WO2023008488A1

WO2023008488A1 - Polymer composition and single-layer retardation material

Info

Publication number: WO2023008488A1
Application number: PCT/JP2022/028970
Authority: WO
Inventors: 大輝山極; 司藤枝
Original assignee: 日産化学株式会社
Priority date: 2021-07-28
Filing date: 2022-07-27
Publication date: 2023-02-02
Also published as: JPWO2023008488A1; TW202313936A; KR20240037250A; CN117677669A

Abstract

Provided is a polymer composition that makes it possible to manufacture a retardation film with less turbidity by means of a simpler process, said polymer composition containing: (A) a block copolymer that contains a photosensitive side-chain polymer block capable of exhibiting liquid crystallinity and a polymer block derived from a polymeric polymerization initiator; and (B) an organic solvent.

Description

Polymer composition and single layer retardation material

The present invention relates to a composition containing a polymer and a single-layer retardation material.

Due to the demand for improved display quality and lighter weight of liquid crystal display devices, there is an increasing demand for polymer films with a controlled internal molecular orientation structure as optical compensation films such as polarizing plates and retardation plates. In order to meet this demand, films utilizing the optical anisotropy possessed by polymerizable liquid crystal compounds have been developed. The polymerizable liquid crystal compound used here is generally a liquid crystal compound having a polymerizable group and a liquid crystal structure portion (a structure portion having a spacer portion and a mesogen portion), and an acrylic group is widely used as the polymerizable group. ing.

Such a polymerizable liquid crystal compound is generally made into a polymer (film) by a method of polymerizing by irradiating it with radiation such as ultraviolet rays. For example, a method of obtaining a polymer by supporting a specific polymerizable liquid crystal compound having an acrylic group between supports and irradiating the compound with radiation while maintaining the compound in a liquid crystal state (Patent Document 1); A method is known in which a photopolymerization initiator is added to a mixture of two types of polymerizable liquid crystal compounds or a composition obtained by mixing this mixture with a chiral liquid crystal, and the mixture is irradiated with ultraviolet rays to obtain a polymer (Patent Document 2).

In addition, alignment films using a polymerizable liquid crystal compound or polymer that does not require a liquid crystal alignment film (Patent Documents 3 and 4), alignment films using a polymer containing a photocrosslinking site (Patent Documents 5 and 6), etc. Various single layer coated oriented films have been reported. A polymer exhibiting a high degree of orientation has a low polymer solubility, and causes problems such as haze (haze, turbidity) and insufficient retardation as a retardation material. A material that solves such problems has not been found so far.

JP-A-62-70407 JP-A-9-208957 European Patent Application Publication No. 1090325 WO2008/031243 JP 2008-164925 A JP-A-11-189665

The present invention has been made in view of the above problems, and a polymer composition that enables the production of a single-layer retardation material with less turbidity by a simpler process, and a single layer obtained from the polymer composition An object is to provide a retardation material.

As a result of intensive studies to solve the above problems, the present inventors have found that by using a composition containing a specific polymer and a specific additive, it is possible to obtain a liquid crystal with little turbidity without using a liquid crystal alignment film. The inventors have found that it is possible to produce a single-layer retardation material having an anisotropy (Δn), and completed the present invention.

Specifically, the present invention provides the following polymer composition and single-layer retardation material.
1. (A) A block copolymer containing a photosensitive side chain type polymer block capable of exhibiting liquid crystallinity and a polymer block derived from a polymer type polymerization initiator, and (B) a polymer composition containing an organic solvent. .
2. 1. The polymer composition of 1, wherein the side chain type polymer block has a side chain represented by any one of the following formulas (a1) to (a6).

(In the formula, n1 and n2 are each independently 0, 1, 2 or 3.
L is a single bond or an alkylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms in the alkylene group may be substituted with halogen atoms.
T ¹ is a single bond or an alkylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms in the alkylene group may be substituted with halogen atoms.
A ¹ , A ² and D ¹ are each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C(= O) —NH— or —NH—C(=O)—. However, when T ¹ is a single bond, A ² is also a single bond.
Y ¹ and Y ² are a phenylene group or a naphthylene group, and part or all of the hydrogen atoms of the phenylene group and naphthylene group are a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. It may be substituted with an alkylcarbonyl group of 5 or an alkoxy group having 1 to 5 carbon atoms.
P ¹ , Q ¹ and Q ² are each independently a single bond, a phenylene group or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and part or all of the hydrogen atoms of the phenylene group are , a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. When the number of Q ¹ is 2 or more, each Q ¹ may be the same or different, and when the number of Q ² is 2 or more, each Q ² may be the same or different.
R is a hydrogen atom, a cyano group, a halogen atom, a carboxy group, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms or a cycloalkyl group having 1 to 5 carbon atoms It is an alkoxy group.
X ¹ and X ² are each independently a single bond, -O-, -C(=O)-O-, -O-C(=O)-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-C(=O)-O- or -O-C(=O)-CH=CH-. When the number of X ¹ is 2 or more, each X ¹ may be the same or different, and when the number of X ² is 2 or more, each X ² may be the same or different.
Cou is a coumarin-6-yl group or a coumarin-7-yl group, and some of the hydrogen atoms bonded to them are -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH- It may be substituted with CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-.
G ¹ and G ² are each independently N or CH.
A dashed line is a bond. )
3. 1 or 2 polymer compositions, wherein the side chain type polymer block further has side chains that are neither photodimerizable nor photoisomerizable.
4. 3. The polymer composition of 3, wherein the side chain that neither photodimerizes nor photoisomerizes is represented by any one of the following formulas (b1) to (b11).

(wherein A ³ and A ⁴ are each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C( =O)-NH- or -NH-C(=O)- When the number of A ⁴ is 2 or more, each A ⁴ may be the same or different.
R ¹ is —NO ₂ , —CN, halogen atom, phenyl group, naphthyl group, biphenylyl group, furanyl group, monovalent nitrogen-containing heterocyclic group, monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, carbon It is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.
R ² is a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group or a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and part of the hydrogen atoms of these groups Alternatively, all of them may be substituted with —NO ₂ , —CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
R ³ is a hydrogen atom, —NO ₂ , —CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, or a monovalent alicyclic hydrocarbon having 5 to 8 carbon atoms; , an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.
E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-.
a is an integer from 1 to 12;
k1 to k5 are each independently an integer of 0 to 2, but the sum of k1 to k5 is 2 or more.
k6 and k7 are each independently an integer of 0 to 2, and the sum of k6 and k7 is 1 or more.
m1, m2 and m3 are each independently an integer of 1-3.
n is 0 or 1;
Z ¹ and Z ² are each independently a single bond, -C(=O)-, -CH ₂ -O-, or -CF ₂ -.
A dashed line is a bond. )
5. 4. The polymer composition according to any one of 1 to 4, wherein the polymer type polymerization initiator has a repeating unit represented by the following formula (1).

In the formula, R ^a1 to R ^a4 are each independently a linear or branched alkyl group having 1 to 6 carbon atoms or a cyano group. R ^L1 and R ^L2 are each independently an alkylene group having 1 to 10 carbon atoms. L ¹ and L ² each independently represent -C(=O)-O-, -OC(=O)-, -C(=O)-NH- or -NH-C(=O)- is. X is a divalent group represented by the following formula (2) or (3).

In the formula, R ^a5 to R ^a8 are linear or branched C 1-6 alkyl groups or C 6-12 aryl groups. R ^a9 and R ^a10 are each independently an alkylene group having 1 to 10 carbon atoms. R ^L3 and R ^L4 are each independently an alkylene group having 1 to 10 carbon atoms. x and y are each independently positive integers.
6. 5. The polymer composition of 5, wherein the polymer type polymerization initiator is represented by any one of the following formulas (In-1) to (In-2).

(Wherein, x and y are the same as above. n is a positive integer.)
7. (I) a step of applying the polymer composition of any one of 1 to 6 onto a substrate to form a coating film;
(II) a step of irradiating the coating film with polarized ultraviolet rays; and (III) a step of heating the coating film irradiated with the ultraviolet rays to obtain a retardation material.
8. A single-layer retardation material obtained from the polymer composition of any one of 1 to 6.

According to the present invention, it is possible to provide a single-layer retardation material that exhibits retardation with little turbidity, and a polymer composition that provides it.

As a result of intensive research, the inventors of the present invention have obtained the following knowledge and completed the present invention.
The polymer composition of the present invention comprises a photosensitive side-chain polymer block capable of exhibiting liquid crystallinity (hereinafter also simply referred to as a side-chain polymer block) and a polymer derived from a polymer-type polymerization initiator (hereinafter , Also simply referred to as an initiator-derived polymer block. The film becomes a film having photosensitive side chains capable of exhibiting liquid crystallinity. This coating film is subjected to an orientation treatment by irradiating polarized light without performing a rubbing treatment. After irradiating polarized light, the polymer film is heated to obtain a film imparted with optical anisotropy (hereinafter also referred to as a single-layer retardation material). At this time, the slight anisotropy generated by polarized light irradiation becomes a driving force, and the side chain type block copolymer itself is efficiently reoriented by self-organization. As a result, a highly efficient orientation treatment is realized, and a single-layer retardation material imparted with high optical anisotropy can be obtained.

