CN105283512B

CN105283512B - Cured film is formed with composition, orientation material and phase difference material

Info

Publication number: CN105283512B
Application number: CN201480031811.6A
Authority: CN
Inventors: 畑中真; 石田智久; 汤川升志郎; 后藤耕平
Original assignee: Nissan Chemical Corp
Current assignee: Misao Kusano
Priority date: 2013-04-16
Filing date: 2014-04-09
Publication date: 2018-12-11
Anticipated expiration: 2034-04-09
Also published as: TW201510024A; JP6458949B2; WO2014171376A1; CN105283512A; TWI623572B; KR102165703B1; KR20150143540A; JPWO2014171376A1

Abstract

Problem of the present invention is that providing the cured film formation composition to form the cured film for having excellent light reaction efficiency and solvent resistance and high adhesion, light orientation orientation material and the phase difference material formed using the orientation material are provided.Solution is a kind of cured film formation composition, contain: (A) has the compound of light orientation group with the one kind or two or more substituent group in hydroxyl, carboxyl, trialkoxysilyl and amino, (B) there is the hydrophilic polymer of the one kind or two or more substituent group in hydroxyl, carboxyl and amino, (C) with the compound of 2 or more trialkoxysilyls, and (D) crosslinking catalyst.Using the cured film formation composition, cured film is formed, forms orientation material using light orientation technology.It is coated with polymerizable liquid crystal on the orientation material, it is made to solidify and obtain phase difference material.

Description

Cured film is formed with composition, orientation material and phase difference material

Technical field

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

Background technique

In recent years, in the field of display such as the TV for having used liquid crystal display panel, as the effort for being directed to high performance, energy The exploitation for enough appreciating the 3D display device of 3D rendering is promoting.In terms of 3D display device, for example, can be by making the right side of observer Eye identification right eye image, makes the left eye of observer recognize left eye image, so that display has relief image.

There are various ways in the mode of the 3D display device of display 3D rendering, as the mode for not needing special eyeglasses, It has been known that there is biconvex lens modes and disparity barrier mode etc..

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

In the case where the 3D display device of rotatory polarization glasses mode, the display element of image is usually formed in liquid crystal display panel etc. It is upper to be configured with phase difference material.The phase difference material distinguishes multiple, regularly 2 kinds of different phase difference regions of configuration phase difference characteristic, To constitute the phase difference material for having carried out pattern formation.In addition, hereinafter, in the present specification, it will be to configure such phase difference The phase difference material that the mode in the different multiple phase difference regions of characteristic has patterned is known as patterning phase difference material.

Phase difference material is patterned, for example, as disclosed in Patent Document 2, it can be by that will include polymerizable liquid crystal Phase difference material carries out optical design and is formed to make.The optical design of phase difference material comprising polymerizable liquid crystal, which is formed, to be utilized The known light orientation technology in the orientation material of liquid crystal display panel is formed.That is, material of the setting comprising light orientation on substrate Film irradiates 2 kinds of different polarisations of polarization direction to it.Then, as different 2 kinds in the tropism control direction for foring liquid crystal The orientation material in liquid crystal aligning region obtains optical alignment film.Solution shape of the coating comprising polymerizable liquid crystal on the optical alignment film Phase difference material realizes the orientation of polymerizable liquid crystal.Then, the polymerizable liquid crystal being orientated is solidified to form patterning phase Poor material.

Material in the orientation material of the light orientation technology using liquid crystal display panel is formed, as the light orientation that can be utilized Material, it is known that side chain has acrylic resin, the polyimide resin etc. at the photodimerization such as cinnamoyl and chalcone base position.According to Report, these resins are irradiated by polarisation UV, show performance (the hereinafter also referred to liquid crystal aligning of the orientation of control liquid crystal.) (referring to 3~patent document of patent document 5.).

Existing technical literature

Patent document

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

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

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

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

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

Summary of the invention

Problems to be solved by the invention

However, the research of people according to the present invention, it is thus identified that such side chain is had the light such as cinnamoyl, chalcone base In the case that the acrylic resin at dimerization position is suitable for the formation of phase difference material, sufficient characteristic cannot be obtained.In particular, Orientation material is formed in order to irradiate polarisation UV to these resins, carries out the phase difference material comprising polymerizable liquid crystal using the orientation material The optical design of material is formed, and big polarisation UV light exposure is needed.Polarisation UV light exposure, and for using common liquid crystal display panel Liquid crystal be orientated for adequately polarisation UV light exposure (for example, 100mJ/cm²Left and right.) compared to becoming more significantly.

It as the reason more than polarisation UV exposure quantitative change, can enumerate: in the case where the formation of phase difference material, be used with liquid crystal display panel Liquid crystal it is different, polymerizable liquid crystal uses in the state of solution, is coated on orientation material.

In side chain to be used there is acrylic resins at photodimerization position such as cinnamoyl etc. to form orientation material, makes to gather In the case that conjunction property liquid crystal is orientated, the acrylic resin etc. is made to carry out photo-crosslinking by photodimerizationization reaction.Then, until Until showing patience to polymerizable liquid crystal solution, need to continue the polarisation irradiation of big light exposure.In order to make the liquid of liquid crystal display panel Crystalline substance is orientated, as long as in general, only carrying out dimerization on the surface of the orientation material of light orientation.But it if wants Make to be orientated material performance solvent resistance using current materials such as above-mentioned acrylic resins, then needs to react until in orientation material Portion needs more light exposures.As a result, the orientation sensitivity there are current material becomes very small problem.

In addition, in order to make the above-mentioned resin as current material show such solvent resistance, it is known that add crosslinking agent Technology.However it is found that 3 dimension structures are formed being formed by inside film, light is anti-after having carried out heat cure reaction by crosslinking agent Answering property declines.That is, orientation sensitivity declines to a great extent, come even if adding crosslinking agent into current material using institute can not be obtained Desired effect.

According to the above, it is required to the orientation sensitivity for improving orientation material, the light orientation technology for reducing polarisation UV light exposure, With the cured film formation composition for being used to form the orientation material.Then, it is desirable that patterning phase difference can be expeditiously provided The technology of material.

The present invention is based on above opinion, results of study to form.That is, the object of the present invention is to provide take for providing To the cured film formation composition of material, which has excellent light reaction efficiency and has solvent resistance, can be with High sensitivity is orientated polymerizable liquid crystal.

Then, another object of the present invention is to provide obtained, by cured film formation composition with excellent light Reaction efficiency and has solvent resistance, the orientation material that polymerizable liquid crystal can be made to be orientated with high sensitivity and be taken using this The phase difference material formed to material.

Another object of the present invention and advantage can become clear by record below.

Means for solving the problems

1st scheme of the invention is related to cured film formation composition, which is characterized in that contains:

(A) with light orientation group and a kind or 2 in hydroxyl, carboxyl, trialkoxysilyl and amino Kind or more substituent group compound,

(B) there is the hydrophilic polymer of the one kind or two or more substituent group in hydroxyl, carboxyl and amino,

(C) with the compound of 2 or more trialkoxysilyls, and

(D) crosslinking catalyst.

In the 1st scheme of the invention, the light orientation group of preferably (A) ingredient is to carry out photodimerization or photoisomerization Structure functional group.

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

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

In the 1st scheme of the invention, preferably the compound of (A) ingredient has 2 or more hydroxyls.

In the 1st scheme of the invention, preferably (B) ingredient is more selected from polyether polyol, polyester polyol, polycarbonate At least one kind of hydrophilic polymer in first alcohol and polycaprolactone polyol.

In the 1st scheme of the invention, preferably (B) ingredient is cellulose or derivatives thereof.

In the 1st scheme of the invention, preferably (B) ingredient is the hydroxyl with polyethylene glycol ester group and carbon atom number 2~5 At least one of alkyl ester group, the acrylic polymer at least one of carboxyl and phenolic hydroxyl group.

