Oriented film forming material, oriented film, and high-molecular dispersion type liquid crystal element

Abstract

The present invention provides an alignment film forming material which provides an alignment film having high light transmittance in a transmissive state and high adhesion between a polymer liquid crystal layer and a substrate. An alignment film forming material characterized by containing the following (A) component and (B) component. (A) component: a polymer component (A) having a carboxyl group and a structure represented by the following formula (S). Wherein the polymer constituting the above polymer component (A) is at least one polymer (A) selected from the group consisting of a polyimide precursor, a polyimide which is an imidized product thereof, and a polymer of a monomer having a polymerizable unsaturated bond. (B) component: a compound (B) having a molecular weight of 2000 or less, having at least one epoxy group and one group having a polymerizable unsaturated bond in the molecule, and having the epoxy group and the group having a polymerizable unsaturated bond linked via a divalent organic group having 4 to 20 carbon atoms. (X and J are as defined in the specification.)*-X-J (S).

Description

Technical Field

[0001] This invention relates to alignment film forming materials, alignment films, and polymer-dispersed liquid crystal elements. Background Technology

[0002] Polymer-dispersed liquid crystal elements do not require polarizers, thus they have the advantage of achieving brighter displays compared to existing TN, STN, IPS, or VA mode liquid crystal display elements that use polarizers. The elements are also simple in structure, so they are used in applications such as dimming glass for light shutters and segmented displays such as clocks.

[0003] Several types of polymer-dispersed liquid crystal elements have been proposed, such as: the type called NCAP (Nematic Curvilinear Aligned Phase) (Patent Document 1), the type called PDLC (Polymer Dispersed Liquid Crystal) (Patent Document 2, Patent Document 3), the type called PNLC (Polymer Network Liquid Crystal) (Patent Document 4), and the polymer-stabilized cholesteric texture (PSCT) which uses cholesteric liquid crystals.

[0004] Among them, liquid crystal elements using PDLC and PNLC were actively studied. It is known that a normal mode type polymer dispersion liquid crystal element is a state in which the liquid crystal is oriented in a random direction when no voltage is applied and the liquid crystal is aligned along the direction of the electric field when a voltage is applied, thus transmitting light and becoming a transmission state. A reverse mode type polymer dispersion liquid crystal element is a state in which the liquid crystal is in a transmission state when no voltage is applied and in a scattering state when a voltage is applied (Patent Document 6).

[0005] In dimming applications, dimming elements with the following structure have been studied: a polymer liquid crystal layer composed of polymer encapsulating liquid crystal molecules is used as a dimming layer, and the dimming layer is sandwiched from both sides by a pair of glass substrates and plastic substrates having transparent electrodes formed on transparent conductive films. Sometimes an alignment film for orienting liquid crystal molecules is also formed on the surface of the transparent electrodes.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Publication No. 58-501631

[0009] Patent Document 2: Japanese Patent Application Publication No. 2-15236

[0010] Patent Document 3: Japanese Patent Application Publication No. 63-271233

[0011] Patent Document 4: Japanese Patent Application Publication No. 1-198725

[0012] Patent Document 5: International Publication 2020 / 184420

[0013] Patent Document 6: International Publication 2014 / 133154 Summary of the Invention

[0014] The problem that the invention aims to solve

[0015] In recent years, dimming elements using the aforementioned polymer liquid crystal layers have been studied for their high light transmittance and applications in dimming windows such as car sunroofs, shop windows that can display text and patterns, and smart windows that can block infrared rays.

[0016] In applications like those described above, it is necessary to block the field of view in the light-scattering state while ensuring a sufficient field of view in the transmission state. Therefore, in dimming elements using PDLC and PNLC, it is required to increase the transmittance in the transmission state as much as possible compared to the past.

[0017] Furthermore, when the adhesion between the polymer liquid crystal layer and the substrate in the dimming element is low, the light scattering changes over time, and there is a possibility that the function of blocking the field of view may be lost. Therefore, an alignment film with high adhesion between the polymer liquid crystal layer and the substrate is required.

[0018] The present invention was made to solve the above-mentioned problems and provides an alignment film forming material, an alignment film, and a polymer-dispersed liquid crystal element having the alignment film. The alignment film forming material provides an alignment film with high light transmittance in the transmission state and high adhesion between the polymer liquid crystal layer and the substrate.

[0019] Solution for solving the problem

[0020] In order to solve the above problems, the inventors conducted in-depth research and found that an orientation film forming material comprising the following components is effective in achieving the above objectives, thereby completing the present invention.

[0021] The present invention is based on the following content.

[0022] An orientation film forming material, characterized in that it contains the following components (A) and (B).

[0023] (A) Component: A polymer component (A) having a carboxyl group and the structure shown in the following formula (S). The polymer constituting the above polymer component (A) is at least one polymer (A) selected from the group consisting of a polyimide precursor, a polyimide as its imide derivative, and a polymer of a monomer having a polymerizable unsaturated bond.

[0024] (B) Composition: A compound with a molecular weight of less than 2000, having at least one epoxy group and one polymerizable unsaturated group in the molecule, wherein the epoxy group and the polymerizable unsaturated group are linked by a divalent organic group having 4 to 20 carbon atoms.

[0025] *-XJ (S)

[0026] (X represents a single bond, -(CH2)) a - (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -COO-, -OCO-, or -((CH2)- a1 -A1) m1 - (a1 is an integer from 1 to 15, A1 represents an oxygen atom or -COO-, and m1 is an integer from 1 to 2. When m1 is 2, multiple a1 and A1 independently have the above definitions).

[0027] J represents a monovalent organic group having at least one group selected from the group consisting of an alicyclic hydrocarbon group having 4 to 40 carbon atoms and an aromatic hydrocarbon group having 6 to 40 carbon atoms, wherein at least one hydrogen atom of the aforementioned alicyclic hydrocarbon group and aromatic hydrocarbon group is substituted by a substituent selected from the group consisting of: a halogen atom, a halogen-containing alkyl group, a halogen-containing alkoxy group, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, an alkenyl group having 3 to 10 carbon atoms, and a heteroatom-containing group formed by the interruption of the carbon-carbon bond of any methylene group of the aforementioned halogen-containing alkyl group, halogen-containing alkoxy group, alkyl group, alkoxy group and alkenyl group by an oxygen atom. * indicates a bond.

[0028] Invention Effects

[0029] According to the present invention, it is possible to obtain an alignment film forming material, an alignment film, and a polymer-dispersed liquid crystal element having the above-mentioned alignment film, which provides an alignment film with high light transmittance in the transmission state and high adhesion between the polymer liquid crystal layer and the substrate.

[0030] The mechanism by which the above-mentioned effects of the present invention are obtained may not be clear, but the following is considered to be one of the reasons.

[0031] Regarding the alignment film forming material of the present invention, while the carboxyl groups of the polymer component (A) crosslink with the epoxy groups of the compound (B), the polymeric unsaturated bonds of the compound (B) crosslink with the polymeric liquid crystal layer, thus achieving high adhesion. By making the number of carbon atoms in the alkylene group of the compound (B) four or more, the hydrophobicity is improved, and the polymeric unsaturated bond sites become more readily present on the surface of the alignment film, thus achieving even higher adhesion. Furthermore, the compound (B) has a small number of polymeric unsaturated bonds within its molecule, thus maintaining high liquid crystal alignment in the alignment film and achieving high transmittance in the transmission state. Attached Figure Description

[0032] Figure 1 This is a schematic cross-sectional view illustrating an example of a liquid crystal element according to the present invention. Detailed Implementation

[0033] The alignment film forming material, alignment film, and polymer-dispersed liquid crystal element having the above-described alignment film of the present invention will be described in detail below. However, the description of the constituent elements described below is an example of one embodiment of the present invention and is not specific to these contents.

[0034] It should be noted that, in this specification, fluorine, chlorine, bromine, and iodine atoms can be listed as halogen atoms.

[0035] <Polymer Component (A)>

[0036] The orientation film forming material of the present invention contains the following component (A) (polymer component (A)).

[0037] (A) Component: A polymer component (A) having a carboxyl group and the structure shown in formula (S) above. The polymer constituting the polymer component (A) is at least one polymer (A) selected from the group consisting of a polyimide precursor, a polyimide as its imide derivative, and a polymer of a monomer having a polymerizable unsaturated bond.

[0038] It should be noted that polymer components refer to components containing polymers, which can consist of one type of polymer or multiple types of polymers. Polymer (A) can be one type or two or more types.

[0039] The polymer component (A) is preferably: (i) a polymer (A-1) composed of a polymer selected from the group consisting of a polyimide precursor having a carboxyl group and the structure shown in the above formula (S) within the same molecule, a polyimide as an imide derivative thereof, and a monomer having a polymerizable unsaturated bond; or (ii) a polymer (A-2) composed of a polymer selected from the group consisting of a polyimide precursor having a carboxyl group, a polyimide as an imide derivative thereof, and a monomer having a polymerizable unsaturated bond; and at least one polymer (A-3) composed of a polyimide precursor having the structure shown in the above formula (S), a polyimide as an imide derivative thereof, and a monomer having a polymerizable unsaturated bond.

[0040] The polymer component (A) may include the polymer (A-1), or it may include the polymer (A-2) and the polymer (A-3).

[0041] It should be noted that polymers (A-1) to (A-3) are all included in the scope of polymer (A).

[0042] The composition of polymer (A) in the orientation film forming material can be appropriately selected according to the application and environment, but as preferred examples for achieving the effects of the present invention, the following [a] to [c] are examples.

[0043] [a] The polymer (A) is a scheme consisting of at least one selected from the group consisting of a polyimide precursor and a polyimide as an imide thereof.

[0044] [b] As polymer (A), a polymer comprising at least one selected from the group consisting of a polyimide precursor and a polyimide as an imide thereof, and a monomer having a polymerizable unsaturated bond.

[0045] [c] The polymer (A) is a polymer of monomers having polymerizable unsaturated bonds.

[0046] Of these, from the viewpoint of obtaining the effects of the present invention more preferably, the embodiments [a] or [c] are preferred. In the case of [b] above, relative to the total amount of polymer (A) contained in the orientation film forming material, the total content of the polyimide precursor and the polyimide as its imide derivative is preferably set to 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more. Furthermore, the upper limit of this content is preferably set to 99% by mass or less, and even more preferably 97% by mass or less.

[0047] In terms of achieving the effects of the present invention more preferably, as a preferred example of the above-mentioned polymer component (A), the following schemes [a1] to [c2] are listed as examples.

[0048] [a1] A scheme comprising at least one polymer selected from the group consisting of a polyimide precursor having a carboxyl group and the structure shown in the above formula (S) within the same molecule and a polyimide as its imide derivative.

[0049] [a2] A scheme comprising at least one polymer selected from the group consisting of a polyimide precursor having a carboxyl group and a polyimide as an imide thereof, and at least one polymer selected from the group consisting of a polyimide precursor having the structure shown in the above formula (S) and a polyimide as an imide thereof.

[0050] [b1] A scheme comprising at least one polymer selected from the group consisting of a polyimide precursor having a carboxyl group and a polyimide as an imide thereof, and a polymer having a monomer having a polymerizable unsaturated bond having the structure shown in the above formula (S).

[0051] [b2] A scheme comprising at least one polymer selected from the group consisting of a polyimide precursor having the structure shown in the above formula (S) and a polyimide as its imide derivative, and a polymer of a monomer having a carboxyl group and a polymerizable unsaturated bond.

[0052] [c1] A polymer containing monomers having a carboxyl group and a structure shown in the above formula (S) within the same molecule and having polymerizable unsaturated bonds.

[0053] [c2] A polymer containing a monomer having a carboxyl group and a monomer having a polymeric unsaturated bond, and a polymer having a monomer having a polymeric unsaturated bond with the structure shown in the above formula (S).

[0054] Of these, from the viewpoint of more preferably obtaining the effects of the present invention, the solution of [a1] or [c1] is preferred.

[0055] In the case described above [a1], the total amount of repeating units having carboxyl groups and repeating units having the structure shown in formula (S) is preferably 10 mol% or more of the repeating units constituting the polyimide precursor and the polyimide as its imide derivative. Furthermore, the content ratio of repeating units having the structure shown in formula (S) is preferably 10 mol% to 90 mol% of the repeating units constituting the polyimide precursor and the polyimide as its imide derivative, and more preferably 20 mol% to 80 mol% of the repeating units constituting the polyimide precursor and the polyimide as its imide derivative.

[0056] In the case of [c1] above, the total amount of monomers having carboxyl groups and polymerizable unsaturated bonds, and monomers having the structure and polymerizable unsaturated bonds shown in the above formula (S), is preferably 10 mol% or more of the monomer component with polymerizable unsaturated bonds used in the synthesis of the above polymer. Furthermore, when using monomers with polymerizable unsaturated bonds other than those having carboxyl groups and polymerizable unsaturated bonds, and monomers having the structure and polymerizable unsaturated bonds shown in the above formula (S), the total amount of monomers having carboxyl groups and polymerizable unsaturated bonds, and monomers having the structure and polymerizable unsaturated bonds shown in the above formula (S), is preferably 99 mol% or less, preferably 95 mol% or less, and more preferably 90 mol% or less.

[0057] Examples of alicyclic hydrocarbon groups with 4 to 40 carbon atoms in formula (S) include: monocyclic alicyclic hydrocarbon groups such as cyclobutane, cyclopentane, cyclohexane, and cyclodecane; and fused polycyclic alicyclic hydrocarbon groups such as norbornene, adamantane, and steroidal skeletons, formed by the condensation of two or more monocyclic alicyclic hydrocarbon groups. The steroidal skeleton uses a cyclopentane-perhydrophenanthrene core as its basic framework, and the aliphatic ring in the core may have double bonds or substituents. Substituents in the aforementioned alicyclic hydrocarbon groups can be selected from the group consisting of: halogen atoms, alkyl groups containing halogen atoms, alkoxy groups containing halogen atoms, alkyl groups with 3 to 10 carbon atoms, alkoxy groups with 3 to 10 carbon atoms, alkenyl groups with 3 to 10 carbon atoms, and any methylene group of the aforementioned alkyl groups containing halogen atoms, alkoxy groups containing halogen atoms, alkyl groups, alkoxy groups, and alkenyl groups where the carbon-carbon bond is interrupted by an oxygen atom. However, substituents other than these may also be present. The halogen atom is preferably a fluorine atom, and the alkyl group containing a fluorine atom is preferably a trifluoromethyl group.

[0058] Examples of aromatic hydrocarbon groups with 6 to 40 carbon atoms in formula (S) include monocyclic aromatic hydrocarbon groups such as benzene; and fused polycyclic aromatic hydrocarbon groups formed by the condensation of two or more monocyclic aromatic hydrocarbon groups such as naphthalene and anthracene. Examples of substituents in the above aromatic hydrocarbon groups include substituents selected from the group consisting of: halogen atoms, alkyl groups containing halogen atoms, alkoxy groups containing halogen atoms, alkyl groups with 3 to 10 carbon atoms, alkoxy groups with 3 to 10 carbon atoms, alkenyl groups with 3 to 10 carbon atoms, and heteroatom-containing groups formed by the interruption of the carbon-carbon bond of any methylene group of the above-mentioned alkyl groups containing halogen atoms, alkoxy groups containing halogen atoms, alkyl groups, alkoxy groups, and alkenyl groups by an oxygen atom. However, substituents other than these may also be present. The halogen atom is preferably a fluorine atom, and the alkyl group containing a fluorine atom is preferably trifluoromethyl.

[0059] It should be noted that when the above formula (S) is a monovalent organic group having at least one group selected from the group consisting of alicyclic hydrocarbon groups with 4 to 40 carbon atoms and aromatic hydrocarbon groups with 6 to 40 carbon atoms, at least one alicyclic hydrocarbon group or aromatic hydrocarbon group has a substituent as exemplified above (i.e., a substituent selected from the group consisting of a group consisting of a halogen atom, a halogen-containing alkyl group, a halogen-containing alkoxy group, an alkyl group with 3 to 10 carbon atoms, an alkoxy group with 3 to 10 carbon atoms, an alkenyl group with 3 to 10 carbon atoms, and a heteroatom-containing group formed by the carbon-carbon bond of any methylene group of the above-mentioned halogen-containing alkyl group, halogen-containing alkoxy group, alkyl group, alkoxy group and alkenyl group having a carbon-carbon bond interrupted by an oxygen atom). Other alicyclic hydrocarbon groups or aromatic hydrocarbon groups in the above formula (S) can be unsubstituted or have substituents other than those exemplified above.

