JP2000309771A - Tackifying resin emulsion and aqueous pressure-sensitive adhesive composition - Google Patents
Tackifying resin emulsion and aqueous pressure-sensitive adhesive compositionInfo
- Publication number
- JP2000309771A JP2000309771A JP11119375A JP11937599A JP2000309771A JP 2000309771 A JP2000309771 A JP 2000309771A JP 11119375 A JP11119375 A JP 11119375A JP 11937599 A JP11937599 A JP 11937599A JP 2000309771 A JP2000309771 A JP 2000309771A
- Authority
- JP
- Japan
- Prior art keywords
- rosin
- resin emulsion
- tackifying resin
- parts
- acid value
- 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]
【発明の属する技術分野】本発明は、粘着付与樹脂エマ
ルジョンおよび水系粘着剤組成物に関する。かかる本発
明の粘着付与樹脂エマルジョンが配合された水系粘着剤
組成物は、ラベル、シート、テープ等の各種の用途に利
用できる。The present invention relates to a tackifier resin emulsion and an aqueous pressure-sensitive adhesive composition. The aqueous pressure-sensitive adhesive composition containing the tackifier resin emulsion of the present invention can be used for various uses such as labels, sheets, and tapes.
【０００２】[0002]
【従来の技術】水系粘着剤は、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
々の利点を有するため、現在ラベル、シート、テープ等
多くの粘着製品をはじめ、各種被着体の貼り合せ等に利
用されている。この様に水系粘着剤の用途が拡大するに
つれて、水系粘着剤に求められる性能もより高度になっ
ている。かかる要求性能として、基材及び被着材の多様
化によりポリプロピレン、ポリエチレン等のポリオレフ
ィンに対する接着性と耐熱性の両立が重視されている。2. Description of the Related Art Water-based pressure-sensitive adhesives have various advantages such as no air pollution, excellent safety and hygiene, and suitability for resource saving. First, it is used for bonding various adherends. As the use of the water-based pressure-sensitive adhesive has expanded in this way, the performance required of the water-based pressure-sensitive adhesive has also become higher. As such required performance, compatibility between adhesiveness to polyolefins such as polypropylene and polyethylene and heat resistance have been emphasized due to diversification of base materials and adherends.
【０００３】一般に、アクリル系重合体エマルジョンま
たはゴム系ラテックスを主成分とする水系粘着剤には、
ポリオレフィンに対する接着性等の改善ため、通常、粘
着付与樹脂エマルジョンを配合した水系粘着剤組成物と
して用いられる。当該粘着付与樹脂エマルジョンとして
は、ポリオレフィンに対する接着性を向上させる効果が
大きいことから、ロジンまたはロジンエステル等のロジ
ン誘導体の粘着付与樹脂エマルジョンが好適に用いられ
ている。Generally, an aqueous pressure-sensitive adhesive containing an acrylic polymer emulsion or a rubber-based latex as a main component includes:
In order to improve the adhesion to polyolefin and the like, it is usually used as an aqueous pressure-sensitive adhesive composition containing a tackifier resin emulsion. As the tackifier resin emulsion, a tackifier resin emulsion of a rosin derivative such as rosin or a rosin ester is preferably used because it has a large effect of improving the adhesion to polyolefin.
【０００４】しかし、ロジン系粘着付与樹脂の分子量
は、アクリル系重合体エマルジョン、またはゴム系ラテ
ックスのベースポリマーの分子量に比較して小さいた
め、ロジン系粘着付与樹脂を配合した水系粘着剤の耐熱
性が低いものとなる。However, since the molecular weight of the rosin-based tackifying resin is smaller than the molecular weight of the base polymer of the acrylic polymer emulsion or rubber latex, the heat resistance of the water-based adhesive containing the rosin-based tackifying resin is low. Is low.
【０００５】ロジン系粘着付与樹脂による水系粘着剤組
成物の耐熱性を改良する検討としては、粘着付与樹脂の
高軟化点化の検討もなされており、軟化点の高い重合ロ
ジンエステルを粘着付与樹脂として用いる試みもなされ
ている。しかし、かかる粘着付与樹脂によっても十分な
耐熱性を有する水系粘着剤組成物は得られていない。In order to improve the heat resistance of an aqueous pressure-sensitive adhesive composition using a rosin-based tackifying resin, studies have been made to increase the softening point of the tackifying resin, and a polymerized rosin ester having a high softening point is converted to a tackifying resin. Attempts have also been made to use them. However, an aqueous pressure-sensitive adhesive composition having sufficient heat resistance has not been obtained even with such a tackifying resin.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、耐熱性が良
好で、かつポリオレフィンに対する接着性も良好な粘着
付与樹脂エマルジョンを提供するとともに、当該粘着付
与樹脂エマルジョンを配合して得られる水系粘着剤組成
物を提供することを目的とする。SUMMARY OF THE INVENTION The present invention provides a tackifier resin emulsion having good heat resistance and good adhesion to polyolefin, and an aqueous pressure-sensitive adhesive obtained by blending the tackifier resin emulsion. It is intended to provide a composition.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、既存のア
クリル系重合体エマルジョンまたはゴム系ラテックスに
粘着付与樹脂エマルジョンを配合してなる水系粘着剤組
成物の有する前記課題を解決すべく鋭意研究を重ねた結
果、粘着付与樹脂エマルジョンとして、ロジン類および
／または酸価を有するロジン誘導体のカルボキシル基を
金属化合物により金属塩化した構造の化合物を、乳化剤
の存在下で乳化して得られるものを用いることにより前
記課題を解決できることを見出し、本発明を完成するに
至った。Means for Solving the Problems The present inventors have been keen to solve the above-mentioned problems of an aqueous pressure-sensitive adhesive composition obtained by blending a tackifier resin emulsion with an existing acrylic polymer emulsion or rubber-based latex. As a result of repeated studies, as a tackifying resin emulsion, a resin obtained by emulsifying a rosin and / or a rosin derivative having an acid value with a metal compound at the carboxyl group of a rosin derivative in the presence of an emulsifier is used. It has been found that the above problems can be solved by using the same, and the present invention has been completed.
