TW201712366A - Optical laminate - Google Patents

Abstract

Provided is an optical laminate in which color unevenness resulting from an antireflection film is prevented, the optical laminate being thin and excellent in neutral black reflection hue. The optical laminate includes: a first substrate; a second substrate arranged on one side of the first substrate; an antireflection film arranged between the first substrate and the second substrate; and a resin layer arranged between the first substrate and the second substrate to cover the antireflection film, in which: the antireflection film includes a polarizer and a retardation layer bonded to the polarizer; and the resin layer has a storage modulus of elasticity at 25 DEG C of 1*10<SP>6</SP> Pa or more.

Description

Optical laminate

The present invention relates to an optical laminate.

Various optical films have been used for image display devices typified by liquid crystal display devices and organic EL display devices to improve viewing angle characteristics and reflection characteristics. For example, in an organic EL display device having a highly reflective metal layer, problems such as reflection of external light or reflection of a background are apt to occur. Therefore, a circularly polarizing plate having a λ/4 plate is sometimes used as an antireflection film.

On the other hand, in the above image display device, the occurrence of color unevenness due to the end portion used for many years becomes a problem. It is known to use a method having an optical film having a small photoelastic coefficient to prevent color unevenness caused by an optical film, and a cycloolefin film is often used as an optical film having a small photoelastic coefficient. A cycloolefin film can also be used as the λ/4 plate. However, due to the wavelength dispersion inherent in the material, the cycloolefin film relates to the problem that the neutral black reflection hue cannot be obtained by using the film alone. When attempting to obtain a neutral black reflection hue while using a cycloolefin film, it is necessary to further use an optical film which functions as a λ/2 plate, and thus there is a problem that the productivity of the image display device is lowered and the thickness thereof is increased. .

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-154176

The present invention has been made to solve the above-mentioned problems, and a main object of the present invention is to provide an optical laminate which prevents color unevenness caused by an anti-reflection film which is thin and neutral black reflection Excellent hue.

The optical layered body of the present invention includes: a first substrate; a second substrate disposed on one side of the first substrate; an antireflection film disposed between the first substrate and the second substrate; and a resin layer The first substrate and the second substrate are disposed to cover the anti-reflection film; and the anti-reflection film includes a polarizing element and a phase difference layer adjacent to the polarizing element; and the resin layer is 25 The storage elastic modulus of °C is 1 × 10 ⁶ Pa or more.

In one embodiment, the phase difference layer functions as a λ/4 plate.

In one embodiment, the phase difference layer exhibits an inverse dispersion wavelength characteristic.

In one embodiment, the retardation layer includes a polycarbonate resin film.

In one embodiment, the retardation layer contains a resin having a photoelastic coefficient of 30 × 10 ^-12 Pa or less.

In one embodiment, the angle between the slow phase axis of the retardation layer and the absorption axis of the polarizing element is 35° to 55°.

In one embodiment, the polarizing element and the retardation layer are laminated via an adhesive layer, and the thickness of the adhesive layer is 1 μm or less.

According to the present invention, by providing an anti-reflection film including a polarizing element and a retardation layer next to the polarizing element, and covering the anti-reflection film with a resin layer having a specific storage elastic modulus, a thin shape can be obtained. An optical laminate that prevents uneven color. Further, according to the present invention, the material constituting the phase difference layer of the antireflection film may be selected from a wide range (for example, a material having a relatively large photoelastic coefficient may be used or a reverse dispersion wavelength may be formed). The material of the phase difference layer of the characteristic). Therefore, an optical layered body excellent in neutral black reflection hue while forming a phase difference layer by a single layer can be obtained.

10‧‧‧1st substrate

20‧‧‧Anti-reflective film

21‧‧‧Polarized components

22‧‧‧ phase difference layer

23‧‧‧Adhesive layer

24‧‧‧Protective film

30‧‧‧ resin layer

40‧‧‧2nd substrate

100‧‧‧Optical laminate

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an optical layered body according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the embodiments.

(Definition of terms and symbols)

The definitions of terms and symbols used in this specification are as follows.

(1) Refractive index (nx, ny, nz)

"nx" represents the refractive index of the direction in which the in-plane refractive index is the largest (ie, the direction of the slow axis), and "ny" represents the refractive index of the direction perpendicular to the axis of the late phase (ie, the direction of the phase axis), and "nz" "Represents the refractive index in the thickness direction.

(2) In-plane phase difference (Re)

"Re(λ)" refers to the in-plane phase difference measured by light at a wavelength of λ nm at 23 °C. For example, "Re(550)" refers to the in-plane phase difference measured by light having a wavelength of 550 nm at 23 °C. When the thickness of the layer (film) is represented by d (nm), Re (λ) is determined according to the equation: Re (λ) = (nx - ny) × d.

(3) Phase difference in the thickness direction (Rth)

"Rth(λ)" means a phase difference in the thickness direction measured by light having a wavelength of λ nm at 23 °C. For example, "Rth(550)" means a phase difference in the thickness direction measured by light having a wavelength of 550 nm at 23 °C. When the thickness of the layer (film) is represented by d (nm), Rth (λ) is determined according to the equation: Rth (λ) = (nx - nz) × d.

(4) Nz coefficient

The Nz coefficient is determined according to the equation Nz = Rth / Re.

(5) Birefringence (Δn _xy )

The birefringence Δn _{xy is} determined according to the equation: Δn _xy = nx-ny.

A. The overall composition of the optical laminate

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic cross-sectional view showing an optical layered body according to an embodiment of the present invention. The optical layered body 100 of the present embodiment includes a first substrate 10, a second substrate 40 disposed on one side of the first substrate 10, and an anti-reflection film 20 disposed between the first substrate 10 and the second substrate 40. And a resin layer 30 formed between the first substrate 10 and the second substrate 40 to cover and seal the anti-reflection film 20. The anti-reflection film 20 includes a polarizing element 21 and a phase difference layer 22. The phase difference layer 22 is followed by the polarizing element 21.

The inventors of the present invention have found that the phase difference (especially the end) of the phase difference layer in the conventional anti-reflection film (i.e., the anti-reflection film formed by laminating the phase difference layer and the polarizing element with each other only by the adhesive layer) The phase difference of the portion varies with time due to shrinkage of the phase difference layer due to temperature change, and the change in the phase difference causes color unevenness. In the present invention, the phase difference layer and the polarizing element are laminated by the subsequent layer, and the anti-reflection film including the phase difference layer is covered with the resin layer. Therefore, an optical laminate which prevents color unevenness can be obtained. More specifically, in the optical layered body having the above configuration, the deformation of the phase difference layer is suppressed, and the expansion and contraction of the phase difference layer due to the temperature change are small. In such an optical laminate, the phase difference of the phase difference layer is small, and color unevenness occurring over time is prevented. Further, as described later, setting the storage elastic modulus E' of the resin layer to a specific range makes the effect more conspicuous.

Preferably, the phase difference layer and the polarizing element are directly adjacent to each other. That is, it is preferable that a layer other than the adhesive layer (for example, a film such as a protective film, an adhesive layer, or the like) is not present between the retardation layer and the polarizing element. In the optical laminate of the present invention, the retardation layer may function as a protective layer of the polarizing element. When the retardation layer which functions as a protective layer of the polarizing element as described above is directly followed by the polarizing element, a thin optical laminate can be obtained.

