JP2005330436A - Tackifier resin emulsion - Google Patents

Tackifier resin emulsion Download PDF

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JP2005330436A
JP2005330436A JP2004151919A JP2004151919A JP2005330436A JP 2005330436 A JP2005330436 A JP 2005330436A JP 2004151919 A JP2004151919 A JP 2004151919A JP 2004151919 A JP2004151919 A JP 2004151919A JP 2005330436 A JP2005330436 A JP 2005330436A
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resin
tackifier resin
emulsion
acrylic oligomer
rosin
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JP4732710B2 (en
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Ichiro Yanaka
一朗 谷中
Keiichi Ogawa
啓一 小川
Toshiyuki Mizumoto
敏之 水本
Daigo Kiga
大悟 木賀
Satoshi Kashiwamori
聡 栢森
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Harima Chemical Inc
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Abstract

<P>PROBLEM TO BE SOLVED: To efficiently water-emulsify a tackifier resin having high softening point (for example, rosin resin or the like) without use of organic solvent. <P>SOLUTION: A tackifier resin having a softening point of 120 to 190°C is emulsified in water without solvent in the presence of an acrylic oligomer having a weight-average molecular weight of 500 to 50,000 under application of a pressure thereby producing the tackifier emulsion of this invention. This emulsion is different from the conventional emulsion using an acrylic polymer of high molecular weight, several ten thousands, which has been widely used as base polymer, and contains the acrylic oligomer having specific low molecular weight, particularly, oligomer prepared by continuous block polymerization as an auxiliary component, therefore, it can be smoothly water-emulsified by the non-solvent phase inversion method using simple equipment, even in the case where the resin has high softening temperature, and can be smoothly water-emulsified as the production cost is suppressed lower. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は粘着付与剤樹脂エマルションに関して、高圧を要しない簡便な設備を利用して生産コストの上昇を抑えながら、高軟化点樹脂を効率良く水性エマルション化できるものを提供する。   The present invention provides a tackifier resin emulsion capable of efficiently converting a high softening point resin into an aqueous emulsion while suppressing an increase in production cost using a simple facility that does not require high pressure.

粘着付与剤樹脂エマルションは、一般的に、アクリルエマルションや天然ゴムラテックス、ＳＢＲ及びＣＲなどの合成ゴム系の各種ラテックスに代表されるベースポリマーに対して粘着特性等の向上を目的として添加され、紙や各種プラスチックス基材に塗布したラベル、テープ、シートなどの粘・接着製品に広く使用されている。
特に、近年は、シックハウス症候群などのＶＯＣの問題、作業衛生面や安全性などの観点から、従来の溶剤型粘着剤は環境に優しい水系エマルション型のものに大きく転換されつつある。また、粘着剤に求められる性能も高度化し、被着体として多用されるポリオレフィンなどの非極性プラスチックに対する粘着力の向上や、耐熱性を付与する見地から、ロジン系樹脂などの粘着付与剤樹脂の中でも特に高軟化点樹脂の使用が一般的になっている。 A tackifier resin emulsion is generally added for the purpose of improving adhesive properties and the like to base polymers represented by various latexes of synthetic rubbers such as acrylic emulsion, natural rubber latex, SBR and CR. It is widely used for sticky / adhesive products such as labels, tapes and sheets applied to various plastics substrates.
In particular, in recent years, from the viewpoints of VOC problems such as sick house syndrome, occupational hygiene, and safety, conventional solvent-based pressure-sensitive adhesives are being largely converted to environmentally friendly water-based emulsion types. In addition, the performance required for pressure-sensitive adhesives has also been improved, and from the viewpoint of imparting heat resistance to improved adhesion to non-polar plastics such as polyolefins frequently used as adherends, tackifier resins such as rosin resins can be used. Among them, the use of a high softening point resin is particularly popular.

そこで、先ず、高軟化点を含む特定組成のロジン系樹脂のエマルションを含有する水性粘着剤として、次の特許文献１〜２が挙げられる。
上記特許文献１には、ポリオレフィン基材の特に曲面に対する密着性などを改善することを目的として、ベースポリマーとしてのアクリル系重合体エマルションと、ロジン変性フェノール樹脂や重合ロジンの多価アルコールエステルなどから選ばれ、且つ、１１０〜１５０℃の高軟化点を有する粘着付与剤樹脂のエマルションとを配合した水性粘着剤組成物が開示されている(特許請求の範囲、第２頁右上欄参照)。
当該文献１の実施例では、高軟化点樹脂をエマルション化する方法として、トルエンに溶解した後に乳化剤水溶液を添加し、高圧乳化機でエマルション化してから溶剤を除去する方法が行われているが(第４頁の実施例１参照)、この方法では完全に溶剤を取り除くことが困難であり、上記ＶＯＣや環境保全の問題を解消できない。 Then, the following patent documents 1-2 are mentioned as an aqueous adhesive containing the emulsion of the rosin resin of the specific composition containing a high softening point first.
Patent Document 1 discloses an acrylic polymer emulsion as a base polymer, a rosin-modified phenolic resin, a polyhydric alcohol ester of polymerized rosin, and the like for the purpose of improving the adhesion of a polyolefin base material particularly to a curved surface. An aqueous pressure-sensitive adhesive composition that is selected and blended with an emulsion of a tackifier resin having a high softening point of 110 to 150 ° C. is disclosed (see claims, upper right column on page 2).
In the example of the document 1, as a method of emulsifying a high softening point resin, a method of adding an aqueous emulsifier solution after dissolving in toluene and emulsifying with a high-pressure emulsifier and then removing the solvent is performed ( (See Example 1 on page 4), it is difficult to completely remove the solvent by this method, and the above VOC and environmental conservation problems cannot be solved.

また、上記特許文献２には、デヒドロアビエチン酸残基を６０重量％以上含有する特定組成のロジンエステル（軟化点は７５〜１３０℃が好ましい；第３頁右上欄参照）を(メタ)アクリル酸アルキルエステルを主成分とする単量体混合物に溶解し、これを水性媒体中で重合することにより、凝集力が大きく、タックと接着性に優れるエマルション型粘着剤を製造する方法が開示されている(特許請求の範囲、第２頁左上欄参照)。
この粘着剤は、上記特許文献１とは異なり、有機溶剤を使用しないで粘着性付与のための高軟化点樹脂を水性媒体中で重合するものであり、環境保全などには有効であるが、デヒドロアビエチン酸量が低減するとポリマーの重合度が低下する問題があり、使用できる粘着付与剤樹脂が制限されてしまう。 Further, in Patent Document 2, a rosin ester having a specific composition containing a dehydroabietic acid residue of 60% by weight or more (softening point is preferably 75 to 130 ° C .; see the upper right column on page 3) is (meth) acrylic acid. Disclosed is a method for producing an emulsion-type pressure-sensitive adhesive having a high cohesive force and excellent tack and adhesiveness by dissolving in a monomer mixture containing an alkyl ester as a main component and polymerizing the mixture in an aqueous medium. (See Claims, page 2, upper left column).
Unlike the above-mentioned Patent Document 1, this pressure-sensitive adhesive polymerizes a high softening point resin for imparting tackiness in an aqueous medium without using an organic solvent, and is effective for environmental conservation. When the amount of dehydroabietic acid is reduced, there is a problem that the degree of polymerization of the polymer is lowered, and the tackifier resin that can be used is limited.

一方、環境保全などに資する見地から、有機溶剤を使用しない塊状重合法で製造したアクリル系重合体を主成分とする粘・接着剤が、次の特許文献３〜５に列挙されている。
上記特許文献３には、塊状重合により得られた高分子量アクリル系重合体であって、アクリル酸、アクリル酸アルキルエステル等のアクリル酸系単量体単位を主成分とし、架橋性官能基を所定割合で有し、且つ、数平均分子量、ガラス転移温度並びに分子量分布（Ｍｗ／Ｍｎ）を特定化することにより、界面活性剤を含まず、重合体組成の制限が少なく、平均分子量付近の成分の量が多くて、凝集性、耐水性、耐熱性などに優れる感圧接着剤が開示されている(請求項４〜５、段落３９〜４１参照)。この場合、上記高分子量アクリル系重合体の数平均分子量は、請求項１では１万〜１００万である。また、ロジン系樹脂、テルペン系樹脂、石油系樹脂などの粘着付与剤樹脂を配合可能なことが開示されている(段落１９参照)。 On the other hand, the following patent documents 3-5 list the adhesives and adhesives which have as a main component the acrylic polymer manufactured by the block polymerization method which does not use an organic solvent from the viewpoint of contributing to environmental conservation.
Patent Document 3 discloses a high molecular weight acrylic polymer obtained by bulk polymerization, mainly composed of acrylic acid monomer units such as acrylic acid and alkyl acrylate, and has a crosslinkable functional group. By specifying the number average molecular weight, glass transition temperature, and molecular weight distribution (Mw / Mn), the surfactant is not included, the polymer composition is less restricted, and the components around the average molecular weight are included. There is disclosed a pressure-sensitive adhesive which is large in amount and excellent in cohesion, water resistance, heat resistance and the like (see claims 4 to 5 and paragraphs 39 to 41). In this case, the number average molecular weight of the high molecular weight acrylic polymer is 10,000 to 1,000,000 in claim 1. Further, it is disclosed that a tackifier resin such as rosin resin, terpene resin, and petroleum resin can be blended (see paragraph 19).

上記特許文献４には、(メタ)アクリル酸、アルキル(メタ)アクリレートなどのアクリル系モノマーと、所定の重量平均分子量とガラス転移温度を有する非重合性ポリマーが結合した重合性ポリマー（即ち、凝集力向上用に添加されるマクロモノマー；重量平均分子量は２,０００〜５万(段落１３参照)）と、ラジカル性重合開始剤とを、スクリュー押出機中で所定の重合温度にて塊状重合法でラジカル共重合し、その際に重合開始剤の半減期と上記スクリュー押出機での重合性組成物の平均滞留時間との比率を特定化することにより、基材強度低下の原因となる低分子量分含有量を低減したアクリル系ホットメルト粘着剤の製法が開示されている(特許請求の範囲、段落６、段落３３、段落４４参照)。   Patent Document 4 discloses a polymerizable polymer (that is, agglomerated) in which an acrylic monomer such as (meth) acrylic acid or alkyl (meth) acrylate, and a non-polymerizable polymer having a predetermined weight average molecular weight and glass transition temperature are combined. Macromonomer added to improve force; weight average molecular weight of 2,000 to 50,000 (see paragraph 13)) and radical polymerization initiator in bulk polymerization method at a predetermined polymerization temperature in a screw extruder By specifying the ratio between the half-life of the polymerization initiator and the average residence time of the polymerizable composition in the screw extruder, a low molecular weight that causes a reduction in substrate strength A method for producing an acrylic hot melt pressure-sensitive adhesive with a reduced content is disclosed (see claims, paragraphs 6, 33, and 44).

上記特許文献５には、アクリル系重合体（重量平均分子量は１０万〜５０万(段落１４参照)）を特定の塊状重合により得るとともに、これに２−ヒドロキシ−３−フェノキシプロピル(メタ)アクリレートなどの放射線反応性単量体を加えて、無溶剤で放射線硬化型の粘着剤組成物とし、これを支持体上に塗布した後、放射線で硬化させることにより、耐熱性と耐水性を改善し、接着力と保持力のバランスに優れる粘着シート類の製法が開示されている(請求項１と段落４参照)。   In Patent Document 5, an acrylic polymer (weight average molecular weight is 100,000 to 500,000 (see paragraph 14)) is obtained by specific bulk polymerization, and 2-hydroxy-3-phenoxypropyl (meth) acrylate is obtained. Add a radiation-reactive monomer such as a solvent-free radiation-curable adhesive composition, apply it on a support, and then cure with radiation to improve heat resistance and water resistance. A method for producing pressure-sensitive adhesive sheets having an excellent balance between adhesive force and holding force is disclosed (see claim 1 and paragraph 4).

さらに、特許文献６には、透明性を損なうことなく、熱成形性や耐摩擦性などを改善する目的で、(メタ)アクリル酸アルキルエステルなどのアクリル系モノマーにシリコーン系モノマーを塊状重合法などで反応させて得られた、重量平均分子量が５０００〜１００万、好ましくは５万〜３０万である高透明性のシリコーンアクリル系ランダム共重合体であって(請求項１〜５、段落１、段落１３、段落３２、段落６２、段落１０７参照)、熱硬化型接着剤などを用途にする(段落８３参照)ものが開示されている。   Furthermore, in Patent Document 6, for the purpose of improving thermoformability, friction resistance, etc. without impairing transparency, a silicone-based monomer is mass-polymerized with an acrylic monomer such as (meth) acrylic acid alkyl ester. A highly transparent silicone acrylic random copolymer having a weight average molecular weight of 5,000 to 1,000,000, preferably 50,000 to 300,000, obtained by reacting in (Claim 1-5, Paragraph 1, Paragraph 13, Paragraph 32, Paragraph 62, and Paragraph 107), and thermosetting adhesives and the like (see Paragraph 83) are disclosed.

