JP6896787B2 - Optical film, optical laminate and flexible image display device - Google Patents

Description

The present invention relates to an optical film containing at least one selected from the group consisting of polyimide, polyamide and polyamideimide.

In recent years, optical films containing polyimide resins have been used as functional films for imparting functions to image display devices such as televisions, personal computers, smartphones, tabbeds, and electronic paper. Since a user of such an image display device directly visually recognizes an image displayed visually through an optical film applied to the display device, the optical film is required to have an excellent film appearance.

Poor film appearance includes, for example, defects derived from the composition of the optical film and defects derived from the method for producing the optical film. The former is, for example, a defect in which an additive (more specifically, silica particles or the like) interacts with visible light to impair the appearance. In the latter case, when the optical film is manufactured by the roll-to-roll method having excellent mass productivity, the optical film is not smoothly drawn out from the roll due to improper tacking of the optical film, for example, and the optical films are not fed to each other smoothly. Is a defect that causes scratches on the surface of the optical film due to sliding. Therefore, in the latter case, the feeding stability (unwinding stability) of the optical film is required.

Japanese Unexamined Patent Publication No. 2009-2154412

However, according to the study of the present inventor, the above two appearance defects are in a trade-off relationship, and for example, an optical film containing a polyimide resin and silica particles as described in Patent Document 1 is such. In some cases, it was not possible to achieve both at a high level.

Therefore, an object of the present invention is to provide an optical film having excellent feeding stability and excellent film appearance, and an optical laminate including the optical film and a flexible image display device.

As a result of diligent studies to solve the above problems, the present inventors have conducted reflection (SCE) b * / reflection (SCI) in an optical film containing at least one selected from the group consisting of polyimide, polyamide and polyamide-imide. ) B * was adjusted to a predetermined range to solve the above-mentioned problems, and the present invention was completed. That is, the present invention includes the following aspects.
[1] An optical film containing at least one selected from the group consisting of polyimide, polyamide and polyamide-imide, wherein the formula (1) is used.
0.04 ≤ reflection (SCE) b * / reflection (SCI) b * ≤ 1.50 ... (1)
[In the formula (1), the reflection (SCE) b * indicates b * in the L * a * b * color system of the light reflected by the optical film obtained by the SCE method, and the reflection (SCI) b * is the SCI. Indicates b * in the L * a * b * color system of the light reflected by the optical film obtained by the method]
An optical film that meets the requirements.
[2] Equation (2)
Reflection (SCE) a * / Reflection (SCI) a * ≤ 2.5 ... (2)
[In the formula (2), the reflection (SCE) a * indicates a * in the L * a * b * color system of the light reflected by the optical film obtained by the SCE method, and the reflection (SCI) a * is the SCI. Indicates a * in the L * a * b * color system of the light reflected by the optical film obtained by the method]
The optical film according to [1], which further satisfies the above.
[3] The optical film according to [1] or [2], wherein the haze is 1% or less and the total light transmittance Tt is 85% or more.
[4] The optical film according to any one of [1] to [3], further containing silica particles.
[5] The optical film according to [4], wherein the silica particles are silica particles obtained by subjecting the water-soluble alcohol-dispersed silica sol to a solvent.
[6] The optical film according to any one of [1] to [5], further comprising an ultraviolet absorber.
[7] Further containing silica particles
The three-dimensional distance Ra determined by the Hansen melting sphere method is Eq. (3).
Ra ≤ 8.0 ... (3)
[In formula (3), Ra indicates the three-dimensional distance between the silica particles and at least one selected from the group consisting of the polyimide, the polyamide and the polyamide-imide in the solubility parameter space].
The optical film according to any one of [1] to [6], which satisfies the above conditions.
[8] An optical laminate having the optical film according to any one of [1] to [7] and a hard coat layer on at least one surface of the optical film.
[9] A flexible image display device including the optical laminate according to [8].
[10] The flexible image display device according to [9], further comprising a polarizing plate.
[11] The flexible image display device according to [9] or [10], further including a touch sensor.

According to the present invention, it is possible to provide an optical film having excellent feeding stability and excellent film appearance when used as an optical film in an image display device. Further, according to the present invention, it is possible to provide an optical laminate including an optical film having excellent feeding stability and excellent film appearance, and a flexible image display device.

Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited to the embodiments described here, and various modifications can be made without departing from the spirit of the present invention.

<Optical film>
The optical film of the present invention contains at least one selected from the group consisting of polyimide, polyamide and polyamide-imide, and formula (1).
0.04 ≤ reflection (SCE) b * / reflection (SCI) b * ≤ 1.50 ... (1)
[In the formula (1), the reflection (SCE) b * indicates b * in the L * a * b * color system of the light reflected by the optical film obtained by the SCE method, and the reflection (SCI) b * is the SCI. Indicates b * in the L * a * b * color system of the light reflected by the optical film obtained by the method]
Meet.

[1. Equation (1)]
When the ratio [reflection (SCE) b * / reflection (SCI) b *] of the formula (1) of the optical film of the present invention is 0.1 or more, the surface of the optical film has appropriate smoothness. The film has an appropriate tack, is excellent in feeding stability, and is less likely to cause appearance defects due to sliding between optical films. On the other hand, when the ratio [reflection (SCE) b * / reflection (SCI) b *] of the formula (1) of the optical film of the present invention is 1.9 or less, appearance defects due to the composition of the optical film are unlikely to occur. Therefore, the film appearance is excellent. Therefore, when the formula (1) is satisfied, it has both excellent feeding stability and excellent film appearance. The ratio [reflection (SCE) b * / reflection (SCI) b *] of the formula (1) of the optical film is preferably 0.05 or more, more preferably, from the viewpoint of further improving the feeding stability and / or the appearance of the film. Is 0.1 or more, more preferably 0.13 or more. Further, the ratio [reflection (SCE) b * / reflection (SCI) b *] of the formula (1) of the optical film is preferably 1.4 or less from the viewpoint of further improving the feeding stability and / or the appearance of the film. It is more preferably 1.2 or less, still more preferably 1.1 or less. These plurality of upper limit values and lower limit values can be arbitrarily combined.

(Reflection (SCE) b *)
The reflection (SCE) b * of the optical film is b * in the L * a * b * color system of the light reflected by the optical film, which is obtained by the SCE (Special Component Excluded) method. In the present specification, CIE1976L * a of diffusely reflected light excluding positively reflected light among reflected light with respect to incident light in a wavelength range of 380 to 780 nm, which is incident from a direction tilted by a predetermined angle from the vertical direction of the optical film plane. * B * Refers to the b * value of the color system. The reflection (SCE) b * is preferably −2.5 or higher, preferably -2.4 or higher, and more preferably -2.3 or higher. The reflection (SCE) b * is preferably −0.08 or less, preferably −0.1 or less, and more preferably −0.3 or less. These plurality of upper limit values and lower limit values can be arbitrarily combined. The reflection (SCE) b * of the optical film can be measured, for example, using a spectrophotometer. The measuring method can be measured by the method described in Examples.

(Reflection (SCI) b *)
The reflection (SCI) b * of the optical film is b * in the L * a * b * color system of the light reflected by the optical film, which is obtained by the SCI (Specular Component Integrated) method. In the present specification, CIE1976L * a * b * of reflected light (reflected light including specular reflected light) with respect to incident light in the wavelength range of 380 to 780 nm, which is incident from a direction tilted by a predetermined angle from the vertical direction of the optical film plane. Refers to the b * value of the color system. The reflection (SCI) b * is preferably -2.9 or more, more preferably -2.7 or more, still more preferably -2.5 or more. The reflection (SCI) b * is preferably −1.4 or less, more preferably −1.6 or less, still more preferably −2.0 or less. These plurality of upper limit values and lower limit values can be arbitrarily combined. The reflection (SCI) b * of the optical film can be measured, for example, using a spectrophotometer. The measuring method can be measured by the method described in Examples.

As a means for adjusting the numerical value of the formula (1) within a predetermined numerical range, for example, a means for reducing the interaction between the white light and the components in the optical film can be mentioned. As means for reducing the interaction, for example, the film thickness of the optical film, the addition of additives (more specifically, silica particles, ultraviolet absorbers, whitening agents, etc.), and the characteristics of the additives (more specifically). Specific examples include means for adjusting the particle size, surface modification, content, etc.) within a predetermined range. Among these, the adjustment of the particle size, surface modification, and content of the silica particles makes it possible for the silica particles to be less likely to aggregate in the optical film and to exist in the form of primary particles, so that the silica particles are uniform in the optical film. It becomes easy to disperse in. Then, the interaction with white light due to the uneven shape on the surface of the optical film is reduced, and the interaction between the aggregate and the white light in the optical film is reduced, so that the deterioration of visibility is suppressed (film). It is considered to contribute to the suppression of deterioration of appearance quality).

[2. Equation (2)]
The optical film of the present invention preferably has the formula (2).
Reflection (SCE) a * / Reflection (SCI) a * ≤ 2.5 ... (2)
[In the formula (2), the reflection (SCE) a * indicates a * in the L * a * b * color system of the light reflected by the optical film obtained by the SCE method, and the reflection (SCI) a * is the SCI. Indicates a * in the L * a * b * color system of the light reflected by the optical film obtained by the method]
Meet.
When the optical film satisfies the formula (2), the feeding stability and / or the film appearance of the optical film is further improved. The ratio [reflection (SCE) a * / reflection (SCI) a *] of the formula (2) of the optical film is preferably 2.2 or less from the viewpoint of further improving the feeding stability and / or the film appearance of the optical film. , More preferably 2.0 or less, still more preferably 1.8 or less. Further, the ratio [reflection (SCE) a * / reflection (SCI) a *] of the formula (2) of the optical film is preferably 0. It is 0 or more, more preferably 0.1 or more. These plurality of upper limit values and lower limit values can be arbitrarily combined. As a means for adjusting the numerical value of the formula (2) within a predetermined numerical range, for example, a means for adjusting the numerical value of the above formula (1) within a predetermined numerical range can be mentioned.

(Reflection (SCE) a *)
The reflection (SCE) a * of the optical film is a * in the L * a * b * color system of the light reflected by the optical film determined by the SCE method, and in the present specification, the vertical direction of the optical film plane. Of the reflected light with respect to the incident light in the wavelength range of 380 to 780 nm, which is incident from a direction tilted by a predetermined angle, the a * value of the diffused reflected light excluding the normal reflected light is the a * value of the CIE1976L * a * b * color system. Say. The reflection (SCE) a * is preferably −0.01 or higher, preferably 0.0 or higher. The reflection (SCE) a * is preferably 0.6 or less, preferably 0.5 or less, and more preferably 0.4 or less. These plurality of upper limit values and lower limit values can be arbitrarily combined. The reflection (SCE) a * of the optical film can be measured, for example, using a spectrophotometer. The measuring method can be measured by the method described in Examples.

(Reflection (SCI) a *)
The reflection (SCI) a * of the optical film is a * in the L * a * b * color system of the light reflected by the optical film determined by the SCI method, and in the present specification, the vertical direction of the optical film plane. Refers to the a * value of the CIE1976L * a * b * color system of the reflected light (reflected light including the normal reflected light) with respect to the incident light in the wavelength range of 380 to 780 nm, which is incident from the direction tilted by a predetermined angle. The reflection (SCI) a * is preferably −0.03 or more, more preferably 0.0 or more, and further preferably 0.1 or more. The reflection (SCI) a * is preferably 0.28 or less, more preferably 0.27 or less, still more preferably 0.26 or less. These plurality of upper limit values and lower limit values can be arbitrarily combined. The reflection (SCI) a * of the optical film can be measured, for example, using a spectrophotometer. The measuring method can be measured by the method described in Examples.

[3. Haze]
The haze of the optical film of the present invention is preferably 1% or less, more preferably 0.8% or less, still more preferably 0.5% or less, from the viewpoint of further improving the feeding stability and / or film appearance of the optical film. , Especially preferably 0.3% or less. The haze of the optical film can be measured according to JIS K 7136: 2000. The measuring method will be described in detail in Examples. Since the haze of the optical film indicates the degree of dispersibility of the additive in the optical film, when the haze of the optical film is within the above range, the feeding stability of the optical film and / or the appearance of the film is excellent.

[4. Total light transmittance]
The total light transmittance of the optical film of the present invention is preferably 85% or more, more preferably 87% or more, still more preferably 89% or more. The total light transmittance of the optical film can be measured according to JIS K 7361-1: 1997. The measuring method will be described in detail in Examples. When the total light transmittance of the optical film is within the above numerical range, a sufficient film appearance can be ensured when incorporated into an image display device. Further, when the total light transmittance of the optical film is within the above numerical range, it is possible to easily secure a constant brightness, so that it is possible to suppress the light emission intensity of the display element or the like, and the power consumption of the image display device is consumed. Can be reduced.

[5. Yellowness]
The yellowness of the optical film of the present invention is preferably 3.0 or less, more preferably 2.7 or less, still more preferably 2.5 or less. The yellowness of the optical film can be measured according to JIS K 7373: 2006. The measuring method will be described in detail in Examples.

[6. Film thickness]
The film thickness of the optical film of the present invention is preferably 10 μm or more, more preferably 20 μm or more, still more preferably 30 μm or more. The film thickness is preferably 120 μm or less, more preferably 100 μm or less, still more preferably 80 μm or less, and particularly preferably 60 μm or less. When the film thickness is 30 μm or more, it is advantageous from the viewpoint of internal protection when the optical film is used as a device, and when the film thickness is 120 μm or less, it is advantageous from the viewpoint of folding resistance, cost, transparency and the like. The measuring method will be described in detail in Examples.

