JP2005097353A - Delayed-tack pressure-sensitive adhesive composition and pressure-sensitive adhesive label - Google Patents
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本発明は、常温では非粘着性であるが加熱により粘着性が発現し、しかも粘着性発現後、加熱源を取り去っても粘着性が持続する感熱性ディレードタック型粘着剤組成物及び感熱性粘着ラベルに関するものである。 The present invention is a heat-sensitive delayed tack-type pressure-sensitive adhesive composition and a heat-sensitive adhesive that are non-adhesive at room temperature but exhibit adhesiveness upon heating, and that remain adhesive even after the heating source is removed after the occurrence of adhesiveness. It is about labels.
従来の感熱性ディレードタック型粘着剤は、例えば「接着便覧」第12版（高分子刊行会発行、昭和55年）に記載されており、基本的に、（ａ）ポリ酢酸ビニル、ポリメタクリル酸ブチル、塩化ビニル−塩化ビニリデンコポリマー、合成ゴム、酢酸ビニル−アクリル酸２−エチルヘキシルコポリマー、酢酸ビニル−エチレンコポリマー、ビニルピロリドン−スチレンコポリマー、スチレン−ブダジエンコポリマー、ビニルピロリドン−アクリル酸エチルコポリマー等の高分子樹脂と、（ｂ）フタル酸ジフェニル、フタル酸ジヘキシル、フタル酸ジシクロルヘキシル、フタル酸ジヒドロアビエチル、イソフタル酸ジメチル、安息香酸スクロース、二安息香酸エチレングリコール、三安息香酸トリメチロールエタン、三安息香酸グリセリド、四安息香酸ペンタエリトリット、八酢酸スクロース、クエン酸トリシクロヘキシル、Ｎ−シクロヘキシル−ｐ−トルエンスルホンアミド等の常温で固体の可塑剤と、（ｃ）ロジン誘導体（ロジン、重合ロジン、水添ロジン及びそれらのグリセリン、ペンタエリスリトール等とのエステル、樹脂酸ダイマー等）、テルペン樹脂系、石油樹脂系、フェノール樹脂系、キシレン樹脂系等の粘着性付与剤とを含有する感熱性粘着剤である。 The conventional heat-sensitive delayed tack type pressure-sensitive adhesive is described in, for example, “Adhesion Handbook”, 12th edition (published by Kobunshi Shuppankai, 1980). Basically, (a) polyvinyl acetate, polymethacrylic acid Polymers such as butyl, vinyl chloride-vinylidene chloride copolymer, synthetic rubber, vinyl acetate-2-ethylhexyl acrylate copolymer, vinyl acetate-ethylene copolymer, vinyl pyrrolidone-styrene copolymer, styrene-budadiene copolymer, vinyl pyrrolidone-ethyl acrylate copolymer And (b) diphenyl phthalate, dihexyl phthalate, dicyclohexyl phthalate, dihydroabiethyl phthalate, dimethyl isophthalate, sucrose benzoate, ethylene glycol dibenzoate, trimethylolethane tribenzoate, tribenzoic acid Glycerides, benzoic acid A plasticizer that is solid at room temperature, such as acid pentaerythritol, sucrose octaacetate, tricyclohexyl citrate, N-cyclohexyl-p-toluenesulfonamide, and (c) a rosin derivative (rosin, polymerized rosin, hydrogenated rosin and their (Ester with glycerin, pentaerythritol, resin acid dimer, etc.), terpene resin, petroleum resin, phenol resin, xylene resin, and other tackifiers.
ここで高分子樹脂は粘着・接着力の根源を為すものであり、粘着性付与剤は、加熱により活性化された際に粘着性を増すための成分である。固体可塑剤はディレードタック型粘着剤たる特性を与える成分であって、常温では固体であるので高分子樹脂に可塑性を与えず、加熱により溶融し、高分子樹脂を膨潤・溶解して粘着性を発現させる。そして固体可塑剤は一旦溶融した後は高分子樹脂との相溶性に応じてゆっくりと結晶化するので、熱活性化後の粘着性を長く保持できる。 Here, the polymer resin serves as a source of adhesion / adhesive strength, and the tackifier is a component for increasing the adhesion when activated by heating. The solid plasticizer is a component that gives the characteristics of a delayed tack type adhesive, and since it is solid at room temperature, it does not give plasticity to the polymer resin, melts by heating, and swells and dissolves the polymer resin to make it sticky. To express. And since a solid plasticizer once melt | dissolves, it crystallizes slowly according to compatibility with a polymer resin, Therefore The adhesiveness after heat activation can be kept long.
そのためディレードタック型粘着剤としては、固形可塑剤が融解、又は溶解する工程がなく、固体状態のまま塗工するために、塗工液をすべて水性分散体とすることとが肝要である。これにより、乾燥条件として粘着シートが熱活性化しない程度の条件を選択すればロール状に巻き取ってもブロッキングを生じない感熱性粘着シートを直接製造することができる。 Therefore, as a delayed tack type pressure-sensitive adhesive, there is no step of melting or dissolving the solid plasticizer, and it is important to use an aqueous dispersion as the entire coating liquid in order to perform coating in a solid state. Thereby, if the conditions which do not heat-activate an adhesive sheet are selected as drying conditions, the heat-sensitive adhesive sheet which does not block even if it winds up in roll shape can be manufactured directly.
