JP5094641B2 - Porous optical material for antireflection and method for producing the same - Google Patents
Porous optical material for antireflection and method for producing the same Download PDFInfo
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- JP5094641B2 JP5094641B2 JP2008220428A JP2008220428A JP5094641B2 JP 5094641 B2 JP5094641 B2 JP 5094641B2 JP 2008220428 A JP2008220428 A JP 2008220428A JP 2008220428 A JP2008220428 A JP 2008220428A JP 5094641 B2 JP5094641 B2 JP 5094641B2
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- fluorine
- photopolymerization initiator
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Landscapes
- Surface Treatment Of Optical Elements (AREA)
- Polymerisation Methods In General (AREA)
Description
本発明は、屈折率を低下させる反射防止用多孔質光学材料およびその製造方法に関し、反射防止膜、光導波路、レンズ、プリズム等に好適に用いられる反射防止用多孔質光学材料およびその製造方法に関する。 The present invention relates to an antireflection porous optical material that lowers the refractive index and a method for producing the same, and relates to an antireflection porous optical material suitably used for an antireflection film, an optical waveguide, a lens, a prism, and the like, and a method for producing the same. .
低屈折材料は、ＣＲＴ、ＰＤＰ、ＥＬＤ、ＬＣＤのようなディスプレイ装置表面に配置される光学フィルム（特に反射防止フィルム）材料として使用され、外光の反射によるコントラスト低下や像の映り込み防止の役割を担っている。反射防止フィルムは、光学干渉の原理を用いて反射率を低減するもので、一般的には、屈折率の高い材料と屈折率の低い材料を交互に積層する多層膜による方法と、支持体上にそれより低屈折率で適当な膜厚の層を形成することにより方法等がある。後者の場合、低い反射率を実現するためには、支持体上の層は、可能な限り空気の屈性率（屈折率：１．０）に近づけるほど、その効果は大きい。 Low refractive materials are used as optical film (especially anti-reflection film) materials that are placed on the surface of display devices such as CRT, PDP, ELD, and LCD, and play a role in preventing contrast degradation and image reflection due to reflection of external light. Is responsible. An antireflection film is a film that reduces the reflectivity by using the principle of optical interference. Generally, an antireflection film is a method using a multilayer film in which a material having a high refractive index and a material having a low refractive index are alternately laminated, and a substrate. In addition, there is a method by forming a layer having a lower refractive index and an appropriate film thickness. In the latter case, in order to achieve a low reflectance, the effect of the layer on the support becomes greater as close as possible to the refractive index of air (refractive index: 1.0).
また光学フィルムは、ディスプレイの最表面に用いられるため、高い耐傷性が要求され、低屈折率、耐傷性を有する廉価な光学材料の開発が切望されていた。従来、屈折率の低い材料としては、フッ化マグネシウムのような無機フッ素化物（屈折率：１．３４〜１．３８）、粒子の内部に空孔（空気）を含む中空シリカ粒子（屈折率：１．２５〜１．３５）、およびそれらの微粒子を樹脂等に分散させて形成したもの、フッ素含有モノマー、フッ素含有ポリマーのような含F有機化合物（屈折率：１．３５〜１．４２）が知られている。 Further, since the optical film is used on the outermost surface of the display, high scratch resistance is required, and development of an inexpensive optical material having a low refractive index and scratch resistance has been desired. Conventionally, as a material having a low refractive index, inorganic fluorinated materials such as magnesium fluoride (refractive index: 1.34 to 1.38), hollow silica particles containing pores (air) inside the particles (refractive index: 1.25 to 1.35), and those formed by dispersing these fine particles in a resin, etc., fluorine-containing monomers, fluorine-containing organic compounds such as fluorine-containing polymers (refractive index: 1.35 to 1.42) It has been known.
しかしながら、これらの材料では、塗膜の屈折率として、高々、１．３程度であり、これより低いものを得ることはできなかった。中空シリカ微粒子を多量に使用すれば、屈折率１．３より小さくすることは可能であるが、柔軟な膜にならない、コストが高い等の別の問題を生じる。 However, with these materials, the refractive index of the coating film is at most about 1.3, and it was not possible to obtain a material lower than this. If hollow silica fine particles are used in a large amount, it is possible to make the refractive index smaller than 1.3. However, other problems such as not being a flexible film and high cost arise.
また、屈折率１．３以下の低屈折率層を得る方法としては、樹脂等のマトリックス材料中に、上記低屈折微粒子の代わりに、真空、空気、あるいは窒素等のガスからなる微小な空孔を分散させることによりマトリックス材料より低い屈折率を得る方法がいくつか提案されている（例えば、特許文献１参照）。例えば、（１）加熱、光あるいは電子線の照射により分解して窒素等のガスを発生する物質をマトリックスとなる樹脂中に分散あるいは溶解させ、乾燥後、加熱、光、あるいは電子線照射により気泡を発生させ、多孔質体を得る方法、（２）樹脂モノマーに発泡物質を分散あるいは溶解させ、重合後あるいはその前又は同時に、加熱、光照射、電子線照射により発泡させて多孔質体を作る方法、（３）重合による体積収縮率の大きい樹脂モノマーの重合により空孔を作る方法、（４）重合する際に体積の膨張率が極端に異なる２種以上のモノマーからの共重合体を合成する際に発生する局部的な体積の収縮を利用して微小な空孔を発生させる方法、（５）樹脂モノマーと相分離状態を示す材料とシリコーンオイル、液晶を混合させて多孔質体を作る方法、（６）空気等のガスを含むマイクロカプセル（マイクロバルーン）をマトリックスに分散させ、乾燥して多孔質体を得る方法等が提案されている。 In addition, as a method for obtaining a low refractive index layer having a refractive index of 1.3 or less, a fine hole made of a gas such as vacuum, air, or nitrogen is used instead of the low refractive fine particles in a matrix material such as a resin. Several methods have been proposed for obtaining a refractive index lower than that of a matrix material by dispersing s (see, for example, Patent Document 1). For example, (1) a substance that decomposes by heating, irradiation with light or electron beam to generate a gas such as nitrogen is dispersed or dissolved in a matrix resin, and after drying, bubbles are formed by heating, light, or electron beam irradiation. (2) A foamed substance is dispersed or dissolved in a resin monomer and foamed by heating, light irradiation, or electron beam irradiation after polymerization or before or simultaneously to produce a porous body. Method, (3) Method of creating voids by polymerization of resin monomer with large volume shrinkage by polymerization, (4) Synthesis of copolymer from two or more monomers having extremely different volume expansion coefficients during polymerization (5) A porous material obtained by mixing a resin monomer, a material showing a phase separation state, silicone oil, and liquid crystal. Making method, (6) a microcapsule containing a gas such as air (microballoons) are dispersed in a matrix, and a method of obtaining a porous body and dried have been proposed.
しかし、これらの方法では、空孔が発生し、層全体の屈折率がマトリックスの屈折率より低くなることが原理的に確認されているが、屈折率の低下率は０．１％程度であり、屈折率１．３以下の層を実用化するには大きな技術的な障害があった。
本発明の目的は、従来にない低屈折率を可能にする反射防止用多孔質光学材料およびその製造方法を提供することにある。本発明の他の目的は、皮膜性を有し、耐傷性が高く、廉価に製造可能な反射防止用多孔質光学材料およびその製造方法を提供することにある。更に本発明の別の目的は、指紋等による汚れが付着し難い反射防止用多孔質光学材料およびその製造方法を提供することにある。 An object of the present invention is to provide an antireflective porous optical material that enables an unprecedented low refractive index and a method for producing the same. Another object of the present invention is to provide an antireflection porous optical material having a film property, high scratch resistance, and capable of being produced at low cost, and a method for producing the same. Furthermore, another object of the present invention is to provide a porous optical material for antireflection which is difficult to be contaminated by fingerprints and the like, and a method for producing the same.
上記目的を達成すべく、本発明者は、マトリックス材料中に微小な空孔を分散させて発生させる方法を研究した結果、少なくとも光重合性モノマーおよび光重合開始剤を含有する感光性組成物を、例えばＴＡＣ（トリアセチルセルロース）、またはＰＥＴ（ポリエチレンテレフタレート）等の透明支持体上に塗布し、乾燥させ、塗膜を形成する際に、光重合開始剤として気体を発生する化合物を使用し、かつその量と光重合開始剤の分解前の感光組成物の硬さとを調整することにより、多数の微小な空孔を容易に作成することができることを発見し、本発明に到った。 In order to achieve the above object, the present inventors have studied a method of generating fine pores by dispersing them in a matrix material, and as a result, have found a photosensitive composition containing at least a photopolymerizable monomer and a photopolymerization initiator. For example, when a TAC (triacetyl cellulose) or PET (polyethylene terephthalate) is applied on a transparent support and dried to form a coating film, a compound that generates gas is used as a photopolymerization initiator, In addition, it was discovered that a large number of minute holes can be easily formed by adjusting the amount and the hardness of the photosensitive composition before decomposition of the photopolymerization initiator, and the present invention has been achieved.
すなわち以下の手段により、前記課題を解決した。
１． 少なくとも光重合性モノマーおよび光重合開始剤を含有する感光性組成物を用いて形成される直径１０オングストローム〜３００ｎｍの微小空孔を有する反射防止用多孔質光学材料であって、
該光重合開始剤が、光照射、または、光照射および加熱により分解して気体を発生する光重合開始剤であり、該光重合開始剤の含有量が前記感光性組成物の全固形分の４〜２０質量％であり、かつ光照射前の感光性組成物の下記数式（１）で表されるダイナミック硬度（ＤＨ）が、１０〜１００（ｍＮ/μｍ２）である反射防止用多孔質光学材料。
ＤＨ＝αＰ／Ｄ２ …（１）
Ｐ：荷重（ｇｆ）、Ｄ：押し込み深さ（μｍ）
α：圧子の形による定数（三角錘の場合、α＝３７．８４）
２． 前記光重合性モノマーが、少なくとも重合性基を２つ有する含フッ素化合物であって、該含フッ素化合物のフッ素含有率が、３０％以上である上記１に記載の反射防止用多孔質光学材料。（ここでフッ素含有率とは、含フッ素化合物中のフッ素の質量％である）
３． 前記感光性組成物が、更にフッ素系界面活性剤またはシリコーン系界面活性剤を含有する上記１または２に記載の反射防止用多孔質光学材料。
４． 前記光重合開始剤が、光照射、または、光照射および加熱により分解して窒素または炭酸ガスを発生する光重合開始剤である上記１〜３のいずれかに記載の反射防止用多孔質光学材料。
５． 少なくとも光重合性モノマーおよび光重合開始剤を含有する感光性組成物に、光照射処理、または、光照射および加熱処理を行い、直径１０オングストローム〜３００ｎｍの微小空孔を有する反射防止用多孔質光学材料を製造する方法であって、
該光重合開始剤が、光照射、または、光照射および加熱により分解して気体を発生する光重合開始剤であり、該光重合開始剤の含有量が該感光性組成物の全固形分の４〜２０質量％であり、かつ光照射前の感光性組成物の下記数式（１）で表されるダイナミック硬度（ＤＨ）が、１０〜１００（ｍＮ/μｍ２）である反射防止用多孔質光学材料の製造方法。
ＤＨ＝αＰ／Ｄ２ …（１）
Ｐ：荷重（ｇｆ）、Ｄ：押し込み深さ（μｍ）
α：圧子の形による定数（三角錘の場合、α＝３７．８４）
６． 前記光重合性モノマーが、少なくとも重合性基を２つ有する含フッ素化合物であって、該含フッ素化合物のフッ素含有率が、３０％以上である上記５に記載の反射防止用多孔質光学材料の製造方法。（ここでフッ素含有率とは、含フッ素化合物中のフッ素の質量％である）
７． 前記感光性組成物が、更にフッ素系界面活性剤またはシリコーン系界面活性剤を含有する上記５または６に記載の反射防止用多孔質光学材料の製造方法。
That is, the said subject was solved by the following means.