[7. Solubility parameter]
The present inventor has found that the composition in the optical film causes aggregation and the like due to poor dispersion and deteriorates the appearance quality of the film, and solutes in solid systems such as optical films (for example, additives, more specifically). A UV absorber, silica particles, whitening agent, etc.) and a medium (for example, a resin, more specifically, at least one resin selected from the group consisting of polyimide, polyamide, and polyamide-imide). The Hansen solubility parameter (hereinafter, may be abbreviated as HSP) was introduced as an index for evaluating the affinity. As a result of diligent studies by the present inventor, the following equations (3) to (5) have been derived. That is, the optical film of the present invention has the formula (3) related to HSP from the viewpoint of suppressing deterioration of film appearance quality (particularly, from the viewpoint of suppressing the occurrence of whitish defects).
Ra ≤ 8.0 ... (3)
[In formula (3), Ra represents the three-dimensional distance between the solute and the medium in the HSP space]
It is preferable to satisfy.
Further, the optical film of the present invention has the formula (4) related to HSP in addition to the formula (3) from the viewpoint of further suppressing the deterioration of the film appearance quality.
Δδ _t ≤ 2.0 ... (4) [In formula (4), Δδ _t represents the difference _{of the total δ t} of the dispersion term, polarity term and hydrogen bond term of HSP between the solute and the medium. ]
, Or formula (5)
Δδ _p ≤ 4.5 ... (5) [In formula (5), Δδ _p represents the difference in _{the polarity term δ p} of HSP between the solute and the medium]
It is more preferable to satisfy.
Further, the optical film of the present invention more preferably satisfies all of the formulas (3) to (5) from the viewpoint of further suppressing the deterioration of the film appearance quality.

(7-1. Method of calculating HSP value)
The HSP value is calculated using the Hansen Solubility Sphere method. The details will be described below. The composition of interest (the solute and the medium) is dissolved or dispersed in a solvent having a known HSP value, and the solubility or dispersibility of the composition in a specific solvent is evaluated. The solubility and dispersibility are evaluated by visually determining whether or not the target composition is dissolved in a solvent and whether or not it is dispersed. This is done for multiple solvents. As the type of the _{solvent, it is preferable to use a solvent having a wide range of δ t} , more specifically, 10 kinds or more, more preferably 15 kinds or more, and further preferably 18 kinds or more. Next, the obtained solubility or dispersibility evaluation results are plotted in a three-dimensional space (HSP space) consisting _{of the dispersion term δ d} , the polarity term δ _p and the hydrogen bond term δ _{h of HSP.} A sphere (Hansen sphere) is created in which a solvent in which the target composition dissolves or disperses is contained inside, and a solvent in which the target composition does not dissolve or disperse is on the outside, and the radius is further minimized. _Let the HSP of the composition targeting the center coordinates (δ _d , δ p, δ _{h) of the obtained Hansen sphere.}

(7-2.δ _t, Δδ _t, method of calculating the .DELTA..delta _p and Ra)
7-1. _{Using the method of calculating HSP value, HSP value (δ d1} , δ _p1 , δ _h1 : HSP of component 1) when two kinds of components in the optical film, for example, resin is component 1 and silica is component 2. It is assumed that the value, δ _d2 , δ _p2 , δ _h2 : HSP value of component 2) is calculated.
HSP variance terms of the total [delta] _t and the total difference .DELTA..delta _t of between components 1 and 2 of the polarity term and hydrogen bond is calculated using the respective formulas (6) and (7). The obtained δ _t corresponds to the HSP of Hildebrand.
δ _t ² = δ _d ² + δ _p ² + δ _h ² ... (6)
Δδ _t = | δ _t2- δ _t1 | ... (7)
Δδ _t is preferably 3.5 or less, more preferably 3.0 or less, still more preferably 2.0 or less, still more preferably 1.0 or less, particularly preferably, from the viewpoint of further suppressing deterioration of film appearance quality. Is 0.5 or less.
_{The difference Δδ p} of the polar terms of HSP between component 1 and component 2 is calculated using the formula (8).
Δδ _p = | δ _p2- δ _p1 | ... (8)
Δδ _p is preferably 4.5 or less, more preferably 3.5 or less, still more preferably 3.0 or less, still more preferably 2.0 or less, particularly preferably, from the viewpoint of further suppressing deterioration of film appearance quality. Is 1.0 or less.
The three-dimensional distance Ra (> 0) between the component 1 and the component 2 in the HSP space is calculated using the equation (9).
Ra ² = 4 (δ _d2- δ _d1 ) ² + (δ _p2- δ _p1 ) ² + (δ _h2- δ _h1 ) ² ... (9)
The smaller the Ra value, the better the affinity between the component 1 and the component 2. The Ra value is preferably 8.0 or less, more preferably 7.0 or less, still more preferably 6.0 or less, still more preferably 5.5 or less, particularly preferably, from the viewpoint of further suppressing deterioration of film appearance quality. Is 5.0 or less.

[8. Polyimide, polyamide, polyamide-imide]
The optical film of the present invention contains at least one resin selected from the group consisting of polyimide-based resins and polyamide-based resins. The polyimide-based resin is a polymer containing a repeating structural unit containing an imide group (hereinafter, may be referred to as polyimide) and a polymer containing a repeating structural unit containing both an imide group and an amide group (hereinafter, referred to as a polyimide). , Polyamidoimide) to be selected from the group consisting of at least one polymer. Further, the polyamide-based resin indicates a polymer containing a repeating structural unit containing an amide group.

The polyimide resin preferably has a repeating structural unit represented by the formula (10). Here, G is a tetravalent organic group and A is a divalent organic group. The polyimide-based resin may contain two or more types of repeating structural units represented by the formula (10), which differ in G and / or A.

The polyimide resin contains one or more selected from the group consisting of the repeating structural units represented by the formulas (11), (12) and (13) as long as the various physical properties of the optical film are not impaired. May be good.

In formulas (10) and (11), G and G ¹ are independently tetravalent organic groups, and may be preferably substituted with a hydrocarbon group or a hydrocarbon group substituted with fluorine. It is an organic group. Examples of G and G ¹ include formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), and formula (28). ) Or a group represented by the formula (29) and a chain hydrocarbon group having a tetravalent carbon number of 6 or less. Since it is easy to suppress the yellowness (YI value) of the optical film, among them, the formula (20), the formula (21), the formula (22), the formula (23), the formula (24), the formula (25), the formula The group represented by (26) or the formula (27) is preferable.

In equations (20) to (29),
* Represents a bond
Z is a single _{bond, -O -, - CH 2 -} , - CH 2 -CH 2 -, - CH (CH 3) -, - C (CH 3) 2 -, - C (CF 3) 2 -, - _{Ar -, - SO 2 -,} - CO -, - O-Ar-O -, - Ar-O-Ar -, - Ar-CH 2 -Ar -, - Ar-C (CH 3) 2 -Ar- , or Represents −Ar−SO ₂ −Ar−. Ar represents an arylene group having 6 to 20 carbon atoms which may be substituted with a fluorine atom, and specific examples thereof include a phenylene group.

In formula (12), G ² is a trivalent organic group, preferably an organic group that may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. The G ^2, equation (20), equation (21), equation (22), equation (23), equation (24), equation (25), equation (26), equation (27), equation (28) or Examples thereof include a group in which any one of the bonds of the group represented by the formula (29) is replaced with a hydrogen atom, and a chain hydrocarbon group having a trivalent carbon number of 6 or less.

In formula (13), G ³ is a divalent organic group, preferably an organic group which may be substituted with a hydrocarbon group or a hydrocarbon group substituted with fluorine. The G ^3, equation (20), equation (21), equation (22), equation (23), equation (24), equation (25), equation (26), equation (27), equation (28) or Among the group bonds represented by the formula (29), a group in which two non-adjacent groups are replaced with hydrogen atoms and a chain hydrocarbon group having 6 or less carbon atoms are exemplified.

In formulas (10) to (13), A, A ¹ , A ² and A ³ are independently divalent organic groups, preferably substituted with a hydrocarbon group or a hydrocarbon group substituted with fluorine. It is an organic group that may be used. As A, A ¹ , A ² and A ³ , the formula (30), the formula (31), the formula (32), the formula (33), the formula (34), the formula (35), the formula (36), the formula ( 37) or a group represented by the formula (38); a group in which they are substituted with a methyl group, a fluoro group, a chloro group or a trifluoromethyl group; and a chain hydrocarbon group having 6 or less carbon atoms are exemplified.

In equations (30) to (38),
* Represents a bond
Z ^{1, Z 2} and ^{Z 3} are each independently a single _{bond, -O -, - CH 2 -} , - CH 2 -CH 2 -, - CH (CH 3) -, - C (CH 3) 2 Represents −, −C (CF ₃ ) _2- , −SO _2- or −CO−.
One example is that Z ¹ and Z ³ are -O- and Z ² is -CH _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- or -SO _2- . is there. It is preferable that the bonding position of Z ¹ and Z ² with respect to each ring and the bonding position of Z ² and Z ³ with respect to each ring are in the meta position or the para position with respect to each ring, respectively.

The polyimide resin is a polyamide-imide having at least a repeating structural unit represented by the formula (10) and a repeating structural unit represented by the formula (13) from the viewpoint of easily improving visibility (film appearance). preferable. Further, the polyamide resin preferably has at least a repeating structural unit represented by the formula (13).

In one embodiment of the present invention, the polyimide-based resin is a diamine and a tetracarboxylic acid compound (a tetracarboxylic acid compound analog such as an acid chloride compound and a tetracarboxylic acid dianhydride), and, if necessary, a dicarboxylic acid compound. (Dicarboxylic acid compound analogs such as acid chloride compounds), tricarboxylic acid compounds (tricarboxylic acid compound analogs such as acid chloride compounds and tricarboxylic acid anhydrides), etc. are reacted (hypercondensation) to obtain condensed polymers. .. The repeating structural unit represented by the formula (10) or the formula (11) is usually derived from a diamine and a tetracarboxylic acid compound. The repeating structural unit represented by the formula (12) is usually derived from a diamine and a tricarboxylic acid compound. The repeating structural unit represented by the formula (13) is usually derived from a diamine and a dicarboxylic acid compound.

In one embodiment of the present invention, the polyamide resin is a condensation type polymer obtained by reacting (polycondensing) a diamine and a dicarboxylic acid compound. That is, the repeating structural unit represented by the formula (13) is usually derived from a diamine and a dicarboxylic acid compound.

Examples of the tetracarboxylic acid compound include aromatic tetracarboxylic acid compounds such as aromatic tetracarboxylic dianhydride; and aliphatic tetracarboxylic acid compounds such as aliphatic tetracarboxylic dianhydride. The tetracarboxylic acid compound may be used alone or in combination of two or more. The tetracarboxylic dian compound may be a tetracarboxylic dian compound analog such as an acid chloride compound in addition to the dianhydride.

Specific examples of aromatic tetracarboxylic dianhydrides include 4,4'-oxydiphthalic acid dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,. 3'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-Diphenylsulfonetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane Dihydride, 2,2-bis (3,4-dicarboxyphenoxyphenyl) propane dianhydride, 4,4'-(hexafluoroisopropyridene) diphthalic acid dianhydride (6FDA), 1,2-bis ( 2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,2-bis (3,4-dicarboxyphenyl) ethane dianhydride , 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride and Examples thereof include 4,4'-(p-phenylenedioxy) diphthalic acid dianhydride and 4,4'-(m-phenylenedioxy) diphthalic acid dianhydride. These can be used alone or in combination of two or more.

Examples of the aliphatic tetracarboxylic dianhydride include cyclic or acyclic aliphatic tetracarboxylic dianhydride. The cyclic aliphatic tetracarboxylic dianhydride is a tetracarboxylic dianhydride having an alicyclic hydrocarbon structure, and specific examples thereof include 1,2,4,5-cyclohexanetetracarboxylic dianhydride. Cycloalkanetetracarboxylic dianhydride such as 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, bicyclo [2.2] .2] Oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, dicyclohexyl3,3', 4,4'-tetracarboxylic dianhydride and their positional isomers can be mentioned. .. These can be used alone or in combination of two or more. Specific examples of the acyclic aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride and the like. These can be used alone or in combination of two or more. Further, a cyclic aliphatic tetracarboxylic dianhydride and an acyclic aliphatic tetracarboxylic dianhydride may be used in combination.

Among the above tetracarboxylic dianhydrides, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2.2.2] octo-7-ene, from the viewpoint of high transparency and low colorability. -2,3,5,6-tetracarboxylic dianhydride and 4,4'-(hexafluoroisopropyridene) diphthalic acid dianhydride, and mixtures thereof are preferred. Further, as the tetracarboxylic acid, a water adduct of the anhydride of the tetracarboxylic acid compound may be used.

Examples of the tricarboxylic acid compound include aromatic tricarboxylic acids, aliphatic tricarboxylic acids, acid chloride compounds related thereto, acid anhydrides, and the like, and two or more of them may be used in combination.
As a specific example, an anhydride of 1,2,4-benzenetricarboxylic acid; 2,3,6-naphthalenetricarboxylic acid-2,3-anhydride; a single bond of phthalic anhydride and benzoic acid, -CH _{2 -, - C (CH 3)} 2 -, - C (CF 3) 2 -, - SO 2 - or a compound linked phenylene group.

Examples of the dicarboxylic acid compound include aromatic dicarboxylic acids, aliphatic dicarboxylic acids, acid chloride compounds related thereto, acid anhydrides, and the like, and two or more of them may be used in combination. Specific examples thereof include terephthalic acid dichloride (terephthaloyl chloride (TPC)); isophthalic acid dichloride; naphthalenedicarboxylic acid dichloride; 4,4'-biphenyldicarboxylic acid dichloride; 3,3'-biphenyldicarboxylic acid dichloride; 4 , 4'-Oxybis (benzoyl chloride) (OBBC); a dicarboxylic acid compound of a chain hydrocarbon having 8 or less carbon atoms and two benzoic acids are single-bonded, -CH _2- , -C (CH ₃ ) _2- , Examples thereof include compounds linked by -C (CF ₃ ) _2- , -SO _{2- or a phenylene group.}

Examples of the diamine include aliphatic diamines, aromatic diamines, and mixtures thereof. In addition, in this embodiment, "aromatic diamine" represents a diamine in which an amino group is directly bonded to an aromatic ring, and an aliphatic group or other substituent may be contained in a part of the structure. The aromatic ring may be a monocyclic ring or a condensed ring, and examples thereof include, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring. Among these, it is preferable that the aromatic ring is a benzene ring. Further, the "aliphatic diamine" represents a diamine in which an amino group is directly bonded to an aliphatic group, and an aromatic ring or other substituent may be contained as a part of the structure thereof.

Examples of the aliphatic diamine include an acyclic aliphatic diamine such as hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, norbornanediamine, 4,4'-. Examples thereof include cyclic aliphatic diamines such as diaminodicyclohexylmethane. These can be used alone or in combination of two or more.

Examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, m-xylylene diamine, p-xylylene diamine, 1,5-diaminonaphthalene, and 2,6-diaminonaphthalene. Aromatic amines having one aromatic ring, such as, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'. -Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis ( 4-Aminophenoxy) benzene, 4,4'-diaminodiphenyl sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [ 4- (4-Aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) benzidine (2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl (TFMB)), 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diaminodiphenyl ether, 3,4 '-Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) fluorene, 9,9-bis (4) Examples thereof include aromatic diamines having two or more aromatic rings, such as −amino-3-chlorophenyl) fluorene and 9,9-bis (4-amino-3-fluorophenyl) fluorene. These can be used alone or in combination of two or more.

Among the above diamines, from the viewpoint of high transparency and low colorability, it is preferable to use one or more selected from the group consisting of aromatic diamines having a biphenyl structure. One selected from the group consisting of 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) benzidine, 4,4'-bis (4-aminophenoxy) biphenyl and 4,4'-diaminodiphenyl ether. It is even more preferable to use the above, and even more preferably to use 2,2'-bis (trifluoromethyl) benzidine.

In the polyimide-based resin, each raw material such as the diamine, the tetracarboxylic acid compound, the tricarboxylic acid compound, and the dicarboxylic acid compound is mixed by a conventional method, for example, a method such as stirring, and then the obtained intermediate is used as an imidization catalyst and an imidization catalyst. It is obtained by imidization in the presence of a dehydrating agent, if necessary. The polyamide resin can be obtained by mixing each of the raw materials such as the diamine and the dicarboxylic acid compound by a conventional method, for example, a method such as stirring.

The imidization catalyst used in the imidization step is not particularly limited, and is, for example, an aliphatic amine such as tripropylamine, dibutylpropylamine, ethyldibutylamine; N-ethylpiperidin, N-propylpiperidin, N-butylpyrolidin. , N-butylpiperidin, and alicyclic amines such as N-propylhexahydroazepine (monocyclic); azabicyclo [2.2.1] heptane, azabicyclo [3.2.1] octane, azabicyclo [2.2] .2] Alicyclic amines (polycyclic) such as octane and azabicyclo [3.2.2] nonane; and 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3- Fragrances such as ethylpyridine, 4-ethylpyridine, 2,4-dimethylpyridine, 2,4,6-trimethylpyridine, 3,4-cyclopentenopyridine, 5,6,7,8-tetrahydroisoquinoline, and isoquinolin. Amine can be mentioned.

The dehydrating agent used in the imidization step is not particularly limited, and examples thereof include acetic anhydride, propionic anhydride, isobutyric anhydride, pivalic acid anhydride, butyric anhydride, and isovaleric acid anhydride.

In the mixing and imidization steps of each raw material, the reaction temperature is not particularly limited, but is, for example, 15 to 350 ° C, preferably 20 to 100 ° C. The reaction time is also not particularly limited, but is, for example, about 10 minutes to 10 hours. If necessary, the reaction may be carried out under conditions of an inert atmosphere or reduced pressure. The reaction may be carried out in a solvent, and examples of the solvent include those used for preparing a varnish. After the reaction, the polyimide resin or the polyamide resin is purified. Examples of the purification method include a method in which a poor solvent is added to the reaction solution, the resin is precipitated by a reprecipitation method, dried to remove the precipitate, and if necessary, the precipitate is washed with a solvent such as methanol and dried. Can be mentioned.
For the production of the polyimide resin, for example, the production method described in JP-A-2006-199945 or JP-A-2008-163107 may be referred to. As the polyimide resin, a commercially available product can be used, and specific examples thereof include Neoprim (registered trademark) manufactured by Mitsubishi Gas Chemical Company, Ltd., KPI-MX300F manufactured by Kawamura Sangyo Co., Ltd., and the like.

The weight average molecular weight of the polyimide resin or the polyamide resin is preferably 200,000 or more, more preferably 250,000 or more, still more preferably 300,000 or more, preferably 600,000 or less, more preferably 500, It is 000 or less. The larger the weight average molecular weight of the polyimide resin or the polyamide resin, the more likely it is that high bending resistance when formed into a film is exhibited. Therefore, from the viewpoint of enhancing the bending resistance of the optical film, it is preferable that the weight average molecular weight is at least the above lower limit. On the other hand, the smaller the weight average molecular weight of the polyimide resin or the polyamide resin, the easier it is to lower the viscosity of the varnish and improve the processability. In addition, the stretchability of the polyimide resin or the polyamide resin tends to be improved. Therefore, from the viewpoint of processability and stretchability, the weight average molecular weight is preferably not more than the above upper limit. In the present application, the weight average molecular weight can be obtained by gel permeation chromatography (GPC) measurement and converted to standard polystyrene, and can be calculated by, for example, the method described in Examples.

The imidization ratio of the polyimide resin is preferably 95 to 100%, more preferably 97 to 100%, still more preferably 98 to 100%, and particularly preferably 100%. From the viewpoint of the stability of the varnish and the mechanical properties of the obtained optical film, the imidization ratio is preferably at least the above lower limit. The imidization rate can be determined by an IR method, an NMR method, or the like. From the above viewpoint, it is preferable that the imidization ratio of the polyimide resin contained in the varnish is within the above range.

In a preferred embodiment of the present invention, the polyimide resin or the polyamide resin contained in the optical film of the present invention contains a halogen atom such as a fluorine atom which can be introduced by, for example, the above-mentioned fluorine-containing substituent or the like. Good. When the polyimide resin or the polyamide resin contains halogen atoms, it is easy to improve the elastic modulus of the optical film and reduce the yellowness (YI value). When the elastic modulus of the optical film is high, it is easy to suppress the occurrence of scratches and wrinkles in the film, and when the yellowness of the optical film is low, it is easy to improve the transparency of the film. The halogen atom is preferably a fluorine atom. Preferred fluorine-containing substituents for containing a fluorine atom in the polyimide-based resin or the polyamide-based resin include, for example, a fluoro group and a trifluoromethyl group.

The content of the halogen atom in the polyimide resin or the polyamide resin is preferably 1 to 40% by mass, more preferably 5 to 40% by mass, still more preferably 5 to 40% by mass, based on the mass of the polyimide resin or the polyamide resin. It is 5 to 30% by mass. When the content of the halogen atom is 1% by mass or more, the elastic modulus at the time of film formation is further improved, the water absorption rate is lowered, the yellowness (YI value) is further reduced, and the transparency is more likely to be improved. When the halogen atom content is 40% by mass or less, the synthesis tends to be easy.

In one embodiment of the present invention, the content of the polyimide resin and / or the polyamide resin in the optical film is preferably 40% by mass or more, more preferably 50% by mass or more, based on the total mass of the optical film. More preferably, it is 70% by mass or more. It is preferable that the content of the polyimide resin and / or the polyamide resin is at least the above lower limit from the viewpoint of easily improving the bending resistance and the like. The content of the polyimide resin and / or the polyamide resin in the optical film is usually 100% by mass or less based on the total mass of the optical film.

[9. Additive]
The optical film of the present invention may further contain additives. Examples of such additives include silica particles, ultraviolet absorbers, whitening agents, silica dispersants, antioxidants, pH regulators, and leveling agents.

(Silica particles)
The optical film of the present invention may further contain silica particles as an additive. The content of the silica particles is preferably 1 part by mass or more, more preferably 3 parts by mass or more, further preferably 5 parts by mass or more, and preferably 60 parts by mass or less, based on the total mass of the optical film. It is preferably 50 parts by mass or less, more preferably 45 parts by mass or less. Further, the content of the silica particles can be combined by selecting an arbitrary lower limit value and upper limit value among these upper limit values and lower limit values. When the content of the silica particles is within the numerical range of the upper limit value and / or the lower limit value, the silica particles are less likely to aggregate in the optical film of the present invention and tend to be uniformly dispersed in the state of the primary particles. It is possible to suppress a decrease in visibility of the optical film of the present invention.

The particle size of the silica particles is preferably 1 nm or more, more preferably 3 nm or more, further preferably 5 nm or more, particularly preferably 8 nm or more, preferably 30 nm or less, more preferably 28 nm or less, still more preferably 25 nm or less, particularly. It is preferably 20 nm or less. The particle size of the silica particles can be combined by selecting any lower limit value and upper limit value among these upper limit values and lower limit values. When the content of silica particles is in the numerical range of the upper limit value and / or the lower limit value, it is difficult for the optical film of the present invention to interact with light of a specific wavelength in white light. It is possible to suppress a decrease in visibility. In the present specification, the particle size of silica particles indicates the average primary particle size. The particle size of the silica particles in the optical film can be measured by imaging with a transmission electron microscope (TEM). The particle size of the silica particles before the optical film is produced (for example, before being added to the varnish) can be measured by a laser diffraction type particle size distribution meter. The method for measuring the particle size of the silica particles will be described in detail in Examples.

Examples of the form of the silica particles include a silica sol in which the silica particles are dispersed in an organic solvent and the like, and a silica powder prepared by a vapor phase method. Among these, silica sol is preferable from the viewpoint of workability.

The silica particles may be surface-treated, and may be, for example, silica particles obtained by substituting a solvent (more specifically, γ-butyrolactone, etc.) with a water-soluble alcohol-dispersed silica sol. The water-soluble alcohol is an alcohol having 3 or less carbon atoms per hydroxy group in one water-soluble alcohol molecule, and examples thereof include methanol, ethanol, 1-propanol, and 2-propanol. Although it depends on the compatibility between the silica particles and the type of polyimide polymer, when the silica particles are surface-treated, the affinity with the polyimide polymer contained in the optical film is usually improved, and the dispersibility of the silica particles is improved. Therefore, it is possible to suppress a decrease in visibility of the present invention.

(UV absorber)
The optical film of the present invention may further contain an ultraviolet absorber. For example, a triazine-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a benzoate-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, and the like can be mentioned. These may be used alone or in combination of two or more. Suitable commercially available UV absorbers include, for example, Sumisorb® 340 manufactured by Sumika Chemtex Co., Ltd., ADEKA STAB® LA-31 manufactured by ADEKA Corporation, and BASF Japan Co., Ltd. Chinubin (registered trademark) 1577 and the like can be mentioned. The content of the ultraviolet absorber is preferably 1 phr or more and 10 phr or less, more preferably 3 phr or more and 6 phr or less, based on the mass of the optical film of the present invention.

(Whitening agent)
The optical film of the present invention may further contain a whitening agent. The whitening agent can be added to adjust the color when an additive other than the whitening agent is added, for example. Examples of the whitening agent include monoazo dyes, triarylmethane dyes, phthalocyanine dyes, and anthraquinone dyes. Among these, anthraquinone dyes are preferable. Suitable commercially available whitening agents include, for example, Macrolex® Violet B manufactured by LANXESS, Sumiplast® Violet B manufactured by Sumika Chemtex Co., Ltd., and Diaresin manufactured by Mitsubishi Chemical Corporation. (Registered trademark) Blue G and the like can be mentioned. These may be used alone or in combination of two or more. The content of the whitening agent is preferably 5 ppm or more and 40 ppm or less based on the mass of the optical film of the present invention.

[10. Optical film manufacturing method]

The use of the optical film of the present invention is not particularly limited, and it may be used for various purposes. As described above, the optical film of the present invention may be a single layer or a laminated body, the optical film of the present invention may be used as it is, or a laminated body with another film. May be used as. Since the optical film of the present invention has excellent surface quality, it is useful as an optical film in an image display device or the like.

The optical film of the present invention is useful as a front plate of an image display device, particularly a front plate (window film) of a flexible display. The flexible display has, for example, a flexible functional layer and the polyimide-based film that is superposed on the flexible functional layer and functions as a front plate. That is, the front plate of the flexible display is arranged on the visible side above the flexible functional layer. This front plate has a function of protecting the flexible functional layer.

[11. Optical film manufacturing method]
The optical film of the present invention is not particularly limited, but for example, the following steps:
(A) A step of preparing a liquid containing the resin and the filler (hereinafter, may be referred to as varnish) (varnish preparation step).
(B) A step of applying varnish to a base material to form a coating film (coating step), and (c) a step of drying the applied liquid (coating film) to form an optical film (optical film forming step). )
It can be manufactured by a method including.

In the varnish preparation step, the varnish is prepared by dissolving the resin in a solvent, adding the filler and, if necessary, other additives, and stirring and mixing. When silica is used as the filler, a silica sol obtained by substituting a dispersion liquid of silica sol containing silica with a solvent in which the resin can be dissolved, for example, a solvent used for preparing the following varnish may be added to the resin.

The solvent used for preparing the varnish is not particularly limited as long as the resin can be dissolved. Examples of such a solvent include amide-based solvents such as N, N-dimethylacetamide and N, N-dimethylformamide; lactone-based solvents such as γ-butyrolactone (GBL) and γ-valerolactone; dimethyl sulfoxide, dimethyl sulfoxide, sulfolane and the like. Sulfur-containing solvent; carbonate solvent such as ethylene carbonate and propylene carbonate; and combinations thereof. Among these, an amide solvent or a lactone solvent is preferable. These solvents can be used alone or in combination of two or more. Further, the varnish may contain water, an alcohol solvent, a ketone solvent, an acyclic ester solvent, an ether solvent and the like. The solid content concentration of the varnish is preferably 1 to 25% by mass, more preferably 5 to 20% by mass.

In the coating step, a varnish is applied onto the substrate by a known coating method to form a coating film. Known coating methods include, for example, wire bar coating method, reverse coating, roll coating method such as gravure coating, die coating method, comma coating method, lip coating method, spin coating method, screen coating method, fountain coating method, dipping method, and the like. Examples include a spray method and a salivation molding method.

In the optical film forming step, the optical film can be formed by drying the coating film and peeling it from the base material. After the peeling, a drying step of further drying the optical film may be performed. The coating film can be dried at a temperature of usually 50 to 350 ° C. If necessary, the coating film may be dried under an inert atmosphere or under reduced pressure conditions.

Examples of the base material are a SUS plate for metal, PET film, PEN film for resin, other polyimide resin or polyamide resin film, cycloolefin polymer (COP) film, acrylic film. And so on. Among them, PET film, COP film and the like are preferable from the viewpoint of excellent smoothness and heat resistance, and PET film is more preferable from the viewpoint of adhesion to an optical film and cost.

<Optical laminate>
The optical laminate of the present invention has the optical film of the present invention and a hard coat layer (protective film) on at least one of the optical films. The optical laminate may further have an adhesive layer. The optical laminate of the present invention may be formed, for example, by adhering the optical film of the present invention and the hard coat layer via an adhesive layer.

