CN115916853A - Novel polymer, and photo-alignment film and retardation film using same - Google Patents

Novel polymer, and photo-alignment film and retardation film using same Download PDF

Info

Publication number
CN115916853A
CN115916853A CN202180041285.1A CN202180041285A CN115916853A CN 115916853 A CN115916853 A CN 115916853A CN 202180041285 A CN202180041285 A CN 202180041285A CN 115916853 A CN115916853 A CN 115916853A
Authority
CN
China
Prior art keywords
group
carbon atoms
oxy
ring
photo
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.)
Granted
Application number
CN202180041285.1A
Other languages
Chinese (zh)
Other versions
CN115916853B (en
Inventor
阿波茂树
椿幸树
幸田光弘
川月喜弘
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.)
Osaka Organic Chemical Industry Co Ltd
Original Assignee
Osaka Organic Chemical Industry Co Ltd
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 Osaka Organic Chemical Industry Co Ltd filed Critical Osaka Organic Chemical Industry Co Ltd
Publication of CN115916853A publication Critical patent/CN115916853A/en
Application granted granted Critical
Publication of CN115916853B publication Critical patent/CN115916853B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/303—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one or more carboxylic moieties in the chain
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • 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
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • 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
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00—Adapting or protecting infrastructure or their operation
    • Y02A30/24—Structural elements or technologies for improving thermal insulation
    • Y02A30/249—Glazing, e.g. vacuum glazing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B80/00—Architectural or constructional elements improving the thermal performance of buildings
    • Y02B80/22—Glazing, e.g. vaccum glazing

Landscapes

  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention provides a compound represented by the general formula (I) [ wherein, M a‑c Is a moiety that forms the backbone of the copolymer; l, m and n are the mole percent of the copolymer; SPCRa-c are interval units; rings A to C are a predetermined alicyclic hydrocarbon or aromatic ring; x is a covalent single bond, C 1‑10 Alkylene chain or C 3‑8 A cycloalkylene chain; y is a covalent single bond, defined as C 1‑10 Alkylene chain, C 3‑8 Cycloalkylene chain-O-, -COO-or combinations thereof; z is-O-CO-CH = CH 2 －；R 1 is-CW = CH 2 or-V-CW = CH 2 ；R 2 Is a hydrogen atom, C 1‑6 Alkyl or phenyl having specified substituents]The polymer having the repeating unit, and a photo-alignment film and a retardation film comprising the polymer.