【０００８】[0008]
【発明の実施の形態】本発明の粘着付与樹脂エマルジョ
ンは、ロジン類および／または酸価を有するロジン誘導
体のカルボキシル基を金属化合物により金属塩化した構
造の化合物（以下、当該化合物を金属塩化ロジンとい
う。）を、乳化剤の存在下で乳化して得られる粘着付与
樹脂エマルジョンを含有してなるものである。BEST MODE FOR CARRYING OUT THE INVENTION The tackifying resin emulsion of the present invention is a compound having a structure in which a carboxyl group of a rosin and / or a rosin derivative having an acid value is metallized with a metal compound (hereinafter the compound is referred to as metal chloride rosin). ) Is emulsified in the presence of an emulsifier to obtain a tackifier resin emulsion.
【０００９】本発明でいうロジン類とはガムロジン、ウ
ッドロジンもしくはトール油ロジンといったロジン、ま
たは前記ロジンを用いて不均化もしくは水素添加処理し
た安定化ロジンや重合ロジン、さらには、マレイン酸、
フマル酸、（メタ）アクリル酸等で変性した不飽和酸変
性ロジンといったものが挙げられる。なお、これらのロ
ジン類の酸価は、通常、１３０〜３４０程度である。The rosins referred to in the present invention are rosins such as gum rosin, wood rosin or tall oil rosin, or stabilized rosins or polymerized rosins disproportionated or hydrogenated using the rosin, and furthermore, maleic acid,
Examples thereof include unsaturated acid-modified rosin modified with fumaric acid and (meth) acrylic acid. In addition, the acid value of these rosins is usually about 130 to 340.
【００１０】また、酸価を有するロジン誘導体として
は、前記ロジン類から誘導される酸価を有する各種公知
のものを使用できる。なお、これら酸価を有するロジン
誘導体の酸価は２〜１００程度である。これら酸価を有
するロジン誘導体としては、具体的には前記ロジン類の
エステル化物、フェノール変成物およびそのエステル化
物といったものが挙げられる。As the rosin derivative having an acid value, various known rosin derivatives having an acid value derived from the rosins can be used. In addition, the acid value of these rosin derivatives having an acid value is about 2 to 100. Specific examples of the rosin derivative having such an acid value include an esterified product of the rosin, a phenol modified product and an esterified product thereof.
【００１１】ロジン類のエステル化物としては、前記ロ
ジン類と多価アルコールとをエステル化反応させて得ら
れたものをいう。エステル化反応は、ロジン類と多価ア
ルコールとをエステル化反応させる、通常のロジン類の
エステル化条件をそのまま採用することができる。たと
えば、不活性ガス気流下に前記ロジン類と多価アルコー
ルとを通常大気圧下で１５０〜３００℃程度に加熱して
反応生成水を系外に除去することにより行う。ロジン類
と多価アルコールとの仕込み比率は、得られるロジンエ
ステル類が酸価を有するように適宜に調製する。通常は
ロジン類のカルボキシル基当量に対して０．５〜１．５
倍当量程度の水酸基を有する量の多価アルコールを使用
するのがよい。The rosin esterified product is obtained by subjecting the rosin and a polyhydric alcohol to an esterification reaction. In the esterification reaction, ordinary rosin esterification conditions for causing an esterification reaction between a rosin and a polyhydric alcohol can be employed as they are. For example, the rosin and the polyhydric alcohol are usually heated to about 150 to 300 ° C. under atmospheric pressure in an inert gas stream to remove water produced by the reaction outside the system. The charging ratio of the rosin and the polyhydric alcohol is appropriately adjusted so that the obtained rosin ester has an acid value. Usually, 0.5 to 1.5 relative to the carboxyl equivalent of rosin.
It is preferable to use an amount of polyhydric alcohol having about twice equivalent of hydroxyl groups.
【００１２】多価アルコールとしては、たとえばエチレ
ングリコール、ジエチレングリコール、プロピレングリ
コール、ネオペンチルグリコールなどの２価アルコー
ル；グリセリン、トリメチロールエタン、トリメチロー
ルプロパンなどの３価アルコール；ペンタエリスリトー
ル、ジグリセリンなどの４価アルコール；ジペンタエリ
スリトールなどの６価アルコールがあげられ、これらの
１種を単独でまたは２種以上を組合せて使用できる。Examples of the polyhydric alcohol include dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and neopentyl glycol; trihydric alcohols such as glycerin, trimethylolethane, and trimethylolpropane; and tetrahydric alcohols such as pentaerythritol and diglycerin. And a hexahydric alcohol such as dipentaerythritol. One of these can be used alone, or two or more can be used in combination.
【００１３】なお、反応に際しては、必ずしもエステル
化触媒を必要としないが、反応時間の短縮のために、た
とえば酢酸、パラトルエンスルホン酸などの酸触媒、水
酸化リチウムなどのアルカリ金属の水酸化物、水酸化カ
ルシウムなどのアルカリ土類金属の水酸化物、酸化カル
シウム、酸化マグネシウムなどの金属酸化物などを使用
することもできる。The reaction does not necessarily require an esterification catalyst. However, in order to shorten the reaction time, for example, an acid catalyst such as acetic acid or paratoluenesulfonic acid, or an alkali metal hydroxide such as lithium hydroxide is used. And hydroxides of alkaline earth metals such as calcium hydroxide, and metal oxides such as calcium oxide and magnesium oxide.
