JPH08157686A - Tackifier for styrene-conjugated diene-based block copolymer, its production and tacky agent composition - Google Patents
Tackifier for styrene-conjugated diene-based block copolymer, its production and tacky agent compositionInfo
- Publication number
- JPH08157686A JPH08157686A JP32363694A JP32363694A JPH08157686A JP H08157686 A JPH08157686 A JP H08157686A JP 32363694 A JP32363694 A JP 32363694A JP 32363694 A JP32363694 A JP 32363694A JP H08157686 A JPH08157686 A JP H08157686A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- hydrocarbon resin
- styrene
- tackifier
- weight
- 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
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、スチレン−共役ジエン
系ブロック共重合体用粘着付与剤、その製造方法および
粘着剤組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tackifier for styrene-conjugated diene block copolymer, a method for producing the same and a pressure-sensitive adhesive composition.
【０００２】[0002]
【従来の技術】従来より、スチレン−共役ジエン系ブロ
ック共重合体をベースポリマーとし、これに粘着付与剤
として、脂肪族系石油樹脂、芳香族系石油樹脂、テルペ
ン系樹脂、ロジン系樹脂等の炭化水素樹脂を加えた粘着
剤組成物が知られている。一般に、こうした粘着剤組成
物には、粘着三特性としてタック、接着力および保持力
が要求される。これら粘着三特性を満足させるために、
粘着付与剤の種類を変えたり、ベースポリマー、粘着付
与剤またはオイル等の配合比率の調整がなされている
が、一般的にタックと保持力とは相反する性能であり、
上記粘着剤組成物で粘着三特性をすべて満足するものは
知られていない。BACKGROUND OF THE INVENTION Conventionally, a styrene-conjugated diene block copolymer has been used as a base polymer, and an aliphatic petroleum resin, an aromatic petroleum resin, a terpene resin, a rosin resin or the like has been used as a tackifier for the base polymer. A pressure-sensitive adhesive composition containing a hydrocarbon resin is known. Generally, such a pressure-sensitive adhesive composition is required to have tack, adhesive strength and holding power as three adhesive characteristics. In order to satisfy these three adhesive properties,
Although the type of tackifier is changed or the blending ratio of the base polymer, tackifier or oil is adjusted, tack and holding power are generally contradictory properties,
There is no known adhesive composition that satisfies all three adhesive properties.
【０００３】また、粘着付与剤のなかには、色調や臭気
の点でも好ましくないものがある。こうした色調や臭気
の改善には、通常、粘着付与剤として炭化水素樹脂の水
素化物が用いられる。しかし、これら水素化樹脂は色調
や臭気を改善できるのみで、粘着三特性を満足するもの
ではない。Also, some tackifiers are not preferable in terms of color tone and odor. To improve such color tone and odor, a hydride of a hydrocarbon resin is usually used as a tackifier. However, these hydrogenated resins can only improve the color tone and odor and do not satisfy the three adhesive properties.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、タック、接
着力および保持力の粘着三特性に優れ、かつ色調や臭気
にも優れるスチレン−共役ジエン系ブロック共重合体用
粘着付与剤、その製造方法および粘着剤組成物を提供す
ることを目的とする。DISCLOSURE OF THE INVENTION The present invention provides a tackifier for styrene-conjugated diene block copolymer, which is excellent in tack, adhesive strength and holding power, and has excellent color tone and odor. It is an object to provide a method and an adhesive composition.
【０００５】[0005]
【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、スチレン−共役ジエン系ブロック共重合
体に用いる粘着付与剤について鋭意検討した。その結
果、比較的高い軟化点を有する芳香族系炭化水素樹脂の
微水素化物と比較的低い軟化点の非芳香族系炭化水素樹
脂を特定割合で用いることにより、前記目的を達成でき
ることを見出した。本発明はかかる新たな知見に基づい
て完成されたものである。Means for Solving the Problems In order to solve the above problems, the present inventors have made extensive studies on a tackifier used in a styrene-conjugated diene block copolymer. As a result, it has been found that the above-mentioned object can be achieved by using a micro hydride of an aromatic hydrocarbon resin having a relatively high softening point and a non-aromatic hydrocarbon resin having a relatively low softening point in a specific ratio. . The present invention has been completed based on this new finding.
【０００６】詳しくは、本発明は、粘着付与剤として用
いられる炭化水素樹脂のなかで、芳香族系炭化水素樹脂
はその芳香族性から極性が高く、スチレン−共役ジエン
系ブロック共重合体のスチレン相に相溶すること、また
非芳香族系炭化水素樹脂はその非芳香族性から極性が低
く、ブロック共重合体のゴム相（共役ジエン成分）に相
溶することから、これら炭化水素樹脂を併用することに
着目したものである。そして、芳香族系炭化水素樹脂と
して高軟化点物を用いることによりスチレン相を補強し
て保持力を維持するとともに、非芳香族系炭化水素樹脂
として低軟化点物を用いることによりタックを発現させ
ながら、芳香族系炭化水素樹脂を微水素化物とすること
で色調や臭気の問題も改善したものである。More specifically, the present invention relates to a hydrocarbon resin used as a tackifier, wherein an aromatic hydrocarbon resin has a high polarity due to its aromaticity, and is a styrene-conjugated diene block copolymer styrene. The non-aromatic hydrocarbon resin has low polarity due to its non-aromatic nature and is compatible with the rubber phase (conjugated diene component) of the block copolymer. It focuses on the combined use. And, by using a high softening point as an aromatic hydrocarbon resin to maintain the coercive force by reinforcing the styrene phase, and by using a low softening point as a non-aromatic hydrocarbon resin to develop tack. However, the problem of color tone and odor is improved by using aromatic hydrocarbon resin as a micro hydride.
【０００７】すなわち本発明は、（１）（ａ）オレフィ
ン性二重結合の全部と芳香環の２０％以下が水素化され
ている軟化点１４０〜１８０℃の芳香族系炭化水素樹脂
１０重量部、および（ｂ）軟化点７０〜１１０℃の非芳
香族系炭化水素樹脂５〜２００重量部を含有してなるス
チレン−共役ジエン系ブロック共重合体用粘着付与剤、
（２）軟化点１４０〜１８０℃の未水素化芳香族系炭化
水素樹脂１０重量部、および軟化点７０〜１１０℃の非
芳香族系炭化水素樹脂５〜２００重量部を混合した後、
該炭化水素樹脂混合物のオレフィン性二重結合の全部と
芳香環の３０％以下を水素化することを特徴とする前記
粘着付与剤の製造方法、ならびに（３）前記粘着付与剤
１５〜２１０重量部、スチレン−共役ジエン系ブロック
共重合体４〜２００重量部およびオイル４〜２００重量
部を含有してなる粘着剤組成物に関する。That is, the present invention relates to (1) 10 parts by weight of (a) an aromatic hydrocarbon resin having a softening point of 140 to 180 ° C. in which all of olefinic double bonds and 20% or less of aromatic rings are hydrogenated. And (b) a tackifier for a styrene-conjugated diene block copolymer, containing 5 to 200 parts by weight of a non-aromatic hydrocarbon resin having a softening point of 70 to 110 ° C.
