JPH09169966A - Tackiness-providing resin for acrylic pressure-sensitive adhesive and acrylic pressure-sensitive adhesive composition - Google Patents
Tackiness-providing resin for acrylic pressure-sensitive adhesive and acrylic pressure-sensitive adhesive compositionInfo
- Publication number
- JPH09169966A JPH09169966A JP28739696A JP28739696A JPH09169966A JP H09169966 A JPH09169966 A JP H09169966A JP 28739696 A JP28739696 A JP 28739696A JP 28739696 A JP28739696 A JP 28739696A JP H09169966 A JPH09169966 A JP H09169966A
- Authority
- JP
- Japan
- Prior art keywords
- sensitive adhesive
- resin
- acrylic pressure
- tackifying resin
- aromatic hydrocarbon
- 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
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- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はアクリル系感圧接着
剤用粘着付与樹脂及びアクリル系感圧接着剤組成物に関
する。詳しくは、本発明のアクリル系感圧接着剤組成物
は、包装、装飾、ラベル（たとえば、フイルムラベ
ル）、粘接着テープ、両面接着テープ等に利用できる。TECHNICAL FIELD The present invention relates to a tackifying resin for an acrylic pressure-sensitive adhesive and an acrylic pressure-sensitive adhesive composition. Specifically, the acrylic pressure-sensitive adhesive composition of the present invention can be used for packaging, decoration, labels (for example, film labels), adhesive tapes, double-sided adhesive tapes and the like.
【０００２】[0002]
【従来の技術】アクリル系重合体を主成分とするアクリ
ル系感圧接着剤は、無色透明で耐老化性に優れることか
ら広く使用されている。またアクリル系感圧接着剤に
は、各種用途に応じた接着力、保持力、タック等の粘着
特性を付与するために粘着付与樹脂が配合されている。2. Description of the Related Art Acrylic pressure-sensitive adhesives containing an acrylic polymer as a main component are widely used because they are colorless and transparent and have excellent aging resistance. Further, the acrylic pressure-sensitive adhesive contains a tackifying resin for imparting adhesive properties such as adhesive strength, holding power and tack according to various uses.
【０００３】しかし、アクリル系感圧接着剤の粘着付与
樹脂として知られているロジン系樹脂、テルペン系樹脂
や石油樹脂等は一般に色調が悪く、食品包装用や衛生材
料用等の色調を重視する分野等においては使用し難い。
一方、水素化ロジン系樹脂（たとえば、無色化したロジ
ン）等は色調には優れるが、保持力、タック、耐光性、
耐候性が十分でなく、また非常にコストが高いため実用
的でない。また、水素化石油樹脂等は色調に優れ比較的
安価であるが、ベースポリマーであるアクリル系重合体
との相溶性が悪く、接着性やタックも悪いため実用化さ
れていない。However, rosin-based resins, terpene-based resins, petroleum resins, etc., which are known as tackifying resins for acrylic pressure-sensitive adhesives, generally have poor color tones, and importance is attached to color tones for food packaging and sanitary materials. It is difficult to use in the field.
On the other hand, hydrogenated rosin-based resins (for example, colorless rosin) and the like have excellent color tone, but retain power, tack, light resistance,
It is not practical because the weather resistance is not sufficient and the cost is very high. Further, hydrogenated petroleum resins and the like have excellent color tone and are relatively inexpensive, but they have not been put into practical use because they have poor compatibility with the acrylic polymer as the base polymer and poor adhesion and tack.
【０００４】また、アクリル系重合体との相溶性が良
く、接着性を向上したアクリル系感圧接着剤の粘着付与
樹脂として、フェノール類を含有させて極性を持たせた
水酸基含有芳香族系炭化水素樹脂（特公平７−６５０２
０号公報）が知られているが、未水素化の水酸基含有芳
香族系炭化水素樹脂では色調、臭気が悪いため、前記食
品包装用や衛生材料用等の分野における要求を満たすこ
とができない。なお、かかる水酸基含有芳香族系炭化水
素樹脂を水素化すれば色調を改善することもできる。し
かし、当該水素化物を淡色化するためには芳香環の水素
化率を高く（芳香環の水素化率９０％以上）設定しなけ
ればならないため、得られる水酸基含有芳香族系炭化水
素樹脂の水素化物とアクリル系重合体との相溶性が悪
く、接着性やタックも悪い。一方、アクリル系重合体と
の良好な相溶性を維持するために芳香環の水素化率を低
く設定した場合には既知の技術では十分に色調を改善で
きず、淡色のものは得られない。Further, as a tackifying resin for an acrylic pressure-sensitive adhesive having good compatibility with an acrylic polymer and having improved adhesiveness, a hydroxyl group-containing aromatic carbonization containing a polar compound by containing phenols Hydrogen resin (Japanese Patent Publication 7-6502)
No. 0) is known, but the unhydrogenated hydroxyl group-containing aromatic hydrocarbon resin has poor color tone and odor, and therefore cannot meet the requirements in the fields such as food packaging and sanitary materials. The color tone can be improved by hydrogenating the hydroxyl group-containing aromatic hydrocarbon resin. However, in order to lighten the hydride, the hydrogenation rate of the aromatic ring must be set high (the hydrogenation rate of the aromatic ring is 90% or more). The compatibility between the compound and the acrylic polymer is poor, and the adhesion and tack are also poor. On the other hand, when the hydrogenation ratio of the aromatic ring is set low in order to maintain good compatibility with the acrylic polymer, the color tone cannot be sufficiently improved by the known technique, and a light-colored product cannot be obtained.
【０００５】[0005]
【発明が解決しようとする課題】本発明は接着力、保持
力、タック等の粘着特性に優れ、アクリル系重合体と相
溶するもので、しかも淡色で実用的な価格のアクリル系
感圧接着剤用粘着付与樹脂を提供するとともに、当該粘
着付与樹脂をアクリル系重合体に配合してなるアクリル
系感圧接着剤組成物を提供することを目的とする。SUMMARY OF THE INVENTION The present invention has excellent adhesive properties such as adhesive strength, holding power, tackiness, etc., is compatible with acrylic polymers, and is a light-colored and practically priced acrylic pressure-sensitive adhesive. It is an object of the present invention to provide a tackifying resin for an agent and an acrylic pressure-sensitive adhesive composition obtained by blending the tackifying resin with an acrylic polymer.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、前記課題
を解決すべく水酸基含有芳香族系炭化水素樹脂の水素化
物に着目して鋭意検討を行なった結果、特定の手段によ
り水酸基含有芳香族系炭化水素樹脂を水素化すれば、上
記目的に合致したアクリル系感圧接着剤用粘着付与樹脂
が得られ、また当該粘着付与樹脂が、溶剤型、エマルジ
ョン型のいずれのアクリル系感圧接着剤組成物にも適用
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] The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems by paying attention to a hydride of a hydroxyl group-containing aromatic hydrocarbon resin. By hydrogenating a group-type hydrocarbon resin, a tackifying resin for acrylic pressure-sensitive adhesive which meets the above-mentioned purpose can be obtained, and the tackifying resin can be solvent-type or emulsion-type acrylic pressure-sensitive adhesive. It has been found that it can also be applied to an agent composition. The present invention has been completed based on such new findings.
【０００７】すなわち、本発明は、水酸基含有芳香族系
炭化水素樹脂の水素化物であって、該水素化物がアクリ
ル系重合体と相溶し、かつ淡色のものを含有してなるア
クリル系感圧接着剤用粘着付与樹脂および当該粘着付与
樹脂エマルジョン、ならびにアクリル系重合体またはア
クリル系重合体エマルジョンに、前記アクリル系感圧接
着剤用粘着付与樹脂または当該粘着付与樹脂エマルジョ
ンを配合してなる溶剤型およびエマルジョン型のアクリ
ル系感圧接着剤組成物に関する。That is, the present invention relates to a hydride of a hydroxyl group-containing aromatic hydrocarbon resin, the hydride being compatible with an acrylic polymer and containing a light-colored acrylic pressure-sensitive resin. Adhesive tackifier resin and tackifier resin emulsion, and acrylic polymer or acrylic polymer emulsion, and the acrylic pressure-sensitive adhesive tackifier resin or solvent type solvent mixture prepared by blending the tackifier resin emulsion. And an emulsion-type acrylic pressure-sensitive adhesive composition.
