共重合体（Ａ）１００重量部に対して、２
０部未満ではタック、接着力が十分ではなく、逆に３０
０部を超えて配合すると、シーリング材組成物が柔らか
くなるため、耐熱クリープ力が低下する傾向にあり、前
記スチレン系ブロック共重合体用改質剤（Ｂ）の改質効
果が発揮されない可能性がある。The amount of the tackifier (C) is 2 parts by weight with respect to 100 parts by weight of the styrene-based block copolymer (A).
If it is less than 0 parts, tack and adhesive strength are not sufficient, and conversely 30
If the amount is more than 0 part, the sealing material composition becomes soft, so that the heat-resistant creep force tends to decrease, and the modifying effect of the styrene-based block copolymer modifier (B) may not be exhibited. There is.

【００３０】前記可塑剤（Ｄ）を用いる場合には配合量
が、スチレン系ブロック共重合体（Ａ）１００重量部に
対して、２００部を超えて配合すると、粘着剤組成物が
柔らかくなり、組成物の強度、耐熱クリープ力が低下す
る傾向がある。なお可塑剤を５部以上使用することによ
りシーリング材組成物の溶融粘度を適度に保つことがで
きるため好ましい。When the plasticizer (D) is used in an amount exceeding 200 parts by weight per 100 parts by weight of the styrene-based block copolymer (A), the pressure-sensitive adhesive composition becomes soft, The strength and the heat creep resistance of the composition tend to decrease. It is preferable to use 5 parts or more of a plasticizer because the melt viscosity of the sealing material composition can be kept at an appropriate level.

【００３１】なお、本発明のシーリング材組成物には、
さらに必要に応じて、充填剤、酸化防止剤、紫外線吸収
剤等の添加剤を加えることができる。The sealing material composition of the present invention includes:
Further, if necessary, additives such as a filler, an antioxidant, and an ultraviolet absorber can be added.

【００３２】[0032]

【発明の効果】本発明によれば、耐熱クリープ力を向上
させ、耐候性も良好なスチレン系ブロック共重合体用改
質剤および該改質剤を添加したスチレン系ブロック共重
合体をベースポリマーとしてなる耐熱クリープ力に優れ
た粘着剤、シーリング材等を提供できる。本発明のスチ
レン系ブロック共重合体用改質剤は、スチレン系ブロッ
ク共重合体中のスチレン類相の補強効果に優れることか
ら特に耐熱性を必要とされるスチレン系ブロック共重合
体をベースポリマーとする粘着剤、シーリング材等とし
て有用である。また、本発明のスチレン系ブロック共重
合体用改質剤は、初期色調、加熱安定性、耐候性等も良
好で、粘着剤、シーリング材等に少量添加し耐熱クリー
プ力を向上させる樹脂であるため、タック・接着力とい
った各種組成物独自の特性低下を抑え、その特性に加え
さらに耐熱クリープ力に優れた粘着剤、シーリング材等
を安価に提供できる。According to the present invention, a modifier for a styrenic block copolymer having improved heat creep force and good weatherability and a styrenic block copolymer to which the modifier is added are used as a base polymer. Pressure-sensitive adhesives, sealing materials, etc., which have excellent heat creep strength. The modifier for styrenic block copolymer of the present invention is a styrene-based block copolymer which is particularly required to have heat resistance because of its excellent styrene phase reinforcing effect in the styrenic block copolymer. It is useful as an adhesive, a sealing material, and the like. The styrenic block copolymer modifier of the present invention is a resin that has good initial color tone, heat stability, weather resistance, etc., and is added in a small amount to a pressure-sensitive adhesive, a sealing material, etc., to improve the heat creep resistance. Therefore, it is possible to suppress a decrease in the unique properties of various compositions such as tack and adhesive strength, and to provide an inexpensive pressure-sensitive adhesive, sealing material, and the like having excellent heat creep strength in addition to the properties.

【００３３】[0033]

【実施例】以下に、実施例および比較例をあげて本発明
を説明するが、本発明はこれら各例に制限されるもので
はない。なお、各例中、部は重量基準である。The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. In each example, parts are based on weight.