(2) After mixing 10 parts by weight of an unhydrogenated aromatic hydrocarbon resin having a softening point of 140 to 180 ° C. and 5 to 200 parts by weight of a non-aromatic hydrocarbon resin having a softening point of 70 to 110 ° C.,
A method for producing the above tackifier, which comprises hydrogenating all of the olefinic double bonds and 30% or less of the aromatic ring of the hydrocarbon resin mixture, and (3) 15 to 210 parts by weight of the above tackifier. , A styrene-conjugated diene block copolymer 4 to 200 parts by weight and an oil 4 to 200 parts by weight.
【０００８】本発明では、スチレン−共役ジエン系ブロ
ック共重合体の粘着付与剤として、（ａ）オレフィン性
二重結合の全部と芳香環の２０％以下が水素化されてい
る軟化点１４０〜１８０℃の芳香族系炭化水素樹脂（以
下、樹脂（ａ）という）と、（ｂ）軟化点７０〜１１０
℃の非芳香族系炭化水素樹脂（以下、樹脂（ｂ）とい
う）を使用することを必須とする。In the present invention, as a tackifier for a styrene-conjugated diene block copolymer, (a) all of the olefinic double bonds and 20% or less of the aromatic ring are hydrogenated, and the softening point is 140 to 180. C. aromatic hydrocarbon resin (hereinafter referred to as resin (a)) at (.degree. C.), and (b) softening point 70 to 110.
It is essential to use a non-aromatic hydrocarbon resin (hereinafter referred to as resin (b)) having a temperature of 0 ° C.
【０００９】樹脂（ａ）の原料である芳香族系炭化水素
樹脂としては、たとえば、Ｃ９系炭化水素樹脂、クマロ
ン−インデン樹脂およびスチレン系重合体等があげられ
る。Examples of the aromatic hydrocarbon resin which is a raw material of the resin (a) include C9 hydrocarbon resin, coumarone-indene resin and styrene polymer.
【００１０】Ｃ９系炭化水素樹脂とは、ナフサのクラッ
キングにより得たＣ９留分（たとえば、スチレン、ビニ
ルトルエン、α−メチルスチレン、インデン類等）をカ
チオン重合して得られる石油樹脂をいう。The C9 hydrocarbon resin means a petroleum resin obtained by cationically polymerizing a C9 fraction (for example, styrene, vinyltoluene, α-methylstyrene, indenes, etc.) obtained by cracking naphtha.
【００１１】クマロン−インデン樹脂とは、一般にコー
クス炉ガス中の軽質留分であるソルベントナフサ（沸点
１５０〜２００℃）を原料油として、これに含まれるク
マロン、インデン、スチレン等を共重合させて得られる
熱可塑性樹脂であり、インデン、メチルインデン等のイ
ンデン類を構成モノマーとして５０重量％以上、好まし
くはかかるインデン類とクマロン、メチルクマロン等の
クマロン類を構成モノマーとして６０重量％以上含有す
るものをいう。また、必要によりスチレン、メチルスチ
レン等のスチレン類や、フェノール、アルキルフェノー
ル等のフェノール類等により変性または重合度を調整し
たものでもよい。The coumarone-indene resin is generally prepared by copolymerizing coumarone, indene, styrene and the like contained in solvent naphtha (boiling point 150 to 200 ° C.), which is a light fraction in coke oven gas, as a raw material oil. A thermoplastic resin to be obtained, which contains indenes such as indene and methylindene as constituent monomers in an amount of 50% by weight or more, and preferably contains indones and coumarones such as coumarone and methylcoumarone in an amount of 60% by weight or more. Say. Further, if necessary, those modified or adjusted in polymerization degree with styrenes such as styrene and methylstyrene, phenols such as phenol and alkylphenol may be used.
【００１２】また、スチレン系重合体とは、スチレン、
ビニルトルエン、α−メチルスチレン、ジメチルスチレ
ン等のピュアモノマーをカチオン重合等により重合して
得られるいわゆるピュアモノマー樹脂をいう。The styrene polymer is styrene,
It is a so-called pure monomer resin obtained by polymerizing a pure monomer such as vinyltoluene, α-methylstyrene, dimethylstyrene by cationic polymerization or the like.
【００１３】なお、樹脂（ａ）のなかでＣ９系炭化水素
樹脂やクマロン−インデン樹脂等は、水素化触媒の触媒
毒になる硫黄化合物等を高濃度に含有しているため、該
硫黄化合物等を可及的に低減しているものを使用しても
よい。かかる硫黄化合物等の除去は原料油の段階で行っ
てもよく、重合したのちに行ってもよい。除去方法とし
ては、酸またはアルカリによる抽出（洗浄）法、吸着剤
による吸着法、水素化等による分解法等があげられる。Among the resins (a), the C9 hydrocarbon resin, coumarone-indene resin and the like contain a high concentration of a sulfur compound which becomes a catalyst poison of the hydrogenation catalyst. You may use what has reduced as much as possible. The removal of such sulfur compounds and the like may be carried out at the stage of the feed oil or after the polymerization. Examples of the removal method include an extraction (washing) method with an acid or an alkali, an adsorption method with an adsorbent, a decomposition method with hydrogenation and the like.
【００１４】樹脂（ａ）は、前記芳香族系炭化水素樹脂
のオレフィン性二重結合の全部および芳香核の２０％以
下、好ましくは１０％以下を水素化してなるものであ
る。オレフィン性二重結合が残存していては、原料樹脂
である芳香族系炭化水素樹脂の脱臭が不十分であり、熱
安定性の点でも好ましくない。また、芳香核の水素化率
が２０％を越える場合には、スチレン−共役ジエン系ブ
ロック共重合体のスチレン相と相溶する割合が少なくな
り、保持力向上の効果が低下し、更には該ブロック共重
合体のゴム相へ相溶して粘着剤組成物のガラス転移点が
上がり、むしろタックが悪くなるため好ましくない。な
お、芳香核の水素化率は０％であってもよい。オレフィ
ン性二重結合の水素化は芳香核の水素化に比べて容易で
あるが、オレフィン性二重結合を完全に水素化できる条
件であれば、硫黄化合物等が水素化分解され臭気成分の
殆どは除去されるからである。The resin (a) is obtained by hydrogenating all of the olefinic double bonds of the aromatic hydrocarbon resin and 20% or less, preferably 10% or less of the aromatic nucleus. When the olefinic double bond remains, deodorization of the aromatic hydrocarbon resin as the raw material resin is insufficient, which is not preferable in terms of thermal stability. Further, when the hydrogenation rate of the aromatic nucleus exceeds 20%, the proportion of the styrene-conjugated diene block copolymer which is compatible with the styrene phase decreases, and the effect of improving the holding power decreases. It is not preferable because it is compatible with the rubber phase of the block copolymer to raise the glass transition point of the pressure-sensitive adhesive composition, which rather deteriorates tack. The hydrogenation rate of the aromatic nucleus may be 0%. Hydrogenation of olefinic double bonds is easier than hydrogenation of aromatic nuclei, but if the conditions are such that olefinic double bonds can be completely hydrogenated, sulfur compounds will be hydrolyzed and most of the odorous components will be decomposed. Is removed.
【００１５】樹脂（ａ）は、軟化点が１４０〜１８０℃
と比較的高いものを使用する。樹脂（ａ）の軟化点が１
４０℃未満の場合にはスチレン相の補強効果が低下し、
保持力が低下する。１８０℃を越える場合にはスチレン
相への相溶性が低下して、粘着剤組成物のガラス転移点
が上がり、タックが悪くなる。The resin (a) has a softening point of 140 to 180 ° C.
And use a relatively expensive one. The softening point of resin (a) is 1
When the temperature is lower than 40 ° C, the reinforcing effect of the styrene phase decreases,
Holding power decreases. If it exceeds 180 ° C., the compatibility with the styrene phase decreases, the glass transition point of the pressure-sensitive adhesive composition rises, and the tack becomes worse.
【００１６】なお、樹脂（ａ）の軟化点は原料である前
記芳香族系炭化水素樹脂と殆ど同じ値であるため、原料
である芳香族系炭化水素樹脂は同程度の軟化点（すなわ
ち１４０〜１８０℃程度）のものを使用すればよい。ま
た、樹脂（ａ）の数平均分子量は、原料である芳香族系
炭化水素樹脂の数平均分子量を前記水素化率となるよう
に水素化した場合の理論値と殆ど同じと考えればよい。
樹脂（ａ）の数平均分子量は、通常８００〜３０００、
好ましくは９００〜１６００である。Since the softening point of the resin (a) is almost the same as that of the aromatic hydrocarbon resin as a raw material, the aromatic hydrocarbon resin as a raw material has the same softening point (that is, 140 to What is about 180 ° C.) may be used. The number average molecular weight of the resin (a) may be considered to be almost the same as the theoretical value when the number average molecular weight of the aromatic hydrocarbon resin as the raw material is hydrogenated so as to have the above hydrogenation rate.
The number average molecular weight of the resin (a) is usually 800 to 3000,
It is preferably 900 to 1600.
【００１７】樹脂（ａ）の製造は、原料である前記芳香
族系炭化水素樹脂の水素化率が前記範囲内（オレフィン
性二重結合の全部および芳香核の２０％以下）となるよ
うに、水素化触媒の存在下に、条件を適宜に調整して水
素化反応を行う。The resin (a) is produced in such a manner that the hydrogenation rate of the aromatic hydrocarbon resin as a raw material is within the above range (the total of olefinic double bonds and the aromatic nucleus is 20% or less). The hydrogenation reaction is carried out in the presence of a hydrogenation catalyst by appropriately adjusting the conditions.
【００１８】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−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、
原料樹脂である芳香族系炭化水素樹脂脂の０．１〜３重
量％程度、好ましくは０．１〜１重量％である。０．１
重量％に満たない場合は水素化が進み難く、３重量％を
越える場合には水素化が進みすぎる傾向がある。As the hydrogenation catalyst, various kinds of metals such as nickel, palladium, platinum, cobalt, rhodium, ruthenium, molybdenum and the like or metal compounds such as oxides and sulfides thereof can be used. Such a hydrogenation catalyst may be used by supporting it on a carrier such as alumina, silica (diatomaceous earth), carbon or titania, which is porous and has a large surface area. In the present invention, among these catalysts, it is preferable to use the nickel-diatomaceous earth catalyst because it is easy to adjust the hydrogenation ratio within the above range and from the viewpoint of cost. The amount of catalyst used is
It is about 0.1 to 3% by weight, preferably 0.1 to 1% by weight, of the aromatic hydrocarbon resin fat as the raw material resin. 0.1
If it is less than 5% by weight, hydrogenation tends to be difficult to proceed, and if it exceeds 3% by weight, hydrogenation tends to proceed too much.
【００１９】水素化反応の条件は、水素化圧力は通常３
０〜３００Ｋｇ／ｃｍ2 程度の範囲、反応温度は通常１
５０〜３００℃程度の範囲で行う。好ましくは水素化圧
力は１００〜２００Ｋｇ／ｃｍ2 であり、反応温度は２
００〜２８０℃である。水素化圧力が３０Ｋｇ／ｃｍ2
に満たない場合または反応温度が１５０℃満たない場合
には水素化が進み難く、水素化圧力が３００Ｋｇ／ｃｍ
2 を越える場合または反応温度が３００℃を越える場合
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。前記水素化反応は芳香族系炭化水素樹脂を溶融し
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 hydrogenation reaction is usually carried out at a hydrogenation pressure of 3
The reaction temperature is usually 1 in the range of 0 to 300 kg / cm 2.
It is performed in the range of about 50 to 300 ° C. Preferably the hydrogenation pressure is 100-200 Kg / cm 2 and the reaction temperature is 2
It is 00-280 degreeC. Hydrogenation pressure is 30 Kg / cm 2
If the reaction temperature is less than 150 ° C or the reaction temperature is less than 150 ° C, hydrogenation is difficult to proceed, and the hydrogenation pressure is 300 Kg / cm.
If it exceeds 2 , or if the reaction temperature exceeds 300 ° C, decomposition tends to occur and the softening point tends to decrease. The reaction time is usually about 1 to 7 hours, preferably 2 to 7 hours. The hydrogenation reaction is performed in a state where the aromatic hydrocarbon resin is melted or dissolved in a solvent. As a solvent,
Cyclohexane, n-hexane, n-heptane, decalin and the like can be used.
【００２０】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。Regarding the amount of the catalyst used and the reaction time, the batch system was used as the reaction system, but a flow system (fixed bed system, fluidized bed system, etc.) may be used as the reaction system. it can.
【００２１】樹脂（ｂ）としては、たとえば、Ｃ５系炭
化水素樹脂、テルペン系樹脂等の脂肪族系または脂環肪
族系の非芳香族系炭化水素樹脂があげられる。Examples of the resin (b) include aliphatic or alicyclic aliphatic nonaromatic hydrocarbon resins such as C5 hydrocarbon resins and terpene resins.
【００２２】Ｃ５系炭化水素樹脂とは、ナフサのクラッ
キングにより得たＣ４〜Ｃ５留分（たとえば、ペンテ
ン、メチルブテン、ピペレリン、シクロペンタジエン、
ジシクロペンタジエン等）をカチオン重合して得られる
石油樹脂をいう。The C5 hydrocarbon resin is a C4 to C5 fraction obtained by cracking naphtha (for example, pentene, methylbutene, piperelin, cyclopentadiene,
Petroleum resin obtained by cationic polymerization of dicyclopentadiene and the like.
【００２３】テルペン系樹脂とは、α−ピネン、β−ピ
ネン、ジペンテン、リモネン等のテルペン類を重合させ
た樹脂をいう。The terpene resin means a resin obtained by polymerizing terpenes such as α-pinene, β-pinene, dipentene and limonene.
【００２４】また、樹脂（ｂ）には、前記Ｃ５系炭化水
素樹脂またはテルペン系樹脂中に、スチレン等の芳香族
モノマーを樹脂全量の２０重量％程度未満の割合で共重
合させたものや、前記Ｃ５系炭化水素樹脂やテルペン系
樹脂等の水素化物も含まれる。該水素化物は、色調、臭
気の点で好ましい。なお、水素化条件は、樹脂（ａ）の
製造条件と同様の条件を採用できる。The resin (b) is obtained by copolymerizing the above C5 hydrocarbon resin or terpene resin with an aromatic monomer such as styrene at a ratio of less than about 20% by weight of the total amount of the resin. Also included are hydrides such as the C5 hydrocarbon resins and terpene resins. The hydride is preferable in terms of color tone and odor. The hydrogenation conditions may be the same as the production conditions for the resin (a).
