KR20200010080A - Polyamideimide resin - Google Patents

Abstract

Provided by the present invention is polyamideimide resin capable of forming a polyamideimide film having a high elastic modulus. The polyamideimide resin includes a composition unit representing the following characteristics. In formula 1 and formula 2, each X independently represents a divalent organic group, Y represents a tetravalent organic group, each R^a independently represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, each hydrogen atom contained in R^a may be independently substituted with a halogen atom and n represents an integer of 0-6. The weight average molecular weight of the polyamideimide resin is 100,000 to 1,000,000.

Description

Polyamideimide Resin {POLYAMIDEIMIDE RESIN}

The present invention relates to a polyamideimide resin and a polyamideimide film capable of forming a polyamideimide film used as a front plate material of an image display device and the like, and a flexible display device including the polyamideimide film.

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. Although glass has been used as the front plate of such an image display device, since glass is very rigid and brittle, it is difficult to use it as a front plate material, such as a flexible display, for example. As one of the materials which replace glass, the polyamideimide film formed from the polyamideimide resin is examined (for example, patent document 1).

Japanese Patent Publication No. 2015-521687

On the other hand, high elastic modulus is required for the polyamide-imide film used for an optical film use. However, according to examination by the present inventor, it turned out that the conventional polyamide-imide film may not have enough elastic modulus.

Accordingly, an object of the present invention is to provide a polyamideimide resin and a polyamideimide film capable of forming a polyamideimide film having a high modulus of elasticity, and a flexible display device including the polyamideimide film.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, as a structural unit derived from the dicarboxylic acid compound which comprises a polyamideimide resin, this inventor includes the structural unit derived from the dicarboxylic acid compound which has a naphthalene skeleton, When the said polyamideimide resin was the weight average molecular weight of a predetermined range, it discovered that the said subject could be solved and came to complete this invention. That is, the following preferable aspect is contained in this invention.

[1] Formula (1) and Formula (2)

[In Formula (1) and Formula (2), X represents a bivalent organic group each independently, Y represents a tetravalent organic group, R ^<a> respectively independently represents ^a halogen atom, a C1-C6 alkyl group, and carbon number An alkoxy group of 1 to 6 or an aryl group of 6 to 12 carbon atoms is represented, and the hydrogen atoms contained in R ^a may be each independently substituted with a halogen atom, and n represents an integer of 0 to 6;

The polyamideimide resin which contains the structural unit represented by and whose weight average molecular weight is 100,000-1,000,000.

[2] The polyamideimide resin according to [1], wherein the content of the structural unit represented by Formula (2) is 0.1 to 10 mol with respect to 1 mol of the structural unit represented by Formula (1).

[3] Formula (2 ')

[In Formula (2 '), X and K each independently represent a divalent organic group, and at least one part of K represents Formula (3).

(Formula (3) of, R ¹ ~ R ⁸ is each independently represents a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms alkyl group, having 1 to 6 carbon atoms, or an aryl group having a carbon number of ^{6 ~ 12, R 1 ~ R} 8 The hydrogen atoms contained in each may be independently substituted with a halogen atom, and A is a single bond, -O-, -CH _2- , -CH ₂ -CH _2- , -CH (CH ₃ )-,- C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -SO _2- , -S-, -CO- or -N (R ⁹ )-, and R ⁹ is substituted with a hydrogen atom or a halogen atom Represents a hydrocarbon group having 1 to 12 carbon atoms, m is an integer of 0 to 4, and * represents a bond.)

Appears]

The polyamideimide resin as described in [1] or [2] which further contains the structural unit represented by these.

[4] A polyamideimide film, comprising the polyamideimide resin according to any one of [1] to [3].

[5] A flexible display device comprising the polyamideimide film according to [4].

[6] The flexible display device according to [5], further comprising a touch sensor.

[7] The flexible display device according to [5] or [6], further comprising a polarizing plate.

The polyamideimide film comprising the polyamideimide resin of the present invention has a high modulus of elasticity. For this reason, it can use suitably as a front plate material etc. of an image display apparatus.

<Polyamideimide resin>

The polyamideimide resin of the present invention is formula (1) and formula (2)

[In Formula (1) and Formula (2), X represents a bivalent organic group each independently, Y represents a tetravalent organic group, R ^<a> respectively independently represents ^a halogen atom, a C1-C6 alkyl group, and carbon number An alkoxy group of 1 to 6 or an aryl group of 6 to 12 carbon atoms is represented, and the hydrogen atoms contained in R ^a may be each independently substituted with a halogen atom, and n represents an integer of 0 to 6;

The structural unit represented by this is a weight average molecular weight 100,000-100,000. The polyamideimide resin of this invention can improve elastic modulus by including the structural unit (it may be called the structural unit which has a naphthalene skeleton) represented by Formula (2), and the polyamideimide film obtained has high elastic modulus. Can have. Moreover, since the said polyamide-imide film is also excellent in bending resistance, it can also make high elastic modulus and high bending resistance compatible. In addition, in this specification, the "structural unit" in polyamideimide resin represents the repeating structural unit which comprises polyamideimide resin.

In Formula (2), R ^<a> represents ^a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a C6-C12 aryl group each independently. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example. 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. 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. Examples of the alkoxy group having 1 to 6 carbon atoms include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group and cyclohexyl octa Season, etc. can be mentioned. From the viewpoint of easily improving the elastic modulus and flexural resistance of the resulting polyamideimide film, R ^a is preferably a halogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a halogen atom or an alkyl group having 1 to 3 carbon atoms, It is more preferable that it is a methyl group or an ethyl group. Here, the hydrogen atoms contained in R ^a may be each independently substituted with a halogen atom. Moreover, from a viewpoint of the elasticity modulus and the bending resistance improvement of the polyamideimide film obtained, n is an integer of 0-6, Preferably it is an integer of 0-4, More preferably, it is an integer of 0-2, More preferably Is zero.

In Formula (2), two amide groups (-NHCO-) may be substituted by each of the two benzene rings which comprise a naphthalene ring one by one, and both of them are substituted by a benzene ring of a benzene ring among two benzene rings. You may be. That is, in two amide groups, one amide group may be substituted at the 1-4 position of a naphthalene ring, the other amide group may be substituted at the 5-8 position of a naphthalene ring, and both amide groups may be 1-4 positions of a naphthalene ring (or 5-8 position) may be substituted.

In one Embodiment of this invention, when one amide group is substituted by the 1-position or 2 position of a naphthalene ring in Formula (2), the other amide group may be substituted by the 5-8 position of a naphthalene ring, and it is preferable. May be substituted at the 5 or 6 position. From the viewpoint of easily improving the elastic modulus and flexural resistance of the polyamideimide film, more preferably, the two amide groups are substituted in the relationship of 2, 6, 1, 4 or 1, 5 position, and more preferably 2 , 6 positions are substituted.

In addition, in one embodiment of the present invention, from the viewpoint of easily improving the modulus of elasticity, in Formula (2), one amide group is substituted at 1 position of the naphthalene ring, and the other amide group is 3 or 4 position of the naphthalene ring, preferably May be substituted in the 4 position.

In Formula (1) and Formula (2), X represents a divalent organic group each independently, Preferably it is a C4-C40 divalent organic group, More preferably, C4-C40 which has a cyclic structure Represents a divalent organic group. Examples of the cyclic structure include an alicyclic, aromatic ring, and heterocyclic structure. In the organic group, the hydrogen atom in the organic group may be substituted with a hydrocarbon group or a fluorine-substituted hydrocarbon group, and in that case, the carbon number of the hydrocarbon group and the fluorine-substituted hydrocarbon group is preferably 1-8. The polyamideimide 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). ; A group in which a hydrogen atom in the group represented by the formulas (10) to (18) is substituted with a methyl group, a fluoro group, a chloro group, or a trifluoromethyl group; And a C6 or less chain hydrocarbon group is illustrated.

In formulas (10) to (18), * represents a bonding hand,

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 -NQ. Here, Q represents the C1-C12 hydrocarbon group which may be substituted by the halogen atom.

One example is that 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 preferably a meta position or a para position, more preferably a para position for each ring.

Among the groups represented by the formulas (10) to (18), the surface hardness, the bending resistance and the elastic modulus of the polyamide-imide film tend to be increased, and thus, the formulas (13), (14), (15), and (16) ) And groups represented by formula (17) are preferable, and groups represented by formulas (14), (15) and (16) are more preferable. In addition, since V ¹ , V ² and V ³ tend to increase the surface hardness, elastic modulus and flexibility of the polyamide-imide film, each independently, preferably a single bond, -O- or -S-, more preferably Single bond or -O-.

In a preferred embodiment of the invention, at least some of the plurality of X in formulas (1) and (2) are formula (4):

[In formula (4), R <^10> -R <^17> represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group, or a C6-C12 aryl group each independently, and R <^10> -R The hydrogen atoms contained in ¹⁷ may be each independently substituted with a halogen atom, and * represents a bond.]

Is represented by. If at least one part of some X in Formula (1) and Formula (2) is group represented by Formula (4), a polyamide-imide film will improve elasticity modulus, transparency, etc. easily.

In Formula (4), R <^10> , R <^11> , R <^12> , R <^13> , R <^14> , R <^15> , R <^16> and R <^17> are respectively independently a hydrogen atom, a C1-C6 alkyl group, and C1-C6 An alkoxy group or a C6-C12 aryl group. As a C1-C6 alkyl group, a C1-C6 alkoxy group, or a C6-C12 aryl group, a C1-C6 alkyl group, C1-C6 alkoxy group, or carbon number in R ^<a> of Formula (2) The thing illustrated as an aryl group of 6-12 is mentioned. R ¹⁰ to R ¹⁷ each independently preferably represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, wherein R ¹⁰ to R ¹⁷ The hydrogen atoms contained in each may be independently substituted with a halogen atom. As a halogen atom, what was illustrated as the halogen atom in R ^<a> of Formula (2) is mentioned. R ¹⁰ to R ¹⁷ each independently represent a hydrogen atom, a methyl group, a fluoro group, a chloro group or a trifluoromethyl group from the viewpoint of increasing the elastic modulus, flex resistance and transparency of the polyamideimide film. , Particularly preferably R ¹⁰ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , and R ¹⁶ are hydrogen atoms, R ¹¹ and R ¹⁷ are hydrogen atoms, methyl groups, fluoro groups, chloro groups or trifluoromethyl groups And particularly preferably R ¹¹ and R ¹⁷ are a methyl group or a trifluoromethyl group.

In a preferred embodiment of the invention, the group represented by formula (4) is represented by the formula (4 '):

In other words, at least a part of the plurality of X's is a group represented by Formula (4 '). In this case, the polyamideimide film tends to improve the elastic modulus and transparency, and also improves the solubility of the polyamideimide resin in the solvent by a skeleton containing a fluorine element, and suppresses the viscosity of the resin varnish low. It is also possible to facilitate the processability of the film.

In a preferred 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 said polyamideimide resin is of formula (4), in particular It is represented by formula (4 '). When X in the said range in the said polyamideimide resin is represented by Formula (4), especially Formula (4 '), a polyamideimide film tends to improve elasticity modulus and transparency, and contains a fluorine element. It is also possible to improve the solubility of the polyamide-imide resin in the solvent by reducing the viscosity of the polyamide-imide resin, to lower the viscosity of the resin varnish and to facilitate the processability of the film. Moreover, Preferably, 100 mol% or less of X in the said polyamideimide resin is represented by Formula (4), especially Formula (4 '). X in the said polyamide-imide resin may be Formula (4), especially Formula (4 '). Ratio of the group represented by the formula (4) in the X in the polyamide-imide resin, 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 represents a C4-C40 tetravalent organic group, More preferably, it is C4-C40 tetravalent organic which has a cyclic structure. Group. Examples of the cyclic structure include an alicyclic, aromatic ring, and heterocyclic structure. The said organic group 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, In that case, carbon number of a hydrocarbon group and a fluorine-substituted hydrocarbon group becomes like this. Preferably it is 1-8. . The polyamideimide resin which is one embodiment of the present invention may include a plurality of Y, and the plurality of Y may be the same as or different from each other. As Y, the following formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27), formula (28) and A group represented by formula (29); A group in which a hydrogen atom in the group represented by the formulas (20) to (29) is substituted with a methyl group, a fluoro group, a chloro group, or a trifluoromethyl group; And the tetravalent hydrocarbon group of 6 or less carbon atoms is illustrated.

