TW202138178A - Polarization film, image display device and polarization film production method - Google Patents

Abstract

The present invention provides a polarizing film, which can sufficiently inhibit the iodine contained in a polarizer from leaking to the outside under a high temperature and high humidity environment. The polarizing film of the present invention is provided with a polarizer containing iodine and a resin layer, and the resin layer contains a polymer having a structural unit derived from (meth)acrylate. _{The value of y 1} calculated by the following formula (1) for the polarizing film is less than 1.3. y ₁ =(0.279)x ₁ +(-1.51)x ₂ +(0.178)x ₃ +0.386 (1) In formula (1), x ₁ is the rotatable contained in the monomer used to form the polymer The number of bonds, x ₂ is the number of reaction points contained in the monomer, and x ₃ ^{is the polarization term δP (MPa 1/2} ) in the Hansen solubility parameter of the monomer.

Description

Polarizing film, image display device and manufacturing method of polarizing film

The present invention relates to a polarizing film, an image display device and a manufacturing method of the polarizing film.

Image display devices such as liquid crystal display devices and organic EL display devices are provided with a polarizing film for reasons such as the display principle. The polarizing film is, for example, a laminate including a polarizer and a transparent protective film. The polarizer can generally be produced by adsorbing a dichroic dye on a hydrophilic polymer film such as a polyvinyl alcohol (PVA) film, and then uniaxially stretching the film. From the viewpoint of improving the transmittance and polarization of the polarizer, iodine can be widely used as a dichroic dye.

Patent Document 1 discloses an optical laminate in which a polarizer and a protective film are bonded via a hardened layer of a curable resin composition. It can be understood from Patent Document 1 that by appropriately adjusting the content of the alicyclic epoxy compound in the curable resin composition, even when the optical laminate is placed in a high-temperature and high-humidity environment, the iodine of the hardened layer can still be reduced. The content rate is maintained low. Prior art literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2018-169512

The problem to be solved by the invention In a high temperature and humidity environment, the iodine contained in the polarizer tends to move from the polarizer to the transparent protective film, or to the adhesive layer used to attach the polarizer film to the image display panel. Especially when the thickness of the polarizer is small and the iodine concentration in the polarizer is high, the iodine is easily moved from the polarizer to the transparent protective film or the adhesive layer. The iodine moved to the transparent protective film or the adhesive layer will pass through the transparent protective film or the adhesive layer to the outside of the polarizing film. If the iodine content in the polarizer decreases, the degree of polarization of the polarizing film will decrease.

Taking the conventional polarizing film as an example, the iodine contained in the polarizer cannot be sufficiently prevented from leaking to the outside of the polarizing film under a high temperature and high humidity environment. For example, Patent Document 1 focuses on keeping the iodine content in the hardened layer low when the optical laminate is placed in a high-temperature and high-humidity environment. However, Patent Document 1 does not consider that iodine will leak out from the polarizer to the outside of the optical laminate.

Therefore, the object of the present invention is to provide a polarizing film that can sufficiently suppress the iodine contained in the polarizer from leaking to the outside under a high temperature and high humidity environment.

Means to solve the problem After active review by the inventors, it was discovered that the characteristics of the resin layer of the polarizing film can be predicted based on the monomer used to form the polymer contained in the resin layer. According to the review conducted by the inventors, this prediction has particularly high reliability for a resin layer containing a polymer having a structural unit derived from (meth)acrylate. Based on this knowledge, the inventors conducted further studies to complete the present invention.

The present invention provides a polarizing film comprising: a polarizer containing iodine; and a resin layer containing a polymer having a structural unit derived from (meth)acrylate; and the polarizing film is calculated using the following formula (1) The value of y ₁ is less than 1.3. y ₁ =(0.279)x ₁ +(-1.51)x ₂ +(0.178)x ₃ +0.386 (1) In the aforementioned formula (1), x ₁ is the monomer used to form the aforementioned polymer. The number of bonds of rotation, x ₂ is the number of reaction points contained in the monomer used to form the aforementioned polymer, and x ₃ is the polarization in the Hansen solubility parameter of the aforementioned monomer used to form the aforementioned polymer The term δP (MPa ^1/2 ).

In addition, the present invention provides a method of manufacturing a polarizing film, the polarizing film is provided with a polarizer containing iodine and a resin layer, and the resin layer includes a polymer having a structural unit derived from (meth)acrylate; and the foregoing manufacturing method _{It includes the following steps: polymerizing a monomer whose value of y 1} calculated by the following formula (1) is less than 1.3 to obtain the aforementioned polymer. y ₁ =(0.279)x ₁ +(-1.51)x ₂ +(0.178)x ₃ +0.386 (1) In the aforementioned formula (1), x ₁ is the number of rotatable bonds contained in the aforementioned monomer, x ₂ is the number of reaction points contained in the aforementioned monomer, and x ₃ ^{is the polarization term δP (MPa 1/2} ) in the Hansen solubility parameter of the aforementioned monomer.

Furthermore, the present invention provides a polarizing film comprising: a polarizer containing iodine; and a resin layer containing a polymer having a structural unit derived from (meth)acrylate; and the polarizing film uses the following formula (2 ) The calculated _{value of y 2} is less than 1.3. y ₂ =(0.255)x ₁ +(-1.57)x ₂ +(0.151)x ₃ +(-18.0)x ₄ +(0.0987)x ₅ +(-8.26) (2) In the foregoing formula (2), x ₁ is the number of rotatable bonds contained in the monomer used to form the aforementioned polymer, x ₂ is the number of reaction points contained in the aforementioned monomer used to form the aforementioned polymer, and x ₃ is used to form ^{The polarization term δP (MPa 1/2} ) in the Hansen solubility parameter of the aforementioned monomer of the aforementioned polymer, x ₄ is among the aforementioned monomers used to form the aforementioned polymer, among the atoms that function as hydrogen bond acceptors The charge (C) of the most negatively charged atom, x ₅ is used to form the x component (Debye) of the dipole moment of the aforementioned monomer of the aforementioned polymer.

In addition, the present invention provides a method of manufacturing a polarizing film, the polarizing film is provided with a polarizer containing iodine and a resin layer, and the resin layer includes a polymer having a structural unit derived from (meth)acrylate; and the foregoing manufacturing method _{It includes the following steps: polymerizing a monomer whose value of y 2} calculated by the following formula (2) is less than 1.3 to obtain the aforementioned polymer. y ₂ =(0.255)x ₁ +(-1.57)x ₂ +(0.151)x ₃ +(-18.0)x ₄ +(0.0987)x ₅ +(-8.26) (2) In the foregoing formula (2), x ₁ is the number of rotatable bonds contained in the monomer used to form the aforementioned polymer, x ₂ is the number of reaction points contained in the aforementioned monomer used to form the aforementioned polymer, and x ₃ is used to form ^{The polarization term δP (MPa 1/2} ) in the Hansen solubility parameter of the aforementioned monomer of the aforementioned polymer, x ₄ is among the aforementioned monomers used to form the aforementioned polymer, among the atoms that function as hydrogen bond acceptors The charge (C) of the most negatively charged atom, x ₅ is used to form the x component (Debye) of the dipole moment of the aforementioned monomer of the aforementioned polymer.

Invention effect According to the present invention, a polarizing film can be provided, which can sufficiently suppress the iodine contained in the polarizing member from leaking to the outside under a high temperature and high humidity environment.

The details of the present invention will be described below, but the following description is not intended to limit the present invention to specific embodiments.

(Implementation form of polarizing film) As shown in FIG. 1, the polarizing film 10 of this embodiment includes a polarizer 1 containing iodine and a resin layer 2 containing polymer P. The polymer P contained in the resin layer 2 has a structural unit derived from (meth)acrylate. In this specification, "(meth)acrylic acid" means acrylic acid and/or methacrylic acid. For example, the resin layer 2 is located closer to the visibility side than the polarizer 1 and directly contacts the polarizer 1. However, between the resin layer 2 and the polarizer 1, other layers such as an adhesive layer and an easy-to-bond layer may be arranged within a range that does not hinder the effects of the present invention. The resin layer 2 may also be located on the side of the image display panel described later than the polarizer 1. In other words, the polarizer 1 can also be located on the side of the resin layer 2 to be more visible. The resin layer 2 is located, for example, on the outermost side of the polarizing film 10. In addition, in this specification, "film" means a member whose thickness is sufficiently smaller than the length and width.

The polarizing film 10 may further include an adhesive layer 3, a transparent protective film (first transparent protective film) 4, and an adhesive layer 5. The transparent protective film 4 is attached to the polarizer 1 through the adhesive layer 3, for example. The adhesive layer 5 functions, for example, as a member for bonding the polarizing film 10 to an image display panel described later. Therefore, the adhesive layer 5 is, for example, located on the outermost side of the polarizing film 10 and located closer to the image display panel than the polarizing member 1. In other words, the polarizer 1 is, for example, located closer to the visibility side than the adhesive layer 5. The resin layer 2, the polarizer 1, the adhesive layer 3, the transparent protective film 4, and the adhesive layer 5 are arranged in order in the stacking direction, for example.

In the polarizing film 10 of this embodiment, _{the value of y 1} calculated by the following formula (1) is less than 1.3. y ₁ =(0.279)x ₁ +(-1.51)x ₂ +(0.178)x ₃ +0.386 (1)

In the formula (1), x ₁ is the number of rotatable bonds contained in the monomer M used to form the polymer P. x ₁ will be used to predict the extent to which the molecular motion of the polymer P is restricted. In this specification, "rotatable bond" refers to the single bond connecting heavy atoms, excluding the single bond included in the ring structure and the single bond connecting the heavy atom at the terminal to other heavy atoms. Heavy atoms mean atoms other than hydrogen atoms and helium atoms, and specifically include heteroatoms such as nitrogen atoms and oxygen atoms, and carbon atoms. Specific examples of single bonds connecting heavy atoms are carbon-carbon bonds and carbon-heteroatom bonds. For example, when the polymer P is formed of dimethylol-tricyclodecane diacrylate, the value of _{x 1 is 8.} The number of rotatable bonds can also be calculated using software used to calculate molecular descriptors. The software can be Dragon (version7.0), alvaDesc, etc.

When the polymer is formed from a plurality of P-based monomers M, x may be a particular value of ₁ by the following method. First, calculate the number of rotatable bonds for a plurality of monomers M. The calculated number of rotatable bonds is weighted and averaged according to the molar ratio of each monomer M. The resulting weighted average can be regarded as x ₁ . In this embodiment, _{the value of x 1} is not particularly limited, and is, for example, 2-20.

x ₂ is the number of reaction points contained in the monomer M used to form the polymer P. x ₂ will be used as an index for predicting the extent to which the low-molecular-weight compound can pass through the gap of the polymer P. In this specification, "reaction point" refers to a polymerizable group or a crosslinkable group. Specific examples of these groups include groups having polymerizable double bonds such as (meth)acryloyl groups, and crosslinkable functional groups such as epoxy groups and oxetanyl groups. For example, when the polymer P is formed of dimethylol-tricyclodecane diacrylate, the value of _{x 2 is 2.} The number of reaction points can also be calculated using the software described above for calculating molecular descriptors.

