WO2007004447A1 - Composition durcissable antistatique, film durci de celle-ci et corps multicouche antistatique - Google Patents

Composition durcissable antistatique, film durci de celle-ci et corps multicouche antistatique Download PDF

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Publication number
WO2007004447A1
WO2007004447A1 PCT/JP2006/312631 JP2006312631W WO2007004447A1 WO 2007004447 A1 WO2007004447 A1 WO 2007004447A1 JP 2006312631 W JP2006312631 W JP 2006312631W WO 2007004447 A1 WO2007004447 A1 WO 2007004447A1
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Prior art keywords
group
particles
formula
meth
compound
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PCT/JP2006/312631
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English (en)
Japanese (ja)
Inventor
Yasunobu Suzuki
Noriyasu Shinohara
Takayoshi Tanabe
Hiroomi Shimomura
Takaro Yashiro
Tetsuya Yamamura
Ryoji Tatara
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Jsr Corporation
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Priority claimed from JP2005191247A external-priority patent/JP5157046B2/ja
Priority claimed from JP2005191246A external-priority patent/JP2007007984A/ja
Application filed by Jsr Corporation filed Critical Jsr Corporation
Publication of WO2007004447A1 publication Critical patent/WO2007004447A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/30—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being formed of particles, e.g. chips, granules, powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/025—Particulate layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/21—Anti-static
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/536—Hardness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/20—Displays, e.g. liquid crystal displays, plasma displays

Definitions

  • Antistatic curable composition cured film thereof and antistatic laminate
  • the present invention relates to an antistatic laminate. More specifically, it has excellent curability and is made of various base materials such as plastic (polycarbonate, polymethylmetatalylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cell mouthwater resin, ABS resin, AS resin, norbornene resin, etc.), metal, wood, paper, glass, ceramic, slate, etc., surface coating with excellent antistatic properties, hardness, scratch resistance and transparency ( The present invention relates to a curable composition capable of forming a coating film), a cured film obtained by curing the composition, and an antistatic laminate including the cured film layer.
  • plastic polycarbonate, polymethylmetatalylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cell mouthwater resin, ABS resin, AS resin, norbornene resin, etc.
  • the present invention relates to a curable composition capable of forming a coating film), a cured film obtained
  • curable compositions capable of forming a cured film having a high refractive index are required in addition to the above-described requirements for the use of antireflection films such as film-type liquid crystal elements, touch panels, and plastic optical components.
  • the composition has excellent coating properties as a curable composition, and has a high hardness and a cured film. It has a high refractive index and is excellent in scratch resistance and adhesion to the low refractive index layer used in the base material and the laminated body described later, and a laminated body in which a low refractive index film is laminated on the cured film by coating. In some cases, it is still possible to obtain a product having a low reflectivity and excellent antistatic properties and transparency.
  • Patent Document 1 describes a conductive coating agent comprising an ultrafine powder of a conductive filler and an ultraviolet curable resin as a binder.
  • the coated cured film can be formed without increasing the temperature, and the conductive coated cured film can be easily formed on a transparent substrate without heat resistance.
  • the conductive filler it is described that titanium oxide oxide doped with antimony is preferable in terms of dispersibility and surface area of low haze.
  • acrylic resin, urethane resin or silicone resin is used as the ultraviolet curable resin.
  • the conductive coating agent described in Patent Document 1 contains a solvent.
  • Patent Document 2 includes (meth) acrylic acid ester mixture (A), photopolymerization initiator (B), ethylenically unsaturated group-containing urethane oligomer (C), colloidal silica sol (D) and diluent ( E)
  • a photosensitive resin composition for hard coat agent that also has strength and a hard coat film comprising the same are described, and it is described that the obtained film has good pencil hardness, curl, and adhesion to a substrate.
  • the inorganic particles ((D)) used in the examples are only silica particles, and the silica particles are not subjected to surface modification of the particles. Moreover, since the silica particle is used, electroconductivity is not provided.
  • Patent Documents 3 and 4 disclose a curable composition containing tin-containing indium oxide (ITO) particles and a cured film (laminated body) having high conductivity obtained by curing the composition. Yes.
  • ITO indium oxide
  • a radiation curable composition has been used on the surface of the equipment to provide a scratch-resistant and adhesive coating (hard coat) and an antistatic function.
  • a coating film antistatic film
  • a multilayer structure (antireflection film) of a low refractive index layer and a high refractive index layer is formed on the surface of the optical article.
  • optical articles such as plastic lenses are required to prevent dust from being attached due to static electricity and to improve the reduction in transmittance due to reflection. Therefore, it is required to prevent dust from adhering due to static electricity and to prevent reflection on the screen. It is becoming.
  • Such techniques include, for example, a composition containing sulfonic acid and phosphoric acid monomers as ion-conductive components (Patent Document 5), and a composition containing chain metal powder (Patent Document 6). ), Tin oxide particles, polyfunctional acrylate, and a composition mainly composed of a copolymer of methyl methacrylate and polyether acrylate (Patent Document 7), a conductive coating composition containing a pigment coated with a conductive polymer Material (Patent Document 8), trifunctional acrylic acid ester, monofunctional ethylenically unsaturated group-containing compound, photopolymerization initiator, and conductive powder material (Patent Document 9), dispersed with silane coupler Conductive paint containing hydrolyzate of antimony-doped tin oxide particles and tetraalkoxysilane, photosensitizer, and organic solvent (Patent Document 10) A curable resin composition containing a reaction product of an alkoxysilane containing
  • an antireflection film including a low refractive index layer made of a cured product having excellent property and stain resistance.
  • These display panels are required to have scratch resistance that is often wiped with gauze impregnated with ethanol or the like in order to remove attached fingerprints, dust, and the like. There is also a demand for contamination resistance that can easily wipe off attached fingerprints and dust.
  • the antireflection film is provided on the liquid crystal unit in a state of being bonded to a polarizing plate.
  • the base material for example, triacetyl cellulose is used, but in the antireflection film using such a base material, in order to increase the adhesion when bonded to the polarizing plate, In general, it is necessary to carry out the quenching with an aqueous alkaline solution. Therefore, in applications of liquid crystal display panels, there is a demand for an antireflection film excellent in alkali resistance, particularly in durability.
  • a fluorine-based resin coating containing a hydroxyl group-containing fluoropolymer is known (for example, Patent Documents 13 to 15).
  • the obtained coating film had excellent weather resistance, but was poor in scratch resistance and durability!
  • an isocyanate group-containing unsaturated compound having at least one isocyanate group and at least one addition-polymerizable unsaturated group, and a hydroxyl group-containing fluorine-containing weight.
  • a coating composition containing an unsaturated group-containing fluorinated vinyl polymer obtained by reacting a polymer with an isocyanate group at a ratio of the number of isocyanate groups to the number of Z hydroxyl groups of 0.01 to 1.0.
  • a coating composition containing such a polymer can be cured at a low temperature in a short time, but a curing agent such as melamine resin is further used to react the remaining hydroxyl groups. Needed to be cured. Furthermore, the coating film obtained in the above publication has a problem that it is sufficient in terms of coatability and scratch resistance.
  • Patent Document 1 Japanese Patent Laid-Open No. 7-196956 Claims 1, 4, 5, Paragraph No. 0022, Table 1
  • Patent Document 2 Japanese Patent Laid-Open No. 2002-235018 Patent Claim, Paragraph No. 0037
  • Patent Document 3 JP-A-6-232586
  • Patent Document 4 JP-A-7-242843
  • Patent Document 5 JP-A-47-34539
  • Patent Document 6 Japanese Patent Application Laid-Open No. 55-78070
  • Patent Document 7 Japanese Patent Laid-Open No. 60-60166
  • Patent Document 8 Japanese Patent Laid-Open No. 2-194071
  • Patent Document 9 Japanese Patent Laid-Open No. 4 172634
  • Patent Document 10 JP-A-6-2644009
  • Patent Document 11 Japanese Unexamined Patent Publication No. 2000-143924
  • Patent Document 12 Japanese Patent Laid-Open No. 2001-131485
  • Patent Document 13 Japanese Unexamined Patent Publication No. 57-34107
  • Patent Document 14 Japanese Patent Laid-Open No. 59-189108
  • Patent Document 15 JP-A-60-67518
  • Patent Document 16 Japanese Patent Laid-Open No. 61-296073
  • the conventional techniques as described in the above prior art documents have the following problems.
  • the composition described in Patent Document 5 uses an ion conductive material, but its performance fluctuates due to drying which is not sufficient in antistatic performance. Since the composition described in Patent Document 6 disperses the chain-like metal powder having a large particle size, the transparency is lowered. Since the composition described in Patent Document 7 contains a large amount of a non-curable dispersant, the strength of the cured film decreases. Since the material described in Patent Document 9 contains high-concentration chargeable inorganic particles, transparency is lowered.
  • the paint described in Patent Document 10 has insufficient long-term storage stability. Patent Document 11 does not disclose any method for producing a composition having antistatic performance. When a transparent conductive film is formed by applying and drying the paint described in Patent Document 12, the organic matrix made of Noinda's blend does not have a cross-linked structure, so it cannot be said that the organic solvent resistance is sufficient. .
  • the present invention has been made in view of the above-mentioned problems, has excellent coating properties, and has high hardness and high refractive index on the surface of various base materials, as well as scratch resistance and It is an object of the present invention to provide a curable composition capable of forming a coating film (coating) excellent in adhesion with a substrate and a low refractive index layer, and a cured product excellent in antistatic property and transparency.
  • An object of the present invention is to provide a curable composition capable of forming a cured film capable of simultaneously achieving high refractive index, high transparency, and excellent antistatic function.
  • the present invention can also exhibit sufficient antistatic performance even when the amount of the conductive particles is small, has excellent curability, and has antistatic properties on the surface of various substrates.
  • An object of the present invention is to provide an antireflection film laminate having an anti-reflection function.
  • the inventors of the present invention have made extensive studies and have combined tin-containing indium oxide (ITO) particles with oxide particles of a specific element and an organic compound containing a polymerizable unsaturated group.
  • the curable composition containing the combined particles By using the curable composition containing the combined particles, the antistatic property and transparency are excellent even when the ITO content is reduced, and the tin-containing indium oxide (ITO) particles are more than single particles.
  • the inventors have found that a cured film having a high refractive index can be formed, and completed the present invention.
  • conductive particles having a specific particle size, having two or more polymerizable unsaturated groups in the molecule has been completed by finding that the above object can be achieved by a laminate having a cured film layer obtained by curing a composition containing a compound, a photopolymerization initiator, and a solvent.
  • the anti-reflective laminate has scratch resistance and resistance.
  • the present inventors have found that the contamination property is improved and completed the present invention. That is, the present invention provides the following curable composition, a cured film thereof, a method for producing the cured film, a laminate, and a method for producing the laminate.
  • a laminate comprising the layer in a proportion of (A) component 7 to 40% by mass and (Ba) component 20 to 60% by mass.
  • the laminated product according to any one of 1 to 6 above which is a cured product of a curable resin composition containing an antireflective film in which a layer having a refractive index of 1.30 to 1.45 at a wavelength of 589 nm is formed. body. 8.
  • the total of the following structural units (a) to (c) is 100 mol%, (&) 20 to 70 mol% (1)) 10 to 70 mol% And (.)
  • R 11 represents a fluorine atom, a fluoroalkyl group or a group represented by —OR 12 (R 12 represents an alkyl group or a fluoroalkyl group)]
  • R 13 is a hydrogen atom or a methyl group
  • R 14 is an alkyl group,-(CH) —OR 15
  • R 15 represents an alkyl group or a glycidyl group, c represents a number of 0 or 1), a carboxyl group or an alkoxycarbo group] [Chemical 3]
  • R 16 represents a hydrogen atom or a methyl group
  • R 17 represents a hydrogen atom or a hydroxyalkyl group
  • V represents a number of 0 or 1
  • Compound 33-1 Porous silica particles (HI) consisting of 1 mol% hydrolyzate and Z or hydrolysis condensate and having an average particle size of 5-50 nm
  • X each independently represents an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group, an alkyloxycarbon group having 2 to 4 carbon atoms, or an alkylamino group having 1 to 4 carbon atoms.