[0060] As a more preferred specific example of the structure shown in the above formula (S), the structure shown in any one of the following formulas (S1) to (S2) can be listed.

[0061]

[0062] (X 1 Indicates a single bond, -(CH2) a - (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -COO-, -OCO-, or -((CH2)- a1 -A1) m1 - (a1 is an integer from 1 to 15, A1 represents an oxygen atom or -COO-, and m1 is an integer from 1 to 2. When m1 is 2, multiple a1 and A1 independently have the above definitions).

[0063] G 1 This refers to a divalent cyclic group selected from divalent aromatic hydrocarbon groups with 6 to 12 carbon atoms and divalent alicyclic hydrocarbon groups with 4 to 8 carbon atoms. Any hydrogen atom on the above-mentioned cyclic group may optionally be replaced by an alkyl group with 1 to 3 carbon atoms, an alkoxy group with 1 to 3 carbon atoms, an alkyl group containing a fluorine atom with 1 to 3 carbon atoms, an alkoxy group containing a fluorine atom with 1 to 3 carbon atoms, or a fluorine atom.

[0064] m is an integer from 1 to 4. When m is 2 or greater, there are multiple X... 1 G 1 Each of them independently possesses the above definition.

[0065] R 1This refers to a fluorine atom, an alkyl group containing fluorine atoms with 1 to 10 carbon atoms, an alkoxy group containing fluorine atoms with 1 to 10 carbon atoms, an alkyl group with 3 to 10 carbon atoms, an alkoxy group with 3 to 10 carbon atoms, or an alkoxyalkyl group with 3 to 10 carbon atoms.

[0066] *-X 2 -G 2 (S2)

[0067] (X 2 This indicates -CONH-, -NHCO-, -O-, -CH2O-, -OCH2-, -COO-, or -OCO-. G 2 This indicates a structure having a steroidal skeleton. In the aforementioned structure having a steroidal skeleton, at least one of the hydrogen atoms is substituted by a substituent selected from the group consisting of: a halogen atom, a halogen-containing alkyl group, a halogen-containing alkoxy group, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, an alkenyl group having 3 to 10 carbon atoms, and a heteroatom-containing group formed by interrupting the carbon-carbon bond of any methylene group in the aforementioned halogen-containing alkyl group, halogen-containing alkoxy group, alkyl group, alkoxy group, and alkenyl group by an oxygen atom.

[0068] In the above equation (S1), as G 1 The divalent cyclic groups in the cyclic group include, for example, cyclopropylene, cyclohexylene, and phenylene. Any hydrogen atom on these cyclic groups may optionally be replaced by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms containing a fluorine atom, an alkoxy group having 1 to 3 carbon atoms containing a fluorine atom, or a fluorine atom.

[0069] In the above equation (S2), as G 2 Structures with a steroidal skeleton, including those containing cholesteryl, cholesteryl, or lanostane, can be listed.

[0070] As a preferred embodiment of formula (S1), the following formulas (S1-x1)~(S1-x7) can be listed.

[0071]

[0072] In the above formula, X p For -(CH2) a - (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -CH2O-, -CH2OCO-, -COO-, or -OCO-. A1 is an oxygen atom or -COO-* (where the bond marked with "*" is with (CH2). a2 (bonding), A2 is an oxygen atom, or *-COO- (where the bond marked with "*" is with (CH2)a2 (bonded), a3 is 0 or 1, a1 and a2 are each independent integers from 1 to 10, Cy is 1,4-cyclohexene or 1,4-phenylene. R 1 It is a fluorine atom, an alkyl group containing fluorine atoms with 1 to 10 carbon atoms, an alkoxy group containing fluorine atoms with 1 to 10 carbon atoms, an alkyl group with 3 to 10 carbon atoms, an alkoxy group with 3 to 10 carbon atoms, or an alkoxyalkyl group with 3 to 10 carbon atoms.

[0073] As a preferred embodiment of the above formula (S2), the following formula (S2-x) can be listed. It should be noted that in formula (S2-x), X represents formula (X1), formula (X2), or formula (X3), Col represents formula (Col1), formula (Col2), or formula (Col3), and G represents formula (G1), formula (G2), formula (G3), or formula (G4). Me represents a methyl group. * represents a bond.

[0074]

[0075] (Polyimide precursor)

[0076] The polymer (A) (hereinafter also referred to as polyimide precursor (A)) is obtained by reacting a diamine component with a tetracarboxylic acid component. Examples of diamines contained in the diamine component include those described later. It should be noted that a single diamine may be used alone, or a combination of two or more may be used.

[0077] When the polyimide precursor (A) has a carboxyl group, the carboxyl group may be a carboxyl group derived from tetracarboxylic dianhydride or its derivatives (e.g., a carboxyl group generated by ring opening of tetracarboxylic dianhydride or its derivatives), or it may be a carboxyl group derived from a carboxyl-containing diamine.

[0078] The polyimide precursor (A) with a carboxyl group can be synthesized using a carboxyl-containing diamine.

[0079] Examples of carboxyl-containing diamines include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, and the diamines shown in formulas (3b-1) to (3b-4) below. Preferred specific examples of the diamines represented by formulas (3b-1) to (3b-4) above are 4,4'-diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 4,4'-diaminodiphenylethane-3-carboxylic acid, 4,4'-diaminobiphenyl-3,3'-dicarboxylic acid, 4,4'-diaminobiphenyl-2,2'-dicarboxylic acid, 3,3'-diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 4,4'-diaminodiphenylethane-3,3'-dicarboxylic acid, and 4,4'-diaminodiphenyl ether-3,3'-dicarboxylic acid.

[0080]

[0081] (In equation (3b-1), A) 1 The following represent single bonds: -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -O-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2O-, -OCH2-, -COO-, -OCO-, -CON(CH3)-, or -N(CH3)CO-. m1 and m2 are each independent integers from 0 to 4, and m1 + m2 is an integer from 1 to 4. In equation (3b-2), m3 and m4 are each independent integers from 1 to 5. In equation (3b-3), A... 2 This represents a straight-chain or branched alkyl group with 1 to 5 carbon atoms, where m5 is an integer from 1 to 5. In formula (3b-4), A 3 and A 4 Each of these can independently represent a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -O-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH2O-, -OCH2-, -COO-, -OCO-, -CON(CH3)-, or -N(CH3)CO-, where m6 is an integer from 1 to 4.

[0082] From the viewpoint of obtaining more favorable effects of the present invention, the proportion of the carboxyl-containing diamine used is preferably 10 mol% to 80 mol% relative to the overall diamine content, and more preferably 30 mol% to 70 mol%.

[0083] Furthermore, when the polyimide precursor (A) has the structure shown in the above formula (S), the structure shown in the above formula (S) of the polyimide precursor (A) can be derived from an aromatic diamine (d) having the structure shown in the above formula (S) in its side chain.

[0084] The polyimide precursor (A) having the structure shown in formula (S) above can be synthesized using an aromatic diamine (d) having the structure shown in formula (S) above in its side chain.

[0085] From the viewpoint of obtaining a more favorable effect of the present invention, the proportion of the aromatic diamine (d) having the structure shown in the above formula (S) used relative to the total diamine component is preferably 10 mol% to 90 mol%, more preferably 20 mol% to 80 mol%.

[0086] The aromatic diamine (d) described above preferably has at least one benzene ring.

[0087] As specific examples of aromatic diamines (d), diamines represented by the following formula (d1) or formula (d2) can be listed.

[0088]

[0089] (X represents a single bond, -O-, -C(CH3)2-, -NH-, -CO-, -(CH2) m -, -SO2-, -O-(CH2) m -O-, -O-C(CH3)2-, -CO-(CH2) m -、-NH-(CH2) m -, -SO2-(CH2) m -, -CONH-(CH2) m -CONH-(CH2) m -NHCO- or -COO-(CH2) m -OCO- is a divalent organic group. m is an integer from 1 to 8. Y represents the structure shown in formula (S) above. In formula (d2) above, the two Ys may be optionally the same or different from each other.

[0090] Preferred examples of the diamine represented by formula (d1) above can be listed as formulas (d1-1) to (d1-6). Preferred examples of the diamine represented by formula (d2) above can be listed as formulas (d2-1) to (d2-6).

[0091]

[0092]

[0093] (X v1~X v4 X p1 ~X p8 Each can be represented independently as -(CH2) a - (a is an integer from 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -CH2O-, -CH2-OCO-, -COO-, or -OCO-, X V5 ~X V6 X s1 ~X s4 Each can be independently represented as -O-, -CH2O-, -OCH2-, -COO-, or -OCO-. X a ~X f Represents single bonds, -O-, -NH-, -O-(CH2). m -O-, -C(CH3)2-, -CO-, -COO-, -CONH-, -(CH2) m -, -SO2-, -O-C(CH3)2-, -CO-(CH2) m -、-NH-(CH2) m -、-NH-(CH2) m -NH-, -SO2-(CH2) m -, -SO2-(CH2) m -SO2-, -CONH-(CH2) m -CONH-(CH2) m -NHCO- or -COO-(CH2) m -OCO-, R v1 ~R v4 R 1a ~R 1h Each is represented independently – C n H 2n+1 (n is an integer from 3 to 10), or -O-C n H 2n+1 (n is an integer from 3 to 10. m is an integer from 1 to 8.)

[0094] As a diamine that can be used in the synthesis of polyimide precursor (A), diamines other than the carboxyl-containing diamines and aromatic diamines (d) mentioned above (hereinafter also referred to as other diamines) can be used. The following diamines can be listed as examples of the other diamines mentioned above.

[0095] diamines with photo-oriented groups, such as p-phenylenediamine, m-phenylenediamine, 4-(2-(methylamino)ethyl)aniline, and diamines shown in formulas (g-1) to (g-5) below; 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1,2-bis(4-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,2-bis(4-aminophenoxy)ethane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-amino-2-methylphenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 4-(2-(4-aminophenoxy)ethoxy)-3-fluoroaniline, di(2-(4-aminophenoxy)ethyl) ether, 4-amino-4'-(2-(4-aminophenoxy)ethoxy)biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2, 2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, diamines represented by formulas (nh-1) to (nh-8), 1-(4-aminophenyl)-1,3,3-trimethyl-1H-indane-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indane-6-amine, 1,3-bis(4-aminophenylethyl)urea, diamines with photopolymerizable groups at the ends of formulas (4b-1) to (4b-12), diamines with free radical initiation functions such as formulas (R1) to (R5), 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 9,9-bis(4-aminophenyl)fluorene, etc. Diamines with photosensitizing properties that enhance sensitization upon light irradiation, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, 9-methyl-3,6-diaminocarbazole, 9-ethyl-3,6-diaminocarbazole, and 9-phenyl-3,6-diaminocarbazole, heterocyclic diamines of formulas (z-1) to (z-13), diamines with a diphenylamine skeleton of formulas (Dp-1) to (Dp-9), and diamines of formulas (5-1) to (5-13) containing the group "-N(D)-" (D represents a protecting group that is removed and substituted with a hydrogen atom upon heating, D is preferably tert-butoxycarbonyl) or the group "*-L-O-D'" (* represents a bond with a nitrogen atom), etc.L represents an alkylene group with 1 to 5 carbon atoms, and D' represents a protecting group that is removed and substituted with a hydrogen atom upon heating. D' is preferably a diamine with a siloxane bond, such as tert-butoxycarbonyl diamine, 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, or a diamine with a siloxane bond as shown in formula (Ds-1); diamines with an oxazoline structure, such as those with formulas (Ox-1) to (Ox-2); aliphatic diamines such as 1,1-m-phenylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine; and alicyclic diamines such as 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and 1,3-bis(aminomethyl)cyclohexane.

[0096]

[0097] (n1 is an integer from 2 to 12.)

[0098]

[0099] (n2 is an integer from 0 to 12, and n3 is an integer from 2 to 12.)

[0100]

[0101] (In equations (R3) to (R5), n is an integer from 2 to 6.)

[0102]

[0103]

[0104]

[0105] (Boc represents tert-butyloxycarbonyl.)

[0106]

[0107] Of the other diamines mentioned above, from the viewpoint of preferably obtaining the effects of the present invention, it is more preferable to use at least one diamine selected from the group consisting of the diamine having a photo-orientation group, the diamine having a photopolymerization group at the end, the diamine having a free radical initiation function, and the diamine having a photosensitive function (hereinafter, they are also collectively referred to as "specific photoreactive diamines").

[0108] In a more preferred embodiment of the present invention, the polyimide precursor (A) is obtained using a diamine component comprising the above-described aromatic diamine (d) and the above-described specific photoreactive diamine, as well as a tetracarboxylic acid component. The total amount of the above-described aromatic diamine (d) and the above-described specific photoreactive diamine is 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more, relative to the total amount of the diamine component.

[0109] The polymer component (A) described above may further possess photopolymerizable groups. By further possessing photopolymerizable groups in polymer component (A), the light transmittance in the transmission state, which is an effect of the present invention, and the adhesion between the polymer liquid crystal layer and the substrate can be further improved. In the case where the polyimide precursor (A) has photopolymerizable groups, the photopolymerizable groups possessed by the polyimide precursor (A) may be derived from the diamine having photopolymerizable groups at the ends described above.

[0110] The polyimide precursor (A) with photopolymerizable groups described above can be synthesized using the diamine with photopolymerizable groups at the ends described above.

[0111] From the viewpoint of obtaining a more favorable effect of the present invention, the proportion of the diamine having photopolymerizable groups at the ends is preferably 5 mol% to 70 mol% relative to the overall diamine content, more preferably 10 mol% to 70 mol%, and even more preferably 10 mol% to 50 mol%.

[0112] Examples of tetracarboxylic acid components that can be used in the synthesis of polyimide precursor (A) include acyclic aliphatic tetracarboxylic dianhydrides or derivatives thereof, alicyclic tetracarboxylic dianhydrides or derivatives thereof, or aromatic tetracarboxylic dianhydrides or derivatives thereof. More preferably, tetracarboxylic dianhydrides or derivatives thereof contain at least one partial structure selected from the group consisting of cyclobutane ring structures, cyclopentane ring structures, and cyclohexane ring structures. The tetracarboxylic acid component that can be used in the synthesis of polyimide precursor (A) is preferably the tetracarboxylic dianhydride or derivative thereof shown in the following formula (T). Examples of derivatives of the above-mentioned tetracarboxylic dianhydrides include tetracarboxylic acid dihalides, tetracarboxylic acid dialkyl esters, or tetracarboxylic acid dialkyl ester dihalides. The above-mentioned tetracarboxylic dianhydrides or derivatives thereof can be used alone or in combination of two or more.

[0113] It should be noted that aromatic tetracarboxylic acid dianhydrides are obtained by intramolecular dehydration of four carboxyl groups, including at least one carboxyl group bonded to the aromatic ring.

[0114] Acyclic aliphatic tetracarboxylic dianhydrides are obtained by intramolecular dehydration of four carboxyl groups bonded to a chain hydrocarbon structure. The structure need not consist solely of a chain hydrocarbon; it can also have alicyclic or aromatic ring structures in some parts.

[0115] Alicyclic tetracarboxylic dianhydrides are acidic dianhydrides obtained by intramolecular dehydration of four carboxyl groups, including at least one carboxyl group bonded to the alicyclic structure. None of these four carboxyl groups are bonded to an aromatic ring. Furthermore, it is not necessary for the structure to consist solely of an alicyclic structure; it can also have a chain hydrocarbon structure or an aromatic ring structure in a portion thereof.

[0116]

[0117] (X represents a structure selected from any one of the following formulas (x-1)~(x-13).)

[0118]

[0119] (R 1 ~R 4 Each can independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 6 carbon atoms, an alkenyl group with 2 to 6 carbon atoms, an alkynyl group with 2 to 6 carbon atoms, a monovalent organic group containing a fluorine atom with 1 to 6 carbon atoms, or a phenyl group. R 5 and R 6 Each A1 and A2 independently represents a hydrogen atom or a methyl group. j and k are integers of 0 or 1. A1 and A2 independently represent a single bond, -O-, -CO-, -COO-, phenylene, sulfonyl, or amide group. *1 is a bond bonded to an anhydride group on one side, and *2 is a bond bonded to an anhydride group on the other side. In the above formula (x-13), the two A2 groups may optionally be the same or different from each other.

[0120] As a more preferred specific example of the above formula (x-1), the following formulas (X1-1) to (X1-6) can be listed. In the formulas, * represents a bond.

[0121]

[0122] As preferred examples of the above formulas (x-12) and (x-13), the following formulas (x-14) to (x-29) can be listed. * indicates a bond.

[0123]

[0124]

[0125] As a preferred example of the tetracarboxylic dianhydride or its derivatives shown in the above formula (T), examples can be listed where X is the tetracarboxylic dianhydride or its derivatives shown in formula (T) with formulas (x-1) to (x-7) and (x-11) to (x-13) above, and more preferably the tetracarboxylic dianhydride or its derivatives shown in formula (T) with X being (x-1), (x-3), or (x-5).

[0126] Regarding the proportion of tetracarboxylic acid dianhydride or its derivatives used as shown in the above formula (T), it is preferably 10 mol% or more, more preferably 20 mol% or more, and even more preferably 50 mol% or more, relative to 1 mole of all tetracarboxylic acid components used.

[0127] <Preparation of Polyimide Precursors and Polyimide>

[0128] The polyimide in the polymer (A) of the present invention is an imide of the polyimide precursor (A), obtained by dehydrating and cyclizing the polyimide precursor (A). Specific examples of the above-mentioned polyimide precursors include polyamic acid and polyamic ester.

[0129] (Synthesis of polyamic acid)

[0130] The synthesis of polyamic acid is carried out by reacting a diamine component containing the aforementioned diamine with a tetracarboxylic acid component containing the aforementioned tetracarboxylic dianhydride or its derivative in an organic solvent. Regarding the ratio of tetracarboxylic dianhydride to diamine used in the polyamic acid synthesis reaction, a ratio of 0.2 to 2 equivalents of the anhydride group of the tetracarboxylic dianhydride relative to 1 equivalent of the amino group of the diamine is preferred, and a ratio of 0.3 to 1.2 equivalents is more preferred. Similar to conventional polycondensation reactions, the closer the equivalent of the anhydride group of the tetracarboxylic dianhydride is to 1 equivalent, the larger the molecular weight of the resulting polyamic acid.

[0131] The reaction temperature in the synthesis of polyamic acid is preferably -20°C to 150°C, more preferably 0°C to 100°C. Furthermore, the reaction time is preferably 0.1 hours to 24 hours, more preferably 0.5 hours to 12 hours.

[0132] The synthesis reaction of polyamic acid can be carried out at any concentration, preferably 1% to 50% by mass, more preferably 5% to 30% by mass. The reaction can be carried out at a high concentration initially, followed by the addition of solvent.

[0133] Specific examples of the aforementioned organic solvents include cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and 1,3-dimethyl-2-imidazolinone. Furthermore, where the polymer has high solvent solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or solvents represented by formulas [D-1] to [D-3] can be used.

[0134]

[0135] (In formula [D-1], D) 1 In formula [D-2], D represents an alkyl group with 1 to 3 carbon atoms. 2 In formula [D-3], D represents an alkyl group having 1 to 3 carbon atoms. 3 (This refers to alkyl groups having 1 to 4 carbon atoms.)

[0136] Specific examples of solvents represented by the above formulas [D-1] to [D-3] include propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether.

[0137] Polyamates can be obtained, for example, by known methods such as: [I] reacting the polyamic acid obtained in the above methods with an esterifying agent; [II] reacting a tetracarboxylic acid diester with a diamine; [III] reacting a tetracarboxylic acid diester dihalide with a diamine.

[0138] Furthermore, polyimide can be obtained by cyclizing (imidizing) the above-mentioned polyimide precursor. It should be noted that the imidization rate mentioned in this specification refers to the proportion of imide groups in the total amount of imide groups and carboxyl groups (or their derivatives) derived from tetracarboxylic dianhydride or its derivatives. The imidization rate does not necessarily have to be 100% and can be adjusted arbitrarily according to the application and purpose.

[0139] Methods for imidizing polyimide precursors include thermal imidization by directly heating a solution of the polyimide precursor or catalytic imidization by adding a catalyst to a solution of the polyimide precursor.

[0140] The temperature at which the polyimide precursor is thermally imidized in solution is 100°C to 400°C, preferably 120°C to 250°C, and preferably the process is carried out while removing the water generated by the imidization reaction from the system.

[0141] Catalytic imidization of polyimide precursors can be carried out by adding a basic catalyst and an acid anhydride to a solution of the polyimide precursor, preferably under stirring at -20°C to 250°C, more preferably at 0°C to 180°C. The amount of the basic catalyst is preferably 0.5 to 30 molar times that of the ammonium acid groups, more preferably 2 to 20 molar times, and the amount of the acid anhydride is preferably 1 to 50 molar times that of the ammonium acid groups, more preferably 3 to 30 molar times. Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, or trioctylamine, among which pyridine is preferred due to its moderate basicity for the reaction to proceed. Examples of acid anhydrides include acetic anhydride, trimellitic anhydride, or pyromellitic anhydride, among which acetic anhydride is preferred because it facilitates purification after the reaction. The imidization rate based on catalytic imidization can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

[0142] In recovering the generated polyimide precursor or polyimide from the reaction solution of the polyimide precursor or polyimide, the reaction solution can simply be added to a solvent to precipitate it. Examples of solvents for precipitation include methanol, ethanol, isopropanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water. The polymer precipitated in the solvent can be filtered, recovered, and then dried at room temperature or under normal or reduced pressure, or by heating. Furthermore, by repeatedly dissolving and reprecipitating the recovered polymer in an organic solvent 2 to 10 times, impurities in the polymer can be reduced. Examples of solvents used in this process include alcohols, ketones, or hydrocarbons; using three or more solvents further improves the purification efficiency and is therefore preferred.

[0143] <End-capping agent>

[0144] Alternatively, when synthesizing the polyimide precursor and polyimide of this invention, a suitable capping agent can be used together with a tetracarboxylic acid component containing tetracarboxylic dianhydride or its derivative as described above, and a diamine component containing the aforementioned diamine, to synthesize a capped polymer. The capped polymer has the effect of increasing the film hardness of the oriented film obtained from the coating and improving the adhesion between the sealant and the oriented film.

[0145] Examples of polyimide precursors and ends of polyimides in this invention include amino, carboxyl, anhydride, or derivatives thereof. Amino, carboxyl, anhydride, and isocyanate groups can be obtained through conventional condensation reactions or by end-capping with the following end-capping agents; similarly, the aforementioned derivatives can be obtained using the following end-capping agents.

[0146] Examples of capping agents include: acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, benzotriac anhydride, 3-((3-trimethoxysilyl)propyl)-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, 4-ethynyl phthalic anhydride, etc.; di-tert-butyl dicarbonate, diallyl dicarbonate, etc.; acryloyl chloride, methyl... Chlorocarbonyl compounds such as acryloyl chloride and nicotinyl chloride; monoamine compounds such as aniline, 2-aminophenol, 3-aminophenol, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine; monoisocyanate compounds with unsaturated bonds such as ethyl isocyanate, phenyl isocyanate, naphthyl isocyanate, and structures shown in formulas [1a] to [1d].

[0147]

[0148] (X 3 X represents an alkylene ring, benzene ring, or cyclohexane ring with 1 to 5 carbon atoms. 4 This refers to alkylene rings, benzene rings, or cyclohexane rings with 1 to 5 carbon atoms.

[0149]

[0150] (X 5 X represents an alkylene ring, benzene ring, or cyclohexane ring with 1 to 5 carbon atoms. 6 This refers to alkylene rings, benzene rings, or cyclohexane rings with 1 to 5 carbon atoms.

[0151] Regarding the proportion of the capping agent used, it is preferably set to 0.01 to 20 moles, more preferably 0.01 to 10 moles, relative to a total of 100 moles of the diamine component used.

[0152] (Polymers of monomers with polymerizable unsaturated bonds)

[0153] In polymers containing monomers with polymerizable unsaturated bonds (hereinafter also referred to as polymer (uA)), examples of monomers with polymerizable unsaturated bonds include: (meth)acrylic acid compounds (including unsaturated carboxylic acids, unsaturated carboxylic esters, and unsaturated polycarboxylic anhydrides), (meth)acrylamide compounds, aromatic vinyl compounds, conjugated diene compounds, compounds containing maleimide groups, α-methylene-γ-butyrolactone compounds, vinyl compounds, etc. From the viewpoint of transparency and material strength, polymer (uA) is preferably a polymer containing monomer components of the (meth)acrylic acid compounds mentioned above. When synthesizing polymer (uA), the proportion of the (meth)acrylic acid compounds used relative to the total amount of monomers used in the synthesis is preferably set to 50 mol% or more, more preferably 60 mol% or more.

[0154] The monomers with polymerizable unsaturated bonds mentioned above can be used alone or in combination of two or more.

[0155] The polymer (uA) can be obtained, for example, by polymerizing monomers having polymerizable unsaturated bonds in the presence of a polymerization initiator. Examples of polymerization initiators used include azo compounds such as 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(2,4-dimethylpentanonitrile). The proportion of the polymerization initiator used is preferably 0.01 to 30 parts by mass relative to 100 parts by mass of all monomers used in the reaction. The polymerization reaction is preferably carried out in an organic solvent. Examples of organic solvents used in the reaction include alcohols, ethers, ketones, amides, esters, and hydrocarbon compounds, preferably diethylene glycol ethyl methyl ether and propylene glycol monomethyl ether acetate. The reaction temperature is preferably set to 30°C to 120°C. The amount (a) of the organic solvent used is preferably set such that the total amount (b) of the monomers used in the reaction is 0.1% to 60% by mass relative to the total amount (a+b) of the reaction solution.

[0156] As the polymer (uA), when the orientation film forming material contains a polymer having the aforementioned carboxyl groups in its side chains and the structure shown in formula (S), the target polymer (uA) can be obtained, for example, by: (i) synthesizing a polymer having epoxy groups in its side chains by using a monomer having epoxy groups and polymerizable unsaturated bonds in the polymerization of at least a portion of the raw materials; and (iii) subsequently reacting the epoxy-containing polymer with a carboxylic acid having two or more carboxyl groups or a carboxylic acid having the structure shown in formula (S). Alternatively, a polymerization method based on monomers having carboxyl groups and polymerizable unsaturated bonds, or monomers having the structure shown in formula (S) and polymerizable unsaturated bonds, can also be used.

[0157] When the polymers of the monomers having polymerizable unsaturated bonds mentioned above have carboxyl groups, specific examples of monomers having both carboxyl groups and polymerizable unsaturated bonds include: acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, 2-hydroxyethyl methacrylate, 2-carboxyethyl methacrylate, 2-carboxypropyl methacrylate, 5-carboxypentyl methacrylate, 2-acryloyloxyethyl succinate, 2-methacryloyloxyethyl succinate, etc., which contain carboxyl groups; vinyl aromatic carboxylic acids such as 4-vinylbenzoic acid; maleimides such as 4-maleimide benzoic acid, which contain carboxyl groups; N-(carboxyphenyl)methacrylamide and N-(carboxyphenyl)acrylamide, etc., which contain carboxyl groups, and (meth)acrylamide compounds.

[0158] The carboxyl groups in the polymers of the monomers with polymerizable unsaturated bonds described above can be derived from compounds selected from the group consisting of carboxyl-containing (meth)acrylate compounds, vinyl-containing aromatic carboxylic acids, carboxyl-containing maleimides, and carboxyl-containing (meth)acrylamide compounds.

[0159] When the polymer of the monomer having polymerizable unsaturated bonds has the structure shown in the above formula (S), as a specific example of a monomer having the structure shown in the above formula (S) and polymerizable unsaturated bonds, the compound shown in the following formula (S-mA) can be listed.

[0160] PXJ (S-mA)

[0161] (P represents (meth)acryloyloxy, styrene, ethyleneoxy (CH2=CH-O-), maleimide, or α-methylene-γ-butyrolactone structure. X and J, including preferred embodiments, have the same meaning as X and J in the above formula (S). Wherein, when P is (meth)acryloyloxy, ethyleneoxy (CH2=CH-O-), or maleimide, X represents a single bond, -(CH2) a - (a is an integer from 1 to 15), -CONH-, -CON(CH3)-, -COO-, or -((CH2)- a1 -A1) m1 —(a1 is an integer from 1 to 15, A1 represents an oxygen atom or -COO-, m1 is an integer from 1 to 2. When m1 is 2, multiple a1 and A1 independently have the above definitions), J represents the same group as J in the above formula (S).

[0162] The polymer of the monomer with polymerizable unsaturated bonds has the structure shown in the above formula (S), which can be derived from compounds selected from the group consisting of compounds shown in the above formula (S-mA).

[0163] As monomers for obtaining polymer (uA), other monomers having polymeric unsaturated bonds besides the monomers having carboxyl groups and polymerizable unsaturated bonds described above, and monomers having the structure shown in formula (S) and polymerizable unsaturated bonds described above, can be used. The following monomers can be listed as other monomers having polymerizable unsaturated bonds described above.

[0164] Aminoethyl methacrylate and aminopropyl methacrylate, etc., containing amino groups of (meth)acrylates;

[0165] N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide and other (meth)acrylamide compounds containing hydroxymethyl or alkoxymethyl groups;

[0166] Allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, 2-methyl glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6,7-epoxyheptyl acrylate, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, 3-vinyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, 1,7-octadiene monoepoxide, and other compounds with an epoxy skeleton;

[0167] Compounds with an oxetane skeleton, such as 3-(acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)-2-methyloxetane, 3-(methacryloyloxymethyl)-2-methyloxetane, 3-(acryloyloxymethyl)-3-ethyloxetane, and 3-(methacryloyloxymethyl)-3-ethyloxetane;

[0168] Compounds containing nitrogen-containing aromatic heterocycles, such as 2-(2-pyridylcarbonyloxy)ethyl methacrylate, 2-(3-pyridylcarbonyloxy)ethyl methacrylate, and 2-(4-pyridylcarbonyloxy)ethyl methacrylate.

[0169] Methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantane methacrylate, 2-propyl-2-adamantane methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, etc. (meth)acrylate compounds;

[0170] Acrylamide, methacrylamide, N-methacrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide and other (meth)acrylamide compounds;

[0171] Vinyl ether compounds such as methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, and vinyl carbazole; aromatic vinyl compounds such as styrene, methylstyrene, chlorostyrene, and bromostyrene; and compounds containing maleimide groups such as maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0172] For the polymer contained in the oriented film forming material, the weight-average molecular weight (Mw) of polystyrene, determined by gel permeation chromatography (GPC), is appropriately set according to the type of polymer, but preferably 1,000 to 500,000, more preferably 2,000 to 300,000. Furthermore, the molecular weight distribution (Mw / Mn), expressed as the ratio of Mw to the number-average molecular weight (Mn) of polystyrene determined by GPC, is preferably 15 or less, more preferably 10 or less. The solution viscosity of the polymer is appropriately set according to the type of polymer. For example, when polyimide precursors and polyimides are prepared into a 10% by mass solution, a solution viscosity of 10 mPa·s to 800 mPa·s is preferred, more preferably 15 mPa·s to 500 mPa·s. It should be noted that the solution viscosity (mPa·s) is a value determined using an E-type rotational viscometer at 25°C for a 10% by mass polymer solution prepared with good solvents (e.g., γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) using these polymers.

[0173] (Compound (B))

[0174] The orientation film forming material of the present invention contains the following component (B) (compound (B)) (hereinafter also referred to as "specific adhesion compound").

[0175] (B) Composition: A compound with a molecular weight of less than 2000, having at least one epoxy group and one polymerizable unsaturated group in the molecule, wherein the epoxy group and the polymerizable unsaturated group are linked by a divalent organic group having 4 to 20 carbon atoms.

[0176] Compound (B) may optionally be one or more.