【００１４】ロジン類のフェノール変性物、およびその
エステル化物としては、前記ロジン類にフェノール類を
付加させたもの、前記ロジン類にフェノールを付加させ
次いでエステル化したもの、ならびにレゾール型フェノ
ール樹脂とロジン類を反応させて得られるいわゆるロジ
ン変性フェノール樹脂とそのエステル化物といったもの
が挙げられる。前記ロジン類のフェノール変性物のエス
テル化物は、前記ロジン類のエステル化物と同様の反応
条件、多価アルコール、触媒によって製造することがで
きる。Examples of the phenol-modified rosins and esterified products thereof include those obtained by adding phenols to the rosins, those obtained by adding phenol to the rosins and then esterification, and resole-type phenol resins and rosins. And rosin-modified phenolic resins obtained by reacting phenols and their esterified products. The phenol-modified rosin esterified product can be produced under the same reaction conditions, polyhydric alcohol, and catalyst as those for the rosin esterified product.
【００１５】本発明における、ロジン類および／または
酸価を有するロジン誘導体のカルボキシル基を金属塩化
する金属化合物としては、何ら制限されることなく、ロ
ジン類および／または酸価を有するロジン誘導体中のカ
ルボキシル基と金属塩を形成するものならばいずれも有
効に使用できる。たとえば、リチウム等の１価金属；亜
鉛、カルシウム等の２価金属；アルミニウム等の３価金
属等の各種化合物を使用できる。また、金属化合物の形
態については、特に限定しないが、前記金属の酸化物、
塩化物、水酸化物、硫酸塩等の形態で用いるのが好まし
い。なかでも、耐熱性およびロジン誘導体中のカルボキ
シル基との反応性に優れる２価の金属の化合物、特に水
酸化カルシウムを用いるのが好ましい。なお、金属化合
物の使用量は、ロジン類および／または酸価を有するロ
ジン誘導体１００重量部に対し、通常、０．１〜５重量
部程度である。In the present invention, the metal compound which metallizes a carboxyl group of a rosin and / or a rosin derivative having an acid value is not particularly limited, and the metal compound in the rosin and / or the rosin derivative having an acid value may be used. Any one that forms a metal salt with a carboxyl group can be effectively used. For example, various compounds such as a monovalent metal such as lithium; a divalent metal such as zinc and calcium; and a trivalent metal such as aluminum can be used. Further, the form of the metal compound is not particularly limited, but an oxide of the metal,
It is preferably used in the form of chloride, hydroxide, sulfate and the like. Among them, it is preferable to use a divalent metal compound having excellent heat resistance and reactivity with a carboxyl group in the rosin derivative, particularly calcium hydroxide. The amount of the metal compound used is usually about 0.1 to 5 parts by weight based on 100 parts by weight of the rosin and / or the rosin derivative having an acid value.
【００１６】ロジン類および／または酸価を有するロジ
ン誘導体のカルボキシル基を金属化合物により金属塩化
して金属塩化ロジンとする方法としては、たとえば、ロ
ジン類および／または酸価を有するロジン誘導体に、金
属化合物を添加して反応させる方法があげられる。かか
る方法としては、具体的には、ロジン類および／または
酸価を有するロジン誘導体を溶融した系に金属化合物を
添加して反応する方法、ロジン類および／または酸価を
有するロジン誘導体をベンゼン、トルエン、キシレン等
の溶剤に溶解した系に金属化合物を添加して反応し溶剤
を除去する方法等が挙げられる。As a method for converting a carboxyl group of a rosin and / or a rosin derivative having an acid value into a metal chloride by a metal compound to obtain a metal chloride rosin, for example, a method of adding a rosin and / or a rosin derivative having an acid value to a metal A method in which a compound is added and reacted is exemplified. As such a method, specifically, a method in which a metal compound is added to a system in which a rosin and / or a rosin derivative having an acid value is melted and reacted, a rosin and / or a rosin derivative having an acid value is converted to benzene, A method of adding a metal compound to a system dissolved in a solvent such as toluene or xylene and reacting to remove the solvent may be used.
【００１７】なお、金属塩化ロジンは、ロジン類および
／または酸価を有するロジン誘導体のカルボキシル基が
金属化合物により金属塩化した構造のものであればその
製法は制限されない。たとえば、金属塩化ロジンを一部
エステル化した構造を有するものとする場合には、前記
ロジン誘導体（ロジンエステル）のカルボキシル基を金
属化合物で金属塩化する方法の他に、前記ロジン類のカ
ルボキシル基を金属化合物で一部金属塩化した後、多価
アルコールでエステル化する方法や、前記ロジン類に金
属化合物と多価アルコールを同時に反応させ、ロジン類
のカルボキシル基の金属塩化とエステル化を同時に行う
方法も採用することもできる。The production method of the metal chloride rosin is not limited as long as it has a structure in which the carboxyl group of a rosin and / or a rosin derivative having an acid value is metal salted by a metal compound. For example, when a metal chloride rosin has a partially esterified structure, the carboxyl group of the rosin derivative (rosin ester) may be metallized with a metal compound. A method in which a metal compound is partially salified and then esterified with a polyhydric alcohol, or a method in which the rosin is simultaneously reacted with a metal compound and a polyhydric alcohol to simultaneously perform metal salification and esterification of a carboxyl group of the rosin. Can also be adopted.
【００１８】これら金属塩化ロジンの酸価は、通常、ロ
ジン類を用いて金属塩化した場合には６０〜２６０程
度、ロジン誘導体を用いて金属塩化した場合には０〜８
０程度である。これら金属塩化ロジンでは、ロジン誘導
体を用いた金属塩化ロジンの方が、ロジン類を用いた金
属塩化ロジンに比べて、接着性が良好であり好ましい。
特に、ロジン誘導体としてはロジン類のエステル化物が
好ましい。The acid value of the metal chloride rosin is generally about 60 to 260 when metal salt is used with rosin, and 0 to 8 when metal salt is used with rosin derivative.
