JP2007084781A - Method for producing acrylic aqueous adhesive composition - Google Patents
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本発明は、アクリル系水性粘着剤組成物の製造方法に関する。更に詳しくは、接着力と保持力に優れ、特に粗面に対する接着力に優れるアクリル系水性粘着剤組成物の製造方法に関する。 The present invention relates to a method for producing an acrylic aqueous pressure-sensitive adhesive composition. More specifically, the present invention relates to a method for producing an acrylic water-based pressure-sensitive adhesive composition that is excellent in adhesive strength and holding power, and particularly excellent in adhesive strength on rough surfaces.
近年、環境問題の点で溶剤型樹脂から、より環境への付加が少ない水性樹脂への移行が進んでいる。粘着剤分野においても、水性粘着剤に置換することが望まれている。そして、この水性粘着剤の代表的なものとして、水性媒体中で各種エチレン性不飽和単量体を乳化重合して得られるアクリルエマルジョン型粘着剤がある。 In recent years, there has been a shift from solvent-based resins to water-based resins with less environmental addition in terms of environmental problems. In the field of pressure-sensitive adhesives, replacement with water-based pressure-sensitive adhesives is desired. A typical example of this aqueous pressure-sensitive adhesive is an acrylic emulsion-type pressure-sensitive adhesive obtained by emulsion polymerization of various ethylenically unsaturated monomers in an aqueous medium.
アクリル系粘着剤を使用する場合、溶剤型、水性樹脂に限らず、保持力（粘着剤層にかかる剪断方向に対する抵抗性）を付与するため、架橋剤を添加する方法が一般的に用いられる。この方法により、保持力は向上するが接着力は低下する傾向にあり、接着力と保持力をバランス良く発現させることが必要である。しかし、アクリルエマルジョン型粘着剤は、一般的に溶剤型粘着剤と比較して、接着力と保持力をバランス良く発現することが難しく、特にウレタンフォームなどの凹凸のある粗面に対する接着力が低下し易い。 When an acrylic pressure-sensitive adhesive is used, not only a solvent type and an aqueous resin, but a method of adding a crosslinking agent is generally used in order to impart holding power (resistance to the shearing direction applied to the pressure-sensitive adhesive layer). By this method, the holding force is improved, but the adhesive force tends to decrease, and it is necessary to express the adhesive force and the holding force in a well-balanced manner. However, acrylic emulsion type pressure-sensitive adhesives are generally difficult to express in a good balance between adhesion and holding power compared to solvent-type pressure-sensitive adhesives, and in particular the adhesion to rough surfaces such as urethane foam is reduced. Easy to do.
この粗面接着性が低下する原因として、一つは溶剤型樹脂と水性樹脂によるポリマー構造の違いが考えられる。一般に乳化重合によって得られるポリマーは反応系内に過剰に存在するラジカルによりポリマー鎖の水素引き抜き反応等の副反応、すなわち枝分かれ反応が起き、ポリマー鎖が架橋構造をとってしまう。この架橋構造により、粘着剤被膜の柔軟性が低下し、更に架橋剤を添加することで一層被膜の柔軟性が損なわれるためと考えられる。このことは水性粘着剤へ移行する上での課題の一つである。 One possible cause of the rough surface adhesion deterioration is the difference in polymer structure between the solvent-type resin and the aqueous resin. In general, a polymer obtained by emulsion polymerization causes a side reaction such as a hydrogen abstraction reaction of a polymer chain, that is, a branching reaction, due to excessive radicals in the reaction system, and the polymer chain takes a crosslinked structure. This is considered to be because the flexibility of the pressure-sensitive adhesive film is lowered by this cross-linked structure, and the flexibility of the film is further impaired by adding a cross-linking agent. This is one of the problems in moving to an aqueous adhesive.
このような粗面に対する接着性を解決する方法として、アクリル系単量体を１０時間半減期温度が７０℃以下の重合開始剤を用いて乳化重合した水性分散体と、アクリル系単量体の乳化物を滴下しながら乳化重合した水分散体とを混合するアクリル系水性粘着剤組成物の製造方法が開示されている（例えば、特許文献１参照）。しかし、この方法によって得られる粘着剤は、特にウレタンフォームなどの粗面に対する接着力は不充分である。 As a method for solving such adhesion to a rough surface, an aqueous dispersion obtained by emulsion polymerization of an acrylic monomer using a polymerization initiator having a 10-hour half-life temperature of 70 ° C. or less, and an acrylic monomer A method for producing an acrylic aqueous pressure-sensitive adhesive composition in which an emulsion-polymerized aqueous dispersion is mixed while dropping an emulsion is disclosed (for example, see Patent Document 1). However, the pressure-sensitive adhesive obtained by this method has an inadequate adhesion particularly to rough surfaces such as urethane foam.
したがって、本発明の課題は、乳化重合時の枝分かれ反応を抑制することで、架橋剤を添加した後でも被膜の柔軟性を維持し、接着力と保持力ともに優れ、特にウレタンフォームのような粗面に対する接着力に優れるアクリル系水性粘着剤組成物の製造方法を提供することにある。 Therefore, an object of the present invention is to suppress the branching reaction at the time of emulsion polymerization, so that the flexibility of the film is maintained even after the addition of the crosslinking agent, and the adhesion and holding power are excellent. An object of the present invention is to provide a method for producing an acrylic water-based pressure-sensitive adhesive composition having excellent adhesion to a surface.
発明者等は、上記の課題を解決すべく、鋭意検討の結果、下記の知見を得た。
（１）使用する重合開始剤量から計算上求められるラジカル発生量を、反応系内に存在する重合性単量体成分１リットル当たり、毎分２×１０-13〜１５０×１０-13モルの範囲に制御することで枝分かれ反応が抑制され、得られるポリマー鎖は直線構造となること。
（２）分岐構造の少ないポリマーを架橋した場合、粘着剤被膜の柔軟性を維持することができ、接着力、特にウレタンフォームのような粗面に対する接着力を維持したまま保持力が向上すること。
The inventors obtained the following knowledge as a result of intensive studies to solve the above problems.
(1) The amount of radical generation calculated from the amount of polymerization initiator used is 2 × 10 −13 to 150 × 10 −13 mol per minute per liter of the polymerizable monomer component present in the reaction system. The branching reaction is suppressed by controlling the range, and the resulting polymer chain has a linear structure.
(2) When a polymer having a small branched structure is crosslinked, the flexibility of the pressure-sensitive adhesive film can be maintained, and the holding power is improved while maintaining the adhesive strength, particularly the adhesive strength to a rough surface such as urethane foam. .
本発明は、このような知見に基づくものである。 The present invention is based on such knowledge.
即ち、本発明は、（ａ）カルボキシル基含有エチレン性不飽和単量体、０．１〜１０重量％と（ｂ）炭素原子数が１〜１２のアルキル基を有するアルキル（メタ）アクリレート４５〜９９．９重量％とを含有する重合性単量体成分を、重合開始剤存在下、水性媒体中で、乳化重合する製造方法であって、使用する重合開始剤量から計算上求められるラジカル発生量が、反応系内に存在する重合性単量体成分１リットル当たり、毎分２×１０-13〜１５０×１０-13モルの範囲であり、かつ、該製造方法によって得られる水分散体から形成される乾燥被膜のガラス転移温度が−２５℃以下であることを特徴とするアクリル系水性粘着剤組成物の製造方法、を提供する。 That is, the present invention relates to (a) a carboxyl group-containing ethylenically unsaturated monomer, 0.1 to 10% by weight, and (b) an alkyl (meth) acrylate 45 to 5 having an alkyl group having 1 to 12 carbon atoms. Radical generation that is calculated from the amount of polymerization initiator used, wherein the polymerization monomer component containing 99.9% by weight is emulsion-polymerized in an aqueous medium in the presence of a polymerization initiator. The amount is from 2 × 10 −13 to 150 × 10 −13 mol per minute per liter of the polymerizable monomer component present in the reaction system, and from the aqueous dispersion obtained by the production method Provided is a method for producing an acrylic water-based pressure-sensitive adhesive composition, wherein a glass transition temperature of a dry film to be formed is −25 ° C. or lower.
本発明は、ポリマー鎖を分岐の少ない直線構造とすることで、架橋剤を添加し架橋反応させた後でも粘着剤被膜の柔軟性を維持し、接着力と保持力が両立でき、特にウレタンフォフォームなどの粗面に対する接着力に優れるアクリル系水性粘着剤組成物の製造方法として好適である。 In the present invention, the polymer chain has a linear structure with few branches, so that the flexibility of the pressure-sensitive adhesive film can be maintained even after a crosslinking agent is added and subjected to a crosslinking reaction, and both adhesive force and holding force can be achieved. It is suitable as a method for producing an acrylic water-based pressure-sensitive adhesive composition having excellent adhesion to rough surfaces such as foam.
まず、本発明の製造方法、すなわち乳化重合時のラジカル発生量であるが、使用する重合開始剤量から計算上求められるラジカル発生量を、反応系内に存在する重合性単量体成分１リットル当たり、毎分２×１０-13〜１５０×１０-13モルの範囲に制御することで、枝分かれ反応が抑制され、得られるポリマー鎖は直線構造となる。ここで言う「使用する重合開始剤量から計算上求められるラジカル発生量」とは、後記実施例に記載の計算式によって求められる反応系内に存在する重合性単量体成分１リットル当たり、毎分発生するラジカルの量であり、以下、２×１０-13〜１５０×１０-13ｍｏｌ／ｌ／ｍｉｎのように記載する。また、ラジカル発生量は、５×１０-13〜１２０×１０-13ｍｏｌ／ｌ／ｍｉｎであるとより好ましく、更には１０×１０-13〜１００×１０-13ｍｏｌ／ｌ／ｍｉｎであると、重合安定性が良く、かつポリマーの枝分かれ反応が更に抑制され、より柔軟な粘着剤被膜となり、ウレタンフォームに対する接着性が向上するため特に好ましい。 First, the production method of the present invention, that is, the amount of radicals generated during emulsion polymerization, the amount of radicals calculated from the amount of polymerization initiator used is calculated as 1 liter of polymerizable monomer component present in the reaction system. By controlling the range of 2 × 10 −13 to 150 × 10 −13 mol per minute, the branching reaction is suppressed and the resulting polymer chain has a linear structure. The “radical generation amount calculated from the amount of polymerization initiator to be used” here means that per 1 liter of the polymerizable monomer component present in the reaction system determined by the calculation formula described in the Examples below. This is the amount of radicals generated in minutes, and is described as 2 × 10 −13 to 150 × 10 −13 mol / l / min. The radical generation amount is more preferably 5 × 10 −13 to 120 × 10 −13 mol / l / min, and further preferably 10 × 10 −13 to 100 × 10 −13 mol / l / min. It is particularly preferable because the polymerization stability is good, the branching reaction of the polymer is further suppressed, a more flexible pressure-sensitive adhesive film is obtained, and the adhesion to urethane foam is improved.
計算上求められるラジカル発生量が、１５０×１０-13ｍｏｌ／ｌ／ｍｉｎを超えると、反応系内に過剰に存在するラジカルにより副反応、すなわち枝分かれ反応が起こり易くなる。そのため、得られるポリマー鎖は架橋構造をとるため、形成される被膜の柔軟性が損なわれ、粘着剤として使用するため架橋剤を添加した場合に接着力、特にウレタンフォームに対する接着力が低下する。また、２×１０-13ｍｏｌ／ｌ／ｍｉｎより少ないと発生するラジカルの濃度が低すぎて反応が進行しない。 If the radical generation amount calculated in the calculation exceeds 150 × 10 −13 mol / l / min, a side reaction, that is, a branching reaction is liable to occur due to an excessive amount of radicals present in the reaction system. Therefore, the obtained polymer chain has a crosslinked structure, so that the flexibility of the formed film is impaired, and when used as a pressure-sensitive adhesive, the adhesive strength, particularly the adhesive strength to urethane foam, is reduced when a crosslinking agent is added. On the other hand, if the concentration is less than 2 × 10 −13 mol / l / min, the concentration of the generated radicals is too low and the reaction does not proceed.