  • R 29 Is an alkenyl group having 2 to 8 carbon atoms, an attaryloxyalkyl group having 4 to 8 carbon atoms, or a methacryloxyalkyl group having 5 to 8 carbon atoms, and j is an integer of 1 to 3.
  • Formula (22) X in formula (23) and X in formula (23) may be the same or different.
  • X each independently represents an alkoxy group having 1 to 4 carbon atoms, a halogeno group, an isocyanate group, an alkyloxycarbon group having 2 to 4 carbon atoms, or an alkylamino group having 1 to 4 carbon atoms.
  • R 29 Is an alkenyl group having 2 to 8 carbon atoms, an attaryloxyalkyl group having 4 to 8 carbon atoms, or a methacryloxyalkyl group having 5 to 8 carbon atoms
  • j is an integer of 1 to 3.
  • R 3 is 1 carbon number -12 fluorine-substituted alkyl group
  • k represents an integer of 1 to 3.
  • X in formula (22), X in formula (23) and X in formula (24) may be the same or different. May be.
  • the total of the components (A) to (D) is 100% by mass, the component (A) is 7 to 40% by mass, and the component (B) is 20 to 60% by mass. 14.
  • Y represents ⁇ , 0 (oxygen atom) or S (Yu atom), and V represents O or S. ]
  • a cured film obtained by curing the curable composition according to any one of the above 13 to 16.
  • a method for producing a cured film comprising a step of irradiating the curable composition according to any one of 13 to 16 above with radiation to cure the composition.
  • the coating material has excellent coating properties, and has high hardness and high refractive index on the surface of various substrates, and has antistatic properties, substrates, low refractive index layers, and other hard materials. It is possible to provide a curable composition capable of forming a coating film (film) excellent in adhesion and transparency with a coating layer and the like, and a cured film thereof.
  • the curability is excellent and can form a coating film (film) having excellent antistatic property, hardness, scratch resistance, and transparency on the surface of various substrates.
  • An antistatic laminate having a cured film formed by curing the composition can be provided.
  • tin-containing indium oxide ( ⁇ ) particles in order to obtain sufficient conductivity using tin-containing indium oxide ( ⁇ ), expensive tin-containing indium oxide ( ⁇ ) particles must be blended at a high content (usually about 60% by weight). According to the present invention, even when the content of tin-containing indium oxide ( ⁇ ) particles is low, sufficient conductivity can be exhibited, and the antistatic laminate having a cured film excellent in antistatic performance. You can get a body.
  • the laminate of the present invention is useful as an optical component having an antistatic function, particularly as an antireflection film having an antistatic function.
  • FIG. 1 is a schematic view showing a basic configuration of a laminate of the present invention.
  • FIG. 2A is a schematic view showing a first form of an antireflection film with an antistatic function of the present invention.
  • FIG. 2B is a schematic diagram showing another form of the first form of the antireflection film with an antistatic function of the present invention.
  • FIG. 2C is a schematic view showing another form of the first form of the antireflection film with an antistatic function of the present invention.
  • FIG. 2D is a schematic view showing a second embodiment of the antireflection film with an antistatic function of the present invention.
  • FIG. 2E is a schematic view showing another form of the second form of the antireflection film with an antistatic function of the present invention.
  • FIG. 2F is a schematic view showing another form of the second form of the antireflection film with an antistatic function of the present invention.
  • FIG. 2G is a schematic view showing a third embodiment of the antireflection film with an antistatic function of the present invention.
  • FIG. 2H is a schematic view showing another form of the third form of the antireflection film with an antistatic function of the present invention.
  • FIG. 21 is a schematic view showing another form of the third form of the antireflection film with an antistatic function of the present invention.
  • FIG. 3A Containing tin-containing indium oxide (ITO) particles and zirconium oxide (ZrO) particles of the present invention
  • FIG. 2 is an electron micrograph showing a substrate side interface in a cured film obtained by curing the curable composition to be formed, showing a state where ITO particles are unevenly distributed on the substrate side interface.
  • FIG. 3B Containing tin-containing indium oxide (ITO) particles and zircoure (ZrO) particles of the present invention
  • the laminate of the present invention comprises a base material, (A) tin-containing indium oxide fine particles, (Ba) oxide particles of at least one element selected from the group force consisting of zirconium, titanium, aluminum, cerium, tin and zinc; C) Polymer-containing layer (hereinafter referred to as “cured film layer” t Force S).
  • the cured film layer can be formed by curing a curable composition containing the following components (A) to (D).
  • (B) Group power consisting of zirconium, titanium, aluminum, cerium, tin, and zinc. At least one element selected from acid-rich particles (Ba) and an organic compound (Bb) containing a polymerizable unsaturated group. Particles formed by binding (hereinafter referred to as “Reactive Particles (B)”)
  • the antireflection film which is a preferred embodiment of the laminate of the present invention, has an antistatic layer and a low refractive index layer composed of at least the cured film layer close to the base material on the base material.
  • the side force is also an antireflection film laminated in this order, and the low refractive index layer is a cured product of a curable resin composition containing the following components (G) and (H).
  • the laminate 1 of the present invention has a base film 10 and a cured film layer 12 formed by curing the curable composition.
  • the laminate of the present invention may be provided with various layers depending on the purpose as long as it has at least the substrate 10 and the cured film layer 12.
  • the layer provided according to the purpose will be described later.
  • the laminate 1 of the present invention has the cured film layer 12 having excellent scratch resistance and adhesion, it is particularly useful as a hard coat.
  • the laminate 1 of the present invention has an antistatic function by providing a cured film layer 12 having an excellent antistatic function on a substrate having various shapes such as a film, a plate, or a lens. Useful as a laminate.
  • an antireflection film having an antistatic function for various display panels such as a CRT, a liquid crystal display panel, a plasma display panel, an electret luminescence display panel (hereinafter, referred to as “antireflection film”)
  • an antireflection film with an antistatic function such as a plastic lens, a polarizing film, and a solar battery panel.
  • composition or “antistatic layer-forming composition”.
  • the laminate can be given a function as a conductive film and a function as Z or a hard coat.
  • composition for forming an antistatic layer composition for forming an antistatic layer
  • the tin-containing indium oxide fine particles (A) used in the present invention are components for imparting conductivity (antistatic properties) to a cured film obtained by curing the composition of the present invention.
  • the tin-containing indium oxide fine particles (A) used in the present invention are not particularly limited, but are preferably in the form of powder or solvent-dispersed sol.
  • the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility.
  • organic solvents examples include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, Esters such as ethyl acetate, y butyrolatatatone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and polyethylene glycol monobutyl ether; aromatic carbonization such as benzene, toluene and xylene Hydrogen: Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclo
  • methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene And xylene are preferred.
  • the primary particle diameter of the tin-containing indium oxide particles (A) is preferably in the range of 1 to 20 nm, more preferably in the range of 5 to 15 nm.
  • the primary particle diameter exceeds 20 nm, the transparency when cured is reduced, and the surface state when coated is apt to deteriorate.
  • various surfactants and amines may be added to improve the dispersibility of the particles.
  • the primary particle diameter of the tin-containing indium oxide particles (A) can be measured, for example, as the number average particle diameter by observation with a transmission electron microscope. If the particles are not spherical, the average of the major axis and minor axis is the particle size.
  • the shape of the tin-containing indium oxide particles (A) is spherical, hollow, porous, rod-like, plate-like, fiber-like, or indefinite, and preferably spherical.
  • the usage form of the tin-containing indium oxide particles (A) can be used in a dry state, or in a state dispersed in water or an organic solvent.
  • a dispersion of fine oxide particles known in the art as a solvent dispersion sol of the above tin-containing indium oxide can be directly used.
  • solvent-dispersed sols of tin-containing indium oxide include, for example, Fuji Chemical Co., Ltd., trade name: Hout form NID-20 (—second particle size: 13 nm; isopropanol dispersion), manufactured by CY Kasei Co., Ltd.
  • Examples of the water-dispersed sol of tin-containing indium oxide include trade name: Pastoran (primary particle size: 30 nm) manufactured by Mitsui Metal Mining Co., Ltd.
  • Examples of the tin-containing indium oxide powder include products manufactured by Fuji Chemical Co., Ltd., Mitsui Metal Mining Co., Ltd., and Mitsubishi Materials Corporation.
  • the amount of component (A) in the curable composition of the present invention is usually within the range of 7 to 40% by mass, preferably 10 with the total of components (A) to (D) as 100% by mass. Within the range of ⁇ 40% by mass. When the content of component (A) is less than 7% by mass, sufficient antistatic properties can be obtained. When the amount exceeds 40% by mass, the transparency of the resulting cured film may be impaired.
  • the amount of component (A) means a solid content, and when component (A) is used in the form of a solvent-dispersed sol, the amount of the component does not include the amount of solvent.
  • the reactive particles (B) constituting the component (B) of the present invention are oxide particles of at least one element (hereinafter referred to as “a group power” consisting of zirconium, titanium, aluminum, cerium, tin and zinc).
  • Acid oxide particles (Ba) ”and organic compounds containing a polymerizable unsaturated group (hereinafter also referred to as“ organic compound (Bb) ”) (preferably the above formula (1) Reactive particles obtained by reacting with a specific organic compound containing a group represented by
  • the reactive particles (B) By using the reactive particles (B), good scratch resistance and high transparency can be maintained, and the resulting cured film can have a high refractive index.
  • the oxide particles (Ba) used in the present invention are at least one selected from the group power consisting of zirconium, titanium, aluminum, cerium, tin and zinc from the viewpoint of achromaticity of the cured film of the resulting curable composition. Elemental oxide particles.
  • oxide particles (Ba) examples include particles such as alumina, zirconium oxide, titanium oxide, zinc oxide, tin oxide, and cerium oxide.
  • zircoua is preferable from the viewpoint of scratch resistance, which is preferable for alumina and zircoua particles.
  • the oxide particles (Ba) are preferably in the form of powder or solvent-dispersed sol.
  • the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility.
  • organic solvents examples include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, Esters such as ethyl lactate, ⁇ -butyrolatatone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc .; ethylene glycol monoremonomethylenoatenore, diethyleneglycolenobutinoreatenoate, etc.
  • alcohols such as methanol, ethanol, isopropanol, butanol, and octanol
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone
  • Aromatic hydrocarbons such as benzene, toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
  • methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.
  • the number average particle diameter of the oxide particles (Ba) is preferably 0.001 ⁇ m to 2 ⁇ m, more preferably 0.001 ⁇ m to 0.2 ⁇ m force, and 0.001 ⁇ m to 0.1 ⁇ m force ⁇ Especially preferred.
  • the number average particle diameter exceeds 2 m, the transparency when cured is reduced, and the surface state when coated is liable to deteriorate.
  • various surfactants and amines may be added to improve the dispersibility of the particles.
  • the number average particle diameter of the oxide particles (Ba) can be measured by, for example, a dynamic light scattering particle size distribution measuring apparatus manufactured by Horiba, Ltd.
  • aqueous dispersion of alumina product names manufactured by Nissan Chemical Industries, Ltd .: Alumina sol 100, 1 200, 1 520; As isopropanol dispersions of alumina, products manufactured by Sumitomo Osaka Cement Co., Ltd. AS-1501; Toluene dispersion of alumina manufactured by Sumitomo Osaka Cement Co., Ltd. Product name: AS-150T; Zircoyu toluene dispersion manufactured by Sumitomo Osaka Cement Co., Ltd.
  • Product name HXU-110JC; For powders and solvent dispersions of alumina, titanium oxide, tin oxide, zinc oxide, etc., manufactured by CIA Kasei Co., Ltd.
  • ITO powder is a product manufactured by Mitsubishi Materials Co., Ltd .;
  • the oxide particles (Ba) have a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indefinite shape, and preferably a spherical shape.
  • the specific surface area of the oxide particles (Ba) (by the BET specific surface area measurement method using nitrogen) is preferably 10 to: L000m 2 Zg, and more preferably 100 to 500 m 2 Zg.
  • These acid oxide particles (Ba) can be used in a dry powder, or dispersed in water or an organic solvent. For example, a finely divided dispersion of acid oxide particles known in the art as a solvent dispersion sol of the above-described oxide can be directly used.
