JP2007076297A - Laminate for surface coating of optical article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate having a cured film layer made by curing a curable composition capable of forming a coating film (a film) being superior in hardness and scratching resistance, and conbining good transparency and surface resistance, especially to provide an anti-reflecting film laminate. <P>SOLUTION: The laminate comprises a substrate and a cured film layer made by curing a curable composition comprising components (A), (B), (E) and (F) described below. [The curable composition] contains (A) particles containing an oxide of at least one element selected from the group consisting of Si, Al, Zr, Ti, Zn, Ge, In, Sn, Sb and Ce as a main component and a polymerizable unsaturated group, (B) a compound having a methacryloyl group and an acryloyl group in a molecule, (E) a photo-polymerization initiator and (F) a solvent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a laminate for surface coating of an optical article. More specifically, it is excellent in curability and various substrates such as plastic (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene-based resin, etc.), curable composition capable of forming a coating film (film) excellent in hardness, scratch resistance and transparency on the surface of metal, wood, paper, glass, ceramics, slats, etc. The present invention relates to a laminate including a cured film layer obtained by curing an object.

Conventionally, from the viewpoint of ensuring the performance of information communication equipment and taking safety measures, a radiation curable composition has been used on the equipment surface to provide a coating film (hard coat) having scratch resistance and adhesion, and a coating having an antistatic function. A film (antistatic film) is formed.
In addition, in order to impart an antireflection function to an optical article, 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.
In recent years, there has been remarkable development and general use of information communication devices, and further improvements in performance and productivity of hard coats, antistatic films, antireflection films and the like have been demanded.

In particular, optical articles such as plastic lenses are required to be improved in scratch resistance and reduction in transmittance due to reflection. Also in display panels, scratch resistance and reflection on the screen are required. Prevention is now required.
In response to these demands, various radiation curable materials have been proposed with a focus on high productivity and curing at room temperature.

As a material for a low refractive index layer of an antireflection film, for example, fluororesin-based paints containing a hydroxyl group-containing fluoropolymer are known (for example, Patent Documents 1 to 3).
However, in such a fluororesin-based paint, it is necessary to heat and crosslink a hydroxyl group-containing fluoropolymer and a curing agent such as a melamine resin under an acid catalyst in order to cure the coating film. Depending on the conditions, there is a problem that the curing time becomes excessively long and the types of base materials that can be used are limited.
Moreover, although the obtained coating film was excellent in weather resistance, there was a problem that scar resistance and durability were poor.

  Therefore, in order to solve the above-mentioned problems, 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 fluoropolymer are converted into an isocyanate group. A coating composition containing an unsaturated group-containing fluorine-containing vinyl polymer obtained by reacting at a ratio of number / hydroxyl number of 0.01 to 1.0 has been proposed (for example, Patent Document 4). .

However, in the above publication, when preparing an unsaturated group-containing fluorine-containing vinyl polymer, an isocyanate group-containing unsaturated compound in an amount sufficient to react all the hydroxyl groups of the hydroxyl group-containing fluorine-containing polymer is used, Actively left unreacted hydroxyl groups in the polymer.
Therefore, the coating composition containing such a polymer can be cured at a low temperature in a short time, but is further cured using a curing agent such as a melamine resin in order to react the remaining hydroxyl group. There was a need. Furthermore, the coating film obtained in the above publication has a problem that the coating property and scratch resistance are not sufficient.

JP 57-34107 A JP 59-189108 A JP 60-67518 A JP 61-296073 A

  However, although such conventional techniques each exhibit a certain effect, as a cured film that is required to have all functions as a hard coat and an antireflection film in recent years, It was not satisfactory enough.

  The present invention has been made in view of the above-mentioned problems, and is capable of forming a coating film (coating) excellent in hardness and scratch resistance and having both transparency and surface resistance value on the surface of various substrates. It aims at providing the laminated body which has a cured film layer formed by hardening an adhesive composition, especially an antireflection film laminated body.

As a result of earnest research to solve the above-mentioned problems, the present inventor hardens a composition containing specific metal oxide particles, a compound having a methacryloyl group and an acryloyl group, a photopolymerization initiator, and a solvent. It has been found that the above object can be achieved by a laminate having a cured film layer, and the present invention has been completed.
Furthermore, the present inventors have found that the combination of a low refractive index film improves the scratch resistance and stain resistance of the antireflection laminate, thereby completing the present invention.

That is, this invention provides the following laminated bodies and the manufacturing method of a laminated body.
[1] at least a substrate;
A cured film layer obtained by curing a curable composition containing the following components (A), (B), (E) and (F);
A laminate having
[Curable composition]
(A) particles having a polymerizable unsaturated group, the main component being an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium;
(B) a compound having a methacryloyl group and an acryloyl group in one molecule;
(E) Photopolymerization initiator, and (F) Solvent [2] The laminate according to [1], wherein the total number of methacryloyl groups and acryloyl groups of the component (B) is 3 or more.
[3] The laminate according to [1] or [2], wherein the particles having a polymerizable unsaturated group in the component (A) have a group represented by the following formula (1) in addition to the polymerizable unsaturated group. body.
-X-C (= Y) -NH- (1)
[In the formula (1), X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]
[4] At least a base material, the cured film layer, and a layer having a refractive index at a wavelength of 589 nm (hereinafter simply referred to as “refractive index”) lower than the refractive index of the cured film layer (hereinafter referred to as “low refractive index”). The layered product according to any one of the above [1] to [3], which is laminated in this order from the side close to the substrate.
[5] The laminate according to [4], wherein the low refractive index layer comprises (G) a curable fluorinated polymer.
[6] The laminate according to any one of [1] to [5], further including a conductive layer.
[7] The laminate according to any one of [1] to [6], wherein the cured film layer has a thickness of 0.5 to 50 μm.
[8] The laminate according to any one of [1] to [6], wherein the cured film layer has a thickness of 0.05 to 0.5 μm.
[9] At least a substrate;
A layer having a refractive index lower than that of the cured film layer and a refractive index higher than that of the low refractive index layer (hereinafter referred to as “medium refractive index layer”);
The cured film layer;
The low refractive index layer,
The laminate according to [8] above, which is laminated in this order from the side close to the substrate.
[10] At least a substrate;
The cured film layer;
A layer having a refractive index higher than that of the cured layer (hereinafter referred to as “high refractive index layer”);
The low refractive index layer,
The laminate according to [8] above, which is laminated in this order from the side close to the substrate.

  According to the present invention, there is provided a curable composition that is excellent in curability and can form a coating film (film) excellent in hardness, scratch resistance, antistatic property, and transparency on the surface of various substrates. The laminated body which has the cured film formed by hardening can be provided.

Hereinafter, embodiments of the present invention will be specifically described.
The laminate of the present invention includes at least a base material and a cured film layer (hereinafter referred to as “HC cured film layer”) obtained by curing a curable composition containing the following components (A) to (D). It is characterized by having.
[Curable composition]
(A) particles having a polymerizable unsaturated group, the main component being an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium;
(B) a compound having a methacryloyl group and an acryloyl group in one molecule;
(E) a photopolymerization initiator, and (F) a solvent.

  Further, the antireflection film which is a preferable embodiment / use of the laminate of the present invention is an antireflection film in which at least the cured film layer and the low refractive index layer are laminated in this order from the side close to the substrate on the substrate. It is a film, and the low refractive index layer is a cured product of a curable resin composition containing (G) a curable fluorinated polymer.

I. Laminate The most basic configuration of the laminate of the present invention is shown in FIG. The laminate 1 of the present invention has a base material 10 and an HC cured film layer 12.
Since the laminate 1 of the present invention has the HC cured film layer 12 having excellent scratch resistance and adhesion, the laminate 1 is particularly useful as a hard coat. When used as, it is also useful as a high refractive index layer that exhibits high refractive index properties.

  As an application example of the laminate of the present invention, for example, as a hard coat film for various display panels such as CRT, liquid crystal display panel, plasma display panel, electroluminescence display panel, etc., as an antireflection film with a hard coat function Examples thereof include use as an antireflection film with an antistatic function.

Next, the configuration of each layer when the laminate of the present invention is used as an antireflection film having a hard coat function will be described with reference to FIGS. 2A to 2C. The HC cured film layer is used as a layer having various functions by changing the physical properties such as the refractive index by selecting the component (A). For example, the HC cured film layer can be used as a high refractive index layer, a medium refractive index layer, or an antistatic layer that forms an antireflection layer.
When providing an optical article with an antireflection function, 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 substrate or a substrate that has been hard-coated. It is known that this method is effective.
FIG. 2A shows a first embodiment when the laminate of the present invention is used as an antireflection film with a hard coat function. The antireflection film 2 with a hard coat function is formed by forming an HC cured film layer 12 on a substrate 10 and further forming a low refractive index layer 18 thereon. In the first embodiment, the HC cured film layer 12 has both a function as a hard coat layer and a function as a high refractive index layer. In the first embodiment, the refractive index of the HC cured film layer 12 at a wavelength of 589 nm (hereinafter simply referred to as “refractive index”) needs to be higher than the refractive index of the low refractive index layer 18.

  As another form, the HC cured film layer 12 of the antireflection film 2 of the present invention can also function as a hard coat layer, but an antistatic layer can also be provided separately. In this case, the antistatic layer 11 is provided either between the base material 10 and the HC cured film layer 12 or between the HC cured film layer 12 and the low refractive index layer 18. When the antistatic layer 11 is provided between the HC cured film layer 12 and the low refractive index layer 18, the refractive index of the antistatic layer 11 must be higher than the refractive index of the low refractive index layer 18. These aspects are shown in FIGS. 2B and 2C.

  FIG. 2D shows a second embodiment when the laminate of the present invention is used as an antireflection film with a hard coat function. In the second form, the antireflection film 2 with a hard coat function forms the HC cured film layer 12 on the base material 10, and further, the high refractive index layer 16 and the low refractive index layer 18 are formed thereon in this order. Formed. In the second embodiment, the HC cured film layer 12 may have both a function as a hard coat layer and a function as a medium refractive index layer. In the second embodiment, in order for the HC cured film layer 12 to function as a medium refractive index layer, the refractive index of the HC cured film layer 12 is lower than the refractive index of the high refractive index layer 16, and the low refractive index layer It needs to be higher than the refractive index of 18.

  The 3rd form in the case of using the laminated body of this invention as an antireflection film with a hard-coat function is shown to FIG. 2E. In the third embodiment, the antireflection film 2 with a hard coat function forms an HC cured film layer 12 on the substrate 10, and further has a medium refractive index layer 14, a high refractive index layer 16, and a low refractive index. The rate layer 18 is formed in this order.

  In the third embodiment, it is also possible to provide an antistatic layer separately. The antistatic layer 11 can be provided either between the base material 10 and the HC cured film layer 12 or between the HC cured film layer 12 and the medium refractive index layer 14. These forms are shown in FIGS. 2F and 2G.

  The 4th form in the case of using the laminated body of this invention as an antireflection film with a hard-coat function is shown to FIG. 2H. In the fourth embodiment, the antireflection film 2 with a hard coat function is formed by forming a medium refractive index layer 14 on the substrate 10, then forming an HC cured film layer 12, and further forming a low refractive index thereon. Layer 18 is formed in this order. In this case, the HC cured film layer 12 functions exclusively as a high refractive index layer.

  In the fourth embodiment, it is also possible to provide an antistatic layer separately. The antistatic layer 11 can usually be provided between the base material 10 and the medium refractive index layer 14.

