JP6460471B2 - Laminated body, polarizing plate, and image display device - Google Patents

Description

  The present invention relates to a laminate, a polarizing plate, and an image display device.

  A laminate may be disposed on the surface of a flooring material, an electric appliance or the like in order to obtain scratch resistance and antifouling properties (see Patent Document 1). In order to obtain scratch resistance, the slipperiness of the surface of the laminate is also important. Currently, a silicon-containing compound for improving the slipperiness and a fluorine-containing compound for obtaining antifouling properties are provided on the uppermost layer of the laminate. May be included.

JP 2004-225456 A

  However, the scratch resistance and antifouling property on the surface of the laminate are not sufficient, and at present, further improvement of the scratch resistance and antifouling property is required. In particular, when fine particles such as hollow silica fine particles are included in the uppermost layer of the laminate, silicon-containing compounds and fluorine-containing compounds are unlikely to precipitate (bleed out) on the surface of the laminate due to the presence of fine particles. Scratch and antifouling properties are difficult to improve. Here, the slipperiness of the laminate is determined by the amount of the silicon-containing compound present on the surface of the uppermost layer, and the antifouling property is determined by the amount of the fluorine-containing compound present on the surface of the uppermost layer. In order to further improve the soiling, an important point is how many silicon-containing compounds and fluorine-containing compounds are present on the surface of the uppermost layer. In this regard, in order to further improve the scratch resistance and antifouling property, if the addition amount of the silicon-containing compound or fluorine-containing compound is increased with respect to the uppermost layer of the laminate, the silicon-containing compound or Although it is considered that a large amount of fluorine-containing compound can be present, when the amount of silicon-containing compound or fluorine-containing compound added is increased, the scratch resistance and antifouling properties are improved up to a certain amount, but the amount added Even if it increases, scratch resistance and antifouling property do not improve any more, and as a result, desired scratch resistance and antifouling property cannot be obtained.

  The present invention has been made to solve the above problems. That is, it aims at providing the laminated body which can obtain the outstanding abrasion resistance and antifouling property, and the polarizing plate and image display apparatus provided with this laminated body.

  According to one aspect of the present invention, the laminate includes a transparent base material, a first functional layer, and a second functional layer in this order, and the surface of the second functional layer is The first functional layer includes a non-crosslinkable fluorine-containing compound and a binder resin, and the second functional layer includes fine particles, a crosslinkable silicon-containing compound, and a crosslinkable fluorine. A laminate is provided that is a layer made of a cured product of the second functional layer composition containing at least the containing compound and the curable resin precursor.

  According to another aspect of the present invention, the polarizing element is formed on the surface of the laminated body opposite to the surface on which the first functional layer is formed in the transparent base material. A polarizing plate is provided.

  According to another aspect of the present invention, there is provided an image display device comprising a display element and a laminated body disposed closer to an observer side than the display element.

  According to another aspect of the present invention, there is provided an image display device, comprising: a display element; and the above polarizing plate positioned closer to an observer than the display element, wherein the polarizing plate is the low refractive index layer. An image display device is provided in which the surface of the image display device is arranged to be a surface on the viewer side of the image display device.

  According to the laminate of one embodiment of the present invention, the polarizing plate of another embodiment, and the image display device of another embodiment, the first functional layer contains a non-crosslinkable fluorine compound, and the second functional layer contains fine particles. And a second functional layer composition comprising a crosslinkable silicon-containing compound, a crosslinkable fluorine-containing compound, and a curable resin precursor. The silicon-containing compound and the crosslinkable fluorine-containing compound are likely to precipitate (bleed out) on the surface of the second functional layer. For this reason, even if fine particles are present, many crosslinkable silicon-containing compounds and crosslinkable fluorine-containing compounds can be present on the surface of the second functional layer. Thereby, the outstanding abrasion resistance and antifouling property can be obtained.

It is a schematic block diagram of the laminated body which concerns on embodiment. It is a schematic block diagram of the polarizing plate which concerns on embodiment. It is a schematic block diagram of the liquid crystal panel which is an example of the display panel which concerns on embodiment. It is a schematic block diagram of the liquid crystal display which is an example of the image display apparatus which concerns on embodiment.

  Hereinafter, a laminate, a polarizing plate, a display panel, and an image display device according to embodiments of the present invention will be described with reference to the drawings. In the present specification, the “laminate” includes members called “laminate film”, “laminate sheet”, “laminate” and the like. In the present specification, the “weight average molecular weight” is a value obtained by dissolving in a solvent such as tetrahydrofuran (THF) and converting to polystyrene by a conventionally known gel permeation chromatography (GPC) method. FIG. 1 is a schematic configuration diagram of a laminate according to the present embodiment.

<<< laminate >>>
The laminated body 10 shown by FIG. 1 is equipped with the transparent base material 11, the 1st functional layers 12 and 13, and the 2nd functional layer 14 in this order. Although the laminated body 10 shown by FIG. 1 functions as an antireflection film, a use will not be specifically limited if it is arrange | positioned on the surface of a certain member or apparatus.

  The “functional layer” is a single layer intended to exhibit some function in the laminate, and specifically includes, for example, hard coat property, antireflection property, antistatic property, scratch resistance, or Examples include a layer for exhibiting functions such as antifouling properties. The function of the first functional layer is not particularly limited, but the second functional layer has at least scratch resistance and antifouling functions.

  The first functional layer may be a single layer, but a plurality (two or more layers) are preferably present in the thickness direction of the laminate from the viewpoint of obtaining a lift-up effect more reliably. When there are a plurality of first functional layers, other components may be different from each other as long as the first functional layer includes a non-crosslinkable fluorine-containing compound and a binder resin described later. In the present embodiment, the first functional layers 12 and 13 are present between the transparent substrate 11 and the second functional layer 14. If the first functional layer 12 is provided, the first functional layer 13 may not be provided. If the first functional layer 13 is provided, the first functional layer 12 is not provided. May not be provided. As will be described later, since the first functional layer 12 functions as a hard coat layer and the first functional layer 13 functions as a high refractive index layer, the first functional layer 13 is provided. If not, a high refractive index layer that does not contain a non-crosslinkable fluorine-containing compound may be provided between the first functional layer 12 and the second functional layer 14, and the first functional layer 12 is provided. If not, a hard coat layer in which the first functional layer does not contain a non-crosslinkable fluorine-containing compound may be provided.

  The first functional layer is preferably in contact with the second functional layer, but the second functional layer is not necessarily in direct contact with the first functional layer. For example, a third functional layer that does not contain at least a non-crosslinkable fluorine-containing compound may be disposed between the first functional layer and the second functional layer.

  In the laminated body 10, it is preferable that the reflection Y value measured from the second functional layer 14 side is less than 0.3%. The reflection Y value is more preferably 0.15% or less, and still more preferably 0.1% or less, from the viewpoint of further suppressing reflection.

  The reflection Y value is based on JIS Z8722. The reflection Y value is, for example, regular reflection reflected by the laminate by irradiating light with an incident angle of 5 degrees from the low refractive index layer side of the laminate using a spectrophotometer such as MPC3100 manufactured by Shimadzu Corporation. The reflected light in the direction is received, the reflectance in the wavelength range of 380 nm to 780 nm is measured, and then calculated as software (for example, software built in the MPC 3100) that is converted into brightness that is perceived by human eyes. . In this specification, “light having an incident angle of 5 degrees” means light inclined by 5 degrees with respect to the normal direction when the normal direction of the film surface of the laminate is set to 0 degrees. The “film surface” refers to a surface that coincides with the planar direction when the target laminate is viewed as a whole and globally. In addition, when measuring a reflection Y value, in order to prevent the back surface reflection of a laminated body, it is preferable to stick a black tape on the surface on the opposite side to the surface in which the 1st functional layer in a transparent base material is previously formed. .

In the laminate 10, when a steel wool test in which the surface 14 A of the second functional layer 14 is rubbed 10 times while applying a load using steel wool is subjected to scratches on the surface 14 A of the second functional layer 14. It is preferable that the maximum load in which no is confirmed is 200 g / cm ² or more. The maximum load is more preferably 300 g / cm ² or more. In the steel wool resistance test, # 0000 steel wool (product name “Bonstar”, manufactured by Nippon Steel Wool Co., Ltd.) is used.

  From the viewpoint of suppressing the cloudiness, the total haze value of the laminate 10 is preferably 0.5% or less, and more preferably 0.3% or less. The lower limit of the total haze can be 0.2% or more. The total haze value can be measured by a method based on JIS K7136 using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory).

<< Transparent substrate >>
The transparent substrate 11 is not particularly limited as long as it has optical transparency. For example, a cellulose acylate substrate, a cycloolefin polymer substrate, a polycarbonate substrate, an acrylate polymer substrate, a polyester substrate, or a glass group is used. Materials.

