KR102042677B1 - Optical multilayer body - Google Patents

Abstract

[PROBLEMS] To provide an optical laminate having excellent surface hardness.
SOLUTION The optical laminated body which has a base film containing polyamide resin and an aromatic compound, and a hard coat layer in at least one surface of the said base film.

Description

Optical laminated body {OPTICAL MULTILAYER BODY}

This invention relates to the optical laminated body used as a front plate etc. of an image display apparatus.

Image display apparatuses, such as a liquid crystal display device and an organic electroluminescence display, are widely utilized for various uses, such as a mobile telephone and a smart watch. Glass has been used as the front plate of such an image display device. While glass has high transparency and can express high hardness depending on the type of glass, it is very rigid and brittle, making it difficult to use a flexible display as a front panel material. Therefore, utilization of a polymeric material is examined as a material which replaces glass. Since the front plate which consists of a polymeric material tends to express a flexible characteristic, it can be expected to use for various uses. Although various things can be mentioned as resin which has flexibility, One of them is polyamideimide. Polyamide-imide is used for various uses from a viewpoint of transparency and heat resistance (for example, Unexamined-Japanese-Patent No. 2016-125063).

Japanese Unexamined Patent Application Publication No. 2016-125063

The front plate of such an image display device requires high surface hardness because the user touches directly or the surrounding objects directly contact each other. However, according to examination by the present inventor, it turned out that the optical laminated body containing polyamide-type resin may not have enough surface hardness.

Therefore, the objective of this invention is providing the optical laminated body which has the outstanding surface hardness.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, in this optical laminated body which has a hard-coat layer in at least one surface of the base film containing polyamide-type resin, When the aromatic compound is contained, it has been found that the above object is achieved, and the present invention has been completed. That is, the following is included in this invention.

[1] An optical laminate having a base film containing a polyamide resin and an aromatic compound and a hard coat layer on at least one surface of the base film.

[2] The optical laminate according to [1], wherein the polyamide resin is polyamideimide.

[3] The optical laminate according to [1] or [2], wherein the aromatic compound is an ultraviolet absorber.

[4] The optical laminate according to [3], wherein the content of the ultraviolet absorber is 0.01 to 10 parts by mass with respect to 100 parts by mass of the polyamide-based resin.

[5] The polyamideimide is formula (1) and formula (2):

[In Formula (1) and Formula (2), X and Z respectively independently represent a divalent organic group, and Y represents a tetravalent organic group.]

Content of the structural unit represented by Formula (2) which has a structural unit represented by is represented by any of [2]-[4] which is 0.1-3.9 mol with respect to 1 mol of structural units represented by Formula (1). The optical laminate described.

[6] The optical laminate according to any one of [3] to [5], wherein the content of the ultraviolet absorbent contained in the base film is larger than the content of the ultraviolet absorbent in the hard coat layer.

[7] The optical laminate according to any one of [1] to [6], in which the base film contains inorganic particles.

[8] The optical laminate according to any one of [1] to [7], wherein the light transmittance at 390 nm is 35% or less.

[9] The polyamideimide is formula (1) and formula (2):

[In Formula (1) and Formula (2), X and Z respectively independently represent a divalent organic group, Y represents a tetravalent organic group,

At least part of Z is of the formula (3):

(Formula (3) of, R ¹ ~R ⁸ are, each independently, a hydrogen atom contained in the hydrogen atom and represents an alkyl group having 1 to 6 carbon atoms or 6 to 12 carbon atoms of the aryl, R ¹ ~R ⁸ are each Independently, they may be substituted by a halogen atom,

A represents -O-, -S-, -CO- or -NR ^9- , R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom,

m is an integer of 0 to 4,

* Represents a bonding hand)

Is a structural unit represented by

The optical laminated body in any one of [2]-[8] which has a structural unit represented by the following.

[10] A flexible image display device comprising the optical laminate according to any one of [1] to [9].

[11] The flexible image display device according to [10], further comprising a polarizing plate.

[12] The flexible image display device according to [10] or [11], further containing a touch sensor.

The optical laminated body of this invention has the outstanding surface hardness.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows an example of the laminated constitution in the optical laminated body of this invention.

The optical laminated body of this invention has a base film containing a polyamide-type resin and an aromatic compound, and the hard coat layer in at least one surface of the said base film.

<Base film>

The base film contains a polyamide resin and an aromatic compound.

(Polyamide Resin)

The polyamide resin refers to polyamide and polyamideimide. Polyamide means the polymer containing the structural unit containing an amide group. Polyamide-imide means the polymer containing the structural unit containing both an imide group and an amide group.

Polyamide may be polyamide resin, and it is preferable that it is polyamide imide from a viewpoint of the surface hardness of an optical laminated body.

It is preferable that polyamide has a structural unit represented by Formula (2), and it is preferable that polyamideimide has a structural unit represented by Formula (1) and a structural unit represented by Formula (2).

In Formula (2), Z is a divalent organic group, Preferably it is a C4-C40 organic group which may be substituted by the C1-C8 hydrocarbon group or the fluorine-substituted C1-C8 hydrocarbon group. . As the organic group of Z, formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), formula (28) And a group in which two non-adjacent groups are substituted with hydrogen atoms and a divalent chain hydrocarbon group having 6 or less carbon atoms are exemplified among the bonds of the group represented by the formula (29). Since the yellowness of the film obtained is easy to be suppressed (YI value is reduced), group represented by Formula (20)-Formula (27) is preferable.

In one embodiment of the present invention, the polyamide-based resin may include 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, in view of the fact that the optical laminate can express low yellowness (YI value) in addition to high surface hardness, at least a part of Z is represented by the formula (3):

Equation (3) of, R ¹ ~R ⁸ are, each independently, a hydrogen atom contained in the hydrogen atom and represents an alkyl group having 1 to 6 carbon atoms or 6 to 12 carbon atoms of the aryl, R ¹ ~R ⁸ are each Independently, they may be substituted by a halogen atom,

A is -O-, -S-, -CO- or -N (R ⁹⁾ - represents a, R ⁹ represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which is optionally substituted by halogen atoms,

m is an integer of 0 to 4,

* Represents a bonding hand]

It is preferable that it is a structural unit represented by.

In the formula (3), A is each independently, -O-, -S-, -CO- or -N (R ⁹⁾ - a represents, in terms of the flexibility of the optical laminate, preferably -O Or -S-, more preferably -O-.

R ¹ to R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Examples of the alkyl group 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-butyl group , 3-methylbutyl group, 2-ethyl-propyl group, n-hexyl group and the like. Moreover, as a C6-C12 aryl group, a phenyl group, a tolyl group, a xylyl group, a naphthyl group, a biphenyl group etc. are mentioned, for example. From the viewpoint of surface hardness and flexibility of the optical laminate, R ¹ to R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or 1 to 3 carbon atoms. An alkyl group is represented, More preferably, a hydrogen atom is represented. Here, the hydrogen atoms contained in R ¹ to R ⁸ may be each independently substituted with a halogen atom.

R <^9> represents the C1-C12 monovalent hydrocarbon group which may be substituted by the halogen atom. Examples of the monovalent hydrocarbon group having 1 to 12 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 -Butyl group, 3-methylbutyl group, 2-ethyl-propyl group, n-hexyl group, n-heptyl group, n-octyl group, tert-octyl group, n-nonyl group, n-decyl group, etc. are mentioned. These may be substituted by the halogen atom. As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned.

In Formula (3), m is an integer of the range of 0-4, and if m is in this range, the flexibility of an optical laminated body is favorable. Moreover, in Formula (3), m is preferably an integer in the range of 0-3, More preferably, it is an integer in the range of 0-2, More preferably, it is 0 or 1, and if m is in this range, While the flexibility of the optical laminate is good, the availability of raw materials is relatively good. Moreover, Z may contain 1 type, or 2 or more types of structural units represented by Formula (3), and it is a viewpoint of the surface hardness of an optical laminated body, the elasticity modulus, the bending resistance improvement, and the yellowness (YI value) reduction. In particular, in particular, two or more kinds of structural units having different values of m, preferably two kinds of structural units having different values of m may be included. In that case, it is preferable to include both the structural units whose m is 0 and 1 from a viewpoint that an optical laminated body is easy to express high surface hardness, elasticity modulus, bending resistance, and low yellowness (YI value).

In a suitable embodiment of the present invention, formula (3) is a structural unit or formula (3 ') wherein m = 0 and R ¹ to R ⁸ are hydrogen atoms:

It is a structural unit shown by these, It can also use together. In this case, the optical laminated body which consists of polyamide resin can exhibit high surface hardness, low elasticity modulus, and can have high flexibility.

In a preferred embodiment of the present invention, the structural unit represented by formula (3) when m is 0 to 4 with respect to the sum of Y and Z of the polyamide-based resin is preferably 20 mol% or more. It is preferably at least 30 mol%, more preferably at least 40 mol%, particularly preferably at least 50 mol%, most preferably at least 60 mol%, preferably at most 90 mol%, more preferably 85 It is mol% or less, More preferably, it is 80 mol% or less. When the structural unit represented by Formula (3) when m is 0-4 is more than the said lower limit with respect to the sum total of Y and Z in polyamide resin, the optical laminated body containing polyamide resin will have a high surface. In addition to being able to express hardness, the elastic modulus may be low and the flexibility may be excellent. When the structural unit represented by Formula (3) when m is 0-4 with respect to the sum total of Y and Z in polyamide-type resin is below the said upper limit, Thickening by hydrogen bond between amide bonds derived from Formula (3) By suppressing (i), the viscosity of the polyamide-based resin varnish described later can be suppressed, and the processing of the optical laminate can be facilitated.

In a preferred embodiment of the present invention, the structural unit represented by formula (3) in the case where m is 1 to 4 with respect to the sum of Y and Z of the polyamide-based resin is preferably 3 mol% or more. It is preferably at least 5 mol%, more preferably at least 7 mol%, particularly preferably at least 9 mol%, preferably at most 90 mol%, more preferably at most 70 mol%, even more preferably 50 mol It is% or less, Especially preferably, it is 30 mol% or less. When the structural unit represented by Formula (3) when m is 1-4 is more than the said lower limit with respect to the sum total of Y and Z in polyamide resin, the optical laminated body containing polyamide resin will have a high surface. In addition to being able to express hardness, the elastic modulus may be low and the flexibility may be excellent. If the surface hardness is high, scratches are less likely to occur on the optical laminate, particularly the substrate, and as a result, the yield of the product is improved, which can contribute to energy saving. When the structural unit represented by Formula (3) when m is 1-4 is less than the said upper limit with respect to the sum total of Y and Z in polyamide-type resin, Thickening by hydrogen bond between amide bonds derived from Formula (3) By suppressing the viscosity, the viscosity of the polyamide-based resin varnish described later can be suppressed, and the processing of the optical laminate can be facilitated.

In a suitable embodiment of the present invention, Z in the polyamide-based resin, preferably 30 mol% or more, more preferably 50 mol% or more, even more preferably 70 mol% or more, m is 0 to 4 It is represented by Formula (3) in the case of. When more than the said lower limit of Z of polyamide-type resin is represented by Formula (3) when m is 1-4, the optical laminated body containing polyamide-type resin expresses high surface hardness, and has an elastic modulus This can have a low, high flexibility. Moreover, it is preferable that preferably 100 mol% or less of Z in polyamide resin is represented by Formula (3) when m is 0-4. When the said upper limit below Z of polyamide-type resin is represented by Formula (3) when m is 0-4, the polyamide mentioned later by suppressing the thickening by the hydrogen bond between amide bonds derived from Formula (3) The viscosity of the system resin varnish can be suppressed and the processing of the optical laminate can be facilitated. In addition, the ratio between the structural unit represented by the polyamide-based resin of the formula (3) is, for example, can be measured by using a ¹ H-NMR, or may be calculated from the raw material doipbi.

In a suitable embodiment of the present invention, Z in the polyamide-based resin, preferably 5 mol% or more, more preferably 8 mol% or more, still more preferably 10 mol% or more, particularly preferably 12 mol % Or more is represented by Formula (3) when m is 1-4. When more than the said lower limit of Z of polyamide resin is represented by Formula (3) when m is 1-4, the optical laminated body containing a polyamide resin will express high surface hardness, and will have an elastic modulus. This can have a low, high flexibility. Further, Z in the polyamide-based resin is preferably 90 mol% or less, more preferably 70 mol% or less, still more preferably 50 mol% or less, particularly preferably 30 mol% or less, and m is 1 to 1. It is preferable that it is represented by Formula (3) in the case of 4. The polyamide mentioned later by suppressing the thickening by the hydrogen bond between the amide bonds derived from Formula (3) when below the said upper limit of Z of polyamide resin is represented by Formula (3) when m is 1-4. The viscosity of the system resin varnish can be suppressed and the processing of the optical laminate can be facilitated. In addition, the ratio between the structural unit represented by the polyamide-based resin of the formula (3) is, for example, can be measured by using a ¹ H-NMR, or may be calculated from the raw material doipbi.

In Formulas (1) and (2), X each independently represents a divalent organic group, and 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. The polyamide-based resin which is one embodiment of the present invention may include 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, the group represented by Formula (10), Formula (11), Formula (12), Formula (13), Formula (14), Formula (15), Formula (16), Formula (17) and Formula (18). ; Groups in which the hydrogen atoms in the groups represented by those formulas (10) to (18) are substituted by a methyl group, a fluoro group, a chloro group or a trifluoromethyl group; And a chain hydrocarbon group having 6 or less carbon atoms.

In formulas (10) to (18), * represents a bond.

