Adhesive compositions, compounds, adhesive layers, optical laminates, methods for manufacturing optical laminates, and image display devices

Abstract

The objective of this invention is to provide an adhesive composition, compound, adhesive layer, optical laminate, method for manufacturing the optical laminate, and image display device that can suppress wind spots and exhibit excellent topcoatability after being formed into a layer. The adhesive composition of this invention is an adhesive composition containing an adhesive and a compound having a group represented by the following formula (B1) or (B2). In the above formulas (B1) and (B2), Z represents an aliphatic hydrocarbon group or an organosiloxane group having a fluorine atom.

Description

TECHNICAL FIELD

[0001] The present application relates to an adhesive composition, a compound, an adhesive layer, an optical laminate, a method for manufacturing an optical laminate, and an image display device. BACKGROUND

[0002] In recent years, polymer materials are used in various fields. At the same time, depending on the field, the properties of the polymer as a matrix and the properties of the interface of the laminated film when the surface of the coating film or the laminated film is formed by adding the polymer are also important. For example, semiconductor devices, optical components, liquid crystal-related components, and the like are generally produced by laminating a coating film. In order to improve the wettability of the coating composition and the smoothness of the surface of the coating film or the wettability when further coating a composition on the surface of the coating film, a silicone-based or fluorine-based surfactant is sometimes added to the composition.

[0003] For example, in Patent Literature 1, a composition containing a fluorine-containing polymer surfactant obtained by polymerizing a prescribed fluorine-containing urethane (meth) acrylate as an essential component of a polymerizable olefinically unsaturated monomer class is described ([Claim 1] [Claim 6]

[0070] ).

[0004] Also, in Patent Literature 2, an adhesive composition containing a photo-orienting polymer and an adhesive is described, the photo-orienting polymer having a repeating unit having a fluorine atom or a silicon atom at a prescribed position ([Claim 1] [Claim 7]).

[0005] PRIOR ART DOCUMENTS

[0006] PATENT LITERATURE

[0007] Patent Literature 1: Japanese Patent Application Publication No. 2008-115258

[0008] Patent Literature 2: International Publication No. 2018 / 216812 SUMMARY

[0009] PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] If a fluorine-based surfactant or a silicone-based surfactant is used, the coatability of the composition becomes good, and film thickness unevenness (hereinafter, also referred to as "wind marks") caused by drying air at the time of drying can also be suppressed, but since the surface energy of the coating film is low, the surfactant has a tendency to be unevenly present on the surface of the coating film. The water and oil repellency of such a surface becomes high, so when attempting to further coat an upper layer to form a film to produce a laminated film, the coatability (hereinafter, also referred to as "upper layer coatability") of the composition for forming the upper layer is sometimes poor.

[0011] The present inventors and others have conducted research on the composition described in Patent Document 1 from the viewpoint of windmilling and overcoat applicability, and as a result, have confirmed that the windmilling prevention effect is excellent, but there is room for improvement in overcoat applicability.

[0012] Likewise, as a result of conducting research on the composition described in Patent Document 2, it was confirmed that the windmilling prevention effect is excellent, but although the overcoat applicability satisfies the conventional required level, further improvement is required in order to satisfy the higher required level today.

[0013] Therefore, the present application has as an object to provide an adhesive composition capable of inhibiting windmilling and having excellent overcoat applicability after being formed into a layer, a compound, an adhesive layer, an optical laminate, a method for manufacturing an optical laminate, and an image display device.

[0014] Means for solving the technical problem

[0015] As a result of intensive research conducted by the present inventors and others in order to solve the above problem, it was found that if a compound having a group represented by a prescribed structure is formulated, windmilling can be inhibited and excellent overcoat applicability is obtained after being formed into a layer, and the present application was completed.

[0016] That is, the present inventors and others have found that the above problem can be solved by the following structure.

[0017] [1] An adhesive composition comprising an adhesive and a compound having a group represented by the following formula (B1) or (B2).

[0018] [2] The adhesive composition according to [1], further comprising a photoacid generator.

[0019] [3] The adhesive composition according to [1] or [2], wherein the compound is a compound further having a photo-orienting group.

[0020] [4] The adhesive composition according to any one of [1] to [3], wherein the compound is a polymer having a repeating unit B comprising a group represented by the following formula (B1) or (B2).

[0021] [5] The adhesive composition according to [4], wherein the repeating unit B is a repeating unit represented by the following formula (1) or (2).

[0022] [6] The adhesive composition according to [4] or [5], wherein the compound is a copolymer having a repeating unit A comprising a photo-orienting group and the repeating unit B.

[0023] [7] The adhesive composition according to [6], wherein the repeating unit A is a repeating unit represented by the following formula (A).

[0024] [8] The adhesive composition according to [6] or [7], wherein the compound is a copolymer having repeating unit C, repeating unit B and repeating unit A containing crosslinking groups.

[0025] [9] An adhesive composition according to any one of [1] to [8], wherein the weight-average molecular weight of the compound is 10,000 to 500,000.

[0026]

[10] A compound having a group represented by the formula (B1) or (B2) described later.

[0027]

[11] The compound according to

[10] also has a group represented by the formula (P0) described later.

[0028]

[12] The compound according to

[10] is a polymer having repeating unit B containing a group represented by the formula (B1) or (B2) described below.

[0029]

[13] According to the compound described in

[12] , wherein the repeating unit B is the repeating unit represented by formula (1) or (2) described later.

[0030]

[14] The compound according to

[12] or

[13] is a copolymer having repeating unit A and repeating unit B containing photooriented groups.

[0031]

[15] According to the compound described in

[14] , the repeating unit A is the repeating unit represented by the formula (A) described later.

[0032]

[16] The compound according to

[14] or

[15] is a copolymer having repeating unit C, repeating unit B and repeating unit A containing crosslinking groups.

[0033]

[17] The compound according to any one of

[10] to

[16] , wherein the weight-average molecular weight is 10,000 to 500,000.

[0034]

[18] An adhesive layer formed using any one of the adhesive compositions described in [1] to [9].

[0035]

[19] An optical laminate having:

[0036] The adhesive layer described above

[18] ; and

[0037] An optically anisotropic layer disposed on an adhesive layer.

[0038]

[20] A method for manufacturing an optical laminate, comprising:

[0039] The step of supplying a coating obtained using the adhesive composition of any one of [6] to [8] with at least one of the group consisting of light, heat, acid and alkali, and then performing a photo-alignment treatment to form an adhesive layer; and

[0040] The process of forming an optically anisotropic layer by coating a polymeric liquid crystal composition containing a polymeric liquid crystal compound onto an adhesive layer.

[0041]

[21] An image display device having the adhesive layer described in

[18] or the optical laminate described in

[19] .

[0042] Invention Effects

[0043] According to the present invention, an adhesive composition, compound, adhesive layer, optical laminate, method for manufacturing optical laminate, and image display device are provided that can suppress wind spots and have excellent coatability after being formed into a layer. Detailed Implementation

[0044] The present invention will now be described in detail.

[0045] The following description of the constituent elements is based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment.

[0046] In addition, in this specification, the numerical range represented by “~” indicates the range included by the values ​​recorded before and after “~” as the lower limit and upper limit values.

[0047] Furthermore, in this specification, for each component, the corresponding substance may be used individually or in combination with two or more substances. Where two or more substances are used simultaneously as components, unless otherwise specified, the content of each component refers to the total content of the substances used simultaneously.

[0048] Furthermore, in this specification, "(meth)acrylic acid" is a term used to refer to "acrylic acid" or "methacrylic acid".

[0049] Furthermore, the bonding direction of the divalent groups (e.g., -O-CO-) described in this specification is not particularly limited; for example, in "L 1 -L 2 -L 3 In the bonding of ", in L 2 In the case of -O-CO-, if it is combined with L 1 The side bond position is set to *1 and will be connected to L 3 If the side bond position is set to *2, then L 2 It can be *1-O-CO-*2 or *1-CO-O-*2.

[0050] [Adhesive Composition]

[0051] The adhesive composition of the present invention is a composition containing an adhesive and a compound having a group represented by the formula (B1) or (B2) described below (hereinafter also simply referred to as "specific cleavage group").

[0052] In this invention, if a specific compound is formulated, wind spots can be suppressed and the upper coating properties become good after the layer is formed.

[0053] While the details are not yet clear, the inventor makes the following speculations.

[0054] First, it is believed that if an adhesive layer is formed by coating the adhesive composition of the present invention, specific compounds containing aliphatic hydrocarbon groups or organosiloxane groups having fluorine atoms are unevenly present on the air interface side of the adhesive, thus suppressing wind spots.

[0055] Then, it is believed that if at least one of the groups consisting of light, heat, acid and base is applied to a specific compound that is unevenly present on the air interface side, the ketal structure contained in the specific cleavage group is easily cleaved, and the aliphatic hydrocarbon group or organosilicon alkyl group with fluorine atom is released, so the upper coating properties become good after the layer is formed.

[0056] [Specific compound]

[0057] The specific compounds contained in the adhesive compositions of the present invention are compounds having groups represented by the following formula (B1) or (B2).

[0058] Furthermore, considering that the ability to suppress wind spots can be adjusted by controlling surface tension and the performance of the upper coating can be adjusted by controlling the pyrolysis rate of the pyrolysis component, the specific compound is preferably a compound having the group represented by the following formula (B1).

[0059]

[0060] In equations (B1) and (B2) above, * indicates the bonding position.

[0061] Furthermore, n represents an integer greater than or equal to 1. Multiple n values ​​can be the same or different.

[0062] Furthermore, m represents an integer greater than 2.

[0063] Furthermore, R b1 It represents a hydrogen atom or a substituent.

[0064] Furthermore, R b2 R b3 and Rb4 Each can be represented independently by a hydrogen atom or a substituent. Among them, the two R's... b3 They can bond together to form a ring, multiple R b2 They can be the same or different; multiple R's b3 They can be the same or different; multiple R's b4 They can be the same or different.

[0065] Furthermore, L b1 This represents a linking group with an n+1 valence. Multiple L... b1 They can be the same or different.

[0066] Furthermore, L b2 This indicates a linking group with a valence of m+1.

[0067] Furthermore, Z represents an aliphatic hydrocarbon group or an organosiloxane group containing a fluorine atom. The aforementioned aliphatic hydrocarbon group may contain an oxygen atom, and multiple Zs may be identical or different.

[0068] In the above formula (B1), R b1 It represents a hydrogen atom or a substituent, preferably a substituent.

[0069] R b1 The types of substituents represented by the method are not particularly limited, and well-known substituents can be cited.

[0070] Examples of substituents include aliphatic hydrocarbon groups that can have a monovalent oxygen atom and aromatic hydrocarbon groups that can have a monovalent oxygen atom. More specifically, examples include alkyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, acyl, acyloxy, and groups formed by combining these. Furthermore, the above substituents can be further substituted with other substituents.

[0071] Among them, as R b1 The substituent represented by one of the methods is preferably an aliphatic hydrocarbon group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably a straight-chain alkyl group having 1 to 8 carbon atoms or a branched alkyl group having 3 to 8 carbon atoms, and especially preferably methyl.

[0072] In the above formula (B1), R b2 This represents a hydrogen atom or a substituent. Multiple R groups are involved. b2 They can be the same or different.

[0073] R b2 The type of substituent represented by this method is not particularly limited; well-known substituents can be cited, such as R in the above formula (B1). b1The substituents are the groups exemplified in the representation of a certain method. Preferably, they are alkyl groups having 1 to 12 carbon atoms, more preferably straight-chain alkyl groups having 1 to 8 carbon atoms or branched alkyl groups having 3 to 8 carbon atoms, and even more preferably methyl groups.

[0074] Furthermore, R b2 The preferred representation is a hydrogen atom.

[0075] In the above formula (B1), L b1 This represents a linking group with an n+1 valence. Multiple L... b1 They can be the same or different.

[0076] As an n+1 valence linking group, considering that the ability to control surface tension can be adjusted to suppress wind spots and the performance of the upper coating can be adjusted by controlling the pyrolysis rate of the pyrolysis component, it is preferable to be a hydrocarbon group with an n+1 valence that has 1 to 24 carbon atoms having substituents and a portion of the carbon atoms constituting the hydrocarbon group can be replaced by heteroatoms, and more preferably an aliphatic hydrocarbon group that can contain oxygen or nitrogen atoms having 1 to 10 carbon atoms.

[0077] The number of carbon atoms contained in the n+1 valence linking group is not particularly limited. Considering that the ability to suppress wind spots can be adjusted by controlling the surface tension and the performance of the upper coating can be adjusted by controlling the pyrolysis rate of the pyrolysis component, the preferred number is 1 to 24, and more preferably 1 to 10.

[0078] As an n+1 valent linking group, it is preferably a 2-4 valent linking group, more preferably a 2-3 valent linking group, and even more preferably a 2 valent linking group.

[0079] Examples of divalent linking groups include divalent hydrocarbon groups, divalent heterocyclic groups, -O-, -S-, -N(Q)-, -CO-, or combinations thereof, which may have substituents. Q represents a hydrogen atom or a substituent.

[0080] Examples of divalent hydrocarbon groups include alkylene groups with 1 to 10 carbon atoms (preferably 1 to 5), alkenyl groups with 1 to 10 carbon atoms, and alkyne groups with 1 to 10 carbon atoms; and aromatic hydrocarbon groups such as arylene groups.

[0081] Examples of divalent heterocyclic groups include divalent aromatic heterocyclic groups, such as pyridilene, pyridazine, imidazole, thienylene, and quinolene.

[0082] Furthermore, as the group to be combined, examples can be groups composed of at least two of the groups selected from the group consisting of divalent hydrocarbon groups, divalent heterocyclic groups, -O-, -S-, -N(Q)- and -CO-. For example, -O- divalent hydrocarbon groups and -(O- divalent hydrocarbon groups) can be cited. p -O- (p represents an integer greater than or equal to 1. There is no particular upper limit, but it is preferably 20 or less, more preferably 10 or less.) and divalent hydrocarbon groups such as -O-, CO-, etc.

[0083] Among these divalent linking groups, the preferred ones are straight-chain alkylene groups with 1 to 10 carbon atoms, branched alkylene groups with 3 to 10 carbon atoms, cyclic alkylene groups with 3 to 10 carbon atoms, arylene groups with 6 to 12 carbon atoms, and -O-.

[0084] Substituents that can be present in hydrocarbon groups and heterocyclic groups, as well as substituents represented by Q, include, for example, halogen atoms, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, cyano groups, carboxyl groups, alkoxycarbonyl groups, and hydroxyl groups.

[0085] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with fluorine or chlorine atoms being preferred.

[0086] As an alkyl group, it is preferably a straight-chain alkyl group with 1 to 18 carbon atoms, a branched alkyl group with 3 to 18 carbon atoms, or a cyclic alkyl group, more preferably a straight-chain alkyl group with 1 to 4 carbon atoms, and even more preferably methyl or ethyl.