It is about 0. Among these metal chloride rosins, a metal chloride rosin using a rosin derivative is preferable because it has better adhesiveness than a metal chloride rosin using a rosin.
Particularly, as the rosin derivative, an esterified product of rosin is preferable.
【００１９】前記金属塩化ロジンからなる粘着付与樹脂
は乳化剤の存在下で乳化してエマルジョン化される。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、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
化剤や、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を例示できる。乳化剤量は特に限
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。The tackifying resin comprising the metal rosin chloride is emulsified and emulsified in the presence of an emulsifier. Emulsifiers used to emulsify the tackifier resin include α-olefin sulfonates, alkyl sulfates, alkyl phenyl sulfates, polyoxyethylene alkyl phenyl ether sulfates, half-ester salts of sulfosuccinic acid of polyoxyethylene aralkyl phenyl ether, Examples thereof include anionic emulsifiers such as rosin soap and nonionic emulsifiers such as polyoxyethylene alkylphenyl ether. The amount of the emulsifier is not particularly limited, but usually, based on 100 parts by weight of the tackifying resin,
It is about 1 to 10 parts by weight, preferably 1 to 5 parts by weight in terms of solid content.
【００２０】乳化方法としては、従来より知られている
高圧乳化法、反転乳化法等を採用できる。具体的には前
記粘着付与樹脂をベンゼン、トルエン等の溶剤に溶解し
たのち前記乳化剤及び軟水を添加し、高圧乳化機を用い
てエマルジョン化した後、減圧下に溶剤を除去する方
法、粘着付与樹脂に少量のベンゼン、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たの
ち溶剤を減圧下に除去またはそのまま使用する方法、加
圧下または常圧下にて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行き転相乳化させて
エマルジョン化する方法等をあげることができる。As the emulsification method, a conventionally known high-pressure emulsification method, inversion emulsification method and the like can be employed. Specifically, a method of dissolving the tackifying resin in a solvent such as benzene and toluene, adding the emulsifier and soft water, emulsifying the mixture using a high-pressure emulsifier, and then removing the solvent under reduced pressure. A small amount of a solvent such as benzene or toluene is mixed with the mixture, and then an emulsifier is kneaded, and further hot water is gradually added to perform phase inversion emulsification to obtain an emulsion, and then the solvent is removed under reduced pressure or used as it is. Examples thereof include a method of raising the temperature above the softening point of the resin under pressure or normal pressure, kneading an emulsifier, gradually adding hot water, and performing phase inversion emulsification to emulsify.
【００２１】かくして得られた粘着付与樹脂エマルジョ
ンの固形分濃度は特に限定されるものではないが、通常
２０〜７０重量％程度となるように適宜に調整して用い
る。また、得られたエマルジョンの平均粒子径は、通常
０．２〜２μｍ程度であり、大部分は０．５μｍ以下の
粒子として均一に分散している。また、該エマルジョン
は白色ないし乳白色の外観を呈し、２〜９程度のｐＨを
有する。The solid content concentration of the tackifier resin emulsion thus obtained is not particularly limited, but is usually adjusted appropriately to be about 20 to 70% by weight. The average particle size of the obtained emulsion is usually about 0.2 to 2 μm, and most of the particles are uniformly dispersed as particles of 0.5 μm or less. The emulsion has a white to milky appearance and has a pH of about 2 to 9.
【００２２】本発明の水系粘着剤組成物はアクリル系重
合体エマルジョンおよび／またはゴム系ラテックスに前
記粘着付与樹脂エマルジョンを配合してなるものであ
る。The water-based pressure-sensitive adhesive composition of the present invention is obtained by blending the above-mentioned tackifying resin emulsion with an acrylic polymer emulsion and / or a rubber-based latex.
【００２３】アクリル系重合体エマルジョンは、一般に
各種のアクリル系粘着剤に用いられているものを使用で
き、（メタ）アクリル酸エステルを一括仕込み重合法、
モノマー逐次添加重合法、乳化モノマー逐次添加重合
法、シード重合法等の公知の乳化重合法により容易に製
造することができる。As the acrylic polymer emulsion, those generally used for various acrylic pressure-sensitive adhesives can be used.
It can be easily produced by a known emulsion polymerization method such as a monomer sequential addition polymerization method, an emulsion monomer sequential addition polymerization method, and a seed polymerization method.
【００２４】使用される（メタ）アクリル酸エステルと
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、（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
エチル等をあげることができ、これらを単独でもしくは
二種以上を混合して用いる。また、得られるエマルジョ
ンに貯蔵安定性を付与するため前記（メタ）アクリル酸
エステルに換えて（メタ）アクリル酸を少量使用しても
よい。さらに所望により（メタ）アクリル酸エステル重
合体の接着特性を損なわない程度において、たとえば、
酢酸ビニル、スチレン等の共重合可能なモノマーを併用
できる。これら（メタ）アクリル酸エステルを主成分と
する重合体のガラス転移温度は通常−７０〜０℃程度、
好ましくは−６０〜−１０℃である。０℃を越える場合
にはタックが著しく低下し好ましくない。なお、アクリ
ル系重合体エマルジョンに用いられる乳化剤にはアニオ
ン系乳化剤、部分ケン化ポリビニルアルコール等を使用
でき、その使用量は重合体１００重量部に対して０．１
〜５重量部程度、好ましくは０．５〜３重量部である。As the (meth) acrylate used, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
Examples thereof include 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. These may be used alone or as a mixture of two or more. Further, a small amount of (meth) acrylic acid may be used in place of the (meth) acrylic ester in order to impart storage stability to the obtained emulsion. Further, if desired, to the extent that the adhesive properties of the (meth) acrylate polymer are not impaired, for example,
Copolymerizable monomers such as vinyl acetate and styrene can be used in combination. The glass transition temperature of these (meth) acrylate-based polymers is usually about -70 to 0 ° C,
Preferably it is −60 to −10 ° C. If the temperature exceeds 0 ° C., the tack is remarkably reduced, which is not preferable. As the emulsifier used for the acrylic polymer emulsion, an anionic emulsifier, partially saponified polyvinyl alcohol, or the like can be used.
About 5 parts by weight, preferably 0.5 to 3 parts by weight.
【００２５】アクリル系重合体エマルジョンと粘着付与
樹脂エマルジョンの使用割合は、アクリル系重合体エマ
ルジョン１００重量部（固形分換算）に対して、粘着付
与剤樹脂エマルジョンを通常２〜４０重量部程度（固形
分換算）とするのがよい。粘着付与剤樹脂エマルジョン
が２重量部に満たない場合には、粘着付与樹脂を添加す
ることによる改質がほとんど認められず、また４０重量
部を越える場合には凝集力が低下する傾向にありいずれ
の場合も適当ではない。The ratio of the acrylic polymer emulsion and the tackifier resin emulsion used is usually about 2 to 40 parts by weight (solid content) per 100 parts by weight (solid content) of the acrylic polymer emulsion. Minute conversion). When the amount of the tackifier resin emulsion is less than 2 parts by weight, the modification by adding the tackifier resin is hardly observed, and when the amount exceeds 40 parts by weight, the cohesive strength tends to decrease. Is not appropriate.
【００２６】また、ゴム系ラテックスとしては、天然ゴ
ムラテックス、スチレン−ブタジエン共重合体ラテック
ス、クロロプレンラテックス等があげられる。天然ゴム
ラテックスとしては、水系粘着剤組成物に用いられる公
知のものを使用でき、解重合したもの、解重合しないも
ののいずれも使用できる。スチレン−ブタジエン共重合
体ラテックス、クロロプレンラテックスも通常、粘着剤
用として市販されているものを使用できる。またスチレ
ン−ブタジエン共重合体ラテックス、クロロプレンラテ
ックスはカルボキシ変性されたものでもよい。Examples of the rubber latex include natural rubber latex, styrene-butadiene copolymer latex, and chloroprene latex. As the natural rubber latex, any known natural rubber latex used in the water-based pressure-sensitive adhesive composition can be used, and any of those depolymerized and those not depolymerized can be used. Styrene-butadiene copolymer latex and chloroprene latex can also be used generally as those commercially available for pressure-sensitive adhesives. The styrene-butadiene copolymer latex and chloroprene latex may be carboxy-modified.
【００２７】ゴム系ラテックスと粘着付与樹脂エマルジ
ョンの使用割合は、ゴム系ラテックス１００重量部（固
形分換算）に対して、粘着付与樹脂エマルジョンを通常
１０〜１５０重量部程度（固形分換算）とするのがよ
い。粘着付与樹脂エマルジョンが１０重量部に満たない
場合は、粘着付与樹脂を添加することによる改質がほと
んど認められず、また１５０重量部を越える場合には凝
集力が低下する傾向にありいずれの場合も適当ではな
い。The ratio of the rubber-based latex to the tackifier resin emulsion is usually about 10 to 150 parts by weight (as solids) based on 100 parts by weight (as solids) of the rubber-based latex. Is good. When the amount of the tackifying resin emulsion is less than 10 parts by weight, almost no modification by adding the tackifying resin is recognized, and when the amount exceeds 150 parts by weight, the cohesive strength tends to decrease, and in any case, Is also not appropriate.
【００２８】本発明の水系粘着剤組成物は、ベース樹脂
としてアクリル系重合体エマルジョンとゴム系ラテック
スを併用することもでき、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、造膜助剤等を
使用することができる。The water-based pressure-sensitive adhesive composition of the present invention can use an acrylic polymer emulsion and a rubber-based latex in combination as a base resin.
Thickeners, fillers, antioxidants, water-proofing agents, film-forming auxiliaries and the like can be used.
【００２９】[0029]
【発明の効果】本発明のアクリル系重合体エマルジョン
またはゴム系ラテックスに当該粘着付与樹脂エマルジョ
ンを配合した水系粘着剤組成物は、耐熱性に優れ、かつ
ポリオレフィンに対する接着性も良好であるといった特
徴を有する。The water-based pressure-sensitive adhesive composition comprising the acrylic polymer emulsion or rubber-based latex of the present invention and the tackifier resin emulsion is characterized by having excellent heat resistance and good adhesion to polyolefin. Have.
【００３０】[0030]
【実施例】以下に製造例、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。尚、各例中、部及び％は特
記しない限りすべて重量基準である。EXAMPLES The present invention will be described in more detail with reference to Production Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples. In each example, all parts and percentages are by weight unless otherwise specified.
【００３１】実施例１ （１）（粘着付与樹脂の製造） ガムロジン（酸価１７５）５００部を１リットル容の４
つ口フラスコにとり、窒素気流下で１８０℃に昇温し、
溶融撹拌下２００℃で水酸化カルシウム１５部を加えた
後２５０℃まで昇温し、同温度で２時間反応を行い、同
温度で生成水除去のため減圧を１時間実施し、酸価１０
０、軟化点１２０℃の粘着付与樹脂を得た。Example 1 (1) (Production of tackifying resin) 500 parts of gum rosin (acid value: 175) was added to 1 liter of 4
In a two-necked flask, heated to 180 ° C under a nitrogen stream,
After adding 15 parts of calcium hydroxide at 200 ° C. under melt stirring, the temperature was raised to 250 ° C., and the reaction was carried out at the same temperature for 2 hours.