【０００８】[0008]
【発明の実施の形態】本発明のアクリル系感圧接着剤用
粘着付与樹脂は、水酸基含有芳香族系炭化水素樹脂を水
素化することにより製造することができる。BEST MODE FOR CARRYING OUT THE INVENTION The tackifying resin for an acrylic pressure-sensitive adhesive of the present invention can be produced by hydrogenating a hydroxyl group-containing aromatic hydrocarbon resin.
【０００９】原料となる水酸基含有芳香族系炭化水素樹
脂としては特に限定されないが、一般に、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、フェノール類の存在下で、カチオン重合して得られ
たものを用いることができる。The hydroxyl group-containing aromatic hydrocarbon resin used as a raw material is not particularly limited, but generally, a C9 fraction obtained by cracking naphtha (for example, styrene, vinyltoluene, α-methylstyrene, indene, etc.)
What was obtained by cationically polymerizing in the presence of phenols can be used.
【００１０】フェノール類としては、フェノールまたは
クレゾール、キシレノール、ｐ−ｔ−ブチルフェノー
ル、ｐ−オクチルフェノール、ｐ−ノニルフェノール等
のアルキルフェノール類を使用できる。これらのなかで
もフェノールが接着性の点で好ましい。これらフェノー
ル類は、単独で用いてもよく、また２種以上を併用して
もよい。フェノール類の使用量は特に限定されないが、
水酸基含有芳香族系炭化水素樹脂の水酸基価が、水素化
の際に水素化条件等により減少する場合があることを考
慮すれば、通常は、得られる水酸基含有芳香族系炭化水
素樹脂の水酸基価が２０〜１２０の範囲になるようにフ
ェノール類を配合するのが好ましい。その使用量は、通
常、前記Ｃ９留分１００重量部に対して、５〜４０重量
部程度、好ましくは１０〜３０重量部である。As the phenols, phenol or alkylphenols such as cresol, xylenol, pt-butylphenol, p-octylphenol and p-nonylphenol can be used. Of these, phenol is preferable in terms of adhesiveness. These phenols may be used alone or in combination of two or more. The amount of phenols used is not particularly limited,
Considering that the hydroxyl value of the hydroxyl group-containing aromatic hydrocarbon resin may be reduced during hydrogenation due to hydrogenation conditions, etc., the hydroxyl value of the resulting hydroxyl group-containing aromatic hydrocarbon resin is usually It is preferable to blend the phenols so that the ratio is in the range of 20 to 120. The amount used is usually about 5 to 40 parts by weight, preferably 10 to 30 parts by weight, based on 100 parts by weight of the C9 fraction.
【００１１】前記原料である水酸基含有芳香族系炭化水
素樹脂の水素化は、以下に示す特定の水素化触媒の存在
下、水素化条件を適宜に調整して、得られる水素化物が
アクリル系重合体と相溶し、かつ淡色物となるように行
う。通常は、該原料の水酸基含有芳香族系炭化水素樹脂
のオレフィン性二重結合の全部と芳香環の０〜８０％程
度を水素化する。In the hydrogenation of the hydroxyl group-containing aromatic hydrocarbon resin which is the above-mentioned raw material, the hydrogenation condition is appropriately adjusted in the presence of the following specific hydrogenation catalyst so that the obtained hydride is an acrylic heavy resin. Do so that it becomes compatible with the coalescence and becomes a light-colored product. Usually, all of the olefinic double bonds of the hydroxyl group-containing aromatic hydrocarbon resin as the raw material and about 0 to 80% of the aromatic ring are hydrogenated.
【００１２】当該水素化物がアクリル系重合体と相溶す
るとは、アクリル系重合体１００重量部（固形分）と当
該水素化物１〜４０重量部を混合した場合に、両者が均
一に混和し、相分離を起こしていない状態をいう。一般
には、相溶している場合にはアクリル系重合体と当該水
素化物からなる混合物は無色透明であり、相分離を起こ
すと白濁した状態になるため、目視で十分判断できる。
なお、当該水素化物がアクリル系重合体に部分相溶して
いる場合には少し濁ってるが、こうした部分相溶してい
る状態も相溶している範疇である。また、当該水素化物
を含むアクリル系重合体組成物のガラス転移点が、アク
リル系重合体のガラス転移点と異なる場合に、当該水素
化物がアクリル系重合体と相溶していると判断すること
ができる。通常、相溶している場合にはアクリル系重合
体組成物のガラス転移点はアクリル系重合体のガラス転
移点より高くなる。その他に、当該水素化物がアクリル
系重合体と相溶していることを示す判断基準としては、
得られたアクリル系重合体組成物（膜厚３５μｍ）のＵ
Ｖ透過率（波長５００ｎｍ）を測定し、ＵＶ透過率が５
０％以上あれば相溶しているとされる。好ましくは７０
％以上である。The fact that the hydride is compatible with the acrylic polymer means that when 100 parts by weight (solid content) of the acrylic polymer and 1 to 40 parts by weight of the hydride are mixed, both are uniformly mixed, The state in which phase separation has not occurred. Generally, when they are compatible with each other, the mixture of the acrylic polymer and the hydride is colorless and transparent, and when phase separation occurs, it becomes a cloudy state, which can be visually judged sufficiently.
When the hydride is partially compatible with the acrylic polymer, it is a little cloudy, but such a partially compatible state is also in the category of compatibility. Further, when the glass transition point of the acrylic polymer composition containing the hydride is different from the glass transition point of the acrylic polymer, it is determined that the hydride is compatible with the acrylic polymer. You can Generally, when they are compatible, the glass transition point of the acrylic polymer composition is higher than the glass transition point of the acrylic polymer. In addition, as a criterion for indicating that the hydride is compatible with the acrylic polymer,
U of the obtained acrylic polymer composition (film thickness 35 μm)
V transmittance (wavelength 500 nm) was measured and UV transmittance was 5
If it is 0% or more, it is considered to be compatible. Preferably 70
% Or more.
【００１３】当該水素化物が淡色物となるとは、色調が
重視される分野において、当該水素化物をアクリル系重
合体に混合してなる組成物が、当該分野で使用できる程
度に当該水素化物が淡色化されていることをいう。一般
的に淡色化されているとは、当該水素化物の色調がガー
ドナー３程度以下、好ましくはガードナー２以下、より
好ましくはガードナー１以下であることをいう。In the field where color tone is important, it means that the composition obtained by mixing the hydride with an acrylic polymer is light-colored to such an extent that it can be used in the field. It is said that it has been made. Generally, being lightened means that the hydride has a color tone of about 3 or less, preferably Gardner 2 or less, more preferably Gardner 1 or less.
【００１４】また、オレフィン性二重結合が残存する程
度の水素化では脱色が不十分である。一方、芳香環の水
素化率が８０％を越える場合にはアクリル系重合体との
相溶性が悪く接着性が著しく低下する傾向があるため好
ましくない。アクリル系重合体との相溶性の点からは芳
香環の水素化率は０〜５０％が好ましい。芳香環の水素
化率が８０％を越える場合には、芳香環に由来する極性
が低くなることに加え、水酸基が分解してしまったり、
おそらくは樹脂中のフェノールの芳香環が水素化される
結果、水酸基がフェノール性からアルコール性に変わ
り、接着性へ影響を及ぼしているためであると考えられ
る。なお、芳香環の水素化率は少ないほど極性を有し、
接着力が向上する傾向にあるため芳香環の水素化率は０
％でもよい。Further, decolorization is insufficient by hydrogenation to the extent that olefinic double bonds remain. On the other hand, when the hydrogenation rate of the aromatic ring exceeds 80%, the compatibility with the acrylic polymer is poor and the adhesiveness tends to remarkably decrease, which is not preferable. From the viewpoint of compatibility with the acrylic polymer, the hydrogenation rate of the aromatic ring is preferably 0 to 50%. When the hydrogenation rate of the aromatic ring exceeds 80%, the polarity derived from the aromatic ring becomes low, and the hydroxyl group is decomposed,
Presumably, this is because the hydroxyl group changed from phenolic to alcoholic as a result of hydrogenation of the phenolic aromatic ring in the resin, which affects the adhesiveness. Incidentally, the smaller the hydrogenation rate of the aromatic ring, the more polar the
Since the adhesive strength tends to improve, the hydrogenation rate of the aromatic ring is 0.
% May be used.
