JP2005305392A - Method for preparing antimony-containing tin oxide particle dispersion and transparent electrically-conductive film - Google Patents
Method for preparing antimony-containing tin oxide particle dispersion and transparent electrically-conductive film Download PDFInfo
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Description
本発明は、アンチモン含有酸化スズ（ＡＴＯ）粒子分散液の製造方法に関する。さらに詳しくは、各種基材の表面に、高硬度、高屈折率及び導電性を有するとともに耐擦傷性並びに基材及び低屈折率層との密着性に優れた塗膜（被膜）を形成し得る光硬化性組成物に用いられるＡＴＯ粒子分散液の製造方法に関する。 The present invention relates to a method for producing an antimony-containing tin oxide (ATO) particle dispersion. More specifically, a coating film (coating) having high hardness, high refractive index and electrical conductivity and excellent scratch resistance and adhesion to the base material and the low refractive index layer can be formed on the surface of various base materials. The present invention relates to a method for producing an ATO particle dispersion used in a photocurable composition.
近年、各種基材表面の傷付き（擦傷）防止や汚染防止のための保護コーティング材；各種基材の接着剤、シーリング材；印刷インクのバインダー材として、優れた塗工性を有し、かつ各種基材の表面に、硬度、耐擦傷性、耐摩耗性、低カール性、密着性、透明性、耐薬品性及び塗膜面の外観のいずれにも優れた硬化膜を形成し得る硬化性組成物が要請されている。
また、フィルム型液晶素子、タッチパネル、プラスチック光学部品等の反射防止膜の用途においては、上記要請に加えて、高屈折率の硬化膜を形成し得る硬化性組成物が要請されている。
このような硬化性組成物に、高屈折率、高硬度、導電性及び耐擦傷性を付与するために、アンチモン含有酸化スズ粒子分散液が使用されている（例えば、特許文献１参照。）
In recent years, it has excellent coating properties as a protective coating material for preventing scratches (scratching) on various substrate surfaces and preventing contamination; adhesives and sealing materials for various substrates; and a binder material for printing inks. Curability that can form a cured film with excellent hardness, scratch resistance, abrasion resistance, low curl, adhesion, transparency, chemical resistance, and coating surface appearance on the surface of various substrates. A composition is required.
In addition to the above requirements, curable compositions capable of forming a cured film having a high refractive index are required in addition to the above requirements in applications of antireflection films such as film-type liquid crystal elements, touch panels, and plastic optical components.
In order to provide such a curable composition with a high refractive index, high hardness, electrical conductivity, and scratch resistance, an antimony-containing tin oxide particle dispersion is used (see, for example, Patent Document 1).
上記のＡＴＯ粒子分散液は、硬化膜等の透明性向上のため、分散粒径が小さく分散安定性に優れていることが求められている。
しかしながら、本発明者らの検討によると、ＡＴＯ粒子の分散粒径を小さくしていくと、硬化膜の透明性は向上するものの、導電性が低下することがわかった。従って、透明性と導電性の両特性が優れている硬化膜を得るためには、ＡＴＯ粒子の分散形態を制御する必要があることがわかった。
However, according to the study by the present inventors, it was found that when the dispersed particle size of the ATO particles is reduced, the transparency of the cured film is improved but the conductivity is lowered. Therefore, it was found that in order to obtain a cured film having both excellent transparency and conductivity characteristics, it is necessary to control the dispersion form of ATO particles.
本発明は、上述の課題に鑑みてなされたものであり、優れた透明性及び導電性を有する硬化膜を形成するために、好適なＡＴＯ粒子分散液の製造方法を提供することを目的とする。 This invention is made | formed in view of the above-mentioned subject, and aims at providing the manufacturing method of suitable ATO particle dispersion liquid in order to form the cured film which has the outstanding transparency and electroconductivity. .
本発明者らは、この課題を解決するべく鋭意研究した結果、ＡＴＯ粒子、分散剤及び分散溶媒を含む混合液を、所定の粒径の分散ビーズを使用した分散機により分散して、ＡＴＯ粒子の分散粒径を、特定の範囲内に制御することにより、透明性及び導電性が共に優れている硬化膜が得られることを見出し、本発明を完成させた。 As a result of diligent research to solve this problem, the present inventors dispersed a mixed solution containing ATO particles, a dispersant and a dispersion solvent by a disperser using dispersed beads having a predetermined particle size, and thereby obtained ATO particles. The present inventors have found that a cured film having both excellent transparency and electrical conductivity can be obtained by controlling the dispersed particle size of the composition within a specific range, thereby completing the present invention.
本発明によれば、以下のアンチモン含有酸化スズ粒子分散液の製造方法及び透明性導電膜が提供される。
１．アンチモン含有酸化スズ粒子、分散剤及び分散溶媒を含む混合液を、粒径が０．０５〜０．２０ｍｍの分散ビーズを使用した分散機により分散することを特徴とする、メタノール中で動的光散乱法により測定したメジアン径が７５〜１１０ｎｍのアンチモン含有酸化スズ粒子の分散液の製造方法。
２．前記分散機の周速度を、６ｍ／ｓ〜１２ｍ／ｓとする１に記載の分散液の製造方法。
３．メタノール中で動的光散乱法により測定したメジアン径が７５〜１１０ｎｍのアンチモン含有酸化スズ粒子の分散液を用いて作製した透明性導電膜。
According to the present invention, the following method for producing an antimony-containing tin oxide particle dispersion and a transparent conductive film are provided.
