JP7152841B2 - Coating liquid for forming transparent film and base material with transparent film - Google Patents
Coating liquid for forming transparent film and base material with transparent film Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2502/00—Acrylic polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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Description
本発明は、水に対する接触角が低く、しかも、硬度(鉛筆硬度)及び強度(耐擦傷性)が高い透明被膜を形成できる塗布液、及びこれを用いた透明被膜付基材に関する。 TECHNICAL FIELD The present invention relates to a coating liquid capable of forming a transparent film having a low contact angle with water, high hardness (pencil hardness) and high strength (scratch resistance), and a substrate with a transparent film using the same.
従来、ガラス、プラスチック等で形成されたシートやレンズ等の基材には、その表面の耐擦傷性を向上させるため、基材表面にハードコート膜が設けられている。 2. Description of the Related Art Conventionally, substrates such as sheets and lenses made of glass, plastic, etc. are provided with a hard coat film on the substrate surface in order to improve the scratch resistance of the surface.
ハードコート膜は、最表面で使用されるディスプレイ用途では、防汚性付与のために高接触角タイプが求められる。一方、タブレットやスマートフォンといったタッチパネル用途では、ハードコートの上に更に層を設けたり、接着剤や樹脂を貼り合せたりするため、低接触角タイプが求められる。 For display applications where the hard coat film is used on the outermost surface, a high contact angle type is required in order to impart antifouling properties. On the other hand, for touch panel applications such as tablets and smartphones, a low contact angle type is required because an additional layer is provided on the hard coat or an adhesive or resin is attached.
また、塗布液を乾燥・硬化させる際に、透明被膜が収縮して、基材が引っ張られ、透明被膜付基材がカーリング(湾曲)するという問題がある。例えば、溶媒の多い塗布液の場合には、乾燥時の溶剤揮発(濃縮)によるウェット膜からドライ膜への収縮により、カーリングが起こり易い。また、多官能アクリルモノマー等の硬化収縮率が大きい樹脂を用いる場合には、硬化時の収縮によりカーリングが起こり易い。近年、更に透明性を向上させるため、あるいは透明被膜付基材を使用した表示装置や携帯電話等の軽量化のために薄い基材が使用されており、カーリングの問題がより顕著になっている。 Moreover, when the coating liquid is dried and cured, the transparent coating shrinks, the substrate is pulled, and there is a problem that the substrate with the transparent coating curls (curves). For example, in the case of a coating liquid containing a large amount of solvent, curling is likely to occur due to shrinkage from a wet film to a dry film due to evaporation (concentration) of the solvent during drying. In addition, when a resin such as a polyfunctional acrylic monomer having a large cure shrinkage rate is used, curling is likely to occur due to shrinkage during curing. In recent years, thin substrates have been used to further improve transparency, or to reduce the weight of display devices and mobile phones using substrates with transparent coatings, and the problem of curling has become more pronounced. .
そこで、特許文献1には、基材の少なくとも片面に活性エネルギー線硬化樹脂層を積層してなるハードコートフィルムおよびその製造方法が開示されている。このハードコートフィルムは、硬化樹脂層の表面硬度がH以上でかつ水滴接触角が60°以下である。具体的には、プラスチックフィルムの基材に、不飽和ポリエステル樹脂系、アクリル系、付加重合系、チオール・アクリルのハイブリッド系、カチオン重合系、カチオン重合とラジカル重合のハイブリッド系などの硬化用樹脂組成物を塗布した後に、紫外線等の活性エネルギー線を照射して架橋硬化させて、特定量のフッ素ガスを含有する気体を接触処理して活性エネルギー線硬化樹脂層を形成している。 Therefore, Patent Document 1 discloses a hard coat film obtained by laminating an active energy ray-curable resin layer on at least one side of a substrate, and a method for producing the same. In this hard coat film, the cured resin layer has a surface hardness of H or more and a water droplet contact angle of 60° or less. Specifically, resin compositions for curing such as unsaturated polyester resin, acrylic, addition polymerization, thiol-acrylic hybrid, cationic polymerization, cationic polymerization and radical polymerization hybrid system are applied to plastic film substrates. After the material is applied, it is irradiated with active energy rays such as ultraviolet rays to be cross-linked and cured, and is contacted with a gas containing a specific amount of fluorine gas to form an active energy ray-curable resin layer.
特許文献2には、薄い基材でもカーリングが小さく、基材との密着性、硬度、耐擦傷性、透明性等に優れた透明被膜を形成する塗料が開示されている。具体的には、4以上の官能基を持つ多官能ウレタンアクリレート樹脂と、官能基数が2又は3の低官能アクリレート樹脂と、平均粒子径が5~500nmの範囲にある金属酸化物微粒子と、有機溶媒とを含み、多官能ウレタンアクリレート樹脂の濃度(CA)と低官能アクリレート樹脂の濃度(CB)との濃度比(CB/CA)が0.05~0.5の範囲にある塗料が開示されている。 Patent Literature 2 discloses a paint that forms a transparent film that is less curled even on a thin substrate and has excellent adhesion to the substrate, hardness, scratch resistance, transparency, and the like. Specifically, a polyfunctional urethane acrylate resin having 4 or more functional groups, a low-functional acrylate resin having 2 or 3 functional groups, metal oxide fine particles having an average particle size in the range of 5 to 500 nm, and an organic and a solvent, and the concentration ratio (C B /C A ) between the concentration (C A ) of the polyfunctional urethane acrylate resin and the concentration (C B ) of the low-functional acrylate resin is in the range of 0.05 to 0.5. A paint is disclosed.
しかしながら、特許文献1では、硬化樹脂層が主体のために、ハードコートフィルムの硬度はH~2H程度までしかなく、それ以上の高硬度化は困難であり、低い接触角と高い硬度を両立したハードコート膜が得られない。 However, in Patent Document 1, since the cured resin layer is the main component, the hardness of the hard coat film is only about H to 2H, and it is difficult to increase the hardness beyond that. A hard coat film cannot be obtained.
次に、特許文献2では、多官能ウレタンアクリレート樹脂が疎水性であるため、透明被膜表面も疎水性となり、水に対する接触角が高くなる。また、高硬度化を図るために、透明被膜中の表面処理金属酸化物微粒子の含有量を増加させると、得られる透明被膜が白化したり、カーリングしたりする。これは、多官能ウレタンアクリレート樹脂が疎水性であるのに対して、表面処理金属酸化物微粒子が親水性なので充分な相溶性が得られないためと考えられる。更に、多官能ウレタンアクリレート樹脂は、特殊な化合物なので高価であり、耐候性、耐光性も低い。 Next, in Patent Document 2, since the polyfunctional urethane acrylate resin is hydrophobic, the surface of the transparent film is also hydrophobic, and the contact angle with water increases. In addition, when the content of the surface-treated metal oxide fine particles in the transparent coating is increased in order to increase the hardness, the resulting transparent coating is whitened or curled. This is probably because the polyfunctional urethane acrylate resin is hydrophobic, whereas the surface-treated metal oxide fine particles are hydrophilic, so sufficient compatibility cannot be obtained. Furthermore, the polyfunctional urethane acrylate resin is a special compound, so it is expensive and has low weather resistance and light resistance.
本発明は、水に対する接触角が低くてかつ硬度が高く、しかも、薄い基材でもカーリングが抑制されるハードコート透明被膜を得られる塗布液(透明被膜形成用の塗布液)及びこれを用いた透明被膜付基材を提供することを目的とする。 The present invention provides a coating liquid (coating liquid for forming a transparent film) that can obtain a hard-coated transparent film that has a low contact angle with water, high hardness, and suppresses curling even on a thin substrate, and a coating solution that uses the same. An object of the present invention is to provide a base material with a transparent film.
本発明に係る透明被膜用の塗布液は、アルキレンオキサイド変性(メタ)アクリレート樹脂と、金属酸化物粒子の表面に有機珪素化合物を設けた表面処理金属酸化物粒子と、有機溶媒とを含む塗布液である。このアルキレンオキサイド変性(メタ)アクリレート樹脂は、(メタ)アクリレート官能基数が3~10、アルキレンオキサイド基数が3~40の多官能(メタ)アクリレートモノマー樹脂である。この表面処理金属酸化物粒子は、有機珪素化合物が金属酸化物粒子100質量部に対し、Rn-SiO(4-n)/2として0.1~50質量部設けられている。その平均粒子径は、5~500nmである。この表面処理金属酸化物粒子は、塗布液中にアルキレンオキサイド変性(メタ)アクリレート樹脂と表面処理金属酸化物粒子の固形分の合計量に対して30~90質量%含まれる。
また、アルキレンオキサイド変性(メタ)アクリレート樹脂が、エチレンオキサイド変性(メタ)アクリレート樹脂であることが好ましい。
A coating liquid for a transparent film according to the present invention comprises an alkylene oxide-modified (meth)acrylate resin, surface-treated metal oxide particles having an organosilicon compound on the surface of the metal oxide particles, and an organic solvent. is. This alkylene oxide-modified (meth)acrylate resin is a polyfunctional (meth)acrylate monomer resin having 3 to 10 (meth)acrylate functional groups and 3 to 40 alkylene oxide groups. The surface-treated metal oxide particles are provided with an organosilicon compound of 0.1 to 50 parts by mass as R n —SiO 2 (4-n)/2 with respect to 100 parts by mass of the metal oxide particles. Its average particle size is 5 to 500 nm. The surface-treated metal oxide particles are contained in the coating liquid in an amount of 30 to 90% by mass based on the total solid content of the alkylene oxide-modified (meth)acrylate resin and the surface-treated metal oxide particles.
Also, the alkylene oxide-modified (meth)acrylate resin is preferably an ethylene oxide-modified (meth)acrylate resin.
本発明に係る透明被膜付基材では、透明被膜が、アルキレンオキサイド変性(メタ)アクリレート樹脂と、金属酸化物粒子の表面に有機珪素化合物を設けた表面処理金属酸化物粒子とを含んでいる。表面処理金属酸化物粒子の平均粒子径は、5~500nmである。この表面処理金属酸化物粒子は、透明被膜中にアルキレンオキサイド変性(メタ)アクリレート樹脂と表面処理金属酸化物粒子の固形分の合計量に対して30~90質量%含まれる。ここで、透明被膜は水に対する接触角が70°未満、鉛筆硬度が3H以上であることが好ましい。
また、透明被膜の接触角が前記表面処理酸化物粒子を含まない透明被膜の接触角よりも低いことが好ましい。
In the substrate with a transparent film according to the present invention, the transparent film contains an alkylene oxide-modified (meth)acrylate resin and surface-treated metal oxide particles having an organosilicon compound on the surface of the metal oxide particles. The average particle size of the surface-treated metal oxide particles is 5-500 nm. The surface-treated metal oxide particles are contained in the transparent coating in an amount of 30 to 90% by mass based on the total solid content of the alkylene oxide-modified (meth)acrylate resin and the surface-treated metal oxide particles. Here, the transparent film preferably has a contact angle with water of less than 70° and a pencil hardness of 3H or more.
Further, the contact angle of the transparent film is preferably lower than that of the transparent film not containing the surface-treated oxide particles.
本発明においては、塗布液に含まれる極性の高いアルキレンオキサイド基を含むアルキレンオキサイド変性(メタ)アクリレート樹脂は、表面処理金属酸化物粒子との相溶性が良いため、表面処理金属酸化物粒子がアルキレンオキサイド変性(メタ)アクリレート樹脂に十分に分散され、接触角が低く、20~70μmの薄い基材でも、硬度及び強度が高く、カーリングの小さい透明被膜付基材が得られる。 In the present invention, since the alkylene oxide-modified (meth)acrylate resin containing a highly polar alkylene oxide group contained in the coating liquid has good compatibility with the surface-treated metal oxide particles, the surface-treated metal oxide particles are alkylene oxide groups. It is sufficiently dispersed in an oxide-modified (meth)acrylate resin, has a low contact angle, and even a thin substrate of 20 to 70 μm provides a transparent coated substrate with high hardness and strength and little curling.
《透明被膜形成用の塗布液》
本発明の塗布液は、アルキレンオキサイド変性(メタ)アクリレート樹脂と、金属酸化物粒子の表面に有機珪素化合物が設けられた平均粒子径が5~500nmの表面処理金属酸化物粒子と、有機溶媒とを含む。この塗布液は、更に重合開始剤等の添加剤を含んでもよい。
具体的には、このアルキレンオキサイド変性(メタ)アクリレート樹脂は、(メタ)アクリレート官能基数が3~10、アルキレンオキサイド基数が3~40の多官能(メタ)アクリレートモノマー樹脂である。表面処理金属酸化物粒子は、有機珪素化合物が、金属酸化物粒子表面に、金属酸化物粒子100質量部に対し、Rn-SiO(4-n)/2として0.1~50質量部設けられた表面処理金属酸化物粒子である。この表面処理金属酸化物粒子は、平均粒子径が5~500nmであり、塗布液中にアルキレンオキサイド変性(メタ)アクリレート樹脂と表面処理金属酸化物粒子の固形分の合計量に対して30~90質量%含まれる。
<<Coating liquid for forming transparent film>>
The coating liquid of the present invention comprises an alkylene oxide-modified (meth)acrylate resin, surface-treated metal oxide particles having an average particle size of 5 to 500 nm in which an organosilicon compound is provided on the surface of the metal oxide particles, and an organic solvent. including. This coating liquid may further contain an additive such as a polymerization initiator.
Specifically, this alkylene oxide-modified (meth)acrylate resin is a polyfunctional (meth)acrylate monomer resin having 3 to 10 (meth)acrylate functional groups and 3 to 40 alkylene oxide groups. In the surface-treated metal oxide particles, an organosilicon compound is provided on the surface of the metal oxide particles in an amount of 0.1 to 50 parts by mass as R n —SiO (4-n)/2 with respect to 100 parts by mass of the metal oxide particles. surface-treated metal oxide particles. The surface-treated metal oxide particles have an average particle diameter of 5 to 500 nm, and the total solid content of the alkylene oxide-modified (meth)acrylate resin and the surface-treated metal oxide particles in the coating liquid is 30 to 90 nm. % by mass.