V ¹ , V ² and V ³ are each independently a single bond, -O-, -S-, -CH _2- , -CH ₂ -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -SO _2- , -CO- or -N (Q)-. Here, Q represents the C1-C12 monovalent hydrocarbon group which may be substituted by the halogen atom, and the group similar to what was listed by R <^9> can be mentioned specifically ,.

In one example, V ¹ and V ³ are a single bond, -O- or -S-, and V ² is -CH _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- Or -SO _2- . The bonding position for each ring of V ¹ and V ² , and the bonding position for each ring of V ² and V ³ are each independently of each other, preferably a meta position or a para position, more preferably Para position.

Among the groups represented by the above formulas (10) to (18), the groups represented by the formulas (13) to (17) are preferred from the viewpoint of the surface hardness and the flexibility of the optical laminate comprising the polyamide-based resin. And group represented by Formula (14)-Formula (16) is more preferable. In addition, V ¹ , V ² and V ³ are each independently from the viewpoint of surface hardness and flexibility of the optical laminate comprising the polyamide-based resin, preferably a single bond, -O- or -S- More preferably, it is a single bond or -O-.

In a suitable embodiment of the present invention, at least a portion of the plurality of X in Formulas (1) and (2) is represented by Formula (4):

[In Formula (4), R <^10> -R <^17> respectively independently represents a hydrogen atom, a C1-C6 alkyl group, or a C6-C12 aryl group, and the hydrogen atom contained in R <^10> -R <^17> is respectively Independently, they may be substituted by a halogen atom, and * represents a bond.]

It is a structural unit represented by. If at least a part of a plurality of X in Formulas (1) and (2) is a group represented by Formula (4), the optical laminated body containing polyamide resin can express high surface hardness, High transparency can be expressed.

In Formula (4), R <^10> -R <^17> represents a hydrogen atom, a C1-C6 alkyl group, or a C6-C12 aryl group each independently. As a C1-C6 alkyl group or a C6-C12 aryl group, an exemplary thing is mentioned as a C1-C6 alkyl group or C6-C12 aryl group in Formula (3). R ¹⁰ to R ¹⁷ are each independently, preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, where R ¹⁰ to R ¹⁷ are The hydrogen atoms contained may be each independently substituted with a halogen atom. R ¹⁰ to R ¹⁷ each independently represent, in terms of surface hardness, transparency and flexibility of the optical laminate comprising the polyamide-based resin, more preferably a hydrogen atom, a methyl group, a fluoro group, a chloro group or It is a trifluoromethyl group, Especially preferably, it is a hydrogen atom or a trifluoromethyl group.

In a suitable embodiment of the present invention, the structural unit represented by formula (4) is represented by formula (4 '):

In other words, at least a part of the plurality of X's is a structural unit represented by Formula (4 '). In this case, the optical laminated body which contains the said polyamide-type resin expresses high transparency, and improves the solubility to the solvent of the said polyamide-based resin by the skeleton containing a fluorine element, The viscosity of resin varnish can be suppressed low, and the process of an optical laminated body can be made easy.

In a suitable embodiment of the present invention, at least 30 mol%, more preferably at least 50 mol%, even more preferably at least 70 mol% of X in the polyamide-based resin is formula (4), in particular Preferably, it is represented by Formula (4 '). When X in the said range in the said polyamide-type resin is represented by Formula (4), especially Formula (4 '), the optical laminated body containing a polyamide-type resin will express high transparency, The frame | skeleton containing a fluorine element can improve the solubility to the solvent of the said polyamide resin, can suppress the viscosity of a polyamide resin varnish low, and can also process the optical laminated body easily. Moreover, Preferably, 100 mol% or less of X in the said polyamide resin is represented by Formula (4), especially Formula (4 '). Formula (4), especially Formula (4 ') may be sufficient as X in the said polyamide resin. The ratio between the structural unit represented by the formula (4) in the X in the polyamide-based resin is, for example, can be measured by using a ¹ H-NMR, or may be calculated from the raw material doipbi.

In Formula (1), Y represents a tetravalent organic group each independently, Preferably it is the organic group in which the hydrogen atom in the organic group may be substituted by the hydrocarbon group or the fluorine-substituted hydrocarbon group. The polyamide-based resin which is one embodiment of the present invention may include a plurality of Y's, and the plurality of Y's may be the same as or different from each other. As Y, formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), formula (28) and formula (29) Group represented by; Groups in which the hydrogen atoms in the groups represented by formulas (20) to (29) are substituted by a methyl group, a fluoro group, a chloro group or a trifluoromethyl group; And a tetravalent hydrocarbon group having 6 or less carbon atoms is exemplified.

In formulas (20) to (29),

* Represents a bonding hand,

W ¹ is a single bond, -O-, -CH _2- , -CH ₂ -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,- Ar-, -SO _2- , -CO-, -O-Ar-O-, -Ar-O-Ar-, -Ar-CH ₂ -Ar-, -Ar-C (CH ₃ ) ₂ -Ar- or -Ar-SO ₂ -Ar- is represented. Ar represents the C6-C20 arylene group in which a hydrogen atom may be substituted by the fluorine atom, and a phenylene group is mentioned as a specific example.

Among the groups represented by the formulas (20) to (29), from the viewpoint of the surface hardness and the flexibility of the optical laminate comprising the polyamide-based resin, the formulas (26), (28) and (29) The group represented is preferable, and the group represented by Formula (26) is more preferable. In addition, W ¹ is each independently a single bond, -O-, -CH _2- , -CH ₂ -CH ₂ -from the viewpoint of surface hardness and flexibility of the optical laminate comprising the polyamide-based resin. , -CH (CH ₃ )-, -C (CH ₃ ) ₂ -or -C (CF ₃ ) ₂ -is preferable, and is a single bond, -O-, -CH _2- , -CH (CH ₃ )- , -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- , more preferably a single bond, -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- .

In a preferred embodiment of the present invention, at least some of the plurality of Y in Formula (1) are represented by Formula (5):

[In Formula (5), R <^18> -R <^25> respectively independently represents a hydrogen atom, a C1-C6 alkyl group, or a C6-C12 aryl group, and the hydrogen atom contained in R <^18> -R <^25> respectively Independently, they may be substituted by a halogen atom,

* Represents a bonding hand]

It is a structural unit represented by. When at least one part of the some Y in Formula (1) is group represented by Formula (5), the optical laminated body containing polyamide-type resin expresses high transparency and originates in a high flexible frame | skeleton, The solubility of the polyamide-based resin in the solvent can be improved, the viscosity of the polyamide-based resin varnish can be suppressed low, and the processing of the optical laminate can be facilitated.

In Formula (5), R <^18> -R <^25> represents a hydrogen atom, a C1-C6 alkyl group, or a C6-C12 aryl group each independently. As a C1-C6 alkyl group or a C6-C12 aryl group, an exemplary thing is mentioned as a C1-C6 alkyl group or C6-C12 aryl group in Formula (3). R ¹⁸ to R ²⁵ each independently, preferably represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and here, R ¹⁸ to R ²⁵ The hydrogen atoms contained may be each independently substituted with a halogen atom. R ¹⁸ to R ²⁵ are each independently, from the viewpoint of the surface hardness and flexibility of the optical laminate comprising the polyamide-based resin, more preferably a hydrogen atom, a methyl group, a fluoro group, a chloro group or a trifluoro It is a romethyl group, Especially preferably, it is a hydrogen atom or a trifluoromethyl group.

In a suitable embodiment of the present invention, the structural unit represented by formula (5) is represented by formula (5 '):

In other words, at least a part of the plurality of Y's is a structural unit represented by the formula (5 '). In this case, the optical laminated body containing the said polyamide resin can have high transparency.

In a suitable embodiment of the invention, preferably at least 50 mol%, more preferably at least 60 mol%, even more preferably at least 70 mol% of Y in the polyamide-based resin is formula (5), in particular It is represented by Formula (5 '). When Y in the said range in the said polyamide resin is represented by Formula (5), especially Formula (5 '), the optical laminated body containing this polyamide resin can have high transparency, and further The frame | skeleton containing a fluorine element can improve the solubility to the solvent of the said polyamide resin, can suppress the viscosity of a polyamide resin varnish low, and it is easy to manufacture an optical laminated body. Moreover, Preferably, 100 mol% or less of Y in the said polyamide resin is represented by Formula (5), especially Formula (5 '). Formula (5), especially Formula (5 ') may be sufficient as Y in the said polyamide resin. The ratio between the structural unit represented by the formula (5) of the Y in the polyamide-based resin is, for example, can be measured by using a ¹ H-NMR, or may be calculated from the raw material doipbi.

In the polyamide resin, the weight average molecular weight in terms of the standard polystyrene is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 50,000 or more, particularly preferably 100,000 or more, most preferably 150,000 It is more than 800,000, Preferably it is 800,000 or less, More preferably, it is 600,000 or less, More preferably, it is 500,000 or less. When the weight average molecular weight of polyamide-type resin is more than the said lower limit, the optical laminated body containing polyamide-type resin has more favorable bending tolerance. Moreover, when the weight average molecular weight of polyamide-type resin is below the said upper limit, since the viscosity of a polyamide-based resin varnish can be suppressed low and also an optical laminated body, especially extending | stretching of a base film is easy, workability becomes favorable. . In addition, in this specification, a weight average molecular weight can be calculated | required by standard polystyrene conversion, for example by GPC measurement, and can be calculated | required specifically by the method as described in an Example.

In the polyamide-imide, the content of the structural unit represented by the formula (2) is preferably 0.1 mol or more, more preferably 0.5 mol or more, and further, per 1 mol of the structural unit represented by the formula (1). Preferably it is 1.0 mol or more, Especially preferably, it is 1.5 mol or more, Preferably it is 3.9 mol or less, More preferably, it is 3.0 mol or less, More preferably, it is 2.5 mol or less. When content of the structural unit represented by Formula (2) is more than the said lower limit, the optical laminated body containing polyamide-type resin can express higher surface hardness. Moreover, when content of the structural unit represented by Formula (2) is below the said upper limit, the thickening by the hydrogen bond between the amide bonds in Formula (2) can be suppressed, and the viscosity of a polyamide-based resin varnish can be reduced, and optical The manufacture of a laminate is easy.

The polyamide-based resin may include a structural unit represented by formula (30) and / or a structural unit represented by formula (31) in addition to the structural units represented by formula (1) and formula (2).

In Formula (30), Y <^1> is a tetravalent organic group each independently, Preferably it is the organic group in which the hydrogen atom in the organic group may be substituted by the hydrocarbon group or the fluorine-substituted hydrocarbon group. As Y ^1, Formula (20), Formula (21), Formula (22), Formula (23), Formula (24), Formula (25), Formula (26), Formula (27), Formula (28), and Formula ( The group represented by 29) and a trivalent C6 or less chain hydrocarbon group are illustrated. One embodiment of the present invention taeyangin polyamide may already include lifting, Y ¹ of a plurality of types, Y ¹ of a plurality of species may be the same or different from each other.

In Formula (31), Y <^2> is a trivalent organic group, Preferably it is the organic group by which the hydrogen atom in the organic group may be substituted by the hydrocarbon group or the fluorine-substituted hydrocarbon group. As Y ^2, formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), formula (28) and formula ( The group by which any one of the bonds of group represented by 29) is substituted by the hydrogen atom, and a trivalent C6 or less chain hydrocarbon group are illustrated. May include an exemplary taeyangin polyamide imide, Y ² a plurality of types of the present invention, Y ² of the plurality of types are be the same or different from each other.

In Formula (30) and Formula (31), X <^1> and X <^2> are respectively independently divalent organic groups, Preferably the hydrogen atom in the organic group may be substituted by the hydrocarbon group or the fluorine-substituted hydrocarbon group. It is an organic group. As X <^1> and X <^2> , group represented by Formula (10)-formula (18); Groups in which the hydrogen atoms in the groups represented by those formulas (10) to (18) are substituted by a methyl group, a fluoro group, a chloro group or a trifluoromethyl group; And a chain hydrocarbon group having 6 or less carbon atoms.

In one embodiment of the present invention, the polyamide-imide is a structural unit represented by formulas (1) and (2), and optionally, a structural unit represented by formulas (30) and / or formulas (31) Is made of. Moreover, from the viewpoint of the surface hardness and the flexibility of the optical laminate including the polyamideimide, in the polyamideimide, the structural units represented by formulas (1) and (2) are represented by formulas (1) and Based on the formula (2) and, if appropriate, the entire structural units represented by the formulas (30) and (31), preferably 80 mol% or more, more preferably 90 mol% or more, even more preferably 95 More than mole%. In addition, in the said polyamideimide, the structural unit represented by Formula (1) and Formula (2) is represented by Formula (1) and Formula (2), and if necessary by Formula (30) and Formula (31). Paper is usually 100% or less based on the entire structural unit. In addition, the said ratio can be measured using <^1> H-NMR, for example, or it can also calculate from the introduction ratio of a raw material.

In polyamide-based resin, polyamide can be produced using, for example, a dicarboxylic acid compound and a diamine compound, which will be described later as main raw materials, and polyamideimide, for example, a tetracarboxylic acid compound, which will be described later, A dicarboxylic acid compound and a diamine compound can be manufactured as a main raw material. Here, it is preferable that a dicarboxylic acid compound contains the compound represented by at least Formula (3 ").

[Formula (3 ') of, R ¹ ~R ⁸ are, each independently, a hydrogen atom contained in the hydrogen atom, an alkyl group or an aryl group having a carbon number of 6 to 12 carbon atoms of 1~6, R ¹ ~R ⁸ are, Each independently may be substituted by a halogen atom,

A is -O-, -S-, -CO- or -N (R ⁹⁾ - represents a, R ⁹ represents a monovalent hydrocarbon group having 1 to 12 carbon atoms which is optionally substituted by halogen atoms,

m is an integer of 0 to 4,

R ³¹ and R ³² each independently represent —OH, —OCH ₃ , —OCH ₂ CH ₃ , —OCH ₂ CH ₂ CH ₃ , —OCH (CH ₃ ) ₂ , —OCH ₂ CH ₂ CH ₂ CH ₃ , -OCH (CH ₃ ) CH ₂ CH ₃ , -OCH ₂ CH (CH ₃ ) ₂ , -OC (CH ₃ ) ₃ or -Cl.

In a suitable embodiment, the dicarboxylic acid compound is a compound represented by formula (3 ″) wherein A is —O—. In another suitable embodiment, the dicarboxylic acid compound is R ³¹ and R ^32. Are each -Cl, and are compounds represented by the formula (3 "). Moreover, you may use a diisocyanate compound instead of a diamine compound.

As a tetracarboxylic acid compound used for the synthesis | combination of polyamide resin, Aromatic tetracarboxylic acid compounds, such as aromatic tetracarboxylic dianhydride; And aliphatic tetracarboxylic acid compounds such as aliphatic tetracarboxylic dianhydride, and the like. The tetracarboxylic acid compound may be used independently or may use 2 or more types together. The tetracarboxylic acid compound may be a tetracarboxylic acid compound flexible body such as an acid chloride compound, in addition to the anhydride.

As a specific example of aromatic tetracarboxylic dianhydride, non-condensed polycyclic aromatic tetracarboxylic dianhydride, monocyclic aromatic tetracarboxylic dianhydride, and condensed polycyclic aromatic tetracarboxylic dianhydride are mentioned. As a non-condensed polycyclic aromatic tetracarboxylic dianhydride, For example, 4,4'- oxydiphthalic acid dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-benzophenonetetracarboxylic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid dianhydride, 3 , 3 ', 4,4'-diphenylsulfontetracarboxylic acid 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 '-(hexafluoroisopropylidene) diphthalic dianhydride (may be described as 6FDA) , 1,2-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,2-bis (3,4-dicarboxyphenyl Ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, 4,4 '-(p-phenylenedioxy) diphthalic acid dianhydride, 4,4'-(m-phenylenedioxy) diphthalic acid dianhydride is mentioned. . Moreover, as monocyclic aromatic tetracarboxylic dianhydride, 1,2,4,5-benzene tetracarboxylic dianhydride is mentioned, for example, As condensed polycyclic aromatic tetracarboxylic dianhydride, for example 2,3,6,7-naphthalene tetracarboxylic dianhydride is mentioned.

Among these, 4,4'- oxydiphthalic acid dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic acid dianhydride, 2,2', 3,3'- benzophenone tetracarboxylic acid 2 Anhydride, 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride, 2,2', 3,3'-biphenyltetracarboxylic acid 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 '-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA), 1,2-bis (2,3-dicarboxyphenyl) ethane 2 Anhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, 1,2-bis (3,4-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxy Phenyl) ethane 2 anhydride, bis (3,4-dicarboxyphenyl) methane 2 anhydride, bis (2,3-dicarboxyphenyl) methane 2 anhydride, 4,4 '-(p-phenylenedioxy) diphthalic acid 2 Anhydrides and 4,4 '-(m-phenylenedioxy) diphthalic acid dianhydrides, and more preferably 4,4'-oxydiphthalic acid dianhydride, 3,3', 4,4'-biphenyl Tetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA), bis (3,4 -Dicarboxyphenyl) methane dianhydride and 4,4 '-(p-phenylenedioxy) diphthalic acid dianhydride are mentioned. These can be used individually or in combination of 2 or more types.

As aliphatic tetracarboxylic dianhydride, a cyclic or acyclic aliphatic tetracarboxylic dianhydride is mentioned. Cyclic aliphatic tetracarboxylic dianhydride is tetracarboxylic dianhydride which has alicyclic hydrocarbon structure, As a specific example, 1,2,4,5-cyclohexane tetracarboxylic dianhydride, 1,2,3,4-cyclo Cycloalkanetetracarboxylic dianhydride, such as butanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene-2,3,5 And 6-tetracarboxylic dianhydride, dicyclohexyl-3,3 ', 4,4'-tetracarboxylic dianhydride and regioisomers thereof. These can be used individually or in combination of 2 or more types. Specific examples of the acyclic aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, and the like. Or it can use in combination of 2 or more type. Moreover, you may use combining cyclic aliphatic tetracarboxylic dianhydride and acyclic aliphatic tetracarboxylic dianhydride.

Among the tetracarboxylic dianhydrides, 4,4'-oxydiphthalic acid dianhydride, 3,3 ', 4,4 from the viewpoint of high surface hardness, high transparency, high flexibility, high flex resistance and low colorability of the optical laminate '-Benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3' , 4,4'-diphenylsulfontetracarboxylic acid dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic acid dianhydride , And mixtures thereof, and 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride and 4,4'-(hexafluoroisopropylidene) diphthalic acid dianhydride, and mixtures thereof More preferred is 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride.

As dicarboxylic acid compound used for the synthesis | combination of polyamide-type resin, aromatic dicarboxylic acid, aliphatic dicarboxylic acid, those flexible acid chloride compounds, an acid anhydride, etc. are mentioned, You may use 2 or more types together. Specific examples include terephthalic acid; Isophthalic acid; Naphthalenedicarboxylic acid; 4,4'-biphenyldicarboxylic acid; 3,3'-biphenyldicarboxylic acid; The dicarboxylic acid compound of the chain hydrocarbon having 8 or less carbon atoms and the two benzoic acids are formed by a single bond, -CH _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -SO ₂ -or phenylene group. Linked compounds and their acid chloride compounds. Among these dicarboxylic acid compounds, 4,4'-oxybisbenzoic acid and their acid chlorides are preferable, 4,4'-oxybis (benzoyl chloride) and terephthaloyl chloride are preferable, and 4,4'-oxybis ( Benzoyl chloride) and terephthaloyl chloride are more preferably used together.

In addition, the polyamide-based resin, in addition to the tetracarboxylic acid compound used for synthesizing the polyamide-based resin in the range that does not impair various physical properties of the optical laminate comprising the polyamide-based resin, tetra The carboxylic acid and tricarboxylic acid and their anhydrides and derivatives may be further reacted.

As tetracarboxylic acid, the water adduct of the anhydride of the said tetracarboxylic acid compound is mentioned.

Examples of the tricarboxylic acid compound include aromatic tricarboxylic acid, aliphatic tricarboxylic acid, their flexible acid chloride compounds, and acid anhydrides, and two or more kinds thereof may be used in combination. Specific examples include anhydrides of 1,2,4-benzenetricarboxylic acid; 2,3,6-naphthalenetricarboxylic acid-2,3- anhydride; And phthalic anhydride and benzoic acid are linked by a single bond, -O-, -CH _2- , -C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -SO ₂ -or a phenylene group. .

As a diamine compound used for the synthesis | combination of polyamide-type resin, aliphatic diamine, aromatic diamine, and mixtures thereof are mentioned, for example. In addition, in this embodiment, "aromatic diamine" represents the diamine which the amino group couple | bonded with the aromatic ring directly, and may contain the aliphatic group or other substituent in a part of the structure. The aromatic ring may be monocyclic or condensed ring, and examples thereof include, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, and the like. Among these, Preferably they are a benzene ring. Moreover, "aliphatic diamine" shows the diamine which the amino group couple | bonded with the aliphatic group directly, and may contain the aromatic ring and other substituent in a part of the structure.

As aliphatic diamine, For example, acyclic aliphatic diamine, such as hexamethylenediamine, and 1, 3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane, norbornane diamine, and 4, Cyclic aliphatic diamine, such as 4'- diamino dicyclohexyl methane, etc. are mentioned. These can be used individually or in combination of 2 or more types.

Examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, m-xylylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene, 2, Aromatic diamines having one aromatic ring, such as 6-diaminonaphthalene, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylether, 3,3'-diaminodiphenylether, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-dia Minodiphenyl sulfone, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, bis [4- (4-amino phenoxy) 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 (may be referred to as TFMB), 4,4'-bis (4- Ah Nophenoxy) biphenyl, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) fluorene, 9,9-bis (4-amino-3- And aromatic diamines having two or more aromatic rings, such as chlorophenyl) fluorene and 9,9-bis (4-amino-3-fluorophenyl) fluorene. These can be used individually or in combination of 2 or more types.

As aromatic diamine, Preferably, 4,4'- diamino diphenylmethane, 4,4'- diamino diphenyl propane, 4,4'- diamino diphenyl ether, 3,3'- diamino diphenyl ether , 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 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 (TFMB), 4,4'-bis (4-aminophenoxy C) biphenyl, more preferably 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylether, 4,4'-diamino Diphenylsulfone, 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'- (Trifluoromethyl) scan is 4,4'-diaminodiphenyl (TFMB), 4,4'- bis (4-aminophenoxy) biphenyl. These can be used individually or in combination of 2 or more types.

Among the diamine compounds, from the viewpoint of high surface hardness, high transparency, high flexibility, high flex resistance, and low colorability of the optical laminate, it is preferable to use at least one member selected from the group consisting of aromatic diamines having a biphenyl structure. Do. Consisting of 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) benzidine, 4,4'-bis (4-aminophenoxy) biphenyl and 4,4'-diaminodiphenylether It is more preferable to use one or more selected from the group, and even more preferably 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl (TFMB).

The polyamideimide which is one embodiment of the present invention is a diamine compound, a tetracarboxylic acid compound (tetracarboxylic acid compound flexible body such as an acid chloride compound or tetracarboxylic dianhydride) and a dicarboxylic acid compound (acid chloride compound or the like) Condensation type polymer which is a polycondensation product of a carboxylic acid compound flexible body) and optionally a tricarboxylic acid compound (tricarboxylic acid compound flexible body such as an acid chloride compound and a tricarboxylic acid anhydride). The structural units represented by the formulas (1) and (30) are usually derived from diamines and tetracarboxylic acid compounds. The structural unit represented by Formula (2) is usually derived from a diamine and a dicarboxylic acid compound. The structural unit represented by Formula (31) is usually derived from a diamine and a tricarboxylic acid compound.

In a preferred embodiment of the present invention, the polyamide resin may contain a halogen atom as described above. As a specific example of a fluorine-containing substituent, a fluoro group and a trifluoromethyl group are mentioned. When a polyamide resin contains a halogen atom, the yellowness (YI value) of the optical laminated body which consists of polyamide resin may be reduced, and also tends to be compatible with high flexibility and bending resistance. There is this. In addition, the halogen atom is preferably a fluorine atom from the viewpoint of reducing the yellowness of the optical laminate, that is, improving transparency, decreasing the water absorption rate, and bending resistance.

The content of the halogen atoms in the polyamide-based resin is preferably based on the mass of the polyamide-based resin from the viewpoint of reducing the yellowness, that is, improving transparency, reducing water absorption and suppressing deformation of the optical laminate. Is 1-40 mass%, More preferably, it is 3-35 mass%, More preferably, it is 5-32 mass%.

In one embodiment of the present invention, an imidation catalyst may be present in the synthesis reaction of the polyamide-based resin. As an imidation catalyst, For example, aliphatic amines, such as tripropylamine, dibutylpropylamine, and ethyl dibutylamine; Alicyclic amines (monocyclic) such as N-ethylpiperidine, N-propylpiperidine, N-butylpyrrolidine, N-butylpiperidine, and N-propylhexahydroazepine; Alicyclic amines (polycyclic) such as azabicyclo [2.2.1] heptane, azabicyclo [3.2.1] octane, azabicyclo [2.2.2] octane, and azabicyclo [3.2.2] nonane; And pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, 2,4-dimethylpyridine, 2,4,6-trimethylpyridine, 3 And aromatic amines such as, 4-cyclopentenopyridine, 5,6,7,8-tetrahydroisoquinoline and isoquinoline.

Although the reaction temperature of a diamine compound, a tetracarboxylic acid compound, and a dicarboxylic acid compound is not specifically limited, For example, it is 50-350 degreeC. Although reaction time is not specifically limited, for example, It is about 30 minutes-about 10 hours. As needed, you may react on inert atmosphere or the conditions of pressure reduction. Moreover, reaction may be performed in a solvent, and the solvent mentioned later used for preparation of a polyamide-based resin varnish is mentioned as a solvent, for example.

(Aromatic compound)

An aromatic compound should just be a compound which has one or more aromatic hydrocarbon rings which may have a substituent, For example, As an aromatic hydrocarbon ring, Monocyclic hydrocarbon rings, such as a benzene ring; Polycyclic hydrocarbon rings, such as condensed bicyclic hydrocarbon rings, such as naphthalene, and ring aggregated hydrocarbon rings, such as biphenyl, are mentioned. As the substituent, for example, halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and an alkyl group having 1 to 6 carbon atoms similar to those of the examples as the alkyl group having 1 to 6 carbon atoms in the formula (3). Alkyl group, a phenyl group, a nitro group, a cyano group, a hydroxyl group, a phenyloxy group, etc. are mentioned. One or two or more of these substituents may be substituted with the aromatic hydrocarbon ring.