The anti-reflection film may be laminated on the first substrate via the adhesive layer 23. Further, the anti-reflection film 20 may include a protective film 24 disposed on the opposite side of the polarizing element 21 from the phase difference layer 22. Preferably, the anti-reflection film 20 is disposed such that the polarizing element 21 (and The protective film 24) can be on the side of the second substrate 40 with respect to the phase difference layer 22. When the optical layered body 100 of the present invention is used in an image display device or the like, it is preferable that the anti-reflection film 20 is disposed such that the polarizing element 21 (and the protective film 24) can be based on the phase difference layer 22 On the observer's side. For example, in the case of forming a phase difference layer functioning as a λ/4 plate, the polarizing element can be disposed closer to the observer side than the phase difference layer (λ/4 plate). Further, the optical layered body 100 of the present invention can be disposed while the second substrate 40 is disposed on the observer side.

B. Anti-reflection film

As described above, the anti-reflection film includes a polarizing element and a phase difference layer. The phase difference layer is disposed on one side of the polarizing element and functions as a protective layer of the polarizing element. In one embodiment, the phase difference layer is a single layer. Actually, the protective film can be disposed on the side of the polarizing element opposite to the phase difference layer.

(polarizing element)

Any suitable polarizing element can be employed as the above polarizing element. For example, the resin film for forming the polarizing element may be a single layer resin film, or may be a laminate of two or more layers.

Specific examples of the polarizing element including the single-layer resin film include hydrophilicity of a polyvinyl alcohol (PVA) resin film, a partially formaldehydeized PVA resin film, and an ethylene-vinyl acetate copolymer partial saponified film. The polymer film is a polarizing element obtained by dyeing and stretching treatment of a dichroic substance such as iodine or a dichroic dye; a polyene-based alignment film such as a dehydrated product of PVA or a dehydrochlorination product of polyvinyl chloride. It is preferable to use a polarizing element obtained by dyeing a PVA-based resin film with iodine and uniaxially stretching the resultant, since it is excellent in optical characteristics.

The above dyeing by iodine is carried out, for example, by immersing a PVA-based resin film in an aqueous solution of iodine. The stretching ratio of the uniaxial stretching is preferably from 3 times to 7 times. The extension can be carried out after the dyeing treatment, or can be carried out while dyeing one side. In addition, the dyeing can be carried out after the stretching has been carried out. The PVA-based resin film is subjected to a swelling treatment, a crosslinking treatment, a washing treatment, a drying treatment, and the like as needed. For example, immersing the PVA resin film in water before dyeing By washing with water, the contaminant or anti-blocking agent on the surface of the PVA-based resin film can be washed, and the PVA-based resin film can be swollen and uneven dyeing can be prevented.

Specific examples of the polarizing element obtained by using the laminated body include a polarizing element obtained by using a laminate of a resin substrate and a PVA-based resin layer (PVA-based resin film) laminated on the resin substrate, or a resin substrate and a coating. A polarizing element obtained by laminating a PVA-based resin layer formed on a resin substrate. The polarizing element obtained by using a resin substrate and a laminate body via a PVA-based resin layer formed on the resin substrate can be produced, for example, by a method comprising: applying a PVA-based resin solution to a resin base The solution is dried to form a PVA-based resin layer on a resin substrate to provide a laminate of a resin substrate and a PVA-based resin layer, and the laminate is stretched and dyed to form a PVA-based resin layer as a polarizing element. In the present embodiment, the stretching generally includes extending the laminate in a state where the laminate is immersed in an aqueous boric acid solution. The extension may further comprise extending the laminate in air at a high temperature (e.g., above 95 °C) prior to extending in the aqueous boric acid solution as needed. The laminate of the obtained resin substrate/polarizing element can be used as it is (that is, the resin substrate can be used as a protective film for a polarizing element), and a product obtained as follows can be used: a resin substrate from a resin substrate/ The laminate of the polarizing element is peeled off, and any suitable protective film according to the purpose is laminated on the peeling surface. The details of the manufacturing method of such a polarizing element are described, for example, in Japanese Laid-Open Patent Publication No. 2012-73580. The entire contents of this publication are incorporated herein by reference.

The thickness of the polarizing element is preferably 15 μm or less, more preferably 13 μm or less, further preferably 10 μm or less, and particularly preferably 8 μm or less. The thickness of the polarizing element is limited to 2 μm in one embodiment, and is 3 μm in another embodiment.

The polarizing element preferably exhibits absorption dichroism at any wavelength in the range of 380 nm to 780 nm. The uniaxial transmittance of the polarizing element is preferably from 44.0% to 45.5%, more preferably from 44.5% to 45.0%.

The polarizing element has a degree of polarization of preferably 98% or more, more preferably 98.5% or more, still more preferably 99% or more.

(phase difference layer)

The retardation layer may comprise a retardation film having any suitable optical and/or mechanical properties depending on the purpose. The phase difference layer typically has a slow phase axis. In one embodiment, the angle θ between the slow phase axis of the phase difference layer and the absorption axis of the polarizing element is preferably 35° to 55°, more preferably 38° to 52°, and further preferably 42°. 48°, particularly preferably about 45°. When the angle θ is in such a range, by using the phase difference layer as the λ/4 plate as described later, antireflection having extremely excellent circularly polarized light characteristics (as a result, very excellent antireflection property) can be obtained. membrane.

The refractive index characteristic of the phase difference layer is preferably such that nx>ny The relationship between nz. In one embodiment, the phase difference layer can function as a λ/4 plate. In this case, the in-plane retardation Re (550) of the retardation layer is preferably from 80 nm to 200 nm, more preferably from 100 nm to 180 nm, still more preferably from 110 nm to 170 nm. Furthermore, "ny=nz" here includes not only the case where ny and nz are completely equal to each other, but also the case where ny and nz are substantially equal. Therefore, it is possible to have a condition of ny < nz within a range not impairing the effects of the present invention.

The birefringence Δn _{xy of} the retardation layer is preferably 0.0025 or more, and more preferably 0.0028 or more. On the other hand, the upper limit of the birefringence Δn _{xy is} , for example, 0.0060, preferably 0.0050. When the birefringence is optimized to such a range, a phase difference layer which is thin and has desired optical characteristics can be obtained.

The Nz coefficient of the retardation layer is preferably from 0.9 to 3, more preferably from 0.9 to 2.5, still more preferably from 0.9 to 1.5, still more preferably from 0.9 to 1.3. When such a relationship is satisfied, a very excellent reflected hue can be achieved when the optical laminate obtained is used in an image display device.

The phase difference layer can exhibit an inverse dispersion wavelength characteristic in which the phase difference value increases as the wavelength of the measurement light increases, and can exhibit a positive wavelength dispersion characteristic in which the phase difference value decreases as the wavelength of the measurement light increases, or It shows a flat wavelength dispersion characteristic in which the phase difference value hardly changes even when the wavelength of the light is changed. The retardation layer preferably exhibits an inverse dispersion wavelength characteristic. In this case, the ratio of the retardation layer Re(450)/Re(550) is preferably 0.8 or more and less than 1, more preferably 0.8 or more and 0.95 or less. With such a configuration, very excellent anti-reflection characteristics can be achieved, and in particular, a neutral black reflection color can be realized by using only one single layer of the phase difference layer. In the present invention, even when a phase difference layer exhibiting an inverse dispersion wavelength characteristic is formed, a change in phase difference of the phase difference layer is small and color unevenness occurring over time is prevented.