1. Dynamic light in methanol, characterized in that a mixed liquid containing antimony-containing tin oxide particles, a dispersant and a dispersion solvent is dispersed by a disperser using dispersion beads having a particle size of 0.05 to 0.20 mm. A method for producing a dispersion of antimony-containing tin oxide particles having a median diameter measured by a scattering method of 75 to 110 nm.
2. 2. The method for producing a dispersion liquid according to 1, wherein a peripheral speed of the disperser is 6 m / s to 12 m / s.
3. The transparent conductive film produced using the dispersion liquid of the antimony containing tin oxide particle | grains whose median diameter measured by the dynamic light-scattering method in methanol is 75-110 nm.
本発明のＡＴＯ粒子分散液の製造方法は、ＡＴＯ粒子の機能を効率よく発揮させることができるように、粒子の分散状態を容易に制御することができ、分散状態を最適に制御した分散液を使用した硬化膜は、透明性及び導電性のバランスに優れている。 The production method of the ATO particle dispersion of the present invention can easily control the dispersion state of the particles so that the function of the ATO particles can be efficiently exhibited. The used cured film has an excellent balance between transparency and conductivity.
以下、本発明のアンチモン含有酸化スズ粒子分散液の製造方法を具体的に説明する。 Hereinafter, the method for producing the antimony-containing tin oxide particle dispersion of the present invention will be specifically described.
アンチモン含有酸化スズ粒子は、その一次粒径が、通常、５ｎｍ〜５０ｎｍのものを使用できる。また、結晶構造は特に限定されないが、単斜晶系等を使用できる。
アンチモン含有酸化スズ粒子の形状は球状、中空状、多孔質状、針状、板状、繊維状、又は不定形状であり、好ましくは、球状である。
As the antimony-containing tin oxide particles, those having a primary particle size of usually 5 nm to 50 nm can be used. The crystal structure is not particularly limited, but a monoclinic system or the like can be used.
The antimony-containing tin oxide particles have a spherical shape, a hollow shape, a porous shape, a needle shape, a plate shape, a fiber shape, or an indefinite shape, and preferably a spherical shape.
このようなアンチモン含有酸化スズ粒子の市販品としては、三井金属（株）製 商品名：パストラン、石原産業（株）製 商品名：ＳＮ−１００Ｐ、日産化学工業（株）製 商品名：ＡＴＯ等が挙げられる。 As commercial products of such antimony-containing tin oxide particles, Mitsui Kinzoku Co., Ltd., trade name: Pastoran, Ishihara Sangyo Co., Ltd., trade name: SN-100P, Nissan Chemical Industries, Ltd., trade name: ATO, etc. Is mentioned.
分散剤は、一般に市販されているものを使用できるが、好ましくは下記式（１）で表される化合物である。
繰り返し数ｘ、ｙは、それぞれ１〜１２０の整数であり、式（１）の化合物の分子量は、１０００〜３００００であることが好ましい。
このような分散剤の市販品としては、花王（株）製：エマルゲン１０５、レオドールＳＰ−Ｏ１０、ネオペレックＮｏ．６；旭電化工業（株）製：アデカプルロニックＴＲ−７０１、ＴＲ−７０２、ＴＲ−７０４；楠本化成（株）：ＰＬＡＡＤ ＥＤ２１１等が挙げられる。
The repeating numbers x and y are each an integer of 1 to 120, and the molecular weight of the compound of the formula (1) is preferably 1000 to 30000.
Commercially available products of such dispersants are Kao Corporation: Emulgen 105, Rheodor SP-O10, Neo-Perec No. 6; Asahi Denka Kogyo Co., Ltd .: Adeka Pluronic TR-701, TR-702, TR-704; Enomoto Kasei Co., Ltd .: PLAAD ED211 and the like.
分散媒は、メタノール、エタノール、イソプロパノール、ブタノール、オクタノール等のアルコール類；酢酸エチル、酢酸ブチル、乳酸エチル、γ−ブチロラクトン、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等のエステル類；エチレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルジエチレングリコールモノブチルエーテル等のエーテル類；ジメチルフォルムアミド、Ｎ，Ｎ−ジメチルアセトアセトアミド、Ｎ−メチルピロリドン等のアミド類を用いることができる。中でも、メタノール、イソプロパノール、ブタノール、プロピレングリコールモノメチルエーテルが好ましく、メタノール、プロピレングリコールモノメチルエーテルがより好ましい。分散媒は一種又は二種以上を混合して用いることができる。
一方、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類やベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素類は分散性の観点から好ましくなく、添加量を少なく抑えるか、できれば添加しないことが好ましい。
Dispersion medium: alcohols such as methanol, ethanol, isopropanol, butanol, octanol; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ethylene glycol Ethers such as monomethyl ether and propylene glycol monomethyl ether diethylene glycol monobutyl ether; amides such as dimethylformamide, N, N-dimethylacetoacetamide and N-methylpyrrolidone can be used. Among these, methanol, isopropanol, butanol, and propylene glycol monomethyl ether are preferable, and methanol and propylene glycol monomethyl ether are more preferable. A dispersion medium can be used 1 type or in mixture of 2 or more types.
On the other hand, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene are not preferable from the viewpoint of dispersibility. Is preferred.
