JP5080217B2 - Laminated film - Google Patents
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- JP5080217B2 JP5080217B2 JP2007304700A JP2007304700A JP5080217B2 JP 5080217 B2 JP5080217 B2 JP 5080217B2 JP 2007304700 A JP2007304700 A JP 2007304700A JP 2007304700 A JP2007304700 A JP 2007304700A JP 5080217 B2 JP5080217 B2 JP 5080217B2
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Description
本発明は積層フィルムに関し、詳しくは硫酸バリウム粒子を多量に含有するポリエステル組成物の反射層を備える積層フィルムに関する。 The present invention relates to a laminated film, and more particularly to a laminated film provided with a reflective layer of a polyester composition containing a large amount of barium sulfate particles.
ポリエステルに硫酸バリウム粒子を含有させて白色のフィルムを得ることが知られている（特開２０００−３７８３５号公報、特開２００５−１２５７００号公報）。
フィルムを製造する際には、異物によるフィルム欠点を作らないために、溶融した原料組成物をフィルターで濾過することが行われるが、硫酸バリウム粒子をポリエステルに高濃度で添加した組成物では、急激な濾過圧上昇が発生する。濾過圧上昇が発生すると、溶融押出し時の吐出圧が変動し、場合によっては吐出自体ができなくなる。
It is known that a white film is obtained by containing polyester with barium sulfate particles (JP 2000-37835 A, JP 2005-125700 A).
When producing a film, in order not to create a film defect due to foreign matter, the molten raw material composition is filtered through a filter. However, in a composition in which barium sulfate particles are added to polyester at a high concentration, the composition is rapidly increased. Increase in filtration pressure. When the filtration pressure rises, the discharge pressure during melt extrusion fluctuates, and in some cases, the discharge itself cannot be performed.
本発明は、高濃度で硫酸バリウム粒子を含有して高い反射率を備えながら、フィルム製造の際の溶融押出において急激な濾過圧上昇が発生することがなく、生産性の高い積層フィルムを提供することを目的とする。 The present invention provides a highly productive laminated film that contains barium sulfate particles at a high concentration and has a high reflectivity, and does not cause a sudden increase in filtration pressure in melt extrusion during film production. For the purpose.
すなわち本発明は、積層フィルム全体厚みの６０〜９５％を占め硫酸バリウム粒子２０〜８０重量％およびポリエステル２０〜８０重量％の組成物からなる反射層と、積層フィルム全体厚みの５〜４０％を占めポリエステルからなる支持層とから構成される総厚み１０〜５００μｍの積層フィルムであって、反射層に用いられる硫酸バリウム粒子を小粒径側から積算した５０％体積粒径（Ｄ５０）が１．０〜３．０μｍの範囲にあり、反射層に用いられる硫酸バリウム粒子を小粒径側から積算した９０％体積粒径（Ｄ９０）と１０％体積粒径（Ｄ１０）との比（Ｄ９０／Ｄ１０）が１０以下であり、上記硫酸バリウム粒子は、粒径０．５μｍ以下の粒子が全粒子に占める割合が８体積％以下である、ことを特徴とする積層フィルムである。 That is, the present invention occupies 60 to 95% of the total thickness of the laminated film and comprises a reflective layer composed of 20 to 80% by weight of barium sulfate particles and 20 to 80% by weight of polyester, and 5 to 40% of the total thickness of the laminated film. It is a laminated film having a total thickness of 10 to 500 μm composed of a supporting layer made of polyester, and has a 50% volume particle size (D50) obtained by integrating the barium sulfate particles used in the reflective layer from the small particle size side. The ratio (D90 / D10) of 90% volume particle diameter (D90) and 10% volume particle diameter (D10) obtained by integrating the barium sulfate particles used in the reflective layer from the small particle diameter side in the range of 0 to 3.0 μm. ) is Ri der 10 or less, the barium sulfate particles, the ratio of the particle diameter of 0.5μm or less of the particles to the total particles Ru der than 8% by volume, a laminated film, characterized in that.
本発明によれば、高濃度で硫酸バリウム粒子を含有して高い反射率を備えながら、フィルム製造の際の溶融押出において急激な濾過圧上昇が発生することがなく、生産性の高い積層フィルムを提供することができる。 According to the present invention, it is possible to obtain a laminated film having a high productivity without containing a rapid increase in filtration pressure in melt extrusion during film production while containing barium sulfate particles at a high concentration and having a high reflectance. Can be provided.
以下、本発明を詳細に説明する。
［積層厚み］
本発明の積層フィルムは、反射層と支持層とからなる。反射層は積層フィルム全体厚みの６０〜９５％を占め、支持層は積層フィルム全体厚みの５〜４０％を占める。反射層が積層フィルムの全体厚みに占める割合が６０％未満であると、反射特性が劣り高い反射率を得ることができず、９５％を超えると製膜できない。
Hereinafter, the present invention will be described in detail.