When the polymer P is formed from a plurality of monomers M, the following method can be used to specify the value of _{x 2.} First, calculate the number of reaction points for a plurality of monomers M. The calculated number of reaction points is weighted and averaged according to the molar ratio of each monomer M. The resulting weighted average can be regarded as x ₂ . In this embodiment, _{the value of x 2} is not particularly limited, and is, for example, 1 to 6.

x ₃ ^{is the polarization term δP (MPa 1/2} ) in the Hansen solubility parameter of the monomer M used to form the polymer P. x ₃ will be used as an index to predict the interaction between the polymer P and water molecules or iodine. The Hansen solubility parameter refers to the solubility parameter imported by Hildebrand is divided into three components of dispersion term D, polarization term δP, and hydrogen bonding term δH. The polarization term δP represents the energy generated by the dipole moment interaction between molecules. The details of Hansen Solubility Parameters are disclosed in "Hansen Solubility Parameters; A Users Handbook (CRC Press, 2007)". The polarization term δP can be calculated using, for example, well-known software such as HSPiP (version 5). In addition, the value of the polarization term δP may vary slightly depending on the software used. However, the error is usually a magnitude that can be ignored when _{calculating the value of y 1.}

When the polymer is formed from a plurality of P-based monomers M, ₃ may be of particular value x by the following method. ^{First, the polarization term δP (MPa 1/2} ) of the Hansen solubility parameter is calculated for the plural monomers M. The calculated polarization term δP is weighted and averaged according to the molar ratio of each monomer M. The resulting weighted average can be regarded as x ₃ . In this embodiment, _{the value of x 3} is not particularly limited, and is, for example, 1 to 10 (MPa ^1/2 ). The value of x ₃ is preferably 6 (MPa ^1/2 ) or less, more preferably 5 (MPa ^1/2 ) or less, and more preferably 4 (MPa ^1/2 ) or less.

In the polarizing film 10 of this embodiment, _{the value of y 2} calculated by the following formula (2) may be less than 1.3. y ₂ =(0.255)x ₁ +(-1.57)x ₂ +(0.151)x ₃ +(-18.0)x ₄ +(0.0987)x ₅ +(-8.26) (2)

Another aspect of the present invention provides a polarizing film 10 comprising: a polarizer 1 containing iodine; and a resin layer 2, which includes a polymer P having a structural unit derived from (meth)acrylate; and the _{The value of y 2} calculated by formula (2) for the polarizing film is less than 1.3.

In formula (2), x ₁ to x _{3 are the} same as formula (1). _{Therefore, the specific methods of x 1} to x _{3 in} formula (2) are the same as those described previously.

In the formula (2), x ₄ is the charge (C) of the most negatively charged atom among the atoms that function as hydrogen bond acceptors in the monomer M used to form the polymer P. x ₄ will become an index for predicting the interaction between the polymer P and water molecules, that is, an index for predicting the degree of hydrophobicity of the polymer P. The _{closer the value of x 4} is to 0, the more the polymer P tends to be hydrophobic. A hydrogen bond acceptor means an atom that can form a hydrogen bond with a hydrogen atom contained in a water molecule. Examples of atoms functioning as hydrogen bond acceptors include oxygen atoms and nitrogen atoms, which have relatively high electronegativity.

x ₄ can be specified by the following method, for example. First, the monomer M used to form the polymer P is specified. For the monomer M, by performing molecular simulations, the charge (Mulliken charge) of each atom constituting the monomer M can be calculated. Molecular simulation can be performed using known software such as Materials Studio (manufactured by BIOVIA, ver.8.0.0.843) and WebMO (ver.19.0.009e).

Molecular simulation can be performed by the following method, for example. First, use Materials Studio to make a molecular model of monomer M. Regarding the molecular model, the force field of COMPASS (Condensed-phase Optimized Molecular Potentials for Atomistic Simulation Studies) II is used to optimize the structure. Next, the molecular model of monomer M is processed with WebMO. In detail, the Gaussian program (Queue:g09) is used in WebMO to perform structural optimization calculations for the molecular model of monomer M. In this case, B3LYP can be used as a generic function, and 6-31G(d) can also be used as a basis function. Through the above molecular simulation, the charge of each atom constituting the monomer M can be calculated.

Next, among the atoms constituting the monomer M, the atoms functioning as hydrogen bond acceptors are identified. And from the specified atoms, the most negatively charged atom (the atom with the negative charge and the largest absolute value of the charge) is specified. The charge (C) of the atom can be regarded as x ₄ . In addition, when the monomer M does not have an atom that functions as a hydrogen bond acceptor, x ₄ can be regarded as zero.

When the polymer P is formed of a plurality of monomers M, the following method can be used to specify x ₄ . First, for a plurality of monomers M, the charge (C) of the most negatively charged atom among the atoms functioning as hydrogen bond acceptors is specified by the above-mentioned method. The specific charge is weighted and averaged according to the molar ratio of each monomer M. The resulting weighted average can be regarded as x ₄ . When multiple monomers M are structural isomers of each other, the specific charges can also be weighted and averaged according to the molar ratio of each structural isomer, thereby specifying x ₄ . In this embodiment, _{the value of x 4} is not particularly limited, and is, for example, -0.55 to -0.45C.

x ₅ is the x component (Debye) used to form the dipole moment of the monomer M of the polymer P. x ₅ will be an index used to predict the interaction between the polymer P and water molecules, that is, it will be used to predict the degree of hydrophobicity or humidification durability of the polymer P. The _{closer the value of x 5} is to 0, the smaller the dipole moment of the monomer M, and the polymer P tends to be hydrophobic.

x ₅ can be specified by the following method, for example. First, the monomer M used to form the polymer P is specified. For monomer M, the x component of the dipole moment can be calculated by molecular simulation. Molecular simulation may be performed for the previous method described the use of x ₄ Suo. When performing molecular simulations, the internal coordinates of the atoms constituting the monomer M are defined in the form of Z-matrix. When using the Z matrix form, the x-axis, y-axis, and z-axis used to determine the internal coordinates are automatically determined according to the structure of the single M. In addition, the dipole moment is a vector calculated from the x component, the y component, and the z component.

When the polymer P is formed of a plurality of monomers M, the following method can be used to specify x ₅ . First, for a plurality of types of monomers M, the x component of the dipole moment is calculated by the above-mentioned method. For the x component of the calculated dipole moment, weighted and averaged according to the molar ratio of each monomer M. The resulting weighted average can be regarded as x ₅ . When a plurality of monomers M are structural isomers with each other, the calculated dipole moment x component can also be weighted and averaged according to the molar ratio of each structural isomer, thereby specifying x ₅ . In this embodiment, _{the value of x 5} is not particularly limited, and is, for example, -2.0 to 5.0 Debye. The value of x ₅ can be 3.0 Debye or less, or 1.0 Debye or less.

_{The value of y 1} calculated by formula (1) _{and the value of y 2} calculated by formula (2) should be 0.8 or less, more preferably 0.7 or less, more preferably 0.5 or less, and particularly preferably 0.3 or less.

_{The value of y 1} calculated by the formula (1) _{and the value of y 2} calculated by the formula (2) are indicators of the monomer M used to form the polymer P contained in the resin layer 2. However, according to the review of the inventors, _{the value of y 1 and} the value of y ₂ can also be effectively used as indicators for selecting the resin layer 2 suitable for suppressing the iodine contained in the polarizer 1 from leaking to the outside. In addition, the number of factors (x ₁ ~x ₅ ) used to calculate y ₂ is more than the number of factors (x ₁ ~x ₃ ) _{used to calculate y 1.} Generally speaking, the number of factors tends to affect the predictive performance of the predictive formula.

In the polarizing film 10 of the present embodiment, for example, at least one of the following requirements (i) to (v) is satisfied, and it is preferable that the requirement (iii) is satisfied. In the polarizing film 10, all the requirements (i) to (v) may be satisfied. (i) The tensile storage elastic modulus E1 of the resin layer 2 in water at 65°C is 1×10 ⁸ Pa or more. (ii) The tensile storage elastic modulus E2 of the resin layer 2 in water at 85°C is 1×10 ⁸ Pa or more. (iii) When the resin layer 2 is heated from 25°C to 65°C and the measuring gas environment is humidified from 10%RH to 90%RH, the linear expansion coefficient α1 of the resin layer 2 is 400×10 ^-6 /K or less. (iv) When the resin layer 2 is heated from 25°C to 85°C and the measuring gas environment is humidified from 10%RH to 85%RH, the linear expansion coefficient α2 of the resin layer 2 is 300×10 ^-6 /K or less. (v) The dipole moment D of the monomer M used to form the polymer P contained in the resin layer 2 is 2 Debye or less.

First, the requirement (i) is explained. The tensile storage elastic modulus E1 of the resin layer 2 is preferably 5×10 ⁸ Pa or more, more preferably 10×10 ⁸ Pa or more, and more preferably 15×10 ⁸ Pa or more. The upper limit of the tensile storage elastic modulus E1 is not particularly limited, but from the viewpoint of suppressing cracks in the resin layer 2, it may be, for example, 100×10 ⁸ Pa.

The tensile storage elastic modulus E1 of the resin layer 2 can be measured by the following method, for example. First, the resin layer 2 of the evaluation object is cut into a short stick shape with a width of 5 mm and a length of 30 mm to form a test piece. Next, the test piece was set in a commercially available dynamic viscoelasticity measuring device. In this case, use what can immerse the test piece in the solvent as a jig. The distance between the clamps of the fixed test piece is set to 15mm. Then, the test piece was immersed in water. After confirming that the temperature of the test piece is 25°C, the dynamic viscoelasticity of the test piece is measured. The measurement was performed by the tensile vibration-non-resonance method specified in the Japanese Industrial Standards (JIS) K7244-4: 1999. The vibration frequency is set to 1 Hz. From the start of the measurement, the test piece was heated to 95°C at a temperature increase rate of 5°C/min. The measured value of the tensile storage elastic modulus when the temperature of the test piece is 65° C. can be regarded as the tensile storage elastic modulus E1 of the resin layer 2.

Next, the requirement (ii) will be explained. The tensile storage elastic modulus E2 of the resin layer 2 is preferably 5×10 ⁸ Pa or more, more preferably 10×10 ⁸ Pa or more, and more preferably 15×10 ⁸ Pa or more. The upper limit of the tensile storage elastic modulus E2 is not particularly limited, but from the viewpoint of suppressing cracks in the resin layer 2, it may be, for example, 100×10 ⁸ Pa. The tensile storage elastic modulus E2 of the resin layer 2 can be measured, for example, by the same method as the tensile storage elastic modulus E1. In detail, the method described previously for the tensile storage elastic modulus E1 can be used to measure the dynamic viscoelasticity of the test piece. The measured value of the tensile storage elastic modulus at 85°C is regarded as Is the tensile storage elastic modulus E2 of the resin layer 2.