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-. 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), the group represented by the formula (26), the formula (28) or the formula (29), from the viewpoint of the tendency of the elastic modulus, the surface hardness and the bending resistance of the polyamide-imide film to be increased, etc. It is preferable and the group represented by Formula (26) is more preferable. In addition, from the viewpoint that W ¹ tends to increase the elastic modulus, the surface hardness, the bending resistance, and the like of the polyamideimide film, and the yellowness (YI value) is easily suppressed, each independently, preferably a single bond, -O- , -CH _2- , -CH ₂ -CH _2- , -CH (CH ₃ )-, -C (CH ₃ ) ₂ -or -C (CF ₃ ) _2- , more preferably 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, a C1-C6 alkoxy group, or a C6-C12 aryl group, and ^R18 -R The hydrogen atoms contained in ²⁵ may be each independently substituted with a halogen atom, and * represents a bond.]

Is represented by. If at least one part of several Y in Formula (1) is group represented by Formula (5), a polyamide-imide film will tend to improve elasticity modulus, transparency, bendability, etc., and will be made into the solvent of a polyamideimide resin. It is also possible to improve the solubility to the resin, and to lower the viscosity of the resin varnish to facilitate the processability of the film.

In Formula (5), R <^18> , R <^19> , R <^20> , R <^21> , R <^22> , R <^23> , R <^24> and R <^25> respectively independently represent a hydrogen atom, a C1-C6 alkyl group, and C1-C6 An alkoxy group or a C6-C12 aryl group. As a C1-C6 alkyl group, a C1-C6 alkoxy group, or a C6-C12 aryl group, a C1-C6 alkyl group, C1-C6 alkoxy group, or carbon number in R ^<a> of Formula (2) The thing illustrated as an aryl group of 6-12 is mentioned. 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, wherein R ¹⁸ to R ²⁵ The hydrogen atoms contained in each may be independently substituted with a halogen atom. As a halogen atom, what was illustrated as the halogen atom in R ^<a> of Formula (2) is mentioned. R ¹⁸ to R ²⁵ are each independently, from the viewpoint of increasing the surface hardness, bending resistance and transparency of the polyamide-imide film, etc., more preferably a hydrogen atom, a methyl group, a fluoro group, a chloro group or a trifluoromethyl group. More preferably, R ¹⁸ , R ¹⁹ , R ²⁰ , R ²³ , R ²⁴ and R ²⁵ are hydrogen atoms, R ²¹ and R ²² are hydrogen atoms, methyl group, fluoro group, chloro group or trifluoromethyl group Especially preferably, R <^21> and R <^22> is a methyl group or a trifluoromethyl group.

In a preferred embodiment of the present invention, the group represented by formula (5) is formula (5 '):

In other words, at least a part of the plurality of Y's is a group represented by Formula (5 '). In this case, it is easy to improve the elasticity modulus, transparency, etc. of a polyamideimide film.

In a preferred embodiment of the invention, preferably at least 50 mol%, more preferably at least 60 mol%, even more preferably at least 70 mol% of Y of the polyamideimide resin is of formula (5), in particular It is represented by the formula (5 '). When Y in the said range in the said polyamideimide resin is represented by Formula (5), especially Formula (5 '), the polyamideimide film containing this polyamideimide resin has high elastic modulus, high transparency, and high flexibility. There exists a tendency to have a tendency to have, and the skeleton which further contains a fluorine element improves the solubility to the solvent of the said polyamideimide resin, can suppress the viscosity of resin varnish low, and manufacture of a film becomes easy. Moreover, Preferably, 100 mol% or less of Y in the said polyamideimide resin is represented by Formula (5), especially Formula (5 '). Y in the said polyamide-imide resin may be Formula (5), especially Formula (5 '). Ratio of the group represented by the formula (5) of the Y in the polyamide-imide resin, for example, can be measured by using a ¹ H-NMR, or may be calculated from the raw material doipbi.

In a preferred embodiment of the present invention, in the polyamideimide resin of the present invention, the content of the structural unit represented by the formula (2) is 0.1 mol or more, more preferably to 1 mol of the structural unit represented by the formula (1). Preferably it is 0.5 mol or more, More preferably, it is 1.0 mol or more, Especially preferably, it is 1.5 mol or more, Preferably it is 10.0 mol or less, More preferably, it is 6.0 mol or less, More preferably, it is 5.0 mol or less, Especially preferably, It is 4.5 mol or less, and arbitrary combinations of these upper limits and lower limits may be sufficient. When content of the structural unit represented by Formula (2) is more than the said minimum, a polyamide-imide film tends to express higher elastic modulus and bending resistance. 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 varnish can be reduced and a polyamide-imide film of Manufacturing becomes easy. In addition, the content (ratio) of the constituent unit represented by the formula (2) in the polyamide-imide resin, for example, it can be measured by using a ¹ H-NMR, or may be calculated from the raw material doipbi.

The polyamideimide resin of the present invention is formula (2 ')

[In formula (2 '), X and K each independently represent a divalent organic group.]

It may further include the structural unit shown by.

In Formula (2 '), K is a bivalent organic group each independently, Preferably carbon number which may be substituted by the C1-C8 hydrocarbon group or the fluorine-substituted C1-C8 hydrocarbon group It is a 4-40 organic group, More preferably, a C4-C40 divalent organic group which has a cyclic structure which may be substituted by the C1-C8 hydrocarbon group or the fluorine-substituted C1-C8 hydrocarbon group Indicates. Examples of the cyclic structure include an alicyclic, aromatic ring, and heterocyclic structure. As the organic group of K, formula (20), formula (21), formula (22), formula (23), formula (24), formula (25), formula (26), formula (27) and formula (28) Among the bonds of the group represented by the above, groups in which two non-adjacent groups are substituted with a hydrogen atom and a divalent chain hydrocarbon group having 6 or less carbon atoms are exemplified. Since it is easy to suppress the yellowness of a polyamideimide film (reduces YI value), group represented by Formula (20)-Formula (27) is preferable, and Formula (22), Formula (26), and Formula (27) are More preferably, formula (26) is especially preferable. In one embodiment of the present invention, the polyamide-imide resin may each include a plurality of types of K, and the plurality of types of K may be the same as or different from each other.

In a preferred embodiment of the present invention, at least part of K in the formula (2 ') is represented by the formula (3) from the viewpoint of further improving the surface hardness of the polyamide-imide film and making it possible to achieve high elastic modulus and high surface hardness.

(Formula (3) of, R ¹ ~ R ⁸ is each independently represents a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms alkyl group, having 1 to 6 carbon atoms, or an aryl group having a carbon number of ^{6 ~ 12, R 1 ~ R} 8 The hydrogen atoms contained in each may be independently substituted with a halogen atom, and A is a single bond, -O-, -CH _2- , -CH ₂ -CH _2- , -CH (CH ₃ )-,- C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -SO _2- , -S-, -CO- or -N (R ⁹ )-, and R ⁹ is substituted with a hydrogen atom or a halogen atom Represents a hydrocarbon group having 1 to 12 carbon atoms, m is an integer of 0 to 4, and * represents a bond.)

Include groups represented by

In the formula (3), A is, each independently, a single _{bond, -O-, -CH 2 -, -CH} 2 -CH 2 -, -CH (CH 3) -, -C (CH 3) 2 - , -C (CF ₃ ) _2- , -SO _2- , -S-, -CO- or -N (R ⁹ )-, from the viewpoint of improving the elastic modulus, surface hardness, and flexibility of the polyamideimide film. Preferably, -O- or -S- is represented, More preferably, -O- is represented. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or 6 carbon atoms An aryl group of 12 is represented. As a C1-C6 alkyl group, a C1-C6 alkoxy group, or a C6-C12 aryl group, a C1-C6 alkyl group, C1-C6 alkoxy group, or carbon number in R ^<a> of Formula (2) The thing illustrated above as an aryl group of 6-12 is mentioned. From the viewpoint of easily improving the surface hardness, elastic modulus, bending resistance and the like of the polyamideimide film, each of R ¹ to R ⁸ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably A hydrogen atom or a C1-C3 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 hydrocarbon group which may be substituted by the hydrogen atom and the halogen atom. Moreover, what was illustrated above as X of Formula (1) and Formula (2) is mentioned as X.

In Formula (3), m is an integer of the range of 0-4, and when m is in this range, there exists a tendency for the elasticity modulus, surface hardness, bending resistance, etc. of a polyamide-imide film to become favorable. Moreover, in Formula (3), m is preferably an integer of the range of 0-3, More preferably, it is an integer of the range of 0-2, More preferably, it is 0 or 1, Especially preferably, it is 1 . When m is in this range, there exists a tendency for the elasticity modulus, surface hardness, bending resistance, etc. of a polyamideimide film to become favorable, and the availability of a raw material is comparatively favorable. Moreover, K may contain 1 type (s) or 2 or more types of group represented by Formula (3), and it is more preferable to include the group whose m is 1 from a viewpoint which is easy to improve the elasticity modulus and surface hardness of a polyamide-imide film more. Do.

In a preferred embodiment of the invention, formula (3) is formula (3 '):

In other words, at least a part of the plurality of K's is a group represented by Formula (3 '). In this case, the polyamideimide film tends to exhibit high surface hardness, may have high bending resistance, and yellowness is also easily reduced.

In a preferred embodiment in which the polyamideimide resin of the present invention includes a group represented by formula (3), the content of the group represented by m in formula (3) is 0 to 4, preferably 1 to 4, is represented by formula (1): ), The structural unit represented by Formula (2), and the structural unit represented by Formula (2 ') (Hereinafter, it may be represented by the structural unit represented by Formula (1)-Formula (2').) The molar amount is preferably 3 mol% or more, more preferably 5 mol% or more, even more preferably 7 mol% or more, particularly preferably 9 mol% or more, preferably 90 mol% or less, more preferably Preferably it is 70 mol% or less, More preferably, it is 50 mol% or less, Especially preferably, it is 30 mol% or less, and arbitrary combinations of these upper limits and lower limits may be sufficient. When m in Formula (3) is 0-4, Preferably content of group represented by 1-4 is more than the said minimum, while a polyamideimide film has sufficient bending resistance, it is compatible with high elastic modulus and high surface hardness. easy to do. When the content of the group represented by m to 1 to 4 in formula (3) is equal to or less than the above upper limit, the viscosity of the resin varnish can be suppressed by suppressing the thickening due to hydrogen bonding between amide bonds derived from formula (3), Processing of a polyamideimide film can be made easy.

In a preferred embodiment in which the polyamideimide resin of the present invention includes a group represented by formula (3), the content of the group represented by m of formula (3) is 0 to 4, preferably 1 to 4, is represented by formula (2) Regarding the total molar amount of the structural unit represented by) and the structural unit represented by the formula (2 '), preferably 5 mol% or more, more preferably 8 mol% or more, even more preferably 10 mol% or more, particularly preferably Is 12 mol% or more, 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 any of these upper and lower limits It may be a combination. When m in Formula (3) is 0-4, Preferably content of group represented by 1-4 is more than the said minimum, while a polyamideimide film has sufficient bending resistance, it is compatible with high elastic modulus and high surface hardness. easy to do. Moreover, when m of Formula (3) is 0-4, Preferably content of group represented by 1-4 is below the said upper limit, by suppressing the thickening by the hydrogen bond between the amide bonds derived from Formula (3), The viscosity of the varnish can be suppressed and the processing of the polyamideimide film can be facilitated. Further, from the polyamide-imide resin in, m is 1 to 4 when the equation (3) the content (ratio) of groups represented by, for example, be measured by using a ¹ H-NMR, and or doipbi of the raw material for the It can also be calculated.

In preferable embodiment of this invention, content of the structural unit represented by Formula (2) in polyamideimide resin becomes like this with respect to the total molar amount of the structural unit represented by Formula (1)-Formula (2 '), Preferably it is 20 At least mol, more 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 it is 85 mol% or less, More preferably, it is 80 mol% or less, and arbitrary combinations of these upper limits and lower limits may be sufficient. If the structural unit represented by Formula (2) in polyamide-imide resin is the said range, it will be easy to improve the elasticity modulus and bending resistance of a polyamide-imide film more.

In a preferred embodiment of the present invention, the content of the structural unit represented by formula (2) in the polyamideimide resin is relative to the total molar amount of the structural unit represented by the formula (2) and the structural unit represented by the formula (2 '), Preferably it is 40 mol% or more, More preferably, it is 60 mol% or more, More preferably, it is 80 mol% or more, Preferably it is 95 mol% or less, More preferably, it is 90 mol% or less, and these upper and lower limits Any combination may be sufficient. If the structural unit represented by Formula (2) in polyamide-imide resin is the said range, it will be easy to improve the elasticity modulus and bending resistance of a polyamide-imide film more. In addition, the content (ratio) of the constituent unit represented by the formula (2) in the polyamide-imide resin, for example, it can be measured by using a ¹ H-NMR, or may be calculated from the raw material doipbi.

The polyamideimide resin may further include the structural unit represented by Formula (30) and / or the structural unit represented by Formula (31).

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 A group in which the hydrogen atom in the group represented by (29), the group represented by formulas (20) to (29) is substituted with a methyl group, a fluoro group, a chloro group or a trifluoromethyl group, and a tetravalent hydrocarbon having 6 or less carbon atoms Groups are illustrated. One embodiment of the polyamide-imide resin of the present invention, may include a plurality of types of Y ^1, Y ¹ may be a plurality of types it is 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. Examples of 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) was substituted by the hydrogen atom, and a trivalent C6 or less chain hydrocarbon group are illustrated. One embodiment of the polyamide-imide resin of the present invention, may include a plurality of types of Y ^2, Y ² is a plurality of types, and may 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, even if the hydrogen atom in an organic group is substituted by the hydrocarbon group or the fluorine-substituted hydrocarbon group, It is organic group. As X ¹ and X ² , formula (10), formula (11), formula (12), formula (13), formula (14), formula (15), formula (16), formula (17), and formula ( Group represented by 18); A group in which a hydrogen atom in the group represented by the formulas (10) to (18) is substituted with a methyl group, a fluoro group, a chloro group, or a trifluoromethyl group; And a C6 or less chain hydrocarbon group is illustrated.

In one embodiment of the present invention, the polyamideimide resin is added to the structural units represented by the formulas (1) and (2) and, if necessary, the structural units represented by the formula (2 '), the formula (30). At least 1 sort (s) of structural unit chosen from the structural unit shown and the structural unit represented by Formula (31) is included. From the viewpoint of easily improving the elastic modulus, the surface hardness, the bending resistance and the like of the polyamideimide film, in the polyamideimide resin, formulas (1), (2), (2 '), (30) and formula The total content of the structural units represented by (31) is preferably 80 mol% or more, more preferably 90 mol% or more, further preferably based on the total molar amount of all the structural units constituting the polyamideimide resin. 95 mol% or more, Especially preferably, it is 99 mol% or more, and it is 100 mol% or less normally. In addition, content (ratio) of the structural unit represented by Formula (1), Formula (2), Formula (2 '), Formula (30), and Formula (31) is measured using <^1> H-NMR, for example. It can also calculate or from the introduction ratio of a raw material.

The weight average molecular weight (Mw) of the polyamideimide resin is preferably 100,000 or more, more preferably 150,000 or more, still more preferably 200,000 or more, particularly preferably 250,000 or more, and 300,000 or more, in terms of standard polystyrene. Preferably it is 1,000,000 or less, More preferably, it is 800,000 or less, More preferably, it is 700,000 or less, Especially preferably, it is 500,000 or less, You may combine these upper limits and lower limits arbitrarily. If the weight average molecular weight of a polyamideimide resin is more than the said minimum, characteristics, such as the elasticity modulus of a polyamideimide film, and bending resistance, will improve easily, and if it is below the said upper limit, it will be easy to suppress the gel of a resin varnish, and will be obtained. The optical characteristic and external appearance of a polyamide-imide resin tend to become favorable. In addition, a weight average molecular weight can be measured by gel permeation chromatography (GPC), for example, can be measured by the method as described in an Example.

<Method for producing polyamideimide resin>

The polyamideimide resin of this invention can be manufactured using a tetracarboxylic acid compound, a dicarboxylic acid compound, and a diamine compound as a main raw material, For example, the structural unit represented by Formula (1) and Formula (2) is used. The polyamideimide resin to contain reacts the diamine compound represented by Formula (6) with the tetracarboxylic-acid compound represented by Formula (7), and produces | generates a polyamic acid, and the dicara represented by the said polyamic acid and Formula (8) It can manufacture by the method including the process of reacting an acid compound, and producing | generating a polyamideimide precursor, and the process of imidating the said polyamideimide precursor.

[In Formulas (6) to (8), X corresponds to X in Formulas (1) and (2), Y corresponds to Y in Formula (1), and R ^a and n are Each corresponds to R ^a and n in formula (2), and R ^b and R ^c are each independently —OH, —OMe, —OEt, —OPr, —OBu, or —Cl];

In the said manufacturing method, when using the dicarboxylic acid compound further represented by Formula (9) as a dicarboxylic acid compound, the structural unit represented by Formula (1), Formula (2), and Formula (2 ') is used. The polyamideimide resin containing can be manufactured.

[In Formula (9), K corresponds to K in Formula (2 '), and R ^d and R ^e are each independently -OH, -OMe, -OEt, -OPr, -OBu or -Cl. ]

Specifically, as a diamine compound, aliphatic diamine, aromatic diamine, and a mixture thereof are mentioned, for example. In addition, in this embodiment, "aromatic diamine" shows 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 and a fluorene ring. 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. A diamine compound can be used individually or in combination of 2 or more types.

As a specific example of aliphatic diamine, Acyclic aliphatic diamine, such as hexamethylenediamine; And cyclic aliphatic diamines such as 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, norbornanediamine, and 4,4'-diaminodicyclohexylmethane. These can be used individually or in combination of 2 or more types.

Specific examples of the aromatic diamine include p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, m-xylylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene, 2,6-dia Aromatic diamines having one aromatic ring, such as minonaphthalene; 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4,4'-diaminodiphenylether, 3,4'-diaminodiphenylether, 3,3'-dia Minodiphenylether, 4,4'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 1,4-bis (4-aminophenoxy) Benzene, 1,3-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 (tri Fluoromethyl) benzidine (sometimes referred to as TFMB), 4,4 '-(hexafluoroisopropylidene) dianiline, 4,4'-bis (4-aminophenoxy) biphenyl, 9,9 -Bis (4-aminophenyl) fluorene, 9,9-bis (4-amino-3-methylphenyl) fluorene, 9,9-bis (4-amino-3-chlorophenyl) fluorene, 9,9- Bis (4-amino-3-fluorophenyl) fluorene and the like , There may be mentioned aromatic diamine having an aromatic ring at least two. 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, 4,4'-bis (4-aminophenoxy) ratio Phenyl, 4,4 '-(hexafluoroisopropylidene) dianiline, and more preferably 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylpropane, 4, 4'-diaminodiphenylether, 4,4'-diaminodiphenylsulfone, 1,4-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy) phenyl] sulfone, 2 , 2-bis [4- (4- Minophenoxy) phenyl] propane, 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) benzidine, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4 ' -(Hexafluoroisopropylidene) dianiline is mentioned. These can be used individually or in combination of 2 or more types.

It is preferable to use at least 1 sort (s) chosen from the group which consists of aromatic diamine which has a biphenyl structure from a viewpoint of easy to improve the elasticity modulus and optical characteristic of a polyamideimide film among the said diamine compounds. 2,2'-dimethylbenzidine, 2,2'-bis (trifluoromethyl) benzidine, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diaminodiphenylether and 4 It is more preferable to use at least one selected from the group consisting of, 4 '-(hexafluoroisopropylidene) dianiline, and more preferably 2,2'-bis (trifluoromethyl) benzidine.

The tetracarboxylic acid compound represents a tetracarboxylic acid or tetracarboxylic acid derivative. The tetracarboxylic acid derivatives include anhydrides of tetracarboxylic acids, preferably dianhydrides, acid chlorides, and the like. As a tetracarboxylic-acid compound, For example, aromatic tetracarboxylic acid compounds, such as aromatic tetracarboxylic acid and its anhydride, Preferably its dianhydride; Aliphatic tetracarboxylic acid and its anhydride, Preferably aliphatic tetracarboxylic-acid compounds, such as the dianhydride, etc. are mentioned. These tetracarboxylic acid compounds can be used individually or in combination of 2 or more types.

Specific examples of the aromatic tetracarboxylic dianhydride include non-condensed polycyclic aromatic tetracarboxylic dianhydrides, monocyclic aromatic tetracarboxylic dianhydrides and condensed polycyclic aromatic tetracarboxylic dianhydrides. As a non-condensed polycyclic aromatic tetracarboxylic dianhydride, 4,4'- oxydiphthalic dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 2,2', 3 , 3'-benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (may be referred to as BPDA), 2,2', 3,3 ' -Biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylsulfontetracarboxylic 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) di Phthalic dianhydride (may be referred to 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 dianhydride and 4,4' -(m-phenylenedioxy) diphthalic dianhydride is mentioned. Moreover, 1,2,4,5-benzene tetracarboxylic dianhydride is mentioned as monocyclic aromatic tetracarboxylic dianhydride, As condensed polycyclic aromatic tetracarboxylic dianhydride, 2,3 is mentioned. And 6,7-naphthalene tetracarboxylic dianhydride.

Among these, 4,4'- oxydiphthalic dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 2,2', 3,3'- benzophenone tetracarr Acid dianhydrides, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydrides, 2,2', 3,3'-biphenyltetracarboxylic dianhydrides, 3,3 ', 4, 4'-diphenylsulfontetracarboxylic 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, 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-pe Rendioxy) diphthalic dianhydride and 4,4 '-(m-phenylenedioxy) diphthalic dianhydride, More preferably, 4,4'- oxydiphthalic dianhydride, 3,3', 4 , 4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride, And bis (3,4-dicarboxyphenyl) methane dianhydride and 4,4 '-(p-phenylenedioxy) diphthalic dianhydride. 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. A 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, Cycloalkanetetracarboxylic dianhydride, such as 3, 4- cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7 -En-2,3,5,6-tetracarboxylic dianhydride, dicyclohexyl-3,3 ', 4,4'-tetracarboxylic dianhydride and these positional isomers are mentioned. 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. These can be used individually or in combination of 2 or more types. Moreover, you may use combining a cyclic aliphatic tetracarboxylic dianhydride and an acyclic aliphatic tetracarboxylic dianhydride.

Among the tetracarboxylic acid compounds, the alicyclic tetracarboxylic dianhydride or the non-condensed polycyclic aromatic tetracarboxylic acid from the viewpoint of easily improving the elastic modulus, flex resistance, surface hardness, optical properties and the like of the polyamideimide film. Dianhydrides are preferred. As a specific example, 4,4'- oxydiphthalic dianhydride, 3,3 ', 4,4'- benzophenone tetracarboxylic dianhydride, 3,3', 4,4'-biphenyl tetracarboxylic dianhydride Water, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfontetracarboxylic dianhydride, 2,2-bis (3,4 -Dicarboxyphenyl) propane dianhydride, 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride and mixtures thereof are preferred, and 3,3', 4,4'-biphenyltetracarboxylic acid More preferred are dianhydrides and 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride and mixtures thereof, more preferred 4,4'-(hexafluoroisopropylidene) diphthalic dianhydride. .

The dicarboxylic acid compound represents a dicarboxylic acid or a dicarboxylic acid derivative, and examples of the dicarboxylic acid derivative include acid chlorides and esters of the dicarboxylic acid. Dicarboxylic acid compounds can be used individually or in combination of 2 or more types.

As a specific example of a dicarboxylic acid compound, 4,4'- oxybis benzoic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,4-, for example Naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, two benzoic acids are a single bond, -CH _2- , -C (CH ₃ ) _2- Aromatic dicarboxylic acids such as compounds linked with -C (CF ₃ ) _2- , -SO ₂ -or phenylene groups and derivatives thereof (for example, acid chlorides, acid anhydrides); And aliphatic dicarboxylic acids such as dicarboxylic acid compounds of chain hydrocarbons having 8 or less carbon atoms, and derivatives thereof (for example, acid chlorides and esters). These dicarboxylic acid compounds can be used individually or in combination of 2 or more types. Among these, terephthalic acid or its derivatives, 2,6-naphthalenedicarboxylic acid or its derivatives, 1,5-naphthalenedicarboxylic acid or its derivatives from the viewpoint of satisfactory elastic modulus and flexural resistance of the polyamideimide film And naphthalenedicarboxylic acids or derivatives thereof such as 1,4-naphthalenedicarboxylic acid or derivatives thereof, particularly 2,6-naphthalenedicarboxylic acid dichloride (called NADOC) are preferable. Moreover, it is preferable to use naphthalenedicarboxylic acid or its derivative (s) and 4,4'-oxybisbenzoic acid or its derivative (s) together from a viewpoint of improving the surface hardness of a polyamideimide film further, Especially, 2,6 It is more preferable to use naphthalenedicarboxylic acid dichloride (NADOC) and 4,4'-oxybis (benzoyl chloride) (called OBBC) together.

In manufacture of polyamideimide resin, the usage-amount of a diamine compound, a tetracarboxylic acid compound, and a dicarboxylic acid compound can be suitably selected according to the ratio of each structural unit of a desired polyamideimide resin.

In the production of the polyamideimide resin, the reaction temperature of the diamine compound, the tetracarboxylic acid compound and the dicarboxylic acid compound is not particularly limited, but is 50 to 350 ° C, for example. Although reaction time is not specifically limited, for example, It is about 30 minutes-about 24 hours. If necessary, the reaction may be performed under inert atmosphere or reduced pressure. In a preferred embodiment, the reaction is performed while stirring under normal pressure and / or inert gas atmosphere. Moreover, it is preferable to perform reaction in the solvent inactive to reaction. The solvent is not particularly limited as long as it does not affect the reaction. For example, water, methanol, ethanol, ethylene glycol, isopropyl alcohol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, 1-methoxy- Alcohol solvents such as 2-propanol, 2-butoxyethanol, and propylene glycol monomethyl ether; Ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, γ-valerolactone, propylene glycol methyl ether acetate, and ethyl lactate; Ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; Aliphatic hydrocarbon solvents such as pentane, hexane and heptane; Alicyclic hydrocarbon solvents such as ethylcyclohexane; Aromatic hydrocarbon solvents such as toluene and xylene; Nitrile solvents such as acetonitrile; Ether solvents such as tetrahydrofuran and dimethoxyethane; Chlorine-containing solvents such as chloroform and chlorobenzene; Amide solvents such as N, N-dimethylacetamide (DMAc) and N, N-dimethylformamide (DMF); Sulfur-containing solvents such as dimethyl sulfone, dimethyl sulfoxide and sulfolane; Carbonate solvents such as ethylene carbonate and propylene carbonate; And combinations thereof (mixed solvents). Among these, an amide solvent can be used suitably from a soluble viewpoint.

In the imidation process in manufacture of polyamide-imide resin, it can imidate in presence of an imidation catalyst. As an imidation catalyst, For example, aliphatic amines, such as tripropylamine, dibutyl propylamine, and ethyl dibutyl amine; 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 (2-picoline), 3-methylpyridine (3-picoline), 4-methylpyridine (4-picoline), 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine And aromatic amines such as 2,4-dimethylpyridine, 2,4,6-trimethylpyridine, 3,4-cyclopentenopyridine, 5,6,7,8-tetrahydroisoquinoline, and isoquinoline. . Moreover, it is preferable to use an acid anhydride with an imidation catalyst from a viewpoint which is easy to promote the imidation reaction. Examples of the acid anhydride include conventional acid anhydrides used for the imidization reaction, and specific examples thereof include aliphatic acid anhydrides such as acetic anhydride, propionic anhydride and butyric anhydride, and aromatic acid anhydrides such as phthalic acid.

The polyamideimide resin obtained by imidation is isolated by conventional methods, for example, separation means such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, and separation means combining these (separation and purification). In a preferred embodiment, a large amount of alcohol such as methanol can be added to the reaction solution containing the polyamideimide resin to precipitate the polyamideimide resin, and can be isolated by concentrating, filtration and drying. .

<Polyamideimide film>

The present invention includes a polyamideimide film comprising a polyamideimide resin. The polyamideimide has a high modulus of elasticity. Moreover, in one preferable aspect, the polyamide-imide film is also excellent in bending resistance and surface hardness. The content of the polyamideimide resin in the polyamideimide film is preferably 40% by mass or more, and more preferably, based on the mass of the polyamideimide film, from the viewpoint of easily exhibiting good elastic modulus, flex resistance and surface hardness. 60 mass% or more, More preferably, it is 80 mass% or more, Especially preferably, it is 90 mass% or more, Especially, it is 95 mass% or more. The upper limit of content of polyamide-imide resin is 100 mass% or less.

The polyamideimide film may further contain inorganic materials such as inorganic particles. Examples of the inorganic material include inorganic particles such as titania particles, alumina particles, zirconia particles, and silica particles, and silicon compounds such as quaternary alkoxysilanes such as tetraethyl ortho silicate. In view of the stability of the polyamideimide varnish for producing the polyamideimide film, the inorganic material is preferably inorganic particles, in particular silica particles. The inorganic particles may be bonded by a molecule having a siloxane bond.

The average primary particle size of the inorganic particles is, for example, from 1 to 100 nm, preferably from 5 to 80 nm, more preferably from 7 to 10 in view of transparency of the polyamideimide film, mechanical properties, and suppression of aggregation of the inorganic particles. 50 nm, Especially preferably, it is 10-30 nm. An average primary particle diameter can be determined by measuring the 10-point average value of the forward diameter by a transmission electron microscope.

Content of the inorganic material of a polyamideimide film is based on the total mass of a polyamideimide film, Preferably it is 0-90 mass%, More preferably, it is 0.01-60 mass%, More preferably, it is 5-40 mass %to be. When the content rate of the inorganic material is within the above range, there is a tendency to make the transparency and mechanical properties of the polyamideimide film compatible.

The polyamideimide film may further contain the ultraviolet absorber. A ultraviolet absorber can be suitably selected from the thing normally used as a ultraviolet absorber in the field of resin materials. The ultraviolet absorber may contain the compound which absorbs the light of the wavelength of 400 nm or less. As a ultraviolet absorber, the at least 1 sort (s) of compound chosen from the group which consists of a benzophenone type compound, a salicylate type compound, a benzotriazole type compound, and a triazine type compound is mentioned, for example. A ultraviolet absorber can be used individually or in combination of 2 or more types. Since the deterioration of a polyamideimide resin is suppressed because a polyamideimide film contains a ultraviolet absorber, visibility can be improved when a polyamideimide film is applied to an image display apparatus etc. In this specification, a "system compound" represents the derivative of the compound in which the said "system compound" is contained. For example, a "benzophenone type compound" represents the compound which has a benzophenone as a mother skeleton and a substituent couple | bonded with benzophenone.

When the polyamideimide film contains a ultraviolet absorber, the content of the ultraviolet absorber is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass with respect to the mass of the polyamideimide film. It is% or more, Preferably it is 10 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 6 mass% or less. Although preferable content changes with the ultraviolet absorber to be used, if the content of an ultraviolet absorber is adjusted so that the light transmittance of 400 nm may be about 20 to 60%, the light resistance of a polyamideimide film can be improved, and the polyamideimide film with high transparency Can be obtained.

The polyamideimide film may further contain other additives other than the inorganic material and the ultraviolet absorber. As another additive, antioxidant, a mold release agent, a stabilizer, a bluing agent, a flame retardant, a pH adjuster, a silica dispersing agent, a lubricating agent, a thickening agent, a leveling agent, etc. are mentioned, for example. When it contains another additive, the content is with respect to the mass of a polyamide-imide film, Preferably it is 0.005-20 mass%, More preferably, it is 0.01-15 mass%, More preferably, it is about 0.1-10 mass%. .

The thickness of a polyamideimide film can be suitably selected according to a use, Preferably it is 25 micrometers or more, More preferably, it is 30 micrometers or more, Preferably it is 100 micrometers or less, More preferably, it is 80 micrometers or less, More preferably, it is 60 micrometers or less. Any combination of these upper and lower limits may be sufficient. The thickness of a polyamideimide film can be measured using a micrometer, for example.

The elastic modulus of the polyamide-imide film is preferably 5.0 GPa or more, more preferably 5.2 GPa or more, still more preferably 5.5 GPa or more. The upper limit of the elasticity modulus is 10 GPa or less, More preferably, it is 8 GPa or less. An elastic modulus can be measured using a tensile tester, a precision universal testing machine, etc., for example, and can be measured by the method as described in an Example, for example.

The surface hardness of a polyamideimide film can be evaluated by pencil hardness, for example. The pencil hardness of the said polyamide-imide film is 6 B or more normally, Preferably it is B or more, More preferably, it is HB or more, More preferably, it is F or more, Especially preferably, it is H or more. If the pencil hardness is in the above range, scratches on the surface of the film can be effectively prevented. Surface hardness can be measured based on JISK5600-5-4: 1999, and can be measured by the method as described in an Example, for example.

In a preferable aspect of the present invention, the polyamideimide film comprising the polyamideimide resin of the present invention has high transparency and also has excellent optical properties. For this reason, the said polyamideimide film can be used as an optical film, and can be used suitably for the member of image display apparatuses, such as a liquid crystal display device and an organic electroluminescence display, especially the front plate (window film) of a flexible display. The front panel has a function of protecting an image display element in the flexible display. More specifically, 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, are mentioned. As a flexible display, the image display apparatus which has a flexible characteristic, for example, 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, a wearable device, etc. are mentioned.

Haze of a polyamideimide film becomes like this. Preferably it is 3.0% or less, More preferably, it is 2.0% or less, More preferably, it is 1.0% or less. If the haze of a polyamideimide film is below the said upper limit, transparency will become favorable, and when used for the front plate of an image display apparatus, for example, it can contribute to high visibility. Moreover, the minimum of haze is 0.01% or more normally. In addition, a haze can be measured by a haze computer, for example.

Yellowness of a polyamideimide film becomes like this. Preferably it is 8 or less, More preferably, it is 5 or less, More preferably, it is 3 or less, Especially preferably, it is 2 or less. If the yellowness of a polyamideimide film is below the said upper limit, transparency will become favorable, and when used for the front plate of an image display apparatus, for example, it can contribute to high visibility. Moreover, yellowness is -5 or more normally, Preferably it is -2 or more. In addition, the yellowness (YI value) is measured using a UV-visible near-infrared spectrophotometer to measure the transmittance for light of 300 to 800 nm, to obtain tristimulus values (X, Y, Z), and YI = 100 × (1.2769X). Can be calculated based on the formula -1.0592Z) / Y.

In the polyamide-imide film, the total light transmittance in a thickness of 50 µm is preferably 80% or more, more preferably 85% or more, still more preferably 89% or more, and particularly preferably 90% or more. Transparency becomes favorable that a total light transmittance is more than the said minimum, and when it is used for the front plate of an image display apparatus, for example, it can contribute to high visibility. In addition, the upper limit of total light transmittance is 100% or less normally. In addition, total light transmittance can be measured using a haze computer based on JISK7105: 1981, for example.

<Method for producing polyamideimide film>

Although the polyamideimide film containing the polyamideimide resin of this invention is not specifically limited, For example, the following processes:

(a) step (varnish preparation step) of preparing the liquid containing the said polyamide-imide resin (it may be called polyamide-imide varnish),

(b) applying a polyamideimide varnish to the substrate to form a coating film (coating step), and

(c) The process of drying the apply | coated liquid (coating film) and forming a polyamide-imide film (film formation process)

It can manufacture by the method containing these.

In the varnish preparation step, the polyamideimide resin is dissolved in a solvent, and the polyamideimide varnish is prepared by adding the above additives or the like and stirring the mixture as necessary.

The solvent used for preparation of the varnish is not particularly limited as long as it can dissolve the polyamideimide resin. As such a solvent, the solvent illustrated in the term of <polyamideimide resin> is mentioned, for example. Among these solvents, an amide solvent or a lactone solvent can be suitably used. These solvents can be used alone or in combination of two or more thereof. Solid content concentration of a polyamide-imide varnish becomes like this. Preferably it is 1-25 mass%, More preferably, it is 5-15 mass%.

In a coating process, a polyamide-imide varnish is apply | coated on a base material by a well-known coating method, and a coating film is formed. 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, a di A ping method, a spray method, the casting molding method, etc. are mentioned.

In a film formation process, a polyamideimide film can be formed by drying a coating film and peeling from a base material. You may provide the process of drying a polyamideimide film further after peeling. Drying of a coating film can be performed at the temperature of 50-350 degreeC normally. You may perform the said drying on condition of inert atmosphere or reduced pressure as needed.

As an example of a base material, metal belts, such as SUS, and resin films, such as PET film, a PEN film, a polyimide film, a polyamide film, and another polyamideimide film, are mentioned, From a viewpoint of excellent heat resistance, Preferably it is a PET film , PEN film, and the like, and more preferably, a PET film may be mentioned from the viewpoints of adhesion, ease of peeling, and cost when forming a film with a polyamideimide film.

<Laminated body>

The polyamideimide film containing the polyamideimide resin of the present invention may be a single layer or a laminate, may be used as it is, or may be used as a laminate with another film or layer. In this invention, when a polyamideimide film is a laminated body, it is called a polyamideimide film including all the layers laminated | stacked on the single side | surface or both surfaces of a polyamideimide film. In addition, for convenience, the polyamide-imide film in the form of a laminate may be referred to as a laminate.

When the polyamideimide film of this invention is a laminated body, you may have one or more functional layers in at least one surface of a polyamideimide film. As a functional layer, an ultraviolet absorber layer, a hard coat layer, a primer layer, a gas barrier layer, an adhesion layer, a color adjustment layer, a refractive index adjustment layer, etc. are mentioned, for example. A functional layer can be used individually or in combination of 2 or more types.

The polyamideimide film of this invention can be made into the laminated body with the protective film etc. which are shown below. That is, the polyamideimide film of this invention may contain a protective film etc. in at least one surface. When having a functional layer in the single side | surface or both surfaces of a polyamideimide film, you may have a protective film on the surface of a functional layer.