【００３４】実施例１ ナフサのクラッキングで得られた通常のＣ９系石油留分
（重合性モノマー組成：ビニルトルエン３７％、インデ
ン３５％、その他２８％）を蒸留することにより、高沸
点成分を減少させた精製Ｃ９系石油留分（重合性モノマ
ー組成：ビニルトルエン５０％、インデン２３％、その
他２７％）１００部を、反応温度２０℃で三弗化ホウ素
ガスを０．３部用いカチオン重合によって重合して特殊
Ｃ９系石油樹脂（軟化点１２０℃，数平均分子量８４
０）を得た。得られた特殊Ｃ９系石油樹脂１００部およ
びニッケルーシリカ触媒（「ＳＮＯ−７０９」、堺化学
工業（株）製）０．３部をオートクレーブに仕込み、水
素圧１９．６ＭＰａ、反応温度２６５℃、反応時間５時
間の条件下に、水素化反応を行った。反応終了後、得ら
れた樹脂をシクロヘキサン３００部に溶解し、ろ過によ
り触媒を除去した。その後、撹拌羽根、還流コンデンサ
ー、温度計、温度調節器及び圧力表示計の取り付けられ
た１リットル容のセパラブルフラスコにろ液および、酸
化防止剤（「イルガノックス１０１０」、チバ・スペシ
ャルティ・ケミカルズ（株）製）０．３５部を入れ、２
００℃、２.７ｋＰａまで徐々に昇温・減圧して溶媒を
除去し、数平均分子量８２０、軟化点１１７．０℃、オ
レフィン含有率０．０％、芳香環の水素化率０．０％、
色調６０Ｈの水素化Ｃ９系石油樹脂（改質剤ａ）９８部
を得た。得られたスチレン系ブロック共重合体用改質剤
（ａ）の物性を表１に示す。Example 1 A high-boiling component was reduced by distilling a normal C9 petroleum fraction (polymerizable monomer composition: vinyl toluene 37%, indene 35%, other 28%) obtained by cracking naphtha. 100 parts of the refined C9 petroleum fraction (polymerizable monomer composition: vinyl toluene 50%, indene 23%, other 27%) was subjected to cationic polymerization at a reaction temperature of 20 ° C. using 0.3 part of boron trifluoride gas. Polymerize to special C9 petroleum resin (softening point 120 ° C, number average molecular weight 84
0) was obtained. 100 parts of the obtained special C9 petroleum resin and 0.3 part of a nickel-silica catalyst (“SNO-709”, manufactured by Sakai Chemical Industry Co., Ltd.) were charged into an autoclave, hydrogen pressure was 19.6 MPa, reaction temperature was 265 ° C., The hydrogenation reaction was performed under the conditions of a reaction time of 5 hours. After completion of the reaction, the obtained resin was dissolved in 300 parts of cyclohexane, and the catalyst was removed by filtration. Thereafter, the filtrate and an antioxidant (“Irganox 1010”, Ciba Specialty Chemicals (Chemical Chemicals)) are placed in a 1-liter separable flask equipped with a stirring blade, a reflux condenser, a thermometer, a temperature controller and a pressure indicator. 0.35 parts)
The solvent was removed by gradually increasing the temperature and reducing the pressure to 00 kC and 2.7 kPa to remove the solvent. ,
98 parts of a hydrogenated C9 petroleum resin (modifier a) having a color tone of 60H were obtained. Table 1 shows the physical properties of the obtained styrenic block copolymer modifier (a).

【００３５】実施例２ 実施例１において原料樹脂を軟化点１２０℃（ビニルト
ルエン３８％、インデン３４％）に変えた他は、実施例
１と同様にして改質剤（ｂ）を製造した。得られた改質
剤（ｂ）の物性を表１に示す。Example 2 A modifier (b) was produced in the same manner as in Example 1 except that the raw material resin was changed to a softening point of 120 ° C. (vinyl toluene 38%, indene 34%). Table 1 shows the physical properties of the resulting modifier (b).

【００３６】実施例３ 実施例１において、反応条件を表１に示すように変えた
他は、実施例１と同様にして（ｃ）を製造した。得られ
た改質剤（ｃ）の物性を表１に示すExample 3 (c) was prepared in the same manner as in Example 1 except that the reaction conditions were changed as shown in Table 1. Table 1 shows the physical properties of the obtained modifier (c).

【００３７】実施例４ 実施例１において原料樹脂をネオポリマーＳ−１１０
（日本石油化学（株）製）に変えた他は、実施例１と同
様にして改質剤（ｄ）を製造した。得られた改質剤
（ｄ）の物性を表１に示す。Example 4 In Example 1, the starting resin was Neopolymer S-110.
A modifier (d) was produced in the same manner as in Example 1 except that the product was changed to (Nippon Petrochemical Co., Ltd.). Table 1 shows the physical properties of the resulting modifier (d).