[Lamination thickness]
The laminated film of the present invention comprises a reflective layer and a support layer. The reflective layer accounts for 60 to 95% of the total thickness of the laminated film, and the support layer accounts for 5 to 40% of the total thickness of the laminated film. When the ratio of the reflective layer to the total thickness of the laminated film is less than 60%, the reflection characteristics are inferior and high reflectance cannot be obtained, and when it exceeds 95%, film formation cannot be performed.
本発明の積層フィルムの総厚みは１０〜５００μｍ、好ましくは２５〜３４０μｍである。積層フィルムの総厚みが１０μｍ未満であると白色濃度が不足し、積層フィルムを光線を反射する部材として用いるときのハンドリング性が低下し、例えばバックライトユニットに組み込むときのハンドリグ性が低下する。他方、５００μｍを超えると、薄さが求められるバックライト用途において厚すぎて嫌われる。そもそも、５００μｍを超えるとフィルムが厚すぎて延伸できない。 The total thickness of the laminated film of the present invention is 10 to 500 μm, preferably 25 to 340 μm. When the total thickness of the laminated film is less than 10 μm, the white density is insufficient, and handling properties when the laminated film is used as a member that reflects light rays are lowered, for example, handling properties when incorporated in a backlight unit are lowered. On the other hand, if it exceeds 500 μm, it is hated because it is too thick in backlight applications where thinness is required. In the first place, if it exceeds 500 μm, the film is too thick to be stretched.
［組成］
反射層は、硫酸バリウム粒子２０〜８０重量％およびポリエステル２０〜８０重量％の組成物からなる。硫酸バリウム粒子が２０重量％未満であると白色度および反射特性が不十分であり、８０重量％を超えると硫酸バリウム粒子が脱落しやすくなったりフィルムの製膜性が低下する。反射層の組成物における硫酸バリウム粒子の含有量は、好ましくは３０〜７０重量％、さらに好ましくは３５〜６５重量％、特に好ましくは４０〜６０重量％である。
支持層はポリエステルからなるが、例えば１５重量％以下、さらに例えば１０重量％以下の量で硫酸バリウム粒子を含んでもよい。
[composition]
The reflective layer is composed of a composition of 20 to 80% by weight of barium sulfate particles and 20 to 80% by weight of polyester. If the barium sulfate particles are less than 20% by weight, the whiteness and reflection characteristics are insufficient, and if it exceeds 80% by weight, the barium sulfate particles are likely to fall off or the film-forming property of the film is lowered. The content of barium sulfate particles in the composition of the reflective layer is preferably 30 to 70% by weight, more preferably 35 to 65% by weight, and particularly preferably 40 to 60% by weight.
The support layer is made of polyester, and may contain barium sulfate particles in an amount of, for example, 15% by weight or less, further, for example, 10% by weight or less.
［ポリエステル］
本発明の積層フィルムを構成するポリエステルとしては、芳香族ポリエステルを用いることができ、例えばポリエチレンテレフタレート、ポリエチレンナフタレートを用いることができる。これらのポリエステルは、例えば３０モル％以下の割合で共重合成分を含んでもよい。ポリエチレンテレフタレートの共重合成分として、例えばナフタレンジカルボン酸を挙げることができ、ポリエチレンナフタレンジカルボキシレートの共重合成分として、例えばテレフタル酸を挙げることができる。ポリエチレンテレフタレートおよびポリエチレンナフタレートに共通する共重合成分として、例えばイソフタル酸を挙げることができる。
[polyester]
As polyester which comprises the laminated | multilayer film of this invention, aromatic polyester can be used, for example, a polyethylene terephthalate and a polyethylene naphthalate can be used. These polyesters may contain a copolymer component in a proportion of, for example, 30 mol% or less. Examples of the copolymer component of polyethylene terephthalate include naphthalene dicarboxylic acid, and examples of the copolymer component of polyethylene naphthalene dicarboxylate include terephthalic acid. Examples of the copolymer component common to polyethylene terephthalate and polyethylene naphthalate include isophthalic acid.
［硫酸バリウム粒子］
次に、本発明における硫酸バリウム粒子を説明する。なお、硫酸バリウム粒子は、個々の粒子としてではなく、特定の粒度分布を示す粒子の集合体として、ポリエステルに配合されるので、硫酸バリウム粒子を「硫酸バリウム粒子の集合体」ということがある。「集合体」は粒子の集合を意味し、凝集体の意味ではない。
[Barium sulfate particles]
Next, the barium sulfate particles in the present invention will be described. The barium sulfate particles are blended with the polyester as an aggregate of particles exhibiting a specific particle size distribution, not as individual particles, and thus the barium sulfate particles are sometimes referred to as an “aggregate of barium sulfate particles”. “Aggregate” means an aggregate of particles, not an aggregate.
［５０％体積粒径］
本発明の積層フィルムで反射層に用いられる硫酸バリウム粒子の集合体は、小粒径側から積算した５０％体積粒径（Ｄ５０）が１．０〜３．０μｍ、好ましくは１．２〜２．５μｍ、さらに好ましくは１．４〜２．２μｍである集合体である。５０％体積粒径（Ｄ５０）は、レーザー散乱測定法により測定された粒度分布から算出する。５０％体積粒径が１．０μｍ未満であると、フィルムの製造にダイに押し出す前のフィルターで凝集して生産性が低下し、また積層フィルムの白色度や反射特性が損なわれる。他方、３．０μｍを超えると、フィルターの昇圧が早くなって生産性が低下し、またフィルムの反射特性も劣ったものとなる。
[50% volume particle size]
The aggregate of barium sulfate particles used for the reflective layer in the laminated film of the present invention has a 50% volume particle size (D50) integrated from the small particle size side of 1.0 to 3.0 μm, preferably 1.2 to 2. The aggregate is 0.5 μm, more preferably 1.4 to 2.2 μm. The 50% volume particle size (D50) is calculated from the particle size distribution measured by the laser scattering measurement method. When the 50% volume particle size is less than 1.0 μm, the product is agglomerated by a filter before being extruded onto a die for production of the film and the productivity is lowered, and the whiteness and reflection characteristics of the laminated film are impaired. On the other hand, if it exceeds 3.0 μm, the pressure increase of the filter is accelerated, the productivity is lowered, and the reflection characteristics of the film are also inferior.
［９０％体積粒径／１０％体積粒径］
本発明の積層フィルムで反射層に用いられる硫酸バリウム粒子の集合体は、小粒径側から積算した９０％体積粒径（Ｄ９０）と１０％体積粒径（Ｄ１０）との比（Ｄ９０／Ｄ１０）が１０以下、好ましくは９以下、さらに好ましくは７以下である集合体である。Ｄ９０／Ｄ１０が１０を超えると、フィルターを目詰まりさせる粗大粒子の割合が増え、濾過圧上昇の抑制効果が得られない。Ｄ９０／Ｄ１０の下限は特に制限されないが、風力分級などで極めて狭い粒径範囲の粒子だけを取り出したとしても、通常２程度である。
[90% volume particle size / 10% volume particle size]
The aggregate of barium sulfate particles used for the reflective layer in the laminated film of the present invention has a ratio (D90 / D10) of 90% volume particle diameter (D90) and 10% volume particle diameter (D10) integrated from the small particle diameter side. ) Is 10 or less, preferably 9 or less, more preferably 7 or less. When D90 / D10 exceeds 10, the ratio of coarse particles that clog the filter increases, and the effect of suppressing the increase in filtration pressure cannot be obtained. The lower limit of D90 / D10 is not particularly limited, but is usually about 2 even if only particles having a very narrow particle size range are taken out by air classification or the like.
［粒径０．５μｍ以下の粒子の量］
本発明の積層フィルムに用いる硫酸バリウム粒子の集合体は、粒径０．５μｍ以下の粒子が全粒子に占める割合が、好ましくは８体積％以下、さらに好ましくは６体積％以下、特に好ましくは５体積％以下である。この割合はレーザー散乱測定法により測定された粒度分布から算出する。
[Amount of particles having a particle size of 0.5 μm or less]
In the aggregate of barium sulfate particles used in the laminated film of the present invention, the proportion of particles having a particle size of 0.5 μm or less in the total particles is preferably 8% by volume or less, more preferably 6% by volume or less, and particularly preferably 5%. % By volume or less. This ratio is calculated from the particle size distribution measured by the laser scattering measurement method.
粒径０．５μｍ以下の粒子が全粒子に占める割合が、８体積％を超えるとフィルムの製造時にフィルターでの濾過圧の上昇を招き、フィルター交換を要することになり生産性が劣る。他方、粒径０．５μｍ以下の粒子が全粒子に占める割合の下限は任意であるが、風力分級などで極めて狭い粒径範囲の粒子だけを取り出したとしても１体積％程度である。 When the ratio of particles having a particle size of 0.5 μm or less to the total particles exceeds 8% by volume, the filtration pressure in the filter increases during the production of the film, and the filter needs to be replaced, resulting in poor productivity. On the other hand, the lower limit of the ratio of particles having a particle size of 0.5 μm or less to all particles is arbitrary, but even if only particles having a very narrow particle size range are taken out by air classification or the like, it is about 1% by volume.