  • the refractive index of the oxide particles (Ba) (refractive index of wavelength 589 nm (Na-D line), measuring temperature 25 ° C) is usually in the range of 1.2 to 3.0, preferably 1 3 to 2.5, more preferably 1.4 to 2.2.
  • the refractive index of the cured film can be set to an appropriate range by selecting the type of oxide particles according to the use of the obtained cured film.
  • the organic compound (Bb) is preferably a compound having a silanol group in the molecule or a compound that generates a silanol group by hydrolysis.
  • the polymerizable unsaturated group contained in the organic compound (Bb) is not particularly limited, but examples thereof include attalyloyl group, methacryloyl group, vinyl group, probe group, butagel group, styryl group, ethynyl group, cinnamoyl. Preferred examples include a group, a maleate group, and an acrylamide group.
  • This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with active radical species.
  • These groups can be used alone or in combination of two or more.
  • the organic compound (Bb) is a compound having a silanol group in the molecule (hereinafter referred to as “silanol group-containing compound” t) or a compound that generates a silanol group by hydrolysis (hereinafter referred to as “silanol group-generating compound”). It is preferable that Examples of such a silanol group-forming compound include compounds in which an alkoxy group, an aryloxy group, an acetoxy group, an amino group, a halogen atom, and the like are bonded to a silicon atom. An alkoxy group or an aryloxy group is bonded to the silicon atom. A compound in which is bonded, that is, an alkoxysilyl group-containing compound or an aryloxysilyl group-containing compound is preferable.
  • the silanol group-forming site of the silanol group or the silanol group-generating compound is a structural unit that binds to the oxide particles (Ba) by a condensation reaction or a condensation reaction that occurs following hydrolysis.
  • organic compound (Bb) examples include, for example, compounds represented by the following formula (2).
  • R 2 may be the same or different, but is a hydrogen atom or an alkyl group or an aryl group having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, octyl, phenol, xylyl group.
  • u represents o (oxygen atom) or S (io atom).
  • p is an integer of 1 to 3.
  • Examples of the group represented by [(R'O) R 2 Si—] include, for example, a trimethoxysilyl group, a triethoxy group.
  • R 3 is a divalent organic group having an aliphatic or aromatic structure having 1 to 12 carbon atoms and may contain a chain, branched or cyclic structure.
  • R 4 is a divalent organic group, and is usually selected from among divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500.
  • R 5 is a (q + 1) -valent organic group, preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.
  • Z represents a monovalent organic group having a polymerizable unsaturated group in the molecule that undergoes an intermolecular crosslinking reaction in the presence of an active radical species.
  • q is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.
  • the amount of the organic compound (Bb) used in the production of the reactive particles (B) is preferably 1 to 95, with the total of the oxide particles (Ba) and the organic compound (Bb) being 100% by mass. % By mass, and more preferably 2 to 90% by mass.
  • the amount of the organic compound (Bb) is less than 1% by mass, the dispersibility of the reactive particles (B) in the composition is insufficient, and the transparency and scratch resistance of the resulting cured product are not sufficient.
  • the amount of the organic compound (Bb) exceeds 95% by mass, the organic compound (Ba) becomes excessive.
  • the blending amount of component (B) in the curable composition of the present invention is preferably 30 to 60% by mass, with the total of components (A) to (D) being 100% by mass, preferably 20 to 60% by mass. % Is more preferable. If it is less than 20% by mass, it may not be possible to obtain a high refractive index. If it exceeds 60% by mass, the film formability may be insufficient.
  • the amount of the reactive particles (B) means a solid content, and when the reactive particles (B) are used in the form of a solvent-dispersed sol, the blending amount does not include the amount of the solvent.
  • Compound having two or more polymerizable unsaturated groups in the molecule (hereinafter sometimes referred to as “polymerizable unsaturated group-containing compound (Ca)”, “compound (Ca)” or “(Ca) component”) Is preferably used to improve the film-forming property of the composition.
  • a compound (Ca) having two or more polymerizable unsaturated groups in the molecule can be obtained by curing the curable composition to produce two or more polymerizable unsaturated groups in the molecule. It becomes a polymer or copolymer of a compound having a sum group, that is, a polymer (C).
  • the compound (Ca) is not particularly limited as long as it contains two or more polymerizable unsaturated groups in the molecule, and examples thereof include melamine acrylates, (meth) acrylic esters, and vinyl compounds. be able to. Of these, (meth) acrylic esters are preferred.
  • (Meth) acrylic esters include trimethylol propane tri (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate
  • dipentaerythritol hexa (meth) acrylate dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, and ditrimethylolpropane tetra (meth) acrylate are preferred.
  • vinyl compounds include dibutene benzene, ethylene glycol dibule ether, diethylene glycol divininole ether, and triethylene glycol divinino etherate.
  • Ca polymerizable unsaturated group-containing compound
  • Commercially available products of such a polymerizable unsaturated group-containing compound (Ca) include, for example, Sanwa Chemical Co., Ltd., trade name: Yucarac MX-302, Toagosei Co., Ltd., trade name: Aronix M — 400, M—408, M—450, M—305, M—309, M—310, M—315, M— 320, M-350, M-360, M-208, M-210, M-215, M-220, M-225, M-233, M-240, M-245, M-260, M-270, M—1100, M—1200, M—1210, M—1310, M—1600, M—221, M—203, TO—924, TO—1270, TO—1231, TO—595, TO—756, TO— 1343, TO-902, TO-904, TO-905, TO-1330, manufactured by Nippon Kayaku Co., Ltd.
  • the amount of the (Ca) component in the curable composition of the present invention is preferably 1 to 70% by mass, with the total of components (A) to (D) being 100% by mass. More preferred is ⁇ 60 mass%.
  • the photopolymerization initiator (D) is combined with the tin-containing indium oxide fine particles (A), the reactive particles (B), and the polymerizable unsaturated group-containing compound (Ca). .
  • Examples of the photopolymerization initiator (D) include compounds that generate cationic species by radiation (light) irradiation and compounds that generate active radical species by radiation (light) irradiation (radiation (photo) polymerization initiator). The thing currently used widely can be mentioned.
  • an ohmic salt having a structure represented by the following formula (3) can be mentioned as a preferred example.
  • This ohmic salt is a compound that releases a Lewis acid upon receiving light.
  • the cation is an onium ion
  • W is S, Se, Te, P, As, Sb, Bi ⁇ 0, I, Br, Cl, or N ⁇ N—
  • R 9 , R 10 , R 11 and R 12 are the same or different organic groups
  • a, b, c and d are each an integer of 0 to 3
  • (a + b + c + d) is W M is the metal or metalloid that forms the central atom of the halide complex [ML] e + f
  • B B, P, As ⁇ Sb, Fe ⁇ Sn, Bi ⁇ Al, Ca ⁇ In, Ti ⁇ Zn, Sc ⁇ V, Cr ⁇ Mn, Co, and the like.
  • L is, for example, a halogen atom such as F, Cl, Br, etc.
  • e is the net charge of the halide complex ion, and f is the valence of M.
  • an onium salt having an anion represented by the formula [ML (OH) "] can also be used.
  • CIO- perchlorate ion
  • CFSO- trifluoromethanesulfonate ion
  • An onium salt having other anions such as phosphosulfonic acid anion and tri-tolutoluene sulfonic acid anion.
  • aromatic salts particularly effective as the photopolymerization initiator (D) are aromatic onium salts.
  • Aromatic diazo-um salts described in Japanese Patent Publication No. 4, etc., and thiobililium salts described in US Pat. No. 4,139,655 are preferable.
  • an iron Z allene complex, an aluminum complex Z photodecomposition silicon compound type initiator, etc. can be mentioned. These can be used alone or in combination of two or more.
  • photopolymerization initiators suitably used as the photopolymerization initiator (D) include Mitsui Cytec Co., Ltd. trade name: KYATALIST 4050, Union Carnoid Co., Ltd. trade name: UV
  • UVI— 6970 UVI— 6974
  • UVI— 6990 manufactured by Asahi Denki Kogyo Co., Ltd.
  • the radiation (photo) polymerization initiator is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization.
  • acetophenone acetophenone benzil ketal, 1-hydroxycyclohexyl.
  • Radial (photo) polymerization initiators include, for example, Ciba 'Specialty' Chemicals Co., Ltd. trade names: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI1700, CGI1750, CGI1850, CG24-61, Darocur 1116, 1173, manufactured by BAS F
  • Product name Lucyrin TPO, manufactured by UCB
  • Product name Nubekril P36, Fratteri 'made by Lamberti Co., Ltd.
  • Product name Ezacure I KIP150, KIP65LT, KIP100F, KT37, KT55, ⁇ 046, ⁇ 75 ⁇ , etc.
  • a photopolymerization initiator and a thermal polymerization initiator can be used in combination as necessary.
  • Preferable thermal polymerization initiators include, for example, peroxides and azo compounds, and specific examples include benzoyl peroxide, t-butyl-peroxybenzoate, azobisisobutyrate-tolyl and the like. Can be mentioned.
  • the blending amount of the photopolymerization initiator (D) in the curable composition of the present invention is 0.01 to 20% by mass, where the total of the components (A) to (D) is 100% by mass. It is more preferable that the content is 0.1 to 10% by mass. If the content is less than 0.01% by mass, the hardness of the cured product may be insufficient, and if it exceeds 20% by mass, the interior (lower layer) may not be cured.
  • the curable composition of the present invention can be used after being diluted with a solvent in order to adjust the thickness of the coating film.
  • the viscosity when used as an antireflection film or a coating material is usually 0.1 to 50, OOOmPa 'seconds (25.C), preferably 0.5 to: LO, OOOmPa' seconds (25.C). )
  • Examples of the solvent that can be used for adjusting the coating thickness include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
  • alcohols such as methanol, ethanol, isopropanol, butanol, and octanol
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.
  • Ethyl acetate vinegar Esters such as butyl acid, lactic acid ethyl, butyrolatatone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomono methyl ether and diethylene glycol mono mono butino ether ether; benzene, Aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
  • Esters such as butyl acid, lactic acid ethyl, butyrolatatone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate
  • ethers such as ethylene glycol monomono methyl ether and diethylene glycol mono mono butino ether ether
  • benzene Aromatic hydrocarbons such as toluene and xylene
  • the blending amount of the solvent (E) in the curable composition of the present invention is not particularly limited, but is usually 5 to: LOO, based on 100 parts by mass of the total solid content of the curable composition of the present invention. 000 parts by mass, preferably 10 to 10,000 parts by mass.
  • the dispersion medium may be used as it is as a solvent. Only a solvent different from the medium may be used, or a dispersion medium and another solvent may be combined and used as the solvent (E).
  • one polymerizable unsaturated group is contained in the molecule. It can also contain compound (F).
  • Examples of the polymerizable unsaturated group possessed by the compound (F) used in the present invention include the groups described in the description of the component (Ca), and specific examples of the compound (F) include, for example, N — Bulle pyrrolidone, N-bearcaprolatatam-containing ratatam, isovolyl (meth) acrylate, boryl (meth) acrylate, tricyclodecal (meth) acrylate, dicyclopental (meth) acrylate , Cyclohexane (meth) acrylate, cyclohexyl (meth) alicyclic structure-containing (meth) acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, Ataliloyl morpholine, butyl imidazole, butyl pyridine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Tallylate
  • the compounding amount of the compound (F) in the curable composition of the present invention is preferably 0.1 to 35 parts by mass with respect to 100 parts by mass in total of the components (A) to (D). It is preferably 1 to 30 parts by mass.
  • a photosensitizer for the purpose of the present invention, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, and a surface active agent are used as necessary.
  • Agents, plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, inorganic fillers, pigments, dyes and the like can be appropriately blended.
  • the curable composition of the present invention contains a photopolymerization initiator (D) as a polymerization initiator, but in addition, a compound that generates a cationic species thermally and Z or a thermally active radical.
  • a thermal polymerization initiator such as a compound generating seeds can be blended.
  • Examples of the compound that generates a cationic species thermally include, for example, aliphatic sulfonic acid, acid-fatty acid sulfonate, aliphatic carboxylic acid, aliphatic carboxylate, aromatic carboxylic acid, Examples include aromatic carboxylates, alkylbenzene sulfonic acids, alkyl benzene sulfonates, phosphate esters, metal salts and the like.