【００３８】実施例５ 実施例１において原料樹脂をネオポリマーＳ−１００
（日本石油化学（株）製）に変えた他は、実施例１と同
様にして改質剤（ｅ）を製造した。得られた改質剤
（ｅ）の物性を表１に示す。Example 5 In Example 1, the starting resin was Neopolymer S-100.
A modifier (e) was produced in the same manner as in Example 1, except that the product was changed to Nippon Petrochemical Co., Ltd. Table 1 shows the physical properties of the obtained modifier (e).

【００３９】比較製造例１ 実施例１において、ナフサのクラッキングで得られた通
常のＣ９系石油留分（重合性モノマー組成：ビニルトル
エン３７％、インデン３５％、その他２８％）１００部
を反応温度２０℃で三弗化ホウ素フェノール錯体を０．
５部用いカチオン重合によってＣ９系石油樹脂（軟化点
１２０℃、数平均分子量８５０）を得た。該樹脂を用
い、水素化条件を表１に示すように変えた他は実施例１
と同様にして芳香環の水素化率５．５％の改質剤（ｆ）
を製造した。得られた改質剤（ｆ）の物性を表１に示
す。Comparative Production Example 1 In Example 1, 100 parts of a normal C9 petroleum fraction (polymerizable monomer composition: vinyl toluene 37%, indene 35%, other 28%) obtained by cracking of naphtha was reacted at a reaction temperature of 100%. The boron trifluoride phenol complex was added at 20 ° C.
Five parts were used to obtain a C9 petroleum resin (softening point: 120 ° C., number average molecular weight: 850) by cationic polymerization. Example 1 except that the resin was used and the hydrogenation conditions were changed as shown in Table 1.
Modifier (f) having an aromatic ring hydrogenation rate of 5.5% in the same manner as described above.
Was manufactured. Table 1 shows the physical properties of the obtained modifier (f).

【００４０】比較製造例２ 実施例１において、原料樹脂の軟化点を９０℃（数平均
分子量５８０）にした他は実施例１と同様にして改質剤
（ｇ）を製造した。得られた改質剤（ｇ）の物性を表１
に示す。Comparative Production Example 2 A modifier (g) was produced in the same manner as in Example 1 except that the softening point of the raw material resin was 90 ° C. (number average molecular weight: 580). Table 1 shows the physical properties of the obtained modifier (g).
Shown in

【００４１】比較製造例３ 実施例１において、反応条件を表１にように変えた他は
実施例１と同様にして、芳香環の水素化率が３９％の改
質剤（ｈ）を製造した。得られた改質剤（ｈ）の物性を
表１に示す。Comparative Production Example 3 In the same manner as in Example 1, except that the reaction conditions were changed as shown in Table 1, a modifier (h) having an aromatic ring hydrogenation rate of 39% was produced. did. Table 1 shows the physical properties of the resulting modifier (h).

【００４２】[0042]

【表１】 [Table 1]

【００４３】表１中の原料樹脂において、Ａは特殊Ｃ９
系石油樹脂（重合性モノマー組成：ビニルトルエン５０
％、インデン２３％、その他２７％、軟化点１２０℃、
数平均分子量８４０）を示し、ＢはＣ９系石油樹脂（重
合性モノマー組成：ビニルトルエン３８％、インデン３
４％、その他２８％、軟化点１２０℃、数平均分子量８
５０）、ＣはＣ９系石油樹脂（重合性モノマー組成：ビ
ニルトルエン３７％、インデン３５％、その他２８％、
軟化点１２０℃、数平均分子量８５０）、Ｄは特殊Ｃ９
系石油樹脂（重合性モノマー組成：ビニルトルエン６０
％、インデン９％、その他３１％、軟化点９０℃、数平
均分子量５８０）を示す。また、水素化反応において水
素化圧力は１９．６ＭＰａ、反応時間は５時間で全て同
じである。なお、改質剤（ｉ）としてスチレン系モノマ
ーと脂肪族系モノマーの共重合体樹脂であるＦＴＲ６１
００（軟化点１０２℃、三井化学（株）製）を用いた。In the raw material resins in Table 1, A represents special C9
Petroleum resin (polymerizable monomer composition: vinyl toluene 50
%, Indene 23%, other 27%, softening point 120 ° C,
B is a C9 petroleum resin (polymerizable monomer composition: vinyl toluene 38%, indene 3)
4%, other 28%, softening point 120 ° C, number average molecular weight 8
50), C is a C9 petroleum resin (polymerizable monomer composition: vinyl toluene 37%, indene 35%, other 28%,
Softening point 120 ° C, number average molecular weight 850), D is special C9
Petroleum resin (polymerizable monomer composition: vinyl toluene 60
%, Indene 9%, others 31%, softening point 90 ° C, number average molecular weight 580). In the hydrogenation reaction, the hydrogenation pressure is 19.6 MPa, and the reaction time is 5 hours, all being the same. Note that FTR61 which is a copolymer resin of a styrene monomer and an aliphatic monomer is used as the modifier (i).
00 (softening point: 102 ° C., manufactured by Mitsui Chemicals, Inc.) was used.