特開昭６３−２５６６７２号公報JP 63-256672 A 特開平１−１６１０７８号公報Japanese Patent Laid-Open No. 1-161078 特開平６−８０７３５号公報Japanese Patent Laid-Open No. 6-80735 特開平８−６０１１８号公報JP-A-8-60118 特開平８−２６９４１１号公報Japanese Patent Laid-Open No. 8-269411 特開２００２−８０５４８号公報JP 2002-80548 A

一般に、有機溶剤を使用しないで粘着付与剤樹脂をエマルション化する方法として転相乳化法が知られているが、この方式で高軟化点樹脂をエマルション化すると、転相水の沸騰を抑えるために乳化系を高圧に保持する必要があり、軟化点の上昇に伴って、より高圧に耐える設備が必要となり、コストが嵩むという問題がある。
この点を詳述すると、高軟化点樹脂を転相乳化法で乳化するには、軟化点以上の温度で樹脂を保持し、液状化させる必要があり、その際、安定して転相乳化させるために、樹脂の軟化点より約３０〜５０℃以上に加温させることが一般に行われている。
その一方、当該転相乳化は、溶融した樹脂中に任意の乳化剤を溶かし込んでおき、水(一般的には温水)を徐々に滴下していき、Ｗ／Ｏ(油中水)型エマルションからＯ／Ｗ(水中油)型エマルションに相反転させることを基本原理とするため、いうまでもなく、滴下する水が沸騰することを抑制する必要があり、樹脂温度が１００℃（厳密にいうと９０℃程度）以上になるような場合には、反応容器を加圧する必要がある。
従って、例えば、樹脂軟化点が１２０℃であれば反応容器の温度は約１７０℃とする必要があり、その場合の反応容器内の圧力は約１ＭＰａ(１０ｋｇ／ｃｍ2)で良いが、樹脂軟化点が１２０℃を越えると容器内圧力を１ＭＰａ以上に保持する必要があり、圧力容器のパッキンや配管等に対する耐圧性の付与を考慮すると、装置が高価になってしまう。 Generally, a phase inversion emulsification method is known as a method for emulsifying a tackifier resin without using an organic solvent, but when a high softening point resin is emulsified with this method, in order to suppress boiling of phase inversion water. It is necessary to maintain the emulsification system at a high pressure, and as the softening point increases, a facility that can withstand a higher pressure is required, which increases the cost.
In detail, in order to emulsify the high softening point resin by the phase inversion emulsification method, it is necessary to hold the resin at a temperature equal to or higher than the softening point and liquefy it. For this reason, it is generally performed to heat to about 30 to 50 ° C. or more from the softening point of the resin.
On the other hand, in the phase inversion emulsification, an arbitrary emulsifier is dissolved in a molten resin, and water (generally warm water) is gradually added dropwise from a W / O (water-in-oil) emulsion. Since the basic principle is to invert the phase to an O / W (oil-in-water) emulsion, it is needless to say that it is necessary to suppress boiling of the dropped water, and the resin temperature is 100 ° C. (strictly speaking, In such a case, it is necessary to pressurize the reaction vessel.
Therefore, for example, if the resin softening point is 120 ° C., the temperature of the reaction vessel needs to be about 170 ° C., and the pressure in the reaction vessel in that case may be about 1 MPa (10 kg / cm 2 ). When the point exceeds 120 ° C., it is necessary to maintain the pressure in the container at 1 MPa or more, and the apparatus becomes expensive considering the provision of pressure resistance to the packing or piping of the pressure container.

前述したように、粘・接着剤においては、非極性プラスチックへの接着性の向上や、耐熱性の付与などが強く要請されており、樹脂の軟化点が高いほどこの要請により良く応えられるが、上記理由により高軟化点樹脂ほど転相乳化により水性エマルション化することが困難になる。
本発明は、環境保全や労働衛生に資する見地から、ロジン系樹脂などの粘着付与剤樹脂に有機溶剤を用いない方法、特に転相乳化法を適用するに際して、高軟化点樹脂であっても、生産コストの上昇を抑えながら円滑に水性エマルション化することを技術的課題とする。 As described above, in adhesives and adhesives, there is a strong demand for improved adhesion to non-polar plastics and the provision of heat resistance, and the higher the softening point of the resin, the better this request can be met. For the above reasons, it becomes difficult to form an aqueous emulsion by phase inversion emulsification as the resin has a higher softening point.
The present invention is a method that does not use an organic solvent for a tackifier resin such as a rosin resin from the viewpoint of contributing to environmental protection and occupational health, and particularly when applying a phase inversion emulsification method, even if it is a high softening point resin, A technical problem is to make an aqueous emulsion smoothly while suppressing an increase in production cost.

本発明者らは、無溶剤方式で高軟化点の粘着付与剤樹脂をエマルション化することを鋭意研究した結果、当該エマルション化には粘着剤のベースポリマーとして汎用されるアクリル系共重合体の共存が大きく寄与すること、特に、このアクリル系共重合体の分子量がその操作の難易性に大きく影響することを突き止めた。
即ち、従来のベースポリマーに汎用される数十万以上の高分子量のアクリル系ポリマー、或は、上記特許文献３〜５に示されたアクリル系共重合体とは異なり、特定の低分子量を有するアクリル系オリゴマー（中でも連続塊状重合で得られたものが好ましい）を補助成分として共存させると、ロジン系樹脂などの粘着付与剤樹脂の軟化点が高い場合であっても、無溶剤方式、特に公知の転相乳化法により、高圧を要しない簡便な設備で効率良く容易に水性エマルション化できることを見い出して、本発明を完成した。 As a result of diligent research into emulsification of a tackifier resin having a high softening point in a solvent-free manner, the present inventors coexisted with an acrylic copolymer that is widely used as a base polymer for an adhesive. Has made a great contribution, and in particular, it has been found that the molecular weight of the acrylic copolymer greatly affects the difficulty of the operation.
That is, it has a specific low molecular weight unlike the acrylic polymer having a high molecular weight of several hundreds of thousands or more commonly used for the conventional base polymer, or the acrylic copolymer shown in Patent Documents 3 to 5 above. When an acrylic oligomer (especially one obtained by continuous bulk polymerization) is coexistent as an auxiliary component, even if the softening point of a tackifier resin such as a rosin resin is high, a solvent-free method, particularly known Thus, the present invention has been completed by finding that it is possible to efficiently and easily form an aqueous emulsion with simple equipment that does not require high pressure.

即ち、本発明１は、軟化点が１２０〜１９０℃の粘着付与剤樹脂を、重量平均分子量が５００〜５０,０００のアクリル系オリゴマーの共存下で、無溶剤且つ加圧条件にて水中に分散させたことを特徴とする粘着付与剤樹脂エマルションである。   That is, the present invention 1 disperses a tackifier resin having a softening point of 120 to 190 ° C. in water in a solvent-free and pressurized condition in the presence of an acrylic oligomer having a weight average molecular weight of 500 to 50,000. It is a tackifier resin emulsion characterized by having been made.

本発明２は、上記本発明１において、アクリル系オリゴマーが、連続塊状重合で製造した低分子量の共重合体であることを特徴とする粘着付与剤樹脂エマルションである。   The present invention 2 is the tackifier resin emulsion according to the present invention 1, wherein the acrylic oligomer is a low molecular weight copolymer produced by continuous bulk polymerization.

本発明３は、上記本発明１又は２において、粘着付与剤樹脂とアクリル系オリゴマーを溶融混合し、転相乳化で樹脂分を水中に分散することを特徴とする粘着付与剤樹脂エマルションである。   The present invention 3 is the tackifier resin emulsion according to the present invention 1 or 2, wherein the tackifier resin and the acrylic oligomer are melt-mixed and the resin component is dispersed in water by phase inversion emulsification.

本発明４は、上記本発明１〜３のいずれかにおいて、粘着付与剤樹脂がロジン系樹脂、テルペン系樹脂、石油系樹脂の少なくとも一種であることを特徴とする請求項１〜３のいずれか１項に記載の粘着付与剤樹脂エマルションである。   Invention 4 is any one of Inventions 1 to 3, wherein the tackifier resin is at least one of a rosin resin, a terpene resin, and a petroleum resin. It is a tackifier resin emulsion described in item 1.

本発明５は、上記本発明１〜４のいずれかにおいて、粘着付与剤樹脂とアクリル系オリゴマーの混合割合が、固形分換算でアクリル系オリゴマー／粘着付与剤樹脂＝２０〜８０重量部／８０〜２０重量部であることを特徴とする粘着付与剤樹脂エマルションである。   The present invention 5 is the invention according to any one of the present inventions 1 to 4, wherein the mixing ratio of the tackifier resin and the acrylic oligomer is acrylic oligomer / tackifier resin = 20-80 parts by weight / 80-in terms of solid content. It is a tackifier resin emulsion characterized by being 20 parts by weight.

本発明６は、上記本発明１〜５のいずれかにおいて、粘着付与剤樹脂エマルションの平均粒子経が０.１０〜０.５０μｍであることを特徴とする粘着付与剤樹脂エマルションである。   The present invention 6 is the tackifier resin emulsion according to any one of the present inventions 1 to 5, wherein the tackifier resin emulsion has an average particle size of 0.10 to 0.50 μm.

本発明７は、連続塊状重合で製造した重量平均分子量が５００〜５０,０００のアクリル系オリゴマーと軟化点が１２０〜１９０℃の粘着付与剤樹脂とを、固形分換算でアクリル系オリゴマー／粘着付与剤樹脂＝２０〜８０重量部／８０〜２０重量部の割合で溶融混合し、
上記溶融樹脂中に乳化剤の存在下で水を添加することにより、油中水型エマルションを水中油型エマルションに相反転させることを特徴とする粘着付与剤樹脂エマルションの製造方法である。 The present invention 7 is an acrylic oligomer / tackifier in terms of solid content, prepared by continuous mass polymerization, an acrylic oligomer having a weight average molecular weight of 500 to 50,000 and a tackifier resin having a softening point of 120 to 190 ° C. Agent resin = 20-80 parts by weight / 80-20 parts by weight,
It is a method for producing a tackifier resin emulsion, wherein the water-in-oil emulsion is phase-inverted to an oil-in-water emulsion by adding water to the molten resin in the presence of an emulsifier.

(1)従来、有機溶剤を使用しないで高軟化点の粘着付与剤樹脂をエマルション化するには転相乳化法が知られているが、樹脂の軟化点が１２０℃を越えると、水の沸騰を抑制するために反応容器の内圧を１ＭＰａ以上の高圧にする必要がある。このため、パッキンや配管などに耐圧設計を施した特別の高圧設備が必要になり、耐圧設計を要しない簡便な反応設備を使用できないことから、生産コストが嵩み、管理も煩雑になる。
本発明では、転相乳化などの無溶剤乳化に際して、高軟化点(１２０〜１９０℃)の粘着付与剤樹脂を特定の低分子量を有するアクリル系オリゴマーを共存させて乳化するため、反応容器内を低い圧力に保持しても容易に水性エマルション化でき、例えば、転相乳化においては、１７０℃以下で且つ１ＭＰａ以下の反応容器であっても充分に流動性のある状態で乳化分散物を得ることができる。従って、高軟化点の粘着付与剤樹脂に無溶剤の乳化方式を適用しても、高圧を要しない簡便な設備で生産コストの上昇を抑えながら、高軟化点樹脂を効率良く円滑にエマルション化できる。
また、この際に使用されるアクリル系オリゴマーは、粘着剤のベースポリマーに汎用されるアクリル系共重合体に属するため、当該オリゴマーを共存させても粘着付与剤樹脂エマルションの特性に支障を来すことはない。 (1) Conventionally, a phase inversion emulsification method is known for emulsifying a tackifier resin having a high softening point without using an organic solvent. However, when the softening point of the resin exceeds 120 ° C., boiling of water occurs. In order to suppress this, it is necessary to set the internal pressure of the reaction vessel to a high pressure of 1 MPa or more. For this reason, special high-pressure equipment in which pressure-resistant design is applied to packing, piping, etc. is required, and since a simple reaction equipment that does not require pressure-resistant design cannot be used, production cost increases and management becomes complicated.
In the present invention, during solvent-free emulsification such as phase inversion emulsification, a tackifier resin having a high softening point (120 to 190 ° C.) is emulsified in the presence of an acrylic oligomer having a specific low molecular weight. Even when kept at a low pressure, it can be easily formed into an aqueous emulsion. For example, in phase inversion emulsification, an emulsified dispersion can be obtained in a sufficiently fluid state even in a reaction vessel of 170 ° C. or lower and 1 MPa or lower. Can do. Therefore, even if a solvent-free emulsification method is applied to the high softening point tackifier resin, the high softening point resin can be efficiently and smoothly emulsified while suppressing an increase in production cost with simple equipment that does not require high pressure. .
In addition, since the acrylic oligomer used at this time belongs to an acrylic copolymer that is widely used for the base polymer of the pressure-sensitive adhesive, even if the oligomer coexists, the characteristics of the tackifier resin emulsion are hindered. There is nothing.

(2)溶剤乳化法で粘着付与剤樹脂の水性エマルションを製造するには、溶剤除去の際の発泡を抑制するための消泡剤を必要としたが、この消泡剤が粘着剤の濡れ性を損なうため、最終工程で粘着剤を塗布する際にハジキを起こして、均質に塗布できないという問題があった。
これに対して、本発明は無溶剤型の高軟化点樹脂エマルションであり、製造工程中で溶剤除去のための消泡剤を必要としないため、水性エマルションに消泡剤を含まず、最終の粘着剤を塗布する際のハジキの問題を解消して、粘着剤を均質、良好に塗布できる。 (2) In order to produce an aqueous emulsion of a tackifier resin by a solvent emulsification method, an antifoaming agent for suppressing foaming during solvent removal was required. Therefore, there is a problem in that the application of the pressure-sensitive adhesive in the final process causes repelling and cannot be applied uniformly.
In contrast, the present invention is a solvent-free high-softening point resin emulsion and does not require an antifoaming agent for solvent removal in the production process. The problem of repelling at the time of applying the adhesive can be solved, and the adhesive can be applied uniformly and satisfactorily.

本発明は、特定の低分子量を有するアクリル系オリゴマーを補助成分として共存させながら、高軟化点の粘着付与剤樹脂を無溶剤且つ加圧条件にて水中に分散した粘着付与剤樹脂エマルションであり、特に、転相乳化により水性エマルション化したものである。   The present invention is a tackifier resin emulsion in which a tackifier resin having a high softening point is dispersed in water in a solventless and pressurized condition while coexisting an acrylic oligomer having a specific low molecular weight as an auxiliary component, In particular, it is an aqueous emulsion by phase inversion emulsification.

上記粘着付与剤樹脂は、ロジン系樹脂、テルペン系樹脂、石油系樹脂を初め、ダンマル、コーパル、シェラック、アルキルフェノール樹脂、キシレン樹脂などを単用又は併用することができ、特に、本発明４に示すように、ロジン系樹脂、テルペン系樹脂、石油系樹脂が好ましい。
上記ロジン系樹脂はロジン類及びロジン誘導体を単用又は併用できる。当該ロジン類は、トールロジン、ガムロジン、ウッドロジンであり、また、不均斉化ロジン、重合ロジン、水素化ロジン、或いはその他の化学的に修飾されたロジン、又はこれらの精製物を含む概念である。 As the tackifier resin, rosin resin, terpene resin, petroleum resin, dammar, copal, shellac, alkylphenol resin, xylene resin and the like can be used singly or in combination. Thus, rosin resin, terpene resin, and petroleum resin are preferable.
As the rosin resin, rosins and rosin derivatives can be used alone or in combination. The rosins are tall rosin, gum rosin and wood rosin, and are a concept including a disproportionated rosin, a polymerized rosin, a hydrogenated rosin, other chemically modified rosins, or purified products thereof.

