JP2003240906A - Antireflection body and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antireflection body in which the adhesiveness between a low refractive index layer on the surface of the reflective body and a hard coat layer or a high refractive index layer as a lower layer is improved, and to provide a method of manufacturing the same. <P>SOLUTION: The antireflection body 1 has a multilayer structure of a base body 2, a hard coat layer 3 and a low refractive index layer, or of a base body 2, a hard coat layer 3, a high refractive index layer 6 and a low refractive index layer. The structure has an impregnated part 5A or 5B by impregnating the lower layer of the low refractive index layer with the component of the composition for the formation of the low refractive index layer while the lower layer is partially hardened and then hardening the layer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has a laminated structure in which a low refractive index layer is laminated directly on a hard coat layer or via another layer. Alternatively, the present invention relates to an antireflection body having improved adhesion between another layer provided in the hard coat layer and the low refractive index layer. The present invention also relates to a method for producing an antireflection body, which includes a laminating method capable of improving the adhesion between the layers.

[0002]

2. Description of the Related Art To maintain the transparency of a glass plate, a plastic film, etc. and prevent reflection on the surface, or
It is common practice to prevent reflections on the surface of various articles that are not transparent in their own right. Above all, it is particularly important to have both the transparency and the antireflection property in terms of their functions in a building or a vehicle window that needs to be seen through, or an instrument or a display device (= display) of various devices.

In order to suppress the reflection on the surface, it is necessary to provide a low refractive index layer having a refractive index lower than that of the material forming the target surface as the antireflection layer. The antireflection layer is located on the outermost surface. Therefore, the physical and chemical durability of the surface is required at the same time, and the scratch resistance of the surface is particularly required. Therefore, a hard coat layer is usually provided below the low refractive index layer which is the antireflection layer.

The hard coat layer literally refers to a hard coating layer, and as the resin constituting the paint layer composition for forming such a layer, a resin capable of providing a hard coating layer is selected. However, a resin that gives a hard coating layer generally has a low solubility in a solvent due to its high molecular weight or high density. Therefore, a coating composition for forming a low refractive index layer is formed on a hard coat layer once formed. When the low refractive index layer is formed using a material, the adhesion between the hard coat layer and the low refractive index layer tends to be insufficient. The tendency that the adhesion tends to be insufficient is more remarkable when the hard coat layer is formed using a coating composition containing a thermosetting resin or an ionizing radiation curable resin as a resin component. In this case, the adhesion of the low-refractive index layer provided on the hard coat layer becomes considerably low, and this may cause problems such as reduced scratch resistance and peeling of the low-refractive index layer during handling.

The same phenomenon occurs when a low refractive index layer is laminated on a hard coat layer via another layer. A high-refractive-index layer is often provided between the hard coat layer and the low-refractive-index layer in order to enhance antireflection property, but the adhesion between the high-refractive-index layer and the low-refractive-index layer is also high. Like the adhesion between the hard coat layer and the low refractive index layer, it tends to be low. In the sense of improving antireflection property, there are various laminated structures such as a middle refractive index layer, a high refractive index layer, and a low refractive index layer other than such a high refractive index layer and a low refractive index layer. However, the object of laminating the last low refractive index layer is often a high refractive index layer. Further, in the case of imparting conductivity to the surface, the low refractive index layer may be laminated on the laminated conductive layer.

[0006]

In the present invention, when a low refractive index layer is laminated on the outermost surface to prevent reflection, the adhesion between the low refractive index layer and the hard coat layer, or the low refractive index layer. It is an object of the present invention to provide an antireflection body having improved adhesion between the antireflection film and other layers, and to provide a production method capable of producing such an antireflection body.

[0007]

According to a study by the inventor, another layer and a low refractive index layer interposed between the hard coat layer and the low refractive index layer or between the hard coat layer and the low refractive index layer The problem can be solved by adopting a laminated structure in which an impregnated portion is formed near the interface between the two. Also,
In the present invention, to form such an impregnated portion,
While the lower layer formed by the coating method is not yet completely cured, coating for forming the low refractive index layer is performed, and the coated coating composition is allowed to penetrate into the surface layer portion of the lower layer, thereby forming the lower layer and the upper layer. It became possible to realize the above-mentioned laminated structure by setting the impregnated portion in the vicinity of the interface with and hardening the whole.

The first invention has a laminated structure in which a hard coat layer and a low refractive index layer, both of which are made of a resin composition containing a resin, are sequentially laminated on a substrate. The present invention relates to an antireflection body having an impregnated portion in which the components of the low refractive index layer are impregnated in the surface layer portion. The second invention has a laminated structure in which a hard coat layer, a high refractive index layer or a conductive layer, and a low refractive index layer, each of which is made of a resin composition containing a resin, are sequentially laminated on a substrate. The surface layer portion of the hard coat layer has an impregnated portion impregnated with the components of the high refractive index layer or the conductive layer, and / or the low refractive index layer or the surface layer portion of the conductive layer has a low content. The present invention relates to an antireflection body having an impregnated portion impregnated with a component of a refractive index layer. Third
In the first or second invention, the hard coat layer is an ionizing radiation curable resin composition in which the hard coat layer contains a thermosetting resin and / or an ionizing radiation curable resin. The present invention relates to an antireflection body comprising a cured resin composition composed of the cured product. A fourth invention is the thermosetting resin composition according to the second invention, wherein the high refractive index layer contains a thermosetting resin and / or an ionizing radiation curable resin composition containing an ionizing radiation curable resin. The present invention relates to an antireflection body comprising a cured resin composition composed of the cured product. A fifth invention relates to the antireflection member according to the fourth invention, wherein the high refractive index layer further contains inorganic ultrafine particles. A sixth invention relates to the antireflection member according to any one of the first to fifth inventions, wherein the high refractive index layer has a refractive index of higher than 1.46. A seventh invention is the ionizing radiation according to any one of the first to sixth inventions, wherein the low refractive index layer contains a thermosetting resin composition containing a thermosetting resin and / or an ionizing radiation curable resin. The present invention relates to an antireflection body comprising a cured resin composition composed of a cured product of a curable resin composition. 8th
The present invention relates to the antireflection member according to the seventh invention, characterized in that the low refractive index layer contains a fluoropolymer component. A ninth invention relates to the antireflection member according to the seventh invention, wherein the low refractive index layer contains a fluorine-containing oligomer component.
A tenth aspect of the present invention relates to the antireflection member according to the seventh aspect, wherein the low refractive index layer contains a polysiloxane component. An eleventh invention is the first to tenth inventions, wherein the low refractive index layer has a refractive index of 1.1.
It is related with the antireflection body characterized by being 0 to 1.46. A twelfth invention comprises a hard coat layer mainly comprising a resin composition and a low refractive index layer which are sequentially laminated on a substrate, and a hard coat layer forming coating material containing a resin on the substrate. By coating the composition and performing partial curing, a hard coat layer that is not yet completely cured is formed, and then a resin is applied onto the hard coat layer that is not yet completely cured. A coating composition for forming a low refractive index layer containing the composition is laminated to form an uncured low refractive index layer, and after the lamination, the composition for forming a low refractive index layer in the uncured low refractive index layer. A method for producing an antireflection body, which comprises impregnating the hard coat layer that has not been completely cured to form an impregnated portion in the surface layer portion of the hard coat layer, and then curing the whole. It is a thing. A thirteenth invention comprises a hard coat layer mainly composed of a resin composition, a high refractive index layer, and a low refractive index layer, which are sequentially laminated on a substrate, and a hard layer containing a resin on the substrate. A hard coat layer is formed by coating the coating composition for forming a coat layer and curing it, and then coating the composition for forming a high refractive index layer containing a resin on the hard coat layer. By performing partial curing by forming a high refractive index layer that is not yet completely cured,
Furthermore, after that, on the high refractive index layer which is not yet completely cured, a coating composition for forming a low refractive index layer containing a resin is coated, and an uncured low refractive index layer is laminated, After lamination, the composition for forming a low refractive index layer in the uncured low refractive index layer is impregnated into the high refractive index layer that has not yet been completely cured, and the high refractive index layer of The present invention relates to a method for producing an antireflection body, which comprises forming an impregnated portion on the surface layer portion and then curing the whole. 14th
The invention comprises a hard coat layer mainly comprising a resin composition, a high refractive index layer, and a low refractive index layer, which are sequentially laminated on a substrate, and a hard coat layer containing a resin is formed on the substrate. A hard coating layer that is not yet completely cured is formed by coating the coating composition for forming and performing partial curing, and then, on the hard coat layer that is not yet completely cured. , Coating a coating composition for forming a high refractive index layer containing a resin, laminating an uncured high refractive index layer, and forming the high refractive index layer in the uncured high refractive index layer after laminating The composition for use is impregnated into the hard coat layer which has not been completely cured to form a first impregnated portion on the surface layer portion of the hard coat layer, and then partial curing is performed to complete curing. Uncured high refractive index layer is formed on Further, after that, a coating composition for forming a low refractive index layer containing a resin is coated on the high refractive index layer which is not yet completely cured, and an uncured low refractive index layer is laminated. After the lamination, the composition for forming a low refractive index layer in the uncured low refractive index layer is impregnated in the high refractive index layer which is not yet completely cured to form the high refractive index layer. Forming a second impregnated portion on the surface layer of
The present invention relates to a method for producing an antireflection body, which comprises curing the whole.

[0009]

1 is a sectional view showing a laminated structure of a typical antireflection member of the present invention. As shown in FIG. 1A, the antireflection body 1 of the present invention is, for example, a substrate 2
The hard coat layer 3 and the low-refractive index layer 4 are laminated in this order on the top, and the surface layer portion (a portion near the upper surface) of the hard coat layer 3 has an impregnated portion 5A impregnated with the components of the low-refractive index layer. It has a laminated structure. In addition, including the following
“Upper” and “lower” are based on the upper and lower sides in the figure. “Upper” corresponds to the observation side, and “lower” corresponds to the side opposite to the observation side.

As shown in FIG. 1 (b), the antireflection member 1 of the present invention comprises a substrate 2 on which a hard coat layer 3, a high refractive index layer 6 and a low refractive index layer 4 are sequentially laminated. Alternatively, the high refractive index layer 6 may have a laminated structure having an impregnated portion 5B impregnated with a component of the low refractive index layer on the surface layer portion thereof.

Each of the impregnated portions 5A and 5B may be in a state in which the coating composition for forming the upper layer is infiltrated, or in a state in which the lower surface layer portion is infiltrated and dissolved, or both of them. The mixed state may be any, and the upper side of the impregnated portions 5A and 5B has a high dissolution rate and the lower side has a high permeation rate. It does not have to be in such a state. Further, the impregnation referred to here includes not only the case where all the components of the coating composition permeate while maintaining the composition ratio, but also the case where a part of the components permeates.

The laminated structure described with reference to FIG. 1 (b) may have various variations. For example, the high refractive index layer 6 in the above-mentioned laminated structure may be replaced with two layers of a medium refractive index layer and a high refractive index layer from the bottom, or may be replaced with another laminated structure for antireflection. . Alternatively, the high refractive index layer 6 may be replaced with a functional layer having a function, such as a conductive layer for imparting conductivity to the surface.

The material of the substrate 2 may be a transparent resin film or a transparent resin sheet, a transparent resin plate (eg, an acrylic resin plate) or a transparent glass plate, but industrially, continuous processing is easy and flexible and transparent. It is preferable to use a resin film. Since the substrate 2 may be colored and transparent depending on the application, the term “transparent” here includes both colorless and colored transparent. The substrate 2 is often transparent, but is not necessarily limited to being transparent, and any substrate can be used as long as the surface has reflectivity and it is necessary to suppress the reflectivity. Good.

Examples of the transparent resin film or transparent resin sheet include triacetyl cellulose (abbreviated as TAC and cellulose triacetate), diacetyl cellulose, acetate butyrate cellulose, polyether sulfone, acrylic or methacrylic type, polyurethane type, Polyester such as polyethylene terephthalate, polycarbonate, polysulfone, polyether,
Cyclic polyolefins such as trimethylpentene, polyetherketone, (meth) acrylonitrile and polynorbornene, and thermoplastic resins such as polyimide, polyamide, polyamideimide or polysiloxane can be used. It should be noted that the term (meta) is used to mean both an item with meta and an item without meta.

The film or sheet made of the above-mentioned thermoplastic resin is flexible and easy to use, but it does not need to be bent even during handling, and when a hard material is desired, such as a plate of the above resin or a glass plate. Plate-shaped ones can also be used. The thickness of the substrate 2 is preferably about 8 to 1000 μm when a flexible one is desired,
In the case of a sheet or plate, this range may be exceeded. The substrate 2 is usually flat, but when the substrate 2 constitutes a surface material for various articles, it may have an uneven shape or a three-dimensional shape for that purpose. The substrate 2 may be subjected to various treatments for the purpose of improving the adhesiveness on the side on which the antireflection layer is laminated. Further, the side other than the side on which the antireflection layer is laminated may be processed to be a surface material for various articles.

The hard coat layer 3 is provided on the substrate 2 to improve the hardness of the surface of an antireflection layer such as an upper low refractive index layer. The thickness of the hard coat layer 3 is, for example, 0.5 μm or more, and preferably 20 μm or less. The hard coat layer 3 can be formed by using a resin having a relatively high hardness selected from thermoplastic resins, but a thermosetting resin composition containing a thermosetting resin or / and an ionizing radiation curable resin is used. It is preferably composed of a cured product of the ionizing radiation-curable resin composition contained therein (hereinafter referred to as a cured resin composition), more preferably composed of a cured resin composition and inorganic ultrafine particles. The "hard coat layer" refers to a layer which is obtained by coating with a coating composition and has a surface hardness of at least H or higher in a pencil hardness test according to JIS K5400.

As the thermosetting resin, phenol resin,
A urea resin, a diallyl phthalate resin, a melamine resin, a guanamine resin, an unsaturated polyester resin, a polyurethane resin, an epoxy resin, an aminoalkyd resin, a melamine-urea co-condensation resin, a silicon resin, a polysiloxane resin and the like can be used. These resins are used by adding a crosslinking agent, a curing agent such as a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier, etc., if necessary.

The ionizing radiation-curable resin may be either one of photopolymerization or thermal polymerization in terms of reaction energy, and radical polymerization, cationic polymerization, or anion in terms of active species. It may belong to any of the polymerizations. When it contains an ethylenically unsaturated bond, photoradical polymerization and thermal radical polymerization are possible, and when it contains an epoxy group, thermosetting and photocationic polymerization are possible. In particular, when it contains an ethylenically unsaturated bond, it is polymerized directly by irradiation with visible light, ionizing radiation (ultraviolet rays or electron beams), other invisible light, or indirectly by the action of an initiator. Therefore, as in the case of photo-curing, handling from application to curing becomes easy, which is particularly preferable.

As those containing an ethylenically unsaturated bond, polyacrylic acid, polymethacrylic acid, polyacrylate, polymethacrylate, polyolefin, polystyrene, polyamide, polyimide, polyvinyl chloride,
An example of the reaction-curable polymer is an unreactive polymer having no polymerizable functional group, such as polyvinyl alcohol, polyvinyl butyral, or polycarbonate, into which an ethylenically unsaturated bond is introduced.

Further, those containing an ethylenically unsaturated bond include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate and carboxy. Monofunctional (meth) acrylates such as polycaprolactone (meth) acrylate, acrylic acid, methacrylic acid, or acrylamide, ethylene glycol diacrylate, or diacrylates such as pentaerythritol diacrylate monostearate, trimethylolpropane triacrylate, or penta. Radical polymerizable compounds such as triacrylates such as erythritol triacrylate and polyfunctional acrylates such as pentaerythritol tetraacrylate. Mer, or it can be exemplified oligomers these polymerizable monomers are polymerized. In particular, it is more preferable to use a polyfunctional acrylate in order to improve the crosslink density.

When the above radical-polymerizable oligomer or monomer having an ethylenically unsaturated bond is used, a photo-radical polymerization initiator is added, if necessary. As the photo-radical polymerization initiator, acetophenones, benzophenones, ketals, anthraquinones, thioxanthones, azo compounds, lower oxides, 2,3
-Dialkyldione compounds, disulfide compounds,
A thiuram compound, a fluoroamine compound, or the like can be used, and 3 to 8 (mass ratio) is preferably added to the above radically polymerizable oligomer and monomer 100.

Specific examples of the radical photopolymerization initiator include:
1-Hydroxy-cyclohexyl-phenyl-ketone (Ciba Specialty Chemicals Co., Ltd., trade name; available as Irgacure 184), 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropane- 1-one (Ciba Specialty Chemicals Co., Ltd., trade name; available as Irgacure 907), benzyl dimethyl ketone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1
-One, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl)
2-Hydroxy-2-methylpropan-1-one, benzophenone and the like can be exemplified, and one kind or a combination of two or more kinds can be used.

The ionizing radiation curable resin composition and the thermosetting resin composition may be used in combination with a polysiloxane component, more specifically, several types of organic reactive silicon compounds such as the following. . When an organic reactive silicon compound is used in combination, the hardness and strength of the coating film are maintained, the slipperiness of the coating film surface increases, scratch resistance is improved, and the release property is imparted to the surface. There is an advantage that the property is improved.
In any of the ionizing radiation curable resin composition and the thermosetting resin composition, a hydroxyl group as a resin component,
It is possible to further improve the hardness and strength of the coating film by using a product introduced with a polar group such as a carboxyl group, an amino group, or an amide group because it forms a covalent bond with the organic reactive silicon compound. Therefore, it is more preferable.

One of the organosilicon compounds has the general formula R _m Si
(OR ') _n , where R and R'have 1 carbon
Each of the subscript m of R and the subscript n of OR ′ represents an alkyl group of 10 to 10 and is an integer satisfying the relationship of m + n = 4.

Specifically, tetramethoxysilane, tetraethoxysilane, tetra-iso-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-tert-butoxysilane. , Tetrapentaethoxysilane, tetrapenta-iso-propoxysilane, tetrapenta-n-propoxysilane, tetrapenta-n-
Butoxysilane, tetrapenta-sec-butoxysilane, tetrapenta-tert-butoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane,
Dimethyldiethoxysilane, dimethylethoxysilane,
Dimethylmethoxysilane, dimethylpropoxysilane,
Examples thereof include dimethylbutoxysilane, methyldimethoxysilane, methyldiethoxysilane and hexyltrimethoxysilane.

The organosilicon compound 2 which can be used in combination with the ionizing radiation curable resin composition and the thermosetting resin composition is a silane coupling agent.

Specifically, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ
-Methacryloxypropyl methoxysilane, N-β-
(N-Vinylbenzylaminoethyl) -γ-aminopropylmethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxysilane, aminosilane, methylmethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ- Examples thereof include chloropropyltrimethoxysilane, hexamethyldisilazane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, methyltrichlorosilane and dimethyldichlorosilane.

The organosilicon compound 3, which can be used in combination with the ionizing radiation curable resin composition and the thermosetting resin composition, is an ionizing radiation curable silicon compound. Specific examples thereof include a plurality of functional groups that react and crosslink upon irradiation with ionizing radiation, for example, an organosilicon compound having a molecular weight of 5,000 or less and having a polymerizable double bond group, and more specifically, one end thereof. Examples thereof include vinyl-functional polysilanes, vinyl-functional polysilanes at both ends, vinyl-functional polysiloxanes at both ends, vinyl-functional polysiloxanes at both ends, or vinyl-functional polysilanes obtained by reacting these compounds, or vinyl-functional polysiloxanes. More specifically, they are the following compounds.

[0029]

[Chemical 1]

A urethane acrylate, particularly a polyurethane acrylate, may be used in combination with the ionizing radiation curable resin composition and the thermosetting resin composition. Generally speaking, acrylates, especially polyfunctional acrylates, give coating films with excellent hardness, but on the other hand, the impact resistance of the coating film becomes low and it becomes brittle. However, by adding polyurethane acrylate, impact resistance is improved. Is improved and the coating film becomes flexible. Further, a polymer having a (meth) acryloyl group introduced therein and a polymer such as a silicone resin can also be preferably used as long as the physical properties of the hard coat thin layer 4 are not deteriorated. The hard coat layer 3 may be composed mainly of the resin component described above.
It is more preferable to contain ultrafine inorganic particles.

The hard coat layer 3 is prepared by adding a solvent, an ultraviolet blocking agent, an ultraviolet absorbing agent, a surface conditioning agent (leveling agent), or other additives, if necessary, in addition to the above-mentioned components. It can be formed by coating with a coating composition for forming a coat layer. As a coating method, a roll coating method, a gravure coating method, a slide coating method, a spray coating method, a dip coating method, a screen printing method or the like can be used, and after coating, for the purpose of curing if necessary. It can be formed by drying, heating, or heating, or ultraviolet irradiation or electron beam irradiation to cure it.

The low-refractive index layer 4 is a resin formed by coating with a suitable transparent resin for coating and a low-refractive-index layer-forming coating composition containing low-refractive-index particles, preferably ultrafine particles. It consists of a composition. Alternatively, the low-refractive index layer 4 is formed by using a coating composition prepared with or without a low-refractive-index resin component having a low refractive index of its own, with inorganic particles or ultrafine inorganic particles. And a resin composition.

Examples of low refractive index inorganic particles or inorganic ultrafine particles include LiF, MgF ₂ , and 3NaF.
AlF ₃ or AlF ₃ (N = 1.
4), Na ₃ AlF ₆ (cryolite, n = 1.33), or SiO _x (1.50 ≦ x ≦ 2.00, n = 1.35)
1.48) and the like. A low-refractive index layer is prepared by preparing a coating composition using particles or ultrafine particles selected from these, coating it on the substrate 2, and drying it to solidify it. It can be 4. Examples of low refractive index particles or ultrafine particles include fluororesin and silicone resin alone, or resin particles containing these resins. These have a refractive index of 1.30
It can be preferably used in the range of ˜1.46.

However, the transparent resin for general coating materials does not have a very low refractive index, and it is more preferable to use a coating composition prepared by using a fluorine-containing polymer or a fluorine-containing oligomer as a resin component. Forming the refractive index layer 4 is preferable in terms of realizing a low refractive index. Alternatively, the above-mentioned polysiloxane component may be contained.

The fluorine-containing polymer or fluorine-containing oligomer is obtained by polymerizing or copolymerizing a fluorine-containing monomer having an ethylenically unsaturated bond. Examples of the fluorine-containing monomer having an ethylenically unsaturated bond include fluoroethylene, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene ethylene, perfluorobutadiene, and perfluoro-2,2-dimethyl-1,3-dioxole. Fluoroolefins, fully or partially fluorinated alkyl, alkenyl, or aryl esters of acrylic acid or methacrylic acid (the following "Chemical Formula 2" or "Chemical Formula 3"), and further, complete or partially fluorinated vinyl ethers, complete Alternatively, partially fluorinated vinyl esters, completely or partially fluorinated vinyl ketone and the like can be mentioned.

[0036]

[Chemical 2]

[0037]

[Chemical 3]

However, in the above formula "Chemical Formula 2", R ¹ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a halogen atom. R ^f represents a fully or partially fluorinated alkyl group, alkenyl group, heterocycle, or aryl group. R ² and R ³ are each independently a hydrogen atom,
It represents an alkyl group, an alkenyl group, a hetero group, an aryl group, or a group defined by the above R ^f . R ¹ , R ² , R ³ , and R ^f may each have a substituent other than a fluorine atom. Further, arbitrary two or more groups may be bonded to R ² , R ³ and R ^f to form a ring structure.

In the above formula "Chemical formula 3", A represents a completely or partially fluorinated n-valent organic group. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a halogen atom. R ⁴ may have a substituent other than a fluorine atom. n represents an integer of 2-8. )

When a fluorine-containing polymer having a polymerizable functional group capable of polymerizing with each other and a fluorine-containing monomer and / or oligomer are combined, the fluorine-containing polymer improves the film-forming property of the coating composition for coating, Crosslink density and coating suitability are improved by the contained monomer and / or oligomer, and the balance of both components makes
It is preferable because the hardness and strength of the coating film are realized. In particular, the fluorine-containing polymer has a number average molecular weight of 20,
000 to 100,000 and a number average molecular weight of 2 as a fluorine-containing monomer and / or oligomer.
It is more preferable to use a combination of 10,000 or less because it is easy to balance various physical properties including coating suitability, film-forming property, coating film hardness, coating film strength and the like. When the refractive index of the fluoropolymer is sufficiently low, it is preferable to combine with a monomer and / or oligomer not containing fluorine because the strength of the coating film can be more easily improved. Fluorine-free monomer,
Examples of the oligomer include radically polymerizable monomers and oligomers having an ethylenically unsaturated bond, which have already been described as the materials for forming the hard coat layer 3.

In the above, the fluorine-containing monomer or oligomer is a homopolymer or copolymer of one or more selected from the above-mentioned fluorine-containing monomers, or a fluorine-containing monomer as described above. With one or more selected types,
A copolymer with one or more fluorine-free monomers that do not contain fluorine can be used. In order to improve the mechanical strength of the low refractive index layer 4, it is effective to improve the adhesiveness between the low refractive index layer 4 and the lower layer, and for that purpose, a coating composition for forming the low refractive index layer is used. It is preferable that one of the constituent resin components is introduced with a polar group such as a hydroxyl group, a carboxyl group, an amino group, or an amide group.

Further, a fluorine-containing monomer having no polymerizable functional group can also be used. Specifically, polytetrafluoroethylene, 4-fluoroethylene-6-fluoropropylene copolymer, 4-fluoroethylene- Perfluoroalkyl vinyl ether copolymer, 4-fluoroethylene-ethylene copolymer, polyvinyl fluoride, polyvinylidene fluoride, fully or partially fluorinated alkyl, alkenyl, or aryl ester of acrylic acid or methacrylic acid (for example,
Polymers or copolymers of the above "Chemical formula 2" or "Chemical formula 3", fluoroethylene-hydrocarbon type vinyl ether copolymers, or fluorine-modified epoxy, polyurethane, cellulosic, phenol, polyimide, or silicone Resin can be mentioned. In addition, amorphous transparent fluororesin (trade name of Asahi Glass Co., Ltd .;
"Cytop" etc.) can also be used.

When the low refractive index layer 4 is formed using the coating composition prepared by using the above-mentioned fluorine-containing polymer, fluorine-containing oligomer or the like as a resin component, the particles having the low refractive index described above should be used. You can From the viewpoint of ensuring more transparency, it is more preferable to contain ultrafine particles.

Here, the ultrafine particles are smaller than those generally called fine particles having a particle diameter of several μm to several 100 μm. The specific particle size of the ultrafine particles used in the present invention is different from the optical performance required depending on the application, so it is difficult to say unconditionally, but the primary particle size is preferably in the range of 1 nm to 500 nm. Even if a primary particle size of less than 1 nm is used, the hardness and strength of the coating film are not improved. The primary particle size is 50
If it exceeds 0 nm, the transparency of the coating film is impaired, and it may not be used at all depending on the application. The ultrafine particles may be spherical, needle-like, or any other shape as long as they can be uniformly dispersed in the resin and the hardness and strength of the coating film can be secured.

In order to form the low refractive index layer 4 using a fluorine-containing polymer, a fluorine-containing oligomer or the like as a resin component, a photoradical polymerization initiator is blended if necessary, and if necessary, a solvent and an ultraviolet ray shield are also added. It can be formed by coating with a coating composition for forming a low refractive index layer prepared by adding an agent, an ultraviolet absorber, a surface modifier (leveling agent), or other additives. As the coating method, a roll coating method, a gravure coating method, a slide coating method, a spray coating method, a dip coating method, or a screen printing method can be used.After coating, if necessary, drying, heating, for the purpose of curing,
Alternatively, it can be formed by heating, or irradiation with ultraviolet rays or irradiation with an electron beam to cure. The low refractive index layer 4 has a refractive index of 1.1.
The thickness is preferably 0 to 1.46, and the thickness is 3
It is preferably 0 nm to 200 nm.

When the high refractive index layer 6 described with reference to FIG. 1 (b) is interposed, the high refractive index layer 6 has a refractive index of
The thickness is preferably 1.46 to 1.90, and the thickness is preferably 50 nm to 200 nm.

The high-refractive-index layer 6 contains the same resin component as in the case of forming the hard coat layer 3 and further contains inorganic fine particles, preferably an inorganic super-particle, for making the layer 6 have a high refractive index. It is formed using a coating composition for forming a high refractive index layer containing fine particles, and as the resin component, one having hardness among thermoplastic resins is used, and more preferably, a thermosetting resin. Alternatively, it is formed by using an ionizing radiation curable resin, and those resin components are cured, and the formation can be performed according to the method for forming the hard coat layer 3.

As the inorganic fine particles, preferably the inorganic ultrafine particles, titania having a generally high refractive index (refractive index n = 1.
9-2.3), zirconia (n = 1.6-2.0), zinc oxide (n = 1.6-2.0), alumina (n = 1.5)
.About.1.7), tin oxide (n = 1.7 to 2.0), indium-doped tin oxide (= ITO, n = 1.6 to 1.
9), antimony-doped tin oxide (= ATO, n = 1.
6 to 1.9), aluminum-doped zinc oxide (= AZ
O, n = 1.7 to 2.0) and the like can be used as long as they are within the range of the refractive index required for the hard coat thin layer 4. Further, when these inorganic fine particles having a high refractive index or inorganic ultrafine particles exhibit conductivity, the high refractive index layer 6 can be used as a conductive layer, and the high refractive index layer, and by extension,
It is preferable because the surface layer of the antireflection layer and further the antireflection material can be provided with conductivity, and as a result, antistatic performance can be provided.

The antireflection body 1 of the present invention is formed on the surface layer portion of the hard coat layer 3 or the high refractive index layer 6 as outlined above with reference to FIGS. 1 (a) and 1 (b). , And has an impregnated portion 5A (or 5B) of the components of the low refractive index layer. In this way, the impregnated portion 5a or 5b is formed as follows.

First, the example described with reference to FIG. 1A will be described with reference to FIG. First, a substrate 2 shown in FIG. 2 (a) is coated with a coating composition for forming a hard coat layer, and the coating film is cured by an appropriate means. The curing is a so-called "partial curing". The hard coat layer 3p that is not completely cured by stopping at the stage of
a), which is the acronym for “al” (FIG. 2B).

Next, the hard coat layer 3p which has not been completely cured is coated with a coating composition for forming a low refractive index layer, and at this point an uncured low refractive index layer 4a is formed. (FIG. 2 (c)). The subscript a indicates that it is uncured. Immediately after coating, the coating composition for forming the low refractive index layer in the uncured low refractive index layer 4a is impregnated into the lower hard coat layer 3p without taking any measures for curing. Then, the impregnated portion is formed on the surface layer portion of the hard coat layer 3p which has not been completely cured. Therefore, the underlying hard coat layer 3p
The degree of partial curing, the viscosity that imparts the impregnating property of the coating composition for forming a low refractive index layer, the chemical affinity, and the like are determined so that the above-mentioned impregnation is appropriately performed.

When the impregnation has proceeded to an appropriate degree, the whole is completely cured, that is, the lower hard coat layer 3p including the impregnated portion and the upper uncured low refractive index layer 4a are completely cured. An antireflection body 1 having a hard coat layer 3 and a low refractive index layer 4 laminated on a substrate 2 and a cured impregnated portion 5A on the surface layer portion of the hard coat layer 3 (FIG. 2 (d)).
And the hard coat layer 3 and the low refractive index layer 4 are not simply laminated, but the hard coat layer 3 is impregnated with the coating composition for forming the low refractive index layer when forming the low refractive index layer. Since it has a hardened portion, the hard coat layer 3 and the low refractive index layer 4 can be in a laminated state in which they are firmly adhered.

As described with reference to FIG. 1B, in the case where the high refractive index layer 6 is interposed and the surface portion of the high refractive index layer 6 has the impregnated portion 5B impregnated with the component of the low refractive index layer. Can also be carried out according to the above method. As described with reference to FIG. 1 (b), when the impregnated portion 5B is provided only in the surface layer portion of the high refractive index layer 6, the above If the hard coat layer 3 in the description is replaced with the high refractive index layer 6, the same operation can be performed.

When the high-refractive index layer 6 is interposed, the impregnated portion may also occur due to the relationship between the hard coat layer 3 and the high-refractive index layer 6. In this case, the hard coat layer 3 is formed by partially curing it to a state where it is not completely cured, and coating the coating composition for forming a high refractive index layer on the hard coat layer 3 The lower layer is impregnated to form the first impregnated portion, and thereafter, a curing means is used to partially cure the high refractive index layer 6 to a state where it is not yet completely cured. At this point, the lower hard coat layer 3 may be completely cured or may not be completely cured. Then, the composition for forming a low refractive index layer is coated on the high refractive index layer 6 which is not yet completely cured, and the lower layer is impregnated while it is uncured to form a second impregnated portion, Finally, by taking a curing means to completely cure the whole, the surface layer portion of the hard coat layer 3 and the surface layer portion of the high refractive index layer 6 each have a cured impregnated portion. Between the hard coat layer 3 and the high refractive index layer 6, and between the high refractive index layer 6 and the low refractive index layer 4.
It is possible to obtain the antireflection body 1 in which the adhesion between and is enhanced.

In the above description, in order to realize a state where the resin is not completely cured, it is a means for curing.
It is carried out by changing the time and conditions under which the curing means is taken and the integrated amount of energy applied to the coating film, based on the conditions of complete curing such as drying, heating, heating, ultraviolet ray irradiation, or electron beam irradiation. As an example, the condition of complete curing by UV irradiation is 80 to 2000 mJ /
When it is cm ^2, it is about 5 to 80 mJ / cm ^{2 in} order to realize a half-cured state that is not yet completely cured, which is several% to several tens% of the irradiation dose in the case of complete curing.

[0056]

Example 1 A composition for forming a hard coat layer having the following composition was prepared on a triacetyl cellulose film having a thickness of 80 μm, bar-coated, dried to remove the solvent, and then exposed to ultraviolet rays. Irradiation device (Fusion U
V system Japan Co., Ltd., light source; H bulb) was used and irradiation was carried out under the conditions of 20 mJ / cm ² for partial curing to form a 4 μm thick transparent hard coat layer to obtain a hard coat film. . The number of parts and the blending ratio are based on the mass, including the following. (Composition for forming hard coat layer) -Pentaerythritol tetraacrylate 20.0 parts-Photopolymerization initiator 1.0 part (Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 184) -Methyl isobutyl ketone 80 parts

On the formed hard coat layer, a fluorine-based UV-curable coating composition (manufactured by JSR Corporation, trade name; Opstar JM5010) was bar-coated, dried to remove the solvent, and then the same as above. Was used to irradiate and cure at a dose of 300 mJ / cm ² to form a low refractive index layer having a refractive index of 1.41 to obtain an antireflection film. The film thickness of the low refractive index layer was set so that the minimum value of the reflectance was around a wavelength of 550 nm when the reflectance was measured using a spectrophotometer (manufactured by Shimadzu Corporation).

Example 2 As in Example 1, except that the irradiation dose of ultraviolet rays was 100 mJ / cm ^2.
As a result, it was completely cured to obtain a hard coat film.
As the composition for forming a high refractive index layer to be applied on the hard coat layer of this hard coat film, in the following compositions, those other than the photoinitiator were used in an amount of about 4 times the amount of zirconia beads (diameter: 0.3 mm). ) Was used as a medium and shaken with a paint shaker for 10 hours, and a photoinitiator was added after shaking to obtain a composition for forming a high refractive index layer.

[0059] (Coating composition for forming high refractive index layer)   ・ Rutile type titanium oxide 10 parts     (Ishihara Sangyo Co., Ltd., product number; TTO51 (C), primary particle size; 0.01-       0.03 μm)   ・ Pentaerythritol triacrylate 4 parts     (Nippon Kayaku Co., Ltd., trade name; PET30)   ・ 2 parts dispersant     (Made by Big Chemie Japan, Disperbic 163)   ・ Photoinitiator 0.2 parts     (Ciba Specialty Chemicals Co., Ltd., trade name; Irgacure       184)   ・ Methyl isobutyl ketone 37.3 parts

The above composition for forming a high refractive index layer was applied onto a hard coat layer of a hard coat film in the same manner as in the formation of the hard coat layer, except that the irradiation dose of ultraviolet rays was 20 mJ / cm ^2. Cured. The film thickness of the high refractive index layer was set so that the minimum value of the reflectance was around a wavelength of 550 nm when the reflectance was measured using a spectrophotometer (manufactured by Shimadzu Corporation).

On the formed high refractive index layer, a low refractive index layer was formed by using the same composition as in Example 1 and the same method. Again, the film thickness of the low-refractive index layer was set so that the minimum value of the reflectance was around the wavelength of 550 nm when the reflectance was measured using a spectrophotometer (manufactured by Shimadzu Corporation).

Comparative Example 1 An antireflection film was prepared in the same manner as in Example 1 except that the irradiation dose of ultraviolet rays at the time of forming the hard coat layer was 300 mJ / cm ² .

Comparative Example 2 An antireflection film was prepared in the same manner as in Example 3 except that the irradiation dose of ultraviolet rays at the time of forming the high refractive index layer was 150 mJ / cm ² .

The antireflection films of Examples and Comparative Examples obtained as described above were evaluated for the three items of reflectance, film strength, and adhesion. The reflectance is a wavelength measured using a spectrophotometer (manufactured by Shimadzu Corporation);
It is at 550 nm, and the reflectance is preferably 1.2% or less, although it depends on the application. Further, using a # 0000 steel wool, rubbed 20 times with a constant load, a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name;
NDH2000) and the mass (unit: g) of the weight when the haze changed was defined as the film strength. This film strength is used in applications where it is easy to touch human hands, etc.
It is preferably 200 g or more, but even less than 200, it can be used as long as it is used infrequently in contact with human hands. Further, the adhesiveness was evaluated by a cross-cut peeling test using cellophane tape.

[0065]

[Table 1]

[0066]

According to the first aspect of the present invention, the component of the upper low-refractive index layer is impregnated in the lower hard coat layer to provide an antireflection body in which the adhesion between both layers is improved. be able to. According to the invention of claim 2, a hard coat layer, a high-refractive index layer or a conductive layer, and a low-refractive index layer are laminated, and at any one interface or two interfaces of these layers, the component of the upper layer becomes the lower layer. By being impregnated, it is possible to provide an antireflection body in which the adhesiveness of both layers in contact with each other is improved. According to the invention of claim 3, in addition to the effect of the invention of claim 1 or claim 2, since the hard coat layer is composed of a thermosetting resin and / or an ionizing radiation curable resin, it is more closely adhered. It is possible to provide an antireflective body having high property and high surface hardness. According to the invention of claim 4, in addition to the effect of the invention of claim 2, since the high refractive index layer is composed of a thermosetting resin and / or an ionizing radiation curable resin, the adhesion is higher. It is possible to provide an antireflection body having a high surface hardness. According to the invention of claim 5, in addition to the effect of the invention of claim 4, since the refractive index of the high refractive index layer is improved by further containing the inorganic ultrafine particles, the antireflection property is further improved. The body can be provided. According to the invention of claim 6, in the invention of any one of claims 1 to 5, the refractive index of the high refractive index layer is defined, and therefore, an antireflection body exhibiting antireflection properties more reliably is provided. be able to. According to the invention of claim 7, in addition to the effect of any one of claims 1 to 6, the low refractive index is constituted by using a thermosetting resin and / or an ionizing radiation curable resin. Due to the contribution of the hardness of the low refractive index layer, it is possible to provide an antireflection body having a high surface hardness. According to the invention of claim 8, in addition to the effect of the invention of claim 7, it is possible to provide an antireflection body having a lower refractive index of the low refractive index layer and high antireflection properties. According to the invention of claim 9, in addition to the effect of the invention of claim 7, the refractive index of the low refractive index layer is lower, the antireflection property is high, and the hardness of the low refractive index layer contributes. An antireflection body having a high surface hardness can be provided. According to the invention of claim 10, in addition to the effect of the invention of claim 7, since the slip property of the surface of the low refractive index layer is increased, the scratch resistance is improved, and the surface is given releasability. An antireflection body having improved antifouling property can be provided. According to the invention of claim 11, in addition to the effect of the invention of any one of claims 1 to 10, by defining the refractive index of the low refractive index layer, antireflection capable of more reliably realizing antireflection property The body can be provided.
According to the invention of claim 12, when the hard coat layer and the low refractive index layer are sequentially laminated, the upper layer is formed in a state where the lower layer is partially cured, and the lower layer is impregnated with the components of the upper layer, It is possible to provide a method for producing an antireflection body capable of improving the adhesion between both layers. Claim 13
According to the invention, when the hard coat layer, the high-refractive index layer, and the low-refractive index layer are sequentially laminated, the lowermost layer is cured, and the intermediate layer is partially cured to form the upper layer. By impregnating the intermediate layer with the component (1), it is possible to provide a method for producing an antireflection body capable of improving the adhesion between both layers. According to the invention of claim 14, when the hard coat layer, the high refractive index layer, and the low refractive index layer are sequentially laminated, the middle layer is formed with the lowermost layer partially cured,
By impregnating the lowermost layer with the components of the middle layer, the adhesion of both layers is improved.By forming the upper layer with the middle layer partially cured, and impregnating the components of the upper layer into the middle layer, the adhesion of both layers is improved. To provide a method for producing an antireflection body capable of improving adhesion between a hard coat layer and a high refractive index layer, and between a high refractive index layer and a low refractive index layer by improving the property. You can

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an antireflection body of the present invention.

FIG. 2 is a cross-sectional view showing the manufacturing process of the antireflection body of the present invention.

[Explanation of symbols]

1 Anti-reflective body 2 base 3 hard coat layer 4 Low refractive index layer 5 compatible parts 6 High refractive index layer

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2K009 AA04 AA05 AA15 BB02 BB14                       BB24 BB25 BB28 CC02 CC03                       CC06 CC09 CC26 CC34 CC35                       CC42 DD02 DD05 DD06                 4F100 AA01D AA21 AA27 AJ05                       AK01B AK01C AK01D AK17C                       AK25 AK52C AL05B AL05C                       AT00A BA03 BA04 BA07                       BA10A BA10C CA30 DE01D                       GB07 GB31 GB41 JB13B                       JB13C JB13D JB14B JB14C                       JB14D JG01D JK12B JN18C                       JN18D JN30 YY00C YY00D

Claims (14)

[Claims] 1. A laminated structure in which a hard coat layer and a low refractive index layer, both of which are made of a resin composition containing a resin, are sequentially laminated on a substrate, and a surface layer portion of the hard coat layer comprises: An antireflection body having an impregnated portion impregnated with the component of the low refractive index layer. 2. A laminated structure in which a hard coat layer, a high refractive index layer or a conductive layer, and a low refractive index layer, each of which is made of a resin composition containing a resin, are sequentially laminated on a substrate, The surface layer of the hard coat layer has an impregnated portion impregnated with the components of the high refractive index layer or the conductive layer, and / or the low refractive index of the surface layer portion of the high refractive index layer or the conductive layer. An antireflection body having an impregnated portion impregnated with a component of the refractive index layer. 3. A cured resin composition in which the hard coat layer is a cured product of a thermosetting resin composition containing a thermosetting resin and / or an ionizing radiation curable resin composition containing an ionizing radiation curable resin. The antireflection body according to claim 1 or 2, wherein the antireflection body is composed of a thing. 4. A cured resin, wherein the high refractive index layer is a cured product of a thermosetting resin composition containing a thermosetting resin and / or an ionizing radiation curable resin composition containing an ionizing radiation curable resin. The antireflection body according to claim 2, which is composed of a composition. 5. The antireflection body according to claim 4, wherein the high refractive index layer further contains inorganic ultrafine particles. 6. The antireflection body according to claim 1, wherein the high refractive index layer has a refractive index of more than 1.46. 7. A cured resin in which the low refractive index layer is a cured product of a thermosetting resin composition containing a thermosetting resin and / or an ionizing radiation curable resin composition containing an ionizing radiation curable resin. The antireflection body according to any one of claims 1 to 6, which is composed of a composition. 8. The antireflection body according to claim 7, wherein the low refractive index layer contains a fluoropolymer component. 9. The antireflection body according to claim 7, wherein the low refractive index layer contains a fluorine-containing oligomer component. 10. The antireflection body according to claim 7, wherein the low refractive index layer contains a polysiloxane component. 11. The low refractive index layer has a refractive index of 1.10 to 10.
It is 1.46, It is characterized by the above-mentioned.
Antireflection body described. 12. A coating composition for forming a hard coat layer, which comprises a resin, which comprises a hard coat layer mainly composed of a resin composition and a low refractive index layer, which are sequentially laminated on a base. A hard coat layer that has not yet been completely cured is formed by coating an article and performing partial curing, and then containing a resin on the hard coat layer that has not been completely cured. The coating composition for forming a low-refractive-index layer is laminated to form an uncured low-refractive-index layer, and after lamination, the composition for forming a low-refractive-index layer in the uncured low-refractive-index layer A method for producing an antireflection body, which comprises impregnating the hard coat layer which has not been completely cured to form an impregnated portion in the surface layer portion of the hard coat layer, and then curing the whole. 13. A hard coat containing a resin, which comprises a hard coat layer mainly comprising a resin composition, a high refractive index layer, and a low refractive index layer, which are sequentially laminated on a base. A hard coat layer is formed by coating the coating composition for layer formation and curing the composition.
Next, a coating composition for forming a high refractive index layer containing a resin is coated on the hard coat layer and partially cured to form a high refractive index layer which is not yet completely cured. Further, thereafter, a coating composition for forming a low refractive index layer containing a resin is coated on the high refractive index layer which is not yet completely cured, and an uncured low refractive index layer is laminated. After the lamination, the composition for forming a low refractive index layer in the uncured low refractive index layer is impregnated in the high refractive index layer which is not yet completely cured to form the high refractive index layer. A method for producing an antireflection body, which comprises forming an impregnated portion on the surface layer portion and then curing the whole. 14. A hard coat containing a resin, which comprises a hard coat layer mainly comprising a resin composition, a high refractive index layer, and a low refractive index layer, which are sequentially laminated on a substrate. By coating the layer-forming coating composition and performing partial curing, a hard coat layer that is not yet completely cured is formed, and then, on the above-mentioned hard coat layer that is not yet completely cured. A coating composition for forming a high refractive index layer containing a resin,
Laminating an uncured high refractive index layer, after lamination, the high refractive index layer forming composition in the uncured high refractive index layer in the yet not completely hardened hard coat layer After impregnating and forming a first impregnated portion on the surface layer portion of the hard coat layer, partial curing is performed to form a high refractive index layer which is not yet completely cured, and then, On the high-refractive index layer which has not been completely cured, a coating composition for forming a low-refractive index layer containing a resin is coated,
Laminating an uncured low refractive index layer, and after laminating the low refractive index layer forming composition in the uncured low refractive index layer in the high refractive index layer not yet completely cured Impregnate
A method for producing an antireflection body, which comprises forming a second impregnated portion on the surface layer portion of the high refractive index layer and then curing the whole.