【００１５】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、レニウ
ム、モリブデン等の金属またはこれらの酸化物等に、さ
らにマグネシウム、カルシウム、バリウム等のアルカリ
土類金属を含むものを使用する。このようなアルカリ土
類金属を含む水素化触媒を水酸基含有芳香族系炭化水素
樹脂の水素化に使用することにより、初めて得られる水
素化物の水素化率が前記範囲（オレフィン性二重結合の
全部と芳香環の０〜８０％程度）であっても色調がガー
ドナー１以下のものが得られるようになった。また、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。これら水素化触媒のなかでもア
ルカリ土類金属を含むニッケル−ケイソウ土触媒が、水
素化率を前記範囲内に調整し易く、色調に優れたものが
得られる点で好ましい。このような水素化触媒として
は、たとえば、安定化ニッケル−ケイソウ土触媒（「Ｓ
Ｎ−２５０」、堺化学（株）製）等があげられる。水素
化触媒の使用量は、原料樹脂である水酸基含有芳香族系
炭化水素樹脂の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。The hydrogenation catalyst includes a metal such as nickel, palladium, platinum, cobalt, rhodium, ruthenium, rhenium or molybdenum, or an oxide thereof, and an alkaline earth metal such as magnesium, calcium or barium. To use. By using such a hydrogenation catalyst containing an alkaline earth metal for hydrogenation of a hydroxyl group-containing aromatic hydrocarbon resin, the hydrogenation rate of the hydride obtained for the first time is within the above range (all of the olefinic double bonds are And about 0 to 80% of the aromatic ring), a color tone of Gardner 1 or less can be obtained. Further, such a hydrogenation catalyst may be used by being supported on a carrier such as alumina, silica (diatomaceous earth), carbon, and titania having a large surface area and being porous. Among these hydrogenation catalysts, a nickel-diatomaceous earth catalyst containing an alkaline earth metal is preferable because it is easy to adjust the hydrogenation rate within the above range and a catalyst excellent in color tone is obtained. Examples of such a hydrogenation catalyst include, for example, a stabilized nickel-diatomaceous earth catalyst (“S
N-250 ", manufactured by Sakai Chemical Co., Ltd., and the like. The amount of the hydrogenation catalyst used is about 0.1 to 3% by weight of the hydroxyl group-containing aromatic hydrocarbon resin which is the raw material resin, and preferably 0.1.
1 to 1% by weight. If the amount is less than 0.1% by weight, the hydrogenation tends to be difficult to proceed, while if it exceeds 3% by weight, the hydrogenation tends to proceed too much.
【００１６】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℃程度の範囲で適宜に調整して行う。好ま
しくは水素化圧力は１００〜２００Ｋｇ／ｃｍ2 であ
り、反応温度は２２０〜３００℃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１５
０℃に満たない場合には水素化が進み難い。水素化圧力
が３００Ｋｇ／ｃｍ2 を越える場合には設備上の問題が
あり、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２〜６時間である。前記水素
化反応は水酸基含有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 in the range of about 0 to 300 Kg / cm 2.
The temperature is adjusted appropriately in the range of about 50 to 300 ° C. Preferably, the hydrogenation pressure is 100 to 200 Kg / cm 2 , and the reaction temperature is 220 to 300 ° C. If the hydrogenation pressure is less than 30 Kg / cm 2 or the reaction temperature is 15
If it is less than 0 ° C, hydrogenation is difficult to proceed. If the hydrogenation pressure exceeds 300 Kg / cm 2 , there is a problem in equipment, and if the reaction temperature exceeds 300 ° C., decomposition tends to occur and the softening point tends to decrease. The reaction time is usually 1
It is about 7 hours, preferably 2 to 6 hours. In the hydrogenation reaction, a hydroxyl group-containing aromatic hydrocarbon resin is melted,
Alternatively, it is performed in a state of being dissolved in a solvent. As the solvent, cyclohexane, n-hexane, n-heptane, decalin or the like can be used.
【００１７】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 case of using the batch system as the reaction system has been described. However, the flow system (fixed bed system, fluidized bed system, etc.) may be adopted as the reaction system. it can.
【００１８】得られた前記水酸基含有芳香族系炭化水素
樹脂の水素化物の水酸基価は、通常１２０以下、好まし
くは２０〜１２０であり、上限としては１００以下、下
限としては４０以上がより好ましい。水酸基価が２０未
満の場合には、当該水素化物の芳香環の水素化率が高い
場合にアクリル系重合体との相溶性が悪く水酸基による
接着性向上の効果が現れにくい。一方、水酸基価が１２
０を越える場合には、アクリル系重合体との相溶性、接
着特性は良好なものの、原料の水酸基含有芳香族系炭化
水素樹脂自体の色相が非常に悪いため、当該水素化物の
色調改善が非常に困難である。なお、通常、水酸基含有
芳香族系炭化水素樹脂は、その水酸基価が１００程度以
下のため、その水素化物の水酸基価も１００程度以下と
なる。The hydroxyl value of the obtained hydride of the hydroxyl group-containing aromatic hydrocarbon resin is usually 120 or less, preferably 20 to 120, more preferably 100 or less as the upper limit and 40 or more as the lower limit. When the hydroxyl value is less than 20, when the hydrogenation rate of the aromatic ring of the hydride is high, the compatibility with the acrylic polymer is poor and the effect of improving the adhesiveness due to the hydroxyl group is difficult to appear. On the other hand, the hydroxyl value is 12
When it exceeds 0, the compatibility with the acrylic polymer and the adhesive property are good, but the hue of the raw material hydroxyl group-containing aromatic hydrocarbon resin itself is very poor, and the color tone of the hydride is greatly improved. Difficult to do. Since the hydroxyl group-containing aromatic hydrocarbon resin usually has a hydroxyl value of about 100 or less, the hydride has a hydroxyl value of about 100 or less.
【００１９】また、水酸基含有芳香族系炭化水素樹脂の
水素化物の軟化点は、通常７０〜１５０℃程度が好まし
く、上限としては１２０℃以下、下限としては８０℃以
上がより好ましい。また、数平均分子量は、通常５００
〜１６００、好ましくは５００〜９００である。なお、
原料（未水素化物）も、水素化物と同程度の軟化点、数
平均分子量である。The softening point of the hydride of the hydroxyl group-containing aromatic hydrocarbon resin is preferably about 70 to 150 ° C., more preferably 120 ° C. or lower as the upper limit and 80 ° C. or higher as the lower limit. The number average molecular weight is usually 500.
-1600, preferably 500-900. In addition,
The raw material (unhydrogenated material) also has a softening point and a number average molecular weight similar to those of hydrides.
【００２０】記本発明の水酸基含有芳香族系炭化水素樹
脂の水素化物（粘着付与樹脂）は、エマルジョン化して
粘着付与樹脂エマルジョンとして用いることもできる。
当該粘着付与樹脂をエマルジョン化する方法は、特に限
定されず各種の方法を採用できる。たとえば、前記粘
着付与樹脂をベンゼン、トルエン等の溶剤に溶解し、さ
らに乳化剤と軟水を添加し、高圧乳化機を用いてエマル
ジョン化したのち、減圧下に溶剤を除去する方法、前
記粘着付与樹脂の軟化点が約９０℃以下となるよう少量
のベンゼン、トルエン等の溶剤を混合し、つづいて乳化
剤を練り込み、さらに熱水を徐々に添加してゆき転相乳
化させてエマルジョンを得、必要により溶剤を減圧下に
除去しもしくは除去せずそのまま使用する方法、または
オートクレーブ中にて粘着付与樹脂の軟化点以上に昇
温して乳化剤を練り込み、熱水を徐々に添加してゆき転
相乳化させてエマルジョン化する方法等をあげることが
できる。なお、得られる粘着付与樹脂エマルジョンの固
形分濃度は、通常４０〜６５重量％程度に調製するのが
好ましい。The hydride (tackifying resin) of the hydroxyl group-containing aromatic hydrocarbon resin of the present invention can be emulsified and used as a tackifying resin emulsion.
The method of emulsifying the tackifying resin is not particularly limited, and various methods can be adopted. For example, the tackifying resin is dissolved in a solvent such as benzene and toluene, an emulsifier and soft water are further added, and the mixture is emulsified using a high-pressure emulsifier, and then the solvent is removed under reduced pressure. Mix a small amount of solvent such as benzene, toluene, etc. so that the softening point is about 90 ° C. or lower, then knead the emulsifier, and then add hot water gradually to obtain an emulsion by phase inversion emulsification, if necessary. The solvent is removed under reduced pressure or used as it is, or the temperature is raised to above the softening point of the tackifying resin in the autoclave, the emulsifier is kneaded, and hot water is gradually added to carry out phase inversion emulsification. The method of emulsification can be mentioned. The solid content concentration of the obtained tackifying resin emulsion is usually preferably adjusted to about 40 to 65% by weight.