The retardation layer contains a photoelastic coefficient of preferably 30 × 10 ^-12 Pa or less, more preferably 10 × 10 ^-12 Pa to 20 × 10 ^-12 Pa, and still more preferably 1 × 10 ^-12 Pa to 10 × 10 ^-12 Pa resin. When the photoelastic coefficient is within such a range, a phase difference layer which is less likely to cause a phase difference change when a contraction stress is generated during heating can be formed.

The thickness of the retardation layer is preferably 50 μm or less, more preferably 20 μm to 50 μm.

The above retardation layer may include any suitable resin film. Typical examples of the resin constituting the resin film include a cyclic olefin resin, a polycarbonate resin, a cellulose resin, a polyester resin, a polyvinyl alcohol resin, a polyamine resin, and a polysiloxane. An amine resin, a polyether resin, a polystyrene resin, or an acrylic resin. Among them, a polycarbonate resin is preferred.

Any suitable polycarbonate resin is used as the above polycarbonate resin. In one embodiment, a polycarbonate-based resin containing a structural unit derived from a dihydroxy compound can be used. The dihydroxy compound is, for example, a dihydroxy compound represented by the following formula (1).

(In the above formula (1), R ₁ to R ₄ each independently represent a hydrogen atom, a substituted or unsubstituted carbon number of 1 to 20 carbon atoms, a substituted or unsubstituted carbon a 6- to 20-membered cycloalkyl group, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and X represents a substituted or unsubstituted carbon number to a C 10 alkyl group a substituted or unsubstituted carbon 6 to a carbon number 20 cycloalkyl group, or a substituted or unsubstituted carbon number 6 to a carbon number 20 exoaryl group, and m and n are independently Indicates an integer from 0 to 5.)

Specific examples of the dihydroxy compound represented by the general formula (1) include 9,9-bis(4-hydroxyphenyl)fluorene and 9,9-bis(4-hydroxy-3-methylphenyl). Ruthenium, 9,9-bis(4-hydroxy-3-ethylphenyl)anthracene, 9,9-bis(4-hydroxy-3-n-propylphenyl)anthracene, 9,9-bis(4-hydroxyl 3-isopropylphenyl)anthracene, 9,9-bis(4-hydroxy-3-n-butylphenyl)anthracene, 9,9-bis(4-hydroxy-3-second butylphenyl) Indole, 9,9-bis(4-hydroxy-3-t-butylphenyl)anthracene, 9,9-bis(4-hydroxy-3-cyclohexylphenyl)anthracene, 9,9-bis(4- Hydroxy-3-phenylphenyl)anthracene, 9,9-bis(4-(2-hydroxyethoxy)phenyl)anthracene, 9,9-bis(4-(2-hydroxyethoxy)-3 -methylphenyl)anthracene, 9,9-bis(4-(2-hydroxyethoxy)-3-isopropylphenyl)anthracene, 9,9-bis(4-(2-hydroxyethoxy) )-3-isobutylphenyl)indole, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butylphenyl)anthracene, 9,9-bis(4-(2) -hydroxyethoxy)-3-cyclohexylphenyl)anthracene, 9,9-bis(4-(2-hydroxyethoxy)-3-phenylphenyl)anthracene, 9,9-bis(4- (2-hydroxyethoxy)-3,5-dimethylphenyl)anthracene, 9,9-bis(4-(2-hydroxyethoxy)-3-tert-butyl-6-methylbenzene芴,9,9-bis(4-(3-hydroxy-2,2-dimethylpropoxy)benzene ) Fluorene.

The polycarbonate resin may contain isosorbide, isomannide, isoidide, spiro diol, dioxane, in addition to the structural unit derived from the above dihydroxy compound. A structural unit derived from a dihydroxy compound such as a diol, diethylene glycol (DEG), triethylene glycol (TEG), polyethylene glycol (PEG), or bisphenol.

A polycarbonate-based resin containing a structural unit derived from a dihydroxy compound is described in, for example, Japanese Patent No. 5204200, Japanese Patent Laid-Open No. Hei. No. 2012-67300, Japanese Patent No. 3325560, and WO2014/061677A. The disclosure of this patent document serves as a reference Quoted in this article.

In one embodiment, a polycarbonate-based resin containing an oligomeric fluorene structural unit can be used. The polycarbonate resin containing an oligomeric fluorene structural unit is, for example, a resin containing a structural unit represented by the following general formula (2) and/or a structural unit represented by the following general formula (3).

(In the above formula (2) and formula (3), R ₅ and R ₆ each independently represent a direct bond or a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms (preferably the main chain) The carbon number is 2 to 3 alkyl groups, and R ₇ represents a direct bond or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms (preferably having a carbon number of 1 in the main chain) The alkyl group of ~2, R ₈ to R ₁₃ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 4, more preferably 1 to 2) carbon atoms. The substituted or unsubstituted carbon number of 4 to 10 (preferably 4 to 8, more preferably 4 to 7), substituted or unsubstituted carbon number 1 to 10 (preferably 1~) 4, more preferably 1 to 2) thiol, substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms (preferably 1 to 4, more preferably 1 to 2), substituted or not The substituted aryloxy group having 1 to 10 carbon atoms (preferably 1 to 4, more preferably 1 to 2), substituted or unsubstituted carbon number 1 to 10 (preferably 1 to 4, more preferably 1 to 2) an anthracene group, a substituted or unsubstituted amine group, a substituted or unsubstituted carbon number of 1 to 10 (preferably 1 to 4), substituted by a substituted generation An ethynyl group having a carbon number of 1 to 10 (preferably 1 to 4), Sulfur atom of the substituted group, the substituent having a silicon atom, a halogen atom, a nitro group, or a cyano group, and R ₈ ~ R ₁₃ in at least two of adjacent groups may be combined with each other to form a ring.)

In one embodiment, the anthracene ring contained in the oligomeric fluorene structural unit has a structure in which all of R ₈ to R ₁₃ represent a hydrogen atom, or R ₈ and/or R ₁₃ each represent a halogen atom, a fluorenyl group, and a nitrate. Any of a group consisting of a cyano group, a cyano group, and a sulfo group, and R ₉ to R ₁₂ represent a structure of a hydrogen atom.

A polycarbonate-based resin containing an oligomeric fluorene structural unit is described, for example, in JP-A-2015-212816. The disclosure of this patent document is incorporated herein by reference.

The glass transition temperature of the polycarbonate resin is preferably from 110 ° C to 150 ° C, more preferably from 120 ° C to 140 ° C. If the glass transition temperature is too low, the heat resistance of the resin tends to be deteriorated and the resin may cause dimensional change after the film is formed. If the glass transition temperature is too high, the molding stability of the resin at the time of film formation may be deteriorated, and the transparency of the film may be impaired. Further, the glass transition temperature was determined in accordance with JIS K 7121 (1987).

The resin film can be obtained by any suitable method. For example, the resin film can be obtained by extending an unextended resin film.

The above extension may employ any suitable extension method, extension conditions (e.g., elongation temperature, extension ratio, direction of extension). Specifically, various extension methods such as free end extension, fixed end extension, free end contraction, and fixed end contraction may be used alone, or may be employed simultaneously or sequentially. The extending direction can be extended in each direction or dimension such as the longitudinal direction, the width direction, the thickness direction, and the oblique direction. The stretching temperature is preferably from Tg -30 ° C to Tg + 60 ° C, more preferably from Tg - 10 ° C to Tg + 50 ° C with respect to the glass transition temperature (Tg) of the resin film.

The above stretching method can obtain a resin film having the above-described desired optical characteristics (for example, refractive index characteristics, in-plane retardation, Nz coefficient) by appropriately selecting the stretching conditions.