【００４４】表１中の原料樹脂中のフェノール分の検出
方法については以下の方法で行なった。Ｃ９系石油樹脂
中に含まれる、フェノール成分を、塩化鉄（III）を使
用する呈色法（船久保英一著 有機化合物確認法Ｉ 第
１章 第９〜１２頁 （株）養賢堂発行）によって検出
した。即ち、Ｃ９系石油樹脂０．３ｇをクロロホルムに
溶解させた後、塩化鉄（III）試薬を５滴加えた後の、
色調の変化の度合いで、フェノール類の有無を判定し
た。クロロホルム溶液の色調（淡黄色）に変化が無かっ
た場合、すなわちフェノールが存在しない場合を○とし
て、濃黄色に変化した場合、すなわちフェノールが存在
する場合を×とした。なお、塩化鉄（III）試薬は、無
水塩化鉄（III）１．０ｇをクロロホルム１００ｍｌに
溶解し、これにピリジンを８ｍｌ加え十分に混合した後
に、濾過した溶液を使用した。The method of detecting the phenol content in the raw material resin in Table 1 was carried out by the following method. Coloring method using iron (III) chloride for the phenol component contained in C9 petroleum resin (Eiichi Funakubo, Organic Compound Confirmation Method I, Chapter 1, pages 9-12 Published by Yokendo Co., Ltd.) ). That is, after dissolving 0.3 g of C9 petroleum resin in chloroform, and then adding 5 drops of iron (III) chloride reagent,
The presence or absence of phenols was determined based on the degree of color change. The case where there was no change in the color tone (light yellow) of the chloroform solution, that is, the case where phenol was not present, was evaluated as ○, and the case where it changed to dark yellow, that is, the case where phenol was present was evaluated as x. The iron (III) chloride reagent used was a solution obtained by dissolving 1.0 g of anhydrous iron (III) chloride in 100 ml of chloroform, adding 8 ml of pyridine to the solution, mixing well, and then filtering.

【００４５】実施例６ ＳＩＳ型ブロック共重合体（商品名「カリフレックスＴ
Ｒ１１０７」、シェル化学（株）製）５０部およびパラ
フィン系オイル（商品名「ＤＩプロセスＰＷ９０」、出
光興産（株）製）５０部を溶融混合してゴム状物を調製
した。このゴム状物１００部に、表１の改質剤（ａ）３
０部と粘着付与剤（商品名「アルコンＰ−１００」荒川
化学工業（株）製）１２０部を加え１８０℃で混練し、
ＳＩＳ系粘着剤組成物を調製した。Example 6 SIS type block copolymer (trade name “Califlex T”)
R1107 "(manufactured by Shell Chemical Co., Ltd.) and 50 parts of paraffinic oil (trade name" DI Process PW90 ", manufactured by Idemitsu Kosan Co., Ltd.) were melt-mixed to prepare a rubber-like material. To 100 parts of this rubber-like material, the modifier (a) 3 shown in Table 1 was added.
0 parts and 120 parts of a tackifier (trade name “ALCON P-100” manufactured by Arakawa Chemical Industries, Ltd.) are added and kneaded at 180 ° C.
An SIS-based pressure-sensitive adhesive composition was prepared.

【００４６】実施例７〜実施例１０および比較例１〜比
較例５ 改質剤を表２の様に代えた他は実施例６と同様にしてＳ
ＩＳ系粘着剤組成物を得た。Examples 7 to 10 and Comparative Examples 1 to 5 The same procedure as in Example 6 was carried out except that the modifier was changed as shown in Table 2.
An IS-based pressure-sensitive adhesive composition was obtained.

【００４７】実施例１１ ＳＢＳ型ブロック共重合体（商品名「タフプレンＡ」、
旭化成工業（株）製）５０部およびナフテン系オイル
（商品名「シェルフレックス３７１ＪＹ」、シェルジャ
パン（株）製）５０部を溶融混合してゴム状物を調製し
た。このゴム状物１００部に改質剤（ａ）３０部および
粘着付与剤（商品名「アルコンＭ−１００」荒川化学工
業（株）製）１２０部を加え１８０℃で混練し、ＳＢＳ
系粘着剤組成物を調製した。Example 11 An SBS type block copolymer (trade name “TUFPRENE A”,
50 parts of Asahi Kasei Kogyo Co., Ltd.) and 50 parts of a naphthenic oil (trade name "Shellflex 371JY", manufactured by Shell Japan K.K.) were melt-mixed to prepare a rubber-like material. 30 parts of the modifier (a) and 120 parts of a tackifier (trade name "Alcon M-100" manufactured by Arakawa Chemical Industries, Ltd.) were added to 100 parts of the rubber-like material, and kneaded at 180 ° C.
A pressure-sensitive adhesive composition was prepared.

【００４８】実施例１２〜実施例１５および比較例６〜
比較例１０ 改質剤を表３の様に代えた他は実施例１１と同様にして
ＳＢＳ系粘着剤組成物を得た。Examples 12 to 15 and Comparative Examples 6 to
Comparative Example 10 An SBS-based pressure-sensitive adhesive composition was obtained in the same manner as in Example 11, except that the modifier was changed as shown in Table 3.

【００４９】実施例１６ ＳＥＢＳ型ブロック共重合体（商品名「クレイトンＧ−
１６５２」シェル化学（株）製）、旭化成工業（株）
製）５０部およびポリブテン（商品名「ＨＶ−１０
０」、日本石油化学（株）製）５０部を溶融混合してゴ
ム状物を調製した。このゴム状物１００部に、改質剤ａ
３０部および粘着付与剤（商品名「アルコンＰ−１０
０」荒川化学工業（株）製）１２０部を加え１８０℃で
混練しＳＥＢＳ系粘着剤組成物を調製した。Example 16 SEBS type block copolymer (trade name "Clayton G-
1652 "Shell Chemical Co., Ltd.); Asahi Kasei Corporation
50 parts and polybutene (trade name "HV-10")
50 "(manufactured by Nippon Petrochemical Co., Ltd.) was melt-mixed to prepare a rubber-like material. A modifier a
30 parts and a tackifier (trade name "Alcon P-10")
0 "(Arakawa Chemical Industries, Ltd.) and kneaded at 180 ° C to prepare a SEBS-based pressure-sensitive adhesive composition.

【００５０】実施例１７〜実施例２０および比較例１１
〜比較例１５ 改質剤を表４の様に代えた他は実施例１６と同様にして
ＳＥＢＳ系粘着剤組成物を得た。Examples 17 to 20 and Comparative Example 11
Comparative Example 15 An SEBS-based pressure-sensitive adhesive composition was obtained in the same manner as in Example 16 except that the modifier was changed as shown in Table 4.

【００５１】ＳＩＳ系粘着剤組成物およびＳＢＳ系粘着
剤組成物、ＳＥＢＳ系粘着剤組成物の性能評価を以下の
試験により評価した。ＳＩＳ系粘着剤組成物の評価結果
を表２、ＳＢＳ系粘着剤組成物の評価結果を表３、ＳＥ
ＢＳ系粘着剤組成物の評価結果を表４に示す。なお、試
験片は粘着剤組成物１０部をトルエン１０部で溶解さ
せ、１５０μｍサイコロ型アプリケーターを用い、ポリ
エチレンテレフタレートフィルム上に塗布し（以下、粘
着フィルムという）作製した。The performance of the SIS-based pressure-sensitive adhesive composition, SBS-based pressure-sensitive adhesive composition, and SEBS-based pressure-sensitive adhesive composition was evaluated by the following tests. Table 2 shows the evaluation results of the SIS-based pressure-sensitive adhesive composition, and Table 3 shows the evaluation results of the SBS-based pressure-sensitive adhesive composition.
Table 4 shows the evaluation results of the BS-based pressure-sensitive adhesive composition. The test piece was prepared by dissolving 10 parts of the pressure-sensitive adhesive composition in 10 parts of toluene and applying the solution to a polyethylene terephthalate film using a 150 μm die-type applicator (hereinafter referred to as a pressure-sensitive adhesive film).

【００５２】接着力：ＪＩＳ Ｚ ０２３７法に従い、上
記粘着フィルムを、２ｋｇのゴムローラーを用いて、被
着体であるステンレス鋼板に接着面積２５ｍｍ×１２５
ｍｍで圧着後、２３℃で２４時間放置した。その後テン
シロンで１８０度剥離試験を行い接着力（Ｎ／ｃｍ）を
測定した。Adhesive strength: According to JIS Z 0237 method, the adhesive film was adhered to a stainless steel plate as an adherend using a 2 kg rubber roller with an adhesive area of 25 mm × 125.
mm, and left at 23 ° C. for 24 hours. Thereafter, a 180 ° peel test was performed with Tensilon to measure the adhesive strength (N / cm).