A layer and a substrate other than the HC cured film layer provided in each form of the antireflection film with a hard coat function will be described.
(2) Low refractive index layer By providing a low refractive index layer in the outermost layer (layer farthest from the base material) of the laminate of the present invention, the laminate of the present invention can have an antireflection function.
The low refractive index layer is a layer whose refractive index is lower than any of the high refractive index layer, the middle refractive index layer, and the HC cured film layer. Therefore, the low refractive index layer has a refractive index lower than that of the HC cured film layer, even when the HC cured film layer is used as a layer having any function. The refractive index of the low refractive index layer is usually 1.30 to 1.50. The low refractive index layer is usually a thin film having a thickness of 0.05 to 0.5 μm. The HC cured film layer is not used as the low refractive index layer.
The material used for the low refractive index layer is not particularly limited as long as the desired properties can be obtained. And cured products such as epoxy group-containing compounds and fluorine-containing epoxy group-containing compounds. Moreover, in order to raise the intensity | strength of a low refractive index layer, a silica fine particle etc. can also be mix | blended.
In a preferred embodiment in which the laminate of the present invention is used as an antireflection film, the low refractive index layer is formed using a curable resin composition containing a curable fluorinated polymer (G) described later.
The curable resin composition used for the low refractive index layer will be described in detail later.

(3) High Refractive Index Layer By further providing a high refractive index layer in contact with the substrate side of the low refractive index layer in the laminate of the present invention, the antireflection effect of the laminate of the present invention can be further enhanced. it can.
The high refractive index layer is a layer whose refractive index is higher than any of the low refractive index layer and the middle refractive index layer. Therefore, the high refractive index layer has a higher refractive index than the HC cured film layer even when the HC cured film layer is used as a layer having any function other than the high refractive index layer. The refractive index of the high refractive index layer is usually 1.55 to 2.20. The thickness of the high refractive index layer is usually a thin film of 0.05 to 0.5 μm, but it may be a thick film of 0.5 to 50 μm when it also functions as a hard coat layer.
In order to form a high refractive index layer, high refractive index inorganic particles, for example, metal oxide particles can be blended. The HC cured film layer can also be used as a high refractive index layer.

Specific examples of metal oxide particles that can be used in the high refractive index layer include antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, zinc oxide (ZnO) particles, antimony-containing ZnO, and Al-containing materials. Examples thereof include ZnO particles ZrO ₂ particles, TiO ₂ particles, silica-coated TiO ₂ particles, Al ₂ O ₃ / ZrO ₂ -coated TiO ₂ particles, and CeO ₂ particles. Antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, phosphorus-containing tin oxide (PTO) particles, Al-containing ZnO particles, and Al ₂ O ₃ / ZrO ₂ -coated TiO ₂ particles are preferable. These metal oxide particles can be used singly or in combination of two or more. Since the refractive index of the high refractive index layer needs to be higher than the refractive index of the HC cured film layer, (A) an oxide of a metal species having a higher refractive index than the metal oxide particles used in the HC cured film layer By using the particles, or even if the oxide particles of the same metal type as the (A) metal oxide particles used in the HC cured film layer, it is possible to take measures such as mixing and using a larger amount. .

(4) Middle Refractive Index Layer By providing the low refractive index layer, the high refractive index layer, and the middle refractive index layer in order from the outermost layer of the laminate of the present invention, antireflection for light in a wider wavelength range is provided. The effect can be enhanced.
The middle refractive index layer is a layer whose refractive index is higher than that of the low refractive index layer and lower than that of the high refractive index layer. Therefore, even when the HC cured film layer is used as a layer having any function other than the medium refractive index layer, it has a lower refractive index than the HC cured film layer. The refractive index of the medium refractive index layer is usually 1.50 to 1.90, preferably 1.50 to 1.75. The thickness of the medium refractive index layer is usually a thin film of 0.05 to 0.5 μm.
In order to form the middle refractive index layer, inorganic particles having a high refractive index, for example, metal oxide particles can be blended. The HC cured film layer can also be used as a middle refractive index layer.

Specific examples of metal oxide particles that can be used for the medium refractive index layer include antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, ZnO particles, antimony-containing ZnO, Al-containing ZnO particles, and ZrO. ₂ particles, TiO ₂ particles, silica-coated TiO ₂ particles, Al ₂ O ₃ / ZrO ₂ -coated TiO ₂ particles, CeO ₂ particles and the like. Antimony-containing tin oxide (ATO) particles, tin-containing indium oxide (ITO) particles, phosphorus-containing tin oxide (PTO) particles, Al-containing ZnO particles, and ZrO ₂ particles are preferable. These 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 lowered by combining the low refractive index layer, the high refractive index layer, and the middle refractive index layer. In addition to being able to reduce color glare.

(5) Hard coat layer other than the HC cured film layer Since the HC cured film layer is excellent in scratch resistance, it is not usually necessary to provide a separate hard coat layer, but a hard coat layer other than the HC cured film layer is provided. That is not excluded. The hard coat layer other than the HC cured film layer is not particularly limited as long as it has a configuration different from that of the HC cured film layer. Specifically, materials such as SiO ₂ , epoxy resin, acrylic resin, and melamine resin are used. It is preferable to comprise. Moreover, you may mix | blend a silica particle with these resin.
Hard coat layers other than the HC cured film layer have the effect of increasing the mechanical strength of the laminate. The thickness of the hard coat layer other than the HC cured film layer is usually in the range of 0.5 to 50 μm, preferably 1 to 30 μm. The refractive index of the hard coat layer is usually 1.45 to 1.70, preferably 1.45 to 1.60.

(6) Antistatic layer The antistatic layer is not particularly limited as long as it is a conductive layer. In order to form the antistatic layer, conductive metal oxide particles, a conductive polymer, or the like can be blended. The HC cured film layer can also be used as an antistatic layer by blending conductive metal oxide particles as the component (A). The film thickness of the antistatic layer is usually from 0.05 to 30 μm.

(7) Substrate The substrate used in the laminate of the present invention is not particularly limited, such as metal, ceramics, glass, plastic, wood, slate, etc., but exhibits high productivity and industrial utility such as radiation curability. As a material that can be used, it is preferably applied to, for example, a film or a fiber-like substrate. Particularly preferred materials are plastic film and plastic plate. Examples of such plastics include polycarbonate, polymethyl methacrylate, polystyrene / polymethyl methacrylate copolymer, polystyrene, polyester, polyolefin, triacetyl cellulose resin, diallyl carbonate of diethylene glycol (CR-39), ABS resin, AS resin. , Polyamide, epoxy resin, melamine resin, cyclized polyolefin resin (for example, norbornene resin), and the like.

  Although the thickness of a base material is not specifically limited, Usually, 30-300 micrometers, Preferably it is the range of 50-200 micrometers.

(8) Other layers In the production of the laminate of the present invention, in order to further impart other functions such as non-glare effect, selective light absorption effect, weather resistance, durability, transferability, etc. Adding a layer containing light-scattering particles of 1 μm or more, adding a layer containing a dye, adding a layer containing an ultraviolet absorber, adding an adhesive layer, adding an adhesive layer and a release layer Etc. are possible.

  The laminate of the present invention can prevent or contaminate, for example, a plastic optical component, a touch panel, a film-type liquid crystal element, a plastic casing, a plastic container, a flooring material as a building interior material, a wall material, and artificial marble. It can be suitably used as a hard coating material for preventing; an adhesive for various substrates, a sealing material; a binder material for printing ink, and the like.

Only one of these layers may be formed, or two or more different layers may be formed.
In the present invention, a method for producing a layer other than the HC cured film layer can be produced by a known method such as coating and curing, vapor deposition, or sputtering.

II. HC cured film layer The HC cured film layer provided on the substrate of the laminate of the present invention is obtained by curing the following curable composition, and the laminate is hard-coated, high refractive index layer, medium refractive index layer And / or a function as an antistatic layer can be imparted.
The thickness of the HC cured film layer may be used as a thick film or a thin film depending on the function of the layer. Here, the thick film usually means a cured film having a thickness of 0.5 to 50 μm, preferably 1 to 30 μm, and the thin film has a thickness of 0.05 to 0.5 μm, preferably 0.05 to This refers to a 0.3 μm cured film. When the HC cured film layer is used as a hard coat layer or as an antistatic layer, it may be used as a thick film or a thin film. When the HC cured film layer is used as a high refractive index layer or a medium refractive index layer constituting the antireflection layer, it is usually used as a thin film. However, since the function as a hard coat layer and the function as a high refractive index layer or a medium refractive index layer may be used in some cases, the function of the HC cured film layer and its film thickness are not fixed. .
More specifically, in the embodiment of FIGS. 1 to 2D, it may be used as a thick film or a thin film. In the embodiment of FIGS. 2E to 2G, the thick film is usually used. In the embodiment of FIG. 2H, the thin film is usually used.

Hereinafter, each component of the curable composition will be specifically described.
I. Curable composition The curable composition used in the present invention comprises (A) an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. Particles having a polymerizable unsaturated group as a main component, (B) a compound having a methacryloyl group and an acryloyl group, (C) a compound other than the component (B) having two or more polymerizable unsaturated groups, (D ) It contains a compound having one polymerizable unsaturated group in the molecule, (E) a photopolymerization initiator, and (F) a solvent. Among these components, the components (A), (B), (E) and (F) are essential components, and the other components are non-essential components.

Hereinafter, each structural component of the curable composition used by this invention is demonstrated concretely.
1. Metal oxide particles having a polymerizable unsaturated group (A)
The metal oxide particle (A) having a polymerizable unsaturated group used in the present invention is at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium. Particles mainly composed of oxides (hereinafter sometimes referred to as “oxide particles (Aa)”) and organic compounds containing polymerizable unsaturated groups (hereinafter referred to as “organic compounds (Ab)”) )) (Hereinafter also referred to as “reactive particles”).

(1) Oxide particles (Aa)
The oxide particles (Aa) used in the present invention are composed of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony, and cerium from the viewpoint of the colorlessness of the cured film of the resulting curable composition. Particles whose main component is an oxide of at least one element selected from the group. Among these, since zirconium, titanium, and the like have a large refractive index of 1.50 or more, by using oxide particles of these elements, the refractive index of the cured film can be increased and the scratch resistance can be improved. . Further, by using particles of aluminum-containing zinc oxide, tin-containing indium oxide (ITO), antimony-containing tin oxide (ATO), or the like as oxide particles of zinc, indium and antimony, conductivity is imparted to the cured film. be able to.

  Examples of these oxide particles (Aa) mainly include silica, alumina, zirconia, titanium oxide, zinc oxide, germanium oxide, indium oxide, tin oxide, tin-containing indium oxide (ITO), antimony oxide, cerium oxide, and the like. The particle | grains used as a component can be mentioned. Among these, silica, alumina, zirconia and antimony oxide particles are preferable from the viewpoint of high hardness. These can be used singly or in combination of two or more.

  Furthermore, the oxide particles (Aa) are preferably in the form of powder or solvent dispersion sol. In the case of a solvent dispersion sol, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), and cyclohexanone; ethyl acetate, butyl acetate, Esters such as ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; Examples include amides such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. Of these, 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 (Aa) is preferably 0.001 μm to 2 μm, more preferably 0.001 μm to 0.2 μm, and particularly preferably 0.001 μm to 0.1 μm. When the number average particle diameter exceeds 2 μm, the transparency when the cured film is formed tends to be lowered, or the surface state when the film is formed tends to be deteriorated. Various surfactants and amines may be added to improve the dispersibility of the particles.
The number average particle diameter of the oxide particles (Aa) can be measured by, for example, a dynamic light scattering particle size distribution measuring apparatus manufactured by Horiba, Ltd.

  As a product marketed as silicon oxide particles (for example, silica particles), for example, colloidal silica, manufactured by Nissan Chemical Industries, Ltd., trade names: methanol silica sol, IPA-ST, MEK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL and the like can be mentioned. Moreover, as a powder silica, Nippon Aerosil Co., Ltd. product name: Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Asahi Glass Co., Ltd. Product name: Sildex H31, H32, H51, H52, H121 H122, manufactured by Nippon Silica Kogyo Co., Ltd. Trade names: E220A, E220, manufactured by Fuji Silysia Co., Ltd., trade names: SYLYSIA470, manufactured by Nippon Sheet Glass Co., Ltd.

  Moreover, as an aqueous dispersion product of alumina, product names manufactured by Nissan Chemical Industries, Ltd .: Alumina sol-100, -200, -520; As an isopropanol dispersion product of alumina, product names manufactured by Sumitomo Osaka Cement Co., Ltd .: AS- As a toluene dispersion of alumina 150I, manufactured by Sumitomo Osaka Cement Co., Ltd. Product name: AS-150T; As a zirconia toluene dispersion, manufactured by Sumitomo Osaka Cement Co., Ltd. Product name: HXU-110JC; zinc antimonate powder Product name: Celnax; Alumina, titanium oxide, tin oxide, indium oxide, zinc oxide and other powder and solvent dispersion products are manufactured by C-Chemicals Co., Ltd. Name: Nanotech; Antimony-containing tin oxide aqueous dispersion sol manufactured by Ishihara Sangyo Co., Ltd. Product name: SN-100D The ITO powder, Mitsubishi Materials Co., Ltd. product; a cerium oxide aqueous dispersion, Taki Chemical Co., trade name: Nidoraru like.

The oxide particles (Aa) have a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, or an indeterminate shape, and preferably a spherical shape. The specific surface area of the oxide particles (Aa) (by the BET specific surface area measurement method using nitrogen) is preferably 10 to 1000 m ² / g, and more preferably 100 to 500 m ² / g. These oxide particles (Aa) can be used in a dry state, or dispersed in water or an organic solvent. For example, a dispersion of fine oxide particles known in the art as a solvent dispersion sol of the above oxide can be used directly. In particular, use of a solvent-dispersed sol of an oxide is preferable in applications that require excellent transparency in a cured film.

  The refractive index of the cured film can be increased by using particles having a high refractive index such as zirconia and titanium oxide among the oxide particles (Aa). Moreover, electroconductivity can also be provided to a cured film by using an ITO particle and an antimony containing tin oxide particle. Furthermore, the scratch resistance can be further improved by using silica particles.

(2) Organic compound (Ab)
The organic compound (Ab) used in the present invention is a compound containing a polymerizable unsaturated group in the molecule, and is a specific organic compound containing a group represented by the following formula (1) in addition to the polymerizable unsaturated group. Preferably there is.
-X-C (= Y) -NH- (1)
[In the formula (1), X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]
More preferably, it includes a [—O—C (═O) —NH—] group, and further includes a [—O—C (═S) —NH—] group and a [—S—C (═O) —NH— group. ] Containing at least one of the groups. Moreover, it is preferable that this organic compound (Ab) is a compound which has a silanol group in a molecule | numerator, or a compound which produces | generates a silanol group by hydrolysis.

(I) Polymerizable unsaturated group The polymerizable unsaturated group contained in the organic compound (Ab) is not particularly limited, and examples thereof include acryloyl group, methacryloyl group, vinyl group, propenyl group, butadienyl group, styryl group, and ethynyl. Preferred examples include a group, a cinnamoyl group, a maleate group and an acrylamide group.
This polymerizable unsaturated group is a structural unit that undergoes addition polymerization with active radical species.

(Ii) The group represented by the formula (1) The group [—X—C (═Y) —NH—] represented by the formula (1) contained in the specific organic compound is specifically represented by [—O—C (═O) —NH—], [—O—C (═S) —NH—], [—S—C (═O) —NH—], [—NH—C (═O) —NH—]. , [—NH—C (═S) —NH—], and [—S—C (═S) —NH—]. These groups can be used individually by 1 type or in combination of 2 or more types. Among them, from the viewpoint of thermal stability, [—O—C (═O) —NH—] group, [—O—C (═S) —NH—] group and [—S—C (═O) — It is preferable to use in combination with at least one of the NH-] groups.
The group [—X—C (═Y) —NH—] represented by the formula (1) generates an appropriate cohesive force due to hydrogen bonding between molecules, and has excellent mechanical strength and group when formed into a cured film. It is considered that it gives properties such as adhesion to the material and heat resistance.

(Iii) A silanol group or a group that generates a silanol group by hydrolysis The organic compound (Ab) is a compound having a silanol group in the molecule (hereinafter sometimes referred to as “silanol group-containing compound”) or a silanol group by hydrolysis. It is preferable that it is a compound (hereinafter, sometimes referred to as “silanol group-generating compound”). 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 a silicon atom. Bonded compounds, that is, alkoxysilyl group-containing compounds or aryloxysilyl group-containing compounds are preferred.
The silanol group-generating site of the silanol group or the silanol group-generating compound is a structural unit that binds to the oxide particles (Aa) by a condensation reaction or a condensation reaction that occurs following hydrolysis.

(Iv) Preferred Embodiment As a preferred specific example of the organic compound (Ab), for example, a compound represented by the following formula (2) can be mentioned.

In the formula, R ³³ and R ³⁴ may be the same or different, and are a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, for example, methyl, ethyl, propyl, butyl, octyl, phenyl, A xylyl group etc. can be mentioned. Here, c is an integer of 1 to 3.
Examples of the group represented by [(R ³³ O) _c R ³⁴ _3-c Si—] include a trimethoxysilyl group, a triethoxysilyl group, a triphenoxysilyl group, a methyldimethoxysilyl group, a dimethylmethoxysilyl group, and the like. Can be mentioned. Of these groups, a trimethoxysilyl group or a triethoxysilyl group is preferable.
R ³⁵ 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 ³⁶ is a divalent organic group, and is usually selected from divalent organic groups having a molecular weight of 14 to 10,000, preferably a molecular weight of 76 to 500.
R ³⁷ is a (d + 1) -valent organic group, and is preferably selected from a chain, branched or cyclic saturated hydrocarbon group and unsaturated hydrocarbon group.
Q 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. Moreover, d 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.

  Specific examples of the compound represented by the formula (2) include compounds represented by the following formula (3) or formula (4).

［式（３）及び式（４）中、「Ａｃｒｙｌ」は、アクリロイル基を示す。］

[In the formulas (3) and (4), “Acryl” represents an acryloyl group. ]

  For the synthesis of the organic compound (Ab) used in the present invention, for example, a method described in JP-A-9-100111 can be used. Preferably, mercaptopropyltrimethoxysilane and isophorone diisocyanate are mixed in the presence of dibutyltin dilaurate and reacted at 60 to 70 ° C. for several hours, then pentaerythritol triacrylate is added, and further at 60 to 70 ° C. for several hours. Produced by reacting to some extent. Typically, a mixture of the compound represented by the above formula (3) and the compound represented by the above formula (4) is obtained.

  The amount of the organic compound (Ab) bonded to the oxide particles (Aa) is preferably 0, based on 100% by mass of the reactive particles (A) (the total of the oxide particles (Aa) and the organic compound (Ab)). 0.01 mass% or more, more preferably 0.1 mass% or more, and particularly preferably 1 mass% or more. When the binding amount of the organic compound (Ab) bound to the oxide particles (Aa) is less than 0.01% by mass, the dispersibility of the reactive particles (A) in the composition is not sufficient, and the cured film obtained Transparency and scratch resistance may not be sufficient. Moreover, the compounding ratio of the oxide particles (Aa) in the raw material during the production of the reactive particles (A) is preferably 5 to 99% by mass, and more preferably 10 to 98% by mass.

5 to 90 mass% is preferable with respect to the composition whole quantity except a solvent, and, as for the compounding (content) amount in the curable composition of a reactive particle (A), 15 to 85 mass% is more preferable. When it is less than 5% by mass, the hardness of the cured film becomes insufficient, or when a high refractive index particle such as zirconia particles is used, a cured film having a high refractive index may not be obtained, and exceeds 90% by mass. In this case, the film formability may be insufficient.
In this case, the content of the oxide particles (Aa) constituting the reactive particles (A) in the composition is preferably 65 to 90% by mass.
The amount of the reactive particles (A) means a solid content, and when the reactive particles (A) are used in the form of a solvent-dispersed sol, the amount of the solvent does not include the amount of the solvent.

2. (B) Compound having methacryloyl group and acryloyl group The component (B) used in the present invention is not particularly limited as long as it is a compound having a methacryloyl group and an acryloyl group in one molecule. However, it is preferable not to contain silicon or fluorine.
Since the component (B) has a methacryloyl group and an acryloyl group in the same molecule, it is laminated on the upper layer of the hard coat film formed by curing the composition of the present invention by the contribution of the methacryloyl group having a relatively low curing rate. It is a component that improves the adhesion to the low refractive index film and gives a laminate excellent in scratch resistance. In addition, since it also has an acryloyl group, it can give a cured film with excellent flatness without deteriorating the curability in the vicinity of the surface of the cured film, thereby obtaining a laminate having excellent optical performance. it can.

Specific examples of the component (B) include compounds represented by the following formulas (5) and (6).

  (B) As a commercial item which can be used as a component, NK oligo U-6HA (the compound of said Formula (6); Shin-Nakamura Chemical Co., Ltd.) can be mentioned, for example.

  The total number of methacryloyl groups and acryloyl groups possessed by the component (B) is necessarily 2 or more, preferably 3 or more, and more preferably 4 or more. Moreover, it is preferable that the ratio with respect to the total number of the methacryloyl group and acryloyl group of the number of the methacryloyl group which (B) component has is 15 to 85%, and it is further more preferable that it is 20% to 75%.

  The component (B) of the present invention is not particularly limited, and can be obtained, for example, by reacting (a) a polyisocyanate compound and (b) a hydroxy group-containing (meth) acrylate monomer. By changing the ratio of (a) polyisocyanate compound and (b) hydroxy group-containing (meth) acrylate monomer used for the synthesis of component (B), the number of methacryloyl groups in component (B) and The ratio with respect to the total number of acryloyl groups can be adjusted.

  The blending (content) amount of component (B) used in the present invention is preferably 1 to 80% by weight, more preferably 5 to 80% by weight, based on the total amount of the composition excluding the solvent. 60% by mass is particularly preferred. If it is less than 1% by mass or more than 80% by mass, it may not be possible to obtain a high hardness when it is used as a cured film, and the adhesion of the coating film may be lowered.

3. (C) Compound other than the component (B) having two or more polymerizable unsaturated groups Compounds other than the component (B) having two or more polymerizable unsaturated groups in the molecule used in the present invention ( Hereinafter, the “polymerizable unsaturated group-containing compound (C)” or “compound (C)”) is an optional additive component that is suitably used to improve the film-forming property of the composition. The compound (C) 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. . Of these, (meth) acrylic esters are preferred.

［式（７）中、「Ａｃｒｙｌ」は、アクリロイル基を示す。］

［式（８）中、「Ａｃｒｙｌ」は、アクリロイル基を示す。］ Hereinafter, specific examples of the compound (C) used in the present invention include (meth) acrylic esters such as trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth). Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, Ethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, bis (2-hydroxyethyl) isocyanurate Di (meth) acrylates, poly (meth) acrylates of ethylene oxide or propylene oxide adducts to these starting alcohols, oligoesters (meth) acrylates having two or more (meth) acryloyl groups in the molecule, oligos Examples include ether (meth) acrylates, oligourethane (meth) acrylates, oligoepoxy (meth) acrylates, compounds represented by the following formula (7) or the following formula (8). Among them, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, 7) or a compound represented by the following formula (8) is preferable.

[In the formula (7), “Acryl” represents an acryloyl group. ]

[In the formula (8), “Acryl” represents an acryloyl group. ]

  Examples of vinyl compounds include divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, and triethylene glycol divinyl ether.

  Commercially available products that can be used as the polymerizable unsaturated group-containing compound (C) include, for example, Sanwa Chemical Co., Ltd. Product Name: Nicalak MX-302, Toagosei Co., Ltd. Product 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, Nippon Kayaku Co., Ltd. Product name: KAYARAD D-310, D-330, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR-295, SR-355, SR-399E SR-494, SR-9041, SR-368, SR-415, SR-444, SR-454, SR-492, SR-499, SR-502, SR-9020, SR-9035, SR-111, SR -212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003, PET-30 , T-1420, GPO-303, TC-120S, HDDA, NPGDA, TPGDA, PEG400DA, MAN A, HX-220, HX-620, R-551, R-712, R-167, R-526, R-551, R-712, R-604, R-684, TMPTA, THE-330, TPA- 320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA, Kyoeisha Chemical Co., Ltd. product name: Light acrylate PE-4A, DPE-6A, DTMP-4A, and the like.

  The compounding (containing) amount of compound (C) optionally used in the present invention is preferably 0 to 80% by mass, more preferably 0 to 75% by mass, based on the total amount of the composition excluding the solvent.

4). Compound (D) having one polymerizable unsaturated group in the molecule
In the composition of the present invention, in addition to the compound having two or more polymerizable unsaturated groups in the molecule of the component (C), if necessary, a compound having one polymerizable unsaturated group in the molecule (D) (hereinafter sometimes referred to as “compound (D)”) may also be contained.

  Examples of the polymerizable unsaturated group possessed by the compound (D) used in the present invention include the groups described in the description of the component (C), and specific examples of the compound (D) include, for example, N-vinylpyrrolidone. , Vinyl group-containing lactams such as N-vinylcaprolactam, isobornyl (meth) acrylate, bornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, Cyclohexyl (meth) acrylate and other alicyclic structure-containing (meth) acrylate, benzyl (meth) acrylate, 4-butylcyclohexyl (meth) acrylate, acryloylmorpholine, vinylimidazole, vinylpyridine, 2-hydroxyethyl (meth) acrylate, 2-Hide Xylpropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, Sil (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) ) Acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxy Polypropylene glycol (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth ) Acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) Examples include acrylate, N, N-diethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and the like.

  It is preferable that the compounding quantity (content) of the compound (D) in the composition of this invention is 0-30 mass parts with respect to the composition whole quantity except a solvent.

5. Photopolymerization initiator (E)
The photopolymerization initiator (E) of the present invention is not particularly limited as long as it can be decomposed by light irradiation to generate radicals to initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexylphenyl Ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'- Dimethoxybenzophenone, 4,4′-diaminobenzophenone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2- Droxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2, 4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, oligo (2-hydroxy-2-methyl-1- (4- ( 1-methylvinyl) phenyl) propanone) and the like. . Among these, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one, and the like are preferable.

  As a commercial item of a photoinitiator, for example, Ciba Specialty Chemicals Co., Ltd. trade name: Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG 24-61, Darocur 1116, 1173, manufactured by BASF, Inc. Product name: Lucillin TPO, manufactured by UCB, Inc. Product name: Ubekrill P36, manufactured by Fratteri Lamberti, Inc. Product names: Ezacure KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B, etc. be able to.

When hardening the composition of this invention, a photoinitiator and a thermal-polymerization initiator can be used together as needed.
Preferable thermal polymerization initiators include, for example, peroxides and azo compounds, and specific examples include benzoyl peroxide, t-butyl-peroxybenzoate, azobisisobutyronitrile, and the like. it can.

  The blending amount (content) of the photopolymerization initiator (E) used in the present invention is preferably 0.01 to 20% by mass, and preferably 0.1 to 10% by mass with respect to the total amount of the composition excluding the solvent. % Is more preferred. If it is less than 0.01% by mass, the film formability may be insufficient. If it exceeds 20% by mass, a cured film having a high hardness may not be obtained.

6). (F) Solvent The solvent that can be used in the present invention is not particularly limited as long as it does not inhibit the solubility / dispersibility of components other than the solvent. For example, methanol, ethanol, isopropanol, butanol, octanol, etc. Alcohols such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc .; esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ethylene glycol Ethers such as monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbons such as benzene, toluene and xylene; dimethylformamide, dimethylacetamide, N-methyl Amides such as Rupiroridon like. Moreover, the usage-amount of this solvent is although it does not restrict | limit in particular, It is 5-100,000 mass parts normally with respect to 100 mass parts of composition whole quantity except a solvent, Preferably it is 10-10,000 mass parts.
The thickness of the coating film can be adjusted by diluting with a solvent. For example, the viscosity when used as an antireflection film or a coating material is usually 0.1 to 50,000 mPa · sec / 25 ° C., and preferably 0.5 to 10,000 mPa · sec / 25 ° C.

7). Other components In the curable composition used in the present invention, as long as the effects of the present invention are not impaired, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, Surfactants, plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, inorganic fillers, pigments, dyes and the like can be appropriately blended.

8). Methacryloyl group concentration in the composition The methacryloyl group concentration in the curable composition used in the present invention is the amount of methacryloyl groups in the composition 100 g excluding the solvent (F) (hereinafter referred to as “methacryloyl group concentration”). It is preferable that it is 0.001-0.5 mol. There exists a tendency for the abrasion resistance of a laminated body to fall that a methacryloyl group density | concentration is less than 0.001 mol / 100g. When the methacryloyl group concentration exceeds 0.5 mol / 100 g, the surface curability of the cured film is lowered, so that the flatness of the cured film is deteriorated and the optical properties of the laminate tend to be lowered. . For these reasons, the methacryloyl group concentration is preferably 0.002 to 0.3 mol / 100 g.

9. Method of Applying Composition (Coating) The composition of the present invention is suitable for use as an antireflection film or a coating material. Examples of the base material to be antireflection or coated include plastics (polycarbonate, polymethacrylate, polystyrene). Polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal, wood, paper, glass, slate and the like. The shape of these substrates may be a plate, film or three-dimensional molded body, and the coating method is a normal coating method such as dipping coating, spray coating, flow coating, shower coating, roll coating, spin coating, brush coating, etc. Can be mentioned. The thickness of the coating film in these coatings is usually 0.1 to 400 μm, preferably 1 to 200 μm after drying and curing.

10. Method of Curing Composition The composition of the present invention can be cured by heat and / or radiation (light). When using heat, as the heat source, for example, an electric heater, an infrared lamp, hot air, or the like can be used. In the case of radiation (light), the radiation source is not particularly limited as long as the composition can be cured in a short time after coating. For example, as an infrared radiation source, a lamp, a resistance heating plate, Commercially available lasers, etc., as visible ray sources, sunlight, lamps, fluorescent lamps, lasers, etc., ultraviolet ray sources, mercury lamps, halide lamps, lasers, etc., and electron beam sources Using thermionic electrons generated from tungsten filaments, cold cathode method for generating metal through high voltage pulse, and secondary electron method using secondary electrons generated by collision between ionized gaseous molecules and metal electrode Can be mentioned. Moreover, as a source of alpha rays, beta rays, and gamma rays, for example, a fission material such as Co ⁶⁰ can be cited. For the gamma rays, a vacuum tube or the like that causes accelerated electrons to collide with the anode can be used. These radiations can be irradiated alone or in combination of two or more at a certain time.

III. Low Refractive Index Layer In order to use the laminate of the present invention as an antireflection film, it is necessary to form a low refractive index layer on at least the cured film layer. The low refractive index layer formed in the laminate of the present invention is preferably a cured product containing (G) a curable fluorinated polymer, and (H) a curable resin composition containing silica particles. More preferably, it is a cured product composed of a product (hereinafter referred to as “a composition for forming a low refractive index layer”).
Hereinafter, components (G) and (H) will be described.

1. (G) Curable fluorine-containing polymer The curable fluorine-containing polymer (G) used in the composition for forming a low refractive index layer is not particularly limited as long as it is a thermosetting or radiation-curable fluorine-containing polymer. As the thermosetting fluoropolymer, from the viewpoint of affinity with other components in the composition for forming a low refractive index layer, a thermosetting fluoropolymer containing a hydroxyl group (hereinafter referred to as “hydroxyl group-containing fluoropolymer”). "Fluoropolymer"). The radiation-curable fluorine-containing polymer is a radiation-curable fluorine-containing polymer obtained by reacting a hydroxyl group-containing fluorine-containing polymer with a compound containing one isocyanate group and at least one ethylenically unsaturated group. A radiation curable fluorine-containing polymer obtained by adding acrylic acid or a halogen salt of acrylic acid to a polymer or a hydroxyl group-containing fluorine-containing polymer is preferable.

(1) Hydroxyl group-containing fluorine-containing polymer The hydroxyl group-containing fluorine-containing polymer is not particularly limited as long as it is a fluorine-containing polymer having a hydroxyl group. And (c).
(A) A structural unit represented by the following formula (9).
(B) A structural unit represented by the following formula (10).
(C) A structural unit represented by the following formula (11).

［式（９）中、Ｒ^１はフッ素原子、フルオロアルキル基又は−ＯＲ^２で表される基（Ｒ^２はアルキル基又はフルオロアルキル基を示す）を示す］

[In formula (9), R ¹ represents a fluorine atom, a fluoroalkyl group or a group represented by —OR ² (R ² represents an alkyl group or a fluoroalkyl group)]

［式（１０）中、Ｒ^３は水素原子又はメチル基を、Ｒ^４はアルキル基、−(ＣＨ₂)_ｘ−ＯＲ^５若しくは−ＯＣＯＲ^５で表される基（Ｒ^５はアルキル基又はグリシジル基を、ｘは０又は１の数を示す）、カルボキシル基又はアルコキシカルボニル基を示す］

[In formula (10), R ³ represents a hydrogen atom or a methyl group, R ⁴ represents an alkyl group, and a group represented by — (CH ₂ ) _x —OR ⁵ or —OCOR ⁵ (R ⁵ represents an alkyl group or a glycidyl group. , X represents a number of 0 or 1, and represents a carboxyl group or an alkoxycarbonyl group]

［式（１１）中、Ｒ^６は水素原子又はメチル基を、Ｒ^７は水素原子又はヒドロキシアルキル基を、ｖは０又は１の数を示す］

[In formula (11), R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a hydrogen atom or a hydroxyalkyl group, and v represents a number of 0 or 1]

(I) Structural unit (a)
In the above formula (9), examples of the fluoroalkyl group of R ¹ and R ² include a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluorohexyl group, a perfluorocyclohexyl group, and the like. A C1-C6 fluoroalkyl group is mentioned. The alkyl group R ^2, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an alkyl group having 1 to 6 carbon atoms such as a cyclohexyl group.

The structural unit (a) can be introduced by using a fluorine-containing vinyl monomer as a polymerization component. Such a fluorine-containing vinyl 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 thereof include fluororefines such as tetrafluoroethylene, hexafluoropropylene and 3,3,3-trifluoropropylene; alkyl perfluorovinyl ethers or alkoxyalkyl perfluorovinyl ethers; perfluoro (methyl vinyl ether), perfluoro Perfluoro (alkyl vinyl ethers) such as (ethyl vinyl ether), perfluoro (propyl vinyl ether), perfluoro (butyl vinyl ether), perfluoro (isobutyl vinyl ether); perfluoro (alkoxyalkyl vinyl ether) such as perfluoro (propoxypropyl vinyl ether) ) Class of single species or a combination of two or more species.
Among these, hexafluoropropylene and perfluoro (alkyl vinyl ether) or perfluoro (alkoxyalkyl vinyl ether) are more preferable, and a combination of these is more preferable.

In addition, the content rate of a structural unit (a) is 20-70 mol% when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mol%. The reason for this is that when the content is less than 20 mol%, it is sometimes difficult to develop a low refractive index, which is the characteristic of the optically fluorine-containing material as intended by the present application. If the ratio exceeds 70 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent, transparency, or adhesion to the substrate may be lowered.
For these reasons, the content of the structural unit (a) is more preferably 25 to 65 mol%, and more preferably 30 to 60 mol%, based on the total amount of the hydroxyl group-containing fluoropolymer. Is more preferable.

(Ii) Structural unit (b)
In the formula (10), examples of the alkyl group represented by R ³ or R ⁴ 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, and R ⁵ Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

  The structural unit (b) can be introduced by using the above-mentioned vinyl monomer having a substituent as a polymerization component. Examples of such vinyl monomers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n -Alkyl vinyl ethers or cycloalkyl vinyl ethers such as octyl vinyl ether, n-dodecyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether; allyl ethers such as ethyl allyl ether, butyl allyl ether; vinyl acetate, vinyl propionate, vinyl butyrate, pivalin Carboxylic acid vinyl ester such as vinyl acid vinyl, vinyl caproate, vinyl vinyl versatate, vinyl stearate Tellurium; methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- ( (Meth) acrylic acid esters such as n-propoxy) ethyl (meth) acrylate; (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and other unsaturated carboxylic acids, etc. The combination of is mentioned.

In addition, the content rate of a structural unit (b) is 10-70 mol% when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mol%. This is because when the content is less than 10 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced. On the other hand, when the content exceeds 70 mol%, the hydroxyl group This is because optical properties such as transparency and low reflectivity of the fluorinated polymer may be deteriorated.
For such reasons, the content of the structural unit (b) is more preferably 20 to 60 mol%, and more preferably 30 to 60 mol%, based on the total amount of the hydroxyl group-containing fluoropolymer. Is more preferable.

(Iii) Structural unit (c)
In the formula (11), as the hydroxyalkyl group of R ⁷ , 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 5-hydroxypentyl group , 6-hydroxyhexyl group and the like.

The structural unit (c) can be introduced by using a hydroxyl group-containing vinyl monomer as a polymerization component. Examples of such hydroxyl group-containing vinyl monomers include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 5-hydroxypentyl vinyl ether, Examples include hydroxyl group-containing vinyl ethers such as 6-hydroxyhexyl vinyl ether, hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether, allyl alcohol, and the like.
In addition to the above, the hydroxyl group-containing vinyl monomer includes 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone (meth) acrylate, and polypropylene. Glycol (meth) acrylate or the like can be used.

In addition, it is preferable that the content rate of a structural unit (c) shall be 5-70 mol% when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mol%. This is because when the content is less than 5 mol%, the solubility of the hydroxyl group-containing fluoropolymer in the organic solvent may be reduced, whereas when the content exceeds 70 mol%, the hydroxyl group This is because optical properties such as transparency and low reflectivity of the fluorinated polymer may be deteriorated.
For such reasons, the content of the structural unit (c) is more preferably 5 to 40 mol%, and more preferably 5 to 30 mol%, based on the total amount of the hydroxyl group-containing fluoropolymer. Is more preferable.

(Iv) Structural unit (d) and structural unit (e)
The hydroxyl group-containing fluoropolymer preferably further comprises the following structural unit (d).

［式（１２）中、Ｒ^８及びＲ^９は、同一でも異なっていてもよく、水素原子、アルキル基、ハロゲン化アルキル基又はアリール基を示す］ (D) A structural unit represented by the following formula (12).

[In Formula (12), R ⁸ and R ⁹ may be the same or different and each represents a hydrogen atom, an alkyl group, a halogenated alkyl group or an aryl group]

In the formula (12), the alkyl group of R ⁸ or R ^{9 is} an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group, and the halogenated alkyl group is a trifluoromethyl group or perfluoro group. C1-C4 fluoroalkyl groups, such as an ethyl group, a perfluoropropyl group, a perfluorobutyl group, etc., A phenyl group, a benzyl group, a naphthyl group etc. are mentioned as an aryl group, respectively.

  The structural unit (d) can be introduced by using an azo group-containing polysiloxane compound having a polysiloxane segment represented by the formula (12). Examples of such azo group-containing polysiloxane compounds include compounds represented by the following formula (13).

［式（１３）中、Ｒ^１８〜Ｒ^２１は、同一でも異なっていてもよく、水素原子、アルキル基又はシアノ基を示し、Ｒ^２２〜Ｒ^２５は、同一でも異なっていてもよく、水素原子又はアルキル基を示し、ｐ、ｑは１〜６の数、ｓ、ｔは０〜６の数、ｙは１〜２００の数、ｚは１〜２０の数を示す。］

[In the formula (13), R ^{18 to} R ²¹ may be the same or different and each represents a hydrogen atom, an alkyl group or a cyano group, and R ^{22 to} R ²⁵ may be the same or different and represent a hydrogen atom. Alternatively, it represents an alkyl group, p and q are numbers 1 to 6, s and t are numbers 0 to 6, y is a number 1 to 200, and z is a number 1 to 20. ]

  When the compound represented by the formula (13) is used, the structural unit (d) is included in the hydroxyl group-containing fluoropolymer as a part of the structural unit (e).

［式（１４）中、Ｒ^１８〜Ｒ^２１、Ｒ^２２〜Ｒ^２５、ｐ、ｑ、ｓ、ｔ及びｙは、上記式（１３）と同じである。］ (E) A structural unit represented by the following formula (14).

[In formula (14), R ^{18 to} R ²¹ , R ^{22 to} R ²⁵ , p, q, s, t, and y are the same as those in the above formula (13). ]

In the formulas (13) and (14), examples of the alkyl group represented by R ^{18 to} R ²¹ include alkyl groups having 1 to 12 carbon atoms such as a methyl group, an ethyl group, a propyl group, a hexyl group, and a cyclohexyl group. ²² to R ²⁵ alkyl the methyl group, an ethyl group, an alkyl group having 1 to 3 carbon atoms such as a propyl group.

  In the present invention, the azo group-containing polysiloxane compound represented by the above formula (13) is particularly preferably a compound represented by the following formula (15).

［式（１５）中、ｙ及びｚは、上記式（１３）と同じである。］

[In the formula (15), y and z are the same as in the above formula (13). ]

In addition, it is preferable that the content rate of a structural unit (d) shall be 0.1-10 mol% when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mol%. The reason for this is that when the content is less than 0.1 mol%, the surface slipperiness of the coated film after curing is lowered, and the scratch resistance of the coated film may be lowered. If it exceeds 10 mol%, the transparency of the hydroxyl group-containing fluoropolymer is inferior, and when used as a coating material, repelling or the like may occur easily during coating.
For these reasons, the content of the structural unit (d) is more preferably 0.1 to 5 mol% with respect to the total amount of the hydroxyl group-containing fluoropolymer, More preferably, it is mol%. For the same reason, the content of the structural unit (e) is desirably determined so that the content of the structural unit (d) contained therein is in the above range.

(V) Structural unit (f)
It is also preferred that the hydroxyl group-containing fluoropolymer further comprises the following structural unit (f).

［式（１６）中、Ｒ^２６は乳化作用を有する基を示す］ (F) A structural unit represented by the following formula (16).

[In the formula (16), R ²⁶ represents a group having an emulsifying action]

In the formula (16), the group having an emulsifying action of R ²⁶ includes a group having both a hydrophobic group and a hydrophilic group, and the hydrophilic group having a polyether structure such as polyethylene oxide and polypropylene oxide. preferable.

［式（１７）中、ｎは１〜２０の数、ｍは０〜４の数、ｕは３〜５０の数を示す］ An example of the group having such an emulsifying action is a group represented by the following formula (17).

[In formula (17), n is a number from 1 to 20, m is a number from 0 to 4, and u is a number from 3 to 50]

  The structural unit (f) can be introduced by using a reactive emulsifier as a polymerization component. Examples of such reactive emulsifiers include compounds represented by the following formula (18).

［式（１８）中、ｎ、ｍ及びｕは、上記式（１７）と同様である］

[In the formula (18), n, m and u are the same as in the above formula (17)].

In addition, when the whole quantity of a hydroxyl-containing fluoropolymer is 100 mol%, it is preferable that the content rate of a structural unit (f) shall be 0.1-5 mol%. The reason for this is that when the content is 0.1 mol% or more, the solubility of the hydroxyl group-containing fluoropolymer in the solvent is improved. On the other hand, if the content is within 5 mol%, a low refractive index layer is formed. This is because the adhesiveness of the composition does not increase excessively, the handling becomes easy, and the moisture resistance does not decrease even when used for a coating material or the like.
For such reasons, the content of the structural unit (f) is more preferably 0.1 to 3 mol% based on the total amount of the hydroxyl group-containing fluoropolymer, and 0.2 to 3 More preferably, it is mol%.

(Vi) Molecular Weight The hydroxyl group-containing fluoropolymer preferably has a polystyrene-equivalent number average molecular weight of 5,000 to 500,000 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 lowered. On the other hand, when 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.
For these reasons, the number average molecular weight in terms of polystyrene of the hydroxyl group-containing fluoropolymer is more preferably 10,000 to 300,000, and even more preferably 10,000 to 100,000.

(2) Compound containing one isocyanate group and at least one ethylenically unsaturated group As a compound containing one isocyanate group and at least one ethylenically unsaturated group, The compound is not particularly limited as long as it is a compound containing one isocyanate group and at least one ethylenically unsaturated group.
In addition, when two or more isocyanate groups are contained, there is a possibility of causing gelation when reacting with a hydroxyl group-containing fluoropolymer.
Moreover, since the composition for low-refractive-index layer formation mentioned later can be hardened more easily as said ethylenically unsaturated group, the compound which has a (meth) acryloyl group is more preferable.
As such a compound, 2- (meth) acryloyloxyethyl isocyanate and 2- (meth) acryloyloxypropyl isocyanate may be used singly or in combination of two or more.

Such a compound can also be synthesized by reacting diisocyanate and a hydroxyl group-containing (meth) acrylate.
As examples of diisocyanates, 2,4-tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, methylene bis (4-cyclohexylisocyanate), and 1,3-bis (isocyanatomethyl) cyclohexane are preferred.

As examples of the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate and pentaerythritol tri (meth) acrylate are preferable.
In addition, as a commercial item of a hydroxyl-containing polyfunctional (meth) acrylate, for example, Osaka Organic Chemical Co., Ltd. product name HEA, Nippon Kayaku Co., Ltd. product name KAYARAD DPHA, PET-30, Toagosei Co., Ltd. Product name Aronix M-215, M-233, M-305, M-400, etc. can be obtained.

(3) Reaction of a hydroxyl group-containing fluoropolymer with a compound containing one isocyanate group and at least one ethylenically unsaturated group The ethylenically unsaturated group-containing fluoropolymer is It is obtained by reacting a compound containing an isocyanate group and at least one ethylenically unsaturated group with a hydroxyl group-containing fluoropolymer. The compound containing one isocyanate group and at least one ethylenically unsaturated group and the hydroxyl group-containing fluorine-containing polymer react at a molar ratio of isocyanate group / hydroxyl group of 1.1 to 1.9. It is preferable to do so. The reason for this is that when the molar ratio is less than 1.1, the scratch resistance and the durability may be lowered. On the other hand, when the molar ratio exceeds 1.9, This is because the scratch resistance of the coating film after immersion in an alkaline aqueous solution may be reduced.
For this reason, the molar ratio of isocyanate group / hydroxyl group is preferably 1.1 to 1.5, and more preferably 1.2 to 1.5.

(4) Reaction of hydroxyl group-containing fluoropolymer with acrylic acid or halogen salt of acrylic acid Ethylenically unsaturated group-containing fluoropolymer is prepared by dissolving the above-mentioned hydroxyl group-containing fluoropolymer in an organic solvent, It can also be produced by reacting with acrylic acid or a halogen salt of acrylic acid in the presence of a functional compound.

  Specifically, the hydroxyl group-containing fluorine-containing polymer is dissolved in an organic solvent to obtain a solution of the hydroxyl group-containing fluorine-containing copolymer having a concentration of 5% by mass or more (step (1)). A solution of a hydroxyl group-containing fluorine-containing copolymer and acrylic acid or a halogen salt of acrylic acid are mixed in the presence of a basic compound to synthesize the aforementioned ethylenically unsaturated group-containing fluorine-containing polymer (step) (2)).

Hereinafter, each step will be described.
Step (1):
The organic solvent (hereinafter referred to as “organic solvent 1”) used in the step (1) has a property that does not affect the reaction of the hydroxyl group-containing fluorine-containing copolymer with acrylic acid and a halide of acrylic acid. Although not particularly limited, methyl isobutyl ketone (MIBK), methyl ethyl ketone (MEK), methyl amyl ketone, acetone, butyl acetate, and ethyl acetate are preferable. These organic solvents 1 can be used individually by 1 type or in mixture of 2 or more types.

  The concentration of the hydroxyl group-containing fluoropolymer in the solution is preferably 5% by mass or more. The reason is that if it is less than 5% by mass, the reactivity with acrylic acid or the like is lowered in the step (2) described later. The upper limit of the concentration is naturally determined by the solubility of the hydroxyl group-containing fluoropolymer, but is usually about 30% by mass.

Step (2):
This is a step of reacting a hydroxyl group-containing fluoropolymer with acrylic acid or a halogen salt of acrylic acid (also referred to herein as “acrylic acid or the like”). As the halogen salt of acrylic acid, acrylic acid chloride is preferred.
This reaction is performed using a basic compound as a catalyst. Specific examples of basic compounds include strong acids such as sulfuric acid and p-toluenesulfonic acid in the case of reaction with acrylic acid, and dimethylaniline and diethylamine in the case of reaction with a halogen salt of acrylic acid. Is preferred.

Specifically, acrylic acid or the like and a basic compound are added to the solution of the hydroxyl group-containing fluoropolymer obtained in the step (1), and the reaction is performed while stirring at 120 to 130 ° C. for 4 to 8 hours. During the reaction, it is preferable to dehydrate using, for example, a Dean-Stark tube.
The addition amount of acrylic acid or the like is 5 to 120 mol% with respect to the number of moles of the structural unit (b) contained in the hydroxyl group-containing fluoropolymer, and the addition amount of the basic compound is the hydroxyl group-containing fluorine-containing polymer. It is 5-120 mol% with respect to the number-of-moles of the structural unit (b) contained in a polymer.

  According to the production method of the present invention, an ethylenically unsaturated group-containing fluoropolymer having a fluorine content of 45% by mass or more, more preferably 47% by mass or more is obtained.

The addition amount of the component (G) in the composition for forming a low refractive index layer is not particularly limited, but is usually 1 to 95% by mass with respect to 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 mass, the refractive index of the cured coating film of the composition for forming a low refractive index layer increases, and a sufficient antireflection effect may not be obtained. This is because if the added amount exceeds 95% by mass, the scratch resistance of the cured coating film of the composition for forming a low refractive index layer may not be obtained.
For this reason, the amount of component (G) added is more preferably 2 to 90% by mass, and even more preferably 3 to 85% by mass.

2. (H) Particles mainly composed of silica (H) The particles mainly composed of silica used in the curable resin composition for the low refractive index layer are an example of the component (A) used in the HC cured film layer. The same particles as the silica particles may be used.

Moreover, what carried out surface treatments, such as chemical modification, on the colloidal silica surface can be used, for example, a hydrolyzable silicon compound having one or more alkyl groups in the molecule or one containing a hydrolyzate thereof. Can be reacted. Such hydrolyzable silicon compounds include trimethylmethoxysilane, tributylmethoxysilane, dimethyldimethoxysilane, dibutyldimethoxysilane, methyltrimethoxysilane, butyltrimethoxysilane, octyltrimethoxysilane, dodecyltrimethoxysilane, 1,1. , 1-trimethoxy-2,2,2-trimethyl-disilane, hexamethyl-1,3-disiloxane, 1,1,1-trimethoxy-3,3,3-trimethyl-1,3-disiloxane, α-trimethylsilyl -Ω-dimethylmethoxysilyl-polydimethylsiloxane, α-trimethylsilyl-ω-trimethoxysilyl-polydimethylsiloxane hexamethyl-1,3-disilazane, and the like. A hydrolyzable silicon compound having one or more reactive groups in the molecule can also be used. Hydrolyzable silicon compounds having one or more reactive groups in the molecule are, for example, urea propyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyl having NH ₂ groups as reactive groups. Trimethoxysilane or the like having an OH group, bis (2-hydroxyethyl) -3-aminotripropylmethoxysilane or the like having an isocyanate group, 3-isocyanatopropyltrimethoxysilane or the like having a thiocyanate group As those having an thiol group, such as 3-thiocyanate propyltrimethoxysilane, etc. having an epoxy group, such as (3-glycidoxypropyl) trimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-mercaptopropyltrimeth Examples include xylsilane. 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. For example, the reactive silica particles can be obtained by reacting the silica particles having a number average particle size of 10 to 100 nm with a reactive surface treatment agent.

  Here, examples of the surface treatment agent include an alkoxysilane compound, tetrabutoxy titanium, tetrabutoxy zirconium, tetraisopropoxy aluminum, 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 γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and the following general formula ( 19).

In the formula, R ¹² is a methyl group, R ¹³ is an alkyl group having 1 to 6 carbon atoms, R ¹⁴ is a hydrogen atom or a methyl group, a is 1 or 2, b is an integer of 1 to 5, and A is 1 to 5 carbon atoms. 6 divalent alkylene group, B is a chain, cyclic or branched divalent hydrocarbon group having 3 to 14 carbon atoms, Z is a (b + 1) valent chain, cyclic or branched group A divalent hydrocarbon group having 2 to 14 carbon atoms. Z may contain an ether bond.
When the silica particle has an ethylenically unsaturated group, it can be co-crosslinked with a UV curable (meth) acrylic monomer described later, and the scratch resistance is improved.

  In addition, the (H) silica-based particles are particles formed by bonding with the organic compound (Ab) described above in the same manner as the (A) component used in the HC cured film layer. From the viewpoint of affinity.

The addition amount of the component (H) in the composition for forming a low refractive index layer is not particularly limited, but is usually 5 to 95% by mass with respect to the total amount of the composition other than the organic solvent. The reason for this is that if the amount added is less than 5% by mass, the scratch resistance may be insufficient. On the other hand, if the amount added exceeds 95% by mass, the component (G) having a low refractive index may be used. This is because the refractive index may be too high because the content decreases.
For such reasons, it is preferable that the amount of component (H) added is 10 to 95% by mass,
A value in the range of 15 to 90% by mass is more preferable.

3. Optional Addition Components The following components can be added to the composition for forming a low refractive index layer used in the present invention, if necessary.

(I) Polymerizable unsaturated group-containing compound (I-1) Polyfunctional (meth) acrylate compound containing one or more (meth) acryloyl groups This compound comprises (C) component used for HC cured film layer and It is the same as the component (D).

(I-2) Fluorine-containing (meth) acrylate compound containing one or more (meth) acryloyl groups The compound may be a fluorine-containing (meth) acrylate compound containing one or more (meth) acryloyl groups. There is no particular limitation. Examples of such include perfluorooctylethyl (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 mass with respect to the total amount of the composition other than the organic solvent. The reason for this is that when the addition amount exceeds 90% by mass, the content of the component (G) having a low refractive index is lowered, so that the refractive index of the cured coating film of the composition for forming a low refractive index layer becomes high and sufficient. This is because the antireflection effect may not be obtained.
For this reason, the amount of component (I) added is more preferably 80% by mass or less, and still more preferably 60% by mass or less.

(J) Compound that generates active species by irradiation of active energy rays or heat In the present invention, 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.

(1) Compound that generates active species upon irradiation with active energy rays This compound is the same as the component (E) used for the HC cured film layer.

(Ii) Addition amount The addition amount of the photopolymerization initiator is not particularly limited, but is preferably 0.01 to 20% by mass with respect to the total amount of the composition other than the organic solvent. The reason for this is that when the amount added is less than 0.01% by mass, 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, when the addition amount of the photopolymerization initiator exceeds 20% by mass, the refractive index of the cured film increases and the antireflection effect may be lowered.
Moreover, it is more preferable to set it as 0.05-15 mass% with respect to such composition for the addition amount of a photoinitiator with respect to composition whole quantity other than an organic solvent, and shall be 0.1-15 mass%. More preferably.

(2) Compound that generates active species by heat Examples of the compound that generates active species by heat (hereinafter referred to as “thermal polymerization initiator”) include a thermal radical generator that generates radicals as the active species.

(I) Type Examples of thermal radical generators include benzoyl peroxide, tert-butyl-oxybenzoate, azobisisobutyronitrile, acetyl peroxide, lauryl peroxide, tert-butyl peracetate, cumyl peroxide, tert -One kind of butyl peroxide, tert-butyl hydroperoxide, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), etc. Single or 2 or more types of combinations can be mentioned.

(Ii) Addition amount The addition amount of the thermal polymerization initiator is not particularly limited, but is preferably 0.01 to 20% by mass with respect to the total amount of the composition other than the organic solvent. The reason for this is that when the amount added is less than 0.01% by mass, 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, when the addition amount of the photopolymerization initiator exceeds 20% by mass, the refractive index of the cured film increases and the antireflection effect may be lowered.
For this reason, the addition amount of the thermal polymerization initiator is more preferably 0.05 to 15% by mass with respect to the total amount of the composition other than the organic solvent, and is within the range of 0.1 to 15% by mass. More preferably, the value of

(K) Organic solvent It is preferable to further add an organic solvent to the composition for forming a low refractive index layer. Thus, by adding an organic solvent, a thin antireflection film can be formed uniformly. As such an organic solvent, an alcohol solvent having 1 to 8 carbon atoms, a ketone solvent having 3 to 10 carbon atoms, and an ester solvent having 3 to 10 carbon atoms can be preferably used, such as methyl isobutyl ketone, methyl ethyl ketone, methyl amyl Ketones, methanol, ethanol, t-butanol, isopropanol, propylene glycol monomethyl ether, propylene glycol ethyl ether, propylene glycol monopropyl ether and the like are particularly preferable examples. 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 mass with respect to 100 parts by mass of the composition other than the organic solvent. The reason for this is that when the amount added is less than 100 parts by mass, it may be difficult to adjust the viscosity of the composition for forming a low refractive index layer, while when the amount added exceeds 100,000 parts by mass, This is because the storage stability of the composition for forming a low refractive index layer may be decreased, or the viscosity may be excessively decreased to make it difficult to handle.

(L) Additive In the composition for forming a low refractive index layer, a photosensitizer, a polymerization inhibitor, a polymerization initiation assistant, a leveling agent, a wettability improver, as long as the purpose and effect of the present invention are not impaired. Surfactants, plasticizers, ultraviolet absorbers, antioxidants, antistatic agents, silane coupling agents, inorganic fillers other than the component (H), and the like can be added.

4). Method for preparing composition for forming low refractive index layer The composition for forming a low refractive index layer comprises the above-mentioned (G) curable fluorinated polymer and (H) silica-based particles, and if necessary, the above-mentioned It can prepare by adding (I) component, (J) polymerization initiator, (K) organic solvent, and (L) additive, respectively, and mixing under room temperature or heating conditions. Specifically, it can be prepared using a mixer such as a mixer, a kneader, a ball mill, or a three roll. However, when mixing under heating conditions, it is preferable to carry out at or below the decomposition start temperature of the thermal polymerization initiator.

5. Curing Method of Low Refractive Index Layer Composition The curing conditions of the low refractive index layer composition are not particularly limited. For example, when active energy rays are used, the exposure dose is 0.01 to 10 J. A value within the range of / cm ² is preferable.
This is because when the exposure dose is less than 0.01 J / cm ² , curing failure may occur. On the other hand, when the exposure dose exceeds 10 J / cm ² , the curing time may become excessively long. Because there is.
For these reasons, the exposure dose is more preferably set to a value in the range of 0.1 to 5 J / cm ² , and more preferably set to a value in the range of 0.3 to 3 J / cm ^2. .

When the composition for forming a low refractive index layer is heated and cured, 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.
For these reasons, it is more preferable to heat at a temperature in the range of 50 to 180 ° C. for 1 to 120 minutes, and further to heat at a temperature in the range of 80 to 150 ° C. for 1 to 60 minutes. preferable.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In the following, “part” and “%” respectively represent “part by mass” and “% by mass” unless otherwise specified.

Production Example 1: Production of compound represented by formula (5) (component (B)) 23.1 parts Karenz MOI (2-methacryloyloxyethyl isocyanate) manufactured by Showa Denko in a vessel equipped with a stirrer and dibutyltin dilaurate 0 76.9 parts of NK ester A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd. (only the pentaerythritol triacrylate having a hydroxyl group is involved in the reaction) After dropwise addition at 1 ° C. for 1 hour, the reaction solution was stirred at 60 ° C. for 3 hours.
When the amount of residual isocyanate in the product in this reaction solution was measured by FT-IR, it was 0.1% by mass or less, and it was confirmed that the reaction was carried out almost quantitatively. Moreover, it confirmed that a urethane bond and an acryloyl group (polymerizable unsaturated group) were included in the molecule | numerator.
As a result, 69 parts of the compound represented by the formula (5) and 31 parts of pentaerythritol tetraacrylate were obtained.

Production Example 2: Production of organic compound (Ab) containing polymerizable unsaturated group In dry air, 222 parts of isophorone diisocyanate was stirred with respect to a solution consisting of 221 parts of mercaptopropyltrimethoxysilane and 1 part of dibutyltin dilaurate. However, after dropwise addition at 50 ° C. over 1 hour, the mixture was stirred with heating at 70 ° C. for 3 hours. This is composed of NK ester A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Co., Ltd.) comprising 60% by mass of pentaerythritol triacrylate and 40% by mass of pentaerythritol tetraacrylate. 549 parts were added dropwise at 30 ° C. over 1 hour, and then heated and stirred at 60 ° C. for 10 hours to obtain an organic compound (Ab) containing a polymerizable unsaturated group. When the amount of residual isocyanate in the product was analyzed by FT-IR, it was 0.1% or less, indicating that the reaction was almost quantitatively completed. In the infrared absorption spectrum of the product, the absorption peak of 2550 Kaiser characteristic of mercapto group in the raw material and the absorption peak of 2260 Kaiser characteristic of raw material isocyanate compound disappeared, and new urethane A 1660 Kaiser peak characteristic of the bond and the S (C = O) NH- group and a 1720 Kaiser peak characteristic of the acryloxy group are observed, with an acryloxy group as the polymerizable unsaturated group It was shown that -S (C = O) NH- and an acryloxy group-modified alkoxysilane having both urethane bonds were formed. As a result, a total of 773 parts of the mixture of the compound represented by the formula (3) and the compound represented by the formula (4) (Ab) and 220 parts of pentaerythritol tetraacrylate not involved in the reaction were obtained. .

Production Example 3: Production of reactive zirconia particles (A-1) (component (A)) 2.23 parts of an organic compound (Ab) containing a polymerizable unsaturated group produced in Production Example 2, a zirconia particle dispersion (Aa) ) (Methyl ethyl ketone dispersion of 33.3% by mass of zirconia particles) A mixture of 97.37 parts, 0.03 part of ion-exchanged water, and 0.02 part of p-hydroxyphenyl monomethyl ether was stirred at 60 ° C. for 4 hours. Then, 0.34 part of orthoformate methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain reactive particles (A-1). 2 g of this dispersion was weighed in an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour, and weighed to determine the solid content, which was 34.5%. Further, 2 g of the dispersion was weighed in a magnetic crucible, preliminarily dried on an 80 ° C. hot plate for 30 minutes, and calcined in a muffle furnace at 750 ° C. for 1 hour to obtain the inorganic content in the solid content. As a result, it was 85.8%.

Production Example 4: Production of reactive silica particles (A-2) (component (A)) 2.32 parts of an organic compound (Ab) containing a polymerizable unsaturated group produced in Production Example 2, silica particle sol (methyl ethyl ketone silica sol , Nissan Chemical Industries, Ltd. MEK-ST, number average particle size 0.022 μm, silica concentration 30%) 95.9 parts, ion-exchanged water 0.12 parts, and p-hydroxyphenyl monomethyl ether 0.01 parts After the mixture was stirred at 60 ° C. for 4 hours, 1.36 parts of orthoformate methyl ester was added, and the mixture was further heated and stirred at the same temperature for 1 hour to obtain reactive particles (A-2). 2 g of this dispersion was weighed in an aluminum dish, dried on a hot plate at 175 ° C. for 1 hour, and weighed to determine the solid content, which was 31%. Further, 2 g of the dispersion was weighed in a magnetic crucible, preliminarily dried on an 80 ° C. hot plate for 30 minutes, and calcined in a muffle furnace at 750 ° C. for 1 hour to obtain the inorganic content in the solid content. As a result, it was 90%.

Production Example 5: Production of polyfunctional acrylate represented by formula (7) (component (C)) For a solution consisting of 18.8 parts of isophorone diisocyanate and 0.2 part of dibutyltin dilaurate in a container equipped with a stirrer , 93 parts of NK ester A-TMM-3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd. The mixture was stirred at 60 ° C. for 6 hours to prepare a reaction solution.
The product in this reaction solution, that is, the amount of residual isocyanate was measured by FT-IR in the same manner as in Production Example 2 and found to be 0.1% by mass or less, confirming that the reaction was carried out almost quantitatively. did. Moreover, it confirmed that a urethane bond and an acryloyl group (polymerizable unsaturated group) were included in the molecule | numerator.
As a result, 75 parts of the compound represented by the formula (7) and 37 parts of pentaerythritol tetraacrylate which was not involved in the reaction were obtained.

Production Example 6: Production of polyfunctional acrylate represented by formula (8) (component (C)) Consists of 16 parts of 2,4-tolylene diisocyanate in a container equipped with a stirrer and 0.2 parts of dibutyltin dilaurate NK ester A-TMM-3LM-N (manufactured by Shin-Nakamura Chemical Co., Ltd. (only the pentaerythritol triacrylate having a hydroxyl group is involved in the reaction)) 93 parts was added dropwise to the solution at 10 ° C. for 1 hour. Then, the mixture was stirred at 60 ° C. for 6 hours to obtain a reaction solution.
The product in this reaction solution, that is, the amount of residual isocyanate was measured by FT-IR in the same manner as in Production Example 2 and found to be 0.1% by mass or less, confirming that the reaction was carried out almost quantitatively. did. Moreover, it confirmed that a urethane bond and an acryloyl group (polymerizable unsaturated group) were included in the molecule | numerator.
As a result, 72 parts of the compound represented by the formula (8) and 37 parts of pentaerythritol tetraacrylate were obtained.

Production Example 7 Synthesis of Hydroxyl-Containing Fluoropolymer Polymer A stainless steel autoclave with an internal volume of 2.0 liters equipped with a magnetic stirrer was sufficiently replaced with nitrogen gas, and then 1200 g of ethyl acetate, 346 g of perfluoro (propyl vinyl ether), 94 g of ethyl vinyl ether, 115 g of hydroxyethyl vinyl ether, 4 g of lauroyl peroxide, 23 g of azo group-containing polydimethylsiloxane (VPS1001 (trade name), manufactured by Wako Pure Chemical Industries, Ltd.) and nonionic reactive emulsifier (NE-30 (trade name), Asahi Denka) 450 g of Kogyo Co., Ltd.) was charged and cooled to −50 ° C. with dry ice-methanol, and then oxygen in the system was removed again with nitrogen gas.
Next, 215 g of hexafluoropropylene was charged and the temperature increase was started. The pressure when the temperature in the autoclave reached 60 ° C. was 5.3 × 10 ⁵ Pa. Thereafter, the reaction was continued with stirring at 70 ° C. for 20 hours. When the pressure dropped to 1.7 × 10 ⁵ Pa, the autoclave was cooled with water to stop the reaction. After reaching room temperature, unreacted monomers were released and the autoclave was opened to obtain a polymer solution having a solid content concentration of 30%. The obtained polymer solution was put into methanol to precipitate a polymer, washed with methanol, and vacuum dried at 50 ° C. to obtain 850 g of a hydroxyl group-containing fluoropolymer.

Production Example 8: Production of ethylenically unsaturated group-containing fluorine-containing polymer Hydroxyl-containing fluorine-containing polymer obtained in Production Example 7 in a 1-liter separable flask equipped with an electromagnetic stirrer, a glass condenser, and a thermometer 70.0 g of the polymer, 0.01 g of 2,6-di-t-butylmethylphenol and 520 g of MIBK as a polymerization inhibitor were charged, and the hydroxyl group-containing fluoropolymer was dissolved in MIBK at 20 ° C., and the solution was transparent and uniform. Stirring was continued until Next, 22 g of 2-methacryloyloxyethyl isocyanate was added to this system and stirred until the solution became homogeneous, then 0.2 g of dibutyltin dilaurate was added to start the reaction, and the temperature of the system was changed to 55 to 65 ° C. And stirring for 5 hours to obtain a MIBK solution of an ethylenically unsaturated group-containing fluoropolymer. 2 g of this solution was weighed in an aluminum dish, dried on a hot plate at 150 ° C. for 5 minutes, and weighed to determine the solid content, which was 15.0%.

Production Example 9: Preparation of curable resin composition for low refractive index layer 20 g of reactive silica particle (A-2) sol obtained in Production Example 4 (6.2 g as reactive particles), obtained in Production Example 8 101.0 g of an ethylenically unsaturated group-containing fluoropolymer (15.2 g as an ethylenically unsaturated group-containing fluoropolymer), 1.7 g of dipentaerythritol pentaacrylate, 2-methyl-1- [4- (methylthio ) Phenyl] -2-morpholinopropan-1-one (E-2) 1.2 g, 0.4 g of the compound represented by formula (7) obtained in Production Example 5, organic copolymer-containing special silicon (Floren) AC-901, Kyoeisha Chemical Co., Ltd.) 0.1 g and methyl isobutyl ketone 505.6 g were added and stirred at room temperature for 1 hour to obtain a composition 1 for forming a low refractive index layer. When solid content was calculated | required, it was 4 mass%.

Production Example 10: Preparation of silica particle-containing composition for hard coat layer 98.6 g of reactive silica particle (A-2) sol obtained in Production Example 4 (30.6 g as reactive particles), obtained in Production Example 5 3.4 g of a solution containing the obtained compound represented by the formula (7), 2.1 g of 1-hydroxycyclohexyl phenyl ketone (E-1), 2-methyl-1- [4- (methylthio) phenyl] -2-morpho 1.2 g of linopropan-1-one (E-2), 33.2 g of dipentaerythritol hexaacrylate, and 7 g of cyclohexanone were mixed and stirred to obtain 145 g of a composition for silica particle-containing hard coat layer (solid content concentration 50%). It was.

Production Example 11: Preparation of HC cured film layer forming composition 1 23.3 parts of reactive zirconia particles (A-1) produced in Production Example 3 (20.0 parts of zirconia particles (Aa) and organic bonded to the particles) Compound (Ab) consisting of 3.3 parts), 10.0 parts of the compound represented by the formula (5) produced in Production Example 1, 61.7 parts of pentaerythritol triacrylate, 0.42 parts of pentaerythritol tetraacrylate , 0.62 part of polyfunctional acrylate represented by the formula (7) produced in Production Example 5, 5.0 part of 1-hydroxycyclohexyl phenyl ketone, 20 parts of methyl ethyl ketone (dispersion medium of reactive zirconia particles (A-1)) And 30 parts of methyl isobutyl ketone were stirred at 25 ° C. for 1 hour to obtain a uniform composition. The obtained composition is referred to as “HC cured film layer forming composition 1”. Among these, pentaerythritol tetraacrylate is derived from pentaerythritol tetraacrylate mixed in the organic compound (Ab) and the polyfunctional acrylate represented by the formula (7) obtained in Production Example 5. The solid content of this composition was determined to be 50%.
When the methacryloyl group concentration in 100 g of the composition 1 for forming an HC cured film excluding the obtained solvent was calculated from the charged amount, it was 0.015 mol.

Example 1
Production of Antireflection Laminate 1 The HC cured film layer forming composition 1 obtained in Production Example 11 was coated on a triacetyl cellulose (TAC) film (film thickness of 80 μm) using a wire bar coater # 12. And dried in an oven at 80 ° C. for 3 minutes. Next, the coating film was UV-cured under a light irradiation condition of 1 J / cm ² using a metal halide lamp in the atmosphere to produce a film having a hard coat layer. It was 6 micrometers when the film thickness of the hard-coat layer was measured with the stylus type surface shape measuring device. On this film with a hard coat, the composition 1 for forming a low refractive index layer obtained in Production Example 9 was applied using a wire bar coater # 3 and dried in an oven at 80 ° C. for 1 minute. did. Next, under a nitrogen atmosphere, the coating film was UV-cured under a light irradiation condition of 1 J / cm ² using a metal halide lamp, and a low refractive index layer was formed to produce the antireflection laminate 1. The film thickness of the low refractive index layer was calculated from the reflectance of the obtained antireflection laminate 1 and found to be 0.1 μm.

Examples 2-4 and Comparative Examples 1-6
An antireflection laminate was obtained in the same manner as in Example 1 except that each composition shown in Table 1 was used instead of the HC cured film layer forming composition 1.

Example 5
Production of Antireflection Laminate 2 A composition 2 for forming an HC cured film layer was obtained in the same manner as in Production Example 11 except that the composition shown in Table 2 was used. Next, the silica particle-containing composition for hard coat layer obtained in Production Example 10 was coated on a TAC film (film thickness of 80 μm) using a wire bar coater # 6, and in an oven at 80 ° C. for 3 minutes. It dried on the conditions of. Next, the coating film was UV-cured under a light irradiation condition of 1 J / cm ² using a metal halide lamp in the atmosphere to produce a film having a hard coat layer. It was 3 micrometers when the film thickness of the hard-coat layer was measured with the stylus type surface shape measuring device. On this film with hard coat, HC cured film layer-forming composition 2 is diluted with methyl isobutyl ketone to a solid content concentration of 5%, and coated with wire bar coater # 6, and is heated at 80 ° C. in an oven. Dried for 1 minute. Next, the coating film was UV-cured under a light irradiation condition of 1 J / cm ² using a metal halide lamp in a nitrogen atmosphere to form a high refractive index layer. When the film thickness of the high refractive index layer was calculated in the same manner as in Example 1, it was 0.1 μm. The obtained laminate was coated with the composition 1 for forming a low refractive index layer obtained in Production Example 9 using a wire bar coater # 3 and dried in an oven at 80 ° C. for 1 minute. . Next, under a nitrogen atmosphere, the coating film was UV-cured under a light irradiation condition of 1 J / cm ² using a metal halide lamp, and a low refractive index layer was formed to produce an antireflection laminate 2. It was 0.1 micrometer when the film thickness of the low-refractive-index layer was computed from the reflectance of the obtained antireflection laminated body 2.

Comparative Example 7
An antireflection laminate was obtained in the same manner as in Example 5 except that the composition shown in Table 2 was used instead of the HC cured film layer forming composition 2.

Evaluation Examples The following characteristics were evaluated for the antireflection laminates obtained in Examples 1 to 5 and Comparative Examples 1 to 7, and are shown in Tables 1 and 2.

1. Scratch resistance (steel wool resistance)
The surface of the antireflection film laminate obtained in Examples 1 to 5 and Comparative Examples 1 to 7 was rubbed 10 times with # 0000 steel wool under a load of 400 g / cm ² , and the antireflection film laminate was scratch resistant. Was visually evaluated.
The case where there were no scratches or several scratches or less was judged as “◯”, the case where the entire surface was scratched was judged as “X”, and the intermediate state between “○” and “x” was judged as “Δ”. In the case of “△”, typically about ten or more scratches are attached.

2. Reflectance The reflectance of the obtained antireflection laminate is measured by a spectral reflectance measuring device (a self-recording spectrophotometer U-3410 incorporating a large sample chamber integrating sphere attachment device 150-09090, manufactured by Hitachi, Ltd.), The reflectance was measured and evaluated in the wavelength range of 340 to 700 nm. Specifically, the reflectance of the antireflection laminate (antireflection film) at each wavelength was measured using the reflectance of the aluminum deposited film as a reference (100%). Tables 1 and 2 show the reflectance at a wavelength of 550 nm.

3. Transparency (haze)
(1-1) Preparation of measurement sample The composition obtained in the corner example and the comparative example was applied to a TAC film (film thickness of 80 μm) using a coater equipped with a wire bar coater, and in an oven, 80 Drying was performed under the conditions of 3 ° C. for 3 minutes to form a coating film. Subsequently, the coating film was UV-cured under a light irradiation condition of 0.3 J / cm ² using a high-pressure mercury lamp under nitrogen to form a cured film having a thickness of 6 to 7 μm.
(1-2) Measurement of transparency (haze) Using a color haze meter manufactured by Suga Seisakusho Co., Ltd., the haze value (%) was measured according to ASTM D1003 and evaluated as a value including a base film.

Abbreviations used in Tables 1 and 2 represent the following.
TMPTMA: trimethylolpropane trimethacrylate; NK ester TMPT, Shin-Nakamura Chemical Co., Ltd. PETriA: pentaerythritol triacrylate PETetraA: pentaerythritol tetraacrylate U-4H: compound represented by the following formula (20); NK oligo U-4H; Shinnakamura Chemical Co., Ltd. DPHA: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate; Nippon Kayaku Co., Ltd. Irgacure 184: 1-hydroxycyclohexyl phenyl ketone; Ciba Specialty Chemicals Co., Ltd. Irgacure 907: 2-methyl-1 -[4- (Methylthio) phenyl] -2-morpholino-propan-1-one; Ciba Specialty Chemicals Co., Ltd.

The% value described in the column of the component names of the (B) component and the (C) component in Table 1 and Table 2 is the ratio (%) of the number of methacryloyl groups that each component has to the total number of methacryloyl groups and acryloyl groups. Indicates. The amount of MEK, which is the dispersion medium for component (A), is included in the amount of solvent (F).
From the results shown in Table 1, it can be seen that the antireflection laminate having the HC cured film layer constituting the laminate of the present invention has an excellent balance of scratch resistance, minimum reflectance, and transparency.

According to the present invention, a curable composition capable of forming a coating film (film) having excellent hardness and scratch resistance and having both transparency and surface resistance value is cured on the surface of various substrates. A laminate having a cured film layer, particularly an antireflection film laminate, can be provided.
The laminate of the present invention is mainly a product such as a protective film for a touch panel, a transfer foil, a hard coat for an optical disc, a window film for an automobile, a hard coat film for a lens, a surface protective film of a high-design container such as a cosmetic container. Plastic lenses as hard coats for the purpose of preventing surface flaws and preventing dust from adhering to static electricity, and as antireflection films for various display panels such as CRTs, liquid crystal display panels, plasma display panels, and electroluminescence display panels It can be used as an antireflection film for polarizing films, solar battery panels, and the like.
The laminated body of the present invention can be used to prevent or damage (scratch) or contaminate, for example, plastic optical components, touch panels, film-type liquid crystal elements, plastic housings, plastic containers, flooring materials as building interior materials, wall materials, and artificial marble. It can be suitably used as a hard coating material for preventing; an adhesive for various substrates, a sealing material; a binder material for printing ink, and the like.

It is a schematic diagram which shows the basic composition of the laminated body of this invention. It is a schematic diagram which shows the 1st form of the anti-reflective film with a hard-coat function of this invention. It is a schematic diagram which shows another form of the 1st form of the antireflection film with a hard-coat function of this invention. It is a schematic diagram which shows another form of the 1st form of the antireflection film with a hard coat of this invention. It is a schematic diagram which shows the 2nd form of the anti-reflective film with a hard-coat function of this invention. It is a schematic diagram which shows another form of the 2nd form of the antireflection film with a hard-coat function of this invention. It is a schematic diagram which shows another form of the 3rd form of the antireflection film with a hard-coat function of this invention. It is a schematic diagram which shows another form of the 3rd form of the antireflection film with a hard-coat function of this invention. It is a schematic diagram which shows another form of the 4th form of the antireflection film with a hard-coat function of this invention.

Explanation of symbols

1: Laminated body 10: Base material 11: Antistatic layer 12: HC cured film layer 14: Medium refractive index layer 16: High refractive index layer 18: Low refractive index layer

Claims (10)

At least a substrate;
A cured film layer obtained by curing a curable composition containing the following components (A), (B), (E) and (F);
A laminate having
[Curable composition]
(A) particles having a polymerizable unsaturated group, the main component being an oxide of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, germanium, indium, tin, antimony and cerium;
(B) a compound having a methacryloyl group and an acryloyl group in one molecule;
(E) a photopolymerization initiator, and (F) a solvent.   The laminated body of Claim 1 whose sum total of the number of the methacryloyl group and acryloyl group which the said (B) component has is 3 or more. The laminate according to claim 1 or 2, wherein the particles having a polymerizable unsaturated group in the component (A) have a group represented by the following formula (1) in addition to the polymerizable unsaturated group.
-X-C (= Y) -NH- (1)
[In the formula (1), X represents NH, O (oxygen atom) or S (sulfur atom), and Y represents O or S. ]   At least a base material, the cured film layer, and a layer having a refractive index at a wavelength of 589 nm (hereinafter simply referred to as “refractive index”) lower than the refractive index of the cured film layer (hereinafter referred to as “low refractive index layer”). .), And is laminated in this order from the side close to the base material.   The laminate according to claim 4, wherein the low refractive index layer comprises (G) a curable fluorinated polymer.   Furthermore, the laminated body as described in any one of Claims 1-5 which has a layer which has electroconductivity.   The laminated body as described in any one of Claims 1-6 whose thickness of the said cured film layer is 0.5-50 micrometers.   The laminate according to any one of claims 1 to 6, wherein the cured film layer has a thickness of 0.05 to 0.5 µm. At least a substrate;
A layer having a refractive index lower than that of the cured film layer and a refractive index higher than that of the low refractive index layer (hereinafter referred to as “medium refractive index layer”);
The cured film layer;
The low refractive index layer,
The laminate according to claim 8, wherein the laminate is laminated in this order from the side close to the substrate. At least a substrate;
The cured film layer;
A layer having a refractive index higher than that of the cured layer (hereinafter referred to as “high refractive index layer”);
The low refractive index layer,
The laminate according to claim 8, wherein the laminate is laminated in this order from the side close to the substrate.

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