【００２１】前記粘着付与樹脂をエマルジョン化するの
に使用する乳化剤としては各種のものを例示でき、たと
えば、α−オレフィンスルホン化物、アルキルサルフェ
ート、アルキルフェニルサルフェート、ポリオキシエチ
レンアルキルフェニルエーテルサルフェート、ポリオキ
シエチレンアラルキルフェニルエーテルのスルホコハク
酸のハーフエステル塩、ロジン石鹸等のアニオン系乳化
剤、ポリオキシエチレンアルキルフェニルエーテル等の
ノニオン系乳化剤があげられる。また、乳化剤の使用量
は特に限定されないが通常、粘着付与樹脂１００重量部
に対し、固形分換算で１〜１０重量部程度、好ましくは
１〜５重量部である。As the emulsifier used for emulsifying the tackifying resin, various emulsifiers can be exemplified, for example, α-olefin sulfonate, alkyl sulfate, alkylphenyl sulfate, polyoxyethylene alkylphenyl ether sulfate, polyoxy. Examples thereof include sulfosuccinic acid half ester salts of ethylene aralkyl phenyl ether, anionic emulsifiers such as rosin soap, and nonionic emulsifiers such as polyoxyethylene alkylphenyl ether. The amount of the emulsifier used is not particularly limited, but is usually about 1 to 10 parts by weight, preferably 1 to 5 parts by weight in terms of solid content, relative to 100 parts by weight of the tackifying resin.
【００２２】上記のようにして得られた本発明の水酸基
含有芳香族系炭化水素樹脂の水素化物からなるアクリル
系感圧接着剤用粘着付与樹脂または当該粘着付与樹脂の
エマルジョンは、一般にアクリル系感圧接着剤に使用さ
れているベースポリマー（アクリル系重合体またはアク
リル系重合体エマルジョン）に配合されて、溶剤型また
はエマルジョン型のアクリル系感圧接着剤組成物を構成
する。The tackifying resin for an acrylic pressure-sensitive adhesive or the emulsion of the tackifying resin, which is obtained by the above-mentioned method and comprises a hydride of a hydroxyl group-containing aromatic hydrocarbon resin of the present invention, is generally an acrylic type tackifying resin. It is mixed with the base polymer (acrylic polymer or acrylic polymer emulsion) used in the pressure-sensitive adhesive to form a solvent-type or emulsion-type acrylic pressure-sensitive adhesive composition.
【００２３】アクリル系重合体に使用されるモノマーと
しては、各種（メタ）アクリル酸エステル（なお、（メ
タ）アクリル酸エステルとはアクリル酸エステルおよび
／またはメタクリル酸エステルをいい、以下（メタ）と
は同様の意味である）を使用できる。かかる（メタ）ア
クリル酸エステルの具体例としては、たとえば、（メ
タ）アクリル酸メチル、（メタ）アクリル酸エチル、
（メタ）アクリル酸ブチル、（メタ）アクリル酸２−エ
チルヘキシル等を例示でき、これらを単独もしくは組合
せて使用できる。また、得られるアクリル系重合体に極
性を付与するために前記（メタ）アクリル酸エステルの
一部に代えて（メタ）アクリル酸を少量使用することも
できる。さらに、架橋性単量体として（メタ）アクリル
酸グリシジル、（メタ）アクリル酸２−ヒドロキシエチ
ル、Ｎ−メチロール（メタ）アクリルアミド等も併用し
うる。更に所望により、（メタ）アクリル酸エステル重
合体の粘着特性を損なわない程度において他の共重合可
能な単量体、たとえば酢酸ビニル、スチレン等を併用し
うる。As the monomer used for the acrylic polymer, various (meth) acrylic acid esters (wherein (meth) acrylic acid ester means acrylic acid ester and / or methacrylic acid ester, and hereinafter referred to as (meth)) Have the same meaning). Specific examples of such (meth) acrylic acid ester include, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
Examples include butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate, which can be used alone or in combination. In addition, a small amount of (meth) acrylic acid may be used instead of a part of the (meth) acrylic acid ester in order to impart polarity to the obtained acrylic polymer. Furthermore, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-methylol (meth) acrylamide, etc. may be used in combination as the crosslinkable monomer. Furthermore, if desired, other copolymerizable monomers such as vinyl acetate and styrene may be used in combination to the extent that the adhesive property of the (meth) acrylic acid ester polymer is not impaired.
【００２４】これら（メタ）アクリル酸エステルを主成
分とするアクリル系重合体のガラス転移温度は特に制限
はされないが、通常は−９０〜０℃程度であり、上限と
しては−１０℃以下、下限としては−８０℃以上とする
のが好ましい。ガラス転移温度が０℃よりもあまりにも
高い場合にはタックが低下し、−９０℃よりもあまりに
も低い場合には接着力が低下する傾向がある。また、分
子量は特に限定されないが、通常、重量分子量が２０万
〜１００万程度である。The glass transition temperature of the acrylic polymer containing these (meth) acrylic acid ester as a main component is not particularly limited, but is usually about -90 to 0 ° C, and the upper limit is -10 ° C or lower and the lower limit. Is preferably -80 ° C or higher. If the glass transition temperature is higher than 0 ° C, the tack tends to decrease, and if the glass transition temperature is lower than -90 ° C, the adhesive force tends to decrease. The molecular weight is not particularly limited, but the weight molecular weight is usually about 200,000 to 1,000,000.
【００２５】前記アクリル系重合体は、各種公知の方法
により製造でき、たとえば、バルク重合法、溶液重合
法、懸濁重合法等のラジカル重合法を適宜選択できる。
ラジカル重合開始剤としては、アゾ系、過酸化物系の各
種公知のものを使用でき、反応温度は通常５０〜８５℃
程度、反応時間は１〜８時間程度とされる。また、アク
リル系重合体の溶媒としては一般に酢酸エチル、トルエ
ン等の極性溶剤が用いられ、溶液濃度は通常４０〜６０
重量％程度とされる。The acrylic polymer can be produced by various known methods, and for example, radical polymerization methods such as bulk polymerization method, solution polymerization method and suspension polymerization method can be appropriately selected.
As the radical polymerization initiator, various known azo-based and peroxide-based initiators can be used, and the reaction temperature is usually 50 to 85 ° C.
The reaction time is about 1 to 8 hours. As a solvent for the acrylic polymer, a polar solvent such as ethyl acetate or toluene is generally used, and the solution concentration is usually 40 to 60.
It is set to about% by weight.
【００２６】一方、アクリル系重合体エマルジョンは、
一般的な乳化重合により製造することができる。たとえ
ば、（メタ）アクリル酸エステル等のモノマーの一括仕
込み重合法、モノマー逐次添加重合法、、シード重合法
等を採用できる。またアクリル系重合体エマルジョンに
用いられる乳化剤としては前記アニオン系乳化剤、部分
ケン化ポリビニルアルコール等の各種のものを使用で
き、その使用量はアクリル系重合体１００重量部に対し
て通常０．１〜５重量部程度、好ましく０．１〜３重量
部である。アクリル系重合体エマルジョンの固形分濃度
は、通常４０〜７０重量％程度に調製するのが好まし
い。On the other hand, the acrylic polymer emulsion is
It can be produced by general emulsion polymerization. For example, a batch charge polymerization method of monomers such as (meth) acrylic acid ester, a monomer sequential addition polymerization method, and a seed polymerization method can be adopted. As the emulsifier used in the acrylic polymer emulsion, various anionic emulsifiers, partially saponified polyvinyl alcohol and the like can be used, and the amount thereof is usually 0.1 to 100 parts by weight of the acrylic polymer. It is about 5 parts by weight, preferably 0.1 to 3 parts by weight. The solid content concentration of the acrylic polymer emulsion is usually preferably adjusted to about 40 to 70% by weight.