A protective film is bonded to the surface which does not have a base material which is a support body of a polyamideimide film. When winding up a laminated body in roll shape, when there exists a problem in winding properties, such as blocking, you may bond a protective film to the surface on the opposite side to the polyamideimide film of a support body in addition to the above. The protective film bonded to a polyamideimide film is a film for temporarily protecting the surface of a polyamideimide film, and it is not specifically limited as long as it is a peelable film which can protect the surface of a polyamideimide film. For example, Polyester resin films, such as a polyethylene terephthalate, a polybutylene terephthalate, and a polyethylene naphthalate; Polyolefin resin films, such as polyethylene and a polypropylene film, an acrylic resin film, etc. are mentioned, It is preferable to select from the group which consists of a polyolefin resin film, a polyethylene terephthalate resin film, and an acrylic resin film. When including a protective film on both surfaces of a laminated body (polyamideimide film), the protective film of each surface may be mutually same or different.

Although the thickness of a protective film is not specifically limited, Usually, 10-100 micrometers, Preferably it is 10-80 micrometers, More preferably, it is 10-50 micrometers. When a protective film is included on both surfaces of a laminated body (polyamideimide film), the thickness of the protective film of each surface may be same or different.

(Laminated Film Roll)

In this specification, the thing by which the said laminated body (for example, a support body, a polyamideimide film, and a protective film as needed) was wound by roll shape to the core is called a laminated body film roll. In the continuous production, the laminated film roll is often stored in the form of a film roll once from space and other constraints, and the laminated film roll is one of them. In the form of a laminated film roll, since a laminated body is wound more strongly, the haze-causing substance on a support body becomes easy to be transferred on a polyamideimide film. However, when the support having the predetermined logarithmic contact angle of the present invention is used, the clouding material from the support is hard to be transferred to the polyamideimide film, and even if it is wound with a laminate film roll, clouding is unlikely to occur.

As a material which comprises the core of a laminated film roll, a polyethylene resin, a polypropylene resin, a polyvinyl chloride resin, a polyester resin, an epoxy resin, a phenol resin, a melamine resin, a silicon resin, a polyurethane resin, a polycarbonate resin, for example Synthetic resins such as ABS resin; Metals such as aluminum; Fiber-reinforced plastics (FRP: a composite material in which fibers such as glass fibers are contained in plastics to improve strength); The core forms a cylindrical or cylindrical shape, and the diameter thereof is, for example, 80 to 170 mm. Moreover, although the diameter after the winding of a film roll is not specifically limited, Usually, it is 200-800 mm.

<Flexible Display Device>

The present invention includes a flexible display device comprising the polyamideimide film. The flexible display device (optical laminate) may further include one layer selected from the group consisting of a polarizing plate and a touch sensor on one surface of the polyamideimide film. That is, the flexible display device of the present invention may further include a touch sensor and / or a polarizing plate. As described above, in the flexible display device, the polyamideimide film of the present invention is used as a front plate (window film). Therefore, the polyamideimide film of this invention may be called the window film. The window film may be provided with the window hard coating layer. In addition, the window film may be provided with a polarizing plate or a touch sensor with an adhesive layer interposed as needed.

At least one surface of the window film or the polarizing plate may be provided with a colored light shielding pattern printed around the edge, and the light shielding pattern may be in the form of a single layer or a multilayer. In addition, a polarizing plate may be bonded to one surface of the window film directly or with an adhesive layer therebetween. For example, the polarizing plate may extend continuously over the non-display area or the bezel portion, and may be a conventional polarizing plate including a polyvinyl alcohol polarizer and a protective film affixed on at least one surface of the polyvinyl alcohol polarizer. do.

As an aspect of the present invention, the polarizing plate and the touch sensor are integrated on one surface of the window film, and the arrangement order of the polarizing plate and the touch sensor is not limited, and the polarizing plate and the touch sensor may be arranged in the order of the window film, the polarizing plate, the touch sensor, and the display panel. You may arrange | position in order of a window film, a touch sensor, a polarizing plate, and a display panel. When arrange | positioning in order of a window film, a polarizing plate, a touch sensor, and a display panel, when the image display apparatus is seen from the visual recognition side, since a touch sensor exists under a polarizing plate, there exists an advantage that the pattern of a touch sensor is hard to be recognized. In this case, it is preferable that the substrate of the touch sensor has a front phase difference of ± 2.5 nm or less. As such a raw material, as a non-stretched film, the film of 1 or more types of materials chosen from the group which consists of raw materials, such as a triacetyl cellulose, a cycloolefin, a cycloolefin copolymer, a polynorbornene copolymer, may be sufficient, for example. Meanwhile, only the pattern without the substrate of the touch sensor may have a structure transferred to the window film and the polarizing plate.

Although the said polarizing plate and a touch sensor can be arrange | positioned between a window film and a display panel with a transparent adhesive layer or a transparent adhesive bond layer, a transparent adhesive layer is preferable. When arrange | positioned in order of a window film, a polarizing plate, a touch sensor, and a display panel, a transparent adhesive layer may be located between a window film and a polarizing plate, and between a touch sensor and a display panel. When arrange | positioned in order of a window film, a touch sensor, a polarizing plate, and a display panel, a transparent adhesive layer may be located between a window film and a touch sensor, between a touch sensor and a polarizing plate, and between a polarizing plate and a display panel.

The thickness of the said transparent adhesive layer is not specifically limited, For example, 1-100 micrometers may be sufficient. In the transparent adhesive layer which concerns on this invention, it is preferable that the thickness of a lower adhesion layer is more than the thickness of an upper adhesion layer, and viscoelasticity is 0.2 Mpa or less at -20-80 degreeC. In this case, the noise generated by the interference between the touch sensor and the display panel can be reduced, and the interfacial stress during bending can be alleviated to prevent breakage of the upper and lower substrates. More preferably, 0.01 to 0.15 MPa may be sufficient as the said viscoelasticity from the surface which suppresses the cohesive failure of an adhesive and relieves interfacial stress.

(Polarizing plate)

The polarizing plate laminated | stacked on the said window film may be the structure provided with the polarizer alone or the polarizer and the protective film affixed on at least one surface thereof. The thickness of the said polarizing plate is not specifically limited, For example, 100 micrometers or less may be sufficient. If thickness is 100 micrometers or less, flexibility will hardly fall. Within this range, for example, 5 to 100 µm may be sufficient.

The polarizer may be a film-type polarizer commonly used in the art produced by a step including a step of swelling, dyeing, crosslinking, stretching, washing with water, drying, or the like for a polyvinyl alcohol-based film. As another example, It can form by apply | coating the composition for liquid crystal coating as a polarizing coating layer. The liquid crystal coating composition may include a polymerizable liquid crystal compound and a dichroic dye as a coating layer forming composition. For example, the polarizing coating layer is coated with an alignment film forming composition on a substrate to provide an alignment property to form an alignment film, and a coating layer forming composition containing a liquid crystal compound and a dichroic dye is formed on the alignment film to form a liquid crystal coating layer. It can manufacture by doing. Such a polarizing coating layer can form a thin thickness compared with the polarizing plate containing the protective film affixed on both surfaces of a polyvinyl alcohol-type polarizer by an adhesive agent. The thickness of the said polarizing coating layer may be 0.5-10 micrometers, Preferably 2-4 micrometers may be sufficient.

(Orientation film formation composition)

The alignment layer forming composition may include an alignment agent, a photopolymerization initiator, and a solvent which are commonly used in the art. As the aligning agent, an aligning agent usually used in the art can be used without particular limitation. For example, a polyacrylate-based polymer, a polyamic acid, a polyimide-based polymer, or a polymer containing cinnamate groups can be used as the alignment agent, and when a photoalignment is applied, it is preferable to use a polymer containing cinnamate groups. Do.

Examples of the coating of the alignment layer forming composition include spin coating, extrusion molding, dip coating, flow coating, spray coating, roll coating, gravure coating, micro gravure coating, in-line coating, and the like. After the said alignment film formation composition is apply | coated and dried as needed, an orientation treatment is performed. The said orientation process can employ | adopt various well-known methods in the said field | area without limitation, Preferably, photo-alignment film formation can be used. A photo-alignment film is obtained by apply | coating the composition for photo-alignment film formation containing a polymer or monomer which has a photoreactive group, and a solvent to a base material normally, and irradiating polarized light (preferably polarized UV). The photo-alignment film is more preferable at the point which can arbitrarily control the direction of the orientation regulation force by selecting the polarization direction of the polarized light to irradiate.

The thickness of the photo-alignment film is usually 10 to 10,000 nm, preferably 10 to 1,000 nm, and more preferably 10 to 500 nm. When the thickness of the photo-alignment film is in the above range, the orientation regulation force is sufficiently expressed.

(Polarizing Coating Layer Formation Composition)

The polarizing coating layer may be formed by applying a polarizing coating layer forming composition. Specifically, the polarizing coating layer-forming composition, in addition to the dichroic dye, contains a composition containing one or more polymerizable liquid crystals (hereinafter, sometimes referred to as polymerizable liquid crystals (B)) as host compounds (hereinafter referred to as composition B). May be called).

A "dichroic dye" means the pigment | dye which has the property which the absorbance in the major axis direction of a molecule | numerator differs from the absorbance in a short axis direction. As long as it has such a property, a dichroic dye does not have a restriction | limiting and may be a dye or a pigment. Two or more types of dyes may be used in combination, two or more types of pigments may be used in combination, and dyes and pigments may be used in combination.

It is preferable that a dichroic dye has maximum absorption wavelength ((lambda) _MAX ) in the range of 300-700 nm. As such a dichroic dye, an acridine pigment, an oxazine pigment, a cyanine pigment, a naphthalene pigment, an azo pigment, and an anthraquinone pigment is mentioned, Especially, an azo pigment is preferable. As an azo pigment | dye, a monoazo pigment | dye, bis azo pigment | dye, a tris azo pigment | dye, a tetrakis azo pigment | dye, and a stilbenazo pigment | dye are mentioned, A bis azo pigment | dye and a tris azo pigment | dye are preferable.

It is preferable that it is a smectic phase, and, as for the liquid crystal state represented by a polymeric liquid crystal (B), it is more preferable that it is a higher order smectic phase from the point which can manufacture a polarizing layer with a higher degree of orientation order. The polymeric liquid crystal (B) which shows a smectic phase is called a polymeric smectic liquid crystal compound. The polymerizable liquid crystal (B) can be used alone or in combination. Moreover, when combining 2 or more types of polymerizable liquid crystals, at least 1 type is preferable if it is a polymerizable liquid crystal (B), and it is more preferable if 2 or more types are polymerizable liquid crystals (B). By combining, it may be possible to hold | maintain liquid crystal temporarily even at the temperature below liquid crystal-crystal phase transition temperature. The polymerizable liquid crystal (B) is, for example, Lub et al. Recl. Trav. Chim. It is manufactured by the well-known method described in Pays-Bas, 115, 321-328 (1996) or Unexamined-Japanese-Patent No. 4919156. Although content of the dichroic dye in the composition B can be suitably adjusted according to the kind etc. of a dichroic dye, Preferably it is 0.1 mass part or more and 50 mass parts or less with respect to 100 mass parts of polymeric liquid crystals (B), More preferably, 0.1 mass part or more and 20 mass parts or less, More preferably, they are 0.1 mass part or more and 10 mass parts or less. When content of a dichroic dye is in the said range, it can superpose | polymerize without disturbing the orientation of a polymeric liquid crystal (B), and the tendency which inhibits the orientation of a polymeric liquid crystal (B) is small.

It is preferable that composition B contains a solvent. Generally, since a smectic liquid crystal compound has a high viscosity, the composition containing a solvent is easy to apply | coat, and as a result, formation of a polarizing film is easy in many cases. As a solvent, the thing similar to the solvent contained in the orientation polymer composition mentioned above can be mentioned, It can select suitably according to the solubility of a polymeric liquid crystal (B) and a dichroic dye. Content of a solvent becomes like this. Preferably it is 50-98 mass% with respect to the total amount of the composition B. In other words, solid content in the composition B becomes like this. Preferably it is 2-50 mass%.

It is preferable that composition B contains at least 1 leveling agent. The leveling agent has a function of adjusting the fluidity of the composition B and flattening the coating film obtained by applying the composition B, and specifically, a surfactant may be mentioned. When composition B contains a leveling agent, the content becomes like this. Preferably it is 0.05 mass part or more and 5 mass parts or less, More preferably, it is 0.05 mass part or more and 3 mass parts or less with respect to 100 mass parts of polymeric liquid crystals. When content of a leveling agent exists in said range, it is easy to horizontally align a polymeric liquid crystal, and there exists a tendency for the polarizing layer obtained to become more smooth. When content of the leveling agent with respect to a polymeric liquid crystal is in the said range, there exists a tendency for a deviation not to generate | occur | produce so much in the polarizing layer obtained.

It is preferable that composition B contains 1 or more types of polymerization initiators. A polymerization initiator is a compound which can start the polymerization reaction of a polymeric liquid crystal (B), and a photoinitiator is preferable at the point which can start a polymerization reaction on lower temperature conditions. Specifically, the photoinitiator which can generate | occur | produce an active radical or an acid by the action of light is mentioned, Especially the photoinitiator which generate | occur | produces a radical by the action of light is preferable. Examples of the polymerization initiator include benzoin compounds, benzophenone compounds, alkylphenone compounds, acylphosphine oxide compounds, triazine compounds, iodonium salts and sulfonium salts.

When composition B contains a polymerization initiator, although the content can be suitably adjusted according to the kind and quantity of the polymeric liquid crystal contained in the composition, Preferably it is 0.1-30 mass parts with respect to 100 mass parts of polymeric liquid crystals. More preferably, it is 0.5-10 mass parts, More preferably, it is 0.5-8 mass parts. If content of a polymerization initiator exists in this range, it can superpose | polymerize without disturbing the orientation of a polymeric liquid crystal (B). When composition B contains a photoinitiator, the said composition may further contain the photosensitizer. When composition B contains a photoinitiator and a photosensitizer, the polymerization reaction of the polymeric liquid crystal contained in this composition can be accelerate | stimulated more. Although the usage-amount of a photosensitizer can be suitably adjusted according to the kind and quantity of a photoinitiator and a polymeric liquid crystal, Preferably it is 0.1-30 mass parts, More preferably, it is 0.5-10 mass with respect to 100 mass parts of polymeric liquid crystals. Part, More preferably, it is 0.5-8 mass parts.

In order to advance the polymerization reaction of a polymeric liquid crystal more stably, the composition B may contain an appropriate amount of polymerization inhibitors, and thereby, it becomes easy to control the progress of the polymerization reaction of a polymeric liquid crystal. When composition B contains a polymerization inhibitor, the content can be suitably adjusted according to the kind and quantity of a polymeric liquid crystal, the usage-amount of a photosensitizer, etc., Preferably it is 0.1 with respect to 100 mass parts of polymeric liquid crystals. -30 mass parts, More preferably, it is 0.5-10 mass parts, More preferably, it is 0.5-8 mass parts. If content of a polymerization inhibitor exists in this range, it can superpose | polymerize without disturbing the orientation of a polymeric liquid crystal.

(Production method of polarizing coating layer)

A polarizing coating layer is normally formed by apply | coating a polarizing coating layer forming composition on the base material on which the orientation process was performed, and polymerizing the polymerizable liquid crystal in the coating film obtained. The method of apply | coating the said polarizing coating layer forming composition is not limited. Examples of the orientation treatment include those exemplified above. A dry film is formed by apply | coating a polarizing coating layer forming composition and drying-drying a solvent on the conditions which the polymerizable liquid crystal contained in the coating film obtained does not superpose | polymerize. As a drying method, a natural drying method, ventilation drying method, heat drying, and reduced pressure drying method are mentioned. When a polymerizable liquid crystal is a polymeric smectic liquid crystal compound, it is preferable to make the liquid crystal state of the polymeric smectic liquid crystal compound contained in a dry film into a nematic phase (nematic liquid crystal state), and then transfer to a smectic phase. In order to form a smectic phase via a nematic phase, for example, the polymerizable smectic liquid crystal compound included in the dry coating is heated to a temperature above the temperature at which the nematic phase liquid crystal phase transitions, and then the polymerizable smudge The method of cooling to the temperature in which a mextic liquid crystal compound shows the liquid crystal state of a smectic phase is employ | adopted. Subsequently, after making the liquid crystal state of the polymeric liquid crystal in a dry film into a smectic phase, the method of photopolymerizing a polymeric liquid crystal with the smectic phase liquid crystal state maintained is demonstrated. In photopolymerization, the light irradiated to a dry film can be suitably selected according to the kind of photoinitiator contained in the said dry film, the kind of polymeric liquid crystal (especially the kind of photopolymerizer which a polymeric liquid crystal has), and its quantity, And the specific examples thereof include an active energy ray selected from the group consisting of visible light, ultraviolet light and laser light. Among these, ultraviolet light is preferable because it is easy to control the progress of the polymerization reaction, or because it can be used as a photopolymerization device in a wide range of fields. By performing photopolymerization, the polymerizable liquid crystal is polymerized while maintaining a liquid crystal state of a smectic phase, preferably a higher order smectic phase, thereby forming a polarizing layer.

(Phase difference coating layer)

In one embodiment of the present invention, the polarizing plate may include a phase difference coating layer. The retardation coating layer generally refers to the lambda / 2 layer, the lambda / 4 layer, the positive C layer and the like according to the optical properties. The retardation coating layer is, for example, after coating the coating layer forming composition containing the liquid crystal compound on the substrate film subjected to the alignment treatment to form a liquid crystal coating layer, and after attaching the liquid crystal coating layer with the polarizing plate through the adhesive layer, the substrate film Although it can form by peeling, it is not limited to this method. As the base film, the polymer film exemplified as the protective film can be used, and surface treatment may be performed before the alignment film is formed on the base material surface on the side where the alignment film and the retardation layer are formed. Since the said oriented film formation composition, its application | coating, drying method, etc. are the same as what was demonstrated by the polarizing coating layer, description is abbreviate | omitted in order to avoid duplication. The composition of the coating layer forming composition is the same as that described in the polarizing coating layer, except that the dichroic dye is not included. Moreover, since application | coating, drying, and a hardening method of the said coating layer forming composition are also the same as what was demonstrated by the said polarizing coating layer, description is abbreviate | omitted in order to avoid duplication.

The thickness of the retardation coating layer is usually 0.5 to 10 m, preferably 1 to 4 m.

In one embodiment of this invention, a retardation coating layer can adjust an optical characteristic by thickness of a coating layer, the orientation state of a polymeric liquid crystal compound, etc. Specifically, by adjusting the thickness of the retardation layer, a retardation layer that gives a desired in-plane retardation can be produced. In-plane retardation value (in-plane retardation value, Re) is a value defined by Formula (1), and what is necessary is just to adjust (DELTA) n and thickness d to obtain desired Re.

Re = d × Δn (λ)... Equation (1), where Δn = nx-ny

(In Formula (1), Re represents an in-plane retardation value, d represents a thickness, and Δn represents a birefringence. When considering an index ellipsoid formed according to the orientation of the polymerizable liquid crystal compound, the refractive index in three directions, In other words, nx, ny, and nz are defined as follows: nx represents a major refractive index in a direction parallel to the base plane of the refractive index ellipsoid formed by the retardation layer, and ny represents a refractive index ellipsoid formed by the retardation layer. Represents a refractive index in a direction parallel to the substrate plane of and perpendicular to the direction of nx, where nz represents a refractive index in a direction perpendicular to the substrate plane in the refractive index ellipsoid formed by the phase difference layer. In the case of four layers, the in-plane retardation value Re (550) is in the range of 113 to 163 nm, preferably in the range of 130 to 150 nm, and when the retardation layer is a λ / 2 layer, Re (550) is preferably in the range of 250 to 300 nm. Is above.)

Moreover, the phase difference layer which expresses the phase difference of the thickness direction can be produced according to the orientation state of a polymeric liquid crystal compound. Expressing the phase difference in the thickness direction indicates the characteristic that the phase difference value Rth in the thickness direction becomes negative in the formula (2).

Rth = [(nx + ny) / 2-nz] × d... Formula (2)

(In formula (2), nx, ny, nz, and d are the same as the definition mentioned above.)

The in-plane retardation value Re (550) of the positive C layer is usually in the range of 0 to 10 nm, preferably in the range of 0 to 5 nm, and the retardation value Rth in the thickness direction is usually in the range of -10 to -300 nm, preferably -20. It is in the range of -200nm. The polarizing plate of this invention may have two or more retardation coating layers, and when it has two retardation coating layers, a 1st retardation coating layer is (lambda) / 4 layer for making circularly polarized light, and a 2nd retardation coating layer has the color sense seen obliquely. Positive C layer may be used to improve the efficiency. Further, the first retardation coating layer may be a positive C layer for improving the color sense seen obliquely, and the second retardation coating layer may be a λ / 4 layer for producing circularly polarized light.

(Adhesive or adhesive)

In one embodiment of the present invention, the polarizing coating layer and the first retardation coating layer, or the first retardation coating layer and the second retardation coating layer can be bonded to each other via an adhesive or an adhesive. As an adhesive agent which forms an adhesive bond layer, an aqueous adhesive agent, an active energy ray curable adhesive agent, or a thermosetting adhesive agent can be used, Preferably it is an aqueous adhesive agent and an active energy ray curable adhesive agent. As an adhesive layer, what is mentioned later can be used.

As an aqueous adhesive agent, the adhesive agent which consists of polyvinyl alcohol-type resin aqueous solution, an aqueous two-component urethane emulsion adhesive, etc. are mentioned. Especially, the aqueous adhesive which consists of aqueous solution of polyvinyl alcohol-type resin is used suitably. As polyvinyl alcohol-type resin, in addition to the vinyl alcohol homopolymer obtained by saponifying polyvinyl acetate which is a homopolymer of vinyl acetate, the polyvinyl alcohol-type air obtained by saponifying the copolymer of vinyl acetate and the other monomer copolymerizable with this. The modified polyvinyl alcohol polymer etc. which partially modified | polymerized or these hydroxyl groups can be used. The aqueous adhesive may include a crosslinking agent such as an aldehyde compound (glyoxal, etc.), an epoxy compound, a melamine compound, a methylol compound, an isocyanate compound, an amine compound, a polyvalent metal salt, and the like.

When using an aqueous adhesive agent, after bonding a coating layer, it is preferable to perform the drying process for removing the water contained in an aqueous adhesive agent.

The said active energy ray curable adhesive agent is an adhesive agent containing the curable compound hardened | cured by irradiation of active energy rays, such as an ultraviolet-ray, visible light, an electron beam, and an X-ray, Preferably it is an ultraviolet curable adhesive agent.

The curable compound may be a cation polymerizable curable compound or a radical polymerizable curable compound. As a cationic polymerizable curable compound, For example, an epoxy type compound (compound which has one or two or more epoxy groups in a molecule), an oxetane type compound (compound which has one or two or more oxetane rings in a molecule), Or a combination thereof. As a radically polymerizable curable compound, For example, (meth) acrylic-type compound (compound which has one or two or more (meth) acryloyloxy groups in a molecule), the other vinyl type compound which has a radically polymerizable double bond, Or a combination thereof. You may use together a cationically polymerizable curable compound and a radically polymerizable curable compound. The active energy ray curable adhesive usually further contains a cationic polymerization initiator and / or a radical polymerization initiator for initiating the curing reaction of the curable compound.

When bonding a coating layer, in order to improve adhesiveness, you may perform surface activation treatment to at least one bonding surface of the surface to adhere | attach. Examples of the surface activation treatment include dry treatment such as corona treatment, plasma treatment, discharge treatment (glow discharge treatment, and the like), flame treatment, ozone treatment, UV ozone treatment, ionizing active line treatment (ultraviolet treatment, electron beam treatment, and the like); And wet treatments such as ultrasonic treatment using a solvent such as water or acetone, saponification treatment, and anchor coating treatment. This surface activation process may be performed independently and may combine 2 or more.

The thickness of the said adhesive layer can be adjusted according to the adhesive force, Preferably it is 0.1-10 micrometers, More preferably, it may be 1-5 micrometers. In one embodiment of the present invention, in the case of a configuration in which a plurality of the adhesive layers are used, they may be made of the same material or different materials, and may have the same thickness or different thicknesses.

An adhesive layer can be comprised by the adhesive composition which has resin, such as (meth) acrylic-type resin, rubber type resin, polyurethane type resin, polyester type resin, silicone type resin, and polyvinyl ether type resin as a main component. Especially, the adhesive composition which uses polyester resin or (meth) acrylic-type resin which is excellent in transparency, weather resistance, heat resistance, etc. as a base polymer is preferable. An active energy ray hardening type and a thermosetting type may be sufficient as an adhesive composition.

As adhesive resin used by this invention, the thing of the range of 300,000-4,000,000 in weight average molecular weight is used normally. In consideration of durability, particularly heat resistance, the weight average molecular weight is preferably 500,000 to 3,000,000, more preferably 650,000 to 2,000,000. A weight average molecular weight of more than 300,000 is preferable in terms of heat resistance, and a weight average molecular weight of less than 4,000,000 is also preferable in that adhesiveness and adhesion decrease. In addition, a weight average molecular weight is measured by GPC (gel chromatography chromatography), and says the value computed by polystyrene conversion.

In addition, the pressure-sensitive adhesive composition may contain a crosslinking agent. As a crosslinking agent, an organic type crosslinking agent and a polyfunctional metal chelate can be used. As an organic type crosslinking agent, an isocyanate type crosslinking agent, a peroxide type crosslinking agent, an epoxy type crosslinking agent, an imine type crosslinking agent, etc. are mentioned. A polyfunctional metal chelate is a thing in which a polyvalent metal is covalently bonded or coordinated with an organic compound. Examples of the polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like. have. As an atom in the organic compound covalently bonded or coordinated, an oxygen atom etc. are mentioned, As an organic compound, an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, a ketone compound, etc. are mentioned.

When it contains a crosslinking agent, the usage-amount is preferably 0.01-20 mass parts, More preferably, it is 0.03-10 mass parts with respect to 100 mass parts of adhesive resin. When the crosslinking agent exceeds 0.01 parts by mass, the cohesive force of the pressure-sensitive adhesive layer tends not to be insufficient, and there is little fear that foaming occurs during heating. On the other hand, when the crosslinking agent is less than 20 parts by mass, moisture resistance is sufficient and peeling is prevented in reliability tests or the like. It is difficult to occur.

It is preferable to mix | blend a silane coupling agent as an additive. Examples of the silane coupling agent include silicon having an epoxy structure such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. compound; Amino group-containing silicon compounds such as 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane and N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane; 3-chloropropyltrimethoxysilane; (Meth) acryl group containing silane coupling agents, such as acetoacetyl group containing trimethoxysilane, 3-acryloxypropyl trimethoxysilane, and 3-methacryloxypropyl triethoxysilane; Isocyanate group containing silane coupling agents, such as 3-isocyanatopropyl triethoxysilane, etc. are mentioned. A silane coupling agent can provide the effect which suppresses peeling in durability, especially a humidification environment. The usage-amount of a silane coupling agent is 1 mass part or less with respect to 100 mass parts of adhesive resin, More preferably, it is 0.01-1 mass part, More preferably, it is 0.02-0.6 mass part.

Furthermore, the adhesive composition may contain other well-known additives, For example, in an adhesive composition, powder, such as a coloring agent and a pigment, dye, surfactant, a plasticizer, a tackifier, and a surface lubricant , Leveling agents, softeners, antioxidants, antioxidants, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, particulates, thin powders and the like may be appropriately added depending on the intended use. Can be. Moreover, you may employ | adopt the redox system which added the reducing agent within the range which can be controlled.

The thickness of an adhesive layer is not specifically limited, For example, about 1-100 micrometers, Preferably it is 2-50 micrometers, More preferably, it is 3-30 micrometers. By making thickness of an adhesive layer thin, the total amount of the acid in an adhesive layer falls. This makes it difficult for an acid component to corrode wiring of a board | substrate. Moreover, the adhesive layer which a 2nd layer has can be adjusted with the thickness of the flexible printed circuit board which fits.

(Protective layer)

In one Embodiment of this invention, the said polarizing plate may be a form which has at least 1 or more protective layers, and when one surface of the polarizer which comprises the polarizing plate, or the polarizer has a phase difference layer, the surface opposite to the polarizer of a phase difference layer It can be located at

There is no restriction | limiting in particular as a protective layer as long as it is a film excellent in transparency, mechanical strength, thermal stability, moisture shielding, isotropy, etc. Specifically, polyester-based films such as polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate; Cellulose films such as diacetyl cellulose and triacetyl cellulose; Polycarbonate film; Acrylic films such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene films such as polystyrene and acrylonitrile-styrene copolymers; Polyolefin-based films such as cycloolefin, cycloolefin copolymer, polynorbornene, polypropylene, polyethylene, and ethylene propylene copolymer; Vinyl chloride film; Polyamide-based films such as nylon and aromatic polyamide; Imide film; Sulfone type films; Polyether ketone film; Sulfided polyphenylene-based films; Vinyl alcohol film; Vinylidene chloride-based film; Vinyl butyral film; Arylate film; Polyoxymethylene film; Urethane film; Epoxy film; Silicone film etc. are mentioned. Among these, especially the cellulose type film which has the surface saponified by alkali etc. is preferable in consideration of polarization characteristic or durability. The protective layer may also have an optical compensation function such as a phase difference function.

The protective layer may have been subjected to an easy-adhesion process for improving adhesive strength on the surface bonded to the polarizer or the retardation coating layer. The easily-adhesive treatment is not particularly limited as long as it can improve the adhesive strength, and examples thereof include dry treatments such as primer treatment, plasma treatment and corona treatment; Chemical treatments such as alkali treatment (saponification treatment); Low pressure UV treatment; and the like.

(Touch sensor)

The touch sensor has a substrate, a lower electrode provided on the substrate, an upper electrode facing the lower electrode, an insulating layer sandwiched between the lower electrode and the upper electrode.

A base material can employ | adopt various things, if it is a flexible resin film which has light transparency. For example, as a base material, the film illustrated as a material of the above-mentioned transparent base material can be used.

The lower electrode has, for example, a plurality of small electrodes of square shape in plan view. The plurality of small electrodes are arranged in a matrix.

Further, the plurality of small electrodes are connected to adjacent small electrodes in one diagonal direction of the small electrode, thereby forming a plurality of electrode rows. The plurality of electrode strings are connected to each other at the end, and the capacitance between adjacent electrode strings can be detected.

The upper electrode has, for example, a plurality of small electrodes having a square shape in plan view. The plurality of small electrodes are complementarily arranged in a matrix at positions where the lower electrodes are not arranged in plan view. That is, the upper electrode and the lower electrode are arranged without a gap in plan view.

Further, the plurality of small electrodes are connected to adjacent small electrodes in the other diagonal direction of the small electrode to form a plurality of electrode strings. The plurality of electrode strings are connected to each other at the end, and the capacitance between adjacent electrode strings can be detected.

The insulating layer insulates the lower electrode and the upper electrode. As a material for forming the insulating layer, a material commonly known as a material for the insulating layer of the touch sensor can be used.

In addition, in this embodiment, although the touch sensor was demonstrated as what is what is called a projected capacitive touch sensor, in the range which does not impair the effect of this invention, a touch sensor of another method, such as a film resistance method, is employable. It may be.

(Shading Pattern)

The light blocking pattern may be provided as at least a part of a bezel or a housing of a window film or a display device to which the window film is applied. For example, the wiring of the display device may be blocked by the light shielding pattern and may not be visually recognized by the user. The color and / or material of the light shielding pattern is not particularly limited, and may be formed of a resin material having various colors such as black, white, and gold. For example, the light shielding pattern may be formed of a resin material such as an acrylic resin, an ester resin, an epoxy resin, polyurethane, silicone, or the like, in which a pigment for realizing color is mixed. The material and thickness of the light blocking pattern may be determined in consideration of protection and flexible characteristics of the window film or the display device. Moreover, these can also be used individually or in mixture of 2 or more types.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. "%" And "part" in an example mean a mass% and a mass part unless there is particular notice. First, the evaluation method is described.

<Measurement of elastic modulus>

The elasticity modulus of the polyamide-imide film obtained in the Example and the comparative example was measured using "Autograph AG-IS" by Shimadzu Corporation. A 10 mm wide film was produced, and the stress-strain curve was measured under the condition of the distance between the chucks 50 mm and the tensile speed 20 mm / min, and the elastic modulus was calculated from the inclination.

<Measurement of surface hardness>

As surface hardness of the polyamide-imide film obtained in the Example and the comparative example, the pencil hardness of the film surface was employ | adopted based on JISK5600-5-4: 1999. The load was 100 g and the scanning speed was 60 mm / minute, and the presence or absence of a scratch was evaluated in the environment of 4,000 lux, and pencil hardness was measured.

Measurement of Flexural Resistance

The bending resistance of the polyamideimide film obtained in the Example and the comparative example was made using the "MIT anti-fatigue tester (type 0530)" by Toyo Seiki Seisaku-sho, Ltd. Measured. A film having a thickness of 50 µm and a width of 10 mm in length and width was produced, and the number of reciprocating bends until fracture was evaluated when 135 ° at R = 1 mm was measured at a speed of 175 cpm at a load of 0.75 kgf.

<Measurement of weight average molecular weight (Mw)>

Gel Permeation Chromatography (GPC) Measurement

(1) pretreatment method

DMF eluent (10 mmol / L lithium bromide solution) was added to the sample so that it might be set to a concentration of 2 mg / mL, heated with stirring at 80 ° C. for 30 minutes, and cooled, followed by 0.45 μm membrane filter filtration, as a measurement solution.

(2) measurement conditions

Column: TSKgel α-2500 ((7) 7.8 mm diameter × 300 mm) x 1, α-M ((13) 7.8 mm diameter × 300 mm) × 2 made by TOSOH CORPORATION

Eluent: DMF (with 10 mmol / L lithium bromide)

Flow rate: 1.0 mL / min

Detector: RI Detector

Column temperature: 40 ℃

Injection volume: 100 μL

Molecular Weight Standard: Standard Polystyrene

<Measurement of thickness>

The thickness of the polyamide-imide film obtained by the Example and the comparative example was measured using the micrometer ("ID-C112XBS" by Mitutoyo Corporation).

<Example 1>

[Preparation of polyamideimide resin (1)]

In a 1 L separable flask with stirring blades under nitrogen atmosphere, 17.08 g (53.33 mmol) of 2,2'-bis (trifluoromethyl) benzidine (TFMB) and 313.57 g of N, N-dimethylacetamide (DMAc) were added. TFMB was dissolved in DMAc with addition and stirring at room temperature. Next, 9.58 g (21.66 mmol) of 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA) was added to the flask, and the mixture was stirred at room temperature for 3 hours. Thereafter, 8.18 g (32.32 mmol) of 2,6-naphthalenedicarboxylic acid dichloride (NADOC) was added to the flask, followed by stirring at room temperature for 1 hour. Subsequently, 3.01 g (32.32 mmol) of 4-picoline and 15.40 g (150.85 mmol) of acetic anhydride were added to the flask, stirred at room temperature for 30 minutes, and then heated to 70 ° C. using an oil bath, and further 3 hours. It stirred and obtained the reaction liquid.

The obtained reaction liquid was cooled to room temperature, poured into a large amount of methanol in a real shape, and the precipitate which precipitated was taken out, immersed in methanol for 6 hours, and wash | cleaned with methanol. Next, the precipitate was dried under reduced pressure at 60 ° C to obtain polyamideimide resin (1). The weight average molecular weight (Mw) of the polyamideimide resin (1) was 380,000.

[Production of Polyamide-imide Film (1)]

DMAc was added to the obtained polyamide-imide resin (1) so that a density | concentration might be 10 mass%, and the polyamide-imide varnish (1) was produced. Coating the obtained polyamideimide varnish (1) on the smooth surface of a polyester base material (Toyobo Co., Ltd. make, brand name "A4100") using an applicator so that the thickness of a freestanding film may be 50 micrometers. It dried at 50 degreeC for 30 minutes and then at 140 degreeC for 15 minutes, and obtained the self-supporting film. The freestanding film was fixed to a metal frame, and further dried at 200 ° C. for 60 minutes to obtain a polyamideimide film (1) having a thickness of 45 μm. The elasticity modulus, bending resistance, and pencil hardness of the polyamide-imide film 1 were measured by the said measuring method, and the elasticity modulus was 5.2 GPa, the bending resistance was 120,000 times, and the pencil hardness was 6B.

<Example 2>

[Preparation of polyamideimide resin (2)]

In a 1 L separable flask with stirring blades under nitrogen atmosphere, 17.40 g (54.33 mmol) of 2,2'-bis (trifluoromethyl) benzidine (TFMB) and 313.57 g of N, N-dimethylacetamide (DMAc) were added. TFMB was dissolved in DMAc with addition and stirring at room temperature. Next, 7.39 g (16.71 mmol) of 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA) was added to the flask, and the mixture was stirred at room temperature for 3 hours. Then, 8.42 g (33.27 mmol) of 2,6-naphthalenedicarboxylic acid dichloride (NADOC) and 1.64 g (5.56 mmol) of 4,4'-oxybis (benzoyl chloride) (OBBC) were added to the flask, It stirred at room temperature for 1 hour. Subsequently, 3.61 g (38.76 mmol) of 4-picoline and 11.90 g (116.56 mmol) of acetic anhydride were added to the flask, and the mixture was stirred at room temperature for 30 minutes, then heated to 70 ° C. using an oil bath, and further 3 hours. It stirred and obtained the reaction liquid.

The obtained reaction solution was cooled to room temperature, poured into a large amount of methanol in a solid form, and the precipitate deposited was taken out and immersed in methanol for 6 hours, and then washed with methanol. Next, the precipitate was dried under reduced pressure at 60 ° C to obtain a polyamideimide resin (2). The weight average molecular weight (Mw) of the polyamideimide resin (2) was 380,000.

[Production of Polyamide-imide Film (2)]

DMAc was added to the obtained polyamide-imide resin (2) so that a density | concentration might be 10 mass%, and the polyamide-imide varnish (2) was produced. The obtained polyamideimide varnish (2) is coated on the smooth surface of a polyester base material (Toyobo Co., Ltd. brand name "A4100") using an applicator so that the thickness of a freestanding film may be 55 micrometers, and it is 30 minutes at 50 degreeC, Then, it dried for 15 minutes at 140 degreeC, and obtained the self-supporting film. The freestanding film was fixed to a metal frame, and further dried at 200 ° C. for 60 minutes to obtain a polyamideimide film (2) having a thickness of 50 μm. The elasticity modulus, the bending resistance, and the pencil hardness of the polyamide-imide film 2 were measured by the said measuring method, and the elasticity modulus was 5.2 GPa, the bending resistance was 70,000 times, and the pencil hardness was H.

Comparative Example 1

[Preparation of polyamideimide resin (3)]

In a 1 L separable flask with stirring blades under nitrogen atmosphere, 14.29 g (44.62 mmol) of 2,2'-bis (trifluoromethyl) benzidine (TFMB) and 250.00 g of N, N-dimethylacetamide (DMAc) were added. TFMB was dissolved in DMAc with addition and stirring at room temperature. Next, 8.01 g (18.11 mol) of 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA) was added to the flask, and it stirred at room temperature for 3 hours. Then, 5.49 g (27.04 mmol) of terephthaloyl dichloride (TPC) was added to the flask, and it stirred at room temperature for 1 hour. Subsequently, 2.52 g (27.06 mmol) of 4-picoline and 12.88 g (126.16 mmol) of acetic anhydride were added to the flask, and the mixture was stirred at room temperature for 30 minutes, and then heated to 70 ° C. using an oil bath, and further 3 hours. It stirred and obtained the reaction liquid.

The obtained reaction solution was cooled to room temperature, poured into a large amount of methanol in a solid form, and the precipitate deposited was taken out and immersed in methanol for 6 hours, and then washed with methanol. Next, the precipitate was dried under reduced pressure at 60 ° C to obtain a polyamideimide resin (3). The weight average molecular weight (Mw) of the polyamideimide resin (3) was 290,000.

[Production of Polyamide-imide Film (3)]

DMAc was added to the obtained polyamide-imide resin (3) so that a density | concentration might be 10 mass%, and the polyamide-imide varnish (3) was produced. The obtained polyamideimide varnish (3) is coated on the smooth surface of a polyester base material (Toyobo Co., Ltd. product, brand name "A4100") using an applicator so that the thickness of a freestanding film may be 55 micrometers, and it is 30 minutes at 50 degreeC, Then, it dried for 15 minutes at 140 degreeC, and obtained the self-supporting film. The freestanding film was fixed to a metal frame, and further dried at 200 ° C. for 60 minutes to obtain a polyamideimide film (3) having a thickness of 50 μm. The elasticity modulus, bending resistance, and pencil hardness of the polyamide-imide film 3 were measured by the said measuring method, and the elasticity modulus was 4.8 GPa, the bending resistance was 70,000 times, and the pencil hardness was 6B.

<Example 3>

[Preparation of polyamideimide resin (4)]

In a 1 L separable flask with stirring blades under nitrogen atmosphere, 17.95 g (56.03 mmol) of 2,2'-bis (trifluoromethyl) benzidine (TFMB) and 313.57 g of N, N-dimethylacetamide (DMAc) were added. TFMB was dissolved in DMAc with addition and stirring at room temperature. Next, 5.08 g (11.44 mmol) of 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA) was added to the flask, and the mixture was stirred at room temperature for 3 hours. Then 10.13 g (40.02 mmol) of 2,6-naphthalenedicarboxylic acid dichloride (NADOC) and 1.69 g (5.72 mmol) of 4,4'-oxybis (benzoyl chloride) (OBBC) were added to the flask, It stirred at room temperature for 1 hour. Subsequently, 4.26 g (45.74 mmol) of 4-picoline and 8.17 g (80.05 mmol) of acetic anhydride were added to the flask, and the mixture was stirred at room temperature for 30 minutes, then heated to 70 ° C. using an oil bath, and further 3 hours. It stirred and obtained the reaction liquid.

The obtained reaction solution was cooled to room temperature, poured into a large amount of methanol in a solid form, and the precipitate deposited was taken out and immersed in methanol for 6 hours, and then washed with methanol. Next, the precipitate was dried under reduced pressure at 60 ° C to obtain a polyamideimide resin (4). The weight average molecular weight (Mw) of the polyamideimide resin (4) was 370,000.

[Production of Polyamide-imide Film (4)]

DMAc was added to the obtained polyamide-imide resin (4) so that a density | concentration might be 10 mass%, and the polyamide-imide varnish (4) was produced. The obtained polyamideimide varnish (4) is coated on the smooth surface of a polyester base material (Toyobo Co., Ltd. product, brand name "A4100") using an applicator so that the thickness of a self-supporting film may be 55 micrometers, and it is 30 minutes at 50 degreeC, Then, it dried for 15 minutes at 140 degreeC, and obtained the self-supporting film. The freestanding film was fixed to a metal frame, and further dried at 200 ° C. for 60 minutes to obtain a polyamideimide film (4) having a thickness of 50 μm. The elasticity modulus, the bending resistance, and the pencil hardness of the polyamide-imide film 4 were measured by the above measuring method. The elasticity modulus was 5.8 GPa, the bending resistance was 90,000 times, and the pencil hardness was H.

<Example 4>

[Preparation of polyamideimide resin (5)]

In a 1 L separable flask with stirring blades under nitrogen atmosphere, 18.11 g (56.56 mmol) of 2,2'-bis (trifluoromethyl) benzidine (TFMB) and 313.57 g of N, N-dimethylacetamide (DMAc) TFMB was dissolved in DMAc with addition and stirring at room temperature. Next, 5.10 g (11.48 mmol) of 4,4 '-(hexafluoroisopropylidene) diphthalic dianhydride (6FDA) was added to the flask, and the mixture was stirred at room temperature for 3 hours. Thereafter, 11.63 g (45.94 mmol) of 1,4-naphthalenedicarboxylic acid dichloride (14NADOC) was added to the flask, followed by stirring at room temperature for 1 hour. Subsequently, 4.28 g (45.94 mmol) of 4-picoline and 8.21 g (80.39 mmol) of acetic anhydride were added to the flask, and the mixture was stirred at room temperature for 30 minutes, and then heated to 70 ° C. using an oil bath, and further 3 hours. It stirred and obtained the reaction liquid.

The obtained reaction solution was cooled to room temperature, poured into a large amount of methanol in a solid form, and the precipitate deposited was taken out and immersed in methanol for 6 hours, and then washed with methanol. Next, the precipitate was dried under reduced pressure at 60 ° C to obtain a polyamideimide resin (5). The weight average molecular weight (Mw) of the polyamideimide resin (5) was 280,000.

[Production of Polyamide-imide Film (5)]

DMAc was added to the obtained polyamide-imide resin (5) so that a density | concentration might be 10 mass%, and the polyamide-imide varnish (5) was produced. The obtained polyamide-imide varnish (5) was coated on the smooth surface of a polyester base material (Toyobo Co., Ltd. product, brand name "A4100") using an applicator so that the film thickness of a self-supporting film might be 55 micrometers, and it carried out at 50 degreeC for 30 minutes. Then, it dried for 15 minutes at 140 degreeC, and obtained the self-supporting film. The self-supporting film was fixed to a metal frame and further dried at 200 ° C. for 60 minutes to obtain a polyamideimide film (5) having a film thickness of 50 μm. The elasticity modulus, bending resistance, and pencil hardness of the polyamide-imide film 5 were measured by the said measuring method, and the elasticity modulus was 5.6 GPa, the bending resistance was 30,000 times, and the pencil hardness was 6B.

Example 5

[Preparation of polyamideimide resin (6)]

16.91 g (52.80 mmol) of 2,2'-bis (trifluoromethyl) benzidine (TFMB), 4,4 '-(hexafluoroisopropylidene) in a 1 L separable flask with stirring blades under nitrogen atmosphere 1.96 g (5.87 mmol) of dianiline (6FDAM) and 313.57 g of N, N-dimethylacetamide (DMAc) were added and TFMB and 6FDAM were dissolved in DMAc with stirring at room temperature. Next, 6.97 g (23.70 mmol) of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) was added to the flask, and the mixture was stirred at room temperature for 3 hours. Thereafter, 9.00 g (35.55 mmol) of 2,6-naphthalenedicarboxylic acid dichloride (NADOC) was added to the flask, and the mixture was stirred at room temperature for 1 hour. Subsequently, 3.31 g (35.55 mmol) of 4-picoline and 16.94 g (165.92 mmol) of acetic anhydride were added to the flask, and the mixture was stirred at room temperature for 30 minutes, then heated to 70 ° C. using an oil bath, and further 3 hours. It stirred and obtained the reaction liquid.

The obtained reaction solution was cooled to room temperature, poured into a large amount of methanol in a solid form, and the precipitate deposited was taken out and immersed in methanol for 6 hours, and then washed with methanol. Next, the precipitate was dried under reduced pressure at 60 ° C to obtain a polyamideimide resin (6). The weight average molecular weight (Mw) of the polyamideimide resin (6) was 460,000.

[Production of Polyamide-imide Film (6)]

DMAc was added to the obtained polyamide-imide resin (6) so that a density | concentration might be 10 mass%, and the polyamide-imide varnish (6) was produced. The obtained polyamideimide varnish (6) is coated on the smooth surface of a polyester base material (Toyobo Co., Ltd. product, brand name "A4100") using an applicator so that the thickness of a freestanding film may be 55 micrometers, and it is 30 minutes at 50 degreeC, Then, it dried for 15 minutes at 140 degreeC, and obtained the self-supporting film. The freestanding film was fixed to a metal frame and further dried at 200 ° C. for 60 minutes to obtain a polyamideimide film (6) having a thickness of 50 μm. The elasticity modulus, bending resistance, and pencil hardness of the polyamide-imide film 6 were measured by the said measuring method, and the elasticity modulus was 6.8 GPa, the bending resistance was 70,000 times, and the pencil hardness was HB.

Table 1 shows the thickness and elastic modulus of the structural unit of the polyamideimide resin obtained in Examples 1 to 5 and Comparative Example 1, and the polyamideimide film. In addition, in the structural unit, the number in parentheses shows the introduction ratio of each structural unit. For example, in Example 1, it shows that it is NADOC unit: 6FDA unit: TFMB unit = 60: 40: 100.

As shown in Table 1, it was confirmed that the polyamideimide films obtained in Examples 1 to 5 had a higher elastic modulus as compared with the polyamideimide film obtained in Comparative Example 1. In particular, it was found that the polyamide-imide films obtained in Examples 2, 3, and 5 had a high pencil hardness and were compatible with high elastic modulus and high surface hardness. Moreover, the polyamideimide films obtained in Examples 1-3 and 5 may satisfy | fill high flexibility simultaneously, and it turned out that it can use suitably as a member of an image display apparatus.

Claims (7)

Equation (1) and (2)

[In Formula (1) and Formula (2), X represents a bivalent organic group each independently, Y represents a tetravalent organic group, R ^<a> respectively independently represents ^a halogen atom, a C1-C6 alkyl group, and carbon number An alkoxy group of 1 to 6 or an aryl group of 6 to 12 carbon atoms is represented, and the hydrogen atoms contained in R ^a may be each independently substituted with a halogen atom, and n represents an integer of 0 to 6;
The polyamideimide resin which contains the structural unit represented by and whose weight average molecular weight is 100,000-1,000,000. The method of claim 1,
Content of the structural unit represented by Formula (2) is polyamideimide resin which is 0.1-10 mol with respect to 1 mol of structural units represented by Formula (1). The method of claim 1,
Formula (2 ')

[In Formula (2 '), X and K each independently represent a divalent organic group, and at least one part of K represents Formula (3).

(Formula (3) of, R ¹ ~ R ⁸ is each independently represents a hydrogen atom, an alkoxy group having 1 to 6 carbon atoms alkyl group, having 1 to 6 carbon atoms, or an aryl group having a carbon number of ^{6 ~ 12, R 1 ~ R} 8 The hydrogen atoms contained in each may be independently substituted with a halogen atom, and A is a single bond, -O-, -CH _2- , -CH ₂ -CH _2- , -CH (CH ₃ )-,- C (CH ₃ ) _2- , -C (CF ₃ ) _2- , -SO _2- , -S-, -CO- or -N (R ⁹ )-, and R ⁹ is substituted with a hydrogen atom or a halogen atom Represents a hydrocarbon group having 1 to 12 carbon atoms, m is an integer of 0 to 4, and * represents a bond.)
Appears]
The polyamide-imide resin which further contains the structural unit represented by these. The polyamideimide film which contains the polyamideimide resin in any one of Claims 1-3. The flexible display device provided with the polyamideimide film of Claim 4. The method of claim 5,
Furthermore, the flexible display apparatus provided with a touch sensor. The method of claim 5,
Furthermore, the flexible display apparatus provided with a polarizing plate.