一方、清涼飲料水などの液体商品を収容する容器としては、ポリエチレンテレフタレートを主体としたポリエステル樹脂をブロー成形したＰＥＴボトルが一般的に使用されてきており、こういったＰＥＴボトルには、シュリンクラベルやストレッチラベル以外に、内面に感熱粘着剤を塗布する事によって形成された粘着層を有する感熱粘着性ラベルが装着される場合がある。このようなＰＥＴボトルに装着される感熱粘着性ラベルは、二軸延伸ポリプロピレンフィルム（ＯＰＰ）によって形成されたラベル基材の内側に感熱性粘着剤を塗布されることによって粘着剤層が形成し、この粘着層を形成された感熱粘着性ラベルは加熱工程を経た後にＰＥＴボトルの外面に貼着される。 On the other hand, as a container for storing liquid products such as soft drinks, PET bottles made by blow molding a polyester resin mainly composed of polyethylene terephthalate have been generally used. In addition to or a stretch label, a heat-sensitive adhesive label having an adhesive layer formed by applying a heat-sensitive adhesive on the inner surface may be attached. The heat-sensitive adhesive label attached to such a PET bottle has a pressure-sensitive adhesive layer formed by applying a heat-sensitive adhesive to the inside of a label substrate formed by a biaxially oriented polypropylene film (OPP), The heat-sensitive adhesive label formed with this adhesive layer is attached to the outer surface of the PET bottle after undergoing a heating step.
このようにして感熱粘着性ラベルが装着した使用済みのＰＥＴボトルをリサイクルする場合は、ＰＥＴボトルに装着されている感熱粘着性ラベルをＰＥＴボトルから外した状態で粉砕し、これを原料としてＰＥＴボトルを再生するか、他の樹脂製品の原料として使用するのが一般的であるので、ＰＥＴボトルのリサイクルを効率よく行うためには、感熱粘着性ラベルが外されたＰＥＴボトルの表面には、ＰＥＴボトルとは異なる樹脂成分によって形成されている感熱粘着性ラベルの粘着層が残存付着していないことが望ましい。 When recycling a used PET bottle with a heat-sensitive adhesive label attached in this way, the heat-sensitive adhesive label attached to the PET bottle is crushed with the PET bottle removed, and this is used as a raw material for the PET bottle. In order to efficiently recycle the PET bottle, the surface of the PET bottle from which the heat-sensitive adhesive label has been removed is disposed on the surface of the PET bottle. It is desirable that the adhesive layer of the heat-sensitive adhesive label formed of a resin component different from the bottle does not remain attached.
このように、ＰＥＴボトルの表面に感熱粘着性ラベルの粘着層が残存付着しないようにするためには、感熱粘着性ラベルの粘着層を形成している感熱粘着剤のＰＥＴボトルに対する接着強度をＯＰＰフィルムに対する接着強度より小さくすることが好ましい。ところが、従来公知の前記のような高分子樹脂はいずれも組成面からポリプロピレン、ポリエチレンのような極性の低いプラスチック材料よりむしろポリエステル樹脂に対する接着力が強いものであった。 Thus, in order to prevent the adhesive layer of the heat-sensitive adhesive label from remaining and adhering to the surface of the PET bottle, the adhesive strength of the heat-sensitive adhesive forming the adhesive layer of the heat-sensitive adhesive label to the PET bottle is set to OPP. It is preferable to make it smaller than the adhesive strength to the film. However, all of the above known polymer resins have a strong adhesive force to the polyester resin rather than a plastic material having a low polarity such as polypropylene and polyethylene.
ポリプロピレン、ポリエチレンのような極性の低いプラスチック材料に対して接着強度を高めたディレードタック粘着剤を得る方法として、高分子樹脂としては、酢酸ビニル含有量が２０重量％以下であるエチレン−酢酸ビニル共重合体を少なくとも１重量％、好ましくは１〜５０重量％含有し、他の樹脂としては、前述のポリ酢酸ビニル、ポリメタクリル酸ブチル、塩化ビニル−塩化ビニリデンコポリマー、合成ゴム、酢酸ビニル−アクリル酸２−エチルヘキシルコポリマー、酢酸ビニル−エチレンコポリマー、ビニルピロリドン−スチレンコポリマー、スチレン−ブタジエンコポリマー、ビニルピロリドン−アクリル酸エチルコポリマーがあげられている（例えば、特許文献１，２参照）。同公報には、この場合の酢酸ビニル−エチレンコポリマーは通常は乳化重合法によって製造された酢酸ビニル−エチレン共重合体水性エマルジョンを指し、酢酸ビニル含有量が７０重量％以上の共重合体であると記載されている。 As a method for obtaining a delayed tack pressure-sensitive adhesive having an increased adhesive strength with respect to a plastic material having a low polarity such as polypropylene or polyethylene, as a polymer resin, an ethylene-vinyl acetate copolymer having a vinyl acetate content of 20% by weight or less is used. The polymer contains at least 1% by weight, preferably 1 to 50% by weight. Examples of other resins include the aforementioned polyvinyl acetate, polybutyl methacrylate, vinyl chloride-vinylidene chloride copolymer, synthetic rubber, vinyl acetate-acrylic acid. Examples include 2-ethylhexyl copolymer, vinyl acetate-ethylene copolymer, vinyl pyrrolidone-styrene copolymer, styrene-butadiene copolymer, and vinyl pyrrolidone-ethyl acrylate copolymer (see, for example, Patent Documents 1 and 2). In this publication, the vinyl acetate-ethylene copolymer in this case usually refers to a vinyl acetate-ethylene copolymer aqueous emulsion produced by an emulsion polymerization method, and is a copolymer having a vinyl acetate content of 70% by weight or more. It is described.