Further, in the polymer composition of the present invention, the polymer of component (A) comprises a photosensitive side-chain polymer block capable of exhibiting liquid crystallinity and a polymer block derived from a polymer-type polymerization initiator. It is characterized by being a block copolymer containing. As a result, the molecular mobility in the solvent of the side chain type block copolymer of the component (A) is improved. As a result, the visible haze is suppressed. It should be noted that these include the opinion of the inventor regarding the mechanism of the present invention, and do not limit the present invention.

Hereinafter, embodiments of the present invention will be described in detail.
The polymer composition of the present invention comprises (A) a block copolymer containing a side chain type polymer block having a side chain having a photoreactive site and a polymer block derived from a polymer type polymerization initiator, and (B ) containing an organic solvent.

[(A) Side chain type block copolymer]
Component (A) is a photosensitive side chain type block copolymer that exhibits liquid crystallinity in a predetermined temperature range, and is a side chain type polymer block having a side chain having a photoreactive site and a polymer type polymerization. and a polymer block derived from the initiator. The side chain type polymer block has a photoreactive site that reacts with ultraviolet light in the side chain. It contains a side chain. The initiator-derived polymer block has a main chain derived from a predetermined polymerization initiator described later. A coating film obtained from a polymer composition containing such a side chain type block copolymer has liquid crystallinity and photosensitivity due to the side chain type polymer block, and high solvent solubility due to the initiator-derived polymer block. , it becomes a film having film flexibility (ability to lower the glass transition temperature). This coating film is subjected to an orientation treatment by irradiating polarized light without performing a rubbing treatment. After irradiation with polarized light, the side chain type polymer film is heated to obtain a film (single-layer retardation film) imparted with optical anisotropy. At this time, the slight anisotropy generated by polarized light irradiation becomes a driving force, and the side chain type block copolymer itself is efficiently reoriented by self-organization. As a result, a highly efficient orientation treatment is realized as a single-layer retardation film, and a single-layer retardation film imparted with high optical anisotropy can be obtained.

In the present invention, photoreactivity refers to (A-1) photocrosslinking (photodimerization) reaction, (A-2) photoisomerization, or (A-3) photofries rearrangement reaction; or a plurality of reactions ; refers to the property that causes

The side chain type block copolymer is (i) a polymer that exhibits liquid crystallinity in a predetermined temperature range and has a photoreactive side chain. The side-chain type block copolymer (ii) preferably reacts with light in the wavelength range of 200 to 400 nm, preferably 240 to 400 nm, and exhibits liquid crystallinity in the temperature range of 50 to 300.degree. The side-chain type block copolymer preferably has (iii) a photoreactive side chain that reacts with light in the wavelength range of 200 to 400 nm, preferably 240 to 400 nm, particularly polarized ultraviolet light. The side chain type block copolymer (iv) preferably has a mesogenic group in order to exhibit liquid crystallinity in the temperature range of 50 to 300°C.

The side chain type block copolymer has a photoreactive side chain having photoreactivity as described above. The structure of the side chain is not particularly limited, but has a structure that causes the reactions (A-1), (A-2) and/or (A-3), particularly (A-1) photocrosslinking It preferably has a structure that causes reaction and/or (A-2) photoisomerization reaction. (A-1) The structure that causes the photocrosslinking reaction is such that the orientation of the side chain type polymer block can be stably maintained for a long period of time even when the structure after the reaction is exposed to external stress such as heat. is preferred. In addition, (A-2) the structure that causes a photoisomerization reaction enables alignment treatment with a low exposure amount compared to photocrosslinking and photofleece transfer, and can increase production efficiency during retardation film production. preferable.

The structure of the side chain of the side chain type polymer block preferably has a rigid mesogenic component because the alignment of the liquid crystal is stabilized. Mesogenic moieties include, but are not limited to, biphenyl groups, terphenyl groups, phenylcyclohexyl groups, phenylbenzoate groups, and the like.

The side chain having a photoreactive site that photoreacts with ultraviolet light contained in the side chain type polymer block (hereinafter also referred to as side chain a) is represented by any of the following formulas (a1) to (a6). is preferred. From the viewpoint of solubility in a solvent, the number of benzene rings possessed by one side chain a is preferably 3 or less.

In formulas (a1) to (a6), n1 and n2 are each independently 0, 1, 2 or 3. L is a single bond or an alkylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms in the alkylene group may be substituted with halogen atoms. T ¹ is a single bond or an alkylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms in the alkylene group may be substituted with halogen atoms. A ¹ , A ² and D ¹ are each independently a single bond, -O-, -CH ₂ -, -C(=O)-O-, -OC(=O)-, -C(= O) —NH— or —NH—C(=O)—. However, when T ¹ is a single bond, A ² is also a single bond. Y ¹ and Y ² are a phenylene group or a naphthylene group, and part or all of the hydrogen atoms of the phenylene group and naphthylene group are a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. It may be substituted with an alkylcarbonyl group of 5 or an alkoxy group having 1 to 5 carbon atoms. P ¹ , Q ¹ and Q ² are each independently a single bond, a phenylene group or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and part or all of the hydrogen atoms of the phenylene group are , a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. When the number of Q ¹ is 2 or more, each Q ¹ may be the same or different, and when the number of Q ² is 2 or more, each Q ² may be the same or different. R is a hydrogen atom, a cyano group, a halogen atom, a carboxy group, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms or a cycloalkyl group having 1 to 5 carbon atoms It is an alkoxy group. X ¹ and X ² are each independently a single bond, -O-, -C(=O)-O-, -O-C(=O)-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-C(=O)-O- or -O-C(=O)-CH=CH-. When the number of X ¹ is 2 or more, each X ¹ may be the same or different, and when the number of X ² is 2 or more, each X ² may be the same or different. Cou is a coumarin-6-yl group or a coumarin-7-yl group, and some of the hydrogen atoms bonded to them are -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH- It may be substituted with CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-. G ¹ and G ² are each independently N or CH. A dashed line is a bond.

The alkylene group having 1 to 12 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methylene group, ethylene group, propane-1,3-diyl group, butane-1,4 -diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane -1,10-diyl group and the like.

The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like.

The alkyl group having 1 to 5 carbon atoms may be linear or branched, and specific examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and tert-butyl. group, n-pentyl group, and the like.

Specific examples of the alkylcarbonyl group having 1 to 5 carbon atoms include methylcarbonyl (acetyl) group, ethylcarbonyl group, n-propylcarbonyl group, n-butylcarbonyl group, n-pentylcarbonyl group and the like.

Specific examples of the alkoxy group having 1 to 5 carbon atoms include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, n-pentyloxy group and the like.

Specific examples of the divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms include a cyclopentanediyl group, a cyclohexanediyl group, a cycloheptanediyl group, and a cyclooctanediyl group.

Specific examples of the cycloalkyl group having 3 to 7 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.

As the side chain a, the following formula (a1-1), (a1-2), (a2-1), (a3-1), (a4-1), (a5-1) or (a6-1) Those represented are more preferred.

(In the formula, L, A ¹ , A ² , Y ¹ , Y ² , Q ¹ , T ¹ , R, X ¹ , Cou, E, G ¹ , G ² , n1 and dashed line are the same as above. P ^{1 '} is a phenylene group or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and part or all of the hydrogen atoms of the phenylene group are a cyano group, a halogen atom, or an alkyl group having 1 to 5 carbon atoms. group, an alkylcarbonyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.)

The side chain represented by the formula (a1-1) is preferably a side chain represented by the following formula (a1-1-1), and the side chain represented by the formula (a1-2) is represented by the formula ( A side chain represented by a1-2-1) is preferred.

(In the formula, L, R and dashed lines are the same as above.)

The side chain represented by formula (a2-1) is preferably a side chain represented by formula (a2-1-1) below.

(In the formula, L, A ² , Q ¹ , T ¹ , R and dashed lines are the same as above.)

The side chain represented by formula (a3-1) is preferably a side chain represented by formula (a3-1-1), (a3-1-2) or (a3-1-3) below.

(In the formula, L, Cou and dashed line are the same as above.)

The side chain represented by formula (a4-1) is represented by the following formula (a4-1-1), (a4-1-2), (a4-1-3) or (a4-1-4) are preferred.

(In the formula, L, R and dashed lines are the same as above.)

The side chain represented by formula (a5-1) is preferably a side chain represented by formula (a5-1-1) or (a5-1-2) below.

(In the formula, L, R and dashed lines are the same as above.)

The side chain represented by formula (a6-1) is preferably a side chain represented by formula (a6-1-1), (a6-1-2) or (a6-1-3) below.

(In the formula, L, R and dashed lines are the same as above.)

(A) The side-chain block copolymer has a photosensitive side chain bonded to the main chain of the side-chain type polymer block, and has an optimum light selected from a wavelength of 200 to 400 nm, particularly a wavelength of 254 nm. , 313 nm or 365 nm light to cause cross-linking reactions, isomerization reactions or Fries rearrangements. The structure of the photosensitive side-chain type polymer block is not particularly limited as long as it satisfies such properties, but it is preferable to have a rigid mesogenic component in the side-chain structure. A stable optical anisotropy can be obtained when the side chain type block copolymer is formed into a single-layer retardation film.

More specific examples of the structure of the side-chain polymer block include radically polymerizable groups such as (meth)acrylate, itaconate, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide and norbornene. and siloxane, and a structure having a side chain a is preferred.