In the 1st scheme of the invention, preferably (B) ingredient is by the inclusion of monomer and tool with polyethylene glycol ester group There is at least one of monomer of hydroxyalkyl ester group of carbon atom number 2~5, with the monomer with carboxyl and with phenolic hydroxyl group At least one of monomer monomer polymerization reaction and the acrylic copolymer that obtains.

In the 1st scheme of the invention, preferably (B) ingredient is cyclodextrin or derivatives thereof.

In the 1st scheme of the invention, preferably (D) ingredient is acid or thermal acid generator.

In the 1st scheme of the invention, the ratio of preferably (A) ingredient and (B) ingredient is 5:95~65 by quality ratio: 35。

In the 1st scheme of the invention, 100 mass parts of total amount of (A) ingredient Yu (B) ingredient are preferably based on, contain 10 Mass parts~100 mass parts (C) ingredient.

In the 1st scheme of the invention, 100 mass parts of total amount of (A) ingredient Yu (B) ingredient are preferably based on, contain 0.5 Mass parts~20 mass parts (D) ingredient.

2nd scheme of the invention is related to being orientated material, which is characterized in that is formed by the heat cured film of the 1st scheme of the invention It is made of composition.

3rd scheme of the invention is related to phase difference material, which is characterized in that uses the cured film by the 1st scheme of the invention Formation composition obtain cured film and formed.

The effect of invention

1st scheme according to the present invention is capable of providing for providing the cured film formation composition of orientation material, the orientation Material has excellent light reaction efficiency and solvent resistance, polymerizable liquid crystal can be made to be orientated with high sensitivity.

2nd scheme according to the present invention, be capable of providing have excellent light reaction efficiency and solvent resistance, can be with Gao Ling The orientation material that sensitivity is orientated polymerizable liquid crystal.

3rd scheme according to the present invention, optical design formation can be formed with high efficiency and be able to carry out by being capable of providing Phase difference material.

Specific embodiment

The cured film formation of present embodiment uses composition to contain (A) low molecular light orientation ingredient and as (B) ingredient Hydrophilic polymer, the compound as (C) ingredient with 2 or more trialkoxysilyls and as (D) at The crosslinking catalyst divided.The cured film of present embodiment, which is formed, uses composition, in addition to (A) ingredient, (B) ingredient, (C) ingredient and (D) other than ingredient, as long as not damaging effect of the invention, other additives can be contained.

Hereinafter, illustrating the details of each ingredient.

<(A) ingredient>

It is with light orientation group and choosing that the cured film of present embodiment, which forms (A) ingredient contained in composition, From the compound of the one kind or two or more substituent group in hydroxyl, carboxyl, trialkoxysilyl and amino.

Then, in the compound of (A) ingredient, light orientation group and light reaction and constitute hydrophobic light orientation portion, On the other hand the substituent group in carboxyl, trialkoxysilyl and amino constitutes hydrophilic thermal response portion.Also To say, (A) ingredient is to confer to the ingredient of cured film light orientation, in the present specification, (A) ingredient be also referred to as light orientation ingredient or Low molecular light orientation ingredient.

In addition, in the present invention, as light orientation group, referring to the structure position for carrying out photodimerization or photoisomerization Functional group.

The so-called structure position for carrying out photodimerization, is that the position to form dimer is irradiated by light, as its concrete example Son can enumerate cinnamoyl, chalcone base, cumarin base, anthryl etc..Wherein, preferably there is high transparency in visible light region With the reactive cinnamoyl of photodimerizationization.In addition, the so-called structure position for carrying out photoisomerization, referring to is become by light irradiation The structure position of cis- body and trans- body, it is sub as its concrete example, the position comprising azobenzene structure, Stilbene structure etc. can be enumerated. Wherein, from reactive height, preferably azobenzene structure.Compound with light orientation group and hydroxyl, for example, by Following formula indicates.The specific example of such compound is shown in following formula [A1]~formula [A5].

In previously described formula, X¹Indicate via selected from singly-bound, ehter bond, ester bond, amido bond, urethane bond, amino bond or it Combination in one kind or two or more key, in alkyl, phenyl, xenyl or their combination selected from carbon atom number 1~18 1~3 kind of substituent group bonding made of structure.X²Indicate hydrogen atom, halogen atom, cyano, carbon atom number 1~18 alkyl, Phenyl, xenyl or cyclohexyl.At this point, the alkyl of carbon atom number 1~18, phenyl, xenyl and cyclohexyl can also be via altogether Valence link, ehter bond, ester bond, amido bond or urea bond and be bonded.X³Indicate hydroxyl, phenyl, the alkyl of carbon atom number 1~4, carbon atom number 1~4 alkoxy or alkoxy.X⁴Separately indicate singly-bound, the alkylidene of carbon atom number 1~20, aromatic series ring group or Aliphatic ring group.Wherein, the alkylidene of carbon atom number 1~20 can be branched and be also possible to straight-chain.X⁵Indicate hydroxyl, carboxylic Base, amino or alkoxysilyl.X indicates singly-bound, oxygen atom or sulphur atom.

In addition, phenyl and xenyl can also be by alkyl, carbon atoms selected from carbon atom number 1~4 in these substituent groups One or more identical or different substituent groups in the alkoxy of number 1~4, halogen atom, trifluoromethyl and cyano replace.

In above-mentioned formula, R¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸Separately indicate the alkane of hydrogen atom, carbon atom number 1~4 Base, the alkoxy of carbon atom number 1~4, halogen atom, trifluoromethyl or cyano.

In addition, in above-mentioned formula, A¹Indicate hydrogen atom or methyl.A2 indicates hydrogen atom or methyl.