この様に上記公報はオレフィンポリマーへの接着性向上を目指すものではあるが、ＰＥＴへの粘着性低減を目指すものではない。実際極性の高い樹脂を併用しており、更に低分子量の粘着付与剤も添加されているので、ＰＥＴへの粘着性が低下するわけではなく、感熱粘着性ラベル剥離時にＰＥＴボトル側にも粘着剤が残存付着すると考えられる。 Thus, although the above publication aims to improve the adhesion to olefin polymers, it does not aim to reduce the adhesion to PET. In fact, a highly polar resin is used in combination, and a low molecular weight tackifier is also added, so the adhesiveness to PET does not decrease, and the adhesive is also applied to the PET bottle side when peeling the heat-sensitive adhesive label. Is considered to remain attached.
本発明の課題は、ＰＥＴボトルに一旦装着された感熱粘着性ラベルが外れにくく、しかも、ＰＥＴボトルから感熱粘着性ラベルを強制的に外す際は、ＰＥＴボトルに感熱粘着性ラベルの粘着層がＯＰＰ側に残存してＰＥＴ側には残存付着しにくい感熱粘着性ラベルができるとともに、保管時の耐ブロッキング性に優れ、且つ塗工基材の熱変形温度以下の温度で、粘着性を発現できるディレードタック型粘着剤組成物及びそれを用いた粘着ラベルを提供することにある。 The problem of the present invention is that the heat-sensitive adhesive label once attached to the PET bottle is difficult to be removed, and when the heat-sensitive adhesive label is forcibly removed from the PET bottle, the adhesive layer of the heat-sensitive adhesive label is attached to the PET bottle. A delayed adhesive that can remain on the PET side and hardly adhere to the PET side, has excellent blocking resistance during storage, and can exhibit adhesiveness at a temperature lower than the thermal deformation temperature of the coated substrate. The object is to provide a tack-type pressure-sensitive adhesive composition and a pressure-sensitive adhesive label using the same.
本発明者等は、本発明者らは、前記の課題を解決するために種々研究を重ねた結果、以下の構成を採ることにより本発明の目的を達成できることを見出し、本発明を完成した。 As a result of various studies conducted by the inventors to solve the above-mentioned problems, the present inventors have found that the object of the present invention can be achieved by adopting the following configuration, and have completed the present invention.
すなわち、本発明は第一に、熱可塑性樹脂及び固形可塑剤を含有する水性分散型ディレードタック型粘着剤組成物であって、該熱可塑性樹脂が、エチレン含量５０〜９０質量％である高圧法エチレン共重合体を含有することを特徴とするディレードタック型粘着剤組成物を提供する。 That is, the first aspect of the present invention is an aqueous dispersion type delayed tack pressure-sensitive adhesive composition containing a thermoplastic resin and a solid plasticizer, wherein the thermoplastic resin has an ethylene content of 50 to 90% by mass. A delayed tack type pressure-sensitive adhesive composition comprising an ethylene copolymer is provided.
本発明は第二に、前記したディレードタック型粘着剤組成物の乾燥塗膜層をラベル用基材上に設けたことを特徴とするディレードタック型粘着ラベルを提供する。 Secondly, the present invention provides a delayed tack-type pressure-sensitive adhesive label characterized in that a dry coating layer of the above-described delayed tack-type pressure-sensitive adhesive composition is provided on a label substrate.
感熱性ディレードタック型粘着剤組成物用の熱可塑性樹脂成分として特定の高圧法エチレン共重合体を用いることにより、該粘着剤組成物を塗布形成したＯＰＰ基材の粘着ラベルはオレフィンポリマーへの密着性に優れ、且つ、ＰＥＴから外力により剥離した際に粘着剤層がＯＰＰ側に残存してＰＥＴ側には残存することなく剥離できる。又、該ディレードタック型粘着剤組成物の塗工物は耐ブロッキング性に優れ、且つ粘着性にも優れることからＰＥＴボトルに用いるＯＰＰラベル粘着剤として利用できる。本発明の感熱性ディレードタック型粘着剤及び粘着ラベルにより、ＰＥＴボトルのリサイクル促進に貢献できることは環境保全及び経済的な有益性を追求する上での産業的意義は、極めて多大である。 By using a specific high-pressure ethylene copolymer as a thermoplastic resin component for a heat-sensitive delayed-tack-type pressure-sensitive adhesive composition, the pressure-sensitive adhesive label of the OPP substrate on which the pressure-sensitive adhesive composition is formed is adhered to the olefin polymer. It has excellent properties, and when peeled from PET by external force, the pressure-sensitive adhesive layer remains on the OPP side and can be peeled without remaining on the PET side. Moreover, since the coated product of the delayed tack type adhesive composition is excellent in blocking resistance and adhesiveness, it can be used as an OPP label adhesive used in PET bottles. The industrial significance in pursuing environmental conservation and economic benefits is that the contribution of the thermosensitive delayed-tack-type pressure-sensitive adhesive and pressure-sensitive adhesive label of the present invention to the promotion of PET bottle recycling is extremely great.
本発明の構成要件である、熱可塑性樹脂及び固形可塑剤に関して以下に詳説する。 The thermoplastic resin and the solid plasticizer, which are constituent elements of the present invention, will be described in detail below.