一般的にハードコート性が良い樹脂としては、多官能(メタ)アクリレートモノマー樹脂や多官能(メタ)ウレタンアクリレートオリゴマー樹脂が使用されることが多い。多官能(メタ)アクリレートモノマー樹脂は、比較的低接触角のものもあるが、一般的にカーリングを起こし易い。また、多官能(メタ)ウレタンアクリレートオリゴマー樹脂は、一般的にカーリングは低いが接触角は高い。一方、多官能アルキレンオキサイド変性(メタ)アクリレート樹脂は、アルキレンオキサイド基と(メタ)アクリレート官能基の比を最適化することで、硬度は低いものの、比較的低接触角で低カーリングを発現し易い。後述のように、アルキレンオキサイド変性(メタ)アクリレート樹脂のアクリレート官能基やアルキレンオキサイド基の数、表面処理金属酸化物粒子の有機珪素化合物による表面処理量、表面処理金属酸化物粒子の平均粒子径、および塗布液中の表面処理有機珪素化合物の量を最適な条件で組み合わせることで、高硬度、低接触角、低カーリング性のすべてを実現したハードコート塗料が得られる。 Generally, polyfunctional (meth)acrylate monomer resins and polyfunctional (meth)urethane acrylate oligomer resins are often used as resins having good hard coat properties. Some polyfunctional (meth)acrylate monomer resins have relatively low contact angles, but they generally tend to curl. Polyfunctional (meth)urethane acrylate oligomer resins generally have low curling but high contact angles. On the other hand, by optimizing the ratio of alkylene oxide groups and (meth)acrylate functional groups, polyfunctional alkylene oxide-modified (meth)acrylate resins have low hardness, but tend to exhibit relatively low contact angles and low curling. . As described below, the number of acrylate functional groups and alkylene oxide groups in the alkylene oxide-modified (meth)acrylate resin, the amount of surface treatment of the surface-treated metal oxide particles with the organosilicon compound, the average particle diameter of the surface-treated metal oxide particles, and the amount of the surface-treated organosilicon compound in the coating solution are combined under optimum conditions to obtain a hard coat paint that achieves all of high hardness, low contact angle, and low curling properties.
塗布液に含まれる主要な成分について以下に詳細に説明する。
《アルキレンオキサイド変性(メタ)アクリレート樹脂》
アルキレンオキサイド変性(メタ)アクリレート樹脂は、アルキレンオキサイド基と(メタ)アクリレート官能基((メタ)アクリロイル基)の比を最適化することで、比較的低接触角で低カーリングを発現し易い。アクリレート官能基数が3よりも小さい場合は、結合部位が少なくなるため、緻密で硬度の高い膜が得られにくい。逆に、アクリレート官能基数が10よりも大きい場合は、単位体積/単位容積/単位ユニットに対する結合基が相対的に多くなるため、膜の収縮が強く、カーリングを起こす場合がある。
また、アルキレンオキサイド基は、極性が高い官能基であり、得られた被膜表面が親水性であるために被膜の水接触角は低くなる。アルキレンオキサイド基が3よりも小さい場合は、被膜表面の親水性化が不充分で、水接触角が充分に低くならない。逆に、アルキレンオキサイド基が40よりも大きい場合は、単位体積/単位容積/単位ユニットに対する結合基が相対的に少なくなるために、膜の緻密化が充分とならない場合があるため、所望する鉛筆硬度が得られない可能性がある。
Main components contained in the coating liquid are described in detail below.
《Alkylene oxide-modified (meth)acrylate resin》
By optimizing the ratio of the alkylene oxide group and the (meth)acrylate functional group ((meth)acryloyl group), the alkylene oxide-modified (meth)acrylate resin tends to develop low curling at a relatively low contact angle. If the number of acrylate functional groups is less than 3, the number of bonding sites is reduced, making it difficult to obtain a dense and highly rigid film. Conversely, when the number of acrylate functional groups is more than 10, the number of binding groups per unit volume/unit volume/unit unit is relatively large, so that the film shrinks strongly and curling may occur.
In addition, the alkylene oxide group is a highly polar functional group, and the resulting film surface is hydrophilic, so that the water contact angle of the film is low. If the number of alkylene oxide groups is less than 3, hydrophilization of the film surface is insufficient and the water contact angle is not sufficiently low. Conversely, when the number of alkylene oxide groups is greater than 40, the number of bonding groups per unit volume/unit volume/unit unit becomes relatively small, and the film may not be sufficiently densified. Hardness may not be obtained.
このアルキレンオキサイド(AO)基としては、エチレンオキサイド(EO)基、プロピレンオキサイド(PO)基、ブチレンオキサイド基が好ましい。特に、単位基内の酸素原子の割合が高く極性が高いエチレンオキサイド基が好ましい。
(メタ)アクリレート官能基数が3以上のアルキレンオキサイド変性(メタ)アクリレート樹脂は、比較的収縮が大きいため、必要に応じて、(メタ)アクリレート官能基数が2以下、好ましくは1の低官能(メタ)アクリレートモノマー樹脂を配合して膜全体の収縮を制御することで、基材との密着性がより向上すると共に、収縮がより抑制され、残留応力を緩和することができる。
アルキレンオキサイド変性(メタ)アクリレート樹脂と表面処理金属酸化物粒子との相溶性を更に向上させる場合には、低官能(メタ)アクリレートモノマー樹脂を配合することが好ましい。低官能(メタ)アクリレートモノマー樹脂を配合することで、造膜中の急激な収縮を抑制でき、膜中の粒子が収縮サイトから排除されることを防止し、結果的に表面処理金属酸化物粒子の膜内への分散性、相溶性が向上する。また、塗料の粘度を下げ易い点でも有効である。ただし、低官能(メタ)アクリレートモノマー樹脂の高配合は硬度低下に繋がるため含有量はできる限り少ない方が好ましく、カーリング特性、密着性、硬度のバランスをみて配合することが好ましい。
The alkylene oxide (AO) group is preferably an ethylene oxide (EO) group, a propylene oxide (PO) group, or a butylene oxide group. In particular, an ethylene oxide group having a high proportion of oxygen atoms in the unit group and high polarity is preferred.
Alkylene oxide-modified (meth)acrylate resins having 3 or more (meth)acrylate functional groups have relatively large shrinkage. ) By blending the acrylate monomer resin and controlling the shrinkage of the entire film, the adhesiveness to the substrate is further improved, the shrinkage is further suppressed, and the residual stress can be alleviated.
In order to further improve the compatibility between the alkylene oxide-modified (meth)acrylate resin and the surface-treated metal oxide particles, it is preferable to blend a low-functional (meth)acrylate monomer resin. By blending a low-functional (meth)acrylate monomer resin, rapid shrinkage during film formation can be suppressed, preventing particles in the film from being expelled from the shrinkage site, and as a result, surface-treated metal oxide particles improves dispersibility and compatibility in the film. It is also effective in that the viscosity of the paint can be easily lowered. However, since a high blending of the low-functional (meth)acrylate monomer resin leads to a decrease in hardness, the content is preferably as small as possible, and it is preferable to blend the resin in consideration of the balance of curling properties, adhesion and hardness.
本発明のアルキレンオキサイド変性(メタ)アクリレート樹脂としては、エチレンオキサイド変性(メタ)アクリレート樹脂、プロピレンオキサイド変性(メタ)アクリレート樹脂およびブチレンオキサイド変性(メタ)アクリレート樹脂が好適である。
エチレンオキサイド変性(メタ)アクリレート樹脂としては、エトキシ化グリセリントリ(メタ)アクリレート、エトキシ化ペンタエリスリトールトリ(メタ)アクリレート、エトキシ化ペンタエリスリトールテトラ(メタ)アクリレート、エトキシ化ジトリメチロールプロパンテトラ(メタ)アクリレート、エトキシ化ジペンタエリスリトールペンタ(メタ)アクリレート、エトキシ化ジペンタエリスリトールヘキサ(メタ)アクリレートを例示できる。これらは、エチレンオキサイド基を各々3~40個もっている。
プロピレンオキサイド変性(メタ)アクリレート樹脂としては、プロポキシ化グリセリントリ(メタ)アクリレート、プロポキシ化ペンタエリスリトールトリ(メタ)アクリレート、プロポキシ化ペンタエリスリトールテトラ(メタ)アクリレート、プロポキシ化ジトリメチロールプロパンテトラ(メタ)アクリレート、プロポキシ化ジペンタエリスリトールペンタ(メタ)アクリレート、プロポキシ化ジペンタエリスリトールヘキサ(メタ)アクリレートを例示できる。これらは、プロピレンオキサイド基を各々3~40個もっている。
ブチレンオキサイド変性(メタ)アクリレート樹脂としては、ブトキシ化グリセリントリ(メタ)アクリレート、ブトキシ化ペンタエリスリトールトリ(メタ)アクリレート、ブトキシ化ペンタエリスリトールテトラ(メタ)アクリレート、ブトキシ化ジトリメチロールプロパンテトラ(メタ)アクリレート、ブトキシ化ジペンタエリスリトールペンタ(メタ)アクリレート、ブトキシ化ジペンタエリスリトールヘキサ(メタ)アクリレートを例示できる。これらは、ブチレンオキサイド基を各々3~40個もっている。
これらの樹脂は単独で使用してもよく、また2種以上を混合して使用してもよい。
As the alkylene oxide-modified (meth)acrylate resin of the present invention, ethylene oxide-modified (meth)acrylate resin, propylene oxide-modified (meth)acrylate resin and butylene oxide-modified (meth)acrylate resin are suitable.
Ethylene oxide-modified (meth)acrylate resins include ethoxylated glycerol tri(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, and ethoxylated ditrimethylolpropane tetra(meth)acrylate. , ethoxylated dipentaerythritol penta(meth)acrylate, and ethoxylated dipentaerythritol hexa(meth)acrylate. They each have 3 to 40 ethylene oxide groups.
Propylene oxide-modified (meth)acrylate resins include propoxylated glycerol tri(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, and propoxylated ditrimethylolpropane tetra(meth)acrylate. , propoxylated dipentaerythritol penta(meth)acrylate, and propoxylated dipentaerythritol hexa(meth)acrylate. They each have 3 to 40 propylene oxide groups.
Butylene oxide-modified (meth)acrylate resins include butoxylated glycerin tri(meth)acrylate, butoxylated pentaerythritol tri(meth)acrylate, butoxylated pentaerythritol tetra(meth)acrylate, butoxylated ditrimethylolpropane tetra(meth)acrylate. , butoxylated dipentaerythritol penta(meth)acrylate, and butoxylated dipentaerythritol hexa(meth)acrylate. They each have 3 to 40 butylene oxide groups.
These resins may be used alone or in combination of two or more.
《表面処理金属酸化物粒子》
表面処理金属酸化物粒子は、従来公知の金属酸化物粒子を従来公知の有機珪素化合物で表面処理して得られる。金属酸化物粒子としては、例えば、シリカ、アルミナ、チタニア、シリカ-アルミナ、シリカ-ジルコニア等の他、酸化錫、SbまたはPがドープされた酸化錫、酸化インジウム、SnまたはFがドーピングされた酸化インジウム、酸化アンチモン、酸化チタン等の導電性粒子も好適に用いることができる。
《Surface-treated metal oxide particles》
The surface-treated metal oxide particles are obtained by surface-treating conventionally known metal oxide particles with a conventionally known organosilicon compound. Examples of metal oxide particles include silica, alumina, titania, silica-alumina, silica-zirconia, tin oxide, Sb- or P-doped tin oxide, indium oxide, Sn- or F-doped oxide. Conductive particles such as indium, antimony oxide, and titanium oxide can also be suitably used.
〈平均粒子径〉
表面処理金属酸化物粒子の平均粒子径は、5~500nmの範囲である。平均粒子径が5nm未満のものは得ることが困難であり、得られたとしても表面処理剤での表面処理、及びゾルの安定性が不十分となることが多い。また、平均粒子径が500nmを超える場合、表面処理金属酸化物粒子の含有量にもよるが、膜表面で光散乱を生じたり、透明被膜のヘーズが悪化して、透明性が低下する。表面処理金属酸化物粒子の平均粒子径は、10~200nmの範囲がさらに好ましい。
<Average particle size>
The average particle size of the surface-treated metal oxide particles is in the range of 5-500 nm. It is difficult to obtain particles having an average particle size of less than 5 nm, and even if they are obtained, the surface treatment with a surface treatment agent and the stability of the sol are often insufficient. On the other hand, if the average particle size exceeds 500 nm, depending on the content of the surface-treated metal oxide particles, light scattering occurs on the film surface, haze of the transparent film deteriorates, and transparency decreases. The average particle size of the surface-treated metal oxide particles is more preferably in the range of 10-200 nm.
〈表面処理:表面処理剤、表面処理量〉
金属酸化物粒子を下記式(1)で表される有機珪素化合物で表面処理することが好ましい。
Rn-SiX4-n・・・(1)
但し、式中、Rは炭素数1~10の非置換または置換炭化水素基で、互いに同一であっても異なっていてもよい。置換基としては、エポキシ基、アルコキシ基、(メタ)アクリロイロキシ基、メルカプト基、ハロゲン原子、アミノ基、フェニルアミノ基が挙げられる。Xは炭素数1~4のアルコキシ基、水酸基、ハロゲン原子、水素原子であり、nは1~3の整数を示す。
表面処理金属酸化物粒子は、固形分として、有機珪素化合物が金属酸化物粒子100質量部に対し、Rn-SiO(4-n)/2として0.1~50質量部の範囲にあれば相溶性が向上する。ここで、有機珪素化合物量が0.1質量部よりも少ないと、表面処理金属酸化物粒子の分散性が不充分となり、得られる透明被膜にヘーズが発生するおそれがある。得られる接触角については低下するが、バインダー((メタ)アクリレートモノマー樹脂)との結合力が弱くなるので、基材との密着性や硬度が不充分となることがある。逆に、表面処理量が50質量部より多くても、分散性がさらに向上する訳ではなく、表面処理金属酸化物粒子の高密度充填が阻害されるおそれがある。接触角は高くなるが、バインダーと結合するサイトが増えるので、収縮が大きくなり、カーリングしたり、密着性が不充分となるおそれがある。さらに、未反応(微粒子と結合しない)の表面処理剤(有機珪素化合物)同士が結合すると収縮が大きくなるため、未反応の表面処理剤を少なくすることが好ましい。
<Surface treatment: surface treatment agent, amount of surface treatment>
It is preferable to surface-treat the metal oxide particles with an organosilicon compound represented by the following formula (1).
