KR20190042065A - Retardation film having water vapor barrier property and manufacturing method thereof - Google Patents

Abstract

And a liquid crystal polymer having a photosensitive side chain, wherein the film thickness is more than 300 nm but not more than 50,000 nm.

Description

Retardation film having water vapor barrier property and manufacturing method thereof

The present invention relates to a retardation film having water vapor barrier property and a method of manufacturing the same.

In addition to high definition, there is a growing demand for weight reduction and flexibility in the fields of display devices such as organic electroluminescence (EL) displays and liquid crystal displays. Under such circumstances, a resin substrate has attracted attention in place of a glass substrate.

A substrate for an organic EL display requires a very high water vapor barrier property. Conventionally, a resin substrate having water vapor barrier property has been used in which a water vapor barrier layer is formed on the surface of a substrate made of a resin. For example, Patent Document 1 discloses a method of forming a multilayer structure by forming an inorganic layer formed by a counter target sputtering method, an inorganic layer formed by a vacuum evaporation method, an inorganic layer formed by a chemical vapor deposition method, A gas barrier film having an inorganic layer in this order is disclosed. However, this technique is complicated in the manufacturing process and has a problem in terms of productivity.

In the organic EL display, a retarder is used in order to suppress reflection of external light and improve visibility. If a high vapor barrier property can be imparted to the retarder, it is possible to simultaneously have both a function as a substrate and a function as a retardation film of the organic EL display. However, the gas barrier film using an inorganic material has a problem in that it can not satisfy a demand for flexibility and the like because the flexibility is insufficient.

International Publication No. 2013/168739

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and it is an object of the present invention to provide a retardation film having a water vapor barrier property which can be manufactured by a simple method at a lower cost than in the prior art and can be produced from an organic material, and a method for producing the same.

The inventors of the present invention have made intensive investigations in order to achieve the above object. As a result, the inventors have found that a retardation film comprising a polymer capable of exhibiting liquid crystallinity having a predetermined photosensitive side chain has a water vapor barrier property and can be produced by a simpler method The present inventors have completed the present invention.

Accordingly, the present invention provides a retardation film having the following water vapor barrier property and a method for producing the same.

1. A retardation film having a water vapor barrier property, which comprises a liquid crystalline polymer having photosensitive side chains and has a film thickness of more than 300 nm but not more than 50,000 nm.

2. A retardation film of 1 wherein said photosensitive side chain causes photo-crosslinking, photoisomerization or light-free transition.

3. The retardation film of 2, wherein the photosensitive side chain is at least one selected from the groups represented by the following formulas (1) to (6).

[Chemical Formula 1]

(Wherein, A ^1, A ² and A ³ are, each independently, a single _{bond, -O-, -CH 2 -, -C} (= O) -O-, -OC (= O) -, -C (= O) -NH-, -NH-C (= O) -, -CH = CH-C (= O) -O- or -OC (= O) -CH = CH-;

T ¹ represents an alkylene group having 1 to 12 carbon atoms which may be substituted with a halogen atom;

T ² represents a single bond or an alkylene group having 1 to 12 carbon atoms which may be substituted with a halogen atom;

Y ¹ represents a monovalent aromatic group selected from a phenyl group, a naphthyl group, a biphenyl group, a furanyl group and a pyrrolyl group, a monovalent cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, group represents a group formed by binding via a linking group a ^2, a part of hydrogen atoms bonded to the -COOR ⁰ these (R ⁰ represents a hydrogen atom or an alkyl group having a carbon number of _{1 ~ 5.), -NO 2} , -CN , -CH = C (CN) ₂ , -CH = CH-CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms;

Y ² is selected from a divalent aromatic group selected from a phenylene group, a naphthalenediyl group, a biphenylene group, a furandiyl group and a pyrrodiyl group, a divalent cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, represents a group of 2 to 6 groups formed by binding through a linking group is a ^2, a part of hydrogen atoms bonded to these _{-NO 2, -CN, -CH = C} (CN) 2, -CH = CH-CN, A halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;

R represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ¹ ;

X is a single bond, -C (= O) -O-, -OC (= O) -, -N = N-, -CH = CH-, -C = C-, O) -O- or -OC (= O) -CH = CH-; when X is 2 or more, each X may be the same or different;

C _ou represents a coumarin-6-yl group or a coumarin-7-yl group, and some of the hydrogen atoms bonding to these groups are -NO ₂ , -CN, -CH═C (CN) ₂ , A halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;

Q ¹ and Q ² each independently represent a divalent aromatic group selected from a phenylene group, a naphthalenediyl group, a biphenylylene group, a furandiyl group and a pyrrodiyl group, a divalent cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms , Or a group formed by bonding 2 to 6 groups selected from these substituents via a linking group A ² , but when X is -CH = CH-CO-O- or -O-CO-CH = CH- , Q ¹ or Q ² on the side bonded to -CH = CH- is a divalent aromatic group, and when Q ¹ is 2 or more, each Q ¹ may be the same or different, and when the number of Q ² is 2 or more, Each Q < ² > may be the same or different;

E represents -C (= O) -O- or -O-C (= O) -;

W ¹ and W ² each independently represent a group selected from the group consisting of a phenylene group, a naphthalenediyl group, a biphenylene group, a furandiyl group, a pyrrodiyl group, or a group having 2 to 6 substituents selected therefrom via a linking group A ² ≪ / RTI >

a1 represents 0 or 1;

a2 represents an integer of 0 to 2;

When a1 and a2 are both 0 and T ² is a single bond, A ¹ represents a single bond;

and a1 is 1, T ^2, when the unity sum, A ² denotes a single bond;

b represents 0 or 1;

The dashed line represents the bonding hand with the main chain.)

4. The retardation film of 3 wherein the photosensitive side chain is selected from the groups represented by the following formulas (7) to (10).

(2)

(Wherein A ¹ , A ² , A ³ , Y ¹ , Y ² , R, X and the broken line are the same as above, but when n is 0, A ² is a single bond;

R ¹ represents -NO ₂ , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;

c represents an integer of 1 to 12;

m represents an integer of 0 to 2;

m1 and m2 each independently represent an integer of 1 to 3;

d represents an integer of 0 to 4;

and n represents an integer of 0 to 12.)

5. The retardation film of 3 wherein the photosensitive side chain is selected from the groups represented by the following formulas (11) to (13).

(3)

(Wherein A ¹ , R, R ¹ , X, c, d, m ¹ and the broken line are the same as above and e represents an integer of 0 to 6)

6. A retardation film of 3 wherein the photosensitive side chain is a group represented by the following formula (14) or (15).

[Chemical Formula 4]

(Wherein A ¹ , R ¹ , Y ¹ , c, d, m ¹ , and m 2 and the broken line are the same as above)

7. A retardation film of 3 wherein the photosensitive side chain is a group represented by the following formula (16) or (17).

[Chemical Formula 5]

(Wherein A ¹ , R ¹ , X, c, d, m and the broken line are the same as above and f represents an integer of 0 to 5)

8. A retardation film of 3 wherein the photosensitive side chain is a group represented by the following formula (18) or (19).

[Chemical Formula 6]

(Wherein A ¹ , A ² , E, R ¹ , Y ¹ , c, d, m 1 and m 2 are the same as above and g is an integer of 0 to 5)

9. A retardation film of 3 wherein the photosensitive side chain is a group represented by the following formula (20).

(7)

(Wherein A ¹ , R ¹ , X, Y ¹ , c, d and m and the broken line are the same as above)

10. The retardation film of any one of 1 to 9, wherein the liquid crystalline polymer further comprises at least one liquid crystalline side chain selected from the groups represented by the following formulas (21) to (35).

[Chemical Formula 8]

[Chemical Formula 9]

(Wherein A ¹ , A ² , E, R ¹ , c, d, e, m ¹ , m 2 and the broken line are the same as above;

R ² represents a hydrogen atom, -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furanyl group, A ring-containing group, a cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;

Y ³ represents a group selected from the group consisting of a phenyl group, a naphthyl group, a biphenyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, ² , and a part of the hydrogen atoms bonded to these may be replaced by -NO ₂ , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;

Z ¹ and Z ² each independently represent a single bond, -C (= O) -, -CH ₂ O-, -CH = N- or -CF ₂ -;

h represents an integer of 0 to 5;

k represents an integer of 0 to 2 independently of each other, but in the formulas (25) and (26), the sum of all k is 2 or more,

and m3 represents an integer of 1 to 3.)

11. The retardation film of 10, wherein the liquid crystalline polymer comprises a repeating unit represented by the following formula (A) and a repeating unit represented by the following formula (B).

 [Chemical formula 10]

(Wherein R ^A is at least one species selected from the groups represented by the formulas (1) to (6) and R ^B is at least one species selected from the groups represented by the formulas (21) to (31) M ^A and M ^B each independently represent a group derived from a polymerizable group.)

12. An eleventh retardation film wherein the group derived from the polymerizable group is at least one selected from groups represented by the following formulas.

(11)

(Wherein, R ^C is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a carboxyl group or represents a carboxylic group, R ^D is a single bond, -C (= O) -O-, -C (= O) - NH- or phenylene group, R ^E represents a hydroxyl group, an alkyl group or an alkoxy group of 1 to 10 carbon atoms, or a phenyl group, and the broken line represents a bond with R ^A or R ^B )

13. The retardation film of any one of 1 to 12, wherein the temperature range in which the liquid crystalline polymer exhibits liquid crystallinity is 50 to 300 占 폚.

14. An organic EL display comprising a retardation film of any one of 1 to 13.

15. A process for forming a coating film having a film thickness of more than 300 nm but not more than 50,000 nm by applying a composition for forming a retardation film including a resin component containing a liquid crystalline polymer having photosensitive side chains and an organic solvent to a substrate,

A step of irradiating the coating film with polarized ultraviolet light, and

A step of heating the film irradiated with the polarized ultraviolet rays to obtain a film having a film thickness of more than 300 nm but not more than 50,000 nm

Wherein the film has a water vapor barrier property.

16. The method for producing a retardation film of 15, wherein the photosensitive side chain causes photo-crosslinking, photoisomerization, or light-free transition.

17. The method for producing a retardation film of 16, wherein the photosensitive side chain is at least one selected from the groups represented by the formulas (1) to (6).

18. The method for producing a retardation film according to any one of 14 to 17, wherein the liquid crystalline polymer further comprises at least one liquid crystalline side chain selected from the groups represented by the formulas (21) to (35).

19. A method for producing a retardation film of any one of 14 to 18, wherein the liquid crystalline polymer exhibits liquid crystallinity in a temperature range of 50 to 300 占 폚.

The retardation film of the present invention has high water vapor barrier properties and functions as a retardation film and can be suitably used for a display device such as an organic EL display. Further, the retardation film of the present invention can be manufactured by a simple method at a lower cost than the conventional method, and the productivity is also good.

[Retardation film having water vapor barrier property]

The retardation film having water vapor barrier property of the present invention includes a liquid crystalline polymer having photosensitive side chains and has a film thickness of more than 300 nm and 50,000 nm or less.

The structure of the photosensitive side chain is not particularly limited, but a structure which causes a crosslinking reaction, an isomerization reaction or a light-free potential in response to light is preferable, a structure which causes a crosslinking reaction or a light-free potential is more preferable, It is even more desirable to produce it.

The photosensitive side chain is preferably at least one selected from the groups represented by the following formulas (1) to (6).

[Chemical Formula 12]

Wherein A ¹ , A ² and A ³ are each independently a single bond, -O-, -CH ₂ -, -C (═O) -O-, -OC (═O) -, -C = O) -NH-, -NH-C (= O) -, -CH = CH-C (= O) -O- or -OC (= O) -CH = CH-.

T ¹ represents an alkylene group having 1 to 12 carbon atoms which may be substituted with a halogen atom. T ² represents a single bond or an alkylene group having 1 to 12 carbon atoms which may be substituted with a halogen atom.

Y ¹ represents a monovalent aromatic group selected from a phenyl group, a naphthyl group, a biphenyl group, a furanyl group and a pyrrolyl group, a monovalent cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, group represents a group formed by binding via a linking group a ^2, a part of hydrogen atoms bonded to the -COOR ⁰ these (R ⁰ represents a hydrogen atom or an alkyl group having a carbon number of _{1 ~ 5.), -NO 2} , -CN , -CH = C (CN) ₂ , -CH = CH-CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.

Y ² is selected from a divalent aromatic group selected from a phenylene group, a naphthalenediyl group, a biphenylene group, a furandiyl group and a pyrrodiyl group, a divalent cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, represents a group of 2 to 6 groups formed by binding through a linking group is a ^2, a part of hydrogen atoms bonded to these _{-NO 2, -CN, -CH = C} (CN) 2, -CH = CH-CN, A halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

R represents a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ¹ .

X is a single bond, -C (= O) -O-, -OC (= O) -, -N = N-, -CH = CH-, -C = C-, O) -O- or -OC (= O) -CH = CH-, and when the number of X's is 2 or more, each X may be the same or different.

C _ou represents a coumarin-6-yl group or a coumarin-7-yl group, and some of the hydrogen atoms bonding to these groups are -NO ₂ , -CN, -CH═C (CN) ₂ , A halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

Q ¹ and Q ² each independently represent a divalent aromatic group selected from a phenylene group, a naphthalenediyl group, a biphenylylene group, a furandiyl group and a pyrrodiyl group, a divalent cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms , Or a group formed by bonding 2 to 6 groups selected from these substituents via a linking group A ² , but when X is -CH = CH-CO-O- or -O-CO-CH = CH- , Q ¹ or Q ² on the side bonded to -CH = CH- is a divalent aromatic group, and when Q ¹ is 2 or more, each Q ¹ may be the same or different, and when the number of Q ² is 2 or more, Each Q < ² > may be the same or different.

E represents -C (= O) -O- or -OC (= O) -. W ¹ and W ² each independently represent a group selected from the group consisting of a phenylene group, a naphthalenediyl group, a biphenylene group, a furandiyl group, a pyrrodiyl group, or a group having 2 to 6 substituents selected therefrom via a linking group A ² ≪ / RTI >

a1 represents 0 or 1; a2 represents an integer of 0 to 2; When a1 and a2 are both 0 and T ² is a single bond, A ¹ represents a single bond. and a1 is 1, and when T ² is unity sum, A ² represents a single bond. b represents 0 or 1; The dashed line represents the bonding hand with the main chain.)

The photosensitive side chain is preferably represented by the following formulas (7) to (10).

[Chemical Formula 13]

In the formula, A ¹ , A ² , A ³ , Y ¹ , Y ² , R, X and the broken line are the same as above, but when n is 0, A ² is a single bond. R ¹ represents -NO ₂ , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. and c represents an integer of 1 to 12. m represents an integer of 0 to 2; m1 and m2 each independently represent an integer of 1 to 3; d represents an integer of 0 to 4; n represents an integer of 0 to 12;

Examples of the alkyl group having 1 to 5 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, have. Examples of the alkoxy group having 1 to 5 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec- Time and so on.

The photosensitive side chain is also preferably represented by the following formulas (11) to (13).

[Chemical Formula 14]

(Wherein A ¹ , X, R, R ¹ , c, d, m, m ¹ and the broken line represent the same as above and e represents an integer of 0 to 6)

The photosensitive side chain is also preferably represented by the following formula (14) or (15).

[Chemical Formula 15]

(Wherein A ¹ , R ¹ , Y ¹ , c, d, m ¹ , and m2 and the broken line are the same as above)

The photosensitive side chain is also preferably represented by the following formula (16) or (17).

[Chemical Formula 16]

(Wherein A ¹ , R ¹ , X, c, d, m and d are the same as above and f is an integer of 0 to 5)

The photosensitive side chain is also preferably represented by the following formula (18) or (19).

[Chemical Formula 17]

(Wherein A ¹ , A ² , E, R ¹ , Y ¹ , c, d, m 1 and m 2 and the broken line represent the same as above and g represents an integer of 0 to 5)

The photosensitive side chain is also preferably represented by the following formula (20).

[Chemical Formula 18]

(Wherein A ¹ , R ¹ , X, Y ¹ , c, d and m and the broken line are the same as above)

It is preferable that the photosensitive side chain reacts with light in a wavelength range of 250 to 400 nm.

The photosensitive side chain is preferably represented by formulas (7), (8), (9), (14) and (15).

The liquid crystalline polymer is bonded to a side chain having photosensitivity to the main chain, and can react with light to cause a crosslinking reaction, an isomerization reaction, or a light-free potential. The structure of the side chain having photosensitivity is not particularly limited, but a structure which causes a crosslinking reaction or a light-free potential in response to light is preferable, and it is more preferable to cause a crosslinking reaction. The structure of the polymer film having photosensitive side chains capable of exhibiting liquid crystallinity is not particularly limited as long as it satisfies such properties, but it is preferable that the polymer film has a mesogen component which is rigid in the side chain structure.

The liquid crystalline polymer preferably exhibits liquid crystallinity in a temperature range of 50 to 300 캜. The liquid crystal display temperature is more preferably 60 to 280 ° C, further preferably 70 to 250 ° C, and even more preferably 80 to 200 ° C. When the liquid crystal property is within the above-mentioned range, it is possible to produce a film capable of stably maintaining the resulting vapor barrier property and retardation for a long time even when exposed to external stress such as heat or light.

In addition to the photosensitive side chain, the liquid crystalline polymer preferably includes a liquid crystalline side chain having a rigid mesogen portion. As such a side chain, at least one species selected from the groups represented by the following formulas (21) to (35) is preferable.

[Chemical Formula 19]

[Chemical Formula 20]

In the formula, A ¹ , A ² , E, R ¹ , c, d, e, m ¹ , m 2 and dashed lines are the same as described above.

R ² represents a hydrogen atom, -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furanyl group, A ring-containing group, a cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.

Y ³ represents a group selected from the group consisting of a phenyl group, a naphthyl group, a biphenyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, ² , and a part of the hydrogen atoms bonded to these may be substituted with -NO ₂ , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.

Z ¹ and Z ² each independently represent a single bond, -C (= O) -, -CH ₂ O-, -CH = N- or -CF ₂ -.

h represents an integer of 0 to 5; k represents an integer of 0 to 2 independently of each other, but in the formulas (25) and (26), the sum of all k is 2 or more. m3 represents an integer of 1 to 3;

The liquid crystalline side chain is preferably represented by the formulas (21), (22), (23), (24), (27), (29), (30) and (31).

The liquid crystalline polymer has a main chain and side chains bonded thereto, and includes the photosensitive side chain or the liquid crystal side chain as a side chain. The polymer preferably includes polyimide, polyester, polyurea, or a repeating unit represented by the following formula (A) and a repeating unit represented by the following formula (B), including the side chain.

[Chemical Formula 21]

Wherein R ^A is at least one species selected from the groups represented by formulas (1) to (6), R ^B is at least one species selected from the groups represented by formulas (21) to (35) ^A and M ^B each independently represent a group derived from a polymerizable group.

The main chain may be one derived from a radical polymerizable monomer such as (meth) acrylic acid, itaconic acid, fumaric acid, maleic acid,? -Methylene-? -Butyrolactone, ethylene, styrene, maleimide or norbornene, Structure is preferable.

Specifically, it is preferable that the group derived from the polymerizable group is at least one selected from groups represented by the following formulas.

[Chemical Formula 22]

Wherein R ^C represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a carboxyl group or a carboxylmethyl group, R ^D is a single bond, -C (= O) -O-, -C (= O) -NH - or a phenylene group, R ^E represents a hydroxyl group, an alkyl group or an alkoxy group of 1 to 10 carbon atoms, or a phenyl group, and the broken line represents a bond with R ^A or R ^B.

Among them, the polymerizable group is preferably derived from (meth) acrylic acid,? -Methylene-? -Butyrolactone, styrene or maleimide, and is preferably derived from (meth) acrylic acid,? -Methylene-? -Butyrolactone, Styrene, and more preferably those derived from (meth) acrylic acid and? -Methylene-? -Butyrolactone.

In the liquid crystalline polymer, the content of the photosensitive side chain is preferably 5 mol% or more, more preferably 10 mol% or more, of all the side chains. The content of the liquid crystalline side chain is preferably 95 mol% or less, more preferably 90 mol% or less, of all the side chains. The total content of the photosensitive side chain and the liquid crystalline side chain is preferably 70 mol% or more, more preferably 80 mol% or more, of the total side chains.

It is preferable that the liquid crystalline polymer includes a polar group in at least one of the photosensitive side chain and the liquid crystalline side chain. The polar group is preferably a hydroxyl group, a carboxyl group, an amide group or an amino group, and more preferably a carboxyl group. The liquid crystalline polymer may contain a crosslinking structure to such an extent that it does not inhibit liquid crystallinity. Examples of the cross-linking structure include those derived from an oxirane ring-containing group such as glycidyl group, an oxetane ring-containing group, and the like.

The liquid crystalline polymer may contain other side chains other than the photosensitive side chain and the liquid crystalline side chain within a range that does not impair the effect of the present invention. Examples of such a side chain include a linear or branched alkyl group having 1 to 15 carbon atoms, a linear or branched halogenated alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 20 carbon atoms, a hetero An aryl group, an aralkyl group having 7 to 20 carbon atoms, a heteroaralkyl group having 3 to 20 carbon atoms, an oxirane ring-containing group such as a glycidyl group, and an oxetane ring-containing group. In the liquid crystalline polymer, the content of the other side chain is preferably 30 mol% or less in the total side chain.

 Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- An n-decyl group, an n-dodecyl group, an n-tridecyl group, a n-tetradecyl group, and an n-pentadecyl group. Examples of the halogenated alkyl groups include groups in which some or all of the hydrogen atoms of these alkyl groups are substituted with halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, A 4-phenanthryl group, and a 9-phenanthryl group.

Examples of the heteroaryl group include an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom and the like. Specific examples of the heteroaryl group include a 2-thienyl group, a 3-thienyl group, a 2-furanyl group, Thiazolyl group, 4-thiazolyl group, 4-thiazolyl group, 4-thiazolyl group, 4-thiazolyl group, 4-thiazolyl group, Thiazolyl group, 3-isothiazolyl group, 4-isothiazolyl group, 5-isothiazolyl group, 2-imidazolyl group, 4-imidazolyl group, 2-pyridyl group, , 4-pyridyl group, and the like.

Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group.

The heteroaralkyl group preferably includes an oxygen atom, a nitrogen atom, a sulfur atom, a selenium atom and the like. Specific examples thereof include a thienylmethyl group, a furanylmethyl group, an oxazolylmethyl group, a 3-isoxazolylmethyl group, An isothiazolylmethyl group, an imidazolylmethyl group, and a pyridylmethyl group.

The repeating unit having such a side chain is preferably represented by the following formula (C).

(23)

In the formula, R ^C represents a linear or branched alkyl group having 1 to 15 carbon atoms, a linear or branched halogenated alkyl group having 1 to 15 carbon atoms, an aryl group having 6 to 20 carbon atoms, a hetero An arylene group, an aralkyl group having 7 to 20 carbon atoms, a heteroaralkyl group having 3 to 20 carbon atoms, an oxirane ring-containing group such as a glycidyl group, an oxetane ring-containing group, and the like. M ^C represents a group derived from a polymerizable group. Examples of the polymerizable group include those exemplified for the explanation of M ^A and M ^B.

The weight average molecular weight (Mw) of the polymer is preferably from 2,000 to 1,000,000, more preferably from 5,000 to 100,000, in view of the strength of the obtained coating film, the workability at the time of forming the coating film, and the uniformity of the coating film. In the present invention, Mw is measured value by polystyrene conversion by gel permeation chromatography (GPC).

The polymer can be synthesized, for example, according to the method described in WO 2014/054785.

[Manufacturing method of phase difference film having water vapor barrier property]

In the method for producing a retardation film of the present invention,

[I] a step of applying a composition for forming a retardation film including a resin component containing the liquid crystalline polymer and an organic solvent to a substrate to form a coating film having a film thickness of more than 300 nm but not more than 50,000 nm,

[II] a step of irradiating the coating film with polarized ultraviolet light, and

[III] The step of heating the film irradiated with the polarized ultraviolet rays to obtain a film having a film thickness of more than 300 nm but not more than 50,000 nm

.

In the step [I], the substrate is not particularly limited, but a glass substrate, an acetate substrate, an acrylic substrate, a polycarbonate substrate, a polyethylene terephthalate substrate, a polyethylene naphthalate substrate, a cycloolefin polymer substrate, a polyimide substrate A plastic substrate of the above-mentioned substrate can be used.

The composition for forming a retardation film includes a resin component containing the liquid crystalline polymer and an organic solvent. It is preferable that the composition for forming a retardation film is a solution in which the polymer is dissolved in an organic solvent from the viewpoint of being suitable for forming a retardation film.

All of the resin components may be the liquid crystalline polymer, but may include other polymers (hereinafter referred to as other polymers) within a range that does not impair the liquid crystal developing ability and photosensitive performance. Examples of other polymers include poly (meth) acrylate, polyamic acid, polyimide and the like. When the resin component contains other polymer, the content of other polymer in the resin component is preferably 0.5 to 80 mass%, more preferably 1 to 50 mass%.

The content of the resin component in the retardation film-forming composition is preferably from 1 to 20 mass%, more preferably from 3 to 15 mass%, still more preferably from 3 to 10 mass%.

Examples of the organic solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2- , N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide,? -Butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy- N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3-dimethyl- imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, Methylene-2-pentanone, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, ethylene glycol monomethyl ether, , Dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene Recol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, Ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, and the like. These may be used alone or in combination of two or more.

In addition, a poor solvent may be added in order to improve the uniformity of the film thickness and the surface smoothness. Examples of the poor solvent include isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, diisobutyl carbinol, butyl And examples thereof include carbitol, ethylcarbitol, ethylcarbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, Butyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, di Propylene glycol monomethyl ether, dipropylene glycol Propyleneglycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl- But are not limited to, 3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, , n-pentane, n-octane, diethyl ether, methyl lactate, methyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, Methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3- 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol monoacetate, Propylene glycol monoethyl ether-2-acetate, propylene glycol di-acetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol- And a solvent having a low surface tension such as ethyl lactate, n-propyl lactate, n-butyl lactate, and lactic acid-isoamyl.

The content of the poor solvent is preferably 5 to 80% by mass, and more preferably 20 to 60% by mass in the total solvent, so as not to significantly lower the solubility of the solvent as a whole. The poor solvent may be used alone or in combination of two or more.

The retardation film-forming composition may contain a surfactant such as a fluorine-based surfactant, a silicon-based surfactant, or a nonionic-based surfactant from the viewpoint of improving film thickness uniformity and surface smoothness. Examples of the surfactant include FEPTOR (registered trademark) 301, EF303, EF352 (manufactured by Mitsubishi Materials Engineering Co., Ltd.), Megapack (registered trademark) F171, F173, R-30 SC101, SC102, SC103, SC104, SC105 (manufactured by Asahi Glass Co., Ltd.), Fluorad (registered trademark) FC430, FC431 , SC106 (manufactured by AGC Seiyaku Chemical Co., Ltd.), and the like. The content of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the resin component.

The composition for forming a retardation film may contain a functional silane-containing compound. Examples of the functional silane-containing compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3- , N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxy Silane triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl- Diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl- Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxysilane, N -Bis (oxyethylene) -3-aminopropyltriethoxysilane, and the like. These may be used alone or in combination of two or more.

The content of the functional silane-containing compound is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the resin component. Within this range, an effect of improving the adhesion can be obtained.

The retardation film-forming composition may further contain an additive such as a phenoplast compound, an epoxy group-containing compound, or an oxetane ring-containing compound for the purpose of improving reliability, lowering the barrier property and retardation do.

Examples of the phenoplast compound include, but are not limited to, the following compounds.

≪ EMI ID =

Examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6 -Tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl ) Cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane and the like.

The composition for forming a retardation film may further contain a photosensitizer. As the photosensitizer, a colorless sensitizer and a triplet sensitizer are preferable. Examples of the photosensitizer include an aromatic nitro compound, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), ketocoumarin, carbonylbiscumarin, aromatic 2-hydroxy ketone 2-hydroxybenzophenone), an amino substituted aromatic 2-hydroxy ketone (mono- or di- p- (dimethylamino) -2-hydroxybenzophenone), acetophenone, anthraquinone, xanthone, thiosantone, benz (2-benzoylmethylene-3-methyl-? -Naphthothiazoline, 2- (? -Naphthoylmethylene) -3-methylbenzothiazoline, 2- -Methyl-β-naphthothiazoline, 2- (4-biphenoylmethylene) -3-methylbenzothiazoline, 2- Methyl-β-naphthothiazoline, 2- (p-fluorobenzoylmethylene) -3-methyl-β-naphthothiazoline), an oxazoline derivative (2-benzoylmethylene- Naphthooxazoline, 2- (? - 2- (4-biphenoylmethylene) -3-methylbenzooxazoline, 2- (? - naphthoylmethylene) -Naphthoylmethylene) -3-methyl- beta -naphthoxazoline, 2- (4-biphenoylmethylene) -3-methyl- beta -naphthoxazoline, 2- (p- fluorobenzoylmethylene) -3 (Methyl- beta -naphthoxazoline), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4,6-trinitroaniline), nitroascenaphthene Alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone), naphthalene derivatives (2-naphthalene methanol, 2-naphthalene-2- 2-naphthalenecarboxylic acid), anthracene derivatives (9-anthracene methanol, 9-anthracenecarboxylic acid), benzopyran, azoindolizine and merocoumarin. Of these, aromatic 2-hydroxy ketone (benzophenone), coumarin, ketocoumarin, carbonylbiscumarin, acetophenone, anthraquinone, xanthone, thioxanthone, and acetophenone ketal are preferred.

The content of the additive and photosensitizer is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, per 100 parts by mass of the resin component. Within this range, a sufficient effect is obtained and the liquid crystal property is not impaired.

 In addition to the above-mentioned composition, a dielectric substance or a conductive substance, and further, a crosslinking compound may be added to the retardation film forming composition within the range that does not impair the effect of the present invention.

The method of applying the composition for forming a retardation film to a substrate is not particularly limited. As a coating method, screen printing, gravure printing, offset printing, flexographic printing, inkjet printing, and the like are generally used industrially. As other coating methods, there are dip coating, die coating, roll coating, slit coating, spin coating, spray coating and the like, depending on the purpose.

After the composition for forming a retardation film is coated on a substrate, it is preferably baked at a temperature of 50 to 200 캜, more preferably 50 to 150 캜, by heating means such as a hot plate, a heat circulation type oven, The solvent is evaporated to obtain a coating film. The temperature at this time is preferably lower than the liquid crystal phase expression temperature of the polymer.

The film thickness of the coating film is more than 300 nm but not more than 50,000 nm, but the lower limit thereof is preferably 350 nm, more preferably 400 nm, still more preferably 1,000 nm, and most preferably 1,500 nm . On the other hand, the upper limit is preferably 20,000 nm, more preferably 10,000 nm, still more preferably 6,000 nm, and most preferably 5,000 nm.

After the step [I] and before the step [II], a step of cooling the substrate having the coated film to room temperature may be provided.

In the step [II], when polarizing ultraviolet rays are irradiated on the film surface of the coated film, polarized ultraviolet rays are irradiated to the substrate from a certain direction through the polarizing plate. As the ultraviolet ray to be used, those having a wavelength of 100 to 400 nm are suitable. The optimum wavelength is selected through a filter or the like depending on the type of the coating film to be used. For example, ultraviolet rays having a wavelength in the range of 290 to 400 nm can be selectively used so as to cause photo-crosslinking reaction selectively. As ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

The irradiation amount of the polarized ultraviolet ray depends on the coating film to be used. The amount of irradiation is set such that the amount of the polarized ultraviolet light (1) realizing the maximum value of? A (hereinafter also referred to as? Amma), which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet light and the ultraviolet absorbance in the direction perpendicular to that direction To 70%, and more preferably in the range of 1 to 50%.

In the step [III], a large anisotropy (phase difference) can be given to the coating film by heating the coating film irradiated with the polarized ultraviolet rays.

As the heating, a heating means such as a hot plate, a heat circulation type oven, and an infrared type oven may be used. The heating temperature can be determined in consideration of the temperature at which the liquid crystal property of the coating film to be used is expressed.

The heating temperature is preferably within the range of the temperature at which the liquid crystalline polymer exhibits liquid crystallinity (hereinafter referred to as liquid crystal temperature). In the case of a thin film surface such as a coating film, it is expected that the liquid crystal development temperature at the surface of the coating film is lower than the liquid crystal expression temperature when the photosensitive side chain polymer capable of exhibiting liquid crystallinity is observed in bulk. For this reason, it is more preferable that the heating temperature is within the temperature range of the liquid crystal forming temperature on the surface of the coating film. That is, the temperature range of the heating temperature after irradiation with the polarized ultraviolet light is set to a temperature lower by 10 占 폚 than the lower limit of the temperature range of the liquid crystal display temperature of the chain polymer to be used as the lower limit and a temperature 10 占 폚 lower than the upper limit of the liquid crystal temperature range, The temperature is preferably in the range of < RTI ID = 0.0 > If the heating temperature is lower than the above temperature range, the effect of amplifying the anisotropy due to heat in the coating film tends to become insufficient. If the heating temperature is too high than the above temperature range, the coating film state becomes isotropic liquid state ). In this case, it may become difficult to reorient in one direction by self-organization.

The liquid crystal display temperature refers to a temperature equal to or higher than the glass transition temperature at which the liquid crystalline polymer undergoes phase transition from the solid phase to the liquid crystal phase and below the isotropic phase transition temperature at which phase transition occurs from the liquid crystal phase to the isotropic phase (isotropic phase).

The film thickness of the coating film formed after heating is more than 300 nm but not more than 50,000 nm, but the lower limit thereof is preferably 350 nm, more preferably 400 nm, still more preferably 1,000 nm, Is 1,500 nm. On the other hand, the upper limit is preferably 20,000 nm, more preferably 10,000 nm, still more preferably 6,000 nm, and most preferably 5,000 nm.

With this manufacturing method, introduction of anisotropy into the coating film can be realized with high efficiency. In short, a phase difference is expressed. In addition, a base material having a retardation film can be produced with high efficiency.

The retardation film of the present invention thus obtained also has a water vapor barrier property. It is believed that since the mesogen skeleton is neatly oriented, the π conjugation and the π-π stacking effect can be obtained, thereby improving the barrier property. Specifically, it is preferable that the water vapor transmission rate when the film thickness of the retardation film is 1,000 nm is 500 g / m < 2 > day or less. In the present invention, the water vapor transmission rate is a value measured under conditions of a temperature of 40 DEG C and a relative humidity of 90% according to JIS Z 0208 " moisture permeability test method (cup method) of moisture-proof wrapping material ".

The retardation film having water vapor barrier property of the present invention is particularly useful as a retardation film for an organic EL display. The organic EL display provided with the retardation film of the present invention has high reliability of water vapor barrier property, and thus it is possible to manufacture a large-sized, high-precision display.

Example

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured using Shodex GPC-101 (solvent: tetrahydrofuran, calibration curve: standard polystyrene) manufactured by Showa Denko K.K.

[1] Synthesis of monomers

[Synthesis Example 1-1] Synthesis of monomer MA1

According to the method described in International Publication No. 2011/084546, a monomer MA1 represented by the following formula was synthesized.

(25)

[Synthesis Example 1-2] Synthesis of monomer MA2

A monomer MA2 represented by the following formula was synthesized according to the method described in JP-A-9-118717.

(26)

[Synthesis Example 1-3] Synthesis of monomer MA3

Macromolecules (2012), 45 (21), pp. The monomer MA3 represented by the following formula was synthesized according to the method described in EP-A-8547-8554.

(27)

[Synthesis Example 1-4] Synthesis of monomer MA4

According to the method described in International Publication No. 2013/133078, a monomer MA4 represented by the following formula was synthesized.

(28)

[Synthesis Example 1-4] Synthesis of monomer MA5

According to the method described in International Publication No. 2013/133078, a monomer MA5 represented by the following formula was synthesized.

[Chemical Formula 29]

[2] Synthesis of polymer

[Synthesis Example 2-1] Synthesis of polymer P1

6.64 g of the monomer MA1 and 9.19 g of the monomer MA2 were dissolved in 146.42 g of tetrahydrofuran (THF) and deaerated by a diaphragm pump, and then 0.82 g of 2,2'-azobisisobutyronitrile (AIBN) was added , And then degassed again. Thereafter, the reaction was carried out at 60 DEG C for 8 hours. The resulting reaction solution was added dropwise to 300 ml of methanol, and the resulting precipitate was filtered, washed with methanol, and dried under reduced pressure to obtain polymer P1 in the form of powder (yield: 12.67 g, yield: 80%). The composition ratio of the polymer P1 was monomer MA1: monomer MA2 = 40: 60. The polymer P1 had Mn of 16,000 and Mw / Mn of 1.75.

[Synthesis Example 2-2] Synthesis of polymer P2

A powdered polymer P2 was obtained in the same manner as in Example 1 except that 1.66 g of the monomer MA1 and 2.06 g of the monomer MA3 were used as the raw materials. The composition ratio of the polymer P2 was monomer MA1: monomer MA3 = 50:50. The Mn of the polymer P2 was 27,000 and the Mw / Mn was 2.25.

[Synthesis Example 2-3] Synthesis of polymer P3

To a flask equipped with a condenser tube were added 2.16 g (4.8 mmol) of monomer MA4, 1.80 g (3.6 mmol) of monomer MA5, 0.84 g (3.6 mmol) of n-dodecyl acrylate, 48.0 g of N-methylpyrrolidone (NMP), and 0.10 g of AIBN were charged, the inside of the flask was purged with nitrogen, and the mixture was reacted at 60 ° C for 20 hours with stirring. The resulting reaction solution was poured into 400 ml of methanol, and a white powder was precipitated. The white powder was filtered and vacuum-dried at room temperature to obtain a polymer P3 represented by the following formula (yield: 3.60 g, yield: 75%). The polymer P3 had an Mn of 13,258 and an Mw / Mn of 2.0.

(30)

[Synthesis Example 2-4] Synthesis of polymer P4

To a flask equipped with a cooling tube were added 1.80 g (4 mmol) of monomer MA4, 1.50 g (3 mmol) of monomer MA5, 0.48 g (2 mmol) of n-dodecyl acrylate, (1 mmol), NMP (40.0 g) and AIBN (0.085 g) were charged, and the inside of the flask was purged with nitrogen. The mixture was reacted at 60 ° C for 20 hours with stirring. The resulting reaction solution was poured into 400 ml of methanol, and a white powder was precipitated. This white powder was filtered and vacuum-dried at room temperature to obtain polymer P4 represented by the following formula (yield: 2.80 g, yield: 71%). The polymer P4 had Mn of 12,000 and Mw / Mn of 2.00.

(31)

[3] Preparation of composition for forming retardation film

[Preparation Example 1] Preparation of composition C1 for forming retardation film

To 7.5 g of NMP, 1.5 g of polymer P1 was added and dissolved by stirring at room temperature for 1 hour. To this solution, 1.0 g of butyl cellosolve (BC) was added and stirred to obtain a retardation film-forming composition C1.

[Preparation Example 2] Preparation of Composition C2 for forming retardation film

To 3.2 g of propylene glycol monomethyl ether (PGME), 1.0 g of polymer P2 was added and dissolved by stirring at room temperature for 1 hour. To this solution, 1.4 g of cyclohexanone (CHN) was added and stirred to obtain a retardation film-forming composition C2.

[Preparation Example 3] Preparation of composition C3 for retardation film formation

To 5.0 g of toluene, 1.0 g of polymer P3 was added and dissolved by stirring at room temperature for 1 hour. To this solution, 2.3 g of CHN was added and stirred to obtain a composition C3 for retardation film formation.

[Preparation Example 4] Preparation of composition C4 for retardation film formation

To 5.0 g of toluene, 1.0 g of polymer P4 was added and dissolved by stirring at room temperature for 1 hour. To this solution, 2.3 g of CHN was added and stirred to obtain a retardation film-forming composition C4.

[4] Evaluation of water vapor barrier property

[Example 1-1]

The composition C1 for forming a retardation film was spin-coated on an acetate film (manufactured by HOLBEIN ART MATERIALS) having a thickness of 80 mu m as a substrate and dried with a hot plate at 70 DEG C for 3 minutes to form a polymer layer having a thickness of 1,000 nm. Subsequently, the coating film surface was irradiated with ultraviolet rays of 313 nm through a polarizing plate at 10 mJ / cm 2, and then heated on a hot plate at 140 캜 for 10 minutes to produce a film F1 having a water vapor-barrier retardation film with a film thickness of 1,000 nm.

Using the resulting film having the vapor-barrier retardation film, the water vapor barrier property was evaluated by the following technique in accordance with various conditions of JIS Z 0208 " Water vapor permeability test method (cup method) of moisture-proof packaging material ".

Using a square film having a wetting area of 28.27 cm 2, about 20 g of calcium chloride was sealed as a moisture absorbent in a screw-tight type moisture-permeable cup, and the weighing operation was repeated at intervals of 1 hour or more. Respectively. The results are shown in Table 1.

Water vapor permeability [g / m 2 · day] = (m / s) / t

m: increasing mass in constant weighing interval (g)

s: permeable area (㎡)

t: constant interval time (h) / 24 (h)

[Example 1-2]

Except that the retardation film-forming composition C2 was used in place of the retardation film-forming composition C1 and the ultraviolet ray irradiation at 313 nm was changed to 4 mJ / cm2, a retardation film having a vapor- Film F2-1 was prepared and evaluated for water vapor barrier properties. The results are shown in Table 1.

[Example 1-3]

Except that the retardation film-forming composition C2 was used in place of the retardation film-forming composition C1 and the ultraviolet ray irradiation at 313 nm was changed to 7 mJ / cm2, a retardation film having a vapor- Film F2-2 was prepared and evaluated for water vapor barrier properties. The results are shown in Table 1.

[Example 1-4]

A film F2-3 having a water vapor-barrier retardation film adhered was produced in the same manner as in Example 1-1 except that the retardation film-forming composition C2 was used in place of the retardation film-forming composition C1 to evaluate the water vapor barrier property . The results are shown in Table 1.

[Example 1-5]

Except that the retardation film forming composition C3 was used in place of the retardation film forming composition C1 and the ultraviolet ray irradiation at 313 nm was changed to 100 mJ / cm2, a retardation film having a vapor- Film F3 was prepared and evaluated for water vapor barrier properties. The results are shown in Table 1.

[Example 1-6]

Except that the retardation film-forming composition C4 was used in place of the retardation film-forming composition C1 and the ultraviolet ray irradiation at 313 nm was changed to 100 mJ / cm2, the retardation film having the vapor- Film F4 was prepared and evaluated for water vapor barrier properties. The results are shown in Table 1.

[Comparative Example 1-1]

A film F1 'was produced in the same manner as in Example 1-1 except that irradiation with ultraviolet light was not performed, and the vapor barrier property was evaluated. The results are shown in Table 1.

[Comparative Example 1-2]

A film F2 'was produced in the same manner as in Example 1-4 except that the ultraviolet ray irradiation was not performed, and the vapor barrier property was evaluated. The results are shown in Table 1.

[Comparative Example 1-3]

A film F3 'was produced in the same manner as in Example 1-5 except that irradiation with ultraviolet light was not performed, and the vapor barrier property was evaluated. The results are shown in Table 1.

[Comparative Example 1-4]

A film F4 'was produced in the same manner as in Example 1-6 except that the ultraviolet ray irradiation was not performed, and the vapor barrier property was evaluated. The results are shown in Table 1.

The results are shown in Table 1. The vapor transmissivity when the retardation film is not formed is also shown in Table 1 as a reference.

[5] Evaluation of phase difference value

[Example 2-1]

The retardation film-forming composition C1 was spin-coated on a glass substrate having an ITO film of 40 mm length x 30 mm width x 0.7 mm thickness and dried for 3 minutes on a hot plate at 70 DEG C to form a polymer layer having a thickness of 1,000 nm Respectively. Subsequently, the coated film surface was irradiated with ultraviolet rays of 313 nm through a polarizing plate at 10 mJ / cm 2, and then heated on a hot plate at 140 캜 for 10 minutes to obtain a glass substrate G 1 having a retardation film with a thickness of 1,000 nm.

For the glass substrate having the retardation film thus obtained, the retardation value was evaluated using a Muller matrix-polar limiter (Axoscans, product name: Axoscan). The measurement wavelength was 550 nm and the measurement temperature was 23 占 폚. The results are shown in Table 2.

[Example 2-2]

A glass substrate G2 having a retardation film attached thereto was obtained in the same manner as in Example 2-1 except that the retardation film forming composition C2 was used in place of the retardation film forming composition C1 and the ultraviolet ray irradiation at 313 nm was set to 4 mJ / -1 was prepared, and the retardation value was evaluated. The results are shown in Table 2.

[Example 2-3]

A glass substrate G2 having a retardation film attached thereto was obtained in the same manner as in Example 2-1 except that the retardation film forming composition C2 was used in place of the retardation film forming composition C1 and the ultraviolet ray irradiation at 313 nm was changed to 7 mJ / -2 was prepared, and the retardation value was evaluated. The results are shown in Table 2.

[Example 2-4]

A glass substrate G2-3 having a retardation film attached thereto was produced in the same manner as in Example 2-1 except that the retardation film forming composition C2 was used in place of the retardation film forming composition C1 to evaluate the retardation value. The results are shown in Table 2.

[Example 2-5]

A glass substrate G3 having a retardation film attached thereto was obtained in the same manner as in Example 2-1 except that the retardation film forming composition C3 was used in place of the retardation film forming composition C1 and the ultraviolet ray irradiation at 313 nm was changed to 100 mJ / Was prepared, and the retardation value was evaluated. The results are shown in Table 2.

[Example 2-6]

Except that the retardation film forming composition C4 was used in place of the retardation film forming composition C 1 and the ultraviolet ray irradiation at 313 nm was changed to 100 mJ / cm 2. And the retardation value was evaluated. The results are shown in Table 2.

[Comparative Example 2-1]

A glass substrate G1 'with a retardation film attached thereto was produced in the same manner as in Example 2-1 except that the irradiation with ultraviolet light was not performed, and the retardation value was evaluated. The results are shown in Table 2.

[Comparative Example 2-2]

A glass substrate G2 'having a retardation film attached thereto was produced in the same manner as in Example 2-4, except that the irradiation with ultraviolet light was not performed, and the retardation value was evaluated. The results are shown in Table 2.

[Comparative Example 2-3]

A glass substrate G3 'having a retardation film attached thereto was produced in the same manner as in Example 2-5, except that the irradiation with ultraviolet light was not performed, and the retardation value was evaluated. The results are shown in Table 2.

[Comparative Example 2-4]

A glass substrate G4 'with a retardation film attached thereto was produced in the same manner as in Example 2-6 except that the irradiation with ultraviolet light was not performed, and the retardation value was evaluated. The results are shown in Table 2.

From the results shown in Tables 1 and 2, it was found that the retardation film of the present invention is excellent in water vapor barrier property and can also function as a retardation film.

Claims (19)

A retardation film having a water vapor barrier property, which comprises a liquid crystalline polymer having photosensitive side chains and has a film thickness of more than 300 nm but not more than 50,000 nm. The method according to claim 1,
Wherein the photosensitive side chain causes photo-crosslinking, photoisomerization, or light-free transition. 3. The method of claim 2,
Wherein the photosensitive side chain is at least one selected from the groups represented by the following formulas (1) to (6).

(Wherein, A ^1, A ² and A ³ are, each independently, a single _{bond, -O-, -CH 2 -, -C} (= O) -O-, -OC (= O) -, -C (= O) -NH-, -NH-C (= O) -, -CH = CH-C (= O) -O- or -OC (= O) -CH = CH-;
T ¹ represents an alkylene group having 1 to 12 carbon atoms which may be substituted with a halogen atom;
T ² represents a single bond or an alkylene group having 1 to 12 carbon atoms which may be substituted with a halogen atom;
Y ¹ represents a monovalent aromatic group selected from a phenyl group, a naphthyl group, a biphenyl group, a furanyl group and a pyrrolyl group, a monovalent cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, group represents a group formed by binding via a linking group a ^2, a part of hydrogen atoms bonded to the -COOR ⁰ these (R ⁰ represents a hydrogen atom or an alkyl group having a carbon number of _{1 ~ 5.), -NO 2} , -CN , -CH = C (CN) ₂ , -CH = CH-CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms;
Y ² is selected from a divalent aromatic group selected from a phenylene group, a naphthalenediyl group, a biphenylene group, a furandiyl group and a pyrrodiyl group, a divalent cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, represents a group of 2 to 6 groups formed by binding through a linking group is a ^2, a part of hydrogen atoms bonded to these _{-NO 2, -CN, -CH = C} (CN) 2, -CH = CH-CN, A halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;
R represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ¹ ;
X is a single bond, -C (= O) -O-, -OC (= O) -, -N = N-, -CH = CH-, -C = C-, O) -O- or -OC (= O) -CH = CH-; when X is 2 or more, each X may be the same or different;
C _ou represents a coumarin-6-yl group or a coumarin-7-yl group, and some of the hydrogen atoms bonding to these groups are -NO ₂ , -CN, -CH═C (CN) ₂ , A halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;
Q ¹ and Q ² each independently represent a divalent aromatic group selected from a phenylene group, a naphthalenediyl group, a biphenylylene group, a furandiyl group and a pyrrodiyl group, a divalent cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms , Or a group formed by bonding 2 to 6 groups selected from these substituents via a linking group A ² , but when X is -CH = CH-CO-O- or -O-CO-CH = CH- , Q ¹ or Q ² on the side bonded to -CH = CH- is a divalent aromatic group, and when Q ¹ is 2 or more, each Q ¹ may be the same or different, and when the number of Q ² is 2 or more, Each Q < ² > may be the same or different;
E represents -C (= O) -O- or -OC (= O) -;
W ¹ and W ² each independently represent a group selected from the group consisting of a phenylene group, a naphthalenediyl group, a biphenylene group, a furandiyl group, a pyrrodiyl group, or a group having 2 to 6 substituents selected therefrom via a linking group A ² ≪ / RTI >
a1 represents 0 or 1;
a2 represents an integer of 0 to 2;
When a1 and a2 are both 0 and T ² is a single bond, A ¹ represents a single bond;
and a1 is 1, T ^2, when the unity sum, A ² denotes a single bond;
b represents 0 or 1;
The dashed line represents the bonding hand with the main chain.) The method of claim 3,
Wherein the photosensitive side chain is selected from groups represented by the following formulas (7) to (10).

(Wherein A ¹ , A ² , A ³ , Y ¹ , Y ² , R, X and the broken line are the same as above, but when n is 0, A ² is a single bond;
R ¹ represents -NO _2, -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;
c represents an integer of 1 to 12;
m represents an integer of 0 to 2;
m1 and m2 each independently represent an integer of 1 to 3;
d represents an integer of 0 to 4;
and n represents an integer of 0 to 12.) The method of claim 3,
Wherein the photosensitive side chain is selected from groups represented by the following formulas (11) to (13).

(Wherein A ¹ , X, R and the broken line are the same as above;
R ¹ represents -NO ₂ , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;
c represents an integer of 1 to 12;
d represents an integer of 0 to 4;
e represents an integer of 0 to 6;
m represents an integer of 0 to 2;
and m1 represents an integer of 1 to 3.) The method of claim 3,
The retardation film having water vapor barrier property, wherein the photosensitive side chain is a group represented by the following formula (14) or (15).

(Wherein A ¹ , Y ¹ and the broken line are the same as above;
R ¹ represents -NO ₂ , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;
c represents an integer of 1 to 12,
d represents an integer of 0 to 4;
m1 and m2 each independently represent an integer of 1 to 3.) The method of claim 3,
The retardation film having water vapor barrier property, wherein the photosensitive side chain is a group represented by the following formula (16) or (17).

(Wherein A ¹ , X and the broken line are the same as above;
R ¹ represents -NO ₂ , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;
d represents an integer of 0 to 4;
f represents an integer of 0 to 5;
c represents an integer of 1 to 12;
and m represents an integer of 0 to 2.) The method of claim 3,
The retardation film having water vapor barrier property, wherein the photosensitive side chain is a group represented by the following formula (18) or (19).

(Wherein A ¹ , A ² , E, Y ¹ and the broken line are the same as above;
R ¹ represents -NO ₂ , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;
c represents an integer of 1 to 12;
d represents an integer of 0 to 4;
g represents an integer of 0 to 5;
m1 and m2 each independently represent an integer of 1 to 3.) The method of claim 3,
The retardation film having water vapor barrier property, wherein the photosensitive side chain is a group represented by the following formula (20).

(Wherein A ¹ , X, Y ¹ and the broken line are the same as above;
R ¹ represents -NO ₂ , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;
c represents an integer of 1 to 12; d represents an integer of 0 to 4;
and m represents an integer of 0 to 2.) 10. The method according to any one of claims 1 to 9,
Wherein the liquid crystalline polymer further comprises at least one liquid crystalline side chain selected from the groups represented by the following formulas (21) to (35).

(Wherein, A ¹ and A ² are, each independently, a single _{bond, -O-, -CH 2 -, -C} (= O) -O-, -OC (= O) -, -C (= O ) -NH-, -NH-C (= O) -, -CH = CH-C (= O) -O- or -OC (= O) -CH = CH-;
E represents -C (= O) -O- or -OC (= O) -;
R ¹ represents -NO ₂ , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;
R ² represents a hydrogen atom, -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furanyl group, A ring-containing group, a cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
Y ³ represents a group selected from the group consisting of a phenyl group, a naphthyl group, a biphenyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, ² , and a part of the hydrogen atoms bonded to these may be replaced by -NO ₂ , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;
Z ¹ and Z ² each independently represent a single bond, -C (= O) -, -CH ₂ O-, -CH = N- or -CF ₂ -;
c represents an integer of 1 to 12;
d represents an integer of 0 to 4;
e represents an integer of 0 to 6;
h represents an integer of 0 to 5;
k represents, independently of each other, an integer of 0 to 2, in the formulas (25) and (26), the sum of all k is 2 or more;
m1 and m2 each independently represent an integer of 1 to 3;
and m3 represents an integer of 1 to 3.) 11. The method of claim 10,
Wherein the liquid crystalline polymer comprises a repeating unit represented by the following formula (A) and a repeating unit represented by the following formula (B).

(Wherein R ^A is at least one species selected from the groups represented by the formulas (1) to (6) and R ^B is at least one species selected from the groups represented by the formulas (21) to (31) M ^A and M ^B each independently represent a group derived from a polymerizable group.) 12. The method of claim 11,
Wherein the group derived from the polymerizable group is at least one selected from groups represented by the following formulas.

(Wherein, R ^C is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a carboxyl group or represents a carboxylic group, R ^D is a single bond, -C (= O) -O-, -C (= O) - NH- or phenylene group, R ^E represents a hydroxyl group, an alkyl group or an alkoxy group of 1 to 10 carbon atoms, or a phenyl group, and the broken line represents a bond with R ^A or R ^B ) 13. The method according to any one of claims 1 to 12,
Wherein the liquid crystalline polymer exhibits liquid crystallinity at a temperature in the range of 50 to 300 占 폚. An organic electroluminescence display comprising the retardation film according to any one of claims 1 to 13. A step of applying a composition for forming a retardation film including a resin component containing a liquid crystalline polymer having photosensitive side chains and an organic solvent to a substrate to form a coating film having a film thickness of more than 300 nm but not more than 50,000 nm,
A step of irradiating the coating film with polarized ultraviolet light, and
A step of heating the film irradiated with the polarized ultraviolet rays to obtain a film having a film thickness of more than 300 nm but not more than 50,000 nm
Wherein the film has a water vapor barrier property. 16. The method of claim 15,
Wherein the photosensitive side chain causes photo-crosslinking, photoisomerization, or light-free transition. 17. The method of claim 16,
Wherein the photosensitive side chain is at least one selected from the groups represented by the following formulas (1) to (6).

(Wherein, A ^1, A ² and A ³ are, each independently, a single _{bond, -O-, -CH 2 -, -C} (= O) -O-, -OC (= O) -, -C (= O) -NH-, -NH-C (= O) -, -CH = CH-C (= O) -O- or -OC (= O) -CH = CH-;
T ¹ represents an alkylene group having 1 to 12 carbon atoms which may be substituted with a halogen atom;
T ² represents a single bond or an alkylene group having 1 to 12 carbon atoms which may be substituted with a halogen atom;
Y ¹ represents a monovalent aromatic group selected from a phenyl group, a naphthyl group, a biphenyl group, a furanyl group and a pyrrolyl group, a monovalent cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, group represents a group formed by binding via a linking group a ^2, a part of hydrogen atoms bonded to the -COOR ⁰ these (R ⁰ represents a hydrogen atom or an alkyl group having a carbon number of _{1 ~ 5.), -NO 2} , -CN , -CH = C (CN) ₂ , -CH = CH-CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms;
Y ² is selected from a divalent aromatic group selected from a phenylene group, a naphthalenediyl group, a biphenylene group, a furandiyl group and a pyrrodiyl group, a divalent cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, represents a group of 2 to 6 groups formed by binding through a linking group is a ^2, a part of hydrogen atoms bonded to these _{-NO 2, -CN, -CH = C} (CN) 2, -CH = CH-CN, A halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;
R represents a hydroxyl group, an alkoxy group having 1 to 6 carbon atoms, or the same definition as Y ¹ ;
X is a single bond, -C (= O) -O-, -OC (= O) -, -N = N-, -CH = CH-, -C = C-, O) -O- or -OC (= O) -CH = CH-; when X is 2 or more, each X may be the same or different;
C _ou represents a coumarin-6-yl group or a coumarin-7-yl group, and some of the hydrogen atoms bonding to these groups are -NO ₂ , -CN, -CH═C (CN) ₂ , A halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;
Q ¹ and Q ² each independently represent a divalent aromatic group selected from a phenylene group, a naphthalenediyl group, a biphenylylene group, a furandiyl group and a pyrrodiyl group, a divalent cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms , Or a group formed by bonding 2 to 6 groups selected from these substituents via a linking group A ² , but when X is -CH = CH-CO-O- or -O-CO-CH = CH- , Q ¹ or Q ² on the side bonded to -CH = CH- is a divalent aromatic group, and when Q ¹ is 2 or more, each Q ¹ may be the same or different, and when the number of Q ² is 2 or more, Each Q < ² > may be the same or different;
E represents -C (= O) -O- or -OC (= O) -;
W ¹ and W ² each independently represent a group selected from the group consisting of a phenylene group, a naphthalenediyl group, a biphenylene group, a furandiyl group, a pyrrodiyl group, or a group having 2 to 6 substituents selected therefrom via a linking group A ² ≪ / RTI >
a1 represents 0 or 1;
a2 represents an integer of 0 to 2;
When a1 and a2 are both 0 and T ² is a single bond, A ¹ represents a single bond;
and a1 is 1, T ^2, when the unity sum, A ² denotes a single bond;
b represents 0 or 1;
The dashed line represents the bonding hand with the main chain.) 18. The method according to any one of claims 14 to 17,
Wherein the liquid crystalline polymer further comprises at least one liquid crystalline side chain selected from the groups represented by the following formulas (21) to (35).

(Wherein, A ¹ and A ² are, each independently, a single _{bond, -O-, -CH 2 -, -C} (= O) -O-, -OC (= O) -, -C (= O ) -NH-, -NH-C (= O) -, -CH = CH-C (= O) -O- or -OC (= O) -CH = CH-;
E represents -C (= O) -O- or -OC (= O) -;
R ¹ represents -NO ₂ , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;
R ² represents a hydrogen atom, -NO ₂ , -CN, -CH═C (CN) ₂ , -CH═CH-CN, a halogen atom, a phenyl group, a naphthyl group, a biphenyl group, a furanyl group, A ring-containing group, a cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms;
Y ³ represents a group selected from the group consisting of a phenyl group, a naphthyl group, a biphenyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, a cyclic aliphatic hydrocarbon group having 5 to 8 carbon atoms, ² , and a part of the hydrogen atoms bonded to these may be replaced by -NO ₂ , -CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms;
Z ¹ and Z ² each independently represent a single bond, -C (= O) -, -CH ₂ O-, -CH = N- or -CF ₂ -;
c represents an integer of 1 to 12;
d represents an integer of 0 to 4;
e represents an integer of 0 to 6;
h represents an integer of 0 to 5;
k represents, independently of each other, an integer of 0 to 2, in the formulas (25) and (26), the sum of all k is 2 or more;
m1 and m2 each independently represent an integer of 1 to 3;
and m3 represents an integer of 1 to 3.) 19. The method according to any one of claims 14 to 18,
Wherein the temperature range in which the liquid crystalline polymer exhibits liquid crystallinity is 50 to 300 占 폚.