Description

Novel polymer, and photo-alignment film and retardation film using same
Technical Field
The present disclosure relates to a novel polymer, a photo-alignment film, and a retardation film, and more particularly, to a novel polymer having a side chain having a carboxylic acid group at a terminal, a side chain having a polymerizable group at a terminal, and a side chain having an aryl acrylate moiety in a molecule, a composition for a photo-alignment film including the novel polymer, a photo-alignment film in which a liquid crystal alignment ability is imparted to a film formed of the composition, and a retardation film in which a liquid crystal compound is aligned on the photo-alignment film.
Background
In recent years, in the field of displays (liquid crystal displays, organic EL displays, and the like), retardation films (optically anisotropic films) have been used in various forms. The retardation film is produced by applying a liquid crystal compound, a dye, a conductive compound, or the like to an alignment film (or a substrate) having liquid crystal alignment ability and aligning the film. As an alignment method, photo-alignment is known in which an alignment film is irradiated (exposed) with light such as ultraviolet rays to generate an alignment regulating force and/or change the alignment regulating direction of the alignment film, and the alignment film used for photo-alignment is called a photo-alignment film. Further, with the recent trend toward higher functionality and flexibility of displays, diversification of laminates has been advanced. Therefore, the alignment film is required to have high alignment properties to various laminates and adhesion to the laminate.
In general, it is known that a liquid crystal is introduced into a photo-alignment group in order to improve the alignment property of a photo-alignment film. In addition, the adhesion to the photo-alignment film is provided by introducing a crosslinking group. However, since liquid crystals often have a structure that deteriorates adhesion, and a crosslinking group introduced to impart adhesion is not liquid crystal, high alignment properties and improvement in adhesion in a photo-alignment film are in a trade-off relationship.
As an attempt to improve the adhesion of a photo-alignment film having photo-alignment ability, for example, patent document 1 describes a technique of providing adhesion between an a layer formed of a composition containing a photo-alignment polymer and a compound having at least 2 isocyanate groups and a B layer formed of a composition containing a polymerizable liquid crystal compound, a compound having at least 2 isocyanate groups and a photopolymerization initiator, using the a layer and the B layer.
Patent document 2 discloses a polyimide compound obtained by reacting a diamine component having a photodimerization-type photo-alignment group and an acrylic group in the same side chain with a tetracarboxylic acid anhydride, as a liquid crystal aligning agent capable of improving the response speed of a liquid crystal display device without adding a photopolymerizable compound. Since the polyimide compound has an acrylic group at the end of a side chain, good adhesion can be expected.
Documents of the prior art
Patent literature
Patent document 1: japanese patent laid-open publication No. 2013-148805
Patent document 2: international publication No. 2013/099804
Disclosure of Invention
In the technique of patent document 1, since both the a layer and the B layer need to contain an isocyanate compound, the degree of freedom of materials is low, and since the isocyanate compound is mixed, the pot life of the resist can be expected to be deteriorated.
The material of patent document 2 requires a high-temperature process for forming a polyimide film, and thus is difficult to apply to a flexible film or the like, resulting in a problem of high production cost.
In view of the above problems, it is an object of the present disclosure to provide a novel polymer that can exhibit good alignment properties that can exhibit liquid crystal alignment ability of a liquid crystal layer and good adhesion to the liquid crystal layer when used in a photo-alignment film, and a photo-alignment film and a retardation film comprising the novel polymer.
The present disclosure relates to:
[1] a polymer having a repeating unit represented by the general formula (I),
[ solution 1]
Figure BDA0003987788100000031
[ in the formula,
M a 、M b and M c Represents a portion of a monomer unit of the copolymer that forms a main chain of the copolymer;
l, m and n represent the molar percentages of the copolymer, in each case 0 < l < 1 and 0 < m < 1 and 0 < n < 1;
SPCRa, SPCRb, and SPCRc each independently represent a spacing unit;
ring a, ring B and ring C are each independently an unsubstituted or substituted alicyclic hydrocarbon or an unsubstituted or substituted aromatic ring;
x is a covalent single bond, an alkylene chain having 1 to 10 carbon atoms or a cycloalkylene chain having 3 to 8 carbon atoms;
y is selected from the group consisting of a covalent single bond; an alkylene chain having 1 to 10 carbon atoms which is unsubstituted or substituted with a hydroxyl group and/or a carbonyl group; a cycloalkylene chain having 3 to 8 carbon atoms; -O-; -COO-; and combinations thereof;
z is-O-CO-CH = CH 2 - (any bonding site may be bonded to ring C);
R 1 is-CW = CH 2 or-V-CW = CH 2 (wherein W is hydrogen or methyl, and V is-O-CO-or-CO-);
R 2 is a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; having a structure selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group and a halogen atomPhenyl group having at least 1 substituent in the group, wherein, in the case where ring C is an alicyclic hydrocarbon, R is 2 Is a phenyl group having at least 1 substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group and a halogen atom]；
[2] The polymer according to the above [1], wherein each of the ring A, the ring B and the ring C is independently a group represented by the following general formula (any bonding site may be bonded to the respective spacer unit),
[ solution 2]
Figure BDA0003987788100000041
[ in the formula, R 3 ～R 64 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a cyano group]；
[3] The polymer according to the above [2], wherein the ring A is a group represented by the following general formula,
[ solution 3]
Figure BDA0003987788100000051
[ in the formula, R 3 ～R 14 Each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a cyano group]；
Ring B is a group represented by the following general formula (any bonding site may be bonded to the spacer unit),
[ solution 4]
Figure BDA0003987788100000052
[ wherein, R 7 ～R 14 、R 33 ～R 64 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a cyano group]；
Ring C is a group represented by the following general formula (any bonding site may be bonded to the spacer unit),
[ solution 5]
Figure BDA0003987788100000053
[ in the formula, R 3 ～R 6 、R 33 ～R 40 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a cyano group]；
[4]According to the above [1]]～[3]The polymer of any one of, wherein SPCRa, SPCRb, and SPCRc are each independently a covalent single bond; an alkylene chain having 1 to 20 carbon atoms which is unsubstituted or substituted with a hydroxyl group and/or a carbonyl group; a 3-8 carbon cycloalkylene chain unsubstituted or substituted with a hydroxyl group; unsubstituted or selected from the group consisting of alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, -CN, -NO 2 And phenylene substituted with at least 1 substituent of the group consisting of halogen; -O-; -COO-; or a combination thereof;
[5] the polymer according to the above [4], wherein SPCRa, SPCRb and SPCRc are each independently an alkylene chain having 1 to 20 carbon atoms which is unsubstituted or substituted with a hydroxyl group and/or a carbonyl group; -O-; -COO-; or a combination thereof;
[6] the polymer according to any one of the above [1] to [5], wherein Y is a combination of an alkylene chain having 1 to 10 carbon atoms which is unsubstituted or substituted with a hydroxyl group and/or a carbonyl group and-O-or-COO-;
[7] a composition for a photo-alignment film, comprising the polymer according to any one of the above [1] to [6 ];
[8] a photo-alignment film formed from the composition for a photo-alignment film according to [7 ];
[9] a retardation film obtained by further aligning a liquid crystalline compound on the photo-alignment film according to [8 ].
When used in a photo-alignment film, the polymer of the present disclosure exhibits good alignment properties that can exhibit the liquid crystal alignment ability of a liquid crystal layer and good adhesion to the liquid crystal layer, and by using the photo-alignment film, a retardation film having good photo-alignment properties and excellent adhesion to a liquid crystal compound can be obtained.
Detailed Description
In the present specification, the terms "(meth) acrylic acid", "meth) acrylate" and the like are general terms of "methacrylic acid" and "acrylic acid", "methacrylate" and "acrylate", respectively.
In the present specification, the dotted line used in the structural formula means that any dotted line can be bonded to each structural unit, and the polymer of the present disclosure may be a random copolymer or a block copolymer obtained from each structural unit as long as the polymer is within a predetermined molar percentage range.
According to a first embodiment of the present disclosure, there is provided a polymer (also referred to as polymer (I) in the present specification) having a repeating unit represented by general formula (I),
[ solution 6]
Figure BDA0003987788100000071
[ in the formula,
M a 、M b and M c Represents a portion of a monomer unit of the copolymer that forms a main chain of the copolymer;
l, m and n represent the molar percentages of the copolymer, in each case 0 < l < 1 and 0 < m < 1 and 0 < n < 1;
SPCRa, SPCRb, and SPCRc each independently represent a spacing unit;
ring a, ring B and ring C are each independently an unsubstituted or substituted alicyclic hydrocarbon or an unsubstituted or substituted aromatic ring;
x is a covalent single bond, an alkylene chain with 1-10 carbon atoms or a cycloalkylene chain with 3-8 carbon atoms;
y is selected from the group consisting of a covalent single bond; an alkylene chain having 1 to 10 carbon atoms which is unsubstituted or substituted with a hydroxyl group and/or a carbonyl group; a cycloalkylene chain having 3 to 8 carbon atoms; -O-; -COO-; and combinations thereof;
z is-O-CO-CH = CH 2 - (any bonding site may be bonded to ring C);
R 1 is-CW = CH 2 or-V-CW = CH 2 (wherein W is hydrogen or methyl, and V is-O-CO-or-CO-);
R 2 is a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; a phenyl group having at least 1 substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group and a halogen atom, wherein, when ring C is an alicyclic hydrocarbon, R is 2 Is a phenyl group having at least 1 substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group and a halogen atom]。
In the polymer (I), M a 、M b And M c The moiety forming the main chain of the copolymer among the monomer units of the copolymer is not particularly limited as long as it can form the main chain of a general copolymer in the art, and is, for example, independently selected from the group consisting of ethylene, alkoxysilane, acrylate, methacrylate, 2-chloroacrylate, 2-phenylacrylate, acryloylphenylene (1245012525125125251251252412591125125125125125125125125125, 12463, 2-chloroacrylamide, 2-phenylacrylamide, vinyl ether, styrene derivatives, vinyl esters, maleic acid derivatives, fumaric acid derivatives, siloxane and epoxides. Among these, ethylene, acrylic acid esters, methacrylic acid esters, acrylamide, methacrylamide and the like are preferable.
In the polymer (I), for example, M a Monomer unit having a carboxylic acid group at the terminal (hereinafter referred to as a constituent unit α), M b The monomer unit having a polymerizable group at the terminal (hereinafter referred to as a constituent unit. Beta.) and M c The monomer unit having an aryl acrylate moiety (hereinafter referred to as a constituent unit γ) of (2) may be in a predetermined molar percentageThe form of the block copolymer may be random copolymer. In the formula, the constituent unit α, the constituent unit β and the constituent unit γ are represented by l, m and n, respectively, and in each case, 0 < l < 1 and 0 < m < 1 and 0 < n < 1, preferably 0.1. Ltoreq. L.ltoreq.0.9, 0.01. Ltoreq. M.ltoreq.0.4, 0.05. Ltoreq. N.ltoreq.0.5, more preferably 0.5. Ltoreq. L.ltoreq.0.8, 0.05. Ltoreq. M.ltoreq.0.1, 0.1. Ltoreq. N.ltoreq.0.4. When l is 0.1 or more, the orientation can be further improved, and when l is 0.9 or less, the polymer (I) tends to be easily dissolved in a versatile solvent. When m is 0.01 or more, the laminate can be aligned with a smaller amount of light irradiation, and when m is 0.4 or less, the alignment properties can be further improved. When n is 0.05 or more, the adhesiveness to the laminate can be further improved, and when n is 0.5 or less, the orientation can be further improved.
In the polymer (I), SPCRa, SPCRb and SPCRc each independently represent a spacer unit, preferably each independently selected from a covalent single bond; an alkylene chain having 1 to 20 carbon atoms which is unsubstituted or substituted with a hydroxyl group and/or a carbonyl group; a cycloalkylene chain having 3 to 8 carbon atoms which is unsubstituted or substituted with a hydroxyl group; unsubstituted or selected from alkyl having 1-6 carbon atoms, alkoxy having 1-6 carbon atoms, -CN, -NO 2 And phenylene substituted with at least 1 substituent of the group consisting of halogen; -O-; -COO-; or a combination thereof, more preferably an alkylene chain of 1 to 20 carbon atoms each independently unsubstituted or substituted with a hydroxyl group and/or a carbonyl group; -O-; -COO-; or a combination thereof.
The "alkylene chain having 1 to 20 carbon atoms" in the above-mentioned options for the spacer unit is not particularly limited, but an alkylene chain having 1 to 10 carbon atoms is more preferable, an alkylene chain having 2 to 8 carbon atoms is further preferable, and an alkylene chain having 4 to 6 carbon atoms is most preferable.
The "cycloalkylene chain having 3 to 8 carbon atoms" in the above-mentioned option for the spacer unit is not particularly limited, and a cycloalkylene chain having 3 to 6 carbon atoms is more preferable.
Specific examples of SPCRa, SPCRb, and SPCRc include－(CH 2 ) 3 －、－(CH 2 ) 6 -and the like.
In addition, SPCRa, SPCRb, and SPCRc are independently selected, and are preferably selected so that they have the same chain length from the viewpoint of orientation and the like.
In the polymer (I), the ring A is an unsubstituted or substituted alicyclic hydrocarbon or an unsubstituted or substituted aromatic ring, and is preferably a group represented by the following general formula (any bonding site may be bonded to each spacer unit),
[ solution 7]
Figure BDA0003987788100000101
[ in the formula, R 3 ～R 64 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a cyano group]；
More preferably a group represented by the following general formula,
[ solution 8]
Figure BDA0003987788100000102
[ in the formula, R 3 ～R 14 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a cyano group]。
