CN110325886A - Cured film is formed with composition, orientation material and phase difference material - Google Patents

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

Info

Publication number
CN110325886A
CN110325886A CN201880013114.6A CN201880013114A CN110325886A CN 110325886 A CN110325886 A CN 110325886A CN 201880013114 A CN201880013114 A CN 201880013114A CN 110325886 A CN110325886 A CN 110325886A
Authority
CN
China
Prior art keywords
carbon atom
group
atom number
base
chain
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201880013114.6A
Other languages
Chinese (zh)
Inventor
古川优树
伊藤润
菅野裕太
畑中真
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nissan Chemical Corp
Original Assignee
Nissan Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp
Publication of CN110325886A publication Critical patent/CN110325886A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/13363—Birefringent elements, e.g. for optical compensation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Optics & Photonics (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Liquid Crystal (AREA)
  • Polarising Elements (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

The subject of the invention is to provide having excellent vertical orientation, the orientation material of polymerizable liquid crystal vertical orientation can be made with high sensitivity on resin film, and for providing the cured film formation composition of the phase difference material using such orientation material.Solution is cured film formation composition, orientation material, phase difference material, and above-mentioned cured film formation composition is characterized in that, contain: (A) has the polymer of vertical orientation group；(B) compound with 2 or more the polymerizable groups comprising C=C double bond；And (C) radical polymerization initiator, substantially only (B) ingredient has the polymerizable group comprising C=C double bond.