  As a cellulose acylate base material, a cellulose triacetate base material and a cellulose diacetate base material are mentioned, for example. As a cycloolefin polymer base material, the base material which consists of polymers, such as a norbornene-type monomer and a monocyclic cycloolefin monomer, is mentioned, for example.

  Examples of the polycarbonate substrate include aromatic polycarbonate substrates based on bisphenols (bisphenol A and the like), aliphatic polycarbonate substrates such as diethylene glycol bisallyl carbonate, and the like.

  Examples of the acrylate polymer base material include a poly (meth) methyl acrylate base material, a poly (meth) ethyl acrylate base material, and a (meth) methyl acrylate- (meth) butyl acrylate copolymer base material. Can be mentioned.

  Examples of the polyester base material include base materials containing at least one of polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate as constituent components.

  Examples of the glass substrate include glass substrates such as soda lime silica glass, borosilicate glass, and alkali-free glass.

  Among these, a cellulose acylate base material is preferable because of excellent retardation and easy adhesion with a polarizer, and among the cellulose acylate base materials, a triacetyl cellulose base material (TAC base material) is preferable. A triacetyl cellulose base material is a light-transmitting base material capable of setting an average light transmittance to 50% or more in a visible light region of 380 to 780 nm. The average light transmittance of the triacetyl cellulose base material is preferably 70% or more, and more preferably 85% or more.

  In addition, as a triacetyl cellulose base material, in addition to pure triacetyl cellulose, cellulose acetate propionate, cellulose acetate butyrate and the like may be used in combination with components other than acetic acid as a fatty acid forming an ester with cellulose. Good. Further, these triacetylcelluloses may be added with other additives such as other cellulose lower fatty acid esters such as diacetylcellulose, or plasticizers, ultraviolet absorbers, and lubricants as necessary.

  A cycloolefin polymer substrate is preferred from the standpoint of retardation and heat resistance, and a polyester substrate is preferred from the standpoint of mechanical properties and heat resistance.

  The thickness of the transparent substrate 11 is not particularly limited, but can be 5 μm or more and 100 μm or less. The lower limit of the thickness of the transparent substrate 11 is preferably 15 μm or more, more preferably 25 μm or more from the viewpoint of handling properties. . The upper limit of the thickness of the transparent substrate 11 is preferably 80 μm or less from the viewpoint of thinning.

<< first functional layer >>
The first functional layers 12 and 13 are layers including a non-crosslinkable fluorine-containing compound and a binder resin. As described above, the function of the first functional layer is not particularly limited, but the first functional layer preferably functions as a hard coat layer or a high refractive index layer. The first functional layer 12 of the laminate 10 according to the present embodiment functions as a hard coat layer, and the first functional layer 13 functions as a high refractive index layer.

  The hard coat layer is a layer having a hardness of “H” or more in a pencil hardness test (4.9 N load) defined by JIS K5600-5-4 (1999). By setting the pencil hardness of the first functional layer 12 to “H” or higher, the hardness of the first functional layer 12 can be sufficiently reflected on the surface of the second functional layer 14 to improve durability. Can be made. From the viewpoint of adhesion to the first functional layer 13 formed on the first functional layer 12, toughness and prevention of curling, the upper limit of the pencil hardness on the surface of the first functional layer 12 is about 4H. It is preferable to do.

  The film thickness of the first functional layer 12 is preferably 1 μm or more and 10 μm or less. If the film thickness of the first functional layer 12 is within this range, desired hardness can be obtained, and the first functional layer can be made thinner. The film thickness of the first functional layer 12 can be measured by observation with a cross-sectional microscope.

  The lower limit of the film thickness of the first functional layer 12 is more preferably 8 μm or less from the viewpoint of suppressing cracking of the first functional layer. The thickness of the first functional layer 12 is more preferably not less than 0.5 μm and not more than 5.0 μm from the viewpoint of suppressing curling while reducing the thickness of the first functional layer.

  The refractive index of the first functional layer 12 may be 1.50 or more and 1.60 or less. The lower limit of the refractive index of the first functional layer 12 may be 1.52 or more, and the upper limit of the refractive index of the first functional layer 12 may be 1.56 or less. The refractive index difference between the transparent substrate 11 and the first functional layer 12 is preferably within 0.10, more preferably within 0.06, from the viewpoint of suppressing the occurrence of interference fringes.

  The refractive index of the first functional layer 12 can be measured with an Abbe refractometer (NAR-4T manufactured by Atago Co., Ltd.) or an ellipsometer after forming a single layer. Further, as a method for measuring the refractive index after forming the laminated body 10, the first functional layer 12 is scraped off with a cutter or the like to prepare a powder sample, and JIS K7142 (2008) B method (powder or granular) The Becke method according to (for transparent material) (using a Cargill reagent with a known refractive index, placing the powder sample on a glass slide, dropping the reagent on the sample, and immersing the sample in the reagent. Observe the state by microscopic observation, and use a method in which the refractive index of the reagent is such that the bright line (Becke line) generated in the sample outline cannot be visually observed due to the difference in refractive index between the sample and the reagent. Can do.

  As described above, the first functional layer 12 includes the non-crosslinkable fluorine-containing compound and the binder resin, but may further include fine particles.

<Non-crosslinkable fluorine-containing compound>
Although the function of the non-crosslinkable fluorine-containing compound in the first functional layer 12 is not particularly limited, for example, the non-crosslinkable fluorine-containing compound functions as a leveling agent. As the non-crosslinkable fluorine-containing compound, a compound having a weight average molecular weight of 10,000 to 50,000 is preferable. Examples of such commercially available non-polymerizable fluorine-containing compounds include F568 and F477 manufactured by DIC.

  The content of the non-crosslinkable fluorine-containing compound in the first functional layer composition is preferably 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the curable resin precursor. By setting the content of the non-crosslinkable fluorine-containing compound within this range, the flatness of the surface of the first functional layer 12 can be sufficiently ensured.

<Binder resin>
The binder resin contains a cured product (polymer, cross-linked product) of a curable resin precursor. The “curable resin precursor” in the present specification means a resin precursor in which the resin precursor has photocurability or thermosetting and becomes a resin by photocuring or thermosetting. The resin may contain a solvent-drying resin in addition to the cured product of the curable resin precursor. The photocurable resin precursor having photocurability has at least one photopolymerizable functional group. In the present specification, the “photopolymerizable functional group” is a functional group capable of undergoing a polymerization reaction by light irradiation. Examples of the photopolymerizable functional group include ethylenic double bonds such as a (meth) acryloyl group, a vinyl group, and an allyl group. In the present specification, “(meth) acryloyl group” means both “acryloyl group” and “methacryloyl group”. Moreover, examples of the light irradiated when the photocurable resin precursor is cured include visible light and ionizing radiation such as ultraviolet rays, X-rays, electron beams, α rays, β rays, and γ rays. The thermosetting resin precursor having thermosetting properties has at least one thermopolymerizable functional group.

  Examples of the photocurable resin precursor include a photopolymerizable monomer, a photopolymerizable oligomer, and a photopolymerizable polymer, which can be appropriately adjusted and used. As the photocurable resin precursor, a combination of a photopolymerizable monomer and a photopolymerizable oligomer or photopolymerizable polymer is preferable.

(Photopolymerizable monomer)
The photopolymerizable monomer has a weight average molecular weight of less than 1000. The photopolymerizable monomer is preferably a polyfunctional monomer having two or more photopolymerizable functional groups (that is, bifunctional).

  Examples of the bifunctional or higher monomer include trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, and pentaerythritol tri (meth). Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditri Methylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentaerythritol octa (meth) acrylate, Lapentaerythritol deca (meth) acrylate, isocyanuric acid tri (meth) acrylate, isocyanuric acid di (meth) acrylate, polyester tri (meth) acrylate, polyester di (meth) acrylate, bisphenol di (meth) acrylate, diglycerin tetra ( (Meth) acrylate, adamantyl di (meth) acrylate, isoboronyl di (meth) acrylate, dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and these are PO, EO And the like modified.

  Among these, from the viewpoint of obtaining a first functional layer having high hardness, pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), pentaerythritol tetraacrylate (PETTA), dipentaerythritol pentaacrylate (DPPA), etc. Is preferred.

(Photopolymerizable oligomer)
The photopolymerizable oligomer has a weight average molecular weight of 1000 or more and less than 10,000. The photopolymerizable oligomer is preferably a bifunctional or higher polyfunctional oligomer. Polyfunctional oligomers include polyester (meth) acrylate, urethane (meth) acrylate, polyester-urethane (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, melamine (meth) acrylate, and isocyanurate (meth). Examples include acrylate and epoxy (meth) acrylate.

(Photopolymerizable polymer)
The photopolymerizable polymer has a weight average molecular weight of 10,000 or more, and the weight average molecular weight is preferably from 10,000 to 80,000, more preferably from 10,000 to 40,000. When the weight average molecular weight exceeds 80,000, the viscosity is high, so that the coating suitability is lowered, and the appearance of the obtained optical laminate may be deteriorated. Examples of the polyfunctional polymer include urethane (meth) acrylate, isocyanurate (meth) acrylate, polyester-urethane (meth) acrylate, and epoxy (meth) acrylate.

  The thermosetting resin precursor is not particularly limited. For example, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy resin, aminoalkyd resin, melamine-urea Examples thereof include respective precursors such as co-condensation resins, silicon resins, and polysiloxane resins.

  The solvent-drying resin is a resin that forms a film only by drying a solvent added to adjust the solid content during coating, such as a thermoplastic resin. When the solvent-drying type resin is added, film defects on the coating surface of the coating liquid can be effectively prevented when the first functional layer 12 is formed. It does not specifically limit as solvent dry type resin, Generally, a thermoplastic resin can be used.

  Examples of thermoplastic resins include styrene resins, (meth) acrylic resins, vinyl acetate resins, vinyl ether resins, halogen-containing resins, alicyclic olefin resins, polycarbonate resins, polyester resins, polyamide resins. , Cellulose derivatives, silicone resins and rubbers or elastomers.

  The thermoplastic resin is preferably amorphous and soluble in an organic solvent (particularly a common solvent capable of dissolving a plurality of polymers and curable compounds). In particular, from the viewpoint of transparency and weather resistance, styrene resins, (meth) acrylic resins, alicyclic olefin resins, polyester resins, cellulose derivatives (cellulose esters, etc.) and the like are preferable.

<Fine particles>
The fine particles may be inorganic fine particles, organic fine particles, or a mixture thereof. Examples of the inorganic fine particles include inorganic oxide fine particles such as silica (SiO ₂ ) fine particles, alumina fine particles, titania fine particles, tin oxide fine particles, antimony-doped tin oxide (abbreviated as ATO) fine particles, and zinc oxide fine particles.

  Examples of the organic fine particles include plastic fine particles. Specific examples of the plastic fine particles include polystyrene fine particles, melamine resin fine particles, acrylic fine particles, acrylic-styrene copolymer fine particles, silicone fine particles, benzoguanamine fine particles, benzoguanamine / formaldehyde condensation fine particles, polycarbonate fine particles, polyethylene fine particles, and the like.

  In order to form the first functional layer 12, first, a first functional layer composition containing at least a non-crosslinkable fluorine-containing compound and a curable resin precursor is applied to the surface of the transparent substrate 11. Subsequently, in order to dry the coating-form 1st composition for functional layers, it conveys to the heated zone, the 1st composition for functional layers is dried by various well-known methods, and a solvent is evaporated. Thereafter, the first functional layer is formed by irradiating the film-like first functional layer composition with light such as ultraviolet rays and / or applying heat to cure (polymerize, crosslink) the curable resin precursor. The first functional layer 12 is formed by curing the composition.

  Examples of the method for applying the first functional layer composition include known coating methods such as spin coating, dipping, spraying, slide coating, bar coating, roll coating, gravure coating, and die coating. It is done.

  When ultraviolet rays are used as the light for curing the first functional layer composition, ultraviolet rays emitted from an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, etc. can be used. . Moreover, as a wavelength of an ultraviolet-ray, the wavelength range of 190-380 nm can be used. Specific examples of the electron beam source include various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type.

  In addition to the non-crosslinkable fluorine-containing compound and the curable resin precursor, the fine particles, the thermoplastic resin, the solvent, and a polymerization initiator may be added to the first functional layer composition as necessary. . Furthermore, the hard coat layer composition includes conventionally known dispersants, surfactants and antistatic agents depending on purposes such as increasing the hardness of the hard coat layer, suppressing cure shrinkage, and controlling the refractive index. , Silane coupling agents, thickeners, colorants, colorants (pigments, dyes), antifoaming agents, flame retardants, UV absorbers, adhesion promoters, polymerization inhibitors, antioxidants, surface modifiers, An easy lubricant or the like may be added.

<Solvent>
Examples of the solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, n-butanol, s-butanol, t-butanol, benzyl alcohol, PGME, ethylene glycol), ketones (acetone, methyl ethyl ketone (MEK), cyclohexanone. , Methyl isobutyl ketone, diacetone alcohol, cycloheptanone, diethyl ketone, etc.), ethers (1,4-dioxane, dioxolane, diisopropyl ether dioxane, tetrahydrofuran, etc.), aliphatic hydrocarbons (hexane, etc.), alicyclic Hydrocarbons (cyclohexane, etc.), aromatic hydrocarbons (toluene, xylene, etc.), halogenated carbons (dichloromethane, dichloroethane, etc.), esters (methyl formate, methyl acetate, ethyl acetate, vinegar) Propyl, butyl acetate, ethyl lactate, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, butyl cellosolve, etc.), cellosolve acetates, sulfoxides (dimethylsulfoxide etc.), amides (dimethylformamide, dimethylacetamide etc.), etc. A mixture thereof may be used.

<Polymerization initiator>
The polymerization initiator is a component that is decomposed by light irradiation to generate radicals to initiate or advance polymerization (crosslinking) of the photocurable resin precursor.

  The polymerization initiator is not particularly limited as long as it can release a substance that initiates radical polymerization by light irradiation. The polymerization initiator is not particularly limited, and known ones can be used. Specific examples include, for example, acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, thioxanthones, propiophenone. , Benzyls, benzoins, acylphosphine oxides. In addition, it is preferable to use a mixture of photosensitizers, and specific examples thereof include n-butylamine, triethylamine, poly-n-butylphosphine, and the like.

  As the polymerization initiator, when the binder resin is a resin system having a radically polymerizable unsaturated group, it is preferable to use acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether or the like alone or in combination. .

  The content of the polymerization initiator in the first functional layer composition is preferably 0.5 parts by mass or more and 10.0 parts by mass or less with respect to 100 parts by mass of the photocurable resin precursor. By setting the content of the polymerization initiator within this range, the hard coat performance can be sufficiently maintained, and curing inhibition can be suppressed.

  Although it does not specifically limit as a content rate (solid content) of the raw material in the composition for 1st functional layers, Usually, 5 to 70 mass% is preferable, and it is set to 25 to 60 mass%. More preferred.

  The first functional layer 13 is a layer provided between the first functional layer 12 and the second functional layer 14, and is in contact with the first functional layer 12 and the second functional layer 14.

  The refractive index of the first functional layer 13 may be 1.50 or more and 2.00 or less. The lower limit of the refractive index of the first functional layer 13 may be 1.60 or more, and the upper limit of the refractive index of the first functional layer 13 may be 1.75 or less. The refractive index of the first functional layer 13 can be measured by the same method as the refractive index of the first functional layer 12. The refractive index difference between the first functional layer 12 and the first functional layer 13 may be 0.05 or more and 0.25 or less.

  The film thickness of the first functional layer 13 is preferably 200 nm or less. The lower limit of the film thickness of the third functional layer 13 is preferably 40 nm or more, and more preferably 50 nm or more. The upper limit of the film thickness of the first functional layer 13 is preferably 170 nm or less, and more preferably 160 nm or less.

  As described above, the first functional layer 13 includes a non-crosslinkable fluorine-containing compound and a binder resin. However, the first functional layer 13 functions as a high refractive index layer. Contains refractive index fine particles.

<Non-crosslinkable fluorine-containing compound>
As the non-crosslinkable fluorine-containing compound, the same compounds as the non-crosslinkable fluorine-containing compound described in the first functional layer 12 can be used.

<Binder resin>
The binder resin constituting the first functional layer 13 is not particularly limited, but from the viewpoint of increasing the surface hardness, the thermosetting resin precursor and / or photocurability described in the first functional layer 12 is used. A binder resin made of a cured product of a resin precursor is preferable, and among them, a binder resin that is a cured product of a photocurable resin precursor is more preferable.

<High refractive index fine particles>
Examples of the high refractive index fine particles include metal oxide fine particles. Specific examples of the metal oxide fine particles include titanium oxide (TiO ₂ , refractive index: 2.3 to 2.7), niobium oxide (Nb ₂ O ₅ , refractive index: 2.33), and zirconium oxide. (ZrO ₂ , refractive index: 2.10), antimony oxide (Sb ₂ O ₅ , refractive index: 2.04), tin oxide (SnO ₂ , refractive index: 2.00), tin-doped indium oxide (ITO, refractive index) : 1.95 to 2.00), cerium oxide (CeO _2, refractive index: 1.95), aluminum-doped zinc oxide (AZO, refractive index: 1.90 to 2.00), gallium-doped zinc oxide (GZO, Refractive index: 1.90 to 2.00), zinc antimonate (ZnSb ₂ O ₆ , refractive index: 1.90 to 2.00), zinc oxide (ZnO, refractive index: 1.90), yttrium oxide (Y ₂ O _3, the refractive index: 1 87), antimony-doped tin oxide (ATO, refractive index: 1.75 to 1.85), phosphorus-doped tin oxide (PTO, refractive index: 1.75 to 1.85), and the like. Among these, zirconium oxide is preferable from the viewpoint of refractive index.

  The first functional layer 13 can be formed by a method similar to the method for forming the first functional layer 12, for example. Specifically, first, the first functional layer composition containing at least the high refractive index fine particles, the curable resin precursor, the non-crosslinkable fluorine-containing compound, and the solvent is applied to the surface of the first functional layer 12. .

<Solvent>
As the solvent used for the first functional layer composition, the same solvents as those described for the first functional layer 12 can be used.

  Next, the film-shaped first functional layer composition is conveyed to a heated zone for drying, and the first functional layer composition is dried by various known methods to evaporate the solvent. . Then, the composition for the first functional layer is polymerized (crosslinked) by irradiating the film-form first functional layer composition with light such as ultraviolet rays and / or applying heat to polymerize (crosslink) the first functional layer composition. The product can be cured to form the first functional layer 13.

<< second functional layer >>
The second functional layer is a layer having at least scratch resistance and antifouling property. The second functional layer 14 of the stacked body 10 according to the present embodiment also functions as a low refractive index layer having a lower refractive index than the first functional layers 12 and 13. Specifically, the refractive index of the second functional layer 14 may be 1.20 or more and 1.50 or less. The upper limit of the refractive index of the second functional layer 14 may be 1.49 or less and may be 1.32 or less. The refractive index of the second functional layer 14 can be measured by the same method as the refractive index of the first functional layer 12. The refractive index difference between the second functional layer 14 and the first functional layer 13 may be 0.10 or more and 0.25 or less.

  The surface 14A of the second functional layer 14 forms the surface 10A of the stacked body 10. “The surface of the laminate” means a surface opposite to the surface on the transparent substrate side of the laminate, and “the surface of the second functional layer” means the first function of the second functional layer. It means the surface opposite to the layer side surface.

  The film thickness of the second functional layer 14 is preferably 120 nm or less. The lower limit of the film thickness of the second functional layer 14 is preferably 70 nm or more, and more preferably 75 nm or more. The upper limit of the film thickness of the second functional layer 14 is preferably 110 nm or less, and more preferably 100 nm or less.

  The second functional layer 14 is a layer made of a cured product of the second functional layer composition applied on the first functional layer 13. The second functional layer composition includes fine particles, a crosslinkable silicon-containing compound, a crosslinkable fluorine-containing compound, and a curable resin precursor. Furthermore, a solvent can be appropriately included in the second functional layer composition as long as the effects of the present invention are not impaired. The 2nd functional layer 14 can be formed by apply | coating the composition for 2nd functional layers on the 1st functional layer 12, drying, and making it harden | cure after that. Specifically, first, the second functional layer composition is applied on the first functional layer 13. Subsequently, in order to dry the coating-like 2nd composition for functional layers, it conveys to the zone heated, and the 2nd composition for functional layers is dried by various well-known methods, and a solvent is evaporated. Thereafter, the second functional layer is formed by irradiating the film-like second functional layer composition with light such as ultraviolet rays and / or applying heat to cure (polymerize, crosslink) the curable resin precursor. The second functional layer 14 can be formed by curing the composition for use.

  The crosslinkable silicon-containing compound and the crosslinkable fluorine-containing compound constituting the second functional layer 14 are present at least on the surface 14A of the second functional layer 14. Whether or not the crosslinkable silicon-containing compound and the crosslinkable fluorine-containing compound are present on the surface of the second functional layer can be confirmed by an X-ray photoelectron spectrometer (XPS). The crosslinkable silicon-containing compound and the crosslinkable fluorine-containing compound may be present inside the second functional layer in addition to the surface 14A of the second functional layer 14.

<Fine particles>
The fine particles are not particularly limited, but hollow silica fine particles are preferable, and among the hollow silica fine particles, hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less are preferable. The average primary particle size of the hollow silica fine particles is a value obtained using an image processing software from an image of a cross-sectional electron microscope (a transmission type such as TEM or STEM and preferably having a magnification of 50,000 times or more). The lower limit of the average primary particle size of the hollow silica fine particles may be 68 nm or more, or 70 nm or more. The upper limit of the average primary particle size of the hollow silica fine particles may be 82 nm or less, or 80 nm or less. The hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less are preferred because, when the average primary particle size of the hollow silica fine particles is within this range, more excellent slipperiness can be achieved when low reflectance is realized. In addition, when the void ratio of the hollow silica fine particles is not so large and a desired hardness is obtained, and the film thickness of the second functional layer is about 100 nm, the hollow silica fine particles are obtained. Since there is no possibility that part of the fine particles protrude from the low refractive index layer, there is no possibility that the second low refractive index layer becomes cloudy, and in the steel wool resistance test, the hollow where steel wool protrudes from the low refractive index layer. This is because there is no risk of being caught by silica fine particles and causing scratches.

  The hollow silica fine particles preferably have a photopolymerizable functional group on the surface. Such silica fine particles having a photopolymerizable functional group on the surface can be prepared by surface-treating the silica fine particles with a silane coupling agent or the like. As a method of treating the surface of the silica fine particles with a silane coupling agent, a dry method in which the silane coupling agent is sprayed on the silica fine particles, or a wet method in which the silica fine particles are dispersed in a solvent and then reacted by adding the silane coupling agent. Etc.

<Crosslinkable silicon-containing compound>
The crosslinkable silicon-containing compound is for improving slip resistance and improving scratch resistance. The crosslinkable silicon-containing compound has the photopolymerizable functional group described above as a crosslinkable group. By using such a crosslinkable silicon-containing compound, the crosslinkable silicon-containing compound and the curable resin precursor constituting the binder resin are cross-linked at the time of curing the second functional layer composition, and the binder resin and the crosslinkable resin are cross-linked. A crosslinkable silicon-containing compound is obtained. Therefore, in the state of the second functional layer, the crosslinkable silicon-containing compound is crosslinked with the binder resin.

  The crosslinkable silicon-containing compound may contain fluorine. Examples of commercially available crosslinkable silicon-containing compounds include X22-164E manufactured by Shin-Etsu Chemical Co., Ltd. and RS-55 manufactured by DIC. X22-164E is a crosslinkable silicon-containing compound containing no fluorine, and RS-55 is a crosslinkable silicon-containing compound containing fluorine.

  Among the crosslinkable silicon-containing compounds, crosslinkable silicon-containing compounds having a weight average molecular weight of 2,000 to 30,000 are preferable. By using a crosslinkable silicon-containing compound having a weight average molecular weight of 2,000 to 30,000, the lift-up effect described later can be reliably obtained.

  The blending ratio of the total amount of the hollow silica fine particles and the curable resin precursor constituting the binder resin and the crosslinkable silicon-containing compound is preferably 95: 5 to 85:15 on a weight basis. This range is preferred because, when the ratio of the crosslinkable silicon-containing compound is within the above range, the slipping property is further improved, so that the steel wool resistance is further improved and there is no possibility of causing coating unevenness. Because.

<Crosslinkable fluorine-containing compound>
The crosslinkable fluorine-containing compound is for improving the antifouling property. The crosslinkable fluorine-containing compound has the photopolymerizable functional group described above as a crosslinkable group. By using such a crosslinkable fluorine-containing compound, the crosslinkable fluorine-containing compound and the curable resin precursor constituting the binder resin are crosslinked at the time of curing of the second functional layer composition, and the binder resin and the crosslinkable resin are crosslinked. A crosslinkable fluorine-containing compound is obtained. Therefore, in the state of the second functional layer, the crosslinkable fluorine-containing compound is crosslinked with the binder resin.

  The crosslinkable fluorine-containing compound may contain silicon. However, when the crosslinkable silicon-containing compound contains fluorine and the crosslinkable fluorine-containing compound contains silicon, the crosslinkable fluorine-containing compound has a higher proportion of fluorine atoms to silicon atoms than the crosslinkable silicon-containing compound (F / Si ) Tend to be high.

  Among the crosslinkable fluorine-containing compounds, a crosslinkable fluorine-containing compound having a weight average molecular weight of 2,000 to 30,000 is preferable. By using a crosslinkable fluorine-containing compound having a weight average molecular weight of 2,000 to 30,000, the lift-up effect described later can be reliably obtained.

  Commercially available products of the crosslinkable fluorine-containing compound include, for example, OPTOOL DAC manufactured by Daikin, LINC-3A-MI20 (triacryloylheptadecafluorononenyl pentaerythritol) and LINC-102A (1,2- LINC series such as diacryloxymethyl perfluorocyclohexane), Fluorolink series manufactured by Solvay Solexis, RS-71 manufactured by DIC, and the like.

  The blending ratio (by weight) of the total amount of the hollow silica fine particles and the curable resin precursor constituting the binder resin and the fluorine-containing compound is preferably 95: 5 to 85:15. The reason why this range is preferred is that when the ratio of the crosslinkable fluorine-containing compound is within the above range, the antifouling property is further improved, and there is no possibility of causing a decrease in scratch resistance and uneven coating. .

<Curable resin precursor>
Although it does not specifically limit as a curable resin precursor used as the binder resin of the 2nd functional layer 14, A thermosetting resin precursor and / or a photocurable resin precursor are preferable, and a photocurable resin precursor is especially preferable. More preferred.

  Examples of the thermosetting resin precursor include precursors such as acrylic resin, urethane resin, phenol resin, urea melamine resin, epoxy resin, unsaturated polyester resin, and silicone resin. When curing the thermosetting resin precursor, a curing agent may be used.

  Although it does not specifically limit as a photocurable resin precursor, A photopolymerizable monomer, an oligomer, and a polymer can be used. Examples of the monofunctional photopolymerizable monomer include ethyl (meth) acrylate, ethylhexyl (meth) acrylate, styrene, methylstyrene, and N-vinylpyrrolidone. Examples of the bifunctional or higher photopolymerizable monomer include polymethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and pentaerythritol tris. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) Examples include acrylates, compounds obtained by modifying these compounds with ethylene oxide, polyethylene oxide, and the like.

  Moreover, you may use a curable fluororesin precursor as a curable resin precursor. By using a curable fluororesin precursor as the curable resin precursor, it is possible to further reduce the refractive index. The “curable fluororesin precursor” means a fluororesin precursor that has a curability and becomes a fluororesin by curing. The curable fluororesin precursor preferably has a lower functional group equivalent than the crosslinkable fluorine-containing compound as the surface modifier.

  In addition, it is considered that the curable fluororesin precursor preferably contains more fluorine atoms in the main chain than in the side chain, from the viewpoint of suppressing a decrease in hardness. On the other hand, it is considered that the crosslinkable fluorine-containing compound as the surface modifier is likely to bleed out and preferably contains more fluorine atoms in the side chain than in the main chain in order to improve antifouling properties.

式中、Ｒｆ_１は、少なくとも炭素原子およびフッ素原子を含み、酸素原子および／または水素原子を含んでいてもよい、鎖状または環状の（ｍ＋ｎ）価のフッ化炭化水素基を表す。Ｒｆ_２は、それぞれ独立して、少なくとも炭素原子およびフッ素原子を含み、酸素原子および／または水素原子を含んでもよい、鎖状または環状の２価のフッ化炭化水素基を表す。Ｑは重合性基を表す。ｍおよびｎは、それぞれ独立して、０以上の整数（ただし、ｍ＋ｎ≧２）を表す。 As a curable fluororesin precursor, the curable fluororesin precursor of following formula (1) is mentioned, for example.

In the formula, Rf ₁ represents a chain or cyclic (m + n) -valent fluorinated hydrocarbon group containing at least a carbon atom and a fluorine atom, and optionally containing an oxygen atom and / or a hydrogen atom. Rf ₂ independently represents a chain or cyclic divalent fluorinated hydrocarbon group that contains at least a carbon atom and a fluorine atom, and may contain an oxygen atom and / or a hydrogen atom. Q represents a polymerizable group. m and n each independently represent an integer of 0 or more (provided that m + n ≧ 2).

The number of hydrogen atoms / number of fluorine atoms in Rf ₁ is preferably 1/4 or less, more preferably 1/9 or less, and particularly preferably substantially free of hydrogen atoms. Specific examples of Rf ₁ are shown in the following formulas (2) to (11), but Rf ₁ is not limited thereto.

Rf ₂ is preferably a linear or branched perfluoroalkylene group having 1 to 12 carbon atoms. Examples of the perfluoroalkylene group include a difluoromethylene group (—CF ₂ —), a perfluoromethylmethylene group (—CF (CF ₃ ) —), and a perfluoroethylmethylene group (—CF (CF ₂ CF ₃ ) —). Perfluoroethylene group (—CF ₂ CF ₂ —), perfluoropropylene group (—CF ₂ CF ₂ CF ₂ —) and the like. Among these, a perfluoroethylene group is preferable.

Q is preferably a radical, a cation, or a polycondensable group, and —COC (R ₀ ) ═CH ₂ , an allyl group, an epoxyalkylene group, — (CH ₂ ) _x Si (OW) ₃ , — More preferably, it is (CH ₂ ) _y NCO or — (CH ₂ ) _z CN. Here, R ₀ represents a hydrogen atom, a halogen atom or an alkyl group which may have a substituent, W represents an alkoxy group or a hydroxyl group, x, y and z each represents an integer of 1 or more, 3 The number W may be different from each other. The substituent for the alkyl group in R ₀ may be any substituent, but is preferably a halogen atom. When n is 2 or more, the plurality of Q may be the same or different.

  In the curable fluororesin precursor represented by the above formula (1), the fluorine content is preferably 35% by mass or more and 35% by mass or more and 70% by mass or less of the molecular weight of the fluorine-containing compound. More preferably, it is 37 mass% or more and 60 mass% or less.

式中、Ｒｆ_１、Ｒｆ_２、ｍおよびｎはそれぞれ上記式（１）と同じ意味であり、Ｒは水素原子、フッ素原子、メチル基またはトリフルオロメチル基を表し、これらの中でもＲは水素原子であることが好ましい。 The curable fluororesin precursor represented by the above formula (1) is preferably a compound represented by the following formula (1A).

In the formula, Rf ₁ , Rf ₂ , m and n each have the same meaning as in the above formula (1), R represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group, and among these, R is a hydrogen atom It is preferable that

  Although the specific example of the curable fluororesin precursor shown by the said Formula (1) is shown below, it is not limited to this.

  Among these, from the viewpoint of obtaining a low refractive index and good steel wool resistance, the compound represented by the above formula (25) is preferable.

In addition to the above formula (1), the curable fluororesin precursor is a curable fluororesin precursor represented by the following formulas (33) to (36) or a group represented by the following formula (37). Examples thereof include a curable fluororesin precursor having at least one selected segment.

式（３７）中、ｘ、ｙはＦまたは（ＣＦ_２）_０〜１０ＣＦ_３を表す。

Wherein (37), x, y is F or _{(CF 2) 0~10} CF _3.

<Solvent>
As a solvent used for the composition for 2nd functional layers, the solvent similar to the solvent used for the composition for 1st functional layers can be used.

  The first functional layers 12 and 13 include a non-crosslinkable fluorine-containing compound, and the second functional layer composition includes a crosslinkable silicon-containing compound, a crosslinkable fluorine-containing compound, a curable resin precursor, and a solvent. Therefore, scratch resistance and antifouling properties can be significantly improved. The reason for this is not clear, but is presumed as follows. When a coating film of the second functional layer composition is formed on the first functional layer in a state where the non-crosslinkable fluorine-containing compound is present in the first functional layer, for example, the second functional layer composition When the solvent of the substance penetrates into the first functional layer, the non-crosslinkable fluorine-containing compound in the first functional layer is eluted and enters the coating film of the second functional layer composition. Then, the non-crosslinkable fluorine-containing compound that has entered the coating film of the second functional layer composition causes the crosslinkable silicon-containing compound and the crosslinkable fluorine-containing compound in the coating film to be the second functional layer composition. It is pushed up to the vicinity of the surface of the coating film (lift-up effect). Thereby, even if hollow silica fine particles are present, the crosslinkable silicon-containing compound and the crosslinkable fluorine-containing compound are deposited on the surface of the coating film, so that excellent scratch resistance and antifouling properties are obtained. be able to. In addition, it is also conceivable to add a non-crosslinkable fluorine-containing compound to the second functional layer composition. However, when a non-crosslinkable fluorine-containing compound is added to the second functional layer composition, the non-crosslinkable fluorine-containing compound is added. Is deposited on the surface of the second functional layer, and the scratch resistance and antifouling properties are lowered, so that such a method cannot be adopted. In addition, it is conceivable to use a crosslinkable fluorine-containing compound in place of the non-crosslinkable fluorine-containing compound contained in the first functional layer, but in the case of the crosslinkable fluorine-containing compound, the first functional layer is cured at the time of curing. Since it crosslinks with the binder resin in the functional layer, it is difficult to elute from the first functional layer, and as a result, a lift-up effect cannot be expected. Furthermore, it is conceivable to use a non-crosslinkable fluorine-free silicon-containing compound instead of the non-crosslinkable fluorine-containing compound contained in the first functional layer. However, although the reason is not clear, the crosslinkable silicon-containing compound and the crosslinkable fluorine-containing compound are unlikely to precipitate on the surface of the second functional layer.

  When a large amount of a crosslinkable silicon-containing compound and a crosslinkable fluorine-containing compound are added to the second functional layer, the total haze value of the laminate is increased and a cloudiness may occur. On the other hand, according to this embodiment, since the scratch resistance and antifouling property are improved by pushing up the crosslinkable silicon-containing compound and the crosslinkable fluorine-containing compound with the non-crosslinkable fluorine-containing compound, a large amount of the crosslinkable silicon-containing compound is contained. No compound or crosslinkable fluorine-containing compound is required. For this reason, the total haze value of the laminated body 10 can be 0.5% or less, and as a result, the cloudiness is less likely to occur.

According to the present embodiment, hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less are used as the hollow silica fine particles of the second functional layer 14, so that the low reflectance of the laminate 10 can be realized. As well as excellent scratch resistance and antifouling properties. That is, when the hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less are used as the hollow silica fine particles of the second functional layer, compared to the case of using the hollow silica fine particles having an average primary particle size of 60 nm or less, The reflectance can be lowered with a small amount. On the other hand, the amount of hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less in the second functional layer is smaller than that when hollow silica fine particles having an average primary particle size of 60 nm or less are used. When the functional layer is formed, the crosslinkable silicon-containing compound tends to precipitate (bleed out) on the surface of the second functional layer. For this reason, more crosslinkable silicon-containing compounds can be present on the surface of the second functional layer. Further, since the hollow silica fine particles have voids, the strength of the hollow silica fine particles is not so high, and when a large amount of hollow silica fine particles are present in the second functional layer, the binder resin in the second functional layer is present. The amount of will decrease. Therefore, when a large amount of hollow silica fine particles are present in the second functional layer, the hardness of the second functional layer is lowered. In contrast, when hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less are used, the hollow silica in the second functional layer is compared with the case where hollow silica fine particles having an average primary particle size of 60 nm or less are used. The amount of fine particles can be reduced, and the amount of the binder resin in the second functional layer can be increased. For this reason, the hardness of the second functional layer can be increased. This confirms that the surface of the second functional layer is scratched when a steel wool test is performed in which a # 0000 steel wool is applied to the surface of the second functional layer and the load is rubbed 10 times. The maximum load that is not performed can be 200 g / cm ² or more. As described above, the hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less in the second functional layer are used in a smaller amount than when hollow silica fine particles having an average primary particle size of 60 nm or less are used. Therefore, the fluorine-containing compound is likely to be deposited on the surface of the second functional layer when the second functional layer is formed. For this reason, since more fluorine-containing compounds can be present on the surface of the low refractive index layer, the antifouling property can be improved. As a result, low reflectance can be realized, and further excellent scratch resistance and antifouling properties can be obtained.

  According to the present embodiment, since the second functional layer 14 includes hollow silica fine particles having an average primary particle size of 65 nm or more and 85 nm or less, the surface of the low refractive index layer has irregularities sufficiently smaller than the wavelength of visible light. Can be formed. Thereby, the same antireflection effect as a laminated body having a moth-eye structure can be expected.

<<< Polarizing plate >>>
The laminate 10 can be used by being incorporated into a polarizing plate, for example. FIG. 2 is a schematic configuration diagram of a polarizing plate incorporating the laminate according to the present embodiment. As shown in FIG. 2, the polarizing plate 20 includes a laminate 10, a polarizing element 21, and a protective film 22. The polarizing element 21 is formed on the surface of the transparent substrate 11 opposite to the surface on which the first functional layer 12 is formed. The protective film 22 is provided on the surface opposite to the surface on which the laminated body 10 of the polarizing elements 21 is provided. The protective film 22 may be a retardation film.

  Examples of the polarizing element 21 include a polyvinyl alcohol film, a polyvinyl formal film, a polyvinyl acetal film, an ethylene-vinyl acetate copolymer saponified film, which are dyed and stretched with iodine or the like. When the laminate 10 and the polarizing element 21 are laminated, it is preferable to saponify the light-transmitting substrate 11 in advance. By performing the saponification treatment, the adhesiveness is improved and an antistatic effect can be obtained.

<<< LCD panel >>>
The laminate 10 and the polarizing plate 20 can be used by being incorporated in a display panel. FIG. 3 is a schematic configuration diagram of a liquid crystal panel which is an example of a display panel incorporating the laminate according to the present embodiment.

  The liquid crystal panel 30 shown in FIG. 3 has a protective film 31, such as a triacetyl cellulose film (TAC film), a polarizing element 32, a retardation film 33, a transparent film, from the light source side (backlight unit side) to the viewer side. The adhesive layer 34, the display element 35, the transparent adhesive layer 36, the retardation film 37, the polarizing element 21, and the laminate 10 are sequentially laminated. The display panel 20 only needs to include the display element 25 and the laminated body 29 arranged on the viewer side with respect to the display element 25, and may not include the protective film 21 or the like.

  The display element 25 is a liquid crystal display element. However, when the display panel is not a liquid crystal panel, for example, when the display panel is an organic EL panel, the display element is an organic EL display element. In the liquid crystal display element, a liquid crystal layer, an alignment film, an electrode layer, a color filter, and the like are disposed between two glass substrates.

<<< Image display device >>>
The laminate 10, the polarizing plate 20, and the liquid crystal panel 30 can be used by being incorporated in an image display device. Examples of the image display device include a liquid crystal display (LCD), a cathode ray tube display device (CRT), a plasma display (PDP), an electroluminescence display (ELD), a field emission display (FED), a touch panel, a tablet PC, and electronic paper. Can be mentioned. FIG. 4 is a schematic configuration diagram of a liquid crystal display which is an example of an image display device incorporating the laminate according to the present embodiment.

  The image display device 40 shown in FIG. 4 includes a backlight unit 41 and a liquid crystal panel 30 including the laminate 10 that is disposed closer to the viewer than the backlight unit 41. A known backlight unit can be used as the backlight unit 41.

  In order to describe the present invention in detail, examples will be described below, but the present invention is not limited to these descriptions. In addition, the following “100% solid content conversion value” is a value when the solid content in the solvent diluted product is 100%.

<Preparation of composition for hard coat layer>
First, each component was mix | blended so that it might become the composition shown below, and the composition for hard-coat layers was obtained.
(Composition 1 for hard coat layer)
Dipentaerythritol hexaacrylate (product name “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass Polymerization initiator (product name “Irgacure 184” manufactured by BASF Japan Ltd.): 4 parts by mass Non-crosslinkable fluorine Containing compound (product name “F568”, manufactured by DIC Corporation): 0.1 part by mass (100% solid content conversion value)
・ Methyl isobutyl ketone (MIBK): 120 parts by mass

(Composition 2 for hard coat layer)
Dipentaerythritol hexaacrylate (product name “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass Polymerization initiator (product name “Irgacure 184” manufactured by BASF Japan Ltd.): 4 parts by mass Non-crosslinkable fluorine Containing compound (product name “F568”, manufactured by DIC Corporation): 0.3 part by mass (100% solid content conversion value)
・ Methyl isobutyl ketone (MIBK): 120 parts by mass

(Composition 3 for hard coat layer)
Dipentaerythritol hexaacrylate (product name “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass Polymerization initiator (product name “Irgacure 184” manufactured by BASF Japan Ltd.): 4 parts by mass Non-crosslinkable fluorine Containing compound (product name “F568”, manufactured by DIC Corporation): 0.5 part by mass (100% solid content conversion value)
・ Methyl isobutyl ketone (MIBK): 120 parts by mass

(Composition 4 for hard coat layer)
Dipentaerythritol hexaacrylate (product name “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass Polymerization initiator (product name “Irgacure 184” manufactured by BASF Japan Ltd.): 4 parts by mass Non-crosslinkable fluorine Containing compound (product name “F477”, manufactured by DIC Corporation): 0.1 part by mass (100% solid content conversion value)
・ Methyl isobutyl ketone (MIBK): 120 parts by mass

(Composition 5 for hard coat layer)
Dipentaerythritol hexaacrylate (product name “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass Polymerization initiator (product name “Irgacure 184” manufactured by BASF Japan Ltd.): 4 parts by mass Non-crosslinkable fluorine Containing compound (product name “F556”, manufactured by DIC Corporation): 0.1 part by massMethyl isobutyl ketone (MIBK): 120 parts by mass

(Composition 6 for hard coat layer)
Dipentaerythritol hexaacrylate (product name “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass Polymerization initiator (product name “Irgacure 184” manufactured by BASF Japan Ltd.): 4 parts by mass Non-crosslinkable fluorine Containing compound (product name “F558”, manufactured by DIC Corporation): 0.1 part by massMethyl isobutyl ketone (MIBK): 120 parts by mass

(Composition 7 for hard coat layer)
-Dipentaerythritol hexaacrylate (product name "KAYARAD DPHA", manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass-Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan): 4 parts by mass-methyl isobutyl ketone ( MIBK): 120 parts by mass

(Composition 8 for hard coat layer)
Dipentaerythritol hexaacrylate (product name “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass Polymerization initiator (product name “Irgacure 184” manufactured by BASF Japan Ltd.): 4 parts by mass Non-crosslinkable fluorine Non-containing silicon-containing compound (product name “KP112”, manufactured by Shin-Etsu Chemical Co., Ltd.): 0.1 parts by mass / methyl isobutyl ketone (MIBK): 120 parts by mass

(Composition 9 for hard coat layer)
Dipentaerythritol hexaacrylate (product name “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass Polymerization initiator (product name “Irgacure 184” manufactured by BASF Japan Ltd.): 4 parts by mass Non-crosslinkable fluorine Non-containing silicon-containing compound (product name “KP341”, manufactured by Shin-Etsu Chemical Co., Ltd.): 0.1 parts by mass / methyl isobutyl ketone (MIBK): 120 parts by mass

<Preparation of composition for high refractive index layer>
Each component was mix | blended so that it might become a composition shown below, and the composition for high refractive index layers was obtained.
(Composition 1 for high refractive index layer)
Antimony pentoxide fine particles (average primary particle size 20 nm): 400 parts by mass (converted to a solid content of 100%)
Dipentaerythritol hexaacrylate (product name “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass Polymerization initiator (product name “Irgacure 184” manufactured by BASF Japan Ltd.): 4 parts by mass Non-crosslinkable fluorine Containing compound (product name “F568”, manufactured by DIC Corporation): 15 parts by mass (100% solid content conversion)
・ Methyl isobutyl ketone (MIBK): 16000 parts by mass

(Composition 2 for high refractive index layer)
Antimony pentoxide fine particles (average primary particle size 20 nm): 400 parts by mass (converted to a solid content of 100%)
Dipentaerythritol hexaacrylate (product name “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass Polymerization initiator (product name “Irgacure 184” manufactured by BASF Japan Ltd.): 4 parts by mass Non-crosslinkable fluorine Containing compound (product name “F477”, manufactured by DIC Corporation): 15 parts by mass (converted to a solid content of 100%)
・ Methyl isobutyl ketone (MIBK): 16000 parts by mass

(Composition 3 for high refractive index layer)
Antimony pentoxide fine particles (average primary particle size 20 nm): 400 parts by mass (converted to a solid content of 100%)
Dipentaerythritol hexaacrylate (product name “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass Polymerization initiator (product name “Irgacure 184” manufactured by BASF Japan Ltd.): 4 parts by mass Non-crosslinkable fluorine Containing compound (product name “F556”, manufactured by DIC Corporation): 15 parts by massMethyl isobutyl ketone (MIBK): 16000 parts by mass

(Composition 4 for high refractive index layer)
Antimony pentoxide fine particles (average primary particle size 20 nm): 400 parts by mass (converted to a solid content of 100%)
Dipentaerythritol hexaacrylate (product name “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass Polymerization initiator (product name “Irgacure 184” manufactured by BASF Japan Ltd.): 4 parts by mass Non-crosslinkable fluorine Containing compound (product name “F558”, manufactured by DIC Corporation): 15 parts by massMethyl isobutyl ketone (MIBK): 16000 parts by mass

(Composition 5 for high refractive index layer)
Antimony pentoxide fine particles (average primary particle size 20 nm): 400 parts by mass (converted to a solid content of 100%)
-Dipentaerythritol hexaacrylate (product name "KAYARAD DPHA", manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass-Polymerization initiator (product name "Irgacure 184", manufactured by BASF Japan): 4 parts by mass-methyl isobutyl ketone ( MIBK): 16000 parts by mass

(Composition 6 for high refractive index layer)
Antimony pentoxide fine particles (average primary particle size 20 nm): 400 parts by mass (converted to a solid content of 100%)
Dipentaerythritol hexaacrylate (product name “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass Polymerization initiator (product name “Irgacure 184” manufactured by BASF Japan Ltd.): 4 parts by mass Non-crosslinkable fluorine Non-containing silicon-containing compound (product name “KP112”, manufactured by Shin-Etsu Chemical Co., Ltd.): 15 parts by mass / methyl isobutyl ketone (MIBK): 16000 parts by mass

(Composition 7 for high refractive index layer)
Antimony pentoxide fine particles (average primary particle size 20 nm): 400 parts by mass (converted to a solid content of 100%)
Dipentaerythritol hexaacrylate (product name “KAYARAD DPHA” manufactured by Nippon Kayaku Co., Ltd.): 100 parts by mass Polymerization initiator (product name “Irgacure 184” manufactured by BASF Japan Ltd.): 4 parts by mass Non-crosslinkable fluorine Non-containing silicon-containing compound (product name “KP341”, manufactured by Shin-Etsu Chemical Co., Ltd.): 15 parts by mass / methyl isobutyl ketone (MIBK): 16000 parts by mass

<Preparation of composition for low refractive index layer>
Each component was mix | blended so that it might become the composition shown below, and the composition for low refractive index layers was obtained.
(Composition 1 for low refractive index layer)
・ Hollow silica fine particles (average primary particle size 75 nm): 150 parts by mass (100% solid content conversion value)
Pentaerythritol triacrylate (product name “KAYARAD PET-30”, manufactured by Nippon Kayaku Co., Ltd.): 20 parts by mass • Curable fluorine-containing polymer (product name “OPSTAR JN35”, manufactured by JSR): 80 parts by mass (solid content) (100% conversion value)
-Polymerization initiator (product name "Irgacure 127", manufactured by BASF Japan): 4 parts by mass-Crosslinkable silicon-containing compound (product name "X22-164E", manufactured by Shin-Etsu Chemical Co., Ltd.): 15 parts by mass-Contains crosslinkable fluorine Compound (Product name “OPTOOL DAC”, manufactured by Daikin): 25 parts by mass (100% solid content conversion value)
・ Methyl isobutyl ketone (MIBK): 8000 parts by mass

(Composition 2 for low refractive index layer)
・ Hollow silica fine particles (average primary particle size 75 nm): 150 parts by mass (100% solid content conversion value)
Pentaerythritol triacrylate (product name “KAYARAD PET-30”, manufactured by Nippon Kayaku Co., Ltd.): 20 parts by mass • Curable fluorine-containing polymer (product name “OPSTAR JN35”, manufactured by JSR): 80 parts by mass (solid content) (100% conversion value)
-Polymerization initiator (product name "Irgacure 127", manufactured by BASF Japan): 4 parts by mass-Crosslinkable silicon-containing compound (product name "X22-164E", manufactured by Shin-Etsu Chemical Co., Ltd.): 30 parts by mass-Contains crosslinkable fluorine Compound (Product name “OPTOOL DAC”, manufactured by Daikin): 50 parts by mass (100% solid content conversion value)
・ Methyl isobutyl ketone (MIBK): 8000 parts by mass

<Example 1>
A triacetyl cellulose base material (product name “KC4UAW”, manufactured by Konica Minolta Co., Ltd.) having a thickness of 40 μm as a transparent base material was prepared, and the hard coat composition 1 was applied to one side of the triacetyl cellulose base material, A coating film was formed. Next, 70 ° C. dry air was passed through the formed coating film at a flow rate of 0.2 m / s for 15 seconds, and then 70 ° C. dry air was passed through for 30 seconds at a flow rate of 10 m / s. By evaporating the solvent in the coating film and irradiating the ultraviolet light with an integrated light amount of 100 mJ / cm ² under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) to cure the coating film, the refractive index is increased. A hard coat layer having a thickness of 1.52 and a thickness of 8 μm was formed. Next, the composition 1 for a high refractive index layer was applied on the hard coat layer to form a coating film. And after drying the formed coating film for 1 minute at 40 degreeC, under a nitrogen atmosphere (oxygen concentration 200 ppm or less), it hardens | cures by irradiating with an ultraviolet-ray with the integrated light quantity of 100 mJ / cm < ² >, and refractive index is 1. .63 and a high refractive index layer having a thickness of 150 nm were formed. Subsequently, the composition 1 for low refractive index layers was apply | coated on the high refractive index layer, and the coating film was formed. And after drying the formed coating film for 1 minute at 40 degreeC, under a nitrogen atmosphere (oxygen concentration 200 ppm or less), it hardens | cures by irradiating with an ultraviolet-ray with the integrated light quantity of 100 mJ / cm < ² >, and refractive index is 1. A low refractive index layer having a thickness of .29 and a thickness of 100 nm was formed. This produced the laminated body which concerns on Example 1. FIG.

<Example 2>
In Example 2, a laminate was produced in the same manner as in Example 1 except that the hard coat layer composition 2 was used instead of the hard coat layer composition 1 to form a hard coat layer.

<Example 3>
In Example 3, a laminate was produced in the same manner as in Example 1 except that the hard coat layer composition 3 was used instead of the hard coat layer composition 1 to form a hard coat layer.

<Example 4>
In Example 4, a hard coat layer is formed using the hard coat layer composition 4 instead of the hard coat layer composition 1, and the high refractive index layer composition 1 is used instead of the high refractive index layer composition 1. A laminate was produced in the same manner as in Example 1 except that the high refractive index layer was formed using the composition 2.

<Example 5>
In Example 5, a hard coat layer is formed using the hard coat layer composition 5 instead of the hard coat layer composition 1, and the high refractive index layer composition 1 is used instead of the high refractive index layer composition 1. A laminate was produced in the same manner as in Example 1 except that the high refractive index layer was formed using the composition 3.

<Example 6>
In Example 6, a hard coat layer was formed using the hard coat layer composition 6 instead of the hard coat layer composition 1, and the high refractive index layer composition 1 was replaced with the high refractive index layer composition 1. A laminate was produced in the same manner as in Example 1 except that the high refractive index layer was formed using the composition 4.

<Example 7>
In Example 7, a laminate was produced in the same manner as in Example 1, except that the hard coat layer composition 7 was used instead of the hard coat layer composition 1 to form a hard coat layer.

<Example 8>
In Example 8, a laminate was produced in the same manner as in Example 1 except that the high refractive index layer was formed using the high refractive index layer composition 5 instead of the high refractive index layer composition 1. did.

<Comparative Example 1>
In Comparative Example 1, a hard coat layer was formed using the hard coat layer composition 7 instead of the hard coat layer composition 1, and the high refractive index layer composition 1 was used instead of the high refractive index layer composition 1. A laminate was produced in the same manner as in Example 1 except that the high refractive index layer was formed using the composition 5.

<Comparative Example 2>
In Comparative Example 2, a hard coat layer was formed using the hard coat layer composition 7 instead of the hard coat layer composition 1, and the high refractive index layer composition 1 was replaced with the high refractive index layer composition 1. Example 1 except that the high refractive index layer was formed using the product 5 and the low refractive index layer was formed using the low refractive index layer composition 2 instead of the low refractive index layer composition 1. Similarly, a laminate was produced.

<Comparative Example 3>
In Comparative Example 3, a hard coat layer was formed using the hard coat layer composition 8 instead of the hard coat layer composition 1, and the high refractive index layer composition 1 was used instead of the high refractive index layer composition 1. A laminate was produced in the same manner as in Example 1 except that the high refractive index layer was formed using the composition 6.

<Comparative example 4>
In Comparative Example 4, a hard coat layer was formed using the hard coat layer composition 9 instead of the hard coat layer composition 1, and the high refractive index layer composition 1 was used instead of the high refractive index layer composition 1. A laminate was produced in the same manner as in Example 1 except that the high refractive index layer was formed using the composition 7.

<Comparative Example 5>
In Comparative Example 5, a laminate was produced in the same manner as in Example 1 except that the high refractive index layer was formed using the high refractive index layer composition 6 instead of the high refractive index layer composition 1. did.

<Comparative Example 6>
In Comparative Example 6, a laminate was produced in the same manner as in Example 1 except that the high refractive index layer was formed using the high refractive index layer composition 7 instead of the high refractive index layer composition 1. did.

<Abrasion resistance evaluation>
Steel wool # 0000 (product name “Bonster”, manufactured by Nippon Steel Wool Co., Ltd.) was used as the surface of the low refractive index layer (the surface of the laminate) of the laminates according to Examples and Comparative Examples, and the load was 200 g / cm ^2. Then, after rubbing 10 times at a speed of 100 mm / sec, a black tape is applied to the surface opposite to the surface on which the hard coat layer is formed in each triacetyl cellulose base material, and the presence or absence of scratches is determined for 3 wavelengths. Evaluation was made by visual observation under a fluorescent lamp. The evaluation criteria were as follows.
○: There was no scratch.
Δ: There were several scratches.
X: There were many scratches.

<Anti-fouling evaluation>
Evaluation of antifouling property against fingerprints After each fingerprint was attached to the surface of the low refractive index layer (the surface of the laminate) of the laminates according to Examples and Comparative Examples, the samples were wiped with Bencot M-3 manufactured by Asahi Kasei Corporation. The ease of removal and wiping was visually confirmed. The evaluation criteria were as follows.
A: Fingerprints were easily or relatively easily wiped off.
○: The fingerprint could be wiped off, but it was not easy.
X: The fingerprint could not be wiped off.

<Measurement of reflection Y value>
About the laminated body which concerns on an Example and a comparative example, the reflection Y value was measured using the spectrophotometer (MPC3100, Shimadzu Corporation make). Specifically, light with an incident angle of 5 degrees is irradiated from the surface side of the low refractive index layer in each film, and the reflected light in the specular direction reflected by each film is received, and the wavelength of 380 nm to 780 nm. The reflectance of the range was measured, and then the reflection Y value was calculated by software (for example, software built in the MPC 3100) that was converted as lightness felt by human eyes. The reflection Y value was measured in a state where a black tape (manufactured by Teraoka Seisakusho) was attached to the surface (back surface) opposite to the surface on which the hard coat layer was formed in the triacetyl cellulose base material.

The results are shown in Table 1.

  As shown in Table 1, in Comparative Examples 1 to 6, since the hard coat layer and the high refractive index layer did not contain a non-crosslinkable fluorine-containing compound, the low refractive index layer contains a crosslinkable silicon-containing compound and Even if a crosslinkable fluorine-containing compound was contained, the scratch resistance and antifouling property were poor. On the other hand, in Examples 1 to 8, since the hard coat layer and / or the high refractive index layer contained a non-crosslinkable fluorine-containing compound, the scratch resistance and antifouling property were good. This is because the crosslinkable silicon-containing compound and the crosslinkable fluorine-containing compound are lifted up by the non-crosslinkable fluorine-containing compound during the formation of the low refractive index layer, and the crosslinkable silicon-containing compound and the crosslinkable fluorine-containing compound This is thought to be because there were many.

DESCRIPTION OF SYMBOLS 10 ... Laminated body 10A ... Surface 11 ... Transparent base material 12 ... 1st functional layer 13 ... 1st functional layer 14 ... 2nd functional layer 14A ... Surface 20 ... Polarizing element 21 ... Polarizing element 30 ... Liquid crystal display panel 40 ... Image display device

Claims (5)

And the product layer body,
A polarizing plate comprising a polarizing element formed on a surface opposite to the surface on which the first functional layer is formed in the transparent substrate of the laminate ,
The laminate includes a transparent substrate, a first functional layer, and a second functional layer in this order,
The surface of the second functional layer forms the surface of the laminate,
The first functional layer includes a non-crosslinkable fluorine-containing compound and a binder resin,
The second functional layer is a layer made of a cured product of the second functional layer composition containing at least fine particles, a crosslinkable silicon-containing compound, a crosslinkable fluorine-containing compound, and a curable resin precursor. ,Polarizer. The polarizing plate according to claim 1, wherein a plurality of the first functional layers are present between the transparent base material and the second functional layer and in the thickness direction of the laminate. The polarizing plate according to claim 1, wherein the fine particles are hollow silica fine particles. The polarizing plate according to claim 1, wherein the first functional layer is in contact with the second functional layer. An image display device,
A display element;
An image display apparatus provided with the polarizing plate as described in any one of Claims 1-4 arrange | positioned at the observer side rather than the said display element.

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