WO2006030871A1 - Composite sheet - Google Patents

Composite sheet Download PDF

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Publication number
WO2006030871A1
WO2006030871A1 PCT/JP2005/017066 JP2005017066W WO2006030871A1 WO 2006030871 A1 WO2006030871 A1 WO 2006030871A1 JP 2005017066 W JP2005017066 W JP 2005017066W WO 2006030871 A1 WO2006030871 A1 WO 2006030871A1
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WO
WIPO (PCT)
Prior art keywords
mass
composite sheet
resin
styrene
monomer
Prior art date
Application number
PCT/JP2005/017066
Other languages
French (fr)
Japanese (ja)
Inventor
Takeshi Miyakawa
Yutaka Aoki
Original Assignee
Denki Kagaku Kogyo Kabushiki Kaisha
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Application filed by Denki Kagaku Kogyo Kabushiki Kaisha filed Critical Denki Kagaku Kogyo Kabushiki Kaisha
Priority to JP2006535207A priority Critical patent/JP5154081B2/en
Publication of WO2006030871A1 publication Critical patent/WO2006030871A1/en

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/06Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/18Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/30Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10Inorganic particles
    • B32B2264/107Ceramic
    • B32B2264/108Carbon, e.g. graphite particles

Definitions

  • the present invention relates to a composite sheet having a resin composition strength, and the composite sheet can be suitably used, for example, for packaging various electronic parts.
  • Vacuum forming trays, embossed carrier tapes, and the like obtained by thermoforming sheets are used for packaging containers for intermediate products of all industrial products such as electronic devices and automobiles.
  • a sheet in which a polystyrene resin or an ABS resin is laminated with a polystyrene resin has been proposed (see, for example, Patent Documents 1 to 3).
  • sheets obtained by extrusion molding, etc. are molded by various known molding methods such as vacuum molding, pressure molding, press molding, etc.
  • ABS-based resins and polystyrene-based resins have adhesive properties. Depending on the bad usage method, there is a problem that peeling occurs between the base material layer and the skin layer.
  • the outer periphery and in some cases the internal force of the embossed carrier tape is called a sprocket hole or center hole.
  • burrs are generated on the end face with little force. In the process where the packaging container is used, burrs fall off and become contaminated.
  • electronic components to be packaged have been downsized rapidly, and the demand for reducing the contamination caused by the dropping of the paste has become strict.
  • Patent Document 1 Japanese Patent Laid-Open No. 57-205145
  • Patent Document 2 JP-A-9-076425
  • Patent Document 3 Japanese Patent Laid-Open No. 9-076422
  • the present invention solves a significant problem, improves adhesion between each layer of the sheet to prevent peeling, and at the same time, is a punching caloe used in a manufacturing process of a tray or an embossed carrier tape.
  • the aim is to provide a composite sheet that reduces the contamination of electronic parts, etc., which is a content that generates less burr due to burrs.
  • the present invention solves the above problems and has the following gist.
  • a composite sheet characterized by laminating a skin layer mainly composed of polystyrene based resin and carbon black on at least one surface of a base material layer mainly composed of ABS based resin.
  • ABS system ⁇ is, Jen rubber 5 to 23 weight 0/0, the main component an aromatic vinyl monomer 55 to 80 wt%, and Shiani spoon Bulle monomer 15-27 wt% ABS
  • the composite sheet according to the above (1) characterized in that the composite sheet is made of a resinous resin.
  • ABS-based ⁇ force diene rubber 40 to 60 mass 0/0, the aromatic vinyl monomer 25 to 45 mass%, the graft mainly cyanide Bulle monomer 5-25% by weight 15 to 60 parts by mass of a polymer, and 40 to 85 parts by mass of a binary vinyl copolymer mainly composed of 60 to 85% by mass of an aromatic vinyl monomer and 15 to 40% by mass of a vinyl cyanide monomer.
  • the composite sheet as described in (1) or (2) above.
  • the composite sheet of the present invention is suitable for packaging electronic parts and the like that need countermeasures against static electricity.
  • a packaging container such as a tray or an embossed carrier tape
  • the skin layer In addition, the substrate layer does not peel off, and the occurrence of burr at that time is small. It is possible to reduce the contamination caused by the removal of this glue.
  • the ABS-based resin used in the base material layer in the composite sheet of the present invention is composed mainly of a terpolymer of gen-based rubber, aromatic vinyl monomer, and vinyl cyanide monomer.
  • a resin or a resin composition mainly composed of a terpolymer of acrylonitrile butadiene styrene.
  • Specific examples thereof include acrylonitrile-butadiene styrene terpolymer, a mixture of acrylonitrile butadiene styrene terpolymer and acrylo-tolyl styrene terpolymer, and polybutadiene polymer acrylonitrile styrene terpolymer.
  • an acrylonitrile-butadiene-styrene terpolymer it is preferable to use an acrylonitrile-butadiene-styrene terpolymer, and a mixture of acrylonitrile-butadiene-styrene terpolymer and acrylonitrile-styrene terpolymer is used. Is more preferable.
  • the acrylonitrile butadiene styrene terpolymer includes, for example, an aromatic butyl monomer such as styrene, and a cyanhibi such as acrylonitrile in the presence of a gen-based rubber such as polybutadiene styrene butadiene copolymer. It can be obtained by graft copolymerization of dil monomer.
  • acrylonitrile-butadiene styrene terpolymer is Jen rubber 40-60 mass 0/0, preferably 4 0-55% by weight, aromatic vinyl monomer 25-45% by weight, preferably 30-40% by weight, cyanobimer monomer 5-25% by weight, preferably 5-20% by weight, More preferably, it is preferable to use a graft copolymer containing 5 to 18% by mass as a main component.
  • an aromatic butyl monomer is 60 to 85 mass 0/0, preferably 65-80% by weight
  • cyanide Bulle monomer is 15 to 40 wt%, preferably to use a copolymer mainly composed of 20 to 35 wt%.
  • the mixing ratio of acrylonitrile-butagen-styrene terpolymer and acrylonitrile styrene terpolymer is preferably 15 to 60 parts by mass of acrylonitrile-butadiene-styrene terpolymer and acrylonitrile-styrene terpolymer.
  • diene rubber content in the ABS system ⁇ is preferably from 5 to 30 weight 0/0 device is 5-23 wt%, more preferably from 8 to 20 mass%. If the Gen rubber content is less than 5% by mass, the strength will decrease, and if it is more than 30% by mass, burrs will increase.
  • the content of the cyanated butyl monomer in the ABS-based rosin is 10 to 40% by mass, preferably 15 to 27% by mass, and preferably 20 to 25% by mass. If the content of the vinyl cyanide monomer is less than this range, the rigidity decreases, and if it exceeds this range, peeling between layers with the laminated polystyrene resin tends to occur.
  • the content of the aromatic vinyl monomer which is the remaining component in the ABS-based resin is preferably 40 to 80% by mass, more preferably 55 to 80% by mass, and particularly preferably 65 to 72% by mass. Use.
  • the polystyrene-based resin used for the skin layer of the present invention is styrene, o-methylol styrene, p-methyl styrene, p-tert-butyl styrene, 1,3 dimethyl styrene, ⁇ -methylol styrene, vinylenonaphthalene, Preferred is a resin mainly composed of a polymer having an aromatic bur compound such as vinylolanthracene or 1,1-diphenylenoethylene, or an impact-resistant polystyrene styrene resin.
  • Impact resistant polystyrene resin is based on butadiene. Polystyrene resin obtained by graft polymerization of rubber. These polystyrene resins and impact-resistant polystyrene resins can be used alone or in combination.
  • the carbon black to be blended in the resin of the skin layer is furnace black, channel black, acetylene black, etc., and preferably high conductivity is obtained with a small amount added to the resin having a large specific surface area. It is what For example, there are SCF (Super Conductive Furnace), ECF (Electric Conductive Furnace), Ketchen Hook, a product name of Fion AKZO), and acetylene black.
  • the addition amount is preferably a surface-specific resistance of 10 2 to: a amount can be ⁇ ⁇ ⁇ , and carbon black 1 to the total amount 100 mass% of the set formed of the skin layer 50% by mass is preferred.
  • the composite sheet of the present invention is obtained by laminating a skin layer (wrinkle) on at least one surface of the base material layer (wrinkle). Specifically, it is possible to take a structure of skin layer ( ⁇ ) ⁇ base material layer ( ⁇ ), skin layer ( ⁇ ) ⁇ base material layer (A) ⁇ skin layer ( ⁇ ). In particular, the structure of skin layer ( ⁇ ) ⁇ base material layer (A) ⁇ skin layer ( ⁇ ) is preferred from the viewpoint of suppressing the generation of static electricity on both sides of the composite sheet.
  • the total thickness of the composite sheet of the present invention is preferably 0.1 to 3. Omm, more preferably 0.15 to 2. Omm.
  • a sheet having an overall thickness of 0.15 to 0.6 mm can be suitably used as an electronic component packaging sheet that is secondarily formed on an embossed carrier tape.
  • the overall wall thickness is 0.5mn! ⁇ 2.
  • Omm can be suitably used as a packaging sheet for storing electronic parts, machine parts, etc. by secondary forming as a tray.
  • the thickness of the base material layer (A) in the total thickness is preferably 40% to 98%.
  • the thickness of the skin layer (B) occupying the entire thickness is preferably 2 to 30% (in the case of having both surfaces).
  • Carbon black is used for the base material layer in a small amount, preferably AB, without impairing fluidity.
  • other resin components can be added as modifiers to the base material layer and the Z or skin layer, and if necessary, lubricants, plasticizers, Various additives such as processing aids can be added.
  • the other resin components include styrene butadiene-butylene styrene block copolymer (hereinafter also referred to as SBBS), styrene gen block copolymer resin, styrene gen block copolymer hydrogenated resin, and At least one kind of thermoplastic resin that can be selected from a group consisting of resin obtained by graft copolymerization of styrene and polyolefin can be suitably used.
  • SBBS styrene butadiene-butylene styrene block copolymer
  • styrene gen block copolymer resin styrene gen block copolymer hydrogenated resin
  • At least one kind of thermoplastic resin that can be selected from a group consist
  • coffins can be added alone or a plurality of them can be used simultaneously.
  • impact strength is improved, adhesion to the skin layer is improved, delamination is suppressed, and generation of crumbs of sheet edge force is suppressed.
  • the addition amount is preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the total amount of polystyrene-based and ABS-based resins.
  • Styrene butadiene-butylene A styrene block copolymer is a copolymer having repeating units represented by the following chemical formulas (1), (2) and (3).
  • a, b and c represent a positive integer.
  • the styrene butadiene-butylene styrene block copolymer is not particularly limited as long as it has the structure described above.
  • SBBS thermoplastic elastomer
  • Styrene Butadiene-Butylene Styrene block copolymer can be used as it is.
  • Styrene content of the styrene-butadiene-butylene-styrene block copolymer is more preferably preferably from 10 to 80% by weight instrument is 2 0-70 mass 0/0. Further, it is preferable that the copolymer has a melt flow index (190 ° C, 2.16 kgf) of 1 to 9 gZl0 min, and more preferably 2 to 6 gZl0 min.
  • the gen of the styrene gen block copolymer resin or the hydrogenated resin of the styrene gen block copolymer is preferably butadiene or isoprene.
  • the styrene content of the styrene gen block copolymer resin or the hydrogenated styrene resin of the styrene gen block copolymer is preferably 10 to 80% by mass, more preferably 20 to 70% by mass.
  • olefin-based resins include polyethylene resin, polypropylene resin, ethylene-OC-olefin resin, ethylene acetate butyl copolymer resin, ethylene ethyl acrylate copolymer resin, and the like.
  • polyester-based resin include polyethylene terephthalate resin and polybutylene terephthalate resin.
  • the composite sheet of the present invention can be produced by a known method using an extruder, calendar molding or the like.
  • a method of laminating each layer of the sheet it is also possible to form each in a sheet or film form by using a separate extruder and then laminate stepwise by a thermal laminating method, a dry laminating method, an extrusion laminating method, or the like.
  • a method such as extrusion coating it is also possible to obtain a laminated sheet by a multi-layer coextrusion method using a multi-hold die or a feed block.
  • an electronic component packaging container having a free shape By using a known sheet forming method such as vacuum forming, pressure forming, press forming or the like from the above-mentioned sheet, an electronic component packaging container having a free shape can be obtained.
  • This container has excellent mechanical strength with less contamination of the end surface force of the container, and can be suitably used particularly as a tray or carrier tape for packaging electronic components.
  • acrylonitrile-butadiene-styrene terpolymer having the composition shown in Table 1, acrylonitrile styrene binary copolymer (AS), and, if necessary, SBBS are used.
  • the mixture was uniformly mixed with a mixer at the ratio shown in the above to obtain a resin composition for the base material layer.
  • the thickness ratio of skin layer: base material layer: skin layer is 1: 8: 1 It was formed into a three-layer sheet having a thickness of 0.3 mm.
  • Table 3 shows the evaluation results of each example. Evaluation was carried out by the following method.
  • DuPont impact strength Using a DuPont impact tester Z Toyo Seiki Co., Ltd., a 300g, 500g or lkg load was dropped to obtain a 50% fracture height, and the energy value was calculated from the load at that time. Calculation was performed according to IS-K-7211.
  • Formability Molded into an embossed carrier tape with a width of 24 mm using a compressed air embossed tape molding machine manufactured by EDG. A five-step evaluation was performed with 5 having good formability and 1 having poor formability.
  • the rosin used as the skin layer in each example is as follows.
  • Polystyrene resin Toyostyrene HI-SQ (Toyo Styrene Co., Ltd.)
  • Examples 1 to 6 are superior to Examples 7 to 11 in terms of removing burrs and peeling resistance.
  • Graft copolymer Acrylonitrile-butadiene-styrene terpolymer AS: Acrylonitrile styrene-original copolymer AN: Acrylonitrile monomer
  • a to E Represents different types of polymers of the same type.
  • SBBS Styrene Butadiene Butylene Styrene Block Copolymer Resin
  • Vacuum forming trays, embossed carrier tapes, and the like obtained by thermoforming the composite sheet according to the present invention are widely and suitably used as packaging containers for intermediate products in the fields of electronic equipment and automobiles.

Abstract

A composite sheet, characterized in that it comprises a base material layer having, as a main component, an ABS based resin containing a diene based rubber preferably in an amount of 5 to 23 mass %, and, laminated on at least one surface thereof, a surface skin layer having a polystyrene based resin and carbon black as a main component. The above composite sheet exhibits an improved adhesion between respective layers and thus is reduced in the amount of burrs (punching burrs) generated in a punching step carried out in a process for producing a tray or an embossed carrier tape.

Description

明 細 書  Specification
複合シート  Composite sheet
技術分野  Technical field
[0001] 本発明は榭脂組成物力 なる複合シートに関し、該複合シートは例えば各種電子 部品包装用に好適に用いることができる。  [0001] The present invention relates to a composite sheet having a resin composition strength, and the composite sheet can be suitably used, for example, for packaging various electronic parts.
背景技術  Background art
[0002] 電子機器や自動車などあらゆる工業製品の中間製品の包装容器にはシートを加熱 成形して得られる真空成形トレー、エンボスキャリアテープなどが使用されている。こ れら包装容器用シートとしてはポリスチレン系榭脂若しくは ABS系榭脂にポリスチレ ン系榭脂を積層したシートが提案され (例えば特許文献 1〜3参照)使用されている。 トレー、エンボスキャリアテープは押し出し成形等により得られたシートを真空成形、 圧空成形、プレス成形等、公知の各種成形法で成形されるが、 ABS系榭脂とポリスチ レン系榭脂は接着性が悪ぐ使用方法によってはその基材層と表皮層の層間で剥離 が生じるという問題があった。  [0002] Vacuum forming trays, embossed carrier tapes, and the like obtained by thermoforming sheets are used for packaging containers for intermediate products of all industrial products such as electronic devices and automobiles. As these packaging container sheets, a sheet in which a polystyrene resin or an ABS resin is laminated with a polystyrene resin has been proposed (see, for example, Patent Documents 1 to 3). For trays and embossed carrier tapes, sheets obtained by extrusion molding, etc. are molded by various known molding methods such as vacuum molding, pressure molding, press molding, etc. ABS-based resins and polystyrene-based resins have adhesive properties. Depending on the bad usage method, there is a problem that peeling occurs between the base material layer and the skin layer.
また、トレーの成形においてはその外周や場合によってはその内部力 エンボスキ ャリアテープにおいてはスプロケットホールやセンターホールと呼ばれる穴力 また、 打ち抜き加工される際に、その端面に少な力もずバリが生じ、これらの包装容器が使 用される工程でバリが脱落しコンタミとなる。近年、包装される電子部品が急激に小 型化しており、このノ リの脱落により生じるコンタミの低減に対する要望が厳しくなつて いる。  Also, in the molding of trays, the outer periphery and in some cases the internal force of the embossed carrier tape is called a sprocket hole or center hole. Also, when punching is performed, burrs are generated on the end face with little force. In the process where the packaging container is used, burrs fall off and become contaminated. In recent years, electronic components to be packaged have been downsized rapidly, and the demand for reducing the contamination caused by the dropping of the paste has become strict.
特許文献 1:特開昭 57— 205145号公報  Patent Document 1: Japanese Patent Laid-Open No. 57-205145
特許文献 2 :特開平 9— 076425号公報  Patent Document 2: JP-A-9-076425
特許文献 3 :特開平 9— 076422号公報  Patent Document 3: Japanese Patent Laid-Open No. 9-076422
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0003] 本発明は力かる問題点を解決し、シートの各層間の接着性を改善し剥離の防止を 図ると同時に、トレーやエンボスキャリアテープの製造工程で行われる打ち抜きカロェ によるバリ(抜きバリ)の発生が少なぐ内容物である電子部品等に対するコンタミを低 減した複合シートを提供しょうとするものである。 [0003] The present invention solves a significant problem, improves adhesion between each layer of the sheet to prevent peeling, and at the same time, is a punching caloe used in a manufacturing process of a tray or an embossed carrier tape. The aim is to provide a composite sheet that reduces the contamination of electronic parts, etc., which is a content that generates less burr due to burrs.
課題を解決するための手段 Means for solving the problem
本発明は、上記の課題を解決するものであり、下記の要旨を有するものである。 The present invention solves the above problems and has the following gist.
(1) ABS系榭脂を主成分とする基材層の少なくとも片面にポリスチレン系榭脂及び カーボンブラックを主成分とする表皮層を積層したことを特徴とする複合シート。(1) A composite sheet characterized by laminating a skin layer mainly composed of polystyrene based resin and carbon black on at least one surface of a base material layer mainly composed of ABS based resin.
(2) ABS系榭脂がジェン系ゴム 5〜23質量0 /0を含有することを特徴とする上記(1) に記載の複合シート。 (2) the composite sheet according to (1) the ABS system榭脂is characterized by containing a diene-based rubber 5 to 23 weight 0/0.
(3) ABS系榭脂が、ジェン系ゴム 5〜23質量0 /0、芳香族ビニル単量体 55〜80質量 %、及びシアンィ匕ビュル単量体 15〜27質量%を主成分とする ABS系榭脂からなる ことを特徴とする上記(1)に記載の複合シート。 (3) ABS system榭脂is, Jen rubber 5 to 23 weight 0/0, the main component an aromatic vinyl monomer 55 to 80 wt%, and Shiani spoon Bulle monomer 15-27 wt% ABS The composite sheet according to the above (1), characterized in that the composite sheet is made of a resinous resin.
(4) ABS系榭脂力 ジェン系ゴム 40〜60質量0 /0、芳香族ビニル単量体 25〜45質 量%、シアン化ビュル単量体 5〜25質量%を主成分とするグラフト共重合体 15〜60 質量部、及び芳香族ビニル単量体 60〜85質量%、シアン化ビニル単量体 15〜40 質量%を主成分とする二元ビニル共重合体 40〜85質量部からなることを特徴とする 上記(1)又は(2)に記載の複合シート。 (4) ABS-based榭脂force diene rubber 40 to 60 mass 0/0, the aromatic vinyl monomer 25 to 45 mass%, the graft mainly cyanide Bulle monomer 5-25% by weight 15 to 60 parts by mass of a polymer, and 40 to 85 parts by mass of a binary vinyl copolymer mainly composed of 60 to 85% by mass of an aromatic vinyl monomer and 15 to 40% by mass of a vinyl cyanide monomer. The composite sheet as described in (1) or (2) above.
(5)ジェン系ゴム 5〜30質量0 /0、芳香族ビュル単量体 40〜80質量0 /0、シアン化ビ- ル単量体 10〜40質量%を主成分とする ABS系榭脂 100質量部と、スチレンーブタ ジェンーブチレン スチレンブロック共重合体榭脂、スチレン ジェンブロック共重 合体榭脂、スチレン ジェンブロック共重合体に水素添加した榭脂及びポリオレフィ ンにスチレンをグラフト共重合した榭脂から選ばれる少なくとも 1種類の熱可塑性榭 脂 1〜20質量部と、力もなる基材層の少なくとも片面にポリスチレン系榭脂及びカー ボンブラックを主成分とする表皮層を積層したことを特徴とする上記(1)に記載の複 合シート。 (5) diene-based rubber 5 to 30 mass 0/0, the aromatic Bulle monomer 40 to 80 weight 0/0, cyan mold - ABS system composed mainly of Le monomer 10 to 40 wt%榭脂100 parts by mass, styrene-but-gen-butylene styrene block copolymer resin, styrene gen block copolymer resin, hydrogenated styrene gen block copolymer resin, and resin obtained by graft copolymerization of styrene with polyolefin 1 to 20 parts by mass of at least one kind of thermoplastic resin, and a skin layer mainly composed of polystyrene-based resin and carbon black is laminated on at least one surface of the base material layer which is also powerful ( Composite sheet as described in 1).
(6) ABS系榭脂力 ジェン系ゴム 40〜60質量0 /0、芳香族ビニル単量体 25〜45質 量%、及びシアンィ匕ビュル単量体 5〜25質量%を主成分とするグラフト共重合体 15 〜60質量部と、芳香族ビニル単量体 60〜85質量%、及びシアン化ビニル単量体 1 5〜40質量%を主成分とする二元ビニル共重合体 40〜85質量部と、力 なることを 特徴とする上記(5)に記載の複合シート。 (6) ABS-based榭脂force diene rubber 40 to 60 mass 0/0, the aromatic vinyl monomer 25 to 45 mass%, and a graft composed mainly of Shiani spoon Bulle monomer 5-25% by weight Copolymer 15 to 60 parts by mass, aromatic vinyl monomer 60 to 85% by mass, and vinyl cyanide monomer 15 to 40% by mass binary vinyl copolymer 40 to 85% by mass Department and power The composite sheet according to (5) above, which is characterized.
(7)上記(1)〜(6)の 、ずれか 1項記載の複合シートを用いた容器。  (7) A container using the composite sheet according to any one of (1) to (6) above.
(8)上記(1)〜(6)のいずれか 1項記載の複合シートを用いたエンボスキャリアテー プ。  (8) An embossed carrier tape using the composite sheet according to any one of (1) to (6) above.
(9)上記(1)〜(6)のいずれか 1項記載の複合シートを用いた包装体。  (9) A package using the composite sheet according to any one of (1) to (6) above.
発明の効果  The invention's effect
[0005] 本発明の複合シートは、静電気対策の必要な電子部品等の包装に適しており、本 発明の複合シートを用いてトレーやエンボスキャリアテープ等の包装容器を製造する 工程において、表皮層と基材層が剥離することが無ぐまた、その際の抜きバリの発 生が少なぐこのノ リの脱落により生じるコンタミを減少させることが可能となる。 発明を実施するための最良の形態  [0005] The composite sheet of the present invention is suitable for packaging electronic parts and the like that need countermeasures against static electricity. In the process of manufacturing a packaging container such as a tray or an embossed carrier tape using the composite sheet of the present invention, the skin layer In addition, the substrate layer does not peel off, and the occurrence of burr at that time is small. It is possible to reduce the contamination caused by the removal of this glue. BEST MODE FOR CARRYING OUT THE INVENTION
[0006] 本発明の複合シートにおいて基材層に用いる ABS系榭脂とは、ジェン系ゴム一芳 香族ビニル単量体 シアン化ビニル単量体の 3元共重合体を主成分とするもので、 代表的には、アクリロニトリル ブタジエン スチレンの 3元共重合体を主成分とする 榭脂又は榭脂組成物を意味する。その具体例としては、アクリロニトリル—ブタジエン スチレン三元共重合体、アクリロニトリル ブタジエン スチレン三元共重合体とァ クリロ-トリルースチレン二元共重合体の混合物、アクリロニトリル スチレン二元共重 合体にポリブタジエンをポリマーァロイ化したものがあげられる。本発明ではこれらの 中でアクリロニトリル—ブタジエン—スチレン三元共重合体を用いるのが好ましぐ更 にアクリロニトリル一ブタジエン一スチレン三元共重合体とアクリロニトリル一スチレン 二元共重合体の混合物を使用するのがより好ましい。 [0006] The ABS-based resin used in the base material layer in the composite sheet of the present invention is composed mainly of a terpolymer of gen-based rubber, aromatic vinyl monomer, and vinyl cyanide monomer. Typically, it means a resin or a resin composition mainly composed of a terpolymer of acrylonitrile butadiene styrene. Specific examples thereof include acrylonitrile-butadiene styrene terpolymer, a mixture of acrylonitrile butadiene styrene terpolymer and acrylo-tolyl styrene terpolymer, and polybutadiene polymer acrylonitrile styrene terpolymer. Can be given. In the present invention, it is preferable to use an acrylonitrile-butadiene-styrene terpolymer, and a mixture of acrylonitrile-butadiene-styrene terpolymer and acrylonitrile-styrene terpolymer is used. Is more preferable.
[0007] 前記アクリロニトリル ブタジエン スチレン三元共重合体は、例えば、ポリブタジ ェンゃスチレン ブタジエン共重合体等のジェン系ゴムの存在下で、スチレン等の 芳香族ビュル単量体や、アクリロニトリル等のシアンィヒビ二ル単量体をグラフト共重合 すること〖こよって得られる。  [0007] The acrylonitrile butadiene styrene terpolymer includes, for example, an aromatic butyl monomer such as styrene, and a cyanhibi such as acrylonitrile in the presence of a gen-based rubber such as polybutadiene styrene butadiene copolymer. It can be obtained by graft copolymerization of dil monomer.
[0008] ABS系榭脂として、アクリロニトリル ブタジエン スチレン三元共重合体とアタリ口 二トリル—スチレン二元共重合体の混合物を使用する場合には、アクリロニトリル—ブ タジェン一スチレン三元重合体として、ジェン系ゴムが 40〜60質量0 /0、好ましくは 4 0〜55質量%、芳香族ビニル単量体が 25〜45質量%、好ましくは 30〜40質量%、 シアンィ匕ビ二ル単量体が 5〜25質量%、好ましくは 5〜20質量%、更に好ましくは 5 〜18質量%を主成分とするグラフト共重合体を使用するのが好ましぐまた、アタリ口 二トリル—スチレン二元共重合体としては、芳香族ビュル単量体が 60〜85質量0 /0、 好ましくは 65〜80質量%、シアン化ビュル単量体が 15〜40質量%、好ましくは 20 〜35質量%を主成分とする共重合体を使用するのが好ましい。アクリロニトリル—ブ タジェン—スチレン三元共重合体とアクリロニトリル スチレン二元共重合体の混合 比率は、好ましくは、アクリロニトリル—ブタジエン—スチレン三元共重合体 15〜60 質量部とアクリロニトリル スチレン二元共重合体 40〜85質量部であり、より好ましく は、アクリロニトリル—ブタジエン—スチレン三元共重合体 30〜45質量部とアタリ口- トリル—スチレン二元共重合体 55〜70質量部である。アクリロニトリル—ブタジエン スチレン三元共重合体のグラフト率は 30〜90%が好ましぐより好ましくは 30〜60 %である。 [0008] When a mixture of acrylonitrile butadiene styrene terpolymer and alicyclic nitrile styrene terpolymer is used as the ABS resin, acrylonitrile-butadiene styrene terpolymer is Jen rubber 40-60 mass 0/0, preferably 4 0-55% by weight, aromatic vinyl monomer 25-45% by weight, preferably 30-40% by weight, cyanobimer monomer 5-25% by weight, preferably 5-20% by weight, More preferably, it is preferable to use a graft copolymer containing 5 to 18% by mass as a main component. Also, as the attalyl nitrile-styrene binary copolymer, an aromatic butyl monomer is 60 to 85 mass 0/0, preferably 65-80% by weight, cyanide Bulle monomer is 15 to 40 wt%, preferably to use a copolymer mainly composed of 20 to 35 wt%. The mixing ratio of acrylonitrile-butagen-styrene terpolymer and acrylonitrile styrene terpolymer is preferably 15 to 60 parts by mass of acrylonitrile-butadiene-styrene terpolymer and acrylonitrile-styrene terpolymer. The amount is 40 to 85 parts by mass, and more preferably 30 to 45 parts by mass of acrylonitrile-butadiene-styrene terpolymer and 55 to 70 parts by mass of tali-tril-styrene binary copolymer. The graft ratio of acrylonitrile-butadiene styrene terpolymer is preferably 30 to 90%, more preferably 30 to 60%.
[0009] ABS系榭脂中のジェン系ゴム含有量は 5〜30質量0 /0が好ましぐより好ましくは 5 〜23質量%であり、更に好ましくは 8〜20質量%である。ジェン系ゴムの含有量が 5 質量%より少ないと強度が低下してしまい、 30質量%より多いとバリの発生が多くな る。 [0009] More preferably diene rubber content in the ABS system榭脂is preferably from 5 to 30 weight 0/0 device is 5-23 wt%, more preferably from 8 to 20 mass%. If the Gen rubber content is less than 5% by mass, the strength will decrease, and if it is more than 30% by mass, burrs will increase.
[0010] ABS系榭脂中のシアン化ビュル単量体含有量は 10〜40質量%であり、好ましく は 15〜27質量%であり、好ましくは 20〜25質量%である。シアン化ビニル単量体の 含有量がこの範囲より少ないと剛性が低下し、この範囲より多いと積層したポリスチレ ン系榭脂との層間で剥離を生じやすくなつてしまう。尚、 ABS系榭脂中の残りの成分 である芳香族ビニル単量体含有量は好ましくは 40〜80質量%、より好ましくは 55〜 80質量%、特に好ましくは 65〜72質量%の範囲で用いる。  [0010] The content of the cyanated butyl monomer in the ABS-based rosin is 10 to 40% by mass, preferably 15 to 27% by mass, and preferably 20 to 25% by mass. If the content of the vinyl cyanide monomer is less than this range, the rigidity decreases, and if it exceeds this range, peeling between layers with the laminated polystyrene resin tends to occur. The content of the aromatic vinyl monomer which is the remaining component in the ABS-based resin is preferably 40 to 80% by mass, more preferably 55 to 80% by mass, and particularly preferably 65 to 72% by mass. Use.
[0011] 本発明の表皮層に用いるポリスチレン系榭脂とは、スチレン、 o—メチノレスチレン、 p ーメチルスチレン、 p—tert—ブチルスチレン、 1, 3 ジメチルスチレン、 α—メチノレ スチレン、ビニノレナフタレン、ビニノレアントラセン、 1, 1ージフエニノレエチレン等の芳 香族ビュル化合物を単量体とするポリマーを主成分とする榭脂、又は、耐衝撃性ポリ スチレン榭脂が好ましい。耐衝撃性ポリスチレン榭脂とは、ブタジエンを主成分とする ゴムをグラフト重合したポリスチレン榭脂である。これらポリスチレン榭脂及び耐衝撃 性ポリスチレン榭脂はそれぞれ単独で用いることもできるし、併用してもよ 、。 [0011] The polystyrene-based resin used for the skin layer of the present invention is styrene, o-methylol styrene, p-methyl styrene, p-tert-butyl styrene, 1,3 dimethyl styrene, α-methylol styrene, vinylenonaphthalene, Preferred is a resin mainly composed of a polymer having an aromatic bur compound such as vinylolanthracene or 1,1-diphenylenoethylene, or an impact-resistant polystyrene styrene resin. Impact resistant polystyrene resin is based on butadiene. Polystyrene resin obtained by graft polymerization of rubber. These polystyrene resins and impact-resistant polystyrene resins can be used alone or in combination.
[0012] 表皮層の樹脂に配合するカーボンブラックは、ファーネスブラック、チャンネルブラ ック、アセチレンブラック等であり、好ましくは比表面積が大きぐ榭脂への添加量が 少量で高度の導電性が得られるものである。例えば S. C. F. (Super Conductive Furnace)、 E. C. F. (Electric Conductive Furnace)、ケッチェンフフック、フ イオン AKZO社製商品名)、アセチレンブラック等がある。その添加量は、表面固 有抵抗値を好ましくは 102〜: ίΟω Ωとすることのできる添加量であり、かつ表皮層の組 成物の合計量 100質量%に対してカーボンブラック 1〜50質量%が好ましい。添カロ 量が 1質量%未満では十分な導電性が得られず表面固有抵抗値が上昇してしまい、 50質量%を越えると榭脂との均一分散性の悪化、成形加工性の著しい低下、機械 的強度等の特性値が低下してしまう。 [0012] The carbon black to be blended in the resin of the skin layer is furnace black, channel black, acetylene black, etc., and preferably high conductivity is obtained with a small amount added to the resin having a large specific surface area. It is what For example, there are SCF (Super Conductive Furnace), ECF (Electric Conductive Furnace), Ketchen Hook, a product name of Fion AKZO), and acetylene black. The addition amount is preferably a surface-specific resistance of 10 2 to: a amount can be ίΟ ω Ω, and carbon black 1 to the total amount 100 mass% of the set formed of the skin layer 50% by mass is preferred. If the amount of added calories is less than 1% by mass, sufficient electrical conductivity cannot be obtained and the surface resistivity increases, and if it exceeds 50% by mass, the uniform dispersibility with the resin is deteriorated, and the molding processability is significantly reduced. Characteristic values such as mechanical strength will decrease.
[0013] 本発明の複合シートは、基材層 (Α)の少なくとも片面に表皮層(Β)を積層するもの である。具体的には、表皮層 (Β) Ζ基材層 (Α)、表皮層 (Β) Ζ基材層 (A) Ζ表皮層 (Β)、の構成をとることが可能である。特に、複合シートの両面で静電気の発生を抑 制する意味からは、表皮層(Β) Ζ基材層 (A) Ζ表皮層(Β)の構成が好ま ヽ。  [0013] The composite sheet of the present invention is obtained by laminating a skin layer (wrinkle) on at least one surface of the base material layer (wrinkle). Specifically, it is possible to take a structure of skin layer (Β) Ζ base material layer (Α), skin layer (Β) Ζ base material layer (A) 皮 skin layer (Β). In particular, the structure of skin layer (Β) Ζ base material layer (A) が skin layer (Β) is preferred from the viewpoint of suppressing the generation of static electricity on both sides of the composite sheet.
[0014] 本発明の複合シート全体の肉厚は 0. 1〜3. Ommが好ましぐ更に好ましくは 0. 1 5〜2. Ommである。特に全体の肉厚が 0. 15〜0. 6mmのものはエンボスキャリアテ ープに二次成形して使用する電子部品包装用シートとして好適に用いることができる 。また、全体の肉厚が、 0. 5mn!〜 2. Ommのものはトレーとして二次成形して電子 部品、機械部品等を収納する包装用シートとして好適に用いることができる。全体の 肉厚に占める基材層(A)の肉厚は 40%〜98%が好ましい。また全体の肉厚に占め る表皮層(B)の肉厚は(両面に有する場合にはそれぞれ) 2〜30%が好ましい。  [0014] The total thickness of the composite sheet of the present invention is preferably 0.1 to 3. Omm, more preferably 0.15 to 2. Omm. In particular, a sheet having an overall thickness of 0.15 to 0.6 mm can be suitably used as an electronic component packaging sheet that is secondarily formed on an embossed carrier tape. Also, the overall wall thickness is 0.5mn! 〜 2. Omm can be suitably used as a packaging sheet for storing electronic parts, machine parts, etc. by secondary forming as a tray. The thickness of the base material layer (A) in the total thickness is preferably 40% to 98%. Further, the thickness of the skin layer (B) occupying the entire thickness is preferably 2 to 30% (in the case of having both surfaces).
[0015] 基材層にはカーボンブラックを、流動性を損なわな 、程度に少量、好ましくは、 AB [0015] Carbon black is used for the base material layer in a small amount, preferably AB, without impairing fluidity.
S系榭脂成分に対して 0. 1〜30質量部の範囲で添加することが可能である。カーボ ンブラックの添カ卩によりシートを包装容器に成形した際にシート厚みが薄くなり成形品 のコーナー部等が透けてしまうといった問題点を解決することが可能となる。基材層 に添加するカーボンブラックに特に制限はなくファーネスブラック、チャンネルブラック 、アセチレンブラック等公知ものもが使用可能である。 It is possible to add in the range of 0.1 to 30 parts by mass with respect to the S-based resin component. When the sheet is formed into a packaging container by using carbon black, the problem that the sheet thickness becomes thin and the corners of the molded product can be seen through can be solved. There is no particular restriction on the carbon black added to the base material layer. Furnace black, channel black Well-known ones such as acetylene black can be used.
[0016] 基材層及び Z又は表皮層には、前記の榭脂成分に加えて他の榭脂成分を改質剤 として添加することも可能であり、更に必要に応じて滑剤、可塑剤、加工助剤などの 各種添加剤を添加することが可能である。前記の他の榭脂成分としては、スチレン ブタジエンーブチレン スチレンブロック共重合体(以下、 SBBSともいう)、スチレン ジェンブロック共重合体榭脂、スチレン ジェンブロック共重合体に水素添加した 榭脂、及びポリオレフインにスチレンをグラフト共重合した榭脂からなる群力も選ばれ る少なくとも 1種の熱可塑性榭脂は好適に用いることができる。  [0016] In addition to the above-mentioned resin components, other resin components can be added as modifiers to the base material layer and the Z or skin layer, and if necessary, lubricants, plasticizers, Various additives such as processing aids can be added. Examples of the other resin components include styrene butadiene-butylene styrene block copolymer (hereinafter also referred to as SBBS), styrene gen block copolymer resin, styrene gen block copolymer hydrogenated resin, and At least one kind of thermoplastic resin that can be selected from a group consisting of resin obtained by graft copolymerization of styrene and polyolefin can be suitably used.
これらの榭脂は単独で添加することも可能であるし、複数を同時に用いることも可能 である。これらの熱可塑性榭脂を添加することで、衝撃強度の向上が図られるととも に、表皮層との接着性が向上し層間剥離の抑制やシート端面力 のケバゃ粉の発生 が抑制される。添加量はポリスチレン系榭脂と ABS系榭脂の合計量 100質量部に対 し 1〜20質量部好ましく、更に好ましくは 3〜 15質量部である。  These coffins can be added alone or a plurality of them can be used simultaneously. By adding these thermoplastic resins, impact strength is improved, adhesion to the skin layer is improved, delamination is suppressed, and generation of crumbs of sheet edge force is suppressed. . The addition amount is preferably 1 to 20 parts by mass, more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the total amount of polystyrene-based and ABS-based resins.
[0017] スチレン ブタジエンーブチレン スチレンブロック共重合体とは次の(1)、 (2)及 び(3)の化学式で表わされる繰り返し単位を有する共重合体である。なお、(1)、 (2) 及び(3)の化学式における、 a、 b、 cは、正の整数を表わす。  [0017] Styrene butadiene-butylene A styrene block copolymer is a copolymer having repeating units represented by the following chemical formulas (1), (2) and (3). In the chemical formulas (1), (2) and (3), a, b and c represent a positive integer.
[0018] [化 1]  [0018] [Chemical 1]
Figure imgf000007_0001
Figure imgf000007_0001
[0019] [化 2] [0019] [Chemical 2]
-(C H— C H = C H— C H — - ( 2 ) -(C H— C H = C H— C H —-(2)
[0020] [化 3] C H— C H [0020] [Chemical 3] CH— CH
T 2 3  T 2 3
-t C H— C H "^- ( 3 ) -t CH— CH "^-( 3 )
[0021] スチレン ブタジエンーブチレン スチレンブロック共重合体は、前記の構造を有 するものであればこのものの製造方法には特に限定されない。例えば、製造方法とし ては「新規スチレン系熱可塑性エラストマ一(SBBS)の構造と性能」(栄秀司等、第 9 回ポリマー材料フォーラム、 125〜126頁、 2000年;)、特開昭 64— 38402号、特開 昭 60— 220147号、特開昭 63— 5402号、特開昭 63— 4841号、特開昭 61— 331 32号、特開昭 63— 5401号、特開昭 61— 28507号、特開昭 61— 57524号等に報 告されている。スチレン ブタジエンーブチレン スチレンブロック共重合体は巿販 のものをそのまま使用することもできる。スチレン ブタジエンーブチレン スチレン ブロック共重合体中のスチレン含有量は 10〜80質量%が好ましぐ更に好ましくは 2 0〜70質量0 /0である。また、該共重合体のメルトフローインディックス(190°C、 2. 16 kgf)が l〜9gZl0minのものが好適であり、 2〜6gZl0minのものが更に好適に用 いることがでさる。 [0021] The styrene butadiene-butylene styrene block copolymer is not particularly limited as long as it has the structure described above. For example, as a manufacturing method, “Structure and performance of a new styrenic thermoplastic elastomer (SBBS)” (Eiji Hideshi et al., 9th Polymer Material Forum, pages 125 to 126, 2000;), JP-A 64- 38402, JP-A 60-220147, JP-A 63-5402, JP-A 63-4841, JP-A 61-331 32, JP-A 63-5401, JP-A 61-28507 No., JP-A 61-57524, and the like. Styrene Butadiene-Butylene Styrene block copolymer can be used as it is. Styrene content of the styrene-butadiene-butylene-styrene block copolymer is more preferably preferably from 10 to 80% by weight instrument is 2 0-70 mass 0/0. Further, it is preferable that the copolymer has a melt flow index (190 ° C, 2.16 kgf) of 1 to 9 gZl0 min, and more preferably 2 to 6 gZl0 min.
[0022] スチレン ジェンブロック共重合体榭脂又はスチレン ジェンブロック共重合体に 水素添カ卩した樹脂のジェンとしてはブタジエン又はイソプレンが好まし 、。スチレン ジェンブロック共重合体榭脂又はスチレン ジェンブロック共重合体に水素添カ卩した 榭脂のスチレン含有量は 10〜80質量%が好ましぐ更に好ましくは 20〜70質量% である。ポリオレフインにスチレンをグラフト共重合した榭脂のポリオレフインとしてはェ チレン、プロピレンのホモポリマー又はコポリマーであり、特にポリエチレン、ポリプロ ピレン、又はエチレン 酢酸ビュル共重合体が好まし 、。  [0022] The gen of the styrene gen block copolymer resin or the hydrogenated resin of the styrene gen block copolymer is preferably butadiene or isoprene. The styrene content of the styrene gen block copolymer resin or the hydrogenated styrene resin of the styrene gen block copolymer is preferably 10 to 80% by mass, more preferably 20 to 70% by mass. Polyolefins of rosin obtained by graft copolymerization of styrene with polyolefin are homopolymers or copolymers of ethylene and propylene, particularly polyethylene, polypropylene, or ethylene acetate butyl copolymer.
[0023] 表皮層に用いるポリスチレン系榭脂にはスチレン ブタジエンーブチレンースチレ ンブロック(SBBS)共重合体榭脂、スチレン ジェンブロック共重合体榭脂、スチレ ンージェンブロック共重合体に水素添加した榭脂、ポリオレフインにスチレンをグラフ ト共重合した榭脂、エチレン若しくはプロピレンを主成分とするホモポリマーゃコポリ マーに代表されるポリオレフイン系榭脂、ポリエステル系榭脂、 ABS系榭脂等の他の 榭脂成分を改質剤として添加することも可能である。更に必要に応じて滑剤、可塑剤 、加工助剤などの各種添加剤を添加することが可能である。 [0023] Polystyrene resin used for the skin layer was hydrogenated to a styrene butadiene-butylene polystyrene block (SBBS) copolymer resin, a styrene gen block copolymer resin, and a styrene block copolymer. Other resins such as resin, grafted styrene with polyolefin, polyolefin resin represented by homopolymer mainly composed of ethylene or propylene, polyester resin, ABS resin, etc. It is also possible to add a resin component as a modifier. Furthermore, various additives such as a lubricant, a plasticizer, and a processing aid can be added as necessary.
[0024] ォレフィン系榭脂の代表例としては、ポリエチレン榭脂、ポリプロピレン榭脂、ェチレ ンー OCーォレフイン榭脂、エチレン 酢酸ビュル共重合体榭脂、エチレン ェチル アタリレート共重合体榭脂等があげられる。ポリエステル系榭脂の代表例としてはポリ エチレンテレフタレート榭脂、ポリブチレンテレフタレート榭脂等があげられる。  [0024] Representative examples of olefin-based resins include polyethylene resin, polypropylene resin, ethylene-OC-olefin resin, ethylene acetate butyl copolymer resin, ethylene ethyl acrylate copolymer resin, and the like. . Representative examples of polyester-based resin include polyethylene terephthalate resin and polybutylene terephthalate resin.
[0025] 本発明の複合シートは、押出機、カレンダー成形等を用いた公知の方法によって 製造することができる。シートの各層を積層する方法としては、それぞれを別々の押 出機によりシートもしくはフィルム状に成形した後、熱ラミネート法、ドライラミネート法 、押出ラミネート法等により段階的に積層することも可能である。また、予め成形した シートの基材層の上に押出コーティング等の法により他の層を積層することも可能で ある。より安価に製造するにはマルチマ-ホールドダイやフィードブロックを用 、た多 層共押出法により一括して積層シートを得ることが好ましい。  [0025] The composite sheet of the present invention can be produced by a known method using an extruder, calendar molding or the like. As a method of laminating each layer of the sheet, it is also possible to form each in a sheet or film form by using a separate extruder and then laminate stepwise by a thermal laminating method, a dry laminating method, an extrusion laminating method, or the like. . It is also possible to laminate another layer on a preformed sheet base layer by a method such as extrusion coating. In order to manufacture at a lower cost, it is preferable to obtain a laminated sheet by a multi-layer coextrusion method using a multi-hold die or a feed block.
[0026] 上述のシートから真空成形、圧空成型、プレス成形等公知のシートの成形方法を 使用することにより、自由な形状の電子部品包装容器を得ることができる。この容器 は、容器の端面力 のコンタミが少なぐ機械的強度も優れており、特に電子部品を 包装するトレーやキャリアテープとして好適に使用可能である。 [0026] By using a known sheet forming method such as vacuum forming, pressure forming, press forming or the like from the above-mentioned sheet, an electronic component packaging container having a free shape can be obtained. This container has excellent mechanical strength with less contamination of the end surface force of the container, and can be suitably used particularly as a tray or carrier tape for packaging electronic components.
実施例  Example
[0027] 以下、本発明を実施例によりさらに詳細に説明する。  Hereinafter, the present invention will be described in more detail with reference to examples.
実施例 1〜11  Examples 1-11
表皮層として、ポリスチレン榭脂 70質量部、カーボンブラック 20質量部及びェチレ ン—ェチルアタリレート榭脂 10質量部からなる原料を高速混合機により均一混合し た。得られる混合物を φ 45mmのベント式二軸押出機を用いて混練し、ストランドカツ ト法によりペレツトイ匕した。  Raw materials consisting of 70 parts by mass of polystyrene resin, 20 parts by mass of carbon black, and 10 parts by mass of ethylene-ethyl acrylate resin were uniformly mixed by a high-speed mixer as the skin layer. The resulting mixture was kneaded using a vented twin screw extruder having a diameter of 45 mm and pelletized by a strand cutting method.
一方、表 1に示す組成のアクリロニトリル—ブタジエン—スチレン三元共重合体 (グ ラフト共重合体)、アクリロニトリル スチレン二元共重合体 (AS)、及び必要に応じて 、 SBBSを使用し、表 2に示す割合にて混合機により均一混合し基材層の榭脂組成 物とした。この基材層用榭脂組成物と上記の表皮層用ペレットを使用し、 φ 65mm押 出機(LZD = 28)、 φ 40mm押出機(LZD= 26) 2台とフィードブロック及び Tダイ を用いて、表皮層:基材層:表皮層の厚み比率が 1 : 8 : 1で全体の厚さ 0. 3mmを有 する 3層のシート状に成形した。 On the other hand, acrylonitrile-butadiene-styrene terpolymer (graft copolymer) having the composition shown in Table 1, acrylonitrile styrene binary copolymer (AS), and, if necessary, SBBS are used. The mixture was uniformly mixed with a mixer at the ratio shown in the above to obtain a resin composition for the base material layer. Using this resin composition for base material layer and the above pellets for skin layer, press φ65mm Extruder (LZD = 28), φ40mm Extruder (LZD = 26) Using a feed block and T-die, the thickness ratio of skin layer: base material layer: skin layer is 1: 8: 1 It was formed into a three-layer sheet having a thickness of 0.3 mm.
[0028] 各実施例の評価結果を表 3に示す。評価は以下の方法によって実施した。 [0028] Table 3 shows the evaluation results of each example. Evaluation was carried out by the following method.
(1) 耐折強度: JIS— P— 8115 (2001年)に準拠し荷重5008、角度 135度で評価 を行った。 (1) Folding strength: Evaluation was performed at a load of 500 8 and an angle of 135 degrees in accordance with JIS-P-8115 (2001).
(2) 引張強度: JIS—K— 7127 (1999年)に準拠し 4号評価を行った。  (2) Tensile strength: No. 4 evaluation was performed based on JIS-K-7127 (1999).
(3) 表面抵抗値:メガオームメーター Mode卜 800 (ets社製)を使用しシート幅方向に 3点測定し、その対数平均値を表面固有抵抗値とした。  (3) Surface resistance: Using a mega ohm meter Mode 卜 800 (manufactured by ets), three points were measured in the sheet width direction, and the logarithmic average value was defined as the surface resistivity.
(4) デュポンインパクト強度:デュポン衝撃試験機 Z東洋精機社製を使用し、 300g 、 500g若しくは lkgの荷重を落下させ 50%破壊高さを求め、その時の荷重からエネ ルギー値を計算した。計算 ίお IS—K— 7211に準じて行った。  (4) DuPont impact strength: Using a DuPont impact tester Z Toyo Seiki Co., Ltd., a 300g, 500g or lkg load was dropped to obtain a 50% fracture height, and the energy value was calculated from the load at that time. Calculation was performed according to IS-K-7211.
(5) 成形性: EDG社製圧空エンボステープ成形機で 24mm幅のエンボスキャリア テープに成形した。賦形性が良好なものを 5、賦形性が不良なものを 1とし 5段階評 価を行った。  (5) Formability: Molded into an embossed carrier tape with a width of 24 mm using a compressed air embossed tape molding machine manufactured by EDG. A five-step evaluation was performed with 5 having good formability and 1 having poor formability.
(6) 抜きノ リ率: EDG社成形機で成形したエンボスキャリアテープのスプロケットホー ル部を測定顕微鏡 (ミツトヨ社製)で観察した。バリの無い状態を 0%とし、スプロケット ホール中に占めるバリの面積の割合を計算した。  (6) Pulling rate: The sprocket hole part of the embossed carrier tape formed with an EDG molding machine was observed with a measuring microscope (manufactured by Mitutoyo Corporation). The ratio of burr area in the sprocket hole was calculated with 0% as the burr-free state.
(7) 耐剥離性: EDG成形機で成形した 24mm幅のエンボスキャリアテープに対し、 カバーテープをシールする部分に 16mm間隔で片側 60力所、計 120力所の表面に カッターナイフで浅い傷を付け、その後シール強度の平均値が約 1. ONとなるような 条件でシールした。このサンプルを約 200mmZminの速度で 90°C剥離し、カバーテ ープに付着したシート表層材の数を長さ別に 0. 2m以下を S、 0. 2〜lmmを M、 lm m以上を Lとして整理した。尚、カバーテープとしてはデンカサーモフィルム ALS— A S (電気化学工業社製)を使用した。  (7) Peeling resistance: 24mm wide embossed carrier tape molded with an EDG molding machine, with 60mm on one side at 16mm intervals in the area to seal the cover tape, with a knife knife on the surface for a total of 120 scratches. After that, sealing was performed under the condition that the average value of the seal strength was about 1. ON. This sample was peeled at 90 ° C at a speed of about 200 mmZmin. Tidy. As the cover tape, Denka Thermofilm ALS-AS (manufactured by Denki Kagaku Kogyo Co., Ltd.) was used.
[0029] 各実施例で表皮層として使用した榭脂は以下の通りである。  [0029] The rosin used as the skin layer in each example is as follows.
ポリスチレン榭脂:トーヨースチロール HI-SQ (東洋スチレン社製)  Polystyrene resin: Toyostyrene HI-SQ (Toyo Styrene Co., Ltd.)
カーボンブラック:デンカブラック 粒状 (電気化学工業社製) エチレン ェチルアタリレート共重合体: DPDJ— 6169 (日本ュ-カー社製)Carbon black: Denka black granular (manufactured by Denki Kagaku Kogyo) Ethylene ethyl acrylate copolymer: DPDJ— 6169 (manufactured by Nippon Car Company)
SBBS: タフテック P - 2000 (旭化成ケミカルズ社製) SBBS: Tuftec P-2000 (Asahi Kasei Chemicals)
[0030] 実施例 1〜6は、実施例 7〜11に比べて 、ずれも抜きバリ性及び耐剥離性にお!ヽ て優れている。 [0030] Examples 1 to 6 are superior to Examples 7 to 11 in terms of removing burrs and peeling resistance.
[0031] [表 1] [0031] [Table 1]
Figure imgf000011_0001
Figure imgf000011_0001
[0032] [表 2] 表 2 [0032] [Table 2] Table 2
実 施 1 ¾ Implementation 1 ¾
1 2 3 4 5 6 71 2 3 4 5 6 7
A 質量部 20 20 35 35 20 グラフ卜共重合体 B 質量部 20 A part by mass 20 20 35 35 20 Graphite copolymer B part by mass 20
C 質量部 100  C parts by mass 100
D 質量部 80 65 D Mass part 80 65
A S A S
E 質量部 80 80 65 80 E Mass part 80 80 65 80
S B B S 5 S B B S 5
AN 質量% 28. 0 22. 4 28. 6 24. 0 25. 0 20. 5 28. 0 AN Mass% 28. 0 22. 4 28. 6 24. 0 25. 0 20. 5 28. 0
A B S樹脂の成分比 St 65. 0 67. 6 61. 4 66. 0 57. 5 62. 0 62. 0 Component ratio of A B S resin St 65. 0 67. 6 61. 4 66. 0 57. 5 62. 0 62. 0
Bd 質 10. 0 10. 0 10. 0 10. 0 17. 5 17. 5 10. 0 Bd quality 10. 0 10. 0 10. 0 10. 0 17. 5 17. 5 10. 0
table
実 施 例  Example
1 2 3 4 5 6 抜きバリ率 % 1. 12 0.99 1.17 1.31 1.57 1.35  1 2 3 4 5 6 Burr ratio% 1. 12 0.99 1.17 1.31 1.57 1.35
MD 54 54 50 49 47 51 降伏強度 Mpa  MD 54 54 50 49 47 51 Yield strength Mpa
TD 51 51 51 50 46 49 TD 51 51 51 50 46 49
MD 42 39 42 38 38 39 破断強度 Mpa MD 42 39 42 38 38 39 Breaking strength Mpa
TD 38 40 39 41 36 47 引張特性  TD 38 40 39 41 36 47 Tensile properties
MD 165 39 140 78 137 50 伸び率 %  MD 165 39 140 78 137 50 Elongation%
TD 50 11 23 13 22 7 TD 50 11 23 13 22 7
MD 2, 360 2, 340 2, 230 2, 140 2, 060 2, 190 弾性率 Mpa MD 2, 360 2, 340 2, 230 2, 140 2, 060 2, 190 Elastic modulus Mpa
TD 2, 300 2, 270 2, 260 2, 180 2, 060 2, 120 デュポン衝撃強度 J 0.97 0.35 0.97 0.40 1.40 0.42  TD 2, 300 2, 270 2, 260 2, 180 2, 060 2, 120 Dupont impact strength J 0.97 0.35 0.97 0.40 1.40 0.42
MD 36 22 29 255 160 213 耐折強度 回  MD 36 22 29 255 160 213 Folding strength times
TD 52 16 27 22 134 53 TD 52 16 27 22 134 53
MD 196 201 212 204 178 205 引裂強度 N MD 196 201 212 204 178 205 Tear strength N
TD 184 62 190 175 182 174 表面抵抗率 Ώ/sq 2.6X104 3.1X104 2.3X104 3.5X 104 3.9X104 2.8X104 成形性 5 5 5 5 5 5 TD 184 62 190 175 182 174 Surface resistivity Ώ / sq 2.6X10 4 3.1X10 4 2.3X10 4 3.5X 10 4 3.9X10 4 2.8X10 4 Formability 5 5 5 5 5 5
S 4 0 S 4 0
M 0 0 耐剥離性 M 0 0 Peel resistance
L 0 0 a al 4 0 L 0 0 a al 4 0
Figure imgf000014_0001
なお、表 1、表 2及び表 3において、以下の記号は、それぞれ、以下の意味を表わ す。
Figure imgf000014_0001
In Table 1, Table 2, and Table 3, the following symbols represent the following meanings.
グラフト共重合体:アクリロニトリル—ブタジエン—スチレン三元共重合体 AS:アクリロニトリル スチレン-元共重合体 AN:アクリロニトリル単量体 Graft copolymer: Acrylonitrile-butadiene-styrene terpolymer AS: Acrylonitrile styrene-original copolymer AN: Acrylonitrile monomer
St:スチレン単量体  St: Styrene monomer
Bd:ブタジエン単量体  Bd: butadiene monomer
A〜E :同種の重合体でも種類が異なるものを表わす。  A to E: Represents different types of polymers of the same type.
SBBS:スチレン ブタジエン ブチレン スチレンブロック共重合体榭脂 SBBS: Styrene Butadiene Butylene Styrene Block Copolymer Resin
MD: Machine Direction MD: Machine Direction
TD: Traverse Direction  TD: Traverse Direction
産業上の利用可能性  Industrial applicability
[0036] 本発明による複合シートを加熱成形して得られる真空成形トレー、エンボスキャリア テープなどは、電子機器や自動車などの分野における中間製品などの包装容器とし て広範に好適に使用される。 [0036] Vacuum forming trays, embossed carrier tapes, and the like obtained by thermoforming the composite sheet according to the present invention are widely and suitably used as packaging containers for intermediate products in the fields of electronic equipment and automobiles.
[0037] なお、 2004年 9月 16曰に出願された曰本特許出願 2004— 269346号、 2004年[0037] It should be noted that the Japanese patent application 2004-269346, filed on September 16, 2004, 2004
9月 16曰に出願された曰本特許出願 2004— 269347号、及び 2004年 9月 16曰に 出願された日本特許出願 2004— 269348号、の明細書、特許請求の範囲、図面及 び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるもので ある。 Japanese Patent Application 2004-269347 filed September 16th, and Japanese Patent Application 2004-269348 filed September 16th 2004, Claims, Drawings and Abstract Is hereby incorporated by reference as a disclosure of the specification of the present invention.

Claims

請求の範囲 The scope of the claims
[1] ABS系榭脂を主成分とする基材層の少なくとも片面にポリスチレン系榭脂及び力 一ボンブラックを主成分とする表皮層を積層したことを特徴とする複合シート。  [1] A composite sheet characterized by laminating a surface layer mainly composed of polystyrene-based resin and force bon black on at least one surface of a base material layer mainly composed of ABS-based resin.
[2] ABS系榭脂が、ジェン系ゴム 5〜23質量0 /0を含有することを特徴とする請求項 1に 記載の複合シート。 [2] The composite sheet of claim 1 ABS system榭脂, characterized in that it contains a diene-based rubber 5 to 23 weight 0/0.
[3] ABS系榭脂力 ジェン系ゴム 5〜23質量0 /0、芳香族ビュル単量体 55〜80質量0 /0 [3] ABS system榭脂force diene-based rubber 5 to 23 weight 0/0, the aromatic Bulle monomer 55 to 80 weight 0/0
、及びシアン化ビニル単量体 15〜27質量%を含有することを特徴とする請求項 1に 記載の複合シート。 And a vinyl cyanide monomer in an amount of 15 to 27% by mass.
[4] ABS系榭脂力 ジェン系ゴム 40〜60質量0 /0、芳香族ビュル単量体 25〜45質量[4] ABS system榭脂force diene rubber 40 to 60 mass 0/0, the aromatic Bulle monomer from 25 to 45 weight
%及びシアンィ匕ビ二ル単量体 5〜25質量%を主成分とするグラフト共重合体 15〜6 0質量部と、芳香族ビニル単量体 60〜85質量%及びシアン化ビニル単量体 15〜4 0質量%を主成分とする二元ビニル共重合体 40〜85質量部と、力 なることを特徴 とする請求項 1又は 2に記載の複合シート。 % And cyan vinyl monomer 15 to 60 parts by mass of graft copolymer based on 5 to 25% by mass, aromatic vinyl monomer 60 to 85% by mass and vinyl cyanide monomer 3. The composite sheet according to claim 1, wherein the composite sheet comprises 40 to 85 parts by mass of a binary vinyl copolymer containing 15 to 40% by mass as a main component.
[5] ジェン系ゴム 5〜30質量0 /0、芳香族ビュル単量体 40〜80質量0 /0、シアン化ビュル 単量体 10〜40質量%を主成分とする ABS系榭脂 100質量部と、スチレン—ブタジ ェンーブチレン スチレンブロック共重合体榭脂、スチレン ジェンブロック共重合 体榭脂、スチレン ジェンブロック共重合体に水素添加した榭脂及びポリオレフイン にスチレンをグラフト共重合した榭脂から選ばれる少なくとも 1種類の熱可塑性榭脂 1[5] Jen rubber 5-30 wt 0/0, ABS system榭脂100 mass for aromatic Bulle monomer 40 to 80 weight 0/0, 10 to 40 wt% cyanide Bulle monomer as a main component Styrene-butadiene-butylene styrene block copolymer resin, styrene gen block copolymer resin, hydrogenated styrene gen block copolymer resin, and polyolefin resin grafted with styrene. At least one thermoplastic resin 1
〜20質量部と、力もなる基材層の少なくとも片面にポリスチレン系榭脂及びカーボン ブラックを主成分とする表皮層を積層したことを特徴とする請求項 1に記載の複合シ ート。 2. The composite sheet according to claim 1, wherein a skin layer mainly composed of polystyrene-based resin and carbon black is laminated on at least one surface of the base material layer having a force of 20 parts by mass.
[6] ABS系榭脂力 ジェン系ゴム 40〜60質量0 /0、芳香族ビニル単量体 25〜45質量[6] ABS system榭脂force diene rubber 40 to 60 mass 0/0, the aromatic vinyl monomer 25 to 45 weight
%、及びシアンィ匕ビュル単量体 5〜25質量%を主成分とするグラフト共重合体 15〜 60質量部と、芳香族ビニル単量体 60〜85質量%及びシアン化ビニル単量体 15〜 40質量%を主成分とする二元ビニル共重合体 40〜85質量部と、力 なることを特徴 とする請求項 5に記載の複合シート。 %, And 15 to 60 parts by mass of a graft copolymer mainly composed of 5 to 25% by mass of cyanobyl monomer, 60 to 85% by mass of aromatic vinyl monomer and 15 to 6. The composite sheet according to claim 5, wherein the composite sheet comprises 40 to 85 parts by mass of a binary vinyl copolymer containing 40% by mass as a main component.
[7] 請求項 1〜6の 、ずれか 1項記載の複合シートを用いた容器。 [7] A container using the composite sheet according to any one of claims 1 to 6.
[8] 請求項 1〜6のいずれか 1項記載の複合シートを用いたエンボスキャリアテープ。 [9] 請求項 1〜6のいずれか 1項記載の複合シートを用いた包装体。 [8] An embossed carrier tape using the composite sheet according to any one of claims 1 to 6. [9] A package using the composite sheet according to any one of claims 1 to 6.
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WO2011118522A1 (en) * 2010-03-24 2011-09-29 電気化学工業株式会社 Surface conductive laminated sheet and electronic part packaging container
JP2011219693A (en) * 2010-04-14 2011-11-04 Umg Abs Ltd Resin composition for coating polystyrene-based resin and coated molding
JP2012051249A (en) * 2010-09-01 2012-03-15 Denki Kagaku Kogyo Kk Surface conducting laminated sheet
WO2012046807A1 (en) 2010-10-07 2012-04-12 電気化学工業株式会社 Surface conductive multilayered sheet
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CN103153614B (en) * 2010-10-07 2015-04-29 电气化学工业株式会社 Surface conductive multilayered sheet
WO2012046807A1 (en) 2010-10-07 2012-04-12 電気化学工業株式会社 Surface conductive multilayered sheet
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CN103153614A (en) * 2010-10-07 2013-06-12 电气化学工业株式会社 Surface conductive multilayered sheet
WO2012099068A1 (en) 2011-01-17 2012-07-26 電気化学工業株式会社 Multilayer styrenic resin sheet
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WO2014007135A1 (en) * 2012-07-02 2014-01-09 住友ベークライト株式会社 Base sheet for electronic component packaging, multilayer sheet for electronic component packaging, carrier tape for electronic component packaging, and electronic component carrier
CN104395397A (en) * 2012-07-02 2015-03-04 住友电木株式会社 Base sheet for electronic component packaging, multilayer sheet for electronic component packaging, carrier tape for electronic component packaging, and electronic component carrier
JP2014009337A (en) * 2012-07-02 2014-01-20 Sumitomo Bakelite Co Ltd Substrate sheet for electronic component packaging, multilayer sheet for electronic component packaging, carrier tape for electronic component packaging, and electronic component transportation body
WO2018084129A1 (en) * 2016-11-01 2018-05-11 デンカ株式会社 Surface-conductive laminated sheet and electronic component packaging container
WO2022149420A1 (en) * 2021-01-08 2022-07-14 デンカ株式会社 Sheet for packaging electronic part
KR20230128364A (en) 2021-01-08 2023-09-04 덴카 주식회사 Sheets for Electronic Components Packaging
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TWI402166B (en) 2013-07-21

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