JP6807463B2 - Hot melt pressure sensitive adhesive for clear on clear label - Google Patents

Hot melt pressure sensitive adhesive for clear on clear label Download PDF

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Publication number
JP6807463B2
JP6807463B2 JP2019543021A JP2019543021A JP6807463B2 JP 6807463 B2 JP6807463 B2 JP 6807463B2 JP 2019543021 A JP2019543021 A JP 2019543021A JP 2019543021 A JP2019543021 A JP 2019543021A JP 6807463 B2 JP6807463 B2 JP 6807463B2
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Japan
Prior art keywords
weight
sensitive adhesive
hot melt
melt pressure
less
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JP2019543021A
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Japanese (ja)
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JP2020510715A (en
Inventor
パン，シャオミン
ワン，ミン
シン，シンユ
ワン，シャオフア
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Avery Dennison Corp
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Avery Dennison Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/334—Applications of adhesives in processes or use of adhesives in the form of films or foils as a label
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/304—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being heat-activatable, i.e. not tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2453/00—Presence of block copolymer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2491/00—Presence of oils, fats or waxes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Theoretical Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)

Description

本発明は、一般に、感圧接着剤用組成物、特に、改善された接着剤を配合してコーティングすることを含む方法により良好な加工性を維持しつつ、高品質のラベルを提供する改善された接着剤に関する。 The present invention has generally been improved to provide high quality labels while maintaining good processability by methods comprising blending and coating pressure sensitive adhesive compositions, in particular improved adhesives. Regarding adhesives.

接着ラベル及びテープがよく知られている。通常のラベル構成において、接着剤の１つ以上の層が離型ライナー上にコーティングまたは適用され、その後、紙、重合性フィルム、またはその他のインク受容性柔軟材等の表面材に積層される。通常のテープ構成において、重合性フィルム及び織紙は、一方の表面上に接着剤でコーティングされ、その後巻かれる。テープとラベルいずれにも使用される接着剤は、ゴム系及びアクリル系感圧接着剤（ＰＳＡ）を含む。ＰＳＡは、有機溶剤から、水分散剤から、またはホットメルトとして離型ライナーや表面材に適用できる。 Adhesive labels and tapes are well known. In a typical label configuration, one or more layers of adhesive are coated or applied on the release liner and then laminated on a surface material such as paper, polymerizable film, or other ink-accepting softener. In a normal tape configuration, the polymerizable film and woven paper are coated with an adhesive on one surface and then rolled. Adhesives used for both tapes and labels include rubber-based and acrylic pressure-sensitive adhesives (PSA). PSA can be applied to mold release liners and surface materials from organic solvents, water dispersants, or as hot melts.

ホットメルトＰＳＡ（ＨＭＰＳＡ）は、消費材及び産業製品用のガラス、金属、並びにプラスチック容器等の商品をラベル付けする便利で経済的な方法を提供することができる。ＨＭＰＳＡは、固体状のため扱いやすく、如何なる追加加工もなく迅速に接着結合し、一般に保存期間が長い。また、ＨＭＰＳＡは、通常、溶剤を含まないので、環境にやさしく、費用面で効率的である。 Hot melt PSA (HMPSA) can provide a convenient and economical way to label commodities such as glass, metal, and plastic containers for consumer and industrial products. HMPSA is solid and easy to handle, has a rapid adhesive junction without any additional processing, and generally has a long shelf life. In addition, since HMPSA usually does not contain a solvent, it is environmentally friendly and cost-effective.

ＨＭＰＳＡの一例は、米国特許第５，９４２，５６９号にあり、ａ）約５重量％〜約９０重量％の熱可塑性重合体、ｂ）約０重量％〜約６５重量％の粘着付与樹脂、ｃ）約０重量％〜約５０重量％の可塑剤、ｄ）最大で約２重量％の酸化防止剤、及びペレット化補助剤を含む粘着性ホットメルト組成物を含むペレット状の重合性組成物を開示している。前記粘着性ホットメルト組成物は、ある程度の最小量の粘着付与剤または可塑剤を有し、約２５℃における貯蔵弾性率Ｇ’が約５×１０６ｄｙｎｅｓ／ｃｍ２未満である感圧接着剤であり、それぞれのペレットは、実質的に粘着性のない表面を有する。前記開示内容は、物品の成形に好適なペレット状の重合性組成物をさらに含む。前記組成物は、少なくとも１つの一般的な構成Ａ―Ｂ―Ａの高分子量トリブロック共重合体と、可塑剤と、ペレット化補助剤とを含む粘着性ホットメルト組成物を含む。ペレット化補助剤は、成形品に表面粘着性が実質的にないように粘着性組成物を実質的に囲んでいる。ペレットの形成方法も開示されている。 An example of HMPSA is in US Pat. No. 5,942,569, a) about 5% to about 90% by weight thermoplastic polymer, b) about 0% to about 65% by weight of tackifier resin, c) Pellet-like polymerizable composition containing an adhesive hot melt composition containing about 0% by weight to about 50% by weight of a plasticizer, d) up to about 2% by weight of an antioxidant, and a pelletizing aid. Is disclosed. The tacky hot melt composition has a certain minimum amount of tackifier or plasticizer and has a storage elastic modulus G'at less than about 5 × 10 6 dynes / cm 2 at about 25 ° C. And each pellet has a substantially non-sticky surface. The disclosure further includes a pellet-like polymerizable composition suitable for molding an article. The composition comprises a sticky hot melt composition comprising at least one general composition ABA high molecular weight triblock copolymer, a plasticizer and a pelleting aid. The pelleting aid substantially encloses the adhesive composition so that the part is substantially non-surface adhesive. A method for forming pellets is also disclosed.

米国特許第７，５９５，３６５号のＨＭＰＳＡには、粘着付与剤の軟化点特性を変形するために、ポリアルファオレフィンオイルまたはポリアルファオレフィンオイルの組み合わせを使用することが開示されている。前記開示内容は、粘着付与剤及びポリアルファオレフィンオイルを含有する組成物をさらに含む。 HMPSA of US Pat. No. 7,595,365 discloses the use of polyalphaolefin oils or combinations of polyalphaolefin oils to alter the softening point properties of tackifiers. The disclosure further includes a composition containing a tackifier and a polyalphaolefin oil.

米国特許第８，０７６，４２２号には、エチレン及び／またはプロピレンとＣ４〜Ｃ１２アルファオレフィンに基づいて３０〜９０重量％の少なくとも１つの共重合体を含有する再封止可能な包装用ホットメルト接着剤が開示されており、これは溶融指数が５〜１００ｇ／１０分（ＤＩＮ ＩＳＯ １１３３）であるメタロセン触媒重合によって得られる。接着剤は、軟化点が８０〜１４０℃である５〜５０重量％の粘着付与剤樹脂、融点が１２０〜１７０℃である０〜１５重量％のワックス、並びに０．１〜２０重量％の添加剤及び補助剤をさらに含む。接着剤は、１７０〜１９０℃の温度で測定された粘度が２５，０００ｍＰａｓ〜２５０，０００ｍＰａｓである。 US Pat. No. 8,076,422 states that for resealable packaging containing at least one copolymer of ethylene and / or propylene and 30-90% by weight based on C 4- C 12 alpha olefin. A hot melt adhesive has been disclosed, which is obtained by metallocene catalytic polymerization with a melt index of 5-100 g / 10 min (DIN ISO 1133). The adhesive is 5 to 50% by weight of tackifier resin having a softening point of 80 to 140 ° C., 0 to 15% by weight of wax having a melting point of 120 to 170 ° C., and 0.1 to 20% by weight of addition. Further includes agents and auxiliaries. The adhesive has a viscosity of 25,000 mPas to 250,000 mPas measured at a temperature of 170 to 190 ° C.

さらに、ＨＭＰＳＡ組成物はまた、米国特許第９，２４２，４３７号、米国特許出願公開ＵＳ２００５／００１３９９６、ＵＳ２００６／０２５１８９０、ＵＳ２０１０／０１９３１２７、ＵＳ２０１６／０２７２８５６、国際特許出願公開ＷＯ２００２／０７４８３７、ＷＯ２００６/１０７７６３によって提供される。 In addition, the HMPSA composition is also according to US Pat. No. 9,242,437, US Patent Application Publication US2005 / 0013996, US2006 / 0251890, US2010 / 0193127, US2016 / 0272856, International Patent Application Publication WO2002 / 074837, WO2006 / 107763. Provided.

これらの参照文献を勘案しても、性能特性、例えば、水白化耐性、再配置性、及び／または光学的鮮明度の改善を提供する高性能のＨＭＰＳＡが必要である。 With these references in mind, there is a need for a high performance HMPSA that provides improved performance characteristics such as water whitening resistance, rearrangement and / or optical sharpness.

本発明の一実施形態において、本発明は、ホットメルト感圧接着剤に関する。接着剤は、ベース重合体を含み、前記ベース重合体は、スチレンイソプレン共重合体を含む。好ましいベース重合体は、３０重量％未満のジブロックのグレードを有する。接着剤は、粘着付与剤をさらに含み、前記粘着付与剤は、水素化脂環式炭化水素樹脂を含む。粘着付与剤は、好ましくは、３００〜８００の範囲内の重量平均分子量を有する。接着剤は、可塑剤をさらに含み、前記可塑剤は、４０℃における動粘度が４００〜１０００ｍｍ２／秒の範囲内であるパラフィンオイルを含む。可塑剤は、好ましくは、数平均分子量が４００〜１０００の範囲内であり、４０℃における動粘度が４００〜７００ｍｍ２／秒の範囲内である。接着剤は、ポリエチレンワックスをさらに含み得る。ポリエチレンワックスは、好ましくは、１４０℃における動的粘度が１５０〜５００センチポアズの範囲内であり、流動点が１００℃を超える。 In one embodiment of the invention, the invention relates to a hot melt pressure sensitive adhesive. The adhesive comprises a base polymer, and the base polymer comprises a styrene isoprene copolymer. Preferred base polymers have a diblock grade of less than 30% by weight. The adhesive further comprises a tackifier, and the tackifier comprises a hydrogenated alicyclic hydrocarbon resin. The tackifier preferably has a weight average molecular weight in the range of 300-800. The adhesive further comprises a plasticizer, said plasticizer containing paraffin oil having a kinematic viscosity at 40 ° C. in the range of 400-1000 mm 2 / sec. The plasticizer preferably has a number average molecular weight in the range of 400 to 1000 and a kinematic viscosity at 40 ° C. in the range of 400 to 700 mm 2 / sec. The adhesive may further include polyethylene wax. The polyethylene wax preferably has a dynamic viscosity at 140 ° C. in the range of 150-500 centipores and a pour point of more than 100 ° C.

他の実施形態において、本発明はラベルに関する。ラベルは、印刷された表示（ｉｎｄｉｃｉａ）を収容するための表面材層を含む。ラベルは、一実施形態によるホットメルト感圧接着剤層をさらに含む。 In other embodiments, the present invention relates to labels. The label includes a surface material layer for accommodating the printed indication (indicia). The label further comprises a hot melt pressure sensitive adhesive layer according to one embodiment.

他の実施形態において、本発明はラベル付き容器に関する。ラベル付き容器は、外表面を規定する容器を含む。ラベル付き容器は、前記容器の外表面に接着された一実施形態によるラベルをさらに含む。 In other embodiments, the present invention relates to labeled containers. Labeled containers include containers that define the outer surface. The labeled container further includes a label according to one embodiment that is adhered to the outer surface of the container.

他の実施形態において、本発明は、ラベルを容器に適用する方法に関する。前記方法は、外表面を規定する容器を提供するステップを含む。前記方法は、一実施形態によるラベルを提供するステップをさらに含む。前記方法は、容器の外表面にラベルを接着させることにより、ラベルを容器に適用するステップをさらに含む。 In another embodiment, the invention relates to a method of applying a label to a container. The method comprises providing a container that defines the outer surface. The method further comprises the step of providing a label according to one embodiment. The method further comprises applying the label to the container by adhering the label to the outer surface of the container.

本発明を添付の図面を参照して以下で詳細に説明し、本明細書において、同一の符号は、同一の部分を示す。 The present invention will be described in detail below with reference to the accompanying drawings, and in the present specification, the same reference numerals indicate the same parts.

本発明の一実施形態によるボトル等のラベル付き容器の概略図である。It is the schematic of the container with the label such as a bottle by one Embodiment of this invention. 本発明の一実施形態による表面材層と、ホットメルト感圧接着剤層と、ライナーと、を有するラベルの断面概略図である。FIG. 5 is a schematic cross-sectional view of a label having a surface material layer, a hot melt pressure sensitive adhesive layer, and a liner according to an embodiment of the present invention.

本発明は、一般に、ラベルの適用に用いる際に、良好な加工性を維持しつつ、性能特性の有利な組み合わせを提供するホットメルト感圧接着剤（ＨＭＰＳＡ）に関する。例えば、湿潤な環境または湿度の高い環境に露出した接着剤は、高レベルの水白化耐性を有することが有利である。かかる湿度の高い条件は、飲料、パーソナルケア用品、またはその他の物品を入れるのに用いられるガラスまたはペットボトルに適用される接着ラベルでよく見られる。また、ラベルが除去されたボトルまたは他の容器に接着剤の残留物が著しく残ることなく、ラベルを除去及び／または再配置できることが有用であり得る。かかる特性は、再使用またはリサイクルされる容器の場合、特に重要であり得る。さらに、光学的にクリアなまたは透明な接着剤は、ラベルが接着しているガラスボトル等の、同様にクリアなまたは透明な容器を通して前記接着ラベルが見えることを可能にする。また、接着剤が容易に加工される能力は、接着剤がラベルや他の物品に高品質のコーティング層をさらによく形成することを可能にする好ましい特性であり得る。 The present invention generally relates to hot melt pressure sensitive adhesives (HMPSAs) that, when used in label applications, provide an advantageous combination of performance characteristics while maintaining good processability. For example, an adhesive exposed to a moist or humid environment would preferably have a high level of water whitening resistance. Such high humidity conditions are common in adhesive labels applied to glass or PET bottles used to hold beverages, personal care products, or other items. It may also be useful to be able to remove and / or reposition the label without significant adhesive residue remaining in the bottle or other container from which the label has been removed. Such properties can be particularly important for containers that are reused or recycled. In addition, an optically clear or transparent adhesive allows the adhesive label to be visible through a similarly clear or transparent container, such as a glass bottle to which the label is attached. Also, the ability of the adhesive to be easily processed can be a preferred property that allows the adhesive to better form a high quality coating layer on labels and other articles.

しかし、ＨＭＰＳＡが前記特性を全て同時に示すことは困難である。その理由の１つは、１つの特性を改善させる構成要素が他の特性に不利な影響を与えるためである。例えば、低水白化及び再配置性が求められる特性は、高分子量及び高粘度を有する接着剤成分の使用と関係し得る。しかしながら、配合の容易さ及びコーティングの高品質が求められる特性は、高分子量及び高粘度を有する接着剤の構成要素の使用によって否定的な影響を受ける場合がある。 However, it is difficult for HMPSA to exhibit all of the above characteristics at the same time. One of the reasons is that the components that improve one property adversely affect the other. For example, the required properties of low water whitening and rearrangement may be related to the use of adhesive components with high molecular weight and high viscosity. However, the ease of formulation and the high quality required properties of the coating can be negatively affected by the use of high molecular weight and high viscosity adhesive components.

驚くことに、本発明者らは、選択的に特定量が用いられる構成要素の特定の組み合わせが、性能特性、例えば、水白化耐性、再配置性、及び／または光学的鮮明度の非常に好ましい組み合わせを示す高性能のＨＭＰＳＡを提供するということを見付けた。有利には、これらのＨＭＰＳＡはまた、接着剤及びラベルを製造・適用の際、加工性の改善、そして、最終的な使用者の製品において良好な接着剤及びラベルの品質を示す。 Surprisingly, we find that certain combinations of components in which certain amounts are selectively used are highly preferred for performance characteristics such as water whitening resistance, rearrangement and / or optical sharpness. We have found that it provides a high performance HMPSA that shows the combination. Advantageously, these HMPSAs also show improved processability when manufacturing and applying adhesives and labels, and good adhesive and label quality in the final user's product.

特に、ＨＭＰＳＡ組成物は、パラフィンオイルを含む可塑剤と、水素化脂環式炭化水素樹脂とを含む粘着付与剤を含み、それぞれ、特定の範囲内の分子量及び粘度を選択的に有し、驚くことに、上述の性能特性の組み合わせを有するＨＭＰＳＡを提供するということを見付けた。例えば、接着剤は、良好な透明性、再配置性、及び、耐白化性、耐オイル移動性、耐膨潤性、または耐しわ性を有すると共に、標準配合及びコーティングの適用において依然として使いやすいラベルの製造に使用できる。 In particular, the HMPSA composition comprises a plasticizer containing paraffin oil and a tackifier containing a hydrogenated alicyclic hydrocarbon resin, each of which selectively has a molecular weight and viscosity within a specific range, which is surprising. In particular, it has been found to provide an HMPSA having the combination of performance characteristics described above. For example, adhesives have good transparency, rearrangement, and whitening resistance, oil transfer resistance, swelling resistance, or wrinkle resistance, and are still easy to use in standard formulations and coating applications. Can be used for manufacturing.

特定の理論にとらわれることなく、パラフィンオイルとＳＩＳブロック共重合体は何れも線状分子構造を有するので、パラフィンオイルは、ＨＭＰＳＡのベースであるＳＩＳブロック共重合体と良好な相用性を有すると考えられる。接着剤層のこれらの構成要素における内部の相互作用は、例えば、オイルの移動を制限し、接着された重合体構造化フィルム型の表面材の膨潤性及びしわを制御するように作用できる。また、線状脂肪族炭化水素樹脂に比べて低分子量の水素化脂環式炭化水素樹脂は、水素化脂環式樹脂がその軟化点に否定的な影響を与えることなく、ＨＭＰＳＡの加工性を高めることを可能とする。ＨＭＰＳＡ組成物は、全体的にバルク疎水性を有するので、接着剤の水白化も最小化される。 Without being bound by any particular theory, paraffin oil and SIS block copolymers both have a linear molecular structure, so that paraffin oil has good compatibility with the SIS block copolymer, which is the base of HMPSA. Conceivable. Internal interactions in these components of the adhesive layer can act, for example, to limit the movement of oil and control the swelling and wrinkling of the adhered polymer-structured film-type surface material. Further, the hydrogenated alicyclic hydrocarbon resin having a lower molecular weight than the linear aliphatic hydrocarbon resin can improve the processability of HMPSA without the hydrogenated alicyclic resin having a negative influence on the softening point. It is possible to increase. Since the HMPSA composition has bulk hydrophobicity as a whole, water whitening of the adhesive is also minimized.

一実施形態において、ＨＭＰＳＡは、ベース重合体と、粘着付与剤と、可塑剤と、を含む。一部の実施形態において、ＨＭＰＳＡはまた、ポリエチレンワックスを含む。一部の実施形態において、ベース重合体は、スチレンイソプレンスチレン（ＳＩＳ）共重合体を含み、粘着付与剤は、水素化脂環式炭化水素樹脂を含み、可塑剤は、パラフィンオイルを含む。好ましい実施形態において、可塑剤は、４０℃における動粘度が４００〜１０００ｍｍ２／秒の範囲内である。 In one embodiment, HMPSA comprises a base polymer, a tackifier and a plasticizer. In some embodiments, HMPSA also comprises polyethylene wax. In some embodiments, the base polymer comprises a styrene isoprene styrene (SIS) copolymer, the tackifier comprises a hydride alicyclic hydrocarbon resin, and the plasticizer comprises a paraffin oil. In a preferred embodiment, the plasticizer has a kinematic viscosity at 40 ° C. in the range of 400-1000 mm 2 / sec.

ＨＭＰＳＡのベース重合体は、ＳＩＳブロック共重合体を含み、ここで、「Ｓ」は、スチレン単量体の重合セグメントまたは「ブロック」を意味し、「Ｉ」は、イソプレン単量体の重合セグメントまたは「ブロック」を意味する。ＳＩＳブロック共重合体は、ＳＩジブロックを含有しない純粋なトリブロック共重合体であり得るか、または所定比率のＳＩジブロックを含有できる。より高いジブロック含量は、ＳＩＳブロック共重合体の粘着性の増加と関係し、より低いジブロック含量は、共重合体の弾性増加と関係し得るということが明らかになっている。ＨＭＰＳＡのベース重合体のジブロック含量は、０〜５０重量％、例えば、０〜３０重量％、５〜３５重量％、１０〜４０重量％、１５〜４５重量％、または２０〜５０重量％の範囲内であり得る。上限の観点から、前記ジブロック含量は、５０重量％未満、例えば、４５重量％未満、４０重量％未満、３５重量％未満、３０重量％未満、２５重量％未満、２０重量％未満、１５重量％未満、１０重量％未満、または５重量％未満であり得る。下限の観点から、前記ジブロック含量は、少なくとも５重量％、少なくとも１０重量％、少なくとも１５重量％、少なくとも２０重量％、少なくとも２５重量％、少なくとも３０重量％、少なくとも３５重量％、少なくとも４０重量％、または少なくとも４５重量％であり得る。一部の実施形態において、ベース重合体は、３０重量％未満のジブロックのグレードを有する。 The HMPSA base polymer comprises a SIS block copolymer, where "S" means a styrene monomer polymerization segment or "block" and "I" is an isoprene monomer polymerization segment. Or it means "block". The SIS block copolymer can be a pure triblock copolymer that does not contain SI diblock, or it can contain a predetermined proportion of SI diblock. It has been shown that a higher diblock content may be associated with an increase in the tackiness of the SIS block copolymer and a lower diblock content may be associated with an increase in the elasticity of the copolymer. The diblock content of the base polymer of HMPSA is 0-50% by weight, for example 0-30% by weight, 5-35% by weight, 10-40% by weight, 15-45% by weight, or 20-50% by weight. Can be within range. From the viewpoint of the upper limit, the diblock content is less than 50% by weight, for example, less than 45% by weight, less than 40% by weight, less than 35% by weight, less than 30% by weight, less than 25% by weight, less than 20% by weight, 15% by weight. It can be less than%, less than 10% by weight, or less than 5% by weight. From the viewpoint of the lower limit, the diblock content is at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight. , Or at least 45% by weight. In some embodiments, the base polymer has a diblock grade of less than 30% by weight.

また、ＳＩＳブロック共重合体のスチレン含量は、ベース重合体の性能特性に影響を与え得る。特定のジブロック含量と共に特定のスチレン含量は、（１９０℃で１０分当たり２０ｇを超える）高いメルトフロー指数及び低い粘性への所望の特性をベース重合体に提供できるということが明らかになっている。これらの特性を共に用いると、配合工程及びコーティング工程により好適な重合体を作製することができる。ベース重合体のスチレン含量は、０〜５０重量％、例えば、０〜３０重量％、５〜３５重量％、１０〜４０重量％、１５〜４５重量％、または２０〜５０重量％の範囲内であり得る。上限の観点から、前記スチレン含量は、５０重量％未満、例えば、４５重量％未満、４０重量％未満、３５重量％未満、３０重量％未満、２５重量％未満、２０重量％未満、１５重量％未満、１０重量％未満、または５重量％未満であり得る。下限の観点から、前記スチレン含量は、少なくとも５重量％、少なくとも１０重量％、少なくとも１５重量％、少なくとも２０重量％、少なくとも２５重量％、少なくとも３０重量％、少なくとも３５重量％、少なくとも４０重量％、または少なくとも４５重量％であり得る。一部の実施形態において、前記ベース重合体は、２５重量％未満のスチレン含量を有する。 In addition, the styrene content of the SIS block copolymer can affect the performance characteristics of the base polymer. It has been shown that a particular styrene content, along with a particular diblock content, can provide the base polymer with the desired properties for a high melt flow index (more than 20 g per 10 minutes at 190 ° C.) and a low viscosity. .. When these properties are used together, a suitable polymer can be produced by the compounding step and the coating step. The styrene content of the base polymer is in the range of 0-50% by weight, for example 0-30% by weight, 5-35% by weight, 10-40% by weight, 15-45% by weight, or 20-50% by weight. possible. From the viewpoint of the upper limit, the styrene content is less than 50% by weight, for example, less than 45% by weight, less than 40% by weight, less than 35% by weight, less than 30% by weight, less than 25% by weight, less than 20% by weight, 15% by weight. Less than, less than 10% by weight, or less than 5% by weight. From the viewpoint of the lower limit, the styrene content is at least 5% by weight, at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, at least 40% by weight. Or it can be at least 45% by weight. In some embodiments, the base polymer has a styrene content of less than 25% by weight.

ＨＭＰＳＡ組成物中のＳＩＳブロック共重合体の量は、１５〜６５重量％、例えば、１５〜４５重量％、２０〜５０重量％、２５〜５５重量％、３０〜６０重量％、または３５〜６５重量％の範囲内であり得る。ＨＭＰＳＡ組成物中のＳＩＳブロック共重合体の量は、３０〜５０重量％、例えば、３０〜４２重量％、３２〜４４重量％、３４〜４６重量％、３６〜４８重量％、または３８〜５０重量％の範囲内であり得る。上限の観点から、ＨＭＰＳＡ組成物中のＳＩＳブロック共重合体の量は、７０重量％未満、６５重量％未満、６０重量％未満、５５重量％未満、５０重量％未満、４５重量％未満、または４０重量％未満であり得る。下限の観点から、ＨＭＰＳＡ組成物中のＳＩＳブロック共重合体の量は、少なくとも１０重量％、少なくとも１５重量％、少なくとも２０重量％、少なくとも２５重量％、少なくとも３０重量％、少なくとも３５重量％、または少なくとも４０重量％であり得る。 The amount of SIS block copolymer in the HMPSA composition is 15-65% by weight, for example 15-45% by weight, 20-50% by weight, 25-55% by weight, 30-60% by weight, or 35-65% by weight. It can be in the range of% by weight. The amount of SIS block copolymer in the HMPSA composition is 30-50% by weight, for example 30-42% by weight, 32-44% by weight, 34-46% by weight, 36-48% by weight, or 38-50% by weight. It can be in the range of% by weight. From the point of view of the upper limit, the amount of SIS block copolymer in the HMPSA composition is less than 70% by weight, less than 65% by weight, less than 60% by weight, less than 55% by weight, less than 50% by weight, less than 45% by weight, or It can be less than 40% by weight. From a lower limit perspective, the amount of SIS block copolymer in the HMPSA composition is at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight, or It can be at least 40% by weight.

商業的に利用可能な好適な線状のＳＩＳブロック共重合体は、例えば、Ｓｈａｎｄｏｎｇ Ｊｕｓａｇｅ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏｍｐａｎｙ，Ｌｔｄ．（中国山東省）から入手可能なＳＩＳ １２２０、Ｎｉｐｐｏｎ Ｚｅｏｎ Ｃｏｍｐａｎｙ，Ｌｔｄ．（ケンタッキー州ルイビル）から入手可能なＱｕｉｎｔａｃ ３４３３及びＱｕｉｎｔａｃ ３４２１、Ｅｘｘｏｎ Ｃｈｅｍｉｃａｌ Ｃｏ．（テキサス州ヒューストン）とＤｏｗ Ｃｈｅｍｉｃａｌ Ｃｏ．（ミシガン州ミッドランド）のパートナーシップであるＤｅｘｃｏから入手可能なＶｅｃｔｏｒ ＤＰＸ５５９、Ｖｅｃｔｏｒ ４１１１及びＶｅｃｔｏｒ ４１１３、及びＳｈｅｌｌ Ｃｈｅｍｉｃａｌ Ｃｏ．（テキサス州ヒューストン）から入手可能なＫｒａｔｏｎ ６０４ｘ、Ｋｒａｔｏｎ Ｄ―１１１７、Ｋｒａｔｏｎ Ｄ―１１０７及びＫｒａｔｏｎ Ｄ―１１１３等のＫＲＡＴＯＮＴＭゴムを含む。 Suitable linear SIS block copolymers commercially available are described, for example, in Shandong Technology Technology Company, Ltd. SIS 1220, Nippon Zeon Company, Ltd., available from Shandong Province, China. (Louisville, Kentucky), Quintac 3433 and Quintac 3421, Exxon Chemical Co., Ltd. (Houston, Texas) and Dow Chemical Co., Ltd. Vector DPX559, Vector 4111 and Vector 4113, available from Vector (Midland, Michigan), and Cell Chemical Co., Ltd. Includes Kraton TM rubbers such as Kraton 604x, Kraton D-1117, Kraton D-1107 and Kraton D-1113 available from (Houston, Texas).

一実施形態において、可塑剤、例えば、パラフィンオイル可塑剤は、高分子量のパラフィンオイルである。この高分子量の可塑剤を使用することは、従来のＨＭＰＳＡ組成物では観察されなかった多くの利点を接着剤に提供するということが明らかになった。例えば、得られた接着剤は、基材に最初に適用された後、再配置できるという改善された能力を有する。より具体的に、一部の実施形態において、５℃を超える温度で初期適用した後、最初の１２時間以内（例えば、最初の１１時間、１０時間、９時間、８時間、７時間、６時間、５時間、または４時間以内）で接着剤を用いたラベルを除去でき、例えば、ポリエチレンテレフタレート（ＰＥＴ）またはガラスボトル等の基材から実質的に完全に除去でき、且つ、前記基材に再適用できる。図１は、かかるラベル付きボトル１００の一例を示しており、ラベル１０１は、前記ボトル１００の外表面１０２に適用される。特定のＨＭＰＳＡ組成物により、かかるラベルはまた、長時間の後、ガラス容器またはＰＥＴ容器の外表面から接着剤を実質的に完全に除去することによってきれいに除去できる。本明細書において、「実質的に完全に除去」という用語は、ラベルが接着された容器の外表面ではなく、ラベルと共に保たれる接着剤の少なくとも９０％、少なくとも９１％、少なくとも９２％、少なくとも９３％、少なくとも９４％、少なくとも９５％、少なくとも９６％、少なくとも９７％、少なくとも９８％、または少なくとも９９％が除去されることを指すときに用いられる。 In one embodiment, the plasticizer, eg, paraffin oil plasticizer, is a high molecular weight paraffin oil. It has been revealed that the use of this high molecular weight plasticizer provides the adhesive with many advantages not observed with conventional HMPSA compositions. For example, the resulting adhesive has the improved ability to be rearranged after being first applied to the substrate. More specifically, in some embodiments, within the first 12 hours (eg, first 11 hours, 10 hours, 9 hours, 8 hours, 7 hours, 6 hours) after initial application at temperatures above 5 ° C. The label with the adhesive can be removed within 5, 5 or 4 hours), substantially completely from a substrate such as polyethylene terephthalate (PET) or a glass bottle, and reapplied to the substrate. Applicable. FIG. 1 shows an example of such a labeled bottle 100, the label 101 being applied to the outer surface 102 of the bottle 100. With certain HMPSA compositions, such labels can also be removed cleanly after a long period of time by removing the adhesive from the outer surface of the glass or PET container substantially completely. As used herein, the term "substantially completely removed" refers to at least 90%, at least 91%, at least 92%, at least of the adhesive that is retained with the label, rather than the outer surface of the container to which the label is attached. It is used to refer to the removal of 93%, at least 94%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99%.

高分子量パラフィンオイルのまた別の利点は、さらに優れた構造的完全性を有するラベルを作るのに接着剤が用いられ得るということにある。例えば、ＨＭＰＳＡを含むラベルは、しわの低下と膨潤性の低下を示し得る。低下した膨潤性は、所定の測定期間の間、５％未満、４％未満、３％未満、２％未満、または１％未満の大きさの変化を示し得る。膨潤性及びしわの測定期間は、３日超え、４日超え、５日超え、６日超え、７日超え、８日超え、９日超え、または１０日超えであり得る。膨潤性の低下としわの低下は、４５℃超え、５０℃超え、５５℃超え、６０℃超え、６５℃超え、または７０℃超えの温度で保管中に観察できる。膨潤性の低下としわの低下は、８０％超え、８２％超え、８４％超え、８６％超え、８８％超え、または９０％超えの相対湿度で保管中に観察できる。一部の実施形態において、ＨＭＰＳＡを含むラベルは、８５％の相対湿度において、６５℃を超える温度で４日間、または５０℃を超える温度で７日間保管する場合、大きさに変化がないか、または２％未満の各々の寸法（例えば、縦方向及び横方向）に変化がある。 Another advantage of high molecular weight paraffin oils is that adhesives can be used to make labels with even better structural integrity. For example, a label containing HMPSA may show reduced wrinkles and reduced swelling. Reduced swelling may exhibit a magnitude change of less than 5%, less than 4%, less than 3%, less than 2%, or less than 1% over a given measurement period. The measurement period for swelling and wrinkles can be more than 3 days, more than 4 days, more than 5 days, more than 6 days, more than 7 days, more than 8 days, more than 9 days, or more than 10 days. Decreased swellability and wrinkles can be observed during storage at temperatures above 45 ° C, above 50 ° C, above 55 ° C, above 60 ° C, above 65 ° C, or above 70 ° C. Decreased swelling and wrinkling can be observed during storage at relative humidity greater than 80%, greater than 82%, greater than 84%, greater than 86%, greater than 88%, or greater than 90%. In some embodiments, labels containing HMPSA do not change in size when stored at 85% relative humidity for 4 days at temperatures above 65 ° C. or for 7 days at temperatures above 50 ° C. Or there is a variation in each dimension (eg, vertical and horizontal) of less than 2%.

また、驚くことに、これらのパラフィンオイルは、ラベルの層内及び層間におけるオイルの移動が少なく、接着ラベルの元々の占用面積（ｆｏｏｔｐｒｉｎｔ）を超えた接着漏れが少ないということを見付けた。これらの改善は、物品に接着し、印刷表示を固定及び維持するにあたって、ラベルの効果を増加させるだけでなく、最終的な使用者の観点からラベルの視覚的表現を増加させる。重要な情報を表したり、消費者製品の可視性またはアピール性を高めるためにラベルを用いる場合があるので、これらの改善は、ラベルの価値を著しく向上させることができる。 Surprisingly, they also found that these paraffin oils had less oil transfer within and between layers of the label and less adhesive leakage beyond the original footprint of the adhesive label. These improvements not only increase the effectiveness of the label in adhering to the article and fixing and maintaining the printed display, but also increase the visual representation of the label from the perspective of the ultimate user. These improvements can significantly increase the value of the label, as labels may be used to represent important information or enhance the visibility or appeal of consumer products.

ＨＭＰＳＡ組成物中のパラフィンオイル可塑剤の量は、５〜３５重量％、例えば、５〜２３重量％、８〜２６重量％、１１〜２９重量％、１４〜３２重量％、または１７〜３５重量％の範囲内であり得る。ＨＭＰＳＡ組成物中のパラフィンオイル可塑剤の量は、１４〜２６重量％、例えば、１４〜２１．２重量％、１５．２〜２２．４重量％、１６．４〜２３．６重量％、１７．６〜２４．８重量％、または１８．８〜２６重量％の範囲内であり得る。上限の観点から、ＨＭＰＳＡ組成物中のパラフィンオイル可塑剤の量は、３８重量％未満、３５重量％未満、３２重量％未満、２９重量％未満、２６重量％未満、２３重量％未満、または２０重量％未満であり得る。下限の観点から、ＨＭＰＳＡ組成物中のパラフィンオイル可塑剤の量は、少なくとも２重量％、少なくとも５重量％、少なくとも８重量％、少なくとも１１重量％、少なくとも１４重量％、少なくとも１７重量％、または少なくとも２０重量％であり得る。 The amount of paraffin oil plasticizer in the HMPSA composition is 5 to 35% by weight, for example 5 to 23% by weight, 8 to 26% by weight, 11 to 29% by weight, 14 to 32% by weight, or 17 to 35% by weight. It can be in the range of%. The amount of paraffin oil plasticizer in the HMPSA composition is 14 to 26% by weight, for example 14 to 21.2% by weight, 15.2 to 22.4% by weight, 16.4 to 23.6% by weight, 17 It can be in the range of .6 to 24.8% by weight, or 18.8 to 26% by weight. From the point of view of the upper limit, the amount of paraffin oil plasticizer in the HMPSA composition is less than 38% by weight, less than 35% by weight, less than 32% by weight, less than 29% by weight, less than 26% by weight, less than 23% by weight, or 20. It can be less than% by weight. From a lower limit perspective, the amount of paraffin oil plasticizer in the HMPSA composition is at least 2% by weight, at least 5% by weight, at least 8% by weight, at least 11% by weight, at least 14% by weight, at least 17% by weight, or at least. It can be 20% by weight.

パラフィンオイル可塑剤は、４００〜１０００、例えば、４００〜７００、５００〜８００、６００〜９００、７００〜１０００、４００〜５００、５００〜６００、６００〜７００、７００〜８００、８００〜９００、または９００〜１０００の範囲の数平均分子量を有し得る。上限の観点から、可塑剤は、１０００未満、例えば、９００未満、８００未満、７００未満、６００未満、または５００未満の数平均分子量を有し得る。下限の観点から、可塑剤は、少なくとも４００、例えば、少なくとも５００、少なくとも６００、少なくとも７００、少なくとも８００、または少なくとも９００の数平均分子量を有し得る。 Paraffin oil plasticizers are 400-1000, for example 400-700, 500-800, 600-900, 700-1000, 400-500, 500-600, 600-700, 700-800, 800-900, or 900. It can have a number average molecular weight in the range of ~ 1000. From an upper limit perspective, the plasticizer may have a number average molecular weight of less than 1000, eg, less than 900, less than 800, less than 700, less than 600, or less than 500. In terms of the lower bound, the plasticizer can have a number average molecular weight of at least 400, eg, at least 500, at least 600, at least 700, at least 800, or at least 900.

また、パラフィンオイル可塑剤は、高粘度を有し得る。動粘度は、例えば、中国標準ＢＧ／Ｔ ２６５―１９８８の手順を用いて測定できる。パラフィンオイル可塑剤は、４０℃における動粘度が、４００ｍｍ２／秒〜１０００ｍｍ２／秒、例えば、４００〜７００ｍｍ２／秒、５００〜８００ｍｍ２／秒、６００〜９００ｍｍ２／秒、７００〜１０００ｍｍ２／秒、４００〜５００ｍｍ２／秒、５００〜６００ｍｍ２／秒、６００〜７００ｍｍ２／秒、７００〜８００ｍｍ２／秒、８００〜９００ｍｍ２／秒、または９００〜１０００ｍｍ２／秒の範囲内であり得る。上限の観点から、可塑剤は、１０００ｍｍ２／秒未満、例えば、９００ｍｍ２／秒未満、８００ｍｍ２／秒未満、７００ｍｍ２／秒未満、６００ｍｍ２／秒未満、または５００ｍｍ２／秒未満の動粘度を有し得る。下限の観点から、可塑剤は、４００ｍｍ２／秒超え、例えば、５００ｍｍ２／秒超え、６００ｍｍ２／秒超え、７００ｍｍ２／秒超え、８００ｍｍ２／秒超え、または９００ｍｍ２／秒超えの動粘度を有し得る。 Also, paraffin oil plasticizers can have high viscosities. The kinematic viscosity can be measured using, for example, the procedure of Chinese standard BG / T 265-1988. Paraffin oil plasticizer, kinematic viscosity at 40 ° C., 400 mm 2 / sec ~1000mm 2 / sec, for example, 400~700mm 2 / sec, 500~800mm 2 / sec, 600~900mm 2 / sec, 700～1000Mm 2 Within the range of / sec, 400-500 mm 2 / sec, 500-600 mm 2 / sec, 600-700 mm 2 / sec, 700-800 mm 2 / sec, 800-900 mm 2 / sec, or 900-1000 mm 2 / sec. obtain. From the perspective of the upper limit, the plasticizer has a kinematic viscosity of less than 1000 mm 2 / sec, for example 900 mm less than 2 / sec, 800 mm less than 2 / sec, 700 mm less than 2 / sec, 600 mm less than 2 / sec, or 500 mm less than 2 / sec. Can have. In terms of the lower limit, plasticizer, 400 mm 2 / Byokoe, for example, 500 mm 2 / Byokoe, 600 mm 2 / Byokoe, 700 mm 2 / Byokoe, 800 mm 2 / Byokoe or kinematic viscosity 900 mm 2 / sec than, Can have.

低分子量及び低粘度を有する粘着付与剤の使用は、可塑剤の高分子量及び高粘度を有利に（部分的に）相殺するということを見付けた。本発明者らは、ＨＭＰＳＡの全体の粘度が高過ぎると、接着剤の加工性が損われ得るということを見付けた。特に、より高い粘度を有する接着剤は、接着剤ラベルの製造に関する標準的な配合工程及びコーティング工程における使用において、より困難であり得る。通常、接着剤の粘度が低くなるにつれて接着剤の加工性が向上し、得られる接着剤のコーティング層は、より均一、且つ一定である。 It has been found that the use of tackifiers with low molecular weight and low viscosity advantageously (partially) offsets the high molecular weight and high viscosity of the plasticizer. The present inventors have found that if the overall viscosity of HMPSA is too high, the processability of the adhesive can be impaired. In particular, adhesives with higher viscosities can be more difficult to use in standard compounding and coating steps for the manufacture of adhesive labels. Generally, as the viscosity of the adhesive decreases, the processability of the adhesive improves, and the coating layer of the obtained adhesive is more uniform and constant.

多数の一般的な線状脂肪族炭化水素粘着付与剤は、１０００〜４０００の範囲内の重量平均分子量を有する。本発明者らは、ＨＭＰＳＡにおいて、脂環式炭化水素粘着付与剤樹脂を用いることにより、高分子量の線状脂肪族炭化水素が有利に回避できるということを見付けた。脂環式炭化水素粘着付与剤は、３００〜１０００または３００〜８００、例えば、３００〜６００、４００〜７００、５００〜８００、３００〜４００、４００〜５００、５００〜６００、６００〜７００、または７００〜８００の範囲内の低い重量平均分子量を有し得る。上限の観点から、粘着付与剤は、８００未満、例えば、７００未満、６００未満、５００未満、または４００未満の重量平均分子量を有し得る。下限の観点から、粘着付与剤は、少なくとも３００、例えば、少なくとも４００、少なくとも５００、少なくとも６００、または少なくとも７００の重量平均分子量を有し得る。さらなる利点として、脂環式炭化水素の化学構造の比較的高い極性及び立体障害の効果は、関連ラベルの層内及び層間におけるオイルの移動を減少させる作用をする。また、樹脂の水素化は、減少した色相、臭気、及びチャー（ｃｈａｒ）粒子を有する接着剤層及びラベルを生成する。 Many common linear aliphatic hydrocarbon tackifiers have a weight average molecular weight in the range of 1000-4000. The present inventors have found that high molecular weight linear aliphatic hydrocarbons can be advantageously avoided by using an alicyclic hydrocarbon tackifier resin in HMPSA. The alicyclic hydrocarbon tackifier is 300-1000 or 300-800, for example 300-600, 400-700, 500-800, 300-400, 400-500, 500-600, 600-700, or 700. It may have a low weight average molecular weight in the range of ~ 800. In view of the upper limit, the tackifier can have a weight average molecular weight of less than 800, eg, less than 700, less than 600, less than 500, or less than 400. From the viewpoint of the lower limit, the tackifier may have a weight average molecular weight of at least 300, such as at least 400, at least 500, at least 600, or at least 700. As a further advantage, the relatively high polarity and steric hindrance effects of the alicyclic hydrocarbon chemical structure act to reduce oil transfer within and between layers of the relevant label. Hydrogenation of the resin also produces an adhesive layer and label with reduced hue, odor, and char particles.

ＨＭＰＳＡ組成物中の脂環式炭化水素粘着付与剤の量は、１５〜６５重量％、例えば、１５〜４５重量％、２０〜５０重量％、２５〜５５重量％、３０〜６０重量％、または３５〜６５重量％の範囲内であり得る。ＨＭＰＳＡ組成物中の脂環式炭化水素粘着付与剤の量は、３０〜５０重量％、例えば、３０〜４２重量％、３２〜４４重量％、３４〜４６重量％、３６〜４８重量％、または３８〜５０重量％の範囲内であり得る。上限の観点から、ＨＭＰＳＡ組成物中の脂環式炭化水素粘着付与剤の量は、７０重量％未満、６５重量％未満、６０重量％未満、５５重量％未満、５０重量％未満、４５重量％未満、または４０重量％未満であり得る。下限の観点から、ＨＭＰＳＡ組成物中の脂環式炭化水素粘着付与剤の量は、少なくとも１０重量％、少なくとも１５重量％、少なくとも２０重量％、少なくとも２５重量％、少なくとも３０重量％、少なくとも３５重量％、または少なくとも４０重量％であり得る。 The amount of the alicyclic hydrocarbon tackifier in the HMPSA composition is 15-65% by weight, for example 15-45% by weight, 20-50% by weight, 25-55% by weight, 30-60% by weight, or It can be in the range of 35-65% by weight. The amount of the alicyclic hydrocarbon tackifier in the HMPSA composition is 30-50% by weight, for example 30-42% by weight, 32-44% by weight, 34-46% by weight, 36-48% by weight, or It can be in the range of 38-50% by weight. From the viewpoint of the upper limit, the amount of the alicyclic hydrocarbon tackifier in the HMPSA composition is less than 70% by weight, less than 65% by weight, less than 60% by weight, less than 55% by weight, less than 50% by weight, 45% by weight. It can be less than, or less than 40% by weight. From the viewpoint of the lower limit, the amount of the alicyclic hydrocarbon tackifier in the HMPSA composition is at least 10% by weight, at least 15% by weight, at least 20% by weight, at least 25% by weight, at least 30% by weight, at least 35% by weight. %, Or at least 40% by weight.

ＨＭＰＳＡは、ポリエチレンワックスを選択的に含んでもよい。ＨＭＰＳＡの選択的なポリエチレンワックスは、接着剤の疎水性を増加させる役割をすることができる。かかる増加した疎水性は、接着剤の水白化に対する耐性、及び接着剤がきれいに除去されたり再配置できる能力を向上させるのに役立ち得る。ポリエチレンワックスはまた、ＨＭＰＳＡの全体の粘度をさらに低下させ、接着剤の透明性に及ぶ影響を最小化するように選択できる。 HMPSA may selectively contain polyethylene wax. HMPSA's selective polyethylene wax can serve to increase the hydrophobicity of the adhesive. Such increased hydrophobicity can help improve the resistance of the adhesive to water whitening and the ability of the adhesive to be removed or rearranged cleanly. Polyethylene wax can also be selected to further reduce the overall viscosity of the HMPSA and minimize its effect on the transparency of the adhesive.

ポリエチレンワックスは、特定の硬度値を有するように選択できる。硬度値は、例えば、米国材料試験協会（ＡＳＴＭ）の標準手順であるＡＳＴＭ Ｄ５のように、貫通試験により測定できる。この手順における硬度は、標準針が被試験材料のサンプルを貫通するミリメートルの１／１０の距離として規定される。ポリエチレンワックスは、３〜１０、例えば、３〜６、４〜７、５〜８、６〜９、７〜１０、３〜４、４〜５、５〜６、６〜７、７〜８、８〜９、または９〜１０の範囲内の硬度値を有し得る。上限の観点から、ポリエチレンワックスは、１０未満、例えば、９未満、８未満、７未満、６未満、５未満、または４未満の硬度値を有し得る。下限の観点から、ポリエチレンワックスは、少なくとも３、例えば、少なくとも４、少なくとも５、少なくとも６、少なくとも７、少なくとも８、または少なくとも９の硬度値を有し得る。 Polyethylene wax can be selected to have a particular hardness value. The hardness value can be measured by a penetration test, for example, like ASTM D5, which is a standard procedure of the American Society for Testing and Materials (ASTM). Hardness in this procedure is defined as the distance of 1/10 of a millimeter through which a standard needle penetrates a sample of material under test. Polyethylene wax is 3 to 10, for example, 3 to 6, 4 to 7, 5 to 8, 6 to 9, 7 to 10, 3 to 4, 4 to 5, 5 to 6, 6 to 7, 7 to 8, It can have a hardness value in the range of 8-9, or 9-10. In view of the upper limit, the polyethylene wax can have a hardness value of less than 10, for example, less than 9, less than 8, less than 7, less than 6, less than 5, or less than 4. In terms of the lower bound, the polyethylene wax may have a hardness value of at least 3, for example at least 4, at least 5, at least 6, at least 7, at least 8, or at least 9.

ポリエチレンワックスは、ブルックフィールド粘度計によって測定された動的粘度等の比較的低い粘度を有し得る。ポリエチレンワックスは、１４０℃における動的粘度が、１５０センチポアズ（ｃｐｓ）〜５００ｃｐｓ、例えば、１５０〜３００ｃｐｓ、２５０〜４００ｃｐｓ、３５０〜５００ｃｐｓ、１５０〜２００ｃｐｓ、２００〜２５０ｃｐｓ、２５０〜３００ｃｐｓ、３００〜３５０ｃｐｓ、または３５０〜４００ｃｐｓの範囲内であり得る。上限の観点から、ポリエチレンワックスは、１４０℃における動的粘度が、５００ｃｐｓ未満、４５０ｃｐｓ未満、４００ｃｐｓ未満、３５０ｃｐｓ未満、３００ｃｐｓ未満、２５０ｃｐｓ未満、または２００ｃｐｓ未満であり得る。下限の観点から、ポリエチレンワックスは、１４０℃における動的粘度が、少なくとも１５０ｃｐｓ、例えば、少なくとも２００ｃｐｓ、少なくとも２５０ｃｐｓ、少なくとも３００ｃｐｓ、少なくとも３５０ｃｐｓ、少なくとも４００ｃｐｓ、または少なくとも４５０ｃｐｓであり得る。 Polyethylene wax may have a relatively low viscosity, such as the dynamic viscosity measured by a Brookfield viscometer. Polyethylene wax has a dynamic viscosity at 140 ° C. of 150 centipores (cps) to 500 cps, for example, 150 to 300 cps, 250 to 400 cps, 350 to 500 cps, 150 to 200 cps, 200 to 250 cps, 250 to 300 cps, 300 to 350 cps. Alternatively, it can be in the range of 350 to 400 cps. From the viewpoint of the upper limit, the polyethylene wax may have a dynamic viscosity at 140 ° C. of less than 500 cps, less than 450 cps, less than 400 cps, less than 350 cps, less than 300 cps, less than 250 cps, or less than 200 cps. From the viewpoint of the lower limit, the polyethylene wax can have a dynamic viscosity at 140 ° C. of at least 150 cps, for example at least 200 cps, at least 250 cps, at least 300 cps, at least 350 cps, at least 400 cps, or at least 450 cps.

また、ポリエチレンワックスは、標準手順のＡＳＴＭ Ｄ５９４９によって測定された特定の流動点を有するように選択できる。流動点は、液体が半固体となってその流動特性を失う温度として定義される。ポリエチレンワックスは、９０℃超え、９１℃超え、９２℃超え、９３℃超え、９４℃超え、９５℃超え、９６℃超え、９７℃超え、９８℃超え、９９℃超え、１００℃超え、１０１℃超え、１０２℃超え、１０３℃超え、１０４℃超え、１０５℃超え、１０６℃超え、１０７℃超え、１０８℃超え、１０９℃超え、または１１０℃超えの流動点を有し得る。一部の実施形態において、ポリエチレンワックスは、１００℃超えの流動点を有する。 Polyethylene wax can also be selected to have a particular pour point as measured by ASTM D5949 in standard procedures. The pour point is defined as the temperature at which a liquid becomes semi-solid and loses its pour point. Polyethylene wax exceeds 90 ° C, 91 ° C, 92 ° C, 93 ° C, 94 ° C, 95 ° C, 96 ° C, 97 ° C, 98 ° C, 99 ° C, 100 ° C, 101 ° C. It can have pour points above, over 102 ° C, over 103 ° C, over 104 ° C, over 105 ° C, over 106 ° C, over 107 ° C, over 108 ° C, over 109 ° C, or over 110 ° C. In some embodiments, the polyethylene wax has a pour point above 100 ° C.

ＨＭＰＳＡ組成物中のポリエチレンワックスの量は、０〜５重量％、例えば、０〜３重量％、０．５〜３．５重量％、１〜４重量％、１．５〜４．５重量％、または２〜５重量％の範囲内であり得る。ＨＭＰＳＡ組成物中のポリエチレンワックスの量は、０〜２重量％、例えば、０〜１．２重量％、０．２〜１．４重量％、０．４〜１．６重量％、０．６〜１．８重量％、または０．８〜２重量％の範囲内であり得る。上限の観点から、ＨＭＰＳＡ組成物中のポリエチレンワックスの量は、５重量％未満、４重量％未満、３重量％未満、２重量％未満、１．５重量％未満、１重量％未満、または０．５重量％未満であり得る。下限の観点から、ＨＭＰＳＡ組成物中のポリエチレンワックスの量は、０重量％、または、少なくとも０．５重量％、少なくとも１重量％、少なくとも１．５重量％、少なくとも２重量％、若しくは少なくとも２．５重量％であり得る。 The amount of polyethylene wax in the HMPSA composition is 0-5% by weight, for example 0-3% by weight, 0.5-3.5% by weight, 1-4% by weight, 1.5-4.5% by weight. , Or in the range of 2-5% by weight. The amount of polyethylene wax in the HMPSA composition is 0 to 2% by weight, for example 0 to 1.2% by weight, 0.2 to 1.4% by weight, 0.4 to 1.6% by weight, 0.6. It can be in the range of ~ 1.8% by weight, or 0.8-2% by weight. From the perspective of the upper limit, the amount of polyethylene wax in the HMPSA composition is less than 5% by weight, less than 4% by weight, less than 3% by weight, less than 2% by weight, less than 1.5% by weight, less than 1% by weight, or 0. It can be less than 5.5% by weight. From the viewpoint of the lower limit, the amount of polyethylene wax in the HMPSA composition is 0% by weight, or at least 0.5% by weight, at least 1% by weight, at least 1.5% by weight, at least 2% by weight, or at least 2. It can be 5% by weight.

ＨＭＰＳＡの全体の粘度は、ブルックフィールド粘度計によって測定された１４０℃における接着剤の動的粘度が、１０，０００ｃｐｓ〜２０，０００ｃｐｓ、例えば、１０，０００〜１４，０００ｃｐｓ、１２，０００〜１６，０００ｃｐｓ、１４，０００〜１８，０００ｃｐｓ、１６，０００〜２０，０００ｃｐｓ、１０，０００〜１２，０００ｃｐｓ、１２，０００〜１４，０００ｃｐｓ、１４，０００〜１６，０００ｃｐｓ、１６，０００〜１８，０００ｃｐｓ、または１８，０００〜２０，０００ｃｐｓの範囲内とすることができる。上限の観点から、ＨＭＰＳＡは、１４０℃における動的粘度が、２０，０００ｃｐｓ未満、例えば、１８，０００ｃｐｓ未満、１６，０００ｃｐｓ未満、１４，０００ｃｐｓ未満、または１２，０００ｃｐｓ未満であり得る。下限の観点から、ＨＭＰＳＡは、１４０℃における動的粘度が、少なくとも１０，０００ｃｐｓ、例えば、少なくとも１２，０００ｃｐｓ、少なくとも１４，０００ｃｐｓ、少なくとも１６，０００ｃｐｓ、または少なくとも１８，０００ｃｐｓであり得る。 The overall viscosity of HMPSA is that the dynamic viscosity of the adhesive at 140 ° C. as measured by a Brookfield viscometer is 10,000 cps to 20,000 cps, eg 10,000 to 14,000 cps, 12,000 to 16, 000 cps, 14,000 to 18,000 cps, 16,000 to 20,000 cps, 10,000 to 12,000 cps, 12,000 to 14,000 cps, 14,000 to 16,000 cps, 16,000 to 18,000 cps, Alternatively, it can be in the range of 18,000 to 20,000 cps. In view of the upper limit, HMPSA can have a dynamic viscosity at 140 ° C. of less than 20,000 cps, for example less than 18,000 cps, less than 16,000 cps, less than 14,000 cps, or less than 12,000 cps. In view of the lower limit, the HMPSA can have a dynamic viscosity at 140 ° C. of at least 10,000 cps, for example at least 12,000 cps, at least 14,000 cps, at least 16,000 cps, or at least 18,000 cps.

ＨＭＰＳＡは、若干白いかまたは無色の外観を有するように前記のように製剤化できる。また、ＨＭＰＳＡは、高鮮明度及び高透明度を有するように製剤化できる。これは、クリアか透明な接着剤またはラベルが求められる用途において、接着剤または関連ラベルに利点を提供できる。例えば、クリアなラベルは、これらの付着表面の色相またはテクスチャーがラベルを通して見える状態が保たれるよう、様々な異なる付着表面や材料と共に用いることができる。さらに、クリアか透明な接着剤またはラベルは、クリアか透明な容器と共に用いることができる。かかる「クリア・オン・クリア（ｃｌｅａｒ ｏｎ ｃｌｅａｒ）」のラベル付けは、例えば、ガラスボトルまたはペットボトルを使用する飲料産業において一般的である。クリア・オン・クリアラベル付けにより、ラベル上の任意の印刷物は、接着剤の透明性及び無色性の部分により、まるで容器そのものに直接印刷されているかのように見える傾向がある。所望の無色性を有する接着剤を製造するために、粘着付与剤樹脂、可塑剤オイル、ワックス、充填剤、及びその他の成分は、接着剤組成物において、着色がほとんどなく、及び／または良好な溶解性を有するようにそれぞれ選択される。 HMPSA can be formulated as described above to have a slightly white or colorless appearance. In addition, HMPSA can be formulated so as to have high clarity and high transparency. This can provide advantages for adhesives or related labels in applications where clear or transparent adhesives or labels are required. For example, clear labels can be used with a variety of different adherent surfaces and materials so that the hue or texture of these adherent surfaces remains visible through the label. In addition, clear or clear adhesives or labels can be used with clear or clear containers. Such "clear on clear" labeling is common, for example, in the beverage industry where glass bottles or PET bottles are used. With clear-on-clear labeling, any printed matter on the label tends to appear as if it were printed directly on the container itself, due to the transparent and colorless parts of the adhesive. To produce an adhesive with the desired colorlessness, tackifier resins, plasticizer oils, waxes, fillers, and other ingredients have little or no coloration in the adhesive composition and / or are good. Each is selected to have solubility.

ＨＭＰＳＡの鮮明度及び透明度は、標準プロトコルＡＳＴＭ Ｄ１００３によるヘイズ値、または、標準プロトコルＡＳＴＭ Ｄ２８０５による不透明度コントラスト比として測定できる。ヘイズ値は、試験片を通じて見られる物体のコントラスト低下の原因となる試験片によって散乱した透過光の百分率として定義される。ＨＭＰＳＡのヘイズ値は、例えば、１０未満、９未満、８未満、７未満、６未満、５未満、４未満、３未満、２未満、または１未満であり得る。一部の実施形態において、ＨＭＰＳＡは、５未満のヘイズ値を有する。不透明度コントラスト比は、黒色基材上のフィルムにおける反射率と、白色基材上の同一のフィルムにおける反射率との比として定義される。ＨＭＰＳＡの不透明度コントラスト値は、例えば、４０未満、３５未満、３０未満、２５未満、２０未満、１５未満、１０未満、または５未満であり得る。一部の実施形態において、ＨＭＰＳＡは、２０未満の不透明度コントラスト比を有する。 The sharpness and transparency of HMPSA can be measured as a haze value according to the standard protocol ASTM D1003 or an opacity contrast ratio according to the standard protocol ASTM D2805. The haze value is defined as the percentage of transmitted light scattered by the test piece that causes the contrast loss of the object seen through the test piece. The haze value of HMPSA can be, for example, less than 10, less than 9, less than 8, less than 7, less than 6, less than 5, less than 4, less than 3, less than 2, or less than 1. In some embodiments, HMPSA has a haze value of less than 5. The opacity contrast ratio is defined as the ratio of the reflectance of a film on a black substrate to the reflectance of the same film on a white substrate. The opacity contrast value of HMPSA can be, for example, less than 40, less than 35, less than 30, less than 25, less than 20, less than 15, less than 10, or less than 5. In some embodiments, HMPSA has an opacity contrast ratio of less than 20.

ＨＭＰＳＡ製剤のまた別の利点は、温度や湿度の変化に大きく影響されない白色度、鮮明度、及び透明度である。例えば、接着剤を６５℃で１時間加熱した場合、ヘイズ値及び不透明度コントラスト比は、それぞれ独立に、３０％未満、２８％未満、２６％未満、２４％未満、２２％未満、２０％未満、１８％未満、１６％未満、１４％未満、１２％未満、１０％未満、８％未満、６％未満、４％未満、または２％未満の変化があり得る。前記加熱は、接着剤を６５℃に加熱された水と接触させることを含み得る。前記加熱は、接着剤を６５℃の水に浸すことを含み得る。 Another advantage of HMPSA formulations is whiteness, sharpness, and clarity that are not significantly affected by changes in temperature or humidity. For example, when the adhesive is heated at 65 ° C. for 1 hour, the haze value and opacity contrast ratio are independently less than 30%, less than 28%, less than 26%, less than 24%, less than 22%, less than 20%, respectively. , Less than 18%, less than 16%, less than 14%, less than 12%, less than 10%, less than 8%, less than 6%, less than 4%, or less than 2%. The heating may include contacting the adhesive with water heated to 65 ° C. The heating may include immersing the adhesive in water at 65 ° C.

食品接触の要件を満たすよう、ＨＭＰＳＡ組成物の成分を選択でき、一般に食品安全として分類される。例えば、水素化粘着付与剤及び食品レベルのパラフィンオイルを用いる場合、ＨＭＰＳＡを食品安全接着剤にすることが可能となる。 Ingredients of the HMPSA composition can be selected to meet food contact requirements and are generally classified as food safety. For example, when a hydrogenated tackifier and a food-level paraffin oil are used, HMPSA can be used as a food safety adhesive.

また、本発明は、本発明のホットメルト感圧接着剤を含むラベルに関する。ラベルは、印刷表示を収容する表面材層と、上述のような組成物を有するホットメルト感圧接着剤層と、を含む。ラベルはまた、１つ以上の表面材層と、１つ以上の選択的な印刷層と、１つ以上の接着剤層と、選択的なライナー層と、を含み得る。本発明は、印刷のないラベルにも用いられるが、多くの実施形態において、ラベルは、１つ以上の印刷領域を含む。 The present invention also relates to a label containing the hot melt pressure sensitive adhesive of the present invention. The label includes a surface material layer accommodating the printed display and a hot melt pressure sensitive adhesive layer having the composition as described above. The label may also include one or more surface material layers, one or more selective printing layers, one or more adhesive layers, and a selective liner layer. Although the present invention is also used for unprinted labels, in many embodiments the label comprises one or more printed areas.

図２は、一実施形態による多層ラベルを示している。表面材層２０１と、ＨＭＰＳＡ層２０２と、ライナー層２０３とを含むラベル２００が示されている。ＨＭＰＳＡ層は、ライナー層にさらに近い表面材層の表面２０４上に配置される。表面材層の反対側の表面２０５は、印刷表示を収容するように構成できる。かかる選択的な表示は、前記表面２０５上に直接印刷でき、任意の層２０１，２０２，または２０３のいずれかに埋め込まれるか、或いはラベル２００の任意の他の表面上に印刷できる。図２に示されている層は、図示しているように互いに直接隣接して位置するか、またはそれらの間に１つ以上のさらなる層を有することができる。さらなる層は、例えば、１つ以上のコーティング層、支持層、印刷層、反射層、積層層、またはその他の層を含み得る。さらに、示している任意の１つ以上の層は、それぞれ相違する組成、構成、及び機能を有する２つ以上の下位層を含み得る。 FIG. 2 shows a multilayer label according to one embodiment. A label 200 including a surface material layer 201, an HMPSA layer 202, and a liner layer 203 is shown. The HMPSA layer is arranged on the surface 204 of the surface material layer closer to the liner layer. The surface 205 on the opposite side of the surface material layer can be configured to accommodate the printed display. Such selective display can be printed directly on the surface 205, embedded in any of the layers 201, 202, or 203, or printed on any other surface of the label 200. The layers shown in FIG. 2 may be located directly adjacent to each other as shown, or may have one or more additional layers between them. Further layers may include, for example, one or more coating layers, support layers, printing layers, reflective layers, laminated layers, or other layers. Further, any one or more layers shown may include two or more lower layers, each having a different composition, composition and function.

表面材は、例えば、紙表面材、板紙表面材、プラスチック表面材、紙層及びプラスチック層をともに含む多層積層の表面材、または産業で一般に用いられる任意の他の材料を含み得る。多層積層の表面材は、プラスチック層を覆う紙層を含み得る。多層積層表面材のプラスチック層は、紙層上に押し出され得るか、或いはコーティングされ得る。紙層は、例えば、高光沢紙、半光沢紙、石版紙、または電子データ処理（ＥＤＰ）用紙を含んでもよく、例えば、多色印刷、タイプライター印刷、或いはインクジェット印刷に用いられるように構成されてもよい。プラスチック層は、例えば、ＰＥＴ等のポリエステルと、ポリプロピレン（ＰＰ）、エチレンプロピレン共重合体、ポリエチレン（ＰＥ）等のポリオレフィンと、その他の材料を含み得る。その他の重合性フィルム材料は、ポリエーテルウレタン及びポリエステルウレタン等のウレタン系重合体、ポリエーテルポリアミド共重合体を含むアミド系重合体、ポリアクリレート、エチレン／ビニルアセテート重合体を含むアクリル系重合体、ポリエーテルポリエステルを含むポリエステル系重合体、塩化ビニル、塩化ビニリデン、ポリスチレン、ポリアクリロニトリル、ポリカーボネート、ポリイミド等を含み得る。表面材は、柔軟な表面材を含み得る。表面材は、透明な重合性フィルムを含む。所定の適用において、「収縮」フィルムまたは配向フィルムを表面材層として用いることが有用であり得る。本発明は、例えば、表面材層としてＰＥＴ等の二軸配向フィルムを含む。 The surface material may include, for example, a paper surface material, a paperboard surface material, a plastic surface material, a multi-layered surface material containing both a paper layer and a plastic layer, or any other material commonly used in the industry. The multi-layered surface material may include a paper layer covering the plastic layer. The plastic layer of the multi-layer laminated surface material can be extruded or coated onto the paper layer. The paper layer may include, for example, high-gloss paper, semi-glossy paper, lithograph paper, or electronic data processing (EDP) paper, and is configured to be used, for example, for multicolor printing, typewriter printing, or inkjet printing. You may. The plastic layer may include, for example, polyester such as PET, polyolefin such as polypropylene (PP), ethylene propylene copolymer, polyethylene (PE), and other materials. Other polymerizable film materials include urethane-based polymers such as polyether urethane and polyester urethane, amide-based polymers including polyether polyamide copolymers, polyacrylates, and acrylic polymers containing ethylene / vinyl acetate polymers. It may contain a polyester polymer containing a polyether polyester, vinyl chloride, vinylidene chloride, polystyrene, polyacrylonitrile, polycarbonate, polyimide and the like. The surface material may include a flexible surface material. The surface material contains a transparent polymerizable film. In certain applications, it may be useful to use a "shrink" or oriented film as the surface material layer. The present invention includes, for example, a biaxially oriented film such as PET as a surface material layer.

一部の実施形態において、ラベルは、表面材層上に配置された印刷物をさらに含む。前記印刷物は、インク、染料、顔料または同様の材料の層若しくは領域を含み得る。理解されるように、「染料」及び同様の用語は、分子的に分散したり溶解した形態で存在する可視光吸収化合物を意味する。「顔料」及び同様の用語は、非分子的に分散した形態或いは粒子状の形態で存在する、可視光吸収材料または可視光吸収化合物を意味する。「インク」及び同様の用語は、染料及び／または顔料を含有するコーティング可能な或いは印刷可能な製剤を意味する。本発明は、主に、視覚的に認知可能な印刷物を含むラベルに向けられたものであるが、ラベルは、ＵＶ光または他の条件下で独占的に示されたり主に示される印刷物を含み得るということが考慮される。 In some embodiments, the label further comprises a printed matter placed on the surface material layer. The printed matter may include layers or regions of inks, dyes, pigments or similar materials. As will be understood, "dye" and similar terms mean visible light absorbing compounds that are present in a molecularly dispersed or dissolved form. The term "pigment" and similar terms mean a visible light absorbing material or a visible light absorbing compound that exists in a non-molecularly dispersed or particulate form. The term "ink" and similar terms mean a coatable or printable formulation containing dyes and / or pigments. The present invention is primarily directed to labels that include visually recognizable printed matter, which includes printed matter that is shown or predominantly shown exclusively under UV light or other conditions. To get is considered.

ＨＭＰＳＡ層は、表面材に直接隣接して適用され、表面材と接触している。ＨＭＰＳＡ層と表面材との間に介在層が存在し得る。ラベルは、２つ以上のＨＭＰＳＡ及び／または表面材層を含み得る。ラベルのＨＭＰＳＡ層は、例えば、５ｇ／ｍ２（ｇｓｍ）〜３０ｇｓｍのコーティング重量で表面材上にコーティングされ得る。接着剤層のコーティング重量は、６ｇｓｍ〜２０ｇｓｍ、８ｇｓｍ〜２０ｇｓｍ、２２ｇｓｍ〜３０ｇｓｍ、１６ｇｓｍ〜４０ｇｓｍであり得る。一部の実施形態において、接着剤層のコーティング重量は、５ｇｓｍ〜４０ｇｓｍの範囲内である。上限の観点から、接着剤層のコーティング重量は、４０ｇｓｍ未満、例えば、３５ｇｓｍ未満、３０ｇｓｍ未満、２５ｇｓｍ未満、２０ｇｓｍ未満、１５ｇｓｍ未満、または１０ｇｓｍ未満であり得る。下限の観点から、接着剤層のコーティング重量は、少なくとも５ｇｓｍ、例えば、少なくとも１０ｇｓｍ、少なくとも１５ｇｓｍ、少なくとも２０ｇｓｍ、少なくとも２５ｇｓｍ、少なくとも３０ｇｓｍ、または少なくとも３５ｇｓｍであり得る。 The HMPSA layer is applied directly adjacent to the surface material and is in contact with the surface material. An intervening layer may be present between the HMPSA layer and the surface material. The label may include more than one HMPSA and / or surface material layer. The HMPSA layer of the label can be coated on the surface material, for example, with a coating weight of 5 g / m 2 (gsm) to 30 gsm. The coating weight of the adhesive layer can be 6 gsm to 20 gsm, 8 gsm to 20 gsm, 22 gsm to 30 gsm, 16 gsm to 40 gsm. In some embodiments, the coating weight of the adhesive layer is in the range of 5 gsm to 40 gsm. From the viewpoint of the upper limit, the coating weight of the adhesive layer can be less than 40 gsm, for example less than 35 gsm, less than 30 gsm, less than 25 gsm, less than 20 gsm, less than 15 gsm, or less than 10 gsm. From the viewpoint of the lower limit, the coating weight of the adhesive layer can be at least 5 gsm, for example at least 10 gsm, at least 15 gsm, at least 20 gsm, at least 25 gsm, at least 30 gsm, or at least 35 gsm.

本発明は、本明細書に開示している任意のラベル構成において、１つ以上のクリアなまたは透明な層の導入を含み得る。また、本発明は、本明細書に開示している任意のラベル構成において、１つ以上の金属層または金属箔の導入を含み得る。さらに、ラベル構成は、１つ以上の透明層と１つ以上の金属層との組み合わせを含み得るということが考慮される。一部の実施形態において、ラベルは、透明な二軸配向ポリプロピレン（ＢＯＰＰ）フィルム、透明なＨＭＰＳＡ層、及び透明なＰＥＴライナーを含む積層組成を有するクリア・オン・クリアラベルである。 The present invention may include the introduction of one or more clear or transparent layers in any label configuration disclosed herein. The invention may also include the introduction of one or more metal layers or metal foils in any of the label configurations disclosed herein. Further, it is considered that the label configuration may include a combination of one or more transparent layers and one or more metal layers. In some embodiments, the label is a clear-on-clear label having a laminated composition that includes a clear biaxially oriented polypropylene (BOPP) film, a clear HMPSA layer, and a clear PET liner.

一部の実施形態において、ラベルは、ＨＭＰＳＡ層上に配置されたライナーをさらに含む。離型可能なライナーは、表面材の底表面と離型可能なライナーとの間に接着剤層が直接的または間接的に配置されるか挟まれるように接着剤層に隣接して位置し得る。離型可能なライナーは、ラベルが物体に付着する準備がされるまで離型ライナーが定位置に維持されるよう、保護カバーとして機能できる。ライナーまたは離型ライナーがラベルに含まれる場合、ライナーに多様な材料と構成が用いられ得る。多くの実施形態において、ライナーは、紙または紙ベースの材料である。他の多くの実施形態において、ライナーは、１つ以上の重合性材料の重合性フィルムである。通常、ライナーの少なくとも一方の面は、シリコーンまたはシリコーン系材料等の離型材料でコーティングされる。理解されるように、ライナーの離型コーティング面は、接着剤層の他の露出面と接触して配置される。ラベルを対象の表面に適用する前に、ライナーを除去してラベルの接着剤面を露出させる。ライナーは、単一シートの形態であり得る。代案として、ライナーは、多数のセクションまたはパネルの形態であり得る。 In some embodiments, the label further comprises a liner placed on the HMPSA layer. The releasable liner may be located adjacent to the adhesive layer such that the adhesive layer is placed or sandwiched directly or indirectly between the bottom surface of the surface material and the releasable liner. .. The releasable liner can act as a protective cover to keep the releasable liner in place until the label is ready to adhere to the object. If a liner or release liner is included in the label, a variety of materials and configurations may be used for the liner. In many embodiments, the liner is a paper or paper-based material. In many other embodiments, the liner is a polymerizable film of one or more polymerizable materials. Usually, at least one surface of the liner is coated with a release material such as silicone or silicone-based material. As will be appreciated, the release coated surface of the liner is placed in contact with the other exposed surfaces of the adhesive layer. Before applying the label to the surface of interest, the liner is removed to expose the adhesive side of the label. The liner can be in the form of a single sheet. Alternatively, the liner can be in the form of multiple sections or panels.

所定の所望する特性を得るために、他の添加剤がＨＭＰＳＡ、表面材、またはライナー層のうち１つ以上に添加され得る。これらの添加剤は、例えば、１つ以上のワックス、界面活性剤、タルク、粉末状シリケート、充填剤、消泡剤、着色剤、酸化防止剤、ＵＶ安定剤、発光剤、架橋剤、緩衝剤、ブロッキング防止剤、湿潤剤、艶消し剤、帯電防止剤、酸スカベンジャー、難燃剤、加工助剤、押出助剤等を含み得る。 Other additives may be added to one or more of the HMPSA, surface material, or liner layers to obtain the desired desired properties. These additives include, for example, one or more waxes, surfactants, talc, powdered silicates, fillers, defoamers, colorants, antioxidants, UV stabilizers, luminescent agents, crosslinkers, buffers. , Antiblocking agents, wetting agents, matting agents, antistatic agents, acid scavengers, flame retardants, processing aids, extrusion aids and the like.

また、本発明は、本発明のホットメルト感圧接着剤を含むラベル付き容器に関する。ラベル付き容器は、外表面を規定する容器と、容器の外表面に接着される上述のラベルと、を含む。一部の実施形態において、前記容器はボトルである。ＨＭＰＳＡが接着される外表面は、多様な基材を含み得る。外表面は、ガラス、プラスチック、木材、金属、これらの組み合わせ、及びその他の材料を含み得る。一部の実施形態において、容器の外表面は、ガラスを含む。 The present invention also relates to a labeled container containing the hot melt pressure sensitive adhesive of the present invention. The labeled container includes a container that defines the outer surface and the above-mentioned label that is adhered to the outer surface of the container. In some embodiments, the container is a bottle. The outer surface to which the HMPSA is adhered may contain a variety of substrates. The outer surface may include glass, plastic, wood, metal, combinations thereof, and other materials. In some embodiments, the outer surface of the container comprises glass.

一部の実施形態において、容器の外表面は、プラスチックを含む。前記外表面は、任意の好適な重合体または重合体の混合物を含むか、任意の好適な重合体または重合体の混合物から形成され得る。重合体または重合体の混合物は、例えば、ＰＥＴ、リサイクルポリエチレンテレフタレート（ｒＰＥＴ）、高密度ポリエチレン（ＨＤＰＥ）、ポリ塩化ビニル（ＰＶＣ）、ポリ乳酸（ＰＬＡ）、セルロース、生体高分子フィルム、低密度ポリエチレン（ＬＤＰＥ）、ＰＰ、ポリスチレン（ＰＳ）、ポリエステル、または他のタイプの重合体若しくはプラスチックを含み得る。一部の実施形態において、プラスチックは、ＰＥＴを含む。 In some embodiments, the outer surface of the container comprises plastic. The outer surface may contain any suitable polymer or mixture of polymers, or may be formed from a mixture of any suitable polymer or polymer. Polymers or mixtures of polymers include, for example, PET, recycled polyethylene terephthalate (rPET), high density polyethylene (HDPE), polyvinyl chloride (PVC), polylactic acid (PLA), cellulose, biopolymer films, low density polyethylene. (LDPE), PP, polystyrene (PS), polyester, or other types of polymers or plastics may be included. In some embodiments, the plastic comprises PET.

ラベルは、一般に、容器から除去できるものの、容器の外表面は、ラベルを容器に接着するために用いた接着剤の一部が保たれる場合がある。かかる接着剤の残留物は、その後の洗浄、再ラベル付け、または容器リサイクル等の後続する容器の作業を汚染させたり妨害し得る。一部の実施形態において、提供されたラベルは、外表面から除去できるが、実質的に全ての接着剤が外表面に残っているというよりは、ラベルと共に配置及び／または保たれたまま残っている。 Although the label can generally be removed from the container, the outer surface of the container may retain some of the adhesive used to bond the label to the container. Residues of such adhesives can contaminate or interfere with subsequent container operations such as subsequent cleaning, relabeling, or container recycling. In some embodiments, the provided label can be removed from the outer surface, but substantially all the adhesive remains placed and / or retained with the label rather than remaining on the outer surface. There is.

また、本発明は、ラベルを容器に適用する方法に関する。前記方法は、外表面を規定する容器、及び、一実施形態によるラベルを提供するステップを含む。前記方法は、ラベルを容器の外表面に接着させてラベルを容器に適用するステップをさらに含む。 The present invention also relates to a method of applying a label to a container. The method comprises providing a container defining the outer surface and a label according to one embodiment. The method further comprises the step of adhering the label to the outer surface of the container and applying the label to the container.

ラベルは、１つ以上の容器または物品に、バッチ式、連続式、または半連続式により接着できる。適用する前に、ラベルから１つ以上のライナーを除去して、ラベルの接着剤面を露出できる。その後、接着剤面とラベルは、容器または物品と接触し、前記ラベルは容器または物品に適用される。また、接着は、容器との接触及び／または接着を促進するように、ラベルに押し付けたりラベルに押圧力を加える１つ以上の作業、熱及び／若しくはＵＶ光への露出による接着剤の活性化及び／若しくは硬化、並びに／または、乾燥作業を含む。 The label can be attached to one or more containers or articles in batch, continuous, or semi-continuous manner. Prior to application, one or more liners can be removed from the label to expose the adhesive surface of the label. The adhesive surface and label then come into contact with the container or article, and the label is applied to the container or article. Adhesion also activates the adhesive by exposure to heat and / or UV light, one or more operations that press against the label or apply pressure to the label to facilitate contact and / or adhesion with the container. And / or curing and / or including drying operations.

次の実施形態が考慮される。特徴及び実施形態のあらゆる組み合わせが考慮される。
実施形態１：ホットメルト感圧接着剤は、スチレンイソプレンスチレン共重合体と、水素化脂環式炭化水素樹脂を含む粘着付与剤と、４０℃における動粘度が４００〜１０００ｍｍ２／秒の範囲内であるパラフィンオイルを含む可塑剤と、５重量％未満のポリエチレンワックスと、を含む。 The following embodiments are considered. Any combination of features and embodiments will be considered.
Embodiment 1: The hot melt pressure-sensitive adhesive is a tackifier containing a styrene isoprene styrene copolymer and a hydride alicyclic hydrocarbon resin, and a kinematic viscosity at 40 ° C. is within the range of 400 to 1000 mm 2 / sec. Contains a plasticizer containing paraffin oil and less than 5% by weight polyethylene wax.

実施形態２：実施形態１において、前記粘着付与剤は、３００〜１０００の範囲の重量平均分子量を有する。 Embodiment 2: In Embodiment 1, the tackifier has a weight average molecular weight in the range of 300-1000.

実施形態３：実施形態１または実施形態２において、前記可塑剤は、４００〜１０００の範囲内の数平均分子量を有する。 Embodiment 3: In Embodiment 1 or 2, the plasticizer has a number average molecular weight in the range of 400-1000.

実施形態４：実施形態３において、前記粘着付与剤の重量平均分子量は、前記可塑剤の数平均分子量の１０％以内である。 Embodiment 4: In the third embodiment, the weight average molecular weight of the tackifier is within 10% of the number average molecular weight of the plasticizer.

実施形態５：実施形態１〜実施形態４のいずれか１つの実施形態において、前記ホットメルト感圧接着剤中における前記スチレンイソプレンスチレン共重合体の濃度は、１５〜６５重量％の範囲内であり、前記ホットメルト感圧接着剤中における前記粘着付与剤の濃度は、１５〜６５重量％の範囲内であり、前記ホットメルト感圧接着剤中における前記可塑剤の濃度は、５〜３５重量％の範囲内である。 Embodiment 5: In any one of Embodiments 1 to 4, the concentration of the styrene isoprene styrene copolymer in the hot melt pressure-sensitive adhesive is in the range of 15 to 65% by weight. The concentration of the pressure-sensitive adhesive in the hot-melt pressure-sensitive adhesive is in the range of 15 to 65% by weight, and the concentration of the plasticizer in the hot-melt pressure-sensitive adhesive is 5 to 35% by weight. Is within the range of.

実施形態６：実施形態１〜実施形態４のいずれか１つの実施形態において、前記ホットメルト感圧接着剤中における前記スチレンイソプレンスチレン共重合体の濃度は、２５〜５５重量％の範囲内であり、前記ホットメルト感圧接着剤中における前記粘着付与剤の濃度は、２５〜５５重量％の範囲内であり、前記ホットメルト感圧接着剤中における前記可塑剤の濃度は、１５〜２５重量％の範囲内であり、前記ホットメルト感圧接着剤中における前記ポリエチレンワックスの濃度は、２重量％未満である。 Embodiment 6: In any one of the first to fourth embodiments, the concentration of the styrene-isoprene styrene copolymer in the hot-melt pressure-sensitive adhesive is in the range of 25 to 55% by weight. The concentration of the pressure-sensitive adhesive in the hot-melt pressure-sensitive adhesive is in the range of 25 to 55% by weight, and the concentration of the plasticizer in the hot-melt pressure-sensitive adhesive is 15 to 25% by weight. The concentration of the polyethylene wax in the hot melt pressure sensitive adhesive is less than 2% by weight.

実施形態７：実施形態１〜実施形態６のいずれか１つの実施形態において、前記スチレンイソプレンスチレン共重合体は、３０重量％未満のジブロックのグレードを有する。 Embodiment 7: In any one embodiment of Embodiments 1 to 6, the styrene isoprene styrene copolymer has a diblock grade of less than 30% by weight.

実施形態８：実施形態１〜実施形態７のいずれか１つの実施形態において、前記スチレンイソプレンスチレン共重合体は、２５重量％未満のスチレン含量を有する。 Embodiment 8: In any one embodiment of Embodiments 1 to 7, the styrene isoprene styrene copolymer has a styrene content of less than 25% by weight.

実施形態９：実施形態１〜実施形態８のいずれか１つの実施形態において、前記可塑剤は、４０℃における動粘度が４００〜７００ｍｍ２／秒の範囲内である。 Embodiment 9: In any one embodiment of Embodiments 1 to 8, the plasticizer has a kinematic viscosity at 40 ° C. in the range of 400 to 700 mm 2 / sec.

実施形態１０：実施形態１〜実施形態９のいずれか１つの実施形態において、前記ポリエチレンワックスは、１４０℃における動的粘度が１５０〜５００ｃｐｓの範囲内である。 Embodiment 10: In any one embodiment of Embodiments 1 to 9, the polyethylene wax has a dynamic viscosity at 140 ° C. in the range of 150 to 500 cps.

実施形態１１：実施形態１〜実施形態１０のいずれか１つの実施形態において、前記ポリエチレンワックスは、１００℃を超える流動点を有する。 Embodiment 11: In any one of the first to tenth embodiments, the polyethylene wax has a pour point of more than 100 ° C.

実施形態１２：実施形態１〜実施形態１１のいずれか１つの実施形態において、前記ホットメルト感圧接着剤は、５未満のヘイズ値を有する。 12: In any one of the first to eleventh embodiments, the hot melt pressure sensitive adhesive has a haze value of less than 5.

実施形態１３：実施形態１〜実施形態１２のいずれか１つの実施形態において、前記ホットメルト感圧接着剤は、２０未満の不透明度コントラスト比を有する。 13: In any one of the first to twelfth embodiments, the hot melt pressure sensitive adhesive has an opacity contrast ratio of less than 20.

実施形態１４：実施形態１２において、前記ホットメルト感圧接着剤を６５℃で１時間加熱したとき、前記ヘイズ値に２０％未満の変化がある。 Embodiment 14: In the twelfth embodiment, when the hot melt pressure sensitive adhesive is heated at 65 ° C. for 1 hour, the haze value has a change of less than 20%.

実施形態１５：実施形態１３において、前記ホットメルト感圧接着剤を６５℃で１時間加熱したとき、前記不透明度コントラスト比に２０％未満の変化がある。 Embodiment 15: In the thirteenth embodiment, when the hot melt pressure sensitive adhesive is heated at 65 ° C. for 1 hour, the opacity contrast ratio changes by less than 20%.

実施形態１６：実施形態１〜実施形態１５のいずれか１つの実施形態において、前記ホットメルト感圧接着剤は、１４０℃における動的粘度が１０，０００〜２０，０００ｃｐｓの範囲内である。 Embodiment 16: In any one of the first to fifteenth embodiments, the hot melt pressure sensitive adhesive has a dynamic viscosity at 140 ° C. in the range of 10,000 to 20,000 cps.

実施形態１７：ラベルは、印刷表示を収容することが可能な表面材と、実施形態１〜実施形態１６のいずれか１つの実施形態に記載のホットメルト感圧接着剤を含むホットメルト感圧接着剤と、を含む。 Embodiment 17: The label is a hot melt pressure sensitive adhesive containing a surface material capable of accommodating a printed display and a hot melt pressure sensitive adhesive according to any one of Embodiments 1 to 16. Including the agent.

実施形態１８：実施形態１７において、ホットメルト感圧接着剤層上に配置されたライナーをさらに含む。 Embodiment 18: In Embodiment 17, a liner arranged on the hot melt pressure sensitive adhesive layer is further included.

実施形態１９：実施形態１７または実施形態１８のいずれか１つの実施形態において、前記ラベルは、縦方向長さ及び横方向長さを有し、６５℃を超える温度で４日間８５％の相対湿度で保管したとき、前記縦方向長さ及び横方向長さにそれぞれ２％未満の変化がある。 Embodiment 19: In any one embodiment of Embodiment 17 or 18, the label has a longitudinal length and a lateral length and has a relative humidity of 85% for 4 days at a temperature above 65 ° C. When stored in, there is a change of less than 2% in the vertical length and the horizontal length, respectively.

実施形態２０：ラベル付き容器は、外表面を有する容器と、前記容器の外表面に接着された実施形態１７〜実施形態１９のいずれか１つの実施形態に記載のラベルと、を含む。 20: The labeled container includes a container having an outer surface and the label according to any one of embodiments 17 to 19 adhered to the outer surface of the container.

実施形態２１：実施形態２０において、前記容器の外表面は、ガラス、ポリエチレンテレフタレート、またはその他のプラスチックを含む。 21: In embodiment 20, the outer surface of the container comprises glass, polyethylene terephthalate, or other plastic.

実施形態２２：実施形態２０または実施形態２１において、前記容器はボトルである。
実施形態２３：実施形態２０〜実施形態２２のいずれか１つの実施形態において、前記ラベルは、剥離により前記容器から実質的に完全に除去されることが可能である。 22: In the 20th or 21st embodiment, the container is a bottle.
23: In any one of the 20th to 22nd embodiments, the label can be substantially completely removed from the container by peeling.

実施形態２４：ラベルを容器に適用する方法は、外表面を規定する容器を提供するステップと、実施形態１７〜実施形態１９のいずれか１つの実施形態に記載のラベルを提供するステップと、前記ラベルを前記容器の外表面に接着することにより前記ラベルを前記容器に適用するステップと、を含む。 Embodiment 24: The method of applying the label to the container includes a step of providing a container defining an outer surface, a step of providing the label according to any one of the 17th to 19th embodiments, and the above-mentioned step. It comprises applying the label to the container by adhering the label to the outer surface of the container.

実施形態２５：実施形態２４において、前記容器の外表面は、ガラス、ポリエチレンテレフタレート、またはその他のプラスチックを含む。 25: In embodiment 24, the outer surface of the container comprises glass, polyethylene terephthalate, or other plastic.

実施形態２６：実施形態２４または実施形態２５において、前記ラベルは、５℃を超える温度で接着された後、最初の８時間以内で前記容器から実質的に完全に除去でき、且つ、前記容器に再適用できる。 Embodiment 26: In Embodiment 24 or 25, the label can be substantially completely removed from the container within the first 8 hours after being adhered at a temperature above 5 ° C. and into the container. Can be reapplied.

本発明は、次の非制限的な実施例を考慮してさらによく理解される。
実施例
８つのＨＭＰＳＡ組成物を下記表１に示した製剤により製造した。ＨＭＰＳＡの物理的特性及び性能特性、例えば、膨潤性、動的粘度、及び加工性能について試験を行った。その結果を表１に提供する。 The present invention is better understood in light of the following non-limiting examples.
Example Eight HMPSA compositions were prepared by the formulations shown in Table 1 below. The physical and performance characteristics of HMPSA, such as swellability, dynamic viscosity, and processing performance, were tested. The results are provided in Table 1.

ラベルは、比較例ＡとＢ及び実施例１のＨＭＰＳＡを用いて製造し、膨潤性について試験を行った。実施例１のＨＭＰＳＡを用いたラベル（及び比較例ＡとＢを用いたラベル）は、非常に良好な膨潤の結果を示した。上述のように、膨潤性が減少した接着剤は、構造的完全性においてより優れており、且つ、膨潤傾向がより大きな接着剤に比べて、少ないオイル移動を示すことができる。さらに、実施例１のＨＭＰＳＡを用いたラベルは、性能特性、例えば、水白化耐性、再配置性、及び／または光学的鮮明度の優れた組み合わせを示した。重要なことに、実施例１のＨＭＰＳＡは、低粘度を有し、加工しやすく、高品質のラベルを生成する。反面、比較例ＡとＢのＨＭＰＳＡは、遥かに高い粘度を示し、これは、加工の困難性と低品質のラベルを生成する。 Labels were prepared using HMPSA of Comparative Examples A and B and Example 1 and tested for swellability. The labels using HMPSA of Example 1 (and the labels using Comparative Examples A and B) showed very good swelling results. As mentioned above, an adhesive with reduced swellability is better in structural integrity and can exhibit less oil transfer than an adhesive with a greater swelling tendency. In addition, the HMPSA-based label of Example 1 showed an excellent combination of performance characteristics, such as water whitening resistance, rearrangeability, and / or optical sharpness. Importantly, the HMPSA of Example 1 has a low viscosity, is easy to process, and produces high quality labels. On the other hand, the HMPSAs of Comparative Examples A and B show much higher viscosities, which results in processing difficulties and poor quality labels.

表１に示すように、実施例１〜４及び８の製剤は、４０℃における動粘度が４００〜１０００ｍｍ２／秒の範囲内である可塑剤を用いる。これらの製剤は、特に、優れた加工性と共に性能特性の有利な組み合わせを有するホットメルトＰＳＡを提供する。かかる例示的な接着剤は、高いレベルの水白化耐性、良好な除去性、光学的鮮明度、及び、低い膨潤性とオイル移動性を有する。重要なことに、実施例１〜４は、例えば、１００００〜２００００センチポアズの範囲の低い動的粘度を示し、これは、高品質のコーティング層の形成、即ち、優れた加工性を提供する。反面、比較例Ａ〜Ｄは、（２００００センチポアズより遥かに高く、一部の場合においては８００００センチポアズを超える）遥かに高い動的粘度を示す。これらの比較例は、少なくとも部分的に高粘度の可塑剤により、加工性が悪いことを示した。 As shown in Table 1, the formulations of Examples 1 to 4 and 8 use plasticizers having kinematic viscosities in the range of 400 to 1000 mm 2 / sec at 40 ° C. These formulations in particular provide hot melt PSAs that have an advantageous combination of performance properties as well as excellent processability. Such exemplary adhesives have a high level of water whitening resistance, good removability, optical sharpness, and low swelling and oil mobility. Importantly, Examples 1 to 4 exhibit low dynamic viscosities, eg, in the range of 1000 to 20000 centipores, which provides the formation of a high quality coating layer, i.e., excellent workability. On the other hand, Comparative Examples A to D show much higher dynamic viscosities (much higher than 20000 centipores and in some cases more than 80,000 cmpores). These comparative examples showed that the processability was poor due to at least a partially high viscosity plasticizer.

また、表１に示すように、実施例１〜４のＨＭＰＳＡ製剤は、それぞれ、３００〜８００の好ましい範囲内の分子量を有する粘着付与剤を含む。かかる比較的低い粘着付与剤の分子量は、可塑剤の数平均分子量を部分的に相殺させる役割を行うことが可能であり、これは、例えば、１００００〜２００００センチポアズの有利な範囲内の動的粘度全体を低下させるのにさらに寄与する。反面、比較例Ａ〜Ｄの製剤は、１０００を超える数平均分子量を有する粘着付与剤を用いる。得られたＨＭＰＳＡは、例えば、３５０００センチポアズを超える遥かに高い動的粘度を有し、これは、配合やコーティング等の加工ステップの難易度を上げる。よって、実施例１〜４及び比較例Ａ〜Ｄは、低膨潤性、低いオイル移動性、及び低粘度に対する所望の特性を同時に満たす接着剤を製剤化するにあたって、低い重量平均分子量の粘着付与剤と高い水平均分子量の可塑剤とを組み合わせることの重要性を立証する。 In addition, as shown in Table 1, the HMPSA preparations of Examples 1 to 4 each contain a tackifier having a molecular weight in the preferable range of 300 to 800. The molecular weight of such a relatively low tackifier can serve to partially offset the number average molecular weight of the plasticizer, which is, for example, a dynamic viscosity within an advantageous range of 1000 to 20000 centipores. Further contributes to lowering the whole. On the other hand, the preparations of Comparative Examples A to D use a tackifier having a number average molecular weight of more than 1000. The resulting HMPSA has a much higher dynamic viscosity, for example exceeding 35,000 centipores, which increases the difficulty of processing steps such as compounding and coating. Therefore, Examples 1 to 4 and Comparative Examples A to D are tackifiers having a low weight average molecular weight in formulating an adhesive that simultaneously satisfies the desired properties for low swelling property, low oil mobility, and low viscosity. Demonstrate the importance of combining with a plasticizer with a high water average molecular weight.

要約すると、表１のデータは、比較例の製剤が本明細書で論じた粘度及び／または分子量の範囲を外れた高粘度の可塑剤（並びに、選択的に可塑剤及び／または粘着付与剤）を用いることを示している。これらの比較例は、好ましくない物理的特性及び／または性能特性を有する。これらのデータは、上述の構成要素の重要性及び臨界性を示している。 In summary, the data in Table 1 show high-viscosity plasticizers (and optionally plasticizers and / or tackifiers) for which the formulations of Comparative Examples are outside the range of viscosity and / or molecular weight discussed herein. Is shown to be used. These comparative examples have unfavorable physical and / or performance characteristics. These data show the importance and criticality of the above components.

本発明を詳細に説明したが、本発明の思想及び範囲内における変形は、当業者には容易に明らかであろう。上述の議論に鑑みて、当技術分野の関連知識及び背景技術と詳細な説明に関して上述した参照文献は、その開示内容が全て参照として本明細書に含まれる。また、本発明の態様及び多様な実施形態の部分、並びに、下記及び／または添付の請求範囲に記述された多様な特徴は、全体的なまたは部分的な組み合わせや互換が可能であるということを理解すべきである。多様な実施形態に関する上述の説明において、他の実施形態を参照するそれらの実施形態は、当業者によって理解される他の実施形態と共に適切に組み合わせられる。さらに、当業者は、上述の説明は単に例示であるだけであって、本発明を限定しようとする意図ではないということを理解するであろう。 Although the present invention has been described in detail, variations within the ideas and scope of the invention will be readily apparent to those skilled in the art. In view of the above discussion, all of the references mentioned above with respect to relevant knowledge and background techniques in the art and detailed description are included herein as references. It is also noted that the aspects of the invention and the various embodiments, as well as the various features described in the following and / or the appended claims, can be combined or compatible in whole or in part. Should be understood. In the above description of the various embodiments, those embodiments that reference other embodiments are appropriately combined with other embodiments understood by those skilled in the art. Moreover, one of ordinary skill in the art will appreciate that the above description is merely exemplary and is not intended to limit the invention.

Claims (26)

スチレンイソプレンスチレン共重合体と、
水素化脂環式炭化水素樹脂を含む粘着付与剤と、
４０℃における動粘度が４００〜１０００ｍｍ２／秒の範囲内であるパラフィンオイルを含む可塑剤と、
５重量％未満のポリエチレンワックスと、を含む、ホットメルト感圧接着剤。 Styrene isoprene Styrene copolymer and
A tackifier containing a hydrogenated alicyclic hydrocarbon resin,
Plasticizers containing paraffin oil with kinematic viscosities in the range of 400-1000 mm 2 / sec at 40 ° C.
A hot melt pressure sensitive adhesive containing less than 5% by weight of polyethylene wax. 前記粘着付与剤は、３００〜１０００の範囲の重量平均分子量を有する、請求項１に記載のホットメルト感圧接着剤。 The hot melt pressure-sensitive adhesive according to claim 1, wherein the tackifier has a weight average molecular weight in the range of 300 to 1000. 前記可塑剤は、４００〜１０００の範囲内の数平均分子量を有する、請求項１または２に記載のホットメルト感圧接着剤。 The hot melt pressure sensitive adhesive according to claim 1 or 2, wherein the plasticizer has a number average molecular weight in the range of 400 to 1000. 前記粘着付与剤の重量平均分子量は、前記可塑剤の数平均分子量の１０％以内である、請求項３に記載のホットメルト感圧接着剤。 The hot melt pressure-sensitive adhesive according to claim 3, wherein the weight average molecular weight of the tackifier is within 10% of the number average molecular weight of the plasticizer. 前記ホットメルト感圧接着剤中における前記スチレンイソプレンスチレン共重合体の濃度は、１５〜６５重量％の範囲内であり、前記ホットメルト感圧接着剤中における前記粘着付与剤の濃度は、１５〜６５重量％の範囲内であり、前記ホットメルト感圧接着剤中における前記可塑剤の濃度は、５〜３５重量％の範囲内である、請求項１〜４のいずれか１項に記載のホットメルト感圧接着剤。 The concentration of the styrene isoprene styrene copolymer in the hot melt pressure sensitive adhesive is in the range of 15 to 65% by weight, and the concentration of the tackifier in the hot melt pressure sensitive adhesive is 15 to 65% by weight. The hot according to any one of claims 1 to 4, which is in the range of 65% by weight and the concentration of the plasticizer in the hot melt pressure sensitive adhesive is in the range of 5 to 35% by weight. Melt pressure sensitive adhesive. 前記ホットメルト感圧接着剤中における前記スチレンイソプレンスチレン共重合体の濃度は、２５〜５５重量％の範囲内であり、前記ホットメルト感圧接着剤中における前記粘着付与剤の濃度は、２５〜５５重量％の範囲内であり、前記ホットメルト感圧接着剤中における前記可塑剤の濃度は、１５〜２５重量％の範囲内であり、前記ホットメルト感圧接着剤中における前記ポリエチレンワックスの濃度は、２重量％未満である、請求項１〜４のいずれか１項に記載のホットメルト感圧接着剤。 The concentration of the styrene isoprene styrene copolymer in the hot melt pressure sensitive adhesive is in the range of 25 to 55% by weight, and the concentration of the tackifier in the hot melt pressure sensitive adhesive is 25 to 55% by weight. The concentration of the plasticizer in the hot melt pressure sensitive adhesive is in the range of 15 to 25% by weight, and the concentration of the polyethylene wax in the hot melt pressure sensitive adhesive is in the range of 55% by weight. Is the hot melt pressure sensitive adhesive according to any one of claims 1 to 4, wherein is less than 2% by weight. 前記スチレンイソプレンスチレン共重合体は、３０重量％未満のジブロックのグレードを有する、請求項１〜６のいずれか１項に記載のホットメルト感圧接着剤。 The hot melt pressure sensitive adhesive according to any one of claims 1 to 6, wherein the styrene isoprene styrene copolymer has a diblock grade of less than 30% by weight. 前記スチレンイソプレンスチレン共重合体は、２５重量％未満のスチレン含量を有する、請求項１〜７のいずれか１項に記載のホットメルト感圧接着剤。 The hot melt pressure-sensitive adhesive according to any one of claims 1 to 7, wherein the styrene isoprene styrene copolymer has a styrene content of less than 25% by weight. 前記可塑剤は、４０℃における動粘度が４００〜７００ｍｍ２／秒の範囲内である、請求項１〜８のいずれか１項に記載のホットメルト感圧接着剤。 The hot melt pressure-sensitive adhesive according to any one of claims 1 to 8, wherein the plasticizer has a kinematic viscosity at 40 ° C. in the range of 400 to 700 mm 2 / sec. 前記ポリエチレンワックスは、１４０℃における動的粘度が１５０〜５００ｃｐｓの範囲内である、請求項１〜９のいずれか１項に記載のホットメルト感圧接着剤。 The hot melt pressure-sensitive adhesive according to any one of claims 1 to 9, wherein the polyethylene wax has a dynamic viscosity at 140 ° C. in the range of 150 to 500 cps. 前記ポリエチレンワックスは、１００℃を超える流動点を有する、請求項１〜１０のいずれか１項に記載のホットメルト感圧接着剤。 The hot melt pressure-sensitive adhesive according to any one of claims 1 to 10, wherein the polyethylene wax has a pour point exceeding 100 ° C. ５未満のヘイズ値を有する、請求項１〜１１のいずれか１項に記載のホットメルト感圧接着剤。 The hot melt pressure sensitive adhesive according to any one of claims 1 to 11, which has a haze value of less than 5. 前記ホットメルト感圧接着剤を６５℃で１時間加熱したとき、前記ヘイズ値に２０％未満の変化がある、請求項１２に記載のホットメルト感圧接着剤。 The hot melt pressure sensitive adhesive according to claim 12, wherein the haze value changes by less than 20% when the hot melt pressure sensitive adhesive is heated at 65 ° C. for 1 hour. ２０未満の不透明度コントラスト比を有する、請求項１〜１３のいずれか１項に記載のホットメルト感圧接着剤。 The hot melt pressure sensitive adhesive according to any one of claims 1 to 13, which has an opacity contrast ratio of less than 20. 前記ホットメルト感圧接着剤を６５℃で１時間加熱したとき、前記不透明度コントラスト比に２０％未満の変化がある、請求項１４に記載のホットメルト感圧接着剤。 The hot melt pressure sensitive adhesive according to claim 14, wherein when the hot melt pressure sensitive adhesive is heated at 65 ° C. for 1 hour, the opacity contrast ratio changes by less than 20%. １４０℃における動的粘度が１０，０００〜２０，０００ｃｐｓの範囲内である、請求項１〜１５のいずれか１項に記載のホットメルト感圧接着剤。 The hot melt pressure sensitive adhesive according to any one of claims 1 to 15, wherein the dynamic viscosity at 140 ° C. is in the range of 10,000 to 20,000 cps. 印刷表示を収容することが可能な表面材と、
請求項１〜１６のいずれか１項に記載のホットメルト感圧接着剤を含むホットメルト感圧接着剤と、を含む、ラベル。 A surface material that can accommodate printed displays and
A label comprising a hot melt pressure sensitive adhesive comprising the hot melt pressure sensitive adhesive according to any one of claims 1 to 16. ホットメルト感圧接着剤層上に配置されたライナーをさらに含む、請求項１７に記載のラベル。 17. The label of claim 17, further comprising a liner disposed on the hot melt pressure sensitive adhesive layer. 前記ラベルは、縦方向長さ及び横方向長さを有し、６５℃を超える温度で４日間８５％の相対湿度で保管したとき、前記縦方向長さ及び横方向長さにそれぞれ２％未満の変化がある、請求項１７または１８に記載のラベル。 The label has a vertical length and a horizontal length, and when stored at a temperature exceeding 65 ° C. and a relative humidity of 85% for 4 days, the vertical length and the horizontal length are each less than 2%. The label according to claim 17 or 18, wherein there is a change in. 外表面を有する容器と、
前記容器の外表面に接着された請求項１７〜１９のいずれか１項に記載のラベルと、を含む、ラベル付き容器。 A container with an outer surface and
A labeled container comprising the label according to any one of claims 17 to 19, which is adhered to the outer surface of the container. 前記容器の外表面は、ガラス、ポリエチレンテレフタレート、またはその他のプラスチックを含む、請求項２０に記載のラベル付き容器。 The labeled container according to claim 20, wherein the outer surface of the container contains glass, polyethylene terephthalate, or other plastic. 前記容器はボトルである、請求項２０または２１に記載のラベル付き容器。 The labeled container according to claim 20 or 21, wherein the container is a bottle. 前記ラベルは、剥離により前記容器から実質的に完全に除去されることが可能である、請求項２０〜２２のいずれか１項に記載のラベル付き容器。 The labeled container according to any one of claims 20 to 22, wherein the label can be substantially completely removed from the container by peeling. 外表面を規定する容器を提供するステップと、
請求項１７〜１９のいずれか１項に記載のラベルを提供するステップと、
前記ラベルを前記容器の外表面に接着することにより前記ラベルを前記容器に適用するステップと、を含む、ラベルを容器に適用する方法。 Steps to provide a container that defines the outer surface,
The step of providing the label according to any one of claims 17 to 19.
A method of applying a label to a container, comprising the step of applying the label to the container by adhering the label to the outer surface of the container. 前記容器の外表面は、ガラス、ポリエチレンテレフタレート、またはその他のプラスチックを含む、請求項２４に記載の方法。 24. The method of claim 24, wherein the outer surface of the container comprises glass, polyethylene terephthalate, or other plastic. 前記ラベルは、５℃を超える温度で接着された後、最初の８時間以内で前記容器から実質的に完全に除去でき、且つ、前記容器に再適用できる、請求項２４または２５に記載の方法。 The method of claim 24 or 25, wherein the label can be substantially completely removed from the container and reapplied to the container within the first 8 hours after being adhered at a temperature above 5 ° C. ..
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