The specific example of the compound with light orientation group and hydroxyl as (A) ingredient, can enumerate for example, 4- (8- hydroxy octyl oxygroup) methyl cinnamate, 4- (6- hydroxyl hexyl oxygroup) methyl cinnamate, 3- methoxyl group -4- (6- hydroxyl oneself Base oxygroup) methyl cinnamate, 4- (4- hydroxybutyl oxygroup) methyl cinnamate, 4- (3- hydroxypropyl oxygroup) methyl cinnamate, 4- (2- hydroxyethyl oxygroup) methyl cinnamate, 4- hydroxymethyl oxygroup methyl cinnamate, 4- hydroxy-methyl cinnamate, 4- (8- Hydroxy octyl oxygroup) ethyl cinnamate, 4- (6- hydroxyl hexyl oxygroup) ethyl cinnamate, 4- (4- hydroxybutyl oxygroup) cinnamic acid Ethyl ester, 4- (3- hydroxypropyl oxygroup) ethyl cinnamate, 4- (2- hydroxyethyl oxygroup) ethyl cinnamate, 4- hydroxymethyl oxygroup Ethyl cinnamate, 4- hydroxy cinnamate acetoacetic ester, 4- (8- hydroxy octyl oxygroup) phenyl cinnamate, 4- (6- hydroxyl hexyl oxygroup) meat Phenyl cinnamate, 4- (4- hydroxybutyl oxygroup) phenyl cinnamate, 4- (3- hydroxypropyl oxygroup) phenyl cinnamate, 4- (2- hydroxyl Ethyl oxygroup) phenyl cinnamate, 4- hydroxymethyl oxygroup phenyl cinnamate, 4- hydroxy cinnamate acid phenenyl ester, 4- (8- hydroxy octyl oxygen Base) cinnamic acid Biphenyl Ester, 4- (6- hydroxyl hexyl oxygroup) cinnamic acid Biphenyl Ester, 4- (4- hydroxybutyl oxygroup) cinnamic acid biphenyl Ester, 4- (3- hydroxypropyl oxygroup) cinnamic acid Biphenyl Ester, 4- (2- hydroxyethyl oxygroup) cinnamic acid Biphenyl Ester, 4- hydroxymethyl oxygen Base cinnamic acid Biphenyl Ester, 4- hydroxycinnamic acid Biphenyl Ester, cinnamic acid 8- hydroxyl 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, cinnamic acid hydroxy methyl, 4- (8- hydroxy octyl oxygroup) Azobenzene, 4- (6- hydroxyl hexyl oxygroup) azobenzene, 4- (4- hydroxybutyl oxygroup) azobenzene, 4- (3- hydroxypropyl oxygroup) are even Pyridine, 4- (2- hydroxyethyl oxygroup) azobenzene, 4- hydroxymethyl oxygroup azobenzene, 4- hydroxyazobenzene, 4- (8- hydroxy octyl Oxygroup) chalcone, 4- (6- hydroxyl hexyl oxygroup) chalcone, 4- (4- hydroxybutyl oxygroup) chalcone, 4- (3- hydroxypropyl oxygen Base) chalcone, 4- (2- hydroxyethyl oxygroup) chalcone, 4- hydroxymethyl oxygroup chalcone, 4- hydroxy chalcone, 4 '-(8- hydroxyls Base octyl oxygroup) chalcone, 4 '-(6- hydroxyl hexyl oxygroup) chalcone, 4 '-(4- hydroxybutyl oxygroup) chalcone, 4 '-(3- Hydroxypropyl oxygroup) chalcone, 4 '-(2- hydroxyethyl oxygroup) chalcone, 4 '-hydroxymethyl oxygroup chalcone, 4 '-hydroxyls look into Ear ketone, 7- (8- hydroxy octyl oxygroup) cumarin, 7- (6- hydroxyl hexyl oxygroup) cumarin, 7- (4- hydroxybutyl oxygroup) tonka-bean Element, 7- (3- hydroxypropyl oxygroup) cumarin, 7- (2- hydroxyethyl oxygroup) cumarin, 7- hydroxymethyl oxygroup cumarin, 7- Hydroxycoumarin, 6- hydroxy octyl oxygroup cumarin, 6- hydroxyl hexyl oxygroup cumarin, 6- (4- hydroxybutyl oxygroup) tonka-bean Element, 6- (3- hydroxypropyl oxygroup) cumarin, 6- (2- hydroxyethyl oxygroup) cumarin, 6- hydroxymethyl oxygroup cumarin, 6- Hydroxycoumarin, 4- [4- (8- hydroxy octyl oxygroup) benzoyl] methyl cinnamate, 4- [4- (6- hydroxyl hexyl oxygroup) benzene first Acyl group] methyl cinnamate, 4- [4- (4- hydroxybutyl oxygroup) benzoyl] methyl cinnamate, 4- [4- (3- hydroxypropyl oxygen Base) benzoyl] methyl cinnamate, 4- [4- (2- hydroxyethyl oxygroup) benzoyl] methyl cinnamate, 4- [4- hydroxymethyl Oxygroup benzoyl] methyl cinnamate, 4- [4- hydroxy benzoyl] methyl cinnamate, 4- [4- (8- hydroxy octyl oxygroup) benzene Formoxyl] ethyl cinnamate, 4- [4- (6- hydroxyl hexyl oxygroup) benzoyl] ethyl cinnamate, 4- [4- (4- hydroxybutyl oxygen Base) benzoyl] ethyl cinnamate, 4- [4- (3- hydroxypropyl oxygroup) benzoyl] ethyl cinnamate, 4- [4- (2- hydroxyl Ethyl oxygroup) benzoyl] ethyl cinnamate, 4- [4- hydroxymethyl oxygroup benzoyl] ethyl cinnamate, 4- [4- hydroxy benzenes Formoxyl] ethyl cinnamate, 4- [4- (8- hydroxy octyl oxygroup) benzoyl] cortex cinnamomi tert-butyl acrylate, 4- [4- (6- hydroxyl hexyl Oxygroup) benzoyl] cortex cinnamomi tert-butyl acrylate, 4- [4- (4- hydroxybutyl oxygroup) benzoyl] cortex cinnamomi tert-butyl acrylate, 4- [4- (3- hydroxypropyl oxygroup) benzoyl] cortex cinnamomi tert-butyl acrylate, 4- [4- (2- hydroxyethyl oxygroup) benzoyl] cinnamic acid uncle Butyl ester, 4- [4- hydroxymethyl oxygroup benzoyl] cortex cinnamomi tert-butyl acrylate, 4- [4- (8- hydroxy octyl oxygroup) benzoyl] meat Phenyl cinnamate, 4- [4- (6- hydroxyl hexyl oxygroup) benzoyl] phenyl cinnamate, 4- [4- (4- hydroxybutyl oxygroup) benzoyl Base] phenyl cinnamate, 4- [4- (3- hydroxypropyl oxygroup) benzoyl] phenyl cinnamate, 4- [4- (2- hydroxyethyl oxygroup) Benzoyl] phenyl cinnamate, 4- [4- hydroxymethyl oxygroup benzoyl] phenyl cinnamate, 4- [4- hydroxy benzoyl] meat Phenyl cinnamate, 4- [4- (8- hydroxy octyl oxygroup) benzoyl] cinnamic acid Biphenyl Ester, 4- [4- (6- hydroxyl hexyl oxygroup) benzene first Acyl group] cinnamic acid Biphenyl Ester, 4- [4- (4- hydroxybutyl oxygroup) benzoyl] cinnamic acid Biphenyl Ester, 4- [4- (3- hydroxypropyl Oxygroup) benzoyl] cinnamic acid Biphenyl Ester, 4- [4- (2- hydroxyethyl oxygroup) benzoyl] cinnamic acid Biphenyl Ester, 4- [4- hydroxyl Ylmethyl oxygroup benzoyl] cinnamic acid Biphenyl Ester, 4- [4- hydroxy benzoyl] cinnamic acid Biphenyl Ester, 4- benzoyl cortex cinnamomi Sour 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- hydroxy methacrylate, 4- benzoyl cinnamic acid hydroxy methyl, 4- [4- (8- Hydroxy octyl oxygroup) benzoyl] chalcone, 4- [4- (6- hydroxyl hexyl oxygroup) benzoyl] chalcone, 4- [4- (4- hydroxyl Base butyl oxygroup) benzoyl] chalcone, 4- [4- (3- hydroxypropyl oxygroup) benzoyl] chalcone, 4- [4- (2- hydroxyl Ethyl oxygroup) benzoyl] chalcone, 4- (4- hydroxymethyl oxygroup benzoyl) chalcone, 4- (4- hydroxy benzoyl) Chalcone, 4 '-[4- (8- hydroxy octyl oxygroup) benzoyl] chalcone, 4 '-[4- (6- hydroxyl hexyl oxygroup) benzoyls] Chalcone, 4 '-[4- (4- hydroxybutyl oxygroup) benzoyl] chalcone, 4 '-[4- (3- hydroxypropyl oxygroup) benzoyls] Chalcone, 4 '-[4- (2- hydroxyethyl oxygroup) benzoyl] chalcone, 4 '-(4- hydroxymethyl oxygroup benzoyls) look into ear Ketone, 4 '-(4- hydroxy benzoyl) chalcone.

As the specific example with light orientation group and the compound of carboxyl, cinnamic acid, ferulic acid, 4- nitre can be enumerated Base cinnamic acid, 4- methoxy cinnamic acid, 3,4- dimethoxy-cinnamic acid, coumarin-3-carboxylic acid, 4- (N, N- dimethylamino) meat Cinnamic acid etc..

As the specific example of the compound with light orientation group and carboxyl and amino, methyl -4- ammonia can be enumerated Base cinnamic acid, ethyl -4- amino-cinnamic acid, methyl -3- amino-cinnamic acid, ethyl -3- amino-cinnamic acid etc..

As (A) ingredient, compound with light orientation group and amino specific example, 4- amino meat can be enumerated Acid methylester, 4- amino cinnamate, 3- amino-cinnamic acid methyl esters, 3- amino cinnamate etc..

It, can as (A) ingredient, compound with light orientation group and trialkoxysilyl specific example Enumerate 4- (3- trimethoxy-silylpropyl oxygroup) methyl cinnamate, 4- (3- triethoxysilylpropyltetrasulfide oxygroup) meat Acid methylester, 4- (3- trimethoxy-silylpropyl oxygroup) ethyl cinnamate, 4- (3- triethoxysilylpropyltetrasulfide oxygen Base) ethyl cinnamate, 4- (3- trimethoxysilyl hexyl oxygroup) methyl cinnamate, 4- (3- triethoxysilyl Hexyl oxygroup) methyl cinnamate, 4- (3- trimethoxysilyl hexyl oxygroup) ethyl cinnamate and 4- (3- triethoxy first Silylation hexyl oxygroup) ethyl cinnamate etc..