また、本発明の製造方法で用いる重合開始剤としては、ラジカル重合開始剤が用いられる。ラジカル重合開始剤の種類は特に制限は無く、例えば、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の過硫酸塩類、過酸化ベンゾイル、クメンハイドロパーオキサイド、ｔ−ブチルハイドロパーオキサイド等の有機過酸化物類、過酸化水素、または、４，４’−アゾビス（４−シアノ吉草酸）、２，２’−アゾビス（２−アミジノプロパン）二塩酸塩等のアゾ系開始剤などの種々の開始剤を使用できる。これらのなかでも過硫酸塩類、アゾ系開始剤が水素引き抜きなどの副反応が起こりづらいため好ましい。 Moreover, a radical polymerization initiator is used as a polymerization initiator used with the manufacturing method of this invention. The type of radical polymerization initiator is not particularly limited, and examples thereof include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, and organic peroxidations such as benzoyl peroxide, cumene hydroperoxide, and t-butyl hydroperoxide. Various initiators such as compounds, hydrogen peroxide, or azo-based initiators such as 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-amidinopropane) dihydrochloride Can be used. Of these, persulfates and azo initiators are preferred because side reactions such as hydrogen abstraction are difficult to occur.
乳化重合の反応温度は特に制限されるものでは無いが、これらの中でも３０〜９０℃の範囲で行うことが好ましい。３０℃より低い場合はラジカルが発生しづらく、重合安定性が低下する。また、９０℃を超える場合は、反応中のラジカル発生量を前述の範囲に制御しようとすると、開始剤量が非常に少なくなるため、反応操作上困難である。また、重合中のラジカル発生量を前述の範囲内に制御することが容易であることから、反応に用いる重合開始剤の１０時間半減期温度以下で反応することが特に好ましい。 The reaction temperature of the emulsion polymerization is not particularly limited, but among these, it is preferably performed in the range of 30 to 90 ° C. When it is lower than 30 ° C., radicals are not easily generated, and the polymerization stability is lowered. On the other hand, when the temperature exceeds 90 ° C., it is difficult to carry out the reaction operation because the amount of the initiator becomes very small if the radical generation amount during the reaction is controlled within the aforementioned range. Moreover, since it is easy to control the amount of radicals generated during the polymerization within the above-mentioned range, it is particularly preferable to react at a 10-hour half-life temperature or less of the polymerization initiator used for the reaction.
また、重合中のラジカル発生量を前述の範囲に制御すると、重合中の枝分かれ反応が抑えられるため、得られるアクリル系ポリマーから形成される被膜のゲル分率を２０重量％以下に制御することができる。このゲル分率は、架橋前のゲル分率、すなわち架橋剤等で故意に架橋反応を起こさせる前のゲル分率を指す。架橋剤を添加する前のポリマーから形成される被膜のゲル分率は低いほど好ましく、具体的には１０重量％以下とすると架橋剤を添加した後でも被膜の柔軟性が維持できるため好ましい。更には５％重量以下に制御すると特に好ましい。本発明で使用するゲル分率とは、アクリル系ポリマーから形成される被膜のトルエンに対する不溶解分の比率を意味する。ゲル分率は、後記実施例に記載した測定方法及び式により求められる数値に基づくものである。 In addition, when the radical generation amount during polymerization is controlled within the above range, branching reaction during polymerization is suppressed, so that the gel fraction of the film formed from the acrylic polymer obtained can be controlled to 20% by weight or less. it can. This gel fraction refers to a gel fraction before crosslinking, that is, a gel fraction before intentionally causing a crosslinking reaction with a crosslinking agent or the like. The lower the gel fraction of the film formed from the polymer before the addition of the cross-linking agent, the more preferable, and specifically 10% by weight or less is preferable because the flexibility of the film can be maintained even after the addition of the cross-linking agent. Furthermore, it is particularly preferable to control the weight to 5% or less. The gel fraction used by this invention means the ratio of the insoluble matter with respect to toluene of the film formed from an acrylic polymer. A gel fraction is based on the numerical value calculated | required by the measuring method and formula described in the postscript Example.
被膜の架橋前ゲル分率が２０重量％を超えた場合、ポリマー鎖の直線構造が損なわれる、すなわちポリマー鎖の分岐度合いが高くなり、被膜の柔軟性は低下する傾向にある。 When the pre-crosslinking gel fraction of the coating exceeds 20% by weight, the linear structure of the polymer chain is impaired, that is, the degree of branching of the polymer chain is increased, and the flexibility of the coating tends to decrease.
また、本発明で得られるアクリル系ポリマーを、実際に粘着剤として使用する場合の実質的なゲル分率としては、架橋剤等の添加等により１０〜５０重量％に調整することが好ましく、更に１５〜４５重量％であると特に好ましい。かかる範囲にあると接着力と保持力を維持しつつ、ウレタンフォームに対する接着性に優れるため好ましい。 In addition, the substantial gel fraction when the acrylic polymer obtained in the present invention is actually used as an adhesive is preferably adjusted to 10 to 50% by weight by addition of a crosslinking agent, etc. 15 to 45% by weight is particularly preferable. When it is in such a range, it is preferable because the adhesiveness to the urethane foam is excellent while maintaining the adhesive force and holding force.
上記範囲にゲル分率を調整する場合の架橋剤は特に制限は無く、架橋性を有する単量体を乳化重合することや、水溶性、或いは水分散性の架橋剤を重合後に添加しても良い。この場合、架橋剤としては、例えば、多官能性エポキシ化合物、多官能性メラミン化合物、多官能性ポリアミン化合物、多官能性ポリエチレンイミン化合物、多官能性（ブロック）イソシアネート化合物、金属塩化合物等が挙げられ、これらの１種または２種以上の混合物として使用することができる他に、水溶性または水分散性の熱硬化性樹脂、例えば、フェノール樹脂、尿素樹脂、メラミン樹脂、ウレタン樹脂等を混和して使用することもできる。中でも、粘着剤被膜の柔軟性を維持し易いことから、重合後に添加することが好ましい。 The crosslinking agent in the case of adjusting the gel fraction within the above range is not particularly limited, and emulsion polymerization of a monomer having crosslinking property or addition of a water-soluble or water-dispersible crosslinking agent after polymerization is possible. good. In this case, examples of the crosslinking agent include polyfunctional epoxy compounds, polyfunctional melamine compounds, polyfunctional polyamine compounds, polyfunctional polyethylenimine compounds, polyfunctional (block) isocyanate compounds, metal salt compounds, and the like. In addition to being able to be used as one or a mixture of two or more of these, a water-soluble or water-dispersible thermosetting resin such as a phenol resin, urea resin, melamine resin, urethane resin or the like is mixed. Can also be used. Especially, since it is easy to maintain the softness | flexibility of an adhesive film, it is preferable to add after superposition | polymerization.
また、本発明の製造方法により得られるアクリル系水性粘着剤組成物から形成される被膜のガラス転移温度（以下、Ｔｇという。）は−２５℃以下であることが好ましい。中でも−２５℃〜−６０℃の範囲にあることが、接着力と保持力等の物性のバランスに優れるため特に好ましい。本発明におけるＴｇは後記実施例に記載した測定方法で得られた数値に基づく。 Moreover, it is preferable that the glass transition temperature (henceforth Tg) of the film formed from the acrylic aqueous adhesive composition obtained by the manufacturing method of this invention is -25 degrees C or less. Especially, it is especially preferable that it exists in the range of -25 degreeC--60 degreeC, since it is excellent in the balance of physical properties, such as adhesive force and holding power. Tg in the present invention is based on numerical values obtained by the measurement methods described in the Examples below.
また、本発明の製造方法により得られるアクリル系水性粘着剤組成物に含有されるアクリル系ポリマーの分子量は、ポリマーのＴＨＦ溶解分をＧＰＣで測定した場合の重量平均分子量が１０万〜１５０万の範囲であると、粗面接着性と保持力を両立できる。中でも、２０万〜１２０万の範囲であることが好ましく、更には、２５万〜１００万の範囲であることが特に好ましい。なお、ＧＰＣの測定は、ポリマーを濃度が０．４％となるようにＴＨＦに完全に溶解し、不溶分を濾過で取り除いた後、溶解分のみを測定した。 Moreover, the molecular weight of the acrylic polymer contained in the acrylic aqueous pressure-sensitive adhesive composition obtained by the production method of the present invention is such that the weight-average molecular weight of the polymer dissolved in THF by GPC is 100,000 to 1,500,000. When it is within the range, both rough surface adhesion and holding power can be achieved. Especially, it is preferable that it is the range of 200,000 to 1,200,000, and it is especially preferable that it is the range of 250,000 to 1,000,000. GPC was measured by dissolving the polymer completely in THF so that the concentration was 0.4%, and removing insoluble matter by filtration, and then measuring only the dissolved matter.
本発明の製造方法で使用する単量体成分は、（ａ）カルボキシル基含有エチレン性不飽和単量体０．１〜１０重量％、（ｂ）炭素原子数が１〜１２のアルキル基を有するアルキル（メタ）アクリレート４５〜９９．９重量％の範囲で使用することが好ましい。その他の単量体成分は特に制限は無く、必要に応じて前述のＴｇの範囲内で任意の比率で組み合わせることができる。 The monomer component used in the production method of the present invention has (a) 0.1 to 10% by weight of a carboxyl group-containing ethylenically unsaturated monomer, and (b) an alkyl group having 1 to 12 carbon atoms. The alkyl (meth) acrylate is preferably used in the range of 45 to 99.9% by weight. There is no restriction | limiting in particular in other monomer components, It can combine in arbitrary ratios within the above-mentioned Tg range as needed.
前記カルボキシル基含有エチレン性不飽和単量体（ａ）としては、分子内にカルボキシル基とエチレン性不飽和基を有するものであれば特に限定されず使用することができる。かかるエチレン性不飽和単量体としては、例えば、アクリル酸、メタクリル酸、β−カルボキシエチル（メタ）アクリレート、２−（メタ）アクリロイルプロピオン酸、クロトン酸、イタコン酸、マレイン酸、フマル酸、イタコン酸ハーフエステル、マレイン酸ハーフエステル、無水マレイン酸、無水イタコン酸、ω−カルボキシ−ポリカプロラクトン（メタ）アクリレート、β−（メタ）アクリロイルオキシエチルハイドロゲンサクシネート、β−（メタ）ヒドロキシエチルハイドロゲンフタレート、及びこれらの塩等が挙げられ、これらの１種または２種以上の混合物を使用することができる。これらの中でも、特に、単量体成分の重合時の安定性及び接着物性、耐水白化性に優れる点で、アクリル酸、またはメタクリル酸を用いることが好ましい。前記カルボキシル基を有するエチレン性不飽和単量体の使用量は０．１〜１０重量％の範囲であることが好ましく、１〜１０重量％の範囲がより好ましく、２．５〜１０重量％が更に好ましい。この範囲にある時に優れた接着力と保持力が発現する。 The carboxyl group-containing ethylenically unsaturated monomer (a) is not particularly limited as long as it has a carboxyl group and an ethylenically unsaturated group in the molecule. Examples of the ethylenically unsaturated monomer include acrylic acid, methacrylic acid, β-carboxyethyl (meth) acrylate, 2- (meth) acryloylpropionic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, and itacone. Acid half ester, maleic acid half ester, maleic anhydride, itaconic anhydride, ω-carboxy-polycaprolactone (meth) acrylate, β- (meth) acryloyloxyethyl hydrogen succinate, β- (meth) hydroxyethyl hydrogen phthalate, And salts thereof and the like, and one or a mixture of two or more thereof can be used. Among these, it is particularly preferable to use acrylic acid or methacrylic acid in terms of excellent stability during polymerization of the monomer component, adhesive properties, and water whitening resistance. The amount of the ethylenically unsaturated monomer having a carboxyl group is preferably 0.1 to 10% by weight, more preferably 1 to 10% by weight, and 2.5 to 10% by weight. Further preferred. When in this range, excellent adhesive strength and holding power are exhibited.