In one embodiment, the resin film is produced by uniaxially extending the unstretched resin film or uniaxially extending the fixed end. Specific examples of the uniaxial stretching of the fixed end include a method of extending the resin film in the width direction (lateral direction) while advancing the resin film in the longitudinal direction. The stretching ratio is preferably from 1.1 to 3.5 times.

In another embodiment, the retardation film can be formed by continuously stretching the elongated resin film continuously in the direction of the angle θ with respect to the longitudinal direction. By using an oblique extension, an elongated stretch film having an alignment angle (having a slow phase axis in the direction of the angle θ) with respect to the longitudinal direction of the film is obtained, and can be used, for example, with a polarizing element. Roll-to-roll manufacturing is carried out in the laminate, and the manufacturing steps can be simplified. The angle θ may be an angle formed by the absorption axis of the polarizing element in the anti-reflection film and the slow phase axis of the phase difference layer. As described above, the angle θ is preferably from 38 to 52, more preferably from 42 to 48, still more preferably about 45.

As the stretching machine for obliquely extending, for example, a tenter stretching machine which can add a supply force of a right and left different speed, or a tensile force or an extraction force in the lateral direction and/or the longitudinal direction can be cited. The tenter type extender includes a lateral uniaxial stretching machine, a synchronous biaxial stretching machine, and any suitable stretching machine can be used as long as the elongated resin film can be continuously extended obliquely.

By appropriately controlling the left and right speeds in the above-described stretching machine, a phase difference layer (substantially elongated retardation film) having the above-described desired in-plane phase difference and having a slow phase axis in the desired direction can be obtained. .

The extension temperature of the film may be changed according to the in-plane retardation value and thickness required for the retardation layer, the kind of the resin to be used, the thickness of the film to be used, and the stretching ratio. Specifically, the stretching temperature is preferably from Tg-30 ° C to Tg + 30 ° C, further preferably from Tg - 15 ° C to Tg + 15 ° C, most preferably from Tg - 10 ° C to Tg + 10 ° C. By this temperature By extending, a phase difference layer having characteristics suitable for the present invention can be obtained. Further, Tg means the glass transition temperature of the material constituting the film.

(protective film)

The above protective film is formed of any suitable resin. Examples of the resin for forming the protective film include a cellulose resin such as triethylenesulfonyl cellulose (TAC); or a polyester resin, a polyvinyl alcohol resin, a polycarbonate resin, or a polyamido compound. A transparent resin such as a polyimide, a polyether, a polyfluorene, a polystyrene, a polynorbornene, a polyolefin, a (meth)acrylic or an acetate. Further, examples thereof include thermosetting resins such as (meth)acrylic acid, urethane-based, (meth)acrylic acid urethane-based, epoxy-based, and organofluorene-based resins, and ultraviolet curable resins. Further, a glass-based polymer such as a siloxane-based polymer may also be mentioned. Further, a polymer film described in JP-A-2001-343529 (WO01/37007) can also be used. As the material of the film: for example, a thermoplastic resin having a substituted or unsubstituted quinone imine group on its side chain and a substituted or unsubstituted phenyl and nitrile group on its side chain can be used. The resin composition of the thermoplastic resin may, for example, be a resin composition having an alternating copolymer of isobutylene and N-methylmaleimide and an acrylonitrile-styrene copolymer. The polymer film may be, for example, an extrusion molded article of the above resin composition.

The thickness of the above protective film may be any suitable thickness as long as the effect of the present invention is obtained. The thickness of the protective film is, for example, 20 μm to 40 μm, preferably 25 μm to 35 μm.

(adhesive layer)

The polarizing element, the retardation layer, and the protective film laminate may be laminated via an adhesive layer. As the adhesive constituting the adhesive layer, any appropriate adhesive can be used. For example, the adhesive layer is formed of a polyvinyl alcohol-based adhesive.

The thickness of the subsequent layer is preferably 1 μm or less, more preferably 0.8 μm or less. As long as the thickness is within this range, the phase difference variation of the phase difference layer can be obtained small and prevented over time An optical laminate that is uneven in color. The lower limit of the thickness of the above adhesive layer is, for example, 0.01 μm.

(adhesive layer)

As described above, the antireflection film has an adhesive layer and can be attached to the first substrate via the adhesive layer. Any suitable adhesive is used as the adhesive constituting the adhesive layer. For example, the adhesive layer is formed of an acrylic adhesive.

The thickness of the above adhesive layer is preferably from 5 μm to 30 μm, more preferably from 5 μm to 15 μm. In the present invention, by forming the resin layer, expansion and contraction of the antireflection film are suppressed, so that foaming and peeling of the adhesive layer can be prevented. Therefore, the thickness of the adhesive layer can be reduced, and thus a thin optical laminate can be obtained.

(other layers)

The antireflection film may further have other layers. As the other layer, for example, a phase difference layer different from the above-described phase difference layer can be cited. In one embodiment, the anti-reflection film may further include a retardation layer (retardation film or liquid crystal layer) having a refractive index distribution of nz>nx=ny and functioning as a positive C-plate. Here, "nx=ny" includes not only the case where nx and ny are completely equal to each other, but also the case where nx and ny are substantially equal to each other. That is, it means that Re is less than 10 nm. The thickness direction phase difference Rth of the phase difference layer which functions as a positive C-plate is preferably from -20 nm to -200 nm, further preferably from -40 nm to -180 nm, particularly preferably from -40 nm to -160 nm. The thickness of the phase difference layer in which such Rth can be obtained can vary depending on the materials used and the like. The thickness is preferably from 0.5 μm to 60 μm, more preferably from 0.5 μm to 50 μm, most preferably from 0.5 μm to 40 μm.

C. Resin layer

The resin layer is disposed between the first substrate and the second substrate and covers the anti-reflection film. Such a resin layer can be formed by laminating an antireflection film on the first substrate, for example, and then coating the composition for forming a curable resin so as to seal the antireflection film, and then curing the composition for forming the resin layer. In addition, the resin layer forming composition can be applied to another substrate Then, the resin layer forming composition is formed into a semi-hardened state to form a precursor layer; the precursor layer is transferred onto the laminate of the first substrate and the antireflection film; and thereafter, the precursor layer is cured to form a resin layer.

The resin layer-forming composition contains a curable compound (monomer or oligomer). Examples of the curable compound include an acrylic compound, an epoxy compound, and a urethane compound.

The acrylic compound preferably has a hydroxyl group, a carboxyl group, a cyano group, an amine group, a decylamino group, a heterocyclic group, a lactone ring group, and/or an isocyanate ring group. When a resin layer-forming composition containing an acrylic compound having such a functional group is used, a resin layer excellent in adhesion to the first substrate and the second substrate can be formed.

Specific examples of the acrylic compound include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, or 4-hydroxybutyl (meth)acrylate having a hydroxyl group. Acrylic compound; acrylic compound having a carboxyl group such as acrylic acid or methacrylic acid; acrylic compound having a cyano group such as acrylonitrile or methacrylonitrile; dimethylaminoethyl (meth)acrylate; Acrylic acid-based compound having dimethylaminopropyl acrylate, diethylaminoethyl (meth)acrylate, diisopropylaminoethyl (meth)acrylate, amine; acrylamide, dimethyl An acrylic compound having a guanamine group such as acrylamide, dimethylaminopropyl acrylamide, isopropyl acrylamide, diethyl acrylamide, hydroxyethyl acrylamide, acryl hydrazinomorph (tetramethyl methacrylate), glycidyl (meth)acrylate, pentamethylpiperidyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, etc. Acrylic compound; γ-butyrolactone (meth) acrylate monomer, etc. Rings acrylate compound; (meth) acrylate, 2-isocyanatoethyl acrylate monomer having the acrylic group of the isocyanate compound and the like. The acrylic compounds may be used singly or in combination.

The resin layer-forming composition may contain a polyfunctional acrylic monomer (i.e., an acrylic monomer having a plurality of acryloxy groups), and an oligomerization derived from a polyfunctional acrylic monomer. And a prepolymer derived from a polyfunctional acrylic monomer as an acrylic compound. Examples of the polyfunctional acrylic monomer include tricyclodecane dimethanol diacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane triacrylate, and pentaerythritol. Tetra(meth)acrylate, dimethylolpropane tetraacrylate, dipentaerythritol hexa(meth) acrylate, 1,6-hexanediol (meth) acrylate, 1,9-nonanediol diacrylate Ester, 1,10-nonanediol (meth) acrylate, polyethylene glycol di(meth) acrylate, polypropylene glycol di(meth) acrylate, dipropylene glycol di acrylate, isocyanuric acid tri Methyl) acrylate, ethoxylated glycerin triacrylate, pentylene glycol tetraacrylate, and the like. The polyfunctional acrylic monomers may be used singly or in combination of plural kinds.

The content ratio of the polyfunctional acrylic monomer in the resin layer-forming composition is preferably 5 parts by weight or less, more preferably 1 part by weight, based on 100 parts by weight of the curable compound in the resin layer-forming composition. the following. In one embodiment, a composition for forming a resin layer containing no polyfunctional acrylic monomer is used. When such a resin composition is used, shrinkage due to the hardening process can be suppressed, and as a result, a resin layer excellent in adhesion to the substrate can be formed.

Examples of the epoxy-based compound include bisphenol A type, bisphenol F type, bisphenol S type, and hydrogenated product bisphenol type; and phenol novolak type such as phenol novolak type or cresol novolak type. a nitrogen-containing cyclic type such as an isocyanuric acid triglycidyl ester type or an urethane type; an alicyclic type; an aliphatic type; a naphthalene type; a glycidyl ether type or a biphenyl type low water absorption type; a dicyclic type such as a diene type; an ester type; an ether ester type; and an epoxy compound such as the modified type. Examples of the bisphenol epoxy compound include diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diglycidyl ether of bisphenol S. Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate and 3,4-epoxy-6-methylcyclohexylcarboxylic acid 3. , 4-epoxy-6-methylcyclohexylmethyl ester. Examples of the aliphatic epoxy compound include diglycidyl ether of 1,4-butanediol. Diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerol, triglycidyl ether of trimethylolpropane.

In one embodiment, an epoxy-based compound and an oxetane-based compound are used in combination. By adding an oxetane-based compound, the viscosity of the resin layer-forming composition can be lowered or the curing rate can be increased.

The resin layer-forming composition may contain an oligomer of a urethane (meth) acrylate and/or a urethane (meth) acrylate as an urethane-based compound. The above urethane (meth) acrylate can be obtained by reacting a hydroxy ester of (meth) acrylate obtained from (meth)acrylic acid or a (meth) acrylate and a polyhydric alcohol with a diisocyanate. The oligomer of urethane (meth) acrylate and urethane (meth) acrylate may be used singly or in combination of plural.

Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and (methyl). Cyclohexyl acrylate.

Examples of the polyhydric alcohol include ethylene glycol, 1,3-propanediol, 1,2-propanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, and 1,4- Butylene glycol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentanediol, 3-methyl -1,5-pentanediol, neopentyl glycol hydroxypivalate, tricyclodecane dimethanol, 1,4-cyclohexanediol, spirodiol, hydrogenated bisphenol A, bisphenol A-ring Oxyethane adduct, bisphenol A-propylene oxide adduct, trimethylolethane, trimethylolpropane, glycerol, 3-methylpentane-1,3,5-triol, pentaerythritol , dipentaerythritol, tripentaerythritol, glucose, and the like.

For example, an aromatic, aliphatic or alicyclic various diisocyanate can be used as the above diisocyanate. Specific examples of the diisocyanate include tetramethylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 2,4-toluene diisocyanate, and 4,4-diphenyl diisocyanate. , 5-naphthalene diisocyanate, 3,3-dimethyl-4,4-diphenyl diisocyanate, xylene diisocyanate, trimethylhexamethylene diisocyanate An acid ester, 4,4-diphenylmethane diisocyanate, and such hydrogenated products.

The above resin layer-forming composition may or may not contain a solvent. Examples of the solvent include dibutyl ether, dimethoxymethane, methyl acetate, ethyl acetate, isobutyl acetate, methyl propionate, ethyl propionate, methanol, ethanol, and methyl isobutyl. Ketone (MIBK) and the like. These may be used alone or in combination.

The above resin layer-forming composition may further contain any appropriate additives. Examples of the additive include a polymerization initiator, a crosslinking agent, a leveling agent, an anti-blocking agent, a dispersion stabilizer, a thixotropic agent, an antioxidant, an ultraviolet absorber, an antifoaming agent, a tackifier, and a dispersing agent. , surfactant, catalyst, filler, lubricant, antistatic agent.

In one embodiment, the resin layer-forming composition contains a coupling agent. The resin layer containing a coupling agent is preferable in terms of excellent adhesion to the first substrate, the second substrate, and the antireflection film. Examples of the coupling agent include an epoxy-terminated coupling agent, an amine group-containing coupling agent, a methacryl oxime group-containing coupling agent, and a thiol group-containing coupling agent.

As a coating method of the composition for forming a resin layer, any appropriate method can be employed. For example, a bar coating method, a roll coating method, a gravure coating method, a rod coating method, a slit hole coating method, a curtain coating method, a curtain coating method, and a comma coating method are mentioned. Comma coating method.

As the hardening method of the composition for forming a resin layer, any appropriate hardening treatment can be employed. Representatively, the hardening treatment is carried out by ultraviolet irradiation. The cumulative amount of light by ultraviolet irradiation is preferably from 500 mJ/cm ² to 5000 mJ/cm ² . Further, the resin layer-forming composition can be cured by heating. The heating temperature at the time of thermal curing is, for example, 90 ° C to 150 ° C.

The thickness of the thinnest portion of the resin layer (i.e., the distance between the second substrate and the antireflection film) is preferably from 1 μm to 300 μm, more preferably from 1 μm to 100 μm, still more preferably from 1 μm to 30 μm. As long as it is within such a range, the dimensional change of the phase difference layer can be effectively suppressed.

The storage elastic modulus E' of the resin layer at 25 ° C is preferably 1.0 × 10 ⁶ Pa or more, more preferably 1.0 × 10 ⁷ Pa or more, still more preferably 1.0 × 10 ⁸ Pa or more, and particularly preferably 1.0. ×10 ⁹ Pa to 1.0 × 10 ¹¹ Pa. As long as it is within such a range, the dimensional change of the phase difference layer can be effectively suppressed. The method of measuring the storage elastic modulus E' will be described later.

The glass transition temperature (Tg) of the above resin layer is preferably from 10 ° C to 200 ° C, more preferably from 20 ° C to 150 ° C, still more preferably from 40 ° C to 130 ° C.