In the polymer (I), the ring B is an unsubstituted or substituted alicyclic hydrocarbon or an unsubstituted or substituted aromatic ring, preferably a group represented by the following general formula (any bonding site may be bonded to the spacer unit),
[ solution 9]
Figure BDA0003987788100000111
[ in the formula, R 3 ～R 64 Each independently hydrogen atom, C1-6 alkyl, C1EAlkoxy of 6, halogen atom or cyano]；
More preferably a group represented by the following general formula (any bonding site may be bonded to the spacer unit),
[ solution 10]
Figure BDA0003987788100000121
[ in the formula, R 7 ～R 14 、R 33 ～R 64 Each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a cyano group]。
In the polymer (I), the ring C is an unsubstituted or substituted alicyclic hydrocarbon or an unsubstituted or substituted aromatic ring, and is preferably a group represented by the following general formula (any bonding site may be bonded to each spacer unit),
[ solution 11]
Figure BDA0003987788100000131
[ wherein, R 3 ～R 64 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a cyano group]；
More preferably a group represented by the following general formula (any bonding site may be bonded to the spacer unit),
[ solution 12]
Figure BDA0003987788100000132
[ in the formula, R 3 ～R 6 、R 33 ～R 40 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a cyano group]。
As R in ring A, ring B and ring C 3 ～R 64 Preferably, all of them are hydrogen atoms.
In the polymer (I), as described above, the structures of the ring a, the ring B, and the ring C are independently determined, but the ring a, the ring B, and the ring C are preferably selected in consideration that the monomer units are preferably similar in length as a side chain in the polymer (I). In addition, from the viewpoint of improving the orientation, each monomer unit preferably has a structure exhibiting liquid crystallinity.
Therefore, as the combination of ring a, ring B and ring C, specifically, a combination selected from the following is preferable:
[ solution 13]
Ring A and ring C:
Figure BDA0003987788100000141
/>
and ring B:
Figure BDA0003987788100000142
(either bonding site may be bonded to a spacer unit);
[ chemical 14]
Ring A and ring C:
Figure BDA0003987788100000143
ring B:
Figure BDA0003987788100000144
(either bonding site may be bonded to a spacer unit);
[ solution 15]
Ring A and ring C:
Figure BDA0003987788100000145
ring B:
Figure BDA0003987788100000146
(either bonding site may be bonded to a spacer unit);
[ chemical 16]
Ring A and ring C:
Figure BDA0003987788100000147
and ring B:
Figure BDA0003987788100000148
and
[ chemical formula 17]
Ring A:
Figure BDA0003987788100000151
ring B and ring C:
Figure BDA0003987788100000152
(either of the bonding sites may be bonded to a respective spacer unit).
In the polymer (I), X is a single covalent bond, an alkylene chain having 1 to 10 carbon atoms, or a cycloalkylene chain having 3 to 8 carbon atoms, and is preferably a single covalent bond.
In the polymer (I), Y is selected from the group consisting of a covalent single bond; an alkylene chain having 1 to 10 carbon atoms which is unsubstituted or substituted with a hydroxyl group and/or a carbonyl group; a cycloalkylene chain having 3 to 8 carbon atoms; -O-; -COO-; and a combination thereof, preferably an alkylene chain of 1 to 10 carbon atoms which is unsubstituted or substituted with a hydroxyl group and/or a carbonyl group and bonded to the ring B by-O-, or an alkylene chain of 1 to 10 carbon atoms which is unsubstituted or substituted with a hydroxyl group and/or a carbonyl group and bonded to the ring B by-COO-.
The alkylene chain having 1 to 10 carbon atoms in X and Y is not particularly limited, and may be a linear or branched alkylene chain, more preferably an alkylene chain having 1 to 6 carbon atoms, and still more preferably a linear alkylene chain having 1 to 6 carbon atoms.
The cycloalkylene chain having 3 to 8 carbon atoms in X and Y is not particularly limited, and a cycloalkylene chain having 3 to 6 carbon atoms is more preferable.
In the polymer (I), Z is-O-CO-CH = CH 2 - (any bonding site may be bonded to ring C), preferably the bonding site of the oxygen atom is bonded to ring C.
In the polymer (I), R 1 is-CW = CH 2 or-V-CW = CH 2 (wherein W is hydrogen or methyl, V is-O-CO-or-CO-), more preferably-O-CO-CH 2 ＝CH 2 or-O-CO-CH (CH) 3 )＝CH 2 。
In the polymer (I), R 2 Is a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; a phenyl group having at least 1 substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group and a halogen atom, wherein, when ring C is an alicyclic hydrocarbon, R is 2 Is a phenyl group having at least 1 substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group and a halogen atom. As R 2 Preferable examples thereof include a phenyl group having an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, more preferable examples thereof include a phenyl group having an alkoxy group having 1 to 3 carbon atoms, still more preferable examples thereof include a p-alkoxyphenyl group, and most preferable example thereof is a p-methoxyphenyl group.
The molecular weight of the polymer (I) is preferably 5,000 to 200,000, more preferably 20,000 to 120,000 in terms of the weight average molecular weight (Mw). When the weight average molecular weight is 5,000 or more, the photoalignment film can be easily prevented from being dissolved in a solvent when the composition including the laminate is applied to the photoalignment film including the polymer, and when the weight average molecular weight is 200,000 or less, the solubility in the solvent can be further improved, and the curable resin composition can be easily applied to an object to be coated. In addition, the weight average molecular weight affects the heating temperature at the time of forming the phase difference film. The higher the weight average molecular weight, the more the heating at a high temperature is required, and the weight average molecular weight is more preferably 200,000 or less. In the present specification, the weight average molecular weight (Mw) is measured by Gel Permeation Chromatography (GPC) and expressed as a value in terms of polystyrene, as described in examples described later.
Next, a method for producing the polymer (I) of the present disclosure will be described. Since the polymer (I) has a polymerizable group at the end of the constituent unit β, even if the constituent unit α, the constituent unit β, and the constituent unit γ are directly copolymerized as monomers, the polymerizable group at the end of the constituent unit β participates in polymerization, and the intended polymer (I) of the present disclosure cannot be obtained. Therefore, in the production of the polymer (I), a two-stage reaction method may be employed in which a precursor of the constituent unit β (hereinafter referred to as a constituent unit β precursor) is used in place of the constituent unit β, and the constituent unit α and the constituent unit γ are copolymerized (first reaction step), and then a polymerizable group is introduced to prepare the constituent unit β (second reaction step). In this case, for example, in the second reaction step, when the compound for introducing the polymerizable group is reacted with a carboxylic acid at the terminal of the constituent unit α in the reaction of introducing the polymerizable group into the precursor of the constituent unit β, the constituent unit α of the carboxylic acid in which the constituent unit α is protected with a protecting group (hereinafter, referred to as a constituent unit α derivative) can be used as the constituent unit α used in the first reaction step. That is, the method for producing the polymer (I) of the present disclosure is not particularly limited, and examples thereof include a method for producing the polymer (I) by copolymerizing a constituent unit α derivative, a constituent unit β precursor, and a constituent unit γ in a first reaction step, introducing a polymerizable group into the constituent unit β precursor to produce the constituent unit β in a second reaction step, and deprotecting the constituent unit α derivative to produce the constituent unit α.
The first reaction step will be specifically described. In the first reaction step, for example, the constituent unit α derivative, the constituent unit β precursor, and the constituent unit γ are dissolved in an appropriate organic solvent together with an appropriate polymerization initiator to obtain a solution. After the inert gas such as nitrogen is introduced into the obtained solution, the reaction is carried out at a temperature and for a time suitable for the completion of the reaction (for example, heating to 60 ℃ C. And maintaining for about 10 hours), and the obtained reaction solution is cooled to room temperature.
The constituent unit α is not particularly limited, and examples thereof include 4- ((6- (methacryloyloxy) hexyl) oxy) benzoic acid, 4- (methacryloyloxy) benzoic acid, 4- ((6- (methacryloyloxy) methyl) oxy) benzoic acid, 4- ((6- (methacryloyloxy) ethyl) oxy) benzoic acid, 4- ((6- (methacryloyloxy) propyl) oxy) benzoic acid, 4- ((6- (methacryloyloxy) butyl) oxy) benzoic acid, 4- ((6- (methacryloyloxy) pentyl) oxy) benzoic acid, 4- ((6- (methacryloyloxy) heptyl) oxy) benzoic acid, 4- ((6- (methacryloyloxy) octyl) oxy) benzoic acid, 4- ((6- (methacryloyloxy) nonyl) oxy) benzoic acid, 4- ((6- (methacryloyloxy) decyl) oxy) benzoic acid, 4- ((6- (methacryloyloxy) dodecyl) oxy) benzoic acid, 4' - ((6- (methacryloyloxy) hexyl) oxy) - [1,1' -carboxylic acid, 4' - ((6- (methacryloyloxy) hexyl) oxy ] -4-carboxylic acid, ([ biphenyl ] ([ 6- (methacryloyloxy) propyl) oxy ] -4-biphenylcarboxylic acid 4'- (methacryloyloxy) - [1,1' -biphenyl ] -4-carboxylic acid, 6- ((6- (methacryloyloxy) hexyl) oxy) -2-naphthoic acid, 6- ((6- (methacryloyloxy) propyl) oxy) -2-naphthoic acid, 6- (methacryloyloxy) -2-naphthoic acid, 2-fluoro-4- ((6- (methacryloyloxy) hexyl) oxy) benzoic acid, 4- ((6- (acryloyloxy) hexyl) oxy) benzoic acid, 4- (acryloyloxy) benzoic acid, 4- ((6- (acryloyloxy) methyl) oxy) benzoic acid, 4- ((6- (acryloyloxy) ethyl) oxy) benzoic acid, 4- ((6- (acryloyloxy) propyl) oxy) benzoic acid, 4- ((6- (acryloyloxy) butyl) oxy) benzoic acid, 4- ((6- (acryloyloxy) pentyl) oxy) benzoic acid, 4- ((6- (acryloyloxy) heptyl) oxy) benzoic acid, 4- ((6- (acryloyloxy) octyl) oxy) benzoic acid, 4- ((6- (acryloyloxy) nonyl) oxy) benzoic acid, 4- ((6- (acryloyloxy) decyl) oxy) benzoic acid, 4- ((6- (acryloyloxy) dodecyl) oxy) benzoic acid, 4'- ((6- (acryloyloxy) hexyl) oxy) - [1,1' -biphenyl ] -4-carboxylic acid, 4'- ((6- (acryloyloxy) propyl) oxy) - [1,1' -biphenyl ] -4-carboxylic acid, 4'- (acryloyloxy) - [1,1' -biphenyl ] -4-carboxylic acid, 6- ((6- (acryloyloxy) hexyl) oxy) -2-naphthoic acid, 6- ((6- (acryloyloxy) propyl) oxy) -2-naphthoic acid, 6- (acryloyloxy) -2-naphthoic acid, 2-fluoro-4- ((6- (acryloyloxy) hexyl) oxy) benzoic acid, and the like. These constituent units α may be used singly or in combination of two or more. As described above, the constituent unit α can be used in the form of a derivative of the constituent unit α in which the carboxylic acid of the constituent unit α is protected, if necessary. The protecting group for protecting the carboxylic acid constituting the unit α is not particularly limited, and examples thereof include a methoxymethyl group, a benzyl ether group, a p-methoxybenzyl group, a 3, 4-dimethoxybenzyl group, a naphthylmethyl group, a methyl group, a t-butyldimethylsilyl group, a triethylsilyl group, a t-butyldiphenylsilyl group, a triisopropylsilyl group, and a tetrahydropyranyl group.
As the precursor of the constituent unit β, a compound containing Mb-SPCRb-ring B in the formula (I) and having a functional group such as a hydroxyl group introduced into ring B can be used. Specific examples thereof include, but are not particularly limited to, 6- (4-hydroxyphenoxy) hexyl methacrylate, 6- ((4 '- (3-hydroxypropoxy) - [1,1' -biphenyl ] -4-yl) oxy) hexyl methacrylate, 6- ((4 '-hydroxy- [1,1' -biphenyl ] -4-yl) oxy) hexyl methacrylate, 4-hydroxyphenyl methacrylate, 6- (4-hydroxyphenoxy) methyl methacrylate, 6- (4-hydroxyphenoxy) ethyl methacrylate, 6- (4-hydroxyphenoxy) propyl methacrylate, 6- (4-hydroxyphenoxy) butyl methacrylate, 6- (4-hydroxyphenoxy) pentyl methacrylate, 6- (4-hydroxyphenoxy) heptyl methacrylate, 6- (4-hydroxyphenoxy) octyl methacrylate, 6- (4-hydroxyphenoxy) nonyl methacrylate, 6- (4-hydroxyphenoxy) decyl methacrylate, 6- (4-hydroxyphenoxy) dodecyl methacrylate, 6- ((4 '- (3-hydroxypropoxy) - [1,1' -biphenyl ] -4-yl) oxy) methyl acrylate, 6- ((4 '- (3-hydroxypropoxy) - [1,1' -biphenyl ] -4-yl) oxy) propyl) methyl acrylate, 6- ((4-hydroxypropoxy) propyl) methyl acrylate, 6- ((4-hydroxy-propyl) oxy ] -4-propyl) methyl acrylate, 6- ((4-hydroxy-propyl) methyl acrylate, and 1- ((4-hydroxy-propoxy) - [1, 4-hydroxy-propyl) oxy) methyl acrylate, and so Enoate, 6- ((4 '- (3-hydroxypropoxy) - [1,1' -biphenyl ] -4-yl) oxy) butyl methacrylate, 6- ((4 '- (3-hydroxypropoxy) - [1,1' -biphenyl ] -4-yl) oxy) pentyl methacrylate, 6- ((4 '- (3-hydroxypropoxy) - [1,1' -biphenyl ] -4-yl) oxy) heptyl methacrylate, 6- ((4 '- (3-hydroxypropoxy) - [1,1' -biphenyl ] -4-yl) oxy) octyl methacrylate, 6- ((4 '- (3-hydroxypropoxy) - [1,1' -biphenyl ] -4-yl) oxy) nonyl methacrylate, 6- ((4 '- (3-hydroxypropoxy) - [1,1' -biphenyl ] -4-yl) oxy) decyl methacrylate, 6- ((4 '- (3-hydroxypropoxy) - [1,1' -biphenyl ] -4-yl) oxy) dodecyl methacrylate, 6- ((4 '- (3-hydroxymethoxy) - [1,1' -biphenyl ] -4-yl) oxy) hexyl methacrylate, 6- ((4 '- (3-hydroxyethoxy) - [1,1' -biphenyl ] -4-yl) oxy) hexyl methacrylate, 6- ((4-hexyl) acrylate, 6- ((4 '- (3-hydroxypentyloxy) - [1,1' -biphenyl ] -4-yl) oxy) hexyl methacrylate, 6- ((4 '- (3-hydroxyhexyloxy) - [1,1' -biphenyl ] -4-yl) oxy) hexyl methacrylate, and the like. These precursors of the constituent unit β may be used alone, or two or more of them may be used in combination.
