CN106459324B

CN106459324B - Cured film, which is formed, uses composition, oriented material and phase difference material

Info

Publication number: CN106459324B
Application number: CN201580034050.4A
Authority: CN
Inventors: 伊藤润; 汤川升志郎; 菅野裕太; 后藤耕平; 畑中真
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2014-06-30
Filing date: 2015-06-29
Publication date: 2019-09-27
Anticipated expiration: 2035-06-29
Also published as: JP6823295B2; WO2016002722A1; CN106459324A; CN110408159A; JPWO2016002722A1; JP2020019964A; KR20170023840A; CN110408159B; TWI678389B; JP6604483B2; KR102318651B1; TW201615715A

Abstract

The subject of the invention is to provide surface layer has the optical film, oriented material and the phase difference material using the oriented material of the cured film of excellent liquid crystal aligning and adaptation.Solution of the invention is a kind of cured film formation composition, oriented material, with phase difference material, the cured film formation composition is characterized in that, contain (A) ingredient, (B) ingredient and (C) ingredient, (A) ingredient: there is at least one of light orientation group and the compound of heat cross-linking group, (B) ingredient: the polymer comprising the repetitive unit with N- alkoxy methyl and the repetitive unit with the side chain comprising polymerism C=C double bond, (C) ingredient is selected from (C-1), (C-2) and at least one of (C-3) polymer, (C-1): having and be selected from hydroxyl, carboxyl, amide groups, the polymer of at least one of amino and alkoxysilyl substituent group, (C-2): there is the substituent group that thermal response can be carried out with (A) ingredient, And the polymer of self-crosslinking, (C-3): melamine resin can be carried out.

Description

Cured film, which is formed, uses composition, oriented material and phase difference material

Technical field

The present invention relates to cured film formation composition, oriented material and phase difference materials.

Background technique

In recent years, in the field of the display of the TV for having used liquid crystal display panel etc., as exerting for high performance Power constantly develops the 3D display device that can appreciate 3D rendering.In 3D display device, for example, the right side by making observer The visible right eye image of eye, makes the visible left eye image of the left eye of observer, so as to show with relief image.

Show that the mode of the 3D display device of 3D rendering is varied, as the mode for not needing special eyeglasses, it is known that biconvex Lens mode and disparity barrier mode etc..

Moreover, one of the mode of display for observing 3D rendering as observer's wearing spectacles, it is known that rotatory polarization glasses Mode etc. is (for example, referring to patent document 1.).

In the case where the 3D display device of rotatory polarization glasses mode, the display element of image is usually formed in liquid crystal display panel etc. Upper configuration phase difference material.On the phase difference material, 2 kinds of different phase difference regions of multiple phase difference characteristics are regularly matched respectively It sets, constitutes the phase difference material for foring pattern.In addition, below in the present specification, it will be to configure such phase difference characteristics The mode in different multiple phase difference regions and the phase difference material that has been patterned is known as patterning phase difference material.

It, can be by that will include polymerism about patterning phase difference material, such as disclosed in patent document 2 The phase difference material of liquid crystal carries out optical design and is formed to make.The optical design shape of phase difference material comprising polymerizable liquid crystal At, using the oriented material in liquid crystal display panel formed in known light orientation technology.That is, being arranged on substrate by light orientation The film that material is formed, 2 kinds of different polarisations of polarization direction are irradiated to it.Then, as the tropism control side for foring liquid crystal To the oriented material in 2 kinds of different liquid crystal aligning regions, optical alignment film is obtained.Coating includes polymerism liquid on the optical alignment film Brilliant solution shape phase difference material, realizes the orientation of polymerizable liquid crystal.Then, the polymerizable liquid crystal being orientated is solidified to form Pattern phase difference material.

Material in the oriented material for having used light orientation technology of liquid crystal display panel is formed, as available light orientation Material, it is known that side chain has acrylic resin, the polyimide resin etc. at the photodimerization such as cinnamoyl and chalcone base position. Report: these resins are by carrying out the performance of polarisation UV irradiation display control liquid crystal aligning (hereinafter also referred to as liquid crystal aligning Property.) (referring to 3~patent document of patent document 5.).

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 10-232365 bulletin

Patent document 2: Japanese Unexamined Patent Publication 2005-49865 bulletin

Patent document 3: No. 3611342 specifications of Japanese Patent Publication No.

Patent document 4: Japanese Unexamined Patent Publication 2009-058584 bulletin

Patent document 5: Japanese Unexamined Patent Application Publication 2001-517719 bulletin

Summary of the invention

Problems to be solved by the invention

As described above, patterning phase difference material is the layer for the polymerizable liquid crystal that will be had cured in the light as oriented material Alignment films superimposed layer and constitute.Moreover, the patterning phase difference material with such laminated construction can be with the lamination shape State is directly used in the composition of 3D display device.

3D display device is also sometimes used as home-use TV, it is desirable that high reliability, especially after prolonged durability. Therefore, for the member of formation of 3D display device, durability is also required.Therefore, in patterning phase difference material, with high precision Whiles carrying out optical design formation, have high light transmittance characteristic etc., long durability becomes required performance.

However, for previous patterning phase difference material, it is closely sealed between optical alignment film and polymerizable liquid crystal layer There are problems for property.For example, existing between optical alignment film and polymerizable liquid crystal layer and being easy for generating removing since formation initial stage Although the problem of or formed initial stage excellent adhesion, as time goes by, adaptation decline and be easy to produce removing Problem.

Wherein, as time goes by and removing generate, between optical alignment film and polymerizable liquid crystal layer becomes in reality Used in 3D display device defect, become make 3D display device display quality decline the reason of.It is therefore desirable to be able to carry out height The optical design of precision is formed, and optical transmission characteristics are excellent, and then the patterning phase difference material of excellent in te pins of durability.Special requirement exist Excellent adhesion between the optical alignment film and polymerizable liquid crystal layer at formation initial stage is provided simultaneously with and maintains this excellent close for a long time The durability of conjunction property (hereinafter, be closely sealed durability in the present specification.) patterning phase difference material.

The present invention be based on above understanding, result of study and propose.That is, the object of the present invention is to provide be suitable for Being formed has excellent liquid crystal aligning and optical transmission characteristics, and the cured film of the cured film of closely sealed excellent in te pins of durability is formed with combination Object.Especially it is to provide the cured film formation composition to form following cured films, the cured film is used as oriented material, And when being configured with polymerizable liquid crystal layer on it, excellent liquid crystal aligning and transmitance are shown, while can maintain for a long time With the adaptation between polymerizable liquid crystal layer, closely sealed excellent in te pins of durability.

The object of the present invention is to provide the orientation materials of liquid crystal aligning and excellent, the closely sealed excellent in te pins of durability of optical transmission characteristics Material.

The object of the present invention is to provide be able to carry out the phase difference material of high-precision optical design formation, excellent in te pins of durability Material.

Other objects and advantages of the present invention can be defined by below record.

The method used for solving the problem

1st scheme of the invention is related to a kind of cured film formation composition, contains (A) ingredient and (B) ingredient,

(A) ingredient is that have at least one of light orientation group and the compound of heat cross-linking group,

(B) ingredient is the polymer comprising following repetitive unit,

Repetitive unit with N- alkoxy methyl and

Repetitive unit with the side chain comprising polymerism C=C double bond.

In the 1st scheme of the invention, the light orientation group of (A) ingredient is preferably capable carrying out photodimerization or light is different The functional group of the structure of structure.

In the 1st scheme of the invention, the light orientation group of (A) ingredient is preferably cinnamoyl or azobenzene structure Group.

In the 1st scheme of the invention, preferably it also contains (C) ingredient, and (C) ingredient is selected from (C-1), (C-2) And at least one of (C-3) polymer,

(C-1): having selected from least one of hydroxyl, carboxyl, amide groups, amino and alkoxysilyl substituent group Polymer,

(C-2): the substituent group of thermal response can be carried out with (A) ingredient and can carry out the polymer of self-crosslinking by having,

(C-3): melamine formaldehyde resin.

In the 1st scheme of the invention, preferably it also contains (D) crosslinking catalyst.

In the 1st scheme of the invention, preferably it also contains (E) crosslinking agent.

In the 1st scheme of the invention, preferably in the polymer of (B) ingredient, the repetition list with N- alkoxy methyl Member there are ratios relative to 100 moles of whole repetitive units of the polymer is 40 moles of %~90 mole %, have comprising 100 moles of whole repetitive units there are ratio relative to the polymer of the repetitive unit of the side chain of polymerism C=C double bond are 10 moles of %~60 mole %.

In the 1st scheme of the invention, preferably the content of (A) ingredient and (B) ingredient than being 5:95~60 by quality ratio: 40。

In the 1st scheme of the invention, it is based on 100 mass parts of total amount of (A) ingredient and (B) ingredient, said curing film Formation preferably comprises 5 mass parts~500 mass parts (C) ingredient with composition.

2nd scheme of the invention is related to a kind of oriented material, which is characterized in that is the heat using the 1st scheme of the invention What cured film formation was obtained with composition.

3rd scheme of the invention is related to a kind of phase difference material, which is characterized in that is using by the 1st scheme of the invention Cured film formation composition obtain cured film and formed.

Invention effect

1st scheme according to the present invention is capable of providing a kind of cured film formation composition, be used for provide have it is excellent Light reaction efficiency and solvent resistance, can make on resin film polymerizable liquid crystal with high sensitivity be orientated take To material.

2nd scheme according to the present invention is capable of providing and has excellent light reaction efficiency and solvent resistance, even if in resin The oriented material that on film also polymerizable liquid crystal can be orientated with high sensitivity.

3rd scheme according to the present invention, being capable of providing on resin film can be with high efficiency formation and can be into The phase difference material that row optical design is formed.

Specific embodiment

As described above, in order to manufacture the patterning phase difference material of excellent durability, it is desirable that closely sealed excellent in te pins of durability Oriented material, the especially oriented material of the closely sealed excellent in te pins of durability between cured polymerizable liquid crystal layer.And, it is desirable that it is suitable Close the cured film formation composition for forming the oriented material of such performance.

Present inventor in response to above-mentioned and have made intensive studies, as a result, it has been found that, by with specific composition Cured film formation is excellent with the transmitance for the cured film that composition obtains, furthermore, it is possible to be used as display by polarisation exposure come Control the oriented material of the liquid crystal aligning of liquid crystal aligning.Moreover, the inventors have found that, it should be by the cured film with specific composition The cured film that formation is obtained with composition shows excellent closely sealed durable between the polymerizable liquid crystal layer of polymerizing curable thereon Property.It may be constructed by the cured film formation with specific composition with the cured film that composition obtains and polymerism that is, of the invention The optical alignment film of closely sealed excellent in te pins of durability between liquid crystal layer.

Below for cured film formation composition of the invention, in detail while enumerating the concrete example of ingredient etc. into Row explanation.Then, for the cured film and oriented material of the invention for using cured film formation composition of the invention and Using the oriented material, the phase difference material formed and liquid crystal display element etc. are illustrated.

Cured film formation of the invention uses composition can be containing (A) ingredient, (B) ingredient, (C) ingredient and as (D) The crosslinking catalyst of ingredient, (A) ingredient are at least one of the compound with light orientation group and heat cross-linking group Kind, (B) ingredient is comprising the repetitive unit with N- alkoxy methyl and with the side chain comprising polymerism C=C double bond Repetitive unit polymer, (C) ingredient be selected from least one of (C-1), (C-2) and (C-3) polymer, (C-1): there is the polymerization selected from least one of hydroxyl, carboxyl, amide groups, amino and alkoxysilyl substituent group Object, (C-2): the substituent group of thermal response can be carried out with (A) ingredient and can carry out the polymer of self-crosslinking, (C-3): trimerization by having Cyanogen amine-formaldehyde resin.Furthermore, it is possible to contain the crosslinking agent as (E) ingredient.In turn, in the model for not damaging effect of the invention In enclosing, other additives can be contained.Solvent can further be contained.

Illustrate the detailed content of each ingredient below.

[(A) ingredient]

It is with light orientation group and heat cross-linking group that cured film of the invention, which is formed with (A) ingredient in composition, Compound at least one.As (A) ingredient, polymer can be used, the compound other than polymer also can be used.? This, the compound other than so-called polymer specifically indicates the compound for not having repetitive unit in molecule, usually low molecule Compound.Therefore, (A) ingredient can be the polymer with light orientation group and heat cross-linking group at least one, At least one of compound other than polymer with light orientation group and heat cross-linking group has light orientation base The polymer of group and heat cross-linking group and the compound other than the polymer with light orientation group and heat cross-linking group Mixture.

(A) ingredient be the cured film by cured film formation composition acquisition of the invention is assigned light orientation at Point, in the present specification, (A) ingredient is also known as light orientation ingredient.

The detailed content for the case where explanation (A) ingredient is the compound other than polymer below.

In the case where the compound other than (A) ingredient is polymer, in general, aftermentioned (B) ingredient with based on Polymer phase ratio be low molecular weight light orientation ingredient.

In cured film formation composition of the invention, in the case where the compound other than (A) ingredient is polymer, (A) ingredient is the compound with light orientation group, and then it can be made with selected from hydroxyl, carboxyl, amide groups, amino With the compound of one of alkoxysilyl group.

In addition, in the present invention, so-called light orientation group generally refers to irradiate the property for playing orientation by light Functional group, it is representative to refer to the functional group for carrying out the structure position of photodimerization or photoisomerization.As other light orientations Property group, can enumerate for example cause light fries' rearrangement (photo Fries rearrangement) react functional group (illustrate Compound: benzoic acid ester compounds etc.), the group (exemplary compounds: cyclobutane ring etc.) for causing photolysis reactions etc..

(A) the progress photodimerization that can have as light orientation group of compound other than the polymer of ingredient Structure position is that can irradiate the position to form dimer by light, as its concrete example, can enumerate cinnamoyl, chalcone Base, cumarin base, anthryl etc..Wherein, from visible light region the transparency height, the reactive height of photodimerizationization, Preferably cinnamoyl.

In addition, the carry out light that can have as light orientation group of the compound other than the polymer of (A) ingredient is different The structure position of structure refers to that the structure position for becoming cis- body and trans- body by light irradiation can be lifted as its concrete example Position out comprising azobenzene structure, Stilbene structure etc..Wherein, from reactive height, preferably azobenzene structure.

With light orientation group and selected from one of hydroxyl, carboxyl, amide groups, amino and alkoxysilyl base Compound other than the polymer of group is for example, following formula compound represented.

In previously described formula, A¹And A²Separately indicate hydrogen atom or methyl.

X¹¹It is selected from singly-bound, ehter bond, ester bond, amido bond, urea bond, urethane bond, amino bond, carbonyl or their group One kind or two or more key in conjunction, or selected from carbon atom number be 1~18 alkylidene, phenylene, biphenylene or they Structure made of 1~3 kind of substituent group in combination is closed via the one kind or two or more bond, is also possible to foregoing substituents Via previous key be separately connected it is multiple made of structure.

X¹²Indicate hydrogen atom, halogen atom, cyano, alkyl, phenyl, xenyl or the cyclohexyl that carbon atom number is 1~18. At this point, two or more group in alkyl, phenyl, xenyl and cyclohexyl that carbon atom number is 1~18 can via covalent bond, Ehter bond, ester bond, amido bond or urea bond and combine.

X¹³Indicate the alkylthio group that alkoxy, carbon atom number that hydroxyl, sulfydryl, carbon atom number are 1~10 are 1~10, benzene oxygen Base, biphenylyloxy or phenyl.

X¹⁴Indicate singly-bound, alkylidene, the aromatic series ring group of divalent or the aliphatic ring group of divalent that carbon atom number is 1~20. Here, the alkylidene that carbon atom number is 1~20 can be branched and be also possible to straight-chain.

X¹⁵Indicate hydroxyl, carboxyl, amide groups, amino or alkoxysilyl.But in X¹⁴When for singly-bound, X¹⁵For hydroxyl Base or amino.

X indicates singly-bound, oxygen atom or sulphur atom.But in X¹⁴When for singly-bound, X is also singly-bound.

In addition, the phenyl ring can be 1~4 selected from carbon atom number in the case where including phenyl ring in these substituent groups Identical or different one or more in the alkoxy, halogen atom, trifluoromethyl and cyano that alkyl, carbon atom number are 1~4 Substituent group replaces.

In above-mentioned formula, R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷And R¹⁸Separately indicate hydrogen atom, carbon atom number 1 ~4 alkyl, alkoxy, halogen atom, trifluoromethyl or the cyano that carbon atom number is 1~4.

In addition, the alkyl for being 1~18 as carbon atom number defined in above-mentioned, can enumerate for example, methyl, ethyl, positive third Base, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, n-pentyl, 1- methyl-normal-butyl, 2- methyl-normal-butyl, 3- first Base-normal-butyl, 1,1- dimethyl-n-propyl, 1,2- dimethyl-n-propyl, 2,2- dimethyl-n-propyl, 1- ethyl-positive third Base, n-hexyl, 1- methyl-n-pentyl, 2- methyl-n-pentyl, 3- methyl-n-pentyl, 4- methyl-n-pentyl, 1,1- dimethyl- Normal-butyl, 1,2- dimethyl-normal-butyl, 1,3- dimethyl-normal-butyl, 2,2- dimethyl-normal-butyl, 2,3- dimethyl-positive fourth Base, 3,3- dimethyl-normal-butyl, 1- ethyl-normal-butyl, 2- ethyl-normal-butyl, 1,1,2- trimethyl-n-propyl, 1,2,2- tri- Methyl-n-propyl, 1- ethyl -1- methyl-n-propyl, 1- Ethyl-2-Methyl-n-propyl, n-heptyl, 1- methyl-n-hexyl, 2- Methyl-n-hexyl, 3- methyl-n-hexyl, 1,1- dimethyl-n-pentyl, 1,2- dimethyl-n-pentyl, 1,3- dimethyl-positive penta Base, 2,2- dimethyl-n-pentyl, 2,3- dimethyl-n-pentyl, 3,3- dimethyl-n-pentyl, 1- ethyl-n-pentyl, 2- second Base-n-pentyl, 3- ethyl-n-pentyl, 1- methyl-1-ethyl-normal-butyl, 1- methyl-2- ethyl-normal-butyl, 1- ethyl-2- first Base-normal-butyl, 2- methyl -2- ethyl-normal-butyl, 2- ethyl -3- methyl-normal-butyl, n-octyl, 1- methyl-n-heptyl, 2- first Base-n-heptyl, 3- methyl-n-heptyl, 1,1- dimethyl-n-hexyl, 1,2- dimethyl-n-hexyl, 1,3- dimethyl-just oneself Base, 2,2- dimethyl-n-hexyl, 2,3- dimethyl-n-hexyl, 3,3- dimethyl-n-hexyl, 1- ethyl-n-hexyl, 2- second Base-n-hexyl, 3- ethyl-n-hexyl, 1- methyl-1-ethyl-n-pentyl, 1- methyl-2- ethyl-n-pentyl, 1- methyl-3- second Base-n-pentyl, 2- methyl -2- ethyl-n-pentyl, 2- methyl -3- ethyl-n-pentyl, 3- methyl -3- ethyl-n-pentyl, positive nonyl Base, positive decyl, n-undecane base, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base, n-hexadecyl, N-heptadecane base and n-octadecane base etc..The alkyl for being 1~4 similarly as carbon atom number, can enumerate enumerated group In have the group of corresponding carbon atom number.In addition, as carbon atom number be 1~10 alkoxy, carbon atom number be 1~4 alkane Oxygroup, the alkylthio group that carbon atom number is 1~10, can enumerate in group obtained by enumerated alkyl is aoxidized or vulcanized There is the group of corresponding carbon atom number.In turn, the alkylidene for being 1~20 as carbon atom number, can enumerate from abovementioned alkyl and Remove bivalent group obtained by 1 hydrogen atom in the alkyl that the carbon atom numbers such as NSC 77136 base, n-eicosane base are 1~20.

As the concrete example of the compound other than the polymer with light orientation group and hydroxyl of (A) ingredient, such as As the compound other than above-mentioned formula [A11]~[A15] compound represented and the formula, can enumerate for example, 4- (8- hydroxyl is pungent Base oxygroup) methyl cinnamate, 4- (6- hydroxyl hexyl oxygroup) methyl cinnamate, 4- (4- hydroxybutyl oxygroup) methyl cinnamate, 4- (3- hydroxypropyl oxygroup) methyl cinnamate, 4- (2- hydroxyethyl oxygroup) methyl cinnamate, 4- hydroxymethyl oxygroup cortex cinnamomi Sour methyl esters, 4- hydroxy-methyl cinnamate, 4- (8- hydroxy octyl oxygroup) ethyl cinnamate, 4- (6- hydroxyl hexyl oxygroup) cinnamic acid Ethyl ester, 4- (4- hydroxybutyl oxygroup) ethyl cinnamate, 4- (3- hydroxypropyl oxygroup) ethyl cinnamate, 4- (2- hydroxyethyl Oxygroup) ethyl cinnamate, 4- hydroxymethyl oxygroup ethyl cinnamate, 4- hydroxy cinnamate acetoacetic ester, 4- (8- hydroxy octyl oxygroup) Phenyl cinnamate, 4- (6- hydroxyl hexyl oxygroup) phenyl cinnamate, 4- (4- hydroxybutyl oxygroup) phenyl cinnamate, 4- (3- hydroxyl Base propyl oxygroup) phenyl cinnamate, 4- (2- hydroxyethyl oxygroup) phenyl cinnamate, 4- hydroxymethyl oxygroup phenyl cinnamate, 4- hydroxy cinnamate acid phenenyl ester, 4- (8- hydroxy octyl oxygroup) cinnamic acid Biphenyl Ester, 4- (6- hydroxyl hexyl oxygroup) cinnamic acid biphenyl Ester, 4- (4- hydroxybutyl oxygroup) cinnamic acid Biphenyl Ester, 4- (3- hydroxypropyl oxygroup) cinnamic acid Biphenyl Ester, 4- (2- hydroxyl second Base oxygroup) cinnamic acid Biphenyl Ester, 4- hydroxymethyl oxygroup cinnamic acid Biphenyl Ester, 4- hydroxycinnamic acid Biphenyl Ester, cinnamic acid 8- hydroxyl Base monooctyl ester, the own ester of cinnamic acid 6- hydroxyl, cinnamic acid 4- hydroxybutyl, cinnamic acid 3- hydroxy propyl ester, cinnamic acid 2- hydroxy methacrylate, meat Cinnamic acid hydroxy methyl, 4- (8- hydroxy octyl oxygroup) azobenzene, 4- (6- hydroxyl hexyl oxygroup) azobenzene, 4- (4- hydroxybutyl Oxygroup) azobenzene, 4- (3- hydroxypropyl oxygroup) azobenzene, 4- (2- hydroxyethyl oxygroup) azobenzene, 4- hydroxymethyl oxygroup Azobenzene, 4- hydroxyazobenzene, 4- (8- hydroxy octyl oxygroup) chalcone, 4- (6- hydroxyl hexyl oxygroup) chalcone, 4- (4- hydroxyl Base butyl oxygroup) chalcone, 4- (3- hydroxypropyl oxygroup) chalcone, 4- (2- hydroxyethyl oxygroup) chalcone, 4- hydroxyl first Base oxygroup chalcone, 4- hydroxy chalcone, 4 '-(8- hydroxy octyl oxygroup) chalcone, 4 '-(6- hydroxyl hexyl oxygroups) look into ear Ketone, 4 '-(4- hydroxybutyl oxygroup) chalcone, 4 '-(3- hydroxypropyl oxygroup) chalcone, 4 '-(2- hydroxyethyl oxygroups) are looked into Ear ketone, 4 '-hydroxymethyl oxygroup chalcone, 4'-hydroxychalcone, 7- (8- hydroxy octyl oxygroup) cumarin, 7- (6- hydroxyl oneself Base oxygroup) cumarin, 7- (4- hydroxybutyl oxygroup) cumarin, 7- (3- hydroxypropyl oxygroup) cumarin, 7- (2- hydroxyethyl Oxygroup) cumarin, 7- hydroxymethyl oxygroup cumarin, umbelliferone, 6- hydroxy octyl oxygroup cumarin, 6- hydroxyl hexyl Oxygroup cumarin, 6- (4- hydroxybutyl oxygroup) cumarin, 6- (3- hydroxypropyl oxygroup) cumarin, 6- (2- hydroxyethyl oxygen Base) cumarin, 6- hydroxymethyl oxygroup cumarin, 6- Hydroxycoumarin, 4- [4- (8- hydroxy octyl oxygroup) benzoyl] meat Acid methylester, 4- [4- (6- hydroxyl hexyl oxygroup) benzoyl] methyl cinnamate, 4- [4- (4- hydroxybutyl oxygroup) benzoyl Base] methyl cinnamate, 4- [4- (3- hydroxypropyl oxygroup) benzoyl] methyl cinnamate, 4- [4- (2- hydroxyethyl oxygroup) Benzoyl] methyl cinnamate, 4- [4- hydroxymethyl oxygroup benzoyl] methyl cinnamate, 4- [4- hydroxy benzoyl] meat Acid methylester, 4- [4- (8- hydroxy octyl oxygroup) benzoyl] ethyl cinnamate, 4- [4- (6- hydroxyl hexyl oxygroup) benzoyl Base] ethyl cinnamate, 4- [4- (4- hydroxybutyl oxygroup) benzoyl] ethyl cinnamate, 4- [4- (3- hydroxypropyl oxygroup) Benzoyl] ethyl cinnamate, 4- [4- (2- hydroxyethyl oxygroup) benzoyl] ethyl cinnamate, 4- [4- hydroxymethyl oxygen Base benzoyl] ethyl cinnamate, 4- [4- hydroxy benzoyl] ethyl cinnamate, 4- [4- (8- hydroxy octyl oxygroup) benzene first Acyl group] cortex cinnamomi tert-butyl acrylate, 4- [4- (6- hydroxyl hexyl oxygroup) benzoyl] cortex cinnamomi tert-butyl acrylate, 4- [4- (4- hydroxybutyl Oxygroup) benzoyl] cortex cinnamomi tert-butyl acrylate, 4- [4- (3- hydroxypropyl oxygroup) benzoyl] cortex cinnamomi tert-butyl acrylate, 4- [4- (2- hydroxyethyl oxygroup) benzoyl] cortex cinnamomi tert-butyl acrylate, 4- [4- hydroxymethyl oxygroup benzoyl] cortex cinnamomi tert-butyl acrylate, 4- [4- (8- hydroxy octyl oxygroup) benzoyl] phenyl cinnamate, 4- [4- (6- hydroxyl hexyl oxygroup) benzoyl] cinnamic acid Phenyl ester, 4- [4- (4- hydroxybutyl oxygroup) benzoyl] phenyl cinnamate, 4- [4- (3- hydroxypropyl oxygroup) benzoyl] Phenyl cinnamate, 4- [4- (2- hydroxyethyl oxygroup) benzoyl] phenyl cinnamate, 4- [4- hydroxymethyl oxygroup benzoyl Base] phenyl cinnamate, 4- [4- hydroxy benzoyl] phenyl cinnamate, 4- [4- (8- hydroxy octyl oxygroup) benzoyl] cortex cinnamomi Sour Biphenyl Ester, 4- [4- (6- hydroxyl hexyl oxygroup) benzoyl] cinnamic acid Biphenyl Ester, 4- [4- (4- hydroxybutyl oxygroup) benzene first Acyl group] cinnamic acid Biphenyl Ester, 4- [4- (3- hydroxypropyl oxygroup) benzoyl] cinnamic acid Biphenyl Ester, 4- [4- (2- hydroxyethyl Oxygroup) benzoyl] cinnamic acid Biphenyl Ester, 4- [4- hydroxymethyl oxygroup benzoyl] cinnamic acid Biphenyl Ester, 4- [4- hydroxy benzenes Formoxyl] cinnamic acid Biphenyl Ester, 4- benzoyl cinnamic acid 8- hydroxyl monooctyl ester, the own ester of 4- benzoyl cinnamic acid 6- hydroxyl, 4- Benzoyl cinnamic acid 4- hydroxybutyl, 4- benzoyl cinnamic acid 3- hydroxy propyl ester, 4- benzoyl cinnamic acid 2- hydroxyl second Ester, 4- benzoyl cinnamic acid hydroxy methyl, 4- [4- (8- hydroxy octyl oxygroup) benzoyl] chalcone, 4- [4- (6- hydroxyl Hexyl oxygroup) benzoyl] chalcone, 4- [4- (4- hydroxybutyl oxygroup) benzoyl] chalcone, 4- [4- (3- hydroxyl third Base oxygroup) benzoyl] chalcone, 4- [4- (2- hydroxyethyl oxygroup) benzoyl] chalcone, 4- (4- hydroxymethyl oxygroup Benzoyl) chalcone, 4- (4- hydroxy benzoyl) chalcone, 4 '-[4- (8- hydroxy octyl oxygroup) benzoyls] look into ear Ketone, 4 '-[4- (6- hydroxyl hexyl oxygroup) benzoyl] chalcone, 4 '-[4- (4- hydroxybutyl oxygroup) benzoyls] look into ear Ketone, 4 '-[4- (3- hydroxypropyl oxygroup) benzoyl] chalcone, 4 '-[4- (2- hydroxyethyl oxygroup) benzoyls] look into ear Ketone, 4 '-(4- hydroxymethyl oxygroup benzoyl) chalcone, 4 '-(4- hydroxy benzoyl) chalcone etc..

As the concrete example of the compound other than (A) ingredient, polymer with light orientation group and carboxyl, can lift Cinnamic acid, ferulic acid, 4- methoxy cinnamic acid, 4- ethoxy-cinnamic acid, 4- n-propyl oxygroup cinnamic acid, 3,4- dimethoxy out Cinnamic acid, coumarin-3-carboxylic acid, 4- (N, N- dimethylamino) cinnamic acid etc..

It, can as the concrete example of the compound other than (A) ingredient, polymer with light orientation group and amide groups Enumerate cinnamic acid, 4- methyl cinnamic acid amide, 4- ethyl-cinnamic acid amide, 4- methoxy cinnamic acid amide, 4- ethyoxyl Cinnamic acid etc..

As the concrete example of the compound other than (A) ingredient, polymer with light orientation group and amino, can lift 4- amino-cinnamic acid methyl esters, 4- amino cinnamate, 3- amino-cinnamic acid methyl esters, 3- amino cinnamate etc. out.

As the compound other than (A) ingredient, polymer with light orientation group and alkoxysilyl Concrete example can enumerate 4- (3- trimethoxy-silylpropyl oxygroup) methyl cinnamate, 4- (3- triethoxysilyl third Base oxygroup) methyl cinnamate, 4- (3- trimethoxy-silylpropyl oxygroup) ethyl cinnamate, 4- (3- triethoxy first silicon Alkyl propyl oxygroup) ethyl cinnamate, 4- (3- trimethoxysilyl hexyl oxygroup) methyl cinnamate, 4- (tri- ethoxy of 3- Base silicyl hexyl oxygroup) methyl cinnamate, 4- (3- trimethoxysilyl hexyl oxygroup) ethyl cinnamate and 4- (3- Triethoxysilyl hexyl oxygroup) ethyl cinnamate etc..

As (A) ingredient, further preferably the light orientation position shown in following formula (1) and heat reactivity position are tied The compound other than polymer obtained by polymerizable group is combined via spacer on group obtained by conjunction.

(in formula, R¹⁰¹Indicate hydroxyl, amino, hydroxyphenoxy, carboxyphenoxy, amino-benzene oxygen, amino carbonyl benzene oxygen Base, phenyl amino, hydroxyphenylamino, carboxyl phenyl amino, aminophenyiamino, hydroxyalkylamino or bis- (hydroxy alkyl) Amino, X¹⁰¹Indicate that phenylene, the phenyl ring in the definition of these substituent groups can be substituted with a substituent.)

Substituent group in the case where being substituted with a substituent as phenyl ring can enumerate methyl, ethyl, propyl, butyl, different The alkyl such as butyl；The alkylhalide groups such as trifluoromethyl；The alkoxies such as methoxyl group, ethyoxyl；The halogen atoms such as iodine, bromine, chlorine, fluorine；Cyano； Nitro etc..

Above-mentioned R¹⁰¹In, preferably hydroxyl and amino, particularly preferably hydroxyl.

As spacer, the divalent in straight-chain alkylidene, branched alkylidene, cyclic alkylidene and phenylene is indicated The group that group or multiple bivalent groups are combined into.In this case, each other as the bivalent group of composition spacer Between key, the key between group shown in spacer and above-mentioned formula (1), the key between spacer and polymerizable group, can lift Singly-bound, ester bond, amido bond, urea bond or ehter bond out.In the case where above-mentioned bivalent group is multiple, bivalent group each other can phase Same or different, in the case where above-mentioned key is multiple, key each other can be identical or different.

As such (A) ingredient, at light orientation position in conjunction with heat reactivity position obtained by combine on group The concrete example of monomer obtained by polymerizable group, can enumerate 4- (6- Methacryloxyhexyl -1- oxygroup) cinnamic acid, 4- (6- acryloxy hexyl -1- oxygroup) cinnamic acid, 4- (3- methacryloxypropyl -1- oxygroup) cinnamic acid, 4- (4- (3- methacryloxypropyl -1- oxygroup) acryloxy) benzoic acid, 4- (4- (6- Methacryloxyhexyl -1- Oxygroup) benzoyl oxygroup) cinnamic acid, 4- (6- Methacryloxyhexyl -1- oxygroup) cinnamamide, 4- (6- methyl-prop Alkene acyloxy hexyl -1- oxygroup)-N- (4- cyano-phenyl) cinnamamide, 4- (6- Methacryloxyhexyl -1- oxygroup) - Bis- hydroxyethyl cinnamamides of N- etc..

Light orientation ingredient as the compound other than the polymer of (A) ingredient can enumerate more than concrete example, but not It is limited by these concrete examples.

The detailed content when polymer that (A) ingredient is polymer, i.e. high molecular weight will be illustrated next.

The case where (A) ingredient contained in cured film formation composition of the invention is the polymer of high molecular weight Under, preferably (A) ingredient is the polymer with light orientation group, that is, has the carry out photodimerization as light orientation group The polymer of the functional group of the structure position of change or photoisomerization, particularly preferably at least with the acrylic acid series at photodimerization position Copolymer.And then preferably, other than photodimerization position, have and be selected from hydroxyl, carboxyl, amide groups, amino and alcoxyl The acrylic copolymer of one of base silicyl group (hereinafter, heat cross-linking position is also referred to as including these groups) Object.

In the present invention, so-called acrylic acid series copolymer is that acrylate, methacrylate, styrene etc. is instigated to have There is copolymer obtained by the monomer polymerization of unsaturated double-bond.

(A) acrylic acid series copolymer with photodimerization position and heat cross-linking position of ingredient is (hereinafter also referred to specific Copolymer.As long as) acrylic acid series copolymer with the structure being related to, for constituting the high score of acrylic acid series copolymer The skeleton of the main chain of son and the type of side chain etc. are not particularly limited.

As photodimerization position, cinnamoyl, chalcone base, cumarin base, anthryl etc. can be enumerated.Wherein, from The height and the reactive height of photodimerizationization of the transparency in light region are set out, preferably cinnamoyl.Meat more preferably Osmanthus acyl group and substituent group comprising cinnamoyl structure, can enumerate structure shown in following formula [1] or formula [2].In addition, in this explanation In book, the phenyl ring in cinnamoyl is that the group of naphthalene nucleus is also contained in " cinnamoyl " and " substituent group comprising cinnamoyl structure " In.

In above-mentioned formula [1], X¹Indicate hydrogen atom, alkyl, phenyl or the xenyl that carbon atom number is 1~18.At this point, phenyl It can be replaced by any one of halogen atom and cyano with xenyl.As carbon atom number be 1~18 alkyl, can enumerate with The alkyl same group of group illustrated by among the above for being 1~18 as carbon atom number.

In above-mentioned formula [2], X²Indicate hydrogen atom, cyano, the alkyl that carbon atom number is 1~18, phenyl, xenyl, hexamethylene Base.The alkyl for being 1~18 as carbon atom number, with the alkyl group illustrated by among the above for being 1~18 as carbon atom number Same group.At this point, carbon atom number be 1~18 alkyl, phenyl, xenyl, cyclohexyl can via be selected from covalent bond, ether One kind or two or more key in key, ester bond, amido bond, urea bond, urethane bond, amino bond, carbonyl or their combination And it combines a variety of.

In above-mentioned formula [1] and formula [2], in A expression [A1], formula [A2], formula [A3], formula [A4], formula [A5] and formula [A6] It is any.

In above-mentioned formula [A1], formula [A2], formula [A3], formula [A4], formula [A5] and formula [A6], R³¹、R³²、R³³、R³⁴、R³⁵、R³⁶、 R³⁷And R³⁸Separately indicate the alkoxy, halogen that alkyl, carbon atom number that hydrogen atom, carbon atom number are 1~4 are 1~4 Atom, trifluoromethyl or cyano.

Heat cross-linking position is that the position by heating in conjunction with (B) ingredient can enumerate hydroxyl, carboxylic as its concrete example Base, amide groups, amino, alkoxysilyl etc..

(A) weight average molecular weight of the acrylic acid series copolymer of ingredient is preferably 3,000~200,000.If Weight-average molecular Amount is excessive more than 200,000, then dissolubility in a solvent declines sometimes, and operability declines sometimes, on the other hand, such as Fruit weight average molecular weight is too small less than 3,000, then solidification is insufficient sometimes upon thermal curing, and solvent resistance can decline, Huo Zhenai It is hot to decline.

(A) in the synthetic method of the acrylic acid series copolymer with photodimerization position and heat cross-linking position of ingredient, make The method that monomer with photodimerization position and the monomer with heat cross-linking position are copolymerized is easy.

As the monomer with photodimerization position, can enumerate for example, have cinnamoyl, chalcone base, cumarin base, The monomer of anthryl etc..Wherein, the height and the reactive height of photodimerizationization of the transparency from visible light region, it is special Not preferably with the monomer of cinnamoyl.

Wherein, more preferably there is the cinnamoyl of structure shown in above-mentioned formula [1] or formula [2] and include cinnamoyl structure The monomer of substituent group.If the concrete example of such monomer is enumerated, for monomer shown in following formula [3] or formula [4].

In above-mentioned formula [3], X¹Indicate hydrogen atom, alkyl, phenyl or the xenyl that carbon atom number is 1~18.At this point, phenyl It can be replaced by any one of halogen atom and cyano with xenyl.As carbon atom number be 1~18 alkyl, can enumerate with The alkyl same group of group illustrated by among the above for being 1~18 as carbon atom number.

L¹And L²Separately indicate covalent bond, ehter bond, ester bond, amido bond, urea bond or urethane bond.

In above-mentioned formula [4], X²Indicate hydrogen atom, cyano, the alkyl that carbon atom number is 1~18, phenyl, xenyl, hexamethylene Base.The alkyl for being 1~18 as carbon atom number, can enumerate be 1~18 as carbon atom number alkyl illustrated among the above The same group of group.At this point, carbon atom number be 1~18 alkyl, phenyl, xenyl, cyclohexyl can via covalent bond, Ehter bond, ester bond, amido bond, urea bond are combined.

In above-mentioned formula [3] and formula [4], X³And X⁵Separately indicate singly-bound, the alkylidene that carbon atom number is 1~20,2 The aliphatic ring of the aromatic ring of valence, divalent.Here, the alkylidene that carbon atom number is 1~20 can be branched or straight-chain. The alkylidene for being 1~20 as carbon atom number, can enumerate be 1~20 as carbon atom number alkylidene as defined among the above The same group of group.

In above-mentioned formula [3] and formula [4], X⁴And X⁶Indicate polymerizable group.As the concrete example of the polymerizable group, can lift Out for example, acryloyl group, methylacryloyl, styryl, dimaleoyl imino, acrylamido, methacryl amido Deng.

In above-mentioned formula [3] and formula [4], A expression [A1], formula [A2], formula [A3], formula [A4], formula in the same manner as aforementioned Any one of [A5] and formula [A6].

As the monomer with heat cross-linking position, can enumerate for example, acrylic acid 2- hydroxy methacrylate, methacrylic acid 2- hydroxyl Ethyl ester, acrylic acid 2- hydroxy propyl ester, methacrylic acid 2- hydroxy propyl ester, acrylic acid 4- hydroxybutyl, methacrylic acid 4- hydroxyl Butyl ester, acrylic acid 2,3- dihydroxy propyl ester, methacrylic acid 2,3- dihydroxy propyl ester, diethylene glycol monoacrylate, diethyl two Alcohol monomethacrylates, caprolactone 2- (acryloxy) ethyl ester, caprolactone 2- (methacryloxy) ethyl ester, poly- (second Glycol) ethyl ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, 5- acryloxy -6- hydroxy norbomene - 2- carboxyl -6- lactone, 5- methacryloxy -6- hydroxy norbomene -2- carboxyl -6- lactone etc. have the monomer of hydroxyl； Acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloxy) ethyl) phthalic acid ester, mono- (2- (methacryl Oxygroup) ethyl) phthalic acid ester, N- (carboxyl phenyl) maleimide, N- (carboxyl phenyl) Methacrylamide, N- (carboxyl Phenyl) monomer with carboxyl such as acrylamide；Hydroxy styrenes, N- (hydroxy phenyl) Methacrylamide, N- (hydroxy benzenes Base) list with phenolic hydroxyl group such as acrylamide, N- (hydroxy phenyl) maleimide, N- (hydroxy phenyl) maleimide Body；Acrylamide, Methacrylamide etc. have the monomer of amide groups；Methacryloxypropyl trimethoxy silane, first Base acryloxypropyl triethoxysilane, acryloyloxypropyltrimethoxysilane, three ethoxy of acryloxypropyl Base silane etc. has the monomer etc. of alkoxysilyl.

About the monomer used to obtain specific copolymer with photodimerization position and there is heat cross-linking position The usage amount of monomer photodimerization portion is had based on the total amount of the whole monomers used to obtain specific copolymer The monomer of position is preferably the 40 mass % of mass %~95, and the monomer with heat cross-linking position is preferably 5 mass of mass %~60 %. By the 40 mass % of content of monomer or more for making that there is photodimerization position, highly sensitive and good liquid crystal can be assigned and taken Tropism.On the other hand, by making 95 mass % of the content of monomer with photodimerization position hereinafter, sufficient heat can be assigned Curability is able to maintain that highly sensitive and good liquid crystal aligning.

In addition, in cured film formation composition of the invention, when obtaining specific copolymer, can be used together can be with The monomer that monomer with photodimerization position and heat cross-linking position (being also referred to as particular functional group below) is copolymerized (hereinafter also referred to the monomer of non-reacted functional group).

As the concrete example of such monomer, acrylate compounds, methacrylate compound, Malaysia acyl can be enumerated Group with imine moiety, acrylamide compound, acrylonitrile, maleic anhydride, distyryl compound and vinyl compound etc..

The concrete example of above-mentioned monomer is enumerated below, but is not limited by these examples.

As above-mentioned acrylate compounds, can enumerate for example, methyl acrylate, ethyl acrylate, isopropyl acrylate, Benzyl acrylate, acrylic acid naphthalene ester, acrylic acid anthracene ester, acrylic acid anthrylmethyl, phenyl acrylate, glycidyl acrylate, Acrylic acid 2,2,2- trifluoro ethyl ester, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, acrylic acid 2- methoxyl group Ethyl ester, methoxyethyl triglycol ester, acrylic acid 2- ethoxy ethyl ester, tetrahydrofurfuryl acrylate, acrylic acid 3- methoxyl group Butyl ester, 2- methyl -2- adamantyl acrylate, 2- propyl -2- adamantyl acrylate, acrylic acid 8- methyl -8- tricyclic Last of the ten Heavenly stems ester and acrylic acid 8- ethyl -8- tricyclodecyl etc..

As above-mentioned methacrylate compound, can enumerate for example, methyl methacrylate, ethyl methacrylate, Isopropyl methacrylate, benzyl methacrylate, methacrylic acid naphthalene ester, methacrylic acid anthracene ester, methacrylic acid anthryl Methyl esters, phenyl methacrylate, glycidyl methacrylate, methacrylic acid 2,2,2- trifluoro ethyl ester, methacrylic acid The tert-butyl ester, cyclohexyl methacrylate, isobornyl methacrylate, methacrylic acid 2- methoxy acrylate, methacrylic acid Methoxy triethylene ester, methacrylic acid 2- ethoxy ethyl ester, tetrahydrofurfuryl methacrylate, methacrylic acid 3- methoxyl group Butyl ester, 2-Methacryloyloxy-2-methyladamantane, gamma-butyrolacton methacrylate, methacrylic acid 2- propyl -2- gold Rigid alkyl ester, methacrylic acid 8- methyl -8- tricyclodecyl and methacrylic acid 8- ethyl -8- tricyclodecyl etc..

As above-mentioned vinyl compound, can enumerate for example, methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, second Alkenyl carbazole, allyl glycidyl ether, 3- vinyl -7- oxabicyclo [4.1.0] heptane, 1,2- epoxy group -5- hexene And 1,7- octadiene monoepoxide etc..

As above-mentioned distyryl compound, can enumerate for example, styrene, methyl styrene, chlorostyrene and bromstyrol Deng.

As above-mentioned maleimide compound, can enumerate for example, maleimide, N- methylmaleimido, N- benzene Base maleimide and N- N-cyclohexylmaleimide etc..

The method for obtaining the specific copolymer for cured film formation composition of the invention is not particularly limited, example It such as, can be by the monomer (monomer with photodimerization position and with heat cross-linking position for making there is particular functional group Monomer), in the solvent that is coexisted according to the desired monomer with non-reacted functional group and polymerization initiator etc., 50~110 Polymerization reaction is carried out at a temperature of DEG C and is obtained.As long as at this point, used solvent dissolution have particular functional group monomer, The solvent of the monomer and polymerization initiator etc. with non-reacted functional group used according to expectation is just not particularly limited.As tool Body example can enumerate the solvent recorded in aftermentioned solvent.

Thus obtained specific copolymer is usually the state of lysed solution in a solvent, in the present invention it is possible to Solution as (A) ingredient directly uses.

In addition, the solution of the specific copolymer obtained as described above is put into ether, water under stirring etc., make it again Precipitating, the sediment of generation is filtered, is washed, and then carries out air drying or heat drying under normal or reduced pressure, from And the powder of specific copolymer can be made.Operation in this way can remove and polymerize initiation with what specific copolymer coexisted Agent and unreacted monomer, result can obtain the powder of sublimed specific copolymer.It cannot be filled by once-through operation In the case where dividing ground purifying, it is re-dissolved in powder obtained in solvent, repeats above-mentioned operation.

In cured film formation composition of the invention, as (A) ingredient, above-mentioned specific copolymer can be directly used Powder, or the powder can be re-dissolved in for example aftermentioned solvent, be used with the state of solution.

In addition, in the present embodiment, the acrylic acid series copolymer of (A) ingredient can be the mixing of a variety of specific copolymers Object.

As described above, in the present invention, as (A) ingredient, the compound or high molecular weight of low molecular weight can be used Specific copolymer.In addition, (A) ingredient is also possible to the compound of respectively a kind or more of low molecular weight and the spy of high molecular weight Determine the mixture of copolymer.

[(B) ingredient]

Cured film formation of the invention is comprising the repetition with N- alkoxy methyl with (B) ingredient contained in composition The polymer (hereinafter also referred to specific copolymer 2) of unit and the repetitive unit with the side chain comprising polymerism C=C double bond.

As the N of N- alkoxy methyl, i.e. nitrogen-atoms, the nitrogen-atoms of amide, the nitrogen-atoms of thioamides, urea can be enumerated Nitrogen-atoms, the nitrogen-atoms of thiocarbamide, the nitrogen-atoms of carbamate, the nitrogen-atoms that is incorporated on the ortho position of nitrogenous heterocyclic nitrogen-atoms Deng.Therefore, as N- alkoxy methyl, can enumerate alkoxy methyl and nitrogen-atoms, thioamides selected from amide nitrogen-atoms, The nitrogen-atoms of urea, the nitrogen-atoms of thiocarbamide, the nitrogen-atoms of carbamate, the nitrogen that is incorporated on the ortho position of nitrogenous heterocyclic nitrogen-atoms Structure obtained by nitrogen-atoms in atom etc. combines.

As the monomer (hereinafter also referred to specific monomer X1) for assigning the repetitive unit with N- alkoxy methyl, as long as Monomer with above-mentioned group is just not particularly limited, but can preferably enumerate example formula described as follows (b1) compound represented.

(in formula, R¹Indicate hydrogen atom or methyl, R²Indicate the alkane that the carbon atom number of hydrogen atom or linear chain or branched chain is 1~10 Base.)

As abovementioned alkyl, can enumerate for example, methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, Tert-butyl, n-pentyl, 1- methyl-normal-butyl, 2- methyl-normal-butyl, 3- methyl-normal-butyl, 1,1- dimethyl-n-propyl, 1, 2- dimethyl-n-propyl, 2,2- dimethyl-n-propyl, 1- ethyl-n-propyl, n-hexyl, 1- methyl-n-pentyl, 2- methyl- N-pentyl, 3- methyl-n-pentyl, 4- methyl-n-pentyl, 1,1- dimethyl-normal-butyl, 1,2- dimethyl-normal-butyl, 1,3- bis- Methyl-normal-butyl, 2,2- dimethyl-normal-butyl, 2,3- dimethyl-normal-butyl, 3,3- dimethyl-normal-butyl, 1- ethyl-positive fourth Base, 2- ethyl-normal-butyl, 1,1,2- trimethyl-n-propyl, 1,2,2- trimethyl-n-propyl, 1- ethyl -1- methyl-positive third Base, 1- Ethyl-2-Methyl-n-propyl, n-heptyl, 1- methyl-n-hexyl, 2- methyl-n-hexyl, 3- methyl-n-hexyl, 1,1- Dimethyl-n-pentyl, 1,2- dimethyl-n-pentyl, 1,3- dimethyl-n-pentyl, 2,2- dimethyl-n-pentyl, 2,3- diformazan Base-n-pentyl, 3,3- dimethyl-n-pentyl, 1- ethyl-n-pentyl, 2- ethyl-n-pentyl, 3- ethyl-n-pentyl, 1- methyl- 1- ethyl-normal-butyl, 1- methyl -2- ethyl-normal-butyl, 1- Ethyl-2-Methyl-normal-butyl, 2- methyl -2- ethyl-normal-butyl, 2- ethyl -3- methyl-normal-butyl, n-octyl, 1- methyl-n-heptyl, 2- methyl-n-heptyl, 3- methyl-n-heptyl, 1,1- bis- Methyl-n-hexyl, 1,2- dimethyl-n-hexyl, 1,3- dimethyl-n-hexyl, 2,2- dimethyl-n-hexyl, 2,3- dimethyl- N-hexyl, 3,3- dimethyl-n-hexyl, 1- ethyl-n-hexyl, 2- ethyl-n-hexyl, 3- ethyl-n-hexyl, 1- methyl-1- Ethyl-n-pentyl, 1- methyl -2- ethyl-n-pentyl, 1- methyl -3- ethyl-n-pentyl, 2- methyl -2- ethyl-n-pentyl, 2- Methyl -3- ethyl-n-pentyl, 3- methyl -3- ethyl-n-pentyl, n-nonyl, positive decyl etc..

As the concrete example of such monomer, N- hydroxymethyl (methyl) acrylamide, N- methoxy (first can be enumerated Base) acrylamide, N- ethoxyl methyl (methyl) acrylamide, N- butoxymethyl (methyl) acrylamide etc. be by hydroxymethyl Or alkoxy methyl instead of acrylamide compound or methacrylamide compounds.In addition, so-called (methyl) acryloyl Amine indicates both Methacrylamide and acrylamide.

As the group comprising polymerism C=C double bond, acrylic, methacrylic acid group, vinyl, allyl can be enumerated Base, dimaleoyl imino etc..

(B) the preferred carbon atom of specific side chain in the repetitive unit with the side chain comprising polymerism C=C double bond of ingredient Number is 3~16, end has the side chains of unsaturated bond, particularly preferred formula (b2) like that shown in specific side chain.Such as formula (b2-1) Shown, specific side chain shown in formula (b2) is in conjunction with the ester bond part of acrylic acid series polymeric compounds.

In formula (b2), R⁵¹Be carbon atom number it is 1~14, and is from aliphatic group, comprising the fatty group of ring structures In the group of group and aromatic group the organic group that selects or comprising selected from the group multiple organic groups combination it is organic Group.R⁵¹It may include ester bond, ehter bond, amido bond or urethane bond etc..

In formula (b2), R⁵²For hydrogen atom or methyl, preferably R⁵²For the specific side chain of hydrogen atom, more preferably end For the specific side chain of acryloyl group, methylacryloyl or styryl.

In formula (b2-1), R⁵³For hydrogen atom or methyl.

The method for obtaining the above-mentioned polymer with specific side chain like that is not particularly limited.If enumerating an example, in advance The acrylic acid series polymeric compounds with particular functional group are generated by polymerizations such as free radical polymerizations.Then, make the particular functional Group, compound (the hereinafter referred to as specific compound with end with unsaturated bond.) reacted and generate specific side chain, thus The side chain comprising polymerism C=C double bond can be imported into the polymer as (B) ingredient.

Here, so-called particular functional group, refers to carboxyl, glycidyl, hydroxyl, the amino of active hydrogen, phenol hydroxyl The functional groups such as base or isocyanate group, or a variety of functional groups selected from these functional groups.

In the reaction of the specific side chain of above-mentioned generation, particular functional group, have to specific compound with react relevant Preferred group of group is combined into, carboxyl and epoxy group, hydroxyl and isocyanate group, phenolic hydroxyl group and epoxy group, carboxyl and isocyanide Perester radical, amino and isocyanate group or hydroxyl and acyl chlorides etc..In turn, carboxyl and methacrylic acid contracting are combined into for preferred group Water glyceryl ester or hydroxyl and isocyanatomethyl ethyl acrylate.

In addition, the polymer with particular functional group is with specific monomer X1 in the reaction of the specific side chain of above-mentioned generation With the monomer with the functional group (particular functional group) for being reacted with specific compound, that is, there is carboxyl, glycidol The monomer (hereinafter also referred to specific monomer X2) of base, hydroxyl, the amino of active hydrogen, phenolic hydroxyl group or isocyanate group etc. is Copolymer obtained by essential component, number-average molecular weight 2,000~25,000.Here, there is particular functional for polymerization Group monomer can be used alone, as long as the combination not reacted in polymerization also can be used together it is a variety of.

Monomer necessary to being enumerated below in order to obtain the polymer with particular functional group, i.e., specific monomer X2's is specific Example.But it is not limited by these concrete examples.

As the monomer with carboxyl, can enumerate for example, acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyl Oxygroup) ethyl) phthalic acid ester, mono- (2- (methacryloxy) ethyl) phthalic acid ester, N- (carboxyl phenyl) Malaysia acyl Imines, N- (carboxyl phenyl) Methacrylamide and N- (carboxyl phenyl) acrylamide etc..

As the monomer with glycidyl, can enumerate for example, glycidyl methacrylate, acrylic acid shrink Glyceride, allyl glycidyl ether, 3- vinyl -7- oxabicyclo [4.1.0] heptane, 1,2- epoxy group -5- hexene and 1,7- octadiene monoepoxide etc..

As the monomer with hydroxyl, can enumerate for example, acrylic acid 2- hydroxy methacrylate, 2-hydroxyethyl methacrylate, Acrylic acid 2- hydroxy propyl ester, methacrylic acid 2- hydroxy propyl ester, acrylic acid 4- hydroxybutyl, methacrylic acid 4- hydroxybutyl, Acrylic acid 2,3- dihydroxy propyl ester, methacrylic acid 2,3- dihydroxy propyl ester, diethylene glycol monoacrylate, diethylene glycol list first Base acrylate, caprolactone 2- (acryloxy) ethyl ester, caprolactone 2- (methacryloxy) ethyl ester, poly(ethylene glycol) second Base ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, 5- acryloxy -6- hydroxy norbomene -2- carboxyl - 6- lactone and 5- methacryloxy -6- hydroxy norbomene -2- carboxyl -6- lactone etc..

As the monomer with amino, can enumerate for example, acrylic acid 2- amino ethyl ester and methacrylic acid 2- amino first Ester etc..

As the monomer with phenolic hydroxyl group, can enumerate for example, hydroxy styrenes, N- (hydroxy phenyl) acrylamide, N- (hydroxy phenyl) Methacrylamide and N- (hydroxy phenyl) maleimide etc..

As the monomer with isocyanate group, can enumerate for example, acryloyl ethyl isocyanate, methacryloylethyl Isocyanates and tetramethyl xylene isocyanate etc..

In the side chain shown in thus obtained formula (b2), as R⁵¹Concrete example, following formula (B-1)~formula can be enumerated (B-11) etc..

In addition, in the present invention, in the polymer of acquisition (B) ingredient, in addition to specific monomer X1 and specific monomer X2 with Outside, monomer can be copolymerized with the monomer, without aforementioned thermally cross-linkable substituent group can be used together.

As the concrete example of such monomer, can enumerate with the structure different from specific monomer X1 and specific monomer X2 Acrylate compounds or methacrylate compound, maleimide compound, acrylamide compound, acrylonitrile, horse Come acid anhydrides, distyryl compound and vinyl compound etc..

The concrete example of aforementioned monomer is enumerated below, but is not limited by these concrete examples.

As have from the acrylate compounds of the different structure such as aforementioned specific monomer X1, can enumerate for example, propylene Sour methyl esters, ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid The tert-butyl ester, benzyl acrylate, acrylic acid naphthalene ester, acrylic acid anthracene ester, acrylic acid anthrylmethyl, phenyl acrylate, acrylic acid shrink Glyceride, acrylic acid 2,2,2- trifluoro ethyl ester, cyclohexyl acrylate, isobornyl acrylate, acrylic acid 2- methoxy acrylate, third Olefin(e) acid methoxy triethylene ester, acrylic acid 2- ethoxy ethyl ester, tetrahydrofurfuryl acrylate, acrylic acid 3- methoxybutyl, third Olefin(e) acid 2- methyl -2- Buddha's warrior attendant alkyl ester, acrylic acid 2- propyl -2- Buddha's warrior attendant alkyl ester, acrylic acid 8- methyl -8- tricyclodecyl, Yi Jibing Olefin(e) acid 8- ethyl -8- tricyclodecyl etc..

As have from the methacrylate compound of the different structure such as aforementioned specific monomer X1, can enumerate for example, Methyl methacrylate, ethyl methacrylate, n propyl methacrylate, isopropyl methacrylate, methacrylic acid are just Butyl ester, Isobutyl methacrylate, Tert-butyl Methacrylate, benzyl methacrylate, methacrylic acid naphthalene ester, metering system Sour anthracene ester, methacrylic acid anthrylmethyl, phenyl methacrylate, glycidyl methacrylate, methacrylic acid 2,2, 2- trifluoro ethyl ester, cyclohexyl methacrylate, isobornyl methacrylate, methacrylic acid 2- methoxy acrylate, methyl-prop Olefin(e) acid methoxy triethylene ester, methacrylic acid 2- ethoxy ethyl ester, tetrahydrofurfuryl methacrylate, methacrylic acid 3- first Oxygroup butyl ester, 2-Methacryloyloxy-2-methyladamantane, gamma-butyrolacton methacrylate, methacrylic acid 2- propyl- 2- Buddha's warrior attendant alkyl ester, methacrylic acid 8- methyl -8- tricyclodecyl and methacrylic acid 8- ethyl -8- tricyclodecyl etc..

As aforementioned vinyl compound, can enumerate for example, methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, second Alkenyl carbazole, allyl glycidyl ether, 3- vinyl -7- oxabicyclo [4.1.0] heptane, 1,2- epoxy group -5- hexene, And 1,7- octadiene monoepoxide etc..

As aforementioned distyryl compound, can enumerate for example, styrene, methyl styrene, chlorostyrene, bromstyrol Deng.

As aforementioned maleimide compound, can enumerate for example, maleimide, N- methylmaleimido, N- benzene Base maleimide and N- N-cyclohexylmaleimide etc..

In the polymer of (B) ingredient, with N- alkoxy methyl repetitive unit there are ratios relative to the polymerization 100 moles of whole repetitive units of object are preferably 40 moles of %~90 mole %, and further preferably 50 moles of %~85 are rubbed You are %.

Namely based on the total amount of the whole monomers used to obtain the specific copolymer 2 as (B) ingredient, in order to As (B) ingredient specific copolymer 2 and the usage amount of specific monomer X1 that uses is preferably that 40 moles of %~90 are rubbed You are %, further preferably 50 moles of %~85 mole %.

In the case where adding up to less than 40 moles of %, solidification caused by the heat cross-linking with (A) ingredient becomes not fill sometimes Point；In the case where total than 90 moles % are big, adverse effect is generated to the adaptation of substrate sometimes.

In the polymer of (B) ingredient, with the side chain comprising polymerism C=C double bond repetitive unit there are ratios Relative to 100 moles of whole repetitive units preferably 10 moles of %~60 mole % of the polymer, further preferably 15 rub You are %~50 mole %.

Namely based on the total amount of the whole monomers used to obtain the specific copolymer 2 as (B) ingredient, in order to As (B) ingredient specific copolymer 2 and the usage amount of specific monomer X2 that uses is preferably that 10 moles of %~60 are rubbed You are %, further preferably 15 moles of %~50 mole %.

In the case where adding up to less than 10 moles of %, become inadequate sometimes with the adaptation of liquid crystal layer；In total ratio In the case that 60 moles of % are big, solidification caused by the heat cross-linking with (A) ingredient becomes inadequate sometimes.

The method of the specific copolymer 2 for the example for being used as (B) ingredient is not particularly limited, but for example, can be passed through In the monomer and polymerization initiator in addition to specific monomer for making specific monomer X1, specific monomer X2 and being added according to expectation Etc. in the solvent coexisted, 50~110 DEG C at a temperature of carry out polymerization reaction and obtain.As long as at this point, used solvent Dissolve monomer shown in above-mentioned Formula X, according to the molten of the monomer and polymerization initiator etc. for it is expected to use in addition to specific monomer Agent is just not particularly limited.As its concrete example, it is documented in aftermentioned<solvent>item.

The acrylic acid series polymeric compounds of the example as (B) ingredient obtained by above method are usually molten in a solvent The state of the solution solved, in the present invention it is possible to which the solution as (B) ingredient directly uses.

In addition, the solution of the acrylic acid series polymeric compounds of the example as (B) ingredient obtained by the above method is put into In ether, water under stirring etc., makes its reprecipitation, the sediment of generation is filtered, is washed, then under normal or reduced pressure Carry out air drying or heat drying, so as to be made (B) ingredient specific copolymer 2 powder.By above-mentioned operation, It can remove the polymerization initiator and unreacted monomer coexisted with the specific copolymer 2 of (B) ingredient, result can obtain pure The powder of the specific copolymer 2 for the example as (B) ingredient changed.The case where cannot fully be purified by once-through operation Under, it is re-dissolved in powder obtained in solvent, repeats above-mentioned operation.

In the composition of the cured film on the surface of formation optical film of the invention, the specific copolymer 2 of (B) ingredient can be with It is used with powder morphology or powder after purification is re-dissolved in solution morphology obtained by aftermentioned solvent.

In addition, (B) ingredient can be conduct in the composition of the cured film on the surface of formation optical film of the invention (B) a variety of mixtures of specific copolymer 2 shown in the example of ingredient.

The weight average molecular weight of such polymer is 1,000~500,000, preferably 2,000~200,000, more preferably It is 3,000~150,000, further preferably 3,000~50,000.

These polymer can be used alone or in combination of two kinds or more.

About the content of (B) ingredient in cured film formation composition of the invention, preferably (A) ingredient and (B) ingredient Content than by quality ratio be 5:95~60:40.In the case where the content of the polymer of (B) ingredient is too small, by cured film The solvent resistance and heat resistance of the cured film that formation is obtained with composition decline, orientation sensitivity decline when light orientation.It is another Aspect, in the case where the content of the polymer of (B) ingredient is excessive, light orientation and storage stability decline sometimes.

[(C) ingredient]

(C) ingredient contained in composition of the invention is selected from least one of (C-1), (C-2) or (C-3) polymerization (C-1): object has selected from the poly- of at least one of hydroxyl, carboxyl, amide groups, amino and alkoxysilyl substituent group Close object, (C-2): the substituent group of thermal response can be carried out with (A) ingredient and can carry out the polymer of self-crosslinking, (C-3): three by having Paracyanogen amine-formaldehyde resin.Each ingredient is described in detail below.

[(C-1) ingredient]

(C-1) ingredient is with selected from least one of hydroxyl, carboxyl, amide groups, amino and alkoxysilyl Polymer (the hereinafter also referred to specific (co) polymer 1 of substituent group.).

As the polymer of (C-1) ingredient, can enumerate for example, acrylic acid series polymeric compounds, urethane-modified acrylic Based polymer, polyamic acid, polyimides, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, Polycarbonate polyol, polycaprolactone polyol, polyalkyleneimine, polyallylamine, cellulose family (cellulose or its derivative Object), cyclic polymers such as polymer, the cyclodextrin with linear chain structure or branched structure such as phenol resol resins etc..

Wherein, as acrylic acid series polymeric compounds, can apply has acrylate, methacrylate, styrene etc. Polymer obtained by the monomer polymerization of unsaturated double-bond.

The synthetic method of the acrylic acid series polymeric compounds of example as (C-1) ingredient makes to have selected from hydroxyl, carboxyl, acyl The monomer of at least one of amido, amino and alkoxysilyl substituent group, with according to desired monomer in addition to this The method of (co) polymerization is easy.

At least one of hydroxyl, carboxyl, amide groups, amino and alkoxysilyl substituent group is selected from as having Monomer can be enumerated for example, acrylic acid 2- hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid 2- hydroxy propyl ester, methyl-prop Olefin(e) acid 2- hydroxy propyl ester, acrylic acid 4- hydroxybutyl, methacrylic acid 4- hydroxybutyl, acrylic acid 2,3- dihydroxy propyl ester, first Base acrylic acid 2,3- dihydroxy propyl ester, diethylene glycol monoacrylate, diethylene glycol monomethyl acrylate, caprolactone 2- (third Alkene acyloxy) ethyl ester, caprolactone 2- (methacryloxy) ethyl ester, poly(ethylene glycol) ethyl ether acrylate, poly- (second two Alcohol) ethyl ether methacrylate, 5- acryloxy -6- hydroxy norbomene -2- carboxyl -6- lactone, 5- methacryl Oxygroup -6- hydroxy norbomene -2- carboxyl -6- lactone etc. have hydroxyl monomer, acrylic acid, methacrylic acid, crotonic acid, Mono- (2- (acryloxy) ethyl) phthalic acid ester, mono- (2- (methacryloxy) ethyl) phthalic acid ester, ethylene Yl benzoic acid, N- (carboxyl phenyl) maleimide, N- (carboxyl phenyl) Methacrylamide, N- (carboxyl phenyl) acrylamide Deng monomer and 4-Vinyl phenol, hydroxy styrenes, o-hydroxystyrene, N- (hydroxy phenyl) methyl with carboxyl The monomer with phenolic hydroxyl group such as acrylamide, N- (hydroxy phenyl) acrylamide and N- (hydroxy phenyl) maleimide, third Acrylamide, Methacrylamide, N methacrylamide, N, N- dimethylacrylamide, N, the tool such as N- acrylamide There are the monomer of amide groups, acrylic-amino ethyl ester, methacrylic acid amino-ethyl ester, acrylic-amino propyl diester and methyl-prop Olefin(e) acid aminopropan base ester etc. has the monomer of amino, trimethoxy-silylpropyl acrylate, trimethoxysilyl Propyl methacrylate, triethoxysilylpropyltetrasulfide acrylate and triethoxysilylpropyltetrasulfide methacrylic acid Ester etc. has the monomer etc. of alkoxysilyl.

In addition, in the present invention, when being used as the acrylic acid series polymeric compounds of example of (C-1) ingredient, in addition to using It, can other than the monomer selected from least one of hydroxyl, carboxyl, amide groups, amino and alkoxysilyl substituent group With and with can with the monomer be copolymerized, without in hydroxyl, carboxyl, amide groups, amino and alkoxysilyl The monomer of substituent group.

As the concrete example of such monomer, acrylate compounds, methacrylate compound, Malaysia acyl can be enumerated Group with imine moiety, acrylonitrile, maleic anhydride, distyryl compound and vinyl compound etc..

As foregoing acrylates compound, can enumerate for example, methyl acrylate, ethyl acrylate, propyl acrylate, third Isopropyl gadoleate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, benzyl acrylate, acrylic acid naphthalene ester, propylene Sour anthracene ester, acrylic acid anthrylmethyl, phenyl acrylate, glycidyl acrylate, acrylic acid 2,2,2- trifluoro ethyl ester, acrylic acid Cyclohexyl, isobornyl acrylate, acrylic acid 2- methoxy acrylate, methoxyethyl triglycol ester, acrylic acid 2- ethoxy Base ethyl ester, acrylic acid 2- amino ethyl ester, tetrahydrofurfuryl acrylate, acrylic acid 3- methoxybutyl, acrylic acid 2- methyl -2- Buddha's warrior attendant Alkyl ester, acrylic acid 2- propyl -2- Buddha's warrior attendant alkyl ester, acrylic acid 8- methyl -8- tricyclodecyl and acrylic acid 8- ethyl -8- tricyclic Last of the ten Heavenly stems ester etc..

As aforementioned methacrylate compound, can enumerate for example, methyl methacrylate, ethyl methacrylate, Propyl methacrylate, isopropyl methacrylate, n-BMA, Isobutyl methacrylate, methacrylic acid The tert-butyl ester, benzyl methacrylate, methacrylic acid naphthalene ester, methacrylic acid anthracene ester, methacrylic acid anthrylmethyl, methyl-prop Olefin(e) acid phenyl ester, glycidyl methacrylate, methacrylic acid 2,2,2- trifluoro ethyl ester, cyclohexyl methacrylate, methyl Isobornyl acrylate, methacrylic acid 2- methoxy acrylate, methacrylic acid methoxyl group triglycol ester, methacrylic acid 2- Ethoxy ethyl ester, methacrylic acid 2- amino methyl, tetrahydrofurfuryl methacrylate, methacrylic acid 3- methoxybutyl, first Base acrylic acid 2- methyl -2- Buddha's warrior attendant alkyl ester, gamma-butyrolacton methacrylate, methacrylic acid 2- propyl -2- Buddha's warrior attendant alkyl ester, Methacrylic acid 8- methyl -8- tricyclodecyl and methacrylic acid 8- ethyl -8- tricyclodecyl etc..

For be used as the example of (C-1) ingredient acrylic acid series polymeric compounds, have selected from hydroxyl, carboxyl, amide The usage amount of the monomer of at least one of base, amino and alkoxysilyl substituent group, based on for being used as (C-1) The total amount of whole monomers of the acrylic acid series polymeric compounds of the example of ingredient is preferably 5 moles of %~100 mole %.

The method of the acrylic acid series polymeric compounds for the example for being used as (C-1) ingredient is not particularly limited, for example, can lead to Cross make with selected from least one of hydroxyl, carboxyl, amide groups, amino and alkoxysilyl substituent group monomer, According to the list for not having the substituent group in hydroxyl, carboxyl, amide groups, amino and alkoxysilyl of expectation addition In the solvent that body and polymerization initiator etc. coexist, 50 DEG C~110 DEG C at a temperature of carry out polymerization reaction and obtain.At this point, As long as used solvent dissolution has at least one in hydroxyl, carboxyl, amide groups, amino and alkoxysilyl The monomer of kind substituent group is selected from hydroxyl, carboxyl, amide groups, amino and alkoxysilyl according to not having for expectation addition In the monomer of substituent group and the solvent of polymerization initiator etc. be just not particularly limited.As concrete example, it is recorded in aftermentioned [solvent] item.

The acrylic acid series polymeric compounds of the example as (C-1) ingredient obtained by above method are usually in a solvent Lysed solution state.

In addition, the solution of the acrylic acid series polymeric compounds of the example as (C-1) ingredient obtained by the above method is put into In ether, water under to stirring etc., makes its reprecipitation, the sediment of generation is filtered, is washed, then in normal pressure or decompression Lower progress air drying or heat drying, so as to be made as (C-1) ingredient example acrylic acid series polymeric compounds powder Body.By above-mentioned operation, it can remove and polymerize initiation with what the acrylic acid series polymeric compounds of the example as (C-1) ingredient coexisted Agent and unreacted monomer, as a result, the acrylic acid series polymeric compounds of the sublimed example as (B) ingredient can be obtained Powder.By once-through operation cannot fully purify in the case where, be re-dissolved in powder obtained in solvent, repeat into Row aforesaid operations.

The weight average molecular weight of the acrylic acid series polymeric compounds of example as (C-1) ingredient is preferably 3000~200000, more Preferably 4000~150000, further preferably 5000~100000.If weight average molecular weight is more than 200000 and excessive, Dissolubility in a solvent declines sometimes, and operability declines sometimes；If weight average molecular weight is too small less than 3000, heat Solidify deficiency when solidification sometimes, solvent resistance and heat resistance decline sometimes.In addition, weight average molecular weight is to pass through gel infiltration Chromatography (GPC) uses polystyrene as value obtained by standard sample.It is all same in the present specification below.

Then, the polyether polyol as preferred an example of the specific (co) polymer 1 of (C-1) ingredient, can enumerate pair The polyalcohols addition such as polyethylene glycol, polypropylene glycol, propylene glycol, bisphenol-A, triethylene glycol, D-sorbite propylene oxide and/or poly- Polyether polyol obtained by ethylene glycol, polypropylene glycol etc..As the concrete example of polyether polyol, ADEKA アデカ can be enumerated Port リエーテ Le P series, G series, EDP series, BPX series, FC series, CM series, day oil ユニオッ Network ス (registrar Mark) HC-40, HC-60, ST-30E, ST-40E, G-450, G-750, mono- Le of ユニオ (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400, ノニオ Application (registered trademark) LT-221, ST- 221, OT-221 etc..

The polyester polyol of preferred an example of the specific (co) polymer as (C-1) ingredient, can enumerate make adipic acid, The glycol such as the polybasic carboxylic acids such as decanedioic acid, M-phthalic acid and ethylene glycol, propylene glycol, butanediol, polyethylene glycol, polypropylene glycol carry out Polyester polyol obtained by reaction.As the concrete example of polyester polyol, DIC Port リライト (registered trademark) OD- can be enumerated X-286、OD-X-102、OD-X-355、OD-X-2330、OD-X-240、OD-X-668、OD-X-2108、OD-X-2376、OD-X- 2044、OD-X-688、OD-X-2068、OD-X-2547、OD-X-2420、OD-X-2523、OD-X-2555、OD-X-2560、クラレ polyalcohol P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, F- 2010, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016 etc..

The polycaprolactone polyol of preferred an example of the specific (co) polymer as (C-1) ingredient, can enumerate with three The polyalcohols such as hydroxymethyl-propane, ethylene glycol are initiator, and 6-caprolactone is made to carry out polycaprolactone polyol obtained by ring-opening polymerisation. As the concrete example of polycaprolactone polyol, can enumerate DIC Port リライト (registered trademark) OD-X-2155, OD-X-640, OD-X-2568, ダイセ Le chemistry プラ Network セ Le (registered trademark) 205, L205AL, 205U, 208,210,212, L212AL, 220,230,240,303,305,308,312,320 etc..

The polycarbonate polyol of preferred an example of the specific (co) polymer as (C-1) ingredient, can enumerate makes three The polyalcohols such as hydroxymethyl-propane, ethylene glycol and diethyl carbonate, diphenyl carbonate, ethylene carbonate etc. gather obtained by being reacted Carbonate polyol.As the concrete example of polycarbonate polyol, ダイセ Le chemistry プラ Network セ Le (registrar can be enumerated Mark) CD205, CD205PL, C-590, C-1050, C-2050, C-2090, C-3090 of CD210, CD220, Network ラレ etc..

The cellulose of preferred an example of the specific (co) polymer 1 as (C-1) ingredient, can enumerate hydroxyethyl cellulose The hydroxy alkyl celluloses class such as element, hydroxy propyl cellulose, hydroxy ethylmethylcellulose, HYDROXY PROPYL METHYLCELLULOSE, hydroxyl The hydroxyalkylalkyls element class such as base hydroxyethyl ethyl cellulose and cellulose etc., for example, it is preferable to be hydroxy ethyl cellulose, hydroxyl The hydroxy alkyl celluloses class such as base propyl cellulose.

The cyclodextrin of preferred an example of the specific (co) polymer 1 as (C-1) ingredient, can enumerate alpha-cyclodextrin, β- The cyclodextrin such as cyclodextrin and γ cyclodextrin, the methyl such as methyl-alphacyclodextrin, methyl-B-cyclodextrin and methyl-y-cyclodextrin Change cyclodextrin, hydroxymethyl-alpha-cyclodextrin, hydroxymethyl-beta-cyclodextrin, hydroxymethyl-gamma-cyclodextrin, 2- hydroxyethyl-α- Cyclodextrin, 2- hydroxyethyl-beta-cyclodextrin, 2- hydroxyethyl-gamma-cyclodextrin, 2- hydroxypropyl-alpha-cyclodextrin, 2- hydroxyl third Group-beta-cyclodextrin, 2- hydroxypropyl-gamma-cyclodextrin, 3- hydroxypropyl-alpha-cyclodextrin, 3- hydroxypropyl-beta-cyclodextrin, 3- hydroxyl Base propyl-gamma-cyclodextrin, 2,3- dihydroxypropyl-alpha-cyclodextrin, 2,3- dihydroxypropyl-beta-cyclodextrin, 2,3- dihydroxy third Hydroxyalkylcyclodextrins such as base-gamma-cyclodextrin etc..

Urethane-modified acrylic's based polymer of the preference of specific (co) polymer 1 as (C-1) ingredient, As commercially available product, great achievement Off ァイ Application ケミカ Le ア Network リット (registered trademark) 8UA-017,8UA-239,8UA- can be enumerated 239H, 8UA-140,8UA -146,8UA-585H, 8UA-301,8UA-318,8UA-347A, 8UA-347H, 8UA-366 etc..

The phenol resol resins of the preference of specific (co) polymer 1 as (C-1) ingredient, can enumerate for example, Phenol-formaldehyde condensation polymer etc..

In the present compositions, the polymer of (C-1) ingredient can be with powder morphology or by sublimed powder again It is dissolved in the use of solution morphology obtained by aftermentioned solvent.

In addition, in the present compositions, (C-1) ingredient can be as polymer illustrated by (C-1) ingredient A variety of mixtures.

[(C-2) ingredient]

In the cured film formation composition of present embodiment, (C-2) ingredient can also be made with can be with (A) ingredient It carries out the substituent group of thermal response and the polymer (hereinafter also referred to specific (co) polymer 2) of self-crosslinking can be carried out.

More specifically, specific (co) polymer 2 is the thermal response and self-crosslinking reaction occurred with (A) ingredient, and is had The bridging property substituent group reacted at a temperature of lower than the sublimation temperature of (A) ingredient is (below by bridging property substituent group and hydroxyl Base, carboxyl, amino, amide groups and alkoxysilyl together be known as particular functional group) polymer.By (A) ingredient with (C-2) thermal response of ingredient can inhibit (A) ingredient to distil.Moreover, as described above, the cured film of present embodiment forms use Composition can form the high-efficient oriented material of light reaction as cured film.

The preferred bridging property substituent group that polymer as (C-2) ingredient contains, can enumerate methylolamide base, Alkoxysilyl etc..The content for the bridging property substituent group being related to is relative to 1 unit of repetitive unit of (C-2) ingredient 0.5~1, from the viewpoint of the solvent resistance of oriented material, further preferably 0.8~1.

As the polymer of (C-2) ingredient, can be used for example, using N- hydroxymethylacrylamide, N- methoxy methyl Butylmethacrylamide, N- ethoxymethyl acrylamide, N- butoxymethyl Methacrylamide etc. are by hydroxymethyl or alkane Polymer manufactured by the methyl substituted acrylamide compound of oxygroup or methacrylamide compounds.

As such polymer, can enumerate for example, poly- (N- butoxy methyl acrylamide), N- butoxymethyl propylene The copolymer of amide and styrene, the copolymer of N- hydroxymethyl Methacrylamide and methyl methacrylate, N- ethyoxyl The copolymer and (N- butoxymethyl) acrylamide and methyl-prop of methyl methacrylamide and benzyl methacrylate The copolymer etc. of olefin(e) acid benzyl ester and methacrylic acid 2- hydroxy propyl ester.

In addition, also can use and gather using manufactured by the compound with alkoxysilyl as (C-2) ingredient Close object.

As such polymer, can enumerate for example, poly- (3- methacryloxypropyl trimethoxy silane), 3- first The copolymer of base acryloyloxypropyltrimethoxysilane and styrene, poly- (3- acryloxypropyl trimethoxy silicon Alkane), 3- acryloyloxypropyltrimethoxysilane and the copolymer of methyl methacrylate etc..

In addition, in the specific (co) polymer 2 used in the cured film formation composition of present embodiment, it can be simultaneously With the monomer that can be copolymerized with the monomer with particular functional group (hereinafter also referred to the monomer of non-reacted functional group).

Shown in specific such as (C-1) ingredient part of above-mentioned monomer is recorded.

To obtain the specific (co) polymer 2 used in the cured film formation composition of present embodiment method not It is particularly limited to, for example, can be by making the monomer with particular functional group, there is non-reacted function according to expectation addition In the solvent that monomer and polymerization initiator etc. of group coexist, 50 DEG C~110 DEG C at a temperature of so that it is carried out polymerization reaction and obtain ?.As long as at this point, monomer of the used solvent dissolution with particular functional group, according to expectation use with non-reacted The solvent of the monomer and polymerization initiator of functional group etc. is just not particularly limited.As concrete example, can enumerate in aftermentioned solvent The solvent of record.

The specific (co) polymer 2 so obtained is usually lysed solution state in a solvent.

In addition, the solution of the specific (co) polymer 2 obtained as described above is put into ether, water under stirring etc., Make its reprecipitation, the sediment of generation is filtered, is washed, then carries out air drying under normal or reduced pressure or heating is dry It is dry, so as to which the powder of specific (co) polymer 2 is made.Operation in this way can remove and specific (co) polymer 2 The polymerization initiator and unreacted monomer coexisted, as a result, the powder of sublimed specific (co) polymer 2 can be obtained. By once-through operation cannot fully purify in the case where, be re-dissolved in powder obtained in solvent, repeat on The operation stated.

It, can be directly using above-mentioned specific (co) polymer 2 in the cured film formation composition of present embodiment Powder, or the powder can also be re-dissolved in for example aftermentioned solvent, it is used with the state of solution.

In addition, in the present embodiment, the polymer of (C-2) ingredient can be the mixing of a variety of specific (co) polymers 2 Object.

The weight average molecular weight of such polymer is 1000~500000, preferably 1000~200000, more preferably 1000~100000, further preferably 2000~50000.

These polymer may be used singly or in combination of two or m.

[(C-3) ingredient]

As the melamine formaldehyde resin of (C-3) ingredient, be by resin obtained by melamine and formaldehyde condensation polymer, by Following formula indicates.

In above-mentioned formula, R²¹Hydrogen atom or carbon atom number are indicated as 1~4 alkyl, n is oneself for indicating the number of repetitive unit So number.The alkyl for being 1~4 as carbon atom number, can enumerate the group of corresponding carbon atom number in above-mentioned enumerated alkyl.

About the melamine formaldehyde resin of (C-3) ingredient, from the viewpoint of storage stability, melamine is being carried out The methylol preferably generated when the polycondensation of amine and formaldehyde is partially alkylated or alkylated.

The method of the melamine formaldehyde resin of acquisition (C-3) ingredient is not particularly limited, but generally by by melamine Amine is mixed with formaldehyde, is tuned into alkalescent using sodium carbonate, ammonia etc., is then heated and is synthesized at 60 DEG C~100 DEG C.It is logical Cross react it with alcohol can be by methylol alkoxylate.

About the melamine formaldehyde resin of (C-3) ingredient, weight average molecular weight is preferably 250~5000, more preferably 300~4000, further preferably 350~3500.If weight average molecular weight is more than 5000 and excessive, dissolution in a solvent Property decline sometimes, operability decline sometimes；It is solid sometimes when heat cure if weight average molecular weight is too small less than 250 Change is insufficient, and the improvement effect of solvent resistance and heat resistance cannot sufficiently show sometimes.

In embodiments of the present invention, the melamine formaldehyde resin of (C-3) ingredient can be with liquid form or general Sublimed liquid is re-dissolved in the use of solution morphology obtained by aftermentioned solvent.

In addition, in embodiments of the present invention, (C) ingredient can be a variety of in (C-1), (C-2) and (C-3) The mixture of polymer.

Cured film of the invention, which is formed, is based on the total of (A) ingredient and (B) ingredient with the content of (C) ingredient in composition Measuring 100 mass parts is 5 mass parts~500 mass parts.In the case where the content of the polymer of (C) ingredient is too small, by cured film The solvent resistance and heat resistance of the cured film that formation is obtained with composition decline, orientation sensitivity decline when light orientation.It is another Aspect, in the case where the content of the polymer of (C) ingredient is excessive, light orientation and storage stability decline sometimes.

[(D) ingredient]

Other than above-mentioned (A) ingredient, (B) ingredient and (C) ingredient, the surface cure film of formation optical film of the invention Composition can also contain crosslinking catalyst be used as (D) ingredient.

As the crosslinking catalyst of (D) ingredient, can enumerate for example, acid or thermal acid generator.Using formation light of the invention It is effective to promotion heat cure reaction when forming cured film, to be somebody's turn to do (D) ingredient to learn the composition of the surface cure film of film.

Use acid or thermal acid generator as (D) ingredient in the case where, (D) as long as ingredient contain sulfonic chemical combination Object, hydrochloric acid or its salt are thermally decomposed in prebake conditions or rear baking and generate the compound of acid i.e. at 80 DEG C~250 DEG C of temperature The compound that heat decomposes and generates acid is issued, is just not particularly limited.

As such compound, can enumerate for example, hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propane sulfonic acid, fourth sulfonic acid, penta sulfonic acid, Pungent sulfonic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2- naphthalene sulfonic acids, mesitylene sulphur Acid, paraxylene -2- sulfonic acid, meta-xylene -2- sulfonic acid, 4- ethyl phenenyl azochlorosulfonate acid, 1H, 1H, 2H, 2H- perfluorooctane sulfonate, perfluor The sulfonic acid such as (2- Ethoxyethane) sulfonic acid, five fluorine ethanesulfonic acids, nine fluorine butane -1- sulfonic acid, dodecyl benzene sulfonic acid or its hydrate, Salt etc..

In addition, can enumerate as the compound for generating acid by heat for example, bis- (tosyloxy) ethane, bis- (first Phenylsulfonyloxy) propane, bis- (tosyloxy) butane, to nitrobenzyl tosylat, adjacent nitro benzyl toluene sulfonic acid Ester, 1,2,3- benzene three (methanesulfonate ester), p-methyl benzenesulfonic acid pyridineSalt, p-methyl benzenesulfonic acid morpholineSalt, p-methyl benzenesulfonic acid second Ester, propyl p-toluenesulfonate, butyl p-toluenesulfonate, p-methyl benzenesulfonic acid isobutyl ester, methyl tosylate, p-methyl benzenesulfonic acid benzene Ethyl ester, p-methyl benzenesulfonic acid cyano methyl ester, p-methyl benzenesulfonic acid 2,2,2- trifluoro ethyl ester, p-methyl benzenesulfonic acid 2- hydroxybutyl, N- ethyl- 4- toluenesulfonamide and following formula [TAG-1]~formula [TAG-41] compound represented etc..

The cured films of embodiments of the present invention forms the content with (D) ingredient in composition, relative to as (A) at At least one of the compound with light orientation group and heat cross-linking group divided, polymer and work as (B) ingredient 100 mass parts for the total amount of the polymer of (C) ingredient are 0.01 mass parts~20 mass parts, preferably 0.01 mass parts~ 10 mass parts, more preferably 0.05 mass parts~8 mass parts, further preferably 0.1 mass parts~6 mass parts.By making (D) The content of ingredient is 0.01 mass parts or more, can assign sufficient Thermocurable and solvent resistance, can also impart to exposure High sensitivity.In addition, the content 20 by making (D) ingredient is below the mass, cured film formation composition can be made Storage stability is good.

[(E) ingredient]

The cured film formation of present embodiment uses composition to contain crosslinking agent as needed as (E) ingredient.In more detail and Speech, (E) ingredient is the crosslinking agent reacted with above-mentioned (A) ingredient and (C) ingredient.(E) ingredient can with as (A) ingredient Compound the substituent group in hydroxyl, carboxyl, amide groups, amino and trialkoxysilyl, in (C) ingredient include Substituent group in hydroxyl, carboxyl, amino and trialkoxysilyl combine.Moreover, the cured film of present embodiment Formation composition can form the high-efficient oriented material of light reaction in the form of cured film.

As the crosslinking agent of (E) ingredient, epoxy compounds, methylol compound and isocyanate compound etc. can be enumerated Compound, but preferably methylol compound.

As the concrete example of above-mentioned methylol compound, can enumerate for example, aikoxymethytated glycolurils, alkoxy methyl Change the compounds such as benzoguanamine and alkoxymethylated melamine.

As the concrete example of aikoxymethytated glycolurils, can enumerate for example, 1,3,4,6- tetra- (methoxy) glycoluril, 1, 3,4,6- tetra- (butoxymethyl) glycoluril, 1,3,4,6- tetra- (hydroxymethyl) glycoluril, bis- (hydroxymethyl) ureas of 1,3-, 1,1,3,3- Bis- (the hydroxymethyl) -4,5- dihydroxy -2- imidazoles of four (butoxymethyl) ureas, 1,1,3,3- tetra- (methoxy) urea, 1,3- Quinoline ketone and bis- (the methoxy) -4,5- dimethoxy -2- imidazolones of 1,3- etc..As commercially available product, three can be enumerated Well サイテッ Network (strain) glycoluril compounds processed (trade name: サイメ Le (registered trademark) 1170, パウダーリ Application Network (registration Trade mark) 1174) etc. compounds, methylation carbamide resin (trade name: UFR (registered trademark) 65), butylation carbamide resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), big Japan イ Application キ chemical industry (strain) urea processed/ Diaion (high condensed type, trade name: ベッカミ Application (registered trademark) J-300S, ベッカミ Application P-955, ベッカミ Application N) Deng.

As the concrete example of aikoxymethytated benzoguanamine, can enumerate for example, tetramethoxymethyl benzoguanamine etc..As city Product are sold, three well サイテッ Network (strain) system (trade name: サイメ Le (registered trademark) 1123), (strain) three and ケミカ Le can be enumerated Make (trade name: ニカラッ Network (registered trademark) BX-4000, ニカラッ Network BX-37, ニカラッ Network BL-60, ニカラッ Network BX-55H) etc..

As the concrete example of alkoxymethylated melamine, can enumerate for example, hexamethoxymethyl melamine etc..Make For commercially available product, three well サイテッ Network (strain) methoxy methyl fundamental mode melamine compounds processed (trade name: サイメ Le can be enumerated (registered trademark) 300, サイメ Le 301, サイメ Le 303, サイメ Le 350), butoxymethyl type melamine compound (trade name: マイ U ート (registered trademark) 506, マイ U ート 508), three and ケミカ Le methoxy methyl fundamental mode melamine Amine compounds (trade name: ニカラッ Network (registered trademark) MW-30, ニカラッ Network MW-22, ニカラッ Network MW-11, ニカラッ Network MS-001, ニカラッ Network MX-002, ニカラッ Network MX-730, ニカラッ Network MX-750, ニカラッ Network MX-035), fourth Oxygroup methyl type melamine compound (trade name: ニカラッ Network (registered trademark) MX-45, ニカラッ Network MX-410, ニカラッ Network MX-302) etc..

In addition it is also possible to be such melamine obtained by replacing the hydrogen atom of amino by methylol or alkoxy methyl Compound obtained by amine compounds, carbamide compound, glycoluril compounds and benzoguanamine compound are condensed.It can enumerate for example, beauty The chemical combination of the high molecular weight manufactured documented by state's patent the 6323310th by melamine compound and benzoguanamine compound Object.As the commercially available product of aforementioned melamine compound, trade name can be enumerated: (the three well サイ of サイメ Le (registered trademark) 303 テッ Network (strain) system) etc., as the commercially available product of aforementioned benzoguanamine compound, trade name can be enumerated: サイメ Le (registered trademark) 1123 (three well サイテッ Network (strain) systems) etc..

These crosslinking agents may be used singly or in combination of two or m.

The total amount of polymer based on the compound as (A) ingredient, the polymer as (B) ingredient and (C) ingredient 100 mass parts, it is preferably 50 mass that the cured film of present embodiment, which is formed with the content of the crosslinking agent of (E) ingredient in composition, Part hereinafter, more preferably 30 below the mass.In the case where the content of crosslinking agent is excessive, light orientation and storage stability have When can decline.

[other additives]

The cured film of embodiments of the present invention, which is formed, to be used in composition, as long as not damaging effect of the invention, Ke Yihan There are other additives.

It, can be containing for example, sensitizer as other additives.Sensitizer is forming the surface of optical film of the invention When cured film, become effective in terms of promoting its light reaction.

As sensitizer, the derivative and nitrophenyl compound of benzophenone, anthracene, anthraquinone and thioxanthones etc. can be enumerated Deng.The wherein N particularly preferably as the derivative of benzophenone, N- diethylamino benzophenone and as nitrobenzene 2- nitrofluorene, 2- nitryl fluorenone, 5- nitro acenaphthene, 4- nitrobiphenyl, 4- nitrocinnamic, the 4- nitro Stilbene, 4- nitre of based compound Base benzophenone, 5- nitroindoline.

These sensitizers are not limited by above compound.The compound that they may be used singly or in combination of two or more kinds.

In embodiments of the present invention, the use ratio of sensitizer is preferably relative to 100 mass parts of (A) ingredient 0.1 mass parts~20 mass parts, more preferably 0.2 mass parts~10 mass parts.In the case where the ratio is too small, sometimes cannot Fully obtain the effect as sensitizer；In the case where the ratio is excessive, it is formed by the transmissivity of cured film sometimes Decline or film are coarse sometimes.

As long as in addition, do not damage effect of the invention, the cured film formation compositions of embodiments of the present invention can be with Make containing silane coupling agent, surfactant, rheology control agent, pigment, dyestuff, preserving stabilizer, defoaming agent, antioxidant etc. For other additives.

[solvent]

The cured film formation of embodiments of the present invention is mostly used with composition with lysed solution state in a solvent. At this time used solvent be dissolution (A) ingredient and (B) ingredient, according to expectation add (C) ingredient, (D) ingredient, (E) ingredient, And/or the solvent of other additives, as long as the solvent with such solvability, then not special to its type and structure etc. It limits.

If enumerating the concrete example of solvent, can enumerate for example, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, methyl Cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol Monomethyl ether, propylene glycol monomethyl ether, propylene glycol propyl ether, propylene glycol propyl ether acetic acid esters, cyclopentyl-methyl ether, first Benzene, dimethylbenzene, butanone, cyclopentanone, cyclohexanone, 2- butanone, 3- methyl -2 pentanone, 2 pentanone, 2-HEPTANONE, gamma-butyrolacton, 2- Hydroxypropionate, 2- hydroxy-2-methyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2- hydroxy-3-methyl Methyl butyrate, 3- methoxy methyl propionate, 3- methoxypropionate, 3- ethoxypropanoate, 3- ethoxyl ethyl propionate, Methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, n-propyl acetate, isopropyl acetate Ester, isopropanol, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and n-methyl-2-pyrrolidone etc..

These solvents can be used alone, or combination is two or more uses.In these solvents, propylene glycol monomethyl Ether, propylene glycol monomethyl ether, butanone, cyclohexanone, 2-HEPTANONE, propylene glycol propyl ether, propylene glycol propyl ether acetic acid esters, second Acetoacetic ester, ethyl lactate, butyl lactate, 3- methoxy methyl propionate, 3- methoxypropionate, 3- ethoxyl ethyl propionate and The film forming of 3- ethoxypropanoate is good and highly-safe, therefore more preferably.

The cured film formation of embodiments of the present invention is the cured film with the Thermocurable of light orientation with composition Formation composition.As described above, the cured film formation of present embodiment uses composition to contain: there is light as (A) ingredient At least one of the compound of orientation group and heat cross-linking group, as (B) ingredient comprising having N- alkoxy methyl Repetitive unit and the repetitive unit with the side chain comprising polymerism C=C double bond polymer, as needed containing being selected from (C-1), at least one of (C-2) and (C-3) polymer are used as (C) ingredient, (C-1): having and be selected from hydroxyl, carboxyl, acyl The polymer of at least one of amido, amino and alkoxysilyl substituent group, (C-2): having can carry out with (A) ingredient The substituent group of thermal response and the polymer that self-crosslinking can be carried out, (C-3): melamine formaldehyde resin, and contain as needed Crosslinking catalyst is used as (D) ingredient.Furthermore, it is possible to which containing crosslinking agent as needed is used as (E) ingredient.As long as moreover, not damaging Evil effect of the invention can contain other additives, may further contain solvent.

The cured film of present embodiment forms as follows with the preferred example of composition.

[1]: a kind of cured film formation composition contains (A) ingredient, (B) ingredient, (C) ingredient and solvent, as (A) at least one of the compound with light orientation group and heat cross-linking group of ingredient includes with as (B) ingredient The polymer of repetitive unit with N- alkoxy methyl and the repetitive unit with the side chain comprising polymerism C=C double bond Match ratio is 5:95~60:40 by quality ratio, and at least one and (B) ingredient based on the compound as (A) ingredient are gathered 100 mass parts of total amount for closing object, containing 5 mass parts~500 mass parts (C) ingredient, (C) ingredient be selected from (C-1), (C-2) and at least one of (C-3) polymer, (C-1): have and be selected from hydroxyl, carboxyl, amide groups, amino and alkoxy The polymer of at least one of silicyl substituent group, (C-2): have can with (A) ingredient carry out thermal response substituent group and It can carry out the polymer of self-crosslinking, (C-3): melamine formaldehyde resin.

[2]: a kind of cured film, which is formed, uses composition, contains (A) ingredient, (B) ingredient, (C) ingredient, (D) ingredient and molten The match ratio of agent, (A) ingredient and (B) ingredient is 5:95~60:40 by quality ratio, based on as (A) ingredient compound and (B) 100 mass parts of total amount of the polymer of ingredient, containing 5 mass parts~500 mass parts (C) ingredient, relative to conduct (A) 100 mass parts of total amount of the polymer of the compound of ingredient, the polymer of (B) ingredient and (C) ingredient contain 0.1 mass The crosslinking catalyst of part~40 mass parts is used as (D) ingredient.

[3]: a kind of cured film, which is formed, uses composition, containing (A) ingredient, (B) ingredient, (C) ingredient, (D) ingredient, (E) at Point and solvent, the match ratio of (A) ingredient and (B) ingredient is 5:95~60:40 by quality ratio, based on as (A) ingredient 100 mass parts of total amount of the polymer of compound and (B) ingredient, containing 5 mass parts~500 mass parts (C) ingredient, relatively In 100 mass parts of total amount of the polymer of the polymer and (C) ingredient of compound, (B) ingredient as (A) ingredient, contain 0.1 mass parts~40 mass parts (D) ingredient, relative to compound, (B) ingredient as (A) ingredient polymer and (C) at 100 mass parts of total amount of the polymer divided, contain 0.01 mass parts~10 mass parts (E) ingredient.

Matching in the case where using the cured film formation composition of present embodiment as a solution described below Composition and division in a proportion example, modulator approach etc..

As long as each ingredient is dissolves uniformly in solvent, to consolidating in the cured film formation composition of present embodiment The ratio of body ingredient is not particularly limited, and is the 1 mass % of mass %~80, preferably 2 mass %~60 mass %, and more preferably 3 The mass of quality %~40 %.Here, so-called solid component, refer to removed from the whole components of cured film formation composition it is molten Ingredient obtained by agent.

The modulator approach of the cured film formation composition of present embodiment is not particularly limited.As modulation method, can lift Out for example, into the solution of (B) ingredient for being dissolved in solvent with defined ratio mixing (A) ingredient and (C) ingredient, (D) ingredient, And (E) ingredient, the method that uniform solution is made, or in the stage appropriate of the modulation method, further add as needed Add other additives and mixed method.

It, can be directly using anti-by the polymerization in solvent when modulating the cured film formation composition of present embodiment The solution of specific copolymer obtained by answering.At this point, for example, being added in the solution for having modulated (B) ingredient acrylic acid series polymeric compounds (A) ingredient, (C) ingredient, (D) ingredient and (E) ingredient etc. and uniform solution is made.At this point it is possible to be adjusted to mesh with concentration And further additional input solvent.At this point, group is used in solvent used in the modulated process of (B) ingredient and cured film formation Closing solvent used in the concentration adjustment of object can be identical, furthermore can also be different.

In addition, the solution about the cured film formation composition modulated, preferably in the mistake using 0.2 μm or so of aperture Filter etc. uses after being filtered.

As described above, the cured film formation composition of present embodiment of the invention contain (A) ingredient, (B) ingredient, (C) ingredient and (D) ingredient and be configured, as (A) ingredient be the chemical combination with light orientation group and heat cross-linking group At least one of object, as (B) ingredient be comprising with N- alkoxy methyl repetitive unit and have include polymerism C=C The polymer of the repetitive unit of the side chain of double bond is at least one in (C-1), (C-2) and (C-3) as (C) ingredient (C-1): kind polymer has and replaces selected from least one of hydroxyl, carboxyl, amide groups, amino and alkoxysilyl The polymer of base, (C-2): the substituent group of thermal response can be carried out with (A) ingredient and can carry out the polymer of self-crosslinking, (C- by having 3): melamine formaldehyde resin is crosslinking catalyst as (D) ingredient.In the compound as (A) ingredient, light orientation Group constitutes hydrophobic light reaction portion, replaces selected from least one of hydroxyl, carboxyl, amino and trialkoxysilyl Base constitutes hydrophilic thermal response portion.(C) polymer of ingredient be selected from hydroxyl, carboxyl, amino and trialkoxysilyl At least one of substituent group be also hydrophilic.

Accordingly, with respect to the cured film formed by the cured film formation of present embodiment with composition, due to the property of (C) ingredient Matter, inside become hydrophily and be formed so that membrane structure stabilize.Moreover, the compound of (A) ingredient in cured film is inclined To being distributed near the surface of cured film.More specifically, the compound of (A) ingredient takes hydrophilic thermal response portion towards admittedly Change the private side of film, hydrophobic light reaction portion towards the structure of surface side, and is biased to be distributed near the surface of cured film. As a result, the cured film of present embodiment realizes the ratio for making to be present in the photoreactive group of (A) near surface ingredient The increased structure of example.Moreover, the cured film of present embodiment in the case where using as oriented material, can make to take for light To and carry out light reaction efficiency improve, can have excellent orientation sensitivity.In turn, become and be suitble to patterning phase difference The oriented material of the formation of material, the patterning phase difference material manufactured using the oriented material can have excellent pattern shape It becomes second nature.

In addition, as described above, the cured film formation composition of present embodiment contains comprising having N- alkoxy methyl Repetitive unit and the polymer of repetitive unit with the side chain comprising polymerism C=C double bond be used as (B) ingredient.Therefore, exist By the inside for the cured film that the cured film formation of present embodiment is obtained with composition, light is carried out in the compound of (A) ingredient and is taken It, can be by carrying out cross-linking reaction with the thermal response of (B) ingredient before light reaction caused by tropism group.As a result, in conduct In the case where oriented material use, the patience to the polymerizable liquid crystal and/or its solvent that are coated on the material can be improved.

In addition, used in the cured film for using composition to obtain by the cured film formation of present embodiment as oriented material In the case of, the polymer as (B) ingredient, which plays, to be strengthened and is formed on the material and between cured polymerizable liquid crystal layer The function of adaptation.

By the solution of the cured film formation composition of present embodiment in substrate (for example, silicon/silicon dioxide is coated base Plate, silicon nitride board, the substrate being coated by metal such as aluminium, molybdenum, chromium etc., glass substrate, quartz base plate, ito substrate etc.), Film is (for example, triacetyl cellulose (TAC) film, cyclo-olefin-polymer films, polyethylene terephthalate film, acrylic acid mesentery Equal resin films) etc. on, pass through spin coating, ink-jet application, printing after stick painting, spin coating, flow coat, roller coating, slot coated, slot coated Film is formed etc. being coated, is then thermally dried in heating plate or baking oven etc., so as to form cured film.

As the condition of heat drying, as long as the ingredient of the oriented material formed by cured film is coated on it not dissolve out On polymerizable liquid crystal solution in degree carry out curing reaction, for example, using from temperature 60 C~200 DEG C, time 0.4 Minute~60 minutes ranges in the heating temperature that suitably selects and heating time.Heating temperature and heating time are preferably 70 DEG C ~160 DEG C, 0.5 minute~10 minutes.

It the use of the film thickness that the solidification compound of present embodiment is formed by cured film is such as 0.05 μm~5 μm, it can With consider the difference of height of substrate used, optical property, electrical property and suitably select.

The cured film being thusly-formed can be by carrying out polarisation UV irradiation as oriented material, that is, makes comprising polymerism Component that the compound with liquid crystal liquid crystal property including liquid crystal etc. is orientated and function.

As the illuminating method of polarisation UV, usually using ultraviolet light~visible light of wavelength 150nm~450nm, by Room temperature is carried out from vertical or oblique direction linear polarization in the state of heated.

Since there is solvent resistance and heat resistance by the oriented material that film composition is formed that solidifies of present embodiment, After coating is comprising the phase difference material of polymerizable liquid crystal solution on the oriented material, by the phase transition temperature for being heated to the liquid crystal It spends and makes phase difference material mesomorphic state, be orientated it on oriented material.Then, desired state of orientation is become Phase difference material directly solidify, the phase difference material with optically anisotropic layer can be formed.

As phase difference material, it is, for example, possible to use the liquid crystal monomer with polymerizable group and contain the liquid crystal monomer Composition etc..Moreover, in the case where forming the substrate of oriented material is film, the phase difference material with present embodiment Film is useful as phase difference film.There is the phase difference material of phase difference material as being capable of forming becomes mesomorphic state, The material that the state of orientation such as horizontal alignment, cholesterine orientation, vertical orientation, hybrid orientation are taken on oriented material, can distinguish Phase difference characteristics as needed and be used separately.

In addition, in the case where manufacturing patterning phase difference material used in 3D display device, to by present embodiment The cured film for solidifying film composition and being formed by the above method, via the mask of line and space pattern according to the benchmark of regulation, For example, carrying out polarisation UV exposure with the direction of+45 degree, then, removes the direction spent after mask with -45 and expose polarisation UV, thus Obtain the oriented material for foring the different 2 kinds of liquid crystal aligning regions in tropism control direction of liquid crystal.Then, coating includes polymerization After the phase difference material of property liquid crystal solution, it is heated to the phase transition temperature of liquid crystal, to make phase difference material mesomorphic state.Become Be orientated on the oriented material for being formed with 2 kinds of liquid crystal aligning regions for the polymerizable liquid crystal of mesomorphic state, formed respectively with The corresponding state of orientation in each liquid crystal aligning region.Then, solidify such phase difference material for realizing state of orientation directly, By above-mentioned state of orientation immobilization, it can obtain and regularly be configured respectively by 2 kinds of different phase difference regions of phase difference characteristics Phase difference material is patterned made of multiple.

In addition, being also used as liquid crystal display element by the oriented material that film composition is formed that solidifies of present embodiment Liquid crystal orientation film.For example, using having 2 plate bases formed as described above, the oriented material of present embodiment, with via The mode that parting faces each other the oriented material on two substrates is bonded, and then injects liquid crystal between these substrates, can be made The liquid crystal display element that liquid making crystalline substance is orientated.

Therefore, the cured film formation composition of present embodiment can be adapted for manufacturing various phase difference material (phases Poor film), liquid crystal display element etc..

Embodiment

Embodiment is enumerated below further present embodiment is described in detail.But the present invention is not implemented by these Example limits.

[constituent used in embodiment etc. and its abbreviation]

Each constituent used in embodiment below and comparative example is as follows.

CIN1:4- (6- Methacryloxyhexyl -1- oxygroup) cinnamic acid

CIN2:4- (3- methacryloxypropyl -1- oxygroup) cinnamic acid

CIN3:4- propyl oxygroup cinnamic acid

CIN4:4- (6- hydroxyl hexyl oxygroup) methyl cinnamate

CIN5:3- methoxyl group -4- (6- hydroxyl hexyl oxygroup) methyl cinnamate

PEPO: polyol polyester polymer (adipic acid/diethylene glycol copolymer with following structural units.Molecular weight 4800。)

(in above-mentioned formula, R indicates alkylidene.)

PTSA: p-methyl benzenesulfonic acid

HMM: [the サイメ Le (CYMEL) (registered trademark) 303 (three of melamine crosslinkers shown in following structural formulas Well サイテッ Network (strain) system)]

CIN1:4- (6- Methacryloxyhexyl -1- oxygroup) cinnamic acid

HEMA: 2-hydroxyethyl methacrylate

MMA: methyl methacrylate

BMAA:N- (butoxymethyl) acrylamide

AIBN: α, α '-azodiisobutyronitrile

Each phase difference material formation composition of embodiment and comparative example contains solvent, as the solvent, uses the third two Alcohol monomethyl ether (PM), butyl acetate (BA), butanone (MEK), cyclohexanone (CHN).

The molecular weight of polyimides, polyamic acid or acrylic acid series polymeric compounds in synthesis example uses (strain) Shodex society system Room temperature gel permeation chromatography (GPC) device (GPC-101), Shodex society column (KD -803, KD-805), are surveyed as follows It is fixed.

Column temperature: 50 DEG C

Eluent: n,N-Dimethylformamide is (as additive, lithium bromide monohydrate (LiBrH₂It O) is 30mmol/ L, phosphoric acid anhydrous crystal (orthophosphoric acid) are 30mmol/L, and tetrahydrofuran (THF) is 10mL/L)

Flow velocity: 1.0mL/ minutes

Make standard curve with standard sample: Dong ソー society TSK standard polyethylene oxide (molecular weight about 900,000, 150,000,100,000,30,000) and Port リマーラボラトリー society polyethylene glycol (molecular weight about 12,000,4,000, 1,000)。

<¹H-NMR analysis >

For¹The analytical equipment and analysis condition of H-NMR analysis are as follows.

Nuclear magnetic resonance device: Varian NMR System 400NB (400MHz)

Measure solvent: DMSO-d₆

Primary standard substance: tetramethylsilane (TMS) (δ 0.0ppm for¹H)

By M6CA 4.0g, styrene 4.0g, HEMA 2.0g, as the AIBN0.1g of polymerization catalyst it is dissolved in PM In 90.9g, react within 20 hours by making it at 80 DEG C, to obtain acrylic acid series copolymer solution, (solid component is dense Spend 10 mass %) (CIN6).The Mn of resulting acrylic acid series copolymer is 20,000, Mw 55,000.

Tetrahydrofuran 204.0g is dissolved in by BMAA 32.0g, HEMA 8.0g, as the AIBN 0.8g of polymerization catalyst In, react within 20 hours by making it at 60 DEG C, to obtain acrylic acid series copolymer solution.By acrylic acid series copolymer Solution is slowly added drop-wise in hexane 1000.0g, and solid is precipitated, and is filtered and is dried under reduced pressure, so that it is total to obtain acrylic acid series Polymers (PB-1).The Mn of resulting acrylic acid series copolymer is 7,000, Mw 20,000.

Tetrahydrofuran 204.0g is dissolved in by BMAA 28.0g, HEMA 12.0g, as the AIBN 0.8g of polymerization catalyst In, react within 20 hours by making it at 60 DEG C, to obtain acrylic acid series copolymer solution.By acrylic acid series copolymer Solution is slowly added drop-wise in hexane 1000.0g, and solid is precipitated, and is filtered and is dried under reduced pressure, so that it is total to obtain acrylic acid series Polymers (PB-2).The Mn of resulting acrylic acid series copolymer is 8,300, Mw 25,000.

Tetrahydrofuran 204.0g is dissolved in by BMAA 24.0g, HEMA 16.0g, as the AIBN 0.8g of polymerization catalyst In, react within 20 hours by making it at 60 DEG C, to obtain acrylic acid series copolymer solution.By acrylic acid series copolymer Solution is slowly added drop-wise in hexane 1000.0g, and solid is precipitated, and is filtered and is dried under reduced pressure, so that it is total to obtain acrylic acid series Polymers (PB-3).The Mn of resulting acrylic acid series copolymer is 9,800, Mw 35,000.

Tetrahydrofuran 204.0g is dissolved in by BMAA 32.0g, GMA 8.0g, as the AIBN 0.8g of polymerization catalyst In, react within 20 hours by making it at 60 DEG C, to obtain acrylic acid series copolymer solution.By acrylic acid series copolymer Solution is slowly added drop-wise in hexane 1000.0g, and solid is precipitated, and is filtered and is dried under reduced pressure, so that it is total to obtain acrylic acid series Polymers (PB-4).The Mn of resulting acrylic acid series copolymer is 7,000, Mw 18,000.

It is dissolved in tetrahydrofuran 204.0g by GMA 40.0g, as the AIBN 0.8g of polymerization catalyst, by 60 It is set react within 20 hours at DEG C, to obtain acrylic polymer solution.Acrylic polymer solution is slowly dripped It is added in hexane 1000g, solid is precipitated, be filtered and be dried under reduced pressure, to obtain acrylic acid series polymeric compounds (PB-5).Institute The Mn of the acrylic acid series polymeric compounds obtained is 8,000, Mw 20,000.

It is dissolved in PM 450.0g by MMA 100.0g, HEMA 11.1g, as the AIBN 5.6g of polymerization catalyst, It is set react within 20 hours at 80 DEG C, to obtain acrylic acid series copolymer solution (20 mass % of solid component concentration) (PC- 1).The Mn of resulting acrylic acid series copolymer is 4,200, Mw 7,600.

It is dissolved in PM 193.5g by BMAA 100.0g, as the AIBN 4.2g of polymerization catalyst, makes it at 90 DEG C React within 20 hours, to obtain acrylic polymer solution (35 mass % of solid component concentration) (PC-2).It is resulting The Mn of acrylic acid series copolymer is 2,700, Mw 3,900.

Make acrylic acid series copolymer (PB-1) 10.0g, 2- acryloyloxyethyl isocyanate obtained by polymerization example 2 4.3g, dibutyl hydroxy toluene 0.4g, tetrahydrofuran 60g is dissolved in as the dibutyl tin dilaurate 10mg of catalysts In, so that it react within 5 hours at 60 DEG C.The solution is slowly added drop-wise in hexane 500g, solid is precipitated, is filtered Be dried under reduced pressure, thus obtain have acryloyl group acrylic acid series copolymer (PB-6).It carries out¹H-NMR analysis, confirms propylene Sour based copolymer (PB-6) has acryloyl group.

Make acrylic acid series copolymer (PB-1) 10.0g, 2- the methacryloxyethyl isocyanic acid obtained by polymerization example 2 Ester 4.3g, dibutyl hydroxy toluene 0.4g, tetrahydrofuran is dissolved in as the dibutyl tin dilaurate 10mg of catalysts In 60g, it is made react within 5 hours at 60 DEG C.The solution is slowly added drop-wise in hexane 500g, solid is precipitated, is carried out It filters and is dried under reduced pressure, to obtain the acrylic acid series copolymer (PB-7) with methylacryloyl.It carries out¹H-NMR analysis, Confirm that acrylic acid series copolymer (PB-7) has methylacryloyl.

Make acrylic acid series copolymer (PB-2) 10.0g, 2- acryloyloxyethyl isocyanate obtained by polymerization example 3 6.5g, dibutyl hydroxy toluene 0.6g, tetrahydrofuran 60g is dissolved in as the dibutyl tin dilaurate 10mg of catalysts In, so that it react within 5 hours at 60 DEG C.The solution is slowly added drop-wise in hexane 500g, solid is precipitated, is filtered Be dried under reduced pressure, thus obtain have acryloyl group acrylic acid series copolymer (PB-8).It carries out¹H-NMR analysis, confirms propylene Sour based copolymer (PB-8) has acryloyl group.

Make acrylic acid series copolymer (PB-3) 10.0g, 2- acryloyloxyethyl isocyanate obtained by polymerization example 4 8.7g, dibutyl hydroxy toluene 0.9g, tetrahydrofuran 60g is dissolved in as the dibutyl tin dilaurate 10mg of catalysts In, so that it react within 5 hours at 60 DEG C.The solution is slowly added drop-wise in hexane 500g, solid is precipitated, is filtered Be dried under reduced pressure, thus obtain have acryloyl group acrylic acid series copolymer (PB-9).It carries out¹H-NMR analysis, confirms propylene Sour based copolymer (PB-9) has acryloyl group.

Make acrylic acid series copolymer (PB-4) 10.0g, the acrylic acid 2.2g, dibutyl hydroxy toluene obtained by polymerization example 5 0.2g, it is dissolved in PM60g as the benzyltriethylammoinium chloride 10mg of catalysts, carries out it 20 hours Reaction.The solution is slowly added drop-wise in hexane 500g, solid is precipitated, is filtered and is dried under reduced pressure, to be had The acrylic acid series copolymer (PB-10) of acryloyl group.It carries out¹H-NMR analysis, confirmation acrylic acid series copolymer (PB-10) have Acryloyl group.

Make acrylic acid series copolymer (PB-4) 10.0g, the methacrylic acid 2.2g, dibutyl hydroxy obtained by polymerization example 5 Toluene 0.2g, it is dissolved in PM 60g as the benzyltriethylammoinium chloride 10mg of catalysts, its progress is made at 90 DEG C It reacts within 20 hours.The solution is slowly added drop-wise in hexane 500g, solid is precipitated, is filtered and is dried under reduced pressure, to obtain There must be the acrylic acid series copolymer (PB-11) of methylacryloyl.It carries out¹H-NMR analysis, confirms acrylic acid series copolymer (PB-11) there is methylacryloyl.

Make acrylic acid series copolymer (PB-5) 10.0g, the acrylic acid 2.0g, dibutyl hydroxy toluene obtained by polymerization example 6 0.2g, it is dissolved in PM60g as the benzyltriethylammoinium chloride 10mg of catalysts, carries out it 20 hours Reaction.The solution is slowly added drop-wise in hexane 500g, solid is precipitated, is filtered and is dried under reduced pressure, to be had The acrylic acid series copolymer (PB-12) of acryloyl group.It carries out¹H-NMR analysis, confirmation acrylic acid series copolymer (PB-12) have Acryloyl group.

The acrylic acid mesentery used as substrate can be made for example, by the following method.That is, making comprising with methyl-prop E pioic acid methyl ester is that the feed particles of copolymer of principal component etc. melt in an extruder at 250 DEG C, makes it through T-die, By casting roll and dryer roll etc., 40 μm of thickness of acrylic acid mesentery can be made.

<embodiment, comparative example>

According to each cured film formation composition of composition modulation embodiment and comparative example shown in table 1.Then, using each The formation of phase difference material forms cured film with composition, carries out orientation and adaptation respectively for each resulting cured film Evaluation.

[table 1]

[evaluation of orientation]

Each cured film formation of embodiment and comparative example is coated on film with composition using bar coater, then in temperature At 100 DEG C, 2 minutes heat dryings are carried out in heat-circulation type baking oven, form cured film.To each cured film with 20mJ/cm²'s Light exposure vertically irradiates the linear polarization of 313nm, forms oriented material.It is applied on the oriented material on substrate using bar coater Cloth horizontal alignment polymerizable liquid crystal solution then at 70 DEG C, carries out 60 seconds prebake conditions on hot plate, forms film thickness 1.0 μm film.With 300mJ/cm²Film on the substrate is exposed, phase difference material is made.It will be on the substrate of production Phase difference material is clamped with a pair of of polarizer, observes the current status of the phase difference characteristics of phase difference material, and phase difference is intact The case where the case where showing sunkenly is denoted as zero, and phase difference is not showed be denoted as ×, and they are documented in " orientation " Column.

[evaluation of adaptation]

Each cured film formation of embodiment and comparative example is coated on film with composition using bar coater, then in temperature At 100 DEG C, 2 minutes heat dryings are carried out in heat-circulation type baking oven, form cured film.To each cured film with 20mJ/cm²'s Light exposure vertically irradiates the linear polarization of 313nm, forms oriented material.It is applied on the oriented material on substrate using bar coater Cloth horizontal alignment polymerizable liquid crystal solution then at 70 DEG C, carries out 60 seconds prebake conditions on hot plate, forms film thickness 1.0 μm film.With 300mJ/cm²Film on the substrate is exposed, phase difference material is made.Using cutter to the phase Potential difference material is divided into 10 × 10 grids with the interval of 1mm in length and breadth.Using adhesive tape (Scotch tape) on the cut-in grid Carry out cellophane tape disbonded test.Using evaluation result as " initial stage ", 100 grids are all unstripped and feelings that left behind Condition is denoted as zero, though will have the removing of 1 grid the case where be denoted as ×.Evaluation result summarizes in the table 2 after being shown in.

[evaluation of durable adaptation]

It is set as being put by the phase difference material on the film of the same method production of evaluation with above-mentioned adaptation 80 DEG C of temperature, humidity 90% baking oven in, carry out 72 hours or more standing.Then, take out phase difference material, by with it is above-mentioned The same method of the evaluation of adaptation evaluates adaptation.Evaluation result summarizes as " durable " to be shown in Table 2.

[result of evaluation]

As described above, the result of evaluation more than progress is shown in Table 2.

[table 2]

Using embodiment 1~17, comparative example 1~2 each phase difference material formation composition and the cured film that obtains can By down to 20mJ/cm²Light exposure formed phase difference material.In contrast, using each phase difference material shape of comparative example 3 Orientation is not obtained at the cured film obtained with composition.

Even if the cured film obtained with composition using each phase difference material formation of embodiment 1~17 is in the early stage and high temperature Also high adhesion is maintained after high humidity treatment, it is shown that excellent adaptation.

In contrast, the cured film obtained using the cured film formation composition of comparative example 1~3 is in the early stage and high temperature It is all difficult to maintain adaptation after high humidity treatment.

Industrial availability

Phase difference material formation of the invention uses composition as being used to form the liquid crystal orientation film of liquid crystal display element, set Set the oriented material in the internal or external optical anisotropic film of liquid crystal display element be it is highly useful, especially as The forming material of the patterning phase difference material of 3D display device is suitable.In turn, as formation thin film transistor (TFT) (TFT) type liquid The material of the cured films such as protective film, planar film and insulating film in the various displays such as crystal display element, organic EL element, especially It is as the interlayer dielectric of formation TFT type liquid crystal display element, the protective film of colour filter or insulating film of organic EL element etc. Material be also suitable.

Claims

1. a kind of cured film, which is formed, uses composition, contain (A) ingredient and (B) ingredient,

(A) ingredient: having at least one of light orientation group and the compound of heat cross-linking group,

(B) ingredient: include the repetitive unit with N- alkoxy methyl and the weight with the side chain comprising polymerism C=C double bond The polymer of multiple unit.

2. cured film according to claim 1, which is formed, uses composition, the light orientation group of (A) ingredient is to carry out photodimerization The functional group of the structure of change or photoisomerization.

3. cured film according to claim 1 or 2, which is formed, uses composition, the light orientation group of (A) ingredient is cinnamoyl Base.

4. cured film according to claim 1 or 2, which is formed, uses composition, the light orientation group of (A) ingredient is azobenzene The group of structure.

5. cured film according to claim 1 or 2, which is formed, uses composition, also contain (C) ingredient, (C) ingredient is Selected from least one of (C-1), (C-2) and (C-3) polymer,

(C-1): having selected from the poly- of at least one of hydroxyl, carboxyl, amide groups, amino and alkoxysilyl substituent group Object is closed,

(C-3): melamine formaldehyde resin.

6. cured film according to claim 1 or 2, which is formed, uses composition, also contain (D) crosslinking catalyst.

7. cured film according to claim 1 or 2, which is formed, uses composition, also contain (E) crosslinking agent.

8. cured film according to claim 1 or 2, which is formed, uses composition, in the polymer of (B) ingredient, there is N- alcoxyl 100 moles of whole repetitive units there are ratio relative to the polymer of the repetitive unit of ylmethyl rub for 40 moles of %~90 You are %, and the whole there are ratio relative to the polymer of the repetitive unit with the side chain comprising polymerism C=C double bond repeats 100 moles of unit are 10 moles of %~60 mole %.

9. cured film according to claim 1 or 2, which is formed, uses composition, the content ratio of (A) ingredient and (B) ingredient is with quality Than being calculated as 5:95~60:40.

10. cured film according to claim 5, which is formed, uses composition, it is based on the total amount 100 of (A) ingredient and (B) ingredient Mass parts contain 5 mass parts~500 mass parts (C) ingredient.

11. a kind of optical film is to be obtained by cured film formation according to any one of claims 1 to 10 with composition.

12. a kind of liquid crystal aligning material is formed using the optical film described in claim 11.

13. a kind of phase difference material is formed using the optical film described in claim 11.