In this invention, since the polyamide type resin and an aromatic compound are contained in a base film, the optical laminated body excellent in the surface hardness of a hard-coat layer can be obtained. This is because the aromatic compound enters the space in the crosslinked structure formed by the hydrogen bonds between the amide bonds of the polyamide-based resin contained in the base film, thereby increasing the hardness of the base film, thereby improving the surface hardness of the hard coat layer. It is assumed that this is because.

It is preferable that an aromatic compound is a ultraviolet absorber. When an ultraviolet absorber is used as an aromatic compound contained in a base film, the surface hardness of the hard coat layer in an optical laminated body can be improved more.

Examples of the ultraviolet absorber include benzotriazole derivatives (benzotriazole ultraviolet absorbers), triazine derivatives such as 1,3,5-triphenyltriazine derivatives (triazine ultraviolet absorbers), and benzophenone derivatives (benzophenone ultraviolet rays). Absorbers) and salicylate derivatives (salicylate ultraviolet absorbers), and at least one selected from the group consisting of these can be used. In addition to improving the surface hardness of the optical laminate and having a good ultraviolet absorbing ability at 370 to 400 nm, the polarizing plate can be protected when laminated with a polarizing plate. It is preferable to use at least 1 sort (s) chosen from the group which consists of, and a benzotriazole type ultraviolet absorber is more preferable.

As a specific example of a benzotriazole type ultraviolet absorber, the compound represented by Formula (I), the product of Sumitomo Chemical Co., Ltd. make: Sumisorb (R) 250 (2- [2-hydroxy-3- (3,4,5) , 6-tetrahydrophthalimide-methyl) -5-methylphenyl] benzotriazole) and BASF Japan Co., Ltd. product name: Tinuvin (R) 360 (2,2'-methylenebis [6- (2H) -Benzotriazol-2-yl) -4-tert-octylphenol]) and Tinuvin 213 (methyl 3- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxy Phenyl] propionate and the reaction product of PEG300), These can be used individually or in combination of 2 or more types. As a specific example of the compound represented by Formula (I), Sumitomo Chemical Co., Ltd. brand name: Sumisorb 200 (2- (2-hydroxy-5-methylphenyl) benzotriazole), 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), and BASF Japan Co., Ltd. product name: Tinuvin 327 (2- (2'-hydroxy-3 ', 5'-di) -tert-butylphenyl) -5-chlorobenzotriazole), Tinuvin 571 (2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl-phenol) and Tinuvin 234 (2- ( 2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol) and ADEKA Co., Ltd. product name: Adecastab LA-31 (2,2 '-Methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol]). The ultraviolet absorber is preferably a compound represented by formula (I) and Tinuvin 213 (methyl 3- [3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl] prop It is a reaction product of a cionate and PEG300, More preferably, the brand names of Sumitomo Chemical Co., Ltd. make: Sumisorb 200 (2- (2-hydroxy-5-methylphenyl) benzotriazole), 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), ADEKA Co., Ltd. product name: Adecastave LA-31 (2,2'-methylenebis [6- (2H-benzo) Triazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol]) and BASF Japan Co., Ltd. product name: Tinuvin 327 (2- (2'-hydroxy-3 ') , 5'-di-tert-butylphenyl) -5-chlorobenzotriazole) and Tinuvin 571 (2- (2H-benzotriazol-2-yl) -6-dodecyl-4-methyl-phenol), Most preferably Mitomo Chemical Co., Ltd. product name: Sumisorb 340 (2- (2-hydroxy-5-tert-octylphenyl) benzotriazole), Sumisorb 350 (2- (2-hydroxy-3,5-di-) tert-pentylphenyl) benzotriazole), and the product name of ADEKA Co., Ltd .: Adecastab LA-31 (2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- ( 1,1,3,3-tetramethylbutyl) phenol]).

In formula (I), X <^I> is a hydrogen atom, a fluorine atom, a chlorine atom, a C1-C5 alkyl group, or a C1-C5 alkoxy group, R <^I1> and R <^I2> respectively independently represent a hydrogen atom or C1-C5 at least one of a 20 hydrocarbon group, R ^{I1 I2} R or one is a hydrocarbon group of 1 to 20 carbon atoms.

Examples of the alkyl group having 1 to 5 carbon atoms in X ^I are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, 2-methyl-butyl Group, 3-methylbutyl group, 2-ethyl-propyl group, etc. are mentioned.

As the alkoxy group having 1 to 5 carbon atoms in the X ^I, methoxy, ethoxy, n- propoxy, iso-propoxy, n- butoxy group, sec- butoxy group, tert- butoxy group, n- pen tilok time , 2-methyl-butoxy group, 3-methylbutoxy group, 2-ethyl-propoxy group, and the like.

X ^I 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 ^I1 and R ^I2 are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and at least one of R ^I1 and R ^I2 is a hydrocarbon group. When R <^I1> and R <^I2> are a hydrocarbon group, respectively, Preferably they are a C1-C12 hydrocarbon group, More preferably, they are a C1-C8 hydrocarbon group. Specifically, a methyl group, tert-butyl group, tert-pentyl group, and tert-octyl group are illustrated.

The ultraviolet absorber which concerns on another preferable aspect is a triazine type ultraviolet absorber in the optical laminated body containing polyamide resin. As a triazine type ultraviolet absorber, the compound represented by following formula (II) is mentioned. As a specific example, the product name of ADEKA Co., Ltd .: Adecastab LA-46 (2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [2- (2-ethyl Hexanoyloxy) ethoxy] phenol) and BASF Japan Co., Ltd. make a brand name: Tinuvin 400 (2- [4- [2-hydroxy-3- tridecyloxy propyl] oxy] -2-hydroxy phenyl]- 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4- [2-hydroxy-3-didecyloxypropyl] oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine), Tinuvin 405 (2- [4 (2-hydroxy-3- (2'-ethyl) hexyl) oxy] 2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine), Tinuvin 460 (2,4-bis (2-hydroxy-4-butyloxy) Phenyl) -6- (2,4-bis-butyloxyphenyl) -1,3,5-triazine), Tinuvin 479 (hydroxyphenyltriazine-based ultraviolet absorber), and Chemiprofase Co., Ltd. product name: KEMISORB® 102 (2- [4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- (n-octyloxy) phenol) And these alone Or it can use in combination of 2 or more type. The compound represented by formula (II) is preferably adecastab LA-46 (2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [2- ( 2-ethylhexanoyloxy) ethoxy] phenol).

In formula (II), Y <^I1> -Y <^I4> is respectively independently a hydrogen atom, a fluorine atom, a chlorine atom, a hydroxyl group, a C1-C20 alkyl group, or a C1-C20 alkoxy group, Preferably it is a hydrogen atom, It is a C1-C12 alkyl group or a C1-C12 alkoxy group, More preferably, it is a hydrogen atom.

In formula (II), R <^I3> is C1-C20 substituted by a hydrogen atom, a C1-C20 hydrocarbon group, a C1-C20 alkoxy group containing 1 oxygen atom, or a C1-C12 alkylketooxy group It is a 1-4 alkoxy group, Preferably it is a C2-C4 alkoxy group substituted by the C1-C12 alkoxy group containing 1 oxygen atom, or a C8-C12 alkyl ketooxy group, More Preferably it is a C2-C4 alkoxy group substituted by C8-C12 alkyl ketooxy group.

Examples of the alkyl group having 1 to 20 carbon atoms as Y ^{I1 to} Y ^I4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group and n-hex A real group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-undecyl group is mentioned.

In one embodiment, the ultraviolet absorber is preferably easily dissolved in N, N-dimethylacetamide (hereinafter sometimes referred to as DMAc), which exhibits high solubility in polyamide resins. Such a ultraviolet absorber may be a compound which dissolves 1.0 g or more in 100 g of 25 ° C DMAc, in other words, 1.0 g / 100 g or more in solubility in 25 ° C DMAc. The solubility of the ultraviolet absorber is preferably 5 g / 100 g or more, and more preferably 10 g / 100 g or more with respect to a solvent such as DMAc. There is no restriction | limiting in the upper limit of the solubility of a ultraviolet absorber, For example, 100g / 100g may be sufficient. Since the ultraviolet absorbent having high solubility in DMAc is easy to homogenize with a polyamide resin, the surface hardness of the optical laminated body can be improved, and also has high transparency and high ultraviolet absorbing ability, and further prevents coloring and the like. You may.

It is preferable that a ultraviolet absorber has ultraviolet absorbency, such that the light transmittance at 390 nm of a base film can be 35% or less, More preferably, it is 25% or less, More preferably, it is 20% or less.

In a base film, content of a ultraviolet absorber becomes like this. Preferably it is 0.01-10 mass parts, More preferably, it is 1-8 mass parts, More preferably, it is 3-7 mass parts with respect to 100 mass parts of polyamide resins. . If content of a ultraviolet absorber is more than the said lower limit, the surface hardness of an optical laminated body can be improved. Moreover, if content of a ultraviolet absorber is below the said upper limit, the yellowness of an optical laminated body can be suppressed (YI value can be reduced), and transparency of an optical laminated body can be improved.

In the base film, the content of the polyamide-based resin is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, particularly preferably based on the mass of the base film. 80 mass% or more, very preferably 90 mass% or more. If content of polyamide-type resin is more than the said lower limit, the surface hardness and the flexibility of an optical laminated body are favorable. In addition, content of polyamide-type resin in a base film is less than 100 mass% normally on the basis of the total mass of a base film.

The base film may further contain inorganic particles in addition to the polyamide resin and the aromatic compound from the viewpoint of easily improving the surface hardness of the optical laminate. Examples of the inorganic particles include titania particles, alumina particles, zirconia particles, silica particles, and the like. In view of the stability of the polyamide resin varnish for producing the optical laminate and the improvement of the surface hardness of the optical laminate, the inorganic particles are preferably silica particles. The inorganic particles may be bonded by a molecule having a siloxane bond.

The average primary particle diameter of the inorganic particles is preferably 10 to 100 nm, more preferably 20 to 80 nm, in view of transparency of the optical laminate, mechanical properties, and suppression of aggregation of the inorganic particles. In this invention, an average primary particle diameter can be determined by measuring the 10-point average value of the positive direction diameter by a transmission electron microscope (TEM).

When a base film contains an inorganic particle, content of the inorganic particle in an optical laminated body becomes like this. Preferably it is 5 mass% or more, More preferably, it is 10 mass% or more, More preferably, 20 mass with respect to the mass of a base film. % Or more, Especially preferably, it is 30 mass% or more, Preferably it is 70 mass% or less, More preferably, it is 60 mass% or less. If content of an inorganic particle is more than the said lower limit, it is advantageous for the improvement of the surface hardness of a hard coat layer, and if it is below the said upper limit, it is advantageous for the reduction of the YI value of an optical laminated body.

The base film may further contain other additives. Examples of other additives include antioxidants, mold release agents, stabilizers, bluing agents, flame retardants, pH adjusters, silica dispersants, lubricants, thickeners and leveling agents.

Content of other additives becomes like this. Preferably it is 0-20 mass% with respect to the mass of a base film, More preferably, it is 0-10 mass%.

Although the thickness of a base film is suitably adjusted according to a use, it is 10-200 micrometers normally, Preferably it is 20-100 micrometers, More preferably, it is 25-80 micrometers, More preferably, it is 30-50 micrometers. In addition, in this invention, the thickness of a base film can be measured by the method as described in an Example, for example.

<Hard Coating Layer>

The optical laminated body of this invention has a hard coat layer in at least one surface of a base film. The hard coat layer may be provided on one side or both sides of the base film.

As a hard coat layer, well-known hard coat layers, such as an acryl type, an epoxy type, a urethane type, benzyl chloride type, a vinyl type, are mentioned, for example. Among these, an acrylic hard coating layer can be used preferably. It is preferable that an acryl-type hard coat layer is the hardened | cured material of the curable composition containing a curable compound. A curable compound is a compound which superposes | polymerizes and hardens | cures by irradiation of an active energy ray, As an example, a polyfunctional (meth) acrylate type compound is mentioned. A polyfunctional (meth) acrylate type compound is a compound which has at least 2 (meth) acryloyloxy group in a molecule | numerator.

As a polyfunctional (meth) acrylate type compound, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, pentaglycerol Tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris ((meth) acrylo Oxyethyl) isocyanurate; Phosphazene (meth) acrylate compounds in which a (meth) acryloyloxy group is introduced into the phosphazene ring of the phosphazene compound; Urethane (meth) acrylate compounds obtained by the reaction of a polyisocyanate having at least two isocyanate groups in a molecule with a polyol compound having at least one (meth) acryloyloxy group and a hydroxyl group; Polyester (meth) acrylate compounds obtained by the reaction of a polyol compound having at least two carboxylic acid halides and at least one (meth) acryloyloxy group and a hydroxyl group in a molecule; And oligomers such as dimers, trimers, etc. of the above compounds. These compounds are used individually or in mixture of 2 or more types, respectively.

A curable compound may contain a monofunctional (meth) acrylate type compound other than the said polyfunctional (meth) acrylate type compound. As a monofunctional (meth) acrylate type compound, for example, hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) ) Acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (meth) acrylate, etc. are mentioned. These compounds are used individually or in mixture of 2 or more types. It is preferable that content of a monofunctional (meth) acrylate type compound is 10 mass% or less in solid content of the compound contained in curable composition.