In addition, the side chain type polymer block may further include a side chain that neither photodimerizes nor photoisomerizes (hereinafter also referred to as side chain b). Such a side chain b is preferably represented by one of the following formulas (b1) to (b11), but is not limited thereto.

In formulas (b1) to (b11), A ³ and A ⁴ are each independently a single bond, —O—, —CH ₂ —, —C(=O)—O—, —OC(=O )-, -C(=O)-NH-, or -NH-C(=O)-. When the number of A ⁴ is 2 or more, each A ⁴ may be the same or different. R ¹ is —NO ₂ , —CN, halogen atom, phenyl group, naphthyl group, biphenylyl group, furanyl group, monovalent nitrogen-containing heterocyclic group, monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, carbon It is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. R ² is a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group or a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and part of the hydrogen atoms of these groups Alternatively, all of them may be substituted with —NO ₂ , —CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. R ³ is a hydrogen atom, —NO ₂ , —CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, or a monovalent alicyclic hydrocarbon having 5 to 8 carbon atoms; , an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-. a is an integer from 1 to 12; k1 to k5 are each independently an integer of 0 to 2, but the sum of k1 to k5 is 2 or more. k6 and k7 are each independently an integer of 0 to 2, and the sum of k6 and k7 is 1 or more. m1, m2 and m3 are each independently an integer of 1-3. n is 0 or 1; Z ¹ and Z ² are each independently a single bond, -C(=O)-, -CH ₂ -O-, or -CF ₂ -. A dashed line is a bond.

Specific examples of the monovalent nitrogen-containing heterocyclic group include a pyrrolidinyl group, a piperidinyl group, a piperazinyl group, a pyrrolyl group, a pyridyl group, and the like. Specific examples of the monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms include cyclopentyl and cyclohexyl groups. Further, examples of the alkyl group and alkoxy group include the same groups as those exemplified in the description of the formulas (a1) to (a6).

The side chain type polymer block can be obtained by polymerizing a monomer that provides the side chain a and, if necessary, a monomer that provides the side chain b.

Examples of the monomer that provides the side chain a (hereinafter also referred to as monomer MA) include compounds represented by the following formulas (M1), (M2), (M3), (M4), (M5) and (M6). be done.

(wherein A ¹ , A ² , D ¹ , L, T ¹ , Y ¹ , Y ² , P ¹ , Q ¹ , Q ² , R, Cou, E, X ¹ , X ² , G ¹ , G ² , n1 and n2 are the same as above.)

In the formulas (M1) to (M6), PG is a polymerizable group, preferably a group represented by any one of the following formulas (PG1) to (PG6). Among them, the acryl group or methacryl group represented by the formula (PG1) is preferable from the viewpoint of easy control of the polymerization reaction and stability of the polymer.

(Wherein, ^RA is a hydrogen atom or a methyl group, and the dashed line is a bond with L.)

As the compound represented by formula (M1), one represented by the following formula (M1-1) or (M1-2) is preferable.

(In the formula, PG, L, Y ¹ , P ^1' and R are the same as above.)

As the compound represented by formula (M2), one represented by the following formula (M2-1) is preferable.

(In the formula, PG, A ² , L, T ¹ , Y ¹ , P ¹ , Q ¹ and R are the same as above.)

As the compound represented by formula (M3), one represented by the following formula (M3-1) is preferable.

(In the formula, PG, A ¹ , L, X ¹ , Q ¹ , Cou and n1 are the same as above.)

As the compound represented by formula (M4), one represented by the following formula (M4-1) is preferable.

(In the formula, PG, A ¹ , L, X ¹ , Y ¹ , Y ² , Q ¹ , E, R and n1 are the same as above.)

As the compound represented by formula (M5), one represented by the following formula (M5-1) is preferable.

(In the formula, PG, A ¹ , L, X ¹ , Y ¹ , Y ² , Q ¹ , R and n1 are the same as above.)

As the compound represented by formula (M6), one represented by the following formula (M6-1) is preferable.

(wherein PG, A ¹ , L, X ¹ , Y ¹ , Y ² , Q ¹ , G ¹ , G ² , R and n1 are the same as above).

The compound represented by formula (M1-1) is preferably represented by the following formula (M1-1-1), and the compound represented by formula (M1-2) is preferably represented by the following formula (M1- 2-1) is preferred.

(In the formula, PG, L and R are the same as above.)

As the compound represented by the formula (M2-1), one represented by the following formula (M2-2) is preferable.

(In the formula, PG, A ² , L, T ¹ , Q ¹ and R are the same as above.)

As the compound represented by the formula (M3-1), those represented by the following formulas (M3-2), (M3-3) or (M3-4) are preferable.

(In the formula, PG, L and Cou are the same as above.)

As the compound represented by the formula (M4-1), those represented by the following formulas (M4-2), (M4-3), (M4-4) or (M4-5) are preferable.

(In the formula, PG, L and R are the same as above.)

As the compound represented by the formula (M5-1), those represented by the following formula (M5-2) or (M5-3) are preferable.

(In the formula, PG, L and R are the same as above.)

As the compound represented by the formula (M6-1), those represented by the following formulas (M6-2), (M6-3), or (M6-4) are preferable.

(In the formula, PG, L and R are the same as above.)

Examples of the compound represented by formula (M1) include those represented by any one of the following formulas (A-1-1-1) to (A-1-1-12). In the following formulas (A-1-1-1) to (A-1-1-12), PG is a polymerizable group, s1 represents the number of methylene groups and is an integer of 2-9. R ¹¹ is -H, -CH ₃ , -OCH ₃ , -C(CH ₃ ) ₃ , -C(=O)-CH ₃ or -CN, and R ¹² is -H, -CH ₃ , - CN or -F.

Furthermore, the compound represented by formula (M1) includes, for example, those represented by any one of the following formulas (A-1-2-1) to (A-1-2-4). In the formula below, PG is a polymerizable group, and s1 is the same as above.

Specific examples of the compound represented by formula (M1) include 4-(6-methacryloxyhexyl-1-oxy)cinnamic acid, 4-(6-acryloxyhexyl-1-oxy)cinnamic acid, 4 -(3-methacryloxypropyl-1-oxy)cinnamic acid, 4-[4-(6-methacryloxyhexyl-1-oxy)benzoyloxy]cinnamic acid and the like.

Examples of the compound represented by formula (M2) include those represented by any one of the following formulas (A-2-1) to (A-2-9). In the following formulas (A-2-1) to (A-2-9), PG is a polymerizable group, s1 and s2 represent the number of methylene groups, each independently an integer of 2 to 9 be. R ²¹ is -CH ₃ , -OCH ₃ , -C(CH ₃ ) ₃ , -C(=O)-CH ₃ , -CN or -F.

Examples of the compound represented by formula (M3) include those represented by any one of the following formulas (A-3-1) to (A-3-5). In the formula below, PG is a polymerizable group, and s1 is the same as above.

Examples of the compound represented by formula (M4) include those represented by any one of the following formulas (A-4-1) to (A-4-4). In the formula below, PG is a polymerizable group, and s1 is the same as above.

Examples of the compound represented by formula (M5) include those represented by any one of the following formulas (A-5-1) to (A-5-3). In the formula below, PG is a polymerizable group, and s1 is the same as above.

Examples of the compound represented by formula (M6) include those represented by any one of the following formulas (A-6-1) to (A-6-3). In the formula below, PG is a polymerizable group, and s1 is the same as above.

Some of the above monomers are commercially available, and others can be produced by the method described in, for example, International Publication No. 2014/074785.

An example of a monomer that gives a side chain b that does not undergo photodimerization or photoisomerization (hereinafter also referred to as monomer MB) is a monomer capable of forming a mesogenic group on the side chain.

The mesogenic group may be a group such as biphenyl or phenylbenzoate that forms a mesogenic structure by itself, or a group such as benzoic acid that forms a mesogenic structure by hydrogen bonding between side chains. As the mesogenic group having a side chain, the following structure is preferable.

Specific examples of the monomer MB include radically polymerizable groups such as hydrocarbons, (meth)acrylates, itaconates, fumarate, maleates, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norbornene, and siloxanes. and a polymerizable group derived from at least one of the formulas (b1) to (b11). In particular, the monomer MB preferably has a polymerizable group derived from (meth)acrylate.

Preferred examples of the monomer MB include those represented by the following formulas (MB-1) to (MB-8). In the formula below, PG is a polymerizable group, p represents the number of methylene groups and is an integer of 2-9.

In addition, other monomers can be copolymerized within a range that does not impair the ability to express photoreactivity and/or liquid crystallinity. Examples of the other monomers include industrially available radical polymerizable monomers. Specific examples of the other monomers include unsaturated carboxylic acids, acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

Specific examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.

Specific examples of the acrylic ester compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert -butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclo[5.2.1.0(2,6)]decyl acrylate, 8-ethyl-8-tricyclo[5.2.1.0(2 , 6)] and decyl acrylate.

Specific examples of the methacrylate compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthrylmethyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert. -butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclo[5.2.1.0(2,6)]decyl methacrylate, 8-ethyl-8-tricyclo[5.2.1.0(2 , 6)] and decyl methacrylate.

Specific examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

Specific examples of the styrene compound include styrene, 4-methylstyrene, 4-chlorostyrene, 4-bromostyrene and the like.

Specific examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like.