(A) the low molecular light orientation ingredient of ingredient, can enumerate more than specific example, but not by these examples limit It is fixed.

In addition, being that there is the case where compound of light orientation group and hydroxyl in the light orientation ingredient as (A) ingredient Under, as (A) ingredient, compound of the intramolecular with 2 or more light orientation groups and/or 2 or more hydroxyl can be used. Specifically, as (A) ingredient, can be used intramolecular with 1 hydroxyl and 2 or more the compound of light orientation group, There is intramolecular the compound of 1 light orientation group and 2 or more hydroxyl, intramolecular to be respectively provided with 2 or more light orientations The compound of group and hydroxyl.For example, the compound of 2 or more light orientation groups and hydroxyl is respectively provided with about intramolecular, As its an example, the compound indicated by following formula can be shown.

By proper choice of such compound, the molecular weight for improving the light orientation ingredient as (A) ingredient can be carried out Control.As a result, as described later, in the light orientation ingredient as (A) ingredient and polymer and conduct as (B) ingredient (C) when thermal response occurs for the crosslinking agent of ingredient, the light orientation ingredient as (A) ingredient can be inhibited to distil.Then, this embodiment party The cured film formation of formula can form the high-efficient orientation material of light reaction as cured film with composition.

In addition, the compound as (A) ingredient in the cured film formation composition of present embodiment, can be has Light orientation group and any one substituent group in hydroxyl, carboxyl and amino, multiple compounds mixture.

<(B) ingredient>

It is hydrophilic polymer that the cured film of present embodiment, which forms (B) ingredient contained in composition,.

Moreover, the hydrophilic polymer as (B) ingredient, can be with a kind in hydroxyl, carboxyl and amino or The polymer of two or more substituent group is (hereinafter also referred to as particular polymers.).

In the cured film formation composition of present embodiment, as the particular polymers of (B) ingredient, in order to (A) The compound of ingredient is comparably hydrophily, preferably selects the high-hydrophilic polymer for having high-hydrophilic.Moreover, particular polymers Polymer preferably with the hydrophilic radicals such as hydroxyl, carboxyl, amino, specifically, it is preferable that have selected from hydroxyl, carboxyl and The polymer of one kind or two or more substituent group in amino.That is, in the hydrophilic polymer of (B) ingredient of this specification So-called " hydrophily ", mean that the compound at least with (A) ingredient is comparably hydrophily.

As the hydrophilic polymer of (B) ingredient, can enumerate for example, acrylic polymer, polyamic acid, polyamides are sub- Amine, polyvinyl alcohol, polyester, polyester polycarboxylic acid, polyether polyol, polyester polyol, polycarbonate polyol, polycaprolactone are more First alcohol, polyalkyleneimine, polyallylamine, cellulose family (cellulose or derivatives thereof), phenol resol resins, trimerization Cyanamide formaldehyde resin etc. has cyclic polymers such as polymer, the cyclodextrin of linear chain structure or branched structure etc..

Wherein, applicable to have acrylate, methacrylate, styrene etc. no as acrylic polymer It is saturated polymer obtained by the monomer polymerization of double bond.

As the particular polymers of (B) ingredient, preferably hydroxyalkylcyclodextrins class, cellulose family, there is polyethylene glycol At least one of ester group and the hydroxyalkyl ester group of carbon atom number 2~5 and at least one of carboxyl and phenolic hydroxyl group Acrylic polymer, side chain have acrylic polymer, polyether polyol, polyester polyol, the poly- carbonic acid of aminoalkyl Ester polyol and polycaprolactone polyol.

Preferred an example of particular polymers as (B) ingredient, have polyethylene glycol ester group and carbon atom number 2~5 Acrylic polymer at least one of carboxyl and phenolic hydroxyl group of at least one of hydroxyalkyl ester group, as long as Acrylic polymer with this spline structure, for constitute acrylic polymer high molecular main chain skeleton with And type of side chain etc. is not particularly limited.

Structure list as at least one of hydroxyalkyl ester group with polyethylene glycol ester group and carbon atom number 2~5 Member, preferred structural unit are indicated by following formula [B1].

As the structural unit at least one of carboxyl and phenolic hydroxyl group, preferred structural unit is by following formula [B2] is indicated.

In above-mentioned formula [B1] and formula [B2], X¹¹And X¹²Separately indicate hydrogen atom or methyl, Y¹Indicate H- (OCH₂CH₂)_n(wherein, the value of n is 2~50, preferably 2~10 to base.) or carbon atom number 2~5 hydroxyalkyl, Y²Indicate carboxyl Or phenolic hydroxyl group.

The acrylic polymer of example as (B) ingredient, weight average molecular weight is preferably 3,000~200,000, more excellent It is selected as 4,000~150,000, further also preferably 5,000~100,000.If weight average molecular weight is more than 200,000 and mistake Greatly, then there is the case where declining to the decreased solubility and operability of solvent；If weight average molecular weight is too small less than 3,000, Become the case where insufficient solidification, solvent resistance and heat resistance decline when then there is heat cure.In addition, weight average molecular weight is to pass through Gel permeation chromatography (GPC), the value for using polystyrene to obtain as standard sample.Hereinafter, also same in the present specification Sample.

The synthetic method of the acrylic polymer of example as (B) ingredient, makes with polyethylene glycol ester group and carbon Monomer (the hereinafter also referred to b1 monomer of at least one of the hydroxyalkyl ester group of atomicity 2~5.) and with carboxyl and phenol Monomer (the hereinafter also referred to b2 monomer of at least one of property hydroxyl.) copolymerization method be easy.

As the above-mentioned monomer with polyethylene glycol ester group, H- (OCH can be enumerated₂CH₂)_nThe mono acrylic ester of-OH or single first Base acrylate.The value of n is 2~50, preferably 2~10.

As the monomer of the above-mentioned hydroxyalkyl ester group with carbon atom number 2~5, can enumerate for example, methacrylic acid 2- hydroxyl Ethyl ester, 2-hydroxyethyl acrylate, methacrylic acid 2- hydroxypropyl ester, acrylic acid 2- hydroxypropyl ester, acrylic acid 4- hydroxyl butyl Ester, methacrylic acid 4- hydroxyl butyl ester.

As the above-mentioned monomer with carboxyl, can enumerate for example, acrylic acid, methacrylic acid, vinyl benzoic acid.

As the above-mentioned monomer with phenolic hydroxyl group, can enumerate for example, 4-Vinyl phenol, hydroxy styrenes, adjacent hydroxyl Base styrene.

In addition, in the present embodiment, when synthesizing the acrylic polymer as the example of (B) ingredient, as long as not damaging Evil effect of the invention, can be used together the monomer other than b1 monomer and b2 monomer, specifically, not having hydroxyl and carboxyl Any one of monomer.

As such monomer, can enumerate for example, methyl acrylate, ethyl acrylate, propyl acrylate, acrylic acid isopropyl The acrylate compounds such as ester, butyl methacrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, methyl-prop E pioic acid methyl ester, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, Isobutyl methacrylate, methyl The methacrylate compounds such as tert-butyl acrylate, maleimide, N- methylmaleimido, N- benzyl maleimide The maleimide compounds such as amine and N- N-cyclohexylmaleimide, acrylamide compound, acrylonitrile, maleic anhydride, benzene Vinyl compound and vinyl compound etc..

B1 monomer and b2 monomer used in the acrylic polymer for being used as the example of (B) ingredient Usage amount, based on for being used as the total amount of whole monomer used in the acrylic polymer of (B) ingredient, preferably b1 Monomer is 2 moles of %~95 mole %, and b2 monomer is 5 moles of %~98 mole %.