Next, the requirement (iii) will be explained. The resin layer 2 should be a linear expansion coefficient α1 of 200 × 10 ^-6 / K or less, more appropriate to 180 × 10 ^-6 / K or less, more suitably from 150 × 10 ^-6 / K or less, especially appropriate for the 120 × 10 ^{- Below 6} /K. The lower limit of the coefficient of linear expansion α1 is not particularly limited, but from the viewpoint of suppressing cracks in the resin layer 2, for example, it may be 10×10 ^-6 /K.

The coefficient of linear expansion α1 of the resin layer 2 can be measured by the following method, for example. First, the resin layer 2 of the evaluation object is cut into a short stick shape with a width of 5 mm and a length of 30 mm to form a test piece. Next, set the test piece in a commercially available thermomechanical analysis device. At this time, the distance between the clamps of the fixed test piece was set to 15 mm. For the test piece, put it in a measuring gas environment at 25°C and 10%RH for at least 10 minutes. Next, the test piece was heated to 65°C over a period of 60 minutes, and the test piece was held for 10 minutes. Then, it took 30 minutes to humidify the measurement gas environment from 10% RH to 90% RH, and the test piece was kept for 10 minutes. Based on the length change ΔL (mm) of the test piece before and after the test, the linear expansion coefficient α calculated from the following formula (3) can be regarded as the linear expansion coefficient α1 of the resin layer 2. In addition, in formula (3), L ₀ means the length of the test piece at 25° C., and ΔT means the temperature change of the test piece before and after the test. In requirement (iii), ΔT is 40°C. Coefficient of linear expansion α=ΔL/(L ₀ ×ΔT) (3)

Next, the requirement (iv) will be explained. The resin layer 2 should be a linear expansion coefficient α2 of 200 × 10 ^-6 / K or less, more appropriate to 170 × 10 ^-6 / K or less, more suitably from 150 × 10 ^-6 / K or less, especially appropriate for the 100 × 10 ^{- Below 6} /K. The lower limit of the linear expansion coefficient α2 is not particularly limited, but from the viewpoint of suppressing cracks in the resin layer 2, it may be, for example, 10×10 ^-6 /K. The coefficient of linear expansion α2 of the resin layer 2 can be eliminated, for example, that it takes 60 minutes to heat the test piece to 85°C, and it takes 30 minutes to humidify the measuring gas environment from 10%RH to 85%RH. α1 is measured in the same way. In requirement (iv), ΔT in the above formula (3) is 60°C.

Next, the requirement (v) will be explained. The dipole moment D of the monomer M used to form the polymer P is preferably 1.7 Debye or less, more preferably 1.5 Debye or less, and more preferably 1.3 Debye or less. The lower limit of the dipole moment D is not particularly limited, and is 0.5 Debye, for example.

The dipole moment D can be calculated by the following method, for example. First, the monomer M used to form the polymer P is specified. For monomer M, the dipole moment D can be calculated by molecular simulation. Molecular simulation can be performed using known software such as Materials Studio (manufactured by BIOVIA, ver.8.0.0.843) and WebMO (ver.19.0.009e).

The calculation of the dipole moment D by molecular simulation can be performed, for example, by the following method. First, use Materials Studio to make a molecular model of monomer M. Regarding the molecular model, the force field of COMPASS (Condensed-phase Optimized Molecular Potentials for Atomistic Simulation Studies) II is used to optimize the structure. Next, the molecular model of monomer M is processed with WebMO. In detail, the Gaussian program (Queue:g09) is used in WebMO to perform structural optimization calculations for the molecular model of monomer M. In this case, B3LYP can be used as a generic function, and 6-31G(d) can also be used as a basis function. From this, the dipole moment D of the monomer M can be calculated.

When the polymer P is formed of a plurality of monomers M, the following method can be used to specify the dipole moment D. First, for a plurality of types of monomers M, the dipole moments are calculated using the above-mentioned method. The calculated dipole moment is weighted and averaged according to the molar ratio of each monomer M. The resulting weighted average value can be regarded as the dipole moment D. When a plurality of monomers M are structural isomers of each other, the calculated dipole moment can also be weighted and averaged according to the molar ratio of each structural isomer, thereby specifying the dipole moment D.

When at least one of the requirements (i) and (ii) is established, the polymer P contained in the resin layer 2 tends to be maintained in a state of low molecular mobility even in a high temperature and high humidity environment. If the molecular mobility of the polymer P is low, the resin layer 2 will not easily generate a space in which iodine can invade. Thereby, the movement of iodine from the polarizer 1 to the resin layer 2 is suppressed, and there is a tendency to suppress the iodine from penetrating out of the polarizing film 10.

When at least one of the requirements (iii) and (iv) is established, the polymer P contained in the resin layer 2 tends to maintain a small free volume even in a high-temperature and high-humidity environment. If the free volume of the polymer P is small, the resin layer 2 will not easily generate a space in which iodine can invade. Thereby, the movement of iodine from the polarizer 1 to the resin layer 2 is suppressed, and there is a tendency to suppress the iodine from penetrating out of the polarizing film 10.

When the requirement (v) is established, there is a tendency that electrostatic interaction between the polymer P and iodine is unlikely to occur. That is, iodine is not easily attracted by the polymer P. Thereby, the movement of iodine from the polarizer 1 to the resin layer 2 is suppressed, and there is a tendency to suppress the iodine from penetrating out of the polarizing film 10.

[Polarizer] The polarizing member 1 is not particularly limited as long as it contains iodine. Examples include hydrophilic polymer films such as polyvinyl alcohol-based films, partially formalized polyvinyl alcohol-based films, and ethylene-vinyl acetate copolymer-based partially saponified films. And add uniaxial extensions and so on. The polarizing member 1 is preferably composed of a polyvinyl alcohol-based film and iodine.

The thickness of the polarizer 1 is not particularly limited. For example, it is 30 μm or less, preferably 20 μm or less, more preferably 18 μm or less, more preferably 15 μm or less, particularly preferably 12 μm or less, and particularly preferably 10 μm or less. The thickness of the polarizer 1 can be 2 µm or more, 4 µm or more, or 5 µm or more. The thickness of the polarizer 1 can be 7~12µm, 1~7µm depending on the situation, especially 4~6µm. In this specification, the polarizer 1 with a thickness of 10 µm or less may be referred to as a thin polarizer. Thin polarizers tend to have less variation in thickness and excellent visibility. In addition, the thin polarizer has the advantages of suppressing dimensional changes and excellent durability. With the thin polarizer, the polarizing film 10 can be thinned. When the polarizer 1 is a thin polarizer, in order for the polarizing film 10 to have a practically sufficient degree of polarization, the iodine concentration of the polarizer 1 must be adjusted to be high. In the polarizing film 10 of this embodiment, even when the thickness of the polarizing member 1 is small and the iodine concentration of the polarizing member 1 is high, it is still possible to sufficiently suppress the iodine from passing through the polarizing member 1 to the outside.

The polarizer 1 can be produced by, for example, immersing a hydrophilic polymer film such as a polyvinyl alcohol-based film in an aqueous solution of iodine for dyeing, and extending it to 3 to 7 times its original length. The hydrophilic polymer film can also be immersed in an aqueous solution containing boric acid, potassium iodide, etc., if required. More depending on needs, for hydrophilic polymer films, immerse in water for washing before dyeing. By washing the hydrophilic polymer film with water, the dirt or anti-adhesive agent adhering to the surface can be washed away. If the hydrophilic polymer film is washed with water, the hydrophilic polymer film will swell, so it also has the effect of suppressing uneven dyeing. The extension of the hydrophilic polymer film can be carried out after dyeing with iodine, can be carried out while dyeing, or before dyeing with iodine. The extension of the hydrophilic polymer film can be carried out in an aqueous solution containing boric acid, potassium iodide, etc. or in water.

Representative examples of thin polarizers include Japanese Patent Application Publication No. 51-069644, Japanese Patent Application Publication No. 2000-338329, International Publication No. 2010/100917, Japanese Patent Application Publication No. 2014-59328, Japanese Patent Application Publication No. 2012 -73563 Bulletin, etc. These thin polarizers can be manufactured by a manufacturing method including the following steps: a step of stretching a laminate comprising a polyvinyl alcohol-based resin (PVA-based resin) layer and a resin substrate for stretching; and, the resulting stretched film Perform the dyeing steps. In this manufacturing method, the PVA-based resin layer is supported by the resin base material for stretching, so defects such as breakage due to stretching are less likely to occur.

From the point of view that the thin polarizer can be stretched at high magnification and the polarization performance can be improved, the above-mentioned manufacturing method is preferably manufactured by the manufacturing method of the stretching step included in the boric acid aqueous solution, especially by being included in It is preferable to perform the manufacturing method of the auxiliary aerial extension step before the extension step in the boric acid aqueous solution. The manufacturing method of the extension step included in the boric acid aqueous solution has been disclosed in International Publication No. 2010/100917, Japanese Patent Application Publication No. 2014-59328, Japanese Patent Application Publication No. 2012-73563, and the like. The manufacturing method including the step of performing aerial extension has been disclosed in Japanese Patent Laid-Open No. 2014-59328, Japanese Patent Laid-Open No. 2012-73563, and the like.

[Resin layer] As long as the polymer P has a structural unit derived from (meth)acrylate, and _{the value of y 1 calculated by the above formula (1) or the value of y 2} calculated by the formula (2) is less than 1.3, then The resin layer 2 and the polymer P contained in the resin layer 2 are not particularly limited.

The (meth)acrylate can be a monofunctional (meth)acrylate having one (meth)acrylic acid group, or a multifunctional (meth)acrylic acid having two or more (meth)acrylic acid groups ester. The polymer P preferably contains structural units derived from polyfunctional (meth)acrylates. According to the polymer P containing the structural unit derived from the polyfunctional (meth)acrylate, there is a tendency that the migration of iodine from the polarizer 1 to the resin layer 2 can be more suppressed. The number of (meth)acrylic groups contained in the polyfunctional (meth)acrylate is not particularly limited, and is, for example, 2-6, preferably 2-4. If the number of (meth)acrylic groups contained in the polyfunctional (meth)acrylate is too large, unreacted (meth)acrylic groups may remain in the polymer P.

The carbon number of the part other than the (meth)acryloyl group in the (meth)acrylate (hereinafter referred to as the ester part) is not particularly limited. For example, it is 1-18, preferably 4-10. The ester moiety may also contain a ring structure. The ring structure may contain heteroatoms such as nitrogen atoms and oxygen atoms, but is preferably composed only of alicyclic hydrocarbons. The ring structure may be a condensed ring structure such as tricyclodecane or a monocyclic structure such as cyclohexane. In addition, the ring structure may be a lactone ring. The ester moiety may also contain functional groups such as ether groups.