1. An antireflection porous optical material having micropores having a diameter of 10 angstroms to 300 nm formed using a photosensitive composition containing at least a photopolymerizable monomer and a photopolymerization initiator,
The photopolymerization initiator is a photopolymerization initiator that decomposes by light irradiation or light irradiation and heating to generate gas, and the content of the photopolymerization initiator is the total solid content of the photosensitive composition 4 to 20% by mass and an anti-reflection porous material having a dynamic hardness (DH) represented by the following formula (1) of the photosensitive composition before light irradiation of 10 to 100 (mN / μm 2 ) Optical material.
DH = αP / D 2 (1)
P: Load (gf), D: Indentation depth (μm)
α: Constant depending on the shape of the indenter (α = 37.84 for triangular pyramid)
2. 2. The antireflection porous optical material according to 1 above, wherein the photopolymerizable monomer is a fluorine-containing compound having at least two polymerizable groups, and the fluorine content of the fluorine-containing compound is 30% or more. (Here, the fluorine content is the mass% of fluorine in the fluorine-containing compound)
3. 3. The antireflection porous optical material according to 1 or 2 above, wherein the photosensitive composition further contains a fluorine-based surfactant or a silicone-based surfactant.
4). 4. The antireflection porous optical material according to any one of 1 to 3, wherein the photopolymerization initiator is a photopolymerization initiator that decomposes by light irradiation or light irradiation and heating to generate nitrogen or carbon dioxide gas. .
5. Porous optics for antireflection having micropores having a diameter of 10 angstroms to 300 nm by subjecting a photosensitive composition containing at least a photopolymerizable monomer and a photopolymerization initiator to light irradiation treatment or light irradiation and heat treatment. A method of manufacturing a material comprising:
The photopolymerization initiator is a photopolymerization initiator that decomposes by light irradiation or light irradiation and heating to generate gas, and the content of the photopolymerization initiator is the total solid content of the photosensitive composition 4 to 20% by mass and an anti-reflection porous material having a dynamic hardness (DH) represented by the following formula (1) of the photosensitive composition before light irradiation of 10 to 100 (mN / μm 2 ) Manufacturing method of optical material.
DH = αP / D 2 (1)
P: Load (gf), D: Indentation depth (μm)
α: Constant depending on the shape of the indenter (α = 37.84 for triangular pyramid)
6). 6. The antireflection porous optical material according to 5 above, wherein the photopolymerizable monomer is a fluorine-containing compound having at least two polymerizable groups, and the fluorine content of the fluorine-containing compound is 30% or more. Production method. (Here, the fluorine content is the mass% of fluorine in the fluorine-containing compound)
7). 7. The method for producing an antireflection porous optical material according to 5 or 6, wherein the photosensitive composition further contains a fluorine-based surfactant or a silicone-based surfactant.
本発明の反射防止用多孔質光学材料は、少なくとも光重合性モノマーおよび光重合開始剤を含有する感光性組成物を用いて形成される直径１０オングストローム〜３００ｎｍの微小空孔を有する反射防止用多孔質光学材料であって、該光重合開始剤が、光照射、または、光照射および加熱により分解して気体を発生する光重合開始剤であり、該光重合開始剤の含有量が前記感光性組成物の全固形分の４〜２０質量％であり、かつ光照射前の感光性組成物の下記数式（１）で表されるダイナミック硬度（ＤＨ）が、１０〜１００（ｍＮ/μｍ２）である。
ＤＨ＝αＰ／Ｄ２ …（１）
Ｐ：荷重（ｇｆ）、Ｄ：押し込み深さ（μｍ）
α：圧子の形による定数（三角錘の場合、α＝３７．８４）
The antireflection porous optical material of the present invention is an antireflection porous material having a micropore having a diameter of 10 angstroms to 300 nm formed using a photosensitive composition containing at least a photopolymerizable monomer and a photopolymerization initiator. The photopolymerization initiator is a photopolymerization initiator that generates gas upon decomposition by light irradiation or light irradiation and heating, and the content of the photopolymerization initiator is the photosensitivity. The dynamic hardness (DH) represented by the following formula (1) of the photosensitive composition before irradiation with light is 4 to 20% by mass of the total solid content of the composition, and is 10 to 100 (mN / μm 2 ). It is.
DH = αP / D 2 (1)
P: Load (gf), D: Indentation depth (μm)
α: Constant depending on the shape of the indenter (α = 37.84 for triangular pyramid)
以下、本発明における感光性組成物の光重合性モノマー（含む含フッ素化合物）、光重合開始剤、必要に応じて用いられるフッ素系界面活性剤、シリコーン系界面活性剤等の感光性材料、およびその硬化過程と平行して行われる微細な空孔形成過程について説明するが、本発明は、本実施の形態に制限されるものではない。 Hereinafter, a photopolymerizable monomer (including a fluorine-containing compound), a photopolymerization initiator, a photosensitive material such as a fluorine-based surfactant and a silicone-based surfactant used as necessary, and the photosensitive composition of the present invention, and Although a fine pore formation process performed in parallel with the curing process will be described, the present invention is not limited to this embodiment.
（光重合性モノマー）
本発明で使用される光重合性モノマーとしては、好ましくは１分子中に少なくとも１個の（メタ）アクリロイル基、ビニル基、スチリル基、アリル基等の重合性官能基を有する化合物であり、より好ましくは１分子中に２〜１０個の重合性官能基を有する化合物である。その中でも１分子中に２個以上の（メタ）アクリロイル基を含有する化合物は、適度な架橋密度を有する皮膜を得やすいため、耐擦傷性や耐薬品性に優れ、好適に使用される。
(Photopolymerizable monomer)
The photopolymerizable monomer used in the present invention is preferably a compound having a polymerizable functional group such as at least one (meth) acryloyl group, vinyl group, styryl group, and allyl group in one molecule. Preferably, it is a compound having 2 to 10 polymerizable functional groups in one molecule. Among them, a compound containing two or more (meth) acryloyl groups in one molecule is easily used because it is easy to obtain a film having an appropriate crosslinking density and is excellent in scratch resistance and chemical resistance.
これらの光重合性モノマーの具体例としては、種々の多価アルコールと（メタ）アクリル酸とのエステル類が広く知られており、例えば２官能の（メタ）アクリル酸エステル類としては、ネオペンチルグリコール、１，６−ヘキサンジオール、プロピレングリコール、トリエチレングリコール、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール等の２価のアルコール、トリメチロールプロパン、ペンタエリスリトール等の多価アルコールと（メタ）アクリル酸を反応させて得られるジ（メタ）アクリル酸エステルをあげることができる。更に２，２−ビス｛４−（アクリロキシ・ジエトキシ）フェニル｝プロパン、２，２−ビス｛４−（アクリロキシ・ポリプロポキシ）フェニル｝プロパン等のエチレンオキシドあるいはプロピレンオキシド付加物の（メタ）アクリル酸ジエステル、変性イソシアヌレートジ（メタ）アクリル酸ジエステル等、２官能のエポキシ（メタ）アクリレート類、ウレタン（メタ）アクリレート類、ポリエステル（メタ）アクリレート等を挙げることができる。 As specific examples of these photopolymerizable monomers, esters of various polyhydric alcohols and (meth) acrylic acid are widely known. For example, as bifunctional (meth) acrylic acid esters, neopentyl is used. Dihydric alcohols such as glycol, 1,6-hexanediol, propylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol and polypropylene glycol, polyhydric alcohols such as trimethylolpropane and pentaerythritol, and (meth) acrylic acid. The di (meth) acrylic acid ester obtained by making it react can be mention | raise | lifted. Further, (meth) acrylic acid diesters of ethylene oxide or propylene oxide adducts such as 2,2-bis {4- (acryloxydiethoxy) phenyl} propane and 2,2-bis {4- (acryloxypolypropoxy) phenyl} propane And bifunctional epoxy (meth) acrylates, urethane (meth) acrylates, polyester (meth) acrylates, and the like such as modified isocyanurate di (meth) acrylic acid diester.
３官能以上の多官能の（メタ）アクリル酸エステル類としては、例えばペンタエリスリトールテトラ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、EO変性トリメチロールプロパントリ（メタ）アクリレート、PO変性トリメチロールプロパントリ（メタ）アクリレート、EO変性リン酸トリ（メタ）アクリレート、トリメチロールエタントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ペンタエリスリトールヘキサ（メタ）アクリレート、１，２，３−クロロヘキサンテトラ（メタ）アクリレート、ポリウレタンポリ（メタ）アクリレート、ポリエステルポリアクリレート、カプロラクトン変性トリス（アクリロキシエチル）イソシアヌレート等が挙げられる。 Examples of the trifunctional or higher polyfunctional (meth) acrylic acid esters include pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri ( (Meth) acrylate, PO-modified trimethylolpropane tri (meth) acrylate, EO-modified tri (meth) acrylate phosphate, trimethylolethane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, 1,2,3-chlorohe Santetora (meth) acrylates, polyurethane poly (meth) acrylate, polyester polyacrylate and caprolactone-modified tris (acryloyloxyethyl) isocyanurate.
また（メタ）アクリロイル基を有する多官能アクリレート系化合物類の具体化合物は多くの材料メーカーから市販されており、これらの中から適宜選択して使用することができる。市販されている多官能アクリレート化合物の具体例としては、日本化薬（株）製ＫＡＹＡＲＡＤ ＤＰＨＡ、同ＤＰＨＡ−２Ｃ、同ＰＥＴ−３０、同ＴＭＰＴＡ、同ＴＰＡ−３２０、同ＴＰＡ−３３０、同ＲＰ−１０４０、同Ｔ−１４２０、同Ｄ−３１０，同ＤＰＣＡ−２０，同ＤＰＣＡ−３０、同ＤＰＣＡ−６０、同ＧＰＯ−３０３、大阪有機化学工業（株）製Ｖ＃３ＰＡ、Ｖ＃４００、Ｖ＃３６０９５Ｄ、Ｖ＃１０００、Ｖ＃１０８０等のポリオールと（メタ）アクリル酸のエステル化物を挙げることができる。また紫外光ＵＶ−１４００Ｂ、同ＵＶ−１７００Ｂ、同ＵＶ−６３００Ｂ，同ＵＶ−７５５０Ｂ、同ＵＶ−７６００Ｂ、同ＵＶ−７６０５Ｂ、同ＵＶ−７６１０Ｂ，同ＵＶ−７６２０ＥＡ、同ＵＶ−７６３０Ｂ、同ＵＶ−７６４０Ｂ、同ＵＶ−６６３０Ｂ、同ＵＶ−７０００Ｂ、同ＵＶ−７５１０Ｂ、同ＵＶ−７４６１ＴＥ，同ＵＶ−３０００Ｂ、同ＵＶ−３２００Ｂ、同ＵＶ−３２１０Ｂ、同ＵＶ−３２１０ＥＡ、同ＵＶ−３３１０ＥＡ、同ＵＶ−３３１０Ｂ，同ＵＶ−３５００ＢＡ，同ＵＶ−３５２０ＴＬ、同ＵＶ−３７００Ｂ、同ＵＶ−６１００Ｂ、同ＵＶ−６６４０Ｂ、同ＵＶ−２０００Ｂ、同ＵＶ−２０１０Ｂ、同ＵＶ−２２５０ＥＡ，同ＵＶ−２７５０Ｂ（日本合成化学（株）製）、ＵＬ−５０３ＬＮ（共栄社化学（株）製）、ユニディック１７−８０６、同１７−８１３、同Ｖ−４０３０、同Ｖ−４０００ＢＡ（大日本インキ化学工業（株）製）、ＥＢ−１２９０Ｋ，ＥＢ−２２０，ＥＢ−５１２９，ＥＢ−１８３０、ＥＢ−４８５８（ダイセルＵＣＢ（株）製）、ハイコープＡＵ−２０１０、同ＡＵ−２０２０（（株）トクシキ製）、アロニックスＭ−１９６０（東亜合成（株）製、根上工業（株）製アートレジンＵＮ−３３２０ＨＡ、ＵＮ−３３２０ＨＣ，ＵＮ−３３２０ＨＳ，ＵＮ−９０４，ＨＤＰ−４Ｔなどの３官能以上のウレタンアクリレート化合物、アロニックスＭ−８１００，Ｍ−８０３０，Ｍ−９０５０（東亜合成（株）製、ＫＲＭ−８３０７（ダイセルサイテック（株）製）などの３官能以上のポリエステル化合物などをあげることができるがこれに限定されるものではない。 Specific compounds of polyfunctional acrylate compounds having a (meth) acryloyl group are commercially available from many material manufacturers, and can be used by appropriately selecting from these. Specific examples of commercially available polyfunctional acrylate compounds include KAYARAD DPHA, DPHA-2C, PET-30, TMPTA, TPA-320, TPA-330, and RP- manufactured by Nippon Kayaku Co., Ltd. 1040, T-1420, D-310, DPCA-20, DPCA-30, DPCA-60, GPO-303, Osaka Organic Chemical Industry Co., Ltd. V # 3PA, V # 400, V # Examples include esterified products of polyols such as 36095D, V # 1000, and V # 1080 and (meth) acrylic acid. Further, ultraviolet light UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B, UV-7610B, UV-7620EA, UV-7630B, UV-7630B, UV- 7640B, UV-6630B, UV-7000B, UV-7510B, UV-7461TE, UV-3000B, UV-3200B, UV-3210B, UV-3210EA, UV-3210EA, UV-3310EA, UV- 3310B, UV-3500BA, UV-3520TL, UV-3700B, UV-6100B, UV-6640B, UV-2000B, UV-2010B, UV-2250EA, UV-2250EA, UV-2750B Manufactured by), UL-503LN (manufactured by Kyoeisha Chemical Co., Ltd.), Nidick 17-806, 17-813, V-4030, V-4000BA (manufactured by Dainippon Ink and Chemicals, Inc.), EB-1290K, EB-220, EB-5129, EB-1830, EB-4858 (Manufactured by Daicel UCB Co., Ltd.), Hicorp AU-2010, AU-2020 (manufactured by Tokushiki Co., Ltd.), Aronix M-1960 (manufactured by Toagosei Co., Ltd., Art Resin UN-3320HA manufactured by Negami Kogyo Co., Ltd.) Trifunctional or more urethane acrylate compounds such as UN-3320HC, UN-3320HS, UN-904, HDP-4T, Aronix M-8100, M-8030, M-9050 (manufactured by Toa Gosei Co., Ltd., KRM-8307 (Daicel) This can include tri- or higher functional polyester compounds such as Cytec Co., Ltd. The present invention is not limited to.