Description

Cured film is formed with composition, orientation material and phase difference material
Technical field
The present invention relates to the cured film formation compositions for the vertically oriented material for being suitable for making liquid crystal molecule vertical orientation.Especially It is to be formed the present invention relates to useful cured film for production+C plate (positive c plate) with composition, orientation material and phase difference The material ,+C plate (positive c plate) are to improve and be filled with the IPS liquid crystal of the liquid crystal with positive dielectric anisotropy (△ ε > 0) Showing device (In-plane Switching LCD；In face orientation conversion LCD) etc. liquid crystal display devices (liquid crystal display；LCD viewing angle characteristic), as organic el display the viewing angle characteristic of circular polarization light board that uses of antireflection film and It uses.
Background technique
IPS-LCD is characterized in that, the inclination of the vertical direction since liquid crystal molecule does not occur, as caused by visual angle Brightness change/color change is few, but can enumerate as weakness and be not easy to make contrast and brightness, this high point of response speed.Such as As disclosed in Patent Document 1, propose that the compensation film at visual angle, such unused visual angle is not used in the IPS-LCD at initial stage Compensation film IPS-LCD due to light leakage relatively large under the dark state at inclination angle, have display low contrast value this The shortcomings that sample.
The IPS-LCD compensation film for having used+C plate He+A plate (positive a plate) is disclosed in patent document 2.In the document about Wherein documented liquid crystal display element shows following composition.
1) clipping between the two substrates of the electrode supply by that can apply parallel electric field to liquid crystal level has level The liquid crystal layer of orientation.
2) one piece or more of+A plate and+C plate are clipped by two polarizing films.
3) primary optical axis of+A plate and the primary optical axis of liquid crystal layer are vertical.
4) the phase difference value R of liquid crystal layer is determined in a manner of meeting following formulaLC,+C plate phase difference value R+C,+A plate phase Difference R+A。
RLC: R+C: R+A≒ 1:0.5:0.25
5) phase difference value of the phase difference value of the thickness direction of the protective film of polarizing film relative to+A plate and+C plate is not shown Relationship (TAC, COP, PNB).
Furthermore there is disclosed to provide by the way that the light leakage of the dark state under inclination angle to be minimized to have front and inclination The IPS-LCD of high contrast features, low gamut (Color Shift) under angle as a purpose, it is with+A plate and+C plate IPS-LCD (patent document 3).It is inclined further to also proposed the circle used for the antireflection film improved as organic el display The viewing angle characteristic of vibration tabula rasa, and the motion (patent document 5) of use+C plate.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2-256023 bulletin
Patent document 2: Japanese Unexamined Patent Publication 11-133408 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2009-122715 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2001-281669 bulletin
Patent document 5: Japanese Unexamined Patent Publication 2015-79256 bulletin
Summary of the invention
Problems to be solved by the invention
Such as previous propose, the light leakage of+C plate due to the big place in the visual angle that can compensate for polarizing film, conduct IPS-LCD, the optical compensation films of circular polarization light board that the antireflection film of organic el display uses are highly useful.However, The previous commonly known method using stretch processing is difficult to make vertically oriented (positive c plate) sex expression.
In addition, what is proposed has used the vertical alignment layer of polyimides to need to use N- methyl -2- in film production in the past The solvent of the polyimides such as pyrrolidones.Thus while not becoming problem for glass baseplate, but in the feelings that substrate is film Under condition, has and such problems is damaged to substrate in forming the alignment film.Moreover, for having used vertically taking for polyimides To film, the firing under high temperature is needed, there is film base material non-refractory such problems.
It further also proposed by directly being handled substrate with the silane coupling agent etc. with chain alkyl, thus The method for forming vertical alignment layer, but in the case where hydroxyl is not present in substrate surface, there is processing difficult, substrate is restricted this The problem of sample (patent document 4).
The requirement reduced in recent years according to manufacturing cost, it is desirable that in TAC (cellulose triacetate) film, COP (cyclic olefin polymerization Object) on the cheap resin film such as film, passes through so-called roll-to-roll (roll to roll) and produce.However, by it is as described above with The alignment films formed toward material are difficult to the manufacture+C plate on resin film.
It is therefore desirable to be capable of forming the orientation material of highly reliable+C plate on the resin films such as TAC film and for shape At the cured film formation composition of such orientation material.
The present invention be based on the above understanding, result of study and propose, project to be solved is to provide following solidifications Film, which is formed, uses composition, and being used to provide has excellent vertical orientation, and has transparent required by optical compensation films Property, solvent resistance, can steadily make under the firing condition between low-temperature short-time on resin film polymerizable liquid crystal hang down The orientation material being directly orientated.
Moreover, it is a further object of the present invention to provide obtained by above-mentioned cured film formation composition, have excellent hang down Straight orientation and has solvent resistance, can also steadily make under the firing condition between low-temperature short-time even if on resin film The orientation material of polymerizable liquid crystal vertical orientation and the phase difference material useful for+C plate formed using the orientation material.
Other objects and advantages of the present invention is specified by following record.
The method used for solving the problem
The inventors of the present invention have made intensive studies to achieve the goals above, as a result, it has been found that, have by selecting vertical Solidification based on the compound of the polymer of orientation group and the polymerizable group with 2 or more comprising C=C double bond Film, which is formed, completes the present invention with material so as to form the cured film with excellent vertical orientation.
That is, as the 1st viewpoint, being related to a kind of cured film formation composition, which is characterized in that contain in the present invention:
(A) there is polymer of the group as vertical orientation group shown in following formula [1]；
(B) compound with 2 or more the polymerizable groups comprising C=C double bond；And
(C) radical polymerization initiator,
Substantially only (B) ingredient has the polymerizable group comprising C=C double bond.
(in formula [1],
Y1It indicates singly-bound, or indicates to combine base, above-mentioned combination base is selected from-O- ,-CH2O-、-COO-、-OCO-、- Group in NHCO- ,-NH-CO-O- and-NH-CO-NH-,
Y2(alkylidene can be by 1~3 for the alkylidene of the carbon atom number 1~15 of expression singly-bound, straight-chain or branched It interrupts in conjunction with base A, still, is not combined each other in conjunction with base A.) or-CH2-CH(OH)-CH2Or Y2It indicates to be selected from phenyl ring, hexamethylene (any hydrogen atom in the cyclic group of the divalent cyclic group can be by straight-chain or branched for divalent cyclic group in ring or heterocycle The alkyl of carbon atom number 1~3, the alkoxy of carbon atom number 1~3 of straight-chain or branched, straight-chain or branched carbon The alkoxy or fluorine atom containing fluorine of the carbon atom number 1~3 of the alkyl containing fluorine of atomicity 1~3, straight-chain or branched Replace.),
Y3(alkylidene can be in straight-chain, branched and ring-type for expression singly-bound or the alkylidene of carbon atom number 1~15 Any one or their combination, which can combine base A to interrupt, still, not tie each other in conjunction with base A by 1~3 It closes.),
Y4Indicate singly-bound, or indicate in phenyl ring, cyclohexane ring or heterocycle divalent cyclic group (the divalent cyclic group should Any hydrogen atom in cyclic group can be by the alkyl of straight-chain or the carbon atom number 1~3 of branched, straight-chain or branched The alkyl containing fluorine, straight-chain or the branch of the carbon atom number 1~3 of the alkoxy of carbon atom number 1~3, straight-chain or branched The alkoxy containing fluorine or fluorine atom of the carbon atom number 1~3 of shape replace.) or Y4Indicate the carbon atom with steroid skeleton The divalent organic group of number 17~30,
Y5Indicate the divalent cyclic group in phenyl ring, cyclohexane ring or heterocycle (in the cyclic group of the divalent cyclic group Any hydrogen atom can be by the carbon atom number 1 of the alkyl of straight-chain or the carbon atom number 1~3 of branched, straight-chain or branched The carbon atom of the alkyl containing fluorine of the carbon atom number 1~3 of~3 alkoxy, straight-chain or branched, straight-chain or branched The alkoxy containing fluorine or fluorine atom of number 1~3 replace.),
N indicates 0~4 integer, in the case where n is 2 or more, each Y5It can be the same or different,
Y6Indicate hydrogen atom, the alkyl of carbon atom number 1~18, the alkyl containing fluorine of carbon atom number 1~18, carbon atom number 1~18 alkoxy or alkoxy (alkyl of the carbon atom number 1~18, carbon atom number 1 containing fluorine of carbon atom number 1~18 The alkoxy containing fluorine of~18 alkyl containing fluorine, the alkoxy of carbon atom number 1~18 and carbon atom number 1~18 can be Any one of straight-chain, branched and ring-type or their combination can combine base A to interrupt, still, in conjunction with base by 1~3 A is not combined each other.),
In Y2And Y3In the case where indicating the group other than singly-bound, Y2With Y3Combination can be singly-bound, can also be via knot It closes base A and combines,
In Y3And Y4In the case where indicating the group other than singly-bound, Y3With Y4Combination can be singly-bound, can also be via knot It closes base A and combines,
In Y4And Y5In the case where indicating the group other than singly-bound, Y4With Y5Combination can be singly-bound, can also be via knot It closes base A and combines,
In Y5And Y6In the case where indicating the group other than singly-bound, Y5With Y6Combination can be singly-bound, can also be via knot It closes base A and combines,
In the case where n is 2 or more, 1 Y5With the Y adjacent with its5Combination can be singly-bound, can also be via combination Base A and combine,
It indicates to be selected from-O- ,-CH in conjunction with base A2In O- ,-COO- ,-OCO- ,-NHCO- ,-NH-CO-O- and-NH-CO-NH- Group,
Wherein, the number for the carbon atom for including in group shown in formula [1] adds up to 6~30.).
As the 2nd viewpoint, it is related to cured film formation composition described in the 1st viewpoint, (B) ingredient includes C=C double bond Polymerizable group be in acryloyl group, methylacryloyl, vinyl, allyl and dimaleoyl imino at least one Kind.
As the 3rd viewpoint, it is related to cured film formation composition described in the 1st viewpoint or the 2nd viewpoint, is based on (A) ingredient 100 mass parts contain 10 mass parts~2000 mass parts (B) ingredient.
As the 4th viewpoint, it is related to cured film formation composition described in any one of the 1st viewpoint~the 3rd viewpoint, relatively In (A) ingredient of every 100 mass parts, contain 0.1 mass parts~50 mass parts (C) ingredient.
As the 5th viewpoint, it is related to a kind of orientation material, which is characterized in that be to make any one of the 1st viewpoint~the 4th viewpoint institute The cured film formation composition stated solidifies and obtains.