前記炭素原子数が１〜１２のアルキル基を有するアルキル（メタ）アクリレート（ｂ）としては、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ−ブチル（メタ）アクリレート、ｉ−ブチル（メタ）アクリレート、ｔ−ブチル（メタ）アクリレート、ｎ−ヘキシル（メタ）アクリレート、ｎ−オクチル（メタ）アクリレート、ｉ−オクチル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、ｎ−ノニル（メタ）アクリレート、ｉｓｏ−ノニル（メタ）アクリレート、ｎ−デシル（メタ）アクリレート、ｎ−ラウリル（メタ）アクリレート等を挙げることができ、これらの１種または２種以上の混合物を使用することができる。これらのうち、炭素原子数４〜９のアルキル基を有するアルキル（メタ）アクリレートが、重合性が良好であり好ましい。かかる、炭素原子数が１〜１２のアルキル基を有するアルキル（メタ）アクリレートの使用量は４５〜９９．９重量％の範囲になる量であり、より好ましくは８０〜９９．９重量％である。この範囲にある時、前述した粘着剤被膜のＴｇを所望の範囲に調整でき、優れた接着力と保持力が発現するため好ましい。 Examples of the alkyl (meth) acrylate (b) having an alkyl group having 1 to 12 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl ( (Meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, n-octyl (meth) acrylate, i-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-nonyl (meth) An acrylate, iso-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-lauryl (meth) acrylate etc. can be mentioned, These 1 type (s) or 2 or more types of mixtures can be used. Among these, an alkyl (meth) acrylate having an alkyl group having 4 to 9 carbon atoms is preferable because of good polymerizability. The use amount of the alkyl (meth) acrylate having an alkyl group having 1 to 12 carbon atoms is an amount in the range of 45 to 99.9% by weight, and more preferably 80 to 99.9% by weight. . When it is in this range, the Tg of the pressure-sensitive adhesive film described above can be adjusted to a desired range, and an excellent adhesive force and holding force are exhibited, which is preferable.
これらの炭素原子数が１〜１２のアルキル基を有するアルキル（メタ）アクリレート（ｂ）の中でも、炭素原子数が４以上アルキル基を有するアルキル（メタ）アクリレート、例えば、ブチルアクリレート、２−エチルヘキシルアクリレート等を単量体成分の８０重量％以上用いると、本発明の組成物を用いた粘着剤被膜のＴｇを所望の範囲に調整できることから好ましい。 Among these alkyl (meth) acrylates (b) having an alkyl group having 1 to 12 carbon atoms, alkyl (meth) acrylates having an alkyl group having 4 or more carbon atoms, such as butyl acrylate and 2-ethylhexyl acrylate It is preferable to use 80% by weight or more of the monomer component because the Tg of the pressure-sensitive adhesive film using the composition of the present invention can be adjusted to a desired range.
また、前記これらの炭素原子数が１〜１２のアルキル基を有するアルキル（メタ）アクリレート（ｂ）の中でも、炭素原子数が１〜３のアルキル基を有するアルキル（メタ）アクリレート、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート等を単量体成分の１〜１５重量％の範囲で用いると、本発明の組成物を用いた粘着剤被膜の凝集力を向上することから好ましい。 Among these alkyl (meth) acrylates (b) having an alkyl group having 1 to 12 carbon atoms, alkyl (meth) acrylates having an alkyl group having 1 to 3 carbon atoms such as methyl ( Use of (meth) acrylate, ethyl (meth) acrylate or the like in the range of 1 to 15% by weight of the monomer component is preferable because the cohesive force of the pressure-sensitive adhesive film using the composition of the present invention is improved.
前記共重合反応の際、必要に応じて、（ａ）、（ｂ）以外のエチレン性不飽和単量体（ｃ）を共重合させることが出来る。（ａ）、（ｂ）以外のエチレン性不飽和単量体（ｃ）として、例えば、ステアリル（メタ）アクリレート、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート等の（メタ）アクリル酸エステル類；２，２，２−トリフルオロエチル（メタ）アクリレート、パーフルオロシクロヘキシル（メタ）アクリレート、２，２，３，３，−テトラフルオロプロピル（メタ）アクリレート、β−（パーフルオロオクチル）エチル（メタ）アクリレート等のフッ素含有エチレン性不飽和単量体；酢酸ビニル、プロピオン酸ビニル、ビニルブチラート、バーサチック酸ビニル等のビニルエステル類；メチルビニルエーテル、エチルビニルエーテル、プロピルビニルエーテル、ブチルビニルエーテル、アミルビニルエーテル、ヘキシルビニルエーテル等のビニルエーテル類；（メタ）アクリロニトリル等のニトリル基含有エチレン性不飽和単量体；スチレン、α−メチルスチレン、ビニルトルエン、ビニルアニソール、α−ハロスチレン、ビニルナフタリン、ジビニルスチレン等の芳香族環を有するビニル化合物；イソプレン、クロロプレン、ブタジエン、エチレン、テトラフルオロエチレン、フッ化ビニリデン、Ｎ−ビニルピロリドン等が挙げられる。これらの中でも、特に、単量体成分の重合時の安定性に優れる点で、（メタ）アクリル酸エステル類を用いることが好ましい。 In the copolymerization reaction, an ethylenically unsaturated monomer (c) other than (a) and (b) can be copolymerized as necessary. Examples of the ethylenically unsaturated monomer (c) other than (a) and (b) include (meth) acrylic acid esters such as stearyl (meth) acrylate, phenyl (meth) acrylate, and benzyl (meth) acrylate; 2,2,2-trifluoroethyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3, -tetrafluoropropyl (meth) acrylate, β- (perfluorooctyl) ethyl (meth) Fluorine-containing ethylenically unsaturated monomers such as acrylates; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl versatate; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, amyl vinyl ether, hexyl vinyl Ete Vinyl ethers such as; nitrile group-containing ethylenically unsaturated monomers such as (meth) acrylonitrile; aromatic rings such as styrene, α-methylstyrene, vinyltoluene, vinylanisole, α-halostyrene, vinylnaphthalene, divinylstyrene, etc. Vinyl compounds having: isoprene, chloroprene, butadiene, ethylene, tetrafluoroethylene, vinylidene fluoride, N-vinylpyrrolidone and the like. Among these, it is preferable to use (meth) acrylic acid esters in terms of excellent stability during polymerization of the monomer component.
また、（ａ）、（ｂ）以外のエチレン性不飽和単量体（ｃ）として、水性粘着剤のゲル分率を所望の範囲まで向上させることを目的とした場合は、カルボニル基やカルボキシル基以外の架橋性反応基を含有するエチレン性不飽和単量体を使用することもできる。これらの例としては、グリシジル（メタ）アクリレート、アリルグリシジルエーテル等のグリシジル基含有重合性単量体；２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、グリセロールモノ（メタ）アクリレート等の水酸基含有重合性単量体；アミノエチル（メタ）アクリレート、Ｎ−モノアルキルアミノアルキル（メタ）アクリレート、Ｎ，Ｎ−ジアルキルアミノアルキル（メタ）アクリレート等のアミノ基含有重合性単量体；Ｎ−メチロール（メタ）アクリルアミド、Ｎ−イソプロポキシメチル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、Ｎ−イソブトキシメチル（メタ）アクリルアミド等のメチロールアミド基またはそのアルコキシ化物含有重合性単量体；ビニルトリクロロシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、γ−（メタ）アクリロキシプロピルトリメトキシシラン、γ−（メタ）アクリロキシプロピルトリエトキシシラン、γ−（メタ）アクリロキシプロピルメチルジメトキシシラン、γ−（メタ）アクリロキシプロピルメチルジエトキシシラン、γ−（メタ）アクリロキシプロピルトリイソプロポキシシラン、Ｎ−β−（Ｎ−ビニルベンジルアミノエチル）−γ−アミノプロピルトリメトキシシラン及びその塩酸塩等のシリル基含有重合性単量体；２−アジリジニルエチル（メタ）アクリレート等のアジリジニル基含有重合性単量体；（メタ）アクリロイルイソシアナート、（メタ）アクリロイルイソシアナートエチルのフェノール或いはメチルエチルケトオキシム付加物等のイソシアナート基及び／またはブロック化イソシアナート基含有重合性単量体；２−イソプロペニル−２−オキサゾリン、２−ビニル−２−オキサゾリン等のオキサゾリン基含有重合性単量体；（メタ）アクリルアミド、Ｎ−モノアルキル（メタ）アクリルアミド、Ｎ，Ｎ−ジアルキル（メタ）アクリルアミド等のアミド基含有重合性単量体；ジシクロペンテニル（メタ）アクリレート等のシクロペンテニル基含有重合性単量体；アリル（メタ）アクリレート等のアリル基含有重合性単量体；アクロレイン、ジアセトン（メタ）アクリルアミド等のカルボニル基含有重合性単量体；アセトアセトキシエチル（メタ）アクリレート等のアセトアセチル基含有重合性単量体等が挙げられる。 In addition, as the ethylenically unsaturated monomer (c) other than (a) and (b), when it is intended to improve the gel fraction of the aqueous pressure-sensitive adhesive to a desired range, a carbonyl group or a carboxyl group An ethylenically unsaturated monomer containing a crosslinkable reactive group other than can also be used. Examples of these include glycidyl group-containing polymerizable monomers such as glycidyl (meth) acrylate and allyl glycidyl ether; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) Hydroxyl group-containing polymerizable monomers such as acrylate and glycerol mono (meth) acrylate; amino such as aminoethyl (meth) acrylate, N-monoalkylaminoalkyl (meth) acrylate, and N, N-dialkylaminoalkyl (meth) acrylate Group-containing polymerizable monomer: methylol amide such as N-methylol (meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) acrylamide Group or an alkoxylate-containing polymerizable monomer; vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ- (meth) acryloxypropyltrimethoxysilane, γ- ( (Meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, N-β Silyl group-containing polymerizable monomers such as-(N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane and its hydrochloride; aziridinyl group-containing polymerizable monomers such as 2-aziridinylethyl (meth) acrylate Mer; (meth) acryloyl isocyana Isocyanate- and / or blocked isocyanate group-containing polymerizable monomers such as phenol or methyl ethyl ketoxime adduct of (meth) acryloyl isocyanate ethyl; 2-isopropenyl-2-oxazoline, 2-vinyl-2 -Oxazoline group-containing polymerizable monomers such as oxazoline; Amide group-containing polymerizable monomers such as (meth) acrylamide, N-monoalkyl (meth) acrylamide, N, N-dialkyl (meth) acrylamide; Dicyclopentenyl Cyclopentenyl group-containing polymerizable monomers such as (meth) acrylate; Allyl group-containing polymerizable monomers such as allyl (meth) acrylate; Carbonyl group-containing polymerizable monomers such as acrolein and diacetone (meth) acrylamide; Such as acetoacetoxyethyl (meth) acrylate Setoasechiru group-containing polymerizable monomer, and the like.
