JP2021021855A - Light-selective film and manufacturing method therefor - Google Patents

Abstract

To provide a light-selective film which is superior in terms of base material transparency and process durability, and to provide a manufacturing method therefor.SOLUTION: A light-selective film of the present invention comprises a base material containing a polyimide-based resin, and a dielectric multilayer film provided on at least one surface of the base material, the base material having a total light transmittance of 85% or greater and an elastic modulus of 4 GPa or greater as measured by pressing the base material in the light-selective film by the nanoindentation method.SELECTED DRAWING: None

Description

The present invention relates to an optical selection film having a base material and a dielectric multilayer film, a method for producing the same, an optical sensor including the optical selection film, and a fingerprint authentication device including the optical sensor.

Devices such as smartphones, which have been rapidly developing in recent years, are provided with a fingerprint authentication device or the like, and the fingerprint authentication device or the like uses an optical selection film that reflects and cuts a predetermined wavelength band such as near infrared rays. There is. The optical selection film is, for example, a film in which a metal such as silver is vapor-deposited on the surface of a transparent base material such as glass to reflect near infrared rays, or a transparent base material such as glass, acrylic resin, or polycarbonate resin absorbs near infrared rays. Those to which a dye is added have been put into practical use. However, the optical selection film in which a metal is vapor-deposited on a glass base material not only requires a manufacturing cost, but also has a problem that glass pieces of the base material are mixed as foreign matter during cutting (during punching) and cracks occur. There is.

On the other hand, as a near-infrared cut filter, an optical selection film having a cyclic olefin resin base material and a dielectric multilayer film is also known (for example, Patent Document 1). The optical selection film is excellent in dimensional stability and transparency because the cyclic olefin resin constituting the base material has high transparency and heat resistance.

Japanese Unexamined Patent Publication No. 2010-23235

A fingerprint authentication device or the like using such an optical selection film is manufactured, for example, via a process of attaching the optical selection film to a panel with a laminator or the like via an adhesive or the like. In recent years, such products have been further reduced in size and height, and the optical selection film is also required to be further thinned.

However, according to the study of the present inventor, although the optical selection film having a cyclic olefin resin base material has high transparency, when it is thinned, cracks and cracks occur when it is bonded to a panel with a laminator or the like. It was found that the process durability was inferior.

Therefore, an object of the present invention is to provide an optical selection film having excellent transparency and process durability of a base material, a method for producing the same, an optical sensor containing the optical selection film, and a fingerprint authentication device including the optical sensor. It is in.

As a result of diligent studies to solve the above problems, the present inventor has made a base material in an optical selection film having a base material containing a polyimide resin and a dielectric multilayer film on at least one surface of the base material. The present invention is completed by finding that the above problems can be solved by adjusting the total light transmittance of the above to 85% or more and adjusting the elastic modulus measured by pushing the substrate in the light selection film to 4 GPa or more. It came to. That is, the present invention includes the following preferred embodiments.

[1] An optical selection film having a base material containing a polyimide resin and a dielectric multilayer film on at least one surface of the base material.
The total light transmittance of the base material is 85% or more.
A photoselective film having an elastic modulus of 4 GPa or more measured by pushing a substrate in the photoselective film by the nanoindentation method.
[2] The optical selection film according to [1], wherein the thickness of the base material is less than 100 μm.
[3] The optical selection film according to [1] or [2], wherein the thickness of the base material is 40 μm or less.
[4] The optical selection film according to any one of [1] to [3], wherein the dielectric multilayer film has a structure in which low refractive index layers and high refractive index layers are alternately laminated.
[5] The light-selective film according to [4], wherein the low refractive index layer contains silica and the high refractive index layer contains titania.
[6] The optical selection film according to any one of [1] to [5], which has a dielectric multilayer film on both sides of the base material.
[7] An optical sensor comprising the optical selection film according to any one of [1] to [6].
[8] A fingerprint authentication device including the optical sensor according to [7].
[9] [1] to [6] include a step (I) of forming a base material containing a polyimide resin and a step (II) of forming a dielectric multilayer film on at least one surface of the base material. ], Which is the method for producing an optical selection film according to any one of
The method (I) comprises the step (A) of imidizing the polyimide resin precursor in the presence of a catalyst.
[10] The method according to [9], wherein step (A) is performed at a temperature of 250 ° C. or lower.

The optical selection film of the present invention is excellent in the transparency of the base material and the process durability. Therefore, it can be suitably used as an optical sensor or a fingerprint authentication device.

[Light selection film]
The optical selection film of the present invention has a base material containing a polyimide resin and a dielectric multilayer film on at least one surface of the base material.

<Base material>
The base material in the optical selection film of the present invention contains a polyimide resin. The polyimide resin refers to at least one polymer selected from a polyimide resin and a polyamide-imide resin. The polyimide resin represents a polymer containing a repeating structural unit containing an imide group, and the polyamide-imide resin represents a polymer containing a repeating structural unit containing an imide group and a repeating structural unit containing an amide group. In this specification, the repeating structural unit may be referred to as a constituent unit.

In one embodiment of the present invention, the polyimide resin preferably contains a structural unit represented by the formula (1), and the polyamide-imide resin is represented by the structural unit represented by the formula (1) and the formula (2). It is preferable to include the structural unit to be used.

In the formulas (1) and (2), X independently represents a divalent organic group, preferably a divalent organic group having 4 to 40 carbon atoms, and more preferably 4 carbon atoms having a cyclic structure. Represents a divalent organic group of ~ 40. Examples of the cyclic structure include an alicyclic ring, an aromatic ring, and a heterocyclic structure. In the organic group, the hydrogen atom in the organic group may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group, in which case the carbon number of the hydrocarbon group and the fluorine-substituted hydrocarbon group is preferable. Is 1-8. The polyimide resin according to one embodiment of the present invention may contain a plurality of types of X, and the plurality of types of X may be the same as or different from each other. As X, it is represented by the formula (10), the formula (11), the formula (12), the formula (13), the formula (14), the formula (15), the formula (16), the formula (17) and the formula (18). Groups; Groups in which the hydrogen atom in the groups represented by the formulas (10) to (18) is substituted with a methyl group, a fluoro group, a chloro group or a trifluoromethyl group; and a group having 6 or less carbon atoms. A chain hydrocarbon group is exemplified.

In equations (10) to (18), * represents a bond,
V ^{1, V 2} and ^{V 3} each independently represent a single _{bond, -O -, - S -,} - CH 2 -, - CH 2 -CH 2 -, - CH (CH 3) -, - C (CH ₃ ) Represents _2- , -C (CF ₃ ) _2- , -SO _2- , -CO- or -N (Q)-. Here, Q represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom. Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group. , 2-Methyl-butyl group, 3-methylbutyl group, 2-ethyl-propyl group, n-hexyl, n-heptyl group, n-octyl group, tert-octyl group, n-nonyl group, n-decyl group, etc. These may be substituted with halogen atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
In one example, V ¹ and V ³ are single bonds, -O- or -S-, and V ² is -CH _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2. -Or -SO _2- . The bonding position of V ¹ and V ² with respect to each ring and the bonding position of V ² and V ³ with respect to each ring are preferably meta-position or para-position with respect to each ring, and more preferably para. The rank.

Among the groups represented by the formulas (10) to (18), the formulas (13), the formula (14), the formula (15), and the formula (from the viewpoint of easily increasing the elastic modulus and the bending resistance of the optical selection film). The groups represented by the formulas (16) and (17) are preferable, and the groups represented by the formulas (14), (15) and (16) are more preferable. Further, V ¹ , V ² and V ³ are preferably single-bonded, -O- or -S-, respectively, independently from the viewpoint of easily increasing the elastic modulus and flexibility of the photoselective film, and are single-bonded or -S-. -O- is more preferable.

［式（４）中、Ｒ^１０〜Ｒ^１７は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基又は炭素数６〜１２のアリール基を表し、Ｒ^１０〜Ｒ^１７に含まれる水素原子は、それぞれ独立に、ハロゲン原子で置換されていてもよく、＊は結合手を表す］
で表される基である。式（１）及び式（２）中の複数のＸの少なくとも一部が式（４）で表される基であると、光選択フィルムは、弾性率及び透明性を向上しやすい。 In a preferred embodiment of the present invention, at least a part of the plurality of Xs in the formula (1) and the formula (2) is the formula (4) :.

[In formula (4), R ^{10 to} R ¹⁷ independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and hydrogen contained in R ^{10 to} R ¹⁷ is contained. Atoms may be independently substituted with halogen atoms, with * representing a bond]
It is a group represented by. When at least a part of the plurality of Xs in the formulas (1) and (2) is a group represented by the formula (4), the photoselective film tends to improve the elastic modulus and transparency.

In formula (4), R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms or 6 carbon atoms, respectively. Represents ~ 12 aryl groups. Examples of alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and 2-methyl-. Examples thereof include a butyl group, a 3-methylbutyl group, a 2-ethyl-propyl group, and an n-hexyl group. Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a tolyl group, a xsilyl group, a naphthyl group, a biphenyl group and the like. R ^{10 to} R ¹⁷ independently represent hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, more preferably hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, and here, R ¹⁰ to R ¹⁷ The hydrogen atom contained in R ¹⁷ may be independently substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R ^{10 to} R ¹⁷ are each independently composed of a hydrogen atom, a methyl group, a fluoro group, a chloro group or a trifluoromethyl group from the viewpoint of easily increasing the elasticity, transparency and bending resistance of the photoselective film. Yes, particularly preferably R ¹⁰ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are hydrogen atoms, and R ¹¹ and R ¹⁷ are hydrogen atoms, methyl groups, fluoro groups, chloro groups or trifluoromethyl groups. In particular, it is preferable that R ¹¹ and R ¹⁷ are methyl groups or trifluoromethyl groups.

で表される。すなわち、複数のＸの少なくとも一部は式（４’）で表される基である。この場合、光選択フィルムは、弾性率及び透明性を向上しやすい。また、フッ素元素を含有する骨格により該ポリイミド系樹脂の溶媒への溶解性を向上し、ポリイミド系樹脂ワニスの粘度を低く抑制することができ、基材の加工を容易にすることができる。 In a preferred embodiment of the present invention, formula (4) is formula (4'):

It is represented by. That is, at least a part of the plurality of Xs is a group represented by the formula (4'). In this case, the photoselective film tends to improve the elastic modulus and transparency. Further, the skeleton containing a fluorine element can improve the solubility of the polyimide resin in a solvent, suppress the viscosity of the polyimide resin varnish to a low level, and facilitate the processing of the base material.

In a preferred embodiment of the present invention, preferably 30 mol% or more, more preferably 50 mol% or more, still more preferably 70 mol% or more of X in the polyimide resin is the formula (4), particularly the formula (4). It is represented by'). When X within the above range in the polyimide resin is represented by the formula (4), particularly the formula (4'), the photoselective film tends to improve the elastic modulus and transparency. Further, the skeleton containing a fluorine element can improve the solubility of the polyimide resin in a solvent, suppress the viscosity of the polyimide resin varnish to a low level, and facilitate the processing of the base material. It should be noted that preferably, 100 mol% or less of X in the polyimide resin is represented by the formula (4), particularly the formula (4'). The ratio of the groups represented by the formula (4) of X in the polyimide resin can be measured using, for example, ^{1 1} H-NMR, or can be calculated from the charging ratio of the raw materials.