0, a tackifying resin having a softening point of 120 ° C. was obtained.
【００３２】（２）（粘着付与樹脂エマルジョンの製
造） 実施例１（１）で得られた粘着付与樹脂１００部をトル
エン６０部に１００℃にて約１時間溶解した後、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時間強撹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２９．４ＭＰａ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２０
０部を仕込み、５０℃、１３３ｈＰａの条件下に６時間
減圧蒸留を行ない、固形分５０％の粘着付与樹脂エマル
ジョンを得た。(2) (Production of tackifier resin emulsion) 100 parts of the tackifier resin obtained in Example 1 (1) were dissolved in 60 parts of toluene at 100 ° C for about 1 hour, and then dissolved at 80 ° C.
The mixture was cooled to 3 parts of an anionic emulsifier (sodium dodecylbenzenesulfonate) in terms of solid content and 160 parts of water.
And stirred vigorously at 75 ° C. for 1 hour to perform preliminary emulsification. The obtained preliminary emulsified product was emulsified under a high pressure of 29.4 MPa using a high-pressure emulsifier (manton gauulin) to obtain an emulsified product. Next, the emulsion 20 was placed in a vacuum distillation apparatus.
0 parts were charged and vacuum distillation was performed at 50 ° C. and 133 hPa for 6 hours to obtain a tackifier resin emulsion having a solid content of 50%.
【００３３】実施例２ （１）（粘着付与樹脂の製造） ガムロジン（酸価１７５）５００部を１リットル容の４
つ口フラスコにとり、窒素気流下で１８０℃に昇温し、
溶融撹拌下２００℃でペンタエリスリトール６２部を加
えた後２８０℃まで昇温し、同温度で１２時間エステル
化反応を行った（酸価２２）後、水酸化カルシウム５部
を添加し、さらに同温度で２時間反応を行い、同温度で
生成水除去のため減圧を１時間実施し、酸価１５、軟化
点１０１℃の粘着付与樹脂を得た。Example 2 (1) (Production of tackifying resin) 500 parts of gum rosin (acid value: 175) was added to 1 liter of 4
In a two-necked flask, heated to 180 ° C under a nitrogen stream,
After adding 62 parts of pentaerythritol at 200 ° C. under melt stirring, the temperature was raised to 280 ° C., and an esterification reaction was performed at the same temperature for 12 hours (acid value 22), and 5 parts of calcium hydroxide was added. The reaction was carried out at a temperature for 2 hours, and the pressure was reduced for 1 hour at the same temperature to remove generated water, thereby obtaining a tackifier resin having an acid value of 15 and a softening point of 101 ° C.
【００３４】（２）（粘着付与樹脂エマルジョンの製
造） 実施例１（２）において、粘着付与樹脂を実施例２
（１）で得られた粘着付与樹脂に変えた他は同様の操作
を行い、固形分５０％の粘着付与樹脂エマルジョンを得
た。(2) (Production of tackifier resin emulsion) In Example 1 (2),
The same operation was performed except that the tackifier resin obtained in (1) was used, to obtain a tackifier resin emulsion having a solid content of 50%.
【００３５】実施例３ （１）（粘着付与樹脂の製造） ガムロジン（酸価１７５）５００部を１リットル容の４
つ口フラスコにとり、窒素気流下で１８０℃に昇温し、
溶融撹拌下２００℃でフマル酸２０部、ペンタエリスリ
トール６５部および水酸化カルシウム５部を加えた後２
８０℃まで昇温し、同温度で１２時間エステル化反応を
行い、同温度で生成水除去のため減圧を１時間実施し、
酸価７、軟化点１２９℃の粘着付与樹脂を得た。Example 3 (1) (Production of tackifying resin) 500 parts of gum rosin (acid value: 175) was added to 1 liter of 4
In a two-necked flask, heated to 180 ° C under a nitrogen stream,
After adding 20 parts of fumaric acid, 65 parts of pentaerythritol and 5 parts of calcium hydroxide at 200 ° C. under melt stirring, 2
The temperature was raised to 80 ° C., the esterification reaction was carried out at the same temperature for 12 hours, and reduced pressure was carried out at the same temperature for 1 hour to remove generated water.
A tackifier resin having an acid value of 7 and a softening point of 129 ° C. was obtained.
【００３６】 （２）（粘着付与樹脂エマルジョンの製造）実施例１
（２）において粘着付与樹脂を実施例３（１）で得られ
た粘着付与樹脂に変えた他は同様の操作を行い、固形分
５０％の粘着付与樹脂エマルジョンを得た。(2) (Production of Tackifying Resin Emulsion) Example 1
The same operation was performed in (2) except that the tackifying resin was changed to the tackifying resin obtained in Example 3 (1) to obtain a tackifying resin emulsion having a solid content of 50%.
【００３７】実施例４ （１）（粘着付与樹脂の製造） 重合ロジン（酸価１４５）５００部を１リットル容の４
つ口フラスコにとり、窒素気流下で１８０℃に昇温し、
溶融撹拌下２２０℃でペンタエリスリトール６２部およ
び水酸化カルシウム５部を加えた後２８０℃まで昇温
し、同温度で１２時間エステル化反応を行い、同温度で
生成水除去のため減圧を１時間実施し、酸価１２、軟化
点１６５℃の粘着付与樹脂を得た。Example 4 (1) (Production of tackifying resin) 500 parts of polymerized rosin (acid value: 145) was added to 1 liter of 4
In a two-necked flask, heated to 180 ° C under a nitrogen stream,
After adding 62 parts of pentaerythritol and 5 parts of calcium hydroxide at 220 ° C. under melt stirring, the temperature was raised to 280 ° C., and an esterification reaction was carried out at the same temperature for 12 hours. The operation was performed to obtain a tackifier resin having an acid value of 12 and a softening point of 165 ° C.