上記ロジン誘導体としては、ロジンエステル類、不飽和カルボン酸変性ロジン類、不飽和カルボン酸変性ロジンエステル類、或は、ロジン変性フェノール類、或は、ロジン類や不飽和カルボン酸で変性したロジン類のカルボキシル基を還元処理したロジンアルコール類などが挙げられる。
上記ロジンエステル類は、上記ロジン類と多価アルコールを公知のエステル化法により製造したものをいう。エステル化反応の条件としては、ロジン類と多価アルコールの仕込比率はロジンのカルボキシル基当量に対してアルコールの水酸基当量比換算でＣＯＯＨ／ＯＨ＝１／(０.２〜２.０)程度、反応温度は１５０〜３００℃程度、反応時間は２〜３０時間程度が夫々適当である。
上記多価アルコールとしては、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、トリメチレングリコール、テトラメチレングリコール、１,３−ブタンジオール、１,６−ヘキサンジオール等の２価アルコール、グリセリン、トリメチロールプロパン、トリメチロールエタン、トリエチロールエタン等の３価アルコール、ペンタエリスリトール、ジグリセリン等の４価アルコール、ジペンタエリスリトール等の６価アルコール、或いは、トリエタノールアミン、トリプロパノールアミン、トリイソプロパノールアミン、Ｎ−イソブチルジエタノールアミン、Ｎ−ノルマルブチルジエタノールアミン等のアミノアルコールなどが挙げられる。 Examples of the rosin derivatives include rosin esters, unsaturated carboxylic acid-modified rosins, unsaturated carboxylic acid-modified rosin esters, rosin-modified phenols, or rosins modified with rosins and unsaturated carboxylic acids. And rosin alcohols obtained by reducing the carboxyl group.
The said rosin ester means what manufactured the said rosin and polyhydric alcohol by the well-known esterification method. As the conditions for the esterification reaction, the charge ratio of rosins and polyhydric alcohol is about COOH / OH = 1 / (0.2 to 2.0) in terms of the hydroxyl group equivalent ratio of alcohol to the carboxyl group equivalent of rosin, The reaction temperature is suitably about 150 to 300 ° C., and the reaction time is suitably about 2 to 30 hours.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, neopentyl glycol, trimethylene glycol, tetramethylene glycol, dihydric alcohols such as 1,3-butanediol and 1,6-hexanediol, glycerin, trimethylolpropane, Trivalent alcohols such as trimethylolethane and triethylolethane, tetravalent alcohols such as pentaerythritol and diglycerin, hexavalent alcohols such as dipentaerythritol, or triethanolamine, tripropanolamine, triisopropanolamine, N-isobutyl Examples include amino alcohols such as diethanolamine and N-normal butyl diethanolamine.

上記不飽和カルボン酸変性ロジン類は、公知の方法により上記ロジン類にα,β−不飽和カルボン酸類を反応させたものをいう。この場合、反応温度は１５０〜３００℃程度、反応温度時間は１〜２４時間程度である。α,β−不飽和カルボン酸類の仕込量は、ロジン類１００重量部に対してα,β−不飽和カルボン酸類２０重量部程度以下である。
上記α,β−不飽和カルボン酸類としては、フマル酸、(無水)マレイン酸、イタコン酸、(無水)シトラコン酸、アクリル酸、メタクリル酸などが挙げられる。 The unsaturated carboxylic acid-modified rosin is obtained by reacting the rosin with an α, β-unsaturated carboxylic acid by a known method. In this case, the reaction temperature is about 150 to 300 ° C., and the reaction temperature time is about 1 to 24 hours. The charged amount of α, β-unsaturated carboxylic acids is about 20 parts by weight or less of α, β-unsaturated carboxylic acids with respect to 100 parts by weight of rosins.
Examples of the α, β-unsaturated carboxylic acids include fumaric acid, (anhydrous) maleic acid, itaconic acid, (anhydrous) citraconic acid, acrylic acid, and methacrylic acid.

上記不飽和カルボン酸変性ロジンエステル類は、上記ロジン類に多価アルコール類とα,β−不飽和カルボン酸類を順次、又は同時に反応させることにより得られる。
多価アルコールとのエステル化反応、α,β−不飽和カルボン酸類との強化反応は前述の通りである。 The unsaturated carboxylic acid-modified rosin esters can be obtained by reacting the rosins with polyhydric alcohols and α, β-unsaturated carboxylic acids sequentially or simultaneously.
The esterification reaction with polyhydric alcohol and the strengthening reaction with α, β-unsaturated carboxylic acids are as described above.

上記テルペン系樹脂としては、α−ピネンやβ−ピネンの重合物、これらのフェノール又は芳香族変性物、水素添加変性物、炭化水素変性物等が挙げられる。
上記石油系樹脂としては、脂肪族(Ｃ5)系樹脂、芳香族(Ｃ9)系樹脂、共重合(Ｃ5／Ｃ9)系樹脂、クマロン樹脂及びクマロン−インデン樹脂、ジシクロペンタジエン系石油樹脂、水素添加石油樹脂、スチレン系などのピュアーモノマー系石油樹脂などが挙げられる。 Examples of the terpene resin include α-pinene and β-pinene polymers, phenol or aromatic modified products, hydrogenated modified products, and hydrocarbon modified products.
Examples of the petroleum resins include aliphatic (C 5 ) resins, aromatic (C 9 ) resins, copolymerized (C 5 / C 9 ) resins, coumarone resins and coumarone-indene resins, and dicyclopentadiene oils. Examples include resins, hydrogenated petroleum resins, and pure monomer petroleum resins such as styrene.

本発明で使用する粘着付与剤樹脂は、耐熱性や対オレフィン粘着性を保持する見地から、１２０〜１９０℃の高軟化点樹脂であることが必要である。
軟化点が１２０℃未満では、オレフィン基材への密着性や耐熱性が不足し、また、軟化点が１９０℃を越えるとタックなどが低下する恐れがあるうえ、１９０℃を越える樹脂を製造するのは実質上容易でない。
一般に、樹脂の分子量が増大すると樹脂軟化点は高くなる傾向があるため、例えば、ロジン系樹脂を粘着付与剤樹脂とする場合、不均斉化ロジンや重合ロジンを不飽和カルボン酸で変性し、又は多価アルコールでエステル化し、或は変性化とエステル化を組み合わせることなどにより、高軟化点樹脂が得られる。 The tackifier resin used in the present invention needs to be a high softening point resin at 120 to 190 ° C. from the viewpoint of maintaining heat resistance and olefin adhesion.
If the softening point is less than 120 ° C, the adhesion to the olefin substrate and the heat resistance are insufficient, and if the softening point exceeds 190 ° C, the tack may be lowered, and a resin exceeding 190 ° C is produced. It is not easy in practice.
Generally, since the resin softening point tends to increase as the molecular weight of the resin increases, for example, when a rosin resin is used as a tackifier resin, a disproportionated rosin or a polymerized rosin is modified with an unsaturated carboxylic acid, or A high softening point resin can be obtained by esterification with a polyhydric alcohol or a combination of modification and esterification.

本発明で補助成分として使用するアクリル系共重合体は、重量平均分子量が５００〜５万である比較的低分子量の共重合体（即ち、アクリル系オリゴマー）である。
分子量が５万を越えると、高軟化点の粘着付与剤樹脂を転相乳化などでエマルション化することが難しくなり、水性エマルションを得るという本発明の本来の目的が達成できない。分子量が５００より小さいと、オリゴマー自体が揮発性を有して、ＶＯＣなどの問題を引き起こし、環境保全や労働衛生に資するという本発明の所期の目的に反する恐れがある。
また、当該アクリル系オリゴマーのガラス転移温度は０℃以下が適当であり、好ましくは−１０℃〜−８０℃である。ガラス転移温度が０℃より高いと、粘着剤にした場合にベースポリマーとの相溶性が低下する恐れがある。
上記アクリル系オリゴマーは、塊状重合、乳化重合、懸濁重合などの公知の重合方法で得られたものであれば特に制限はなく、共重合体の分子量分布及び組成分布を狭くする見地から、重合方法は連続塊状重合が好ましい。但し、環境保全や労働衛生などに資するという本発明の目的から、有機溶剤を使用する溶液重合法は上記重合方法から排除される。 また、連続塊状重合法でアクリル系オリゴマーを得る場合、基本的に溶剤は用いないか、ごく少量である。さらに、重合開始剤は用いないか、ごく少量であり、ジ−ｔ−ブチル−ペルオキシド、ベンゾイルパーオキシド、２,２′−アゾビス−イソブチロニトリルなどの公知のラジカル重合開始剤が使用できる。連鎖移動剤は使用しない方が好ましく、反応温度は高温であり、反応時間はごく短時間であることが好ましい。
上記アクリル系オリゴマーの組成に特に制限はなく、(メタ)アクリル酸、(メタ)アクリル酸エステルを主要な構成モノマーとして、必要に応じて、マレイン酸、スチレン、ビニルエステルなどのビニルモノマーが使用できることはいうまでもなく、すべてのモノマーを(メタ)アクリル酸、(メタ)アクリル酸エステルで構成したオールアクリル系オリゴマーや、アクリル／スチレン系のオリゴマーなどが挙げられる。
当該アクリル系オリゴマーの市販品としては、ＡＲＵＦＯＮシリーズ（東亞合成化学工業社製）がある。 The acrylic copolymer used as an auxiliary component in the present invention is a relatively low molecular weight copolymer (that is, an acrylic oligomer) having a weight average molecular weight of 500 to 50,000.
When the molecular weight exceeds 50,000, it becomes difficult to emulsify a tackifier resin having a high softening point by phase inversion emulsification or the like, and the original purpose of the present invention of obtaining an aqueous emulsion cannot be achieved. If the molecular weight is less than 500, the oligomer itself has volatility, which causes problems such as VOC, which may be contrary to the intended purpose of the present invention, which contributes to environmental protection and occupational health.
In addition, the glass transition temperature of the acrylic oligomer is suitably 0 ° C. or less, preferably −10 ° C. to −80 ° C. When the glass transition temperature is higher than 0 ° C., the compatibility with the base polymer may be lowered when the pressure-sensitive adhesive is used.
The acrylic oligomer is not particularly limited as long as it is obtained by a known polymerization method such as bulk polymerization, emulsion polymerization, suspension polymerization or the like, and is polymerized from the viewpoint of narrowing the molecular weight distribution and composition distribution of the copolymer. The method is preferably continuous bulk polymerization. However, the solution polymerization method using an organic solvent is excluded from the above polymerization method for the purpose of the present invention which contributes to environmental protection and occupational health. When an acrylic oligomer is obtained by a continuous bulk polymerization method, basically no solvent is used or a very small amount is used. Further, a polymerization initiator is not used or is very small amount, and a known radical polymerization initiator such as di-t-butyl-peroxide, benzoyl peroxide, 2,2'-azobis-isobutyronitrile can be used. It is preferable not to use a chain transfer agent, the reaction temperature is high, and the reaction time is preferably very short.
The composition of the acrylic oligomer is not particularly limited, and (meth) acrylic acid, (meth) acrylic acid ester as the main constituent monomer, and vinyl monomers such as maleic acid, styrene, vinyl ester can be used as necessary. Needless to say, all acrylic oligomers in which all monomers are composed of (meth) acrylic acid and (meth) acrylic acid esters, acrylic / styrene oligomers, and the like can be mentioned.
As a commercial product of the acrylic oligomer, there is an ARUFON series (manufactured by Toagosei Co., Ltd.).

前記ロジン系樹脂、テルペン系樹脂、石油系樹脂などの高軟化点樹脂は単用又は併用でき、アクリル系オリゴマーと粘着付与剤樹脂との混合割合は、本発明５に示すように、固形分換算でアクリル系オリゴマー／粘着付与剤樹脂＝２０〜８０重量部／８０〜２０重量部であり、３０〜４０重量部／７０〜６０重量部が好ましい。
高軟化点樹脂が８０重量部より多くアクリル系オリゴマーが少なくなると、高軟化点樹脂を無溶剤でエマルション化することが難しくなり、また、高軟化点樹脂が２０重量部より少なくアクリル系オリゴマーが多くなると、対オレフィン密着性や耐熱性が充分でなくなる。 High softening point resins such as the rosin resin, terpene resin, petroleum resin and the like can be used alone or in combination, and the mixing ratio of the acrylic oligomer and the tackifier resin is calculated as solid content as shown in the present invention 5. And acrylic oligomer / tackifier resin = 20 to 80 parts by weight / 80 to 20 parts by weight, preferably 30 to 40 parts by weight / 70 to 60 parts by weight.
When the amount of the high softening point resin is more than 80 parts by weight and the amount of the acrylic oligomer is small, it becomes difficult to emulsify the high softening point resin without solvent, and the amount of the high softening point resin is less than 20 parts by weight and the amount of the acrylic oligomer is large. As a result, adhesion to olefins and heat resistance are not sufficient.