The (meth)acrylate may also contain a polar group, but preferably does not contain a polar group. In this specification, a polar group means a group containing a bond between a hydrogen atom and a heteroatom such as an oxygen atom and a nitrogen atom. Examples of the polar group include a hydroxyl group, a carboxyl group, a primary amino group, and a secondary amino group.

Examples of (meth)acrylates include: dicyclopentyl (meth)acrylate, 4-tert-butylcyclohexyl (meth)acrylate, lauryl (meth)acrylate, 5-(meth)propylene Anoxy-2,6-norbornane carbolactone, 3,3,5-trimethylcyclohexyl (meth)acrylate, 4-tert-butylphenyl (meth)acrylate, (methyl) ) Isobornyl acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl 2-adamantyl (meth)acrylate, 2-isopropyl-2-adamantyl (meth)acrylate, 4-biphenyl (meth)acrylate, 1-(meth)acrylate Naphthyl ester, 2-naphthyl (meth)acrylate, 1-anthracene (meth)acrylate, 1-anthracene methyl (meth)acrylate, 9-anthracene methyl (meth)acrylate and other monofunctional (methyl) ) Acrylate; Dimethylol-tricyclodecane di(meth)acrylate, 1,3-adamantanediol di(meth)acrylate, 1,3,5-adamantantriol-1, 2-functional (meth)acrylates such as 5-di(meth)acrylate, 9,9-bis[4-(2-(meth)acryloyloxyethoxy)phenyl]茀; trimethylol Propane tri (meth) acrylate, glycerol tri (meth) acrylate, 1,3,5-adamantane triol tri (meth) acrylate and other trifunctional (meth) acrylates; neopentaerythritol tetra 4-functional (meth)acrylates such as (meth)acrylate; 6-functional (meth)acrylates such as dineopentaerythritol hexa(meth)acrylate, etc.

The polymer P preferably contains a (meth)acrylate-derived structural unit as a main component, and is substantially composed of a (meth)acrylate-derived structural unit. In this specification, the "main component" means the most structural unit contained in the polymer P on a weight basis. The content of the (meth)acrylate-derived structural unit in the polymer P is, for example, 50% by weight or more, preferably more than 70% by weight, more preferably 80% by weight or more, and more preferably 90% by weight or more, especially It is preferably 95% by weight or more, and particularly preferably 99% by weight or more.

The polymer P may further include structural units derived from other radically polymerizable monomers other than (meth)acrylate, or structural units derived from other anionic monomers other than (meth)acrylate. In addition, the polymer P may contain a structural unit derived from a cationically polymerizable monomer.

Examples of radical polymerizable monomers other than (meth)acrylate include styrene-based compounds. The styrene-based compound includes, for example, an aromatic ring and one or more kinds of vinyl groups. Like (meth)acrylates, the styrenic compound may also contain a polar group, but preferably does not contain a polar group. Examples of styrene-based compounds include styrene, α-methylstyrene, vinylbenzyl chloride, butoxystyrene, vinylpyridine, and the like.

Examples of the cationically polymerizable monomer include vinyl ether compounds, epoxy compounds, and oxetane compounds. Examples of vinyl ether compounds include aliphatic vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether; phenyl vinyl ether, 2-phenoxy Aromatic vinyl ethers such as ethyl vinyl ether and p-methoxyphenyl vinyl ether; butanediol-1,4-divinyl ether, triethylene glycol divinyl ether, dipropylene glycol divinyl ether, etc. Multifunctional vinyl ether, etc.

Examples of epoxy compounds include aromatic epoxy compounds, alicyclic epoxy compounds, and aliphatic epoxy compounds. Examples of aromatic epoxy compounds include: diglycidyl ether compounds of bisphenols (bisphenol type epoxy resins) such as bisphenol A, bisphenol F, and bisphenol S; phenol novolac epoxy resin, cresol novolac ring Novolac epoxy resins such as oxygen resin and hydroxybenzaldehyde phenol novolac epoxy resin; glycidyl ether compounds of polyhydric alcohols such as tetrahydroxyphenylmethane, tetrahydroxydiphenylketone, polyvinylphenol, etc.

Examples of the alicyclic epoxy compound include: vinyl cyclohexene dioxide, 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, azulene dioxide, Bis(3,4-epoxycyclohexylmethyl) adipate, dicyclopentadiene diepoxide, dicyclononadiene diepoxide, tricyclopentadiene diepoxide, dodecahydro -2,6-methyl bridge-2H-oxirano[3',4']cyclopenta[1',2':6,7]naphtho[2,3-b]oxirane etc. .

Aliphatic epoxy compounds include: 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane Triglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, etc.

Examples of the oxetane compound include: 3-ethyl-3-hydroxymethyloxetane, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl Base]benzene, 3-ethyl-3-(phenoxymethyl)oxetane, bis[(3-ethyl-3-oxetanyl)methyl]ether, 3-ethyl -3-(2-ethylhexyloxymethyl)oxetane and the like.

The polymer P preferably contains structural units derived from multifunctional monomers. Examples of the polyfunctional monomer include the aforementioned polyfunctional (meth)acrylates, polyfunctional vinyl ether compounds, polyfunctional epoxy compounds, and polyfunctional oxetane compounds. The content of the structural unit derived from the polyfunctional monomer in the polymer P is, for example, 20% by weight or more, preferably 40% by weight or more, more preferably 50% by weight or more, and may be 70% by weight or more depending on the situation. The upper limit of the content rate of the structural unit derived from a polyfunctional monomer is not specifically limited, For example, it is 95 weight%.

The polymer P may also contain a structural unit derived from a monomer having a polar group, but it is better not to contain it. When the polymer P contains a structural unit derived from a monomer having a polar group, the iodine contained in the polarizer 1 tends to be easily accessible to the resin layer 2. Therefore, the content of the structural unit derived from the monomer having a polar group in the polymer P is preferably 20% by weight or less, more preferably 10% by weight or less, more preferably 5% by weight or less, and particularly preferably 2% by weight the following.

The resin layer 2 contains polymer P as a main component, for example. The content of the polymer P in the resin layer 2 is, for example, 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more, and more preferably 95% by weight or more. It is preferable that the resin layer 2 consists essentially of the polymer P only. However, in addition to the polymer P, the resin layer 2 may also contain additives such as antistatic agents, antioxidants, inorganic particles, and leveling agents.

The thickness of the resin layer 2 is not particularly limited. For example, it is 10 µm or less, preferably 5 µm or less, and more preferably 3 µm or less. From the viewpoint of sufficiently suppressing the iodine contained in the polarizer 1 from leaking to the outside, the thickness of the resin layer 2 is preferably 0.3 µm or more, and may also be 0.5 µm or more.

The resin layer 2 can also be attached to the polarizer 1 through an adhesive layer or an easy-to-bond layer. The adhesive layer for bonding the resin layer 2 to the polarizer 1 can be, for example, the one exemplified for the adhesive layer 3 described later. The easy-adhesive layer may be formed of a resin containing a polymer having, for example, the following skeleton: polyester skeleton, polyether skeleton, polycarbonate skeleton, polyurethane skeleton, polysiloxane, polyamide skeleton, polyamide Amine skeleton, polyvinyl alcohol skeleton, etc. The polymer contained in the resin may be one type or two or more types. The easy bonding layer may also contain additives. Examples of additives include stabilizers such as thickeners, ultraviolet absorbers, antioxidants, and heat-resistant stabilizers. The thickness of the easy bonding layer is not particularly limited, and is preferably 0.01~5µm, more preferably 0.02~2µm, and more preferably 0.05~1µm. The easy bonding layer may also be a laminate of multiple layers.

[Adhesive layer] The adhesive layer 3 is a layer containing an adhesive. The material of the adhesive is not particularly limited, and known materials can be used. Examples of the adhesive contained in the adhesive layer 3 include water-based adhesives and active energy ray-curable adhesives. As the active energy ray-curable adhesive, for example, those disclosed in Japanese Patent Laid-Open No. 2019-147865 and Japanese Patent Laid-Open No. 2016-177248 can be used.

The thickness of the adhesive layer 3 is not particularly limited. For example, it is 3.0 µm or less, preferably 0.01 to 3.0 µm, more preferably 0.1 to 2.5 µm, and more preferably 0.5 to 1.5 µm. If the thickness of the adhesive layer 3 is too small, the cohesive force of the adhesive layer 3 will be insufficient, and the peeling force may decrease. When the thickness of the adhesive layer 3 is too large, if stress is applied to the cross section of the polarizing film 10, the adhesive layer 3 may peel off. That is, there is a case where the polarizing film 10 has a bad peeling caused by impact.

[Transparent protective film] The transparent protective film 4 is preferably one that is excellent in transparency, mechanical strength, thermal stability, moisture barrier properties, and isotropy. The material of the transparent protective film 4 may include, for example, polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate; cellulose-based polymers such as cellulose diacetate and cellulose triacetate; and poly (Meth)acrylic polymers such as methyl methacrylate; styrene polymers such as polystyrene, acrylonitrile-styrene copolymer (AS resin); polycarbonate polymers; polyethylene, polypropylene, Olefin-based polymers such as ethylene-propylene copolymers; cyclic olefin-based polymers such as polynorbornene; vinyl chloride-based polymers; amide-based polymers such as nylon and aromatic polyamides; amide-based polymers; Tungsten polymers; polyether ether polymers; polyether ether ketone polymers; polyphenylene sulfide polymers; vinyl alcohol polymers; vinylidene chloride polymers; vinyl butyral polymers; Arylate-based polymers; polyoxymethylene-based polymers; epoxy-based polymers; mixtures of these polymers, etc.

The transparent protective film 4 preferably contains a polymer that functions as a thermoplastic resin among the above-mentioned polymers. The content of the thermoplastic resin in the transparent protective film 4 is preferably 50% by weight to 100% by weight, more preferably 50% by weight to 99% by weight, more preferably 60% by weight to 98% by weight, and particularly preferably 70% by weight~ 97% by weight. When the content of the thermoplastic resin in the transparent protective film 4 is less than 50% by weight, it may not be able to fully express the original functions of the thermoplastic resin, such as high transparency.

The transparent protective film may also contain one or more additives. Examples of additives include ultraviolet absorbers, antioxidants, slip agents, plasticizers, mold release agents, anti-coloring agents, flame retardants, nucleating agents, antistatic agents, pigments, colorants, and the like.

The transparent protective film 4 may be a polymer film described in Japanese Patent Laid-Open No. 2001-343529, International Publication No. 01/37007, etc. The material of the polymer film may include, for example, a thermoplastic resin having a substituted and/or unsubstituted amide group in the side chain, and a resin having a thermoplastic resin having a substituted and/or unsubstituted phenyl group and a nitrile group in the side chain Composition. A specific example of the polymer film can be a film formed of a resin composition containing an alternating copolymer composed of isobutylene and N-methylmaleimide and an acrylonitrile-styrene copolymer. The film can be obtained, for example, by mixing and extruding a resin composition. Due to the small phase difference and low photoelastic coefficient of the film, the polarizing film 10 can eliminate the unevenness caused by the strain of the polarizing film 10. In addition, the moisture permeability of the film is small, so it has good durability in a humid environment.