(Hard coat layer)
The thickness of the hard coat layer is not particularly limited and may be, for example, 2 to 100 μm. When the thickness of the hard coat layer is within the above range, sufficient scratch resistance can be ensured, bending resistance is unlikely to decrease, and the problem of curl generation due to curing shrinkage tends to be less likely to occur. ..
The hard coat layer can be formed by curing a hard coat composition containing a reactive material capable of forming a crosslinked structure by irradiation with active energy rays or by applying heat energy, and those by irradiation with active energy rays are preferable. Active energy rays are defined as energy rays that can generate active species by decomposing compounds that generate active species, and are visible light, ultraviolet rays, infrared rays, X-rays, α rays, β rays, γ rays, and electron beams. And the like, preferably ultraviolet rays. The hard coat composition contains at least one polymer of a radically polymerizable compound and a cationically polymerizable compound.

The radically polymerizable compound is a compound having a radically polymerizable group. The radically polymerizable group contained in the radically polymerizable compound may be a functional group capable of causing a radical polymerization reaction, and examples thereof include a group containing a carbon-carbon unsaturated double bond, and specifically, a vinyl group. , (Meta) acryloyl group and the like. When the radically polymerizable compound has two or more radically polymerizable groups, these radically polymerizable groups may be the same or different from each other. The number of radically polymerizable groups contained in one molecule of the radically polymerizable compound is preferably 2 or more from the viewpoint of improving the hardness of the hard coat layer. Examples of the radically polymerizable compound include compounds having a (meth) acryloyl group, preferably from the viewpoint of high reactivity, and specifically, 2 to 6 (meth) acryloyl groups in one molecule. Compounds called polyfunctional acrylate monomers and epoxy (meth) acrylates, urethane (meth) acrylates, and polyester (meth) acrylates have a molecular weight of several hundreds of (meth) acryloyl groups in the molecule. Thousands of oligomers are mentioned, preferably one or more selected from epoxy (meth) acrylates, urethane (meth) acrylates and polyester (meth) acrylates.

The cationically polymerizable compound is a compound having a cationically polymerizable group such as an epoxy group, an oxetanyl group, and a vinyl ether group. The number of cationically polymerizable groups contained in one molecule of the cationically polymerizable compound is preferably 2 or more, more preferably 3 or more, from the viewpoint of improving the hardness of the hard coat layer.
Further, as the cationically polymerizable compound, a compound having at least one of an epoxy group and an oxetanyl group as the cationically polymerizable group is preferable. A cyclic ether group such as an epoxy group or an oxetanyl group is preferable because the shrinkage associated with the polymerization reaction is small. Further, among the cyclic ether groups, compounds having an epoxy group are easily available, compounds having various structures are easily available, the durability of the obtained hard coat layer is not adversely affected, and the affinity with the radically polymerizable compound is easily controlled. There is an advantage. Further, among the cyclic ether groups, the oxetanyl group tends to have a higher degree of polymerization than the epoxy group, accelerates the network formation rate obtained from the cationically polymerizable compound of the obtained hard coat layer, and is mixed with the radically polymerizable compound. There are advantages such as forming an independent network without leaving unreacted monomers in the film even in the region where the polymer is formed.
Examples of the cationically polymerizable compound having an epoxy group include polyglycidyl ether of a polyhydric alcohol having an alicyclic ring, or a cyclohexene ring or cyclopentene ring-containing compound with an appropriate oxidizing agent such as hydrogen peroxide or peracid. Alicyclic epoxy resin obtained by epoxidation; polyglycidyl ether of aliphatic polyhydric alcohol or its alkylene oxide adduct, polyglycidyl ester of aliphatic long chain polybasic acid, homopolymer of glycidyl (meth) acrylate, An aliphatic epoxy resin such as a copolymer; a glycidyl ether produced by reacting bisphenols such as bisphenol A, bisphenol F and hydrogenated bisphenol A, or derivatives such as their alkylene oxide adducts and caprolactone adducts with epichlorohydrin And novolak epoxy resin, and examples thereof include glycidyl ether type epoxy resin derived from bisphenols.

The hard coat composition may further contain a polymerization initiator. Examples of the polymerization initiator include a radical polymerization initiator, a cationic polymerization initiator, a radical and a cationic polymerization initiator, and the like, which are appropriately selected and used. These polymerization initiators are decomposed by at least one of active energy ray irradiation and heating to generate radicals or cations to promote radical polymerization and cation polymerization.
The radical polymerization initiator may be any as long as it can release a substance that initiates radical polymerization by at least one of irradiation with active energy rays and heating. For example, examples of the thermal radical polymerization initiator include organic peroxides such as hydrogen peroxide and perbenzoic acid, and azo compounds such as azobisbutyronitrile.
Active energy ray radical polymerization initiators include Type 1 radical polymerization initiators, which generate radicals by decomposition of molecules, and Type 2 radical polymerization initiators, which coexist with tertiary amines and generate radicals by hydrogen abstraction type reaction. Yes, they are used alone or in combination.
The cationic polymerization initiator may be any one as long as it can release a substance that initiates cationic polymerization by at least one of activation energy ray irradiation and heating. As the cationic polymerization initiator, an aromatic iodonium salt, an aromatic sulfonium salt, a cyclopentadienyl iron (II) complex and the like can be used. These can initiate cationic polymerization by either irradiation with active energy rays or heating, depending on the structure.

The content of the polymerization initiator is preferably 0.1 to 10% by mass with respect to 100% by mass of the entire hard coat composition. When the content of the polymerization initiator is in the above range, curing can proceed sufficiently, and the mechanical properties and adhesive strength of the finally obtained coating film can be in a good range. , Poor adhesive strength due to curing shrinkage, cracking phenomenon and curling phenomenon tend to be less likely to occur.

The hard coat composition can further contain one or more selected from the group consisting of solvents and additives.
The solvent can dissolve or disperse the polymerizable compound and the polymerization initiator, and any solvent known as a solvent for hard coat compositions in the present art does not impair the effects of the present invention. In the range, it can be used.
The additive may further contain inorganic particles, a leveling agent, a stabilizer, a surfactant, an antistatic agent, a lubricant, an antifouling agent and the like.

The laminate of the present invention can be used, for example, in a flexible image display device, and is particularly preferably used in a foldable display device and a rollable display device.

(Manufacturing method of an optical laminate having a circularly polarizing plate)
An example of a method for manufacturing an optical laminate having a circularly polarizing plate will be described. When manufacturing an optical laminate having a circularly polarizing plate including a polarizing layer / a retardation layer in this order, first, an optical film, a polarizing layer, and a retardation layer are separately formed. An optical film is produced by the method described above. For example, an alignment layer, a polarizer, and a protective layer are laminated in this order on a protective film as a base material to form a polarizing layer. Further, the λ / 4 retardation plate and the positive C plate are bonded together with an adhesive to form a retardation layer.
Next, the formed optical film, polarizing layer, and retardation layer are bonded together using an adhesive to produce an optical laminate having a circular polarizing plate. In bonding the polarizing layer and the retarding layer, the polarizing layer and the retarding layer are separated so that the absorption axis of the polarizing layer is substantially 45 ° with respect to the slow axis (optical axis) of the retarding layer. Let them stick together. In this way, the optical film / adhesive layer / polarizing layer (protective film / alignment layer / polarizer / protective layer) / adhesive layer / retardation layer (λ / 4 retardation plate / positive C plate) are laminated in this order. It is possible to manufacture an optical laminate having a circularly polarizing plate.

The optical laminate having the circularly polarizing plate of the present invention (hereinafter, also referred to as a laminate) includes the optical film of the present invention.
(Equation (39))
The laminate having the circularly polarizing plate of the present invention has the formula (39).
Transmission b * -reflection (SCE) b * ≧ 4.0 ... (39)
[In the formula (39), the transmitted b * indicates b * in the L * a * b * color system of the light transmitted through the laminated body, and the reflected (SCE) b * indicates the laminated body obtained by the SCE method. Indicates b * in the L * a * b * color system of the reflected light]
Meet. When the formula (39) is satisfied, the laminated body having the circularly polarizing plate of the present invention has excellent visibility because the light transmission from the light source is large and the reflection of external light is small, which is close to the neutral hue. ..
The numerical value of the formula (39) (transmission b * -reflection (SCE) b *) is preferably 4.2 or more, more preferably 4.5, from the viewpoint of further improving the visibility of the laminated body having the circularly polarizing plate. Above, more preferably 5.0 or more, particularly preferably 6.5 or more.

(Transparent b *)
The transmission b * of the laminated body having the circular polarizing plate is b * in the L * a * b * color system of the light transmitted through the laminated body having the circular polarizing plate, and in the present specification, it has the circular polarizing plate. CIE1976L * a * b * B * value of the transmitted light with respect to the incident light (white light) in the wavelength range of 380 to 780 nm, which is incident from the vertical direction of the laminated body plane. The transmission b * is preferably 4.0 or more, more preferably 5.0 or more, still more preferably 6.0 or more. The transmission b * of the laminate having a circularly polarizing plate can be measured using an ultraviolet-visible near-infrared spectrophotometer, for example, by the method described in Examples.

(Reflection (SCE) b *)
The reflection (SCE) b * of the laminated body having the circular polarizing plate is b * in the L * a * b * color system of the light reflected from the laminated body having the circular polarizing plate, which is obtained by the SCE method. In the specification, diffused reflected light excluding normal reflected light among the reflected light with respect to the incident light in the wavelength range of 380 to 780 nm, which is incident from the direction inclined by a predetermined angle from the vertical direction of the laminate plane having the circular polarizing plate. CIE1976L * a * b * Refers to the b * value of the color system. The reflection (SCE) b * is preferably 1.5 or less, preferably 1.0 or less, more preferably 0 or less, and particularly preferably -1.5 or less. The reflection (SCE) b * of the circularly polarizing plate can be measured using a spectrophotometer, for example, by the method described in Examples.
(Reflection (SCI) b *)
The reflection (SCI) b * of the circular polarizing plate is b * in the L * a * b * color system of the light reflected by the circular polarizing plate obtained by the SCI method, and in the present specification, the circular polarizing plate plane. CIE1976L * a * b * CIE1976L * a * b * color system b * value of the reflected light (reflected light including normal reflected light) for the incident light in the wavelength range of 380 to 780 nm, which is incident from the direction tilted by a predetermined angle from the vertical direction Say. The reflection (SCI) b * of the circularly polarizing plate can be measured using a spectrophotometer, for example, by the method described in Examples.

As a means for adjusting the transmission b * -reflection (SCE) b * in the formula (39) within a predetermined numerical range, for example, the transmission b * -reflection (SCE) b * of the optical film is the numerical value of the formula (1). Means for adjusting within the range and hue adjustment by changing the composition of the optical film can be mentioned.

<Flexible image display device>
The flexible image display device of the present invention includes the optical laminate of the present invention. For example, the flexible image display device includes an optical laminate (a laminate for a flexible image display device) and an organic EL display panel, and the flexible image display device laminate is arranged on the visual side with respect to the organic EL display panel. , It is configured to be foldable. The laminated body for a flexible image display device may further contain a window, a polarizing plate, and a touch sensor, and the stacking order thereof is arbitrary, but the window, the polarizing plate, the touch sensor or the window, and the touch sensor are viewed from the visual side. , It is preferable that the polarizing plates are laminated in this order. The presence of a polarizing plate on the visual side of the touch sensor is preferable because the pattern of the touch sensor is difficult to see and the visibility of the displayed image is improved. Each member can be laminated using an adhesive, an adhesive, or the like. Further, a light-shielding pattern formed on at least one surface of any layer of the window, the polarizing plate, and the touch sensor can be provided. The polarizing plate may be a circular polarizing plate.

(Window)
The window is arranged on the visual side of the flexible image display device, and plays a role of protecting other components from external impacts or environmental changes such as temperature and humidity. Conventionally, glass has been used as such a protective layer, but the window in the flexible image display device is not rigid and hard like glass, but has flexible characteristics. The window is made of a flexible transparent substrate and may include a hard coat layer on at least one surface. The hard coat layer optionally included in the window is synonymous with the hard coat layer of the above-mentioned optical laminate.

(Transparent base material)
The transmittance of the transparent substrate in the visible region is usually 70% or more, preferably 80% or more. As the transparent substrate, any transparent polymer film can be used as long as it does not impair the effects of the present invention. Specifically, as the polymer film used, polyolefins such as cycloolefin-based derivatives having a monomer unit containing polyethylene, polypropylene, polymethylpentene, norbornene or cycloolefin, diacetylcellulose, triacetylcellulose, etc. (Modified) celluloses such as propionyl cellulose, acrylics such as methyl methacrylate (co) polymer, polystyrenes such as styrene (co) polymer, acrylonitrile / butadiene / styrene copolymers, acrylonitrile / styrene copolymers , Ethylene-vinyl acetate copolymers, polyvinyl chlorides, polyvinylidene chlorides, polyethylene terephthalates, polybutylene terephthalates, polyethylene naphthalates, polycarbonates, polyesters such as polyarylates, polyamides such as nylon, polyimides, polyamides Examples of films such as imides, polyetherimides, polyether sulfones, polysulfones, polyvinyl alcohols, polyvinyl acetals, polyurethanes, and epoxy resins are preferable because they are excellent in transparency and heat resistance. , Polyethyleneimide, Polyethylene, Polyester, Olefin, Acrylic or Cellulosic films. Each of these polymers can be used alone or in combination of two or more. These films are used unstretched or as uniaxially or biaxially stretched films.
It is also preferable to disperse inorganic particles such as silica, organic fine particles, rubber particles and the like in the polymer film. In addition, colorants such as pigments and dyes, optical brighteners, dispersants, plasticizers, heat stabilizers, light stabilizers, infrared absorbers, UV absorbers, antistatic agents, antioxidants, lubricants, solvents, etc. May contain a combination of the above. The thickness of the transparent substrate is usually 5 to 200 μm, preferably 20 to 100 μm.