The constituent unit γ is not particularly limited, and examples thereof include 4- ((6- (methacryloyloxy) hexyl) oxy) phenyl (E) -3- (4-methoxyphenyl) acrylate, 4- (methacryloyloxy) phenyl (E) -3- (4-methoxyphenyl) acrylate, 4- ((6- (methacryloyloxy) methyl) oxy) phenyl (E) -3- (4-methoxyphenyl) acrylate, 4- ((6- (methacryloyloxy) ethyl) oxy) phenyl (E) -3- (4-methoxyphenyl) acrylate, 4- ((6- (methacryloyloxy) propyl) oxy) phenyl (E) -3- (4-methoxyphenyl) acrylate, 4- ((6- (methacryloyloxy) butyl) oxy) phenyl (E) -3- (4-methoxyphenyl) acrylate, 4- ((6- (methacryloyloxy) pentyl) oxy) phenyl (E) -3- (4-methoxyphenyl) acrylate, 4- ((6- (methacryloyloxy) heptyl) oxy) phenyl (E) -3- (4-methoxyphenyl) acrylate, and 4- ((6- (methacryloyloxy) octyl) oxy) phenyl (E) -3- (4-methoxyphenyl) acrylate ) -3- (4-methoxyphenyl) acrylate, 4- ((6- (methacryloyloxy) nonyl) oxy) phenyl (E) -3- (4-methoxyphenyl) acrylate, 4- ((6- (methacryloyloxy) decyl) oxy) phenyl (E) -3- (4-methoxyphenyl) acrylate, 4- ((6- (methacryloyloxy) dodecyl) oxy) phenyl (E) -3- (4-methoxyphenyl) acrylate, (E) -3- (4- ((6- (methacryloyloxy) hexyl) oxy) phenyl) acrylic acid, (E) -3- (4- ((3- (methacryloyloxy) propyl) oxy) phenyl) acrylic acid, (E) -3- (4- (methacryloyloxy) phenyl) acrylic acid, (E) -6- (4- (3-methoxy-3-oxoprop-1-en-1-yl) phenoxy) hexyl methacrylate, (E) -6- (4- (3-methoxy-3-oxoprop-1-en-1-yl) phenoxy) propyl methacrylate, (E) -4- (3-methoxy-3-oxoprop-1-en-1-yl) phenyl methacrylate, (E) -6- (4- (3- (4-methoxyphenoxy) -3-oxoprop-1-en-1-yl) phenoxy) hexyl methacrylate, (E) -6- (4- (3- (4-methoxyphenoxy) -3-oxoprop-1-en-1-yl) phenoxy) propyl methacrylate, (E) -4- (3- (4-methoxyphenoxy) -3-oxoprop-1-en-1-yl) phenyl methacrylate, (E) -6- (4- (3- (4-butoxyphenoxy) -3-oxoprop-1-en-1-yl) phenoxy) hexyl methacrylate, (E) -6- (4- (3- (4-hexyloxyphenoxy) -3-oxoprop-1-en-1-yl) phenoxy) hexyl methacrylate, (E) -4- (3-methoxy-3-oxoprop-1-en-1-yl) phenyl 4- ((6- (methacryloyloxy) hexyl) oxy) benzoate, (E) -4- (3-methoxy-3-oxoprop-1-en-1-yl) phenyl 4- (6- (methacryloyloxy) phenyl) oxy) propyl methacrylate, (E) -4- (3-methoxy-3-oxoprop-1-en-1-yl) phenyl 4- ((6- (methacryloyloxy) hexyl) benzoate, (E) -6- (4- ((3- (4- (butoxy) phenyl) acryloyl) oxy) phenoxy) hexyl methacrylate, (E) -6- (4- ((3- (4- (hexyloxy) phenyl) acryloyl) oxy) phenoxy) hexyl methacrylate, (E) -6- (4- ((3- (4-fluorophenyl) acryloyl) oxy) phenoxy) hexyl methacrylate, (E) -6- (4- ((3- (4-chlorophenyl) acryloyl) oxy) phenoxy) hexyl methacrylate, (E) -6- (4- ((3- (4-bromophenyl) acryloyl) oxy) phenoxy) hexyl methacrylate, (E) -6- (4- ((3- (4-cyanophenyl) acryloyl) oxy) phenoxy) hexyl methacrylate, (E) -6- (4- ((3- (3, 4-dimethoxyphenyl) acryloyl) oxy) phenoxy) hexyl methacrylate, 4- ((6- (acryloyloxy) hexyl) oxy) phenyl (E) -3- (4-methoxyphenyl) acrylate, (E) -3- (4- ((6- (acryloyloxy) hexyl) oxy) Phenyl) acrylic acid, (E) -6- (4- (3- (4-methoxyphenoxy) -3-oxoprop-1-en-1-yl) phenoxy) hexyl acrylate, (E) -6- (4- (3-methoxy-3-oxoprop-1-en-1-yl) phenoxy) hexyl acrylate, (E) -4- (3-methoxy-3-oxoprop-1-en-1-yl) phenyl 4- ((6- (acryloyloxy) hexyl) oxy) benzoate, (E) -2- (((4- (3-methoxy-3-oxoprop-1-en-1-yl) phenoxy) carbonyl) amino) ethyl methacrylate, 2- (((4-methyl-3-oxopent-4-en-1-yl) carbamoyl) oxy) cyclohexyl (E) -3- (4-methoxyphenyl) acrylate, and the like. These constituent units γ may be used alone or in combination of two or more.
The polymerization initiator is not particularly limited, and examples thereof include diacyl peroxides such as 2,2 '-azobis (2, 4-dimethylvaleronitrile), azonitrile compounds such as 2,2' -azobiscyclohexanecarbonitrile, benzoyl peroxide, 2, 4-dichlorobenzoyl peroxide, p-chlorobenzoyl peroxide, o-methylbenzoyl peroxide, and bis-3, 5-trimethylhexanol peroxide; dialkyl peroxides such as diisopropylphenyl peroxide, 2, 5-dimethyl-2, 5-di- (t-butylperoxy) -hexane, t-butylcumyl peroxide, di-t-butyl peroxide, and 1, 3-bis- (t-butylperoxyisopropyl) -benzene; peroxyketals such as 1, 1-di-t-butylperoxycyclohexane, and alkyl peroxyesters such as t-butylperoxybenzoate; organic peroxides such as peroxycarbonates including diisopropyl peroxydicarbonate, α -amino ketone photopolymerization initiators such as Irgacure 907 (manufactured by BASF JAPAN Co., ltd.) and Irgacure369 (manufactured by BASF JAPAN Co., ltd.), acetophenone photopolymerization initiators such as 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1-hydroxycyclohexylphenylketone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin dimethyl ketal, benzoin-based photopolymerization initiators such as benzoin dimethyl ketal, benzophenone, benzoylbenzoic acid, and the like benzophenone-based photopolymerization initiators such as methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone and 4-benzoyl-4' -methyldiphenylsulfide, thioxanthone-based photopolymerization initiators such as 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone and 2, 4-diisopropylthioxanthone, 2,4, 6-trichloro-s-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4, 6-bis (trichloromethyl) -s-triazine, 2, 4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphthalen-1-yl) -4, 6-bis (trichloromethyl) -s-triazine, and mixtures thereof, triazine-based photopolymerization initiators such as 2- (4-methoxy-naphthalen-1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2, 4-trichloromethyl- (piperonyl) -6-triazine, and 2, 4-trichloromethyl (4' -methoxystyryl) -6-triazine, carbazole-based photopolymerization initiators, and imidazole-based photopolymerization initiators; and photopolymerization initiators such as α -acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzil, 9, 10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4' -diethylisophthalophenone (4, 4' -diethyl isophthalophenone), 3', 4' -tetrakis (t-butylperoxycarbonyl) benzophenone, 4' -diethylaminobenzophenone, and thioxanthone. These polymerization initiators may be used alone or in combination of two or more.
Suitable organic solvents are not particularly limited, and include, in addition to tetrahydrofuran, alcohol solvents such as ethanol, propanol, and butanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone, ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate, ether solvents such as diethyl ether and diethylene glycol dimethyl ether, hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, toluene, and xylene, nitrile solvents such as acetonitrile, and amide solvents such as N-methylpyrrolidone and dimethylacetamide. These organic solvents may be used alone or in combination of two or more.
Next, the second reaction step will be explained. In the second reaction step, for example, a compound for introducing a polymerizable group into the precursor of the constituent unit β, a carboxyl group activator, and an appropriate catalyst are added to the reaction solution obtained in the first reaction step to obtain a mixed solution. The mixture is allowed to react at a temperature and for a time suitable for completion of the reaction (for example, heated to 40 ℃ for 10 hours), and then the reaction solution is cooled. After the reaction is carried out at a temperature and for a time suitable for completion of deprotection by adding an acid catalyst to the reaction solution (for example, heating to 70 ℃ C. And maintaining for about 12 hours), the reaction solution is cooled to around room temperature. The cooled reaction solution is dropped in an appropriate organic solvent to form a precipitate, which is recovered and dried under reduced pressure to obtain a polymer (I).
The compound for introducing a polymerizable group into the precursor of the constituent unit β is not particularly limited as long as it contains R1 in the formula (I) and can react with a functional group introduced into the precursor of the constituent unit β to form the constituent unit β. Specific examples thereof include 4- ((6- (methacryloyloxy) hexyl) oxy) benzoic acid, 4'- ((6- (acryloyloxy) hexyl) oxy) - [1,1' -biphenyl ] -4-carboxylic acid, 4- (3- (methacryloyloxy) propyl) benzoic acid, 4- (3- (acryloyloxy) propyl) benzoic acid, acrylic acid, glycidyl methacrylate, methacrylic acid, 4- (methacryloyloxy) benzoic acid, 4- ((6- (methacryloyloxy) methyl) oxy) benzoic acid, 4- ((6- (methacryloyloxy) ethyl) oxy) benzoic acid, 4- ((6- (methacryloyloxy) butyl) oxy) benzoic acid, 4- ((6- (methacryloyloxy) pentyl) oxy) benzoic acid, 4- ((6- (methacryloyloxy) heptyl) oxy) benzoic acid, 4- ((6- (methacryloyloxy) octyl) oxy) benzoic acid, 4- ((6- (methacryloyloxy) nonyl) oxy) benzoic acid, 4- ((6- (methacryloyloxy) decyl) oxy) benzoic acid, 4- ((6- (methacryloyloxy) dodecyl) oxy) benzoic acid, 4'- ((6- (methacryloyloxy) hexyl) oxy) - [1,1' -biphenyl ] -4-carboxylic acid, 4'- ((6- (methacryloyloxy) propyl) oxy) - [1,1' -biphenyl ] -4-carboxylic acid, 4'- (methacryloyloxy) - [1,1' -biphenyl ] -4-carboxylic acid, 6- ((6- (methacryloyloxy) hexyl) oxy) -2-naphthoic acid, 6- ((6- (methacryloyloxy) propyl) oxy) -2-naphthoic acid, 6- (methacryloyloxy) -2-naphthoic acid, 2-fluoro-4- ((6- (methacryloyloxy) hexyl) oxy) benzoic acid, 4- ((6- (acryloyloxy) hexyl) oxy) benzoic acid, 4- (acryloyloxy) benzoic acid, 4- ((6- (acryloyloxy) methyl) oxy) benzoic acid, 4- ((6- (acryloyloxy) ethyl) oxy) benzoic acid, 4- ((6- (acryloyloxy) butyl) oxy) benzoic acid, 4- ((6- (acryloyloxy) pentyl) oxy) benzoic acid, 4) acryloyloxy) heptyl) oxy) heptyl oxy) benzoic acid, 4- ((6- (acryloyloxy) octyl) oxy) benzoic acid, 4- ((6- (acryloyloxy) nonyl) oxy) benzoic acid, 4- ((6- (acryloyloxy) decyl) oxy) benzoic acid, 4- ((6- (acryloyloxy) dodecyl) oxy) benzoic acid, 4'- ((6- (acryloyloxy) propyl) oxy) - [1,1' -biphenyl ] -4-carboxylic acid, 4'- (acryloyloxy) - [1,1' -biphenyl ] -4-carboxylic acid, 6- ((6- (acryloyloxy) hexyl) oxy) -2-naphthoic acid, 6- ((6- (acryloyloxy) propyl) oxy) -2-naphthoic acid, 6- (acryloyloxy) -2-naphthoic acid, 2-fluoro-4- ((6- (acryloyloxy) hexyl) oxy) benzoic acid and the like. These polymerizable group-introducing compounds may be used alone or in combination of two or more.
The carboxyl activating agent is not particularly limited, and examples thereof include 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, dicyclohexylcarbodiimide, and 2-ethoxy-1-ethoxycarbonyl-1, 2-dihydroquinoline. These carboxyl group activators may be used alone or in combination of two or more.
Suitable catalysts are not particularly limited, and in addition to 4- (dimethylamino) pyridine and tetraphenylphosphine, there may be mentioned amine catalysts such as amine, benzylamine, dibutylamine, triethanolamine, benzylamine and triethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, triethylbenzylammonium chloride, tetraethylammonium acetate, tetra-n-butylammonium bromide, tetra-n-butylammonium iodide, triethylbenzylammonium bromide, diphenyliodine bromide, triphenylsulfonium bromide, tri-n-octylsulfonium bromide, triphenylsulfonium chloride and tetraethylammonium bromide, phosphorus catalysts such as trimethylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine and chlorodiphenylphosphine, and the like. These catalysts may be used alone or in combination of two or more.
Suitable acid catalysts are not particularly limited, and examples thereof include sulfonic acids such as methanesulfonic acid, p-benzenesulfonic acid and sulfuric acid, carboxylic acids such as acetic acid, phosphoric acids, hydrochloric acid, photoacid generators and thermal acid generators. These acid catalysts may be used alone or in combination of two or more.
Suitable organic solvents are not particularly limited, and examples thereof include alcohol solvents such as N-hexane, cyclohexanone, ethanol, propanol, and butanol, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone, ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate, ether solvents such as diethyl ether and diethylene glycol dimethyl ether, hydrocarbon solvents such as hexane, cyclohexane, methylcyclohexane, toluene, and xylene, nitrile solvents such as acetonitrile, and amide solvents such as N-methylpyrrolidone and dimethylacetamide. These solvents may be used alone or in combination of two or more.
In another embodiment, in the production of the polymer (I), the constituent unit α may be used in the first reaction step and may be used as a precursor of the constituent unit β. In this case, the constituent unit α may be used in a mole percentage of l + m, and in the second reaction step, a compound for introducing a polymerizable group into the precursor of the constituent unit β may be added in an amount corresponding to the mole percentage m. In this embodiment, deprotection is not required in the second reaction step.
The polymer (I) may be dissolved in an organic solvent to prepare a composition for a photo-alignment film, and it is generally preferable to dissolve the polymer (I) in the organic solvent at a concentration of about 1 to 10% by mass.
(optical alignment film sample composition)
According to a second embodiment of the present disclosure, there is provided a composition for a photoalignment film, comprising the polymer (I) described above. In addition to the polymer (I), a component generally contained in a polymerizable composition that is polymerized by light and heat, such as an organic solvent, a photo/thermal polymerization initiator, a surfactant, and a crosslinking agent, if necessary, may be appropriately added to the composition for a photo-alignment film. The content of any of these optional components is not particularly limited, and generally, the photo-thermal polymerization initiator is preferably contained in an amount of about 70 to about 99 mass%, preferably about 1 to about 10 mass%, preferably about 0.1 to about 5 mass%, and preferably about 10 to about 40 mass% of the crosslinking agent, based on the total weight of the polymer (I) contained in the photo-alignment film composition.
As the organic solvent which can be blended in the composition for a photo-alignment film, any of the organic solvents generally used in this field can be used, and specific examples of such organic solvents include toluene, ethylbenzene, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol methyl ether, dibutyl ether, acetone, methyl ethyl ketone, ethanol, propanol, cyclohexane, cyclopentanone, methylcyclohexane, tetrahydrofuran, dioxane (dioxane), cyclohexanone, N-hexane, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, methoxybutyl acetate, N-methylpyrrolidone, dimethylacetamide, and the like. These may be used alone or in combination of two or more.
Examples of the photo/thermal polymerization initiator that can be blended in the composition for a photo-alignment film include diacyl peroxides such as 2,2' -azobis (2, 4-dimethylvaleronitrile), 2' -azobisisobutyronitrile, 2' -azobiscyclohexylnitrile and the like, benzoyl peroxide, 2, 4-dichlorobenzoyl peroxide, p-chlorobenzoyl peroxide, o-methylbenzoyl peroxide, bis-3, 5-trimethylhexanol peroxide and the like; dialkyl peroxides such as diisopropylphenyl peroxide, 2, 5-dimethyl-2, 5-di- (t-butylperoxy) -hexane, t-butylcumyl peroxide, di-t-butyl peroxide, and 1, 3-bis- (t-butylperoxyisopropyl) -benzene; peroxyketals such as 1, 1-di-tert-butylperoxycyclohexane, and alkyl peroxyesters such as tert-butylperoxybenzoate; organic peroxides such as peroxycarbonates including diisopropyl peroxydicarbonate, α -amino ketone photopolymerization initiators such as Irgacure 907 (manufactured by BASF JAPAN Co., ltd.) and Irgacure369 (manufactured by BASF JAPAN Co., ltd.), acetophenone photopolymerization initiators such as 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-1-one, 1-hydroxycyclohexylphenylketone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin dimethyl ketal, benzoin-based photopolymerization initiators such as benzoin dimethyl ketal, benzophenone, benzoylbenzoic acid, and the like benzophenone-based photopolymerization initiators such as methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone and 4-benzoyl-4' -methyldiphenylsulfide, thioxanthone-based photopolymerization initiators such as 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone and 2, 4-diisopropylthioxanthone, 2,4, 6-trichloro-s-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4, 6-bis (trichloromethyl) -s-triazine, 2, 4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphthalen-1-yl) -4, 6-bis (trichloromethyl) -s-triazine, and mixtures thereof, triazine-based photopolymerization initiators such as 2- (4-methoxy-naphthalen-1-yl) -4, 6-bis (trichloromethyl) -s-triazine, 2, 4-trichloromethyl- (piperonyl) -6-triazine, and 2, 4-trichloromethyl (4' -methoxystyryl) -6-triazine, carbazole-based photopolymerization initiators, and imidazole-based photopolymerization initiators; and photopolymerization initiators such as α -acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzil, 9, 10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4 '-diethylisophthalophenone, 3',4 '-tetrakis (t-butylperoxycarbonyl) benzophenone, 4' -diethylaminobenzophenone, and thioxanthone. These photo-thermal polymerization initiators may be used alone or in combination of two or more.