【００２７】本発明の溶剤型のアクリル系感圧接着剤組
成物の組成比は、固形分換算量でアクリル系重合体１０
０重量部に対して、前記粘着付与樹脂の１〜４０重量部
程度である。粘着付与樹脂の使用量の上限として３０重
量部以下、下限としては５重量部以上が好ましい。一
方、エマルジョン型のアクリル系感圧接着剤組成物の組
成比は、固形分換算量でアクリル系重合体エマルジョン
１００重量部に対して、前記粘着付与樹脂エマルジョン
１〜４０重量部程度である。粘着付与樹脂エマルジョン
の使用量の上限として２０重量部以下、下限としては３
重量部以上が好ましい。粘着付与樹脂または粘着付与樹
脂エマルジョンの使用量が前記範囲に満たない場合には
十分な粘着特性を付与することが困難となる。前記使用
量を越える場合には相溶性の低下のみならず接着剤組成
物が固くなり接着力及びタックも低下するため好ましく
ない。The composition ratio of the solvent-type acrylic pressure-sensitive adhesive composition of the present invention is such that the acrylic polymer 10 is calculated in terms of solid content.
It is about 1 to 40 parts by weight of the tackifying resin with respect to 0 parts by weight. The upper limit of the amount of the tackifying resin used is preferably 30 parts by weight or less, and the lower limit thereof is preferably 5 parts by weight or more. On the other hand, the composition ratio of the emulsion type acrylic pressure-sensitive adhesive composition is about 1 to 40 parts by weight of the tackifying resin emulsion with respect to 100 parts by weight of the acrylic polymer emulsion in terms of solid content. The upper limit of the amount of the tackifying resin emulsion used is 20 parts by weight or less, and the lower limit is 3
It is preferably at least part by weight. When the amount of the tackifying resin or the tackifying resin emulsion used is less than the above range, it becomes difficult to impart sufficient tackiness characteristics. If the amount used exceeds the above range, not only the compatibility decreases but also the adhesive composition becomes hard and the adhesive strength and tack decrease, which is not preferable.
【００２８】なお、溶媒型のアクリル系感圧接着剤組成
物は、前記アクリル系重合体および粘着付与樹脂に、ポ
リイソシアネート化合物、ポリアミン化合物、メラミン
樹脂、尿素樹脂、エポキシ樹脂等の架橋剤を加えること
により、凝集力、耐熱性を更に向上させることもでき
る。これら架橋剤のなかでも、特にポリイソシアネート
化合物を使用するのが好ましく、その具体例としては、
１，６−ヘキサメチレンジイソシアネート、テトラメチ
レンジイソシアネート、イソホロンジイソシアネート、
キシリレンジイソシアネート、トリレンジイソシアネー
ト、４，４−ジフェニルメタンジイソシアネート等の各
種公知のものがあげられる。さらに、必要に応じて充填
剤、酸化防止剤、紫外線吸収剤等を、また本発明の目的
を逸脱しない範囲で各種公知の粘着付与樹脂を適宜に使
用することもできる。In the solvent type acrylic pressure-sensitive adhesive composition, a cross-linking agent such as polyisocyanate compound, polyamine compound, melamine resin, urea resin or epoxy resin is added to the acrylic polymer and tackifying resin. As a result, the cohesive force and heat resistance can be further improved. Among these crosslinking agents, it is particularly preferable to use a polyisocyanate compound, and specific examples thereof include:
1,6-hexamethylene diisocyanate, tetramethylene diisocyanate, isophorone diisocyanate,
Various known compounds such as xylylene diisocyanate, tolylene diisocyanate and 4,4-diphenylmethane diisocyanate can be used. Further, if necessary, a filler, an antioxidant, an ultraviolet absorber, etc., and various known tackifying resins may be appropriately used within a range not departing from the object of the present invention.
【００２９】また、エマルジョン型のアクリル系感圧接
着剤組成物は必要に応じて消泡剤、増粘剤、充填剤、酸
化防止剤、耐水化剤、造膜助剤等を、また本発明の目的
を逸脱しない範囲で各種公知の粘着付与樹脂のエマルジ
ョンを併用することもできる。The emulsion type acrylic pressure-sensitive adhesive composition may further contain a defoaming agent, a thickening agent, a filler, an antioxidant, a water-proofing agent, a film-forming aid, etc., if necessary. An emulsion of various known tackifying resins may be used in combination within the range not deviating from the purpose.
【００３０】[0030]
【発明の効果】本発明によれば、接着力、凝集力（保持
力）、タック等の粘着特性に優れ、淡色であって、しか
もアクリル系重合体との相溶性に優れた粘着付与樹脂お
よび粘着付与樹脂エマルジョンを提供でき、また当該粘
着付与樹脂または粘着付与樹脂エマルジョンを用いた溶
剤型またはエマルジョン型のアクリル系感圧接着剤組成
物を提供できる。また、本発明の粘着付与樹脂を用いた
アクリル系感圧接着剤組成物は、粘着付与樹脂としてロ
ジン系樹脂等を用いたものに比べて、保持力、タック、
耐光性、耐候性に優れ、紙等との接着性もよい。さらに
は、粘着付与樹脂の原料が石油等から得られる安価な芳
香族留分であり、実用的な価格のものを提供することが
できる。また、エマルジョン型のアクリル系感圧接着剤
組成物は、大気汚染がないこと、安全衛生に優れている
こと及び省資源に適すること等の種々の利点を有する。EFFECTS OF THE INVENTION According to the present invention, a tackifying resin having excellent adhesive properties such as adhesive force, cohesive force (holding power), tack, etc., a light color, and excellent compatibility with an acrylic polymer, A tackifying resin emulsion can be provided, and a solvent-type or emulsion-type acrylic pressure-sensitive adhesive composition using the tackifying resin or the tackifying resin emulsion can be provided. Further, the acrylic pressure-sensitive adhesive composition using the tackifying resin of the present invention has a holding power, tack, as compared with those using a rosin resin or the like as the tackifying resin.
It has excellent light resistance and weather resistance, and has good adhesion to paper and the like. Further, the raw material of the tackifying resin is an inexpensive aromatic distillate obtained from petroleum or the like, which can be provided at a practical price. Further, the emulsion type acrylic pressure-sensitive adhesive composition has various advantages such as no air pollution, excellent safety and health, and suitable for resource saving.
【００３１】[0031]
【実施例】以下に実施例及び比較例をあげて本発明をさ
らに詳細に説明するが、本発明はこれら実施例に限定さ
れるものではない。なお、各例中、部は重量基準であ
る。EXAMPLES The present invention will be described in more detail 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.
【００３２】製造例１（アクリル系重合体の製造） 攪拌装置、冷却管、滴下ロートおよび窒素導入管を備え
た反応装置に酢酸エチル５７部、トルエン３３部、アク
リル酸ブチル９７部およびアクリル酸３部を仕込んだ
後、窒素気流下に系内温度が約７５℃となるまで昇温し
た。次いで、あらかじめアゾビスイソブチロニトリル
０．５部および酢酸エチル１０部を仕込んだ滴下ロート
から約３時間を要して系内に滴下し、更に５時間同温度
に保って重合反応を完結させ、固形分４９．６％、粘度
（２３℃）１１０００ｃｐｓのアクリル系重合体を得
た。Production Example 1 (Production of Acrylic Polymer) 57 parts of ethyl acetate, 33 parts of toluene, 97 parts of butyl acrylate and 3 parts of acrylic acid were placed in a reactor equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube. After charging the parts, the temperature was raised under a nitrogen stream until the temperature in the system reached about 75 ° C. Then, it was added dropwise to the system from a dropping funnel charged with 0.5 parts of azobisisobutyronitrile and 10 parts of ethyl acetate in advance over about 3 hours and kept at the same temperature for 5 hours to complete the polymerization reaction. An acrylic polymer having a solid content of 49.6% and a viscosity (23 ° C.) of 11000 cps was obtained.
【００３３】製造例２（アクリル系重合体エマルジョン
の製造） （１）水４４．４６部 （２）アニオン系乳化剤（商品名ハイテノールＳ、固形
分５０％、第一工業製薬（株）製）０．９０部、 （３）アクリル酸ブチルエステル４３．９０部およびア
クリル酸１．３６部 （４）触媒（過硫酸カリウム）０．２３部、ｐＨ調整剤
（重ソウ）０．１１部および水９．０４部 攪拌装置、冷却管、滴下ロートおよび窒素導入管を備え
た四つ口フラスコ中、７０℃の窒素ガス気流下で、上記
（１）および（２）を溶解した後、攪拌下に上記（３）
および（４）の合計の１／１０量を添加し７０℃で窒素
ガス気流下にて３０分間予備反応を行ない、その後、
（３）および（４）の合計の９／１０量を２時間かけて
滴下し、滴下重合を行なった。（３）および（４）の全
量を滴下し終った後、１時間完結反応を７０℃で行ない
室温に冷却後、１００メッシュ金網ろ過を行ないながら
取り出し、固形分４５．７％のアクリル系重合体のエマ
ルジョンを得た。Production Example 2 (Production of acrylic polymer emulsion) (1) Water 44.46 parts (2) Anionic emulsifier (trade name Hitenol S, solid content 50%, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) 0.90 parts, (3) butyl acrylate 43.90 parts and acrylic acid 1.36 parts (4) catalyst (potassium persulfate) 0.23 parts, pH adjuster (heavy saw) 0.11 parts and water 9.04 parts In a four-necked flask equipped with a stirrer, a cooling tube, a dropping funnel and a nitrogen introducing tube, under nitrogen gas flow at 70 ° C, the above (1) and (2) were dissolved, and then stirred. Above (3)
1/10 of the total of (4) and (4) were added, and a preliminary reaction was performed at 70 ° C. for 30 minutes under a nitrogen gas stream.
9/10 of the total of (3) and (4) was added dropwise over 2 hours to carry out dropwise polymerization. After dropping the total amount of (3) and (4), the reaction was completed at 70 ° C. for 1 hour, cooled to room temperature, taken out while performing 100 mesh wire mesh filtration, and an acrylic polymer having a solid content of 45.7%. Emulsion was obtained.
【００３４】実施例１（粘着付与樹脂） 未水素化のフェノール変性芳香族系炭化水素樹脂（「ネ
オポリマーＥ−１００（軟化点９０℃，色調１５ガード
ナー，水酸基価７３）」、日本石油化学（株）製）１０
０部と安定化ニッケル−ケイソウ土触媒（「ＳＮ−２５
０」、堺化学（株）製）０．５部をオートクレーブに仕
込み、水素圧２００ｋｇ／ｃｍ2 、反応温度２８０℃、
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、攪拌羽根、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５３８、軟化点９
２℃、色調１ガードナー以下、芳香環の水素化率１５
％、水酸基価６９のフェノール変性芳香族系炭化水素樹
脂の水素化物（粘着付与樹脂）９８部を得た。得られた
粘着付与樹脂の物性を表１に示す。Example 1 (Tackifying Resin) Unhydrogenated phenol-modified aromatic hydrocarbon resin (“Neopolymer E-100 (softening point 90 ° C., color tone 15 Gardner, hydroxyl value 73)”, Nippon Petrochemical ( Made) 10)
0 part and a stabilized nickel-diatomaceous earth catalyst (“SN-25
0 ", 0.5 part of Sakai Chemical Co., Ltd.) was charged into an autoclave, hydrogen pressure was 200 kg / cm 2 , reaction temperature was 280 ° C.,
The hydrogenation reaction was carried out under the condition that the reaction time was 5 hours. After the reaction was completed, the obtained resin was dissolved in 300 parts of cyclohexane and the catalyst was removed by filtration. Then, the filtrate was put into a 1 liter separable flask equipped with a stirring blade, a reflux condenser, a thermometer, a temperature controller and a pressure indicator, and the solvent was gradually heated to 200 ° C. and depressurized to 20 torr. Removed, number average molecular weight 538, softening point 9
2 ° C, color tone less than 1 Gardner, aromatic ring hydrogenation rate 15
%, And 98 parts of a hydride (tackifying resin) of a phenol-modified aromatic hydrocarbon resin having a hydroxyl value of 69 was obtained. Table 1 shows the physical properties of the obtained tackifying resin.
【００３５】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（％）。軟化点
は、ＪＩＳ Ｋ ２５３１の環球法による。また、色調
は、１８０℃に溶融後ガードナースタンダードカラー
（Ｇ）により目視判定した。The hydrogenation rate was calculated based on the following formula from the H-spectral area of the aromatic ring appearing in the vicinity of 7 ppm of 1H-NMR of the raw material resin and the obtained hydrogenated resin. Hydrogenation rate = {1- (spectrum area of hydrogenated resin /
Spectral area of raw material resin)} × 100 (%). The softening point is based on the ring and ball method of JIS K 2531. Further, the color tone was visually judged by Gardner Standard Color (G) after melting at 180 ° C.
【００３６】また、粘着付与樹脂の相溶性は、製造例１
で得られたアクリル重合体８０重量部と粘着付与樹脂２
０重量部をトルエンに溶解した溶液をサイコロアプリケ
ーター（１５０μｍ）でガラス板上に塗工厚が３５μｍ
となるように塗工した後、循風乾燥機中で乾燥し、トル
エンを除去した後、目視により、以下の基準で評価し
た。 ○−−−透明で相溶している。 △−−−少し濁っていて部分相溶している。 ×−−−白濁していて相溶していない。The compatibility of the tackifying resin is shown in Production Example 1
80 parts by weight of the acrylic polymer obtained in 1. and tackifying resin 2
A solution of 0 parts by weight dissolved in toluene was coated on a glass plate with a dice applicator (150 μm) to a thickness of 35 μm.
After being coated so as to have the following values, it was dried in a circulating air dryer to remove toluene, and then visually evaluated according to the following criteria. ○ ---- Transparent and compatible. △ ---- Slightly cloudy and partially compatible. × −−− It is cloudy and not compatible.
【００３７】実施例２（粘着付与樹脂） 実施例１において、触媒量を０．５部から１．０部、水
素圧を２００Ｋｇ／ｃｍ2 から１８０Ｋｇ／ｃｍ2 、反
応時間を５時間から３時間にそれぞれ変更した他は、実
施例１と同様にして粘着付与樹脂を製造した。得られた
粘着付与樹脂の物性を表１に示す。Example 2 (Tackifying Resin) In Example 1, the catalyst amount is 0.5 part to 1.0 part, the hydrogen pressure is 200 kg / cm 2 to 180 kg / cm 2 , and the reaction time is 5 hours to 3 hours. A tackifying resin was produced in the same manner as in Example 1 except that the above were changed. Table 1 shows the physical properties of the obtained tackifying resin.
【００３８】実施例３（粘着付与樹脂） 実施例１において、未水素化のフェノール変性芳香族系
炭化水素樹脂（「ネオポリマーＥ−１００」、日本石油
化学（株）製）を、（「ハイレジンＰＭ−１３０（軟化
点１２８．５℃，色調９ガードナー，水酸基価２
５）」，東邦化学（株）社製）に代えた他は、実施例１
と同様にして粘着付与樹脂を製造した。得られた粘着付
与樹脂の物性を表１に示す。Example 3 (Tackifying Resin) In Example 1, an unhydrogenated phenol-modified aromatic hydrocarbon resin (“Neopolymer E-100”, manufactured by Nippon Petrochemical Co., Ltd.) was used (“high resin”). PM-130 (softening point 128.5 ° C, color tone 9 Gardner, hydroxyl value 2
5) ”, manufactured by Toho Chemical Co., Ltd.)
A tackifying resin was produced in the same manner as in. Table 1 shows the physical properties of the obtained tackifying resin.
【００３９】比較例１（粘着付与樹脂） 粘着付与樹脂として、未水素化のフェノール変性芳香族
系炭化水素樹脂（「ネオポリマーＥ−１００」、日本石
油化学（株）社製）を用いた。粘着付与樹脂の物性を表
１に示す。Comparative Example 1 (Tackifying Resin) As the tackifying resin, an unhydrogenated phenol-modified aromatic hydrocarbon resin (“Neopolymer E-100”, manufactured by Nippon Petrochemical Co., Ltd.) was used. Table 1 shows the physical properties of the tackifying resin.
【００４０】比較例２（粘着付与樹脂） 粘着付与樹脂として、芳香族系炭化水素石油樹脂の水素
化物（「アルコンＭ−１００」、荒川化学工業（株）
製）を用いた。粘着付与樹脂の物性を表１に示す。Comparative Example 2 (Tackifying Resin) As a tackifying resin, a hydride of an aromatic hydrocarbon petroleum resin (“ALCON M-100”, Arakawa Chemical Industry Co., Ltd.)
Was used. Table 1 shows the physical properties of the tackifying resin.
【００４１】比較例３（粘着付与樹脂の製造） 未水素化のフェノール変性芳香族系炭化水素樹脂（「ハ
イレジンＰＭ−９０（軟化点８９．５℃，色調１１ガー
ドナー，水酸基価６７」、東邦化学（株）製）１００部
とニッケル−ケイソウ土触媒（「Ｎ−１１３」、日揮化
学（株）製）３部をオートクレーブに仕込み、水素圧２
００ｋｇ／ｃｍ2 、反応温度２５０℃、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、攪拌羽根、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、２
００℃、２０ｔｏｒｒまで徐々に昇温・減圧して溶媒を
除去し、粘着付与樹脂を製造した。得られた粘着付与樹
脂の物性を表１に示す。Comparative Example 3 (Production of Tackifying Resin) Unhydrogenated phenol-modified aromatic hydrocarbon resin (“High Resin PM-90 (softening point 89.5 ° C., color tone 11 Gardner, hydroxyl value 67”, Toho Kagaku Co., Ltd.) Co., Ltd.) 100 parts and nickel-diatomaceous earth catalyst (“N-113”, JGC Chemical Co., Ltd.) 3 parts were charged into an autoclave, and hydrogen pressure was 2
The hydrogenation reaction was carried out under the conditions of 00 kg / cm 2 , reaction temperature of 250 ° C., and reaction time of 5 hours. After the reaction was completed, the obtained resin was dissolved in 300 parts of cyclohexane and the catalyst was removed by filtration. After that, the filtrate was put into a 1-liter separable flask equipped with a stirring blade, a reflux condenser, a thermometer, a temperature controller and a pressure indicator.
The solvent was removed by gradually increasing the temperature and reducing the pressure to 00 ° C. and 20 torr to produce a tackifying resin. Table 1 shows the physical properties of the obtained tackifying resin.
【００４２】[0042]
【表１】 [Table 1]
【００４３】実施例４（アクリル系感圧接着剤組成物） 製造例１で得たアクリル系重合体８０部（固形分換算）
と実施例１で得られた水素化フェノール変性芳香族系炭
化水素樹脂（粘着付与樹脂）２０部を十分混練したの
ち、ポリイソシアネート系化合物（日本ポリウレタン
（株）製、商品名「コロネートＬ」）１．８部を添加
し、架橋型アクリル系感圧接着剤組成物を得た。Example 4 (Acrylic pressure-sensitive adhesive composition) 80 parts of the acrylic polymer obtained in Production Example 1 (solid content conversion)
And 20 parts of the hydrogenated phenol-modified aromatic hydrocarbon resin (tackifying resin) obtained in Example 1 were sufficiently kneaded, and then a polyisocyanate compound (manufactured by Nippon Polyurethane Co., Ltd., trade name “Coronate L”) 1.8 parts was added to obtain a crosslinked acrylic pressure-sensitive adhesive composition.
【００４４】実施例５〜６、比較例４〜６（アクリル系
感圧接着剤組成物） 実施例４において、表２に示すように粘着付与樹脂の種
類を実施例２〜３または比較例１〜３で得られたものに
代えた他は、実施例４と同様に行い架橋型アクリル系感
圧接着剤組成物を得た。Examples 5-6, Comparative Examples 4-6 (Acrylic Pressure-Sensitive Adhesive Compositions) In Example 4, as shown in Table 2, the type of tackifying resin is Examples 2-3 or Comparative Example 1. ~ 3 to obtain a cross-linked acrylic pressure-sensitive adhesive composition in the same manner as in Example 4 except that it was replaced with.
【００４５】［テープの性能試験］実施例４〜５または
比較例４〜６で調製した架橋型アクリル系感圧接着剤組
成物を、厚さ３８μｍのポリエチレンフィルムにサイコ
ロ型アプリケーターにて乾燥膜厚が３０μｍ程度となる
ように塗布し、ついで該接着剤組成物中の溶剤を除去し
て糊厚３０μｍのテープを作成した。得られたテープを
７日間放置し熟成した後、以下の試験方法により性能を
評価した。性能試験の結果を表２に示す。[Tape Performance Test] The crosslinked acrylic pressure-sensitive adhesive composition prepared in Examples 4 to 5 or Comparative Examples 4 to 6 was dried on a polyethylene film having a thickness of 38 μm with a dice type applicator. Of about 30 μm, and then the solvent in the adhesive composition was removed to prepare a tape having a paste thickness of 30 μm. The obtained tape was left to stand for 7 days for aging, and the performance was evaluated by the following test methods. The results of the performance test are shown in Table 2.
【００４６】（常温接着力）：得られたテープ（２５ｍ
ｍ×１００ｍｍ）をポリエチレン板に貼り付け、万能引
張試験機を使用して２０℃、３００ｍｍ／分の条件にお
ける１８０゜剥離強度（Ｋｇ／２５ｍｍ）を測定した。(Adhesive strength at room temperature): The obtained tape (25 m)
m × 100 mm) was attached to a polyethylene plate, and the 180 ° peel strength (Kg / 25 mm) under the conditions of 20 ° C. and 300 mm / min was measured using a universal tensile tester.
【００４７】（保持力）：得られたテープ（２５ｍｍ×
２５ｍｍ）をステンレス板に貼り付け、昇温クリープテ
スターを用いて１ｋｇ荷重し、６０℃から毎分２℃のペ
ースで昇温を行い、重りが落下したときの温度（℃）を
測定した。(Holding power): The obtained tape (25 mm ×
25 mm) was attached to a stainless steel plate, 1 kg was loaded using a temperature rising creep tester, the temperature was raised from 60 ° C. at a rate of 2 ° C./min, and the temperature (° C.) when the weight dropped was measured.
【００４８】（タック）：ＪＩＳ Ｚ ０２３７に記載
のＪ．Ｄｏｗ法により傾斜角３０度、測定温度２０℃の
条件で測定した。表２の数字はボールＮｏ．１４の転が
り距離（ｃｍ）を示す。(Tack): J. J. described in JIS Z 0237. It was measured by the Dow method under the conditions of an inclination angle of 30 degrees and a measurement temperature of 20 ° C. The numbers in Table 2 are the ball numbers. The rolling distance (cm) of 14 is shown.
【００４９】（耐光性）：得られたテープの表面に１５
ｃｍ離れたところからキセノン光を２４時間照射した
後、タックを上記と同様の方法に測定した。(Light resistance): 15 on the surface of the obtained tape
After irradiating with xenon light for 24 hours from a place separated by cm, the tack was measured by the same method as above.
【００５０】[0050]
【表２】 [Table 2]
【００５１】実施例７ （１）粘着付与樹脂エマルジョンの調製 実施例１で得られた粘着付与樹脂１００部をトルエン６
０部に１００℃にて約１時間かけて溶解した後、８０℃
まで冷却してアニオン系乳化剤（ドデシルベンゼンスル
ホン酸ナトリウム）を固形分換算で３部および水１６０
部を添加し７５℃にて１時間強攪拌し予備乳化を行なっ
た。得られた予備乳化物を高圧乳化機（マントンガウリ
ン社製）により３００ｋｇ／ｃｍ2 の圧力で高圧乳化し
て乳化物を得た。次いで、減圧蒸留装置に前記乳化物２
００部を仕込み、５０℃、１００ｍｍＨｇの条件下に６
時間減圧蒸留を行ない固形分５０％の粘着付与樹脂のエ
マルジョンを得た。Example 7 (1) Preparation of tackifying resin emulsion 100 parts of the tackifying resin obtained in Example 1 was mixed with toluene 6
After dissolving in 0 part at 100 ° C for about 1 hour, then 80 ° C
After cooling to 3 parts of anionic emulsifier (sodium dodecylbenzene sulfonate) in terms of solid content and water 160
Part was added, and preliminarily emulsified by strongly stirring at 75 ° C. for 1 hour. The obtained pre-emulsion was emulsified at a pressure of 300 kg / cm 2 with a high-pressure emulsifier (manton gauulin) to obtain an emulsion. Then, the emulsion 2 is placed in a vacuum distillation apparatus.
Charge 100 parts, and under conditions of 50 ° C and 100 mmHg, 6
After vacuum distillation for an hour, an emulsion of tackifying resin having a solid content of 50% was obtained.
【００５２】（２）エマルジョン型のアクリル系感圧接
着剤組成物の調製 上記（１）で得られた粘着付与樹脂のエマルジョン１０
部（固形分換算）と製造例２で得られたアクリル系重合
体のエマルジョン９０部（固形分換算）を混合し、さら
に、アクリル系の増粘剤としてプライマルＡＳＥ−６０
（日本アクリル社製）０．５部（固形分換算）を添加し
アンモニア水にて増粘させてエマルジョン型のアクリル
系感圧接着剤組成物を得た。(2) Preparation of emulsion type acrylic pressure-sensitive adhesive composition Emulsion 10 of tackifying resin obtained in (1) above
Parts (as solid content) and 90 parts (as solid content) of the emulsion of the acrylic polymer obtained in Production Example 2 are mixed, and further Primal ASE-60 as an acrylic thickener.
0.5 part (manufactured by Nippon Acrylic Co., Ltd.) (in terms of solid content) was added and thickened with aqueous ammonia to obtain an emulsion type acrylic pressure-sensitive adhesive composition.
【００５３】実施例８〜９、比較例７〜９ 実施例７（１）において、粘着付与樹脂の種類を表３に
示すように実施例２〜３または比較例１〜３で得られた
ものに代えた他は、実施例７と同様にして粘着付与樹脂
のエマルジョンを調製し、また実施例７（２）と同様に
してエマルジョン型のアクリル系感圧接着剤組成物を調
製した。Examples 8-9, Comparative Examples 7-9 In Example 7 (1), the types of tackifying resins obtained in Examples 2-3 or Comparative Examples 1-3 are shown in Table 3. A tackifier resin emulsion was prepared in the same manner as in Example 7 except that the above was used, and an emulsion type acrylic pressure-sensitive adhesive composition was prepared in the same manner as in Example 7 (2).
【００５４】［テープの性能試験］前記架橋型アクリル
系感圧接着剤組成物の性能試験に用いたテープを作成し
た方法と同様の方法により、実施例８〜９または比較例
８〜９で調製したエマルジョン型のアクリル系感圧接着
剤組成物を用いて、性能試験用のテープを作成した。得
られたテープにより、前記常温接着力、保持力、タッ
ク、耐光性の性能評価を行った。性能試験の結果を表３
に示す。[Tape Performance Test] Prepared in Examples 8 to 9 or Comparative Examples 8 to 9 by a method similar to the method of preparing the tape used for the performance test of the crosslinked acrylic pressure-sensitive adhesive composition. A tape for performance test was prepared using the emulsion type acrylic pressure-sensitive adhesive composition. The obtained tape was used to evaluate the performances of the room temperature adhesive strength, the holding power, the tack and the light resistance. Table 3 shows the results of the performance test.
Shown in
【００５５】[0055]
【表３】 [Table 3]
───────────────────────────────────────────────────── フロントページの続き (72)発明者 高木 芳徳 大阪市鶴見区鶴見１丁目１番９号荒川化学 工業株式会社研究所内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshinori Takagi 1-9, Tsurumi, Tsurumi-ku, Osaka Arakawa Chemical Industry Co., Ltd.
Claims (9)
化物であって、該水素化物がアクリル系重合体と相溶
し、かつ淡色のものを含有してなるアクリル系感圧接着
剤用粘着付与樹脂。1. A pressure-sensitive adhesive for an acrylic pressure-sensitive adhesive, comprising a hydride of a hydroxyl group-containing aromatic hydrocarbon resin, the hydride being compatible with an acrylic polymer and containing a light-colored one. Imparting resin.
化物の水酸基価が、１２０以下である請求項１記載のア
クリル系感圧接着剤用粘着付与樹脂。2. The tackifying resin for acrylic pressure-sensitive adhesives according to claim 1, wherein the hydride of the hydroxyl group-containing aromatic hydrocarbon resin has a hydroxyl value of 120 or less.
化物の軟化点が、７０〜１５０℃である請求項１または
２記載のアクリル系感圧接着剤用粘着付与樹脂。3. The tackifying resin for an acrylic pressure-sensitive adhesive according to claim 1, wherein the hydride of the hydroxyl group-containing aromatic hydrocarbon resin has a softening point of 70 to 150 ° C.
化物が、水酸基含有芳香族系炭化水素樹脂のオレフィン
性二重結合の全部と芳香環の０〜８０％を水素化したも
のである請求項１、２または３記載のアクリル系感圧接
着剤用粘着付与樹脂。4. The hydride of a hydroxyl group-containing aromatic hydrocarbon resin is obtained by hydrogenating 0 to 80% of all olefinic double bonds and aromatic rings of a hydroxyl group-containing aromatic hydrocarbon resin. Item 4. A tackifying resin for an acrylic pressure-sensitive adhesive according to Item 1, 2 or 3.
化物の色調がガードナー３以下である請求項１、２、３
または４記載のアクリル系感圧接着剤用粘着付与樹脂。5. The color tone of the hydride of the hydroxyl group-containing aromatic hydrocarbon resin is Gardner 3 or less.
Alternatively, the tackifying resin for acrylic pressure-sensitive adhesive according to 4 above.
化物の色調がガードナー１以下である請求項１、２、３
または４記載のアクリル系感圧接着剤用粘着付与樹脂。6. The color tone of the hydride of the hydroxyl group-containing aromatic hydrocarbon resin is Gardner 1 or less.
Alternatively, the tackifying resin for acrylic pressure-sensitive adhesive according to 4 above.
ル系感圧接着剤用粘着付与樹脂をエマルジョン化したも
のを含有してなるアクリル系感圧接着剤用粘着付与樹脂
エマルジョン。7. A tackifying resin emulsion for an acrylic pressure-sensitive adhesive, which comprises an emulsion of the tackifying resin for an acrylic pressure-sensitive adhesive according to claim 1.
て、固形分換算量で請求項１〜６のいずれかに記載のア
クリル系感圧接着剤用粘着付与樹脂１〜４０重量部を配
合してなる溶剤型のアクリル系感圧接着剤組成物。8. 1 to 40 parts by weight of the tackifying resin for an acrylic pressure-sensitive adhesive according to claim 1 is added to 100 parts by weight of the acrylic polymer in terms of solid content. A solvent-based acrylic pressure-sensitive adhesive composition comprising:
重量部に対して、固形分換算量で請求項７に記載のアク
リル系感圧接着剤用粘着付与樹脂エマルジョン１〜４０
重量部を配合してなるエマルジョン型のアクリル系感圧
接着剤組成物。9. An acrylic polymer emulsion 100.
The tackifying resin emulsion for acrylic pressure-sensitive adhesives 1 to 40 according to claim 7, in terms of solid content based on parts by weight.
An emulsion-type acrylic pressure-sensitive adhesive composition containing 1 part by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28739696A JP4168351B2 (en) | 1995-10-19 | 1996-10-08 | Tackifying resin for acrylic pressure-sensitive adhesive and acrylic pressure-sensitive adhesive composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7-297354 | 1995-10-19 | ||
| JP29735495 | 1995-10-19 | ||
| JP28739696A JP4168351B2 (en) | 1995-10-19 | 1996-10-08 | Tackifying resin for acrylic pressure-sensitive adhesive and acrylic pressure-sensitive adhesive composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH09169966A true JPH09169966A (en) | 1997-06-30 |
| JP4168351B2 JP4168351B2 (en) | 2008-10-22 |
Family
ID=26556710
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28739696A Expired - Lifetime JP4168351B2 (en) | 1995-10-19 | 1996-10-08 | Tackifying resin for acrylic pressure-sensitive adhesive and acrylic pressure-sensitive adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4168351B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002038117A (en) * | 2000-07-31 | 2002-02-06 | Arakawa Chem Ind Co Ltd | Tackifying resin emulsion and aqueous adhesive mass/ adhesive composition |
| US7758958B2 (en) | 2004-10-18 | 2010-07-20 | Nitto Denko Corporation | Pressure-sensitive adhesive sheet |
-
1996
- 1996-10-08 JP JP28739696A patent/JP4168351B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002038117A (en) * | 2000-07-31 | 2002-02-06 | Arakawa Chem Ind Co Ltd | Tackifying resin emulsion and aqueous adhesive mass/ adhesive composition |
| US7758958B2 (en) | 2004-10-18 | 2010-07-20 | Nitto Denko Corporation | Pressure-sensitive adhesive sheet |
| US7867610B2 (en) | 2004-10-18 | 2011-01-11 | Nitto Denko Corporation | Pressure-sensitive adhesive sheet |
| US8227533B2 (en) | 2004-10-18 | 2012-07-24 | Nitto Denko Corporation | Pressure-sensitive adhesive sheet |
| US8299156B2 (en) | 2004-10-18 | 2012-10-30 | Nitto Denko Corporation | Pressure-sensitive adhesive sheet |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4168351B2 (en) | 2008-10-22 |
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