本発明の粘着付与剤樹脂エマルションは、連続塊状重合などで得られた特定の低分子量を有するアクリル系オリゴマーを共存させながら、上記高軟化点樹脂を無溶剤且つ加圧条件にて水中に分散させて水性エマルション化したものである。このエマルション化は常圧より高いが、例えば、１ＭＰａを越える高圧には及ばない領域での加圧条件で実施される。
水性エマルションを得るには、転相乳化法、高圧無溶剤型乳化法、或はその他の任意の無溶剤乳化法が適用できるが、設備の簡易性や生産コストの低減に鑑みて、転相乳化法が特に好ましい。
上記転相乳化法は、加圧下で粘着付与剤樹脂を加熱溶融した後、乳化剤と水を混合溶解した乳化水を撹拌しながら徐々に加えることにより、或は、溶融樹脂に乳化剤を添加し、次いで水を徐々に加えることにより、油中水型エマルションを、樹脂分が水中に分散した水中油型エマルションに相反転させる方法である。
上記高圧無溶剤乳化法は、加圧下で溶融した粘着付与剤樹脂と乳化水を予備混合し、粗粒子の水性エマルションを調製した後、各種ミキサー、コロイドミル、高圧乳化機、高圧吐出型乳化機などの各種乳化機を用いて微細乳化させる方法である。
また、本発明では、無溶剤下で粘着付与剤樹脂エマルションを得ることを目的とするため、粘着付与剤樹脂を有機溶剤に溶解させ、乳化水を予備混合して粗乳化した後、微細乳化し、常圧或は減圧下で加熱して上記有機溶剤を除去する溶剤型乳化法は、本発明の水性エマルションを得る方法から排除される。
一方、本発明７は、粘着付与剤樹脂エマルションを製造する際に、上述の通り、アクリル系オリゴマーの重合方法を連続塊状重合に、粘着付与剤樹脂とアクリル系オリゴマーの配合比を適正な範囲に、また、エマルションの製法を転相乳化法に夫々特定化したもので、具体的には、連続塊状重合で得られた重量平均分子量が５００〜５万のアクリル系オリゴマーと軟化点が１２０〜１９０℃の粘着付与剤樹脂とを、固形分換算でアクリル系オリゴマー／粘着付与剤樹脂＝２０〜８０重量部／８０〜２０重量部の割合で溶融混合し、上記溶融樹脂中に乳化剤の存在下で水を添加することにより、油中水型エマルションを水中油型エマルションに相反転させる粘着付与剤樹脂エマルションの製造方法である。 The tackifier resin emulsion of the present invention disperses the above high softening point resin in water without solvent and under pressure conditions while coexisting with an acrylic oligomer having a specific low molecular weight obtained by continuous bulk polymerization or the like. It is an aqueous emulsion. This emulsification is carried out under a pressurizing condition in a region that is higher than normal pressure but does not reach a high pressure exceeding 1 MPa, for example.
In order to obtain an aqueous emulsion, a phase inversion emulsification method, a high-pressure solventless emulsification method, or any other solventless emulsification method can be applied. However, in view of simplicity of equipment and reduction in production cost, phase inversion emulsification is possible. The method is particularly preferred.
In the phase inversion emulsification method, after the tackifier resin is heated and melted under pressure, the emulsified water and the emulsifier mixed with water are gradually added with stirring, or the emulsifier is added to the molten resin, Next, by gradually adding water, the water-in-oil emulsion is phase-inverted to an oil-in-water emulsion in which the resin content is dispersed in water.
The above high-pressure solventless emulsification method involves premixing a tackifier resin melted under pressure and emulsified water to prepare an aqueous emulsion of coarse particles, and then various mixers, colloid mills, high-pressure emulsifiers, high-pressure discharge type emulsifiers. This is a method of finely emulsifying using various emulsifiers.
In the present invention, in order to obtain a tackifier resin emulsion in the absence of a solvent, the tackifier resin is dissolved in an organic solvent, pre-mixed with emulsified water, coarsely emulsified, and then finely emulsified. The solvent-type emulsification method in which the organic solvent is removed by heating under normal pressure or reduced pressure is excluded from the method for obtaining the aqueous emulsion of the present invention.
On the other hand, when manufacturing the tackifier resin emulsion according to the present invention 7, as described above, the polymerization method of the acrylic oligomer is changed to the continuous bulk polymerization, and the mixing ratio of the tackifier resin and the acrylic oligomer is set to an appropriate range. In addition, the emulsion production method is specified as a phase inversion emulsification method, specifically, an acrylic oligomer having a weight average molecular weight of 500 to 50,000 obtained by continuous bulk polymerization and a softening point of 120 to 190. C. Tackifier resin at 0.degree. C. is melt-mixed at a ratio of acrylic oligomer / tackifier resin = 20 to 80 parts by weight / 80 to 20 parts by weight in terms of solid content, and in the presence of an emulsifier in the molten resin. This is a method for producing a tackifier resin emulsion in which a water-in-oil emulsion is phase-inverted into an oil-in-water emulsion by adding water.

上記粘着付与剤樹脂を転相乳化などでエマルション化する際に使用する乳化剤は特に制限されることなく、アニオン系、ノニオン系、カチオン系の各種の乳化剤が使用できるが、アニオン系乳化剤及びノニオン系乳化剤などを単用または併用することが好ましい。また、その使用量は固形の粘着付与剤樹脂１００重量部に対して１〜１０重量部、好ましくは１〜５重量部とするのが適当である。   The emulsifier used when emulsifying the tackifier resin by phase inversion emulsification is not particularly limited, and various anionic, nonionic, and cationic emulsifiers can be used. Anionic emulsifier and nonionic emulsifier It is preferable to use an emulsifier or the like alone or in combination. The amount used is suitably 1 to 10 parts by weight, preferably 1 to 5 parts by weight per 100 parts by weight of the solid tackifier resin.

上記アニオン系乳化剤には、有機スルホン酸、硫酸エステルのアルカリ金属塩、アンモニウム塩などが挙げられ、具体的には下記の(1)〜(6)などである。
(1)ドデシルベンゼンスルホン酸ナトリウムなどのアルキルアリールスルホン酸塩類。
(2)ラウリル硫酸ナトリウム、オレイル硫酸ナトリウムなどのアルキル（又はアルケニル）硫酸エステル塩類
(3)ポリオキシエチレンラウリルエーテル硫酸ナトリウム、ポリオキシエチレンオレイルエーテル硫酸ナトリウムなどのポリオキシエチレンアルキル（又はアルケニル）エーテル硫酸エステル塩類。
(4)ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム、ポリオキシエチレンスチリルフェニルエーテル硫酸ナトリウムなどのポリオキシエチレンアルキルアリールエーテル硫酸エステル塩類。
(5)モノオクチルスルホコハク酸ナトリウム、ジオクチルスルホコハク酸ナトリウム、ポリオキシエチレンラウリルスルホコハク酸２ナトリウムなどのアルキルスルホコハク酸エステル塩並びにその誘導体類。
(6)アルキルジフェニルエーテルジスルホン酸ナトリウムなどのアルキルジアリールエーテルジスルホン酸塩並びにその誘導体類。 Examples of the anionic emulsifier include organic sulfonic acids, alkali metal salts of sulfuric esters, ammonium salts, and the like, and specifically include the following (1) to (6).
(1) Alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate.
(2) Alkyl (or alkenyl) sulfate esters such as sodium lauryl sulfate and oleyl sulfate
(3) Polyoxyethylene alkyl (or alkenyl) ether sulfates such as sodium polyoxyethylene lauryl ether sulfate and sodium polyoxyethylene oleyl ether sulfate.
(4) Polyoxyethylene alkylaryl ether sulfate salts such as sodium polyoxyethylene nonylphenyl ether sulfate and sodium polyoxyethylene styryl phenyl ether sulfate.
(5) Alkylsulfosuccinic acid ester salts such as sodium monooctylsulfosuccinate, sodium dioctylsulfosuccinate, disodium polyoxyethylene laurylsulfosuccinate, and derivatives thereof.
(6) Alkyl diaryl ether disulfonates such as sodium alkyl diphenyl ether disulfonate and derivatives thereof.

また、上記ノニオン系乳化剤としては下記の(1)〜(7)などが挙げられる。
(1)ポリオキシエチレンラウリルエーテル、ポリオキシエチレンオレイルエーテルなどのポリオキシエチレンアルキル（又はアルケニル）エーテル類。
(2)ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンスチリルフェニルエーテルなどのポリオキシエチレンアルキルフェニルエーテル類。
(3)ソルビタンモノラウレート、ソルビタントリオレエートなどのソルビタン高級脂肪酸エステル類。
(4)ポリオキシエチレンソルビタンモノラウレートなどのポリオキシエチレンソルビタン高級脂肪酸エステル類。
(5)ポリオキシエチレンモノラウレート、ポリオキシエチレンモノオレエートなどのポリオキシエチレン高級脂肪酸エステル類。
(6)オレイン酸モノグリセライド、ステアリン酸モノグリセライドなどのグリセリン高級脂肪酸エステル類。
(7)ポリオキシエチレン・ポリオキシプロピレン・ブロックコポリマー。 Examples of the nonionic emulsifier include the following (1) to (7).
(1) Polyoxyethylene alkyl (or alkenyl) ethers such as polyoxyethylene lauryl ether and polyoxyethylene oleyl ether.
(2) Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonyl phenyl ether and polyoxyethylene styryl phenyl ether.
(3) Higher sorbitan fatty acid esters such as sorbitan monolaurate and sorbitan trioleate.
(4) Polyoxyethylene sorbitan higher fatty acid esters such as polyoxyethylene sorbitan monolaurate.
(5) Polyoxyethylene higher fatty acid esters such as polyoxyethylene monolaurate and polyoxyethylene monooleate.
(6) Glycerin higher fatty acid esters such as oleic acid monoglyceride and stearic acid monoglyceride.
(7) Polyoxyethylene / polyoxypropylene block copolymer.

粘着付与剤樹脂の水性エマルションを製造する際の乳化剤としては、その他、必要に応じて合成高分子系の乳化剤を使用することもできる。
合成高分子系乳化剤とは、スチレン、α−メチルスチレン、ビニルトルエン、(メタ)アクリル酸、マレイン酸、(メタ)アクリル酸エステル類、アクリルアマイド、酢酸ビニル、スチレンスルホン酸、イソプレンスルホン酸、ビニルスルホン酸、アリルスルホン酸、２−(メタ)アクリルアミド−２−メチルプロパンスルホン酸などの重合性モノマーを２種以上重合させて得られる重合体を水酸化ナトリウム、水酸化カリウム、アンモニアなどのアルカリ類で塩形成させて水に分散又は可溶化させた水分散性重合体である。また、上記モノマーの他にも、重合可能なモノマー類を限定されることなく使用でき、重合方法も特に制約されることはない。 As an emulsifier for producing an aqueous emulsion of a tackifier resin, a synthetic polymer emulsifier may be used as necessary.
Synthetic polymer emulsifiers include styrene, α-methylstyrene, vinyltoluene, (meth) acrylic acid, maleic acid, (meth) acrylic esters, acrylic amide, vinyl acetate, styrene sulfonic acid, isoprene sulfonic acid, vinyl Polymers obtained by polymerizing two or more polymerizable monomers such as sulfonic acid, allyl sulfonic acid, and 2- (meth) acrylamide-2-methylpropane sulfonic acid are converted to alkalis such as sodium hydroxide, potassium hydroxide, and ammonia. It is a water-dispersible polymer which is salt-formed and dispersed or solubilized in water. In addition to the above monomers, polymerizable monomers can be used without limitation, and the polymerization method is not particularly limited.

得られた粘着付与剤樹脂のエマルションは、本発明６に示すように、平均粒子径は０.１０〜０.５０μｍ、好ましくは０.２０〜０.４０μｍである。０.５０μｍを越えると、エマルションの貯蔵安定性、機械安定性などが低下する恐れがあり(後述の試験例参照)、０.１０μｍより小さいと、粘度が増す恐れがある。   The resulting tackifier resin emulsion has an average particle size of 0.10 to 0.50 μm, preferably 0.20 to 0.40 μm, as shown in the present invention 6. If it exceeds 0.50 μm, the storage stability and mechanical stability of the emulsion may be lowered (see test examples described later), and if it is less than 0.10 μm, the viscosity may increase.

以下、高軟化点の粘着付与剤樹脂としてのロジン系樹脂の製造例、当該製造例で得られたロジン系樹脂をアクリル系オリゴマーの共存下で無溶剤転相乳化した本発明の粘着付与剤樹脂エマルションの実施例、当該実施例で得られた粘着付与剤樹脂エマルションの安定性、平均粒子径などの各種評価試験例を順次説明する。製造例、実施例、試験例中の「％」、「部」は基本的に重量基準である。
尚、本発明は下記の実施例、試験例などに拘束されるものではなく、本発明の技術的思想の範囲内で任意の変形をなし得ることは勿論である。 Hereinafter, a production example of a rosin resin as a tackifier resin having a high softening point, a tackifier resin of the present invention obtained by solvent-free phase inversion emulsification of the rosin resin obtained in the production example in the presence of an acrylic oligomer Examples of the emulsion, various evaluation test examples such as stability and average particle diameter of the tackifier resin emulsion obtained in the examples will be described in order. “%” And “parts” in production examples, examples and test examples are basically based on weight.
It should be noted that the present invention is not limited to the following examples and test examples, and can be arbitrarily modified within the scope of the technical idea of the present invention.

《粘着付与剤樹脂の製造例》
製造例１〜３のうち、製造例１は軟化点１２０℃のアクリル酸変性不均斉化ロジンエステルの例、製造例２は軟化点１６６℃のアクリル酸変性重合ロジンエステルの例、製造例３は軟化点１８５℃のアクリル酸・無水マレイン酸変性重合ロジンエステルの例である。 << Example of production of tackifier resin >>
Among Production Examples 1 to 3, Production Example 1 is an example of an acrylic acid-modified disproportionated rosin ester having a softening point of 120 ° C., Production Example 2 is an example of an acrylic acid-modified polymerized rosin ester having a softening point of 166 ° C., and Production Example 3 is It is an example of acrylic acid / maleic anhydride modified polymerized rosin ester having a softening point of 185 ° C.

(1)製造例１
攪拌装置、冷却器、温度計及び窒素導入管を備えた反応容器に、ガムロジン１００部を仕込んだ後、窒素ガスを吹き込みながら加熱溶融させた。その後、攪拌を開始して１６０℃で９８％アクリル酸４.８部を滴下しながら加えた。添加後１９０℃まで昇温して２時間反応させた。
次いで、不均斉化触媒として５％パラジウムカーボン０.０７部を添加し、２６０℃まで昇温して不均斉化反応を行った。反応終了後、触媒を濾過して容器より排出し、アクリル酸変性不均斉化ロジンを得た。得られた樹脂の性状は、酸価１８６.５、軟化点９８℃であった。
続いて、上記アクリル酸変性不均斉化ロジン１００部を再度反応容器に仕込み、窒素ガスを吹き込みながら加熱溶融した後、１９０℃まで昇温してペンタエリスリトール１４.４部を加えた。次いで、２８０℃まで昇温して同温度下で８時間脱水縮合反応させた。
得られたアクリル酸変性不均斉化ロジンエステルの軟化点は１２０℃、酸価は１２.５であった。 (1) Production example 1
A reaction vessel equipped with a stirrer, a cooler, a thermometer and a nitrogen introduction tube was charged with 100 parts of gum rosin and then heated and melted while blowing nitrogen gas. Then, stirring was started and 4.8 parts of 98% acrylic acid was added dropwise at 160 ° C. After the addition, the temperature was raised to 190 ° C. and reacted for 2 hours.
Next, 0.07 part of 5% palladium carbon was added as a disproportionation catalyst, and the temperature was raised to 260 ° C. to carry out a disproportionation reaction. After completion of the reaction, the catalyst was filtered and discharged from the container to obtain acrylic acid-modified disproportionated rosin. The properties of the obtained resin were an acid value of 186.5 and a softening point of 98 ° C.
Subsequently, 100 parts of the acrylic acid-modified disproportionated rosin was charged again into the reaction vessel, heated and melted while blowing nitrogen gas, heated to 190 ° C., and 14.4 parts of pentaerythritol was added. Next, the temperature was raised to 280 ° C., and a dehydration condensation reaction was performed at the same temperature for 8 hours.
The resulting acrylic acid-modified disproportionated rosin ester had a softening point of 120 ° C. and an acid value of 12.5.