また、さらに（ａ）、（ｂ）以外のエチレン性不飽和単量体（ｃ）としては、水性粘着剤のゲル分率を所望の範囲まで向上させることを目的とした場合には、分子中に２個以上のエチレン性不飽和基を含有する多官能性エチレン性不飽和単量体を使用することもできる。これらの例としては、具体的には、エチレングリコールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ジアリルフタレート、ジビニルベンゼン、アリル（メタ）アクリレート等が挙げられる。 Further, as the ethylenically unsaturated monomer (c) other than (a) and (b), in the case where the purpose is to improve the gel fraction of the aqueous pressure-sensitive adhesive to a desired range, A polyfunctional ethylenically unsaturated monomer containing two or more ethylenically unsaturated groups can also be used. Specific examples thereof include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and polyethylene. Examples include glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, diallyl phthalate, divinylbenzene, and allyl (meth) acrylate.
前記多官能性エチレン性不飽和単量体を使用すると粘着剤の凝集力を向上させ、保持力が良好なものとなるが、接着力と保持力を共に優れたものとするためには、多官能性エチレン性不飽和単量体の使用量は、前述の如く粘着剤被膜のゲル分率が１０〜５０重量％、好ましくは１５〜４５重量％の範囲となる量で使用することが好ましい。 When the polyfunctional ethylenically unsaturated monomer is used, the cohesive force of the pressure-sensitive adhesive is improved and the holding power is good, but in order to improve both the adhesive strength and the holding power, As described above, the functional ethylenically unsaturated monomer is preferably used in such an amount that the gel fraction of the pressure-sensitive adhesive film is 10 to 50% by weight, preferably 15 to 45% by weight.
また、（ａ）、（ｂ）以外のエチレン性不飽和単量体（ｃ）として、乳化重合時の安定性、水分散型アクリル系ポリマーの貯蔵安定性を向上させることを目的とした場合には、必要に応じてスルホン酸基及び／またはサルフェート基（及び／またはその塩）、リン酸基及び／またはリン酸エステル基（及び／またはその塩）を含有する単量体を使用することができ、例えばビニルスルホン酸、スチレンスルホン酸等のビニルスルホン酸類またはその塩、アリルスルホン酸、２−メチルアリルスルホン酸等のアリル基含有スルホン酸類またはその塩、（メタ）アクリル酸２−スルホエチル、（メタ）アクリル酸２−スルホプロピル等の（メタ）アクリレート基含有スルホン酸類またはその塩、（メタ）アクリルアミド−ｔ−ブチルスルホン酸等の（メタ）アクリルアミド基含有スルホン酸類またはその塩が挙げられる。リン酸基を有するエチレン性不飽和単量体の市販品としては、「アデカリアソープＰＰ−７０、ＰＰＥ−７１０」［旭電化工業(株)製］等が挙げられる。 In addition, as the ethylenically unsaturated monomer (c) other than (a) and (b), when the purpose is to improve the stability during emulsion polymerization and the storage stability of the water-dispersed acrylic polymer May use a monomer containing a sulfonic acid group and / or a sulfate group (and / or a salt thereof), a phosphoric acid group and / or a phosphate ester group (and / or a salt thereof) as necessary. For example, vinyl sulfonic acids such as vinyl sulfonic acid and styrene sulfonic acid or salts thereof, allyl group-containing sulfonic acids such as allyl sulfonic acid and 2-methylallyl sulfonic acid or salts thereof, 2-sulfoethyl (meth) acrylate, ( (Meth) acrylate group-containing sulfonic acids such as 2-sulfopropyl methacrylate or salts thereof, (meth) acrylamide-t-butylsulfonic acid, etc. (Meth) acrylamide group-containing sulfonic acids or salts thereof. As a commercial item of the ethylenically unsaturated monomer which has a phosphoric acid group, "Adekalia soap PP-70, PPE-710" [Asahi Denka Kogyo Co., Ltd. product] etc. are mentioned.
また、本発明の製造方法において、前述の分子量の範囲内に調整するために分子量調整剤を使用しても良い。その場合に単量体成分を乳化重合する際に、連鎖移動能を有する化合物、例えばラウリルメルカプタン、オクチルメルカプタン、ドデシルメルカプタン、２−メルカプトエタノール、チオグリコール酸オクチル、３−メルカプトプロピオン酸、チオグリセリン等のメルカプタン類、またはα−メチルスチレン・ダイマー等を添加してもよい。 In the production method of the present invention, a molecular weight adjusting agent may be used to adjust the molecular weight within the aforementioned range. In this case, when emulsion polymerization of the monomer component, a compound having chain transfer ability, such as lauryl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-mercaptoethanol, octyl thioglycolate, 3-mercaptopropionic acid, thioglycerin, etc. Mercaptans or α-methylstyrene dimer may be added.
次に、本発明の製造方法で、単量体成分を水性媒体中で乳化重合する際には、乳化剤やその他の分散安定剤を使用して重合することができる。本発明で使用できる乳化剤としては、陰イオン性乳化剤、非イオン性乳化剤、陽イオン性乳化剤の種々のものが使用できる。本発明で使用する陰イオン性乳化剤としては、例えば、高級アルコールの硫酸エステル及びその塩、アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルフェニルスルホン酸塩、ポリオキシエチレンアルキルジフェニルエーテルスルホン酸塩、アルキルジフェニルエーテルジスルホン酸塩、コハク酸ジアルキルエステルスルホン酸塩等が挙げられ、非イオン性乳化剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンジフェニルエーテル、ポリオキシエチレン−ポリオキシプロピレンブロック共重合体等が挙げられ、これらの１種または２種以上の混合物を使用することができる。 Next, in the production method of the present invention, when the monomer component is emulsion-polymerized in an aqueous medium, it can be polymerized using an emulsifier or other dispersion stabilizer. As the emulsifier that can be used in the present invention, various anionic emulsifiers, nonionic emulsifiers, and cationic emulsifiers can be used. Examples of the anionic emulsifier used in the present invention include sulfates of higher alcohols and salts thereof, alkylbenzene sulfonates, polyoxyethylene alkylphenyl sulfonates, polyoxyethylene alkyl diphenyl ether sulfonates, alkyl diphenyl ether disulfonic acids. And nonionic emulsifiers include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene diphenyl ether, polyoxyethylene-polyoxypropylene block copolymer Etc., and one or a mixture of two or more of these can be used.
更に、一般的に「反応性乳化剤」と称される重合性不飽和基を分子内に有する乳化剤を使用することもできる。本発明で使用できる反応性乳化剤としては、例えば、スルホン酸基及びその塩を有する「ラテムルＳ−１８０」［花王(株)製］、「エレミノールＪＳ−２、ＲＳ−３０」［三洋化成工業(株)製］等；硫酸基及びその塩を有する「アクアロンＨＳ−１０、ＨＳ−２０、ＫＨ−０５、ＫＨ−１０」［第一工業製薬(株)製］、「アデカリアソープＳＥ−１０、ＳＥ−２０、ＳＲ−１０Ｎ、ＳＲ−２０Ｎ」［旭電化工業(株)製］等；リン酸基を有する「ニューフロンティアＡ−２２９Ｅ」［第一工業製薬(株)製］等；非イオン性親水基を有する「アクアロンＲＮ−１０、ＲＮ−２０、ＲＮ−３０、ＲＮ−５０、ＥＲ−１０、ＥＲ−２０、ＥＲ−３０、ＥＲ−４０」［第一工業製薬(株)製］等が挙げられ、これらの１種または２種以上の混合物が使用できる。反応性乳化剤を使用することは、重合安定性に加え被膜の耐水性が向上するため好ましい。 Furthermore, an emulsifier having a polymerizable unsaturated group in the molecule generally called “reactive emulsifier” can also be used. Examples of reactive emulsifiers that can be used in the present invention include “Latemul S-180” (manufactured by Kao Corporation) having a sulfonic acid group and a salt thereof, “Eleminol JS-2, RS-30” [Sanyo Chemical Industries ( "Aqualon HS-10, HS-20, KH-05, KH-10" [Daiichi Kogyo Seiyaku Co., Ltd.] having a sulfate group and a salt thereof, "Adekaria soap SE-10, SE-20, SR-10N, SR-20N ”[Asahi Denka Kogyo Co., Ltd.] etc .;“ New Frontier A-229E ”having a phosphate group [Daiichi Kogyo Seiyaku Co., Ltd.] etc .; nonionic “AQUALON RN-10, RN-20, RN-30, RN-50, ER-10, ER-20, ER-30, ER-40” [Daiichi Kogyo Seiyaku Co., Ltd.] etc. having a hydrophilic group One or a mixture of two or more of these can be used.The use of a reactive emulsifier is preferred because the water resistance of the coating is improved in addition to the polymerization stability.
また、前記製造方法で使用することのできる乳化剤以外のその他の分散安定剤としては、例えば、ポリビニルアルコール、繊維素エーテル、澱粉、マレイン化ポリブタジエン、マレイン化アルキッド樹脂、ポリアクリル酸（塩）、ポリアクリルアミド、水性アクリル樹脂、水性ポリエステル樹脂、水性ポリアミド樹脂、水性ポリウレタン樹脂等の合成或いは天然の水溶性高分子物質が挙げられ、これらの１種または２種以上の混合物を使用することができる。 Examples of other dispersion stabilizers other than the emulsifier that can be used in the production method include, for example, polyvinyl alcohol, fiber ether, starch, maleated polybutadiene, maleated alkyd resin, polyacrylic acid (salt), poly Synthetic or natural water-soluble polymer materials such as acrylamide, water-based acrylic resin, water-based polyester resin, water-based polyamide resin, water-based polyurethane resin and the like can be mentioned, and one or a mixture of two or more of these can be used.
本発明のアクリル系水性粘着剤の製造方法としては、例えば、以下の（１）〜（３）の方法が挙げられる。即ち、（１）水、重合性単量体成分、重合開始剤、必要に応じて乳化剤及び分散安定剤を一括混合して乳化重合する方法、（２）水、エチレン性不飽和単量体、乳化剤を予め混合したものと、重合開始剤を並行して供給して乳化重合する、いわゆるプレエマルジョン法、（３）水、重合性単量体成分、重合開始剤、必要に応じて乳化剤及び分散安定剤を別々に並行して供給して乳化重合する方法が挙げられる。 Examples of the method for producing the acrylic aqueous pressure-sensitive adhesive of the present invention include the following methods (1) to (3). That is, (1) water, a polymerizable monomer component, a polymerization initiator, and a method of emulsion polymerization by mixing together an emulsifier and a dispersion stabilizer as needed, (2) water, an ethylenically unsaturated monomer, A pre-emulsion method in which an emulsifier is mixed in advance and a polymerization initiator is supplied in parallel to perform emulsion polymerization, (3) water, a polymerizable monomer component, a polymerization initiator, and an emulsifier and dispersion as necessary A method of emulsion polymerization by separately supplying stabilizers in parallel can be mentioned.
これら本発明のアクリル系水性粘着剤の製造方法においては、乳化重合の最初からラジカル発生量をコントロールして行ってもよいが、中でも重合性単量体成分と重合開始剤のそれぞれ一部を用いて乳化重合して、初期に樹脂粒子の分散体を製造した後、これをシードとして、ラジカル発生量を制御した乳化重合を行うことが好ましい。ここで用いる重合性単量体成分量は、通常、全ての重合性単量体成分量の０．３〜５重量％の範囲であり、ラジカル発生量に制限はないが、重合開始剤の８０％以上が消費されるまで反応させることが好ましい。 In the method for producing the acrylic water-based pressure-sensitive adhesive of the present invention, the radical generation amount may be controlled from the beginning of the emulsion polymerization. Among them, a part of each of the polymerizable monomer component and the polymerization initiator is used. It is preferable to carry out emulsion polymerization by initially producing a dispersion of resin particles and then using this as a seed to carry out emulsion polymerization with controlled radical generation. The amount of the polymerizable monomer component used here is usually in the range of 0.3 to 5% by weight of the total amount of the polymerizable monomer components, and the amount of radical generation is not limited, but 80% of the polymerization initiator. It is preferable to make it react until more than% is consumed.