Moreover, the curable compound may contain the polymeric oligomer. By containing a polymerizable oligomer, the hardness of a hard coat layer can be adjusted. As a polymerizable oligomer, terminal (meth) acrylate polymethyl methacrylate, terminal styryl poly (meth) acrylate, terminal (meth) acrylate polystyrene, terminal (meth) acrylate polyethylene glycol, terminal (meth) acrylate acrylic Macro monomers, such as a ronitrile styrene copolymer and terminal (meth) acrylate styrene-methyl (meth) acrylate copolymer, are mentioned. It is preferable that content of a polymeric oligomer is 5-50 mass% in solid content of the compound contained in a curable composition.

The curable composition may contain a polymerization initiator. As a polymerization initiator, for example, acetophenone, acetophenonebenzyl ketal, anthraquinone, 1- (4-isopropylphenyl-2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 4-chloro Benzophenone, 4,4'-diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3'-dimethyl-4-methoxybenzophenone, thioxanthone, 2,2-dimethoxy-2 -Phenylacetophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino Propane-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, phenylbis (2,4,6-trimethylbenzoyl) -phosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoisopropyl ether, benzophenone, Michler's ketone, 3-methylacetophenone, 3 , 3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone (BTTB), 2- ( Dimethylamino) -1- [4- (morpholinyl) phenyl] -2-phenylmethyl) -1-butanone, 4-benzoyl-4'-methyldiphenylsulfide, benzyl, derivatives thereof and the like. . These polymerization initiators may be used independently, and may mix and use several types as needed. The polymerization initiators exemplified above are all photopolymerization initiators that generate radicals by irradiation of active energy rays.

The content of the polymerization initiator is preferably 0.1 to 10 parts by mass, and more preferably 1 to 7 parts by mass with respect to 100 parts by mass of the curable compound. If content of a polymerization initiator is the said range, sclerosis | hardenability of a curable composition will become favorable and the surface hardness of a hard coat layer can be raised.

A curable composition can contain the thing similar to the ultraviolet absorber as described in the term of <substrate film>. When a hard coat layer contains a ultraviolet absorber, when content of an ultraviolet absorber is excessive, the curability of a curable composition may fall, and as a result, the surface hardness of a hard coat layer may fall. Therefore, content of the ultraviolet absorber in a hard coat layer becomes like this. Preferably it is less than 5.0 mass parts with respect to 100 mass parts of curable compositions, More preferably, it is 2.0 mass parts or less, More preferably, it is 0 mass parts. In order to improve the surface hardness of a hard coat layer, it is advantageous to improve the hardenability of the curable composition which forms a hard coat layer, and to raise the hardness of the base film resulting from containing a ultraviolet absorber. For this purpose, it is preferable that content of the ultraviolet absorber contained in a base film is larger than content of the ultraviolet absorber in a hard coat layer. In addition, content of the ultraviolet absorber contained in a base film and content of the ultraviolet absorber in a hard coat layer can be compared based on the total mass of an optical laminated body, for example.

The curable composition may contain a solvent in order to improve the coating property on a base film. As a solvent, For example, Aliphatic hydrocarbons, such as hexane and an octane; Aromatic hydrocarbons such as toluene and xylene; Alcohols such as ethanol, 1-propanol, isopropanol and 1-butanol; Ketones such as methyl ethyl ketone and methyl isobutyl ketone; Esters such as ethyl acetate, butyl acetate and isobutyl acetate; Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether; It can select suitably from esterification glycol ethers, such as ethylene glycol monomethyl ether acetate and a propylene glycol monomethyl ether acetate, etc., and can use. These solvents can be used individually or in combination of 2 or more types. The kind and content of a solvent are suitably selected according to the kind and content of the curable compound to be used, the material, shape of a base film, a coating method, the thickness of the target hard coat layer, etc.

The curable composition may further contain other additives. Examples of the other additives include the inorganic particles, antistatic agents, antioxidants, mold release agents, stabilizers, bluing agents, flame retardants, pH adjusters, silica dispersants, lubricants, thickeners and leveling agents described in the section of <Base Film>. . When the curable composition contains other additives, the content of the other additives is preferably 0.01 to 20% by mass, more preferably 0.1 to 10% by mass with respect to the mass of the curable composition.

The thickness of the hard coat layer is preferably 1 to 20 µm, more preferably 3 to 17 µm, and still more preferably 5 to 15 µm from the viewpoint of making the flex resistance and the pencil hardness of the optical laminated body compatible. In addition, the thickness of a hard coat layer can be measured by the method as described in an Example, for example.

The curable composition can be obtained by mixing a component contained in the composition, for example, a curable compound, a polymerization initiator, a ultraviolet absorber, a solvent, and other additives as required, for example, by mixing. The mixing order is not particularly limited.

<Optical laminated body>

The optical laminated body of this invention has a hard coat layer in the said base film and at least one surface of the said base film. Although one Embodiment of this invention is shown in FIG. 1, this invention is not limited to this aspect. The optical laminated body 1 shown in FIG. 1 has the base film 2 and the hard-coat layer 3 on the single side | surface of the said base film 2. FIG.

Since the optical laminated body of this invention contains a polyamide resin and an aromatic compound in a base film, it has the outstanding surface hardness and is excellent in transparency and ultraviolet absorbency. By having excellent surface hardness, when using it as a front plate (window film) of an image display apparatus, the damage of the surface of an image display apparatus can be suppressed effectively. Therefore, the optical laminated body of this invention is useful as a front plate of an image display apparatus, especially a front plate (window film) of a flexible display. This optical laminated body can be arrange | positioned as a front plate on the visual side of an image display apparatus, especially a flexible display. This front plate has a function of protecting the image display element in the flexible display. The image display apparatus provided with the said optical laminated body has the outstanding surface hardness, and also has the outstanding transparency and ultraviolet absorption. As an image display apparatus, wearable devices, such as a television, a smart phone, a mobile telephone, car navigation, a tablet PC, a portable game machine, an electronic paper, an indicator, a bulletin board, a clock, and a smart watch, etc. are mentioned. As a flexible display, the image display apparatus which has a flexible characteristic, for example, a television, a smart phone, a mobile phone, car navigation, a tablet PC, a portable game machine, an electronic paper, an indicator, a bulletin board, a clock, a wearable device, etc. are mentioned. .

The pencil hardness of the optical laminate is preferably at least 2B, more preferably at least B, even more preferably at least HB, particularly preferably at least H, very preferably at least 2H, particularly preferably at least 3H. If the pencil hardness of an optical laminated body is more than a lower limit, the scratch of the surface of an image display apparatus can be suppressed effectively, when used as a front plate of an image display apparatus. Moreover, the surface hardness of an optical laminated body is 9H or less normally. In addition, a pencil hardness can be measured by the method as described in an Example, for example.

YI value (yellowness) of an optical laminated body becomes like this. Preferably it is 10 or less, More preferably, it is 8 or less, More preferably, it is 5 or less, Especially preferably, it is 3 or less. The optical laminated body whose YI value (yellowness) is below the said upper limit has favorable transparency, and when used for the front plate of an image display apparatus, it can contribute to high visibility. Moreover, YY value (yellowness) of an optical laminated body becomes like this. Preferably it is zero or more. In addition, a YI value (yellowness) can be measured by the method as described in an Example, for example.

The light transmittance at 390 nm of the optical laminate is preferably 35% or less, more preferably 30% or less, still more preferably 25% or less, particularly preferably 20% or less. If the light transmittance of an optical laminated body is below the said upper limit, ultraviolet absorbency is favorable and it can contribute to the prevention of deterioration of a liquid crystal or a polarizing film, when used for the front plate of an image display apparatus. In addition, the light transmittance at 390 nm can be measured by the method as described in an Example, for example.

Although the manufacturing method of an optical laminated body is not specifically limited, For example, the following processes:

(a) applying a liquid containing a polyamide resin and an aromatic compound (sometimes referred to as polyamide resin varnish) to a resin substrate to form a coating film (coating step A), and

(b) Process of drying apply | coated liquid (coating film) and forming base film (base film formation process)

(c) Process of apply | coating the said curable composition to at least one surface of the said base film, and forming a coating film (coating process B)

(d) Process of irradiating high energy ray to apply | coated liquid (coating film), hardening coating film and forming hard coating layer (hard coating layer formation process)

It can manufacture by the manufacturing method containing these.

In the coating step A, first, a liquid (polyamide resin varnish) containing a polyamide resin and an aromatic compound is prepared. In order to prepare a polyamide resin varnish, the diamine compound, the tetracarboxylic acid compound, the dicarboxylic acid compound, and other components such as tertiary amines and dehydrating agents, which act as imidization catalysts, may be mixed as necessary. And reaction to prepare a polyamide resin mixture. As tertiary amine, the aromatic amine, aliphatic amine, etc. which were mentioned above are mentioned. Examples of the dehydrating agent include acetic anhydride, propionic anhydride, isobutyric anhydride, pivalic anhydride, butyric anhydride, and isovaleric anhydride. A poor solvent is added to this polyamide-based resin mixture, and a polyamide-based resin is precipitated by reprecipitation method, dried, and a precipitate is taken out. If necessary, the precipitate is washed with a solvent such as methanol and dried to obtain a polyamide resin. Subsequently, the polyamide resin is dissolved in a solvent, and the above-mentioned aromatic compound and other additives are added and stirred to prepare a liquid (polyamide resin varnish) containing the polyamide resin.

The solvent used for preparation of the polyamide-based resin varnish is not particularly limited as long as it can dissolve the polyamide-based resin. As such a solvent, For example, Amide type solvents, such as N, N- dimethylacetamide and N, N- dimethylformamide; lactone solvents such as γ-butyrolactone and γ-valerolactone; Sulfur-based 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 solvents, amide solvents or lactone solvents are preferable. The polyamide resin varnish may include water, an alcohol solvent, a ketone solvent, an acyclic ester solvent, an ether solvent, and the like.

Next, a polyamide-based resin varnish is applied to a substrate such as a resin substrate, an SUS belt, or a glass substrate by a known coating method to form a coating film. As a well-known coating method, for example, a roll coating method such as a wire bar coating method, reverse coating, gravure coating, a die coating method, a comma coating method, a lip coating method, a spin coating method, a screen coating method, a fountain coating method, The dipping method, the spray method, the casting molding method, etc. are mentioned.

In a base film formation process, a base film can be formed by drying a coating film and peeling from a resin base material. You may perform the drying process which dries a base film further after peeling. Drying of a coating film can be performed at the temperature of 50-350 degreeC normally. As needed, you may dry a coating film under conditions of inert atmosphere or reduced pressure.

As an example of a resin base material, a PET film, a PEN film, a polyimide film, a polyamideimide film, etc. are mentioned. Among them, PET film, PEN film, polyimide film and other polyamideimide film are preferred from the viewpoint of excellent heat resistance. Moreover, PET film is more preferable from a viewpoint of adhesiveness with an optical laminated body, and cost.

In the coating step B, the curable composition dissolved in the solvent may be applied to the base film. As a solvent, the thing similar to the solvent of the term of <hard coat layer> is mentioned, As said coating method, said well-known coating method is mentioned.

You may dry the coating film formed on the base film. Drying of a coating film can be performed by evaporating a solvent at the temperature of 50-150 degreeC, and a drying time is 30 to 180 second normally. As needed, you may dry a coating film under conditions of inert atmosphere or reduced pressure.

In the hard coat layer forming step, the coating film is irradiated with high energy rays (for example, active energy rays), and the coating film is cured to form a hard coating layer. Irradiation intensity is suitably determined according to the composition of a curable composition, and although it does not specifically limit, irradiation of the wavelength range effective for activation of a polymerization initiator is preferable. The irradiation intensity is preferably 0.1 to 6,000 mW / cm 2, more preferably 10 to 1,000 mW / cm 2 and even more preferably 20 to 500 mW / cm 2. If irradiation intensity is in the said range, appropriate reaction time can be ensured and the yellowing and deterioration of resin by the heat radiated | emitted from a light source and the heat generation at the time of hardening reaction can be suppressed. The irradiation time may be appropriately selected depending on the composition of the curable composition, and is not particularly limited, but the amount of accumulated light expressed as the product of the irradiation intensity and the irradiation time is preferably 10 to 10,000 mJ / cm 2, more preferably 50. It is set so that it may become -1,000 mJ / cm <2>, More preferably, it is 80-500 mJ / cm <2>. When the accumulated light amount is within the above range, a sufficient amount of active species derived from the polymerization initiator can be generated, and the curing reaction can be progressed more reliably, and the irradiation time is not too long, and good productivity can be maintained. Moreover, since the hardness of a hard-coat layer can be raised further by going through the irradiation process in this range, it is useful.

The optical laminated body of this invention may have a layer separate from a base film and a hard coat layer. As another layer, a functional layer is mentioned, for example, As a functional layer, the layer which has various functions, such as an ultraviolet-ray absorption layer, an adhesion layer, a color adjustment layer, and a refractive index adjustment layer, can be illustrated. The optical laminated body may be equipped with single or multiple functional layers. In addition, one functional layer may have a plurality of functions.

The ultraviolet absorbing layer is a layer having a function of absorbing ultraviolet rays, and includes, for example, a main material selected from an ultraviolet curable transparent resin, an electron beam curable transparent resin, and a thermosetting transparent resin, and ultraviolet rays dispersed in the main material. It consists of an absorbent (for example, the said ultraviolet absorber). By providing an ultraviolet absorbing layer as a functional layer, the change of the yellowness by light irradiation can be suppressed easily.

An adhesive layer is a layer which has a sticky function, and has a function which adhere | attaches an optical laminated body to another member. As a formation material of an adhesion layer, a well-known thing can be used normally. For example, a thermosetting resin composition or a photocurable resin composition can be used.