さらに、ＵＶ・ＥＢ硬化技術の現状と展望、市村国宏監修、株式会社シーエムシー出版、２００２年１２月２７日発行の１０頁から３８頁に記載のアクリル系モノマー、オリゴマー等を使用することができる。 Furthermore, use of acrylic monomers and oligomers described in pages 10 to 38 of UV / EB curing technology, supervised by Kunihiro Ichimura, supervised by Kunihiro Ichimura, published by CMC Publishing Co., Ltd., December 27, 2002. Can do.
さらに、３個以上の（メタ）アクリロイル基を有する樹脂、たとえば比較的低分子量のポリエステル樹脂、ポリエーテル樹脂、アクリル樹脂、エポキシ樹脂、ウレタン樹脂、アルキッド樹脂、スピロアセタール樹脂、ポリブタジエン樹脂、ポリオールポリエン樹脂、多価アルコール等の多官能化合物のオリゴマーまたはプレポリマー等もあげられる。
本発明の感光性組成物の露光前のダイナミック硬度（ＤＨ）１０〜１００（ｍＮ/μｍ２）は、主要素材の光重合性モノマー、光重合開始剤、後述の硬さ調整用のバインダー、微粒子等の種類、添加量に依存するため、光重合性モノマーとしては広い範囲のモノマーを選択することが可能である。例えば光重合性モノマーが感光性組成物の固形分全量の５０質量％以上である場合においては、分子量３００〜１０００の多官能アクリル系モノマーを使用することが好ましい。
Furthermore, resins having three or more (meth) acryloyl groups, such as relatively low molecular weight polyester resins, polyether resins, acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polyol polyene resins. And oligomers or prepolymers of polyfunctional compounds such as polyhydric alcohols.
The dynamic hardness (DH) before exposure of the photosensitive composition of the present invention is 10 to 100 (mN / μm 2 ). The main material is a photopolymerizable monomer, a photopolymerization initiator, a binder for adjusting hardness described later, and fine particles. Therefore, a wide range of monomers can be selected as the photopolymerizable monomer. For example, when the photopolymerizable monomer is 50% by mass or more of the total solid content of the photosensitive composition, it is preferable to use a polyfunctional acrylic monomer having a molecular weight of 300 to 1,000.
光重合性モノマーの内、含フッ素化合物、とくに含フッ素多官能モノマーは、低屈折率を達成する目的で本発明では好適に使用される。含フッ素多官能モノマーは、主に複数のフッ素原子と炭素原子から成る（但し一部に酸素原子及び／又は水素原子を含んでも良い）、実質的に重合に関与しない原子団（以下「含フッ素コア部」という）と、エステル結合やエーテル結合などの連結基を介して、アクリロイル基やメタクリロイル基等の２つ以上の重合性基を有する含フッ素化合物である。含フッ素化合物は、十分な低屈折率を得るために、そのフッ素含有率が３０％以上であることが好ましく、３０％〜６５％の化合物を使用することが可能である。なお、フッ素含有率とは、含フッ素化合物中のフッ素の質量％である。光重合性モノマーが、少なくとも重合性基を２つ有する含フッ素化合物であって、かつ該含フッ素化合物のフッ素含有率が、３０％以上であることが特に好ましい。 Of the photopolymerizable monomers, fluorine-containing compounds, particularly fluorine-containing polyfunctional monomers, are preferably used in the present invention for the purpose of achieving a low refractive index. The fluorine-containing polyfunctional monomer mainly comprises a plurality of fluorine atoms and carbon atoms (however, oxygen atoms and / or hydrogen atoms may be included in part), and is an atomic group that does not substantially participate in polymerization (hereinafter referred to as “fluorine-containing monomers”). And a fluorine-containing compound having two or more polymerizable groups such as an acryloyl group and a methacryloyl group via a linking group such as an ester bond and an ether bond. In order to obtain a sufficiently low refractive index, the fluorine-containing compound preferably has a fluorine content of 30% or more, and a compound of 30% to 65% can be used. In addition, a fluorine content rate is the mass% of the fluorine in a fluorine-containing compound. It is particularly preferable that the photopolymerizable monomer is a fluorine-containing compound having at least two polymerizable groups, and the fluorine content of the fluorine-containing compound is 30% or more.
本発明に好適に用いられる含フッ素多官能モノマーは、好ましくは下記一般式（２）で表される。
一般式（２） Ｒｆ［−（Ｌ）ｍ−Ｙ］ｎ
一般式（２）中、Ｒｆは少なくとも炭素原子及びフッ素原子を含み、酸素原子及び／または水素原子を含んでもよい、鎖状または環状の、ｎ価のフッ素炭化水素基を表し、ｎは２以上の整数を表す。Ｌは二価の連結基を表し、ｍは０又は１を表す。Ｙは重合性基を表す。
Ｒｆ（含フッ素コア部）における水素原子数／フッ素原子数は１／４以下のものが好ましく、ｎは３以上であることが好ましい。Ｒｆの代表的なものとしては、下記の具体例が挙げられる。
The fluorine-containing polyfunctional monomer suitably used in the present invention is preferably represented by the following general formula (2).
General formula (2) Rf [-(L) m- Y] n
In the general formula (2), Rf represents a chain or cyclic n-valent fluorine hydrocarbon group which contains at least a carbon atom and a fluorine atom and may contain an oxygen atom and / or a hydrogen atom, and n is 2 or more. Represents an integer. L represents a divalent linking group, and m represents 0 or 1. Y represents a polymerizable group.
The number of hydrogen atoms / number of fluorine atoms in Rf (fluorine-containing core part) is preferably 1/4 or less, and n is preferably 3 or more. Specific examples of Rf include the following specific examples.
Ｙはラジカル重合性基であることが好ましく、例えば（メタ）アクリロイル基、アリル基、α―フルオロアクリロイル基、および−CO―OCH=CH２等である。 Y is preferably a radically polymerizable group, such as (meth) acryloyl group, allyl group, α-fluoroacryloyl group, and —CO—OCH═CH 2 .
Ｌは２価の連結基を表し、詳しくは、炭素数１〜１０のアルキレン基、炭素数６〜１０のアリーレン基、−Ｏ−、−Ｓ−、−Ｎ（Ｒ）−、炭素数１〜１０のアルキレン基と−Ｏ−、−Ｓ−、−Ｎ（Ｒ）−を組み合わせて得られる基、炭素数６〜１０のアリーレン基と−Ｏ−、−Ｓ−、−Ｎ（Ｒ）−を組み合わせて得られる基を表す。Ｒは水素原子、または炭素数１〜５のアルキル基を表す。Ｌがアルキレン基またはアリーレン基を表す場合、それらの基はハロゲン原子で置換されていることが好ましく、フッ素原子で置換されていることがより好ましい。 L represents a divalent linking group, specifically, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, -O-, -S-, -N (R)-, 1 to carbon atoms. A group obtained by combining 10 alkylene groups with —O—, —S—, —N (R) —, an arylene group with 6 to 10 carbon atoms, and —O—, —S—, —N (R) —. The group obtained by combining is represented. R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. When L represents an alkylene group or an arylene group, these groups are preferably substituted with a halogen atom, and more preferably substituted with a fluorine atom.
本発明の含フッ素多官能モノマーとして、下記一般式（３）または一般式式（４）で表されるモノマーは、屈折率および重合性の観点からより好ましい。 As the fluorine-containing polyfunctional monomer of the present invention, a monomer represented by the following general formula (3) or general formula (4) is more preferable from the viewpoint of refractive index and polymerizability.
一般式（３） Ｒｆ［−ＣＨ２−ＯＣＯＣＨ＝ＣＨ２］ｎ
一般式（４） Ｒｆ［−ＣＯ−Ｏ−ＣＨ＝ＣＨ２］ｎ
Formula (3) Rf [-CH 2 -OCOCH = CH 2] n
Formula (4) Rf [-CO-O -CH = CH 2] n
上記一般式中Ｒｆ、ｎは一般式（２）と同じ意味を表す。 In the above general formula, Rf and n represent the same meaning as in the general formula (2).
以下に、本発明の含フッ素多官能モノマーの具体例を挙げるが、本発明はこれらによって限定されない。 Although the specific example of the fluorine-containing polyfunctional monomer of this invention is given to the following, this invention is not limited by these.
また、特開２００６−２８４７６１号公報の段落番号〔００６２〕から〔００６５〕に記載のＭ−１〜Ｍ−１６も好ましく用いることができる。 Also, M-1 to M-16 described in paragraph numbers [0062] to [0065] of JP-A-2006-284761 can be preferably used.
また、以下に示す化合物ＭＡ１〜ＭＡ２０も好ましく用いることができる。 Moreover, the compounds MA1-MA20 shown below can also be used preferably.
更に特開平１０−１８２７４６号公報、特開２００２−１０５１４１号公報、特開２００６−２８２８０公報、特開２００６−２８４０９号公報等に記載されている含フッ素多官能モノマーを好適に使用することができる。 Furthermore, fluorine-containing polyfunctional monomers described in JP-A-10-182746, JP-A-2002-105141, JP-A-2006-28280, JP-A-2006-28409, and the like can be suitably used. .
本発明において光重合性モノマーの含有量は、感光層中に微細な空孔を均一に生成するおよび皮膜強度を確保するという理由から、感光性組成物の全固形分の５〜８０質量％の範囲であることが好ましく、より好ましくは１０〜６０質量％であり、更に好ましくは２０〜５０質量％である。 In the present invention, the content of the photopolymerizable monomer is 5 to 80% by mass of the total solid content of the photosensitive composition because it uniformly generates fine pores in the photosensitive layer and ensures film strength. It is preferable that it is a range, More preferably, it is 10-60 mass%, More preferably, it is 20-50 mass%.