R n —SiX 4-n (1)
However, in the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, which may be the same or different. Substituents include epoxy groups, alkoxy groups, (meth)acryloyloxy groups, mercapto groups, halogen atoms, amino groups, and phenylamino groups. X is an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, a halogen atom or a hydrogen atom; n is an integer of 1 to 3;
The surface-treated metal oxide particles have a solid content in the range of 0.1 to 50 parts by mass as R n —SiO (4−n)/2 with respect to 100 parts by mass of the metal oxide particles. Compatibility is improved. Here, if the amount of the organosilicon compound is less than 0.1 parts by mass, the dispersibility of the surface-treated metal oxide particles becomes insufficient, and haze may occur in the resulting transparent coating. Although the obtained contact angle is lowered, the bonding strength with the binder ((meth)acrylate monomer resin) is weakened, so that the adhesiveness and hardness to the substrate may be insufficient. Conversely, even if the surface treatment amount is more than 50 parts by mass, the dispersibility is not further improved, and there is a possibility that the high-density packing of the surface-treated metal oxide particles may be hindered. Although the contact angle is increased, the number of sites that bond with the binder is increased, resulting in increased shrinkage, curling, and insufficient adhesion. Furthermore, when unreacted surface treatment agents (organosilicon compounds) that do not bond with fine particles are bound together, shrinkage increases, so it is preferable to reduce the amount of unreacted surface treatment agents.
《有機溶媒》
有機溶媒としては、アルキレンオキサイド変性(メタ)アクリレート樹脂、重合開始剤等の添加物を溶解あるいは分散できるとともに、表面処理金属酸化物粒子を均一に分散できるものが用いられる。
有機溶媒としては、親水性溶媒や極性溶媒が好ましい。親水性溶媒としては、アルコール類、エステル類、グリコール類、エーテル類等が使用でき、極性溶媒としては、エステル類、ケトン類等が使用できる。
有機溶媒は、具体的には、アルコール類としては、メタノール、エタノール、プロパノール、2-プロパノール、ブタノール、ジアセトンアルコール、フルフリルアルコール、テトラヒドロフルフリルアルコール等があり、エステル類としては、酢酸メチル、酢酸エチル、酢酸イソプロピル、酢酸プロピル、酢酸イソブチル、酢酸ブチル、酢酸イソペンチル、酢酸ペンチル、酢酸3-メトキシブチル、酢酸2-エチルブチル、酢酸シクロヘキシル、エチレングリコールモノアセテート等があり、グリコール類としては、エチレングリコール、ヘキシレングリコール等があり、エーテル類としては、ジエチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールイソプルピルエーテル、ジエチ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エチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル等があり、ケトン類としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、ブチルメチルケトン、シクロヘキサノン、メチルシクロヘキサノン、ジプロピルケトン、メチルペンチルケトン、ジイソブチルケトン等があり、極性溶媒としては他に、炭酸ジメチル、トルエン等がある。これらは単独で使用してもよく、また2種以上を混合して使用してもよい。
特に、プロピ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エチルエーテル、ジアセトンアルコールは、膜の造膜性制御に有効で、塗膜の外観(スジ、ムラ、透明性)制御の点から好ましい。また、トリアセチルセルロース基材(TAC基材)を使用する場合は、酢酸エチル、アセトン、メチルエチルケトン、シクロヘキサノン、炭酸ジメチル等を配合すると、基材を溶解するため、基材との密着性向上及び干渉縞減少の点から好ましい。
また、有機溶媒の沸点は50~200℃の範囲にあることが好ましい。有機溶媒の沸点が50℃より低いものは、塗膜の乾燥が早いため、急激な造膜が起こり、粒子成分等のパッキングが不十分な場合は、膜の緻密化が不充分になり易く、また、膜厚が不均一になり易い。そのため、得られる透明被膜の硬度が不充分となることがある。有機溶媒の沸点が200℃より高いものは、有機溶媒が残存する場合があり、残存溶媒を含んだまま硬化させるとボイドが発生して、得られる透明被膜の硬度が不充分となることがある。この有機溶媒の沸点は、55~180℃の範囲にあることが更に好ましい。
《Organic solvent》
As the organic solvent, one capable of dissolving or dispersing additives such as the alkylene oxide-modified (meth)acrylate resin and the polymerization initiator and capable of uniformly dispersing the surface-treated metal oxide particles is used.
As the organic solvent, a hydrophilic solvent or a polar solvent is preferable. Alcohols, esters, glycols, ethers and the like can be used as hydrophilic solvents, and esters, ketones and the like can be used as polar solvents.
Specific examples of organic solvents include alcohols such as methanol, ethanol, propanol, 2-propanol, butanol, diacetone alcohol, furfuryl alcohol, and tetrahydrofurfuryl alcohol, and esters such as methyl acetate, Ethyl acetate, isopropyl acetate, propyl acetate, isobutyl acetate, butyl acetate, isopentyl acetate, pentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, cyclohexyl acetate, ethylene glycol monoacetate, etc. Glycols include ethylene glycol. , Hexylene glycol, etc. Ethers include diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol. There are monomethyl ether, propylene glycol monoethyl ether, etc. Ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methylpentyl ketone, diisobutyl ketone, etc. Polar solvents Other examples include dimethyl carbonate and toluene. These may be used alone or in combination of two or more.
In particular, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and diacetone alcohol are effective in controlling the film-forming property of the film, and are preferable from the viewpoint of controlling the appearance (streaks, unevenness, transparency) of the coating film. In addition, when using a triacetyl cellulose base material (TAC base material), if ethyl acetate, acetone, methyl ethyl ketone, cyclohexanone, dimethyl carbonate, etc. are blended, the base material will dissolve, improving adhesion and interference with the base material. This is preferable in terms of reduction of streaks.
Also, the boiling point of the organic solvent is preferably in the range of 50 to 200°C. When the boiling point of the organic solvent is lower than 50° C., the coating film dries quickly, resulting in rapid film formation. In addition, the film thickness tends to be uneven. Therefore, the hardness of the obtained transparent film may be insufficient. If the boiling point of the organic solvent is higher than 200° C., the organic solvent may remain, and voids may be generated when the resin is cured while containing the residual solvent, resulting in insufficient hardness of the resulting transparent film. . The boiling point of this organic solvent is more preferably in the range of 55 to 180°C.
《その他の成分》
塗布液には、必要に応じて光重合開始剤を添加してもよい。重合開始剤としては、公知のものを特に制限なく使用することが可能であり、例えば、ビス(2,4,6-トリメチルベンゾイル)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サイド、2-ヒドロキシ-メチル-2-メチル-フェニル-プロパン-1-ケトン、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、1-ヒドロキシ-シクロヘキシル-フェニル-ケトン、2-メチル-1-[4-(メチルチオ)フェニル]-2-モルフォリノプロパン-1-オン等がある。重合開始剤の使用量としては、有機樹脂の固形分濃度の2~20質量%が好ましく、4~16質量%にあることが更に好ましい。
ところで、従来公知の添加剤であるレベリング剤や界面活性剤は、被膜を形成する際に、金属酸化物粒子よりも更に表面に偏在する傾向がある。このため、その使用量が過剰に多いと、望むべく水接触角が得られない場合や、添加剤が膜表面に析出してブリードアウトの問題が起こる場合がある。このため、これら添加剤を使用する場合は、透明被膜付基材の性能に影響を及ぼさない範囲で使用することが好ましい。
《Other Ingredients》
A photopolymerization initiator may be added to the coating liquid, if necessary. As the polymerization initiator, known ones can be used without particular limitation. 4,4-trimethyl-pentylphosphine oxide, 2-hydroxy-methyl-2-methyl-phenyl-propane-1-ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy- cyclohexyl-phenyl-ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and the like. The amount of the polymerization initiator to be used is preferably 2 to 20 mass %, more preferably 4 to 16 mass % of the solid content concentration of the organic resin.
By the way, leveling agents and surfactants, which are conventionally known additives, tend to be more unevenly distributed on the surface than metal oxide particles when forming a coating. Therefore, if the amount used is excessively large, the desired contact angle with water may not be obtained, or the additive may precipitate on the surface of the film, causing the problem of bleeding out. Therefore, when using these additives, it is preferable to use them within a range that does not affect the performance of the base material with a transparent film.
《透明被膜形成用の塗布液の濃度》
塗布液の固形分濃度(アルキレンオキサイド変性(メタ)アクリレート樹脂の固形分と表面処理金属酸化物粒子の固形分を合計した固形分の濃度)は、5~70質量%の範囲にあることが好ましい。5質量%より低いと、塗料の濃縮安定性が低いために、均一な膜が得られ難い場合がある。また、得られた透明被膜は、硬度や耐擦傷性が不充分となったり、ヘーズあるいは外観が悪くなったりして、生産性、製造信頼性等が低下する場合がある。70質量%より高くても、塗布液の粘度が高くなり、塗布性が低下したり、得られる透明被膜のヘーズが高くなったり、表面粗さが大きくなり、耐擦傷性が不充分となる場合がある。
上記塗布液の固形分濃度は、10~60質量%の範囲にあることが更に好ましい。
<<Concentration of coating liquid for forming transparent film>>
The solid content concentration of the coating liquid (concentration of the total solid content of the solid content of the alkylene oxide-modified (meth)acrylate resin and the solid content of the surface-treated metal oxide particles) is preferably in the range of 5 to 70% by mass. . If it is less than 5% by mass, it may be difficult to obtain a uniform film due to the low concentration stability of the paint. In addition, the resulting transparent film may have insufficient hardness and scratch resistance, or may have haze or poor appearance, resulting in a decrease in productivity, production reliability, and the like. Even if it is higher than 70% by mass, the viscosity of the coating liquid increases, the coating property decreases, the haze of the resulting transparent film increases, the surface roughness increases, and the scratch resistance becomes insufficient. There is
More preferably, the solid content concentration of the coating liquid is in the range of 10 to 60% by mass.
〈表面処理金属酸化物粒子の濃度〉
塗布液中の表面処理金属酸化物粒子は、アルキレンオキサイド変性(メタ)アクリレート樹脂の固形分量と表面処理金属酸化物粒子の固形分の合計量に対して、固形分として30~90質量%である。ここで、表面処理金属酸化物粒子が30質量%より少ないと、塗膜化した時に、カーリングの抑制効果、硬度および耐擦傷性が不充分となる場合や、被膜の表面の親水性化が不充分となり、望むべく低い水接触角は得られない場合がある。逆に、表面処理金属酸化物粒子が90質量%より多くても、透明被膜にクラックが発生する場合がある。また、被膜が得られたとしても、基材との密着性が不十分となる場合や、膜強度や耐擦傷性、透明性、ヘーズ等が悪化する場合がある。この表面処理金属酸化物粒子成分は、アルキレンオキサイド変性(メタ)アクリレート樹脂成分の固形分量と表面処理金属酸化物粒子成分の固形分の合計量に対して、固形分として50~85質量%にあることがより好ましく、60~80質量%にあることが更に好ましい。
<Concentration of surface-treated metal oxide particles>
The surface-treated metal oxide particles in the coating liquid have a solid content of 30 to 90% by mass with respect to the total solid content of the alkylene oxide-modified (meth)acrylate resin and the surface-treated metal oxide particles. . If the amount of the surface-treated metal oxide particles is less than 30% by mass, the effect of suppressing curling, hardness, and scratch resistance may be insufficient when the coating is formed, or the hydrophilicity of the surface of the coating may be insufficient. sufficient and the desired low water contact angle may not be obtained. Conversely, cracks may occur in the transparent film even if the surface-treated metal oxide particles are more than 90% by mass. Moreover, even if a coating is obtained, the adhesion to the substrate may be insufficient, or the coating strength, scratch resistance, transparency, haze, etc. may be deteriorated. The surface-treated metal oxide particle component has a solid content of 50 to 85% by mass with respect to the total solid content of the alkylene oxide-modified (meth)acrylate resin component and the surface-treated metal oxide particle component. is more preferable, and 60 to 80% by mass is even more preferable.
〈アルキレンオキサイド変性(メタ)アクリレート樹脂の濃度〉
塗布液中のアルキレンオキサイド変性(メタ)アクリレート樹脂は、アルキレンオキサイド変性(メタ)アクリレート樹脂の固形分量と表面処理金属酸化物粒子の固形分の合計量に対して、固形分として10~70質量%にあることが好ましい。
ここで、アルキレンオキサイド変性(メタ)アクリレート樹脂が10質量%より少ないと、塗膜化した時に、透明被膜にクラックが発生する場合がある。逆に、アルキレンオキサイド変性(メタ)アクリレート樹脂が70質量%より多すぎても、透明被膜の硬度、耐擦傷性が不充分となる場合がある。このアルキレンオキサイド変性(メタ)アクリレート樹脂成分は、アルキレンオキサイド変性(メタ)アクリレート樹脂成分の固形分量と表面処理金属酸化物粒子成分の固形分の合計量に対して、固形分として15~50質量%であることがより好ましく、20~40質量%であることが更に好ましい。
<Concentration of alkylene oxide-modified (meth)acrylate resin>
The alkylene oxide-modified (meth)acrylate resin in the coating liquid has a solid content of 10 to 70% by mass with respect to the total solid content of the alkylene oxide-modified (meth)acrylate resin and the surface-treated metal oxide particles. preferably in
Here, if the alkylene oxide-modified (meth)acrylate resin is less than 10% by mass, cracks may occur in the transparent coating when formed into a coating. Conversely, if the amount of the alkylene oxide-modified (meth)acrylate resin exceeds 70% by mass, the hardness and scratch resistance of the transparent film may become insufficient. The alkylene oxide-modified (meth)acrylate resin component has a solid content of 15 to 50% by mass based on the total solid content of the alkylene oxide-modified (meth)acrylate resin component and the surface-treated metal oxide particle component. and more preferably 20 to 40% by mass.
このような表面処理金属酸化物粒子及びアルキレンオキサイド変性(メタ)アクリレート樹脂の濃度割合の塗布液においては、塗布液中の表面処理金属酸化物粒子の濃度が、固形分として、1.5~63質量%の範囲にあることが好ましく、アルキレンオキサイド変性(メタ)アクリレート樹脂が、固形分として、0.5~49質量%の範囲にあることが好ましい。 In the coating liquid having such a concentration ratio of the surface-treated metal oxide particles and the alkylene oxide-modified (meth)acrylate resin, the concentration of the surface-treated metal oxide particles in the coating liquid is 1.5 to 63 as solids. % by mass, and the alkylene oxide-modified (meth)acrylate resin is preferably in the range of 0.5 to 49% by mass as a solid content.
本発明の塗布液の構成は、上述のように、アルキレンオキサイド変性(メタ)アクリレート樹脂と、金属酸化物粒子の表面に有機珪素化合物が設けられた平均粒子径が5~500nmの表面処理金属酸化物粒子と、有機溶媒とを含むことである。このアルキレンオキサイド変性(メタ)アクリレート樹脂には、(メタ)アクリレート官能基数が3~10、アルキレンオキサイド基数が3~40含まれる。表面処理金属酸化物粒子には、有機珪素化合物が金属酸化物粒子100質量部に対し、Rn-SiO(4-n)/2として0.1~50質量部含まれる。塗布液中には、この表面処理金属酸化物粒子が、アルキレンオキサイド変性(メタ)アクリレート樹脂と表面処理金属酸化物粒子の固形分の合計量に対して30~90質量%含まれる。
より好ましい塗布液の構成要件を挙げると、まず、アルキレンオキサイド変性(メタ)アクリレート樹脂には、(メタ)アクリレート官能基数が4~8、アルキレンオキサイド基数が6~30含まれる。次に、表面処理金属酸化物粒子には、有機珪素化合物が、金属酸化物粒子100質量部に対し、Rn-SiO(4-n)/2として1~30質量部含まれる。塗布液中には、この表面処理金属酸化物粒子が、アルキレンオキサイド変性(メタ)アクリレート樹脂と表面処理金属酸化物粒子の固形分の合計量に対して50~85質量%含まれる。
さらに好ましい塗布液の構成要件を挙げると、まず、アルキレンオキサイド変性(メタ)アクリレート樹脂には、(メタ)アクリレート官能基数が4~6、アルキレンオキサイド基数が12~24含まれる。次に、表面処理金属酸化物粒子には、有機珪素化合物が、金属酸化物粒子100質量部に対し、Rn-SiO(4-n)/2として5~20質量部含まれる。塗布液中には、この表面処理金属酸化物粒子が、アルキレンオキサイド変性(メタ)アクリレート樹脂と表面処理金属酸化物粒子の固形分の合計量に対して60~80質量%含まれる。
As described above, the coating liquid of the present invention comprises an alkylene oxide-modified (meth)acrylate resin and a surface-treated metal oxide having an average particle size of 5 to 500 nm, in which an organosilicon compound is provided on the surface of metal oxide particles. and an organic solvent. This alkylene oxide-modified (meth)acrylate resin contains 3 to 10 (meth)acrylate functional groups and 3 to 40 alkylene oxide groups. The surface-treated metal oxide particles contain 0.1 to 50 parts by mass of an organosilicon compound as R n —SiO (4-n)/2 per 100 parts by mass of the metal oxide particles. The coating liquid contains the surface-treated metal oxide particles in an amount of 30 to 90% by mass based on the total solid content of the alkylene oxide-modified (meth)acrylate resin and the surface-treated metal oxide particles.
Constituent elements of a more preferable coating liquid include, first, the alkylene oxide-modified (meth)acrylate resin contains 4 to 8 (meth)acrylate functional groups and 6 to 30 alkylene oxide groups. Next, the surface-treated metal oxide particles contain 1 to 30 parts by mass of an organosilicon compound as R n —SiO 2 (4-n)/2 with respect to 100 parts by mass of the metal oxide particles. The coating liquid contains the surface-treated metal oxide particles in an amount of 50 to 85% by mass based on the total solid content of the alkylene oxide-modified (meth)acrylate resin and the surface-treated metal oxide particles.
Further preferable constituents of the coating liquid are as follows. First, the alkylene oxide-modified (meth)acrylate resin contains 4 to 6 (meth)acrylate functional groups and 12 to 24 alkylene oxide groups. Next, the surface-treated metal oxide particles contain 5 to 20 parts by mass of an organosilicon compound as R n —SiO 2 (4-n)/2 with respect to 100 parts by mass of the metal oxide particles. The coating liquid contains the surface-treated metal oxide particles in an amount of 60 to 80% by mass based on the total solid content of the alkylene oxide-modified (meth)acrylate resin and the surface-treated metal oxide particles.
[透明被膜付基材]
上述の塗布液を用いて、透明被膜を基材に直接的又は間接的に形成する。透明被膜は、主に表面処理金属酸化物粒子と樹脂成分で形成される。本発明の透明被膜は、水に対する接触角が低いことから、本発明の被膜上にさらに樹脂層等の上層を設けるような場合に特に有用である。すなわち、本発明の透明被膜付基材は、基板上に透明被膜が設けられ、透明被膜上にさらに樹脂層等の上層が設けられる構成であることが好ましい。
《基材》
基材としては、公知のものを特に制限なく使用することが可能であり、ポリカーボネート、アクリル樹脂、ポリエチレンテレフタラート(PET)、トリアセチルセルロース(TAC)、ポリメタクリル酸メチル樹脂(PMMA)、シクロオレフィンポリマー(COP)等の透明な樹脂基材が好ましい。これらの樹脂基材は、上述の塗布液によって形成される透明被膜との密着性が優れ、硬度、耐擦傷性等に優れた透明被膜付基材を得ることができる。このため、薄い基材に好適に用いることができる。基材の厚みは、20~70μmの範囲にあることが好ましい。中でもTAC基材は、基材が薄いとカーリングしやすいので、カーリングを抑制するために本発明の透明被膜用の塗布液を用いることが好ましい。
基材の厚みは、30~60μmの範囲にあることが更に好ましい。
[Substrate with transparent film]
A transparent film is directly or indirectly formed on a substrate using the coating liquid described above. A transparent film is mainly formed of surface-treated metal oxide particles and a resin component. Since the transparent film of the present invention has a low contact angle with water, it is particularly useful when an upper layer such as a resin layer is provided on the film of the present invention. That is, the substrate with a transparent film of the present invention preferably has a structure in which a transparent film is provided on a substrate, and an upper layer such as a resin layer is further provided on the transparent film.
"Base material"
As the base material, known ones can be used without particular limitation, and polycarbonate, acrylic resin, polyethylene terephthalate (PET), triacetyl cellulose (TAC), polymethyl methacrylate resin (PMMA), cycloolefin A transparent resin substrate such as a polymer (COP) is preferred. These resin substrates have excellent adhesion to the transparent coating formed from the above-described coating solution, and can provide a substrate with a transparent coating excellent in hardness, scratch resistance, and the like. Therefore, it can be suitably used for thin base materials. The thickness of the substrate is preferably in the range of 20-70 μm. Among them, the TAC substrate tends to curl if the substrate is thin, and therefore it is preferable to use the coating liquid for the transparent film of the present invention in order to suppress the curling.
More preferably, the thickness of the substrate is in the range of 30-60 μm.
《透明被膜》
本発明に係る透明被膜は、塗布液中のアルキレンオキサイド変性(メタ)アクリレート樹脂成分と表面処理金属酸化物粒子成分との量が、そのまま被膜中の成分割合となる。 すなわち、アルキレンオキサイド変性(メタ)アクリレート樹脂成分の固形分量と平均粒子径が5~500nm、好ましくは10~200nmの表面処理金属酸化物粒子成分の固形分の合計量に対して、アルキレンオキサイド変性(メタ)アクリレート樹脂成分は、固形分として10~70質量%にあることが好ましい。ここで、アルキレンオキサイド変性(メタ)アクリレート樹脂が10質量%より少ないと、透明被膜にクラックが発生する場合がある。逆に、アルキレンオキサイド変性(メタ)アクリレート樹脂が70質量%より多くても、透明被膜の硬度、耐擦傷性が不充分となる場合がある。このアルキレンオキサイド変性(メタ)アクリレート樹脂成分は、アルキレンオキサイド変性(メタ)アクリレート樹脂成分の固形分量と表面処理金属酸化物粒子成分の固形分の合計量に対して、固形分として15~50質量%であることがより好ましく、20~40質量%であることが更に好ましい。
《Transparent Coating》
In the transparent film according to the present invention, the amounts of the alkylene oxide-modified (meth)acrylate resin component and the surface-treated metal oxide particle component in the coating solution are directly the proportions of the components in the film. That is, with respect to the total amount of the solid content of the alkylene oxide-modified (meth)acrylate resin component and the solid content of the surface-treated metal oxide particle component having an average particle diameter of 5 to 500 nm, preferably 10 to 200 nm, the alkylene oxide-modified ( The meth)acrylate resin component is preferably present in a solids content of 10 to 70% by mass. Here, if the alkylene oxide-modified (meth)acrylate resin is less than 10% by mass, cracks may occur in the transparent coating. Conversely, even if the alkylene oxide-modified (meth)acrylate resin is more than 70% by mass, the hardness and scratch resistance of the transparent film may be insufficient. The alkylene oxide-modified (meth)acrylate resin component has a solid content of 15 to 50% by mass based on the total solid content of the alkylene oxide-modified (meth)acrylate resin component and the surface-treated metal oxide particle component. and more preferably 20 to 40% by mass.
一方、表面処理金属酸化物粒子成分は、アルキレンオキサイド変性(メタ)アクリレート樹脂成分の固形分量と表面処理金属酸化物粒子成分の固形分の合計量に対して、固形分として30~90質量%にあることが好ましい。ここで、表面処理金属酸化物粒子が30質量%より少ないと、カーリングの抑制効果、硬度および耐擦傷性が不充分となる場合や、被膜の表面の親水性化が不充分となり、望むべく低い水接触角は得られない場合がある。逆に、表面処理金属酸化物粒子が90質量%より多くても、透明被膜にクラックが発生する場合がある。また、被膜が得られたとしても、基材との密着性が不十分となる場合や、膜強度や耐擦傷性、透明性、ヘーズ等が悪化する場合がある。この表面処理金属酸化物粒子成分は、アルキレンオキサイド変性(メタ)アクリレート樹脂成分の固形分量と表面処理金属酸化物粒子成分の固形分の合計量に対して、固形分として50~85質量%にあることがより好ましく、60~80質量%にあることが更に好ましい。 On the other hand, the surface-treated metal oxide particle component has a solid content of 30 to 90% by mass with respect to the total solid content of the alkylene oxide-modified (meth)acrylate resin component and the surface-treated metal oxide particle component. Preferably. Here, if the amount of the surface-treated metal oxide particles is less than 30% by mass, the effect of suppressing curling, hardness and scratch resistance may be insufficient, or the hydrophilicity of the surface of the film may be insufficient. Water contact angles may not be obtained. Conversely, cracks may occur in the transparent film even if the surface-treated metal oxide particles are more than 90% by mass. Moreover, even if a coating is obtained, the adhesion to the substrate may be insufficient, or the coating strength, scratch resistance, transparency, haze, etc. may be deteriorated. The surface-treated metal oxide particle component has a solid content of 50 to 85% by mass with respect to the total solid content of the alkylene oxide-modified (meth)acrylate resin component and the surface-treated metal oxide particle component. is more preferable, and 60 to 80% by mass is even more preferable.
表面処理金属酸化物粒子の平均粒子径が5nmよりも小さいと得ることが困難であり、得られたとしても表面処理剤での表面処理、及びゾルの安定性が不十分となることが多い。また、表面処理金属酸化物粒子の平均粒子径が500nmより大きいと、表面処理金属酸化物粒子の含有量にもよるが、膜表面で光散乱を生じたり、透明被膜のヘーズが悪化して、透明性が低下する。得られる透明被膜は、従来、一般的に樹脂成分単独で構成された被膜の方が、表面処理金属酸化物粒子が含まれる被膜よりも接触角は低くなるが、本発明の表面処理金属酸化物粒子を含む被膜は、樹脂成分単独で構成された被膜よりも接触角が低下するという特徴を有する。その理由は明らかではないが、被膜表面に粒子が存在して膜表面にテクスチャを形成し、被膜表面積が相対的に増大して、低接触角を助長すること(Wenzel効果)が要因の1つと考えられる。 If the average particle size of the surface-treated metal oxide particles is smaller than 5 nm, it is difficult to obtain them, and even if they are obtained, the surface treatment with a surface-treating agent and the stability of the sol are often insufficient. Further, when the average particle size of the surface-treated metal oxide particles is larger than 500 nm, depending on the content of the surface-treated metal oxide particles, light scattering occurs on the film surface, haze of the transparent film deteriorates, Reduces transparency. Conventionally, the obtained transparent film has a lower contact angle with a film composed of a resin component alone than a film containing surface-treated metal oxide particles, but the surface-treated metal oxide of the present invention has a lower contact angle. A film containing particles has a characteristic that the contact angle is lower than that of a film composed of a resin component alone. Although the reason is not clear, one of the factors is that particles exist on the film surface to form a texture on the film surface, and the surface area of the film relatively increases to promote a low contact angle (Wenzel effect). Conceivable.
透明被膜の膜厚は1~10μmが好ましい。透明被膜が1μmより薄いと、透明被膜の硬度、耐擦傷性が不充分となる場合がある。透明被膜が10μmより厚いと、膜の収縮が大きくなり、カーリングが起こり易く、基材との密着性が不充分となる場合がある。また、収縮が非常に大きい場合には、クラックが発生する場合もある。この透明被膜の膜厚は、2~10μmが更に好ましい。 The film thickness of the transparent film is preferably 1 to 10 μm. If the thickness of the transparent coating is less than 1 μm, the hardness and scratch resistance of the transparent coating may be insufficient. If the transparent coating is thicker than 10 μm, the shrinkage of the coating is increased, curling is likely to occur, and adhesion to the substrate may be insufficient. Also, if the shrinkage is too great, cracks may occur. The film thickness of this transparent film is more preferably 2 to 10 μm.
透明被膜の接触角は、水に対して、70°未満であることが好ましい。接触角が70°以上であると、親水性が不充分であり、上層との接着性が低下する場合がある。この透明被膜の接触角は、水に対して、50°未満であることが更に好ましい。
透明被膜の鉛筆硬度は、3H以上であることが好ましい。3H未満の鉛筆硬度では、ハードコート膜として硬度が不充分である。この透明被膜の鉛筆硬度は、4H以上であることが更に好ましい。
透明被膜のカーリング性は、20mm未満であることが好ましく、10mm未満であることが更に好ましい。
The contact angle of the transparent coating with water is preferably less than 70°. If the contact angle is 70° or more, the hydrophilicity may be insufficient and the adhesiveness to the upper layer may be lowered. More preferably, the contact angle of this transparent coating with water is less than 50°.
The pencil hardness of the transparent coating is preferably 3H or more. A pencil hardness of less than 3H is insufficient for a hard coat film. The pencil hardness of this transparent coating is more preferably 4H or more.
The curling property of the transparent coating is preferably less than 20 mm, more preferably less than 10 mm.