該熱可塑性樹脂として用いる高圧法エチレン共重合体とは、エチレンと各種官能基含有コモノマーとの高圧法ラジカル共重合反応によって製造されたエチレン共重合体のことであって、官能基コモノマーとして酢酸ビニル、アクリル酸及びそのエステル、メタアクリル酸及びそのエステル、無水マレイン酸等が用いられる。本発明においては、これらの高圧法エチレン共重合体は水性エマルジョン化したものを用いる。該高圧法エチレン共重合体の官能基コモノマー量は１０〜５０％が好ましい、官能基コモノマー量が少ないとエチレン共重合体水性エマルジョンの最低造膜温度が高くなり、単独では固形可塑剤の融点以下の温度では塗工膜が形成されなくなる。感熱粘着剤の塗工膜がラベル基材に形成されていない場合は塗工ラベルを切断したり、打ち抜きを行った際に塗工膜が割れたり、剥落したりする。官能基コモノマー量が多いと共重合体の極性が高くなってＯＰＰフィルムよりはＰＥＴボトルへの密着性が上がり、感熱粘着性ラベルを剥離する際に粘着剤がＰＥＴボトルに残存付着しやすくなる。その際に好ましくは高圧法エチレン共重合体エマルジョンの最低造膜温度は６０〜１００℃である。更に好ましくは酢酸ビニルを２０〜３５％含有するエチレン−酢酸ビニル共重合体が挙げられる。 The high-pressure ethylene copolymer used as the thermoplastic resin is an ethylene copolymer produced by a high-pressure radical copolymerization reaction between ethylene and various functional group-containing comonomers, and vinyl acetate is used as the functional group comonomer. Acrylic acid and its ester, methacrylic acid and its ester, and maleic anhydride. In the present invention, these high-pressure ethylene copolymers are used as aqueous emulsions. The amount of the functional group comonomer of the high-pressure ethylene copolymer is preferably 10 to 50%. If the amount of the functional group comonomer is small, the minimum film-forming temperature of the ethylene copolymer aqueous emulsion becomes high, and the melting point of the solid plasticizer alone is lower. The coating film is not formed at the temperature of. When the coating film of the heat-sensitive adhesive is not formed on the label substrate, the coating film is broken or peeled off when the coating label is cut or punched. When the amount of the functional group comonomer is large, the polarity of the copolymer is increased, the adhesion to the PET bottle is higher than that of the OPP film, and the adhesive is likely to remain and adhere to the PET bottle when the heat-sensitive adhesive label is peeled off. In that case, the minimum film-forming temperature of the high-pressure ethylene copolymer emulsion is preferably 60 to 100 ° C. More preferred is an ethylene-vinyl acetate copolymer containing 20 to 35% vinyl acetate.
又、前記した共重合体の分散粒子径も造膜性に影響を与え、粒子径が大きすぎると塗工膜が形成されにくいので、該高圧法エチレン共重合体水性エマルジョンの平均粒子径（体積基準中央値）は３μｍ以下が好ましい。 Further, the dispersed particle size of the copolymer also affects the film forming property, and if the particle size is too large, it is difficult to form a coating film. Therefore, the average particle size (volume) of the high-pressure ethylene copolymer aqueous emulsion can be reduced. The reference median value is preferably 3 μm or less.
水性エマルジョン化する方法としては、一例を挙げれば、特開昭５８−１２０６５５や特開昭５９−４６３７号明細書に記載されているような、有機溶剤を用いない方法が好ましく、多軸押出機に高圧法エチレン共重合体を供給して、これをまず加熱・混練した後に引き続き押出機の途中に設けた供給口より保護コロイドである水溶性高分子水溶液を供給して、これらを剪断下に混練すれば水性エマルジョンが得られる。 As an example of a method for forming an aqueous emulsion, a method that does not use an organic solvent as described in JP-A Nos. 58-120655 and 59-4637 is preferable. A high-pressure ethylene copolymer is supplied to the mixture, heated and kneaded first, and then a water-soluble polymer aqueous solution as a protective colloid is supplied from a supply port provided in the middle of the extruder, and these are subjected to shearing. If kneaded, an aqueous emulsion is obtained.
又、本発明の目的を阻害しない範囲で他の熱可塑樹脂の水性エマルジョンを併用する事ができる。他の熱可塑性樹脂として、例えば、アクリル酸エステル、スチレン−アクリル酸エステル、スチレン−ブタジエン、酢酸ビニル、酢酸ビニル−エチレン、酢酸ビニル−アクリル酸エステル、エチレン−アクリル酸エステル、エチレン−アクリル酸、ブタジエンコポリマー、ウレタン、スチレン−イソプレンブロックポリマ−等の熱可塑性樹脂が挙げられる。 Also, other thermoplastic resin aqueous emulsions can be used in combination as long as the object of the present invention is not impaired. Other thermoplastic resins include, for example, acrylic ester, styrene-acrylic ester, styrene-butadiene, vinyl acetate, vinyl acetate-ethylene, vinyl acetate-acrylic ester, ethylene-acrylic ester, ethylene-acrylic acid, butadiene Examples thereof include thermoplastic resins such as copolymers, urethane, and styrene-isoprene block polymers.
本発明に用いる固形可塑剤としては、「接着便覧」（第12版、昭和55年、高分子刊行会発行）に記載されているようフタル酸ジフェニル、フタル酸ジヘキシル、フタル酸ジシクロルヘキシル、フタル酸ジヒドロアビエチル、イソフタル酸ジメチル、安息香酸スクロース、二安息香酸エチレングリコール、三安息香酸トリメチロールエタン、三安息香酸グリセリド、四安息香酸ペンタエリトリット、八酢酸スクロース、クエン酸トリシクロヘキシル、Ｎ−シクロヘキシル−ｐ−トルエンスルホンアミドなど熱可塑性樹脂と相溶する結晶性のエステル化合物がある。 Solid plasticizers used in the present invention include diphenyl phthalate, dihexyl phthalate, dicyclohexyl phthalate, and phthalate as described in "Adhesion Handbook" (12th edition, 1980, published by Kobunshi Publishing Co., Ltd.). Dihydroabiethyl acid, dimethyl isophthalate, sucrose benzoate, ethylene glycol dibenzoate, trimethylolethane tribenzoate, glyceride tribenzoate, pentaerythritol tetrabenzoate, sucrose octaacetate, tricyclohexyl citrate, N-cyclohexyl There are crystalline ester compounds that are compatible with thermoplastic resins such as -p-toluenesulfonamide.