As the 6th viewpoint, it is related to a kind of phase difference material, which is characterized in that be using by appointing in the 1st viewpoint~the 4th viewpoint Cured film formation composition described in one obtain cured film and formed.
The effect of invention
1st scheme according to the present invention can provide cured film formation composition, be used for offer and have excellent hang down Straight orientation can steadily be such that polymerizable liquid crystal vertically takes on resin film under the firing condition between low-temperature short-time To orientation material and it is useful.
2nd scheme according to the present invention, can provide and have excellent vertical orientation, can be in the burning between low-temperature short-time Steadily make the orientation material of polymerizable liquid crystal vertical orientation under the conditions of.
3rd scheme according to the present invention, can provide can be formed on resin film with high efficiency, high transparency, Phase difference material with high solvent resistance.
Specific embodiment
< cured film, which is formed, uses composition >
Cured film of the invention, which is formed, uses composition, which is characterized in that containing has vertical orientation as (A) ingredient The polymer of group, as (B) ingredient with 2 or more include C=C double bond polymerizable groups compound and conduct (C) radical polymerization initiator of ingredient, substantially only (B) ingredient has the polymerizable group comprising C=C double bond.Moreover, only Otherwise damage effect of the invention, so that it may contain other additives.
Hereinafter, illustrating the detailed content of each ingredient.
< (A) ingredient >
It is the polymerization with vertical orientation group that cured film of the invention, which is formed with (A) ingredient contained by composition, Object.
More specifically, vertical orientation group is group shown in following formula [1].
In formula [1], singly-bound being indicated, or indicating to combine base, above-mentioned combination base is selected from-O- ,-CH2O-、-COO-、- Group in OCO- ,-NHCO- ,-NH-CO-O- and-NH-CO-NH-.
In formula [1], Y2Indicate the alkylidene of the carbon atom number 1~15 of singly-bound or straight-chain or branched, the alkylene Base can combine base A to interrupt by 1~3, still, not combine each other in conjunction with base A.
As Y2,-CH can also be enumerated2-CH(OH)-CH2-。
In addition, as Y2, the divalent cyclic group in phenyl ring, cyclohexane ring or heterocycle can be enumerated, in these cyclic groups Any hydrogen atom can be by the carbon atom number 1 of the alkyl of straight-chain or the carbon atom number 1~3 of branched, straight-chain or branched The carbon atom of the alkyl containing fluorine of the carbon atom number 1~3 of~3 alkoxy, straight-chain or branched, straight-chain or branched The alkoxy containing fluorine or fluorine atom of number 1~3 replace.
As above-mentioned heterocycle, can enumerate pyrrole ring, imidazole ring,Azoles ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, Quinoline ring, pyrazoline ring, isoquinolin ring, carbazole ring, purine ring, Thiadiazole, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine Ring, triazole ring, pyridine ring, benzimidazole ring, cinnolines ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenthazine Ring,Diazole ring, acridine ring etc., more preferably pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyrazoline ring, click Azoles ring, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyridine ring, benzimidazole ring.
As the alkyl enumerated as above-mentioned substituent group, methyl, ethyl, n-propyl, isopropyl, cyclopropyl can be enumerated, As above-mentioned alkoxy, obtained by oxygen atom-O- can be enumerated in conjunction with the group that the concrete example as abovementioned alkyl is enumerated Group.In addition, as the above-mentioned alkyl containing fluorine, containing the alkoxy of fluorine, can enumerate among abovementioned alkyl and alkoxy The group that any hydrogen atom has been replaced by fluorine atoms.
Wherein, from the aspect of the easiness of synthesis, Y2Preferably phenyl ring or cyclohexane ring.
In above-mentioned formula [1], Y3Indicate the alkylidene of singly-bound or carbon atom number 1~15, the alkylidene can for straight-chain, Any one of branched and ring-type or their combination can combine base A to interrupt, still, each other not in conjunction with base A by 1~3 In conjunction with.
In above-mentioned formula [1], Y4It indicates singly-bound, or indicates the divalent cyclic group in phenyl ring, cyclohexane ring or heterocycle, Any hydrogen atom in these cyclic groups can be by alkyl, straight-chain or the branch of straight-chain or the carbon atom number 1~3 of branched The alkyl containing fluorine of the carbon atom number 1~3 of the alkoxy of the carbon atom number 1~3 of shape, straight-chain or branched, straight-chain or The alkoxy containing fluorine or fluorine atom of the carbon atom number 1~3 of branched replace.
Alkyl enumerated as above-mentioned heterocycle and substituent group etc. can be in above-mentioned Y2In the example enumerated.
Further, as Y4, can be the divalent in the organic group selected from the carbon atom number 17~30 with steroid skeleton Organic group.Its preferred example is with from selected from cholestene, androstene, β-cholestene, epiandrosterone, ergostene, female steroid Ketone, 11 Alpha-hydroxy methylsterols, 11 α-progesterone, lanostene, norquen mestranol, methyltestosterone, norethindrone, pregnenolone, 2 of structure obtained by 2 hydrogen atoms are eliminated in structure in β-sitostene, stigmastene, stosterone and cholesteryl acetate etc. Valence group.More specifically, such as described below.
(in formula, * indicates binding site.)
Wherein, from the aspect of the easiness of synthesis, Y4Preferably phenyl ring, cyclohexane ring or the carbon with steroid skeleton The divalent organic group of atomicity 17~30.
In formula [1], Y5Indicate the divalent cyclic group in phenyl ring, cyclohexane ring or heterocycle, appointing in these cyclic groups Anticipating hydrogen atom can be by the carbon atom number 1~3 of the alkyl of straight-chain or the carbon atom number 1~3 of branched, straight-chain or branched Alkoxy, the alkyl containing fluorine of carbon atom number 1~3 of straight-chain or branched, straight-chain or branched carbon atom number 1 ~3 alkoxy containing fluorine or fluorine atom replaces.Above-mentioned heterocycle and the alkyl enumerated as substituent group etc. can for Above-mentioned Y4In the example enumerated.
Wherein, Y5Preferably phenyl ring or cyclohexane ring.
In addition, n indicates 0~4 integer in formula [1], and in the case where n is 2 or more, Y5It each other can be identical base Group or different groups.Wherein, from the aspect of acquired, synthesis the easiness of raw material, n is preferably 0~3.It is more excellent It is selected as 0~2.
In formula [1], Y6Indicate hydrogen atom, the alkyl of carbon atom number 1~18, carbon atom number 1~18 the alkane containing fluorine The alkoxy containing fluorine of base, the alkoxy of carbon atom number 1~18 or carbon atom number 1~18, the alkane of the carbon atom number 1~18 Base, the alkyl containing fluorine of carbon atom number 1~18, the alkoxy of carbon atom number 1~18 and carbon atom number 1~18 containing fluorine Alkoxy can be any one of straight-chain, branched and ring-type or their combination, can be combined in base A by 1~3 It is disconnected, still, do not combined each other in conjunction with base A.
Wherein, Y6The preferably alkyl of carbon atom number 1~18, the alkyl containing fluorine of carbon atom number 1~10, carbon atom number 1~18 alkoxy or the alkoxy containing fluorine of carbon atom number 1~10.More preferable Y6For carbon atom number 1~12 alkyl or The alkoxy of carbon atom number 1~12.Particularly preferred Y6For the alkyl of carbon atom number 1~9 or the alkoxy of carbon atom number 1~9.
In addition, in Y4In the case where the divalent organic group with steroid skeleton, Y6Preferably hydrogen atom.
Such as the alkyl of above-mentioned carbon atom number 1~18 can enumerate for example methyl, ethyl, n-propyl, isopropyl, normal-butyl, Isobutyl group, sec-butyl, tert-butyl, n-pentyl, 1- methyl-normal-butyl, 2- methyl-normal-butyl, 3- methyl-normal-butyl, 1,1- bis- Methyl-n-propyl, 1,2- dimethyl-n-propyl, 2,2- dimethyl-n-propyl, 1- ethyl-n-propyl, n-hexyl, 1- methyl- N-pentyl, 2- methyl-n-pentyl, 3- methyl-n-pentyl, 4- methyl-n-pentyl, 1,1- dimethyl-normal-butyl, 1,2- diformazan Base-normal-butyl, 1,3- dimethyl-normal-butyl, 2,2- dimethyl-normal-butyl, 2,3- dimethyl-normal-butyl, 3,3- dimethyl-are just Butyl, 1- ethyl-normal-butyl, 2- ethyl-normal-butyl, 1,1,2- trimethyl-n-propyl, 1,2,2- trimethyl-n-propyl, 1- second Base -1- methyl-n-propyl, 1- Ethyl-2-Methyl-n-propyl, n-heptyl, 1- methyl-n-hexyl, 2- methyl-n-hexyl, 3- first Base-n-hexyl, 1,1- dimethyl-n-pentyl, 1,2- dimethyl-n-pentyl, 1,3- dimethyl-n-pentyl, 2,2- dimethyl-are just Amyl, 2,3- dimethyl-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- dimethyl-n-hexyl, 1,2- dimethyl-n-hexyl, 1,3- dimethyl-n-hexyl, 2,2- dimethyl-just oneself Base, 2,3- dimethyl-n-hexyl, 3,3- dimethyl-n-hexyl, 1- ethyl-n-hexyl, 2- ethyl-n-hexyl, 3- ethyl-are just Hexyl, 1- methyl-1-ethyl-n-pentyl, 1- methyl-2- ethyl-n-pentyl, 1- methyl-3- ethyl-n-pentyl, 2- methyl-2- Ethyl-n-pentyl, 2- methyl -3- ethyl-n-pentyl, 3- methyl -3- ethyl-n-pentyl, n-nonyl, positive decyl, n-undecane Base, dodecyl, n-tridecane base, n-tetradecane base, n-pentadecane base etc..
As the alkylidene of above-mentioned carbon atom number 1~15, it can enumerate from abovementioned alkyl and eliminate 1 any hydrogen atom Bivalent group.
As the alkoxy of above-mentioned carbon atom number 1~18, oxygen atom-O- and the concrete example as abovementioned alkyl can be enumerated And group obtained by the group combination enumerated.
In addition, as the alkyl containing fluorine of above-mentioned carbon atom number 1~18, the alcoxyl containing fluorine of carbon atom number 1~18 Base can enumerate any hydrogen atom among the alkyl of above-mentioned carbon atom number 1~18 and the alkoxy of carbon atom number 1~18 by fluorine Atom instead of group.
Further, in Y2And Y3In the case where indicating the group other than singly-bound, Y2With Y3Combination can be singly-bound, can also To be combined via in conjunction with base A, in Y3And Y4In the case where indicating the group other than singly-bound, Y3With Y4Combination can be single Key can also be combined, in Y via in conjunction with base A4And Y5In the case where indicating the group other than singly-bound, Y4With Y5Combination can Think singly-bound, can also be combined via in conjunction with base A, in Y5And Y6In the case where indicating the group other than singly-bound, Y5With Y6's In conjunction with that can be singly-bound, can also be combined via in conjunction with base A, in the case where n is 2 or more, 1 Y5It is adjacent with its Y5Combination can be singly-bound, can also be combined via in conjunction with base A.
In addition, above-mentioned combination base A indicates to be selected from-O- ,-CH2O-、-CO-、-COO-、-OCO-、-NHCO-、-CONH-、- Group in NH-CO-O- ,-O-CO-NH- and-NH-CO-NH-.
In addition, the number for the carbon atom for including in group shown in formula [1] adds up to 6~30, for example, 6~20.
Wherein, if it is considered that the coating of vertical orientation and polymerizable liquid crystal, then be used as vertical orientation shown in formula [1] Property group, the preferably group of the alkyl comprising carbon atom number 7~18, particularly 8~15, further preferably carbon atom number 7 The alkyl of~18, especially 8~15.
The method for obtaining the polymer of (A) ingredient of the invention is not particularly limited.For example, poly- by free radical polymerization etc. Conjunction method makes the monomer with vertical orientation group and any monomer reaction, it is hereby achieved that the polymer of (A) ingredient.
The concrete example of any monomer is enumerated below.But it is not limited to this.
As the monomer with carboxyl, can enumerate for example, acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyl Oxygroup) ethyl) phthalic acid ester, mono- (2- (methacryloxy) ethyl) phthalic acid ester, N- (carboxyl phenyl) Malaysia acyl Imines, N- (carboxyl phenyl) Methacrylamide and N- (carboxyl phenyl) acrylamide etc..