【００２５】さらには、樹脂（ｂ）として、前記芳香族
系炭化水素樹脂（たとえば、Ｃ９系炭化水素樹脂、クマ
ロン−インデン樹脂またはスチレン系共重合体）のオレ
フィン性二重結合の全部と芳香環の８０％以上を水素化
したものを使用することもできる。芳香環の水素化率が
８０％未満の場合には、もはや非芳香族系炭化水素樹脂
とはいえず、スチレン−共役ジエン系ブロック共重合体
のスチレン相に相溶して、スチレン相を可塑化し、保持
力が悪くなる。なお、芳香族系炭化水素樹脂の水素化
は、芳香環の水素化率が８０％以上となるように、樹脂
（ａ）の製造条件と同様の条件下で行えばよい。Further, as the resin (b), all of the olefinic double bonds and aromatic rings of the aromatic hydrocarbon resin (for example, C9 hydrocarbon resin, coumarone-indene resin or styrene copolymer) are used. It is also possible to use hydrogenated products of 80% or more of. When the hydrogenation rate of the aromatic ring is less than 80%, it can no longer be said to be a non-aromatic hydrocarbon resin and is compatible with the styrene phase of the styrene-conjugated diene block copolymer to plasticize the styrene phase. And the holding power deteriorates. The aromatic hydrocarbon resin may be hydrogenated under the same conditions as the resin (a) production conditions so that the hydrogenation rate of the aromatic ring is 80% or more.
【００２６】樹脂（ｂ）は、軟化点が７０〜１１０℃と
比較的低いものを使用する。樹脂（ｂ）の軟化点が７０
℃未満の場合には接着力、保持力の性能が低下する。１
１０℃を越える場合には十分なタックが得られない。樹
脂（ｂ）の数平均分子量は、組成により異なるため、適
宜に調製すればよいが、通常３００〜２０００、好まし
くは３５０〜１５００である。なお、樹脂（ａ）と同
様、樹脂（ｂ）が水素化物の場合も未水素化の樹脂と同
程度の軟化点、数平均分子量である。As the resin (b), one having a relatively low softening point of 70 to 110 ° C. is used. The softening point of resin (b) is 70
If the temperature is less than ℃, the adhesive strength and the holding power are deteriorated. 1
If it exceeds 10 ° C, sufficient tack cannot be obtained. Since the number average molecular weight of the resin (b) varies depending on the composition, it may be appropriately prepared, but is usually 300 to 2000, preferably 350 to 1500. Similar to the resin (a), when the resin (b) is a hydride, it has the same softening point and number average molecular weight as the unhydrogenated resin.
【００２７】本発明のスチレン−共役ジエン系ブロック
共重合体用粘着付与剤は、前記樹脂（ａ）１０重量部
と、樹脂（ｂ）５〜２００重量部、好ましく１０〜１０
０重量部を含有してなる。樹脂（ｂ）の使用量が５重量
部未満では、タックが十分でなく好ましくない。また樹
脂（ｂ）の使用量が２００重量部を越える場合には、保
持力は殆ど向上せず好ましくない。The tackifier for styrene-conjugated diene block copolymer of the present invention is 10 parts by weight of the resin (a) and 5 to 200 parts by weight of the resin (b), preferably 10 to 10 parts.
It contains 0 parts by weight. When the amount of the resin (b) used is less than 5 parts by weight, tack is not sufficient, which is not preferable. When the amount of the resin (b) used exceeds 200 parts by weight, the holding power is hardly improved, which is not preferable.
【００２８】得られた前記樹脂（ａ）と樹脂（ｂ）を含
有してなる本発明のスチレン−共役ジエン系ブロック共
重合体用粘着付与剤の、軟化点は、通常８０〜１５０℃
程度、好ましくは９０〜１３０℃である。The softening point of the obtained tackifier for a styrene-conjugated diene block copolymer of the present invention containing the resin (a) and the resin (b) is usually 80 to 150 ° C.
The degree is preferably 90 to 130 ° C.
【００２９】本発明のスチレン−共役ジエン系ブロック
共重合体用粘着付与剤は、前記樹脂（ａ）と樹脂（ｂ）
を混合することにより容易に調製できる。また、本発明
のスチレン−共役ジエン系ブロック共重合体用粘着付与
剤は、樹脂（ａ）の原料である軟化点１４０〜１８０℃
の未水素化芳香族系炭化水素樹脂１０重量部と、樹脂
（ｂ）である軟化点７０〜１１０℃の非芳香族系炭化水
素樹脂５〜２００重量部を混合した後、該炭化水素樹脂
混合物のオレフィン性二重結合の全部と芳香環の２０％
以下を水素化することによっても製造できる。この方法
によれば、樹脂（ｂ）として、Ｃ５系炭化水素樹脂やテ
ルペン系樹脂等を使用する場合に、水素化を一度に行う
ことができる点で有利である。なお、水素化の条件は、
炭化水素樹脂混合物の水素化率が前記範囲内（オレフィ
ン性二重結合の全部および芳香核の２０％以下）となる
ように、樹脂（ａ）の製造条件と同様の条件下で行えば
よい。The tackifier for styrene-conjugated diene block copolymer of the present invention comprises the resin (a) and the resin (b).
It can be easily prepared by mixing The tackifier for styrene-conjugated diene block copolymer of the present invention has a softening point of 140 to 180 ° C., which is a raw material of the resin (a).
10 parts by weight of the non-hydrogenated aromatic hydrocarbon resin of (4) is mixed with 5 to 200 parts by weight of the non-aromatic hydrocarbon resin having a softening point of 70 to 110 ° C., which is the resin (b), and then the hydrocarbon resin mixture. 20% of all olefinic double bonds and aromatic rings of
It can also be produced by hydrogenating the following. According to this method, when a C5 hydrocarbon resin, a terpene resin, or the like is used as the resin (b), hydrogenation can be performed at one time, which is advantageous. The hydrogenation conditions are as follows:
It may be carried out under the same conditions as the production conditions of the resin (a) so that the hydrogenation rate of the hydrocarbon resin mixture is within the above range (the total of olefinic double bonds and 20% or less of the aromatic nucleus).
【００３０】本発明の粘着剤組成物は、前記樹脂（ａ）
と樹脂（ｂ）を含有してなる本発明のスチレン−共役ジ
エン系ブロック共重合体用粘着付与剤１５〜２１０重量
部、スチレン−共役ジエン系ブロック共重合体４〜２０
０重量部およびオイル４〜２００重量部を含有してなる
ものである。The pressure-sensitive adhesive composition of the present invention comprises the resin (a)
15-210 parts by weight of a tackifier for styrene-conjugated diene block copolymer of the present invention, containing styrene-conjugated diene block copolymer 4-20
It contains 0 parts by weight and 4 to 200 parts by weight of oil.
【００３１】スチレン−共役ジエン系ブロック共重合体
が４重量部未満の場合には、保持力が不十分であり、２
００重量部を越える場合には得られる粘着剤組成物の溶
融粘度が高くなりいずれも好ましくない。また、オイル
が４重量部未満の場合には、粘着剤組成物の溶融粘度が
高くなり、２００重量部を越える場合には保持力が不十
分でいずれも好ましくない。When the amount of the styrene-conjugated diene block copolymer is less than 4 parts by weight, the coercive force is insufficient and 2
If it exceeds 100 parts by weight, the melt viscosity of the obtained pressure-sensitive adhesive composition becomes high, which is not preferable. Further, when the amount of oil is less than 4 parts by weight, the melt viscosity of the pressure-sensitive adhesive composition becomes high, and when it exceeds 200 parts by weight, the holding power is insufficient, which is not preferable.
【００３２】前記本発明のスチレン−共役ジエン系ブロ
ック共重合体とは、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、１０／９０〜５０／５０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
スチレン類（Ｓ）／ブダジエン（Ｂ）の重量比が、１０
／９０〜５０／５０の範囲にあるＳＢＳ型ブロック共重
合体、スチレン類（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
−共役ジエン系ブロック共重合体には、前記ブロック共
重合体の共役ジエン成分を水素化したものも含まれる。The styrene-conjugated diene-based block copolymer of the present invention is a copolymer of styrenes such as styrene and methylstyrene, and conjugated dienes such as butadiene and isoprene, which are appropriately selected according to the purpose of use. It is a polymerized block copolymer. Usually, the weight ratio of styrenes / conjugated dienes is from 10/90 to 50/50. As a preferred specific example of such a block copolymer, for example, the weight ratio of styrenes (S) / budadiene (B) is 10
SBS type block copolymer in the range of 90/50 to 50/50, SIS type block copolymer in which the weight ratio of styrene (S) / isoprene (I) is in the range of 10/90 to 30/70, etc. Can be given. Further, the styrene-conjugated diene-based block copolymer of the present invention also includes the block copolymer obtained by hydrogenating the conjugated diene component.
【００３３】また、オイルとしては、ナフテン系オイ
ル、パラフィン系オイルや、芳香族系オイル等の可塑化
オイルがあげられる。凝集力の低下が少ない点からすれ
ば、ナフテン系オイル、パラフィン系オイルが好まし
い。具体的には、ナフテン系プロセス油、パラフィン系
プロセス油、液状ポリブテン等があげられる。Examples of oils include naphthenic oils, paraffinic oils, and plasticizing oils such as aromatic oils. Naphthenic oils and paraffinic oils are preferable from the viewpoint of less reduction in cohesive force. Specific examples thereof include naphthene-based process oil, paraffin-based process oil, liquid polybutene, and the like.
【００３４】なお、本発明の粘着剤組成物には、さら
に、必要に応じて消泡剤、増粘剤、充填剤、酸化防止
剤、耐水化剤、造膜助剤等の添加剤を加えることができ
る。If necessary, the pressure-sensitive adhesive composition of the present invention may further contain additives such as defoaming agents, thickeners, fillers, antioxidants, water-proofing agents and film-forming aids. be able to.
【００３５】[0035]
【発明の効果】本発明によれば、タック、接着力および
保持力の粘着三特性に優れ、かつ色調や臭気にも優れる
スチレン−共役ジエン系ブロック共重合体用の粘着付与
剤を提供できる。また、本発明の製造方法によれば、本
発明の粘着付与剤を効率よく製造できる。こうして得ら
れる本発明の粘着付与剤を用いることに、上記特性を有
するスチレン−共役ジエン系ブロック共重合体を用いた
粘着剤組成物を提供することができる。かかる本発明の
粘着剤組成物は、各種粘着テープ、ラベル、自動車、弱
電部品の仮止剤、各種アッセンブリー用途等の各種用途
に使用できる。According to the present invention, it is possible to provide a tackifier for a styrene-conjugated diene block copolymer, which is excellent in tackiness, adhesiveness and holding power, and is excellent in color tone and odor. Further, according to the production method of the present invention, the tackifier of the present invention can be efficiently produced. By using the tackifier of the present invention thus obtained, it is possible to provide a pressure-sensitive adhesive composition using the styrene-conjugated diene block copolymer having the above properties. The pressure-sensitive adhesive composition of the present invention can be used in various applications such as various adhesive tapes, labels, automobiles, temporary fixing agents for light electric components, and various assembly applications.
【００３６】[0036]
【実施例】以下に実施例および比較例を挙げて本発明を
具体的に説明するが、本発明はこれら実施例のみに限定
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 specifically 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.
【００３７】実施例１ （１）樹脂（ａ）の製造 軟化点１５０℃のＣ９系炭化水素樹脂（「ネオポリマー
１５０」、日本石油（株）製）１００部とニッケル−ケ
イソウ土触媒（日揮化学（株）製、「Ｎ−１１３」）
０．４部をオートクレーブに仕込み、水素圧２００ｋｇ
／ｃｍ2 、反応温度２６０℃、反応時間５時間の条件で
撹拌下に、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を入れ、２００
℃、２０ｔｏｒｒまで徐々に昇温・減圧して溶媒を除去
し、数量平均分子量１４６５、軟化点１５０℃、芳香環
の水素化率１０％の水素化Ｃ９系炭化水素樹脂９８部を
得た。Example 1 (1) Production of Resin (a) 100 parts of a C9 hydrocarbon resin (“Neopolymer 150”, manufactured by Nippon Oil Co., Ltd.) having a softening point of 150 ° C. and a nickel-diatomaceous earth catalyst (JGC Corporation) ("N-113" manufactured by Co., Ltd.)
Charge 0.4 parts into an autoclave, hydrogen pressure 200 kg
/ Cm 2 , the reaction temperature was 260 ° C, and the reaction time was 5 hours, and the hydrogenation reaction was carried out under stirring. After the reaction was completed, the obtained resin was dissolved in 300 parts of cyclohexane and the catalyst was removed by filtration. After that, stirring blade, reflux condenser,
1 with thermometer, temperature controller and pressure indicator
Add the filtrate to a liter separable flask and
The solvent was removed by gradually raising the temperature to 20 torr and reducing the pressure to 20 torr to obtain 98 parts of a hydrogenated C9-based hydrocarbon resin having a number average molecular weight of 1465, a softening point of 150 ° C., and a hydrogenation rate of an aromatic ring of 10%.
【００３８】なお、水素化率は、原料樹脂及び得られた
水素化樹脂の 1Ｈ−ＮＭＲの７ｐｐｍ付近に現れる芳香
環のＨ−スペクトル面積から以下の式に基づき算出し
た。水素化率＝｛１−（水素化樹脂のスペクトル面積／
原料樹脂のスペクトル面積）｝×１００（％）。また、
軟化点は、ＪＩＳ Ｋ ２５３１の環球法による。The hydrogenation rate was calculated from the H-spectral area of the aromatic ring appearing in the vicinity of 7 ppm of 1 H-NMR of the raw material resin and the obtained hydrogenated resin based on the following formula. Hydrogenation rate = {1- (spectrum area of hydrogenated resin /
Spectral area of raw material resin)} × 100 (%). Also,
The softening point is according to the ring and ball method of JIS K 2531.
【００３９】（２）粘着付与剤の調製 上記（１）で得られた水素化Ｃ９系炭化水素樹脂（樹脂
（ａ））５０部と、樹脂（ｂ）として軟化点１００℃の
Ｃ５系炭化水素樹脂（「マルカレッツＴ１００Ａ」、丸
善石油（株）製）５０部を溶融混合して、軟化点１２５
℃の粘着付与剤を調製した。(2) Preparation of tackifier 50 parts of hydrogenated C9 hydrocarbon resin (resin (a)) obtained in the above (1) and C5 hydrocarbon having a softening point of 100 ° C. as resin (b) 50 parts of resin (“Marukalets T100A”, manufactured by Maruzen Sekiyu KK) is melt mixed to give a softening point of 125
A ° C tackifier was prepared.
【００４０】（３）粘着剤組成物の調製 ＳＩＳ型ブロック共重合体（「カリフレックスＴＲ１１
０７」、シェル化学（株）製）およびパラフィン系オイ
ル（「ＤＩプロセスＰＷ９０」、出光興産（株）製）を
溶融混合（前者：後者の重量比が３０：１８）してゴム
状物を調製した。このゴム状物９２部を、（２）で調製
した粘着付与剤１００部に、１８０℃まで加熱、撹拌し
ながら徐々に加え、粘着剤組成物を調製した。(3) Preparation of adhesive composition SIS type block copolymer ("Califlex TR11
07 ", Shell Chemical Co., Ltd.) and paraffin oil (" DI Process PW90 ", Idemitsu Kosan Co., Ltd.) are melt mixed (the weight ratio of the former to the latter is 30:18) to prepare a rubber-like material. did. 92 parts of this rubber-like material was gradually added to 100 parts of the tackifier prepared in (2) with heating to 180 ° C. with stirring to prepare a pressure-sensitive adhesive composition.
【００４１】実施例２〜４ 実施例１の（１）において、原料の種類を表１に示すよ
うに変えた他は、実施例１の（１）と同様にして表１に
示す水素化率の樹脂（ａ）を製造した。また、実施例１
の（２）において樹脂（ａ）もしくは樹脂（ｂ）の種
類、または樹脂（ａ）と樹脂（ｂ）の溶融混合量を表１
に示すように変えた他は、実施例１の（２）と同様にし
て粘着付与剤を調製した。調製した粘着付与剤の軟化点
を表１に示す。得られた粘着付与剤を用いて実施例１の
（３）と同様にして粘着剤組成物を調製した。Examples 2 to 4 Hydrogenation rates shown in Table 1 are the same as in Example 1 (1) except that the kind of raw material is changed as shown in Table 1 in Example 1 (1). Of resin (a) was produced. In addition, Example 1
In (2) of Table 1, the types of the resin (a) or the resin (b), or the melt-mixed amount of the resin (a) and the resin (b) are shown in Table 1.
A tackifier was prepared in the same manner as in (2) of Example 1 except that the change was made as shown in FIG. Table 1 shows the softening points of the prepared tackifiers. A pressure-sensitive adhesive composition was prepared in the same manner as in (3) of Example 1 using the obtained tackifier.
【００４２】実施例５ 実施例１の（１）において、原料としてＣ９系炭化水素
樹脂（「ネオポリマー１５０」、日本石油（株）製）１
０部とＣ５系炭化水素樹脂（「マルカレッツＴ１００
Ａ」、丸善石油（株）製）９０部を仕込み、触媒の使用
量を０．５部、反応温度を２６０℃に変えて水素化した
他は実施例１の（１）と同様にして表１に示す水素化率
の樹脂（ａ）を含む粘着付与剤を製造した。製造した粘
着付与剤の軟化点を表１に示す。得られた粘着付与剤を
用いて実施例１の（３）と同様にして粘着剤組成物を調
製した。Example 5 In (1) of Example 1, as a raw material, a C9 hydrocarbon resin (“Neopolymer 150”, manufactured by Nippon Oil Co., Ltd.) 1
0 parts and C5 hydrocarbon resin ("Marukaletz T100
A ”, manufactured by Maruzen Petroleum Co., Ltd., was charged, and the amount of the catalyst used was 0.5 part and the reaction temperature was changed to 260 ° C., and hydrogenation was performed in the same manner as in Example 1 (1). A tackifier containing the resin (a) having the hydrogenation rate shown in 1 was produced. Table 1 shows the softening points of the produced tackifiers. A pressure-sensitive adhesive composition was prepared in the same manner as in (3) of Example 1 using the obtained tackifier.
【００４３】[0043]
【表１】 [Table 1]
【００４４】表１中、樹脂（ａ）の＊１はＣ９系炭化水
素樹脂（「ネオポリマー１５０」、日本石油（株）製）
を表し、＊２はインデン樹脂（「ユニレジン７８０」、
日本石油（株）製）を表す。樹脂（ｂ）の＊３は、Ｃ５
系炭化水素樹脂（「マルカレッツＴ１００Ａ」、丸善石
油（株）製）を表し、＊４はＣ９系炭化水素樹脂（「ア
ルコンＰ９０」、芳香環の水素化率９０％、荒川化学工
業（株）製）を表す。In Table 1, * 1 of resin (a) is a C9 hydrocarbon resin ("Neopolymer 150", manufactured by Nippon Oil Co., Ltd.).
* 2 is indene resin (“Uniresin 780”,
Represents Nippon Oil Co., Ltd. * 3 of resin (b) is C5
-Based hydrocarbon resin (“Marukalets T100A”, manufactured by Maruzen Petroleum Co., Ltd.), * 4 is C9-based hydrocarbon resin (“Alcon P90”, aromatic ring hydrogenation rate 90%, manufactured by Arakawa Chemical Industry Co., Ltd.) ) Represents.
【００４５】比較例１ 粘着付与剤として、軟化点１２５℃のＣ９系炭化水素樹
脂（「アルコンＰ１２５」、芳香環の水素化率９０％、
荒川化学工業（株）製）を使用した他は実施例１の
（３）と同様にして粘着剤組成物を調製した。Comparative Example 1 As a tackifier, a C9 hydrocarbon resin having a softening point of 125 ° C. (“ALCON P125”, aromatic ring hydrogenation rate of 90%,
A pressure-sensitive adhesive composition was prepared in the same manner as in (3) of Example 1 except that Arakawa Chemical Industry Co., Ltd. was used.
【００４６】比較例２ 粘着付与剤として、軟化点１００℃のＣ５系炭化水素樹
脂（「マルカレッツＴ１００Ａ」、丸善石油（株）製）
を使用した他は実施例１の（３）と同様にして粘着剤組
成物を調製した。Comparative Example 2 As a tackifier, a C5 hydrocarbon resin having a softening point of 100 ° C. (“Marukalets T100A”, manufactured by Maruzen Petroleum Co., Ltd.)
A pressure-sensitive adhesive composition was prepared in the same manner as in (3) of Example 1 except that was used.
【００４７】比較例３ 粘着付与剤として、軟化点１５０℃のＣ９系炭化水素樹
脂（「ネオポリマー１５０」、芳香環の水素化率０％、
日本石油（株）製）を使用した他は実施例１の（３）と
同様にして粘着剤組成物を調製した。Comparative Example 3 As a tackifier, a C9 hydrocarbon resin having a softening point of 150 ° C. (“Neopolymer 150”, aromatic ring hydrogenation rate of 0%,
A pressure-sensitive adhesive composition was prepared in the same manner as in (3) of Example 1 except that Nippon Oil Co., Ltd. was used.
