JP2014062199A - Hot-melt adhesive film and molded body - Google Patents
Hot-melt adhesive film and molded body Download PDFInfo
- Publication number
- JP2014062199A JP2014062199A JP2012208760A JP2012208760A JP2014062199A JP 2014062199 A JP2014062199 A JP 2014062199A JP 2012208760 A JP2012208760 A JP 2012208760A JP 2012208760 A JP2012208760 A JP 2012208760A JP 2014062199 A JP2014062199 A JP 2014062199A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- ethylene
- hot
- adhesive film
- melt adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 239000004831 Hot glue Substances 0.000 title claims abstract description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000011347 resin Substances 0.000 claims abstract description 38
- 239000004711 α-olefin Substances 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 29
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 26
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 16
- 150000003505 terpenes Chemical class 0.000 claims abstract description 14
- 235000007586 terpenes Nutrition 0.000 claims abstract description 14
- 150000001993 dienes Chemical class 0.000 claims abstract description 9
- 229920001400 block copolymer Polymers 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 239000003208 petroleum Substances 0.000 claims abstract description 5
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 4
- 229920001577 copolymer Polymers 0.000 claims description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 239000005977 Ethylene Substances 0.000 claims description 12
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical group CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 6
- 229920005672 polyolefin resin Polymers 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 239000004925 Acrylic resin Substances 0.000 claims description 4
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- 239000007769 metal material Substances 0.000 claims description 3
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- 239000002245 particle Substances 0.000 abstract description 2
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- 239000000047 product Substances 0.000 description 33
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- 229920006223 adhesive resin Polymers 0.000 description 18
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- 239000000853 adhesive Substances 0.000 description 15
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- 238000000034 method Methods 0.000 description 13
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- 238000012986 modification Methods 0.000 description 11
- 230000004048 modification Effects 0.000 description 11
- 239000008188 pellet Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 229920000098 polyolefin Polymers 0.000 description 9
- 238000000465 moulding Methods 0.000 description 8
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- 239000004743 Polypropylene Substances 0.000 description 6
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 6
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 6
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 6
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 5
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- 229910000831 Steel Inorganic materials 0.000 description 5
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- 238000002156 mixing Methods 0.000 description 5
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 229920002725 thermoplastic elastomer Polymers 0.000 description 4
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical class OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
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- 239000000499 gel Substances 0.000 description 3
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- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
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- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 2
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- 150000001336 alkenes Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
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- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- JFHBKKGEVRVZPE-UHFFFAOYSA-N oxiran-2-ylmethyl 4-ethenylbenzoate Chemical compound C1=CC(C=C)=CC=C1C(=O)OCC1OC1 JFHBKKGEVRVZPE-UHFFFAOYSA-N 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Laminated Bodies (AREA)
Abstract
Description
本発明はホットメルト接着剤に関する。さらに詳しくはポリオレフィン系樹脂、アクリル系樹脂、ポリカーボネート系樹脂などの難接着性材料との接着性に優れたホットメルト型接着フィルムに関する。 The present invention relates to a hot melt adhesive. More specifically, the present invention relates to a hot-melt adhesive film excellent in adhesiveness to difficult-to-adhere materials such as polyolefin resin, acrylic resin, and polycarbonate resin.
熱可塑性エラストマー、オレフィン系重合体、ビニル系重合体およびエンジニアリングプラスチックス等の熱可塑性樹脂は、物性、成形性および表面特性等に優れているため、目的に応じて塊状、シート状、フィルム状等に加工して自動車、家電、エレクトロニクス、建築、雑貨等の分野で多く使用されている。そして、これらの成形品は、所望形状の製品とするため、あるいは性能の高度化、機能の多様化を図るため複数の成形品を接着させ、複合化することが行われている。中でも、力学的な物性に富む樹脂製の成形品を基材とし、その外層に表面特性、耐候性、装飾性に優れる表皮材、加飾シートを積層することが幅広く行われており、積層体は自動車内装、住宅内装、家電機器の筐体などに多く利用されている。しかしながら、このような積層体は一般に各層間の接着力に乏しく、接着層を設けて積層される例が多い。接着剤としては、溶剤型接着剤とホットメルト型接着剤使用されているが、溶剤型接着剤は、塗布むらが出やすいこと、有機溶剤の使用により環境、衛生上の悪影響を生じるという欠点を有する。そのため、簡便かつ接着強度の優れたホットメルト接着剤が求められている。 Thermoplastic resins such as thermoplastic elastomers, olefin polymers, vinyl polymers, and engineering plastics are excellent in physical properties, moldability, surface properties, etc., so that they can be used in bulk, sheet, film, etc. It is used in many fields such as automobiles, home appliances, electronics, architecture, and sundries. In order to make these molded products into products having a desired shape, or to improve performance and diversify functions, a plurality of molded products are bonded and combined. In particular, it is widely used to laminate a surface material, weather resistance, and decorative sheet with excellent surface properties, weather resistance, and decorativeness on the outer layer of a resin molded product with rich mechanical properties. Is widely used in automobile interiors, house interiors, and housings for home appliances. However, such a laminated body generally has poor adhesion between the layers, and there are many examples in which an adhesive layer is provided and laminated. As adhesives, solvent-type adhesives and hot-melt type adhesives are used, but solvent-type adhesives tend to have uneven coating and have the disadvantages of adversely affecting the environment and hygiene due to the use of organic solvents. Have. Therefore, there is a demand for a hot melt adhesive that is simple and excellent in adhesive strength.
このようなホットメルト型接着剤としては、エチレン系共重合体、スチレン系ブロック共重合体およびオレフィン系（共）重合体からなる群から選ばれる1種以上のベースポリマーと粘着付与樹脂、結晶性極性基含有化合物を含有するもの（特許文献１）、アモルファスポリα−オレフィン、粘着付与樹脂およびポリプロピレン系ワックスを必須成分とするもの（特許文献２）、スチレン−エチレンプロピレン−スチレンブロック共重合ゴムあるいはスチレン−ブタジエン−スチレンブロック共重合ゴムに、粘着付与樹脂成分およびプロセスオイルなどの液状可塑剤を添加してなるもの（特許文献３、４）、変性ポリオレフィンと粘着付与剤を配合してなるもの（特許文献５）、スチレン系ブロック共重合体と酸変性ワックスを配合してなるもの（特許文献６）、酸変性ポリプロピレンと酸変性スチレン系ブロック共重合体を配合してなるもの（特許文献７）、スチレン系ブロック共重合体と粘着付与剤、エチレン系重合体を配合してなるもの（特許文献８、９、１０）などが提案されている。 Such hot melt adhesives include one or more base polymers selected from the group consisting of ethylene copolymers, styrene block copolymers, and olefin (co) polymers, tackifying resins, crystallinity, and the like. A material containing a polar group-containing compound (Patent Document 1), an amorphous poly α-olefin, a tackifier resin and a polypropylene-based wax (Patent Document 2), a styrene-ethylenepropylene-styrene block copolymer rubber, or A styrene-butadiene-styrene block copolymer rubber added with a liquid plasticizer such as a tackifier resin component and process oil (Patent Documents 3 and 4), and a mixture of a modified polyolefin and a tackifier ( Patent Document 5), which is a blend of a styrene block copolymer and an acid-modified wax (Patent Document 6), an acid-modified polypropylene and an acid-modified styrene block copolymer (Patent Document 7), a styrene block copolymer, a tackifier, and an ethylene polymer A thing (patent documents 8, 9, 10) etc. is proposed.
一般的な熱可塑性樹脂の成形品に対して、種々の接着剤はいまだ満足できる接着性を示すには至っていない。成形体の用途としては、自動車内装、住宅内装、家電など意匠性を必要とする用途への要請も多く、意匠性を損なわない為にできるかぎり限りマイルドな加工温度、圧力で使用できる接着剤樹脂組成物が有用であると考えられる。また、これら内装材や筐体は、一般に表皮材と成形品から成り、両者の接着は、通常、成形品の形状に合わせて表皮材を加熱成形しつつ行われることから、予め表皮材に均一かつ簡便に加熱ラミネートして使用できるフィルム状接着剤が好ましい。さらに、表皮材に接着フィルムを加熱ラミネートする際には、接着フィルムの表面形状が表皮材に転写され、表皮材の意匠性が損なわれることがあるため、フィルム状接着剤にはフィッシュアイやブツなどの外観不良が少ないことが好ましい。 Various adhesives have not yet shown satisfactory adhesiveness to general thermoplastic resin molded articles. There are many requests for applications that require design properties such as automobile interiors, house interiors, and home appliances as molded products, and adhesive resin that can be used at the mildest processing temperature and pressure as much as possible so as not to impair the design properties. The composition is considered useful. In addition, these interior materials and casings are generally composed of a skin material and a molded product, and the adhesion between the two is usually performed while heat-molding the skin material according to the shape of the molded product. A film adhesive that can be used by simply laminating by heating is preferred. Furthermore, when the adhesive film is heat laminated to the skin material, the surface shape of the adhesive film is transferred to the skin material, and the design of the skin material may be impaired. It is preferable that there are few appearance defects, such as.