As the monomer with epoxy group, can enumerate for example, glycidyl methacrylate, glycidyl Ester, allyl glycidyl ether, 3- vinyl -7- oxabicyclo [4.1.0] heptane, 1,2- epoxy -5- hexene and 1,7- are pungent 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, diethyleneglycol monoacrylate, diethylene glycol monomethyl third Olefin(e) acid ester, caprolactone 2- (acryloxy) ethyl ester, caprolactone 2- (methacryloxy) ethyl ester, poly(ethylene glycol) second Base ether acrylate, poly(ethylene glycol) ethyl ether methacrylate, 5- acryloxy -6- hydroxy norbomene -2- carboxyl - 6- lactone and 5- methacryloxy -6- hydroxy norbomene -2- carboxyl -6- lactone etc..
As the monomer with amino, can enumerate for example, acrylic acid 2- amino ethyl ester and methacrylic acid 2- amino methyl Deng.
As the monomer with phenolic hydroxyl group, can enumerate for example, hydroxy styrenes, N- (hydroxy phenyl) acrylamide, N- (hydroxy phenyl) Methacrylamide and N- (hydroxy phenyl) maleimide etc..
As the monomer with isocyanate group, can enumerate for example, acryloyl ethyl isocyanates, methylacryloyl Ethyl isocyanate and tetramethyl xylene isocyanate etc..
As acrylate compounds, can enumerate for example, methyl acrylate, ethyl acrylate, n-propyl, propylene Isopropyl propionate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, benzyl acrylate, acrylic acid naphthalene ester, acrylic acid Anthracene ester, acrylic acid anthracene methyl esters, phenyl acrylate, glycidyl acrylate, acrylic acid 2,2,2- trifluoro ethyl ester, acrylate Ester, isobornyl acrylate, acrylic acid 2- methoxy acrylate, methoxyethyl triethyleneglycol ester, acrylic acid 2- ethoxy ethyl ester, Tetrahydrofurfuryl acrylate, acrylic acid 3- methoxybutyl, acrylic acid 2- methyl -2- adamantane esters, acrylic acid 2- propyl -2- gold Rigid Arrcostab, acrylic acid 8- methyl -8- tricyclodecyl ester and acrylic acid 8- ethyl -8- tricyclodecyl ester etc..
As methacrylate compound, can enumerate for example, methyl methacrylate, ethyl methacrylate, methyl N-propyl, isopropyl methacrylate, n-BMA, Isobutyl methacrylate, methacrylic acid uncle Butyl ester, benzyl methacrylate, methacrylic acid naphthalene ester, methacrylic acid anthracene ester, methacrylic acid anthracene methyl esters, methacrylic acid Phenyl ester, glycidyl methacrylate, methacrylic acid 2,2,2- trifluoro ethyl ester, cyclohexyl methacrylate, metering system Sour isobornyl thiocyanoacetate, methacrylic acid 2- methoxy acrylate, methacrylic acid methoxyl group triethyleneglycol ester, methacrylic acid 2- ethyoxyl Ethyl ester, tetrahydrofurfuryl methacrylate, methacrylic acid 3- methoxybutyl, methacrylic acid 2- methyl -2- adamantane esters, Methacrylic acid gamma-butyrolacton ester, methacrylic acid 2- propyl -2- adamantane esters, the methacrylic acid 8- methyl -8- tricyclic last of the ten Heavenly stems Base ester and methacrylic acid 8- ethyl -8- tricyclodecyl ester etc..
As vinyl compound, can enumerate for example, methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl Carbazole, allyl glycidyl ether, 3- vinyl -7- oxabicyclo [4.1.0] heptane, 1,2- epoxy -5- hexene and 1,7- Octadiene monoepoxide etc..
As distyryl compound, can enumerate for example, styrene, methyl styrene, chlorostyrene, bromstyrol etc..
As maleimide compound, can enumerate for example, maleimide, N- methylmaleimido, N- phenyl horse Come acid imide and N- N-cyclohexylmaleimide etc..
(A) weight average molecular weight of the polymer of ingredient is preferably 1,000~200,000, more preferably 2,000~150, 000, further preferably 3,000~100,000.If weight average molecular weight is more than 200,000 and excessive, then sometimes in a solvent Dissolubility reduce, operability reduces, if weight average molecular weight is too small less than 1,000, then solvent resistance and heat resistance sometimes It reduces.
In the polymer of (A) ingredient, vertical orientation group there are ratios to be, the whole weight relative to the polymer Multiple every 100 moles of unit, preferably 3 moles of %~90 mole %, further preferably 5 moles of %~80 mole %.Less than 3 In the case where mole %, vertical orientation is become inadequate sometimes, in the case where excessive compared with 90 moles of %, is had to liquid A possibility that brilliant coating causes adverse effect.
Polymer with vertical orientation group can be suitble to enumerate using commercially available product for example, ARUFON UF- 5041, UF-5080, UF-5022 [more than, be all East Asia synthesis (strain) system] etc..
< (B) ingredient >
Cured film of the invention forms the polymerization with (B) ingredient in composition with 2 or more to include C=C double bond The compound of property group.
As the polymerizable group comprising C=C double bond, acryloyl group, methylacryloyl, vinyl, allyl can be enumerated Base and dimaleoyl imino etc..
(B) it is 3~16 that the polymerizable group comprising C=C double bond of ingredient, which is preferably carbon atom number, and end has not The polymerizable group of saturated bond, the specific side chain particularly preferably indicated as formula (b2).
In formula (b2), R51Be carbon atom number be 1~14, and selected from by fatty group, include the aliphatic of ring structures Organic group in group composed by base and aromatic series base is made of organic the combination of multiple organic groups in the group Base.R51It may include ester bond, ehter bond, amido bond or urethane bond etc..
In formula (b2), R52For hydrogen atom or methyl, preferably R52For the specific side chain of hydrogen atom, more preferably end For the specific side chain of acryloyl group, methylacryloyl or styryl.
In addition, (methyl) acrylate compounds so-called in this specification, refer to acrylate compounds and metering system Both ester compounds.Such as (methyl) acrylic acid refers to acrylic acid and methacrylic acid.In addition, (methyl) acryloyl group indicates CH2=CHCO- and CH (CH3)=CHCO-.
As the compound with the polymerizable group comprising C=C double bond, hereinafter, an example of suitable compound is enumerated, But (B) ingredient is not limited to these illustrations.
As the compound with 2 (methyl) acryloyl groups, such as ethylene glycol two (methyl) acrylate, two can be enumerated Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, 1,4- butanediol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexylene glycols two (methyl) acrylate, 1,9- nonanediol Two (methyl) acrylate, 2- methyl-1,8- ethohexadiol two (methyl) acrylate, 1,10- decanediol two (methyl) acrylic acid Ester, pentaerythrite two (methyl) acrylate, two (methyl) acrylate of tricyclic [5.2.1.02,6] decane dimethanol, dioxa Cyclohexane diol two (methyl) acrylate, 2- hydroxyl -1- acryloxy -3- methacryloxy propane, hydroxyl -1 2-, (methyl) acryloxy of 3- bis- propane, trihydroxy ethyl isocyanurate two (methyl) acrylate, the bis- [4- (2- (first of 9,9- Base) acryloyloxyethoxy) phenyl] fluorenes, undecylenoyl ethylene glycol two (methyl) acrylate, 1,3- adamantane glycol Two (methyl) acrylate, 1,3- adamantane dimethanol two (methyl) acrylate, Ethoxylated bisphenol A bis- (methyl) acrylic acid Ester etc..
Compound with 2 or more (methyl) acryloyl groups can be suitble to enumerate using commercially available product for example, ラ イ ト アクリレート3EG-A、ライトアクリレート4EG-A、ライトアクリレート9EG-A、ライトアクリレート 14EG-A、ライトアクリレートPTMGA-250、ライトアクリレートNP-A、ライトアクリレートMPD-A、ライ トアクリレート1.6HX-A、ライトアクリレート1.9ND-A、ライトアクリレートMOD-A、ライトアクリレー トDCP-A、ライトアクリレートBP-4EAL、ライトアクリレートBP-4PA、ライトアクリレートHPP-A、ライ トエステルG-201P、ライトエステルP-2M、ライトエステルEG、ライトエステル2EG、ライトエス テル3EG、ライトエステル4EG、ライトエステル9EG、ライトエステル14EG、ライトエステル 1.4BG、ライトエステルNP、ライトエステル1.6HX、ライトエステル1.9ND、ライトエステルG- 101P, ラ イ ト エ ス テ Le G-201P, ラ イ ト エ ス テ Le BP-2EMK [more than, be all common prosperity society chemical (strain) system]；NKエ ステル701A、NKエステルA-200、NKエステルA-400、NKエステルA-600、NKエステルA-1000、 NKエステルA-B1206PE、NKエステルABE-300、NKエステルA-BPE-10、NKエステルA-BPE-20、 NKエステルA-BPE-30、NKエステルA-BPE-4、NKエステルA-BPEF、NKエステルA-BPP-3、NKエ ステルA-DCP、NKエステルA-DOD-N、NKエステルA-HD-N、NKエステルA-NOD-N、NKエステル APG-100、NKエステルAPG-200、NKエステルAPG-400、NKエステルAPG-700、NKエステルA- PTMG-65、NKエステル1G、NKエステル2G、NKエステル3G、NKエステル4G、NKエステル9G、NKエ ステル14G、NKエステル23G、NKエステルBPE-80N、NKエステルBPE-100、NKエステルBPE- 200、NKエステルBPE-500、NKエステルBPE-900、NKエステルBPE-1300N、NKエステルDCP、NK エステルDCP-N、NKエステルHD-N、NKエステルNOD-N、NKエステルNPG、NKエステル1206PE、 NK エ ス テ Le 701, NK エ ス テ Le 9PG [more than, the village Dou Shixinzhong chemical industry (strain) system]；FANCRYL FA-124AS, FANCRYL FA-129AS、FANCRYL FA-222A、FANCRYL FA-240A、FANCRYL FA-P240A、FANCRYL FA- P270A、FANCRYL FA-321A、FANCRYL FA-324A、FANCRYL FA-PTG9A、FANCRYL FA-121M、 FANCRYL FA-124M、FANCRYL FA-125M、FANCRYL FA-220M、FANCRYL FA-240M、FANCRYL FA- 320M, FANCRYL FA-321M, FANCRYL FA-3218M, FANCRYL FA-PTG9M [more than, be all Hitachi chemical conversion (strain) System]；DPGDA, HODA, TPGDA, EBECRYL (registered trademark) 145, EBECRYL 150, IRR214-K, PEG400DA-D, EBECRYL (registered trademark) 11, HPDNA [ダ イ セ Le オ Le ネ Network ス (strain) system]；ビスコート#195,ビスコー ト#230、ビスコート#260、ビスコート#310HP、ビスコート#335HP、ビスコート#700HV、ビスコー ト #540, ビ ス コ ー ト #802, ビ ス コ ー ト #295 [more than, be all Japanese synthetic chemical industry (strain) system] etc..
As the compound (3 functional compound) with 3 (methyl) acryloyl groups, can enumerate for example, ethylene oxide changes Property 1,1,1- trimethylolethane trimethacrylate (methyl) acrylate [ethylene oxide addition molal quantity 3~30], ethylene oxide denatured three The modified trimethylolpropane of hydroxymethyl-propane three (methyl) acrylate [ethylene oxide addition molal quantity 3~30], propylene oxide Three (methyl) acrylate [propylene oxide addition molal quantity 3~30], ethylene oxide denatured glycerol three (methyl) acrylate [oxygen Change Addition on ethylene molal quantity 3~30], propylene oxide modified glycerol three (methyl) acrylate [propylene oxide addition molal quantity 3~ 30], modified three (2- (acryloxy) ethyl) isocyanide ureas of three (2- (acryloxy) ethyl) isocyanuric acid esters, 6-caprolactone Acid esters [6-caprolactone addition molal quantity 1~30], 1,1,1- trimethylolethane trimethacrylate (methyl) acrylate, trimethylolpropane Three (methyl) acrylate, double trimethylolpropane three (methyl) acrylate, pentaerythrite three (methyl) acrylate, glycerol Three (methyl) acrylate etc..
Above-mentioned 3 functional compound can be suitble to using commercially available product, and can enumerating such as ビ ス コ ー ト #360, [Osaka organises Learn industrial (strain) system]；NK エ ス テ Le A-GLY-9E, NK エ ス テ Le A-GLY-20E, NK エ ス テ Le AT-20E [more than, all It is the village Xin Zhong chemical industry (strain) system]；TMPEOTA, OTA480, EBECRYL (registered trademark) 135 [more than, it is all ダ イ セ Le オ Le ネ Network ス (strain) system], ビ ス コ ー ト #295, ビ ス コ ー ト #300 [more than, be all Osaka Organic Chemical Industry (strain) system]；ラ イ ト ア Network リ レ ー ト TMP-A, ラ イ ト ア Network リ レ ー ト PE-3A, ラ イ ト エ ス テ Le TMP [more than, be all Common prosperity society chemistry (strain) system]；NKエステルA-9300,NKエステルA-9300-1CL,NKエステルA-TMM-3,NK エ ス テ Le A-TMM-3L, NK エ ス テ Le A-TMM-3LM-N, NK エ ス テ Le A-TMPT, NK エ ス テ Le TMPT [more than, The village Dou Shixinzhong chemical industry (strain) system]；PETIA, PETRA, TMPTA, EBECRYL (registered trademark) 180 [more than, it is all ダ イ セ Le オ Le ネ Network ス (strain) system] etc..
As the compound (4 functional compound) with 4 (methyl) acryloyl groups, can enumerate for example, ethylene oxide changes Property double trimethylolpropane four (methyl) acrylate [ethylene oxide addition molal quantity 4~40], ethylene oxide denatured Ji Wusi Alcohol four (methyl) acrylate [ethylene oxide addition molal quantity 4~40], double trimethylolpropane four (methyl) acrylate, season Penta tetrol four (methyl) acrylate etc..
Above-mentioned 4 functional compound can be suitble to that such as NK エ ス テ Le ATM-4E, NK エ ス テ can be enumerated using commercially available product Le ATM-35E [more than, the village Dou Shixinzhong chemical industry (strain) system]；[the ダ イ セ Le オ Le ネ of EBECRYL (registered trademark) 40 Network ス (strain) system] etc., ビ ス コ ー ト #300 [Osaka Organic Chemical Industry (strain) system]；ラ イ ト ア Network リ レ ー ト PE-4A [common prosperity Society's chemistry (strain) system]；NK エ ス テ Le AD-TMP, NK エ ス テ Le A-TMMT [more than, the village Dou Shixinzhong chemical industry (strain) System]；EBECRYL (registered trademark) 140, EBECRYL 1142, EBECRYL 180 [more than, be all ダ イ セ Le オ Le ネ Network ス (strain) system] etc..
As with 5 or more (methyl) acryloyl groups compound (compounds more than 5 functions), can enumerate for example, It is ethylene oxide denatured dipentaerythritol six (methyl) acrylate [ethylene oxide addition molal quantity 6~60], ethylene oxide denatured Tripentaerythritol eight (methyl) acrylate [ethylene oxide addition molal quantity 6~60], dipentaerythritol five (methyl) acrylic acid Ester, dipentaerythritol six (methyl) acrylate, tripentaerythritol eight (methyl) acrylate etc..