  • thermal polymerization initiator examples include peroxides and azo compounds, and specific examples thereof include benzoyl peroxide, t-butyl-peroxybenzoate, and azobisisobutyrate. Mouth-tolyl and the like can be mentioned.
  • the amount of the radical polymerization initiator used as necessary is (
  • a total of 100 parts by mass of components (A) to (D) is preferably 0.01 to 20 parts by mass, more preferably 0.1 to: LO parts by mass. If the amount is less than 01 parts by mass, the hardness of the cured product may be insufficient. If the amount exceeds 20 parts by mass, the cured product will not be cured to the inside (lower layer). There is.
  • the curable composition of the present invention comprises the above tin-containing indium oxide fine particles (A), reactive particles (B), reactive particles (B), reactive particles (B), reactive particles (B), reactive particles (B), reactive particles (B), reactive particles (B), reactive particles (B), reactive particles (B), reactive particles (B).
  • B a polymerizable unsaturated group-containing compound (Ca), a photopolymerization initiator (D), and, if necessary, a solvent (E), a compound (F), and other additives. can get.
  • the cured film of the present invention can be obtained by coating and curing the curable composition of the present invention on various substrates, for example, plastic substrates. Specifically, after coating the composition and preferably drying the volatile component at 0 to 200 ° C., it is obtained as a coated molded body by performing the above-described curing treatment with heat and Z or radiation. it can.
  • the preferable curing condition when using heat is 20 to 150 ° C., and is performed within a range of 10 seconds to 24 hours.
  • radiation it is preferable to use ultraviolet rays or electron beams.
  • the preferable irradiation amount of ultraviolet rays is 0.01 to 10 jZcm 2 , and more preferably 0.1 to 2 jZcm 2 .
  • preferable electron beam irradiation conditions are a pressurization voltage of 10 to 300 KV, an electron density of 0.02 to 0.30 mAZcm 2 , and an electron beam irradiation amount of 1 to: LOMrad.
  • the liquid curable composition of the present invention containing tin-containing indium oxide (ITO) fine particles (A) and reactive particles (B) as particle components was subjected to an easy adhesion treatment on the surface, which will be described later.
  • Polyester, polyethylene terephthalate (PET) etc. Resulting in layer separation. That is, the ITO fine particles (A) are unevenly distributed on the side in contact with the substrate and the reactive particles (B) are unevenly distributed on the air interface side.
  • An electron micrograph showing a state in which the ITO fine particles (A) in the cured film obtained by curing the composition of the present invention are unevenly distributed on the substrate side is shown in FIG. Fig. 3A shows the substrate side interface, and Fig. 3B shows the air side interface.
  • component (A) In the cured film of the present invention, effective conductivity can be realized with a smaller amount of component (A). In addition, since the amount of component (A) added can be reduced and the particle size of component (A) is small, a more transparent film with less light absorption and scattering by component (A) is formed. That's right.
  • the cured film of the present invention has characteristics of being able to form a coating film (film) having high hardness and high refractive index and excellent scratch resistance and adhesion to the substrate and the low refractive index layer. Therefore, it is particularly suitably used as a hard coat or antireflection film for film type liquid crystal elements, touch panels, plastic optical parts and the like.
  • the cured film of the present invention is excellent in antistatic properties and transparency, and is useful as an antistatic film in various plastic optical parts and the like.
  • the cured film layer of the laminate of the present invention can be obtained by coating the antistatic layer-forming composition described above on the substrate, drying it, and then irradiating it with radiation to cure the composition. .
  • the surface resistance of the obtained cured film layer is 1 X 10 13 ⁇ or lower, preferably 1 X 10 12 ⁇ or lower, more preferably ⁇ ⁇ ⁇ ⁇ or lower, and more preferably IX 10 8 ⁇ or lower. is there. If the surface resistance exceeds 1 X 10 13 ⁇ , the antistatic performance may be insufficient and the dust may not be easily removed.
  • the surface resistance of the laminate (antireflection film with an antistatic function) of the present invention when a low refractive index layer or the like described later is formed on the cured film layer having a surface resistance value in the above range is 1 X 10 13 ⁇ or less, preferably 1 ⁇ 10 12 ⁇ or less, more preferably 1 ⁇ 10 10 ⁇ / ⁇ or less, and further preferably 1 ⁇ 10 8 ⁇ .
  • the application method of the composition for forming an antistatic layer is not particularly limited! /, For example, roll coating, spray coating, flow coating, diving, screen printing, inkjet printing. A known method such as the above can be applied.
  • the radiation source used for curing the composition for forming an antistatic layer is not particularly limited as long as it can be cured in a short time after the composition is applied.
  • Examples of the visible ray source include direct sunlight, lamps, fluorescent lamps, and lasers.
  • Examples of the ultraviolet ray source include mercury lamps, halide lamps, and lasers, and electron beam source.
  • a method using thermoelectrons generated from a commercially available tungsten filament a cold cathode method in which metal is generated through a high voltage pulse, and collision between ionized gaseous molecules and a metal electrode 2
  • Examples include secondary electron systems that use secondary electrons.
  • Examples of the source of ⁇ rays, j8 rays, and ⁇ rays include fission materials such as 6 ° Co.
  • fission materials such as 6 ° Co.
  • vacuum tubes that collide accelerated electrons with the anode can be used. .
  • These radiations may be irradiated alone or in combination of two or more kinds. Alternatively, one or more kinds of radiation may be irradiated for a certain period.
  • the thickness of the cured film layer is preferably 0.05-30 ⁇ m! /.
  • the thickness is relatively thick, preferably 2 to 15 m.
  • 0.05 ⁇ : LO m is preferable.
  • the total light transmittance is preferably 85% or more.
  • the cured film layer formed as described above contains the component (A) in the range of 7 to 40% by mass and the component (Ba) in the range of 20 to 60% by mass. It is necessary to be. If this ratio is exceeded, the disadvantages described in the explanation of each component of the curable composition may occur.
  • the substrate used in the laminate of the present invention may be appropriately selected according to the intended use without any particular limitation, such as metal, ceramics, glass, plastic, wood, slate, etc., but has high productivity of radiation curability, As a material that can exhibit industrial utility, it is preferably applied to, for example, a film or a fiber-like substrate. Particularly preferred materials are plastic fibres. Lum, a plastic plate. Examples of such plastics include polycarbonate, polymethyl methacrylate, polystyrene Z polymethyl methacrylate copolymer, polystyrene, polyester, polyolefin, triacetyl cellulose resin, and diethylene glycol diaryl. Examples include carbonate (CR-39), ABS resin, AS resin, polyamide, epoxy resin, melamine resin, cyclized polyolefin resin (for example, norbornene-based resin).
  • the antistatic layer forming composition is applied.
  • the base material to be used is preferably a base material such as polyester or polyethylene terephthalate (PET) in which the surface to which the composition for forming an antistatic layer is applied is subjected to an easy adhesion treatment.
  • Examples of such easy adhesion treatment include corona discharge treatment and easy adhesion layer coating treatment.
  • a preferred example of a commercially available base material subjected to easy adhesion treatment is polyester film A4300 (manufactured by Toyobo Co., Ltd.).
  • the thickness of the base material should be appropriately set according to the purpose and is not particularly limited.
  • a method of forming a low refractive index layer or a multilayer structure of a low refractive index layer and a high refractive index layer is formed on a base material or a hard-coated base material. It is known that the method to do is effective.
  • FIG. 2A shows a first embodiment in which the laminate of the present invention is used as an antireflection film with an antistatic function.
  • the antireflection film 2 with an antistatic function is obtained by forming an antistatic layer 12 which is a cured film layer obtained by curing the curable composition on a base material 10, and further forming a low refractive index layer thereon. 18 is formed.
  • the antistatic layer 12 has both an antistatic function and a hard coat layer function.
  • the refractive index of the antistatic layer 12 needs to be higher than the refractive index of the low refractive index layer 18.
  • the antistatic layer 12 of the antireflection film 2 of the present invention can also function as a hard coat layer, but a hard coat layer can be provided separately.
  • the hard coat layer n is provided between the antistatic layer 12 and the low refractive index layer 18 or between the substrate 10 and the antistatic layer 12.
  • the refractive index of the hard coat layer 11 must be higher than the refractive index of the low refractive index layer 18.
  • FIG. 2D shows a second embodiment in which the laminate of the present invention is used as an antireflection film with an antistatic function.
  • the antireflection film 2 with an antistatic function is obtained by forming an antistatic layer 12 which is a cured film layer obtained by curing the curable composition on a base material 10, and further A high refractive index layer 16 and a low refractive index layer 18 are formed in this order.
  • the antistatic layer 12 may have both an antistatic function, a function as a coating, and a function as a medium refractive index layer.
  • the refractive index of the antistatic layer 12 is lower than the refractive index of the high refractive index layer 16. It must be higher than the refractive index.
  • the second mode a mode in which a hard coat layer is separately provided is possible as in the first mode.
  • the hard coat layer 11 can be provided between the antistatic layer 12 and the high refractive index layer 16 or between the substrate 10 and the antistatic layer 12. These configurations are shown in FIGS. 2E and 2F.
  • FIG. 2G shows a third embodiment in which the laminate of the present invention is used as an antireflection film with an antistatic function.
  • the antireflection film 2 with an antistatic function is obtained by forming an antistatic layer 12 which is a cured film layer obtained by curing the curable composition on a base material 10, and further A middle refractive index layer 14, a high refractive index layer 16, and a low refractive index layer 18 are formed in this order.
  • the antistatic layer 12 has both an antistatic function and a hard coat function.
  • a hard coat layer can be separately provided as in the first embodiment.
  • the hard coat layer 11 can be provided between the antistatic layer 12 and the medium refractive index layer 14 or between the substrate 10 and the antistatic layer 12. These forms are shown in FIG. 2H and FIG.
  • the low refractive index layer is a layer having a thickness of 0.05 to 0.20 m and a refractive index of 1.30 to L45.
  • the material used for the low refractive index layer is not particularly limited as long as the desired properties are obtained.
  • a curable composition containing an fluorinated polymer, an acrylic monomer, and a fluorinated acrylic monomer. And cured products such as epoxy group-containing compounds and fluorine-containing epoxy group-containing compounds.
  • silica fine particles and the like can be blended.
  • a low refractive index layer is formed using a curable resin composition containing components (E) and (F) described later.
  • the high refractive index layer has a thickness in the range of 0.05 to 0.20 m and a refractive index in the range of 1.55 to 2.20.
  • high refractive index inorganic particles such as metal oxide particles can be mixed.
  • metal oxide particles include antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, acid-zinc zinc (ZnO) particles, antimony-containing ZnO, and A1-containing Z ⁇ . Particles ZrO particles, TiO particles, silica-coated TiO particles, Al 2 O 3 / ZrO-coated TiO particles,
  • Examples include CeO particles.
  • antimony-containing tin oxide (ATO) particles are preferred.
  • ITO indium oxide
  • PTO phosphorus-containing tin oxide
  • A1-containing ZnO particles Al 2 O 3 / ZrO-coated TiO particles.
  • metal oxide particles are one kind alone or
  • the high refractive index layer can have a function of a hard coat layer.
  • a layer having a refractive index of 1.50 to: L 90 and having a refractive index higher than that of the low refractive index layer and lower than that of the high refractive index layer is set to the medium refractive index.
  • the refractive index of the middle refractive index layer is preferably 1.50 to L80, more preferably 1.50 to L75.
  • the thickness of the medium refractive index layer is in the range of 0.05 to 0.20 / z m.
  • high refractive index inorganic particles such as metal oxide particles are used. You can join yourself.
  • metal oxide particles include antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, ZnO particles, antimony-containing ZnO, A1-containing ZnO particles, ZrO particles, TiO Particles, silica-coated TiO particles, Al 2 O 3 / ZrO-coated TiO particles, CeO particles
  • antimony-containing tin oxide (ATO) particles tin-containing indium oxide (ITO) particles, phosphorus-containing tin oxide (PTO) particles, A1-containing ZnO particles, ZrO particles
  • metal oxide particles can be used singly or in combination of two or more.
  • the reflectance can be lowered by combining the low refractive index layer and the high refractive index layer, and the reflectance can be reduced by combining the low refractive index layer, the high refractive index layer, and the medium refractive index layer. Can be reduced and the glare can be reduced.
  • hard coat layer examples include SiO, epoxy resin, acrylic resin, melamine
  • silica particles may be blended with these rosins.
  • the hard coat layer has the effect of increasing the mechanical strength of the laminate.
  • the thickness of the hard coat layer is
  • the refractive index of the coated layer is usually in the range of 1.45 to 1.70, preferably 1.45 to L60.
  • the material of the substrate when the laminate of the present invention is used as an antireflection film must be transparent.
  • the base subjected to the easy adhesion treatment is used.
  • Good material Good examples include corona discharge treatment and easy adhesion layer coating treatment.
  • a preferred example of a commercially available base material subjected to easy adhesion treatment is polyester film A4300 (manufactured by Toyobo Co., Ltd.).
  • the thickness of the substrate is not particularly limited, but is usually in the range of 30 to 300 ⁇ m, preferably 50 to 200 ⁇ m.
  • the laminate of the present invention In the production of the laminate of the present invention, other functions such as non-glare effect, selective light absorption effect, weather resistance, durability, transferability, etc. are further added, for example, light of 1 ⁇ m or more. It is possible to add a layer containing scattering particles, add a layer containing a dye, add a layer containing an ultraviolet absorber, add an adhesive layer, add an adhesive layer and a release layer, etc. Further, these function-imparting components can be added as one component of the composition for forming an antistatic layer and Z or a composition for forming a low refractive index layer of the present invention.
  • the laminate of the present invention has scratches on, for example, plastic optical parts, touch panels, film-type liquid crystal elements, plastic housings, plastic containers, flooring materials as building interior materials, wall materials, artificial stones, etc. It can be suitably used as a hard coating material for preventing (scratching) and preventing contamination; an adhesive for various substrates, a sealing material; a binder material for printing ink, and the like.
  • These layers may be formed in only one layer, or two or more different layers may be formed.
  • the film thickness of the low, medium and high refractive index layers is usually 60 to 150 nm
  • the film thickness of the hard coat layer is usually 1 to 20 111
  • the film thickness of the antistatic layer is usually 0.05 to 30 / ⁇ ⁇ . It is.
  • the layer can be produced by a known method such as coating and curing, vapor deposition, or sputtering.
  • the low refractive index layer formed in the laminate of the present invention comprises (G) a curable resin composition containing (E) an ethylenically unsaturated group-containing fluoropolymer and (i) silica particles (hereinafter referred to as “low refractive index”). Curing made of a composition for forming a rate layer " It is preferable that it is a thing.
  • the ethylenically unsaturated group-containing fluoropolymer (G) used in the composition for forming a low refractive index layer is composed of a compound containing one isocyanate group and at least one ethylenically unsaturated group, and a hydroxyl group-containing polymer. It can be obtained by reacting with a fluoropolymer.
  • the compound containing one isocyanate group and at least one ethylenically unsaturated group contains one isocyanate group and at least one ethylenically unsaturated group in the molecule. If it is a compound, it is not particularly limited.
  • gelling may occur when reacting with a hydroxyl group-containing fluoropolymer.
  • a curable rosin composition to be described later can be hardened more easily, and therefore a compound having a (meth) atallyloyl group is more preferable.
  • examples of such a compound include 2- (meth) atalylooxychetyl isocyanate and 2- (meth) atalylooxypropylisocyanate alone or in combination of two or more.
  • Such a compound can be synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate.
  • diisocyanates examples include 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexylenoisocyanate).
  • hydroxyl-containing (meth) acrylate examples include 2-hydroxyethyl (meth) acrylate.
  • Pentaerythritol tri (meth) acrylate is preferred.
  • hydroxyl group-containing polyfunctional (meth) atalylate examples include, for example, Osaka Organic Chemical Co., Ltd., trade name HEA, Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA, PET-30, Toagosei ( Product name Alonics M-215, M-233, M-305, M -400 etc. can be obtained.
  • the hydroxyl group-containing fluoropolymer preferably comprises the following structural units (a), (b) and (c).
  • R 11 represents a fluorine atom, a fluoroalkyl group or a group represented by —OR ”(R represents an alkyl group or a fluoroalkyl group)]
  • R represents a hydrogen atom or a methyl group
  • R 14 represents an alkyl group,-(CH) -OR 15
  • R 15 represents an alkyl group or a glycidyl group, c represents a number of 0 or 1), a carboxyl group or an alkoxycarbo group
  • the fluoroalkyl group of R 11 and R 12 includes a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a no-fluorine hexyl group. And a fluoroalkyl group having 1 to 6 carbon atoms such as perfluorocyclohexyl group.
  • the alkyl group for R 12 include alkyl groups having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a cyclohexyl group.
  • the structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component.
  • a fluorine-containing butyl monomer is not particularly limited as long as it is a compound having at least one polymerizable unsaturated double bond and at least one fluorine atom. Examples of this include fluoroolefins such as tetrafluoroethylene, hexafluoropropylene, 3, 3, 3-trifluoropropylene; alkyl perfluoro oral ether or alkoxyalkyl perfluorobule.
  • Perfluoro (alkyl vinyl ether) such as perfluoro (methyl vinyl ether), perfluoro (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether), etc .
  • Perfluoro (alkoxyalkyl butyl ether) s such as propoxypropyl butyl ether may be used singly or in combination of two or more.
  • hexafluoropropylene and perfluoro (alkyl butyl ether) or perfluoro (alkoxy alkyl butyl ether) are more preferred and used in combination!
  • the content of the structural unit (a) is 20 to 70 mol% when the total of the structural units (a) to (c) is 100 mol%. This is because if the content is less than 20 mol%, it may be difficult to develop a low refractive index, which is an optically characteristic fluorine-containing material intended by the present application. This is because if the ratio exceeds 70 mol%, the solubility of the hydroxyl group-containing fluorine-containing polymer in an organic solvent, transparency, or adhesion to a substrate may be lowered.
  • the content of the structural unit (a) is set to the total of the structural units (a) to (c) 1 against 00 mole 0/0, more preferably force S to the 25 to 65 mole 0/0 and more preferably to instrument 30 to 60 mole 0/0.
  • examples of the alkyl group of R 13 or R 14 include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, a cyclohexyl group, and a lauryl group.
  • examples of the alkoxycarbonyl group represented by R 15 include a methoxycarbonyl group and an ethoxycarbonyl group.
  • the structural unit (b) can be introduced by using the above-mentioned butyl monomer having a substituent as a polymerization component.
  • bur monomers include methyl vinyl ethere, ethino levinino le ethere, n- propino levinino ethere, isopropino levinino ether, n-butyl vinyl ether, isobutyl vinyl ether, tert -Butyl vinyl etherenole, n-pentinolevinoreethenole, n-hexenolevinoreethenore, n-year-old cubinorebi-noreethenore, n-dodecinolevinorethenore, 2-ethinorehexinolevinoreteol, cyclohexyl vinyl ether Alkyl butyl ethers or cycloalkyl alkyl ethers such as: ethyl
  • the content of the structural unit (b) is 10 to 70 mol%, where the total of the structural units (a) to (c) is 100 mol%.
  • the reason for this is that when the content is less than 10 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced.
  • the content exceeds 70 mol%, This is because optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluoropolymer may be deteriorated.
  • the content of structural unit (b) is set to the total of structural units (a) to (c) 1 against 00 mole 0/0, more preferably force S of 20 to 60 mole 0/0 and more preferred instrument 30 to 60 mole 0/0 to.
  • the structural unit (c) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component.
  • hydroxyl-containing butyl monomers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl.
  • Hydroxyl-containing butyl ethers such as vinyl ether, 6-hydroxyhexyl vinyl ether, hydroxyl-containing butyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxy butyl allyl ether, glycerol monoallyl ether, allyl alcohol, etc. Can be mentioned.
  • hydroxyl group-containing vinyl monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and force prolatatone ( (Meth) acrylate, polypropylene glycol (meth) atrelate, etc. can be used.
  • the content of the structural unit (c) is preferably 5 to 70 mol% when the total of the structural units (a) to (c) is 100 mol%.
  • the reason for this is that when the content is less than 5 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may decrease, whereas when the content exceeds 70 mol%, This is because the optical properties such as transparency and low reflectivity of the hydroxyl group-containing fluoropolymer may be deteriorated.
  • the content of the structural unit (c), the total 1 00 mole 0/0 of the structural units (a) ⁇ (c), that 5 to 40 mol 0/0 preferred is the et to a more preferred instrument 5-30 mol 0/0.
  • the hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit (d). Good.
  • R 18 and R 19 may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenialkyl group or an aryl group]
  • the alkyl group of R 18 or R 19 is an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, or a propyl group.
  • the halogenoalkyl group is a trifluoromethyl group, C1-C4 fluoroalkyl group, such as perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, etc.
  • aryl groups include a phenyl group, a benzyl group, and a naphthyl group. It is done.
  • the structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the formula (14).
  • an azo group-containing polysiloxane compound having a polysiloxane segment represented by the formula (14) examples include compounds represented by the following formula (15).
  • R 2 to R 23 represent a hydrogen atom, an alkyl group or a cyan group which may be the same or different
  • R 24 to R 27 represent a hydrogen atom or an alkyl group which may be the same or different.
  • I and r are numbers from 1 to 6
  • s and t are numbers from 0 to 6
  • y is a number from 1 to 200
  • z is a number from 1 to 20.
  • the structural unit (d) is contained in the hydroxyl group-containing fluoropolymer as a part of the structural unit (e).
  • R 1 to R 4 R 24 to R 27 , i, r, s, t and y are the same as those in the above formula (15). ]
  • a compound represented by the following formula (17) is particularly preferable.
  • the content of the structural unit (d) is preferably 0.1 to 10 mole parts when the total of the structural units (a) to (c) is 100 mole parts.
  • the reason for this is that when the content is less than 0.1 mol part, the surface slipperiness of the coated film after curing may be lowered, and the scratch resistance of the coated film may be lowered.
  • the ratio exceeds 10 parts by mole, the transparency of the hydroxyl group-containing fluoropolymer is inferior, and when used as a coating material, repelling and the like may easily occur during coating.
  • the content of the structural unit (d) is 0.1 to 5 mole parts with respect to 100 mole parts in total of the structural units (a) to (c).
  • the strength of 0.1 to 3 mole parts S is more preferable.
  • the content of the structural unit (e) should be determined so that the content of the structural unit (d) contained therein falls within the above range.
  • the hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit (f). Good.
  • R 28 represents an emulsifying group
  • the group having an emulsifying action of R 28 has both a hydrophobic group and a hydrophilic group, and the hydrophilic group has a polyether structure such as polyethylene oxide and polypropylene oxide. Some groups are preferred.
  • Examples of such a group having an emulsifying action include a group represented by the following formula (19).
  • the structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component.
  • a reactive emulsifier examples include compounds represented by the following formula (20).
  • the content of the structural unit (f) is 0.1 to 5 mole parts is preferable.
  • the reason for this is that when the content is 0.1 mol part or more, the solubility of the hydroxyl group-containing fluoropolymer in the solvent is improved.
  • the content is 5 mol parts or less, the refractive index is low. This is because the adhesiveness of the composition for forming the rate layer does not increase excessively, handling V becomes easy, and the moisture resistance does not decrease even when used as a coating material.
  • the content of the structural unit (f) is preferably more than 0.1 to 3 monolayers with respect to a total of 100 monolayers of the structural units (a) to (c). 0.2 to 3 monolayer power S is more preferable.
  • the hydroxyl group-containing fluoropolymer preferably has a polystyrene equivalent number average molecular weight of 5,000 to 500,000 as measured by gel permeation chromatography using tetrahydrofuran as a solvent.
  • the reason for this is that when the number average molecular weight is less than 5,000, the mechanical strength of the hydroxyl group-containing fluoropolymer may be reduced.
  • the number average molecular weight exceeds 500,000, it will be described later. This is because the viscosity of the composition for forming a low refractive index layer becomes high and thin film coating may be difficult.
  • the hydroxyl group-containing fluoropolymer has a polystyrene-reduced number average molecular weight of preferably 10,000 to 300,000, more preferably 10,000 to 100,000.
  • the ethylenically unsaturated group-containing fluorine-containing polymer is obtained by reacting the above-described compound containing one isocyanate group and at least one ethylenically unsaturated group with a hydroxyl group-containing fluorine-containing polymer. Obtained.
  • a compound containing one isocyanate group and at least one ethylenically unsaturated group and a hydroxyl group-containing fluoropolymer react at a molar ratio of isocyanate group Z hydroxyl group of 1.1 to 1.9. It is preferable to do so. The reason for this is that if the molar ratio is less than 1.1, the scratch resistance and durability may be lowered. On the other hand, if the molar ratio exceeds 1.9, the composition for forming a low refractive index layer may be reduced. This is because the scratch resistance of the coating film after immersion in an alkaline aqueous solution may be reduced.
  • the molar ratio of the isocyanate group Z hydroxyl group is preferably 1.1 to 1.5, more preferably 1.2 to 1.5.
  • the amount of component (G) added to the composition for forming a low refractive index layer is not particularly limited, but is usually 1 to 95% by weight based on the total amount of the composition other than the organic solvent. .
  • the reason for this is that when the addition amount is less than 1% by weight, the refractive index of the cured coating film of the curable resin composition becomes high, and a sufficient antireflection effect may not be obtained. This is because, if the amount of caro exceeds 95% by weight, the scratch resistance of the cured coating film of the curable resin composition may not be obtained! /.
  • the addition amount of the component (G) is more preferably 2 to 90% by weight, and further preferably 3 to 85% by weight.
  • particles containing silica as a main component can be blended, and the scratch resistance of the cured product of the composition for forming a low refractive index layer, particularly steel wool resistance. Can be improved.
  • particles having silica as a main component particles having silica having a number average particle diameter of 1 to lOOnm as a main component are preferable.
  • the particle size is measured with a transmission electron microscope.
  • the particle size of the component (H) is preferably 5 to 80 nm, more preferably 10 to 60 nm.
  • known particles can be used, and the shape is not particularly limited.
  • colloidal silica As long as it is spherical, it is not limited to ordinary colloidal silica, and may be hollow particles, porous particles, core-shell type particles, or the like. Further, it is not limited to a spherical shape, and may be an amorphous particle. Colloidal silica having a solid content of 10 to 40% by weight is preferred.
  • the dispersion medium is water! /
  • an organic solvent is preferred.
  • organic solvents include alcohols such as methanol, isopropyl alcohol, ethylene glycolol, butanol, ethylene glycol monopolypropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic carbonization such as toluene and xylene.
  • Hydrogens Amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate, and ⁇ -butalate Rataton; Organic solvents such as ethers such as tetrahydrofuran and 1,4 dioxane Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in admixture of two or more as a dispersion medium.
  • silica for example, colloidal silica, manufactured by Nissan Chemical Industries, Ltd., trade names: methanol silica sol, IPA-ST, MEK-ST, MEK-S T-S, ⁇ — ST— L, IPA— ZL, NBA— ST, XBA— ST, DMAC— ST, ST— UP ⁇ ST— OUP ⁇ ST— 20, ST— 40, ST— C, ST— N, ST— 0, ST-50, ST-OL, etc. can be mentioned.
  • the surface of the colloidal silica that has been subjected to a surface treatment such as chemical modification can be used.
  • it contains a hydrolyzable silicon compound having one or more alkyl groups in the molecule or a hydrolyzate thereof.
  • hydrolyzable silicon compounds include trimethylmethoxysilane, tryptylmethoxysilane, dimethyldimethoxysilane, dibutinoresimethoxysilane, methyltrimethoxysilane, butinoretrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxy.
  • Examples of those having a thiol group, such as ethyltrimethoxysilane include 3-mercaptopropyltrimethoxysilane.
  • a preferred compound is 3-mercaptopropyltrimethoxysilane.
  • the silica particles used in the present invention preferably have an ethylenically unsaturated group. (Hereinafter referred to as “reactive silica particles”).
  • the method for producing reactive silica particles is not particularly limited.
  • the reactive silica particles can be obtained by reacting the silica particles having a number average particle size of 10 to LOONm and a reactive surface treatment agent. .
  • examples of the surface treatment agent include alkoxysilane compounds, tetrabutoxysilane, tetrabutoxyzirconium, tetraisopropoxyaluminum, and the like. These can be used alone or in combination of two or more.
  • Specific examples of the surface treatment agent include compounds having an unsaturated double bond in the molecule such as y-methacryloxypropyltrimethoxysilane, ⁇ -acryloxypropyltrimethoxysilane, and vinyltrimethoxysilane.
  • the compounds represented by the following general formula (21) can be mentioned.
  • R 31 is a methyl group
  • R 32 is an alkyl group having 1 to 6 carbon atoms
  • R 33 is a hydrogen atom or a methyl group
  • m is 1 or 2
  • n is an integer of 1 to 5
  • A is A divalent alkylene group having 1 to 6 carbon atoms
  • B is a chain, cyclic or branched divalent hydrocarbon group having 3 to 14 carbon atoms
  • D is an (n + 1) valent chain or cyclic
  • D may contain an ether bond.
  • the silica particles have an ethylenically unsaturated group, they can be co-crosslinked with a UV curable acrylic monomer, and scratch resistance is improved.
  • porous silica particles are preferred.
  • the first porous silica particles (HI) are hydrolyzed and hydrolyzed of a key compound represented by the following formula (22) and a key compound represented by the following formula (23). And Z or obtained by hydrolysis condensation. That is, it is obtained by hydrolyzing and Z or hydrolytically condensing the silicon compound represented by the formula (22), and subjecting the keen compound represented by the formula (23) to hydrohydrolysis and Z or hydrolytic condensation. It is done.
  • the key compound represented by the formula (22) and the key compound represented by the formula (23) may be mixed and subjected to hydrolysis and Z or hydrolytic condensation at the same time.
  • the second porous silica particles (H2) are a key compound represented by the following formula (22), a key compound represented by the following formula (23), and a key compound represented by the following formula (24). Obtained by hydrolysis of Z and Z or hydrolytic condensation. That is, hydrolysis and Z or hydrolysis condensation of the key compound represented by the formula (22), and hydrolysis and Z or hydrolysis condensation of the key compound represented by the formula (23), and It is obtained by hydrolyzing and Z or hydrolytically condensing the silicon compound represented by the formula (24).
  • the key compound represented by the formula (22), the key compound represented by the formula (23), and the key compound represented by the formula (24) are mixed and simultaneously hydrolyzed and Z or hydrolyzed.
  • the key compound represented by formula (22) is hydrolyzed and Z or hydrolyzed, and then the key compound represented by formula (23) and formula (24) are used.
  • hydrolysis and Z or hydrolysis condensation may be carried out by adding the above-mentioned key compound.
  • each X is independently an alkoxy group having 1 to 4 carbon atoms, a hydrogen group, a logeno group, an isocyanate group, a carboxyl group, or an alkyl group having 2 to 4 carbon atoms. It is a xycarbonyl group or an alkylamino group having 1 to 4 carbon atoms, preferably an alkoxy group or a halogeno group, more preferably an alkoxy group.
  • Xs may be the same or different.
  • Examples of the compound represented by the formula (22) include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, and tetrachlorosilane.
  • R 29 is an alkenyl group having 2 to 8 carbon atoms, or an talyloxyalkyl having 4 to 8 carbon atoms. Or a methacryloxyalkyl group having 5 to 8 carbon atoms, preferably a bur group, an allyl group, an attaryloxychetyl group, an atalyloxypropyl group, an atalyloxybutyl group, a methacryloxycetyl group, a methacryloxypropyl group, a methacryloxypropyl group. Roxybutyl group.
  • j is an integer of 1-3, Preferably it is 1-2.
  • Examples of the compound represented by the formula (23) include vinyltrimethoxysilane, butyltrioxysilane, vinyltrichlorosilane, talyloxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, and the like.
  • the porous silica particles can contain an ethylenically unsaturated group.
  • the scratch resistance of the antireflection film of the present invention having a cured film obtained by curing the curable composition is improved.
  • R 3 is a fluorine-substituted alkyl group having 1 to 12 carbon atoms, preferably a fluorine-substituted alkyl group having 3 to 12 carbon atoms, more preferably fluorine having 3 to 10 carbon atoms. Substituted alkyl group.
  • k is an integer of 1 to 3, preferably 1 to 2.
  • Examples of the compound represented by the formula (24) include 3, 3, 3-trifluoropropyltrimethoxysilane, 2-perfluorohexylmethyltrimethoxysilane, and 2-perfluorohexylsilyltrimethoxy.
  • the porous silica particles can contain a fluorine-containing alkyl group.
  • the stain resistance of the cured film obtained by curing the curable composition can be improved.
  • Two or more kinds of the key compound represented by the formula (22), the key compound represented by the formula (23), and the key compound represented by the formula (24) may be used.
  • the total of the key compound represented by the formula (22), the key compound represented by the formula (23) and the key compound represented by (24) is 100.
  • the key compound represented by the formula (22), the key compound represented by the formula Z (23), and the key compound represented by the formula Z (2 4) are preferably 60 to 9871. It is hydrolyzed and / or hydrolyzed and condensed at a ratio of ⁇ 301 to 20 (mol%), preferably 65 to 962 to 202 to 15 (mol%).
  • the first and second porous silica particles (HI) and (H2) used in the present invention have an average particle size force of ⁇ 50 nm, preferably 5 to 45 nm, more preferably 5 to 40 nm.
  • the average particle diameter is a number average particle diameter, and is measured with a transmission electron microscope image.
  • the term “porous” means that the specific surface area is 50 to: L000m 2 Zg, preferably 50 to 800 m 2 Zg, and more preferably 100 to 800 m 2 / g. The specific surface area is measured by the BET method.
  • the average particle size is within the above range, scattering of the obtained coating film in the visible light region can be suppressed. Moreover, due to being porous, the density is lowered and the refractive index of the film containing such porous silica particles is lowered.
  • porous silica particles (H) are obtained by the production method described below.
  • the first or second porous silica particles (HI) and (H2) are at least one selected from water, alcohols having 1 to 3 carbon atoms, basic compounds, and acid amides, diols, and semi-ethers of diols.
  • the key compound represented by the above formula (22) and the key compound represented by the formula (23), or the key compound represented by the above formula (22), the formula (23 ) And the compound represented by the formula (24) can be produced by hydrolysis and Z or hydrolysis condensation.
  • an amine compound for example, an amine compound is used.
  • Specific examples include pyridine, pyrrole, piperazine, pyrrolidine, piperidine, picoline, monoethanolamine, diethylanolamine, dimethylmonoethanol.
  • ammonia, ethanolamine, hydroxy-tetramethylamine or the like is used.
  • the acid amide, diol or diol half-ether is preferably compatible with water and alcohol.
  • N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, etc. are used, preferably N, N-dimethylformamide, N, N-dimethylacetamide is used.
  • the diol for example, ethylene glycol, propylene glycol, 1,2-butanediol and the like are used, and preferably ethylene glycol and propylene glycol are used.
  • ethylene glycol monomethyl ether or propylene glycol monomethyl ether is used as the half ether of the diol.
  • porous silica particles used in the present invention can be made porous by the coexistence of acid amide, diol or diol half ether during synthesis.
  • the total concentration of the key compound of formula (22) and the key compound of formula (23) or the key compound of formulas (22) to (24) in the reaction solution is usually 0 in terms of complete hydrolysis condensate. 5 to 10% by weight, preferably 1 to 8% by weight.
  • “in terms of complete hydrolyzed condensate” is a theoretical value calculated on the assumption that the key compound has been completely hydrolyzed and condensed, and the key compound of formula (22) and This corresponds to the weight when X in the key compound of (23) or the key compounds of formulas (22) to (24) is replaced by 2 mol of 1Z of oxygen atoms.
  • the compound of formula (22) and the compound of formula (23), or the compound of formula (22), the compound of formula (23) and the compound of formula (24) are mixed simultaneously. Hydrolysis and Z or hydrolytic condensation, water, alcohols having 1 to 3 carbon atoms, basic compounds, and acid ethers, diols, and semi-ether powers of diols in the presence of at least one selected, Hydrolysis and Z or hydrolytic condensation of the key compound represented by the formula (22), followed by the key compound represented by the formula (23) or the key element represented by the formula (23), respectively.
  • the compound and the key compound represented by the formula (24) may be added to further perform hydrolysis and Z or hydrolysis condensation.
  • the reaction temperature for hydrolysis and Z or hydrolysis condensation can be arbitrarily determined in consideration of the boiling point and reaction time of the alcohol and acid amide to be used.
  • the reaction time is the type of the key compound represented by formula (22), the key compound represented by formula (23) and the key compound represented by formula (24), the reaction rate, the type and amount of base, etc.
  • the optimum value varies depending on the value, and is not limited.
  • the porous silica particles become organic.
  • a dispersion liquid dispersed in a solvent can be obtained.
  • the dispersion medium is water! /
  • an organic solvent is preferred.
  • the organic solvent include alcohols such as methanol, isopropyl alcohol, ethylene glycolate, butanol, ethylene glycol monopolypropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; aromatic carbonization such as toluene and xylene.
  • Hydrogens Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; Esters such as ethyl acetate, butyl acetate, ⁇ -butalate ratatones; Organic solvents such as ethers such as tetrahydrofuran and 1,4 dioxane Of these, alcohols and ketones are preferred. These organic solvents can be used alone or in admixture of two or more as a dispersion medium.
  • the compounding amount of the porous silica particles ( ⁇ ) in the resin composition is usually 5 to 99% by weight, preferably 10 to 98% by weight, based on the total amount of the composition other than the organic solvent. More preferred is -97% by weight. If it is less than 5% by weight, the hardness of the cured film may be insufficient. If it exceeds 99% by weight, sufficient film strength may not be obtained.
  • the amount of particles means the solid content, and when the particles are used in the form of a solvent dispersion, the amount of the particles is The total amount does not include the amount of solvent.
  • the following components can be added to the composition for a low refractive index layer used in the present invention, if necessary.
  • the curable resin composition contains, if necessary, a polyfunctional (meth) acrylate compound containing two or more (meth) atalyloyl groups and Z or one or more (meth) atteroyl groups. Fluorine-containing (meth) atare toy compound can also be added.
  • the compound is not particularly limited as long as it is a compound containing two or more (meth) attalyloyl groups in the molecule.
  • examples of this include neopentyl daldiol di (meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, penta erythritol.
  • neopentyl glycol di (meth) acrylate, dipentaerythritol hex (meth) acrylate, penta Particularly preferred are erythritol tetra (meth) acrylate, dipentaerythr
  • a fluorine-containing (meth) containing one or more (meth) attalyloyl groups If it is an atta relay toy compound, it will not be restrict
  • examples thereof include perfluorooctyl (meth) acrylate, octafluoropentyl (meth) acrylate, trifluoroethyl (meth) acrylate, and the like. These can be used alone or in combination of two or more.
  • the amount of component (I) to be added is not particularly limited, but is usually 0 to 90% by weight based on the total amount of the composition other than the organic solvent. The reason for this is that if the addition amount exceeds 90% by weight, the refractive index of the cured coating film of the composition for forming a low refractive index layer becomes high, and a sufficient antireflection effect may not be obtained. .
  • the amount of component (I) added is more preferably 80% by weight or less, and further preferably 60% by weight or less.
  • a compound that generates active species by irradiation of active energy rays or heat can also be added.
  • a compound that generates active species upon irradiation with active energy rays or heat is used to cure the composition for forming a low refractive index layer.
  • photopolymerization initiators examples include photoradical generators that generate radicals as active species.
  • the active energy ray is defined as an energy ray capable of decomposing a compound that generates active species to generate active species.
  • active energy rays include optical energy rays such as visible light, ultraviolet rays, infrared rays, X rays, ⁇ rays, j8 rays, and ⁇ rays.
  • ultraviolet rays it is preferable to use ultraviolet rays from the viewpoint of having a certain energy level, a high curing speed, and a relatively inexpensive irradiation apparatus, and a small size.
  • photo radical generators include, for example, acetophenone, acetophenone benzil ketal, anthraquinone, 1- (4-isopropylphenol) 2 hydroxy-1-methylpropanone 1-on, carbazole, xanthone, 4-clobenbenzophenone. 4,4'-mino minobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3,1-dimethyl-1,4-meth Xibenzophenone, Chi-xanthone, 2, 2-dimethoxy-2-ferulacetophenone,
  • photopolymerization initiators 2, 2 dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2, 4, 6 Trimethylbenzoyl diphosphine phosphine oxide, 2-methyl- 1 1 [4 (methylthio) phenol] 2 Morpholinopropane 1-one, 2- (dimethylamino) 1 1 [4 (morpholyl) phenol] 2 phenol 1-butanone and the like are more preferable, 1-hydroxycyclohexyl phenyl ketone,
  • the addition amount of the photopolymerization initiator is not particularly limited, but is preferably 0.01 to 20% by weight based on the total amount of the composition other than the organic solvent. This is because when the amount added is less than 0.01% by weight, the curing reaction becomes insufficient, and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may be lowered. On the other hand, when the addition amount of the photopolymerization initiator exceeds 20% by weight, the refractive index of the cured film increases and the antireflection effect may be lowered. For these reasons, it is more preferable to add the photopolymerization initiator to 0.05 to 15% by weight with respect to the total amount of the composition other than the organic solvent. It is more preferable to do this.
  • thermal polymerization initiator examples include a thermal radical generator that generates a radical as the active species.
  • thermal radical generators examples include benzoyl peroxide, tert-butyloxybenzoate, azobisisobutyoxy-tolyl, acetylyl peroxide, lauryl peroxide, tert-butyl peracetate, tamil peroxide, tert-butyl peroxide, tert-butyl hydride Oral peroxide, 2,2, -azobis (2,4-dimethylvale-tolyl), 2,2, -azobis (4-methoxy-2,4-dimethylvale-tolyl), etc., alone or in combination of two or more Can be mentioned.
  • the addition amount of the thermal polymerization initiator is not particularly limited, but is preferably 0.01 to 20% by weight based on the total amount of the composition other than the organic solvent. The reason for this is that if the amount of added calories is less than 0.01% by weight, the curing reaction becomes insufficient, and the scratch resistance and the scratch resistance after immersion in an alkaline aqueous solution may decrease. On the other hand, if the amount of addition of the photopolymerization initiator exceeds S20% by weight, the refractive index of the cured film increases and the antireflection effect may decrease.
  • the thermal polymerization initiator it is more preferable to add the thermal polymerization initiator to 0.05 to 15% by weight with respect to the total amount of the composition other than the organic solvent. It is more preferable that the value be within the range.
  • an organic solvent it is preferable to further add an organic solvent to the composition for forming a low refractive index layer.
  • an organic solvent an alcohol solvent having 1 to 8 carbon atoms, an alcohol solvent having 3 to carbon atoms: a ketone system having L0, or an ester system having 3 to 10 carbon atoms can be preferably used.
  • Ketones methyl ethyl ketone, methyl amyl ketone, methanol, ethanol, t-butanol, isopropanol, propylene glycol methanol monomethyl ether, propylene glycol ether ether, propylene glycol monopropyl ether and the like are particularly preferable. These organic solvents can be used singly or in combination of two or more.
  • the addition amount of the organic solvent is not particularly limited, but is preferably 100 to 100,000 parts by weight with respect to 100 parts by weight of the composition other than the organic solvent. This is because when the amount added is less than 100 parts by weight, it may be difficult to adjust the viscosity of the composition for forming a low refractive index layer. On the other hand, when the amount added exceeds 100,000 parts by weight, the refractive index is low. This is because the storage stability of the composition for forming the rate layer may be decreased, or the viscosity may be excessively decreased to make the handling difficult.
  • the composition for forming a low refractive index layer includes a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, and a surfactant as long as the object and effect of the present invention are not impaired.
  • additives such as plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, silane coupling agents, inorganic fillers other than the component (H), pigments, dyes, and the like can also be contained.
  • the composition for forming a low refractive index layer used in the present invention comprises the above (G) ethylenically unsaturated group-containing fluoropolymer and the above (H) component, or, if necessary, the above (I) component, ⁇ component (Ii)
  • It can be prepared by adding an organic solvent and an additive and mixing at room temperature or under heating conditions. Specifically, it can be prepared using a mixer such as a mixer, a kneader, a ball mill, or a three-necked roll. However, when mixing under heating conditions, it is preferable to carry out at a temperature lower than the decomposition start temperature of the thermal polymerization initiator.
  • the exposure dose is within the range of 0.01 to 10 j / cm 2 .
  • the value is preferred. This is because when the exposure amount is less than 0. OljZcm 2 , curing failure may occur, whereas when the exposure amount exceeds lOjZcm 2 , the curing time may become excessively long. .
  • composition for forming a low refractive index layer is cured by heating, it is preferably heated at a temperature in the range of 30 to 200 ° C for 0.5 to 180 minutes. By heating in this way, an antireflection film having excellent scratch resistance can be obtained more efficiently without damaging the substrate and the like.
  • Spherical ITO fine powder (manufactured by Fuji Chemical Co., Ltd., number average primary particle size 0.013; ⁇ ⁇ ) 200 parts is added to 800 parts of isopropyl alcohol, and dispersed with glass beads for 12 hours. The crow beads were removed to obtain 950 parts of isopropyl alcohol sol (A-1). 2 g of the dispersed sol was weighed on an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour and weighed to determine the solid content, which was 20%. As a result of observing this solid matter with an electron microscope, the minor axis average particle size was 12 nm, the major axis average particle size was 14 nm, and the aspect ratio was 1.2.
  • Production Example 3 Production of organic compound (Bb) containing polymerizable unsaturated group
  • TMM- 3LM- N (consisting of 40 wt% pentaerythritol Atari rate 60 mass 0/0 and pentaerythritol Lumpur tetra strike rate Among them, involved in the reaction It is only pentaerythritol triatalylate having a hydroxyl group.)
  • the organic compound containing a polymerizable unsaturated group Compound (Bb) was obtained.
  • the amount of isocyanate remaining in the product was analyzed by FT-IR, it was 0.1% or less, indicating that the reaction was almost quantitatively completed.
  • the amount of residual isocyanate was measured by FT-IR in the same manner as in Production Example 3. As a result, it was 0.1% by mass or less, confirming that the reaction was almost quantitative. did. In addition, it was confirmed that the molecule contained a urethane bond and an allyloyl group (polymerizable unsaturated group).
  • Production Example 5 Production of reactive zirconia (ZrO) fine powder sol (B-1)
  • Organic compound containing polymerizable unsaturated group produced in Production Example 3 (Bb) l. 9 parts, methyl ethyl ketone zircoazole (Ba) prepared in Production Example 2 (zircon concentration 50%) 142. 2 Part, After mixing 0.1 part of ion-exchanged water and 0.03 part of p-hydroxyphenol monomethyl ether at 60 ° C for 3 hours, add 1.0 part of orthoformate methyl ester and keep the same for 1 hour. Reactive particles (dispersion (B-1)) were obtained by heating and stirring at a temperature. 2 g of this dispersion (B 1) was weighed into an aluminum dish, dried on a hot plate at 120 ° C. for 1 hour, and weighed to obtain a solid content of 51%.
  • Thritol pentaatarylate (C-1; Nippon Kayaku Co., Ltd. product name: KAYADAR DPH A-2C) 39.
  • compound (C 2) 2 represented by formula (5) prepared in Production Example 4 1 part, 1-hydroxycyclohexyl phenol ketone (D-1) 1.0 part, 2-methyl 1- [4- (methylthio) phenol] 2 morpholinopropane 1-one (D-2) 0. 5 parts, 9.9 parts of IPA and 5.4 parts of MEK were mixed and stirred at 30 ° C. for 2 hours to obtain a uniform solution composition.
  • the solid content of this composition was measured in the same manner as in Production Example 5. As a result, it was 50%.
  • compositions of Examples 2 to 8 and Comparative Examples 1 to 7 were obtained in the same manner as in Example 1, except that the compositions shown in Table 1 or Table 2 were changed.
  • the wire bar coater (# 6) on the base material (polyester film A4300 (made by Toyobo Co., Ltd., film thickness: 188 ⁇ m) on which surface easy adhesion treatment was applied)
  • the composition was applied and dried in an oven at 80 ° C for 3 minutes to form a coating film, and then irradiated with 0.3jZcm 2 light in the atmosphere using a metalno and ride lamp. Under conditions, the coating film was cured with ultraviolet rays to form a cured film with a thickness of 3 ⁇ m.
  • Base material Polymer film A4300 with surface easy adhesion treatment (Toyobo Co., Ltd., The composition obtained in the above examples and comparative examples was coated on the film thickness (188 ⁇ m) using a wire bar coater (# 6), and dried in an oven at 80 ° C. for 3 minutes. A coating film was formed. Next, the coating film was UV-cured under a light irradiation condition of 0.3 jZcm 2 in the atmosphere using a metalno and ride lamp to form a cured film having a thickness of 0.1 ⁇ m.
  • the refractive index (n 25 ) at a wavelength of 589 nm at 25 ° C was measured.
  • the surface on which the cured film of the laminate consisting of the base material and the cured film was formed was set on the electrode side and measured at an applied voltage of 100V.
  • the blending amount of the ITO fine powder sol (A-1) represents the dry weight of the fine powder contained in the charged amount of the dispersion sol (excluding the organic solvent).
  • the compounding amount of the reactive ZrO fine powder sol (B-1) is the dispersion sol.
  • the dry weight of fine powder (excluding organic solvent) contained in the amount charged is the dry weight of fine powder (excluding organic solvent) contained in the amount charged.
  • DPHA dipentaerythritol pentaatalylate; trade name KAYADAR D PHA— 2C; manufactured by Nippon Gyaku Co., Ltd.
  • Photopolymerization initiator (D-1) 1-hydroxycyclohexyl phenol ketone; trade name Irgacu re 184; manufactured by Chinoku 'Specialty' Chemicals
  • Photopolymerization initiator (D-2) 2-methyl-1 [4 (methylthio) phenol] 2 morpholinopropane 1-one; trade name Irgacure 907; manufactured by Chinoku's Specialty Chemicals
  • both the surface resistance value and the haze are high, or those having a low surface resistance value have a high haze. Those with a low haze have a high surface resistance, indicating that conductivity and transparency are not compatible.
  • Production Example 6 Production of reactive silica particle sol bonded with an organic compound having a polymerizable unsaturated group
  • Silica particle sol (Methyl ethyl ketone silica sol, MEK-ST — L, Nissan Chemical Industries, Ltd., number average particle size 0.05 ⁇ m, silica concentration 30%) 143g (43g as silica particles), Production Example 3 2.8 g of the solution containing the organic compound (Bb) having a polymerizable unsaturated group produced in the above, 0.1 g of distilled water and 0. Olg of p-hydroquinone monomethyl ether were mixed, and the mixture was heated and stirred at 65 ° C. After 4 hours, 1.Og of orthoformate methyl ester was added, and the mixture was further heated for 1 hour to obtain a reactive silica particle sol having a solid content of 31%.
  • Hexafluoropropylene 86. Og was then added and heating was started.
  • the pressure when the temperature in the autoclave reached 60 ° C was 2.9 X 10 5 Pa.
  • the reaction was continued with stirring at 70 ° C for 20 hours.
  • the pressure dropped to 2.
  • OX 10 5 Pa autoclay The reaction was stopped by cooling the tube with water. After reaching room temperature, the unreacted monomer was released and the autoclave was released to obtain a polymer solution having a solid content concentration of 30.0%.
  • the obtained polymer solution was poured into methanol to precipitate a polymer, which was then washed with methanol and vacuum dried at 50 ° C. to obtain 220 g of a hydroxyl group-containing fluoropolymer.
  • Production Example 8 Production of ethylenically unsaturated group-containing fluoropolymer
  • Reactive silica particle sol 20g obtained in Production Example 6 (6.2g as reactive particles), ethylenically unsaturated group-containing fluorinated polymer obtained in Production Example 8 101.Og (ethylenically unsaturated group-containing) 15.2 g) as a fluoropolymer, 1.7 g dipentaerythritol pentatalylate, 2-methyl-1 [4 (methylthio) phenol] 2 morpholinopropane 1 on (D-2) 1.2 g, Production Example 4 0.4 g of the compound represented by the formula (6) obtained in the above, organic copolymer-containing special silicon (Floren AC-901, Kyoeisha Chemical Co., Ltd.) 0.lg, methyl isobutyl ketone 505.6 g, and at room temperature The mixture was stirred for 1 hour to obtain a composition 1 for forming a low refractive index layer. The solid content was determined in the same manner as in Production Example 8 and found to be 4% by weight.
  • porous silica particle 1 powder sample 10 g was placed in an aluminum dish and dried on a hot plate at 150 ° C. for 1 hour to obtain a porous silica particle 1 powder sample.
  • the BET specific surface area of the obtained porous silica particle powder was measured using AUTOSORB-1 manufactured by Quantachrome Instruments, the specific surface area was 200 m 2 Zg.
  • the curable composition 1 obtained in Example 1 was coated on a polyester film A4300 (manufactured by Toyobo Co., Ltd., film thickness 188 m) subjected to surface easy adhesion treatment using a wire bar coater # 6. And dried in an oven at 80 ° C for 3 minutes. Then in the atmosphere, metal ( 2) Using a ride lamp, the coating film was cured with UV light under the light irradiation condition of UZcm 2 to prepare a film having an antistatic hard coat layer. When the film thickness of the antistatic hard coat layer was measured with a stylus type surface profile measuring instrument, it was 3 m.
  • the composition 1 for forming a low refractive index layer obtained in Production Example 9 was applied using a wire bar coater # 3, and then in an oven at 80 ° C for 1 minute. It dried on the conditions of.
  • the coating film was UV-cured under a light irradiation condition of UZcm 2 under a nitrogen atmosphere under a nitrogen atmosphere, and a low refractive index layer was formed to produce an antireflection laminate 1.
  • the reflectance power of the obtained antireflection laminate 1 was calculated as 0 .: m when the film thickness of the low refractive index layer was calculated.
  • Antireflection laminates 2 to 10 were obtained in the same manner as in Example 9, except that the curable composition and the low refractive index layer-forming composition shown in Table 3 were used.
  • the haze (%) of the cured film was measured according to JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.). The results obtained are shown in Table 3.
  • the reflectance of the resulting anti-reflection laminate was measured with a spectral reflectance measuring device (instant multi-photometering system, MCPD-3000, manufactured by Otsuka Electronics Co., Ltd.). The absolute reflectance was measured in the wavelength range of 400 to 800 nm. And evaluated. Table 3 shows the reflectance at a wavelength of 550 nm.
  • MCPD-3000 instant multi-photometering system
  • Table 3 shows the reflectance at a wavelength of 550 nm.
  • the steel wool resistance test of the antireflection laminate was performed by the following method.
  • steel wool (Bonster No. 0000, manufactured by Nippon Steel Wool Co., Ltd.) was attached to the Gakushin friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film was loaded with a load of 200 g.
  • Gakushin friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.
  • the cloth rubbing resistance test of the antireflection laminate was carried out by the following method. That is, a non-woven fabric (B EMCOT S-2, manufactured by Asahi Kasei Kogyo Co., Ltd.) is attached to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film is subjected to a load lOOOg. By rubbing repeatedly 20 times, the presence or absence of scratches on the surface of the cured film was visually confirmed according to the following criteria. The results obtained are shown in Table 3.
  • the ethanol resistance test of the cured film was performed by the following method. That is, a non-woven fabric soaked with ethanol (BEMCOT S-2, manufactured by Asahi Kasei Kogyo Co., Ltd.) is attached to a Gakushin type friction fastness tester (AB-301, manufactured by Tester Sangyo Co., Ltd.), and the surface of the cured film was repeatedly rubbed 20 times under the condition of a load of 500 g, and the presence or absence of scratches on the surface of the cured film was visually confirmed according to the following criteria. The results obtained are shown in Table 3.
  • Example 9 in which the cured film layer contains soot particles and acid oxide (ZrO) particles.
  • the surface resistance value at which haze is low is also 10 9 ⁇ : ⁇ ⁇ ⁇ / Mouth order and low reflectance is low.
  • Example 17 in which no reactive particles are used as the oxide particles in the cured film layer, it is understood that the haze increases.
  • the curable composition of the present invention, the cured film and the laminate thereof are, for example, plastic optical components, touch panels, film-type liquid crystal elements, plastic containers, floor materials as building interior materials, wall materials, artificial marble, and the like.
  • Protective coating material to prevent scratches (scratches) and prevent contamination of films are, for example, plastic optical components, touch panels, film-type liquid crystal elements, plastic containers, floor materials as building interior materials, wall materials, artificial marble, and the like.
  • Protective coating material to prevent scratches (scratches) and prevent contamination of films are, for example, plastic optical components, touch panels, film-type liquid crystal elements, plastic containers, floor materials as building interior materials, wall materials, artificial marble, and the like.
  • Protective coating material to prevent scratches (scratches) and prevent contamination of films are, for example, plastic optical components, touch panels, film-type liquid crystal elements, plastic containers, floor materials as building interior materials, wall materials, artificial marble, and the like.
  • Protective coating material to prevent scratches (scratches) and prevent contamination of films are
  • an antistatic laminate having a cured film excellent in curability and having a cured film excellent in antistatic properties, hardness, scratch resistance, and transparency on the surface of various substrates. can do.
  • the laminate of the present invention mainly includes, for example, a protective film for touch panels, a transfer foil, a hard coat for optical disks, a window film for automobiles, an antistatic protective film for lenses, and a surface protective film for high-design containers such as cosmetic containers.
  • Anti-static function for various display panels such as CRT, liquid crystal display panel, plasma display panel, electo-luminescence display panel, etc. as a hard coat for the purpose of preventing product surface scratches and electrostatic dust.
  • As an attached antireflection film it can be used as an antireflection film with an antistatic function for plastic lenses, polarizing films, solar battery panels and the like.
  • the laminate of the present invention can prevent scratches (scratches) on, for example, plastic optical parts, touch panels, film-type liquid crystal elements, plastic housings, plastic containers, flooring materials as building interior materials, wall materials, artificial stones, etc. And hard coating materials to prevent contamination; It can be suitably used as an adhesive, a sealing material, a binder material for printing ink, and the like.

Landscapes

  • Laminated Bodies (AREA)

Abstract

L'invention concerne un corps multicouche comprenant une base et une couche contenant les composants (A), (Ba) et (C) décrits ci-dessous. La couche contient de 7 à 40 % en masse du composant (A) et de 20 à 60 % en masse du composant (Ba). (A) est constitué de particules d’oxyde d’indium à base d'étain, (Ba) de particules d'oxyde d'au moins un élément choisi dans le groupe incluant le zirconium, le titane, l’aluminium, le cérium, l’étain et le zinc et (C) est un polymère.
PCT/JP2006/312631 2005-06-30 2006-06-23 Composition durcissable antistatique, film durci de celle-ci et corps multicouche antistatique WO2007004447A1 (fr)

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JP2005191246A JP2007007984A (ja) 2005-06-30 2005-06-30 帯電防止用積層体

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CN112111715A (zh) * 2020-09-22 2020-12-22 长沙壹纳光电材料有限公司 一种改善高阻膜方阻稳定性的方法及系统

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JP5141596B2 (ja) * 2008-03-26 2013-02-13 Ｊｓｒ株式会社 ポリジアルキルポリシロキサン基、パーフルオロポリエーテル基、ウレタン基及び（メタ）アクリロイル基を有する化合物、それを含有する硬化性組成物及び硬化膜
JP5480608B2 (ja) * 2009-12-10 2014-04-23 富士フイルム株式会社 光学フィルム及びその製造方法

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JP2004307735A (ja) * 2003-04-10 2004-11-04 Jsr Corp 液状硬化性組成物、硬化膜及び帯電防止用積層体
JP2005068369A (ja) * 2003-08-27 2005-03-17 Jsr Corp 液状硬化性組成物、硬化膜及び帯電防止用積層体
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JP2004307735A (ja) * 2003-04-10 2004-11-04 Jsr Corp 液状硬化性組成物、硬化膜及び帯電防止用積層体
JP2005068369A (ja) * 2003-08-27 2005-03-17 Jsr Corp 液状硬化性組成物、硬化膜及び帯電防止用積層体
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CN112111715A (zh) * 2020-09-22 2020-12-22 长沙壹纳光电材料有限公司 一种改善高阻膜方阻稳定性的方法及系统

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