本発明において、光重合性モノマーは上記に記載した化合物を単独あるいは二種類以上を併用して用いることができる。低屈折率実現のためには、２官能以上の含フッ素モノマーを用いることが好ましいが、相溶性、皮膜強度の観点を加え、フッ素を含有しないモノマーと併用する場合は、２官能以上の含フッ素モノマー：フッ素を含有しないモノマー（質量比）で１９：１〜１：１の範囲が好ましく使用される。 In the present invention, as the photopolymerizable monomer, the above-described compounds can be used alone or in combination of two or more. In order to realize a low refractive index, it is preferable to use a bifunctional or higher fluorine-containing monomer. However, in view of compatibility and film strength, when using in combination with a monomer not containing fluorine, a bifunctional or higher fluorine-containing monomer is used. A monomer: a monomer (mass ratio) not containing fluorine is preferably used in a range of 19: 1 to 1: 1.
（光重合開始剤）
本発明で使用される光重合開始剤は、光照射、または、光照射および加熱により分解して気体を発生するものが好ましく、窒素または炭酸ガスを発生する光重合開始剤であることがより好ましい。
本発明で使用される光照射、または、光照射および加熱により分解して気体を発生する光重合開始剤としては、特許文献、学術文献等で公知の開始剤の中から選択して用いることができる。これらの内、光照射による分解により、窒素を発生する光重合開始剤としては、２−アゾ−ビス−イソブチロニトリル、２−アゾ−ビス−プロビオニトリル、２−アゾ−ビス−シクロヘキサンジニトリル、２−アゾ−ビス−バレロニトリル、２，２’−アゾ−ビス−（２，４−ジメチルバレロニトリル）等の有機アゾ化合物、ジアゾアミノベンゼン塩、ｐ−ニトロベンゼンジアゾニウム塩、ｏ−ニトロベンゼンジアゾニウム塩等のジアゾ化合物をあげることができる。
(Photopolymerization initiator)
The photopolymerization initiator used in the present invention is preferably one that decomposes by light irradiation or light irradiation and heating to generate a gas, and more preferably a photopolymerization initiator that generates nitrogen or carbon dioxide gas. .
The light polymerization used in the present invention, or a photopolymerization initiator that decomposes by light irradiation and heating to generate a gas, can be selected from known initiators in patent literature, academic literature, etc. it can. Among them, 2-azo-bis-isobutyronitrile, 2-azo-bis-probionitrile, 2-azo-bis-cyclohexanedinitrile are photopolymerization initiators that generate nitrogen by decomposition by light irradiation. Organic azo compounds such as 2-azo-bis-valeronitrile, 2,2′-azo-bis- (2,4-dimethylvaleronitrile), diazoaminobenzene salt, p-nitrobenzenediazonium salt, o-nitrobenzenediazonium salt And the like.
また光照射および加熱により分解して気体を発生する光重合開始剤としては、炭酸ガスを発生するものとしてｏ−アシルオキシム型光重合開始剤が知られている。また、炭酸ガスを発生する光重合開始剤として下記構造式で示される化合物の群から選ばれる少なくとも一つを選択することができる。本発明はこれら化合物の群に限定されるものではない。 As a photopolymerization initiator that decomposes by light irradiation and heating to generate a gas, an o-acyloxime photopolymerization initiator is known as one that generates carbon dioxide gas. Further, at least one selected from the group of compounds represented by the following structural formula can be selected as a photopolymerization initiator that generates carbon dioxide gas. The present invention is not limited to these groups of compounds.
これらの光重合開始剤の分解により、生成したラジカルは光重合性モノマーの重合・架橋を起こし、発生した気体はその中に封じ込められることにより、層中に微細な空孔が生じる。直径１０オングストローム（１ｎｍ）〜３００ｎｍの微細な空孔が比較的均一に多数できるためには、光重合・硬化前の層の硬さ、光重合開始剤の量、重合過程の速度が重要な因子と推定される。直径１０オングストローム未満の空孔は均一に作成しにくく、直径３００ｎｍより大きい空孔だと層中で光散乱が生じるため、透明性の低下、着色等の問題が生じる。空孔の直径は好ましくは１〜１００ｎｍであり、より好ましくは２〜２０ｎｍである。 The radicals generated by the decomposition of these photopolymerization initiators cause polymerization / crosslinking of the photopolymerizable monomer, and the generated gas is confined therein, thereby forming fine pores in the layer. In order to make a relatively large number of fine pores having a diameter of 10 angstroms (1 nm) to 300 nm, the hardness of the layer before photopolymerization / curing, the amount of photopolymerization initiator, and the speed of the polymerization process are important factors. It is estimated to be. Holes having a diameter of less than 10 angstroms are difficult to create uniformly, and holes having a diameter of more than 300 nm cause light scattering in the layer, resulting in problems such as a decrease in transparency and coloring. The diameter of the pores is preferably 1 to 100 nm, more preferably 2 to 20 nm.
本発明での光重合開始剤の量は、感光性組成物の全固形分の４〜２０質量％の範囲であり、４質量％未満では空孔の発生量が少なく、２０質量％を超えると空孔の直径が大きくなってしまうため濁りを生じてしまう等の問題が発生する。好ましくは５〜１５質量％であり、更に好ましくは５〜１０質量％である。 The amount of the photopolymerization initiator in the present invention is in the range of 4 to 20% by mass with respect to the total solid content of the photosensitive composition. Problems such as turbidity occur because the diameter of the pores increases. Preferably it is 5-15 mass%, More preferably, it is 5-10 mass%.
光照射前の感光性組成物の硬さは、一定の荷重速度で徐々に荷重を加えながら、稜間角１１５°の三角錘ダイヤモンド圧子を膜面に押し込んだときの荷重を押し込み深さの２乗で除すことで算出されるダイナミック硬度（ＤＨ）で表され、下記の数式（１）で定義される。 The hardness of the photosensitive composition before light irradiation is the depth by which the load when the triangular pyramid diamond indenter with a ridge angle of 115 ° is pushed into the film surface is gradually pushed in at a constant load speed. It is represented by dynamic hardness (DH) calculated by dividing by power and is defined by the following mathematical formula (1).
ＤＨ＝αＰ／Ｄ２ …（１） DH = αP / D 2 (1)
Ｐ：荷重（ｇｆ）、Ｄ：押し込み深さ（μｍ）
α：圧子の形による定数（三角錘の場合、α＝３７．８４）
P: Load (gf), D: Indentation depth (μm)
α: Constant depending on the shape of the indenter (α = 37.84 for triangular pyramid)
本発明では、光照射前の感光性組成物のダイナミック硬度が１０〜１００ｍＮ/μｍ２であることが重要な因子で、１０ｍＮ/μｍ２より小さいと、発生した気体が有効に層中に滞留されずに逃げてしまい、空孔の発生が少なく、１００ｍＮ/μｍ２より大きい場合は、空孔の直径が数μｍ単位となり、直径１０オングストロームから３００ｎｍ程度の空孔を多数作成することができなかったり、ヘイズを生じたり、空孔のために表面の防汚性が著しく劣化したりといった問題が発生することが明らかになった。
さらに好ましいダイナミック硬度は、２０〜７０ｍＮ/μｍ２である。
In the present invention, an important factor that the dynamic hardness of 10~100mN / μm 2 of the photosensitive composition before irradiation, and 10 mN / [mu] m 2 less than generated gas is accumulated in the effective layer If there is little generation of vacancies and greater than 100 mN / μm 2 , the diameter of the vacancies will be in units of several μm, and many vacancies with diameters from 10 Å to 300 nm cannot be created. It has become clear that problems such as haze and the deterioration of the antifouling property of the surface due to pores occur.
Further preferred dynamic hardness is 20 to 70 mN / μm 2 .
本発明の反射防止用多孔質光学材料は、少なくとも前記光重合性モノマーと光重合開始剤を含有し、層の固さを調整する目的や、塗布面状を改良する目的で、高分子バインダーや、有機、無機の微粒子、界面活性剤等を含有させることが可能である。 The antireflection porous optical material of the present invention contains at least the photopolymerizable monomer and a photopolymerization initiator, and is used for the purpose of adjusting the hardness of the layer and improving the coating surface, Organic, inorganic fine particles, surfactants and the like can be contained.
硬さ調整用の高分子バインダーとしては、公知のアルキッド樹脂、アクリル樹脂等を使用することができるが、低屈折率を得るためには、含フッ素ポリマー（含フッ素共重合体）を使用することが好ましい。 As the polymer binder for adjusting the hardness, known alkyd resins, acrylic resins, and the like can be used, but in order to obtain a low refractive index, a fluorine-containing polymer (fluorine-containing copolymer) should be used. Is preferred.
含フッ素共重合体としては、例えば、含フッ素ビニルモノマーを構成成分とするものなどが挙げられる。含フッ素ビニルモノマーとしてはフルオロオレフィン類（例えばフルオロエチレン、ビニリデンフルオライド、テトラフルオロエチレン、ヘキサフルオロプロピレン等）、（メタ）アクリル酸の部分または完全フッ素化アルキルエステル誘導体類（例えばビスコート６ＦＭ（商品名、大阪有機化学製）やＲ−２０２０（商品名、ダイキン製）等）、完全または部分フッ素化ビニルエーテル類等が挙げられるが、好ましくはパーフルオロオレフィン類であり、屈折率、溶解性、透明性、入手性等の観点から特に好ましくはヘキサフルオロプロピレンである。これらの含フッ素ビニルモノマーの組成比を上げれば屈折率を下げることができるが、皮膜強度は低下する。本発明では共重合体のフッ素含率が２０〜６０質量％となるように含フッ素ビニルモノマーを導入することが好ましく、より好ましくは２５〜５５質量％の場合であり、特に好ましくは３０〜５０質量％の場合である。 Examples of the fluorinated copolymer include those containing a fluorinated vinyl monomer as a constituent component. Examples of the fluorine-containing vinyl monomer include fluoroolefins (for example, fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, etc.), (meth) acrylic acid moieties or fully fluorinated alkyl ester derivatives (for example, biscoat 6FM (trade name) , Osaka Organic Chemical Co., Ltd.) and R-2020 (trade name, manufactured by Daikin Co., Ltd.), fully or partially fluorinated vinyl ethers, and the like. Preferred are perfluoroolefins, refractive index, solubility, and transparency. From the viewpoint of availability, hexafluoropropylene is particularly preferable. Increasing the composition ratio of these fluorinated vinyl monomers can lower the refractive index but lowers the film strength. In the present invention, the fluorine-containing vinyl monomer is preferably introduced so that the fluorine content of the copolymer is 20 to 60% by mass, more preferably 25 to 55% by mass, and particularly preferably 30 to 50%. This is a case of mass%.
上記含フッ素ビニルモノマーと架橋反応性付与のために下記（ａ）、（ｂ）、（ｃ）で示される単位との共重合体が好ましく利用できる。 For the purpose of imparting crosslinking reactivity to the above-mentioned fluorine-containing vinyl monomer, a copolymer of the following units (a), (b) and (c) can be preferably used.
（ａ）：グリシジル（メタ）アクリレート、グリシジルビニルエーテルのように分子内にあらかじめ自己架橋性官能基を有するモノマーの重合によって得られる構成単位、
（ｂ）：カルボキシル基やヒドロキシ基、アミノ基、スルホ基等を有するモノマー（例えば（メタ）アクリル酸、メチロール（メタ）アクリレート、ヒドロキシアルキル（メタ）アクリレート、アリルアクリレート、ヒドロキシエチルビニルエーテル、ヒドロキシブチルビニルエーテル、マレイン酸、クロトン酸等）の重合によって得られる構成単位、
（ｃ）：分子内に上記（ａ）、（ｂ）の官能基と反応する基とそれとは別に架橋性官能基を有する化合物を、上記（ａ）、（ｂ）の構成単位と反応させて得られる構成単位、（例えばヒドロキシル基に対してアクリル酸クロリドを作用させる等の手法で合成できる構成単位）が挙げられる。
(A): a structural unit obtained by polymerization of a monomer having a self-crosslinkable functional group in the molecule in advance such as glycidyl (meth) acrylate or glycidyl vinyl ether,
(B): a monomer having a carboxyl group, a hydroxy group, an amino group, a sulfo group, etc. (for example, (meth) acrylic acid, methylol (meth) acrylate, hydroxyalkyl (meth) acrylate, allyl acrylate, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether) , Maleic acid, crotonic acid, etc.)