前記（１）〜（３）の方法の中でも、（２）の方法は重合安定性が高いため好ましい。更には、方法（４）として、予め調製した乳化液の一部を滴下した後、残りの乳化液とともに反応性乳化剤を滴下する方法がある。この方法（４）であると、重合安定性が向上するだけでなく、得られるアクリル系水性粘着剤組成物の被膜の耐水性が向上するため好ましい。 Among the methods (1) to (3), the method (2) is preferable because of high polymerization stability. Furthermore, as the method (4), there is a method in which a part of an emulsion prepared in advance is dropped and then a reactive emulsifier is dropped together with the remaining emulsion. This method (4) is preferable because not only the polymerization stability is improved but also the water resistance of the resulting acrylic aqueous pressure-sensitive adhesive coating film is improved.
このとき後から添加する反応性乳化剤の供給方法は、特に制限されるものではなく、残りの乳化液に混合して供給する方法、または乳化液と別々に並行して反応容器内に供給する方法などがある。 The method for supplying the reactive emulsifier to be added later is not particularly limited, and is a method of supplying the remaining emulsified liquid by mixing it or a method of supplying it into the reaction vessel separately from the emulsion liquid in parallel. and so on.
また、後から添加する反応性乳化剤は特に制限されるものでは無く前述の反応性乳化剤から任意に使用することができる。これらの中でも、下記一般式で表される乳化剤を使用すると、理由ははっきりしないが、ウレタンフォームに対する接着性に優れるため特に好ましい。 Further, the reactive emulsifier added later is not particularly limited and can be arbitrarily used from the above-mentioned reactive emulsifiers. Among these, when an emulsifier represented by the following general formula is used, the reason is not clear, but it is particularly preferable because of excellent adhesion to urethane foam.
（式中、Ｒはアルキル基、ｎは整数を示す。） (In the formula, R represents an alkyl group, and n represents an integer.)
上記一般式で表される反応性乳化剤を添加する乳化液（残りの乳化液）の割合は、全乳化液の１０〜９０重量％であると、粗面接着性に優れる。また、２０〜８０重量％であることが好ましい。更には３０〜７０重量％であると、ウレタンフォームに対する接着性に優れるため特に好ましい。 When the ratio of the emulsion (remaining emulsion) to which the reactive emulsifier represented by the above general formula is added is 10 to 90% by weight of the total emulsion, the rough surface adhesion is excellent. Moreover, it is preferable that it is 20 to 80 weight%. Furthermore, it is especially preferable that it is 30 to 70% by weight because of excellent adhesion to urethane foam.
また、重合開始剤の供給方法は、常に一定速度（一定のラジカル発生量）で供給する方法、供給速度が徐々に変化する方法、更に、前記した重合性単量体成分を分割して供給する場合は、一段目と二段目で異なる速度で重合開始剤を供給する方法などがあるが、前述のラジカル発生量の範囲内になるように供給する方法であれば特に制限はない。中でも、常に一定速度（一定のラジカル発生量）で供給することが、重合安定性や、ポリマー構造のコントロールが容易であるため好ましい。 In addition, the polymerization initiator is supplied at a constant rate (a constant radical generation amount), a method in which the supply rate is gradually changed, and the polymerizable monomer component is supplied in a divided manner. In this case, there is a method of supplying the polymerization initiator at different speeds in the first stage and the second stage, but there is no particular limitation as long as it is a method of supplying the polymerization initiator within the above-mentioned range of radical generation amount. Among them, it is preferable to always supply at a constant rate (a constant radical generation amount) because polymerization stability and control of the polymer structure are easy.
また、本発明の水性粘着剤組成物の製造方法で得られるアクリル系水性粘着剤組成物の平均粒子径は特に制限されるものではない。一般的な使用範囲として考えられる５０〜１０００ｎｍが好ましい。ここでの粒子の平均粒子径とは、エマルジョン粒子の体積基準での５０％メジアン径をいい、数値は後記実施例に記載の動的光散乱法により測定して得られる値に基づくものである。 Moreover, the average particle diameter of the acrylic water-based pressure-sensitive adhesive composition obtained by the method for producing the water-based pressure-sensitive adhesive composition of the present invention is not particularly limited. 50-1000 nm considered as a general use range is preferable. Here, the average particle diameter of the particles refers to the 50% median diameter of the emulsion particles on the volume basis, and the numerical values are based on values obtained by measurement by the dynamic light scattering method described in Examples below. .
また、本発明の製造方法により得られるアクリル系水性粘着剤組成物の固形分濃度は、特に制限されるものではないが、製造時の作業性や輸送コストという点、及び乾燥して使用する際の乾燥性に優れるという点から、固形分濃度が４０〜７０重量％であることが好ましい。 In addition, the solid content concentration of the acrylic aqueous pressure-sensitive adhesive composition obtained by the production method of the present invention is not particularly limited, but is in terms of workability at the time of production and transportation cost, and when used by drying. From the viewpoint of excellent dryability, the solid content concentration is preferably 40 to 70% by weight.
また、本発明の製造方法においては、必要に応じて、アクリル系水性粘着剤組成物の所望の効果を阻害しない範囲で、充填剤、顔料、ｐＨ調整剤、被膜形成助剤、レベリング剤、増粘剤、撥水剤、粘着付与剤、消泡剤等公知のものを適宜添加して使用することができる。 In addition, in the production method of the present invention, if necessary, the filler, pigment, pH adjuster, film forming aid, leveling agent, increase agent can be used as long as the desired effect of the acrylic aqueous pressure-sensitive adhesive composition is not impaired. Known agents such as a sticking agent, a water repellent, a tackifier, and an antifoaming agent can be appropriately added and used.
本発明で得られるアクリル系水性粘着剤組成物は、種々の粘着製品に利用できる。その粘着製品は、基材と上記のアクリル系水性粘着剤組成物の層とから構成されている。この基材には特に制限は無く、紙、プラスチックフィルム、不織布等用途に応じて選択し、使用することができる。 The acrylic water-based pressure-sensitive adhesive composition obtained in the present invention can be used for various pressure-sensitive adhesive products. The pressure-sensitive adhesive product is composed of a base material and a layer of the above acrylic aqueous pressure-sensitive adhesive composition. There is no restriction | limiting in particular in this base material, According to uses, such as paper, a plastic film, and a nonwoven fabric, it can select and use.
本発明で得られるアクリル系水性粘着剤組成物を用いて粘着剤組成物の層を形成する方法としては、上記基材の上に、該アクリル系水性粘着剤組成物を直接塗工して乾燥させる直接法、シリコーン等で離型処理された紙、またはプラスチックフィルム等の離型材の上に、該水性粘着材組成物を塗工して乾燥させ、粘着剤層を形成させた後、該粘着剤層の上に基材を重ねて加圧し、該基材上に粘着剤層を転写する転写法が挙げられる。 As a method of forming a layer of the pressure-sensitive adhesive composition using the acrylic water-based pressure-sensitive adhesive composition obtained in the present invention, the acrylic water-based pressure-sensitive adhesive composition is directly applied on the substrate and dried. The water-based pressure-sensitive adhesive composition is coated on a release material such as a silicone film or a release material such as a plastic film or dried to form a pressure-sensitive adhesive layer. There is a transfer method in which a base material is stacked on the adhesive layer and pressed to transfer the pressure-sensitive adhesive layer onto the base material.
塗工方法としては、塗工機としてロールコーター、コンマコーター、リップコーター、ファウンテンダイコーター、グラビアコーター等を使用する方法が挙げられる。 Examples of the coating method include a method using a roll coater, a comma coater, a lip coater, a fountain die coater, a gravure coater or the like as a coating machine.
アクリル系水性粘着剤組成物は、一般に固形分濃度が４０〜７０重量％、粘度が１０〜１０，０００ｍＰａ・ｓ（ＢＭ型粘度計、６０回転、２５℃）、ｐＨが６〜９程度である。上記の直接法で塗工する場合には、塗工方法の種類にもよるが、一般的により高速に塗工するためには低粘度であることが求められることが多い。また転写法で塗工する場合には、粘度が３００〜１０，０００ｍＰａ・ｓ（同上）のものが好ましい。 The acrylic aqueous pressure-sensitive adhesive composition generally has a solid content concentration of 40 to 70% by weight, a viscosity of 10 to 10,000 mPa · s (BM type viscometer, 60 rotations, 25 ° C.), and a pH of about 6 to 9. . In the case of coating by the above direct method, although it depends on the type of coating method, in general, a low viscosity is often required for coating at a higher speed. Moreover, when applying by a transfer method, a thing with a viscosity of 300-10,000 mPa * s (same as the above) is preferable.
以下、本発明を実施例と比較例により、一層、具体的に説明するが、本発明の範囲はこれら実施例に限定されるものではない。以下において、特に断らない限り、「％」は重量％、「部」は重量部をそれぞれ示すものとする。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples. In the following, unless otherwise specified, “%” represents “% by weight”, and “part” represents “part by weight”.
［ラジカル発生量の計算方法］
反応系内に存在する重合性単量体成分１リットル当たり、毎分発生するラジカルの量（Ｃ）は、以下の式で求めた。
[Calculation method of radical generation amount]
The amount (C) of radicals generated per minute per liter of the polymerizable monomer component present in the reaction system was determined by the following equation.
Ｃ＝ｃ／２／ｔ／６０ （ｍｏｌ／ｌ／ｍｉｎ）
ｃ；重合開始剤の濃度（ｍｏｌ／ｌ）
ｔ；半減期（ｈ）
前述の式中の半減期（ｔ）は、以下の式で求めた。
C = c / 2 / t / 60 (mol / l / min)
c: Concentration of polymerization initiator (mol / l)
t: Half-life (h)
The half-life (t) in the above formula was determined by the following formula.
ｔ＝ｌｎ２／ｋ
ｋ；分解速度定数
前述の分解速度定数（ｋ）は以下のＡｒｒｈｅｎｉｕｓの式より求めた。
t = ln2 / k
k: Decomposition rate constant The above-described decomposition rate constant (k) was determined from the following Arrhenius equation.
ｋ＝Ａ×ｅｘｐ（−ΔＥ／ＲＴ）
Ａ；頻度因子
ΔＥ；活性化エネルギー（Ｊ／ｍｏｌ）
Ｒ ；気体定数
Ｔ ；温度（Ｋ）
k = A × exp (−ΔE / RT)
A; Frequency factor ΔE; Activation energy (J / mol)
R: Gas constant T: Temperature (K)
［ゲル分率の測定方法］
厚さ２５μｍのポリエチレンテレフタレートフィルムの表面に、乾燥後における膜厚が２５μｍとなるように後記実施例で得られたアクリル系水性粘着剤組成物を塗布し、１００℃で２分間乾燥して粘着シートを作成し、これを５０ｍｍ×５０ｍｍの大きさに切り取ったものを試料とした。次に、予め上記試料のトルエン浸漬前の重量（Ｇ１）と粘着剤塗布前（基材のみ）の重量（Ｇ０）を測定しておき、トルエン溶液中に常温で２４時間浸漬した。そして、浸漬後の試料のトルエン不溶解分を３００メッシュ金網で濾過することにより分離し、１１０℃で１時間乾燥した後の残さの重量（Ｇ２）を測定し、以下の式に従ってゲル分率を求めた。
[Measurement method of gel fraction]
On the surface of a 25 μm thick polyethylene terephthalate film, the acrylic aqueous pressure-sensitive adhesive composition obtained in Examples below was applied so that the film thickness after drying was 25 μm, and dried at 100 ° C. for 2 minutes to give a pressure sensitive adhesive sheet Was prepared and cut into a size of 50 mm × 50 mm as a sample. Next, the weight (G1) of the sample before immersion in toluene and the weight (G0) before application of the adhesive (base material only) were measured in advance and immersed in a toluene solution at room temperature for 24 hours. And the toluene insoluble matter of the sample after immersion is separated by filtering with a 300 mesh wire mesh, the weight (G2) of the residue after drying at 110 ° C. for 1 hour is measured, and the gel fraction is determined according to the following formula: Asked.