The contents of the side chain a and the side chain b in the side chain type polymer block are not particularly limited. A homopolymer containing 100 mol % of side chains a may be used, or two or more types of side chains a may be used. In the case of a copolymer of side chain a and side chain b, the side chain a is preferably 5 to 99.9 mol%, more preferably 5 to 95 mol%, from the viewpoint of photoreactivity, and from the viewpoint of photostability. 5 to 50 mol % is even more preferred. From the viewpoint of photoreactivity, the side chain b is preferably 95 mol % or less, more preferably 5 to 95 mol %, and still more preferably 50 mol % or more from the viewpoint of photostability. Even in the case of a copolymer, two or more types of side chains a and side chains b may be used.

The side chain type polymer block may contain other side chains. The content of other side chains is the remainder when the total content of side chains a and b is less than 100 mol %.

The method for producing the side chain type block copolymer is not particularly limited, and a general-purpose method that is industrially used can be used. Specifically, it can be produced by mixing a monomer MA, optionally a monomer MB and other monomers, and a polymer-type polymerization initiator, and subjecting the mixture to radical polymerization in a solvent. In the present invention, a polymer type polymerization initiator means a polymerization initiator having a polymer segment and a polymerization initiation active group. In addition, the polymer segment is a portion that becomes the initiator-derived polymer block in the side chain type block copolymer.

As the polymer-type polymerization initiator, one having a repeating unit represented by the following formula (1) is preferable.

In formula (1), R ^a1 to R ^a4 are each independently a linear or branched alkyl group having 1 to 6 carbon atoms or a cyano group. R ^L1 and R ^L2 are each independently an alkylene group having 1 to 10 carbon atoms. L ¹ and L ² each independently represent -C(=O)-O-, -OC(=O)-, -C(=O)-NH- or -NH-C(=O)- is. X is a divalent group represented by the following formula (2) or (3).

In formulas (2) and (3), R ^a5 to R ^a8 are linear or branched C 1-6 alkyl groups or C 6-12 aryl groups.
R ^a9 and R ^a10 are each independently an alkylene group having 1 to 10 carbon atoms.
R ^L3 and R ^L4 are each independently an alkylene group having 1 to 10 carbon atoms.
Each of x and y is independently a positive integer, usually 5 to 2,000, preferably 5 to 1,000, more preferably 10 to 300, still more preferably 10 to 200.

Linear or branched C 1-6 alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group and n-pentyl group. , isopentyl group, neopentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like.

The alkylene group having 1 to 10 carbon atoms may be linear, branched or cyclic, and specific examples include methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hepta methylene group, octamethylene group, nonamethylene group, decamethylene group, 2-methylpropylene group, 1-methylethylidene group, cyclohexylene group and the like.

Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-biphenylyl group and 2-biphenylyl group.

R ^a1 to R ^a4 are preferably an alkyl group having 1 to 3 carbon atoms or a cyano group, more preferably a methyl group or a cyano group.
R ^L1 and R ^L2 are preferably C 1-5 alkylene groups, more preferably C 1-3 alkylene groups.
L ¹ is preferably -C(=O)-O- or -C(=O)-NH-. L ² is preferably -OC(=O)- or -NH-C(=O)-. In particular, L ¹ is -C(=O)-O- and L ² is -O-C(=O)-, and L ¹ is -C(=O)-NH- and L ² is -NH A combination of -C(=O)- is more preferred.
Regarding X, R ^a5 to R ^a8 are preferably alkyl groups having 1 to 3 carbon atoms, more preferably methyl groups or ethyl groups.
R ^a9 and R ^a10 are preferably C 1-5 alkylene groups, more preferably C 1-3 alkylene groups.
R ^L3 and R ^L4 are preferably C 1-5 alkylene groups, more preferably C 1-3 alkylene groups.

Specific examples of the polymer type polymerization initiator include a polyethylene glycol unit-containing polymeric azo polymerization initiator represented by the following formula (In-1), and a polydimethylsiloxane unit-containing polymer represented by the following formula (In-2). Molecular azo polymerization initiators and the like can be mentioned.

In formulas (In-1) and (In-2), x and y are the same as above. n is a positive integer, usually 1-100, preferably 3-50, more preferably 5-30.

Commercially available products can be used as the polymer-type polymerization initiator. For example, VPE-0201 as the polymerization initiator represented by the formula (In-1) and polymerization represented by the formula (In-2) Examples of the initiator include VPS-1001N (both manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.).

The organic solvent used for the polymerization reaction is not particularly limited as long as it dissolves the polymer produced. Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-ε-caprolactam, dimethylsulfoxide, and tetramethylurea. , pyridine, dimethylsulfone, hexamethylphosphoric acid triamide, γ-butyrolactone, γ-valerolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl Cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol Monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono Acetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1,4-dioxane, n-hexane, n-pentane, n-octane, diethyl ether, Cyclohexanone, cyclopentanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate , 3-ethoxypro ethyl pyonate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone , 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide and the like. These organic solvents may be used singly or in combination of two or more.

Furthermore, even a solvent that does not dissolve the generated polymer may be mixed with the above-described organic solvent and used as long as the generated polymer does not precipitate.

In radical polymerization, oxygen in an organic solvent inhibits the polymerization reaction, so it is preferable to use an organic solvent that has been degassed to the extent possible.

The polymerization temperature during radical polymerization can be selected from any temperature in the range of 20 to 150°C, preferably in the range of 30 to 100°C. In addition, the reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a high-molecular-weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high, making uniform stirring difficult. Therefore, the monomer concentration is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction can be carried out at a high concentration, and then the organic solvent can be added.

In the radical polymerization reaction described above, the amount of the polymer polymerization initiator to be used is determined, in consideration of the half-life of the polymer polymerization initiator, in order to facilitate the progress of the radical polymerization. It is preferably 0.01 to 0.2 with respect to 1 of the total amount of monomers that provide blocks. Further, various monomer components, solvents, initiators, etc. may be added during polymerization.

The side-chain block copolymer produced from the reaction solution obtained by the above reaction can be recovered by putting the reaction solution into a poor solvent to precipitate it, but this reprecipitation treatment is not essential. Poor solvents used for precipitation include methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer precipitated by putting it into the poor solvent can be filtered and recovered, and then dried at room temperature or under heat under normal pressure or reduced pressure. In addition, impurities in the polymer can be reduced by repeating the operation of redissolving the recovered polymer in an organic solvent and recovering it by reprecipitation 2 to 10 times. Examples of the poor solvent in this case include alcohols, ketones, hydrocarbons, and the like. It is preferable to use three or more poor solvents selected from these, because the purification efficiency is further improved.

The ratio (molar ratio) of the side chain type polymer block and the initiator-derived polymer block in the side chain type block copolymer is roughly the total amount of the monomers providing the side chain type polymer block and the total amount of the polymer type polymerization initiator. Conforms to usage.

The weight-average molecular weight (Mw) of the side chain type block copolymer used in the present invention is 2,000 to 2,000 to 2,000, considering the strength of the resulting coating film, the workability during coating film formation, and the uniformity of the coating film. 000,000 is preferred, 2,000 to 1,000,000 is more preferred, and 5,000 to 200,000 is even more preferred. In addition, in this invention, Mw is a polystyrene equivalent measurement value by a gel permeation chromatography (GPC) method.

[(B) Organic solvent]
The polymer composition of the present invention contains an organic solvent (good solvent). The organic solvent (good solvent) is not particularly limited as long as it dissolves the polymer component. Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methyl-ε-caprolactam, 2-pyrrolidone, N-ethyl-2-pyrrolidone, N- Vinyl-2-pyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphoramide, γ-butyrolactone, 3-methoxy-N,N-dimethylpropanamide, 3-ethoxy-N,N-dimethylpropane amide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl-2-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, cyclopentanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, tetrahydrofuran, tetrahydrofurfuryl alcohol and the like. These may be used individually by 1 type, and may be used in mixture of 2 or more types.

In addition, the polymer composition may contain components other than the side-chain block copolymer and the organic solvent (good solvent). Examples thereof include solvents (poor solvents) and compounds that improve the film thickness uniformity and surface smoothness when the polymer composition is applied, and compounds that improve the adhesion between the retardation film and the substrate. but not limited to these.

Specific examples of the solvent (poor solvent) that improves the film thickness uniformity and surface smoothness include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether (butyl cellosolve), propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, Dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl Ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl Butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, 1-hexanol, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, n-propyl lactate, lactic acid n-butyl, isoamyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxy ethyl propionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy- 2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, etc. Solvents can be mentioned.

The poor solvent may be used singly or in combination of two or more. When a poor solvent is used, its content is preferably 5 to 80% by mass, more preferably 10 to 60% by mass in the solvent so as not to significantly lower the solubility of the polymer.

Compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. Specific examples thereof include Ftop (registered trademark) 301, EF303, EF352 (manufactured by Tochem Products), Megafac (registered trademark) F171, F173, F560, F563, R-30, R-40, R- 41 (manufactured by DIC), Florard FC430, FC431 (manufactured by 3M), Asahiguard (registered trademark) AG710 (manufactured by AGC), Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Seimi Chemical Co., Ltd.), BYK-302, BYK-331, BYK-348, BYK-360N, BYK-381, BYK-3441 (manufactured by BYK) and the like. The content of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of component (A).