分散液におけるアンチモン含有酸化スズの配合量は、分散液に対して８．０〜５０．０重量％、好ましくは１５〜４０．０重量％である。この範囲内であれば、良好な導電性の透明膜を得ることができる。アンチモン含有酸化スズの含有量が１５重量％未満のときは、導電性が悪化するおそれがあり、５０．０重量％を超えると透明性が低下するおそれがある。
分散剤の添加量は、分散液に対して０．２〜５０．０重量％が好ましい。この範囲内であれば、良好な分散液を得ることができる。含有量が０．２重量％未満では、散液の安定性が悪化するおそれがあり、５０．０重量％を超えると導電性が低下するおそれがある。好ましくは０．５〜３０．０重量％、さらに好ましくは０．５〜１０．０重量％である。
分散媒の配合量は、５０〜９０重量％が好ましく、６０〜８０重量％であることが特に好ましい。
The amount of antimony-containing tin oxide in the dispersion is 8.0 to 50.0% by weight, preferably 15 to 40.0% by weight, based on the dispersion. If it is in this range, a favorable conductive transparent film can be obtained. When the content of the antimony-containing tin oxide is less than 15% by weight, the conductivity may be deteriorated, and when it exceeds 50.0% by weight, the transparency may be lowered.
The addition amount of the dispersant is preferably 0.2 to 50.0% by weight with respect to the dispersion. Within this range, a good dispersion can be obtained. If the content is less than 0.2% by weight, the stability of the spray may be deteriorated, and if it exceeds 50.0% by weight, the conductivity may be lowered. Preferably it is 0.5-30.0 weight%, More preferably, it is 0.5-10.0 weight%.
The blending amount of the dispersion medium is preferably 50 to 90% by weight, particularly preferably 60 to 80% by weight.
本発明の分散液の製造方法においては、上記の成分の他に、その特性を損なわない範囲において、カップリング剤等を含むことができる。また、後述の多官能（メタ）アクリレートモノマーを含むこともできる。 In the method for producing the dispersion of the present invention, in addition to the above components, a coupling agent and the like can be included as long as the characteristics are not impaired. Moreover, the below-mentioned polyfunctional (meth) acrylate monomer can also be included.
本発明の分散液の製造方法は、分散媒、分散剤、及びＡＴＯ粒子を含む混合液を、分散ビーズを使用した分散機により分散して行われる。
分散機は、分散ビーズを用いて分散するものであれば特に限定されないが、好ましくは、ビーズミルを用いられる。ビーズミルとしては、例えば、ペイントシェーカ、ＳＣミル、アニュラー型ミル、ピン型ミル等を挙げることができる。
分散ビーズとして、ガラスビーズ、ジルコニアビーズ等を使用できる。分散時間が短くなることから、ジルコニアビーズを用いることが好ましい。
ビーズの粒子径は、０．０５〜０．２ｍｍである。粒子径が０．２ｍｍを超えると、ＡＴＯ粒子を所定のメジアン径まで分散を行なうことが困難になる。０．０５ｍｍより小さいと、ＡＴＯ粒子の分散そのものが困難になる。
The method for producing a dispersion of the present invention is carried out by dispersing a mixed solution containing a dispersion medium, a dispersant, and ATO particles by a disperser using dispersion beads.
The disperser is not particularly limited as long as it disperses using dispersed beads, but a bead mill is preferably used. Examples of the bead mill include a paint shaker, an SC mill, an annular mill, and a pin mill.
As the dispersed beads, glass beads, zirconia beads, or the like can be used. It is preferable to use zirconia beads because the dispersion time is shortened.
The particle diameter of the beads is 0.05 to 0.2 mm. When the particle diameter exceeds 0.2 mm, it becomes difficult to disperse ATO particles to a predetermined median diameter. If it is smaller than 0.05 mm, dispersion of ATO particles itself becomes difficult.
ビーズの使用量は、分散機のベッセル容積に対して２０〜９０容量％、好ましくは３０〜８５容量％、さらに好ましくは４０〜８０容量％の範囲内であれば、良好な分散液を得る事が出来る。分散ビーズの充填量が２０容量％未満では、分散に時間がかかりすぎ、９０容量％を超えると分散液の不安定化が起こるおそれがある。 If the amount of beads used is in the range of 20 to 90% by volume, preferably 30 to 85% by volume, more preferably 40 to 80% by volume, based on the vessel volume of the disperser, a good dispersion can be obtained. I can do it. When the filling amount of the dispersed beads is less than 20% by volume, it takes too much time to disperse, and when it exceeds 90% by volume, the dispersion may become unstable.
ビーズミルの周速は６〜１２ｍ／ｓの条件で行なうことが好ましい。周速が６ｍ／ｓよりも小さいと、所定の粒子径までＡＴＯ粒子を分散する時間が長くなり実用的ではなく、１２ｍ／ｓを超えると、分散が急激に進み、所定の粒子径にコントロールできなくなるおそれがある。
ビーズミルの周速は、好ましくは６．０〜１１．０ｍ／ｓ、より好ましくは、７．０〜１１．０ｍ／ｓである。
尚、ビーズミルの周速は、回転部（撹拌部）外周の線速度である。
The peripheral speed of the beads mill is preferably 6 to 12 m / s. When the peripheral speed is less than 6 m / s, it takes a long time to disperse the ATO particles up to the predetermined particle diameter, which is not practical. When the peripheral speed exceeds 12 m / s, the dispersion rapidly proceeds and can be controlled to the predetermined particle diameter. There is a risk of disappearing.