［粒径３．０μｍを超える硫酸バリウム粒子の量］
本発明の積層フィルムに用いる硫酸バリウム粒子の集合体は、粗大粒子によるフィルム欠点の発生や押出時の濾過圧上昇を抑制する観点から、粒径３．０μｍを越える硫酸バリウム粒子の量が、全粒子の体積を基準として３０体積％以下であることが好ましく、１５体積％以下であることがさらに好ましい。
[Amount of barium sulfate particles having a particle size exceeding 3.0 μm]
The aggregate of barium sulfate particles used in the laminated film of the present invention has a total amount of barium sulfate particles having a particle size exceeding 3.0 μm from the viewpoint of suppressing the occurrence of film defects due to coarse particles and the increase in filtration pressure during extrusion. It is preferably 30% by volume or less, more preferably 15% by volume or less, based on the volume of the particles.
これらの条件を満足する硫酸バリウム粒子の集合体は、例えば後述の風力分級を行い、小粒径の硫酸バリウム粒子および小粒径となりやすい硫酸バリウム粒子を取り除くことで得ることができる。 An aggregate of barium sulfate particles satisfying these conditions can be obtained, for example, by performing air classification described later to remove barium sulfate particles having a small particle diameter and barium sulfate particles that tend to have a small particle diameter.
［製造方法］
本発明の積層フィルムは、溶融押出成形によって未延伸シートを得、これを延伸して得ることができる。溶融押出成形に供する原料の硫酸バリウム粒子として、小粒径側から積算した５０％体積粒径（Ｄ５０）が１．０〜３．０μｍの範囲にあり、反射層に用いられる硫酸バリウム粒子を小粒径側から積算した９０％体積粒径（Ｄ９０）と１０％体積粒径（Ｄ１０）との比（Ｄ９０／Ｄ１０）が１０以下である硫酸バリウム粒子の集合体を用いるのであるが、この硫酸バリウム粒子の集合体は、通常の硫酸バリウム粒子に風力分級を施して小粒径の粒子を取り除くことで得ることができる。
[Production method]
The laminated film of the present invention can be obtained by obtaining an unstretched sheet by melt extrusion molding and stretching it. As the raw material barium sulfate particles used for melt extrusion molding, the 50% volume particle size (D50) integrated from the small particle size side is in the range of 1.0 to 3.0 μm, and the barium sulfate particles used in the reflective layer are small. An aggregate of barium sulfate particles having a ratio (D90 / D10) of 90% volume particle size (D90) and 10% volume particle size (D10) integrated from the particle size side of 10 or less is used. An aggregate of barium particles can be obtained by subjecting ordinary barium sulfate particles to air classification and removing particles having a small particle size.
なお、この硫酸バリウム粒子の集合体は、通常の市販されている硫酸バリウム粒子をそのまま用いたり、単にフィルターによって小粒径のものを取り除くだけでは、得ることができない。 This aggregate of barium sulfate particles cannot be obtained by using ordinary commercially available barium sulfate particles as they are or simply removing small particles with a filter.
風力分級に供する硫酸バリウム粒子は、沈殿法により好ましく製造することができる。具体的には、例えばクンストストッフ−ジャーナル（Ｋｕｎｓｔｓｔｏｆｆ−Ｊｏｕｒｎａｌ）８、Ｎｏ．１０、３０−３６頁、またはＮｏ．１１、３１−３６頁に記載される方法で、バリウム塩と硫酸塩または硫酸から製造することができる。平均粒径は反応条件により制御することができる。この沈降性硫酸バリウムとしては、例えば堺化学製 沈降性硫酸バリウム＃１００、＃３００、ＳＳ−５０、Ｂ−５５を用いることができる。 Barium sulfate particles used for air classification can be preferably produced by a precipitation method. Specifically, for example, Kunststoff-Journal 8; 10, pages 30-36, or no. 11, 31-36. It can be produced from barium salt and sulfate or sulfuric acid. The average particle size can be controlled by reaction conditions. As the sedimentary barium sulfate, for example, sedimentary barium sulfate # 100, # 300, SS-50, and B-55 manufactured by Sakai Chemical can be used.
なお、風力分級の条件は、用いる装置によって異なり、一般的に特定することはできないが、本発明で規定される粒度分布になるように適宜調整すればよく、風力分級処理装置の風力を調整したり、分級処理を繰り返すことによってより、進めることができる。 Note that the air classification conditions vary depending on the device used and cannot generally be specified, but may be adjusted as appropriate so that the particle size distribution defined in the present invention is obtained, and the wind force of the air classification processing device is adjusted. Or by repeating the classification process.
硫酸バリウム粒子の集合体のポリエステルへの添加は、ポリエステルの重合段階で行ってもよく、ポリエステルを重合した後で溶融混練する際に添加してもよい。
高濃度で硫酸バリウム粒子の集合体をポリエステルに添加するために、重合反応への影響を無くし、重合反応容器の汚染を防ぐなどの観点から、ポリエステルを重合したあと後で溶融混練する際に添加することが好ましい。
The aggregate of the barium sulfate particles may be added to the polyester during the polymerization stage of the polyester, or may be added when the polyester is polymerized and melt-kneaded.
In order to add a high concentration of barium sulfate particles to the polyester, it is added when the polyester is polymerized and then melt-kneaded from the viewpoint of eliminating the influence on the polymerization reaction and preventing contamination of the polymerization reaction vessel. It is preferable to do.
例えば、硫酸バリウム粒子の集合体を粉体の状態で供給する場合、原料であるポリエステル用の押出機と当該押出機に定量的に粉体供給できる供給装置を兼ね備える溶融混錬押出機を用意し、これにポリエステルと硫酸バリウム粒子の集合体とを供給して溶融混錬し、押出し、冷却すればよい。 For example, when supplying an aggregate of barium sulfate particles in a powder state, prepare a melt-kneading extruder that combines an extruder for polyester, which is a raw material, and a supply device that can quantitatively supply powder to the extruder. Then, polyester and an aggregate of barium sulfate particles may be supplied thereto, melted and kneaded, extruded, and cooled.
押出機は、均一な混錬が可能で粒子の分散に効果的な二軸タイプが好ましく、例えばニーディングディスクおよび逆ねじの混錬用エレメントを配したスクリュー構成を有するベント式二軸混錬押出機を用いることができる。 The extruder is preferably a twin-screw type capable of uniform kneading and effective in dispersing particles. For example, a vent type twin-screw kneading extrusion having a screw configuration in which kneading disks and reverse screw kneading elements are arranged. A machine can be used.
溶融混練したポリエステル組成物は、フィードブロックを用いた同時多層押出法により、積層未延伸シートを製造し、これを製膜方向もしくは幅方向、好ましくはその両方向に延伸し、必要に応じて熱固定処理い、フィルムとすることができる。 The melt-kneaded polyester composition produces a laminated unstretched sheet by a simultaneous multilayer extrusion method using a feed block, and stretches it in the film forming direction or width direction, preferably in both directions, and heat-set as necessary. Can be processed and filmed.
製膜方向の延伸としては、２個以上のロールの周速差を利用して行うのが好ましい。延伸温度は、好ましくはポリエステルのガラス転移点（Ｔｇ）以上の温度、さらに好ましくはＴｇ〜Ｔｇ＋７０℃の温度である。延伸倍率は、用途の要求特性にもよるが、製膜方向、幅方向とも、好ましくは２．５〜４．０倍、さらに好ましくは２．８〜３．９倍である。 The stretching in the film forming direction is preferably performed by utilizing the peripheral speed difference between two or more rolls. The stretching temperature is preferably a temperature equal to or higher than the glass transition point (Tg) of the polyester, more preferably a temperature of Tg to Tg + 70 ° C. The draw ratio is preferably 2.5 to 4.0 times, more preferably 2.8 to 3.9 times in both the film forming direction and the width direction, although it depends on the required characteristics of the application.
以下、実施例により本発明をさらに説明する。特性の測定および評価は、下記のとおり行った。 Hereinafter, the present invention will be further described by examples. The characteristics were measured and evaluated as follows.
（１）極限粘度数（ＩＶ）
ポリエステル０．６ｇをオルトクロロフェノール５０ｍｌ中に、加熱溶解した後、一旦冷却させ、その溶液をオストワルド式粘度管を用いて３５℃の温度条件で測定した溶液粘度から算出した。
(1) Intrinsic viscosity number (IV)
After 0.6 g of polyester was dissolved by heating in 50 ml of orthochlorophenol, it was once cooled, and the solution was calculated from the solution viscosity measured at 35 ° C. using an Ostwald viscosity tube.
（２）硫酸バリウム粒子の集合体の粒度分布
粒度分布は、超音波発信器を有するフローセル方式供給装置（多機能サンプラーＳＡＬＤ−ＭＳ７０）を有する島津製作所製レーザー散乱式粒度分布測定装置ＳＡＬＤ−７０００を使用して測定した。
粒子は測定前にエチレングリコール中に分散するが、この分散は硫酸バリウム粒子の粉体を５重量％スラリー濃度相当になるよう計量して家庭用ミキサーＮａｔｉｏｎａｌ ＭＸＶ２５３型料理用ミキサーにて１０分間攪拌し、常温まで冷却することで行った。測定対象の硫酸バリウム粒子を含有するエチレングリコール分散液をフローセル方式供給装置に供給し、この供給装置中で脱泡のために３０秒間超音波処理（超音波処理の強度は超音波処理装置のつまみを、ＭＡＸ値を示す位置から６０％の位置）してから粒度分布の測定を行った。粒度分布の測定結果から小粒径から積算した粒径０．５μｍ以下の粒子の量（体積分率）、粒径３．０μｍを超える粒子の量（体積分率）、１０％体積粒径（Ｄ１０）、５０％体積粒径（Ｄ５０）、９０％体積粒径（Ｄ９０）を求めた。なお、この測定で超音波処理を試料に施しているが、これは脱泡のためであり、この程度の超音波処理では粒子の状態は変わらない。
(2) Particle size distribution of aggregates of barium sulfate particles The particle size distribution is obtained by using a laser scattering particle size distribution analyzer SALD-7000 manufactured by Shimadzu Corporation having a flow cell type supply device (multifunctional sampler SALD-MS70) having an ultrasonic transmitter. Measured using.
The particles are dispersed in ethylene glycol before measurement, and this dispersion is measured by stirring the barium sulfate particle powder so as to correspond to a 5% by weight slurry concentration and stirring for 10 minutes with a domestic mixer National MXV253 type cooking mixer. It was performed by cooling to room temperature. An ethylene glycol dispersion containing barium sulfate particles to be measured is supplied to a flow cell type supply device, and sonication is performed for 30 seconds in this supply device for defoaming (the intensity of ultrasonic treatment is a knob of the ultrasonic treatment device). Was measured 60% from the position showing the MAX value), and the particle size distribution was measured. From the measurement result of the particle size distribution, the amount of particles with a particle size of 0.5 μm or less (volume fraction) integrated from a small particle size, the amount of particles with a particle size exceeding 3.0 μm (volume fraction), 10% volume particle size ( D10), 50% volume particle size (D50), and 90% volume particle size (D90) were determined. In this measurement, the sample was subjected to sonication, but this was for defoaming, and with this degree of sonication, the state of the particles did not change.
（３）硫酸バリウム粒子の平均粒径
上記Ｄ９０同様に、島津製作所製レーザー散乱式粒度分布測定装置ＳＡＬＤ−７０００を使用して測定した。粒度分布測定結果より５０％体積粒径（Ｄ５０）の値を平均粒子径とした。
(3) Average particle diameter of barium sulfate particles The measurement was performed using a laser scattering particle size distribution analyzer SALD-7000 manufactured by Shimadzu Corporation in the same manner as D90. From the particle size distribution measurement results, the value of 50% volume particle size (D50) was defined as the average particle size.
（４）濾過性評価
硫酸バリウム粒子の集合体を含有するポリエステル組成物をペレットの状態で、吐出部に２０００メッシュの金網フィルターを取り付けた（株）東洋精機製作所製小型二軸押出機（ラボプラストミル:二軸スクリュウフルフライト２Ｄ２５Ｓ型）に３００℃にて２Ｋｇ／Ｈｒの流速で供給し、フィルター圧力の変化を測定した。そして、下記式より濾過圧上昇度（△Ｐ値）を算出した。
△Ｐ＝Ｐ６０−Ｐ１５
（ここでＰ１５はテスト開始１５分後のフィルター圧力（ＭＰａ）を、Ｐ６０はテスト開始６０分後のフィルター圧力（ＭＰａ）をそれぞれ示す。）
(4) Evaluation of filterability A small twin-screw extruder manufactured by Toyo Seiki Seisakusho Co., Ltd. (laboplast) in which a polyester composition containing an aggregate of barium sulfate particles is in a pellet state and a 2000-mesh wire mesh filter is attached to the discharge part. Mill: biaxial screw full flight 2D25S type) at 300 ° C. at a flow rate of 2 Kg / Hr, and the change in filter pressure was measured. And the filtration pressure rise degree ((DELTA) P value) was computed from the following formula.
ΔP = P 60 −P 15
(Here, P 15 indicates the filter pressure (MPa) 15 minutes after the start of the test, and P 60 indicates the filter pressure (MPa) 60 minutes after the start of the test.)
（５）フィルム製膜性評価
安定に製膜できるかどうか、下記基準で評価した。
○：１時間以上安定に製膜できる。
×：１時間以内に切断や、フィルター昇圧が発生し、安定に製膜できない。
(5) Evaluation of film formability Whether the film can be stably formed was evaluated according to the following criteria.
○: A film can be stably formed for 1 hour or more.
X: Cutting or filter pressurization occurs within 1 hour, and stable film formation cannot be achieved.
（６）ポリエステルの製造
テレフタル酸ジメチル８９部およびイソフタル酸ジメチル１１部とエチレングリコール７０部の混合物に、テトラ−ｎ−ブチルチタネート（Ｔｉ元素として０．００２５部）を加圧反応が可能なＳＵＳ製容器に仕込み、０．０７ＭＰａの加圧を行い１４０℃から２４０℃に昇温しながらエステル交換反応させた後常圧に戻し、リン酸トリメチル０．００８７部を添加し、エステル交換反応を終了させた。
その後重合触媒として酸化ゲルマニウム０．０２１部を加え、混合物を重合容器に移し、常法にて高真空のもと重縮合反応を行い、最終内温が２９０℃まで昇温し反応を終了させ、極限粘度０．７１、融点が２２６℃のポリエステルを得た。
(6) Production of polyester Tetra-n-butyl titanate (0.0025 part as Ti element) can be pressure-reacted in a mixture of 89 parts of dimethyl terephthalate and 11 parts of dimethyl isophthalate and 70 parts of ethylene glycol. Charge into a container, pressurize to 0.07 MPa, let it transesterify while raising the temperature from 140 ° C to 240 ° C, then return to normal pressure, add 0.0087 parts of trimethyl phosphate, and terminate the transesterification reaction It was.
Thereafter, 0.021 part of germanium oxide is added as a polymerization catalyst, the mixture is transferred to a polymerization vessel, a polycondensation reaction is performed under high vacuum in a conventional manner, the final internal temperature is raised to 290 ° C., and the reaction is terminated. A polyester having an intrinsic viscosity of 0.71 and a melting point of 226 ° C. was obtained.
（７）硫酸バリウム粒子の用意
沈降法により製造された平均粒径１．９２μｍの硫酸バリウム粒子を用意した。
(7) Preparation of barium sulfate particles Barium sulfate particles having an average particle diameter of 1.92 μm produced by a sedimentation method were prepared.
［実施例１］
用意した硫酸バリウム粒子を株式会社セイシン企業製気流分級機クラッシールＮ−２０型機にて回転数３０００ｒｐｍ、処理速度２０Ｋｇ／Ｈｒにて風力分級処理し、粗粉と微粉に分級して微粉を除去した。このときの粗粉の収率は７０重量％であった。この粗粉を硫酸バリウム粒子の集合体として用いた。硫酸バリウム粒子の集合体の状態は表１に示すとおりであった。
[Example 1]
The prepared barium sulfate particles are air-classified with an airflow classifier “Classeal N-20” manufactured by Seishin Enterprise Co., Ltd. at a rotational speed of 3000 rpm and a processing speed of 20 Kg / Hr, and are classified into coarse powder and fine powder to remove fine powder. did. The yield of the coarse powder at this time was 70% by weight. This coarse powder was used as an aggregate of barium sulfate particles. The state of the aggregate of barium sulfate particles was as shown in Table 1.
この硫酸バリウム粒子の集合体とポリエステルとを、神戸製鋼所製混錬押出機ＮＥＸＴ−６０型機に、それぞれ定量性を持つフィーダーより連続供給し、６００回転／分、樹脂温度３１０℃にて混錬し、続いて押出機にて２５０℃にてストランド状に押し出し、これをカッティングして、極限粘度数（ＩＶ）０．５５ｄｌ／ｇ、硫酸バリウム粒子濃度４４重量％のポリエステル組成物からなるペレットＡ１を得た。このときのペレットの生産能力（速度）は１２０Ｋｇ／Ｈｒとした。
得られたペレットＡ１を１４０℃で４時間乾燥した後、濾過性評価を行ったところ、濾過圧上昇度（△Ｐ）は０．５４ＭＰａであった。このペレットＡ１を用いてフィルムを製膜した結果を表２に示す。
The aggregate of barium sulfate particles and polyester are continuously fed to the Kobe Steel Kneading Extruder NEXT-60 from a feeder with quantitative properties, mixed at 600 rpm and at a resin temperature of 310 ° C. Kneaded, then extruded into a strand at 250 ° C. by an extruder, and cut into pellets made of a polyester composition having an intrinsic viscosity (IV) of 0.55 dl / g and a barium sulfate particle concentration of 44% by weight. A1 was obtained. The production capacity (speed) of the pellets at this time was 120 kg / hr.
When the obtained pellet A1 was dried at 140 ° C. for 4 hours and then evaluated for filterability, the degree of increase in filtration pressure (ΔP) was 0.54 MPa. Table 2 shows the results of film formation using the pellet A1.
［実施例２］
実施例１の風力分級処理において、実施例１と同様の条件にて風力分級を２回繰り返し、粗粉と微粉に分級して微粉を除去した。このときの粗粉の収率は２回の風力分級を行った後の時点で３０重量％であった。この粗粉を硫酸バリウム粒子の集合体として用い、実施例１と同様にしてポリエステル組成物のペレットＡ２を製造した。なお、硫酸バリウム粒子の集合体の状態は表１に示すとおりであった。
得られたペレットＡ２を１４０℃で４時間乾燥した後、濾過性評価を行ったところ、濾過圧上昇度（△Ｐ）は０．３５ＭＰａであった。このペレットＡ２を用いてフィルムを製膜した結果を表２に示す。
[Example 2]
In the air classification treatment of Example 1, the air classification was repeated twice under the same conditions as in Example 1 to classify into coarse powder and fine powder to remove the fine powder. The yield of the coarse powder at this time was 30% by weight after performing the air classification twice. Using this coarse powder as an aggregate of barium sulfate particles, a polyester composition pellet A2 was produced in the same manner as in Example 1. The state of the aggregate of barium sulfate particles was as shown in Table 1.
The obtained pellet A2 was dried at 140 ° C. for 4 hours and then evaluated for filterability. As a result, the degree of increase in filtration pressure (ΔP) was 0.35 MPa. Table 2 shows the result of forming a film using the pellet A2.
［比較例１］
実施例１において、風力分級後の粗粉に工業用の超音波発生器で超音波処理を１０分間行うことで硫酸バリウム粒子をさらに解砕し、粗粉と微粉に分級して微粉を除去した。このときの粗粉の収率は５０重量％であった。この粗粉を硫酸バリウム粒子の集合体として用い、硫酸バリウム粒子濃度６重量％のポリエステル組成物からなるペレットＢ１を製造した。なお、硫酸バリウム粒子の集合体の状態は表１に示すとおりであった。
得られたペレットＢ１を１４０℃で４時間乾燥した後、濾過性評価を行ったところ、濾過圧上昇度（△Ｐ）は３．８ＭＰａであった。さらに、このペレットＢ１を用いてフィルムを製膜した。製膜性の評価結果を表２に示す。
[Comparative Example 1]
In Example 1, barium sulfate particles were further pulverized by subjecting the coarse powder after wind classification to ultrasonic treatment with an industrial ultrasonic generator for 10 minutes, and classified into coarse powder and fine powder to remove the fine powder. . The yield of the coarse powder at this time was 50% by weight. Using this coarse powder as an aggregate of barium sulfate particles, a pellet B1 made of a polyester composition having a barium sulfate particle concentration of 6% by weight was produced. The state of the aggregate of barium sulfate particles was as shown in Table 1.
The obtained pellet B1 was dried at 140 ° C. for 4 hours and then evaluated for filterability. As a result, the degree of increase in filtration pressure (ΔP) was 3.8 MPa. Furthermore, a film was formed using the pellet B1. Table 2 shows the evaluation results of film forming properties.
［比較例２］
実施例２において、風力分級後の粗粉に工業用の超音波発生器で超音波処理を１０分間行うことで硫酸バリウム粒子をさらに解砕し、粗粉と微粉に分級して微粉を除去した。このときの粗粉の収率は５０重量％であった。この粗粉を硫酸バリウム粒子の集合体として用い、硫酸バリウム粒子濃度６重量％のポリエステル組成物からなるペレットＢ２を得た。硫酸バリウム粒子の集合体の状態は表１に示すとおりであった。
得られたペレットＢ２を１４０℃で４時間乾燥した後、濾過性評価を行ったところ、濾過圧上昇度（△Ｐ）は５ＭＰａを超えた。さらに、このペレットＢ１を用いてフィルムを製膜した。製膜性の評価結果を表２に示す。
[Comparative Example 2]
In Example 2, barium sulfate particles were further pulverized by subjecting the coarse powder after wind classification to ultrasonic treatment with an industrial ultrasonic generator for 10 minutes, and classified into coarse powder and fine powder to remove fine powder. . The yield of the coarse powder at this time was 50% by weight. Using this coarse powder as an aggregate of barium sulfate particles, a pellet B2 made of a polyester composition having a barium sulfate particle concentration of 6% by weight was obtained. The state of the aggregate of barium sulfate particles was as shown in Table 1.
When the obtained pellet B2 was dried at 140 ° C. for 4 hours and then evaluated for filterability, the degree of increase in filtration pressure (ΔP) exceeded 5 MPa. Furthermore, a film was formed using the pellet B1. Table 2 shows the evaluation results of film forming properties.
本発明の積層フィルムは、光反射のために面光源に組み込まれる板状材として好ましく用いることができる。例えば、液晶表示装置におけるエッジ型バックライトの反射板、直下型バックライトの面光源の反射板、および冷陰極管の周囲のランプリフレクター等の用途に好ましく用いることができる。 The laminated film of the present invention can be preferably used as a plate-like material incorporated in a surface light source for light reflection. For example, it can be preferably used for applications such as a reflector for an edge type backlight in a liquid crystal display device, a reflector for a surface light source of a direct type backlight, and a lamp reflector around a cold cathode tube.
Claims (3)
硫酸バリウム粒子として、小粒径側から積算した５０％体積粒径（Ｄ５０）が１．０〜３．０μｍの範囲にあり、小粒径側から積算した９０％体積粒径（Ｄ９０）と１０％体積粒径（Ｄ１０）との比（Ｄ９０／Ｄ１０）が１０以下であり、粒径０．５μｍ以下の粒子が全粒子に占める割合が８体積％以下である硫酸バリウム粒子の集合体を用いる、As barium sulfate particles, the 50% volume particle size (D50) integrated from the small particle size side is in the range of 1.0 to 3.0 μm, and the 90% volume particle size (D90) integrated from the small particle size side is 10 An aggregate of barium sulfate particles having a ratio (D90 / D10) to% volume particle diameter (D10) of 10 or less and a ratio of particles having a particle diameter of 0.5 μm or less to all particles being 8 volume% or less is used. ,
積層フィルムの製造方法。A method for producing a laminated film.
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