The adhesion layer may be comprised with the resin composition containing the component which has a polymeric functional group. In this case, firm adhesion can be realized by further polymerizing the resin composition constituting the pressure-sensitive adhesive layer after the optical laminate is brought into close contact with another member. The adhesive strength of the optical laminate and the adhesive layer is preferably 0.1 N / cm or more, more preferably 0.5 N / cm or more.

The adhesion layer may contain the thermosetting resin composition or the photocurable resin composition as a material. In this case, the resin composition can be polymerized and cured by supplying energy afterwards.

The pressure-sensitive adhesive layer may be a layer composed of an adhesive that is adhered to an object by pressure, called a pressure sensitive adhesive (PSA). The pressure-sensitive adhesive may be an adhesive which is "a substance which has adhesiveness at room temperature and adheres to the adherend at light pressure" (JIS K 6800), and "contains a specific component in a protective film (microcapsule), and is suitable. It may be a capsule adhesive, which is an adhesive capable of holding stability until the film is broken by means (pressure, heat, etc.) (JIS K 6800).

A color adjustment layer is a layer which has a function of color adjustment, and is a layer which can be adjusted to the color aimed at an optical laminated body. A color adjustment layer is a layer containing resin and a coloring agent, for example. As this coloring agent, For example, inorganic pigments, such as a titanium oxide, zinc oxide, a bengalah, a titanium oxide type baking pigment, a ultramarine blue, cobalt aluminate, and carbon black; Organic pigments such as azo compounds, quinacridone compounds, anthraquinone compounds, perylene compounds, isoindolinone compounds, phthalocyanine compounds, quinophthalone compounds, styrene compounds and diketopyrrolopyrrole compounds; Extender pigments such as barium sulfate and calcium carbonate; And dyes such as basic dyes, acid dyes, and mordant dyes.

The refractive index adjusting layer is a layer having a function of adjusting the refractive index, and has a refractive index different from that of the optical laminated body, and is a layer capable of providing a predetermined refractive index to the optical laminated body. The refractive index adjusting layer may be, for example, a resin that is appropriately selected, and a resin layer further containing a pigment, as the case may be, or a thin film of metal.

Examples of the pigment for adjusting the refractive index include silicon oxide, aluminum oxide, antimony oxide, tin oxide, titanium oxide, zirconium oxide and tantalum oxide. The average primary particle diameter of a pigment may be 0.1 micrometer or less. By making the average primary particle diameter of a pigment into 0.1 micrometer or less, the diffuse reflection of the light which permeate | transmits a refractive index adjustment layer can be prevented, and the fall of transparency can be prevented.

Examples of the metal used for the refractive index adjusting layer include metal oxides such as titanium oxide, tantalum oxide, zirconium oxide, zinc oxide, tin oxide, silicon oxide, indium oxide, titanium oxynitride, titanium nitride, silicon oxynitride, and silicon nitride. Metal nitrides.

[Flexible Image Display Device]

In the present invention, the flexible image display device includes the optical laminate of the present invention. The optical laminated body of this invention is preferably used as a front plate in a flexible image display apparatus, and the said front plate may be called a window film. The said flexible image display apparatus consists of a laminated body for flexible image display apparatuses, and an organic electroluminescent display panel, The flexible image display apparatus laminated body is arrange | positioned at the visual recognition side with respect to an organic electroluminescent display panel, and is comprised so that it is bendable. As a laminated body for flexible image display apparatuses, the polarizing plate, Preferably the circularly polarizing plate, and a touch sensor may be contained further, Although the lamination order is arbitrary, it is a window film, a polarizing plate, a touch sensor, or a window film, a touch sensor from the visual recognition side. It is preferable to laminate | stack in order of the polarizing plate. When a polarizing plate exists in the visual recognition side rather than a touch sensor, since the pattern of a touch sensor becomes difficult to visually recognize and the visibility of a display image improves, it is preferable. Each member can be laminated | stacked using an adhesive agent, an adhesive, etc. The light shielding pattern may be provided on at least one surface of any of the window film, the polarizing plate, and the touch sensor.

[Circular polarizing plate]

It is preferable that a flexible display apparatus is provided with a polarizing plate and a circular polarizing plate especially among these. A circular polarizing plate is a functional layer which has a function which transmits only a right or left circular polarizing component by laminating | stacking (lambda) / 4 phase (s) difference plate in a linear polarizing plate. For example, by converting external light into right polarized light to block external light reflected by the organic EL panel and left circularly polarized light, and by transmitting only the light emitting components of the organic EL, the effect of reflected light is suppressed to view an image. It is used to make it easier. In order to achieve the circularly polarized light function, the absorption axis of the linear polarizing plate and the ground axis of the λ / 4 phase difference plate need to be 45 ° in theory, but are practically 45 ± 10 °. The linear polarizing plate and the λ / 4 retardation plate do not necessarily have to be stacked adjacent to each other, and the relationship between the absorption axis and the slow axis only needs to satisfy the aforementioned range. Although it is preferable to achieve complete circular polarization in all wavelengths, since it does not necessarily need to be practical, the circular polarizing plate in this invention also includes an elliptical polarizing plate. It is also preferable to improve the visibility in the state which wore polarized sunglasses by laminating | stacking (lambda) / 4 phase (s) difference film further on the visual recognition side of a linear polarizing plate, and making outgoing light circularly polarized.

The linear polarizing plate is a functional layer having a function of passing light that vibrates in the transmission axis direction but blocking polarization of the vibration component perpendicular to the linear polarizing plate. The linear polarizing plate may be a structure including a linear polarizer alone or a linear polarizer and a protective film affixed on at least one surface thereof. The thickness of the said linear polarizing plate may be 200 micrometers or less, Preferably it is 0.5-100 micrometers. When the thickness of a linear polarizing plate exists in the said range, it exists in the tendency for the flexibility of a linear polarizing plate to fall easily.

The linear polarizer may be a film polarizer produced by dyeing and stretching a polyvinyl alcohol (hereinafter, sometimes referred to as PVA) -based film. A dichroic dye is orientated and exhibits polarization performance by extending | stretching in the state which the dichroic dye, such as iodine, adsorb | sucked to PVA system film oriented by extending | stretching, or adsorb | sucking to PVA. In manufacture of the said film polarizer, you may have other processes, such as swelling, bridge | crosslinking by boric acid, washing | cleaning by aqueous solution, and drying. The stretching or dyeing step may be performed by a PVA film alone, or may be performed in a state of being laminated with other films such as polyethylene terephthalate. Preferably the film thickness of the PVA system film used is 10-100 micrometers, and the said draw ratio is 2-10 times preferably.

As another example of the said polarizer, the liquid crystal coating type polarizer formed by apply | coating and forming a liquid crystal polarizing composition is mentioned. The liquid crystal polarizing composition may contain a liquid crystal compound and a dichroic dye compound. The said liquid crystalline compound should just have the property to show a liquid crystal state, and especially since it can exhibit high polarization performance, if it has high order orientation states, such as a smectic phase, it is preferable. Moreover, it is preferable that a liquid crystalline compound has a polymeric functional group.

The said dichroic dye compound may have a polymeric functional group as a pigment | dye which orientates with the said liquid crystal compound, and shows dichroism, and the dichroic dye itself may have liquid crystallinity.

Any of the compounds contained in the liquid crystal polarizing composition have a polymerizable functional group. The liquid crystal polarizing composition may further include an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a crosslinking agent, a silane coupling agent, and the like.

The said liquid crystal polarizing layer is manufactured by apply | coating a liquid crystal polarizing composition on an oriented film, and forming a liquid crystal polarizing layer. The liquid crystal polarizing layer can be formed thinner than the film polarizer, and the thickness thereof is preferably 0.5 to 10 µm, more preferably 1 to 5 µm.

The said oriented film is manufactured by apply | coating an oriented film formation composition on a base material, and providing an orientation by rubbing, polarized light irradiation, etc., for example. The alignment film forming composition contains an alignment agent, and may further include a solvent, a crosslinking agent, an initiator, a dispersant, a leveling agent, a silane coupling agent, and the like. As said aligning agent, polyvinyl alcohol, polyacrylates, polyamic acid, polyimide is mentioned, for example. When using the aligning agent which provides orientation by polarized light irradiation, it is preferable to use the aligning agent containing a cinnamate group. The weight average molecular weight of the polymer used as the aligning agent is, for example, about 10,000 to 1,000,000. The film thickness of the said oriented film becomes like this. Preferably it is 5-10,000 nm, In the point that the orientation regulation force fully expresses, More preferably, it is 10-500 nm.

The liquid crystal polarizing layer may be peeled off from the substrate, transferred and laminated, or the substrate may be laminated as it is. It is also preferable that the said base material plays a role as a transparent base material of a protective film, a retardation plate, and a window film.

As said protective film, what is necessary is just a transparent polymer film, and the thing similar to the material and additive used for the transparent base material of the said window film can be used. Moreover, the coating type protective film obtained by apply | coating and hardening radical curable compositions, such as a cation hardening composition, such as an epoxy resin, and an acrylate, may be sufficient. The protective film may contain a plasticizer, an ultraviolet absorber, an infrared absorber, a colorant such as a pigment or a dye, a fluorescent brightener, a dispersant, a heat stabilizer, a light stabilizer, an antistatic agent, an antioxidant, a lubricant, a solvent, and the like. . The thickness of the said protective film becomes like this. Preferably it is 200 micrometers or less, More preferably, it is 1-100 micrometers. When the thickness of a protective film exists in said range, there exists a tendency for the flexibility of the said film to fall easily.

The said (lambda) / 4 phase (s) difference plate is a film which provides the phase difference of (lambda) / 4 in the direction (in-plane direction of a film) which is perpendicular to the advancing direction of incident light. The lambda / 4 phase difference plate may be a stretchable phase difference plate produced by stretching a polymer film such as a cellulose film, an olefin film, a polycarbonate film. The λ / 4 retardation plate may be a phase difference regulator, a plasticizer, an ultraviolet absorber, an infrared absorber, a colorant such as a pigment or a dye, a fluorescent brightener, a dispersant, a heat stabilizer, a light stabilizer, an antistatic agent, an antioxidant, a lubricant, a solvent, and the like. Etc. may be included.

The thickness of the stretched retardation plate is preferably 200 µm or less, and more preferably 1 to 100 µm. When the thickness of the stretchable retardation plate is in the above range, the flexibility of the stretched retardation plate tends to be less likely to be lowered.

Furthermore, as another example of the said (lambda) / 4 phase (s) difference plate, the liquid crystal coating type phase difference plate formed by apply | coating and forming a liquid crystal composition is mentioned.

The liquid crystal composition includes a liquid crystal compound exhibiting liquid crystal states such as nematic, cholesteric, and smectic. The liquid crystal compound has a polymerizable functional group.

The liquid crystal composition may further include an initiator, a solvent, a dispersant, a leveling agent, a stabilizer, a surfactant, a crosslinking agent, a silane coupling agent, and the like.

The said liquid crystal coating type phase difference plate can be manufactured similarly to the said liquid crystal polarizing layer by apply | coating and hardening a liquid crystal composition on a base, and forming a liquid crystal phase difference layer. The liquid crystal coating retardation plate can be formed thinner than the stretchable retardation plate. Thickness of the said liquid crystal polarizing layer becomes like this. Preferably it is 0.5-10 micrometers, More preferably, it is 1-5 micrometers.

The liquid crystal coating type retardation plate may be peeled off from the substrate, transferred and laminated, or the substrate may be laminated as it is. It is also preferable that the said base material plays a role as a transparent base material of a protective film, a retardation plate, and a window film.

In general, the shorter the wavelength, the larger the birefringence, and the longer the wavelength, the more material exhibits the small birefringence. In this case, since the phase difference of lambda / 4 cannot be achieved in the entire visible light region, the in-plane phase difference is preferably 100 to 180 nm so that the lambda / 4 is around 560 nm with high visibility. More preferably, it is designed to be 130-150 nm. The reverse dispersion (lambda) / 4 phase (s) difference plate which used the material which has a birefringence wavelength dispersion characteristic opposite to the normal is preferable at the point that visibility is favorable. As such a material, what is described, for example in Unexamined-Japanese-Patent No. 2007-232873, etc. can be used for a stretchable retardation plate, etc., and a liquid crystal coating retardation plate can be used.

As another method, a technique for obtaining a wideband [lambda] / 4 phase difference plate by combining with a [lambda] / 2 phase difference plate is also known (for example, JP-A-10-90521). [lambda] / 2 retardation plates are also manufactured from the same materials and methods as [lambda] / 4 retardation plates. Although the combination of an extending | stretching retardation plate and a liquid crystal coating type retardation plate is arbitrary, film thickness can be made thin by using a liquid crystal coating type retardation plate in either case.

In order to improve the visibility of a diagonal direction, the said circularly polarizing plate is known by laminating | stacking a positive C plate (for example, Unexamined-Japanese-Patent No. 2014-224837 etc.). The positive C plate may be a liquid crystal coating type retardation plate or a stretched retardation plate. The phase difference in the thickness direction of the retardation plate is preferably -200 to -20 nm, more preferably -140 to -40 nm.

[Touch sensor]

It is preferable that a flexible display apparatus is provided with a touch sensor as mentioned above. The touch sensor is used as an input means. As a touch sensor, various forms, such as a resistive film system, a surface acoustic wave system, an infrared system, an electromagnetic induction system, and a capacitive system, are mentioned, Preferably, a capacitive system is mentioned.

The capacitive touch sensor is divided into an active region and an inactive region located at an outer portion of the active region. The active area is an area corresponding to an area (display) where a screen is displayed on the display panel. The active area is an area where a user's touch is detected. The inactive area is an area corresponding to an area (non-display area) where a screen is not displayed on the display device. . The touch sensor includes a substrate having a flexible characteristic, a sensing pattern formed in an active region of the substrate, and a sensing line formed in an inactive region of the substrate, and connected to an external driving circuit through the sensing pattern and the pad unit. It may include. As a board | substrate which has a flexible characteristic, the material similar to the transparent substrate of the said window film can be used.

The sensing pattern may include a first pattern formed in a first direction and a second pattern formed in a second direction. The first pattern and the second pattern are disposed in different directions. The first pattern and the second pattern are formed on the same layer, and each pattern must be electrically connected in order to detect a touched point. Although the first pattern has a form in which a plurality of unit patterns are connected to each other via a seam, the second pattern has a structure in which a plurality of unit patterns are separated from each other in an island form. A bridge electrode is needed. A well-known transparent electrode can be applied to the electrode for connection of a 2nd pattern. Examples of the material of the transparent electrode include indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium zinc oxide (IZTO), cadmium tin oxide (CTO), and PEDOT (poly ( 3,4-ethylenedioxythiophene)), carbon nanotubes (CNT), graphene, metal wires, and the like, and preferably ITO. These can be used individually or in mixture of 2 or more types. The metal used for a metal wire is not specifically limited, For example, silver, gold, aluminum, copper, iron, nickel, titanium, selenium, chromium, etc. are mentioned, These can be used individually or in mixture of 2 or more types. .

The bridge electrode may be formed on the insulating layer through the insulating layer on the sensing pattern, the bridge electrode is formed on the substrate, and the insulating layer and the sensing pattern may be formed thereon. The bridge electrode may be formed of the same material as the sensing pattern, or may be formed of molybdenum, silver, aluminum, copper, palladium, gold, platinum, zinc, tin, titanium, or an alloy of two or more thereof.

Since the first pattern and the second pattern must be electrically insulated, an insulating layer is formed between the sensing pattern and the bridge electrode. The insulating layer may be formed only between the joint of the first pattern and the bridge electrode, or may be formed as a layer covering the entire sensing pattern. In the case of the layer covering the entire sensing pattern, the bridge electrode may connect the second pattern through the contact hole formed in the insulating layer.

The touch sensor includes a difference in light transmittance caused by a difference in transmittance between a pattern region in which a sensing pattern is formed and a non-pattern region in which a sensing pattern is not formed, specifically, a difference in refractive index in these regions. The optical control layer may be further included between the substrate and the electrode as a means for properly compensating for the C. The optical adjusting layer may include an inorganic insulating material or an organic insulating material. The optical control layer may be formed by coating a photocurable composition including a photocurable organic binder and a solvent on a substrate. The photocurable composition may further include inorganic particles. By the said inorganic particle, the refractive index of an optical adjusting layer can be made high.

The photocurable organic binder may include, for example, a copolymer of each monomer such as an acrylate monomer, a styrene monomer, a carboxylic acid monomer, and the like within a range that does not impair the effects of the present invention. The said photocurable organic binder may be a copolymer containing each different repeating unit, such as an epoxy group containing repeating unit, an acrylate repeating unit, and a carboxylic acid repeating unit, for example.

As said inorganic particle, a zirconia particle, a titania particle, an alumina particle, etc. are mentioned, for example.

The said photocuring composition may further contain each additive, such as a photoinitiator, a polymerizable monomer, and a hardening adjuvant.

[Adhesive layer]

Each layer (window film, circular polarizing plate, touch sensor) which forms the said laminated body for flexible image display apparatuses, and the film member (linear polarizing plate, (lambda) / 4 phase (s) difference plate, etc.) which comprise each layer can be bonded by an adhesive agent. . Examples of the adhesive include a water-based adhesive, an organic solvent-based adhesive, a solvent-free adhesive, a solid adhesive, a solvent vaporized adhesive, a moisture curable adhesive, a heat curable adhesive, an anaerobic curable adhesive, an active energy ray curable adhesive, a curing agent mixed adhesive, Commonly used adhesives such as hot melt adhesives, pressure-sensitive adhesives (adhesives), re-wetting adhesives, and the like can be used. Preferably, aqueous solvent volatilized adhesives, active energy ray-curable adhesives, and adhesives can be used. have. The thickness of an adhesive bond layer can be adjusted suitably according to the adhesive force requested | required etc., Preferably it is 0.01-500 micrometers, More preferably, it is 0.1-300 micrometers. Although the some adhesive layer exists in the said laminated body for flexible image display apparatuses, each thickness and the kind of the said adhesive layer may be same or different.

As the aqueous solvent volatilizing adhesive, a polymer in a water dispersion state such as a polyvinyl alcohol polymer, a water-soluble polymer such as starch, an ethylene-vinyl acetate emulsion, a styrene-butadiene emulsion, or the like can be used as the main polymer. have. In addition to the said main polymer and water, you may mix | blend a crosslinking agent, a silane compound, an ionic compound, a crosslinking catalyst, antioxidant, dye, a pigment, an inorganic filler, an organic solvent, etc. In the case of adhering with the aqueous solvent volatilized adhesive, the aqueous solvent volatilized adhesive may be injected between the adhered layers to bond the adhered layer, and then adhesiveness may be imparted by drying. When using the said aqueous solvent volatilization type adhesive agent, the thickness of the contact bonding layer becomes like this. Preferably it is 0.01-10 micrometers, More preferably, it is 0.1-1 micrometer. When using the said aqueous solvent volatilization adhesive agent in multiple layers, the thickness of each layer and the kind of aqueous solvent volatilization adhesive agent used may be same or different.

The said active energy ray hardening-type adhesive agent can be formed by hardening of the active energy ray hardening composition containing the reactive material which irradiates an active energy ray and forms an adhesive bond layer. The said active energy ray hardening composition can contain the at least 1 sort (s) of polymer of the radically polymerizable compound and cationic polymerizable compound similar to what is contained in a hard coat composition. As the radically polymerizable compound, the same compound as the radically polymerizable compound in the hard coating composition can be used.

As the cationically polymerizable compound, the same compound as the cationically polymerizable compound in the hard coating composition can be used.

As a cationically polymerizable compound used for an active energy ray hardening composition, an epoxy compound is especially preferable. It is also preferable to include a monofunctional compound as a reactive diluent in order to lower the viscosity as an adhesive composition.

The active energy ray composition may contain a monofunctional compound in order to lower the viscosity. As the monofunctional compound, an acrylate monomer having one (meth) acryloyl group in one molecule or a compound having one epoxy group or oxetanyl group in one molecule, for example, glycidyl (meth) Acrylates and the like.

The active energy ray composition may further comprise a polymerization initiator. Examples of the polymerization initiator include radical polymerization initiators, cationic polymerization initiators, radicals and cationic polymerization initiators, and these may be appropriately selected and used. These polymerization initiators are decomposed by at least one of active energy ray irradiation and heating to generate radicals or cations to advance radical polymerization and cation polymerization. In the base material of a hard coat composition, the initiator which can start at least any of radical polymerization or cationic polymerization by active energy ray irradiation can be used.

The active energy ray-curing composition may further include an ion trapping agent, an antioxidant, a chain transfer agent, an adhesion agent, a thermoplastic resin, a filler, a fluid viscosity modifier, a plasticizer, an antifoaming agent, an additive, and a solvent. In the case of adhering two adherend layers with the active energy ray-curable adhesive, the active energy ray curable composition is applied to any one or both of the adherend layers, and then bonded to each other, to which of the adherend layers or both. It can adhere | attach by irradiating and hardening an active energy ray to a to-be-bonded layer. When using the said active energy ray hardening-type adhesive agent, the thickness of this contact bonding layer becomes like this. Preferably it is 0.01-20 micrometers, More preferably, it is 0.1-10 micrometers. When using the said active energy ray hardening-type adhesive agent for formation of several adhesive layer, the thickness of each layer and the kind of active energy ray hardening-type adhesive agent used may be same or different.

As an adhesive, the thing similar to said adhesive can be used. When using more than one layer of the said adhesive, the thickness of each layer and the kind of adhesive used may be same or different.

[Shielding pattern]

The light shielding pattern can be applied as at least a part of the bezel or the housing of the flexible image display device. The visibility of an image improves by making the wiring arrange | positioned at the edge part of the said flexible image display apparatus hidden by a light shielding pattern, and making it hard to see. The light shielding pattern may be in the form of a single layer or a multilayer. The color of the light shielding pattern is not particularly limited, and various colors such as black, white, and metal may be used. The light shielding pattern may be formed of a pigment for realizing color, and a polymer such as an acrylic resin, an ester resin, an epoxy resin, polyurethane, or silicone. It can also be used by these single or 2 or more types of mixtures. The light shielding pattern may be formed by various methods such as printing, lithography, inkjet, and the like. The thickness of the light shielding pattern is preferably 1 to 100 µm, more preferably 2 to 50 µm. Moreover, it is also preferable to provide shapes, such as an inclination, in the thickness direction of a light shielding pattern.

EXAMPLE

EMBODIMENT OF THE INVENTION Although this invention is demonstrated further more concretely based on an Example and a comparative example below, this invention is not limited to a following example.

1. Measurement method and evaluation

(1) Yellowness (YI value)

Example using the three stimulus values X, Y and Z calculated by the calculation method specified in JIS Z 8701: 1982 using Hitachi Manufacturing Co., Ltd., a spectrophotometer (U-4100). And the yellowness (YI value) of the optical laminated body obtained by the comparative example was calculated. The evaluation method is shown below.

YI = 100 (1.28X-1.06Z) / Y

<Evaluation method>

The thing of YI <= 3 was made very favorable, and was described with (circle).

3 <YI <= 10 was made favorable and it described with (circle).

10 <YI was made into defects, and it described with x.

(2) light transmittance (Tt)

Using the spectrophotometer (U-4100) by Hitachi Ltd., it irradiated to the hard-coating surface side of the optical laminated body obtained by the Example and the comparative example, and the transmittance | permeability with respect to the light of 390 nm was measured. The measurement results are shown in Table 1.

(3) pencil hardness

The pencil hardness of the surface of the hard-coating surface side of an optical laminated body was measured based on JISK5600-5-4: 1999 using the unimeter manufactured by Mitsubishi Pencil Co., Ltd. The optical laminated body provided for the measurement was fixed on the glass plate of thickness 2mm, and it measured on the conditions of the load of 750g of angle 90 degrees, and the scanning speed of 60mm / min. The presence or absence of a scratch was evaluated under the illumination condition of 4,000 lux light quantity, and the pencil hardness was determined. The measurement results are shown in Table 1.

(4) Measurement of the weight average molecular weight (Mw)

The weight average molecular weight (Mw) of polyamideimide was calculated | required by standard polystyrene conversion by the gel permeation chromatography (GPC) measurement. Specific measurement conditions were as follows.

a. Pretreatment method

A solution obtained by adding DMF eluent (10 mM lithium bromide solution) to a polyamideimide (sample) to a concentration of 2 mg / mL, stirring with stirring at 80 ° C. for 30 minutes, cooling, and then filtering with a 0.45 μm membrane filter. Was taken as the measurement solution.

b. Measuring conditions

Column: TSKgel SuperAWM-H × 2 + SuperAW2500 × 1 (6.0 mm I.D. × 150 mm × 3 pieces)

Eluent: DMF (with 10 mM lithium bromide)

Flow rate: 1.0 mL / min.

Detector: RI Detector

Column temperature: 40 ℃

Injection volume: 100 μL

Molecular Weight Standard: Standard Polystyrene

(5) thickness measurement

The thickness of the base film was measured using a Micrometer (Mitutoyo Co., Ltd.), the thickness of the hard coating layer was measured by the F20 tabletop film thickness system made by Filmetrics.

2. UV absorbers

The following ultraviolet absorbers were prepared.

Sumisorb 340 (brand name: Sumitomo Chemical Co., Ltd. product, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole)

3. Polyamide Resin

(1) polyamideimide A (6FDA / TPC / BPDA = 3/6/1 (molar ratio))

53.05 g (165.66 mmol) of 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl (TFMB) in a 1 L separable flask with stirring blades under a nitrogen gas atmosphere and 670.91 g of N, N-dimethylacetamide (hereinafter sometimes referred to as DMAc) was added, and TFMB was dissolved in DMAc while stirring at room temperature. Next, 22.11 g (49.77 mmol) of 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), 3,3', 4,4'-biphenyltetracarboxylic acid 2 were added to the flask. 4.88 g (16.59 mmol) of anhydride (BPDA) were added, followed by 20.21 g (99.54 mmol) of terephthaloylchloride (TPC) and stirred at room temperature for 1 hour. Subsequently, 10.53 g (133.08 mmol) of pyridine and 13.77 g (134.83 mmol) of acetic anhydride were added to the flask, and after stirring for 30 minutes at room temperature, the temperature was raised to 70 ° C. using an oil bath, followed by further stirring for 3 hours. And the reaction liquid was obtained.

The obtained reaction solution was cooled to room temperature, poured into a large amount of methanol in a yarn shape, and the precipitate precipitated was taken out, and immersed in methanol for 6 hours, and then washed with methanol. Next, the precipitate was dried under reduced pressure at 100 ° C to obtain polyamideimide A. The weight average molecular weight of polyamideimide A was 190,000.