(C): reacting a compound having a crosslinkable functional group separately from the group reacting with the functional group of (a) or (b) in the molecule with the structural unit of (a) or (b). Examples of the structural unit to be obtained (for example, a structural unit that can be synthesized by a technique such as allowing acrylic acid chloride to act on a hydroxyl group).
上記（ｃ）の構成単位は該架橋性官能基が光重合性基であることが好ましい。ここに、光重合性基としては、例えば（メタ）アクリロイル基、アルケニル基、シンナモイル基、シンナミリデンアセチル基、ベンザルアセトフェノン基、スチリルピリジン基、α−フェニルマレイミド基、フェニルアジド基、スルフォニルアジド基、カルボニルアジド基、ジアゾ基、ｏ−キノンジアジド基、フリルアクリロイル基、クマリン基、ピロン基、アントラセン基、ベンゾフェノン基、スチルベン基、ジチオカルバメート基、キサンテート基、１，２，３−チアジアゾール基、シクロプロペン基、アザジオキサビシクロ基などを挙げることができ、これらは１種のみでなく２種以上であってもよい。これらのうち、（メタ）アクリロイル基およびシンナモイル基が好ましく、特に好ましくは（メタ）アクリロイル基である。 In the structural unit (c), the crosslinkable functional group is preferably a photopolymerizable group. Here, examples of the photopolymerizable group include (meth) acryloyl group, alkenyl group, cinnamoyl group, cinnamylideneacetyl group, benzalacetophenone group, styrylpyridine group, α-phenylmaleimide group, phenylazide group, sulfonylazide. Group, carbonyl azide group, diazo group, o-quinonediazide group, furylacryloyl group, coumarin group, pyrone group, anthracene group, benzophenone group, stilbene group, dithiocarbamate group, xanthate group, 1,2,3-thiadiazole group, cyclo A propene group, an azadioxabicyclo group, etc. can be mentioned, These may be not only 1 type but 2 or more types. Of these, a (meth) acryloyl group and a cinnamoyl group are preferable, and a (meth) acryloyl group is particularly preferable.
光重合性基含有共重合体を調製するための具体的な方法としては、下記の方法を挙げることができるが、これらに限定されるものではない。 Specific methods for preparing the photopolymerizable group-containing copolymer include, but are not limited to, the following methods.
ａ．水酸基を含有してなる架橋性官能基含有共重合体に、（メタ）アクリル酸クロリドを反応させてエステル化する方法、
ｂ．水酸基を含有してなる架橋性官能基含有共重合体に、イソシアネート基を含有する（メタ）アクリル酸エステルを反応させてウレタン化する方法、
ｃ．エポキシ基を含有してなる架橋性官能基含有共重合体に、（メタ）アクリル酸を反応させてエステル化する方法、
ｄ．カルボキシル基を含有してなる架橋性官能基含有共重合体に、エポキシ基を含有する含有（メタ）アクリル酸エステルを反応させてエステル化する方法。
上記光重合性基の導入量は任意に調節することができ、塗膜面状安定性・無機粒子共存時の面状故障低下・膜強度向上などの点からカルボキシル基やヒドロキシル基等を一定量残すことも好ましい。
a. A method of esterifying by reacting a (meth) acrylic acid chloride with a crosslinkable functional group-containing copolymer containing a hydroxyl group,
b. A method of urethanization by reacting a (meth) acrylic acid ester containing an isocyanate group with a crosslinkable functional group-containing copolymer containing a hydroxyl group,
c. A method of reacting (meth) acrylic acid with a crosslinkable functional group-containing copolymer containing an epoxy group,
d. A method in which a crosslinkable functional group-containing copolymer containing a carboxyl group is reacted with a containing (meth) acrylic acid ester containing an epoxy group for esterification.
The amount of the photopolymerizable group introduced can be arbitrarily adjusted, and a certain amount of carboxyl groups, hydroxyl groups, etc., from the viewpoints of surface stability of the coating film, reduction of surface failure when coexisting with inorganic particles, and improvement of film strength. It is also preferable to leave.
本発明に有用な共重合体では上記含フッ素ビニルモノマーから導かれる繰返し単位および側鎖に（メタ）アクリロイル基を有する繰返し単位以外に、基材への密着性、ポリマーのＴｇ（皮膜硬度に寄与する）、溶剤への溶解性、透明性、滑り性、防塵・防汚性等種々の観点から適宜他のビニルモノマーを共重合することもできる。これらのビニルモノマーは目的に応じて複数を組み合わせてもよく、合計で共重合体中の０〜６５モル％の範囲で導入されていることが好ましく、０〜４０モル％の範囲であることがより好ましく、０〜３０モル％の範囲であることが特に好ましい。本発明に有用な共重合体では上記含フッ素ビニルモノマーから導かれる繰返し単位および側鎖に（メタ）アクリロイル基を有する繰返し単位以外に、基材への密着性、ポリマーのＴｇ（皮膜硬度に寄与する）、溶剤への溶解性、透明性、滑り性、防塵・防汚性等種々の観点から適宜他のビニルモノマーを共重合することもできる。これらのビニルモノマーは目的に応じて複数を組み合わせてもよく、合計で共重合体中の０〜６５モル％の範囲で導入されていることが好ましく、０〜４０モル％の範囲であることがより好ましく、０〜３０モル％の範囲であることが特に好ましい。 In the copolymer useful for the present invention, in addition to the repeating unit derived from the above-mentioned fluorine-containing vinyl monomer and the repeating unit having a (meth) acryloyl group in the side chain, it contributes to adhesion to the substrate and Tg of the polymer (film hardness). And other vinyl monomers can be copolymerized as appropriate from various viewpoints such as solubility in a solvent, transparency, slipperiness, dust resistance and antifouling properties. A plurality of these vinyl monomers may be combined depending on the purpose, and are preferably introduced in the range of 0 to 65 mol% in the copolymer in total, and in the range of 0 to 40 mol%. More preferably, it is particularly preferably in the range of 0 to 30 mol%. In the copolymer useful for the present invention, in addition to the repeating unit derived from the above-mentioned fluorine-containing vinyl monomer and the repeating unit having a (meth) acryloyl group in the side chain, it contributes to adhesion to the substrate and Tg of the polymer (film hardness). And other vinyl monomers can be copolymerized as appropriate from various viewpoints such as solubility in a solvent, transparency, slipperiness, dust resistance and antifouling properties. A plurality of these vinyl monomers may be combined depending on the purpose, and are preferably introduced in the range of 0 to 65 mol% in the copolymer in total, and in the range of 0 to 40 mol%. More preferably, it is particularly preferably in the range of 0 to 30 mol%.
併用可能なビニルモノマー単位には特に限定はなく、例えばオレフィン類（エチレン、プロピレン、イソプレン、塩化ビニル、塩化ビニリデン等）、アクリル酸エステル類（アクリル酸メチル、アクリル酸メチル、アクリル酸エチル、アクリル酸２−エチルヘキシル、アクリル酸２‐ヒドロキシエチル）、メタクリル酸エステル類（メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸２−ヒドロキシエチル等）、スチレン誘導体（スチレン、ｐ−ヒドロキシメチルスチレン、ｐ−メトキシスチレン等）、ビニルエーテル類（メチルビニルエーテル、エチルビニルエーテル、シクロヘキシルビニルエーテル、ヒドロキシエチルビニルエーテル、ヒドロキシブチルビニルエーテル等）、ビニルエステル類（酢酸ビニル、プロピオン酸ビニル、桂皮酸ビニル等）、不飽和カルボン酸類（アクリル酸、メタクリル酸、クロトン酸、マレイン酸、イタコン酸等）、アクリルアミド類（Ｎ、Ｎ−ジメチルアクリルアミド、Ｎ−ｔｅｒｔ−ブチルアクリルアミド、Ｎ−シクロヘキシルアクリルアミド等）、メタクリルアミド類（Ｎ、Ｎ−ジメチルメタクリルアミド）、アクリロニトリル等を挙げることができる。 The vinyl monomer unit that can be used in combination is not particularly limited. For example, olefins (ethylene, propylene, isoprene, vinyl chloride, vinylidene chloride, etc.), acrylic esters (methyl acrylate, methyl acrylate, ethyl acrylate, acrylic acid) 2-ethylhexyl, 2-hydroxyethyl acrylate), methacrylic acid esters (methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, etc.), styrene derivatives (styrene, p-hydroxymethylstyrene, p -Methoxystyrene, etc.), vinyl ethers (methyl vinyl ether, ethyl vinyl ether, cyclohexyl vinyl ether, hydroxyethyl vinyl ether, hydroxybutyl vinyl ether, etc.), vinyl esters (vinyl acetate) Vinyl propionate, vinyl cinnamate, etc.), unsaturated carboxylic acids (acrylic acid, methacrylic acid, crotonic acid, maleic acid, itaconic acid, etc.), acrylamides (N, N-dimethylacrylamide, N-tert-butylacrylamide, N -Cyclohexyl acrylamide, etc.), methacrylamides (N, N-dimethylmethacrylamide), acrylonitrile and the like.
本発明で特に有用な含フッ素ポリマーは、パーフルオロオレフィンとビニルエーテル類またはビニルエステル類とのランダム共重合体である。特に単独で架橋反応可能な基（（メタ）アクリロイル基等のラジカル反応性基、エポキシ基、オキセタニル基等の開環重合性基等）を有していることが好ましい。 The fluorine-containing polymer particularly useful in the present invention is a random copolymer of perfluoroolefin and vinyl ethers or vinyl esters. In particular, it preferably has a group capable of undergoing a crosslinking reaction alone (a radical reactive group such as a (meth) acryloyl group, a ring-opening polymerizable group such as an epoxy group or an oxetanyl group).
これらの架橋反応性基含有重合単位はポリマーの全重合単位の５〜７０ｍｏｌ％を占めていることが好ましく、特に好ましくは３０〜６０ｍｏｌ％の場合である。 These crosslinkable group-containing polymerized units preferably occupy 5 to 70 mol% of the total polymerized units of the polymer, particularly preferably 30 to 60 mol%.
好ましいポリマーについては、特開２００２−２４３９０７号、特開２００２−３７２６０１号、特開２００３−２６７３２号、特開２００３−２２２７０２号、特開２００３−２９４９１１号、特開２００３−３２９８０４号、特開２００４−４４４４、特開２００４−４５４６２号に記載のものを挙げることができる。 Regarding preferred polymers, JP-A-2002-243907, JP-A-2002-372601, JP-A-2003-26732, JP-A-2003-222702, JP-A-2003-294911, JP-A-2003-329804, JP-A-2004. -4444 and JP, 2004-45462, A can be mentioned.
本発明の含フッ素ポリマーには防汚性を付与する目的で、ポリシロキサン構造が導入されていることが好ましい。ポリシロキサン構造の導入方法に制限はないが例えば特開平６−９３１００号、特開平１１−１８９６２１号、同１１−２２８６３１号、特開２０００−３１３７０９号の各公報に記載のごとく、シリコーンマクロアゾ開始剤を用いてポリシロキサンブロック共重合成分を導入する方法、特開平２−２５１５５５号、同２−３０８８０６号の各公報に記載のごとくシリコーンマクロマーを用いてポリシロキサングラフト共重合成分を導入する方法が好ましい。 For the purpose of imparting antifouling properties, it is preferable that a polysiloxane structure is introduced into the fluoropolymer of the present invention. There is no limitation on the method of introducing the polysiloxane structure, but for example, as described in JP-A-6-93100, JP-A-11-189621, JP-A-11-228631 and JP-A-2000-313709, the initiation of silicone macroazo A method of introducing a polysiloxane block copolymer component using an agent, and a method of introducing a polysiloxane graft copolymer component using a silicone macromer as described in JP-A-2-251555 and JP-A-2-308806. preferable.