(2)製造例２
攪拌装置、冷却器、温度計及び窒素導入管を備えた反応容器に、重合ロジン(重合部６６.０％、酸価１５０.１、軟化点１３３℃)１００部を仕込んだ後、窒素ガスを吹き込みながら加熱溶融させた。その後、攪拌を開始して１６０℃で９８％アクリル酸２.６部を 滴下しながら加えた。添加後１９０℃まで昇温して２時間反応させた後、容器より排出し、アクリル酸変性重合ロジンを得た。得られた樹脂の性状は、酸価１６０.９、軟化点１４３℃であった。
続いて、上記アクリル酸変性重合ロジン１００部を再度反応容器に仕込み、窒素ガスを吹き込みながら加熱溶融した後、１９０℃まで昇温してペンタエリスリトール１２.２部を加えた。次いで、２８０℃まで昇温して同温度下で８時間脱水縮合反応させた。
得られたアクリル酸変性重合ロジンエステルの軟化点は１６６℃、酸価は１５.６であった。 (2) Production example 2
Into a reaction vessel equipped with a stirrer, a cooler, a thermometer, and a nitrogen introduction tube, 100 parts of polymerized rosin (polymerization part 66.0%, acid value 150.1, softening point 133 ° C.) was charged, and then nitrogen gas was supplied. It was heated and melted while blowing. Thereafter, stirring was started, and 2.6 parts of 98% acrylic acid was added dropwise at 160 ° C. After the addition, the temperature was raised to 190 ° C. and reacted for 2 hours, and then discharged from the container to obtain an acrylic acid-modified polymerized rosin. The properties of the obtained resin were an acid value of 160.9 and a softening point of 143 ° C.
Subsequently, 100 parts of the acrylic acid-modified polymerized rosin was charged again into the reaction vessel, heated and melted while blowing nitrogen gas, heated to 190 ° C., and 12.2 parts of pentaerythritol was added. Next, the temperature was raised to 280 ° C., and a dehydration condensation reaction was performed at the same temperature for 8 hours.
The resulting acrylic acid-modified polymerized rosin ester had a softening point of 166 ° C. and an acid value of 15.6.

(3)製造例３
攪拌装置、冷却器、温度計及び窒素導入管を備えた反応容器に、重合ロジン（重合部６６.０％、酸価１５０.１、軟化点１３３℃）１００部を仕込んだ後、窒素ガスを吹き込みながら加熱溶融させた。その後、攪拌を開始して１６０℃で無水マレイン酸３.０部を仕込んだ後、９８％アクリル酸４.０部を滴下しながら加えた。添加後１９０℃まで昇温して２時間反応させた後、容器より排出し、アクリル酸・無水マレイン酸変性重合ロジンを得た。得られた樹脂の性状は、酸価１７５.０、軟化点１４８℃であった。
続いて、当該アクリル酸・無水マレイン酸変性重合ロジン１００部を再度反応容器に仕込み、窒素ガスを吹き込みながら加熱溶融した後、１９０℃まで昇温してペンタエリスリトール１４.４部を加えた。次いで、２８０℃まで昇温して同温度下で８時間脱水縮合反応させた。
得られたアクリル酸・無水マレイン酸変性重合ロジンエステルの軟化点は１８５℃、酸価は１８.７であった。 (3) Production example 3
Into a reaction vessel equipped with a stirrer, a cooler, a thermometer and a nitrogen introduction tube, 100 parts of a polymerized rosin (polymerization part 66.0%, acid value 150.1, softening point 133 ° C.) was charged, and then nitrogen gas was introduced. It was heated and melted while blowing. Thereafter, stirring was started and 3.0 parts of maleic anhydride was charged at 160 ° C., and 4.0 parts of 98% acrylic acid was added dropwise. After the addition, the temperature was raised to 190 ° C. and reacted for 2 hours, and then discharged from the container to obtain acrylic acid / maleic anhydride modified polymerized rosin. The properties of the obtained resin were an acid value of 175.0 and a softening point of 148 ° C.
Subsequently, 100 parts of the acrylic acid / maleic anhydride modified polymerized rosin was charged again into the reaction vessel, heated and melted while blowing nitrogen gas, heated to 190 ° C., and 14.4 parts of pentaerythritol was added. Next, the temperature was raised to 280 ° C., and a dehydration condensation reaction was performed at the same temperature for 8 hours.
The resulting acrylic acid / maleic anhydride-modified polymerized rosin ester had a softening point of 185 ° C. and an acid value of 18.7.

《粘着付与剤樹脂エマルションの実施例》
そこで、上記製造例１〜３で得られた高軟化点の各ロジン系樹脂を特定の低分子量を有するアクリル系オリゴマーの共存下で無溶剤転相乳化して、粘着付与剤樹脂エマルションを製造した。
実施例１〜１２のうち、実施例１は後述のアクリル系オリゴマー１の共存下で上記製造例１のロジン系樹脂をエマルション化した例、実施例２はアクリル系オリゴマー１の共存下で上記製造例２のロジン系樹脂をエマルション化した例、実施例３〜６はアクリル系オリゴマー１の共存下で上記製造例３のロジン系樹脂をエマルション化した例、実施例７は後述のアクリル系オリゴマー２の共存下で製造例３のロジン系樹脂をエマルション化した例、実施例８は後述のアクリル系オリゴマー３の共存下で製造例３のロジン系樹脂をエマルション化した例、実施例１１は後述のアクリル系オリゴマー４の共存下で製造例１のロジン系樹脂をエマルション化した例、実施例１２はアクリル系オリゴマー１の共存下で製造例３のロジン系樹脂をエマルション化した例である。実施例１１は重量平均分子量１.１万の上記アクリル系オリゴマー４を使用した例、他の実施例は重量平均分子量が１千〜５千の範囲内のアクリル系オリゴマー１〜３を使用した例である。実施例３はロジン系樹脂とアクリル系オリゴマーの混合量がアクリル系オリゴマー：ロジン系樹脂＝２０％：８０％の例、実施例５はアクリル系オリゴマー：ロジン系樹脂＝５０％：５０％の例、実施例６はアクリル系オリゴマー：ロジン系樹脂＝７０％：３０％の例、その他の実施例はアクリル系オリゴマー：ロジン系樹脂＝３０％：７０％の例である。実施例１２は転相乳化の際の水を添加する行程で、ディスクタービンの回転数を他の実施例より低減した例である。実施例９はロジン系樹脂(製造例１と３)を併用した例、実施例１０はアクリル系オリゴマー(オリゴマー１と２)を併用した例、他の実施例はロジン系樹脂とアクリル系オリゴマーを夫々単用した例である。
一方、比較例１〜２のうち、比較例１はアクリル系オリゴマーを共存させず、ロジン系樹脂のみを使用して転相乳化したブランク例である。比較例２はアクリル系オリゴマーを共存させながら、粘着付与剤樹脂を転相乳化ではなく溶剤乳化法でエマルション化した例である。 << Example of tackifier resin emulsion >>
Therefore, each rosin resin having a high softening point obtained in Production Examples 1 to 3 was subjected to solvent-free phase inversion emulsification in the presence of an acrylic oligomer having a specific low molecular weight to produce a tackifier resin emulsion. .
Among Examples 1 to 12, Example 1 is an example in which the rosin resin of Production Example 1 is emulsified in the coexistence of acrylic oligomer 1 described later, and Example 2 is the above production in the coexistence of acrylic oligomer 1. Examples of emulsifying the rosin resin of Example 2, Examples 3 to 6 are examples of emulsifying the rosin resin of Production Example 3 in the presence of the acrylic oligomer 1, and Example 7 is an acrylic oligomer 2 described later. Example 8 in which the rosin resin of Production Example 3 was emulsified under the coexistence of Example 3, Example 8 was an example in which the rosin resin of Production Example 3 was emulsified in the presence of the acrylic oligomer 3 described later, and Example 11 was described later. Example 12 in which the rosin resin of Production Example 1 was emulsified in the presence of acrylic oligomer 4, Example 12 emulsified the rosin resin of Production Example 3 in the presence of acrylic oligomer 1 ® is the emission of the example. Example 11 is an example using the above acrylic oligomer 4 having a weight average molecular weight of 11,000, and other examples are examples using acrylic oligomers 1 to 3 having a weight average molecular weight in the range of 1,000 to 5,000. It is. Example 3 is an example in which the mixing amount of rosin resin and acrylic oligomer is acrylic oligomer: rosin resin = 20%: 80%, and Example 5 is an example of acrylic oligomer: rosin resin = 50%: 50%. Example 6 is an example of acrylic oligomer: rosin resin = 70%: 30%, and other examples are examples of acrylic oligomer: rosin resin = 30%: 70%. Example 12 is an example in which the number of rotations of the disk turbine is reduced compared to other examples in the process of adding water during phase inversion emulsification. Example 9 is an example in which a rosin resin (Production Examples 1 and 3) is used in combination, Example 10 is an example in which an acrylic oligomer (Oligomer 1 and 2) is used in combination, and other examples are a rosin resin and an acrylic oligomer. This is an example of single use.
On the other hand, of Comparative Examples 1 and 2, Comparative Example 1 is a blank example obtained by phase inversion emulsification using only a rosin resin without coexisting an acrylic oligomer. Comparative Example 2 is an example in which the tackifier resin is emulsified by a solvent emulsification method instead of phase inversion emulsification while an acrylic oligomer coexists.

(1)実施例１
(ａ)ロジン系樹脂
上記製造例１で得られたロジン系樹脂
(ｂ)アクリル系オリゴマー１
東亞合成株式会社製のＡＲＵＦＯＮ ＵＰ−１０４１
（重量平均分子量：１,８００、ガラス転移温度：−２５℃（ＤＳＣ法））
上記(ａ)のロジン系樹脂（製造例１）と上記(ｂ)のアクリル系オリゴマー１を、製造例１：アクリル系オリゴマー１＝７０％：３０％の割合で含有した混合物の合計１００部を、反応容器（Ｔ.Ｋ.タービンミクサー：特殊機化工業株式会社製）に入れ、約０.８５ＭＰａの加圧下にて約１７０℃で加熱し、溶融させた。当該反応容器はダブルメカニカルシールで軸封された回転軸にディスクタービンを具備した攪拌装置を有するとともに、耐久圧力は０.８８ＭＰａである。
そして、同圧力（約０.８５ＭＰａ）に保持された滴下用容器に、予め乳化剤（ソフタノール ＭＥＳ−９：日本触媒株式会社製（有効成分２４％））を２０部入れておき、溶融した樹脂が入った上記反応容器中に、ディスクタービンの回転数を５００ｒｐｍとして攪拌しながら徐々に添加していった。
次いで、同圧力（約０.８５ＭＰａ）に保持された滴下用容器に予め水８０部を入れておき、内温を約１７０℃に保持し、且つ、ディスクタービンの回転数を１,５００ｒｐｍとして攪拌しながら、乳化剤が添加された上記樹脂中に約１時間かけて水を徐々に添加することにより、油中水型を水中油型エマルションに相反転して粘着付与剤樹脂エマルションを得た。その後、得られた粘着付与剤樹脂エマルションにトリエタノールアミンを添加し、ｐＨを７.５に調整した。また、固形分も適量の水を添加することにより５０％に調整した。 (1) Example 1
(a) Rosin resin Resin resin obtained in Production Example 1
(b) Acrylic oligomer 1
ARUFON UP-1041 manufactured by Toagosei Co., Ltd.
(Weight average molecular weight: 1,800, glass transition temperature: −25 ° C. (DSC method))
A total of 100 parts of a mixture containing the rosin resin of (a) (Production Example 1) and the acrylic oligomer 1 of (b) in the ratio of Production Example 1: Acrylic oligomer 1 = 70%: 30% , Put in a reaction vessel (TK turbine mixer: manufactured by Tokushu Kika Kogyo Co., Ltd.), heated at about 170 ° C. under a pressure of about 0.85 MPa, and melted. The reaction vessel has a stirrer equipped with a disk turbine on a rotating shaft sealed with a double mechanical seal, and has a durable pressure of 0.88 MPa.
Then, 20 parts of an emulsifier (SOFTANOL MES-9: manufactured by Nippon Shokubai Co., Ltd. (active ingredient 24%)) was previously placed in a dropping container kept at the same pressure (about 0.85 MPa), and the molten resin The disk reactor was gradually added to the above reaction vessel while stirring at a rotation speed of 500 rpm.
Next, 80 parts of water is put in a dropping container kept at the same pressure (about 0.85 MPa) in advance, the internal temperature is kept at about 170 ° C., and the rotation speed of the disk turbine is set at 1,500 rpm. Meanwhile, by gradually adding water to the resin to which the emulsifier was added over about 1 hour, the water-in-oil type was inverted to the oil-in-water emulsion to obtain a tackifier resin emulsion. Thereafter, triethanolamine was added to the obtained tackifier resin emulsion to adjust the pH to 7.5. The solid content was also adjusted to 50% by adding an appropriate amount of water.

(2)実施例２
上記実施例１を基本として、ロジン系樹脂を製造例１から前記製造例２のものに変更し、その他の条件を実施例１と同様に操作して、粘着付与剤樹脂エマルションを得た。 (2) Example 2
Based on Example 1 above, the rosin resin was changed from Production Example 1 to that of Production Example 2, and the other conditions were operated in the same manner as in Example 1 to obtain a tackifier resin emulsion.

(3)実施例３
前記実施例１を基本として、ロジン系樹脂を製造例１から前記製造例３のものに変更し、ロジン系樹脂とアクリル系オリゴマーの混合量をロジン系樹脂：アクリル系オリゴマー＝８０％：２０％の割合に変更し、その他の条件を実施例１と同様に操作して、粘着付与剤樹脂エマルションを得た。 (3) Example 3
Based on Example 1, the rosin resin was changed from Production Example 1 to Production Example 3, and the mixing amount of rosin resin and acrylic oligomer was rosin resin: acrylic oligomer = 80%: 20% The other conditions were changed in the same manner as in Example 1 to obtain a tackifier resin emulsion.

(4)実施例４
前記実施例１を基本として、ロジン系樹脂を製造例１から前記製造例３のものに変更し、その他の条件を実施例１と同様に操作して、粘着付与剤樹脂エマルションを得た。 (4) Example 4
Based on Example 1, the rosin resin was changed from Production Example 1 to Production Example 3, and other conditions were operated in the same manner as in Example 1 to obtain a tackifier resin emulsion.