D. First substrate, second substrate

The first substrate can comprise any suitable material. Examples of the material constituting the first substrate include glass and a resin film. In one embodiment, the first substrate may be a substrate that constitutes the outermost layer of the image display panel (for example, an organic EL panel). In this case, the antireflection film constituting the optical laminate of the present invention is disposed on the image. On the viewer's side surface of the display panel.

The second substrate described above may comprise any suitable material. Examples of the material constituting the second substrate include glass, a resin film, and the like.

The optical laminate of the present invention can be formed by laminating the anti-reflection film on the first substrate, and then laminating the first substrate and the anti-reflection film with the second substrate by sandwiching the anti-reflection film. This is followed by a resin layer. The method of forming the resin layer is as described in the above item C.

Example

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited by the examples.

[Production Example 1-1] Production of retardation film A constituting the retardation layer

(Production of polycarbonate resin film)

The polymerization was carried out using a batch polymerization apparatus comprising two vertical reactors each having a stirring blade and a reflux condenser controlled at 100 °C. 9,9-[4-(2-hydroxyethoxy)phenyl]indole (BHEPF), isosorbide (ISB), diethylene glycol (DEG), diphenyl carbonate (DPC), and tetrahydrate Magnesium acetate was loaded into the first reactor at a molar ratio of BHEPF/ISB/DEG/DPC/magnesium acetate = 0.348/0.490/0.162/1.005/1.00 x 10 ^-5 . After the reactor was sufficiently substituted with nitrogen (oxygen concentration: 0.0005 to 0.001 vol%), the temperature was raised with a heat medium, and stirring was started at a time when the internal temperature became 100 °C. The internal temperature was brought to 220 ° C 40 minutes after the start of the temperature rise, and the reactor was controlled to maintain the temperature while starting the pressure reduction at 90 minutes after the temperature had reached 220 ° C to lower the pressure in the reactor to 13.3 kPa. The phenol vapor produced as a by-product related to the polymerization reaction is introduced into a reflux condenser at 100 ° C, the monomer component present in a certain amount in the phenol vapor is returned to the reactor, and the uncondensed phenol vapor is introduced to In a 45 ° C condenser and recovered.

The introduction of nitrogen into the first reactor immediately restores the pressure to atmospheric pressure. Thereafter, the oligomerized reaction liquid in the first reactor is transferred to the second reactor. Then, the temperature rise and the pressure reduction in the second reactor were started for 50 minutes, and the internal temperature and pressure were set to 240 ° C and 0.2 kPa, respectively. Thereafter, the polymerization is carried out until the predetermined stirring power is reached. At the point of time when the predetermined power is reached, nitrogen is introduced into the reactor to restore the pressure to atmospheric pressure, and the reaction liquid is extracted in the form of strands, which are granulated by a rotary cutter to obtain BHEPF/ISB/DEG= A polycarbonate resin composed of a copolymer of 34.8/49.0/16.2 [mol%]. The polycarbonate resin had a reduced viscosity of 0.430 dL/g and a glass transition temperature of 128 °C.

The obtained polycarbonate resin was vacuum-dried at 80 ° C for 5 hours, and then used with a single-screw extruder (manufactured by Isuzu Kakoki Co., Ltd., screw diameter: 25 mm, cylinder preset temperature: 220 ° C), T-die ( Width: 900 mm, preset temperature: 220 ° C), cooling roll (preset temperature: 120 ° C to 130 ° C), and a film forming apparatus of the tensioning unit to produce a polycarbonate resin film having a thickness of 140 μm.

(production of retardation film)

The above unstretched modified polycarbonate film was obliquely extended to provide a retardation film A (thickness: 50 μm, photoelastic coefficient: 30 × 10 ^-12 Pa, wavelength dispersion property Re (450) / Re (550): 0.91) . At this time, the extending direction was set to be 45° with respect to the longitudinal direction of the film. Further, the elongation ratio is adjusted from 2 times to 3 times, so that the retardation film A represents a phase difference of λ/4. Further, the stretching temperature was set to 133 ° C (i.e., Tg + 5 ° C of the unstretched modified polycarbonate film).

[Production Example 1-2] Production of retardation film B constituting a phase difference layer

(Production of polycarbonate resin film)

38.06 parts by weight (0.059 mol) of bis[9-(2-phenoxycarbonylethyl)fluoren-9-yl]methane, 53.73 parts by weight (0.368 mol) of isosorbide (manufactured by Roquette Frères, Name: "POLYSORB"), 9.64 parts by weight (0.067 mol) of 1,4-cyclohexanedimethanol (cis-trans mixture, manufactured by SK Chemicals), 81.28 parts by weight (0.379 mol) of diphenyl carbonate An ester (manufactured by Mitsubishi Chemical Corporation) and 3.83 × 10 ^-4 parts by weight (2.17 × 10 ^-6 mol) of one of the catalysts, calcium acetate hydrate, were placed in a reaction vessel, and the inside of the reaction apparatus was replaced with a reduced pressure nitrogen gas. The raw material was dissolved while stirring at 150 ° C for about 10 minutes under a nitrogen atmosphere. As a first step of the reaction, the temperature was raised to 220 ° C over 30 minutes, and the solution was allowed to react under normal pressure for 60 minutes. Then, the pressure was lowered from normal pressure to 13.3 kPa over 90 minutes, and the pressure was maintained at 13.3 kPa for 30 minutes, and then the produced phenol was extracted to the outside of the reaction system. Then, as a second step of the reaction, the temperature of the heat medium was raised to 240 ° C over 15 minutes, and the pressure was lowered to 0.10 kPa or less over 15 minutes, and the produced phenol was extracted to the outside of the reaction system. After the predetermined agitation torque has been reached, the reaction is stopped by returning the pressure to normal pressure with nitrogen, the resulting polyester carbonate is extruded into water and the strand is cut to provide polycarbonate resin pellets.

(production of retardation film)

The above film including the polycarbonate resin pellets was obliquely extended to provide a retardation film B (thickness: 50 μm, photoelastic coefficient: 16 × 10 ^-12 Pa, wavelength dispersion property Re (450) / Re (550): 0.83) . At this time, the extending direction was set to be 45° with respect to the longitudinal direction of the film. Further, the stretching ratio is adjusted from 2 times to 3 times, so that the retardation film B represents a phase difference of λ/4. Further, the extension temperature was set to 148 ° C (i.e., Tg + 5 ° C of the unstretched modified polycarbonate film).

[Manufacturing Example 2] Production of a polarizing element

The PVA-based resin film having a polymerization degree of 2,400, a degree of saponification of 99.9 mol%, and a thickness of 30 μm was immersed in warm water of 30° C., and the film was swollen while being uniaxially stretched so that the length of the PVA-based resin film became 2.0 of its original length. Times. Then, the PVA-based resin film was immersed in an aqueous solution (dye bath) containing a mixture of iodine and potassium iodide (weight ratio: 0.5:8) at a concentration of 0.3% by weight, and the film was uniaxially stretched while being dyed to a PVA system. The length of the resin film was changed to 3.0 times the initial length. After that, the PVA-based resin film was immersed in an aqueous solution (cross-linking bath 1) containing 5% by weight of boric acid and 3% by weight of potassium iodide to extend the PVA-based resin film so that the length thereof became 3.7 times the initial length. Thereafter, the PVA-based resin film was stretched in an aqueous solution (cross-linking bath 2) containing 4% by weight of boric acid and 5% by weight of potassium iodide to have a length of 6 times the original length. Further, the film was subjected to iodide ion immersion treatment in an aqueous solution containing 3 wt% of potassium iodide (iodine immersion bath), and then dried in an oven at 60 ° C for 4 minutes to obtain a polarizing element.

[Production Example 3-1] Production of Antireflection Film Using Phase Difference Film A

The retardation film A produced in Production Example 1-1 was laminated on one surface of the polarizing element produced in Production Example 2 via an adhesive layer containing a polyvinyl alcohol-based adhesive, and passed through a polyvinyl alcohol-based adhesive. Next, a layer of a triacetyl cellulose (TAC) film (manufactured by Konica Minolta Co., Ltd., trade name: "KC2UA", thickness: 25 μm) as a protective film was laminated on the other surface of the polarizing element to obtain antireflection. Film AI (protective film/adhesive layer/polarizing element/adhesive layer/phase difference layer). As a polyvinyl alcohol-based adhesive, a polyvinyl alcohol-based resin containing an ethyl acetonitrile group at a temperature of 30 ° C (average degree of polymerization: 1200, degree of saponification: 98.5 mol%, degree of acetylation: 5 mol%) was dissolved in pure water; the solid content concentration of the solution was adjusted to 4%.

[Production Example 3-2] Production of Antireflection Film Using Phase Difference Film A

A triethylenesulfonated cellulose (TAC) film (manufactured by Konica Minolta Co., Ltd., trade name: "KC2UA", which is a protective film of two surface areas of the polarizing element produced in Production Example 2 via an adhesive layer containing an aqueous adhesive. "Thickness: 25 μm), and a polarizing plate was obtained. The retardation film A produced in Production Example 1-1 was laminated on one surface of the polarizing element via an adhesive layer containing an acrylic adhesive. Thereby, the antireflection film A-II (protective film/adhesive layer/polarizing element/adhesive layer/protective film/adhesive layer/phase difference layer) was obtained.

[Manufacturing Example 3-3] Production of Antireflection Film Using Phase Difference Film B

The retardation film B produced in Production Example 1-2 was laminated on one surface of the polarizing element produced in Production Example 2 via an adhesive layer containing a polyvinyl alcohol-based adhesive, and passed through a polyvinyl alcohol-based adhesive. Next, a layer of a triacetyl cellulose (TAC) film (manufactured by Konica Minolta Co., Ltd., trade name: "KC2UA", thickness: 25 μm) as a protective film was laminated on the other surface of the polarizing element to obtain antireflection. Film BI (protective film/adhesive layer/polarizing element/adhesive layer/phase difference layer). Further, as a polyvinyl alcohol-based adhesive, a polyvinyl alcohol-based resin containing an ethyl acetonitrile group at a temperature of 30 ° C (average degree of polymerization: 1200, degree of saponification: 98.5 mol%, acetamidine) Degree of chemistry: 5 mol%) dissolved in pure water; the solid content concentration of the solution was adjusted to 4%.

[Manufacturing Example 3-4] Production of Antireflection Film Using Phase Difference Film B

A triethylenesulfonated cellulose (TAC) film (manufactured by Konica Minolta Co., Ltd., trade name: "KC2UA", which is a protective film of two surface areas of the polarizing element produced in Production Example 2, via an adhesive layer containing a water-based adhesive. "Thickness: 25 μm), and a polarizing plate was obtained. The retardation film B produced in Production Example 1-2 was laminated on one surface of the polarizing plate via an adhesive layer containing an acrylic adhesive to obtain an antireflection film B-II (protective film/adhesive layer/polarizing element) / adhesive layer / protective film / adhesive layer / phase difference layer).

[Production Example 4-1] Preparation of Resin Layer Forming Composition

Mix 100 parts by weight of 2-hydroxyethyl acrylamide (manufactured by Xingren Company; below) Also known as HEAA), 1 part by weight of a photopolymerization initiator (manufactured by BASF, trade name: "Irgacure 819") was used to prepare a composition 1 for forming a resin layer.

[Production Example 4-2] Preparation of Resin Layer Forming Composition

In addition to using 70 parts by weight of HEAA and 30 parts by weight of 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.; hereinafter also referred to as 4-HBA) instead of 100 parts by weight of HEAA, and Production Example 4 Composition 2 for forming a resin layer was prepared in the same manner as in -1.

[Production Example 4-3] Preparation of Resin Layer Forming Composition

The resin layer-forming composition 3 was prepared in the same manner as in Production Example 4-1, except that 50 parts by weight of HEAA and 50 parts by weight of 4-HBA were used instead of 100 parts by weight of HEAA.

[Production Example 4-4] Preparation of Resin Layer Forming Composition

The resin layer-forming composition 4 was prepared in the same manner as in Production Example 4-1, except that 30 parts by weight of HEAA and 70 parts by weight of 4-HBA were used instead of 100 parts by weight of HEAA.

[Production Example 4-5] Preparation of Resin Layer Forming Composition

The resin layer-forming composition 5 was prepared in the same manner as in Production Example 4-1, except that 22 parts by weight of HEAA and 78 parts by weight of 4-HBA were used instead of 100 parts by weight of HEAA.

[Production Example 4-6] Preparation of Resin Layer Forming Composition

The resin layer-forming composition 6 was prepared in the same manner as in Production Example 4-1, except that 15 parts by weight of HEAA and 85 parts by weight of 4-HBA were used instead of 100 parts by weight of HEAA.

[Production Example 4-7] Preparation of Resin Layer Forming Composition

The resin layer-forming composition 7 was prepared in the same manner as in Production Example 4-1, except that 100 parts by weight of 4-HBA was used instead of 100 parts by weight of HEAA.

[Production Example 4-8] Preparation of Resin Layer Forming Composition

In addition to 70 parts by weight of 4-propenylmercaptomorph (manufactured by Xingren Co., Ltd.; hereinafter also referred to as ACMO) and 30 parts by weight of tetrahydrofurfuryl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name Resin composition 8 was prepared in the same manner as in Production Example 4-1 except that "Viscoat #150"; hereinafter also referred to as THFA) was used instead of 100 parts by weight of HEAA.

[Production Example 4-9] Preparation of Resin Layer Forming Composition

Resin composition 9 was prepared in the same manner as in Production Example 4-1, except that 45 parts by weight of ACMO and 55 parts by weight of THFA were used instead of 100 parts by weight of HEAA.

[Production Example 4-10] Preparation of Resin Layer Forming Composition

Resin composition 10 was prepared in the same manner as in Production Example 4-1, except that 25 parts by weight of ACMO and 75 parts by weight of THFA were used instead of 100 parts by weight of HEAA.

[Production Example 5-1] Preparation of Composition of Resin Layer

90 parts by weight of an epoxy compound (manufactured by Kyoeisha Chemical Co., Ltd., trade name "EPOLIGHT 80MF"), and 10 parts by weight of an oxetane compound (manufactured by Toagosei Co., Ltd., trade name "OXT-221") 3 parts by weight of a photopolymerization initiator (manufactured by San-Apro Co., Ltd., trade name "CPI-100P"), and 0.5 part by weight of a sensitizer (manufactured by Kawasaki Kasei Kogyo Co., Ltd., trade name "UVS-1331") A composition 11 for forming a resin layer was prepared.

[Production Example 5-2] Preparation of Resin Layer Forming Composition

In place of 90 parts by weight of an epoxy compound (trade name "EPOLIGHT 100MF" manufactured by Kyoeisha Chemical Co., Ltd.), 90 parts by weight of an epoxy compound (manufactured by Kyoeisha Chemical Co., Ltd., trade name: "EPOLIGHT 80MF") was used. Further, the resin layer-forming composition 12 was prepared in the same manner as in Production Example 5-1.

[Preparation Example 5-3] Preparation of Resin Layer Forming Composition

In place of 90 parts by weight of an epoxy compound (trade name: "EPOLIGHT 40E" manufactured by Kyoeisha Chemical Co., Ltd.), 90 parts by weight of an epoxy compound (manufactured by Kyoeisha Chemical Co., Ltd., trade name: "EPOLIGHT 80MF") was used. The resin layer-forming composition 13 was prepared in the same manner as in Production Example 5-1.

[Example 1-1]

An acrylic glass (manufactured by Matsuron Glass Industry Co., Ltd.) was used as the first substrate, and an adhesive layer was formed on the first substrate via an adhesive layer containing an acrylic adhesive. Anti-reflection film A-I made in 3-1. At this time, lamination is performed so that the retardation layer of the anti-reflection film A-I is on the first substrate side.

Then, the composition 1 for forming a resin layer prepared in Production Example 4-1 was applied to cover the antireflection film AI, and further, a second substrate was laminated on the coating layer of the composition 1 for forming a resin layer (by Songlang Glass Industry) Acrylic glass manufactured by the company). Then, ultraviolet rays (irradiation amount: 5 J/cm ² ) were irradiated with a UV irradiator, and the resin layer-forming composition was cured in the formed laminate to obtain an optical layered body having the configuration shown in Fig. 1 .

[Examples 1-2 to 1-11, Comparative Examples 1-1 to 1-2]

An optical layered body was obtained in the same manner as in Example 1-1, except that the composition for forming a resin layer shown in Table 1 was used instead of the composition for forming a resin layer.

[Comparative Example 1-3~1-15]

The resin layer-forming composition shown in Table 1 was used instead of the resin layer-forming composition 1; and the anti-reflection film A-II produced in Production Example 3-2 was used instead of the anti-reflection produced in Production Example 3-1. An optical laminate was obtained in the same manner as in Example 1-1 except for the film AI.

[Comparative Example 1-16]

The composition 1 for resin layer formation is not used; and the barrier layer antireflection film and the second substrate are used in a state where a gap exists between the antireflection film and the second substrate, and is the same as in the embodiment 1-1. The optical laminate is obtained in a manner.

[Example 2-1]

An optical layered body was obtained in the same manner as in Example 1-1, except that the antireflection film B-I produced in Production Example 3-3 was used instead of the antireflection film A-I produced in Production Example 3-1.

[Examples 2-2 to 2-11, Comparative Examples 2-1 to 2-2]

An optical layered body was obtained in the same manner as in Example 2-1, except that the composition for forming a resin layer shown in Table 2 was used instead of the composition for forming a resin layer.

[Comparative Example 2-3~2-15]

In addition to using the resin layer forming composition shown in Table 2, instead of the resin layer forming combination The optical layered body was obtained in the same manner as in Example 2-1 except that the antireflection film B-II produced in Production Example 3-4 was used instead of the antireflection film B-I produced in Production Example 3-3.

[Comparative Example 2-16]

The composition 1 for forming a resin layer was not used; and in the same manner as in Example 2-1, the gap between the antireflection film and the second substrate was passed through the barrier film antireflection film and the second substrate. An optical laminate is obtained.

<evaluation>

The optical laminates obtained in the examples and the comparative examples were subjected to the following evaluations. The results are shown in Tables 1 and 2.

(1) Storage elastic modulus E'

A phase difference layer (phase difference film) sample having a width of 5 mm × a length of 30 mm was prepared, and its storage elastic modulus E' at -40 ° C to 120 ° C was measured using "DMA RSA-III" manufactured by TA Instruments. The measurement conditions were as follows: a stretching mode, a heating rate of 10 ° C/min, a frequency of 1 Hz, and an initial strain of 0.1%.

(2) Glass transition temperature (Tg) of the resin layer

A resin layer sample having a width of 5 mm × a length of 30 mm was prepared, and the storage elastic modulus E' and the loss elastic modulus E" at -40 ° C to 120 ° C were measured by "DMA RSA-III" manufactured by TA Instruments, according to The peak of tan δ = E" / E' determines its glass transition temperature Tg. The measurement conditions were as follows: tensile mode, heating rate 10 ° C / min, frequency 1 Hz, initial strain 0.1%.

(3) Appearance after heating test

The obtained optical layered body was placed in an oven at 85 ° C for 240 hours, and the change in appearance was visually observed. The distance from the test sample to the eyes of the measurer was set to 5 cm, 30 cm, and 60 cm, and evaluated by the following criteria.

◎ ◎: No color unevenness was observed when the distance between the test sample and the eye of the measurer was 5 cm.

◎: No color unevenness was observed when the distance between the test sample and the eye of the measurer was 30 cm.

○: Color unevenness was slightly observed when the distance between the test sample and the eye of the measurer was 30 cm.

×: Color unevenness was observed when the distance between the test sample and the eye of the measurer was 60 cm.

××: Color unevenness was clearly observed when the distance between the test sample and the eye of the measurer was 60 cm.

(4) Uneven phase difference after heating test

The obtained optical laminate was placed in an oven at 85 ° C for 240 hours. After heating, the phase difference between the in-plane end portion and the in-plane center portion of the optical layered body was measured by "KOBRA-PR" manufactured by Oji Scientific Co., Ltd., and according to the equation (phase difference of the end portion) - (center portion Phase difference) to evaluate the phase difference unevenness.

(5) Dimensional change after heating test

The obtained optical laminate was placed in an oven at 85 ° C for 240 hours. The size of the antireflection film before and after heating was measured using a biaxial length measuring machine manufactured by Mitutoyo Corporation, and the dimensional change caused by heating (size change in the direction in which the polarizing element was extended) was evaluated.

[Industrial availability]

The optical layered body of the present invention is suitably used for an image display device of a liquid crystal display device and an organic EL display device.

10‧‧‧1st substrate

20‧‧‧Anti-reflective film

21‧‧‧Polarized components

22‧‧‧ phase difference layer

23‧‧‧Adhesive layer

24‧‧‧Protective film

30‧‧‧ resin layer

40‧‧‧2nd substrate

100‧‧‧Optical laminate

Claims (7)

An optical laminate comprising: a first substrate; a second substrate disposed on one side of the first substrate; an anti-reflection film disposed between the first substrate and the second substrate; and a resin layer Arranging between the first substrate and the second substrate to cover the anti-reflection film; and the anti-reflection film includes a polarizing element and a phase difference layer adjacent to the polarizing element; and the resin layer is at 25 ° C The storage elastic modulus is 1 × 10 ⁶ Pa or more. The optical layered body of claim 1, wherein the phase difference layer functions as a λ/4 plate. The optical layered body of claim 1, wherein the phase difference layer exhibits an inverse dispersion wavelength characteristic. The optical layered body according to claim 1, wherein the phase difference layer comprises a polycarbonate resin film. The optical layered body according to claim 1, wherein the phase difference layer contains a resin having a photoelastic coefficient of 30 × 10 ^-12 Pa or less. The optical layered body according to claim 1, wherein the retardation axis of the phase difference layer and the absorption axis of the polarizing element form an angle of 35 to 55. The optical layered body according to claim 1, wherein the polarizing element and the retardation layer are laminated via an adhesive layer, and the thickness of the adhesive layer is 1 μm or less.