【００５３】タック：ＪＩＳ Ｚ ０２３７法に従い、３
０度の角度を有する斜面から、Ｎｏ．１４の鋼球を転が
し、水平面に置いた上記粘着フィルム面上で鋼球が転が
る距離（ｃｍ）を測定した。距離（ｃｍ）が短いほどタ
ックに優れる。測定雰囲気温度は、２３℃である。Tack: 3 according to JIS Z 0237 method
From the slope having an angle of 0 degree, Fourteen steel balls were rolled, and the rolling distance (cm) of the steel balls on the adhesive film surface placed on a horizontal surface was measured. The shorter the distance (cm), the better the tack. The measurement atmosphere temperature is 23 ° C.

【００５４】保持力：ＪＩＳ Ｚ ０２３７法に従い、上
記粘着フィルムとステンレス鋼板を２ｋｇのゴムローラ
ーを用いて、接着面積２５ｍｍ×２５ｍｍで圧着した
後、２３℃で２４時間放置した。その後クリープテスタ
ーで６０℃、０．５ｋｇ、１時間の条件で荷重をかけた
ときの粘着フィルムとステンレス鋼板とのズレ（ｃｍ）
を測定した。なお、表中「剥れる」とは測定終了時に試
験片が荷重により引き剥がされたことを意味する。ま
た、ズレ（ｃｍ）が短いほど保持力に優れる。Holding force: According to JIS Z 0237 method, the pressure-sensitive adhesive film and the stainless steel plate were pressed with an adhesive area of 25 mm × 25 mm using a 2 kg rubber roller, and then left at 23 ° C. for 24 hours. Thereafter, the gap between the pressure-sensitive adhesive film and the stainless steel plate when a load is applied with a creep tester at 60 ° C. and 0.5 kg for 1 hour (cm)
Was measured. In the table, “peeling” means that the test piece was peeled off by the load at the end of the measurement. Also, the shorter the deviation (cm), the better the holding power.

【００５５】耐候性：粘着剤組成物１０ｇを溶融後、内
径５５ｍｍの軟膏缶に入れ、放冷後、キセノンランプ
（Ｈｅｒａｅｕｓ社製、「ＳＵＮＴＥＳＴ」）を７２時
間連続照射し、色調を以下の基準により目視判定した。
◎：着色無し。○：ほとんど着色無し。△：僅かに着色
あり。×：著しく着色。Weather resistance: 10 g of the pressure-sensitive adhesive composition was melted, put in an ointment can having an inner diameter of 55 mm, allowed to cool, and then continuously irradiated with a xenon lamp (“SUNEST”, manufactured by Heraeus) for 72 hours. Was visually determined.
A: No coloring. ：: almost no coloring. Δ: Slightly colored. X: markedly colored.

【００５６】加熱着色性：粘着剤組成物５ｇを試験管に
入れ、１８０℃循風乾燥機中に静置し、１２時間後の粘
着剤組成物の色調を目視判定した。◎：１ガードナーカ
ラー未満。○：２ガードナーカラー未満。△：３ガード
ナーカラー未満。×：３ガードナーカラー以上。Heat coloring property: 5 g of the pressure-sensitive adhesive composition was placed in a test tube, and allowed to stand in a circulating air dryer at 180 ° C., and the color tone of the pressure-sensitive adhesive composition after 12 hours was visually determined. A: Less than 1 Gardner color. ：: Less than 2 Gardner colors. Δ: Less than 3 Gardner colors. X: 3 or more Gardner colors.

【００５７】[0057]

【表２】 [Table 2]

【００５８】[0058]

【表３】 [Table 3]

【００５９】[0059]

【表４】 [Table 4]

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｌ 101/00 Ｃ０８Ｌ 101/00 Ｃ０９Ｊ 153/02 Ｃ０９Ｊ 153/02 157/02 157/02 Ｃ０９Ｋ 3/10 Ｃ０９Ｋ 3/10 Ｚ Ｆターム(参考） 4H017 AA04 AB11 AB17 AC17 AD06 4J002 AE054 AF023 BA003 BA012 BA013 BB174 BK003 BL014 BP011 EH046 EH146 EW046 FD024 FD026 FD343 GJ01 GJ02 4J040 BA172 BA202 CA052 DA132 DK012 DK022 DM011 DN032 DN072 EL012 HB31 HB32 HB34 HD23 JB09 KA26 KA31 LA06 LA07 LA08 4J100 AU03P CA01 HA05 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C08L 101/00 C08L 101/00 C09J 153/02 C09J 153/02 157/02 157/02 C09K 3/10 C09K 3/10 ZF term (reference) 4H017 AA04 AB11 AB17 AC17 AD06 4J002 AE054 AF023 BA003 BA012 BA013 BB174 BK003 BL014 BP011 EH046 EH146 EW046 FD024 FD026 FD343 GJ01 GJ02 4J040 BA172 BA202 CA052 DA071 012012 KA31 LA06 LA07 LA08 4J100 AU03P CA01 HA05