Specific examples of the compound that improves the adhesion between the retardation film and the substrate include functional silane-containing compounds, and specific examples thereof include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxy Silane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane Silane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyl triethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3, 6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl- 3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltriethoxy Silane etc. are mentioned.

The polymer composition contains a phenoplast-based compound and an epoxy group-containing compound for the purpose of improving the adhesion between the substrate and the retardation film and preventing deterioration of characteristics due to backlight when the polarizing plate is constructed. It's okay.

Specific examples of the phenoplast-based compound include, but are not limited to, those shown below.

Specific examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N' , N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, etc. is mentioned.

When using a compound that improves adhesion to the substrate, the content thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the side chain block copolymer contained in the polymer composition. ~20 parts by mass is more preferable. If the content is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.

A photosensitizer can also be used as an additive. Preferred photosensitizers are colorless sensitizers and triplet sensitizers.

Examples of photosensitizers include aromatic nitro compounds, coumarin (7-diethylamino-4-methylcoumarin, 7-hydroxy-4-methylcoumarin), ketocoumarin, carbonylbiscoumarin, aromatic 2-hydroxyketone, aromatic 2-hydroxy Ketones (2-hydroxybenzophenone, mono- or di-p-(dimethylamino)-2-hydroxybenzophenone, etc.), acetophenone, anthraquinone, xanthone, thioxanthone, benzantrone, thiazoline (2-benzoylmethylene-3-methyl-β- Naphthothiazoline, 2-(β-naphthoylmethylene)-3-methylbenzothiazoline, 2-(α-naphthoylmethylene)-3-methylbenzothiazoline, 2-(4-biphenoylmethylene)-3-methylbenzothiazoline , 2-(β-naphthoylmethylene)-3-methyl-β-naphthothiazoline, 2-(4-biphenoylmethylene)-3-methyl-β-naphthothiazoline, 2-(p-fluorobenzoylmethylene)-3 -methyl-β-naphthothiazoline, etc.), oxazoline (2-benzoylmethylene-3-methyl-β-naphthoxazoline, 2-(β-naphthoylmethylene)-3-methylbenzoxazoline, 2-(α-naphthoylmethylene) )-3-methylbenzoxazoline, 2-(4-biphenoylmethylene)-3-methylbenzoxazoline, 2-(β-naphthoylmethylene)-3-methyl-β-naphthoxazoline, 2-(4-biphenoyl methylene)-3-methyl-β-naphthoxazoline, 2-(p-fluorobenzoylmethylene)-3-methyl-β-naphthoxazoline, etc.), benzothiazole, nitroaniline (m- or p-nitroaniline, 2,4 , 6-trinitroaniline, etc.), nitroacenaphthene (5-nitroacenaphthene, etc.), 2-[(m-hydroxy-p-methoxy)styryl]benzothiazole, benzoin alkyl ether, N-alkylated phthalone, acetophenone ketal (2,2-dimethoxyphenylethanone, etc.), naphthalene (2-naphthalenemethanol, 2-naphthalenecarboxylic acid, etc.), anthracene (9-anthracenemethanol, 9-anthracenecarboxylic acid, etc.), benzopyran, azoindolizine, merocumarin, etc. is mentioned. Among these, aromatic 2-hydroxyketones (benzophenones), coumarins, ketocoumarins, carbonylbiscoumarins, acetophenones, anthraquinones, xanthones, thioxanthones and acetophenone ketals are preferred.

In addition to those described above, the polymer composition may contain a dielectric substance or a conductive substance for the purpose of changing the electrical properties of the retardation film, such as the dielectric constant and conductivity, as long as the effects of the present invention are not impaired. Furthermore, a cross-linking compound may be added for the purpose of increasing the hardness and denseness of the retardation film.

The polymer composition is preferably prepared as a coating liquid so as to be suitable for forming a single-layer retardation film. That is, the polymer composition used in the present invention includes a side chain type block copolymer, a compound that improves film thickness uniformity and surface smoothness described above, a compound that improves adhesion to a substrate, etc. It is preferably prepared as a solution dissolved in (a good solvent).

The content of the side chain type block copolymer in the polymer composition is preferably 1 to 30% by mass, more preferably 3 to 25% by mass.

In addition to the side chain block copolymer, the polymer composition may contain other polymers within a range that does not impair the ability to develop liquid crystals and the photosensitive performance. Examples of the other polymers include polymers that do not contain photosensitive side chains capable of exhibiting liquid crystallinity, such as poly(meth)acrylates, polyamic acids, and polyimides. When the other polymer is included, the content thereof is preferably 0.5 to 80% by mass, more preferably 1 to 50% by mass, based on the total polymer components.

In the polymer composition of the present invention, in addition to those described above, dielectrics and A cross-linking compound may be added for the purpose of increasing the hardness and denseness of the film when used as a retardation material, as well as the conductive substance.

[Preparation of polymer composition]
The polymer composition of the present invention is preferably prepared as a coating liquid so as to be suitable for forming a single-layer retardation material. That is, the polymer composition used in the present invention includes the component (A), the solvents and compounds that improve the film thickness uniformity and surface smoothness described above, the compounds that improve the adhesion between the liquid crystal alignment film and the substrate, and the like. is preferably prepared as a solution in the organic solvent of component (B). Here, the content of component (A) is preferably 1 to 30% by mass, more preferably 3 to 25% by mass, in the polymer composition of the present invention.

[Single layer retardation material]
The single-layer retardation material of the present invention can be produced by a method including the following steps (I) to (III).
(I) a step of applying the polymer composition of the present invention onto a substrate to form a coating film;
(II) a step of irradiating the coating film with polarized ultraviolet rays; and (III) a step of heating the coating film irradiated with the ultraviolet rays to obtain a retardation material.

[Step (I)]
Step (I) is a step of applying the polymer composition of the present invention onto a substrate to form a coating film. More specifically, the polymer composition of the present invention can be applied to substrates (e.g., silicon/silicon dioxide coated substrates, silicon nitride substrates, metal (e.g., aluminum, molybdenum, chromium, etc.) coated substrates, glass substrates, Quartz substrate, ITO substrate, etc.) or film (for example, triacetyl cellulose (TAC) film, cycloolefin polymer film, polyethylene terephthalate film, resin film such as acrylic film), etc., are bar-coated, spin-coated, flow-coated, It is applied by a method such as roll coating, slit coating, spin coating subsequent to slit coating, inkjet method, or printing method. After coating, the solvent is evaporated at 50 to 200° C., preferably 50 to 150° C., by heating means such as a hot plate, thermal circulation oven, IR (infrared) oven, etc., to obtain a coating film.

[Step (II)]
In step (II), the coating film obtained in step (I) is irradiated with polarized ultraviolet rays. When the film surface of the coating film is irradiated with polarized ultraviolet rays, the substrate is irradiated with the polarized ultraviolet rays from a certain direction through a polarizing plate. As the ultraviolet rays, ultraviolet rays having a wavelength of 100 to 400 nm can be used. Preferably, the optimum wavelength is selected through a filter or the like depending on the type of coating film to be used. Then, for example, ultraviolet light with a wavelength in the range of 290 to 400 nm can be selected and used so as to selectively induce a photocrosslinking reaction. As ultraviolet rays, for example, light emitted from a high-pressure mercury lamp can be used.

The amount of polarized UV light depends on the coating film used. The irradiation amount is 1 to 70% of the amount of polarized ultraviolet rays that realizes the maximum value of ΔA, which is the difference between the ultraviolet absorbance in the direction parallel to the polarization direction of the polarized ultraviolet rays and the ultraviolet absorbance in the direction perpendicular to the polarized ultraviolet rays in the coating film. is preferably within the range of , and more preferably within the range of 1 to 50%.

[Step (III)]
In step (III), the coating film irradiated with the polarized ultraviolet rays in step (II) is heated. Heating can impart alignment control ability to the coating film.

For heating, heating means such as a hot plate, thermal circulation oven, IR (infrared) oven, etc. can be used. The heating temperature can be determined in consideration of the temperature at which the coating film to be used exhibits liquid crystallinity.

The heating temperature is preferably within the temperature range at which the polymer of component (A) contained in the polymer composition of the present invention exhibits liquid crystallinity (hereinafter referred to as liquid crystal expression temperature). In the case of a thin film surface such as a coating film, the temperature at which liquid crystals appear on the surface of the coating film is expected to be lower than the temperature at which liquid crystals appear when the polymer of component (A) is observed in bulk. For this reason, the heating temperature is more preferably within the temperature range of the liquid crystal manifestation temperature of the coating film surface. That is, the temperature range of the heating temperature after irradiation with polarized ultraviolet rays is set to a temperature 10°C lower than the lower limit of the temperature range of the liquid crystal manifestation temperature of the polymer of component (A), and a temperature lower than the upper limit of the liquid crystal temperature range by 10°C. It is preferable that the temperature is in the range with the upper limit of If the heating temperature is lower than the temperature range, the effect of amplifying the anisotropy in the coating film tends to be insufficient, and if the heating temperature is too high than the temperature range, the state of the coating film tend to approach an isotropic liquid state (isotropic phase), in which case self-assembly can make it difficult to reorient in one direction.

In addition, the liquid crystal manifestation temperature is the liquid crystal transition temperature at which the polymer or coating surface undergoes a phase transition from the solid phase to the liquid crystal phase, and is isotropic that causes the phase transition from the liquid crystal phase to the isotropic phase (isotropic phase). The temperature below the phase transition temperature (Tiso). For example, exhibiting liquid crystallinity at 130° C. or lower means that the liquid crystal transition temperature at which a phase transition occurs from a solid phase to a liquid crystal phase is 130° C. or lower.

The thickness of the coating film formed after heating can be appropriately selected in consideration of the steps of the substrate to be used and the optical and electrical properties, and is preferably 0.5 to 10 μm, for example.

The single-layer retardation material of the present invention thus obtained is a material having optical properties suitable for applications such as display devices and recording materials. It is suitable as an optical compensation film.

The present invention will be described in more detail below with reference to Synthesis Examples, Production Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples.

MA-1 and MA-3 are shown below as monomers having a photoreactive group, and MA-2 as a monomer having a non-photoreactive group used in the examples. MA-1 was synthesized according to the synthetic method described in WO2011/084546. MA-2 was synthesized according to the synthesis method described in JP-A-9-118717. MA-3 was synthesized according to the synthesis method described in JP-A-2012-27354. MA-4 was synthesized using MA-2 as a raw material according to the synthesis method described in WO 2013/133078. MA-5 was synthesized according to the synthetic method described in WO2014/054785. MA-6 was synthesized by the synthesis method described in Non-Patent Document (Macromolecules 2007, 40, 6355-6360). MA-7 was synthesized by the synthesis method described in WO2014/054785. The side chains derived from MA-1, MA-3, and MA-6 exhibit photoreactivity and liquid crystallinity, and the side chains derived from MA-7 exhibit photoreactivity. Side chains derived from MA-5 exhibit only liquid crystallinity.

In addition, abbreviations of reagents used in this example are shown below.
(organic solvent)
NMP: N-methyl-2-pyrrolidone BCS: butyl cellosolve CPN: cyclopentanone (polymerization initiator)
AIBN: 2,2'-azobisisobutyronitrile In-1: Polyethylene glycol unit-containing polymeric azo polymerization initiator represented by the formula (In-1) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. VPE-0201 , molecular weight of polyethylene glycol unit: about 2,000)
In-2: Polydimethylsiloxane unit-containing polymeric azo polymerization initiator represented by the formula (In-2) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. VPS-1001N, molecular weight of polysiloxane unit: about 10,000)
(Surfactant)
R40: Megaface R-40 (manufactured by DIC)
F563: Megafac F-563 (manufactured by DIC)
(Molecular weight measurement of polymer)
Polymer molecular weight measurement conditions are as follows.
Apparatus: Shimadzu Nexera GPC system (Shimadzu SCL-40)
Column: Shodex column (LF-804, KF-801)
Column temperature: 40°C
Eluent: Tetrahydrofuran (HPLC grade)
Flow rate: 1.0 ml/min Standard sample for creating a calibration curve: Polystyrene (PStQuick E/PStQuick F (manufactured by Tosoh Corporation))

[1] Methacrylate polymer polymerization [Synthesis Example 1]
10.3 g (23.5 mmol) of MA-3 was weighed into a 50 mL eggplant flask, and 26.7 g of NMP was added and dissolved. After adding 4.0 g (2.0 mmol) of In-1 to the solution after dissolution, after degassing with a diaphragm pump, the pressure was restored with nitrogen (hereinafter also referred to as N ₂ degassing), and stirred. Dissolved. This solution was added dropwise to 6.7 g of NMP heated to 80°C over 1.5 hours while stirring, and after the dropwise addition was completed, reaction was allowed to proceed at 80°C for 20 hours. After the reaction, the solution was returned to room temperature to obtain a methacrylate block copolymer solution with a solid concentration of 30% by mass. This polymer solution was added dropwise to methanol (1,000 mL), and the precipitate formed was filtered off. The filter cake was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder MB1. MB1 had a number average molecular weight of 11,000 and a weight average molecular weight of 31,700.

[Synthesis Example 2]
15.4 g (35.1 mmol) of MA-3 was weighed into a 100 mL eggplant flask, and 29.9 g of NMP was added and dissolved. After 0.6 g (0.3 mmol) of In-1 was added to the solution after dissolution, N ₂ degassing treatment was performed and dissolved by stirring. This solution was added dropwise to 7.5 g of NMP heated to 80° C. over 1.5 hours while stirring, and after the drop was completed, reaction was allowed to proceed at 60° C. for 20 hours. After the reaction, the solution was returned to room temperature to obtain a methacrylate block copolymer solution. This polymer solution was added dropwise to methanol (1,000 mL), and the precipitate formed was filtered off. The resulting filter cake was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder MB2. MB2 had a number average molecular weight of 12,900 and a weight average molecular weight of 33,800.

[Synthesis Example 3]
15.4 g (35.1 mmol) of MA-3 was weighed into a 50 mL eggplant flask, and 29.5 g of NMP was added and dissolved. After 0.36 g (0.18 mmol) of In-1 was added to the solution after dissolution, N ₂ degassing treatment was performed and dissolved by stirring. This solution was added dropwise to 7.4 g of NMP heated to 80°C over 1.5 hours with stirring, and after the dropwise addition was completed, the solution was allowed to react at 80°C for 20 hours. After the reaction, the solution was returned to room temperature to obtain a methacrylate block copolymer solution with a solid content of 30%. This polymer solution was added dropwise to methanol (1,000 mL), and the precipitate formed was filtered off. The resulting filter cake was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder MB3. MB3 had a number average molecular weight of 14,800 and a weight average molecular weight of 38,100.

[Synthesis Example 4]
1.3 g (3.0 mmol) of MA-3 was weighed into a 50 mL eggplant flask, and 11.7 g of NMP was added and dissolved. 5.0 g (0.5 mmol) of In-2 was added to the solution after dissolution, followed by N ₂ degassing and stirring for dissolution. This solution was added dropwise to 2.9 g of NMP heated to 60°C over 1.5 hours while stirring, and after the dropwise addition was completed, reaction was allowed to proceed at 60°C for 20 hours. After the reaction, the solution was returned to room temperature to obtain a methacrylate block copolymer solution. This polymer solution was added dropwise to methanol (1,000 mL), and the precipitate formed was filtered off. The resulting filter cake was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder MB4.

[Synthesis Example 5]
2.6 g (5.9 mmol) of MA-3 was weighed into a 50 mL eggplant flask, and 14.1 g of NMP was added and dissolved. 5.0 g (0.5 mmol) of In-2 was added to the solution after dissolution, followed by N ₂ degassing and stirring for dissolution. This solution was added dropwise to 3.5 g of NMP heated to 60° C. over 1.5 hours while stirring, and after the drop was completed, reaction was allowed to proceed at 60° C. for 20 hours. After the reaction, the solution was returned to room temperature to obtain a methacrylate block copolymer solution. This polymer solution was added dropwise to methanol (1,000 mL), and the precipitate formed was filtered off. The resulting filter cake was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder MB5.

[Synthesis Example 6]
5.1 g (12 mmol) of MA-3 was weighed into a 50 mL eggplant flask, and 18.9 g of NMP was added and dissolved. 5.0 g (0.5 mmol) of In-2 was added to the solution after dissolution, followed by N ₂ degassing and stirring for dissolution. This solution was added dropwise to 4.7 g of NMP heated to 60°C over 1.5 hours while stirring, and after the dropwise addition was completed, the solution was allowed to react at 60°C for 20 hours. After the reaction, the solution was returned to room temperature to obtain a methacrylate block copolymer solution. This polymer solution was added dropwise to methanol (1,000 mL), and the precipitate formed was filtered off. The resulting filter cake was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder MB6.

[Synthesis Example 7]
2.0 g (6.0 mmol) of MA-1 and 10.4 g (34 mmol) of MA-2 were weighed into a 100 mL eggplant flask, and 38.1 g of NMP was added and dissolved. After 8.0 g (4.0 mmol) of In-1 was added to the solution after dissolution, N ₂ degassing treatment was performed and dissolved by stirring. This solution was added dropwise to 9.5 g of NMP heated to 80°C over 1.5 hours while stirring, and after the dropwise addition was completed, reaction was allowed to proceed at 80°C for 20 hours. After the reaction, the solution was returned to room temperature to obtain a methacrylate block copolymer (MB7) solution with a solid concentration of 30% by mass. MB7 had a number average molecular weight of 17,000 and a weight average molecular weight of 42,500.

[Synthesis Example 8]
1.1 g (3.3 mmol) of MA-1 and 5.7 g (18.7 mmol) of MA-2 were weighed into a 100 mL eggplant flask, and 16.9 g of NMP was added and dissolved. 2.2 g (1.1 mmol) of In-1 was added to the solution after dissolution, followed by N ₂ degassing and stirring for dissolution. This solution was added dropwise to 4.2 g of NMP heated to 80° C. over 1.5 hours while stirring, and after the drop was completed, reaction was allowed to proceed at 80° C. for 20 hours. After the reaction, the solution was returned to room temperature to obtain a methacrylate block copolymer (MB8) solution with a solid concentration of 30% by mass.

[Synthesis Example 9]
1.2 g (3.6 mmol) of MA-1 and 6.5 g (21 mmol) of MA-2 were weighed into a 50 mL eggplant flask, and 17.3 g of NMP was added and dissolved. After adding 1.5 g (0.75 mmol) of In-1 to the solution after dissolution, N ₂ degassing treatment was performed and dissolved by stirring. This solution was added dropwise to 4.3 g of NMP heated to 80°C over 1.5 hours while stirring, and after the dropwise addition was completed, reaction was allowed to proceed at 80°C for 20 hours. After the reaction, the solution was returned to room temperature to obtain a methacrylate block copolymer (MB9) solution with a solid concentration of 30% by mass.

[Synthesis Example 10]
2.2 g (5.0 mmol) of MA-3 and 2.0 g (5.0 mmol) of MA-4 were weighed into a 50 mL eggplant flask, and 12.3 g of CPN was added and dissolved. After 2.0 g (1.0 mmol) of In-1 was added to the solution after dissolution, N ₂ degassing treatment was performed and dissolved by stirring. This solution was added dropwise to 3.08 g of CPN heated to 80° C. over 1.5 hours while stirring, and after the drop was completed, reaction was allowed to proceed at 80° C. for 20 hours. After the reaction, this polymer solution was added dropwise to methanol (200 mL), and the produced precipitate was separated by filtration. The resulting filter cake was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder MB10. MB10 had a number average molecular weight of 13,500 and a weight average molecular weight of 48,330.

[Synthesis Example 11]
2.2 g (5.0 mmol) of MA-3 and 1.8 g (5.0 mmol) of MA-5 were weighed into a 50 mL eggplant flask, and 14.9 g of CPN was added and dissolved. After 2.0 g (1.0 mmol) of In-1 was added to the solution after dissolution, N ₂ degassing treatment was performed and dissolved by stirring. This solution was added dropwise to 3.00 g of CPN heated to 80° C. over 1.5 hours while stirring, and after the drop was completed, the solution was allowed to react at 80° C. for 20 hours. After the reaction, this polymer solution was added dropwise to methanol (200 mL), and the produced precipitate was separated by filtration. The resulting filter cake was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder MB11. MB11 had a number average molecular weight of 10,140 and a weight average molecular weight of 33,400.

[Synthesis Example 12]
2.29 g (4.0 mmol) of MA-6 and 0.40 g (0.20 mmol) of In-1 were weighed into a 50 mL eggplant flask, and 10.8 g of CPN was added and dissolved. The solution after dissolution was deaerated with N ₂ and reacted under heating conditions of 80° C. for 20 hours. After the reaction, the polymer solution was added dropwise to methanol (200 mL), and the generated precipitate was separated by filtration. The resulting filter cake was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder MB12. MB12 had a number average molecular weight of 23,800 and a weight average molecular weight of 55,900.

[Synthesis Example 13]
Weigh 0.68 g (1.5 mmol) of MA-7, 2.60 g (8.5 mmol) of MA-2, and 0.40 g (0.20 mmol) of In-1 into a 50 mL eggplant flask. 7 g was added and dissolved. After dissolution, N ₂ degassing treatment was performed, and reaction was carried out under heating conditions of 80° C. for 20 hours. After the reaction, this polymer solution was added dropwise to methanol (200 mL), and the produced precipitate was separated by filtration. The resulting filter cake was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder MB13. MB13 had a number average molecular weight of 25,000 and a weight average molecular weight of 51,100.

[Comparative Synthesis Example 1]
13.2 g (30 mmol) of MA-3 and 37.5 g of NMP were weighed and dissolved in a 100 mL eggplant flask. After performing N ₂ degassing, 0.24 g (1.5 mmol) of AIBN was added, and N ₂ degassing was performed again. After that, the mixture was reacted at 60° C. for 8 hours to obtain a methacrylate polymer solution. This polymer solution was added dropwise to methanol (1,000 mL), and the precipitate formed was filtered off. The resulting filter cake was washed with methanol and dried under reduced pressure to obtain a methacrylate polymer powder (P1). P1 had a number average molecular weight of 13,400 and a weight average molecular weight of 48,900.

[Comparative Synthesis Example 2]
1.5 g (4.5 mmol) of MA-1 and 7.8 g (25.4 mmol) of MA-2 were weighed into a 50 mL eggplant flask, and 22.9 g of NMP was added and dissolved. After performing N ₂ degassing, 0.49 g (3.0 mmol) of AIBN was added, and N ₂ degassing was performed again. After that, the mixture was reacted at 60° C. for 8 hours to obtain a methacrylate polymer solution (P2). P2 had a number average molecular weight of 34,000 and a weight average molecular weight of 97,800.

[Comparative Synthesis Example 3]
2.86 g (5.0 mmol) of MA-6 and 0.41 g (0.25 mmol) of AIBN were weighed into a 50 mL eggplant flask, and 11.6 g of CPN was added and dissolved. After dissolution, N ₂ degassing treatment was performed, and the mixture was reacted under heating conditions of 60° C. for 20 hours. After the reaction, this polymer solution was added dropwise to methanol (200 mL), and the produced precipitate was separated by filtration. The resulting filter cake was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder P3. P3 had a number average molecular weight of 35,000 and a weight average molecular weight of 106,000.

[Comparative Synthesis Example 4]
Weigh 1.35 g (3.0 mmol) of MA-7, 5.21 g (17.0 mmol) of MA-2, 0.16 g (1.00 mmol) of AIBN, and 18.8 g of NMP into a 50 mL eggplant flask, Dissolved. After degassing with N ₂ , this solution was dropped into 8.10 g of NMP heated to 60° C. over 2 hours with stirring, and after the dropping was completed, the reaction was allowed to proceed at 60° C. for 20 hours. . After the reaction, this polymer solution was added dropwise to a mixed solvent of methanol (200 mL) and pure water (80 mL), and the produced precipitate was separated by filtration. The resulting filter cake was washed with methanol and dried under reduced pressure to obtain methacrylate polymer powder P4. P4 had a number average molecular weight of 28,000 and a weight average molecular weight of 63,000.

Table 1 summarizes the components used in each of the above synthesis examples and comparative synthesis examples.

[2] Preparation of polymer solution [Production Example 1]
The polymer powder MB1 (3.0 g) obtained in Synthesis Example 1 was weighed, and CPN (8.85 g), BCS (3.0 g), and R40 (0.05% by mass relative to the polymer solid content) were added. , to obtain a polymer solution T1. This polymer solution T1 was directly used as a retardation material for forming a retardation film.

[Production Examples 2 to 6]
Polymer solutions T2 to T6 were obtained in the same manner as in Production Example 1, except that polymer powders MB2 to MB6 were used instead of polymer powder MB1. The obtained polymer solutions T2 to T6 were directly used as retardation materials for forming retardation films.

[Production Example 7]
The polymer solution MB7 (10.0 g) obtained in Synthesis Example 7 was weighed, and CPN (1.85 g), BCS (3.0 g), and R40 (0.05% by mass relative to the polymer solid content) were added. , to obtain a polymer solution T7. The obtained polymer solution T7 was directly used as a retardation material for forming a retardation film.

[Production Examples 8-9]
Polymer solutions T8 to T9 were obtained in the same manner as in Production Example 7, except that polymer solutions MB8 to MB9 were used instead of polymer solution MB7. The obtained polymer solutions T8 and T9 were directly used as retardation materials for forming retardation films.

[Production Examples 10 and 11]
Polymer solutions T10 and T11 were obtained in the same manner as in Production Example 1, except that polymer powders MB10 and MB11 were used instead of polymer powder MB1. The obtained polymer solutions T10 and T11 were directly used as retardation materials for forming retardation films.

[Production Example 12]
Polymer powder MB12 (1.50 g) obtained in Synthesis Example 12 was weighed, CPN (8.49 g) and F563 (7.5 mg) were added, and the mixture was stirred to obtain polymer solution T12. This polymer solution T12 was directly used as a retardation material for forming a retardation film.

[Production Example 13]
Polymer solution T13 was obtained in the same manner as in Production Example 12, except that polymer powder MB13 was used instead of polymer powder MB12.

[Comparative Production Example 1]
Polymer solution C1 was obtained in the same manner as in Production Example 1, except that polymer solution P1 was used instead of polymer powder MB1. The obtained polymer solution C1 was used as a retardation material for forming a retardation film as it was.

[Comparative Production Example 2]
Polymer solution C2 was obtained in the same manner as in Production Example 7, except that polymer solution P2 was used instead of polymer solution MB7. The obtained polymer solution C2 was used as a retardation material for forming a retardation film as it was.

[Comparative Production Examples 3 and 4]
Polymer solutions C3 and C4 were obtained in the same manner as in Production Example 12, except that polymer powders P3 and P4 were used instead of polymer powder MB12.

Table 2 summarizes the components used in each of the above production examples and comparative production examples.

[3] Production of single-layer retardation material [Example 1]
The polymer solution T1 obtained in Production Example 1 was filtered through a filter with a pore size of 5.0 μm, spin-coated onto a non-alkali glass substrate, dried on a hot plate at 60° C. for 4 minutes, and coated with a film thickness of 2.0 μm. A retardation film was formed. Next, as shown in Table 3, the coated film surface was irradiated with ultraviolet rays of 365 nm at 50, 100, 200, 400, and 800 mJ/cm ² through a polarizing plate, and then placed in a thermal circulation oven at 120°C for 20 minutes. It was heated for a minute to produce a substrate S1 with a retardation film.

[Examples 2 to 9]
Substrates S2 to S9 with a retardation film were produced in the same manner as in Example 1, except that T2 to T9 were used instead of the polymer solution T1.

[Examples 10 to 13]
In the same manner as in Example 1, except that T10 and T11 were used instead of the polymer solution T1, the polarized ultraviolet exposure conditions were changed, and the baking temperature was changed to 100° C. and 120° C., a substrate S10 to S13 was produced. When exposing to polarized ultraviolet rays, exposure was performed through a 325 nm long wave pass filter (325LWPF) and a 365 nm polarizing plate.

[Example 14]
After the polymer solution T12 was filtered through a 5.0 μm filter, it was applied onto a non-alkali glass substrate using a bar coater. The coated film was dried in a thermal circulation oven at 50° C. for 3 minutes, and then the substrate was irradiated with 200 mJ/cm ² of polarized ultraviolet rays of 365 nm from a high-pressure mercury lamp through a 365 nm bandpass filter (365BPF) and a polarizing plate. It was heated in an IR oven at 130° C. for 20 minutes to prepare a substrate S14 with a retardation film.

[Example 15]
After the polymer solution T13 was filtered through a 5.0 μm filter, it was applied onto an alkali-free glass substrate using a bar coater. The coated film was dried in a thermal circulation oven at 50° C. for 3 minutes, and then the substrate was irradiated with 1,600 mJ/cm ² of polarized ultraviolet rays of 313 nm from a high-pressure mercury lamp through a 313 nm bandpass filter (313BPF) and a polarizing plate. bottom. It was heated in an IR oven at 140° C. for 20 minutes to prepare a substrate S15 with a retardation film.

[Comparative Example 1]
A substrate Q1 with a retardation film was produced in the same manner as in Example 1 except that C1 was used instead of the polymer solution T1 and the baking temperature was changed to 140.degree.

[Comparative Example 2]
A substrate Q2 with a retardation film was produced in the same manner as in Example 1, except that C1 was used instead of the polymer solution T1.

[Comparative Example 3]
A substrate Q3 with a retardation film was produced in the same manner as in Example 1 except that C2 was used instead of the polymer solution T1 and the baking temperature was changed to 140.degree.

[Comparative Example 4]
A substrate Q4 with a retardation film was produced in the same manner as in Example 1, except that C2 was used instead of the polymer solution T1.

[Comparative Example 5]
A substrate Q5 with a retardation film was produced in the same manner as in Example 14, except that C3 was used instead of the polymer solution T12.

[Comparative Example 6]
A substrate Q6 with a retardation film was produced in the same manner as in Example 15, except that C4 was used instead of the polymer solution T13.

The Haze value of each of the substrates S1 to S15 and Q1 to Q6 produced in each of the examples and comparative examples was evaluated by the following method.
[Haze value evaluation]
The haze value of the retardation film was evaluated using a haze meter (HZ-V3) manufactured by SUGA Test Instruments Co., Ltd. Tables 3 and 4 show the results.

From the results in Tables 3 and 4, in the test pieces prepared using the side chain type block copolymer, the softening (lowering of Tg) of the film occurs, which increases the crystallization accuracy during film sintering ( (The number of structural defects in the crystal is reduced), or the flexibility of the crystal makes it difficult for the crystal molecules to form polydomains, which reduces the scattering of light that passes through the film and suppresses the turbidity (haze) of the film. It is considered that

The retardation values of the substrates S1 to S15 and Q1 to Q6 produced in the above examples and comparative examples were evaluated by the following method.
[Phase difference value evaluation]
A linear phase difference (Linear Re) at a wavelength of 550 nm was evaluated using Axo Scan manufactured by Axometrics. Tables 5 and 6 show the results.

From the results in Tables 5 and 6, it was confirmed that the test pieces produced using the side-chain block copolymer exhibited a phase difference despite a decrease in the haze. It is considered that this is due to the fact that the crystallinity in the film is maintained while the Tg is lowered by the application of the side chain type block copolymer.

Claims

(A) A block copolymer containing a photosensitive side chain type polymer block capable of exhibiting liquid crystallinity and a polymer block derived from a polymer type polymerization initiator, and (B) a polymer composition containing an organic solvent. .
2. The polymer composition according to claim 1, wherein the side chain type polymer block has a side chain represented by any one of the following formulas (a1) to (a6).

(In the formula, n1 and n2 are each independently 0, 1, 2 or 3.
L is a single bond or an alkylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms in the alkylene group may be substituted with halogen atoms.
T 1 is a single bond or an alkylene group having 1 to 12 carbon atoms, and some or all of the hydrogen atoms in the alkylene group may be substituted with halogen atoms.
A 1 , A 2 and D 1 are each independently a single bond, -O-, -CH 2 -, -C(=O)-O-, -OC(=O)-, -C(= O) —NH— or —NH—C(=O)—. However, when T 1 is a single bond, A 2 is also a single bond.
Y 1 and Y 2 are a phenylene group or a naphthylene group, and part or all of the hydrogen atoms of the phenylene group and naphthylene group are a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms. It may be substituted with an alkylcarbonyl group of 5 or an alkoxy group having 1 to 5 carbon atoms.
P 1 , Q 1 and Q 2 are each independently a single bond, a phenylene group or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and part or all of the hydrogen atoms of the phenylene group are , a cyano group, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. When the number of Q 1 is 2 or more, each Q 1 may be the same or different, and when the number of Q 2 is 2 or more, each Q 2 may be the same or different.
R is a hydrogen atom, a cyano group, a halogen atom, a carboxy group, an alkyl group having 1 to 5 carbon atoms, an alkylcarbonyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 7 carbon atoms or a cycloalkyl group having 1 to 5 carbon atoms It is an alkoxy group.
X 1 and X 2 are each independently a single bond, -O-, -C(=O)-O-, -O-C(=O)-, -N=N-, -CH=CH-, -C≡C-, -CH=CH-C(=O)-O- or -O-C(=O)-CH=CH-. When the number of X 1 is 2 or more, each X 1 may be the same or different, and when the number of X 2 is 2 or more, each X 2 may be the same or different.
Cou is a coumarin-6-yl group or a coumarin-7-yl group, and some of the hydrogen atoms bonded to them are -NO 2 , -CN, -CH=C(CN) 2 , -CH=CH- It may be substituted with CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-.
G 1 and G 2 are each independently N or CH.
A dashed line is a bond. )
The polymer composition according to claim 1 or 2, wherein the side chain type polymer block further has a side chain that neither photodimerizes nor photoisomerizes.
4. The polymer composition according to claim 3, wherein the side chain that neither photodimerizes nor photoisomerizes is represented by any one of the following formulas (b1) to (b11).

(wherein A 3 and A 4 are each independently a single bond, -O-, -CH 2 -, -C(=O)-O-, -OC(=O)-, -C( =O)-NH- or -NH-C(=O)- When the number of A 4 is 2 or more, each A 4 may be the same or different.
R 1 is —NO 2 , —CN, halogen atom, phenyl group, naphthyl group, biphenylyl group, furanyl group, monovalent nitrogen-containing heterocyclic group, monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, carbon It is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.
R 2 is a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group or a monovalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and part of the hydrogen atoms of these groups Alternatively, all of them may be substituted with —NO 2 , —CN, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms.
R 3 is a hydrogen atom, —NO 2 , —CN, a halogen atom, a phenyl group, a naphthyl group, a biphenylyl group, a furanyl group, a monovalent nitrogen-containing heterocyclic group, or a monovalent alicyclic hydrocarbon having 5 to 8 carbon atoms; , an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms.
E is -C(=O)-O-, -OC(=O)-, -C(=O)-S- or -SC(=O)-.
a is an integer from 1 to 12;
k1 to k5 are each independently an integer of 0 to 2, but the sum of k1 to k5 is 2 or more.
k6 and k7 are each independently an integer of 0 to 2, and the sum of k6 and k7 is 1 or more.
m1, m2 and m3 are each independently an integer of 1-3.
n is 0 or 1;
Z 1 and Z 2 are each independently a single bond, -C(=O)-, -CH 2 -O-, or -CF 2 -.
A dashed line is a bond. )
The polymer composition according to any one of claims 1 to 4, wherein the polymer type polymerization initiator has a repeating unit represented by the following formula (1).

In the formula, R a1 to R a4 are each independently a linear or branched alkyl group having 1 to 6 carbon atoms or a cyano group. R L1 and R L2 are each independently an alkylene group having 1 to 10 carbon atoms. L 1 and L 2 each independently represent -C(=O)-O-, -OC(=O)-, -C(=O)-NH- or -NH-C(=O)- is. X is a divalent group represented by the following formula (2) or (3).

In the formula, R a5 to R a8 are linear or branched C 1-6 alkyl groups or C 6-12 aryl groups. R a9 and R a10 are each independently an alkylene group having 1 to 10 carbon atoms. R L3 and R L4 are each independently an alkylene group having 1 to 10 carbon atoms. x and y are each independently positive integers.
6. The polymer composition according to claim 5, wherein the polymer type polymerization initiator is represented by any one of the following formulas (In-1) to (In-2).

(Wherein, x and y are the same as above. n is a positive integer.)
(I) a step of applying the polymer composition according to any one of claims 1 to 6 onto a substrate to form a coating film;
(II) a step of irradiating the coating film with polarized ultraviolet rays; and (III) a step of heating the coating film irradiated with the ultraviolet rays to obtain a retardation material.
A single-layer retardation material obtained from the polymer composition according to any one of claims 1 to 6.