JP2009110842A - Laminated resin body for button switch coating - Google Patents

Laminated resin body for button switch coating Download PDF

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Publication number
JP2009110842A
JP2009110842A JP2007283069A JP2007283069A JP2009110842A JP 2009110842 A JP2009110842 A JP 2009110842A JP 2007283069 A JP2007283069 A JP 2007283069A JP 2007283069 A JP2007283069 A JP 2007283069A JP 2009110842 A JP2009110842 A JP 2009110842A
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Prior art keywords
resin layer
layer
laminated
bis
button switch
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JP2007283069A
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Japanese (ja)
Inventor
Tomohiro Maekawa
智博 前川
Hiroshi Koyama
浩士 小山
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Priority to JP2007283069A priority Critical patent/JP2009110842A/en
Priority to TW097141641A priority patent/TW200937471A/en
Priority to CNA2008101683984A priority patent/CN101425413A/en
Priority to KR1020080107852A priority patent/KR20090045121A/en
Publication of JP2009110842A publication Critical patent/JP2009110842A/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H13/00—Switches having rectilinearly-movable operating part or parts adapted for pushing or pulling in one direction only, e.g. push-button switch
    • H01H13/02—Details
    • H01H13/12—Movable parts; Contacts mounted thereon
    • H01H13/14—Operating parts, e.g. push-button
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H13/00—Switches having rectilinearly-movable operating part or parts adapted for pushing or pulling in one direction only, e.g. push-button switch
    • H01H13/02—Details
    • H01H13/04—Cases; Covers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H13/00—Switches having rectilinearly-movable operating part or parts adapted for pushing or pulling in one direction only, e.g. push-button switch
    • H01H13/70—Switches having rectilinearly-movable operating part or parts adapted for pushing or pulling in one direction only, e.g. push-button switch having a plurality of operating members associated with different sets of contacts, e.g. keyboard
    • H01H13/702—Switches having rectilinearly-movable operating part or parts adapted for pushing or pulling in one direction only, e.g. push-button switch having a plurality of operating members associated with different sets of contacts, e.g. keyboard with contacts carried by or formed from layers in a multilayer structure, e.g. membrane switches
    • H01H13/704—Switches having rectilinearly-movable operating part or parts adapted for pushing or pulling in one direction only, e.g. push-button switch having a plurality of operating members associated with different sets of contacts, e.g. keyboard with contacts carried by or formed from layers in a multilayer structure, e.g. membrane switches characterised by the layers, e.g. by their material or structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H13/00—Switches having rectilinearly-movable operating part or parts adapted for pushing or pulling in one direction only, e.g. push-button switch
    • H01H13/70—Switches having rectilinearly-movable operating part or parts adapted for pushing or pulling in one direction only, e.g. push-button switch having a plurality of operating members associated with different sets of contacts, e.g. keyboard
    • H01H13/702—Switches having rectilinearly-movable operating part or parts adapted for pushing or pulling in one direction only, e.g. push-button switch having a plurality of operating members associated with different sets of contacts, e.g. keyboard with contacts carried by or formed from layers in a multilayer structure, e.g. membrane switches
    • H01H13/705—Switches having rectilinearly-movable operating part or parts adapted for pushing or pulling in one direction only, e.g. push-button switch having a plurality of operating members associated with different sets of contacts, e.g. keyboard with contacts carried by or formed from layers in a multilayer structure, e.g. membrane switches characterised by construction, mounting or arrangement of operating parts, e.g. push-buttons or keys

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating member for a button switch which is hard to have scratches and is hardly broken. <P>SOLUTION: The laminated resin body in which acrylic resin layer is laminated on at least one of the surfaces of polycarbonate resin layer and the thickness of the polycarbonate resin layer is 50% or more of the total thickness is used as a coating member of a button switch. It is preferable that the polycarbonate resin layer and acrylic resin layer are laminated by coextrusion forming, and the acrylic resin layer is a layer consisting of a methacrylic resin and a rubber-like copolymer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、ボタンスイッチを被覆するための積層樹脂体に関する。   The present invention relates to a laminated resin body for covering a button switch.

携帯電話、デジタルカメラ、電子手帳、リモコン、パーソナルコンピューターのキーボードを始め、工業用や医療用の精密機械などに使用されている押ボタンスイッチやタッチセンサーボタンスイッチの如きボタンスイッチは、機器本体の薄型化が進んだ結果、小さくかつ薄いものに移りつつある。ボタンスイッチが小さくなると、可動部分の隙間調整が難しくなり、ボタン自体が連続使用により歪んだり、機器の内側へ入り込んだりするトラブルが発生しやすくなる。また、最近は防水仕様にするため、ボタンと本体の隙間をできるだけ小さくしたり、機器本体内側にゴム張りなどの加工を行ったりする工夫もされているが、ボタンが早期に稼動しなくなったり、設計の都合上、本体が大きくなったりするなど、不具合が発生しやすくなる。   Button switches such as push button switches and touch sensor button switches used in mobile phones, digital cameras, electronic notebooks, remote controls, personal computer keyboards, industrial and medical precision machines, etc. As a result of the progress of development, it is shifting to small and thin. When the button switch is small, it becomes difficult to adjust the gap between the movable parts, and the button itself is apt to be distorted by continuous use or to enter the inside of the device. Also, recently, in order to make it waterproof, the gap between the button and the main unit is made as small as possible, and processing such as rubber tension inside the device main unit has been devised, but the button does not work early, Due to design reasons, problems such as the main body becoming larger are more likely to occur.

これらの問題を解決するため、ボタンスイッチを被覆することが検討されており、例えば特開２００５−３１０５４０号公報（特許文献１）には、アクリル樹脂フィルムをボタンスイッチの被覆部材として用いることが開示されている。   In order to solve these problems, it has been studied to cover a button switch. For example, Japanese Patent Laying-Open No. 2005-310540 (Patent Document 1) discloses using an acrylic resin film as a covering member for a button switch. Has been.

特開２００５−３１０５４０号公報JP 2005-310540 A

特許文献１に開示の如く、ボタンスイッチの被覆部材としてアクリル樹脂フィルムを用いれば、傷が付きにくいという点で有利であるが、機器が落下したり、物が当たったりした際、割れやすいという問題がある。そこで、本発明の目的は、傷が付きにくく、かつ割れにくいボタンスイッチの被覆部材を提供することにある。   As disclosed in Patent Document 1, if an acrylic resin film is used as the covering member of the button switch, it is advantageous in that it is difficult to be damaged, but it is easy to break when the device falls or hits it. There is. Accordingly, an object of the present invention is to provide a covering member for a button switch which is not easily damaged and is not easily broken.

本発明者らは、鋭意検討の結果、特定の積層樹脂体をボタンスイッチの被覆部材として採用することにより、上記目的が達成できることを見出し、本発明を完成するに至った。すなわち、本発明は、ポリカーボネート樹脂層の少なくとも一方の面にアクリル樹脂層が積層されてなり、ポリカーボネート樹脂層の厚みが全体の厚みの５０％以上であることを特徴とするボタンスイッチ被覆用積層樹脂体を提供するものである。   As a result of intensive studies, the present inventors have found that the above object can be achieved by employing a specific laminated resin body as a covering member for a button switch, and have completed the present invention. That is, the present invention relates to a laminated resin for button switch coating, characterized in that an acrylic resin layer is laminated on at least one surface of a polycarbonate resin layer, and the thickness of the polycarbonate resin layer is 50% or more of the total thickness. Provide the body.

本発明のボタンスイッチ被覆用積層樹脂体は、傷が付きにくく、かつ割れにくいので、ボタンスイッチを効果的に被覆することができる。   Since the laminated resin body for covering a button switch of the present invention is hardly scratched and hardly cracked, the button switch can be effectively covered.

本発明の積層樹脂体は、ポリカーボネート樹脂層の少なくとも一方の面にアクリル樹脂層が積層されてなり、ボタンスイッチを被覆するために用いられるものである。   The laminated resin body of the present invention comprises an acrylic resin layer laminated on at least one surface of a polycarbonate resin layer, and is used for covering a button switch.

ポリカーボネート層を構成するポリカーボネート樹脂としては、例えば、二価フェノールとカルボニル化剤とを界面重縮合法や溶融エステル交換法などで反応させることにより得られるものの他、カーボネートプレポリマーを固相エステル交換法などで重合させることにより得られるもの、環状カーボネート化合物を開環重合法で重合させることにより得られるものなどが挙げられる。   Examples of the polycarbonate resin constituting the polycarbonate layer include those obtained by reacting a dihydric phenol and a carbonylating agent by an interfacial polycondensation method, a melt transesterification method, or the like, or a carbonate prepolymer by a solid phase transesterification method. And those obtained by polymerizing a cyclic carbonate compound by a ring-opening polymerization method.

二価フェノールとしては、例えば、ハイドロキノン、レゾルシノール、４，４’−ジヒドロキシジフェニル、ビス（４−ヒドロキシフェニル）メタン、ビス｛（４−ヒドロキシ−３，５−ジメチル）フェニル｝メタン、１，１−ビス（４−ヒドロキシフェニル）エタン、１，１−ビス（４−ヒドロキシフェニル）−１−フェニルエタン、２，２−ビス（４−ヒドロキシフェニル）プロパン（通称ビスフェノールＡ）、２，２−ビス｛（４−ヒドロキシ−３−メチル）フェニル｝プロパン、２，２−ビス｛（４−ヒドロキシ−３，５−ジメチル）フェニル｝プロパン、２，２−ビス｛（４−ヒドロキシ−３，５−ジブロモ）フェニル｝プロパン、２，２−ビス｛（３−イソプロピル−４−ヒドロキシ）フェニル｝プロパン、２，２−ビス｛（４−ヒドロキシ−３−フェニル）フェニル｝プロパン、２，２−ビス（４−ヒドロキシフェニル）ブタン、２，２−ビス（４−ヒドロキシフェニル）−３−メチルブタン、２，２−ビス（４−ヒドロキシフェニル）−３，３−ジメチルブタン、２，４−ビス（４−ヒドロキシフェニル）−２−メチルブタン、２，２−ビス（４−ヒドロキシフェニル）ペンタン、２，２−ビス（４−ヒドロキシフェニル）−４−メチルペンタン、１，１−ビス（４−ヒドロキシフェニル）シクロヘキサン、１，１−ビス（４−ヒドロキシフェニル）−４−イソプロピルシクロヘキサン、１，１−ビス（４−ヒドロキシフェニル）−３，３，５−トリメチルシクロヘキサン、９，９−ビス（４−ヒドロキシフェニル）フルオレン、９，９−ビス｛（４−ヒドロキシ−３−メチル）フェニル｝フルオレン、α，α’−ビス（４−ヒドロキシフェニル）−ｏ−ジイソプロピルベンゼン、α，α’−ビス（４−ヒドロキシフェニル）−ｍ−ジイソプロピルベンゼン、α，α’−ビス（４−ヒドロキシフェニル）−ｐ−ジイソプロピルベンゼン、１，３−ビス（４−ヒドロキシフェニル）−５，７−ジメチルアダマンタン、４，４’−ジヒドロキシジフェニルスルホン、４，４’−ジヒドロキシジフェニルスルホキシド、４，４’−ジヒドロキシジフェニルスルフィド、４，４’−ジヒドロキシジフェニルケトン、４，４’−ジヒドロキシジフェニルエーテル、４，４’−ジヒドロキシジフェニルエステルなどが挙げられ、必要に応じてそれらの２種以上を用いることもできる。   Examples of the dihydric phenol include hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-dimethyl) phenyl} methane, 1,1- Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis { (4-hydroxy-3-methyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(4-hydroxy-3,5-dibromo) ) Phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl} propane, 2,2-bis {(4 Hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4 -Methylpentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3 5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy 3-methyl) phenyl} fluorene, α, α′-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α′-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfoxide, 4 , 4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl ester, etc., and if necessary, use two or more of them You can also.

なかでも、ビスフェノールＡ、２，２−ビス｛（４−ヒドロキシ−３−メチル）フェニル｝プロパン、２，２−ビス（４−ヒドロキシフェニル）ブタン、２，２−ビス（４−ヒドロキシフェニル）−３−メチルブタン、２，２−ビス（４−ヒドロキシフェニル）−３，３−ジメチルブタン、２，２−ビス（４−ヒドロキシフェニル）−４−メチルペンタン、１，１−ビス（４−ヒドロキシフェニル）−３，３，５−トリメチルシクロヘキサン及びα，α’−ビス（４−ヒドロキシフェニル）−ｍ−ジイソプロピルベンゼンから選ばれる二価フェノールを単独で又は２種以上用いるのが好ましく、特に、ビスフェノールＡの単独使用や、１，１−ビス（４−ヒドロキシフェニル）−３，３，５−トリメチルシクロヘキサンと、ビスフェノールＡ、２，２−ビス｛（４−ヒドロキシ−３−メチル）フェニル｝プロパン及びα，α’−ビス（４−ヒドロキシフェニル）−ｍ−ジイソプロピルベンゼンから選ばれる１種以上の二価フェノールとの併用が好ましい。   Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl)- 3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) ) -3,3,5-trimethylcyclohexane and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene are preferably used alone or in combination of two or more. In particular, bisphenol A Of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and bisphenol A, Use in combination with one or more dihydric phenols selected from 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene preferable.

カルボニル化剤としては、例えば、ホスゲンの如きカルボニルハライド、ジフェニルカーボネートの如きカーボネートエステル、二価フェノールのジハロホルメートの如きハロホルメートなどが挙げられ、必要に応じてそれらの２種以上を用いることもできる。   Examples of the carbonylating agent include carbonyl halides such as phosgene, carbonate esters such as diphenyl carbonate, haloformates such as dihaloformates of dihydric phenols, and two or more of them can be used as necessary.

アクリル樹脂層を構成するアクリル樹脂としては、一般的にメタクリル樹脂が用いられる。メタクリル樹脂は、メタクリル酸メチル単位を主成分とするもの、具体的にはメタクリル酸メチル単位を通常５０重量％以上、好ましくは７０重量％以上含むメタクリル酸メチル樹脂であるのが好ましく、メタクリル酸メチル単位１００重量％のメタクリル酸メチル単独重合体であってもよいし、メタクリル酸メチルと他の単量体との共重合体であってもよい。   As the acrylic resin constituting the acrylic resin layer, methacrylic resin is generally used. The methacrylic resin is preferably a methyl methacrylate resin containing a methyl methacrylate unit as a main component, specifically a methyl methacrylate resin containing usually 50% by weight or more, preferably 70% by weight or more of a methyl methacrylate unit. A homopolymer of methyl methacrylate having a unit of 100% by weight may be used, or a copolymer of methyl methacrylate and another monomer may be used.

