JP2008230138A - Foamed resin structural material, optical reflecting board and method for producing foamed resin structural material - Google Patents
Foamed resin structural material, optical reflecting board and method for producing foamed resin structural material Download PDFInfo
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本発明は、微細な気泡を有し、かつ表面硬度に優れる樹脂発泡構造体に関する。本発明の樹脂発泡構造体は、光反射板、外装材、筐体材料などに好適に使用される。 The present invention relates to a resin foam structure having fine bubbles and excellent surface hardness. The resin foam structure of the present invention is suitably used for a light reflecting plate, an exterior material, a housing material, and the like.
従来、微細な気泡を有する種々の樹脂発泡体製品あるいはその製造方法が提案されている（例えば、特許文献１、２参照）。特許文献１は、熱可塑性ポリエステル樹脂シートとセパレータとを重ねて巻くことによりロールを形成し、該ロールを加圧不活性ガス雰囲気中に保持して熱可塑性ポリエステル樹脂シートに不活性ガスを含有させて結晶化度を３０％以上にする工程と、不活性ガスを含有させた熱可塑性ポリエステル樹脂シートを常圧下で加熱して発泡させる工程とを具備する熱可塑性ポリエステル樹脂発泡シートの製造方法を開示している。特許文献２は、平均気泡径５０μｍ以下の微細気泡を含有し、厚さが２００μｍ以上、比重が０．７以下の熱可塑性ポリエステル発泡体からなる光反射板を開示している。 Conventionally, various resin foam products having fine bubbles or methods for producing the same have been proposed (see, for example, Patent Documents 1 and 2). In Patent Document 1, a roll is formed by winding a thermoplastic polyester resin sheet and a separator, and the roll is held in a pressurized inert gas atmosphere so that the thermoplastic polyester resin sheet contains an inert gas. Disclosed is a method for producing a thermoplastic polyester resin foam sheet, comprising: a step of crystallinity of 30% or more; and a step of heating and foaming a thermoplastic polyester resin sheet containing an inert gas under normal pressure. is doing. Patent Document 2 discloses a light reflection plate made of a thermoplastic polyester foam containing fine bubbles having an average cell diameter of 50 μm or less, a thickness of 200 μm or more, and a specific gravity of 0.7 or less.
しかし、特許文献１の製造方法により得られる樹脂発泡体は、表面が傷付きやすく、表面硬度が十分とは言えない。そこで、樹脂発泡体の表面硬度を高めるために、樹脂発泡体表面への塗料塗布、樹脂発泡体表面への未発泡樹脂シートの接着あるいはラミネートなどの対策が採られているが、それらは全て樹脂発泡体への後加工であることから、コスト増の原因となり、また、樹脂発泡体と表面硬度向上用材料との密着性が十分ではないため、その密着界面から表面硬度向上用材料が剥離する問題がある。 However, the resin foam obtained by the production method of Patent Document 1 is easily scratched on the surface, and the surface hardness is not sufficient. Therefore, in order to increase the surface hardness of the resin foam, measures such as coating of the resin foam surface, adhesion of an unfoamed resin sheet to the resin foam surface, or laminating are taken. Since it is post-processing to foam, it causes an increase in cost, and since the adhesion between the resin foam and the surface hardness improving material is not sufficient, the surface hardness improving material peels from the adhesion interface. There's a problem.
また、特許文献２の光反射板は、気泡径が小さく、光反射率が高いため、液晶テレビや電飾看板の光反射板として多く利用されているが、ポリエステル系樹脂の共通の欠点である紫外線劣化により、長期間が経過すると光反射板が茶色に変色することがあり、そのため樹脂に紫外線吸収剤を練り込んだり、紫外線吸収剤を混合した塗料を光反射板表面に塗布したりする対策が採られているが、この対策によるコスト増は免れない。 In addition, the light reflecting plate of Patent Document 2 has a small bubble diameter and high light reflectivity, and thus is widely used as a light reflecting plate for liquid crystal televisions and electric signboards, but is a common drawback of polyester resins. Due to UV degradation, the light reflector may turn brown over a long period of time. Therefore, measures to knead the UV absorber into the resin or apply paint mixed with the UV absorber to the surface of the light reflector. However, an increase in costs due to this measure is inevitable.
本発明は、前述した事情に鑑みてなされたもので、微細な気泡を有し、かつ表面硬度に優れ、光反射板、外装材、筐体材料などに好適に使用される樹脂発泡構造体を安価に提供することを第１の目的とする。また、本発明は、微細な気泡を有し、かつ表面硬度に優れるとともに、紫外線により劣化しにくく、光反射板、外装材、筐体材料などに好適に使用される樹脂発泡構造体を安価に提供することを第２の目的とする。 The present invention has been made in view of the above-described circumstances, and has a resin foam structure that has fine bubbles and is excellent in surface hardness and is suitably used for a light reflecting plate, an exterior material, a housing material, and the like. The first object is to provide it at low cost. In addition, the present invention provides a resin foam structure that has fine bubbles, has excellent surface hardness, is hardly deteriorated by ultraviolet rays, and is suitably used for light reflectors, exterior materials, housing materials, and the like. The second purpose is to provide it.
本発明者は、前記目的を達成するために種々検討を行った結果、微細発泡体の両面に非晶性樹脂層を積層して樹脂発泡構造体を形成した場合、この樹脂発泡構造体の表面硬度が高くなることを見出した。 As a result of various investigations to achieve the above object, the present inventors have found that when a resin foam structure is formed by laminating an amorphous resin layer on both sides of a fine foam, the surface of the resin foam structure It has been found that the hardness increases.
