JP2018112655A - Dispersion body for adjusting electromagnetic waves and electromagnetic waves adjusting element - Google Patents
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- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Abstract
Description
本発明は、電磁波調整用分散体及び電磁波調整素子に関する。 The present invention relates to an electromagnetic wave adjusting dispersion and an electromagnetic wave adjusting element.
省エネルギー、プライバシー保護、防眩等の観点から、可視光線、近赤外線等の電磁波の透過率又は散乱強度を電気的に制御可能な電磁波調整素子への関心が高まっている。これまで、電磁波調整素子としては、電磁波調整方式としてエレクトロクロミック現象、液晶、粒子分散液等を用いたタイプのものがそれぞれ実用化されている。この中で、エレクトロクロミック現象を用いたタイプは大面積化が困難であるという課題がある。また、液晶を用いたタイプは光の透過状態と散乱状態とを切り替えるものであり、遮光状態にできないという課題がある。 From the viewpoints of energy saving, privacy protection, anti-glare and the like, there is an increasing interest in electromagnetic wave adjusting elements that can electrically control the transmittance or scattering intensity of electromagnetic waves such as visible light and near infrared rays. Up to now, as electromagnetic wave adjusting elements, those using electrochromic phenomenon, liquid crystal, particle dispersion liquid, etc. as an electromagnetic wave adjusting method have been put into practical use. Among these, the type using the electrochromic phenomenon has a problem that it is difficult to increase the area. Further, the type using liquid crystal switches between a light transmission state and a light scattering state, and there is a problem that it cannot be in a light shielding state.
それに対して粒子分散液を用いたタイプは、電圧を印加して粒子の非配向状態（粒子がランダムに分散した状態）と、配向状態（粒子が方向性をもって配向した状態、整列状態ともいう）とを切り替えることによって電磁波の透過率を制御するものであり、大面積化が可能であることから、自動車、航空機、建築物等の窓等への適用が進んでいる。粒子分散液を用いたタイプの電磁波調整素子では、分散状態と配向状態（整列状態）とで電磁波の透過率が異なる性質を有する粒子に電圧を印加してその配向状態を制御することにより、電磁波の透過率を制御する。例えば、紫外線を照射することにより硬化する高分子媒体と、ポリ過ヨウ化物（以下、本明細書ではポリヨウ素化物ともいう）の針状小結晶等の粒子が流動可能な状態で分散媒中に分散した光偏光懸濁液と、を含有する調光材料を用いて調光フィルムを形成し、作製した調光フィルムに電界を印加することで入射光の透過を調整する方法が特許文献１に記載されている。 On the other hand, in the type using a particle dispersion liquid, a non-oriented state of particles (state in which particles are randomly dispersed) and an oriented state (state in which particles are oriented with orientation, or an aligned state) are applied by applying voltage. Since the transmittance of the electromagnetic wave is controlled by switching between and, and the area can be increased, it is being applied to windows of automobiles, aircrafts, buildings, and the like. In an electromagnetic wave adjusting element of a type using a particle dispersion, an electromagnetic wave is controlled by applying a voltage to particles having a property that electromagnetic wave transmittance is different between a dispersed state and an aligned state (aligned state) to control the aligned state. To control the transmittance. For example, in a dispersion medium in a state in which particles such as a polymer medium that is cured by irradiation with ultraviolet rays and needle-like small crystals of polyperiodide (hereinafter also referred to as polyiodide in this specification) can flow. Patent Document 1 discloses a method of adjusting the transmission of incident light by forming a light control film using a light control material containing a dispersed light polarization suspension and applying an electric field to the manufactured light control film. Have been described.
しかしながら、ポリヨウ素化物は溶剤による劣化が顕著であるために、ポリヨウ素化物を用いた電磁波調整素子を作製するにあたり、選択できる溶剤が限定されるという課題がある。したがって本発明は、ポリヨウ素化物に耐溶剤性を付与し、耐溶剤性の良好な電磁波調整粒子を用いた電磁波調整用分散体、及び電磁波調整素子を提供することを目的とする。 However, since polyiodide is remarkably deteriorated by a solvent, there is a problem that a solvent that can be selected is limited in producing an electromagnetic wave adjusting element using the polyiodide. Accordingly, an object of the present invention is to provide a dispersion for electromagnetic wave adjustment using an electromagnetic wave adjusting particle having good solvent resistance by imparting solvent resistance to a polyiodide, and an electromagnetic wave adjusting element.
本実施態様は以下を含む。
＜１＞ ポリヨウ素化物の表面の少なくとも一部に、高分子共重合体を有してなる、長軸の長さの平均値が１００ｎｍ〜７００ｎｍであり、アスペクト比（長軸の長さ／短軸の長さ）の平均値が２．０以上である電磁波調整粒子と、分散媒とを含む、電磁波調整用分散体。
＜２＞ 前記高分子共重合体が、アクリロニトリルモノマー由来の構造単位、（メタ）アクリレートモノマー由来の構造単位、及びシリコーンモノマー由来の構造単位からなる群から選択される少なくとも１つの構造単位を有する、＜１＞に記載の電磁波調整用分散体。
＜３＞ 前記電磁波調整粒子の粒子表面にマクロモノマーが付与されている、＜１＞又は＜２＞に記載の電磁波調整用分散体。
＜４＞ 前記マクロモノマーが、アクリロニトリルモノマー由来の構造単位、（メタ）アクリレートモノマー由来の構造単位及びシリコーンモノマー由来の構造単位からなる群から選択される少なくとも１つの構造単位を有する、＜３＞に記載の電磁波調整用分散体。
＜５＞ 前記分散媒は２５℃での粘度が１ｍＰａ・ｓ〜５０００ｍＰａ・ｓである、＜１＞〜＜４＞のいずれか１項に記載の電磁波調整用分散体。
＜６＞ さらにマトリックス樹脂を含み、前記マトリックス樹脂が液滴を含み、前記液滴が前記電磁波調整粒子と前記分散媒とを含む、＜１＞〜＜５＞のいずれか１項に記載の電磁波調整用分散体。
＜７＞ 一対の導電性基材と、前記一対の導電性基材の間に配置される＜１＞〜＜６＞のいずれか１項に記載の電磁波調整用分散体と、を有する電磁波調整素子。
This embodiment includes:
<1> The average value of the length of the major axis comprising a polymer copolymer on at least a part of the surface of the polyiodide is 100 nm to 700 nm, and the aspect ratio (length of the major axis / short A dispersion for electromagnetic wave adjustment, comprising electromagnetic wave adjusting particles having an average value of (axis length) of 2.0 or more and a dispersion medium.
<2> The polymer copolymer has at least one structural unit selected from the group consisting of a structural unit derived from an acrylonitrile monomer, a structural unit derived from a (meth) acrylate monomer, and a structural unit derived from a silicone monomer. The dispersion for electromagnetic wave adjustment according to <1>.
<3> The dispersion for electromagnetic wave adjustment according to <1> or <2>, wherein a macromonomer is provided on a particle surface of the electromagnetic wave adjustment particle.
<4> The <3>, wherein the macromonomer has at least one structural unit selected from the group consisting of a structural unit derived from an acrylonitrile monomer, a structural unit derived from a (meth) acrylate monomer, and a structural unit derived from a silicone monomer. The dispersion for electromagnetic wave adjustment as described.
<5> The dispersion for electromagnetic wave adjustment according to any one of <1> to <4>, wherein the dispersion medium has a viscosity at 25 ° C. of 1 mPa · s to 5000 mPa · s.
<6> The electromagnetic wave according to any one of <1> to <5>, further including a matrix resin, wherein the matrix resin includes droplets, and the droplet includes the electromagnetic wave adjusting particles and the dispersion medium. Dispersion for adjustment.
<7> An electromagnetic wave adjustment comprising: a pair of conductive base materials; and the dispersion for electromagnetic wave adjustment according to any one of <1> to <6>, disposed between the pair of conductive base materials. element.
本発明によれば、耐溶剤性の良好な電磁波調整粒子を用いた電磁波調整用分散体、及び電磁波調整素子が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the dispersion for electromagnetic waves adjustment using the electromagnetic wave adjustment particle with favorable solvent resistance, and an electromagnetic wave adjustment element are provided.
以下、本発明を実施するための形態について詳細に説明する。但し、本発明は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素（要素ステップ等も含む）は、特に明示した場合、原理的に明らかに必須であると考えられる場合等を除き、必須ではない。数値及びその範囲についても同様であり、本発明を制限するものではない。 Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless explicitly specified, unless otherwise clearly considered essential in principle. The same applies to numerical values and ranges thereof, and the present invention is not limited thereto.
本明細書において「工程」との語は、独立した工程に加え、他の工程と明確に区別できない場合であってもその工程の目的が達成されれば、当該工程も本用語に含まれる。
本明細書において「〜」を用いて示された数値範囲には、「〜」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
本明細書中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本明細書において組成物中の各成分の含有率又は含有量は、組成物中に各成分に該当する物質が複数種存在する場合、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
本明細書において組成物中の各成分の粒子径は、組成物中に各成分に該当する粒子が複数種存在する場合、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。
本明細書において「層」又は「膜」との語は、当該層又は膜が存在する領域を観察したときに、当該領域の全体に形成されている場合に加え、当該領域の一部にのみ形成されている場合も含まれる。
本明細書において、「（メタ）アクリレートモノマー」はアクリレートモノマー及びメタクリレートモノマーからなる群から選択される少なくとも一方を意味し、「（メタ）アクリル酸エステル」はアクリル酸エステル及びメタクリル酸エステルからなる群から選択される少なくとも一方を意味する。
In this specification, the term “process” includes an independent process, and even if it cannot be clearly distinguished from other processes, the process is included in the term as long as the purpose of the process is achieved.
In the present specification, the numerical ranges indicated by using “to” include numerical values described before and after “to” as the minimum value and the maximum value, respectively.
In the numerical ranges described stepwise in this specification, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range. Good. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
In the present specification, the content rate or content of each component in the composition is such that when there are a plurality of substances corresponding to each component in the composition, the plurality of kinds present in the composition unless otherwise specified. It means the total content or content of substances.
In the present specification, the particle diameter of each component in the composition is a mixture of the plurality of types of particles present in the composition unless there is a specific indication when there are a plurality of types of particles corresponding to each component in the composition. Means the value of.
In this specification, the term “layer” or “film” refers to only a part of the region in addition to the case where the layer or film is formed over the entire region. The case where it is formed is also included.
In the present specification, “(meth) acrylate monomer” means at least one selected from the group consisting of acrylate monomer and methacrylate monomer, and “(meth) acrylic acid ester” means group consisting of acrylic acid ester and methacrylic acid ester. Means at least one selected from
＜電磁波調整用分散体＞
本実施の形態の電磁波調整用分散体（以下、単に分散体とも称する）は、ポリヨウ素化物の表面の少なくとも一部に、高分子共重合体を有してなる、長軸の長さの平均値が１００ｎｍ〜７００ｎｍであり、アスペクト比（長軸の長さ／短軸の長さ）の平均値が２．０以上である電磁波調整粒子と、分散媒とを含む。
電磁波調整用分散体中のポリヨウ素化物の表面の少なくとも一部に高分子共重合体を有することで、ポリヨウ素化物が溶剤と接する領域が減り、耐溶剤性が向上する傾向にある。
電磁波調整粒子の長軸の長さの平均値が１００ｎｍ〜７００ｎｍであると、電磁波調整粒子の分散状態及び配向状態における電磁波の透過率の適切な調整が可能となり、さらに電圧の印加に対する応答性が良好に維持される傾向にある。このため、ポリヨウ素化物の表面に高分子共重合体が存在する場合であっても、電磁波調整粒子として優れた機能を発揮できる傾向にある。
電磁波調整粒子のアスペクト比の平均値が２．０以上であると、電磁波調整粒子が分散媒中にランダムに分散している状態と、電場の方向に沿うように配向している状態とで、電磁波調整粒子による電磁波透過率を充分に変化させることができる。このため、ポリヨウ素化物の表面に高分子共重合体が存在する場合であっても、電磁波調整粒子として優れた機能を発揮できる傾向にある。
<Dispersion for electromagnetic wave adjustment>
The dispersion for electromagnetic wave adjustment of the present embodiment (hereinafter also simply referred to as dispersion) has an average length of the long axis comprising a polymer copolymer on at least a part of the surface of the polyiodide. It includes electromagnetic wave adjusting particles having a value of 100 nm to 700 nm and an average aspect ratio (length of major axis / length of minor axis) of 2.0 or more, and a dispersion medium.
By having the polymer copolymer on at least a part of the surface of the polyiodide in the electromagnetic wave adjusting dispersion, the region where the polyiodide is in contact with the solvent is reduced, and the solvent resistance tends to be improved.
When the average length of the major axis of the electromagnetic wave adjusting particles is 100 nm to 700 nm, it is possible to appropriately adjust the transmittance of the electromagnetic waves in the dispersed state and the aligned state of the electromagnetic wave adjusting particles, and further, the responsiveness to voltage application is improved. It tends to be well maintained. For this reason, even when a polymer copolymer is present on the surface of the polyiodide, it tends to exhibit an excellent function as electromagnetic wave adjusting particles.
When the average value of the aspect ratio of the electromagnetic wave adjusting particles is 2.0 or more, the electromagnetic wave adjusting particles are randomly dispersed in the dispersion medium, and the state is oriented along the direction of the electric field, The electromagnetic wave transmittance by the electromagnetic wave adjusting particles can be sufficiently changed. For this reason, even when a polymer copolymer is present on the surface of the polyiodide, it tends to exhibit an excellent function as electromagnetic wave adjusting particles.
本実施の形態では、分散体に電圧を印加していない状態の電磁波調整粒子は分散媒中にランダムに分散しており、電磁波調整粒子による電磁波の吸収が電磁波調整粒子の長軸表面で行われるか、短軸で行われるかは個々の電磁波調整粒子の分散体中における向きによって異なる。他方、分散体に電圧を印加した状態では、個々の電磁波調整粒子は長軸が電場の方向に沿うように配向し、電磁波の吸収は主に電磁波調整粒子の短軸の表面で行われる。このような電磁波調整粒子の動きを利用して、電圧の印加の有無によって電磁波の透過率を変化させたり、吸収波長を変化させたりしている。 In the present embodiment, the electromagnetic wave adjusting particles in a state where no voltage is applied to the dispersion are randomly dispersed in the dispersion medium, and the electromagnetic wave is absorbed by the electromagnetic wave adjusting particles on the long axis surface of the electromagnetic wave adjusting particles. Whether it is performed on the short axis or not depends on the orientation of the individual electromagnetic wave adjusting particles in the dispersion. On the other hand, in a state where a voltage is applied to the dispersion, the individual electromagnetic wave adjusting particles are oriented so that the major axis is along the direction of the electric field, and the electromagnetic wave is absorbed mainly on the surface of the minor axis of the electromagnetic wave adjusting particles. Utilizing such movement of the electromagnetic wave adjusting particles, the transmittance of the electromagnetic wave is changed or the absorption wavelength is changed depending on whether or not a voltage is applied.
［電磁波調整粒子］
本実施の形態で使用する電磁波調整粒子は、ポリヨウ素化物の表面の少なくとも一部に、高分子共重合体を有する。電磁波調整粒子の長軸の長さの平均値は１００ｎｍ〜７００ｎｍであり、アスペクト比の平均値は２．０以上である。さらに高分子共重合体の表面にマクロモノマーが付与されていてもよい。
本明細書において電磁波調整粒子の長軸及びその長さは、電磁波調整粒子の撮影像を観察したときに、電磁波調整粒子表面の任意の点ａから点ａと異なる電磁波調整粒子表面の任意の点ｂまでの距離が最長となる線分及びその長さとする。電磁波調整粒子の短軸及びその長さは、長軸に垂直であって電磁波調整粒子表面の二点を結ぶ線分のうち、長さが最長となる線分及びその長さとする。電磁波調整粒子の長軸の長さ及び短軸の長さは、例えば、走査型電子顕微鏡（ＳＥＭ）、透過型電子顕微鏡（ＴＥＭ）等による観察によって測定できる。また、電磁波調整粒子の長軸の長さの平均値及び短軸の長さの平均値は、例えば、走査型電子顕微鏡（ＳＥＭ）、透過型電子顕微鏡（ＴＥＭ）等の電子顕微鏡で電磁波調整粒子を撮影し、撮影した画像より任意に１００個の電磁波調整粒子を抽出し、各電磁波調整粒子の長軸の長さ及び短軸の長さのそれぞれの算術平均値として算出することができる。
[Electromagnetic wave adjusting particles]
The electromagnetic wave adjusting particles used in the present embodiment have a polymer copolymer on at least a part of the surface of the polyiodide. The average value of the major axis length of the electromagnetic wave adjusting particles is 100 nm to 700 nm, and the average value of the aspect ratio is 2.0 or more. Further, a macromonomer may be provided on the surface of the polymer copolymer.
In the present specification, the long axis of the electromagnetic wave adjusting particle and the length thereof are the arbitrary point on the surface of the electromagnetic wave adjusting particle different from the point a on the surface of the electromagnetic wave adjusting particle when the photographed image of the electromagnetic wave adjusting particle is observed. The line segment with the longest distance to b and its length are used. The short axis and the length of the electromagnetic wave adjusting particles are the line segment that is perpendicular to the long axis and connects the two points on the surface of the electromagnetic wave adjusting particle and has the longest length and the length thereof. The major axis length and minor axis length of the electromagnetic wave adjusting particles can be measured, for example, by observation with a scanning electron microscope (SEM), a transmission electron microscope (TEM), or the like. Moreover, the average value of the major axis length and the average value of the minor axis length of the electromagnetic wave adjusting particles can be determined, for example, with an electron microscope such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM). , And 100 electromagnetic wave adjusting particles can be arbitrarily extracted from the taken image, and can be calculated as the arithmetic average value of the length of the major axis and the length of the minor axis of each electromagnetic wave adjusting particle.
電磁波調整粒子の長軸の長さの平均値は１００ｎｍ〜７００ｎｍであり、１５０ｎｍ〜６７０ｎｍであることが好ましく、２００ｎｍ〜６５０ｎｍであることがより好ましい。電磁波調整粒子の長軸の長さの平均値が１００ｎｍ以上であると、分散状態の電磁波調整粒子により電磁波が充分に吸収され、電磁波透過率を有効に低下させることができる傾向にある。電磁波調整粒子の長軸の長さの平均値が７００ｎｍ以下であると、分散状態の電磁波調整粒子による電磁波の散乱が抑制されてヘイズの上昇が抑制される傾向にあり、また、電圧の印加に対する応答性（配向性）が良好に維持される傾向にある。 The average value of the major axis length of the electromagnetic wave adjusting particles is 100 nm to 700 nm, preferably 150 nm to 670 nm, and more preferably 200 nm to 650 nm. When the average value of the major axis length of the electromagnetic wave adjusting particles is 100 nm or more, the electromagnetic wave is sufficiently absorbed by the dispersed electromagnetic wave adjusting particles, and the electromagnetic wave transmittance tends to be effectively reduced. When the average value of the major axis length of the electromagnetic wave adjusting particles is 700 nm or less, scattering of the electromagnetic waves by the dispersed electromagnetic wave adjusting particles tends to be suppressed, and haze increase tends to be suppressed. Response (orientation) tends to be maintained well.
電磁波調整粒子のアスペクト比の平均値は、電磁波の透過率の適切な調整を可能とする観点から、２．０以上であり、２．５以上であることが好ましく、３．０以上であることがより好ましい。アスペクト比の平均値の上限は特に制限されず、電磁波調整粒子の材料、調製方法等に応じて適宜決定することができる。例えば、２０以下であってよく、１０以下であってよい。 The average value of the aspect ratio of the electromagnetic wave adjusting particles is 2.0 or more, preferably 2.5 or more, and preferably 3.0 or more from the viewpoint of enabling appropriate adjustment of the electromagnetic wave transmittance. Is more preferable. The upper limit of the average aspect ratio is not particularly limited, and can be appropriately determined according to the material of the electromagnetic wave adjusting particles, the preparation method, and the like. For example, it may be 20 or less, and may be 10 or less.
電磁波調整粒子の含有率は特に限定されないが、電磁波調整粒子と分散媒の合計量に対して０．１質量％〜３０質量％であることが好ましく、０．２質量％〜２５質量％であることがより好ましく、０．３質量％〜２０質量％であることがさらに好ましい。電磁波調整粒子と分散媒の合計量に対して電磁波調整粒子の含有率が０．１質量％以上であると、電圧を印加していない状態での電磁波を充分に吸収できる傾向にあり、３０質量％以下であると、電圧を印加した状態での電磁波透過率を充分に維持できる傾向にある。 The content of the electromagnetic wave adjusting particles is not particularly limited, but is preferably 0.1% by mass to 30% by mass, and preferably 0.2% by mass to 25% by mass with respect to the total amount of the electromagnetic wave adjusting particles and the dispersion medium. It is more preferable that the content is 0.3% by mass to 20% by mass. When the content of the electromagnetic wave adjusting particles is 0.1% by mass or more with respect to the total amount of the electromagnetic wave adjusting particles and the dispersion medium, the electromagnetic waves in a state where no voltage is applied tend to be sufficiently absorbed, and 30% by mass. % Or less, the electromagnetic wave transmittance in a state where a voltage is applied tends to be sufficiently maintained.
電磁波調整用分散体は、長軸の長さの平均値が１００ｎｍ〜７００ｎｍであり、アスペクト比の平均値が２．０以上であって、本実施の形態の効果が充分に達成される限りにおいて、長軸の長さが１００ｎｍ〜７００ｎｍであり、アスペクト比が２．０以上であるという条件を満たす電磁波調整粒子のみを含んでもよく、長軸の長さ及びアスペクト比の両方又はいずれかを満たさない電磁波調整粒子を含んでもよい。本発明の効果を充分に得る観点からは、長軸の長さが１００ｎｍ〜７００ｎｍであり、アスペクト比が２．０以上であるという条件をいずれも満たす電磁波調整粒子の、電磁波調整粒子全体に対する割合が６０個％以上であることが好ましく、７５個％以上であることがより好ましい。前記割合は、例えば、電子顕微鏡像等を観察した際に任意に選択される電磁波調整粒子１００個中における条件を満たす電磁波調整粒子の割合とすることができる。 As long as the average value of the length of the major axis is 100 nm to 700 nm, the average value of the aspect ratio is 2.0 or more, and the dispersion for electromagnetic wave adjustment has a sufficient effect of the present embodiment, In addition, it may include only electromagnetic wave adjusting particles satisfying the condition that the length of the major axis is 100 nm to 700 nm and the aspect ratio is 2.0 or more, and satisfies both or both of the length of the major axis and the aspect ratio. There may be no electromagnetic wave adjusting particles. From the viewpoint of sufficiently obtaining the effects of the present invention, the ratio of the electromagnetic wave adjusting particles satisfying all the conditions that the length of the major axis is 100 nm to 700 nm and the aspect ratio is 2.0 or more to the whole electromagnetic wave adjusting particles. Is preferably 60% or more, and more preferably 75% or more. The said ratio can be made into the ratio of the electromagnetic wave adjustment particles which satisfy | fill the conditions in 100 electromagnetic wave adjustment particles arbitrarily selected, for example when an electron microscope image etc. are observed.
（ポリヨウ素化物）
ポリヨウ素化物は特に限定されず、前駆体であるピラジン−２，３−ジカルボン酸２水和物、ピラジン−２，５−ジカルボン酸水和物、及びピリジン−２，５−ジカルボン酸１水和物からなる群より選択される少なくとも１種の物質とヨウ素とヨウ化物とニトロセルロースとを反応させて得られるポリヨウ素化物の針状結晶が好ましく用いられる。ヨウ化物としてはヨウ化カルシウム等が挙げられる。
(Polyiodide)
The polyiodide is not particularly limited and is a precursor of pyrazine-2,3-dicarboxylic acid dihydrate, pyrazine-2,5-dicarboxylic acid hydrate, and pyridine-2,5-dicarboxylic acid monohydrate. A needle-like crystal of polyiodide obtained by reacting at least one substance selected from the group consisting of substances, iodine, iodide and nitrocellulose is preferably used. Examples of the iodide include calcium iodide.
ポリヨウ素化物の粒子サイズは、電磁波調整粒子の長軸の長さの平均値が１００ｎｍ〜７００ｎｍであり、アスペクト比の平均値が２．０以上となる限り限定されないが、印加電圧に対する応答時間と、ポリヨウ素化物分散液中の凝集及び沈殿との関係から、以下のサイズが好ましい。
ポリヨウ素化物の長軸の長さの平均値は、７０ｎｍ〜６２５ｎｍが好ましく、８０ｎｍ〜５５０ｎｍがより好ましく、９０ｎｍ〜５００ｎｍがさらに好ましい。ポリヨウ素化物のアスペクト比の平均値は３．０〜８．０が好ましく、３．３〜７．０がより好ましく、３．６〜６．０がさらに好ましい。
前記ポリヨウ素化物の長軸の長さ及び短軸の長さ、並びにそれらの平均値は、電磁波調整用分散体の長軸の長さ及び短軸の長さ、並びにそれらの平均値と同様の方法で決定することができる。
The particle size of the polyiodide is not limited as long as the average value of the major axis length of the electromagnetic wave adjusting particles is 100 nm to 700 nm, and the average value of the aspect ratio is 2.0 or more. In view of the relationship between aggregation and precipitation in the polyiodide dispersion, the following sizes are preferable.
The average value of the major axis length of the polyiodide is preferably 70 nm to 625 nm, more preferably 80 nm to 550 nm, and still more preferably 90 nm to 500 nm. The average value of the aspect ratio of the polyiodide is preferably 3.0 to 8.0, more preferably 3.3 to 7.0, and still more preferably 3.6 to 6.0.
The major axis length and minor axis length of the polyiodide and the average value thereof are the same as the major axis length and minor axis length of the electromagnetic wave adjusting dispersion, and the average value thereof. Can be determined by the method.
製造されたポリヨウ素化物には、未反応物又は副生成物、サイズが小さい粒子又は大きい粒子、アスペクト比が小さい粒子又は大きい粒子が含まれる場合がある。通常は精製して用いることが好ましい。この精製方法としては、例えば、遠心分離を行う方法が挙げられる。また、処理回数は２回以上が好ましい。遠心後は上澄みを傾斜して廃棄し、粒子が凝集せずに分散可能な有機溶剤を加えることが好ましい。このとき、加える有機溶剤に制限はないが、例えば、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、酢酸ペンチル、酢酸イソアミル、酢酸ヘキシル、アセトン、エチルメチルケトン、イソブチルケトン等が挙げられ、中でも、酢酸エチル、酢酸プロピル、酢酸ブチル、酢酸ペンチル、酢酸イソアミル、及び酢酸ヘキシルからなる群より選択される少なくとも１種を好適に使用することができる。溶剤は１種を単独で用いてもよく、２種類以上を混合して用いてもよい。また、遠心分離処理を２回以上行う場合、最初の遠心分離処理にはニトロセルロースを溶解させた溶剤を用いてもよい。このとき、ニトロセルロースの濃度に特に制限はないが、例えば３質量％〜２０質量％であり、好ましくは５質量％〜１５質量％である。また、溶剤を加えた後は、ポリヨウ素化物が溶剤中で分散しやすいように、ホモジナイザー又は超音波で処理することが好ましい。
以上のようにしてポリヨウ素化物の溶剤分散液を得ることができる。
The produced polyiodide may include unreacted or by-products, small or large particles, small or large aspect ratio particles. Usually, it is preferably used after purification. Examples of the purification method include a method of performing centrifugation. The number of treatments is preferably 2 times or more. After centrifugation, it is preferable to incline and discard the supernatant and add an organic solvent that can disperse without aggregation of particles. At this time, the organic solvent to be added is not limited, for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, isoamyl acetate, hexyl acetate, acetone, ethyl methyl ketone, isobutyl ketone, etc. At least one selected from the group consisting of ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, isoamyl acetate, and hexyl acetate can be preferably used. A solvent may be used individually by 1 type and may be used in mixture of 2 or more types. Moreover, when performing the centrifugation process twice or more, you may use the solvent which dissolved nitrocellulose for the first centrifugation process. At this time, although there is no restriction | limiting in particular in the density | concentration of nitrocellulose, For example, they are 3 mass%-20 mass%, Preferably they are 5 mass%-15 mass%. Moreover, after adding a solvent, it is preferable to process with a homogenizer or an ultrasonic wave so that a polyiodide may disperse | distribute easily in a solvent.
As described above, a solvent dispersion of polyiodide can be obtained.
（高分子共重合体）
電磁波調整粒子はポリヨウ素化物の表面の少なくとも一部に、高分子共重合体を有してなる。
本実施の形態において、ポリヨウ素化物の表面の少なくとも一部に高分子共重合体を有するとは、ポリヨウ素化物の表面の少なくとも一部に高分子共重合体が配置されている状態を意味し、ポリヨウ素化物の表面全体に高分子共重合体が配置されていてもよい。高分子共重合体はポリヨウ素化物の表面に化学的に結合していてもよく、化学的に結合していなくてもよい。
本実施の形態における「高分子共重合体」とは、数平均分子量が１，０００以上の共重合体を表す。
(Polymer copolymer)
The electromagnetic wave adjusting particles have a polymer copolymer on at least a part of the surface of the polyiodide.
In the present embodiment, having a polymer copolymer on at least a part of the surface of the polyiodide means a state in which the polymer copolymer is disposed on at least a part of the surface of the polyiodide. The polymer copolymer may be disposed on the entire surface of the polyiodide. The polymer copolymer may be chemically bonded to the surface of the polyiodide or may not be chemically bonded.
The “polymer copolymer” in the present embodiment represents a copolymer having a number average molecular weight of 1,000 or more.
前記高分子重合体の材料は特に制限されないが、良好な電磁波透過率を達成する観点からは、分散媒と屈折率の近い材料が好ましく、例えば、アクリロニトリルモノマー由来の構造単位、（メタ）アクリレートモノマー由来の構造単位、及びシリコーンモノマー由来の構造単位からなる群から選択される少なくとも１つの構造単位を有する材料が好ましい。さらに、ポリヨウ素化物に高分子共重合体を付与する際に使用する溶剤に対して、未重合のモノマーは溶解し、重合してポリマーになると不溶となる材料が好ましく、そのような高分子共重合体の構造単位としては、例えば、アクリロニトリルモノマー、メチルメタクリレートモノマー等が挙げられる。高分子共重合体は、１種を単独で用いても、２種以上を併用してもよい。ポリヨウ素化物の表面の少なくとも一部に高分子重合体を付与することで、ポリヨウ素化物が溶剤と接する領域が減り、耐溶剤性が向上する傾向にある。 The material of the polymer is not particularly limited, but a material having a refractive index close to that of the dispersion medium is preferable from the viewpoint of achieving good electromagnetic wave transmittance. For example, a structural unit derived from an acrylonitrile monomer, a (meth) acrylate monomer A material having at least one structural unit selected from the group consisting of a structural unit derived from and a structural unit derived from a silicone monomer is preferred. Furthermore, a material that dissolves the unpolymerized monomer in the solvent used for applying the polymer copolymer to the polyiodide and becomes insoluble when polymerized to form a polymer is preferable. Examples of the structural unit of the polymer include acrylonitrile monomer and methyl methacrylate monomer. A high molecular copolymer may be used individually by 1 type, or may use 2 or more types together. By applying a polymer to at least a part of the surface of the polyiodide, the region where the polyiodide is in contact with the solvent is reduced, and the solvent resistance tends to be improved.
ポリヨウ素化物への高分子重合体の付与方法は特に限定されず、例えば、ポリヨウ素化物に重合性官能基を付与した後、高分子重合体の材料を重合させて付与してもよい。 The method for applying the high molecular polymer to the polyiodide is not particularly limited. For example, after applying a polymerizable functional group to the polyiodide, the high molecular material may be polymerized for application.
（マクロモノマー）
ポリヨウ素化物の表面の少なくとも一部に高分子共重合体を有する電磁波調整粒子は、粒子表面にマクロモノマーが付与されていてもよい。
本実施の形態において、マクロモノマーとは、分子内に重合性官能基を有し、数平均分子量が１，０００以上である化合物をいう。
本実施の形態において、高分子共重合体表面にマクロモノマーが付与されるとは、高分子共重合体の表面の少なくとも一部にマクロモノマーが配置されている状態を意味し、高分子共重合体の表面全体にマクロモノマーが配置されていてもよい。マクロモノマーは高分子共重合体の表面に化学的に結合していてもよく、化学的に結合していなくてもよい。電磁波調整粒子の分散性の観点から、マクロモノマーは高分子共重合体の表面に化学的に結合していることが好ましい。また、電磁波調整粒子の分散性の観点から、マクロモノマーは、その一部が高分子共重合体表面に接するように配置され、他の一部が分散媒に接するように配置されることが好ましい。電磁波調整粒子の分散性の観点から、マクロモノマーは一端が高分子共重合体に結合し、他の一端が分散媒に接するように（ヘア状に）配置されていることがより好ましい。ヘア状に配置されたマクロモノマーが高分子共重合体に複数配置されている（コロナ状に配置されている）ことがさらに好ましい。
(Macromonomer)
The electromagnetic wave control particles having a polymer copolymer on at least a part of the surface of the polyiodide may have a macromonomer provided on the particle surface.
In the present embodiment, the macromonomer refers to a compound having a polymerizable functional group in the molecule and having a number average molecular weight of 1,000 or more.
In the present embodiment, the addition of a macromonomer to the surface of the polymer copolymer means a state in which the macromonomer is disposed on at least a part of the surface of the polymer copolymer. Macromonomer may be arranged on the entire surface of the coalescence. The macromonomer may or may not be chemically bonded to the surface of the polymer copolymer. From the viewpoint of dispersibility of the electromagnetic wave adjusting particles, the macromonomer is preferably chemically bonded to the surface of the polymer copolymer. Further, from the viewpoint of dispersibility of the electromagnetic wave adjusting particles, the macromonomer is preferably arranged so that a part thereof is in contact with the surface of the polymer copolymer and the other part is in contact with the dispersion medium. . From the viewpoint of dispersibility of the electromagnetic wave adjusting particles, it is more preferable that the macromonomer is arranged (in a hair shape) so that one end is bonded to the polymer copolymer and the other end is in contact with the dispersion medium. More preferably, a plurality of macromonomers arranged in a hair shape are arranged in the polymer copolymer (arranged in a corona shape).
前記マクロモノマーの材料は特に制限されないが、良好な電磁波透過率を達成する観点からは、分散媒と屈折率の近い材料が好ましく、例えば、アクリロニトリルモノマー由来の構造単位、（メタ）アクリレートモノマー由来の構造単位、及びシリコーンモノマー由来の構造単位からなる群から選択される少なくとも１つの構造単位を有する材料が好ましい。さらに、電磁波調整粒子の分散性の観点からは、分散媒と相溶性の高い材料が好ましく、例えば分散媒がシリコーン樹脂の場合には、シリコーンモノマー由来の構造単位を有する材料が好ましい。マクロモノマーの構造単位は１種の構造単位からなるものでも、２種以上の構造単位を含むものでもよい。マクロモノマーは調製したものを用いても、市販品を用いてもよい。市販品としては、例えば、ジメチルシリコーンマクロモノマー（ＦＭ−０７２１、ＪＮＣ株式会社）が挙げられる。 The material of the macromonomer is not particularly limited, but from the viewpoint of achieving good electromagnetic wave transmittance, a material having a refractive index close to that of the dispersion medium is preferable. For example, a structural unit derived from an acrylonitrile monomer or a (meth) acrylate monomer A material having at least one structural unit selected from the group consisting of a structural unit and a structural unit derived from a silicone monomer is preferred. Furthermore, from the viewpoint of dispersibility of the electromagnetic wave adjusting particles, a material highly compatible with the dispersion medium is preferable. For example, when the dispersion medium is a silicone resin, a material having a structural unit derived from a silicone monomer is preferable. The structural unit of the macromonomer may be composed of one type of structural unit or may contain two or more types of structural units. As the macromonomer, a prepared product or a commercially available product may be used. As a commercial item, a dimethyl silicone macromonomer (FM-0721, JNC Corporation) is mentioned, for example.
マクロモノマーの高分子共重合体への付与方法は特に制限されない。ポリヨウ素化物の表面への高分子共重合体の付与と共通の反応系で付与してもよく、ポリヨウ素化物の表面へ高分子共重合体を付与した後に、異なる反応系で付与してもよい。 The method for applying the macromonomer to the polymer copolymer is not particularly limited. It may be applied in the same reaction system as the application of the polymer copolymer to the surface of the polyiodide, or it may be applied in a different reaction system after the polymer copolymer is applied to the surface of the polyiodide. Good.
（電磁波調整粒子の調製方法）
電磁波調整粒子を、長軸の長さの平均値が１００ｎｍ〜７００ｎｍであり、アスペクト比の平均値が２．０以上となるよう調製する方法は特に限定されない。例えば、長軸の長さが目的の長さよりも短いポリヨウ素化物を用いて高分子共重合体を付与することができる。また、高分子共重合体をポリヨウ素化物に付与する反応において、ポリヨウ素化物、高分子共重合体等の組成に応じて反応時間を調整することによって電磁波調整粒子の長軸の長さ及びアスペクト比を調整してもよい。
(Method for preparing electromagnetic wave adjusting particles)
The method for preparing the electromagnetic wave adjusting particles so that the average value of the major axis length is 100 nm to 700 nm and the average value of the aspect ratio is 2.0 or more is not particularly limited. For example, a polymer copolymer can be provided using a polyiodide having a major axis shorter than the target length. Further, in the reaction for imparting the polymer copolymer to the polyiodide, the length and aspect of the major axis of the electromagnetic wave adjusting particles are adjusted by adjusting the reaction time according to the composition of the polyiodide, polymer copolymer, etc. The ratio may be adjusted.
［分散媒］
本実施の形態で使用する分散媒の種類は特に制限されず、電磁波調整粒子及びその材料の種類、電磁波調整素子の使用環境等に応じて選択できる。電磁波調整粒子の材質が水溶性である場合は、例えば、非水系又は低極性のアクリル樹脂、シリコーン樹脂等の非水溶性の分散媒などを分散媒として選択することが好ましい。一方で電磁波調整粒子の材質が脂溶性である場合は、水、低級アルコール等の極性溶媒、極性基を有する樹脂などを用いることが好ましい。電磁波調整素子を温度変化の大きい環境で使用する場合は、温度変化による応答速度の差を小さくする観点から、粘度の温度依存性が小さい分散媒を選択することが好ましい。
[Dispersion medium]
The type of the dispersion medium used in the present embodiment is not particularly limited, and can be selected according to the type of electromagnetic wave adjusting particles and their materials, the usage environment of the electromagnetic wave adjusting element, and the like. When the material of the electromagnetic wave adjusting particles is water-soluble, for example, a water-insoluble dispersion medium such as a non-aqueous or low-polar acrylic resin or silicone resin is preferably selected as the dispersion medium. On the other hand, when the material of the electromagnetic wave adjusting particles is fat-soluble, it is preferable to use a polar solvent such as water or a lower alcohol, a resin having a polar group, or the like. When the electromagnetic wave adjusting element is used in an environment with a large temperature change, it is preferable to select a dispersion medium having a small temperature dependency of viscosity from the viewpoint of reducing a difference in response speed due to a temperature change.
非水溶性の分散媒としては、シリコーン樹脂、変性シリコーン樹脂、及びアクリル樹脂とシリコーン樹脂とからなるグラフト共重合体等の構造を有する樹脂が挙げられる。シリコーン樹脂は一般に疎水性であるため、吸湿による性能低下を抑制する観点からも好ましい。シリコーン樹脂は、直鎖型であっても分岐鎖型であってもよい。また、ジアルキルシリコーン樹脂、アルキルアリールシリコーン樹脂、ジアリールシリコーン樹脂等のいずれであってもよい。中でも低ガス透過性、低含水率、後述するマトリックス樹脂と組み合わせた場合の屈折率制御等の観点からは、ジメチルジフェニルシリコーン樹脂が好ましい。
分散媒は、１種を単独で用いても、２種以上を併用してもよい。
Examples of the water-insoluble dispersion medium include a resin having a structure such as a silicone resin, a modified silicone resin, and a graft copolymer composed of an acrylic resin and a silicone resin. Since the silicone resin is generally hydrophobic, it is also preferable from the viewpoint of suppressing performance degradation due to moisture absorption. The silicone resin may be a linear type or a branched type. Moreover, any of a dialkyl silicone resin, an alkylaryl silicone resin, a diaryl silicone resin, and the like may be used. Among them, dimethyldiphenyl silicone resin is preferable from the viewpoint of low gas permeability, low water content, and refractive index control when combined with a matrix resin described later.
A dispersion medium may be used individually by 1 type, or may use 2 or more types together.
変性シリコーン樹脂は、直鎖型であっても分岐鎖型であってもよい。また、変性シリコーン樹脂は、主鎖であるポリシロキサン鎖の側鎖に変性基を有する側鎖型、主鎖であるポリシロキサン鎖の両末端に変性基を有する両末端型、主鎖であるポリシロキサン鎖の片末端に変性基を有する片末端型、主鎖であるポリシロキサン鎖の側鎖及び末端の両方に変性基を有する側鎖両末端型、主鎖であるポリシロキサン鎖の側鎖及び末端の片方に変性基を有する側鎖片末端型等のいずれであってもよい。変性シリコーン樹脂における変性基は、目的等に応じて適宜選択することができる。変性基としては、例えば、アミノ基、モノアルキルアミノ基、ジアルキルアミノ基、モノアリールアミノ基、ジアリールアミノ基、エポキシ基、脂環式エポキシ基、ヒドロキシ基、メルカプト基、カルボキシ基、ポリエーテル基、アラルキル基、フルオロアルキル基、長鎖アルキル基、高級脂肪酸エステル基、高級脂肪酸アミド基等を挙げることができる。これらの変性基をもつ変性シリコーンを樹脂適宜選択することにより、電磁波調整粒子との親和性が向上して電磁波調整粒子の分散が安定したり、後述するマトリックス樹脂に対して安定的に液滴を形成したりすることができる。 The modified silicone resin may be a linear type or a branched type. Further, the modified silicone resin is composed of a side chain type having a modifying group at the side chain of the polysiloxane chain that is the main chain, a double-end type having a modifying group at both ends of the polysiloxane chain that is the main chain, and a polysiloxane that is the main chain. One-end type having a modifying group at one end of the siloxane chain, both side chains of the polysiloxane chain as the main chain and both ends of the side chain having a modifying group at the end, the side chain of the polysiloxane chain as the main chain, and Any one of a side-chain single-end type having a modifying group on one end may be used. The modifying group in the modified silicone resin can be appropriately selected depending on the purpose and the like. Examples of the modifying group include an amino group, a monoalkylamino group, a dialkylamino group, a monoarylamino group, a diarylamino group, an epoxy group, an alicyclic epoxy group, a hydroxy group, a mercapto group, a carboxy group, a polyether group, Examples thereof include an aralkyl group, a fluoroalkyl group, a long chain alkyl group, a higher fatty acid ester group, a higher fatty acid amide group, and the like. By appropriately selecting the modified silicone having these modifying groups as the resin, the affinity with the electromagnetic wave adjusting particles is improved and the dispersion of the electromagnetic wave adjusting particles is stabilized. Or can be formed.
アクリル樹脂とシリコーン樹脂とを含むグラフト共重合体は、主鎖がアクリル樹脂に由来する構造の化合物であっても、主鎖がシリコーン樹脂に由来する構造の化合物であってもよい。 The graft copolymer containing an acrylic resin and a silicone resin may be a compound having a structure in which the main chain is derived from an acrylic resin or a compound having a structure in which the main chain is derived from a silicone resin.
分散媒は調整したものを用いても、市販品を用いてもよい。市販品としては、例えば、ジメチルフェニルシリコーン（ＫＦ−５３、信越化学工業株式会社）が挙げられる。 A dispersion medium may be used, or a commercially available product may be used. As a commercial item, dimethylphenyl silicone (KF-53, Shin-Etsu Chemical Co., Ltd.) is mentioned, for example.
分散媒の粘度は特に制限されず、目的等に応じて適宜選択できる。電磁波調整素子の応答速度の観点からは、２５℃での粘度が１ｍＰａ・ｓ〜５０００ｍＰａ・ｓであることが好ましく、１００ｍＰａ・ｓ〜５０００ｍＰａ・ｓであることがより好ましい。本明細書において、分散媒を２種以上併用する場合には、分散媒の粘度とは、併用する分散媒の混合物の粘度を意味する。温度変化による電磁波調整素子の応答速度の変動を小さくする観点からは、−２０℃〜１００℃の温度範囲での分散媒の粘度変化率（％）が、２桁以内であることが好ましい。なお、分散媒の粘度は、レオメーター（例えば、ＭＣＲ３０２、株式会社Ａｎｔｏｎ Ｐａａｒ）を用いて、常法により測定できる。 The viscosity of the dispersion medium is not particularly limited and can be appropriately selected depending on the purpose and the like. From the viewpoint of the response speed of the electromagnetic wave adjusting element, the viscosity at 25 ° C. is preferably 1 mPa · s to 5000 mPa · s, and more preferably 100 mPa · s to 5000 mPa · s. In this specification, when two or more kinds of dispersion media are used in combination, the viscosity of the dispersion medium means the viscosity of the mixture of the dispersion media used together. From the viewpoint of reducing fluctuations in the response speed of the electromagnetic wave adjusting element due to temperature changes, the viscosity change rate (%) of the dispersion medium in the temperature range of −20 ° C. to 100 ° C. is preferably within two digits. The viscosity of the dispersion medium can be measured by a conventional method using a rheometer (for example, MCR302, Anton Paar Co., Ltd.).
分散媒の屈折率は特に制限されず、目的とする吸収波長、及び、電磁波調整粒子、後述のマトリックス樹脂、絶縁層等の電磁波調整素子の構成材料の種類などに応じて適宜選択できる。電磁波調整素子における可視光調整の観点からは、屈折率は１．３３〜１．５８であることが好ましく、１．３９〜１．５１であることがより好ましい。分散媒を２種以上併用する場合には、分散媒の屈折率についても粘度と同様に、併用する分散媒の混合物の屈折率を意味する。なお、分散媒の屈折率はアッべ屈折計（例えば、ＤＲ−Ａ１、株式会社アタゴ）、デジタル屈折計（例えば、ＲＸ−９０００α、株式会社アタゴ）等を用いて、２５℃で常法により測定できる。 The refractive index of the dispersion medium is not particularly limited, and can be appropriately selected according to the intended absorption wavelength and the type of constituent material of the electromagnetic wave adjusting element such as the electromagnetic wave adjusting particles, the matrix resin described later, and the insulating layer. From the viewpoint of visible light adjustment in the electromagnetic wave adjusting element, the refractive index is preferably 1.33 to 1.58, and more preferably 1.39 to 1.51. When two or more kinds of dispersion media are used in combination, the refractive index of the dispersion medium means the refractive index of the mixture of the dispersion media to be used in the same manner as the viscosity. The refractive index of the dispersion medium is measured by an ordinary method at 25 ° C. using an Abbe refractometer (for example, DR-A1, Atago Co., Ltd.), a digital refractometer (for example, RX-9000α, Atago Co., Ltd.), or the like. it can.
分散媒の含有量は、電磁波調整粒子の分散性に応じて適宜調整してよい。電磁波調整粒子の分散性の観点からは、分散媒の含有量は、電磁波調整粒子と分散媒の合計量に対して７０質量％〜９９．９質量％であることが好ましく、７５質量％〜９９.８質量％であることがより好ましく、８０質量％〜９９．７質量％であることがさらに好ましい。 The content of the dispersion medium may be appropriately adjusted according to the dispersibility of the electromagnetic wave adjusting particles. From the viewpoint of dispersibility of the electromagnetic wave adjusting particles, the content of the dispersion medium is preferably 70% by mass to 99.9% by mass with respect to the total amount of the electromagnetic wave adjusting particles and the dispersion medium, and 75% by mass to 99%. It is more preferable that it is 0.8 mass%, and it is further more preferable that it is 80 mass%-99.7 mass%.
［マトリックス樹脂］
分散体は、さらにマトリックス樹脂を含んでもよく、当該マトリックス樹脂が液滴を含み、当該液滴が電磁波調整粒子と分散媒とを含む状態で、電磁波調整粒子が存在していてもよい。分散体がさらにマトリックス樹脂を含み、当該マトリックス樹脂が液滴を含み、当該液滴が電磁波調整粒子と分散媒とを含む状態で電磁波調整粒子が存在すると、電磁波調整素子を構成したときに電磁波調整粒子の凝集、沈降等が抑制され、ムラのない電磁波調整効果が得られる傾向にある。また、マトリックス樹脂を硬化させることで、マトリックス樹脂中に液滴状に存在している分散体の位置が安定し、よりムラのない電磁波調整効果が得られる傾向にある。
[Matrix resin]
The dispersion may further contain a matrix resin, and the electromagnetic wave adjusting particles may be present in a state where the matrix resin contains liquid droplets and the liquid droplets contain the electromagnetic wave adjusting particles and the dispersion medium. If the dispersion further includes a matrix resin, the matrix resin includes droplets, and the electromagnetic wave adjusting particles are present in a state where the droplets include the electromagnetic wave adjusting particles and the dispersion medium, the electromagnetic wave adjusting element is configured when the electromagnetic wave adjusting element is configured. Aggregation, sedimentation, and the like of particles are suppressed, and an electromagnetic wave adjustment effect without unevenness tends to be obtained. Further, by curing the matrix resin, the position of the dispersion existing in the form of droplets in the matrix resin is stabilized, and there is a tendency that a more uniform electromagnetic wave adjusting effect can be obtained.
マトリックス樹脂は、分散媒と相分離しうるものであって、分散媒と混合した際にマトリックス樹脂中に分散媒が液滴状に存在しうるものであれば特に制限されない。マトリックス樹脂は、紫外線照射等により硬化するものであることが好ましい。このような分散媒とマトリックス樹脂の組み合わせとしては、例えば、分散媒が（メタ）アクリル酸エステルオリゴマーであり、マトリックス樹脂が紫外線硬化型シリコーン樹脂である組み合わせが挙げられる。良好な電磁波透過率を達成する観点からは、マトリックス樹脂と分散媒の屈折率差は０．０１以内であることが好ましく、０．００５以内であることがより好ましい。 The matrix resin can be phase-separated from the dispersion medium, and is not particularly limited as long as the dispersion medium can be present in the form of droplets in the matrix resin when mixed with the dispersion medium. The matrix resin is preferably one that is cured by ultraviolet irradiation or the like. Examples of such a combination of the dispersion medium and the matrix resin include a combination in which the dispersion medium is a (meth) acrylate oligomer and the matrix resin is an ultraviolet curable silicone resin. From the viewpoint of achieving good electromagnetic wave transmittance, the difference in refractive index between the matrix resin and the dispersion medium is preferably within 0.01, and more preferably within 0.005.
マトリックス樹脂が液滴を含み、当該液滴が電磁波調整粒子と分散媒とを含む状態とする方法は特に制限されない。例えば、特開２００２−１８９１２３号公報（特許文献１）の［０００９］〜［００３６］に記載の方法を参照することができる。 There is no particular limitation on the method in which the matrix resin contains droplets and the droplets contain electromagnetic wave adjusting particles and a dispersion medium. For example, the method described in [0009] to [0036] of JP-A-2002-189123 (Patent Document 1) can be referred to.
マトリックス樹脂が液滴を含み、当該液滴が電磁波調整粒子と分散媒とを含む場合、マトリックス樹脂の含有量は特に限定されない。分散体の均一性及び良好な電磁波調整効果を両立する観点からは、マトリックス樹脂の含有量は、マトリックス樹脂を含む分散体の総質量に対して、５５質量％〜９９質量％であることが好ましく、６０質量％〜９８質量％であることがより好ましく、６５質量％〜９７質量％であることがさらに好ましい。 When the matrix resin includes droplets and the droplets include electromagnetic wave adjusting particles and a dispersion medium, the content of the matrix resin is not particularly limited. From the viewpoint of achieving both uniformity of the dispersion and good electromagnetic wave adjusting effect, the content of the matrix resin is preferably 55% by mass to 99% by mass with respect to the total mass of the dispersion containing the matrix resin. 60 mass% to 98 mass% is more preferable, and 65 mass% to 97 mass% is even more preferable.
［その他の成分］
分散体は、必要に応じて電磁波調整粒子、分散媒及びマトリックス樹脂以外の成分を含んでもよい。このような成分としては、例えば、界面活性剤等の分散安定剤、粘度調整のための増粘剤、遮光及び透過状態における電磁波調整素子の色調を補正するための顔料、染料等の着色剤などが挙げられる。分散体が顔料を含む場合、ヘイズ抑制の観点から、顔料の平均粒子径は５００ｎｍ以下であることが好ましく、１００ｎｍ以下であることがより好ましい。なお、平均粒子径は、走査型電子顕微鏡（ＳＥＭ）、透過型電子顕微鏡（ＴＥＭ）等による観察によって測定できる。例えば、走査型電子顕微鏡（ＳＥＭ）、透過型電子顕微鏡（ＴＥＭ）等の電子顕微鏡で顔料を撮影し、撮影した画像より任意に１００個の顔料を抽出し、顔料のそれぞれの最大直径の長さの算術平均値として算出することができる。
[Other ingredients]
The dispersion may contain components other than the electromagnetic wave adjusting particles, the dispersion medium, and the matrix resin as necessary. Examples of such components include dispersion stabilizers such as surfactants, thickeners for viscosity adjustment, pigments for correcting the color tone of the electromagnetic wave adjusting element in a light-shielding and transmitting state, and colorants such as dyes. Is mentioned. When the dispersion contains a pigment, the average particle diameter of the pigment is preferably 500 nm or less, and more preferably 100 nm or less from the viewpoint of haze suppression. The average particle diameter can be measured by observation with a scanning electron microscope (SEM), a transmission electron microscope (TEM), or the like. For example, a pigment is photographed with an electron microscope such as a scanning electron microscope (SEM) or a transmission electron microscope (TEM), 100 pigments are arbitrarily extracted from the photographed image, and the length of each maximum diameter of the pigment. It can be calculated as an arithmetic average value of
＜電磁波調整素子＞
本実施の形態の電磁波調整素子は、一対の導電性基材と、前記一対の導電性基材の間に配置される電磁波調整用分散体と、を有する。電磁波調整用分散体は、電磁波調整粒子と、分散媒とを含み、その詳細及び好ましい態様は上述したとおりである。
電磁波調整素子の構造の一例とその駆動原理について、図１を参照して説明する。しかし、本発明はこれに限定されるものではない。また、各図における部材の大きさは概念的なものであり、部材間の大きさの相対的な関係はこれに限定されない。
<Electromagnetic wave adjusting element>
The electromagnetic wave adjusting element of the present embodiment has a pair of conductive substrates and an electromagnetic wave adjusting dispersion disposed between the pair of conductive substrates. The electromagnetic wave adjusting dispersion includes electromagnetic wave adjusting particles and a dispersion medium, and details and preferred embodiments thereof are as described above.
An example of the structure of the electromagnetic wave adjusting element and its driving principle will be described with reference to FIG. However, the present invention is not limited to this. Moreover, the magnitude | size of the member in each figure is notional, The relative relationship of the magnitude | size between members is not limited to this.
電磁波調整素子１は、導電層５、７がそれぞれコーティングされた基材４、６からなる導電性基材２、３を備えている。導電性基材２と導電性基材３との間には、電磁波調整用分散体８が層状に配置されている。電磁波調整用分散体８は、電磁波調整粒子９及び分散媒１０を含有している。電磁波調整粒子９の材料が低抵抗である場合は必要に応じ、電磁波調整粒子９の分散状態変化等による短絡を防止するために、導電層５、７と電磁波調整用分散体８との間に絶縁層を形成してもよい。絶縁層は透明性が高く、導電性基材２、３を損傷せずに作製できることが好ましい。また、分散媒に対して親和性を持つが、変質したり分散体中に溶出したりせず、分散媒との屈折率差が小さいものが好ましい。材質は特に制限されず、例えば、ＳｉＯ２、Ａｌ２Ｏ３等の酸化物、層状ケイ酸鉱物等のアルミノケイ酸塩、シリコン窒化物などの無機物；ポリイミド系、アクリル系等の有機樹脂；これらの無機物と有機樹脂の複合物などが挙げられ、電磁波調整用分散体８、マトリックス樹脂、透明導電性基材２、３、後述の封着剤に対する親和性、化学的な安定性、さらには温度、湿度、日射等の使用環境条件などに応じて選択される。
また、電磁波調整粒子９を含めた電磁波調整素子構成材料の耐久性向上のため、基材４、６の外側に、水、酸素等の雰囲気ガス、紫外線、赤外線などが電磁波調整素子内に進入するのを遮断するフィルムを設置したり保護膜を形成しても構わない。
電磁波調整素子１には、スイッチ１１を介して電源１２が接続されている。電磁波調整素子１を作動させるための使用電源は、例えば、交流で、５Ｖ〜３００Ｖの電圧範囲（実効値）、３０Ｈｚ〜５００ｋＨｚの周波数範囲とすることができる。
The electromagnetic wave adjusting element 1 includes conductive base materials 2 and 3 composed of base materials 4 and 6 coated with conductive layers 5 and 7, respectively. Between the conductive substrate 2 and the conductive substrate 3, the electromagnetic wave adjusting dispersion 8 is arranged in a layered manner. The electromagnetic wave adjusting dispersion 8 contains electromagnetic wave adjusting particles 9 and a dispersion medium 10. If the material of the electromagnetic wave adjusting particles 9 has a low resistance, the conductive layers 5 and 7 and the electromagnetic wave adjusting dispersion 8 are interposed between the conductive layers 5 and 7 and the electromagnetic wave adjusting dispersion 8 in order to prevent a short circuit due to a dispersion state change of the electromagnetic wave adjusting particles 9 and the like. An insulating layer may be formed. It is preferable that the insulating layer is highly transparent and can be produced without damaging the conductive substrates 2 and 3. In addition, it is preferable to have an affinity for the dispersion medium, but it does not deteriorate or elute in the dispersion and has a small refractive index difference from the dispersion medium. The material is not particularly limited, and examples thereof include oxides such as SiO 2 and Al 2 O 3 , aluminosilicates such as layered silicate minerals, inorganic materials such as silicon nitrides; organic resins such as polyimides and acrylics; Examples include a composite of an inorganic substance and an organic resin, an electromagnetic wave adjusting dispersion 8, a matrix resin, transparent conductive substrates 2, 3, affinity for a sealing agent described later, chemical stability, temperature, It is selected according to the environmental conditions such as humidity and solar radiation.
Further, in order to improve the durability of the electromagnetic wave adjusting element constituent material including the electromagnetic wave adjusting particles 9, atmospheric gases such as water and oxygen, ultraviolet rays, infrared rays, etc. enter the electromagnetic wave adjusting element outside the substrates 4 and 6. You may install the film which interrupts | blocks this and may form a protective film.
A power source 12 is connected to the electromagnetic wave adjusting element 1 via a switch 11. The power source used for operating the electromagnetic wave adjusting element 1 can be, for example, an AC voltage range of 5 V to 300 V (effective value) and a frequency range of 30 Hz to 500 kHz.
図１（ａ）に示す状態では、電磁波調整素子１のスイッチ１１が切られ、電界が印加されていないため、電磁波調整用分散体８中の電磁波調整粒子９は、ブラウン運動により、それぞれランダムな方向を向いている。そのため、電磁波調整素子１に入射した電磁波は、個々の電磁波調整粒子９の向きによって、短軸又は長軸で吸収される。主には、電磁波調整粒子９の長軸方向での吸収により、透過率が低下する。
図１（ｂ）に示すように電磁波調整素子１のスイッチ１１を接続して電界を印加すると、電磁波調整粒子９の長軸が電場に沿うように配列する。入射した電磁波の電磁波調整粒子９による吸収は、長軸よりも吸収の小さい短軸によって主に行われるため、電磁波調整素子１に電界が印加されていない状態に比べて小さい。その結果、電磁波調整素子１に電界が印加されていない状態に比べて電磁波透過率が高く維持される。
In the state shown in FIG. 1 (a), the switch 11 of the electromagnetic wave adjusting element 1 is turned off and no electric field is applied. Therefore, the electromagnetic wave adjusting particles 9 in the electromagnetic wave adjusting dispersion 8 are each random due to Brownian motion. Facing the direction. Therefore, the electromagnetic wave incident on the electromagnetic wave adjusting element 1 is absorbed by the short axis or the long axis depending on the direction of the individual electromagnetic wave adjusting particles 9. The transmittance decreases mainly due to absorption of the electromagnetic wave adjusting particles 9 in the major axis direction.
When the switch 11 of the electromagnetic wave adjusting element 1 is connected and an electric field is applied as shown in FIG. 1B, the long axes of the electromagnetic wave adjusting particles 9 are arranged so as to follow the electric field. The absorption of the incident electromagnetic wave by the electromagnetic wave adjusting particles 9 is mainly performed by the short axis whose absorption is smaller than the long axis, and thus is smaller than the state where no electric field is applied to the electromagnetic wave adjusting element 1. As a result, the electromagnetic wave transmittance is maintained higher than that in the state where no electric field is applied to the electromagnetic wave adjusting element 1.
［電磁波調整素子の製造方法］
電磁波調整素子の製造方法は特に制限されない。例えば、以下の工程（１）及び（２）を含む方法によって製造することができる。
[Method of manufacturing electromagnetic wave adjusting element]
The manufacturing method of the electromagnetic wave adjusting element is not particularly limited. For example, it can be produced by a method including the following steps (1) and (2).
（１）一対の導電性基材を対向させて配置し、その間に封着剤を付与し、一対の導電性基材を接着する。これにより、電磁波調整用分散体の厚みに相当する空間が一対の導電性基材の間に形成される。封着剤を付与する位置は、例えば、導電性基材の端部とすることができる。また、封着剤がスペーサービーズ等を含む場合には、導電性基材の対向面の全体又は一部とすることができる。導電性基材間の距離は、特に制限されない。例えば、２５μｍ〜３００μｍの範囲内とすることができる。導電性基材間の距離が２５μｍ以上であると、電磁波調整素子の厚みの均一性を保持しやすい傾向があり、３００μｍ以下であると、駆動電圧を小さくできる傾向がある。 (1) A pair of conductive substrates are arranged to face each other, a sealing agent is applied therebetween, and the pair of conductive substrates are bonded. Thereby, a space corresponding to the thickness of the electromagnetic wave adjusting dispersion is formed between the pair of conductive substrates. The position where the sealing agent is applied can be, for example, an end portion of the conductive base material. Moreover, when a sealing agent contains spacer beads etc., it can be set as the whole or one part of the opposing surface of an electroconductive base material. The distance between the conductive substrates is not particularly limited. For example, it can be in the range of 25 μm to 300 μm. When the distance between the conductive substrates is 25 μm or more, the thickness uniformity of the electromagnetic wave adjusting element tends to be easily maintained, and when it is 300 μm or less, the driving voltage tends to be reduced.
（２）次いで、一対の導電性基材間の空間に分散体を充填する。分散体は、例えば、上述した分散体の調製方法によって調製することができる。分散体の充填方法は特に制限されない。例えば、導電性基材の端部の封着剤で封止していない場所から毛細管現象によって充填することができる。導電性基材の間に分散液を充填後、導電性基材の端部の封着剤で封着していない場所を封着剤で封止する。これにより、分散液は外気から隔離される。 (2) Next, the dispersion is filled in the space between the pair of conductive substrates. The dispersion can be prepared, for example, by the dispersion preparation method described above. The method for filling the dispersion is not particularly limited. For example, it can be filled by capillarity from a place not sealed with the sealing agent at the end of the conductive substrate. After filling the dispersion between the conductive substrates, the portions of the conductive substrate that are not sealed with the sealing agent are sealed with the sealing agent. Thereby, the dispersion is isolated from the outside air.
他の方法としては、例えば、分散体を一方の導電性基材の面上に付与し、その後、分散体を付与した面にもう一方の導電性基材を貼り合わせて接着し、封止する方法が挙げられる。分散液の付与方法としては、例えば、バーコーター、アプリケーター、ドクターブレード、ロールコーター、ダイコーター、コンマコーター等を用いる方法、真空下での滴下注入法（ＯＤＦ）などが挙げられる。分散体を導電性基材に付与する際は、必要に応じて、電磁波調整粒子等の構成材料の溶解性等に応じて適当な溶剤で分散液を希釈してもよい。溶剤を用いた場合には、導電性基材上に分散液を付与した後で溶剤を揮発させることが好ましい。 As another method, for example, a dispersion is applied on the surface of one conductive substrate, and then the other conductive substrate is bonded and bonded to the surface to which the dispersion is applied, followed by sealing. A method is mentioned. Examples of the method for applying the dispersion include a method using a bar coater, an applicator, a doctor blade, a roll coater, a die coater, a comma coater and the like, and a dropping injection method (ODF) under vacuum. When the dispersion is applied to the conductive substrate, the dispersion may be diluted with an appropriate solvent according to the solubility of constituent materials such as electromagnetic wave adjusting particles, if necessary. When a solvent is used, it is preferable to volatilize the solvent after applying the dispersion on the conductive substrate.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.
〔比較例１〕
＜ポリヨウ素化物の酢酸イソアミル分散液の調製＞
ヨウ素（ＪＩＳ試薬特級、和光純薬工業株式会社）と酢酸イソアミル（試薬特級、和光純薬工業株式会社）から８．５質量％ヨウ素の酢酸イソアミル溶液（ヨウ素溶液）を調製し、ニトロセルロース（１／４ＬＩＧ、ベルジュラックＮＣ社）と酢酸イソアミルから２０．０質量％ニトロセルロースの酢酸イソアミル溶液（ニトロセルロース溶液）を調製した。ヨウ化カルシウム水和物（化学用、和光純薬工業株式会社）を加熱乾燥して無水化して酢酸イソアミルに溶解させ、２０．９質量％ヨウ化カルシウム溶液を調製した。２０Ｌフラスコに撹拌機と冷却管を備え、ヨウ素溶液６９０５ｇ及びニトロセルロース溶液８７２３ｇを加え水浴温度を３５℃〜４０℃としてフラスコを加熱した。ニトロセルロース溶液中の水分比（質量％）を平沼産業株式会社、平沼水分測定装置ＡＱ−７（発生液：ハイドラナールアクアライトＲＳ、対極液：アクアライトＣＮ）を用いて測定したところ、０．６１質量％であり、加えた溶液質量からニトロセルロース溶液中の水分量は５３．２ｇと算出された。
[Comparative Example 1]
<Preparation of polyiodide isoamyl acetate dispersion>
An 8.5 mass% iodine isoamyl acetate solution (iodine solution) was prepared from iodine (JIS reagent special grade, Wako Pure Chemical Industries, Ltd.) and isoamyl acetate (reagent special grade, Wako Pure Chemical Industries, Ltd.), and nitrocellulose (1 / 4LIG, Bergerac NC) and an isoamyl acetate solution (nitrocellulose solution) of 20.0% by mass nitrocellulose was prepared. Calcium iodide hydrate (chemical use, Wako Pure Chemical Industries, Ltd.) was dried by heating, dehydrated and dissolved in isoamyl acetate to prepare a 20.9 mass% calcium iodide solution. A 20 L flask was equipped with a stirrer and a condenser, 6905 g of iodine solution and 8723 g of nitrocellulose solution were added, and the flask was heated at a water bath temperature of 35 ° C. to 40 ° C. The water ratio (% by mass) in the nitrocellulose solution was measured using Hiranuma Sangyo Co., Ltd., Hiranuma moisture measuring device AQ-7 (generated liquid: Hydranal Aqualite RS, counter electrode liquid: Aqualite CN). The amount of water in the nitrocellulose solution was calculated to be 53.2 g from the added solution mass.
フラスコ内容物の温度が３５℃〜４０℃となった後、脱水メタノール（試薬特級、和光純薬工業株式会社）２６０ｇ及び精製水（和光純薬工業株式会社）５５．６ｇを加えて撹拌した。ここにヨウ化カルシウム溶液１６４３ｇを加え、次いでピラジン−２，５−ジカルボン酸（日立化成テクノサービス株式会社）３９０ｇを加えた。水浴温度を４２℃〜４４℃として４時間撹拌した後、放冷した。 After the temperature of the flask contents reached 35 ° C. to 40 ° C., 260 g of dehydrated methanol (special grade reagent, Wako Pure Chemical Industries, Ltd.) and 55.6 g of purified water (Wako Pure Chemical Industries, Ltd.) were added and stirred. To this, 1643 g of calcium iodide solution was added, and then 390 g of pyrazine-2,5-dicarboxylic acid (Hitachi Chemical Techno Service Co., Ltd.) was added. The water bath temperature was set to 42 ° C. to 44 ° C. and the mixture was stirred for 4 hours and then allowed to cool.
得られた合成液を９２６０Ｇで５時間遠心分離後、傾斜して上澄み液を除き、底部に残存した沈殿に、この沈殿の質量の５倍に相当する酢酸イソアミルを加えて、超音波で沈殿を分散した。次に７１０Ｇで１０分間遠心分離後、上澄みを９２６０Ｇで３時間遠心分離した。再び傾斜して上澄みを除き、底部に残存した沈殿に、この沈殿の質量の５倍に相当する酢酸イソアミルを加え、超音波で沈殿を分散して、電磁波調整粒子としてのポリヨウ素化物の酢酸イソアミル分散液を調製した。 The resulting synthesis solution is centrifuged at 9260 G for 5 hours, and the supernatant is removed by inclining. To the precipitate remaining at the bottom, isoamyl acetate corresponding to 5 times the mass of the precipitate is added, and the precipitate is ultrasonicated. Distributed. Next, after centrifuging at 710 G for 10 minutes, the supernatant was centrifuged at 9260 G for 3 hours. Inclined again, the supernatant was removed, and isoamyl acetate corresponding to 5 times the mass of the precipitate was added to the precipitate remaining at the bottom, and the precipitate was dispersed with ultrasound to obtain isoamyl acetate of polyiodide as electromagnetic wave adjusting particles. A dispersion was prepared.
得られた電磁波調整粒子１００個を透過型電子顕微鏡で観察したところ、形状異方性があることが確認され、アスペクト比の平均値は４．７、長軸の長さの平均値は４２０ｎｍであった。 When 100 pieces of the obtained electromagnetic wave adjusting particles were observed with a transmission electron microscope, it was confirmed that there was shape anisotropy, the average value of the aspect ratio was 4.7, and the average value of the length of the major axis was 420 nm. there were.
＜ポリヨウ素化物の耐溶剤性の評価＞
メタノール及びエタノール１ｍＬに対して、得られたポリヨウ素化物の酢酸イソアミル分散液を加え、ポリヨウ素化物の濃度が１質量％になるよう調製した。得られた溶液を３分間静置し、電磁波調整粒子の様子を観察したところ、ポリヨウ素化物はメタノール及びエタノールに溶解した。
<Evaluation of solvent resistance of polyiodide>
An isoamyl acetate dispersion of the resulting polyiodide was added to 1 mL of methanol and ethanol to prepare a polyiodide concentration of 1% by mass. When the obtained solution was allowed to stand for 3 minutes and the state of the electromagnetic wave adjusting particles was observed, the polyiodide was dissolved in methanol and ethanol.
＜ポリヨウ素化物のシリコーン分散液の調製＞
ナスフラスコに前記電磁波調整粒子の酢酸イソアミル分散液１０ｇとジメチルジフェニルシリコーン樹脂（ＫＦ−５３、信越化学工業株式会社）を１０ｇ加え、湯浴で５０℃〜６０℃に加温しながらエバポレーターで酢酸イソアミルを留去したところ、ポリヨウ素化物が凝集してしまい、ポリヨウ素化物のシリコーン分散液は作製できなかった。
<Preparation of silicone dispersion of polyiodide>
10 g of isoamyl acetate dispersion of the electromagnetic wave adjusting particles and 10 g of dimethyldiphenyl silicone resin (KF-53, Shin-Etsu Chemical Co., Ltd.) are added to the eggplant flask, and isoamyl acetate is heated with an evaporator while heating to 50 ° C. to 60 ° C. When distilling off, polyiodide aggregated, and a silicone dispersion of polyiodide could not be prepared.
〔実施例１〕
＜ポリヨウ素化物の表面への高分子共重合体付与とマクロモノマーの付与＞
ポリヨウ素化物の合成は比較例１に記載の通り行った。
ナスフラスコに６質量％の前記ポリヨウ素化物の酢酸イソアミル分散液１６．７ｇ、ジラウリン酸ジブチル錫（ＩＶ）（アルドリッチ株式会社）０．２４ｇ、酢酸イソアミル８３．３ｇ、メタクリロイルオキシエチルイソシアナート（昭和電工株式会社）２．９６ｇを加え、真空雰囲気下、６０℃で２１時間撹拌した。得られた分散溶液を分散溶液質量の４倍に相当するヘキサン（関東化学株式会社）に加え、９０００ｒｐｍ（回転／分）で１０分間遠心分離を行い、上澄みを除去し、酢酸イソアミル４０ｇを加え、３０分間超音波処理を施した。この操作を２回繰り返し行い、重合性官能基を付与した１．８質量％のポリヨウ素化物の酢酸イソアミル分散液を得た。ナスフラスコに１０分間超音波処理を施した。
[Example 1]
<Applying high molecular copolymer and macromonomer to the surface of polyiodide>
The synthesis of polyiodide was performed as described in Comparative Example 1.
In an eggplant flask, 16.7 g of an isoamyl acetate dispersion of 6% by mass of the polyiodide, 0.24 g of dibutyltin (IV) dilaurate (Aldrich), 83.3 g of isoamyl acetate, methacryloyloxyethyl isocyanate (Showa Denko) Inc.) 2.96 g was added and stirred at 60 ° C. for 21 hours in a vacuum atmosphere. The obtained dispersion solution is added to hexane (Kanto Chemical Co., Ltd.) corresponding to 4 times the mass of the dispersion solution, centrifuged at 9000 rpm (rotation / min) for 10 minutes, the supernatant is removed, and 40 g of isoamyl acetate is added, Sonication was performed for 30 minutes. This operation was repeated twice to obtain an isoamyl acetate dispersion of 1.8% by mass of polyiodide having a polymerizable functional group. The eggplant flask was sonicated for 10 minutes.
上記の重合性官能基を有するポリヨウ素化物の酢酸イソアミル分散液２．７９ｇ、アクリロニトリル（関東化学株式会社）０．１５９ｇ、メチルメタクリレート（和光純薬工業株式会社）０．０３４ｇ、ジメチルシリコーンマクロモノマー（ＦＭ−０７２１、ＪＮＣ株式会社）を０．１７０ｇ、酢酸イソアミル１．８４９ｇを加えて１０分間窒素バブリングを行い脱気した。その後窒素雰囲気下、６０℃で２４時間撹拌した。得られた分散液を分散液の質量の４倍に相当するエタノール（和光純薬工業株式会社）に加え、６０００ｒｐｍ（回転/分）で１０分間遠心分離を行い、上澄みを除去し、酢酸イソアミル４ｇを加え、３０分間超音波処理を施した。この操作を３回繰り返し行い、ポリヨウ素化物の粒子表面に高分子共重合体を付与し、さらに高分子共重合体表面にシリコーンマクロモノマーが付与された電磁波調整粒子の酢酸イソアミル分散液を得た。
得られた電磁波調整粒子１００個を透過型電子顕微鏡で観察したところ、形状異方性があることが確認された。電磁波調整粒子のアスペクト比の平均値は６．３、長軸の長さの平均値は５６０ｎｍであった。また、透過型電子顕微鏡により、ポリヨウ素化物の表面への高分子共重合体の付与を確認した。
2.79 g of an isoamyl acetate dispersion of polyiodide having the above polymerizable functional group, 0.159 g of acrylonitrile (Kanto Chemical Co., Ltd.), 0.034 g of methyl methacrylate (Wako Pure Chemical Industries, Ltd.), dimethyl silicone macromonomer ( FM-0721, JNC Corporation) 0.170 g and isoamyl acetate 1.849 g were added and degassed by bubbling with nitrogen for 10 minutes. Thereafter, the mixture was stirred at 60 ° C. for 24 hours under a nitrogen atmosphere. The obtained dispersion is added to ethanol (Wako Pure Chemical Industries, Ltd.) corresponding to 4 times the mass of the dispersion, centrifuged at 6000 rpm (rotation / min) for 10 minutes, the supernatant is removed, and isoamyl acetate 4 g And sonicated for 30 minutes. This operation was repeated three times to obtain an isoamyl acetate dispersion of electromagnetic wave adjusting particles in which a polymer copolymer was imparted to the surface of polyiodide particles and a silicone macromonomer was further imparted to the surface of the polymer copolymer. .
When 100 obtained electromagnetic wave adjusting particles were observed with a transmission electron microscope, it was confirmed that there was shape anisotropy. The average aspect ratio of the electromagnetic wave adjusting particles was 6.3, and the average length of the major axis was 560 nm. Moreover, the provision of the high molecular copolymer to the surface of the polyiodide was confirmed by a transmission electron microscope.
＜電磁波調整粒子のシリコーン分散液の調製＞
前記電磁波調整粒子の酢酸イソアミル分散液２ｇをエタノール８ｇに加え、６０００ｒｐｍ（回転/分）で１０分間遠心分離を行い、上澄みを除去し、ヘキサン１．７ｇを加え、３０分間超音波処理を施した。ナスフラスコに得られたヘキサン分散液１．７ｇとジメチルジフェニルシリコーン（ＫＦ−５３、信越化学工業株式会社）を１．０ｇ加え、湯浴で４０℃〜５０℃に加温しながらエバポレーターで酢酸イソアミル、ヘキサン、エタノールを留去し、４０℃で５時間以上真空乾燥して、１．０質量％の電磁波調整粒子のシリコーン分散液を得た。
<Preparation of silicone dispersion of electromagnetic wave adjusting particles>
2 g of isoamyl acetate dispersion of the electromagnetic wave adjusting particles was added to 8 g of ethanol, centrifuged at 6000 rpm (rotation / min) for 10 minutes, the supernatant was removed, 1.7 g of hexane was added, and sonication was performed for 30 minutes. . Add 1.7 g of the hexane dispersion obtained in the eggplant flask and 1.0 g of dimethyldiphenyl silicone (KF-53, Shin-Etsu Chemical Co., Ltd.), and heat to 40 ° C to 50 ° C in a hot water bath with isoamyl acetate with an evaporator. Then, hexane and ethanol were distilled off, followed by vacuum drying at 40 ° C. for 5 hours or longer to obtain 1.0 mass% silicone dispersion of electromagnetic wave adjusting particles.
＜電磁波調整特性の評価＞
電磁波調整特性の評価用のガラスセルを作製した。ＩＴＯ電極を片面に有するガラス基板（２０ｍｍ×３０ｍｍ×０．７ｍｍ）を２枚用意し、１枚のガラス基板のＩＴＯ電極が形成された面上の端部の周囲に厚み５０μｍのＰＥＴフィルムを配置した。もう１枚のガラス基板のＩＴＯ電極が前記シリコーン分散液に接するように、ＰＥＴフィルムを介して重ね合わせ、向かい合う端部２箇所に紫外線硬化性樹脂を塗布し、紫外線を照射することで封止し、２枚のガラス板を貼り合わせた。次いで貼り合わせたガラス板の封止していない端部に電磁波調整粒子のシリコーン分散液０．０４ｇを滴下し、毛細管現象によって前記分散液を充填した。前記分散液が充填されたら、封止していない残りの２箇所に紫外線硬化性樹脂を塗布し、紫外線を照射することで２枚のガラス板の４辺を封止し、ガラスセルを作製した。これにより、分散液は外気から隔離される。
ガラス板の全光線透過率は８９％、ヘイズは０．３％であった。ガラス基板の厚さはマイクロメータで測定した。なお、ガラス板の全光線透過率は分光式測色ヘイズメーター（商品名：ＴＣ−１８００Ｈ、（有限会社東京電色製）を用いて測定した。なお、全光線透過率測定におけるブランクは空気とした。
作製したガラスセルを用いて、電圧を印加していない状態（ＯＦＦ）、２８０Ｖの電圧を印加した状態での透過率を測定した。駆動電圧は５００Ｈｚとした。測定は紫外可視近赤外分光光度計（Ｖ−６７０、日本分光株式会社）を用いて、室温（２５℃）で行った。結果を図３に示す。
<Evaluation of electromagnetic wave adjustment characteristics>
A glass cell for evaluation of electromagnetic wave adjusting characteristics was produced. Prepare two glass substrates (20mm x 30mm x 0.7mm) with ITO electrodes on one side, and place a 50μm thick PET film around the edge of the surface of the glass substrate on which the ITO electrodes are formed. did. The other glass substrate ITO electrode is placed over the PET dispersion so that it comes into contact with the silicone dispersion, and UV curable resin is applied to the two opposite ends and sealed by irradiation with ultraviolet rays. Two glass plates were bonded together. Next, 0.04 g of the silicone dispersion liquid of electromagnetic wave adjusting particles was dropped onto the unsealed end of the bonded glass plate, and the dispersion liquid was filled by capillary action. When the dispersion liquid was filled, an ultraviolet curable resin was applied to the remaining two unsealed portions, and four sides of the two glass plates were sealed by irradiating with ultraviolet rays, thereby producing a glass cell. . Thereby, the dispersion is isolated from the outside air.
The total light transmittance of the glass plate was 89%, and the haze was 0.3%. The thickness of the glass substrate was measured with a micrometer. The total light transmittance of the glass plate was measured using a spectroscopic colorimetric haze meter (trade name: TC-1800H, (manufactured by Tokyo Denshoku Co., Ltd.). did.
Using the produced glass cell, the transmittance was measured in a state where no voltage was applied (OFF) and a voltage of 280 V was applied. The driving voltage was 500 Hz. The measurement was performed at room temperature (25 ° C.) using an ultraviolet-visible near-infrared spectrophotometer (V-670, JASCO Corporation). The results are shown in FIG.
〔実施例２〕
ポリヨウ素化物の表面へ高分子共重合体を付与する際の窒素雰囲気下での反応時間を１８時間としたことを除いては、実施例１と同様にしてポリヨウ素化物の粒子表面に高分子共重合体を付与し、さらに高分子共重合体表面にシリコーンマクロモノマーが付与された電磁波調整粒子の酢酸イソアミル分散液を作製した。得られた電磁波調整粒子を透過型電子顕微鏡で観察したところ、形状異方性があることが確認された。電磁波調整粒子のアスペクト比の平均値は６．０、長軸の長さの平均値は５５０ｎｍであった。得られた電磁波調整粒子の電子顕微鏡写真を図２に示す。
また、透過型電子顕微鏡によるポリヨウ素化物の表面への高分子共重合体付与の確認、電磁波調整粒子のシリコーン分散液の調製、及び電磁波調整特性の評価用のガラスセル作製は実施例１と同様にして行った。
[Example 2]
Except that the reaction time in a nitrogen atmosphere when applying the polymer copolymer to the surface of the polyiodide was 18 hours, the polymer was applied to the surface of the polyiodide particles in the same manner as in Example 1. An isoamyl acetate dispersion of electromagnetic wave adjusting particles to which a copolymer was applied and a silicone macromonomer was further applied to the surface of the polymer copolymer was prepared. When the obtained electromagnetic wave adjusting particles were observed with a transmission electron microscope, it was confirmed that there was shape anisotropy. The average value of the aspect ratio of the electromagnetic wave adjusting particles was 6.0, and the average value of the long axis length was 550 nm. An electron micrograph of the obtained electromagnetic wave adjusting particles is shown in FIG.
In addition, the confirmation of the application of the polymer copolymer to the surface of the polyiodide using a transmission electron microscope, the preparation of a silicone dispersion of electromagnetic wave adjusting particles, and the production of a glass cell for evaluating the electromagnetic wave adjusting characteristics were the same as in Example 1. I went there.
〔実施例３〕
ナスフラスコに６質量％の前記ポリヨウ素化物の酢酸イソアミル分散液２６．７ｇ、ジラウリン酸ジブチル錫（ＩＶ）（アルドリッチ株式会社）０．４０ｇ、酢酸イソアミル（和光純薬工業株式会社）１３３．２ｇ、メタクリロイルオキシエチルイソシアナート（昭和電工株式会社）４．７９ｇを加え、真空雰囲気下、６０℃で２１時間撹拌した。得られた分散液を分散液の質量の４倍に相当するヘキサン（関東化学株式会社）に加え、９０００ｒｐｍ（回転/分）で１０分間遠心分離を行い、上澄みを除去し、酢酸イソアミル７０ｇを加え、３０分間超音波処理を施した。この操作を２回繰り返し行い、重合性官能基を付与した３．０質量％のポリヨウ素化物の酢酸イソアミル分散液を得た。ナスフラスコに上記の重合性官能基を有するポリヨウ素化物の酢酸イソアミル分散液３．３１ｇ、アクリロニトリル（関東化学株式会社）０．５４５ｇ、メチルメタクリレート（和光純薬工業株式会社）０．０５４ｇ、ジメチルシリコーンマクロモノマー（ＦＭ−０７２１、ＪＮＣ株式会社）０．５５８ｇ、酢酸イソアミル５．５３ｇを加えて１０分間窒素バブリングを行い脱気した。その後窒素雰囲気下、６０℃で８時間撹拌した。得られた分散液を分散液の質量の４倍に相当するエタノール（和光純薬工業株式会社）に加え、６０００ｒｐｍ（回転/分）で１０分間遠心分離を行い、上澄みを除去し、酢酸イソアミル６ｇを加え、３０分間超音波処理を施した。この操作を３回繰り返し行い、ポリヨウ素化物の粒子表面に高分子共重合体を付与し、さらに高分子共重合体表面にシリコーンマクロモノマーが付与された電磁波調整粒子の酢酸イソアミル分散液を得た。
得られた電磁波調整粒子を透過型電子顕微鏡で観察したところ、形状異方性があることが確認された。電磁波調整粒子のアスペクト比の平均値は５．４、長軸の長さの平均値は５８０ｎｍであった。
また、透過型電子顕微鏡によるポリヨウ素化物の表面への高分子共重合体付与の確認、電磁波調整粒子のシリコーン分散液の調製、及び電磁波調整特性の評価用のガラスセル作製は実施例１と同様にして行った。
Example 3
In an eggplant flask, 26.7 g of an isoamyl acetate dispersion of 6% by weight of the above polyiodide, 0.40 g of dibutyltin (IV) dilaurate (Aldrich Corporation), 133.2 g of isoamyl acetate (Wako Pure Chemical Industries, Ltd.), 4.79 g of methacryloyloxyethyl isocyanate (Showa Denko KK) was added, and the mixture was stirred at 60 ° C. for 21 hours in a vacuum atmosphere. The obtained dispersion is added to hexane (Kanto Chemical Co., Ltd.) corresponding to 4 times the mass of the dispersion, centrifuged at 9000 rpm (revolutions / minute) for 10 minutes, the supernatant is removed, and 70 g of isoamyl acetate is added. For 30 minutes. This operation was repeated twice to obtain a 3.0 mass% polyiodide isoamyl acetate dispersion having a polymerizable functional group. 3.31 g of isoamyl acetate dispersion of polyiodide having the above polymerizable functional group in an eggplant flask, 0.545 g of acrylonitrile (Kanto Chemical Co., Ltd.), 0.054 g of methyl methacrylate (Wako Pure Chemical Industries, Ltd.), dimethyl silicone Macromonomer (FM-0721, JNC Co., Ltd.) 0.558 g and isoamyl acetate 5.53 g were added and degassed by nitrogen bubbling for 10 minutes. Thereafter, the mixture was stirred at 60 ° C. for 8 hours under a nitrogen atmosphere. The obtained dispersion was added to ethanol (Wako Pure Chemical Industries, Ltd.) corresponding to 4 times the mass of the dispersion, centrifuged at 6000 rpm (rotation / min) for 10 minutes, the supernatant was removed, and isoamyl acetate 6 g And sonicated for 30 minutes. This operation was repeated three times to obtain an isoamyl acetate dispersion of electromagnetic wave adjusting particles in which a polymer copolymer was imparted to the surface of polyiodide particles and a silicone macromonomer was further imparted to the surface of the polymer copolymer. .
When the obtained electromagnetic wave adjusting particles were observed with a transmission electron microscope, it was confirmed that there was shape anisotropy. The average aspect ratio of the electromagnetic wave adjusting particles was 5.4, and the average length of the major axis was 580 nm.
In addition, the confirmation of the application of the polymer copolymer to the surface of the polyiodide using a transmission electron microscope, the preparation of a silicone dispersion of electromagnetic wave adjusting particles, and the production of a glass cell for evaluating the electromagnetic wave adjusting characteristics were the same as in Example 1. I went there.
〔実施例４〕
ポリヨウ素化物の表面への高分子共重合体付与する際の、窒素雰囲気下での反応時間を１２時間としたことを除いては実施例３と同様にして、ポリヨウ素化物の表面への高分子共重合体を有する電磁波調整粒子の酢酸イソアミル分散液を作製した。得られた電磁波調整粒子を透過型電子顕微鏡で観察したところ、形状異方性があることが確認された。電磁波調整粒子のアスペクト比の平均値は４．２、長軸の長さの平均値は５９０ｎｍであった。
また、透過型電子顕微鏡によるポリヨウ素化物の表面への高分子共重合体付与の確認、電磁波調整粒子のシリコーン分散液の調製、及び電磁波調整特性の評価用のガラスセル作製は実施例１と同様にして行った。
Example 4
In the same manner as in Example 3 except that the reaction time in a nitrogen atmosphere was 12 hours when the polymer copolymer was applied to the surface of the polyiodide, the surface of the polyiodide was increased. An isoamyl acetate dispersion of electromagnetic wave adjusting particles having a molecular copolymer was prepared. When the obtained electromagnetic wave adjusting particles were observed with a transmission electron microscope, it was confirmed that there was shape anisotropy. The average value of the aspect ratio of the electromagnetic wave adjusting particles was 4.2, and the average value of the long axis length was 590 nm.
In addition, the confirmation of the application of the polymer copolymer to the surface of the polyiodide using a transmission electron microscope, the preparation of a silicone dispersion of electromagnetic wave adjusting particles, and the production of a glass cell for evaluating the electromagnetic wave adjusting characteristics were the same as in Example 1. I went there.
〔実施例５〕
ポリヨウ素化物の表面への高分子共重合体を付与する際の、窒素雰囲気下での反応時間を１８時間としたことを除いては実施例３と同様にして、ポリヨウ素化物の表面への高分子共重合体を有する電磁波調整粒子の酢酸イソアミル分散液を作製した。得られた電磁波調整粒子を透過型電子顕微鏡で観察したところ、形状異方性があることが確認された。電磁波調整粒子のアスペクト比の平均値は３．３、長軸の長さの平均値は５５０ｎｍであった。
また、透過型電子顕微鏡によるポリヨウ素化物の表面への高分子共重合体付与の確認、電磁波調整粒子のシリコーン分散液の調製、及び電磁波調整特性の評価用のガラスセル作製は実施例１と同様にして行った。
Example 5
In the same manner as in Example 3 except that the reaction time in a nitrogen atmosphere when applying a polymer copolymer to the surface of the polyiodide was 18 hours, the surface of the polyiodide was applied to the surface of the polyiodide. An isoamyl acetate dispersion of electromagnetic wave adjusting particles having a polymer copolymer was prepared. When the obtained electromagnetic wave adjusting particles were observed with a transmission electron microscope, it was confirmed that there was shape anisotropy. The average value of the aspect ratio of the electromagnetic wave adjusting particles was 3.3, and the average value of the long axis length was 550 nm.
In addition, the confirmation of the application of the polymer copolymer to the surface of the polyiodide using a transmission electron microscope, the preparation of a silicone dispersion of electromagnetic wave adjusting particles, and the production of a glass cell for evaluating the electromagnetic wave adjusting characteristics were the same as in Example 1. I went there.
＜電磁波調整粒子の耐溶剤性の評価＞
比較例１のポリヨウ素化物の耐薬剤性評価と同様の方法で、実施例１〜５で得られた電磁波調整粒子の耐溶剤性を評価した。実施例１〜実施例５の電磁波調整粒子はメタノール及びエタノールに溶解せず、ポリヨウ素化物の表面の高分子共重合体を付与することで耐溶剤性が向上した。
<Evaluation of solvent resistance of electromagnetic wave adjusting particles>
The solvent resistance of the electromagnetic wave adjusting particles obtained in Examples 1 to 5 was evaluated in the same manner as the chemical resistance evaluation of the polyiodide of Comparative Example 1. The electromagnetic wave adjusting particles of Examples 1 to 5 were not dissolved in methanol and ethanol, and the solvent resistance was improved by adding a polymer copolymer on the surface of polyiodide.
１ ：電磁波調整素子
２、３：導電性基材
４、６：基材
５、７：導電層
８ ：電磁波調整用分散体
９ ：電磁波調整粒子
１０ ：分散媒
１１ ：スイッチ
１２ ：電源
DESCRIPTION OF SYMBOLS 1: Electromagnetic wave adjustment element 2, 3: Conductive base material 4, 6: Base material 5, 7: Conductive layer 8: Dispersion for electromagnetic wave adjustment 9: Electromagnetic wave adjustment particle 10: Dispersion medium 11: Switch 12: Power supply
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