(5)実施例５
前記実施例１を基本として、ロジン系樹脂を製造例１から前記製造例３のものに変更し、ロジン系樹脂とアクリル系オリゴマーの混合量をロジン系樹脂：アクリル系オリゴマー＝５０％：５０％の割合に変更し、その他の条件を実施例１と同様に操作して、粘着付与剤樹脂エマルションを得た。 (5) Example 5
Based on Example 1, the rosin resin was changed from Production Example 1 to Production Example 3, and the mixing amount of rosin resin and acrylic oligomer was changed to rosin resin: acrylic oligomer = 50%: 50%. The other conditions were changed in the same manner as in Example 1 to obtain a tackifier resin emulsion.

(6)実施例６
前記実施例１を基本として、ロジン系樹脂を製造例１から前記製造例３のものに変更し、ロジン系樹脂とアクリル系オリゴマーの混合量をロジン系樹脂：アクリル系オリゴマー＝３０％：７０％の割合に変更し、その他の条件を実施例１と同様に操作して、粘着付与剤樹脂エマルションを得た。 (6) Example 6
Based on Example 1, the rosin resin was changed from Production Example 1 to Production Example 3, and the mixing amount of rosin resin and acrylic oligomer was changed to rosin resin: acrylic oligomer = 30%: 70%. The other conditions were changed in the same manner as in Example 1 to obtain a tackifier resin emulsion.

(7)実施例７
前記実施例１を基本として、ロジン系樹脂を製造例１から前記製造例３のものに変更し、アクリル系オリゴマーをオリゴマー１から下記のアクリル系オリゴマー２に変更し、その他の条件を実施例１と同様に操作して、粘着付与剤樹脂エマルションを得た。
アクリル系オリゴマー２：東亞合成株式会社製のＡＲＵＦＯＮ ＵＰ−１０００
（重量平均分子量：３,０００、ガラス転移温度：−７７℃（ＤＳＣ法）） (7) Example 7
Based on Example 1, the rosin resin was changed from Production Example 1 to Production Example 3, the acrylic oligomer was changed from Oligomer 1 to the following acrylic oligomer 2, and other conditions were changed to Example 1. In the same manner as described above, a tackifier resin emulsion was obtained.
Acrylic oligomer 2: ARUFON UP-1000 manufactured by Toagosei Co., Ltd.
(Weight average molecular weight: 3,000, glass transition temperature: -77 ° C. (DSC method))

(8)実施例８
前記実施例１を基本として、ロジン系樹脂を製造例１から前記製造例３のものに変更し、アクリル系オリゴマーをオリゴマー１から下記のアクリル系オリゴマー３に変更し、その他の条件を実施例１と同様に操作して、粘着付与剤樹脂エマルションを得た。
アクリル系オリゴマー３：東亞合成株式会社製のＡＲＵＦＯＮ ＵＰ−３９００
（重量平均分子量：４,６００、ガラス転移温度：６０℃（ＤＳＣ法）） (8) Example 8
Based on Example 1, the rosin resin was changed from Production Example 1 to Production Example 3, the acrylic oligomer was changed from Oligomer 1 to the following acrylic oligomer 3, and other conditions were changed to Example 1. In the same manner as described above, a tackifier resin emulsion was obtained.
Acrylic oligomer 3: ARUFON UP-3900 manufactured by Toagosei Co., Ltd.
(Weight average molecular weight: 4,600, glass transition temperature: 60 ° C. (DSC method))

(9)実施例９
前記実施例７を基本として、ロジン系樹脂を製造例３の単用から製造例１と製造例３の併用に変更し、ロジン系樹脂とアクリル系オリゴマーの混合量を製造例１：製造例３：アクリル系オリゴマー＝３５％：３５％：３０％の割合に変更し、その他の条件を実施例７と同様に操作して、粘着付与剤樹脂エマルションを得た。 (9) Example 9
Based on Example 7, the rosin resin was changed from single use in Production Example 3 to combined use in Production Example 1 and Production Example 3, and the mixing amount of the rosin resin and acrylic oligomer was produced in Production Example 1: Production Example 3. : Acrylic oligomer = 35%: 35%: 30% The other conditions were changed in the same manner as in Example 7 to obtain a tackifier resin emulsion.

(10)実施例１０
前記実施例７を基本として、アクリル系オリゴマーをオリゴマー２の単用からオリゴマー１とオリゴマー２の併用に変更し、ロジン系樹脂とアクリル系オリゴマーの混合量を製造例３：アクリル系オリゴマー１：アクリル系オリゴマー２＝７０％：１５％：１５％の割合に変更し、その他の条件を実施例７と同様に操作して、粘着付与剤樹脂エマルションを得た。 (10) Example 10
Based on the Example 7, the acrylic oligomer is changed from the single use of the oligomer 2 to the combined use of the oligomer 1 and the oligomer 2, and the mixed amount of the rosin resin and the acrylic oligomer is produced. Production Example 3: Acrylic oligomer 1: Acrylic The system oligomer 2 was changed to a ratio of 70%: 15%: 15%, and other conditions were operated in the same manner as in Example 7 to obtain a tackifier resin emulsion.

(11)実施例１１
前記実施例１を基本として、アクリル系オリゴマーをオリゴマー１から下記のアクリル系オリゴマー４に変更し、その他の条件を実施例１と同様に操作して、粘着付与剤樹脂エマルションを得た。
アクリル系オリゴマー４：東亞合成株式会社製のＡＲＵＦＯＮ ＵＨ−２０００
（重量平均分子量：１１,０００、ガラス転移温度：−５５℃（ＤＳＣ法）） (11) Example 11
Based on Example 1, the acrylic oligomer was changed from oligomer 1 to the following acrylic oligomer 4, and the other conditions were operated in the same manner as in Example 1 to obtain a tackifier resin emulsion.
Acrylic oligomer 4: ARUFON UH-2000 manufactured by Toagosei Co., Ltd.
(Weight average molecular weight: 11,000, glass transition temperature: -55 ° C. (DSC method))

(12)実施例１２
前記実施例１を基本として、ロジン系樹脂とアクリル系オリゴマーとの混合物を無溶剤転相乳化するに際して、水を添加していく相反転の工程でのディスクタービンの回転数を１,５００ｒｐｍから１,０００ｒｐｍに低減し、その他の条件を実施例１と同様に操作して、粘着付与剤樹脂エマルションを得た。 (12) Example 12
Based on Example 1, when the mixture of rosin resin and acrylic oligomer is subjected to solventless phase inversion emulsification, the rotation speed of the disk turbine in the phase inversion process in which water is added is changed from 1,500 rpm to 1. The pressure was reduced to 1,000 rpm, and other conditions were operated in the same manner as in Example 1 to obtain a tackifier resin emulsion.

(13)比較例１
前記実施例４を基本として、アクリル系オリゴマーを共存させず、製造例３のロジン系樹脂のみを使用し(従って、製造例３：アクリル系オリゴマー１＝１００％：０％である)、その他の条件を実施例４と同様に操作して粘着付与剤樹脂エマルションを得ようとしたが、水を滴下していく段階で水の沸騰を抑制できなくなり、製造を中止した。 (13) Comparative Example 1
Based on Example 4 above, the acrylic oligomer is not used together, and only the rosin resin of Production Example 3 is used (therefore, Production Example 3: Acrylic oligomer 1 = 100%: 0%), and the other The conditions were operated in the same manner as in Example 4 to obtain a tackifier resin emulsion, but boiling of water could not be suppressed at the stage of dropping water, and production was stopped.

(14)比較例２
アクリル系オリゴマー１の共存下で、製造例３のロジン系樹脂を転相乳化に替えて溶剤乳化法でエマルション化したものである。
即ち、製造例３のロジン系樹脂とアクリル系オリゴマー１を、ロジン系樹脂：アクリル系オリゴマー＝７０％：３０％の割合にて含有する混合物の合計１００部をトルエン１００部に溶解させてトルエン溶液を得た。
次いで、乳化剤（ソフタノール ＭＥＳ−９：日本触媒株式会社製（有効成分２４％））２０部を水１１０部に希釈溶解して乳化水溶液を調整し、この乳化水溶液を上記トルエン溶液に添加した後、攪拌混合して予備乳化を行った。
得られた予備乳化物を高圧乳化機(マウントガウリン社製)によって３００ｋｇ／ｃｍ2の圧力で乳化し、乳化物を得た。
この乳化物を蒸留時の発泡を抑制するため、消泡剤（アデカネートＢ−９４０：旭電化工業株式会社製）を０.１部添加し、１１０ｍｍＨｇの条件下で加熱減圧蒸留してトルエンを除去した後、トリエタノールアミンを添加し、ｐＨを７.５に調整した。また、固形分も適量の水を添加することにより５０％に調整した。 (14) Comparative example 2
In the coexistence of the acrylic oligomer 1, the rosin resin of Production Example 3 is emulsified by a solvent emulsification method instead of phase inversion emulsification.
That is, a total of 100 parts of a mixture containing the rosin resin and acrylic oligomer 1 of Production Example 3 in a ratio of rosin resin: acrylic oligomer = 70%: 30% was dissolved in 100 parts of toluene to obtain a toluene solution. Got.
Next, 20 parts of emulsifier (Softanol MES-9: manufactured by Nippon Shokubai Co., Ltd. (active ingredient 24%)) was diluted and dissolved in 110 parts of water to prepare an emulsified aqueous solution, and this emulsified aqueous solution was added to the toluene solution. Pre-emulsification was performed by stirring and mixing.
The obtained preliminary emulsion was emulsified with a high-pressure emulsifier (manufactured by Mount Gaurin) at a pressure of 300 kg / cm 2 to obtain an emulsion.
In order to suppress foaming during distillation of this emulsion, 0.1 part of an antifoaming agent (Adecanate B-940: manufactured by Asahi Denka Kogyo Co., Ltd.) is added, and toluene is removed by heating under reduced pressure at 110 mmHg. After that, triethanolamine was added to adjust the pH to 7.5. The solid content was also adjusted to 50% by adding an appropriate amount of water.

《粘着付与剤樹脂エマルションの評価試験例》
そこで、上記実施例１〜１２及び比較例２で得られた各粘着付与剤樹脂エマルションについて、下記に示す通り、エマルションの貯蔵安定性及び機械安定性、平均粒子径、塗布時のハジキ抑制度合、ＶＯＣ放散速度の各種評価試験を行った。
尚、前述したように、比較例１においては製造を途中で中止したために、試験は行わなかった。 << Evaluation test example of tackifier resin emulsion >>
Therefore, for each tackifier resin emulsion obtained in Examples 1-12 and Comparative Example 2, as shown below, the storage stability and mechanical stability of the emulsion, the average particle size, the degree of repellency during application, Various evaluation tests of the VOC emission rate were conducted.
Note that, as described above, in Comparative Example 1, the test was not performed because the production was stopped halfway.

(1)粘着付与剤樹脂エマルションの貯蔵安定性
先ず、実施例及び比較例で得られた製造直後の各粘着付与剤樹脂エマルションについて、予め赤外線式固形分測定装置にて固形分を測定し、その測定値を初期値Ａとした。
次いで、内径が４０ｍｍで長さが１ｍの透明ポリカーボネート管の一端をゴム栓で封印し、上記各エマルション１ｋｇを挿入した後、他端についてもゴム栓で封印し、２３℃の恒温室内でポリカーボネート管を直立させて１ヶ月間放置した。
放置後の粘着付与剤樹脂エマルションを上部液面より約５ｃｍのところからスポイトで採取し、初期と同様に赤外線式固形分測定装置にて固形分を測定し、測定値Ｂとした。
そして、初期値Ａより測定値Ｂを差し引いた値を貯蔵安定性指標値として、この指標値に基づいて、次の基準により貯蔵安定性を評価した。
○：貯蔵安定性指標値が０.５％未満であった。
△：貯蔵安定性指標値が０.５％〜１.５％であった。
×：貯蔵安定性指標値が１.５％以上であった。 (1) Storage stability of tackifier resin emulsion First, for each tackifier resin emulsion immediately after production obtained in Examples and Comparative Examples, the solid content was measured in advance with an infrared solid content measuring device, The measured value was designated as initial value A.
Next, one end of a transparent polycarbonate tube having an inner diameter of 40 mm and a length of 1 m is sealed with a rubber stopper. After 1 kg of each emulsion is inserted, the other end is also sealed with a rubber stopper, and the polycarbonate tube is placed in a thermostatic chamber at 23 ° C. Was left standing for 1 month.
The tackifier resin emulsion after being allowed to stand was collected with a dropper from about 5 cm from the upper liquid surface, and the solid content was measured with an infrared solid content measuring device in the same manner as in the initial stage, and the measured value B was obtained.
And the value which deducted measured value B from initial value A was made into the storage stability index value, and based on this index value, storage stability was evaluated by the following criteria.
○: The storage stability index value was less than 0.5%.
Δ: Storage stability index value was 0.5% to 1.5%.
X: The storage stability index value was 1.5% or more.

(2)粘着付与剤樹脂エマルションの機械安定性試験
実施例及び比較例の各粘着付与剤樹脂エマルションを固形分５０％に調整した後、荷重１０ｋｇ、回転数１,０００ｒｐｍ、シェア時間５分間の条件でマーロン試験を行い、凝集物の重量を測定し、下式により凝集物の発生率を算出して、
凝集物の発生率（％）＝（凝集物／初期固形分）×１００
この発生率(％)から下記の基準により機械安定性を評価した。
○：凝集物の発生率が０.５％未満であった。
△：凝集物の発生率が０.５％〜５.０％であった。
×：凝集物の発生率が５.０％以上であった。 (2) Mechanical stability test of tackifier resin emulsion After adjusting each tackifier resin emulsion of Examples and Comparative Examples to a solid content of 50%, conditions of load 10 kg, rotation speed 1,000 rpm, share time 5 minutes Perform a Marlon test with, measure the weight of the aggregates, calculate the rate of occurrence of aggregates by the following formula,
Aggregate generation rate (%) = (aggregate / initial solid content) × 100
From this occurrence rate (%), mechanical stability was evaluated according to the following criteria.
A: The occurrence rate of aggregates was less than 0.5%.
(Triangle | delta): The generation | occurrence | production rate of the aggregate was 0.5%-5.0%.
X: The occurrence rate of aggregates was 5.0% or more.