Claims (10)

【特許請求の範囲】[Claims] 【請求項１】 フェノール類を含有しないＣ９系石油樹
脂を水素化することにより、オレフィン含有率を０．３
％以下かつ芳香環水素化率を３０％以下とした、軟化点
１００℃以上の水素化Ｃ９系石油樹脂であることを特徴
とするスチレン系ブロック共重合体用改質剤。1. An olefin content of 0.3% by hydrogenating a C9 petroleum resin containing no phenols.
%. A hydrogenated C9 petroleum resin having a softening point of 100 ° C. or higher and an aromatic ring hydrogenation ratio of 30% or lower. 【請求項２】 Ｃ９留分中のモノマー比がビニルトルエ
ンを５０重量％以上、インデンを２５重量％以下の割合
で含有してなることを特徴とする請求項１記載のスチレ
ン系ブロック共重合体用改質剤。2. The styrene block copolymer according to claim 1, wherein the monomer ratio in the C9 fraction is at least 50% by weight of vinyl toluene and at most 25% by weight of indene. Modifier. 【請求項３】 水素化Ｃ９系石油樹脂の色調が１ガード
ナー以下である請求項１または２記載のスチレン系ブロ
ック共重合体用改質剤。3. The styrenic block copolymer modifier according to claim 1, wherein the color tone of the hydrogenated C9 petroleum resin is 1 Gardner or less. 【請求項４】 軟化点が１１５℃以上である請求項１〜
３のいずれかに記載のスチレン系ブロック共重合体用改
質剤。4. The method according to claim 1, wherein the softening point is 115 ° C. or higher.
4. The modifier for a styrenic block copolymer according to any one of 3. 【請求項５】 スチレン系ブロック共重合体（Ａ）１０
０重量部に対して、請求項１〜４のいずれかに記載のス
チレン系ブロック共重合体用改質剤（Ｂ）５〜１００重
量部および粘着付与剤（Ｃ）２０〜３００重量部を配合
してなる粘着剤組成物。5. A styrenic block copolymer (A) 10
5 to 100 parts by weight of the modifier (B) for styrenic block copolymer according to any one of claims 1 to 4 and 20 to 300 parts by weight of a tackifier (C) based on 0 part by weight. An adhesive composition comprising: 【請求項６】 スチレン系ブロック共重合体（Ａ）１０
０重量部に対して、請求項１〜４のいずれかに記載のス
チレン系ブロック共重合体用改質剤（Ｂ）５〜１００重
量部、粘着付与剤（Ｃ）２０〜３００重量部および可塑
剤（Ｄ）を０重量部を超えて２００重量部以下配合して
なる粘着剤組成物。6. Styrene block copolymer (A) 10
The styrenic block copolymer modifier (B) of 5 to 100 parts by weight, the tackifier (C) of 20 to 300 parts by weight, and the plasticizer, based on 0 parts by weight. An adhesive composition comprising the agent (D) in an amount of more than 0 parts by weight and 200 parts by weight or less. 【請求項７】 スチレン系ブロック共重合体（Ａ）がＳ
ＢＳ、ＳＩＳ、ＳＥＢＳ、ＳＥＰＳおよびこれらの変性
物からなる群より選ばれる少なくとも一種である請求項
５または６記載の粘着剤組成物。7. The styrenic block copolymer (A) is S
The pressure-sensitive adhesive composition according to claim 5, which is at least one selected from the group consisting of BS, SIS, SEBS, SEPS, and modified products thereof. 【請求項８】 スチレン系ブロック共重合体（Ａ）１０
０重量部に対して、請求項１〜４のいずれかに記載のス
チレン系ブロック共重合体用改質剤（Ｂ）５〜１００重
量部および粘着付与剤（Ｃ）２０〜３００重量部可塑剤
を配合してなるシーリング材組成物。8. A styrenic block copolymer (A) 10
The modifier (B) for a styrenic block copolymer according to any one of claims 1 to 4, 5 to 100 parts by weight, and a tackifier (C) 20 to 300 parts by weight, based on 0 parts by weight. The sealing material composition which mix | blends. 【請求項９】 スチレン系ブロック共重合体（Ａ）１０
０重量部に対して、請求項１〜４のいずれかに記載のス
チレン系ブロック共重合体用改質剤（Ｂ）５〜１００重
量部、粘着付与剤（Ｃ）２０〜３００重量部および可塑
剤（Ｄ）０重量部を超えて２００重量部以下を配合して
なるシーリング材組成物。9. A styrenic block copolymer (A) 10
The styrenic block copolymer modifier (B) of 5 to 100 parts by weight, the tackifier (C) of 20 to 300 parts by weight, and the plasticizer, based on 0 parts by weight. A sealing material composition comprising more than 0 parts by weight and 200 parts by weight or less of the agent (D). 【請求項１０】 スチレン系ブロック共重合体（Ａ）が
ＳＥＢＳ、ＳＥＰＳ、またはこれらの変性物からなる群
より選ばれる少なくとも一種である請求項８または９記
載のシーリング材組成物。10. The sealing material composition according to claim 8, wherein the styrenic block copolymer (A) is at least one selected from the group consisting of SEBS, SEPS, and modified products thereof.
JP2000225275A 2000-07-26 2000-07-26 A modifier for a styrene block copolymer, and a pressure-sensitive adhesive composition and a sealing material composition containing the modifier. Expired - Lifetime JP4507036B2 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004162065A (en) * 2002-11-08 2004-06-10 Tesa Ag Adhesive and its use for an at least one-layer psa sheet strip which can be redetached without residue or destruction by extensive stretching substantially in the bonded surface
JP2006111758A (en) * 2004-10-15 2006-04-27 Kitagawa Ind Co Ltd Viscous gasket
KR20150143660A (en) * 2013-04-15 2015-12-23 테사 소시에타스 유로파에아 Self-adhesive compound and use thereof in an adhesive tape
CN114479726A (en) * 2020-10-26 2022-05-13 昆山太田新材料有限公司 Preparation method of high-strength hot melt adhesive special for bonding glass