特に好ましい化合物としては、特開平１１−１８９６２１号の実施例１、２、及び３のポリマー、又は特開平２−２５１５５５号の共重合体Ａ−２及びＡ−３を挙げることができる。これらのポリシロキサン成分はポリマー中の０．５〜１０質量％であることが好ましく、特に好ましくは１〜５質量％である。 Particularly preferred compounds include the polymers of Examples 1, 2, and 3 of JP-A-11-189621, and the copolymers A-2 and A-3 of JP-A-2-251555. These polysiloxane components are preferably 0.5 to 10% by mass in the polymer, and particularly preferably 1 to 5% by mass.
本発明に好ましく用いることのできるポリマーの好ましい分子量は、質量平均分子量が５０００以上、好ましくは１００００〜５０００００、最も好ましくは１５０００〜２０００００である。平均分子量の異なるポリマーを併用することで塗膜面状の改良や耐傷性の改良を行うこともできる。 The preferred molecular weight of the polymer that can be preferably used in the present invention is a mass average molecular weight of 5,000 or more, preferably 10,000 to 500,000, most preferably 15,000 to 200,000. By using polymers having different average molecular weights in combination, it is possible to improve the surface state of the coating film and the scratch resistance.
また本発明では、塗布面状の改良、防汚性付与の目的で、感光性組成物がさらにフッ素系化合物（フッ素系界面活性剤）やポリシロキサン化合物（シリコーン系界面活性剤）を含有することが好ましい。 In the present invention, the photosensitive composition further contains a fluorine compound (fluorine surfactant) or a polysiloxane compound (silicone surfactant) for the purpose of improving the coating surface condition and imparting antifouling properties. Is preferred.
フッ素系化合物としては、フルオロアルキル基を有する化合物が好ましい。該フルオロアルキル基は炭素数１〜２０であることが好ましく、より好ましくは１〜１０であり、直鎖（例えば−ＣＦ２ＣＦ３，−ＣＨ２（ＣＦ２）４Ｈ，−ＣＨ２（ＣＦ２）８ＣＦ３，−ＣＨ２ＣＨ２（ＣＦ２）４Ｈ等）であっても、分岐構造（例えばＣＨ（ＣＦ３）２，ＣＨ２ＣＦ（ＣＦ３）２，ＣＨ（ＣＨ３）ＣＦ２ＣＦ３，ＣＨ（ＣＨ３）（ＣＦ２）５ＣＦ２Ｈ等）であっても、脂環式構造（好ましくは５員環または６員環、例えばパーフルオロシクロへキシル基、パーフルオロシクロペンチル基またはこれらで置換されたアルキル基等）であっても良く、エーテル結合を有していても良い（例えばＣＨ２ＯＣＨ２ＣＦ２ＣＦ３，ＣＨ２ＣＨ２ＯＣＨ２Ｃ４Ｆ８Ｈ，ＣＨ２ＣＨ２ＯＣＨ２ＣＨ２Ｃ８Ｆ１７，ＣＨ２ＣＨ２ＯＣＦ２ＣＦ２ＯＣＦ２ＣＦ２Ｈ等）。該フルオロアルキル基は同一分子中に複数含まれていてもよい。 As the fluorine compound, a compound having a fluoroalkyl group is preferable. The fluoroalkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and a straight chain (for example, —CF 2 CF 3 , —CH 2 (CF 2 ) 4 H, —CH 2 (CF 2 ) 8 CF 3 , —CH 2 CH 2 (CF 2 ) 4 H, etc.), even branched structures (eg, CH (CF 3 ) 2 , CH 2 CF (CF 3 ) 2 , CH (CH 3 ) CF 2 CF 3 , CH (CH 3 ) (CF 2 ) 5 CF 2 H, etc.), alicyclic structures (preferably 5-membered or 6-membered rings such as perfluorocyclohexyl group, perfluorocyclopentyl, etc. Group or an alkyl group substituted with these, and may have an ether bond (for example, CH 2 OCH 2 CF 2 CF 3 , CH 2 CH 2 OCH 2 C 4 F 8 H, CH 2 CH 2 CH 2 CH 2 C 8 F 17 , CH 2 CH 2 OCF 2 CF 2 OCF 2 CF 2 H , etc.). A plurality of the fluoroalkyl groups may be contained in the same molecule.
フッ素系化合物は、さらに感光性組成物からなる層との結合形成あるいは相溶性に寄与する置換基を有していることが好ましい。該置換基は同一であっても異なっていても良く、複数個あることが好ましい。好ましい置換基の例としてはアクリロイル基、メタクリロイル基、ビニル基、アリール基、シンナモイル基、エポキシ基、オキセタニル基、水酸基、ポリオキシアルキレン基、カルボキシル基、アミノ基などが挙げられる。フッ素化合物はフッ素原子を含まない化合物とのポリマーであってもオリゴマーであってもよく、分子量に特に制限はない。 It is preferable that the fluorine-based compound further has a substituent that contributes to bond formation or compatibility with the layer made of the photosensitive composition. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, epoxy group, oxetanyl group, hydroxyl group, polyoxyalkylene group, carboxyl group, amino group and the like. The fluorine compound may be a polymer or an oligomer with a compound not containing a fluorine atom, and the molecular weight is not particularly limited.
フッ素系化合物のフッ素原子含有量には特に制限は無いが２０質量％以上であることが好ましく、３０〜７０質量％であることが特に好ましく、４０〜７０質量％であることが最も好ましい。好ましいフッ素化合物の例としてはダイキン化学工業（株）製、Ｒ−２０２０、Ｍ−２０２０、Ｒ−３８３３、Ｍ−３８３３（以上商品名）、大日本インキ（株）製、メガファックＦ−１７１、Ｆ−１７２、Ｆ−１７９Ａ、ディフェンサＭＣＦ−３００（以上商品名）などが挙げられるがこれらに限定されるものではない。 Although there is no restriction | limiting in particular in fluorine atom content of a fluorine-type compound, It is preferable that it is 20 mass% or more, It is especially preferable that it is 30-70 mass%, It is most preferable that it is 40-70 mass%. Examples of preferred fluorine compounds include Daikin Chemical Industries, R-2020, M-2020, R-3833, M-3833 (named above), Dainippon Ink, Megafac F-171, Examples include, but are not limited to, F-172, F-179A, and defender MCF-300 (trade name).
ポリシロキサン構造を有する化合物は、化合物の構造は特に制限はなく、ジメチルシリルオキシ単位を繰り返し単位として複数個含む、化合物鎖の末端及び／又は側鎖に置換基を有するものが挙げられる。また、ジメチルシリルオキシを繰り返し単位として含む化合物鎖中にはジメチルシリルオキシ以外の構造単位を含んでもよい。 The compound having a polysiloxane structure is not particularly limited as to the structure of the compound, and examples thereof include those having a substituent at the terminal end and / or side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy.
ポリシロキサン構造を有する化合物の分子量には特に制限はないが、１０万以下であることが好ましく、５万以下であることが特に好ましく、３０００〜３００００であることが最も好ましい。 Although there is no restriction | limiting in particular in the molecular weight of the compound which has a polysiloxane structure, It is preferable that it is 100,000 or less, It is especially preferable that it is 50,000 or less, It is most preferable that it is 3000-30000.
ポリシロキサン構造を有する化合物は、転写を防ぐという観点で、水酸基又は水酸基と反応して結合を形成する官能基を含有することが好ましい。この結合形成反応は、加熱条件下及び／又は触媒存在下で速やかに進行することが好ましい。そのような置換基としては、エポキシ基やカルボキシル基などが挙げられる。好ましい化合物の例としては以下のものが挙げられるが、これらに限定されるものではない。 From the viewpoint of preventing transfer, the compound having a polysiloxane structure preferably contains a hydroxyl group or a functional group that forms a bond by reacting with a hydroxyl group. This bond formation reaction preferably proceeds rapidly under heating conditions and / or in the presence of a catalyst. Examples of such a substituent include an epoxy group and a carboxyl group. Although the following are mentioned as an example of a preferable compound, It is not limited to these.
（水酸基を含むもの）
“Ｘ−２２−１６０ＡＳ”、“ＫＦ−６００１”、“ＫＦ−６００２”、“ＫＦ−６００３”、“Ｘ−２２−１７０ＤＸ”、“Ｘ−２２−１７４ＤＸ”、“Ｘ−２２−１７６ＤＸ”、“Ｘ−２２−１７６Ｄ”、“Ｘ−２２−１７６Ｆ”｛以上、信越化学工業（株）製｝；“ＦＭ−４４１１”、“ＦＭ−４４２１”、“ＦＭ−４４２５”、“ＦＭ−０４１１”、“ＦＭ−０４２１”、“ＦＭ−０４２５”、“ＦＭ−ＤＡ１１”、“ＦＭ−ＤＡ２１”、“ＦＭ−ＤＡ２５”｛以上、チッソ（株）製｝；“ＣＭＳ−６２６”、“ＣＭＳ−２２２”｛以上、Ｇｅｌｅｓｔ社製｝。
(Including hydroxyl group)
“X-22-160AS”, “KF-6001”, “KF-6002”, “KF-6003”, “X-22-170DX”, “X-22-174DX”, “X-22-176DX”, “X-22-176D”, “X-22-176F” {manufactured by Shin-Etsu Chemical Co., Ltd.}; “FM-4411”, “FM-4421”, “FM-4425”, “FM-0411” "FM-0421", "FM-0425", "FM-DA11", "FM-DA21", "FM-DA25" {above, manufactured by Chisso Corporation}; "CMS-626", "CMS-222""{The above, made by Gelest Co.}.
（水酸基と反応する官能基を含むもの）
“Ｘ−２２−１６２Ｃ”、“ＫＦ−１０５”｛以上、信越化学工業（株）製｝；“ＦＭ−５５１１”、“ＦＭ−５５２１”、“ＦＭ−５５２５”、“ＦＭ−６６１１”、“ＦＭ−６６２１”、“ＦＭ−６６２５”｛以上、チッソ（株）製｝。
(Containing functional groups that react with hydroxyl groups)
"X-22-162C", "KF-105" {manufactured by Shin-Etsu Chemical Co., Ltd.}; "FM-5511", "FM-5521", "FM-5525", "FM-6611", " FM-6621 "," FM-6625 "{above, manufactured by Chisso Corporation}.
上記ポリシロキサン系化合物に加えて、更に別のポリシロキサン系化合物を併用することもできる。好ましい例としてはジメチルシリルオキシ単位を繰り返し単位として複数個含む化合物鎖の末端および／または側鎖に置換基を有するものが挙げられる。ジメチルシリルオキシを繰り返し単位として含む化合物鎖中にはジメチルシリルオキシ以外の構造単位を含んでもよい。置換基は同一であっても異なっていても良く、複数個あることが好ましい。好ましい置換基の例としてはアクリロイル基、メタクリロイル基、ビニル基、アリール基、シンナモイル基、オキセタニル基、フルオロアルキル基、ポリオキシアルキレン基、カルボキシル基、アミノ基などを含む基が挙げられる。 In addition to the polysiloxane compound, another polysiloxane compound may be used in combination. Preferable examples include those having a substituent at the terminal and / or side chain of a compound chain containing a plurality of dimethylsilyloxy units as repeating units. The compound chain containing dimethylsilyloxy as a repeating unit may contain a structural unit other than dimethylsilyloxy. The substituents may be the same or different, and a plurality of substituents are preferable. Examples of preferred substituents include groups containing acryloyl group, methacryloyl group, vinyl group, aryl group, cinnamoyl group, oxetanyl group, fluoroalkyl group, polyoxyalkylene group, carboxyl group, amino group and the like.
ポリシロキサン構造を有する化合物の分子量に特に制限はないが、１０万以下であることが好ましく、５万以下であることがより好ましく、３０００〜３００００であることが特に好ましく、１００００〜２００００であることが最も好ましい。 Although there is no restriction | limiting in particular in the molecular weight of the compound which has a polysiloxane structure, It is preferable that it is 100,000 or less, It is more preferable that it is 50,000 or less, It is especially preferable that it is 3000-30000, It is 10,000-20000 Is most preferred.
