CN106459324A

CN106459324A - Cured film-forming composition, alignment material, and phase-difference material

Info

Publication number: CN106459324A
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: 2017-02-22
Anticipated expiration: 2035-06-29
Also published as: WO2016002722A1; TW201615715A; JP6604483B2; JP2020019964A; TWI678389B; CN110408159A; KR20170023840A; JPWO2016002722A1; JP6823295B2; KR102318651B1; CN110408159B; CN106459324B

Abstract

The invention discloses a cured film-forming composition, an alignment material, and a phase-difference material. The purpose is to provide an alignment material, a phase-difference material using said alignment material, and an optical film having, in a surface layer, a cured film that has excellent adhesiveness and liquid crystal alignment properties. The alignment material, the phase-difference material, and the cured film-forming composition are characterized by comprising: (A) at least one compound having a photo-alignable group and a thermally crosslinkable group; (B) a polymer that contains a recurring unit having an N-alkoxymethyl group and a recurring unit having a side chain containing a polymerizable C=C double bond; and (C) at least one polymer selected from the group consisting of: (C-1) a polymer having at least one substituent selected from the group consisting of a hydroxy group, a carboxyl group, amide groups, amino groups, and alkoxysilyl groups; (C-2) a self-crosslinkable polymer having a substituent that can thermally react with component (A); and (C-3) a melamine formaldehyde resin.

Description

Cured film is formed with compositionss, oriented material and phase contrast material

Technical field

The present invention relates to cured film is formed with compositionss, oriented material and phase contrast material.

Background technology

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

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

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

In the case of the 3D display of rotatory polarization glasses mode, generally form the display element of image in liquid crystal panel etc. Upper configuration phase difference material.On this phase contrast material, 2 kinds of different phase contrast regions of multiple phase difference characteristics are regularly joined respectively Put, constitute the phase contrast material defining pattern.In addition, below in this manual, will be to configure such phase difference characteristics The different modes in multiple phase contrast regions and the phase contrast material that has been patterned is referred to as patterning phase contrast material.

With regard to patterning phase contrast material, such as disclosed in patent documentation 2, can pass through to comprise polymerism The phase contrast material of liquid crystal carries out optical design and is formed to make.Comprise the optical design shape of the phase contrast material of polymerizable liquid crystal Become, using light orientation technology known in being formed in the oriented material of liquid crystal panel.That is, substrate is arranged by light orientation The film that material is formed, irradiates 2 kinds of different polarisations of polarization direction to it.Then, as the tropism control side defining liquid crystal To the oriented material in 2 kinds of different liquid crystal aligning regions, obtain optical alignment film.On this optical alignment film, coating comprises polymerism liquid Brilliant solution shape phase contrast material, realizes the orientation of polymerizable liquid crystal.Then, the polymerizable liquid crystal being orientated is solidified to form Patterning phase contrast material.

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

Prior art literature

Patent documentation

Patent documentation 1：Japanese Unexamined Patent Publication 10-232365 publication

Patent documentation 2：Japanese Unexamined Patent Publication 2005-49865 publication

Patent documentation 3：No. 3611342 description of Japanese Patent Publication No.

Patent documentation 4：Japanese Unexamined Patent Publication 2009-058584 publication

Patent documentation 5：Japanese Unexamined Patent Application Publication 2001-517719 publication

Content of the invention

Invent problem to be solved

As described above, patterning phase contrast material is in the light as oriented material using the layer of the polymerizable liquid crystal that have cured Alignment films superimposed layer and constitute.And, the patterning phase contrast material with such laminated construction can be with this laminated State is directly used in the composition of 3D display.

3D display is also sometimes used as home-use TV it is desirable to high reliability, particularly after long durability. Therefore, for the member of formation of 3D display, also require that durability.Therefore, in patterning phase contrast material, with high accuracy While carrying out optical design formation, have high light transmittance characteristic etc., long durability becomes necessary performance.

However, for conventional patterning phase contrast material, closely sealed between optical alignment film and polymerizable liquid crystal layer Property existing problems.For example, between optical alignment film and polymerizable liquid crystal layer, exist and start to be easy for being peeling from the formation initial stage Although problem or forming initial stage excellent adhesion, pass through over time, adaptation declines and is easily peeling Problem.

Wherein, over time through and produce, the stripping between optical alignment film and polymerizable liquid crystal layer becomes in reality Used in 3D display defect, become the reason make the display quality of 3D display decline.It is therefore desirable to height can be carried out The optical design of precision is formed, and optical transmission characteristics are excellent, and then the patterning phase contrast material of excellent in te pins of durability.Special requirement exist Excellent adhesion between the optical alignment film at formation initial stage and polymerizable liquid crystal layer, is provided simultaneously with maintaining for a long time this excellent close The durability of conjunction property is (below, in this manual for closely sealed durability.) patterning phase contrast material.

The present invention is to be proposed based on above understanding, result of study.That is, it is an object of the invention to provide, be suitable for Formed and there are excellent liquid crystal aligning and optical transmission characteristics, the cured film formation combination of the cured film of closely sealed excellent in te pins of durability Thing.The cured film formation compositionss forming following cured film are particularly provided, described cured film using as oriented material, And when being configured with polymerizable liquid crystal layer thereon, show excellent liquid crystal aligning and transmitance, can maintain for a long time simultaneously Adaptation and polymerizable liquid crystal layer between, closely sealed excellent in te pins of durability.

It is an object of the invention to provide, liquid crystal aligning and optical transmission characteristics are excellent, closely sealed excellent in te pins of durability orientation material Material.

It is an object of the invention to provide, the phase contrast material of high-precision optical design formation, excellent in te pins of durability can be carried out Material.

Other objects of the present invention and advantage can be clear and definite by following record.

Method for solving problem

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

(A) composition is at least one having in light orientation group and the compound of heat cross-linking group,

(B) composition is the polymer comprising following repetitives,

Have N- alkoxy methyl repetitives and

There are the repetitives of the side chain comprising polymerism C=C double bond.

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

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

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

(C-1)：There is at least one substituent group in hydroxyl, carboxyl, amide groups, amino and alkoxysilyl Polymer,

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

(C-3)：Melamine formaldehyde resin.

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

In the 1st scheme of the present invention, preferably it also contains (E) cross-linking agent.

In the 1st scheme of the present invention, preferably in the polymer of (B) composition, there is the repetition list of N- alkoxy methyl The presence ratio of unit is 40 moles of %～90 mole % with respect to 100 moles of whole repetitives of this polymer, has and comprises The presence ratio of the repetitives of side chain of polymerism C=C double bond with respect to 100 moles of whole repetitives of this polymer is 10 moles of %～60 mole %.

In the 1st scheme of the present invention, the content ratio of preferably (A) composition and (B) composition is 5 by quality ratio:95～60: 40.

In the 1st scheme of the present invention, based on total amount 100 mass parts of (A) composition and (B) composition, said curing film Formation compositionss preferably comprise (C) composition of 5 mass parts～500 mass parts.

2nd scheme of the present invention is related to a kind of oriented material it is characterised in that being the heat of the 1st scheme using the present invention Cured film formation compositionss obtain.

3rd scheme of the present invention is related to a kind of phase contrast material it is characterised in that being using the 1st scheme by the present invention Cured film formation compositionss obtain cured film and formed.

Invention effect

A kind of the 1st scheme according to the present invention, using the teaching of the invention it is possible to provide cured film formation compositionss, it is used for being provided with excellent Photoreaction efficiency and solvent resistance, even if polymerizable liquid crystal also can be made on resin film with taking that high sensitivity is orientated To material.

The 2nd scheme according to the present invention, using the teaching of the invention it is possible to provide possess excellent photoreaction efficiency and solvent resistance, even if in resin The oriented material that polymerizable liquid crystal is orientated with high sensitivity also can be made on film.

The 3rd scheme according to the present invention, using the teaching of the invention it is possible to provide even if also being formed with high efficiency on resin film and can entering The phase contrast material that row optical design is formed.

Specific embodiment

As described above, in order to manufacture the patterning phase contrast material of excellent durability it is desirable to closely sealed excellent in te pins of durability Oriented material, the particularly oriented material of the closely sealed excellent in te pins of durability and the polymerizable liquid crystal layer of solidification between.And it is it is desirable to suitable Close the cured film formation compositionss of the oriented material forming such performance.

Present inventor has made intensive studies to respond above-mentioned requirement, it was found that by having specific composition The transmitance of the cured film that cured film formation is obtained with compositionss is excellent, furthermore, it is possible to expose by polarisation as display Control the oriented material of the liquid crystal aligning of liquid crystal aligning.And, the inventors have found that, should be by the cured film with specific composition The cured film that formation compositionss obtain shows excellent closely sealed durable between the polymerizable liquid crystal layer of polymerizing curable thereon Property.That is, being formed by the cured film with specific composition of the present invention be may be constructed and polymerism with the cured film of compositionss acquisition The optical alignment film of the closely sealed excellent in te pins of durability between liquid crystal layer.

Below for the cured film formation compositionss of the present invention, the concrete example enumerating composition etc. enters in detail Row explanation.Then, the cured film for the present invention of the cured film formation compositionss using the present invention and oriented material and The phase contrast material being formed using this oriented material and liquid crystal display cells etc. are illustrated.

The cured film formation compositionss of the present invention can contain (A) composition, (B) composition, (C) composition and conduct (D) The crosslinking catalyst of composition, described (A) composition is at least one of the compound with light orientation group and heat cross-linking group Kind, described (B) composition is to comprise to have the repetitives of N- alkoxy methyl and have the side chain comprising polymerism C=C double bond Repetitives polymer, described (C) composition is at least one polymer in (C-1), (C-2) and (C-3), (C-1)：There is the polymerization of at least one substituent group in hydroxyl, carboxyl, amide groups, amino and alkoxysilyl Thing, (C-2)：Have and can carry out the substituent group of thermal response with (A) composition and the polymer of self-crosslinking can be carried out, (C-3)：Trimerization Cyanamide-formaldehyde resin.Furthermore, it is possible to containing the cross-linking agent as (E) composition.And then, in the model of the effect not damaging the present invention In enclosing, other additives can be contained.Solvent can be contained further.

The detailed content of each composition is below described.

[(A) composition]

(A) composition in the cured film formation compositionss of the present invention is with light orientation group and heat cross-linking group Compound at least one.As (A) composition, it is possible to use polymer, it is possible to use the compound beyond polymer.? This, the compound beyond so-called polymer, specifically represent the compound in molecule without repetitives, usually low molecule Compound.Therefore, (A) composition can be the polymer with light orientation group and heat cross-linking group at least one, There is at least one of compound beyond light orientation group and the polymer of heat cross-linking group or there is light orientation base The polymer of group and heat cross-linking group and the compound beyond there is the polymer of light orientation group and heat cross-linking group Mixture.

(A) composition is to the one-tenth being formed the cured film imparting light orientation being obtained with compositionss by the cured film of the present invention Point, in this manual, also (A) composition is referred to as light orientation composition.

The detailed content of the situation of compound beyond below explanation (A) composition is polymer.

(A) composition be polymer beyond compound in the case of, generally, with based on (B) described later composition Polymer be in a ratio of the light orientation composition of low-molecular-weight.

In the cured film formation compositionss of the present invention, in the case of the compound beyond (A) composition is polymer, (A) composition is the compound with light orientation group, and then can be and have selected from hydroxyl, carboxyl, amide groups, amino Compound with one of alkoxysilyl group.