従って本発明の課題は、低温での積層体の製造が可能で、フィッシュアイ、ブツ、ゲルなどの外観不良が少ないホットメルト型接着フィルムを提供することである。 Accordingly, an object of the present invention is to provide a hot-melt adhesive film that can produce a laminate at a low temperature and has few appearance defects such as fish eyes, butts and gels.
本発明者らは、上述の現状に鑑み、鋭意検討した結果、特定の変性ポリオレフィンとスチレン系熱可塑性エラストマー、粘着付与剤からなる樹脂組成物が、ペレットハンドリング性がよくフィルムへの加工性に優れ、外観の良好なホットメルト型接着フィルムを与え、上記課題を解決することを見いだし、以下の本発明を完成するに至った。すなわち、本発明は、以下の構成をなす。 As a result of intensive studies in view of the above-described present situation, the present inventors have found that a resin composition comprising a specific modified polyolefin, a styrene-based thermoplastic elastomer, and a tackifier has good pellet handling properties and excellent workability into a film. The present inventors have found that a hot-melt adhesive film having a good appearance is provided and solve the above-mentioned problems, and have completed the following present invention. That is, the present invention has the following configuration.
１）（Ａ）（a）エポキシ基含有ビニル単量体および（ｂ）芳香族ビニル単量体で変性された、変性エチレンーαオレフィン共重合体６０〜９０重量部および（Ｂ）スチレン共役ジエン系ブロック共重合体４０〜１０重量部からなるベース樹脂〔ただし、（Ａ）＋（Ｂ）＝１００重量部〕に対し、（C）テルペン樹脂、芳香族変性テルペン樹脂、脂環族系石油樹脂のいずれかから選れた粘着付与剤３０〜６０重量部を必須成分として含有してなるホットメルト型接着フィルム。
２）（a）エポキシ基含有ビニル単量体がメタクリル酸グリシジルである、１）に記載のホットメルト型接着フィルム。
３）変性エチレンーαオレフィンが、密度が０．８５ｇ/ｃｍ3〜０．８７ｇ/ｃｍ3であるエチレンーαオレフィン共重合体を変性してなる、１）、２）に記載のホットメルト型接着フィルム。
４）エチレンーαオレフィンが、エチレン含量が１０〜２０重量％のエチレンープロピレン共重合体である、３）に記載のホットメルト型接着フィルム。
５）１）〜４）いずれか一項に記載のホットメルト型接着フィルムと、ポリオレフィン系樹脂、スチレン系樹脂、ポリカーボネート系樹脂、アクリル系樹脂、ポリアミド系樹脂、ポリエステル系樹脂および金属製材料からなる群より選ばれた少なくとも１種以上が接着してなる積層体。
1) (A) (a) 60 to 90 parts by weight of a modified ethylene-α-olefin copolymer modified with an epoxy group-containing vinyl monomer and (b) an aromatic vinyl monomer, and (B) a styrene conjugated diene system (C) terpene resin, aromatic modified terpene resin, and alicyclic petroleum resin based on 40 to 10 parts by weight of the base copolymer (however, (A) + (B) = 100 parts by weight) A hot-melt adhesive film comprising 30 to 60 parts by weight of a tackifier selected from any of the essential components.
2) (a) The hot melt adhesive film according to 1), wherein the epoxy group-containing vinyl monomer is glycidyl methacrylate.
3) the modified ethylene-α-olefin, formed by modifying ethylene-α-olefin copolymer density of 0.85g / cm 3 ~0.87g / cm 3 , 1), hot-melt adhesive film according to 2) .
4) The hot melt adhesive film according to 3), wherein the ethylene-α-olefin is an ethylene-propylene copolymer having an ethylene content of 10 to 20% by weight.
5) The hot-melt adhesive film according to any one of 1) to 4), a polyolefin resin, a styrene resin, a polycarbonate resin, an acrylic resin, a polyamide resin, a polyester resin, and a metal material. A laminate formed by adhering at least one selected from the group.
本発明の接着性樹脂組成物は、難接着基材に対し優れた接着力を確保することができ、文具、雑貨、食品などの包装材、自動車用部品、住宅資材、家電などの電気電子部品、各種産業用資材などの幅広い分野に用いられる。特に低温、低圧の接着加工で良好な接着強度が得られることから、意匠性の必要な、自動車内装、住宅内装、家電製品表面部材に好適に用いられる。 The adhesive resin composition of the present invention can ensure excellent adhesion to difficult-to-adhere base materials, and is a packaging material for stationery, miscellaneous goods, foods, etc., electrical and electronic parts such as automobile parts, housing materials, and home appliances. Used in a wide range of fields such as various industrial materials. In particular, since good adhesive strength can be obtained by low-temperature and low-pressure adhesive processing, it is suitably used for automobile interiors, house interiors, and home appliance surface members that require design.
以下に本発明の詳細について述べる。
（１）変性エチレン−αオレフィン共重合体
変性エチレン−αオレフィン共重合体とは、エチレン−αオレフィン共重合体に芳香族ビニル単量体とエポキシ基含有ビニル単量体をグラフト重合したものである。特に、低温加工での難接着樹脂への接着性を得るためには、変性に用いるエチレン−αオレフィン共重合体の密度が０．８５ｇ/ｃｍ3〜０．８７ｇ/ｃｍ3の、低結晶性、非晶性のエチレンーαオレフィンランダム共重合体であることが好ましい。エチレンーαオレフィンランダム共重合体を形成するα−オレフィンとしては、通常炭素数３〜２０のα−オレフィン、例えばプロピレン、１−ブテン、１−ヘキセン、４−メチル−１−ペンテン、１−オクテン、１−デセン、１−テトラデセン、１−オクタデセンが挙げられるが、グラフト変性の際、ポリオレフィン上にラジカルが発生しやすくなる点および耐熱性の観点から、プロピレンであることが好ましい。エチレンープロピレン共重合体中のエチレンとプロピレンの含有比率としては、プロピレン含量が８０〜９０重量％、エチレン含量が１０〜２０重量％であることが好ましい。エチレン含量がこの範囲より多いと、エチレンープロピレン共重合体の密度が高く低温接着性能が低下するか、耐熱性の面で実用に耐えないといった問題が生じる。さらに、変性時にエチレン部分で架橋反応が先行し、低温接着性が低下するだけでなく、接着性フィルムとして良好な外観のものとして取得できない可能性がある。一方、エチレン含量がこの範囲より少ないと、低温接着性が低下する傾向がある。
Details of the present invention will be described below.
(1) Modified ethylene-α olefin copolymer The modified ethylene-α olefin copolymer is obtained by graft-polymerizing an aromatic vinyl monomer and an epoxy group-containing vinyl monomer to an ethylene-α olefin copolymer. is there. In particular, in order to obtain adhesion to difficult-to-bond resin at a low temperature processing, the density of the ethylene -α-olefin copolymer used for the modification of 0.85g / cm 3 ~0.87g / cm 3 , low crystalline It is preferably an amorphous ethylene-α-olefin random copolymer. The α-olefin forming the ethylene-α-olefin random copolymer is usually an α-olefin having 3 to 20 carbon atoms such as propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, Although 1-decene, 1-tetradecene, and 1-octadecene are mentioned, propylene is preferable from the viewpoint of heat generation and a point that radicals are easily generated on the polyolefin during graft modification. As a content ratio of ethylene and propylene in the ethylene-propylene copolymer, it is preferable that the propylene content is 80 to 90% by weight and the ethylene content is 10 to 20% by weight. When the ethylene content is higher than this range, the ethylene-propylene copolymer has a high density, resulting in a problem that the low-temperature adhesion performance is deteriorated or the heat resistance is not practical. Furthermore, there is a possibility that the cross-linking reaction is preceded at the ethylene portion at the time of modification, not only the low-temperature adhesiveness is lowered, but also cannot be obtained as an adhesive film having a good appearance. On the other hand, when the ethylene content is less than this range, the low-temperature adhesiveness tends to decrease.
変性に使用する共重合体には、上述の、変性樹脂の熱特性を損なわない範囲であれば、他のジエン、ビニルエステルなどを第３成分として共重合してもよい。また、これらの変性エチレン−αオレフィン共重合体は、２種以上を混合して用いてもよく、２種以上の共重合体を混合したものを変性して用いてもかまわない。これらは、粒子状のものであってもペレット状のものであってもよく、その大きさや形はとくに制限されるものではない。 The copolymer used for modification may be copolymerized with another diene, vinyl ester, or the like as the third component as long as the above-described thermal properties of the modified resin are not impaired. These modified ethylene-α olefin copolymers may be used as a mixture of two or more, or a mixture of two or more copolymers may be used after modification. These may be in the form of particles or pellets, and the size and shape are not particularly limited.
変性エチレン−αオレフィン共重合体の製造には、溶融混練による方法、溶液による方法、懸濁法などの一般的なラジカルグラフト法によって行うことが出来る。この中で、経済的で、簡便かつ生産性に富む点では溶融混練法が好ましい。 The modified ethylene-α-olefin copolymer can be produced by a general radical grafting method such as a melt kneading method, a solution method, or a suspension method. Of these, the melt-kneading method is preferred because it is economical, simple and highly productive.