In the case where using only has the monomer of carboxyl as b2 monomer, based on for being used as the third of (B) ingredient The total amount of whole monomer used in olefin(e) acid quasi polymer, preferably b1 monomer are 60 moles of %~95 mole %, and b2 monomer is 5 Mole %~40 mole %.

On the other hand, in the case where using only has the monomer of phenolic hydroxyl group as b2 monomer, preferably b1 monomer rubs for 2 You are %~80 mole %, and b2 monomer is 20 moles of %~98 mole %.In the case where b2 monomer is too small, liquid crystal aligning is easy It becomes inadequate；In the case where excessive, decline is easy with the intermiscibility of (A) ingredient.

The method of the acrylic polymer of example as (B) ingredient is not particularly limited, for example, making b1 monomer In the solvent coexisted with b2 monomer and according to monomer of the expectation other than b1 monomer and b2 monomer and polymerization initiator etc., 50 DEG C~110 DEG C at a temperature of acrylic polymer obtained by polymerization reaction.At this point, about used solvent, as long as Dissolve b1 monomer and b2 monomer, according to the monomer and polymerization initiator used in expectation other than b1 monomer and b2 monomer Deng solvent be just not particularly limited.As specific example, it is recorded in aftermentioned<solvent>item.

The side chain of preferred an example of the particular polymers as (B) ingredient has the acrylic polymer of aminoalkyl, It can enumerate for example, making acrylic-amino ethyl ester, methacrylic acid amino-ethyl ester, acrylic-amino propyl diester and methyl-prop The polymer of the aminoalkyl esters monomer polymerizations such as olefin(e) acid aminopropan base ester, or make the aminoalkyl ester monomer and be selected from above-mentioned third The polymer of one kind or two or more monomer copolymerization in alkene acrylic monomer.

The acrylic polymer of example as (B) ingredient obtained by preceding method, is usually dissolved in solvent The state of solution.

In addition, the solution as the acrylic polymer of the example of (B) ingredient obtained by the above method is put into Ether, water etc. under stirring make its reprecipitation, and the sediment of generation is filtered, is washed, then under normal or reduced pressure, into Row air drying or heat drying can be made as the powder of the acrylic polymer of the example of (B) ingredient.By aforementioned Operation can remove the polymerization initiator and unreacted list coexisted with the acrylic polymer of the example as (B) ingredient Body, as a result, obtaining the powder of the acrylic polymer of the example as (B) ingredient refined.Passing through once In the case that operation cannot be refined fully, as long as resulting powder is made to be re-dissolved in solvent, above-mentioned operation is repeated i.e. It can.

The polyether polyol of preferred an example of the particular polymers as (B) ingredient can be enumerated to polyethylene glycol, poly- the third two The polyalcohols addition such as alcohol, propylene glycol, bisphenol-A, triethylene glycol, D-sorbite propylene oxide, polyethylene glycol, polypropylene glycol etc. it is poly- Close object.As the specific example of polyether polyol, ADEKA アデカ Port リエーテ Le P series, G series, EDP system can be enumerated Column, BPX series, FC series, CM series, day oil ユニオッ Network ス (registered trademark) HC-40, HC-60, ST-30E, ST- 40E, G-450, G-750, ユニオー Le (registered trademark) TG-330, TG-1000, TG-3000, TG-4000, HS-1600D, DA-400, DA-700, DB-400, ノニオ Application (registered trademark) LT-221, ST-221, OT-221 etc..

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

The polycaprolactone polyol of preferred an example of the particular polymers as (B) ingredient, can enumerate with trihydroxy methyl third The polyalcohols such as alkane, ethylene glycol are initiator, make the polymer of 6-caprolactone ring-opening polymerisation.As the specific of polycaprolactone polyol Example can enumerate DIC Port リライト (registered trademark) OD-X-2155, OD-X-640, OD-X-2568, ダイセ Le chemistry system プラ Network セ Le (registered trademark) 205, L205AL, 205U, 208,210,212, L212AL, 220,230,240,303,305, 308,312,320 etc..

The polycarbonate polyol of preferred an example of the particular polymers as (B) ingredient, can enumerate makes trihydroxy methyl third Polymer obtained by the polyalcohols such as alkane, ethylene glycol and diethyl carbonate, diphenyl carbonate, ethylene carbonate etc. react.As poly- The specific example of carbonate polyol, can enumerate ダイセ Le chemistry プラ Network セ Le (registered trademark) CD205, CD205PL, C-590, C-1050, C-2050, C-2090, C-3090 etc. of CD210, CD220, Network ラレ.

It is fine can to enumerate hydroxyethyl cellulose, hydroxypropyl for the cellulose of preferred an example of the particular polymers as (B) ingredient Tie up the hydroxy alkyl celluloses classes such as element, the hydroxyls such as hydroxyethylmethylcellulose, hydroxypropyl methyl cellulose, hydroxyethyl ethylcellulose Base alkyl-alkyl cellulose family and cellulose etc., for example, it is preferable to which the hydroxy alkyls such as hydroxyethyl cellulose, hydroxypropyl cellulose are fine Tie up plain class.

The cyclodextrin of preferred an example of the particular polymers as (B) ingredient, can enumerate alpha-cyclodextrin, beta-cyclodextrin and The cyclodextrin such as gamma-cyclodextrin, the methylation ring paste such as methyl-alphacyclodextrin, methyl-B-cyclodextrin and methyl-y-cyclodextrin Essence, hydroxymethyl-alpha-cyclodextrin, hydroxymethyl-beta-cyclodextrin, hydroxymethyl-gamma-cyclodextrin, 2- hydroxyethyl-α-ring paste Essence, 2- hydroxyethyl-beta-cyclodextrin, 2- hydroxyethyl-gamma-cyclodextrin, 2- hydroxypropyl-alpha-cyclodextrin, 2- hydroxypropyl-β- Cyclodextrin, 2- hydroxypropyl-gamma-cyclodextrin, 3- hydroxypropyl-alpha-cyclodextrin, 3- hydroxypropyl-beta-cyclodextrin, 3- hydroxyl third Base-gamma-cyclodextrin, 2,3- dihydroxypropyl-alpha-cyclodextrin, 2,3- dihydroxypropyl-beta-cyclodextrin, 2,3- dihydroxypropyl- Hydroxyalkylcyclodextrins such as gamma-cyclodextrin etc..

The melamine resin of preferred an example of the particular polymers as (B) ingredient is by melamine and first Resin obtained by aldehyde polycondensation, is indicated by following formula.

In above-mentioned formula, R indicates the alkyl of hydrogen atom or carbon atom number 1~4, and n is to indicate number of repeat unit purpose natural number.

From the viewpoint of storage stability, preferably the melamine resin of (B) ingredient is in melamine and formaldehyde The methylol generated when polycondensation is partially alkylated or alkylated.

The method of melamine resin for obtaining (B) ingredient is not particularly limited, but usually by by melamine with Formaldehyde mixing, makes its alkalescent using sodium carbonate, ammonia etc., then heats and synthesize at 60-100 DEG C.By making it into one Step is reacted with alcohol, can be by methylol alkoxide.

(B) weight average molecular weight of the melamine resin of ingredient is preferably 250~5,000, more preferably 300~4, 000, further also preferably 350~3,500.If weight average molecular weight is more than 5,000 and excessive, then there is the dissolution to solvent Property decline and operability decline the case where；If weight average molecular weight is too small less than 250, there are become solidification when heat cure not The case where foot, solvent resistance and heat resistance decline.

In the present invention, the melamine resin of (B) ingredient can be used with liquid form, or will refine after Liquid be re-dissolved in the solution morphology in aftermentioned solvent use.

In addition, in the present invention, the melamine resin of (B) ingredient can be the melamine of a variety of (B) ingredients The mixture of formaldehyde resin.

The phenol resol resins of preferred an example of the particular polymers as (B) ingredient, can enumerate for example, phenol- Formaldehyde condensation products etc..

In the cured film formation composition of present embodiment, the polymer of (B) ingredient can use with powder morphology, Or it is used so that the powder after purification is re-dissolved in the solution morphology in aftermentioned solvent.

In addition, the polymer of (B) ingredient can be a variety of (B) in the cured film formation composition of present embodiment The mixture of the polymer of ingredient.

<(C) ingredient>

It is to have 2 or more tri-alkoxies that the cured film of present embodiment, which forms (C) ingredient contained in composition, The compound of silicyl.It is also possible to the polymer with trialkoxysilyl.

As the specific example of the compound with 2 or more trialkoxysilyls, the bis- (trimethoxies of Isosorbide-5-Nitrae-can be enumerated Base silicyl) benzene, bis- (triethoxysilyl) benzene of 1,4-, 4,4 '-bis- (trimethoxysilyl) biphenyl, 4,4 '- It is bis- (triethoxysilyl) biphenyl, bis- (trimethoxysilyl) ethane, bis- (triethoxysilyl) ethane, double It is (trimethoxysilyl) methane, bis- (triethoxysilyl) methane, bis- (trimethoxysilyl) ethylene, double Bis- (trimethoxysilylethylgroup group) tetramethyl disiloxanes of (triethoxysilyl) ethylene, 1,3-, bis- (three second of 1,3- Oxygroup silyl ether) tetramethyl disiloxane, bis- (triethoxysilylmethyl) amine, bis- (trimethyoxysilanes Ylmethyl) amine, bis- (triethoxysilylpropyltetrasulfide) amine, bis- (trimethoxy-silylpropyl) amine, bis- (3- trimethoxies Silylpropyl) carbonic ester, bis- (3- triethoxysilylpropyltetrasulfide) carbonic esters, bis- [(3- trimethoxysilyls) Propyl] disulphide, bis- [(3- triethoxysilyl) propyl] disulphide, bis- [(3- trimethoxysilyls) third Base] it is thiocarbamide, bis- [(3- triethoxysilyl) propyl] thiocarbamides, bis- [(3- trimethoxysilyl) propyl] ureas, double [(3- triethoxysilyl) propyl] urea, bis- (trimethoxysilyl methyl) benzene of 1,4-, bis- (the triethoxy first of 1,4- Silyl methyl) benzene, three (trimethoxy-silylpropyl) amine, three (triethoxysilylpropyltetrasulfide) amine, 1,1,2- tri- (trimethoxysilyl) ethane, 1,1,2- tri- (triethoxysilyl) ethane, three (3- trimethoxysilyls third Base) compounds, methacryloxypropyl such as isocyanuric acid ester, three (3- triethoxysilylpropyltetrasulfide) isocyanuric acid esters The homopolymer or copolymer of trimethoxy silane, acryloxypropyl triethoxysilane.

There is the compound of 2 or more trialkoxysilyls can use alone or in combination of two kinds or more for these.

The cured film of present embodiment, which is formed, has 2 or more tri-alkoxy monosilanes with (C) ingredient in composition The content of the compound of base, 100 mass parts of total amount of the polymer based on the compound and (B) ingredient as (A) ingredient are excellent It is selected as 10 mass parts~100 mass parts, more preferably 15 mass parts~80 mass parts.There are 2 or more three alkane in (C) ingredient In the case that the content of the compound of oxygroup silicyl is too small, the cured film that is obtained by cured film formation composition it is resistance to molten Agent and heat resistance decline, sensitivity decline when light orientation.On the other hand, in the case where content is excessive, light orientation sometimes Property and storage stability decline.

<(D) ingredient>

The cured film of present embodiment, which is formed, uses composition, other than above-mentioned (A) ingredient, (B) ingredient and (C) ingredient, Contain crosslinking catalyst as (D) ingredient.

As the crosslinking catalyst of (D) ingredient, for example, can be acid or thermal acid generator.In consolidating using present embodiment Change in the formation that film is formed with the cured film of composition, being somebody's turn to do (D) ingredient becomes effective to the promotion that heat cure is reacted.

Use acid or thermal acid generator as (D) ingredient in the case where, (D) as long as ingredient contain sulfonic chemical combination It thermally decomposes when object, hydrochloric acid or its salt, prebake conditions or rear baking and generates sour compound heat point at 80 DEG C~250 DEG C of temperature The compound for solving and generating acid is just not particularly limited.

As such compound, can enumerate for example, hydrochloric acid, methanesulfonic acid, ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid, penta Alkyl sulfonic acid, perfluoroetane sulfonic acid, benzene sulfonic acid, p-methyl benzenesulfonic acid, camphorsulfonic acid, trifluoromethayl sulfonic acid, p-phenolsulfonic acid, 2- naphthalene sulfonic acids, Sym-toluenesulfonic acid, paraxylene -2- sulfonic acid, meta-xylene -2- sulfonic acid, 4- ethyl phenenyl azochlorosulfonate acid, 1H, 1H, 2H, 2H- perfluor are pungent The sulphurs such as alkyl sulfonic acid, perfluor (2- Ethoxyethane) sulfonic acid, pentafluoroethane sulfonic acid, nine fluorine butane -1- sulfonic acid, dodecyl benzene sulfonic acid Acid or its water and object, salt etc..

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

The cured films of embodiments of the present invention forms the content with (D) ingredient in composition, relative to as (A) at 100 mass parts of total amount of the polymer of the compound and (B) ingredient that divide, preferably 0.5 mass parts~20 mass parts, more preferably For 0.8 mass parts~15 mass parts, further preferably 0.8 mass parts~6 mass parts.By the content 0.5 for making (D) ingredient More than mass parts, sufficient Thermocurable and solvent resistance can be assigned, the high sensitivity to exposure can also be assigned.In addition, Content 20 by making (D) ingredient below the mass, can make the storage stability of cured film formation composition good.

The cured film formation composition of present embodiment is mainly used with the solution state for being dissolved in solvent.It uses at this time Solvent, as long as (A) ingredient, (B) ingredient, (C) ingredient and (D) ingredient, and/or other aftermentioned additives can be dissolved, Its type and structure etc. are not particularly limited.

As the specific example of solvent, can enumerate for example, the molten fibre of ethylene glycol single methyl ether, ethylene glycol monomethyl ether, methyl Agent acetic acid esters, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol list first Base ether, propylene glycol monomethyl ether, propylene glycol propyl ether acetic acid esters, toluene, dimethylbenzene, methyl ethyl ketone, cyclopentanone, ring Hexanone, 2- butanone, 3- methyl -2 pentanone, 2 pentanone, 2-HEPTANONE, gamma-butyrolacton, 2 hydroxy propanoic acid ethyl ester, 2- hydroxyl -2- first Base ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2- hydroxy-3-methyl methyl butyrate, 3- methoxypropionic acid first Ester, 3- methoxypropionate, 3- ethoxyl ethyl propionate, 3- ethoxypropanoate, methyl pyruvate, ethyl pyruvate, Ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide and N- Methyl pyrrolidone etc..

These solvents can be come in a manner of individually one kind or two or more combination using.

Further, the cured film of present embodiment, which is formed, uses composition can basis as long as not damaging effect of the invention It needs containing polymerization initiator, sensitizer, silane coupling agent, surfactant, rheology control agent, pigment, dyestuff, save and stablize Agent, defoaming agent, antioxidant etc..

For example, sensitizer using present embodiment cured film formation with composition formed heat cured film after, to promotion Light reaction is effective.

The sensitizer of an example as other additives can enumerate benzophenone, anthracene, anthraquinone, thioxanthones etc. and its derive Object and nitrophenyl compound etc..Wherein, preferably benzophenone derivates and nitrophenyl compound.As preferred chemical combination The specific example of object can enumerate N, N- diethylamino benzophenone, 2- nitrofluorene, 2- nitryl fluorenone, 5- nitro acenaphthene, 4- nitro Biphenyl, 4- nitrocinnamic, 4- nitro Stilbene, 4- nitro benzophenone, 5- nitroindoline etc..Particularly preferable as benzophenone The N of derivative, N- diethylamino benzophenone.

These sensitizers are not limited by above compound.In addition, sensitizer can compound alone or in combination of two kinds or more And it is used in combination.

The cured film of present embodiment forms the use ratio with the sensitizer in composition, relative to (A) ingredient and (B) 100 mass parts of total quality of ingredient, preferably 0.1 mass parts~20 mass parts, more preferably 0.2 mass parts~10 mass Part.If there is the case where cannot fully obtaining the effect as sensitizer in the case where the ratio is too small；Excessive In the case of, sometimes generate transmissivity decline and film it is coarse.

The cured film formation of present embodiment uses composition to contain the low molecular light orientation ingredient as (A) ingredient, make For (B) ingredient and (A) ingredient light orientation ingredient be comparably hydrophilic polymer, as (C) ingredient have 2 with The compound of upper trialkoxysilyl and crosslinking catalyst as (D) ingredient.Then, as long as not damaging of the invention Effect can contain other additives.

(A) match ratio of ingredient and (B) ingredient is preferably 5:95~65:35 by quality ratio.In the content mistake of (B) ingredient In the case where big, liquid crystal aligning is easy decline；In the case where too small, since solvent resistance declines, orientation is easy decline.

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

[1]: the match ratio of (A) ingredient and (B) ingredient is 5:95~65:35 by quality ratio, based on (A) ingredient and (B) 100 mass parts of total amount of ingredient, (D) containing 10 mass parts~100 mass parts (C) ingredient and 0.5~20 mass parts at Composition is used in the cured film formation divided.

[2]: the match ratio of (A) ingredient and (B) ingredient is 5:95~65:35 by quality ratio, based on (A) ingredient and (B) 100 mass parts of total amount of ingredient, (D) containing 10 mass parts~100 mass parts (C) ingredient and 0.5~20 mass parts at Divide and composition is used in the formation of the cured film of solvent.

Matching by the cured film formation composition use in the form of a solution of present embodiment described below Composition and division in a proportion example, modulator approach etc..

About the ratio of the solid component in the cured film formation composition of present embodiment, as long as each ingredient is equably Be dissolved in solvent, be just not particularly limited, be the 1 mass % of mass %~80, the preferably 3 mass % of mass %~60, more preferably For 5 mass of mass %~40 %.At this point, so-called solid component, refers to and removes from the whole components of cured film formation composition Remove the ingredient of solvent.

The modulator approach of the cured film formation composition of present embodiment is not particularly limited.As modulation method, can enumerate For example, mixing (A) ingredient, (C) ingredient and (D) ingredient, shape into the solution of (B) ingredient for being dissolved in solvent with defined ratio At the method for uniform solution, or in the appropriate stage of the modulation method, other additives are further added as needed and are mixed The method of conjunction.

In the modulation of the cured film formation composition of present embodiment, can directly it use anti-by the polymerization in solvent The solution for the particular polymers that should be obtained.In this case, for example, to making the monomer with polyethylene glycol ester group and there is carbon At least one of monomer of hydroxyalkyl ester group of atomicity 2~5 is with the monomer with carboxyl and with the list of phenolic hydroxyl group At least one of body copolymerization and obtain (B) ingredient solution in, in the same manner as aforementioned be added (A) ingredient, (C) ingredient and (D) ingredient and form uniform solution.It, can further additional input solvent at this point, for the purpose of being adjusted by concentration.At this point, (B) Solvent used in the generating process of ingredient, can be with solvent used in the adjustment of the concentration of cured film formation composition It is identical, furthermore it can also be different.

In addition, the solution for the cured film formation composition modulated, it is preferable to use 0.2 μm or so of aperture filter etc. It is used after being filtered.

By in substrate (for example, silicon/silicon dioxide is substrate coated, silicon nitride board, is coated with metal such as aluminium, molybdenum, chromium Deng substrate, glass substrate, quartz base plate, ito substrate etc.), film is (for example, triacetyl cellulose (TAC) film, cyclic olefin polymerization The resin films such as object film, polyethylene terephthalate film, acrylic films) etc. on, by stick painting, rotary coating, flow coat, The cured film of the coating present embodiment such as roller coating, slot coated, the rotary coating for being connected in slit, ink-jet application, printing is formed Film is formed with the solution of composition, then, is thermally dried using hot plate or baking oven etc., cured film can be formed.

As the condition of heat drying, as long as the ingredient of the orientation material formed by cured film is with insoluble for being coated on Polymerizable liquid crystal solution in degree cross-linking reaction is carried out by crosslinking agent, for example, using from temperature 60 C~200 DEG C, the heating temperature that suitably selects in the time 0.4 minute~60 minutes ranges and heating time.Heating temperature and heating Time is preferably 70 DEG C~160 DEG C, 0.5 minute~10 minutes.

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

The cured film formed in this way, can be by carrying out polarisation UV irradiation as orientation material, that is, make liquid crystal The component being orientated Deng the compound with liquid crystal liquid crystal property functions.

Pass through as the illuminating method of polarisation UV usually using ultraviolet light~visible light of the wavelength of 150nm~450nm It is carried out in room temperature or in the state of heated from vertical or oblique direction linear polarization.

Since there is solvent resistance and heat resistance by the orientation material that film composition is formed that solidifies of present embodiment, so After coating is comprising the phase difference material of polymerizable liquid crystal solution on the orientation material, and being heated to the phase transition temperature of liquid crystal Make phase difference material mesomorphic state, is orientated it on orientation material.Then, the phase difference material of state of orientation is become Directly solidify, phase difference material can be formed in a manner of with optically anisotropic layer.

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

In addition, in the case where manufacturing patterning phase difference material used in 3D display device, to by present embodiment Solidify the cured film that film composition is formed by the above method, via the mask of line and space pattern according to the benchmark of regulation, example Such as, polarisation UV exposure is carried out with the direction of+45 degree, then, removes the direction spent after mask with -45 and expose polarisation UV, obtain shape At the orientation material in 2 kinds of different liquid crystal aligning regions of the tropism control direction of liquid crystal.Then, coating is molten comprising polymerizable liquid crystal It after the phase difference material of liquid, is heated to the phase transition temperature of liquid crystal and makes phase difference material mesomorphic state, make on orientation material It is orientated.Then, solidify the phase difference material for becoming state of orientation directly, can obtain respectively it is multiple, regularly match The patterning phase difference material in 2 kinds of different phase difference regions of phase difference characteristics is set.

In addition, formed using mode as described above, with present embodiment orientation material 2 plate bases, with via The mode that spacer faces each other the orientation material on two substrates is bonded, and then, injects liquid crystal between these substrates, can also be with The liquid crystal display element that liquid crystal is orientated is made.

Therefore, the cured film formation composition of present embodiment can be adapted for various phase difference materials (phase difference film), The manufacture of liquid crystal display element etc..

Embodiment

Hereinafter, enumerating embodiment, further present embodiment is described in detail, but present embodiment is not by these Embodiment limits.

[dummy suffix notation used in embodiment]

The meaning of the dummy suffix notation used below in an example is as follows.

CIN1:4- (6- hydroxyl hexyl oxygroup) methyl cinnamate

CIN2:3- methoxyl group -4- (6- hydroxyl hexyl oxygroup) methyl cinnamate

MAA: methacrylic acid

MMA: methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

AIBN: α, α '-azodiisobutyronitrile

HPCEL: hydroxypropyl cellulose

AADEG: polyester (adipic acid/diethylene glycol)

TTMSI: three (3- trimethoxy-silylpropyl) isocyanuric acid esters

BTMSE: bis- (trimethoxysilyl) ethane

PTSA: p-methyl benzenesulfonic acid monohydrate

PPTS: para-methylbenzenepyridinsulfonate sulfonate

PM: propylene glycol monomethyl ether

According to the number-average molecular weight and weight average molecular weight of the acrylic copolymer that synthesis example below obtains, day is used This light splitting (strain) GPC device processed (Shodex (registered trademark) カラ system KF803L and KF804L), will dissolve out solvent tetrahydro Furans with flow 1mL/ minutes in column (40 DEG C of column temperature) flowing eluted under conditions of be measured.In addition, following numbers Average molecular weight (hereinafter referred to as Mn.) and weight average molecular weight (hereinafter referred to as Mw.) indicated with polystyrene scaled value.

By MAA 2.5g, MMA 9.2g, HEMA 5.0g, as the AIBN 0.2g of polymerization catalyst it is dissolved in PM 50.7g obtains acrylic copolymer solution (25 matter of solid component concentration and reacting it 20 hours Measure %) (P1).The Mn of resulting acrylic copolymer is 19,600, Mw 45,200.

Modulate each cured film formation composition of embodiment and comparative example using composition shown in table 1, respectively into Gone adaptation, orientation sensitivity, patternability, transmissivity evaluation.

[table 1]

Table 1

[evaluation of adaptation]

Using spin coater by each cured film formation composition of embodiment and comparative example with 2000rpm in alkali-free On glass after rotary coating 30 seconds, 120 seconds heat dryings are carried out in heat-circulation type baking oven at 130 DEG C of temperature and form solidification Film.To the cured film with 50mJ/cm²Vertically irradiate the linear polarization of 313nm.Solidification is formed by substrate after exposure Film surface uses the horizontal alignment polymerizable liquid crystal solution RMS03- of spin coater coating メ Le Network Co. Ltd. system 013C then carries out 60 seconds prebake conditions on hot plate at 60 DEG C, forms 1.0 μm of film thickness of film.The film is existed 1000mJ/cm²Lower exposure is produced on the phase difference material in cured film with polymerizable liquid crystal layer.Using cutter to resulting Grid (1mm × 1mm × 100 piece) are drawn on phase difference material surface on substrate, then, are pasted adhesive tape and are then counted out and shelling Of phase difference material (cured film and polymerizable liquid crystal layer) unstripped and remaining grid when from the adhesive tape on substrate Number.The situation that the unstripped and remaining grid of phase difference material remains 90 or more is judged as that adaptation is good.

[evaluation of orientation sensitivity]

Using spin coater with 2000rpm by each cured film formation composition of embodiment and comparative example in alkali-free On glass after rotary coating 30 seconds, 120 seconds heat dryings are carried out in heat-circulation type baking oven at 130 DEG C of temperature, form solidification Film.The linear polarization of 313nm is vertically irradiated to the cured film, forms orientation material.Orientation material surface on substrate, uses rotation The horizontal alignment polymerizable liquid crystal solution RMS03-013C for turning coating machine coating メ Le Network Co. Ltd. system, then, at 60 DEG C 60 seconds prebake conditions are carried out on hot plate, form 1.0 μm of film thickness of film.With 1000mJ/cm²The film is exposed, is made The phase difference material with polymerizable liquid crystal layer on orientation material.By a pair of of polarizer folder of the phase difference material on made substrate Enter, observe the current status of the phase difference characteristics in phase difference material, measurement orientation material shows polarisation required for liquid crystal aligning The light exposure of UV.Orientation material with highly oriented sensitivity can make the polymerizable liquid crystal layer being orientated on material aobvious under low light exposure Show orientation.

[evaluation of patternability]

Using spin coater with 2000rpm rotary coating embodiment and each cured film of comparative example on alkali-free glass It is formed after using composition 30 seconds, carries out 120 seconds heat dryings in heat-circulation type baking oven at 130 DEG C of temperature and form cured film. Via 100 μm of lines and gap mask to the cured film with 30mJ/cm²Vertically irradiate the linear polarization of 313nm.Removing is covered Mould, after being rotated by 90 ° substrate, with 15mJ/cm²The linear polarization for vertically irradiating 313nm, obtains the orientation for foring liquid crystal Control the orientation material in 90 degree of different 2 kind in direction liquid crystal aligning region.On orientation material on the substrate, rotary coating is used Machine is coated with the horizontal alignment polymerizable liquid crystal solution RMS03-013C of メ Le Network Co. Ltd. system, then, at 60 DEG C in hot plate 60 seconds prebake conditions of upper progress form 1.0 μm of film thickness of film.With 1000mJ/cm²The film is exposed, polymerism liquid is made Crystalline substance polymerization, the patterning phase difference material arranged with making 2 kinds of regional rules with out of phase difference characteristic.Use polarized light microscopy Patterning phase difference material on substrate made by sem observation, the case where No yield point defect is formed with to phase difference pattern evaluation Be zero, it will be seen that orientation defect the case where be evaluated as ×.

[evaluation of light transmittance (transparency)]

Using spin coater with 2000rpm rotary coating embodiment and each cured film of comparative example on a quartz substrate It is formed after using composition 30 seconds, carries out heat drying baking in 120 seconds on hot plate at 130 DEG C of temperature and form film thickness 300nm Cured film.Film thickness is measured using FILMETRICS society F20.Use ultraviolet light visible spectrophotometer ((strain) Shimadzu Make made SHIMADZU UV-2550 model) cured film is measured to the transmissivity of the light of wavelength 400nm.

[result of evaluation]

The result for having carried out the above evaluation is shown in table 2.

[table 2]

Table 2

The orientation material obtained using the heat cured film formation composition modulated by Examples 1 to 5 is to be less than 100mJ/cm²Light exposure show liquid crystal aligning, it can be understood as it is with highly oriented sensitivity.Furthermore, it is possible to carry out Optical design is formed.Further, high transparency is shown.

Comparative example 1 and comparative example 2 are difficult to be orientated, and not can be carried out light pattern and are formed.

Industrial availability

Cured film according to the present invention, which is formed, uses composition, as be used to form liquid crystal display element liquid crystal orientation film, Be set to the orientation material of internal, the external optical anisotropic film of liquid crystal display element be it is highly useful, particularly suitable as The forming material of the patterning phase difference material of 3D display device.

Claims

1. a kind of cured film, which is formed, uses composition, which is characterized in that contain:

(A) with light orientation group with a kind or 2 kinds in hydroxyl, carboxyl, trialkoxysilyl and amino with The compound of upper substituent group,

(B) at least one kind of in following polymer: polyether polyol, polyester polyol, cellulose or derivatives thereof have In at least one of polyethylene glycol ester group and the hydroxyalkyl ester group of carbon atom number 2~5 and carboxyl and phenolic hydroxyl group extremely Acrylic polymer and cyclodextrin of few one or derivatives thereof,

(C) with the compound of 2 or more trialkoxysilyls, and

(D) crosslinking catalyst,

100 mass parts of total amount based on (A) ingredient Yu (B) ingredient, containing 10 mass parts~100 mass parts (C) at Point.

2. cured film according to claim 1, which is formed, uses composition, which is characterized in that the polyester polyol is selected from poly- carbon It is at least one kind of in acid esters polyalcohol and polycaprolactone polyol.

3. cured film according to claim 1, which is formed, uses composition, which is characterized in that the light orientation of (A) ingredient Group is the functional group for carrying out the structure of photodimerization or photoisomerization.

4. cured film according to claim 1, which is formed, uses composition, which is characterized in that the light orientation of (A) ingredient Group is cinnamoyl.

5. cured film according to claim 1, which is formed, uses composition, which is characterized in that the light orientation of (A) ingredient Group is the group of azobenzene structure.

6. cured film according to claim 1, which is formed, uses composition, which is characterized in that the compound of (A) ingredient has There are 2 or more hydroxyls.

7. cured film according to claim 1, which is formed, uses composition, which is characterized in that (D) ingredient is that acid or heat produce Sour agent.

8. cured film according to claim 1, which is formed, uses composition, which is characterized in that (A) ingredient and (B) ingredient Ratio is 5:95~65:35 by quality ratio.

9. cured film according to claim 1, which is formed, uses composition, which is characterized in that based on (A) ingredient and (B) at 100 mass parts of total amount divided, contain 0.5 mass parts~20 mass parts (D) ingredient.

10. a kind of orientation material, which is characterized in that by cured film formation composition system according to any one of claims 1 to 9 At.

11. a kind of phase difference material, which is characterized in that using by cured film formation group according to any one of claims 1 to 9 It closes the cured film that object obtains and is formed.