該固形可塑剤は、粘着剤組成物を塗工・乾燥時及び塗工したシートをロール状にして保管する際に、粘着性の発現を示さないように、融点が６０℃以上、好ましくは７０℃〜１１０℃である。該固形可塑剤の融点が６０℃未満であると、高圧法エチレン共重合体水性エマルジョンの最低造膜温度より低くなった場合、粘着剤組成物の塗工・乾燥時にすでに粘着性が発現してしまうという問題があり、また、融点が高くなりすぎると、粘着性を発現させるための加熱温度が高くなり、ＯＰＰ等基材の熱変形劣化を招く事になる。 The solid plasticizer has a melting point of 60 ° C. or higher, preferably 70 ° C. so as not to exhibit adhesiveness when the pressure-sensitive adhesive composition is applied and dried and when the coated sheet is stored in a roll shape. ° C to 110 ° C. When the melting point of the solid plasticizer is less than 60 ° C., when the pressure-sensitive ethylene copolymer aqueous emulsion is lower than the minimum film-forming temperature, adhesiveness has already been developed when the adhesive composition is applied and dried. In addition, if the melting point is too high, the heating temperature for expressing the adhesiveness becomes high, and the base material such as OPP is deteriorated by thermal deformation.
好ましい固形可塑剤としては安息香酸エステル化合物、ヒンダードフェノールエステル化合物等が好ましく用いられる。例えば安息香酸エステル化合物として安息香酸スクロース、安息香酸ジエチレングリコールエステル、安息香酸グリセリド、安息香酸ペンタエリトリットエステル、安息香酸トリメチロールエタンエステル、安息香酸トリメチロールプロパンエステル等が挙げられるが、安息香酸トリメチロールプロパンエステルが特に好ましく用いられる。 As a preferable solid plasticizer, a benzoic acid ester compound, a hindered phenol ester compound and the like are preferably used. Examples of the benzoic acid ester compound include sucrose benzoate, diethylene glycol benzoate, glyceryl benzoate, pentaerythritol benzoate, trimethylolethane benzoate, and trimethylolpropane benzoate. Esters are particularly preferably used.
他の好ましい固形可塑剤としてはヒンダードフェノールエステル化合物がある。例えばトリエチレングリコールビス〔３−（３−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕、トリエチレングリコールビス〔３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオネート〕、トリエチレングリコールビス〔３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシ−フェニル）プロピオネート〕、１，６−ヘキサンジオールビス〔３−（３−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕、１，６−ヘキサンジオールビス〔３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオネート〕、１，６−ヘキサンジオールビス〔３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕、チオビス〔エチレン３−（３−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕、チオビス〔エチレン３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオネート〕、チオビス〔エチレン３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕が挙げられる。特に好ましい固体可塑剤としては、トリエチレングリコールビス〔３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオネート〕、１，６−ヘキサンジオールビス〔３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕、チオビス〔エチレン３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕が挙げられる。 Another preferred solid plasticizer is a hindered phenol ester compound. For example, triethylene glycol bis [3- (3-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], tri Ethylene glycol bis [3- (3,5-di-t-butyl-4-hydroxy-phenyl) propionate], 1,6-hexanediol bis [3- (3-t-butyl-4-hydroxyphenyl) propionate] 1,6-hexanediol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 1,6-hexanediol bis [3- (3,5-di-t-butyl -4-hydroxyphenyl) propionate], thiobis [ethylene 3- (3-tert-butyl-4-hydroxypheny) ) Propionate], thiobis [ethylene 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], thiobis [ethylene 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ]. Particularly preferred solid plasticizers include triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 1,6-hexanediol bis [3- (3,5-di- -T-butyl-4-hydroxyphenyl) propionate] and thiobis [ethylene 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate].
これらの固形可塑剤は二種類以上の混合物としても使用することができる。固形可塑剤の水性分散液は沈降を防止し、塗工物の平滑性を保つためにも一定以下の粒径（体積基準中央値）を保つことが好ましく、そのため必要に応じてボールミル、ハンディミル等により粉砕分散される。 These solid plasticizers can also be used as a mixture of two or more. The aqueous dispersion of the solid plasticizer is preferably kept to a certain particle size (volume median) to prevent sedimentation and maintain the smoothness of the coated product. Etc. and pulverized and dispersed.
又、本発明の目的を阻害しない範囲で本粘着剤組成物に粘着付与剤、架橋剤、界面活性剤、消泡剤、滑剤、着色剤、フィラーを配合しても良いが、リサイクルを意図したＰＥＴボトルラベル用途の場合、粘着付与剤を含有しないことが好ましい。ディレードタック型粘着剤の塗工基材への塗工量は少ないと被着体との初期密着性が不足し、多すぎると平滑な塗工面が得られ難く、又乾燥性も低下するので、基材にもよるが、５〜２０ｇ／ｍ２が好ましく、特に８〜１５ｇ／ｍ２が好ましい。塗工はグラビアコーター、ロールコーター、リップコーター及びバーコーター等、汎用の塗工機を用いることができる。 In addition, a tackifier, a crosslinking agent, a surfactant, an antifoaming agent, a lubricant, a colorant, and a filler may be added to the pressure-sensitive adhesive composition as long as the object of the present invention is not impaired, but recycling is intended. In the case of PET bottle label use, it is preferable not to contain a tackifier. If the coating amount of the delayed tack type adhesive on the coating substrate is small, the initial adhesion with the adherend is insufficient, and if it is too large, it is difficult to obtain a smooth coated surface, and the drying property also decreases. Although depending on the substrate, 5 to 20 g / m 2 is preferable, and 8 to 15 g / m 2 is particularly preferable. For the coating, a general-purpose coating machine such as a gravure coater, a roll coater, a lip coater or a bar coater can be used.