変性に用いるモノマーとしては、極性のある被着体との接着性を向上させるため、極性基含有ビニルモノマーが一般に用いられるが、中でも（a）エポキシ基含有ビニル単量体が、得られる接着剤組成物の接着性、フィルム成形性の面で好適である。a）エポキシ基含有ビニル単量体としては、特に制限されないが、好ましくは炭素数４〜２０、より好ましくは４〜１０のエポキシ基含有ビニル単量体であり、メタクリル酸グリシジル、アクリル酸グリシジル、マレイン酸モノグリシジル、マレイン酸ジグリシジル、イタコン酸モノグリシジル、イタコン酸ジグリシジル、アリルコハク酸モノグリシジル、アリルコハク酸ジグリシジル、ｐ−スチレンカルボン酸グリシジル、アリルグリシジルエーテル、メタアリルグリシジルエーテル、スチレン−ｐ−グリシジルエーテル、ｐ−グリシジルスチレンなどのグリシジル基含有ビニル単量体、３，４−エポキシ−１−ブテン、３，４−エポキシ−３−メチル−１−ブテンなどのエポキシオレフィン、ビニルシクロヘキセンモノオキシドなどの１種または２種以上が挙げられる。これらのうち、メタクリル酸グリシジルが安価で、溶融変性で適用しやすい点で好ましく、不飽和カルボン酸モノマーと比較して押出変性時に真空脱揮することで容易に除去でき、フィッシュアイや、発泡による穴あきなどの少ない外観の良好なホットメルト型接着フィルムの製造に好適である。 As a monomer used for modification, a polar group-containing vinyl monomer is generally used in order to improve adhesion to a polar adherend. Among them, (a) an epoxy group-containing vinyl monomer is obtained. It is suitable in terms of the adhesiveness and film moldability of the composition. a) Although it does not restrict | limit especially as an epoxy-group containing vinyl monomer, Preferably it is C4-C20, More preferably, it is an epoxy-group containing vinyl monomer of 4-10, glycidyl methacrylate, glycidyl acrylate, Monoglycidyl maleate, diglycidyl maleate, monoglycidyl itaconate, diglycidyl itaconate, monoglycidyl allyl succinate, diglycidyl allyl succinate, glycidyl p-styrenecarboxylate, allyl glycidyl ether, methallyl glycidyl ether, styrene-p-glycidyl ether, Glycidyl group-containing vinyl monomers such as p-glycidylstyrene, epoxy olefins such as 3,4-epoxy-1-butene and 3,4-epoxy-3-methyl-1-butene, and one kind such as vinylcyclohexene monoxide Or 2 or more types are mentioned. Among these, glycidyl methacrylate is preferable because it is inexpensive and easy to apply by melt modification, and can be easily removed by vacuum devolatilization during extrusion modification compared to unsaturated carboxylic acid monomers. It is suitable for producing a hot-melt adhesive film having a good appearance with few holes.
変性エチレン−αオレフィン共重合体中のエポキシ基含有ビニル単量体の含有量は、ベース樹脂１００重量部に対して、０．１〜５重量％であることが好ましい。０．１重量％より少ないと接着性が不充分であり、５重量％より多いと溶融混練中にグラフト鎖が反応して一部架橋を起こし、成形性が劣ると同時にフィッシュアイ、ブツなどによる製品外観が悪化し、且つ、かつ接着性も低下する。（a）エポキシ基含有ビニル単量体の添加量は、エチレン−αオレフィン共重合体１００重量部に対して、０．５〜１０重量部であることが好ましい。添加量が少なすぎると接着性が充分に改善されない傾向があり、添加量が多すぎるとグラフトに寄与しないフリーポリマーの副生が増大する傾向や、好適な形状や外観を有するフィルム状接着剤組成物として取得できない傾向がある。 The content of the epoxy group-containing vinyl monomer in the modified ethylene-α-olefin copolymer is preferably 0.1 to 5% by weight with respect to 100 parts by weight of the base resin. If it is less than 0.1% by weight, the adhesiveness is insufficient, and if it exceeds 5% by weight, the graft chain reacts during melt-kneading to cause partial crosslinking, resulting in poor moldability and at the same time due to fish eyes, butts, etc. The appearance of the product deteriorates and the adhesiveness also decreases. (A) It is preferable that the addition amount of an epoxy group containing vinyl monomer is 0.5-10 weight part with respect to 100 weight part of ethylene-alpha olefin copolymers. If the addition amount is too small, the adhesiveness tends not to be improved sufficiently. If the addition amount is too large, the by-product of free polymer that does not contribute to the graft tends to increase, and a film-like adhesive composition having a suitable shape and appearance. There is a tendency that it cannot be acquired as a thing.
ラジカル重合開始剤としては、有機過酸化物が一般的に用いられ、例えば水素引き抜き能が高いものとして、１，１−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、ｎ−ブチル−４，４−ビス（ｔ−ブチルパーオキシ）バレレート、２，２−ビス（ｔ−ブチルパーオキシ）ブタンなどのパーオキシケタール；ジクミルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、α，α´−ビス（ｔ−ブチルパーオキシ−ｍ−イソプロピル）ベンゼン、ｔ−ブチルクミルパーオキサイド、ジ−ｔ−ブチルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキシン−３などのジアルキルパーオキサイド；ベンゾイルパーオキサイドなどのジアシルパーオキサイド；ｔ−ブチルパーオキシオクテート、ｔ−ブチルパーオキシイソブチレート、ｔ−ブチルパーオキシラウレート、ｔ−ブチルパーオキシ−３，５，５−トリメチルヘキサノエート、ｔ−ブチルパーオキシイソプロピルカーボネート、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン、ｔ−ブチルパーオキシアセテート、ｔ−ブチルパーオキシベンゾエート、ジ−ｔ−ブチルパーオキシイソフタレートなどのパーオキシエステルが好ましい。これらは、２種以上を組み合わせて用いてもよい。 As the radical polymerization initiator, an organic peroxide is generally used. For example, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, Peroxyketals such as 1,2-bis (t-butylperoxy) cyclohexane, n-butyl-4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane; Dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide Dialkyl peroxides such as di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3; Diacyl peroxides such as yl peroxide; t-butyl peroxyoctate, t-butyl peroxyisobutyrate, t-butyl peroxylaurate, t-butyl peroxy-3,5,5-trimethylhexanoate , T-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxybenzoate, di-t-butylperoxyisophthalate Peroxyesters such as are preferred. You may use these in combination of 2 or more type.
前記ラジカル重合開始剤の添加量は、エチレン−αオレフィン共重合体１００重量部に対して、０．０１〜１０重量部の範囲内にあることが好ましく、０．０５〜５重量部の範囲内にあることがさらに好ましい。０．０１重量部未満では変性が充分に進行せず、１０重量部を超えると架橋反応による流動性の低下やゲル分の増加により、接着性が低下することがある。 The addition amount of the radical polymerization initiator is preferably in the range of 0.01 to 10 parts by weight, and in the range of 0.05 to 5 parts by weight with respect to 100 parts by weight of the ethylene-α-olefin copolymer. More preferably. If the amount is less than 0.01 parts by weight, the modification does not proceed sufficiently. If the amount exceeds 10 parts by weight, the adhesiveness may be lowered due to a decrease in fluidity due to a crosslinking reaction or an increase in gel content.
（a）エポキシ基含有ビニル単量体のグラフト率を向上させる目的で、（ｂ）芳香族ビニル単量体を添加することが好ましい。また、芳香族ビニル単量体を共存させることで、ポリオレフィンの主鎖切断による機械的特性が低下するのを抑えることができ、接着剤組成物の耐熱性を保つことができる。 For the purpose of improving the graft ratio of (a) the epoxy group-containing vinyl monomer, it is preferable to add (b) an aromatic vinyl monomer. In addition, the coexistence of the aromatic vinyl monomer can suppress the deterioration of the mechanical properties due to the main chain cleavage of the polyolefin, and the heat resistance of the adhesive composition can be maintained.
（ｂ）芳香族ビニル単量体としては、特に制限されないが、好ましくは炭素数４〜２０、より好ましくは６〜１５の芳香族ビニル単量体である。例示するならば、スチレン；ｏ−メチルスチレン、ｍ−メチルスチレン、ｐ−メチルスチレン、α−メチルスチレン、β−メチルスチレン、ジメチルスチレン、トリメチルスチレンなどのメチルスチレン；ｏ−クロロスチレン、ｍ−クロロスチレン、ｐ−クロロスチレン、α−クロロスチレン、β−クロロスチレン、ジクロロスチレン、トリクロロスチレンなどのクロロスチレン；ｏ−ブロモスチレン、ｍ−ブロモスチレン、ｐ−ブロモスチレン、ジブロモスチレン、トリブロモスチレンなどのブロモスチレン；ｏ−フルオロスチレン、ｍ−フルオロスチレン、ｐ−フルオロスチレン、ジフルオロスチレン、トリフルオロスチレンなどのフルオロスチレン；ｏ−ニトロスチレン、ｍ−ニトロスチレン、ｐ−ニトロスチレン、ジニトロスチレン、トリニトロスチレンなどのニトロスチレン；ｏ−ヒドロキシスチレン、ｍ−ヒドロキシスチレン、ｐ−ヒドロキシスチレン、ジヒドロキシスチレン、トリヒドロキシスチレンなどのビニルフェノール；ｏ−ジビニルベンゼン、ｍ−ジビニルベンゼン、ｐ−ジビニルベンゼンなどのジビニルベンゼン；ｏ−ジイソプロペニルベンゼン、ｍ−ジイソプロペニルベンゼン、ｐ−ジイソプロペニルベンゼンなどのジイソプロペニルベンゼン；などの１種または２種以上が挙げられる。これらのうちスチレン、α−メチルスチレン、ｐ−メチルスチレンなどのメチルスチレン、ジビニルベンゼン単量体またはジビニルベンゼン異性体混合物が安価であるという点で好ましい。 (B) Although it does not restrict | limit especially as an aromatic vinyl monomer, Preferably it is C4-C20, More preferably, it is a C6-C15 aromatic vinyl monomer. For example, styrene; methyl styrene such as o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, β-methyl styrene, dimethyl styrene, trimethyl styrene; o-chloro styrene, m-chloro Chlorostyrene such as styrene, p-chlorostyrene, α-chlorostyrene, β-chlorostyrene, dichlorostyrene, trichlorostyrene; o-bromostyrene, m-bromostyrene, p-bromostyrene, dibromostyrene, tribromostyrene, etc. Bromostyrene; fluorostyrene such as o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, difluorostyrene, trifluorostyrene; o-nitrostyrene, m-nitrostyrene, p-nitrostyrene, dinitrostyrene, Nitrostyrene such as renitrostyrene; vinylphenols such as o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, dihydroxystyrene, trihydroxystyrene; o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, etc. 1 type, or 2 or more types, such as divinylbenzene; diisopropenylbenzene, such as o-diisopropenylbenzene, m-diisopropenylbenzene, p-diisopropenylbenzene; Of these, methylstyrene such as styrene, α-methylstyrene, p-methylstyrene, divinylbenzene monomer or divinylbenzene isomer mixture is preferable in that it is inexpensive.
前記（ｂ）芳香族ビニル単量体の添加量は、エチレン−αオレフィン共重合体１００重量部に対して、０．１〜１０重量部であることが好ましく、１〜５重量部であることがさらに好ましい。添加量が少なすぎるとエチレン−αオレフィン共重合体に対する（a）エポキシ基含有ビニル単量体のグラフト率が劣る傾向がある。一方、添加量が１０重量部を超えると（a）エポキシ基含有ビニル単量体のグラフト効率が飽和域に達するとともに、過剰な架橋反応が進行して、接着性が低下する恐れがある。 The amount of the (b) aromatic vinyl monomer added is preferably 0.1 to 10 parts by weight, and 1 to 5 parts by weight with respect to 100 parts by weight of the ethylene-α-olefin copolymer. Is more preferable. If the amount added is too small, the graft ratio of the (a) epoxy group-containing vinyl monomer to the ethylene-α-olefin copolymer tends to be poor. On the other hand, when the addition amount exceeds 10 parts by weight, the graft efficiency of the (a) epoxy group-containing vinyl monomer reaches a saturation region, and an excessive crosslinking reaction proceeds, whereby the adhesiveness may be lowered.
溶融混練時の添加順序及び方法については、エチレン−αオレフィン共重合体とラジカル重合開始剤を溶融混練した混合物に不飽和カルボン酸及び／又はその誘導体、あるいは芳香族ビニル単量体を加え溶融混練する添加順序がよく、この添加順序で行うことでグラフトに寄与しない低分子量体の生成を抑制することができる。なお、そのほか必要に応じ添加される材料の混合や溶融混練の順序及び方法はとくに制限されるものではない。 Regarding the order and method of addition at the time of melt kneading, an unsaturated carboxylic acid and / or a derivative thereof, or an aromatic vinyl monomer is added to the mixture obtained by melting and kneading an ethylene-α olefin copolymer and a radical polymerization initiator. The order of addition is good, and the formation of low molecular weight substances that do not contribute to grafting can be suppressed by carrying out in this order of addition. In addition, the order and method of mixing and melt-kneading the materials added as necessary are not particularly limited.
溶融混練時の加熱温度は、エチレン−αオレフィン共重合体が充分に溶融し、過剰な熱分解、架橋反応、およびフィッシュアイの増加が抑えられるという点で、１８０〜２００℃が好ましい。また前記の溶融混練の装置としては、一軸又は多軸押出機、バンバリーミキサー、プラストミル、加熱ロールニーダー、などを使用することができるが、生産性の面から減圧装置を装備した単軸あるいは二軸押出機を用いる方法が好ましい。溶融混練の時間（ラジカル重合開始剤を混合してからの時間）は、通常３０秒間〜６０分間である。 The heating temperature at the time of melt kneading is preferably 180 to 200 ° C. from the viewpoint that the ethylene-α-olefin copolymer is sufficiently melted and excessive thermal decomposition, crosslinking reaction, and increase of fish eyes are suppressed. As the melt kneading apparatus, a single-screw or multi-screw extruder, a Banbury mixer, a plast mill, a heated roll kneader, and the like can be used. From the viewpoint of productivity, a single screw or a twin screw equipped with a pressure reducing device. A method using an extruder is preferred. The melt kneading time (the time after mixing the radical polymerization initiator) is usually 30 seconds to 60 minutes.
（２）スチレン共役ジエン系ブロック共重合体
本発明の（Ｂ）成分のスチレン共役ジエン系ブロック共重合体とは、ビニル芳香族化合物を主成分とする重合体ブロックからなるハードセグメントと、共役ジエン化合物を主成分とする重合体からなるソフトセグメントを有するブロック共重合体であり、ブロックＡがビニル芳香族化合物、ブロックＢが共役ジエン化合物であるとしたときに、一般式Ａ−Ｂ、Ａ−Ｂ−Ａ、Ｂ−Ａ−Ｂ−Ａ、Ａ−Ｂ−Ａ−Ｂ−Ａ等で表される。ブロック共重合体を用いることで、各種粘着付与剤との併用で、低温加工での各種基材との接着性が得られると共に、低タック性、耐熱性のバランスの取れた接着性樹脂組成物の製造が可能である。
(2) Styrene conjugated diene block copolymer The styrene conjugated diene block copolymer of the component (B) of the present invention is a hard segment composed of a polymer block mainly composed of a vinyl aromatic compound, and a conjugated diene. A block copolymer having a soft segment composed of a polymer having a compound as a main component, wherein the block A is a vinyl aromatic compound and the block B is a conjugated diene compound, the general formulas AB, A- It is represented by B-A, B-A-B-A, A-B-A-B-A, and the like. By using a block copolymer, it is possible to obtain adhesiveness with various base materials in low temperature processing in combination with various tackifiers, and an adhesive resin composition with a balance between low tack and heat resistance. Can be manufactured.
スチレン共役ジエン系ブロック共重合体の好ましい例としては、スチレン−ブタジエンジブロックコポリマー、スチレンーブタジエントリブロックコポリマー、スチレンーイソプレンジブロックコポリマー、スチレンーイソプレントリブロックコポリマー、水素添加スチレン−ブタジエンジブロックコポリマー、水素添加スチレンーブタジエントリブロックコポリマー、水素添加スチレンーイソプレンジブロックコポリマー、水素添加スチレンーイソプレントリブロックコポリマーなどが挙げられ、耐熱性および耐候性が良好なものとなる点から、水素添加スチレン−イソプレントリブロックコポリマー（ＳＥＰＳ）、水素添加スチレン−ブタジエントリブロックコポリマー（ＳＥＢＳ）、が特に好ましい。 Preferred examples of the styrene conjugated diene block copolymer include styrene-butadiene diblock copolymer, styrene-butadiene triblock copolymer, styrene-isoprene block copolymer, styrene-isoprene triblock copolymer, hydrogenated styrene-butadiene diblock copolymer. , Hydrogenated styrene-butadiene triblock copolymer, hydrogenated styrene-isoprene diblock copolymer, hydrogenated styrene-isoprene triblock copolymer, and the like. From the point that heat resistance and weather resistance are good, hydrogenated styrene- Isoprene triblock copolymer (SEPS), hydrogenated styrene-butadiene triblock copolymer (SEBS) are particularly preferred.
（３）粘着付与剤
（Ｃ）成分の粘着付与剤としては、種々のものがあるが、変性エチレンーαオレフィン中のエポキシ基と反応する構造を含まない脂環族系石油樹脂、テルペン樹脂（α−ピネン、β-ピネン、リモネンなどの重合体）、芳香族変性テルペン樹脂が好ましく、中でも濡れ性、ハンドリング性、耐熱性の観点から芳香族変性テルペン樹脂がより好ましく、入手のしやすさからスチレン変性テルペン樹脂が特に好ましい。テルペンフェノール樹脂や、ロジン系樹脂は、その構造上、低酸価、低水酸基価とすることが困難であるため、溶融混練、変性樹脂中のエポキシ基と反応して、フィッシュアイ、ゲルが増加するだけでなく、樹脂組成物が増粘し、フィルム成形性が悪く傾向がある。低温加工での接着性、耐熱性、接着剤樹脂組成物のハンドリングの観点から、環球法による軟化点が９０℃以上、好ましくは１００〜１７０℃より好ましくは、１３０〜１６０℃の範囲ものを用いることが好ましい。軟化点が９０℃よりも低いものであると接着剤組成物の耐熱性が低下するとともに、スチレン系熱可塑性エラストマーやエチレン−αオレフィン共重合体との溶融混練が困難となるばかりか、接着剤樹脂組成物の常温タックが強くなりすぎてフィルム成形が困難となる。粘着付与剤としては、単独あるいは２種以上をあわせて用いることができる。
(3) Tackifiers (C) There are various types of tackifiers, but alicyclic petroleum resins and terpene resins (α that do not contain a structure that reacts with epoxy groups in modified ethylene-α-olefins) -Polyene, β-pinene, limonene, and the like) and aromatic modified terpene resins are preferred. Among them, aromatic modified terpene resins are more preferred from the viewpoint of wettability, handling properties, and heat resistance, and styrene is easily available. A modified terpene resin is particularly preferred. Because terpene phenol resin and rosin resin are difficult to have low acid value and low hydroxyl value due to their structure, fish eyes and gel increase due to reaction with epoxy groups in melt-kneaded and modified resins In addition, the resin composition tends to thicken and the film moldability tends to be poor. From the viewpoint of adhesion at low temperature processing, heat resistance, and handling of the adhesive resin composition, a softening point by the ring and ball method is 90 ° C. or higher, preferably 100 to 170 ° C., more preferably 130 to 160 ° C. It is preferable. When the softening point is lower than 90 ° C., the heat resistance of the adhesive composition is lowered, and not only the melt-kneading with a styrene-based thermoplastic elastomer or an ethylene-α-olefin copolymer is difficult, but the adhesive The room temperature tack of the resin composition becomes too strong, making film formation difficult. As a tackifier, it can use individually or in combination of 2 or more types.
（４）接着性樹脂組成物
本発明のホットメルト型接着フィルムをなす接着性樹脂組成物の各成分の配合割合としては、（１）変性エチレン−αオレフィン共重合体６０〜９０重量部および（２）スチレン共役ジエン系ブロック共重合体４０〜１０重量部［ただし、（Ａ）＋（Ｂ）＝１００重量部］のベース樹脂に対し、粘着付与剤３０〜６０重量部である。（C）成分の粘着付与剤の配合量としては、４０〜５０重量部であることがより好ましい。（Ｃ）成分の粘着付与剤の配合量が、３０重量部より少ないと被着体へのぬれ性が乏しくなり接着性が低下し、６０重量部より多いと凝集力が乏しくなり接着性、耐熱性が低下するとともに、接着性樹脂組成物のタックが強くなりすぎて、配合およびフィルム成形時の取り扱いが困難となる。一方で、ベース樹脂中（Ａ）変性エチレン−αオレフィン共重合体と（Ｂ）スチレン系熱可塑性エラストマーの配合比としては、（Ａ）６５〜８５重量部、（Ｂ）３５〜１５重量部がより好ましく、（A）７０〜８０重量部、（B）３０〜２０重量部であることがさらに好ましい。この配合比とすることで、低温接着加工での被着体への充分な濡れ性と、常温でのタックのバランスが取れた接着剤樹脂組成物を得ることができる。
なお、接着性樹脂組成物には必要に応じて、酸化防止剤、金属不活性剤、燐系加工安定剤、紫外線吸収剤、紫外線安定剤、蛍光増白剤、金属石鹸、制酸吸着剤などの安定剤、または架橋剤、連鎖移動剤、核剤、滑剤、可塑剤、充填材、強化材、顔料、染料、難燃剤、帯電防止剤などの添加剤を本発明の効果を損なわない範囲内で添加してもよい。これらの安定剤および添加剤を用いる場合は、予めスチレン系熱可塑性エラストマーまたは、エチレン−αオレフィン共重合体に添加されているものであってもよく、これらの溶融変性の際に添加されるものであってもよく、接着性樹脂組成物を溶融混錬により製造する際に添加されるものであってもよく、後述のホットメルト型接着フィルムの製造の際に添加されるものであってもよい。
(4) Adhesive resin composition The blending ratio of each component of the adhesive resin composition forming the hot melt adhesive film of the present invention includes (1) 60 to 90 parts by weight of a modified ethylene-α-olefin copolymer and ( 2) It is 30-60 weight part of tackifiers with respect to the base resin of 40-10 weight part [however, (A) + (B) = 100 weight part] of a styrene conjugated diene block copolymer. (C) As a compounding quantity of the tackifier of a component, it is more preferable that it is 40-50 weight part. When the blending amount of the component (C) tackifier is less than 30 parts by weight, the wettability to the adherend is poor and the adhesiveness is lowered, and when it is more than 60 parts by weight, the cohesive force is poor and the adhesiveness and heat resistance In addition, the tackiness of the adhesive resin composition becomes too strong and handling during compounding and film forming becomes difficult. On the other hand, (A) 65 to 85 parts by weight and (B) 35 to 15 parts by weight of (A) modified ethylene-α-olefin copolymer and (B) styrene-based thermoplastic elastomer in the base resin. More preferably, (A) 70 to 80 parts by weight and (B) 30 to 20 parts by weight are more preferable. By setting it as this compounding ratio, the adhesive resin composition with sufficient wettability to the to-be-adhered body in a low-temperature-adhesion process and the tack | tuck at normal temperature can be obtained.
If necessary, the adhesive resin composition includes an antioxidant, a metal deactivator, a phosphorus processing stabilizer, an ultraviolet absorber, an ultraviolet stabilizer, a fluorescent brightener, a metal soap, an antacid adsorbent, etc. Stabilizers, or additives such as cross-linking agents, chain transfer agents, nucleating agents, lubricants, plasticizers, fillers, reinforcing materials, pigments, dyes, flame retardants, antistatic agents, etc. May be added. When these stabilizers and additives are used, they may be added in advance to the styrenic thermoplastic elastomer or ethylene-α olefin copolymer, and are added at the time of melt modification May be added when the adhesive resin composition is produced by melt kneading, or may be added during the production of a hot-melt adhesive film described later. Good.
（４）ホットメルト型接着フィルムの製造方法
本発明のホットメルト型接着フィルムの製造方法は、特に限定されるものではないが、例えば本発明の接着性樹脂組成物を溶融混練により得た後に、各種の押出成形機、射出成形機、カレンダー成形機、インフレーション成形機、ロール成形機、あるいは加熱プレス成形機などを用いてシート状成形体に成形加工することが可能である。中でも、先端にＴ型ダイスを備えた単軸押出機を使う方法が汎用的で好ましい。溶融混錬の装置としては、一軸又は多軸押出機、バンバリーミキサー、プラストミル、加熱ロールニーダー、などを使用することができる。生産性の面から減圧装置を装備した単軸あるいは二軸押出機を用いる方法が好ましい。 また、各々の材料を充分に均一に混合するために、前記溶融混練を複数回繰返してもよい。
(4) Manufacturing method of hot melt type adhesive film The manufacturing method of the hot melt type adhesive film of the present invention is not particularly limited. For example, after the adhesive resin composition of the present invention is obtained by melt kneading, It can be formed into a sheet-like molded body using various types of extrusion molding machines, injection molding machines, calendar molding machines, inflation molding machines, roll molding machines, or hot press molding machines. Among these, a method using a single-screw extruder having a T-shaped die at the tip is versatile and preferable. As an apparatus for melt kneading, a single-screw or multi-screw extruder, a Banbury mixer, a plast mill, a heated roll kneader, or the like can be used. From the viewpoint of productivity, a method using a single-screw or twin-screw extruder equipped with a pressure reducing device is preferable. Moreover, in order to mix each material sufficiently uniformly, the melt kneading may be repeated a plurality of times.
（５）ホットメルト型接着フィルムを含む積層体
本発明のホットメルト型接着フィルムを用いれば、比較的低い処理温度で種々の基材を接着させて多層積層体を得ることが可能になる。本発明の積層体を構成する材料としては、紙、木綿，麻，布、木板などのセルロース系高分子材料、ポリプロピレン，ポリエチレンなどのポリオレフィン系樹脂、ポリスチレン，スチレン−ブタジエンブロック共重合体（ＳＢＳ樹脂），スチレン−アクリロニトリル共重合体（ＡＳ樹脂），アクリロニトリル−エチレン／プロピレン−スチレン共重合体（ＡＥＳ樹脂）、アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ樹脂）などのスチレン系樹脂、ポリカーボネート系樹脂、（メタ）アクリル系樹脂、ポリエステル系樹脂、ナイロン、ポリウレタンなどのポリアミド系樹脂、フェノール樹脂、エポキシ樹脂等の合成高分子材料、金、銀、銅、鉄、錫、鉛、アルミニウムなどの金属材料が挙げられる。基材の材料として、異なる２種類以上の材料を混合、複合してもよい。また、積層体が本発明の接着性フィルムを介して、異なる２つの被着体が接着してなるものである場合、２つの基材を構成する材料は、同じ種類の材料でも異なる種類の材料のいずれでもよい。本発明のホットメルト型接着フィルムは、特に基材の表面処理をすることなく、強力な接着が可能であるが、必要に応じて、プラズマやレーザーなどによる表面改質、表面酸化、エッチングなどの表面処理等を実施してもよい。
(5) Laminate including hot melt adhesive film If the hot melt adhesive film of the present invention is used, it becomes possible to obtain a multilayer laminate by adhering various substrates at a relatively low processing temperature. The material constituting the laminate of the present invention includes cellulosic polymer materials such as paper, cotton, hemp, cloth, and wood board, polyolefin resins such as polypropylene and polyethylene, polystyrene, styrene-butadiene block copolymer (SBS resin). ), Styrene-acrylonitrile copolymer (AS resin), acrylonitrile-ethylene / propylene-styrene copolymer (AES resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), and other styrene resins, polycarbonate resins, (Meth) acrylic resins, polyester resins, polyamide resins such as nylon and polyurethane, synthetic polymer materials such as phenolic resins and epoxy resins, metal materials such as gold, silver, copper, iron, tin, lead, and aluminum Can be mentioned. As the base material, two or more different materials may be mixed and combined. When the laminate is formed by adhering two different adherends via the adhesive film of the present invention, the materials constituting the two substrates may be the same type of materials or different types of materials. Either of these may be used. The hot-melt adhesive film of the present invention can be strongly bonded without particularly treating the surface of the substrate, but if necessary, such as surface modification by plasma or laser, surface oxidation, etching, etc. A surface treatment or the like may be performed.