ゲル分率（重量％）＝〔（Ｇ２−Ｇ０）／（Ｇ１−Ｇ０）〕×１００ Gel fraction (% by weight) = [(G2-G0) / (G1-G0)] × 100
［Ｔｇの測定方法］
後記実施例で得られた水分散型アクリル系ポリマーを乾燥後の膜厚が０．３ｍｍとなるようにガラス板に塗工し、２５℃で２４時間乾燥した後、ガラス板から剥離し、更に１００℃で５分間乾燥したものを試料とし、直径５ｍｍ、深さ２ｍｍのアルミニウム製円筒型セルに試料約１０ｍｇを秤取し、ＴＡインスツルメント社製のＤＳＣ−２９２０モジュレイテッド型示差走査型熱量計を用い、窒素雰囲気下で−１５０℃から昇温速度２０℃／分で１００℃まで昇温した時の吸熱曲線を測定して求めた。
[Method for measuring Tg]
The water-dispersed acrylic polymer obtained in Examples below is applied to a glass plate so that the film thickness after drying is 0.3 mm, dried at 25 ° C. for 24 hours, and then peeled off from the glass plate. A sample dried at 100 ° C. for 5 minutes was weighed in an aluminum cylindrical cell having a diameter of 5 mm and a depth of 2 mm, and a DSC-2920 modulated differential scanning calorie manufactured by TA Instruments was used. Using a meter, an endothermic curve was measured when the temperature was raised from −150 ° C. to 100 ° C. at a rate of temperature rise of 20 ° C./min in a nitrogen atmosphere.
［平均粒子径の測定方法］
日機装(株)製マイクロトラックＵＰＡ型粒度分布測定装置にて測定した平均粒子径（体積基準での５０％メジアン径）の値を求めた。
[Measurement method of average particle size]
The value of the average particle diameter (50% median diameter based on volume) measured with a Nikkiso Co., Ltd. Microtrac UPA type particle size distribution analyzer was determined.
［接着力の測定方法］
厚さ２５μｍのポリエチレンテレフタレートフィルムの表面に、乾燥後における膜厚が２５μｍとなるように後記実施例で得られたアクリル系水性粘着剤組成物を塗布し、１００℃で２分間乾燥して粘着シートを作成した。粘着シートおよび被着体として鏡面仕上げしたステンレス板を用い、ＪＩＳ Ｚ−０２３７に準じて２３℃、５０％ＲＨの雰囲気下で１８０度剥離強度を測定し、接着力とした。
[Measurement method of adhesive strength]
On the surface of a 25 μm thick polyethylene terephthalate film, the acrylic aqueous pressure-sensitive adhesive composition obtained in Examples below was applied so that the film thickness after drying was 25 μm, and dried at 100 ° C. for 2 minutes to give a pressure sensitive adhesive sheet It was created. A 180-degree peel strength was measured under an atmosphere of 23 ° C. and 50% RH in accordance with JIS Z-0237 using a mirror-finished stainless steel plate as the pressure-sensitive adhesive sheet and the adherend to determine the adhesive strength.
［ウレタンフォームに対する接着性の測定方法］
厚さ２５μｍのポリエチレンテレフタレートフィルムの表面に、乾燥後における膜厚が２５μｍとなるように後記実施例で得られたアクリル系水性粘着剤組成物を塗布し、１００℃で２分間乾燥して粘着シートを作成した。この基材を２３℃、５０％ＲＨの雰囲気下でＥＣＳ系ウレタンフォームへ２ｋｇロールにて貼り合わせ、直後に手でゆっくりと引き剥がした。このときのウレタンフォーム表面の破壊状態を以下の基準で評価した。
[Measurement method of adhesion to urethane foam]
On the surface of a 25 μm thick polyethylene terephthalate film, the acrylic aqueous pressure-sensitive adhesive composition obtained in Examples below was applied so that the film thickness after drying was 25 μm, and dried at 100 ° C. for 2 minutes to give a pressure sensitive adhesive sheet It was created. This base material was bonded to an ECS urethane foam with a 2 kg roll under an atmosphere of 23 ° C. and 50% RH, and immediately after that, it was slowly peeled off by hand. The destruction state of the urethane foam surface at this time was evaluated according to the following criteria.
○；ウレタンフォーム材破
△；ウレタンフォーム表面の粘着剤層への転着あり
×；ウレタンフォーム表面の粘着剤層への転着なし
○: Urethane foam material breakage △: Transfer of urethane foam surface to adhesive layer ×: No transfer of urethane foam surface to adhesive layer
［保持力の測定方法］
接着力測定時と同様にして粘着シートを作成し、ステンレス板に接着面積が２５ｍｍ×２５ｍｍとなるように粘着シートを貼付け、４０℃にて１ｋｇの荷重をかけてずれ落ちるまでの時間を測定し、その保持時間を保持力とした。また、１２時間後にも保持されていた場合には、保持時間を１２時間以上とし、初期貼付け位置からのずれ幅を測定し、併記した。
[Method of measuring holding force]
Create a pressure-sensitive adhesive sheet in the same way as when measuring the adhesive strength, affix the pressure-sensitive adhesive sheet to the stainless steel plate so that the bonding area is 25 mm x 25 mm, and measure the time until it slips off under a load of 1 kg at 40 ° C. The holding time was defined as holding power. Moreover, when it was hold | maintained after 12 hours, the holding time was made into 12 hours or more, the shift | offset | difference width from the initial sticking position was measured, and it described together.
［タックの測定方法］
接着力測定時と同様にして粘着シートを作成し、ＪＩＳ Ｚ−０２３７の球転法に準じて２３℃、５０％ＲＨの雰囲気下で測定した。
[Tack measurement method]
A pressure-sensitive adhesive sheet was prepared in the same manner as when measuring the adhesive force, and measured under an atmosphere of 23 ° C. and 50% RH according to the ball rolling method of JIS Z-0237.
実施例１
(1)乳化液Ａの調製
容器に、ラテムルＥ−１１８Ｂ［花王（株）製；有効成分２５％］１０部と脱イオン水１００部を入れ、均一に溶解した。そこに、２−エチルヘキシルアクリレート２４５部、ｎ−ブチルアクリレート２４５部、アクリル酸１０部、ラウリルメルカプタン１部を加えて乳化し、乳化液Ａを得た。
Example 1
(1) Preparation of Emulsion A A Lattemul E-118B [manufactured by Kao Corporation; active ingredient 25%] 10 parts and 100 parts of deionized water were uniformly dissolved in a container. Thereto, 245 parts of 2-ethylhexyl acrylate, 245 parts of n-butyl acrylate, 10 parts of acrylic acid and 1 part of lauryl mercaptan were added and emulsified to obtain an emulsion A.
(2)水分散型アクリル系ポリマーの製造
攪拌機、還流冷却管、窒素導入管、温度計、滴下漏斗を備えた反応容器に、ラテムルＥ−１１８Ｂを０．２部と、脱イオン水３７５部を入れ、窒素を吹き込みながら５５℃まで昇温した。攪拌下、過硫酸アンモニウム水溶液５．２部（有効成分５％）を添加し、続いて乳化液Ａを６．１部仕込み、５５℃を保ちながら１時間で重合させた。引き続き、残りの乳化液Ａの一部（３００部）と、過硫酸アンモニウム水溶液１０部（有効成分５％）を、別々の滴下漏斗を使用して反応容器を５５℃に保ちながら３時間かけて滴下して重合した。この間、滴下しなかった乳化液Ａ（３０４．９部）に、アクアロンＫＨ−１０［第一工業製薬（株）製反応性乳化剤；有効成分１００％］５部を加え、均一になるまで攪拌し、乳化液Ｂを調製した。
(2) Production of water-dispersed acrylic polymer In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 0.2 part of Latemul E-118B and 375 parts of deionized water The temperature was raised to 55 ° C. while blowing nitrogen. Under stirring, 5.2 parts of an aqueous ammonium persulfate solution (active ingredient 5%) was added, and then 6.1 parts of Emulsion A was charged and polymerized in 1 hour while maintaining 55 ° C. Subsequently, a part (300 parts) of the remaining emulsion A and 10 parts of an aqueous ammonium persulfate solution (active ingredient 5%) were dropped over 3 hours while keeping the reaction vessel at 55 ° C. using a separate dropping funnel. And polymerized. During this time, 5 parts of Aqualon KH-10 [Reactive emulsifier manufactured by Daiichi Kogyo Seiyaku Co., Ltd .; active ingredient 100%] is added to emulsion A (304.9 parts) that was not added dropwise, and stirred until uniform. Emulsion B was prepared.
乳化液Ａの滴下終了後、直ちに乳化液Ｂ（３０９．９部）と、過硫酸アンモニウム１０部（有効成分５％）を別々の滴下漏斗を使用して反応容器を５５℃に保ちながら３時間かけて滴下重合した。 Immediately after the end of dropping of emulsion A, emulsion B (309.9 parts) and 10 parts of ammonium persulfate (active ingredient 5%) were taken for 3 hours while maintaining the reaction vessel at 55 ° C. using separate dropping funnels. The polymerization was conducted dropwise.
滴下終了後、同温度にて２時間攪拌した後、内容物を冷却し、ｐＨが８．０になるようにアンモニア水（有効成分１０％）で調整した。これを２００メッシュ金網で濾過し、本発明の水分散型アクリル系ポリマーを得た。ここで得られた水分散型アクリル系ポリマーは、固形分濃度４９．９％、粘度３１０ｍＰａ・ｓ、平均粒子径は２９０ｎｍであった。 After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, and then the contents were cooled and adjusted with aqueous ammonia (10% active ingredient) so that the pH was 8.0. This was filtered through a 200-mesh wire mesh to obtain the water-dispersed acrylic polymer of the present invention. The water-dispersed acrylic polymer obtained here had a solid content concentration of 49.9%, a viscosity of 310 mPa · s, and an average particle size of 290 nm.
(3)水性粘着剤組成物の製造
上記の水分散型アクリル系ポリマーに、レベリング剤としてサーフィノール４２０［エアー・プロダクツ・ジャパン（株）製：有効成分１００％］１．２部、エポクロスＷＳ−５００［（株）日本触媒製；有効成分５０％］１部を添加した後、１００メッシュ金網で濾過し、本発明のアクリル系水性粘着剤組成物を得た。このアクリル系水性粘着剤組成物を用いて得た被膜のガラス転移温度（実測Ｔｇ）、ゲル分率（トルエン不溶解分率）、および粘着シートの接着力、粗面接着力、保持力、タックの評価結果を第１表に示した。
(3) Manufacture of aqueous pressure-sensitive adhesive composition 1.2 parts of Surfynol 420 [manufactured by Air Products Japan Ltd .: active ingredient 100%] as a leveling agent to the above water-dispersed acrylic polymer, Epocross WS- After adding 1 part of 500 [manufactured by Nippon Shokubai Co., Ltd .; active ingredient 50%], the mixture was filtered through a 100 mesh wire netting to obtain an acrylic aqueous pressure-sensitive adhesive composition of the present invention. The glass transition temperature (actually measured Tg), gel fraction (toluene insoluble fraction) of the film obtained using this acrylic aqueous pressure-sensitive adhesive composition, and adhesive strength, rough surface adhesive strength, holding strength, and tackiness of the pressure-sensitive adhesive sheet The evaluation results are shown in Table 1.