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JPH08157686A (en) * 1994-11-30 1996-06-18 Arakawa Chem Ind Co Ltd Tackifier for styrene-conjugated diene-based block copolymer, its production and tacky agent composition
JPH08325338A (en) * 1995-03-31 1996-12-10 Arakawa Chem Ind Co Ltd Tackifying agent for ethylenic copolymer and its adhesive composition
JPH09268209A (en) * 1996-03-29 1997-10-14 Arakawa Chem Ind Co Ltd Phenol-modified 9c-based hydrogenated petroleum resin and its production
JP2000103820A (en) * 1998-09-30 2000-04-11 Arakawa Chem Ind Co Ltd Production of hydrogenated 9c petroleum resin and hydrogenated 9c petroleum resin obtained thereby

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Publication number Priority date Publication date Assignee Title
JPH08157686A (en) * 1994-11-30 1996-06-18 Arakawa Chem Ind Co Ltd Tackifier for styrene-conjugated diene-based block copolymer, its production and tacky agent composition
JPH08325338A (en) * 1995-03-31 1996-12-10 Arakawa Chem Ind Co Ltd Tackifying agent for ethylenic copolymer and its adhesive composition
JPH09268209A (en) * 1996-03-29 1997-10-14 Arakawa Chem Ind Co Ltd Phenol-modified 9c-based hydrogenated petroleum resin and its production
JP2000103820A (en) * 1998-09-30 2000-04-11 Arakawa Chem Ind Co Ltd Production of hydrogenated 9c petroleum resin and hydrogenated 9c petroleum resin obtained thereby

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004162065A (en) * 2002-11-08 2004-06-10 Tesa Ag Adhesive and its use for an at least one-layer psa sheet strip which can be redetached without residue or destruction by extensive stretching substantially in the bonded surface
JP2006111758A (en) * 2004-10-15 2006-04-27 Kitagawa Ind Co Ltd Viscous gasket
KR20150143660A (en) * 2013-04-15 2015-12-23 테사 소시에타스 유로파에아 Self-adhesive compound and use thereof in an adhesive tape
JP2016519710A (en) * 2013-04-15 2016-07-07 テーザ・ソシエタス・ヨーロピア Self-adhesive compounds and their use in adhesive tapes
US10717906B2 (en) 2013-04-15 2020-07-21 Tesa Se Self-adhesive compound and use thereof in an adhesive tape
KR102200965B1 (en) * 2013-04-15 2021-01-08 테사 소시에타스 유로파에아 Self-adhesive compound and use thereof in an adhesive tape
CN114479726A (en) * 2020-10-26 2022-05-13 昆山太田新材料有限公司 Preparation method of high-strength hot melt adhesive special for bonding glass

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