In addition, in the present invention, so-called light orientation group, generally refers to play the property of orientation by light irradiation Functional group, representational refers to carry out the functional group of the structure position of photodimerization or photoisomerization.As other light orientations Property group, can enumerate for example cause light fries' rearrangement (photo Fries rearrangement) to react functional group (illustrate Compound：Benzoic acid ester compounds etc.), cause the group (exemplary compounds of photolysis reactionses：Tetramethylene. ring etc.) etc..

(A) compound beyond the polymer of composition carry out photodimerization as what light orientation group can have Structure position, is can to form dimeric position by light irradiation, as its concrete example, can enumerate cinnamoyl, chalcone derivative Base, coumarin base, anthryl etc..Wherein, from the height of the height of the transparency of visible region, photodimerizationization reactivity, It is preferably cinnamoyl.

Additionally, compound beyond the polymer of (A) composition as light orientation group can have to carry out light different The structure position of structure, refers to be changed into the structure position of cis body and trans body by light irradiation, as its concrete example, can lift Go out to comprise the position of azobenzene structure, structure etc..Wherein, from reactive height, preferably azobenzene structure.

There is light orientation group and selected from one of hydroxyl, carboxyl, amide groups, amino and alkoxysilyl base Compound beyond the polymer of group is for example, the compound shown in following formula.

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

X¹¹It is selected from singly-bound, ehter bond, ester bond, amido link, urea bond, amino-formate bond, amino linkage, carbonyl or their group One kind or two or more key in conjunction, or selected from carbon number be 1～18 alkylidene, phenylene, biphenylene or they Structure that 1～3 kind of substituent group in combination is combined into via this one kind or two or more key or by foregoing substituents Connect multiple structures via previous key respectively.

X¹²Represent alkyl, phenyl, xenyl or cyclohexyl that hydrogen atom, halogen atom, cyano group, carbon number are 1～18. Now, carbon number be two or more group in 1～18 alkyl, phenyl, xenyl and cyclohexyl can via covalent bond, Ehter bond, ester bond, amido link or urea bond and combine.

X¹³Represent alkylthio group, benzene oxygen that alkoxyl, carbon number that hydroxyl, sulfydryl, carbon number are 1～10 are 1～10 Base, biphenylyloxy or phenyl.

X¹⁴Represent the aliphatic ring group that singly-bound, carbon number are 1～20 alkylidene, the aromatic series ring group of divalent or divalent. Here, the alkylidene that carbon number is 1～20 can be branched can also be straight-chain.

X¹⁵Represent hydroxyl, carboxyl, amide groups, amino or alkoxysilyl.But, in X¹⁴During for singly-bound, X¹⁵For hydroxyl Base or amino.

X represents singly-bound, oxygen atom or sulphur atom.But, in X¹⁴During for singly-bound, X is also singly-bound.

In addition, in the case of comprising phenyl ring in these substituent groups, it is 1～4 that this phenyl ring can be selected from carbon number Alkyl, carbon number are identical or different one or more in 1～4 alkoxyl, halogen atom, trifluoromethyl and cyano group Substituent group replaces.

In above-mentioned formula, R¹¹、R¹²、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷And R¹⁸Separately represent that hydrogen atom, carbon number are 1 ～4 alkyl, carbon number are 1～4 alkoxyl, halogen atom, trifluoromethyl or cyano group.

Additionally, the alkyl being 1～18 as the carbon number defined in above-mentioned, can enumerate for example, methyl, ethyl, positive third Base, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, 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-pro-pyl, 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 isophthalic acid-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 own 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 isophthalic acid-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, Pentadecane base, n-hexadecyl, N-heptadecane base and n-octadecane base etc..The alkyl being 1～4 similarly as carbon number, can enumerate the above-mentioned group enumerating In have the group of corresponding carbon number.Additionally, as carbon number be 1～10 alkoxyl, carbon number be 1～4 alkane Epoxide, carbon number are 1～10 alkylthio group, can enumerate in group obtained by being aoxidized the above-mentioned alkyl enumerating or vulcanizing There is the group of corresponding carbon number.And then, the alkylidene being 1～20 as carbon number, can enumerate from abovementioned alkyl and The carbon numbers such as AI3-36122 base, AI3-28404 base be 1～20 alkyl in remove divalent group obtained by 1 hydrogen atom.

As the concrete example of the compound having beyond the polymer of light orientation group and hydroxyl of (A) composition, for example As the compound shown in above-mentioned formula [A11]～[A15] and the compound beyond this formula, can enumerate for example, (8- hydroxyl is pungent for 4- Base epoxide) methyl cinnamate, 4- (6- hydroxyl hexyl epoxide) methyl cinnamate, 4- (4- hydroxybutyl epoxide) methyl cinnamate, 4- (3- hydroxypropyl epoxide) methyl cinnamate, 4- (2- hydroxyethyl epoxide) methyl cinnamate, 4- hydroxymethyl epoxide Cortex Cinnamomi Sour methyl ester, 4- hydroxy-methyl cinnamate, 4- (8- hydroxy octyl epoxide) ethyl cinnamate, 4- (6- hydroxyl hexyl epoxide) cinnamic acid Ethyl ester, 4- (4- hydroxybutyl epoxide) ethyl cinnamate, 4- (3- hydroxypropyl epoxide) ethyl cinnamate, 4- (2- hydroxyethyl Epoxide) ethyl cinnamate, 4- hydroxymethyl epoxide ethyl cinnamate, 4- hydroxy cinnamate acetoacetic ester, 4- (8- hydroxy octyl epoxide) Phenyl cinnamate, 4- (6- hydroxyl hexyl epoxide) phenyl cinnamate, 4- (4- hydroxybutyl epoxide) phenyl cinnamate, 4- (3- hydroxyl Base propyl group epoxide) phenyl cinnamate, 4- (2- hydroxyethyl epoxide) phenyl cinnamate, 4- hydroxymethyl epoxide phenyl cinnamate, 4- hydroxy cinnamate acid phenenyl ester, 4- (8- hydroxy octyl epoxide) cinnamic acid Biphenyl Ester, 4- (6- hydroxyl hexyl epoxide) cinnamic acid biphenyl Ester, 4- (4- hydroxybutyl epoxide) cinnamic acid Biphenyl Ester, 4- (3- hydroxypropyl epoxide) cinnamic acid Biphenyl Ester, 4- (2- hydroxyl second Base epoxide) cinnamic acid Biphenyl Ester, 4- hydroxymethyl epoxide 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 epoxide) diphenyl diimide, 4- (6- hydroxyl hexyl epoxide) diphenyl diimide, 4- (4- hydroxybutyl Epoxide) diphenyl diimide, 4- (3- hydroxypropyl epoxide) diphenyl diimide, 4- (2- hydroxyethyl epoxide) diphenyl diimide, 4- hydroxymethyl epoxide Diphenyl diimide, 4- hydroxyazobenzene, 4- (8- hydroxy octyl epoxide) chalcone derivative, 4- (6- hydroxyl hexyl epoxide) chalcone derivative, 4- (4- hydroxyl Base butyl epoxide) chalcone derivative, 4- (3- hydroxypropyl epoxide) chalcone derivative, 4- (2- hydroxyethyl epoxide) chalcone derivative, 4- hydroxyl first Base epoxide chalcone derivative, 4- hydroxy chalcone, 4 '-(8- hydroxy octyl epoxide) chalcone derivative, 4 '-(6- hydroxyl hexyl epoxide) look into ear Ketone, 4 '-(4- hydroxybutyl epoxide) chalcone derivative, 4 '-(3- hydroxypropyl epoxide) chalcone derivative, 4 '-(2- hydroxyethyl epoxide) are looked into (6- hydroxyl is own for ear ketone, 4 '-hydroxymethyl epoxide chalcone derivative, 4'-hydroxychalcone, 7- (8- hydroxy octyl epoxide) coumarin, 7- Base epoxide) coumarin, 7- (4- hydroxybutyl epoxide) coumarin, 7- (3- hydroxypropyl epoxide) coumarin, 7- (2- hydroxyethyl Epoxide) coumarin, 7- hydroxymethyl epoxide coumarin, umbelliferone, 6- hydroxy octyl epoxide coumarin, 6- hydroxyl hexyl Epoxide coumarin, 6- (4- hydroxybutyl epoxide) coumarin, 6- (3- hydroxypropyl epoxide) coumarin, 6- (2- hydroxyethyl oxygen Base) coumarin, 6- hydroxymethyl epoxide coumarin, 6- Hydroxycoumarin, 4- [4- (8- hydroxy octyl epoxide) benzoyl] meat Acid methylester, 4- [4- (6- hydroxyl hexyl epoxide) benzoyl] methyl cinnamate, 4- [4- (4- hydroxybutyl epoxide) benzoyl Base] methyl cinnamate, 4- [4- (3- hydroxypropyl epoxide) benzoyl] methyl cinnamate, 4- [4- (2- hydroxyethyl epoxide) Benzoyl] methyl cinnamate, 4- [4- hydroxymethyl epoxide benzoyl] methyl cinnamate, 4- [4- hydroxy benzoyl] meat Acid methylester, 4- [4- (8- hydroxy octyl epoxide) benzoyl] ethyl cinnamate, 4- [4- (6- hydroxyl hexyl epoxide) benzoyl Base] ethyl cinnamate, 4- [4- (4- hydroxybutyl epoxide) benzoyl] ethyl cinnamate, 4- [4- (3- hydroxypropyl epoxide) Benzoyl] ethyl cinnamate, 4- [4- (2- hydroxyethyl epoxide) benzoyl] ethyl cinnamate, 4- [4- hydroxymethyl oxygen Base benzoyl] ethyl cinnamate, 4- [4- hydroxy benzoyl] ethyl cinnamate, 4- [4- (8- hydroxy octyl epoxide) benzene first Acyl group] Cortex Cinnamomi tert-butyl acrylate, 4- [4- (6- hydroxyl hexyl epoxide) benzoyl] Cortex Cinnamomi tert-butyl acrylate, 4- [4- (4- hydroxybutyl Epoxide) benzoyl] Cortex Cinnamomi tert-butyl acrylate, 4- [4- (3- hydroxypropyl epoxide) benzoyl] Cortex Cinnamomi tert-butyl acrylate, 4- [4- (2- hydroxyethyl epoxide) benzoyl] Cortex Cinnamomi tert-butyl acrylate, 4- [4- hydroxymethyl epoxide benzoyl] Cortex Cinnamomi tert-butyl acrylate, 4- [4- (8- hydroxy octyl epoxide) benzoyl] phenyl cinnamate, 4- [4- (6- hydroxyl hexyl epoxide) benzoyl] cinnamic acid Phenyl ester, 4- [4- (4- hydroxybutyl epoxide) benzoyl] phenyl cinnamate, 4- [4- (3- hydroxypropyl epoxide) benzoyl] Phenyl cinnamate, 4- [4- (2- hydroxyethyl epoxide) benzoyl] phenyl cinnamate, 4- [4- hydroxymethyl epoxide benzoyl Base] phenyl cinnamate, 4- [4- hydroxy benzoyl] phenyl cinnamate, 4- [4- (8- hydroxy octyl epoxide) benzoyl] Cortex Cinnamomi Sour Biphenyl Ester, 4- [4- (6- hydroxyl hexyl epoxide) benzoyl] cinnamic acid Biphenyl Ester, 4- [4- (4- hydroxybutyl epoxide) benzene first Acyl group] cinnamic acid Biphenyl Ester, 4- [4- (3- hydroxypropyl epoxide) benzoyl] cinnamic acid Biphenyl Ester, 4- [4- (2- hydroxyethyl Epoxide) benzoyl] cinnamic acid Biphenyl Ester, 4- [4- hydroxymethyl epoxide benzoyl] cinnamic acid Biphenyl Ester, 4- [4- hydroxy benzeness 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 epoxide) benzoyl] chalcone derivative, 4- [4- (6- hydroxyl Hexyl epoxide) benzoyl] chalcone derivative, 4- [4- (4- hydroxybutyl epoxide) benzoyl] chalcone derivative, 4- [4- (3- hydroxyl third Base epoxide) benzoyl] chalcone derivative, 4- [4- (2- hydroxyethyl epoxide) benzoyl] chalcone derivative, 4- (4- hydroxymethyl epoxide Benzoyl) chalcone derivative, 4- (4- hydroxy benzoyl) chalcone derivative, 4 '-[4- (8- hydroxy octyl epoxide) benzoyl] look into ear Ketone, 4 '-[4- (6- hydroxyl hexyl epoxide) benzoyl] chalcone derivative, 4 '-[4- (4- hydroxybutyl epoxide) benzoyl] look into ear Ketone, 4 '-[4- (3- hydroxypropyl epoxide) benzoyl] chalcone derivative, 4 '-[4- (2- hydroxyethyl epoxide) benzoyl] look into ear Ketone, 4 '-(4- hydroxymethyl epoxide benzoyl) chalcone derivative, 4 '-(4- hydroxy benzoyl) chalcone derivative etc..

As (A) composition, there is light orientation group and the polymer of carboxyl beyond compound concrete example, can lift Go out cinnamic acid, ferulic acid, 4- methoxy cinnamic acid, 4- ethoxy-cinnamic acid, 4- n-pro-pyl epoxide cinnamic acid, 3,4- dimethoxy Cinnamic acid, coumarin-3-carboxylic acid, 4- (N, N- dimethylamino) cinnamic acid etc..

As (A) composition, there is light orientation group and the polymer of amide groups beyond compound concrete example, can Enumerate cinnamic acid, 4- methyl cinnamic acid amide, 4- ethyl-cinnamic acid amide, 4- methoxy cinnamic acid amide, 4- ethyoxyl Cinnamic acid etc..

As (A) composition, there is light orientation group and the polymer of amino beyond compound concrete example, can lift Go out 4- amino-cinnamic acid methyl ester, 4- amino cinnamate, 3- amino-cinnamic acid methyl ester, 3- amino cinnamate etc..

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

As (A) composition, the light orientation position shown in more preferably in following formula (1) is tied with heat reactivity position Compound beyond polymer obtained by polymerizable group is combined via sept on group obtained by conjunction.

(in formula, R¹⁰¹Represent hydroxyl, amino, hydroxyphenoxy, carboxyphenoxy, amino-benzene oxygen, amino carbonyl benzene oxygen Base, phenyl amino, hydroxyphenylamino, carboxyl phenyl amino, aminophenyiamino, hydroxyalkylamino or double (hydroxy alkyl) Amino, X¹⁰¹Represent phenylene, the phenyl ring in the definition of these substituent groups can be substituted with a substituent.)

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

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

As sept, represent the bivalence in straight-chain alkylidene, branched alkylidene, cyclic alkylidene and phenylene The group that group or this divalent group multiple are combined into.In this case, as the divalent group constituting sept each other Between key, the key between sept and the group shown in above-mentioned formula (1), the key between sept and polymerizable group, can lift Go out singly-bound, ester bond, amido link, urea bond or ehter bond.In the case that above-mentioned divalent group is multiple, divalent group each other can phase Same or different, in the case that above-mentioned key is multiple, key each other can be identical or different.

As such (A) composition, be combined with heat reactivity position at light orientation position obtained by combine on group The concrete example of monomer obtained by polymerizable group, can enumerate 4- (6- Methacryloxyhexyl -1- epoxide) cinnamic acid, 4- (6- acryloxy hexyl -1- epoxide) cinnamic acid, 4- (3- methacryloxypropyl -1- epoxide) cinnamic acid, 4- (4- (3- methacryloxypropyl -1- epoxide) acryloxy) benzoic acid, 4- (4- (6- Methacryloxyhexyl -1- Epoxide) benzoyl epoxide) cinnamic acid, 4- (6- Methacryloxyhexyl -1- epoxide) cinnamamide, 4- (6- methyl-prop Alkene acyloxy hexyl -1- epoxide)-N- (4- cyano-phenyl) cinnamamide, 4- (6- Methacryloxyhexyl -1- epoxide) - Double hydroxyethyl cinnamamide of N- etc..

Light orientation composition as the compound beyond the polymer of (A) composition can enumerate above concrete example, but not Limited by these concrete examples.

Next explanation (A) composition is polymer, i.e. detailed content during the polymer of high molecular.

(A) composition containing in the cured film formation compositionss of the present invention is the situation of the polymer of high molecular Under, preferably (A) composition is the polymer with light orientation group, i.e. has and carries out photodimerization as light orientation group The polymer of the functional group of structure position of change or photoisomerization, particularly preferably at least has the acrylic acid seriess at photodimerization position Copolymer.And then preferably, in addition to photodimerization position, have selected from hydroxyl, carboxyl, amide groups, amino and alcoxyl The acrylic copolymer of one of base silicyl group (below, being also referred to as heat cross-linking position including these groups) Thing.

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

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

As photodimerization position, cinnamoyl, chalcone derivative base, coumarin base, anthryl etc. can be enumerated.Wherein, from The height of the height of the transparency in light region and photodimerizationization reactivity sets out, preferably cinnamoyl.As preferred meat Osmanthus acyl group and the substituent group comprising cinnamoyl structure, can enumerate the 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 " comprising the substituent group of cinnamoyl structure " In.

In above-mentioned formula [1], X¹Represent alkyl, phenyl or xenyl that hydrogen atom, carbon number are 1～18.Now, phenyl Can be by any one replacement in halogen atom and cyano group with xenyl.The alkyl being 1～18 as carbon number, can enumerate with The same group of the group illustrated in above-mentioned of alkyl being 1～18 as carbon number.

In above-mentioned formula [2], X²Represent alkyl, phenyl, xenyl, hexamethylene that hydrogen atom, cyano group, carbon number are 1～18 Base.The alkyl being 1～18 as carbon number, the group illustrated in above-mentioned with the alkyl being 1～18 as carbon number Same group.Now, carbon number is 1～18 alkyl, phenyl, xenyl, cyclohexyl can be via selected from covalent bond, ether One kind or two or more key in key, ester bond, amido link, urea bond, amino-formate bond, amino linkage, carbonyl or combinations thereof And combine multiple.

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

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

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

(A) weight average molecular weight of the acrylic acid series copolymer of composition 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 solidify deficiency sometimes in heat cure, solvent resistance can decline, or resistance to Hot can decline.

(A), in the synthetic method of acrylic acid series copolymer with photodimerization position and heat cross-linking position of composition, make It is easy for having the monomer at photodimerization position and the method for the monomer copolymerization with heat cross-linking position.

As the monomer with photodimerization position, can enumerate for example, have cinnamoyl, chalcone derivative base, coumarin base, The monomer of anthryl etc..Wherein, from the height of the transparency in visible region and the height of photodimerizationization reactivity, special Preferably there is no the monomer of cinnamoyl.

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

In above-mentioned formula [3], X¹Represent alkyl, phenyl or xenyl that hydrogen atom, carbon number are 1～18.Now, phenyl Can be by any one replacement in halogen atom and cyano group with xenyl.The alkyl being 1～18 as carbon number, can enumerate with The same group of the group illustrated in above-mentioned of alkyl being 1～18 as carbon number.

L¹And L²Separately represent covalent bond, ehter bond, ester bond, amido link, urea bond or amino-formate bond.

In above-mentioned formula [4], X²Represent alkyl, phenyl, xenyl, hexamethylene that hydrogen atom, cyano group, carbon number are 1～18 Base.The alkyl being 1～18 as carbon number, can enumerate illustrated in above-mentioned with the alkyl being 1～18 as carbon number The same group of group.Now, carbon number be 1～18 alkyl, phenyl, xenyl, cyclohexyl can via covalent bond, Ehter bond, ester bond, amido link, urea bond are combined.

In above-mentioned formula [3] and formula [4], X³And X⁵Separately represent alkylidene, 2 that singly-bound, carbon number are 1～20 The aromatic ring of valency, the aliphatic ring of divalent.Here, the alkylidene that carbon number is 1～20 can be branched or straight-chain. The alkylidene being 1～20 as carbon number, can enumerate with the alkylidene being 1～20 as carbon number specified in above-mentioned The same group of group.

In above-mentioned formula [3] and formula [4], X⁴And X⁶Represent polymerizable group.As the concrete example of this polymerizable group, can lift Go 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 in [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, PEG 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 .beta.-methylacrylic acid, list-(2- (acryloxy) ethyl) phthalic acid ester, list-(2- (methacryl Epoxide) ethyl) phthalic acid ester, N- (carboxyl phenyl) maleimide, N- (carboxyl phenyl) Methacrylamide, N- (carboxyl Phenyl) acrylamide etc. has the monomer of carboxyl；Hydroxy styrenes, N- (hydroxy phenyl) Methacrylamide, N- (hydroxy benzeness Base) acrylamide, N- (hydroxy phenyl) maleimide, N- (hydroxy phenyl) maleimide etc. have the list of phenolic hydroxyl group Body；Acrylamide, Methacrylamide etc. have the monomer of amide groups；Methacryloxypropyl trimethoxy silane, first Base acryloxypropyl triethoxysilane, acryloxypropyl trimethoxy silane, acryloxypropyl three ethoxy Base silane etc. has monomer of alkoxysilyl etc..

There is the monomer at photodimerization position and there is heat cross-linking position with regard to use to obtain specific copolymer Monomer usage amount, based on the total amount of the whole monomers using to obtain specific copolymer, there is photodimerization portion The monomer of position is preferably 40 mass %～95 mass %, and the monomer with heat cross-linking position is preferably 5 mass %～60 mass %. It is more than 40 mass % by making the content of monomer with photodimerization position, high sensitivity can be given and good liquid crystal takes Tropism.On the other hand, it is below 95 mass % by making to have the content of monomer at photodimerization position, sufficient heat can be given Curable, is able to maintain that high sensitivity and good liquid crystal aligning.

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

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

Hereinafter enumerate the concrete example of above-mentioned monomer, but do not limited by these examples.

As aforesaid propylene ester compound, can enumerate for example, acrylic acid methyl ester., 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 group -2- adamantyl acrylate, acrylic acid 8- methyl -8- three ring 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 ester, 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 group -2- gold Just 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 Thiazolinyl carbazole, allyl glycidyl ether, 3- vinyl -7- oxabicyclo [4.1.0] heptane, 1,2- epoxy radicals -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 of the specific copolymer of the cured film formation compositionss obtaining for the present invention is not particularly limited, example As the monomer making to have particular functional group can be passed through (be there is the monomer at photodimerization position and there is heat cross-linking position Monomer), in the solvent that coexisted according to the desired monomer with non-reacted functional group and polymerization initiator etc., 50～110 Carry out polyreaction at a temperature of DEG C and obtain.Now, as long as used solvent dissolving have particular functional group monomer, Just it is not particularly limited according to the solvent with monomer and the polymerization initiator of non-reacted functional group etc. that expectation uses.As tool Style, can enumerate the solvent described in solvent described later.

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

Additionally, the solution of specific copolymer obtained as above is put into the ether under stirring, in water etc. so as to again Precipitation, the precipitate of generation is carried out filtering, washs, then carries out normal temperature drying or heat drying under normal or reduced pressure, from And the powder body of specific copolymer can be made.By such operation, can remove coexist with specific copolymer be polymerized initiation Agent and unreacted monomer, its result is obtained in that the powder body of sublimed specific copolymer.Can not filled by once-through operation In the case of dividing ground purification, so that obtained powder body is re-dissolved in solvent, repeat above-mentioned operation.

In the cured film formation compositionss of the present invention, as (A) composition, can be directly using above-mentioned specific copolymer Powder body, or this powder body can be re-dissolved in solvent for example described later, be used with the state of solution.

Additionally, in the present embodiment, the acrylic acid series copolymer of (A) composition can be the mixing of multiple specific copolymer Thing.

As described above, in the present invention, as (A) composition, it is possible to use the compound of low-molecular-weight or high molecular Specific copolymer.Additionally, (A) composition can also be respectively more than a kind of the compound of low-molecular-weight and the spy of high molecular Determine the mixture of copolymer.

[(B) composition]

(B) composition containing in the cured film formation compositionss of the present invention is the repetition comprising to have N- alkoxy methyl Unit and the polymer (hereinafter also referred to specific copolymer 2) with the repetitives of 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 thiourea, the nitrogen-atoms of carbamate, the nitrogen-atoms combining on the ortho position of nitrogenous heterocyclic nitrogen-atoms Deng.Accordingly, as N- alkoxy methyl, can enumerate alkoxy methyl and the nitrogen-atoms selected from amide, the nitrogen-atoms of thioamides, The nitrogen-atoms of urea, the nitrogen-atoms of thiourea, the nitrogen-atoms of carbamate, the nitrogen combining on the ortho position of nitrogenous heterocyclic nitrogen-atoms Structure obtained by nitrogen-atoms combination in atom etc..

As the monomer (hereinafter also referred to specific monomer X1) giving the repetitives with N- alkoxy methyl, as long as The monomer with above-mentioned group is just not particularly limited, but preferably can enumerate the compound shown in example formula described as follows (b1).

(in formula, R¹Represent hydrogen atom or methyl, R²The carbon number of expression hydrogen atom or straight or branched is 1～10 alkane Base.)

As abovementioned alkyl, can enumerate for example, methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, The tert-butyl group, 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-pro-pyl, 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-pro-pyl, 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 isophthalic acid- 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 the acrylamide compound that instead of of alkoxy methyl or methacrylamide compounds.In addition, so-called (methyl) acryloyl Amine, represents 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 having in the repetitives of side chain comprising polymerism C=C double bond of composition Number is the side chain that 3～16, end has unsaturated bond, particularly preferred formula (b2) specific side chain shown like that.As formula (b2-1) Shown, the specific side chain shown in formula (b2) is combined with the ester bond part of acrylic acid series polymeric compounds.

In formula (b2), R⁵¹Be carbon number be 1～14, and be from aliphatic group, the fatty group that comprises ring structures Roll into a ball the organic group selecting in the group with aromatic group or comprise to select the organic of the combination of multiple organic groups from this group Group.R⁵¹Ester bond, ehter bond, amido link or amino-formate bond etc. can be comprised.

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

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

The method obtaining the above-mentioned polymer with specific side chain is not particularly limited.If enumerating one, in advance Generate the acrylic acid series polymeric compounds with particular functional group by polymerizations such as radical polymerizations.Then, make this particular functional Group and end have compound (the hereinafter referred to as specific compound of unsaturated bond.) reacted and generated specific side chain, thus The side chain comprising polymerism C=C double bond can be imported in the polymer as (B) composition.

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

In the reaction of the specific side chain of above-mentioned generation, it is related with reaction that particular functional group is had to specific compound Preferably being combined as of group, carboxyl and epoxy radicals, hydroxyl and NCO, phenolic hydroxyl group and epoxy radicals, carboxyl and isocyanide Perester radical, amino and NCO or hydroxyl and acyl chlorides etc..And then, more preferably it is combined as carboxyl and contract with methacrylic acid Water glycerol base ester or hydroxyl and isocyanatomethyl ethyl acrylate.

Additionally, in the reaction of the specific side chain of above-mentioned generation, the polymer with particular functional group is with specific monomer X1 Monomer with having for the functional group (particular functional group) reacted with specific compound, that is, have carboxyl, (+)-2,3-Epoxy-1-propanol The monomer (hereinafter also referred to specific monomer X2) of base, hydroxyl, the amino of active hydrogen, phenolic hydroxyl group or NCO etc. is Copolymer obtained by required composition, its number-average molecular weight is 2,000～25,000.Here, there is particular functional for be polymerized The monomer of group can be used alone, as long as the combination not reacted in polymerization can also and with multiple.

Hereinafter enumerate to obtain monomer necessary to the polymer with particular functional group, that is, specific monomer X2 is concrete Example.But, do not limited by these concrete examples.

As the monomer with carboxyl, can enumerate for example, acrylic acid, methacrylic acid .beta.-methylacrylic acid, list-(2- (acryloyl Epoxide) ethyl) phthalic acid ester, list-(2- (methacryloxy) ethyl) phthalic acid ester, N- (carboxyl phenyl) maleoyl 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 radicals -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, PEG second Base ether acrylate, PEG 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 NCO, can enumerate for example, acryloyl ethyl isocyanate, methacryloylethyl Isocyanates and a tetramethyl xylene isocyanate etc..

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

Additionally, in the present invention, when obtaining the polymer of (B) composition, except specific monomer X1 and specific monomer X2 with Outward, can be used together can be with this monomer copolymerization, substituent group not having aforementioned thermally cross-linkable monomer.

As the concrete example of such monomer, can enumerate and there are the structures different from specific monomer X1 and specific monomer X2 Acrylate compounds or methacrylate compound, maleimide compound, acrylamide compound, acrylonitrile, horse Come anhydride, distyryl compound and vinyl compound etc..

Hereinafter enumerate the concrete example of aforementioned monomer, but do not limited by these concrete examples.

As the acrylate compounds with the structures different from aforementioned specific monomer X1 etc., can enumerate for example, propylene Sour methyl ester, ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, Isobutyl 2-propenoate, 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 group -2- Buddha's warrior attendant alkyl ester, acrylic acid 8- methyl -8- tricyclodecyl, Yi Jibing Olefin(e) acid 8- ethyl -8- tricyclodecyl etc..

As the methacrylate compound with the structures different from aforementioned specific monomer X1 etc., 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 Epoxide butyl ester, 2-Methacryloyloxy-2-methyladamantane, gamma-butyrolacton methacrylate, methacrylic acid 2- propyl group- 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 Thiazolinyl carbazole, allyl glycidyl ether, 3- vinyl -7- oxabicyclo [4.1.0] heptane, 1,2- epoxy radicals -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) composition, the presence ratio of repetitives with N- alkoxy methyl is with respect to this polymerization 100 moles of whole repetitives of thing are preferably 40 moles of %～90 mole %, rub in more preferably 50 moles %～85 You are %.

Namely be based on the total amount in order to obtain the whole monomers using as the specific copolymer 2 of (B) composition, in order to Rub in usage amount preferably 40 moles of %～90 obtaining specific monomer X1 using as the specific copolymer 2 of (B) composition You are %, more preferably 50 moles %～85 mole %.

In the case of adding up to less than 40 moles of %, the solidification causing with the heat cross-linking of (A) composition becomes not fill sometimes Point；Total compare 90 moles of % big in the case of, produce harmful effect to the adaptation of base material sometimes.

In the polymer of (B) composition, there is the presence ratio of the repetitives of side chain comprising polymerism C=C double bond It is preferably 10 moles of %～60 mole % with respect to 100 moles of whole repetitives of this polymer, more preferably 15 rub You are %～50 mole %.

Namely be based on the total amount in order to obtain the whole monomers using as the specific copolymer 2 of (B) composition, in order to Rub in usage amount preferably 10 moles of %～60 obtaining specific monomer X2 using as the specific copolymer 2 of (B) composition You are %, more preferably 15 moles %～50 mole %.

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

The method obtaining as the specific copolymer 2 of the example of (B) composition is not particularly limited, but for example, it is possible to passes through Make specific monomer X1, specific monomer X2 and the monomer in addition to specific monomer according to expectation interpolation and polymerization initiator Etc. in the solvent coexisting, carry out polyreaction at a temperature of 50～110 DEG C and obtain.Now, as long as the solvent being used Dissolve the molten of the monomer shown in above-mentioned Formula X, the monomer in addition to specific monomer according to expectation use and polymerization initiator etc. Agent is just not particularly limited.As its concrete example, it is documented in aftermentioned<Solvent>Xiang Zhong.

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

Additionally, the solution of the acrylic acid series polymeric compounds of the example being obtained by said method as (B) composition is put into So as to reprecipitation in ether under stirring, water etc., the precipitate of generation is carried out filtering, washs, then under normal or reduced pressure Carry out normal temperature drying or heat drying, such that it is able to make the powder body of the specific copolymer 2 of (B) composition.By above-mentioned operation, The polymerization initiator coexisting with the specific copolymer 2 of (B) composition and unreacted monomer can be removed, its result is obtained in that pure The powder body of the specific copolymer 2 of the example as (B) composition changed.By once-through operation can not fully purification situation Under, so that obtained powder body is re-dissolved in solvent, repeat above-mentioned operation.

In the compositionss of the cured film on the surface of the formation blooming of the present invention, the specific copolymer 2 of (B) composition is permissible Use with powder morphology or with solution morphology obtained by powder after purification is re-dissolved in solvent described later.

Additionally, in the compositionss of the cured film on the surface of the formation blooming of the present invention, (B) composition can be conduct (B) multiple mixture of the specific copolymer 2 shown in the example of composition.

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

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

With regard to the content of (B) composition in the cured film formation compositionss of the present invention, preferably (A) composition and (B) composition Content than by quality ratio be 5:95～60:40.In the case that the content of the polymer of (B) composition is too small, by cured film The solvent resistance of the cured film that formation compositionss obtain and thermostability decline, and orientation sensitivity during light orientation declines.Another Aspect, in the case that the content of the polymer of (B) composition is excessive, light orientation and storage stability decline sometimes.

[(C) composition]

(C) composition containing in the compositionss of the present invention is at least one polymerization in (C-1), (C-2) or (C-3) Thing, (C-1)：There is gathering of at least one substituent group in hydroxyl, carboxyl, amide groups, amino and alkoxysilyl Compound, (C-2)：Have and can carry out the substituent group of thermal response with (A) composition and the polymer of self-crosslinking can be carried out, (C-3)：Three Poly cyanamid-formaldehyde resin.Hereinafter each composition is described in detail.

[(C-1) composition]

(C-1) composition is at least one having in 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) composition, 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, PEPA, Polycarbonate polyol, polycaprolactone polyol, polyalkyleneimine, PAH, cellulose family (cellulose or it is derivative Thing), phenol resol resins etc. there is cyclic polymers such as the polymer of linear chain structure or branched structure, cyclodextrin etc..

Wherein, as acrylic acid series polymeric compounds, can apply and acrylate, methacrylate, styrene etc. are had The polymer obtained by monomer polymerization of unsaturated double-bond.

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

As at least one substituent group having in hydroxyl, carboxyl, amide groups, amino and alkoxysilyl Monomer, can enumerate 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, PEG ethyl ether acrylate, poly- (second two Alcohol) ethyl ether methacrylate, 5- acryloxy -6- hydroxy norbomene -2- carboxyl -6- lactone, 5- methacryl Epoxide -6- hydroxy norbomene -2- carboxyl -6- lactone etc. has a monomer of hydroxyl, acrylic acid, methacrylic acid .beta.-methylacrylic acid, List-(2- (acryloxy) ethyl) phthalic acid ester, list-(2- (methacryloxy) ethyl) phthalic acid ester, ethylene Yl benzoic acid, N- (carboxyl phenyl) maleimide, N- (carboxyl phenyl) Methacrylamide, N- (carboxyl phenyl) acrylamide Etc. the monomer with carboxyl and 4-Vinyl phenol, a hydroxy styrenes, o-hydroxystyrene, N- (hydroxy phenyl) methyl Acrylamide, N- (hydroxy phenyl) acrylamide and N- (hydroxy phenyl) maleimide etc. have a monomer of phenolic hydroxyl group, and third Acrylamide, Methacrylamide, N methacrylamide, N, N- DMAA, N, N- acrylamide etc. has 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 monomer of alkoxysilyl etc..

Additionally, in the present invention, when obtaining the acrylic acid series polymeric compounds as the example of (C-1) composition, except using Have beyond the monomer of at least one substituent group in hydroxyl, carboxyl, amide groups, amino and alkoxysilyl, can With and with can with this monomer copolymerization, do not have in hydroxyl, carboxyl, amide groups, amino and alkoxysilyl The monomer of substituent group.

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

As foregoing acrylates compound, can enumerate for example, acrylic acid methyl ester., ethyl acrylate, propyl acrylate, third Isopropyl gadoleate, n-butyl acrylate, Isobutyl 2-propenoate, 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 group -2- Buddha's warrior attendant alkyl ester, acrylic acid 8- methyl -8- tricyclodecyl and acrylic acid 8- ethyl -8- three ring 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 group -2- Buddha's warrior attendant alkyl ester, Methacrylic acid 8- methyl -8- tricyclodecyl and methacrylic acid 8- ethyl -8- tricyclodecyl etc..

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

The method obtaining as the acrylic acid series polymeric compounds of the example of (C-1) composition is not particularly limited, for example, it is possible to logical Cross the monomer making to have at least one substituent group in hydroxyl, carboxyl, amide groups, amino and alkoxysilyl, The list of the substituent group not having in hydroxyl, carboxyl, amide groups, amino and alkoxysilyl added according to expectation In the solvent that body and polymerization initiator etc. coexist, carry out polyreaction at a temperature of 50 DEG C～110 DEG C and obtain.Now, As long as the solvent dissolving being used has in hydroxyl, carboxyl, amide groups, amino and alkoxysilyl at least one Plant the monomer of substituent group, not had selected from hydroxyl, carboxyl, amide groups, amino and alkoxysilyl according to what expectation was added 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 described later [solvent] item.

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

Additionally, the solution of the acrylic acid series polymeric compounds of the example being obtained by said method as (C-1) composition is put into So as to reprecipitation in ether under stirring, water etc., the precipitate of generation is carried out filtering, washs, then in normal pressure or decompression Under carry out normal temperature drying or heat drying, such that it is able to be made as the powder of the acrylic acid series polymeric compounds of the example of (C-1) composition Body.By above-mentioned operation, can remove and be polymerized initiation with the acrylic acid series polymeric compounds of the example as (C-1) composition coexist Agent and unreacted monomer, its result is to be obtained in that the acrylic acid series polymeric compounds of the sublimed example as (B) composition Powder body.Fully in the case of purification, obtained powder body can not being made to be re-dissolved in solvent by once-through operation, repeat into Row aforesaid operations.

Weight average molecular weight as the acrylic acid series polymeric compounds of the example of (C-1) composition is preferably 3000～200000, more It is preferably 4000～150000, more preferably 5000～100000.If weight average molecular weight is excessive more than 200000, Dissolubility in a solvent declines sometimes, and operability declines sometimes；If weight average molecular weight is less than 3000 and too small, heat Solidify deficiency sometimes, solvent resistance and thermostability decline sometimes during solidification.In addition, weight average molecular weight is by gel infiltration Chromatography (GPC), polystyrene is used as value obtained by standard specimen.Hereinafter it is all same in this manual.

Then, the polyether polyol as preferred of specific (co) polymer 1 of (C-1) composition, it is right to enumerate The polyhydric alcohol addition such as Polyethylene Glycol, polypropylene glycol, propylene glycol, bisphenol-A, triethylene glycol, Sorbitol expoxy propane 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 リエテ Le P series, G are serial, EDP series, BPX series, FC are serial, CM series, day oily ユニオッ Network ス (registrar processed Mark) HC-40, HC-60, ST-30E, ST-40E, G-450, G-750, ユニオ mono- Le (registered trade mark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400, ノニオ Application (registered trade mark) LT-221, ST- 221st, OT-221 etc..

As the PEPA of preferred of specific (co) polymer of (C-1) composition, 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 is carried out PEPA obtained by reaction.As the concrete example of PEPA, DIC Port リライト (registered trade mark) 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 polyhydric alcohol P-510, P-1010, P-2010, P-3010, P-4010, P-5010, P-6010, F-510, F-1010, F- 2010th, F-3010, P-1011, P-2011, P-2013, P-2030, N-2010, PNNA-2016 etc..

As the polycaprolactone polyol of preferred of specific (co) polymer of (C-1) composition, can enumerate with three The polyhydric alcohol such as hydroxymethyl-propane, ethylene glycol are initiator, make 6-caprolactone 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 trade mark) OD-X-2155, OD-X-640, OD-X-2568, ダイセ Le chemistry プラ Network セ Le (registered trade mark) 205 processed, L205AL, 205U, 208,210,212, L212AL, 220,230,240,303,305,308,312,320 etc..

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

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

As the cyclodextrin of preferred of specific (co) polymer 1 of (C-1) composition, 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-schardinger dextrin-, hydroxymethyl-gamma-cyclodextrin, 2- hydroxyethyl-α- Cyclodextrin, 2- hydroxyethyl-beta-schardinger dextrin-, 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-schardinger dextrin-, 3- hydroxyl Base propyl group-gamma-cyclodextrin, 2,3- dihydroxypropyl-alpha-cyclodextrin, 2,3- dihydroxypropyl-beta-schardinger dextrin-, 2,3- dihydroxy third Hydroxyalkylcyclodextrins such as base-gamma-cyclodextrin etc..

As urethane-modified acrylic's based polymer of the preference of the specific (co) polymer 1 of (C-1) composition, As commercially available product, great achievement Off ァイ Application ケミカ Le ア Network リット (registered trade mark) 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..

As the phenol resol resins of the preference of the specific (co) polymer 1 of (C-1) composition, can enumerate for example, P-F condensation polymer etc..

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

Additionally, in the present compositions, (C-1) composition can be as the polymer illustrated in (C-1) composition Multiple mixture.

[(C-2) composition]

It is also possible to make (C-2) composition be that have can be with (A) composition in the cured film formation compositionss of present embodiment The substituent group carrying out thermal response and the polymer (hereinafter also referred to specific (co) polymer 2) that self-crosslinking can be carried out.

More specifically, specific (co) polymer 2 is that the thermal response with (A) composition and self-crosslinking reaction occur, and has The bridging property substituent group reacted at a temperature of lower than the sublimation temperature of (A) composition is (below by bridging property substituent group and hydroxyl Base, carboxyl, amino, amide groups and alkoxysilyl in the lump be referred to as particular functional group) polymer.By (A) composition with (C-2) thermal response of composition, can suppress (A) composition to distil.And, as described above, the cured film of present embodiment is formed using Compositionss, as cured film, can form the oriented material of photoreaction efficiency high.

The preferred bridging property substituent group containing as the polymer of (C-2) composition, can enumerate methylolamide base, Alkoxysilyl etc..The content of the bridging property substituent group being related to respect to 1 unit of repetitives of (C-2) composition is 0.5～1, from the viewpoint of the solvent resistance of oriented material, more preferably 0.8～1.

Polymer as (C-2) composition, it is possible to use 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 epoxide or methacrylamide compounds.

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

Additionally, as (C-2) composition it is also possible to be had poly- manufactured by the compound of alkoxysilyl using use Compound.

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

Additionally, in specific (co) polymer 2 used in the cured film formation compositionss of present embodiment, can be simultaneously With can be with the monomer (hereinafter also referred to there is the monomer of non-reacted functional group) of the monomer copolymerization with particular functional group.

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

To the method obtaining specific (co) polymer 2 used in the cured film formation compositionss of present embodiment not It is particularly limited to, for example, it is possible to pass through, in the monomer making to have particular functional group, according to what expectation was added, there is non-reacted sense In the solvent that the monomer of group and polymerization initiator etc. coexist, make it carry out polyreaction at a temperature of 50 DEG C～110 DEG C and obtain ?.Now, as long as used solvent dissolving have particular functional group monomer, according to expectation use have non-reacted The solvent of the monomer of functional group and polymerization initiator etc. is just not particularly limited.As concrete example, can enumerate in solvent described later The solvent recorded.

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

Additionally, the solution of specific (co) polymer 2 obtained as above is put in the ether under stirring, water etc., Make its reprecipitation, the precipitate of generation is carried out filtering, washs, then carry out normal temperature drying under normal or reduced pressure or heating is dry Dry, such that it is able to make the powder body of specific (co) polymer 2.By such operation, can remove and specific (co) polymer 2 The polymerization initiator coexisting and unreacted monomer, its result is to be obtained in that the powder body of sublimed specific (co) polymer 2. On fully in the case of purification, obtained powder body can not being made to be re-dissolved in solvent by once-through operation, repeating The operation stated.

In the cured film formation compositionss of present embodiment, can be directly using above-mentioned specific (co) polymer 2 Powder body, or this powder body can also be re-dissolved in solvent for example described later, used with the state of solution.

Additionally, in the present embodiment, the polymer of (C-2) composition can be the mixing of multiple specific (co) polymer 2 Thing.

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

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

[(C-3) composition]

As the melamine formaldehyde resin of (C-3) composition, it is by tripolycyanamide and resin obtained by formaldehyde condensation polymer, by Following formula represents.

In above-mentioned formula, R²¹Represent hydrogen atom or alkyl that carbon number is 1～4, n be represent repetitives number from So count.The alkyl being 1～4 as carbon number, can enumerate the group of corresponding carbon number in above-mentioned enumerated alkyl.

With regard to the melamine formaldehyde resin of (C-3) composition, from the viewpoint of storage stability, carrying out melamine The methylol preferably generating during the polycondensation of amine and formaldehyde is partially alkylated or alkylated.

The method of the melamine formaldehyde resin obtaining (C-3) composition is not particularly limited, but typically passes through melamine Amine is mixed with formaldehyde, is tuned into alkalescence using sodium carbonate, ammonia etc., is then heated at 60 DEG C～100 DEG C and synthesizes.Logical Cross so that itself and alcohol is reacted further can be by methylol alkoxylate.

With regard to the melamine formaldehyde resin of (C-3) composition, weight average molecular weight is preferably 250～5000, more preferably 300～4000, more preferably 350～3500.If weight average molecular weight is excessive more than 5000, dissolving in a solvent Property declines sometimes, and operability declines sometimes；If weight average molecular weight is too small less than 250, solid sometimes during heat cure Change not enough, the raising effect of solvent resistance and thermostability can not fully manifest sometimes.

In embodiments of the present invention, the melamine formaldehyde resin of (C-3) composition with liquid form or can be incited somebody to action Sublimed liquid is re-dissolved in solution morphology obtained by solvent described later and uses.

Additionally, in embodiments of the present invention, (C) composition can be multiple in (C-1), (C-2) and (C-3) The mixture of polymer.

The content of (C) composition in the cured film formation compositionss of the present invention is based on the total of (A) composition and (B) composition Measuring 100 mass parts is 5 mass parts～500 mass parts.In the case that the content of the polymer of (C) composition is too small, by cured film The solvent resistance of the cured film that formation is obtained with compositionss and thermostability decline, and orientation sensitivity during light orientation declines.Another Aspect, in the case that the content of the polymer of (C) composition is excessive, light orientation and storage stability decline sometimes.

[(D) composition]

In addition to above-mentioned (A) composition, (B) composition and (C) composition, the surface cure film of the formation blooming of the present invention Compositionss can also contain crosslinking catalyst as (D) composition.

As the crosslinking catalyst of (D) composition, can enumerate for example, sour or thermal acid generator.In the formation light using the present invention When the compositionss of the surface cure film of film are to form cured film, should (D) composition be reacted effectively by promotion heat cure.

Be used acid or thermal acid generator as (D) composition in the case of, (D) as long as composition contain sulfonic chemical combination Thing, hydrochloric acid or its salt, prebake conditions or rear toast when thermally decomposed and produced the compound of acid in 80 DEG C～250 DEG C of temperature Issue the compound that heat is decomposed and produced acid, be just not particularly limited.

As such compound, can enumerate for example, hydrochloric acid, methanesulfonic acid, ethyl sulfonic acid, propane sulfonic acid, fourth sulfonic acid, penta sulfonic acid, Pungent sulfonic acid, benzenesulfonic acid, p-methyl benzenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2- LOMAR PWA EINECS 246-676-2, sym-trimethylbenzene. sulphur Acid, xylol -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 ethyl sulfonic acids, nine fluorine butane -1- sulfonic acid, DBSA or its hydrate, Salt etc..

Additionally, as the compound producing acid by heat, can enumerate for example, double (tosyloxy) ethane, double (first Phenylsulfonyloxy) propane, double (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- Compound shown in 4- toluenesulfonamide and following formula [TAG-1]～formula [TAG-41] etc..

The content of (D) composition in the cured film formation compositionss of embodiments of the present invention, becomes with respect to as (A) At least one of compound, the polymer as (B) composition and the work with light orientation group and heat cross-linking group dividing 100 mass parts for the total amount of the polymer of (C) composition 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, more preferably 0.1 mass parts～6 mass parts.By making (D) The content of composition is more than 0.01 mass parts, can give sufficient Thermocurable and solvent resistance, can also impart to exposure High sensitivity.Additionally, being below 20 mass parts by making the content of (D) composition, cured film formation compositionss can be made Storage stability is good.

[(E) composition]

The cured film formation of present embodiment compositionss contain cross-linking agent as needed as (E) composition.In more detail and Speech, (E) composition is the cross-linking agent being reacted with above-mentioned (A) composition and (C) composition.(E) composition can with as (A) composition The comprising in the substituent group in hydroxyl, carboxyl, amide groups, amino and trialkoxysilyl, (C) composition of compound Substituent group in hydroxyl, carboxyl, amino and trialkoxysilyl combine.And, the cured film of present embodiment Formation compositionss can form the oriented material of photoreaction efficiency high in the form of cured film.

As the cross-linking agent of (E) composition, 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 compound 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, 1,3- double (hydroxymethyl) urea, 1,1,3,3- Double (the hydroxymethyl) -4,5- dihydroxy -2- imidazoles of four (butoxymethyl) urea, 1,1,3,3- tetra- (methoxy) urea, 1,3- Quinoline ketone and double (the methoxy) -4,5- dimethoxy -2- imidazolone of 1,3- etc..As commercially available product, three can be included Well サイテッ Network (strain) glycoluril compounds (trade name processed：(the registration of サイメ Le (registered trade mark) 1170, パウダリ Application Network Trade mark) 1174) etc. compound, methylate carbamide resin (trade name：UFR (registered trade mark) 65), butylation carbamide resin (trade name： UFR (registered trade mark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), Japanese greatly イ Application キ chemical industry (strain) urea processed/ Diaion (high condensed type, trade name：ベッカミ Application (registered trade mark) 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 Sell product, three well サイテッ Network (strain) system (trade names can be enumerated：サイメ Le (registered trade mark) 1123), (strain) three and ケミカ Le System (trade name：ニカラッ Network (registered trade mark) 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, HMMM etc..Make For commercially available product, three well サイテッ Network (strain) methoxy methyl processed fundamental mode melamine compound (trade names can be enumerated：サイメル (registered trade mark) 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 ト (registered trade mark) 506, マイ U ト 508), three and ケミカ Le methoxy methyl fundamental mode melamine Amines (trade name：ニカラッ Network (registered trade mark) 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 Epoxide methyl type melamine compound (trade name：ニカラッ Network (registered trade mark) 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 the hydrogen atom making amino by methylol or such melamine obtained by alkoxy methyl replacement Amines, carbamide compound, glycoluril compounds and benzoguanamine compound be condensed obtained by compound.Can enumerate for example, beautiful The chemical combination of the high molecular being manufactured by melamine compound and benzoguanamine compound described in state's patent the 6323310th Thing.As the commercially available product of aforementioned melamine compound, trade name can be enumerated：サイメ Le (registered trade mark) 303 (three well サイテッ Network (strain) makes) etc., as the commercially available product of aforementioned benzoguanamine compound, trade name can be enumerated：サイメ Le (registered trade mark) 1123 (three well サイテッ Network (strain) systems) etc..

These cross-linking agent may be used singly or in combination of two or m.

The total amount of the polymer based on compound, the polymer as (B) composition and (C) composition as (A) composition 100 mass parts, the content of the cross-linking agent of (E) composition in the cured film formation compositionss of present embodiment is preferably 50 mass Below part, below more preferably 30 mass parts.In the case that the content of cross-linking agent is excessive, light orientation and storage stability have When can decline.

[other additives]

In the cured film formation compositionss of embodiments of the present invention, as long as not damaging the effect of the present invention, Ke Yihan There are other additives.

As other additives, can contain for example, sensitizer.Sensitizer is on the surface of the blooming forming the present invention During cured film, in terms of promoting its photoreaction, become effective.

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

These sensitizers are not limited by above-claimed cpd.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 with respect to 100 mass parts of (A) composition 0.1 mass parts～20 mass parts, more preferably 0.2 mass parts～10 mass parts.In the case that this ratio is too small, sometimes can not Fully obtain the effect as sensitizer；In the case that this ratio is excessive, the absorbance of the cured film being formed is sometimes Decline or film is coarse sometimes.

As long as additionally, not damaging the effect of the present invention, the cured film of embodiments of the present invention is formed uses compositionss permissible Make containing silane coupler, surfactant, rheology control agent, pigment, dyestuff, preserving stabilizer, defoamer, antioxidant etc. For other additives.

[solvent]

The cured film formation compositionss of embodiments of the present invention are many to be used with lysed solution state in a solvent. The solvent now being used be dissolving (A) composition and (B) composition, according to expectation add (C) composition, (D) composition, (E) composition, And/or the solvent of other additives, as long as having the solvent of such solvability, then not special to its species and structure etc. Limit.

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, TC, propylene glycol, propylene glycol Monomethyl ether, propylene glycol monomethyl ether, propylene glycol propyl ether, propylene glycol propyl ether acetass, cyclopentyl-methyl ether, first Benzene, dimethylbenzene, butanone, Ketocyclopentane, Ketohexamethylene, 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 METHYLPYRROLIDONE etc..

These solvents can be used alone one kind, or combination two or more using.In these solvents, propylene glycol monomethyl Ether, propylene glycol monomethyl ether, butanone, Ketohexamethylene, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetass, second Acetoacetic ester, ethyl lactate, butyl lactate, 3- methoxy methyl propionate, 3- methoxypropionate, 3- ethoxyl ethyl propionate and The film property of 3- ethoxypropanoate is good and safe, therefore more preferably.

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

The preferred example of the cured film formation compositionss of present embodiment is as follows.

[1]：A kind of cured film formation compositionss, containing (A) composition, (B) composition, (C) composition and solvent, as (A) composition has light orientation group and at least one of compound of heat cross-linking group and comprising as (B) composition There are the repetitives of N- alkoxy methyl and there is the polymer of the repetitives of side chain comprising polymerism C=C double bond Match ratio is 5 by quality ratio:95～60:40, at least one based on the compound as (A) composition is poly- with (B) composition Total amount 100 mass parts of compound, (C) composition containing 5 mass parts～500 mass parts, described (C) composition be selected from (C-1), (C-2) at least one polymer and in (C-3), (C-1)：Have selected from hydroxyl, carboxyl, amide groups, amino and alkoxyl The polymer of at least one substituent group in silicyl, (C-2)：Have can with (A) composition carry out thermal response substituent group and The polymer of self-crosslinking, (C-3) can be carried out：Melamine formaldehyde resin.

[2]：A kind of cured film formation compositionss, containing (A) composition, (B) composition, (C) composition, (D) composition and molten Agent, (A) composition is 5 with the match ratio of (B) composition by quality ratio:95～60:40, based on as (A) composition compound with (B) total amount 100 mass parts of the polymer of composition, (C) composition containing 5 mass parts～500 mass parts, with respect to conduct (A) total amount 100 mass parts of the polymer of the compound of composition, the polymer of (B) composition and (C) composition, containing 0.1 mass The crosslinking catalyst of part～40 mass parts is as (D) composition.

[3]：A kind of cured film formation compositionss, become containing (A) composition, (B) composition, (C) composition, (D) composition, (E) Divide and solvent, (A) composition is 5 with the match ratio of (B) composition by quality ratio:95～60:40, based on as (A) composition Total amount 100 mass parts of the polymer of compound and (B) composition, (C) composition containing 5 mass parts～500 mass parts, relatively In total amount 100 mass parts of the polymer of the compound as (A) composition, the polymer of (B) composition and (C) composition, contain (D) composition of 0.1 mass parts～40 mass parts, becomes with (C) with respect to as the compound of (A) composition, the polymer of (B) composition Total amount 100 mass parts of the polymer dividing, (E) composition containing 0.01 mass parts～10 mass parts.

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

As long as each composition is dissolves uniformly in solvent, just to consolidating in the cured film formation compositionss of present embodiment The ratio of body composition is not particularly limited, and is 1 mass %～80 mass %, preferably 2 mass %～60 mass %, and more preferably 3 Quality %～40 mass %.Here, so-called solid constituent, refer to remove from whole compositions of cured film formation compositionss molten Composition obtained by agent.

The modulator approach of the cured film formation compositionss of present embodiment is not particularly limited.As modulation method, can lift Go out for example, in the solution of (B) composition being dissolved in solvent with regulation ratio mixing (A) composition and (C) composition, (D) composition, And (E) composition, the method making uniform solution, or the suitable stage in this modulation method, add further as needed Plus other additives the method that mixes.

When modulating the cured film formation compositionss of present embodiment, can be directly using anti-by the polymerization in solvent The solution of specific copolymer obtained by answering.Now, for example, add in the solution having modulated (B) composition acrylic acid series polymeric compounds (A) composition, (C) composition, (D) composition and (E) composition etc. and make uniform solution.At this point it is possible to mesh is adjusted to concentration And further additional input solvent.Now, the solvent used in the modulated process of (B) composition and cured film formation group Solvent used in the concentration adjustment of compound can be identical, in addition can also be different.

Additionally, the solution of the cured film formation compositionss with regard to being modulated, preferably in the mistake using 0.2 μm about of aperture Filter etc. uses after being filtered.

As described above, the cured film formation compositionss of the present embodiment of the present invention contain (A) composition, (B) composition, (C) composition and (D) composition and be configured, be the chemical combination with light orientation group and heat cross-linking group as (A) composition At least one of thing, is to comprise to have the repetitives of N- alkoxy methyl and have and comprise polymerism C=C as (B) composition The polymer of the repetitives of the side chain of double bond, as (C) composition be in (C-1), (C-2) and (C-3) at least one Plant polymer, (C-1)：There is at least one replacement in hydroxyl, carboxyl, amide groups, amino and alkoxysilyl The polymer of base, (C-2)：Have and can carry out the substituent group of thermal response with (A) composition and the polymer of self-crosslinking can be carried out, (C- 3)：Melamine formaldehyde resin, is crosslinking catalyst as (D) composition.In the compound as (A) composition, light orientation Group constitutes hydrophobic photoreaction portion, at least one replacement in hydroxyl, carboxyl, amino and trialkoxysilyl Base constitutes hydrophilic thermal response portion.(C) polymer of composition selected from hydroxyl, carboxyl, amino and trialkoxysilyl In at least one substituent group be also hydrophilic.

Form the cured film being formed with compositionss accordingly, with respect to by the cured film of present embodiment, due to the property of (C) composition Matter, is changed into hydrophilic inside it and is formed so that membrane structure stabilisation.And, the compound of (A) composition in cured film is inclined To the near surface being distributed in cured film.More specifically, the compound of (A) composition takes hydrophilic thermal response portion towards admittedly Change the private side of film, hydrophobic photoreaction portion towards the structure of face side, and be partial to the near surface being distributed in cured film. Its result is：The cured film of present embodiment achieves the ratio of the photoreactive group of (A) composition making to be present near surface The structure that example increases.And, the cured film of present embodiment, in the case of using as oriented material, can make to take for light To and the efficiency of photoreaction that carries out improves, can have excellent orientation sensitivity.And then, become and be suitable for patterning phase contrast The oriented material of the formation of material, the patterning phase contrast material using this oriented material manufacture can have excellent pattern shape Become second nature.

Additionally, as described above, the cured film formation compositionss of present embodiment contain comprises with N- alkoxy methyl Repetitives and there is the polymer of the repetitives of side chain comprising polymerism C=C double bond as (B) composition.Therefore, exist Formed the inside of the cured film being obtained with compositionss by the cured film of present embodiment, carry out light in the compound of (A) composition and take Before the photoreaction that tropism group causes, cross-linking reaction can be carried out by the thermal response with (B) composition.Its result is：In conduct In the case that oriented material uses, the patience to the polymerizable liquid crystal coated on this material and/or its solvent can be improved.

Additionally, using as oriented material being formed the cured film with compositionss obtain by the cured film of present embodiment In the case of, the polymer as (B) composition plays between strengthening and the polymerizable liquid crystal layer being formed on the material and solidifying The function of adaptation.

By the solution of the cured film formation compositionss of present embodiment, in substrate, (for example, silicon/silicon dioxide is coated to base Plate, silicon nitride board, by the metal substrate that for example aluminum, molybdenum, chromium etc. have been coated to, glass substrate, quartz base plate, ito substrate etc.), Film (for example, triacetyl cellulose (TAC) film, cyclo-olefin-polymer films, polyethylene terephthalate film, acrylic acid mesentery Deng resin film) etc. on, by spin coating, ink-jet application, printing after excellent painting, spin coating, flow coat, roller coat, slot coated, slot coated Form film etc. being coated, be then thermally dried in heating plate or baking oven etc., such that it is able to form cured film.

As the condition of heat drying, if the composition of the oriented material being formed by cured film with not dissolution to coating it 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～scope of 60 minutes in the heating-up temperature that suitably selects and heat time heating time.Heating-up temperature and heat time heating time are preferably 70 DEG C ～160 DEG C, 0.5 minute～10 minutes.

The thickness of the cured film being formed using the solidification compound of present embodiment is such as 0.05 μm～5 μm, can With consider the difference of height of substrate using, optical property, electrical property and suitably select.

The cured film being thusly-formed can by carry out polarisation UV irradiation and as oriented material, i.e. make to comprise polymerism Component that liquid crystal etc. is orientated in the interior compound with liquid crystal liquid crystal property and function.

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

Due to solvent resistance and thermostability are had by the oriented material that the solidification film composition of present embodiment is formed, therefore After on this oriented material, coating comprises the phase contrast material of polymerizable liquid crystal solution, by being heated to the phase in version temperature of this liquid crystal Spend and make phase contrast material be mesomorphic state so as to be orientated on oriented material.Then, become desired state of orientation Phase contrast material directly solidify, the phase contrast material with optically anisotropic layer can be formed.

As phase contrast material, it is, for example possible to use there is the liquid crystal monomer of polymerizable group and containing this liquid crystal monomer Compositionss etc..And, in the case that the substrate forming oriented material is film, there is the phase contrast material of present embodiment Film is useful as phase retardation film.The phase contrast material that such phase contrast material can be formed has and is changed into mesomorphic state, The material of the state of orientation such as horizontal alignment, cholesterol orientation, vertical orientated, hybrid orientation is taken on oriented material, can distinguish Phase difference characteristics as needed and be used separately.

Additionally, in the case of manufacturing the patterning phase contrast material used in 3D display, to by present embodiment The solidification cured film that formed by said method of film composition, via line and space pattern mask according to the benchmark specifying, For example, polarisation UV exposure is carried out with the direction of+45 degree, then, after removing mask, polarisation UV is exposed with the direction of -45 degree, thus Obtain the oriented material in the different 2 kinds of liquid crystal aligning regions in tropism control direction defining liquid crystal.Then, coating comprises to be polymerized Property liquid crystal solution phase contrast material after, be heated to the phase transition temperature of liquid crystal so that phase contrast material be mesomorphic state.Become Polymerizable liquid crystal for mesomorphic state is orientated on the oriented material being formed with 2 kinds of liquid crystal aligning regions, formed respectively with The corresponding state of orientation in each liquid crystal aligning region.Then, such phase contrast material achieving state of orientation is made directly to solidify, By above-mentioned state of orientation immobilization, it is possible to obtain regularly configured respectively by 2 kinds of different phase contrast regions of phase difference characteristics Multiple patterning phase contrast materials.

Additionally, liquid crystal display cells are also used as by the oriented material that the solidification film composition of present embodiment is formed Liquid crystal orientation film.For example, using 2 plate bases with oriented material formed as discussed above, present embodiment, with via Parting makes the mode that the oriented material on two substrates faces each other fit, and then injects liquid crystal between these substrates, can make The liquid crystal display cells that liquid making crystalline substance is orientated.

Therefore, the cured film formation compositionss of present embodiment go for manufacturing various phase contrast material (phase places Difference film), liquid crystal display cells etc..

Embodiment

Hereinafter enumerate embodiment further present embodiment to be described in detail.But, the present invention is not implemented by these Example limits.

[constituent used in embodiment etc. and its abbreviation]

Used in below example and comparative example, each constituent is as follows.

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

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

CIN3：4- propyl group epoxide cinnamic acid

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

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

PEPO：Polyol polyester polymer (has the adipic acid/diethylene glycol copolymer of following construction units.Molecular weight 4800.)

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

PTSA：P-methyl benzenesulfonic acid

HMM：Melamine crosslinkers [サイメ Le (CYMEL) (registered trade mark) 303 (three shown in following structural formulas Well サイテッ Network (strain) is made)]

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

HEMA：2-hydroxyethyl methacrylate

MMA：Methyl methacrylate

BMAA：N- (butoxymethyl) acrylamide

AIBN：α, α '-azodiisobutyronitrile

Each phase contrast material formation compositionss of embodiment and comparative example contain solvent, as this solvent, using the third two Alcohol monomethyl ether (PM), butyl acetate (BA), butanone (MEK), Ketohexamethylene (CHN).

The molecular weight of the polyimides in synthesis example, polyamic acid or acrylic acid series polymeric compounds uses (strain) Shodex society system Room temperature gel permeation chromatography (GPC) device (GPC-101), Shodex society post (KD -803, KD-805), are carried out as follows survey Fixed.

Column temperature：50℃

Eluent：DMF is (as additive, lithium bromide monohydrate (LiBr H₂O) it is 30mmol/ L, phosphoric acid anhydrous crystal (orthophosphoric acid) is 30mmol/L, and oxolane (THF) is 10mL/L)

Flow velocity：1.0mL/ minute

Make standard curve standard sample：ソ society TSK standard poly(ethylene oxide) (molecular weight about 900,000, 150,000,100,000,30,000) and Port リマラボラトリ society Polyethylene Glycol (molecular weight about 12,000,4,000, 1,000).

<¹H-NMR analyzes>

For¹The analytical equipment of H-NMR analysis and analysis condition 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)

M6CA 4.0g, styrene 4.0g, HEMA 2.0g, the AIBN0.1g as polymerization catalyst are dissolved in PM In 90.9g, carry out reaction in 20 hours by making it at 80 DEG C, (solid constituent is dense thus obtaining acrylic acid series copolymer solution Spend 10 mass %) (CIN6).The Mn of the acrylic acid series copolymer of gained is 55,000 for 20,000, Mw.

BMAA 32.0g, HEMA 8.0g, the AIBN 0.8g as polymerization catalyst are dissolved in oxolane 204.0g In, carry out reaction in 20 hours by making it at 60 DEG C, thus obtaining acrylic acid series copolymer solution.By acrylic acid series copolymer Solution is slowly added drop-wise in hexane 1000.0g, so that solid is separated out, is filtered and drying under reduced pressure, thus obtaining acrylic acid seriess altogether Polymers (PB-1).The Mn of the acrylic acid series copolymer of gained is 20,000 for 7,000, Mw.

BMAA 28.0g, HEMA 12.0g, the AIBN 0.8g as polymerization catalyst are dissolved in oxolane 204.0g In, carry out reaction in 20 hours by making it at 60 DEG C, thus obtaining acrylic acid series copolymer solution.By acrylic acid series copolymer Solution is slowly added drop-wise in hexane 1000.0g, so that solid is separated out, is filtered and drying under reduced pressure, thus obtaining acrylic acid seriess altogether Polymers (PB-2).The Mn of the acrylic acid series copolymer of gained is 25,000 for 8,300, Mw.

BMAA 24.0g, HEMA 16.0g, the AIBN 0.8g as polymerization catalyst are dissolved in oxolane 204.0g In, carry out reaction in 20 hours by making it at 60 DEG C, thus obtaining acrylic acid series copolymer solution.By acrylic acid series copolymer Solution is slowly added drop-wise in hexane 1000.0g, so that solid is separated out, is filtered and drying under reduced pressure, thus obtaining acrylic acid seriess altogether Polymers (PB-3).The Mn of the acrylic acid series copolymer of gained is 35,000 for 9,800, Mw.

BMAA 32.0g, GMA 8.0g, the AIBN 0.8g as polymerization catalyst are dissolved in oxolane 204.0g In, carry out reaction in 20 hours by making it at 60 DEG C, thus obtaining acrylic acid series copolymer solution.By acrylic acid series copolymer Solution is slowly added drop-wise in hexane 1000.0g, so that solid is separated out, is filtered and drying under reduced pressure, thus obtaining acrylic acid seriess altogether Polymers (PB-4).The Mn of the acrylic acid series copolymer of gained is 18,000 for 7,000, Mw.

Using GMA 40.0g, it is dissolved in oxolane 204.0g as the AIBN 0.8g of polymerization catalyst, by 60 It is made to carry out reaction in 20 hours, thus obtaining acrylic polymer solution at DEG C.Acrylic polymer solution is slowly dripped It is added in hexane 1000g, so that solid is separated out, being filtered and drying under reduced pressure, thus obtaining acrylic acid series polymeric compounds (PB-5).Institute The Mn of the acrylic acid series polymeric compounds obtaining is 20,000 for 8,000, Mw.

MMA 100.0g, HEMA 11.1g, the AIBN 5.6g as polymerization catalyst are dissolved in PM 450.0g, It is made to carry out reaction in 20 hours, thus obtaining acrylic acid series copolymer solution (solid component concentration 20 mass %) (PC- at 80 DEG C 1).The Mn of the acrylic acid series copolymer of gained is 7,600 for 4,200, Mw.

Using BMAA 100.0g, it is dissolved in PM 193.5g as the AIBN 4.2g of polymerization catalyst, at 90 DEG C, make it Carry out reaction in 20 hours, thus obtaining acrylic polymer solution (solid component concentration 35 mass %) (PC-2).Gained The Mn of acrylic acid series copolymer is 3,900 for 2,700, Mw.

Make acrylic acid series copolymer (PB-1) 10.0g, 2- acryloyloxyethyl isocyanate being obtained by polymerization example 2 4.3g, dibenzylatiooluene 0.4g, the dibutyl tin laurate 10mg as catalysts are dissolved in oxolane 60g In, make it carry out reaction in 5 hours at 60 DEG C.This solution is slowly added drop-wise in hexane 500g, so that solid is separated out, filtered And drying under reduced pressure, thus obtain the acrylic acid series copolymer (PB-6) with acryloyl group.Carry out¹H-NMR analyzes, and confirms propylene Sour based copolymer (PB-6) has acryloyl group.

Make acrylic acid series copolymer (PB-1) 10.0g, 2- methacryloxyethyl Carbimide. being obtained by polymerization example 2 Ester 4.3g, dibenzylatiooluene 0.4g, the dibutyl tin laurate 10mg as catalysts are dissolved in oxolane In 60g, it is made to carry out reaction in 5 hours at 60 DEG C.This solution is slowly added drop-wise in hexane 500g, so that solid is separated out, carry out Filter and drying under reduced pressure, thus obtaining the acrylic acid series copolymer (PB-7) with methylacryloyl.Carry out¹H-NMR analyzes, Confirm that acrylic acid series copolymer (PB-7) has methylacryloyl.

Make acrylic acid series copolymer (PB-2) 10.0g, 2- acryloyloxyethyl isocyanate being obtained by polymerization example 3 6.5g, dibenzylatiooluene 0.6g, the dibutyl tin laurate 10mg as catalysts are dissolved in oxolane 60g In, make it carry out reaction in 5 hours at 60 DEG C.This solution is slowly added drop-wise in hexane 500g, so that solid is separated out, filtered And drying under reduced pressure, thus obtain the acrylic acid series copolymer (PB-8) with acryloyl group.Carry out¹H-NMR analyzes, and confirms propylene Sour based copolymer (PB-8) has acryloyl group.

Make acrylic acid series copolymer (PB-3) 10.0g, 2- acryloyloxyethyl isocyanate being obtained by polymerization example 4 8.7g, dibenzylatiooluene 0.9g, the dibutyl tin laurate 10mg as catalysts are dissolved in oxolane 60g In, make it carry out reaction in 5 hours at 60 DEG C.This solution is slowly added drop-wise in hexane 500g, so that solid is separated out, filtered And drying under reduced pressure, thus obtain the acrylic acid series copolymer (PB-9) with acryloyl group.Carry out¹H-NMR analyzes, and confirms propylene Sour based copolymer (PB-9) has acryloyl group.

Make by polymerization example 5 obtain acrylic acid series copolymer (PB-4) 10.0g, acrylic acid 2.2g, dibenzylatiooluene 0.2g, the benzyltriethylammoinium chloride 10mg as catalysts are dissolved in PM60g, make it carry out 20 hours at 90 DEG C Reaction.This solution is slowly added drop-wise in hexane 500g, so that solid is separated out, filtered and drying under reduced pressure, thus obtain having The acrylic acid series copolymer (PB-10) of acryloyl group.Carry out¹H-NMR analyzes, and confirms that acrylic acid series copolymer (PB-10) has Acryloyl group.

Make by polymerization example 5 obtain acrylic acid series copolymer (PB-4) 10.0g, methacrylic acid 2.2g, dibutyl hydroxy Toluene 0.2g, the benzyltriethylammoinium chloride 10mg as catalysts are dissolved in PM 60g, so that it is carried out at 90 DEG C Reaction in 20 hours.This solution is slowly added drop-wise in hexane 500g, so that solid is separated out, being filtered and drying under reduced pressure, thus obtaining Must have the acrylic acid series copolymer (PB-11) of methylacryloyl.Carry out¹H-NMR analyzes, and confirms acrylic acid series copolymer (PB-11) there is methylacryloyl.

Make by polymerization example 6 obtain acrylic acid series copolymer (PB-5) 10.0g, acrylic acid 2.0g, dibenzylatiooluene 0.2g, the benzyltriethylammoinium chloride 10mg as catalysts are dissolved in PM60g, make it carry out 20 hours at 90 DEG C Reaction.This solution is slowly added drop-wise in hexane 500g, so that solid is separated out, filtered and drying under reduced pressure, thus obtain having The acrylic acid series copolymer (PB-12) of acryloyl group.Carry out¹H-NMR analyzes, and confirms that acrylic acid series copolymer (PB-12) has Acryloyl group.

Can be made by for example following method as the acrylic acid mesentery that base material uses.That is, make to comprise with methyl-prop E pioic acid methyl ester is that the feed particles of the copolymer of main constituent etc. are melted so as to be had by T-shaped mould at 250 DEG C in an extruder, Through casting roll and dryer roll etc., the acrylic acid mesentery of 40 μm of thickness can be made.

<Embodiment, comparative example>

Modulate embodiment and each cured film formation compositionss of comparative example according to the composition shown in table 1.Then, using each Phase contrast material formation forms cured film with compositionss, and the cured film for each gained carries out orientation and adaptation respectively Evaluate.

[table 1]

[evaluation of orientation]

Using bar coater, each cured film formation compositionss of embodiment and comparative example are coated on film, then in temperature Carry out 2 minutes heat dryings at 100 DEG C, in heat-circulation type baking oven, form cured film.To this each cured film with 20mJ/cm²'s Light exposure vertically irradiates the linear polarization of 313nm, forms oriented material.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 thickness 1.0 μm film.With 300mJ/cm²Film on this substrate is exposed, makes phase contrast material.On the substrate that will make Phase contrast material is clamped with a pair of Polarizer, observes the current status of the phase difference characteristics of phase contrast material, and phase contrast is intact Situation about showing is designated as zero sunkenly, and the situation that phase contrast is not showed is designated as ×, and they are documented in " orientation " Hurdle.

[evaluation of adaptation]

Using bar coater, each cured film formation compositionss of embodiment and comparative example are coated on film, then in temperature Carry out 2 minutes heat dryings at 100 DEG C, in heat-circulation type baking oven, form cured film.To this each cured film with 20mJ/cm²'s Light exposure vertically irradiates the linear polarization of 313nm, forms oriented material.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 thickness 1.0 μm film.With 300mJ/cm²Film on this substrate is exposed, makes phase contrast material.Using cutter to this phase Potential difference material puts 10 × 10 grids under with the interval of 1mm in length and breadth.Put under on grid at this using adhesive tape (Scotch tape) Carry out cellophane tape disbonded test.Using evaluation result as " initial stage ", will be all unstripped for 100 grids and feelings that are left behind Condition is designated as zero, even if the situation having 1 grid to peel off is designated as ×.Evaluation result collects in the table 2 after being shown in.

[evaluation of durable adaptation]

The phase contrast material on film that will be made by the method same with the evaluation of above-mentioned adaptation is put into and is set as In 80 DEG C of temperature, the baking oven of humidity 90%, carry out more than 72 hours standing.Then, take out phase contrast material, by with above-mentioned The same method of evaluation of adaptation, evaluates adaptation.Evaluation result collects as " durable " and is shown in Table 2.

[result of evaluation]

As described above, the result carrying out above evaluation is shown in Table 2.

[table 2]

The cured film being obtained using embodiment 1～17, each phase contrast material formation compositionss of comparative example 1～2 can To pass through as little as 20mJ/cm²Light exposure formed phase contrast material.On the other hand, using each phase contrast material shape of comparative example 3 The cured film that one-tenth compositionss obtain does not obtain orientation.

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

On the other hand, the cured film being obtained using the cured film formation compositionss of comparative example 1～3 is in the early stage and high temperature All it is difficult to after high humidity treatment maintain adaptation.

Industrial applicability

The phase contrast material formation compositionss of the present invention as the liquid crystal orientation film for forming liquid crystal display cells, set The oriented material putting the optical anisotropic film inside or outside liquid crystal display cells is highly useful, especially as The formation material of the patterning phase contrast material of 3D display is suitable.And then, as formation thin film transistor (TFT) (TFT) type liquid The material of the cured film such as the protecting film in the various display such as crystal display element, organic EL element, planar film and dielectric film, especially It is as dielectric film of interlayer dielectric, the protecting film of color filter or organic EL element forming TFT type liquid crystal display cells etc. Material be also suitable.

Claims

1. a kind of cured film formation compositionss, containing (A) composition and (B) composition,

(A) composition：There is at least one in light orientation group and the compound of heat cross-linking group,

(B) composition：Comprise the repetitives 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 formation compositionss according to claim 1, the light orientation group of (A) composition is by photodimerization The functional group of the structure of change or photoisomerization.

3. cured film formation compositionss according to claim 1 and 2, the light orientation group of (A) composition is cinnamoyl Base.

4. cured film formation compositionss according to claim 1 and 2, the light orientation group of (A) composition is diphenyl diimide The group of structure.

5. the cured film formation compositionss according to any one of Claims 1 to 4, it also contains (C) composition, described (C) composition is at least one polymer in (C-1), (C-2) and (C-3),

(C-1)：There is gathering of at least one substituent group in hydroxyl, carboxyl, amide groups, amino and alkoxysilyl Compound,

(C-3)：Melamine formaldehyde resin.

6. the cured film formation compositionss according to any one of Claims 1 to 5, it also contains (D) crosslinking catalyst.

7. the cured film formation compositionss according to any one of claim 1～6, it also contains (E) cross-linking agent.

8. the cured film formation compositionss according to any one of claim 1～7, in the polymer of (B) composition, tool The presence ratio having the repetitives of N- alkoxy methyl is rubbed for 40 with respect to 100 moles of whole repetitives of this polymer You are %～90 mole %, and the presence ratio with the repetitives of side chain comprising polymerism C=C double bond is with respect to this polymer 100 moles of whole repetitives be 10 moles of %～60 mole %.

9. the content of the cured film formation compositionss according to any one of claim 1～8, (A) composition and (B) composition Ratio is 5 by quality ratio:95～60:40.

10. the cured film formation compositionss according to any one of claim 5～9, based on (A) composition and (B) composition Total amount 100 mass parts, (C) composition containing 5 mass parts～500 mass parts.

A kind of 11. bloomings, are to be formed by the cured film any one of claim 1～10 to be obtained with compositionss.

A kind of 12. liquid crystal aligning materials, are that usage right requires the blooming described in 11 to be formed.

A kind of 13. phase contrast materials, are that usage right requires the blooming described in 11 to be formed.

14. polymer using as the composition for the blooming described in manufacturing claims 11, are that (B) comprises with N- The repetitives of alkoxy methyl and the polymer with the repetitives of side chain comprising polymerism C=C double bond.

15. polymer using as the composition for the liquid crystal aligning material described in manufacturing claims 12, are that (B) comprises The repetitives with N- alkoxy methyl and the polymer with the repetitives of side chain comprising polymerism C=C double bond.

16. polymer using as the composition for the phase contrast material described in manufacturing claims 13, are that (B) comprises tool The repetitives having N- alkoxy methyl and the polymer with the repetitives of side chain comprising polymerism C=C double bond.