In the formula (1), Y represents a tetravalent organic group, preferably a tetravalent organic group having 4 to 40 carbon atoms, and more preferably a tetravalent organic group having a cyclic structure and having 4 to 40 carbon atoms. Represents. Examples of the cyclic structure include an alicyclic ring, an aromatic ring, and a heterocyclic structure. The organic group is an organic group in which the hydrogen atom in the organic group may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group, in which case the hydrocarbon group and the fluorine-substituted hydrocarbon group The number of carbon atoms is preferably 1 to 8. The polyimide resin according to one embodiment of the present invention may contain a plurality of types of Y, and the plurality of types of Y may be the same as or different from each other. As Y, the following formulas (20), formulas (21), formulas (22), formulas (23), formulas (24), formulas (25), formulas (26), formulas (27), formulas (28) And groups represented by the formula (29); groups in which the hydrogen atom in the groups represented by the formulas (20) to (29) is substituted with a methyl group, a fluoro group, a chloro group or a trifluoromethyl group. ; And a chain hydrocarbon group having 4 or less tetravalent carbon atoms is exemplified.

In equations (20) to (29),
* Represents a bond
W ¹ represents 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 it represents -Ar-SO _2- Ar-. Ar represents an arylene group having 6 to 20 carbon atoms in which a hydrogen atom may be substituted with a fluorine atom, and specific examples thereof include a phenylene group.

Among the groups represented by the formulas (20) to (29), the formula (26), the formula (28) or the formula (29) from the viewpoint of easily increasing the elastic modulus, transparency and bending resistance of the photoselective film. The group represented by the formula (26) is preferable, and the group represented by the formula (26) is more preferable. Further, W ¹ is a single bond, −O−, −CH ₂ −, −CH ₂ −CH from the viewpoint of easily increasing the elastic modulus and bending resistance of the optical selection film and easily reducing the yellowness (YI). _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- or -C (CF ₃ ) _2- , preferably single bond, -O-, -CH _2- , -CH (CH) ₃ ) −, −C (CH ₃ ) ₂ − or −C (CF ₃ ) ₂ −, more preferably single bond, −C (CH ₃ ) ₂ − or −C (CF ₃ ) ₂ −. Is even more preferable.

［式（５）中、Ｒ^１８〜Ｒ^２５は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基又は炭素数６〜１２のアリール基を表し、Ｒ^１８〜Ｒ^２５に含まれる水素原子は、それぞれ独立に、ハロゲン原子で置換されていてもよく、＊は結合手を表す］
で表される基である。式（１）中の複数のＹの少なくとも一部が式（５）で表される基であると、光選択フィルムは高い透明性を発現しやすい。またポリイミド系樹脂の溶媒への溶解性を向上し、ポリイミド系樹脂ワニスの粘度を低く抑制することができ、かつ基材の加工を容易にすることができる。 In a preferred embodiment of the present invention, at least a part of the plurality of Ys in the formula (1) is the formula (5) :.

[In formula (5), R ^{18 to} R ²⁵ independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and hydrogen contained in R ^{18 to} R ^25. Atoms may be independently substituted with halogen atoms, with * representing a bond]
It is a group represented by. When at least a part of the plurality of Ys in the formula (1) is a group represented by the formula (5), the photoselective film tends to exhibit high transparency. Further, the solubility of the polyimide resin in the solvent can be improved, the viscosity of the polyimide resin varnish can be suppressed to be low, and the processing of the base material can be facilitated.

In formula (5), R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms or 6 carbon atoms, respectively. Represents ~ 12 aryl groups. Examples of the alkyl group having 1 to 6 carbon atoms and the aryl group having 6 to 12 carbon atoms include those exemplified as the alkyl group having 1 to 6 carbon atoms and the aryl group having 6 to 12 carbon atoms in the formula (4), respectively. Be done. Each of R ^{18 to} R ²⁵ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having a hydrogen atom or 1 to 3 carbon atoms, and here, R ¹⁸ to R ²⁵ are represented. The hydrogen atom contained in R ²⁵ may be independently substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Each of R ^{18 to} R ²⁵ is more preferably a hydrogen atom, a methyl group, a fluoro group, a chloro group or a trifluoromethyl group from the viewpoint of easily improving the elasticity, transparency and bending resistance of the photoselective film. More preferably, R ¹⁸ , R ¹⁹ , R ²⁰ , R ²³ , R ²⁴ and R ²⁵ are hydrogen atoms, and R ²¹ and R ²² are hydrogen atoms, methyl groups, fluorogroups, chloro groups or trifluoromethyl groups. In particular, it is preferable that R ²¹ and R ²² are methyl groups or trifluoromethyl groups.

で表される。すなわち、複数のＹの少なくとも一部は、式（５’）で表される基である。この場合、光選択フィルムは、高い透明性を発現しやすい。 In a preferred embodiment of the present invention, formula (5) is formula (5'):

It is represented by. That is, at least a part of the plurality of Ys is a group represented by the formula (5'). In this case, the photoselective film tends to exhibit high transparency.

In a preferred embodiment of the present invention, Y in the polyimide resin is preferably 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more of the formula (5), particularly the formula (5). It is represented by'). When Y in the above range in the polyimide resin is represented by the formula (5), particularly the formula (5'), the photoselective film tends to have high transparency, and the polyimide further has a skeleton containing a fluorine element. The solubility of the based resin in a solvent can be improved, the viscosity of the polyimide resin varnish can be suppressed to a low level, and the base material can be easily produced. It should be noted that preferably, 100 mol% or less of Y in the polyimide resin is represented by the formula (5), particularly the formula (5'). The ratio of the groups represented by the formula (5) of Y in the polyimide resin can be measured using, for example, ^{1 1} H-NMR, or can be calculated from the charging ratio of the raw materials.

In the formula (2), Z is independently a divalent organic group, preferably substituted with a hydrocarbon group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms substituted with fluorine. It may be a divalent organic group having 4 to 40 carbon atoms, more preferably substituted with a hydrocarbon group having 1 to 8 carbon atoms or a hydrocarbon group having 1 to 8 carbon atoms substituted with fluorine. It represents a good divalent organic group having a cyclic structure and having 4 to 40 carbon atoms. Examples of the cyclic structure include an alicyclic ring, an aromatic ring, and a heterocyclic structure. As the organic group of Z, the following formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), formula ( Among the group bonds represented by 28) and the formula (29), a group in which two non-adjacent groups are replaced with a hydrogen atom and a divalent chain hydrocarbon group having 6 or less carbon atoms are exemplified. From the viewpoint of easily reducing the yellowness (YI) of the obtained photoselective film, the groups represented by the formulas (20) to (27) are preferable.

［式（３）中、Ｒ^１〜Ｒ^８は、それぞれ独立に、水素原子、炭素数１〜６のアルキル基又は炭素数６〜１２のアリール基を表し、Ｒ^１〜Ｒ^８に含まれる水素原子は、それぞれ独立に、ハロゲン原子で置換されていてもよく、
Ａは、単結合、−Ｏ−、−ＣＨ_２−、−ＣＨ_２−ＣＨ_２−、−ＣＨ（ＣＨ_３）−、−Ｃ（ＣＨ_３）_２−、−Ｃ（ＣＦ_３）_２−、−ＳＯ_２−、−Ｓ−、−ＣＯ−又は−Ｎ（Ｒ^９）−を表し、Ｒ^９は水素原子、ハロゲン原子で置換されていてもよい炭素数１〜１２の１価の炭化水素基を表し、
ｍは０〜４の整数であり、
＊は結合手を表す］
で表される基であることが好ましい。 In one embodiment of the present invention, the polyimide resin may contain a plurality of types of Z, and the plurality of types of Z may be the same as or different from each other. In particular, from the viewpoint of easily increasing the elastic modulus, transparency and bending resistance of the photoselective film, at least a part of Z is expressed by the formula (3) :.

[In formula (3), R ^{1 to} R ⁸ independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and hydrogen contained in R ^{1 to} R ⁸ is contained. Atoms may be independently substituted with halogen atoms,
A represents a single _{bond, -O -, - CH 2 -} , - CH 2 -CH 2 -, - CH (CH 3) -, - C (CH 3) 2 -, - C (CF 3) 2 -, - It represents SO _2- , -S-, -CO- or -N (R ⁹ )-, and R ⁹ is a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a hydrogen atom or a halogen atom. Represent,
m is an integer from 0 to 4
* Represents a bond]
It is preferably a group represented by.

In the formula (3), A is independently a single _{bond, -O -, - CH 2 -} , - CH 2 -CH 2 -, - CH (CH 3) -, - C (CH 3) 2 -, -C (CF ₃ ) _2- , -SO _2- , -S-, -CO- or -N (R ⁹ )-is preferable from the viewpoint of easily improving the elastic modulus and bending resistance of the optical selection film. Represents -O- or -S-, more preferably -O-.
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently have a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 12 carbon atoms. Represent. Examples of the alkyl group having 1 to 6 carbon atoms and the aryl group having 6 to 12 carbon atoms include those exemplified as the alkyl group having 1 to 6 carbon atoms and the aryl group having 6 to 12 carbon atoms in the formula (4), respectively. Be done. From the viewpoint of easily increasing the elasticity and flexibility of the photoselective film, R ^{1 to} R ⁸ independently represent hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, and more preferably hydrogen atoms or carbon atoms. It represents 1 to 3 alkyl groups, more preferably a hydrogen atom. Here, the hydrogen atoms contained in R ^{1 to} R ⁸ may be independently substituted with halogen atoms.
R ⁹ represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a hydrogen atom or a halogen atom. Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include the monovalent hydrocarbon group having 1 to 12 carbon atoms exemplified above.

In the formula (3), m is an integer in the range of 0 to 4, and when m is in this range, the elastic modulus and bending resistance of the photoselective film are good. Further, in the formula (3), m is preferably an integer in the range of 0 to 3, more preferably an integer in the range of 0 to 2, more preferably 0 or 1, and m is within this range. The elastic modulus and bending resistance of the photoselective film are good, and at the same time, the availability of raw materials is relatively good. Further, Z may contain one or more structural units represented by the formula (3), and is particularly m from the viewpoint of easily improving the elastic modulus, transparency and bending resistance of the optical selection film. It may contain two or more kinds of groups having different values of, preferably two kinds of groups having different values of m. In that case, it is preferable that the photoselective film contains both the structural units of 0 and 1 from the viewpoint of easily exhibiting high elastic modulus, transparency and bending resistance.

で表される基であり、これらは併用することもできる。この場合、光選択フィルムは、弾性率、透明性及び耐屈曲性に優れる。 In a preferred embodiment of the present invention, the formula (3) is a group in which m = 0 and R ^{5 to} R ⁸ are hydrogen atoms or formula (3'):

It is a group represented by, and these can also be used together. In this case, the optical selection film is excellent in elastic modulus, transparency and bending resistance.