実施例２
(1)乳化液Ａの調製
容器に、ラテムルＥ−１１８Ｂ［花王（株）製；有効成分２５％］１０部と脱イオン水１００部を入れ、均一に溶解した。そこに、２−エチルヘキシルアクリレート２４５部、ｎ−ブチルアクリレート２４５部、アクリル酸１０部、ラウリルメルカプタン１部を加えて乳化し、乳化液Ａを得た。
Example 2
(1) Preparation of Emulsion A A Lattemul E-118B [manufactured by Kao Corporation; active ingredient 25%] 10 parts and 100 parts of deionized water were uniformly dissolved in a container. Thereto, 245 parts of 2-ethylhexyl acrylate, 245 parts of n-butyl acrylate, 10 parts of acrylic acid and 1 part of lauryl mercaptan were added and emulsified to obtain an emulsion A.
(2)水分散型アクリル系ポリマーの製造
攪拌機、還流冷却管、窒素導入管、温度計、滴下漏斗を備えた反応容器に、ラテムルＥ−１１８Ｂを０．２部と、脱イオン水３７５部を入れ、窒素を吹き込みながら７０℃まで昇温した。攪拌下、過硫酸アンモニウム水溶液２．６部を添加し、続いて乳化液Ａを６．１部仕込み、７０℃を保ちながら１時間で重合させた。引き続き、残りの乳化液Ａの一部（６０４．９部）と、過硫酸アンモニウム水溶液２０部（有効成分２．５％）を、別々の滴下漏斗を使用して反応容器を７０℃に保ちながら６時間かけて滴下して重合した。
(2) Production of water-dispersed acrylic polymer In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 0.2 part of Latemul E-118B and 375 parts of deionized water The temperature was raised to 70 ° C. while blowing nitrogen. Under stirring, 2.6 parts of an aqueous ammonium persulfate solution was added, and then 6.1 parts of Emulsion A was charged and polymerized in 1 hour while maintaining 70 ° C. Subsequently, a part (604.9 parts) of the remaining emulsion A and 20 parts of an aqueous ammonium persulfate solution (active ingredient 2.5%) were added while maintaining the reaction vessel at 70 ° C. using a separate dropping funnel. It dropped and polymerized over time.
滴下終了後、同温度にて２時間攪拌した後、内容物を冷却し、ｐＨが８．０になるようにアンモニア水（有効成分１０％）で調整した。これを２００メッシュ金網で濾過し、本発明の水分散型アクリル系ポリマーを得た。 After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, and then the contents were cooled and adjusted with aqueous ammonia (10% active ingredient) so that the pH was 8.0. This was filtered through a 200-mesh wire mesh to obtain the water-dispersed acrylic polymer of the present invention.
実施例３
(1)乳化液Ａの調製
容器に、ラテムルＥ−１１８Ｂ［花王（株）製；有効成分２５％］１０部と脱イオン水１００部を入れ、均一に溶解した。そこに、２−エチルヘキシルアクリレート４２５部、メチルメタクリレート７０部、アクリル酸５部、ラウリルメルカプタン０．５部を加えて乳化し、乳化液Ａを得た。
Example 3
(1) Preparation of Emulsion A A Lattemul E-118B [manufactured by Kao Corporation; active ingredient 25%] 10 parts and 100 parts of deionized water were uniformly dissolved in a container. Thereto, 425 parts of 2-ethylhexyl acrylate, 70 parts of methyl methacrylate, 5 parts of acrylic acid and 0.5 part of lauryl mercaptan were added and emulsified to obtain an emulsion A.
(2)水分散型アクリル系ポリマーの製造
攪拌機、還流冷却管、窒素導入管、温度計、滴下漏斗を備えた反応容器に、ラテムルＥ−１１８Ｂを０．２部と、脱イオン水３７５部を入れ、窒素を吹き込みながら８０℃まで昇温した。攪拌下、過硫酸カリウム水溶液５．２部を添加し、続いて乳化液Ａを６．１部仕込み、８０℃を保ちながら１時間で重合させた。引き続き、残りの乳化液Ａの一部（５１３．７部）と、過硫酸カリウム水溶液１７部（有効成分１．５％）を、別々の滴下漏斗を使用して反応容器を８０℃に保ちながら５時間かけて滴下して重合した。この間、滴下しなかった乳化液Ａ（９０．７部）に、アクアロンＫＨ−０５３０［第一工業製薬（株）製反応性乳化剤；有効成分３０％］５部を加え、均一になるまで攪拌し、乳化液Ｂを調製した。
(2) Production of water-dispersed acrylic polymer In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 0.2 part of Latemul E-118B and 375 parts of deionized water The temperature was raised to 80 ° C. while blowing nitrogen. Under stirring, 5.2 parts of an aqueous potassium persulfate solution was added, and then 6.1 parts of Emulsion A was charged and polymerized in 1 hour while maintaining 80 ° C. Subsequently, a part of the remaining emulsion A (513.7 parts) and 17 parts of an aqueous potassium persulfate solution (active ingredient 1.5%) were kept at 80 ° C. using a separate dropping funnel. The polymerization was conducted dropwise over 5 hours. During this time, 5 parts of Aqualon KH-0530 [Daiichi Kogyo Seiyaku Co., Ltd. reactive emulsifier; active ingredient 30%] is added to emulsion A (90.7 parts) that was not added dropwise, and stirred until uniform. Emulsion B was prepared.
乳化液Ａの滴下終了後、直ちに乳化液Ｂ（９５．７部）と、過硫酸カリウム水溶液３部（有効成分１．５％）を別々の滴下漏斗を使用して反応容器を８０℃に保ちながら１時間かけて滴下重合した。 Immediately after the end of dropping of emulsion A, emulsion B (95.7 parts) and 3 parts of potassium persulfate aqueous solution (active ingredient 1.5%) were kept at 80 ° C. using separate dropping funnels. The polymerization was carried out dropwise over 1 hour.
滴下終了後、同温度にて２時間攪拌した後、内容物を冷却し、ｐＨが８．０になるようにアンモニア水（有効成分１０％）で調整した。これを２００メッシュ金網で濾過し、本発明の水分散型アクリル系ポリマーを得た。 After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, and then the contents were cooled and adjusted with aqueous ammonia (10% active ingredient) so that the pH was 8.0. This was filtered through a 200-mesh wire mesh to obtain the water-dispersed acrylic polymer of the present invention.
実施例４
(1)乳化液Ａの調製
容器に、ラテムルＥ−１１８Ｂ［花王（株）製；有効成分２５％］１０部と脱イオン水１００部を入れ、均一に溶解した。そこに、ｎ−ブチルアクリレート４８５部、アクリル酸１５部、グリシジルメタアクリレート２．５部、ラウリルメルカプタン０．５部を加えて乳化し、乳化液Ａを得た。
Example 4
(1) Preparation of Emulsion A A Lattemul E-118B [manufactured by Kao Corporation; active ingredient 25%] 10 parts and 100 parts of deionized water were uniformly dissolved in a container. Thereto, 485 parts of n-butyl acrylate, 15 parts of acrylic acid, 2.5 parts of glycidyl methacrylate and 0.5 part of lauryl mercaptan were added and emulsified to obtain an emulsion A.
(2)水分散型アクリル系ポリマーの製造
攪拌機、還流冷却管、窒素導入管、温度計、滴下漏斗を備えた反応容器に、ラテムルＥ−１１８Ｂを０．２部と、脱イオン水３７５部を入れ、窒素を吹き込みながら７０℃まで昇温した。攪拌下、過硫酸アンモニウム水溶液５．２部を添加し、続いて乳化液Ａを６．１部仕込み、７０℃を保ちながら１時間で重合させた。引き続き、残りの乳化液Ａの一部（４２３．１部）と、過硫酸カリウム水溶液１４部（有効成分５％）を、別々の滴下漏斗を使用して反応容器を７０℃に保ちながら４時間かけて滴下して重合した。この間、滴下しなかった乳化液Ａ（１８１．３部）に、アクアロンＫＨ−０５３０［第一工業製薬（株）製反応性乳化剤；有効成分３０％］８．３部を加え、均一になるまで攪拌し、乳化液Ｂを調製した。
(2) Production of water-dispersed acrylic polymer In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 0.2 part of Latemul E-118B and 375 parts of deionized water The temperature was raised to 70 ° C. while blowing nitrogen. Under stirring, 5.2 parts of an aqueous ammonium persulfate solution was added, and then 6.1 parts of Emulsion A was charged and polymerized in 1 hour while maintaining 70 ° C. Subsequently, a part (423.1 parts) of the remaining emulsion A and 14 parts of an aqueous potassium persulfate solution (active ingredient 5%) were added for 4 hours while maintaining the reaction vessel at 70 ° C. using a separate dropping funnel. The solution was dropped and polymerized. During this time, 8.3 parts of Aqualon KH-0530 [Daiichi Kogyo Seiyaku Co., Ltd. reactive emulsifier; active ingredient 30%] is added to emulsion A (181.3 parts) that was not dripped until uniform. Stirring to prepare Emulsion B.
乳化液Ａの滴下終了後、直ちに乳化液Ｂ（１８９．６部）と、過硫酸アンモニウム６部（有効成分５％）を別々の滴下漏斗を使用して反応容器を７０℃に保ちながら２時間かけて滴下重合した。 Immediately after the end of dropping of emulsion A, emulsion B (189.6 parts) and 6 parts of ammonium persulfate (active ingredient 5%) were taken over 2 hours while maintaining the reaction vessel at 70 ° C. using separate dropping funnels. The polymerization was conducted dropwise.
滴下終了後、同温度にて２時間攪拌した後、内容物を冷却し、ｐＨが８．０になるようにアンモニア水（有効成分１０％）で調整した。これを２００メッシュ金網で濾過し、本発明の水分散型アクリル系ポリマーを得た。 After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, and then the contents were cooled and adjusted with aqueous ammonia (10% active ingredient) so that the pH was 8.0. This was filtered through a 200-mesh wire mesh to obtain the water-dispersed acrylic polymer of the present invention.
実施例５
(1)乳化液Ａの調製
容器に、ラテムルＥ−１１８Ｂ［花王（株）製；有効成分２５％］１０部と脱イオン水１００部を入れ、均一に溶解した。そこに、２−エチルヘキシルアクリレート１５０部、ｎ−ブチルアクリレート２９０部、メチルメタクリレート４０部、アクリル酸２０部、ラウリルメルカプタン０．５部を加えて乳化し、乳化液Ａを得た。
Example 5
(1) Preparation of Emulsion A A Lattemul E-118B [manufactured by Kao Corporation; active ingredient 25%] 10 parts and 100 parts of deionized water were uniformly dissolved in a container. Thereto, 150 parts of 2-ethylhexyl acrylate, 290 parts of n-butyl acrylate, 40 parts of methyl methacrylate, 20 parts of acrylic acid and 0.5 part of lauryl mercaptan were added and emulsified to obtain an emulsion A.
(2)水分散型アクリル系ポリマーの製造
攪拌機、還流冷却管、窒素導入管、温度計、滴下漏斗を備えた反応容器に、ラテムルＥ−１１８Ｂを０．２部と、脱イオン水３５５部を入れ、窒素を吹き込みながら５５℃まで昇温した。攪拌下、４，４−アゾビス（４−シアノ吉草酸）５．２部を添加し、続いて乳化液Ａを６．１部仕込み、５５℃を保ちながら１時間で重合させた。引き続き、残りの乳化液Ａの一部（２４１．８部）と、４，４−アゾビス（４−シアノ吉草酸）水溶液１６部（有効成分５％）を、別々の滴下漏斗を使用して反応容器を５５℃に保ちながら３時間かけて滴下して重合した。この間、滴下しなかった乳化液Ａ（３６２．６部）に、アクアロンＫＨ−１０［第一工業製薬（株）製反応性乳化剤；有効成分１００％］５部を加え、均一になるまで攪拌し、乳化液Ｂを調製した。
(2) Production of water-dispersed acrylic polymer In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping funnel, 0.2 part of Latemul E-118B and 355 parts of deionized water The temperature was raised to 55 ° C. while blowing nitrogen. Under stirring, 5.2 parts of 4,4-azobis (4-cyanovaleric acid) was added, and then 6.1 parts of Emulsion A was charged and polymerized in 1 hour while maintaining 55 ° C. Subsequently, a part (241.8 parts) of the remaining emulsion A and 16 parts of an aqueous solution of 4,4-azobis (4-cyanovaleric acid) (active ingredient 5%) were reacted using separate dropping funnels. While keeping the container at 55 ° C., the polymerization was carried out dropwise over 3 hours. During this time, 5 parts of Aqualon KH-10 [Daiichi Kogyo Seiyaku Co., Ltd. reactive emulsifier; active ingredient 100%] is added to emulsion A (362.6 parts) that was not added dropwise, and stirred until uniform. Emulsion B was prepared.