[0177] By configuring the structure in this way, while the carboxyl groups of polymer component (A) crosslink with the epoxy groups of compound (B), the polymeric unsaturated bonds of compound (B) crosslink with the polymeric liquid crystal layer, thus achieving high adhesion. Furthermore, by setting the number of carbon atoms in the alkylene group of compound (B) to 4 or more, hydrophobicity is improved, and polymeric unsaturated bond sites are more likely to exist on the surface of the alignment film, thus achieving even higher adhesion. Moreover, the low number of polymeric unsaturated bonds within the molecule of compound (B) allows the alignment film to maintain high liquid crystal alignment and achieves high transmittance in the transmission state.

[0178] Examples of groups with polymerizable unsaturated bonds include (meth)acryloyloxy, styryl, (meth)acrylamido, vinyl, vinylidene, ethyleneoxy (CH2=CH-O-), and maleimide.

[0179] From the viewpoint of obtaining the effects of the present invention more preferably, the above-mentioned compound (B) is preferably the compound shown in the following formula (b).

[0180]

[0181] (m is an integer from 1 to 6, P represents a group with a polymerizable unsaturated bond, and R represents an organic group with an alkylene group having a (m+1) valence of 4 to 20 carbon atoms.)

[0182] From the viewpoint of obtaining a more favorable effect of the present invention, the above-mentioned R preferably further contains at least one aromatic hydrocarbon group or alicyclic hydrocarbon group.

[0183] As the organic group with a valence of (m+1) represented by R in the above formula (b), examples include organic groups with a valence of (2k1+1) represented by formula (r1), organic groups with a valence of (k2+1) represented by formula (r2), or organic groups with a valence of (k3+1) represented by formula (r3).

[0184]

[0185] (Ak1 and Ak2 represent alkylene groups with 4 to 20 carbon atoms. Ak3 represents a noncyclic aliphatic hydrocarbon group with a (k3+1) valence and 4 to 20 carbon atoms. A2 and A3 represent alkylene groups with 1 to 10 carbon atoms.)

[0186] Ar1 represents an aromatic hydrocarbon group with a valence of (2k1+1) or an alicyclic hydrocarbon group with a valence of (2k1+1). Ar2 represents an aromatic hydrocarbon group with a valence of (k2+1) or an alicyclic hydrocarbon group with a valence of (k2+1).

[0187] L1, L2, L 2’ L 2” L3, L3’ Each can independently represent a single bond, -O-, -CO-, -NH-, -NHCO-, -CONH-, -OCO-, or -COO-.

[0188] k1 is an integer from 1 to 2. k2 and k3 are integers from 1 to 4. m1 and m2 are integers from 1 to 3. i2 and i3 are integers from 0 to 2.

[0189] In Ar1, Ar2, A2, A3, L1, L2, L 2’ L 2” L3, L 3’ When there are two or more i1, i2, and i3, there are two or more Ar1, Ar2, A2, A3, L1, L2, L 2’ L 2” L3, L 3’ i2 and i3 can be independently chosen to be the same or different.

[0190] *1 indicates a bond bonded to a glycidyl group, and *2 indicates a bond bonded to a p group.

[0191] Specific examples of aromatic hydrocarbon groups in Ar1 and Ar2 mentioned above include benzene, naphthalene, and anthracene. Specific examples of alicyclic hydrocarbon groups in Ar1 and Ar2 mentioned above include cyclobutane, cyclopentane, cyclohexane, cyclodecane, norbornene, adamantane, and steroidal skeletons. The hydrogen atoms in the above aromatic hydrocarbon groups and alicyclic hydrocarbon groups are optionally substituted with substituents.

[0192] Specific examples of the acyclic aliphatic hydrocarbon groups in Ak3 mentioned above include groups obtained by removing k3 hydrogen atoms from the following hydrocarbon groups: alkyl groups with 4 to 20 carbon atoms, such as n-butyl, isobutyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, and decyl; and alkenyl groups with 4 to 20 carbon atoms, such as 1-methyl-2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, and hexenyl. The hydrogen atoms in the aforementioned acyclic aliphatic hydrocarbon groups may optionally be substituted with substituents.

[0193] As specific examples of substituents optionally present in the aforementioned aromatic hydrocarbon groups, alicyclic hydrocarbon groups, and acyclic aliphatic hydrocarbon groups, substituents selected from the group consisting of: halogen atoms, alkyl groups containing halogen atoms, alkoxy groups containing halogen atoms, alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkenyl groups having 2 to 10 carbon atoms, and groups containing heteroatoms formed by the carbon-carbon bond of any methylene group of the aforementioned alkyl groups containing halogen atoms, alkoxy groups containing halogen atoms, alkyl groups, alkoxy groups, and alkenyl groups having the carbon-carbon bond interrupted by an oxygen atom.

[0194] If we list the groups "-(Ar1-L1)" in the above formula (r1),m1 - "and the group "-(Ar2-L" in formula (r2) 2” ) m2 A preferred specific example of "-" is the organic group shown in the following formula (w).

[0195]

[0196] (m represents an integer from 0 to 2. Ring A and ring A' each independently represent a benzene ring or a cyclohexane ring, wherein any hydrogen atom on the benzene ring or cyclohexane ring is optionally substituted with a monovalent organic group. Furthermore, the bonding positions of the benzene ring and cyclohexane ring can be listed as 1,4-position, 1,3-position, preferably 1,4-position. When there are two or more rings A, their respective bonding positions are optionally the same or different. L represents a single bond, -O-, -CO-, -OCO-, or -COO-. *1 and *2 represent bonded bonds, with *2 representing a bond bonded to Ak1 or Ak2. When there are two or more L and rings A, the two or more L and rings A are independently optionally the same or different.)

[0197] As preferred specific examples of the compounds shown in formula (b) above, the compounds shown in formulas (b-1) to (b-10) below can be listed.

[0198]

[0199] As more specific examples of the compounds shown in formula (b) above, compounds shown in formulas (C1) to (C3) below can be listed. It should be noted that the compounds shown in formulas (C2) to (C3) below are novel compounds not disclosed in the literature.

[0200]

[0201] The content of the above-mentioned compound (B) in the orientation film forming material of the present invention is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the total polymer component (A), more preferably 0.1 to 20 parts by mass, and even more preferably 1 to 10 parts by mass.

[0202] (Orientation film forming materials)

[0203] The orientation film forming material of the present invention contains polymer component (A) and compound (B) as essential components as described above, and is preferably prepared by dissolving them in an organic solvent. The proportion of polymer component (A) used in the orientation film forming material of the present invention is not particularly limited; for example, the content of polymer component (A) in the orientation film forming material is 0.1% to 30% by mass relative to the orientation film forming material, preferably 1% to 10% by mass.

[0204] The alignment film forming material of the present invention is preferably an alignment film forming agent, and more preferably a material for forming an alignment film of a polymer-dispersed liquid crystal element (an alignment film forming agent for a polymer-dispersed liquid crystal element).

[0205] The organic solvents contained in the orientation film forming material are not particularly limited as long as they can dissolve the polymer. Examples include lactone solvents such as γ-valerolactone and γ-butyrolactone; γ-butyrolactam, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-n-propyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-n-butyl-2-pyrrolidone, N-tert-butyl-2-pyrrolidone, N-n-pentyl-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, and N-ethoxyethyl-2-pyrrolidone. - Pyrrolidone, N-methoxybutyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone and other lactam solvents; N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, tetramethylurea, N,N-dimethyllacticamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide and other amide solvents; cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, 2,6-dimethyl-4-heptanone ( Diisobutyl ketone), methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monoethyl ether Dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether, propylene glycol diacetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, isoamyl propionate, isoamyl isobutyrate, diisopropyl ether, diisoamyl ether; ethylene carbonate, propylene carbonate and other carbonate solvents, 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 2,6-dimethyl-4-heptanol (diisobutylmethanol), etc. These can be used alone or in mixtures of two or more.

[0206] When the alignment film forming material of the present invention is applied to plastic substrates or the like, the organic solvent used in the alignment film forming material can be composed of a solvent with a boiling point of 190°C or less at 1 atm. As a preferred solvent composition when the material is composed of a solvent with a boiling point of 190°C or less at 1 atm, solvent compositions comprising the following combinations can be listed: cyclohexanone and ethylene glycol monobutyl ether, cyclohexanone and propylene glycol monobutyl ether, cyclopentanone and propylene glycol monobutyl ether, cyclohexanone and diethylene glycol monoethyl ether, cyclopentanone and diethylene glycol monoethyl ether, cyclohexanone and diisobutyl ketone, cyclopentanone and diisobutyl ketone, methyl isobutyl ketone and propylene glycol monobutyl ether. The following organic solvents can be used: methyl ethyl ketone and propylene glycol monobutyl ether, cyclohexanone and 4-hydroxy-4-methyl-2-pentanone, cyclopentanone and 4-hydroxy-4-methyl-2-pentanone, cyclohexanone and diethylene glycol diethyl ether, cyclopentanone and diethylene glycol diethyl ether, cyclohexanone and n-butyl acetate, cyclopentanone and n-butyl acetate, 4-hydroxy-4-methyl-2-pentanone and ethylene glycol monobutyl ether, cyclohexanone and propylene glycol diacetate, or cyclopentanone and propylene glycol diacetate. The type and content of such organic solvents can be appropriately selected based on the coating apparatus, coating conditions, and coating environment of the oriented film forming material.

[0207] The orientation film forming material of the present invention contains the polymer component (A) and compound (B) as described above as essential components, but may also contain other components as needed. Other components mentioned above may include, for example, polymers other than the polymer constituting polymer component (A) (hereinafter also referred to as "other polymers"), crosslinking compounds selected from at least one of the group consisting of crosslinking compound (c-1) and crosslinking compound (c-2), functional silane compounds, metal chelates, curing accelerators, surfactants, antioxidants, sensitizers, preservatives, compounds for adjusting the dielectric constant and resistance of the orientation film, orientation additives (excluding the aforementioned compound (B)), photo-radical generating agents, photo-acid generating agents, photo-alkali generating agents, ultraviolet absorbers, and light stabilizers, etc., wherein the aforementioned crosslinking compound (c-1) is a crosslinking compound other than the aforementioned compound (B) and has one or more substituents selected from epoxy group, isocyanate group, oxetyl group, cyclocarbonate group, terminated isocyanate group, hydroxyl group, and alkoxy group, and the aforementioned crosslinking compound (c-2) is a crosslinking compound other than the aforementioned compound (B) and has polymerizable unsaturated groups.

[0208] In the case that the above-mentioned crosslinking compound (c-1) has an epoxy group, particularly preferred specific examples include: N,N,N',N'-tetraglycidyl-1,4-phenylenediamine, N,N,N',N'-tetraglycidyl-2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2-bis[4-(N,N-diglycidyl-4-aminophenoxy)phenyl]propane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and other compounds in which tertiary nitrogen atoms are bonded to aromatic carbon atoms; N,N,N',N'-tetraglycidyl-1,2-diaminocyclohexane, N,N,N',N'-tetraglycidyl-1,3-diaminocyclohexane, N,N,N',N'-tetraglycidyl-1,4-diaminocyclohexane, bis(N,N- Compounds containing tertiary nitrogen atoms bonded to aliphatic carbon atoms, such as diglycidyl-4-aminocyclohexyl)methane, bis(N,N-diglycidyl-2-methyl-4-aminocyclohexyl)methane, bis(N,N-diglycidyl-3-methyl-4-aminocyclohexyl)methane, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,4-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,3-bis(N,N-diglycidylaminomethyl)benzene, 1,4-bis(N,N-diglycidylaminomethyl)benzene, 1,3,5-tris(N,N-diglycidylaminomethyl)cyclohexane, and 1,3,5-tris(N,N-diglycidylaminomethyl)benzene; and isocyanurate compounds such as TEPIC (manufactured by Nissan Chemical Co., Ltd.) triglycidyl isocyanurate.

[0209] The above is an example of a crosslinking compound and is not limited thereto. Furthermore, the crosslinking compound used in the orientation film forming material of the present invention may optionally be one or a combination of two or more.

[0210] The content of the crosslinking compound in the orientation film forming material of the present invention is 0.1 to 50 parts by mass, or 1 to 50 parts by mass, or 1 to 30 parts by mass relative to 100 parts by mass of all polymer components.

[0211] Other polymers are not particularly limited, but examples include: polyimide precursors that do not have a carboxyl group or the structure shown in formula (S) above, polyimides as their imides, polymers of monomers having polymerizable unsaturated bonds, polysiloxanes, polyesters, polyamides, polyureas, polyorganosiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly(styrene-maleic anhydride) copolymers, poly(isobutylene-maleic anhydride) copolymers, poly(vinyl ether-maleic anhydride) copolymers, poly(styrene-phenylmaleimide) derivatives, etc. Specific examples of poly(styrene-maleic anhydride) copolymers include SMA1000, 2000, 3000 (manufactured by Cray Valley), and GSM301 (manufactured by Gifu Shellac). Specific examples of poly(isobutylene-maleic anhydride) copolymers include Isobam-600 (manufactured by KURARAY). Specific examples of poly(vinyl ether-maleic anhydride) copolymers include GANTREZ AN-139 (methyl vinyl ether maleic anhydride resin, manufactured by ISP Japan). It should be noted that other polymers can be used in combination with more than one type.

[0212] When using other polymers, the proportion of these polymers used is preferably 50% by mass or less, more preferably 0.1% to 40% by mass, and even more preferably 0.1% to 30% by mass, relative to the total amount of polymers contained in the orientation film forming material.

[0213] Preferred specific examples of crosslinking compounds (c-1) and (c-2) include compounds represented by the formulas (CL-1) to (CL-16).

[0214]

[0215]

[0216] (n² represents an integer from 1 to 10. m² represents an integer from 1 to 10.)

[0217] Examples of compounds used to adjust dielectric constant and resistance include monoamines such as 3-aminomethylpyridine, which have nitrogen-containing aromatic heterocycles. When using a monoamine with a nitrogen-containing aromatic heterocycle, the amount is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the polymer component contained in the alignment film forming material.

[0218] Preferred specific examples of functional silane compounds include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane. The compounds include 3-hydroxypropyltrimethoxysilane, 3-hydroxypropylmethyldiethoxysilane, 3-hydroxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatopropyltriethoxysilane. When using functional silane compounds, the amount of polymer component contained in the oriented film forming material is preferably 0.1 to 30 parts by weight, more preferably 0.1 to 20 parts by weight, relative to 100 parts by weight of polymer components.

[0219] As a preferred specific example of the aforementioned orientation additive, a compound with a molecular weight of 2000 or less (also referred to as specific compound Ad) having a structure selected from the group consisting of formulas (p-1) to (p-12) and directly or via a linking group bonded to the orientation side chain structure is provided. The orientation side chain structure preferably comprises at least one cyclic group or steroidal skeleton selected from the group consisting of benzene rings, cyclohexane rings, and heterocycles. By introducing specific compound Ad, transparency and scattering properties can be improved in liquid crystal elements that switch between the transmission and scattering states of the liquid crystal.

[0220]

[0221] B A Represents a hydrogen atom or a benzene ring. B B ~B D Each of these characters independently represents an alkyl group having 1 to 5 carbon atoms. * indicates a bonded bond.

[0222] As a preferred example of a particular compound Ad, compounds represented by the following formula (ad) can be listed.

[0223]

[0224] (P represents a structure selected from the group consisting of equations (p-1) to (p-12) above. When P is an equation (p-1) to (p-3) above, L1 represents -(CH2).) k1 -O- (k1 is an integer from 1 to 12), when P is (p-4) to (p-11), L1 represents a single bond or -(CH2). k1 -O- (k1 is an integer from 1 to 12), when P is the above formula (p-12), L1 represents -L-(CH2). k1 -O- (L represents a single bond, -O-, -CH2O-, -CONH-, -NHCO-, -CON(CH3)-, -N(CH3)CO-, -COO-, or -OCO-. k1 is an integer from 1 to 12).

[0225] C1 represents cyclohexylene or phenylene.

[0226] L2 represents a single bond, -(CH2). c - (c is an integer from 1 to 15), -O-, -CH2O-, -COO-, or -OCO-. Among these, considering the availability of raw materials and ease of synthesis, single bonds, -COO-, or -OCO- are preferred.