シリコーン系化合物のシリコン原子含有量には特に制限はないが、１８．０質量％以上であることが好ましく、２５．０〜３７．０質量％であることが特に好ましく、３０．０〜３７．０質量％であることが最も好ましい。 Although there is no restriction | limiting in particular in silicon atom content of a silicone type compound, it is preferable that it is 18.0 mass% or more, it is especially preferable that it is 25.0-37.0 mass%, and 30.0-37. Most preferably, it is 0 mass%.
好ましいシリコーン系化合物の例としては、信越化学（株）製、Ｘ−２２−１７４ＤＸ、Ｘ−２２−２４２６、Ｘ−２２−１６４Ｂ、Ｘ２２−１６４Ｃ、Ｘ−２２−１８２１（以上商品名）やチッソ（株）製、ＦＭ−０７２５、ＦＭ−７７２５、ＦＭ６６２１、ＦＭ−１１２１やＧｅｌｅｓｔ製ＤＭＳ−Ｕ２２、ＲＭＳ−０３３、ＲＭＳ−０８３、ＵＭＳ−１８２、ＤＭＳ−Ｈ２１、ＤＭＳ−Ｈ３１、ＨＭＳ−３０１、ＦＭＳ１２１、ＦＭＳ１２３、ＦＭＳ１３１、ＦＭＳ１４１、ＦＭＳ２２１（以上商品名）などが挙げられるがこれらに限定されるものではない。 Examples of preferable silicone compounds include X-22-174DX, X-22-2426, X-22-164B, X22-164C, X-22-1821 (trade name) and Chisso manufactured by Shin-Etsu Chemical Co., Ltd. Made by Co., Ltd., FM-0725, FM-7725, FM6621, FM-1121, Gelest DMS-U22, RMS-033, RMS-083, UMS-182, DMS-H21, DMS-H31, HMS-301, FMS121 , FMS123, FMS131, FMS141, FMS221 (and above are trade names), but are not limited thereto.
また、本発明では、層の表面形状や硬度を調製する目的で、無機微粒子を含有させることも可能である。無機粒子としては、珪素、ジルコニウム、チタン、アルミニウム、インジウム、亜鉛、錫、アンチモンのうちより選ばれる少なくとも一つ金属の酸化物、具体例としては、ＺｒＯ２、ＴｉＯ２、Ａｌ２Ｏ３、Ｉｎ２Ｏ３、ＺｎＯ、ＳｎＯ２、Ｓｂ２Ｏ３、ＩＴＯ等が挙げられる。その他ＢａＳＯ４、ＣａＣＯ３、タルクおよびカオリンなどが含まれる。 In the present invention, inorganic fine particles can be contained for the purpose of adjusting the surface shape and hardness of the layer. As the inorganic particles, an oxide of at least one metal selected from silicon, zirconium, titanium, aluminum, indium, zinc, tin, and antimony, specific examples include ZrO 2 , TiO 2 , Al 2 O 3 , In 2 O 3 , ZnO, SnO 2 , Sb 2 O 3 , ITO and the like can be mentioned. In addition, BaSO 4 , CaCO 3 , talc and kaolin are included.
本発明に使用する無機粒子の粒径は、分散媒体中でなるべく微細化されていることが好ましく、質量平均径は１〜２００ｎｍである。好ましくは５〜１５０ｎｍであり、さらに好ましくは１０〜１００ｎｍ、特に好ましくは１０〜８０ｎｍである。無機粒子を１００ｎｍ以下に微細化することで透明性を損なわないフィルムを形成できる。無機粒子の粒子径は、光散乱法や電子顕微鏡写真により測定できる。 The particle diameter of the inorganic particles used in the present invention is preferably as fine as possible in the dispersion medium, and the mass average diameter is 1 to 200 nm. Preferably it is 5-150 nm, More preferably, it is 10-100 nm, Most preferably, it is 10-80 nm. A film that does not impair the transparency can be formed by refining the inorganic particles to 100 nm or less. The particle diameter of the inorganic particles can be measured by a light scattering method or an electron micrograph.
無機粒子の比表面積は、１０〜４００ｍ２／ｇであることが好ましく、２０〜２００ｍ２／ｇであることがさらに好ましく、３０〜１５０ｍ２／ｇであることが最も好ましい。 The specific surface area of the inorganic particles is preferably from 10 to 400 m 2 / g, more preferably from 20 to 200 m 2 / g, and most preferably from 30 to 150 m 2 / g.
光学材料において、低屈折率化を図るには、多孔質又は中空構造の微粒子を使用することが特に好ましい。これら粒子の空隙率は、好ましくは１０〜８０％、さらに好ましくは２０〜６０％、最も好ましくは３０〜６０％である。中空微粒子の空隙率を上述の範囲にすることが、低屈折率化と粒子の耐久性維持の観点で好ましい。 In order to reduce the refractive index in the optical material, it is particularly preferable to use fine particles having a porous or hollow structure. The porosity of these particles is preferably 10 to 80%, more preferably 20 to 60%, and most preferably 30 to 60%. It is preferable that the void ratio of the hollow fine particles be in the above range from the viewpoint of lowering the refractive index and maintaining the durability of the particles.
多孔質又は中空粒子がシリカの場合には、微粒子の屈折率は、１．１０〜１．４０が好ましく、更に好ましくは１．１５〜１．３５、最も好ましくは１．１５〜１．３０である。ここでの屈折率は粒子全体として屈折率を表し、シリカ粒子を形成している外殻のシリカのみの屈折率を表すものではない。 When the porous or hollow particles are silica, the refractive index of the fine particles is preferably 1.10 to 1.40, more preferably 1.15 to 1.35, and most preferably 1.15 to 1.30. is there. The refractive index here represents the refractive index of the entire particle, and does not represent the refractive index of only the outer shell silica forming the silica particles.
多孔質又は中空シリカの製造方法は、例えば特開２００１−２３３６１１や特開２００２−７９６１６に記載されている。特にシェルの内部に空洞を有している粒子で、そのシェルの細孔が閉塞されている粒子が特に好ましい。なお、これら中空シリカ粒子の屈折率は特開２００２−７９６１６号公報に記載の方法で算出することができる。 A method for producing porous or hollow silica is described, for example, in JP-A-2001-233611 and JP-A-2002-79616. In particular, particles having cavities inside the shell and having fine pores in the shell are particularly preferred. The refractive index of these hollow silica particles can be calculated by the method described in JP-A No. 2002-79616.
多孔質又は中空シリカの含有量は、２％〜６０％が好ましく、より好ましくは５％〜５０％、更に好ましくは１０％〜５０％である。少なすぎると、低屈折率化の効果や耐擦傷性の改良効果が減る傾向があり、多すぎると、微細な凹凸ができ、黒の締まりなどの外観や積分反射率が悪化する傾向がある。 The content of porous or hollow silica is preferably 2% to 60%, more preferably 5% to 50%, and still more preferably 10% to 50%. If the amount is too small, the effect of lowering the refractive index and the effect of improving the scratch resistance tend to decrease. If the amount is too large, fine irregularities are formed, and the appearance such as black tightening and the integrated reflectance tend to deteriorate.
多孔質又は中空シリカの平均粒径は、感光性組成物からなる層の厚みの３０％以上１５０％以下が好ましく、より好ましくは３５％以上８０％以下、更に好ましくは４０％以上６０％以下である。即ち、層の厚みが１００ｎｍであれば、中空シリカの粒径は３０ｎｍ以上１５０ｎｍ以下が好ましく、より好ましくは３５ｎｍ以上１００ｎｍ以下、更に好ましくは、４０ｎｍ以上６５ｎｍ以下である。 The average particle size of the porous or hollow silica is preferably 30% or more and 150% or less, more preferably 35% or more and 80% or less, and further preferably 40% or more and 60% or less of the thickness of the layer made of the photosensitive composition. is there. That is, when the thickness of the layer is 100 nm, the particle size of the hollow silica is preferably 30 nm to 150 nm, more preferably 35 nm to 100 nm, and still more preferably 40 nm to 65 nm.
本発明においては、空孔含有微粒子はサイズ分布を有していてもよく、その変動係数は好ましくは６０％〜５％、更に好ましくは５０％〜１０％である。また、平均粒子サイズの異なる２種又は３種以上の粒子を混合して用いることもできる。 In the present invention, the pore-containing fine particles may have a size distribution, and the coefficient of variation thereof is preferably 60% to 5%, more preferably 50% to 10%. In addition, two or more kinds of particles having different average particle sizes can be mixed and used.
シリカ微粒子の粒径が小さすぎると、空腔部の割合が減り屈折率の低下が見込めず、大きすぎると感光性組成物からなる層表面に微細な凹凸ができ、黒の締まりといった外観、積分反射率が悪化する。シリカ微粒子は、結晶質でも、アモルファスのいずれでも良く、また単分散粒子が好ましい。形状は、球径が最も好ましいが、不定形であっても問題無い。 If the particle size of the silica fine particles is too small, the ratio of the voids will decrease and the refractive index will not decrease.If it is too large, fine irregularities will be formed on the surface of the photosensitive composition layer, and the appearance and integration of black tightening will occur. Reflectivity deteriorates. The silica fine particles may be either crystalline or amorphous, and monodisperse particles are preferred. The shape is most preferably a spherical diameter, but there is no problem even if the shape is indefinite.
また、中空シリカは粒子平均粒子サイズの異なるものを２種以上併用して用いることができる。ここで、中空シリカの平均粒径は電子顕微鏡写真から求めることができる。
本発明において中空シリカの比表面積は、２０〜３００ｍ２／ｇが好ましく、更に好ましくは３０〜１２０ｍ２／ｇ、最も好ましくは４０〜９０ｍ２／ｇである。表面積は窒素を用いＢＥＴ法で求めることができる。
Further, two or more kinds of hollow silica having different particle average particle sizes can be used in combination. Here, the average particle diameter of the hollow silica can be determined from an electron micrograph.
The specific surface area of the hollow silica in the present invention is preferably from 20 to 300 m 2 / g, more preferably 30~120m 2 / g, most preferably 40~90m 2 / g. The surface area can be determined by the BET method using nitrogen.
本発明において、中空シリカと併用して空腔のないシリカ粒子を用いることができる。空腔のないシリカの好ましい粒子サイズは、３０ｎｍ以上１５０ｎｍ以下、更に好ましくは３５ｎｍ以上１００ｎｍ以下、最も好ましくは４０ｎｍ以上８０ｎｍ以下である。 In the present invention, silica particles having no voids can be used in combination with hollow silica. The preferred particle size of silica without voids is 30 nm to 150 nm, more preferably 35 nm to 100 nm, and most preferably 40 nm to 80 nm.
本発明における感光性組成物は、通常、水、アルコール（例、メタノール、エタノール、イソプロパノール、ブタノール、ベンジルアルコール）、ケトン（例、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）、エステル（例、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、蟻酸メチル、蟻酸エチル、蟻酸プロピル、蟻酸ブチル）、脂肪族炭化水素（例、ヘキサン、シクロヘキサン）、ハロゲン化炭化水素（例、メチレンクロライド、クロロホルム、四塩化炭素）、芳香族炭化水素（例、ベンゼン、トルエン、キシレン）、アミド（例、ジメチルホルムアミド、ジメチルアセトアミド、ｎ−メチルピロリドン）、エーテル（例、ジエチルエーテル、ジオキサン、テトラハイドロフラン）、エーテルアルコール（例、１−メトキシ−２−プロパノール）が含まれる。トルエン、キシレン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノンおよびブタノール等の溶剤に溶解、または分散して、セルロース系フィルム、ポリエステル系フィルム、ポリカーボネート系フィルム、脂環族系炭化水素樹脂フィルム等の透明フィルム上に、あるいは他の層を介して、塗布、乾燥し、溶剤を除去することにより得られる。 The photosensitive composition in the present invention is usually water, alcohol (eg, methanol, ethanol, isopropanol, butanol, benzyl alcohol), ketone (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone), ester (eg, methyl acetate). , Ethyl acetate, propyl acetate, butyl acetate, methyl formate, ethyl formate, propyl formate, butyl formate), aliphatic hydrocarbons (eg, hexane, cyclohexane), halogenated hydrocarbons (eg, methylene chloride, chloroform, carbon tetrachloride) ), Aromatic hydrocarbons (eg, benzene, toluene, xylene), amides (eg, dimethylformamide, dimethylacetamide, n-methylpyrrolidone), ethers (eg, diethyl ether, dioxane, tetrahydrofuran), ether alcohols Lumpur (e.g., 1-methoxy-2-propanol) are included. Dissolve or disperse in a solvent such as toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and butanol, and then on a transparent film such as a cellulose film, a polyester film, a polycarbonate film, or an alicyclic hydrocarbon resin film. Alternatively, it can be obtained by coating and drying through another layer and removing the solvent.