また、透明被膜付基材の光透過率が90.0%以上であることが好ましい。
透明被膜付基材の光透過率が90.0%よりも低いと、表示装置等に用いた場合、画像の鮮明度不充分となる場合がある。この透明被膜付基材の光透過率は、91.5%以上であることが更に好ましい。
このような透明被膜付基材は、光電気セル、液晶表示セルや携帯電話、パソコン等の軽量化のために、薄くかつ軽量性が求められる用途に好適である。
Moreover, it is preferable that the light transmittance of the base material with a transparent film is 90.0% or more.
If the light transmittance of the substrate with a transparent film is lower than 90.0%, the definition of images may be insufficient when used in a display device or the like. More preferably, the light transmittance of this substrate with a transparent film is 91.5% or more.
Such a transparent film-coated substrate is suitable for applications requiring thinness and lightness in order to reduce the weight of photoelectric cells, liquid crystal display cells, mobile phones, personal computers, and the like.
以下、本発明の実施例を説明するが、本発明はこれら実施例に限定されるものではない。
なお、実施例では、金属酸化物微粒子としてシリカアルミナ微粒子またはシリカ微粒子を用いた。
Examples of the present invention will be described below, but the present invention is not limited to these examples.
In the examples, silica-alumina fine particles or silica fine particles were used as the metal oxide fine particles.
(実施例1)
《塗布液(1)の調製》
シリカアルミナゾル分散液(日揮触媒化成(株)製;OSCAL1132;平均粒子径12nm、固形分濃度40.5質量%、分散媒:メタノールゾル、粒子屈折率1.46)100gにγ-メタアクリロオキシプロピルトリメトキシシラン6.08g(信越シリコ-ン(株)製:KBM-503、SiO2成分81.2質量%)を混合し、超純水を8.80g添加し、5%アンモニア水0.40g添加し、50℃で6時間攪拌した。これにより、表面処理した12nmのシリカアルミナゾル分散液を得た(固形分濃度40.4質量%)。
その後、ロータリーエバポレーターでプロピレングリコールモノメチルエーテル(PGME)に溶剤置換し、固形分46.6質量%のシリカゾルPGME分散液(1)を得た。ついで、このシリカゾルPGME分散液(1)60.11gと、EO変性アクリレートバインダー(新中村化学工業(株)製:NKエステル A-DPH-18E)12.00g、と光重合開始剤(チバジャパン(株))製:イルガキュア184)1.80gとPGME13.59gとアセトン12.50gを充分に混合して、固形分濃度41.8質量%の透明被膜形成用の塗布液(1)を調製した。この塗布液(1)の組成を表1に示す。
《平均粒子径の測定》
平均粒子径は、電子顕微鏡写真を撮影し、任意の100個の粒子について粒子径を測定し、その平均値として得たものである。
(Example 1)
<<Preparation of coating liquid (1)>>
Silica-alumina sol dispersion (manufactured by Nikki Shokubai Kasei Co., Ltd.; OSCAL1132; average particle diameter 12 nm, solid content concentration 40.5% by mass, dispersion medium: methanol sol, particle refractive index 1.46) 100 g of γ-methacryloxy 6.08 g of propyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.: KBM-503, SiO 2 component: 81.2% by mass) was mixed, 8.80 g of ultrapure water was added, and 0.5% of 5% aqueous ammonia was added. 40 g was added and stirred at 50° C. for 6 hours. As a result, a surface-treated 12 nm silica-alumina sol dispersion was obtained (solid concentration: 40.4% by mass).
Thereafter, the solvent was replaced with propylene glycol monomethyl ether (PGME) using a rotary evaporator to obtain a silica sol PGME dispersion (1) having a solid content of 46.6% by mass. Next, 60.11 g of this silica sol PGME dispersion (1), 12.00 g of EO-modified acrylate binder (manufactured by Shin-Nakamura Chemical Co., Ltd.: NK Ester A-DPH-18E), and a photopolymerization initiator (Ciba Japan ( 1.80 g of Irgacure 184), 13.59 g of PGME, and 12.50 g of acetone were sufficiently mixed to prepare a coating liquid (1) for forming a transparent film having a solid concentration of 41.8% by mass. Table 1 shows the composition of this coating liquid (1).
<<Measurement of average particle size>>
The average particle size is obtained by taking an electron micrograph, measuring the particle size of arbitrary 100 particles, and obtaining the average value.
《透明被膜付基材(1)の調製》
透明被膜形成用の塗布液(1)を、TACフィルム(富士フィルム(株)製:FT-PB40UL-M、厚さ:40μm、屈折率:1.51)にバーコーター法(#16)で塗布し、80℃で120秒間乾燥した後、N2雰囲気下300mJ/cm2の紫外線を照射して硬化させて透明被膜付基材(1)を得た。透明被膜の膜厚は8μmであった。
この透明被膜付基材(1)の膜厚、鉛筆硬度、接触角、カーリング性、耐擦傷性、ヘーズ、全光線透過率、密着性及び外観について、以下の方法および評価基準で評価し、結果を表2に示す。
<<Preparation of base material (1) with transparent film>>
Coating solution (1) for forming a transparent film is applied to a TAC film (manufactured by Fuji Film Co., Ltd.: FT-PB40UL-M, thickness: 40 μm, refractive index: 1.51) by a bar coater method (#16). After drying at 80° C. for 120 seconds, the substrate was cured by irradiating with ultraviolet rays of 300 mJ/cm 2 in an N 2 atmosphere to obtain a base material (1) with a transparent film. The film thickness of the transparent film was 8 μm.
The film thickness, pencil hardness, contact angle, curling property, scratch resistance, haze, total light transmittance, adhesion and appearance of this substrate with transparent film (1) were evaluated according to the following methods and evaluation criteria. are shown in Table 2.
《膜厚の測定》
膜厚は、デジタルゲージ((株)小野測器製ゲージスタンドST-0230とデジタルゲージカウンターDG-5100)により測定した。
《鉛筆硬度の測定》
JIS-K-5600に準じて鉛筆硬度試験器により測定した。鉛筆硬度は、3H以上が好適である。
《接触角の測定》
全自動接触角計(協和界面科学(株)製:DM700)により接触角を測定した。水に対する接触角は、70°未満が好適である。
《Film thickness measurement》
The film thickness was measured with a digital gauge (manufactured by Ono Sokki Co., Ltd. gauge stand ST-0230 and digital gauge counter DG-5100).
《Pencil Hardness Measurement》
Measured with a pencil hardness tester according to JIS-K-5600. A pencil hardness of 3H or more is preferable.
《Measurement of contact angle》
The contact angle was measured with a fully automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd.: DM700). The contact angle with water is preferably less than 70°.
《カーリング性の評価》
14cm×25cm×40μm(厚み)のTACフィルム基材上に厚さ8μmの透明被膜が形成できるように塗布液(1)を塗布し、20時間静置し、その後、フィルムを10cm×10cmサイズにカットし、塗布面を下にしてフィルムを平板上に置き、カーリング(湾曲)して浮上した基材の頂点の平板からの高さを測定し、以下の基準で評価した。
〈評価基準〉
10mm未満 :◎
10~20mm未満 :○
20~30mm未満 :△
30mm以上 :×
《耐擦傷性の評価》
#0000スチールウールを用い、荷重500g/cm2で10回摺動し、膜の表面を目視観察し、以下の基準で評価した。
〈評価基準〉
筋状の傷が認められない :◎
筋状に傷が僅かに認められる:○
筋状に傷が多数認められる :△
面が全体的に削られている :×
《全光線透過率、ヘーズの測定》
全光線透過率およびヘーズは、ヘーズメーター(日本電色(株)製NDH-5000)により測定した。なお、未塗布のTACフィルムは全光線透過率が93.0%、ヘーズが0.3%であった。全光線透過率は90.0%以上、ヘーズは0.5%以下が好適である。
《密着性》
透明被膜付基材の表面にナイフで縦横1mmの間隔で11本の平行な傷を付け100個の升目を作り、これにセロハンテ-プを接着し、ついで、セロハンテ-プを剥離したときに被膜が剥離せず残存している升目の数を、以下の4段階に分類することにより密着性を評価した。
〈評価基準〉
残存升目の数100個 :◎
残存升目の数90~99個 :○
残存升目の数85~89個 :△
残存升目の数84個以下 :×
《外観》
透明被膜付基材の表面を目視で観察し、以下の基準で評価した。
〈評価基準〉
表面に、スジ、ムラ、クラック、ブリードアウトの外観不良が確認できない :◎
表面に、スジ、ムラ、クラック、ブリードアウトの外観不良がほぼ確認できない :○
表面に、スジ、ムラ、クラック、ブリードアウトの外観不良が僅かに観察された :△
表面に、スジ、ムラ、クラック、ブリードアウトの外観不良が明らかに観察された:×
<<Evaluation of curling property>>
Coating solution (1) is applied to a TAC film substrate of 14 cm x 25 cm x 40 µm (thickness) so as to form a transparent film with a thickness of 8 µm, left to stand for 20 hours, and then the film is cut into a size of 10 cm x 10 cm. After cutting, the film was placed on a flat plate with the coated surface facing down, and the height from the flat plate of the apex of the substrate that curled (curved) and floated was measured and evaluated according to the following criteria.
<Evaluation criteria>
Less than 10mm: ◎
Less than 10 to 20 mm: ○
Less than 20 to 30 mm: △
30 mm or more: ×
<<Evaluation of abrasion resistance>>
Using #0000 steel wool, the surface of the film was slid 10 times with a load of 500 g/cm 2 , visually observed, and evaluated according to the following criteria.
<Evaluation criteria>
No streaky scratches : ◎
Slightly streak-like scratches are observed: ○
Many streaky scratches are observed: △
The surface is entirely scraped : ×
《Measurement of total light transmittance and haze》
The total light transmittance and haze were measured with a haze meter (NDH-5000 manufactured by Nippon Denshoku Co., Ltd.). The uncoated TAC film had a total light transmittance of 93.0% and a haze of 0.3%. It is preferable that the total light transmittance is 90.0% or more and the haze is 0.5% or less.
《Adhesion》
11 parallel scratches were made on the surface of the base material with a transparent film with a knife at intervals of 1 mm in length and width to make 100 squares, and a cellophane tape was adhered to them, and then the cellophane tape was peeled off. Adhesion was evaluated by classifying the number of remaining squares without peeling off into the following four grades.
<Evaluation criteria>
Number of remaining squares 100: ◎
Number of remaining squares 90 to 99: ○
Number of remaining squares 85 to 89: △
Number of remaining squares 84 or less: ×
"exterior"
The surface of the transparent film-coated substrate was visually observed and evaluated according to the following criteria.
<Evaluation criteria>
No appearance defects such as streaks, unevenness, cracks, or bleeding out can be confirmed on the surface: ◎
Almost no visible defects such as streaks, unevenness, cracks, or bleeding out on the surface: ○
Slight appearance defects such as streaks, unevenness, cracks, and bleeding out were observed on the surface: △
Poor appearance such as streaks, unevenness, cracks, and bleeding out were clearly observed on the surface: ×
(実施例2)
《透明被膜形成用の塗布液(2)の調製》
EO変性アクリレートバインダーを新中村化学工業(株)製:NKエステル A-DPH-24Eに変更した以外は実施例1と同様にして、固形分濃度41.8質量%の塗布液(2)を調製した。得られた塗布液(2)の組成を表1に示す。
《透明被膜付基材(2)の調製》
塗布液(2)を使用した以外は実施例1と同様に透明被膜付基材(2)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Example 2)
<<Preparation of coating liquid (2) for forming transparent film>>
A coating liquid (2) having a solid content concentration of 41.8% by mass was prepared in the same manner as in Example 1, except that the EO-modified acrylate binder was changed to NK Ester A-DPH-24E manufactured by Shin-Nakamura Chemical Co., Ltd. did. Table 1 shows the composition of the obtained coating liquid (2).
<<Preparation of substrate with transparent film (2)>>
A base material (2) with a transparent film was produced and evaluated in the same manner as in Example 1 except that the coating liquid (2) was used. The film thickness of the transparent film was 8 μm.
(実施例3)
《透明被膜形成用の塗布液(3)の調製》
EO変性アクリレートバインダーを新中村化学工業(株)製:NKエステル A-DPH-12Eに変更した以外は実施例1と同様にして、固形分濃度41.8質量%の塗布液(3)を調製した。得られた塗布液(3)の組成を表1に示す。
《透明被膜付基材(3)の調製》
塗布液(3)を使用した以外は実施例1と同様に透明被膜付基材(3)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Example 3)
<<Preparation of coating liquid (3) for forming transparent film>>
A coating solution (3) having a solid content concentration of 41.8% by mass was prepared in the same manner as in Example 1, except that the EO-modified acrylate binder was changed to NK Ester A-DPH-12E manufactured by Shin-Nakamura Chemical Co., Ltd. did. Table 1 shows the composition of the obtained coating liquid (3).
<<Preparation of substrate with transparent film (3)>>
A base material (3) with a transparent film was produced and evaluated in the same manner as in Example 1 except that the coating liquid (3) was used. The film thickness of the transparent film was 8 μm.
(実施例4)
《透明被膜形成用の塗布液(4)の調製》
EO変性アクリレートバインダーを新中村化学工業(株)製:NKエステル ATM-35Eに変更した以外は実施例1と同様にして、固形分濃度41.8質量%の塗布液(4)を調製した。得られた塗布液(4)の組成を表1に示す。
《透明被膜付基材(4)の調製》
塗布液(4)を使用した以外は実施例1と同様に透明被膜付基材(4)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Example 4)
<<Preparation of coating liquid (4) for forming transparent film>>
A coating liquid (4) having a solid concentration of 41.8% by mass was prepared in the same manner as in Example 1, except that the EO-modified acrylate binder was changed to NK Ester ATM-35E manufactured by Shin-Nakamura Chemical Co., Ltd. Table 1 shows the composition of the obtained coating liquid (4).
<<Preparation of substrate with transparent film (4)>>
A base material (4) with a transparent film was produced and evaluated in the same manner as in Example 1 except that the coating liquid (4) was used. The film thickness of the transparent film was 8 μm.
(実施例5)
《透明被膜形成用の塗布液(5)の調製》
EO変性アクリレートバインダーを新中村化学工業(株)製:NKエステル A-GLY-9Eに変更した以外は実施例1と同様にして、固形分濃度41.8質量%の塗布液(5)を調製した。得られた塗布液(5)の組成を表1に示す。
《透明被膜付基材(5)の調製》
塗布液(5)を使用した以外は実施例1と同様に透明被膜付基材(5)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Example 5)
<<Preparation of coating liquid (5) for forming transparent film>>
A coating solution (5) having a solid content concentration of 41.8% by mass was prepared in the same manner as in Example 1, except that the EO-modified acrylate binder was changed to NK Ester A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd. did. Table 1 shows the composition of the obtained coating liquid (5).