(2) polyamideimide B (6FDA / TPC / OBBC = 3/6/1 (molar ratio))

45 g (140.52 mmol) of TFMB and 859.96 g of DMAc were added to the 1 L separable flask with a stirring blade under nitrogen gas atmosphere, and TFMB was dissolved in DMAc while stirring at room temperature. Next, 18.87 g (42.48 mmol) of 6FDA was added to the flask, followed by 4.60 g (14.08 mmol) of 17.14 g (84.42 mmol) of TPC, 4,4′-oxybis (benzoylchloride) (OBBC). Was added and stirred at room temperature for 1 hour. Then, 4.62 g (49.55 mmol) of 4-picoline and 2.96 g (28.96 mmol) of acetic anhydride were added to the flask, and after stirring for 30 minutes at room temperature, the temperature was raised to 70 ° C. using an oil bath, and further 3 It stirred for the time and obtained the reaction liquid.

The obtained reaction solution was cooled to room temperature, poured into a large amount of methanol in a yarn form, and the precipitate precipitated was taken out, and after immersing in methanol for 6 hours, it was washed with methanol. Next, the precipitate was dried under reduced pressure at 100 ° C to obtain polyamideimide B. The weight average molecular weight of polyamideimide B was 430,000.

4. inorganic particles

Γ-butyrolactone (hereinafter sometimes referred to as GBL) substituted silica sol obtained by solvent substitution using an amorphous silica sol having a BET diameter of 27 nm produced by the sol-gel method as a raw material was used. As for all the obtained GBL substituted silica sol, the silica component (inorganic particle) was 30 mass%.

5. Curable composition (hard coating composition)

The following curable compositions (compositions for hard coating) were prepared.

Z-850-AFH (acrylic hard coating) made by Aika Kogyo Co., Ltd.

Example 1

Polyamideimide A was diluted with DMAc to prepare a polyamideimide varnish having a concentration of 22% by mass. There, the ultraviolet absorber [2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, "Sumisorb 340", and the DMAc solution of Sumitomo Chemical Co., Ltd. were mixed, and it stirred for 30 minutes. Content of the ultraviolet absorber was 5.5 mass parts with respect to 100 mass parts of polyamide-imide A. The polyamide-imide varnish containing the obtained ultraviolet absorber was apply | coated using the applicator so that the film thickness of a self-supporting film might be 55 micrometers on the smooth surface of a polyester base material (Toyobo Co., Ltd. make, brand name "A4100"), and 50 degreeC After drying for 30 minutes and then at 140 ° C. for 15 minutes, the obtained coating film was peeled from the polyester substrate to obtain a freestanding film. The self-supporting film was fixed to a metal mold and further dried at 300 ° C. for 40 minutes in the air to obtain a polyamideimide film (base film) having a thickness of 50 μm.

The coating film was apply | coated to the single side | surface of the obtained base film with a bar coater, and it dried for 3 minutes at 80 degreeC, and irradiated and hardened | cured by irradiation of a high pressure mercury lamp (500 mJ / cm <2>, 200 mW / cm <2>) in nitrogen atmosphere. Was formed and the optical laminated body was obtained. The film thickness of the hard coat layer was 10 μm. The light transmittance of 390 nm of the optical laminated body was 11.9%.

Example 2

Polyamideimide B was diluted in the solution which melt | dissolved the ultraviolet absorber [Sumisorb 340, the Sumitomo Chemical Co., Ltd.] in GBL solution, and prepared the polyamideimide varnish of 9.5 mass% in concentration. Content of the ultraviolet absorber was 5.5 mass parts with respect to 100 mass parts of polyamide-imide B. The polyamide-imide varnish containing the obtained ultraviolet absorber was apply | coated using the applicator so that the film thickness of a self-supporting film might be 55 micrometers on the smooth surface of a polyester base material (Toyobo Co., Ltd. make, brand name "A4100"), and 50 degreeC After drying for 30 minutes and then at 140 ° C. for 15 minutes, the obtained coating film was peeled from the polyester substrate to obtain a freestanding film. The self-supporting film was fixed to a metal frame, and further dried in the air at 200 ° C. for 40 minutes to obtain a polyamideimide film (base film) having a thickness of 50 μm.

The coating film was apply | coated to the single side | surface of the obtained base film with a bar coater, and it dried for 3 minutes at 80 degreeC, and irradiated and hardened | cured by irradiation of a high pressure mercury lamp (500 mJ / cm <2>, 200 mW / cm <2>) in nitrogen atmosphere. Was formed and the optical laminated body was obtained. The film thickness of the hard coat layer was 10 μm. The light transmittance of 390 nm of the optical laminated body was 18.5%.

Example 3

The optical laminated body was obtained like Example 2 except having added GBL substituted silica sol to the polyamide-imide varnish. The film thickness of the base film and the film thickness of the hard coat layer were 50 micrometers and 10 micrometers, respectively. The transmittance | permeability with respect to the light of 390 nm of the optical laminated body was 17.5%. Content of the said silica sol was 50 mass parts with respect to 100 mass parts of polyamide-imide B.

Example 4

Polyamideimide B was diluted with the solution which melt | dissolved the ultraviolet absorber (hydroxyphenyl triazine derivative, "Tinuvin 400", BASF Corporation make) in GBL solution, and prepared the polyamideimide varnish of 9.5 mass% in concentration. Content of the ultraviolet absorber was 2.0 mass parts with respect to 100 mass parts of polyamide-imide B. The polyamide-imide varnish containing the obtained ultraviolet absorber was apply | coated using the applicator so that the film thickness of a self-supporting film might be 55 micrometers on the smooth surface of a polyester base material (Toyobo Co., Ltd. make, brand name "A4100"), and 50 degreeC After drying for 30 minutes and then at 140 ° C. for 15 minutes, the obtained coating film was peeled from the polyester substrate to obtain a freestanding film. The self-supporting film was fixed to a metal frame, and further dried in the air at 200 ° C. for 40 minutes to obtain a polyamideimide film (base film) having a thickness of 50 μm.

The coating film was apply | coated to the single side | surface of the obtained base film with a bar coater, and it dried for 3 minutes at 80 degreeC, and irradiated and hardened | cured by irradiation of a high pressure mercury lamp (500 mJ / cm <2>, 200 mW / cm <2>) in nitrogen atmosphere. Was formed and the optical laminated body was obtained. The film thickness of the hard coat layer was 10 μm. The light transmittance of 390 nm of the optical laminated body was 65.1%.

Example 5

Polyamideimide B was diluted in the solution which melt | dissolved the ultraviolet absorber [Sumisorb 340, the Sumitomo Chemical Co., Ltd.] in GBL solution, and prepared the polyamideimide varnish of 9.5 mass% in concentration. Content of the ultraviolet absorber was 2.0 mass parts with respect to 100 mass parts of polyamide-imide B. The polyamide-imide varnish containing the obtained ultraviolet absorber was applied on the smooth surface of the polyester base material (Toyobo, brand name "A4100") using an applicator so that the film thickness of a self-supporting film might be 55 micrometers, and it was 30 minutes at 50 degreeC. Then, after drying at 140 degreeC for 15 minutes, the obtained coating film was peeled from the polyester base material and the self-supporting film was obtained. The self-supporting film was fixed to a metal frame, and further dried in the air at 200 ° C. for 40 minutes to obtain a polyamideimide film (base film) having a thickness of 50 μm.

The coating film was apply | coated to the single side | surface of the obtained base film with a bar coater, and it dried for 3 minutes at 80 degreeC, and irradiated and hardened | cured by irradiation of a high pressure mercury lamp (500 mJ / cm <2>, 200 mW / cm <2>) in nitrogen atmosphere. Was formed and the optical laminated body was obtained. The film thickness of the hard coat layer was 10 μm. The light transmittance of 390 nm of the optical laminated body was 45.3%.

Example 6

Polyamideimide B containing GBL-substituted silica sol was diluted in a solution obtained by dissolving a ultraviolet absorber [hydroxyphenyltriazine derivative, manufactured by Tinuvin 479, BASF Corporation] in a GBL solution, to obtain a polyamide having a concentration of 9.5% by mass. Mid varnish was prepared. Content of the ultraviolet absorber was 1.0 mass part with respect to 100 mass parts of polyamide-imide B. The polyamide-imide varnish containing the obtained ultraviolet absorber was apply | coated using the applicator so that the film thickness of a self-supporting film might be 55 micrometers on the smooth surface of a polyester base material (Toyobo Co., Ltd. make, brand name "A4100"), and 50 degreeC After drying for 30 minutes and then at 140 ° C. for 15 minutes, the obtained coating film was peeled from the polyester substrate to obtain a freestanding film. The self-supporting film was fixed to a metal frame, and further dried in the air at 200 ° C. for 40 minutes to obtain a polyamideimide film (base film) having a thickness of 50 μm. Content of the said silica sol was 50 mass parts with respect to 100 mass parts of polyamide-imide B.

The coating film was apply | coated to the single side | surface of the obtained base film with a bar coater, and it dried for 3 minutes at 80 degreeC, and irradiated and hardened | cured by irradiation of a high pressure mercury lamp (500 mJ / cm <2>, 200 mW / cm <2>) in nitrogen atmosphere. Was formed and the optical laminated body was obtained. The film thickness of the hard coat layer was 10 μm. The light transmittance of 390 nm of the optical laminated body was 58.1%.

Comparative Example 1

Polyamideimide A was diluted with DMAc to prepare a polyamideimide varnish having a concentration of 22% by mass. The obtained polyimide varnish was applied on the smooth surface of the polyester base material (Toyobo Co., Ltd., brand name "A4100") using an applicator so that the film thickness of a self-supporting film might be 55 micrometers, and then it was 140 minutes at 50 degreeC, and then 140 After drying at 15 ° C. for 15 minutes, the obtained coating film was peeled from the polyester substrate to obtain a freestanding film. The self-supporting film was fixed to a metal mold and further dried at 300 ° C. for 40 minutes in the air to obtain a polyamideimide film (base film) having a thickness of 50 μm.

The coating composition for hard coating which contains the ultraviolet absorber which added Sumisorb 340 (made by Sumitomo Chemical Co., Ltd.) to the composition for hard coating used in Example 1 was apply | coated by the bar coater to the obtained base film, After drying, the coating film was formed by irradiating and hardening a high pressure mercury lamp (500 mJ / cm <2>, 200 mW / cm <2>) in nitrogen atmosphere, and the optical laminated body was obtained. The film thickness of the hard coat layer was 10 μm. The quantity of the ultraviolet absorber was 5 mass parts with respect to 100 mass parts of components except the solvent of the composition for hard coating.

Table 1 shows the results of measuring the YI value and the pencil hardness of the optical laminates obtained in Examples 1 to 6 and Comparative Example 1.

Table 1

It was confirmed that the pencil hardness of the optical laminated bodies of Examples 1-6 was remarkably high compared with the optical laminated body of Comparative Example 1. Moreover, it was confirmed that the optical laminated bodies of Examples 2-6 were lower in YI value than the optical laminated body of Comparative Example 1 (evaluation is very good), and the optical laminated body of Example 1 was favorable in evaluation of YI value. Therefore, the optical laminated bodies of Examples 1-6 have the outstanding surface hardness, and can have the outstanding transparency. Moreover, it turned out that the optical laminated bodies of Examples 1-3 are low in the light transmittance at 390 nm, and also excellent in the ultraviolet absorbency.

One … Optical stack
2 … Substrate film
3…. Hard coating layer

Claims (13)

As a base film containing a polyamideimide and an aromatic compound, and the optical laminated body which has a hard-coat layer in at least one surface of the said base film, the said polyamideimide is Formula (1) and Formula (2):

[In Formula (1) and Formula (2), X and Z respectively independently represent a divalent organic group, and Y represents a tetravalent organic group.]
Having a structural unit represented by
Aromatic compounds are ultraviolet absorbers,
The optical laminated body whose content of the ultraviolet absorber contained in a base film is larger than content of the ultraviolet absorber in a hard-coat layer, and the pencil hardness of the said optical laminated body measured under the roughness conditions of 4000 lux is H or more. The method of claim 1,
An ultraviolet absorber is at least 1 sort (s) chosen from the group which consists of a benzotriazole type ultraviolet absorber and a triazine type ultraviolet absorber. The method of claim 1,
The optical laminated body whose content of a ultraviolet absorber is 0.01-10 mass parts with respect to 100 mass parts of polyamide-imide. The method of claim 1,
Content of the structural unit represented by Formula (2) is 0.1-3.9 mol with respect to 1 mol of structural units represented by Formula (1). The method of claim 1,
The base film contains an inorganic particle. The method of claim 1,
The optical laminated body whose light transmittance at 390 nm is 35% or less. The method of claim 1,
Polyamideimide, Formula (1) and Formula (2):

[In Formula (1) and Formula (2), X and Z respectively independently represent a divalent organic group, Y represents a tetravalent organic group,
At least part of Z is of the formula (3):

(Formula (3) of, R ¹ ~R ⁸ are, each independently, a hydrogen atom contained in the hydrogen atom and represents an alkyl group having 1 to 6 carbon atoms or 6 to 12 carbon atoms of the aryl, R ¹ ~R ⁸ are each Independently, they may be substituted by a halogen atom,
A represents -O-, -S-, -CO- or -NR ^9- , R ⁹ represents a hydrocarbon group having 1 to 12 carbon atoms which may be substituted with a halogen atom,
m is an integer of 0 to 4,
* Represents a bonding hand)
Is a structural unit represented by
The optical laminated body which has a structural unit represented by The flexible image display apparatus provided with the optical laminated body of any one of Claims 1-7. The method of claim 8,
Furthermore, the flexible image display apparatus containing a polarizing plate. The method of claim 8,
Furthermore, the flexible image display apparatus containing a touch sensor. delete delete delete

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