(Polarizer)
A polarizing plate, particularly a circular polarizing plate, is a functional layer having a function of transmitting only a right or left circularly polarized light component by laminating a λ / 4 retardation plate on a linear polarizing plate. For example, the external light is converted to right-handed circularly polarized light and reflected by the organic EL panel to block the left-handed circularly polarized light, and only the light emitting component of the organic EL is transmitted to suppress the influence of the reflected light. It is used to make it easier to see. In order to achieve the circularly polarized light function, the absorption axis of the linear polarizing plate and the slow axis of the λ / 4 retardation plate need to be theoretically 45 °, but practically, they are 45 ± 10 °. The linear polarizing plate and the λ / 4 retardation plate do not necessarily have to be laminated adjacent to each other, and the relationship between the absorption axis and the slow phase axis may satisfy the above range. It is preferable to achieve perfect circularly polarized light at all wavelengths, but it is not always necessary in practical use. Therefore, the circularly polarizing plate in the present invention also includes an elliptical polarizing plate. It is also preferable to further laminate a λ / 4 retardation film on the visible side of the linear polarizing plate to convert the emitted light into circularly polarized light to improve the visibility when wearing polarized sunglasses.

The linear polarizing plate is a functional layer having a function of transmitting light vibrating in the transmission axis direction but blocking polarization of a vibration component perpendicular to the linear polarizing plate. The linear polarizing plate may be configured to include a linear polarizing element alone or a linear polarizing element and a protective film attached to at least one surface thereof. The thickness of the linear polarizing plate may be 200 μm or less, preferably 0.5 to 100 μm. If the thickness is within the above range, the flexibility tends to be difficult to decrease.
The linear polarizer may be a film-type polarizer produced by dyeing and stretching a polyvinyl alcohol (PVA) -based film. A dichroic dye such as iodine is adsorbed on the PVA-based film oriented by stretching, or the dichroic dye is oriented in a state of being adsorbed on the PVA to exhibit polarization performance. In the production of the film-type polarizer, other steps such as swelling, cross-linking with boric acid, washing with an aqueous solution, and drying may be included. The stretching and dyeing steps may be performed on the PVA-based film alone, or may be performed in a state of being laminated with another film such as polyethylene terephthalate. The thickness of the PVA-based film used is preferably 10 to 100 μm, and the draw ratio is preferably 2 to 10 times.
Further, as another example of the polarizer, a liquid crystal coating type polarizer formed by coating a liquid crystal polarizing composition may be used. The liquid crystal polarizing composition may contain a liquid crystal compound and a dichroic dye compound. The liquid crystal compound may have a property of exhibiting a liquid crystal state, and is particularly preferable when it has a higher-order orientation state such as a smectic phase because it can exhibit high polarization performance. It is also preferable that the liquid crystal compound has a polymerizable functional group.

The dichroic dye is a dye that is oriented together with the liquid crystal compound to exhibit dichroism, and the dichroic dye itself may have liquid crystal properties or has a polymerizable functional group. You can also do it. Any compound in the liquid crystal polarizing composition has a polymerizable functional group.
The liquid crystal polarizing composition can further contain an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a cross-linking agent, a silane coupling agent and the like.
The circular polarizing plate may be a liquid crystal polarizing layer. The liquid crystal polarizing layer is manufactured by applying a liquid crystal polarizing composition on an alignment film to form a liquid crystal polarizing layer.
The liquid crystal polarizing layer can be formed to be thinner than the film-type polarizing element. The thickness of the liquid crystal polarizing layer may be preferably 0.5 to 10 μm, more preferably 1 to 5 μm.
The alignment film can be produced, for example, by applying an alignment film forming composition on a base material and imparting orientation by rubbing, polarized light irradiation, or the like. The alignment film forming composition may contain a solvent, a cross-linking agent, an initiator, a dispersant, a leveling agent, a silane coupling agent, and the like in addition to the alignment agent. As the alignment agent, for example, polyvinyl alcohols, polyacrylates, polyamic acids, and polyimides can be used. When applying photo-orientation, it is preferable to use an orientation agent containing a synnamate group. The weight average molecular weight of the polymer used as the alignment agent may be about 10,000 to 1,000,000. The thickness of the alignment film is preferably 5 to 10,000 nm, and more preferably 10 to 500 nm from the viewpoint of orientation regulating force. The liquid crystal polarizing layer can be peeled off from the base material, transferred and laminated, or the base material can be laminated as it is. It is also preferable that the base material serves as a protective film, a retardation plate, and a transparent base material for windows.

The protective film may be a transparent polymer film, and the materials and additives used for the transparent substrate can be used. Cellulose-based films, olefin-based films, acrylic films, and polyester-based films are preferable. It may be a coating type protective film obtained by applying a cationic curing composition such as an epoxy resin or a radical curing composition such as acrylate and curing the film. If necessary, plasticizers, UV absorbers, infrared absorbers, colorants such as pigments and dyes, optical brighteners, dispersants, heat stabilizers, light stabilizers, antistatic agents, antioxidants, lubricants, solvents, etc. May include. The thickness of the protective film may be 200 μm or less, preferably 1 to 100 μm. When the thickness of the protective film is within the above range, the flexibility of the protective film is unlikely to decrease. The protective film can also serve as a transparent substrate for the window.

The λ / 4 retardation plate is a film that gives a phase difference of λ / 4 in a direction orthogonal to the traveling direction of incident light (in-plane direction of the film). The λ / 4 retardation plate may be a stretch-type retardation plate manufactured by stretching a polymer film such as a cellulose-based film, an olefin-based film, or a polycarbonate-based film. Phase difference adjusters, plasticizers, UV absorbers, infrared absorbers, colorants such as pigments and dyes, optical brighteners, dispersants, heat stabilizers, light stabilizers, antioxidants, antioxidants as needed , Lubricants, solvents and the like may be contained. The thickness of the stretchable retardation plate may be 200 μm or less, preferably 1 to 100 μm. When the thickness is in the above range, the flexibility of the film tends to be difficult to decrease.
Further, as another example of the λ / 4 retardation plate, a liquid crystal coating type retardation plate formed by coating a liquid crystal composition may be used. The liquid crystal composition contains a liquid crystal compound having a property of exhibiting a liquid crystal state such as nematic, cholesteric, and smectic. Any compound, including the liquid crystal compound in the liquid crystal composition, has a polymerizable functional group. The liquid crystal coating type retardation plate can further contain an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a cross-linking agent, a silane coupling agent, and the like. The liquid crystal coating type retardation plate can be manufactured by coating and curing a liquid crystal composition on an alignment film to form a liquid crystal retardation layer in the same manner as described in the liquid crystal polarizing layer. The liquid crystal coating type retardation plate can be formed to be thinner than the stretch type retardation plate. The thickness of the liquid crystal polarizing layer may be usually 0.5 to 10 μm, preferably 1 to 5 μm. The liquid crystal coating type retardation plate can be peeled off from the base material, transferred and laminated, or the base material can be laminated as it is. It is also preferable that the base material serves as a protective film, a retardation plate, and a transparent base material for windows.

In general, there are many materials that exhibit a larger birefringence as the wavelength becomes shorter and a smaller birefringence as the wavelength becomes longer. In this case, since it is not possible to achieve a phase difference of λ / 4 in the entire visible light region, an in-plane phase difference of 100 to 180 nm, preferably 130, is λ / 4 with respect to the vicinity of 560 nm, which has high visual sensitivity. It is often designed to be ~ 150 nm. It is preferable to use a reverse dispersion λ / 4 retardation plate using a material having a birefringence wavelength dispersion characteristic opposite to the usual one because visibility can be improved. As such a material, it is also preferable to use the material described in JP-A-2007-232873 in the case of a stretch-type retardation plate and in JP-A-2010-30979 in the case of a liquid crystal-coated retardation plate. ..
Further, as another method, a technique for obtaining a wideband λ / 4 retardation plate by combining with a λ / 2 retardation plate is also known (Japanese Patent Laid-Open No. 10-90521). The λ / 2 retardation plate is also manufactured by the same material method as the λ / 4 retardation plate. The combination of the stretchable retardation plate and the liquid crystal coating type retardation plate is arbitrary, but it is preferable to use the liquid crystal coating type retardation plate in both cases because the thickness can be reduced.
A method of laminating a positive C plate on the circularly polarizing plate in order to improve visibility in an oblique direction is also known (Japanese Patent Laid-Open No. 2014-224738). The positive C plate may be a liquid crystal coating type retardation plate or a stretched retardation plate. The phase difference in the thickness direction is usually −200 to −20 nm, preferably −140 to −40 nm.

(Touch sensor)
The touch sensor is used as an input means. As the touch sensor, various types such as a resistance film method, a surface acoustic wave method, an infrared method, an electromagnetic induction method, and a capacitance method have been proposed, and any method may be used. Of these, the capacitance method is preferable. The capacitive touch sensor is divided into an active region and an inactive region located outside the active region. The active area is an area corresponding to the area where the screen is displayed on the display panel (display unit), the area where the user's touch is sensed, and the inactive area is the area where the screen is not displayed on the display device (non-active area). This is the area corresponding to the display unit). The touch sensor is formed on a substrate having flexible characteristics; a sensing pattern formed in an active region of the substrate; and is formed in an inactive region of the substrate, and is connected to an external drive circuit via the sensing pattern and a pad portion. Each sensing line for can be included. As the substrate having flexible characteristics, the same material as the transparent substrate of the window can be used. The substrate of the touch sensor preferably has a toughness of 2,000 MPa% or more from the viewpoint of suppressing cracks in the touch sensor. More preferably, the toughness may be 2,000 to 30,000 MPa%. Here, toughness is defined as the lower area of the curve to the fracture point by the stress-strain curve obtained through the tensile experiment of the polymer material.

The sensing pattern can include a first pattern formed in the first direction and a second pattern formed in the second direction. The first pattern and the second pattern are arranged in different directions from each other. The first pattern and the second pattern are formed in the same layer, and each pattern must be electrically connected in order to sense the touched point. The first pattern is a form in which the unit patterns are connected to each other via a joint, but the second pattern has a structure in which the unit patterns are separated from each other into an island form, so that the second pattern is electrically connected. A separate bridge electrode is required for connection. A well-known transparent electrode material can be applied to the sensing pattern. For example, indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium zinc oxide oxide (IZTO), indium gallium zinc oxide (IGZO), cadmium tin oxide (CTO). , PEDOT (poly (3,4-ethylenedioxythiophene)), carbon nanotubes (CNT), graphene, metal wire and the like, and these can be used alone or in combination of two or more. ITO can be preferably used. The metal used for the metal wire is not particularly limited, and examples thereof include silver, gold, aluminum, copper, iron, nickel, titanium, telenium, and chromium. These can be used alone or in combination of two or more.

The bridge electrode can be formed on the upper part of the insulating layer via the insulating layer on the upper part of the sensing pattern, the bridge electrode is formed on the substrate, and the insulating layer and the sensing pattern can be formed on the bridge electrode. The bridge electrode can also be formed of the same material as the sensing pattern and is made of a metal such as molybdenum, silver, aluminum, copper, palladium, gold, platinum, zinc, tin, titanium or an alloy of two or more of these. You can also do it. Since the first pattern and the second pattern must be electrically insulated, an insulating layer is formed between the sensing pattern and the bridge electrode. The insulating layer can be formed only between the joint of the first pattern and the bridge electrode, or can be formed in a layer structure covering the sensing pattern. In the latter case, the bridge electrode can connect the second pattern through a contact hole formed in the insulating layer. The touch sensor has a difference in transmittance between a patterned region in which a pattern is formed and a non-patterned region in which a pattern is not formed, specifically, a light transmittance induced by a difference in refractive index in these regions. An optical control layer can be further included between the substrate and the electrode as a means for appropriately compensating for the difference, and the optical control layer can include an inorganic insulating material or an organic insulating material. The optical control layer can be formed by coating a photocurable composition containing a photocurable organic binder and a solvent on a substrate. The photocurable composition may further contain inorganic particles. The inorganic particles can increase the refractive index of the optical control layer.
The photocurable organic binder may contain, for example, a copolymer of each monomer such as an acrylate-based monomer, a styrene-based monomer, and a carboxylic acid-based monomer. The photocurable organic binder may be, for example, a copolymer containing different repeating units such as an epoxy group-containing repeating unit, an acrylate repeating unit, and a carboxylic acid repeating unit.
The inorganic particles can include, for example, zirconia particles, titania particles, alumina particles and the like. The photocuring composition may further contain additives such as a photopolymerization initiator, a polymerizable monomer, and a curing aid.

(Adhesive layer (adhesive layer))
Each layer (window, polarizing plate, touch sensor) forming the laminate for the flexible image display device and the film member (linear polarizing plate, λ / 4 retardation plate, etc.) constituting each layer can be formed by an adhesive. .. Adhesives include water-based adhesives, organic solvent-based adhesives, solvent-free adhesives, solid adhesives, solvent volatilization adhesives, moisture-curable adhesives, heat-curable adhesives, anaerobic curable adhesives, and active energy ray-curable adhesives. General-purpose adhesives such as adhesives, hardener-mixed adhesives, heat-melt adhesives, pressure-sensitive adhesives (adhesives), and re-wet adhesives can be used. Of these, water-based solvent volatilization adhesives, active energy ray-curable adhesives, and adhesives are often used. The thickness of the adhesive layer can be appropriately adjusted according to the required adhesive strength and the like, and is usually 0.01 to 500 μm, preferably 0.1 to 300 μm. There are a plurality of them, but the thickness of each and the type of the pressure-sensitive adhesive used may be the same or different.

As the water-based water-based solvent volatilization type adhesive, a polyvinyl alcohol-based polymer, a water-soluble polymer such as starch, an ethylene-vinyl acetate-based emulsion, a styrene-butadiene-based emulsion, or the like in an aqueous-dispersed state can be used as the main polymer. In addition to water and the main polymer, a cross-linking agent, a silane compound, an ionic compound, a cross-linking catalyst, an antioxidant, a dye, a pigment, an inorganic filler, an organic solvent and the like may be blended. When adhering with the water-based water-based solvent volatilization type adhesive, the water-based water-based solvent volatilization type adhesive can be injected between the layers to be adhered, the adherend layers are bonded, and then dried to impart adhesiveness. .. When the water-based water-based solvent volatilization type adhesive is used, the thickness of the adhesive layer may be preferably 0.01 to 10 μm, more preferably 0.1 to 1 μm. When the water-based solvent volatilization type adhesive is used for forming a plurality of layers, the thickness of each layer and the type of the adhesive may be the same or different.