【００４８】比較例４〜１０ 実施例１の（２）において、樹脂（ａ）および樹脂
（ｂ）の代わりに、表２に示す芳香族性または軟化点の
異なる２種類の炭化水素樹脂を用いた他は、実施例１の
（２）と同様にして粘着付与剤を調製した。調製した粘
着付与剤の軟化点を表２に示す。得られた粘着付与剤を
用いて実施例１の（３）と同様にして粘着剤組成物を調
製した。なお、炭化水素樹脂は原料をそのままで、また
は原料のなかで芳香族系炭化水素樹脂は芳香環の水素化
率が表２に示すように水素化して使用した。Comparative Examples 4 to 10 In Example 1 (2), two kinds of hydrocarbon resins having different aromaticity or softening point shown in Table 2 were used instead of the resin (a) and the resin (b). A tackifier was prepared in the same manner as in (2) of Example 1 except that it was used. Table 2 shows the softening points of the prepared tackifiers. A pressure-sensitive adhesive composition was prepared in the same manner as in (3) of Example 1 using the obtained tackifier. The hydrocarbon resin was used as the raw material as it was, or the aromatic hydrocarbon resin was used after being hydrogenated as shown in Table 2 in which the aromatic ring hydrogenation rate was as shown in Table 2.
【００４９】[0049]
【表２】 [Table 2]
【００５０】表２中、＊１はＣ９系炭化水素樹脂（「ネ
オポリマー１５０」、日本石油（株）製）を表し、＊２
はインデン樹脂（「ユニレジン７８０」、日本石油
（株）製）を表し、＊３はＣ５系炭化水素樹脂（「マル
カレッツＴ１００Ａ」、丸善石油（株）製）を表し、＊
５はＣ９系炭化水素樹脂（「ネオポリマー１００」、日
本石油（株）製）を表し、＊６はＣ９系炭化水素樹脂
（「ハイレジンＲＳ−９」、日本石油（株）製）を表
す。In Table 2, * 1 represents a C9 hydrocarbon resin ("Neopolymer 150", manufactured by Nippon Oil Co., Ltd.), * 2
Represents an indene resin (“Uniresin 780”, manufactured by Nippon Oil Co., Ltd.), * 3 represents a C5 hydrocarbon resin (“Marukalets T100A”, manufactured by Maruzen Oil Co., Ltd.), *
5 represents a C9-based hydrocarbon resin (“Neopolymer 100”, manufactured by Nippon Oil Co., Ltd.), and * 6 represents a C9-based hydrocarbon resin (“HIRESIN RS-9”, manufactured by Nippon Oil Co., Ltd.).
【００５１】実施例および比較例で得られた粘着剤組成
物を以下の試験により評価した。評価結果を表３に示
す。The pressure-sensitive adhesive compositions obtained in Examples and Comparative Examples were evaluated by the following tests. The evaluation results are shown in Table 3.
【００５２】（タック）ＪＩＳ Ｚ ０２３７法に従
い、３０度の角度を有する斜面から、Ｎｏ．１４の鋼球
を転がし、水平面に置いた粘着面（粘着剤組成物をポリ
エチレンテレフタレートフィルム上に、塗布厚が７７μ
ｍとなるように溶融塗布したもの（以下、ＰＥＴフィル
ムという））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、２０℃である。(Tack) In accordance with JIS Z 0237 method, from the slope having an angle of 30 degrees, No. The steel ball No. 14 was rolled, and the pressure-sensitive adhesive surface placed on a horizontal surface (the pressure-sensitive adhesive composition was applied onto a polyethylene terephthalate film and the coating thickness was 77 μm).
The rolling distance (cm) of the steel ball was measured on the one (hereinafter referred to as PET film) melt-coated so as to have m. The shorter the distance (cm), the better the tack. The measurement atmosphere temperature is 20 ° C.
【００５３】（接着力）ＪＩＳ Ｚ ０２３７法に従
い、上記ＰＥＴ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
×１２５ｍｍで圧着後、２０℃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（ｋｇ
／２５ｍｍ）を測定した。(Adhesive Strength) According to JIS Z 0237 method, the PET film was adhered to a stainless steel plate as an adherend with an adhesion area of 25 mm using a 2 kg rubber roller.
After pressure-bonding at × 125 mm, it was left at 20 ° C. for 24 hours. After that, a 180 degree peel test was performed with Tensilon to obtain the adhesive strength (kg
/ 25 mm) was measured.
【００５４】（保持力）ＪＩＳ Ｚ ０２３７法に従
い、上記ＰＥＴ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、２０℃で２４時間放置した。その後クリープ
テスターで６０℃、２ｋｇ、１時間の条件で荷重をかけ
たときのＰＥＴフィルムとステンレス鋼板とのズレを測
定（ｍｍ）を測定した。ズレ（ｍｍ）が短いほど保持力
に優れる。(Holding power) According to JIS Z 0237 method, the PET film and the stainless steel plate were pressure-bonded with a bonding roller of 25 mm × 25 mm using a 2 kg rubber roller, and then left at 20 ° C. for 24 hours. After that, the displacement (mm) between the PET film and the stainless steel plate when a load was applied under the condition of 60 ° C., 2 kg, and 1 hour was measured with a creep tester. The shorter the deviation (mm), the better the holding power.
【００５５】（臭気）粘着剤組成物を溶融して調製する
際の臭気を以下の基準で評価した。 ○：ほとんど無臭。 △：やや臭気がある。 ×：臭気が激しい。(Odor) The odor when the pressure-sensitive adhesive composition was prepared by melting was evaluated according to the following criteria. ○: Almost odorless. Δ: There is a slight odor. X: The odor is severe.
【００５６】（色調）粘着付与剤を２００℃に溶融させ
たときの色調を、ガードナースタンダードカーにより目
視判定した。(Color Tone) The color tone when the tackifier was melted at 200 ° C. was visually judged by a Gardner standard car.
【００５７】[0057]
【表２】 [Table 2]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０９Ｊ 125/04 ＪＣＮ 145/02 ＪＤＦ 153/02 ＪＤＪ 157/02 ＬＭＪ 193/00 ＪＡＫ ─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C09J 125/04 JCN 145/02 JDF 153/02 JDJ 157/02 LMJ 193/00 JAK
Claims (6)
香環の２０％以下が水素化されている軟化点１４０〜１
８０℃の芳香族系炭化水素樹脂１０重量部、および
（ｂ）軟化点７０〜１１０℃の非芳香族系炭化水素樹脂
５〜２００重量部を含有してなるスチレン−共役ジエン
系ブロック共重合体用粘着付与剤。1. A softening point 140-1 in which (a) all olefinic double bonds and 20% or less of aromatic rings are hydrogenated.
A styrene-conjugated diene block copolymer containing 10 parts by weight of an aromatic hydrocarbon resin at 80 ° C. and (b) 5 to 200 parts by weight of a non-aromatic hydrocarbon resin having a softening point of 70 to 110 ° C. For tackifier.
素樹脂、クマロン−インデン樹脂およびスチレン系重合
体から選ばれる少なくとも１種である請求項１記載の粘
着付与剤。2. The tackifier according to claim 1, wherein the aromatic hydrocarbon resin is at least one selected from C9 hydrocarbon resins, coumarone-indene resins and styrene polymers.
水素樹脂、テルペン系樹脂およびこれらの水素化物から
選ばれる少なくとも１種である請求項１記載の粘着付与
剤。3. The tackifier according to claim 1, wherein the non-aromatic hydrocarbon resin is at least one selected from C5 hydrocarbon resins, terpene resins and hydrides thereof.
化水素樹脂のオレフィン性二重結合の全部と芳香環の８
０％以上を水素化したものである請求項１記載の粘着付
与剤。4. The non-aromatic hydrocarbon resin comprises all of the olefinic double bonds of the aromatic hydrocarbon resin and 8 of aromatic rings.
The tackifier according to claim 1, wherein 0% or more is hydrogenated.