本発明の反射防止用多孔質光学材料の製造方法は、少なくとも光重合性モノマーおよび光重合開始剤を含有する感光性組成物に、光照射処理、または、光照射および加熱処理を行い、直径１０オングストローム〜３００ｎｍの微小空孔を有する反射防止用多孔質光学材料を製造する方法であって、該光重合開始剤が、光照射、または、光照射および加熱により分解して気体を発生する光重合開始剤であり、該光重合開始剤の含有量が該感光性組成物の全固形分の４〜２０質量％であり、かつ光照射前の感光性組成物の下記数式（１）で表されるダイナミック硬度（ＤＨ）が、１０〜１００（ｍＮ/μｍ２）である反射防止用多孔質光学材料の製造方法である。
ＤＨ＝αＰ／Ｄ２ …（１）
Ｐ：荷重（ｇｆ）、Ｄ：押し込み深さ（μｍ）
α：圧子の形による定数（三角錘の場合、α＝３７．８４）
In the method for producing an antireflection porous optical material according to the present invention, a photosensitive composition containing at least a photopolymerizable monomer and a photopolymerization initiator is subjected to a light irradiation treatment or a light irradiation and a heat treatment to obtain a diameter of 10 A method for producing an antireflection porous optical material having micropores of angstroms to 300 nm, wherein the photopolymerization initiator is decomposed by light irradiation or light irradiation and heating to generate gas. It is an initiator, the content of the photopolymerization initiator is 4 to 20% by mass of the total solid content of the photosensitive composition, and is represented by the following mathematical formula (1) of the photosensitive composition before light irradiation. This is a method for producing an antireflection porous optical material having a dynamic hardness (DH) of 10 to 100 (mN / μm 2 ).
DH = αP / D 2 (1)
P: Load (gf), D: Indentation depth (μm)
α: Constant depending on the shape of the indenter (α = 37.84 for triangular pyramid)
上記の感光性組成物に紫外線等の活性光線で露光、または加熱状態で露光を加えることにより、本発明の反射防止用多孔質光学材料層が得られる。活性光線の光量は光重合開始剤を５割以上分解する光量が好ましく、８割以上分解する光量が更に好ましい。光重合開始剤の種類により最適な光量は異なるが、通常、５０ｍJ/cm2以上、更に好ましくは１５０ｍJ/cm2が好ましい。 The antireflection porous optical material layer of the present invention can be obtained by exposing the photosensitive composition to exposure with an actinic ray such as ultraviolet rays or heating. The amount of actinic rays is preferably a light amount that decomposes 50% or more of the photopolymerization initiator, and more preferably a light amount that decomposes 80% or more. Optimum light quantity varies depending upon the kind of the photopolymerization initiator, usually, 50 mJ / cm 2 or more, still more preferably is 150 mJ / cm 2.
以下に本発明を実施例を挙げて説明するが、本発明はこれら実施例に制限されるものではない。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
実施例１〜１２、比較例１〜５ Examples 1-12, Comparative Examples 1-5
（感光性組成物の調整）
表１に示す各成分を混合し、孔径０．２５μｍのポリテトラフルオロエチレン製フィルターでろ過して、感光性組成物を調製した。なお表２中の括弧内は質量部を示す。
(Adjustment of photosensitive composition)
Each component shown in Table 1 was mixed and filtered through a polytetrafluoroethylene filter having a pore size of 0.25 μm to prepare a photosensitive composition. The parentheses in Table 2 indicate parts by mass.
（塗膜の形成）
調製した感光性組成物をバーコーターを用いて、トリアセリルセルロースフィルム上に塗布し、９０℃で乾燥し、塗布膜を得た。実施例１、３、４、６、７、９〜１２、比較例１〜５は窒素雰囲気下で紫外線を照射し、実施例２、５、８は１００℃の窒素雰囲気の中で１５０ｍＪ／ｃｍ２の紫外線を照射することによって、塗膜を重合・硬化させた。硬化前の塗布膜に関しては、ダイナミック硬度と屈折率を測定、硬化後の塗布膜に関しては鉛筆硬度、屈折率、防汚性の評価を行った。その結果を表２に示す。
(Formation of coating film)
The prepared photosensitive composition was apply | coated on the triaceryl cellulose film using the bar coater, and it dried at 90 degreeC, and obtained the coating film. Examples 1, 3, 4, 6, 7, 9 to 12 and Comparative Examples 1 to 5 were irradiated with ultraviolet rays in a nitrogen atmosphere, and Examples 2, 5, and 8 were 150 mJ / cm in a nitrogen atmosphere at 100 ° C. The coating film was polymerized and cured by irradiating the ultraviolet ray 2 . For the coating film before curing, dynamic hardness and refractive index were measured, and for the coating film after curing, pencil hardness, refractive index and antifouling property were evaluated. The results are shown in Table 2.
（評価方法）
・ダイナミック硬度（ＤＨ）
島津ダイナミック超微小硬度計（型式ＤＵＨ−２０１ｓ、（株）島津製作所製）を使用し、測定モード：ＭＯＤＥ５、押し込み深さ１μｍ、押し込み速度０．０１４，Ｎ／ｓの条件で測定し、前述の計算式に従って換算した。
・屈折率の測定
アッベ屈折率計｛（株）アタゴ製｝にて測定した。
・鉛筆硬度
塗膜を２５℃、湿度６０％ＲＨで２時間放置した後、ＪＩＳ Ｋ ５４００に記載の鉛筆硬度評価を実施した。
・防汚性
塗膜の表面に、赤、黄、黒の油性マジックで線を引き、室温で２４時間放置した後、乾いた布で拭き取った時の、マジックに対する防汚性のレベルを確認した。判定は次の基準に従った。
全くつかない：〇
うっすらと色が残る：△
着色が著しい：×
(Evaluation method)
・ Dynamic hardness (DH)
Using a Shimadzu Dynamic Ultra Hardness Tester (model DUH-201s, manufactured by Shimadzu Corporation), measurement was performed under the conditions of MODE: MODE 5, indentation depth 1 μm, indentation speed 0.014, N / s. It converted according to the calculation formula.
-Measurement of refractive index It measured with the Abbe refractometer {made by Atago Co., Ltd.}.
Pencil hardness After the coating film was allowed to stand at 25 ° C. and a humidity of 60% RH for 2 hours, pencil hardness evaluation described in JIS K 5400 was performed.
・ Anti-fouling property The surface of the paint film was drawn with red, yellow, and black oil-based magic, left at room temperature for 24 hours, and then wiped with a dry cloth to confirm the level of anti-fouling property against magic. . The determination was in accordance with the following criteria.
Not at all: 〇 A slight color remains: △
Coloring is remarkable: ×
実施例１〜１２は、露光または露光、加熱により、その前後で層中に気体空孔を内在することにより、屈折率が０．１２〜０．１７低下しているのに対し、気体を発生しない光重合開始剤を使用した比較例３では変化なし、気体を発生する光重合開始剤の添加量が少ない比較例１では０．０２、露光前の感光層の硬さが乏しい比較例４では０．０２と変化が小さいことが明らかになった。また気体を発生する光重合開始剤を多量使用した比較例２や露光前の感光層の硬さが高すぎ比較例５は防汚性の劣化が大きいことが明らかになった。
また実施例１、２、３において、透過型顕微鏡でフィルムの断面を観測した結果、いずれにおいても、最大１０ｎｍ程度の空孔が比較的均一に形成されていることが分かった。
In Examples 1 to 12, gas is generated while the refractive index is reduced by 0.12 to 0.17 due to the presence of gas vacancies in the layer before and after exposure or exposure and heating. In Comparative Example 3 using a non-photopolymerization initiator, there is no change, in Comparative Example 1 in which the amount of photopolymerization initiator that generates gas is small, 0.02 in Comparative Example 4, and in Comparative Example 4 in which the hardness of the photosensitive layer before exposure is low It became clear that the change was as small as 0.02. Further, it was revealed that the antifouling property is greatly deteriorated in Comparative Example 2 in which a large amount of a photopolymerization initiator that generates gas and Comparative Example 5 in which the photosensitive layer before exposure is too high.
In Examples 1, 2, and 3, the cross section of the film was observed with a transmission microscope, and as a result, it was found that in each case, pores having a maximum of about 10 nm were formed relatively uniformly.
Claims (7)
該光重合開始剤が、光照射、または、光照射および加熱により分解して気体を発生する光重合開始剤であり、該光重合開始剤の含有量が前記感光性組成物の全固形分の４〜２０質量％であり、かつ光照射前の感光性組成物の下記数式（１）で表されるダイナミック硬度（ＤＨ）が、１０〜１００（ｍＮ/μｍ２）である反射防止用多孔質光学材料。
ＤＨ＝αＰ／Ｄ２ …（１）
Ｐ：荷重（ｇｆ）、Ｄ：押し込み深さ（μｍ）
α：圧子の形による定数（三角錘の場合、α＝３７．８４） An antireflection porous optical material having micropores having a diameter of 10 angstroms to 300 nm formed using a photosensitive composition containing at least a photopolymerizable monomer and a photopolymerization initiator,
The photopolymerization initiator is a photopolymerization initiator that decomposes by light irradiation or light irradiation and heating to generate gas, and the content of the photopolymerization initiator is the total solid content of the photosensitive composition 4 to 20% by mass and an anti-reflection porous material having a dynamic hardness (DH) represented by the following formula (1) of the photosensitive composition before light irradiation of 10 to 100 (mN / μm 2 ) Optical material.
DH = αP / D 2 (1)
P: Load (gf), D: Indentation depth (μm)
α: Constant depending on the shape of the indenter (α = 37.84 for triangular pyramid)
該光重合開始剤が、光照射、または、光照射および加熱により分解して気体を発生する光重合開始剤であり、該光重合開始剤の含有量が該感光性組成物の全固形分の４〜２０質量％であり、かつ光照射前の感光性組成物の下記数式（１）で表されるダイナミック硬度（ＤＨ）が、１０〜１００（ｍＮ/μｍ２）である反射防止用多孔質光学材料の製造方法。
ＤＨ＝αＰ／Ｄ２ …（１）
Ｐ：荷重（ｇｆ）、Ｄ：押し込み深さ（μｍ）
α：圧子の形による定数（三角錘の場合、α＝３７．８４） Porous optics for antireflection having micropores having a diameter of 10 angstroms to 300 nm by subjecting a photosensitive composition containing at least a photopolymerizable monomer and a photopolymerization initiator to light irradiation treatment or light irradiation and heat treatment. A method of manufacturing a material comprising:
The photopolymerization initiator is a photopolymerization initiator that decomposes by light irradiation or light irradiation and heating to generate gas, and the content of the photopolymerization initiator is the total solid content of the photosensitive composition 4 to 20% by mass and an anti-reflection porous material having a dynamic hardness (DH) represented by the following formula (1) of the photosensitive composition before light irradiation of 10 to 100 (mN / μm 2 ) Manufacturing method of optical material.
DH = αP / D 2 (1)
P: Load (gf), D: Indentation depth (μm)
α: Constant depending on the shape of the indenter (α = 37.84 for triangular pyramid)
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