<<Preparation of substrate with transparent film (5)>>
A base material (5) with a transparent film was produced and evaluated in the same manner as in Example 1 except that the coating liquid (5) was used. The film thickness of the transparent film was 8 μm.
(実施例6)
《透明被膜形成用の塗布液(6)の調製》
EO変性アクリレートバインダーを新中村化学工業(株)製:NKエステル A-DPH-16Pに変更した以外は実施例1と同様にして、固形分濃度41.8質量%の塗布液(6)を調製した。得られた塗布液(6)の組成を表1に示す。
《透明被膜付基材(6)の調製》
塗布液(6)を使用した以外は実施例1と同様に透明被膜付基材(6)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Example 6)
<<Preparation of coating liquid (6) for forming transparent film>>
A coating solution (6) having a solid content concentration of 41.8% by mass was prepared in the same manner as in Example 1, except that the EO-modified acrylate binder was changed to NK Ester A-DPH-16P manufactured by Shin-Nakamura Chemical Co., Ltd. did. Table 1 shows the composition of the obtained coating liquid (6).
<<Preparation of substrate with transparent film (6)>>
A base material (6) with a transparent film was produced and evaluated in the same manner as in Example 1 except that the coating liquid (6) was used. The film thickness of the transparent film was 8 μm.
(実施例7)
《透明被膜形成用の塗布液(7)の調製》
実施例1で得た固形分濃度46.6質量%のシリカゾルPGME分散液(1)64.41gと、EO変性アクリレート(新中村化学工業(株)製:NKエステル A-DPH-18E)10.00g、と光重合開始剤(チバジャパン(株)製:イルガキュア184)1.50gとPGME11.59gとアセトン12.50gを充分に混合して固形分濃度41.5質量%の塗布液(7)を調製した。得られた塗布液(7)の組成を表1に示す。
《透明被膜付基材(7)の調製》
塗布液(7)を使用した以外は実施例1と同様に透明被膜付基材(7)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Example 7)
<<Preparation of coating liquid (7) for forming transparent film>>
64.41 g of silica sol PGME dispersion (1) having a solid content concentration of 46.6% by mass obtained in Example 1, and EO-modified acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.: NK Ester A-DPH-18E)10. 00 g, and 1.50 g of a photopolymerization initiator (Ciba Japan Co., Ltd.: Irgacure 184), 11.59 g of PGME, and 12.50 g of acetone were sufficiently mixed to obtain a coating liquid (7) having a solid content concentration of 41.5% by mass. was prepared. Table 1 shows the composition of the obtained coating liquid (7).
<<Preparation of substrate with transparent film (7)>>
A substrate with a transparent film (7) was produced and evaluated in the same manner as in Example 1 except that the coating liquid (7) was used. The film thickness of the transparent film was 8 μm.
(実施例8)
《透明被膜形成用の塗布液(8)の調製》
実施例1で得た固形分濃度46.6質量%のシリカゾルPGME分散液(1)42.94gと、EO変性アクリレート(新中村化学工業(株)製:NKエステル A-DPH-18E)20.00g、と光重合開始剤(チバジャパン(株)製:イルガキュア184)3.00gとPGME21.56gとアセトン12.50gを充分に混合して固形分濃度43.0質量%の塗布液(8)を調製した。得られた塗布液(8)の組成を表1に示す。
《透明被膜付基材(8)の調製》
塗布液(8)を使用した以外は実施例1と同様に透明被膜付基材(8)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Example 8)
<<Preparation of coating liquid (8) for forming transparent film>>
42.94 g of the silica sol PGME dispersion (1) having a solid content concentration of 46.6% by mass obtained in Example 1, and EO-modified acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.: NK Ester A-DPH-18E)20. 00 g, and 3.00 g of a photopolymerization initiator (Ciba Japan Co., Ltd.: Irgacure 184), 21.56 g of PGME, and 12.50 g of acetone were sufficiently mixed to obtain a coating liquid (8) having a solid content concentration of 43.0% by mass. was prepared. Table 1 shows the composition of the obtained coating liquid (8).
<<Preparation of base material (8) with transparent film>>
A substrate with a transparent film (8) was produced and evaluated in the same manner as in Example 1 except that the coating liquid (8) was used. The film thickness of the transparent film was 8 μm.
(実施例9)
《透明被膜形成用の塗布液(9)の調製》
実施例1で得た固形分濃度46.6質量%のシリカゾルPGME分散液(1)25.76gと、EO変性アクリレート(新中村化学工業(株)製:NKエステル A-DPH-18E)28.00g、と光重合開始剤(チバジャパン(株)製:イルガキュア184)4.20gとPGME29.54gとアセトン12.50gを充分に混合して固形分濃度44.2質量%の塗布液(9)を調製した。得られた塗布液(9)の組成を表1に示す。
《透明被膜付基材(9)の調製》
塗布液(9)をバーコーター法(#20)で塗布した以外は実施例1と同様にして、透明被膜付基材(9)を製造し、評価した。透明被膜の膜厚は10μmであった。
(Example 9)
<<Preparation of coating liquid (9) for forming transparent film>>
25.76 g of the silica sol PGME dispersion (1) having a solid concentration of 46.6% by mass obtained in Example 1, and EO-modified acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.: NK Ester A-DPH-18E)28. 00 g, and 4.20 g of a photopolymerization initiator (Ciba Japan Co., Ltd.: Irgacure 184), 29.54 g of PGME, and 12.50 g of acetone were sufficiently mixed to obtain a coating liquid (9) having a solid content concentration of 44.2% by mass. was prepared. Table 1 shows the composition of the obtained coating liquid (9).
<<Preparation of substrate with transparent film (9)>>
A base material (9) with a transparent film was produced and evaluated in the same manner as in Example 1, except that the coating liquid (9) was applied by a bar coater method (#20). The film thickness of the transparent film was 10 μm.
(実施例10)
《透明被膜形成用の塗布液(10)の調製》
シリカアルミナゾル分散液(日揮触媒化成(株)製;OSCAL1132;平均粒子径12nm、固形分濃度40.5質量%、分散媒:メタノールゾル、粒子屈折率1.46)100gにγ-メタアクリロオキシプロピルトリメトキシシラン12.15g(信越シリコ-ン(株)製:KBM-503、SiO2成分81.2質量%)を混合し、超純水を17.60g添加し、5%アンモニア水0.40g添加し、50℃で6時間攪拌して表面処理した12nmのシリカアルミナゾル分散液を得た(固形分濃度40.5質量%)。
その後、ロータリーエバポレーターでプロピレングリコールモノメチルエーテル(PGME)に溶剤置換し、固形分52.7質量%のシリカゾルPGME分散液(2)を得た。
ついで、固形分濃度52.7質量%のシリカゾルPGME分散液(2)53.18gと、EO変性アクリレートバインダー(新中村化学工業(株)製:NKエステル A-DPH-18E)12.00g、と光重合開始剤(チバジャパン(株))製:イルガキュア184)1.80gとPGME20.52gとアセトン12.50gを充分に混合して固形分濃度41.8質量%の塗布液(10)を調製した。得られた塗布液(10)の組成を表1に示す。
《透明被膜付基材(10)の調製》
塗布液(10)を使用した以外は実施例1と同様に透明被膜付基材(10)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Example 10)
<<Preparation of coating liquid (10) for forming transparent film>>
Silica alumina sol dispersion (manufactured by Nikki Shokubai Kasei Co., Ltd.; OSCAL1132; average particle diameter 12 nm, solid content concentration 40.5% by mass, dispersion medium: methanol sol, particle refractive index 1.46) 100 g of γ-methacryloxy 12.15 g of propyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.: KBM-503, SiO 2 component: 81.2% by mass) was mixed, 17.60 g of ultrapure water was added, and 0.5% of 5% aqueous ammonia was added. 40 g was added and stirred at 50° C. for 6 hours to obtain a surface-treated 12 nm silica-alumina sol dispersion (solid concentration: 40.5% by mass).
Thereafter, the solvent was replaced with propylene glycol monomethyl ether (PGME) using a rotary evaporator to obtain a silica sol PGME dispersion (2) having a solid content of 52.7% by mass.
Next, 53.18 g of silica sol PGME dispersion (2) having a solid content concentration of 52.7% by mass, and 12.00 g of EO-modified acrylate binder (manufactured by Shin-Nakamura Chemical Co., Ltd.: NK Ester A-DPH-18E), 1.80 g of a photopolymerization initiator (Ciba Japan Co., Ltd.: Irgacure 184), 20.52 g of PGME, and 12.50 g of acetone were sufficiently mixed to prepare a coating liquid (10) having a solid content concentration of 41.8% by mass. did. Table 1 shows the composition of the obtained coating liquid (10).
<<Preparation of base material (10) with transparent film>>
A substrate with a transparent film (10) was produced and evaluated in the same manner as in Example 1 except that the coating liquid (10) was used. The film thickness of the transparent film was 8 μm.
(実施例11)
《透明被膜形成用の塗布液(11)の調製》
シリカアルミナゾル分散液(日揮触媒化成(株)製;OSCAL1132;平均粒子径12nm、固形分濃度40.5質量%、分散媒:メタノールゾル、粒子屈折率1.46)100gにγ-メタアクリロオキシプロピルトリメトキシシラン1.22g(信越シリコ-ン(株)製:KBM-503、SiO2成分81.2質量%)を混合し、超純水を1.76g添加し、5%アンモニア水0.40g添加し、50℃で6時間攪拌して表面処理した12nmのシリカゾル分散液を得た(固形分濃度40.4質量%)。
その後、ロータリーエバポレーターでプロピレングリコールモノメチルエーテル(PGME)に溶剤置換し、固形分41.7質量%のシリカゾルPGME分散液(3)を得た。
ついで、固形分濃度41.7質量%のシリカゾルPGME分散液(3)67.12gと、EO変性アクリレートバインダー(新中村化学工業(株)製:NKエステル A-DPH-18E)12.00g、と光重合開始剤(チバジャパン(株))製:イルガキュア184)1.80gとPGME6.58gとアセトン12.50gを充分に混合して固形分濃度41.8質量%の塗布液(11)を調製した。得られた塗布液(11)の組成を表1に示す。
《透明被膜付基材(11)の調製》
塗布液(11)を使用した以外は実施例1と同様に透明被膜付基材(11)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Example 11)
<<Preparation of coating liquid (11) for forming transparent film>>
Silica-alumina sol dispersion (manufactured by Nikki Shokubai Kasei Co., Ltd.; OSCAL1132; average particle diameter 12 nm, solid content concentration 40.5% by mass, dispersion medium: methanol sol, particle refractive index 1.46) 100 g of γ-methacryloxy 1.22 g of propyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.: KBM-503, SiO 2 component: 81.2% by mass) was mixed, 1.76 g of ultrapure water was added, and 0.2 g of 5% aqueous ammonia was added. 40 g was added and stirred at 50° C. for 6 hours to obtain a surface-treated 12 nm silica sol dispersion (solid concentration: 40.4% by mass).
Thereafter, the solvent was replaced with propylene glycol monomethyl ether (PGME) using a rotary evaporator to obtain a silica sol PGME dispersion (3) having a solid content of 41.7% by mass.
Then, 67.12 g of silica sol PGME dispersion (3) having a solid content concentration of 41.7% by mass, and 12.00 g of EO-modified acrylate binder (manufactured by Shin-Nakamura Chemical Co., Ltd.: NK Ester A-DPH-18E), 1.80 g of a photopolymerization initiator (Ciba Japan Co., Ltd.: Irgacure 184), 6.58 g of PGME, and 12.50 g of acetone were sufficiently mixed to prepare a coating liquid (11) having a solid content concentration of 41.8% by mass. did. Table 1 shows the composition of the obtained coating liquid (11).
<<Preparation of base material (11) with transparent film>>
A base material (11) with a transparent film was produced and evaluated in the same manner as in Example 1 except that the coating liquid (11) was used. The film thickness of the transparent film was 8 μm.
(実施例12)
《透明被膜形成用の塗布液(12)の調製》
シリカアルミナゾル分散液(日揮触媒化成(株)製;OSCAL1132;平均粒子径12nm、固形分濃度40.5質量%、分散媒:メタノールゾル、粒子屈折率1.46)100gにγ-アクリロオキシプロピルトリメトキシシラン6.08g(信越シリコ-ン(株)製:KBM-5103、SiO2成分81.2質量%)を混合し超純水を8.80g添加し、5%アンモニア水を0.40g添加し、50℃で6時間攪拌して表面処理した12nmのシリカアルミナゾル分散液を得た(固形分濃度40.4質量%)。
その後、ロータリーエバポレーターでプロピレングリコールモノメチルエーテル(PGME)に溶剤置換し、固形分46.6質量%のシリカゾルPGME分散液(4)を得た。
ついで、固形分濃度46.6質量%のシリカゾルPGME分散液(4)60.11gと、EO変性アクリレートバインダー(新中村化学工業(株)製:NKエステル A-DPH-18E)12.00g、と光重合開始剤(チバジャパン(株)製:イルガキュア184)1.80gとPGME13.59gとアセトン12.50gを充分に混合して固形分濃度46.6質量%の塗布液(12)を調製した。得られた塗布液(12)の組成を表1に示す。
《透明被膜付基材(12)の調製》
塗布液(12)を使用した以外は実施例1と同様に透明被膜付基材(12)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Example 12)
<<Preparation of coating liquid (12) for forming transparent film>>
Silica alumina sol dispersion (manufactured by Nikki Shokubai Kasei Co., Ltd.; OSCAL1132; average particle diameter 12 nm, solid content concentration 40.5% by mass, dispersion medium: methanol sol, particle refractive index 1.46) 100 g of γ-acrylooxypropyl 6.08 g of trimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.: KBM-5103, SiO 2 component 81.2% by mass) was mixed, 8.80 g of ultrapure water was added, and 0.40 g of 5% aqueous ammonia was added. and stirred at 50° C. for 6 hours to obtain a surface-treated 12 nm silica-alumina sol dispersion (solid concentration: 40.4% by mass).
Thereafter, the solvent was replaced with propylene glycol monomethyl ether (PGME) using a rotary evaporator to obtain a silica sol PGME dispersion (4) having a solid content of 46.6% by mass.