[0227] n is an integer from 1 to 4. From the perspective of the optical characteristics of the liquid crystal element, n is preferably 1 or 2.

[0228] R represents an alkyl group having 1 to 18 carbon atoms, an alkyl group containing fluorine atoms having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or an alkoxy group containing fluorine atoms having 1 to 18 carbon atoms. Preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. More preferably, it is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.

[0229] When there are two or more C1 and L2 values, each of the two or more C1 and L2 values ​​can be independently chosen to be the same or different.

[0230] From the perspective of the optical properties of the liquid crystal element, the proportion of the specific compound Ad used in the alignment film forming material is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of polymer component (A). More preferably, it is 0.5 to 20 parts by mass relative to 100 parts by mass of polymer component (A). Particularly preferably, it is 1 to 10 parts by mass relative to 100 parts by mass of polymer component (A). Furthermore, the specific compound Ad may be used in one or more combinations, depending on its properties.

[0231] Specific examples of photo-generating free radical agents, photo-generating acid agents, and photo-generating alkali agents can be found in the compounds described on pages 54 to 56 of International Publication No. 2014 / 171493 (published on October 23, 2014). Among these, photo-generating free radical agents are preferred from the perspective of the adhesion between the liquid crystal layer and the alignment film of the liquid crystal element.

[0232] Examples of UV absorbers include: inorganic UV absorbers such as titanium dioxide, cerium oxide, zinc oxide, and iron oxide; and organic UV absorbers such as benzotriazole, triazine, and benzophenone. Triazine UV absorbers are preferred. Hydroxyphenyl triazine UV absorbers are more preferred. Examples of hydroxyphenyl triazine UV absorbers include, for example, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, and 2,4-bis[2-hydroxy-4-butoxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine. [2,4-Dibutoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-(2'-ethylhexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, etc. They can be used alone or in combination.

[0233] Examples of such light stabilizers include hindered amine light stabilizers (HALS). Hindered amine light stabilizers having reactive functional groups are preferred.

[0234] As for the aforementioned reactive functional group, there are no particular limitations as long as it is photoreactive. For example, functional groups having alkene double bonds such as (meth)acryloyl, vinyl, and allyl are preferably selected, and at least one of them is preferred. Among them, (meth)acryloyl is preferred. Hindered amine light stabilizers with reactive functional groups include, preferably, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, and 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)amino]-6-(2-hydroxyethylamine)-1,3,5-triazine, etc.

[0235] The concentration of solids in the alignment film forming material (the proportion of the total mass of components other than the organic solvent in the alignment film forming material to the total mass of the alignment film forming material) can be appropriately selected considering viscosity, volatility, etc., and is preferably in the range of 1% to 10% by mass. The preferred range of solids concentration varies depending on the method used to coat the alignment film forming material onto the substrate. For example, in the case of spin coating, the solids concentration is particularly preferably in the range of 1.5% to 4.5% by mass. In the case of printing, it is particularly preferably set to a solids concentration in the range of 3% to 9% by mass, thereby setting the solution viscosity in the range of 12 mPa·s to 50 mPa·s. In the case of inkjet printing, it is particularly preferably set to a solids concentration in the range of 1% to 5% by mass, thereby setting the solution viscosity in the range of 3 mPa·s to 15 mPa·s.

[0236] (Alignment film, liquid crystal element)

[0237] The alignment film of the present invention is obtained from the alignment film forming material described above. The alignment film of the present invention can also be used for horizontally aligned or vertically aligned liquid crystal alignment films, making it suitable for use in PDLC and PNLC type liquid crystal elements. The liquid crystal element of the present invention includes the above-described alignment film.

[0238] The liquid crystal element of the present invention is a liquid crystal element in which a dimming layer comprising a polymer-liquid crystal composite containing a polymer phase and a liquid crystal phase is disposed between a pair of electrode substrates with electrode faces facing each other.

[0239] Here, the aforementioned polymer-liquid crystal composite is formed by polymerization of polymeric compounds contained in the dimming layer forming material described later, and preferably by dispersing liquid crystal in the polymer to obtain a polymer-dispersed liquid crystal.

[0240] Figure 1 This is a schematic cross-sectional view illustrating an example of a liquid crystal element of the present invention. The liquid crystal element 100 includes: a pair of substrates, which are composed of a first substrate 11 and a second substrate 17; transparent electrodes 12 and 16, which are respectively disposed on the first substrate 11 and the second substrate 17; liquid crystal alignment films 13 and 15, which are respectively formed on the transparent electrodes 12 and 16; and a dimming layer 14 disposed between the liquid crystal alignment films 13 and 15.

[0241] The dimming layer 14 is a layer that has the function of changing the transparency according to the applied electric field of the transparent electrodes 12 and 16. As for the thickness of the dimming layer 14, from the viewpoint of controlling the alignment state of the liquid crystal material and appropriately embodying the dimming function, it is preferably 1 μm to 30 μm, more preferably 1 μm to 20 μm, and even more preferably 1 μm to 15 μm.

[0242] The dimming layer 14 is formed of a polymer-dispersed liquid crystal, which is a polymer-liquid crystal complex containing both a polymer phase and a liquid crystal phase. There is no particular limitation on the polymer-dispersed liquid crystal; examples include: liquid crystals (PDLC) in which liquid crystal molecules are dispersed in droplets within a transparent polymer material; polymer network liquid crystals (PNLC) in which a network of polymer resin is formed in a continuous layer of liquid crystal molecules; and polymer-stabilized cholesteric liquid crystals (PSCT) using cholesteric liquid crystal molecules. Hereinafter, an example of a dimming layer 14 formed from the aforementioned PDLC will be described.

[0243] Furthermore, the liquid crystal element of the present invention is characterized in that, in any of the above-mentioned liquid crystal elements, the dimming layer can be controlled by an external electric field to be in a light scattering state and a transmission state.

[0244] More preferably, a conventional type polymer-dispersed liquid crystal element that is in a turbid (light-scattering) state when no voltage is applied and in a transmissive state when a voltage is applied, or a reverse type polymer-dispersed liquid crystal element that is in a transmissive state when no voltage is applied and in a scattering state when a voltage is applied.

[0245] The liquid crystal element of the present invention can be manufactured, for example, by a method including the following steps (1) to (4). Furthermore, if the liquid crystal element of the present invention is a host-guest type dimming element, it can be manufactured by including the dye described later in the liquid crystal composition. Furthermore, the alignment film only needs to be formed on at least one of a pair of substrates; it can be formed on both sides or one side.

[0246] (1) The process of coating an alignment film forming material onto one or both of a pair of electrode substrates.

[0247] The alignment film forming material of the present invention is applied to one side of an electrode-bearing substrate having a patterned transparent conductive film by a suitable coating method such as a roll coater, spin coater, printing, or inkjet coating. Here, the substrate is not particularly limited as long as it is highly transparent; a film substrate made of plastics such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly(alicyclic olefins, preferably cyclic olefin polymers), acrylic resins such as polymethyl methacrylate, polypropylene (PP), and cellulose resins such as triacetyl cellulose can also be used in conjunction with glass substrates or silicon nitride substrates. When the liquid crystal element is used for dimming windows, the above-mentioned film substrate is preferred. Furthermore, in reflective liquid crystal elements, if only a single-sided substrate is used, an opaque material such as a silicon wafer can be used; in this case, the electrode can also be made of a light-reflecting material such as aluminum. From the viewpoint of process simplification, it is preferable to use a substrate having an ITO (Indium Tin Oxide) electrode, an IZO (Indium Zinc Oxide) electrode, an IGZO (Indium Gallium Zinc Oxide) electrode, an organic conductive film, etc., for liquid crystal driving.

[0248] (2) The process of firing the coating film

[0249] After coating the alignment film forming material, it is preferable to first perform preheating (pre-baking) to prevent liquid sagging of the coated alignment film forming material. The pre-baking temperature is preferably 30°C to 150°C, more preferably 40°C to 130°C, and particularly preferably 50°C to 120°C. The pre-baking time is preferably 0.25 minutes to 10 minutes, more preferably 0.5 minutes to 5 minutes, and even more preferably 1 minute to 5 minutes. Furthermore, in order to completely remove the solvent, a further heating (post-baking) process can be performed. The post-baking temperature is preferably 80°C to 190°C, more preferably 120°C to 180°C. The post-baking time is preferably 5 minutes to 30 minutes, more preferably 5 minutes to 20 minutes. The film thickness of the thus formed film is preferably 1 nm to 1000 nm, 5 nm to 1000 nm, and more preferably 10 nm to 1000 nm.

[0250] The coating formed in step (2) above can be kept as is and used as an orientation film, or the coating can be subjected to orientation capability imparting treatment. Examples of orientation capability imparting treatments include: brushing treatment by rubbing the coating in a certain direction with a roll of cloth made of fibers such as nylon, rayon, and cotton; and light orientation treatment by irradiating the coating with polarized or unpolarized radiation.

[0251] In the aforementioned photoalignment process, the radiation used to irradiate the coating can be, for example, ultraviolet light or visible light with wavelengths ranging from 150 nm to 800 nm. When the radiation is polarized, it can be linearly polarized or partially polarized. Furthermore, when the radiation used is linearly or partially polarized, irradiation can be performed from a direction perpendicular to the substrate surface, from an inclined direction, or a combination thereof. When irradiating unpolarized radiation, the irradiation direction is set to an inclined direction.

[0252] (3) Process of preparing dimming layer forming material

[0253] Prepare a pair of electrode-bearing substrates, one or both of which have an alignment film formed as described above, and place a dimming layer forming material between the two opposing substrates. Specifically, three methods can be listed below. The first method is to place the two substrates opposite each other with their respective alignment films facing each other and separated by a gap (cell gap), which is called vacuum injection. In PDLC and PNLC liquid crystal elements, it is preferable to set the cell gap to 1μm to 100μm, more preferably 2μm to 50μm, and even more preferably 5μm to 20μm. Next, use a sealant to bond the peripheries of the two substrates, and inject a liquid crystal composition, a polymeric compound component, and a dimming layer forming material containing a polymerization initiator as needed into the cell gap defined by the substrate surface and the sealant. After contacting the film surface, seal the injection hole.

[0254] Furthermore, a second method is known as the ODF (One Drop Fill) method. In this method, a UV-curable sealant is applied, for example, to a predetermined area on one of two substrates on which an alignment film has been formed. Then, the aforementioned dimming layer forming material is dropped onto several predetermined locations on the alignment film surface. Next, the other substrate is bonded together with the alignment films facing each other, and the liquid crystal composition is spread across the entire surface of the substrate, contacting the film surface. Then, the entire surface of the substrate is irradiated with UV light to cure the sealant.

[0255] Furthermore, the third method is a method known as the roll-to-roll method. Specifically, this can be illustrated by coating the aforementioned dimming layer forming material onto the film surface of the first electrode substrate on the side with the transparent conductive film, and then bonding it to the film surface of the second glass substrate with the transparent conductive film in contact with the dimming layer forming material, thereby achieving uniform thickness. As a method for coating the composite composition used in this invention, conventionally known methods such as coating machine method, rod coating method, roll coating method, direct gravure coating method, reverse gravure coating method, inkjet method, die coating method, and cap coating method can be used. Regardless of the method used, it is ideal to further heat the liquid crystal composition to a temperature at which it becomes an isotropic phase, and then slowly cool it to room temperature, thereby removing the flow orientation during liquid crystal filling.

[0256] (Light-adjusting layer forming material)

[0257] The dimming layer forming material of the present invention comprises a liquid crystal composition, a polymerizable compound component, and a polymerization initiator as needed. Furthermore, the dimming layer forming material may also contain, as needed, orientation additives, anisotropic dyes, ultraviolet absorbers / light stabilizers, and chain transfer agents. Regarding the proportion of the liquid crystal composition contained in the dimming layer forming material, it is preferably 40 parts by weight or more, more preferably 50 parts by weight or more, and even more preferably 60 parts by weight or more, relative to 100 parts by weight of the dimming layer forming material. Furthermore, it is preferably 90 parts by weight or less, more preferably 80 parts by weight or less. The content of the polymerizable compound component is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, relative to 100 parts by weight of the dimming layer forming material. Furthermore, it is preferably 60 parts by weight or less, more preferably 50 parts by weight or less, and even more preferably 40 parts by weight or less.

[0258] (Liquid Crystal Composition)

[0259] Examples of liquid crystals constituting liquid crystal compositions include nematic liquid crystals and smectic liquid crystals, with nematic liquid crystals being preferred. Examples of nematic liquid crystals include Schiff base-based liquid crystals, azo-based liquid crystals, biphenyl-based liquid crystals, phenylcyclohexane-based liquid crystals, ester-based liquid crystals, terphenyl-based liquid crystals, biphenylcyclohexane-based liquid crystals, pyrimidine-based liquid crystals, dioxane-based liquid crystals, bicyclooctane-based liquid crystals, and cubane-based liquid crystals. Furthermore, these liquid crystals can be used with the addition of components such as: cholesterol chloride, cholesterol nonanoate, cholesterol carbonate, and other cholesteric phase liquid crystals; chiral agents sold under trade names "C-15" and "CB-15" (manufactured by MERCK); and strongly dielectric liquid crystals such as p-decoxybenzyl-p-amino-2-methylbutylcinnamate.

[0260] As the above-mentioned liquid crystal composition, various liquid crystal compositions disclosed in Japanese Patent Application Publication No. 2007-009120 and Japanese Patent Application Publication No. 2011-246411 can be used.

[0261] When used as a conventional type polymer-dispersed liquid crystal element, the liquid crystal composition described above can use positive liquid crystal molecules exhibiting positive dielectric anisotropy. When used as a reverse type polymer-dispersed liquid crystal element, the liquid crystal composition described above can use negative liquid crystal molecules exhibiting negative dielectric anisotropy.

[0262] (Polymerized compound components)

[0263] In PDLC and PNLC liquid crystal elements, the dimming layer forming material preferably contains a polymerizable compound component. The polymerizable compound constituting the polymerizable compound component is preferably a free radical polymerizable compound (monomer) or its oligomer. Alternatively, polymers obtained by polymerizing these monomers may also be used. Specifically, examples include phosphate compounds containing (meth)acryloyl groups, monofunctional (meth)acrylate compounds, difunctional (meth)acrylate compounds, and trifunctional or higher (meth)acrylate compounds. Examples include monofunctional, difunctional, and polyfunctional polymerizable compounds described on pages 58-60 of International Publication No. 2015 / 012368 (published on January 29, 2015).

[0264] Examples of phosphate ester compounds containing (meth)acrylyl groups include: 2-(meth)acryloxyethyl acid phosphates (e.g., "LIGHTESTER P-1M" and "LIGHT ACRYLATE P-1A" manufactured by Kyoeisha Chemical Co., Ltd.), bis(2-(meth)acryloxyethyl) acid phosphates (e.g., "LIGHTESTER P-2M" and "LIGHT ACRYLATE P-2A" manufactured by Kyoeisha Chemical Co., Ltd., and "KAYAMERPM-21" manufactured by Nippon Kayaku Co., Ltd.), and triacryloxyethyl phosphates (e.g., "Viscoat#3PA" manufactured by Osaka Organic Chemical Industry Co., Ltd.), which are phosphate-containing unsaturated compounds with three or more olefinic unsaturated groups.

[0265] Preferred examples of monofunctional (meth)acrylate compounds include: isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and other monofunctional (meth)acrylate compounds with an alicyclic structure; 2-hydroxypropyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentenyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and partially ethoxylated 2-hydroxy(meth)acrylates, and other monofunctional (meth)acrylate compounds with an alcoholic hydroxyl group; The compounds may include monofunctional (meth)acrylate compounds having epoxy groups, such as α-ethyl(meth)acrylate, α-n-propyl(meth)acrylate, α-n-butyl(meth)acrylate, (meth)acrylate-3,4-epoxybutyl ester, (meth)acrylate-4,5-epoxypentyl ester, (meth)acrylate-3,4-epoxybutyl ester, (meth)acrylate-6,7-epoxypentyl ester, α-ethyl(meth)acrylate-6,7-epoxypentyl ester, (meth)acrylate-β-methylglycidyl ester, (meth)acrylate-3,4-epoxycyclohexyl ester, or compounds exemplified in the monomers used to obtain the above polymer (uA).

[0266] Preferred examples of difunctional (meth)acrylate compounds and trifunctional or higher (meth)acrylate compounds include: diethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, tetraethylene glycol dimethacrylate, 4,4'-biphenyl dimethacrylate, dicyclopentyl dimethacrylate, glycerol dimethacrylate, 1,9-nonanediol dimethacrylate, polyethylene glycol dimethacrylate, polypropylene glycol dimethacrylate, hydroxypentanoic acid-modified neopentyl glycol dimethacrylate (e.g., "KAYARAD HX-220" and "KAYARAD" manufactured by Nippon Kayaku Co., Ltd.). HX-620, etc.), 2,2,3,3,4,4-hexafluoropentanediol-1,5-di(meth)acrylate, or difunctional (meth)acrylate compounds having a carbamate bond (e.g., as difunctional (meth)acrylate compounds having a carbamate bond and an alicyclic structure, such as "EBECRYL 230", "EBECRYL 270", and "EBECRYL 9270" manufactured by DAICELALLNEX); trimethylolpropane tri(meth)acrylate ("NK ESTER TMPT" manufactured by Shin-Nakamura Kogyo Co., Ltd.), pentaerythritol tri(meth)acrylate ("NK ESTER A-TMMT" manufactured by Shin-Nakamura Kogyo Co., Ltd.), pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetraacrylate ("NK ESTER A-TMMT" manufactured by Shin-Nakamura Kogyo Co., Ltd.), pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetraacrylate ("NK ESTER A-TMMT" manufactured by Shin-Nakamura Kogyo Co., Ltd.), etc. (e.g., ATM-35E), bis(trimethylolpropane)tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate (e.g., "NK ESTER A-DPH" manufactured by Shin-Nakamura Kogyo Co., Ltd.), or dipentaerythritol monohydroxypenta(meth)acrylate, or other trifunctional or higher (meth)acrylate compounds, or their oligomers.

[0267] As a polymerizable compound, an ionic polymerizable compound may also be used. Specifically, it is a compound having at least one crosslinking group selected from the group consisting of hydroxyl, hydroxyalkyl, and lower alkoxyalkyl groups.

[0268] Specifically, examples include: melamine derivatives, benzomelamine derivatives, 1,3,5-tris(methoxymethoxy)benzene, 1,2,4-tris(isopropoxymethoxy)benzene, 1,4-bis(sec-butoxymethoxy)benzene, 2,6-dihydroxymethyl-p-tert-butylphenol, as described on pages 14-15 of International Publication 2014 / 171493 (published on October 23, 2014), and compounds containing epoxy groups or isocyanate groups, as described on pages 15-16 of International Publication 2014 / 171493 (published on October 23, 2014).

[0269] When using ionic polymeric compounds, ionic initiators that generate acids or bases by ultraviolet light may be introduced to promote the polymerization reaction. Specifically, the ionic initiators described on pages 16-17 of International Publication 2014 / 171493 (published on October 23, 2014) can be cited.

[0270] (Polymerization initiator)

[0271] Regarding the material forming the dimming layer, for the purpose of promoting the polymerization reaction of polymerizable compounds, especially promoting the free radical polymerization of polymerizable compounds, it is preferable to introduce a free radical initiator (also called a polymerization initiator) that generates free radicals by ultraviolet light. Specifically, examples include: benzoin and its alkyl ethers, benzoylacetyl ketals, acetophenones, acylphosphine oxides, benzophenones, aminobenzophenones, and the free radical initiators described on pages 13-14 of International Publication No. 2014 / 171493 (published on October 23, 2014). As for the aforementioned acetophenones, for example, hydroxyacetophenone, aminoacetophenone, dialkoxyacetophenone, haloacetophenone, etc., can be used. Commercially available photopolymerization initiators include, for example, Irgacure 907 (2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane) manufactured by BASF, Irgacure 651 (2,2-dimethoxy-2-phenylacetophenone), Irgacure 369 (1-(4-morpholinophenyl)-2-(dimethylamino)-2-benzyl-1-butanone), Irgacure 184, or Omnirad 184 (1-hydroxycyclohexylphenyl ketone) manufactured by IGM Resins. The preferred proportion of the polymerization initiator relative to 100 parts by weight of the light-adjusting layer forming material is 0.01 to 5 parts by weight.

[0272] The aforementioned photopolymerization initiators can be used alone or in combination of two or more. Furthermore, free radical initiators can also be used alone or in combination of two or more, depending on their properties.

[0273] (Orientation additives)

[0274] Examples of orientation additives added to the light-adjusting layer forming material include preferred orientation additives, which are present in the aforementioned orientation film forming material. Specifically, compounds containing the aforementioned specific compound Ad can be listed.

[0275] From the perspective of the optical properties of the element, the amount of orientation additive used in the dimming layer forming material is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the dimming layer forming material, more preferably 0.5 to 30 parts by mass, and particularly preferably 1 to 20 parts by mass. Two or more orientation additives can be mixed and used.

[0276] (Anisotropic dyes)

[0277] The aforementioned dimming layer forming material may also include anisotropic dyes (also known as dichroic dyes or dichroic pigments). The term "isotropic dye" refers to a dye that is capable of anisotropic absorption of light in at least a portion or all of the wavelength range in the visible light region, for example, in the wavelength range of 400 nm to 700 nm.

[0278] There are no particular restrictions on the type of anisotropic dye; for example, black dyes or colored dyes can be used. Various known dyes disclosed in Japanese Patent Application Publication No. 2007-009120 and Japanese Patent Application Publication No. 2011-246411 can be used as such anisotropic dyes. The mixing ratio of the anisotropic dye can be, for example, 0.01 to 5 parts by weight relative to 100 parts by weight of the light-adjusting layer forming material; the above ratio can be changed as needed.

[0279] (UV absorber / light stabilizer)

[0280] The aforementioned dimming layer forming material may further include an ultraviolet absorber / light stabilizer. Specific examples of ultraviolet absorbers / light stabilizers include the exemplary compounds described above. The content of the ultraviolet absorber relative to 100 parts by weight of the liquid crystal composition is preferably 0.1 to 3 parts by weight, more preferably 0.1 to 2 parts by weight, and even more preferably 0.3 to 1.5 parts by weight. The content of the light stabilizer relative to 100 parts by weight of the liquid crystal composition is preferably 1 to 10 parts by weight, more preferably 2 to 8 parts by weight, and even more preferably 3 to 6 parts by weight.

[0281] (Chain transfer agent)

[0282] The dimming layer forming material described above may further include a chain transfer agent. Preferred specific examples of chain transfer agents are butanediol dithiopropionate, pentaerythritol tetra(3-mercaptobutyrate), triethylene glycol dithiol, etc.

[0283] To prevent the degree of cross-linking of the polymer phase from becoming too high, the liquid crystal material can easily respond to the electric field and be driven by low voltage.

[0284] The content of the chain transfer agent relative to 100 parts by mass of the polymerizable compound is preferably 0.05 to 30 parts by mass, and more preferably 0.1 to 20 parts by mass.

[0285] (4) The process of polymerizing the dimming layer forming material to form a dimming layer containing a polymer phase and a liquid crystal phase.

[0286] Methods for polymerizing the dimming layer forming material of the present invention include irradiation with active energy rays and thermal polymerization. Among these, polymerization of the dimming layer forming material is preferably performed by irradiation with ultraviolet light. Furthermore, methods of ultraviolet irradiation include irradiating one of a pair of electrode-bearing substrates with ultraviolet light. Examples of light sources for the ultraviolet irradiation apparatus include metal halide lamps or high-pressure mercury lamps. In this case, the wavelength of the ultraviolet light is preferably 250 nm to 400 nm, and more preferably 310 nm to 370 nm.

[0287] The intensity of ultraviolet light irradiation can be appropriately determined through experiments, or its endpoint can be determined by the concentration of unreacted polymeric compounds in the liquid crystal composition.

[0288] The optimal amount of ultraviolet light irradiation is 0.05 J / cm. 2 The above is particularly preferred to be 1.0 J / cm. 2 The above. The preferred ultraviolet radiation intensity is 1 mW / cm². 2 In order to complete the polymerization of the polymerizable compound, a power of 20 mW / cm² can be used. 2 The irradiation time of ultraviolet light is 1 second to 3600 seconds, more preferably 60 seconds to 3600 seconds, and even more preferably 60 seconds to 1800 seconds. Furthermore, during the ultraviolet irradiation period, a voltage may be applied between the electrodes, or no voltage may be applied between the electrodes.

[0289] Furthermore, both ultraviolet treatment and heat treatment can be performed simultaneously, or heat treatment can be performed after ultraviolet treatment. The preferred temperature for heat treatment is 20°C to 120°C. More preferably, it is 30°C to 100°C.

[0290] The alignment film forming material of the present invention is also preferably used in liquid crystal display elements (hereinafter also referred to as PSA type liquid crystal display elements) manufactured by the following process: having a liquid crystal layer between a pair of substrates having electrodes, disposing a liquid crystal composition containing a polymeric compound polymerized by at least one of active energy rays and heat between the pair of substrates, applying a voltage between the electrodes, and polymerizing the polymeric compound by at least one of irradiation by active energy rays and heat.

[0291] Furthermore, the alignment film forming material of the present invention can also be used in liquid crystal display elements (hereinafter also referred to as SC-PVA type liquid crystal display elements) manufactured by the following process: a liquid crystal layer is provided between a pair of substrates having electrodes, an alignment film containing polymeric groups polymerized by at least one of active energy rays and heat is disposed between the pair of substrates, and a voltage is applied between the electrodes.

[0292] The liquid crystal element of this invention is suitable for use in transportation equipment and machinery such as automobiles, railways, and aircraft. Specifically, it is suitable for use in dimming windows that control light transmission and blocking, and light shutter elements used in interior mirrors. In particular, it exhibits excellent transparency when no voltage is applied and good scattering characteristics when voltage is applied. Therefore, when this liquid crystal element is used in vehicle windows, compared to conventional reverse-type elements, it provides higher light-gathering efficiency at night, and consequently, better protection against glare from external light. This further improves driving safety and passenger comfort. Furthermore, when the liquid crystal element is fabricated using a film substrate and then bonded to vehicle windows, its reliability is higher than that of conventional reverse-type elements. That is, it is less prone to defects and deterioration primarily caused by poor adhesion between the liquid crystal layer and the vertically aligned film.

[0293] Furthermore, the liquid crystal element of the present invention can also be used in light guide plates for display devices such as LCD (Liquid Crystal Display) and OLED (Organic Light-emitting Diode) displays, and in back panels of transparent displays using these displays. Specifically, when used as a back panel for a transparent display, and combining the transparent display with the liquid crystal element of the present invention to display an image on the transparent display, the liquid crystal element of the present invention can be used to suppress light from entering from the back of the transparent display. Thus, when the liquid crystal element displays an image on the transparent display, it becomes a voltage-applied scattering state, enabling a vivid image display; after the image display ends, it becomes a voltage-free transparent state. In addition, the alignment film forming material of the present invention can also be used as a liquid crystal alignment film for retardation films, a liquid crystal alignment film for scanning antennas, a liquid crystal array antenna, or for other applications, such as a protective film for color filters, a gate insulating film for flexible displays, and a substrate material.

[0294] [Example]

[0295] The following examples illustrate the invention in detail, but the invention is not intended to be limited to these examples. The abbreviations of the compounds and the methods for determining their properties are described below.

[0296] (liquid crystal)

[0297] L1: Sb-323010 (negative liquid crystal, manufactured by Champagne).

[0298] (polymeric compounds)

[0299] R1: Isobornyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., IBXA).

[0300] R2: The compound component represented by the following formula [R2] (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HX-220, where m and n are integers whose sum of m and n satisfies 2, and can be a mixture containing multiple compounds.)

[0301] R3: The compound component represented by the following formula [R3] (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HX-620, where m' and n' are integers whose sum of m' and n' is 4, and can be a mixture containing multiple compounds.)

[0302] R4: The compound represented by the following formula [R4] (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., ethoxylated pentaerythritol tetraacrylate, NK ESTER ATM-35E, where a, b, c, and d are integers whose sum satisfies 35, and can be a mixture containing multiple compounds.)

[0303] R5: Pentaerythritol tetra(3-mercaptobutyrate) (manufactured by Showa Denko Co., Ltd., KARENZ MT PE1).

[0304] R6: The compound represented by the following formula [R6].

[0305]

[0306] (Photoradical initiator)

[0307] P1: 1-Hydroxycyclohexylphenyl ketone (IGM Resins, Omnirad 184).

[0308] (Diamine)

[0309] A1: 3,5-Diaminobenzoic acid.

[0310] A2: 1,3-Diamino-4-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxy}benzene.

[0311] A3: 3,5-Diaminobenzoic acid = 2-methacryloyloxyethyl ester (equivalent to the above-mentioned diamine with photopolymerizable groups at the end).

[0312]

[0313] (Tetracarboxylic acid dianhydride)

[0314] B1: 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride.

[0315] B2: Bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid dianhydride.

[0316]

[0317] (amine compounds)

[0318] A4: 3-Aminomethylpyridine.

[0319]

[0320] (additive)

[0321] C1 to C3: Compounds represented by the following formulas (C1) to (C3) (specific binding compounds) (equivalent to component (B) of the present invention).

[0322] D1~D3: The compounds shown in the following formulas (D1)~(D3) (comparative compounds).

[0323]

[0324] (Methylpropene monomer)

[0325] E1~E3: Compounds represented by the following formulas (E1)~(E3).

[0326]

[0327] (solvent)

[0328] NMP: N-methyl-2-pyrrolidone.

[0329] BCS: Ethylene glycol monobutyl ether.

[0330] CHN: Cyclohexanone.

[0331] PGME: Propylene glycol monomethyl ether.

[0332] DMSO: Dimethyl sulfoxide.

[0333] MeCN: Acetonitrile.

[0334] Molecular weight determination of polyimide polymers

[0335] The determination was performed using a room-temperature gel permeation chromatography (GPC) apparatus (GPC-101, manufactured by Showa Denko Corporation) and chromatographic columns (KD-803 and KD-805 in series, manufactured by Showa Denko Corporation) as follows.

[0336] Column temperature: 50℃.

[0337] Eluent: N,N-dimethylformamide (as additives, lithium bromide monohydrate (LiBr·H2O) 30 mmol / L, anhydrous phosphoric acid (orthophosphoric acid) 30 mmol / L, tetrahydrofuran (THF) 10 mL / L).

[0338] Flow rate: 1.0 mL / min.

[0339] Standard samples used for calibration curve preparation: TSK standard polyethylene oxide (molecular weight: approximately 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh) and polyethylene glycol (molecular weight: approximately 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratories).

[0340] "Determination of imidization rate of polyimide polymers"

[0341] NMR (Nuclear Magnetic Resonance) Sample Tubes (NMR Sampling Tube Standard) (Prepared by Kusano Scientific Co., Ltd.) 20 mg of polyimide powder was added, followed by 0.53 mL of a mixture of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% by mass TMS (tetramethylsilane)). The mixture was then sonicated until completely dissolved. The solution was analyzed at 500 MHz using an NMR spectrometer (JNW-ECA500, manufactured by NEC DATUM). Regarding the imidization rate, the proton originating from the structure unchanged before and after imidization was identified as the reference proton. The peak integral value of this proton, along with the peak integral value of the proton originating from the NH group of the ammonium acid appearing around 9.5 ppm to 10.0 ppm, was used to calculate the rate using the following formula.

[0342] Imidification rate (%) = (1 - α·x / y) × 100

[0343] (x is the proton peak integral value derived from the NH group of the ammonium acid, y is the peak integral value of the reference proton, and α is the ratio of the reference proton to the number of NH protons of the ammonium acid in the case of polyammonium (imidization rate of 0%).)

[0344] Synthesis of Additives C1-C3

[0345] The compound represented by formula (C1) was synthesized using the synthetic method described in International Publication No. 2015 / 012341. Formulas (C2) to (C3) are novel compounds not disclosed in the literature, and their synthetic methods are described in detail below.

[0346] < 1 H-NMR determination >

[0347] Apparatus: Fourier transform superconducting nuclear magnetic resonance (FT-NMR) device "AVANCE III" (BRUKER) 500MHz.