本発明の別の構成は、前記した粘着剤組成物を、ラベル基材上に設けたラベルであることを特徴としている。ラベル基材としては、ＯＰＰ等オレフィン系プラスチックフィルム以外にも、紙等他の基材でも用いる事ができる。 Another configuration of the present invention is characterized in that the above-mentioned pressure-sensitive adhesive composition is a label provided on a label substrate. As the label base material, other base materials such as paper can be used besides the olefin plastic film such as OPP.
以下実施例を挙げて、本発明を具体的に説明する。ただし、本発明の範囲は、以下の実施例により何等限定されるものではない。例中、部とは質量部を、％とは質量％をそれぞれ表わす。 Hereinafter, the present invention will be specifically described with reference to examples. However, the scope of the present invention is not limited in any way by the following examples. In the examples, “part” represents part by mass, and “%” represents mass%.
〔実施例１〕
粉粒状トリエチレングリコールビス〔３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオネート（融点７７℃）〕５０部、イオン交換水４５部、粉粒状アクリルエステルーアクリル酸共重合樹脂５部及び２８％アンモニア水０．２部をボールミルに入れて分散粒子が３μｍ以下になるまで所定時間混練した。得られた水分散体５０部に、酢酸ビニルを２８％共重合したエチレン酢酸ビニル共重合体水性分散液（固形分５０％、粒子径１．２μｍ）を５０部配合した水性粘着剤分散液（固形分５３％）を調製した。得られた水性粘着剤分散液を用いて塗布量が、８ｇ／ｍ２となるようにＯＰＰフィルム（二村化学社製、ＦＯＲ３０、厚さ３０μｍ）上に直接塗布し、５０℃で１分間乾燥した。この状態では粘着性はないことを確認した。塗工物について、基材への接着性及びブロッキング性の評価を行った結果を表１に示す。
[Example 1]
50 parts of powdered triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate (melting point 77 ° C.)], 45 parts of ion-exchanged water, powdered acrylic ester-acrylic acid copolymer 5 parts of resin and 0.2 part of 28% ammonia water were placed in a ball mill and kneaded for a predetermined time until the dispersed particles became 3 μm or less. An aqueous pressure-sensitive adhesive dispersion comprising 50 parts of the obtained aqueous dispersion and 50 parts of an ethylene vinyl acetate copolymer aqueous dispersion (solid content 50%, particle diameter 1.2 μm) obtained by copolymerizing 28% of vinyl acetate ( 53% solids) was prepared. Using the obtained aqueous pressure-sensitive adhesive dispersion, the coating amount was directly applied onto an OPP film (Nippon Chemical Co., Ltd., FOR30, thickness 30 μm) so that the coating amount was 8 g / m 2 and dried at 50 ° C. for 1 minute. . It was confirmed that there was no tackiness in this state. Table 1 shows the results of evaluating the adhesion to the substrate and the blocking property of the coated product.
〔実施例２〕
実施例１において酢酸ビニルを２８％共重合したエチレン酢酸ビニル共重合体水性分散液（固形分５０％、分散粒子径１．２μｍ）を５０部の代わりに同水性分散液を８０部配合した以外は実施例１と同様に粘着剤を調製して、得られた粘着剤を実施例１と同様にＯＰＰフィルム上に直接塗布、乾燥後、塗工物の評価を行った結果を表１に示す。
[Example 2]
Except that 50 parts of ethylene vinyl acetate copolymer aqueous dispersion (solid content 50%, dispersed particle diameter 1.2 μm) obtained by copolymerizing 28% of vinyl acetate in Example 1 was mixed with 80 parts of the same aqueous dispersion. Table 1 shows the results of preparing the pressure-sensitive adhesive in the same manner as in Example 1 and applying the obtained pressure-sensitive adhesive directly on the OPP film in the same manner as in Example 1, drying and then evaluating the coated material. .
〔実施例３〕
実施例１において粉粒状トリエチレングリコールビス〔３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオネート（融点７７℃）〕５０部の代わりに粉粒状安息香酸トリメチロールプロパンエステル（融点８５℃）を同量配合した以外は実施例１と同様に粘着剤を調製して、得られた粘着剤を実施例１と同様にＯＰＰフィルム上に直接塗布、乾燥後、塗工物の評価を行った結果を表１に示す。
Example 3
Instead of 50 parts of powdered triethylene glycol bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate (melting point 77 ° C.)] in Example 1, powdered trimethylolpropane ester of benzoic acid ( A pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that the same amount of melting point 85 ° C.) was blended, and the resulting pressure-sensitive adhesive was directly applied onto an OPP film and dried in the same manner as in Example 1, and then the coated product was dried. Table 1 shows the results of the evaluation.