The moisture permeability of the transparent protective film 4 is not particularly limited, and is preferably 150 g/m ² /24h or less. At this time, the intrusion of moisture in the air into the inside of the polarizing film 10 can be suppressed, and the change in the moisture content of the polarizing film 10 can be suppressed. Thereby, it is possible to suppress curling or dimensional change of the polarizing film 10 during storage or the like. Examples of materials forming the transparent protective film 4 with low moisture permeability include polyester-based polymers, polycarbonate-based polymers, arylate-based polymers, amide-based polymers, olefin-based polymers, and cyclic olefin-based polymers. Compounds, (meth)acrylic polymers and mixtures of these. The materials for forming the transparent protective film 4 are preferably polycarbonate polymers, cyclic olefin polymers and (meth)acrylic polymers, and particularly cyclic olefin polymers and (meth)acrylic polymers. good.

The thickness of the transparent protective film 4 is not particularly limited, but from the viewpoints of strength and handling properties, it is preferably 5-100 µm, preferably 10-60 µm, and more preferably 13-40 µm.

The surface of the transparent protective film 4 may also be subjected to corona treatment, plasma treatment and other easy bonding treatments in order to improve the adhesion between the components. The transparent protective film 4 can also be provided with an easy-to-bond layer on the surface. As the easy bonding layer, what has been previously described for the resin layer 2 can be used.

[Adhesive layer] The adhesive layer 5 is a layer containing an adhesive. The material of the adhesive is not particularly limited, and it can be used, for example, including (meth)acrylic polymers, silicone polymers, polyesters, polyurethanes, polyamides, polyethers, fluorine polymers, and rubbers. A polymer, etc. as the base polymer. In particular, acrylic adhesives containing (meth)acrylic polymers are excellent in optical transparency, have adequate wettability, cohesiveness, adhesive properties and other adhesive properties, and are excellent in weather resistance, heat resistance, etc., so they are suitable for adhesive layers 5 of materials.

The adhesive layer 5 may also be a laminate of multiple layers with different compositions. The thickness of the adhesive layer 5 is appropriately determined according to the purpose of use, adhesion, etc., for example, 1 to 500 µm, preferably 1 to 200 µm, and preferably 1 to 100 µm. The thickness of the adhesive layer 5 can also be 50 µm or less.

Before the polarizing film 10 is attached to the image display panel, the adhesive layer 5 may have been attached to the separator. With the separating member, the pollution of the adhesive layer 5 can be prevented. As a separator, for example, films such as plastic film, rubber sheet, paper, cloth, non-woven fabric, mesh, foam sheet, metal foil, and laminates of these can be used. According to needs, polysiloxane series, long-chain alkyl films can be used. Those who are coated with release agents such as fluorine-based, fluorine-based, and molybdenum sulfide.

[Other components] The polarizing film 10 may further include other members than the above-mentioned members. For example, the polarizing film 10 may be further provided with a transparent substrate located on the side of the resin layer 2 to be more visible. The transparent substrate may also be located on the outermost side of the polarizing film 10. The transparent substrate is made of glass or polymer, for example. Examples of the polymer constituting the transparent substrate include polyethylene terephthalate, polycycloolefin, and polycarbonate. The thickness of the transparent substrate made of glass is, for example, 0.1 mm to 1 mm. The thickness of the transparent substrate made of polymer is, for example, 10 µm to 200 µm.

The transparent substrate is bonded to the resin layer 2 through an OCA (optical clear adhesive) layer, for example. As the OCA layer, for example, what has been previously described for the adhesive layer 5 can be used. The thickness of the OCA layer should be 150µm or less.

The polarizing film 10 may be further provided with optical films such as a reflective plate, a transmissive plate, a retardation film, a viewing angle compensation film, and a brightness enhancement film. The retardation film includes, for example, a half-wavelength plate, a quarter-wavelength plate, and the like. In the polarizing film 10, the retardation film can be arranged on the side of the image display panel (for example, between the adhesive layer 5 and the transparent protective film 4) more than the polarizer 1 or can be arranged on the side more visible than the polarizer 1.

The polarizing film 10 may be further provided with functional layers such as a hard coating layer, an anti-reflection layer, an anti-sticking layer, a diffusion layer, and an anti-glare layer. In the polarizing film 10, the hard coat layer may also be arranged on the side that is more visible than the resin layer 2.

[Method for manufacturing polarizing film] The method for manufacturing polarizing film 10 is not particularly limited. For example, it includes the following steps: _{polymerizing monomer M whose value of y 1} calculated by the above formula (1) is less than 1.3 to obtain polymer P. The manufacturing method of the polarizing film 10 may also include the following steps instead of the above steps: _{polymerizing the monomer M whose value of y 2} calculated by the above formula (2) is less than 1.3 to obtain the polymer P. In detail, the polarizing film 10 can be manufactured by the following method. First, the polarizer 1 and the transparent protective film 4 are bonded through the adhesive layer 3. Next, a coating liquid containing the above-mentioned monomer M and a polymerization initiator is prepared. The polymerization initiator can be appropriately selected in accordance with the monomer M contained in the coating liquid. The polymerization initiator is preferably a photopolymerization initiator. When the coating liquid contains a cationically polymerizable monomer, a photoacid generator can also be used as a polymerization initiator.

、2-氯9-氧硫𠮿

、2-甲基9-氧硫𠮿

、2,4-二甲基9-氧硫𠮿

、異丙基-9-氧硫𠮿

、2,4-二氯9-氧硫𠮿

、2,4-二乙基9-氧硫𠮿

、2,4-二異丙基9-氧硫𠮿

、十二基9-氧硫𠮿

等的9-氧硫𠮿

系化合物；樟腦醌；鹵化酮；醯基氧化膦；醯基膦酸酯等。As the photopolymerization initiator, for example, diphenyl ethylene dione (benzil), diphenyl ketone, benzoic acid, 3,3'-dimethyl-4-methoxydiphenyl ketone, etc. Phenyl ketone compounds; 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl) ketone, α-hydroxy-α,α'-dimethylacetophenone, 2-methyl- Aromatic ketone compounds such as 2-hydroxypropiophenone and α-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethyl Acetophenone compounds such as oxyacetophenone, 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinylpropan-1-one; benzoin methyl ether , Benzoin ethyl ether, benzoin isopropyl ether, benzoin butyl ether, anisin methyl ether and other benzoin ether compounds; benzyl dimethyl ketal and other aromatic ketals Compounds; Aromatic sulfonyl chloride compounds such as 2-naphthalenesulfonyl chloride; Photoactive oxime compounds such as 1-phenone-1,1-propanedione-2-(o-ethoxycarbonyl)oxime; 9 -Oxygen Sulfur𠮿

, 2-chloro-9-oxysulfur 𠮿

, 2-Methyl 9-oxysulfur 𠮿

, 2,4-Dimethyl 9-oxysulfur 𠮿

, Isopropyl-9-oxysulfur 𠮿

, 2,4-Dichloro 9-oxysulfur 𠮿

, 2,4-Diethyl 9-oxysulfur 𠮿

, 2,4-Diisopropyl 9-oxysulfur 𠮿

, Dodecyl 9-oxysulfur 𠮿

Waiting for 9-oxysulfur 𠮿

Series compounds; camphorquinone; halogenated ketones; acyl phosphine oxide; acyl phosphonate and the like.

Examples of the photoacid generator include compounds represented by the following formula (i). L ⁺ X ^- (i)

In the formula (i), L ^+-based cation; X ^- is selected from consisting of _{^{PF 6 -, SbF 6 -,}} AsF 6 -, SbCl 6 -, BiCl 5 -, SnCl 6 -, ClO 4 -, two thiamin The relative anion in the group consisting of formate anion and SCN ^-.

Specific examples of photoacid generators include "Cyracure-UVI-6992", "Cyracure-UVI-6974" (the above are manufactured by Dow Chemical Japan Co., Ltd.), "ADEKA OPTOMER SP150", and "ADEKA OPTOMER SP152", "ADEKA OPTOMER SP170", "ADEKA OPTOMER SP172" (the above are manufactured by ADEKA Co., Ltd.), "IRGACURE250" (manufactured by Ciba Specialty Chemicals), "CI-5102" , "CI-2855" (The above is made by Soda Corporation of Japan), "SANEIDO SI-60L", "SANEIDO SI-80L", "SANEIDO SI-100L", "SANEIDO SI-110L", "SANEIDO SI-180L" ( The above is manufactured by Sanxin Chemical Co., Ltd.), "CPI-100P", "CPI-100A" (The above is manufactured by Sanya Pro (SAN-APRO) Co., Ltd.), "WPI-069", "WPI-113", "WPI- 116", "WPI-041", "WPI-044", "WPI-054", "WPI-055", "WPAG-281", "WPAG-567", "WPAG-596" (the above are Wako Pure Chemical Company system).

The content of the polymerization initiator in the coating liquid is, for example, 20% by weight or less, preferably 0.01 to 20% by weight, more preferably 0.05 to 10% by weight, and more preferably 0.1 to 5% by weight.

Next, the coating liquid is coated on the polarizing member 1. Thereby, a film (coating film) containing the monomer M and the polymerization initiator can be formed on the polarizer 1. Next, the monomer M is polymerized to form the resin layer 2 from the coating film. The polymerization of the monomer M can be carried out by a known method. For example, when a photopolymerization initiator or a photoacid generator is used as the polymerization initiator, the monomer M can be polymerized by irradiating the coating film with active energy rays. Examples of active energy rays include visible rays and ultraviolet rays. In this specification, the resin layer 2 produced by polymerizing the monomer M contained in the coating film may be referred to as a cured resin layer. Next, the adhesive layer 5 is attached to the transparent protective film 4, whereby the polarizing film 10 can be obtained.

The resin layer 2 can also be produced by the following method. First, the monomer M is polymerized to obtain the polymer P. The obtained polymer P is added to a solvent to prepare a coating liquid. Examples of the solvent include organic solvents that can dissolve or disperse the polymer P. Next, a coating film is produced by coating the coating liquid on the polarizer 1. By drying the coating film, the resin layer 2 can be obtained.

[Characteristics of Polarizing Film] Taking the polarizing film 10 of this embodiment as an example, the iodine contained in the polarizing member 1 can be sufficiently prevented from leaking to the outside under a high temperature and high humidity environment. That is, there is almost no change in the iodine concentration of the polarizer 1 in a high temperature and high humidity environment. The change of the iodine concentration in the polarizing member 1 can be read from the change of the monomer transmittance of the polarizing film 10, for example. For example, in the state where the polarizing film 10 is attached to the alkali-free glass through the adhesive layer 5, the polarizing film 10 is placed in a 65°C 90%RH gas environment for 24 hours. The monomer of the polarizing film 10 The change in transmittance ΔY1 is, for example, 5 or less, preferably 4 or less, preferably 2 or less, more preferably 1.5 or less, and particularly preferably 1 or less.