The active energy ray-curable adhesive can be formed by curing an active energy ray-curable composition containing a reactive material that is irradiated with active energy rays to form an adhesive layer. The active energy ray-curable composition can contain at least one polymer of a radical-polymerizable compound and a cationically polymerizable compound similar to the hard coat composition. The radically polymerizable compound is the same as the hard coat composition, and the same kind as the hard coat composition can be used. As the radically polymerizable compound used for the adhesive layer, a compound having an acryloyl group is preferable. It is also preferable to include a monofunctional compound in order to reduce the viscosity of the adhesive composition.

The cationically polymerizable compound is the same as the hard coat composition, and the same kind as the hard coat composition can be used. As the cationically polymerizable compound used in the active energy ray-curable composition, an epoxy compound is particularly preferable. It is also preferable to include a monofunctional compound as a reactive diluent in order to reduce the viscosity of the adhesive composition.
The active energy ray composition may further contain a polymerization initiator. The polymerization initiator includes a radical polymerization initiator, a cationic polymerization initiator, a radical and a cationic polymerization initiator, and the like, and can be appropriately selected and used. These polymerization initiators are decomposed by at least one of active energy ray irradiation and heating to generate radicals or cations to promote radical polymerization and cation polymerization. In the description of the hard coat composition, an initiator that can initiate at least one of radical polymerization or cationic polymerization by irradiation with active energy rays can be used.

The active energy ray-curing composition further comprises an ion trapping agent, an antioxidant, a chain transfer agent, an adhesion imparting agent, a thermoplastic resin, a filler, a fluid viscosity modifier, a plasticizer, a defoaming agent solvent, an additive, and a solvent. Can be included. When adhering with the active energy ray-curable adhesive, the active energy ray-curable composition is applied to either or both of the adherend layers and then bonded, and is activated through either or both adherend layers. Adhesion can be achieved by irradiating with energy rays and curing. When the active energy ray-curable adhesive is used, the thickness of the adhesive layer may be preferably 0.01 to 20 μm, more preferably 0.1 to 10 μm. When the active energy ray-curable adhesive is used for forming a plurality of layers, the thickness of each layer and the type of adhesive used may be the same or different.

The pressure-sensitive adhesive may be classified into acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, silicone-based pressure-sensitive adhesives, and the like, depending on the main polymer. In addition to the main polymer, the pressure-sensitive adhesive may contain a cross-linking agent, a silane compound, an ionic compound, a cross-linking catalyst, an antioxidant, a tackifier, a plasticizing agent, a dye, a pigment, an inorganic filler and the like. A pressure-sensitive adhesive layer is formed by dissolving and dispersing each component constituting the pressure-sensitive adhesive in a solvent to obtain a pressure-sensitive adhesive composition, applying the pressure-sensitive adhesive composition onto a substrate, and then drying the mixture. To. The adhesive layer may be directly formed, or a separately formed base material may be transferred. It is also preferable to use a release film to cover the adhesive surface before bonding. When the pressure-sensitive adhesive is used, the thickness of the adhesive layer may be preferably 1 to 500 μm, more preferably 2 to 300 μm. When the pressure-sensitive adhesive is used for forming a plurality of layers, the thickness of each layer and the type of pressure-sensitive adhesive used may be the same or different.

(Shading pattern)
The shading pattern can be applied as at least part of the bezel or housing of the flexible image display device. The light-shielding pattern hides the wiring arranged at the edge of the flexible image display device to make it difficult to see, thereby improving the visibility of the image. The shading pattern may be in the form of a single layer or multiple layers. The color of the light-shielding pattern is not particularly limited, and can have various colors such as black, white, and metallic. The light-shielding pattern can be formed of a pigment for embodying color and a polymer such as an acrylic resin, an ester resin, an epoxy resin, polyurethane, or silicone. They can also be used alone or in mixtures of two or more. The shading pattern can be formed by various methods such as printing, lithography, and inkjet. The thickness of the light-shielding pattern is usually 1 to 100 μm, preferably 2 to 50 μm. It is also preferable to give a shape such as an inclination in the thickness direction of the optical pattern.

Hereinafter, the present invention will be described in more detail with reference to Examples. Unless otherwise specified, "%" and "part" in the example mean mass% and parts by mass. First, the evaluation method will be described.

<1. Measurement method>
(Reflection (SCE) a *, reflection (SCE) b *, reflection (SCI) a *, reflection (SCI) b * of optical film)
The optical films obtained in the examples and comparative examples are cut into a size of 50 mm × 50 mm, and then bonded to black PET (“Kikkari Mieru” manufactured by Tomoegawa Seisakusho Co., Ltd.) to prepare a sample for reflection optical measurement. Obtained.
The hues of the obtained evaluation sample by the SCE method (specular reflection light removal) and the SCI method (including specular light) were measured with a spectrophotometer (“CM-3700A” manufactured by Konica Minolta Co., Ltd.). .. The measurement diameter is LAV: diameter 8 mm, the measurement conditions are di: 8 °, de: 8 ° (diffuse illumination, 8 ° direction reception), the measurement field of view is 2 °, the light source is a D65 light source, and the UV conditions are. It was set to 100% Full. Here, the hue refers to a * and b * in the CIE1976L * a * b * color space. In addition, the reflection (SCE) a * and the reflection (SCI) a * of the optical film were also measured under the same conditions as described above.

(Reflection (SCE) b * and reflection (SCI) b * of a laminate having a circularly polarizing plate)
The reflection (SCE) b * and reflection (SCI) b * of the laminate having the circularly polarizing plate are the same as the measurement method of the optical film except that the measurement target is changed from the optical film to the laminate having the circularly polarizing plate. Was measured. Similarly, reflection (SCE) a * and reflection (SCI) a * were also measured.

(Visible transmittance Y of the laminated body having a circularly polarizing plate)
The visual transmittance Y is a physical characteristic value indicating the brightness of the object color in the XYZ color system. The visual transmittance Y of the SCI method and the SCE method was measured using a spectrocolorimeter (“CM-3700A” manufactured by Konica Minolta Co., Ltd.).

(Transmission b * of optical film)
The optical films obtained in Examples and Comparative Examples were cut into a size of 50 mm × 50 mm, and transmission optical measurements were measured using a spectrocolorimeter (“CM-3700A” manufactured by Konica Minolta Co., Ltd.). The measurement diameter was LAV: 25.4 mm in diameter, and the measurement field of view was 2 °. A D65 light source was used as the measurement light source, and the UV condition was 100% Full. Here, the hue refers to a * and b * in the CIE1976L * a * b * color space.

(Transmission b * of a laminate having a circularly polarizing plate)
The transmission b * of the laminated body having the circularly polarizing plate was measured in the same manner as the measuring method of the optical film except that the measurement target was changed from the optical film to the laminated body having the circularly polarizing plate. Further, in the same manner, the transmission a * of the laminated body having the circularly polarizing plate was also measured.

(Film thickness of optical film and adhesive layer)
Using a micrometer (“ID-C112XBS” manufactured by Mitutoyo Co., Ltd.), the film thickness of 10 or more optical films was measured, and the average value was calculated. In the same manner, the thickness of the pressure-sensitive adhesive layer was measured, and the average value thereof was calculated.

(Total light transmittance and haze of optical film)
The total light transmittance and haze of the optical film are measured using a fully automatic direct reading haze computer HGM-2DP manufactured by Suga Testing Machine Co., Ltd. in accordance with JIS K 7361-1: 1997 and JIS K 7136: 2000, respectively. did. The measurement sample was prepared by cutting the optical films of Examples and Comparative Examples into a size of 30 mm × 30 mm.

(Yellowness of optical film)
The yellowness (Yellow Index: YI value) of the optical film was measured using an ultraviolet-visible near-infrared spectrophotometer (“V-670” manufactured by JASCO Corporation). After performing background measurement in the absence of a sample, the optical films obtained in Examples and Comparative Examples were set in a sample holder, transmittance was measured for light of 300 to 800 nm, and tristimulus values (X, Y, Z) was calculated. From the obtained tristimulus values, the YI value was calculated based on the following formula based on the ASTM D1925 standard.
YI = 100 × (1.2769X-1.0592Z) / Y

(Particle diameter of silica particles)
The particle size of the silica particles was calculated from the specific surface area measurement value by the BET adsorption method according to JIS Z 8830. The specific surface area of the powder obtained by drying the silica sol at 300 ° C. was measured using a specific surface area measuring device (“Monosorb (registered trademark) MS-16” manufactured by Yuasa Ionics Co., Ltd.).

(Weight average molecular weight)
Gel Permeation Chromatography (GPC) Measurement (1) Pretreatment Method After dissolving the sample in γ-butyrolactone (GBL) to make a 20% by mass solution, dilute it 100 times with a DMF eluent and use a 0.45 μm membrane filter. The filtered solution was used as the measurement solution.
(2) Measurement condition column: TSKgel SuperAWM-H × 2 + SuperAW2500 × 1 (6.0 mm ID × 150 mm × 3)
Eluent: DMF (10 mmol lithium bromide added)
Flow rate: 0.6 mL / min Detector: RI detector Column temperature: 40 ° C
Injection volume: 20 μL
Molecular weight standard: Standard polystyrene

(Immidization rate)
The imidization ratio was ^{determined by 1} H-NMR measurement as follows.
(1) Pretreatment Method An optical film containing a polyimide polymer _{was dissolved in deuterated dimethyl sulfoxide (DMSO-d 6} ) to prepare a 2% by mass solution, which was used as a measurement sample.
(2) Measurement conditions Measuring device: JEOL 400MHz NMR device JNM-ECZ400S / L1
Standard substance: DMSO-d ₆ (2.5 ppm)
Sample temperature: Room temperature Accumulation number: 256 times Relaxation time: 5 seconds (3) Imidization rate analysis method (imidization rate of polyimide resin)
^{In the 1} H-NMR spectrum obtained from the measurement sample containing the polyimide resin, the integral value of the benzene proton A derived from the structure that does not change before and after imidization among the observed benzene protons was defined as Int _A. Further, the integral value of the amide proton derived from the amic acid structure remaining in the observed polyimide resin was defined as Int _B. From these integrated values, the imidization rate of the polyimide resin was determined based on the following formula.
Imidization rate (%) = 100 × (1-α × Int _B / Int _A )
In the above formula, α is the number ratio of benzene protons A to one amide proton in the case of polyamic acid (imidization ratio 0%).

(Imidization rate of polyamide-imide resin)
^{In the 1} H-NMR spectrum obtained from the measurement sample containing the polyamide-imide resin, the structure derived from the structure of the observed benzene protons that does not change before and after imidization and the structure derived from the amic acid structure remaining in the polyamide-imide resin. The integrated value of benzene proton C, which is not affected by the above, was defined as Int _C. Further, among the observed benzene protons, the integral value of benzene proton D, which is derived from the structure that does not change before and after imidization and is influenced by the structure derived from the amic acid structure remaining in the polyamide-imide resin, was defined as Int _D. The β value was calculated from the obtained Int _C and Int _D by the following formula.
β = Int _D / Int _C
Next, the β value of the above formula and the imidization rate of the polyimide resin of the above formula were obtained for a plurality of polyamide-imide resins, and the following correlation formula was obtained from these results.
Imidization rate (%) = k × β + 100
In the above correlation equation, k is a constant.
By substituting β into the correlation equation, the imidization rate (%) of the polyamide-imide resin was obtained.

(Calculation of HSP value of resin)
The solubility of the polyamide-imide resin 1 (PAI-1) in a solvent was evaluated. A mixed solution was prepared by putting 10 mL of a solvent having a known solubility parameter as shown in Table 1 (Source: Polymer Handbook 4th Edition) and 0.1 g of a polyamide-imide resin into a transparent container. The resulting mixture was sonicated for a total of 6 hours. The appearance of the mixed solution after the ultrasonic treatment was visually observed, and the solubility of the polyamide-imide resin 1 in the solvent was evaluated based on the following evaluation criteria from the obtained observation results. The evaluation results are shown in Table 1. Similarly, the polyamide-imide resin 2 (PAI-2) and the polyimide resin 1 (PI) are also used in the same manner except that the types of the polyamide-imide resin 1 and the resin in the polyamide-imide resin 1-solvent system are changed. Solubility in was evaluated.
(Evaluation criteria)
1: The appearance of the mixed solution is cloudy.
0: The appearance of the mixed solution is transparent.

From the evaluation result of the solubility of the obtained resin in a solvent, Hansen spheres were prepared by using the above-mentioned Hansen lysing sphere method. The center coordinates of the obtained Hansen sphere were used as the HSP value. The results are shown in Table 2.

(Calculation of HSP value of silica)
The solvent was removed from the silica sol 1 to take out the solid silica 1. The dispersibility of silica 1 in a solvent was evaluated. A mixed solution was prepared by putting 10 mL of a solvent having a known solubility parameter as shown in Table 3 (Source: Polymer Handbook 4th Edition) and 0.1 g of silica into a transparent container. The resulting mixture was sonicated for a total of 6 hours. The appearance of the mixed solution after the ultrasonic treatment was visually observed, and the dispersibility of silica 1 in the solvent was evaluated based on the following evaluation criteria from the obtained observation results. The evaluation results are shown in Table 3. Similarly, for the methanol-dispersed silica sol (“MA-ST-L” manufactured by Nissan Chemical Industry Co., Ltd., primary particle size 20 to 25 nm) and the methanol-dispersed silica sol (silica sol 2, primary particle size 10 to 12 nm). , The dispersibility in the solvent was evaluated in the same manner except that the type of the silica sol as the raw material was changed in the silica 1-solvent system.
(Evaluation criteria)
1: The appearance of the mixed solution is cloudy.
0: The appearance of the mixed solution is transparent.

Hansen spheres were prepared by using the above-mentioned Hansen-dissolved sphere method from the evaluation results of the dispersibility of each silica dispersed in the silica sol in a solvent. The center coordinates of the obtained Hansen sphere were used as the HSP value. The results are shown in Table 4.

(Resin-silica HSP value)
From Tables 2 and 4, the HSP values of the resin-silica system were calculated using the formulas (6) to (9). The results are shown in Table 5.

As shown in Table 5, silica-1,2 resin of Ra, .DELTA..delta _t and .DELTA..delta _p are silica respectively (MA-ST-L) - resin system Ra, compared to .DELTA..delta _t and .DELTA..delta _p, was small. _{Further, Ra, Δδ t} , and Δδ _p of the silica 1,2-resin system satisfied the formulas (3) to (5), respectively.

(Elastic modulus)
The elastic modulus (tensile elastic modulus) G'of the pressure-sensitive adhesive layer was measured by an electromechanical universal tester (manufactured by Instron) by a tensile test conforming to JIS K 7127. The measurement conditions were a test speed of 5 m / min and a load cell of 5 kN.

<2. Evaluation method>
(Evaluation of optical film feeding stability and film appearance)
The optical films of Examples and Comparative Examples were produced by roll-to-roll. The optical film was unwound from the roll, and the state of the optical film when unwound was visually observed. From the observation results, the feeding stability was evaluated based on the following evaluation criteria. Indicated by ◎, △, and × in order from the best.
(Evaluation criteria for the drawability of optical film)
⊚: When the end of the film is fed out from the roll, it can be fed out smoothly.
◯: When the end of the film is extended from the roll, a slight catch is observed, but the film can be extended smoothly.
Δ: Although the film is caught when the edge of the film is extended from the roll, the film is not scratched and the film is not cut.
X: When the end of the film is extended from the roll, catching is recognized, and the film is scratched or the film is cut.

(Evaluation of visibility of laminated body having circular polarizing plate)
A laminate having a circularly polarizing plate is installed on the surface of a reflecting plate (aluminum plate, reflectance 97%), and the observer is circularly polarized from an angle of 45 ° from the vertical direction of the laminated body having the circularly polarizing plate. The laminated body having the plate was visually observed. From the observation results, the visibility of the laminated body having the circularly polarizing plate was evaluated based on the following evaluation criteria. Indicated by 〇, △ and × in order from the best one.
(Evaluation criteria for visibility of laminates with circularly polarizing plates)
〇: No change in hue on the reflector at 45 ° slope compared to the vertical direction Δ: There is a slight change in hue on the reflector at 45 ° slope compared to the vertical direction.
X: On the reflector, the hue change on the 45 ° slope is larger than in the vertical direction.

(Evaluation of suppression of deterioration of film appearance quality)
Optical films of Examples and Comparative Examples were produced. Black paper was placed on the optical film, and the appearance of the optical film was visually observed from the optical film side. It was confirmed whether or not it was whitish (whether or not it was cloudy). From the observation results, the suppression of deterioration of film appearance quality was evaluated based on the following evaluation criteria.
(Evaluation criteria for suppressing deterioration of film appearance quality)
◎ (Very good): Transparent.
○ (Good): Transparent, but slightly whitish.
× (bad): Not transparent but whitish.

<3. Manufacturing of optical film>
[3-1. Manufacture of polyimide-based polymers]
[Manufacturing Example 1: Polyimide Resin 1]
A reaction vessel equipped with a silica gel tube, a stirrer, and a thermometer in a separable flask, and an oil bath were prepared. 75.52 g of 4,4'-(hexafluoroisopropyridene) diphthalic acid dianhydride (6FDA) and 2,2'-bis (trifluoromethyl) -4,4'-in a reaction vessel installed in an oil bath. 54.44 g of diaminodiphenyl (TFMB) was added. While stirring the contents in the reaction vessel at 400 rpm, 519.84 g of N, N-dimethylacetamide (DMAc) was further added to the reaction vessel, and stirring was continued until the contents in the reaction vessel became a uniform solution. Subsequently, stirring was continued for another 20 hours while adjusting the temperature inside the container to be in the range of 20 to 30 ° C. using an oil bath, and the reaction was carried out to generate a polyamic acid. After 30 minutes, the stirring speed was changed to 100 rpm. After stirring for 20 hours, the reaction system temperature is returned to room temperature (25 ° C.), and 649.8 g of DMAc is further added into the reaction vessel to bring the polymer concentration to 10% by weight based on the total weight of the contents in the reaction vessel. Adjusted as follows. Further, 32.27 g of pyridine and 41.65 g of acetic anhydride were put into a reaction vessel, and the mixture was stirred at room temperature for 10 hours for imidization. The polyimide varnish was taken out from the reaction vessel. The obtained polyimide varnish was added dropwise to methanol for reprecipitation. The precipitate was removed by filtration and dried to give a powder. The obtained powder was further heated and dried to remove the solvent, and a polyimide resin 1 was obtained as a solid content. The weight average molecular weight of the obtained polyimide resin 1 was 320,000, and the imidization ratio was 98.6%.

[Production Example 2: Polyamide-imide Resin 1]
Under a nitrogen gas atmosphere, a reaction vessel equipped with a stirring blade and an oil bath were prepared in a separable flask having a capacity of 1 L. 45 g (140.52 mmol) of TFMB and 768.55 g of DMAc were charged into a reaction vessel installed in an oil bath. The contents in the reaction vessel were stirred at room temperature to dissolve TFMB in DMAc. Next, 18.92 g (42.58 mmol) of 6FDA was further charged into the reaction vessel, and the contents in the reaction vessel were stirred at room temperature for 3 hours. Then, 4.19 g (14.19 mmol) of 4,4'-oxybis (benzoyl chloride) (OBBC) and then 17.29 g (85.16 mmol) of terephthaloyl chloride (TPC) were put into the reaction vessel, and the inside of the reaction vessel was charged. The contents of the above were stirred at room temperature for 1 hour. Next, 4.63 g (49.68 mmol) of 4-methylpyridine and 13.04 g (127.75 mmol) of acetic anhydride were further added to the reaction vessel, and the contents in the reaction vessel were stirred at room temperature for 30 minutes. After stirring, the temperature inside the vessel was raised to 70 ° C. using an oil bath, maintained at 70 ° C., and the contents in the reaction vessel were further stirred for 3 hours to obtain a reaction solution.
The obtained reaction solution was cooled to room temperature and poured into a large amount of methanol in the form of filaments to precipitate a precipitate. The precipitated precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Next, the precipitate was dried under reduced pressure at 100 ° C. to obtain a polyamide-imide resin. The weight average molecular weight of the polyamide-imide resin was 400,000, and the imidization rate was 98.8%.

[Production Example 3: Polyamide-imide Resin 2]
Under a nitrogen gas atmosphere, a reaction vessel equipped with a stirring blade and an oil bath were prepared in a separable flask having a capacity of 1 L. 45 g (140.52 mmol) of TFMB and 768.55 g of DMAc were put into a reaction vessel installed in an oil bath. TFMB was dissolved in DMAc while stirring the contents in the reaction vessel at room temperature. Next, 19.01 g (42.79 mmol) of 6FDA was further charged into the reaction vessel, and the contents in the reaction vessel were stirred at room temperature for 3 hours. Then, 4.21 g (14.26 mmol) of OBBC and then 17.30 g (85.59 mmol) of TPC were put into the reaction vessel, and the contents in the reaction vessel were stirred at room temperature for 1 hour. Next, 4.63 g (49.68 mmol) of 4-methylpyridine and 13.04 g (127.75 mmol) of acetic anhydride were further added to the reaction vessel, and the contents in the reaction vessel were stirred at room temperature for 30 minutes. After stirring, the temperature inside the container was raised to 70 ° C. using an oil bath, maintained at 70 ° C., and stirred for another 3 hours to obtain a reaction solution.
The obtained reaction solution was cooled to room temperature and poured into a large amount of methanol in the form of filaments to precipitate a precipitate. The precipitated precipitate was taken out, immersed in methanol for 6 hours, and then washed with methanol. Next, the precipitate was dried under reduced pressure at 100 ° C. to obtain a polyamide-imide resin. The weight average molecular weight of the obtained polyamide-imide resin was 365,000, and the imidization rate was 98.9%.

[3-2. Manufacture of silica particles]
[Production Example 4 Silica Sol 1]
A flask having a capacity of 1 L and a hot water bath were prepared as reaction vessels. 442.6 g of methanol-dispersed silica sol (primary particle size 25 nm, silica solid content 30.5%) and 301.6 g of γ-butyrolactone were charged into a reaction vessel placed in a hot water bath. The temperature inside the vessel was set to 45 ° C. using a hot water bath, the pressure inside the reaction vessel was set to 400 hPa and maintained for 1 hour using an evaporator, and then the pressure inside the reaction vessel was set to 250 hPa and maintained for 1 hour to evaporate methanol. I let you. Further, the pressure inside the reaction vessel was set to 250 hPa, the temperature inside the vessel was raised to 70 ° C., and the mixture was heated for 30 minutes. As a result, a γ-butyrolactone-dispersed silica sol (silica sol 1, SGS7 # 09) was obtained. The solid content of the obtained γ-butyrolactone-dispersed silica sol was 28.9%.

[Production Example 5 Silica Sol 2]
Solvent substitution was carried out in the same manner as in Production Example 4 except that the primary particle size of the methanol-dispersed silica sol was changed to 10 nm and the silica solid content was changed to 22%. 2) was obtained.

[Production Example 6 Silica Sol 3]
Except for changing the methanol-dispersed silica sol (primary particle size 25 nm, silica solid content 30.5%) to methanol-dispersed silica sol (“MA-ST-L” manufactured by Nissan Chemical Industries, Ltd., primary particle size 40-50 nm). Solvent substitution was carried out in the same manner as in Production Example 4 to obtain a γ-butyrolactone-dispersed silica sol (silica sol 3) having a solid content of 30.5% and a primary particle size of 50 nm.

[3-3. Varnish manufacturing]
[Manufacturing Example 7 Varnish 1]
To γ-butyrolactone, the polyamide-imide resin 1, the silica sol 1, the varnish (registered trademark) 340 as an ultraviolet absorber, and the sumiblast (registered trademark) violet B as a whitening agent were added in the composition shown in Table 6. Varnish 1 was prepared so that the solid content was 10.2%.

In Table 6, the unit (wt%) of the contents of the columns "resin" and "silica particles" indicates the ratio (mass%) of the resin and silica particles to the total mass. The unit ph of the content of the column "ultraviolet absorber" indicates the ratio (mass%) to the total mass of the resin and silica particles.

[Production Examples 8 to 13: Varnishes 2 to 8]
The composition (type and / or content of the component) shown in Table 6 was changed, the solvent to be replaced was changed from γ-butyrolactone to N, N-dimethylacetamide, and the solid content concentration of the resin was changed to 11.0%. The varnish 3 was prepared in the same manner as the varnish 1 except that the varnish 1 was prepared. In addition, varnishes 2 and 4 to 8 were prepared in the same manner as in varnish 1 except that the composition (type and / or content of components) shown in Table 6 was changed.

[Example 1]
[3-4. Manufacturing of optical film]
The obtained varnish 1 was salivated on a PET film (“Cosmo Shine (registered trademark) A4100” manufactured by Toyobo Co., Ltd.) to form a coating film. The transport speed of PET in the salivation molding was 0.3 m / min. Then, the coating film was dried by heating at 80 ° C. for 20 minutes and 90 ° C. for 20 minutes, and the coating film was peeled off from the PET film. Then, the coating film was heated with a tenter at 200 ° C. for 12 minutes while laterally stretching the coating film to obtain a polyamide-imide film 1 having a thickness of 51 μm.

[Example 2]
A polyamide-imide film 2 having a film thickness of 29 μm was obtained in the same manner as in Example 1 except that the film thickness of the coating was changed.

[Example 3]
A polyamide-imide film 3 having a film thickness of 50 μm was obtained in the same manner as in Example 1 except that the varnish 1 was changed to the varnish 2.

[Example 4]
A polyamide-imide film 4 having a film thickness of 49 μm was obtained in the same manner as in Example 1 except that the varnish 1 was changed to the varnish 3.

[Example 5]
A polyamide-imide film 5 having a film thickness of 48 μm was obtained in the same manner as in Example 1 except that the varnish 1 was changed to the varnish 4.

[Example 6]
A polyamide-imide film 6 having a film thickness of 48 μm was obtained in the same manner as in Example 1 except that the varnish 1 was changed to the varnish 5.

[Example 7 (reference example) ]
A polyimide film 7 having a film thickness of 78 μm was obtained in the same manner as in Example 1 except that the varnish 1 was changed to the varnish 6.

[Comparative Example 1]
A polyimide film 8 having a film thickness of 52 μm was obtained in the same manner as in Example 1 except that the varnish 1 was changed to the varnish 7.

[Comparative Example 2]
A polyamide-imide film 9 having a film thickness of 50 μm was obtained in the same manner as in Example 1 except that the varnish 1 was changed to the varnish 8.

The appearances of the obtained polyamide-imide films 1 to 6 and 9 and the polyimide films 7 and 8 were visually observed to confirm the presence or absence of cloudiness. The presence of white turbidity was confirmed only in the polyamide-imide film 9, and the presence of white turbidity was not confirmed in the other films.

The optical films of Examples 1 to 7 contained polyamide-imide, satisfied the formula (1), and the evaluation of their feeding stability was any of ⊚, ◯, and Δ. The optical films of Comparative Examples 1 and 2 contained polyamide-imide and did not satisfy the formula (1), and the evaluation results of their feeding stability were all x.

It is clear that the optical films of Examples 1 to 7 are superior in feeding stability and film appearance to the optical films of Comparative Examples 1 and 2.

Further, in the optical films of Examples 1 to 7, the three-dimensional distance Ra determined by the Hansen melting sphere method satisfies the formula (3), and the evaluation results of suppressing the deterioration of the appearance quality of the films are all ◯ (good). )Met. In the optical film of Comparative Example 2, the three-dimensional distance Ra did not satisfy the formula (3), and the evaluation result of suppressing the deterioration of the film appearance quality was × (bad). Shows butyl acrylic rate. MMA indicates methyl methacrylic rate. HEA indicates hydroxyethyl acrylic rate. AA indicates acrylic acid. The amount of the cross-linking agent and the SC agent added is the mass with respect to 100 parts of the monomer.

(Formation of Adhesive Layer 1)
The pressure-sensitive adhesive layer forming composition 1 was applied to the release-treated surface of the release-treated base material (polyethylene terephthalate film, thickness 38 μm) using an applicator to form a coating layer. The coating layer was dried at 100 ° C. for 1 minute to form the pressure-sensitive adhesive layer 1. The thickness of the pressure-sensitive adhesive layer 1 was 25 μm.
Next, another base material (polyethylene terephthalate film, thickness 38 μm) that had been subjected to the mold release treatment was bonded onto the pressure-sensitive adhesive layer 1. Then, it was cured for 7 days under the conditions of a temperature of 23 ° C. and a relative humidity of 50% RH. As a result, a film including the pressure-sensitive adhesive layer 1 was obtained. The elastic modulus G'and the thickness of the obtained pressure-sensitive adhesive layer 1 were measured. The measurement results are summarized in Table 9.
When the pressure-sensitive adhesive layer is laminated below, the base material that has been released from the mold is peeled off after the pressure-sensitive adhesive layer is laminated.

(Formation of Adhesive Layer 2)
The pressure-sensitive adhesive layer 1 except that the pressure-sensitive adhesive layer-forming composition 1 was changed to the pressure-sensitive adhesive layer-forming composition 2 and the pressure-sensitive adhesive layer-forming composition was applied so that the thickness of the pressure-sensitive adhesive layer was 5 μm. The pressure-sensitive adhesive layer 2 was formed in the same manner as in the formation of. The elastic modulus and thickness of the pressure-sensitive adhesive layer 2 are summarized in Table 9.

ＧＰＣ測定より、得られたポリマー１の分子量は数平均分子量２８，２００、分散度（Ｍｗ／Ｍｎ）は１．８２を示し、モノマー含有量は０．５％であった。ポリマー１を濃度５質量％で、シクロペンタノンに溶解した溶液を配向膜形成用組成物として用いた。 [3-6. Manufacture of polarizing plate]
(Preparation of composition for forming alignment film)
Polymer 1 is a polymer having a photoreactive group consisting of the following structural units.

From the GPC measurement, the molecular weight of the obtained polymer 1 was 28,200 on a number average, the dispersity (Mw / Mn) was 1.82, and the monomer content was 0.5%. A solution in which polymer 1 was dissolved in cyclopentanone at a concentration of 5% by mass was used as a composition for forming an alignment film.

(Formation of alignment film)
The composition for forming an alignment film was applied onto a protective film (triacetyl cellulose: TAC) by a bar coating method to form a coating film. The coating was dried at 80 ° C. for 1 minute. Next, using a UV irradiation device (SPOT CURE SP-7, manufactured by Ushio, Inc.) and a wire grid (“UIS-27132 ##” manufactured by Ushio, Inc.), the exposure amount was 100 mJ / cm ² (365 nm standard). ) Conditions, the coating film was irradiated with polarized UV. As a result, an alignment film was formed on the protective film. The alignment film had alignment performance, and its thickness was 100 nm.

化合物（５）および化合物（６）は、Ｌｕｂ ｅｔ ａｌ．Ｒｅｃｌ．Ｔｒａｖ．Ｃｈｉｍ．Ｐａｙｓ−Ｂａｓ、１１５、３２１−３２８（１９９６）記載の方法により合成した。 (Preparation of composition for forming a polarizer)
(Polymerizable liquid crystal compound)
The polymerizable liquid crystal compound is a polymerizable liquid crystal compound represented by the formula (5) [hereinafter, also referred to as compound (5)] and a polymerizable liquid crystal compound represented by the formula (6) [hereinafter, also referred to as compound (6)]. ] And was used.

Compound (5) and compound (6) are described in Lub et al. Recl. Trav. Chim. It was synthesized by the method described in Pays-Bas, 115, 321-328 (1996).

(Dichroic pigment)
As the dichroic dye, the azo dye described in Examples of Japanese Patent Application Laid-Open No. 2013-101328 represented by the following formulas (7), (8) and (9) was used.

(Preparation of composition for forming a polarizer layer)
The composition for forming the polarizer layer is 75 parts by mass of compound (5), 25 parts by mass of compound (6), and each of the azo dyes represented by the above formulas (7), (8), and (9) as a dichroic dye. 2.5 parts by mass, 6 parts by mass of 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1-one (Irgacure 369, manufactured by BASF Japan) as a polymerization initiator, and as a leveling agent. 1.2 parts by mass of the polyacrylate compound (BYK-361N, manufactured by BYK-Chemie) was mixed with 400 parts by mass of toluene, and the obtained mixture was prepared by stirring at 80 ° C. for 1 hour.

(Manufacturing of polarizer)
The above-mentioned composition for forming a polarizer was applied onto the formed alignment film by a bar coating method to form a coating film. The coating film was heated and dried at 100 ° C. for 2 minutes. Then it was cooled to room temperature. Using the above UV irradiation device, the coating film was irradiated with ultraviolet rays under the condition of an integrated light amount of 1200 mJ / cm ^{2 (365 nm standard).} As a result, a polarizer was formed on the alignment film. The thickness of the polarizer was 3 μm.

(Formation of protective layer)
A composition containing polyvinyl alcohol and water was applied onto the polarizer to form a coating film. The coating film was dried at a temperature of 80 ° C. for 3 minutes. As a result, a protective layer was formed on the polarizer. The thickness of the protective layer was 0.5 μm.
From the above, a polarizing layer in which a protective film, an alignment film, a polarizer, and a protective layer are laminated in this order was produced.

下記式で示される化合物ｂ−２：２０質量部

重合開始剤（Ｉｒｇａｃｕｒｅ３６９、２−ジメチルアミノ−２−ベンジル−１−（４−モルホリノフェニル）ブタン−１−オン、ＢＡＳＦジャパン社製）：６質量部
レベリング剤（ＢＹＫ−３６１Ｎ、ポリアクリレート化合物、ＢＹＫ−Ｃｈｅｍｉｅ社製）：０．１質量部
溶剤（シクロペンタノン）：４００質量部 (Formation of λ / 4 retardation plate and positive C plate)
Each of the components shown below was mixed, and the obtained mixture was stirred at 80 ° C. for 1 hour to obtain a composition for forming a λ / 4 retardation layer.
Compound b-1 represented by the following formula: 80 parts by mass

Compound b-2: 20 parts by mass represented by the following formula

Polymerization initiator (Irgacure369, 2-dimethylamino-2-benzyl-1- (4-morpholinophenyl) butane-1-one, manufactured by BASF Japan Ltd.): 6 parts by mass leveling agent (BYK-361N, polyacrylate compound, BYK) -Chemie): 0.1 parts by mass Solvent (cyclopentanone): 400 parts by mass

重合開始剤（Ｉｒｇａｃｕｒｅ ９０７、２−メチル−４’−（メチルチオ）−２−モルホリノプロピオフェノン、ＢＡＳＦジャパン社製）：２．６質量部
レベリング剤（ＢＹＫ−３６１Ｎ、ポリアクリレート化合物、ＢＹＫ−Ｃｈｅｍｉｅ社製）：０．５重質量部
添加剤（ＬＲ９０００、ＢＡＳＦジャパン社製）：５．７質量部
溶剤（プロピレングリコール１−モノメチルエーテル２−アセテート）：４１２質量部 The composition for forming an alignment film was applied onto a first base film (thickness 100 μm, polyethylene terephthalate film (PET)) by a bar coating method, and dried by heating in a drying oven at 80 ° C. for 1 minute. The obtained dry film was subjected to polarized UV irradiation treatment to form a second alignment film. The polarized UV treatment was carried out under the condition that the integrated light amount measured at a wavelength of 365 nm was 100 mJ / cm ^{2 using the above UV irradiation device.} Further, the polarization direction of the polarized UV was set to 45 ° with respect to the absorption axis of the polarizing layer. In this way, a laminate made of "first base film / second alignment film" was obtained. The thickness of the second alignment film was 100 nm.
The composition for forming a λ / 4 retardation layer is applied by the bar coating method on the second alignment film of the laminate composed of the "first base film / second alignment film", and is placed in a drying oven at 120 ° C. for 1 minute. After heat-drying, it was cooled to room temperature. A retardation layer was formed by irradiating the obtained dry film with ultraviolet rays having an integrated light intensity of 1000 mJ / cm ^{2 (365 nm standard) using the above UV irradiation device.} The thickness of the obtained retardation layer was measured with a laser microscope (OLS3000 manufactured by Olympus Corporation) and found to be 2.0 μm. The retardation layer was a λ / 4 plate showing a retardation value of λ / 4 in the in-plane direction. In this way, a laminate composed of "first base film / second alignment film / λ / 4 retardation layer" was obtained.
Each of the components shown below was mixed, and the obtained mixture was stirred at 80 ° C. for 1 hour to obtain a composition for forming a positive c retardation layer.
Compound represented by the following formula (LC242, manufactured by BASF Japan Ltd.): 100 parts by mass

Polymerization initiator (Irgacure 907, 2-methyl-4'-(methylthio) -2-morpholinopropiophenone, manufactured by BASF Japan, Inc.): 2.6 parts by mass leveling agent (BYK-361N, polyacrylate compound, BYK-Chemie) (Manufactured by): 0.5 parts by mass additive (LR9000, manufactured by BASF Japan): 5.7 parts by mass Solvent (propylene glycol 1-monomethyl ether 2-acetate): 412 parts by mass

Similar to the λ / 4 retardation plate, the composition for forming an alignment film is applied onto a second base film (thickness 100 μm, polyethylene terephthalate film (PET)) by a bar coating method, and a drying oven at 90 ° C. A third alignment film was formed by heating and drying in the oven for 1 minute. Then, the composition for forming a positive C retardation layer was applied onto the third alignment film by the bar coating method, heated and dried in a drying oven at 90 ° C. for 1 minute, and then heated and dried in a nitrogen atmosphere using the above UV irradiation device. A positive C plate was formed by irradiating ultraviolet rays with an integrated light amount of 1000 mJ / cm ^{2 (365 nm standard).} The thickness of the obtained positive C plate was measured with a laser microscope (OLS3000 manufactured by Olympus Corporation (formula)) and found to be 1.8 μm.
Then, the retardation layer is formed by bonding the surface of the positive C plate from which the second base film has been peeled off to the opposite side of the first base film of the λ / 4 retardation plate using the pressure-sensitive adhesive layer 2. Made.
Both the λ / 4 retardation plate and the positive C plate formed contained a layer cured in a state in which the polymerizable liquid crystal compound was oriented.

[3-7. Manufacture of laminate with circularly polarizing plate]
The laminate 1 was manufactured by using the polyamide-imide film 1, the polarizing layer, the pressure-sensitive adhesive layer 1, and the pressure-sensitive adhesive layer 2. The laminate 1 includes a polyamide-imide film 1 / adhesive layer 1 / polarizing layer (protective film / alignment film / polarizer / protective layer) / adhesive layer 2 in this order. On the side of the polarizing layer opposite to the protective film side, the surface from which the first base film of the retardation layer was peeled off was bonded via the pressure-sensitive adhesive layer 2. The retardation layer is a layer in which a λ / 4 retardation plate (RWP) and a positive C plate (PosiC) are laminated. After that, the pressure-sensitive adhesive layer 1 was provided on the side of the retardation layer opposite to the polarizing layer. As a result, the laminated body 1 having a circularly polarizing plate was manufactured. The laminate 1 is a polyamide-imide film 1 / adhesive layer 1 / polarizing layer (protective film / alignment film / polarizer / protective layer) / adhesive layer 2 / retardation layer (λ / 4 retardation plate / positive C plate). ) / Adhesive layer 1 was provided in this order. Here, the notation of the alignment film in the retardation layer is omitted.
In the bonding of the polarizing layer and the retardation layer, the absorption axis of the polarizing layer is substantially 45 ° with respect to the slow axis (optical axis) of the retardation layer via the pressure-sensitive adhesive layer 2. The polarizing layer and the retardation layer were bonded together.

The optical characteristic values of the laminated body having the circularly polarizing plate were measured and calculated. Specifically, transmission b *, transmission a *, reflection (SCE) method a *, b *, and Y were measured. From the obtained transmission b *, reflection (SCE) b * and reflection (SCI) b *, transmission b * -reflection (SCE) b * was calculated. The measurement results and calculation results are summarized in Table 10.

[Example 9]
A laminate 2 having a circularly polarizing plate was produced in the same manner as in Example 8 except that the polyamide-imide film 5 was applied to the front plate instead of the polyamide-imide film 1, and the optical characteristic values were measured and calculated.

[Example 10]
A laminate 3 having a circularly polarizing plate was manufactured in the same manner as in Example 8 except that the polyimide film 7 was applied to the front plate instead of the polyamide-imide film 1, and the optical characteristic values were measured and calculated.

[Comparative Example 3]
A laminate 4 having a circularly polarizing plate was manufactured in the same manner as in Example 8 except that the polyimide film 8 was applied to the front plate instead of the polyamide-imide film 1, and the optical characteristic values were measured and calculated.

The laminates having the circularly polarizing plates of Examples 8 to 10 satisfied the formula (39), and the evaluation of their visibility was either ◯ or Δ. Further, the laminate having the circularly polarizing plate of Examples 8 to 10 also satisfied the formula (40).
The circularly polarizing plate of Comparative Example 3 did not satisfy the formula (39), and the evaluation of its visibility was X. Further, the laminated body having the circularly polarizing plate of Comparative Example 3 did not satisfy the formula (40).

It is clear that the laminate having the circularly polarizing plate of Examples 8 to 10 is superior in visibility to the laminate having the circularly polarizing plate of Comparative Example 3.

Claims (9)

An optical film containing a polyamide-imide , wherein the formula (1)
0.1 ≤ reflection (SCE) b * / reflection (SCI) b * ≤ 1.5 ... (1)
[In the formula (1), the reflection (SCE) b * indicates b * in the L * a * b * color system of the light reflected by the optical film obtained by the SCE method, and the reflection (SCI) b * is the SCI. Indicates b * in the L * a * b * color system of the light reflected by the optical film obtained by the method]
An optical film having a haze of 1% or less and a total light transmittance Tt of 85% or more. Further equation (2)
Reflection (SCE) a * / Reflection (SCI) a * ≤ 2.5 ... (2)
[In the formula (2), the reflection (SCE) a * indicates a * in the L * a * b * color system of the light reflected by the optical film obtained by the SCE method, and the reflection (SCI) a * is the SCI. Indicates a * in the L * a * b * color system of the light reflected by the optical film obtained by the method]
The optical film according to claim 1. The optical film according to claim 1 or 2, further comprising silica particles. The optical film according to claim 3, wherein the silica particles are silica particles obtained by subjecting a water-soluble alcohol-dispersed silica sol to a solvent. The optical film according to any one of claims 1 to 4, further comprising an ultraviolet absorber. An optical laminate having the optical film according to any one of claims 1 to 5 and a hard coat layer on at least one surface of the optical film. A flexible image display device including the optical laminate according to claim 6. The flexible image display device according to claim 7, further comprising a circularly polarizing plate. The flexible image display device according to claim 7 or 8, further comprising a touch sensor.