〔比較例１〕
実施例１において使用した酢酸ビニルを２８％共重合したエチレン酢酸ビニル共重合体水性粘着剤分散液（固形分５０％、分散粒子径１．２μｍ）の代わりに酢酸ビニル含有量が７０質量％の酢酸ビニル−エチレン共重合体水性エマルジョンを同部数配合した以外は実施例１と同様に粘着剤を調製して、得られた粘着剤を実施例１と同様にＯＰＰフィルム上に直接塗布、乾燥後、塗工物の評価を行った結果を表１に示す。
[Comparative Example 1]
An ethylene vinyl acetate copolymer aqueous pressure-sensitive adhesive dispersion (solid content 50%, dispersed particle size 1.2 μm) obtained by copolymerizing 28% of vinyl acetate used in Example 1 has a vinyl acetate content of 70% by mass. A pressure-sensitive adhesive was prepared in the same manner as in Example 1 except that the same amount of vinyl acetate-ethylene copolymer aqueous emulsion was blended, and the resulting pressure-sensitive adhesive was directly applied on the OPP film in the same manner as in Example 1 and dried. Table 1 shows the results of the evaluation of the coated products.
〔比較例２〕
実施例１において酢酸ビニルを２８％共重合したエチレン酢酸ビニル共重合体水性粘着剤分散液（固形分５０％、分散粒子径１．２μｍ）を５０部の代わりに酢酸ビニル含有量が７０質量％の酢酸ビニル−エチレン共重合体水性エマルジョンを４０部、酢酸ビニルを２８％共重合したエチレン酢酸ビニル共重合体水性粘着剤分散液（固形分５０％、分散粒子径１．２μｍ）を１０部配合した以外は実施例１と同様に粘着剤を調製して、得られた粘着剤を実施例１と同様に評価を行った結果を表１に示す。
[Comparative Example 2]
An ethylene vinyl acetate copolymer aqueous pressure-sensitive adhesive dispersion (solid content 50%, dispersed particle diameter 1.2 μm) obtained by copolymerizing 28% vinyl acetate in Example 1 was replaced by 50 parts with a vinyl acetate content of 70% by mass. 40 parts of an aqueous vinyl acetate-ethylene copolymer emulsion and 10 parts of an ethylene vinyl acetate copolymer aqueous adhesive dispersion (solid content 50%, dispersed particle size 1.2 μm) copolymerized with 28% vinyl acetate Table 1 shows the results obtained by preparing a pressure-sensitive adhesive in the same manner as in Example 1 and evaluating the obtained pressure-sensitive adhesive in the same manner as in Example 1.
実施例及び比較例に於けるディレードタック型粘着剤水性分散液の塗工物性評価のための接着強度、及び、塗工物の保存安定性を評価するためのブロッキング性を以下の方法によって評価した。 In the examples and comparative examples, the adhesive strength for evaluating the coating physical properties of the delayed tack type adhesive aqueous dispersion and the blocking property for evaluating the storage stability of the coated materials were evaluated by the following methods. .
（接着強度試験）
塗工物から１５ｍｍ幅の短冊状に切り出して、１１０℃に設定した均熱乾燥機中で１０秒間加熱し粘着性を発現させた後、室温でＰＥＴシート（東洋紡績社製Ｅ５１０１、厚さ５０μｍ）に貼合して、ＪＩＳＫ−６８４８に準じて、１８０度剥離により、接着強度を当日及び一週間後の強度を測定し、以下の基準で判定した。結果を表１に示す。
○：接着強度が、１Ｎ／１５ｍｍ以上であってＰＥＴシートに充分接着している。
×：接着強度が、１Ｎ／１５ｍｍ未満でＰＥＴシートから手で力を加えなくても容易に剥離する。
(Adhesive strength test)
A 15 mm wide strip was cut out from the coated material and heated for 10 seconds in a soaking dryer set at 110 ° C. to develop adhesiveness, and then a PET sheet (E5101 manufactured by Toyobo Co., Ltd., thickness 50 μm) at room temperature. ), And according to JISK-6848, the adhesive strength was measured on the day and after one week by 180 degree peeling, and judged according to the following criteria. The results are shown in Table 1.
○: Adhesive strength is 1 N / 15 mm or more, and it is sufficiently adhered to the PET sheet.
X: Adhesive strength is less than 1 N / 15 mm, and it peels easily even if force is not applied manually from a PET sheet.
(糊残り性)
接着強度試験で剥離試験した際の貼着試験片のＰＥＴシートを目視判定した。
○：粘着剤がＰＥＴシートに全く残存付着していない。
△：粘着剤がＰＥＴシートに剥離面積の３割未満に残存付着している。
×：粘着剤がＰＥＴシートに剥離面積の３割以上に残存付着している。
(Adhesive residue)
The PET sheet of the adhesion test piece when the peel test was performed in the adhesive strength test was visually determined.
○: No pressure-sensitive adhesive remains on the PET sheet.
Δ: The adhesive remained on the PET sheet in less than 30% of the peeled area.
X: The adhesive remained on the PET sheet in 30% or more of the peeled area.
（ブロッキング性）
粘着剤塗工物の粘着剤層と裏面の印刷層を重ねて、０．１ｍＰａの荷重をかけて、所定温度（表記載）に５時間保存後に剥離し、以下の基準で判定し、５０℃で４以上を○、３を△、２以下を×とした。
５：剥離時に抵抗なく剥離する。
４：剥離時に若干音がする。
３：剥離時に塗布接着層の跡が残る。
２：剥離時に塗布接着層が一部剥離する。
１：剥離時に塗布接着層が全面剥離する。
(Blocking property)
The pressure-sensitive adhesive layer of the pressure-sensitive adhesive coating and the printed layer on the back surface are overlapped, peeled off after 5 hours of storage at a predetermined temperature (described in the table) under a load of 0.1 mPa, determined according to the following criteria, 50 ° C. 4 or more was evaluated as ◯, 3 as Δ, and 2 or less as X.
5: It peels without resistance at the time of peeling.
4: There is a slight noise when peeling.
3: A trace of the coating adhesive layer remains at the time of peeling.
2: A part of the coating adhesive layer is peeled off at the time of peeling.
1: The coating adhesive layer peels off at the time of peeling.
本発明の感熱性ディレードタック型粘着剤は、オレフィン系のラベル基材への接着性に優れ、且つ、相対的にポリエステル系被着体への粘着性を調整できるため、特にＰＥＴボトル向けに適し、ＰＥＴボトルのリサイクル促進に貢献でき、環境保全及び経済的な有益性を追求する上での産業的意義は、極めて多大である。
The heat-sensitive delayed tack-type pressure-sensitive adhesive of the present invention is particularly suitable for PET bottles because it has excellent adhesion to olefin-based label substrates and can relatively adjust the adhesion to polyester-based adherends. The industrial significance in pursuing environmental conservation and economic benefits that can contribute to promoting the recycling of PET bottles is enormous.
Claims (8)
A delayed tack type pressure-sensitive adhesive label, wherein a dry coating layer of the delayed tack type pressure-sensitive adhesive composition according to any one of claims 1 to 7 is provided on a label substrate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007171239A (en) * | 2005-12-19 | 2007-07-05 | Fuji Seal International Inc | Heat-sensitive label and labeled container |
| JP2007254571A (en) * | 2006-03-23 | 2007-10-04 | The Inctec Inc | Powder adhesive composition |
| CN112771597A (en) * | 2018-09-28 | 2021-05-07 | 优泊公司 | In-mold label and container with the same |
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| JPS5516055A (en) * | 1978-07-21 | 1980-02-04 | Sanyo Chem Ind Ltd | Heat-sensitive adhesive, its preparation and adhesive sheet |
| JPS6389583A (en) * | 1986-10-02 | 1988-04-20 | Mitsubishi Paper Mills Ltd | Heat-sensitive tacky-adhesive composition and heat-sensitive tacky-adhesive sheet prepared by using the same |
| JPS6485269A (en) * | 1987-09-25 | 1989-03-30 | Mitsubishi Paper Mills Ltd | Heat-sensitive pressure-sensitive adhesive composition and heat-sensitive pressure-sensitive adhesive sheet |
| JPH01193381A (en) * | 1988-01-27 | 1989-08-03 | Mitsubishi Paper Mills Ltd | Heat-sensitive tacky composition and heat-sensitive tacky sheet |
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| JPH10276606A (en) * | 1997-04-01 | 1998-10-20 | Furukawa Electric Co Ltd:The | Net for culturing short-neck clam |
| JPH11263949A (en) * | 1998-03-19 | 1999-09-28 | Mitsubishi Paper Mills Ltd | Heat-sensitive adhesive sheet and heat-sensitive adhesive type heat-sensitive recording sheet |
| JP2003206460A (en) * | 2002-01-10 | 2003-07-22 | Daicel Chem Ind Ltd | Aqueous heat sensitive adhesive composition, heat sensitive adhesive sheet and method for producing heat sensitive adhesive sheet |
| JP2003238924A (en) * | 2002-02-14 | 2003-08-27 | Dainippon Ink & Chem Inc | Delayed tack type sticking agent composition and sticking label |
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2003
- 2003-09-22 JP JP2003329834A patent/JP2005097353A/en active Pending
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|---|---|---|---|---|
| JPS5516055A (en) * | 1978-07-21 | 1980-02-04 | Sanyo Chem Ind Ltd | Heat-sensitive adhesive, its preparation and adhesive sheet |
| JPS6389583A (en) * | 1986-10-02 | 1988-04-20 | Mitsubishi Paper Mills Ltd | Heat-sensitive tacky-adhesive composition and heat-sensitive tacky-adhesive sheet prepared by using the same |
| JPS6485269A (en) * | 1987-09-25 | 1989-03-30 | Mitsubishi Paper Mills Ltd | Heat-sensitive pressure-sensitive adhesive composition and heat-sensitive pressure-sensitive adhesive sheet |
| JPH01193381A (en) * | 1988-01-27 | 1989-08-03 | Mitsubishi Paper Mills Ltd | Heat-sensitive tacky composition and heat-sensitive tacky sheet |
| JPH07196997A (en) * | 1993-12-30 | 1995-08-01 | Nitta Gelatin Inc | Production of water-dispersion type heat-sensitive adhesive |
| JPH10276606A (en) * | 1997-04-01 | 1998-10-20 | Furukawa Electric Co Ltd:The | Net for culturing short-neck clam |
| JPH11263949A (en) * | 1998-03-19 | 1999-09-28 | Mitsubishi Paper Mills Ltd | Heat-sensitive adhesive sheet and heat-sensitive adhesive type heat-sensitive recording sheet |
| JP2003206460A (en) * | 2002-01-10 | 2003-07-22 | Daicel Chem Ind Ltd | Aqueous heat sensitive adhesive composition, heat sensitive adhesive sheet and method for producing heat sensitive adhesive sheet |
| JP2003238924A (en) * | 2002-02-14 | 2003-08-27 | Dainippon Ink & Chem Inc | Delayed tack type sticking agent composition and sticking label |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007171239A (en) * | 2005-12-19 | 2007-07-05 | Fuji Seal International Inc | Heat-sensitive label and labeled container |
| JP2007254571A (en) * | 2006-03-23 | 2007-10-04 | The Inctec Inc | Powder adhesive composition |
| CN112771597A (en) * | 2018-09-28 | 2021-05-07 | 优泊公司 | In-mold label and container with the same |
| CN112771597B (en) * | 2018-09-28 | 2023-09-26 | 优泊公司 | In-mold label and container with in-mold label |
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