(3)粘着付与剤樹脂エマルションの平均粒子径
測定装置（ＬＡ−９２０；堀場製作所製）を用いて、タングステンランプの透過率（即ち、測定装置における透過率（Ｈ））で８０〜８５％になるように、実施例及び比較例の各粘着付与剤樹脂エマルションを蒸留水で希釈し、且つ、相対屈折率を１.２とする条件で測定し、その結果をコンピューター処理して、得られた算術平均径をエマルションの平均粒子径とした。 (3) Average particle diameter of tackifier resin emulsion Using a measuring device (LA-920; manufactured by HORIBA, Ltd.), the transmittance of the tungsten lamp (that is, the transmittance (H) in the measuring device) is 80 to 85%. Thus, each tackifier resin emulsion of Examples and Comparative Examples was diluted with distilled water and measured under the condition that the relative refractive index was 1.2, and the result was obtained by computer processing. The arithmetic average diameter was defined as the average particle diameter of the emulsion.

(4)ハジキ抑制度合
一般に、エマルション型粘着剤を剥離紙やフィルムに塗布する際にハジキが起こる現象は、エマルション型粘着剤を塗布する基材に対する濡れ性に大きく寄与しており、より速く濡れる場合には外的要因に左右されることがなくハジキが起こらないが、ゆっくりと濡れていく場合は、外的な要因に左右されてハジキが起こる。従って、後述する試験において、接触角が一定になるまでの平均時間を測定することで、このハジキの抑制度合を評価することができる。
そこで、ハジキ抑制度合の試験方法を述べると、先ず、表面をヘアライン加工したステンレス板（ＳＵＳ３０４）を用意し、実施例及び比較例の各粘着付与剤樹脂エマルションを蒸留水で固形分が３０％になるように希釈した試験サンプルを、このステンレス板にマイクロシリンジを用いて２μＬ着液させ、着液後１０秒間隔でエマルション液滴の接触角を接触角計（Drop Master 500；協和界面科学製）にて測定した。
同様の操作を３回実施し、接触角が一定になるまでの時間の平均値を測定算出した。
そして、溶剤乳化法で得られた比較例２を標準値として、無溶剤下(即ち、転相乳化)で得られた実施例及び比較例の各エマルションについて、接触角が一定になるまでの平均時間を比較例２の標準値と対比することにより、ハジキの発生を抑制する度合の優劣を評価した。
○：比較例２に比べて、接触角が一定になる時間が速かった。
×：比較例２に比べて、接触角が一定となる時間が遅かった。 (4) Degree of repellency In general, the phenomenon that cissing occurs when an emulsion-type adhesive is applied to release paper or film greatly contributes to the wettability of the substrate to which the emulsion-type adhesive is applied, resulting in faster wetting. In some cases, repelling does not occur without being influenced by external factors, but when it gets wet slowly, repelling occurs depending on external factors. Therefore, by measuring the average time until the contact angle becomes constant in the test described later, the degree of suppression of this repellency can be evaluated.
Therefore, a test method for the degree of repellency suppression is described. First, a stainless steel plate (SUS304) having a hairline processed surface is prepared, and the solid content of each tackifier resin emulsion of Examples and Comparative Examples is 30% with distilled water. 2 μL of the diluted test sample is applied to this stainless steel plate using a microsyringe, and the contact angle of the emulsion droplets is measured at an interval of 10 seconds after application (Drop Master 500; manufactured by Kyowa Interface Science). Measured at
The same operation was performed three times, and the average value of the time until the contact angle became constant was measured and calculated.
Then, with Comparative Example 2 obtained by the solvent emulsification method as a standard value, the average until the contact angle becomes constant for each of the emulsions of Examples and Comparative Examples obtained without solvent (that is, phase inversion emulsification) By comparing the time with the standard value of Comparative Example 2, the degree of superiority or inferiority of suppressing the occurrence of repelling was evaluated.
○: Compared with Comparative Example 2, the time for the contact angle to be constant was faster.
X: Compared with Comparative Example 2, the time during which the contact angle was constant was late.

(5)ＶＯＣ放散速度
測定は、JIS A1901：2003「建築材料の揮発性有機化合物（ＶＯＣ）、ホルムアルデヒド及び他のカルボニル化合物放散測定方法−小型チャンバー法」に準拠して行った。
先ず、２０℃、相対湿度７３％の恒温室内で８０ｃｍ2のステンレス製シャーレに実施例及び比較例の各粘着付与剤樹脂エマルションを約２.４ｇ採取し、へらで均一に塗布した後、６０分間放置したものを試験試料とした。
次いで、２０Ｌのチャンバーに試験試料を投入して、温度２８±１℃、相対湿度５０±５％、換気回数０.５±０.０５回／ｈの条件で試験を行い、３日後のチャンバー内の空気を３.２Ｌ採取し、ガスクロマトグラフィー質量分析計にて、トルエン、キシレン、ｐ−ジクロロベンゼン、エチルベンゼン、スチレン、テトラデカン、ノナナールの定量を行った。
この場合、データ分析も同様にJIS A1901：2003に準拠して行った。即ち、試験試料をチャンバーに入れてから測定を開始した経過時間（ｔ）における単位面積当たりの放散速度（ＥＦａ）を下式により算出した。
ＥＦａ＝｛（Ｃt−Ｃtb,t）×Ｑ｝／Ａ
Ｃt ：対象ＶＯＣの濃度
Ｃtb,t：経過時間ｔにおけるトラベルブランク濃度
Ｑ ：換気量（ｍ3／ｈ）
Ａ ：試験試料の表面積（ｍ2）
そして、得られた対象ＶＯＣの３日後の放散速度について、下記の基準により揮発性有機化合物の揮散抑制度合の優劣を評価した。
○：対象ＶＯＣのいずれも放散速度が２μｇ／ｍ2・ｈ未満であった。
△：対象ＶＯＣのうち、少なくとも一種の放散速度が２μｇ／ｍ2・ｈ〜２０μｇ／ ｍ2・ｈであった。
×：対象ＶＯＣのうち、少なくとも一種の放散速度が２０μｇ／ｍ2・ｈ以上であっ た。 (5) VOC emission rate The measurement was performed according to JIS A1901: 2003 “Measurement method for emission of volatile organic compounds (VOC), formaldehyde and other carbonyl compounds in building materials—small chamber method”.
First, about 2.4 g of each of the tackifier resin emulsions of Examples and Comparative Examples was collected in an 80 cm 2 stainless steel petri dish in a constant temperature room at 20 ° C. and a relative humidity of 73%, and evenly applied with a spatula for 60 minutes. The left sample was used as a test sample.
Next, the test sample was put into a 20 L chamber, and the test was performed under the conditions of a temperature of 28 ± 1 ° C., a relative humidity of 50 ± 5%, and a ventilation rate of 0.5 ± 0.05 times / h. 3.2 L of this air was collected, and toluene, xylene, p-dichlorobenzene, ethylbenzene, styrene, tetradecane, and nonanal were quantified with a gas chromatography mass spectrometer.
In this case, data analysis was similarly performed in accordance with JIS A1901: 2003. That is, the emission rate (EFa) per unit area at the elapsed time (t) when the measurement was started after placing the test sample in the chamber was calculated by the following equation.
EFa = {(C t −C tb , t ) × Q} / A
C t : Concentration of target VOC
C tb , t : Travel blank density at elapsed time t
Q: Ventilation rate (m 3 / h)
A: Surface area of test sample (m 2 )
And the superiority or inferiority of the volatilization suppression degree of a volatile organic compound was evaluated by the following reference | standard about the diffusion rate after 3 days of the obtained object VOC.
○: All of the target VOCs had a dissipation rate of less than 2 μg / m 2 · h.
△: Among the target VOC, at least one emission rate was 2μg / m 2 · h~20μg / m 2 · h.
X: At least one type of emission rate of the target VOC was 20 μg / m 2 · h or more.

図１はその試験結果である。
同図１の比較例１では、高軟化点のロジン系樹脂(前記製造例３)をアクリル系オリゴマーを共存させないで無溶剤転相乳化でエマルション化しようとしたため、水の沸騰を抑制できなくなり、乳化が困難であった。
これに対して、実施例１〜１０では、高軟化点のロジン系樹脂を特定の低分子量を有するアクリル系オリゴマーの共存下で無溶剤転相乳化したため、効率良く粘着付与剤樹脂エマルションを得ることができた。特に、比較例１と同様の高軟化点のロジン系樹脂(製造例３：軟化点１８５℃)を使用した実施例３〜１０にあっても、円滑に同エマルションを得ることができた。
ちなみに、上記実施例１〜１０で得られた粘着付与剤樹脂エマルションの試験評価では、平均粒子径は０.２０〜０.４０μｍの好ましい範囲内にあり、貯蔵安定性、機械安定性に優れ、ハジキの抑制評価も良くて優れた塗布性能を具備するとともに、ＶＯＣの問題もないことが認められた。
さらに、この実施例１〜１０においては、(ａ)ロジン系樹脂の軟化点が１２０℃(製造例１)、１６６℃(製造例２)、１８５℃(製造例３)である場合を問わず、(ｂ)アクリル系オリゴマーの分子量が１８００(同オリゴマー１)、３０００(同オリゴマー２)、４６００(同オリゴマー３)である場合を問わず、(ｃ)ロジン系樹脂の単用又は併用(実施例９)を問わず、(ｄ)アクリル系オリゴマーの単用又は併用(実施例１０)を問わず、また、(ｅ)ロジン系樹脂とアクリル系オリゴマーの混合割合が様々に変化しても、夫々優れた総合評価を示した。尚、実施例３において、機械安定性の評価が△であったのは、ロジン系樹脂とアクリル系オリゴマーの混合量がロジン系樹脂：アクリル系オリゴマー＝８０％：２０％であることに起因するものと推定される。
従って、高軟化点樹脂を無溶剤方式で水性エマルション化するには、アクリル系共重合体を補助成分として共存させることが重要であり、特にアクリル系共重合体の中でも特定の低分子量を有するアクリル系オリゴマーの共存が必要であることが判明した。 FIG. 1 shows the test results.
In Comparative Example 1 of FIG. 1, since rosin resin having the high softening point (Preparation Example 3) was attempted to be emulsified by solvent-free phase inversion emulsification without coexistence of the acrylic oligomer, boiling of water could not be suppressed, Emulsification was difficult.
On the other hand, in Examples 1 to 10, since the rosin resin having a high softening point was subjected to solventless phase inversion emulsification in the presence of an acrylic oligomer having a specific low molecular weight, a tackifier resin emulsion was efficiently obtained. I was able to. In particular, even in Examples 3 to 10 using a rosin resin having the same high softening point as in Comparative Example 1 (Production Example 3: softening point 185 ° C.), the same emulsion could be obtained smoothly.
Incidentally, in the test evaluation of the tackifier resin emulsion obtained in Examples 1 to 10 above, the average particle size is within a preferable range of 0.20 to 0.40 μm, and is excellent in storage stability and mechanical stability. It was confirmed that the evaluation of repelling was good and the coating performance was excellent, and there was no VOC problem.
Further, in Examples 1 to 10, regardless of the case (a) the softening point of the rosin resin is 120 ° C. (Production Example 1), 166 ° C. (Production Example 2), or 185 ° C. (Production Example 3). (B) Regardless of whether the molecular weight of the acrylic oligomer is 1800 (same oligomer 1), 3000 (same oligomer 2), or 4600 (same oligomer 3), (c) single or combined use of rosin resin (implemented) Regardless of Example 9), (d) Regardless of whether the acrylic oligomer is used alone or in combination (Example 10), and (e) the mixing ratio of the rosin resin and the acrylic oligomer varies, Each showed excellent overall evaluation. In Example 3, the evaluation of mechanical stability was Δ because the mixing amount of rosin resin and acrylic oligomer was rosin resin: acrylic oligomer = 80%: 20%. Estimated.
Therefore, in order to make a high softening point resin into an aqueous emulsion in a solvent-free manner, it is important that an acrylic copolymer coexists as an auxiliary component, and an acrylic copolymer having a specific low molecular weight among acrylic copolymers is particularly important. It was found that the coexistence of system oligomers was necessary.

比較例２のように、高軟化点のロジン系樹脂(前記製造例３)をアクリル系オリゴマーを共存させながら、無溶剤方式ではなく溶剤乳化法でエマルション化すると、得られたエマルションの平均粒子径、貯蔵安定性、機械安定性は良好であったが、当然ながらＶＯＣの評価に劣り、また、ハジキが発生して（消泡剤の添加による悪影響が推定される）均一な塗布に支障が出ることが明らかになった。
これに対して、無溶剤転相乳化で製造した実施例１〜１０では、上述したように、ＶＯＣやハジキの評価に優れていた。
従って、高軟化点樹脂を効率良く水性エマルション化するには、アクリル系オリゴマーの共存が重要であるが、環境保全や良好な塗布性などを担保するには、無溶剤方式、特に転相乳化などで高軟化点樹脂をエマルション化することが必要である点が確認できた。 When the rosin resin having the high softening point (Preparation Example 3) was emulsified by the solvent emulsification method instead of the solventless method while coexisting the acrylic oligomer as in Comparative Example 2, the average particle size of the obtained emulsion The storage stability and mechanical stability were good, but of course it was inferior in the evaluation of VOC, and repellency occurred (an adverse effect due to the addition of an antifoaming agent was estimated), which hindered uniform application. It became clear.
On the other hand, in Examples 1 to 10 produced by solventless phase inversion emulsification, as described above, VOC and repelling were excellent.
Therefore, coexistence of acrylic oligomers is important to efficiently make a high softening point resin into an aqueous emulsion, but to ensure environmental preservation and good coating properties, a solventless method, particularly phase inversion emulsification, etc. Thus, it was confirmed that it was necessary to emulsify the high softening point resin.