Compound more than above-mentioned 5 function can be suitble to that such as NK エ ス テ Le A-DPH-12E can be enumerated using commercially available product [village Xin Zhong chemical industry (strain) system], ビ ス U ー ト #802 [Osaka Organic Chemical Industry (strain) system]；ライトアクリレート DPE-6A [common prosperity society chemistry (strain) system]；NK エ ス テ Le A-9550, NK エ ス テ Le A-DPH [more than, the village Dou Shixinzhong chemistry Industrial (strain) system]；DPHA [ダ イ セ Le オ Le ネ Network ス (strain) system] etc..
As 2 function carbamate (methyl) acrylate, (methyl) for example, phenylglycidyl ether can be enumerated (methyl) acrylic acid of the carbamate compound of acrylic acid adduct and hexamethylene diisocyanate, phenylglycidyl ether Addition product and the carbamate compound of toluene di-isocyanate(TDI) etc..
Above-mentioned 2 function carbamate (methyl) acrylate can be suitble to using commercially available product, can enumerate such as AH-600, AT-600 [more than, all it is common prosperity society chemical (strain) system]；NKオリゴU-2PPA,NKオリゴU-200PA,NKオリゴUA- 160TM、NKオリゴUA-290TM、NKオリゴUA-4200、NKオリゴUA-4400、NKオリゴUA-122P、NKオリゴUA- W2A [more than, the village Dou Shixinzhong chemical industry (strain) system]；EBECRYL (registered trademark) 210, EBECRYL 215, EBECRYL 230、EBECRYL 244、EBECRYL 245、EBECRYL 270、EBECRYL 280/15IB、EBECRYL 284、EBECRYL 285、EBECRYL 4858、EBECRYL 8307、EBECRYL 8402、EBECRYL 8411、EBECRYL 8804、EBECRYL 8807, EBECRYL 9227EA, 9270 EBECRYL, KRM (registered trademark) 7735 [more than, be all ダ イ セ Le オ Le ネ Network ス (strain) system]；Purple light (registered trademark) UV-6630B, purple light UV-7000B, purple light UV-7461TE, purple light UV-2000B, purple Light UV-2750B, purple light UV-3000, purple light UV-3200B, purple light UV-3210EA, purple light UV-3300B, purple light UV-3310B, Purple light UV-3500BA, purple light UV-3520TL, purple light UV-3700B, purple light UV-6640B [more than, be all that Japan synthesizes chemical work Industry (strain) system] etc..
As the commercially available of polyfunctional carbamate (methyl) acrylate compounds with 3 (methyl) acryloyl groups The concrete example of product can enumerate NK オ リ go UA-7100 [village Xin Zhong chemical industry (strain) system]；EBECRYL (registered trademark) 204, EBECRYL 205、EBECRYL 264、EBECRYL 265、EBECRYL 294/25HD、EBECRYL 1259、EBECRYL 4820, EBECRYL 8311, EBECRYL 8465, EBECRYL 8701, EBECRYL 9260, KRM (registered trademark) 8296, KRM 8667 [more than, all it is ダ イ セ Le オ Le ネ Network ス (strain) system]；Purple light (registered trademark) UV-7550B, purple light UV- 7000B, purple light UV-7510B, purple light UV-7461TE, purple light UV-2750B [more than, be all Japanese synthetic chemical industry (strain) System] etc..
As the commercially available of polyfunctional carbamate (methyl) acrylate compounds with 4 (methyl) acryloyl groups The concrete example of product, can enumerate EBECRYL (registered trademark) 8210, EBECRYL8405, KRM (registered trademark) 8528 [more than, all It is ダ イ セ Le オ Le ネ Network ス (strain) system]；Purple light (registered trademark) UV-7650B [Japanese synthetic chemical industry (strain) system] Deng.
As polyfunctional carbamate (methyl) acrylate compounds (5 with 5 or more (methyl) acryloyl groups Carbamate (methyl) acrylate more than function), it can enumerate for example, pentaerythrite three (methyl) acrylate and 1,6- Carbamate compound, the amino first of pentaerythrite three (methyl) acrylate and toluene di-isocyanate(TDI) of hexamethylene diisocyanate The carbamate compound of acid esters compound, pentaerythrite three (methyl) acrylate and isophorone diisocyanate, two seasons penta (methyl) acrylate of tetrol five and the carbamate compound of hexamethylene diisocyanate etc..
Carbamate (methyl) acrylate more than above-mentioned 5 function can be suitble to enumerate for example using commercially available product UA-306H, UA-306T, UA-306I, UA-510H [more than, all it is common prosperity society chemical (strain) system]；NKオリゴU-6LPA,NKオ リゴU-10HA、NKオリゴU-10PA、NKオリゴU-1100H、NKオリゴU-15HA、NKオリゴUA-53H、NKオリゴUA- 33H [more than, the village Dou Shixinzhong chemical industry (strain) system]；EBECRYL (registered trademark) 220, EBECRYL 1290, EBECRYL 5129, EBECRYL 8254, EBECRYL 8301R, KRM (registered trademark) 8200, KRM 8200AE, 8904 KRM, KRM 8452 [more than, all it is ダ イ セ Le オ Le ネ Network ス (strain) system]；Purple light (registered trademark) UV-1700B, purple light UV- 6300B, purple light UV-7600B, purple light UV-7605B, purple light UV-7610B, purple light UV-7620EA, purple light UV-7630B, purple light UV-7640B, purple light UV-7650B [more than, be all Japanese synthetic chemical industry (strain) system] etc..
(B) ingredient of the invention can be the side chain of polyunsaturated bond to have 1 or more end in the molecule High-molecular compound.As such high-molecular compound with the side chain that end is polyunsaturated bond, can preferably lift 2 or more side chains in the molecule have the high-molecular compound of (methyl) acryloyl group out.
As above-mentioned high-molecular compound, urethane acrylates system, epoxy acrylic system, various (methyl) can be enumerated The high-molecular compound containing 1 or more (methyl) acryloyl group of acrylic ester etc..
(B) weight average molecular weight of the high-molecular compound of ingredient be preferably 1,000~200,000, more preferably 5,000~ 50,000.If molecular weight less than 1,000, does not then play effect of the invention.On the other hand, if molecular weight is more than 100, 000 and it is excessive, then be not dissolved in composition sometimes.
As the compound of such (B) ingredient, can enumerate for example, ア Network リ ッ ト 8BR-930M, ア Network リ ッ ト 8UH-1006, ア Network リ ッ ト 8KQ-2001, ア Network リ ッ ト 8KX-078, ア Network リ ッ ト 1SX-1055 [more than, great achievement Off ァ イ Application ケ ミ カ Le strain formula meeting Society's system], the polymer such as SMP-250A, SMP-360A, SMP-550A [more than, Kyoeisha Chemical Co., Ltd.'s system].
Content in the case where containing (B) ingredient is, is 10 mass parts~2000 relative to every 100 mass parts (A) ingredient Mass parts, preferably 15 mass parts~500 mass parts.
< (C) ingredient >
It is radical polymerization initiator that cured film of the invention, which is formed with (C) ingredient in composition,.
As radical polymerization initiator, well known radical polymerization initiator can be used, can enumerate for example, alkylbenzene Ketone, benzophenone, acylphosphine oxide class, the benzoylbenzoic acid esters of rice Chi, oxime esters, single vulcanization tetra methylthiuram Class, thioxanthene ketone class etc..
Radical polymerization initiator used in the present invention can be enumerated for example, the α such as diacetyl-diones；Benzoin Equal acyloins class；The acyloin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether；Thioxanthones, 2,4- diethyl Thioxanthones, thioxanthones -4- sulfonic acid, benzophenone, 4,4 '-bis- (dimethylamino) benzophenone, 4,4 '-bis- (diethylaminos) The benzophenones such as benzophenone；Acetophenone, to dimethylamino benzoylformaldoxime, α, alpha, alpha-dimethyl oxygroup-α-acetoxy acetophenone, α, alpha, alpha-dimethyl oxygroup-α-phenyl acetophenone, acetanisole, 1- [2- methyl -4- methyl mercapto phenyl] -2- morpholino -1- Acetone, α, alpha, alpha-dimethyl oxygroup-α-morpholino-methylthio phenyl benzoylformaldoxime, 2- benzyl -2- dimethylamino -1- (4- morpholino benzene Base) acetophenones such as-butane -1- ketone；The quinones such as anthraquinone, 1,4- naphthoquinones；Phenacyl chloride, trisbromomethyl phenyl sulfone, three (three Chloromethyl) halogen compounds such as s-triazine；[1,2 '-union II imidazoles] -3,3 ', 4,4 '-tetraphenyls, [1,2 '-union II imidazoles] -1, 2 '-dichlorophenyls -3,3 ', the peroxide such as the union IIs such as 4,4 '-tetraphenyls imidazoles, di-t-butyl peroxide；2,4,6- tri- Acylphosphine oxide class such as toluyl diphenyl phosphine oxide etc..
As commercially available product, can enumerate with イ Le ガ キ ュ ア 184,369,379EG, 651,500,907, CGI369, CG24-61 (more than, チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ (strain) system), Le シ リ Application LR8728, Le シ リ Application TPO (more than, BASF (strain) system), ダ ロ キ ュ ア 1116,1173 (more than, チ バ ス ペ シ ャ Le テ ィ ケ ミ カ Le ズ (strain) system), ユ ベ Network The commercially available commodity of trade names such as リ Le P36 (UCB (strain) system).
Among the above, preferably 1- [2- methyl -4- methyl mercapto phenyl] -2- morpholino -1- acetone, 2- benzyl -2- dimethyl Amino -1- (4- morphlinophenyl)-butane -1- ketone, α, the acetophenones such as alpha, alpha-dimethyl oxygroup-α-phenyl acetophenone, benzoyl first Base chlorine, trisbromomethyl phenyl sulfone, 2,4,6- trimethylbenzoyl diphenyl phosphine oxide, 1,2 '-union II imidazoles and 4,4 '-diethyls Base aminobenzophenone and mercaptobenzothiazoler and use, Le シ リ Application TPO (trade name), 651 (commodity of イ Le ガ キ ュ ア Name), イ Le ガ キ ュ ア 369 (trade name).
Above-mentioned radical polymerization initiator can be used singly or in combination of two or more.Above-mentioned free radical Polymerization initiator relative to 100 mass parts of (A) ingredient, can preferably with 0.1~50 mass parts, more preferably with 1~30 mass parts, Particularly preferably used with the amount of 2~30 mass parts.If the usage amount of radical polymerization initiator is less than above range, it is easy to Inactivation by the free radical as caused by oxygen is influenced (reduction of sensitivity), if being more than above range, there is compatibility change The tendency that difference or storage stability reduce.
< solvent >
Cured film formation composition of the invention is mainly used with the solution state for being dissolved in solvent.What is used at this time is molten As long as agent can dissolve (A) ingredient, (B) ingredient and (C) ingredient, aftermentioned other additives as needed, kind Class and structure etc. are not particularly limited.
As the concrete example of solvent, can enumerate for example, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, 2- Methyl-1-butanol, n-amyl alcohol, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, methylcellosolve acetate, ethyl cellosolve Acetic acid esters, diethylene glycol (DEG), diethylene glycol monomethyl ether, carbiphene, propylene glycol, propylene glycol monomethyl ether, propylene glycol list first Base ether acetic acid ester, propylene glycol monoethyl, propylene glycol propyl ether, propylene glycol propyl ether acetic acid esters, toluene, dimethylbenzene, methyl second Base ketone, isobutyl methyl ketone, cyclopentanone, cyclohexanone, 2- butanone, 3- methyl -2 pentanone, 2 pentanone, 2-HEPTANONE, gamma-butyrolacton, 2 hydroxy propanoic acid ethyl ester, 2- hydroxy-2-methyl ethyl propionate, ethoxy ethyl acetate, hydroxyl ethyl acetate, 2- hydroxyl -3- first Base methyl butyrate, 3- methoxy methyl propionate, 3- methoxypropionate, 3- ethoxypropanoate, 3- ethoxy-propionic acid second Ester, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, cyclopentyl-methyl ether, N, Dinethylformamide, DMAC N,N' dimethyl acetamide and n-methyl-2-pyrrolidone etc..
Cured film formation composition of the invention is being used, cured film is being formed on resin film and manufactures the feelings for being orientated material Under condition, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, 2-methyl-1-butene alcohol, 2-HEPTANONE, isobutyl methyl ketone, diethylene glycol (DEG), Propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether etc. are the solvent that resin film shows patience, are considered from this point It is preferred.
These solvents can be used alone or be used with combination of more than two kinds.
The other additive > of <
Further, cured film of the invention, which is formed, uses in composition, as long as not damaging effect of the invention, so that it may according to It needs containing sensitizer, closely sealed modifier, silane coupling agent, surfactant, rheology control agent, pigment, dyestuff, save and stablize Agent, defoaming agent, antioxidant etc..
< cured film forms the modulation > for using composition
Cured film formation of the invention is with composition: the polymer with vertical orientation group containing (A) ingredient, (B) polymerization initiator of the compound with 2 or more the polymerizable groups comprising C=C double bond of ingredient, (C) ingredient, into one As long as step does not damage effect of the invention, so that it may the composition containing other additives.And in general, their conducts are dissolved in The form of the solution of solvent and use.
Cured film of the invention forms as described below with the preference of composition.
[1]: a kind of cured film formation composition contains: (A) ingredient；It is 10 matter based on 100 mass parts of (A) ingredient Measure part~2000 mass parts (B) ingredient；The polymer as (A) ingredient relative to 100 mass parts is 0.1 mass parts~50 (C) ingredient of mass parts.
[2]: a kind of cured film formation composition contains: (A) ingredient；It is 10 matter based on 100 mass parts of (A) ingredient Measure part~2000 mass parts (B) ingredient；The polymer as (A) ingredient relative to 100 mass parts is 0.1 mass parts~50 (C) ingredient of mass parts；And solvent.
It is described below to be formed in the form of a solution using cured film of the invention with the mixing ratio in the case where composition, tune Method processed etc..
About the ratio of the solid component in cured film formation composition of the invention, as long as each ingredient equably dissolves In solvent, there is no particular limitation, but be the 1 mass % of mass %~60, preferably 2 mass %~50 mass %, more preferably 2 The mass of quality %~20 %.Here, so-called solid component refers to and eliminates from the whole components of cured film formation composition Ingredient after solvent.
The modulator approach of cured film formation composition of the invention is not particularly limited.As modulation method, example can be enumerated Such as, it is mixed, is made with regulated proportion by (B) ingredient, further by (C) ingredient etc. in the solution of (A) ingredient for being dissolved in solvent At the method for homogeneous solution；Alternatively, further adding other additives as needed in the appropriate stage of the modulation method and being mixed The method of conjunction.
In addition, the solution of the cured film formation composition modulated is preferably in the filtering for the use of aperture being 0.2 μm or so Device etc. uses after being filtered.
< cured film, orientation material and phase difference material >
By the solution of cured film formation composition of the invention in substrate (for example, silicon/silicon dioxide is substrate coated, nitrogen SiClx substrate, substrate, glass substrate, quartz base plate, the ito substrate for being coated metal such as aluminium, molybdenum, chromium etc. etc.), ilm substrate (for example, cellulose triacetate (TAC) film, polycarbonate (PC) film, cyclic olefin polymer (COP) film, cyclic olefine copolymer (COC) resin films such as film, polyethylene terephthalate (PET) film, acrylic film, polyethylene film) etc. on, by stick apply, Spin coating, ink-jet application, printing etc. are coated and form film after spin coating, flow coat, roller coating, slot coated, slot coated, so Afterwards, with heat dryings such as electric hot plate or baking ovens, so as to form cured film.The cured film can be answered directly as orientation material With.
As the condition of heat drying, as long as with the insoluble polymerization for coating on it of ingredient of cured film (orientation material) Property liquid crystal solution degree, the cross-linking reaction using crosslinking agent is carried out, for example, using from temperature 60 C~200 DEG C, time The heating temperature suitably selected in 0.4 minute~60 minutes ranges and heating time.Heating temperature and heating time be preferably 70 DEG C~160 DEG C, 0.5 minute~10 minutes.
The film thickness of the cured film (orientation material) formed using solidification compound of the invention is, for example, 0.05 μm~5 μm, It is contemplated that the difference of height of used substrate, optical property, electrical property are suitably selected.
It, can be due to being solidified the orientation material that film composition is formed by of the invention there is solvent resistance and heat resistance Coating has the polymerizable liquid crystal solution equiphase difference material of vertical orientation on the orientation material, makes its orientation on orientation material. Moreover, can be used as with optically anisotropic layer and shape by solidifying the phase difference material for becoming state of orientation directly At phase difference material.Moreover, becoming useful as phase difference film in the case where forming the substrate of orientation material is film.
In addition it is also possible to using 2 pieces of substrates of orientation material formed with operation as described above, of the invention, Jie After bonding it by spacer in the orientation material mode relative to each other on two substrates, liquid crystal is injected between these substrates, is made At the liquid crystal display element of liquid crystal aligning.
Cured film formation composition of the invention in this way can be suitable for various phase difference materials (phase difference film), liquid crystal The manufacture of display element etc..
Embodiment
Hereinafter, citing illustrates the present invention in further detail, but the present invention is not limited to these embodiments.
[shorthand notation used in embodiment]
The meaning of shorthand notation used in the following embodiment is as described below.
The raw material > of < (A) ingredient
LAA: lauryl acrylate
MAA: methacrylic acid
MMA: methyl methacrylate
HEMA: 2-hydroxyethyl methacrylate
MA1:
AIBN: α, α '-azodiisobutyronitrile
ARU: East Asia synthesizes (strain) ARUFON UF-5041 processed
< (B) ingredient >
DPHA: dipentaerythritol hexaacrylate
8KX: great achievement Off ァ イ Application ケ ミ カ Le (strain) 8KX-078 processed (40 mass % of solid component concentration)
8KQ: great achievement Off ァ イ Application ケ ミ カ Le (strain) 8KQ-2001 processed (39 mass % of solid component concentration)
8UH: great achievement Off ァ イ Application ケ ミ カ Le (strain) 8UH-1006 processed (45 mass % of solid component concentration)
< (C) ingredient >
IRG:BASF society IRGACURE 907
< solvent >
Each resin combination of embodiment and comparative example contains solvent, as the solvent, has used propylene glycol monomethyl ether (PM), ethyl acetate (EA), butyl acetate (BA).
The measurement > of the molecular weight of < polymer
The molecular weight for polymerizeing the acrylic acid series copolymer in example uses (strain) Shimadzu Seisakusho Ltd. GPC device (Shodex (note Volume trade mark) column KF803L and KF804L) it operates and measures as described below.In addition, following number-average molecular weights is (hereinafter referred to as Mn it) is indicated with number-average molecular weight (hereinafter referred to as Mw) with polystyrene scaled value.
Eluent: tetrahydrofuran
Flow: 1mL/min
Column temperature: 40 DEG C
Standard curve making standard sample: Showa electrician polystyrene (molecular weight about 197,000,55,100,12, 800、3,950、1,260、580)
The synthesis of 1 > MA1 of < synthesis example
By 4- (trans- -4- pentylcyclohexyl) benzoic acid 4.0g (14.6mmol), HEMA1.0g (13.3mmol), 1- (3- Dimethylaminopropyl) -3- ethyl carbodiimide 2.5g (15.9mmol), 4-dimethylaminopyridine 0.1g, (0.7mmol), Tetrahydrofuran 19.3g mixing, is stirred at room temperature 24 hours.After the completion of reaction, tetrahydrofuran is subjected to vacuum distillation removing Afterwards, it is dissolved in ethyl acetate 150mL, aqueous ammonium chloride solution 100mL is added and washs 3 times.Ethyl acetate is evaporated under reduced pressure and is removed, Obtain 4.3g target substance MA1 (yield: 84%).
< polymerize 1 > of example
It is dissolved in PM15.3g by LAA 1.0g, MAA 3.2g, as the AIBN 0.3g of polymerization catalyst, is made at 80 DEG C It is reacted 20 hours, to obtain acrylic acid series copolymer solution (solid component concentration: 20 mass %) (P1).Resulting third The Mn of olefin(e) acid based copolymer is 5,500, Mw 7,100.
< polymerize 2 > of example
It is dissolved in PM7.8g by LAA 1.0g, MAA 0.8g, as the AIBN 0.1g of polymerization catalyst, is made at 80 DEG C It is reacted 20 hours, to obtain acrylic acid series copolymer solution (solid component concentration: 25 mass %) (P2).Resulting third The Mn of olefin(e) acid based copolymer is 13,700, Mw 24,000.
< polymerize 3 > of example
It is dissolved in PM15.3g by LAA 1.0g, MMA 3.7g, as the AIBN 0.3g of polymerization catalyst, is made at 80 DEG C It is reacted 20 hours, to obtain acrylic acid series copolymer solution (solid component concentration: 25 mass %) (P3).Resulting third The Mn of olefin(e) acid based copolymer is 7,700, Mw 13,600.
< polymerize 4 > of example
It is dissolved in PM14.6g by MMA 3.0g, HEMA 0.3g, as the AIBN 0.3g of polymerization catalyst, at 80 DEG C React it 20 hours, to obtain acrylic acid series copolymer solution (solid component concentration: 30 mass %) (P4).It is resulting The Mn of acrylic acid series copolymer is 18,000, Mw 32,800.
< polymerize 5 > of example
It is dissolved in PM7.7g by MA1 1.0g, MAA 0.8g, as the AIBN 0.1g of polymerization catalyst, is made at 80 DEG C It is reacted 20 hours, to obtain acrylic acid series copolymer solution (solid component concentration: 20 mass %) (P5).Resulting third The Mn of olefin(e) acid based copolymer is 8,900, Mw 30,800.
< embodiment 1~11,1~2 > of comparative example
Each cured film formation composition is modulated to form shown in table 1.
[table 1]
< embodiment 12~28,3~5 > of comparative example
It is carried out respectively next, forming cured film using each phase difference material formation composition about resulting cured film The evaluation of vertically oriented property.
[evaluation of vertical orientation]
Using rod coater by each cured film formation composition obtained in embodiment 1~11 and comparative example 1~2 with Wet 4 μm of (Wet) film thickness are coated on each substrate.It is dry that heating is carried out 60 seconds at 110 DEG C of temperature, in heat-circulation type baking oven respectively It is dry, then, which is exposed, forms respectively cured film on each substrate.
The vertical orientation for being made メ Le Network (strain) using rod coater is with polymerizable liquid crystal solution RMS03-015 with wet film Thick 6 μm are coated in the cured film.60 seconds heat dryings are carried out on electric hot plate under temperature 60 C respectively, then, by the painting Film is with 500mJ/cm2Exposure, produces phase difference material.
By these phase difference materials of production, face is determined using big tomb electronics (strain) measuring difference of phases device RETS100 processed The incident angle dependence of interior phase difference.It is under 0, incident angle ± 50 degree by phase difference value in the face under 0 degree of incident angle Phase difference is judged as vertically oriented in the case where range of 38 ± 5nm in face.Evaluation result is summarized below and is shown in Table 2.
[table 2]
[table 2]
Solidify film composition Base material film Cured film light exposure Vertical orientation
Embodiment 12 A-1 TAC 100mJ/cm2 ○
Embodiment 13 A-1 TAC 300mJ/cm2 ○
Embodiment 14 A-1 TAC 500mJ/cm2 ○
Embodiment 15 A-1 TAC 800mJ/cm2 ○
Embodiment 16 A-1 COP 500mJ/cm2 ○
Embodiment 17 A-1 PET 500mJ/cm2 ○
Embodiment 18 A-1 PC 500mJ/cm2 ○
Embodiment 19 A-2 TAC 500mJ/cm2 ○
Embodiment 20 A-3 TAC 500mJ/cm2 ○
Embodiment 21 A-4 TAC 500mJ/cm2 ○
Embodiment 22 A-5 TAC 500mJ/cm2 ○
Embodiment 23 A-6 TAC 500mJ/cm2 ○
Embodiment 24 A-7 TAC 500mJ/cm2 ○
Embodiment 25 A-8 TAC 500mJ/cm2 ○
Embodiment 26 A-9 TAC 500mJ/cm2 ○
Embodiment 27 A-10 TAC 800mJ/cm2 ○
Embodiment 28 A-11 TAC 500mJ/cm2 ○
Comparative example 3 B-1 TAC 500mJ/cm2 ×
Comparative example 4 B-1 TAC 800mJ/cm2 ×
Comparative example 5 B-2 TAC 500mJ/cm2 ×
As shown in table 2, it is shown using the orientation material that the cured film formation of embodiment is obtained with composition good vertical Orientation.In contrast, it is difficult to obtain vertical orientation with the cured film that composition obtains using the cured film formation of comparative example.
Industry utilizability
Cured film formation of the present invention uses composition as forming the liquid crystal aligning for being used to form liquid crystal display element Film, the orientation material that internal, external optical anisotropic film is set in liquid crystal display element material be it is highly useful, In particular, the material of the optical compensation films of the circular polarization light board used as the antireflection film towards IPS-LCD, organic el display Material is suitable.

Claims (6)

1. a kind of cured film, which is formed, uses composition, which is characterized in that contain:
(A) there is polymer of the group as vertical orientation group shown in following formula [1]；
(B) compound with 2 or more the polymerizable groups comprising C=C double bond；And
(C) radical polymerization initiator,
Substantially only (B) ingredient has the polymerizable group comprising C=C double bond,
In formula [1],
Y1It indicates singly-bound or indicates to combine base, the combination base is selected from-O- ,-CH2O-、-COO-、-OCO-、-NHCO-、-NH- Group in CO-O- and-NH-CO-NH-,
Y2Indicate the alkylidene or-CH of the carbon atom number 1~15 of singly-bound, straight-chain or branched2-CH(OH)-CH2, the alkylene Base can combine base A to interrupt by 1~3, still, not combine each other in conjunction with base A or Y2Indicate selected from phenyl ring, cyclohexane ring or Divalent cyclic group in heterocycle, any hydrogen atom in the cyclic group of the divalent cyclic group can be by the carbon of straight-chain or branched The carbon atom of the alkoxy of the carbon atom number 1~3 of the alkyl of atomicity 1~3, straight-chain or branched, straight-chain or branched The alkoxy containing fluorine or fluorine atom of the carbon atom number 1~3 of the alkyl containing fluorine of number 1~3, straight-chain or branched take Generation,
Y3Indicate that the alkylidene of singly-bound or carbon atom number 1~15, the alkylidene can be appointing in straight-chain, branched and ring-type One or their combination, the alkylidene can combine base A to interrupt, still, not combine each other in conjunction with base A by 1~3,
Y4It indicates singly-bound, or indicates the divalent cyclic group in phenyl ring, cyclohexane ring or heterocycle, the ring-type of the divalent cyclic group Any hydrogen atom on base can be former by the carbon of the alkyl of straight-chain or the carbon atom number 1~3 of branched, straight-chain or branched The alkyl containing fluorine of the carbon atom number 1~3 of the alkoxy of subnumber 1~3, straight-chain or branched, straight-chain or branched The alkoxy containing fluorine or fluorine atom of carbon atom number 1~3 replace or Y4Carbon atom number 17 of the expression with steroid skeleton~ 30 divalent organic group,
Y5Indicate the divalent cyclic group in phenyl ring, cyclohexane ring or heterocycle, any hydrogen in the cyclic group of the divalent cyclic group Atom can be by the alkane of the carbon atom number 1~3 of the alkyl of straight-chain or the carbon atom number 1~3 of branched, straight-chain or branched The carbon atom number 1~3 of the alkyl containing fluorine of the carbon atom number 1~3 of oxygroup, straight-chain or branched, straight-chain or branched The alkoxy containing fluorine or fluorine atom replace,
N indicates 0~4 integer, in the case where n is 2 or more, each Y5It can be the same or different,
Y6Indicate hydrogen atom, the alkyl of carbon atom number 1~18, the alkyl containing fluorine of carbon atom number 1~18, carbon atom number 1~18 Alkoxy or carbon atom number 1~18 the alkoxy containing fluorine, the alkyl of the carbon atom number 1~18, carbon atom number 1~18 The alkoxy containing fluorine of alkyl containing fluorine, the alkoxy of carbon atom number 1~18 and carbon atom number 1~18 can be straight chain Any one of shape, branched and ring-type or their combination, can by 1~3 combine base A interrupt, still, in conjunction with base A that This is not combined,
In Y2And Y3In the case where indicating the group other than singly-bound, Y2With Y3Combination can be singly-bound, can also via combine base A And combine,
In Y3And Y4In the case where indicating the group other than singly-bound, Y3With Y4Combination can be singly-bound, can also via combine base A And combine,
In Y4And Y5In the case where indicating the group other than singly-bound, Y4With Y5Combination can be singly-bound, can also via combine base A And combine,
In Y5And Y6In the case where indicating the group other than singly-bound, Y5With Y6Combination can be singly-bound, can also via combine base A And combine,
In the case where n is 2 or more, 1 Y5With the Y adjacent with its5Combination can be singly-bound, can also via in conjunction with base A and In conjunction with,
It indicates to be selected from-O- ,-CH in conjunction with base A2Base in O- ,-COO- ,-OCO- ,-NHCO- ,-NH-CO-O- and-NH-CO-NH- Group,
Wherein, the number for the carbon atom for including in group shown in formula [1] adds up to 6~30.
2. cured film according to claim 1, which is formed, uses composition, the polymerizable group comprising C=C double bond of (B) ingredient For selected from least one of acryloyl group, methylacryloyl, vinyl, allyl and dimaleoyl imino.
3. cured film according to claim 1 or 2, which is formed, uses composition, 100 mass parts of (A) ingredient are based on, contain 10 matter Measure part~2000 mass parts (B) ingredient.
4. cured film described in any one of claim 1 to 3, which is formed, uses composition, (A) relative to every 100 mass parts Ingredient contains 0.1 mass parts~50 mass parts (C) ingredient.
5. a kind of orientation material, which is characterized in that be to make cured film formation composition according to any one of claims 1 to 4 Solidify and obtains.
6. a kind of phase difference material, which is characterized in that be to form use using by cured film according to any one of claims 1 to 4 Composition obtain cured film and formed.
CN201880013114.6A 2017-02-22 2018-02-22 Cured film is formed with composition, orientation material and phase difference material Pending CN110325886A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2017030736 2017-02-22
JP2017-030736 2017-02-22
PCT/JP2018/006543 WO2018155581A1 (en) 2017-02-22 2018-02-22 Cured film-forming composition, alignment material, and phase difference material

Publications (1)

Publication Number Publication Date
CN110325886A true CN110325886A (en) 2019-10-11

Family

ID=63252895

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201880013114.6A Pending CN110325886A (en) 2017-02-22 2018-02-22 Cured film is formed with composition, orientation material and phase difference material

Country Status (5)

Country Link
JP (1) JP7249271B2 (en)
KR (2) KR20190116319A (en)
CN (1) CN110325886A (en)
TW (1) TWI843698B (en)
WO (1) WO2018155581A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020181148A (en) * 2019-04-26 2020-11-05 日産化学株式会社 Retardation material

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11511194A (en) * 1995-08-21 1999-09-28 ブリューアー サイエンス インコーポレイテッド Thermosetting anti-reflective coating and method for producing the same
JP2002333717A (en) * 2001-05-07 2002-11-22 Nissan Chem Ind Ltd Antireflection film forming composition for lithography
CN102337140A (en) * 2010-07-15 2012-02-01 Jsr株式会社 Liquid crystal aligning agent for retardation film, liquid crystal alignment film for retardation film, and retardation film and process for production thereof
WO2016031917A1 (en) * 2014-08-28 2016-03-03 日産化学工業株式会社 Composition for forming cured film, alignment material, and retardation material
WO2016039337A1 (en) * 2014-09-08 2016-03-17 日産化学工業株式会社 Cured-film-forming composition, alignment material, and phase difference material
CN105452404A (en) * 2013-08-09 2016-03-30 日产化学工业株式会社 Cured film-forming composition, alignment material, and phase difference material
CN105474083A (en) * 2013-08-29 2016-04-06 日产化学工业株式会社 105474083cured-film-forming composition, alignment material, and phase difference material
CN105683828A (en) * 2013-09-03 2016-06-15 日产化学工业株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2857889B2 (en) 1988-11-04 1999-02-17 富士写真フイルム株式会社 Liquid crystal display
JP3204182B2 (en) 1997-10-24 2001-09-04 日本電気株式会社 In-plane switching LCD
JP2001281669A (en) 2000-03-30 2001-10-10 Matsushita Electric Ind Co Ltd Liquid crystal alignment layer, its manufacturing method and liquid crystal display device and its manufacturing method
KR100677050B1 (en) 2003-10-22 2007-01-31 주식회사 엘지화학 In-plane switching liquid crystal display comprising compensation film for angular field of view using +a-plate and +c-plate
KR101042214B1 (en) * 2009-04-09 2011-06-20 주식회사 엘지화학 An alignment film composition, an alignment film prepared therefrom, a method for manufacturing an alignment film, an optical film comprising the same, and a display device including the optical film
WO2013108716A1 (en) * 2012-01-19 2013-07-25 日産化学工業株式会社 Negative photosensitive resin composition
JP6726924B2 (en) * 2014-03-28 2020-07-22 大日本印刷株式会社 Optical film and method of manufacturing optical film
JP2015079256A (en) 2014-11-11 2015-04-23 大日本印刷株式会社 Optical film, transfer body for optical film, and image display device

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11511194A (en) * 1995-08-21 1999-09-28 ブリューアー サイエンス インコーポレイテッド Thermosetting anti-reflective coating and method for producing the same
JP2002333717A (en) * 2001-05-07 2002-11-22 Nissan Chem Ind Ltd Antireflection film forming composition for lithography
CN102337140A (en) * 2010-07-15 2012-02-01 Jsr株式会社 Liquid crystal aligning agent for retardation film, liquid crystal alignment film for retardation film, and retardation film and process for production thereof
CN105452404A (en) * 2013-08-09 2016-03-30 日产化学工业株式会社 Cured film-forming composition, alignment material, and phase difference material
CN105474083A (en) * 2013-08-29 2016-04-06 日产化学工业株式会社 105474083cured-film-forming composition, alignment material, and phase difference material
CN105683828A (en) * 2013-09-03 2016-06-15 日产化学工业株式会社 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element
WO2016031917A1 (en) * 2014-08-28 2016-03-03 日産化学工業株式会社 Composition for forming cured film, alignment material, and retardation material
WO2016039337A1 (en) * 2014-09-08 2016-03-17 日産化学工業株式会社 Cured-film-forming composition, alignment material, and phase difference material

Also Published As

Publication number Publication date
KR20230062899A (en) 2023-05-09
KR20190116319A (en) 2019-10-14
TWI843698B (en) 2024-06-01
JPWO2018155581A1 (en) 2019-12-12
WO2018155581A1 (en) 2018-08-30
TW201840759A (en) 2018-11-16
JP7249271B2 (en) 2023-03-30

Similar Documents

Publication Publication Date Title
CN102460288B (en) Form the compositions of the heat cured film with light orientation
US20160024385A1 (en) Polymerizable liquid crystal compound, polymerizable liquid crystal composition, and optical anisotropic body
CN106459324B (en) Cured film, which is formed, uses composition, oriented material and phase difference material
US20200292861A1 (en) Liquid crystal display device
CN105431752B (en) Phase difference film and the image display device for having the phase difference film
CN105452404A (en) Cured film-forming composition, alignment material, and phase difference material
JP6700609B2 (en) Cured film forming composition, aligning material and retardation material
CN110461965A (en) Cured film is formed with composition, orientation material and phase difference material
CN107532006B (en) Thermosetting resin composition and vertically aligned retardation film
CN110167980A (en) Cured film is formed with composition, orientation material and phase difference material
CN110325886A (en) Cured film is formed with composition, orientation material and phase difference material
TWI723961B (en) Cured film forming composition, alignment material and retardation material
CN102372825B (en) Curable resin composition
JP5136744B2 (en) Thermosetting resin composition for forming a highly planarized film
CN105474083B (en) Cured film is formed with composition, orientation material and phase difference material
CN107207641B (en) Composition for forming cured film, alignment material, and phase difference material
CN113574119B (en) Polymer composition and single layer phase difference material
TWI794261B (en) Cured film forming composition, alignment material and retardation material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication