JP2007270076A - Polylactic acid type stretched film, stretched laminated film and its use - Google Patents
Polylactic acid type stretched film, stretched laminated film and its use Download PDFInfo
- Publication number
- JP2007270076A JP2007270076A JP2006100680A JP2006100680A JP2007270076A JP 2007270076 A JP2007270076 A JP 2007270076A JP 2006100680 A JP2006100680 A JP 2006100680A JP 2006100680 A JP2006100680 A JP 2006100680A JP 2007270076 A JP2007270076 A JP 2007270076A
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- Prior art keywords
- mass
- polylactic acid
- aliphatic
- acid
- stretched
- Prior art date
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- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、隠蔽性、化粧性、紫外線カット性を備えた生分解性の乳白延伸フィルムに関する。また本発明は、グロス、印刷適性、インクジェットプリンター適性、ラミ強度、溶断シール強度に優れてた生分解性の乳白複合フィルムに関する。 The present invention relates to a biodegradable milky-white stretched film having a concealing property, a cosmetic property, and an ultraviolet ray cutting property. The present invention also relates to a biodegradable milky white composite film excellent in gloss, printability, ink jet printer suitability, lamination strength, and fusing seal strength.
プラスチックフィルムの廃棄処理を容易にする目的で生分解性のあるフィルムが注目され、各種フィルムが開発されて来ている。その生分解性フィルムは、土壌中や水中で加水分解や生分解を受け、徐々にフィルムの崩壊や分解が進み、最後には微生物の作用で無害な分解物へと変化するものである。そのようなフィルムとして、芳香族系ポリエステル樹脂やポリ乳酸、ポリブチレンサクシネート等の脂肪族系ポリエステル樹脂、ポリビニルアルコール、酢酸セルロース、デンプン等から成形したフィルムが知られている。 In order to facilitate the disposal of plastic films, biodegradable films have attracted attention, and various films have been developed. The biodegradable film is subject to hydrolysis and biodegradation in soil and water, gradually breaking down and decomposing the film, and finally changing to a harmless degradation product by the action of microorganisms. As such a film, a film formed from an aromatic polyester resin, an aliphatic polyester resin such as polylactic acid or polybutylene succinate, polyvinyl alcohol, cellulose acetate, starch or the like is known.
ポリ乳酸延伸フィルムの機械的強度、耐久性、厚み精度を改良する方法としてポリ乳酸に無機充填剤を配合して延伸する方法がある(たとえば、特許文献1参照)。このようにして得られたポリ乳酸延伸フィルムは、上記機械的強度の改良に加えて、隠蔽性、化粧性、紫外線カット性を備えている。しかし得られるフィルムは表面の凹凸が大きく、また無機物の欠落が起きるため、印刷適性、ラミ強度、溶断シール強度、ヒートシール強度に劣るものであった。
またかかる問題の解決策として無機充填剤を含まない被覆層を有することで、印刷適性、ラミ強度、溶断シール強度、ヒートシール強度を改善する方法を提案している(たとえば、特許文献2、3参照)。
As a method for improving the mechanical strength, durability and thickness accuracy of a polylactic acid stretched film, there is a method of blending polylactic acid with an inorganic filler and stretching (for example, see Patent Document 1). The stretched polylactic acid film thus obtained has a concealing property, a cosmetic property, and an ultraviolet ray cutting property in addition to the improvement of the mechanical strength. However, the resulting film has large irregularities on the surface and lack of inorganic substances, so that it is inferior in printability, lamination strength, fusing seal strength, and heat seal strength.
In addition, as a solution to such a problem, a method for improving printability, lamination strength, fusing seal strength, and heat seal strength by having a coating layer that does not contain an inorganic filler has been proposed (for example, Patent Documents 2 and 3). reference).
しかし上記の基材層には無機充填剤を有しているため、電子部品及び電子材料工程紙などとして用いる際にはフィルムから無機物の異物が析出してクリーン度を落とす可能性があった。
本発明は、隠蔽性、化粧性、紫外線カット性、生分解性を備え、異物析出の虞の少ない乳白二軸延伸フィルムを提供することを目的とする。 An object of the present invention is to provide a milk white biaxially stretched film that has concealing properties, cosmetic properties, UV-cutting properties, and biodegradability and is less likely to cause foreign matter precipitation.
すなわち、ポリ乳酸(A)、ポリ乳酸以外のポリマー5〜25質量%および平均粒径が0.1〜1μmの酸化チタン(C)を0〜20質量%((A)+(B)+(C)=100質量%とする。)からなることを特徴とする延伸フィルムに関する。
ポリ乳酸以外のポリマー(B)としては、ポリエチレン、ポリプロピレン、ポリメチルメタクリレート(PMMA)、変性ポリエステル、生分解性脂肪族ポリエステル、ポリスチレン、環状ポリオレフィンおよびポリカーボネートが好適であり、これらの中から選ばれる。
That is, polylactic acid (A), 5 to 25% by mass of a polymer other than polylactic acid, and 0 to 20% by mass ((A) + (B) + ( C) = 100% by mass)).
As the polymer (B) other than polylactic acid, polyethylene, polypropylene, polymethyl methacrylate (PMMA), modified polyester, biodegradable aliphatic polyester, polystyrene, cyclic polyolefin, and polycarbonate are preferable, and are selected from these.
本発明によれば、隠蔽性、化粧性、紫外線カット性を備えた生分解性の乳白延伸フィルムが提供される。また本発明によれば、グロス、印刷適性、インクジェットプリンター適性、ラミ強度、溶断シール強度に優れた生分解性の乳白複合フィルムが提供される。従来の乳白フィルムのように、炭酸カルシウム等の欠落が起きる虞がなく電子材料等のクリーン度が要求される用途に好適である。 ADVANTAGE OF THE INVENTION According to this invention, the biodegradable milk white stretched film provided with concealment property, cosmetics, and ultraviolet-ray cut property is provided. In addition, according to the present invention, a biodegradable milky white composite film excellent in gloss, printability, ink jet printer suitability, lamination strength and fusing seal strength is provided. Like conventional milky white films, there is no risk of loss of calcium carbonate or the like, which is suitable for applications that require cleanliness such as electronic materials.
本発明の延伸フィルムは、ポリ乳酸(A)、ポリ乳酸以外のポリマー(B)5〜25質量%および平均粒径が0.1〜1μmの酸化チタン(C)を0〜20質量%((A)+(B)+(C)=100質量%とする。)から構成される。
またポリ乳酸以外のポリマー(B)としては、ポリエチレン、ポリプロピレン、ポリメチルメタクリレート(PMMA)、変性ポリエステル、生分解性脂肪族ポリエステル、ポリスチレン、環状ポリオレフィン、およびポリカーボネートが好適である。
The stretched film of the present invention comprises 0 to 20% by mass of polylactic acid (A), 5 to 25% by mass of a polymer (B) other than polylactic acid, and titanium oxide (C) having an average particle size of 0.1 to 1 μm (( A) + (B) + (C) = 100 mass%)).
As the polymer (B) other than polylactic acid, polyethylene, polypropylene, polymethyl methacrylate (PMMA), modified polyester, biodegradable aliphatic polyester, polystyrene, cyclic polyolefin, and polycarbonate are suitable.
ポリ乳酸以外のポリマーの割合は5質量%以上、20質量%以下が好ましく、さらに7質量%以上、17質量%以下が好適である。ポリ乳酸以外のポリマーの割合が5質量%未満では乳白フィルムとしての白化の度合いが小さく、20質量%より多いと得られる延伸フィルムが脆くなる虞がある。
またポリ乳酸以外のポリマーとしてはポリエチレン、ポリプロピレン、ポリメチルメタクリレート(PMMA)、変性ポリエステル、生分解性脂肪族ポリエステル、ポリスチレン、環状ポリオレフィン、ポリカーボネートが好適であり、その他の材料、特に融点が300℃を越えるものは成形時においてポリ乳酸の分解が起こる虞がある。
The proportion of the polymer other than polylactic acid is preferably 5% by mass or more and 20% by mass or less, and more preferably 7% by mass or more and 17% by mass or less. If the ratio of the polymer other than polylactic acid is less than 5% by mass, the degree of whitening as a milky white film is small, and if it exceeds 20% by mass, the resulting stretched film may be brittle.
As polymers other than polylactic acid, polyethylene, polypropylene, polymethylmethacrylate (PMMA), modified polyester, biodegradable aliphatic polyester, polystyrene, cyclic polyolefin, and polycarbonate are suitable, and other materials, particularly those having a melting point of 300 ° C. If it exceeds, polylactic acid may be decomposed during molding.
一方、酸化チタンの割合は0質量%以上、20質量%以下が好ましく、さらに0質量%以上、15質量%以下が好適である。酸化チタンの割合が20質量%より大きいと得られる延伸フィルムのフィルム強度が低下する劣る虞がある。
酸化チタンの平均粒径は0.1μm以上、1μm以下が好ましい、さらに0.15μm以上、0.5μm以下が好適である。酸化チタンの平均粒径は0.1μm未満ではハンドリングが悪く混練時に不均一となる虞があり、1μmより大きいと得られる延伸フィルムの白色発色が不十分で隠蔽性に劣る虞がある。
On the other hand, the proportion of titanium oxide is preferably 0 to 20% by mass, more preferably 0 to 15% by mass. When the proportion of titanium oxide is larger than 20% by mass, the film strength of the obtained stretched film may be deteriorated.
The average particle diameter of titanium oxide is preferably 0.1 μm or more and 1 μm or less, more preferably 0.15 μm or more and 0.5 μm or less. If the average particle size of the titanium oxide is less than 0.1 μm, handling may be poor and there is a risk of non-uniformity during kneading, and if it is greater than 1 μm, the white color of the obtained stretched film may be insufficient and the concealability may be poor.
本発明のフィルムを構成する組成物は、ポリ乳酸(A)、ポリ乳酸(A)以外のポリマー(B)および酸化チタン(C)を夫々上記範囲でヘンシェルミキサー、V−ブレンダー、リボンブレンダー、タンブラーミキサー等で混合する方法、混合後更に単軸押出機、多軸押出機、バンバリーミキサー等で溶融混練する方法等により得られる。 The composition constituting the film of the present invention comprises a polylactic acid (A), a polymer (B) other than polylactic acid (A), and titanium oxide (C) within the above ranges, respectively, in a Henschel mixer, a V-blender, a ribbon blender, and a tumbler. It is obtained by a method of mixing with a mixer or the like, a method of further melt-kneading with a single screw extruder, a multi-screw extruder, a Banbury mixer or the like after mixing.
ポリ乳酸
本発明のフィルム(基材層)やその被覆層(I)に用いられるポリ乳酸(A)は、D−乳酸若しくはL−乳酸の含有量が5質量%未満、好ましくは3質量%未満で、融点が150〜170℃、好ましくは160〜170℃の範囲のものが好適である。
D−乳酸の含有量が5質量%以上の場合、延伸成形性が劣る虞がある。
また本発明に用いられる被覆層(II)を構成するポリ乳酸(F)は、D−乳酸を7〜30質量%、好ましくは8〜25質量%含むD−乳酸とL−乳酸の共重合体である。
Polylactic acid
The polylactic acid (A) used for the film (base material layer) and the coating layer (I) of the present invention has a D-lactic acid or L-lactic acid content of less than 5% by mass, preferably less than 3% by mass, A melting point of 150 to 170 ° C, preferably 160 to 170 ° C is suitable.
When the content of D-lactic acid is 5% by mass or more, stretch moldability may be inferior.
The polylactic acid (F) constituting the coating layer (II) used in the present invention is a copolymer of D-lactic acid and L-lactic acid containing 7 to 30% by mass, preferably 8 to 25% by mass of D-lactic acid. It is.
D−乳酸の含有量が7質量%未満のものは、得られる二軸延伸フィルムの低温ヒートシール性が損なわれるおそれがあり、一方、30質量%を超えると成形性が劣る傾向にある
なお、ポリ乳酸におけるD−乳酸含有量は、クロムバック社製ガスクロマトグラフCPCYCLODEX B236Mを用いて測定した値である。
このようなポリ乳酸としては、D−乳酸またはL−乳酸以外に、乳酸と共重合可能なコモノマーとしては、例えば3−ヒドロキシブチレート、カプロラクトン、グリコール酸などを共重合したものであってもよい。ポリ乳酸の重量平均分子量はフィルム成形能がある限り特に限定はされないが、MFR(ASTM D−1238による、荷重2160g、温度190℃)が、通常、0.1〜100g/10分、好ましくは1〜50g/10分、特に好ましくは2〜10g/10分のものが使用される。
When the content of D-lactic acid is less than 7% by mass, the low-temperature heat sealability of the resulting biaxially stretched film may be impaired. On the other hand, when it exceeds 30% by mass, the moldability tends to be inferior.
In addition, the D-lactic acid content in polylactic acid is a value measured using a gas chromatograph CPCYCLODEX B236M manufactured by Chromeback.
As such polylactic acid, in addition to D-lactic acid or L-lactic acid, as a comonomer copolymerizable with lactic acid, for example, 3-hydroxybutyrate, caprolactone, glycolic acid or the like may be copolymerized. . The weight average molecular weight of polylactic acid is not particularly limited as long as it has film forming ability, but MFR (load 2160 g, temperature 190 ° C. according to ASTM D-1238) is usually 0.1 to 100 g / 10 min, preferably 1 -50 g / 10 min, particularly preferably 2-10 g / 10 min are used.
これらポリ乳酸の重合法としては、縮合重合、開環重合法など公知のいずれの方法を採用することができる。例えば、縮合重合ではL−乳酸またはD−乳酸あるいはこれらの混合物を直接脱水縮合重合して任意の組成のポリ乳酸を得ることができる。
下記のポリ乳酸(A)以外のポリマー(B)はポリ乳酸(A)と混練、シート化、延伸したさい生じる界面、及び界面の剥離、もしくは屈折率の差により白化を起こさせるのに用いられる。
As a polymerization method of these polylactic acids, any known method such as condensation polymerization or ring-opening polymerization method can be employed. For example, in condensation polymerization, polylactic acid having an arbitrary composition can be obtained by directly dehydrating condensation polymerization of L-lactic acid, D-lactic acid or a mixture thereof.
The following polymer (B) other than polylactic acid (A) is used to cause whitening by mixing with polylactic acid (A), forming into a sheet, stretching, peeling of the interface, or difference in refractive index. .
ポリエチレン
本発明に用いられるポリエチレンは、一般にポリエチレンの名称で製造・販売されているポリオレフィン樹脂で、通常、密度が0.910〜0.940g/cm3、MFR(ASTMD1238荷重2160g、温度190℃)は特に限定はされないが、通常、0.5〜10g/10分、好ましくは0.8〜5g/10分の範囲にある。市販品として、ウルトゼックス、ネオゼックス、モアテック、ハイゼックス、エボリュー〔プライムポリマー(株)製、商品名〕等が挙げられる。
polyethylene
The polyethylene used in the present invention is a polyolefin resin that is generally manufactured and sold under the name of polyethylene, and usually has a density of 0.910 to 0.940 g / cm 3 and MFR (ASTMD 1238 load 2160 g, temperature 190 ° C.) is particularly limited. Although not carried out, it is usually in the range of 0.5 to 10 g / 10 minutes, preferably 0.8 to 5 g / 10 minutes. Examples of commercially available products include Ultzex, Neozex, Moretech, Hi-Zex, Evolue [manufactured by Prime Polymer Co., Ltd., trade name] and the like.
ポリプロピレン
本発明に用いられるポリプロピレンは、一般にポリプロピレンの名称で製造・販売されているポリオレフィン樹脂で、通常、密度が0.890〜0.930g/cm3、MFR(ASTMD1238荷重2160g、温度230℃)が0.5〜60g/10分、好ましくは0.5〜10g/10分、更に好ましくは1〜5g/10分のプロピレンの単独重合体若しくはプロピレンと他の少量例えば、5モル%以下のα−オレフィン、例えばエチレン、ブテン、ヘキセン−1等とのランダム重合体である。又、これらプロピレン重合体は1種あるいは2種以上の組成物、例えば分子量が異なるプロピレンの単独重合体の組成物、プロピレン単独重合体とプロピレン・α―オレフィンランダム共重合体との組成物であってもよい。市販品として、プライムポリプロ〔プライムポリマー(株)製、商品名〕等が挙げられる。
polypropylene
Polypropylene for use in the present invention is generally in the polyolefin resin, manufactured and sold under the name of polypropylene, usually, the density is 0.890~0.930g / cm 3, MFR (ASTMD1238 load 2160 g, temperature 230 ° C.) is 0 0.5-60 g / 10 min, preferably 0.5-10 g / 10 min, more preferably 1-5 g / 10 min propylene homopolymer or propylene and other small amounts, for example 5 mol% or less α-olefin For example, a random polymer with ethylene, butene, hexene-1, and the like. These propylene polymers are one or more compositions, for example, compositions of homopolymers of propylene having different molecular weights, compositions of propylene homopolymers and propylene / α-olefin random copolymers. May be. Examples of commercially available products include Prime Polypro [manufactured by Prime Polymer Co., Ltd., trade name].
ポリメチルメタクリレート(PMMA)
本発明に用いられるポリメチルメタクリレートは、一般にポリメチルメタクリレートの名称で製造・販売されている樹脂で、アセトンと青酸あるいはイソブチレンとメタノールから誘導されるメチルメタクリレート(MMA)の重合によって製造される。
通常、密度が1.1〜1.2g/cm3、MFR(ASTM D1238 荷重2160g、温度230℃)が0.1〜30g/10分、の重合体である。
市販品として、アクリペット〔三菱レーヨン(株)製、商品名〕等が挙げられる。
Polymethyl methacrylate (PMMA)
The polymethyl methacrylate used in the present invention is a resin that is generally produced and sold under the name of polymethyl methacrylate, and is produced by polymerization of methyl methacrylate (MMA) derived from acetone and hydrocyanic acid or isobutylene and methanol.
Usually, it is a polymer having a density of 1.1 to 1.2 g / cm 3 and an MFR (ASTM D1238 load of 2160 g, temperature of 230 ° C.) of 0.1 to 30 g / 10 min.
As a commercial product, Acripet [Mitsubishi Rayon Co., Ltd., a brand name] etc. are mentioned.
変性ポリエステル
本発明で用いられる変性ポリエステルは、スルホン酸金属塩基を核置換基として有する芳香族ジカルボン酸を含む芳香族系ポリエステルであり、より具体的には、芳香族ジカルボン酸、脂肪族グリコール、およびスルホン酸金属塩基を核置換基として有する芳香族ジカルボン酸、それに必要に応じて脂肪族ジカルボン酸または脂肪族ヒドロキシカルボン酸を加え、それらの成分間で重縮合反応を行って得られるポリエステルであることが望ましい。ポリエステル樹脂の好ましい組成は、芳香族ジカルボン酸成分に由来する単位が30〜49.9モル%、脂肪族グリコール成分に由来する単位が35〜50モル%、スルホン酸金属塩基を置換基として有する芳香族または脂肪族ジカルボン酸成分に由来する単位が0.1〜5モル%、および脂肪族ジカルボン酸または脂肪族ヒドロキシカルボン酸成分に由来する単位が0〜30モル%(ここで、全単位の合計が100モル%になる)である。
Modified polyester
The modified polyester used in the present invention is an aromatic polyester containing an aromatic dicarboxylic acid having a sulfonic acid metal base as a nucleus substituent, and more specifically, an aromatic dicarboxylic acid, an aliphatic glycol, and a sulfonic acid. An aromatic dicarboxylic acid having a metal base as a nucleus substituent and a polyester obtained by adding an aliphatic dicarboxylic acid or an aliphatic hydroxycarboxylic acid to the base as necessary and conducting a polycondensation reaction between these components are desirable. . The preferred composition of the polyester resin is 30 to 49.9 mol% of units derived from an aromatic dicarboxylic acid component, 35 to 50 mol% of units derived from an aliphatic glycol component, and an aromatic having a sulfonic acid metal base as a substituent. 0.1 to 5 mol% of units derived from an aliphatic or aliphatic dicarboxylic acid component, and 0 to 30 mol% of units derived from an aliphatic dicarboxylic acid or aliphatic hydroxycarboxylic acid component (here, the total of all units) Is 100 mol%).
その重量平均分子量が、10,000〜500,000の範囲が好ましい。また、そのメルトフローレートは、ASTM D−1238に準拠し、220℃、2160g荷重下で測定した値が、0.1〜100(g/10分)であることが好ましい The weight average molecular weight is preferably in the range of 10,000 to 500,000. Further, the melt flow rate is preferably 0.1 to 100 (g / 10 min) as measured under a load of 2160 g at 220 ° C. according to ASTM D-1238.
生分解性脂肪族ポリエステル
本発明に係わる生分解性脂肪族ポリエステル(E)は、脂肪族または脂環式ジカルボン酸成分(e1)、脂肪族または脂環式ジヒドロキシ化合物成分(e2)(及び2官能脂肪族ヒドロキシカルボン酸成分(e3))からなる生分解性脂肪族ポリエステル共重合体である。
脂肪族または脂環式ジカルボン酸成分(e1)は、特に限定はされないが、通常、脂肪族ジカルボン酸成分は2〜10個の炭素原子(カルボキシル基の炭素も含めて)、好ましくは4〜6個の炭素原子を有する化合物であり、線状であっても枝分れしていてもよい。脂環式ジカルボン酸成分は、通常、7〜10個の炭素原子、特に8個の炭素原子を有するものが好ましい。
Biodegradable aliphatic polyester
The biodegradable aliphatic polyester (E) according to the present invention comprises an aliphatic or alicyclic dicarboxylic acid component (e1), an aliphatic or alicyclic dihydroxy compound component (e2) (and a bifunctional aliphatic hydroxycarboxylic acid component). (E3)) is a biodegradable aliphatic polyester copolymer.
The aliphatic or alicyclic dicarboxylic acid component (e1) is not particularly limited, but usually the aliphatic dicarboxylic acid component is 2 to 10 carbon atoms (including the carbon of the carboxyl group), preferably 4 to 6 A compound having one carbon atom, which may be linear or branched. The alicyclic dicarboxylic acid component is usually preferably one having 7 to 10 carbon atoms, particularly 8 carbon atoms.
脂肪族または脂環式ジカルボン酸成分(e1)としては、特に、コハク酸またはそのアルキルエステルまたはそれらの混合物が好ましく、融点(Tm)が低い生分解性脂肪族ポリエステルを得るために、コハク酸を主成分とし、副成分としてアジピン酸を併用してもよい。
脂肪族または脂環式ジヒドロキシ化合物成分(e2)は、特に限定はされないが、通常、脂肪族ジヒドロキシ化合物成分であれば、2〜12個の炭素原子、好ましくは4〜6個の炭素原子を有する枝分かれまたは線状のジヒドロキシ化合物、脂環式ジヒドロキシ化合物成分であれば、5〜10個の炭素原子を有する環状の化合物が挙げられる。
脂肪族または脂環式ジヒドロキシ化合物成分(e2)としては1,4−ブタンジオールが好ましい。
As the aliphatic or alicyclic dicarboxylic acid component (e1), succinic acid or an alkyl ester thereof or a mixture thereof is particularly preferable. In order to obtain a biodegradable aliphatic polyester having a low melting point (Tm), succinic acid is used. You may use adipic acid as a main component and a subcomponent together.
The aliphatic or alicyclic dihydroxy compound component (e2) is not particularly limited, but usually has 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms, as long as it is an aliphatic dihydroxy compound component. Examples of the branched or linear dihydroxy compound and alicyclic dihydroxy compound component include cyclic compounds having 5 to 10 carbon atoms.
As the aliphatic or alicyclic dihydroxy compound component (e2), 1,4-butanediol is preferable.
また2官能脂肪族ヒドロキシカルボン酸成分(e3)は、特に限定はされないが、通常、1〜10個の炭素原子を有する枝分かれまたは線状の二価脂肪族基を有する化合物が挙げられる。
かかる2官能脂肪族ヒドロキシカルボン酸成分(e3)としては、具体的には、例えば、グリコール酸、L−乳酸、D−乳酸、D,L−乳酸、2−メチル乳酸、3−ヒドロキシ酪酸、4−ヒドロキシ酪酸、2−ヒドロキシ−n−酪酸、2−ヒドロキシ−3,3−ジメチル酪酸、2−ヒドロキシ−2−メチル酪酸、2−ヒドロキシ−3−メチル酪酸、ヒドロキシピバリン酸、ヒドロキシイソカプロン酸、ヒドロキシカプロン酸等、かかる2官能脂肪族ヒドロキシカルボン酸のメチルエステル、エチルエステル、プロピルエステル、ブチルエステル、シクロヘキシルエステル等の2官能脂肪族ヒドロキシカルボン酸エステル形成誘導体を挙げることができる。
これらの中では、L―乳酸、D―乳酸、D,L−乳酸などの乳酸を主成分とするものが好適であり、L−乳酸を主成分とするものが望ましい。
In addition, the bifunctional aliphatic hydroxycarboxylic acid component (e3) is not particularly limited, but usually includes a compound having a branched or linear divalent aliphatic group having 1 to 10 carbon atoms.
Specific examples of the bifunctional aliphatic hydroxycarboxylic acid component (e3) include glycolic acid, L-lactic acid, D-lactic acid, D, L-lactic acid, 2-methyllactic acid, 3-hydroxybutyric acid, 4 -Hydroxybutyric acid, 2-hydroxy-n-butyric acid, 2-hydroxy-3,3-dimethylbutyric acid, 2-hydroxy-2-methylbutyric acid, 2-hydroxy-3-methylbutyric acid, hydroxypivalic acid, hydroxyisocaproic acid, Bifunctional aliphatic hydroxycarboxylic acid ester-forming derivatives such as hydroxycaproic acid and the like, such as methyl ester, ethyl ester, propyl ester, butyl ester and cyclohexyl ester of bifunctional aliphatic hydroxycarboxylic acid.
Among these, those containing lactic acid as a main component such as L-lactic acid, D-lactic acid, D, L-lactic acid are preferable, and those containing L-lactic acid as the main component are preferable.
また融点(Tm)は80〜120℃の範囲とすることが好ましく、メルトフローレート(MFR:ASTM D−1238、190℃、荷重2160g)は、特に限定はされないが、通常0.1〜100g/10分、好ましくは0.2〜50g/10分、さらに好ましくは0.5〜20g/10分の範囲にある。
市販品として、例えば、昭和高分子株式会社からビオノーレ(商品名)、ダイセル化学株式会社からセルグリーンCBS(商品名)、三菱化学株式会社からGS Pla(商品名)として製造・販売されている。
The melting point (Tm) is preferably in the range of 80 to 120 ° C., and the melt flow rate (MFR: ASTM D-1238, 190 ° C., load 2160 g) is not particularly limited, but is usually 0.1 to 100 g / It is in the range of 10 minutes, preferably 0.2-50 g / 10 minutes, more preferably 0.5-20 g / 10 minutes.