重量平均分子量が１.１万のアクリル系オリゴマー４を共存させた実施例１１では、ロジン系樹脂(製造例１)の軟化点が１２０℃であるにも拘わらず、平均粒子径、ハジキ、ＶＯＣの評価は良好であったが、貯蔵安定性や機械安定性の評価が△であった。これに対して、同じく軟化点が１２０℃のロジン系樹脂(製造例１)に分子量が１８００のアクリル系オリゴマー１を共存させた実施例１では、貯蔵安定性、機械安定性に優れていた。また、一般的に、粘着付与剤樹脂の軟化点が高くなるほど水性エマルション化することが難しくなるが、軟化点が１８５℃のロジン系樹脂(製造例３)に分子量が１８００のアクリル系オリゴマー１を共存させた実施例４においても、貯蔵安定性、機械安定性は優れていた。ちなみに、この実施例１１、実施例１、実施例４では、ロジン系樹脂とアクリル系オリゴマーの混合割合はすべてロジン系樹脂：アクリル系オリゴマー＝７０％：３０％で共通している。
従って、高軟化点樹脂を効率良く水性エマルション化して、総合評価に優れた粘着付与剤樹脂エマルションを得るためには、５万以下の低分子量を有するアクリル系オリゴマーの共存が必要であり、特に同オリゴマーの重量平均分子量が１０００〜５０００であると、より優れた総合評価のエマルションが得られ、逆に、同分子量が５万を越えると、エマルション安定性などの面で問題が生じることが確認できた。
一方、アクリル系オリゴマーの重量平均分子量が１０００より小さくなると、先述したように、当然ながら同オリゴマーの揮発性が増し、ＶＯＣなどの面で問題が生じる。 In Example 11 in which acrylic oligomer 4 having a weight average molecular weight of 11,000 coexisted, the average particle diameter, repelling, VOC, even though the softening point of rosin resin (Production Example 1) was 120 ° C. The evaluation of was good, but the evaluation of storage stability and mechanical stability was Δ. On the other hand, Example 1 in which acrylic oligomer 1 having a molecular weight of 1800 coexists in rosin resin (Production Example 1) having a softening point of 120 ° C. was excellent in storage stability and mechanical stability. In general, the higher the softening point of the tackifier resin, the more difficult it becomes to form an aqueous emulsion. However, the acrylic oligomer 1 having a molecular weight of 1800 is added to a rosin resin having a softening point of 185 ° C. (Production Example 3). Also in Example 4 where the coexistence was carried out, the storage stability and mechanical stability were excellent. By the way, in Example 11, Example 1, and Example 4, the mixing ratio of the rosin resin and acrylic oligomer is the same for all rosin resin: acrylic oligomer = 70%: 30%.
Therefore, in order to efficiently make a high softening point resin into an aqueous emulsion and obtain a tackifier resin emulsion excellent in comprehensive evaluation, it is necessary to coexist with an acrylic oligomer having a low molecular weight of 50,000 or less. If the weight average molecular weight of the oligomer is 1000 to 5000, a better overall evaluation emulsion can be obtained. Conversely, if the molecular weight exceeds 50,000, problems such as emulsion stability can be confirmed. It was.
On the other hand, if the weight average molecular weight of the acrylic oligomer is less than 1000, as described above, the volatility of the oligomer naturally increases, and problems such as VOC occur.

転相乳化に際して、水を添加していく工程でのディスクタービンの回転数を他の実施例(特に実施例４との対比)より低減した実施例１２では、得られた粘着付与剤樹脂エマルションの平均粒子径が０.５２μｍであり、ハジキ抑制度合やＶＯＣの評価は優れていたが、貯蔵安定性や機械安定性の評価は△であった。
これに対して、粘着付与剤樹脂エマルションの平均粒子径が０.２０〜０.４０μｍである実施例１〜１０では、貯蔵安定性や機械安定性に優れることから、アクリル系オリゴマーを共存させて得られる粘着付与剤樹脂エマルションを安定化するには、同粒子径が０.１０〜０.５０μｍであることが適当であり、さらにエマルションの安定性を増すには同粒子径を０.２０〜０.４０μｍに調整することが好ましい点が確認できた。 In Example 12, in which the rotational speed of the disk turbine in the process of adding water during phase inversion emulsification is reduced as compared with other examples (particularly as compared with Example 4), the obtained tackifier resin emulsion The average particle size was 0.52 μm, and the evaluation of repelling degree and VOC was excellent, but the evaluation of storage stability and mechanical stability was Δ.
On the other hand, in Examples 1-10 whose average particle diameter of tackifier resin emulsion is 0.20-0.40 micrometer, since it is excellent in storage stability and mechanical stability, an acrylic oligomer is made to coexist. In order to stabilize the resulting tackifier resin emulsion, it is appropriate that the particle diameter is from 0.10 to 0.50 μm, and in order to further increase the stability of the emulsion, the particle diameter is from 0.20 to It was confirmed that adjustment to 0.40 μm was preferable.

実施例１〜１２及び比較例１〜２について、ロジン系樹脂とアクリル系オリゴマーの混合割合、並びに得られた各粘着付与剤樹脂エマルション（比較例１を除く）についての貯蔵安定性や機械安定性などの各種評価試験結果を示す図表である。About Examples 1-12 and Comparative Examples 1-2, the mixing ratio of a rosin resin and an acrylic oligomer, and the storage stability and mechanical stability of each obtained tackifier resin emulsion (except for Comparative Example 1) It is a chart which shows various evaluation test results, such as.

Claims (7)

軟化点が１２０〜１９０℃の粘着付与剤樹脂を、重量平均分子量が５００〜５０,０００のアクリル系オリゴマーの共存下で、無溶剤且つ加圧条件にて水中に分散させたことを特徴とする粘着付与剤樹脂エマルション。   A tackifier resin having a softening point of 120 to 190 ° C. is dispersed in water in a solvent-free and pressurized condition in the presence of an acrylic oligomer having a weight average molecular weight of 500 to 50,000. Tackifier resin emulsion. アクリル系オリゴマーが、連続塊状重合で製造した低分子量の共重合体であることを特徴とする請求項１に記載の粘着付与剤樹脂エマルション。   The tackifier resin emulsion according to claim 1, wherein the acrylic oligomer is a low molecular weight copolymer produced by continuous bulk polymerization. 粘着付与剤樹脂とアクリル系オリゴマーを溶融混合し、転相乳化で樹脂分を水中に分散することを特徴とする請求項１又は２に記載の粘着付与剤樹脂エマルション。   The tackifier resin emulsion according to claim 1 or 2, wherein the tackifier resin and the acrylic oligomer are melt-mixed and the resin component is dispersed in water by phase inversion emulsification. 粘着付与剤樹脂がロジン系樹脂、テルペン系樹脂、石油系樹脂の少なくとも一種であることを特徴とする請求項１〜３のいずれか１項に記載の粘着付与剤樹脂エマルション。   The tackifier resin emulsion according to any one of claims 1 to 3, wherein the tackifier resin is at least one of a rosin resin, a terpene resin, and a petroleum resin. 粘着付与剤樹脂とアクリル系オリゴマーの混合割合が、固形分換算でアクリル系オリゴマー／粘着付与剤樹脂＝２０〜８０重量部／８０〜２０重量部であることを特徴とする請求項１〜４のいずれか１項に記載の粘着付与剤樹脂エマルション。   The mixing ratio of the tackifier resin and the acrylic oligomer is acrylic oligomer / tackifier resin = 20 to 80 parts by weight / 80 to 20 parts by weight in terms of solid content. The tackifier resin emulsion of any one of Claims. 粘着付与剤樹脂エマルションの平均粒子経が０.１０〜０.５０μｍであることを特徴とする請求項１〜５のいずれか１項に記載の粘着付与剤樹脂エマルション。   The tackifier resin emulsion according to any one of claims 1 to 5, wherein the average particle size of the tackifier resin emulsion is from 0.10 to 0.50 µm. 連続塊状重合で製造した重量平均分子量が５００〜５０,０００のアクリル系オリゴマーと軟化点が１２０〜１９０℃の粘着付与剤樹脂とを、固形分換算でアクリル系オリゴマー／粘着付与剤樹脂＝２０〜８０重量部／８０〜２０重量部の割合で溶融混合し、
上記溶融樹脂中に乳化剤の存在下で水を添加することにより、油中水型エマルションを水中油型エマルションに相反転させることを特徴とする粘着付与剤樹脂エマルションの製造方法。 Acrylic oligomer having a weight average molecular weight of 500 to 50,000 produced by continuous bulk polymerization and a tackifier resin having a softening point of 120 to 190 ° C., acrylic oligomer / tackifier resin = 20 to in terms of solid content 80 parts by weight / 80-20 parts by weight melt mixed,
A method for producing a tackifier resin emulsion, wherein the water-in-oil emulsion is inverted into an oil-in-water emulsion by adding water to the molten resin in the presence of an emulsifier.
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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006056936A (en) * 2004-08-18 2006-03-02 Toagosei Co Ltd Adhesive composition
JP2007002212A (en) * 2005-05-25 2007-01-11 Arakawa Chem Ind Co Ltd Tackifying resin emulsion, method for producing the same and aqueous pressure-sensitive adhesive/adhesive composition
JP2007186588A (en) * 2006-01-13 2007-07-26 Harima Chem Inc Tackifier resin emulsion
JP2007197482A (en) * 2006-01-23 2007-08-09 Arakawa Chem Ind Co Ltd Tackifier, acrylic polymer composition, process for producing acrylic polymer composition, acrylic viscoadhesive agent, process for producing acrylic viscoadhesive agent and active energy ray curable resin composition
JP2007217564A (en) * 2006-02-17 2007-08-30 Arakawa Chem Ind Co Ltd Tackifier resin emulsion, its manufacturing method and water-based adhesive/joining composition
JP2007262132A (en) * 2006-03-27 2007-10-11 Dainippon Ink & Chem Inc Method for producing resin composition for water-based coating
JP2008007693A (en) * 2006-06-30 2008-01-17 Arakawa Chem Ind Co Ltd Tackifying resin emulsion, its production method and aqueous adhesive composition
JP2008105751A (en) * 2006-10-23 2008-05-08 Packs Co Ltd Resin-made packaging bag
JP2008195888A (en) * 2007-02-15 2008-08-28 Arakawa Chem Ind Co Ltd Stickiness-imparting resin emulsion, its production method, and water-based sticky and adhesive compositions
JP2008231275A (en) * 2007-03-22 2008-10-02 Arakawa Chem Ind Co Ltd Tackifier resin emulsion, its preparation, and water-based adhesive composition
JP2011006662A (en) * 2009-05-22 2011-01-13 Arakawa Chem Ind Co Ltd Tackifier resin emulsion, and method for producing the same, and water-based tacky/adhesive composition
JP2012007027A (en) * 2010-06-23 2012-01-12 Arakawa Chem Ind Co Ltd Stickiness-imparting resin emulsion, its manufacturing method, and aqueous sticky and adhesive composition
JP2012140500A (en) * 2010-12-28 2012-07-26 Arakawa Chem Ind Co Ltd Tackifier resin emulsion, method for producing the same and water-based tacky adhesive composition
CN111072830A (en) * 2019-12-31 2020-04-28 黎月清 Preparation method of phellandrene resin emulsion
JP7468110B2 (en) 2020-04-17 2024-04-16 ａｒｔｉｅｎｃｅ株式会社 Water-based pressure-sensitive adhesive, pressure-sensitive adhesive sheet, and method for producing water-based pressure-sensitive adhesive

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56125431A (en) * 1980-03-07 1981-10-01 Kao Corp Aqueous emulsion of tackifier resin
JPS56143221A (en) * 1980-03-10 1981-11-07 Diamond Shamrock Corp Solvent-free resin emulsion
JPS5861166A (en) * 1981-10-06 1983-04-12 Nitto Electric Ind Co Ltd Preparation of pressure-sensitive adhesive tape
JP2000186266A (en) * 1998-12-22 2000-07-04 Sekisui Chem Co Ltd Adhesive composition and surface decorative material produced by using same
JP2000309771A (en) * 1999-04-27 2000-11-07 Arakawa Chem Ind Co Ltd Tackifying resin emulsion and aqueous pressure-sensitive adhesive composition
JP2004143248A (en) * 2002-10-23 2004-05-20 Harima Chem Inc Tackifier resin emulsion

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS56125431A (en) * 1980-03-07 1981-10-01 Kao Corp Aqueous emulsion of tackifier resin
JPS56143221A (en) * 1980-03-10 1981-11-07 Diamond Shamrock Corp Solvent-free resin emulsion
JPS5861166A (en) * 1981-10-06 1983-04-12 Nitto Electric Ind Co Ltd Preparation of pressure-sensitive adhesive tape
JP2000186266A (en) * 1998-12-22 2000-07-04 Sekisui Chem Co Ltd Adhesive composition and surface decorative material produced by using same
JP2000309771A (en) * 1999-04-27 2000-11-07 Arakawa Chem Ind Co Ltd Tackifying resin emulsion and aqueous pressure-sensitive adhesive composition
JP2004143248A (en) * 2002-10-23 2004-05-20 Harima Chem Inc Tackifier resin emulsion

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4595439B2 (en) * 2004-08-18 2010-12-08 東亞合成株式会社 Adhesive composition
JP2006056936A (en) * 2004-08-18 2006-03-02 Toagosei Co Ltd Adhesive composition
JP2007002212A (en) * 2005-05-25 2007-01-11 Arakawa Chem Ind Co Ltd Tackifying resin emulsion, method for producing the same and aqueous pressure-sensitive adhesive/adhesive composition
JP2007186588A (en) * 2006-01-13 2007-07-26 Harima Chem Inc Tackifier resin emulsion
JP2007197482A (en) * 2006-01-23 2007-08-09 Arakawa Chem Ind Co Ltd Tackifier, acrylic polymer composition, process for producing acrylic polymer composition, acrylic viscoadhesive agent, process for producing acrylic viscoadhesive agent and active energy ray curable resin composition
JP2007217564A (en) * 2006-02-17 2007-08-30 Arakawa Chem Ind Co Ltd Tackifier resin emulsion, its manufacturing method and water-based adhesive/joining composition
JP2007262132A (en) * 2006-03-27 2007-10-11 Dainippon Ink & Chem Inc Method for producing resin composition for water-based coating
JP2008007693A (en) * 2006-06-30 2008-01-17 Arakawa Chem Ind Co Ltd Tackifying resin emulsion, its production method and aqueous adhesive composition
JP2008105751A (en) * 2006-10-23 2008-05-08 Packs Co Ltd Resin-made packaging bag
JP2008195888A (en) * 2007-02-15 2008-08-28 Arakawa Chem Ind Co Ltd Stickiness-imparting resin emulsion, its production method, and water-based sticky and adhesive compositions
JP2008231275A (en) * 2007-03-22 2008-10-02 Arakawa Chem Ind Co Ltd Tackifier resin emulsion, its preparation, and water-based adhesive composition
JP2011006662A (en) * 2009-05-22 2011-01-13 Arakawa Chem Ind Co Ltd Tackifier resin emulsion, and method for producing the same, and water-based tacky/adhesive composition
JP2012007027A (en) * 2010-06-23 2012-01-12 Arakawa Chem Ind Co Ltd Stickiness-imparting resin emulsion, its manufacturing method, and aqueous sticky and adhesive composition
JP2012140500A (en) * 2010-12-28 2012-07-26 Arakawa Chem Ind Co Ltd Tackifier resin emulsion, method for producing the same and water-based tacky adhesive composition
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