Then, 60.11 g of silica sol PGME dispersion (4) having a solid content concentration of 46.6% by mass, and 12.00 g of EO-modified acrylate binder (manufactured by Shin-Nakamura Chemical Co., Ltd.: NK Ester A-DPH-18E), 1.80 g of a photopolymerization initiator (Ciba Japan Co., Ltd.: Irgacure 184), 13.59 g of PGME, and 12.50 g of acetone were sufficiently mixed to prepare a coating liquid (12) having a solid content concentration of 46.6% by mass. . Table 1 shows the composition of the obtained coating liquid (12).
<<Preparation of substrate with transparent film (12)>>
A base material (12) with a transparent film was produced and evaluated in the same manner as in Example 1 except that the coating liquid (12) was used. The film thickness of the transparent film was 8 μm.
(実施例13)
《透明被膜形成用の塗布液(13)の調製》
シリカアルミナゾル分散液(日揮触媒化成(株)製;OSCAL1132;平均粒子径12nm、固形分濃度40.5質量%、分散媒:メタノールゾル、粒子屈折率1.46)100gにテトラエトキシシラン2.74g(多摩化学工業(株)製:正珪酸エチル-A、SiO2成分28.80%)を混合し超純水を4.33g添加し、5%アンモニア水を0.40g添加し、50℃で6時間攪拌して表面処理した12nmのシリカアルミナゾル分散液を得た(固形分濃度38.4質量%)。
その後、ロータリーエバポレーターでプロピレングリコールモノメチルエーテル(PGME)に溶剤置換し、固形分41.3質量%のシリカゾルPGME分散液(5)を得た。
ついで、固形分濃度41.3質量%のシリカゾルPGME分散液(5)67.78gと、EO変性アクリレートバインダー(新中村化学工業(株)製:NKエステル A-DPH-18E)12.00g、と光重合開始剤(チバジャパン(株)製:イルガキュア184)1.80gとPGME5.92gとアセトン12.50gを充分に混合して固形分濃度41.8質量%の塗布液(13)を調製した。得られた塗布液(13)の組成を表1に示す。
《透明被膜付基材(13)の調製》
塗布液(13)を使用した以外は実施例1と同様に透明被膜付基材(13)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Example 13)
<<Preparation of coating liquid (13) for forming transparent film>>
2.74 g of tetraethoxysilane to 100 g of a silica-alumina sol dispersion (manufactured by Nikki Shokubai Kasei Co., Ltd.; OSCAL1132; average particle size 12 nm, solid content concentration 40.5% by mass, dispersion medium: methanol sol, particle refractive index 1.46) (manufactured by Tama Chemical Industry Co., Ltd.: normal ethyl silicate-A, SiO 2 component 28.80%) was mixed, 4.33 g of ultrapure water was added, 0.40 g of 5% aqueous ammonia was added, and the mixture was heated at 50 °C. After stirring for 6 hours, a surface-treated 12 nm silica-alumina sol dispersion was obtained (solid concentration: 38.4% by mass).
Thereafter, the solvent was replaced with propylene glycol monomethyl ether (PGME) using a rotary evaporator to obtain a silica sol PGME dispersion (5) having a solid content of 41.3% by mass.
Then, 67.78 g of silica sol PGME dispersion (5) having a solid content concentration of 41.3% by mass, and 12.00 g of EO-modified acrylate binder (manufactured by Shin-Nakamura Chemical Co., Ltd.: NK Ester A-DPH-18E), 1.80 g of a photopolymerization initiator (Ciba Japan Co., Ltd.: Irgacure 184), 5.92 g of PGME, and 12.50 g of acetone were sufficiently mixed to prepare a coating liquid (13) having a solid content concentration of 41.8% by mass. . Table 1 shows the composition of the obtained coating liquid (13).
<<Preparation of substrate with transparent film (13)>>
A base material (13) with a transparent film was produced and evaluated in the same manner as in Example 1 except that the coating liquid (13) was used. The film thickness of the transparent film was 8 μm.
(実施例14)
《透明被膜形成用の塗布液(14)の調製》
シリカゾル分散液(日揮触媒化成(株)製;SI-30;平均粒子径12nm、SiO2濃度40.5質量%)1000gにイオン交換水6000gを加え、ついで陽イオン交換樹脂(三菱化学(株)製:SK-1BH)800gを添加し、1時間攪拌して脱アルカリ処理した。
次に、陽イオン交換樹脂を分離した後、陰イオン交換樹脂(三菱化学(株)製:SANUPC)400gを添加し、1時間攪拌して脱アニオン処理した。ついで、再び陽イオン交換樹脂(三菱化学(株)製:SK-1BH)400gを添加し、1時間攪拌して脱アルカリ処理してSiO2濃度5質量%のシリカ粒子分散液(A)を調製した。
この分散液を、限外濾過膜を用いてメタノールにて溶媒置換して、固形分濃度40.5質量%のメタノール分散液(A)を得た。
シリカメタノール分散液(A)100gにγ-メタアクリロオキシプロピルトリメトキシシラン6.08g(信越シリコ-ン(株)製:KBM-503、SiO2成分81.2質量%)を混合し、超純水を8.80g添加し、5%アンモニア水0.40g添加し、50℃で6時間攪拌して表面処理した12nmのシリカゾル分散液を得た(固形分濃度40.5質量%)。
その後、ロータリーエバポレーターでプロピレングリコールモノメチルエーテル(PGME)に溶剤置換し、固形分46.6質量%のシリカゾルPGME分散液(6)を得た。
シリカアルミナゾルをシリカゾルPGME分散液(6)に変更した以外は実施例1と同様にして、固形分濃度41.8質量%の塗布液(14)を調製した。得られた塗布液(14)の組成を表1に示す。
《透明被膜付基材(14)の調製》
塗布液(14)を使用した以外は実施例1と同様に透明被膜付基材(14)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Example 14)
<<Preparation of coating liquid (14) for forming transparent film>>
Silica sol dispersion (manufactured by Nikki Shokubai Kasei Co., Ltd.; SI-30; average particle diameter 12 nm, SiO concentration 40.5% by mass) was added to 1000 g of ion-exchanged water 6000 g, and then a cation exchange resin (Mitsubishi Chemical Corporation SK-1BH (manufactured by SK-1BH) (800 g) was added, and the solution was dealkalized by stirring for 1 hour.
Next, after separating the cation exchange resin, 400 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added and stirred for 1 hour for deanion treatment. Next, 400 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK-1BH) was added again, stirred for 1 hour, and dealkalized to prepare a silica particle dispersion (A) having a SiO 2 concentration of 5% by mass. did.
This dispersion liquid was solvent-substituted with methanol using an ultrafiltration membrane to obtain a methanol dispersion liquid (A) having a solid content concentration of 40.5% by mass.
6.08 g of γ-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.: KBM-503, SiO 2 component 81.2% by mass) was mixed with 100 g of silica-methanol dispersion (A). 8.80 g of pure water was added, 0.40 g of 5% aqueous ammonia was added, and the mixture was stirred at 50° C. for 6 hours to obtain a surface-treated 12 nm silica sol dispersion (solid concentration: 40.5 mass %).
Thereafter, the solvent was replaced with propylene glycol monomethyl ether (PGME) using a rotary evaporator to obtain a silica sol PGME dispersion (6) having a solid content of 46.6% by mass.
A coating liquid (14) having a solid content concentration of 41.8% by mass was prepared in the same manner as in Example 1, except that the silica-alumina sol was changed to the silica sol PGME dispersion (6). Table 1 shows the composition of the obtained coating liquid (14).
<<Preparation of base material (14) with transparent film>>
A substrate with a transparent film (14) was produced and evaluated in the same manner as in Example 1 except that the coating liquid (14) was used. The film thickness of the transparent film was 8 μm.
(実施例15)
《透明被膜形成用の塗布液(15)の調製》
シリカゾル分散液(日揮触媒化成(株)製;SI-80P;平均粒子径80nm、SiO2濃度40.5質量%)1000gにイオン交換水6000gを加え、ついで陽イオン交換樹脂(三菱化学(株)製:SK-1BH)800gを添加し、1時間攪拌して脱アルカリ処理した。
次に、陽イオン交換樹脂を分離した後、陰イオン交換樹脂(三菱化学(株)製:SANUPC)400gを添加し、1時間攪拌して脱アニオン処理した。ついで、再び陽イオン交換樹脂(三菱化学(株)製:SK-1BH)400gを添加し、1時間攪拌して脱アルカリ処理してSiO2濃度5質量%のシリカ粒子分散液(B)を調製した。
この分散液を、限外濾過膜を用いてメタノールにて溶媒置換して、固形分濃度40.5質量%のメタノール分散液(B)を得た。
上記シリカメタノール分散液(B)100gを用いた以外は実施例1と同様にして、固形分濃度46.6質量%のシリカからなる表面処理金属酸化物微粒子樹脂PGME分散液(7)を調製した。
シリカアルミナゾルをシリカゾルPGME分散液(7)に変更した以外は実施例1と同様にして、固形分濃度41.8質量%の塗布液(15)を調製した。得られた塗布液(15)の組成を表1に示す。
《透明被膜付基材(15)の調製》
透明被膜形成用塗布液(15)を使用した以外は実施例1と同様に透明被膜付基材(15)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Example 15)
<<Preparation of coating liquid (15) for forming transparent film>>
Silica sol dispersion (manufactured by Nikki Shokubai Kasei Co., Ltd.; SI-80P; average particle diameter 80 nm, SiO concentration 40.5% by mass) was added to 1000 g of ion-exchanged water 6000 g, and then a cation exchange resin (Mitsubishi Chemical Co., Ltd. SK-1BH (manufactured by SK-1BH) (800 g) was added, and the solution was dealkalized by stirring for 1 hour.
Next, after separating the cation exchange resin, 400 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added and stirred for 1 hour for deanion treatment. Next, 400 g of a cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK-1BH) was added again, stirred for 1 hour, and dealkalized to prepare a silica particle dispersion (B) having a SiO 2 concentration of 5% by mass. did.
This dispersion liquid was solvent-substituted with methanol using an ultrafiltration membrane to obtain a methanol dispersion liquid (B) having a solid content concentration of 40.5% by mass.
A surface-treated metal oxide fine particle resin PGME dispersion (7) comprising silica having a solid content concentration of 46.6% by mass was prepared in the same manner as in Example 1, except that 100 g of the silica methanol dispersion (B) was used. .
A coating liquid (15) having a solid content concentration of 41.8% by mass was prepared in the same manner as in Example 1, except that the silica-alumina sol was changed to the silica sol PGME dispersion (7). Table 1 shows the composition of the obtained coating liquid (15).
<<Preparation of base material (15) with transparent film>>
A transparent film-coated substrate (15) was produced and evaluated in the same manner as in Example 1 except that the transparent film-forming coating solution (15) was used. The film thickness of the transparent film was 8 μm.
(実施例16)
《透明被膜形成用の塗布液(16)の調製》
シリカアルミナゾル分散液(日揮触媒化成(株)製;OSCAL1132;平均粒子径12nm、固形分濃度40.5質量%、分散媒:メタノールゾル、粒子屈折率1.46)100gにγ-メタアクリロオキシプロピルトリメトキシシラン6.08g(信越シリコ-ン(株)製:KBM-503、SiO2成分81.2質量%)を混合し超純水を8.80g添加し、5%アンモニア水0.40g添加し、50℃で6時間攪拌して表面処理した12nmのシリカアルミナゾル分散液を得た(固形分濃度40.4質量%)。
その後、ロータリーエバポレーターでプロピレングリコールモノメチルエーテル(PGME)に溶剤置換し、固形分60.0質量%のシリカアルミナゾルPGME分散液(8)を得た。
ついで、固形分濃度60.0質量%のシリカアルミナゾルPGME分散液(8)64.17gと、EO変性アクリレートバインダー(新中村化学工業(株)製:NKエステル A-DPH-18E)16.50g、と光重合開始剤(チバジャパン(株)製:イルガキュア184)2.48gとPGME4.36gとアセトン12.50gを充分に混合して、固形分濃度57.5質量%の塗布液(16)を調製した。得られた塗布液(16)の組成を表1に示す。
《透明被膜付基材(16)の調製》
塗布液(16)をバーコーター法(#12)で塗布した以外は実施例1と同様にして、透明被膜付基材(16)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Example 16)
<<Preparation of coating liquid (16) for forming transparent film>>
Silica-alumina sol dispersion (manufactured by Nikki Shokubai Kasei Co., Ltd.; OSCAL1132; average particle diameter 12 nm, solid content concentration 40.5% by mass, dispersion medium: methanol sol, particle refractive index 1.46) 100 g of γ-methacryloxy 6.08 g of propyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.: KBM-503, 81.2% by mass of SiO 2 component) was mixed, 8.80 g of ultrapure water was added, and 0.40 g of 5% aqueous ammonia was added. and stirred at 50° C. for 6 hours to obtain a surface-treated 12 nm silica-alumina sol dispersion (solid concentration: 40.4% by mass).
Thereafter, the solvent was replaced with propylene glycol monomethyl ether (PGME) using a rotary evaporator to obtain a silica alumina sol PGME dispersion (8) having a solid content of 60.0% by mass.
Then, 64.17 g of silica alumina sol PGME dispersion (8) having a solid content concentration of 60.0% by mass, EO-modified acrylate binder (manufactured by Shin-Nakamura Chemical Co., Ltd.: NK Ester A-DPH-18E) 16.50 g, and a photopolymerization initiator (manufactured by Ciba Japan Co., Ltd.: Irgacure 184) 2.48 g, PGME 4.36 g and acetone 12.50 g are sufficiently mixed to obtain a coating liquid (16) having a solid content concentration of 57.5% by mass. prepared. Table 1 shows the composition of the obtained coating liquid (16).
<<Preparation of base material (16) with transparent film>>
A base material (16) with a transparent film was produced and evaluated in the same manner as in Example 1, except that the coating liquid (16) was applied by a bar coater method (#12). The film thickness of the transparent film was 8 μm.
(実施例17)
《透明被膜形成用の塗布液(17)の調製》
実施例1で調製した固形分濃度46.6質量%のシリカゾルPGME分散液(1)30.06gと、EO変性アクリレートバインダー(新中村化学工業(株)製:NKエステル A-DPH-18E)6.00g、と光重合開始剤(チバジャパン(株)製:イルガキュア184)0.90gとPGME50.54gとアセトン12.50gを充分に混合して、固形分濃度20.9質量%の塗布液(17)を調製した。得られた塗布液(17)の組成を表1に示す。
《透明被膜付基材(17)の調製》
塗布液(17)をバーコーター法(#32)で塗布した以外は実施例1と同様にして、透明被膜付基材(17)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Example 17)
<<Preparation of coating liquid (17) for forming transparent film>>
30.06 g of silica sol PGME dispersion (1) having a solid content concentration of 46.6% by mass prepared in Example 1, and EO-modified acrylate binder (manufactured by Shin-Nakamura Chemical Co., Ltd.: NK Ester A-DPH-18E) 6 .00 g, and 0.90 g of a photopolymerization initiator (Ciba Japan Co., Ltd.: Irgacure 184), 50.54 g of PGME, and 12.50 g of acetone were sufficiently mixed to obtain a coating liquid having a solid content concentration of 20.9% by mass ( 17) was prepared. Table 1 shows the composition of the obtained coating liquid (17).
<<Preparation of substrate with transparent film (17)>>
A substrate with a transparent film (17) was produced and evaluated in the same manner as in Example 1, except that the coating liquid (17) was applied by a bar coater method (#32). The film thickness of the transparent film was 8 μm.
(実施例18)
《透明被膜形成用の塗布液(18)の調製》
アクリルシリコーン系レベリング剤(楠本化成(株)社製 UVX-3750,固形分50.0%)0.001g添加して混合した以外は実施例1と同様にして、固形分濃度41.8質量%の塗布液(18)を調製した。得られた塗布液(18)の組成を表1に示す。
《透明被膜付基材(18)の調製》
塗布液(18)を使用した以外は実施例1と同様に透明被膜付基材(18)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Example 18)
<<Preparation of coating liquid (18) for forming transparent film>>
In the same manner as in Example 1 except that 0.001 g of an acrylic silicone leveling agent (UVX-3750 manufactured by Kusumoto Kasei Co., Ltd., solid content 50.0%) was added and mixed, the solid content concentration was 41.8% by mass. was prepared. Table 1 shows the composition of the obtained coating liquid (18).
<<Preparation of substrate with transparent film (18)>>
A substrate with a transparent film (18) was produced and evaluated in the same manner as in Example 1 except that the coating liquid (18) was used. The film thickness of the transparent film was 8 μm.
(実施例19)
《透明被膜付基材(19)の調製》
基材を50μmPETフィルム(東洋紡(株)製:コスモシャインA4300)に変更した以外は実施例1と同様にして、塗布液(1)を塗布して透明被膜付基材(19)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Example 19)
<<Preparation of substrate with transparent film (19)>>
Coating liquid (1) was applied in the same manner as in Example 1 except that the substrate was changed to a 50 μm PET film (manufactured by Toyobo Co., Ltd.: Cosmoshine A4300) to produce a substrate with a transparent film (19), evaluated. The film thickness of the transparent film was 8 μm.
(比較例1)
《透明被膜形成用の塗布液(R1)の調製》
固形分濃度46.6質量%のシリカゾルPGME分散液(1)51.52gと、ジペンタエリスリトールヘキサアクリレート(共栄社化学(株)製:ライトアクリレート DPE-6A)16.00g、と光重合開始剤(チバジャパン(株)製:イルガキュア184)2.40gとPGME17.58gとアセトン12.50gを充分に混合して固形分濃度42.4質量%の塗布液(R1)を調製した。得られた塗布液(R1)の組成を表に示す。
《透明被膜付基材(R1)の調製》
塗布液(R1)を使用した以外は実施例1と同様に透明被膜付基材(R1)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Comparative example 1)
<<Preparation of coating liquid (R1) for forming transparent film>>
51.52 g of silica sol PGME dispersion (1) having a solid content concentration of 46.6% by mass, 16.00 g of dipentaerythritol hexaacrylate (manufactured by Kyoeisha Chemical Co., Ltd.: light acrylate DPE-6A), and a photopolymerization initiator ( Ciba Japan Co., Ltd.: Irgacure 184) (2.40 g), PGME (17.58 g), and acetone (12.50 g) were thoroughly mixed to prepare a coating liquid (R1) having a solid concentration of 42.4% by mass. The composition of the obtained coating liquid (R1) is shown in the table.
<<Preparation of substrate with transparent film (R1)>>
A substrate with a transparent film (R1) was produced and evaluated in the same manner as in Example 1 except that the coating liquid (R1) was used. The film thickness of the transparent film was 8 μm.
(比較例2)
《透明被膜形成用の塗布液(R2)の調製》
ジペンタエリスリトールヘキサアクリレートをウレタンアクリレート(新中村化学(株)製:NKオリゴ UA-33H、官能基:ウレタンアクリレート、官能基数:9、分子量:4,000、固形分濃度100%)に変更した以外は比較例1と同様にして、固形分濃度42.4質量%の塗布液(R2)を調製した。得られた塗布液(R2)の組成を表1に示す。
《透明被膜付基材(R2)の調製》
塗布液(R2)を使用した以外は実施例1と同様に透明被膜付基材(R2)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Comparative example 2)
<<Preparation of coating liquid (R2) for forming transparent film>>
Except for changing dipentaerythritol hexaacrylate to urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.: NK Oligo UA-33H, functional group: urethane acrylate, number of functional groups: 9, molecular weight: 4,000, solid content concentration 100%) A coating liquid (R2) having a solid concentration of 42.4% by mass was prepared in the same manner as in Comparative Example 1. Table 1 shows the composition of the obtained coating liquid (R2).
<<Preparation of substrate with transparent film (R2)>>
A substrate with a transparent film (R2) was produced and evaluated in the same manner as in Example 1 except that the coating liquid (R2) was used. The film thickness of the transparent film was 8 μm.
(比較例3)
《透明被膜形成用の塗布液(R3)の調製》
EO変性アクリレートバインダーを新中村化学工業(株)製:NKエステル A-DPH-48Eに変更した以外は実施例1と同様にして、固形分濃度41.8質量%の塗布液(R3)を調製した。得られた塗布液(R3)の組成を表1に示す。
《透明被膜付基材(R3)の調製》
塗布液(R3)を使用した以外は実施例1と同様に透明被膜付基材(R3)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Comparative Example 3)
<<Preparation of coating liquid (R3) for forming transparent film>>
A coating liquid (R3) having a solid content concentration of 41.8% by mass was prepared in the same manner as in Example 1, except that the EO-modified acrylate binder was changed to NK Ester A-DPH-48E manufactured by Shin-Nakamura Chemical Co., Ltd. did. Table 1 shows the composition of the obtained coating liquid (R3).
<<Preparation of substrate with transparent film (R3)>>
A substrate with a transparent film (R3) was produced and evaluated in the same manner as in Example 1 except that the coating liquid (R3) was used. The film thickness of the transparent film was 8 μm.
(比較例4)
《透明被膜形成用の塗布液(R4)の調製》
EO変性アクリレートバインダーを新中村化学工業(株)製:NKエステル A-1000に変更した以外は実施例1と同様にして、固形分濃度41.8質量%の塗布液(R4)を調製した。得られた塗布液(R4)の組成を表1に示す。
《透明被膜付基材(R4)の調製》
塗布液(R4)を使用した以外は実施例1と同様に透明被膜付基材(R4)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Comparative Example 4)
<<Preparation of coating liquid (R4) for forming transparent film>>
A coating liquid (R4) having a solid content concentration of 41.8% by mass was prepared in the same manner as in Example 1, except that the EO-modified acrylate binder was changed to NK Ester A-1000 manufactured by Shin-Nakamura Chemical Co., Ltd. Table 1 shows the composition of the obtained coating liquid (R4).
<<Preparation of substrate with transparent film (R4)>>
A substrate with a transparent film (R4) was produced and evaluated in the same manner as in Example 1 except that the coating liquid (R4) was used. The film thickness of the transparent film was 8 μm.
(比較例5)
《透明被膜形成用の塗布液(R5)の調製》
EO変性アクリレートバインダー(新中村化学工業(株)製:NKエステル A-DPH-18E)40.00g、と光重合開始剤(チバジャパン(株)製:イルガキュア184)6.00gとPGME41.50gとアセトン12.50gを充分に混合して固形分濃度46.0質量%の塗布液(R5)を調製した。得られた塗布液(R5)の組成を表1に示す。
《透明被膜付基材(R5)の調製》
塗布液(R5)を使用した以外は実施例1と同様に透明被膜付基材(R5)を製造し、評価した。透明被膜の膜厚は8μmであった。
ここで、表面処理金属酸化物粒子が含まれた実施例1の透明被膜付基材(1)と比較すると、透明被膜付基材(1)の方が、鉛筆硬度、耐擦傷性、全光線透過率および密着性が高く、接触角およびカーリングが低く、外観も良好であることが判った。
(Comparative Example 5)
<<Preparation of coating liquid (R5) for forming transparent film>>
EO-modified acrylate binder (manufactured by Shin-Nakamura Chemical Co., Ltd.: NK Ester A-DPH-18E) 40.00 g, and photopolymerization initiator (manufactured by Ciba Japan Co., Ltd.: Irgacure 184) 6.00 g and PGME 41.50 g 12.50 g of acetone was sufficiently mixed to prepare a coating liquid (R5) having a solid concentration of 46.0% by mass. Table 1 shows the composition of the obtained coating liquid (R5).
<<Preparation of substrate with transparent film (R5)>>
A substrate with a transparent film (R5) was produced and evaluated in the same manner as in Example 1 except that the coating liquid (R5) was used. The film thickness of the transparent film was 8 μm.
Here, when compared with the substrate with a transparent film (1) of Example 1 containing the surface-treated metal oxide particles, the substrate with a transparent film (1) has better pencil hardness, scratch resistance, and total light It was found that the transmittance and adhesion were high, the contact angle and curling were low, and the appearance was good.
(比較例6)
《透明被膜形成用の塗布液(R6)の調製》
シリカアルミナゾル分散液(日揮触媒化成(株)製;OSCAL1132;平均粒子径12nm、固形分濃度40.5質量%、分散媒:メタノールゾル、粒子屈折率1.46)59.26gと、EO変性アクリレートバインダー(新中村化学工業(株)製:NKエステル A-DPH-18E)16.00g、と光重合開始剤(チバジャパン(株)製:イルガキュア184)2.40gとPGME9.84gとアセトン12.50gを充分に混合して固形分濃度42.4質量%の塗布液(R6)を調製した。得られた塗布液(R6)の組成を表1に示す。
《透明被膜付基材(R6)の調製》
塗布液(R6)を使用した以外は実施例1と同様に透明被膜付基材(R6)を製造し、評価した。透明被膜の膜厚は8μmであった。
(Comparative Example 6)
<<Preparation of coating liquid (R6) for forming transparent film>>
Silica alumina sol dispersion (manufactured by Nikki Shokubai Kasei Co., Ltd.; OSCAL1132; average particle diameter 12 nm, solid content concentration 40.5% by mass, dispersion medium: methanol sol, particle refractive index 1.46) 59.26 g, and EO-modified acrylate 16.00 g of a binder (manufactured by Shin-Nakamura Chemical Co., Ltd.: NK Ester A-DPH-18E), 2.40 g of a photopolymerization initiator (manufactured by Chiba Japan Co., Ltd.: Irgacure 184), 9.84 g of PGME, and 12.0 g of acetone. A coating liquid (R6) having a solid content concentration of 42.4% by mass was prepared by thoroughly mixing 50 g. Table 1 shows the composition of the obtained coating liquid (R6).
<<Preparation of substrate with transparent film (R6)>>
A substrate with a transparent film (R6) was produced and evaluated in the same manner as in Example 1 except that the coating liquid (R6) was used. The film thickness of the transparent film was 8 μm.
Claims (4)
金属酸化物粒子の表面に有機珪素化合物が設けられ、平均粒子径が5~500nmの表面処理金属酸化物粒子と、
親水性溶媒または極性溶媒である有機溶媒と、を含み、
前記アルキレンオキサイド変性(メタ)アクリレート樹脂は、(メタ)アクリレート官能基数が4~8、アルキレンオキサイド基数が3~24である多官能アクリレートモノマー樹脂であり、
前記有機珪素化合物は、前記金属酸化物粒子100質量部に対し、Rn-SiO(4-n)/2(但し、式中、Rは炭素数1~10の非置換または置換炭化水素基で、互いに同一であっても異なっていてもよい。nは1~3の整数)として0.1~50質量部、前記表面金属酸化物粒子に含まれ、
前記表面処理金属酸化物粒子は、前記アルキレンオキサイド変性(メタ)アクリレート樹脂と前記表面処理金属酸化物粒子の固形分の合計量に対して50~90質量%含まれ、
固形分濃度が5~70質量%であることを特徴とする透明被膜形成用の塗布液。 Alkylene oxide-modified (meth)acrylate resin,
surface-treated metal oxide particles having an organosilicon compound provided on the surface of the metal oxide particles and having an average particle size of 5 to 500 nm;
an organic solvent that is a hydrophilic solvent or a polar solvent ,
The alkylene oxide-modified (meth)acrylate resin is a polyfunctional acrylate monomer resin having 4 to 8 (meth)acrylate functional groups and 3 to 24 alkylene oxide groups,
The organosilicon compound is R n —SiO (4-n)/2 (where R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms) per 100 parts by mass of the metal oxide particles. , which may be the same or different, n is an integer of 1 to 3), 0.1 to 50 parts by mass, contained in the surface metal oxide particles,
The surface-treated metal oxide particles are contained in an amount of 50 to 90% by mass based on the total solid content of the alkylene oxide-modified (meth)acrylate resin and the surface-treated metal oxide particles,
A coating liquid for forming a transparent film, characterized by having a solid content concentration of 5 to 70% by mass.
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JP2013163765A (en) | 2012-02-10 | 2013-08-22 | Toyo Ink Sc Holdings Co Ltd | Active energy ray-curable composition |
JP2013177339A (en) | 2012-02-28 | 2013-09-09 | Dai Ichi Kogyo Seiyaku Co Ltd | Alkylene oxide-modified dipentaerythritol (meth)acrylate and reactive composition containing the same |
WO2015108834A1 (en) | 2014-01-15 | 2015-07-23 | 3M Innovative Properties Company | Hardcoats comprising alkoxylated multi(meth)acrylate monomers and surface treated nanoparticles |
JP2015193756A (en) | 2014-03-31 | 2015-11-05 | 日揮触媒化成株式会社 | Organic resin dispersed sol, coating liquid for formation of transparent film, method of producing coating liquid for formation of transparent film and substrate with transparent film |
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JP2021165404A (en) | 2021-10-14 |
TW201800504A (en) | 2018-01-01 |
TWI726054B (en) | 2021-05-01 |
CN107129713A (en) | 2017-09-05 |
JP2017155073A (en) | 2017-09-07 |
JP7153114B2 (en) | 2022-10-13 |
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