In a preferred embodiment of the present invention, the formula (when m is 0 to 4 with respect to the total of the structural units represented by the formula (1) and the structural units represented by the formula (2) of the polyimide resin ( The ratio of the groups represented by 3) is preferably 20 mol% or more, more preferably 30 mol% or more, further preferably 40 mol% or more, particularly preferably 50 mol% or more, and most preferably 60 mol% or more. Yes, preferably 90 mol% or less, more preferably 85 mol% or less, still more preferably 80 mol% or less. The group represented by the formula (3) when m is 0 to 4 with respect to the total of the structural units represented by the formula (1) and the structural units represented by the formula (2) in the polyimide resin. When the ratio is not more than the above lower limit, the elastic modulus, transparency and bending resistance of the photoselective film are likely to be improved. The group represented by the formula (3) when m is 0 to 4 with respect to the total of the structural units represented by the formula (1) and the structural units represented by the formula (2) in the polyimide resin. When the ratio is not more than the above upper limit, the viscosity of the polyimide resin varnish can be suppressed by suppressing the thickening due to the hydrogen bond between the amide bonds derived from the formula (3), and the processing of the base material can be facilitated. can do.

In a preferred embodiment of the present invention, m of the formula (3) is 1 to 4 with respect to the total of the structural units represented by the formula (1) and the structural units represented by the formula (2) of the polyimide resin. The ratio of the groups represented by is preferably 3 mol% or more, more preferably 5 mol% or more, further preferably 7 mol% or more, particularly preferably 9 mol% or more, preferably 90 mol% or less, and more. It is preferably 70 mol% or less, more preferably 50 mol% or less, and particularly preferably 30 mol% or less. The ratio of the groups in which m in the formula (3) is represented by 1 to 4 is the ratio of the structural units represented by the formula (1) and the structural units represented by the formula (2) in the polyimide resin. When it is at least the above lower limit, the elastic modulus, transparency and bending resistance of the photoselective film are likely to be improved. The ratio of the groups in which m in the formula (3) is represented by 1 to 4 is the ratio of the structural units represented by the formula (1) and the structural units represented by the formula (2) in the polyimide resin. When it is not more than the above upper limit, the viscosity of the polyimide resin varnish can be suppressed by suppressing the thickening due to the hydrogen bond between the amide bonds derived from the formula (3), and the processing of the base material is facilitated. Can be done. The ratio of the groups represented by the formula (3) can be measured using, for example, ^{1 1} H-NMR, or can be calculated from the raw material charging ratio.

In a preferred embodiment of the present invention, Z in the polyimide resin is preferably 5 mol% or more, more preferably 8 mol% or more, still more preferably 10 mol% or more, and particularly preferably 12 mol% or more. It is expressed by the formula (3) when m is 1 to 4. When the above lower limit or more of Z of the polyimide resin is represented by the formula (3) when m is 1 to 4, the elastic modulus, transparency and bending resistance of the photoselective film can be easily improved. Further, when Z in the polyimide resin is preferably 90 mol% or less, more preferably 70 mol% or less, further preferably 50 mol% or less, particularly preferably 30 mol% or less, and m is 1 to 4. It is preferably represented by the formula (3). When the above upper limit or less of Z of the polyimide resin is represented by the formula (3) when m is 1 to 4, it is due to the hydrogen bond between the amide bonds derived from the formula (3) when m is 1 to 4. By suppressing the thickening, the viscosity of the polyimide resin varnish can be suppressed, and the processing of the base material can be facilitated.

In a preferred embodiment of the present invention, when Z in the polyimide resin is preferably 30 mol% or more, more preferably 50 mol% or more, particularly preferably 70 mol% or more, and m is 0 to 4. It is represented by the equation (3). When the above lower limit or more of Z of the polyimide resin is represented by the formula (3) when m is 0 to 4, the elastic modulus, transparency and bending resistance of the photoselective film are likely to be improved. Further, it is preferable that 100 mol% or less of Z in the polyimide resin is represented by the formula (3) when m is 0 to 4. When the above upper limit or less of Z of the polyimide resin is represented by the formula (3) when m is 0 to 4, it is due to the hydrogen bond between the amide bonds derived from the formula (3) when m is 0 to 4. By suppressing the thickening, the viscosity of the polyimide resin varnish can be suppressed, and the processing of the base material can be facilitated. The ratio of the groups represented by the formula (3) in the polyimide resin can be measured by using, for example, ¹ H-NMR, or can be calculated from the raw material charging ratio.

The weight average molecular weight (Mw) of the polyimide resin in terms of standard polystyrene is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 50,000 or more, still more preferably 100,000 or more, particularly. It is preferably 250,000 or more, more preferably 350,000 or more, preferably 800,000 or less, more preferably 600,000 or less, still more preferably 500,000 or less, and particularly preferably 450,000 or less. .. When the weight average molecular weight of the polyimide resin is at least the above lower limit, the photoselective film tends to have a high elastic modulus and bending resistance. Further, when the weight average molecular weight of the polyimide resin is not more than the above upper limit, the viscosity of the polyimide resin varnish can be suppressed to be low, and the photoselective film, particularly the base material, can be easily stretched, so that the processability is easy. Becomes good. In this specification, the weight average molecular weight can be obtained by, for example, GPC measurement and standard polystyrene conversion.

In the polyimide resin (polyamide-imide resin), the content of the structural unit represented by the formula (2) is preferably 0.1 mol or more with respect to 1 mol of the structural unit represented by the formula (1). It is preferably 0.5 mol or more, more preferably 1.0 mol or more, particularly preferably 1.5 mol or more, preferably 6.0 mol or less, more preferably 5.0 mol or less, still more preferably 4. It is 5 mol or less. When the content of the structural unit represented by the formula (2) is not more than the above lower limit, the photoselective film tends to develop a higher elastic modulus. Further, when the content of the structural unit represented by the formula (2) is not more than the above upper limit, the thickening due to the hydrogen bond between the amide bonds in the formula (2) is suppressed, and the viscosity of the polyimide resin varnish is increased. It can be reduced and the base material can be easily manufactured.

The polyimide resin contains a structural unit represented by the formula (30) and / or a structural unit represented by the formula (31) in addition to the structural units represented by the formulas (1) and (2). be able to.

In the formula (30), Y ¹ is a tetravalent organic group, preferably an organic group in which the hydrogen atom in the organic group may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group. Examples of Y ¹ include formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), formula (28) and Groups represented by the formula (29), groups in which the hydrogen atom in the groups represented by the formulas (20) to (29) is substituted with a methyl group, a fluoro group, a chloro group or a trifluoromethyl group. In addition, a chain hydrocarbon group having a tetravalent carbon number of 6 or less is exemplified. Polyimide resin, which is an embodiment of the present invention may include a plurality of kinds of Y ^1, Y ¹ of the plurality of kinds may be the same or may be different from one another.

In the formula (31), Y ² is a trivalent organic group, preferably an organic group in which the hydrogen atom in the organic group may be substituted with a hydrocarbon group or a hydrocarbon group substituted with fluorine. Examples of Y ² include the above equations (20), (21), (22), (23), (24), (25), (26), (27), and (28). ) And 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 are exemplified. Polyimide resin, which is an embodiment of the present invention may include a plurality of kinds of Y ^2, Y ² a plurality of species may be the same or may be different from one another.

In formulas (30) and (31), X ¹ and X ² are independently divalent organic groups, preferably hydrocarbon groups in which hydrogen atoms in the organic groups are hydrocarbon groups or fluorine-substituted hydrocarbon groups. It is an organic group that may be substituted with. Examples of X ¹ and X ² include the above equations (10), (11), (12), (13), (14), (15), (16), (17) and Groups represented by the formula (18); groups in which the hydrogen atom in the groups represented by the formulas (10) to (18) is substituted with a methyl group, a fluoro group, a chloro group or a trifluoromethyl group; A chain hydrocarbon group having 6 or less carbon atoms is exemplified.

In one embodiment of the present invention, when the polyimide resin (polyimide resin) contains a structural unit represented by the formula (1) and a structural unit represented by the formula (30) and / or the formula (31), light selection is performed. From the viewpoint of easily increasing the elastic modulus and bending resistance of the film, the ratio of the structural units represented by the formula (1) is the structural units represented by the formula (1) and the formulas (30) and / or the formula (31). It is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and preferably 100 mol% or less, based on the total molar amount of the structural unit represented by. Further, when the polyimide-based resin (polyamideimide resin) contains a structural unit represented by the formulas (1) and (2) and a structural unit represented by the formulas (30) and / or the formula (31), optical selection is performed. From the viewpoint of easily increasing the elastic modulus and bending resistance of the film, the ratio of the structural units represented by the formulas (1) and (2) is the structural units represented by the formulas (1) and (2) and the formula. It is preferably 80 mol% or more, more preferably 90 mol% or more, still more preferably 95 mol% or more, and preferably 95 mol% or more, based on the total molar amount of the structural unit represented by (30) and / or the formula (31). Is 100 mol% or less. In the polyimide resin, the ratio can be measured by using, for example, ¹ H-NMR, or can be calculated from the raw material charging ratio.

In a preferred embodiment of the present invention, the polyimide resin may contain halogen atoms as described above. Specific examples of the fluorine-containing substituent include a fluoro group and a trifluoromethyl group. When the polyimide resin contains a halogen atom, the yellowness of the photoselective film may be reduced, and there is a tendency that a higher elastic modulus and bending resistance can be achieved at the same time. Further, the halogen atom is preferably a fluorine atom from the viewpoint of reducing the yellowness of the photoselective film, that is, improving the transparency, reducing the water absorption rate, and bending resistance.

The content of the halogen atom in the polyimide resin is preferably 1 based on the mass of the polyimide resin from the viewpoint of reducing yellowness, that is, improving transparency, reducing water absorption, and suppressing deformation of the photoselective film. It is ~ 40% by mass, more preferably 3 to 35% by mass, and even more preferably 5 to 32% by mass.

The substrate contained in the light-selective film of the present invention preferably contains a near-infrared absorber from the viewpoint of widening the viewing angle of the light-selective film (reducing the angle dependence). Examples of the near-infrared absorber include squarylium pigments, cyanine pigments, phthalocyanine pigments, naphthalocyanine pigments, quaterylene pigments, dithiol metal complex pigments, and transition metal oxide compounds. 10 ”,“ E-Excolor IR-12 ”,“ E-Ex Color IR-14 ”,“ E-Ex Color HA-1 ”,“ E-Ex Color HA-14 ”(all product names, manufactured by Nippon Catalyst Co., Ltd.), "SIR-128", "SIR-130", "SIR-132", "SIR-152", "SIR-159", "SIR-162" (all trade names, manufactured by Mitsui Chemicals, Inc.), "Kayasorb IRG" -022 "," Kayasorb IRG-023 "," Kayasorb IRG-040 "(trade name, manufactured by Nippon Kayaku Co., Ltd.)," CIR-1081 "(trade name, manufactured by Nippon Kalit Co., Ltd.)," NIR-IM1 ", "NIR-AM1" (trade name, manufactured by Nagase ChemteX Corporation), tungsten oxide compound (manufactured by Sumitomo Metal Mining Co., Ltd.), "Lumogen IR765", "Lumogen IR788" (manufactured by BASF), "ARS670T", ""IRA800","IRA850" and "IRA868" (manufactured by Exciton) are preferable. A film containing a near-infrared absorber can be obtained by coating and molding a solution in which a near-infrared absorber is mixed with a polyimide resin solution. By adding a near-infrared absorber, the spectral characteristics can be remarkably improved. The amount of the near-infrared absorber added is preferably 0.1 to 50% by weight, more preferably 0.5 to 30% by weight, in the polyimide resin film. A near-infrared absorber can be included. Examples of the near-infrared absorber include squalylium-based pigments, cyanine-based pigments, phthalocyanine-based pigments, naphthalocyanine-based pigments, quaterylene-based pigments, dithiol metal complex-based dyes, and transition metal oxide-based compounds. Commercially available near-infrared absorbers include, for example, Nippon Kayaku's products "E-Excolor IR-10", "E-Excolor IR-12", "E-Excolor IR-14", and "E-Excolor HA-". 1 ”,“ E-Excolor HA-14 ”; Mitsui Chemicals' products“ SIR-128 ”,“ SIR-130 ”,“ SIR-132 ”,“ SIR-152 ”,“ SIR-159 ”,“ SIR -162 "; Nippon Kayaku Co., Ltd. product" Kayasorb IRG-022 "," Kayasorb IRG-023 "," Kayasorb IRG-040 "; Nippon Kayaku Co., Ltd. product" CIR-1081 "; Nagase ChemteX Co., Ltd. product" NIR " -IM1 "," NIR-AM1 "; Sumitomo Metal Mining Co., Ltd. cesium oxide tungsten compound; BASF company's products" Lumogen IR765 "," Lumogen IR788 ";Exciton'sproducts" ARS670T "," IRA800 "," Examples thereof include "IRA850" and "IRA868".

The content of the near-infrared absorber is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, based on the mass of the base material.

The base material contained in the light selection film of the present invention may contain an ultraviolet absorber. Examples of the ultraviolet absorber include a triazine derivative (triazine-based ultraviolet absorber) such as a benzotriazole derivative (benzotriazole-based ultraviolet absorber), a 1,3,5-triphenyltriazine derivative, and a benzophenone derivative (benzophenone-based ultraviolet absorber). ), And a salicylate derivative (salicylate-based ultraviolet absorber), and at least one selected from the group consisting of these can be used. Since it has good ultraviolet absorbing ability, it is preferable to use at least one selected from the group consisting of benzotriazole-based ultraviolet absorbers and triazine-based ultraviolet absorbers, and benzotriazole-based ultraviolet absorbers are more preferable.

Specific examples of the benzotriazole-based ultraviolet absorber include compounds represented by the formula (9), which can be used alone or in combination of two or more. Specific examples of the compound represented by the formula (9) include trade names: Sumisorb® 200 (2- (2-hydroxy-5-methylphenyl) benzotriazole) manufactured by Sumika Chemtex Co., Ltd., Sumisorb. 300 (2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole), Sumisorb 340 (2- (2-hydroxy-5-tert-octylphenyl) benzotriazole), Sumisorb 350 (2- (2-hydroxy 3,5-di-tert-pentylphenyl) benzotriazole).

In formula (9), T is a hydrogen atom, a fluorine atom, a chlorine atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and R ³⁵ and R ³⁶ are independently hydrogen atoms or or It is a hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ^{35 and} R ³⁶ is a hydrocarbon group having 1 to 20 carbon atoms.

Examples of the alkyl group having 1 to 5 carbon atoms in T include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and 2-. Examples thereof include a methyl-butyl group, a 3-methylbutyl group, and a 2-ethyl-propyl group.
Examples of the alkoxy group having 1 to 5 carbon atoms in T include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, and an n-pentyloxy group. Examples thereof include 2-methyl-butoxy group, 3-methylbutoxy group and 2-ethyl-propoxy group.
T is preferably a hydrogen atom, a fluorine atom, a chlorine atom or a methyl group, and more preferably a hydrogen atom, a fluorine atom or a chlorine atom.

R ³⁵ and R ³⁶ are hydrogen atoms or hydrocarbon groups having 1 to 20 carbon atoms, respectively, and at least one of R ³⁵ and R ³⁶ is a hydrocarbon group. When R ³⁵ and R ³⁶ are hydrocarbon groups, respectively, they are preferably hydrocarbon groups having 1 to 12 carbon atoms, and more preferably hydrocarbon groups having 1 to 8 carbon atoms. Specific examples thereof include a methyl group, a tert-butyl group, a tert-pentyl group and a tert-octyl group.

The content of the ultraviolet absorber is preferably 0.01 to 10 parts by mass, more preferably 1 to 8 parts by mass, and further preferably 3 to 7 parts by mass with respect to 100 parts by mass of the polyimide resin. When the content of the ultraviolet absorber is at least the above lower limit, the ultraviolet absorption can be improved. When the content of the ultraviolet absorber is not more than the above upper limit, the decomposition of the ultraviolet absorber due to heat during the production of the base material can be suppressed, the optical characteristics can be improved, for example, the haze can be reduced.

The base material contained in the photoselective film of the present invention can contain fillers, especially silica particles. The average primary particle size of the silica particles is preferably 5 nm or more, more preferably 10 nm or more, further preferably 15 nm or more, particularly preferably 20 nm or more, preferably 100 nm or less, more preferably 80 nm or less, still more preferably 60 nm or less. , Especially preferably 40 nm or less. When the average primary particle size of the silica particles is in the above range, aggregation of the silica particles can be suppressed, the optical properties of the base material can be improved, for example, haze and yellowness (YI value) can be reduced, and the transmittance can be increased. it can. The average primary particle size can be measured by, for example, the BET method.

The content of the filler, preferably silica particles, is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, based on the mass of the base material. Particularly preferably, it is 30% by mass or more, and preferably 60% by mass or less. When the content of the filler is at least the above lower limit, the elastic modulus is likely to be improved. Further, when the content of the filler is not more than the above upper limit, the optical characteristics can be easily improved, for example, the transmittance can be easily increased, and the haze and the yellowness (YI value) can be easily reduced.

The base material contained in the optical selection film of the present invention may contain other additives in addition to the filler, the near-infrared absorber and the ultraviolet absorber. Examples of other additives include mold release agents, stabilizers, colorants such as bluing agents, flame retardants, lubricants, and leveling agents. When the base material contains other additives, the content of the other additives is preferably about 0.01 to 20% by mass, more preferably about 0.1 to 10% by mass, based on the mass of the base material. is there.

The base material contained in the light selection film of the present invention has a total light transmittance (Tt) of 85% or more. Therefore, the base material can have excellent transparency. On the other hand, if the total light transmittance (Tt) is less than 85%, the substrate cannot exhibit sufficient transparency.
Further, since the transparency of the dielectric multilayer film contained in the light-selective film can be adjusted relatively easily depending on the composition or the like, the transparency of the light-selective film is as long as the total light transmittance of the base material is 85% or more. Can also be excellent. The total light transmittance of the base material can be measured by using a transmission measuring device having an integrating sphere as a measuring device in accordance with JIS K7375: 2008, and can be measured by, for example, the method described in Examples. In the present invention, the composition of the base material, for example, the type and composition ratio of the repeating structural unit (constituent unit) constituting the polyimide resin contained in the base material; the thickness of the base material; or the manufacturing conditions of the base material, etc. are appropriately determined. By adjusting, the total light transmittance can be adjusted to 85% or more. In particular, in the above-mentioned polyimide resin, if the structural units and their ratios capable of enhancing the transparency are selected and the step (A) is included in the base material manufacturing step (I), the total light transmittance is 85% or more. Easy to adjust.

The total light transmittance of the base material contained in the photoselective film of the present invention is preferably 87% or more, more preferably 89% or more, further preferably 90% or more, particularly preferably 91% or more, and even more preferably 92. % Or more. When the total light transmittance is at least the above lower limit, the transparency of the base material can be further improved. The upper limit of the total light transmittance is not particularly limited, but is usually 100% or less.

The base material contained in the optical selection film of the present invention has excellent transparency. Therefore, in a preferred embodiment of the present invention, the substrate has an average spectral transmittance of preferably 85% or more, more preferably 87% or more, still more preferably 89% or more, particularly preferably 89% or more at a wavelength of 450 to 600 nm. Is 90% or more. Further, the upper limit of the average value of the spectral transmittance at a wavelength of 450 to 600 nm of the base material is not particularly limited, but is usually 100% or less. The spectral transmittance of the base material can be measured with an ultraviolet-visible near-infrared spectrophotometer or the like, and the average value can be calculated by averaging the transmittance for each 1 nm at a wavelength of 450 to 600 nm. For example, it can be carried out by the method of the embodiment. Further, the average value of the spectral transmittance of the base material can be adjusted to 85% or more by the same method as the method for adjusting the total light transmittance to 85% or more.

The base material contained in the optical selection film of the present invention has excellent transparency. Therefore, in a preferred embodiment of the present invention, the substrate has a low haze. The haze of the base material is preferably 3.0% or less, more preferably 2.0% or less, still more preferably 1.0% or less, still more preferably 0.5% or less, and particularly preferably 0.3% or less. Is. The lower limit of the haze of the base material is not particularly limited, and is usually 0% or more. The haze can be measured by using a transmission measuring device having an integrating sphere as a measuring device in accordance with JIS K7375: 2008, and can be measured by, for example, the method described in Examples.

Since the optical selection film of the present invention contains a predetermined polyimide resin, it can have excellent process durability even if the thickness (film thickness) of the base material is thin. The thickness of the base material contained in the photoselective film of the present invention is preferably less than 100 μm, more preferably 80 μm or less, still more preferably 50 μm or less, particularly preferably 40 μm or less, more particularly preferably, from the viewpoint of thinning and transparency. Is 30 μm or less. Further, the thickness of the base material is preferably 1 μm or more, more preferably 5 μm or more, and further preferably 10 μm or more from the viewpoint of process durability. The thickness (film thickness) of the base material can be measured using a film thickness meter.
As used herein, the term "process durability" refers to a property that can suppress or prevent cracks and cracks in the film in the process of applying the optical selection film to a device such as a fingerprint authentication device. Specific examples include the property of suppressing or preventing the occurrence of cracks and cracks when the optical selection film is attached to a panel or the like via an adhesive or the like by using a laminate or the like. It can be evaluated in the same manner as the described method. Further, improving the process durability means that the occurrence of cracks and cracks can be more easily suppressed or prevented.

<Dielectric multilayer film>
In the optical selection film of the present invention, the dielectric multilayer film is laminated on at least one surface of the base material.
In one embodiment of the present invention, the dielectric multilayer film preferably has a function of reflecting and cutting near infrared rays (for example, 800 to 1000 nm). In such a case, the optical selection film of the present invention can function as a near-infrared cut filter. From the viewpoint of effectively reflecting near-infrared light, such a dielectric multilayer film preferably has a structure including a low refractive index layer and a high refractive index layer, and the low refractive index layer and the high refractive index layer. It is more preferable to have a structure in which and are alternately laminated. In the present specification, the low refractive index layer means a layer having a lower refractive index than the high refractive index layer, and conversely, the high refractive index layer means a layer having a higher refractive index than the low refractive index layer. ..

The difference in refractive index between the high refractive index layer and the low refractive index layer is preferably 0.5 or more, and more preferably 1.0 or more. When the difference in refractive index is 1.0 or more, the wavelength width in the near-infrared region that can be cut tends to be wide, and a dielectric multilayer film having more excellent near-infrared cut performance can be obtained.

As the material constituting the low refractive index layer, a material having a refractive index of 1.6 or less can be usually used, and a material having a refractive index of 1.2 to 1.6 can be preferably selected. Specific examples thereof include silica (SiO ₂ ), alumina, lanthanum fluoride, magnesium fluoride, and sodium hexafluoride, and silica is preferable from the viewpoint of near-infrared ray blocking property.

As the material constituting the high refractive index layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index of 1.7 to 2.5 can be preferably selected. Specifically, titanium oxide (TiO ₂ , also called titania), zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, ittrium oxide, zinc oxide, zinc sulfide, titanium oxide containing indium oxide as the main components, and oxidation. Examples thereof include those containing a small amount of tin, cerium oxide and the like, and titanium oxide (titania) is preferable.

In a preferred embodiment of the present invention, the low refractive index layer contains silica and the high refractive index layer contains titania because the dielectric multilayer film is excellent in near-infrared ray cutting performance.

In one embodiment of the present invention, the number of layers of the dielectric multilayer film is, for example, 10 to 80 layers, preferably 25 to 50 layers. This indicates the number of layers of one dielectric multilayer film, and when the base material has dielectric multilayer films on both sides, that is, when two dielectric multilayer films are laminated, the respective dielectric multilayer films are laminated. Show the number.

Further, the thickness of each layer of the high refractive index layer and the low refractive index layer in the dielectric multilayer film is the near-infrared wavelength λ (nm) to be blocked from the viewpoint of easily controlling the blocking and transmission of light having a specific wavelength. The thickness is preferably 0.1λ to 0.5λ. When the thickness is within the above range, the product (n × d) of the refractive index (n) and the film thickness (d) becomes almost the same value as the optical film thickness calculated by λ / 4, and the reflection / refraction Due to the optical characteristics, it tends to be easy to control the blocking / transmission of a specific wavelength. The film thickness of the dielectric multilayer film can be determined by measuring the step difference between the non-deposited portion and the film-formed portion using, for example, a fine shape measuring machine.

The film thickness of the dielectric multilayer film is preferably 0.1 μm or more, more preferably 0.5 μm or more, still more preferably 1 μm or more, preferably 50 μm or less, from the viewpoint of cuttability of near infrared rays and thinning. It is preferably 30 μm or less, more preferably 10 μm or less.

<Light selection film>
The present inventor presents an elastic modulus measured by pushing a base material in a light selection film by a nanoindentation method in a light selection film having the base material and a dielectric multilayer film on at least one surface of the base material. When the ratio (sometimes referred to as the indentation elastic modulus) is 4 GPa or more, the process durability is excellent even if the thickness of the base material is thin, especially in the process of applying the optical selection film to equipment such as a fingerprint authentication device. It has been found that the occurrence of cracks and cracks can be suppressed or prevented when the optical selection film is attached to a panel or the like via an adhesive or the like by using a laminate or the like. In addition to this, it has been found that by adjusting the total light transmittance of the base material to 85% or more, both excellent transparency of the base material and process durability can be achieved at the same time.
On the other hand, if the indentation elastic modulus is less than 4 GPa, the process durability is inferior, and cracks and cracks occur when the optical selection film is attached to the panel or the like as described above.

In the photoselective film of the present invention, the indentation elastic modulus is preferably 4.5 GPa or more, more preferably 5.0 GPa or more, still more preferably 5.5 GPa or more, and particularly preferably 6.0 GPa or more. When the indentation elastic modulus is at least the above lower limit, the process durability can be effectively improved. The upper limit of the indentation elastic modulus is not particularly limited, but is usually 15 GPa or less. The indentation elastic modulus can be obtained, for example, by performing indentation measurement by the nanoindentation method on the central portion of the cross section of the base material in the cross section obtained by cutting the optical selection film in the thickness direction. For example, it can be obtained by the method described in Examples.

In the present invention, the composition of the base material, for example, the type and composition ratio of the repeating structural unit (constituent unit) constituting the polyimide resin contained in the base material; the thickness of the base material; or the manufacturing conditions of the base material are appropriately adjusted. Therefore, the elastic modulus can be adjusted to 4 GPa or more. In particular, in the above-mentioned polyimide resin, if a structural unit or a ratio thereof that can increase the elastic modulus is selected, the elastic modulus can be easily adjusted to 4 GPa or more.

In a preferred embodiment of the present invention, the average value of the spectral transmittance, the total light transmittance and the haze of the light selective film of the present invention at a wavelength of 450 to 600 nm are the average of the spectral transmittances of the substrate at a wavelength of 450 to 600 nm. You can choose from values, total light transmittance, and a range similar to haze.

In a preferred embodiment of the present invention, the optical selective film of the present invention has an average spectral transmittance of preferably 60% or more, more preferably 70% or more at a wavelength of 450 to 550 nm. The upper limit of the average value of the spectral transmittance at a wavelength of 450 to 550 nm of the optical selection film is not particularly limited, and is usually 100% or less. The average value of the spectral transmittance at a wavelength of 650 to 1000 nm is preferably 10% or less, more preferably 5% or less, still more preferably 3% or less. The lower limit of the average value of the spectral transmittance at a wavelength of 650 to 1000 nm of the optical selection film is not particularly limited, and is usually 0% or more. The spectral transmittance of the optical selective film can be measured with an ultraviolet-visible near-infrared spectrophotometer or the like, and the average value can be calculated by averaging the transmittance for each 1 nm at a wavelength of 450 to 550 nm or a wavelength of 650 to 1000 nm. For example, it can be carried out by the method described in Examples.

を満たすことが好ましい。ここで、方向ｈ及び方向ｈ’は互いに対応する方向であり、方向ｖ及び方向ｖ’は互いに対応する方向である。これら方向が対応するとは、方位角が同じであることを意味する。
本発明の光選択フィルムにおける基材が上記関係式（Ｘ）を満たすと、基材の面状ムラ、厚みムラ、配向ムラ等のムラが少なく、基材がより優れた均質性を有することができる。これにより、本発明の光選択フィルムは基材と誘電体多層膜の密着性が高く、また、該基材を有する光選択フィルムも均質性に優れ、パネル等に貼合した際の密着性を向上し得る。なお、上記関係式を導き出すための方法等は、特開２０１８−２０３９８６号公報を参照できる。 Since the photoselective film of the present invention has excellent homogeneity between the base material and the film, the adhesion between the base material and the dielectric multilayer film can be improved, and when the film is attached to a panel or the like via an adhesive or the like. Can have excellent adhesion to the film. In addition, in this specification, the homogeneity shows the characteristic that the surface unevenness, the thickness unevenness, the orientation unevenness, etc. of a base material or a film are small.
In the film reciprocal space image obtained by Fourier transforming the projected image obtained by the projection method using the base material in the optical selection film of the present invention, the line profiles in the directions h and v orthogonal to each other are defined as line profiles h and v, respectively. In the background reciprocal space image obtained by Fourier transforming the background image obtained without using the base material in the projection method, the line profiles in the directions h'and v'orthogonal to each other are set as the line profiles h'and v', respectively. The maximum intensity of the line profile (h−h') obtained by subtracting the line profile _h'from the line profile h is Y _mh , the frequency indicating the maximum intensity Y _mh is X _mh , and the line profile v to the line profile v. _Assuming that the maximum intensity of the line profile (vv') obtained by subtracting'is Y _mv and the frequency indicating the maximum intensity Y _mv is X _mv , both Y _mh and Y _mv are 40 or less, and Y _mh. , Y _mv , X _mh and X _mv are the following relational expressions (X):

It is preferable to satisfy. Here, the direction h and the direction h'are directions corresponding to each other, and the direction v and the direction v'are directions corresponding to each other. Correspondence of these directions means that the azimuths are the same.
When the base material in the optical selection film of the present invention satisfies the above relational expression (X), there is little unevenness such as surface unevenness, thickness unevenness, and orientation unevenness of the base material, and the base material has better homogeneity. it can. As a result, the optical selection film of the present invention has high adhesion between the base material and the dielectric multilayer film, and the optical selection film having the base material also has excellent homogeneity, and the adhesion when bonded to a panel or the like is improved. Can be improved. For the method and the like for deriving the above relational expression, Japanese Patent Application Laid-Open No. 2018-203086 can be referred to.

In the above relational expression (X), the value of (Y _mh + Y _mv ) / (X _mh + X _mv ) ^1/2 is more preferably 25 or less, more preferably 22 or less, still more preferably 20 or less, still more preferably. It is 18 or less, particularly preferably 16 or less, more particularly preferably 14 or less, still more preferably 12 or less, and most preferably 9 or less. The smaller the value of (Y _mh + Y _mv ) / (X _mh + X _mv ) ^1/2 , the more advantageous in terms of film homogeneity, and the lower limit thereof is not particularly limited and may be 0 or more, and is usually 0. 5 or more.

The Y _mh and Y _mv are preferably 35 or less, more preferably 32 or less, still more preferably 30 or less, and particularly preferably 28 or less, from the viewpoint of easily improving the homogeneity of the substrate and the film and improving the adhesion. More particularly preferably, it is 26 or less. The smaller Y _mh and Y _mv are, the more advantageous it is in terms of substrate and film homogeneity, and the lower limit thereof may be 0 or more, usually 1 or more.
As a method for forming a base material satisfying the above relational expression (X) and the above ranges of Y _mh and Y _mv , for example, a polyimide-based resin varnish (simply called a varnish) when forming a base material in the step (I) described later is used. A method of adjusting so that the following relational expression (Y) is satisfied and the film thickness distribution of the base material is ± 3 μm or less; the conditions for drying the varnish coating film in step (I) are as described below. A method, for example, a method performed in multiple steps at a relatively low temperature; a method including step (A) in step (I), and the like, and in particular, a method including step (A) in at least step (I) is carried out. Is preferable. In a preferred embodiment of the present invention, step (A) is included in the manufacturing process, and the base material can be produced under relatively low temperature conditions (preferably 250 ° C. or lower), so that the homogeneity of the base material can be increased. The relational expression (X) and the above ranges of Y _mh and Y _mv can be satisfied. As a result, excellent adhesion can be exhibited.

The relational expression (Y) is a relational expression between the viscosity (cps) of the varnish and the resin concentration (mass%) of the varnish, and is as follows.

Here, the viscosity (cps) of the varnish is measured at 25 ° C. using an E-type viscometer according to JIS K8803: 2011. The resin concentration of the varnish represents the concentration (mass%) of the resin contained in the varnish, and is calculated from the mass of the resin contained in the varnish based on the total mass of the varnish. The product of the viscosity of the varnish represented by the above formula and the resin concentration of the varnish is preferably 4,000 or more, more preferably 5,000 or more, from the viewpoint of easily enhancing the optical homogeneity of the base material. The upper limit of the product of the viscosity of the varnish represented by the above formula and the resin concentration of the varnish is not particularly limited, but from the viewpoint of handling the varnish, it is preferably 10,000 or less, more preferably 7,000 or less.

The viscosity of the varnish is preferably 5,000 to 60,000 cps, more preferably 10,000 to 50,000 cps, and even more preferably 15,000 to 45,000 cps. When the viscosity of the varnish is at least the above lower limit, it is easy to increase the optical homogeneity of the base material, and when it is at least the above upper limit, it is preferable from the viewpoint of ease of handling the varnish.

The resin concentration of the varnish is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, still more preferably 10 to 25% by mass, and particularly preferably 15 to 25% by mass. The resin concentration of the varnish is preferably at least the above lower limit from the viewpoint of obtaining a thick film thickness, and is preferably at least the above upper limit from the viewpoint of ease of handling of the varnish.

The film thickness distribution of the base material is preferably ± 3 μm or less, more preferably ± 2.5 μm or less, and further preferably ± 2 μm or less. For the film thickness distribution of the base material, the film thickness at at least 20 points of the base material is measured using a film thickness meter, the average film thickness at 20 points is calculated, and the difference between the film thickness and the average film thickness at each place. Can be calculated from.

The optical selection film of the present invention may include a layer other than the base material and the dielectric multilayer film, for example, a functional layer. Examples of the functional layer include an ultraviolet absorbing layer, a hard coat layer, a primer layer, a gas barrier layer, an adhesive layer, a hue adjusting layer, a refractive index adjusting layer, an antireflection film and the like. The functional layer can be used alone or in combination of two or more.

In a preferred embodiment of the present invention, the optical selective film of the present invention has dielectric multilayer films on both sides of the substrate. In this aspect, it is easy to suppress the warp of the optical selection film and the cracking and cracking of the dielectric multilayer film.

[Manufacturing method of optical selection film]
The method for producing the optical selective film of the present invention is not particularly limited, but an example of the production method in a preferred embodiment is shown below.
The method for producing a photoselective film of the present invention includes a step (I) of forming a base material containing a polyimide resin and a step (II) of forming a dielectric multilayer film on at least one surface of the base material. Including. Further, the step (I) includes a step (A) of imidizing the polyimide-based resin precursor in the presence of a catalyst. As described above, in the present invention, by chemically imidizing in the presence of a catalyst, imidization can be performed at a relatively low temperature, so that the transparency of the obtained polyimide resin can be enhanced. Therefore, if step (A) is included in the production process of the polyimide resin, the total light transmittance can be easily adjusted to 85% or more. In addition, in this specification, a polyimide resin precursor means a polyimide resin before imidization (before ring closure).

<Step (I)>
Step (I) is a step of forming a base material containing a polyimide resin.
Hereinafter, an example of a specific manufacturing process of the polyimide resin (polyimide resin or polyamide-imide resin) and a manufacturing process of the base material containing the polyimide resin will be shown.
(Manufacturing process of polyimide resin)
In the polyimide resin, a diamine compound and a tetracarboxylic acid compound are reacted (also referred to as reaction (I)) to generate a polyimide resin precursor (polyamic acid), and the polyimide resin precursor is subjected to step (A) to provide polyimide. Can produce resin.

［式中、Ｘは式（１）及び／又は式（２）におけるＸと同じである］
で表される化合物（ジアミン化合物（ａ）ともいう）等が挙げられる。ジアミン化合物は単独又は二種以上組み合わせて使用でき、ジアミン化合物を二種以上使用する場合、ジアミン化合物（ａ）のＸの種類が互いに異なる二種以上のジアミン化合物を用いてもよい。 Examples of the diamine compound include the formula (a).

[In the formula, X is the same as X in the formula (1) and / or the formula (2)]
Examples thereof include a compound represented by (also referred to as a diamine compound (a)). The diamine compound can be used alone or in combination of two or more, and when two or more diamine compounds are used, two or more diamine compounds in which the types of X of the diamine compound (a) are different from each other may be used.

More specifically, diamine compounds include, for example, 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, a benzene ring is preferable. 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. The diamine compound can be used alone or in combination of two or more.

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

Specific 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-diamino. Aromatic amines with one aromatic ring, such as naphthalene; 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 (sometimes referred to as TFMB) 4,4'-bis (4-aminophenoxy) biphenyl, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-methyl) Aromatic diamines having two or more aromatic rings, such as phenyl) fluorene, 9,9-bis (4-amino-3-chlorophenyl) fluorene, and 9,9-bis (4-amino-3-fluorophenyl) fluorene. Can be mentioned. These can be used alone or in combination of two or more.

As the aromatic diamine, preferably 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylsulfone, 3,3'-Diaminodiphenyl sulfone, 1,4-bis (4-aminophenoxy) benzene, 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) -4,4'-diaminodiphenyl, 4,4'-bis (4-aminophenoxy) biphenyl, more preferably 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 1,4-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [ 4- (4-Aminophenoxy) phenyl] propane, 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) benzidine, 4,4'-bis (4-aminophenoxy) biphenyl. These can be used alone or in combination of two or more.

Among the above diamine compounds, it is preferable to use one or more selected from the group consisting of aromatic diamines having a biphenyl structure from the viewpoint of easily improving the elastic modulus and transparency of the photoselective film. 1 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 1 It is more preferable to use seeds or more, and it is further preferable to use 2,2'-bis (trifluoromethyl) benzidine.

The tetracarboxylic acid compound represents a tetracarboxylic acid or a tetracarboxylic acid derivative. Examples of the tetracarboxylic acid derivative include an anhydride of the tetracarboxylic acid, preferably a dianhydride, an acid chloride and the like.
Examples of the tetracarboxylic acid compound include an aromatic tetracarboxylic acid and an anhydride thereof, preferably an aromatic tetracarboxylic acid compound such as a dianhydride thereof; an aliphatic tetracarboxylic acid and an anhydride thereof, preferably a dianhydride thereof and the like. Examples of the aliphatic tetracarboxylic dian compound of the above. These tetracarboxylic acid compounds can be used alone or in combination of two or more.

［式中、Ｙは式（１）におけるＹと同じである］
で表される化合物（テトラカルボン酸化合物（ｂ）ともいう）等が挙げられる。テトラカルボン酸化合物は単独又は二種以上組み合わせて使用でき、テトラカルボン酸化合物を二種以上使用する場合、テトラカルボン酸化合物（ｂ）のＹの種類が互いに異なる二種以上のテトラカルボン酸化合物を用いてもよい。 The tetracarboxylic acid compound is more preferably a tetracarboxylic dianhydride. Examples of the tetracarboxylic dianhydride include the formula (b).

[In the equation, Y is the same as Y in equation (1)]
Examples thereof include a compound represented by (also referred to as a tetracarboxylic acid compound (b)). The tetracarboxylic dian compound can be used alone or in combination of two or more, and when two or more tetracarboxylic dian compounds are used, two or more tetracarboxylic dian compounds having different Y types of the tetracarboxylic dian compound (b) are used. You may use it.

Specific examples of the aromatic tetracarboxylic dianhydride include a non-condensed polycyclic aromatic tetracarboxylic dianhydride, a monocyclic aromatic tetracarboxylic dianhydride, and a condensed polycyclic aromatic tetra. Examples include carboxylic dianhydride. Examples of the non-condensed polycyclic aromatic tetracarboxylic dianhydride include 4,4'-oxydiphthalic acid dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride and 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) Phenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenoxyphenyl) propane dianhydride, 4,4'-(hexafluoroisopropyridene) diphthalic dianhydride (6FDA) Yes), 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-) Examples thereof include dicarboxyphenyl) methane dianhydride, 4,4'-(p-phenylenedioxy) diphthalic acid dianhydride and 4,4'-(m-phenylenedioxy) diphthalic acid dianhydride. Examples of the monocyclic aromatic tetracarboxylic dianhydride include 1,2,4,5-benzenetetracarboxylic dianhydride, and the condensed polycyclic aromatic dianhydride dianhydride includes 1,2,4,5-benzenetetracarboxylic dianhydride. Examples include 2,3,6,7-naphthalenetetracarboxylic dianhydride.

Among these, preferably 4,4'-oxydiphthalic acid dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic dianhydride. Anhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenyl Sulfontetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2- Bis (3,4-dicarboxyphenoxyphenyl) propane dianhydride, 4,4'-(hexafluoroisopropyridene) diphthalic acid dianhydride, 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, 4,4'-(p-phenylenedioxy) ) Diphthalic dianhydride and 4,4'-(m-phenylenedioxy) diphthalic dianhydride are mentioned, more preferably 4,4'-oxydiphthalic dianhydride, 3,3', 4,4. '-Biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 4,4'-(hexafluoroisopropyridene) diphthalic dianhydride, bis (3,4 Examples thereof include −dicarboxyphenyl) methane dianhydride and 4,4'-(p-phenylenedioxy) diphthalic 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 tetracarboxylic acid compounds, the alicyclic tetracarboxylic dianhydride or the non-condensation polycyclic aromatic tetracarboxylic dianhydride is used from the viewpoint of easily improving the elasticity, transparency and bending resistance of the photoselective film. Anhydride is preferred. Specific examples include 4,4'-oxydiphthalic acid dianhydride, 3,3', 4,4'-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-di) Carboxyphenyl) propane dianhydride, 4,4'-(hexafluoroisopropyridene) diphthalic acid dianhydride and mixtures thereof are preferred, 3,3', 4,4'-biphenyltetracarboxylic dianhydride and 4 , 4'-(hexafluoroisopropyridene) diphthalic dianhydride and mixtures thereof are more preferred, and 4,4'-(hexafluoroisopropyridene) diphthalic dianhydride is even more preferred.

In the reaction (I), the ratio of the diamine compound and the tetracarboxylic acid compound can be appropriately selected according to the composition ratio of the polyimide resin. The reaction (I) is preferably carried out in a solvent inert to the reaction. The solvent is not particularly limited as long as it does not affect the reaction, and for example, water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy-2-propanol, etc. Alcohol-based solvents such as 2-butoxyethanol and propylene glycol monomethyl ether; ester-based solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, γ-valerolactone, propylene glycol methyl ether acetate and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane and heptane; alicyclic hydrocarbon solvents such as ethyl cyclohexane; toluene and xylene Aromatic hydrocarbon solvents such as; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran and dimethoxyethane; chlorine-containing solvents such as chloroform and chlorobenzene; amides such as N, N-dimethylacetamide and N, N-dimethylformamide. Examples thereof include sulfur-containing solvents such as dimethyl sulfone, dimethyl sulfoxide and sulfolane; carbonate solvents such as ethylene carbonate and propylene carbonate; and combinations thereof (mixed solvents). Among these, a lactone-based solvent or an amide-based solvent can be preferably used from the viewpoint of the solubility of the diamine compound and the tetracarboxylic acid compound.

The reaction temperature of the reaction (I) is not particularly limited, but may be, for example, 5 to 200 ° C., preferably 20 to 190 ° C. The reaction time may be, for example, 1 minute to 72 hours, preferably 10 minutes to 24 hours. Further, the reaction may be carried out in air or in an inert gas atmosphere (for example, nitrogen, argon, etc.) with stirring, and may be carried out under normal pressure, pressure or reduced pressure. In a preferred embodiment, the operation is carried out at normal pressure or reduced pressure under an inert gas atmosphere with stirring.

A polyimide resin can be produced by subjecting the polyimide resin precursor (polyamic acid) obtained in the reaction (I) to the step (A). The step (A) is a step of imidizing the polyimide resin precursor in the presence of a catalyst.

Examples of the catalyst include aliphatic amines such as tripropylamine, dibutylpropylamine and ethyldibutylamine; N-ethylpiperidin, N-propylpiperidin, N-butylpyrolidin, N-butylpiperidin, N-propylhexahydroazepine and the like. Alicyclic amines (monocyclic); azabicyclo [2.2.1] heptane, azabicyclo [3.2.1] octane, azabicyclo [2.2.2] octane, and azabicyclo [3.2.2]. Alicyclic amines such as nonan (polycyclic); and pyridine, 2-methylpyridine (2-picolin), 3-methylpyridine (3-picolin), 4-methylpyridine (4-picolin), 2-ethylpyridine , 3-Ethylpyridine, 4-Ethylpyridine, 2,4-Dimethylpyridine, 2,4,6-trimethylpyridine, 3,4-Cyclopentenopyridine, 5,6,7,8-Tetrahydroisoquinoline, Isoquinolin, etc. Aromatic amines can be mentioned.

The amount of the catalyst used is preferably 0.001 to 10 mol, more preferably 0.01 to 5 mol, based on 1 mol of the tetracarboxylic acid compound used in the reaction (I).

An acid anhydride can also be used together with the imidization catalyst from the viewpoint of facilitating the imidization reaction. Examples of the acid anhydride include conventional acid anhydrides used in the imidization reaction, and specific examples thereof include acetic anhydride, propionic anhydride, butyric anhydride and other aliphatic acid anhydrides, and phthalic acid and other aromatics. Acid anhydride and the like can be mentioned.

When an acid anhydride is used, the amount of the acid anhydride used is preferably 0.5 to 25 mol, more preferably 1 to 20 mol, still more preferably 5 to 15 mol, based on 1 mol of the tetracarboxylic acid compound. Is.

Step (A) can be performed in a solvent. Examples of the solvent include those exemplified above as the solvent in the reaction (I).

The reaction temperature in step (A) is preferably 250 ° C. or lower, more preferably 220 ° C. or lower, still more preferably 200 ° C. or lower, and particularly preferably 180 ° C. or lower. When the reaction temperature is not more than the above upper limit, the transparency of the obtained polyimide resin can be improved, and the total light transmittance of the base material can be easily adjusted to 85% or more. The reaction temperature in step (A) is not particularly limited, but is usually 100 ° C. or higher from the viewpoint of imidization reactivity. The reaction time, atmosphere and pressure of step (A) can be selected from the same as those of reaction (I).

In one embodiment of the present invention, it is preferable to carry out step (A) continuously in the reaction system without purifying the polyimide resin precursor in step (I). In such a case, a catalyst may be charged together with the diamine compound and the tetracarboxylic acid which are the raw materials of the reaction (I) (the catalyst may be added to the reaction system). As a result, after the polyimide resin precursor is produced in the reaction system in the reaction (I), it is continuously imidized, so that the production efficiency can be improved.

The obtained polyimide resin can be isolated (separated and purified) by a conventional method, for example, a separation means such as filtration, concentration, extraction, crystallization, recrystallization, or column chromatography, or a separation means combining these. Often, in a preferred embodiment, the reaction solution containing the polyimide resin can be isolated by adding a large amount of solvent (for example, alcohol, water, etc.) to precipitate the polyimide resin, and performing concentration, filtration, drying, and the like. The polyimide resin may be used to form a base material using the solution after the reaction without isolation.

(Manufacturing process of polyamide-imide resin)
In a polyamide-imide resin, a diamine compound and a tetracarboxylic acid compound are reacted (also referred to as reaction (II)) to produce a polyamic acid, and the polyamic acid and a dicarboxylic acid compound are reacted (sometimes referred to as reaction (III)). To produce a polyamide-imide resin precursor, and subject the polyamide-imide resin precursor to step (A), a polyamide-imide resin can be produced.

［式中、Ｚは式（２）におけるＺと同じであり、Ｒ^１９及びＲ^２０は、それぞれ独立して、−ＯＨ、−ＯＭｅ、−ＯＥｔ、−ＯＰｒ、−ＯＢｕ又は−Ｃｌであり、好ましくは−Ｃｌである］
で表される化合物（ジカルボン酸化合物（ｃ）と称する場合がある）等が挙げられる。ジカルボン酸化合物は単独又は二種以上組み合わせて使用でき、ジカルボン酸化合物を二種以上使用する場合、ジカルボン酸化合物（ｃ）のＺの種類が互いに異なる二種以上のジカルボン酸化合物を用いてよい。 Reaction (II) is the same as the above reaction (I).
The dicarboxylic acid compound used in the reaction (III) shows a dicarboxylic acid or a dicarboxylic acid derivative, and examples of the dicarboxylic acid derivative include an acid chloride and an ester of the dicarboxylic acid. Examples of the dicarboxylic acid compound include the formula (c).

[In the formula, Z is the same as Z in the formula (2), and R ¹⁹ and R ²⁰ are independently -OH, -OMe, -OEt, -OPr, -OBu or -Cl, which are preferable. Is -Cl]
Examples of the compound represented by (may be referred to as a dicarboxylic acid compound (c)) and the like. The dicarboxylic acid compounds can be used alone or in combination of two or more, and when two or more dicarboxylic acid compounds are used, two or more dicarboxylic acid compounds having different Z types of the dicarboxylic acid compound (c) may be used.

Specific examples of the dicarboxylic acid compound include 4,4'-oxybis benzoic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, and two benzoic acids. Aromatic dicarboxylic acids such as compounds in which the acid is single-bonded, -CH _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -SO _2- or a phenylene group and derivatives thereof. (For example, acid chloride, acid anhydride); Examples thereof include aliphatic dicarboxylic acids such as dicarboxylic acid compounds of chain hydrocarbons having 8 or less carbon atoms and derivatives thereof (for example, acid chlorides and esters). These dicarboxylic acid compounds can be used alone or in combination of two or more. Among these, the combined use of 4,4'-oxybis (benzoyl chloride) and terephthaloyl chloride can be mentioned as a preferable example from the viewpoint of easily improving the elastic modulus, transparency and bending resistance of the photoselective film.

In the reaction (III), the amount of the dicarboxylic acid compound to be reacted with the polyamic acid can be appropriately selected according to the ratio of the constituent units of the polyamide-imide resin. Reaction (III) is preferably carried out in the presence of a solvent. Examples of the solvent include those exemplified above as the solvent in the reaction (I). The reaction temperature and reaction time can be selected from the range of reaction temperature and reaction time in reaction (I), and the pressure and atmosphere can also be selected from those in reaction (I).
The polyamic acid obtained in the reaction (II) may be isolated by the above-mentioned separation means, but is usually subjected to the direct reaction (III) without isolation. Further, the polyamide-imide precursor obtained in the reaction (III) may be isolated by the above-mentioned separation means, but usually, it is directly subjected to the step (A) without being isolated.

The step (A) in the polyamide-imide resin manufacturing process can be performed in the same manner as the step (A) in the polyimide resin manufacturing process. In the present invention, as described above, by using a catalyst (chemical imidization) in step (A), imidization can be performed at a relatively low temperature, preferably 250 ° C. or lower, and thus the obtained polyamide-imide resin. Can improve the transparency of.

The polyamide-imide resin obtained in step (A) may be isolated by the above-mentioned separation means. The polyamide-imide resin may be used to form a base material using the solution after the reaction without isolation.

(Formation of base material)
The base material manufacturing process is not particularly limited, but an example of the manufacturing process in a preferred embodiment of the present invention is shown below. The base material is
(A) A step of preparing a liquid containing the polyimide resin (sometimes referred to as a polyimide resin varnish) (varnish preparation step),
(B) A step of applying a polyimide resin varnish to a support material to form a coating film (coating step), and (c) a step of drying the applied liquid (coating film) to form a base material (base). Material forming process)
It can be manufactured by a method including.

In the varnish preparation step, the polyimide resin obtained in the above manufacturing step is dissolved in a solvent, and if necessary, a filler, a near-infrared absorber, an ultraviolet absorber, another additive, etc. are added and mixed by stirring. Prepare a polyimide resin.

The solvent used for preparing the varnish is not particularly limited as long as the polyimide resin can be dissolved. Examples of such a solvent include those exemplified above as the solvent used in the reaction (I). Among these solvents, a lactone-based solvent or an amide-based solvent can be preferably used. These solvents can be used alone or in combination of two or more. The solid content concentration of the polyimide resin varnish is preferably 1 to 40% by mass, more preferably 5 to 30% by mass, still more preferably 10 to 25% by mass, and particularly preferably 15 to 25% by mass.

In the coating step, a polyimide resin varnish is applied onto the support material 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 base material forming step, the base material can be formed by drying the coating film and peeling it from the support material. The drying may be carried out under conditions of an inert atmosphere or reduced pressure, if necessary. The drying is preferably carried out at a relatively low temperature for a long time from the viewpoint of easily increasing the homogeneity of the base material. When drying by heating, the heating temperature at the time of drying is preferably 60 to 150 ° C., more preferably 60 to 130 ° C., still more preferably 70 to 120 ° C. The drying time is preferably 5 to 60 minutes, more preferably 10 to 40 minutes. Drying may be carried out under one-step or multi-step conditions, but is preferably carried out under three-step or higher heating temperature conditions. When drying is carried out under multi-step conditions, it is possible to carry out drying under the same or different temperature conditions and / or drying times in each step, for example, 3 to 10 steps, preferably 3 to 8 steps. Drying may be carried out under the conditions of. When drying is carried out under multi-step conditions, it is easy to improve the homogeneity of the base material. It is preferable to carry out drying under a multi-step condition of 3 or more steps. In one embodiment, the drying temperature profile preferably includes temperature rise and fall. That is, it is more preferable to perform drying under three or more heating temperature conditions in which the temperature profile includes temperature rise and fall. Taking the case of four stages as an example of such a temperature profile, the drying temperatures are 70 to 90 ° C. (first temperature), 90 to 120 ° C. (second temperature), and 70 to 120 ° C. (second temperature), respectively. 3rd temperature) and 70-100 ° C (4th temperature). In this example, the drying temperature is raised from the first temperature to the second temperature, then lowered from the second temperature to the third temperature, and further lowered from the third temperature to the fourth temperature. Raise the temperature. Here, the drying time is, for example, 5 to 15 minutes at each stage. It is preferable to carry out the drying so that the residual amount of the solvent in the dry coating film is preferably 5 to 15% by mass, more preferably 6 to 12% by mass with respect to the mass of the dry coating film. When the residual amount of the solvent is in the above range, the homogeneity of the base material can be easily improved. Further, when the second drying described later is performed, it is easy to improve the peelability when the coating film is peeled from the support. The residual amount of the solvent is reduced by increasing the drying temperature of each step and increasing the drying time. Therefore, the homogeneity of the base material can be improved by adjusting the drying temperature and the drying time so that the residual amount of the solvent is in the desired range. After peeling from the support material, a second drying may be performed to further dry the base material. When performing the second drying, it is preferable to apply tension to the coating film and heat the coating film in a state of being stretched in the in-plane direction. By heating while applying tension, it is easy to suppress a decrease in the homogeneity of the base material caused by shrinkage of the coating film due to drying.

Examples of the support material include a PET film, a PEN film, a polyamide film, a polyimide film different from the base material, a polyamide-imide film, and the like. Among them, PET film, PEN film and the like are preferable from the viewpoint of excellent heat resistance, and PET film is more preferable from the viewpoint of adhesion to a polyimide resin and cost.

<Step (II)>
The step (II) is a step of forming a dielectric multilayer film on at least one surface of the base material obtained in the step (I).
Examples of the method for forming the dielectric multilayer film include a chemical vapor deposition method (CVD method), a sputtering method, and a vacuum vapor deposition method.

The temperature at the time of forming the dielectric multilayer film is preferably 250 ° C. or lower, more preferably 220 ° C. or lower, still more preferably 200 ° C. or lower, and particularly preferably 180 ° C. or lower. When the temperature at the time of forming the dielectric multilayer film is not more than the above upper limit, the transparency of the optical selection film can be easily improved. The temperature at the time of forming the dielectric multilayer film is usually 100 ° C. or higher.

[Application example of optical sensor including optical selection film]
The present invention includes an optical sensor that includes the optical selection film of the present invention. The optical sensor of the present invention can be suitably applied to a detection unit included in various electronic devices such as workstations, personal computers, personal digital assistants, access control systems, digital cameras, and medical devices.

The optical sensor of the present invention includes an image detection unit (image sensor), a fingerprint detection unit, a face detection unit, and a vein detection unit for a solid-state imaging device such as an X-ray imaging device and a CMOS image sensor, which are included in the above-exemplified electronic devices. It can be suitably applied to a detection unit that detects a predetermined feature of a part of a living body such as a unit and an iris detection unit.

Since the optical sensor of the present invention contains an optical selection film having excellent process durability, the yield during manufacturing can be improved. Further, since the optical selection film has high transparency and adhesion, it is possible to form an optical sensor having high transparency and good mechanical strength.
Further, in a preferred embodiment of the present invention, since the photoselective film of the present invention has a function of cutting near infrared light, the optical sensor including the photoselective film is caused by ambient light such as natural light or illumination light. It is possible to suppress or prevent the generation of noise and the like, and improve the optical characteristics.

Examples of the optical sensor include a photodiode, an avalanche photodiode (APD), a photomultiplier tube (PMT), and the like. For example, an optical selection film can be formed by bonding with an adhesive or the like. Above all, an organic photodiode containing an organic semiconductor in a light receiving portion can be manufactured on a film base material, and can be easily bonded to the optical selection film of the present invention.

An example of an electronic device is a fingerprint authentication device. The present invention includes a fingerprint authentication device including the optical sensor of the present invention. The fingerprint authentication device is not particularly limited as long as it includes a function of performing fingerprint authentication, but its configuration includes, for example, a photodiode, the light selection film, and a light source (for example, an organic light emitting diode (OLED)). It is preferable that the configuration includes the components. The fingerprint authentication device according to the embodiment of the present invention includes a photodiode, the optical selection film, a backplane, an OLED, a circular polarizing plate, a touch sensor, and a cover glass in this order.

[Measurement of total light transmittance Tt and haze]
The total light transmittance and haze of the base material in Examples and Comparative Examples were measured using a direct reading haze computer (HGM-2DP, manufactured by Suga Test Instruments Co., Ltd.).

[Measurement of spectral transmittance]
Using an ultraviolet-visible near-infrared spectrophotometer (manufactured by JASCO Corporation, V-670), the spectral transmittance of the substrate in the examples and comparative examples at a wavelength of 450 to 600 nm, and the optical selection film in the examples. The spectral transmittances at wavelengths of 450 to 550 nm and 650 to 1000 nm were measured, and the average values of the spectral transmittances in each wavelength range were calculated by averaging the transmittances for each 1 nm.

[Thickness of base material]
The thickness of the base material in Examples and Comparative Examples was measured using a film thickness meter (manufactured by Mitutoyo Co., Ltd., dial gauge application measuring instrument 547-401).

[Thickness of dielectric multilayer film]
The film thickness of the dielectric multilayer film in Examples and Comparative Examples was determined by using a fine shape measuring machine (Surfcorder ET3000 manufactured by Kosaka Laboratory Co., Ltd.) in a non-deposited portion (base material portion) and a film-formed portion (base). The step difference between the material and the dielectric multilayer film was measured to determine the thickness of the dielectric multilayer film.

[Measurement of elastic modulus]
The elastic modulus was measured by pushing the substrate in the photoselective film in Examples and Comparative Examples. Specifically, after preparing the cross section (cross section cut in the thickness direction) of the optical selection film by the microtome method, the film is fixed to the stage, and a single indentation measurement is performed twice at the center of the cross section of the base material in the cross section. The elastic modulus was calculated by analyzing the obtained data (relationship between load and displacement). The elastic modulus is the average value of the two measurements.
Device name: TriboIndenter manufactured by Hysiron
Indenter used: Berkovich (trigonal pyramid)

[Process durability]
As a transparent adhesive, an acrylic pressure-sensitive organic solvent solution prepared by adding an isocyanate-based cross-linking agent to a copolymer of butyl acrylate, methyl acrylate, and hydroxyethyl acrylate is subjected to a mold release treatment. A sheet-like pressure-sensitive adhesive with a release film was prepared by applying a die coater to the release-treated surface of a 75 μm polyethylene terephthalate film (release film) so that the thickness after drying was 50 μm. Next, the sheet-shaped pressure-sensitive adhesive with a release film was adhered onto one surface of the light-selection film in Examples and Comparative Examples without bubbles with a laminator to obtain a light-selection film with a transparent pressure-sensitive adhesive. After peeling the release film from the obtained optical selective film with transparent adhesive, those with no cracks or cracks when pasted to the panel with a laminator are 〇 (good), and those with cracks or cracks during bonding. Was evaluated as × (defective).

[Weight average molecular weight (Mw)]
Gel Permeation Chromatography (GPC) Measurement (1) Pretreatment Method The polyimide resin obtained in the example was dissolved in γ-butyrolactone (GBL) to make a 20% solution, and then diluted 100-fold with a DMF eluent. A solution filtered by a 0.45 μm polyimide filter was used as a measurement solution.
(2) Measurement condition column: TSKgel SuperAWM-H × 2 + SuperAW2500 × 1 (6.0 mm ID × 150 mm × 3)
Eluent: DMF (10 mM 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

[Example 1]
(Manufacturing of polyimide resin varnish)
Under a nitrogen atmosphere, 1.25 g of isoquinoline was charged into a reaction vessel to which a vacuum pump equipped with a solvent trap and a filter was connected. Next, 375.00 g of γ-butyrolactone (GBL) and 104.12 g of 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl (TFMB) were added to the reaction vessel, and the mixture was stirred to completely dissolve. I let you. Further, 145.88 g of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) was added, and then the temperature was started in an oil bath with stirring. The molar ratio of added TFMB to 6FDA was 1.00: 0.99, and the monomer concentration was 40 wt%. When the internal temperature reached 80 ° C., the pressure was reduced to 650 mmHg, and then the internal temperature was raised to 180 ° C. After reaching 180 ° C., after further heating and stirring for 4 hours, the pressure was restored to atmospheric pressure and cooled to 155 ° C. to obtain a polyimide resin solution. GBL was added at 155 ° C. to prepare a uniform solution having a solid content of the polyimide resin of 24% by mass, and then the polyimide resin varnish was taken out from the reaction vessel. The weight average molecular weight (Mw) of the polyimide resin was 385,000.

(Manufacturing of base material)
To 2000.00 g of the obtained polyimide resin varnish, 38.31 g of GBL and 11.82 g of N, N-dimethylacetamide (DMAc) were added and further diluted. It was salivated on a PET (polyethylene terephthalate) film to form a coating film. The linear velocity was 0.4 m / min. The coating film was dried by heating at 70 ° C. for 7.5 minutes, 120 ° C. for 7.5 minutes, 70 ° C. for 7.5 minutes, and 75 ° C. for 7.5 minutes, and the coating film was peeled off from the PET film. Then, the coating film was heated (post-baked) at 200 ° C. for 25 minutes to obtain a substrate (polyimide film) having a film thickness of 30 μm.

(Manufacturing of optical selection film)
A low refractive index layer (silica layer) (SiO ₂ : film thickness of about 150 nm) and a high refractive index layer (titania layer) (TiO ₂ : film thickness of about 100 nm) on both sides of a substrate having a side of 60 mm at a vapor deposition substrate temperature of 180 ° C. ) And were alternately laminated to form a dielectric multilayer film. A total of 36 layers on one side were vapor-deposited on both sides to form a dielectric multilayer film, and a photoselective film was produced. The film thickness of the dielectric multilayer film was about 5 μm.

[Comparative Example 1]
A photoselective film by forming a dielectric multilayer film on both sides of a cycloolefin polymer film (COP film, manufactured by Nippon Zeon Corporation, "Zeonoa film ZF-16", thickness: 50 μm) in the same manner as in Example 1. Manufactured.

Regarding the base material and the light selective film obtained in the above Examples and Comparative Examples, the total light transmittance (Tt), the average value (%) of the haze and the spectral transmittance of the base material, and the light selective film were obtained according to the above measurement method. The elasticity (GPa) of the substrate inside and the process durability of the photoselective film were measured. The results obtained are shown in Table 1.

[Table 1]

The average value of the spectral transmittance of the optical selection film of Example 1 at a wavelength of 450 nm to 550 nm was 75.1%, and the average value of the spectral transmittance at a wavelength of 650 nm to 1000 nm was less than 2%.

It was confirmed that the photoselective film obtained in Example 1 had good process durability and a total light transmittance of 92.5% as a base material. On the other hand, it was confirmed that the optical selection film obtained in Comparative Example 1 had poor process durability.
Therefore, it was found that the photoselective film of the present invention is excellent in the transparency of the base material and the process durability.

Claims (10)

An optical selection film having a base material containing a polyimide resin and a dielectric multilayer film on at least one surface of the base material.
The total light transmittance of the base material is 85% or more.
A photoselective film having an elastic modulus of 4 GPa or more measured by pushing a substrate in the photoselective film by the nanoindentation method. The optical selection film according to claim 1, wherein the thickness of the base material is less than 100 μm. The optical selection film according to claim 1 or 2, wherein the thickness of the base material is 40 μm or less. The optical selection film according to any one of claims 1 to 3, wherein the dielectric multilayer film has a structure in which low refractive index layers and high refractive index layers are alternately laminated. The light selection film according to claim 4, wherein the low refractive index layer contains silica and the high refractive index layer contains titania. The optical selection film according to any one of claims 1 to 5, which has a dielectric multilayer film on both sides of the base material. An optical sensor comprising the optical selection film according to any one of claims 1 to 6. A fingerprint authentication device including the optical sensor according to claim 7. One of claims 1 to 6, which comprises a step (I) of forming a base material containing a polyimide resin and a step (II) of forming a dielectric multilayer film on at least one surface of the base material. The method for producing an optical selection film according to the above method.
The method (I) comprises the step (A) of imidizing the polyimide resin precursor in the presence of a catalyst. The method according to claim 9, wherein step (A) is performed at a temperature of 250 ° C. or lower.