As the surfactant that can be blended in the composition for a photoalignment film, any of surfactants generally used for forming a film having a uniform thickness can be used. Specific examples thereof include anionic surfactants such as sodium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, polyoxyethylene alkyl ether sulfate, alkyl ether phosphate, sodium oleylsuccinate, potassium myristate, potassium coconut oil fatty acid, and sodium lauroyl sarcosinate; nonionic surfactants such as polyethylene glycol monolaurate, sorbitan stearate, glyceryl myristate, glyceryl dioleate, sorbitan stearate, and sorbitan oleate; cationic surfactants such as stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, and cetyl trimethyl ammonium chloride; amphoteric surfactants such as alkyl betaines (e.g., lauryl betaine, alkyl sulfobetaine, cocamidopropyl betaine, and alkyldimethylaminoacetic acid betaine), alkyl imidazolines, sodium lauroyl sarcosinate, and sodium cocoamphoacetate; and surfactants such as BYK-361, BYK-306, BYK-307 (BYK JAPAN Co., ltd.), fluorad FC430 (3M JAPAN Co., ltd.), megafac F171 and R08 (DIC Co., ltd.). These surfactants may be used alone or in combination of two or more.
As the crosslinking agent that can be blended in the composition for a photoalignment film, any of those generally used in the art may be used, and specific examples of such a crosslinking agent include methylol compounds, polyfunctional thiol compounds, polyfunctional (meth) acrylates, and the like. These crosslinking agents may be used alone or in combination of two or more.
Specific examples of the methylol compound include (1) alkoxymethylated glycolurils such as 1,3,4, 6-tetrakis (methoxymethyl) glycoluril, 1,3,4, 6-tetrakis (butoxymethyl) glycoluril, 1,3,4, 6-tetrakis (hydroxymethyl) glycoluril, 1, 3-bis (hydroxymethyl) urea, 1, 3-tetrakis (butoxymethyl) urea, 1, 3-tetrakis (methoxymethyl) urea, 1, 3-bis (hydroxymethyl) -4, 5-dihydroxy-2-imidazolidinone and 1, 3-bis (methoxymethyl) -4, 5-dimethoxy-2-imidazolidinone; (2) Alkoxymethylated benzoguanamines such as tetramethoxymethylbenzguanamine and tetrabutoxymethylbenzguanamine; and (3) alkoxymethylated melamines such as hexamethoxymethylmelamine and hexabutoxymethylmelamine. These may be used alone or in combination of two or more. Examples of commercially available products of alkoxymethylated glycoluril include glycoluril compounds (trade names Cymel 1170 and POWDERLINK 1174) manufactured by Nihon Cytec Industries, methylated urea resins (trade names UFR 65) and butylated urea resins (trade names UFR300, U-VAN10S60, U-VAN10R and U-VAN11 HV), urea/formaldehyde resins (highly condensed type, trade names BECKAMINE J-300S, BECKAMINE P-955 and BECKAMINE N) manufactured by DIC corporation, and butylated urea resins (trade names BECKAMINE P-138, BECKAMINE P-196-M and BECKAMINE G-1850). Commercially available products of alkoxymethylated benzoguanamine include Nihon Cytec Industries, inc. (trade name Cymel 1123), sanwa Chemical corporation (trade names NIKALACBX-4000, NIKALACBX-37, NIKALAC BL-60, and NIKALAC BX-55H), and butylated benzoguanamine resins (trade names SUPERBECKAMINE TD-126 and SUPERBECKAMINE 15-594) from DIC. Commercially available products of alkoxymethylated melamine include methoxymethyl-type melamine compounds (trade names of Cymel 300, cymel 301, cymel 303, cymel 350) and butoxymethyl-type melamine compounds (trade names of Mycoat 506, mycoat 508) manufactured by Nihon Cytec Industries, methoxymethyl-type melamine compounds (trade names of NIKALAC MW-30, NIKALAC MW-22, NIKALAC MW-11, NIKALAC MS-001, NIKALAC MX-002, NIKALAC MX-730, NIKALAC MX-750, and NIKALAC MX-035), butoxymethyl-type melamine compounds (trade names of NIKALAC 45, NIKALAC MX-410, NIKALAC-302), butylated melamine resins (SUPBER J-60, SUPBERBEL 60-60, SUPERBECKERE-60, SUP-60-SUPERCKBEL-60-SUP-60, BECKAMINE-60-SUP-60, SUP-60-SUPERBECKAMINE-548), and the like. Further, an aqueous melamine resin such as WATERSOL S-695 and S-683-IM, trade name BECKAMINE P-198, which are trade names available from DIC corporation, may be used.
Further, a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound obtained by condensing a hydrogen atom of such an amino group with a hydroxymethyl group or an alkoxymethyl group can also be used as the crosslinking agent. Examples of the commercially available products of such melamine compounds include the trade name Cymel 303 (manufactured by Nihon Cytec Industries), and examples of the commercially available products of such benzoguanamine compounds include the trade name Cymel 1123 (manufactured by Nihon Cytec Industries).
The polyfunctional thiol compound is a compound having 2 or more thiol groups in 1 molecule.
Specific examples of the polyfunctional thiol compound include hexane dithiol, decane dithiol, 1, 4-dimethylmercaptobenzene, butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, neopentyltetraol tetrashiopropionate, neopentyltetraol tetrathioglycolate, triethanol tristhiopropionate, neopentyltetraol tetrakis (3-mercaptobutyrate), 1, 4-bis (3-mercaptobutyryloxy) butane, and the like.
The polyfunctional (meth) acrylate is a (meth) acrylate having 2 or more ethylenically unsaturated bonds in 1 molecule.
Specific examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetradecanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyltetraol tri (meth) acrylate, neopentyltetraol tetra (meth) acrylate, and dineopentylenetetraol hexa (meth) acrylate.
Further, examples of the components generally contained in a polymerizable composition which is polymerized by light and heat include a silane coupling agent typified by an alkoxysilane compound, an epoxy resin, an isocyanate resin typified by a polyfunctional isocyanate or a blocked isocyanate, and a polyfunctional compound including hydrazide, carbodiimide, acetone acetate (12450507512488\\.
The composition for a photoalignment film of the present disclosure thus obtained may be applied to a substrate, and after the solvent is distilled off as necessary, the composition may be irradiated with linearly polarized light to form a photoalignment film.
(optical alignment film)
According to a third embodiment of the present disclosure, there is provided a photo-alignment film including the above composition for a photo-alignment film. The photo-alignment film can be produced, for example, by applying the above-described composition for a photo-alignment film to a substrate, distilling off a solvent if necessary, and then irradiating the substrate with linearly polarized light.
Examples of the substrate constituting the substrate include glass substrates such as quartz glass, alkali glass, and alkali-free glass, resin substrates such as polyimide, polyamide, acrylic resin, polyvinyl alcohol, triacetyl cellulose, polyethylene terephthalate, cycloolefin polymer, polyethylene, polycarbonate, polystyrene, and polytrifluorochloroethylene, and metal substrates such as iron, aluminum, and copper, and glass substrates and triacetyl cellulose are more preferable.
As a method for coating the composition for a photoalignment film, any method generally known in the art may be used, for example, spin coating, bar coating, die coating, screen printing, spray coating, and the like.
The drying step for distilling off the solvent may be carried out by any method generally used in the art, and is not particularly limited as long as a film capable of forming a resin layer can be formed. For example, the drying may be carried out by a warm air dryer, a hot plate, or a far infrared heater.
The linearly polarized light may be irradiated to the photo-alignment film from either the vertical direction or the oblique direction, but is preferably irradiated from the vertical direction.
In the present specification, the linearly polarized light refers to light having one plane including the vibration direction of an electric field (or a magnetic field). The linearly polarized light can be obtained by using a polarizing filter or a polarizing prism for the light from the light source. The light to be irradiated is not particularly limited as long as it is an irradiation ray capable of imparting photo-alignment ability to the photo-alignment sites (a) of the liquid crystal layer by irradiation, such as infrared rays, visible rays, ultraviolet rays (near ultraviolet rays, far ultraviolet rays, etc.), X-rays, charged particle beams (e.g., electron beams, etc.), etc., and the irradiation ray usually has a wavelength of 200nm to 500nm in many cases, and is preferably near ultraviolet rays of 350nm to 450nm from the viewpoint of efficiency. Examples of the light source include a xenon lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, and a metal halide lamp. The ultraviolet light and the visible light obtained by such a light source may be limited in the wavelength range of irradiation by using an interference filter, a color filter, or the like.
The photoalignment film according to the third embodiment of the present disclosure can provide liquid crystal alignment capability to the alignment film by a lower irradiation energy than a conventional photoalignment film. Therefore, although the irradiation energy varies depending on the film thickness, it is usually about 1mJ/cm, for example, in the case of a thickness of 1 μm 2 ～500mJ/cm 2 Preferably about 1 to 100mJ/cm 2 。
When linearly polarized light is irradiated, if a photomask is used, the alignment capability of liquid crystal or the like can be generated in a pattern in 2 or more different directions in the photo-alignment film. Specifically, after the composition for a photoalignment film of the present disclosure is coated and dried, a photomask is coated thereon, and linearly polarized light is irradiated to impart an alignment ability only to an exposed portion, and the alignment ability can be generated in a pattern shape in a plurality of directions by changing the direction as necessary and repeating the process a plurality of times.
The photoalignment film of the present disclosure has a film thickness preferably ranging from about 10nm to about 500nm, more preferably ranging from about 100nm to about 500nm, and still more preferably ranging from about 100nm to about 200 nm.
After the phase difference film material is coated on the photo-alignment film of the present disclosure obtained in this way, the phase difference film material is heated to the phase transition temperature of liquid crystal to bring the phase difference film material into a liquid crystal state, and the liquid crystal state is photo-cured, whereby various optically anisotropic films such as a phase difference film, a viewing angle improving film, a brightness improving film, and a polarizing film can be obtained.
(retardation film)
According to a fourth embodiment of the present disclosure, there is provided a retardation film in which a liquid crystalline compound is further aligned on the photo-alignment film. The retardation film is a film having different refractive indices in the X-axis direction and the Y-axis direction perpendicular to the Z-axis direction (film thickness direction), and is a film in which a difference occurs in the velocity of a wave vibrating in each of the X, Y, and Z-axis directions when light moves in the film. The phase difference film can be obtained by coating a phase difference film material on the photo-alignment film, heating the photo-alignment film material to a phase transition temperature of liquid crystal to bring the phase difference film material into a liquid crystal state, and photocuring the liquid crystal state.
The retardation film material is not particularly limited as long as it is a polymerizable liquid crystal material, and a material containing a liquid crystal monomer having a polymerizable group, particularly a material containing a polyfunctional monomer having 2 or more ethylenically unsaturated bonds in 1 molecule, which is generally used in the art, is preferably used. Such polymerizable liquid crystal materials include those having an alignment property such as a horizontal alignment, a cholesteric alignment, a vertical alignment, or a hybrid (hybrid) alignment, and can be used separately according to a desired retardation. The polymerizable liquid crystal materials may be used alone, or two or more of them may be used in combination as necessary.
Examples of the polyfunctional monomer having 2 or more ethylenically unsaturated bonds in 1 molecule include a polyfunctional (meth) acrylate monomer, a polyfunctional (meth) acrylamide monomer, a polyfunctional vinyl monomer, and a polyfunctional allyl monomer.
Specific examples of the polyfunctional (meth) acrylate monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetradecanediol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, neopentyltetraol tri (meth) acrylate, neopentyltetraol tetra (meth) acrylate, and neopentyltetraol hexa (meth) acrylate.
Specific examples of the polyfunctional (meth) acrylamide monomer include N, N' -methylenebisacrylamide, polyfunctional (meth) acrylamides synthesized from ethylenediamine, phenylenediamine, and the like.
Specific examples of the polyfunctional vinyl monomer include divinylbenzene, ethylene glycol divinyl ether, adipic acid divinyl ester, succinic acid divinyl ester, and the like.
Specific examples of the polyfunctional allyl monomer include diallyl phthalate, diallyl ether, diallyl malonate, and p-allyl styrene.
As the solvent, photopolymerization initiator, crosslinking agent, surfactant and the like that can be used in the composition for retardation film, the same solvents, photopolymerization initiators, crosslinking agents and surfactants as those used in the production of the photo-alignment film composition can be used. In addition, the above-described method of coating the photo-alignment film composition may be used for coating the composition for a retardation film.
Examples
The present disclosure will be specifically described below with reference to examples, but the present disclosure is not limited to the following examples.
[ Synthesis example 1]4- ((6- (methacryloyloxy) hexyl) oxy) benzoic acid (Compound A', compound. Beta.1)
The corresponding monoacrylates were synthesized according to the method described in makromol chem.,190, p2255-2268,1989, using methacryloyl chloride instead of acryloyl chloride.
Synthesis example 2 preparation of methoxymethyl 4- ((6- (methacryloyloxy) hexyl) oxy) benzoate (Compound A)
260.0g (849 mmol) of 4- ((6- (methacryloyloxy) hexyl) oxy) benzoic acid obtained in Synthesis example 1 and 111.6g (1103.3 mmol, manufactured by Tokyo chemical Co., ltd.) of triethylamine were dissolved in 780g of toluene to obtain a solution. To the solution was added dropwise 78.6g (976.0 mmol, manufactured by Tokyo chemical industry Co., ltd.) of chlorodimethyl ether over 1 hour, followed by heating to 40 ℃ and maintaining for 4 hours to allow the reaction to proceed, and then, after cooling the reaction solution, 260g of water was added. To the separated organic layer was added 260g (2164.9 mmol) of 50% aqueous acetic acid solution and stirred. The separated organic layer was concentrated to obtain 291.4g (yield 98.0%) of methoxymethyl 4- ((6- (methacryloyloxy) hexyl) oxy) benzoate as a pale yellow liquid.
[ Synthesis example 3]4'- ((6- (acryloyloxy) hexyl) oxy) - [1,1' -biphenyl ] -4-carboxylic acid (Compound. Beta.2)
The corresponding monoacrylates are synthesized according to the method described in makromol chem.,190, p2255-2268,1989, starting from 4- (4-hydroxyphenyl) benzoic acid.
[ Synthesis example 4]4- ((6- (acryloyloxy) hexyl) oxy) - [1,1' -biphenyl ] -4-carboxylic acid methoxymethyl ester (Compound B)
The compound β 2 produced in synthesis example 3 was synthesized by the same method as in synthesis example 2 using it as a starting material.
Synthesis example 5 6- (4-hydroxyphenoxy) hexyl methacrylate (Compound C)
1, 4-dihydroxybenzene and 1, 6-dibromohexane are heated under alkaline conditions, thereby synthesizing 6- (4-hydroxyphenoxy) -1-bromohexane. The product was reacted with lithium methacrylate to synthesize 6- (4-hydroxyphenoxy) hexyl methacrylate.
Synthesis example 6- ((4 '- (3-hydroxypropoxy) - [1,1' -biphenyl ] -4-yl) oxy) hexyl methacrylate (Compound D)
4-hydroxy-4 '-hydroxypropoxybiphenyl is synthesized by heating 4,4' -biphenyldiol with 2-chloropropanol under alkaline conditions. The product was reacted with 1, 6-dibromohexane under alkaline conditions to synthesize 4- (6-bromohexyloxy) -4' -hydroxypropoxybiphenyl. This product was reacted with lithium methacrylate to synthesize 6- ((4 '- (3-hydroxypropoxy) - [1,1' -biphenyl ] -4-yl) oxy) hexyl methacrylate.
Synthesis example 7- ((4 '-hydroxy- [1,1' -biphenyl ] -4-yl) oxy) hexyl methacrylate (Compound E)
4,4' -biphenyldiol was heated with 1, 6-dibromohexane under basic conditions, whereby 6- ((4 ' -hydroxy- [1,1' -biphenyl ] -4-yl) oxy) -1-bromohexane was synthesized. This product was reacted with lithium methacrylate to synthesize 6- ((4 '-hydroxy- [1,1' -biphenyl ] -4-yl) oxy) hexyl methacrylate.
Synthesis example 8 4- (3- (methacryloyloxy) propyl) benzoic acid (Compound. Beta.3)
The corresponding monoacrylates were synthesized according to the method described in makromol chem.,190, p2255-2268,1989, using 1, 3-dibromopropane instead of 6-chlorohexanol and methacrylic acid instead of acryloyl chloride.
Synthesis example 9 4- (3- (acryloyloxy) propyl) benzoic acid (Compound. Beta.4)
The corresponding monoacrylates were synthesized according to the method described in makromol chem.,190, p2255-2268,1989, using 1, 3-dibromopropane instead of 6-chlorohexanol and acrylic acid instead of acryloyl chloride.
[ Synthesis example 10]4- ((6- (acryloyloxy) hexyl) oxy) benzoic acid (Compound. Beta.5)
Monoacrylates were synthesized according to the method described in Makromol. Chem.,190, p2255-2268, 1989.
[ Synthesis example 11]4- ((6- (methacryloyloxy) hexyl) oxy) phenyl (E) -3- (4-methoxyphenyl) acrylate (Compound F)
P-methoxycinnamoyl chloride was added to the 6- (4-hydroxyphenoxy) hexyl methacrylate prepared in Synthesis example 5 under basic conditions to synthesize 4- ((6- (methacryloyloxy) hexyl) oxy) phenyl (E) -3- (4-methoxyphenyl) acrylate.
[ Synthesis example 12] (E) -6- (4- (3- (4-methoxyphenoxy) -3-oxoprop-1-en-1-yl) phenoxy) hexyl methacrylate (Compound G)
(E) -3- (4- ((6-methacryloyloxy) hexyl) oxy) phenyl) acrylic acid was synthesized according to the method described in Makromol. Chem.,190, p2255-2268,1989, using methacrylic acid instead of acryloyl chloride and 4-hydroxycinnamic acid instead of ethyl 4-hydroxybenzoate. This product was reacted with 4-methoxyphenol in the presence of a condensing agent to synthesize (E) -6- (4- (3- (4-methoxyphenoxy) -3-oxoprop-1-en-1-yl) phenoxy) hexyl methacrylate (Compound G).
[ Synthesis example 13] (E) -4- (3-methoxy-3-oxoprop-1-en-1-yl) phenyl 4- ((6- (methacryloyloxy) hexyl) oxy) benzoate (Compound H)
Using the compound β 1 synthesized in synthesis example 1 as a starting material, methyl 4-hydroxycinnamate was heated in the presence of a condensing agent, thereby synthesizing (E) -4- (3-methoxy-3-oxoprop-1-en-1-yl) phenyl 4- ((6- (methacryloyloxy) hexyl) oxy) benzoate (compound H).
1. Synthesis of polymers
[ example 1]
(production of Polymer I-1)
< first reaction step >
8.8g (25.2 mmol) of methoxymethyl 4- ((6- (methacryloyloxy) hexyl) oxy) benzoate (constituent unit α derivative, compound A), 1.0g (3.6 mmol) of 6- (4-hydroxyphenoxy) hexyl methacrylate (constituent unit β precursor, compound C), 3.2g (7.2 mmol) of 4- ((6- (methacryloyloxy) hexyl) oxy) phenyl (E) -3- (4-methoxyphenyl) acrylate (constituent unit γ, compound F) and 0.2g of 2,2' -azobis (2, 4-dimethylpentanenitrile) (polymerization initiator) prepared in Synthesis example 2 were dissolved in 24.7g of tetrahydrofuran to obtain a solution. After nitrogen gas was introduced into the solution for 1 hour, the reaction was allowed to proceed by heating to 60 ℃ and maintaining the temperature for 10 hours, and the reaction solution was cooled to room temperature.
< second reaction Process >
To the reaction solution obtained in the first reaction step, 1.1g (3.6 mmol) of 4- ((6- (methacryloyloxy) hexyl) oxy) benzoic acid (polymerizable group-introducing compound,. Beta.1), 0.9g (4.7 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (carboxyl activating agent) and 0.1g (0.7 mmol) of 4- (dimethylamino) pyridine (catalyst A) prepared in Synthesis example 1 were added to obtain a mixed solution. The reaction was allowed to proceed by heating the mixture to 40 ℃ for 10 hours, and then the reaction mixture was cooled. 1.8g (12.6 mmol, manufactured by Tokyo chemical Co., ltd.) of 70% methanesulfonic acid was added to the reaction solution at room temperature, and deprotection was carried out by heating to 70 ℃ and maintaining for 12 hours, and then the reaction solution was cooled to near room temperature. The cooled reaction solution was dropwise added to 130g of n-hexane to form a precipitate, and the precipitate was recovered and dried under reduced pressure to obtain polymer I-1. The structure is shown in table 2.
< determination of weight average Molecular Weight (MW) >
The weight average Molecular Weight (MW) of the polymer I-1 obtained above was determined using Gel Permeation Chromatography (GPC). The weight average Molecular Weight (MW) obtained was 43,000 in terms of polystyrene.
Examples 2 to 18
Polymers I-2 to I-18 of examples were produced and the weight average molecular weight (Mw) was measured in the same manner as in example 1, except that the kinds and amounts of the compounds constituting the respective constituent units were changed to the compositions shown in Table 1. The structural formula of the polymer of each example is shown in table 2 below. Here, the polymers I-15 and I-16 have the same structures as those of the polymer I-1, and the polymers I-17 and I-18 have the same structures as those of the polymer I-5, and therefore, the descriptions thereof are omitted.
[ example 19]
< first reaction step >
9.8g (31.9 mmol) (constituent unit α, compound A '), 6.0g (13.7 mmol) (constituent unit γ, compound F) and 0.2g of 2,2' -azobis (2, 4-dimethylvaleronitrile) (polymerization initiator) of 4- ((6- (methacryloyloxy) hexyl) oxy) benzoic acid (constituent unit α, compound A ') were dissolved in 30.1g cyclohexanone to obtain a solution. The solution was aerated with nitrogen for 1 hour. Subsequently, after 10 hours, the reaction solution was cooled to room temperature.
< second reaction Process >
To the reaction solution obtained in the first reaction step, 0.7g (4.56 mmol) (polymerizable group-introduced compound,. Beta.7) of glycidyl methacrylate and 0.02g (0.06 mmol) (catalyst B) of tetraphenylphosphine were added at room temperature. Subsequently, the reaction was allowed to proceed by heating to 100 ℃ for 18 hours, and then the reaction solution was cooled to room temperature. The reaction solution was dropwise added to 130g of n-hexane to form a precipitate, and the precipitate was recovered and dried under reduced pressure to obtain polymer I-19. The structure is shown in table 2.
< determination of weight average Molecular Weight (MW) >
The weight average Molecular Weight (MW) of the polymer I-19 was determined in the same manner as in example 1, and found to be 52,000.
Comparative example 1
9.8g (31.9 mmol) of 4- ((6- (methacryloyloxy) hexyl) oxy) benzoic acid (constituent unit α, compound A '), 6.0g (13.7 mmol) of 4- ((6- (methacryloyloxy) hexyl) oxy) phenyl (E) -3- (4-methoxyphenyl) acrylate (constituent unit γ, compound F) and 0.2g (polymerization initiator) of 2,2' -azobis (2, 4-dimethylpentanenitrile) were dissolved in 30.1g of tetrahydrofuran, and nitrogen gas was purged into the solution for 1 hour. Then, the mixture was heated to 60 ℃. After 10 hours, the reaction liquid was cooled and added dropwise to 130g of n-hexane (1.5 mmol) to obtain a precipitate. Then, the obtained precipitate was dried under reduced pressure, thereby obtaining a polymer II having a structure shown in table 2.
For polymer II, the weight average molecular weight was measured in the same manner as in example 1, and the weight average Molecular Weight (MW) was 35,000.
The details of the reagents shown in table 1 are shown below.
[ alpha derivative of constituent Unit ]
A compound A: preparation of methoxymethyl 4- ((6- (methacryloyloxy) hexyl) oxy) benzoate (Compound prepared in Synthesis example 2)
Compound B: methoxymethyl 4- ((6- (acryloyloxy) hexyl) oxy) - [1,1' -biphenyl ] -4-carboxylate (compound produced in Synthesis example 4)
[ constituent Unit α ]
A' is a compound: 4- ((6- (Methacryloyloxy) hexyl) oxy) benzoic acid (Compound produced in Synthesis example 1)
[ precursor of constituent Unit β ]
Compound C:6- (4-Hydroxyphenoxy) hexyl methacrylate (Compound produced in Synthesis example 5)
Compound D:6- ((4 '- (3-Hydroxypropoxy) - [1,1' -biphenyl ] -4-yl) oxy) hexyl methacrylate (Compound produced in Synthesis example 6)
Compound E:6- ((4 '-hydroxy- [1,1' -biphenyl ] -4-yl) oxy) hexyl methacrylate (compound produced in Synthesis example 7)
[ constituent Unit [ gamma ]
Compound F:4- ((6- (Methacryloyloxy) hexyl) oxy) phenyl (E) -3- (4-methoxyphenyl) acrylate (the compound produced in Synthesis example 11)
Compound G: (E) -6- (4- (3- (4-methoxyphenoxy) -3-oxoprop-1-en-1-yl) phenoxy) hexyl methacrylate (Compound produced in Synthesis example 12)
Compound H: (E) -4- (3-methoxy-3-oxoprop-1-en-1-yl) phenyl 4- ((6- (methacryloyloxy) hexyl) oxy) benzoate (compound produced in Synthesis example 13)
Polymerization initiator: 2,2' -azobis (2, 4-dimethylvaleronitrile) (Fuji film and Wako pure chemical industries, ltd.)
[ polymerizable group-introduced Compound ]
Compound β 1:4- ((6- (methacryloyloxy) hexyl) oxy) benzoic acid (Compound produced in Synthesis example 1)
Compound β 2:4'- ((6- (acryloyloxy) hexyl) oxy) - [1,1' -biphenyl ] -4-carboxylic acid (compound produced in Synthesis example 3)
Compound β 3:4- (3- (methacryloyloxy) propyl) benzoic acid (the compound produced in Synthesis example 8)
Compound β 4:4- (3- (acryloyloxy) propyl) benzoic acid (Compound produced in Synthesis example 9)
Compound β 5:4- ((6- (acryloyloxy) hexyl) oxy) benzoic acid (Compound produced in Synthesis example 10)
Compound β 6: acrylic acid (Osaka organic chemical industry Co., ltd.)
Compound β 7: glycidyl methacrylate (Osaka, manufactured by Okagaku Kogyo Co., ltd.)
Carboxyl activating agent: 1-Ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Tokyo chemical Co., ltd.)
Catalyst A:4- (dimethylamino) pyridine (Tokyo Kasei Co., ltd.)
Catalyst B: tetraphenylphosphine (manufactured by Tokyo chemical industry Co., ltd.)
[ Table 1]
Figure BDA0003987788100000411
[ Table 2]
TABLE 2
Figure BDA0003987788100000421
/>
Figure BDA0003987788100000431
/>
Figure BDA0003987788100000441
/>
Figure BDA0003987788100000451
/>
Figure BDA0003987788100000461
2. Preparation of composition for photo-alignment film
The polymers (1.05 g each) produced in examples 1 to 19 and comparative example 1 were mixed with 98.95g of propylene glycol monomethyl ether in the absence of light to prepare compositions 1 to 20 for photo-alignment films, respectively.
3. Production of photo-alignment film
The above-obtained compositions 1 to 20 for a photo-alignment film were applied to a spin coaterCoated on a glass substrate to have a thickness of about 100 nm. Then, it was dried at 80 ℃ for 2 minutes by a hot plate, followed by irradiation of 10 to 40mJ/cm 2 The photo-alignment films 1 to 20 were produced by linearly polarized UV light.
4. Production of retardation film
A composition for retardation films was prepared by mixing 5.7g of a bifunctional liquid-crystalline acrylate (Paliocolor LC-242, manufactured by BASF corporation), 0.3g of a photopolymerization initiator (Irg OXE-01, manufactured by BASF JAPAN corporation), and 33.8g of toluene in the absence of light.
The obtained retardation film composition was applied to the photo-alignment films 1 to 20 using a spin coater so as to have a thickness of about 1 μm. Then, it was aligned at 120 ℃ and then irradiated at 500mJ/cm 2 Respectively preparing phase difference films 1-20 by using the non-polarized UV rays.
Test example 1: evaluation of orientation
The retardation of the retardation film substrate produced on the photo-alignment film was measured, and the alignment was evaluated. The retardation value Re of the birefringence of the produced retardation film was measured at a wavelength (. Lamda.) of 550nm using a retardation measuring apparatus (OPTIPRO-standard, manufactured by SHINTEC Co., ltd.), and Δ n was determined from the retardation value Re and the film thickness as shown in the following equation. The results are shown in Table 3.
Δ n = (Re/film thickness)/1000
Test example 2: evaluation of haze
The haze of the retardation film substrate produced on the photo-alignment film was measured, and the alignment properties were evaluated. The haze of the retardation film thus produced was measured using a haze meter (HM-150, manufactured by Nikkiso Kogyo Co., ltd.). The results are shown in Table 3.
From the results of test examples 1 and 2, it was found that sufficient alignment properties were observed in any of the retardation films. In the retardation films 4, 8, 11, and 12 (examples 4, 8, 11, and 12) using the photo-alignment films 4, 8, 11, and 12 using the constituent units having high rigidity, respectively, as a result, the alignment property at a low exposure amount is slightly low, but sufficient alignment property can be obtained by adjusting the exposure amount. Further, it is found that even when a constituent unit having high rigidity is used, sufficient alignment properties can be obtained even in a low exposure amount region in the retardation films 3 and 7 (examples 3 and 7) using the photo-alignment films 3 and 7 having high proportions of the constituent unit γ exhibiting photoreactivity, respectively.
Test example 3: evaluation of adhesion
After irradiating polarized UV light of 20mJ/cm 2 The photo-alignment films 1 to 20 thus obtained were each provided with a retardation film, and the resulting substrate of the retardation film was cut with a dicing blade so as to intersect each other (1 mm × 1mm × 100 squares), and then a transparent tape was attached, and the number of remaining squares of the retardation film on the substrate without being peeled off when the transparent tape was peeled off was counted. The adhesion between the photo-alignment film and the retardation film was evaluated by the number of remaining squares. The results are shown in Table 3.
In examples 1 to 19 using the photo-alignment films 1 to 19, the adhesion between the photo-alignment film and the retardation film was good, but in comparative example 1 using the photo-alignment film 20, it was confirmed that the polymerizable liquid crystal layer of the retardation film was completely peeled off in all the cells.
[ Table 3]
TABLE 3
Figure BDA0003987788100000481
/>

Claims (9)

1. A polymer having a repeating unit represented by the general formula (I),
[ solution 1]
Figure FDA0003987788090000011
In the formula (I), the compound is shown in the specification,
M a 、M b and M c Represents a portion of a monomer unit of a copolymer that forms a main chain of the copolymer;
l, m and n represent the molar percentage of the copolymer, in each case 0 < l < 1 and 0 < m < 1 and 0 < n < 1;
SPCRa, SPCRb, and SPCRc each independently represent a spacing unit;
ring a, ring B and ring C are each independently an unsubstituted or substituted alicyclic hydrocarbon or an unsubstituted or substituted aromatic ring;
x is a covalent single bond, an alkylene chain with 1-10 carbon atoms or a cycloalkylene chain with 3-8 carbon atoms;
y is selected from the group consisting of a covalent single bond; an alkylene chain having 1 to 10 carbon atoms which is unsubstituted or substituted with a hydroxyl group and/or a carbonyl group; a cycloalkylene chain having 3 to 8 carbon atoms; -O-; -COO-; and combinations thereof;
z is-O-CO-CH = CH 2 -, any of the bonding sites is optionally bonded to ring C;
R 1 is-CW = CH 2 or-V-CW = CH 2 Wherein W is hydrogen or methyl, V is-O-CO-or-CO-;
R 2 is a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; a phenyl group having at least 1 substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group and a halogen atom, wherein R is R when the ring C is an alicyclic hydrocarbon 2 Is a phenyl group having at least 1 substituent selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a cyano group and a halogen atom.
2. The polymer of claim 1, wherein ring A, ring B and ring C are each independently a group represented by the following general formula, any of the bonding sites being optionally bonded to the respective spacer unit,
[ solution 2]
Figure FDA0003987788090000021
In the formula, R 3 ～R 64 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a cyano group.
3. The polymer according to claim 2, wherein ring A is a group represented by the following general formula,
[ solution 3]
Figure FDA0003987788090000031
In the formula, R 3 ～R 14 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a cyano group,
ring B is a group represented by the following general formula, any of the bonding sites being optionally bonded to a spacer unit,
[ solution 4]
Figure FDA0003987788090000032
In the formula, R 7 ～R 14 、R 33 ～R 64 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a cyano group,
ring C is a group represented by the following general formula, any of the bonding sites being optionally bonded to a spacer unit,
[ solution 5]
Figure FDA0003987788090000041
In the formula, R 3 ～R 6 、R 33 ～R 40 Each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom or a cyano group.
4. The polymer according to any one of claims 1 to 3, wherein SPCRa, SPCRb and SPCRc are each independently a covalent single bond; carbon number of 1 to 20 unsubstituted or substituted by hydroxyl group and/or carbonyl groupAn alkylene chain of; a 3-8 carbon cycloalkylene chain unsubstituted or substituted with a hydroxyl group; unsubstituted or selected from the group consisting of alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, -CN, -NO 2 And phenylene substituted with at least 1 substituent of the group consisting of halogen; -O-; -COO-; or a combination thereof.
5. The polymer according to claim 4, wherein SPCRa, SPCRb and SPCRc are each independently an alkylene chain having 1 to 20 carbon atoms which is unsubstituted or substituted with a hydroxyl group and/or a carbonyl group; -O-; -COO-; or a combination thereof.
6. The polymer according to any one of claims 1 to 5, wherein Y is a combination of an alkylene chain of 1 to 10 carbon atoms which is unsubstituted or substituted with a hydroxyl group and/or a carbonyl group, and-O-or-COO-.
7. A composition for a photo-alignment film, comprising the polymer according to any one of claims 1 to 6.
8. A photo-alignment film formed from the composition for a photo-alignment film according to claim 7.
9. A retardation film obtained by further aligning a liquid crystalline compound on the photoalignment film according to claim 8.
CN202180041285.1A 2020-06-15 2021-06-14 Polymer, and photo-alignment film and retardation film using the same Active CN115916853B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2020103157 2020-06-15
JP2020-103157 2020-06-15
PCT/JP2021/022531 WO2021256428A1 (en) 2020-06-15 2021-06-14 Novel polymer, and photo-alignment film and retardation film each using same

Publications (2)

Publication Number Publication Date
CN115916853A true CN115916853A (en) 2023-04-04
CN115916853B CN115916853B (en) 2024-07-09

Family

ID=79268040

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202180041285.1A Active CN115916853B (en) 2020-06-15 2021-06-14 Polymer, and photo-alignment film and retardation film using the same

Country Status (5)

Country Link
JP (1) JPWO2021256428A1 (en)
KR (1) KR20230025393A (en)
CN (1) CN115916853B (en)
TW (1) TW202204451A (en)
WO (1) WO2021256428A1 (en)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1219651A1 (en) * 2000-12-29 2002-07-03 Rolic AG Photoactive copolymer
CN101470212A (en) * 2007-12-28 2009-07-01 住友化学株式会社 Optical film
WO2012014915A1 (en) * 2010-07-28 2012-02-02 大阪有機化学工業株式会社 Copolymerizable (meth) acrylic acid polymer, optical alignment film and phase difference film
WO2012093682A1 (en) * 2011-01-07 2012-07-12 大阪有機化学工業株式会社 Composition for photoaligned films and optical anisotropic films
JP2014067038A (en) * 2013-10-16 2014-04-17 Dic Corp Optical anisotropic body
JP2015031823A (en) * 2013-08-02 2015-02-16 大阪有機化学工業株式会社 Photo-alignment film composition and novel polymer
JP2016079189A (en) * 2014-10-09 2016-05-16 Dic株式会社 Copolymer for photo-alignment film
WO2018021328A1 (en) * 2016-07-26 2018-02-01 日産化学工業株式会社 Polymer composition
CN107924092A (en) * 2015-07-06 2018-04-17 日产化学工业株式会社 Liquid crystal orientation film manufacture represents element and its manufacture method with composition, the liquid crystal orientation film and its manufacture method using said composition and the liquid crystal with liquid crystal orientation film
CN109416485A (en) * 2016-04-28 2019-03-01 日产化学株式会社 Aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal indicate element and novel monomeric
WO2020111198A1 (en) * 2018-11-29 2020-06-04 日産化学株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and retardation material

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006126820A (en) * 2004-09-30 2006-05-18 Dainippon Printing Co Ltd Composition for alignment layer, method of manufacturing alignment layer, and optical element
JP2011186387A (en) * 2010-03-11 2011-09-22 Fujifilm Corp Optical alignment film, method of manufacturing the same, and optical film
JP6010911B2 (en) 2012-01-23 2016-10-19 住友化学株式会社 Optical film and manufacturing method thereof
KR101406300B1 (en) 2012-02-29 2014-06-12 김두연 Equipment formation of handle receptacle p.e.t
JP2015172756A (en) * 2015-04-21 2015-10-01 大阪有機化学工業株式会社 Method for manufacturing retardation film
WO2019009222A1 (en) * 2017-07-07 2019-01-10 シャープ株式会社 Liquid crystal composition, liquid crystal display device, and production method for liquid crystal display device

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1219651A1 (en) * 2000-12-29 2002-07-03 Rolic AG Photoactive copolymer
CN101470212A (en) * 2007-12-28 2009-07-01 住友化学株式会社 Optical film
KR20090073000A (en) * 2007-12-28 2009-07-02 스미또모 가가꾸 가부시끼가이샤 Optical film
WO2012014915A1 (en) * 2010-07-28 2012-02-02 大阪有機化学工業株式会社 Copolymerizable (meth) acrylic acid polymer, optical alignment film and phase difference film
WO2012093682A1 (en) * 2011-01-07 2012-07-12 大阪有機化学工業株式会社 Composition for photoaligned films and optical anisotropic films
JP2015031823A (en) * 2013-08-02 2015-02-16 大阪有機化学工業株式会社 Photo-alignment film composition and novel polymer
JP2014067038A (en) * 2013-10-16 2014-04-17 Dic Corp Optical anisotropic body
JP2016079189A (en) * 2014-10-09 2016-05-16 Dic株式会社 Copolymer for photo-alignment film
CN107924092A (en) * 2015-07-06 2018-04-17 日产化学工业株式会社 Liquid crystal orientation film manufacture represents element and its manufacture method with composition, the liquid crystal orientation film and its manufacture method using said composition and the liquid crystal with liquid crystal orientation film
CN109416485A (en) * 2016-04-28 2019-03-01 日产化学株式会社 Aligning agent for liquid crystal, liquid crystal orientation film, liquid crystal indicate element and novel monomeric
WO2018021328A1 (en) * 2016-07-26 2018-02-01 日産化学工業株式会社 Polymer composition
WO2020111198A1 (en) * 2018-11-29 2020-06-04 日産化学株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and retardation material

Also Published As

Publication number Publication date
CN115916853B (en) 2024-07-09
WO2021256428A1 (en) 2021-12-23
JPWO2021256428A1 (en) 2021-12-23
TW202204451A (en) 2022-02-01
KR20230025393A (en) 2023-02-21

Similar Documents

Publication Publication Date Title
JP6250324B2 (en) Composition for photo-alignment film and novel polymer
JP6425021B2 (en) Film with cured film, alignment material, and retardation material
JP5075483B2 (en) Polymer film, method for producing molecular alignment element, and liquid crystal alignment film
KR101833572B1 (en) Copolymerizable (meth)acrylic acid polymer, optical alignment film and phase difference film
WO2013191251A1 (en) Cured film-forming composition, oriented material, and phase difference material
WO2014065324A1 (en) Cured-film-forming composition, alignment material, and phase-difference material
CN113614181B (en) Polymer composition and single layer phase difference material
KR101638789B1 (en) Polymerizable optically active imide compound and polymerizable composition containing the compound
CN113557265B (en) Polymer composition and single layer phase difference material
JP5784323B2 (en) Composition for retardation film
JP7319599B2 (en) Liquid crystal alignment agent, liquid crystal alignment film and retardation material
CN115916853B (en) Polymer, and photo-alignment film and retardation film using the same
CN117677669A (en) Polymer composition and single layer phase difference material
TWI822746B (en) Cured film forming composition, alignment material and retardation material
CN116323702A (en) Method for producing single-layer phase difference material
WO2024038887A1 (en) Polymer composition and single-layer retardation material
WO2024071364A1 (en) Polymer composition and single-layer retardation material
KR20220098362A (en) Manufacturing method of patterned single-layer retardation material
CN116601191A (en) Method for producing single-layer retardation film, and polymer composition for forming single-layer retardation film
WO2024071343A1 (en) Composition, liquid crystal film, film, display device, and dispersant
WO2019027045A1 (en) Cured film forming composition, orienting material, and phase contrast material

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant