JP2007284464A - Self-adhesive material, its manufacturing method, and manufacturing method of self-adhesive product and laminated product using the same - Google Patents

Self-adhesive material, its manufacturing method, and manufacturing method of self-adhesive product and laminated product using the same Download PDF

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JP2007284464A
JP2007284464A JP2006109586A JP2006109586A JP2007284464A JP 2007284464 A JP2007284464 A JP 2007284464A JP 2006109586 A JP2006109586 A JP 2006109586A JP 2006109586 A JP2006109586 A JP 2006109586A JP 2007284464 A JP2007284464 A JP 2007284464A
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particles
block
adhesive material
block copolymer
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JP3939738B1 (en
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Tetsuo Yasuike
徹郎 安池
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Idemitsu Unitech Co Ltd
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Priority to JP2006109586A priority Critical patent/JP3939738B1/en
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Priority to KR1020087023864A priority patent/KR20080113390A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/04—Layered products comprising a layer of synthetic resin as impregnant, bonding, or embedding substance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • 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
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2405/00—Adhesive articles, e.g. adhesive tapes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)
  • Adhesive Tapes (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a self-adhesive material exhibiting high re-adhesive strength that can be extruded through a single-screw extruder. <P>SOLUTION: The self-adhesive material comprises particles (A) and (B) below mixed together: (A) particles comprising a rubbery block copolymer (1a) mainly composed of a styrene block and a diene block, and a tackifier resin (2); (B) particles comprising a rubbery block copolymer (1b) mainly composed of a styrene block and a diene block, and a plasticizer (3). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

本発明は、粘着テープや多層体の粘着層等に用いられる粘着物の製造に用いられる粘着材料、及びその製造方法に関する。   The present invention relates to a pressure-sensitive adhesive material used for the production of a pressure-sensitive adhesive used for pressure-sensitive adhesive tapes and multi-layer pressure-sensitive adhesive layers, and a method for producing the same.

粘着材料として従来は有機溶剤に溶かしてコーティングした後、有機溶剤を揮発させて粘着層を設ける方法が行われていたが、近年環境負荷の少ない樹脂系粘着材料を使用する傾向が強くなっている。即ち、粘着材料を加熱して溶融押出しすることにより、基材へコーティングして粘着テープを製造したり（特許文献１）、共押出し法により再封可能な包装材料（特許文献２）にすることが知られている。   Conventionally, a method of providing an adhesive layer by volatilizing an organic solvent after coating by dissolving in an organic solvent as an adhesive material has been performed, but in recent years there has been a growing tendency to use resin-based adhesive materials with less environmental impact. . That is, an adhesive material is heated and melt-extruded to produce a pressure-sensitive adhesive tape by coating on a base material (Patent Document 1), or a packaging material that can be resealed by a co-extrusion method (Patent Document 2). It has been known.

粘着材料としては、特許文献３に見られるように、エチレン−酢酸ビニル共重合体や塩化ビニル共重合体又はスチレン系ゴム質共重合体等に、テルペン樹脂や石油系樹脂等の粘着付与樹脂、及び流動パラフィン、合成ワックス、プロセスオイル等の可塑剤を配合したものがある。
しかしながら、これらの粘着材料は粘着性があるため二軸押出し機やその他の混練機で混合しないと利用できない。二軸押出し機を備えれば、基材へのコーティングや押出しラミネーション又は他の樹脂との共押出が可能になり、粘着材料の再粘着強度が強いという長所はあるものの、設備費が高価になるという欠点や専用設備となり設備が限定されるという欠点がある。 As an adhesive material, as seen in Patent Document 3, an ethylene-vinyl acetate copolymer, a vinyl chloride copolymer, a styrene-based rubbery copolymer, or the like, a tackifier resin such as a terpene resin or a petroleum-based resin, In addition, there are blends of plasticizers such as liquid paraffin, synthetic wax and process oil.
However, since these adhesive materials are sticky, they cannot be used unless they are mixed in a twin screw extruder or other kneader. If equipped with a twin-screw extruder, coating on the substrate, extrusion lamination, or co-extrusion with other resins becomes possible, and although there is an advantage that the re-adhesion strength of the adhesive material is strong, the equipment cost is expensive There is a disadvantage that it becomes a special equipment and the equipment is limited.

一方、特許文献４や特許文献５には、スチレン系ゴム質共重合体に粘着付与樹脂を配合したものが粘着材料として提示されている。   On the other hand, in Patent Document 4 and Patent Document 5, a styrenic rubbery copolymer blended with a tackifying resin is presented as an adhesive material.

これらの原料は単軸材料で押出すことは可能ではあるが、粘着付与樹脂は脆く、しかも軟化点が１５０℃以下のものが多いため、押出機ホッパー下部に粘着付与樹脂の破片がスクリュー溝に付着して溝を埋めたり、熱によりそれが融解してオイル状になり樹脂を滑らせたりすることによる押出し変動を起こす。
さらに、流動パラフィン、合成ワックス、プロセスオイル等の可塑剤を配合していないため、再粘着強度が弱い等の問題があった。
特開昭５５−１３９４７７号公報 特開２００３−１７５５６７号公報 特開昭５５−１３９４７７号公報 特開平０７−２２４２５５号公報 特開２００３−１７５５６７号公報 Although these raw materials can be extruded with a uniaxial material, the tackifying resin is brittle and has a softening point of 150 ° C. or less, so the pieces of tackifying resin are formed in the screw groove at the bottom of the extruder hopper. Adhesion fills the groove, or heat melts it into an oily state by heat, causing the extrusion to fluctuate.
Furthermore, since plasticizers such as liquid paraffin, synthetic wax and process oil are not blended, there are problems such as low re-adhesion strength.
JP-A-55-139477 JP 2003-175567 A JP-A-55-139477 JP 07-224255 A JP 2003-175567 A

本発明は上述の問題に鑑みなされたものであり、単軸押出し機で押出せる、再粘着強度の強い粘着材料を提供することを目的とする。   This invention is made | formed in view of the above-mentioned problem, and it aims at providing the adhesive material with strong re-adhesion intensity | strength which can be extruded with a single screw extruder.

本発明によれば、以下の粘着材料等が提供される。
１．下記粒子（Ａ），（Ｂ）が混合されている粘着材料。
（Ａ）主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ａ）と、粘着付与樹脂（２）からなる粒子
（Ｂ）主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ｂ）と、可塑剤（３）からなる粒子
２．さらに、下記粒子（Ｃ）が混合されている１記載の粘着材料。
（Ｃ）主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ｃ）からなる粒子
３．下記成分が下記配合量で含まれている１又は２に記載の粘着材料。
前記ゴム質ブロック共重合体（１ａ）及び（１ｂ）、又は（１ａ），（１ｂ）及び（１ｃ）を合わせたゴム質ブロック共重合体（１）： ４０〜７０重量％
前記粘着付与樹脂（２）： ２０〜５０重量％
前記可塑剤（３）： １０〜３０重量％
４．主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ａ）と、粘着付与樹脂（２）からなる、１に記載の粘着材料用粒子。
５．前記粘着付与樹脂（２）が４０〜９０重量％含まれる４に記載の粘着材料用粒子。
６．主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ｂ）と、可塑剤（３）からなる、１に記載の粘着材料用粒子。
７．主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ａ）と、粘着付与樹脂（２）を溶融混合して粒子（Ａ）を製造し、主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ｂ）と、可塑剤（３）を溶融混合して粒子（Ｂ）を製造し、前記粒子（Ａ）と前記粒子（Ｂ）をドライブレンドする１に記載の粘着材料の製造方法。
８．主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ａ）と、粘着付与樹脂（２）を溶融混合して粒子（Ａ）を製造し、主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ｂ）と、可塑剤（３）を溶融混合して粒子（Ｂ）を製造し、主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ｃ）を溶融混合して粒子（Ｃ）を製造し、前記粒子（Ａ）、前記粒子（Ｂ）及び前記粒子（Ｃ）をドライブレンドする２に記載の粘着材料の製造方法。
９．ゴム質ブロック共重合体（１）５０〜５５重量％と、粘着付与樹脂（２）２４〜３０重量％と、可塑剤（３）１８〜２１重量％を含む粘着材料。
１０．１〜３のいずれかに記載の粘着材料を単軸押出し機で溶融混練して押出し成形する粘着物の製造方法。
１１．１〜３のいずれかに記載の粘着材料を、単軸押出し機で溶融混練して樹脂と共押出しする粘着層と樹脂層からなる積層体の製造方法。
１２．１０で製造した粘着物又は１１で製造した積層体を、基材に溶融接着する多層体の製造方法。 According to the present invention, the following adhesive materials and the like are provided.
1. An adhesive material in which the following particles (A) and (B) are mixed.
(A) Rubber block copolymer (1a) mainly containing a styrene block and a diene block, and particles comprising a tackifier resin (2) (B) A rubber block copolymer mainly containing a styrene block and a diene block 1. Particles comprising polymer (1b) and plasticizer (3) Furthermore, the adhesive material of 1 with which the following particle | grains (C) are mixed.
(C) Particles comprising a rubbery block copolymer (1c) mainly containing a styrene block and a diene block; The pressure-sensitive adhesive material according to 1 or 2, wherein the following components are contained in the following amounts.
The rubbery block copolymer (1): (1a) and (1b) or (1a), (1b) and (1c) combined rubbery block copolymer (1): 40 to 70% by weight
The tackifier resin (2): 20 to 50% by weight
The plasticizer (3): 10 to 30% by weight
4). 2. The particle for an adhesive material according to 1, comprising a rubbery block copolymer (1a) mainly containing a styrene block and a diene block and a tackifier resin (2).
5). The particle | grains for adhesive materials of 4 in which the said tackifying resin (2) is contained 40 to 90weight%.
6). 2. The particle for an adhesive material according to 1, comprising a rubbery block copolymer (1b) mainly containing a styrene block and a diene block, and a plasticizer (3).
7). A rubber block copolymer (1a) mainly containing a styrene block and a diene block and a tackifying resin (2) are melt-mixed to produce particles (A), and mainly contains a styrene block and a diene block. 2. The pressure-sensitive adhesive material according to 1, wherein the rubber block copolymer (1b) and the plasticizer (3) are melt-mixed to produce particles (B), and the particles (A) and the particles (B) are dry blended. Manufacturing method.
8). A rubber block copolymer (1a) mainly containing a styrene block and a diene block and a tackifying resin (2) are melt-mixed to produce particles (A), and mainly contains a styrene block and a diene block. The rubber block copolymer (1b) and the plasticizer (3) are melt mixed to produce particles (B), and the rubber block copolymer (1c) mainly containing styrene blocks and diene blocks is melted. 3. The method for producing a pressure-sensitive adhesive material according to 2, wherein particles (C) are produced by mixing, and the particles (A), the particles (B), and the particles (C) are dry blended.
9. A pressure-sensitive adhesive material comprising 50 to 55% by weight of a rubbery block copolymer (1), 24 to 30% by weight of a tackifier resin (2), and 18 to 21% by weight of a plasticizer (3).
The manufacturing method of the adhesive material which melt-kneads the adhesive material in any one of 10.1-3 with a single screw extruder, and is extrusion-molded.
11. A method for producing a laminate comprising a pressure-sensitive adhesive layer and a resin layer, wherein the pressure-sensitive adhesive material according to any one of 11.1 to 3 is melt-kneaded with a single screw extruder and co-extruded with a resin.
The manufacturing method of the multilayer body which melt-bonds the adhesive body manufactured by 12.10, or the laminated body manufactured by 11 to a base material.

本発明によれば、単軸押出し機で押出せる、再粘着強度の強い粘着材料を提供することができる。   ADVANTAGE OF THE INVENTION According to this invention, the adhesive material with strong re-adhesion intensity | strength which can be extruded with a single screw extruder can be provided.

本発明の粘着材料は、下記粒子（Ａ），（Ｂ）を混合して含む。
（Ａ）主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ａ）と、粘着付与樹脂（２）からなる粒子
（Ｂ）主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ｂ）と、可塑剤（３）からなる粒子 The pressure-sensitive adhesive material of the present invention contains the following particles (A) and (B) mixed.
(A) Rubber block copolymer (1a) mainly containing a styrene block and a diene block, and particles comprising a tackifier resin (2) (B) A rubber block copolymer mainly containing a styrene block and a diene block Particles comprising polymer (1b) and plasticizer (3)

スチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ａ），（１ｂ）は、スチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体水素添加物も含む。例えば、ポリスチレンブロックとビニル−ポリイソプレンブロックが結合したブロック共重合体、ポリスチレンブロックとエチレン−プロピレンブロックが結合したブロック共重合体、ポリスチレンブロックとエチレン−ブタジエンブロックが結合したブロック共重合体、ポリスチレンブロックとエチレン−エチレン−プロピレンブロックが結合したブロック共重合体等が挙げられる。好ましくは、臭気がないことからゴム質ブロック共重合体水素添加物である。
また、ゴム質ブロック共重合体（１ａ）とゴム質ブロック共重合体（１ｂ）は、同じでも異なってもよい。
尚、本発明のゴム質ブロック共重合体（１ａ），（１ｂ）は、その特性を損なわない範囲において、予め、酸化防止剤及び滑剤等を加えて造粒してもよい。 The rubbery block copolymers (1a) and (1b) containing a styrene block and a diene block also contain a hydrogenated rubbery block copolymer containing a styrene block and a diene block. For example, block copolymer in which polystyrene block and vinyl-polyisoprene block are combined, block copolymer in which polystyrene block and ethylene-propylene block are combined, block copolymer in which polystyrene block and ethylene-butadiene block are combined, polystyrene block And a block copolymer in which an ethylene-ethylene-propylene block is bonded. Preferably, it is a hydrogenated rubber block copolymer because it has no odor.
Further, the rubbery block copolymer (1a) and the rubbery block copolymer (1b) may be the same or different.
The rubbery block copolymers (1a) and (1b) of the present invention may be granulated in advance by adding an antioxidant, a lubricant and the like as long as the properties are not impaired.

粘着付与樹脂（２）としては、例えば、水添ロジン系樹脂、テルペン系樹脂、水添テルペン系樹脂、Ｃ５・Ｃ６系脂肪族石油樹脂、脂環族石油樹脂等が挙げられる。
粒子（Ａ）において、粘着付与樹脂は、通常、４０重量％以上９０重量％以下で配合することが望ましい。粘着付与樹脂が４０重量％未満の場合、造粒品がベタつくことがあり、９０重量％を超える場合、造粒品が脆くスクリューに破片が付着することがある。 Examples of the tackifier resin (2) include hydrogenated rosin resins, terpene resins, hydrogenated terpene resins, C5 / C6 aliphatic petroleum resins, and alicyclic petroleum resins.
In the particles (A), it is usually desirable that the tackifier resin is blended in an amount of 40 wt% to 90 wt%. When the tackifying resin is less than 40% by weight, the granulated product may be sticky, and when it exceeds 90% by weight, the granulated product is brittle and fragments may adhere to the screw.

可塑剤（３）としては、例えば、流動パラフィン、プロセスオイル（芳香族系又はナフテン系又はパラフィン系石油系単価水素）、合成ワックス等が挙げられる。
粒子（Ｂ）において、可塑剤の配合量は、通常、押出し安定性を確保するために４０重量％以上７５重量％未満が好ましい。配合量が４０重量％未満の場合、得られる粘着材料のカット性、剥離のスリップスティック性等の調節範囲が狭くなり、７５重量％以上では混練が不均一になる。 Examples of the plasticizer (3) include liquid paraffin, process oil (aromatic, naphthenic, or paraffinic petroleum unit hydrogen), synthetic wax, and the like.
In the particles (B), the blending amount of the plasticizer is usually preferably 40% by weight or more and less than 75% by weight in order to ensure the extrusion stability. When the blending amount is less than 40% by weight, the adjustment range of the obtained adhesive material such as the cut property and the peel stick property of peeling becomes narrow, and when it is 75% by weight or more, the kneading becomes uneven.

本発明の粘着材料は、上記粒子（Ａ），（Ｂ）に加え、さらに下記粒子（Ｃ）を混合すると、ゴム質ブロック共重合体、粘着付与樹脂及び可塑剤の配合比率を調整することができ、粘着材料の要求に応じた物性変更ができる点で好ましい。
（Ｃ）主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ｃ） The pressure-sensitive adhesive material of the present invention can adjust the blending ratio of the rubber block copolymer, the tackifier resin and the plasticizer by mixing the following particles (C) in addition to the particles (A) and (B). This is preferable in that the physical properties can be changed according to the requirements of the adhesive material.
(C) Rubber block copolymer (1c) mainly containing styrene block and diene block

ゴム質ブロック共重合体（１ｃ）として、上記ゴム質ブロック共重合体（１ａ），（１ｂ）と同じ共重合体を使用できる。また、ゴム質ブロック共重合体（１ｃ）は、ゴム質ブロック共重合体（１ａ），（１ｂ）と同じでも異なってもよい。
尚、ゴム質ブロック共重合体（１ｃ）はその特性を損なわない範囲において、予め、酸化防止剤及び滑剤等を加えて造粒してもよい。 As the rubbery block copolymer (1c), the same copolymer as the rubbery block copolymers (1a) and (1b) can be used. Further, the rubber block copolymer (1c) may be the same as or different from the rubber block copolymers (1a) and (1b).
The rubbery block copolymer (1c) may be granulated in advance by adding an antioxidant, a lubricant and the like as long as the properties are not impaired.

本発明の粘着材料は、粘着材料に含まれる全てのゴム質ブロック共重合体（１）、即ち、上記ゴム質ブロック重合体（１ａ）及び（１ｂ）、又は（１ａ），（１ｂ）及び（１ｃ）を合わせたゴム質ブロック共重合体（１）、粘着付与樹脂（２）及び可塑剤（３）の配合量が、好ましくは４０〜７０重量％：２０〜５０重量％：１０〜３０重量％であり、より好ましくは４０〜６０重量％：２２〜５０重量％：１０〜２８重量％である。
（１）、（２）及び（３）の配合量が上記範囲から外れる場合、再接着強度が弱くなる恐れがある。
特に、ゴム質ブロック共重合体（１）５０〜５５重量％と、粘着付与樹脂（２）２４〜
３０重量％と、可塑剤（３）１８〜２１重量％を含む粘着材料は、新規な粘着材料である。 The pressure-sensitive adhesive material of the present invention comprises all rubbery block copolymers (1) contained in the pressure-sensitive adhesive material, that is, the rubbery block polymers (1a) and (1b), or (1a), (1b) and ( The blending amount of the rubber block copolymer (1) combined with 1c), the tackifier resin (2) and the plasticizer (3) is preferably 40 to 70% by weight: 20 to 50% by weight: 10 to 30% by weight. %, More preferably 40 to 60% by weight: 22 to 50% by weight: 10 to 28% by weight.
If the blending amount of (1), (2) and (3) is out of the above range, the re-adhesion strength may be weakened.
In particular, the rubbery block copolymer (1) 50 to 55% by weight and the tackifier resin (2) 24 to
The pressure-sensitive adhesive material containing 30% by weight and 18 to 21% by weight of the plasticizer (3) is a novel pressure-sensitive adhesive material.

本発明の粘着材料は、例えば、以下の製造方法により作製できる。
主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ａ）と、粘着付与樹脂（２）を溶融混合して粒子（Ａ）を製造する。一方、主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ｂ）と、可塑剤（３）を溶融混合して粒子（Ｂ）を製造する。その後、粒子（Ａ）と粒子（Ｂ）をドライブレンドする。 The pressure-sensitive adhesive material of the present invention can be produced, for example, by the following production method.
A rubbery block copolymer (1a) mainly containing a styrene block and a diene block and a tackifying resin (2) are melt-mixed to produce particles (A). On the other hand, a rubbery block copolymer (1b) mainly containing a styrene block and a diene block and a plasticizer (3) are melt-mixed to produce particles (B). Thereafter, the particles (A) and the particles (B) are dry blended.

粒子（Ａ）は、ゴム質ブロック共重合体（１ａ）と、粘着付与樹脂（２）を二軸押出し機又はバンバリーミキサー等で造粒して得られる。
造粒物がベタつく場合には、ブロッキングを防止するためタルク粉等の滑剤を造粒物に適宜ブレンドするとよい。造粒時に充填剤、酸化防止剤、着色剤等を必要に応じて加える。 The particles (A) are obtained by granulating the rubber block copolymer (1a) and the tackifying resin (2) with a twin screw extruder or a Banbury mixer.
When the granulated product is sticky, a lubricant such as talc powder may be appropriately blended with the granulated product to prevent blocking. During granulation, a filler, an antioxidant, a colorant and the like are added as necessary.

粒子（Ｂ）は、ゴム質ブロック共重合体（１ｂ）と、可塑剤（３）を二軸押出し機又はバンバリーミキサー等で造粒して得られる。
造粒物がベタつく場合には、ブロッキングを防止するためタルク粉等の滑剤を造粒物に適宜ブレンドするとよい。造粒時に充填剤、酸化防止剤、着色剤等を必要に応じて加える。 The particles (B) are obtained by granulating the rubber block copolymer (1b) and the plasticizer (3) with a twin screw extruder or a Banbury mixer.
When the granulated product is sticky, a lubricant such as talc powder may be appropriately blended with the granulated product to prevent blocking. During granulation, a filler, an antioxidant, a colorant and the like are added as necessary.

好ましくは、さらに主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ｃ）を溶融混合して粒子（Ｃ）を製造し、粒子（Ａ）、粒子（Ｂ）と共に、粒子（Ｃ）をドライブレンドする。
ゴム質ブロック共重合体（１ｃ）は予め、剥離強度調整剤、充填剤、酸化防止剤、着色剤等を加えて造粒してもよい。 Preferably, the rubbery block copolymer (1c) mainly containing a styrene block and a diene block is melt-mixed to produce particles (C), and the particles (C) together with the particles (A) and (B). ) Dry blend.
The rubbery block copolymer (1c) may be granulated in advance by adding a peel strength adjusting agent, a filler, an antioxidant, a colorant and the like.

本発明の粘着材料は、上記のような粒子（Ａ），（Ｂ）又は（Ａ），（Ｂ），（Ｃ）を混合しているので、押出し機のホッパー等に付着しにくく、単軸押出し機で溶融混練できる。本発明の粘着材料は、押出し成形して粘着物とすることができる。
尚、押出し機は、単軸押出し機のほか、二軸押出し機、混練機等を用いることもできる。 The pressure-sensitive adhesive material of the present invention is mixed with the particles (A), (B) or (A), (B), (C) as described above. It can be melt-kneaded with an extruder. The pressure-sensitive adhesive material of the present invention can be extruded to form a pressure-sensitive adhesive.
The extruder may be a single screw extruder, a twin screw extruder, a kneader or the like.

押出し成形としては、例えば、共押出し、押出しコーティング及び押出しラミネーションが挙げられる。   Examples of extrusion molding include coextrusion, extrusion coating, and extrusion lamination.

共押出しとは、例えば、樹脂層／粘着材料／樹脂層の様な粘着材料を中間層とした３層以上の共押出し、又は樹脂層／粘着材料の様な粘着材料を片面層とした２層以上の共押出しをいう。樹脂層は、ポリオレフィン等からなる。   Co-extrusion is, for example, co-extrusion of three or more layers using an adhesive material such as resin layer / adhesive material / resin layer as an intermediate layer, or two layers using an adhesive material such as resin layer / adhesive material as one side layer The above coextrusion is said. The resin layer is made of polyolefin or the like.

押出しコーティングでは、例えば、紙、合成樹脂フィルム（ポリエチレンテレフタレート（ＰＥＴ）、エチレン−ビニルアルコール共重合体（ＥＶＯＨ）、メタキシレンダイアミン（ＭＸＤ）ナイロン、ポリプロピレン（ＰＰ）、ポリエチンレン（ＰＥ）、ナイロン）、不織布を基材として、基材上に粘着材料をコーティングする。   For extrusion coating, for example, paper, synthetic resin film (polyethylene terephthalate (PET), ethylene-vinyl alcohol copolymer (EVOH), metaxylene diamine (MXD) nylon, polypropylene (PP), polyethylene (PE), nylon) The adhesive material is coated on the base material using the non-woven fabric as the base material.

押出しラミネーションでは、例えば、紙、合成樹脂フィルム（ＰＥＴ、ＥＶＯＨ、ＭＸＤナイロン、ＰＰ、ＰＥ、ナイロン等）、不織布又はこれらが積層されたフィルムの何れかから選択される２種のフィルムの間に粘着材料を溶融押出しし、２種を圧着し積層する。   In extrusion lamination, for example, paper, synthetic resin film (PET, EVOH, MXD nylon, PP, PE, nylon, etc.), non-woven fabric, or an adhesive between two types of films selected from these laminated films The material is melt-extruded, and the two are pressed and laminated.

本発明の粘着材料を押し出し成形して得られる粘着物、又は共押出しにより得られる粘着層と樹脂層からなる積層体を、基材に溶融接着して多層体を得ることができる。基材としては、上述したものが使用できる。   A multi-layered product can be obtained by melt-bonding a pressure-sensitive adhesive obtained by extruding the pressure-sensitive adhesive material of the present invention or a laminate comprising a pressure-sensitive adhesive layer and a resin layer obtained by coextrusion to a substrate. As the substrate, those described above can be used.

本発明の粘着材料からなる粘着層を含む多層体と、この多層体に接着する部材から、包装体又は少なくとも包装体の開閉部を構成することができる。多層体又は接着部材を剥離すると、多層体が破断して、粘着層が露出する。この露出した粘着層に、再度破断部を合わすことによって包装体を再封できる。   The multilayer body including the adhesive layer made of the adhesive material of the present invention and a member bonded to the multilayer body can constitute a package or at least an opening / closing part of the package. When the multilayer body or the adhesive member is peeled off, the multilayer body is broken and the adhesive layer is exposed. The package can be resealed by fitting the broken portion to the exposed adhesive layer again.

以下、本発明を実施例によってさらに具体的に説明する。
［評価方法］
得られた試料の評価は下記の方法で行った。
（Ｉ）押出し性：サージングやホッパー下のスクリュー汚れを確認し何れの問題無いものを良好、いずれかの不良現象が見られたものを不良と判定した。
（ＩＩ）再接着強度：製作した３層の多層フィルムの高密度ポリエチレン（ＨＤＰＥ）面に対して、ポリエチレンテレフタレート（ＰＥＴ）（１２μｍ）／直鎖状低密度ポリエチレン（Ｌ−ＬＤＰＥ）（６０μｍ）ラミネートフィルムを、１９０℃２Ｍｐａの面圧でＰＥＴ面からヒートシール歯を押し当て面積５０ｍｍ×５０ｍｍのヒートシールを行い接着した。次に１５ｍｍ幅でスリットしてから一度手ではがし、再度手で押圧した後の再接着強度をプッシュプルスケール（（株）イマダ製ＭＸ−５００Ｎ）で測定した。可否判定の目安として１Ｎ／１５ｍｍ〜２Ｎ／１５ｍｍ未満を可、２Ｎ／１５ｍｍ〜３Ｎ／１５ｍｍ未満を良好、３Ｎ／１５ｍｍ以上を最良とした。また、１Ｎ／１５ｍｍ未満を不可とした。 Hereinafter, the present invention will be described more specifically with reference to examples.
[Evaluation methods]
The obtained sample was evaluated by the following method.
(I) Extrudability: Surging and screw contamination under the hopper were confirmed, and any problem was determined to be good, and any defect was determined to be defective.
(II) Re-adhesion strength: Polyethylene terephthalate (PET) (12 μm) / linear low-density polyethylene (L-LDPE) (60 μm) laminate on the high-density polyethylene (HDPE) surface of the three-layer multilayer film produced The film was bonded by performing heat sealing with a surface area of 50 mm × 50 mm by pressing the heat seal teeth from the PET surface at a surface pressure of 190 ° C. and 2 Mpa. Next, after slitting with a width of 15 mm, it was peeled once by hand, and the re-adhesion strength after pressing again by hand was measured with a push-pull scale (MX-500N manufactured by Imada Co., Ltd.). 1N / 15mm to less than 2N / 15mm is acceptable as a guideline for determining whether or not possible, 2N / 15mm to less than 3N / 15mm is good, and 3N / 15mm or more is the best. Moreover, less than 1N / 15mm was made impossible.

実施例１
［粒子状粘着材料の製造］
（１）スチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（スチレン系エラストマーと以下略称する）と粘着付与樹脂との混練造粒（粒子（Ａ１））
ポリスチレン−ポリイソプレンブロック共重合体（日本ゼオン（株）製、クインタック３５２０）（ＭＦＲ＝７ｇ／１０分（２００℃、荷重５ｋｇ）、比重０．９３）５０重量％に対し、Ｃ５−芳香族系共重合水素添加樹脂粒子（出光興産（株）製、アイマーブＰ−１２５）（軟化点１２５℃、密度１．０３ｇ／ｃｍ３（２０℃））５０重量％を混合したもの１００重量部に、酸化防止剤（チバスペシャリティケミカル（株）製、イルガノックス１０１０）を１重量部加えて攪拌混合した。この後、二軸押出し機にて１８０℃の温度で溶融混合して、水冷ストランド押出しし、さらにこれをカッティングし造粒した。 Example 1
[Manufacture of particulate adhesive materials]
(1) Kneading granulation (particle (A1)) of a rubbery block copolymer (hereinafter abbreviated as styrene elastomer) containing a styrene block and a diene block and a tackifier resin
Polystyrene-polyisoprene block copolymer (manufactured by Nippon Zeon Co., Ltd., Quintac 3520) (MFR = 7 g / 10 min (200 ° C., load 5 kg), specific gravity 0.93) 50% by weight with respect to C5-aromatic 100 parts by weight of 50% by weight of a copolymer-copolymerized hydrogenated resin particle (Idemitsu Kosan Co., Ltd., Imabe P-125) (softening point 125 ° C., density 1.03 g / cm 3 (20 ° C.)) One part by weight of an antioxidant (manufactured by Ciba Specialty Chemicals Co., Ltd., Irganox 1010) was added and stirred and mixed. Then, it melt-mixed at the temperature of 180 degreeC with the twin-screw extruder, the water-cooled strand extrusion was carried out, and this was further cut and granulated.

（２）スチレン系エラストマーと可塑剤との混練造粒（粒子（Ｂ１））
ポリスチレン−ポリイソプレンブロック共重合体（日本ゼオン（株）製、クインタック３５２０）（ＭＦＲ＝７ｇ／１０分（２００℃、荷重５ｋｇ）、比重０．９３）６０重量％に対し、プロセスオイル（出光興産（株）製、ダイアナプロセスオイルＰＷ−９０）（密度０．８７２２ｇ／ｃｍ３（１５℃））４０重量％加えて攪拌混合した後、二軸押出し機にて１８０℃の温度で溶融混合して、水冷ストランド押出しし、さらにこれをカッティングし造粒した。
造粒品は梱包保管中粒子同士のブロッキングを防ぐため造粒品１００重量部に対しタルク粉を０．５重量部外添した。 (2) Kneading granulation of styrene elastomer and plasticizer (particle (B1))
Polystyrene-polyisoprene block copolymer (manufactured by Nippon Zeon Co., Ltd., QUINTAC 3520) (MFR = 7 g / 10 min (200 ° C., load 5 kg), specific gravity 0.93) 60% by weight of process oil (Idemitsu Kosan Co., Ltd., Diana Process Oil PW-90) (density 0.8722 g / cm 3 (15 ° C.)) 40 wt% was added and stirred and mixed, then melt mixed at a temperature of 180 ° C. with a twin screw extruder. Then, water-cooled strand extrusion was performed, and this was cut and granulated.
In the granulated product, 0.5 part by weight of talc powder was externally added to 100 parts by weight of the granulated product in order to prevent blocking of particles during packing storage.

（３）粒子（Ａ１），（Ｂ１）の混合
上記粒子（Ａ１）と粒子（Ｂ１）を１：１の重量比率で混合して粘着材料を製造した。スチレン系エラストマー、粘着付与樹脂及び可塑剤の配合比率は５５．０重量％：２５．０重量％：２０．０重量％であった。 (3) Mixing of particles (A1) and (B1) The particles (A1) and particles (B1) were mixed at a weight ratio of 1: 1 to produce an adhesive material. The blending ratio of the styrene elastomer, tackifying resin and plasticizer was 55.0 wt%: 25.0 wt%: 20.0 wt%.

［粘着材料の共押出し］
ＨＤＰＥ（プライムポリマー（株）製、ハイゼックス１１０Ｊ）（ＭＦＲ＝１２ｇ／１０分、密度０．９６２ｇ／ｃｍ３）、上記で得られた粘着材料及びランダムポリプロピレン（ＲＰＰ）（プライムポリマー（株）製、プライムポリプロＦ−７４４ＮＰ）（ＭＦＲ＝６．４ｇ／１０分、密度０．９ｇ／ｃｍ３）を、いずれもＬ／Ｄ＝２６のフルフライトスクリューが備わった３台の３０ｍｍφ単軸押出機と多層フィードブロックとＴダイ（幅４００ｍｍ）からなる多層フィルムキャスト製造装置を用いて、２２０℃で押出し、３層の多層フィルムを製作した。フィルムの厚みは、ＨＤＰＥ層１０μｍ／粘着物層２０μｍ／ＲＰＰ層５０μｍとした。粘着材料は長時間継続してスムーズに押出すことができた。結果を表１に示す。 [Co-extrusion of adhesive materials]
HDPE (manufactured by Prime Polymer Co., Ltd., Hi-Zex 110J) (MFR = 12 g / 10 min, density 0.962 g / cm 3 ), the adhesive material obtained above and random polypropylene (RPP) (manufactured by Prime Polymer Co., Ltd., Prime Polypro F-744NP) (MFR = 6.4 g / 10 min, density 0.9 g / cm 3 ), three 30 mmφ single-screw extruders and multi-layers each equipped with a full flight screw with L / D = 26 Extrusion was performed at 220 ° C. using a multilayer film cast production apparatus consisting of a feed block and a T die (width 400 mm) to produce a three-layer multilayer film. The thickness of the film was HDPE layer 10 μm / adhesive layer 20 μm / RPP layer 50 μm. The adhesive material could be extruded smoothly for a long time. The results are shown in Table 1.

実施例２
［粒子状粘着材料の製造］
（１）スチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（スチレン系エラストマーと以下略称する）と粘着付与樹脂との混練造粒（粒子（Ａ１））
ポリスチレン−ポリイソプレンブロック共重合体（日本ゼオン（株）製、クインタック３５２０）（ＭＦＲ＝７ｇ／１０分（２００℃、荷重５ｋｇ）、比重０．９３）２５重量％に対し、Ｃ５−芳香族系共重合水素添加樹脂粒子（出光興産（株）製、アイマーブＰ−１２５）（軟化点１２５℃、密度１．０３ｇ／ｃｍ３（２０℃））７５重量％を混合したもの１００重量部に、酸化防止剤（チバスペシャリティケミカル（株）製、イルガノックス１０１０）を１重量部加えて攪拌混合した。この後、二軸押出し機にて１８０℃の温度で溶融混合して、水冷ストランド押出しし、さらにこれをカッティングし造粒した。 Example 2
[Manufacture of particulate adhesive materials]
(1) Kneading granulation (particle (A1)) of a rubbery block copolymer (hereinafter abbreviated as styrene elastomer) containing a styrene block and a diene block and a tackifier resin
Polystyrene-polyisoprene block copolymer (manufactured by Nippon Zeon Co., Ltd., Quintac 3520) (MFR = 7 g / 10 min (200 ° C., load 5 kg), specific gravity 0.93) 25% by weight with respect to C5-aromatic To 100 parts by weight of a mixture of 75% by weight of copolymerized hydrogenated resin particles (Idemitsu P-125, Idemitsu Kosan Co., Ltd., softening point 125 ° C., density 1.03 g / cm 3 (20 ° C.)), One part by weight of an antioxidant (manufactured by Ciba Specialty Chemicals Co., Ltd., Irganox 1010) was added and stirred and mixed. Then, it melt-mixed at the temperature of 180 degreeC with the twin-screw extruder, the water-cooled strand extrusion was carried out, and this was further cut and granulated.

（２）スチレン系エラストマーと可塑剤との混練造粒（粒子（Ｂ１））
ポリスチレン−ポリイソプレンブロック共重合体（日本ゼオン（株）製、クインタック３５２０）（ＭＦＲ＝７ｇ／１０分（２００℃、荷重５ｋｇ）、比重０．９３）４０重量％に対し、プロセスオイル（出光興産（株）製、ダイアナプロセスオイルＰＷ−９０）（密度０．８７２２ｇ／ｃｍ３（１５℃））６０重量％加えて攪拌混合した後、二軸押出し機にて１８０℃の温度で溶融混合して、水冷ストランド押出しし、さらにこれをカッティングし造粒した。
造粒品は梱包保管中粒子同士のブロッキングを防ぐため造粒品１００重量部に対しタルク粉を０．５重量部外添した。 (2) Kneading granulation of styrene elastomer and plasticizer (particle (B1))
Polystyrene-polyisoprene block copolymer (manufactured by Nippon Zeon Co., Ltd., Quintac 3520) (MFR = 7 g / 10 min (200 ° C., load 5 kg), specific gravity 0.93) 40% by weight with respect to process oil (Idemitsu Kosan Co., Ltd., Diana Process Oil PW-90) (density 0.8722 g / cm 3 (15 ° C.)) 60% by weight was added and stirred and mixed, then melt mixed at a temperature of 180 ° C. with a twin screw extruder. Then, water-cooled strand extrusion was performed, and this was cut and granulated.
In the granulated product, 0.5 part by weight of talc powder was externally added to 100 parts by weight of the granulated product in order to prevent blocking of particles during packing storage.

（３）粒子（Ａ１），（Ｂ１）の混合
上記粒子（Ａ１）と粒子（Ｂ１）に、スチレン系ゴム質ブロック共重合体粒子（日本ゼオン（株）製、クインタックＳＬ−１２５）（ＭＦＲ＝１７ｇ／１０分（２００℃、荷重５ｋｇ）、比重０．９３）を加えて混合して粘着材料を製造した。スチレン系エラストマー、粘着付与樹脂及び可塑剤の配合比率は５０．８重量％：３０．０重量％：１９．２重量％であった。 (3) Mixing of particles (A1) and (B1) The particles (A1) and particles (B1) are mixed with styrene rubber block copolymer particles (manufactured by Nippon Zeon Co., Ltd., Quintac SL-125) (MFR). = 17 g / 10 min (200 ° C., load 5 kg), specific gravity 0.93) was added and mixed to produce an adhesive material. The blending ratio of the styrene elastomer, the tackifier resin and the plasticizer was 50.8% by weight: 30.0% by weight: 19.2% by weight.

［粘着材料の共押出し］
ＨＤＰＥ（プライムポリマー（株）製、ハイゼックス１１０Ｊ）（ＭＦＲ＝１２ｇ／１０分、密度０．９６２ｇ／ｃｍ３）、上記で得られた粘着材料及びランダムポリプロピレン（ＲＰＰ）（プライムポリマー（株）製、プライムポリプロＦ−７４４ＮＰ）（ＭＦＲ＝６．４ｇ／１０分、密度０．９ｇ／ｃｍ３）を、いずれもＬ／Ｄ＝２６のフルフライトスクリューが備わった３台の３０ｍｍφ単軸押出機と多層フィードブロックとＴダイ（幅４００ｍｍ）からなる多層フィルムキャスト製造装置を用いて、２２０℃で押出し、３層の多層フィルムを製作した。フィルムの厚みは、ＨＤＰＥ層１０μｍ／粘着物層２０μｍ／ＲＰＰ層５０μｍとした。粘着材料は長時間継続してスムーズに押出すことができた。結果を表１に示す。 [Co-extrusion of adhesive materials]
HDPE (manufactured by Prime Polymer Co., Ltd., Hi-Zex 110J) (MFR = 12 g / 10 min, density 0.962 g / cm 3 ), the adhesive material obtained above and random polypropylene (RPP) (manufactured by Prime Polymer Co., Ltd., Prime Polypro F-744NP) (MFR = 6.4 g / 10 min, density 0.9 g / cm 3 ), three 30 mmφ single-screw extruders and multi-layers each equipped with a full flight screw with L / D = 26 Extrusion was performed at 220 ° C. using a multilayer film cast production apparatus consisting of a feed block and a T die (width 400 mm) to produce a three-layer multilayer film. The thickness of the film was HDPE layer 10 μm / adhesive layer 20 μm / RPP layer 50 μm. The adhesive material could be extruded smoothly for a long time. The results are shown in Table 1.

比較例１
実施例２で用いた粒子（Ｂ１）３２重量％に、Ｃ５−芳香族系共重合水素添加樹脂粒子（出光興産（株）製、アイマーブＰ−１２５）（軟化点１２５℃、密度１．０３ｇ／ｃｍ３（２０℃））を３０重量％加え、さらにスチレン系エラストマー粒子としてＳＬ−１２５ ３８重量％を混合することにより、スチレン系エラストマー：粘着付与樹脂：可塑剤の比率を５０．８重量％：３０．０重量％：１９．２重量％とした。
上記の粘着材料を用いた他は実施例２と同様の方法でフィルムを製造した。押出しを始めてから、しばらくすると粘着物層の押出し量が変動し始めた。
この押出し機を停止し、ホッパー下のスクリュー汚れを確認したところスクリュー溝に石油樹脂が軟化付着しており、押出し不良を生じたことが分かった。結果を表１に示す。
尚、比較例１では、サンプルを採取できなかったので、再接着強度は評価していない。 Comparative Example 1
To 32% by weight of the particles (B1) used in Example 2, C5-aromatic copolymer hydrogenated resin particles (Idemitsu Kosan Co., Ltd., Imabe P-125) (softening point 125 ° C., density 1.03 g / cm 3 (20 ° C.)) and 30% by weight of SL-125 as styrene-based elastomer particles are mixed to obtain a ratio of styrene-based elastomer: tackifying resin: plasticizer of 50.8% by weight: 30.0% by weight: 19.2% by weight.
A film was produced in the same manner as in Example 2 except that the above adhesive material was used. After a while from the start of extrusion, the extrusion amount of the adhesive layer started to fluctuate.
When this extruder was stopped and screw contamination under the hopper was confirmed, it was found that petroleum resin was softened and adhered to the screw groove, resulting in poor extrusion. The results are shown in Table 1.
In Comparative Example 1, since the sample could not be collected, the re-adhesion strength was not evaluated.

実施例３−１５
実施例２で用いた粒子（Ａ１）と粒子（Ｂ１）を、スチレン系エラストマー：粘着付与樹脂：可塑剤の比率が表１のようになるように配合して実施例２と同様にフィルムを製造すると共に同様の評価を行った。結果を表１に示す。 Example 3-15
The particles (A1) and particles (B1) used in Example 2 were blended so that the ratio of styrene elastomer: tackifier resin: plasticizer was as shown in Table 1, and a film was produced in the same manner as in Example 2. And the same evaluation was performed. The results are shown in Table 1.

比較例２−５
実施例２で用いた粒子（Ａ１）に、ＳＬ−１２５粒子を、スチレン系エラストマー：粘着付与樹脂：可塑剤の比率が表１のようになるように配合して、実施例２と同様にフィルムを製造すると共に同様の評価を行った。結果を表１に示す。 Comparative Example 2-5
In the same manner as in Example 2, the SL-125 particles were blended with the particles (A1) used in Example 2 so that the ratio of styrene elastomer: tackifier resin: plasticizer was as shown in Table 1. And the same evaluation was performed. The results are shown in Table 1.

Figure 2007284464
Figure 2007284464

実施例１６−１８
粒子（Ａ１）のスチレン系エラストマーと粘着付与樹脂の配合比率を表２に示すように変更した他は、実施例２と同様に粒子を製造した。粒子を２０ｋｇずつ袋に充填包装し２週間保管後のペレット間のブロッキングを評価した。結果を表２に示す。 Examples 16-18
Particles were produced in the same manner as in Example 2 except that the blending ratio of the styrene-based elastomer and the tackifier resin of the particles (A1) was changed as shown in Table 2. Particles were packed and packaged in 20 kg bags, and blocking between pellets after storage for 2 weeks was evaluated. The results are shown in Table 2.

実施例１９−２１
粒子（Ａ１）のスチレン系エラストマーと粘着付与樹脂の配合比率を表２に示すように変更した他は、実施例２と同様に粒子を製造した。実施例１６−１８と同様に評価した。結果を表２に示す。 Example 19-21
Particles were produced in the same manner as in Example 2 except that the blending ratio of the styrene-based elastomer and the tackifier resin of the particles (A1) was changed as shown in Table 2. Evaluation was performed in the same manner as in Examples 16-18. The results are shown in Table 2.

Figure 2007284464
Figure 2007284464

実施例２２
実施例２で製造した粘着材料を４０ｍｍφシングルフライトスクリュー（Ｌ／Ｄ＝２８）押出し機に幅５００ｍｍのＴダイが付き、押出したメルトウェブをゴムロールと冷却金属ロールの２本ロールで圧着する押出しラミネータを用いて、メルトウェブの両側紙及びシリコーンコート工程紙（コート側をメルトウェブ側にする）を通紙した。構成は印刷紙（１５０ｇ／ｍ２）／粘着材層（２０μｍ）／工程紙（１００ｇ／ｍ２）であった。 Example 22
Extrusion laminator in which the adhesive material produced in Example 2 is attached to a 40 mmφ single flight screw (L / D = 28) extruder with a T die having a width of 500 mm, and the extruded melt web is pressure-bonded by two rolls of a rubber roll and a cooling metal roll. Was used to pass both sides of the melt web and the silicone coated process paper (with the coat side on the melt web side). The configuration was printing paper (150 g / m 2 ) / adhesive layer (20 μm) / process paper (100 g / m 2 ).

ラミネートした３層シートを１４０ｍｍ×２１０ｍｍに切断した後、工程紙を剥がし、粘着面をガラスに貼り付けた後、環境温度２３℃に２週間放置した。接着状態は良好で、貼付中の期間は剥がれることなく、２週間後に剥がした時は糊残りなく容易に剥離できた。   After the laminated three-layer sheet was cut into 140 mm × 210 mm, the process paper was peeled off, the adhesive surface was attached to glass, and then left at an environmental temperature of 23 ° C. for 2 weeks. The state of adhesion was good, and it was not peeled off during the sticking period, and when peeled off after 2 weeks, it was easily peeled off without any adhesive residue.

本発明の粘着材料は、ポスター、粘着テープ、ラベル等の産業資材や、再密封食品・医薬品包装資材、保護フィルム等の包装資材として好適に使用できる。
The pressure-sensitive adhesive material of the present invention can be suitably used as industrial materials such as posters, pressure-sensitive adhesive tapes and labels, and packaging materials such as re-sealed food / pharmaceutical packaging materials and protective films.

Claims (12)

下記粒子（Ａ），（Ｂ）が混合されている粘着材料。
（Ａ）主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ａ）と、粘着付与樹脂（２）からなる粒子
（Ｂ）主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ｂ）と、可塑剤（３）からなる粒子 An adhesive material in which the following particles (A) and (B) are mixed.
(A) Rubber block copolymer (1a) mainly containing a styrene block and a diene block, and particles comprising a tackifier resin (2) (B) A rubber block copolymer mainly containing a styrene block and a diene block Particles comprising polymer (1b) and plasticizer (3) さらに、下記粒子（Ｃ）が混合されている請求項１記載の粘着材料。
（Ｃ）主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ｃ）からなる粒子 Furthermore, the adhesive material of Claim 1 with which the following particle | grains (C) are mixed.
(C) Particles mainly composed of a rubbery block copolymer (1c) containing a styrene block and a diene block 下記成分が下記配合量で含まれている請求項１又は２に記載の粘着材料。
前記ゴム質ブロック共重合体（１ａ）及び（１ｂ）、又は（１ａ），（１ｂ）及び（１ｃ）を合わせたゴム質ブロック共重合体（１）： ４０〜７０重量％
前記粘着付与樹脂（２）： ２０〜５０重量％
前記可塑剤（３）： １０〜３０重量％ The pressure-sensitive adhesive material according to claim 1 or 2, wherein the following components are contained in the following amounts.
The rubbery block copolymer (1): (1a) and (1b) or (1a), (1b) and (1c) combined rubbery block copolymer (1): 40 to 70% by weight
The tackifier resin (2): 20 to 50% by weight
The plasticizer (3): 10 to 30% by weight 主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ａ）と、粘着付与樹脂（２）からなる、請求項１に記載の粘着材料用粒子。   The particle | grains for adhesive materials of Claim 1 which consist of a rubbery block copolymer (1a) mainly containing a styrene block and a diene block, and tackifying resin (2). 前記粘着付与樹脂（２）が４０〜９０重量％含まれる請求項４に記載の粘着材料用粒子。   The particles for pressure-sensitive adhesive material according to claim 4, wherein the tackifying resin (2) is contained in an amount of 40 to 90% by weight. 主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ｂ）と、可塑剤（３）からなる、請求項１に記載の粘着材料用粒子。   The particle | grains for adhesive materials of Claim 1 which consist of a rubbery block copolymer (1b) mainly containing a styrene block and a diene block, and a plasticizer (3). 主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ａ）と、粘着付与樹脂（２）を溶融混合して粒子（Ａ）を製造し、
主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ｂ）と、可塑剤（３）を溶融混合して粒子（Ｂ）を製造し、
前記粒子（Ａ）と前記粒子（Ｂ）をドライブレンドする請求項１に記載の粘着材料の製造方法。 A rubber block copolymer (1a) mainly containing a styrene block and a diene block and a tackifying resin (2) are melt-mixed to produce particles (A),
A rubber block copolymer (1b) mainly containing a styrene block and a diene block and a plasticizer (3) are melt-mixed to produce particles (B),
The method for producing an adhesive material according to claim 1, wherein the particles (A) and the particles (B) are dry blended. 主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ａ）と、粘着付与樹脂（２）を溶融混合して粒子（Ａ）を製造し、
主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ｂ）と、可塑剤（３）を溶融混合して粒子（Ｂ）を製造し、
主としてスチレンブロックとジエンブロックとを含有するゴム質ブロック共重合体（１ｃ）を溶融混合して粒子（Ｃ）を製造し、
前記粒子（Ａ）、前記粒子（Ｂ）及び前記粒子（Ｃ）をドライブレンドする請求項２に記載の粘着材料の製造方法。 A rubber block copolymer (1a) mainly containing a styrene block and a diene block and a tackifying resin (2) are melt-mixed to produce particles (A),
A rubber block copolymer (1b) mainly containing a styrene block and a diene block and a plasticizer (3) are melt-mixed to produce particles (B),
A rubber block copolymer (1c) mainly containing a styrene block and a diene block is melt-mixed to produce particles (C),
The method for producing an adhesive material according to claim 2, wherein the particles (A), the particles (B), and the particles (C) are dry blended. ゴム質ブロック共重合体（１）５０〜５５重量％と、粘着付与樹脂（２）２４〜３０重量％と、可塑剤（３）１８〜２１重量％を含む粘着材料。   A pressure-sensitive adhesive material comprising 50 to 55% by weight of a rubbery block copolymer (1), 24 to 30% by weight of a tackifier resin (2), and 18 to 21% by weight of a plasticizer (3). 請求項１〜３のいずれかに記載の粘着材料を単軸押出し機で溶融混練して押出し成形する粘着物の製造方法。   The manufacturing method of the adhesive material which melt-kneads the adhesive material in any one of Claims 1-3 with a single screw extruder, and is extrusion-molded. 請求項１〜３のいずれかに記載の粘着材料を、単軸押出し機で溶融混練して樹脂と共押出しする粘着層と樹脂層からなる積層体の製造方法。   The manufacturing method of the laminated body which consists of the adhesion layer and resin layer which melt-knead the adhesive material in any one of Claims 1-3 with a single screw extruder, and coextrude with resin. 請求項１０で製造した粘着物又は請求項１１で製造した積層体を、基材に溶融接着する多層体の製造方法。

The manufacturing method of the multilayer body which melt-bonds the adhesive body manufactured in Claim 10, or the laminated body manufactured in Claim 11 to a base material.

JP2006109586A 2006-04-12 2006-04-12 Adhesive material, method for producing the same, adhesive material using the same, and method for producing laminate Expired - Fee Related JP3939738B1 (en)

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JP2006109586A JP3939738B1 (en) 2006-04-12 2006-04-12 Adhesive material, method for producing the same, adhesive material using the same, and method for producing laminate
PCT/JP2007/055105 WO2007116626A1 (en) 2006-04-12 2007-03-14 Adhesive material, method for production of the adhesive material, and method for production of adhered article or laminate using the adhesive material
KR1020087023864A KR20080113390A (en) 2006-04-12 2007-03-14 Adhesive material, method for production of the adhesive material, and method for production of adhered article or laminate using the adhesive material

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010132761A (en) * 2008-12-04 2010-06-17 Tosoh Corp Adhesive composition
JP2018111798A (en) * 2017-01-11 2018-07-19 Jsr株式会社 Composition for adhesive
WO2019031354A1 (en) * 2017-08-10 2019-02-14 旭化成株式会社 Composition for pressure-sensitive adhesive, material for pressure-sensitive adhesive, method for forming pressure-sensitive adhesive, pressure-sensitive adhesive, multilayered film, and packaging body
EP3940036A3 (en) * 2020-07-13 2022-08-03 Asahi Kasei Kabushiki Kaisha Material for pressure-sensitive adhesive, method for producing pressure-sensitive adhesive, pressure-sensitive adhesive, multilayer film, and package

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3342117B2 (en) * 1993-06-25 2002-11-05 株式会社クラレ Mixed hot melt adhesive
EP1242535B1 (en) * 1999-12-08 2013-11-20 KRATON Polymers Research B.V. Free flowing powder

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010132761A (en) * 2008-12-04 2010-06-17 Tosoh Corp Adhesive composition
JP2018111798A (en) * 2017-01-11 2018-07-19 Jsr株式会社 Composition for adhesive
WO2019031354A1 (en) * 2017-08-10 2019-02-14 旭化成株式会社 Composition for pressure-sensitive adhesive, material for pressure-sensitive adhesive, method for forming pressure-sensitive adhesive, pressure-sensitive adhesive, multilayered film, and packaging body
JPWO2019031354A1 (en) * 2017-08-10 2020-04-23 旭化成株式会社 Composition for pressure-sensitive adhesive, material for pressure-sensitive adhesive, method for forming pressure-sensitive adhesive, pressure-sensitive adhesive, multilayer film and package
EP3940036A3 (en) * 2020-07-13 2022-08-03 Asahi Kasei Kabushiki Kaisha Material for pressure-sensitive adhesive, method for producing pressure-sensitive adhesive, pressure-sensitive adhesive, multilayer film, and package

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KR20080113390A (en) 2008-12-30
JP3939738B1 (en) 2007-07-04

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