As commercial products, for example, Bionore (trade name) from Showa Polymer Co., Ltd., Cell Green CBS (trade name) from Daicel Chemical Co., Ltd., and GS Pla (trade name) from Mitsubishi Chemical Corporation are manufactured and sold.
ポリスチレン(PS)
本発明に用いられるポリスチレンは、過酸化ベンゾイルをイニシエーター(ラジカル開始剤)としてスチレンをラジカル重合して得られるアタクチック構造を持つプラスチックであり、熱可塑性の非晶性ポリマーである。アタクチックポリスチレンは高い透明性を利用して日用品の容器として広く用いられている。メタロセン触媒による重合ではシンジオタクチック構造を持つポリスチレンを合成することができる。これによって生成するポリスチレンは結晶性の高分子であり、不透明であるが、アタクチックポリスチレンよりも耐熱性に優れている。
通常、密度が1.0〜1.1g/cm3、MFR(ISO 1133 荷重5kgf、温度200℃)が0.1〜100g/10分、の重合体である。
市販品として、JSP―ポリスチレン〔SPジャパン(株)製、商品名〕等が挙げられる。
Polystyrene (PS)
The polystyrene used in the present invention is a plastic having an atactic structure obtained by radical polymerization of styrene using benzoyl peroxide as an initiator (radical initiator), and is a thermoplastic amorphous polymer. Atactic polystyrene is widely used as a container for daily necessities because of its high transparency. Polystyrene having a syndiotactic structure can be synthesized by polymerization using a metallocene catalyst. Polystyrene produced thereby is a crystalline polymer and is opaque, but has better heat resistance than atactic polystyrene.
Usually, it is a polymer having a density of 1.0 to 1.1 g / cm 3 and an MFR (ISO 1133 load 5 kgf, temperature 200 ° C.) of 0.1 to 100 g / 10 min.
Examples of commercially available products include JSP-polystyrene [manufactured by SP Japan Co., Ltd., trade name].
環状ポリオレフィン(COC)
本発明に用いられる環状ポリオレフィンは、1,3−シクロヘキサジエン等のシクロジエンをZr、TiまたはNi触媒下で重合することにより得られ、従来のポリオレフィン材料に比べ、耐熱性や強度・弾性率に優れ、更に極性基を持たないことから、複屈折率が低いなど光学材料としての可能性も広がりつつある。
通常、密度が1.0〜1.1g/cm3、MFR(ISO 1133 荷重21.18N、温度230℃)が0.1〜100g/10分、の重合体である。
市販品として、アペル〔三井化学(株)製、商品名〕、ゼオノア〔日本ゼオン(株)製、商品名〕、スミライト〔住友ベークライト(株)製、商品名〕、等が挙げられる。
Cyclic polyolefin (COC)
The cyclic polyolefin used in the present invention is obtained by polymerizing cyclodiene such as 1,3-cyclohexadiene in the presence of a Zr, Ti or Ni catalyst, and is superior in heat resistance, strength and elastic modulus compared to conventional polyolefin materials. Further, since it does not have a polar group, the possibility as an optical material is expanding, such as low birefringence.
Usually, it is a polymer having a density of 1.0 to 1.1 g / cm 3 and an MFR (ISO 1133 load 21.18 N, temperature 230 ° C.) of 0.1 to 100 g / 10 min.
Examples of commercially available products include Apel (trade name, manufactured by Mitsui Chemicals, Inc.), Zeonore (trade name, manufactured by Nippon Zeon Co., Ltd.), Sumilite (trade name, manufactured by Sumitomo Bakelite Co., Ltd.), and the like.
ポリカーボネート(PC)
本発明に用いられるポリカーボネートは、ビスフェノールAと塩化カルボニル(もしくはジフェニルカーボネート)を原料として生産される非結晶性の熱可塑性樹脂である。
通常、密度が1.1〜1.3g/cm3、荷重たわみ温度(ISO D648 荷重1.82MPa)が100〜150℃の重合体である。
市販品として、Lexan〔日本GEプラスチック(株)製、商品名〕等が挙げられる。
Polycarbonate (PC)
The polycarbonate used in the present invention is an amorphous thermoplastic resin produced using bisphenol A and carbonyl chloride (or diphenyl carbonate) as raw materials.
Usually, it is a polymer having a density of 1.1 to 1.3 g / cm 3 and a deflection temperature under load (ISO D648 load of 1.82 MPa) of 100 to 150 ° C.
As a commercial product, Lexan [manufactured by Nippon GE Plastics Co., Ltd., trade name] and the like can be mentioned.
ポリ4−メチル−1−ペンテン(P4MP1)
本発明に用いられるポリ4−メチル−1−ペンテンとしては、4−メチル−1−ペンテンの単独重合体、もしくは4−メチル−1−ペンテンとエチレンまたは炭素原子数3〜20の他のα−オレフィンや鎖状ジエンとの共重合体であることが好ましい。例えばエチレン、プロピレン、1−ブテン、1−ヘキセン、1−オクテン、1−デセン、1−ドデセン、1−テトラデセン、1−ヘキサデセン、1−オクタデセン等が挙げられ、特に剛性および弾性率が良好であることから、1−デセンが好ましい。
また、これら重合体としては、4−メチル−1−ペンテンから導かれる繰り返し単位を80質量%以上、好ましくは90〜99.9質量%、さらに好ましくは95〜99質量%含む4−メチル−1−ペンテンを主体とした共重合体が好ましく、4−メチル−1−ペンテンから導かれる繰り返し単位が80質量%以上であると、ポリ乳酸と混練した際に生じる相分離した粒径が小さくなることから好ましい。
Poly-4-methyl-1-pentene (P4MP1)
The poly-4-methyl-1-pentene used in the present invention is a homopolymer of 4-methyl-1-pentene or 4-methyl-1-pentene and ethylene or other α-carbon atoms having 3 to 20 carbon atoms. A copolymer with an olefin or a chain diene is preferred. For example, ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, etc. are mentioned, and particularly, rigidity and elastic modulus are good. Therefore, 1-decene is preferable.
Further, as these polymers, 4-methyl-1 containing 80% by mass or more, preferably 90 to 99.9% by mass, more preferably 95 to 99% by mass of a repeating unit derived from 4-methyl-1-pentene. -A copolymer mainly composed of pentene is preferable, and when the repeating unit derived from 4-methyl-1-pentene is 80% by mass or more, the phase-separated particle size generated when kneaded with polylactic acid is reduced. To preferred.
このようなポリ4−メチル−1−ペンテンのMFR(メルトフローレート)は、ASTMD1238に準じ、荷重5.0kg、温度260℃の条件で測定した値が、通常0.001〜10g/10分、好ましくは0.001〜5g/10分、さらに0.001〜1g/10分の範囲にあることが好ましい。
市販品として、TPX〔三井化学株式会社製、商品名〕等が挙げられる。
また下記の酸化チタンは白色を発色するために用いる。
The MFR (melt flow rate) of such poly-4-methyl-1-pentene is usually 0.001 to 10 g / 10 min as measured under conditions of a load of 5.0 kg and a temperature of 260 ° C. according to ASTM D1238. Preferably, it is in the range of 0.001 to 5 g / 10 minutes, more preferably 0.001 to 1 g / 10 minutes.
Examples of commercially available products include TPX [trade name, manufactured by Mitsui Chemicals, Inc.].
The following titanium oxide is used to develop a white color.
酸化チタン
酸化チタンは、その結晶形からアナタース型、ルチル型、ブルカイト型に分類されるが、いずれも使用することができその平均粒径は0.1〜1μmであることが好ましい。さらに好ましくは0.15〜0.5μmである。また、ポリ乳酸への分散性を向上させるために、表面をアルミナ、シリカ、酸化亜鉛等の酸化物で被覆したり、脂肪族ポリオール等で表面処理を施したものを用いることができる。市販品として、タイペーク〔石原産業(株)製、商品名〕、タイトン〔堺化学工業(株)製、商品名〕等が挙げられる。
Titanium oxide
Titanium oxide is classified into anatase type, rutile type, and brookite type from its crystal form, and any of them can be used, and the average particle diameter is preferably 0.1 to 1 μm. More preferably, it is 0.15-0.5 micrometer. Moreover, in order to improve the dispersibility to polylactic acid, what coated the surface with oxides, such as an alumina, a silica, and zinc oxide, or surface-treated with aliphatic polyol etc. can be used. Examples of commercially available products include Taipei [made by Ishihara Sangyo Co., Ltd., trade name], Tyton [made by Sakai Chemical Industry Co., Ltd., trade name] and the like.
被覆層(I)および被覆層(II)
本発明に係る被覆層(I)は、上記記載のポリ乳酸(A)単体またはポリ乳酸(A)と1質量%以下のシリカを配合した組成物からなる。シリカの含有量が1質量%以上のものは印刷適性、ラミ強度、溶断シール強度が劣る虞がある。
本発明に係る被覆層(II)は、前記の生分解性脂肪族ポリエステル共重合体97〜5質量%、好ましくは90〜25質量%、更に好ましくは85〜55質量%と、ポリ乳酸3〜95質量%、好ましくは10〜75質量%、更に好ましくは15〜45質量%との組成物である。
ポリ乳酸の量が3質量%未満の組成物を積層フィルムの被覆層(II)に用いた場合には、基材層と被覆層(II)との接着性に劣ることから、充分なヒートシール強度が得られないおそれがある。
Coating layer (I) and coating layer (II)
The coating layer (I) according to the present invention is composed of the above-described polylactic acid (A) alone or a composition containing polylactic acid (A) and 1% by mass or less of silica. When the content of silica is 1% by mass or more, there is a possibility that the printability, the lamination strength, and the fusing seal strength are inferior.
The coating layer (II) according to the present invention comprises 97-5% by mass of the biodegradable aliphatic polyester copolymer, preferably 90-25% by mass, more preferably 85-55% by mass, and polylactic acid 3-3. The composition is 95% by mass, preferably 10 to 75% by mass, and more preferably 15 to 45% by mass.
When a composition having an amount of polylactic acid of less than 3% by weight is used for the coating layer (II) of the laminated film, the adhesiveness between the base material layer and the coating layer (II) is inferior. There is a risk that strength cannot be obtained.
本発明では、二軸延伸フィルムの両面に被覆層(I)または被覆層(II)を設けることで、印刷適性、ラミ強度、溶断シール強度を向上させることができる。
本発明において、被覆層(II)の表面のラミ強度は10N/15mm幅以上であることが望ましい。
これら、被覆層(I)、(II)を有することから、本発明の延伸積層フィルムは、電子部品及び電子材料の工程紙などに用いても、無機物の異物が析出しない。
In the present invention, by providing the coating layer (I) or the coating layer (II) on both surfaces of the biaxially stretched film, it is possible to improve the printability, the lamination strength, and the fusing seal strength.
In the present invention, the laminar strength of the surface of the coating layer (II) is desirably 10 N / 15 mm width or more.
Since these coating layers (I) and (II) are included, the stretched laminated film of the present invention does not deposit inorganic foreign matter even when used for process paper for electronic parts and electronic materials.
生分解性脂肪族ポリエステル及びポリ乳酸を夫々上記範囲でヘンシェルミキサー、V−ブレンダー、リボンブレンダー、タンブラーミキサー等で混合する方法、混合後更に単軸押出機、多軸押出機、バンバリーミキサー等で溶融混練する方法等により得られる。
またインクジェット記憶媒体等の表面に更にインク受容層(ヒドロキシプロピルセルロース、メチロール化メラミン)を1〜10μm程度保持するために、被覆層(I)(II)の表面に適度の凹凸を要する場合は1質量%を超えない範囲でシリカを含有することができる。
本発明の基材層をなす組成物および被覆層(I)(II)をなす組成物には、予め組成物を製造する際に、または製膜時に直接押出し機に、本発明の目的を損なわない範囲で、通常用いられる酸化防止剤、耐候安定剤、帯電防止剤、防曇剤、アンチブロッキング剤、スリップ剤、耐光安定剤、紫外線吸収剤、蛍光増白剤、抗菌剤、核剤、無機化合物あるいは有機化合物充填材等の添加剤を必要に応じて配合することができる。
A method of mixing biodegradable aliphatic polyester and polylactic acid within the above ranges with a Henschel mixer, V-blender, ribbon blender, tumbler mixer, etc., and after mixing, it is further melted with a single screw extruder, multi-screw extruder, Banbury mixer, etc. It is obtained by a kneading method or the like.
In addition, in order to hold an ink receiving layer (hydroxypropylcellulose, methylolated melamine) on the surface of an ink jet storage medium or the like in an amount of about 1 to 10 μm, the surface of the coating layer (I) (II) requires 1 Silica can be contained in a range not exceeding mass%.
The composition forming the base material layer of the present invention and the composition forming the coating layer (I) (II) are not suitable for the purpose of the present invention when the composition is produced in advance or directly into the extruder during film formation. Antioxidants, weather stabilizers, antistatic agents, antifogging agents, antiblocking agents, slip agents, light stabilizers, UV absorbers, fluorescent brighteners, antibacterial agents, nucleating agents, inorganic Additives such as a compound or an organic compound filler can be blended as necessary.
二軸延伸フィルム
本発明の延伸フィルムはポリ乳酸(A)、ポリ乳酸以外のポリマー(B)5から25質量%、および平均粒径0.1〜1ミクロンの酸化チタン(C)0〜20質量%からなる。フィルムの延伸は少なくとも一軸方向でよいが、中でも二軸方向に延伸することが望ましい。延伸倍率は、それぞれの方向で、それぞれ1.3〜5倍程度が通常である。
Biaxially stretched film
The stretched film of the present invention comprises polylactic acid (A), 5 to 25% by mass of polymer (B) other than polylactic acid, and 0 to 20% by mass of titanium oxide (C) having an average particle size of 0.1 to 1 micron. Although the film may be stretched at least in a uniaxial direction, it is desirable to stretch in a biaxial direction. The stretching ratio is usually about 1.3 to 5 times in each direction.
二軸延伸の条件は、ポリ乳酸を延伸し得る条件、例えば、逐次二軸延伸法では、縦延伸温度を60〜100℃、延伸倍率を2〜6倍の範囲、横延伸温度を60〜120℃、延伸倍率を2〜12倍の範囲にすればよい。又、同時二軸延伸法では、延伸温度を60〜120℃、延伸倍率を2〜12倍(面倍率で4〜150倍)の範囲にすればよい。二軸延伸後は二軸延伸積層フィルムの用途に応じて種々条件でヒートセット(熱処理)を行うことにより、得られる二軸延伸積層フィルムの熱収縮率を任意の範囲、例えば80℃、15分の条件下における縦方向の熱収縮率を1〜5%、横方向の熱収縮率を5〜10%の範囲に、また100℃、15分の条件下における縦方向の熱収縮率を5〜15%、横方向の熱収縮率を10〜20%の範囲にすることができる。 The biaxial stretching conditions are the conditions under which polylactic acid can be stretched, for example, in the sequential biaxial stretching method, the longitudinal stretching temperature is 60 to 100 ° C., the stretching ratio is 2 to 6 times, and the transverse stretching temperature is 60 to 120. What is necessary is just to make a draw ratio into the range of 2 to 12 degreeC. In the simultaneous biaxial stretching method, the stretching temperature may be 60 to 120 ° C., and the stretching ratio may be 2 to 12 times (4 to 150 times in terms of surface magnification). After biaxial stretching, the heat shrinkage rate of the obtained biaxially stretched laminated film can be set within an arbitrary range, for example, 80 ° C. for 15 minutes by performing heat setting (heat treatment) under various conditions depending on the use of the biaxially stretched laminated film. The thermal contraction rate in the vertical direction under the conditions of 1 to 5%, the thermal contraction rate in the horizontal direction within the range of 5 to 10%, and the thermal contraction rate in the vertical direction under the conditions of 100 ° C. and 15 minutes to 5%. 15%, and the heat shrinkage rate in the lateral direction can be in the range of 10 to 20%.
熱収縮フィルムを得るためにはヒートセットを行わないか、あるいは延伸温度近辺またはそれ以下の温度に置くことで、例えば、80℃、15分の条件下における縦方向の熱収縮率を5〜10%、横方向の熱収縮率を10〜15%、また100℃、15分の条件下における縦方向の熱収縮率を20〜70%、横方向の熱収縮率を20〜70%の範囲にすることができる。 In order to obtain a heat-shrinkable film, heat set is not performed, or it is placed at a temperature near or below the stretching temperature. %, The horizontal heat shrinkage rate is in the range of 10 to 15%, the heat shrinkage rate in the vertical direction under the condition of 100 ° C. for 15 minutes is 20 to 70%, and the horizontal heat shrinkage rate is in the range of 20 to 70%. can do.
二軸延伸積層フィルム
本発明の二軸延伸積層フィルムは例えば、二軸延伸フィルム(基材層)としてポリ乳酸(A)、ポリ乳酸以外のポリマー(B)5〜25質量%および平均粒径が0.1〜1μmの酸化チタン(C)を0〜20質量%((A)+(B)+(C)=100質量%とする。))からなる組成物を用い、被覆層(I)としてポリ乳酸(A)単体またはポリ乳酸(A)と1質量%以下のシリカを配合した組成物、または生分解性脂肪族ポリエステル共重合体(E)97〜5質量%及びポリ乳酸(F)3〜95質量%の組成物からなる被覆層(II)を用いて共押出し成形して得た積層シートを、公知の同時二軸延伸法あるいは逐次二軸延伸法等の二軸延伸フィルム製造方法により得られる。
Biaxially stretched laminated film
The biaxially stretched laminated film of the present invention is, for example, a polylactic acid (A) as a biaxially stretched film (base material layer), a polymer (B) other than polylactic acid 5 to 25% by mass, and an average particle size of 0.1 to 1 μm. Of titanium oxide (C) of 0 to 20% by mass ((A) + (B) + (C) = 100% by mass)), and polylactic acid (A) as the coating layer (I) ) A composition comprising a simple substance or polylactic acid (A) and 1% by mass or less of silica, or 97 to 5% by mass of biodegradable aliphatic polyester copolymer (E) and 3 to 95% by mass of polylactic acid (F) A laminated sheet obtained by coextrusion molding using the coating layer (II) made of the composition is obtained by a biaxially stretched film production method such as a known simultaneous biaxial stretching method or a sequential biaxial stretching method.
二軸延伸積層フィルムを製造する方法としては前記共押出し積層シートを延伸せずに、予め前記方法でポリ乳酸(A)およびポリ乳酸(A)以外のポリマー(B)5〜25質量%、および酸化チタン(C)0〜20質量%からなる組成物を用いて二軸延伸フィルムを製造した後、かかる二軸延伸フィルム基材層の片面あるいは両面に、被覆層(I)または被覆層(II)を構成する組成物を押出し被覆する方法(押出しラミ法)、あるいは予め被覆層(I)または被覆層(II)を構成する組成物でフィルムを得た後、二軸延伸フィルム基材層と貼り合せる方法(ラミ法)をとり得るが、共押出し積層シートを延伸する方法が、押出しラミ法と比べると一工程で多層にできるのでコストが安く、またラミ法に比べても加工工程が少なく、また被覆層を例えば0.5〜2μmという厚みまで薄くできるので好ましい。 As a method for producing a biaxially stretched laminated film, 5-25% by mass of the polymer (B) other than the polylactic acid (A) and the polylactic acid (A) by the above method in advance without stretching the co-extruded laminated sheet, and After producing a biaxially stretched film using a composition comprising 0 to 20% by mass of titanium oxide (C), a coating layer (I) or a coating layer (II) is formed on one or both sides of the biaxially stretched film substrate layer. And a biaxially stretched film substrate layer after obtaining a film with a composition comprising the coating layer (I) or the coating layer (II) in advance. The method of laminating can be used, but the method of stretching a co-extruded laminated sheet can be made in multiple layers in one step compared to the extrusion laminating method, so the cost is low, and there are fewer processing steps than the laminating method ,Also Preferred because it thin covering layer to a thickness of, for example 0.5 to 2 [mu] m.
また、二軸延伸積層フィルムを得た後、熱処理を行わないか、あるいは熱処理の条件を種々選択することにより、熱収縮性を備えた二軸延伸積層フィルムあるいは熱収縮性を抑えた二軸 延伸積層フィルムを得ることができる。
また、被覆層(I)面のグロスは10〜90%であることが望ましい。
被覆層(I)面の表面粗さ(SRa)は0.05〜1.0μmであることが望ましい。 二軸延伸フィルム及び二軸延伸積層フィルムにおいて、フィルム(基材層)、被覆層(I)または被覆層(II)の厚さは用途に応じて種々決めることができる。通常はフィルム(基材層)の厚さが5〜500μm、好ましくは10〜200μm、被覆層(I)または被覆層(II)の厚さが0.1〜10μm、好ましくは0.3〜5μmの範囲にあり、二軸延伸積層フィルムの厚さは5〜500μm、好ましくは10〜200μmの範囲にある。
In addition, after obtaining a biaxially stretched laminated film, heat treatment is not performed, or by selecting various conditions for heat treatment, biaxially stretched laminated film with heat shrinkability or biaxial stretching with reduced heat shrinkability A laminated film can be obtained.
Further, the gloss on the surface of the coating layer (I) is desirably 10 to 90%.
The surface roughness (SRa) of the coating layer (I) surface is preferably 0.05 to 1.0 μm. In the biaxially stretched film and the biaxially stretched laminated film, the thickness of the film (base material layer), the coating layer (I) or the coating layer (II) can be variously determined depending on the application. Usually, the thickness of the film (base material layer) is 5 to 500 μm, preferably 10 to 200 μm, and the thickness of the coating layer (I) or the coating layer (II) is 0.1 to 10 μm, preferably 0.3 to 5 μm. The thickness of the biaxially stretched laminated film is in the range of 5 to 500 μm, preferably 10 to 200 μm.
プリンター用紙
本発明の二軸延伸フィルムは、ポリ乳酸(A)、ポリ乳酸(A)以外のポリマー(B)5〜25質量%、および酸化チタン(C)0〜20質量%からなる組成物を用いてなるので、ペーパーライクな白色の発色性、隠蔽性に優れている。
また、被覆層(I)を有する二軸延伸積層フィルムとすると、被覆層(I)がポリ乳酸(A)単体またはポリ乳酸(A)と1質量%以下のシリカを配合した組成物からなることから、インク受容層(ヒドロキシプロピルセルロース、メチロール化メラミン等)を1〜10μm程度保持するために、適度の凹凸を有することができる。
Printer paper
The biaxially stretched film of the present invention uses a composition comprising polylactic acid (A), 5 to 25% by mass of a polymer (B) other than polylactic acid (A), and 0 to 20% by mass of titanium oxide (C). Therefore, it is excellent in paper-like white color development and concealment.
Moreover, when it is set as the biaxially stretched laminated film which has coating layer (I), coating layer (I) consists of a composition which mix | blended polylactic acid (A) single-piece | unit or polylactic acid (A), and 1 mass% or less of silica. Therefore, in order to hold the ink receiving layer (hydroxypropylcellulose, methylolated melamine, etc.) about 1 to 10 μm, it can have appropriate irregularities.
被覆層(I)の表面の表面粗さ(SRa)が0.1μm以上であり、ヒドロキシプロピルセルロース、およびメチロール化メラミンから選ばられる少なくなくとも1種類以上の化合物をその厚さが1μm以上となるように塗布、担持されてなるものは、インクジェット用紙に適している。
これにより従来の紙に比べて耐水性、対摩耗性はもちろん、ポリ乳酸樹脂を原料とすることから、生分解性、植物由来性も有するインクジェットプリンター用紙、レーザープリンター用紙として使用できる。
The surface roughness (SRa) of the surface of the coating layer (I) is 0.1 μm or more, and the thickness of at least one compound selected from hydroxypropylcellulose and methylolated melamine is 1 μm or more. Thus, what is coated and supported is suitable for inkjet paper.
As a result, since it uses polylactic acid resin as a raw material as well as water resistance and abrasion resistance compared to conventional paper, it can be used as ink jet printer paper and laser printer paper having biodegradability and plant origin.
溶断シール袋
本発明の二軸延伸フィルムは、ポリ乳酸(A)、ポリ乳酸以外のポリマー(B)5〜25質量%および酸化チタン(C)0〜20質量%からなる組成物を用いるので、隠蔽性に優れており、溶断シール袋として好適である。
特に被覆層(I)または被覆層(II)を有する二軸延伸積層フィルムは溶断シール強度に優れているため、印刷後溶断シール袋として各種、主要な用途で用いることが出来る。隠蔽性、紫外線カット性に優れることから冷凍食品及びチョコレート、ガム、キャンデー等の菓子類、化粧品等の嗜好品、また隠蔽性に優れることからカセットテープ、ビデオテープ、CD、CDR、DVD、ゲームソフト等の記録材料、およびそれらの集積包装材料等の、箱物包装の包装用フィルムとして好適に使用できる。
Fusing seal bag
The biaxially stretched film of the present invention uses a composition comprising polylactic acid (A), a polymer (B) other than polylactic acid (5) to 25% by mass, and titanium oxide (C) 0 to 20% by mass. It is excellent and suitable as a fusing seal bag.
In particular, since the biaxially stretched laminated film having the coating layer (I) or the coating layer (II) is excellent in fusing seal strength, it can be used for various main applications as a fusing seal bag after printing. Excellent concealment and UV-blocking properties, frozen foods, chocolates, gums, candy and other sweets, cosmetics and other favorite products, and excellent concealment properties such as cassette tape, video tape, CD, CDR, DVD, game software Can be suitably used as a packaging film for box packaging, such as recording materials such as these, and their integrated packaging materials.
これらの溶断シール袋において、被覆層(II)の表面を内面としたときの溶断シール強度が10N/15mm幅以上とすることが望ましい。
さらに、本発明の多層二軸延伸積層フィルムは、前記用途に限らず、例えば、ラーメン、うどん、そば、焼きそば等の即席カップ麺食品、ヨーグルト、プリン、ゼリー等の乳酸菌飲料のような飲料デザート類カップ食品の個別あるいは複数個等の包装用フィルムに限らず、エアゾール製品、インテリア製品、CD類、磁気テープ製品の一般シュリンク包装、缶・瓶詰飲料、調味料などの集積シュリンクパックや、プラスチック容器、ガラス瓶などの胴張りシュリンクラベル、ワイン、ウイスキー等の瓶のキャップシール等、種々の包装用フィルム等に用い得る。
In these fusing seal bags, it is desirable that the fusing seal strength is 10 N / 15 mm width or more when the surface of the coating layer (II) is the inner surface.
Furthermore, the multilayer biaxially stretched laminated film of the present invention is not limited to the above-mentioned uses, for example, beverage desserts such as instant cup noodle foods such as ramen, udon, soba and fried noodles, and lactic acid bacteria beverages such as yogurt, pudding and jelly. In addition to individual or multiple packaging films for cup foods, aerosol products, interior products, CDs, general shrink packaging for magnetic tape products, canned / bottled beverages, concentrated shrink packs such as seasonings, plastic containers, It can be used for various packaging films, such as trunk-shrink labels for glass bottles, cap seals for bottles of wine, whiskey and the like.
オーバーラップ包装用フィルム
本発明の被覆層(II)を有する二軸延伸積層フィルムは、隠蔽性、化粧性、紫外線カット性に優れ、且つ両表面に、生分解性脂肪族ポリエステル共重合体(E)97〜5質量%及びポリ乳酸(F)3〜95質量%の組成物からなる被覆層(II)を有しているので、両表面が低温ヒートシール性、ヒートシール強度を有している。
本発明のオーバーラップ包装用フィルムは、さらに運搬に耐え得る耐衝撃性も有しているので、従来のポリオレフィンフィルムからなるオーバーラップ包装用フィルムが用いられている用途、例えば、冷凍食品及びチョコレート、ガム、キャンデー等の菓子類、化粧品等の嗜好品、カセットテープ、ビデオテープ、CD、CDR、DVD、ゲームソフト等の記録材料、およびそれらの集積包装材料等の、箱物包装の包装用フィルムとして好適に使用できる。
Overwrap packaging film
The biaxially stretched laminated film having the coating layer (II) of the present invention is excellent in concealability, cosmetic properties, and UV-cutting properties, and biodegradable aliphatic polyester copolymer (E) 97-5 mass on both surfaces. % And polylactic acid (F) 3 to 95% by mass of the coating layer (II) composed of the composition, both surfaces have low-temperature heat sealability and heat seal strength.
The overlap wrapping film of the present invention also has impact resistance that can withstand transportation, and therefore uses for which an overlap wrapping film made of a conventional polyolefin film is used, such as frozen food and chocolate, As a packaging film for box packaging such as gum, candy and other sweets, cosmetics and other luxury items, cassette tapes, videotapes, CDs, CDRs, DVDs, game software and other recording materials, and their integrated packaging materials It can be used suitably.
さらに、本発明の二軸延伸積層フィルムは、前記用途に限らず、例えば、ラーメン、うどん、そば、焼きそば等の即席カップ麺食品、ヨーグルト、プリン、ゼリー等の乳酸菌飲料のような飲料デザート類カップ食品の個別あるいは複数個等の包装用フィルムに限らず、エアゾール製品、インテリア製品の一般シュリンク包装、缶・瓶詰飲料、調味料などの集積シュリンクパックや、プラスチック容器、ガラス瓶などの胴張りシュリンクラベル、ワイン、ウイスキー等の瓶のキャップシール等、種々の包装用フィルム等に用いることができる。 Further, the biaxially stretched laminated film of the present invention is not limited to the above-mentioned applications, for example, instant cup noodle foods such as ramen, udon, soba and fried noodles, beverage dessert cups such as lactic acid bacteria beverages such as yogurt, pudding and jelly Not only for individual or multiple packaging films of food, but also for general shrink packaging of aerosol products and interior products, canned / bottled beverages, seasoning and other integrated shrink packs, plastic containers, shelled shrink labels such as glass bottles, It can be used for various packaging films such as caps for bottles of wine and whiskey.
実施例
次に実施例を挙げて本発明を更に具体的に説明するが、本発明はその要旨を越えない限りこれらの実施例に制約されるものではない。
実施例及び比較例等で使用した原料は次の通りである。
Example
EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist.
The raw materials used in Examples and Comparative Examples are as follows.
(1)ポリ乳酸
D−乳酸含有量:1.9質量%、MFR(温度190℃、荷重2160g):6.7g/10分、融点(Tm):168℃、Tg:60℃、密度:1.3g/cm3。
(2)ポリエチレン(PE)
プライムポリマー社製 3300F、MFR(温度190℃、荷重2160g):1.1、融点(Tm):131℃、密度:0.954g/cm3。
(1) Polylactic acid
D-lactic acid content: 1.9% by mass, MFR (temperature 190 ° C., load 2160 g): 6.7 g / 10 min, melting point (Tm): 168 ° C., Tg: 60 ° C., density: 1.3 g / cm 3 .
(2) Polyethylene (PE)
3300F manufactured by Prime Polymer Co., Ltd., MFR (temperature 190 ° C., load 2160 g): 1.1, melting point (Tm): 131 ° C., density: 0.954 g / cm 3 .
(3)ポリプロピレン(PP)
プライムポリマー社製 J103、MFR(温度230℃、荷重2160g):1.4、融点(Tm):160℃、密度:0.91g/cm3。
(4)ポリメチルメタクリレート(PMMA)
三菱レーヨン社製 アグリペットMF 、MFR(温度190℃、荷重2160g):14g/10分、ビカット軟化温度(JIS K7206):88℃、密度:1.19g/cm3。
(3) Polypropylene (PP)
J103 manufactured by Prime Polymer Co., Ltd., MFR (temperature 230 ° C., load 2160 g): 1.4, melting point (Tm): 160 ° C., density: 0.91 g / cm 3 .
(4) Polymethyl methacrylate (PMMA)
Mitsubishi Rayon Agripet MF, MFR (temperature 190 ° C., load 2160 g): 14 g / 10 minutes, Vicat softening temperature (JIS K7206): 88 ° C., density: 1.19 g / cm 3 .
(5)変性ポリエステル(SAE)
テレフタル酸45モル%、エチレングリコール37モル%、ジエチレングリコール9モル%、5−スルホーイソフタル酸ナトリウム1モル%、ヒドロキシ酢酸8モル%、MFR(温度120℃、荷重2160g):15g/10分、融点(Tm):200℃、密度:1.35g/cm3。
(5) Modified polyester (SAE)
Terephthalic acid 45 mol%, ethylene glycol 37 mol%, diethylene glycol 9 mol%, sodium 5-sulfoisoisophthalate 1 mol%, hydroxyacetic acid 8 mol%, MFR (temperature 120 ° C., load 2160 g): 15 g / 10 min, melting point (Tm): 200 ° C., density: 1.35 g / cm 3 .
(6)生分解性脂肪族ポリエステル
(イ)生分解性脂肪族ポリエステル(PBSA/L−1)
三菱化学社製、商品名 GS−Pla AZ91T MFR(190℃、荷重2160g):4.5g/10分、融点(Tm):108.9℃、結晶化温度(Tc):68.0℃、密度:1.25g/cm3。
(ロ)生分解性脂肪族ポリエステル(PBSA/L−2)
三菱化学社製、商品名 GS−Pla AD92W MFR(190℃、荷重2160g):4.5g/10分、融点(Tm):86.9℃、結晶化温度(Tc):40.4℃、密度:1.25g/cm3。
(6) Biodegradable aliphatic polyester
(I) Biodegradable aliphatic polyester (PBSA / L-1)
GS-Pla AZ91T MFR (190 ° C., load 2160 g): 4.5 g / 10 min, melting point (Tm): 108.9 ° C., crystallization temperature (Tc): 68.0 ° C., density : 1.25 g / cm 3 .
(B) Biodegradable aliphatic polyester (PBSA / L-2)
Product name: GS-Pla AD92W MFR (190 ° C., load 2160 g): 4.5 g / 10 min, melting point (Tm): 86.9 ° C., crystallization temperature (Tc): 40.4 ° C., density : 1.25 g / cm 3 .
(7)ポリカーボネート(PC)
日本GEプラスチックス社製、商品名 Lexan HF1110 密度:1.2g/cm3、荷重たわみ温度(ISO D648 荷重1.82MPa):130℃
(8)ポリスチレン(PS)
PSジャパン社製、商品名 HH203 MFR(200℃、荷重5kgf):3.3g/10分、密度:1.05g/cm3。
(7) Polycarbonate (PC)
Product name: Lexan HF1110 Density: 1.2 g / cm 3 , Deflection temperature under load (ISO D648 load 1.82 MPa): 130 ° C
(8) Polystyrene (PS)
Product name HH203 MFR (200 ° C., load 5 kgf): 3.3 g / 10 min, density: 1.05 g / cm 3 , manufactured by PS Japan.
(9)環状ポリオレフィン(COC)
日本ゼオン社製、商品名 ZEONOR 1020R MFR(280℃、荷重21.18N):20g/10分、ガラス転移温度(Tg):102℃、密度:1.01g/cm3。
(10)ポリ−4−メチルペンテン−1(P4MP1)
三井化学株式会社製、商品名 TPX DX845 密度:0.83g/cm3、融点:240℃、MFR(ASTM D1238、260℃):22(g/10分)
(9) Cyclic polyolefin (COC)
ZEONOR 1020R MFR (280 ° C., load 21.18 N): 20 g / 10 minutes, glass transition temperature (Tg): 102 ° C., density: 1.01 g / cm 3 .
(10) Poly-4-methylpentene-1 (P4MP1)
Product name: TPX DX845, manufactured by Mitsui Chemicals, Inc. Density: 0.83 g / cm 3 , Melting point: 240 ° C., MFR (ASTM D1238, 260 ° C.): 22 (g / 10 min)
本発明における各種測定方法は以下のとおりである。
(1)光学特性
日本電色工業社製ヘイズメーター300Aを用いて、ヘイズ(HZ:%)、平行光線透過率(PT:%)及びグロス(%)を測定した。測定値は5回の平均値である。
(2)表面粗さ(SRa)
株式会社小坂研究所製三次元表面粗さ測定器SE−30Kを用いてフィルム表面の中心表面粗さ(SRa)を求めた。
Various measurement methods in the present invention are as follows.
(1) Optical characteristics
Haze (HZ:%), parallel light transmittance (PT:%), and gloss (%) were measured using a haze meter 300A manufactured by Nippon Denshoku Industries Co., Ltd. The measured value is an average value of 5 times.
(2) Surface roughness (SRa)
The center surface roughness (SRa) of the film surface was determined using a 3D surface roughness measuring instrument SE-30K manufactured by Kosaka Laboratory.
(3)引張り試験
試験片として、フィルムから短冊状フィルム片(長さ:150mm、幅:15mm)を切出し、引張り試験機(オリエンテック社製テンシロン万能試験機RTC-1225)を用い、チャック間距離:100mm、クロスヘッドスピード:300mm/分(但し、ヤング率の測定は5mm/分)の条件で引張試験を行い、降伏点及び破断点における強度(MPa)、伸び(%)、ヤング率(MPa)を求めた。なお、伸度(%)はチャック間距離の変化とした。測定値は5回の平均値である。
(3) Tensile test
A strip-shaped film piece (length: 150 mm, width: 15 mm) was cut out from the film as a test piece, and a tensile tester (Orientec Tensilon Universal Tester RTC-1225) was used. Chuck distance: 100 mm, crosshead A tensile test was performed under the conditions of speed: 300 mm / min (however, Young's modulus was measured at 5 mm / min), and the strength (MPa), elongation (%), and Young's modulus (MPa) at the yield point and the break point were obtained. The elongation (%) was the change in the distance between chucks. The measured value is an average value of 5 times.
実施例1
<組成物の製造>
ポリ乳酸:ポリエチレン(PE)を90:10(質量%)の比で80g計量し、東洋精機製ラボプラストミルCモデル(2軸混練機)を用いて250℃、60rpmの条件下で5分間溶融混練し、ポリ乳酸組成物(組成物―1)を得た。
<プレスシートの製造>
組成物―1を厚さ:50μmのポリイミドフィルム(宇部興産製 商品名:ユーピレックスー50S)で挟んだ後、厚さ:0.5mm及び270mm×270mmのステンレス製矩形の金枠に入れ、プレス温度:250℃、初圧:3分(圧力0)、ガス抜き:5回、プレス時間:4分(圧力100kgf)、冷却:5分(圧力10kgf)の条件でプレス成形し、プレスシート(プレスシート−1)を得た。
Example 1
<Production of composition>
80g of polylactic acid: polyethylene (PE) is weighed at a ratio of 90:10 (mass%) and melted for 5 minutes at 250 ° C and 60 rpm using a Laboplast Mill C model (biaxial kneader) manufactured by Toyo Seiki The mixture was kneaded to obtain a polylactic acid composition (Composition-1).
<Manufacture of press sheets>
After sandwiching Composition-1 with a polyimide film having a thickness of 50 μm (trade name: Upilex 50S manufactured by Ube Industries), the composition-1 was placed in a stainless steel rectangular metal frame having a thickness of 0.5 mm and 270 mm × 270 mm, and a press temperature: 250 ° C., initial pressure: 3 minutes (pressure 0), degassing: 5 times, press time: 4 minutes (pressure 100 kgf), cooling: 5 minutes (pressure 10 kgf), press sheet (press sheet- 1) was obtained.
<二軸延伸フィルムの製造>
プレスシート−1を、パンタグラフ式バッチ二軸延伸装置(東洋精機製作所、ヘビー型)を用いて70℃ホットエアーで30秒予熱した後、5m/分の速度で、縦横方向に3.0倍延伸(同時二軸延伸)し、延伸後に直ちに延伸フィルムを扇風機で冷却し、厚さ約50μmの二軸延伸フィルムを得た。
<Manufacture of biaxially stretched film>
Press sheet-1 is preheated with hot air at 70 ° C for 30 seconds using a pantograph batch biaxial stretching device (Toyo Seiki Seisakusho, Heavy type), and then stretched 3.0 times in the vertical and horizontal directions at a speed of 5 m / min. (Simultaneous biaxial stretching), and immediately after stretching, the stretched film was cooled by a fan to obtain a biaxially stretched film having a thickness of about 50 μm.
実施例2〜10
実施例1のPEに替えてポリマー(B)として、表1に記載のポリマーを用いてた以外は実施例1と同様に行った。
比較例1
ポリマー(B)を用いない以外は、実施例1と同様に行った。
Examples 2-10
It replaced with PE of Example 1, and it carried out similarly to Example 1 except having used the polymer of Table 1 as a polymer (B).
Comparative Example 1
It carried out like Example 1 except not using a polymer (B).
参考例1
ポリマー(B)の替わりに、炭酸カルシウムを用いた以外は実施例1と同様に行った。
これら、実施例、比較例1および参考例1で得られたポリ乳酸ニ軸延伸フィルムの物性を評価した。評価結果を表1に示す。
Reference example 1
It carried out similarly to Example 1 except having used calcium carbonate instead of the polymer (B).
The physical properties of the polylactic acid biaxially stretched films obtained in Examples, Comparative Example 1 and Reference Example 1 were evaluated. The evaluation results are shown in Table 1.
表1から明らかなように、ポリ乳酸(A)にポリ乳酸以外のポリマー(B)を10質量%配合、それを延伸した実施例―1ないし9はポリ乳酸単体からなるフィルム(比較例1)のヘイズが2.5%であるのに対して37〜99%と隠蔽性が上がっていることが分かる。
炭酸カルシウムを配合したフィルム(参考例1)もヘイズが92%と隠蔽性は良好であるが、層内に炭酸カルシウムを含むため欠落するおそれがあり、クリーン度を要求される用途に適さない。
As can be seen from Table 1, Examples 1 to 9 were prepared by blending 10% by mass of a polymer (B) other than polylactic acid with polylactic acid (A) and stretching it (Examples 1 to 9 are films made of polylactic acid alone (Comparative Example 1)). It can be seen that the haze is 2.5%, while the concealability is improved by 37 to 99%.
Although the film containing the calcium carbonate (Reference Example 1) has a haze of 92% and good concealability, it may be lost because it contains calcium carbonate in the layer, and is not suitable for applications requiring cleanliness.
Claims (9)
生分解性脂肪族ポリエステル共重合体(E)を構成する2官能脂肪族ヒドロキシカルボン酸成分(e3)が同共重合体(E)に0.1〜25モル%の割合で含まれる〔ただし、脂肪族または脂環式ジカルボン酸成分(e1)、脂肪族または脂環式ジヒドロキシ化合物成分(e2)及び2官能脂肪族ヒドロキシカルボン酸成分(e3)のうち、脂肪族または脂環式ジカルボン酸成分(e1)と脂肪族または脂環式ジヒドロキシ化合物成分(e2)のモル数量は実質的に等しく、(e1)+(e2)+(e3)=100質量%とする。〕ことを特徴とする請求項5記載の延伸積層フィルム。
The bifunctional aliphatic hydroxycarboxylic acid component (e3) constituting the biodegradable aliphatic polyester copolymer (E) is contained in the copolymer (E) at a ratio of 0.1 to 25 mol% [however, Of the aliphatic or alicyclic dicarboxylic acid component (e1), the aliphatic or alicyclic dihydroxy compound component (e2) and the bifunctional aliphatic hydroxycarboxylic acid component (e3), the aliphatic or alicyclic dicarboxylic acid component ( The molar quantity of e1) and the aliphatic or alicyclic dihydroxy compound component (e2) is substantially equal, and (e1) + (e2) + (e3) = 100% by mass. The stretched laminated film according to claim 5.
It is a biaxially stretched film, The stretched film or stretched laminated film in any one of Claims 1-8 characterized by the above-mentioned.
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| JP2008255134A (en) * | 2007-03-30 | 2008-10-23 | Mitsubishi Plastics Ind Ltd | Heat-shrinkable film, molded article using the heat-shrinkable film, heat-shrinkable label, and container using or fitted with the molded article |
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