[0087] The alkoxy group is preferably an alkoxy group with 1 to 18 carbon atoms, more preferably an alkoxy group with 1 to 4 carbon atoms, and even more preferably a methoxy or ethoxy group.

[0088] Examples of aryl groups include those with 6 to 12 carbon atoms, such as phenyl, α-methylphenyl, and naphthyl, with phenyl being the most preferred.

[0089] Examples of aryloxy groups include phenoxy, naphthoxy, imidazoleoxy, benzimidazoleoxy, pyridin-4-yloxy, pyrimidinyloxy, quinazolinyloxy, purinyloxy, and thiophene-3-yloxy.

[0090] Examples of alkoxycarbonyl groups include methoxycarbonyl and ethoxycarbonyl.

[0091] In formula (B1) above, Z represents an aliphatic hydrocarbon group or an organosilicon alkyl group having a fluorine atom. The aliphatic hydrocarbon group may have an oxygen atom, and the multiple Zs may be identical or different.

[0092] Aliphatic hydrocarbon groups containing fluorine atoms, represented as Z, include, for example, alkyl groups containing fluorine atoms, one or more -O-substituted groups of -CH2- constituting an alkyl group containing fluorine atoms, alkenyl groups containing fluorine atoms, etc.

[0093] Wherein, the alkyl group containing fluorine atoms can be an alkyl group in which a portion of the hydrogen atom of the -CH2- constituting the alkyl group is replaced with a fluorine atom, or a group in which a carbon atom constituting a portion of the alkyl group has a substituent containing a fluorine atom (e.g., -CF3). However, it is preferred to be a perfluoroalkyl group in which all hydrogen atoms of the -CH2- constituting the alkyl group are replaced with fluorine atoms, and more preferably -(CF2). fa CF3. Additionally, fa represents an integer from 0 to 12.

[0094] Furthermore, one or more -O-substituted groups constituting the -CH2- of the fluorine-containing alkyl group can be cited as an example, such as -(CF2). fb OC(CF3)3、-CF2CF2O(CF2CF2O) fc Examples include CF2CF2CF3, -CF(CF3)OCF2CF(CF3)OCF2CF2CF3, etc. Additionally, fb represents an integer from 1 to 10, and fc represents an integer from 1 to 10.

[0095] Furthermore, examples of alkenyl groups containing fluorine atoms include -C(CF3)=C(CF(CF3)2)2.

[0096] The number of carbon atoms in the aliphatic hydrocarbon group containing fluorine atoms is not particularly limited, but is preferably 1 to 30, more preferably 3 to 20, and even more preferably 3 to 10.

[0097] The number of fluorine atoms contained in the aliphatic hydrocarbon group having fluorine atoms is not particularly limited, but is preferably 1 to 30, more preferably 5 to 25, and even more preferably 7 to 20.

[0098] As a form of Z, organosiloxane alkyl groups, for example -SiR, can be represented by... 30 R 31 -OR 32 、-(SiR 33 R 34 -O-) sm -R 35 Additionally, R 30 ~R 35 Each can be independently represented by an alkyl, alicyclic, or aromatic hydrocarbon group that may have substituents, and sm represents an integer from 1 to 100.

[0099] In the above formula (B1), n ​​represents an integer greater than or equal to 1. From the viewpoint of applicability to synthesis, it is preferably an integer from 1 to 5, more preferably an integer from 1 to 3, and even more preferably 1.

[0100] In the above formula (B2), R b3 This represents a hydrogen atom or a substituent. Specifically, there are two R atoms. b3 They can bond together to form a ring, and multiple Rs b3 They can be the same or different.

[0101] R b3 The type of substituent represented by this method is not particularly limited; well-known substituents can be cited, such as R in the above formula (B1). b1 The substituents are the groups exemplified in the representation of a certain method. Preferably, they are alkyl groups having 1 to 12 carbon atoms, more preferably straight-chain alkyl groups having 1 to 8 carbon atoms or branched alkyl groups having 3 to 8 carbon atoms, and even more preferably methyl groups.

[0102] Furthermore, R b3 Preferred 2 R b3 They bond together to form a ring, preferably two Rs. b3 They bond together to form a cyclohexane ring.

[0103] In the above formula (B2), R b4 This represents a hydrogen atom or a substituent. Multiple R groups are involved. b4 They can be the same or different.

[0104] R b4 The type of substituent represented by this method is not particularly limited; well-known substituents can be cited, such as R in the above formula (B1). b1 The substituents are the groups exemplified in the representation of a certain method. Preferably, they are alkyl groups having 1 to 12 carbon atoms, more preferably straight-chain alkyl groups having 1 to 8 carbon atoms or branched alkyl groups having 3 to 8 carbon atoms, and even more preferably methyl groups.

[0105] Furthermore, R b4 The preferred representation is a hydrogen atom.

[0106] In the above formula (B2), L b2 This indicates a linking group with a valence of m+1.

[0107] As a linking group with an m+1 valence, considering that the ability to suppress wind spots can be adjusted by controlling surface tension and the performance of the upper coating can be adjusted by controlling the pyrolysis rate of the pyrolysis component, it is preferable to be a hydrocarbon group with an m+1 valence that has 1 to 24 carbon atoms having substituents and a portion of the carbon atoms constituting the hydrocarbon group can be replaced by heteroatoms, and more preferably an aliphatic hydrocarbon group that can contain oxygen or nitrogen atoms with 1 to 10 carbon atoms.

[0108] The number of carbon atoms contained in the m+1 valence linking group is not particularly limited. Considering that the ability to suppress wind spots can be adjusted by controlling the surface tension and the performance of the upper coating can be adjusted by controlling the pyrolysis rate of the pyrolysis component, the number of carbon atoms is preferably 1 to 24, and more preferably 1 to 10.

[0109] As a linking group with an m+1 valence, it is preferably a linking group with a 3 to 4 valence, and more preferably a linking group with a 4 valence.

[0110] As a tetravalent linking group, the linking group represented by the following formula (3) is preferred.

[0111] -C(R b5 )3-b(-L b3 -*) b (3)

[0112] In equation (3) above, R b5 Indicates alkyl group, L b3 The symbol represents a divalent linker, * indicates the bonding position with Z, and b represents an integer from 1 to 3.

[0113] Among them, as R b5 The alkyl group referred to can be, for example, an alkyl group having 1 to 6 carbon atoms, and more specifically, methyl, ethyl and n-propyl.

[0114] Furthermore, as L b3 The divalent linking group represented can be, for example, the L in the above formula (B1). b1 The same group as the divalent linking group represented in one manner.

[0115] In the above formula (B2), Z represents an aliphatic hydrocarbon group or an organosilicon alkyl group having a fluorine atom, and is the same as Z in the above formula (B1).

[0116] In the above formula (B2), m represents an integer greater than 2. From the viewpoint of applicability to synthesis, an integer of 2 to 4 is preferred, and an integer of 2 to 3 is more preferred.

[0117] For reasons that it can impart orientation control capabilities to the adhesive layer of the present invention described later, certain compounds preferably also have photooriented groups.

[0118] As a photo-orientation group, considering the reason that the monomer having the photo-orientation group has good thermal or chemical stability, it is preferred to be a group that produces at least one of dimerization and isomerization by the action of light.

[0119] As a group that dimers through the action of light, specifically, for example, a group having a skeleton of at least one derivative selected from the group consisting of cinnamic acid derivatives, coumarin derivatives, chalcone derivatives, maleimide derivatives and benzophenone derivatives may be preferred.

[0120] On the other hand, as a group that isomerizes by the action of light, specifically, for example, a group having the skeleton of at least one compound selected from the group consisting of azobenzene compounds, stilbene compounds, spiropyran compounds, cinnamic acid compounds and hydrazine-β-keto ester compounds can be preferably included.

[0121] Preferably, the photooriented group has a skeleton of at least one derivative or compound selected from the group consisting of cinnamic acid derivatives, coumarin derivatives, chalcone derivatives, maleimide derivatives, azobenzene compounds, stilbene compounds, and spiropyran compounds, wherein, more preferably, it is a group having a skeleton of cinnamic acid derivatives or azobenzene compounds, and even more preferably, it is a group having a skeleton of cinnamic acid derivatives (hereinafter also simply referred to as "cinnamyl").

[0122] In this invention, a particular compound may be a monomer having polymerizable groups, but is preferably a polymer having repeating units.

[0123] <Repeating Unit B (Specific Cleavage Group)>

[0124] Considering that the ability to suppress wind spots can be adjusted by controlling surface tension and the performance of the upper coating can be adjusted by controlling the pyrolysis rate of the pyrolysis component, the specific compound is preferably a polymer having a repeating unit B containing a group represented by the above formula (B1) or (B2).

[0125] Considering factors such as excellent manufacturing suitability, the repeating unit B is preferably the repeating unit represented by the following formula (1) or (2).

[0126]

[0127] In equations (1) and (2) above, r and s independently represent integers greater than 1.

[0128] Furthermore, R B1 and R B2 Each can be used to represent a hydrogen atom or a substituent independently.

[0129] Furthermore, Y 1 and Y 2 -O- or -NR can be represented independently. Z -. Among them, R Z It represents a hydrogen atom or a substituent.

[0130] Furthermore, L B1 This indicates a linker group with an r+1 valence.

[0131] Furthermore, L B2 This indicates a linking group with a +1 valence.

[0132] Furthermore, B1 represents the group represented by the above formula (B1). In the above formula (B1), * indicates a group related to L. B1 Regarding the bonding positions, when r is an integer greater than 2, multiple B1s can be identical or different.

[0133] Furthermore, B2 represents the group represented by the above formula (B2). In the above formula (B2), * indicates a group related to L. B2 In the case that s is an integer greater than 2, multiple B2s can be the same or different.

[0134] In the above formula (1), R B1 It represents a hydrogen atom or a substituent.

[0135] R B1 The type of substituent represented by this method is not particularly limited; well-known substituents can be cited, such as R in the above formula (B1). b1 The substituents are the groups exemplified in the representation of a certain method. Preferably, they are alkyl groups having 1 to 12 carbon atoms, more preferably straight-chain alkyl groups having 1 to 8 carbon atoms or branched alkyl groups having 3 to 8 carbon atoms, and even more preferably methyl groups.

[0136] Furthermore, as R B1 , preferably representing a hydrogen atom or a methyl group.

[0137] In the above formula (1), Y 1 -O- or -NR can be represented independently. Z -. Among them, R Z It represents a hydrogen atom or a substituent.

[0138] Among them, R Z The type of substituent represented by this method is not particularly limited; well-known substituents can be cited, such as R in the above formula (B1). b1 The substituents are the groups exemplified in the representation of a certain method. Preferably, they are alkyl groups having 1 to 12 carbon atoms, more preferably straight-chain alkyl groups having 1 to 8 carbon atoms or branched alkyl groups having 3 to 8 carbon atoms, and even more preferably methyl groups.

[0139] And, as Y 1 Preferably, it represents -O- or -NH-, and more preferably -O-.

[0140] In the above formula (1), LB1 This indicates a linker group with an r+1 valence.

[0141] As the r+1 valence linking group, considering that the ability to control the surface tension can be adjusted to suppress the freckles and that the performance of the upper coating can be adjusted by controlling the pyrolysis rate of the pyrolysis component, it is preferable to be a hydrocarbon group with an r+1 valence that has 1 to 24 carbon atoms having substituents and a portion of the carbon atoms constituting the hydrocarbon group can be replaced by heteroatoms, and more preferably an aliphatic hydrocarbon group that can contain oxygen or nitrogen atoms having 1 to 10 carbon atoms.

[0142] The number of carbon atoms contained in the r+1 valence linking group is not particularly limited. Considering that the ability to suppress wind spots can be adjusted by controlling surface tension and the performance of the upper coating can be adjusted by controlling the pyrolysis rate of the pyrolysis component, the number of carbon atoms is preferably 1 to 24, and more preferably 1 to 10.

[0143] As the r+1 valence linking group, it is preferably a 2- to 3-valence linking group, and more preferably a 2-valence linking group.

[0144] As a divalent linking group, examples include L in the above formula (B1). b1 The same group as the divalent linking group represented in one manner.

[0145] In equation (1) above, r represents an integer greater than or equal to 1. From the viewpoint of applicability to synthesis, it is preferably an integer from 1 to 3, more preferably an integer from 1 to 2, and even more preferably 1.

[0146] In equation (2) above, R B2 It represents a hydrogen atom or a substituent.

[0147] R B2 The type of substituent represented by this method is not particularly limited; well-known substituents can be cited, such as R in the above formula (B1). b1 The substituents are the groups exemplified in the representation of a certain method. Preferably, they are alkyl groups having 1 to 12 carbon atoms, more preferably straight-chain alkyl groups having 1 to 8 carbon atoms or branched alkyl groups having 3 to 8 carbon atoms, and even more preferably methyl groups.

[0148] Furthermore, as R B2 , preferably representing a hydrogen atom or a methyl group.

[0149] In equation (2) above, Y 2 Indicates -O- or -NR Z -. Among them, R Z It represents a hydrogen atom or a substituent.

[0150] Among them, R ZThe type of substituent represented by this method is not particularly limited; well-known substituents can be cited, such as R in the above formula (B1). b1 The substituents are the groups exemplified in the representation of a certain method. Preferably, they are alkyl groups having 1 to 12 carbon atoms, more preferably straight-chain alkyl groups having 1 to 8 carbon atoms or branched alkyl groups having 3 to 8 carbon atoms, and even more preferably methyl groups.

[0151] And, as Y 2 Preferably, it represents -O- or -NH-, and more preferably -O-.

[0152] In equation (2) above, L B2 This indicates a linking group with a +1 valence.

[0153] As a linking group with an s+1 valence, considering that the ability to suppress wind spots can be adjusted by controlling surface tension and the performance of the upper coating can be adjusted by controlling the pyrolysis rate of the pyrolysis component, it is preferable to be a hydrocarbon group with an s+1 valence that has 1 to 24 carbon atoms having substituents and a portion of the carbon atoms constituting the hydrocarbon group can be replaced by heteroatoms, and more preferably an aliphatic hydrocarbon group that can contain oxygen or nitrogen atoms having 1 to 10 carbon atoms.

[0154] The number of carbon atoms contained in the s+1 valence linking group is not particularly limited. Considering that the ability to suppress wind spots can be adjusted by controlling the surface tension and the performance of the upper coating can be adjusted by controlling the pyrolysis rate of the pyrolysis component, the preferred number is 1 to 24, and more preferably 1 to 10.

[0155] As a linking group with an s+1 valence, a divalent linking group is preferred.

[0156] As a divalent linking group, examples include L in the above formula (B1). b1 The same group as the divalent linking group represented in one manner.

[0157] In equation (2) above, s represents an integer greater than or equal to 1. From the viewpoint of applicability to synthesis, it is preferably an integer from 1 to 2, and more preferably 1.

[0158] As a specific example of a repeating unit B containing the group represented by the above formula (B1), the repeating units represented by the following formulas B-1 to B-22 can be cited. As a specific example of a repeating unit B containing the group represented by the above formula (B2), the repeating units represented by the following formulas B-23 to B-24 can be cited.

[0159]

[0160]

[0161]

[0162] The content of repeating unit B in the specific compound is not particularly limited, but from the perspective of improving the suppression effect of freckles, it is preferably 15 to 75% by mass relative to all repeating units of the specific compound (polymer), more preferably 20 to 50% by mass, and even more preferably 25 to 45% by mass.

[0163] <Repeating Unit A (Photooriented Group)>

[0164] Considering that the liquid crystal compound can be oriented when an optically anisotropic layer is formed as an upper layer using a liquid crystal compound, the preferred compound is a copolymer having repeating unit A containing a photo-orienting group and the aforementioned repeating unit B.

[0165] Among them, as a photo-orientation group, the same group as the group described as a photo-orientation group that a particular compound may have can be cited.

[0166] The structure of the main chain of the repeating unit A is not particularly limited, and well-known structures can be cited. For example, the backbone is preferably selected from the group consisting of (meth)acrylic acid, styrene, siloxane, cycloolefin, methylpentene, amide and aromatic ester systems.

[0167] Among these, a skeleton selected from the group consisting of (meth)acrylic, siloxane, and cycloolefin systems is more preferred, and a (meth)acrylic skeleton is even more preferred.

[0168] As the repeating unit A containing the photo-orientation group, considering the good orientation of the upper layer formed by using a liquid crystal compound as the upper layer (hereinafter simply referred to as "liquid crystal orientation"), the repeating unit represented by the following formula (A) is preferred.

[0169]

[0170] In the above formula (A), R A1 It represents a hydrogen atom or a substituent.

[0171] Furthermore, L A1 This indicates a single bond or a divalent linker.

[0172] Furthermore, R A2 R A3 R A4 R A5 and R A6 Each can be used independently to represent a hydrogen atom or a substituent. R A2 R A3 R A4 RA5 and R A6 Two adjacent groups in a ring can bond together to form a ring.

[0173] In the above formula (A), R A1 It represents a hydrogen atom or a substituent.

[0174] R A1 The type of substituent represented by this method is not particularly limited; well-known substituents can be cited, such as R in the above formula (B1). b1 The substituents are the groups exemplified in the representation of a certain method. Preferably, they are alkyl groups having 1 to 12 carbon atoms, more preferably straight-chain alkyl groups having 1 to 8 carbon atoms or branched alkyl groups having 3 to 8 carbon atoms, and even more preferably methyl groups.

[0175] In the above formula (A), L A1 This indicates a single bond or a divalent linker.

[0176] As L A1 The divalent linking group represented in one manner can be exemplified by, for example, the L in the above formula (B1). b1 The same group as the divalent linking group represented in one manner.

[0177] Among them, as L A1 The divalent linking group, as represented in one embodiment, is preferably a combination of at least two groups selected from the group consisting of a linear alkylene group having 1 to 10 carbon atoms that may have substituents, a branched or cyclic alkylene group having 3 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms that may have substituents, -O-, -CO-, and -N(Q)-. Q represents a hydrogen atom or a substituent.

[0178] The definitions of the above groups are the same as those of the above L. b1 The definitions of the groups described in the divalent linking groups are the same.

[0179] In the above formula (A), R A2 R A3 R A4 R A5 and R A6 Each can be represented independently by a hydrogen atom or a substituent. There is no particular limitation on the types of substituents mentioned above; any known substituents can be cited, such as R in formula (B1). b1 The substituents exemplified in one manner are represented by the group.

[0180] R A2 R A3 R A4R A5 and R A6 Two adjacent groups in a ring can bond together to form a ring.

[0181] As R A2 R A3 R A4 R A5 and R A6 The substituents represented are preferably, independently, a halogen atom, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, a straight-chain haloalkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, a cyano group, an amino group, or a group represented by formula (4) below, for the purpose of improving liquid crystal orientation. Furthermore, the above substituents may include -(CH2). na -or -O-(CH2) na - indicates the linking group. na represents an integer from 1 to 10.

[0182]

[0183] In equation (4) above, * represents the bonding position.

[0184] R A7 Alkyl groups having 1 to 20 carbon atoms.

[0185] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with fluorine or chlorine atoms being preferred.

[0186] As a straight-chain alkyl group, it is preferably an alkyl group having 1 to 6 carbon atoms, for example, methyl, ethyl and n-propyl.

[0187] As a branched alkyl group, it is preferably an alkyl group having 3 to 6 carbon atoms, for example isopropyl and tert-butyl.

[0188] As a cyclic alkyl group, it is preferably an alkyl group having 3 to 6 carbon atoms, for example, cyclopropyl, cyclopentyl and cyclohexyl.

[0189] The alkyl halide is a straight-chain compound with 1 to 20 carbon atoms, preferably a fluoroalkyl group with 1 to 4 carbon atoms, such as trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluorobutyl, 2,2,3,3,4,4,5,5-octafluoropentyl and 2,2,3,3,4,4,5,5,6,6,7,7-dodecylfluoroheptyl. From the viewpoint of good liquid crystal alignment and good topcoatability, 2,2,3,3,4,4,5,5-octafluoropentyl or 2,2,3,3,4,4,5,5,6,6,7,7-dodecylfluoroheptyl is preferred.

[0190] The alkoxy group having 1 to 20 carbon atoms is preferably an alkoxy group having 1 to 18 carbon atoms, more preferably an alkoxy group having 3 to 18 carbon atoms, and even more preferably an alkoxy group having 6 to 18 carbon atoms. Examples include methoxy, ethoxy, n-butoxy, methoxyethoxy, n-hexoxy, n-octoxy, n-decoxy, n-dodecyloxy, and n-tetradecyloxy.

[0191] The aryl group having 6 to 20 carbon atoms is preferred, with 6 to 12 carbon atoms being an example, such as phenyl, α-methylphenyl and naphthyl.

[0192] The aryloxy group having 6 to 20 carbon atoms is preferably an aryloxy group having 6 to 12 carbon atoms, for example, phenoxy and 2-naphthoxy.

[0193] Examples of amino groups include primary amino groups (-NH2); secondary amino groups such as methylamino groups; tertiary amino groups such as dimethylamino, diethylamino, dibenzylamino, and groups in which the nitrogen atom of a nitrogen-containing heterocyclic compound (e.g., pyrrolidine, piperidine, piperazine, etc.) is used as a linking bond.

[0194] From the viewpoint that photo-alignment groups readily interact with liquid crystal compounds and result in improved liquid crystal alignment, R in the above formula (A) is preferred. A2 R A3 R A4 R A5 and R A6 At least R in A4 The above-mentioned substituents (preferably alkoxy or haloalkyl groups having 1 to 20 carbon atoms) are preferred, and considering the reasons of improving the linearity of the obtained specific compound, facilitating interaction with liquid crystal compounds, and improving liquid crystal orientation, R is even more preferred. A2 R A3 R A5 and R A6 Both represent hydrogen atoms.

[0195] As a specific example of a repeating unit A containing a photooriented group, the repeating units represented by the following formulas A-1 to A-30 can be cited.

[0196]

[0197]

[0198] The content of repeating unit A in a particular compound is not particularly limited, but considering the reason that the liquid crystal orientation becomes better, it is preferably 5 to 50% by mass relative to all repeating units in the particular compound (polymer), more preferably 10 to 40% by mass.

[0199] <Repeating Unit C (Crosslinking Group)>

[0200] Considering that the liquid crystal orientation becomes better by suppressing orientation relaxation based on improving solvent resistance, the specific compound is preferably a copolymer having repeating unit C containing crosslinking groups, the repeating unit B and the repeating unit A.

[0201] There is no particular limitation on the type of crosslinking group, and known crosslinking groups can be cited. Among them, cationic polymeric groups or free radical polymeric groups are preferred from the viewpoint of excellent adhesion to the upper layer disposed on the adhesive layer.

[0202] Examples of cationic polymerizable groups include epoxy, epoxycyclohexyl, and oxocyclobutyl.

[0203] Examples of free radical polymerizable groups include acryloyl, methacryloyl, vinyl, styryl, and allyl.

[0204] The structure of the main chain of the repeating unit C containing crosslinking groups is not particularly limited, and well-known structures can be cited, such as a backbone preferably selected from the group consisting of (meth)acrylic acid, styrene, siloxane, cycloolefin, methylpentene, amide and aromatic ester systems.

[0205] Among these, a skeleton selected from the group consisting of (meth)acrylic, siloxane, and cycloolefin systems is more preferred, and a (meth)acrylic skeleton is even more preferred.

[0206] From the perspective of improving liquid crystal orientation, the repeating unit C containing crosslinking groups is preferably the repeating unit represented by the following formula (C).

[0207]

[0208] In the above formula (C), R C1 It represents a hydrogen atom or a substituent.

[0209] Furthermore, L C1 This indicates a single bond or a divalent linker.

[0210] Furthermore, L C2 This indicates a linking group with a valence of q+1.

[0211] Furthermore, P represents a crosslinking group.

[0212] Furthermore, q represents an integer greater than 1. When q is an integer greater than 2, multiple Ps can be the same or different.

[0213] In the above formula (C), RC1 It represents a hydrogen atom or a substituent.

[0214] R C1 The type of substituent represented by this method is not particularly limited; well-known substituents can be cited, such as R in the above formula (B1). b1 The substituents are the groups exemplified in the representation of a certain method. Preferably, they are alkyl groups having 1 to 12 carbon atoms, more preferably straight-chain alkyl groups having 1 to 8 carbon atoms or branched alkyl groups having 3 to 8 carbon atoms, and even more preferably methyl groups.

[0215] Furthermore, as R C1 , preferably representing a hydrogen atom or a methyl group.

[0216] In the above formula (C), L C1 This indicates a single bond or a divalent linker.

[0217] As L C1 The divalent linking group represented in one manner can be exemplified by, for example, the L in the above formula (B1). b1 The same group as the divalent linking group represented in one manner.

[0218] Among them, as L C1 The divalent linking group, as represented in one embodiment, is preferably a combination of at least two groups selected from the group consisting of a linear alkylene group having 1 to 10 carbon atoms that may have substituents, a branched or cyclic alkylene group having 3 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms that may have substituents, -O-, -CO-, and -N(Q)-. Q represents a hydrogen atom or a substituent.

[0219] The definitions of the above groups are the same as those of the above L. b1 The definitions of the groups described in the divalent linking groups are the same.

[0220] L C2 This indicates a linking group with a valence of q+1.

[0221] As a q+1 valence linking group, considering the reason that the liquid crystal orientation is improved, it is preferable to be a q+1 valence hydrocarbon group with 1 to 24 carbon atoms that can have substituents and a hydrocarbon group in which part of the carbon atom constituting the hydrocarbon group can be substituted by heteroatoms, and more preferably an aliphatic hydrocarbon group with 1 to 10 carbon atoms that can contain oxygen or nitrogen atoms.

[0222] The number of carbon atoms contained in the q+1 valence linker is not particularly limited, but from the perspective of improving liquid crystal orientation, it is preferably 1 to 24, and more preferably 1 to 10.

[0223] As a linking group with a valence of q+1, a divalent linking group is preferred. Examples of divalent linking groups include those corresponding to L in formula (B1) above. b1 The same group as the divalent linking group represented in one manner.

[0224] P represents a crosslinking group. The definition of a crosslinking group is as described above.

[0225] q represents an integer greater than or equal to 1. From the perspective of improving liquid crystal alignment, an integer from 1 to 5 is preferred, an integer from 1 to 3 is more preferred, and 1 is even more preferred.

[0226] As a specific example of a repeating unit C containing a crosslinking group, the repeating units represented by the following formulas C-1 to C-8 can be cited.

[0227]

[0228] The content of any repeating unit C in a particular compound is not particularly limited. Considering the reason that the liquid crystal orientation becomes better, it is preferably 10 to 60% by mass relative to all repeating units of the particular compound (polymer), more preferably 10 to 40% by mass.

[0229] As a preferred form of a particular compound, the polymer may have other repeating units besides those described above.

[0230] Examples of monomers (free radical polymerizable monomers) that form other repeating units besides those mentioned above include acrylate compounds, methacrylate compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

[0231] There are no particular limitations on the synthesis method of polymers that are preferred for a particular compound; for example, well-known methods such as one-step polymerization and dropwise addition can be cited.

[0232] As a specific example of a one-step polymerization method, it can be synthesized by mixing the monomers forming repeating unit B, repeating unit A, repeating unit C, and any other repeating units, and then heating them in an organic solvent using a free radical polymerization initiator to achieve one-step polymerization. This synthesis method is very simple, as all reagents are added to a flask and heated.

[0233] Furthermore, as a specific example of the dropwise addition method, the method is as follows: a portion or all of the monomer component consisting of the monomer forming the repeating unit B, the monomer forming the repeating unit A, the monomer forming the repeating unit C, and the monomer forming any other repeating unit is mixed with an organic solvent, heated in advance at a predetermined temperature (preferably 60 to 100°C), and polymerized while dropwise addition of a free radical polymerization initiator or a free radical polymerization initiator and the remaining monomer component (limited to the case where a portion of the monomer component has been used in advance).

[0234] In the dropwise addition method, from the perspective of manufacturing stability, the method of adding the free radical polymerization initiator dropwise only (hereinafter, also referred to as "dropwise addition method A") is superior to the one-time polymerization method.

[0235] Furthermore, in the dropwise addition method, the method of adding the free radical polymerization initiator and a portion of the monomer components dropwise (hereinafter also referred to as "dropwise addition method B") allows for the control of the introduction rate of monomers with different reactivity by changing the loading ratio of monomers in the flask and the dropping solution.

[0236] Furthermore, specific examples of organic solvents can be cited, as described later. In this invention, from the viewpoint of appropriately controlling the decomposition of repeating unit B, aromatic hydrocarbons are preferred as organic solvents during polymerization, and toluene is more preferred.

[0237] The weight-average molecular weight (Mw) of a particular compound is not particularly limited, but from the perspective of improving liquid crystal orientation, it is preferably 10,000 to 500,000, more preferably 10,000 to 300,000, and even more preferably 30,000 to 150,000.

[0238] In this invention, the weight-average molecular weight and number-average molecular weight are values ​​obtained by gel permeation chromatography (GPC) under the conditions shown below.

[0239] • Solvent (eluent): THF (tetrahydrofuran)

[0240] • Device Name: TOSOH HLC-8320GPC

[0241] • String: Connects 3 TOSOH TSKgel Super HZM-H (4.6mm × 15cm) tubes for use

[0242] • Column temperature: 40℃

[0243] • Sample concentration: 0.1% by mass

[0244] • Flow rate: 1.0 ml / min

[0245] • Calibration curves: Calibration curves were obtained using seven samples based on TOSOH-prepared TSK standard polystyrene with Mw values ​​ranging from 2,800,000 to 1,050 (Mw / Mn = 1.03 to 1.06).

[0246] [Adhesive]

[0247] The type of adhesive included in the adhesive composition of the present invention is not particularly limited. It may be a simple dry-curing resin composed only of a non-polymerizable resin (hereinafter also referred to as "resin adhesive"), or a polymerizable compound.

[0248] <Resin Adhesives>

[0249] Examples of resin adhesives include epoxy resins, diallyl phthalate resins, silicone resins, phenolic resins, unsaturated polyester resins, polyimide resins, polyurethane resins, melamine resins, urea-formaldehyde resins, ionomer resins, ethylene ethyl acrylate resins, acrylonitrile-acrylate-styrene copolymer resins, acrylonitrile-styrene resins, acrylonitrile-chlorinated polyethylene-styrene copolymer resins, vinyl acetate resins, ethylene-vinyl alcohol copolymer resins, acrylonitrile-butadiene-styrene copolymer resins, vinyl chloride resins, chlorinated polyethylene resins, polyvinylidene chloride resins, cellulose acetate resins, and fluoropolymers. Polyoxymethylene resin, polyamide resin, polyarylate resin, thermoplastic polyurethane elastomer, polyetheretherketone resin, polyethersulfone resin, polyethylene, polypropylene, polycarbonate resin, polystyrene, polystyrene-maleic acid copolymer resin, polystyrene-acrylic acid copolymer resin, polyphenylene ether resin, polyphenylene sulfide resin, polybutadiene resin, polybutylene terephthalate resin, acrylic resin, methacrylic acid resin, methylpentene resin, polylactic acid, polybutylene succinate resin, butyral resin, formalin resin, polyvinyl alcohol, polyvinylpyrrolidone, ethyl cellulose, carboxymethyl cellulose, gelatin, and their copolymer resins.

[0250] <Polymerizing compounds>

[0251] Examples of polymerizable compounds include epoxy monomers, (meth)acrylic monomers, and oxetyl monomers, with epoxy monomers or (meth)acrylic monomers being preferred.

[0252] Furthermore, polymeric liquid crystal compounds or urethane acrylate monomers can also be used as polymeric compounds.

[0253] Examples of epoxy monomers, i.e., monomers containing epoxy groups, include bisphenol A type epoxy resin, bisphenol F type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol S type epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, phenolic varnish type epoxy resin, o-cresol phenolic varnish type epoxy resin, trihydroxyphenylmethane type epoxy resin, trifunctional epoxy resin, tetraphenolyl ethane type epoxy resin, dicyclopentadienylphenol type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol A nucleating polyol type epoxy resin, polypropylene glycol type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, glyoxal type epoxy resin, alicyclic epoxy resin, and heterocyclic epoxy resin.

[0254] Regarding (meth)acrylic monomers, namely acrylate monomers and methacrylate monomers, examples of trifunctional monomers include trimethylolpropane triacrylate, trimethylolpropane PO (propylene oxide) modified triacrylate, trimethylolpropane EO (ethylene oxide) modified triacrylate, trimethylolpropane triacrylate methacrylate, and pentaerythritol triacrylate. Furthermore, examples of monomers with four or more functionalities include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate.

[0255] There are no particular limitations on polymerizable liquid crystal compounds; for example, compounds capable of any of the following orientations can be cited: vertical orientation, uniform orientation, mixed orientation, and cholesterol orientation.

[0256] Liquid crystal compounds are typically classified into rod-shaped and disc-shaped types based on their shape. Furthermore, they are categorized into low-molecular-weight and high-molecular-weight types. High-molecular-weight compounds generally refer to compounds with a degree of polymerization of 100 or higher (Polymer Physics / Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992). In this invention, any liquid crystal compound can be used, but rod-shaped or disc-shaped liquid crystal compounds (disc-shaped liquid crystal compounds) are preferred. Moreover, liquid crystal compounds with a monomeric or relatively low molecular weight structure and a degree of polymerization of less than 100 are preferred.

[0257] Furthermore, examples of polymerizable groups found in polymerizable liquid crystal compounds include acryloyl, methacryloyl, epoxy, and vinyl groups.

[0258] By polymerizing this polymerizable liquid crystal compound, the orientation of the liquid crystal compound can be fixed. Furthermore, once the liquid crystal compound is fixed through polymerization, it is no longer necessary to exhibit liquid crystal properties.

[0259] As a rod-shaped liquid crystal compound, the compound described in claim 1 of Japanese Patent Application Publication No. 11-513019 or in paragraphs

[0026] to

[0098] of Japanese Patent Application Publication No. 2005-289980 is preferred, and as a disc-shaped liquid crystal compound, the compound described in paragraphs

[0020] to

[0067] of Japanese Patent Application Publication No. 2007-108732 or in paragraphs

[0013] to

[0108] of Japanese Patent Application Publication No. 2010-244038 is preferred.

[0260] As the aforementioned polymerizable liquid crystal compound, a liquid crystal compound with reverse wavelength dispersion can be used.

[0261] In this specification, a liquid crystal compound with "reverse wavelength dispersion" refers to a liquid crystal compound whose in-plane retardation (Re) value becomes equal or higher as the measurement wavelength increases when the in-plane retardation (Re) value of a phase retardation film made using this liquid crystal compound is measured at a specific wavelength (visible light range).

[0262] The liquid crystal compound with reverse wavelength dispersion is not particularly limited as long as it is a compound that can form a film with reverse wavelength dispersion as described above. Examples include compounds represented by general formula (I) as described in Japanese Patent Application Publication No. 2008-297210 (especially the compounds described in paragraphs

[0034] to

[0039] ), compounds represented by general formula (1) as described in Japanese Patent Application Publication No. 2010-084032 (especially the compounds described in paragraphs

[0067] to

[0073] ), and compounds represented by general formula (1) as described in Japanese Patent Application Publication No. 2016-081035 (especially the compounds described in paragraphs

[0043] to

[0055] ).

[0263] Furthermore, examples include the compounds described in paragraphs

[0027] to

[0100] of Japanese Patent Application Publication No. 2011-006360, paragraphs

[0028] to

[0125] of Japanese Patent Application Publication No. 2011-006361, paragraphs

[0034] to

[0298] of Japanese Patent Application Publication No. 2012-207765, paragraphs

[0016] to

[0345] of Japanese Patent Application Publication No. 2012-077055, paragraphs

[0017] to

[0072] of Japanese Patent Application Publication No. WO12 / 141245, paragraphs

[0021] to

[0088] of Japanese Patent Application Publication No. WO12 / 147904, and paragraphs

[0028] to

[0115] of Japanese Patent Application Publication No. WO14 / 147904.

[0264] There are no particular limitations on the orientation state of the liquid crystal compound (orientation state), and known orientation states can be cited. Examples of orientation states include uniform orientation and perpendicular orientation. More specifically, when the liquid crystal compound is rod-shaped, examples of orientation states include nematic orientation (forming a nematic phase), smectic orientation (forming a smectic phase), cholesterol orientation (forming a cholesterol phase), and mixed orientation. When the liquid crystal compound is disc-shaped, examples of orientation states include nematic orientation, columnar orientation (forming a columnar phase), and cholesterol orientation.

[0265] [Photo-acid generator]

[0266] The adhesive composition of the present invention preferably contains a photoacid-generating agent.

[0267] There are no particular limitations on the photoacid-generating agent, but it is preferred to be a compound that generates acid by sensing activation light with a wavelength of 300 nm or higher (preferably 300-450 nm). Furthermore, for photoacid-generating agents that do not directly sense activation light with a wavelength of 300 nm or higher, as long as they are compounds that generate acid by sensing activation light with a wavelength of 300 nm or higher by using a sensitizer simultaneously, they can also be used in combination with a sensitizer and are preferred.

[0268] As a photoacid-generating agent, it is preferable to be a photoacid-generating agent that produces an acid with a pKa of 4 or less, more preferably a photoacid-generating agent that produces an acid with a pKa of 3 or less, and even more preferably a photoacid-generating agent that produces an acid with a pKa of 2 or less. Furthermore, in this invention, pKa basically refers to the pKa in water at 25°C. A pKa that cannot be measured in water refers to the pKa measured using a solvent suitable for measurement. Specifically, pKa can be referred to in chemical handbooks, etc. As an acid with a pKa of 3 or less, sulfonic acid or phosphonic acid is preferred, more preferably sulfonic acid.

[0269] Examples of photoacid generators include onium salts, trichloromethyltriazines, sulfonium salts, iodinated salts, quaternary ammonium salts, diazomethane compounds, imide sulfonates, and oxime sulfonates. Onium salts, imide sulfonates, or oxime sulfonates are preferred, and onium salts or oxime sulfonates are more preferred. One photoacid generator can be used alone or in combination of two or more.

[0270] The adhesive composition of the present invention may contain other components besides the specific compounds, adhesives and photoacid generators described above.

[0271] [Polymerization initiator]

[0272] When using polymerizable compounds as adhesives, the adhesive compositions of the present invention preferably contain a polymerization initiator.

[0273] There are no particular limitations on polymerization initiators, but according to the form of polymerization reaction, examples include thermal polymerization initiators and photopolymerization initiators.

[0274] As a polymerization initiator, a photopolymerization initiator that can initiate a polymerization reaction by ultraviolet irradiation is preferred.

[0275] Examples of photopolymerization initiators include α-carbonyl compounds, azo ethers, α-hydrocarbon-substituted aromatic azo compounds, polynuclear quinone compounds, combinations of triarylimidazolium dimers and p-aminophenyl ketones, acridine and phenazine compounds, oxadiazole compounds, and acylphosphine oxides.

[0276] [Solvent]

[0277] From the viewpoint of operability in forming the adhesive layer, the adhesive composition of the present invention preferably contains a solvent.

[0278] Examples of solvents include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone), ethers (e.g., dioxane and tetrahydrofuran), aliphatic hydrocarbons (e.g., hexane), alicyclic hydrocarbons (e.g., cyclohexane), aromatic hydrocarbons (e.g., toluene, xylene, and trimethylbenzene), carbon halides (e.g., dichloromethane, dichloroethane, dichlorobenzene, and chlorotoluene), esters (e.g., methyl acetate, ethyl acetate, and butyl acetate), water, alcohols (e.g., ethanol, isopropanol, butanol, and cyclohexanol), cellosols (e.g., methyl cellosols and ethyl cellosols), cellosol acetates, sulfoxides (e.g., dimethyl sulfoxide), and amides (e.g., dimethylformamide and dimethylacetamide).

[0279] One solvent can be used alone, or two or more solvents can be used at the same time.

[0280] [Compound]

[0281] The compounds of the present invention are compounds having groups represented by the above formula (B1) or (B2), i.e., the specific compounds described above.

[0282] The compounds of the present invention may be compounds having groups represented by the following formula (P0) or compounds having groups represented by the following formula (P1).

[0283]

[0284] In the above formulas (P0) and (P1), * indicates the bonding position with * in the above formulas (B1) or (B2).

[0285] Furthermore, in the above equation (P0), P 1 It indicates a polymerizable group.

[0286] Furthermore, in the above equation (P1), R 1 and R 2 Each can independently represent a hydrogen atom or a substituent. Multiple R's can be used to represent either a hydrogen atom or a substituent. 1 They can be the same or different.

[0287] Furthermore, in the above equations (P0) and (P1), L 1 This indicates a divalent linker.

[0288] In the above formula (P0), P 1 It indicates a polymerizable group.

[0289] As a polymerizable group, it is preferably a cationic polymerizable group or a free radical polymerizable group, and more preferably a free radical polymerizable group.

[0290] Examples of cationic polymerizable groups include epoxy groups, epoxycyclohexyl groups, and oxocyclobutyl groups.

[0291] Examples of free radical polymerizable groups include methacryloyl, acryloyl, methacrylamide, acrylamide, vinyl, styrene, and allyl. Among these, methacryloyl and acryloyl are preferred.

[0292] In the above formula (P1), R 1 and R 2 Each can be used to represent a hydrogen atom or a substituent independently.

[0293] R 1 and R 2 The type of substituent represented by this method is not particularly limited; well-known substituents can be cited, such as R in the above formula (B1). b1 The substituents are the groups exemplified in the representation of a certain method. Preferably, they are alkyl groups having 1 to 12 carbon atoms, more preferably straight-chain alkyl groups having 1 to 8 carbon atoms or branched alkyl groups having 3 to 8 carbon atoms, and even more preferably methyl groups.

[0294] Furthermore, as R 1 and R 2 Preferably, it contains hydrogen atoms or methyl groups.

[0295] In the above equations (P0) and (P1), L 1 This indicates a divalent linker.

[0296] As a divalent linking group, examples include L in the above formula (B1). b1 The same group as the divalent linking group represented in one manner.

[0297] Furthermore, in the above formula (P1), "R"1 2C = CR 2 -" represents the part and L 1 A portion of it can constitute a polymerizable group. Examples of such polymerizable groups include methacryloyl, acryloyl, methacrylamide, and acrylamide, with methacryloyl and acryloyl being preferred.

[0298] Specific examples of compounds of the present invention having the groups represented by the above formulas (P0) and (P1) include compounds represented by the following formulas mB-1 to mB-23. Furthermore, in the formulas of the following specific examples, Me represents a methyl group.

[0299] [Chemical Formula 10]

[0300]

[0301]

[0302] The adhesive layer of the present invention is a layer formed using the adhesive composition of the present invention described above. More specifically, the adhesive layer is a layer in which at least one of the group consisting of light, heat, acid, and alkali (hereinafter referred to as "acid, etc.") is supplied to the coating of the adhesive composition to cause the ketal structure contained in a specific cleavage group to cleave, thereby removing the aliphatic hydrocarbon group or organosiloxane group having a fluorine atom.

[0303] Furthermore, when the specific compound contained in the adhesive composition of the present invention has photo-orienting groups, the adhesive layer of the present invention is a layer whose surface has orientation control capability. More specifically, the adhesive layer is a layer formed by performing a photo-orientation treatment after supplying an acid or the like to the coating of the adhesive composition. In addition, having orientation control capability means having the function of orienting the liquid crystal compound disposed on the adhesive layer in a predetermined direction. Furthermore, when the adhesive layer contains the aforementioned polymeric liquid crystal compound, having orientation control capability can mean having the function of orienting the aforementioned polymeric liquid crystal compound contained in the adhesive layer in a predetermined direction.

[0304] Furthermore, in the case where the adhesive composition of the present invention contains a photoacid generator, the supply of acid or the like to the coating of the adhesive composition can be in the manner of generating acid from the photoacid generator in the coating.

[0305] That is, when the specific compound contained in the adhesive composition of the present invention has a photo-oriented group and the adhesive composition of the present invention contains a photoacid generator, the method of forming the adhesive layer preferably includes a step (step 1) of performing a photo-oriented treatment on the coating film after the photoacid generator in the coating film obtained using the adhesive composition generates acid.

[0306] When the adhesive composition contains a polymerizable compound, in step 1 above, it is preferable to perform a curing treatment on the coating obtained using the above adhesive composition, and then perform a treatment to generate acid from the photoacid generator in the coating (hereinafter also simply referred to as "acid generation treatment"). After that, the coating is photo-oriented to form an adhesive layer.

[0307] In addition, as will be described later, solidification and acid generation can be carried out simultaneously.

[0308] The following is a detailed description of the method for performing the above-mentioned curing treatment.

[0309] There are no particular limitations on the method of forming a coating film of the adhesive composition. For example, one method is to apply the adhesive composition onto a support and perform a drying process as needed.

[0310] The support structure will be described in detail later.

[0311] Furthermore, an orientation layer can be configured on the support.

[0312] There are no particular limitations on the method of coating the adhesive composition. Examples of coating methods include spin coating, air knife coating, curtain coating, roller coating, wire-wound bar coating, gravure printing coating, and mold coating.

[0313] Next, the coating film of the adhesive composition is subjected to a curing treatment and a treatment in which acid is generated by the photoacid generator in the coating film (hereinafter also referred to as "acid generation treatment").

[0314] As a curing process, examples include light irradiation or heat treatment.

[0315] Furthermore, the curing conditions are not particularly limited, but ultraviolet light is preferred for polymerization caused by light irradiation. The preferred irradiation dose is 10 mJ / cm². 2 ~50J / cm 2 More preferably 20 mJ / cm 2 ~5J / cm 2 Further preferred is 30 mJ / cm 2 ~3J / cm 2 The preferred value is 50–1000 mJ / cm³. 2 Furthermore, to promote the polymerization reaction, it can be carried out under heating conditions.

[0316] The treatment to generate acid from a photoacid-generating agent in the coating film involves irradiating the photoacid-generating agent contained in the adhesive composition with light to generate acid. By performing this treatment, cleavage occurs in the cleavage groups, and groups containing fluorine or silicon atoms are released.

[0317] The light irradiation treatment performed in the above process can be any treatment that sensitizes the photoacid-producing agent; for example, ultraviolet irradiation can be used. As the light source, lamps that emit ultraviolet light, such as high-pressure mercury lamps and metal halide lamps, can be used. Furthermore, the irradiation dose is preferably 10 mJ / cm². 2 ~50J / cm 2 More preferably 20 mJ / cm 2 ~5J / cm 2 Further preferred is 30 mJ / cm 2 ~3J / cm 2 The preferred value is 50–1000 mJ / cm³. 2 .

[0318] Regarding the aforementioned curing and acid-generating treatments, the acid-generating treatment can be performed after the curing treatment, or the curing and acid-generating treatments can be performed simultaneously. In particular, from a productivity point of view, it is preferable to perform the simultaneous acid-generating agent and polymerization initiator in the adhesive composition when they are exposed to light of the same wavelength.

[0319] The method for photo-alignment treatment of the coating film of the adhesive composition formed above (including the cured film of the adhesive composition that has undergone curing treatment) is not particularly limited, and known methods can be cited.

[0320] As a light orientation treatment, examples include irradiating a coating of an adhesive composition (including a cured film of the adhesive composition that has undergone a curing treatment) with polarized light or irradiating it with unpolarized light from an oblique direction relative to the surface of the coating.

[0321] In the optical orientation process, there is no particular limitation on the polarized light irradiated; for example, linearly polarized light, circularly polarized light, and elliptically polarized light can be cited, with linearly polarized light being preferred.

[0322] Furthermore, the "tilt direction" of irradiating unpolarized light is not particularly limited as long as it is a direction tilted at a polar angle θ (0 < θ < 90°) relative to the normal direction of the coating surface, and can be appropriately selected according to the purpose. θ is preferably 20 to 80°.

[0323] The wavelength of polarized or unpolarized light is not particularly limited as long as it is light that is photosensitive by photooriented groups. Examples include ultraviolet light, near-ultraviolet light, and visible light, with near-ultraviolet light of 250 to 450 nm being preferred.

[0324] Furthermore, examples of light sources for irradiating polarized or unpolarized light include xenon lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, and metal halide lamps. For ultraviolet or visible light obtained from such light sources, the wavelength range of the irradiation can be limited by using interference filters or color filters. Moreover, for light from these light sources, linearly polarized light can be obtained by using polarizing filters or polarizing prisms.

[0325] There is no particular limitation on the cumulative light intensity of polarized or unpolarized light, but it is preferably 1 to 300 mJ / cm. 2 More preferably 5–100 mJ / cm 2 .

[0326] There is no particular limitation on the illuminance of polarized or unpolarized light, but it is preferably 0.1 to 300 mW / cm². 2 More preferably 1–100 mW / cm 2 .

[0327] Furthermore, while the above description outlines a method of performing curing and acid generation treatments prior to photoalignment treatment, the present invention is not limited to this method. Curing and acid generation treatments may be performed simultaneously during photoalignment treatment, or they may be performed after photoalignment treatment. In particular, when controlling the orientation of the adhesive layer through photoalignment treatment, it is preferable to perform the following steps after applying the adhesive composition.

[0328] That is, it is preferably manufactured by the following steps: after crosslinking a specific compound in a coating obtained using an adhesive composition through a crosslinking treatment, the coating is subjected to a photo-orientation treatment and a curing treatment in sequence, and then an acid-generating treatment is performed to form an adhesive layer.

[0329] Examples of crosslinking treatments include light irradiation or heat treatment. For instance, when the crosslinking groups of a particular compound react with an acid, acid-producing treatment can be used as a crosslinking treatment.

[0330] Furthermore, from the viewpoint of productivity and the reactivity of crosslinking groups, acid generation treatment is preferred as the crosslinking treatment. Additionally, the crosslinking treatment and acid generation treatment can be performed simultaneously; in this case, it is preferable to perform the photoorientation treatment and curing treatment sequentially after simultaneously performing the crosslinking treatment and acid generation treatment.

[0331] The thickness of the adhesive layer is not particularly limited, but considering the reason that the upper coating properties are improved, it is preferably 0.1 to 10 μm, and more preferably 0.3 to 3 μm.

[0332] [Optical laminate]

[0333] The optical laminate of the present invention has an adhesive layer of the present invention and an optical anisotropy layer disposed on the adhesive layer.

[0334] As one of the preferred embodiments of the optical laminate of the present invention, the optical anisotropic layer disposed on the adhesive layer is formed by using a polymeric liquid crystal composition containing a polymeric liquid crystal compound, and the adhesive layer and the optical anisotropic layer are stacked adjacent to each other.

[0335] Furthermore, the optical laminate of the present invention preferably has a support for supporting the adhesive layer. The support can be peeled off after the optical laminate is formed.

[0336] The preferred embodiments of the optical laminate of the present invention will now be described in detail.

[0337] [Support]

[0338] Examples of supports include glass substrates and polymer films.

[0339] Examples of polymer membrane materials include cellulose-based polymers; acrylic polymers containing acrylate polymers such as polymethyl methacrylate and polymers containing lactone rings; thermoplastic norbornene-based polymers; polycarbonate-based polymers; polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate; styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymers; polyolefin-based polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers; vinyl chloride-based polymers; amide-based polymers such as nylon and aromatic polyamides; imide-based polymers; sulfone-based polymers; polyethersulfone-based polymers; polyetheretherketone-based polymers; polyphenylene sulfide-based polymers; vinylidene chloride-based polymers; vinyl alcohol-based polymers; vinyl butyral-based polymers; aromatic ester-based polymers; polyoxymethylene-based polymers; epoxy-based polymers; or polymers formed by mixing polymers thereof.

[0340] The thickness of the support is not particularly limited, but is preferably 5 to 200 μm, more preferably 10 to 100 μm, and even more preferably 20 to 90 μm.

[0341] [Adhesive layer]

[0342] The adhesive layer is the adhesive layer of the present invention described above.

[0343] [Optical Anisotropy Layer]

[0344] The optical anisotropic layer is preferably formed using a polymeric liquid crystal composition containing a polymeric liquid crystal compound.

[0345] Among them, as a polymeric liquid crystal composition for forming an optical anisotropic layer, examples include compositions formulated with polymeric liquid crystal compounds, polymerization initiators, and solvents as any component described in the adhesive composition of the present invention.

[0346] The thickness of the optical anisotropic layer is not particularly limited, but is preferably 0.1 to 10 μm, and more preferably 0.5 to 5 μm.

[0347] [Manufacturing method of optical laminates]

[0348] The method for manufacturing the optical laminate of the present invention is a preferred method for manufacturing the optical laminate of the present invention described above. The method comprises: a step (step 1) of supplying a coating film obtained by formulating a copolymer having the above-described repeating unit A and repeating unit B as a specific compound into an adhesive composition of the present invention, and then performing a photo-orientation treatment on the coating film to form an adhesive layer; and a step (step 2) of coating the adhesive layer with a polymeric liquid crystal composition containing a polymeric liquid crystal compound to form an optically anisotropic layer.

[0349] [Process 1]

[0350] Step 1 is a step of performing photo-orientation treatment on the coating film to form an adhesive layer after the photoacid generator in the coating film obtained using the above-mentioned adhesive composition generates acid.

[0351] The steps of process 1 are as described above.

[0352] [Process 2]

[0353] Step 2 is a step of forming an optically anisotropic layer by coating a polymeric liquid crystal composition containing a polymeric liquid crystal compound onto an adhesive layer.

[0354] There is no particular limitation on the method of coating the polymerizable liquid crystal composition; the coating method illustrated in step 1 can be cited as an example.

[0355] One method for forming an optically anisotropic layer is to heat-treat a coating of a polymeric liquid crystal composition and then cure it. This heat treatment can orient the polymeric liquid crystal compound.

[0356] In the above, heat treatment and curing treatment were performed respectively, but it is also possible to perform curing treatment under heating conditions.

[0357] Furthermore, if orientation is performed without heat treatment depending on the type of polymerizable liquid crystal compound, heat treatment may be omitted.

[0358] After the coating is heated and before the curing process described later, the coating may be cooled as needed.

[0359] The heat treatment conditions are not particularly limited, as long as they are the temperature at which the polymerizable liquid crystal compound is oriented. The heating temperature is typically preferred to be 30–100°C, more preferably 50–80°C. The heating time is preferably 0.5–20 minutes, more preferably 1–5 minutes.

[0360] The curing method is not particularly limited, and examples include light irradiation and heat treatment, with light irradiation being preferred. Ultraviolet light is preferred as the light used in the light irradiation process.

[0361] There are no particular limitations on the conditions for light irradiation; the preferred irradiation dose is 10 mJ / cm². 2 ~50J / cm 2 More preferably 20 mJ / cm 2 ~5J / cm 2 Further preferred is 30 mJ / cm 2 ~3J / cm 2 .

[0362] Furthermore, the polymerization reaction can be carried out under heating conditions to promote it.

[0363] [Image display device]

[0364] The image display device of the present invention is an image display device having the optical anisotropic layer of the present invention or the optical laminate of the present invention.

[0365] The display element used in the image display device of the present invention is not particularly limited, and examples include liquid crystal cells, organic electroluminescent (hereinafter referred to as "EL") display panels and plasma display panels.

[0366] Among these, liquid crystal cells or organic EL display panels are preferred, and liquid crystal cells are more preferred. That is, as the image display device of the present invention, a liquid crystal display device that uses liquid crystal cells as display elements or an organic EL display device that uses organic EL display panels as display elements is preferred.

[0367] [Liquid Crystal Display Device]

[0368] As an example of the image display device of the present invention, the liquid crystal display device is a liquid crystal display device having the optical anisotropic layer of the present invention or the optical laminate of the present invention and a liquid crystal cell.

[0369] The liquid crystal cells used in the liquid crystal display device are preferably in VA (Vertical Alignment) mode, OCB (Optically Compensated Bend) mode, IPS (In-Plane-Switching) mode, FFS (Fringe-Field-Switching) mode or TN (Twisted Nematic) mode, but are not limited to these.

[0370] Regarding a liquid crystal display device that is an example of an image display device of the present invention, it is preferably provided, for example, in a manner in which a polarizer, the optical laminate of the present invention and a liquid crystal cell are sequentially arranged from the visual recognition side.

[0371] [Organic EL display device]

[0372] As an example of the image display device of the present invention, an organic EL display device may preferably be provided in a manner in which a polarizer, the optical anisotropic layer of the present invention or the optical laminate of the present invention and the organic EL display panel are sequentially arranged from the visual recognition side.

[0373] <Polarizer>

[0374] The polarizers mentioned above are not particularly limited as long as they are components that have the function of converting light into specific linearly polarized light, and conventionally known absorption polarizers and reflection polarizers can be used.

[0375] Examples of absorption-type polarizers include iodine-based polarizers, dye-based polarizers utilizing dichroic dyes, and polyene-based polarizers. Iodine-based and dye-based polarizers include coated polarizers and stretched polarizers, and both are applicable.

[0376] Furthermore, as a method for obtaining a polarizer by stretching and dyeing a laminated film in which a polyvinyl alcohol layer is formed on a substrate, examples include the methods described in Japanese Patent Nos. 5048120, 5143918, 4691205, 4751481, and 4751486.

[0377] Examples of reflective polarizers include polarizers made of different thin films with stacked birefringence, wire grid polarizers, and polarizers made by combining cholesteric liquid crystals with selective reflection regions and quarter-wave plates.

[0378] Among these, from the viewpoint of superior adhesion, a polarizer comprising a polyvinyl alcohol-based resin (a polymer containing -CH2-CHOH- as repeating units. In particular, at least one selected from the group consisting of polyvinyl alcohol and ethylene-vinyl alcohol copolymers) is preferred.

[0379] The thickness of the polarizer is not particularly limited, but is preferably 3 to 60 μm, more preferably 5 to 30 μm, and even more preferably 5 to 15 μm.

[0380] <Organic EL Display Panel>

[0381] An organic EL display panel is a component in which a light-emitting layer or multiple organic compound films, including a light-emitting layer, are formed between a pair of electrodes, namely an anode and a cathode. In addition to the light-emitting layer, it may have a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, and a protective layer, and each of these layers may have other functions. Various materials can be used to form each layer.

[0382] Example

[0383] The present invention will be further described in detail below with reference to specific embodiments. The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be limited by the embodiments shown below.

[0384] Synthesis of monomer mB-4

[0385] According to the following scheme, the monomer mB-4 represented by the following formula was synthesized.

[0386] [Chemical Formula 11]

[0387]

[0388] <By composition>

[0389] 200 g of 2-acetylbutyrolactone (represented by formula a in the above scheme), 320 g of aqueous hydrogen bromide solution (48%), and 300 mL of toluene were weighed into a 2000 mL flask and stirred at 60 °C for 1 hour. The reaction mixture was cooled to room temperature, transferred to a separatory funnel, and 100 mL of hexane was added. The mixture was separated and washed with 100 mL of saturated sodium bicarbonate solution containing 10 g of sodium thiosulfate and 100 mL of saturated saline solution. The obtained organic layer was dried and concentrated with anhydrous magnesium sulfate to obtain 260.0 g of compound b (represented by formula b in the above scheme) as a brown liquid.

[0390] <Composition of c>

[0391] In a 2000 mL flask, 256 g of compound b, 165.6 g of trimethyl formate, 9 g of p-toluenesulfonic acid hydrate, and 400 mL of methanol were weighed and stirred at room temperature for 1 hour. 15 mL of diisopropylethylamine was added, and the solvent was removed by distillation using an evaporator. 500 mL of hexane and 50 mL of ethyl acetate were added, and the mixture was transferred to a separatory funnel. The mixture was washed twice with 500 mL of saturated sodium bicarbonate aqueous solution. The resulting organic layer was dried and concentrated with anhydrous magnesium sulfate to obtain 248.0 g of compound c (represented by formula c in the above scheme) as a brown liquid.

[0392] <Synthesis of d>

[0393] 50 g of compound c, 0.45 g of p-toluenesulfonic acid hydrate, 172.5 g of 1H,1H,2H,2H-perfluorohexane-1-ol, and 100 mL of hexane were weighed into a 500 mL flask. The mixture was placed in a Dean-Stark container at 77 °C and stirred for 6 hours to obtain the reaction solution.

[0394] Next, 1 mL of diisopropylethylamine was added to the reaction solution, and the solvent was removed by distillation using an evaporator to obtain a concentrated solution. The concentrated solution was transferred to a separatory funnel, and 700 mL of hexane and 400 mL of acetonitrile were added. The hexane layer was separated and concentrated using an evaporator to obtain 73.0 g of compound d (represented by formula d in the above scheme) as a brown liquid.

[0395] <Synthesis of monomer mB-4>

[0396] In a 300 mL flask, 50 g of compound d, 50 mg of butylated hydroxytoluene (BHT), 1.23 g of potassium iodide, 12 g of sodium methacrylate, and 50 mL of N,N-dimethylacetamide were weighed and stirred at 80 °C for 5 hours. After cooling to room temperature, 200 mL of water was added and stirred for 5 minutes. The mixture was then transferred to a separatory funnel, and 200 mL of hexane and 20 mL of ethyl acetate were added. The separatory funnel was shaken to remove the aqueous layer. The mixture was then separated and washed with a saturated sodium chloride solution. The obtained organic layer was dried and concentrated with anhydrous sodium sulfate and subjected to column chromatography to obtain 41 g of monomer mB-4.

[0397] In addition, the following monomer mB-4 corresponds to the monomer that forms the repeating unit represented by the following formula B-4.

[0398] [Chemical Formula 12]

[0399]

[0400] For monomers other than those described above, synthesis was performed with reference to the above-described synthesis method and known methods (e.g., the method described in International Publication No. 2018 / 216812).

[0401] Furthermore, the structure of the repeating unit used in the following embodiments corresponds to the specific example of the repeating unit described above. The structure of the repeating unit used in the following comparative example and the individual unit forming the repeating unit is as follows.

[0402] [Chemical Formula 13]

[0403]

[0404] [Example 1 (Synthesis of Polymer P-1)]

[0405] In a flask equipped with a cooling tube, thermometer, and stirrer, 23 parts by mass of 2-butanone as solvent, 2.65 parts by mass of the monomer mA-18, 3.65 parts by mass of the monomer mB-4, 3.70 parts by mass of the monomer mC-4Cl, and 0.081 parts by mass of 2,2'-azobis(isobutyronitrile) as polymerization initiator were added. The mixture was stirred while nitrogen gas was flowing through the flask at a rate of 15 mL / min and heated in a water bath under reflux for 7 hours.

[0406] [Chemical Formula 14]

[0407]

[0408] After the reaction was completed, the mixture was allowed to cool naturally to room temperature. The obtained polymer solution was then added to a large amount of excess methanol to precipitate the polymer. The recovered precipitate was filtered out and washed with a large amount of methanol. The mixture was then vacuum dried at 40°C for 6 hours to obtain the following polymer P-1c, which has repeating units A-18, B-4, and C-4Cl.

[0409] [Chemical Formula 15]

[0410]

[0411] Next, copolymer P-1c (3.3 parts by mass), 4-methoxyphenol (0.016 parts by mass), triethylamine (3.75 parts by mass), and dimethylacetamide (4.95 parts by mass) were charged into a flask equipped with a cooling tube, thermometer, and stirrer. The mixture was heated in a water bath at 60°C and stirred for 4 hours. After the reaction was completed, the mixture was allowed to cool naturally to room temperature. The resulting reaction solution was then added to a large amount of excess methanol / water (1 / 3) to precipitate the polymer. The recovered precipitate was filtered off and washed with a large amount of methanol / water (1 / 3). The mixture was then dried under forced air at 40°C for 12 hours to obtain polymer P-1.

[0412] [Chemical Formula 16]

[0413]

[0414] [Examples 2-7 and Comparative Examples 1-2 (Polymer Synthesis)]

[0415] The monomers that form the repeating units described in Table 1 below were used instead of the various monomers used in Example 1, and were formulated in the amounts described in Table 1 below. Otherwise, polymers P-2 to P-7, as well as H-1 and H-2, were synthesized by the same method as polymer P-1 synthesized in Example 1.

[0416] The structures of polymers P-1 to P-7, H-1, and H-2 synthesized in Examples 1 to 7 and Comparative Examples 1 to 2 are shown below.

[0417] Polymer P-1

[0418] (In the following formula: a~c is a:b:c=25:40:35, and represents the content of each repeating unit relative to all repeating units in the polymer.)

[0419] [Chemical Formula 17]

[0420]

[0421] Polymer P-2

[0422] (In the following formula: a~c is a:b:c=25:35:40, and represents the content of each repeating unit relative to all repeating units in the polymer.)

[0423] [Chemical Formula 18]

[0424]

[0425] Polymer P-3

[0426] (In the following formula: a~c is a:b:c=25:35:40, and represents the content of each repeating unit relative to all repeating units in the polymer.)

[0427] [Chemical Formula 19]

[0428]

[0429] Polymer P-4

[0430] (In the following formula: a~c is a:b:c=25:30:45, and represents the content of each repeating unit relative to all repeating units in the polymer.)

[0431] [Chemical Formula 20]

[0432]

[0433] Polymer P-5

[0434] (In the following formula: a~c is a:b:c=25:30:45, and represents the content of each repeating unit relative to all repeating units in the polymer.)

[0435] [Chemical Formula 21]

[0436]

[0437] Polymer P-6

[0438] (In the following formula: a~c is a:b:c=15:40:45, and represents the content of each repeating unit relative to all repeating units in the polymer.)

[0439] [Chemical Formula 22]

[0440]

[0441] Polymer P-7

[0442] (In the following formula: a~c is a:b:c=26:20:54, and represents the content of each repeating unit relative to all repeating units in the polymer.)

[0443] [Chemical Formula 23]

[0444]

[0445] Polymer H-1

[0446] (In the following formula: a~c is a:b:c=50:30:20, and represents the content of each repeating unit relative to all repeating units in the polymer.)

[0447] [Chemical Formula 24]

[0448]

[0449] Polymer H-2

[0450] (In the following formula: a~c is a:b:c=25:40:35, and represents the content of each repeating unit relative to all repeating units in the polymer.)

[0451] [Chemical Formula 25]

[0452]

[0453] The weight-average molecular weights of polymers P-1 to P-7, H-1, and H-2 synthesized in Examples 1 to 7 and Comparative Examples 1 to 2 were determined using the methods described above. The results are shown in Table 1 below.

[0454] [Example 1 (Fabrication of Optical Laminates)]

[0455] A cellulose acylated membrane (ZRD40, manufactured by Fujifilm Corporation) was prepared as a support. As a composition for forming the adhesive layer, the following rod-shaped liquid crystal compound A (83 parts by mass), rod-shaped liquid crystal compound C (15 parts by mass), rod-shaped liquid crystal compound D (2 parts by mass), urethane acrylate (EBECRYL 1290, manufactured by DAICEL-ALLNEXLTD.) (4 parts by mass), photopolymerization initiator (IRGACURE OXE01, manufactured by BASF) (4.0 parts by mass), photoacid generator B (3.0 parts by mass), hydrophilic polymer A (2.0 parts by mass), and polymer P-1 (2.0 parts by mass) were dissolved in methyl isobutyl ketone (669 parts by mass) to prepare the composition for forming the adhesive layer.

[0456] The prepared adhesive layer forming solution was applied to the aforementioned support using a #3.0 wire rod. The resulting coating was heated at 60°C for 2 minutes and then cooled to 40°C. It was then subjected to nitrogen cleaning in an atmosphere with an oxygen concentration of 1.0% by volume or less, while being irradiated with a 365nm UV-LED at an irradiation dose of 500mJ / cm². 2 The film was then subjected to ultraviolet light. The resulting film was then annealed at 110°C for 1 minute to form an adhesive layer. The adhesive layer had a thickness of 0.5 μm.

[0457] [Chemical Formula 26]

[0458]

[0459] Photoacid generator B

[0460] [Chemical Formula 27]

[0461]

[0462] Hydrophilic polymer A

[0463] [Chemical Formula 28]

[0464]

[0465] [Irradiation process (to impart orientation function)]

[0466] At room temperature, the obtained adhesive layer was irradiated with UV light (ultra-high pressure mercury lamp; UL750; HOYA) passing through a wire-grid polarizer, resulting in a light intensity of 7.9 mJ / cm². 2 (Wavelength: 313nm), thus giving it orientation function.

[0467] [Formation of the optical anisotropic layer]

[0468] A solution for forming an optical anisotropic layer was prepared by dissolving the following polymerizable liquid crystal compound A (65 parts by mass), the following polymerizable liquid crystal compound B (35 parts by mass), a photopolymerization initiator (Irgacure 907, manufactured by BASF) (3 parts by mass), a sensitizer (KAYACURE DETX, manufactured by Nippon Kayaku Co., Ltd.) (1 part by mass), and the following horizontal alignment agent (0.09 parts by mass) in methyl ethyl ketone (193 parts by mass).

[0469] The optical anisotropic layer forming solution was applied to the adhesive layer using a #7 wire rod coater. The mixture was heated at 60°C for 2 minutes, and while maintaining the 60°C, it was irradiated with a 160W / cm gas-cooled metal halide lamp (manufactured by EYE GRAPHICS Co., Ltd.) at an irradiation dose of 300 mJ / cm² under a nitrogen cleaning atmosphere with an oxygen concentration of 1.0% by volume or less. 2 An optical anisotropic layer (thickness: 2.5 μm) is formed by ultraviolet light, thereby creating an optical laminate.

[0470] [Chemical Formula 29]

[0471] Horizontal orientation agent

[0472]

[0473]

[0474] [Examples 2-6 and Comparative Examples 1-2 (Fabrication of Optical Laminates)]

[0475] Polymers P-2 to P-6 and H-1 to H-2 were used instead of polymer P-1. Otherwise, an optical laminate was fabricated using the same method as in Example 1.

[0476] [Example 7 (Fabrication of Optical Laminates)]

[0477] [Formation of the adhesive layer]

[0478] Composition 2 for forming an adhesive layer with the following composition was prepared.

[0479]

[0480] In addition, the group adjacent to the acryloyloxy group in the following liquid crystal compounds R1 and R2 represents a propylene group (a group in which the methyl group is replaced by a vinyl group), and the following liquid crystal compounds R1 and R2 represent a mixture of positional isomers of the methyl group in different positions.

[0481] Liquid crystal compound R1

[0482] [Chemical Formula 30]

[0483]

[0484] Liquid crystal compound R2

[0485] [Chemical Formula 31]

[0486]

[0487] Polymer compound A1

[0488] [Chemical Formula 32]

[0489]

[0490] Polymer compound A2

[0491] [Chemical Formula 33]

[0492]

[0493] Photopolymerization initiator S1

[0494] [Chemical Formula 34]

[0495]

[0496] The above-mentioned adhesive layer forming composition 2 was applied to a cellulose acylated membrane (TG40UL, manufactured by Fujifilm Corporation) using a #7 wire-bar coater, and then annealed at 120°C for 1 minute to crosslink the polymer P-7. Furthermore, through this annealing, the cleavage groups contained in the repeating units represented by content a in the above formula cleave, resulting in crosslinking based on the repeating units represented by content c.

[0497] Then, it was cooled to room temperature and irradiated with UV light (ultra-high pressure mercury lamp; UL750; HOYA) at 7.9 mJ / cm², which had passed through a wire-grid polarizer. 2 (Wavelength: 313nm) Optical orientation processing.

[0498] Then, to cure the orientation of the adhesive layer, it was annealed again at 120°C for 1 minute, then cooled to 60°C, and while maintaining the temperature at 60°C, it was nitrogen-cleaned in an atmosphere with an oxygen concentration of less than 100 ppm, and irradiated with a 365 nm UV-LED at a dose of 200 mJ / cm². 2 The ultraviolet light was used to create adhesive layer 2 (thickness: 2.5 μm).

[0499] [Formation of the optical anisotropic layer]

[0500] Composition 2 for forming an optical anisotropic layer, prepared with the following composition, was coated onto the adhesive layer using a #4 wire bar coater.

[0501] Next, to dry the solvent of the composition and to ripen the orientation of the liquid crystal compound, it was heated with warm air at 70°C for 90 seconds. After nitrogen cleaning, it was irradiated with ultraviolet light at 40°C with an oxygen concentration of 0.1% (300 mJ / cm²). 2 The orientation of the liquid crystal compound is fixed to form an optically anisotropic layer 2 (thickness: 1.5 μm) on the adhesive layer, thereby creating an optical laminate.

[0502]

[0503]

[0504] Liquid crystal compound R3

[0505] A mixture of the following liquid crystal compounds (RA), (RB), and (RC) in an 83:15:2 (mass ratio) ratio (Me represents methyl).

[0506] [Chemical Formula 35]

[0507]

[0508] Compound B1

[0509] [Chemical Formula 36]

[0510]

[0511] Leveling agent P2 (weight-average molecular weight: 15000, the values ​​in the following formulas are by mass%)

[0512] [Chemical Formula 37]

[0513]

[0514] Leveling agent P3 (weight average molecular weight: 11,200)

[0515] (In the following formulas: a~d = a:b:c:d=56:10:29:5, and represent the content (mol%) of each repeating unit relative to all repeating units in the polymer.)

[0516] [Chemical Formula 38]

[0517]

[0518] [Example 8 (Fabrication of Optical Laminates)]

[0519] The liquid crystal compounds R1 and R2 in the adhesive layer forming composition 2 and the optical anisotropic layer forming composition 2 were both replaced with the liquid crystal compound Z1 described below. The polymeric compounds A1 and A2 in the adhesive layer forming composition 2 were both replaced with the polymeric compound A3 described below. The polymeric compound A2 in the optical anisotropic layer forming composition 2 was replaced with the polymeric compound A3 described below. Otherwise, an optical laminate with an optical anisotropic layer formed on the adhesive layer was produced by the same method as in Example 7.

[0520] Liquid crystal compound Z1

[0521] [Chemical Formula 39]

[0522]

[0523] Polymer compound A3

[0524] [Chemical Formula 40]

[0525]

[0526] Synthesis of polymer P-8

[0527] The monomers that form the repeating units described in Table 1 below were used instead of the various monomers used in Example 1, and were formulated in the amounts described in Table 1 below. Otherwise, polymer P-8 was synthesized by the same method as polymer P-1 synthesized in Example 1.

[0528] [Fabrication of Optical Laminates]

[0529] The optical laminate was fabricated using polymer P-8 instead of polymer P-1, except that the optical laminate was fabricated using the same method as in Example 1.

[0530] [Example 10]

[0531] Synthesis of monomer mB-19

[0532] [Chemical Formula 41]

[0533]

[0534] <Synthesis of mB-19a>

[0535] In a 500 mL three-necked flask, 50 g of 1-methylcyclohexanol, 91 g of potassium carbonate, and 150 mL of chloroform were weighed. While stirring in an ice bath, 91 g of bromine diluted in 70 mL of chloroform was added dropwise over 80 minutes. After the addition was complete, the mixture was stirred in a water bath for 2 hours, and then 100 mL of saturated sodium thiosulfate solution was added to stop the reaction. The aqueous layer was then removed, and the resulting organic layer was dried and concentrated with anhydrous magnesium sulfate to obtain 83 g of mB-19a as a colorless liquid (99% yield).

[0536] <Synthesis of mB-19b>

[0537] In a 100 mL three-necked flask, 2 g of 2-acetylbutyrolactone, 4.4 g of mB-19a, 1.7 g of potassium carbonate, and 10 mL of dimethylformamide were weighed and stirred at 80 °C for 6 hours. After naturally cooling to room temperature, 50 mL of water was added to stop the reaction. Then, 20 mL of hexane was added, the aqueous layer was removed, and the obtained organic layer was dried and concentrated with anhydrous magnesium sulfate and purified by silica gel column chromatography to obtain 7 g of mB-19b as a colorless liquid.

[0538] <Synthesis of mB-19c>

[0539] 7 g of mB-19b, 10 g of toluene, and 4 g of hydrobromic acid aqueous solution were weighed into a 50 mL one-necked flask and stirred at 70 °C for 2 hours. After naturally cooling to room temperature, 50 mL of water was added to stop the reaction. Next, 20 mL of hexane was added, the aqueous layer was removed, and the obtained organic layer was dried and concentrated with anhydrous magnesium sulfate and purified by silica gel column chromatography to obtain 0.9 g of mB-19c from the above scheme as a colorless liquid (yield 20%).

[0540] <Synthesis of mB-19d>

[0541] 0.9 g of mB-19c, 0.83 g of trimethyl orthoformate, 19 mg of p-toluenesulfonic acid hydrate, and 3 mL of methanol were weighed into a 50 mL one-necked flask and stirred at room temperature for 1 hour. After naturally cooling to room temperature, 1 mL of diisopropylethylamine was added to stop the reaction. Next, 30 mL of saturated sodium bicarbonate aqueous solution and 20 mL of hexane were added, the aqueous layer was removed, and the obtained organic layer was dried and concentrated with anhydrous magnesium sulfate to obtain 1.2 g of mB-19d from the above scheme as a colorless liquid (100% yield).

[0542] <Synthesis process of mB-19e>

[0543] 15 g of mB-19d, 75 g of 2-(perfluorobutyl)ethanol (UNIMATEC CO.,LTD.), 189 mg of (+)-10-camphorsulfonic acid, and 100 mL of hexane were weighed into a 300 mL three-necked flask. The mixture was heated at 72 °C for 30 minutes with nitrogen gas flowing at 30 mL / min and stirring. Then, the external temperature was raised to 77 °C, and hexane was added dropwise at a rate of 1.7 mL / min over 5 hours using a drop pump. After the addition was complete, the mixture was stirred for 1 hour. All solvent that evaporated during the reaction was removed by distillation using a Dean-Stark tube. The reaction was stopped by adding 2 mL of diisopropylethylamine. After cooling to room temperature, the mixture was diluted with 500 mL of hexane and washed twice with 300 mL of acetonitrile / water / triethylamine (5 / 1 / 0.005). The obtained organic layer was dried and concentrated with anhydrous magnesium sulfate and purified by silica gel column chromatography to obtain 12 g of mB-19e from the above scheme as a colorless liquid (yield 18%).

[0544] <Synthesis of mB-19>

[0545] 12 g of mB-19e, 1.2 g of sodium methacrylate (MCCU Nitech Electronics Co., LTD.), 122 mg of potassium iodide, 12 mg of butylated hydroxytoluene, and 7 mL of dimethylacetamide were weighed into a 2000 mL three-necked flask. The mixture was heated at 85 °C for 8 hours with stirring. After cooling to room temperature, it was diluted with 100 mL of hexane, washed separately with 150 mL of deionized water, dried and concentrated with anhydrous magnesium sulfate, and purified by silica gel column chromatography to obtain 8.4 g of mB-19 as a colorless liquid (yield 80%).

[0546] Synthesis of Polymer P-9

[0547] <Preparation of Flask Reaction Vessels>

[0548] In a flask equipped with a cooling tube, a thermometer, and a stirrer, toluene (55.6 parts by mass) as a solvent, monomer mA-18 (10.0 parts by mass), monomer mB-19 (4.67 parts by mass), and monomer mC-4Cl (9.17 parts by mass) were added. While nitrogen gas was flowing through the flask at a rate of 30 mL / min, the internal temperature was raised to 70°C by heating in a water bath.

[0549] <Preparation of the dropping solution (graded cylinder)>

[0550] The monomer mB-19 (2.33 parts by mass), the monomer mC-4Cl (13.83 parts by mass), toluene (32.4 parts by mass) as solvent, and 2,2'-azobis(isobutyronitrile) (0.668 parts by mass) as polymerization initiator were added to a graduated cylinder and dissolved to prepare a dropping solution.

[0551] Next, the prepared drop solution was added dropwise to the above-mentioned flask reaction vessel over 120 minutes, and then stirred while maintaining reflux (70°C) for 5 hours.

[0552] [Chemical Formula 42]

[0553]

[0554] After the reaction was complete, the mixture was allowed to cool naturally to room temperature. Acetone (8 parts by mass) was added to the obtained polymer solution, and this was designated as polymerization solution A. Approximately one-third of polymerization solution A was added to heptane (1200 mL) at an internal temperature of 20°C over 15–20 minutes. The internal temperature was then cooled to 0–5°C, and the remaining two-thirds of polymerization solution A was added dropwise over 30–40 minutes. After stirring at an internal temperature of 5°C for 10 minutes, the precipitated polymer was filtered out, washed with heptane (200 mL) cooled to below 5°C, and then vacuum dried at 40°C for 6 hours, thereby obtaining copolymer P-9c, which has repeating units A-18, B-19, and C-4Cl, as shown below.

[0555] [Chemical Formula 43]

[0556]

[0557] <Synthesis of Polymer P-9>

[0558] Next, 4-methoxyphenol (0.013 parts by mass) and dimethylacetamide (9.25 parts by mass) were placed in a flask equipped with a cooling tube, thermometer, and stirrer. After heating to 40-45°C in a water bath, copolymer P-9c (6.5 parts by mass) was added in three portions (each portion was confirmed to be dissolved). The internal temperature was then raised to 60°C, and triethylamine (5.72 parts by mass) was added dropwise over 10-15 minutes, followed by stirring for 2 hours.

[0559] After the reaction was complete, the mixture was allowed to cool naturally to room temperature (below 30°C). The triethylamine hydrochloride that precipitated upon the addition of acetone (9.75 parts by mass) was filtered out. The filtrate on the suction filter was washed with acetone (6.50 parts by mass). The obtained filtrate was then added to methanol / water (volume ratio: 3 / 2, 280 mL) cooled to below 5°C for 15–30 minutes to allow the polymer to precipitate. The recovered precipitate was filtered out and washed with water (150 mL) cooled to below 5°C.

[0560] The obtained crude crystals were added to methanol / water (volume ratio: 7 / 3, 280 mL) at an internal temperature of 15–19 °C and stirred for 60 minutes (hereinafter, this operation will also be referred to as "re-slurrying" in this section). The recovered precipitate was filtered off and washed with water (100 mL) cooled to below 5 °C. The above re-slurrying process was repeated.

[0561] Next, the obtained crude crystals were added to methanol / water (volume ratio: 7 / 3, 280 mL) at an internal temperature of 15–19 °C and stirred for 60 minutes. The recovered precipitate was filtered off and washed with methanol / water (volume ratio: 7 / 3, 100 mL) cooled to below 5 °C. The obtained polymer was then vacuum dried at 40 °C for 6 hours to obtain polymer P-9 represented by the following formula.

[0562] [Chemical Formula 44]

[0563]

[0564] [Fabrication of Optical Laminates]

[0565] The optical laminate was fabricated using polymer P-9 instead of polymer P-1, except that the optical laminate was fabricated using the same method as in Example 1.

[0566] [Example 11]

[0567] Synthesis of Polymer P-1 (Other Methods 1)

[0568] A flask equipped with a cooling tube, thermometer, and stirrer was filled with toluene (72.9 parts by mass) as a solvent, monomer mA-18 (10.20 parts by mass), monomer mB-4 (13.86 parts by mass), monomer mC-4Cl (16.60 parts by mass), and 2,2'-azobis(isobutyronitrile) (0.668 parts by mass) as a polymerization initiator. Nitrogen gas was flowed through the flask at a rate of 30 mL / min, and the mixture was stirred while heated in a water bath and kept under reflux for 7 hours.

[0569] [Chemical Formula 45]

[0570]

[0571] After the reaction was complete, the mixture was allowed to cool naturally to room temperature. Acetone (8 parts by mass) was added to the obtained polymer solution, and this was designated as polymerization solution A. Approximately one-third of polymerization solution A was added to heptane (1200 mL) at an internal temperature of 20°C over 15–20 minutes. The internal temperature was then cooled to 0–5°C, and the remaining two-thirds of polymerization solution A was added dropwise over 30–40 minutes. After stirring at an internal temperature of 5°C for 10 minutes, the precipitated polymer was filtered out, washed with heptane (200 mL) cooled to below 5°C, and then vacuum dried at 40°C for 6 hours to obtain copolymer P-1c, which has repeating units A-18, B-4, and C-4Cl, as shown below.

[0572] [Chemical Formula 46]

[0573]

[0574] <Synthesis of Polymer P-1>

[0575] Next, 4-methoxyphenol (0.013 parts by mass) and dimethylacetamide (9.25 parts by mass) were placed in a flask equipped with a cooling tube, thermometer, and stirrer. After heating to 40-45°C in a water bath, copolymer P-1c (6.5 parts by mass) was added in three portions (each portion was confirmed to be dissolved). The internal temperature was then raised to 60°C, and triethylamine (5.72 parts by mass) was added dropwise over 10-15 minutes, followed by stirring for 2 hours.

[0576] After the reaction was complete, the mixture was allowed to cool naturally to room temperature (below 30°C). The triethylamine hydrochloride that precipitated upon the addition of acetone (9.75 parts by mass) was filtered out. The filtrate on the suction filter was washed with acetone (6.50 parts by mass). The obtained filtrate was then added to methanol / water (volume ratio: 3 / 2, 280 mL) cooled to below 5°C for 15–30 minutes to allow the polymer to precipitate. The recovered precipitate was filtered out and washed with water (150 mL) cooled to below 5°C.

[0577] The obtained crude crystals were added to methanol / water (volume ratio: 7 / 3, 280 mL) at an internal temperature of 15–19 °C and stirred for 60 minutes (hereinafter, this operation will also be referred to as "re-slurrying" in this section). The recovered precipitate was filtered off and washed with water (100 mL) cooled to below 5 °C. The above re-slurrying process was repeated.

[0578] Next, the obtained crude crystals were added to methanol / water (volume ratio: 7 / 3, 280 mL) at an internal temperature of 15–19 °C and stirred for 60 minutes. The recovered precipitate was filtered off and washed with methanol / water (volume ratio: 7 / 3, 100 mL) cooled to below 5 °C. The obtained polymer was then vacuum dried at 40 °C for 6 hours to obtain polymer P-1 represented by the following formula.

[0579] [Chemical Formula 47]

[0580]

[0581] [Fabrication of Optical Laminates]

[0582] The polymer P-1 synthesized by the above method was used instead of the polymer P-1 synthesized in Example 1. Otherwise, the optical laminate was fabricated by the same method as in Example 1.

[0583] [Example 12]

[0584] Synthesis of Polymer P-1 (Other Methods 2)

[0585] <Preparation of Flask Reaction Vessels>

[0586] In a flask equipped with a cooling tube, a thermometer, and a stirrer, toluene (67.7 parts by mass) as a solvent, monomer mA-18 (10.20 parts by mass), monomer mB-4 (13.86 parts by mass), and monomer mC-4Cl (16.60 parts by mass) were added. While nitrogen gas was flowing through the flask at a rate of 30 mL / min, the internal temperature was raised to 70°C by heating in a water bath.

[0587] <Preparation of the dropping solution (graded cylinder)>

[0588] A dropping solution was prepared by adding toluene (5.2 parts by mass) as a solvent and 2,2'-azobis(isobutyronitrile) (0.668 parts by mass) as a polymerization initiator to a graduated cylinder and dissolving them.

[0589] Next, the prepared drop solution was added dropwise to the above-mentioned flask reaction vessel over 30 minutes, and then stirred while maintaining reflux (70°C) for 6 hours and 30 minutes.

[0590] [Chemical Formula 48]

[0591]

[0592] After the reaction was complete, the mixture was allowed to cool naturally to room temperature. Acetone (8 parts by mass) was added to the obtained polymer solution, and this was designated as polymerization solution A. Approximately one-third of polymerization solution A was added to heptane (1200 mL) at an internal temperature of 20°C over 15–20 minutes. The internal temperature was then cooled to 0–5°C, and the remaining two-thirds of polymerization solution A was added dropwise over 30–40 minutes. After stirring at an internal temperature of 5°C for 10 minutes, the precipitated polymer was filtered out, washed with heptane (200 mL) cooled to below 5°C, and then vacuum dried at 40°C for 6 hours to obtain polymer P-1c, which has repeating units A-18, B-4, and C-4Cl.

[0593] The subsequent steps were the same as those in Example 11, thereby synthesizing polymer P-1.

[0594] [Fabrication of Optical Laminates]

[0595] The polymer P-1 synthesized by the above method was used instead of the polymer P-1 synthesized in Example 1. Otherwise, the optical laminate was fabricated by the same method as in Example 1.

[0596] [Example 13]

[0597] Synthesis of Polymer P-1 (Other Methods 3)

[0598] <Preparation of Flask Reaction Vessels>

[0599] In a flask equipped with a cooling tube, a thermometer and a stirrer, toluene (55.6 parts by mass) as solvent, the following monomers mA-18 (10.30 parts by mass), mB-4 (9.4 parts by mass) and mC-4Cl (6.5 parts by mass) are added. While nitrogen gas flows through the flask at 30 mL / min, the internal temperature is raised to 70°C by heating in a water bath.

[0600] <Preparation of the dropping solution (graded cylinder)>

[0601] A dropping solution was prepared by adding monomer mB-4 (4.7 parts by mass), monomer mC-4Cl (9.8 parts by mass), toluene (32.4 parts by mass) as solvent, and 2,2'-azobis(isobutyronitrile) (0.668 parts by mass) as polymerization initiator to a graduated cylinder and dissolving them.

[0602] Next, the prepared drop solution was added dropwise to the above-mentioned flask reaction vessel over 120 minutes, and then stirred while maintaining reflux (70°C) for 5 hours.

[0603] [Chemical Formula 49]

[0604]

[0605] After the reaction was complete, the mixture was allowed to cool naturally to room temperature. Acetone (8 parts by mass) was added to the obtained polymer solution, and this was designated as polymerization solution A. Approximately one-third of polymerization solution A was added to heptane (1200 mL) at an internal temperature of 20°C over 15–20 minutes. The internal temperature was then cooled to 0–5°C, and the remaining two-thirds of polymerization solution A was added dropwise over 30–40 minutes. After stirring at an internal temperature of 5°C for 10 minutes, the precipitated polymer was filtered out, washed with heptane (200 mL) cooled to below 5°C, and then vacuum dried at 40°C for 6 hours to obtain copolymer P-1c, which contains repeating units A-18, B-4, and C-4Cl.

[0606] The subsequent steps were the same as those in Example 11, thereby synthesizing polymer P-1.

[0607] [Fabrication of Optical Laminates]

[0608] The polymer P-1 synthesized by the above method was used instead of the polymer P-1 synthesized in Example 1. Otherwise, the optical laminate was fabricated by the same method as in Example 1.

[0609] [evaluate]

[0610] [Liquid Crystal Orientation]

[0611] Two polarizers were placed on orthogonal Nicol plates, and the resulting optical laminate was placed between the two polarizers. The degree of light leakage and the surface morphology under a polarizing microscope were observed. The results are shown in Table 1 below.

[0612] AA: No light leakage, liquid crystal pointing vectors are uniformly aligned and oriented, and the surface morphology is very stable.

[0613] A: There is no light leakage, no disorder of liquid crystal pointing vector, and the surface morphology is stable.

[0614] B: There is no light leakage, the liquid crystal pointing vector disorder is minimal, and the surface morphology is stable.

[0615] C: There is no light leakage, but the liquid crystal pointing vector is disordered and the surface morphology is unstable.

[0616] D: Light leakage was observed, the liquid crystal pointing vector was disordered and the surface morphology was unstable.

[0617] [Inhibition of wind spots]

[0618] Two polarizers were placed on orthogonal Nicol plates, and a sample of the prepared adhesive layer was placed between the two polarizers. The presence of streaky inhomogeneities was observed, and the wind spot suppression was evaluated against the following criteria. The results are shown in Table 1 below.

[0619] <Evaluation Criteria>

[0620] A: Unevenness cannot be visually identified.

[0621] B: Unevenness is almost impossible to visually detect.

[0622] C: Able to visually identify unevenness.

[0623] [Top Coating Properties]

[0624] Regarding the adhesive layer produced, the surface area of ​​A4 size was examined, and defects that appeared to be circular or elliptical peeling were considered as depressions. The coatability of the topcoat was evaluated against the following criteria. The results are shown in Table 1 below.

[0625] <Evaluation Criteria>

[0626] A: 0 to 1 faults were observed.

[0627] B: 2 to 4 faults were observed.

[0628] C: More than 5 faults were observed.

[0629] [Table 1]

[0630]

[0631] ※ Set the content of “repetitive unit A” to a, the content of “repetitive unit B” to b, and the content of “repetitive unit C” to c.

[0632] Based on the results shown in Table 1 above, it can be seen that when a polymer without specific cleavage groups is used, there is a wind spot suppression effect, but the upper layer coating is poor and the liquid crystal orientation is also poor (Comparative Example 1 and Comparative Example 2).

[0633] On the other hand, it has been found that when a polymer with a specific cleavage group is used, wind spots can be suppressed, and the top layer coating properties and liquid crystal alignment become good (Examples 1 to 8 and Examples 10 to 13). Furthermore, it has been found that even when a polymer with a specific cleavage group but without repeating unit A (photoalignment group) is used, wind spots can be suppressed, and the top layer coating properties become good (Example 9).

[0634] Synthesis of monomer mB-4 (other methods)

[0635] According to the following scheme, the monomer mB-4 represented by the following formula was synthesized.

[0636] [Chemical Formula 50]

[0637]

[0638] <Process A>

[0639] 300 g of 5-chloro-2-pentanone (Manchester Organics Ltd.), 2.89 g of (+)-10-camphorsulfonic acid, and 120 mL of methanol were weighed into a 2000 mL three-necked flask. While stirring in a water bath, 277 g of trimethyl orthoformate (NIPPOH CHEMICALS CO.,LTD.) was added dropwise over 30 minutes. After the addition was complete, the mixture was stirred in a water bath for 1 hour, and then 15 mL of diisopropylethylamine was added to stop the reaction. Next, methyl formate was removed by distillation under reduced pressure (100 mmHg), diluted with 1200 mL of hexane, and washed twice with 800 mL of saturated sodium bicarbonate solution. The resulting organic layer was dried and concentrated with anhydrous magnesium sulfate to obtain 441 g of mB-4a as a black liquid (100% yield).

[0640] <Process B>

[0641] 250 g of mB-4a, 911 g of 2-(perfluorobutyl)ethanol (UNIMATEC CO.,LTD.), 3.21 g of (+)-10-camphorsulfonic acid, and 412 mL of hexane were weighed into a 3000 mL three-necked flask. The mixture was heated at 72 °C for 30 minutes with nitrogen flowing at 60 mL / min and stirring. Then, hexane was added dropwise at a rate of 13.7 mL / min over 5 hours with nitrogen flowing at 60 mL / min, while maintaining the internal temperature at 72 °C. After the addition was complete, the mixture was stirred for 1 hour. All solvent evaporated during the reaction was removed by distillation using a Dean-Stark tube. The reaction was stopped by adding 4.6 mL of diisopropylethylamine. After cooling to room temperature, the mixture was diluted with 3300 mL of hexane and washed twice with 1980 mL of acetonitrile / water / triethylamine (5 / 1 / 0.005). The obtained organic layer was dried and concentrated with anhydrous magnesium sulfate to obtain 695 g of mB-4b from the above scheme as a brown liquid (yield 79%).

[0642] <Process C>

[0643] In a 2000 mL three-necked flask, 695 g of mB-4b, 128.4 g of sodium methacrylate (MCCU Nitech Electronics Co., LTD.), 35.9 g of potassium iodide, 70 mg of butylated hydroxytoluene, and 348 mL of dimethylacetamide were weighed. The mixture was heated at 85 °C for 6 hours with stirring. After cooling to room temperature, the mixture was diluted with 2322 mL of hexane, washed separately with 1548 mL of deionized water, and dried with anhydrous magnesium sulfate. 1122 g of activated alumina was added and the mixture was stirred for 10 minutes. The activated alumina was removed by filtration, and the resulting solution was concentrated to obtain 592 g of mB-4 as a pale yellow liquid (yield 79%, 98 wt%).

[0644] [Performance Evaluation of Individual Cells]

[0645] In the optical laminate of Example 1, an optical laminate was fabricated in which mB-4 synthesized above was used instead of polymer P-1.

[0646] Regarding this optical laminate, wind spot suppression and upper layer coating properties were evaluated using the same method, and the results were all rated A.

Claims

1. An adhesive composition comprising an adhesive and a compound having a group represented by the following formula (Bl) or (B2), in the formulae (Bl) and (B2), * indicates a bonding position, n represents an integer of 1 or more, wherein a plurality of n can be the same or different, m represents an integer of 2 or more, R b1 R1is a C1-18aliphatic hydrocarbon group, R b2 , R b3 , and R b4 each independently represent a hydrogen atom or a substituent, wherein 2 R b3 may be bonded to each other to form a ring, a plurality of R b2 may be the same or different, a plurality of R b3 may be the same or different, a plurality of R b4 may be the same or different, L b1 represents an n+1 valent linking group, wherein the plurality of L b1 may be the same or different, respectively, L b2 represents a connecting group of valence m+1, Z represents an aliphatic hydrocarbon group having 5 to 25 fluorine atoms or a silicone alkoxyl group, and the aliphatic hydrocarbon group can have an oxygen atom, and a plurality of Z can be the same or different.

2. The adhesive composition according to claim 1, further comprising a photoacid generator.

3. The adhesive composition according to claim 1 or 2, wherein the compound is a compound further having a photo-orienting group.

4. The adhesive composition according to claim 1 or 2, wherein the compound is a polymer having a repeating unit B comprising the group represented by the formula (Bl) or (B2).

5. The adhesive composition according to claim 4, wherein the repeating unit B is a repeating unit represented by the following formula (1) or (2), in the formulae (1) and (2), r and s each independently represent an integer of 1 or more, 6. The adhesive composition according to claim 4, wherein the compound is a copolymer having a repeating unit A comprising a photo-orienting group and the repeating unit B.

7. The adhesive composition according to claim 6, wherein the repeating unit A is a repeating unit represented by the following formula (A), in the formula (A), R B1 and R B2 each independently represents a hydrogen atom or a substituent, Y 1 and Y 2 each independently represents -O- or -NR Z -, wherein R Z represents a hydrogen atom or a substituent, L B1 represents a linking group of valence r+1, L B2 represents a connecting group of valence s+1, B1represents a group represented by the formula (B1) wherein * in the formula (B1) indicates a bonding position to L B1 In the case where r is an integer of 2 or more, the plurality of B1may be the same or different. B2 represents a group represented by the formula (B2) wherein * in the formula (B2) indicates a bonding position to L B2 In the case where s is an integer of 2 or more, the plurality of B2may be the same or different.

8. The adhesive composition according to claim 6, wherein the compound is a copolymer having a repeating unit C comprising a crosslinking group, the repeating unit B and the repeating unit A.

9. The adhesive composition according to claim 1 or 2, wherein the compound has a weight average molecular weight of 10,000 to 500,000.

10. A compound having a group represented by the following formula (Bl) or (B2), in the formulae (Bl) and (B2), * indicates a bonding position, R A1 represents a hydrogen atom or a substituent, L A1 represents a single bond or a divalent linking group, R A2 R A3 R A4 R A5 and R A6 Each can independently represent a hydrogen atom or a substituent, R A2 R A3 R A4 R A5 and R A6 Two adjacent groups in a ring can bond together to form a ring. a plurality of n can be the same or different, m represents an integer of 2 or more, Z represents an aliphatic hydrocarbon group having 5 to 25 fluorine atoms or a silicone alkoxyl group, and the aliphatic hydrocarbon group can have an oxygen atom, and a plurality of Z can be the same or different.

11. The compound according to claim 10, further having a group represented by the following formula (PO), in the formula (PO), * indicates a bonding position with * in the formula (Bl) or (B2), 12. The compound according to claim 10, which is a polymer having a repeating unit B comprising the group represented by the formula (Bl) or (B2). n represents an integer of 1 or more, wherein 13. The compound according to claim 12, wherein the repeating unit B is a repeating unit represented by the following formula (1) or (2), in the formulae (1) and (2), R b1 R is an aliphatic hydrocarbon group having a carbon number of 1 to 18, R b2 , R b3 , and R b4 each independently represent a hydrogen atom or a substituent, wherein 2 R b3 may be bonded to each other to form a ring, a plurality of R b2 may be the same or different, a plurality of R b3 may be the same or different, a plurality of R b4 may be the same or different, L b1 represents an n+1 valent linking group, wherein, multiple L b1 may be the same or different, respectively, L b2 represents a connecting group of valence m+1, r and s each independently represent an integer of 1 or more, 14. The compound according to claim 12 or 13, which is a copolymer having a repeating unit A comprising a photo-orienting group and the repeating unit B. P 1 -L 1 -* (P0) ​ ​ P 1 represents a polymerizable group, L 1 represents a divalent linking group. ​ ​ ​ ​ ​ R B1 and R B2 each independently represents a hydrogen atom or a substituent, Y 1 and Y 2 each independently represents -O- or -NR Z -, wherein R Z represents a hydrogen atom or a substituent, L B1 represents a linking group of valence r+1, L B2 represents a linking group of valence s+1, B1represents a group represented by the formula (B1) wherein * in the formula (B1) indicates a bonding position to L B1 In the case where r is an integer of 2 or more, the plurality of B1may be the same or different. B2 represents a group represented by the formula (B2) wherein * in the formula (B2) indicates a bonding position to L B2 In the case where s is an integer of 2 or more, the plurality of B2may be the same or different. ​ 15. The compound according to claim 14, wherein the repeating unit A is a repeating unit represented by the following formula (A), in the formula (A), R A1 represents a hydrogen atom or a substituent, L A1 represents a single bond or a divalent linking group, R A2 , R A3 , R A4 , R A5 , and R A6 each independently represent a hydrogen atom or a substituent, R A2 , R A3 , R A4 , R A5 , and R A6 adjacent 2 groups among R A2 , R A3 , R A4 , R A5 , and R A6 may be bonded to form a ring.

16. The compound according to claim 14, which is a copolymer having a repeating unit C containing a crosslinkable group, the repeating unit B, and the repeating unit A.

17. The compound according to any one of claims 10 to 13, wherein the weight average molecular weight is 10,000 to 500,000.

18. An adhesive layer formed using the adhesive composition according to any one of claims 1 to 9.

19. An optical laminate having: the adhesive layer according to claim 18; and an optically anisotropic layer disposed on the adhesive layer.

20. A method for producing an optical laminate having: a step of supplying a coated film obtained using the adhesive composition according to any one of claims 6 to 8 to at least one selected from the group consisting of light, heat, an acid, and a base, and then performing a photo-alignment treatment to form an adhesive layer; and a step of applying a polymerizable liquid crystal composition containing a polymerizable liquid crystal compound on the adhesive layer to form an optically anisotropic layer.

21. An image display device having the adhesive layer according to claim 18 or the optical laminate according to claim 19.

22. A compound having a group represented by the following formula (Bl) or (B2), wherein, As for the compound having the group represented by the formula (B1), it is limited to a polymer having the repeating unit B containing the group represented by the formula (B1), in the formulae (B1) and (B2), * indicates a bonding position, n indicates an integer of 1 or more, wherein a plurality of n can be the same or different, m indicates an integer of 2 or more, R b1 R is an aliphatic hydrocarbon group having a carbon number of 1 to 18, R b2 , R b3 , and R b4 each independently represent a hydrogen atom or a substituent, wherein 2 R b3 may be bonded to each other to form a ring, a plurality of R b2 may be the same or different, a plurality of R b3 may be the same or different, a plurality of R b4 may be the same or different, L b1 represents an n+1 valent linking group, wherein the plurality of L b1 may be the same or different, respectively, L b2 represents a connecting group of valence m+1, Z indicates an aliphatic hydrocarbon group having a fluorine atom or a silicone alkoxyl group, wherein the aliphatic hydrocarbon group can have an oxygen atom, and a plurality of Z can be the same or different.

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