【００３８】（２）（粘着付与樹脂エマルジョンの製
造） 実施例１（２）において粘着付与樹脂を実施例４（１）
で得られた粘着付与樹脂に変えた他は同様の操作を行
い、固形分５０％の粘着付与樹脂エマルジョンを得た。(2) (Production of Tackifying Resin Emulsion) In Example 1 (2), the tackifying resin was replaced with Example 4 (1).
The same operation was carried out except that the tackifier resin obtained in was used was obtained to obtain a tackifier resin emulsion having a solid content of 50%.
【００３９】製造例１（アクリル系重合体エマルジョン
の製造） （１）アクリル酸ブチル３３．００部、アクリル酸２−
エチルヘキシル１１．３０部、アクリル酸０．９６部 （２）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 撹拌装置、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、水４
４．４６部およびアニオン系乳化剤（商品名ハイテノー
ルＳ、固形分５０％、第一工業製薬（株）製）０．９０
部を溶解した後、撹拌下に上記（１）および（２）の合
計の１／１０量を添加し７０℃で窒素ガス気流下にて３
０分間予備反応を行ない、その後、（１）および（２）
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。（１）および（２）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、ア
クリル系重合体エマルジョンを得た。Production Example 1 (Production of acrylic polymer emulsion) (1) 33.00 parts of butyl acrylate, 2-acrylic acid 2-
11.30 parts of ethylhexyl, 0.96 parts of acrylic acid (2) 0.23 part of catalyst (potassium persulfate), 0.11 part of pH adjuster (heavy sodium sulfate) and 9.04 parts of water Stirrer, cooling tube, dropping In a four-necked flask equipped with a funnel and a nitrogen inlet tube, water 4
4.46 parts and 0.90 of an anionic emulsifier (trade name: Hytenol S, solid content: 50%, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
After dissolving the mixture, 1/10 of the total of the above (1) and (2) was added under stirring, and the mixture was added at 70 ° C. under a nitrogen gas stream.
Preliminary reaction was performed for 0 minutes, and then (1) and (2)
Was added dropwise over 2 hours to carry out dropwise polymerization. After dropping all of (1) and (2), the reaction was completed at 70 ° C. for 1 hour and cooled to room temperature to obtain an acrylic polymer emulsion.
【００４０】比較例１ 実施例１（２）において粘着付与樹脂をガムロジン（酸
価１７５）に変えた他は同様の操作を行い固形分５０％
の粘着付与樹脂エマルジョンを得た。Comparative Example 1 A solid content of 50% was obtained in the same manner as in Example 1 (2) except that the tackifying resin was changed to gum rosin (acid value: 175).
Was obtained.
【００４１】実施例１〜４、比較例１〜４（水系粘着剤
組成物の調製） 実施例１で得られたエマルジョン型アクリル系重合体１
００部（固形分換算）に、表１に示す粘着付与樹脂エマ
ルジョン１０部（固形分換算）を混合した調製物に、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アクリル系
粘着剤組成物を得た。得られた水系のアクリル系粘着剤
組成物を厚さ３８μｍのポリエステルフィルムにサイコ
ロ型アプリケーターにて乾燥膜厚が２５μｍ程度となる
ように塗布し、次いで該粘着剤組成物中の水分を除去し
て試料テープを作成し、以下の性能評価方法にて各種試
験を行った。Examples 1 to 4 and Comparative Examples 1 to 4 (Preparation of Aqueous Adhesive Composition) Emulsion type acrylic polymer 1 obtained in Example 1
To a preparation obtained by mixing 10 parts (in terms of solid content) of the tackifier resin emulsion shown in Table 1 with 00 parts (in terms of solid content), Primal ASE-60 was further used as an acrylic thickener.
0.5 part (in terms of solid content) (manufactured by Nippon Acrylic Co., Ltd.) was added, and the mixture was thickened with aqueous ammonia to obtain an emulsion-type acrylic pressure-sensitive adhesive composition. The obtained water-based acrylic pressure-sensitive adhesive composition was applied to a 38 μm-thick polyester film using a dice-type applicator so that the dry film thickness was about 25 μm, and then water in the pressure-sensitive adhesive composition was removed. Sample tapes were prepared, and various tests were performed by the following performance evaluation methods.
【００４２】（性能試験）以下の試験方法により粘着特
性を評価した。評価結果は表１に示す。(Performance Test) The adhesive properties were evaluated by the following test methods. The evaluation results are shown in Table 1.
【００４３】（１）接着性 試料テープ（巾２５ｍｍ×長さ１５０ｍｍ）をポリプロ
ピレン板に貼り付け、ＰＳＴＣ−１に準じて２０℃で、
剥離速度３００ｍｍ／分で１８０゜剥離を行い、その時
の巾２５ｍｍあたりの接着力（ｇ／２５ｍｍ）を測定し
た。(1) Adhesiveness A sample tape (25 mm wide × 150 mm long) was attached to a polypropylene plate, and at 20 ° C. according to PSTC-1,
180 ° peeling was performed at a peeling speed of 300 mm / min, and the adhesive force per 25 mm width (g / 25 mm) was measured.
【００４４】（２）凝集力 試料テープ（２５ｍｍ×２５ｍｍ）をステンレス板に貼
り付け、６０℃で１ｋｇ荷重し、落下時間（分）を測定
した。(2) Cohesive force A sample tape (25 mm × 25 mm) was attached to a stainless steel plate, and a 1 kg load was applied at 60 ° C., and the drop time (minute) was measured.
【００４５】[0045]
【表１】 [Table 1]
【００４６】表１中、エマルジョン：スーパーエステ
ルＥ−７２０（不均化ロジンエステルのエマルジョン、
荒川化学工業（株）製）、エマルジョン：スーパーエ
ステルＥ−６５０（重合ロジンエステルのエマルジョ
ン、荒川化学工業（株）製）を示す。In Table 1, emulsion: superester E-720 (emulsion of disproportionated rosin ester,
Arakawa Chemical Industry Co., Ltd.), Emulsion: Superester E-650 (polymerized rosin ester emulsion, Arakawa Chemical Industry Co., Ltd.).
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｊ 133/06 Ｃ０９Ｊ 133/06 // Ｃ０８Ｌ 33/04 Ｃ０８Ｌ 33/04 93/04 93/04 Ｆターム(参考） 4J002 AC00X AC01X AC08X AC09X AF02W BG03X BG04X BG05X BG06X CD19X FB07W FB08W FD34W GJ00 HA07 4J040 BA202 CA011 CA081 CA151 DF041 DF051 EE022 EE052 HA096 HA136 HA146 HA156 HA256 HB16 HD12 HD16 JA03 JA09 JB09 KA26 KA38 LA06 LA08 MA11 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C09J 133/06 C09J 133/06 // C08L 33/04 C08L 33/04 93/04 93/04 F term ( Reference) 4J002 AC00X AC01X AC08X AC09X AF02W BG03X BG04X BG05X BG06X CD19X FB07W FB08W FD34W GJ00 HA07 4J040 BA202 CA011 CA081 CA151 DF041 DF051 EE022 EE052 HA096 HA136 HA146 HA09 HA16 HA03 HA16 HA16 HA03 HA16 HA09
Claims (9)
ジン誘導体のカルボキシル基を金属化合物により金属塩
化した構造の化合物を、乳化剤の存在下で乳化して得ら
れる粘着付与樹脂エマルジョン。1. A tackifier resin emulsion obtained by emulsifying a compound having a structure in which a carboxyl group of a rosin and / or a rosin derivative having an acid value is metallized with a metal compound in the presence of an emulsifier.
ジン誘導体の酸価が２〜３４０である請求項１記載の粘
着付与樹脂エマルジョン。2. The tackifier resin emulsion according to claim 1, wherein the rosin and / or the rosin derivative having an acid value has an acid value of 2 to 340.
ジン誘導体のカルボキシル基を金属化合物により金属塩
化した構造の化合物の酸価が０〜２６０である請求項１
または２記載の粘着付与樹脂エマルジョン。3. The compound having a structure in which a carboxyl group of a rosin and / or a rosin derivative having an acid value is metallized with a metal compound has an acid value of 0 to 260.
Or the tackifier resin emulsion according to 2 above.
合ロジンおよび不飽和酸変性ロジンからなる群より選ば
れるいずれか少なくとも一種である請求項１〜３のいず
れかに記載の粘着付与樹脂エマルジョン。4. The tackifier resin emulsion according to claim 1, wherein the rosin is at least one selected from the group consisting of rosin, stabilized rosin, polymerized rosin, and unsaturated acid-modified rosin. .
物、フェノール変性物およびそのエステル化物からなる
群より選ばれるいずれか少なくとも一種である請求項１
〜４のいずれか記載の粘着付与樹脂エマルジョン。5. The rosin derivative is at least one selected from the group consisting of esterified rosins, phenol-modified rosins and esterified rosins.
5. The tackifier resin emulsion according to any one of items 4 to 4.
化物、塩化物および硫酸塩からなる群より選ばれるいず
れか少なくとも一種である請求項１〜５のいずれかに記
載の粘着付与樹脂エマルジョン。6. The tackifier according to claim 1, wherein the metal compound is at least one selected from the group consisting of divalent metal oxides, hydroxides, chlorides and sulfates. Resin emulsion.
ゴム系ラテックス、および請求項１〜６のいずれかに記
載の粘着付与樹脂エマルジョンを含有してなる水系粘着
剤組成物。7. A water-based pressure-sensitive adhesive composition comprising an acrylic copolymer emulsion or a rubber-based latex, and the tackifier resin emulsion according to any one of claims 1 to 6.
量部（固形分換算）に対して、粘着付与樹脂エマルジョ
ン２〜４０重量部（固形分換算）を配合してなる請求項
７に記載の水系粘着剤組成物。8. The aqueous pressure-sensitive adhesive according to claim 7, wherein 2 to 40 parts by weight (solid content) of the tackifier resin emulsion is blended with 100 parts by weight (solid content) of the acrylic polymer emulsion. Composition.
換算）に対して、粘着付与樹脂エマルジョン１０〜１５
０重量部（固形分換算）を配合してなる請求項７に記載
の水系粘着剤組成物。9. A tackifier resin emulsion of 10 to 15 parts by weight per 100 parts by weight of rubber latex (in terms of solid content).
The water-based pressure-sensitive adhesive composition according to claim 7, wherein the water-based pressure-sensitive adhesive composition comprises 0 parts by weight (in terms of solid content).
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11937599A JP4446210B2 (en) | 1999-04-27 | 1999-04-27 | Tackifying resin emulsion and aqueous adhesive composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11937599A JP4446210B2 (en) | 1999-04-27 | 1999-04-27 | Tackifying resin emulsion and aqueous adhesive composition |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| JP2000309771A true JP2000309771A (en) | 2000-11-07 |
| JP2000309771A5 JP2000309771A5 (en) | 2006-06-15 |
| JP4446210B2 JP4446210B2 (en) | 2010-04-07 |
Family
ID=14759963
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11937599A Expired - Lifetime JP4446210B2 (en) | 1999-04-27 | 1999-04-27 | Tackifying resin emulsion and aqueous adhesive composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4446210B2 (en) |
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| WO2016076553A1 (en) * | 2014-11-11 | 2016-05-19 | (주)엘지하우시스 | Rubber-based adhesive composition and rubber-based adhesive using same |
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