Specifically, the change in transmittance ΔY1 of the monomer can be measured by the following method. First, the monomer transmittance Ts1 of the laminate obtained by bonding the polarizing film 10 to the alkali-free glass through the adhesive layer 5 is measured. Next, the laminate was placed in a 65°C 90%RH gas environment for 24 hours. The monomer transmittance Ts2 was measured for the laminate after being placed in the gas environment. The value obtained by subtracting the monomer transmittance Ts1 from the monomer transmittance Ts2 is regarded as the change ΔY1 of the monomer transmittance. In addition, the single transmittance of the laminate is the Y value obtained by calibrating the visual sensitivity according to the 2 degree field of view (C light source) of JIS Z8701-1999. The monomer transmittance can be measured using a commercially available spectrophotometer such as DOT-3 manufactured by Murakami Color Research Institute. The measurement wavelength of monomer transmittance is 380~700nm (every 10nm). The alkali-free glass is a glass that does not substantially contain an alkali component (alkali metal oxide). Specifically, the weight ratio of the alkali component in the glass is, for example, 1000 ppm or less, and more preferably 500 ppm or less. The alkali-free glass is, for example, plate-shaped and has a thickness of 0.5 mm or more.

The monomer transmittance Ts1 is not particularly limited. For example, it is 42% to 46%, preferably 43% or more, and more preferably 44% or more. The monomer transmittance Ts2 is not particularly limited. For example, it is 42% to 48%, preferably 47% or less, and more preferably 46% or less.

(Modification of Polarizing Film) In the polarizing film 10, the resin layer 2 may also be located on the side of the image display panel described later than the polarizing member 1. As shown in FIG. 2, in the polarizing film 11 of this modification, the resin layer 2 is located closer to the image display panel than the polarizing member 1. Except for the position of the resin layer 2, the structure of the polarizing film 11 is the same as that of the polarizing film 10. Therefore, the common elements in the polarizing film 10 and the polarizing film 11 of the modified example are given the same reference numerals, and the description thereof is omitted. That is, the following descriptions related to each embodiment can be applied to each other as long as they are not technically contradictory. The following embodiments may be combined with each other as long as they are not technically contradictory.

The resin layer 2 is, for example, located between the polarizer 1 and the adhesive layer 3, and directly contacts the polarizer 1 and the adhesive layer 3, respectively. However, other layers such as an adhesive layer and an easy-to-bond layer may also be arranged between the resin layer 2 and the polarizer 1. For example, the resin layer 2 can also be attached to the polarizer 1 through an adhesive layer or an easy-to-bond layer. Examples of the adhesive layer and the easy-to-bond layer for bonding the resin layer 2 to the polarizer 1 include those previously described for the polarizing film 10. When the resin layer 2 is located closer to the image display panel than the polarizer 1, in a high temperature and humidity environment, the iodine contained in the polarizer 1 can be prevented from moving to the adhesive layer 5 and penetrate the polarizing film 11 through the adhesive layer 5. external.

(Another modification of polarizing film) The polarizing film 10 may further include other members than the above-mentioned members. As shown in FIG. 3, the polarizing film 12 of this modification further has a transparent protective film (second transparent protective film) 6. Except for the second transparent protective film 6, the structure of the polarizing film 12 is the same as that of the polarizing film 10. Therefore, the common elements in the polarizing film 10 and the polarizing film 12 of the modified example are given the same reference numerals, and the description thereof is omitted.

The second transparent protective film 6 is located closer to the viewing side than the polarizer 1. The polarizer 1 is located, for example, between the first transparent protective film 4 and the second transparent protective film 6. The second transparent protective film 6 is, for example, closer to the visibility side than the resin layer 2 and located on the outermost side of the polarizing film 12. However, when the polarizing film 12 includes the above-mentioned transparent substrate, the second transparent protective film 6 may be located between the resin layer 2 and the transparent substrate. The second transparent protective film 6 is in direct contact with the resin layer 2, for example. However, the second transparent protective film 6 may be attached to the resin layer 2 via other layers such as an adhesive layer and a hard coat layer. As the adhesive layer for bonding the second transparent protective film 6 to the resin layer 2, for example, what was previously described for the adhesive layer 3 is mentioned.

As the second transparent protective film 6, what was previously described for the first transparent protective film 4 can be used. The first transparent protective film 4 and the second transparent protective film 6 may be the same or different from each other.

For the polarizing film 12 provided with the second transparent protective film 6, the iodine contained in the polarizing member 1 tends to be more restrained from leaking to the outside under a high temperature and high humidity environment. For example, after the polarizing film 12 is attached to the alkali-free glass through the adhesive layer 5, the polarizing film 12 is placed in an atmosphere of 65°C and 90%RH for 120 hours. The monomer of the polarizing film 12 The change in transmittance ΔY2 is, for example, 3 or less, preferably 2 or less, preferably 1.5 or less, more preferably 1 or less, and particularly preferably 0.8 or less.

Specifically, the change in transmittance ΔY2 of the monomer can be measured by the following method. First, the monomer transmittance Ts3 of the laminate obtained by bonding the polarizing film 12 to the alkali-free glass through the adhesive layer 5 is measured. Next, the laminate was placed in a 65°C 90%RH gas environment for 120 hours. The monomer transmittance Ts4 was measured for the laminate after being placed in the gas environment. The value obtained by subtracting the monomer transmittance Ts3 from the monomer transmittance Ts4 is regarded as the change of the monomer transmittance ΔY2.

The monomer transmittance Ts3 is not particularly limited. For example, it is 42% to 46%, preferably 43% or more, and more preferably 44% or more. The monomer transmittance Ts4 is not particularly limited. For example, it is 42% to 48%, preferably 47% or less, and more preferably 46% or less.

(Another modification of polarizing film) The polarizing film 10 may include two or more resin layers 2. As shown in FIG. 4, the polarizing film 13 of this modification includes two resin layers 2a and 2b. The structure of the polarizing film 13 is the same as that of the polarizing film 10 except for the resin layer 2b. Therefore, the common elements in the polarizing film 10 and the polarizing film 13 of the modified example are given the same reference numerals, and the description thereof is omitted.

In the polarizing film 13, the polarizing member 1 is located between the two resin layers 2a and 2b. In detail, the resin layer 2b is located closer to the image display panel than the polarizer 1 (for example, between the polarizer 1 and the adhesive layer 3). When the polarizer 1 is arranged between the two resin layers 2a and 2b, the polarizing film 13 has a tendency that the iodine contained in the polarizer 1 is more restrained from leaking to the outside.

The resin layer 2b can directly contact the polarizer 1. However, other layers such as an adhesive layer and an easy-to-bond layer may also be arranged between the resin layer 2b and the polarizer 1. For example, the resin layer 2b may also be attached to the polarizer 1 through an adhesive layer or an easy-to-bond layer. As the adhesive layer and the easy-to-bond layer for bonding the resin layer 2b to the polarizing member 1, those described previously for the polarizing film 10 can be cited.

(Implementation form of image display device) As shown in FIG. 5, the image display device 100 of this embodiment includes a polarizing film 10 and an image display panel 20. In the image display device 100, the polarizing film 11, 12 or 13 can also be used instead of the polarizing film 10. In the image display device 100, the polarizing film 10 is attached to the image display panel 20 through the adhesive layer 5, for example. The image display panel 20 may be an organic EL display panel, a liquid crystal display panel, etc., and is preferably an organic EL display panel.

The image display device 100 further includes, for example, an illumination system (not shown). For example, the polarizing film 10, the image display panel 20, and the lighting system are arranged in sequence, and the polarizing film 10 is located on the most visible side. The lighting system has, for example, a backlight or a reflective plate, and irradiates the image display panel 20 with light.

Example The following examples illustrate the present invention in more detail. The present invention is not limited by the examples shown below.

＜Thin Polarizer＞ First, prepare a laminate in which a PVA layer with a thickness of 9 µm is formed on an amorphous polyethylene terephthalate (PET) substrate. With respect to this laminate, a stretched laminate was produced by performing air-assisted stretch at a stretch temperature of 130°C. Next, the stretched laminate was dyed with iodine to obtain a colored laminate. In addition, the colored laminated body was stretched in a boric acid aqueous solution at a stretching temperature of 65 degrees to obtain a laminated body in which an amorphous PET substrate and a PVA layer were integrally stretched. In the laminate, the total extension ratio is 5.94 times, and the thickness of the PVA layer is 5 µm. The PVA molecules of the PVA layer formed on the amorphous PET substrate by the above-mentioned two-stage extension are highly oriented. In addition, the iodine adsorbed by dyeing is highly oriented in one direction in the form of polyiodide ion complexes. The PVA layer contained in the laminate functions as a thin polarizer.

<Transparent protective film> First, a resin composed of an imidized methyl methacrylate-styrene copolymer was prepared using the method described in Production Example 1 of Japanese Patent Application Laid-Open No. 2010-284840 (Imidated MS resin). Next, 100 parts by weight of the imidized MS resin and 0.62 parts by weight of a tri-type ultraviolet absorber (manufactured by ADEKA, trade name: T-712) were mixed at 220°C using a biaxial kneader to prepare resin pellets . The obtained resin pellets were dried in an environment of 100.5 kPa and 100° C. for 12 hours. Next, a uniaxial extruder was used to extrude resin pellets from the T-die at a mold temperature of 270°C to produce a film with a thickness of 160 µm. The thickness of the film is adjusted to 80µm in the direction of conveyance of the film in a 150°C gas environment. Next, after coating the easy-adhesive agent containing the water-based urethane resin on the film, the film was extended in a direction orthogonal to the conveying direction under a gas atmosphere at 150°C, thereby obtaining a transparent protective film with a thickness of 40 µm. The moisture permeability of the transparent protective film is 58 g/m ² /24h.

(日本化藥公司製，商品名：KAYACURE DETX-S)混合並攪拌3小時，藉此獲得活性能量線硬化型接著劑組成物。<Active energy ray curable adhesive composition> 12 parts by weight of hydroxyethyl acrylamide (manufactured by KJ Chemicals Corporation, trade name: HEAA) and 24 parts by weight of 2-hydroxy-3-phenoxypropyl acrylic acid Ester (manufactured by Toagosei Co., Ltd., trade name: ARONIX M-5700), 12 parts by weight of hydroxytrimethylacetate neopentyl glycol acrylate adduct (manufactured by Kyoeisha Chemical Co., Ltd., trade name: LIGHT ACRYLATE HPP-A) ), 38 parts by weight of 1,9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: LIGHT ACRYLATE 1,9ND-A), and 10 parts by weight of acrylic oligomer (manufactured by Toagosei Co., Ltd., Trade name: ARUFON UP-1190), 3 parts by weight of 2-methyl-1-(4-methylphenylsulfanyl)-2-mopholin-1-one (manufactured by IGM Resins, trade name: OMNIRAD 907) and 2 parts by weight of 2,4-diethyl 9-oxysulfur

(Nippon Kayaku Co., Ltd., trade name: KAYACURE DETX-S) was mixed and stirred for 3 hours to obtain an active energy ray hardening type adhesive composition.

<Laminated body containing transparent protective film, adhesive layer and thin polarizer> MCD coater manufactured by Fuji Machinery Co., Ltd. (groove shape: honeycomb shape, gravure roller line number: 1000 lines/inch, rotation speed 140% /To line speed), the active energy ray curable adhesive composition is applied to the bonding surface of the transparent protective film. The thickness of the resulting coating film was 0.7µm. Next, the laminate containing the transparent protective film and the PVA layer was bonded together using a rolling mill. At this time, the coating film is brought into contact with the PVA layer. The production line speed of the roller press is 25m/min. Next, the obtained laminate was irradiated with active energy rays from the side of the transparent protective film. The active energy line uses visible light emitted from a visible light irradiation device (Light HAMMER10 manufactured by Fusion UV Systems). The light source of the visible light irradiation device is a metal halide lamp filled with gallium. The bulb of the visible light irradiation device uses a V bulb. The peak illuminance of the emitted light from the visible light irradiation device is 1600mW/cm ² . In the wavelength range of 380nm~440nm, the cumulative irradiation amount of the emitted light from the visible light irradiation device is 1000mJ/cm ² . The illuminance of the emitted light from the visible light irradiation device was measured using the Sola-Check system manufactured by Solarell. By irradiating the laminate with active energy rays, the active energy ray curable adhesive composition in the coating film is cured. Next, the laminate was dried with hot air at 70° C. for 3 minutes, thereby obtaining a laminate a including a transparent protective film, an adhesive layer, and a thin polarizer.

(日本化藥公司製，商品名：KAYACURE DETX-S)混合，製作出塗佈液。[Example 1] (Polarizing film A) First, 50 parts by weight of dicyclopentyl acrylate (manufactured by Hitachi Chemical Co., Ltd., trade name: FANCRYL FA-513AS) and 50 parts by weight of neopentylerythritol tetraacrylate (total Produced by Eisha Chemical Co., Ltd., trade name: LIGHT ACRYLATE PE-4A), 2 parts by weight of 2-methyl-1-(4-methylphenylthio)-2-mopholin-1-one (IGM Resins Manufactured by the company, trade name: OMNIRAD 907) and 2 parts by weight of 2,4-diethyl 9-oxysulfur

(Nippon Kayaku Co., Ltd., brand name: KAYACURE DETX-S) was mixed to prepare a coating liquid.

Next, the amorphous PET substrate adjacent to the PVA layer was removed from the laminate a. Use Select-Roller #0 (manufactured by OSG SYSTEM PRODUCTS Co., Ltd.) to apply the above-mentioned coating liquid on the exposed PVA layer. The thickness of the resulting coating film is 1 µm. Next, using the visible light irradiation device described above, the coating film was irradiated with visible light under a nitrogen stream, thereby polymerizing the monomer. The coating film is cured by polymerizing the monomer to form a resin layer.

Next, corona treatment was performed on the surface of the transparent protective film. Stick an adhesive layer with a thickness of 20µm on the surface. The adhesive layer is composed of acrylic adhesive. Thereby, a polarizing film A having a resin layer, a polarizer, an adhesive layer, a transparent protective film, and an adhesive layer in this order is obtained.

(Polarizing film B) First, the coating liquid was produced by the same method as the polarizing film A. Use the MCD coating machine made by Fuji Machinery Co. (groove shape: honeycomb shape, gravure roll line: 700 lines/inch, rotation speed 140%/pair line speed), with a thickness of 20 µm tri-cellulose acetate (TAC) Coating liquid is applied to the bonding surface of the film. The thickness of the resulting coating film is 1 µm. Next, the amorphous PET substrate adjacent to the PVA layer was removed from the laminate a. The TAC film and the laminate a were bonded together using a rolling mill. At this time, the coating film is brought into contact with the PVA layer. The production line speed of the roller press is 25m/min. Next, the obtained laminate was irradiated with active energy rays from the TAC film side. The active energy line uses visible light emitted from the above-mentioned visible light irradiation device. By irradiating the laminate with active energy rays, the monomers in the coating film are polymerized. The coating film is hardened by polymerization of monomers. Next, the laminate was dried with hot air at 70°C for 3 minutes. Thus, a resin layer was formed.

Next, corona treatment was performed on the surface of the transparent protective film containing the imidized MS resin. Stick an adhesive layer with a thickness of 20µm on the surface. The adhesive layer is composed of acrylic adhesive. Thereby, a TAC film (the second transparent protective film), a resin layer, a polarizer, an adhesive layer, a transparent protective film containing an imidized MS resin (the first transparent protective film), and an adhesive layer are obtained in this order. Polarizing film B.

[Examples 2-16, Comparative Examples 1, 3 and 5] The monomers contained in the coating solution for forming the resin layer were changed to the monomers described in Table 1, except that the same method as in Example 1 was followed to prepare Examples 2-16, Comparative Examples 1, 3, and 5 Polarizing films A and B.

(日本化藥公司製，商品名：KAYACURE DETX-S)的混合物。[Comparative Example 2] The polarizing films A and B of Comparative Example 2 were produced in the same manner as in Example 1, except that the photocurable resin composition A was used as the coating liquid for forming the resin layer. Light-curable resin composition A is 43 parts by weight of acryloyl mopholine (manufactured by KJ Chemicals Corporation, trade name: ACMO), and 29 parts by weight of 1,9-nonanediol diacrylate (Kyoeisha Chemical Co., Ltd.) Manufactured, trade name: LIGHT ACRYLATE 1,9ND-A), 14 parts by weight of phenoxy diethylene glycol acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: LIGHT ACRYLATE P2H-A), and 10 parts by weight of acrylic acid Oligomer (manufactured by Toagosei Co., Ltd., trade name: ARUFON UP-1190), 2 parts by weight of 2-methyl-1-(4-methylphenylthio)-2-mopholin-1-one ( Produced by IGM Resins, trade name: OMNIRAD 907) and 2 parts by weight of 2,4-diethyl 9-oxysulfur

(Manufactured by Nippon Kayaku Co., Ltd., trade name: KAYACURE DETX-S).

(日本化藥公司製，商品名：KAYACURE DETX-S)的混合物。[Comparative Example 4] The polarizing films A and B of Comparative Example 4 were produced in the same manner as in Example 1, except that the photocurable resin composition B was used as the coating liquid for forming the resin layer. In addition, the photocurable resin composition B is 12 parts by weight of hydroxyethyl acrylamide (manufactured by KJ Chemicals Corporation, trade name: HEAA), and 20 parts by weight of 2-hydroxy-3-phenoxypropyl acrylate ( Toagosei Co., Ltd., trade name: ARONIX M-5700), 12 parts by weight of hydroxytrimethylacetate neopentyl glycol acrylate adduct (Kyoeisha Chemical Co., Ltd., trade name: LIGHT ACRYLATE HPP-A), 34 parts by weight of 1,9-nonanediol diacrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: LIGHT ACRYLATE 1,9ND-A), 10 parts by weight of acrylic oligomer (manufactured by Toagosei Co., Ltd., trade name : ARUFON UP-1190), 5 parts by weight of diethylacrylamide (manufactured by KJ Chemicals Corporation, trade name: DEAA), 3 parts by weight of 2-methyl-1-(4-methylphenylthio)- 2-Mopholin-1-one (manufactured by IGM Resins, trade name: OMNIRAD 907) and 3 parts by weight of 2,4-diethyl 9-oxysulfur

(Manufactured by Nippon Kayaku Co., Ltd., trade name: KAYACURE DETX-S).

＜Change in monomer transmittance ΔY1＞ For the polarizing film A of the examples and comparative examples, the change in monomer transmittance ΔY1 was measured by the following method. First, the polarizing film A is attached to the alkali-free glass through the adhesive layer. The monomer transmittance Ts1 was measured for the obtained laminate. The monomer transmittance Ts1 was measured using a spectroscopic transmittance measuring device with integrating sphere (Dot-3c manufactured by Murakami Color Research Institute). Next, the laminate was placed in a 65°C 90%RH gas environment for 24 hours. With respect to the laminate after being left in this gas environment, the single-body transmittance Ts2 was measured using the above-mentioned spectral transmittance measuring device. The monomer transmittance Ts1 is subtracted from the monomer transmittance Ts2, thereby calculating the change ΔY1 of the monomer transmittance.

＜Change in monomer transmittance ΔY2＞ For the polarizing film B of the embodiment and the comparative example, the monomer transmittance change ΔY2 was measured by the following method. First, the polarizing film B is bonded to the alkali-free glass through the adhesive layer. The monomer transmittance Ts3 was measured for the obtained laminate. The monomer transmittance Ts3 was measured using a spectroscopic transmittance measuring device with integrating sphere (Dot-3c manufactured by Murakami Color Research Institute). Next, the laminate was placed in a 65°C 90%RH gas environment for 120 hours. With respect to the laminate after being left in this gas environment, the single-body transmittance Ts4 was measured using the above-mentioned spectral transmittance measuring device. The monomer transmittance Ts3 is subtracted from the monomer transmittance Ts4 to calculate the change ΔY2 of the monomer transmittance.

_{<The value of y 1} calculated by the formula (1)> For the monomers contained in the coating liquid used in the examples and comparative examples to form the resin layer, the values _{of x 1} to x _{3 are specified by the above method} . In addition, the number of rotatable bonds and the number of reaction points contained in the monomer are calculated using Dragon (version7.0). ^{The polarization term δP (MPa 1/2} ) in the Hansen solubility parameter of the monomer is calculated using HSPiP (version5). And use _{the value of x 1} ~ x ₃ to calculate the value of _{y 1} according to formula (1).

_{<The value of y 2} calculated by the formula (2)> For the monomers contained in the coating solution for forming the resin layer used in the Examples and Comparative Examples, the values _{of x 1} to x _{5 are specified by the above method} . In addition, the number of rotatable bonds and the number of reaction points contained in the monomer are calculated using Dragon (version7.0). ^{The polarization term δP (MPa 1/2} ) in the Hansen solubility parameter of the monomer is calculated using HSPiP (version5). The calculation of the x component of the charge and dipole moment of each atom constituting the monomer was performed using Materials Studio (manufactured by BIOVIA, ver.8.0.0.843) and WebMO (ver.19.0.009e). And use _{the value of x 1} ~ x ₅ to calculate the value of _{y 2} according to formula (2).

＜Tensile storage elastic modulus E1 and E2＞ Regarding the resin layers used in the Examples and Comparative Examples, the tensile storage elastic moduli E1 and E2 were measured by the above-mentioned method. The dynamic viscoelasticity measuring device is a dynamic viscoelasticity measuring device RSA-G2 manufactured by TA Instruments.

＜Linear expansion coefficient α1 and α2＞ Regarding the resin layers used in the Examples and Comparative Examples, the linear expansion coefficients α1 and α2 were measured by the above-mentioned method. The thermomechanical analysis device uses the thermomechanical analysis device TMA 4000 SE manufactured by Netch Company.

＜Dipole moment D＞ With regard to the monomers contained in the coating liquid for forming the resin layer used in the Examples and Comparative Examples, the dipole moment D was calculated by the above-mentioned method. The calculation of the dipole moment D uses Materials Studio (manufactured by BIOVIA, ver.8.0.0.843) and WebMO (ver.19.0.009e).

[Table 1]

In addition, the abbreviations in Table 1 are as follows. FA513AS: Dicyclopentyl acrylate, manufactured by Hitachi Chemical Co., Ltd. TMP-A: Trimethylolpropane triacrylate, manufactured by Kyoeisha Chemical Co., Ltd. TBCHA: 4-tertiary butyl cyclohexyl acrylate, manufactured by KJ Chemicals Corporation DCP-A: Dimethylol-tricyclodecane diacrylate, manufactured by Kyoeisha Chemical Co., Ltd. GBLA: γ-butyrolactone acrylate, manufactured by Osaka Organic Chemical Industry Co., Ltd. ACMO: Acrylic methacrylate, manufactured by KJ Chemicals Corporation PE-4A: Neopentylerythritol tetraacrylate, manufactured by Kyoeisha Chemical Co., Ltd. DPE-6A: Dineopentaerythritol hexaacrylate, manufactured by Kyoeisha Chemical Co., Ltd. 1,9ND-A: 1,9-nonanediol diacrylate, manufactured by Kyoeisha Chemical Co., Ltd. 9EG-A: Polyethylene glycol #400 diacrylate, manufactured by Kyoeisha Chemical Co., Ltd.

It can be seen from Table 1 that _{the value of y 1 calculated by the formula (1) or the value of y 2} calculated by the formula (2) is less than 1.3 in the polarizing film A of the embodiment, the monomer transmittance change ΔY1 is 5 or less, The leakage of iodine to the outside under high temperature and humidity environment is sufficiently suppressed. Similarly, the change ΔY2 of the monomer transmittance of the polarizing film B of the example is 3 or less, and the leakage of iodine to the outside is sufficiently suppressed in a high-temperature and high-humidity environment. On the other hand, compared with the examples, _{the polarizing films A and B of the comparative examples where the value of y 1 and} the value of y ₂ are 1.3 or more have a large change in the transmittance of the monomers, which cannot be sufficiently suppressed in a high temperature and high humidity environment. Iodine leaks to the outside.

In addition, with respect to the monomers contained in the active energy ray-curable resin composition used in Examples 1-4 and Comparative Example 1 of Patent Document 1, the values _{of x 1} to x ₅ , y ₁ and y _{2 were specified by the above-mentioned method.} These active energy ray-curable resin compositions only contain epoxy compounds as monomers, and do not contain (meth)acrylates. The calculated _{values of y 1} and y ₂ cannot sufficiently predict the characteristics of the cured layer of the active energy ray-curable resin composition. This indicates that the equation (1) calculates the sum y ₁ and y is calculated using the equation (2) ₂ are particularly suitable as predictive indicators comprising structural units derived from (meth) acrylate resin of the characteristics of the polymer layers .

Industrial availability The polarizing film of the present invention can be suitably used for, for example, mobile displays such as mobile phones, smart phones, and notebook computers; automotive displays such as panels for car navigation devices, instrument panels, and mirror displays.

1: Polarizing parts 2, 2a, 2b: resin layer 3: Adhesive layer 4: The first transparent protective film 5: Adhesive layer 6: The second transparent protective film 10,11,12,13: Polarizing film 20: Image display panel 100: Video display device

Fig. 1 is a schematic cross-sectional view of a polarizing film according to an embodiment of the present invention. Fig. 2 is a schematic cross-sectional view showing a modification of the polarizing film. Fig. 3 is a schematic cross-sectional view showing another modification of the polarizing film. Fig. 4 is a schematic cross-sectional view showing still another modification of the polarizing film. Fig. 5 is a schematic cross-sectional view of an image display device according to an embodiment of the present invention.

1: Polarizing parts

2: Resin layer

3: Adhesive layer

4: The first transparent protective film

5: Adhesive layer

10: Polarizing film

Claims (19)

A polarizing film comprising: a polarizing member containing iodine; and a resin layer containing a polymer having a structural unit derived from (meth)acrylate; and the polarizing film is calculated using the following formula (1) to calculate the value of y ₁ Value is less than 1.3; y ₁ =(0.279)x ₁ +(-1.51)x ₂ +(0.178)x ₃ +0.386 (1) In the aforementioned formula (1), x ₁ is used to form the aforementioned polymer in the monomer The number of rotatable bonds contained, x ₂ is the number of reaction points contained in the aforementioned monomer used to form the aforementioned polymer, and x ₃ is the Hansen solubility parameter of the aforementioned monomer used to form the aforementioned polymer The polarization term in δP (MPa ^1/2 ). Such as the polarizing film of claim 1, wherein _{the value of y 1} is 0.5 or less. Such as the polarizing film of claim 1 or 2, wherein at least one of the following requirements (i) to (v) is established: (i) The tensile storage elastic modulus E1 of the aforementioned resin layer in water at 65°C is 1. ×10 ⁸ Pa or more; (ii) The tensile storage elastic modulus E2 of the aforementioned resin layer in water at 85°C is 1×10 ⁸ Pa or more; (iii) The aforementioned resin layer is heated from 25°C to 65°C, and When the measured gas environment is humidified from 10%RH to 90%RH, the linear expansion coefficient α1 of the aforementioned resin layer is 400×10 ^-6 /K or less; (iv) The aforementioned resin layer is heated from 25°C to 85°C, and When the measured gas environment is humidified from 10%RH to 85%RH, the linear expansion coefficient α2 of the aforementioned resin layer is 300×10 ^-6 /K or less; (v) The dipole moment of the monomer used to form the aforementioned polymer D is less than 2Debye. The polarizing film according to any one of claims 1 to 3, wherein the content of the aforementioned structural unit derived from the aforementioned (meth)acrylate in the aforementioned polymer is higher than 70% by weight. The polarizing film according to any one of claims 1 to 4, wherein the aforementioned polymer comprises a structural unit derived from a multifunctional monomer. The polarizing film of claim 5, wherein the content of the structural unit derived from the polyfunctional monomer in the polymer is 20% by weight or more. The polarizing film according to any one of claims 1 to 6, wherein the content of the structural unit derived from the monomer having a polar group in the aforementioned polymer is 20% by weight or less. The polarizing film according to any one of claims 1 to 7, wherein the resin layer is located closer to the visual side than the polarizing member. The polarizing film according to any one of claims 1 to 8, wherein the resin layer directly contacts the polarizing member. The polarizing film according to any one of claims 1 to 7, which is provided with two aforementioned resin layers, and The aforementioned polarizer is located between the two aforementioned resin layers. Such as the polarizing film of any one of claims 1 to 10, which is further provided with an adhesive layer and a first transparent protective film, and The polarizer, the adhesive layer, and the first transparent protective film are sequentially arranged in the stacking direction. Such as the polarizing film of claim 11, which further has a second transparent protective film, and The polarizer is located between the first transparent protective film and the second transparent protective film. Such as the polarizing film of any one of claims 1 to 12, which is further provided with an adhesive layer, and The aforementioned polarizer is located closer to the visual side than the aforementioned adhesive layer. An image display device, comprising: the polarizing film according to any one of claims 1 to 13, and an image display panel. A method of manufacturing a polarizing film, the polarizing film is provided with a polarizer containing iodine and a resin layer, and the resin layer includes a polymer having a structural unit derived from (meth)acrylate; and the foregoing manufacturing method includes the following steps: The aforementioned polymer is obtained by polymerizing monomers whose value _{of y 1} is less than 1.3 calculated by the following formula (1) _{; y 1} =(0.279)x ₁ +(-1.51)x ₂ +(0.178)x ₃ +0.386 (1 ) In the aforementioned formula (1), x ₁ is the number of rotatable bonds _{contained in the aforementioned monomer, x 2} is the number of reaction points contained in the aforementioned monomer, and x ₃ is the Hansen solubility of the aforementioned monomer The polarization term in the parameter δP (MPa ^1/2 ). Such as the manufacturing method of claim 15, which further includes the following steps: Forming a film containing the aforementioned monomer and polymerization initiator on the aforementioned polarizing member; and In this manufacturing method, the aforementioned monomer is polymerized to form the aforementioned resin layer from the aforementioned film. The manufacturing method of claim 16, wherein the aforementioned polymerization initiator is a photopolymerization initiator; and In this manufacturing method, the above-mentioned monomer is polymerized by irradiating the above-mentioned film with active energy rays. A polarizing film comprising: a polarizing member containing iodine; and a resin layer containing a polymer having a structural unit derived from (meth)acrylate; and the polarizing film is calculated using the following formula (2) of y ₂ Value is less than 1.3; y ₂ =(0.255)x ₁ +(-1.57)x ₂ +(0.151)x ₃ +(-18.0)x ₄ +(0.0987)x ₅ +(-8.26) (2) The aforementioned formula (2) In ), x ₁ is the number of rotatable bonds contained in the monomer used to form the aforementioned polymer, x ₂ is the number of reaction points contained in the aforementioned monomer used to form the aforementioned polymer, x ₃ ^{It is the polarization term δP (MPa 1/2} ) in the Hansen solubility parameter of the aforementioned monomer used to form the aforementioned polymer, and x ₄ acts as a hydrogen bond acceptor in the aforementioned monomer used to form the aforementioned polymer The charge (C) of the most negatively charged atom among the functional atoms, x ₅ is used to form the x component (Debye) of the dipole moment of the aforementioned monomer of the aforementioned polymer. A method of manufacturing a polarizing film, the polarizing film is provided with a polarizer containing iodine and a resin layer, and the resin layer includes a polymer having a structural unit derived from (meth)acrylate; and the foregoing manufacturing method includes the following steps: The aforementioned polymer is obtained by polymerizing monomers whose _{y 2} value is less than 1.3 calculated by the following formula (2) _{; y 2} =(0.255)x ₁ +(-1.57)x ₂ +(0.151)x ₃ +(-18.0 )x ₄ +(0.0987)x ₅ +(-8.26) (2) In the aforementioned formula (2), x ₁ is the number of rotatable bonds contained in the monomer used to form the aforementioned polymer, and x ₂ is The number of reaction points contained in the aforementioned monomer used to form the aforementioned polymer, x ₃ ^{is the polarization term δP (MPa 1/2} ) in the Hansen solubility parameter of the aforementioned monomer used to form the aforementioned polymer, x ₄ is the charge (C) of the most negatively charged atom among the atoms that function as hydrogen bond acceptors among _{the aforementioned monomers used to form the aforementioned polymer, and x 5} is the charge (C) of the aforementioned monomers used to form the aforementioned polymer The x component of the dipole moment (Debye).

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