乳化液Ａの滴下終了後、直ちに乳化液Ｂ（３６７．６部）と、４，４−アゾビス（４−シアノ吉草酸）２４部（有効成分７．５％）を別々の滴下漏斗を使用して反応容器を５５℃に保ちながら３時間かけて滴下重合した。 Immediately after the addition of emulsion A, emulsion B (367.6 parts) and 4,4-azobis (4-cyanovaleric acid) 24 parts (active ingredient 7.5%) were used in separate dropping funnels. Then, the polymerization was carried out dropwise over 3 hours while maintaining the reaction vessel at 55 ° C.
滴下終了後、同温度にて２時間攪拌した後、内容物を冷却し、ｐＨが８．０になるようにアンモニア水（有効成分１０％）で調整した。これを２００メッシュ金網で濾過し、本発明の水分散型アクリル系ポリマーを得た。 After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, and then the contents were cooled and adjusted with aqueous ammonia (10% active ingredient) so that the pH was 8.0. This was filtered through a 200-mesh wire mesh to obtain the water-dispersed acrylic polymer of the present invention.
比較例１
(1)分散液Ｃの製造
攪拌機、窒素導入管、コンデンンサー（冷却管）、原料仕込口、温度計を備えた内容積が２Ｌの反応容器に、２５℃の脱イオン水７５部を仕込み、攪拌下、窒素導入管から５０ｍＬ／ｍｉｎの流量で窒素ガス導入した。１２０分後、反応容器内の溶存酸素濃度を測定したところ、２．３ｐｐｍであった。反応容器内を攪拌下、窒素ガスを導入しながら、ポリオキシエチレンノニルフェニルエーテル［ＨＬＢ＝１４］１部、ドデシルベンゼンスルホン酸ソーダ１部、２−エチルヘキシルアクリレート７０部、アクリル酸エチル２７部、アクリル酸５部を仕込み、全体を均一に乳化した。その後、反応容器内温度を５０℃に調整した。次に、反応容器内温度が５０℃であることを確認後、２、２−アゾビス［２−メチル−Ｎ−（フェニルメチル）−プロピオンアミジン］ジハイドロクロライド０．０２部を加え、５０℃に８時間維持して乳化重合を行った後、内容物を冷却し、分散液Ｃを得た。
Comparative Example 1
(1) Production of Dispersion C Charged with 75 parts of deionized water at 25 ° C. into a reaction vessel having an internal volume of 2 L equipped with a stirrer, nitrogen inlet tube, condenser (cooling tube), raw material charging port, and thermometer Below, nitrogen gas was introduced from the nitrogen introduction tube at a flow rate of 50 mL / min. After 120 minutes, the dissolved oxygen concentration in the reaction vessel was measured and found to be 2.3 ppm. While introducing nitrogen gas while stirring in the reaction vessel, 1 part of polyoxyethylene nonylphenyl ether [HLB = 14], 1 part of sodium dodecylbenzenesulfonate, 70 parts of 2-ethylhexyl acrylate, 27 parts of ethyl acrylate, acrylic 5 parts of acid was charged and the whole was uniformly emulsified. Thereafter, the temperature in the reaction vessel was adjusted to 50 ° C. Next, after confirming that the temperature in the reaction vessel was 50 ° C., 0.02 part of 2,2-azobis [2-methyl-N- (phenylmethyl) -propionamidine] dihydrochloride was added, and the mixture was heated to 50 ° C. After the emulsion polymerization was carried out for 8 hours, the content was cooled to obtain a dispersion C.
(2)乳化液Ｄの調製
まず、容器内にポリオキシエチレンノニルフェニルエーテル［ＨＬＢ＝１４］４部、ドデシルベンゼンスルホン酸ソーダ４部、脱イオン水６０部を加え、均一に溶解した。そこに、２−エチルヘキシルアクリレート２８０部、アクリル酸エチル１０８部、アクリル酸１０部を仕込み、全体を均一に乳化した。
(2) Preparation of Emulsion D First, 4 parts of polyoxyethylene nonylphenyl ether [HLB = 14], 4 parts of sodium dodecylbenzenesulfonate and 60 parts of deionized water were added to a container and dissolved uniformly. Thereto, 280 parts of 2-ethylhexyl acrylate, 108 parts of ethyl acrylate and 10 parts of acrylic acid were charged, and the whole was uniformly emulsified.
(3)水性粘着剤組成物の製造
攪拌機、窒素導入管、コンデンンサー（冷却管）、原料仕込口、温度計を備えた反応容器に、２５℃の脱イオン水２８０部、過硫酸アンモニウム１部を水４０部に溶解した溶液を加え、窒素置換しながら７０℃に加温した。これに、前述の乳化液Ｄを、滴下漏斗を用いて３時間かけて滴下重合させた。滴下終了後、同温度にて２時間攪拌した後、内容物を冷却した。
(3) Manufacture of aqueous pressure-sensitive adhesive composition In a reaction vessel equipped with a stirrer, nitrogen inlet tube, condenser (cooling tube), raw material charging port, and thermometer, 280 parts of deionized water at 25 ° C. and 1 part of ammonium persulfate are water. A solution dissolved in 40 parts was added and heated to 70 ° C. while purging with nitrogen. To this, the aforementioned emulsion D was subjected to drop polymerization using a dropping funnel over 3 hours. After completion of the dropwise addition, the contents were cooled after stirring for 2 hours at the same temperature.
冷却後、同反応容器内に、別途合成した分散液Ｃを混合し、ｐＨが８．０になるようにアンモニア水（有効成分１０％）で調整した。これを２００メッシュ金網で濾過し、水分散型アクリル系ポリマーを得た。ここで得られた水分散型アクリル系ポリマーは、固形分濃度５０．９％、粘度２３０ｍＰａ・ｓ、平均粒子径は２１０ｎｍであった。 After cooling, separately synthesized dispersion C was mixed in the same reaction vessel, and adjusted with ammonia water (active ingredient 10%) so that the pH was 8.0. This was filtered through a 200-mesh wire mesh to obtain a water-dispersed acrylic polymer. The water-dispersed acrylic polymer obtained here had a solid content concentration of 50.9%, a viscosity of 230 mPa · s, and an average particle size of 210 nm.
上記の水分散型アクリル系ポリマーに、レベリング剤としてサーフィノール４２０［エアー・プロダクツ・ジャパン（株）製：有効成分１００％］２．４部、エポキシ架橋剤ＴＥＰＩＣ［日産化学工業（株）製］を、０．０２５部を水１部に溶解した水溶液を添加した後、１００メッシュ金網で濾過し、アクリル系水性粘着剤組成物を得た。 Surfinol 420 as a leveling agent (available from Air Products Japan Co., Ltd .: active ingredient 100%) 2.4 parts, epoxy crosslinking agent TEPIC [manufactured by Nissan Chemical Industries, Ltd.] After adding an aqueous solution in which 0.025 part was dissolved in 1 part of water, it was filtered through a 100 mesh wire netting to obtain an acrylic aqueous pressure-sensitive adhesive composition.
このアクリル系水性粘着剤組成物を用いて得た被膜のガラス転移温度（実測Ｔｇ）、ゲル分率（トルエン不溶解分率）、および粘着シートの接着力、粗面接着力、保持力、タックの評価結果を表１に示した。 The glass transition temperature (actually measured Tg), gel fraction (toluene insoluble fraction) of the film obtained using this acrylic aqueous pressure-sensitive adhesive composition, and adhesive strength, rough surface adhesive strength, holding strength, and tackiness of the pressure-sensitive adhesive sheet The evaluation results are shown in Table 1.
表１中の略号の正式名称を下記に示す。
２ＥＨＡ ；２−エチルヘキシルアクリレート
ＢＡ ；ｎ−ブチルアクリレート
ＥＡ ；エチルアクリレート
ＭＭＡ ；メチルメタクリレート
ＡＡ ；アクリル酸
ＧＭＡ ；グリシジルメタクリレート
Ｌ−ＳＨ ；ラウリルメルカプタン
ＡＰＳ ；過硫酸アンモニウム
ＫＰＳ ；過硫酸カリウム
ＣＶＡ ；４，４’−アゾビス（４−シアノ吉草酸）
ＡＭＰ ；２，２−アゾビス［２−メチル−Ｎ−（フェニルメチル）−プロピオンアミジン］ジハイドロクロライド
ＫＨ−０５３０；［第一工業製薬（株）製］、アクアロンＫＨ−０５３０
The official names of the abbreviations in Table 1 are shown below.
2EHA; 2-ethylhexyl acrylate BA; n-butyl acrylate EA; ethyl acrylate MMA; methyl methacrylate AA; acrylic acid GMA; glycidyl methacrylate L-SH; lauryl mercaptan APS; ammonium persulfate KPS; Azobis (4-cyanovaleric acid)
AMP; 2,2-azobis [2-methyl-N- (phenylmethyl) -propionamidine] dihydrochloride KH-0530; [Daiichi Kogyo Seiyaku Co., Ltd.], Aqualon KH-0530
Claims (6)
The radical generation amount calculated from the amount of the polymerization initiator used is in the range of 5 × 10 −13 to 120 × 10 −13 mol per minute per liter of the polymerizable monomer component in the reaction system. The manufacturing method of the acrylic water-based adhesive composition as described in any one of 1-3.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2008285221A (en) * | 2007-05-21 | 2008-11-27 | Nitto Denko Corp | Water dispersion acrylic adhesive tape or sheet for transporting electronic component |
| JP2009051894A (en) * | 2007-08-24 | 2009-03-12 | Jsr Corp | Water-based adhesive and method for producing the same |
| JP2012077119A (en) * | 2010-09-30 | 2012-04-19 | Dainippon Toryo Co Ltd | Aqueous resin composition |
| EP2450415A2 (en) | 2010-11-04 | 2012-05-09 | Nitto Denko Corporation | Pressure-sensitive adhesive sheet |
| JP2016121298A (en) * | 2014-12-25 | 2016-07-07 | 花王株式会社 | Method for producing latex |
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| JPH08325309A (en) * | 1995-05-30 | 1996-12-10 | Nitto Denko Corp | Production of water-dispersing type acrylic pressure-sensitive adhesive |
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| JPH07228612A (en) * | 1993-12-23 | 1995-08-29 | Nitto Denko Corp | Water-dispersed acrylic polymer, its production and pressure-sensitive adhesive produced by using the polymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008285221A (en) * | 2007-05-21 | 2008-11-27 | Nitto Denko Corp | Water dispersion acrylic adhesive tape or sheet for transporting electronic component |
| JP2009051894A (en) * | 2007-08-24 | 2009-03-12 | Jsr Corp | Water-based adhesive and method for producing the same |
| JP2012077119A (en) * | 2010-09-30 | 2012-04-19 | Dainippon Toryo Co Ltd | Aqueous resin composition |
| EP2450415A2 (en) | 2010-11-04 | 2012-05-09 | Nitto Denko Corporation | Pressure-sensitive adhesive sheet |
| JP2016121298A (en) * | 2014-12-25 | 2016-07-07 | 花王株式会社 | Method for producing latex |
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