族系炭化水素樹脂１０重量部、および（ｂ）軟化点７０
〜１１０℃の非芳香族系炭化水素樹脂５〜２００重量部
を混合した後、該炭化水素樹脂混合物のオレフィン性二
重結合の全部と芳香環の２０％以下を水素化することを
特徴とする請求項１記載の粘着付与剤の製造方法。5. 10 parts by weight of an unhydrogenated aromatic hydrocarbon resin having a softening point of 140 to 180 ° C., and (b) a softening point of 70.
After mixing 5 to 200 parts by weight of a non-aromatic hydrocarbon resin at ˜110 ° C., all the olefinic double bonds and 20% or less of the aromatic ring of the hydrocarbon resin mixture are hydrogenated. The method for producing the tackifier according to claim 1.
与剤１５〜２１０重量部、スチレン−共役ジエン系ブロ
ック共重合体４〜２００重量部およびオイル４〜２００
重量部を含有してなる粘着剤組成物。6. 15 to 210 parts by weight of the tackifier according to claim 1, 4 to 200 parts by weight of a styrene-conjugated diene block copolymer, and 4 to 200 of oil.
An adhesive composition containing parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32363694A JP3427912B2 (en) | 1994-11-30 | 1994-11-30 | Tackifier for styrene-conjugated diene-based block copolymer, method for producing the same, and pressure-sensitive adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32363694A JP3427912B2 (en) | 1994-11-30 | 1994-11-30 | Tackifier for styrene-conjugated diene-based block copolymer, method for producing the same, and pressure-sensitive adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08157686A true JPH08157686A (en) | 1996-06-18 |
| JP3427912B2 JP3427912B2 (en) | 2003-07-22 |
Family
ID=18156942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32363694A Expired - Fee Related JP3427912B2 (en) | 1994-11-30 | 1994-11-30 | Tackifier for styrene-conjugated diene-based block copolymer, method for producing the same, and pressure-sensitive adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3427912B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000096021A (en) * | 1998-09-25 | 2000-04-04 | Arakawa Chem Ind Co Ltd | Tackifying resin for delayed tack-type tack agent composition and delayed tack-type tack agent composition |
| JP2002038117A (en) * | 2000-07-31 | 2002-02-06 | Arakawa Chem Ind Co Ltd | Tackifying resin emulsion and aqueous adhesive mass/ adhesive composition |
| JP2002037975A (en) * | 2000-07-26 | 2002-02-06 | Arakawa Chem Ind Co Ltd | Modifier for styrene-based block copolymer and adhesive composition and sealant composition each containing the modifier |
| JP2010512428A (en) * | 2006-12-07 | 2010-04-22 | スリーエム イノベイティブ プロパティズ カンパニー | Block copolymer blend adhesive comprising a plurality of tackifiers |
| KR20140098688A (en) * | 2013-01-31 | 2014-08-08 | 닛토덴코 가부시키가이샤 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
-
1994
- 1994-11-30 JP JP32363694A patent/JP3427912B2/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000096021A (en) * | 1998-09-25 | 2000-04-04 | Arakawa Chem Ind Co Ltd | Tackifying resin for delayed tack-type tack agent composition and delayed tack-type tack agent composition |
| JP2002037975A (en) * | 2000-07-26 | 2002-02-06 | Arakawa Chem Ind Co Ltd | Modifier for styrene-based block copolymer and adhesive composition and sealant composition each containing the modifier |
| JP4507036B2 (en) * | 2000-07-26 | 2010-07-21 | 荒川化学工業株式会社 | A modifier for a styrene block copolymer, and a pressure-sensitive adhesive composition and a sealing material composition containing the modifier. |
| JP2002038117A (en) * | 2000-07-31 | 2002-02-06 | Arakawa Chem Ind Co Ltd | Tackifying resin emulsion and aqueous adhesive mass/ adhesive composition |
| JP2010512428A (en) * | 2006-12-07 | 2010-04-22 | スリーエム イノベイティブ プロパティズ カンパニー | Block copolymer blend adhesive comprising a plurality of tackifiers |
| US9458359B2 (en) | 2006-12-07 | 2016-10-04 | 3M Innovative Properties Company | Block copolymer blend adhesives with multiple tackifiers |
| KR20140098688A (en) * | 2013-01-31 | 2014-08-08 | 닛토덴코 가부시키가이샤 | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet |
| JP2015028130A (en) * | 2013-01-31 | 2015-02-12 | 日東電工株式会社 | Adhesive composition and adhesive sheet |
| JP2018053269A (en) * | 2013-01-31 | 2018-04-05 | 日東電工株式会社 | Adhesive composition and adhesive sheet |
| JP2020073703A (en) * | 2013-01-31 | 2020-05-14 | 日東電工株式会社 | Adhesive composition and adhesive sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3427912B2 (en) | 2003-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1299495B1 (en) | Adhesives with improved die-cutting performance | |
| US7288590B2 (en) | Adhesives with improved die-cutting performance | |
| US7906583B2 (en) | Radial block copolymers and adhesives based thereon with improved die-cutting performance | |
| EP0260001B1 (en) | Hydrogenated petroleum resins and their use in adhesives | |
| JP4674089B2 (en) | Method for producing hydrogenated petroleum resin | |
| JPH08157794A (en) | Tackifier for styrene-conjugated diene block copolymer and pressure-sensitive adhesive composition | |
| JP3427912B2 (en) | Tackifier for styrene-conjugated diene-based block copolymer, method for producing the same, and pressure-sensitive adhesive composition | |
| JP3453396B2 (en) | Hot melt adhesive composition | |
| JP3578179B2 (en) | Tackifier for styrene-conjugated diene block copolymer and pressure-sensitive adhesive composition thereof | |
| JP4507036B2 (en) | A modifier for a styrene block copolymer, and a pressure-sensitive adhesive composition and a sealing material composition containing the modifier. | |
| JPH03259981A (en) | Hot-melt adhesive composition | |
| JPH08325540A (en) | Tackifier for styrene-conjugated diene-based block copolymer and its tacky agent composition | |
| JPH01213380A (en) | Tacky agent composition | |
| JPH04351614A (en) | Liquid hydrogenated petroleum resin and hot-melt pressure-sensitive adhesive composition prepared therefrom | |
| WO2019146690A1 (en) | Hydrocarbon resin, hydride of hydrocarbon resin, and hot-melt adhesive composition using hydrocarbon resin and hydride of hydrocarbon resin | |
| JPS588432B2 (en) | Setuchiyakuzaisoseibutsu | |
| JPH08183941A (en) | Tackifier for ethylene-based copolymer and hot melt adhesive composition | |
| EP1905808B1 (en) | Adhesives with improved die-cutting performance | |
| JPH11335645A (en) | Tackiness imparting agent for hot melt sealing material and hot melt sealing material | |
| JPH0689313B2 (en) | Hot melt adhesive / adhesive composition | |
| JPH04309588A (en) | Pressure-sensitive adhesive or adhesive composition | |
| JPS614711A (en) | Low-softening point hydrocarbon polymer and its use | |
| JPH0254845B2 (en) | ||
| JPH09169966A (en) | Tackiness-providing resin for acrylic pressure-sensitive adhesive and acrylic pressure-sensitive adhesive composition | |
| JPH08183940A (en) | Tackifier for ethylene-based copolymer and hot melt adhesive composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |