JP2014027038A - Uniaxially oriented film for piezoelectric laminate and piezoelectric laminate - Google Patents
Uniaxially oriented film for piezoelectric laminate and piezoelectric laminate Download PDFInfo
- Publication number
- JP2014027038A JP2014027038A JP2012164508A JP2012164508A JP2014027038A JP 2014027038 A JP2014027038 A JP 2014027038A JP 2012164508 A JP2012164508 A JP 2012164508A JP 2012164508 A JP2012164508 A JP 2012164508A JP 2014027038 A JP2014027038 A JP 2014027038A
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- Prior art keywords
- uniaxially oriented
- film
- piezoelectric
- oriented film
- layer
- Prior art date
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Abstract
Description
本発明は、圧電積層体用一軸配向フィルムおよびそれを用いた圧電積層体に関する。 The present invention relates to a uniaxially oriented film for a piezoelectric laminate and a piezoelectric laminate using the same.
延伸を施したポリ乳酸フィルムに導電層を設けることで、高分子圧電材料として用いられることが知られている(特許文献1、2)。また、このような高分子圧電材料を積層してバイモルフ構造またはマルチモルフ構造を形成し、圧電特性をより高めて、マイクロホン、ピックアップ、ブザー、スピーカー、光スイッチ、ファン等の振動体や、圧電体アクチュエーターとして用いられることが知られている(特許文献3〜5)
ところで、圧電材料とは関係のない分野において、ポリ乳酸フィルムに、ヒートシール性を有するアクリル系樹脂層を設けることで、環境対応性に優れ、包装材料として必要な優れた透明性と高い機械的強度と優れたヒートシール性とを有するフィルムを提供できることが知られている(特許文献6)。また、商品の展示包装用などの分野で、耐熱性、透明性、耐衝撃性に優れるポリ乳酸系樹脂積層シートとして、ポリ乳酸にポリ(メタ)アクリレート系樹脂を含有させることや、耐衝撃性改良剤を含有させることが知られている(特許文献7)。
It is known that a conductive layer is provided on a stretched polylactic acid film to be used as a polymer piezoelectric material (
By the way, in fields unrelated to piezoelectric materials, by providing a polylactic acid film with an acrylic resin layer having heat-sealability, it has excellent environmental friendliness and excellent transparency and high mechanical properties required for packaging materials. It is known that a film having strength and excellent heat sealability can be provided (Patent Document 6). In addition, as a polylactic acid resin laminate sheet with excellent heat resistance, transparency, and impact resistance in fields such as product display packaging, poly (meth) acrylate resin is added to polylactic acid, and impact resistance It is known to contain an improving agent (Patent Document 7).
前述したバイモルフ構造またはマルチモルフ構造の圧電積層体を形成するために導電層を設けたポリ乳酸フィルムを熱圧着し、圧電積層体の圧電特性を高めるために積層数を増やしていくと、熱圧着後に剥離が生じる欠点があることが判明した。
そこで本発明の目的は、圧電特性を維持しつつ、剥離が生じにくいポリ乳酸フィルムおよびそれを用いた圧電積層体を提供することにある。
When a polylactic acid film provided with a conductive layer is thermocompression-bonded to form the above-described bimorph or multimorph piezoelectric laminate, and the number of layers is increased to increase the piezoelectric properties of the piezoelectric laminate, It has been found that there is a drawback that peeling occurs.
SUMMARY OF THE INVENTION An object of the present invention is to provide a polylactic acid film that does not easily peel while maintaining piezoelectric characteristics, and a piezoelectric laminate using the polylactic acid film.
本発明者らは、熱圧着性とは関係のない耐衝撃改良剤をポリ乳酸フィルムに含有させると、圧電特性に優れ剥離が生じにくい圧電積層体が得られることを見出し、本発明に到達した。 The inventors of the present invention have found that when a polylactic acid film contains an impact resistance improver that is not related to thermocompression bonding, a piezoelectric laminate that has excellent piezoelectric characteristics and is less likely to be peeled off can be obtained. .
かくして本発明によれば、以下の(1)〜(4)のポリ乳酸からなる一軸配向フィルムと、以下の(5)〜(8)の圧電積層体が提供される。
(1) 光学純度が80モル%以上のポリL−乳酸もしくはポリD−乳酸からなる一軸配向フィルムであって、一軸配向フィルムの質量を基準として、耐衝撃性改良剤を0.1〜10質量%の範囲で含有する圧電積層体用一軸配向フィルム。
(2) 耐衝撃性改良剤が、コア層とそれを覆う1以上のシェル層から構成される多層構造重合体である上記1記載の一軸配向フィルム。
(3) 密度が、1.22〜1.27g/cm3である上記1に記載の一軸配向フィルム。
(4) 厚みが15μm以下である上記1に記載の一軸配向フィルム。
(5) 上記1〜4のいずれか一項に記載の一軸配向フィルムと導電層とを交互に積層した圧電積層体。
(6) 一軸配向フィルムの合計層数が2以上である上記5に記載の圧電積層体。
(7) ポリL−乳酸またはポリD−乳酸のいずれか一方からなる一軸配向フィルムが、導電層を介して隣り合い、隣り合う一軸配向フィルムの主配向軸が直交する上記5に記載の圧電積層体。
(8) ポリL−乳酸からなる一軸配向フィルムと、ポリD−乳酸からなる一軸配向フィルムとが、導電層を介して隣り合い、隣り合う一軸配向フィルムの主配向軸が同方向である上記5に記載の圧電積層体。
Thus, according to the present invention, the following uniaxially oriented films made of polylactic acid (1) to (4) and piezoelectric laminates (5) to (8) below are provided.
(1) A uniaxially oriented film made of poly L-lactic acid or poly D-lactic acid having an optical purity of 80 mol% or more, and 0.1 to 10 mass of an impact resistance improver based on the mass of the uniaxially oriented film. % Uniaxially oriented film for piezoelectric laminates.
(2) The uniaxially oriented film according to 1 above, wherein the impact resistance improver is a multilayer structure polymer composed of a core layer and one or more shell layers covering the core layer.
(3) The uniaxially oriented film as described in 1 above, wherein the density is 1.22 to 1.27 g / cm 3 .
(4) The uniaxially oriented film as described in 1 above, wherein the thickness is 15 μm or less.
(5) The piezoelectric laminated body which laminated | stacked the uniaxially oriented film as described in any one of said 1-4, and a conductive layer alternately.
(6) The piezoelectric laminate according to 5 above, wherein the total number of layers of the uniaxially oriented film is 2 or more.
(7) The piezoelectric laminate as described in 5 above, wherein uniaxially oriented films made of either poly L-lactic acid or poly D-lactic acid are adjacent to each other via a conductive layer, and the main orientation axes of the adjacent uniaxially oriented films are orthogonal to each other. body.
(8) The uniaxially oriented film made of poly L-lactic acid and the uniaxially oriented film made of poly D-lactic acid are adjacent to each other through the conductive layer, and the main orientation axes of the adjacent uniaxially oriented films are in the same direction. The piezoelectric laminate according to 1.
本発明によれば、圧電特性を維持しつつ剥離が生じにくいポリ乳酸の一軸配向フィルムおよびそれを用いた圧電積層体が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the uniaxially oriented film of polylactic acid which does not produce peeling easily while maintaining a piezoelectric characteristic, and a piezoelectric laminated body using the same are provided.
(ポリ乳酸)
本発明におけるポリ乳酸は、光学純度が80モル%以上のポリL−乳酸(PLLAと省略する場合がある)もしくはポリD−乳酸(PDLAと省略する場合がある)である。光学純度が下限未満では、圧電特性が低く、本発明の効果が発現され難い。ポリ乳酸の光学純度は、好ましくは90モル%以上、より好ましくは95モル%以上、さらに好ましくは98モル%以上である。実質的にL−乳酸単位のみから構成されるポリL−乳酸もしくはD−乳酸単位のみから構成されるポリD−乳酸が特に好ましい。
またはPLLAもしくはPDLAとその他のモノマーとの共重合体も用いることができる。L−(D−)乳酸単位以外の単位の含有量は、好ましくは0〜10モル%、より好ましくは0〜5モル%、さらに好ましくは0〜2モル%である。
(Polylactic acid)
The polylactic acid in the present invention is poly L-lactic acid (may be abbreviated as PLLA) or poly D-lactic acid (may be abbreviated as PDLA) having an optical purity of 80 mol% or more. If the optical purity is less than the lower limit, the piezoelectric characteristics are low, and the effects of the present invention are hardly exhibited. The optical purity of polylactic acid is preferably 90 mol% or more, more preferably 95 mol% or more, and further preferably 98 mol% or more. Poly L-lactic acid substantially composed only of L-lactic acid units or poly D-lactic acid composed only of D-lactic acid units is particularly preferred.
Alternatively, a copolymer of PLLA or PDLA and other monomers can also be used. The content of units other than L- (D-) lactic acid units is preferably 0 to 10 mol%, more preferably 0 to 5 mol%, and still more preferably 0 to 2 mol%.
具体的な共重合成分としては、特に限定されるものではないが、例えば、グリコール酸、カプロラクトン、ブチロラクトン、プロピオラクトンなどのヒドロキシカルボン酸類、エチレングリコール、1,3−プロパンジオール、1,2−プロパンジオール、1,4−プロパンジオール、1,5−プロパンジオール、ヘキサンジオール、オクタンジオール、デカンジオール、ドデカンジオール、炭素数が2から30の脂肪族ジオール類、コハク酸、マレイン酸、アジピン酸、炭素数2から30の脂肪族ジカルボン酸、テレフタル酸、イソフタル酸、ヒドロキシ安息香酸、ヒドロキノンなど芳香族ジオール、芳香族ジカルボン酸などから選ばれる1種以上のモノマーを選ぶことが出来る。
ポリ乳酸の融点は150℃以上190℃以下であることが好ましく、160℃以上190℃以下であることがさらに好ましい。このような態様であるとフィルムの耐熱性に優れる。また、ポリ乳酸の分子量は、重量平均分子量(Mw)で、8万から25万の範囲であることが好ましく、10万から25万以下であることがより好ましく、特に12万から20万の範囲にあることが好ましい。重量平均分子量Mwが上記数値範囲にあることで、フィルムの厚み斑が良好になり、より圧着後の剥離を抑えやすい。
Specific examples of the copolymer component are not particularly limited. For example, hydroxycarboxylic acids such as glycolic acid, caprolactone, butyrolactone, propiolactone, ethylene glycol, 1,3-propanediol, 1,2- Propanediol, 1,4-propanediol, 1,5-propanediol, hexanediol, octanediol, decanediol, dodecanediol, aliphatic diols having 2 to 30 carbon atoms, succinic acid, maleic acid, adipic acid, One or more monomers selected from aliphatic dicarboxylic acids having 2 to 30 carbon atoms, terephthalic acid, isophthalic acid, hydroxybenzoic acid, hydroquinone, and other aromatic diols, aromatic dicarboxylic acids and the like can be selected.
The melting point of polylactic acid is preferably 150 ° C. or higher and 190 ° C. or lower, and more preferably 160 ° C. or higher and 190 ° C. or lower. With such an embodiment, the film has excellent heat resistance. The molecular weight of polylactic acid is a weight average molecular weight (Mw), preferably in the range of 80,000 to 250,000, more preferably in the range of 100,000 to 250,000, particularly in the range of 120,000 to 200,000. It is preferable that it exists in. When the weight average molecular weight Mw is in the above numerical range, the thickness unevenness of the film becomes good, and it is easier to suppress peeling after pressure bonding.
(一軸配向フィルム)
本発明のポリ乳酸フィルムは、一軸配向フィルムであることが必要である。二軸配向フィルムや無配向フィルムでは、圧電特性が低く、後述の耐衝撃性改良剤を含有させる効果が十分に発現されない。
本発明における一軸配向フィルムとは、フィルムの面内方向におけるもっとも屈折率の高い方向を主配向方向としたとき、主配向方向の破断強度が120MPa以上で、フィルムの面内方向における該主配向方向と直交する方向の破断強度が、80MPa以下であるような偏った配向を有するフィルムを意味する。なお、主配向方向の破断強度の下限は、より好ましくは120MPa以上、さらに150MPa以上、特に180MPa以上が好ましく、他方上限は300MPa以下、さらに好ましくは250MPa以下であることが好ましい。主配向方向の破断強度が上記下限以上あることで、共振特性の向上効果を高くすることができる。破断強度が上記下限よりも低い場合は、共振特性の向上効果が低くなる。他方、主配向方向の破断強度の上限は特に制限されないが、製膜性などの点から300MPa以下であることが好ましい。
(Uniaxially oriented film)
The polylactic acid film of the present invention needs to be a uniaxially oriented film. Biaxially oriented films and non-oriented films have low piezoelectric properties and do not sufficiently exhibit the effect of containing an impact resistance improver described below.
The uniaxially oriented film in the present invention refers to the direction of the highest refractive index in the in-plane direction of the film as the main orientation direction, the breaking strength in the main orientation direction is 120 MPa or more, the main orientation direction in the in-plane direction of the film It means a film having a biased orientation such that the breaking strength in the direction perpendicular to is 80 MPa or less. The lower limit of the breaking strength in the main orientation direction is more preferably 120 MPa or more, further preferably 150 MPa or more, particularly preferably 180 MPa or more, and the upper limit is preferably 300 MPa or less, more preferably 250 MPa or less. When the breaking strength in the main orientation direction is not less than the above lower limit, the effect of improving the resonance characteristics can be enhanced. When the breaking strength is lower than the above lower limit, the effect of improving the resonance characteristics is lowered. On the other hand, the upper limit of the breaking strength in the main orientation direction is not particularly limited, but is preferably 300 MPa or less from the viewpoint of film forming properties.
また、本発明のポリ乳酸一軸配向フィルムの破断強度は、主配向軸方向に直交する方向は、80MPa以下であることが好ましい。破断強度が上記上限以下にあると、共振特性の向上効果を高くすることができる。主配向軸方向に直交する方向の破断強度が上記上限よりも高い場合は、共振特性の向上効果が低くなる。他方、主配向軸方向に直交する方向の破断強度の下限は特に制限されないが、製膜後の取り扱いなどの点から、30MPa以上、さらに50MPa以上であることが好ましい。なお、本発明において、説明の便宜上、ポリ乳酸フィルムの製膜方向を縦方向、MD方向と称することがあり、厚み方向をZ方向、製膜方向と厚み方向とに直交する方向を幅方向、横方向、TD方向と称することがある。 The breaking strength of the polylactic acid uniaxially oriented film of the present invention is preferably 80 MPa or less in the direction orthogonal to the main orientation axis direction. When the breaking strength is less than or equal to the above upper limit, the effect of improving the resonance characteristics can be increased. When the breaking strength in the direction orthogonal to the main alignment axis direction is higher than the above upper limit, the effect of improving the resonance characteristics becomes low. On the other hand, the lower limit of the breaking strength in the direction orthogonal to the main orientation axis direction is not particularly limited, but is preferably 30 MPa or more, and more preferably 50 MPa or more from the viewpoint of handling after film formation. In the present invention, for convenience of explanation, the film forming direction of the polylactic acid film may be referred to as the longitudinal direction and the MD direction, the thickness direction is the Z direction, and the direction perpendicular to the film forming direction and the thickness direction is the width direction. It may be called a horizontal direction and a TD direction.
(耐衝撃性改良剤)
本発明の特徴の一つは、ポリ乳酸一軸配向フィルムに、耐衝撃性改良剤を、ポリ乳酸一軸配向フィルムの質量を基準として、0.1〜10質量%の範囲で含有させたことにある。
本発明で用いられる耐衝撃性改良剤とは、ポリ乳酸の耐衝撃性改良に用いることのできるものであれば特に制限されないが、室温でゴム弾性を示すゴム状物質のことであり、例えば、下記の各種耐衝撃性改良剤などから選ばれる少なくとも1種のものを用いることができる。
(Impact resistance improver)
One of the features of the present invention is that the polylactic acid uniaxially oriented film contains an impact resistance improver in the range of 0.1 to 10% by mass based on the mass of the polylactic acid uniaxially oriented film. .
The impact resistance improver used in the present invention is not particularly limited as long as it can be used to improve the impact resistance of polylactic acid, but is a rubber-like substance that exhibits rubber elasticity at room temperature. At least one selected from the following various impact resistance improvers can be used.
具体的な、耐衝撃性改良剤としては、エチレン−プロピレン共重合体、エチレン−プロピレン−非共役ジエン共重合体、エチレン−ブテン−1共重合体、各種アクリルゴム、エチレン−アクリル酸共重合体およびそのアルカリ金属塩(いわゆるアイオノマー)、エチレン−グリシジル(メタ)アクリレート共重合体、エチレン−(メタ)アクリル酸アルキルエステル共重合体(例えば、エチレン−アクリル酸メチル共重合体、エチレン−アクリル酸エチル共重合体、エチレン−アクリル酸ブチル共重合体、エチレン−メタクリル酸メチル共重合体)、エチレン−酢酸ビニル共重合体、酸変性エチレン−プロピレン共重合体、ジエンゴム(例えば、ポリブタジエン、ポリイソプレン、ポリクロロプレン)、ジエンとビニル単量体との共重合体およびその水素添加物(例えば、スチレン−ブタジエンランダム共重合体、スチレン−ブタジエンブロック共重合体、スチレン−ブタジエン−スチレンブロック共重合体、スチレン−イソプレンランダム共重合体、スチレン−イソプレンブロック共重合体、スチレン−イソプレン−スチレンブロック共重合体、スチレン−エチレン−ブチレン−スチレンブロック共重合体、スチレン−エチレン−プロピレン−スチレンブロック共重合体、ポリブタジエンにスチレンをグラフト共重合せしめたもの、ブタジエン−アクリロニトリル共重合体)、ポリイソブチレン、イソブチレンとブタジエンまたはイソプレンとの共重合体、天然ゴム、チオコールゴム、多硫化ゴム、アクリルゴム、シリコーンゴム、ポリウレタンゴム、ポリエーテルゴム、エピクロロヒドリンゴム、ポリエステル系エラストマーまたはポリアミド系エラストマーなどが挙げることができる。 Specific examples of impact modifiers include ethylene-propylene copolymers, ethylene-propylene-nonconjugated diene copolymers, ethylene-butene-1 copolymers, various acrylic rubbers, and ethylene-acrylic acid copolymers. And its alkali metal salt (so-called ionomer), ethylene-glycidyl (meth) acrylate copolymer, ethylene- (meth) acrylic acid alkyl ester copolymer (for example, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate) Copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl methacrylate copolymer), ethylene-vinyl acetate copolymer, acid-modified ethylene-propylene copolymer, diene rubber (for example, polybutadiene, polyisoprene, poly Chloroprene), a copolymer of diene and vinyl monomer And hydrogenated products thereof (for example, styrene-butadiene random copolymer, styrene-butadiene block copolymer, styrene-butadiene-styrene block copolymer, styrene-isoprene random copolymer, styrene-isoprene block copolymer, styrene) -Isoprene-styrene block copolymer, styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer, polybutadiene grafted with styrene, butadiene-acrylonitrile copolymer ), Polyisobutylene, copolymers of isobutylene and butadiene or isoprene, natural rubber, thiocol rubber, polysulfide rubber, acrylic rubber, silicone rubber, polyurethane rubber, polyether rubber, epic Rohidoringomu can like are mentioned polyester elastomer or polyamide elastomer.
さらに、各種の架橋度を有するものや、各種のミクロ構造、例えばシス構造、トランス構造などを有するもの、コア層とそれを覆う1以上のシェル層から構成される多層構造重合体なども使用することができる。また、本発明において、耐衝撃性改良剤としては、上記具体例に挙げた各種の(共)重合体は、ランダム共重合体、ブロック共重合体またはグラフト共重合体などのいずれも用いることができる。さらに、これらの(共)重合体を製造するに際し、他のオレフィン類、ジエン類、芳香族ビニル化合物、アクリル酸、アクリル酸エステルまたはメタクリル酸エステルなどの単量体を共重合することも可能である。
これらの耐衝撃性改良剤の中でも、アクリル単位を含む重合体や、酸無水物基および/またはグリシジル基を持つ単位を含む重合体が好ましい。ここでいうアクリル単位の好適例としては、メタクリル酸メチル単位、アクリル酸メチル単位、アクリル酸エチル単位またはアクリル酸ブチル単位を挙げることができ、酸無水物基やグリシジル基を持つ単位の好適例としては、無水マレイン酸単位またはメタクリル酸グリシジル単位を挙げることができる。
Further, those having various cross-linking degrees, those having various microstructures such as cis structure and trans structure, and multilayer polymers composed of a core layer and one or more shell layers covering it are also used. be able to. In the present invention, as the impact resistance improver, the various (co) polymers mentioned in the above specific examples may be any of random copolymers, block copolymers or graft copolymers. it can. Furthermore, when producing these (co) polymers, it is also possible to copolymerize monomers such as other olefins, dienes, aromatic vinyl compounds, acrylic acid, acrylic ester or methacrylic ester. is there.
Among these impact modifiers, a polymer containing an acrylic unit and a polymer containing a unit having an acid anhydride group and / or a glycidyl group are preferable. Preferable examples of the acrylic unit here include methyl methacrylate unit, methyl acrylate unit, ethyl acrylate unit or butyl acrylate unit, and preferable examples of the unit having an acid anhydride group or glycidyl group. May include maleic anhydride units or glycidyl methacrylate units.
(多層構造重合体)
耐衝撃性改良剤としては、本発明の効果の点で、コア層とそれを覆う1以上のシェル層から構成される多層構造重合体がより好ましい。なお、本発明において、多層構造重合体とは、コア層とそれを覆う1以上のシェル層から構成され、また、隣接する層が異種の重合体から構成される、いわゆるコアシェル型と呼ばれる構造を有する重合体である。また、多層構造重合体を構成する層の数は、特に限定されるものではなく、2層以上であればよく、3層以上または4層以上であってもよい。
(Multilayer structure polymer)
As the impact resistance improver, a multilayer structure polymer composed of a core layer and one or more shell layers covering the core layer is more preferable from the viewpoint of the effect of the present invention. In the present invention, the multilayer structure polymer is composed of a core layer and one or more shell layers covering the core layer, and a so-called core-shell type structure in which adjacent layers are composed of different polymers. It is a polymer having. In addition, the number of layers constituting the multilayer structure polymer is not particularly limited, and may be two or more, and may be three or more or four or more.
本発明で用いられる多層構造重合体としては、内部に少なくとも1層以上のゴム層を有する多層構造重合体であることが好ましい。ここで、ゴム層の種類は、特に限定されるものではなく、ゴム弾性を有する重合体成分から構成されるものであればよい。例えば、(メタ)アクリル成分、シリコーン成分、スチレン成分、ニトリル成分、共役ジエン成分、ウレタン成分またはエチレンプロピレン成分などを重合させたものから構成されるゴムを挙げることができる。好ましいゴムとしては、例えば、(メタ)アクリル酸エチル単位、(メタ)アクリル酸ブチル単位、(メタ)アクリル酸−2−エチルヘキシル単位または(メタ)アクリル酸ベンジル単位などの(メタ)アクリル成分、ジメチルシロキサン単位やフェニルメチルシロキサン単位などのシリコーン成分、スチレン単位やα−メチルスチレン単位などのスチレン成分、アクリロニトリル単位やメタクリロニトリル単位などのニトリル成分またはブタンジエン単位やイソプレン単位などの共役ジエン成分を重合させたものから構成されるゴムである。また、これらの成分の他に、ジビニルベンゼン単位、(メタ)アクリル酸アリル単位またはブチレングリコールジアクリレート単位などの架橋性成分を共重合して架橋させた架橋ゴムも好ましい。これらの中でも、本発明の効果の点から、ゴム層としては、架橋ゴムが好ましく、ガラス転移温度が0℃以下の架橋ゴムであることがより好ましく、このようなゴム層の種類としては、アクリル酸エチル単位、アクリル酸−2−エチルヘキシル単位、アクリル酸ブチル単位、アクリル酸ベンジル単位、メタクリル酸アリル単位を適宜選択し併用して用いることがさらに好ましく、メタクリル酸アリル単位をゴム層構成単位の0.005〜3質量%の範囲で用いるのが特に好ましい。 The multilayer structure polymer used in the present invention is preferably a multilayer structure polymer having at least one rubber layer therein. Here, the type of the rubber layer is not particularly limited as long as it is composed of a polymer component having rubber elasticity. For example, the rubber | gum comprised from what polymerized the (meth) acryl component, the silicone component, the styrene component, the nitrile component, the conjugated diene component, the urethane component, or the ethylene propylene component can be mentioned. Preferred rubbers include, for example, (meth) acrylic components such as ethyl (meth) acrylate units, butyl (meth) acrylate units, (meth) acrylic acid-2-ethylhexyl units or benzyl (meth) acrylate units, dimethyl Polymerize silicone components such as siloxane units and phenylmethylsiloxane units, styrene components such as styrene units and α-methylstyrene units, nitrile components such as acrylonitrile units and methacrylonitrile units, or conjugated diene components such as butanediene units and isoprene units. It is a rubber made of In addition to these components, a crosslinked rubber obtained by copolymerizing and crosslinking a crosslinkable component such as a divinylbenzene unit, an (meth) acrylate allyl unit, or a butylene glycol diacrylate unit is also preferable. Among these, from the viewpoint of the effects of the present invention, the rubber layer is preferably a crosslinked rubber, more preferably a crosslinked rubber having a glass transition temperature of 0 ° C. or less. It is more preferable to select an ethyl acid unit, an acrylic acid-2-ethylhexyl unit, a butyl acrylate unit, a benzyl acrylate unit, and an allyl methacrylate unit as appropriate. It is particularly preferable to use in the range of 0.005 to 3% by mass.
本発明における多層構造重合体において、ゴム層以外の層の種類は、熱可塑性を有する重合体成分から構成されるものであれば特に限定されるものではないが、透明性、耐熱性および耐衝撃性の点で、ゴム層よりもガラス転移温度が高い重合体成分であることが好ましい。熱可塑性を有する重合体としては、不飽和カルボン酸アルキルエステル系単位、グリシジル基含有ビニル系単位、不飽和ジカルボン酸無水物系単位、脂肪族ビニル系単位、芳香族ビニル系単位、シアン化ビニル系単位、マレイミド系単位、不飽和ジカルボン酸系単位およびその他のビニル系単位などから選ばれる少なくとも1種以上の単位を含有する重合体を挙げることができ、中でも、不飽和カルボン酸アルキルエステル系単位、不飽和グリシジル基含有単位および不飽和ジカルボン酸無水物系単位から選ばれる少なくとも1種以上の単位を含有する重合体が好ましく、さらに不飽和グリシジル基含有単位または不飽和ジカルボン酸無水物系単位から選ばれる少なくとも1種以上の単位を含有する重合体がより好ましい。 In the multilayer polymer in the present invention, the type of layer other than the rubber layer is not particularly limited as long as it is composed of a polymer component having thermoplasticity, but transparency, heat resistance and impact resistance are not limited. From the viewpoint of properties, it is preferably a polymer component having a glass transition temperature higher than that of the rubber layer. Polymers having thermoplastic properties include unsaturated carboxylic acid alkyl ester units, glycidyl group-containing vinyl units, unsaturated dicarboxylic anhydride units, aliphatic vinyl units, aromatic vinyl units, and vinyl cyanide units. Examples include polymers containing at least one unit selected from units, maleimide units, unsaturated dicarboxylic acid units and other vinyl units, among others, unsaturated carboxylic acid alkyl ester units, A polymer containing at least one unit selected from an unsaturated glycidyl group-containing unit and an unsaturated dicarboxylic acid anhydride unit is preferred, and further selected from an unsaturated glycidyl group-containing unit or an unsaturated dicarboxylic acid anhydride unit. More preferred is a polymer containing at least one unit.
本発明で用いられる多層構造重合体としては、シェル層の種類は、特に限定されるものではなく、不飽和カルボン酸アルキルエステル系単位、グリシジル基含有ビニル系単位、脂肪族ビニル系単位、芳香族ビニル系単位、シアン化ビニル系単位、マレイミド系単位、不飽和ジカルボン酸系単位、不飽和ジカルボン酸無水物系単位および/またはその他のビニル系単位などを含む重合体を挙げることができ、本発明の効果の点で、メタクリル酸メチル単位および/またはアクリル酸メチル単位を含む重合体から構成される多層構造重合体であることが好ましい。 As the multilayer structure polymer used in the present invention, the type of the shell layer is not particularly limited, and is an unsaturated carboxylic acid alkyl ester unit, a glycidyl group-containing vinyl unit, an aliphatic vinyl unit, an aromatic Examples of the polymer include vinyl units, vinyl cyanide units, maleimide units, unsaturated dicarboxylic acid units, unsaturated dicarboxylic anhydride units, and / or other vinyl units. From the viewpoint of the effect, a multilayer structure polymer composed of a polymer containing methyl methacrylate units and / or methyl acrylate units is preferable.
本発明で用いられる多層構造重合体としては、上述した条件を満たすものとして、市販品を用いてもよく、また、公知の方法により作製することもでき、市販品としては、例えば、三菱レイヨン製“メタブレン”、カネカ製“カネエース”、ロームアンドハース製“パラロイド”、ガンツ化成製“スタフィロイド”またはクラレ製“パラフェイス”などを挙げることができ、これらは、単独ないし2種以上を用いることができる。また、公知の方法としては、乳化重合法がより好ましい。製造方法としては、まず所望の単量体混合物を乳化重合させてコア粒子を作った後、他の単量体混合物をそのコア粒子の存在下において乳化重合させてコア粒子の周囲にシェル層を形成するコアシェル粒子を作る。さらに該粒子の存在下において他の単量体混合物を乳化重合させて別のシェル層を形成するコアシェル粒子を作る。このような反応を繰り返して所望のコア層とそれを覆う1以上のシェル層から構成される多層構造重合体を得る。各層の(共)重合体を形成させるための重合温度は、各層とも0〜120℃が好ましく、5〜90℃がより好ましい。
本発明で用いられる多層構造重合体としては、本発明の効果の点で、ガラス転移温度が0℃以下の構成成分を含むものであることがより好ましく、−30℃以下の構成成分を含むものであることがさらに好ましく、−40℃以下の構成成分を含むものであることが特に好ましい。なお、本発明において、上記ガラス転移温度は、示差走査熱量計を用い、昇温速度20℃/分で測定した値である。
As the multilayer structure polymer used in the present invention, a commercially available product may be used as a material satisfying the above-mentioned conditions, and it can also be produced by a known method. “Metablene”, Kaneka “Kane Ace”, Rohm and Haas “Paraloid”, Gantz Kasei “Staffyroid” or Kuraray “Paraface” can be used alone or in combination of two or more. Can do. Moreover, as a well-known method, an emulsion polymerization method is more preferable. As a production method, a desired monomer mixture is first emulsion-polymerized to form core particles, and then another monomer mixture is emulsion-polymerized in the presence of the core particles to form a shell layer around the core particles. Make core-shell particles to form. Further, in the presence of the particles, another monomer mixture is emulsion-polymerized to form core-shell particles that form another shell layer. Such a reaction is repeated to obtain a multilayer polymer composed of a desired core layer and one or more shell layers covering it. The polymerization temperature for forming the (co) polymer of each layer is preferably 0 to 120 ° C, more preferably 5 to 90 ° C for each layer.
The multilayer polymer used in the present invention is more preferably a component having a glass transition temperature of 0 ° C. or lower, and a component having a temperature of −30 ° C. or lower in view of the effects of the present invention. More preferably, it is particularly preferable that it contains a constituent component of −40 ° C. or lower. In the present invention, the glass transition temperature is a value measured using a differential scanning calorimeter at a rate of temperature increase of 20 ° C./min.
本発明において、多層構造重合体の平均一次粒子径は、特に限定されるものではないが、本発明の効果の点で、10〜10000nmであることが好ましく、さらに、20〜1000nmであることがより好ましく、50〜700nmであることが特に好ましく、100〜500nmであることが最も好ましい。
本発明において、耐衝撃性改良剤の配合量は、本発明の効果の点で、ポリ乳酸一軸配向フィルムの質量を基準として、0.1〜10質量%の範囲であることが必要である。下限未満では、圧着したときに剥離しやすかったり、電圧をかけたときの振動を安定させるのが困難になる。他方、上限を超えると圧電特性が低下する。そのような観点から、好ましい耐衝撃性改良剤の配合量の下限は、0.5質量%、さらに1質量%であり、他方上限は、9質量%、さらに8質量%である。なお、このような耐衝撃性改良剤を配合させることで、圧電特性を低下させることなく、耐衝撃性とは関係のない圧着後の剥離の抑制や、電圧をかけたときの振動が一定化する理由は定かではないが、得られたポリ乳酸一軸配向フィルムの配向を低下させずに、柔軟性を付与でき、結果圧着時の圧力が均等に伝わり、圧電積層体の界面に局所的に剥離しやすい部分や局所的に強直に圧着している部分が存在しなくなったためではないかと推定される。
以下、本発明の一軸配向フィルムの好ましい態様について、説明する。
In the present invention, the average primary particle diameter of the multilayer structure polymer is not particularly limited, but is preferably 10 to 10,000 nm and more preferably 20 to 1000 nm in terms of the effects of the present invention. More preferably, it is 50-700 nm, and it is most preferable that it is 100-500 nm.
In the present invention, the blending amount of the impact resistance improver needs to be in the range of 0.1 to 10% by mass based on the mass of the polylactic acid uniaxially oriented film in view of the effects of the present invention. If it is less than the lower limit, it will be easy to peel off when crimped, or it will be difficult to stabilize the vibration when a voltage is applied. On the other hand, when the upper limit is exceeded, the piezoelectric characteristics deteriorate. From such a viewpoint, the lower limit of the blending amount of the preferred impact modifier is 0.5% by mass and further 1% by mass, and the upper limit is 9% by mass and further 8% by mass. In addition, by blending such an impact resistance improver, it is possible to suppress peeling after crimping that is not related to impact resistance without deteriorating the piezoelectric properties, and to stabilize vibration when voltage is applied. The reason for this is not clear, but flexibility can be imparted without lowering the orientation of the resulting polylactic acid uniaxially oriented film, resulting in an even transmission of pressure during crimping and local peeling at the interface of the piezoelectric laminate It is presumed that this is because there are no longer any parts that are easily deformed or parts that are locally and strongly crimped.
Hereinafter, the preferable aspect of the uniaxially oriented film of this invention is demonstrated.
(密度)
本発明のポリ乳酸一軸配向フィルムの密度は、1.22〜1.27g/cm3であることが好ましい。密度が上記数値範囲にあると、共振特性の向上効果を高くすることができる。密度が低い場合は、共振特性の向上効果が低くなる傾向にあり、他方、密度が高い場合は、共振特性の向上効果は高いもののフィルムの機械特性に劣る傾向にある。このような観点から、密度は、より好ましくは1.225〜1.26g/cm3、さらに好ましくは1.23〜1.25g/cm3である。
(density)
The density of the polylactic acid uniaxially oriented film of the present invention is preferably 1.22-1.27 g / cm 3 . When the density is in the above numerical range, the effect of improving the resonance characteristics can be enhanced. When the density is low, the effect of improving the resonance characteristics tends to be low. On the other hand, when the density is high, the effect of improving the resonance characteristics is high, but the mechanical characteristics of the film tend to be inferior. From such a viewpoint, the density is more preferably 1.225 to 1.26 g / cm 3 , and still more preferably 1.23 to 1.25 g / cm 3 .
(厚み)
本発明の一軸配向フィルムの厚みは、厚すぎると剛性が高くなりすぎて共振特性を奏さなくなってしまう傾向を考慮して、共振特性を奏する程度の厚さであれば特に限定されない。共振特性の観点からは薄い方が好ましい。特に、積層数を増加させる際には、各層の厚さを薄くして、積層フィルム全体としての厚さが厚くなりすぎないようにすることが好ましい。このような観点から、配向ポリ乳酸フィルム層の1層の厚みは、好ましくは15μm以下、さらに好ましくは12μm以下、特に好ましくは10μm以下である。厚みが上記数値範囲にあると、共振特性の向上効果を高くすることができる。他方、取り扱い性や剛性の観点からは厚い方が好ましく、例えば2μm以上が好ましく、さらに好ましくは3μm以上である。
(Thickness)
The thickness of the uniaxially oriented film of the present invention is not particularly limited as long as it is thick enough to exhibit resonance characteristics in consideration of the tendency that if it is too thick, the rigidity becomes too high to exhibit resonance characteristics. The thinner one is preferable from the viewpoint of resonance characteristics. In particular, when increasing the number of layers, it is preferable to reduce the thickness of each layer so that the thickness of the entire laminated film does not become too large. From such a viewpoint, the thickness of one layer of the oriented polylactic acid film layer is preferably 15 μm or less, more preferably 12 μm or less, and particularly preferably 10 μm or less. When the thickness is in the above numerical range, the effect of improving the resonance characteristics can be enhanced. On the other hand, from the viewpoint of handleability and rigidity, a thicker is preferable, for example, 2 μm or more is preferable, and 3 μm or more is more preferable.
(添加剤等)
本発明の一軸配向フィルムは、本発明の効果を損なわない範囲で、それ自体公知の添加剤や機能剤を含有していてもよく、例えば、耐加水分解抑制剤、滑剤、酸化防止剤、帯電防止剤、着色剤、顔料、蛍光蒼白剤、可塑剤、架橋剤、紫外線吸収剤、その他の樹脂等を必要に応じて添加することができる。
(Additives, etc.)
The uniaxially oriented film of the present invention may contain known additives and functional agents as long as the effects of the present invention are not impaired. For example, the hydrolysis-resistant inhibitor, lubricant, antioxidant, An inhibitor, a colorant, a pigment, a fluorescent whitening agent, a plasticizer, a crosslinking agent, an ultraviolet absorber, other resins, and the like can be added as necessary.
例えば、本発明で使用するポリ乳酸は、カルボキシル基量は10当量/106g以下であることが、フィルムキャスティング時の安定性、加水分解抑制、重量平均分子量低下抑制の観点から好ましく、このような観点から、カルボキシル基量は5当量/106g以下であることがさらに好ましく、2当量/106g以下であることが特に好ましい。このような態様とするために、カルボキシル基封止剤を配合することが好ましい。カルボキシル基封止剤は、ポリ乳酸等のポリエステルの末端カルボキシル基の封止に加え、ポリエステルや各種添加剤の分解反応で生成するカルボキシル基、乳酸、ギ酸などの低分子化合物のカルボキシル基を封止し樹脂を安定化することができ、フィルム化時の樹脂温度を、流動斑を抑えるに足る温度まで昇温できる利点ももたらす。 For example, the polylactic acid used in the present invention preferably has a carboxyl group amount of 10 equivalents / 10 6 g or less from the viewpoint of stability during film casting, suppression of hydrolysis, and suppression of decrease in weight average molecular weight. From such a viewpoint, the amount of carboxyl groups is more preferably 5 equivalents / 10 6 g or less, and particularly preferably 2 equivalents / 10 6 g or less. In order to set it as such an aspect, it is preferable to mix | blend a carboxyl group sealing agent. Carboxyl group sealant seals terminal carboxyl groups of polyesters such as polylactic acid, as well as carboxyl groups generated by decomposition reactions of polyester and various additives, and carboxyl groups of low molecular compounds such as lactic acid and formic acid. The resin can be stabilized, and there is an advantage that the resin temperature at the time of film formation can be raised to a temperature sufficient to suppress flow spots.
かかるカルボキシル基封止剤としては、カルボジイミド化合物、エポキシ化合物、オキサゾリン化合物、オキサジン化合物、イソシアネート化合物から選択される少なくとも1種の化合物を使用することが好ましく、なかでもカルボジイミド化合物が好ましい。
カルボキシル基封止剤の使用量は、各層を構成する樹脂において、ポリ乳酸100質量部あたり、0.01〜10質量部が好ましく、0.03〜5質量部がさらに好ましい。本発明においては、さらに封止反応触媒を使用してもよい。
As such a carboxyl group-capping agent, it is preferable to use at least one compound selected from a carbodiimide compound, an epoxy compound, an oxazoline compound, an oxazine compound, and an isocyanate compound, and among them, a carbodiimide compound is preferable.
As for the usage-amount of a carboxyl group sealing agent, in resin which comprises each layer, 0.01-10 mass parts is preferable per 100 mass parts of polylactic acid, and 0.03-5 mass parts is further more preferable. In the present invention, a sealing reaction catalyst may be further used.
また、本発明の一軸配向フィルムは、巻き取りや走行性を改良する目的で、これらフィルム中に滑剤を含有することができる。かかる滑剤としては、例えば乾式法で製造されたシリカ、湿式法で製造されたシリカ、ゼオライト、炭酸カルシウム、燐酸カルシウム、カオリン、カオリナイト、クレイ、タルク、酸化チタン、アルミナ、ジルコニア、水酸化アルミニウム、酸化カルシウム、グラファイト、カーボンブラック、酸化亜鉛、炭化珪素、酸化スズ等の無機粒子や、架橋アクリル樹脂粒子、架橋ポリスチレン樹脂粒子、メラミン樹脂粒子、架橋シリコーン樹脂粒子等の有機微粒子を好ましく挙げることができる。滑剤としては、平均粒径が0.001〜5.0μmの微粒子が好ましく、1種類で使用することもできるし2種類以上併用することも可能である。また滑剤は、層Lまたは層Dの各層の質量に対して、0.01〜1.0質量%、さらに好ましくは0.1〜0.5質量%の範囲で配合することができる。 Moreover, the uniaxially oriented film of the present invention can contain a lubricant in these films for the purpose of improving winding and running properties. Examples of such lubricants include silica produced by a dry method, silica produced by a wet method, zeolite, calcium carbonate, calcium phosphate, kaolin, kaolinite, clay, talc, titanium oxide, alumina, zirconia, aluminum hydroxide, Preferable examples include inorganic particles such as calcium oxide, graphite, carbon black, zinc oxide, silicon carbide, and tin oxide, and organic fine particles such as crosslinked acrylic resin particles, crosslinked polystyrene resin particles, melamine resin particles, and crosslinked silicone resin particles. . As the lubricant, fine particles having an average particle diameter of 0.001 to 5.0 μm are preferable, and one kind can be used, or two or more kinds can be used in combination. Further, the lubricant can be blended in the range of 0.01 to 1.0% by mass, more preferably 0.1 to 0.5% by mass with respect to the mass of each layer of the layer L or the layer D.
(ポリ乳酸の製造)
つぎに、本発明の一軸配向フィルムについて、その製造方法を説明する。本発明におけるポリL−乳酸およびポリD−乳酸を製造する方法は特別に限定されるものではなく、従来公知の方法が好適に使用できる。例えば、L−乳酸またはD−乳酸を直接脱水縮合する方法、L−またはD−乳酸オリゴマーを固相重合する方法、L−またはD−乳酸を一度脱水環化してラクチドとした後、溶融開環重合する方法等が例示される。なかでも、直接脱水縮合方法、あるいはラクチド類の溶融開環重合法により得られるポリ乳酸が、品質、生産効率の観点から好ましく、中でもラクチド類の溶融開環重合法が特に好ましく選択される。
(Manufacture of polylactic acid)
Next, a method for producing the uniaxially oriented film of the present invention will be described. The method for producing poly L-lactic acid and poly D-lactic acid in the present invention is not particularly limited, and a conventionally known method can be suitably used. For example, a method of directly dehydrating and condensing L-lactic acid or D-lactic acid, a method of solid-phase polymerizing L- or D-lactic acid oligomers, once dehydrating and cyclizing L- or D-lactic acid into lactide, and then melt-opening The method of superposing | polymerizing etc. is illustrated. Among them, polylactic acid obtained by a direct dehydration condensation method or a melt ring-opening polymerization method of lactides is preferable from the viewpoint of quality and production efficiency, and among them, a melt ring-opening polymerization method of lactides is particularly preferably selected.
これらの製造法において使用する触媒は、ポリ乳酸が前述した所定の特性を有するように重合させることができるものであれば特に限定されず、それ自体公知のものを適宜使用できる。
得られたポリL−乳酸およびポリD−乳酸は、従来公知の方法により、重合触媒を除去したり、失活剤を用いて重合触媒の触媒活性を失活、不活性化したりするのが、フィルムの溶融安定性、湿熱安定性のために好ましい。
失活剤を用いる場合、その使用量は、金属含有触媒の金属元素1当量あたり0.3から20当量、より好ましくは0.5から15当量、さらに好ましくは0.5から10当量、特に好ましくは0.6から7当量とすればよい。失活剤の使用量が少なすぎると、触媒金属の活性を十分に低下させることができないし、また過剰に使用すると、失活剤が樹脂の分解を引き起こす可能性があり好ましくない。
The catalyst used in these production methods is not particularly limited as long as polylactic acid can be polymerized so as to have the predetermined characteristics described above, and a known catalyst can be used as appropriate.
The obtained poly L-lactic acid and poly D-lactic acid may be removed by a conventionally known method or the catalytic activity of the polymerization catalyst is deactivated or deactivated using a deactivator. It is preferable for the melt stability and wet heat stability of the film.
When using a deactivator, the amount used is 0.3 to 20 equivalents, more preferably 0.5 to 15 equivalents, still more preferably 0.5 to 10 equivalents, particularly preferably, per equivalent of metal element of the metal-containing catalyst. May be 0.6 to 7 equivalents. If the amount of the deactivator used is too small, the activity of the catalyst metal cannot be lowered sufficiently, and if used excessively, the deactivator may cause decomposition of the resin, which is not preferable.
(押出工程)
上記の方法により得られたポリ乳酸に、耐衝撃性改良剤を配合し、所望により前述のカルボキシル基封止剤、滑剤、その他の添加剤等を配合し、ポリL−乳酸(層Lの場合。層Dの場合はポリD−乳酸とする。以下同様。)を主たる成分とする樹脂L(ポリL−乳酸を用いた場合。ポリD−乳酸を用いた場合は樹脂Dとする。以下同様。)を、押出機において溶融し、ダイから冷却ドラム上に押し出す。尚、押出機に供給する樹脂は、溶融時の分解を抑制するため、押出機供給前に乾燥処理を行い、水分含有量を100ppm以下程度にすることが好ましい。
押出機における樹脂温度は、樹脂が十分に流動性を有する温度、すなわち、樹脂Lの融点をTmとすると、(Tm+20)から(Tm+50)(℃)の範囲で実施されるが、樹脂が分解しない温度で溶融押し出しするのが好ましく、かかる温度としては、好ましくは200〜260℃、さらに好ましくは205〜240℃、特に好ましくは210〜235℃である。上記温度範囲であると流動斑が発生しにくい。
(Extrusion process)
The polylactic acid obtained by the above method is blended with an impact resistance improver, and if desired, the above-mentioned carboxyl group-capping agent, lubricant, other additives, and the like are blended, and poly L-lactic acid (in the case of layer L) In the case of layer D, it is poly D-lactic acid. The same applies hereinafter.) Resin L (when poly L-lactic acid is used. When poly D-lactic acid is used, it is resin D. The same applies hereinafter. .) Is melted in an extruder and extruded from a die onto a cooling drum. In addition, in order to suppress decomposition at the time of melting, the resin supplied to the extruder is preferably subjected to a drying process before being supplied to the extruder so that the water content is about 100 ppm or less.
The resin temperature in the extruder is a temperature at which the resin has sufficient fluidity, that is, when the melting point of the resin L is Tm, it is carried out in the range of (Tm + 20) to (Tm + 50) (° C.), but the resin does not decompose. It is preferable to perform melt extrusion at a temperature, and such a temperature is preferably 200 to 260 ° C, more preferably 205 to 240 ° C, and particularly preferably 210 to 235 ° C. Within the above temperature range, flow spots are unlikely to occur.
(キャスティング工程)
ダイから押し出した後、フィルムを冷却ドラムにキャスティングして未延伸フィルムを得る。その際、静電密着法により電極より静電荷を印加させることによって冷却ドラムに十分に密着させて冷却固化するのが好ましい。この時、静電荷を印加する電極はワイヤー状或いはナイフ状の形状のものが好適に使用される。該電極の表面物質は白金であることが好ましく、フィルムより昇華する不純物が電極表面に付着するのを抑制することができる。また、高温空気流を電極或いはその近傍に噴きつけ電極の温度を170〜350℃に保ち、電極上部に排気ノズルを設置することにより不純物の付着を防ぐこともできる。
(Casting process)
After extruding from the die, the film is cast on a cooling drum to obtain an unstretched film. At that time, it is preferable that the electrostatic charge is applied from the electrode by an electrostatic contact method so that it is sufficiently brought into close contact with the cooling drum and cooled and solidified. At this time, the electrode to which an electrostatic charge is applied preferably has a wire shape or a knife shape. The surface material of the electrode is preferably platinum, and can prevent impurities sublimated from the film from adhering to the electrode surface. Further, it is possible to prevent adhesion of impurities by blowing a high-temperature air flow on or near the electrode, keeping the temperature of the electrode at 170 to 350 ° C., and installing an exhaust nozzle above the electrode.
(延伸工程)
前記で得られた未延伸フィルムは、一軸方向に延伸する。延伸方向は特に制限されないが、製膜方向、幅方向または製膜方向と幅方向に対して、それぞれ45度となるような斜め方向に延伸するのが好ましい。かかる延伸を行うには、未延伸フィルムを延伸可能な温度、例えば樹脂Lのガラス転移点温度(Tg)以上(Tg+80)℃以下の温度に加熱して延伸する。
主配向方向の延伸倍率は、好ましくは3倍以上、より好ましくは3.5倍以上、さらに好ましくは4.0倍以上、特に好ましくは4.5倍以上である。延伸倍率を上記上限以上にとすることによって変位量の向上効果を高くすることができる。一方、延伸倍率の上限は特に制限されないが、製膜性の点から10倍以下であることが好ましく、さらに8倍以下、特に7倍以下であることが好ましい。他方、主配向方向と直交する方向は、延伸を行う必要はないが、前述の破断強度の関係を満足する範囲で延伸を施してもよい。その場合の延伸倍率は1.5倍以下が好ましく、さらに1.3倍以下が好ましい。
(Stretching process)
The unstretched film obtained above is stretched in a uniaxial direction. The stretching direction is not particularly limited, but it is preferable to stretch in a film forming direction, a width direction, or an oblique direction of 45 degrees with respect to the film forming direction and the width direction. In order to perform such stretching, the unstretched film is stretched by being heated to a temperature at which the unstretched film can be stretched, for example, a glass transition temperature (Tg) or higher (Tg + 80) ° C. of the resin L.
The draw ratio in the main orientation direction is preferably 3 times or more, more preferably 3.5 times or more, still more preferably 4.0 times or more, and particularly preferably 4.5 times or more. The effect of improving the amount of displacement can be increased by setting the draw ratio to the above upper limit or more. On the other hand, the upper limit of the draw ratio is not particularly limited, but is preferably 10 times or less, more preferably 8 times or less, and particularly preferably 7 times or less from the viewpoint of film forming property. On the other hand, the direction orthogonal to the main orientation direction does not need to be stretched, but may be stretched within a range satisfying the above-described relationship of breaking strength. In that case, the draw ratio is preferably 1.5 times or less, more preferably 1.3 times or less.
(熱処理工程)
上記で得られた配向ポリ乳酸フィルムは、熱処理することが好ましい。熱処理温度は、前述の延伸温度よりも高く、樹脂の融点(Tm)未満の温度で行えばよく、好ましくはガラス転移点温度(Tg+15)℃以上(Tm−10)℃以下、さらに好ましくは(Tg+20)℃以上(Tm−20)℃、特に好ましくは(Tg+30)℃以上(Tm−35)℃である。熱処理温度が上記範囲にあることで、厚み斑や表面の平坦性を良好にしつつ、主配向軸を揃えやすくなり、機械特性も優れたものとできる。熱処理時間は、好ましくは1〜120秒、さらに好ましくは2〜60秒である。
さらに本発明においては、熱処理工程において弛緩処理して、熱寸法安定性を調整することも可能である。
(Heat treatment process)
The oriented polylactic acid film obtained above is preferably heat-treated. The heat treatment temperature may be higher than the above-mentioned stretching temperature and lower than the melting point (Tm) of the resin, preferably the glass transition temperature (Tg + 15) ° C. or more and (Tm−10) ° C. or less, more preferably (Tg + 20). ) ° C. or higher (Tm−20) ° C., particularly preferably (Tg + 30) ° C. or higher (Tm−35) ° C. When the heat treatment temperature is in the above range, the main alignment axis can be easily aligned and the mechanical properties can be excellent while improving the thickness unevenness and surface flatness. The heat treatment time is preferably 1 to 120 seconds, more preferably 2 to 60 seconds.
Furthermore, in the present invention, it is possible to adjust the thermal dimensional stability by performing a relaxation treatment in the heat treatment step.
(易接着処理)
かくして得られた配向ポリ乳酸フィルム層は、所望により従来公知の方法で、例えば表面活性化処理、例えばプラズマ処理、アミン処理、コロナ処理を施すことも可能である。
なかでも、後述の導電層Mとの密着性を向上し、圧電積層体の耐久性を高めるという観点から、配向フィルム層の少なくとも片面、好ましくは両面に、コロナ処理を施すことが好ましい。かかるコロナ処理の条件としては、例えば電極距離を5mmとした際に、好ましくは1〜20kV、さらに好ましくは5〜15kVの電圧で、好ましくは1〜60秒、さらに好ましくは5〜30秒、特に好ましくは10〜25秒行うとよい。また、かかる処理は大気中で行うことができる。
(Easy adhesion treatment)
The oriented polylactic acid film layer thus obtained can be subjected to surface activation treatment such as plasma treatment, amine treatment or corona treatment by a conventionally known method if desired.
Especially, it is preferable to perform a corona treatment on at least one side, preferably both sides of the oriented film layer, from the viewpoint of improving the adhesion with the conductive layer M described later and enhancing the durability of the piezoelectric laminate. As conditions for such corona treatment, for example, when the electrode distance is 5 mm, the voltage is preferably 1 to 20 kV, more preferably 5 to 15 kV, preferably 1 to 60 seconds, more preferably 5 to 30 seconds, particularly Preferably it is 10 to 25 seconds. Further, such treatment can be performed in the atmosphere.
[圧電積層体]
つぎに、もう一つの本発明である圧電積層体について、以下に説明する。
本発明の圧電積層体は、上記本発明のポリ乳酸一軸配向フィルムと導電層とを交互に積層したものである。この際、隣り合う導電層は逆の電荷がかけられるようにしておき、一方隣り合うポリ乳酸一軸配向フィルムは、逆の電荷を掛けられた状態で、圧電特性が高めあうように主配向軸の向きを配置しておく。
例えば、ポリL−乳酸またはポリD−乳酸のいずれか一方からなる一軸配向フィルムが、導電層を介して隣り合い、隣り合う一軸配向フィルムの主配向軸が直交するように積層する。
またポリL−乳酸からなる一軸配向フィルムと、ポリD−乳酸からなるからなる一軸配向フィルムとが、導電層を介して隣り合い、隣り合う一軸配向フィルムの主配向軸が同方向であるように積層する。
[Piezoelectric laminate]
Next, another piezoelectric laminate according to the present invention will be described below.
The piezoelectric laminate of the present invention is obtained by alternately laminating the polylactic acid uniaxially oriented film of the present invention and a conductive layer. At this time, the adjacent conductive layer is allowed to be charged with the opposite charge, while the adjacent polylactic acid uniaxially oriented film has the main alignment axis so that the piezoelectric characteristics are enhanced in the state where the opposite charge is applied. Arrange the orientation.
For example, uniaxially oriented films made of either one of poly L-lactic acid or poly D-lactic acid are laminated so as to be adjacent to each other via a conductive layer, and the main orientation axes of adjacent uniaxially oriented films are orthogonal to each other.
Further, the uniaxially oriented film made of poly L-lactic acid and the uniaxially oriented film made of poly D-lactic acid are adjacent to each other through the conductive layer, and the main orientation axes of the adjacent uniaxially oriented films are in the same direction. Laminate.
なお、本発明の圧電積層体は、隣り合うポリ乳酸一軸配向フィルムが上記のような関係を満足していればよく、全てのポリ乳酸一軸配向フィルムがL体もしくはD体のいずれかである態様、ポリ乳酸一軸配向フィルムがL体とD体とで、それらが交互に積層された態様、または部分的にそれらが組み合わさった態様のいずれであってもよい。
なお、本発明における隣り合う配向ポリ乳酸フィルムの主配向軸が直交するとは、ほぼ90度の角度であることを意味し、90度に近くなればなるほど圧電特性はより効果的に発現される。そのような観点から、好ましい隣り合う配向ポリ乳酸フィルムの主配向軸がなす鋭角の角度は、80度以上であることが好ましく、さらに85度以上であることが好ましく、特に88度以上であることが好ましい。また本発明における隣り合う配向ポリ乳酸フィルムの主配向軸が同方向とは、ほぼ0度の角度であることを意味し、0度に近くなればなるほど圧電特性はより効果的に発現される。そのような観点から、好ましい隣り合う配向ポリ乳酸フィルムの主配向軸がなす鋭角の角度は、10度以下であることが好ましく、さらに5度以下であることが好ましく、特に2度以下であることが好ましい。
In the piezoelectric laminate of the present invention, the adjacent polylactic acid uniaxially oriented films only need to satisfy the above relationship, and all the polylactic acid uniaxially oriented films are either L-form or D-form. The polylactic acid uniaxially oriented film may be in an L-form and a D-form, in which they are alternately laminated, or in an aspect in which they are partially combined.
In addition, the fact that the main orientation axes of adjacent oriented polylactic acid films in the present invention are orthogonal means an angle of approximately 90 degrees, and the closer to 90 degrees, the more effectively the piezoelectric characteristics are expressed. From such a viewpoint, the acute angle formed by the main orientation axes of the adjacent oriented polylactic acid films is preferably 80 degrees or more, more preferably 85 degrees or more, and particularly 88 degrees or more. Is preferred. In addition, the main orientation axis of adjacent oriented polylactic acid films in the present invention being in the same direction means an angle of almost 0 degrees, and the closer to 0 degrees, the more effectively the piezoelectric characteristics are expressed. From such a viewpoint, the acute angle formed by the main orientation axes of the adjacent oriented polylactic acid films is preferably 10 degrees or less, more preferably 5 degrees or less, particularly 2 degrees or less. Is preferred.
本発明の圧電積層体は、圧電特性を高くする観点から、ポリ乳酸一軸配向フィルムの合計層数は4以上であることが好ましく、さらに8以上あることが好ましく、特に10以上であることが好ましい。他方、ポリ乳酸一軸配向フィルムにある程度取扱い性を具備する厚さを持たせつつ、圧電積層体全体の厚みを、過度に強直にならないようにする観点から、合計総数の上限は、300以下、さらに200以下であることが好ましい。 In the piezoelectric laminate of the present invention, the total number of polylactic acid uniaxially oriented films is preferably 4 or more, more preferably 8 or more, and particularly preferably 10 or more, from the viewpoint of enhancing the piezoelectric characteristics. . On the other hand, the upper limit of the total number is 300 or less, from the viewpoint of preventing the thickness of the entire piezoelectric laminate from becoming excessively strong while giving the polylactic acid uniaxially oriented film a thickness that provides a certain degree of handleability. It is preferable that it is 200 or less.
本発明の圧電体の積層構成について、図1と2を用いて説明する。図1と2は、本発明の圧電体の積層構成の一例を示す模式図である。図1において、符号1は右マージン用の樹脂層で、配向ポリ乳酸フィルム層(1)で、符号2は左マージン用の樹脂層で配向ポリ乳酸フィルム層(1)に隣り合う配向ポリ乳酸フィルム層(2)をそれぞれ示す。本発明の圧電体は、このように、配向ポリ乳酸フィルム層(1)と(2)とが複数交互に積層されている。なお、図2は、配向ポリ乳酸フィルム層(1)が3枚、配向ポリ乳酸フィルム層(2)が3枚、合計6枚の場合である。
符号3は、導電層Mを示す。本発明においては、配向ポリ乳酸フィルム層(1)と(2)の間に導電層M(3)を有する。また、圧電体の少なくとも一方の表面に導電層M(3)を有することが好ましく、さらにもう一方の表面に導電層M(3)を有していてもよい。
The laminated structure of the piezoelectric body of the present invention will be described with reference to FIGS. 1 and 2 are schematic views showing an example of the laminated structure of the piezoelectric body of the present invention. In FIG. 1,
配向ポリ乳酸フィルム層(1)と導電層M、および配向ポリ乳酸フィルム層(2)と導電層Mは、厚み1000nmを超える接着剤層を介さずに固着していることが好ましい。本発明においては、このような態様とすることにより、優れた共振特性を奏することができる。かかる観点から、本発明においては、厚み500nmを超える接着剤層を介さずに固着している態様が好ましく、厚み200nmを超える接着剤層を介さずに固着している態様がさらに好ましい。共振特性の観点から、最も好ましくは、接着剤層を介さずに固着している態様である。
本発明においては、上記のような積層構成を有していれば、本発明の目的を阻害しない範囲において、さらにその他の層を有していても良い。例えば、積層フィルムの表面に、積層フィルムの剛性を高めるための、例えばポリエチレンテレフタレートやポリエチレンナフタレートのような芳香族ポリエステル層を有することができる。一方、共振特性の観点からは、このような層は、その厚みが薄いことが好ましく、有しないことが特に好ましい。
The oriented polylactic acid film layer (1) and the conductive layer M, and the oriented polylactic acid film layer (2) and the conductive layer M are preferably fixed without an adhesive layer having a thickness exceeding 1000 nm. In the present invention, excellent resonance characteristics can be achieved by adopting such an embodiment. From such a viewpoint, in the present invention, an embodiment in which the adhesive layer is fixed without using an adhesive layer having a thickness exceeding 500 nm is preferable, and an embodiment in which the adhesive layer is fixed without using an adhesive layer having a thickness exceeding 200 nm is more preferable. From the viewpoint of resonance characteristics, it is most preferable to fix the adhesive layer without using an adhesive layer.
In the present invention, as long as it has the laminated structure as described above, it may further have other layers within a range not impairing the object of the present invention. For example, an aromatic polyester layer such as polyethylene terephthalate or polyethylene naphthalate for increasing the rigidity of the laminated film can be provided on the surface of the laminated film. On the other hand, from the viewpoint of resonance characteristics, such a layer is preferably thin and particularly preferably not.
(導電層M)
本発明における導電層Mは、本発明の圧電積層体が、電圧印加した際に圧電特性を示すことができる程度の導電性を有していれば、その種類は特に限定されないが、より好適に圧電特性および共振特性を示すことができるという観点から、金属または金属酸化物からなる層であることが好ましい。
かかる金属または金属酸化物としては、特に限定はされないが、インジウム、スズ、亜鉛、ガリウム、アンチモン、チタン、珪素、ジルコニウム、マグネシウム、アルミニウム、金、銀、銅、パラジウム、タングステンからなる群より選択される少なくとも1種の金属、または上記群より選択される少なくとも1種の金属の酸化物が好ましく用いられる。また、金属酸化物には、必要に応じて、さらに上記群に示された金属、または上記群に示された他の金属の酸化物を含んでいてもよい。例えば、酸化スズを含有する酸化インジウム、アンチモンを含有する酸化スズ等が好ましく用いられる。
(Conductive layer M)
The type of the conductive layer M in the present invention is not particularly limited as long as the piezoelectric laminate of the present invention has a conductivity sufficient to exhibit piezoelectric characteristics when a voltage is applied. From the viewpoint that piezoelectric characteristics and resonance characteristics can be exhibited, a layer made of metal or metal oxide is preferable.
Such metal or metal oxide is not particularly limited, but is selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, tungsten. Preferably, at least one metal selected from the group described above or an oxide of at least one metal selected from the above group is preferably used. Further, the metal oxide may further contain an oxide of a metal shown in the above group or another metal shown in the above group, if necessary. For example, indium oxide containing tin oxide and tin oxide containing antimony are preferably used.
導電層Mの厚さは特に制限されないが、その表面抵抗値が好ましくは1×104Ω/□以下、より好ましくは5×103Ω/□以下、さらに好ましくは1×103Ω/□以下となるような厚みを選択すればよく、例えば、厚さ10nm以上とするのが好ましい。さらに、導電性と、層形成のし易さの観点から、15〜35nmであることが好ましく、より好ましくは20〜30nmである。厚さが薄すぎると、表面抵抗値が高くなる傾向にあり、かつ連続被膜になり難くなる。他方、厚すぎると、品質過剰であり、また圧電積層体の形成が困難となったり、圧電積層体の層間の強度が弱くなったりする傾向にある。 The thickness of the conductive layer M is not particularly limited, but the surface resistance value is preferably 1 × 10 4 Ω / □ or less, more preferably 5 × 10 3 Ω / □ or less, and further preferably 1 × 10 3 Ω / □. What is necessary is just to select the thickness which becomes the following, for example, it is preferable to set it as thickness 10nm or more. Furthermore, it is preferable that it is 15-35 nm from a viewpoint of electroconductivity and the ease of layer formation, More preferably, it is 20-30 nm. If the thickness is too thin, the surface resistance value tends to be high, and it becomes difficult to form a continuous film. On the other hand, if it is too thick, the quality is excessive, the formation of the piezoelectric laminate is difficult, and the strength between the layers of the piezoelectric laminate tends to be weak.
(圧電積層体の製造)
本発明における圧電積層体の製造方法は、前述の製造方法で得た一軸配向フィルムの一方の面に導電層を形成した積層体を用意し、前述の主配向方向の関係となるように一軸配向フィルムと導電層とが交互になるように積層する。
導電層Mの形成方法としては特に限定されず、従来公知の方法を採用することができる。具体的には、例えば真空蒸着法、スパッタリング法、イオンプレーティング法を例示でき、優れた導電性を有する導電層を均一に、容易に得ることができるという観点から、蒸着法またはスパッタリング法を採用することが好ましい。なお、金属層を形成した後、必要に応じて、100〜150℃の範囲内でアニール処理を施して結晶化することができる。このため、層Lおよび層Dは、100℃以上、更には110℃以上の耐熱性を有することが好ましい。また、導電層Mは、配向フィルム層の両面に形成してもよいが、密着性の観点からは、片面のみに導電層Mを形成することが好ましい。その場合、隣り合う配向ポリ乳酸フィルム層を裏返して積層することから、配向ポリ乳酸フィルム層の一方の表面に導電層を形成したものと、配向ポリ乳酸フィルム層の他方の表面に導電層を形成したものとを用意するのが好ましい。
上記により得られた導電層Mを有する配向ポリ乳酸フィルム層を、本発明が規定する積層構成となるように積層して積層体を作成し、熱ラミネートにより固着する。ここで熱ラミネートは、接着剤層を用いずに行う。
(Manufacture of piezoelectric laminate)
The piezoelectric laminate manufacturing method of the present invention is prepared by preparing a laminate in which a conductive layer is formed on one surface of a uniaxially oriented film obtained by the above-described manufacturing method, and uniaxially oriented so as to have the above-described main orientation direction relationship. Lamination is performed so that the film and the conductive layer alternate.
It does not specifically limit as a formation method of the conductive layer M, A conventionally well-known method is employable. Specifically, for example, a vacuum deposition method, a sputtering method, and an ion plating method can be exemplified, and a vapor deposition method or a sputtering method is adopted from the viewpoint that a conductive layer having excellent conductivity can be obtained uniformly and easily. It is preferable to do. In addition, after forming a metal layer, it can crystallize by giving an annealing process within the range of 100-150 degreeC as needed. For this reason, it is preferable that the layer L and the layer D have heat resistance of 100 ° C. or higher, more preferably 110 ° C. or higher. Moreover, although the conductive layer M may be formed on both surfaces of the oriented film layer, it is preferable to form the conductive layer M only on one surface from the viewpoint of adhesion. In that case, since the adjacent oriented polylactic acid film layer is turned upside down, the conductive layer is formed on one surface of the oriented polylactic acid film layer and the conductive layer is formed on the other surface of the oriented polylactic acid film layer. It is preferable to prepare the product.
The oriented polylactic acid film layer having the conductive layer M obtained as described above is laminated so as to have a laminated structure defined by the present invention to prepare a laminate, and is fixed by thermal lamination. Here, the thermal lamination is performed without using an adhesive layer.
かかる熱ラミネートにおける温度条件は、(Tg−5)〜(Tsm+20)℃とすることが好ましい。ここでTgは、積層フィルムの形成に用いる配向フィルム層Lを構成する樹脂Lのガラス転移温度および配向フィルム層Dを構成する樹脂Dのガラス転移温度のうち、最も高いガラス転移温度を示す。また、Tsmは、積層フィルムの形成に用いる配向フィルム層Lのサブピーク温度および配向フィルム層Dのサブピーク温度のうち、最も低いサブピーク温度を示す。なお、サブピーク温度とは、フィルム製造プロセスにおける熱固定温度に起因する温度である。上記温度条件を採用することにより、優れた共振特性を奏する積層フィルムを得ることができる。また、同時に、積層フィルムの各層の密着性に優れる。温度が低すぎると密着性に劣る傾向にあり、他方高すぎると配向が崩れてしまい共振特性に劣る傾向にある。このような観点より、さらに好ましい温度条件はTg〜Tsm+15であり、特に好ましくはTg+10〜Tsm+10である。 The temperature condition in such a heat laminate is preferably (Tg-5) to (Tsm + 20) ° C. Here, Tg indicates the highest glass transition temperature among the glass transition temperature of the resin L constituting the oriented film layer L used for forming the laminated film and the glass transition temperature of the resin D constituting the oriented film layer D. Tsm indicates the lowest sub-peak temperature among the sub-peak temperature of the oriented film layer L and the sub-peak temperature of the oriented film layer D used for forming the laminated film. In addition, subpeak temperature is temperature resulting from the heat setting temperature in a film manufacturing process. By adopting the above temperature condition, a laminated film having excellent resonance characteristics can be obtained. At the same time, the adhesion of each layer of the laminated film is excellent. If the temperature is too low, the adhesion tends to be inferior. On the other hand, if the temperature is too high, the orientation is lost and the resonance characteristics tend to be inferior. From such a viewpoint, more preferable temperature conditions are Tg to Tsm + 15, and particularly preferably Tg + 10 to Tsm + 10.
また、圧力条件は、1〜30MPa、2〜28MPa、5〜25MPaとすることが好ましい。これにより優れた共振特性を有しながら、密着性に優れた積層フィルムを得ることができる。圧力が低すぎると密着性に劣る傾向にあり、他方高すぎると共振特性に劣る傾向にある。
以上のような温度条件および圧力条件において、10〜600秒の熱ラミネートを行うことが好ましい。これにより優れた共振特性を有しながら、密着性に優れた積層フィルムを得ることができる。時間が短すぎると密着性に劣る傾向にあり、他方長すぎると共振特性に劣る傾向にある。このような観点より、さらに好ましい時間条件は30〜300秒であり、特に好ましくは60〜180秒である。
そして、本発明によれば、このような圧電特性を損なわないような条件で熱圧着しても、剥離などの問題がなく、高度に圧電特性を発現させることができる。
Moreover, it is preferable that pressure conditions shall be 1-30 MPa, 2-28 MPa, and 5-25 MPa. Thereby, it is possible to obtain a laminated film excellent in adhesion while having excellent resonance characteristics. If the pressure is too low, the adhesion tends to be inferior, whereas if the pressure is too high, the resonance characteristics tend to be inferior.
It is preferable to perform thermal lamination for 10 to 600 seconds under the above temperature and pressure conditions. Thereby, it is possible to obtain a laminated film excellent in adhesion while having excellent resonance characteristics. If the time is too short, the adhesion tends to be inferior, while if too long, the resonance characteristics tend to be inferior. From such a viewpoint, a more preferable time condition is 30 to 300 seconds, and particularly preferably 60 to 180 seconds.
And according to this invention, even if it thermocompression-bonds on the conditions which do not impair such a piezoelectric characteristic, there is no problem of peeling etc. and a piezoelectric characteristic can be expressed highly.
以下、本発明を実施例によりさらに具体的に説明するが、本発明はこれにより何ら限定を受けるものではない。なお、実施例中の各値は以下の方法に従って求めた。 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention does not receive limitation at all by this. In addition, each value in an Example was calculated | required according to the following method.
(1)積層フィルムの剥離
積層フィルムの端部をしごく等して切欠をつくり、各層を剥離し、配向フィルム層Lおよび層Dを剥離して取り出し、各層についての物性評価に用いた。
(1) Peeling of laminated film The ends of the laminated film were squeezed to make notches, each layer was peeled off, the oriented film layer L and the layer D were peeled off, and used for evaluating physical properties of each layer.
(2)密度
積層フィルムから剥離したフィルムサンプルについて、JIS規格 C2151に準じて測定した。
(2) Density The film sample peeled from the laminated film was measured according to JIS standard C2151.
(3)主配向方向
エリプソメーター(型式M−220 ; 日本分光)を用い、得られたフィルムを550nm単色光の入射角度を変化させた透過光測定に供し、フィルムを固定した試料台を、光軸を中心に光軸に対して垂直な面内にて回転させて、面内方向の最も屈折率の高い方向を求め、その方向を主配向方向とした。なお、幅方向を0°とし、製膜方向を90°として、主配向方向の角度を算出した。
(3) Main orientation direction Using an ellipsometer (model M-220; JASCO), the obtained film was subjected to transmitted light measurement in which the incident angle of 550 nm monochromatic light was changed. By rotating in a plane perpendicular to the optical axis about the axis, the direction with the highest refractive index in the in-plane direction was determined, and that direction was defined as the main orientation direction. The angle in the main orientation direction was calculated with the width direction being 0 ° and the film forming direction being 90 °.
(4)ガラス転移温度(Tg)、サブピーク温度(Tsm)、融点(Tm)
製膜により得られた、積層フィルムとする前の配向フィルム層について、サンプル約10mgを測定用のアルミニウム製パンに封入して示差熱量計(TAinstruments社製商品名「DSC2920」)に装着し、25℃から10℃/分の速度で210℃まで昇温させ、フィルムのサブピーク温度(Tsm:℃)および融点(Tm:℃)を測定した。次いで、引き続き210℃で3分間保持した後、取り出し、直ちに氷の上に移して急冷し、このパンを再度示差熱量計に装着し、25℃から10℃/分の速度で昇温させて、フィルムを構成する樹脂のガラス転移温度(Tg:℃)および融点(Tm:℃)を測定した。
(4) Glass transition temperature (Tg), sub-peak temperature (Tsm), melting point (Tm)
About the oriented film layer obtained as a laminated film before forming a laminated film, about 10 mg of a sample is enclosed in an aluminum pan for measurement and attached to a differential calorimeter (trade name “DSC2920” manufactured by TA instruments), 25 The film was heated from 210 ° C. to 210 ° C. at a rate of 10 ° C./min, and the sub-peak temperature (Tsm: ° C.) and melting point (Tm: ° C.) of the film were measured. Next, after continuously holding at 210 ° C. for 3 minutes, it is taken out, immediately transferred onto ice and rapidly cooled, this pan is again attached to the differential calorimeter, and the temperature is raised from 25 ° C. at a rate of 10 ° C./min. The glass transition temperature (Tg: ° C.) and melting point (Tm: ° C.) of the resin constituting the film were measured.
(5)導電性(表面抵抗値)
三菱化学社製、商品名:Lorester MCP−T600を用いて、JIS K7194に準拠して測定した。測定は、1つのフィルムから3つの測定用サンプル片を採取し、それぞれ任意の5箇所について実施し、それらの平均値を表面抵抗値(単位:Ω/□)とした。
(5) Conductivity (surface resistance value)
It measured based on JISK7194 using Mitsubishi Chemical Corporation make and brand name: Lorester MCP-T600. The measurement was performed by taking three measurement sample pieces from one film and carrying out the measurement at five arbitrary locations, and taking the average value as the surface resistance value (unit: Ω / □).
(6)剥離試験
各実施例で作成した長さ7cm幅3cmの圧電積層体を試験片とし、試験片の短辺A片側を固定し、図3に示すように反対側短辺BをA側へ屈曲させて状態変化を観察する。
○:短辺Aと短辺Bを重ねても剥離なし
△:短辺Aと短辺Bを重ねると剥離が見られる
×:短辺Aと短辺Bを重ねる前に剥離が見られる
(6) Peeling test The piezoelectric laminate having a length of 7 cm and a width of 3 cm prepared in each example is used as a test piece, the short side A side of the test piece is fixed, and the opposite short side B is set to the A side as shown in FIG. Observe the state change.
○: No peeling even when the short side A and the short side B are overlapped. Δ: The peeling is observed when the short side A and the short side B are overlapped. ×: The peeling is seen before the short side A and the short side B are overlapped.
(7)圧電特性
得られた圧電積層体の両方の短辺に、図2に示すごとく、導電性接着剤(藤倉化成製、ドータイトD550)を塗布して電極(6)を形成し、圧電性構造体を作成した。これにより、各アルミ蒸着層において、マージンを有する側においてはかかる導電性接着剤とアルミ蒸着層とが短絡せず、マージンを有しない側においてはかかる導電性接着剤とアルミ蒸着層とが短絡した構成となる。
この圧電積層体のそれぞれの電極にアルミ箔を取り付け、図4に示すように、圧電特性測定装置(12)(Agilent Technologies社製、商品名:プレシジョン インピーダンスアナライザ 4294A)に取り付け、二端子法によるアドミッタンスの共振測定を行った。この時、共振に影響が無いよう、図4に示すように圧電積層体は円柱(11)の上に置き、机上面との接触面積が少なくなるように設置した。なお、アドミッタンスの共振測定は、等価回路パターンEにて圧電共振波形を測定する方法で行い、得られた各種パラメータから圧電率(単位:pC/N)を算出した。圧電率が高いほど圧電性能に優れることを意味する。
(7) Piezoelectric characteristics As shown in FIG. 2, a conductive adhesive (manufactured by Fujikura Kasei, Dotite D550) is applied to both short sides of the obtained piezoelectric laminate to form an electrode (6). Created a structure. Thus, in each aluminum vapor deposition layer, the conductive adhesive and the aluminum vapor deposition layer are not short-circuited on the side having a margin, and the conductive adhesive and the aluminum vapor deposition layer are short-circuited on the side having no margin. It becomes composition.
An aluminum foil is attached to each electrode of this piezoelectric laminate, and as shown in FIG. 4, it is attached to a piezoelectric characteristic measuring device (12) (manufactured by Agilent Technologies, trade name: Precision Impedance Analyzer 4294A), and admittance by a two-terminal method. The resonance measurement was performed. At this time, the piezoelectric laminate was placed on the column (11) as shown in FIG. 4 so as not to affect the resonance, and was installed so that the contact area with the desk surface was reduced. The admittance resonance was measured by a method of measuring a piezoelectric resonance waveform with the equivalent circuit pattern E, and the piezoelectric ratio (unit: pC / N) was calculated from the various parameters obtained. Higher piezoelectricity means better piezoelectric performance.
(8)破断強度
東洋ボールドウィン社製テンシロンを使用し、23℃、65%RHの条件下で測定した。ここでいう破断強度とは、引張試験を行った際の試料破断時の荷重の値を試験前の試料の断面積で除した、単位断面積当りの応力の値を意味する。なお、試料幅は10mm、チャック間距離100mm、チャック間スピード100mm/分で測定は行った。
(8) Breaking strength Tensilon manufactured by Toyo Baldwin Co. was used and measured under conditions of 23 ° C. and 65% RH. The term “breaking strength” as used herein means a value of stress per unit cross-sectional area obtained by dividing the value of the load at the time of the sample breaking when the tensile test is performed by the cross-sectional area of the sample before the test. The sample width was 10 mm, the distance between chucks was 100 mm, and the speed between chucks was 100 mm / min.
[参考例1]ポリL−乳酸(PLLA)の合成
真空配管、窒素ガス配管、触媒添加配管、L−ラクチド溶液添加配管、アルコール開始剤添加配管を具備したフルゾーン翼具備縦型攪拌槽(40L)を窒素置換した。その後、L−ラクチド30Kg、ステアリルアルコール0.90kg(0.030モル/kg)、オクチル酸スズ6.14g(5.05×10−4モル/1kg)を仕込み、窒素圧106.4kPaの雰囲気下、150℃に昇温した。内容物が溶解した時点で、攪拌を開始、内温をさらに190℃に昇温した。内温が180℃を超えると反応が始まるため、冷却しながら内温を185℃から190℃に保持し1時間反応を継続した。さらに攪拌しつつ、窒素圧106.4kPa、内温200℃から210℃で1時間反応を行なった後、攪拌を停止しリン系の触媒失活剤を添加した。
[Reference Example 1] Synthesis of poly-L-lactic acid (PLLA) Vertical stirring tank (40L) equipped with full zone blades equipped with vacuum piping, nitrogen gas piping, catalyst addition piping, L-lactide solution addition piping, alcohol initiator addition piping Was replaced with nitrogen. Thereafter, 30 kg of L-lactide, 0.90 kg of stearyl alcohol (0.030 mol / kg), and 6.14 g of tin octylate (5.05 × 10 −4 mol / 1 kg) were charged in an atmosphere with a nitrogen pressure of 106.4 kPa. The temperature was raised to 150 ° C. When the contents were dissolved, stirring was started and the internal temperature was further raised to 190 ° C. Since the reaction started when the internal temperature exceeded 180 ° C., the internal temperature was maintained from 185 ° C. to 190 ° C. while cooling and the reaction was continued for 1 hour. The reaction was further carried out at a nitrogen pressure of 106.4 kPa and an internal temperature of 200 ° C. to 210 ° C. for 1 hour while stirring, and then stirring was stopped and a phosphorus-based catalyst deactivator was added.
さらに20分間静置して気泡除去をおこなった後、内圧を窒素圧で2から3気圧に昇圧し、プレポリマーをチップカッターに押し出し、重量平均分子量13万、分子量分散1.8のプレポリマーをペレット化した。
さらに、ペレットを押出機で溶解させ、無軸籠型反応装置に15kg/hrで投入し、10.13kPaに減圧して残留するラクチドを低減処理し、それを再度チップ化した。得られたポリL−乳酸(PLLA)は、ガラス転移点温度(Tg)55℃、融点(Tm)175℃、重量平均分子量12万、分子量分散1.8、ラクチド含有量0.005質量%であった。
After removing the bubbles by standing still for 20 minutes, the internal pressure was increased from 2 to 3 atm with nitrogen pressure, the prepolymer was pushed out to a chip cutter, and a prepolymer having a weight average molecular weight of 130,000 and a molecular weight dispersion of 1.8 was obtained. Pelletized.
Further, the pellets were dissolved by an extruder, charged into a non-axial vertical reactor at 15 kg / hr, reduced in pressure to 10.13 kPa to reduce the remaining lactide, and chipped again. The obtained poly L-lactic acid (PLLA) has a glass transition temperature (Tg) of 55 ° C., a melting point (Tm) of 175 ° C., a weight average molecular weight of 120,000, a molecular weight dispersion of 1.8, and a lactide content of 0.005% by mass. there were.
[参考例2]ポリD−乳酸(PDLA)の合成
また、L−ラクチドの代わりにD−ラクチドを使用する以外は参考例1と同様にして、ガラス転移点温度(Tg)55℃、融点(Tm)175℃、重量平均分子量12万、分子量分散1.8、ラクチド含有量0.005質量%のポリD−乳酸(PDLA)を得た。
[Reference Example 2] Synthesis of poly-D-lactic acid (PDLA) In the same manner as Reference Example 1 except that D-lactide was used instead of L-lactide, the glass transition temperature (Tg) was 55 ° C, the melting point ( Tm) Poly D-lactic acid (PDLA) having a weight average molecular weight of 120,000, a molecular weight dispersion of 1.8, and a lactide content of 0.005% by mass was obtained.
[実施例1]
参考例1で得られたPLLAを、乾燥機を用いて十分に乾燥させた後、ローム・アンド・ハース・ジャパン株式会社社製、コアシェル構造体(パラロイドTMBPM−500)を5質量%添加し、押出機に投入し、220℃で溶融し、溶融樹脂をダイより押し出して単層のシート状に成形し、かかるシートを表面温度20℃の冷却ドラムで冷却固化して未延伸フィルムを得た。得られた未延伸フィルムを、75℃に加熱したロール群に導き、縦方向に1.1倍に延伸し、25℃のロール群で冷却した。続いて、縦延伸したフィルムの両端をクリップで保持しながらテンターに導き、75℃に加熱された雰囲気中で横方向に4.0倍に延伸した。その後テンター内で110℃の温度条件で30秒間の熱処理を行い、均一に徐冷して室温まで冷やして7μm厚みの一軸配向ポリL−乳酸単層フィルム(PLLA配向フィルム)を得た。
[Example 1]
After sufficiently drying the PLLA obtained in Reference Example 1 using a dryer, 5% by mass of a core shell structure (Paraloid TM BPM-500) manufactured by Rohm and Haas Japan Co., Ltd. is added. The molten resin was poured into an extruder, melted at 220 ° C., the molten resin was extruded from a die and formed into a single-layer sheet, and the sheet was cooled and solidified with a cooling drum having a surface temperature of 20 ° C. to obtain an unstretched film. . The obtained unstretched film was led to a roll group heated to 75 ° C., stretched 1.1 times in the longitudinal direction, and cooled by a roll group at 25 ° C. Subsequently, both ends of the longitudinally stretched film were guided to a tenter while being held with clips, and stretched 4.0 times in the transverse direction in an atmosphere heated to 75 ° C. Thereafter, heat treatment was performed in a tenter for 30 seconds under a temperature condition of 110 ° C., and the mixture was uniformly cooled and cooled to room temperature to obtain a uniaxially oriented poly L-lactic acid monolayer film (PLLA oriented film) having a thickness of 7 μm.
[実施例2]
参考例2で得られたPDLAを用いたほかは、実施例1と同様な操作を繰り返した。
[Example 2]
The same operation as in Example 1 was repeated except that the PDLA obtained in Reference Example 2 was used.
[実施例3〜6]
含有させる耐衝撃性改良剤の種類や量を、表1に示す通り、変更するほかは、実施例1と同様な操作を繰り返した。
[Examples 3 to 6]
The same operation as in Example 1 was repeated except that the type and amount of the impact resistance improver contained were changed as shown in Table 1.
[実施例7〜10]
含有させる耐衝撃性改良剤の種類や量を、表1に示す通り、変更するほかは、実施例2と同様な操作を繰り返した。
[Examples 7 to 10]
The same operation as in Example 2 was repeated except that the type and amount of the impact resistance improver contained were changed as shown in Table 1.
[実施例11]
平均粒子径2μmの架橋ポリメタクリル酸メチル粒子を、フィラーとして、フィルムの質量に対し、0.5質量%含有させたほかは実施例1と同様な操作を繰り返した。
[Example 11]
The same operation as in Example 1 was repeated except that 0.5 mass% of crosslinked polymethyl methacrylate particles having an average particle diameter of 2 μm was contained as a filler with respect to the mass of the film.
[実施例12]
平均粒子径2μmの架橋ポリメタクリル酸メチル粒子を、フィラーとして、フィルムの質量に対し、0.5質量%含有させたほかは実施例2と同様な操作を繰り返した。
[Example 12]
The same operation as in Example 2 was repeated except that 0.5% by mass of crosslinked polymethyl methacrylate particles having an average particle diameter of 2 μm was contained as a filler with respect to the mass of the film.
[比較例1]
耐衝撃性改良剤を添加しなかったほかは、実施例1と同様な操作を繰り返した。
[Comparative Example 1]
The same operation as in Example 1 was repeated except that no impact modifier was added.
[比較例2]
耐衝撃性改良剤を添加しなかったほかは、実施例2と同様な操作を繰り返した。
[Comparative Example 2]
The same operation as in Example 2 was repeated except that no impact modifier was added.
[比較例3]
耐衝撃性改良剤の添加量を15質量%に変更したほかは、実施例1と同様な操作を繰り返した。
[Comparative Example 3]
The same operation as in Example 1 was repeated except that the addition amount of the impact modifier was changed to 15% by mass.
[比較例4]
耐衝撃性改良剤の添加量を15質量%に変更したほかは、実施例2と同様な操作を繰り返した。
[Comparative Example 4]
The same operation as in Example 2 was repeated except that the addition amount of the impact modifier was changed to 15% by mass.
表1中の、Aはローム・アンド・ハース・ジャパン株式会社製、コアシェル構造体(パラロイドTMBPM−500)、Bは株式会社クラレ製、熱可塑性エラストマー(クラリティLA2250)、Cはローム・アンド・ハース・ジャパン株式会社製、コアシェル構造体(パラロイドTMBPM−515)を意味する。 In Table 1, A is a Rohm and Haas Japan Co., Ltd. core shell structure (Paraloid TM BPM-500), B is a Kuraray Co., Ltd. thermoplastic elastomer (Clarity LA2250), and C is a Rohm and Haas. It means a core shell structure (Paraloid TM BPM-515) manufactured by Hearth Japan.
[実施例13]
実施例1のPLLAフィルムと、実施例2のPDLAフィルムとを、主配向軸に沿って長さが7cmの短冊状(幅は3cm)に裁断した。
次いで、図1に示すように片方の短辺から1cmの領域(3cm×1cmの領域)をマージンとしてマスキングし、蒸着しない箇所を残した上で、残りの領域(3cm×6cmの領域)に表面抵抗値が10Ω/□となるような厚みで、それぞれ製膜時に冷却ドラムに接していなかった面にアルミ蒸着を施した。なお、導電層の厚みは50nmであった。また、マージンの位置はPLLA配向フィルムとPDLA配向フィルムとで、反対側の短辺においてマージンを作成した。
[Example 13]
The PLLA film of Example 1 and the PDLA film of Example 2 were cut into strips (width: 3 cm) having a length of 7 cm along the main alignment axis.
Next, as shown in FIG. 1, a 1 cm region (3 cm × 1 cm region) from one short side is masked as a margin to leave a portion not to be deposited, and the remaining region (3 cm × 6 cm region) is surfaced. Aluminum was vapor-deposited on the surface that had a resistance value of 10Ω / □ and was not in contact with the cooling drum at the time of film formation. The conductive layer had a thickness of 50 nm. Moreover, the margin position was created on the short side on the opposite side between the PLLA oriented film and the PDLA oriented film.
(積層)
さらに、蒸着したPLLA配向フィルムとPDLA配向フィルムとを交互に、図2に示すように各10枚ずつ、合計20枚を積層した。積層体は、110℃で20MPaの圧力を3分間かけて、熱ラミネートにより貼りあわせた。
(Laminated)
Furthermore, the vapor deposited PLLA oriented film and the PDLA oriented film were alternately laminated as shown in FIG. The laminate was bonded by thermal lamination at 110 ° C. and a pressure of 20 MPa over 3 minutes.
(電極)
得られた圧電積層体の両方の短辺に、図2に示すごとく、導電性接着剤(藤倉化成製、ドータイトD550)を塗布して電極(6)を形成し、圧電性構造体を作成した。これにより、各アルミ蒸着層において、マージンを有する側においてはかかる導電性接着剤とアルミ蒸着層とが短絡せず、マージンを有しない側においてはかかる導電性接着剤とアルミ蒸着層とが短絡した構成となる。得られた圧電積層体の圧電特性と密着性を表2に示す。
(electrode)
As shown in FIG. 2, a conductive adhesive (manufactured by Fujikura Kasei, Dotite D550) was applied to both short sides of the obtained piezoelectric laminate to form an electrode (6), thereby producing a piezoelectric structure. . Thus, in each aluminum vapor deposition layer, the conductive adhesive and the aluminum vapor deposition layer are not short-circuited on the side having a margin, and the conductive adhesive and the aluminum vapor deposition layer are short-circuited on the side having no margin. It becomes composition. Table 2 shows the piezoelectric properties and adhesion of the obtained piezoelectric laminate.
[実施例14−17、比較例5、6]
実施例1と2のフィルムの代わりに、表2に示す通り、実施例3〜10または比較例1〜4のフィルムを用いたほかは、実施例11と同様な操作を繰り返した。得られた圧電積層体の圧電特性と密着性を表2に示す。
[Examples 14-17, Comparative Examples 5 and 6]
Instead of the films of Examples 1 and 2, as shown in Table 2, the same operations as in Example 11 were repeated except that the films of Examples 3 to 10 or Comparative Examples 1 to 4 were used. Table 2 shows the piezoelectric properties and adhesion of the obtained piezoelectric laminate.
[実施例18]
実施例2のフィルムの代わりに、実施例1のフィルムを用い、主配向軸に対して直交方向に沿って長さが7cmの短冊状(幅は3cm)に裁断した。さらに実施例2の代わりに用いる実施例1のフィルムには、製膜時に冷却ドラムに接していた面にアルミ蒸着を施した他は、実施例13同様な操作を繰り返した。得られた圧電積層体の圧電特性と密着性を表2に示す。
[Example 18]
Instead of the film of Example 2, the film of Example 1 was used and cut into a strip shape (width: 3 cm) having a length of 7 cm along the direction orthogonal to the main orientation axis. Further, the same operation as in Example 13 was repeated for the film of Example 1 used instead of Example 2 except that aluminum deposition was performed on the surface that was in contact with the cooling drum at the time of film formation. Table 2 shows the piezoelectric properties and adhesion of the obtained piezoelectric laminate.
[実施例19、20]
積層数を表2に示す通り変更したほかは、実施例11と同様な操作を繰り返した。得られた圧電積層体の圧電特性と密着性を表2に示す。
[Examples 19 and 20]
The same operation as in Example 11 was repeated except that the number of layers was changed as shown in Table 2. Table 2 shows the piezoelectric properties and adhesion of the obtained piezoelectric laminate.
[実施例21、22]
圧着条件を表2に示す通り変更したほかは、実施例13と同様な操作を繰り返した。得られた圧電積層体の圧電特性と密着性を表2に示す。
[Examples 21 and 22]
The same operation as in Example 13 was repeated except that the crimping conditions were changed as shown in Table 2. Table 2 shows the piezoelectric properties and adhesion of the obtained piezoelectric laminate.
[比較例7、8]
圧着条件を表2に示す通り変更したほかは、比較例5と同様な操作を繰り返した。得られた圧電積層体の圧電特性と密着性を表2に示す。
[Comparative Examples 7 and 8]
The same operation as in Comparative Example 5 was repeated except that the crimping conditions were changed as shown in Table 2. Table 2 shows the piezoelectric properties and adhesion of the obtained piezoelectric laminate.
[比較例9]
比較例5において、蒸着を施した後、各層の間に、接着層としてHuntsman Advanced Materials社製エポキシ系接着剤(アラルダイト スタンダード)を塗布し手持ち型スチールローラーを用いて密着させたほかは、比較例6と同様な操作を繰り返した。なお、接着層の厚みは5μmであった。得られた圧電積層体の圧電特性と密着性を表2に示す。
[Comparative Example 9]
In Comparative Example 5, after vapor deposition, a Huntsman Advanced Materials epoxy adhesive (Araldite Standard) was applied as an adhesive layer between each layer and adhered using a hand-held steel roller. Comparative Example The same operation as 6 was repeated. The thickness of the adhesive layer was 5 μm. Table 2 shows the piezoelectric properties and adhesion of the obtained piezoelectric laminate.
[比較例10]
比較例5において、製膜時の冷却ドラムと接していない側の表面に、カスガ製、高周波電源CG−102型を用いて、電圧10kV、処理時間20秒の条件でコロナ処理を施した。蒸着工程以降、実施例1と同様に圧電積層体と作製した。
[Comparative Example 10]
In Comparative Example 5, the surface on the side not in contact with the cooling drum during film formation was subjected to corona treatment under the conditions of a voltage of 10 kV and a treatment time of 20 seconds using a high-frequency power source CG-102 manufactured by Kasuga. After the vapor deposition step, a piezoelectric laminate was produced in the same manner as in Example 1.
本発明によれば、圧電特性に優れ、剥離も抑制された圧電積層体が提供でき、マイクロホン、ピックアップ、ブザー、スピーカー、光スイッチ、ファン等の振動体や、圧電体アクチュエーターとして用いることができる。 According to the present invention, it is possible to provide a piezoelectric laminate that has excellent piezoelectric characteristics and is prevented from being peeled off, and can be used as a vibrating body such as a microphone, a pickup, a buzzer, a speaker, an optical switch, a fan, or a piezoelectric actuator.
1 右マージン用樹脂層
2 左マージン用樹脂層
3 導電層
4 積層体A
5 積層体B
6 銀ペースト電極
7 把持具
8 導線
9 クリップ
10 アルミ箔
11 円柱
12 圧電特性測定装置
1 Resin layer for
5 Laminate B
6
Claims (8)
6. The uniaxially oriented film made of poly L-lactic acid and the uniaxially oriented film made of poly D-lactic acid are adjacent to each other via a conductive layer, and the main orientation axes of the adjacent uniaxially oriented films are in the same direction. Piezoelectric laminate.
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WO2017155006A1 (en) * | 2016-03-09 | 2017-09-14 | 三井化学株式会社 | Laminated article |
JP2017191951A (en) * | 2017-07-03 | 2017-10-19 | 三井化学株式会社 | Polymer piezoelectric material, method for producing the same, and composition for polymer piezoelectric material |
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