[0348] Solvent: Deuterated dimethyl sulfoxide ([D6]-DMSO).

[0349] Standard substance: Tetramethylsilane (TMS).

[0350] <Example 1 of Additive Synthesis: Synthesis of [C2]>

[0351]

[0352] 4'-[6-(2-methacryloyloxy)hexyloxy]biphenyl-4-carboxylic acid (19.1 g, 50 mmol), epichlorohydrin (23.1 g, 250 mmol), tetrabutylammonium chloride (2.1 g, 7.5 mmol), and DMSO (60 g) were added to a 200 mL four-necked flask and stirred at 80 °C. After the reaction was complete, the reaction system was injected into ethyl acetate (300 g), the organic layer was washed with pure water (1000 g), and the mixture was concentrated to obtain [C2-1] (23.7 g). [C2-1] was used directly in the following steps without further purification.

[0353] The [C2-1] (23.7 g) obtained above, potassium carbonate (10.4 g, 75 mmol), butylated hydroxytoluene (11.0 mg, 0.05 mmol), and MeCN (200 g) obtained above were charged into a 500 mL four-necked flask and stirred at 80 °C. After the reaction was complete, the precipitate was filtered off, and the filtrate was concentrated. The crude product was separated by silica gel column chromatography (chloroform:heptane = 4:1 (v / v)) to obtain [C2] (13.5 g, two-step yield: 61%, white solid). The target analyte is shown below. 1 The results of H-NMR confirmed that the obtained solid was the target [C2].

[0354] 1 H-NMR (500MHz, [D6]-DMSO): δ (ppm) = 8.02-8.03 (d, 2H), 7.79-7.81 (d, 2H), 7.69- 7.70 (d, 2H), 7.04-7.05 (d, 2H), 6.02 (s, 1H), 5.67 (s, 1H), 4.65-4.67 (d, 1H), 4.0 9-4.12 (m, 3H), 4.01-4.04 (m, 2H), 3.35-3.36 (m, 1H), 2.85-2.86 (m, 1H), 2.75-2. 76 (m, 1H), 1.88 (s, 3H), 1.73-1.76 (m, 2H), 1.64-1.66 (m, 2H), 1.41-1.48 (m, 4H).

[0355] <Example 2 of Additive Synthesis: Synthesis of [C3]>

[0356]

[0357] 4-[trans-4-[[6-[(2-methyl-1-oxo-2-propane-1-yl)oxy]hexyl]oxy]cyclohexyl]benzoic acid (19.4 g, 50 mmol), epichlorohydrin (23.1 g, 250 mmol), tetrabutylammonium chloride (2.1 g, 7.5 mmol), and DMSO (60 g) were added to a 200 mL four-necked flask and stirred at 80 °C. After the reaction was complete, the reaction system was injected into ethyl acetate (300 g), the organic layer was washed with pure water (1000 g), and the mixture was concentrated to obtain [C3-1] (25.0 g). [C3-1] was used directly in the following steps without further purification.

[0358] The [C3-1] (25.0 g) obtained above, potassium carbonate (10.4 g, 75 mmol), butylated hydroxytoluene (11.0 mg, 0.05 mmol), and MeCN (250 g) obtained above were charged into a 500 mL four-necked flask and stirred at 80 °C. After the reaction was complete, the precipitate was filtered off, and the filtrate was concentrated. The crude product was separated by silica gel column chromatography (ethyl acetate:heptane = 1:5 (v / v)) to obtain [C3] (12.7 g, two-step yield: 57%, pale yellow liquid solid). The target analyte is shown below. 1 The results of H-NMR confirmed that the obtained solid was the target [C3].

[0359] 1 H-NMR (500MHz, [D6]-DMSO): δ (ppm) = 7.89-7.91 (d, 2H), 7.39-7.40 (d, 2H), 6.01-6.02 (m, 1H), 5.6 7-5.68 (m, 1H), 4.61-4.64 (d, 1H), 4.06-4.10 (m, 3H), 3.41-3.43 (t, 2H), 3.31-3.34 (m, 1H), 3.24-3 .28(m, 1H), 2.83-2.84(t, 1H), 2.72-2.73(m, 1H), 2.56-2.61(m, 1H), 2.05-2.09(m, 2H), 1.88(s, 3 H), 1.80-1.83(d, 2H), 1.59-1.65(m, 2H), 1.46-1.54(m, 4H), 1.33-1.35(m, 4H), 1.23-1.30(m, 2H).

[0360] Synthesis of Polyimide-based Polymers

[0361] <Synthesis example 1>

[0362] B2 (5.35 g, 21.4 mmol), A2 (3.72 g, 8.6 mmol), and A1 (3.04 g, 20.0 mmol) were mixed in NMP (36.3 g) and reacted at 80 °C for 5 hours. Then, B1 (1.28 g, 6.5 mmol) and NMP (3.86 g) were added and reacted at 40 °C for 6 hours to obtain a polyamic acid solution with a resin solids concentration of 25.0% by mass.

[0363] NMP was added to the obtained polyamic acid solution (20.0 g), diluted to 6% by mass, and then acetic anhydride (4.50 g) and pyridine (3.30 g) were added as imidization catalysts. The mixture was reacted at 90 °C for 3 hours. The reaction solution was then added to methanol (400 mL), and the resulting precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 °C to obtain polyimide powder (1). The imidization rate of this polyimide was 80%, the number average molecular weight was 19600, and the weight average molecular weight was 49100.

[0364] <Synthesis example 2>

[0365] B1 (3.30 g, 16.8 mmol), A2 (5.17 g, 11.9 mmol), and A3 (1.35 g, 5.1 mmol) were mixed in NMP (39.3 g) and reacted at 25 °C for 24 hours to obtain a polyamic acid solution with a resin solid content of 20.0% by mass (2).

[0366] It should be noted that the polyamic acid solution (2) has a carboxyl group, the structure shown in the above formula (S), and a photopolymerizable group. The carboxyl group is derived from B1, the structure shown in the above formula (S) is derived from A2, and the photopolymerizable group is derived from A3.

[0367] <Synthesis Example 3>

[0368] B1 (3.30 g, 16.8 mmol), A2 (5.17 g, 11.9 mmol), and A1 (0.78 g, 5.1 mmol) were mixed in NMP (37.0 g) and reacted at 25 °C for 24 hours to obtain a polyamic acid solution with a resin solid content of 20.0% by mass (3).

[0369] Synthesis of Methacrylic Acid Polymers

[0370] <Synthesis example 4>

[0371] E1 (2.44 g, 6.80 mmol), E2 (0.40 g, 1.70 mmol), and E3 (0.73 g, 8.50 mmol) were dissolved in CHN (21.0 g). After degassing and pressure restoration with nitrogen using a diaphragm pump, AIBN (0.14 g, 0.85 mmol) as a polymerization initiator was added, followed by degassing and pressure restoration with nitrogen again. The mixture was then reacted at 60 °C for 13 hours to obtain a solution of methacrylic acid polymer (1).

[0372] Manufacturing of Orientation Film Forming Materials

[0373] The following describes a manufacturing example of an alignment film forming material. This alignment film forming material is also used in the fabrication and evaluation of liquid crystal elements.

[0374] <Example 1>

[0375] NMP (11.3 g) was added to the polyimide powder (1) (2.0 g) obtained in Synthesis Example 1, and the mixture was stirred at 70 °C for 24 hours to dissolve it. A4 (5.0% by mass NMP solution, 2.0 g) was added to this solution, and the mixture was stirred at 70 °C for 15 hours to obtain a polyimide solution (1). A specific binding compound C1 (0.2 g), NMP (9.5 g), and BCS (25.0 g) were added to this polyimide solution, and the mixture was stirred at 25 °C for 2 hours to obtain an orientation film forming material (1). No abnormalities such as turbidity or precipitation were found in this orientation film forming material, confirming it as a homogeneous solution.

[0376] <Example 2>

[0377] Specific binding compound C2 (0.2 g), NMP (9.5 g), and BCS (25.0 g) were added to the polyimide solution (1) (15.3 g) described in Example 1, and the mixture was stirred at 25°C for 2 hours to obtain an orientation film forming material (2). No abnormalities such as turbidity or precipitation were found in this orientation film forming material, confirming it as a homogeneous solution.

[0378] <Example 3>

[0379] Specific binding compound C3 (0.2 g), NMP (9.5 g), and BCS (25.0 g) were added to the polyimide solution (1) (15.3 g) described in Example 1, and the mixture was stirred at 25°C for 2 hours to obtain an orientation film forming material (3). No abnormalities such as turbidity or precipitation were found in this orientation film forming material, confirming it as a homogeneous solution.

[0380] <Example 4>

[0381] Specific binding compounds C1 (0.2 g), D3 (0.2 g), NMP (9.3 g), and BCS (25.0 g) were added to the polyimide solution (1) (15.3 g) described in Example 1, and the mixture was stirred at 25°C for 2 hours to obtain an orientation film forming material (4). No abnormalities such as turbidity or precipitation were found in this orientation film forming material, confirming it as a homogeneous solution.

[0382] <Example 5>

[0383] Specific binding compounds C1 (0.12 g), D3 (0.12 g), CHN (5.2 g), and PGME (16.8 g) were added to a solution (8.0 g) of the methacrylic polymer (1) obtained in Synthesis Example 4, and stirred at room temperature to obtain an orientation film forming material (5). No abnormalities such as turbidity or precipitation were found in this orientation film forming material, confirming it as a homogeneous solution.

[0384] <Example 6>

[0385] Specific binding compounds C2 (0.12 g), D3 (0.12 g), CHN (5.2 g), and PGME (16.8 g) were added to a solution (8.0 g) of the methacrylic polymer (1) obtained in Synthesis Example 4, and stirred at room temperature to obtain an orientation film forming material (6). No abnormalities such as turbidity or precipitation were found in this orientation film forming material, confirming it as a homogeneous solution.

[0386] <Example 7>

[0387] Specific binding compounds C3 (0.12 g), D3 (0.12 g), CHN (5.2 g), and PGME (16.8 g) were added to a solution (8.0 g) of the methacrylic polymer (1) obtained in Synthesis Example 4, and stirred at room temperature to obtain an orientation film forming material (7). No abnormalities such as turbidity or precipitation were found in this orientation film forming material, confirming it as a homogeneous solution.

[0388] <Example 8>

[0389] Specific binding compounds C1 (0.2 g), D3 (0.1 g), NMP (14.7 g), and BCS (25.0 g) were added to the polyamic acid solution (2) (10 g) obtained in Synthesis Example 2, and the mixture was stirred at 25°C for 2 hours to obtain an orientation film forming material (8). No abnormalities such as turbidity or precipitation were found in this orientation film forming material, confirming it as a homogeneous solution.

[0390] <Comparative Example 1>

[0391] NMP (9.7 g) and BCS (25.0 g) were added to the polyimide solution (1) (15.3 g) described in Example 1, and the mixture was stirred at 25°C for 2 hours to obtain an orientation film forming material (9). No abnormalities such as turbidity or precipitation were found in this orientation film forming material, confirming it as a homogeneous solution.

[0392] <Comparative Example 2>

[0393] Comparative compound D1 (0.2 g), NMP (9.5 g), and BCS (25.0 g) were added to the polyimide solution (1) (15.3 g) described in Example 1, and the mixture was stirred at 25°C for 2 hours to obtain an orientation film forming material (10). No abnormalities such as turbidity or precipitation were found in this orientation film forming material, confirming it as a homogeneous solution.

[0394] <Comparative Example 3>

[0395] Comparative compound D2 (0.2 g), NMP (9.5 g), and BCS (25.0 g) were added to the polyimide solution (1) (15.3 g) described in Example 1, and the mixture was stirred at 25°C for 2 hours to obtain an orientation film forming material (11). No abnormalities such as turbidity or precipitation were found in this orientation film forming material, confirming it as a homogeneous solution.

[0396] <Comparative Example 4>

[0397] Comparative compound D3 (0.2 g), NMP (9.5 g), and BCS (25.0 g) were added to the polyimide solution (1) (15.3 g) described in Example 1, and the mixture was stirred at 25°C for 2 hours to obtain an orientation film forming material (12). No abnormalities such as turbidity or precipitation were found in this orientation film forming material, confirming it as a homogeneous solution.

[0398] <Comparative Example 5>

[0399] CHN (5.2 g) and PGME (16.8 g) were added to a solution (8.0 g) of the methacrylic polymer (1) obtained in Synthesis Example 4, and the mixture was stirred at room temperature to obtain an orientation film forming material (13). No abnormalities such as turbidity or precipitation were found in this orientation film forming material, and it was confirmed to be a homogeneous solution.

[0400] <Comparative Example 6>

[0401] Comparative compound D1 (0.12 g), CHN (5.2 g), and PGME (16.8 g) were added to a solution (8.0 g) of the methacrylic polymer (1) obtained in Synthesis Example 4, and stirred at room temperature to obtain an orientation film forming material (14). No abnormalities such as turbidity or precipitation were found in this orientation film forming material, confirming it as a homogeneous solution.

[0402] <Comparative Example 7>

[0403] Comparative compound D2 (0.12 g), CHN (5.2 g), and PGME (16.8 g) were added to a solution (8.0 g) of the methacrylic polymer (1) obtained in Synthesis Example 4, and stirred at room temperature to obtain an orientation film forming material (15). No abnormalities such as turbidity or precipitation were found in this orientation film forming material, confirming it as a homogeneous solution.

[0404] <Comparative Example 8>

[0405] Comparative compound D3 (0.12 g), CHN (5.2 g), and PGME (16.8 g) were added to a solution (8.0 g) of the methacrylic polymer (1) obtained in Synthesis Example 4, and stirred at room temperature to obtain an orientation film forming material (16). No abnormalities such as turbidity or precipitation were found in this orientation film forming material, confirming it as a homogeneous solution.

[0406] <Comparative Example 9>

[0407] Comparative compounds D2 (0.12 g), D3 (0.12 g), CHN (5.2 g), and PGME (16.8 g) were added to a solution (8.0 g) of the methacrylic polymer (1) obtained in Synthesis Example 4, and stirred at room temperature to obtain an orientation film forming material (17). No abnormalities such as turbidity or precipitation were found in this orientation film forming material, confirming it as a homogeneous solution.

[0408] <Comparative Example 10>

[0409] Comparative compound D3 (0.1 g), NMP (14.9 g), and BCS (25.0 g) were added to the polyamic acid solution (3) (10 g) obtained in Synthesis Example 3, and the mixture was stirred at 25°C for 2 hours to obtain an orientation film forming material (18). No abnormalities such as turbidity or precipitation were found in this orientation film forming material, confirming it as a homogeneous solution.

[0410] The compositions of the orientation film-forming materials obtained in the Examples and Comparative Examples are shown in Table 1. It should be noted that the values ​​in parentheses for specific adhesion compounds and comparative compounds represent their respective contents (parts by mass) relative to 100 parts by mass of the polymer.

[0411] [Table 1]

[0412]

[0413] <Fabrication of dimming layer forming material (A)>

[0414] R1 (0.90 g), R2 (1.50 g), R3 (1.50 g), R4 (0.30 g), R5 (0.30 g), and R6 (0.50 g) were mixed and stirred at 25°C for 6 hours to prepare a solution of the polymerizable compound. Then, the prepared solution of the polymerizable compound, L1 (4.0 g), and P1 (0.10 g) were mixed and stirred at 25°C for 6 hours to obtain the dimming layer forming material (A).

[0415] "Fabrication and Evaluation of Optical Properties of Liquid Crystal Components"

[0416] Liquid crystal elements were fabricated by pressurizing and filtering the alignment film forming material of the above-described embodiments or comparative examples using a membrane filter with a pore size of 1 μm. Specifically, the alignment film forming material was rod-coated onto the ITO surface of a PET (polyethylene terephthalate) substrate (length: 150 mm, width: 150 mm, thickness: 0.2 mm) with ITO electrodes, which had been cleaned with pure water. The substrate was then heated on a hot plate at 100°C for 5 minutes, followed by a heating treatment at 120°C for 2 minutes in a thermal cycling cleaning oven, resulting in an ITO substrate with an alignment film thickness of 100 nm. Two of the obtained ITO substrates with alignment films were prepared, and a spacer with a thickness of 6 μm was coated on the alignment film surface of one of the substrates. Subsequently, the dimming layer forming material (A) was dropped onto the alignment film surface of the substrate coated with spacers using the ODF (One Drop Filling) method. Then, the alignment film surfaces of another substrate were bonded together to obtain the liquid crystal element before processing.