本発明は、上記知見に基づいてなされたもので、下記（１）〜（７）に示す樹脂発泡構造体、光反射板および樹脂発泡構造体の製造方法を提供する。
（１）平均気泡径が３０μｍ以下である微細発泡体の両面に、非晶性樹脂層を積層してなることを特徴とする樹脂発泡構造体。
（２）前記非晶性樹脂層は発泡層と未発泡層とからなる２層構造を有し、前記発泡層を前記微細発泡体側に配置したことを特徴とする（１）の樹脂発泡構造体。
（３）前記非晶性樹脂層の発泡層の平均気泡径は０．５μｍ以上５０μｍ以下であることを特徴とする（２）の樹脂発泡構造体。
（４）前記非晶性樹脂層はポリアリレート樹脂を含むことを特徴とする（１）〜（３）の樹脂発泡構造体。
（５）前記非晶性樹脂層は耐紫外線剤を含むことを特徴とする（１）〜（４）の樹脂発泡構造体。
（６）（１）〜（５）の樹脂発泡構造体からなることを特徴とする光反射板。
（７）（１）〜（５）の樹脂発泡構造体の製造方法であって、微細発泡体の原反シートの両面に非晶性樹脂層の原反シートを積層してなる多層シートにガス発泡剤を浸透させ、次いで前記多層シートにおける非晶性樹脂層の原反シートの外側部分のガス抜きを行った後、前記多層シートを発泡させることを特徴とする樹脂発泡構造体の製造方法。
This invention was made | formed based on the said knowledge, and provides the manufacturing method of the resin foam structure shown in following (1)-(7), a light reflection board, and a resin foam structure.
(1) A resin foam structure comprising an amorphous resin layer laminated on both surfaces of a fine foam having an average cell diameter of 30 μm or less.
(2) The resin foam structure according to (1), wherein the amorphous resin layer has a two-layer structure including a foam layer and an unfoam layer, and the foam layer is disposed on the fine foam side. .
(3) The resin foam structure according to (2), wherein an average cell diameter of the foamed layer of the amorphous resin layer is 0.5 μm or more and 50 μm or less.
(4) The resin foam structure according to any one of (1) to (3), wherein the amorphous resin layer contains a polyarylate resin.
(5) The resin foam structure according to any one of (1) to (4), wherein the amorphous resin layer contains a UV-resistant agent.
(6) A light reflecting plate comprising the resin foam structure of (1) to (5).
(7) A method for producing a resin foam structure according to (1) to (5), wherein a gas is applied to a multilayer sheet formed by laminating a raw sheet of an amorphous resin layer on both surfaces of a fine foam original sheet. A method for producing a resin foam structure, comprising: impregnating a foaming agent, and then degassing an outer portion of a raw sheet of an amorphous resin layer in the multilayer sheet, and then foaming the multilayer sheet.
本発明の樹脂発泡構造体は、微細な気泡を有し、かつ表面硬度に優れている。また、本発明の樹脂発泡構造体は、（７）の製造方法により容易に製造することができ、この製造方法によれば、複合構造体でありながら微細発泡体と非晶性樹脂層との接合界面での剥離が生じにくく、光反射板として好適に使用することができる樹脂発泡構造体を得ることができる。さらに、耐紫外線剤を含む非晶性樹脂層を用いれば、紫外線に対して強い樹脂発泡構造体を得ることができる。 The resin foam structure of the present invention has fine bubbles and is excellent in surface hardness. Further, the resin foam structure of the present invention can be easily produced by the production method (7). According to this production method, the fine foam and the amorphous resin layer are formed while being a composite structure. It is difficult to cause peeling at the bonding interface, and a resin foam structure that can be suitably used as a light reflecting plate can be obtained. Furthermore, if an amorphous resin layer containing an ultraviolet resistant agent is used, a resin foam structure strong against ultraviolet rays can be obtained.
以下、本発明につきさらに詳しく説明する。本発明の樹脂発泡構造体は、樹脂からなる微細発泡体の両面に非晶性樹脂層を積層したものである。この場合、樹脂発泡構造体の中心層である微細発泡体は、その断面の平均気泡径が３０μｍ以下である必要がある。３０μｍより大きい気泡径を持つ発泡体では、それ自体の強度があまりにも低いため、表面硬度を高めるために配置した非晶性樹脂層をよほど厚くしない限り、鋭利な物体で傷つけられたときに発泡体が非晶性樹脂層ごと破けてしまうからである。 Hereinafter, the present invention will be described in more detail. The resin foam structure of the present invention is obtained by laminating an amorphous resin layer on both surfaces of a fine foam made of resin. In this case, the fine foam which is the central layer of the resin foam structure needs to have an average cell diameter of 30 μm or less in the cross section. In the foam having a cell diameter larger than 30 μm, the strength of the foam itself is so low that it is foamed when it is damaged by a sharp object unless the amorphous resin layer arranged to increase the surface hardness is made too thick. This is because the body is torn together with the amorphous resin layer.
また、樹脂発泡体を光反射板として用いる場合、発泡体の平均気泡径が１０μｍ以下、より好ましくは３μｍ以下である場合に光反射率が高くなることが知られている。したがって、本発明においても、樹脂発泡構造体を光反射板として用いる場合、微細発泡体の断面の平均気泡径は１０μｍ以下、特に３μｍ以下であることが好ましい。 Moreover, when using a resin foam as a light reflection board, it is known that a light reflectance will become high when the average bubble diameter of a foam is 10 micrometers or less, More preferably, it is 3 micrometers or less. Therefore, also in the present invention, when the resin foam structure is used as a light reflecting plate, the average cell diameter of the cross section of the fine foam is preferably 10 μm or less, particularly 3 μm or less.
微細発泡体に用いる樹脂材料としては、特に制限はないが、微細な気泡を得やすいことなどから、熱可塑性飽和ポリエステルである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、ポリブチレンテレフタレート、ポリブチレンナフタレート、ポリトリメチルテレフタレートや、汎用エンジニアリングプラスチックであるポリカーボネート、ポリアリレート、また、スーパーエンジニアリングプラスチックであるポリフェニレンサルファイド、ポリエーテルサルフォン、ポリエーテルイミド、ポリサルフォン、さらには、アクリル樹脂やポリスチレンなどを好適に用いることができる。 The resin material used for the fine foam is not particularly limited. However, since it is easy to obtain fine bubbles, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polytrimethyl are the thermoplastic saturated polyesters. For example, terephthalate, polycarbonate, polyarylate, which are general-purpose engineering plastics, polyphenylene sulfide, polyethersulfone, polyetherimide, polysulfone, and acrylic resins, polystyrene, etc., which are super engineering plastics, can be preferably used.
本発明においては、微細発泡体の特性に影響を及ぼさない範囲で、微細発泡体の発泡前の樹脂に、結晶化核剤、結晶化促進剤、気泡化核剤、酸化防止剤、帯電防止剤、紫外線防止剤、光安定剤、蛍光増白剤、顔料、染料、相溶化剤、滑剤、強化剤、難燃剤、架橋剤、架橋助剤、可塑剤、増粘剤、減粘剤などの各種添加剤を配合してもよい。 In the present invention, a crystallization nucleating agent, a crystallization accelerator, a bubble nucleating agent, an antioxidant, and an antistatic agent are added to the resin before the foaming of the fine foam within a range that does not affect the characteristics of the fine foam. , UV inhibitors, light stabilizers, fluorescent brighteners, pigments, dyes, compatibilizers, lubricants, reinforcing agents, flame retardants, crosslinking agents, crosslinking aids, plasticizers, thickeners, thickeners, etc. You may mix | blend an additive.
本発明において、非晶性樹脂層に用いる樹脂材料の種類に特に制限はなく、熱可塑性樹脂であってもよく、熱硬化性樹脂であってもよいが、扱い易さの点で熱可塑性非晶性樹脂が好ましい。熱可塑性非晶性樹脂としては、例えば、アクリル樹脂、ポリスチレン、ポリカーボネート、非晶性ポリアリレート、ポリエーテルサルフォン、ポリエーテルイミド、ポリサルフォン、シクロポリオレフィンなどを挙げることができるが、中でも非晶性ポリアリレートが最も好ましい。非晶性ポリアリレート樹脂は、紫外線が照射された際に転移を起こし、ポリマー表面に紫外線吸収骨格を形成するため、非晶性ポリアリレート自身の内部および微細発泡体を紫外線劣化から守ることができるからである。さらに、非晶性樹脂層に非晶性ポリアリレートを用いた場合、難燃剤の配合なしでもＵＬ９４難燃試験においてＶ−２を示す難燃効果を持つので、樹脂発泡構造体の難燃効果を上げることができるからである。 In the present invention, the type of the resin material used for the amorphous resin layer is not particularly limited, and may be a thermoplastic resin or a thermosetting resin. A crystalline resin is preferred. Examples of the thermoplastic amorphous resin include acrylic resin, polystyrene, polycarbonate, amorphous polyarylate, polyethersulfone, polyetherimide, polysulfone, and cyclopolyolefin. Arylate is most preferred. Amorphous polyarylate resin undergoes transition when irradiated with ultraviolet rays, and forms an ultraviolet absorbing skeleton on the polymer surface. Therefore, the amorphous polyarylate itself and the fine foam can be protected from ultraviolet degradation. Because. Furthermore, when amorphous polyarylate is used in the amorphous resin layer, it has a flame retardant effect showing V-2 in the UL 94 flame retardant test even without the addition of a flame retardant. Because it can be raised.
なお、非晶性樹脂か否かの判別は、一般的な手法でかまわない。例えば、示差走査熱量測定装置（ＤＳＣ）で樹脂を昇温してゆき、ガラス転移温度変曲点より高い温度領域で結晶溶融を示す吸熱ピークが存在しないことで確認してもよいし、溶融後に１０℃／分以上のゆっくりとした速度で降温していき、融点とガラス点移転温度との間に結晶化による発熱ピークがないことで確認してもよい。 It should be noted that it is possible to determine whether the resin is an amorphous resin by a general method. For example, the temperature of the resin is raised with a differential scanning calorimeter (DSC), and it may be confirmed that there is no endothermic peak indicating crystal melting in a temperature range higher than the glass transition temperature inflection point. The temperature may be lowered at a slow rate of 10 ° C./min or more, and it may be confirmed that there is no exothermic peak due to crystallization between the melting point and the glass point transition temperature.
本発明における重要な点は、好ましくは、非晶性樹脂層の構造は、未発泡層と発泡層とが重なった２層構造となっており、発泡層が微細発泡体側に配置され、未発泡層が樹脂発泡構造体の外側に配置されることである。当初、本発明者は、微細発泡体の原反の両面に非晶性樹脂層を設け、非晶性樹脂を発泡させることなく、微細発泡体を得ようと努力を重ねた。しかしながら、非晶性樹脂層を全て未発泡状態にすると、非晶性樹脂層と微細発泡体との界面で剥離が生じ、良好な樹脂発泡構造体を得ることができなかった。その後、本発明者は、非晶性樹脂層が上記２層構造を有し、発泡層を微細発泡体側に配置した場合、非晶性樹脂層と微細発泡体との界面で剥離が生じにくいことを見出した。これは、本発明者は、非晶性樹脂層と微細発泡体との接面近傍に気泡が存在することによって、ひずみが緩和され、良好な樹脂発泡構造体が形成されるのではないかと推測している。そのため、非晶性樹脂層の気泡は、面内方向において均一に分散されていることが好ましい。なお、樹脂発泡構造体の外側に非晶性樹脂層の発泡層があると、本発明の目的である表面硬度の高い樹脂発泡構造体を得ることができない。 The important point in the present invention is that preferably the structure of the amorphous resin layer is a two-layer structure in which the non-foamed layer and the foamed layer overlap, and the foamed layer is disposed on the fine foam side, The layer is disposed outside the resin foam structure. Initially, the inventor made an effort to obtain a fine foam without providing an amorphous resin layer on both sides of the raw material of the fine foam and foaming the amorphous resin. However, if all of the amorphous resin layer is in an unfoamed state, peeling occurs at the interface between the amorphous resin layer and the fine foam, and a good resin foam structure cannot be obtained. Thereafter, the present inventor found that when the amorphous resin layer has the above two-layer structure and the foamed layer is disposed on the fine foam side, peeling is unlikely to occur at the interface between the amorphous resin layer and the fine foam. I found. This is because the present inventor presumes that the presence of air bubbles in the vicinity of the contact surface between the amorphous resin layer and the fine foam may ease the distortion and form a good resin foam structure. is doing. Therefore, it is preferable that the bubbles in the amorphous resin layer are uniformly dispersed in the in-plane direction. In addition, if there is a foamed layer of an amorphous resin layer outside the resin foam structure, it is not possible to obtain a resin foam structure having a high surface hardness, which is an object of the present invention.
非晶性樹脂層に存在する気泡の気泡径は、０．５μｍ以上５０μｍ以下であることが好ましい。気泡径が５０μｍを超える大きな気泡では、樹脂発泡構造体の表面の平滑さを阻害する上、気泡のひずみが大きすぎて、非晶性樹脂層と微細発泡体との間の界面剥離を生じかねないからである。また、気泡径が０．５μｍより小さな気泡の場合も、非晶性樹脂層と微細発泡体との間の界面剥離が生じやすくなる。これは、本発明者は、気泡が小さすぎることで、ひずみの緩衝になりにくくなるためではないかと推測している。 The bubble diameter of the bubbles present in the amorphous resin layer is preferably 0.5 μm or more and 50 μm or less. In the case of large bubbles with a bubble diameter exceeding 50 μm, the smoothness of the surface of the resin foam structure may be hindered, and the distortion of the bubbles may be too great, causing interfacial delamination between the amorphous resin layer and the fine foam. Because there is no. Also, in the case of bubbles having a bubble diameter smaller than 0.5 μm, interfacial peeling between the amorphous resin layer and the fine foam tends to occur. The inventor presumes that this is because the bubbles are too small to become a strain buffer.
本発明における非晶性樹脂層には、紫外線吸収剤、紫外線反射剤などの耐紫外線剤を練りこんでおくことで、樹脂発泡構造体の耐紫外線性を向上させることができる。また、本発明における非晶性樹脂層には、非晶性樹脂層の特性に影響を及ぼさない範囲で、酸化防止剤、帯電防止剤、光安定剤、蛍光増白剤、顔料、染料、相溶化剤、滑剤、強化剤、難燃剤、架橋剤、架橋助剤、可塑剤、増粘剤、減粘剤などの各種添加剤を配合してもよい。 In the amorphous resin layer in the present invention, ultraviolet resistance of the resin foam structure can be improved by kneading an ultraviolet resistant agent such as an ultraviolet absorber or an ultraviolet reflector. In addition, the amorphous resin layer in the present invention includes an antioxidant, an antistatic agent, a light stabilizer, a fluorescent whitening agent, a pigment, a dye, a phase, and the like within a range that does not affect the characteristics of the amorphous resin layer. Various additives such as a solubilizer, a lubricant, a reinforcing agent, a flame retardant, a cross-linking agent, a cross-linking aid, a plasticizer, a thickener, and a thickener may be blended.
本発明の樹脂発泡構造体を製造する方法は特に限定されないが、量産性を考慮すると、例えば以下のような方法を用いることが好ましい。すなわち、微細発泡体用の樹脂原反を中心層とし、非晶性樹脂層用の樹脂原反を上下層とした三層押出しで多層シートを作製し、この多層シートとセパレータとを重ねて巻くことによりロールを形成し、このロールを加圧不活性ガス雰囲気中に保持して多層シートに不活性ガスを含有させ、さらに不活性ガスを含有させた多層シートを常圧下で放置することにより、非晶性樹脂層用の樹脂原反の外側部分に含まれる高濃度不活性ガスを抜いた後、多層シートを微細発泡体用樹脂の軟化温度以上に加熱して発泡させる、という方法を好適に用いることができる。この場合、非晶性樹脂は、浸透させた不活性ガスの脱離速度が速いので、常圧下放置で容易にガス抜けが発生し、樹脂発泡構造体の表面部分となる未発泡非晶性樹脂層を得ることができる。 The method for producing the resin foam structure of the present invention is not particularly limited, but considering mass productivity, for example, the following method is preferably used. That is, a multilayer sheet is produced by three-layer extrusion using a resin raw material for a fine foam as a central layer and a resin raw material for an amorphous resin layer as upper and lower layers, and the multilayer sheet and the separator are overlapped and wound. By forming a roll by this, holding the roll in a pressurized inert gas atmosphere, containing the inert gas in the multilayer sheet, and further leaving the multilayer sheet containing the inert gas under normal pressure, A method in which after the high-concentration inert gas contained in the outer portion of the raw resin for the amorphous resin layer is removed, the multilayer sheet is heated to a temperature equal to or higher than the softening temperature of the resin for the fine foam to be foamed suitably. Can be used. In this case, the amorphous resin has a high desorption rate of the permeated inert gas, so that the outgassing easily occurs when left under normal pressure, and the non-foamed amorphous resin that becomes the surface portion of the resin foam structure A layer can be obtained.
上記不活性ガスとしては、ヘリウム、窒素、二酸化炭素、アルゴンなどが挙げられる。樹脂へのガス浸透性（速度、溶解度）を考慮すると、二酸化炭素がより好ましい。また、多層シートが不活性ガス飽和状態になるまでの不活性ガス浸透時間および不活性ガス浸透量は、発泡させる樹脂の種類、不活性ガスの種類、浸透圧力およびシートの厚さによって異なる。 Examples of the inert gas include helium, nitrogen, carbon dioxide, and argon. In consideration of gas permeability (rate, solubility) to the resin, carbon dioxide is more preferable. Further, the inert gas permeation time and the inert gas permeation amount until the multilayer sheet is saturated with the inert gas vary depending on the type of resin to be foamed, the type of inert gas, the permeation pressure, and the thickness of the sheet.
なお、上述した樹脂発泡構造体の製造方法では、多層シートとセパレータとからなるロールを、加圧不活性ガス雰囲気中に保持して多層シートに不活性ガスを含有させる前に、多層シートにエタノールなどの有機溶剤を含有させてもよい。 In the method for producing the resin foam structure described above, the roll made of the multilayer sheet and the separator is held in a pressurized inert gas atmosphere, and the multilayer sheet is made to contain ethanol before containing the inert gas. An organic solvent such as
次に、実施例によって本発明をさらに具体的に示すが、本発明は下記実施例に限定されるものではない。なお、得られた樹脂発泡構造体の各種特性の測定および評価は以下の通りとした。
（平均気泡径）
ＡＳＴＭ Ｄ３５７６−７７に準じて求めた。すなわち、シートの断面のＳＥＭ写真を撮影し、ＳＥＭ写真上に水平方向と垂直方向に直線を引き、直線が横切る気泡の弦の長さｔを平均した。写真の倍率をＭとして、下記式に代入して平均気泡径ｄを求めた。
ｄ＝ｔ／（０．６１６×Ｍ）
（表面硬度）
ＪＩＳ Ｋ ５６００−５−４に従い、鉛筆引っかき試験を行なった。
（剥離試験）
発泡構造体シートを２０ｍｍＲに曲げた後、微細発泡体と非晶性樹脂層との間に剥離が生じているかどうかをルーペで観察した。
（光反射率）
分光光度計（ＵＶ−３１０１ＰＣ：島津製作所社製）を用いて、５５０ｎｍの波長における反射率を測定した。なお、本実施例では、硫酸バリウムの微粉末を固めた白板の全反射率を１００％として、各々の樹脂発泡構造体の全反射率を相対値で示している。
（紫外線劣化試験）
スーパーＵＶ（アイスーパーＵＶテスター ＳＵＶ−Ｗ１５１：岩崎電気社製）にて、８０℃、１００ｍＷ、サンプル表面までの照射距離２３５ｍｍで、紫外線照射を行ない、照射後の色調を目視観察した。また、紫外線照射後のサンプルを２つ折りにし、折り目にクラックが生じているかどうかを目視観察した。
Next, although an example shows the present invention still more concretely, the present invention is not limited to the following example. In addition, the measurement and evaluation of various characteristics of the obtained resin foam structure were as follows.
(Average bubble diameter)
It calculated | required according to ASTMD3576-77. That is, an SEM photograph of the cross section of the sheet was taken, a straight line was drawn on the SEM photograph in the horizontal direction and the vertical direction, and the length t of the bubble chord crossed by the straight line was averaged. Assuming that the magnification of the photograph is M, the average bubble diameter d was determined by substituting it into the following equation.
d = t / (0.616 × M)
(surface hardness)
A pencil scratch test was performed according to JIS K 5600-5-4.
(Peel test)
After the foam structure sheet was bent to 20 mmR, it was observed with a loupe whether peeling occurred between the fine foam and the amorphous resin layer.
(Light reflectance)
The reflectance at a wavelength of 550 nm was measured using a spectrophotometer (UV-3101PC: manufactured by Shimadzu Corporation). In this example, the total reflectance of each resin foam structure is shown as a relative value, assuming that the total reflectance of a white plate made of hard barium sulfate fine powder is 100%.
(UV degradation test)
Ultraviolet rays were irradiated with super UV (eye super UV tester SUV-W151: manufactured by Iwasaki Electric Co., Ltd.) at 80 ° C., 100 mW, and an irradiation distance to the sample surface of 235 mm, and the color tone after irradiation was visually observed. Moreover, the sample after ultraviolet irradiation was folded in half, and it was visually observed whether or not a crack occurred in the fold.
（実施例１）
ポリエチレンテレフタレート（グレード＝ＳＡ−１２０６：ユニチカ社製）に、官能基を有するスチレン−エチレン・ブチレン−スチレンブロック共重合体（ＳＥＢＳ、ダイナロン８６３０Ｐ：ＪＳＲ社製）を１質量部添加して混練した樹脂を中心層とし、ポリアリレート（グレード＝Ｕ−１００：ユニチカ社製）を上下層とする三層押出しを行ない、０．８ｍｍ厚×３００ｍｍ幅×６０ｍ長さの多層シートを成形した。ポリエチレンテレフタレート層は０．５ｍｍ厚、上下のポリアリレート層はそれぞれ０．１５ｍｍ厚であった。この多層シートと、１６０μｍ厚さ×２９０ｍｍ幅×６０ｍ長さ、目付量５５ｇ／ｍ２のオレフィン系不織布のセパレータ（グレード＝ＦＴ３００：日本バイリーン製）を重ねて、多層シートの表面同士が接触する部分がないように巻いてロール状にした。
(Example 1)
Resin obtained by adding 1 part by mass of a styrene-ethylene-butylene-styrene block copolymer having a functional group (SEBS, Dynalon 8630P: manufactured by JSR) to polyethylene terephthalate (grade = SA-1206: manufactured by Unitika) Was used as a central layer, and a three-layer extrusion was carried out using polyarylate (grade = U-100: manufactured by Unitika) as upper and lower layers to form a multilayer sheet of 0.8 mm thickness × 300 mm width × 60 m length. The polyethylene terephthalate layer was 0.5 mm thick, and the upper and lower polyarylate layers were each 0.15 mm thick. This multilayer sheet is overlapped with an olefin-based nonwoven fabric separator (grade = FT300: manufactured by Nippon Vilene) having a thickness of 160 μm × 290 mm width × 60 m and a basis weight of 55 g / m 2 , and the surfaces of the multilayer sheets are in contact with each other It was rolled into a roll shape so that there was not.
その後、上記ロールを圧力容器に入れ、炭酸ガスで６ＭＰａに加圧し、多層シートに炭酸ガスを浸透させた。多層シートへの炭酸ガスの浸透時間は７２時間とした。次に、圧力容器からロールを取り出し、２０分放置することで多層シート表面のガス抜きを行なった。さらに、セパレータを取り除きながら多層シートだけを引き出し、図１に示すように、時間にして２０分間の多層シート表面のガス抜き工程を経た後、２００℃に設定した熱風循環式発泡炉に発泡時間が１分となるように多層シートを連続的に供給して発泡させた。 Thereafter, the roll was put in a pressure vessel, pressurized to 6 MPa with carbon dioxide gas, and carbon dioxide gas was permeated into the multilayer sheet. The carbon dioxide gas permeation time into the multilayer sheet was 72 hours. Next, the roll was taken out from the pressure vessel and left for 20 minutes to degas the multilayer sheet surface. Further, only the multilayer sheet is pulled out while removing the separator, and as shown in FIG. 1, after passing through the degassing process on the surface of the multilayer sheet for 20 minutes, the foaming time is set in a hot-air circulating foaming furnace set at 200 ° C. The multilayer sheet was continuously supplied and foamed so as to be 1 minute.
得られた樹脂発泡構造体の中心層であるポリエチレンテレフタレート層は均一に発泡しており、平均気泡径が１．５μｍと非常に微細であった。また、上下層であるポリアリレート層は、樹脂発泡構造体表面から１２０μｍまでは気泡が確認されず、ポリエチレンテレフタレート層との接面側５０μｍ厚さが発泡層となっていた。気泡はポリエチレンテレフタレート層接面近傍で５μｍ、ポリアリレート未発泡層近傍で２５μｍと、厚さ方向に関しては傾斜傾向にあったが、面内方向には均一に気泡が分散されていた。ポリアリレート発泡層の平均気泡径は１８μｍであった。樹脂発泡構造体の厚さは１．１４ｍｍであり、鉛筆硬度はＨであった。剥離試験で、剥離は観測されなかった。また、光反射率は９９．７％と非常に高い値を示した。さらに、紫外線劣化試験後のサンプルは薄い黄色であり、２つ折りにしてもクラックは観察されなかった。 The polyethylene terephthalate layer, which is the central layer of the obtained resin foam structure, was uniformly foamed, and the average cell diameter was as very fine as 1.5 μm. Further, in the polyarylate layer as the upper and lower layers, no bubbles were confirmed up to 120 μm from the surface of the resin foam structure, and the thickness of 50 μm on the contact surface side with the polyethylene terephthalate layer was a foamed layer. The bubbles were inclined in the thickness direction as 5 μm near the polyethylene terephthalate layer contact surface and 25 μm near the polyarylate unfoamed layer, but the bubbles were uniformly dispersed in the in-plane direction. The average cell diameter of the polyarylate foam layer was 18 μm. The thickness of the resin foam structure was 1.14 mm, and the pencil hardness was H. In the peel test, no peel was observed. Further, the light reflectance was as high as 99.7%. Furthermore, the sample after the UV degradation test was light yellow, and no cracks were observed even when folded in half.
（実施例２）
ポリカーボネート（グレード＝Ｌ１２５０：帝人化成社製）１００質量部に、官能基を有するＳＥＢＳ（ダイナロン８６３０Ｐ：ＪＳＲ社製）を１質量部添加して混練した樹脂を中心層としたこと以外は、実施例１と同様に多層シートを作製し、樹脂発泡構造体を得た。
(Example 2)
Example except that 1 part by mass of SEBS having a functional group (Dynalon 8630P: made by JSR) was added to 100 parts by mass of polycarbonate (grade = L1250: made by Teijin Chemicals Ltd.) and the resin was kneaded as a central layer. A multilayer sheet was produced in the same manner as in Example 1 to obtain a resin foam structure.
得られた樹脂発泡構造体の中心層であるポリカーボネート層は均一に発泡しており、平均気泡径が５μｍと微細であった。また、上下層であるポリアリレート層は、樹脂発泡構造体表面から１００μｍまでは気泡が確認されず、ポリカーボネート層との接面側７０μｍ厚さが発泡層となっていた。気泡はポリカーボネート層接面近傍で８μｍ、ポリアリレート未発泡層近傍で３３μｍと、厚さ方向に関しては傾斜傾向にあったが、面内方向には均一に気泡が分散されていた。ポリアリレート発泡層の平均気泡径は２１μｍであった。樹脂発泡構造体の厚さは１．２ｍｍであり、鉛筆硬度はＨであった。剥離試験で、剥離は観測されなかった。また、光反射率は８６．７％と高い値を示した。さらに、紫外線劣化試験後のサンプルは薄い黄色であり、２つ折りにしてもクラックは観察されなかった。 The polycarbonate layer, which is the central layer of the obtained resin foam structure, was uniformly foamed, and the average cell diameter was as fine as 5 μm. Further, in the polyarylate layer as the upper and lower layers, no bubbles were confirmed up to 100 μm from the surface of the resin foam structure, and the thickness of 70 μm on the side in contact with the polycarbonate layer was a foamed layer. The bubbles were inclined in the thickness direction as 8 μm near the polycarbonate layer contact surface and 33 μm near the polyarylate unfoamed layer, but the bubbles were uniformly dispersed in the in-plane direction. The average cell diameter of the polyarylate foam layer was 21 μm. The thickness of the resin foam structure was 1.2 mm, and the pencil hardness was H. In the peel test, no peel was observed. The light reflectance was as high as 86.7%. Further, the sample after the UV degradation test was pale yellow, and no cracks were observed even when folded in half.
（実施例３）
ポリカーボネート（グレード＝Ｌ１２５０：帝人化成社製）に紫外線吸収剤（グレード＝チヌビン１５７７：チバ・スペシャルティ・ケミカルズ社製）を０．５質量％添加したものを非晶性樹脂に用いたこと以外は、実施例１と同様にして樹脂発泡構造体を得た。
(Example 3)
Except for using 0.5% by mass of an ultraviolet absorber (grade = Tinuvin 1577: manufactured by Ciba Specialty Chemicals) for polycarbonate (grade = L1250: manufactured by Teijin Chemicals Ltd.) as an amorphous resin, A resin foam structure was obtained in the same manner as in Example 1.
得られた樹脂発泡構造体の中心層であるポリエチレンテレフタレート層は均一に発泡しており、平均気泡径が１．５μｍと微細であった。また、上下層であるポリカーボネート層は、樹脂発泡構造体表面から１３０μｍまでは気泡が確認されず、ポリエチレンテレフタレート層との接面側３０μｍ厚さが発泡層となっていた。気泡はポリエチレンテレフタレート層接面近傍で４μｍ、ポリカーボネート未発泡層近傍で１８μｍと、厚さ方向に関しては傾斜傾向にあったが、面内方向には均一に気泡が分散されていた。ポリアリレート発泡層の平均気泡径は１３μｍであった。樹脂発泡構造体の厚さは１．１２ｍｍであり、鉛筆硬度はＨであった。剥離試験で、剥離は観測されなかった。また、光反射率は９９．８％と非常に高い値を示した。さらに、紫外線劣化試験後のサンプルは薄い黄色であり、２つ折りにしてもクラックは観察されなかった。 The polyethylene terephthalate layer as the central layer of the obtained resin foam structure was uniformly foamed, and the average cell diameter was as fine as 1.5 μm. In the polycarbonate layer as the upper and lower layers, no bubbles were confirmed up to 130 μm from the surface of the resin foam structure, and a thickness of 30 μm on the side in contact with the polyethylene terephthalate layer was a foamed layer. Bubbles were 4 μm in the vicinity of the polyethylene terephthalate layer contact surface and 18 μm in the vicinity of the polycarbonate non-foamed layer, and there was an inclination in the thickness direction, but the bubbles were uniformly dispersed in the in-plane direction. The average cell diameter of the polyarylate foam layer was 13 μm. The thickness of the resin foam structure was 1.12 mm, and the pencil hardness was H. In the peel test, no peel was observed. Further, the light reflectance was a very high value of 99.8%. Further, the sample after the UV degradation test was pale yellow, and no cracks were observed even when folded in half.
（比較例１）
実施例１と同一の多層シートを作製し、発泡させた。ただし、多層シート表面のガス抜き工程を限りなく短くし、圧力容器からロールを取り出してから発泡完了まで１５分以内に収まるようにした。
(Comparative Example 1)
The same multilayer sheet as in Example 1 was produced and foamed. However, the degassing process on the surface of the multilayer sheet was made as short as possible so that the foaming could be completed within 15 minutes after the roll was taken out from the pressure vessel.
得られた樹脂発泡構造体の表面スキン層約３０μｍ厚さを除き、全て発泡していた。中心層であるポリエチレンテレフタレート層の平均気泡径が１．５μｍ、ポリアリレート層の平均気泡径が５μｍであり、面内方向には均一に気泡が分散されていた。樹脂発泡構造体の厚さは１．３ｍｍであり、鉛筆硬度は６Ｂ以下であった。剥離試験で、剥離は観測されなかった。また、光反射率は９９．７％と非常に高い値を示した。さらに、紫外線劣化試験後のサンプルは薄い黄色であり、２つ折りにしてもクラックは観察されなかった。 Except for the surface skin layer having a thickness of about 30 μm, the resin foam structure was completely foamed. The average cell diameter of the polyethylene terephthalate layer as the central layer was 1.5 μm, the average cell diameter of the polyarylate layer was 5 μm, and the cells were uniformly dispersed in the in-plane direction. The thickness of the resin foam structure was 1.3 mm, and the pencil hardness was 6B or less. In the peel test, no peel was observed. Further, the light reflectance was a very high value of 99.7%. Furthermore, the sample after the UV degradation test was light yellow, and no cracks were observed even when folded in half.
（比較例２）
実施例１と同一の多層シートを作製し、発泡させた。ただし、多層シート表面のガス抜き工程に２倍の時間をかけ、完全に非晶性樹脂層からガスを抜いた状態で発泡を行なった。
(Comparative Example 2)
The same multilayer sheet as in Example 1 was produced and foamed. However, the degassing process on the surface of the multilayer sheet took twice as much time, and foaming was performed in a state where the gas was completely extracted from the amorphous resin layer.
得られた樹脂発泡構造体のポリアリレート層は未発泡であった。中心層であるポリエチレンテレフタレート層は平均気泡径が２μｍと微細であり、面内方向には均一に気泡が分散されていた。樹脂発泡構造体の厚さは１．１０ｍｍであり、鉛筆硬度はＨであったが、剥離試験で、ポリエチレンテレフタレートとポリアリレート層の界面に剥離が観測された。また、光反射率は９９．７％と非常に高い値を示した。さらに、紫外線劣化試験後のサンプルは薄い黄色であり、２つ折にしてもクラックは観察されなかった。 The polyarylate layer of the obtained resin foam structure was unfoamed. The polyethylene terephthalate layer, which is the central layer, had an average cell diameter as fine as 2 μm, and the cells were uniformly dispersed in the in-plane direction. Although the thickness of the resin foam structure was 1.10 mm and the pencil hardness was H, peeling was observed at the interface between the polyethylene terephthalate and the polyarylate layer in the peeling test. Further, the light reflectance was a very high value of 99.7%. Further, the sample after the UV degradation test was pale yellow, and no cracks were observed even when folded in half.
（比較例３）
実施例１のポリエチレンテレフタレート層のみで発泡体を作製した。得られた発泡体は平均気泡径が１．５μｍと微細であり、面内方向には均一に気泡が分散されていた。発泡体の厚さは０．８ｍｍであり、鉛筆硬度は６Ｂ以下であった。また、光反射率は９９．７％と非常に高い値を示したが、紫外線劣化試験後のサンプルは茶色であり、２つ折にするとクラックを生じ、２つに割れてしまった。
(Comparative Example 3)
A foam was produced using only the polyethylene terephthalate layer of Example 1. The obtained foam had a fine average cell diameter of 1.5 μm, and the bubbles were uniformly dispersed in the in-plane direction. The foam had a thickness of 0.8 mm and a pencil hardness of 6B or less. Moreover, although the light reflectivity showed a very high value of 99.7%, the sample after the ultraviolet ray deterioration test was brown, and when it was folded in two, it cracked and split into two.
（比較例４）
高圧法ポリエチレン（密度０．９２０ｇ／ｃｍ３、ＭＩ＝０．８）１００重量部に対して、アゾジカーボンアミド１７重量部、ジクミルパーオキサイド０．８重量部を配合し、均一に混合し、この混合物を用いて押出機により幅３５０ｍｍ、厚さ２．５ｍｍの発泡用母板シートを製造した。
(Comparative Example 4)
17 parts by weight of azodicarbonamide and 0.8 parts by weight of dicumyl peroxide are blended with 100 parts by weight of high pressure polyethylene (density 0.920 g / cm 3 , MI = 0.8) and mixed uniformly. Using this mixture, a foam base sheet having a width of 350 mm and a thickness of 2.5 mm was produced by an extruder.
次に、この発泡用母板シートを金網製コンベアに載せて加熱炉中で２２０℃ の熱風を５分間送って加熱し発泡させた。得られた架橋ポリエチレン発泡シートの表裏にコロナ放電処理を施し、表面濡れ指数を４５ｄｙｎ／ｃｍとして、さらにその表裏面にＮＢＲ系接着剤を４０ｇ／ｍ２（固形分２０質量％）塗工し、赤外線ヒーターで十分に乾燥して接着剤層を設け、厚さ１２０μｍのポリアリレート（グレード＝Ｕ−１００：ユニチカ社製）フィルムを貼付して、発泡構造体を完成した。 Next, this foaming base sheet was placed on a wire mesh conveyor and heated in a heating furnace with hot air of 220 ° C. for 5 minutes to be foamed. The front and back of the obtained crosslinked polyethylene foam sheet are subjected to corona discharge treatment, the surface wetting index is set to 45 dyn / cm, and NBR adhesive is applied to the front and back surfaces of 40 g / m 2 (solid content 20% by mass), The foamed structure was completed by sufficiently drying with an infrared heater to provide an adhesive layer and attaching a 120 μm thick polyarylate (grade = U-100: manufactured by Unitika) film.
この発泡構造体の鉛筆硬度を測定しようとしたが、発泡層の沈み込みが激しく、測定不能であった。また、光反射率は６０．６％程度しか得ることができなかった。 An attempt was made to measure the pencil hardness of the foam structure, but the foam layer was severely submerged and could not be measured. Moreover, only about 60.6% of the light reflectance could be obtained.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013191032A1 (en) * | 2012-06-18 | 2013-12-27 | 古河電気工業株式会社 | Foamed sheet |
| WO2014024882A1 (en) * | 2012-08-09 | 2014-02-13 | 古河電気工業株式会社 | Thermoplastic-resin-microfoam reflective sheet, optical reflection plate, backlight panel, and method for producing foam reflective sheet |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06155604A (en) * | 1992-11-19 | 1994-06-03 | Furukawa Electric Co Ltd:The | Resin foam and manufacture thereof |
| JPH07285141A (en) * | 1994-04-15 | 1995-10-31 | Mitsuboshi Belting Ltd | Thermoplastic resin bead foam and surface melt molding method thereof |
| JPH1180408A (en) * | 1997-09-12 | 1999-03-26 | Yamaha Corp | Preparation of resin foam |
| JPH11170288A (en) * | 1997-12-10 | 1999-06-29 | Yamaha Corp | Production of foamed resin |
| JP2003145657A (en) * | 2001-11-16 | 2003-05-20 | Furukawa Electric Co Ltd:The | Resin foam |
| JP2005162965A (en) * | 2003-12-05 | 2005-06-23 | Shinseisha:Kk | Decorative film |
| JP2006045259A (en) * | 2004-07-30 | 2006-02-16 | Dueller Corp | Foamed sheet, and method and apparatus for producing the same |
| WO2007026795A1 (en) * | 2005-09-02 | 2007-03-08 | The Furukawa Electric Co., Ltd. | Light reflection plate |
-
2007
- 2007-03-22 JP JP2007075273A patent/JP4999073B2/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06155604A (en) * | 1992-11-19 | 1994-06-03 | Furukawa Electric Co Ltd:The | Resin foam and manufacture thereof |
| JPH07285141A (en) * | 1994-04-15 | 1995-10-31 | Mitsuboshi Belting Ltd | Thermoplastic resin bead foam and surface melt molding method thereof |
| JPH1180408A (en) * | 1997-09-12 | 1999-03-26 | Yamaha Corp | Preparation of resin foam |
| JPH11170288A (en) * | 1997-12-10 | 1999-06-29 | Yamaha Corp | Production of foamed resin |
| JP2003145657A (en) * | 2001-11-16 | 2003-05-20 | Furukawa Electric Co Ltd:The | Resin foam |
| JP2005162965A (en) * | 2003-12-05 | 2005-06-23 | Shinseisha:Kk | Decorative film |
| JP2006045259A (en) * | 2004-07-30 | 2006-02-16 | Dueller Corp | Foamed sheet, and method and apparatus for producing the same |
| WO2007026795A1 (en) * | 2005-09-02 | 2007-03-08 | The Furukawa Electric Co., Ltd. | Light reflection plate |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013191032A1 (en) * | 2012-06-18 | 2013-12-27 | 古河電気工業株式会社 | Foamed sheet |
| JP5503815B1 (en) * | 2012-06-18 | 2014-05-28 | 古河電気工業株式会社 | Foam sheet |
| KR20140110985A (en) * | 2012-06-18 | 2014-09-17 | 후루카와 덴키 고교 가부시키가이샤 | Foamed sheet |
| CN104114365A (en) * | 2012-06-18 | 2014-10-22 | 古河电气工业株式会社 | Foamed sheet |
| KR101589397B1 (en) | 2012-06-18 | 2016-01-27 | 후루카와 덴키 고교 가부시키가이샤 | Foamed sheet |
| WO2014024882A1 (en) * | 2012-08-09 | 2014-02-13 | 古河電気工業株式会社 | Thermoplastic-resin-microfoam reflective sheet, optical reflection plate, backlight panel, and method for producing foam reflective sheet |
| CN103827702A (en) * | 2012-08-09 | 2014-05-28 | 古河电气工业株式会社 | Thermoplastic-resin-microfoam reflective sheet, optical reflection plate, backlight panel, and method for producing foam reflective sheet |
| EP2884313A4 (en) * | 2012-08-09 | 2016-01-20 | Furukawa Electric Co Ltd | Thermoplastic-resin-microfoam reflective sheet, optical reflection plate, backlight panel, and method for producing foam reflective sheet |
| JPWO2014024882A1 (en) * | 2012-08-09 | 2016-07-25 | 古河電気工業株式会社 | Thermoplastic resin fine foamed reflective sheet, light reflective plate, backlight panel, and foamed reflective sheet manufacturing method |
| TWI554386B (en) * | 2012-08-09 | 2016-10-21 | Furukawa Electric Co Ltd | Production method of thermoplastic resin microfoil reflection sheet, light reflection plate, backlight panel and foam reflection sheet |
| US9908300B2 (en) | 2012-08-09 | 2018-03-06 | Furukawa Electric Co., Ltd. | Thermoplastic resin finely-foamed reflective sheet, light-reflecting plate, backlight panel, and method of producing the foamed reflective sheet |
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