本発明の積層体の用途の具体例としては特に限定されないが、基材として表皮材及び成形品を使用する用途、例えば自動車等の内装材料（自動車内装用天井材，自動車内装用ドア部材，自動車内装用ダッシュボード部材、インパネ等）、家電部品（パソコン筺体、薄型テレビのフレーム等）、住居資材（内装壁板、化粧フィルム等）として好適に使用することができる。ここで用いられる表皮材とは、予めフィルム、シート、発泡体、各種不織物、織物に成形されたものであり、例えば、ポリ塩化ビニル、各種ポリオレフィン、ＡＢＳから製造される高分子製加飾シート、ポリエステル不織布、起毛ニット、ファブリック、ポリウレタンレザー、ポリプロピレン、ポリエチレン、ポリブチレン、およびこれらオレフィンの共重合体を主成分として製造されるポリオレフィン系発泡体などが挙げられる。また、ここで用いられる成形品としては、ＡＢＳ、ＰＣ／ＡＢＳ、ポリオレフィン、ガラス繊維強化ポリオレフィン、ガラス繊維強化ナイロンなどの各種高分子材料の射出成形品、木材チップ、木質粉などを熱硬化性樹脂やポリオレフィン樹脂で熱プレス成形により固めた木質成形品や木質ボードが挙げられる。 Although it does not specifically limit as a specific example of the use of the laminated body of this invention, The use which uses a skin material and a molded article as a base material, for example, interior materials, such as a motor vehicle (ceiling material for motor vehicle interior, a door member for motor vehicle interior, a motor vehicle It can be suitably used as an interior dashboard member, an instrument panel, etc.), a home appliance part (such as a personal computer housing, a thin TV frame), and a housing material (an interior wall board, a decorative film, etc.). The skin material used here is a film, sheet, foam, various non-woven fabrics, woven fabrics, for example, a polymer decorative sheet manufactured from polyvinyl chloride, various polyolefins, ABS, for example. Polyester non-woven fabric, raised knit, fabric, polyurethane leather, polypropylene, polyethylene, polybutylene, and polyolefin-based foams produced mainly from copolymers of these olefins. In addition, as molded products used here, ABS, PC / ABS, polyolefin, glass fiber reinforced polyolefin, injection molded products of various polymer materials such as glass fiber reinforced nylon, wood chips, wood powder, etc. are thermosetting resins. And wood molded products and wood boards hardened by hot press molding with polyolefin resin.
本発明の接着性樹脂組成物は、比較的低い温度で強力な接着が可能であり、表皮材及び成形品の素材の風合い、感触等を損なうことなく製造でき、加飾シートを表皮材とする成形品加飾の用途に好適である。 The adhesive resin composition of the present invention is capable of strong adhesion at a relatively low temperature, can be produced without impairing the texture, feel, etc. of the material of the skin material and the molded product, and uses the decorative sheet as the skin material. It is suitable for uses of decorative molded products.
本発明に関わる多層積層体を製造するにあたっては、熱ラミネート、真空成形、真空圧空成形、熱プレス、熱ロール、ホットスタンプ成形など、種々の成形方法を採用できる。中でも真空成形、真空圧空成形、ホットスタンプ成形は、表皮材とアールを有する成形品の接着に適用できる点で好ましい。アールを有する成形品とは、上に例示したような材質の成形品のうち、表皮材と接着する面として、平面円弧状の面を有する成形品を指し、自動車内装や家電筐体の形状骨格をなす成形品である。積層体の製造方法としては、例えば表皮材に接着フィルムを加熱ラミネートしておき、これを各成形に付すことで、成形体の形状に沿って表皮材を積層することができる。熱プレスや熱ロールは、このような成形品の円弧形状を損なう可能性があり好ましくない。特に、真空圧空成形は、表皮と成形品の接着の際、圧空圧をかけることにより、成形品の端部から成形品裏側にかけて表皮材を巻き込ませることができ、さらには、深絞り形状の成形品を被着体とした積層体を製造にも適用できる。 In producing the multilayer laminate according to the present invention, various molding methods such as thermal lamination, vacuum forming, vacuum / pressure forming, hot pressing, hot roll, hot stamping, etc. can be employed. Among these, vacuum forming, vacuum pressure forming, and hot stamping are preferable in that they can be applied to the bonding of a molded product having a skin material and a rounded shape. A molded product having a round shape refers to a molded product having a plane arc-shaped surface as a surface to be bonded to a skin material among molded products of the materials exemplified above, and is a shape skeleton of an automobile interior or home appliance housing. This is a molded product. As a manufacturing method of a laminated body, for example, an adhesive film is heated and laminated on a skin material, and this is applied to each molding, whereby the skin material can be laminated along the shape of the molded body. A hot press or a hot roll is not preferable because it may impair the arc shape of such a molded product. In particular, in vacuum / pressure forming, the skin material can be wound from the end of the molded product to the back side of the molded product by applying compressed air pressure when the skin and the molded product are bonded. A laminate having the product as an adherend can also be applied to production.
真空成形、真空圧空成形、ホットスタンプ成形を用いる場合、表皮材の成形品への追従性から、接着フィルムの厚みは、２５μｍ〜１００μｍが好ましく、３０μｍ〜７０μｍの厚みがより好ましい。２５μｍ未満であると、成形品への接着面積が乏しくなり、接着強度が不充分なものとなり好ましくなく、１００μｍを超えると熱伝導性が低下し、表皮材加熱時に所定時間内で充分軟化せず、接着強度が低下する。また、この厚みとすることで、外観の良好な積層体が得られるだけでなく、積層体を高温雰囲気下に置いた場合に表皮材、成形品が膨張、収縮することによって生じる、表皮材のめくれ、横ずれなどの外観不良の発生を抑えることができる。真空圧空成形で得られた積層体は、表皮材が成形品端部から裏面にかけて巻き込んでいることにより、より高温雰囲気下での外観維持が可能である。 In the case of using vacuum forming, vacuum pressure forming, or hot stamping, the thickness of the adhesive film is preferably 25 μm to 100 μm, more preferably 30 μm to 70 μm, from the followability of the skin material to the molded product. If it is less than 25 μm, the adhesion area to the molded product becomes poor and the adhesive strength becomes insufficient, which is not preferable. If it exceeds 100 μm, the thermal conductivity is lowered, and the skin material is not sufficiently softened within a predetermined time during heating. , The adhesive strength decreases. In addition, by this thickness, not only a laminate having a good appearance can be obtained, but also when the laminate is placed in a high-temperature atmosphere, the skin material and the molded product are expanded and contracted. It is possible to suppress the appearance defects such as turning and lateral slippage. The laminate obtained by vacuum / pressure forming can maintain the appearance in a higher temperature atmosphere because the skin material is wound from the end of the molded product to the back surface.
以下に具体的な実施例および比較例によって本発明をさらに詳細に示すが、本発明は下記実施例に限定されるものではない。下記実施例および比較例中「部」および「％」は、それぞれ「重量部」および「重量％」を表す。 Hereinafter, the present invention will be described in more detail by way of specific examples and comparative examples, but the present invention is not limited to the following examples. In the following examples and comparative examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.
１．変性エチレンーαオレフィンの製造
変性エチレンーαオレフィンの物性測定は以下のようにして行った。
（変性エチレンーαオレフィン共重合体中のメタクリル酸グリシジル、無水マレイン酸含量の分析）メタクリル酸グリシジル、無水マレイン酸含量は、得られた変性エチレンープロピレン共重合体ペレットを１１０℃に加熱したクロロベンゼンに溶解した後、そのクロロベンゼン溶液をアセトン中に滴下し再沈殿物させ、得られた再沈殿物について滴定を行うことにより得た。
1. Production of modified ethylene-α-olefin The physical properties of the modified ethylene-α-olefin were measured as follows.
(Analysis of Glycidyl Methacrylate and Maleic Anhydride Content in Modified Ethylene-α Olefin Copolymer) The glycidyl methacrylate and maleic anhydride contents were obtained by heating the obtained modified ethylene-propylene copolymer pellets to chlorobenzene heated to 110 ° C. After dissolution, the chlorobenzene solution was dropped into acetone to cause reprecipitation, and the obtained reprecipitate was titrated.
（変性エチレンーαオレフィン共重合体中ＤＳＣ測定法）
示差走査型熱量計（ＳＨＩＭＡＤＺＵ社製、ＤＴＧ−５０）を用い、試料を窒素雰囲気下、２４０℃まで、２０℃／分で昇温させ、直ちに４０℃以下まで降温した後、２４０℃まで再度２０℃／分で昇温下時に得られた融解吸熱カーブから観測されるピークのピークトップとして定義される温度を融点（Ｔｍ）、その融解熱量をΔＨ（Ｊ／ｇ）とした。
(DSC measurement method in modified ethylene-α-olefin copolymer)
Using a differential scanning calorimeter (manufactured by SHIMADZU, DTG-50), the sample was heated up to 240 ° C. at 20 ° C./min in a nitrogen atmosphere, immediately cooled to 40 ° C. or lower, and then again up to 240 ° C. The temperature defined as the peak top of the peak observed from the melting endothermic curve obtained when the temperature was raised at 0 ° C./min was the melting point (Tm), and the heat of fusion was ΔH (J / g).
（製造例１）
エチレン−プロピレン共重合体（（株）ダウ製ヴァーシファイDE３４０１．０５、ＭＦＲ８、エチレン含量１５重量％、密度０．８６３ｇ/ｃｍ3）１００部、１，３−ジ（ｔ-ブチルパーオキシイソプロピル）ベンゼン（１分間半減期１７５℃）０.５部をシリンダー温度２００℃、回転数１５０ｒｐｍに設定した二軸押出機（４４ｍｍφ、Ｌ／Ｄ＝３８．５、（株）日本製鋼所製、製品名ＴＥＸ４４ＸＣＴ）に供給して溶融混練した後、次いで、シリンダー途中よりメタクリル酸グリシジル３部、スチレン３部加え溶融混練した後、脱揮してストランド状に押出し、水冷後カッティングして、変性エチレン−プロピレン共重合体（Ａ１）を得た。得られた変性エチレン−プロピレン共重合体（A１）の物性は、表１の通りであった。
(Production Example 1)
100 parts of ethylene-propylene copolymer (Varify DE3401.05, MFR8, ethylene content 15% by weight, density 0.863 g / cm 3 ) manufactured by Dow Co., Ltd., 1,3-di (t-butylperoxyisopropyl) benzene Twin screw extruder (44 mmφ, L / D = 38.5, manufactured by Nippon Steel Co., Ltd., product name TEX44XCT) in which 0.5 part is set at a cylinder temperature of 200 ° C. and a rotation speed of 150 rpm (half-life of 175 ° C. for 1 minute) Then, 3 parts of glycidyl methacrylate and 3 parts of styrene are added and melt-kneaded from the middle of the cylinder, then devolatilized, extruded into a strand, cut with water, cut after cutting, and modified with ethylene-propylene. A polymer (A1) was obtained. Table 1 shows the physical properties of the obtained modified ethylene-propylene copolymer (A1).
（製造例２）
エチレン−プロピレン共重合体（（株）ダウ製ヴァーシファイ４３０１、ＭＦＲ２５、エチレン含量１２重量％、密度０．８６７ｇ/ｃｍ3）１００部、１，３−ジ（ｔ-ブチルパーオキシイソプロピル）ベンゼン（１分間半減期１７５℃）０.５部をシリンダー温度２００℃、回転数１５０ｒｐｍに設定した二軸押出機（４４ｍｍφ、Ｌ／Ｄ＝３８．５、（株）日本製鋼所製、製品名ＴＥＸ４４ＸＣＴ）に供給して溶融混練した後、次いで、シリンダー途中よりメタクリル酸グリシジル３部、スチレン３部加え溶融混練した後、脱揮してストランド状に押出し、水冷後カッティングして、変性エチレン−プロピレン共重合体（Ａ２）を得た。得られた変性エチレン−プロピレン共重合体（Ａ２）の物性は、表１の通りであった。
(Production Example 2)
Ethylene-propylene copolymer (Varphi 4301, MFR25 manufactured by Dow Co., Ltd., ethylene content 12% by weight, density 0.867 g / cm 3 ) 100 parts, 1,3-di (t-butylperoxyisopropyl) benzene (1 In a twin screw extruder (44 mmφ, L / D = 38.5, manufactured by Nippon Steel Co., Ltd., product name TEX44XCT) in which 0.5 part is set to a cylinder temperature of 200 ° C. and a rotation speed of 150 rpm. After supplying and melt-kneading, next, 3 parts of glycidyl methacrylate and 3 parts of styrene were added and melt-kneaded from the middle of the cylinder, then devolatilized, extruded into a strand shape, water-cooled and cut to obtain a modified ethylene-propylene copolymer. (A2) was obtained. Table 1 shows the physical properties of the modified ethylene-propylene copolymer (A2).
（製造例３）
エチレン−プロピレン共重合体（エクソンモービル（製）：Ｖｉｓｔａｍａｘｘ６２０２、ＭＦＲ１８、エチレン含量１５重量％、密度０．８６１ｇ/ｃｍ3）２０部、１，３−ジ（ｔ-ブチルパーオキシイソプロピル）ベンゼン（１分間半減期１７５℃）０.５部をシリンダー温度２００℃、回転数１５０ｒｐｍに設定した二軸押出機（４４ｍｍφ、Ｌ／Ｄ＝３８．５、（株）日本製鋼所製、製品名ＴＥＸ４４ＸＣＴ）に供給して溶融混練した後、次いで、シリンダー途中よりメタクリル酸グリシジル３部、スチレン３部加え溶融混練した後、脱揮してストランド状に押出し、水冷後カッティングして、変性エチレン−プロピレン共重合体（Ａ３）を得た。得られた変性エチレン−プロピレン共重合体（Ａ３）の物性は、表１の通りであった。
(Production Example 3)
Ethylene-propylene copolymer (ExxonMobil (product): Vistamaxx6202, MFR18, ethylene content 15% by weight, density 0.861 g / cm 3 ) 20 parts, 1,3-di (t-butylperoxyisopropyl) benzene (1 In a twin screw extruder (44 mmφ, L / D = 38.5, manufactured by Nippon Steel Co., Ltd., product name TEX44XCT) in which 0.5 part is set to a cylinder temperature of 200 ° C. and a rotation speed of 150 rpm. After supplying and melt-kneading, next, 3 parts of glycidyl methacrylate and 3 parts of styrene were added and melt-kneaded from the middle of the cylinder, then devolatilized, extruded into a strand shape, water-cooled and cut to obtain a modified ethylene-propylene copolymer. (A3) was obtained. Table 1 shows the physical properties of the obtained modified ethylene-propylene copolymer (A3).
（製造例４）
エチレン−プロピレン共重合体（（株）ダウ製ヴァーシファイDE３４０１．０５、エチレン含量１５重量％、密度０．８６３ｇ/ｃｍ3）１００部、１，３−ジ（ｔ-ブチルパーオキシイソプロピル）ベンゼン（１分間半減期１７５℃）０.５部をシリンダー温度２００℃、回転数１５０ｒｐｍに設定した二軸押出機（４４ｍｍφ、Ｌ／Ｄ＝３８．５、（株）日本製鋼所製、製品名ＴＥＸ４４ＸＣＴ）に供給して溶融混練した後、次いで、シリンダー途中より無水マレイン酸３部、スチレン３部加え溶融混練した後、脱揮してストランド状に押出し、水冷後カッティングして、変性エチレン−プロピレン共重合体（Ａ４）を得た。得られた変性エチレン−プロピレン共重合体（Ａ４）の物性は、表１の通りであった。
(Production Example 4)
100 parts of an ethylene-propylene copolymer (Versify DE3401.05, Dow Co., Ltd., ethylene content 15 wt%, density 0.863 g / cm 3 ), 1,3-di (t-butylperoxyisopropyl) benzene (1 In a twin screw extruder (44 mmφ, L / D = 38.5, manufactured by Nippon Steel Co., Ltd., product name TEX44XCT) in which 0.5 part is set to a cylinder temperature of 200 ° C. and a rotation speed of 150 rpm. After supplying and melt-kneading, 3 parts of maleic anhydride and 3 parts of styrene are added and melt-kneaded from the middle of the cylinder, then devolatilized, extruded into a strand shape, water-cooled and cut to obtain a modified ethylene-propylene copolymer. (A4) was obtained. Table 1 shows the physical properties of the obtained modified ethylene-propylene copolymer (A4).
（製造例５）
ポリエチレン（〔三井石油化学（株）製、ミラソン４０３Ｐ、ＭＦＲ７、密度０．９２８ｇ/ｃｍ3）１００部、１，３−ジ（ｔ-ブチルパーオキシイソプロピル）ベンゼン（１分間半減期１７５℃）０.５部をシリンダー温度２００℃、回転数１５０ｒｐｍに設定した二軸押出機（４４ｍｍφ、Ｌ／Ｄ＝３８．５、（株）日本製鋼所製、製品名ＴＥＸ４４ＸＣＴ）に供給して溶融混練した後、次いで、シリンダー途中よりメタクリル酸グリシジル３部、スチレン３部加え溶融混練した後、脱揮してストランド状に押出し、水冷後カッティングして、変性ポリエチレン共重合体（Ａ５）を得た。得られた変性エチレン−プロピレン共重合体（Ａ５）の物性は、表１の通りであった。
(Production Example 5)
100 parts of polyethylene (Mitsui Petrochemical Co., Ltd., Mirason 403P, MFR7, density 0.928 g / cm 3 ), 1,3-di (t-butylperoxyisopropyl) benzene (1 minute half-life 175 ° C.) 0 After supplying 0.5 parts to a twin screw extruder (44 mmφ, L / D = 38.5, manufactured by Nippon Steel Co., Ltd., product name TEX44XCT) set to a cylinder temperature of 200 ° C. and a rotation speed of 150 rpm, Then, after 3 parts of glycidyl methacrylate and 3 parts of styrene were added and melt-kneaded from the middle of the cylinder, they were devolatilized, extruded into a strand shape, cut with water and cut to obtain a modified polyethylene copolymer (A5). Table 1 shows the physical properties of the obtained modified ethylene-propylene copolymer (A5).
２．ホットメルト型接着フィルムの製造
表２の実施例１〜５及び、比較例１〜９の配合比率に従って、上述の製造例１〜５で得られた変性エチレンープロピレン共重合体（Ａ１）〜（Ａ５）および未変性エチレンーαオレフィン共重合体（Ａ６）、下記原料（Ｂ１）、（Ｂ２）、（Ｂ３）、（Ｃ１）〜（Ｃ５）を、水中カットペレタイザーを取り付けた、シリンダー温度１８０℃に設定した上記二軸押出機で溶融混練して、接着性樹脂ペレットを得た。得られた接着性樹脂ペレットを、シリンダー及びダイス温度２００℃に設定した、単軸押出機（４０ｍｍφ、Ｌ／Ｄ＝２２）、ダイス先端に取り付けたＴ型ダイス（６００ｍｍ幅）より、幅約５００ｍｍ、厚み５０μｍのフィルムに成形した。
（Ａ１）〜（Ａ５）変性エチレンーαオレフィン共重合体（製造例１〜５）
（Ａ６）エチレンープロピレン共重合体（（株）ダウ製ヴァーシファイDE３４０１． ０５）
（Ｂ１）水素添加スチレンイソプレントリブロックコポリマー（（株）クラレ製、ＳＥＰＴＯＮ２０６３）
（Ｂ２）水素添加スチレンブタジエンランダムコポリマー（（株）ＪＳＲ製、Ｄｙｎａｒｏｎ１３２１Ｐ）
（Ｃ１）スチレン変性テルペン樹脂（（株）ヤスハラケミカル製、ＹＳレジンTO１２ ５、軟化点１２５℃）
（Ｃ２）炭化水素系石油樹脂（（株）荒川化学製、アルコンP１４０、軟化点１４０℃）
（Ｃ３）テルペン樹脂（（株）ヤスハラケミカル製、クリアロンＰ１３５、軟化点１３５℃）
（Ｃ４）テルペンフェノール樹脂（（株）ヤスハラケミカル製Ｔ１３０、軟化点１３０℃）
（Ｃ５）ロジン系樹脂（（株）荒川化学製、スーパーエステルＡ１２５、軟化点１２５℃）
2. Production of hot-melt adhesive film According to the blending ratios of Examples 1 to 5 and Comparative Examples 1 to 9 in Table 2, modified ethylene-propylene copolymers obtained in the above Production Examples 1 to 5 ( A1) to (A5) and unmodified ethylene-α olefin copolymer (A6), the following raw materials (B1), (B2), (B3), (C1) to (C5), a cylinder equipped with an underwater cut pelletizer It melt-kneaded with the said twin-screw extruder set to the temperature of 180 degreeC, and obtained the adhesive resin pellet. The obtained adhesive resin pellets are about 500 mm wide from a single-screw extruder (40 mmφ, L / D = 22) set at a cylinder and a die temperature of 200 ° C., and a T-type die (600 mm width) attached to the tip of the die. And formed into a film having a thickness of 50 μm.
(A1) to (A5) Modified ethylene-α-olefin copolymer (Production Examples 1 to 5)
(A6) Ethylene-propylene copolymer (Versify DE3401.05 manufactured by Dow Co., Ltd.)
(B1) Hydrogenated styrene isoprene triblock copolymer (Kuraray Co., Ltd., SPTTON 2063)
(B2) Hydrogenated styrene butadiene random copolymer (manufactured by JSR, Dynanar 1321P)
(C1) Styrene-modified terpene resin (manufactured by Yashara Chemical Co., Ltd., YS Resin TO125, softening point 125 ° C.)
(C2) Hydrocarbon petroleum resin (Arakawa Chemical Co., Ltd., Alcon P140, softening point 140 ° C)
(C3) Terpene resin (manufactured by Yashara Chemical Co., Ltd., Clearon P135, softening point 135 ° C.)
(C4) Terpene phenol resin (T130, Yashara Chemical Co., Ltd., softening point 130 ° C.)
(C5) Rosin resin (manufactured by Arakawa Chemical Co., Ltd., Superester A125, softening point 125 ° C.)
３．ホットメルト型接着フィルムの評価
上述の実施例１〜５及び比較例１〜９の接着性樹脂組成物について、フィルム加工性、フィルム外観、接着性を評価し、表２に記載した。各評価は、下記の方法に従って行なった。
3. Evaluation of Hot Melt Type Adhesive Film The adhesive resin compositions of Examples 1 to 5 and Comparative Examples 1 to 9 described above were evaluated in terms of film processability, film appearance, and adhesiveness and listed in Table 2. Each evaluation was performed according to the following method.
＜フィルム加工性＞
フィルム加工性は、接着性樹脂ペレットのハンドリング性、フィルム成形性から判定した。評価基準は、以下の通りである。
（ペレットハンドリング性）
○：ペレットのブロッキングがなく、良好
△：ペレットがブロッキングするが、手でほぐせる
×：ペレットのブロッキングが激しく、Ｔダイフィルム化不可
（フィルム成形性）
○：良好
△：フィルム化できるが、穴あきが生じる
×：発泡が激しく、フィルム化不可
<Film processability>
The film processability was determined from the handling properties and film moldability of the adhesive resin pellets. The evaluation criteria are as follows.
(Pellet handling)
◯: Pellets are not blocked and good △: Pellets are blocked but can be loosened by hand ×: Pellets are severely blocked and cannot be formed into a T-die film (film formability)
○: Good △: Film can be formed, but perforation occurs. ×: Foaming is severe and film cannot be formed.
＜フィルム外観判定＞
得られた６００ｍｍ巾フィルム約１ｍから、無作為に１００ｍｍ×１００ｍｍのフィルム５枚を切り出して目視観察し、目視可能（目視可能なフィッシュアイの直径は、約１ｍｍ以上とした。）なフィッシュアイの数の平均値を算出し、評価した。評価基準は以下の通りである。
○：フィッシュアイ数１〜４
×：フィッシュアイ数５以上
<Film appearance determination>
From about 1 m of the obtained 600 mm wide film, five 100 mm × 100 mm films were randomly cut out and visually observed, and the visible fish eye diameter was about 1 mm or more. The average value of the numbers was calculated and evaluated. The evaluation criteria are as follows.
○: Number of fish eyes 1 to 4
×: Fisheye number 5 or more
＜接着評価＞
上述の方法で取得できた接着フィルムを、厚み５０μｍのＰＰフィルムと厚み２ｍｍのＰＣ／ＡＢＳプレートの間に挟み、加熱温度１４０℃、０．２ＭＰａで４分間圧着して接着評価サンプルとした。得られた接着評価サンプルを２３℃雰囲気中において、引張り速度１００ｍｍ／分でＰＰフィルムを１８０度ピールし、強度（Ｎ／２５ｍｍ）と破壊状態を評価した。破壊状態としては、材破（ＰＰフィルムの破壊）、界面剥離（ＰＣ／ＡＢＳプレートと接着フィルム界面での界面剥離）で表記した。
<Adhesion evaluation>
The adhesive film obtained by the above-described method was sandwiched between a PP film having a thickness of 50 μm and a PC / ABS plate having a thickness of 2 mm, and pressure-bonded at a heating temperature of 140 ° C. and 0.2 MPa for 4 minutes to obtain an adhesion evaluation sample. The obtained adhesion evaluation sample was peeled 180 degrees at a pulling rate of 100 mm / min in an atmosphere of 23 ° C., and the strength (N / 25 mm) and the fracture state were evaluated. The fracture state was expressed by material breakage (PP film breakage) and interface peeling (interface peeling at the PC / ABS plate / adhesive film interface).
表２に示すとおり、実施例１〜４の請求範囲内の接着性樹脂組成物は、フィルム成形性がよく、良好な外観、接着性を有するホットメルト型フィルムを与えたのに対して、比較例に示した接着性樹脂組成物では、評価項目のいずれか、または全てがより低い評価結果となった。 As shown in Table 2, the adhesive resin compositions in the claims of Examples 1 to 4 had a good film moldability and gave a hot-melt type film having a good appearance and adhesiveness. In the adhesive resin composition shown in the examples, any or all of the evaluation items had lower evaluation results.
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