[0417] The liquid crystal element before treatment was irradiated with ultraviolet light using an ultraviolet irradiation device equipped with an ultraviolet light-emitting diode as the light source, at a wavelength of 365 nm, an ultraviolet irradiance of 4 mW, and an irradiation time of 250 seconds. The temperature inside the irradiation device was controlled at 25°C. Thus, a liquid crystal element (reverse-type element) was obtained.

[0418] Evaluation of optical properties (transparency and scattering properties)

[0419] The transparency without applied voltage was evaluated by measuring the haze (also known as HAZE) of the liquid crystal element in the absence of applied voltage. Specifically, the HAZE was measured using a BYK haze-gardi (TETSUTANI). In the evaluation, the lower the HAZE, the better the transparency.

[0420] The scattering characteristics under applied voltage were evaluated as follows: 48V was applied to the liquid crystal element via AC drive, and HAZE was measured under the same conditions as described above. In the evaluation, a higher HAZE indicates better scattering characteristics.

[0421] The evaluation results of the optical properties are shown in Table 2.

[0422] Evaluation of the adhesion between the liquid crystal layer and the alignment film

[0423] For the fabricated liquid crystal element, using a small benchtop testing machine EZ-SX manufactured by Shimadzu Corporation, the lower substrate was fixed to the testing table, the end of the upper substrate was fixed, and the upper substrate was stretched upwards. The peel strength (N / 25mm) between the liquid crystal layer and the alignment film was measured. The higher this value, the better the adhesion in this evaluation.

[0424] The evaluation results of the fit are shown in Table 2.

[0425] [Table 2]

[0426]

[0427] As shown in Table 2, compared with the comparative example using an alignment film forming material containing polymer component (A) and a specific adhesion compound, the liquid crystal layer and the alignment film showed improved adhesion and better optical properties in the example using an alignment film forming material that does not contain both polymer component (A) and the specific adhesion compound.

[0428] Explanation of reference numerals in the attached figures

[0429] 11: First substrate; 12, 16: Transparent electrodes; 13, 15: Liquid crystal alignment film; 14: Dimming layer; 17: Second substrate; 100: Liquid crystal element.

[0430] It should be noted that the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2021-005941 filed on January 18, 2021, and the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2021-096763 filed on June 9, 2021, are incorporated herein by reference as a disclosure of the present invention.

Claims

1. An alignment film forming material, characterized by comprising: A component and a B component containing the following, A component: a polymer component A having a carboxyl group and a structure represented by the following formula (S), wherein the polymer constituting the polymer component A is at least one polymer A selected from the group consisting of a polyimide precursor, a polyimide which is an imidized product thereof, and a polymer of a monomer having a polymerizable unsaturated bond; B component: a compound B having at least one epoxy group and one group having a polymerizable unsaturated bond in a molecule, the epoxy group and the group having a polymerizable unsaturated bond being linked via a divalent organic group having 4 to 20 carbon atoms, the compound B having a molecular weight of 2,000 or less, X represents a single bond, - (CH2) a -, -CONH-, -NHCO-, -CON (CH3) -, -NH-, -0-, -COO-, -OCO- or - ((CH2) a1 - A1) m1 -, wherein a is an integer of 1 to 15, a1 is an integer of 1 to 15, A1 represents an oxygen atom or -COO-, m1 is an integer of 1 to 2, and in the case where m1 is 2, a plurality of a1 and A1 each independently have the definition described above, J represents a monovalent organic group having at least one group selected from the group consisting of an alicyclic hydrocarbon group having 4 to 40 carbon atoms and an aromatic hydrocarbon group having 6 to 40 carbon atoms, wherein at least one of the hydrogen atoms of the alicyclic hydrocarbon group and the aromatic hydrocarbon group is substituted with a substituent selected from the group consisting of a halogen atom, a halogen atom-containing alkyl group, a halogen atom-containing alkoxy group, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, an alkenyl group having 3 to 10 carbon atoms, and a heteroatom-containing group in which a carbon-carbon bond of the halogen atom-containing alkyl group, the halogen atom-containing alkoxy group, the alkyl group, the alkoxy group, and the alkenyl group is interrupted by an oxygen atom, * represents a bonding bond, the compound B is a compound represented by the following formula (b), m is an integer of 1 to 6, P represents a group having a polymerizable unsaturated bond, R represents an organic group of valence m+1 having an alkylene group of 4 to 20 carbon atoms, the m+1-valent organic group represented by R of the formula (b) is a k2+1-valent organic group represented by the following formula (r2), or a k3+1-valent organic group represented by the following formula (r3), Ak2represents an alkylene group having 4 to 20 carbon atoms, Ak3represents a k3+1-valent acyclic aliphatic hydrocarbon group having 4 to 20 carbon atoms, A2, A3represent an alkylene group having 1 to 10 carbon atoms, Ar2 represents a k2+1-valent aromatic hydrocarbon group or a k2+1-valent alicyclic hydrocarbon group, L2, L 2’ , L 2’’ , L3, L 3’ each independently represents a single bond, -O-, -CO-, -NH-, -NHCO-, -CONH-, -OCO-, or -COO-, k2, k3 are integers of 1 to 4, m2 is an integer of 1 to 3, i2, i3 are integers of 0 to 2, In the case where two or more of Ar2, A2, A3, L2, L 2’ , L 2’’ , L3, L 3’ , i2and i3are present, two or more of Ar2, A2, A3, L2, L 2’ , L 2’’ , L3, L 3’ , i2and i3are each independently optionally the same or different, *1 represents a bonding bond to a glycidyl group, and *2 represents a bonding bond to P.

2. The alignment film-forming material according to claim 1, wherein the polymer component A: (i) contains at least one polymer A-1 selected from the group consisting of a polyimide precursor having a carboxyl group and the structure represented by the formula (S), a polyimide which is an imidized product thereof, and a polymer of a monomer having a polymerizable unsaturated bond in the same molecule, or (ii) contains at least one polymer A-2 selected from the group consisting of a polyimide precursor having a carboxyl group, a polyimide which is an imidized product thereof, and a polymer of a monomer having a polymerizable unsaturated bond, and at least one polymer A-3 selected from the group consisting of a polyimide precursor having the structure represented by the formula (S), a polyimide which is an imidized product thereof, and a polymer of a monomer having a polymerizable unsaturated bond.

3. The alignment film-forming material according to claim 1 or 2, wherein The monomer having a polymerizable unsaturated bond is a (meth)acrylic compound, a (meth)acrylamide compound, an aromatic vinyl compound, a conjugated diene compound, a maleimide group-containing compound, an α-methylene-γ-butyrolactone compound, or a vinyl compound.

4. The alignment film forming material according to claim 1, wherein The group "- (Ar2-L 2’’ ) m2 - " in the formula (r2) is an organic group represented by the following formula (w), m represents an integer of 0 to 2, ring A and ring A' each independently represent a benzene ring or a cyclohexane ring, any hydrogen atom on the benzene ring and the cyclohexane ring is optionally substituted with a monovalent organic group, L represents a single bond, -0-, -CO-, -OCO- or -COO-, *1, *2 represent a bond, *2 represents a bond to Ak2, in the case where two or more of L and ring A are present, the two or more of L and ring A are each independently optionally the same or different.

5. The alignment film forming material according to claim 1 or 2, wherein The group having a polymerizable unsaturated bond is a (meth)acryloyloxy group, a styryl group, a (meth)acrylamide group, a vinyl group, a vinylidene group, a vinyloxy group, that is, CH2=CH-O-, or a maleimide group.

6. The alignment film forming material according to claim 1 or 2, wherein The compound B is represented by any one of the following formulae (b-1) to (b-10), 。 7. The alignment film forming material according to claim 6, wherein The compound B is represented by the following formula (C2) or (C3), 。 8. The alignment film forming material according to claim 1 or 2, wherein The polymer component A contains at least one polymer selected from the group consisting of a polyimide precursor having a carboxyl group and the structure represented by the formula (S) in the same molecule and a polyimide as an imidization product thereof.

9. The alignment film forming material according to claim 1 or 2, wherein The polymer component A contains at least one polymer selected from a polymer of a monomer having a polymerizable unsaturated bond having a carboxyl group and the structure represented by the formula (S) in the same molecule.

10. The alignment film forming material according to claim 1 or 2, wherein The structure represented by the formula (S) is a structure represented by any one of the following formulae (S1) to (S2), X 1 represents a single bond, - (CH2) a -, - CONH-, - NHCO-, - CON (CH3) -, - NH-, - O-, - COO-, - OCO- or - ( (CH2) a1 - A1) m1 -, wherein a is an integer of 1 to 15, a1 is an integer of 1 to 15, A1 represents an oxygen atom or - COO-, m1 is an integer of 1 to 2, and in the case where m1 is 2, a plurality of a1 and A1 each independently have the above definition, G 1 represents a divalent cyclic group selected from a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms and a divalent alicyclic hydrocarbon group having 4 to 8 carbon atoms, any hydrogen atom on the cyclic group being optionally substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom-containing alkyl group having 1 to 3 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom, m is an integer of 1 to 4, and in the case where m is 2 or more, a plurality of X 1 , G 1 each independently has the definition, R 1 represents a fluorine atom, a fluorine atom-containing alkyl group having 1 to 10 carbon atoms, a fluorine atom-containing alkoxy group having 1 to 10 carbon atoms, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or an alkoxyalkyl group having 3 to 10 carbon atoms, X 2 represents -CONH-, -NHCO-, -O-, -CH2O-, -OCH2-, -COO- or -OCO-, G 2 represents a structure having a steroid skeleton, at least one of the hydrogen atoms of which is substituted with a substituent selected from the group consisting of a halogen atom, a halogen atom-containing alkyl group, a halogen atom-containing alkoxy group, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, an alkenyl group having 3 to 10 carbon atoms, and a heteroatom-containing group in which a carbon-carbon bond of the halogen atom-containing alkyl group, the halogen atom-containing alkoxy group, the alkyl group, the alkoxy group or the alkenyl group is interrupted by an oxygen atom.

11. The alignment film forming material according to claim 1 or 2, wherein In the case where the polyimide precursor has a carboxyl group, the carboxyl group possessed by the polyimide precursor is derived from a tetracarboxylic dianhydride or a derivative thereof.

12. The alignment film forming material according to claim 1 or 2, wherein In the case where the polyimide precursor has a carboxyl group, the carboxyl group possessed by the polyimide precursor is derived from a diamine selected from 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, and diamines represented by the following formulae (3b-1) to (3b-4), In formula (3b-1), A 1 represents a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -0-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH20-, -OCH2-, -COO-, -OCO-, -CON(CH3)-, or -N(CH3)CO-, each of m1 and m2 independently is an integer of 0 to 4, and m1+m2 is an integer of 1 to 4, in formula (3b-2), each of m3 and m4 independently is an integer of 1 to 5, in formula (3b-3), A 2 represents a linear or branched alkyl group having 1 to 5 carbon atoms, and m5 is an integer of 1 to 5, in formula (3b-4), A 3 and A 4 each independently represents a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -0-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CH20-, -OCH2-, -COO-, -OCO-, -CON(CH3)-, or -N(CH3)CO-, and m6 is an integer of 1 to 4.

13. The alignment film forming material according to claim 1 or 2, wherein In the case where the polyimide precursor has the structure represented by the formula (S), the structure represented by the formula (S) possessed by the polyimide precursor is derived from an aromatic diamine d having the structure represented by the formula (S) in a side chain.

14. The alignment film forming material according to claim 13, wherein The aromatic diamine d is a diamine represented by the following formula (d1) or (d2), X represents a single bond, -0-, -C(CH3)2-, -NH-, -CO-, - (CH2) m -, -SO2-, -0-(CH2) m -, -0-C(CH3)2-, -CO-(CH2) m -, -NH-(CH2) m -, -SO2-(CH2) m -, -CONH-(CH2) m -, -CONH-(CH2) m -NHCO-, or -COO-(CH2) m -OCO- bivalent organic group, m is an integer of 1 to 8, Y represents the structure shown in said formula (S), in said formula (d2), two Ys are optionally the same or different from each other.

15. The alignment film forming material according to claim 1 or 2, wherein The polyimide precursor is obtained using a diamine component including an aromatic diamine d having the structure shown in the formula (S) in a side chain and a tetracarboxylic acid component and a photoreactive diamine, wherein the photoreactive diamine is at least one diamine selected from the group consisting of a diamine having a photo-orienting group, a diamine having a photopolymerizable group at a terminal, a diamine having a radical initiation function, and a diamine having a photosensitive function.

16. The alignment film-forming material according to claim 1 or 2, wherein The polymer component A further has a photopolymerizable group.

17. The alignment film-forming material according to claim 16, wherein In the case where the polyimide precursor has a photopolymerizable group, the photopolymerizable group possessed by the polyimide precursor is derived from a diamine having a photopolymerizable group at a terminal represented by any one of the following formulae (4b-1) to (4b-12), n1 is an integer from 2 to 12, n2 is an integer from 0 to 12 and n3 is an integer from 2 to 12.

18. The alignment film-forming material according to claim 1 or 2, wherein In the case where the polymer of the monomer having a polymerizable unsaturated bond has a carboxyl group and / or the structure shown in the formula (S), the carboxyl group and / or the structure shown in the formula (S) possessed by the polymer of the monomer having a polymerizable unsaturated bond is derived from a compound selected from the group consisting of a carboxyl group-containing (meth)acrylate compound, a vinyl group-containing aromatic carboxylic acid, a carboxyl group-containing maleimide, a carboxyl group-containing (meth)acrylamide compound, and a compound represented by the following formula (S-mA), P represents a (meth)acryloyloxy group, a styryl group, a vinyloxy group, i.e., CH2=CH-O-, a maleimide group, or an α-methylene-γ-butyrolactone structure, X, J have the same meanings as X, J in the formula (S), wherein, in the case where P is a (meth)acryloyloxy group, a vinyloxy group, i.e., CH2=CH-O-, or a maleimide group, X represents a single bond, - (CH2) a a1 m1 -, wherein a is an integer of 1 to 15, a1 is an integer of 1 to 15, A1 represents an oxygen atom or -COO-, m1 is an integer of 1 to 2, in the case where m1 is 2, a plurality of a1 and A1 each independently have the definitions described above, and J represents the same group as J in the formula (S).​​ 19. The alignment film-forming material according to claim 1 or 2, wherein The content of the compound B contained in the alignment film-forming material is 0.1 to 30 parts by mass with respect to 100 parts by mass of the total of the polymer components A.

20. The alignment film-forming material according to claim 1 or 2, wherein The alignment film-forming material is a material for forming an alignment film of a high-molecular dispersion type liquid crystal element.

21. The alignment film-forming material according to claim 1 or 2, wherein The alignment film-forming material further contains at least one additive selected from the group consisting of a crosslinkable compound other than the compound B, a functional silane compound, a metal chelate, a curing accelerator, a surfactant, an antioxidant, a sensitizer, a preservative, a compound for adjusting the dielectric constant and the resistance of an alignment film, an orienting additive other than the compound B, a photogeneration radical agent, a photoacid generator, a photoalkali generator, an ultraviolet absorber, and a light stabilizer.

22. An alignment film formed using the alignment film-forming material according to any one of claims 1 to 21.

23. A high-molecular dispersion type liquid crystal element provided with the alignment film according to claim 22.

24. A method for producing a high-molecular dispersion type liquid crystal element, comprising the following steps (1) to (4): (1) a step of applying the alignment film-forming material according to any one of claims 1 to 21 to one or both of a pair of substrates with electrodes; (2) a step of performing baking on a coating film formed on the substrate of the (1); (3) a step of disposing a light-adjusting layer forming material; and (4) a step of polymerizing the light-adjusting layer forming material to form a light-adjusting layer containing a polymer phase and a liquid crystal phase.

25. An alignment film forming agent for a polymer-dispersed liquid crystal element, comprising the alignment film forming material according to any one of claims 1 to 21.

Images