The peripheral speed of the bead mill is preferably 6.0 to 11.0 m / s, and more preferably 7.0 to 11.0 m / s.
The peripheral speed of the bead mill is the linear velocity of the outer periphery of the rotating part (stirring part).
分散処理は、ＡＴＯ粒子のメジアン径が、７５ｎｍ〜１１０ｎｍになるまで行われる。メジアン径が１１０ｎｍより大きいと、ＡＴＯ粒子分散液を使用して作製した硬化膜の透明性が低下（ヘーズ値が高くなる）し、７５ｎｍより小さいと硬化膜の導電性が低下する。分散処理後のＡＴＯ粒子のメジアン径は、好ましくは８０ｎｍ〜１００ｎｍである。
尚、本明細書においてメジアン径とは、メタノール中で動的光散乱法により測定される。
The dispersion treatment is performed until the median diameter of the ATO particles becomes 75 nm to 110 nm. When the median diameter is larger than 110 nm, the transparency of the cured film produced using the ATO particle dispersion liquid is lowered (haze value is increased), and when it is smaller than 75 nm, the conductivity of the cured film is lowered. The median diameter of the ATO particles after the dispersion treatment is preferably 80 nm to 100 nm.
In the present specification, the median diameter is measured by a dynamic light scattering method in methanol.
本発明のアンチモン含有酸化スズ粒子分散液は、以下の表面変性を加えることが好ましい。表面変性を行うことにより、アンチモン含有酸化スズ粒子分散液を含有する光硬化性組成物の硬化物の耐擦傷性を改善することができる。 The antimony-containing tin oxide particle dispersion of the present invention is preferably subjected to the following surface modification. By performing the surface modification, it is possible to improve the scratch resistance of the cured product of the photocurable composition containing the antimony-containing tin oxide particle dispersion.
表面変性は、公知の方法で用いることができる（例えば、特開２００３−１０５０３４号公報参照）。具体的には、アンチモン含有酸化スズ粒子を、分子内に、（メタ）アクリロイル基やビニル基等の重合性不飽和基及び下記式（２）に示す基を有する化合物（以下、「特定有機化合物」という。）と反応させることにより行うことができる。
−Ｘ−Ｃ（＝Ｙ）ＮＨ− ・・・（２）
［式（２）中、Ｘは、ＮＨ、Ｏ（酸素原子）又はＳ（イオウ原子）を示し、Ｙは、Ｏ又はＳを示す。］
尚、この化合物は、分子内にシラノ−ル基又は加水分解によってシラノ−ル基を生成する基を有する化合物であることが好ましい。
Surface modification can be used by a well-known method (for example, refer Unexamined-Japanese-Patent No. 2003-105034). Specifically, the antimony-containing tin oxide particles are composed of a compound having a polymerizable unsaturated group such as a (meth) acryloyl group or a vinyl group and a group represented by the following formula (2) (hereinafter referred to as “specific organic compound”). It can be carried out by reacting with.
-X-C (= Y) NH- (2)
[In the formula (2), X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]
This compound is preferably a compound having in its molecule a silanol group or a group that generates a silanol group by hydrolysis.
前記式（２）に示す基は、具体的には、［−Ｏ−Ｃ（＝Ｏ）−ＮＨ−］、［−Ｏ−Ｃ（＝Ｓ）−ＮＨ−］、［−Ｓ−Ｃ（＝Ｏ）−ＮＨ−］、［−ＮＨ−Ｃ（＝Ｏ）−ＮＨ−］、［−ＮＨ−Ｃ（＝Ｓ）−ＮＨ−］、及び［−Ｓ−Ｃ（＝Ｓ）−ＮＨ−］の６種である。これらの基は、１種単独で又は２種以上を組合わせて用いることができる。中でも、熱安定性の観点から、［−Ｏ−Ｃ（＝Ｏ）−ＮＨ−］基を必須とし、［−Ｏ−Ｃ（＝Ｓ）−ＮＨ−］基及び［−Ｓ−Ｃ（＝Ｏ）−ＮＨ−］基の少なくとも１を併用することが好ましい。前記式（２）に示す基［−Ｘ−Ｃ（＝Ｙ）−ＮＨ−］は、分子間において水素結合による適度の凝集力を発生させ、硬化物にした場合、優れた機械的強度、基材との密着性及び耐熱性等の特性を付与せしめるものと考えられる。 Specific examples of the group represented by the formula (2) include [—O—C (═O) —NH—], [—O—C (═S) —NH—], [—S—C (= O) —NH—], [—NH—C (═O) —NH—], [—NH—C (═S) —NH—], and [—S—C (═S) —NH—]. There are six types. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, the [—O—C (═O) —NH—] group is essential, the [—O—C (═S) —NH—] group and the [—S—C (═O). ) -NH-] group is preferably used in combination. The group [—X—C (═Y) —NH—] represented by the formula (2) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength and group when cured. It is considered that it gives properties such as adhesion to the material and heat resistance.
本発明の透明性導電膜は、上記のアンチモン含有酸化スズ粒子分散液の他、多官能（メタ）アクリレートモノマー、光重合開始剤等を含んで調製された光硬化性組成物を硬化することにより形成できる。ここで、表面変性したアンチモン含有酸化スズ粒子を用いることが好ましい。 The transparent conductive film of the present invention is obtained by curing a photocurable composition prepared containing a polyfunctional (meth) acrylate monomer, a photopolymerization initiator and the like in addition to the antimony-containing tin oxide particle dispersion. Can be formed. Here, it is preferable to use surface-modified antimony-containing tin oxide particles.
多官能（メタ）アクリレートモノマーは、アンチモン含有酸化スズ分散液に硬化性を付与するために用いる。ここで多官能とは、１分子中に２個以上の（メタ）アクリロイル基を有することをいい、製膜性の観点から、３官能以上の（メタ）アクリレートモノマーが好ましく、５官能以上の（メタ）アクリレートモノマーがさらに好ましい。又は２種以上の多官能（メタ）アクリレートモノマーの混合物を用いることができる。 The polyfunctional (meth) acrylate monomer is used to impart curability to the antimony-containing tin oxide dispersion. Here, polyfunctional means having two or more (meth) acryloyl groups in one molecule, and from the viewpoint of film forming property, a trifunctional or higher (meth) acrylate monomer is preferable, and a pentafunctional or higher ( More preferred are meth) acrylate monomers. Alternatively, a mixture of two or more polyfunctional (meth) acrylate monomers can be used.
多官能（メタ）アクリレートモノマーの好ましい具体例としては、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールペンタアクリレート等を挙げることができる。
多官能（メタ）アクリレートモノマーの市販品としては、ＫＡＹＡＲＡＤ ＤＰＨＡ（日本化薬（株）製）等を挙げることができる。
Preferable specific examples of the polyfunctional (meth) acrylate monomer include dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate and the like.
Examples of commercially available polyfunctional (meth) acrylate monomers include KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.).
光重合開始剤としては、光照射により分解してラジカルを発生して重合を開始せしめるものであれば特に制限はなく、例えば、アセトフェノン、アセトフェノンベンジルケタール、１−ヒドロキシシクロヘキシルフェニルケトン、２，２−ジメトキシ−１，２−ジフェニルエタン−１−オン、３−メチルアセトフェノン、４−クロロベンゾフェノン、４，４’−ジメトキシベンゾフェノン、ベンジルジメチルケタール、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルホリノ−プロパン−１−オン、２，４，６−トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビス−（２，６−ジメトキシベンゾイル）−２，４，４−トリメチルペンチルフォスフィンオキシド、オリゴ（２−ヒドロキシ−２−メチル−１−（４−（１−メチルビニル）フェニル）プロパノン）等を挙げることができる。 The photopolymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2- Dimethoxy-1,2-diphenylethane-1-one, 3-methylacetophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2- Methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, 2 , 4,6-trimethylbenzoyldiphenylphosphine oxide, Su- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- (1-methylvinyl) phenyl) propanone), etc. Can be mentioned.
放射線（光）重合開始剤の市販品としては、例えば、チバスペシャルティケミカルズ（株）製 商品名：イルガキュア １８４、３６９、６５１、５００、８１９、９０７、７８４、２９５９、ＣＧＩ１７００、ＣＧＩ１７５０、ＣＧＩ１８５０、ＣＧ２４−６１、ダロキュア １１１６、１１７３、ＢＡＳＦ社製 商品名：ルシリン ＴＰＯ、ＵＣＢ社製 商品名：ユベクリル Ｐ３６、フラテツリ・ランベルティ社製 商品名：エザキュアー ＫＩＰ１５０、ＫＩＰ６５ＬＴ、ＫＩＰ１００Ｆ、ＫＴ３７、ＫＴ５５、ＫＴＯ４６、ＫＩＰ７５／Ｂ等を挙げることができる。 As a commercial item of a radiation (photo) polymerization initiator, for example, Ciba Specialty Chemicals Co., Ltd. trade name: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG 24- 61, Darocur 1116, 1173, manufactured by BASF, Inc. Product name: Lucillin TPO, manufactured by UCB, Inc. Product name: Ubekrill P36, manufactured by Fratteri Lamberti, Inc. Product names: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B Etc.
この光硬化性組成物中に含まれる各成分の配合量は、用途に応じて適宜設定できるが、通常、アンチモン含有酸化スズ粒子分散液中に含まれるアンチモン含有酸化スズ粒子（表面変性をした場合には、表面変性後のアンチモン含有酸化スズ粒子）１００重量部に対して、多官能（メタ）アクリレートモノマー１０〜２０００重量部、光重合開始剤０．０１〜１００重量部であり、好ましくは、多官能（メタ）アクリレートモノマー２０〜１０００重量部、光重合開始剤０．１〜６０重量部である。 The amount of each component contained in the photocurable composition can be appropriately set according to the application, but usually the antimony-containing tin oxide particles contained in the antimony-containing tin oxide particle dispersion (when the surface is modified) Are 10 to 2000 parts by weight of a polyfunctional (meth) acrylate monomer and 0.01 to 100 parts by weight of a photopolymerization initiator, preferably 100 parts by weight of antimony-containing tin oxide particles after surface modification. They are 20-1000 weight part of polyfunctional (meth) acrylate monomers, 0.1-60 weight part of photoinitiators.
光硬化性組成物は、上記の成分の他に、その特性を損なわない範囲において、単官能（メタ）アクリレート化合物の他、メチルイソブチルケトン等の溶媒、その他レベリング剤等を含むこともできる。 In addition to the above components, the photocurable composition can also contain a monofunctional (meth) acrylate compound, a solvent such as methyl isobutyl ketone, other leveling agents, and the like as long as the characteristics are not impaired.
本発明のアンチモン含有酸化スズ粒子分散液を含んで調製した樹脂組成物を硬化した膜は、アンチモン含有酸化スズ粒子が膜内で凝集し難く、透明性が高く、かつ良好な導電性を有する。 A film obtained by curing a resin composition prepared by including the antimony-containing tin oxide particle dispersion of the present invention is resistant to aggregation of antimony-containing tin oxide particles in the film, has high transparency, and has good conductivity.
以下、本発明のアンチモン含有酸化スズ粒子分散液等について、実施例により具体的に説明する。
尚、各例で作製した分散液、透明性導電膜の評価は以下の方法で行なった。
（１）粒子径（メジアン径）
粒径測定装置（堀場製作所製、動的光散乱式粒径測定装置）を使用して、測定温度を２５℃とし、回収した分散液をそのまま測定した。
データ解析条件：粒子径基準 体積基準
分散粒子 ＡＴＯ粒子 屈折率１．９５
分散媒 メタノール 屈折率１．３２９
（２）全固形分含量（ＴＳＣ）
予め加熱し、油分を飛ばしておいたアルミ皿に、約２．０ｇを量りとり、ホットプレートにて１７５℃で３０分加熱した。その後、残った固形分を測定した。
（３）表面抵抗値
表面抵抗測定機（アジレント・テクノロジー（株）社製：Ａｇｉｌｅｎｔ４３３９Ｂ）を使用して、測定セル（同社製：レジスティビリティ・セル）：２６ｍｍ、電圧：１００Ｖ、測定時間：６０秒の条件で測定した。
（４）ＨＡＺＥ値
測定装置（スガ試験機（株）社製：カラーヘーズメーター）を使用して、ＪＩＳ Ｋ７１０５に準拠して測定した。
Hereinafter, the antimony-containing tin oxide particle dispersion of the present invention will be specifically described with reference to examples.
In addition, evaluation of the dispersion liquid and the transparent conductive film prepared in each example was performed by the following method.
(1) Particle diameter (median diameter)
Using a particle size measuring device (manufactured by Horiba, Ltd., dynamic light scattering type particle size measuring device), the measurement temperature was set to 25 ° C., and the recovered dispersion was measured as it was.
Data analysis conditions: Particle diameter standard Volume standard Dispersed particle ATO particle Refractive index 1.95
Dispersion medium Methanol Refractive index 1.329
(2) Total solid content (TSC)
About 2.0 g was weighed on an aluminum pan that had been heated in advance and the oil content had been removed, and heated at 175 ° C. for 30 minutes on a hot plate. Thereafter, the remaining solid content was measured.
(3) Surface resistance value Using a surface resistance measuring device (Agilent Technology Co., Ltd .: Agilent 4339B), measurement cell (manufactured by: Resistability Cell): 26 mm, voltage: 100 V, measurement time: 60 The measurement was performed under the condition of seconds.
(4) HAZE value It measured based on JISK7105 using the measuring apparatus (Suga Test Instruments Co., Ltd. product: Color haze meter).
［アンチモン含有酸化スズ粒子分散液の作製］
実施例１
一次粒子径が０．０１〜０．０３μｍのアンチモン含有酸化スズ粒子（株式会社 石原テクノ製、商品名：ＳＮ−１００Ｐ）１７４６．０ｇと、分散剤（花王（株）製エマルゲン１０５）５４．０ｇを、メタノール４２００．０ｇに投入し、軽く混合した。
次いで、この混合溶液を分散機（三井鉱山（株）製：ＳＣミル、ベッセル容量２００ｍｌ）に投入し、循環させた。
ジルコニアビーズ（粒子径０．１ｍｍ）８４０ｇ（ベッセル容量に対して７０容量％相当）を徐々に添加し、分散機を周速８ｍ／ｓで３０分運転し、混合液を分散させた。
サンプリングを行いメジアン径が９０ｎｍになったことを確認した時点で分散終了とし、ＴＳＣが３１．２重量％のアンチモン含有酸化スズ分散液を５６００ｇ得た。
[Preparation of antimony-containing tin oxide particle dispersion]
Example 1
Antimony-containing tin oxide particles having a primary particle size of 0.01 to 0.03 μm (trade name: SN-100P, manufactured by Ishihara Techno Co., Ltd.) 1746.0 g and a dispersant (Emulgen 105, manufactured by Kao Corporation) 54.0 g Was added to 4200.0 g of methanol and lightly mixed.
Next, this mixed solution was put into a disperser (manufactured by Mitsui Mining Co., Ltd .: SC mill, vessel capacity 200 ml) and circulated.
840 g of zirconia beads (particle diameter: 0.1 mm) (corresponding to 70% by volume with respect to the vessel capacity) was gradually added, and the disperser was operated at a peripheral speed of 8 m / s for 30 minutes to disperse the mixed solution.
When it was confirmed that the median diameter became 90 nm by sampling, the dispersion was terminated, and 5600 g of an antimony-containing tin oxide dispersion having a TSC of 31.2% by weight was obtained.
実施例２
分散剤（楠本化成（株）製ＰＬＡＡＤ ＥＤ２１１）５４．０ｇを使用した他は、実施例１に同じ条件にて分散を行った。尚、分散はビーズをすべて投入してから、分散機を周速８ｍ／ｓで４０分運転することで行なった。
サンプリングを行い、メジアン径を測定したところ１０５ｎｍになったことを確認し、分散終了とした。ＴＳＣ＝３２．２重量％のアンチモン含有酸化スズ分散液を５６６０ｇ得た。
Example 2
Dispersion was performed under the same conditions as in Example 1 except that 54.0 g of a dispersant (PLAAD ED211 manufactured by Enomoto Kasei Co., Ltd.) was used. Dispersion was performed by operating the disperser at a peripheral speed of 8 m / s for 40 minutes after all the beads had been charged.
Sampling was performed and the median diameter was measured to confirm that it was 105 nm. 5660 g of antimony-containing tin oxide dispersion having TSC = 32.2% by weight was obtained.
実施例３
分散剤（旭電化（株）製アデカプルロニックＴＲ７０１）５４．０ｇを使用した他は、実施例１に示す条件と同じ条件にて、分散を行った。尚、分散はビーズをすべて投入してから、分散機を周速８ｍ／ｓで２０分運転することで行なった。
サンプリングを行い、メジアン径を測定したところ１００ｎｍになったことを確認し、分散終了とした。ＴＳＣ＝３０．８重量％のアンチモン含有酸化スズ分散液を５７００ｇ得た。
Example 3
Dispersion was performed under the same conditions as those shown in Example 1 except that 54.0 g of a dispersant (Adeka Pluronic TR701 manufactured by Asahi Denka Co., Ltd.) was used. Dispersion was performed by operating the disperser at a peripheral speed of 8 m / s for 20 minutes after all the beads were charged.
Sampling was performed and the median diameter was measured to confirm that it was 100 nm. 5700 g of antimony-containing tin oxide dispersion having TSC = 30.8% by weight was obtained.
［透明性導電膜］
実施例４
実施例１で調製した分散液を使用して、表１に示す組成のコート液を調製した。
[Transparent conductive film]
Example 4
Using the dispersion prepared in Example 1, a coating solution having the composition shown in Table 1 was prepared.
このコート液を、ディップ法（液温２３℃、引き上げ速度４００ｍｍ/ｍｉｎ）にてメタクリル酸メチルースチレン重合体（ＭＳ）の基板（２．５ｍｍ厚）上に塗布後、紫外線照射装置にて、片面あたりの照射量０．５Ｊ×２回（１Ｊ相当）の条件で硬化させて、膜厚３〜４μｍの透明性導電膜を形成した。
得られた膜のＨＡＺＥ値は１．１２、表面抵抗値は２．６×１０１２Ω／□であった。
This coating solution was applied on a methyl methacrylate-styrene polymer (MS) substrate (2.5 mm thickness) by the dipping method (liquid temperature: 23 ° C., pulling speed: 400 mm / min), and then with an ultraviolet irradiation device. A transparent conductive film having a thickness of 3 to 4 μm was formed by curing under the condition of an irradiation amount of 0.5 J × 2 times (corresponding to 1 J) per side.
The obtained film had a HAZE value of 1.12 and a surface resistance value of 2.6 × 10 12 Ω / □.
実施例５
実施例２で調製した分散液を使用して、表１に示す組成のコート液を調製した他は、実施例４と同様にして透明性導電膜を形成した。
得られた膜のＨＡＺＥ値は１．２０、表面抵抗値は０．８×１０１２Ω／□であった。
Example 5
A transparent conductive film was formed in the same manner as in Example 4 except that the coating liquid having the composition shown in Table 1 was prepared using the dispersion prepared in Example 2.
The film obtained had a HAZE value of 1.20 and a surface resistance value of 0.8 × 10 12 Ω / □.
実施例６
実施例３で調製した分散液を使用して、表１に示す組成のコート液を調製した他は、実施例４と同様にして透明性導電膜を形成した。
得られた膜のＨＡＺＥ値は１．０２、表面抵抗値は６．６×１０１２Ω／□であった。
Example 6
A transparent conductive film was formed in the same manner as in Example 4 except that the coating liquid having the composition shown in Table 1 was prepared using the dispersion prepared in Example 3.
The obtained film had a HAZE value of 1.02 and a surface resistance value of 6.6 × 10 12 Ω / □.
試験例１
実施例３の配合及び条件で、混合液を分散させたときの、分散機の運転時間と、ＡＴＯ粒子の分散粒径の関係を調査した。また、各分散時間ごとに採取した分散液について、実施例６と同様にして硬化膜を作製し、そのＨＡＺＥ値及び表面抵抗値を測定した。この結果を表２に示す。
Test example 1
The relationship between the operation time of the disperser and the dispersed particle diameter of the ATO particles when the mixed liquid was dispersed under the formulation and conditions of Example 3 was investigated. Moreover, about the dispersion liquid extract | collected for every dispersion | distribution time, the cured film was produced like Example 6, and the HAZE value and the surface resistance value were measured. The results are shown in Table 2.
この結果から、ＡＴＯ粒子の分散が進むと、ＨＡＺＥ値は比例して低下するものの、表面抵抗値は高くなる傾向があることが確認できた。そのため、透明性及び導電性の両特性が優れている硬化膜を作製するには、ＡＴＯ粒子の分散処理後のメジアン径を、７５〜１１０ｎｍとすることが有効であることがわかった。 From this result, it was confirmed that as the dispersion of ATO particles progressed, the HAZE value decreased in proportion, but the surface resistance value tended to increase. Therefore, it was found that it is effective to set the median diameter after the dispersion treatment of ATO particles to 75 to 110 nm in order to produce a cured film having both excellent transparency and conductivity.
試験例２
分散ビーズとして粒径０．３ｍｍのジルコニアビーズ（ベッセル容量に対して７０容量％相当）を使用した他は、実施例１に示す条件と同じ条件にて、分散をさせた。２１０分まで分散処理を行ってもメジアン径は１９０ｎｍ以下にならず、２１０分間、分散を行ったＡＴＯ粒子（メジアン径２２０ｎｍ）を用いて実施例６と同様にして作製した硬化膜の表面抵抗値は、７．０×１０１３Ω／□であった。
Test example 2
Dispersion was performed under the same conditions as those shown in Example 1 except that zirconia beads having a particle diameter of 0.3 mm (corresponding to 70% by volume with respect to the vessel capacity) were used as the dispersion beads. Even if the dispersion treatment is performed up to 210 minutes, the median diameter does not become 190 nm or less, and the surface resistance value of the cured film produced in the same manner as in Example 6 using the ATO particles (median diameter 220 nm) dispersed for 210 minutes. Was 7.0 × 10 13 Ω / □.
試験例３
[５０ｋｇ仕込みの大型分散機での分散液の調整]
実施例１で用いたアンチモン含有酸化スズ粒子１４．５５ｋｇと、分散剤（花王（株）製エマルゲン１０５）０．４５ｋｇを、メタノール３５．００ｋｇに投入し、軽く混合した。
次いで、この混合溶液を分散機（浅田鉄工株式会社製：ＰＣＭＨ−Ｃ２Ｍ型、ベッセル容量４００ｍｌ）に投入し、循環させた。
この際、ジルコニアビーズ（粒子径０．１ｍｍ）を１．８ｋｇ（ベッセル容量に対して７０容量％相当）を徐々に添加し、分散機を周速８ｍ／ｓで３０分運転し、混合液を分散させた。経時的にサンプリングを行い、メジアン径を測定すると共に実施例６と同様にして硬化膜を作製してその表面抵抗値とＨＡＺＥ値を測定した。結果を表３に示す。
尚、分散機の周速を８ｍ／ｓから、６ｍ／ｓ及び１０ｍ／ｓに変更して分散させた試験結果も同様に示す。
Test example 3
[Dispersion adjustment with a 50kg large dispersion machine]
14.55 kg of antimony-containing tin oxide particles used in Example 1 and 0.45 kg of a dispersant (Emulgen 105 manufactured by Kao Corporation) were added to 35.00 kg of methanol and mixed gently.
Next, this mixed solution was charged into a disperser (Asada Tekko Co., Ltd .: PCMH-C2M type, vessel capacity 400 ml) and circulated.
At this time, 1.8 kg of zirconia beads (particle diameter: 0.1 mm) (corresponding to 70% by volume with respect to the vessel capacity) was gradually added, and the disperser was operated at a peripheral speed of 8 m / s for 30 minutes. Dispersed. Sampling was performed over time, the median diameter was measured, and a cured film was prepared in the same manner as in Example 6 to measure the surface resistance value and the HAZE value. The results are shown in Table 3.
The test results obtained by dispersing the peripheral speed of the disperser from 8 m / s to 6 m / s and 10 m / s are also shown.
本発明のアンチモン含有酸化スズ分散液は、保護膜、反射防止膜、接着剤、シーリング材、バインダー材等に用いられる樹脂組成物に含ませて用いることができ、特に反射防止膜の高屈折率膜を形成する樹脂組成物に好適に用いることができる。
本発明の透明性導電膜は、各種基材、例えば、プラスチック（ポリカーボネート、ポリメチルメタクリレート、ポリスチレン、ポリエステル、ポリオレフィン、エポキシ樹脂、メラミン樹脂、トリアセチルセルロース樹脂、ＡＢＳ樹脂、ＡＳ樹脂、ノルボルネン系樹脂等）、金属、木材、紙、ガラス、スレート等の上に形成することにより、これら基材に、ハードコート性、帯電防止性等の機能を付加することができる。本発明の透明性導電膜は、特に、透明性が高いので透明基材の保護膜に適している。
The antimony-containing tin oxide dispersion of the present invention can be used by being included in a resin composition used for a protective film, an antireflection film, an adhesive, a sealing material, a binder material, and the like. It can use suitably for the resin composition which forms a film | membrane.
The transparent conductive film of the present invention is made of various substrates such as plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, etc. ), By forming on metal, wood, paper, glass, slate, etc., functions such as hard coat properties and antistatic properties can be added to these substrates. The transparent conductive film of the present invention is particularly suitable for a protective film on a transparent substrate because of its high transparency.
Claims (3)
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| JP2008247948A (en) * | 2007-03-29 | 2008-10-16 | Jsr Corp | Curable composition, cured film and laminate |
| JP2010050094A (en) * | 2008-08-12 | 2010-03-04 | Boeing Co:The | Durable transparent electrode on polymer substrate |
| JP2010059280A (en) * | 2008-09-02 | 2010-03-18 | Toppan Printing Co Ltd | Hardcoat coating liquid, hardcoat film, and upper electrode plate for touch panel |
| JP2013027852A (en) * | 2011-07-29 | 2013-02-07 | Fujifilm Corp | Dispersion media |
| WO2022210848A1 (en) * | 2021-03-30 | 2022-10-06 | 日揮触媒化成株式会社 | Dispersion of conductive particles, production method for same, coating liquid for conductive film formation, and conductive film–coated substrate |
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