メタクリル酸メチルと共重合しうる他の単量体の例としては、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸シクロヘキシル、メタクリル酸フェニル、メタクリル酸ベンジル、メタクリル酸２−エチルヘキシル、メタクリル酸２−ヒドロキシエチルの如きメタクリル酸メチル以外のメタクリル酸エステル類や、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸シクロヘキシル、アクリル酸フェニル、アクリル酸ベンジル、アクリル酸２−エチルヘキシル、アクリル酸２−ヒドロキシエチルの如きアクリル酸エステル類が挙げられる。また、スチレンや置換スチレン類、例えば、クロロスチレン、ブロモスチレンの如きハロゲン化スチレン類や、ビニルトルエン、α−メチルスチレンの如きアルキルスチレン類なども挙げられる。さらに、メタクリル酸、アクリル酸の如き不飽和酸類、アクリロニトリル、メタクリロニトリル、無水マレイン酸、フェニルマレイミド、シクロヘキシルマレイミドなども挙げられる。これらメタクリル酸メチルと共重合しうる他の単量体は、それぞれ単独で用いてもよいし、２種以上を組み合わせて用いてもよい。   Examples of other monomers copolymerizable with methyl methacrylate include ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate. Methacrylic acid esters other than methyl methacrylate, such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, 2-hydroxyethyl acrylate Such acrylic acid esters can be mentioned. Further, styrene and substituted styrenes, for example, halogenated styrenes such as chlorostyrene and bromostyrene, alkyl styrenes such as vinyltoluene and α-methylstyrene, and the like are also included. Furthermore, unsaturated acids such as methacrylic acid and acrylic acid, acrylonitrile, methacrylonitrile, maleic anhydride, phenylmaleimide, cyclohexylmaleimide and the like can also be mentioned. These other monomers copolymerizable with methyl methacrylate may be used alone or in combination of two or more.

アクリル樹脂は、ゴム状重合体をブレンドして用いてもよい。ゴム状重合体の例としては、アクリル系多層構造重合体や、５〜８０重量部のゴム状重合体にアクリル系不飽和単量体の如きエチレン性不飽和単量体２０〜９５重量部をグラフト重合させてなるグラフト共重合体などが挙げられる。アクリル系多層構造重合体は、ゴム弾性の層又はエラストマーの層を２０〜６０重量％程度内在させるものであるのがよく、最外には硬質層を有するものであるのがよく、さらに最内層として硬質層を含む構造のものでもよい。   The acrylic resin may be used by blending a rubbery polymer. Examples of rubbery polymers include acrylic multilayered polymers and 5 to 80 parts by weight of rubbery polymer with 20 to 95 parts by weight of ethylenically unsaturated monomers such as acrylic unsaturated monomers. Examples include graft copolymers obtained by graft polymerization. The acrylic multi-layered structure polymer should have a rubber elastic layer or an elastomer layer contained in an amount of about 20 to 60% by weight, and should have a hard layer at the outermost layer, and further the innermost layer. A structure including a hard layer may be used.

ゴム弾性の層又はエラストマーの層は、ガラス転移点（Ｔｇ）が２５℃未満のアクリル系重合体の層であるのがよく、具体的には、低級アルキルアクリレート、低級アルキルメタクリレート、低級アルコキシアルキルアクリレート、シアノエチルアクリレート、アクリルアミド、ヒドロキシ低級アルキルアクリレート、ヒドロキシ低級アルキルメタクリレート、アクリル酸及びメタクリル酸から選ばれる単官能単量体の１種以上を、アリルメタクリレートの如き多官能単量体で架橋させてなる重合体の層であるのがよい。   The rubber-elastic layer or the elastomer layer is preferably an acrylic polymer layer having a glass transition point (Tg) of less than 25 ° C., and specifically includes lower alkyl acrylate, lower alkyl methacrylate, and lower alkoxyalkyl acrylate. A polymer obtained by crosslinking one or more monofunctional monomers selected from cyanoethyl acrylate, acrylamide, hydroxy lower alkyl acrylate, hydroxy lower alkyl methacrylate, acrylic acid and methacrylic acid with a polyfunctional monomer such as allyl methacrylate. It should be a coalesced layer.

硬質層は、Ｔｇが２５℃以上のアクリル系重合体の層であるのがよく、具体的には、炭素数１〜４個のアルキル基を有するアルキルメタクリレートを単独で又は主成分として重合させたものであるのがよい。アルキルメタクリレートを主成分として共重合体とする場合、共重合成分としては、他のアルキルメタクリレートやアルキルアクリレート、スチレン、置換スチレン、アクリロニトリル、メタクリロニトリルの如き単官能単量体を用いてもよいし、さらに多官能単量体を加えて架橋重合体としてもよい。   The hard layer may be an acrylic polymer layer having a Tg of 25 ° C. or more, and specifically, an alkyl methacrylate having an alkyl group having 1 to 4 carbon atoms is polymerized alone or as a main component. It should be a thing. When the copolymer is mainly composed of alkyl methacrylate, the copolymer component may be a monofunctional monomer such as other alkyl methacrylate, alkyl acrylate, styrene, substituted styrene, acrylonitrile, or methacrylonitrile. Further, a polyfunctional monomer may be added to form a crosslinked polymer.

アクリル系多層構造重合体は、例えば、特公昭５５−２７５７６号公報、特開平６−８０７３９号公報、特開昭４９−２３２９２2号公報などに記載されている。   Acrylic multilayer structure polymers are described, for example, in JP-B-55-27576, JP-A-6-80739, JP-A-49-232922, and the like.

５〜８０重量部のゴム状重合体にエチレン性不飽和単量体２０〜９５重量部をグラフト重合させてなるグラフト共重合体において、ゴム状重合体としては、例えば、ポリブタジエンゴム、アクリロニトリル／ブタジエン共重合体ゴム、スチレン／ブタジエン共重合体ゴムの如きジエン系ゴム、ポリブチルアクリレート、ポリプロピルアクリレート、ポリ−２−エチルヘキシルアクリレートの如きアクリル系ゴム、エチレン／プロピレン／非共役ジエン系ゴムなどが用いられる。また、このゴム状重合体にグラフト共重合させるのに用いられるエチレン性単量体としては、例えば、スチレン、アクリロニトリル、アルキル（メタ）アクリレートなどが挙げられる。これらのグラフト共重合体は、例えば、特開昭５５−１４７５１４号公報、特公昭４７−９７４０号公報などに記載されている。   In a graft copolymer obtained by graft polymerization of 20 to 95 parts by weight of an ethylenically unsaturated monomer to 5 to 80 parts by weight of a rubbery polymer, examples of the rubbery polymer include polybutadiene rubber and acrylonitrile / butadiene. Diene rubber such as copolymer rubber, styrene / butadiene copolymer rubber, acrylic rubber such as polybutyl acrylate, polypropyl acrylate, poly-2-ethylhexyl acrylate, ethylene / propylene / non-conjugated diene rubber, etc. It is done. Examples of the ethylenic monomer used for graft copolymerization with the rubbery polymer include styrene, acrylonitrile, and alkyl (meth) acrylate. These graft copolymers are described, for example, in JP-A Nos. 55-147514 and 47-9740.

アクリル樹脂にゴム状重合体を分散させる場合の分散割合は、アクリル樹脂１００重量部に対して、通常３〜１５０重量部、好ましくは５〜５０重量部である。ゴム状重合体の量があまり多いと、表面硬度が低下して好ましくない。   When the rubber-like polymer is dispersed in the acrylic resin, the dispersion ratio is usually 3 to 150 parts by weight, preferably 5 to 50 parts by weight with respect to 100 parts by weight of the acrylic resin. If the amount of the rubbery polymer is too large, the surface hardness is lowered, which is not preferable.

なお、ポリカーボネート樹脂層及びアクリル樹脂層にはそれぞれ、必要に応じて、例えば、光拡散剤、艶消剤、染料、光安定剤、紫外線吸収剤、酸化防止剤、離型剤、難燃剤、帯電防止剤などの添加剤を１種又は２種以上、添加してもよい。   In addition, for each of the polycarbonate resin layer and the acrylic resin layer, for example, a light diffusing agent, a matting agent, a dye, a light stabilizer, an ultraviolet absorber, an antioxidant, a release agent, a flame retardant, a charge One or more additives such as an inhibitor may be added.

本発明の積層樹脂体は、ポリカーボネート樹脂層とアクリル樹脂層を共押出成形で積層一体化することにより、好適に製造される。この共押出成形は、２基又は３基の一軸又は二軸の押出機を用いて、ポリカーボネート樹脂層の材料とアクリル樹脂層の材料とをそれぞれ溶融混練した後、フィードブロックダイやマルチマニホールドダイなどを介して積層することにより行うことができ、積層一体化された溶融積層樹脂体は、例えば、ロールユニットを用いて冷却固化し、積層樹脂体とすればよい。共押出成形により製造した積層樹脂体は、粘着剤や接着剤を用いた貼合により製造した積層樹脂体に比べて、ボタン状などに二次成形しやすい点で好ましい。   The laminated resin body of the present invention is preferably produced by laminating and integrating a polycarbonate resin layer and an acrylic resin layer by coextrusion molding. In this co-extrusion molding, a polycarbonate resin layer material and an acrylic resin layer material are melted and kneaded using two or three uniaxial or biaxial extruders, respectively, and then a feed block die, a multi-manifold die, etc. The molten laminated resin body that is laminated and integrated may be cooled and solidified using, for example, a roll unit to form a laminated resin body. A laminated resin body produced by coextrusion molding is preferable in that it can be easily formed into a button shape or the like as compared with a laminated resin body produced by bonding using an adhesive or an adhesive.

本発明の積層樹脂体は、ポリカーボネート樹脂層の片面のみにアクリル樹脂層が積層されてなる２層構造のものであってもよいし、ポリカーボネート樹脂層の両面にアクリル樹脂層が積層されてなる３層構造のものであってもよいが、３層構造のものは、アクリル樹脂層の厚みやアクリル樹脂の種類によっては、面衝撃性が低下して割れやすくなることもあるので、２層構造のものが好ましい。   The laminated resin body of the present invention may have a two-layer structure in which an acrylic resin layer is laminated on only one side of a polycarbonate resin layer, or an acrylic resin layer is laminated on both sides of a polycarbonate resin layer. It may have a layered structure, but a three-layered structure has a two-layered structure because the surface impact may be reduced and cracking may occur depending on the thickness of the acrylic resin layer and the type of acrylic resin. Those are preferred.

本発明の積層樹脂体は、通常、シート状ないしフィルム状であり、その厚みは、通常０．２〜２ｍｍ、好ましくは０．３〜１ｍｍ、さらに好ましくは０．３〜０．７ｍｍである。そして、本発明の積層樹脂体においては、ポリカーボネート樹脂層の厚みを、全体の厚みの５０％以上、好ましくは７０％以上、より好ましくは８０％以上とする。このように、ポリカーボネート樹脂層の厚みを所定の割合以上にすることにより、積層樹脂体がより割れにくいものとなる。なお、ポリカーボネート樹脂層の厚みは、全体の厚みに対し、通常９５％以下、より好ましくは９０％以下である。   The laminated resin body of the present invention is usually in the form of a sheet or film, and the thickness is usually 0.2 to 2 mm, preferably 0.3 to 1 mm, more preferably 0.3 to 0.7 mm. In the laminated resin body of the present invention, the thickness of the polycarbonate resin layer is 50% or more, preferably 70% or more, more preferably 80% or more of the total thickness. Thus, by making the thickness of the polycarbonate resin layer a predetermined ratio or more, the laminated resin body becomes more difficult to break. In addition, the thickness of a polycarbonate resin layer is 95% or less normally with respect to the whole thickness, More preferably, it is 90% or less.

アクリル樹脂層の表面硬度を重視する場合、その厚みを１０μｍ以上とするのが好ましい。なお、３層構造の場合、両アクリル層の厚みは、互いに同一であってもよいし、異なっていてもよい。   When importance is attached to the surface hardness of the acrylic resin layer, the thickness is preferably 10 μm or more. In the case of a three-layer structure, the thicknesses of both acrylic layers may be the same or different.

こうして得られる本発明の積層樹脂体は、例えば、携帯電話や携帯用音楽プレイヤーなどの押ボタンスイッチの被覆部材として用いられる。また、タッチセンサーボタンスイッチの被覆部材としても用いられる。さらに、これらのボタンスイッチ被覆の機能を兼ねた液晶や有機ＥＬパネルの保護被覆部材としても使用できる。   The laminated resin body of the present invention thus obtained is used, for example, as a covering member for a pushbutton switch such as a mobile phone or a portable music player. It is also used as a covering member for touch sensor button switches. Furthermore, it can also be used as a protective covering member for liquid crystal and organic EL panels that also function as these button switch covers.

本発明の積層樹脂体をボタンスイッチの被覆部材として用いるには、例えば、必要に応じて、熱成形の如き二次成形、印刷、穴あけなどの加工を行い、所定の形状ないし大きさに切断処理すればよい。そして、二層構造の積層樹脂体であれば、通常、アクリル樹脂層が表側（外側：人が触れる側）となるように、ボタンスイッチを被覆すればよい。また、三層構造の積層樹脂体であって、両アクリル樹脂層の厚みが互いに異なる場合は、厚みが大きい方のアクリル樹脂層が表側となるように、ボタンスイッチを被覆するのがよい。こうして本発明の積層樹脂体によりボタンスイッチを被覆することにより、傷が付きにくく、かつ割れにくい被覆層をボタンスイッチ表面に形成することができる。また、防水や防塵の効果もある。   In order to use the laminated resin body of the present invention as a covering member for a button switch, for example, if necessary, secondary molding such as thermoforming, printing, drilling, and the like are performed, and cutting into a predetermined shape or size is performed. do it. And if it is a laminated resin body of a two-layer structure, the button switch is usually covered so that the acrylic resin layer is on the front side (outside: the side touched by a person). Further, when the laminated resin body has a three-layer structure and the thicknesses of both acrylic resin layers are different from each other, the button switch is preferably covered so that the acrylic resin layer having the larger thickness is on the front side. Thus, by covering the button switch with the laminated resin body of the present invention, it is possible to form a coating layer on the surface of the button switch which is hard to be scratched and cracked. It also has a waterproof and dustproof effect.

以下、本発明の実施例を示すが、本発明はこれらによって限定されるものではない。各例における押出装置の構成及び評価方法は、次のとおりである。   Examples of the present invention will be described below, but the present invention is not limited thereto. The configuration of the extrusion apparatus and the evaluation method in each example are as follows.

〔押出装置の構成〕
押出機（１）：スクリュー径６５ｍｍ、一軸、ベント付き（東芝機械（株）製）。
押出機（２）：スクリュー径４５ｍｍ、一軸、ベント付き（日立造船（株）製）。
フィードブロック：２種３層及び２種２層分配（日立造船（株）製）。
ダイ：Ｔダイ、リップ幅１４００ｍｍ、リップ間隔１ｍｍ（日立造船（株）製）。
ロール：ポリシングロール３本、横型。 [Configuration of extrusion equipment]
Extruder (1): Screw diameter 65 mm, uniaxial, with vent (manufactured by Toshiba Machine Co., Ltd.).
Extruder (2): Screw diameter 45 mm, uniaxial, with vent (manufactured by Hitachi Zosen).
Feed block: 2 types 3 layers and 2 types 2 layers distribution (manufactured by Hitachi Zosen Corporation).
Die: T-die, lip width 1400 mm, lip interval 1 mm (manufactured by Hitachi Zosen Corporation).
Roll: 3 polishing rolls, horizontal type.

〔評価方法〕
布施真空（株）製の熱成形機（型式：ＣＵＰＦ−１０１５−ＰＷＢ）に１８０×２５０ｍｍの開口部を設け、２２０×３１０ｍｍにカットした樹脂板（１００℃で２０時間乾燥させたもの）をクランプし、１００×５０ｍｍで高さ１００ｍｍの突き上げ成形用木型を用いて、成形温度１８０℃で突き上げ成形を行った。その際、２層構成の板の場合は、アクリル樹脂層が頂部外側（突き上げ木型に接触しない面）になるように成形を行った。得られた突き上げ成形品の頂部の鉛筆硬度を、ＪＩＳ Ｋ５４００に準拠し、１ｋｇ荷重で測定した。また、得られた突き上げ成形品の頂部を上に床置きして、１ｍの高さより５００ｇの鉄球を落下させることにより、落球試験を行い、割れなかったものを○、割れたものを×とした。 〔Evaluation methods〕
A thermoforming machine manufactured by Fuse Vacuum Co., Ltd. (model: CUPF-1015-PWB) is provided with an opening of 180 x 250 mm and a resin plate cut to 220 x 310 mm (dried at 100 ° C for 20 hours) is clamped Then, push-up molding was performed at a molding temperature of 180 ° C. using a push-molding wooden mold of 100 × 50 mm and a height of 100 mm. At that time, in the case of a two-layer plate, the acrylic resin layer was molded so that it was on the outer side of the top (surface not in contact with the raised wooden mold). The pencil hardness of the top of the obtained push-up molded product was measured with a 1 kg load according to JIS K5400. The top of the resulting molded product is placed on the floor, and a ball drop test is performed by dropping an iron ball of 500 g from a height of 1 m. did.

参考例１（ゴム状重合体の製造）
特公昭５５−２７５７６号公報に記載の方法に準拠して、３層構造アクリル系多層弾性体を製造した。すなわち、内容積５Ｌのガラス製反応容器に、イオン交換水１７００ｇ、炭酸ナトリウム０．７ｇ及び過硫酸ナトリウム０．３ｇを仕込み、窒素気流下で撹拌後、ジオクチルスルホコハク酸ナトリウム（（株）花王製のペレックスＯＴ−Ｐ；陰イオン性界面活性剤）４．４６ｇ、イオン交換水１５０ｇ、メチルメタクリレート１５０ｇ及びアリルメタクリレート０．３ｇを加え、７５℃に昇温し１５０分間撹拌を続けた。次いで、ブチルアクリレート６８９ｇ、スチレン１６２ｇ及びアリルメタクリレート１７ｇの混合物と、過硫酸ナトリウム０．８５ｇ、ジオクチルスルホコハク酸ナトリウム（同上）７．４ｇ及びイオン交換水５０ｇの混合物とを、別々の入口から９０分間にわたり添加し、さらに９０分間重合を続けた。その後、さらにメチルアクリレート３２６ｇ及びエチルアクリレート１４ｇの混合物と、過硫酸ナトリウム０．３４ｇを溶解させたイオン交換水３０ｇとを、別々の入口から３０分間にわたって添加した。添加終了後、さらに６０分間保持し重合を完了した。得られたラテックスを０．５重量％塩化アルミニウム水溶液に投入して重合体を凝集させた。これを温水にて５回洗浄後、乾燥して、アクリル系多層弾性体を得た。 Reference Example 1 (Production of rubber-like polymer)
In accordance with the method described in JP-B-55-27576, a three-layer acrylic multilayer elastic body was produced. That is, 1700 g of ion-exchanged water, 0.7 g of sodium carbonate and 0.3 g of sodium persulfate were charged into a glass reaction container having an internal volume of 5 L, stirred under a nitrogen stream, and then sodium dioctylsulfosuccinate (manufactured by Kao Corporation). 4.46 g of PELEX OT-P (anionic surfactant), 150 g of ion-exchanged water, 150 g of methyl methacrylate and 0.3 g of allyl methacrylate were added, the temperature was raised to 75 ° C., and stirring was continued for 150 minutes. Next, a mixture of 689 g of butyl acrylate, 162 g of styrene and 17 g of allyl methacrylate, and a mixture of 0.85 g of sodium persulfate, 7.4 g of sodium dioctyl sulfosuccinate (same as above) and 50 g of ion-exchanged water were added over 90 minutes from separate inlets. The polymerization was continued for an additional 90 minutes. Thereafter, a further mixture of 326 g of methyl acrylate and 14 g of ethyl acrylate and 30 g of ion-exchanged water in which 0.34 g of sodium persulfate was dissolved were added from separate inlets over 30 minutes. After completion of the addition, the polymerization was completed by holding for another 60 minutes. The obtained latex was put into a 0.5 wt% aluminum chloride aqueous solution to aggregate the polymer. This was washed 5 times with warm water and then dried to obtain an acrylic multilayer elastic body.

実施例１〜４
ポリカーボネート樹脂〔住友ダウ（株）製のカリバー３０１−１０〕を押出機（１）で、アクリル樹脂〔メタクリル酸メチル／アクリル酸メチル＝９８／２（重量比）の共重合体〕を押出機（２）で、それぞれ加熱しながら溶融混練して、フィードブロックにて積層一体化し、溶融状態のままＴダイから押し出して、ポリシングロールにて冷却し、表１に示す構成の２層樹脂板を得た。得られた板の評価結果を表１に示す。 Examples 1-4
Polycarbonate resin [Caliber 301-10 manufactured by Sumitomo Dow Co., Ltd.] was used in the extruder (1), and acrylic resin [methyl methacrylate / methyl acrylate = 98/2 (weight ratio) copolymer] was used as the extruder ( In 2), each is melt-kneaded while heating, laminated and integrated with a feed block, extruded from a T-die in a molten state, cooled with a polishing roll, and a two-layer resin plate having the structure shown in Table 1 is obtained. It was. The evaluation results of the obtained plate are shown in Table 1.

実施例５〜６
ポリカーボネート樹脂〔住友ダウ（株）製のカリバー３０１−１０〕を押出機（１）で、アクリル樹脂〔メタクリル酸メチル／アクリル酸メチル＝９６／４（重量比）の共重合体（屈折率１．４９）７０重量部に、参考例１で得たアクリル系多層弾性体３０重量部を配合してなるメタクリル樹脂組成物〕を押出機（２）で、それぞれ加熱しながら溶融混練して、フィードブロックにて積層一体化し、溶融状態のままＴダイから押し出して、ポリシングロールにて冷却し、表１に示す構成の３層樹脂板を得た。得られた板の評価結果を表１に示す。 Examples 5-6
Polycarbonate resin [Caliber 301-10 manufactured by Sumitomo Dow Co., Ltd.] was extruded with an extruder (1), and an acrylic resin [methyl methacrylate / methyl acrylate = 96/4 (weight ratio) copolymer (refractive index 1. 49) Melt and knead each of 70 parts by weight of a methacrylic resin composition obtained by blending 30 parts by weight of the acrylic multilayer elastic body obtained in Reference Example 1 with an extruder (2) while heating, respectively. Were laminated and integrated, extruded from a T-die in a molten state, cooled with a polishing roll, and a three-layer resin plate having the structure shown in Table 1 was obtained. The evaluation results of the obtained plate are shown in Table 1.

比較例１
実施例２において、各押出機原料のアクリル樹脂とポリカーボネート樹脂を入れ替えて、表１に示す構成の２層樹脂板を得た。得られた板の評価結果を表１に示す。 Comparative Example 1
In Example 2, the acrylic resin and polycarbonate resin of each extruder raw material were replaced, and the 2 layer resin board of the structure shown in Table 1 was obtained. The evaluation results of the obtained plate are shown in Table 1.

比較例２
実施例６において、各押出機原料のアクリル樹脂とポリカーボネート樹脂を入れ替えて、表１に示す構成の３層樹脂板を得た。得られた板の評価結果を表１に示す。 Comparative Example 2
In Example 6, the acrylic resin and polycarbonate resin of each extruder raw material were replaced, and the 3 layer resin board of the structure shown in Table 1 was obtained. The evaluation results of the obtained plate are shown in Table 1.

比較例３
実施例３において、押出機（１）を停止し、アクリル樹脂層のみの単層板を得た。得られた板の評価結果を表１に示す。 Comparative Example 3
In Example 3, the extruder (1) was stopped to obtain a single-layer plate having only an acrylic resin layer. The evaluation results of the obtained plate are shown in Table 1.

比較例４
実施例３において、押出機（２）を停止し、ポリカーボネート樹脂層のみの単層板を得た。得られた板の評価結果を表１に示す。 Comparative Example 4
In Example 3, the extruder (2) was stopped to obtain a single-layer plate having only a polycarbonate resin layer. The evaluation results of the obtained plate are shown in Table 1.

Figure 2009110842
Figure 2009110842

表１中、ＰＣはポリカーボネート樹脂層を表し、ＰＭＭＡはアクリル樹脂層を表す。   In Table 1, PC represents a polycarbonate resin layer, and PMMA represents an acrylic resin layer.

Claims (3)

ポリカーボネート樹脂層の少なくとも一方の面にアクリル樹脂層が積層されてなり、ポリカーボネート樹脂層の厚みが全体の厚みの５０％以上であることを特徴とするボタンスイッチ被覆用積層樹脂体。   A laminated resin body for covering button switches, wherein an acrylic resin layer is laminated on at least one surface of a polycarbonate resin layer, and the thickness of the polycarbonate resin layer is 50% or more of the total thickness. ポリカーボネート樹脂層とアクリル樹脂層とが共押出成形により積層されてなる請求項１に記載のボタンスイッチ被覆用積層樹脂体。   The laminated resin body for button switch covering according to claim 1, wherein the polycarbonate resin layer and the acrylic resin layer are laminated by coextrusion molding. アクリル樹脂層がメタクリル樹脂及びゴム状重合体からなる層である請求項１又は２に記載のボタンスイッチ被覆用積層樹脂体。   The laminated resin body for button switch covering according to claim 1 or 2, wherein the acrylic resin layer is a layer made of a methacrylic resin and a rubber-like polymer.
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